Section C

METALS

© Her Majesty the Queen in

Right of the Province of British Columbia
2015
All Rights Reserved
 TABLE OF CONTENTS
SECTION C Metals

INTRODUCTION.........................................................................................................................................4

1.0 SAMPLE PREPARATION .............................................................................................................4

1.1 Aqueous Samples ..........................................................................................................................5
1.1.1 Digestion for Total Metals in Water - Prescriptive ............................................................5
1.1.2 Total and Dissolved Mercury in Water by Bromine Monochloride Digestion – PBM ......10
1.1.3 Total Mercury Digestion ..................................................................................................14
1.2 Non-Aqueous Samples ................................................................................................................16
1.2.1 Strong Acid Leachable Metals (SALM) in Soil - Prescriptive ..........................................16
1.2.2 Digestion of Biota (Tissues, Vegetation) .........................................................................23
1.2.3 Metals in Animal Tissue and Vegetation (Biota) - Prescriptive .......................................24

2.0 INSTRUMENTAL ANALYSIS .................................................................................................... 30

2.1 Atomic Absorption – Direct Flame and Graphite Furnace Methods ............................................30
2.1.1 Introduction .....................................................................................................................30
2.1.2 Method Summary ............................................................................................................30
2.1.3 Definition of Terms ..........................................................................................................32
2.1.4 Interferences ...................................................................................................................33
2.1.5 Apparatus ........................................................................................................................34
2.1.6 Reagents .........................................................................................................................35
2.1.7 Preparation of a Standard Addition Plot .........................................................................36
2.1.8 General Procedure for Analysis by Atomic Absorption ...................................................37
2.1.9 Quality Control for Water Analysis ..................................................................................39
2.2 Hydride Vapour Generation Sample Introduction (HVAAS/HVICP) ............................................40
2.2.1 Introduction .....................................................................................................................40
2.2.2 Method Summary ............................................................................................................40
2.2.3 Interferences ...................................................................................................................40
2.2.4 General Procedure ..........................................................................................................41
2.3 Cold Vapour Generation Sample Introduction (CVAAS) .............................................................41
2.3.1 Introduction .....................................................................................................................41
2.3.2 Method Summary ............................................................................................................41
2.3.3 Interferences and Precautions ........................................................................................41
2.3.4 General Procedure ..........................................................................................................41
2.4 Inductively Coupled Plasma – Atomic Emission Spectrometry (ICP-AES) .................................42
2.4.1 Introduction .....................................................................................................................42
2.4.2 Method Summary ............................................................................................................42
2.4.3 Detection Limits...............................................................................................................42
2.4.4 Interferences and Precautions ........................................................................................43
2.4.5 General Procedure ..........................................................................................................44
2.4.6 Precision .........................................................................................................................46
2.4.7 Accuracy .........................................................................................................................47
2.4.8 Quality Control ................................................................................................................47
2.4.9 References ......................................................................................................................47
2.4.10 Revision History ..............................................................................................................47
2.5 Metal Analysis of Solids by ICP ...................................................................................................48

3.0 SPECIFIC ELEMENTAL CONDITIONS ..................................................................................... 49

Trace Metals Analysis by ICP-MS – PBM.................................................................................................50
Aluminum (Atomic Absorption - Direct Aspiration) ....................................................................................55
Antimony (Atomic Absorption - Direct Aspiration) .....................................................................................57
Antimony (Atomic Absorption - Gaseous Hydride) ...................................................................................59
Antimony (Atomic Absorption - Graphite Furnace) ...................................................................................61
Antimony (Atomic Emission - Inductively Coupled Argon Plasma {ICAP}) ...............................................63

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Arsenic (Atomic Absorption - Direct Aspiration) ........................................................................................65
Arsenic (Atomic Absorption - Gaseous Hydride) ......................................................................................67
Arsenic (Atomic Emission - Inductively Coupled Argon Plasma {ICAP}) ..................................................69
Arsenic Analysis of Solids by HVGAA ......................................................................................................71
Arsenic, Cadmium and Lead in Solids by GFAA ......................................................................................73
Soluble Barium by Calcium Chloride Extraction - Prescriptive .................................................................76
Barium (Atomic Absorption - Direct Aspiration) ........................................................................................79
Barium (Atomic Absorption - Graphite Furnace) .......................................................................................81
Boron, Hot Water Soluble (Prescriptive) ...................................................................................................83
Cadmium (Atomic Absorption - Direct Aspiration) ....................................................................................86
Cadmium (Atomic Absorption - Graphite Furnace) ...................................................................................88
Cadmium (Atomic Emission - Inductively Coupled Argon Plasma {ICAP}) ..............................................90
Calcium (Atomic Absorption - Direct Aspiration) .......................................................................................92
Chromium (Atomic Absorption - Direct Aspiration) ...................................................................................94
Chromium (Atomic Absorption - Graphite Furnace) .................................................................................96
Chromium (Atomic Emission - Inductively Coupled Argon Plasma {ICAP}) .............................................98
Chromium, Hexavalent in Water – PBM .................................................................................................100
Hexavalent Chromium in Solids by Alkaline Digestion - PBM ................................................................103
Trivalent Chromium in Solids by Calculation ..........................................................................................107
Cobalt (Atomic Absorption - Direct Aspiration) .......................................................................................110
Cobalt (Atomic Absorption - Graphite Furnace) ......................................................................................112
Copper (Atomic Absorption - Direct Aspiration) ......................................................................................114
Copper (Atomic Absorption - Graphite Furnace) ....................................................................................116
Copper (Atomic Emission - Inductively Coupled Plasma {ICAP}) ...........................................................118
Iron (Atomic Absorption - Direct Aspiration) ............................................................................................120
Iron (Atomic Absorption - Graphite Furnace) ..........................................................................................122
Lead (Atomic Absorption - Direct Aspiration) ..........................................................................................124
Lead (Atomic Absorption - Graphite Furnace) ........................................................................................126
Lead (Atomic Emission - Inductively Coupled Argon Plasma {ICAP}) ....................................................128
Lead in Solids by Flame AA ....................................................................................................................130
Magnesium (Atomic Absorption - Direct Aspiration) ...............................................................................132
Manganese (Atomic Absorption - Direct Aspiration) ...............................................................................134
Manganese (Atomic Absorption - Graphite Furnace) .............................................................................136
Mercury (Atomic Absorption - Cold Vapour) ...........................................................................................138
Mercury in Solids by Semi-automated Cold Vapour Atomic Absorption (CVAA) ...................................140
Molybdenum (Atomic Absorption - Direct Aspiration) .............................................................................143
Molybdenum (Atomic Absorption - Graphite Furnace) ...........................................................................145
Nickel (Atomic Absorption - Direct Aspiration) ........................................................................................147
Nickel (Atomic Absorption - Graphite Furnace) ......................................................................................149
Potassium (Atomic Absorption - Direct Aspiration) .................................................................................151
Selenium (Atomic Absorption - Direct Aspiration) ...................................................................................153
Selenium (Atomic Absorption - Graphite Furnace) .................................................................................155
Selenium (Atomic Absorption - Gaseous Hydride) .................................................................................157
Selenium (Atomic Emission - Inductively Coupled Argon Plasma {ICAP}) .............................................159
Silver (Atomic Absorption - Direct Aspiration) .........................................................................................161
Silver (Atomic Absorption - Graphite Furnace) .......................................................................................163
Sodium (Atomic Absorption - Direct Aspiration)......................................................................................165
Tin (Atomic Absorption - Direct Aspiration) .............................................................................................167
Tin (Atomic Absorption - Gaseous Hydride) ...........................................................................................169
Uranium, Total or Dissolved ....................................................................................................................171
Zinc (Atomic Absorption - Direct Aspiration) ...........................................................................................173
Zinc (Atomic Absorption - Graphite Furnace) .........................................................................................175

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 Metals
Revision Date: December 31, 2000

INTRODUCTION

The following sections are divided into various topics including:

1.0 Sample Preparation

2.0 Instrumental Analysis

3.0 Specific Elemental Conditions

The intent of these methods is not to exclude other techniques but, rather, to provide information on the
most commonly used protocols. Other acceptable techniques are encouraged providing equivalent or
better performance can be established.

The routine methods proposed in the manual include various atomic spectroscopy techniques. Not all
elements have been covered for each technique even though it may be practical to use that method. For
instance, ICP is well suited for the analysis of calcium although only atomic absorption is described in the
element specific section. Refer to the ICP section 2.4 for a list of capabilities and the associated
detection levels.

Additionally, not all elements are represented in this manual at this time. Future revisions will likely
include these methods as well as any updated information available.

Metals
Revision Date: December 31, 2000

1.0 SAMPLE PREPARATION

Introduction
Environmental samples submitted to a laboratory for metals analyses are subject to a variety of special
handling needs and precautions. The following serves to alert the analyst to most of the common
concerns encountered. Refer to the QA/QC section for additional information.

Sample Contamination
Due to the abundance and mobility of many metals, caution must always be taken to eliminate potential
contamination sources. This includes all materials that contact the samples, exposure to dust and fumes
and reagents used in the preservation, preparation and analysis procedures. All procedures must be
reviewed and appropriate measures taken to address these concerns. Concurrent analysis of method
blanks must be carried out to monitor contamination.

Sample Homogeneity
The ability to obtain a representative subsample for analysis is one of the most important steps in the
measurement process. The analyst must always ensure that samples are properly homogenized and
subsampled prior to analysis. If a unique physical property prohibits this, the analyst must note this
information and alert others of this concern.

Unique Characteristics
Many samples contain physical or chemical attributes that can affect the performance of the analysis
method used. Since most analytical protocols do not address unusual sample characteristics, the analyst
must occasionally make modifications to procedures. These modifications must be validated through
appropriate method validation procedure.

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Sample/Extract Stability
The stability of metals must be considered before, during and after sample preparation. Losses of some
volatile elements could occur during drying and heating operations. In addition, chemical and physical
changes such as precipitation, absorption, adsorption, oxidation, etc., should be considered at all times.
As a general rule, samples should be prepared and analyzed as soon as practical after submission to the
laboratory. Guidelines such as the “EPA Holding Times” exist for many parameters indicating typical
stability of elements in solution.

1.1 Aqueous Samples

Metals
Revision Date: Nov 6, 2015

1.1.1 Digestion for Total Metals in Water - Prescriptive

Parameters Total Metals in Water

Parameter List & This method is applicable to the following parameters:

EMS Codes
EMS EMS EMS
Parameter Parameter Parameter Parameter Parameter Parameter
Code Code Code
Aluminum AL-T Iron FE-T Silver AG-T
Antimony SB-T Lead PB-T Sodium NA-T
Arsenic AS-T Lithium LI-T Strontium SR-T
Barium BA-T Magnesium MG-T Thallium TL-T
Beryllium BE-T Manganese MN-T Thorium TH-T
Bismuth BI-T Mercury HG-T Tin SN-T
Boron B-T Molybdenum MO-T Titanium TI-T
Cadmium CD-T Nickel NI-T Uranium U-T
Calcium CA-T Phosphorus P-T Vanadium V-T
Chromium CR-T Potassium K-T Zinc ZN-T
Cobalt CO-T Selenium SE-T
Copper CU-T Silicon SI-T

EMS Method Code: Refer to EMS Parameter Dictionary on the ministry website
for current EMS codes. EMS Method Codes vary by instrumental technique.

Other metals may be analyzed by this method if acceptable performance is

demonstrated and validated.

Introduction This method was prepared for BC MOE by the BCELTAC to provide improved
consistency of results for total metals in water. All definitive elements of the
method have been prescribed to minimize inter-laboratory variability.

This method uses a prescribed mixture of nitric and hydrochloric acids with a
standardized digestion time and temperature. Laboratories are allowed some
flexibility regarding apparatus and heating methods, but variations in acid type or
concentration, digestion time, or digestion temperature are not permitted.

This method is BC MOE approved for the digestion of 34 metals in waters,

including mercury (subject to performance requirements being met). However,
other methods are also available for mercury, including potassium permanganate
/ potassium persulfate digestion and bromine monochloride oxidation.

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Method Summary Samples are digested with a mixture of nitric and hydrochloric acids. Instrumental
analysis of sample extracts can be performed by a variety of analytical methods.
This method provides the sample preparation procedure for the analysis of total
metals. Total metals include all metals, inorganically and organically bound, both
dissolved and particulate (APHA 3030A). The terms total metals and total
recoverable metals are used interchangeably, and are defined as the
concentration of analyte measured in an unfiltered aqueous sample following
treatment by refluxing with hot dilute mineral acid (US EPA 200.2).

Digestion by this procedure is required for total metals analysis of any water
sample with turbidity >1 NTU, or for any sample that is visibly coloured, or that
has any noticeable odour. Colourless samples with no apparent odour that are
verified by measurement to have turbidity <1 NTU are either analyzed as
received, or are digested.
This method is prescriptive. It must be followed exactly as described. Where
minor deviations are permitted, this is indicated in the text.

Method Limitation This digestion procedure may not be sufficiently vigorous to solubilize all
particulate metals in the sample. Even in these cases, this method does provide
a conservative measure of environmentally or ecologically available metals.
This method is suitable for digestion of water samples containing silver
concentrations of up to 0.1 mg/L (US EPA 200.2). Samples containing higher
levels of silver must be diluted prior to digestion by this procedure.
The solubility and stability of barium is limited in the presence of free sulfate using
this method (US EPA 200.2).
This method is not suitable for the determination of volatile low boiling point
organo-mercury compounds (US EPA 200.2).
Some volatile selenium species (e.g. dimethyl selenide) may be lost or only
partially recovered by this procedure.
Matrix Water, including fresh water, marine water, brackish water, and waste water.

Interferences and The interferences encountered will differ depending on the instrumental method
Precautions used to analyze the sample extracts. Interferences should be clearly outlined and
controlled in the analysis procedure. High concentrations of acids may cause
physical interferences with some instrumental techniques.

Sampling, Handling Sampling should be done by qualified personnel. Samples must be collected and
and Preservation stored such that degradation or alteration of the sample is minimized.

Metals other than Mercury: Collect samples in clean high density polyethylene
(HDPE), glass, or Polytetrafluoroethylene (PTFE) containers. Preserve in the
field with nitric acid to pH < 2. Treatment of samples with approximately 3 mL of
1:3 HNO3 : Deionized water per 250 mL sample is recommended. Adding nitric
acid to the original sample container at the laboratory within 14 days of sampling
is an acceptable alternative to field preservation (equilibrate ≥ 16 hours prior to
sub-sampling).
Mercury: Collect samples using only glass or PTFE containers. Field-preserve
with HCl to pH < 2. Adding BrCl to the original sample container at the laboratory
within 28 days of sampling is an acceptable alternative to field preservation (use ≥
5 mL BrCl solution per litre of sample, equilibrate ≥ 24 hours prior to sub-
sampling).

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Stability Holding Time:
Metals (excluding Mercury): 6 months
Mercury: 28 days

Results reported for samples digested beyond holding times must be qualified.

Storage: No storage temperature requirement (US EPA 40CFR May 18, 2012).

Equipment and 1. Heating source (e.g. block digester, hotplate, water bath) capable of
Supplies maintaining a sample extract temperature of 95 ± 5°C.
2. Acid dispensers.
3. Vapour refluxing cover to fit digestion vessel (e.g. reflux cover, watch glass,
etc.).
4. Digestion Vessels (e.g. block digester tube, beaker, flask, etc.).
5. Gloves.
6. Filters (optional; filtration through large pore size filters, e.g. 20 – 25 µm, may
be necessary for filtration of some samples prior to analysis).
7. Filter funnels (optional).
8. Glass thermometer or suitable temperature sensor.

Reagents 1. Nitric acid (HNO3), concentrated (67 - 70%), ACS or reagent grade minimum.
2. Hydrochloric Acid (HCl), concentrated (36 - 40%), ACS or reagent grade
minimum.
3. Water, de-ionized (ASTM Type I or equivalent recommended).
Safety Wear appropriate PPE (Personal Protective Equipment) including lab coat,
gloves, and safety glasses. Add acid to samples and perform digestions under a
fume hood.
Procedure Samples are prepared and digested using the following procedures:
No-Digestion Option for Samples with Low Turbidity
Digestion is not required for single-phase samples with measured turbidity <1
NTU with no visible colour and no discernable odour. To qualify for this
exception, measured turbidity values from the raw (unacidified) cut, or from the
acidified total metals cut must be measured and recorded. If the raw cut is used
for turbidity measurement, visually confirm that no precipitates exist in the
acidified portion.
For samples that were not acidified in the field, acidify with HNO 3 to pH <2.
Shake the sample to mix. Let samples stand in their original containers for at
least 16 hours prior to analysis to allow potentially adsorbed metals to re-dissolve.
Apply appropriate qualifiers to any total metals samples that have not been
allowed to equilibrate for this time. No further preparation is required.
Digestion is required for all samples that do not meet the above criteria for
turbidity, colour, odour and phase.
Sample Preparation - Digestion
For samples that were not acidified in the field, acidify with HNO 3 to pH < 2.
Shake the sample to mix. Let samples stand in their original containers for at
least 16 hours prior to analysis to allow potentially adsorbed metals to re-dissolve.
Apply appropriate qualifiers to any total metals samples that have not been
allowed to equilibrate for this time.

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The following procedure uses a 50 mL sub-sample. Sample volume may be
scaled up or down if the ratios of HNO3 or HCl to sample are not changed.
1. Shake the sample well to homogenize before sub-sampling for digestion.
2. Take a 50 ± 1 mL sub-sample and dispense the sample into a digestion
vessel, which must be fitted with a reflux cap and which must be capable of
supporting open vessel reflux action. Examples of digestion vessels fitted
with a reflux cap include a beaker fitted with a watch glass, or an Erlenmeyer
flask or digestion tube fitted with a reflux cover or watch glass. Include
Method Blanks, Lab Duplicates and Reference Materials or Laboratory
Control Samples with each batch of samples.
3. Add 1.0 ± 0.1 mL conc. HNO3 and 0.50 ± 0.05 mL conc. HCl to each sample
(assuming 50 mL sample size).
4. Prepare a Method Blank for every batch of samples. Add 50 ± 1 mL of de-
ionized water into a digestion vessel. Add 1.0 ± 0.1 mL of conc. HNO 3 and
0.50 ± 0.05 mL conc. HCl to the water.
5. Prepare a Reference Material or Laboratory Control Sample for every batch
of samples. Add 50 ± 1 mL of the RM or LCS solution into a digestion vessel.
Add 1.0 ± 0.1 mL of conc. HNO3 and 0.50 ± 0.05 mL conc. HCl to the water.
6. Prepare at least one duplicate for every batch of samples.
7. Cover samples with a reflux cover or watch glass and digest for 2.0 – 2.5
hours at 95 ± 5°C (this excludes the time needed to pre-heat the samples to
95°C). The heat for digestion must maintain the sample extract temperature
at 95 ± 5°C. This refers to the temperature of the sample extract in a
digestion vessel covered with a reflux cap, not the temperature setting on the
heating source, and not the temperature of an uncovered digestion vessel. It
is recommended that the sample extract temperature be monitored and
recorded with each batch, using 50 ± 1 mL de-ionized water with 1.0 ± 0.1 mL
conc. HNO3 and 0.50 ± 0.05 mL conc. HCl.
8. After 2.0 – 2.5 hours at 95 ± 5°C, remove the samples from heat source and
let cool for at least 30 minutes (this will reduce any potential harmful fumes
from the sample).
9. Remove the reflux cover or watch glass and reconstitute sample(s) back to 50
± 1 mL with de-ionized water. Shake samples to mix. It is not necessary to
rinse the condensation from the reflux cover or watch glass back into the
sample tube.
10. Analyze the digested sample using appropriate analytical methods. If
significant solids are present in the sample after digestion, decant, centrifuge,
or filter the sample prior to analysis to prevent sample introduction issues. If
any sample extracts are filtered, the method blank must also be filtered.
11. Record and report any anomalies observed during the digestion and analysis.

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Quality Control Summary of QC Requirements
Method QC Component Minimum Frequency Minimum Data Quality
Objectives*
Method Blank 1 per batch Less than reported DL
(max 20 samples)
Reference Material or 1 per batch 80 - 120%
Laboratory Control Sample (max 20 samples)
Matrix Spike 1 per batch 70 - 130%
(recommended) (recommended) (recommended)
Lab Duplicates ≥ 5% ≤ 20% RPD
Field Duplicates Recommended None Specified
* Minimum DQOs apply to individual QC samples at levels above 10x MDL. Laboratories must report
qualified data when DQOs are not met.

Method Validation Initial Method Validation requirements as outlined below must be completed before
Requirements this method may be used to generate results for unknown samples. The method
must be re-evaluated periodically (every two years is recommended as a suitable
frequency). Prepared validation samples must be analyzed by all instrument
methods used for routine analysis.
Demonstration of Accuracy and Precision
Prepare and analyze at least 8 replicates of a Reference Material or Laboratory
Control Sample.
Where the above Reference Material or Laboratory Control Sample is utilized for
routine QC purposes, re-validations should be conducted using all routine QC data
available for the review period.
Accuracy is measured as Percent Difference from the targets for the Reference
Material or Laboratory Control Sample. For each metal, average accuracy must
be within 90-110% of the targets, for results ≥ 5 times the Reported Detection
Limit. Precision must be <10% RSD for results ≥ 5 times the Reported Detection
Limit.
References US EPA Method 200.2, Sample Preparation Procedure for Spectrochemical
Determination of Total Recoverable Elements, National Exposure Research
Laboratory, Office of Water, US EPA, Cincinnati, OH, October 1999.
APHA 3030A, Preliminary Treatment of Samples – Introduction, 2004.
US EPA 40CFR, Table II, Required Containers, Preservation Techniques, and
Holding Times, May 18, 2012.
Revision History Nov 6, 2015 Updated “total metals” definition reference to APHA 3030A.
Updated EPA 40CFR reference to 2012 version. Removed
requirement that 1% solids by weight must be digested with
SALM procedure. Added recommendation for Matrix Spike in QC
section. Updated preservations for mercury to current BC MOE
requirements.
Oct 1, 2013 Replaces BC Lab Manual Methods (December 31, 2000) “Nitric
Acid Digestion for Water Samples” and “Nitric Acid Digestion for
Turbid Water Samples”. Effective October 1, 2013, the use of
this method is required for listed metals, other than mercury, for
BC CSR analysis purposes.

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 Metals
Revision Date: October 1, 2013

1.1.2 Total and Dissolved Mercury in Water by Bromine Monochloride Digestion – PBM

Parameter Total and Dissolved Mercury in Water

Analytical Method Bromine monochloride digestion (followed by appropriate instrumental analysis).

Introduction This method is applicable to the analysis of total or dissolved mercury in water
samples. Bromine monochloride is an extremely strong oxidizer, and is highly
efficient at converting elemental, organic, and inorganic mercury species (including
particulate bound species) to Hg(II). Full oxidation of all mercury species is
necessary to facilitate complete reaction with stannous chloride (SnCl 2), as used
by cold vapour atomic absorption or atomic fluorescence spectroscopic methods.

Method Summary Samples are digested with bromine monochloride. Instrumental analysis of
sample extracts can be performed by a variety of analytical methods (e.g. cold
vapour atomic absorption or fluorescence spectrometry with SnCl2 reduction).

This method is performance-based. Laboratories may adopt alternative options to

improve performance or efficiency provided that all stated performance
requirements and prescribed (mandatory) elements are met.

MDL and EMS Analyte Approx. MDL (units) EMS Code

Codes
Total Mercury 0.00001 mg/L HG-T
Dissolved Mercury 0.00001 mg/L HG-D

Matrix Water, including fresh water, marine water, brackish water, and waste water.

Interferences and The interferences encountered will differ depending on the instrumental method
Precautions used to analyze the sample extracts. These interferences should be clearly
outlined and controlled in the analysis procedure.

Samples high in organic matrices (e.g. sewage effluent), may require higher levels
of BrCl and longer oxidation times, or elevated temperatures (e.g., place sealed
bottles in oven at 50°C for 6 hours). Sample oxidation must be continued until
complete, which is determined by observation of a permanent yellow colour
remaining in the sample, or by the use of starch iodide indicating paper to test for
residual free oxidizer. If necessary, these types of samples can be diluted prior to
digestion with BrCl.

It is critical that significant care is taken to avoid contamination when collecting

and analyzing samples for trace levels of mercury. Refer to US EPA 1669
Sampling Ambient Water for Trace Metals at EPA Water Quality Criteria Levels.

Gold and iodide (at levels above 3 mg/L) have been reported as interferences (US
EPA 1631E). Pre-reducing the sample with SnCl2 can minimize the interference
from iodide.

Clean room conditions are recommended for sample handling and preparation
steps prior to trace level mercury analyses (e.g. below ~ 0.00001 mg/L).

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Sample Handling Sample containers: Glass or PTFE only. Mercury vapours can diffuse through
and Preservation HDPE containers, which can cause either high or low biases.

Preservation: HCl to pH <2 or BrCl (field). Total mercury samples should be field
preserved with HCl or BrCl. Dissolved mercury samples should be field filtered
(0.45µm) and field preserved with HCl or BrCl (lab-filtered results may be low
biased, and must be qualified). For total mercury and for dissolved mercury if field
filtered, an acceptable alternative is to add BrCl to the original sample container
(within 28 days of sampling, 5 mL BrCl solution per L of sample), and to let the
sample oxidize for at least 24 hours prior to sub-sampling or analysis.

Sample collection in HDPE containers and/or preservation with HNO3 are no

longer considered to be recommended practices due to recently highlighted
stability issues. Samples received in HDPE containers or preserved with HNO3
must be qualified.

When samples for dissolved mercury are filtered, filter blanks should be prepared
under the same conditions and analyzed together with the samples.

Field preservation with BrCl is not recommended due to the hazards associated
with this reagent.

Stability Holding Time: Total and Dissolved Mercury: 28 days from sampling.

Results reported for samples digested or analyzed beyond holding times must be
qualified.

Storage: No storage temperature requirement.

Equipment and 1. Acid and reagent dispensers

Supplies 2. Digestion vessels
3. Gloves
4. Spatula
5. Balance, minimum 2 decimal place

Reagents 1. Nitric acid (HNO3), concentrated (67 - 70%), ACS or reagent grade minimum.
2. Hydrochloric acid (HCl), concentrated (36 - 40%), ACS or reagent grade
minimum.
3. Water, de-ionized (ASTM Type I or equivalent recommended).
4. Potassium bromate (KBrO3), ACS or reagent grade minimum.
5. Potassium bromide (KBr), ACS or reagent grade minimum.
.
6. Hydroxylamine hydrochloride (NH2OH HCl), ACS or reagent grade minimum.
7. Stannous chloride (SnCl2), ACS or reagent grade minimum.

As per US EPA 1631E, it is permissible to use quantities of reagents and

procedures other than those suggested in this method, as long as equivalent
performance is demonstrated by the laboratory.

Preparation of Bromine Monochloride (BrCl) Solution:

In a fume hood, dissolve 27 ± 1 g of KBr in 2.5 ± 0.1 L of HCl. Stir for

approximately 1 hr in a fume hood using a clean magnetic stir bar, while slowly
adding 38 ± 1 g KBrO3 to the acid. The solution colour should change from yellow
to red to orange, after all of the KBrO3 has been added. Loosely cap the bottle,
and allow stirring for another hour before tightening the lid.

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 WARNING: Free halogens (Cl2, Br2, BrCl) are generated from this process, which
are released from the bottle. The addition of KBrO3 must be performed slowly in a
fume hood!

Alternatively, commercially prepared BrCl solution may be used, as long as the

same reagent concentrations are maintained, or equivalent performance is
demonstrated by the laboratory.
.
Preparation of Hydroxylamine Hydrochloride (NH2OH HCl) Solution:
.
Dissolve 300 ± 5 g of NH2OH HCl in reagent water and dilute to a 1.0 L final
volume. If necessary, this solution may be purified by the addition of 1.0 ± 0.1 mL
of SnCl2 solution and purging overnight with nitrogen.

Safety Wear appropriate PPE (Personal Protective Equipment) including lab coat, gloves,
and safety glasses. Add acid to samples and perform digestions under a fume
hood.

Due to the toxicological and physical properties of Hg, pure standards should be
handled only by trained personnel thoroughly familiar with the handling and
cautionary procedures and associated risks.
Procedure For dissolved mercury analysis, filter an unacidified sample through a 0.45 µm
filter (preferably done in the field), followed by acidification with HNO 3 or HCl to pH
< 2 and/or addition of BrCl.

Samples preserved with acid have the potential to lose mercury to coagulated
organic materials in the water or condensed on the walls of the bottle. It is
recommended to add BrCl directly to the original sample bottle at the laboratory
(prior to sub-sampling) if BrCl was not added in the field, even if the sample has
been field preserved with HCl.

Include Method Blanks, Lab Duplicates, Matrix Spikes, and Reference Materials or
Laboratory Control Samples with each batch of samples.

Sample Preparation - Digestion

1. Per 100 mL of sample, add 0.50 ± 0.05 mL BrCl solution for clear and filtered
samples, or 1.0 ± 0.1 mL BrCl solution for brown and turbid samples. If
sample containers dedicated to mercury analysis are available, BrCl should
preferably be added directly to the sample container (previously filtered, in the
case of dissolved mercury). If sample containers will be shared for other
metals analyses in addition to mercury, shake the preserved sample well and
treat a sub-sample with BrCl. Cap the sample bottle or digestion vessel (for
sub-samples), and digest at room temperature for a minimum of 30 minutes
(as per US EPA 245.7, 2005). A permanent yellow colour must persist,
otherwise more BrCl must be added and the digestion repeated. Use starch
iodide paper to verify excess BrCl in highly coloured samples.

2. After the BrCl oxidation is complete, add 0.20 - 0.25 mL of hydroxylamine

hydrochloride solution per 100 mL of sample, and cap the bottle or digestion
vessel. Swirl the sample. As the BrCl is destroyed, the yellow colour will
disappear. Allow the sample to react for a minimum of 5 minutes with periodic
swirling.

C-12
 3. Analyze the final extract using appropriate analytical methods (e.g. cold
vapour atomic absorption or atomic fluorescence spectrometry with SnCl 2
reduction).

Record any anomalies observed during the digestion and analysis.

Performance Any analytical method options selected for this analysis must meet or exceed the
Requirements performance requirements specified below.

Accuracy and Precision requirements apply to measures of long term method

performance (averages and standard deviations). Achievement of these
requirements is to be demonstrated during initial and ongoing method re-validation
studies. They do not constitute acceptance criteria or Data Quality Objectives for
individual Quality Control samples. For Initial Validations, averages of at least 8
spikes or CRMs must be assessed (preferably taken from multiple analytical
batches). Ongoing re-validations (performance reviews) should assess QC data
encompassing longer timeframes (e.g. 6 months to 1 year). A minimum frequency
of 2 years is recommended for ongoing re-validations.

Accuracy Requirement: Laboratories must demonstrate method accuracy

(measured as average recovery) of 90 – 110% or better for clean matrix spikes or
certified reference materials at concentrations above ten times the MDL.

Precision Requirement: Laboratories must demonstrate method precision equal

to or better than 10% relative standard deviation for clean matrix spikes at
concentrations above ten times the MDL.

Sensitivity Requirement: Where possible, the method should generate Method

Detection Limits that are less than 1/5 of applicable numerical standards. The
method is not fit-for-purpose if an MDL exceeds a guideline, standard, or
regulatory criteria against which it will be used for evaluation of compliance.

Quality Control Summary of QC Requirements

Method QC Minimum Frequency Minimum Data Quality

Component Objectives*
1 per batch (max 20
Method Blank Less than reported DL
samples)
Reference Material or 1 per batch (max 20
Laboratory Control samples) 80 – 120%
Sample
1 per batch (max 20
Matrix Spike 70 – 130%
samples)
1 per batch (max 20
Lab Duplicate ≤ 20% RPD
samples)
Field Duplicate Recommended None Specified
* Minimum DQOs apply to individual QC samples, not averages, and only at levels above 10x MDL.
Laboratories must report qualified data when DQOs are not met, unless other evidence demonstrates
that the quality of associated sample data has not been adversely affected.

C-13
Prescribed The following components of this method are mandatory:
Elements
1. Completeness of BrCl digestion must be verified by ensuring that digested
samples retain a permanent yellow colour, or by testing with a starch iodide
indicating paper.

2. All Sample Handling, Preservation, Hold Time, Performance Requirements,

and Quality Control requirements must be met.

Apart from these limitations, and provided performance requirements are met,
laboratories may introduce modifications to this method in order to improve quality
or efficiency.

Note that other BC MOE approved sample preparation procedures are also
available for total and dissolved mercury in waters.

References 1. US EPA Method 1631, Revision E, Mercury in Water by Oxidation, Purge and
Trap, and Cold Vapor Atomic Fluorescence Spectrometry, Office of Water, US
EPA, Aug 2002.

2. US EPA Method 245.7, Revision 2.0, Mercury in Water by Cold Vapor Atomic
Fluorescence Spectrometry, Office of Water, US EPA, February 2005.

3. US EPA Method 1669, Sampling Ambient Water for Trace Metals at EPA
Water Quality Criteria Levels, Office of Water, US EPA, July 1996.

4. US EPA 40 CFR Part 136, March 2007.

Revision History October 1, New method added to BC Lab Manual. Effective date for this
2013 method is October 1, 2013. A requirement for the use of new
sample container and preservation requirements for mercury in
water (as described in this method) is also effective October 1,
2013.

1.1.3 Total Mercury Digestion

Sample Type: Fresh Water

Wastewater
Marine Water

Container: Containers are glass with a tightly fitting lid, or Teflon.

Preservation: Unfiltered-field: add 4 mL HNO3 (see section 2.1.6) per litre or 20%
(w/v) K2Cr2O7 in 1:1 HNO3, 2mL/L
Unfiltered-lab: add 4 mL HNO3 (see section 2.1.6) per litre or 20%
(w/v) K2Cr207 in 1:1 HNO3, 2mL/L

Principle of Method: The water sample undergoes a strongly oxidizing digestion to dissolve all the
mercury, break down organics and eliminate any sulfide present in the
sample.
The sample is then introduced to:
a) CVAAS

C-14
Apparatus: (see section 2.1.5)
a) Water bath -minimum temperature requirement: 95°C
b) Fume hood
c) Glassware -300 mL BOD bottles (or equivalent)

Reagents: a) Deionized distilled water

b) Sulfuric acid (H2SO4), concentrated, reagent grade
c) Nitric acid (HNO3), concentrated, reagent grade
d) Potassium permanganate (KMnO4), 5% w/v, mercury-free
e) Potassium persulfate (K2S2O8), 5% w/v, reagent grade
f) Sodium chloride-hydroxylamine sulfate, 12% w/v, reagent grade
Procedure
Sample Preparation: Samples are prepared in batches (25-35) dictated by the size of the water
bath accommodating the glassware containing the samples.

Each batch encompasses:

a) Sample replicates - 10% of samples in duplicate, minimum of one
duplicate per batch.
b) Quality control samples - 5% of samples, minimum of one per batch -
containing elements of known concentrations.
c) Two reagent blanks - 5% of samples, not to exceed two per batch and
minimum of one per batch.
d) Calibration standards, minimum of three per batch, bracketing the
expected concentration of the samples.

All are subjected to the same reagents and treatment for digestion as follows:
a) Pipette 100 mL of sample, or an aliquot diluted to 100 mL, into a 300
mL BOD bottle.
b) Add 5 mL concentrated H2SO4, 2.5 mL of concentrated HNO 3, and 15
mL 5% KMnO4 solution to each bottle. Mix well after each addition.
c) Ensure purple color persists for at least 15 minutes. If not, add
additional portions of 5% KMnO4 solution, mixing well after each
addition, until the purple color persists for longer than 15 minutes.
1. Add 8 mL 5% K2S2O8 solution to each bottle.
2. Heat bottles in a 95°C water bath for 2 hours.
3. Allow the samples to cool.
d) Add 6 mL 12% sodium chloride-hydroxylamine sulfate to reduce
excess KMnO4.
1. Proceed immediately to analyze the solution.

Instrumental Analysis: The sample is now prepared for analysis by CVAAS. See the specific
instrumental analysis section (section 2.3) for details.

C-15
1.2 Non-Aqueous Samples

Metals
Revision Date: Nov 6, 2015

1.2.1 Strong Acid Leachable Metals (SALM) in Soil - Prescriptive

Parameters Metals in Soil and Sediment

Parameter List This method is applicable to the following parameters:

& EMS Codes
EMS EMS EMS
Parameter Parameter Parameter
Code Code Code
Aluminum AL-T Iron FE-T Silver AG-T
Antimony SB-T Lead PB-T Sodium NA-T
Arsenic AS-T Lithium LI-T Strontium SR-T
Barium BA-T Magnesium MG-T Sulfur S-T
Beryllium BE-T Manganese MN-T Thallium TL-T
Boron B-T Mercury HG-T Thorium TH-T
Cadmium CD-T Molybdenum MO-T Tin SN-T
Calcium CA-T Nickel NI-T Titanium TI-T
Chromium CR-T Phosphorus P-T Uranium U-T
Cobalt CO-T Potassium K-T Vanadium V-T
Copper CU-T Selenium SE-T Zinc ZN-T
Other metals may be analyzed by this method if acceptable performance is
demonstrated and validated. This method is not suitable for the determination of
silica or silicon.

Analytical Method Nitric – Hydrochloric acid digestion, Instrumental analysis.

Introduction This revised method was prepared for BC MOE by the BCELTAC to provide
improved consistency of results for metals in soil, in support of the Waste
Management Act, Contaminated Sites Regulation (CSR). All definitive elements
of the method have been prescribed to minimize inter-laboratory variability,
particularly for incompletely recovered elements like barium.

The BC CSR includes Water and Soil as matrix types, but Soil is only broadly
defined (CSR, section 1). Carter’s definition of Soil (Reference: Carter) as being
“less than 2 mm” material is used for this method.
This method may also be used for marine and freshwater sediment applications,
where sediment is defined as being “less than 63 µm” material. However, by
default, laboratories are instructed to apply the method on the “less than 2 mm”
fraction, except by special request.
This method uses a mixture of nitric acid, hydrochloric acid, and de-ionized water,
with a standardized digestion time and temperature. Laboratories are allowed
some flexibility regarding apparatus and heating methods, but variations in acid
mixture composition, digestion time, or digestion temperature are not permitted.
Method Summary Samples are dried at ≤ 60°C, sieved, and digested with a mixture of nitric acid,
hydrochloric acid, and de-ionized water. Instrumental analysis of sample extracts
can be performed by a variety of analytical methods.
This method provides the sample preparation procedure for the analysis of Total
Metals, as referenced within the BC CSR. Total Metals does not imply a
complete dissolution of silicate materials, as would occur with digestions using
perchloric and hydrofluoric acids. The strong acid leach prescribed by this

C-16
 method is intended to dissolve those metals that may be environmentally
available. The method achieves near complete recoveries of some important
metals, but many others are only partially recovered (see Table 1 for examples).
Metals not dissolved with this method are unlikely to be of environmental
consequence.
This method is prescriptive. It must be followed exactly as described. Where
minor deviations are permitted, this is indicated in the text. All results must be
reported on a dry weight basis.
Method Limitations This method does not dissolve all silicate materials and may result in a partial
extraction, depending on the sample matrix, for some metals, including, but not
limited to aluminum, barium, beryllium, chromium, strontium, titanium, thallium,
and vanadium.
Unpublished studies by some BC laboratories have shown that dissolved
antimony and tin may re-sorb to undigested solids over time after the sample
extract has been diluted. Once the solids have been removed from the sample
extract, antimony and tin are more stable.
This method is suitable for the digestion of samples with silver concentrations of
up to 0.5 mg/L in the sample extract after dilution to final volume, which is
equivalent to 50 mg/kg in soils, based on a one gram sample size and 100 mL
final volume (Reference: US EPA 200.2).
This method is suitable for digesting samples with tin concentrations of up to 100
mg/L in the sample extract after dilution to final volume, which is equivalent to 1%
in soils, using a one gram sample size and 100 mL final volume (Reference: US
EPA 200.2).
The solubility and stability of barium is limited in the presence of free sulfate using
this method (Reference: US EPA 200.2).

Matrix Soil and sediment.

Interferences and The interferences encountered will differ depending on the instrumental method
Precautions used to analyze the sample extracts. These interferences should be clearly
outlined and controlled in the analysis procedure. High concentrations of acids
may cause physical interferences with some instrumental techniques.

Sampling, Handling, Sampling should be done by qualified personnel. Samples must be collected and
& Preservation stored such that degradation or alteration of the sample is minimized. Collect the
sample in a clean polyethylene or glass container, and tightly cap immediately
after sampling.
Preservation: None
Stability Holding Time:
Metals (except Mercury): 180 days
Mercury: 28 days

When tin and antimony analyses are required, the sample extracts must be
separated from the undigested solids within 4 hours of diluting to final volume.
The decanted or filtered sample extract must be analyzed within 7 days.

Results reported for samples digested beyond holding times must be qualified.

Storage: No requirement for storage temperature. Ambient storage temperature

conditions are suitable.

C-17
Equipment and 1. Heating source (e.g. block digester, hotplate, water bath) capable of
Supplies maintaining a sample extract temperature of 95 ± 5°C.
2. Balance, minimum 3 place.
3. Drying oven (not required).
4. Sieve, 2 mm (ASTM-E11 Sieve No. 10, US Sieve No. 10, Tyler 9 Mesh) or
Sieve, 63 µm (ASTM-E11 Sieve No. 230, US Sieve No. 230, Tyler 250
Mesh). It is recommended that a stainless steel screen/sieve with all tin
solder be used. Sieves must not be constructed of brass or contain lead
solder. Polypropylene or nylon sieves may also be used.
5. Acid dispensers.
6. Vapor refluxing cover to fit digestion vessel (e.g. reflux cover, watch glass
etc.).
7. Digestion vessels (e.g. block digester tube, beaker, flask, etc.).
8. Gloves.
9. Spatula.

Reagents 1. Nitric acid (HNO3) conc. (67 - 70%), reagent grade minimum.
2. Nitric acid (1+1) – add 500 mL concentrated HNO3 to 400 mL de-ionized
water and dilute to 1 L.
3. Hydrochloric acid (HCl) conc. (34 - 37%), reagent grade minimum.
4. Hydrochloric acid (1+1) – add 500 mL concentrated HCl to 400 mL de-ionized
water and dilute to 1 L.
5. Water, de-ionized (ASTM Type I or equivalent recommended).

Safety Nitric and hydrochloric acid must not be premixed; they should be added
individually to each sample vessel. Mixtures of nitric and hydrochloric acid must
not be stored in closed containers.

Wear appropriate PPE (Personal Protective Equipment) including lab coat,

gloves, and safety glasses. Add acids to samples and perform digestions under a
fume hood.

Procedure Samples are prepared and digested using the following procedures:

Sample Homogenization and Sub-Sampling

1. Inspect the sample and record any unusual or significant characteristics (e.g.
lead shot pellets, metal turnings, nails, shells, etc).
2. Remove any obviously foreign material such as vegetation.

3. If the sample has separated into visually discrete layers (e.g. aqueous,
organic, and sediment phases), the entire sample must be homogenized prior
to sub-sampling. The aqueous phase must not be decanted.

Note: Special project requirements may involve alternative procedures such

as decanting of the aqueous fraction. Indicate any departures or deviations
from the prescribed method with a qualifying statement in the laboratory
report.

4. Homogenize the entire sample by vigorous stirring using a spatula. If it is not

possible to homogenize the sample in the container it was received in, the
sample can be transferred to a larger container prior to homogenization.
Clean the spatula and mixing container between samples.

5. Where moisture determination is required, a separate sub-sample must be

taken prior to drying and sieving.

C-18
Sample Preparation – Drying

1. Dry the sample to a constant weight at a temperature of ≤ 60°C. Freeze

drying is acceptable.

Note: Sample drying temperature must not exceed 60°C to minimize

volatilization of analytes such as mercury (Reference: US EPA 200.2).

2. Alternatively, moist or wet samples may be wet-sieved. If a sample is sieved

when moist, a moisture determination must be done on the sieved portion
(not on the “as received” sample) in order to convert results to dry weight.

Sample Preparation – Sieving

1. Sieve each sample through a 2 mm sieve. By special request, some

sediment applications may require the use of a 63 µm sieve. If a 63 µm sieve
is used, this must be indicated on the laboratory report. DO NOT pulverize
samples to pass through either sieve type. Easily friable materials (dried clay
clods, disintegrating rock, etc.) should be disaggregated prior to screening.
Where necessary, non-pulverizing disaggregating tools like rolling mills,
mortar and pestle, or flail grinders may be used.

2. Where available, it is recommended that a minimum of 25 grams of sample is

sieved to ensure representative sub-sampling for the digestion stage.

3. Discard the portion of sample that did not pass through the sieve.

4. Field sampling personnel may pre-screen the samples in the field.

Sample Preparation - Digestion

1. Weigh 1.0 ± 0.1 g (dry weight) of sample into a digestion vessel, which must
be fitted with a cap that supports open vessel reflux action (e.g. hotblock
digestion tube, beaker, or Erlenmeyer flask with watch glass). At minimum,
include Method Blanks, Lab Duplicates, and Reference Materials with each
batch of samples. Laboratory Control Samples are also recommended.
Weights must be recorded using a minimum 3 place balance.

Note: In cases where one gram of sieved sample is not available, perform
the analysis as described, and qualify the results (results for poorly recovered
metals like Barium may be increased).

2. Add 5 ± 0.2 mL de-ionized water, 2.5 ± 0.2 mL concentrated HNO 3, and 2.5 ±
0.2 mL concentrated HCl. Alternatively, add 5.0 ± 0.2 mL of HNO 3 (1+1) and
5.0 ± 0.2 mL of HCl (1+1).

3. Add a reflux cap to the top of the digestion vessel. Swirl acid and sample to
mix gently. It is permitted to allow samples to cold digest prior to heating to
reduce any potential effervescence from reactive samples.

4. Digest samples for 2 hours ± 15 minutes at a temperature of 95 ± 5°C at

atmospheric pressure. A digestion block or waterbath are the preferred
methods of heating. The heat for digestion must maintain the sample extract
temperature at 95 ± 5°C. This refers to the temperature of the sample extract
in a digestion vessel covered with a reflux cap, not the temperature setting on
the heating source, and not the temperature of an uncovered digestion
vessel. It is recommended that the sample extract temperature be monitored
and recorded with each batch.

C-19
 5. Allow the sample to cool and dilute the entire sample with de-ionized water to
the volume required for the analysis. The dilution volume will depend on the
analytical method and objectives. Typical final dilution volumes will be 25 mL,
50 mL, or 100 mL. Include all undigested solid material as part of the final
diluted volume. Sample extracts should not be stored in glass.

6. When tin and antimony analyses are required, sample extracts must be
separated from the undigested solids within 4 hours of diluting to final volume.
The decanted or filtered sample extract must be analyzed within 7 days.
These steps are necessary to minimize tin and antimony losses due to re-
sorption.

7. Analyze the final extract using appropriate analytical methods and report the
results on a dry weight basis.

8. Report any anomalies observed during the digestion and analysis.

Quality Control Summary of QC Requirements

Method QC Minimum Frequency Minimum Data Quality

Component Objectives*
Method Blank 1 per batch Less than reported DL
(max 20 samples)
Reference Material 1 per batch 70 - 130% of the laboratory’s
(max 20 samples) long term mean value (see
validation section for
additional requirements)
Laboratory Control 1 per batch 80 - 120%
Sample (recommended) (recommended)
(recommended)
Lab Duplicates 1 per batch ≤ 30% RPD for all metals
(max 20 samples) except those indicated below

≤ 40% RPD (Ag, Al, Ba, Hg,

K, Mo, Na, Pb, Sn, Sr, Ti)
Field Duplicates Recommended None Specified

* Minimum DQOs apply to individual QC samples, not averages, and only at levels above 10x MDL.
Laboratories must report qualified data when DQOs are not met.

QC Details Reference Material requirements: Any suitable RM (including in-house RMs)

may be utilized for this method for routine Quality Control purposes, but the RMs
listed below under validation requirements are recommended. RMs provide QC
data that includes digestion elements of the method and which is representative of
method performance for typical samples.

Laboratory Control Sample: Recommended 1 per batch. An LCS for this

method is a spiked Method Blank (no blank matrix exists for metals in soils). An
LCS has more precisely defined targets than soil RMs, can cover all parameters
reported by the method, and allows for better and more precise Quality Control of
basic elements of the method (e.g. volumetric precision and controls and
instrumental analysis).

C-20
Method Validation Initial Method Validation requirements as outlined below must be completed before
Requirements this method may be used to generate results for unknown samples. The method
must be re-evaluated periodically (every two years is recommended as a suitable
frequency). Prepared validation samples must be analyzed by all instrument
methods used for routine analysis.

Demonstration of Accuracy and Precision

Prepare and analyze at least 8 replicates of at least two of the following Certified
Reference Materials:

- NRC PACS-2
- CCRMP TILL-1
- CCRMP TILL-3
- SCP Science SS-2

Where the above RMs are utilized for routine QC purposes, re-validations should
be conducted using all routine QC data available for the review period.

Accuracy is measured as Percent Recovery versus the Interim Targets outlined in

Table 1. For each metal, average accuracy must be within 70-130% of the Interim
Targets, for results ≥ 5 times the Reported Detection Limit. Precision must be
<15% RSD for results ≥ 5 times the Reported Detection Limit.

The Interim SALM Targets and DQOs may be re-assessed in the future if RMs
become unavailable or if otherwise required.

References US EPA Method 200.2, Sample Preparation Procedure for Spectrochemical

Determination of Total Recoverable Elements, National Exposure Research
Laboratory, Office of Water, US EPA, Cincinnati, OH, October 1999.

Soil Sampling and Methods of Analysis, Carter, M.R., editor, for Canadian
Society of Soil Science, Lewis Publishers, 1993.

Revision History Nov 6, 2015 Changed storage temperatures to be consistent with current BC
MOE requirements. Removed requirement for minimum one
hour cold digestion (not necessary with version 2 of SALM
method). Added LCS to QC and Procedure sections
(recommended). Removed unnecessary references.

July 7, 2009 Version 2 of BC SALM Method for 2009 BC Lab Manual.

Method revised from performance based to prescriptive. All key
defining elements of the method are now prescribed. New
interim RM targets assigned.

Feb 2001 Version one of BC SALM Method was introduced. Incorporated

into Lab Manual November 2002.

C-21
 (a)
TABLE 1. Interim Target Values for Reference Materials using BC SALM
Parameter CCRMP CCRMP CCRMP CCRMP NRC NRC SCP SCP
TILL-1 TILL-1 TILL-3 TILL-3 PACS-2 PACS-2 Science Science
Certified SALM Certified SALM Certified SALM SS-2 SS-2
(“Total”) Interim (“Total”) Interim (“Total”) Interim EPA3050A SALM
Target Target Target Digestion Interim
Targets Target

Aluminum - Al (%) 7.25 1.82 6.45 1.15 6.62 1.75 1.33 1.37
Antimony - Sb (mg/kg) 7.8 6.27 0.9 0.724 11.3 7.3 - 4.16
Arsenic - As (mg/kg) 18 15.4 87 82.1 26.2 23.3 75 88.4
Barium - Ba (mg/kg) 702 80.6 489 40 - 294 215 224
Beryllium - Be (mg/kg) 2.4 0.544 2.0 0.369 1.0 0.408 - -
Boron - B (mg/kg) - - - - - 38.1 - -
(b) (b)
Cadmium - Cd (mg/kg) < 0.2 - < 0.2 - 2.11 1.98 - 2.2
Calcium - Ca (%) 1.94 0.332 1.88 0.517 1.96 0.779 11.3 12.3
Chromium - Cr (mg/kg) 65 27.2 123 63.1 90.7 48.1 34 34.6
Cobalt - Co (mg/kg) 18 12.5 15 10.4 11.5 8.75 12 13.1
Copper - Cu (mg/kg) 47 44.9 22 19.8 310 297 191 211
Iron - Fe (%) 4.81 3.33 2.78 2.02 4.09 3.12 2.10 2.53
Lead - Pb (mg/kg) 22 14.4 26 17.3 183 167 126 132
Lithium - Li (mg/kg) 15 - 21 - 32.2 - 14 14.3
Magnesium - Mg (%) 1.30 0.583 1.03 0.609 1.47 0.99 1.11 1.24
Manganese - Mn (mg/kg) 1420 1100 520 315 440 253 457 511
Mercury - Hg (mg/kg) 0.092(b) 0.098 0.107(b) 0.11 3.04 2.88 - 0.33
Molybdenum - Mo (mg/kg) 2 0.738 2 0.619 5.43 4.57 - 2.94
Nickel - Ni (mg/kg) 24 17.4 39 31.7 39.5 31.6 54 63
Phosphorus - P (%) 0.0930 0.0796 0.0490 0.042 0.096 0.0838 0.0752 0.0832
Potassium - K (%) 1.84 0.0619 2.01 0.0965 1.24 0.323 0.342 0.342
Selenium - Se (mg/kg) - - - - 0.92 - - -
Silver - Ag (mg/kg) 0.2(b) - 1.6(b) 1.75 1.22 - - 1.1
Sodium - Na (%) 2.01 0.0340 1.96 0.027 3.45 1.86 0.0558 -
Strontium - Sr (mg/kg) 291 11.6 300 20.3 276 68 214 232
Sulfur - S (%) < 0.05 - < 0.05 - 1.29 1.22 - -
Thallium - Tl (mg/kg) - - - - 0.6(c) - - 0.38
Thorium - Th (mg/kg) 5.6 - 4.6 - - - - -
Tin - Sn (mg/kg) - - - - 19.8 19.1 - 0.74
Titanium - Ti (%) 0.599 0.0764 0.291 0.0645 0.443 0.09 0.0850 0.0969
Uranium - U (mg/kg) 2.2 - 2.1 - 3(c) - - 1.34
Vanadium - V (mg/kg) 99 54.9 62 33.5 133 74.4 34 39.9
Zinc - Zn (mg/kg) 98 67.5 56 40.2 364 337 467 546
(a) Interim Targets from “Report on Results of 2007 Inter-laboratory Study to Re-establish Data Quality Objective for BCMOE Strong Acid Leachable
Metals (SALM) in Soil Method, Prepared for the BC Ministry of Environment, JRD Consulting Company, 2007 June 20. Interim Targets for SS-2 RM
are single lab values provided to BCLQAAC.
(b) Parameter not listed as “Total”. Listed as “Summary of partial extraction elements concentrated HNO 3 – concentrated HCl”.
(c) Parameter not certified, provided as informational value.

C-22
1.2.2 Digestion of Biota (Tissues, Vegetation)

Sample Preparation Samples can be processed wet or dry, and can follow a number of
processing schemes which may include:
a) dissection - isolation of target tissue; ie, liver, muscle (animal), root
systems (plants), etc.
b) drying and lipid removal.
c) homogenizing and sub-sampling.

The specifics of the processing scheme will depend on a number of variables

which may include intended use of data generated, nature of samples to be
analyzed, the specific list of elements to be determined and requirements of
applicable regulation.

Analytical Method: ICP-AES, HVICP-AES, FAAS, CVAAS, GFAAS and HVAAS.

Introduction: The trend in biological sampling is to choose a species of plant or animal

which can be used as an indicator of human-induced environmental impact.
To the analyst this may involve the determination of a number of heavy
metals in, for example, one single small clam, leaves, or sections or organs
of mammals, fish, or invertebrates.

Method Summary: There are two main ashing techniques to decompose biota samples. The
oldest and simplest method is dry ashing, carried out by heating the tissue in
a muffle furnace at 400-800°C in the presence of air. This technique can
lead to a variable loss of many elements, including, Hg, B, Pb, Zn, Cd, Ca,
In, Tl, As, Sb, Fe, Cr, and Cu. The addition of fluxes reduces these losses in
many cases, but increases the risk of contaminating the samples with the
elements of interest. Wet ashing (acid digestion) techniques employing liquid
reagents which are most often applied to biological samples. Relatively low
temperatures are used to achieve decomposition so that losses through
volatilization, adsorption and reaction with vessel materials are limited to only
a few elements. For this reason, substances, which are particularly difficult
to decompose are occasionally not completely solubilized, or require such a
large amount of reagent that the blank values exceed permissible limits.
Other reagents which may be used are; nitric acid alone or in combination
with hydrogen peroxide or perchloric acid.

Matrix: Plant tissue and animal tissue.

Interferences and
Precautions: Note: Standard laboratory safety precautions must be followed.

Volatile chlorides such as Hg+2, Sb+3 and Se+4 tend to be lost from HCl
solutions; in contrast, Cr+3 tends to be lost from perchloric acid solutions at
temperatures above 150°C through the formation of chromyl chloride
(CrO2Cl2). As+3, Sn+2, Ru and Os can be volatilized when samples are
fumed with perchloric or sulfuric acid. When metals are dissolved in non-
oxidizing acids, As and Sb may escape as hydrides.

Some vegetation contains silicates which may not fully dissolve unless a
small amount of HF is used.

C-23
Sample Handling and
Preservation: For all biota the best preservation technique is to freeze the sample. Freeze-
thaw cycles must be avoided to prevent the loss of interstitial and intercellular
fluids.

Apparatus, Materials
and Reagents: See References.

Quality Control: Many biological reference materials (RMs) are available. The RM and
sample matrixes should be matched as closely as possible.

Revision History: February 14, 1994: Publication in 1994 Laboratory Manual.

March 1997: Additional digestion procedures published in
Supplement #1. Nitric acid digestion procedure
formats from 1994 Laboratory Manual replaced by 2
nitric acid digestion procedures from 1997
Supplement. Also metals in soils/sediment
procedure from 1994 Laboratory Manual deleted
and replaced by both Aqua Regia digestion
(preferred) and perchloric digestion procedures from
the 1997 Supplement.
December 31, 2000: SEAM codes removed. Container restriction for
mercury samples added. Minor editing.

1.2.3 Metals in Animal Tissue and Vegetation (Biota) - Prescriptive

Metals
Revision: Aug 15, 2014

Parameter Metals in Tissue and Vegetation (Biota)

Analytical Method Nitric acid, Hydrochloric acid, and Hydrogen peroxide digestion (followed by
appropriate instrumental analysis).

Introduction This method was prepared for BC MOE by the BCELTAC to provide improved
interlaboratory consistency of results for metals in tissue and vegetation. All
definitive elements of the method have been prescribed to minimize inter-
laboratory variability.

This method uses a mixture of nitric acid, hydrochloric acid, and hydrogen
peroxide, with a standardized digestion time and temperature. Laboratories are
allowed some flexibility regarding apparatus and heating methods, but variations
in acid mixture composition, digestion time, or digestion temperature are not
permitted.

Method Summary Samples are homogenized and digested with a mixture of nitric acid, hydrochloric
acid, and hydrogen peroxide. Instrumental analysis of sample extracts can be
performed by a variety of analytical methods.

This method provides the sample preparation procedure for the analysis of Total
Metals, but does not imply a complete dissolution of some materials, as would
occur with digestions using perchloric and hydrofluoric acids. The strong acid
leach prescribed by this method is intended to provide a conservative estimate of
the concentrations of metals that may be bio-available (for example, through
mammalian digestion processes). The method achieves near complete
recoveries of most toxicologically important metals, but some elements
associated with recalcitrant minerals (e.g. aluminosilicates) are only partially

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 recovered, especially those that originate from dust, soil, or sand particles that
can be present in some types of biota samples.

This method is prescriptive. It must be followed exactly as described. Where

minor deviations are permitted, this is indicated in the text.

Method Limitations This method does not dissolve all materials and may result in a partial extraction,
depending on the sample matrix, for some metals, including, but not limited to
aluminum, chromium, iron, nickel, strontium, tin, titanium, uranium, and vanadium,
especially when these elements are present in refractory mineral forms.

Analytes and EMS This method is applicable to the following parameters:

Codes
EMS EMS EMS
Analyte Analyte Analyte
Code Code Code
Aluminum AL-T Iron FE-T Silver AG-T
Antimony SB-T Lead PB-T Sodium NA-T
Arsenic AS-T Lithium LI-T Strontium SR-T
Barium BA-T Magnesium MG-T Sulfur S-T
Beryllium BE-T Manganese MN-T Thallium TL-T
Boron B-T Mercury HG-T Thorium TH-T
Cadmium CD-T Molybdenum MO-T Tin SN-T
Calcium CA-T Nickel NI-T Titanium TI-T
Chromium CR-T Phosphorus P-T Uranium U-T
Cobalt CO-T Potassium K-T Vanadium V-T
Copper CU-T Selenium SE-T Zinc ZN-T

Other metals may be analyzed by this method if acceptable performance is

demonstrated and validated. This method is not suitable for the determination of
silica or silicon.

Reported results must be clearly indicated as being in either dry weight and/or
wet weight concentration units, depending on the application, as requested by the
data-user. The default Ministry preference is for animal tissues to be reported on
a wet weight basis (e.g. “mg/kg wwt”), and for vegetation to be reported on a dry
weight basis (e.g. “mg/kg” or “mg/kg dwt”). Biota samples with excessively high
moisture contents (i.e. >90% moisture, which may occur in periphyton,
macrophyte, benthic invertebrates, eggs, etc.) should be dried at ≤ 60° or freeze
dried and weighed prior to digestion to minimize the error associated with
moisture corrections.

Matrix Tissue and Vegetation (Biota).

Interferences and The interferences encountered will differ depending on the instrumental method
Precautions used to analyze the sample extracts. Applicable interferences should be clearly
identified and controlled in the analysis procedure. High concentrations of acids
may cause physical interferences with some instrumental techniques.

Equipment used for sample homogenization, including various types of

homogenizer probes, grinders, food processors, knife blades, may have the
potential for the contamination of metals including, but not limited to aluminum,
chromium, iron, manganese, molybdenum, nickel, tin, and vanadium. Such
equipment must be tested and validated to ensure it does not introduce significant
metallic contaminants to samples.

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Sample Handling Sampling should be done by qualified personnel. Samples must be collected and
and Preservation stored such that degradation or alteration of the sample is minimized. Collect the
sample in a clean plastic or glass container, appropriately sealed. Paper bags
are suitable collection containers for vegetation where samples will be dried prior
to digestion and where test results will be reported on a dry weight basis.

Where practical, submission of a minimum of 20 wet grams of animal tissue or 5

grams of low moisture vegetation is recommended.

The decision as to which components of animal tissue samples (e.g. organs,

muscle tissue, skin, whole sample, etc.) is critical to this analysis. Specific
instructions for the preparation of vegetation samples can also be critical (e.g.
whether to include or exclude dirt residues, etc.). Ensure that clients have been
adequately consulted for specific instructions.

Stability Preservation: none

Holding time:

Metals (except Mercury): 2 years if frozen at ≤ -18°C (Reference: Puget Sound

Protocols). Freezing is optional for freeze dried tissue samples and for vegetation
that is dried prior to digestion and reported on a dry weight basis; in these cases,
samples may be stored up to 6 months at ambient temperature (based on BC
MOE soil guidelines).

Mercury: 1 year if frozen at ≤ -18°C (Reference: US EPA 1631E Appendix).

Freezing is optional for freeze dried tissue samples and for vegetation that is
dried prior to digestion and reported on a dry weight basis; in these cases,
samples may be stored up to 28 days at ambient temperature (based on BC MOE
soil guidelines).

Results reported for samples digested beyond holding times must be qualified.

Storage: Samples must be kept cool (≤ 10°C) during transport. Biota samples
where freezing is required (e.g. animal tissues, high moisture vegetation like
berries, etc.) should be frozen as soon as possible, preferably within 48 hours of
sampling, or digestion should be initiated within 96 hours of sampling.

Where practical, it is recommended for tissue dissections to be conducted prior to

freezing, unless the whole sample will be homogenized.

Equipment and 1. Heating source (e.g. block digester, hotplate, water bath) capable of
Supplies maintaining a sample extract temperature of 95 ± 5°C
2. Balance (capable of weighing to at least 3 significant figures)
3. Drying oven (may not be required)
4. Freezer (may not be required)
5. Freeze Dryer (may not be required)
6. Acid dispensers
7. Vapour refluxing cover to fit digestion vessel (e.g. reflux cap, watch glass etc.)
8. Digestion Vessels (e.g. block digester tube, beaker, flask, etc.)
9. Gloves
10. Spatula
11. Equipment for sample homogenization

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Reagents 1. Nitric acid (HNO3), concentrated (67 - 70%), reagent grade minimum
2. Hydrochloric acid (HCl), concentrated (34 - 37%), reagent grade minimum
3. Hydrogen peroxide (H2O2) 30%, reagent grade minimum
4. Water, de-ionized (ASTM Type I or equivalent recommended)

Safety Nitric and hydrochloric acid must not be premixed; they should be added
individually to each sample vessel. Mixtures of nitric and hydrochloric acid must
not be stored in closed containers. When mixing concentrated acids with water,
slowly and carefully add the acids to water. Adding water to concentrated acids is
a hazard and can cause a violent exothermic reaction.

Wear appropriate PPE (Personal Protective Equipment) including lab coat,

gloves, and safety glasses. Add reagents to samples and perform digestions
under a fume hood.

Procedure Sample Preparation – Drying and Homogenization

1. Depending on project requirements, samples may require drying prior to

homogenization. Where drying is required, dry the sample at a temperature
of ≤ 60°C. Freeze drying is acceptable.

2. Note: Sample drying temperature must not exceed 60°C to minimize

evaporative loss of volatile analytes such as mercury (Reference: Puget
Sound Protocols).

3. Homogenize the dried or as-received sample to a paste-like consistency

either manually or mechanically using suitable equipment.

Sample Preparation - Digestion

The following procedure is based on the digestion of approximately 5 grams of

wet sample or 1 gram of dry sample. The amount of sample digested can be
scaled up or down as long as the acid ratios are maintained (9 parts HNO 3 : 1 part
HCl). The default minimum total amount of reagents listed below may be used for
sample weights up to 7.5 wet grams or 1.5 dry grams. For sample weights larger
than this, increase the total amount of reagents.

1. Weigh approximately 5 grams of wet sample or 1 gram of dry sample into a

digestion vessel, which must be fitted with a reflux cap and which must be
capable of supporting reflux action. Examples of digestion vessels fitted with
a reflux cap include a beaker, Erlenmeyer flask, or digestion tube fitted with a
watch glass. Include Method Blanks, Lab Duplicates, and Reference
Materials with each batch of samples. Weights must be recorded using a
balance capable of weighing to at least 3 significant figures.

2. Add a minimum of 9 mL concentrated HNO3, and a minimum of 1 mL

concentrated HCl (per ~5 grams wet sample or ~1 gram dry sample).
Optionally, 4 ± 0.5 mL of de-ionized water can be added to dried CRMs to be
representative of the typical water content of wet tissue samples. Adding
water to the CRMs may prevent excessive reactivity after acid addition.

3. Add a reflux cap to the top of the digestion vessel. Swirl acid and sample to
mix gently. To reduce the reactivity of samples during initial heating, it is
recommended to allow samples to equilibrate with the acid mixture at room
temperature for a minimum of 1 hour prior to heating.

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 4. Digest samples for 2 hours ± 15 minutes at a temperature of 95 ± 5°C at
atmospheric pressure. A hotblock or waterbath are the preferred methods of
heating. The heat for digestion must maintain the sample extract temperature
at 95 ± 5°C. This refers to the temperature of the sample extract in a
digestion vessel covered with a reflux cap, not the temperature setting on the
heating source, and not the temperature of an uncovered digestion vessel. It
is recommended that the sample extract temperature be monitored and
recorded with each batch.

5. Allow the sample to cool and add a minimum of 4 mL 30% H 2O2. It is

acceptable to add the H2O2 in multiple additions.

6. Digest samples for a minimum of 1 hour at a temperature of 95 ± 5°C.

7. Dilute the entire sample with de-ionized water to the volume required for the
analysis. The dilution volume will depend on the analytical method and
objectives. Typical final dilution volumes for most instrumental techniques
range from 25 mL to 100 mL. Include all undigested solid material as part of
the final diluted volume.

8. Analyze the final extract using appropriate analytical methods and report the
results on a dry weight and/or wet weight basis, depending on the application,
as requested by the data-user. Refer to Analytes and EMS Codes section for
Ministry preferences on reporting units for biota.

9. Report any anomalies observed during the digestion and analysis.

Quality Control Summary of QC Requirements

Method QC Minimum Frequency Minimum Data Quality

Component Objectives*
Method Blank 1 per batch Less than reported DL
(max 20 samples)
Reference Material 1 per batch 70 – 130% of the laboratory’s long
(max 20 samples) term mean value or of certified
targets for the method (if
available)
Lab Duplicates 1 per batch ≤ 40% RPD for all metals except
(max 20 samples) those indicated below
where sufficient
sample is available ≤ 60% RPD (for Ca & Sr)
Field Duplicates Recommended None Specified

* Minimum DQOs apply to individual QC samples at levels above 10x MDL. Report qualified data
when DQOs are not met.

Reference Material requirements: Any suitable RM (including in-house RMs)

may be utilized for this method for routine Quality Control purposes.

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Method Validation If metallic instruments or equipment are used to process or homogenize test
Requirements samples, validation studies must be conducted to ensure that significant metallic
contaminants are not introduced to test samples.

Specific method validation requirements for accuracy and precision may be

established after interlaboratory consensus targets for appropriate Reference
Materials have been established for this method by interlaboratory study or round
robin.

References US EPA Method 200.3, Sample Preparation Procedure for Spectrochemical

Determination of Total Recoverable Elements in Biological Tissues, United States
Environmental Protection Agency, 1996.

Recommended Guidelines for Measuring Metals in Puget Sound Marine

Water, Sediment and Tissue Samples, Prepared for the US EPA, Puget Sound
Water Quality Action Team, Olympia Washington, 1997.

US EPA Appendix to Method 1631 Total Mercury in Tissue, Sludge, Sediment,

and Soil by Acid Digestion and BrCl Oxidation, United States Environmental
Protection Agency, 1991.

Revision History Aug 15, New prescriptive method added to BC Lab Manual to improve
2014: interlaboratory consistency. Effective date of this method is Jan 1,
2015.

This protocol has been officially approved by the Director of Waste Management. It may be cited in
Waste Management permits, approvals and orders, as well as legislated requirements.

Approval:______________________ Date:__________________ Effective Date: January 1, 2015

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2.0 INSTRUMENTAL ANALYSIS

2.1 Atomic Absorption – Direct Flame and Graphite Furnace Methods

2.1.1 Introduction

Metals in solution may be readily determined by atomic absorption spectroscopy. The method is simple,
rapid, and applicable to a large number of metals in drinking, surface, and saline waters, and domestic
and industrial wastes. While drinking waters free of particulate matter may be analyzed directly, domestic
and industrial wastes require processing to solubilize suspended material. Sludge, sediments and other
solid samples may also be analyzed after proper pretreatment.

Detection limits, sensitivity and optimum concentration ranges of the metals will vary with the various
makes and models of atomic absorption spectrometers. The data shown in Table C-1, however, provide
some indication of the actual concentration ranges measurable by direct aspiration and furnace
techniques. In the majority of instances the concentration range shown in the table under direct
aspiration may be extended much lower with scale expansion and, conversely, extended upwards by
using a less sensitive wavelength or by rotating the burner head. Detection limits by direct aspiration may
also be extended through concentration of the sample and/or through solvent extraction techniques.
Lower concentrations may also be determined using furnace techniques. The concentration ranges given
in Table C-1 are somewhat dependent on equipment, such as the type of spectrometer and furnace
accessory, the energy source and the degree of electrical expansion of the output signal. When using
furnace techniques, however, the analyst should be cautioned as to possible chemical reactions occurring
at elevated temperatures which may result in either suppression or enhancement of the analysis element.
To ensure valid data with furnace techniques, the analyst must examine each matrix for interference
effects and, if detected, treat accordingly using either successive dilution, matrix modification or method
of standard additions.

Where direct aspiration atomic absorption techniques do not provide adequate sensitivity, in addition to
the furnace procedure, reference is made to specialized procedures such as the gaseous hydride method
for arsenic and selenium, the cold vapour technique for mercury, and the chelation-extraction procedure
for selected metals. Reference to approved colorimetric methods is also made.

Atomic spectroscopy procedures are provided as the methods of choice; however, other instrumental
methods have also been shown to be capable of producing precise and accurate analytical data. These
instrumental techniques include mass spectroscopy, X-ray fluorescence, neutron activation, and anodic
stripping, to name but a few. The above mentioned techniques are presently considered as alternate test
procedures providing they meet or exceed individual performance requirements.

2.1.2 Method Summary

In direct aspiration atomic absorption spectroscopy a sample is aspirated and atomized in a flame. A light
beam from a hollow cathode lamp, whose cathode is made of the element to be determined, is directed
through the flame into a monochromator, and onto a detector that measures the amount of light
absorbed. Absorption depends upon the presence of free unexcited ground state atoms in the flame.
Since the wavelength of the light beam is characteristic of only the metal being determined, the light
energy absorbed by the flame is a measure of the concentration of that metal in the sample. This
principle is the basis of atomic absorption spectroscopy. It should be noted that alternate light sources
include electrodeless discharge or “Super” lamps.

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 TABLE C-1
Atomic Absorption Concentration Ranges(1)

Direct Aspiration Furnace Procedure (4,5)

Detection Optimum Detection Optimum

Limit Sensitivity* Concentration Range Limit Concentration Range
Metal mg/L mg/L mg/L mg/L mg/L
Aluminum 0.1 1 5 50 0.003 0.02 0.2
Antimony 0.2 0.5 1 40 0.003 0.02 0.3
Arsenic (2) 0.0001 0.0005 0.02 0.001 0.005 0.1
Barium (p) 0.1 0.4 1 20 0.002 0.01 0.2
Beryllium 0.005 0.025 0.05 2 0.0002 0.001 0.03
Cadmium 0.005 0.025 0.05 2 0.0001 0.0005 0.01
Calcium 0.01 0.08 0.2 7
Chromium 0.05 0.25 0.5 10 0.001 0.005 0.1
Cobalt 0.05 0.2 0.5 5 0.001 0.005 0.1
Copper 0.02 0.1 0.2 5 0.001 0.005 0.1
Gold 0.1 0.25 0.5 20 0.001 0.005 0.1
Iridium (p) 3 8 20 500 0.030 0.1 1.5
Iron 0.03 0.12 0.3 5 0.001 0.001 0.1
Lead 0.1 0.5 1 20 0.001 0.005 0.1
Magnesium 0.001 0.007 0.02 0.5
Manganese 0.01 0.05 0.1 3 0.0002 0.001 0.03
Mercury (3) 0.0002 0.0002 0.01
Molybdenum (p) 0.1 0.4 1 40 0.001 0.003 0.06
Nickel (p) 0.03 0.15 0.3 5 0.001 0.005 0.1
Osmium 0.3 1 2 100 0.020 0.05 0.5
Palladium 0.1 0.25 0.5 15 0.005 0.02 0.4
Platinum (p) 0.2 2 5 75 0.020 0.1 2
Potassium 0.01 0.04 0.1 2
Rhenium (p) 5 15 50 1000 0.20 0.5 5
Rhodium (p) 0.05 0.3 1 30 0.005 0.02 0.4
Ruthenium 0.2 0.5 1 50 0.020 0.1 2
Selenium (2) 0.0005 0.001 0.02 0.002 0.005 0.1
Silver 0.01 0.06 0.1 4 0.0002 0.001 0.025
Sodium 0.002 0.015 0.03 1
Thallium 0.1 0.5 1 20 0.001 0.005 0.1
Tin 0.5 5 10 300 0.005 0.02 0.3
Titanium (p) 0.5 2 5 100 0.010 0.05 0.5
Vanadium (p) 0.2 0.8 2 100 0.005 0.01 0.2
Zinc 0.005 0.02 0.05 1 0.00005 0.0002 0.004

(1) The concentrations shown are not contrived values and should be obtainable with any satisfactory
atomic absorption spectrophotometer.
(2) Gaseous hydride method.
(3) Cold vapour technique.
(4) For furnace sensitivity values consult instrument operating manual.
(5) The listed furnace values are those expected when using a 20 µL injection and normal gas flow except
in the case of arsenic and selenium where gas interrupt is used. The symbol (p) indicates the use of
pyrolytic graphite with the furnace procedure.
* The concentration in milligrams of metal per litre that produces an absorption of 1%.

Although methods have been reported for the analysis of solids by atomic absorption spectroscopy
(Spectrochim Acta, 24B 53, 1969) the technique generally is limited to metals in solution or solubilized
through some form of sample processing.

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 (i) Preliminary treatment of wastewater and/or industrial effluents is usually necessary because
of the complexity and variability of the sample matrix. Suspended material must be subjected
to a solubilization process before analysis. This process may vary because of the metals to
be determined and the nature of the sample being analyzed. When the breakdown of organic
material is required, the process should include a wet digestion with nitric acid.

(ii) In those instances where complete characterization of a sample is desired, the suspended
material must be analyzed separately. This may be accomplished by filtration and acid
digestion of the suspended material. Metallic constituents in this suspended matter will then
contribute to the total concentrations present. The sample should be filtered as soon as
possible after collection and the filtrate acidified immediately.

(iii) The total sample may also be treated with acid without prior filtration to measure what may be
termed “total recoverable” concentrations.

When using the furnace technique in conjunction with an atomic absorption spectrometer, a
representative aliquot of a sample is placed in the graphite tube in the furnace, evaporated to dryness,
charred and atomized. As a greater percentage of available analyte atoms are vaporized and dissociated
for absorption in the tube technique than in the flame technique, the use of small sample volumes or
detection of low concentrations of elements is possible. The principle is essentially the same as with
direct aspiration atomic absorption except a furnace, rather than a flame, is used to atomize the sample.
Radiation from a given excited element is passed through the vapour containing ground state atoms of
that element. The intensity of the transmitted radiation decreases in proportion to the amount of the
ground state element in the vapour.

The metal atoms to be measured are placed in the beam of radiation by increasing the temperature of the
furnace, thereby causing the injected specimen to be volatilized. A monochromator isolates the
characteristic radiation from the hollow cathode lamp and a photosensitive device measures the
attenuated transmitted radiation.

2.1.3 Definition of Terms

Optimum Concentration Range: A range, defined by limits expressed in concentration, below which
scale expansion must be used and above which curve correction should be considered. This range will
vary with the sensitivity of the instrument and the operating conditions employed.

Detection Limit: Detection limits can be expressed as either an instrumental or method parameter. The
limiting factor of the former using acid water standards would be the signal-to-noise ratio and degree of
scale expansion used; the latter would be more affected by the sample matrix and preparation procedure
used. The Scientific Apparatus Makers Association (SAMA) has approved the following definition for
detection limit: that concentration of an element which would yield an absorbance equal to twice the
standard deviation of a series of measurements of a solution, the concentration of which is distinctly
detectable above, but close to, blank absorbance measurement. The detection limit values listed in Table
C-I and on the individual analysis sheets are to be considered minimum working limits achievable with the
procedures given in this manual. These values may differ from the optimum detection limit values
reported by the various instrument manufacturers.

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2.1.4 Interferences

2.1.4.1 Direct Aspiration

The most troublesome type of interference in atomic absorption spectroscopy is usually termed
“chemical” and is caused by lack of absorption of atoms bound in molecular combination in the flame.
This phenomenon can occur when the flame is not sufficiently hot to dissociate the molecule, as in the
case of phosphate interference with magnesium, or because the dissociated atom is immediately oxidized
to a compound that will not dissociate further at the temperature of the flame. The addition of lanthanum
will overcome the phosphate interference in magnesium, calcium and barium determinations. Similarly,
silica interference in the determination of manganese can be eliminated by the addition of calcium.
Chemical interferences may also be eliminated by separating the metal from the interfering material.
While competing agents are primarily employed to increase the sensitivity of the analysis, they may also
be used to eliminate or reduce interferences.

The presence of high dissolved solids in the sample may result in an interference from non-atomic
absorbance such as light scattering. If background correction is not available, a non-absorbing
wavelength should be checked. Preferably, samples containing high levels of dissolved solids should be
extracted.

Ionization interferences occur where the flame temperature is sufficiently high to generate the removal of
an electron from a neutral atom, giving a positively charged ion. This type of interference can generally
be controlled by the addition, to both standard and sample solutions, of a large excess of any easily
ionized element.

Although quite rare, spectral interference can occur when an absorbing wavelength of an element present
in the sample but not being determined falls within the width of the absorption line of the element of
interest. The results of the determination will then be erroneously high, due to the contribution of the
interfering element to the atomic absorption signal. Also, interference can occur when resonant energy
from another element in a multi-element lamp or a metal impurity in the lamp cathode falls within the
bandpass of the slit setting and that metal is present in the sample. This type of interference may
sometimes be reduced by narrowing the slit width.

2.1.4.2 Flameless Atomization

Although the problem of oxide formation is greatly reduced with furnace procedures because atomization
occurs in an inert atmosphere, the technique is still subject to chemical and matrix interferences. The
composition of the sample matrix can have a major effect on the analysis. Those effects must be
determined and taken into consideration in the analysis of each different matrix encountered. To help
verify the absence of matrix or chemical interference use the following serial dilution procedure. Withdraw
from the sample two equal aliquots and dilute to the same predetermined volume. (The dilution volume
should be based on the analysis of the undiluted sample. Preferably, the dilution should then be 1:4 while
keeping in mind the optimum concentration range of the analysis. Under no circumstances should the
dilution be less than 1:1). The diluted aliquots should then be analyzed and the results, multiplied by the
dilution factor, should be compared to the original determination. Agreement of the results (within ± 10%)
indicates the absence of interference. Comparison of the actual signal from the spike to the expected
response from the analyte in an aqueous standard should help confirm the finding from the dilution
analysis. Those samples which indicate the presence of an interferent should be treated in one or more
of the following ways:

a) The samples should be successively diluted and reanalyzed to determine if the interference
can be eliminated.

b) The matrix of the sample should be modified in the furnace. Examples are the addition of
ammonium nitrate to remove alkali chlorides, ammonium phosphate to retain cadmium, and
nickel nitrate for arsenic and selenium analyses. Platinum or palladium is a proven matrix
modifier for many furnace elements. The mixing of hydrogen with the inert purge gas has also

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 been used to suppress chemical interference. The hydrogen acts as a reducing agent and
aids in molecular dissociation.

c) Analyze the sample by method of standard additions while noting the precautions and
limitations of its use.

Gases generated in the furnace during atomization may have molecular absorption bands encompassing
the analytical wavelength. When this occurs, either the use of background correction or choosing an
alternate wavelength outside the absorption band should eliminate this interference. Non-specific broad
band absorption interference can also be compensated for with background correction.

Continuum background correction cannot correct for all types of background interference. When the
background interference cannot be compensated for, chemically remove the analyte or use an alternate
form of background correction; e.g. Zeeman background correction.

Interference from a smoke-producing sample matrix can sometimes be reduced by extending the charring
time at a higher temperature or utilizing an ashing cycle in the presence of air. Care must be taken,
however, to prevent loss of the analyte.

Samples containing large amounts of organic materials should be oxidized by conventional acid digestion
prior to being placed in the furnace. In this way broad band absorption will be minimized.

From anion interference studies in the graphite furnace it is generally accepted that nitrate is the preferred
anion. Therefore nitric acid is preferable for any digestion or solubilization step. If another acid in
addition to HNO3 is required, a minimum amount should be used. This applies particularly to
hydrochloric and, to a lesser extent, sulfuric and phosphoric acids.

Carbide formation resulting from the chemical environment of the furnace has been observed with certain
elements that form carbides at high temperatures. Molybdenum may be cited as an example. When this
takes place, the metal will be released very slowly from the carbide as atomization continues. For
molybdenum, the analyst may be required to atomize for 30 seconds or more before the signal returns to
baseline levels. This problem is greatly reduced and the sensitivity increased with the use of
pyrolytically-coated graphite. Ionization interferences have not been reported to date with furnace
techniques. For comments on spectral interference see section 2.1.4.1.

Contamination of the sample can be a major source of error because of the extreme sensitivities
achieved with the furnace. The sample preparation work area should be kept scrupulously clean. All
glassware should be cleaned as directed in part 2.1.5 of this manual. It is very important that special
attention be given to reagent blanks in both analysis and the correction of analytical results. Lastly,
pyrolytic graphite, because of the production process and handling, can become contaminated. As many
as five or possibly ten high temperature burns may be required to clean the tube before use.

2.1.5 Apparatus

1. Atomic Absorption Spectrometer: Single or dual channel, single or double-beam instrument

having a grating monochromator, photomultiplier detector, adjustable slits, a wavelength range of
190 to 800 nm, and provision for interfacing with a strip chart recorder or computer work station.

2. Burner: The burner recommended by the particular instrument manufacturer should be used.
For certain elements a nitrous oxide burner is required.

3. Hollow cathode lamps: Single element lamps are preferred but multi-element lamps may be
used. Electrodeless discharge lamps or “super” lamps may also be used when available.

4. Graphite furnace: Any furnace device capable of reaching the specified temperatures is
satisfactory.

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5. Strip chart recorder: A recorder is strongly recommended for furnace work so that there will be
permanent record and any problems with the analysis such as drift, incomplete atomization,
losses during charring, changes in sensitivity, etc., can be easily recognized.

6. Pressure-reducing valves: The supplies of fuel and oxidant shall be maintained at pressures
somewhat higher than the controlled operating pressure of the instrument by suitable valves.

7. Containers: All glassware, linear polyethylene, polypropylene or Teflon containers, including

sample bottles, should be washed with detergent then rinsed with tap water, 1:1 nitric acid, tap
water, 1:1 hydrochloric acid, tap water, and deionized distilled water, in that order.

2.1.6 Reagents

1. Type II water (ASTM D1193): Use Type II water for the preparation of all reagents and calibration
standards and as dilution water.

2. Concentrated nitric acid (HNO3): Use a spectrograde acid certified for AA use. Prepare a 1:1
dilution with Type II water by adding the concentrated acid to an equal volume of water.

3. Hydrochloric acid (HCl, 1:1): Use a spectrograde acid certified for AA use. Prepare a 1:1 dilution
with Type II water by adding the concentrated acid to an equal volume of water.

4. Fuel and oxidant: Commercial grade acetylene is generally acceptable. Air may be supplied
from a compressed air line, a laboratory compressor, or a cylinder of compressed air. Reagent
grade nitrous oxide is also required for certain determinations. Standard, commercially available
argon and nitrogen are required for furnace work.

5. Stock standard metal solutions: Stock standard solutions are prepared from high purity metals,
oxides, or nonhygroscopic reagent-grade salts using Type II water and redistilled nitric or
hydrochloric acids. (See individual methods for specific instructions.) Sulfuric or phosphoric
acids should be avoided as they produce an adverse effect on many elements. The stock
solutions are prepared at concentrations of 1,000mg of the metal per litre. Commercially
available standard solutions may also be used. Where the sample viscosity, surface tension, and
components cannot be accurately matched with standards, the method of standard addition
(MSA) may be used. This method has been described in detail in section 2.1.7.

6. Calibration standards: For those instruments which do not read out directly in concentration, a
calibration curve is prepared to cover the appropriate concentration range. Usually, this means
the preparation of standards which produce an absorbance of 0.0 to 0.7. Calibration standards
are prepared by diluting the stock metal solutions at the time of analysis. For best results,
calibration standards should be prepared fresh each time a batch of samples is analyzed.
Prepare a blank and at least three calibration standards in graduated amounts in the appropriate
range of the linear part of the curve. The calibration standards should be prepared using the
same type of acid or combination of acids and at the same concentration as will be found in the
samples following processing. Beginning with the blank and working toward the highest
standard, aspirate the solutions and record the readings. Repeat the operation with both the
calibration standards and the samples a sufficient number of times to secure a reliable average
reading for each solution. Calibration standards for furnace procedures should be prepared as
described on the individual sheets for that metal or as described in a specific instrument manual.

C-35
2.1.7 Preparation of a Standard Addition Plot

In this method, equal volumes of sample are added to a deionized distilled water blank and to three
standards containing different known amounts of the test element. The volume of the blank and the
standards must be the same. The absorbance of each solution is determined and then plotted on the
vertical axis of a graph, with the concentrations of the known standards plotted on the horizontal axis.
When the resulting line is extrapolated back to zero absorbance, the point of interception of the abscissa
is the concentration of the unknown. The abscissa on the left of the ordinate is scaled the same as on the
right side, but in the opposite direction from the ordinate. An example of a plot so obtained is shown in
Figure 1.

A bso rb anc e

Ze ro
A bso rb anc e

Conc entratio n

Figure 1. Standard Addition Plot

Conc. of sample Addn 0 Addn 1 Addn 2 Addn 3

No Addn Addn of 50% Addn of 100% Addn of 150%
of Expected of Expected of Expected
Amount Amount Amount

The method of standard additions can be very useful; however, for the results to be valid the following
limitations must be taken into consideration:

1. The absorbance plot of sample and standards must be linear over the concentration range of
concern. For best results the slope of the plot should be the same as the slope of the aqueous
standard curve. If the slope is significantly different (more than 20%) caution should be
exercised.

2. The effect of the interference should not vary as the ratio of analyte concentration to sample
matrix changes and the standard addition should respond in a similar manner to the analyte.

3. The determination must be free of spectral interference and corrected for non-specific
background interference.

C-36
2.1.8 General Procedure for Analysis by Atomic Absorption

2.1.8.1 Direct Aspiration

Differences between the various makes and models of satisfactory atomic absorption spectrometers
prevent the formulation of detailed instructions applicable to every instrument. The analyst should follow
the manufacturer’s operating instructions for the particular instrument. In general, after choosing the
proper hollow cathode lamp for the analysis, the lamp should be allowed to warm up for a minimum of 15
minutes unless operated in a double beam mode. During this period, align the instrument, position the
monochromator at the correct wavelength, select the proper monochromator slit width, and adjust the
hollow cathode current according to the manufacturer’s recommendation. Subsequently, light the flame
and regulate the flow of fuel and oxidant, adjust the burner and nebulizer flow rate for maximum percent
absorption and stability, and balance the photometer. Run a series of standards of the element under
analysis and construct a calibration curve by plotting the concentrations of the standards against the
absorbance. For those instruments which read directly in concentration set the curve corrector to read
out the proper concentration. Aspirate the samples and determine the concentrations either directly, or
from the calibration curve. Standards must be run each time a sample or series of samples are run.

Calculation - Direct determination of liquid samples:

Read the metal value in mg/L from the calibration curve or directly from the readout system of the
instrument.

1. If dilution of sample was required:

mg metal/L in sample = A ( C+B ) / C

where: A = mg/L of metal in diluted sample from calibration curve

B = mL of deionized water used for dilution
C = mL of sample aliquot

2. For samples containing particulates:

mg metal/L in sample = A(V/C)

where: A = mg/L of metal in processed sample from calibration curve

V = final volume of the processed sample in mL
C = mL of sample aliquot processed

3. For solid samples: report all concentrations as mg/kg dry weight:

Dry sample:

mg metal/kg sample = AxV

D

where: A = mg/L of metal in processed sample from calibration curve

V = final volume of the processed sample in mL
D = weight of dry sample in gram

Wet sample:

mg metal/kg sample = AxV

WxP

where: A = mg/L of metal in processed sample from calibration curve

V = final volume of the processed sample in mL
W = weight of wet sample in grams
P = % solids in wet sample

C-37
2.1.8.2 Furnace Procedure

Furnace devices (flameless atomization) are a most useful means of extending detection limits. Because
of the differences between various makes and models of satisfactory instruments, no detailed operating
instructions can be given for each instrument. Instead, the analyst should follow the instructions provided
by the manufacturer of the particular instrument. In addition, the following points may be helpful.

1. Background correction is important when using flameless atomization, especially below 350nm.
Certain samples, when atomized, may absorb or scatter light from the lamp. This can be caused
by the presence of gaseous molecular species, salt particles, or smoke in the sample beam. If no
correction is made, sample absorbance will be greater than it should be, and the analytical result
will be erroneously high. Zeeman background correction is effective in overcoming composition
or structured background interferences. It is particularly useful when analyzing for As in the
presence of Al and when analyzing for Se in the presence of Fe.

2. Memory effects occur when the analyte is not totally volatilized during atomization. This condition
depends on several factors: volatility of the element and its chemical form, whether pyrolytic
graphite is used, the rate of atomization, and furnace design. This situation is detected through
blank burns. The tube should be cleaned by operating the furnace at full power for the required
time period, as needed, at regular intervals during the series of determinations.

3. Inject a measured microliter aliquot of sample into the furnace and atomize. If the concentration
found is greater than the highest standard, the sample should be diluted in the same acid matrix
and reanalyzed. The use of multiple injections can improve accuracy and help detect furnace
pipetting errors.

4. To verify the absence of interference, follow the serial dilution procedure given in section 2.1.4.2.

5. A check standard should be run after approximately every 10 sample injections. Standards are
run in part to monitor the life and performance of the graphite tube. Lack of reproducibility or
significant change in the signal for the standard indicates that the tube should be replaced. Tube
life depends on sample matrix and atomization temperature. A conservative estimate would be
that a tube will last at least 50 firings. A pyrolytic coating will extend that estimated life by a factor
of three.

Calculation: Read the metal value in µg/L from the calibration curve or directly from the
readout system of the instrument.

1. If different size furnace injection volumes are used for samples and standards:

µg metal/L of sample = Z ( S/U )

where: Z = µg/L of metal read from calibration curve or readout system

S = µL of standard injected into furnace for calibration curve
U = µL of sample injected for analysis

2. If dilution of sample was required but sample injection volume is the same as for
the standard:

µg metal/L of sample = Z ( C+B ) / C

where: Z = µg/L of metal in diluted aliquot from calibration curve

B = mL of deionized distilled water used for dilution
C = mL of sample aliquot

C-38
 3. For sample containing particulates:

µg metal/L of sample = Z(V/C)

where: Z = µg/L of metal in processed sample from calibration curve

V = final volume of processed sample in mL
C = mL of sample aliquot processed

4. For solid samples: Report all concentration as mg/kg dry weight

Dry sample:

mg metal /kg sample = ( Z x V/ 1000 ) / D

where: Z = µg/L of metal in processed sample from calibration curve

V = final volume of processed sample in mL
D = weight of dry sample in grams

Wet sample:

mg metal/kg sample = ( Z x V/ 1000 ) / (WxP)

where: Z = µg/L of metal in processed sample from calibration curve

V = final volume of processed sample in mL
W= weight of wet sample in grams
P = % solids in wet sample

2.1.9 Quality Control for Water Analysis

1. Minimum Requirements
(i) All quality control data should be maintained and available for easy reference or
inspection.

(ii) An unknown performance sample (when available) must be analyzed once per
year for the metals measured. Results must be within the control limits
established by good laboratory practice. If problems arise, they should be
corrected, and a follow-up performance sample should be analyzed.

2. Minimum Daily Control

(i) After a calibration curve composed of a minimum of a reagent blank and three
standards has been prepared subsequent calibration curves must be verified by
use of at least a reagent blank and one standard at or near the median
concentration level (MCL). Daily checks must be within ±10 percent of original
curve.

(ii) If 20 or more samples per day are analyzed, the working standard curve must be
verified by running an additional standard at or near the MCL every 20 samples.
Checks must be within ±10 percent of original curve.

C-39
 3. Optional Requirements
(i) A current service contract should be in effect on balances and the atomic
absorption spectrometer.

(ii) Class S weights should be available to make periodic checks on balances.

(iii) Chemicals should be dated upon receipt and replaced as needed or before shelf
life has been exceeded.

(iv) A known reference sample (when available) should be analyzed once per quarter
for the metals measured. The measured value should be within the control limits
established by good laboratory practice.

(v) At least one duplicate sample should be run every 10 samples, or with each set
of samples, to verify precision of the method. Checks should be within the
control limit established by good laboratory practice.

(vi) Standard deviation should be obtained and documented for all measurements
being conducted.

(vii) Quality control charts or a tabulation of mean and standard deviation should be
used to document validity of data on a daily basis.

2.2 Hydride Vapour Generation Sample Introduction (HVAAS/HVICP)

2.2.1 Introduction

The determination of small traces of a number of metallic hydride-forming elements (especially As, Sb,
Se) has been of importance in toxicology for many years. In many fields of industry, in geochemistry and
in metallurgy, the trace determination of these elements is also of importance.

It is generally agreed that, because of its simplicity and specificity, atomic absorption spectroscopy or
atomic emission spectroscopy, together with a hydride generation sample introduction system, best
meets the requirements for the economical determination of trace concentrations of these elements. [1]

2.2.2 Method Summary

Hydride vapour generation sample introduction systems utilize a chemical reduction to form a volatile
hydride with the metal of interest. This volatile hydride is then swept into either a heated reaction cell, or
directly into the plasma of an ICP, where the metal of interest is freed from the hydride.

Standard FAAS (heated reaction cell) or ICP is then carried out on the volatile metallic species. [1]

See Section 2.1 and 2.4 for details on FAAS and ICP.

2.2.3 Interferences

The following metals, compounds and conditions may interfere:

- easily reduced metals; ie, copper, silver, mercury, etc.
- high concentrations of transition metals (>200 mg/L).
- oxidizing agents remaining following sample digestion; ie, oxides of nitrogen. [2]
- oxidation state of element: sample may require a pre-treatment prior to analysis using a
reducing agent such as potassium iodide (KI).

C-40
2.2.4 General Procedure

Sodium borohydride solution is used as the reductant for the determination of metallic hydride-forming
elements. Sodium borohydride liberates hydrogen on contact with acids. The reaction mechanisms
involved in the reduction of metal ions are complicated and almost certainly take place via the formation
of intermediate radicals. The following equation represents a simplification of the reduction and free
volatile metal forming mechanism:

Mn+ + nBH4- ---> MHn (gas) + H2 (gas) + n/2 B2H6

MHn + heat (900-1000°C) ---> M

M is a metallic element which forms a volatile hydride (ie, arsenic, bismuth, antimony, selenium, tin,
tellurium, etc).

The sample solution is first treated to convert the metal of interest to ionic form in acidic solution.
Reductant is then dispensed into the sample solution where it reacts with liberated hydrogen. A
carrier gas (eg, argon) flushes the hydride into a heated reaction cell or directly into the plasma of
an ICP where it is decomposed and the absorption or emission of the metal is measured. Where a
reaction cell is used, it is heated to between 900°C and 1000°C. [1]

2.3 Cold Vapour Generation Sample Introduction (CVAAS)

2.3.1 Introduction

The determination of small traces of mercury has been of importance in toxicology for many years. In
many fields of industry, in geochemistry and in metallurgy, the trace determination of this element is also
of importance.

It is generally agreed that, because of its simplicity and specificity, atomic absorption spectroscopy,
together with a cold vapour generation sample introduction system, best meets the requirements for the
economical determination of trace concentrations of mercury. [1]

2.3.2 Method Summary

Cold vapour generation sample introduction systems utilize a chemical reduction to form a volatile metal
species. This volatile species is then swept into a cell positioned in the path of a standard AAS.
Concentration is then determined at a specific wavelength. [1]

2.3.3 Interferences and Precautions

Any produced vapour which absorbs at the same wavelength as the metal of interest will interfere. [3]

2.3.4 General Procedure

Stannous chloride is used as the reductant for the determination of room temperature volatile metallic
elements (ie, mercury). Stannous chloride reduces the metal of interest to its elemental form.

The reaction mechanisms involved in the reduction of metal ions are complicated and almost certainly
take place via the formation of intermediate radicals. The following equation represents a simplification of
the reduction and volatilization of mercury:

Hg2+ + Sn2+ ---> Hg (gas) + Sn4+

C-41
The sample is first treated to convert mercury to ionic form in acidic solution. Reductant (usually tin) is
then dispensed into the sample solution to produce volatile elemental mercury. A carrier gas (eg, argon)
flushes the volatile mercury into a cell positioned in the light path of an AAS and concentration is
determined by standard AAS technique. [1]

2.4 Inductively Coupled Plasma – Atomic Emission Spectrometry (ICP-AES)

2.4.1 Introduction

ICP-AES is a rapid multi-element technique which is capable of the simultaneous determination of major,
minor, and trace elements in solution. Reference 1 is recommended as an excellent source of
information on this topic. Some advantages of this technique include:

1. A large linear dynamic range of 5 to 6 decades for each analytical line which permits both trace
and major elements to be analyzed in the same sample dilution.
2. The low sample volume (5 to 20 mL) required for the simultaneous determination of up to 70
elements (depending on the instrument).
3. A low susceptibility to chemical and matrix interferences.
4. The versatility to add a hydride generator, ultrasonic nebulizer, graphite furnace or laser ablation
system to increase sensitivity even further.

Some disadvantages include:

1. A high initial instrument cost.

2. A high initial investment in data handling software.
3. Clogging of some pneumatic nebulizer systems.
4. Spectral interferences - (see interference section 2.1.4).

2.4.2 Method Summary

Atomic emission spectrometry (AES), atomic absorption spectrometry (AAS), and atomic fluorescence
spectrometry (AFS) all measure atomic spectra in the ultra violet, visible, and near infrared region of the
electromagnetic spectrum. All three methods must atomize the sample prior to excitation and
measurement. In AES, the inductively coupled plasma (ICP) provides the energy for atomization and
excitation. The method is applicable to aqueous samples and to digests of sediments, soils, and biota.

2.4.3 Detection Limits

The Detection Limit (DL) is a statistical figure of merit. It can be defined as the smallest signal equal to 2 -
6 times the standard deviation of the background signal and, in deionized water, this definition gives a fair
estimation of the instrument DL. Errors associated with Inter Element Correction (IEC) factors are
thought to be in the order of ±5% [2, 3] although Millward and Kluckner [4] found that ±2.5% is probably
more likely. The EDL (Effective Detection Limit) can then be calculated as follows:
2 2 1/2
EDL = (d + (0.05t) )

where d = 3 times standard deviation of base noise

t = concentration of interfering element times the IEC factor

Experience indicates that as the matrix becomes more complex, the EDL rises. The above calculation,
although not perfect, quantitates to some extent what is observed in practice. In any event, the method of
determining EDLs should accompany any data generated by any analytical technique.

C-42
Table C-2 indicates the detection power of ICP-AES for an argon ICP operated with a pneumatic
nebulizer 1. The detection limits are on a 2 times standard deviation basis. These DLs can vary by a
factor of 10 or more depending on:

1. Source - 27 MHz vs 40 MHz

2. Nebulizer - pneumatic vs ultrasonic vs hydride
3. Operating Conditions - compromise vs optimal
4. Differences in spectral bandwidth
5. Prominent line chosen
6. Concomitants - pure water vs sediment digests

Table C-2
Detection Detection Detection
Element Limit Element Limit Element Limit
µg/L µg/L µg/L

Aluminum Al 10-30 Indium In 30-100 Ruthenium Ru 30-100

Antimony Sb 30-100 Iridium Ir 30-100 Scandium Sc 3-10
Arsenic As 30-100 Iron Fe 3-10 Selenium Se 30-10
Barium Ba 3-10 Lanthanum La 10-30 Silicon Si 30-100
Beryllium Be 3 Lead Pb 30-100 Silver Ag 3-10
Bismuth Bi 30-100 Lithium Li 3-10 Sodium Na 10-30
Boron B 3 Lutetium Lu 3-10 Strontium Sr 3-10
Cadmium Cd 10-30 Magnesium Mg 3-10 Tantalum Ta 10-30
Calcium Ca 10-30 Manganese Mn 3 Tellurium Te 100-300
Carbon C 30-100 Mercury Hg 30-100 Terbium Tb 30-100
Cerium Ce 30-100 Molybdenum Mo 3-10 Thallium Tl 30-100
Chromium Cr 3-10 Neodymium Nd 30-100 Thorium Th 30-100
Cobalt Co 3-10 Nickel Ni 10-30 Thulium Tm 3-10
Copper Cu 3-10 Niobium Nb 30-100 Tin Sn 30-100
Dysprosium Dy 10-30 Osmium Os 3 Titanium Ti 3-10
Erbium Er 10-30 Palladium Pd 30-100 Tungsten W 30-100
Europium Eu 3-10 Phosphorus P 30-100 Uranium U 100-300
Gadolinium Gd 10-30 Platinum Pt 30-100 Vanadium V 3-10
Gallium Ga 30-100 Potassium K 30-300 Ytterbium Yb 3-10
Germanium Ge 30-100 Praseodymium Pr 30-100 Yttrium Y 3-10
Gold Au 10-30 Rhenium Re 10-30 Zinc Zn 3-10
Hafnium Hf 10-30 Rhodium Rh 30-100 Zirconium Zr 10-30
Holmium Ho 3-10

2.4.4 Interferences and Precautions

1. Physical
Samples containing high concentrations of acids and/or dissolved solids will affect surface
tension and hence sample uptake, droplet size distribution, and aerosol transport to the plasma.
High dissolved solids can also cause salt build-up at the tip of some pneumatic nebulizers.
Sample uptake variations due to viscosity differences can be controlled with a peristaltic pump.
Salt build-up can be controlled by wetting the argon prior to nebulization, using a tip washer, or
diluting the sample. Changes in droplet size distribution cannot be compensated for as easily,
other than matching the standard and sample matrix, which is difficult if the sample matrix is
unknown.

2. Chemical [5]
Chemical interferences include molecular compound formation, ionization effects, and solute
vaporization effects. Normally, these effects are not significant with the ICP technique. If
observed, they can be minimized by careful selection of operating conditions (incident power,
viewing height, nebulizer argon flow, etc.), by buffering of the sample, by matrix matching, and by
internal standard procedures. Chemical interferences are highly dependent on matrix type and
the specific analyte element.

C-43
3. Spectral
ICP-AES suffers more from spectral interferences and less from chemical interferences than
FAAS where the opposite is true. Spectral interferences classify as [1]:
- Stray light
- Continua and line wings contributed by the constituents of the sample
- Spectral lines and molecular bands contributed by the discharge atmosphere and the solvent
- Spectral lines and molecular bands contributed by the constituents of the sample

The effect of the above interferences is background enhancement which can be categorized as:
- Simple or “flat” background
- Sloping background
- Direct line overlap
- Complex line overlap

All of the background changes can be corrected to some degree by measuring the background
off-peak then subtracting the value(s) from the peak and/or subtracting empirically calculated
inter-element corrections. This topic is broad and complex but there are many excellent texts and
papers which cover spectral interferences in ICP-AES. For instance, EPA method 200.7 gives
suggested background correction positions for a number of specified analysis lines. The ICP
spectroscopist must carefully choose background correction positions for their particular
instrument and analysis requirements.

2.4.5 General Procedure

1. Aerosol Production
Nebulizers are the weak point in ICP, and are at the root of many ICP problems. The function of
the nebulizer is to convert the solution to a fine, uniform aerosol. The aerosol will consist of
droplets with a range of sizes but most of the aerosol mass should be in the smaller size range.

Pneumatic nebulizers are common and can be divided into two types - concentric (e.g. Meinhard)
and Cross-flow (eg. MAX). Grid nebulizers (e.g. Hildebrand) are becoming more common.
Special nebulizers are available such as the Babington (e.g. GMK) for samples containing high
concentrations of dissolved solids and the Fritted Disc for LC-ICP-AES applications.

Ultrasonic nebulizers have been introduced commercially in the last few years. Their efficiency at
producing an aerosol is typically 10 times the efficiency of the pneumatic nebulizers. Because of
the increase in material reaching the plasma, detection limits for many elements exceed
pneumatic nebulizer detection limits by a factor of 10. However, the upper concentration range
for these elements is decreased by a factor of 10.

The solution to be analyzed is either fed to the nebulizer by a pump or is pulled through as a
result of reduced pressure at the nozzle (Venturi effect).

As for AAS, electrothermal atomizers can be connected to ICP. These devices can be metal
(boat or filament) or graphite (yarn, rod or furnace).

2. Spray Chambers
The aerosol which is produced by the nebulizer consists of various size droplets. The function of
the spray chamber is to sort out the larger droplets and allow the finer droplets through to the
plasma. A major part of the primary aerosol is lost to chamber surfaces - in the order of 98 -
99.5% [1].

The most common spray chamber is the dual concentric or Scott chamber. Cyclone chambers
are starting to become popular. These sort droplets by imparting a spiral motion to the aerosol so
that the larger droplets strike the wall of the chamber preferentially.

C-44
3. Torches
The most critical component of the ICP assembly is the torch and although there are many
different designs, the torch type in most common use for argon plasmas is the three concentric
tube “Fassel” torch. Over the years the Fassel torch has been refined to reflect the following
performance requirements [1]:
1. Easy ignition of the plasma.
2. Continuous, stable plasma generation with a minimum influence of the injected sample,
primarily the absence of risks of extinguishing the plasma and formation of deposits in the
torch.
3. A sufficiently high sample flow through the plasma tunnel to the observation zone.
4. An optimum sample heating efficiency by a long residence time of the sample in the plasma.
5. A low gas consumption rate.
6. Minimal power requirements to reduce size and cost of the RF power supply.

The torch is placed in a water-cooled induction coil of an RF generator. Two or three gas flows
are introduced into the tubes of the torch and the flowing gas is made electrically conductive by
Tesla sparks.

The RF current through the coil generates oscillating magnetic fields which induce electric
currents in the conducting gas, which in turn heats up due to resistance and forms the plasma.
The aerosol from the nebulizer/spray chamber is introduced into the centre of the plasma where it
becomes volatilized and atomized. The resulting spectral lines are separated and their intensity
measured by the spectrometer.

4. Spectrometer Systems
Spectral information from the ICP can be separated in two different ways. Sequential
spectrometers employ a monochrometer and various drive systems (Sine Bar, Direct, Magnetic,
Encoding) under computer control to scan the spectrum, stopping at lines of interest. Scan rate
and integration time at each selected line can be varied. Various peak-finding methods (Single,
Moving Window, Peak Area Fitting, Side Line Indexing) are used to ensure the requested peak is
presented to the detector. Flexibility is the main advantage of sequential spectrometers.

Simultaneous or Direct Reading Spectrometers are commonly based on concave grating mounts:
Rowland Circle, Paschen-Runge or Seya-Namioka or on an Echelle mount. Line selection must
precede the purchase of the instrument, keeping in mind that, due to physical limitations, line
selection compromises may be necessary. Speed is the main advantage of simultaneous
spectrometers.

Characteristics of the ideal spectrometer system for ICP-AES are as follows [1]:

1. Record all spectral information simultaneously.

2. Rapid signal acquisition and recovery.
3. Provide high contrast (high resolution, low stray light).
4. Possess a wide dynamic range - at least 106.
5. Provide accurate, precise wavelength identification and selection for analysis.
6. Highly stable, insensitive to environmental changes (temperature, humidity, vibration).
7. Provide means to identify and correct for interferences including displaying spectra for
operator.
8. Measure and subtract background.
9. Provide a permanent record of spectra and analysis results.
10. Computerized operation: control, readout, storage, data manipulation, statistical analysis,
report generation.

5. Method Validation
Method validation must be performed initially and whenever instrumental modifications are
incorporated. Method validation checks include determination of precision, accuracy, detection
limit, calibration curve linearity, and analytical range.

C-45
 As these items are easily measured it is recommended that they be monitored on a regular basis.
For example, measurement of precision and detection limit could be monitored weekly, or daily if
desired.

It should be noted that the responses of some ICP emission lines are not linear. Where the use
of an alternate analysis line is not possible (e.g. in a fixed - channel instrument). Computer curve
correction may be employed. Curvature of some lines is sensitive to operating conditions; the
validity of computer curve correction should be confirmed by regular analysis of QC solutions.

The extent of the upper range of each ICP channel must be known; detector and measurement
electronic parameters will limit the upper analysis range. Detectors may “saturate”, for some
elements at concentrations under 50 mg/L.

6. Long Term Stability of ICP Conditions

It is desirable to ensure that inter-element correction factors, line curvature, analytical ranges, and
other parameters remain constant. This may be done by setting the ratio of the intensities of an
“atom” line and an “ion” line to a constant value. This is usually accomplished by aspirating a
solution containing the two elements of interest and adjusting the nebulizer argon flow rate using
a mass flow controller until the desired intensities are observed. [6, 7]

7. Daily Instrument Calibration

Most ICP standardization schemes employ “two-point” calibration using a “blank” or “zero”
solution and a single “high-level” concentration for each element. The “high-level” points range
generally from 0.5 to 100 mg/L, although 1.0 to 10.0 mg/L levels are typical.

Since an ICP may analyze over thirty elements simultaneously, it is important to monitor the
integrity of the mixed calibration solutions, since element concentrations may vary due to
contamination or precipitation. A hardcopy of instrument responses for each element should be
produced and examined daily. Also, analysis of calibration verification solutions should be carried
out prior to sample analysis by analyzing a check standard prepared independently from the
calibration solutions. Acceptance criteria for the verification standard should be within
approximately 5% of the “real” value.

It is also important to monitor the stability of calibration over the “long term” by analyzing a check
or calibration standard after every 10 samples. This not only monitors instrument stability but
ensures that other factors such as nebulizer clogging do not go undetected.

2.4.6 Precision

Precision represents the reproducibility of measurement and is usually expressed in terms of percent
relative standard deviation (RSD). At the detection limit (DL) the RSD will be higher than at levels above
the DL. For example when the DL is set at:

2 times standard deviation - RSD is 50%

3 times standard deviation - RSD is 33%
5 times standard deviation - RSD is 10%

At levels equalling a few hundred times the DL, short term precision of 0.5 - 2% can be obtained
depending on [1]:

- nebulizer
- ICP system
- spectrometer
- analyte
- sample type
- definition of “short term”
- “enthusiasm” of the analyst

C-46
2.4.7 Accuracy

Accuracy or agreement between measured and “true” value can best be determined using Standard
Reference Materials (SRM’s).

2.4.8 Quality Control

To ensure accuracy and precision, quality control blanks, duplicates, spikes, and certified reference
materials must be incorporated into the analysis scheme. It should be noted that a wide variety of
certified reference materials for water, geologicals, and biological materials are available at levels suitable
for ICP analysis.

2.4.9 References

1. P. W. J. M. Boumans, Ed., Inductively Coupled Plasma Emission Spectroscopy, Parts I and II,
Chemical Analysis 90. John Wiley & Sons Pub., (1987).

2. M. Thompson & J. N. Walsh, Ed., Handbook of Inductively Coupled Plasma Spectrometry, 2nd
ed., Chapman & Hall Pub., (1989).

3. S. E. Church, Geostand. Newslett., Vol. 2, p. 133, (1981).

4. Christopher G. Millward & Paul D. Kluckner, JAAS, Vol. 6, Feb., (1991).

5. EPA Method 6010A, Revision 1, November (1990).

6. Botto, R.I., Long-term Stability of Spectral Interference Calibrations for Inductively Coupled
Plasma Atomic Emission Spectrometry, Analytical Chemistry, 54:1654 (1982).

7. Methods for Chemical Analysis of Water and Wastes, EPA-600, 4-79-020, March, 1983, Method
200.7.

8. Instructions - MHS-20 Mercury/Hydride System, Publication 338-A2-M 294/12.79. Bodenseewerk

Perkin-Elmer & Co. GMBH/Uberlingen. 1979.

9. Test Methods for Evaluating Solid Wastes - Physical/Chemical Methods. Publication #SW-846
Revision 0. United States Environmental Protection Agency, Washington, DC. 3rd edition, 1986.

10. Test Methods for Evaluating Solid Wastes - Physical/Chemical Methods (Revised). Publication
#SW-846 Revision 1. United States Environmental Protection Agency, Washington, DC. 3rd
edition 1990.

11. Instructions - MHS-20 Mercury/Hydride System, Publication 338-A2-M 294/12.79. Bodenseewerk

Perkin-Elmer & Co. GMBH/UBERLINGEN. 1979.

12. Test Methods for Evaluating Solid Wastes - Physical/Chemical Methods (Revised). Publication
#SW-846 Revision 1. United States Environmental Protection Agency, Washington, DC. 3rd
edition, 1990.

2.4.10 Revision History

February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes removed. Minor editing.

C-47
2.5 Metal Analysis of Solids by ICP

Parameter Metals

Analytical Method D+G; acid digestion; ICP

Introduction Inductively Coupled Argon Plasma - Atomic Emission Spectrometry (ICP) is

a rapid multi-element scanning technique for the analysis of elements
including metals. This analysis is applicable to a large list of elements within
the periodic table but for the purposes of this method, 25 of the more
commonly analyzed metals will be targeted.

Method Summary The soil or sediment sample is initially homogenized to ensure representative
sub-aliquots will be digested and analyzed. An accurate weight of soil is
acid digested and the resulting digestate is analyzed for metals by ICP.

MDL Target Element Detection Limit (ug/g)

Aluminum 10
Antimony 10
Arsenic 30
Barium 0.1
Beryllium 1
Boron 0.5
Cadmium 5
Calcium 1
Chromium 2
Cobalt 1
Copper 1
Iron 2
Lead 10
Magnesium 0.1
Manganese 0.2
Molybdenum 4
Nickel 2
Phosphorus 20
Silver 2
Sodium 5
Strontium 0.1
Tin 5
Titanium 0.3
Vanadium 0.5
Zinc 1

Detection Limits have been derived by multiplying (weight / volume) factors

by the estimated instrument detection limits in solution. These limits are only
given as guidelines and are dependent on the specific instrument
configuration.

Matrix Soil, solids, (marine) sediments.

Interferences and Not available.

Precautions

C-48
Sample Handling Container - Acid Washed Polyethylene Bottle.
and Preservation Digested soils are already in an acid medium and require no extra
preservation chemicals.

Stability Metallic elements in acid digested soil samples have a holding time of six
months.

Instrumentation/ Refer to Specific Instrument Operations Manuals, EPA Method 6010A.

Calibration and
Analysis Procedures

Precision Refer to EPA Method 6010A and Section 2.5.6 of the ICP-AES method in the
B.C. Laboratory Manual for further explanations.

Accuracy Refer to EPA Method 6010A and Section 2.5.7 of the ICP-AES method in the
B.C. Laboratory Manual for further explanations.

Quality Control For each analytical batch include a minimum of the following:
a) Two method blanks
b) 10% Duplication (minimum of one)
c) One Standard Reference Material

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 18th edition, 1992 Section 3120 B.
b) Methods for Chemical Analysis of Water and Wastes, EPA-600 4-79-
020, March 1983, Method 200.7.
c) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication # SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition, 1990.

Revision Date: December 31, 2000

3.0 SPECIFIC ELEMENTAL CONDITIONS

Note: FA = Field acidified LA = Lab acidified

FF = Field filtered LF = Lab filtered

C-49
 Metals
Revision Date: October 1, 2013

Trace Metals Analysis by ICP-MS – PBM

Parameter Metals including major ions and trace metals.

Analytical Method Analysis by ICP-MS.

Introduction This method is applicable to metals in filtered or digested waters, and to total
recoverable metals in solid samples, tissues, and other matrices which have gone
through appropriate digestion procedures.

Method Summary This method describes the multi-elemental determination of trace elements by
ICP-MS. It is used to measure dissolved metals in water, total metals in water,
total recoverable metals in solid samples such as soil, sediment, and vegetation
from a Strong Acid Leachable (SALM) digestate, or other acceptable digestion
procedures.

The method measures ions produced by a radio-frequency inductively coupled

plasma. Analyte species originating in a liquid are nebulized and the resulting
aerosol transported by argon gas into the plasma torch. The metal ions produced
are entrained in the plasma gas and extracted, by means of a differentially
pumped vacuum interface, into a mass spectrometer. The metal ions produced in
the plasma are sorted according to their mass-to-charge ratios by a quadrupole or
magnetic sector mass spectrometer having a minimum resolution capability of 1
AMU peak width at 5% peak height. The ions transmitted through the quadrupole
are quantified by a detector and the ion information is processed by a data
handling system.

This method is performance-based. Laboratories may adopt alternative options

to improve performance or efficiency provided that all stated performance
requirements and prescribed (mandatory) elements are met.

C-50
Parameters and This method is applicable to the following parameters:
Parameter Codes
Parameter Parameter Parameter
Parameter Parameter Parameter
Code Code Code
Aluminum AL-x Copper CU-x Selenium SE-x
Antimony SB-x Iron FE-x Silicon SI-x
Arsenic AS-x Lead PB-x Silver AG-x
Barium BA-x Lithium LI-x Sodium NA-x
Beryllium BE-x Magnesium MG-x Strontium SR-x
Manganes
Bismuth BI-x MN-x Thallium TL-x
e
Boron B--x Mercury HG-x Tin SN-x
Molybdenu
Cadmium CD-x MO-x Titanium TI-x
m
Calcium CA-x Nickel NI-x Uranium U--x
Phosphoru
Chromium CR-x P--x Vanadium V--x
s
Cobalt CO-x Potassium K--x Zinc ZN-x
x may be T or D dependent upon Total or Dissolved as reported parameter.

Other metals may be analyzed by this method if acceptable performance is

demonstrated and validated.

Matrix Water, soils, sediments, sludges, solids, air filters, animal and plant tissues with
appropriate digestion or leachate procedures applied.

Interferences and Interferences associated with ICP-MS analysis may be classified as physical,
Precautions isobaric (elemental or polyatomic), memory (carryover) or contamination in
nature.

a) Physical interferences can be reduced by using internal standards which

compensate for matrix effects. High levels of dissolved solids in the sample
will increase deposition of material on the extraction and/or skimmer cones,
reducing the effective diameter of the orifices and therefore ion transmission.
Dissolved solids of no more than 0.2% have been recommended.

b) Both the isobaric and molecular ion interferences must be fully investigated
and understood prior to the introduction of this methodology. When they
cannot be avoided by the selection of alternative analytical isotopes,
appropriate corrections must be made to the data. Equations for the
correction of data should be established at the time of the analytical run
sequence, as the polyatomic ion interferences will be highly dependent on the
sample matrix and chosen instrument conditions.

c) Memory effects can result from sample deposition on the extraction and
skimmer cones, and from the buildup of sample material in the plasma torch
and spray chamber. The site where these effects occur is dependent on the
element and can be minimized by flushing the system with a rinse blank
between samples. The possibility of memory interferences should be
recognized within an analytical run and suitable rinse times should be used to
reduce them. The rinse times necessary for a particular element should be
estimated prior to analysis.

d) Interferences may also result from contaminants in acids, reagents,

glassware, and other sample processing hardware that lead to artifacts and/or
elevated baseline. All materials used should be routinely monitored and
demonstrated to be free of interferences under the conditions of the analysis.

C-51
Sample Handling Refer to the “Summary of Sample Preservation and Hold Time Requirements”
and Preservation table found in Section A of the British Columbia Environmental Laboratory
Manual.

Stability Refer to the “Summary of Sample Preservation and Hold Time Requirements”
table found in Section A of the British Columbia Environmental Laboratory
Manual.

Procedure Reagents:

Reagents may contain elemental impurities that might affect the integrity of
analytical data. Owing to the high sensitivity of ICP-MS, high-purity reagents
should be used whenever possible.

Digestion:

Refer to British Columbia Environmental Laboratory Manual for appropriate

sample preparation procedures.

Where the Laboratory Manual does not prescribe digestion procedures, other
appropriate digestion methods may be used provided performance requirements
are met.

Instrumental Analysis:

Detailed instrumental procedures are not provided in this method. The

procedures described in the following reference are suitable for general guidance:

 EPA Method 200.8 “Determination of Trace Elements in Waters and Wastes

by Inductively Coupled Plasma - Mass Spectrometry”, Revision 5.4, U.S.
Environmental Protection Agency, May 1994.

 EPA SW846 Method 6020A “Inductively Coupled Plasma - Mass Spectrometry”,

Revision 1, U.S. Environmental Protection Agency, February 2007.

This method is applicable only to ICP-MS analysis. Refer to USEPA Method

200.8 or 6020A for guidelines on establishing quantitation and confirmation ions
for trace metal analytes.

The use of internal standards is required. Internal standards can vastly improve
method accuracy and precision. Instrument drift as well as suppressions or
enhancements of instrument response caused by the sample matrix must be
corrected for by the use of internal standards. Refer to EPA Method 200.8 for
recommended internal standard criteria.

Performance Any analytical method options selected for this analysis must meet or exceed the
Requirements method validation performance requirements specified below:

Accuracy and Precision requirements apply to measures of long term method

performance (averages and standard deviations). Achievement of these
requirements is to be demonstrated during initial and ongoing method re-
validation studies. They do not constitute acceptance criteria or Data Quality
Objectives for individual Quality Control samples.

C-52
For Initial Validations, averages of at least 8 spikes or certified reference
materials (CRMs) must be assessed (preferably taken from multiple analytical
batches).

Ongoing re-validations (performance reviews) should assess QC data

encompassing longer timeframes (e.g. 6 months to 1 year). A minimum
frequency of 2 years is recommended for Ongoing Re-validations.

Accuracy Requirement: Refer to British Columbia Environmental Laboratory

Manual for appropriate sample preparation procedures.

Precision Requirement: Refer to British Columbia Environmental Laboratory

Manual for appropriate sample preparation procedures.

Sensitivity Requirement: Where possible, the method should generate Method

Detection Limits that are less than 1/5 of applicable numerical standards. The
method is not fit-for-purpose if an MDL exceeds a guideline, standard, or
regulatory criteria against which it will be used for evaluation of compliance.

Linear Dynamic Range: Linear range studies are to be performed during the
initial validation of the method to determine the upper limit of linearity on the
specific ICP-MS instrument. It must be determined from a linear calibration. The
LDR should be determined by analyzing at least 3 different standard
concentrations for each analyte and the observed analyte concentration is within
90-110% of the stated concentration of the standard. Note that the LDR
concentration may not be the upper limit of the element, but rather the upper
concentration examined. If a sample concentration exceeds the LDR, it must be
diluted and reanalysed. The frequency of the LDR determination is subject to the
individual laboratory’s Quality Management System.

Internal Standard Recovery Range: The absolute response of any internal

standard must not deviate more than 60-125% from the original response in the
calibration blank. Deviations outside this range must be investigated and
reanalysed.

Interference Analysis: Laboratories must show evidence that elemental isobaric

and polyatomic interference have been fully investigated and corrected for in the
reporting of data by this technique.

Elemental Isobaric Interference: Atoms or elements having the same atomic

weights are naturally occurring and therefore must be compensated for isobaric
overlap. This should be automatically corrected in the instrument software or using
post analysis corrections.

Polyatomic Isobaric Interference: Polyatomic ions are formed from samples

containing high concentrations of particular elements (i.e. Agides, Oxides, Halides,
etc.). These interferences may be automatically corrected in the instrument
software, or using post analysis corrections, while others may be corrected by using
an alternative isotope, or removed by collision/reaction cell or high resolution
technologies. Daily optimisation of the nebulizer gas pressure reduces the formation
of oxides.

C-53
Quality Control Summary of Instrument QC Requirements for Waters

QC Component Minimum Frequency Minimum Data Quality

Objectives*
Instrument Blank 1 per 20 samples Less than reported DL
Control Standard / Initial 90-110% recovery (after
1 per batch
Calibration Verification (ICV) internal standard correction)
1 per 20 samples and 85-115% recovery (after
Continuing Calibration
at the end of each internal standard correction)
Verification (CCV)
run. for mid-level standards.
* Minimum DQOs apply to individual QC samples, not averages, and only at levels above 10x MDL.
Laboratories should report qualified data when DQOs are not met, unless other evidence
demonstrates that the quality of associated sample data has not been adversely affected.

Instrument Blank: Required. Minimum one per batch of 20 or less, or as

necessary to ensure contamination control.

Control Standard / Initial Calibration Verification (ICV): Required. A control

standard from a source separate from the calibration standard must be analyzed to
monitor calibration accuracy.

Continuing Calibration Verification (CCV): Required. Calibration standards

(typically a mid-point standard) must be analyzed periodically throughout the
instrument run to monitor calibration drift (at least 1 per 20 samples). A control
standard may serve the same purpose.

Prescribed The following components of this method are mandatory:

Elements
a) This method is applicable only to analysis by ICP-MS.
b) Initial calibrations must be done daily.
c) Internal standards must be used. Internal standards must cover all analytes
within a 65 AMU Range.
d) All Performance Requirements and Quality Control requirements must be
met.

Apart from these limitations, and provided performance requirements are met,
laboratories may introduce modifications to this method in order to improve quality
or efficiency.

References a) EPA Method 200.8 “Determination of Trace Elements in Waters and Wastes
by Inductively Coupled Plasma - Mass Spectrometry”, Revision 5.4, U.S.
Environmental Protection Agency, May 1994.

b) EPA SW846 Method 6020A “Inductively Coupled Plasma - Mass

Spectrometry”, Revision 1, U.S. Environmental Protection Agency, February
2007.

Revision History First version of BC Lab Manual ICPMS method (PBM format).
May 24, 2011:
Trace Metals Analysis by ICP-MS – PBM method added to
October 1,
2013 version of BC Lab Manual, effective October 1, 2013.
2013:

C-54
 Metals
Revision Date: December 31, 2000

Aluminum (Atomic Absorption - Direct Aspiration)

Parameter Aluminum, total
Aluminum, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) Al-T X073

LA: HNO3: AA (total) Al-T X351
FF, FA: HNO3: AA (dissolved) Al-D X203
LF, LA: HNO3: AA (dissolved) Al-D X085

Method Summary Aqueous solutions of metals are aspirated into a flame and atomized. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.1 mg/L
Range: 0.1-50.0 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. Ionization
should be controlled by the addition of potassium chloride to a level of 0.1%.
The Al signal can be enhanced by the presence of Fe, Ti, fluoroborate and
acetic acid.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Al hollow cathode lamp

Parameters Wavelength: 309.3 nm (primary); 396.2 nm (alternate)
Type of Flame: nitrous oxide-acetylene
Background Correction: recommended

Apparatus, Materials See sections 2.1.5 and 2.1.6 of this manual.

and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

C-55
References a) Standard Methods for the Examination of Water and Wastewater
APHA, AWWA, WEF, 18th edition, 1992, Method 3111 B/D.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-56
 Metals
Revision Date: December 31, 2000

Antimony (Atomic Absorption - Direct Aspiration)

Parameter Antimony, total
Antimony, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) Sb-T X073

LA: HNO3: AA (total) Sb-T X351
FF, FA: HNO3: AA (dissolved) Sb-D X203
LF, LA: HNO3:AA (dissolved) Sb-D X085

Introduction Antimony and its compounds have been reported to cause dermatitis,
keratitis, conjunctivitis and nasal septal ulceration by contact, fumes, or dust.

Method Summary Aqueous solutions of metals are aspirated into a flame and atomized. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.2 mg/L
Range: 0.20-40.0 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, waste water and marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. A decrease in
absorption occurs with increasing acid concentration. To avoid this effect,
matrix-match the acid concentration of the samples and standards.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Sb EDL or hollow cathode lamp

Parameters Wavelength: 217.6 nm (primary)
Type of Flame: air/acetylene
Background Correction: recommended

Apparatus, Materials See section 2.1.5 and 2.1.6 of this manual.

and Reagents

Precision None listed.

Accuracy None listed.

C-57
Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WEF, 18th edition, 1992, Method 3111 B/D.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-58
 Metals
Revision Date: December 31, 2000

Antimony (Atomic Absorption - Gaseous Hydride)

Parameter Antimony, total
Antimony, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section, and section 2.2 the hydride AA
method section.

EMS Code FA: HNO3: HVAAS (total) Sb-T X289

LA: HNO3: HVAAS (total) Sb-T X354
FA: HCl: HVAAS (total) Sb-T X345
LA: HCl: HVAAS (total) Sb-T X355
FF, FA: HNO3: HVAAS (dissolved) Sb-D X202
LF, LA: HNO3: HVAAS (dissolved) Sb-D X359
FF, FA: HCl: HVAAS (dissolved) Sb-D X348
LF, LA: HCl: HVAAS (dissolved) Sb-D X360

Introduction Antimony and its compounds have been reported to cause dermatitis, keratitis,
conjunctivitis, and nasal septal ulceration by contact, fumes, or dust.

Method Summary Antimony is converted to a gaseous hydride and analyzed by atomization in a

heated quartz tube. Conversion to hydrides allows antimony to be detected
with greater sensitivity.

MDL Given an aqueous sample free of interferences, the instrumental performance

characteristics are:
MDL: 0.0001 mg/L
Range: 0.0001-0.010 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences See section 2.2.3 in the hydride AA section of this manual.

and Precautions

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Sb EDL or hollow cathode lamp

Parameters Wavelength: 217.6 nm
Background Correction: not required

Apparatus, Materials See section 2.2 and section 2.1.5 and 2.1.6 of this manual.
and Reagents

C-59
Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater, APHA,
AWWA, WPCF, 18th edition, 1992.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical Methods
(Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-60
 Metals
Revision Date: December 31, 2000

Antimony (Atomic Absorption - Graphite Furnace)

Parameter Antimony, total
Antimony, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: GFAA (total) Sb-T X072

LA: HNO3: GFAA (total) Sb-T X179
FF, FA: HNO3: GFAA (dissolved) Sb-D X116
LF, LA: HNO3: GFAA (dissolved) Sb-D X357

Introduction Antimony and its compounds have been reported to cause dermatitis,
keratitis, conjunctivitis and nasal septal ulceration by contact, fumes, or dust.

Method Summary A discrete sample volume is introduced into the graphite sample boat which
is heated in stages to accommodate drying of the solution, charring and
volatization of organics and other matrix components, and finally, atomization
of the analyte into the light path of the spectrometer. The absorption of light,
at a wavelength specific to the element being analyzed, is measured and the
concentration of the analyte is determined by comparison with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.003 mg/L
Range: 0.003-0.30 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA Methods section of this manual. High lead
concentration may cause a measurable spectral interference on the 217.6
nm line. If this interference is expected, the secondary wavelength should be
employed or Zeeman background correction used.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Sb EDL or hollow cathode lamp

Parameters Wavelength: 217.6 nm
Background Correction: recommended

Apparatus, Materials See sections 2.1.5 and 2.1.6 of this manual.

and Reagents

C-61
Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WEF, 18th edition, 1992, Method 3111 B.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-62
 Metals
Revision Date: December 31, 2000

Antimony (Atomic Emission - Inductively Coupled Argon Plasma

{ICAP})
Parameter Antimony, total
Antimony, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.4, the ICP-AES method section.

EMS Code FA: HNO3: ICAP (total) Sb-T X349

LA: HNO3: ICAP (total) Sb-T X352
FF, FA: HNO3: ICAP (dissolved) Sb-D X350
LF, LA: HNO3: ICAP (dissolved) Sb-D X356

Introduction Antimony and its compounds have been reported to cause dermatitis,
keratitis, conjunctivitis, and nasal septal ulceration by contact, fumes, or dust.

Method Summary Aqueous solutions of metals are converted to aerosols in the nebulizer of the
ICP and injected directly into a high temperature plasma (6000 to 8000°K).
The highly efficient ionization produces ionic emission spectra and
wavelengths specific to the elements of interest can be monitored either
simultaneously or sequentially.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.05 mg/L
Range: 0.05-1000 mg/L
See Table C-2 in section 2.4, the ICP method section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences See section 2.4.4, the ICP-AES section of this manual.

and Precautions

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Wavelength: 206.8 nm

Parameters Background Correction: recommended

Apparatus, Materials See section 2.4, the ICP-AES methods section in this manual.
and Reagents

Precision None listed.

Accuracy None listed.

C-63
Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WEF, 18th edition, 1992, Method 3120B.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-64
 Metals
Revision Date: December 31, 2000

Arsenic (Atomic Absorption - Direct Aspiration)

Parameter Arsenic, total
Arsenic, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) As-T X073

LA: HNO3: AA (total) As-T X351
FF, FA: HNO3: AA (dissolved) As-D X203
LF, LA: HNO3: AA (dissolved) As-D X085

Introduction The determination of trace amounts of arsenic in water and wastewater is

crucial because it is a highly toxic material. The main sources of arsenic
contamination in water and wastewater are coal, petroleum, detergents, and
pesticides.

Method Summary Aqueous solutions of metals are aspirated into a flame and atomized. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.20 mg/L
Range: 0.2-100mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA Methods section of this manual. Background
interferences occur with the use of both the air-acetylene and the nitrous
oxide-acetylene flames, but particularly with the air-acetylene flame, where at
least 60% of the light energy is absorbed. The nitrous oxide-acetylene flame
may be preferred due to its reduced background interferences, although
sensitivity is also decreased. Background correction should be used with
both flames, and will improve the signal to noise ratio.

A sample with high total salt content (greater than 1%) will produce apparent
absorption at the 193.7 nm arsenic line, even when the metal is absent. It is
therefore necessary to check readings for background absorption. A suitable
line for this purpose is the non-absorbing mercury line at 194.2 nm.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

C-65
Instrument Source: As EDL or hollow cathode lamp
Parameters Wavelength: 193.7 nm
Type of flame: air/acetylene
Background correction: recommended

Apparatus, Materials See section 2.1.5 and 2.1.6 of this manual.

and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WEF, 18th edition, 1992, Method 3111 B/D.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes.

C-66
 Metals
Revision Date: December 31, 2000

Arsenic (Atomic Absorption - Gaseous Hydride)

Parameter Arsenic, total
Arsenic, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section, and section 2.2, the hydride AA
method section.

EMS Code FA: HNO3: HVAAS (total) As-T X289

LA: HNO3: HVAAS (total) As-T X354
FA: HCl: HVAAS (total) As-T X345
LA: HCl: HVAAS (total) As-T X355
FF, FA: HNO3: HVAAS (dissolved) As-D X202
LF, LA: HNO3: HVAAS (dissolved) As-D X359
FF, FA: HCl: HVAAS (dissolved) As-D X348
LF, LA: HCl: HVAAS (dissolved) As-D X360

Introduction The determination of trace amounts of arsenic in water and wastewater is

crucial because it is a highly toxic material. The main sources of arsenic
contamination in water and wastewater are coal, petroleum, detergents, and
pesticides.

Method Summary Arsenic is converted to a gaseous hydride and analyzed by atomization in a

heated quartz tube. Conversion to hydrides allows Arsenic to be detected
with greater sensitivity.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.0002 mg/L
Range: 0.0002-0.020 mg/L
See Table C-1 in section 2.1, the AA method section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.2.3 of the hydride AA methods section of this manual. High
concentrations of chromium, cobalt, copper, mercury, molybdenum, nickel,
and silver can cause analytical interferences.

Traces of nitric acid left following the sample work-up can result in analytical
interferences.

Elemental arsenic and many of its compounds are volatile; therefore, certain
samples may be subject to losses of arsenic during sample preparation.

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

C-67
Instrument Source: As EDL or hollow cathode lamp
Parameters Wavelength: 193.7 nm
Background Correction: not required

Apparatus, Materials See section 2.2.3 and section 2.1.5 and 2.1.6 of this manual.
and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) B.C. Ministry of Environment, Laboratory Manual p. 97, 1989.

b) Standard Methods for the Examination of Water and Wastewater,
APHA, AWWA, WPCF, 18th edition, 1992.
c) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-68
 Metals
Revision Date: December 31, 2000

Arsenic (Atomic Emission - Inductively Coupled Argon Plasma

{ICAP})
Parameter Arsenic, total
Arsenic, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.4, the ICP-AES method section.

EMS Code FA: HNO3: ICAP (total) As-T X349

LA: HNO3: ICAP (total) As-T X352
FF, FA: HNO3: ICAP (dissolved) As-D X350
LF, LA: HNO3: ICAP (dissolved) As-D X356

Introduction The determination of trace amounts of arsenic in water and wastewater is

crucial because it is a highly toxic material. The main sources of arsenic
contamination in water and wastewater are coal, petroleum, detergents, and
pesticides.

Method Summary Aqueous solutions of metals are converted to aerosols in the nebulizer of the
ICP and injected directly into a high temperature plasma (6000 to 8000°K).
This highly efficient ionization produces ionic emission spectra and
wavelengths specific to the elements of interest can be monitored either
simultaneously or sequentially.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.050 mg/L
Range: 0.05-1000 mg/L
See Table C-2 in section 2.4, the ICP method section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences See section 2.4.4 of the ICP-AES section of this manual.

and Precautions

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Wavelength: 193.8 nm (primary)

Parameters Background Correction: recommended

Apparatus, Materials See section 2.4 of this manual.

and Reagents

C-69
Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Method for the Examination of Water and Wastewater,

APHA, AWWA, WEF, 18th edition, 1992, Method 3120 B.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-70
 Metals
Revision Date: November 2002

Arsenic Analysis of Solids by HVGAA

Parameter As-T - Arsenic Total

Sample Preparation Nitric-perchloric acid digestion

Analytical Method N/P Digestion: Hydride Generation

Atomic Absorption Spectrophotometry

EMS Codes AS-T 1194 HYDRIDE ATOM. ABSORPTION SPEC

Method Summary The sample undergoes a nitric-perchloric acid hydrochloric acid digestion to
break down all organically bound arsenic. The digestate is diluted 1:1 with
50% HCl. This solution is mixed with sodium borohydride which releases the
volatile hydride of arsenic. The hydride is separated from the aqueous
solution and introduced to a flame heated quartz absorption cell. Atomic
absorption is measured at 193.77 nm.

MDL 0.2 g/g

Matrix Soil, solids, (marine) sediments.

Stability Digested samples are stable for 6 months.

Procedure a) Digest block

Apparatus b) Glassware

Instrumentation A system consisting of:

a) Peristaltic pump
b) Hydride generator, (mixing coils and phase separator)
c) Quartz absorption cell
d) Atomic absorption spectrophotometer

Reagents Digest:
a) Hydrochloric Acid (HCl) conc., analytical grade.
b) Potassium persulfate solution, 4%: Dissolve 40 g of potassium
persulfate, analytical grade K2S2O8, in DI and dilute to 1 litre.

Analysis:
a) Sodium Borohydride solution, 1.5%: Dissolve 15 g of NaBH 4, analytical
grade, and 1 g NaOH, analytical grade in 1 litre of deionized water.
Filter through Whatman #41 filter paper.

Standards a) Stock Arsenic Calibration standards, 1000 mg/L; available

commercially, or:
1) 1000 mg/L As can be prepared by dissolving 1.320 g Arsenic
Trioxide, As2O3, analytical grade, in 10 mL deionized water
containing 4g NaOH, dilute to 500 mL with DI, adjust pH to
slightly acidic with HCl and dilute to 1 litre with DI.

b) Prepare 10 mg/L stock As. Dilute 5 mL of 1000 mg/L As to 500 mL

with DI. Prepare 1 mg/L stock As, dilute 10 mL of 10 mg/L stock
solution to 100 mL with DI.

C-71
 c) Prepare 1 litre of working standards: 0.005, 0.010, 0.025, 0.040 and
0.050 mg/L As by diluting 0.5, 1.0, 2.5, 4.0 and 5 mLs and 10 mLs of 1
mg/L stock and 10 mLs of 10 mg/L stock to 1 litre with DI.

Procedure See "Digestion of Soils for metals Analysis".

Instrumental Analysis a) Set up the Atomic Absorption Spectrophotometer according to the

operating instructions.

b) Install Arsenic electrodeless discharge lamp (EDL) and allow to warm

up for at least 30 minutes.

Calculations Absorbances are read from the instrument and electronically captured into a
Data Collection software package where concentration is calculated based
on Beers Law.

Hydride Generation a) Sample tubing: black/purple; flowrate: 6.8 mL/min.

System b) NaBH4 tubing: black/black; flowrate: 0.8 mL/min.
c) Pump speed: maximum 11 RPM.
d) Argon flowrate: 0.5 LPM.

Diagram of Hydride Generation System:

Precision Synthetic samples at concentrations of 3 and 10 mg/L As gave coefficients of

variation of 2% and 2% respectively.

Accuracy To be determined.

Quality Control a) Arsenic Quality Control Stock Solutions, 1000 mg/L. This solutions is
to be obtained from an alternate supplier than the calibration stock.

b) QCA for As: Solution containing 0.035 mg/L.

c) QCB for As: Solution containing 0.005 mg/L.

d) QC sample QH: 0.020 mg/L As.

References a) Standard Methods for the Examination of Water and Wastewater, 17th
Edition, 1989. Section 3114; p. 3-43 to 3-53.

Revision History: March 1997: Published in Supplement Manual #1.

November 2002: EMS code assigned.

C-72
 Metals
Revision Date: November 2002

Arsenic, Cadmium and Lead in Solids by GFAA

Parameter Arsenic, Cadmium and Lead

Sample Preparation See Section 1.0 for sample preparation.

Analytical Method Analysis of acid digested geological samples for metals by atomic absorption
spectrophotometry with a graphite furnace attachment.

EMS Code EMS codes to be defined on request.

Method Summary Analyte is electro-thermally heated to dry, char and then atomize within the
confines of a graphitic carbon tube. Absorbance is measured at the
atomization stage. Because the atom cloud generated at the atomization
stage is confined, relatively small quantities of analyte are required to
produce a significant signal level thus permitting the detection of picogram
levels of metals in various samples. Background correction is performed to
negate the effect of changing matrices.

Compounds Determined Element Detection Limit (µg/g)

and Detection Limits Arsenic 0.5
Cadmium 0.05
Lead 0.5

Detection limits have been calculated by multiplying the determined solution

detection limits by a common weight to volume factor.

Matrix Soil, solids, (marine) sediments.

Stability and Sample

Storage Soil digestates are stored in acid washed polypropylene bottles. Metals are
considered to be stable in solution for six months at room temperature.

Reagents a) Ultrapure water

b) "Trace Metal" grade nitric acid
c) "Trace Metal" grade hydrochloric acid
d) "Trace Metals grade hydrogen peroxide
e) "Ultrapure" nitric acid. Seastar or equivalent
f) Palladium (Granular) Aldrich 20,399-8 or equivalent
g) Nickel Solution, 1000 mg/L, Certified Atomic Absorption Standard
Solution, obtained from Fisher Scientific or other suitable supplier.

Note: Palladium and Nickel are used as matrix modifiers in specific analyses.
Please refer to specific instrumental analysis techniques for
instructions on uses of matrix modifiers.

C-73
Preparation of Graphite Note: Please see specific instrument operation manual for procedures
Furnace AA Calibration in preparing calibration standard solutions.
Standard Solutions

Apparatus Atomic Absorption Spectrophotometer equipped with a graphite furnace

atomizer attachment. Please refer to specific instrument manufacturers' for
other peripheral devices required for correct instrument set-up.

Examples are PC's, printers

EDL or Super Lamp Power Supplies
Auto-samplers
Hollow Cathode Lamps
Hollow Cathode Super Lamps
Electrodless Discharge Lamps (EDL)

Other required items include but are not limited to the following:
Graphite tubes
Graphite electrodes
Micropipette with disposal tips1000 mL, 250 mL, 100 mL Volumetric Flasks
for dilutions (note1)
50 mL, 25 mL, 10 mL, 5 mL, 1 mL, 0.5 mL pipettes for dilutions (note 1)
50 mL graduated cylinder

Disposal sample cups for systems with autosamplers.

Note 1: All glassware should be Class A and acid washed prior to use.

Analysis Procedure Refer to specific instrument operations manuals for set-up and analysis
procedures.

Quality Control Section

Analysis of Soils a) Digestion Blanks
b) Duplicates: If sample size permits, at a minimum frequency of 10%
c) Certified Reference Materials: If available, an SRM is run which
matches the sample matrix type.
Available Certified Reference Materials include: Environmental
Sediments: National Institute of Standards & Technology (NIST)
1646a Estuarine Sediment National Research Council of Canada
Estuarine Sediments: MESS-1, BCSS-1, PACS-1.

Daily Instrument
Checks Several graphite furnaces have built in QC checks. These include but are
not limited to:

a) Monitoring of calibration curve - at regular intervals the calibration is

checked automatically. If the standard changes by over 20% from the
previous calibration the run is stopped.

b) When two or more replicates are run for each sample, the sample will
be repeated if the % RSD is over 20%. If the % RSD is still over 20%
the sample will be flagged.

c) Internal Spiking - The instrument will make its own spike by adding a
preset quantity of standard solution to a sample. If the spike recovery
is not within the range of 80 to 120 % recovery, the spike is flagged.

C-74
Safety Notes a) These instruments use high voltage in their operation. Unplug
instrument or take other appropriate precautions when servicing.
b) Many of the reagents used in analysis techniques are hazardous. Use
in accordance with guidelines set out in the MSDS for each compound.

c) Heat, vapors and fumes generated by furnace methods can be

hazardous, toxic, or otherwise injurious to personnel.
ALWAYS switch the exhaust fan on BEFORE operating the graphite
tube atomizer.

d) Hazardous ultraviolet radiation can be emitted by the atomizer, hollow

cathode super lamps and electrodeless discharge lamps. This
radiation can cause serious damage to the eyes.

ALWAYS wear safety glasses manufactured to an approved standard

and which are certified or otherwise warranted to protect the eyes from
ultraviolet radiation.

e) When the graphite tube automizer is operating, the magnet, atomizer

chimney and immediate surrounds can present heat hazards which
can result in burns to personnel.

Never touch the magnet, atomizer chimney or the atomizer assembly

while the graphite tube atomizer is operating. Wear protective gloves
when working near the magnet.

f) The magnet produces a variable field of 8000 gauss RMS at mains

frequency in the workhead during the read stage.

To avoid interference with heart pacemakers or magnetic storage

media, keep them at least 300 mm from the magnet.

g) The graphite tube atomizer gas supply system is designed for use with
inert gases and air. The system is not designed for use with pure
hydrogen.

NEVER use pure hydrogen with the graphite tube atomizer since this
could result in leakage and potentially explosive accumulation of
hydrogen.
You may, however, use a proprietary, prepackaged mixture of 95%
argon and 5% hydrogen.

NEVER attempt to create your own mixture of hydrogen and inert gas
through the GTA system.

Method Sources a) Analytical Methods for Atomic Absorption Spectroscopy - Perkin Elmer
(1976).
b) Analytical Methods Using the HGA Graphite Furnace - Perkin Elmer
(1975).
c) Analytical Methods for Zeeman Graphite Tube Atomizer - Varian
(1986).
d) Advanced Furnace Training Manual.
e) Atomic Absorption Newsletter (Various Issues).
Varian Instruments at Work (Various Issues).

Revision History: March 1997: Published in Manual Supplement #1.

November 2002: Method adopted from Supplement #1.

C-75
 Inorganics
Revision Date: Aug 16, 2007

Soluble Barium by Calcium Chloride Extraction - Prescriptive

Parameter Soluble Barium (CaCl2)

Analytical Method 1M Calcium Chloride extraction.

Introduction This method is intended to provide quantification of soluble barium species,

without extracting insoluble and/or sequestered barium (e.g. barite). It is intended
to support CSR regulations for barium for sites where detailed documentary
evidence of barite usage exists.

The method uses excess calcium ions to increase barium solubility in solution,
and to encourage displacement of barium from cation exchange sites.

Method Summary This method is prescriptive. It must be followed exactly as described.

Where minor deviations are permitted, this is indicated in the text.

Samples are dried at low temperature and sieved using a 2 mm (10 mesh) sieve.
Solid samples are extracted for 2 hours with 1.0 M CaCl2 at a 10:1 ratio of
extraction solvent to solid. The extract is filtered and analyzed for barium using
an appropriately sensitive and precise analytical method for barium (e.g. ICP-AES
or ICP-MS).

MDL and EMS Analyte Approx. MDL EMS Code

Codes Soluble Barium (CaCl2) 2 mg/kg Not available

Matrix Soil, sediment, drilling waste solids, waste.

Interferences and Samples with high petroleum or non-petroleum hydrocarbon content (Oil and
Precautions Grease) may require specialized sample pre-treatment using solvent extraction.

Extracts from this method are very high in salt content, and normally require
dilution prior to analysis by most techniques.

Sample Handling Collect samples in a clean polyethylene or glass container. No preservation is

and Preservation required.

Stability Holding and Storage Time: Soils may be stored at room temperature or
refrigerated at ≤6°C for up to 6 months.

Extracts must be stored at room temperature, and must be analyzed within 7 days
of extraction.

Procedure Samples are prepared using the following procedures. All procedures are
mandatory elements, unless otherwise indicated.

1. Reagents
1.1. 1.0 M CaCl2. Volumetrically prepare the extraction solution by dissolving
147.0 g CaCL2.2H20 per 1L of laboratory grade water. Test new lots or
supplies or calcium chloride for barium background before use.
1.2. Laboratory Grade Water: Water free of substances that interfere with
the analytical method.

C-76
 2. Sample Preparation
2.1. Inspect the sample and record any unusual or significant characteristics
(i.e. foreign material, metals etc.).
2.2. Remove any obviously foreign material such as vegetation.
2.3. Homogenize the entire sample and subsample a sufficient quantity for
drying and analysis. Use appropriate subsampling techniques and
quantities to ensure that the sample has been sufficiently represented.
2.4. Dry sub-samples to constant weight at a temperature of <60°C. If no
other metals or temperature-sensitive analytes are to be determined
using the same sub-sample, a drying temperature of up to 105°C may be
used.
2.5. Disaggregate the dried sample by manual or gentle mechanical action.
2.6. Sieve each sample through a 2 mm (10 mesh) sieve. Discard the
“greater than 2 mm” fraction.

3. Sample Extraction Procedure

3.1. Accurately weigh 5.0 ± 0.5 g of dry sample into a vessel appropriate for
mechanical mixing (e.g. 250 mL glass Erlenmeyer). Include method
blanks, duplicates and at least one reference material per batch of
samples. Record sample weights to ± 0.01 g.
3.2. Add 50 ± 0.5 mL of 1.0 M CaCl2 extraction solution.
3.3. Extract the mixture for 2 hours ± 15 minutes using a mechanical agitation
method such as a shaker table or rotary mixer.
3.4. Filter the extract under gravity or suction, using a filter paper fine enough
to yield a clear filtrate. Alternatively extracts can be centrifuged to
remove suspended particles.
3.5. Accurately dilute the entire sample with laboratory grade water to the
volume required for the analysis. The dilution volume will depend on the
analysis technique, the detection limit, and the sample concentration.

4. Sample Analysis for Barium

4.1. Analyze the appropriately diluted extract of samples and QC samples
using an appropriate technique for barium, such as ICP-AES or ICP-MS.
Report results for soluble barium on a dry weight basis.
4.2. Report any anomalies during extraction and analysis.

Performance All laboratories performing this analytical method must conduct validation to
Requirements confirm that the requirements below are met.

Accuracy and Precision requirements apply to measures of long term method

performance (averages and standard deviations). Achievement of these
requirements is to be demonstrated during initial and ongoing method re-
validation studies. They do not constitute acceptance criteria or Data Quality
Objectives for individual Quality Control samples. For Initial Validations, averages
of at least 8 spikes or CRMs must be assessed (preferably taken from multiple
analytical batches). Ongoing Re-validations (performance reviews) should
assess QC data encompassing longer timeframes (e.g. 6 months to 1 year). A
minimum frequency of 2 years is recommended for Ongoing Re-validations.

Accuracy Requirement: Laboratories must demonstrate method accuracy

(measured as average recovery) of 80% or better for a minimum of 8 clean matrix
spikes of barium chloride in clean sand, at concentrations above ten times the
MDL.

C-77
 Precision Requirement: Laboratories must demonstrate method precision equal
to or better than 15% relative standard deviation for a minimum of 8 clean matrix
spikes of barium chloride in clean sand, at concentrations above ten times the
MDL.

Sensitivity Requirement: Where possible, the method should generate Method

Detection Limits that are less than 1/5 of applicable numerical standards. The
method is not fit-for-purpose if an MDL exceeds a guideline, standard, or
regulatory criteria against which it will be used for evaluation of compliance.

Quality Control Summary of QC Requirements

QC Component Minimum Frequency Minimum Data Quality

Objectives*
Method Blank One per batch Less than reported DL
Method Spike or Ref. One per batch 70 – 130% recovery
Material
Lab Duplicates Approximately 5-10% 40% RPD
* Minimum DQOs apply to individual QC samples, not averages, and only at levels above 10x MDL. If
any DQOs are exceeded at a frequency of more than ~5%, the laboratory’s method should be
reviewed in an attempt to improve its performance. Laboratories should report qualified data when
DQOs are not met, unless other evidence demonstrates that the quality of associated sample data has
not been adversely affected.

Method Blank: Required. Minimum one per batch or as necessary to ensure

contamination control.

Lab Duplicates: Required. Replicate all components of the test from start to
finish. Random duplicate selection at an approximate frequency of 5-10% is
recommended.

Reference Material or Method Spike: Required. Use of a Clean Matrix Spike of

Barium Chloride in sand is strongly recommended. In-house prepared RMs are
permitted.

Revision History June 10, 2007: Prepared for BCMOE by the BCLQAAC Barite Task Group
(Mark Hugdahl, Darlene Lintott, John Ashworth and Miles
Tindal).
Aug 16, 2007: BCLQAAC final approved version 1.0, submitted for Director’s
approval. Approved Sept 20, 2007; Effective Date: Oct 15,
2007.

C-78
 Metals
Revision Date: December 31, 2000

Barium (Atomic Absorption - Direct Aspiration)

Parameter Barium, total
Barium, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) Ba-T X073

LA: HNO3: AA (total) Ba-T X351
FF, FA: HNO3: AA (dissolved) Ba-D X203
LF, LA: HNO3: AA (dissolved) Ba-D X085

Introduction Barium is found mainly as barite, BaSO4, and witherite, BaCO3, both of
which are highly insoluble salts.

Barium therefore, usually occurs only in trace amounts in water. Appreciable

levels in water supplies are indicative of undesirable industrial waste
pollution. Ingestion of high doses of barium can be fatal.

Canadian Drinking Water Guidelines stipulates 1mg/L as the IMAC (interim

maximum acceptable concentration).

Method Summary Aqueous solutions of metals are aspirated into a flame and atomized. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.1 mg/L
Range: 0.1-20.0 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. Control
ionization by addition of 0.1% or more potassium chloride to standards and
samples. Use nitrous oxide-acetylene to eliminate or reduce interferences
and increase sensitivity. Potential background absorption from calcium is
possible when using the 553.6 nm line.

Sample Handling See section 1.0, the sample preparation section.

and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

C-79
Instrument Source: Ba hollow cathode lamp
Parameters Wavelength: 553.6 nm
Type of Flame: nitrous oxide/acetylene
Background Correction: recommended

Apparatus, Materials See section 2.1.5 and 2.1.6 of this manual.

and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 18th edition, 1992.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-80
 Metals
Revision Date: December 31, 2000

Barium (Atomic Absorption - Graphite Furnace)

Parameter Barium, total
Barium, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code X072 FA: HNO3: GFAA (total) Ba-T X072

X179 LA: HNO3: GFAA (total) Ba-T X179
X116 FF, FA: HNO3: GFAA (dissolved) Ba-D X116
X357 LF, LA: HNO3: GFAA (dissolved) Ba-D X357

Introduction Barium is found mainly as barite, BaSO4, and witherite, BaCO3, both of
which are highly insoluble salts. Barium therefore, usually occurs only in
trace amounts in water. Appreciable levels in water supplies are indicative of
undesirable industrial waste pollution. Ingestion of high doses of barium can
be fatal.

Canadian Drinking Water Guidelines stipulates 1 mg/L as the IMAC (interim

maximum acceptable concentration).

Method Summary A discrete sample volume is introduced into the graphite sample boat which
is heated in stages to accommodate drying of the solution, charring and
volatilization of organics and other matrix components, and finally,
atomization of the analyte into the light path of the spectrometer. The
concentration of the analyte is determined by comparison with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.002 mg/L
Range: 0.002-0.200 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions Interferences in electrothermal analysis will be more pronounced than those
in flame atomic absorption, and are due mainly to molecular absorption,
chemical and matrix effects. Control of interferences can be achieved by the
use of deuterium, tungsten halide or Zeeman effect background correction.
In some cases matrix modifiers are used to minimize or eliminate
interferences.

Off the wall atomization is recommended for Barium analysis. Memory effect
problems are frequently encountered with this analysis. See also section
2.1.4 of the AA methods section of this manual.

C-81
Sample Handling and See section 1.0, the sample preparation section.
Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Ba hollow cathode lamp

Parameters Wavelength: 553.6 nm
Background Correction: recommended

Apparatus, Materials See section 2.1.5 and 2.1.6 of this manual.

and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 18th edition, 1992.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-82
 Metals
Revision: October 1, 2013

Boron, Hot Water Soluble (Prescriptive)

Parameter Boron, Hot Water Soluble

Analytical Method Hot aqueous 0.01 M CaCl2 extraction followed by ICPOES, colourimetric
determination, or other appropriate instrumental analysis.

Introduction Boron is a plant micronutrient essential for healthy growth and crop yield. Small
amounts are required for normal growth, while higher concentrations of available
Boron can cause toxic effects and yield reductions to plants and crops. Irrigation
water ranging from 0.3 to 2.0 mg/L Boron can cause toxic effects or yield
reductions to crops. However, Boron availability to plants is only related to the
activity of Boron in the soil solutions. Boron adsorbs to soils and especially to clay
minerals, with maximum adsorption occurring at alkaline pH. Leaching of Boron
from soils is greatest at low pH. The Hot Water Soluble Boron procedure is the
most commonly used method for predicting the concentration of Boron that will be
available to plants in a soil solution.

Method Summary Hot Water Soluble Boron is an operationally defined technique used to estimate the
concentration of Boron available for plant uptake. Soil samples are extracted by
boiling a 2:1 mixture of aqueous 0.01 M CaCl2 to soil for 5-15 minutes, prior to
filtration of the extract and Boron determination using ICPOES, colourimetry, or
another suitable instrumental technique. The presence of CaCl2 in the extracting
solution does not alter the amount of Boron (compared with hot water alone), and
after filtration, results in extracts that are clear, colourless, and free of colloidal
matter (References: SSSA, Carter).

This method is prescriptive, and may not be modified.

Parameters and Parameter Approx. MDL

Parameter Codes
Hot Water Soluble Boron 0.1 mg/kg

MDL is dependent on method of determination. An MDL of 0.1 mg/kg is achievable

by ICPOES.

Matrix Although designed for soils the method may also be applicable to solids and
sludges.

Interferences and If a colourimetric determination is used charcoal may be added to the sample prior
Precautions to boiling to produce a colourless extract. Boron may be present in deionized water
from glass distillation equipment or may be introduced from borosilicate glassware.

Sample Handling Samples should be collected in glass or plastic containers.

and Preservation
Samples should be dried and screened to 2 mm (10 mesh) prior to extraction.

Stability Holding Time: 6 months from sampling (field moist), indefinite when dried.

Storage: No storage temperature requirement.

Equipment and 1. Heating source (e.g. block digester, hotplate, water bath)
Supplies 2. Balance, minimum 3 place
3. Drying oven (not required)

C-83
 4. Sieve, 2 mm (ASTM-E11 Sieve No. 10, US Sieve No. 10, Tyler 9 Mesh)
5. Digestion Vessels (e.g. block digester tube, beaker, flask, etc.)
6. Cover to fit digestion vessel (e.g. watch glass etc.)
7. Gloves
8. Spatula
9. Apparatus for filtering

Reagents 1. Water, de-ionized (ASTM Type I or equivalent recommended)

2. Calcium chloride
3. Activated charcoal

Safety Wear appropriate PPE (Personal Protective Equipment) including lab coat, gloves,
and safety glasses. Add acid to samples and perform digestions under a fume
hood.

Procedure Sample Homogenization and Sub-Sampling

1. Inspect the sample and record any unusual or significant characteristics.

2. Remove any obviously foreign material such as vegetation.
3. If the sample has separated into visually discrete layers (e.g. aqueous, organic,
and sediment phases), the entire sample must be homogenized prior to sub-
sampling.
4. The aqueous phase must not be decanted.
5. Homogenize the entire sample by vigorous stirring using a spatula. If it is not
possible to homogenize the sample in the container it was received in, the
sample may be transferred to a larger container prior to homogenization.

Sample Preparation – Drying and Sieving

1. Dry the sample to a constant weight at a temperature of ≤ 60°C. Air drying to

constant weight is acceptable. Freeze drying is acceptable.
2. Sieve each sample through a 2 mm sieve. DO NOT pulverize samples to pass
through either sieve type. Easily friable materials (dried clay clods,
disintegrating rock, etc.) should be disaggregated prior to screening. Where
necessary, non-pulverizing disaggregating tools like rolling mills, mortar and
pestle, or flail grinders may be used.

Sample Preparation - Extraction

1. Extraction procedure is described in “Soil Sampling and Methods of Analysis”

Carter, 2008 Procedure 9.2.2.
2. Weigh a minimum of 5 grams of dried sub 2 mm sample into a hotblock tube,
beaker, or flask.
3. If a colourimetric finish is to be used, activated charcoal may be added if
necessary to produce a colourless filtrate (0.1 grams of activated charcoal per
5 grams sample is recommended).
4. For each 5 grams of dried sample, dispense 10 mL of 0.01 M CaCl2, cover with
a watch glass and bring to a boil for at least 5 minutes (but no longer than 15
minutes) on a hot plate, hot block, or water bath. After cooling, adjust volume
with deionized water to compensate for loss of water during boiling.
5. Filter extract (Whatman No. 42 or equivalent filter paper is recommended) and
store in plastic containers prior to the determination of Boron.

Performance Any analytical method options selected for this analysis must meet or exceed the
Requirements performance requirements specified below.

C-84
 Accuracy and Precision requirements apply to measures of long term method
performance (averages and standard deviations). Achievement of these
requirements is to be demonstrated during initial and ongoing method re-validation
studies. They do not constitute acceptance criteria or Data Quality Objectives for
individual Quality Control samples. For Initial Validations, averages of at least 8
spikes or CRMs must be assessed (preferably taken from multiple analytical
batches). Ongoing re-validations (performance reviews) should assess QC data
encompassing longer timeframes (e.g. 6 months to 1 year). A minimum frequency
of 2 years is recommended for ongoing re-validations.

Accuracy Requirement: Laboratories must demonstrate method accuracy

(measured as average recovery) of 80 – 120% or better for clean matrix spikes or
certified reference materials at concentrations above ten times the MDL.

Precision Requirement: Laboratories must demonstrate method precision equal

to or better than 15% relative standard deviation for clean matrix spikes at
concentrations above ten times the MDL.

Sensitivity Requirement: Where possible, the method should generate Method

Detection Limits that are less than 1/5 of applicable numerical standards. The
method is not fit-for-purpose if an MDL exceeds a guideline, standard, or regulatory
criteria against which it will be used for evaluation of compliance.

Quality Control Summary of QC Requirements

Method QC Component Minimum Frequency Minimum Data Quality

Objectives*
Method Blank 1 per batch (max 20 samples) Less than reported DL
Laboratory Control
Sample or Reference 1 per batch (max 20 samples) 60 – 140%
Material
Lab Duplicate 1 per batch (max 20 samples) ≤ 40% RPD
Field Duplicate Recommended None Specified
* Minimum DQOs apply to individual QC samples, not averages, and only at levels above 10x MDL.
Laboratories must report qualified data when DQOs are not met.

References 1. Soil Sampling and Methods of Analysis. 2008. Canadian Society of Soil
Science, Chapter 9, “Boron, Molybdenum, and Selenium”. Carter and
Gregorich, Editors.

2. Manual on Soil Sampling and methods of Analysis. 1978. Canada Soil

Survey Committee. J.A. McKeague, Editor.

3. Methods of Soil Analysis, Part 3, Chemical Methods, Chapter 21, “Boron”.

Soil Science Society of America, 1996.

Revision History Dec 2002: Method initially developed by BCLQAAC Technical Committee.
July 26, Method revision. Format updated. Changed extraction solution
2013: from hot water to 0.01 M CaCl2 extraction for consistency with
proposed CCME method guidelines, and to improve method
performance. DQOs were revised. Infinite hold time added for
dried soils. Effective date for this version is October 1, 2013.
October 1, Boron, Hot Water Soluble method updated.
2013:

C-85
 Metals
Revision Date: December 31, 2000

Cadmium (Atomic Absorption - Direct Aspiration)

Parameter Cadmium, total
Cadmium, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) Cd-T X073

LA: HNO3: AA (total) Cd-T X351
FF, FA: HNO3: AA (dissolved) Cd-D X203
LF, LA: HNO3: AA (dissolved) Cd-D X085

Introduction Cadmium is toxic to virtually every system in the animal body, whether
ingested, injected, or inhaled. Histological changes have been observed in
the kidneys, liver, gastrointestinal tract, heart, testes, pancreas, bones and
blood vessels. Cadmium in man has a tenacious retention time in the body
with a long half-life estimated at 16-33 years.

The Canadian drinking water guideline for cadmium is 0.005 mg/L. The limit
indicated in Water Criteria for Salmonid Hatcheries is 0.0003 mg/L.

Method Summary Aqueous solutions of metals are aspirated into a flame and atomized. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.005 mg/L
Range: 0.005-2.00 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. Coexisting
elements causing relatively large interferences are Ca, Si, and Ti.

Sample Handling See section 1.0 the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Cd hollow cathode lamp

Parameters Wavelength: 228.8 nm
Type of Flame: air/acetylene
Background Correction: recommended

C-86
Apparatus, Materials See section 2.1.5 and 2.1.6 of the AA methods section of this manual.
and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9 QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 17th edition, 1989 Method 3500-Cd.
b) Methods for Chemical Analysis of Water and Wastes, EPA-600 4-
79-020, March 1983, Method 213.1.
c) Trace Elements in Human and Animal Nutrition, Eric J. Underwood,
4th edition, Academic Press, 1977.
d) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-87
 Metals
Revision Date: December 31, 2000

Cadmium (Atomic Absorption - Graphite Furnace)

Parameter Cadmium, total
Cadmium, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: GFAA (total) Cd-T X072

LA: HNO3: GFAA (total) Cd-T X179
FF, FA: HNO3: GFAA (dissolved) Cd-D X116
LF, LA: HNO3: GFAA (dissolved) Cd-D X357

Introduction Cadmium is toxic to virtually every system in the animal body, whether
ingested, injected, or inhaled. Histological changes have been observed in
the kidneys, liver, gastrointestinal tract, heart, testes, pancreas, bones and
blood vessels. Cadmium in man has a tenacious retention time in the body
with a long half-life estimated at 16-33 years.

The Canadian drinking water guideline for cadmium is 0.005 mg/L. The limit
indicated in Water Criteria for Salmonid Hatcheries is 0.0003 mg/L.

Method Summary A discrete sample volume is introduced into the graphite sample boat which
is heated in stages to accommodate drying of the solution, charring and
volatilization of organics and other matrix components, and finally,
atomization of the analyte into the light path of the spectrometer. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.0001 mg/L
Range: 0.0001-0.010 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. Matrix modifiers
for interference removal are given by Standard Methods as:
NH4H2PO4 & Mg(NO3)2
(NH4)2HPO4 & Mg(NO3)2
(NH4)2SO4, HNO3, (NH4)2S2O8
Mg(NO3)2

C-88
Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation
Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Cd hollow cathode lamp

Parameters Wavelength: 228.8 nm
Background Correction: recommended

Apparatus, Materials See section 2.1.5 and 2.1.6 of the AA methods section of this manual.
and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 17th edition, 1989 Section 3113.
b) Methods for Chemical Analysis of Water and Wastes, EPA-600 4-
79-020, March 1983, Method 213.2.
c) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-89
 Metals
Revision Date: December 31, 2000

Cadmium (Atomic Emission - Inductively Coupled Argon Plasma

{ICAP})
Parameter Cadmium, total
Cadmium, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.4, the ICP-AES method section.

EMS Code FA: HNO3: ICAP (total) Cd-T X349

LA: HNO3: ICAP (total) Cd-T X352
FF, FA: HNO3: ICAP (dissolved) Cd-D X350
LF, LA: HNO3: ICAP (dissolved) Cd-D X356

Introduction Cadmium is toxic to virtually every system in the animal body, whether
ingested, injected, or inhaled. Histological changes have been observed in
the kidneys, liver, gastrointestinal tract, heart, testes, pancreas, bones and
blood vessels. Cadmium in man has a tenacious retention time in the body
with a half-life estimated at 16-33 years.

The Canadian drinking water guideline for cadmium is 0.005 mg/L. The limit
indicated in Water Criteria for Salmonid Hatcheries is 0.0003 mg/L.

Method Summary Aqueous solutions of metals are converted to aerosols in the nebulizer of the
ICP and injected directly into a high temperature plasma (6000 to 8000°K).
The highly efficient ionization produces ionic emission spectra and
wavelengths specific to the elements of interest it can be monitored either
simultaneously or sequentially.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.010 mg/L
Range: 0.010-100 mg/L
See Table C-2 in section 2.4, the ICP-AES method section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences See section 2.4.4 of the ICP-AES method section of this manual.
and Precautions

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Wavelength: 228.8 nm

Parameters Background Correction: recommended

C-90
Apparatus, Materials See section 2.4, the ICP-AES methods section of this manual.
and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 17th edition, 1989 Section 3120 B.
b) Methods for Chemical Analysis of Water and Wastes, EPA-600 4-
79-020, March 1983, Method 200.7.
c) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-91
 Metals
Revision Date: December 31, 2000

Calcium (Atomic Absorption - Direct Aspiration)

Parameter Calcium, total
Calcium, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) Ca-T X073

LA: HNO3: AA (total) Ca-T X351
FF, FA: HNO3: AA (dissolved) Ca-D X203
LF, LA: HNO3: AA (dissolved) Ca-D X085

Method Summary Aqueous solutions of metals are aspirated into a flame and atomized. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.01 mg/L
Range: 0.01-5.0 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. Ionization can
occur in an air-acetylene flame and can be controlled by the addition of
potassium chloride to a level of 0.1%. Elements that form stable oxides (Al,
Be, P, Si, Ti, V, Zr) will reduce calcium sensitivity. These can be controlled
by the addition 0.1-1.0% lanthanum or strontium.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2 has a hold time of 6
months.

Instrument Source: Ca hollow cathode lamp

Parameters Wavelength: 422.7 nm (primary); 239.9 nm (alternate)
Type of Flame: air/acetylene
Background Correction: recommended

Apparatus, Materials See sections 2.1.5 and 2.1.6 of this manual.

and Reagents

Precision None listed.

Accuracy None listed.

C-92
Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater

APHA, AWWA, WEF, 18th edition, 1992, Method 3111 B/D.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-93
 Metals
Revision Date: December 31, 2000

Chromium (Atomic Absorption - Direct Aspiration)

Parameter Chromium, total
Chromium, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code X073 FA: HNO3: AA (total) Cr-T X073

X351 LA: HNO3: AA (total) Cr-T X351
X203 FF, FA: HNO3: AA (dissolved) Cr-D X203
X085 LF, LA: HNO3: AA (dissolved) Cr-D X085

Introduction Chromium is an essential element and is necessary for glucose metabolism,

lipid metabolism, protein synthesis, growth and longevity. Simple chromium
salts are poorly absorbed in animals and man, to the extent of 1-3%.
Hexavalent chromium is much more toxic than the trivalent form.

The Canadian drinking water guideline for chromium is 0.05mg/L. The limit
indicated in Water Criteria for Salmonid Hatcheries is 0.04 mg/L.

Method Summary Aqueous solution of metals are aspirated into a flame and atomized. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.050 mg/L
Range: 0.050-10.0 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. Coexisting
elements causing relatively large interferences are Fe and Ni.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Cr hollow cathode lamp

Parameters Wavelength: 357.9 nm
Type of Flame: air/acetylene
Background Correction: recommended

C-94
Apparatus, Materials See section 2.1.5 and 2.1.6 of the AA methods section of this manual.
and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 17th edition, 1989 Method 3111 B, 3111C.
b) Methods for Chemical Analysis of Water and Wastes, EPA-600 4-
79-020, March 1983, Method 218.1.
c) Trace Elements in Human and Animal Nutrition, Eric J. Underwood,
4th edition, Academic Press, 1977.
d) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-95
 Metals
Revision Date: December 31, 2000

Chromium (Atomic Absorption - Graphite Furnace)

Parameter Chromium, total
Chromium, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: GFAA (total) Cr-T X072

LA: HNO3: GFAA (total) Cr-T X179
FF, FA: HNO3: GFAA (dissolved) Cr-D X116
LF, LA: HNO3: GFAA (dissolved) Cr-D X357

Introduction Chromium is an essential element and is necessary for glucose metabolism,

lipid metabolism, protein synthesis, growth and longevity. Simple chromium
salts are poorly absorbed in animal and man, to the extent of 1-3%.
Hexavalent chromium is much more toxic than the trivalent form.

The Canadian drinking water guideline for chromium is 0.05 mg/L. The limit
indicated in Water Criteria for Salmonid Hatcheries is 0.04 mg/L.

Method Summary A discrete sample volume is introduced into the graphite sample boat which
is heated in stages to accommodate drying of the solution, charring and
volatilization of organics and other matrix components, and finally,
atomization of the analyte into the light path of the spectrometer. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.001 mg/L
Range: 0.001-0.100 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. Matrix modifiers
for interference removal are given by Standard Methods as:

Mg(NO3)2

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

C-96
Instrument Source: Cr hollow cathode lamp
Parameters Wavelength: 357.9 nm
Background Correction: recommended

Apparatus, Materials See section 2.1.5 and 2.1.6 of the AA methods section of this manual.
and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 17th edition, 1989 Section 3113.
b) Methods for Chemical Analysis of Water and Wastes, EPA-600 4-
79-020, March 1983, Method 218.2.
c) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-97
 Metals
Revision Date: December 31, 2000

Chromium (Atomic Emission - Inductively Coupled Argon Plasma

{ICAP})
Parameter Chromium, total
Chromium, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.4, the ICP-AES method section.

EMS Code FA: HNO3: ICAP (total) Cr-T X349

LA: HNO3: ICAP (total) Cr-T X352
FF, FA: HNO3: ICAP (dissolved) Cr-D X350
LF, LA: HNO3: ICAP (dissolved) Cr-D X356

Introduction Chromium is an essential element and is necessary for glucose metabolism,

lipid metabolism, protein synthesis, growth and longevity, Simple chromium
salts are poorly absorbed in animals and man, to the extent of 1-3%.
Hexavalent chromium is much more toxic than the trivalent form.

The Canadian drinking water guideline for chromium is 0.05 mg/L. The limit
indicated in Water Criteria for Salmonid Hatcheries is 0.04 mg/L.

Method Summary Aqueous solutions of metals are converted to aerosols in the nebulizer of the
ICP and injected directly into a high temperature plasma (6000 to 8000°K).
The highly efficient ionization produces ionic emission spectra and
wavelengths specific to the elements of interest can be monitored either
simultaneously or sequentially.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.010 mg/L
Range: 0.010-100.0 mg/L
See Table C-2 in section 2.4, the ICP method section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences See section 2.4.4 of the ICP section of this manual.

and Precautions

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Wavelength: 205.5 nm

Parameters Background Correction: recommended

C-98
Apparatus, Materials See section 2.4 of the ICP methods section of this manual.
and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 17th edition, 1989 Section 3120B.
b) Methods for Chemical Analysis of Water and Wastes, EPA-600 4-
79-020, March 1983, Method 200.7.
c) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-99
 Metals
Revision Date: January 25, 2008

Chromium, Hexavalent in Water – PBM

Parameter Chromium, Hexavalent

Analytical Method Colourimetric Method

Ion Chromatographic Method

Introduction This procedure is applicable to the determination of hexavalent chromium in water

samples. Multiple analytical techniques are possible and as such, the
determinative portion of this method is performance based.

Hexavalent chromium (Cr(VI)) compounds are those which contain the element
chromium in the +6 oxidation state. Industrial uses of hexavalent chromium
compounds include chromate pigments in dyes, paints, inks, and plastics;
chromates added as anticorrosive agents to paints, primers, and other surface
coatings; and chromic acid electroplated onto metal parts to provide a decorative
or protective coating.

Reduction of Cr(VI) to Cr(III) can occur in the presence of reducing species in an

2-
acidic medium. At pH 6.5 or greater, however, CrO 4 , which is less reactive than
-
HCrO4 , is the predominant species. Therefore preservation with NaOH is used to
prevent species conversion (EPA 1636).

The group of hexavalent chromium compounds as a whole have been classified

as “carcinogenic to humans” by the Government of Canada.

Method Summary Various techniques are available for the determination of hexavalent chromium in
water:

Colourimetric Method – Involves the reaction of hexavalent chromium with

diphenylcarbazide in acid solution to produce a red-violet complex that is
measured at 530 or 540 nm.

Ion Chromatographic Method – Involves sample pH adjustment to 9.0-9.5 to

reduce the solubility of trivalent chromium and to preserve the oxidative state of
hexavalent chromium. The sample is introduced into an ion chromatography
system where the hexavalent chromium is separated from trivalent chromium.
The hexavalent chromium reacts with a diphenylcarbazide dye and is measured
colourimetrically at 530 or 540 nm.

MDL and EMS MDL is dependent on analytical technique and instrumental parameters. The
Codes following values provide general guidance:

 Typical MDL: 1 – 5 ug/L depending on technique

 Typical Range: up to 1,000 ug/L depending on technique

Matrix Natural and treated waters.

Interferences and Colourimetric Method – The colourimetric method is nearly specific to chromium,
Precautions and for practical purposes, chemical interferences are minimal. Sample color
may affect absorbance readings, and measures should be taken to mitigate this
effect.

C-100
 Ion Chromatographic Method – Chemical interferences are minimal. High ionic
concentrations my cause column overload, and/or result in changes in peak
geometry.

Sample Handling Container: Plastic or glass, metals free.

and Preservation
Preservation: No preservation is required if analysis will be complete within 24
hours. Preserve as soon as possible after collection (but within 24 hours of
collection) with 1mL of 50% NaOH per 125mL sample (EPA 1669), to extend
holding time to 30 days.

Filtration: Field filter through 0.45um filter when dissolved analysis is required.

Stability Holding Time: Preserved samples are stable for 30 days (EPA 1669).
Unpreserved samples must be analyzed within 24 hours of collection.

Storage: Cool temperatures (≤6ºC).

Procedure As this is a performance based method, and because multiple analytical

approaches are possible, detailed analysis steps are not provided in this method.
Refer to the methods cited in the References section for specific details, and
ensure that Performance Requirements are achieved.

Performance Any analytical method options selected for this analysis must meet or exceed the
Requirements method validation performance requirements specified below:

Accuracy and Precision requirements apply to measures of long term method

performance (averages and standard deviations). Achievement of these
requirements is to be demonstrated during initial and ongoing method re-
validation studies. They do not constitute acceptance criteria or Data Quality
Objectives for individual Quality Control samples.

For Initial Validations, averages of at least 8 spikes must be assessed (preferably

taken from multiple analytical batches).

Ongoing Re-validations (performance reviews) should assess QC data

encompassing longer timeframes (e.g. 6 months to 1 year). A minimum
frequency of 2 years is recommended for Ongoing Re-validations.

Accuracy Requirement: Laboratories must demonstrate method accuracy

(measured as average recovery) through repeat analysis of clean matrix spikes.
Average recovery must be between 85-115%.

Precision Requirement: Laboratories must demonstrate method precision

through repeat analysis. Precision measured as percent relative standard
deviation (%RSD) must be <15%.

Sensitivity Requirement: Where possible, the method should generate Method

Detection Limits that are less than 1/5 of applicable numerical standards. The
method is not fit-for-purpose if an MDL exceeds a guideline, standard, or
regulatory criteria against which it will be used for evaluation of compliance.

C-101
Quality Control Summary of QC Requirements
QC Component Minimum Frequency Minimum Data Quality
Objectives*
Method Blank 1 per batch Less than reported DL

Method Spike 1 per batch 80 – 120% recovery

Duplicates 1 per batch 20% RPD

* Minimum DQOs apply to individual QC samples, not averages, and only at levels above 10x MDL. If
any DQOs are exceeded at a frequency of more than ~5%, the laboratory’s method should be
reviewed in an attempt to improve its performance. Laboratories should report qualified data when
DQOs are not met, unless other evidence demonstrates that the quality of associated sample data has
not been adversely affected.

Prescribed 1. Determinative analysis must be by ion chromatography, or by the diphenyl

Elements carbazide colourimetric method.

2. Ensure that Sample Handling and Preservation requirements are achieved.

3. All Performance Requirements and Quality Control requirements must be

met.

References Standard Methods for the Examination of Water and Wastewater, APHA, AWWA,
st
WEF, 21 Edition 2005, Method 3500-Cr B, Colorimetric Method.

Standard Methods for the Examination of Water and Wastewater, APHA, AWWA,
st
WEF, 21 Edition 2005, Method 3500-Cr C, Ion Chromatographic Method.

EPA Method 1636, US Environmental Protection Agency, Determination of

Hexavalent Chromium by Ion Chromatography, January 1996.

EPA Method 1669, US Environmental Protection Agency, Sampling Ambient

Water for the Determination of Metals at EPA Water Quality Criteria Levels, July
1996 (Reference for preservation technique).

EPA 40CFR Part 136, March 12, 2007 (Reference for storage temperature).

Revision History January 25, 2008: Initial BCLQAAC endorsed version.

C-102
 Metals
Revision: October 1, 2013

Hexavalent Chromium in Solids by Alkaline Digestion - PBM

Parameter Hexavalent Chromium

Analytical Method Alkaline extraction – Colorimetric or IC Determination

Introduction This procedure is applicable to the determination of hexavalent chromium in solid

samples (soils, sediments, sludges, etc.). The analysis portion of this method is
performance based.

Chromium can exist in nine different oxidation states, but trivalent (III) and
hexavalent (VI) are the most common in the environment. Cr(III) is the most
thermodynamically stable species under ambient redox conditions. Complexed
Cr(III) occurs naturally and is ubiquitous in the environment. The principal source
of Cr(VI) in the environment is anthropogenic pollution. Cr(VI) has an affinity to
react with organic matter and other reducing substances. Cr(III) solids are
practically insoluble in water at pH >4, and do not tend to leach from a soil matrix
into groundwaters. At pH > 8.5, Cr(VI) solids are highly soluble and completely
mobile, and can readily leach from soils into groundwater systems.

The group of Cr(VI) compounds as a whole have been classified as “carcinogenic

to humans” by the Government of Canada.

Method Summary Soluble, adsorbed, and precipitated forms of Cr(VI) are extracted from field-moist
solids using a NaOH / Na2CO3 alkaline digestion procedure. Magnesium chloride
in phosphate buffer is added to prevent oxidation of Cr(III) to Cr(VI). The
digestate is filtered through a 0.45μm membrane filter prior to acidification to a
target pH range (dependent upon the analytical method used). The filtered
digestate is normally analyzed by UV-VIS colourimetry or by Ion Chromatography
with colourimetric detection. Other published reference methods may also be
appropriate for analysis of Cr(VI) in alkaline digests.

This method is performance-based. Laboratories may adopt alternative options

to improve performance or efficiency provided that all stated performance
requirements and prescribed (mandatory) elements are met.

MDL MDL is dependent on analytical technique and on instrument parameters. For a

2.5 g dry weight sample free from interference digested into 50 mL and analyzed
by UV-VIS colourimetry, an MDL of 0.5 mg/kg is achievable.

Matrix Soil, sediment, sludges, solid wastes.

Interferences and Concentrations of hexavalent molybdenum or mercury of >200 mg/L in the

Precautions leachate can interfere with the UV-VIS colourimetric determination, as can
Vanadium when present at levels above ten times the Cr(VI) concentration.

Reduction of Cr(VI) to Cr(III) can occur in the presence of reducing species in an

acidic medium. Laboratories are not normally expected to determine the reducing
or oxidizing tendency of samples except by special request (see Method 3060A,
section 3.1, Interferences).[a]

For Ion Chromatography determinations, overloading the analytical column with

high concentrations of anionic species, especially chloride and sulfate, will cause
a loss of Cr(VI).

C-103
Sample Handling Collect samples in plastic or glass containers. No chemical preservative
and Preservation techniques are applicable.

Stability Holding Time: Digest samples within 30 days of sample collection. Analyze
digestate within 7 days of preparation.

Storage: Store field moist at ≤ 6°C.

Digestion Follow the procedure described in US EPA SW846 Method 3060A (Dec, 1996 or
Procedure newer). Add magnesium chloride in phosphate buffer to all samples to prevent
oxidation of Cr(III).

Modifications to the chemistry of the 3060A digestion procedure (including

temperature, reagent compositions or ratios, and the continuous stirring
requirement) are not permitted. Minor physical and procedural changes may be
adopted if performance criteria are met.

Adjustment of the digest pH is generally required for compatibility with standard

analytical methods – consult EPA Method 3060A for details of pH adjustment and
consult the chosen analytical method references for acceptable pH.

Analysis Detailed analysis procedures are not provided in this method. The published
Procedure reference methods below are recommended for general guidance:

APHA Method 3500-Cr B. Colorimetric Method, 2009 or later.

APHA Method 3500-Cr C. Ion Chromatographic Method, 2009 or later.

EPA Method 1636. Determination of Hexavalent Chromium by Ion

Chromatography, January 1996 or later.

EPA SW-846 Method 7196A, Chromium, Hexavalent (Colorimetric), July 1992 or

later.

Other reference methods not listed here may also be employed if performance
requirements can be met.

Performance Any analytical method options selected for this analysis must meet or exceed the
Requirements performance requirements specified below.

Accuracy and Precision requirements apply to measures of long term method

performance (averages and standard deviations). Achievement of these
requirements is to be demonstrated during initial and ongoing method re-
validation studies. They do not constitute acceptance criteria or Data Quality
Objectives for individual Quality Control samples. For Initial Validations, averages
of at least 8 spikes or CRMs must be assessed (preferably taken from multiple
analytical batches). Ongoing Re-validations (performance reviews) should
assess QC data encompassing longer timeframes (e.g. 6 months to 1 year). A
minimum frequency of 2 years is recommended for Ongoing Re-validations.

Accuracy Requirement: Laboratories must demonstrate method accuracy

(measured as average recovery) of 80-120% for Laboratory Control Samples or
Certified Reference Materials at concentrations above ten times the MDL.

Precision Requirement: Laboratories must demonstrate method precision equal

to or better than 15% relative standard deviation for clean matrix spikes at
concentrations above ten times the MDL.

C-104
 Sensitivity Requirement: Where possible, the method should generate Method
Detection Limits that are less than 1/5 of applicable numerical standards. The
method is not fit-for-purpose if an MDL exceeds a guideline, standard, or
regulatory criteria against which it will be used for evaluation of compliance.

Quality Control Summary of QC Requirements

QC Component Minimum Frequency Minimum Data Quality

Objectives*
Method Blank One per 20 samples Less than reported DL
Laboratory Control Sample
One per 20 samples 70 – 130%
(LCS) or Reference Material
Matrix Spikes Not Required n/a
Lab Duplicates One per 20 samples 35% RPD
* Minimum DQOs apply to individual QC samples, not averages, and only at levels above 10x MDL.
Laboratories should report qualified data when DQOs are not met, unless other evidence
demonstrates that the quality of associated sample data has not been adversely affected.

Prepare the LCS using a 1:1 mixture of soluble (e.g. K2Cr2O7) and insoluble (e.g.
PbCrO4) Cr(VI) salts. If recovery problems are experienced, perform separate
Method Spikes with soluble and insoluble Cr(VI) salts to help identify the cause of
the problem.

Sample Matrix Spikes, as described in Method 3060A, are recommended for

specific projects where it is desirable to know whether a sample matrix can support
Cr(VI) species. Reducing sample matrices (e.g. anoxic sediments, clays) tend to
reduce Cr(VI) species to Cr(III), causing low spike recoveries. Method 3060A
provides advice for interpreting low Sample Matrix Spike recoveries.

Prescribed The following components of this method are mandatory:

Elements
1. All primary elements of the alkaline digestion procedure from US EPA SW846
3060A (Dec 1996 or newer) must be followed as described. No significant
modifications to the digestion procedure are permitted.

2. The digestion solution and phosphate buffer must be of the same strengths
and relative amounts as prescribed in EPA 3060A.

3. The ratio of sample to digestion solution and phosphate buffer must be the
same as prescribed by EPA 3060A.

4. Magnesium chloride in phosphate buffer must be added to all samples to

prevent oxidation of Cr(III) to Cr(VI).

5. Soils must not be dried prior to digestion.

6. A minimum of 1.5 grams of soil (wet weight) must be digested, except if

limited by available sample.

7. The pH ranges specified in Method 3060A and the chosen analytical method
must be adhered to.

8. Digestion temperature (solution temperature, not hotblock temperature) must

be 90-95˚C.

9. Digestion time must be at least 1 hour.

C-105
 10. Samples must be stirred continuously during digestion as prescribed by
3060A.

11. Sample digests must be filtered or centrifuged prior to analysis.

12. All QC Requirements and Performance Elements must be met as indicated.

Apart from the limitations above, and provided performance requirements are
met, laboratories may introduce minor physical and procedural modifications to
the method in order to improve quality and/or efficiency.

Reference Test Methods for Evaluating Solid Wastes – Physical / Chemical Methods, SW-
846, 3rd Edition, Method 3060A, Alkaline Digestion for Hexavalent Chromium,
December 1996, Final Update III, US EPA, Washington, D.C.

Revision History Dec, 2002: Method developed by BCLQAAC Technical Sub-Committee,

superceding the method published in Supplement #1.
July 26, Method was modified such that continuous stirring as per EPA
2013: 3060A is required, Other key elements of the method became
prescribed, including minimum sample weight, minimum
digestion time, and requirement for filtration or centrifugation of
digest solution. QC requirements and DQOs were revised.
Effective date for this method is October 1, 2013.
October 1, Hexavalent Chromium in Solids by Alkaline Digestion – PBM
2013: method updated.

C-106
 Metals
Revision History: May 9, 2003

Trivalent Chromium in Solids by Calculation

Parameter Trivalent Chromium

Sample Handling Refer to individual techniques for total and hexavalent chromium.
Preservation

Analytical Method Calculation: SALM-digestable total chromium minus chromium (VI).

EMS Codes To be assigned on request.

Introduction This procedure is applicable to the determination of trivalent chromium in

solid samples (soils, sediments, sludges, etc.).

Chromium can exist in nine different oxidation states, but trivalent (III) and
hexavalent (VI) are the most common in the environment. Cr(III) is the most
thermodynamically stable species under ambient redox conditions.
Complexed Cr(III) occurs naturally and is ubiquitous in the environment. The
principal source of Cr(VI) in the environment is anthropogenic pollution.
Cr(VI) has an affinity to react with organic matter and other reducing
substances. Cr(III) solids are practically insoluble in water at pH > 4, and do
not tend to leach from a soil matrix into groundwaters. At pH > 8.5, Cr(VI)
solids are highly soluble and completely mobile, and can readily leach from
soils into groundwater systems.

Direct determination of Cr(III) requires complex speciation work. However,

Cr(III) concentrations can be conservatively approximated by subtracting
measured Cr(VI) concentrations from measured total chromium
concentrations in the same sample. Note that this method requires the use
of the BC Strong Acid Leachable Metals (SALM) method for determination of
total chromium, so the resulting Cr(III) concentration reflects only those
species liberated by this digestion procedure.

Cr(III) is considered to be an essential trace element in animal and human

nutrition. The Government of Canada has determined that Cr(III) compounds
are “unclassifiable with respect to carcinogenicity in humans”.

Method Summary Chrome(III) is determined by difference of Total Chromium (Cr-T) and

hexavalent chromium (Total Chromium by SALM method minus Hexavalent
Chromium by Alkaline Digestion).

MDL When the Cr(VI) concentration in a sample is less than or equal to one-third
of the Total Chromium concentration, the MDL for calculated Cr(III) is equal
to the MDL for the Cr-T result.

However, as the relative proportion of Cr(VI) in the sample increases, the

uncertainty (and therefore the MDL) in the calculated Cr(III) concentration
increases exponentially with the relative proportion of Cr(VI) in the sample.
Refer to the Calculation Procedure for guidance on how to determine the
MDL for situations where the Cr(VI) value exceeds one-third of the Cr-T
value.

C-107
Matrix Soil, sediment, sludges, solid wastes.

Interferences and
Precautions Refer to individual analytical techniques for total and hexavalent chromium.

In samples where chromium (VI) species dominate, the calculated result for
Cr(III) is subject to high uncertainty (and therefore high detection limits) due
to the propagation of the uncertainties of the total chromium and Cr(VI)
analytical results. This is not normally problematic from a regulatory point of
view because guidelines for Cr(VI) will be exceeded before the variability of
the Cr(III) result becomes an issue.

Stability Refer to individual analytical techniques for total and hexavalent chromium.

Calculation Analyze the sample for total chromium using the BC Strong Acid Leachable.

Procedure Metals (SALM) digestion procedure and an appropriate analytical technique

for chromium (e.g. ICP-OES or AAS).

Analyze the sample for hexavalent chromium using the BC Method for
Hexavalent Chromium in Solids by Alkaline Digestion.

Subtract the hexavalent chromium result from the total chromium result to
approximate the concentration of trivalent chromium.

If the Cr(VI) concentration is less than or equal to one-third of the Cr-T

concentration, then the MDL for the Cr-T result may be used as the MDL for
the Cr(III) result.

If the Cr(VI) concentration exceeds one-third of the Cr-T concentration, then

the MDL for the Cr(III) result is calculated as follows:
2 2
MDLCr(III) = √ [ (UT-Cr ) + (UCr(VI)) ]

UT-Cr and UCr(VI) represent the analytical uncertainties (at the 95% confidence
level) of the results for Cr-T and Cr(VI). Laboratories are referred to the
Eurachem/CITAC Guide "Quantifying Uncertainty in Analytical
Measurement,” and to CAEAL’s “Policy on Uncertainty of Measurement in
Environmental Testing” for more information on the estimation of analytical
uncertainty.

Reported detection limits should be no less than the appropriate MDL. If the
MDL exceeds the relevant action limit, then this method is inappropriate, and
a direct determination of Cr(III) may be necessary.

Report results as mg/kg on a dry weight basis.

Precision and Precision and accuracy for Cr(III) by calculation is a function of the precision
Accuracy and accuracy of the Cr-T and Cr(VI) results for a given sample, and a
function of the relative magnitude of the Cr(VI) result versus the total
chromium result.

C-108
Quality Control Perform calculations to determine Cr(III) concentration on all relevant QC
samples for which total and hexavalent chromium data is available.

References 1. Test Methods for Evaluating Solid Wastes – Physical / Chemical

Methods, SW-846, 3rd Edition, Method 3060A, Alkaline Digestion for
Hexavalent Chromium, December 1996, Final Update III. United States
Environmental Protection Agency, Washington, D.C.

2. Standard Methods for the Examination of Water and Wastewater, APHA,

AWWA, WPCF, 20th edition, 1998. Method 3500 - Cr B, Colorimetric
Method.

3. Test Methods for Evaluating Solid Wastes – Physical / Chemical

Methods, SW-846, 3rd Edition, Method 7196A, Chromium, Hexavalent
(Colorimetric), July 1992, Final Update III. United States Environmental
Protection Agency, Washington, D.C.

4. Standard Methods for the Examination of Water and Wastewater, APHA,

AWWA, WPCF, 20th edition, 1998. Method 3500 - Cr C, Ion
Chromatographic Method.

5. Canadian Soil Quality Guidelines for the Protection of Environmental and

Human Health, Chromium, 1999, Canadian Council of Ministers of the
Environment.

6. CSR Analytical Method 8, “Strong Acid Leachable Metals (SALM) in

Soil”, Version 1.0, February, 2001, British Columbia Ministry of
Environment, Lands and Parks.

7. “Hexavalent Chromium in Solids by Alkaline Digestion”, Version 1.0,

December 2, 2001, British Columbia Ministry of Water, Land and Air
Protection.

8. Eurachem / CITAC Guide, "Quantifying Uncertainty in Analytical

Measurement," Second Edition (QUAM:2000.P1). Editors SLR Ellison,
M Rosslein, A Williams.

9. “CAEAL Policy on Uncertainty of Measurement in Environmental

Testing,” Revision 1.4.

C-109
 Metals
Revision Date: December 31, 2000

Cobalt (Atomic Absorption - Direct Aspiration)

Parameter Cobalt, total
Cobalt, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) Co-T X073

LA: HNO3: AA (total) Co-T X351
FF, FA: HNO3: AA (dissolved) Co-D X203
LF, LA: HNO3: AA (dissolved) Co-D X085

Introduction Cobalt appears to be essential to life, and plays an important part in

vegetation and animal nutrition. Natural waters usually contain less than
0.010 mg/L of cobalt.

Method Summary Aqueous solutions of metals are aspirated into a flame and atomized. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.05 mg/L
Range: 0.05-5.0 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. Excesses of
other transition metals may slightly depress the response of cobalt. Matrix
matching or the method of standard additions is recommended.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Co hollow cathode lamp

Parameters Wavelength: 240.7 nm
Type of flame: air/acetylene
Background correction: recommended

Apparatus, Materials See section 2.1.5 and 2.1.6 of this manual.

and Reagents

C-110
Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WEF, 18th edition, 1992 Method 3111 B/D.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-111
 Metals
Revision Date: December 31, 2000

Cobalt (Atomic Absorption - Graphite Furnace)

Parameter Cobalt, total
Cobalt, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: GFAA (total) Co-T X072

LA: HNO3: GFAA (total) Co-T X179
FF, FA: HNO3: GFAA (dissolved) Co-D X116
LF, LA: HNO3: GFAA (dissolved) Co-D X357

Introduction Cobalt appears to be essential to life, and plays an important part in

vegetation and animal nutrition. Natural waters usually contain less than
0.010 mg/L of cobalt.

Method Summary A discrete sample volume is introduced into the graphite sample boat which
is heated in stages to accommodate drying of the solution, charring and
volatilization of organics and other matrix components, and finally,
atomization of the analyte into the light path of the spectrometer. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.001 mg/L
Range: 0.001-0.100 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. Excess chloride
may interfere. Verification by standard additions may be necessary to
ensure that this interference is absent.

Sample Handling See section 1.0, the sample preparation section of the manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Co hollow cathode lamp

Parameters Wavelength: 240.7 nm
Background Correction: recommended

Apparatus, Materials See section 2.1.5 and 2.1.6 of the AA methods section of this manual.
and Reagents

C-112
Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WEF, 18th edition, 1992, Method 3113B.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-113
 Metals
Revision Date: December 31, 2000

Copper (Atomic Absorption - Direct Aspiration)

Parameter Copper, total
Copper, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) Cu-T X073

LA: HNO3: AA (total) Cu-T X351
FF, FA: HNO3: AA (dissolved) Cu-D X203
LF, LA: HNO3: AA (dissolved) Cu-D X085

Introduction Copper is an essential element in man and animal. Both excesses and
deficiencies of this metal can occur. In soft water areas, corrosion of copper
water pipes can increase the daily intake of copper.

The Canadian drinking water guideline for copper is 1 mg/L. The limit
indicated in Water Criteria for Salmonid Hatcheries is 0.002 mg/L.

Method Summary Aqueous solutions of metals are aspirated into a flame and atomized. The
absorption of light at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.020 mg/L
Range: 0.020-5.0 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. Coexisting
elements causing relatively large interferences are Al, Si, and Ti.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Cu hollow cathode lamp

Parameters Wavelength: 324.7 nm
Type of Flame: air/acetylene
Background Correction: recommended

Apparatus, Materials See section 2.1.5 and 2.1.6 of the AA methods section of this manual.
and Reagents

C-114
Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 17th edition, 1989 Method 3500-Cu.
b) Methods for Chemical Analysis of Water and Wastes, EPA-600 4-
79-020, March 1983 Method 220.1.
c) Trace Elements in Human and Animal Nutrition, Eric J. Underwood,
4th edition, Academic Press, 1977.
d) (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-115
 Metals
Revision Date: December 31, 2000

Copper (Atomic Absorption - Graphite Furnace)

Parameter Copper, total
Copper, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: GFAA (total) Cu-T X072

LA: HNO3: GFAA (total) Cu-T X179
FF, FA: HNO3: GFAA (dissolved) Cu-D X116
LF, LA: HNO3: GFAA (dissolved) Cu-D X357

Introduction Copper is an essential element in man and animal. Both excesses and
deficiencies of this metal can occur. In soft water areas, corrosion of copper
water pipes can increase the daily intake of copper.

The Canadian drinking water guideline for copper is 1 mg/L. The limit
indicated in Water Criteria for Salmonid Hatcheries is 0.002 mg/L.

Method Summary A discrete sample volume is introduced into the graphite sample boat which
is heated in stages to accommodate drying of the solution, charring and
colatilization of organics and other matrix components, and finally,
atomization of the analyte into the light path of the spectrometer. The
absorption of light at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.001 mg/L
Range: 0.001-0.100 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. Matrix modifiers
for interference removal are given by Standard Methods as: NH4NO3,
ascorbic acid.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Cu hollow cathode lamp

Parameter Wavelength: 324.7 nm
Background Correction: recommended

C-116
Apparatus, Materials See section 2.1 of the AA methods section of this manual.
and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 17th edition, 1989 Section 3113.
b) Methods for Chemical Analysis of Water and Wastes, EPA-600 4-
79-020, March 1983, Method 220.2.
c) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-117
 Metals
Revision Date: December 31, 2000

Copper (Atomic Emission - Inductively Coupled Plasma {ICAP})

Parameter Copper, total
Copper, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.4, the ICP-AES method section.

EMS Code FA: HNO3: ICAP (total) Cu-T X349

LA: HNO3: ICAP (total) Cu-T X352
FF, FA: HNO3: ICAP (dissolved) Cu-D X350
LF, LA: HNO3: ICAP (dissolved) Cu-D X356

Introduction Copper is an essential element in man and animal. Both excesses and
deficiencies of this metal can occur. In soft water areas, corrosion of copper
water pipes can increase the daily intake of copper.

The Canadian drinking water guideline for copper is 1 mg/L. The limit
indicated in Water Criteria for Salmonid Hatcheries is 0.002 mg/L.

Method Summary Aqueous solutions of metals are converted to aerosols in the nebulizer of the
ICP and injected directly into a high temperature plasma (6000 to 8000°K).
The highly efficient ionization produces ionic emission spectra and
wavelengths specific to the elements of interest can be monitored either
simultaneously or sequentially.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.005 mg/L
Range: 0.005-1000.0 mg/L
See Table C-2 in section 2.4, the ICP method section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences See section 2.4.4 of the ICP methods section of this manual.
and Precautions

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Wavelength: 324.7 nm

Parameter Background Correction: recommended

Apparatus, Materials See section 2.4 of the ICP-AES methods section of this manual.
and Reagents

C-118
Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 17th edition, 1989 Section 3120 B.
b) Methods for Chemical Analysis of Water and Wastes, EPA-600 4-
79-020, March 1983, Method 200.7.
c) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-119
 Metals
Revision Date: December 31, 2000

Iron (Atomic Absorption - Direct Aspiration)

Parameter Iron, total
Iron, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) Fe-T X073

LA: HNO3: AA (total) Fe-T X351
FF, FA: HNO3: AA (dissolved) Fe-D X203
LF, LA: HNO3: AA (dissolved) Fe-D X085

Introduction Iron is an essential trace element for plants and animals, but is an
undesirable constituent of water supplies if present at appreciable
concentrations.

Iron has a deleterious effect on the taste of potable water and produces
objectionable stains, therefore the Canadian drinking water guideline is set at
a maximum limit of 0.3 mg iron/L. (aesthetic objective - not health related).
Major sources of pollution include mine drainage and industrial waste.

Method Summary Aqueous solutions of metals are aspirated into a flame and atomized. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.03 mg/L
Range: 0.03-5.0 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. Cobalt, copper
and nickel can cause a reduction in sensitivity. A very lean, hot flame can
aid in minimizing these interferences. Treat standards and samples with
0.2% calcium chloride to eliminate silicon depression of the iron signal. A
nitrous oxide-acetylene flame reduces or eliminates most interferences but
sensitivity will be markedly reduced.

Sample Handling See section 1.0, the sample preparation section.

and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

C-120
Instrument Source: Fe hollow cathode lamp
Parameters Wavelength: 248.3 nm
Type of Flame: air/acetylene
Background Correction: recommended

Apparatus, Materials See sections 2.1.5 and 2.1.6 of this manual.

and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/AC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WEF, 18th edition, 1992, Method 3111 B/D.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-121
 Metals
Revision Date: December 31, 2000

Iron (Atomic Absorption - Graphite Furnace)

Parameter Iron, total
Iron, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: GFAA (total) Fe-T X072

LA: HNO3: GFAA (total) Fe-T X179
FF, FA: HNO3: GFAA (dissolved) Fe-D X116
LF, LA: HNO3: GFAA (dissolved) Fe-D X357

Introduction Iron is an essential trace element for plants and animals, but is an
undesirable constituent of water supplies if present in appreciable
concentrations.

Iron has a deleterious effect on the taste of potable water and produces
objectionable stains, therefore the Canadian drinking water guideline is set at
a maximum limit of 0.3 mg iron/L. (aesthetic objective - not health related).
Major sources of pollution include mine drainage and industrial waste.

Method Summary A discrete sample volume is introduced into the graphite sample boat which
is heated in stages to accommodate drying of the solution, charring and
volatilization of organics and other matrix components, and finally,
atomization of the analyte into the light path of the spectrometer. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.001 mg/L
Range: 0.001-0.10 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences
and Precautions See section 2.1.4 of the AA methods section of this manual. Due to the
extreme sensitivity of the method and presence of iron as a trace
contaminant in dust, plastics, glassware, acids and other reagents,
appropriate blanks must be included to allow for correction of results.
Platform atomization is recommended for iron analysis. New platforms and
tubes might require repeated firing at high temperature to reduce background
signal to acceptable levels.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

C-122
Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Fe hollow cathode lamp

Parameters Wavelength: 248.3 nm
Background Correction: recommended

Apparatus, Materials See section 2.1.5 and 2.1.6 of this manual.

and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Method for the Examination of Water and Wastewater,

APHA, AWWA, WEF, 18th edition, 1992, Method 3113B.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-123
 Metals
Revision Date: December 31, 2000

Lead (Atomic Absorption - Direct Aspiration)

Parameter Lead, total
Lead, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) Pb-T X073

LA: HNO3: AA (total) Pb-T X351
FF, FA: HNO3: AA (dissolved) Pb-D X203
LF, LA: HNO3: AA (dissolved) Pb-D X085

Introduction Lead is a highly toxic cumulative poison in man and animals. Chronic lead
poisoning is characterized particularly by neurological defects, renal tubular
dysfunction and anemia. Children will absorb 50% of ingested lead; adults
absorb 10%. In children, even low lead levels have been linked to learning
disabilities and behaviour problems.

The Canadian drinking water guideline for lead is 0.01 mg/L. The limit
indicated in Water Criteria for Salmonid Hatcheries is 0.004 mg/L.

Method Summary Aqueous solutions of metals are aspirated into a flame and atomized. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.10 mg/L
Range: 0.10-20.0 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences See section 2.1.4 of the AA methods section of this manual.

and Precautions Coexisting elements causing relatively large interferences are Fe and Ti.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Pb hollow cathode lamp

Parameters Wavelength: 283.3 nm
Type of Flame: air/acetylene
Background Correction: recommended

C-124
Apparatus, Materials See section 2.1.5 and 2.1.6 of the AA methods section of this manual.
and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 17th edition, 1989 Method 3500-Pb.
b) Method for Chemical Analysis of Water and Wastes EPA-600 4-
79-020, March 1983, Method 239.1.
c) Trace Elements in Human and Animal Nutrition, Eric J. Underwood,
4th edition, Academic Press, 1977.
d) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-125
 Metals
Revision Date: December 31, 2000

Lead (Atomic Absorption - Graphite Furnace)

Parameter Lead, total
Lead, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: GFAA (total) Pb-T X072

LA: HNO3: GFAA (total) Pb-T X179
FF, FA: HNO3: GFAA (dissolved) Pb-D X116
LF, LA: HNO3: GFAA (dissolved) Pb-D X357

Introduction Lead is a highly toxic cumulative poison in man and animals. Chronic lead
poisoning is characterized particularly by neurological defects, renal tubular
dysfunction and anemia. Children will absorb 50% of ingested lead; adults
absorb 10%. In children, even low lead levels have been linked to learning
disabilities and behaviour problems.

The Canadian drinking water guideline for lead is 0.01 mg/L. The limit
indicated in Water Criteria for Salmonid Hatcheries is 0.004 mg/L.

Method Summary A discrete sample volume is introduced into the graphite sample boat which
is heated in stages to accommodate drying of the solution, charring and
volatilization of organics and other matrix components, and finally,
atomization of the analyte into the light path of the spectrometer. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.001 mg/L
Range: 0.001-0.100 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences
and Precautions See section 2.1.4 of the AA methods section of this manual. Matrix modifiers
for interference removal are given by Standard Methods as:
NH4H2PO4, (NH4)2HPO4
Mg(NO3)2, NH4NO3
ascorbic acid, oxalic acid
phosphoric acid, HNO3, LaCl, (NH4)EDTA

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

C-126
Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Pb hollow cathode lamp

Parameters Wavelength: 283.3 nm
Background Correction: recommended

Apparatus, Materials See section 2.1.5 and 2.1.6 of the AA methods section of this manual.
and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 17th edition, 1989 Section 3113.
b) Methods for Chemical Analysis of Water and Wastes, EPA-600 4-
79-020, March 1983, Method 239.2.
c) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-127
 Metals
Revision Date: December 31, 2000

Lead (Atomic Emission - Inductively Coupled Argon Plasma

{ICAP})
Parameter Lead, total
Lead, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.4, the ICP-AES methods section.

EMS Code FA: HNO3: ICAP (total) Pb-T X349

LA: HNO3: ICAP (total) Pb-T X352
FF, FA: HNO3: ICAP (dissolved) Pb-D X350
LF, LA: HNO3: ICAP (dissolved) Pb-D X356

Introduction Lead is a highly toxic cumulative poison in man and animals. Chronic lead
poisoning is characterized particularly by neurological defects, renal tubular
dysfunction and anemia. Children will absorb 50% of ingested lead; adults
absorb 10%. In children, even low lead levels have been linked to learning
disabilities and behaviour problems.

The Canadian drinking water guideline for lead is 0.01 mg/L. The limit
indicated in Water Criteria for Salmonid Hatcheries is 0.004 mg/L.

Method Summary Aqueous solutions of metals are converted to aerosols in the nebulizer of the
ICP and injected directly into a high temperature plasma (6000 to 8000°K).
The highly efficient ionization produces ionic emission spectra and
wavelengths specific to the elements of interest can be monitored either
simultaneously or sequentially.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.050 mg/L
Range: 0.050-500.0 mg/L
See Table C-2 in section 2.4, the ICP method section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.4.4 of the ICP methods section of this manual.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Wavelength: 220.3 nm

Parameters Background Correction: recommended

C-128
Apparatus, Materials See section 2.4 of the ICP methods section of
and Reagents this manual.

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 17th edition, 1989 Section 3120 B.
b) Methods for Chemical Analysis of Water and Wastes, EPA-600 4-
79-020, March 1983, Method 200.7.
c) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-129
 Metals
Revision Date: December 2002

Lead in Solids by Flame AA

Parameter Lead (Pb)

Sample Preparation See Section 1.2 for sample preparation.

Ems Codes EMS Codes assigned on request

Analytical Method US EPA Method 7420 Atomic Absorption, Direct Aspiration.

Introduction Lead is a highly toxic, cumulative poison in man and animals. Chronic lead
poisoning is often characterized by central nervous system disorders.

Method Summary The soil or sediment sample is initially homogenized to ensure representative
sub-aliquots will be analyzed. An accurate weight of soil is acid digested and
the resulting digestate is analyzed for lead content by direct aspiration into a
standard atomic absorption spectrophotometer.

General Operating Element Wavelength Slit Lamp Current Detection Limit

Conditions / Lead 283.3 nm * 0.7 nm 8 mA 1.0 µg/g
Detection Limits
* The wavelength provided is the primary one used, alternatively the 217.0
nm line may be used.

Matrix Soil, solids, (marine) sediments.

Source Lead Hollow Cathode Lamp

Type of Flame Air / Acetylene

Background Correction Required

Interferences The most common type of interferences is "chemical" and is caused by lack
of absorption of atoms bound in molecular combination in the flame. The
addition of chemicals such as lanthanum can reduce this effect. The
presence of high dissolved solids (a common case in digested soils) may
result in light scattering. Background correction should aid in the elimination
of this problem. Refer to instrument operations manual, EPA Method 7420,
and B.C. Laboratory Manual Section 2.1.4.1 in the Laboratory Manual for
other sources and corrective measures.

Sample Handling Container - acid washed polyethylene bottle.

and Preservation Digested soils are already in an acid medium and require no extra
preservation chemicals.

C-130
Stability Lead in digested soil samples have a holding time of six month.

Instrument Direct flame atomic absorption spectrophotometer with background correct

system.

Calibration / Refer to instrument operations manual for set-up and analysis

Analysis Procedures techniques.

Precision Refer to EPA Method 7420.

Accuracy Refer to EPA Method 7420.

Quality Control a) Confirm calibration by analyzing a separate sourced calibration

verification standard.
b) Blanks, Reference Materials and Duplicates prepared with each
digestion batch must meet predetermined QA/QC requirements.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 17th edition, 1989 Method 3500-Pb.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical Methods
(Revised). Publication # SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition, 1990.
Method 7420.

Revision History December 2002: Method adopted from Supplement #1 Manual,

EMS Codes assigned.

C-131
 Metals
Revision Date: December 31, 2000

Magnesium (Atomic Absorption - Direct Aspiration)

Parameter Magnesium, total
Magnesium, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) Mg-T X073

LA: HNO3: AA (total) Mg-T X351
FF, FA: HNO3: AA (dissolved) Mg-D X203
LF, LA: HNO3: AA (dissolved) Mg-D X085

Method Summary Aqueous solutions of metals are aspirated into a flame and atomized. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.001 mg/L
Range: 0.001-0.50 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. Ionization can
occur in an air-acetylene flame and can be controlled by the addition of
potassium chloride to a level of 0.1%. Elements that form stable oxides (Al,
Be, P, Si, Ti, V, Zr) will reduce magnesium sensitivity. These can be
controlled by the addition 0.1-1.0% lanthanum or strontium.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Mg hollow cathode lamp

Parameters Wavelength: 285.2 nm (primary); 202.6 nm (alternate)
Type of Flame: air/acetylene
Background Correction: recommended

Apparatus, Materials See sections 2.1.5 and 2.1.6 of this manual.

and Reagents

Precision None listed.

Accuracy None listed.

C-132
Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater

APHA, AWWA, WEF, 18th edition, 1992, Method 3111 B/D.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-133
 Metals
Revision Date: December 31, 2000

Manganese (Atomic Absorption - Direct Aspiration)

Parameter Manganese, total
Manganese, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) Mn-T X073

LA: HNO3: AA (total) Mn-T X351
FF, FA: HNO3: AA (dissolved) Mn-D X203
LF, LA: HNO3: AA (dissolved) Mn-D X085

Introduction Manganese occurs naturally as salts and minerals in nature. Major

manganese containing substances are pyrolusite (MnO 2), rhodochrosite
(MnCO3) and rhodonite.

Manganese is a vital micronutrient for plants and animals, but can be toxic
when very large doses are ingested. The objective for drinking water
supplies is <0.05 mg/L. This relatively low limit is not due to toxicological
consideration but rather due to the staining effect of manganese on laundry
and plumbing fixtures. Discharges known to contain manganese are
domestic and industrial effluents.

Method Summary Aqueous solutions of metals are aspirated into a flame and atomized. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.01 mg/L
Range: 0.01-3.0 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions Silicon has a suppressing effect on the manganese signal. This interference
can be controlled by the addition of 2000 ppm CaCl2.
See also section 2.1.4 of the AA methods section of this manual.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

C-134
Instrument Source: Mn hollow cathode lamp
Parameters Wavelength: 279.5 nm
Type of flame: Air/Acetylene
Background Correction: recommended

Apparatus, Materials See section 2.1.5 and 2.1.6 of this manual.

and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References 1. Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WEF, 18th edition, 1992, Method 3111 B/D.

2. Test Methods for Evaluating Solid Wastes - Physical/Chemical

Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-135
 Metals
Revision Date: December 31, 2000

Manganese (Atomic Absorption - Graphite Furnace)

Parameter Manganese, total
Manganese, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: GFAA (total) Mn-T X072

LA: HNO3: GFAA (total) Mn-T X179
FF, FA: HNO3: GFAA (dissolved) Mn-D X116
LF, LA: HNO3: GFAA (dissolved) Mn-D X357

Introduction Manganese occurs naturally as salts and minerals. Major manganese

containing substances are pyrolusite (MnO 2), rhodochrosite (MnCO3) and
rhodonite.

Manganese is a vital micronutrient for plants and animals, but can be toxic
when very large doses are ingested. The objective for drinking water
supplies is <0.05 mg/L. This relatively low limit is not due to toxicological
consideration but rather due to the staining effect of manganese on laundry
and plumbing fixtures. Discharges known to contain manganese are
domestic and industrial effluents.

Method Summary A discrete sample volume is introduced into the graphite sample boat which
is heated in stages to accommodate drying of the solution, charring and
volatilization of organics and other matrix components, and finally,
atomization of the analyte into the light path of the spectrometer. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.0002 mg/L
Range: 0.0002-0.030 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and See section 2.1.4 of the AA methods section of this manual.
Precautions

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

C-136
Instrument Source: Mn hollow cathode lamp
Parameters Wavelength: 279.5 nm
Background Correction: recommended

Apparatus, Materials See section 2.1.5 and 2.1.6 of this manual.

and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9 QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WEF, 18th edition, 1992, Method 3113B.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-137
 Metals
Revision Date: December 31, 2000

Mercury (Atomic Absorption - Cold Vapour)

Parameter Mercury, total
Mercury, dissolved

Sample Preparation See section 1.0 the sample preparation section.

Analytical Method See section 2.1, the AA methods section, and section 2.3, the cold vapour
methods section.

EMS Code FA: HNO3/K2Cr2O7: CVAA (total) Hg-T X346

LA: HNO3/K2Cr2O7: CVAA (total) Hg-T X353
FF, FA: HNO3/K2Cr2O7: CVAA (dissolved) Hg-D X347
LF, LA: HNO3/K2Cr2O7: CVAA (dissolved) Hg-D X358

Introduction The determination of small traces of mercury has been of importance in

toxicology for many years. In geochemistry, metallurgy and many industries,
the trace determination of this element is also of importance. Because of its
simplicity and specificity, atomic absorption spectroscopy, with a cold vapour
generation sample introduction system, best meets the requirements for the
economical determination of trace concentrations of mercury.

Method Summary Mercury is converted to its ionic form in solution. This ionic mercury is
reduced to its elemental state and swept from solution into a cell positioned
in the light path of a standard AAS. The concentration of mercury in solution
is determined using conventional AAS techniques.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.00005 mg/L
Range: 0.00005 - 0.001 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences a) specific volatile material which absorbs at 253.7 nm,

and Precautions b) sulfide,
c) copper,
d) chlorides and free chlorine.

Sample Handling See Section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of
28 days. Preservation using a solution of nitric acid and potassium
dichromate has been reported to increase mercury stability in some
instances.

Instrument Source: Hg vapour lamp or electrodeless discharge lamp (EDL)

Parameters Wavelength: 253.7 nm
Background Correction: not required

C-138
Apparatus, Materials See sections 2.1.5 and 2.1.6 of this manual.
and Reagents

Accuracy None listed.

Precision None listed.

Quality Control See Section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WEF, 18th edition, 1992.
b) Instructions - MHS-20 Mercury/Hydride System, Publication 338-A2-M
294/12.79. Bodenseewerk Perkin-Elmer & Co. GMBH/Uberlingen.
1979.
c) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

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 Metals
Revision: December 2002

Mercury in Solids by Semi-automated Cold Vapour Atomic

Absorption (CVAA)
Parameter Hg-T - Mercury Total

Sample Handling Not available.

and Preservation

Analytical Method Aqua Regia digestion; CVAA

EMS Codes

Introduction This method is applicable to the quantitative determination of mercury in soil.

Summary Organomercury compounds are oxidized via Aqua regia/KMnO4 digestion.

The mercury compounds are then reduced to elemental mercury. A stream
of synthetic air introduced into the system passes through a reference cell
and then, after sparging the elemental mercury, passes through the sample
cell. Absorbance is measured at 253.7nm against the reference as a
function of the mercury concentration.

MDL 0.05 µg/g

Matrix Soil, sediments, solids.

Interferences and
Precautions a) Samples containing high chloride may interfere due to the liberation of
free chlorine which absorbs at 253.7nm. Additional permanganate
must be compensated by excess hydroxylamine sulphate-sodium
chloride to avoid this positive interference.
b) Certain volatile organic material which absorbs at 253.7 nm will also
interfere. If this is suspected, run the sample without the addition of
reagents to determine if this type of interference is present.

Stability Not available.

Procedure
Apparatus a) Water Bath with alcohol thermometer able to read to 100°C.
b) Compressed Air with a 2 stage regulator and an adjustable valve able
to deliver between 50 and 500cc/min.
c) An automated system consisting of:
1) sampler,
2) proportioning pump,
3) manifold,
4) phase separating reaction tube,
5) UV monitor equipped with 30cm flow cell and 253.7 nm lamp and
6) data collection.

Reagents a) Hydrochloric Acid (HCl) - Concentrated (Nondetectable Mercury

Content).
b) Nitric Acid (HNO3) - Concentrated (Non-detectable Mercury Content).
c) Potassium Permanganate (KMnO4), 1.2% Dissolve 23.1g KMnO4 into
DI and adjust volume to 2L.

C-140
 d) Aqua Regia, 50% - to 100mL DI, add 25mL conc. HCl and 75mL
HNO3.
e) Hydroxylamine Sulphate-Sodium Chloride, 12% - Dissolve 120g
Hydroxylamine Sulphate and 120g Sodium Chloride (NaCl) into DI and
adjust volume to 1L.
f) Stannous Chloride, 10% - Dissolve 100g SnCl2 into 100mL
concentrated HCl. Warm to dissolve and add to a 1L flask containing
approximately 800mL DI and adjust volume to 1L.
g) Instrument Background Solution - 60mL concentrated HNO3 to 2L DI.
h) Potassium Dichromate (K2Cr2O7), 10% - 100g K2Cr2O7 to 1L DI.
i) Stock Mercury Solution, 100mg/L Hg - Dissolve 0.1678g of phenyl
mercuric acetate in 1L flask of 1% H2SO4. Store at 4°C in an amber
glass bottle.
j) Intermediate Mercury Solution, 500µg/L Hg - Pipet 5mL of the stock
Mercury solution in a 1L flask of 5mL H2SO4, 5mL 10% K2Cr2O7 and
adjust volume to 1L with DI. Store at 4°C in an amber glass bottle.
k) Working Mercury Standards, 1.0mg/L, 0.50mg/L, 0.25mg/L, 0.05mg/L,
and 0.00mg/L Hg - Pipet 5.0, 3.0, 2.0, 1.0, and 0.5mL of the
Intermediate Mercury solution in a 100mL flask of 0.5mL H 2SO4, 0.5mL
10% K2Cr2O7 and adjust volume to 100mL with DI.

Procedure Digestion Procedure:

a) Accurately weigh and record 0.1g of air dried (60°C) and ground soil
into a 50mL falcon tube. For standards, accurately pipet 100µL of
standards into each tube for the 5 standards.
b) Add 5mL of 50% Aqua Regia and mix.
c) Place in a water bath preheated @ 95°C for 2 minutes.
d) Remove samples, allow to cool for 5-10 minutes and add 32mL of
1.2% KMnO4. Cap and gently mix. If sample fails to maintain a
permanganate colour after the addition of the digestion solution, add
5% KMnO4 in 3mL increments until the colour remains constant.
e) Place in a water bath preheated @ 95°C for 30 minutes.
f) Remove samples, allow to cool for 5-10 minutes and add 3mL of 12%
hydroxylamine sulphate-sodium chloride. If extra KMnO4 was added,
add an appropriate addition of hydroxylamine sulphate-sodium chloride
and adjust for this at time of analysis. Cap and gently mix until clear.
g) Allow elemental mercury vapour to enter sample call of AAS.
h) Record absorbance on recording device and calculate mercury
concentration by comparison to calibration standards prepared and
analyzed concurrently.

Calibration According to manufacturer's specifications.

Precision Standard reference material NBS 2704 and NRCC Best1 at concentrations of
1.47 µg/g Hg and 0.092 µg/g gave coefficients of variation of 7% and 8%
respectively.

Accuracy Standard reference material NBS 2704 and NRCC Best1 at concentrations of
1.47 µg/g Hg and 0.092 µg/g gave recoveries of 98% and 100% respectively.

C-141
Quality Control a) Run QCA/QCB daily, run Duplicates 1 in 10, run blanks 1 in 10, run
blank spikes 1 in 10. The acceptable levels should be as follows;
QCA±10%, QCB±15%, duplicate±20%, and blank spikes±20%. Also
run NBS 2704 and NRCC Best1 (see acceptance range from
Certificate).

b) Monitor baseline drift, sensitivity drift, and carryover. Automatic

correcting of these will be done by the Labtronic Data System.

References a) Environmental Protection Agency. Method For Determination of

Mercury. Cincinnati, Ohio. Method 7471 (1992).

Revision History March 1997: Method Published in Manual Supplement #1.

December 2002: Method adopted from Supplement #1.

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 Metals
Revision Date: December 31, 2000

Molybdenum (Atomic Absorption - Direct Aspiration)

Parameter Molybdenum, total
Molybdenum, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) Mo-T X073

LA: HNO3: AA (total) Mo-T X351
FF, FA: HNO3: AA (dissolved) Mo-D X203
LF, LA: HNO3: AA (dissolved) Mo-D X085

Introduction Molybdenum is found in the soil and is an important trace element for the
growth of grasses and vegetables. Its uses include pigments for printing,
inks, alloying agent in steels and cast iron, high temperature alloys, tool
steels, catalysts, solid lubricants, and special batteries.

Method Summary Aqueous solutions of metals are aspirated into a flame and atomized. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.1 mg/L
Range: 0.1 - 40.0 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. Interferences in
an air/acetylene flame from Ca, Sr, SO4, and Fe are severe. These
interferences are greatly reduced in the nitrous oxide flame and by making
the samples and standards 1,000 mg/L in aluminum.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Mo hollow cathode lamp

Parameters Wavelength: 313.3 nm
Type of flame: nitrous oxide/acetylene
Background correction: recommended

C-143
Apparatus, Materials See sections 2.1.5 and 2.1.6 of this manual.
and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WEF, 18th edition, 1992, Method 3111 B/D.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-144
 Metals
Revision Date: December 31, 2000

Molybdenum (Atomic Absorption - Graphite Furnace)

Parameter Molybdenum, total
Molybdenum, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: GFAA (total) Mo-T X072

LA: HNO3: GFAA (total) Mo-T X179
FF, FA: HNO3: GFAA (dissolved) Mo-D X116
LF, LA: HNO3: GFAA (dissolved) Mo-D X357

Introduction Molybdenum is found in the soil and is an important trace element for the
growth of grasses and vegetables. Its uses include pigments for printing,
inks, alloying agent in steels and cast iron, high temperature alloys, tool
steels, catalysts, solid lubricants, and special batteries.

Method Summary A discrete sample volume is introduced into the graphite sample boat which
is heated in stages to accommodate drying of the solution, charring and
volatilization of organics and other matrix components, and finally,
atomization of the analyte into the light path of the spectrometer. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.001 mg/L
Range: 0.001 - 0.06 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences See section 2.1.4 of the AA methods section of this manual.

and Precautions

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Mo hollow cathode lamp.

Parameters Wavelength: 313.3 nm

Background correction: recommended

Apparatus, Materials See sections 2.1.5 and 2.1.6 of this manual.

and Reagents

C-145
Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WEF, 18th edition, 1992, Method 3111 B/D.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-146
 Metals
Revision Date: December 31, 2000

Nickel (Atomic Absorption - Direct Aspiration)

Parameter Nickel, total
Nickel, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) Ni-T X073

LA: HNO3: AA (total) Ni-T X351
FF, FA: HNO3: AA (dissolved) Ni-D X203
LF, LA: HNO3: AA (dissolved) Ni-D X085

Introduction Nickel’s principal ores are of two types; sulfide and oxide. Its uses include
electroplated protective coatings, alloys (low-alloy steels, stainless steel,
copper and brass, permanent magnets, electrical resistance alloys),
electroformed coatings, alkaline storage batteries, fuel cell electrodes, and
as a catalyst.

Method Summary Aqueous solutions of metals are aspirated into a flame and atomized. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.04 mg/L
Range: 0.04-5.0 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. High
concentrations of iron, cobalt, or chromium may interfere, requiring either
matrix matching or use of a nitrousoxide-acetylene flame.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Ni hollow cathode lamp

Parameters Wavelength: 232.0 nm (primary); 352.4 nm (alternate)
Type of Flame: air/acetylene
Background Correction: recommended

Apparatus, Materials See sections 2.1.5 and 2.1.6 of this manual.

and Reagents

C-147
Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater

APHA, AWWA, WEF, 18th edition, 1992, Method 3111 B/D.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-148
 Metals
Revision Date: December 31, 2000

Nickel (Atomic Absorption - Graphite Furnace)

Parameter Nickel, total
Nickel, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: GFAA (total) Ni-T X072

LA: HNO3: GFAA (total) Ni-T X179
FF, FA: HNO3: GFAA (dissolved) Ni-D X116
LF, LA: HNO3: GFAA (dissolved) Ni-D X357

Introduction Nickel’s principle ores are of two types: sulfide and oxide. Its uses include
electroplated protective coatings, alloys (low-alloy steels, stainless steel,
copper and brass, permanent magnets, electrical resistance alloys),
electroformed coatings, alkaline storage batteries, fuel cell electrodes and as
a catalyst.

Method Summary A discrete sample volume is introduced into the graphite sample boat which
is heated in stages to accommodate drying of the solution, charring and
volatilization of organics and other matrix components, and finally,
atomization of the analyte into the light path of the spectrometer. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.001 mg/L
Range: 0.001-0.100 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences See section 2.1.4 of the AA methods section of this manual.

and Precautions

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Ni hollow cathode lamp

Parameters Wavelength: 232.0 nm
Background Correction: recommended

Apparatus, Materials See section 2.1.5 and 2.1.6 of this manual.

and Reagents

C-149
Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Method for the Examination of Water and Wastewater APHA,
AWWA, WEF, 18th edition, 1992, Method 3113B.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-150
 Metals
Revision Date: December 31, 2000

Potassium (Atomic Absorption - Direct Aspiration)

Parameter Potassium, total
Potassium, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) K-TX073

LA: HNO3: AA (total) K-TX351
FF, FA: HNO3: AA (dissolved) K-DX203
LF, LA: HNO3: AA (dissolved) K-DX085

Method Summary Aqueous solutions of metals are aspirated into a flame and atomized. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.01 mg/L
Range: 0.01-2.0 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. Ionization
should be controlled by the addition of lanthanum chloride to a level of 0.1%.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: K hollow cathode lamp

Parameters Wavelength: 766.5 nm (primary); 404.4 nm (alternate)
Type of Flame: air/acetylene
Background Correction: recommended

Apparatus, Materials See sections 2.1.5 and 2.1.6 of this manual.

and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

C-151
References a) Standard Methods for the Examination of Water and Wastewater
APHA, AWWA, WEF, 18th edition, 1992, Method 3111 B/D.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added. Sample matrix added.

C-152
 Metals
Revision Date: December 31, 2000

Selenium (Atomic Absorption - Direct Aspiration)

Parameter Selenium, total
Selenium, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) Se-TX073

LA: HNO3: AA (total) Se-TX351
FF, FA: HNO3: AA (dissolved) Se-DX203
LF, LA: HNO3: AA (dissolved) Se-DX085

Introduction The toxicity of selenium is similar to that of arsenic. It has also been cited as
a potential carcinogen. The presence of selenium in water usually indicates
industrial pollution.

Method Summary Aqueous solutions of metals are aspirated into a flame and atomized. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.20 mg/L
Range: 0.20-20 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. The air-
acetylene flame absorbs or scatters more than 50% of the radiation from the
light source at the 196.0 nm selenium line. Due to this effect, a background
corrector should be used to improve the signal-to-noise ratio. Flame
absorption is reduced with the use of the nitrous oxide-acetylene flame,
although sensitivity is reduced.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Se EDL or hollow cathode lamp

Parameters Wavelength: 196.0 nm
Type of Flame: air/acetylene
Background Correction: recommended

C-153
Apparatus, Materials See section 2.1.5 and 2.1.6 of this manual.
and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 18th edition, 1992.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added. Sample matrix added.

C-154
 Metals
Revision Date: December 31, 2000

Selenium (Atomic Absorption - Graphite Furnace)

Parameter Selenium, total
Selenium, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: GFAA (total) Se-T X072

LA: HNO3: GFAA (total) Se-T X179
FF, FA: HNO3: GFAA (dissolved) Se-D X116
LF, LA: HNO3: GFAA (dissolved) Se-D X357

Introduction The toxicity of selenium is similar to that of arsenic. It has also been cited as
a potential carcinogen. The presence of selenium in water usually indicates
industrial pollution.

Method Summary A discrete sample volume is introduced into the graphite sample boat which
is heated in stages to accommodate drying of the solution, charring and
volatilization of organics and other matrix components, and finally,
atomization of the analyte into the light path of the spectrometer. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.002 mg/L
Range: 0.002-0.100 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. Elemental
selenium and many of its compounds are volatile; therefore, samples may be
subject to losses of selenium during sample preparation. Spike samples and
relevant standard reference materials should be processed to determine if
the chosen dissolution method is appropriate. Likewise, caution must be
employed during the selection of temperatures and times for the dry and char
(ash) cycles. A nickel nitrate solution must be added to all digestates prior to
analysis to minimize volatilization losses during drying and ashing.

In addition to the normal interferences experienced during graphite furnace

analysis, selenium analysis can suffer from severe nonspecific absorption
and light scattering caused by matrix components during atomization.
Selenium analysis is particularly susceptible to these problems because of its
low analytical wavelength (196.0 nm). Simultaneous background correction
is required to avoid erroneously high results. High iron levels can give
overcorrection with deuterium background. Zeeman background correction
can be useful in this situation. If the analyte is not completely volatilized and

C-155
 removed from the furnace during atomization, memory effects will occur. If
this situation is detected, the tube should be cleaned by operating the
furnace at full power at regular intervals in the analytical scheme. Selenium
analysis suffers interference from chlorides (>800 mg/L) and sulfate (>200
mg/L). The addition of nickel nitrate, such that the final concentration is 1%
nickel, will lessen this interference.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Se EDL or hollow cathode lamp

Parameters Wavelength: 196.0 nm
Background Correction: recommended

Apparatus, Materials See section 2.1.5 and 2.1.6 of this manual.

and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 18th edition 1992.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-156
 Metals
Revision Date: December 31, 2000

Selenium (Atomic Absorption - Gaseous Hydride)

Parameter Selenium, total
Selenium, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section, and section 2.2 the hydride AA
method section.

EMS Code FA: HNO3: HVAAS (total) Se-T X289

LA: HNO3: HVAAS (total) Se-T X354
FA: HCl: HVAAS (total) Se-T X345
LA: HCl: HVAAS (total) Se-T X355
FF, FA: HNO3: HVAAS (dissolved) Se-D X202
LF, LA: HNO3: HVAAS (dissolved) Se-D X359
FF, FA: HCl: HVAAS (dissolved) Se-D X348
LF, LA: HCl: HVAAS (dissolved) Se-D X360

Introduction The toxicity of selenium is similar to that of arsenic. It has also been cited as
a potential carcinogen. The presence of selenium in water usually indicates
industrial pollution.

Method Summary Selenium is converted to a gaseous hydride and analyzed by atomization in

a heated quartz tube. Conversion to hydride allows selenium to be detected
with greater sensitivity.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.0005 mg/L
Range: 0.0005-0.020 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences
and Precautions See section 2.2, the hydride AA methods section of this manual. High
concentrations of chromium, cobalt, copper, mercury, molybdenum, nickel,
and silver can cause analytical interferences. Traces of nitric acid left
following the sample work-up can result in analytical interferences.
Elemental selenium and many of its compounds are volatile; therefore,
certain samples may be subject to losses of selenium during sample
preparation.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

C-157
Instrument Source: Se EDL or hollow cathode lamp
Parameters Wavelength: 196.0 nm
Background Correction: not required

Apparatus, Materials See section 2.2, the hydride AA methods section in this manual.
and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 18th edition, 1992.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-158
 Metals
Revision Date: December 31, 2000

Selenium (Atomic Emission - Inductively Coupled Argon Plasma

{ICAP})
Parameter Selenium, total
Selenium, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.4, the ICP-AES method section.

EMS Code FA: HNO3: ICAP (total) Se-T X349

LA: HNO3: ICAP (total) Se-T X352
FF, FA: HNO3: ICAP (dissolved) Se-D X350
LF, LA: HNO3: ICAP (dissolved) Se-D X356

Introduction The toxicity of selenium is similar to that of arsenic. It has also been cited as
a potential carcinogen. The presence of selenium in water usually indicates
industrial pollution.

Method Summary Aqueous solutions of metals are converted to aerosols in the nebulizer of the
ICP and injected directly into a high temperature plasma (6000 to 8000°K).
This highly efficient ionization produces ionic emission spectra and
wavelengths specific to the elements of interest can be monitored either
simultaneously or sequentially.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.050 mg/L
Range: 0.05-1000 mg/L
See Table C-2 in section 2.4, the ICP-AES method section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences See section 2.4, the ICP-AES section of this manual.

and Precautions

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Wavelength: 196.0 nm (primary)

Parameters Background Correction: recommended

Apparatus, Materials See section 2.4, of the ICP-AES methods section in this manual.
and Reagents

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Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 18th edition, 1992.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-160
 Metals
Revision Date: December 31, 2000

Silver (Atomic Absorption - Direct Aspiration)

Parameter Silver, total
Silver, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) Ag-T X073

LA: HNO3: AA (total) Ag-T X351
FF, FA: HNO3: AA (dissolved) Ag-D X203
LF, LA: HNO3: AA (dissolved) Ag-D X085

Introduction Uses of silver include photographic chemicals, lining vats and other
equipment for chemical reaction vessels, water distillation, mirrors, electric
conductors, sterilants, water purification, special batteries, solar cells, table
cutlery, jewellery and dental amalgams.

Method Summary Aqueous solutions of metals are aspirated into a flame and atomized. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.01 mg/L
Range: 0.01 - 4 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. Background
correction is required because nonspecific absorption and light scattering
may occur at the analytical wavelength.

Silver nitrate solutions are light-sensitive and have a tendency to plate out on
container walls. Therefore silver standards should be stored in brown
bottles. Dilutions of the stock/standard should be discarded after use, as
concentrations below 10 mg/L are not stable over a long period of time.

Silver chloride is insoluble; therefore, hydrochloric acid should be avoided

unless the silver is already in solution as a chloride complex.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

C-161
Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Silver nitrate (AgNO3) is light sensitive and known to plate out on container
walls. Therefore, minimize the sample exposure to light or store the samples
in brown bottles.

Instrument Source: Ag hollow cathode lamp

Parameters Wavelength: 328.1 nm
Type of Flame: air/acetylene
Background Correction: recommended

Apparatus, Materials See section 2.1.5 and 2.1.6 of this manual.

and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Methods for Chemical Analysis of Water and Wastes, EPA-600/4-

82-055, December 1982, Method 272.1.
b) Standard Methods for the Examination of Water and Wastewater,
APHA, AWWA, WPCF, 18th edition, 1992.
c) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

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 Metals
Revision Date: December 31, 2000

Silver (Atomic Absorption - Graphite Furnace)

Parameter Silver, total
Silver, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: GFAA (total) Ag-T X072

LA: HNO3: GFAA (total) Ag-T X179
FF, FA: HNO3: GFAA (dissolved) Ag-D X116
LF, LA: HNO3: GFAA (dissolved) Ag-D X357

Introduction Uses of silver include photographic chemicals, lining vats and other
equipment for chemical reaction vessels, water distillation, mirrors, electric
conductors, sterilants, water purification, special batteries, solar cells, table
cutlery, jewellery and dental amalgams.

Method Summary A discrete sample volume is introduced into the graphite sample boat which
is heated in stages to accommodate drying of the solution, charring and
volatilization of organics and other matrix components, and finally,
atomization of the analyte into the light path of the spectrometer. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.0002 mg/L
Range: 0.0002-0.005 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. Background
correction is required because nonspecific absorption and light scattering
may occur at the analytical wavelength.

Silver nitrate solutions are light-sensitive and have a tendency to plate out on
container walls. Therefore silver standards should be stored in brown
bottles. Dilutions of the stock/standard should be discarded after use, as
concentrations below 10 mg/L are not stable over a long period of time.

Silver chloride is insoluble; therefore, hydrochloric acid should be avoided

unless the silver is already in solution as a chloride complex.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

C-163
Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Silver nitrate (AgNO3) is light sensitive and known to plate out on container
walls. Therefore, minimize the sample exposure to light or store the samples
in brown bottles.

Instrument Source: Ag hollow cathode lamp

Parameters Wavelength: 328.1 nm
Background Correction: recommended

Apparatus, Materials See section 2.1.5 and 2.1.6 of this manual.

and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WEF, 18th edition, 1992, Method 3113B.
b) Methods for Chemical Analysis of Water and Wastes, EPA-600/4-
82-055,December 1982, Method 272.2.
c) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-164
 Metals
Revision Date: December 31, 2000

Sodium (Atomic Absorption - Direct Aspiration)

Parameter Sodium, total
Sodium, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) Na-T X073

LA: HNO3: AA (total) Na-T X351
FF, FA: HNO3: AA (dissolved) Na-D X203
LF, LA: HNO3: AA (dissolved) Na-D X085

Method Summary Aqueous solutions of metals are aspirated into a flame and atomized. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.002 mg/L
Range: 0.002-1.0 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4 of the AA methods section of this manual. Ionization
should be controlled by the addition of potassium chloride to a level of 0.1%.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Na hollow cathode lamp

Parameters Wavelength: 589.0 nm (primary); 330.2 nm (alternate)
Type of Flame: air/acetylene
Background Correction: recommended

Apparatus, Materials See sections 2.1.5 and 2.1.6 of this manual.

and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

C-165
References a) Standard Methods for the Examination of Water and Wastewater
APHA, AWWA, WEF, 18th edition, 1992, Method 3111 B/D.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-166
 Metals
Revision Date: December 31, 2000

Tin (Atomic Absorption - Direct Aspiration)

Parameter Tin, total
Tin, dissolved

Sample Preparation See section 1.0, the Sample Preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) Sn-T X073

LA: HNO3: AA (total) Sn-T X351
FF, FA: HNO3: AA (dissolved) Sn-D X203
LF, LA: HNO3: AA (dissolved) Sn-D X085

Introduction Tin is usually present in trace levels in natural waters. The pure metal is
relatively non-toxic; however some organo-tin complexes (i.e., tributyltin) are
known to be acutely toxic. Tributyltin is commonly used as an antifouling
agent for marine paints.

Method Summary Aqueous sample solutions and calibration standards are aspirated into a
flame and atomized. The absorption of light, at a wavelength specific to tin,
is measured and the concentration of the analyte is determined by
comparison to the calibration standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.5 mg/L
Range: 0.5 mg/L - 300 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences See section 2.1.4 of the AAS methods section of this manual.
and Precautions

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Sn EDL or hollow cathode lamp

Parameters Wavelength: 286.3 nm
Type of Flame: Nitrous oxide/Acetylene
Background Correction: recommended

Apparatus, Material See section 2.1.5 and 2.1.6 of this manual.

and Reagents

Precision None listed.

Accuracy None listed.

C-167
Quality Control See Section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WPCF, 18th edition, 1992.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd edition 1990.
c) Analytical Methods For Atomic Absorption Spectrophotometry.
Published by The Perkin-Elmer Corporation. Norwalk, Connecticut,
U.S.A. January 1982.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-168
 Metals
Revision Date: December 31, 2000

Tin (Atomic Absorption - Gaseous Hydride)

Parameter Tin, total
Tin, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section and 2.2, the hydride AA method
section of this manual.

EMS Code FA: HNO3: HVAAS (total) Sn-T X289

LA: HNO3: HVAAS (total) Sn-T X354
FA: HCl: HVAAS (total) Sn-T X345
LA: HCl: HVAAS (total) Sn-T X355
FF, FA: HNO3: HVAAS (dissolved) Sn-D X202
LF, LA: HNO3: HVAAS (dissolved) Sn-D X359
FF, FA: HCl: HVAAS (dissolved) Sn-D X348
LF, LA: HCl: HVAAS (dissolved) Sn-D X360

Introduction Tin is usually present in trace levels in natural waters. The pure metal is
relatively non-toxic; however some organo-tin complexes (i.e., tributyltin) are
known to be acutely toxic. Tributyltin is commonly used as an antifouling
agent for marine paints.

Method Summary Hydride vapour generation sample introduction systems utilize a chemical
reduction to reduce and form a volatile hydride with tin. This volatile hydride
is then swept into a heated quartz cell where the tin is freed from the hydride.
Standard AAS (heated reaction cell) is then carried out on the volatile
metallic species.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.0005 mg/L
Range: 0.0005 - 0.200 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences • easily reduced metals - i.e., copper, silver, mercury, etc.,

and Precautions • high concentrations of transition metals (>200 mg/L), and
• oxidizing agents remaining following sample digestion - i.e., oxides of
nitrogen. (USEPA, 1986)

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

C-169
Instrument Source: Sn EDL or hollow cathode lamp
Parameters Wavelength: 286.3 nm
Background Correction: not required

Apparatus, Material See section 2.1.5 and 2.1.6 of this manual.

and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See Section 2.1.9, QA/QC Guidelines in this manual.

References a) Instructions - MHS-20 Mercury/Hydride System, Publication 338-A2-M

294/12.79. Bodenseewerk Perkin-Elmer & Co. GMBH/UBERLINGEN.
1979.
b) Analytical Methods For Atomic Absorption Spectrophotometry.
Published by the Perkin-Elmer Corporation. Norwalk, Connecticut,
U.S.A. January 1982.
c) Standard Methods for the Examination of Water and Wastewater,
APHA, AWWA, WPCF, 18th edition, 1992.
d) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-170
 Metals
Revision Date: December 31, 2000

Uranium, Total or Dissolved

Parameter Uranium, total
Uranium, dissolved

Analytical Method Laser-induced fluorescence

HNO3 digestion, laser-induced fluorescence

EMS Code a) Dissolved U--D X343

b) Total U--T X344

Introduction Most sources of drinking water, especially groundwaters, contain dissolved

carbonates and bicarbonates that are capable of complexing with uranium
and keeping it in solution.

Method Summary Uranyl ion (UO22+), complexed with pyrophosphate, is excited at 337 nm
with a pulsed nitrogen laser and the resulting fluorescence at 494, 516 or
540 nm is monitored. The method of standard additions is used to minimize
interferences from matrix effects.

MDL Typical: 0.0002 mg/L for uranium, total

0.0001 mg/L for uranium, dissolved

Matrix Fresh water

Interferences and
Precautions Many of the common cations (Ca, Na, K etc.) interfere at normal
concentration levels; however, the interference is minimized by the standard
addition technique. Interference from fluorescing organic material is avoided
by instituting a delay in measurement to allow the short-lived organic
fluorescence to subside.

Sample Handling Plastic or glass bottle, sample acidified in the field with 4mL
and Preservation concentrated HNO3/L

Stability M. H. T.: 14 days

Principle or
Procedure The uranyl ion, when excited at 337 nm, releases energy at 494, 516 and
540 nm. The Scintrex® laser fluorescence analyzer provides a convenient
means of analysis.

Precision Authentic samples at concentrations of 3.9 and 30.4 µg/L gave coefficients of
variation of 5.5% and 4.0% respectively.

Accuracy ±3% at 30 µg/L level

Quality Control The laser intensity (without a cuvette installed) should be recorded each time
a set of analyses is run to monitor laser performance. The slope of the
standard addition plot for the sample should be within 20% of the slope
attained for the standards and blanks; failure indicates excessive
interference and necessitates re-analysis after dilution of the sample.

C-171
References None listed.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Out of
print reference deleted. Sample matrix added.

C-172
 Metals
Revision Date: December 31, 2000

Zinc (Atomic Absorption - Direct Aspiration)

Parameter Zinc, total
Zinc, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: AA (total) Zn-T X073

LA: HNO3: AA (total) Zn-T X351
FF, FA, HNO3: AA (dissolved) Zn-D X203
LF, LA: HNO3: AA (dissolved) Zn-D X085

Introduction Zinc is an essential trace element for human growth. It imparts a bitter taste
to drinking water at concentrations above 5 mg/L. Zinc occurs in nature as
the sulfide and is often associated with sulfides of other heavy metals.
Common sources of zinc are contaminated industrial waste and deteriorated
galvanized steel. It is toxic to aquatic life at a relatively low concentration,
depending on water hardness.

Method Summary Aqueous solutions of metals are aspirated into a flame and atomized. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.005 mg/L
Range: 0.005-1.0 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions No significant interferences. Possible enhancement or depression of
absorbance signal for samples containing high levels of dissolved solids.
Use deuterium background correction if warranted. See also section 2.1.4 of
the AA methods section of this manual.

Sample Handling See section 1.0, the sample preparation section.

and Preservation

Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Zn hollow cathode lamp

Parameters Wavelength: 213.9 nm
Type of Flame: air/acetylene
Background Correction: recommended

C-173
Apparatus, Materials See section 2.1.5 and 2.1.6 of this manual.
and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WEF, 18th edition, 1992, Method 3111 B/D.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-174
 Metals
Revision Date: December 31, 2000

Zinc (Atomic Absorption - Graphite Furnace)

Parameter Zinc, total
Zinc, dissolved

Sample Preparation See section 1.0, the sample preparation section.

Analytical Method See section 2.1, the AA methods section.

EMS Code FA: HNO3: GFAA (total) Zn-T X072

LA: HNO3: GFAA (total) Zn-T X179
FF, FA: HNO3: GFAA (dissolved) Zn-D X116
LF, LA: HNO3: GFAA (dissolved) Zn-D X357

Introduction Zinc is an essential trace element for human growth. It imparts a bitter taste
to drinking water at concentrations above 5 mg/L. Zinc occurs in nature as
the sulfide and is often associated with sulfides of other heavy metals.
Common sources of zinc are contaminated industrial waste and deteriorated
galvanized steel. It is toxic to aquatic life at a relatively low concentration,
depending on water hardness.

Method Summary A discrete sample volume is introduced into the graphite sample boat which
is heated in stages to accommodate drying of the solution, charring and
volatilization of organics and other matrix components, and finally,
atomization of the analyte into the light path of the spectrometer. The
absorption of light, at a wavelength specific to the element being analyzed, is
measured and the concentration of the analyte is determined by comparison
with standards.

MDL Given an aqueous sample free of interferences, the instrumental

performance characteristics are:
MDL: 0.0002 mg/L
Range: 0.0002-0.004 mg/L
See Table C-1 in section 2.1, the AA methods section, for additional
information.

Matrix Water, wastewater, marine water.

Interferences and
Precautions See section 2.1.4, of the AA methods section of this manual. Due to the
extreme sensitivity of the method and presence of zinc as a trace
contaminant in dust, plastics, glassware, acids and other reagents, any
manipulation or treatment of samples must be duplicated in the form of
appropriate blanks to allow for correction of results. Platform atomization is
recommended for zinc analysis.

Sample Handling See section 1.0, the sample preparation section of this manual.
and Preservation

C-175
Stability An aqueous solution preserved with nitric acid to pH <2, has a hold time of 6
months.

Instrument Source: Zn hollow cathode lamp

Parameters Wavelength: 213.9 nm
Background Correction: recommended

Apparatus, Materials See section 2.1.5 and 2.1.6 of this manual.

and Reagents

Precision None listed.

Accuracy None listed.

Quality Control See section 2.1.9, QA/QC Guidelines in this manual.

References a) Standard Methods for the Examination of Water and Wastewater,

APHA, AWWA, WEF, 18th edition, 1992, Method 3113B.
b) Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods (Revised). Publication #SW-846 Revision 1. United States
Environmental Protection Agency, Washington, DC. 3rd Edition 1990.

Revision History February 14, 1994: Publication in 1994 Laboratory Manual.

December 31, 2000: SEAM codes replaced by EMS codes. Sample
matrix added.

C-176