By Authority Of

THE UNITED STATES OF AMERICA

Legally Binding Document
By the Authority Vested By Part 5 of the United States Code § 552(a) and
Part 1 of the Code of Regulations § 51 the attached document has been duly
INCORPORATED BY REFERENCE and shall be considered legally
binding upon all citizens and residents of the United States of America.
HEED THIS NOTICE: Criminal penalties may apply for noncompliance.

e
This Document Posted By Not Affiliated Or
Public.Resource.Org, Inc., Authorized by ASTM
a California Nonprofit or by the United States
Organization. Government

Document Name: ASTM D-3559 (2003): Standard Test Methods for

Lead in Water

CFR Section(s): 40 CFR 136.3(a)

Date of Action: 67 FR 69971, Nov. 19, 2002

Official Incorporator:
THE EXECUTIVE DIRECTOR
OFFICE OF THE FEDERAL REGISTER
WASHINGTON, D.C.
 -~- -------,-,-

''1
ASTM Logo Removed

Designation: D 3559 - 03

Standard Test Methods for

Lead in Water 1
This standard is issu~d under the fixed designation D 3559; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (E) indicates an editorial change since the last revision or reapproval.

This standard has been approved for use by agencies of the Department of Defense.

1. Scope * 1066 Practice for Sampling Steam3

D
1.1 These test methods cover the determination of dissolved D
1068 Test Methods for Iron in Wate2
and total recoverable lead in water and waste water by 1129 Terminology Relating to Water3
D
atomic-absorption spectrophotometry2 and differential pulse D
1192 Specification for Equipment for Sampling Water
anodic stripping voltammetry. Four test methods are included and Steam in Closed Conduits 3
as follows: D 1193 Specification for Reagent Water3
Concentration
D 1687 Test Methods for Chromium in Water3
Range Sections D 1688 Test Methods for Copper in Water3
Test Method A-Atomic Absorption, Direct 1.0 to 10 mg/L 7 to 15 D 1691 Test Methods for Zinc in Water3
D 1886 Test Methods for Nickel in Water3
Test Method B-Atomic Absorption, 100 to 1000 ]1g/L 16 to 24
Chelation-Extraction
Test Method C-Differential Pulse Anodic 1 to 100 ]1g/L 25 to 35 D 2777 Practice for Determination of Precision and Bias of
Stripping Voltammetry Applicable Methods of Committee D-19 on Water3
Test Method D-Atomic Absorption, 5 to 100 ]1g/L 36 to 44
Graphite Furnace D 3370 Practices for Sampling Water from Closed Con-
duits 3
1.2 Test Method B can be used to determine lead in brines. D 3557 Test Methods for Cadmium in Water3
Test Method D has been used successfully with reagent water, D 3558 Test Methods for Cobalt in Wate2
lake water, well water, filtered tap water, condensate from a D 3919 Practice for Measuring Trace Elements in Water by
medium Btu coal gasification process, waste treatment plant Graphite Furnace Atomic Absorption Spectrophotometry3
effluent, and a production plant process water. D 4841 Practice for Estimation of Holding Time for Water
1.3 It is the user's responsibility to ensure the validity of Samples Containing Organic and Inorganic Constituents 3
these test methods for waters of untested matrices. D 5810 Guide for Spiking into Aqueous Samples 3
1.4 T,his
T.his standard does not purport to address all of the D 5847 Practice for the Writing Quality Control Specifica-
safety concerns, if any, associated with its use. It is the tions for Standard Test Methods for Water Analysis 3
responsibility of the user of this standard to establish appro- E 60 Practice for Photometric and Spectrophotometric
priate s(ifety and health practices and determine the applica- Methods for Chemical Analysis of Metals 4
bility o/regulatory limitations prior to use. For specific hazards E 275 Practice for Describing and Measuring Performance
stateme~ts, see 10.4.1, Note 2, 11.2, 11.3, 21.7, 21.8, 21.11, of Ultraviolet, Visible, and Near Infrared Spectrophotom-
23.7, 2l10, 32.2.1, and 33.1. eters5
2. Referenced Documents 3. Terminology
2.1 ASTM Standards: 3.1 Definitions-For definition of terms used in these test
D 858 Test Methods for Manganese in Water3 methods, refer to Terminology D 1129.
3.2 total recoverable lead-an arbitrary analytical term
relating to the recoverable forms of lead that are determined by
I These test methods are under the jurisdiction of ASTM Committee DI9 on the digestion method which are included in the procedure.
Water and are the direct responsibility of Subcommittee D19.05 on Inorganic
Constituents in Water. 4. Significance and Use
Current edition approved Jan. 10, lO, 2003. Published January 2003. Originally
approved in 1977. Last previous edition approved in 1996 as D 3559 - 96. 4.1 The test for lead is necessary because it is a toxicant and
2 Platte, J. A., and Marcy, V. M., "A New Tool for the Water Chemist," Industrial because there is a limit specified for lead in potable water in the
Water Engineering, May 1965. National Interim Primary Drinking Water Regulations. This
Brown, E., Skougstad, M. W., and Fishman, M. J., "Methods for Collection and
Analysis of Water Samples for Dissolved Minerals and Gases," Techniques of
Water-Resources Investigations of the U. S. Geological Survey, Book 5, Chapter,
1970, p. 115. 4 Annual Book of ASTM Standards, Vol 03.05.
3 Annual Book of ASTM Standards, Vol 11.01. S Annual Book of ASTM Standards, Vol 03.06.

*A Summary of Changes section appears at the end of this standard.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

Copyright ASTM International

Provided by IHS under license with ASTM Sold lo:PUBLlC.RESOURCE.ORG, W1218734
No reproduclion or networking permilted without license from IHS 2012/1/1021:52:47 GMT
 ASTM Logo Removed

559-03
test serves to determine whether the lead content of potable 9. Interferences
water is above or below the acceptable limit. 9.1 Other metals usually do not interfere in the determina-
tion of lead by increasing or decreasing the amount of absorbed
5. Purity of Reagents radiation. The most common interference is caused by a
5.1 Reagent grade chemicals shall be used in all tests. chemical reaction in the flame that prevents conversion of the
Unless otherwise indicated, it is intended that all reagents shall lead to the atomic state.
conform to the specifications of the Committee on Analytical 9.2 High concentrations of calcium, such as those connected
Reagents of the American Chemical Society. 6 Other grades with the coal industry, will give lead concentrations higher than
may be used, provided it is first ascertained that the reagent is which actually exist. This can be corrected by using a back-
of sufficiently high purity to permit its use without lessening ground correction technique, or by the chelation-extraction
the accuracy of the determination. procedure (Test Method B).
5.2 Unless otherwise indicated, references to water shall be 9.2.1 The equipment manufacturer's instructions for use of
understood to mean reagent water conforming to Specification specific correction technique shall be followed.
D 1193, Type I. Other reagent water types may be used
provided it is first ascertained that the water is of sufficiently 10. Apparatus
high purity to permit its use without adversely affecting the
10.1 Atomic Absorption Spectrophotometer, for use at 283.3
bias and precision of the test method. Type II water was
nm.
specified at the time of round-robin testing of this test method.
NOTE I-The manufacturer's instructions shall be followed for all
6. Sampling instrumental parameters. Wavelengths other than 283.3 nm may be used if
they have been determined to be equally suitable.
6.1 Collect the samples in accordance with Practice D 1066,
Specification D 1192, and Practices D 3370, as applicable. 10.2 Lead Light Source, hollow-cathode lamps or
6.2 Samples shall be preserved with HN0 3 (sp gr 1.42) to a electrodeless-discharge lamps have been found satisfactory.
pH of 2 or less immediately at the time of collection, normally 10.3 Oxidant:
about 2 mL/L of HN0 3 . If only dissolved lead is to be 10.3.1 Air, which has been passed through a suitable filter to
determined, the sample shall be filtered through a 0.45-J.lm remove oil, water, and other foreign substances, is the usual
membrane filter before acidification. oxidant.
10.4 Fuel:
TEST METHOD A-ATOMIC ABSORPTION, 10.4.1 Acetylene-Standard, commercially available acety-
DIRECT lene is the usual fuel. Acetone, always present in acetylene
cylinders, can affect analytical results. The cylinder should be
7. Scope replaced at 50 psig (345 kPa).
7.1 This test method covers the determination of dissolved 10.4.1.1 Warning-"Purified" grade acetylene containing a
and total recoverable lead in most waters and wastewaters. special proprietary solvent rather than acetone should not be
7.2 The test method is applicable in the range from 1.0 to 10 used with poly(vinyl chloride) tubing as weakening of the
mg/L of lead. The upper limits of detectability can be increased walls can cause a potential hazardous situation.
to concentrations greater than 10 mg/L by dilution of the 10.5 Pressure-Reducing Valves-The supplies of fuel and
sample. oxidant shall be maintained at pressures somewhat higher than
the controlled operating pressure of the instrument by suitable
8. Summary of Test Method valves.
8.1 Lead is determined by atomic absorption spectropho-
tometry. Dissolved lead is determined by aspirating the filtered 11. Reagents
and preserved sample directly with no pretreatment. Total 11.1 Hydrochloric Acid (sp gr 1.19)-Concentrated hydro-
recoverable lead is determined by aspirating the sample fol- chloric acid (HCI).
lowing hydrochloric-nitric acid digestion and filtration. The
NOTE 2-If the reagent blank concentration is greater than the method
same digestion procedure may be used to determine total detection limit, distill the Hel or use a spectrograde acid. Caution-When
recoverable cadmium (Test Methods D 3557), chromium (Test Hel is distilled, an azeotropic mixture is formed (approximately 6 N Hel
Methods D 1687), cobalt (Test Methods D 3558), copper (Test is formed). Therefore, whenever concentrated Hel is used in the prepa-
Methods D 1688), iron (Test Methods D 1068), manganese ration of a reagent or in the procedure, use double the volume specified if
(Test Methods D 858), nickel (Test Methods D 1886), and zinc distilled Hel is used.
(Test Methods D 1691). 11.2 Lead Solution, Stock (I mL = 1 mg lead)-Dissolve
1.5999 g of lead nitrate (Pb (N0 3 h) in a mixture of 10 mL of
HN0 3 (sp gr 1.42) and 100 mL of water. Dilute to 1 L with
6 Reagent Chemicals, American Chemical Society Specifications, American water. Warning-Lead salts are toxic. Handle with care and
Chemical Society, Washington, DC. For suggestions on the testing of reagents not avoid personal contamination.
listed by the American Chemical Society, see Analar Standards for Laborato/y
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
11.3 Lead Solution, Standard (1 mL =0.1 mg lead)-Dilute
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, 100.0 mL of stock lead solution to 1 L with HN0 3 (1 + 499).
MD. Store all solutions in polyethylene bottles. Warning-Lead

Copyright ASTM International 2

Provided by IHS under license wilh ASTM Sold to:PUBLIC.RESOURCE.ORG. W121B734
No reproducllon or networking permitted without license from IHS 201211110 21 :52:47 GMT
 ASTM Logo Removed

03559-03
salts are toxic. Never pipet by mouth. Pipet with the end of a TABLE 1 Determination of Bias, Direct
suction device or employ other conventional means of quanti- Amount Amount
Statistically
tative measurement. Added, Found,
Sr, So,
Bias,%
Significant
mg/L mg/L (95 % Confi-
mg/L mg/L
11.4 Nitric Acid (sp gr 1.42)-Concentrated nitric acid dence Level)
(HN0 3 )· Reagent Water, Type II
1 1.01 0.08 0.04 +1.00 no
NOTE 3-If the reagent blank concentration is greater than the method 6 6.01 0.28 0.14 +0.17 no
detection limit, distill the RN03 or use a trace metal grade acid. 8 8.02 0.34 0.14 +0.25 no
Selected Water Matrices
11.5 Nitric Acid (1 + 499)-Add 1 volume of HN0 3 (sp gr
1.42) to 499 volumes of water. 1 1.00 0.00 0.06 0.00 no
6 6.11 0.25 0.16 +1.83 yes
8 7.99 0.36 0.23 -0.13 no
12. Standardization
12.1 Prepare 100 mL each of a blank and at least four
standard solutions to bracket the expected lead concentration 15. Precision and Bias 7
range to be analyzed by diluting the lead standard solution
(11.3) with HN0 3 (1 + 499). Prepare the standards each time
15.1 Fourteen operators from nine laboratories participated
in this study. One operator performed the analysis in quadru-
the test is to be performed.
plicate, twelve in triplicate and one in duplicate at each
12.2 When determining total recoverable lead, add 0.5 mL concentration level.
of HN0 3 (sp gr 1.42) to each blank and standard solution and 15.2 The bias of this test method for lead is listed in Table
proceed as directed in 13.2 through 13.4. After the digestion of 1.
the blank and standard solutions has been completed in 13.4, 15.3 These data may not apply to waters of other matrices.
return to 12.3 to complete the standardization for total recov- 15.4 This section on precision and bias conforms to Practice
erable determinations. When determining dissolved lead, pro- D 2777 - 77 which was in place at the time of collaborative
ceed with 12.3. testing. Under the allowances made in 1.4 of D 2777 - 98,
12.3 Aspirate the blank and standards and record the instru- these precision and bias data do meet existing requirements of
ment readings. Aspirate HN0 3 (1 + 499) between standards. interlaboratory studies of Committee D19 test methods.
12.4 Prepare an analytical curve by plotting the absorbance
versus the concentration for each standard on linear graph 16. Quality Control
paper. Alternatively, read directly in concentration if this 16.1 In order to be certain that analytical values obtained
capability is provided with an instrument. using these test methods are valid and accurate within the
confidence limits of the test, the following QC procedures must
13. Procedure be followed when analyzing lead.
13.1 Measure 100.0 rnL of a well-mixed acidified sample 16.2 Calibration and Calibration Verification:
into a 125-mL beaker or flask. 16.2.1 Analyze at least three working standards containing
concentrations of lead that bracket the expected sample con-
NOTE 4-If only dissolved lead is to be determined, start with 13.5. centration, prior to analysis of samples, to calibrate the
instrument. The calibration correlation coefficient shall be
13.2 Add 5 rnL of HCI (sp gr 1.19) to each sample.
equal to or greater than 0.990. In addition to the initial
13.3 Heat the samples on a steam bath or hot plate in a calibration blank, a calibration blank shall be analyzed at the
well-ventilated hood until the volume has been reduced to 15 eml of the batch run to ensure contamination was not a problem
to 20 rnL, making certain that the samples do not boil. during the batch analysis.
NOTE 5-For samples having appreciable amounts of suspended matter
16.2.2 Verify instrument calibration after standardization by
or dissolved matter, the amount of reduction in volume is left to the analyzing a standard at the concentration of one of the
discretion of the analyst. calibration standards. The concentration of a mid-range stan-
dard should fall within ± 15 % of the known concentration.
13.4 Cool and filter the samples through a suitable filter
16.2.3 If calibration cannot be verified, recalibrate the
such as fine-textured, acid washed, ashless paper, into 100-rnL
instrument.
volumetric flasks. Wash the filter paper two or three times with
16.3 Initial Demonstration of Laboratory Capability:
water and adjust to volume.
16.3.1 If a laboratory has not performed the test before, or if
13.5 Aspirate each filtered and acidified sample and deter- there has been a major change in the measurement system, for
mine its absorbance or concentration at 283.3 nm. Aspirate example, new analyst, new instrument, etc., a precision and
HN0 3 (1 + 499) between samples. bias study must be performed to demonstrate laboratory
capability.
14. Calculation
14.1 Calculate the concentration of lead in each sample, in
milligrams per litre, using the calibration curve established in 7 Supporting data are available from ASTM Headquarters. Request RR:D
12.4. 19-1030.
... " ... " .. " ........ - ........ , ...... .

Copyright ASTM International 3

Provided by IHS under license with ASTM Sold lo:PUBLlC.RESOURCE.ORG, W1218734
No reproduction or networking permitted without license from IHS 20121111021:52:47 GMT
 ASTM Logo
Removed
03559 .... 03
16.3.2 Analyze seven replicates of a standard solution A = analyte concentration (mg/L) in spiked sample,
prepared from an Independent Reference Material containing a B analyte concentration (mg/L) in unspiked sample,
mid-range concentration of lead. The matrix and chemistry of C concentration (mg/L) of analyte in spiking solution,
the solution should be equivalent to the solution used in the Vs = volume (mL) of sample used, and
collaborative study. Each replicate must be taken through the V = volume (mL) added with spike.
complete analytical test method including any sample preser- 16.6.4 The percent recovery of the spike shall fall within the
vation and pretreatment steps. The replicates may be inter- limits, based on the analyte concentration, listed in Guide
spersed with samples. D 5810, Table 1. If the percent recovery is not within these
16.3.3 Calculate the mean and standard deviation of the limits, a matrix interference may be present in the sample
seven values and compare to the acceptable ranges of bias in selected for spiking. Under these circumstances, one of the
Table 1. This study should be repeated until the recoveries are following remedies must be employed: the matrix interference
within the limits given in Table 1. If a concentration other than must be removed, all samples in the batch must be analyzed by
the recommended concentration is used, refer to Practice a test method not affected by the matrix interference, or the
D 5847 for information on applying the F test and t test in results must be qualified with an indication that they do not fall
evaluating the acceptability of the mean and standard devia- within the performance criteria of the test method.
tion. NOTE 6-Acceptable spike recoveries are dependent on the concentra-
16.4 Laboratory Control Sample (LCS): tion of the component of interest. See Guide D 5810 for additional
16.4.1 To ensure that the test method is in control, analyze information.
a LCS containing a known concentration of lead with each 16.7 Duplicate:
batch or 10 samples. If large numbers of samples are analyzed 16.7.1 To check the precision of sample analyses, analyze a
in the batch, analyze the LCS after every 10 samples. The sample in duplicate with each batch. If the concentration of the
laboratory control samples for a large batch should cover the analyte is less than five times the detection limit for the analyte,
analytical range when possible. The LCS must be taken a matrix spike duplicate (MSD) should be used.
through all of the steps of the analytical method including 16.7.2 Calculate the standard deviation of the duplicate
sample preservation and pretreatment. The result obtained for values and compare to the precision in the collaborative study
a mid-range LCS shall fall within ± 15 % of the known using an F test. Refer to 6.4.4 of Practice D 5847 for
concentration. information on applying the F test.
16.4.2 If the result is not within these limits, analysis of 16.7.3 If the result exceeds the precision limit, the batch
samples is halted until the problem is corrected, and either all must be reanalyzed or the results must be qualified with an
the samples in the batch must be reanalyzed, or the results must indication that they do not fall within the performance criteria
be qualified with an indication that they do not fall within the of the test method.
performance criteria of the test method. 16.8 Independent Reference Material (IRM):
16.5 Method Blank: 16.8.1 In order to verify the quantitative value produced by
16.5.1 Analyze a reagent water test blank with each batch. the test method, analyze an Independent Reference Material
The concentration of lead found in the blank should be less (IRM) submitted as a regular sample (if practical) to the
than 0.5 times the lowest calibration standard. If the concen- laboratory at least once per quarter. The concentration of the
tration of lead is found above this level, analysis of samples is IRM should be in the concentration mid-range for the method
halted until the contamination is eliminated, and a blank shows chosen. The value obtained must fall within the control limits
no contamination at or above this level, or the results must be established by the laboratory.
qualified with an indication that they do not fall within the
performance criteria of the test method. TEST METHOD B-ATOMIC ABSORPTION,
16.6 Matrix Spike (MS): CHELATION-EXTRACTION
16.6.1 To check for interferences in the specific matrix
being tested, perform a MS on at least one sample from each 17. Scope
batch by spiking an aliquot of the sample with a known 17.1 This test method covers the determination of dissolved
concentration of lead and taking it through the analytical and total recoverable lead in most waters and brines.
method. 17.2 This test method is applicable in the range from 100 to
16.6.2 The spike concentration plus the background concen- 1000!! gIL of lead. The range may be extended upward by
tration of lead must not exceed the high calibration standard. dilution of the samples.
The spike must produce a concentration in the spiked sample
that is 2 to 5 times the analyte concentration in the unspiked 18. Summary of Test Method
sample, or 10 to 50 times the detection limit of the test method,
18.1 Lead is determined by atomic absorption spectropho-
whichever is greater.
tometry. The element, either dissolved or total recoverable, is
16.6.3 Calculate the percent recovery of the spike (P) using
chelated with pyrrolidine dithiocarbamic acid and extracted
the following formula:
with chloroform. The extract is evaporated to dryness, treated
P = 100 [AW,· + V) - B v:,] / C V (1) with hot HCl and diluted to a specified volume with water. The
resulting solution is then aspirated into the air-acetylene flame
where:
of the spectrophotometer. The digestion procedure summarized

Copyright ASTM International 4

Provided by IHS under license with ASTM Sold lo:PUBLIC.RESOURCE.ORG, W1218734
No reproduction or networking permUted without license from IHS 20121111021:52:47 GMT
 r

ASTM Logo Removed

03559-03
in 8.1 is used for total recoverable lead. The same chelation- 22.2 When determining total recoverable lead use 125-mL
extraction procedure may be used to determine total recover- beakers or flasks, add 0.5 mL RN0 3 (sp gr 1.42) and proceed as
able cadmium (Test Methods D 3557), cobalt (Test Methods directed in 23.2 thru 23.15. When determining dissolved lead
D 3558), copper (Test Methods D 1688), iron (Test Methods use 250-mL separatory funnels and proceed as directed in 23.5
D 1068), nickel (Test Methods D 1886), and zinc (Test Meth- thru 23.15.
ods D 1691). 22.3 Construct an analytical curve by plotting the absor-
bances of standards versus micrograms of lead. Alternatively,
19. Interferences read directly in concentration if this capability is provided with
19.1 See Section 9. the instrument.
23. Procedure
20. Apparatus
23.1 Measure a volume of a well-mixed acidified sample
20.1 All apparatus described in Section 10 are required. containing less than 100 Ilg lead (100-mL maximum) into a
125-mL beaker or flask and adjust the volume to 100 mL with
21. Reagents water.
21.1 Bromphenol Blue Indicator Solution (1 glL)-Dissolve
NOTE 7-If only dissolved lead is to be determined, measure a volume
0.1 g of bromphenol blue in 100 mL of 50 % ethanol or
of filtered and acidified sample containing less than 100 Ilg of lead
2-propanol. (lOO-mL maximum) into a 250-mL separatory funnel, and start with 23.5.
21.2 Carbon Disulfide (CS 2 ).
23.2 Add 5 mL of HCl (sp gr 1.19) to each sample.
21.3 Chloroform (CRCI 3 ).
21.4 Hydrochloric Acid (sp gr 1.19)-Concentrated hydro- 23.3 Reat the samples on a steam bath or hot plate in a
chloric acid (HCl). well-ventilated hood until the volume has been reduced to 15
21.5 Hydrochloric Acid (1 + 2)-Add 1 volume of HCI (sp to 20 mL, making certain that the samples do not boil.
gr 1.19) to 2 volumes of water. NOTE 8-When analyzing brines and samples containing appreciable
21.6 Hydrochloric Acid (1 + 49)-Add 1 volume ofHCI (sp amounts of suspended matter, the amount of reduction in volume is left to
gr 1.19) to 49 volumes of water. the discretion of the analyst.
21.7 Lead Solution, Stock (1.0 mL =200 Ilg lead)- 23.4 Cool and filter the samples through a suitable filter
Dissolve 0.3198 g of lead nitrate (Pb (N0 3)2) in water such as fine-textured, acid-washed, ashless paper, into 250-mL
containing 1 mL of HN0 3 (sp gr 1.42) and dilute to 1 L with separatory funnels. Wash the filter paper two or three times
water. Warning-Lead salts are toxic. Handle with care and with water and bring to approximately a 100-mL volume.
avoid personal contamination. 23.5 Add 2 drops of bromphenol blue indicator solution and
21.8 Lead Solution, Intermediate (1.0 mL = 2.01l g lead)- mix.
Dilute 10 mL of lead stock solution and 1 mL of RN0 3 (sp gr 23.6 Adjust the pH by addition of NaOH (100 gIL) solution
1.42) to 1 L with water. Warning-Lead salts are toxic. Never until a blue color persists. Add HCI (1 + 49) by drops until the
pipet by mouth. Pipet with the end of a suction device or blue color just disappears; then add 2.5 mL of HCI (1 + 49) in
employ other convenient means of quantitative measurement. excess. The pH at this point should be 2.3.
21.9 Lead Solution, Standard (1.0 mL = 0.2 Ilg lead)-
NOTE 9-The pH adjustment in 23.6 may be made with a pH meter
Immediately before use, dilute 10.0 mL of lead intermediate instead of using an indicator.
solution and 1 mL of HN0 3 (sp gr 1.42) to 100 mL with water.
This standard is used to prepare working standards at the time 23.7 Add 10 mL of pyrrolidine dithiocarbamic acid-
of analysis. chloroform reagent and shake vigorously for 20 min
21.10 Nitric Acid (sp gr 1.42)-Concentrated nitric acid (Warning-See 21.11).
(RN0 3 )· 23.8 Plug the tip of the separatory funnel with cotton, allow
21.11 Pyrrolidine Dithiocarbamic Acid-Chloroform the phases to separate, and drain the chloroform phase into a
Reagent-Add 36 mL of pyrrolidine to 1 L of CHCI3 • Cool the 100-mL beaker.
solut~on and add 30 mL of CS 2 in small portions, swirling
23.9 Repeat the extraction with 10 mL of chloroform and
between additions. Dilute to 2 L with eHCI 3 . The reagent can drain the chloroform layer into the same beaker.
be ti~ed for several months if stored in a cool, dark place. NOTE IO-If color still remains in the CHCl 3 extract, reextract the
Warp-ing: All components of this reagent are highly toxic. aqueous phase until the chloroform layer is colorless.
Carbon disulfide is also highly flammable, prepare and use in 23.10 Place the beaker on a hot plate at low heat and
a we,ll-ventilated hood. Avoid inhalation and direct contact. evaporate just to near dryness. Remove beaker from heat and
2r'.l2 Sodium Hydroxide Solution (100 glL)-Dissolve 100 allow residual solvent to evaporate without further heating.
g of sodium hydroxide (NaOH) in water and dilute to 1 L. Warning-Perform in a well-ventilated hood.
23.11 Hold the beaker at a 45° angle and slowly add
22. Standardization dropwise 2 mL of HN0 3 (sp gr 1.42), rotating the beaker to
22.1 Prepare a blank and sufficient standards from 0.0 to effect thorough contact of the acid with the residue.
1000 IlglL lead from the lead standard solution (21.9) by 23.11.1 If acid is added to the beaker in a vertical position,
making appropriate dilutions in water. Prepare standards im- a violent reaction will occur accompanied by high heat and
mediately prior to use. spattering.

Copyright ASTM International 5

Provided by IHS under license with ASTM Sold to:PUBLlC.RESOURCE.ORG. W1218734
No reproduction or networking permitted without license from IHS 2012/1/1021:52:47 GMT
 ASTM Logo
Removed
559-03
23.12 Place the beaker on a hot plate at low heat and instrument. The calibration correlation coefficient shall be
evaporate just to dryness. equal to or greater than 0.990. In addition to the initial
23.13 Add 2 mL of HCI (1 + 2) to the beaker and heat while calibration blank, a calibration blank shall be analyzed at the
swirling for 1 min. end of the batch run to ensure contamination was not a problem
NOTE II-If a precipitate appears when the Hel (1 + 2) is added to the
during the batch analysis.
dried residue, obtain a fresh supply of pyrrolidine which has a different lot 26.2.2 Verify instrument calibration after standardization by
number or redistill the pyrrolidine just before preparing the pyrrolidine analyzing a standard at the concentration of one of the
dithiocarbamic acid-chloroform reagent. calibration standards. The concentration of a mid-range stan-
23.14 Cool and quantitatively transfer the solution to a dard should fall within ± 15 % of the known concentration.
lO-mL volumetric flask and bring to volume with water. 26.2.3 If calibration cannot be verified, recalibrate the
23.15 Aspirate each sample and record the scale reading or instrument.
concentration. 26.3 Initial Demonstration of Laboratory Capability:
26.3.1 If a laboratory has not performed the test before, or if
24. Calculation there has been a major change in the measurement system, for
24.1 Determine the weight of lead in each sample by example, new analyst, new instrument, etc., a precision and
referring to 22.3. Calculate the concentration of lead in bias study must be performed to demonstrate laboratory
micrograms per litre as follows: capability.
Lead, !!glL = (lOOO/A) X B (2) 26.3.2 Analyze seven replicates of a standard solution
prepared from an Independent Reference Material containing a
where: mid-range concentration of lead. The matrix and chemistry of
A = volume of original sample, mL, and the solution should be equivalent to the solution used in the
B = weight of lead in sample, !!g. collaborative study. Each replicate must be taken through the
complete analytical test method including any sample preser-
25. Precision and Bias
vation and pretreatment steps. The replicates may be inter-
25.1 Seven operators from six laboratories participated in spersed with samples.
this study. Five operators performed the analysis in triplicate 26.3.3 Calculate the mean and standard deviation of the
and two in duplicate at each concentration level. seven values and compare to the acceptable ranges of bias in
25.2 The bias of this test method for lead is listed in Table Table 2. This study should be repeated until the recoveries are
2. within the limits given in Table 2. If a concentration other than
25.3 These data may not apply to waters of other matrices. the recommended concentration is used, refer to Practice
25.4 This section on precision and bias conforms to Practice D 5847 for information on applying the F test and t test in
D 2777 - 77 which was in place at the time of collaborative evaluating the acceptability of the mean and standard devia-
testing. Under the allowances made in 1.4 of D 2777 - 98, tion.
these precision and bias data do meet existing requirements of 26.4 Laboratory Control Sample (LCS):
interlaboratory studies of Committee D 19 test methods.
26.4.1 To ensure that the test method is in control, analyze
26. Quality Control a LCS containing a known concentration of lead with each
batch or 10 samples. If large numbers of samples are analyzed
26.1 In order to be certain that analytical values obtained in the batch, analyze the LCS after every 10 samples. The
using these test methods are valid and accurate within the laboratory control samples for a large batch should cover the
confidence limits of the test, the following QC procedures must analytical range when possible. The LCS must be taken
be followed when analyzing lead. through all of the steps of the analytical method including
26.2 Calibration and Calibration Verification: sample preservation and pretreatment. The result obtained for
26.2.1 Analyze at least three working standards containing a mid-range LCS shall fall within ± 15 % of the known
concentrations of lead that bracket the expected sample con- concentration.
centration, prior to analysis of samples, to calibrate the
26.4.2 If the result is not within these limits, analysis of
samples is halted until the problem is corrected, and either all
TABLE 2 Determination of Bias, Chelation-Extraction the samples in the batch must be reanalyzed, or the results must
Amount Amount
Statistically be qualified with an indication that they do not fall within the
Added. Found. Sr. So. Bias. %
Significant
performance criteria of the test method.
~ gIL ~g/L (95 % Confi-
~g/L ~g/L
dence Level) 26.5 Method Blank:
Reagent Water Type II 26.5.1 Analyze a reagent water test blank with each batch.
100 86.1 17.7 8 -13.9 yes The concentration of lead found in the blank should be less
400 364 55 27 -9.0 yes than 0.5 times the lowest calibration standard. If the concen-
800 674 124 24 -15.8 yes
tration of lead is found above this level, analysis of samples is
Selected Water Matrices
halted until the contamination is eliminated, and a blank shows
100 83 20 6.5 -17 yes no contamination at or above this level, or the results must be
400 352 51 21 -12 yes
800 669 78 50 -16 yes qualified with an indication that they do not fall within the
performance criteria of the test method.

Copyright ASTM International 6

Provided by IHS under license with ASTM Sold lo:PUBLlC.RESOURCE.ORG, W121B734
No reproduction or networking permitted wilhoullicense from IHS 201211/1021:52:47 GMT
r ASTM Logo
Removed
559-03
26.6 Matrix Spike (MS): TEST METHOD C-DIFFERENTIAL PULSE
26.6.1 To check for interferences in the specific matrix ANODIC STRIPPING VOLTAMMETRY
being tested, perform a MS on at least one sample from each
batch by spiking an aliquot of the sample with a known 27. Scope
concentration of lead and taking it through the analytical 27.1 This test method describes the determination of lead in
method. water and waste waters using differential pulse anodic stripping
26.6.2 The spike concentration plus the background concen- voltammetry.
tration of lead must not exceed the high calibration standard. 27.2 This test method is applicable up to a concentration of
The spike must produce a concentration in the spiked sample 100iJ. gIL lead. Higher concentrations can be determined by
that is 2 to 5 times the analyte concentration in the unspiked dilution.
sample, or 10 to 50 times the detection limit of the test method, 27.3 The lower limit of detection for lead is 1.0 iJ.g/L.
whichever is greater. NOTE 13-The lower limit of detection for differential pulse anodic
26.6.3 Calculate the percent recovery of the spike (P) using stripping voltammetry is not absolute and can easily be lowered by
the following formula: changing the experimental parameters as described in Appendix Xl.
However, these variations have not been interlaboratory tested.
P = 100 [AW, + V) - B Y:.J I C V (3)

where: 28. Terminology

A = analyte concentration (mg/L) in spiked sample, 28.1 Definitions-See 3.1.
B = analyte concentration (mg/L) in unspiked sample, 28.2 Definitions of Terms Specific to This Standard:
C concentration (mg/L) of analyte in spiking solution, 28.2.1 spiking solution-the standard solution added to the
Vs volume (mL) of sample used, and polarographic cell that is used to quantitate the sample.
V = volume (mL) added with spike.
28.2.2 stripping peak potential-the applied potential ver-
26.6.4 The percent recovery of the spike shall fall within the sus SCE at which the stripping peak current is a maximum.
limits,:· based on the analyte concentration, listed in Guide 28.2.2.1 SCE-saturated calomel electrode.
D 58tp, Table 2. If the percent recovery is not within these 28.2.3 stripping peak signal-the current measured at the
limits;: a matrix interference may be present in the sample stripping peak maximum for a metal.
select~d for spiking. Under these circumstances, one of the
following remedies must be employed: the matrix interference 29. Summary of Test Method
must be removed, all samples in the batch must be analyzed by
29.1 This test method determines the total recoverable
a test'method not affected by the matrix interference, or the
concentration of lead in water and waste water. The same
results must be qualified with an indication that they do not fall
. digestion, sample preparation, and analysis procedure may be
within the performance criteria of the test method.
used to determine total recoverable cadmium (Test Methods
NOTE 12-Acceptable spike recoveries are dependent on the concen- D 3557) simultaneously with lead.
tration of the component of interest. See Guide D 5810 for additional 29.2 The sample is digested with nitric acid in a polaro-
information. graphic cell: 0.2 M ammonium citrate buffer (pH 3.0) and 10 %
26.7 Duplicate: hydroxylamine solution are added. The solution is warmed to
dissolve the lead. Warming with hydroxylamine eliminates
26.7.1 To check the precision of sample analyses, analyze a
interference from ferric iron by reducing it to ferrous.
sample in duplicate with each batch. If the concentration of the
29.3 After cooling, this sample is deaerated, and the lead is
analyte is less than five times the detection limit for the analyte,
deposited into a hanging mercury drop electrode with surface
a matrix spike duplicate (MSD) should be used.
area of 1.5 to 3.0 mm2 at a constant potential of - 0.80 V
26.7.2 Calculate the standard deviation of the duplicate versus saturated calomel electrode (SCE). The lead is then
values and compare to the precision in the collaborative study stripped back into solution using the differential pulse scanning
using an F test. Refer to 6.4.4 of Practice D 5847 for mode, and the current is measured during the stripping step.
information on applying the F test. 29.4 The stripping peak height is proportional to the con-
26.7.3 If the result exceeds the precision limit, the batch centration of the lead, and the stripping peak potential is a
must be reanalyzed or the results must be qualified with an qualitative measure of the lead in solution.
indication that they do not fall within the performance criteria
of the test method. 30. Interferences
26.8 Independent Reference Material (IRM): 30.1 Selenium does not interfere up to 50 iJ.g/L. Interference
26.8.1 In order to verify the quantitative value produced by from selenium concentration up to 1000 iJ.g/L may be over-
the test method, analyze an Independent Reference Material come by adding ascorbic acid which reduces selenium (IV) to
(IRM) submitted as a regular sample (if practical) to the selenium metal and eliminates the interference.
laboratory at least once per quarter. The concentration of the 30.2 When ferric ions are present at levels greater than
IRM should be in the concentration mid-range for the method cadmium, interference may occur from oxidizing the deposited
chosen. The value obtained must fall within the control limits metal out of the amalgam. Interference by ferric iron at
established by the laboratory. concentrations as high as 20 mg/L is eliminated by warming

Copyright ASTM International 7

ProvIded by IHS under license with ASTM Sold to:PUBLlC.RESQURCE.ORG, W1218734
No reproduction or networking permllted without license from IHS 2012/1/1021 :52:47 GMT
 ASTM Logo
Removed
03559-03
with hydroxylamine. Ferric ions are reduced to ferrous ions by 32.4 Hydrochloric Acid (sp gr 1.19)-Concentrated hydro-
the hydroxylamine, and the interference caused by the presence chloric acid (HCl).
of iron is eliminated. 32.5 Hydroxylamine Solution (100 glL)-Dissolve 5.00 g of
30.3 The presence of a neighboring stripping peak which is hydroxylamine hydrochloride (NH20H·HCl) in reagent water
<100 mV from that of lead will interfere. and dilute to 50 mL.
32.6 Nitric Acid (sp gr 1.42) 12-Redistilled concentrated
31. Apparatus nitric acid (HN0 3).
31.1 Polarographic Instrumentation, capable of performing 32.7 Nitric Acid (sp gr 1.42)-Concentrated nitric acid
differential pulse work. 8 (HN0 3 )·
31.2 Hanging Mercury Drop Electrode. 9 32.8 Nitric Acid (1 + 4)-Add 1 volume of nitric acid (sp gr
31.3 Reagent Purifier System. 10 1.42) to 4 volumes of water.
31.4 Counter Electrode, platinum. 32.9 Nitric Acid (2 + 3)-Add 2 volumes of nitric acid (sp
31.5 Salt Bridge, with slow leakage fritted glass tip, 11 to gr 1.42) reagent grade,6 to 3 volumes of water.
isolate saturated calomel electrode from the test solution. 32.10 Purified Nitrogen-Nitrogen employed for deoxy-
31.6 Magnetic Stirrer-The magnetic stirrer used must have genation must be sufficiently oxygen-free so that a differential
a separate on/off switch, so that uniform rotational speed can pulse polarographic scan from - 0.20 to - 0.80 V versus SCE
be maintained. -mm (0.5-in.) magnetic stirring bar is also of the citrate buffer solution, after 10 min deaeration at 105
required. mm 3/min, gives a signal no more than 0.1[1 A. See Appendix
31.7 pH Meter. X2 to learn methods of gas purification.
31.8 Hot Plate. 32.11 Lead Solution, Stock (1 mL = 0.1 mg Pb )-Clean
31.9 Micropipets incorporating disposable plastic tips are oxide from lead metal with HN0 3 (1 + 4). Wash the cleaned
used. The sizes required are 10, 20, 50, and 100 [1L. metal with water and dry. Dissolve 0.1000 g of the lead in 25
mL of HN0 3 (1 + 4). Dilute to 1 L with water.
32. Reagents
32.1 Citrate Buffer Solution-Dissolve 42 g of citric acid in 33. Caution
800 mL of water and add enough ammonium hydroxide to 33.1 The liquid mercury used for the hanging mercury drop
bring the pH to 3.0 ± 0.2. Dilute to 1000 mL with water and electrode 9 forms a toxic vapor, and the liquid itself is toxic.
place in the cell of the reagent purifier system. Purify for a Handle with gloves in a ventilated hood.
minimum of 36 h at a potential of - 1.3 V versus SCE at a
mercury pool working electrode. Deaerate the supporting 34. Calibration
electrolyte during the purification process. If the buffer con- 34.1 After a differential pulse anodic stripping curve is run
tains less than 1 [1g/L of lead, the purification step may be on the sample solution, the anodic stripping curve is quanti-
omitted, providing new buffer is prepared every 2 weeks. The tated using the technique of standard addition.
electrolyzed buffer is stable against bacterial growth for at least 34.2 Prepare spiking solution as directed in 32.11. Alterna-
1 month. tively, if cadmium is to be quantified too, both metals may be
added to a single spiking solution. The best procedure here is
NOTE 14-To prevent bacterial growth in the unpurified buffer for a
month, sterilize by autoclaving for 15 min at 121°C and 1.03 X 105 Pa (15 to prepare the spiking solution with each metal in the ratio
psi). expected in the sample. (Example: If lead is expected to be 5
times the cadmium, prepare a spiking solution with lead and
32.2 Aqua Regia (1 + I)-Add 1 volume of nitric acid (sp
cadmium in a 5 to 1 ratio).
gr 1.42), reagent grade, to 4 volumes of water. Then add 3
34.3 Add an appropriate aliquot of the lead spiking solution
volumes of hydrochloric acid.
to the sample in the cell. Deaerate for 5 min at 105mm 3/min to
32.2.1 Warning-Toxic fumes may be released. Prepare
mix the solution and remove oxygen added with the spike.
and use in a ventilated hood.
34.4 Repeat the analysis procedure beginning with 35.8.
32.3 Ascorbic Acid Solution (100 g/L)-Dissolve 10.0 g of
L-ascorbic acid in reagent water and dilute to 100 mL. 35. Procedure
35.1 Soak voltammetric cells (or digestion vessels) over-
night in concentrated HN0 3 , and verify that the reagent blank
8 Two suitable instrument are the Princeton Applied Research, Princeton, NJ,
Model 174A polarographic analyzer with mechanical drop timer, and Houston
is less than 1 [1g/L for lead. Omit the soaking step if the reagent
Omnigraphic X-Y Recorder Model 2200·3-3. An equally suitable instrument is the blank of the unsoaked cells is less than 1 [1g/L. Clean other
Environmental Sciences Associates (ESA), Bedford, MA, Model 3040 Charge glassware with HN0 3 (2 + 3). See Annex Al for a procedure to
Transfer Analyzer. For settings on ESA Model 3040 equivalent to those in paragraph clean glassware.
33.10, see ESA Application Note CTA-AN-l.
9 The Model 9323 hanging, mercury drop electrode or the Model 314 automated NOTE IS-Soaking the cells (or digestion vessels) in aqua regia (1 + 1)
hanging mercury drop electrode manufactured by Princeton Applied Research has for 1 h improves blank values.
been found satisfactory. The Metrohm E-410 hanging mercury drop electrode is
equally satisfactory.
10 Both the Model 9500 Electrolyte Purification System (Princeton Applied
Research, Princeton, NJ) and the Model 2014 PM Reagent Cleaning System 12 Acids that may contain suitably low levels of lead (and cadmium) are the
(Environmental Sciences Associates, Bedford, MA) are equally suitable. redistilled reagents or equivalent from G. Frederick Smith Chemical Co., 867
II A Vycor (Corning Glass Works, Corning, NY) tip has been found suitable. McKinley Ave., Columbus, OH 43223.

Copyright ASTM International 8

Provided by lHS under license with ASTM Sold lo:PUBLlC.RESOURCE.ORG, W1218734
No reproduction or networking permitted without license from IHS 2012/111021:52:47 GMT
 --- ~-.----~~------- ..-- .. ~ ..... - . - ~ -.----~-- ----~-

ASTM Logo Removed

03559-03
35.2 Place exactly 10.0 mL of a well-mixed sample con- TABLE 3 Determination of Precision and Bias for Lead by
Differential Pulse Anodic Stripping Voltammetry
taining less than 100 f,tglL of lead into the cell.
Amount Amount Statistically
NOTE16-Concentrations greater than 100 /-lg/L of lead may be ST. So. %
Added. Found. Significant
11 giL Ilg/L Bias
95 % Level
determined by dilution. j.lg/L j.lg/L
35.3 Add 2.0 mL of redistilled HN0 3 to each sample. Reagent Water Type VI

35.4 Evaporate the samples without boiling on a hot plate or 20 21.6 4.00 2.95 + 8.00 No
40 38.4 5.70 3.71 -4.00 No
steam bath until the sample just reaches dryness (do not "bake" 80 78.5 10.21 9.89 -1.88 No
as this may cause losses due to volatilization). Steps 35.3 and Water of Choice
35.4 may be repeated if necessary for samples containing large
20 22.4 5.33 4.65 + 12.0 No
amounts of organic matter. 40 40.3 6.59 6.91 + 0.75 No
35.5 Cool, add 5.0 mL of citrate buffer, and 100 f,tL of 80 78.8 10.27 11.10 - 1.50 No
hydroxylamine solution. Warm the solution 15 min to reduce
the ferric iron and to effect dissolution of the metals in the
buffer.
35.6 Bring to volume of 10 to 12 mL with citrate buffer (pH (4)
3.0). The exact volume need not be known because the
standard additions method will be used to quantitate. where:
35.6.1 To overcome selenium at levels up to 1000 f,tglL, add i1 = stripping peak height for the sample,
1 mL of ascorbic acid. i2 = stripping height for the sample plus standard,
35.7 Deaerate for 10 min at 105 mm 3 /min with an oxygen- v = volume of standard taken for spiking,
free stream of nitrogen. V = volume of sample before digestion,
35.8 After deaeration is complete, extrude with the hanging Cs = concentration of standard used in spike, mglL, and
mercury drop electrode a mercury droplet whose area is 1.5 to CLI = concentration of the unknown in the sample, mglL.
3 mm2, as determined in Annex A2. Turn on the magnetic 36.2 The following is a sample calculation using this
stirrer and adjust the stirring rate so that the solution beneath equation:
the mercury droplet is well stirred but there is no visible i l = 0.459 /-lA (5)
movement of the mercury droplet. The stirrer is turned on 15 s i2 = 1.24 /-lA
prior to deposition to assure uniform rotational speed. v = 0.02mL
35.9 Connect the cell. Deposit at - 0.80 V versus SCE for
V= 1O.0mL
exactly 2 min, switch off stirrer, and wait exactly 30 s before
beginning the scan. The quiescent period between deposition Cs = 10.0 mg/L
and scan allows convection to cease.
35.9.1 Appendix X4 gives typical stripping curve shapes, (0.459)(0.02)(10)
peak potential, and sensitivities (in f,tA/5 f,tglL) for lead CII = (1.24)(0.02) + (1.24 _ 0.459)(10) = 0.01172 mg/L
deposited into a mercury droplet with a 2.9-mm2 area for 2 min
with stirring plus 30 s without stirring. 37. Precision and Bias 13

35.10 The following typical settings are for polarographic 37.1 Eight operators from seven laboratories participated in
instrumentation capable of performing differential pulse this study by determining three replicates at each concentration
work: 8 electrode, hanging mercury drop electrode (area 1.5 to level.
3 mm2); initial potential, - 0.80 V versus SeE; scan rate, 5 37.2 The precision and bias of this test method for lead is
mV/s; scan direction, "+"; modulation amplitude, 25 mY; listed in Table 3.
current range, 1 to 20 f,tA; drop time, 0.5 s; display direc- 37.3 These data may not apply to waters of other matrices.
tion,"-"; low pass filter, off; mode, differential pulse; deposi- 37.4 This section on precision and bias conforms to Practice
tion time, 2 min with stirring plus 30 s quiescent; scan range, D 2777 - 77 which was in place at the time of collaborative
stop - 0.20 V. testing. Under the allowances made in 1.4 of D 2777 - 98,
35.10.1 The linearity of this test method has been tested up these precision and bias data do meet existing requirements of
to currents of 20 f,tA. If the sample gives stripping peaks with interlaboratory studies of Committee D19 test methods.
currents larger than 20 f,tgA, one may decrease the deposition
time (see Appendix Xl), although this technique has not been 38. Quality Control
interlaboratory tested. The recommended procedure is to dilute 38.1 In order to be certain that analytical values obtained
the sample and proceed as directed in 35.2 through 35.10. using these test methods are valid and accurate within the
35.11 To obtain a blank, place exactly 10.0 mL of Type IV confidence limits of the test, the following QC procedures must
water into the cell and proceed as directed in 35.2 through be followed when analyzing lead.
35.10. 38.2 Calibration and Calibration Verification:

36. Calculation
36.1 Calculate the concentration of lead determined by the 13 Supporting data are available from ASTM Headquarters. Request RR: D19-

standard addition procedure as follows: 1048 .

....... ............... .
..... ,,, ..........

Copyright ASTM International 9

Provided by IHS under license wllh ASTM Sold lo:PUBL1C.RESOURCE.ORG. W1218734
No reproduction or networking permitted without license from lHS 201211110 21 :52:47 GMT
 ASTM Logo
Removed
0 3559-03
38.2.1 Analyze at least three working standards containing no contamination at or above this level, or the results must be
concentrations of lead that bracket the expected sample con- qualified with an indication that they do not fall within the
centration, prior to analysis of samples, to calibrate the performance criteria of the test method.
instrument. The calibration correlation coefficient shall be 38.6 Matrix Spike (MS):
equal to or greater than 0.990. In addition to the initial 38.6.1 To check for interferences in the specific matrix
calibration blank, a calibration blank shall be analyzed at the being tested, perform a MS on at least one sample from each
end of the batch run to ensure contamination was not a problem batch by spiking an aliquot of the sample with a known
during the batch analysis. concentration of lead and taking it through the analytical
38.2.2 Verify instrument calibration after standardization by method.
analyzing a standard at the concentration of one of the 38.6.2 The spike concentration plus the background concen-
calibration standards. The concentration of a mid-range stan- tration of lead must not exceed the high calibration standard.
dard should fall within ± 15 % of the known concentration. The spike must produce a concentration in the spiked sample
38.2.3 If calibration cannot be verified, recalibrate the that is 2 to 5 times the analyte concentration in the unspiked
instrument. sample, or 10 to 50 times the detection limit of the test method,
38.3 Initial Demonstration of Laboratory Capability: whichever is greater.
38.3.1 If a laboratory has not performed the test before, or if 38.6.3 Calculate the percent recovery of the spike (P) using
there has been a major change in the measurement system, for the following formula:
example, new analyst, new instrument, etc., a precision and
bias study must be performed to demonstrate laboratory P = 100 [A(Vs + V) - B Vs] / C V (6)
capability. where:
38.3.2 Analyze seven replicates of a standard solution A = analyte concentration (mg/L) in spiked sample,
prepared from an Independent Reference Material containing a B = analyte concentration (mg/L) in unspiked sample,
mid-range concentration of lead. The matrix and chemistry of C concentration (mg/L) of analyte in spiking solution,
the solution should be equivalent to the solution used in the V:, = volume (mL) of sample used, and
collaborative study. Each replicate must be taken through the V = volume (mL) added with spike.
complete analytical test method including any sample preser- 38.6.4 The percent recovery of the spike shall fall within the
vation and pretreatment steps. The replicates may be inter- limits, based on the analyte concentration, listed in Guide
spersed with samples. D 5810, Table 3. If the percent recovery is not within these
38.3.3 Calculate the mean and standard deviation of the limits, a matrix interference may be present in the sample
seven values and compare to the acceptable ranges of bias in selected for spiking. Under these circumstances, one of the
Table 3. This study should be repeated until the recoveries are following remedies must be employed: the matrix interference
within the limits given in Table 3. If a concentration other than must be removed, all samples in the batch must be analyzed by
the recommended concentration is used, refer to Practice a test method not affected by the matrix interference, or the
D 5847 for information on applying the F test and t test in results must be qualified with an indication that they do not fall
evaluating the acceptability of the mean and standard devia- within the performance criteria of the test method.
tion.
NOTE 17-Acceptable spike recoveries are dependent on the concen-
38.4 Laboratory Control Sample (LCS): tration of the component of interest. See Guide D 5810 for additional
38.4.1 To ensure that the test method is in control, analyze information.
a LCS containing a known concentration of lead with each
38.7 Duplicate:
batch or 10 samples. If large numbers of samples are analyzed
in the batch, analyze the LCS after every 10 samples. The 38.7.1 To check the precision of sample analyses, analyze a
laboratory control samples for a large batch should cover the sample in duplicate with each batch. If the concentration of the
analytical range when possible. The LCS must be taken analyte is less than five times the detection limit for the analyte,
through all of the steps of the analytical method including a matrix spike duplicate (MSD) should be used.
sample preservation and pretreatment. The result obtained for 38.7.2 Calculate the standard deviation of the duplicate
a mid-range LCS shall fall within ± 15 % of the known values and compare to the precision in the collaborative study
concentration. using an F test. Refer to 6.4.4 of Practice D 5847 for
38.4.2 If the result is not within these limits, analysis of information on applying the F test.
samples is halted until the problem is corrected, and either all 38.7.3 If the result exceeds the precision limit, the batch
the samples in the batch must be reanalyzed, or the results must must be reanalyzed or the results must be qualified with an
be qualified with an indication that they do not fall within the indication that they do not fall within the performance criteria
performance criteria of the test method. of the test method.
38.5 Method Blank: 38.8 Independent Reference Material (IRM):
38.5.1 Analyze a reagent water test blank with each batch. 38.8.1 In order to verify the quantitative value produced by
The concentration of lead found in the blank should be less the test method, analyze an Independent Reference Material
than 0.5 times the lowest calibration standard. If the concen- (IRM) submitted as a regular sample (if practical) to the
tration of lead is found above this level, analysis of samples is laboratory at least once per quarter. The concentration of the
halted until the contamination is eliminated, and a blank shows IRM should be in the concentration mid-range for the method

Copyright ASTM International 10

Provided by IHS under license wilh ASTM Sold to:PUBLlC.RESOURCE.ORG. W1218734
No reproduction or networking permitted without license from IHS 201211/1021 :52:47 GMT
 ASTM Logo
Removed
03559-03
TABLE 4 Determination of Bias and Overall Precision in Reagent 41. Interferences
Water, Graphite Furnace
41.1 For a complete discussion on general interferences
Amount Amount
Added, Found, ST Bias,:!: Bias,:!: %
Statistically with furnace procedures, the analyst is referred to Practice
Significant D 3919.
Ilg/L Ilg /L
72 75 7 +3 +4.2 No 41.2 To suppress sulfate interference (up to 1500 mg/L)
12 11 2 -1 -8.3 No lanthanum nitrate is added to both samples and calibration
24 25 4 +1 +4.0 No standards. 14

TABLE 5 Determination of Bias and Overall Precision in Water of

42. Apparatus
Choice, Graphite Furnace 42.1 Atomic Absorption Spectrophotometer, for use at 283.3
Amount Amount nm with background correction.
Statistically
Added, Found, ST Bias,:!: Bias,:!: %
Significant NOTE lS-A wavelength other than 283.3 nm may be used if it has been
Ilg/L Ilg/L
72 65 9 -7 -9.7 Yes determined to be suitable.
12 10 3 -2 -13.3 Yes NOTE 19-The manufacturer's instructions should be followed for all
24 21 3 -3 -12.5 Yes instrumental parameters.
42.2 Lead Electrodeless Discharge Lamps are satisfactory.
42.3 Graphite Furnace, capable of reaching temperatures
sufficient to atomize the element of interest.
chosen. The value obtained must fall within the control limits 42.4 Graphite Tubes, compatible with furnace device.
established by the laboratory. 42.5 Pipets, microlitre with disposable tips. Sizes may range
from 5 /-lL to 100 /-lL, as required.
TEST METHOD D-ATOMIC ABSORPTION, 42.6 Argon, standard, welders grade, commercially avail-
GRAPHITE FURNACE able. Nitrogen may also be used if recommended by the
instrument manufacturer.
39. Scope 42.7 Data Storage and Reduction Devices-Computer- and
39.1 This test method covers the determination of dissolved microprocessor-controlled devices, or strip chart recorder,
and total recoverable lead in most waters and wastewaters. should be utilized for data collection, storage, reduction, and
problem recognition (drift, incomplete atomization, changes in
39.2 The test method is applicable in the range from 5 to
sensitivity, etc.). Strip chart recorders shall have a full-scale
100 /-lg/L of lead using a 20-/-lL injection. The range can be
deflection time of 0.2 s or less to ensure accuracy.
increased or decreased by varying the volume of sample
42.8 Automatic sampling is recommended if available.
injected or the instrumental settings. High concentrations may
be diluted but preferably should be analyzed by direct aspira-
43. Reagents
tion atomic absorption spectrophotometry (Test Method A).
39.3 This test method has been used successfully with 43.1 Lanthanum Nitrate Solution, (1mL = 50 mg La)-
reagent water, lake water, river water, well water, filtered tap Dissolve 58.64 g of ACS reagent grade La203 in 100 mL of
concentrated HN0 3 and dilute to 1000 mL with water. This
water, condensate from a medium Btu coal gasification pro-
solution is added to the lead calibration standard and to the
cess, waste treatment plant effluent, and a production plant
sample solution as well at a rate of 10 mL per 100 mL of
process water. It is the user's responsibility to assure validity of
standard or sample solution.
this test method for untested matrices.
43.2 Lead Solution, Stock (1.0 mL = 200 /-lg Pb)-See 21.7.
43.3 Lead Solution, Standard (1.0 mL = 1.0 /-lg Pb)-Dilute
40. Summary of Test Method
5.0 mL of lead solution, stock (43.2) and 1 mL of HN0 3(sp gr
40.1 Lead is determined by an atomic absorption spectro- 1.42) to 1 L with water.
photometer used in conjunction with a graphite furnace. A 43.4 Lead Solution, Working-Prepare the working stan-
sample is placed in a graphite tube, evaporated to dryness, dards at the time of analysis by adding various volumes of
charred (pyrolyzed or ashe d) and atomized. The absorption standard lead solution (43.3) to 50 mL of water containing 0.5
signal generated during atomization is recorded and compared mL of HN0 3(sp gr 1.42) adding 10 mL of lanthanum nitrate
to standards. A general guide for the application of the graphite solution (40.1) and diluting to 100 mL with water in a
furnace is given in Practice D 3919. volumetric flask.
40.2 Dissolved lead is determined on a filtered and pre- 43.5 Nitric Acid (sp gr 1.42)-Concentrated nitric acid
served sample with no pretreatment. (HN0 3). (See Note 3).
43.6 Nitric Acid (1 + I)-Cautiously dilute 50 mL of nitric
40.3 Total recoverable lead is determined following acid
acid (sp gr 1.42) to 100 mL with water.
digestion and filtration. Because chlorides interfere with fur-
nace procedures for some metals, the use of hydrochloric acid
in any digestion or solubilization step is to be avoided. If
suspended material is not present, this digestion and filtration 14 Information regarding sulfate suppression can be found in" Atomic Absorption

may be omitted. Newsletter," Vol IS, No.3, May-June 1976, p. 71.

Copyright ASTM International 11

Provided by IHS under license with ASTM Sold !o:PUBLlC.RESOURCE.ORG, W1218734
No reproduction or networking permitted wilhout license from IHS 201211/1021:52:47 GMT
 ASTM Logo
Removed
3559-03
44. Standardization 47.3 This section on precision and bias conforms to Practice
44.1 Initially, set the~instrument according to the manufac- D 2777 - 77 which was in place at the time of collaborative
turer's specifications. Follow the general instructions as pro- testing. Under the allowances made in 1.4 of D 2777 - 98,
vided in Practice D 3919. these precision and bias data do meet existing requirements of
interlaboratory studies of Committee D19 test methods.
45. Procedure
48. Quality Control
45.1 Clean all glassware to be used for preparation of
48.1 In order to be certain that analytical values obtained
standard solutions or in the solubilization step, or both, by
using these test methods are valid and accurate within the
rinsing first with HN0 3 (1 + 1) and then with water.
confidence limits of the test, the following QC procedures must
45.2 Measure 100.0 mL of a well-mixed sample into a
be followed when analyzing lead.
125-mL beaker or flask. For total recoverable lead add
48.2 Calibration and Calibration Verification:
HN0 3 (sp gr 1.42) to each sample at a rate of 5 mLIL and
48.2.1 Analyze at least three working standards containing
proceed as directed in 45.4 through 45.6.
concentrations of lead that bracket the expected sample con-
45.3 If only dissolved lead is to be determined, filter the
centration, prior to analysis of samples, to calibrate the
sample through a 0.45 !lm membrane filter prior to acidifica-
instrument. The calibration correlation coefficient shall be
tion, add 10 mL of lanthanum nitrate solution (43.1) per 100
equal to or greater than 0.990. In addition to the initial
mL of sample and proceed to 45.6.
calibration blank, a calibration blank shall be analyzed at the
45.4 Heat the samples at 95°C on a steam bath or hotplate
end of the batch run to ensure contamination was not a problem
in a well ventilated fume hood until the volume has been
during the batch analysis.
reduced to 15 to 20 mL, making certain that the samples do not
48.2.2 Verify instrument calibration after standardization by
boil. (See Note 5.)
analyzing a standard at the concentration of one of the
45.5 Cool and filter the sample through a suitable filter
calibration standards. The concentration of a mid-range stan-
(such as fine texture, acid washed, ashless paper) into a
dard should fall within ± 15 % of the known concentration.
100-mL volumetric flask. Wash the filter paper 2 or 3 times
48.2.3 If calibration cannot be verified, recalibrate the
with water, add 10 mL of lanthanum nitrate solution (43.1) and
instrument.
bring to volume.
48.3 Initial Demonstration of Laboratory Capability:
NOTE 20-1f suspended material is not present, this filtration may be 48.3.1 If a laboratory has not performed the test before, or if
omitted. there has been a major change in the measurement system, for
45.6 Inject a measured aliquot of sample into the furnace example, new analyst, new instrument, etc., a precision and
device following the directions as provided by the particular bias study must be performed to demonstrate laboratory
instrument manufacturer. Refer to Practice D 3919. capability.
48.3.2 Analyze seven replicates of a standard solution
46. Calculation prepared from an Independent Reference Material containing a
46.1 Determine the concentration of lead in each sample by mid-range concentration of lead. The matrix and chemistry of
referring to Practice D 3919. the solution should be equivalent to the solution used in the
46.2 The dissolved lead results obtained from a graph or collaborative study. Each replicate must be taken through the
instrument readout must be multiplied by 1.1 to compensate for complete analytical test method including any sample preser-
dilution made by the addition of lanthanum nitrate solution in vation and pretreatment steps. The replicates may be inter-
45.3. spersed with samples.
48.3.3 Calculate the mean and standard deviation of the
47. Precision and Bias 15 seven values and compare to the acceptable ranges of bias in
47.1 The precision of this test method was tested by 13 Tables 4 and 5. This study should be repeated until the
laboratories in reagent water, lake water, river water, well recoveries are within the limits given in Tables 4 and 5. If a
water, filtered tap water, condensate from a medium Btu coal concentration other than the recommended concentration is
gasification process, a waste treatment plant effluent and a used, refer to Practice D 5847 for information on applying the
production plant process water. One laboratory reported data F test and t test in evaluating the acceptability of the mean and
from two operators. Although multiple injections may have standard deviation.
been made, the report sheets provided allowed only for 48.4 Laboratory Control Sample (LCS):
reporting single values. Thus, no single operator precision data 48.4.1 To ensure that the test method is in control, analyze
can be calculated. Bias data and overall precision data are a LCS containing a known concentration of lead with each
given in Table 4 and Table 5. batch or 10 samples. If large numbers of samples are analyzed
47.2 These data may not apply to waters of other matrices, in the batch, analyze the LCS after every 10 samples. The
therefore, it is the responsibility of the analyst to assure the laboratory control samples for a large batch should cover the
validity of the test method in a particular matrix. analytical range when possible. The LCS must be taken
through all of the steps of the analytical method including
sample preservation and pretreatment. The result obtained for
15 Supporting data giving results of cooperative tests are available from ASTM a mid-range LCS shall fall within ± 15 % of the known
Headquarters. Request RR: D 19-1112. concentration.

Copyright ASTM International 12

Provided by IHS under license with ASTM Sold lo:PUBLlC,RESOURCE.ORG, W1218734
No reproduction or networking permitted without license from IHS 2012/1/1021:52:47 GMT
 ASTM Logo
Removed
0 3559-03
48.4.2 If the result is not within these limits, analysis of D 5810, Tables 4 and 5. If the percent recovery is not within
samples is halted until the problem is corrected, and either all these limits, a matrix interference may be present in the sample
the samples in the batch must be reanalyzed, or the results must selected for spiking. Under these circumstances, one of the
be qualified with an indication that they do not fall within the following remedies must be employed: the matrix interference
performance criteria of the test method. must be removed, all samples in the batch must be analyzed by
48.5 Method Blank: a test method not affected by the matrix interference, or the
48.5.1 Analyze a reagent water test blank with each batch. results must be qualified with an indication that they do not fall
The concentration of lead found in the blank should be less within the performance criteria of the test method.
than 0.5 times the lowest calibration standard. If the concen-
NOTE 21-Acceptable spike recoveries are dependent on the concen-
tration of lead is found above this level, analysis of samples is tration of the component of interest. See Guide D 5810 for additional
halted until the contamination is eliminated, and a blank shows information.
no contamination at or above this level, or the results must be
qualified with an indication that they do not fall within the 48.7 Duplicate:
performance criteria of the test method. 48.7.1 To check the precision of sample analyses, analyze a
48.6 Matrix Spike (MS): sample in duplicate with each batch. If the concentration of the
48.6.1 To check for interferences in the specific matrix analyte is less than five times the detection limit for the analyte,
being tested, perform a MS on at least one sample from each a matrix spike duplicate (MSD) should be used.
batch by spiking an aliquot of the sample with a known 48.7.2 Calculate the standard deviation of the duplicate
concentration of lead and taking it through the analytical values and compare to the precision in the collaborative study
method. using an F test. Refer to 6.4.4 of Practice D 5847 for
48.6.2 The spike concentration plus the background concen- information on applying the F test.
tration of lead must not exceed the high calibration standard. 48.7.3 If the result exceeds the precision limit, the batch
The spike must produce a concentration in the spiked sample must be reanalyzed or the results must be qualified with an
that is 2 to 5 times the analyte concentration in the unspiked indication that they do not fall within the performance criteria
sample, or 10 to 50 times the detection limit of the test method, of the test method.
whichever is greater. 48.8 Independent Reference Material (IRM):
48.6.3 Calculate the percent recovery of the spike (P) using 48.8.1 In order to verify the quantitative value produced by
the following formula: the test method, analyze an Independent Reference Material
P = 100 [AW,. + V) - B v:,] / C V (7) (IRM) submitted as a regular sample (if practical) to the
laboratory at least once per quarter. The concentration of the
where: IRM should be in the concentration mid-range for the method
A = analyte concentration (mg/L) in spiked sample, chosen. The value obtained must fall within the control limits
R = analyte concentration (mg/L) in unspiked sample,
established by the laboratory.
C = concentration (mg/L) of analyte in spiking solution,
11., = volume (mL) of sample used, and
V = volume (mL) added with spike. 49. Keywords
48.6.4 The percent recovery of the spike shall fall within the 49.1 atomic absorption; chelation-extraction; graphite fur-
limits, based on the analyte concentration, listed in Guide nace spectrophotometry; lead; voltammetry

ANNEXES

(Mandatory Information)

At. PROCEDURE TO CLEAN GLASSWARE

ALl Leach the voltammetric cells in concentrated HN0 3 A1.2 After the leaching period, rinse the glassware with
for at least 24 h prior to use. During the leaching period for the reagent water and place in an oven to dry. Exclude the oven
cells, fill other glassware with the HN0 3 (2 + 3), cover by a drying step for the platinum wire and outgassing tube. Clean
sheet of plastic film 16 to prevent contamination by trace metals the reference electrode salt bridge tube initially by soaking for
in atmospheric particles, and soak for at least 24 h. Clean all 24 h with HNOi2 + 3) but thereafter keep it immersed in a
glassware that may contact the sample solution. This includes small amount of the purified buffer solution. Again, use plastic
the voltammetric cells, digestion beakers, stirring bars, plati- film 16 to cover any areas that might tend to accumulate dust.
num wire, and outgassing tubes. For very low-level determi-
nations leach instead in aqua regia (1 + 1) for 1 h prior to use. A1.3 Remember when pelforming trace analyses that any
solution or any equipment that is left open to the air can
become contaminated by the trace metals from atmospheric
16 Parafilm available from Fisher Scientific Co., Fairlawn, NJ, has been found particles. Care should be taken to prevent this from happening
satisfactory. by liberal use of plastic film. 16

Copyright ASTM International 13

Provided by IHS under license with ASTM Sold lo:PUBLlC.RESOURCE.ORG, W1218734
, No reproduction or networking permUted wilhout license from IHS 20121111021:52:47 GMT
 ASTM Logo
Removed
3559-03

A2. DETERMINATION OF HANGING MERCURY DROP AREA

A2.1 Place 4 mL of water into a 5-mL beaker and submerge 20 13.5462

a hanging mercury drop electrode (HMDE) capillary tip under 21 15.5438
22 13.5413
the surface of water. 23 13.5389
24 13.5364
A2.2 Extrude and dislodge 10 drops from HMDE into the 25 13.5340
5-mL beaker. 26 13.5315
27 13.5291
28 12.5266
A2.3 Decant the water and rinse with three 3-mL portions 29 13.5242
of acetone. 30 13.5217

A2.4 Obtain the weight of the beaker plus the mercury A2.6.3 Area of Hg drop = 4 'IT i
(3WH 4 'TI'PHg) 2/3

(WT )·
A2.7 Sample Calculation:
A2.5 Discard the mercury and obtain the weight of the WHg = 0.006228 for 1 Hg drop
beaker (WB ). (3)(0.006228 g)
Area of 1 Hg drop = 4 'IT ( 3) 2/3
A2.6 Calculate the mercury drop area (assuming a spherical 4'IT 0.0135438 g/mm
drop) as follows: = 12.56636 (1.0978 X 10 -I) 2/3
A2.6.1 = 2.881 mm 2.
WHg = (WT - WB)/l0 = weight of a single mercury drop.
A2.6.2 Obtain the density of mercury at room temperature, A2.8 Tabulated here are typical surface areas for each small
pHg, from the following table 17. If the room temperature used vertical division on a manually operated hanging mercury drop
is not listed here, find the density at the correct temperature electrode. 9
from a suitable reference source. Surface Area, mm 2 Reading, Small Vertical Division
Temperature,O C pHg, g/mL17 1.42 2
1.86 3
2.23 4
2.60 5
17 Reproduction from Handbook of ChemistJy and Physics, 44th Edition, The 2.92 6
Chemical Rubber Publishing Co., Cleveland, OH, 1963, p. 2199. 3.23 7

APPENDIXES

(N onmandatory Information)

Xl. THE SENSITIVITY OF DIFFERENTIAL PULSE ANODIC STRIPPING VOLTAMMETRY

XU The sensitivity of DPASV is dependent upon a time. The use of deposition times as long as 30 min has been
number of factors and thus can be varied if so desired. The reported in the literature when detection limits below 0.1 /-tglL
experimental conditions chosen for this work are those which (ppb) were required. When sensitivity such as this is required,
are best suited for the concentration range covered by the the additional time required is well spent.
samples which were analyzed. Experimental settings that can
be varied to improve the sensitivity include: hanging mercury X1.4 Another procedure to improve the sensitivity is to use
drop electrode size, deposition time, modulation amplitude, larger pulse modulation amplitudes. For typical differential
instrument gain, and stirring rate. pulse polarographic instrumentation, 8 the pulse modulation
amplitude may be increased to 50 mV with no significant loss
X1.2 The size of the mercury drop can be decreased to of resolution.
increase the sensitivity of this method. The recommended
mercury droplet size is six divisions (see Annex A2), but X1.5 One may also change the gain on the instrument to
mercury droplets of eight divisions can be used. 9 Droplets improve the sensitivity. The highest gain that can be used in
larger than this are not practical because they are very easily this experiment gives a current of 0.1 /-tNin. This gain can be
dislodged from the capillary. increased by a factor of 2 to 5, and sensitivity is increased by
a corresponding amount. When using the higher gain on the
Xl.3 The sensitivity of DPASV is variable over a wide instrument, it should be noted that the current at the beginning
range by increasing the deposition time. A deposition time of 2 of the deposition may be well above the limiting value and the
min is chosen for the concentration range investigated because instrument overload light will be on. This does not mean the
this time gives adequate sensitivity in a reasonable length of instrument is malfunctioning and the experiment can be

Copyright ASTM International 14

Provided by IHS under license with ASTM Sold to:PUBLlC.RESOURCE.ORG, W1218734
No reproduction or networking permitted without license from IHS 2012/1/1021:52:47 GMT
 ASTM Logo Removed
l 559-03
allowed to proceed as planned. It may also be necessary to use Xl.7 The variable sensitivity is one of the major advan-
offset to bring the curves on scale because, without the offset, tages of differential pulse anodic stripping voltammetry. The
the d-c current may be larger than the maximum current which sensitivity can be conveniently increased or decreased to meet
the recorder will accept at that particular gain setting. the needs of the experiment by changing the deposition time,
mercury droplet size, instrument gain, stirring rate, and pulse
X1.6 The final procedure that increases the sensitivity is to
modulation amplitude. However, no factor that affects the
increase the rate of stirring during the deposition step. The
sensitivity should be changed between the time the sample and
maximum stirring rate that is practical depends on the kind of
stirrer and the geometry of the cell. spiked sample are analyzed.

X2. METHODS FOR REMOVING OXYGEN FROM NITROGEN GAS

X2.l Remove oxygen from nitrogen by anyone of a variety technique because of the critical dependence of the scrubbing
of techniques. It is recommended that the nitrogen be scrubbed efficiency on the acid concentration. Note that several com-
with 0.1 M chromous chloride in 2.4 M Hel containing mercial systems are available for removing oxygen at room
amalgamated zinc 18 with a 0.8 to 3.2-mm pore size 19 or be temperature 20 or at high temperatures. 21
scrubbed with vanadous chloride, 18 which is a less suitable
20 One suitable system is available from Applied Science Laboratories, State
College, PA. It removes oxygen at room temperature with a Dow gas purifier
18 Meites, L., Polarographic Techniques, 2nd edition, Interscience Publishers, preceded by a Hydro-Purge Unit.
New York, NY, 1967, pp. 89-90. 21 Hewlett-Packard, Avondale, PA, Model 19046A gas purifier uses a furnace at
19 Amalgamated zinc with a pore size of 0.8 to 3.2 mm for a Jones reductor 475°C that is packed with copper, and SupeIco (Bellefonte, PAl Model 02-2315 gas
(Fisher Scientific Co., Fairlawn, NJ) has been found satisfactory. purifier uses a furnace at 600°C containing a special catalytic converter.

X3. CHEMICAL MATRIX MODIFIERS FOR LEAD DETERMINATIONS USING GRAPHITE FURNACE
SPECTROPHOTOMETRY

X3.l The determination of lead using graphite furnace used. Table X3.1 is a summary of the most commonly used
spectrophotometry may require the use of a chemical matrix modifiers.
modifier. Numerous chemical modifiers have been reportedly

TABLE X3.1 Lead Chemical Matrix Modifiers

Matrix Modifier Concentration Matrix
Lanthanum nitrate A 1 mL= 50 mg La sulfate
Phosphoric acid B 1% any
Ammonium phosphate e 1% any
Reduced palladium D 50 to 1000 ppm any
A Refer to Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-
020, U.S. Environmental Protection Agency, Cincinnati, OH, 1979.
B Refer to Test Methods for Evaluating Solid Waste, SW-846, Third edition, U.S.
Environmental Protection Agency, Washington, DC, 1986.
e Refer to Welz B., Atomic Absorption Spectrometry, Second edition, VCH
Publishers, Deerfield Beach, FL, 1985, p. 209.
D Refer to Rettberg T. M., and Beach, L. M., "Peak Profile Characteristics in the
Presence of Palladium for Graphite Furnace Atomic Absorption Spectroscopy,"
Journal of Analytical Atomic Spectrometry, Vol. 4, July 1989.

X4. VOLTAMMOGRAM

X4.l The voltammogram shown in Fig. X4.1 gives typical droplet with a 2.9-mm2 area for 2 min with stirring plus 30 s
stripping curve shapes, peak potentials, and sensitivities (in [.LA without stirring.
per 5 [.LglL) for cadmium and lead deposited into a mercury

Copyright ASTM International 15

Provided by IHS under license with ASTM Sold lo:PUBLlC.RESOURCE.ORG, W1218734
No reproduction or networking permiUed without license from IHS 2012/1/1021:52:47 GMT
 ASTM Logo
Removed
03559-03

DIFFERENTIAL PULSE ANo.DIC STRIPPING

Vo.LTAMMETRY o.F 5 ppb Cd and Pb IN
0..2 M AMMo.NIUM CITRATE, pH 3

A = BLANK CURVE
B = SAMPLE CURVE

i
SIGNAL

o..lo.lj.lA/5j.1g/L Cd /0050~A/5~9/L Pb

-0.9 -0.8 -0.7 -0.6 -0..5 -0..4 -0.3 -0.2

Po.TENTIAL [E vs SCE]
FIG. X4.1 Differential Pulse Anodic Stripping Voltammetry

SUMMARY OF CHANGES

This section identifies the location of selected changes to these test methods that have been incorporated since
the last issue. For the convenience of the user, Committee D19 has highlighted those changes that may impact
the use of these test methods. This section may also include descriptions of the changes or reasons for the
changes, or both.

(1) The QC sections were added to the test method. (2) Sections 15.4,25.4,37.4, and 47.3 were added.

ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed evel}' five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, at the address shown below.

This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or service@astm.org (e-mail); or through the ASTM website
(www.astm.org).

CopyrIght ASTM International 16

ProvIded by IHS under license with ASTM Sold lo:PUBLlC.RESOURCE.ORG, W1218734
No reproduction or networking permitted without license from IHS 2012/1/1021 :52:47 GMT