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TABLE OF CONTENTS

1.0 INTRODUCTION .................................................................................................. 1

2.0 ACRONYMS......................................................................................................... 1
3.0 DEFINITIONS ....................................................................................................... 2
4.0 PROGRAM ROLES AND RESPONSIBILITIES................................................... 8
5.0 PERSONNEL TRAINING ..................................................................................... 9
6.0 STANDARDS AND STANDARD SOLUTIONS ................................................. 11
7.0 SAMPLING MEDIA ............................................................................................ 13
8.0 EQUIPMENT, INSTRUMENTATION, AND ENVIRONMENTAL ROOMS ......... 13
9.0 ANALYTICAL METHODS .................................................................................. 15
10.0 STANDARD OPERATING PROCEDURES ....................................................... 18
11.0 ANALYTICAL QUANTITATION......................................................................... 20
12.0 QUALITY CONTROL ......................................................................................... 25
13.0 SAMPLE MANAGEMENT.................................................................................. 31
14.0 DATA MANAGEMENT ...................................................................................... 33
15.0 QUALITY CONTROL REPORTS ....................................................................... 41
16.0 CONFIDENTIAL INFORMATION....................................................................... 41
17.0 HAZARDOUS MATERIAL AND WASTE MANAGEMENT................................ 41
18.0 REFERENCES ................................................................................................... 42
19.0 REVISION HISTORY ......................................................................................... 43

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Laboratory Quality Control Manual

1.0 INTRODUCTION

The purpose of this Laboratory Quality Control Manual is to detail the quality system
policies and procedures that ensure consistent validation of the data generated by the
Northern Laboratory Branch (NLB). It is meant to be used in conjunction with system
wide policies and procedures, including California Air Resources Board’s (CARB)
Quality Assurance (QA) Manual, federal and State regulations, and laboratory Standard
Operating Procedures (SOP) which contain method specific details to ensure accuracy,
precision, and completeness of both the individual results and the supporting quality
control (QC) measurements, resulting in a scientifically defensible program.

NLB provides analytical services to support regulatory and non-regulatory programs

requiring data quality objectives (DQO) that meet a variety of client requirements.
Clients may include CARB’s Primary Quality Assurance Organization, other CARB
divisions, federal and State agencies, and local air pollution control/air quality
management districts.

2.0 ACRONYMS

% RSD – Percent Relative Standard Deviation

ACS - American Chemical Society
AD – Absolute Difference
AQDA – Air Quality Data Action
AQS – Air Quality System
AQSB – Air Quality Surveillance Branch
ASTM International – American Standards for Testing and Materials International
CAN – Corrective Action Notification
CARB – California Air Resources Board
CCV – Continuing Calibration Verification
CFR – Code of Federal Regulations
COC – Chain of Custody
DOC – Demonstration of Capabilities
DQO – Data Quality Objective
EQL – Estimated Quantitation Limit
IDOC – Initial Demonstration of Capabilities
IDL – Instrument Detection Limit
ILS – Inorganic Laboratory Section
LIMS – Laboratory Information Management System
LOQ – Limit of Quantitation
LSS – Laboratory Support Section
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MDL – Method Detection Limit

MLD – Monitoring and Laboratory Division
NIOSH – National Institute of Occupational Safety and Health
NIST – National Institute of Standards and Technology
NLB – Northern Laboratory Branch
OLS – Organics Laboratory Section
PD – Percent Difference
PFTE - Polytetrafluoroethylene
QA – Quality Assurance
QC – Quality Control
QCM – Quality Control Manual
QMB – Quality Management Branch
RH – Relative Humidity
RL – Reporting Limit
RPD – Relative Percent Difference
SA – Standard Addition
SAS – Special Analysis Section
SOP – Standard Operating Procedure
SRM – Standard Reference Material
U.S. EPA – United States Environmental Protection Agency

3.0 DEFINITIONS

ACCURACY – the degree of agreement of a measured value with the true or expected
value of the quantity of concern.

BATCH – an analytical batch is a set of prepared samples (i.e., extracts) analyzed

together as a group in an uninterrupted sequence. A preparation (extraction) batch is a
set of samples which is processed all in one group using the same equipment and
reagents.

BIAS – a systematic or persistent distortion of a measurement process which causes

error in one direction.

BLANK – a sample that has not been exposed to the sample stream in order to monitor
contamination during sampling, transport, storage, extraction, and/or analysis. The
blank is subjected to the usual analytical and measurement process to establish a zero
baseline or background value. The different types of blanks used include:

METHOD BLANK or LABORATORY BLANK – used to monitor the laboratory

preparation and analysis systems for interferences and contamination from
glassware, reagents, sample manipulations, and the general laboratory
environment. This blank is an analyte-free matrix to which all reagents are added in
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the same volumes or proportions as used in sample processing, and which is taken
through the entire sample preparation and analysis process.

INSTRUMENT BLANK or SYSTEM BLANK – used to monitor the cleanliness of the

instrument used for sample analyses. Instrument blanks consist of the gas, solvent,
or acid solution used during sample analyses. System blanks will be specified in
SOPs as to type and frequency.

FIELD BLANK – used to monitor processes undertaken in the field. In some cases,
sampling media will be installed onto monitoring equipment then removed without
turning on the equipment then shipped back to the laboratory with other samples.
This blank indicates any contamination from shipping and handling in the field.

SOLVENT BLANK – a sample consisting of reagent(s), without the target analyte or

sample matrix, introduced into the analytical procedure at the appropriate point and
carried through all subsequent steps to determine the contribution of the reagents
and of the involved analytical steps.

TRIP BLANK – used to assess any contamination attributable to shipping consisting

of a sample of analyte-free media in the same type of container that is required for
the analytical test, taken from the laboratory (or other point of origination) to the
sampling site and returned to the laboratory unopened.

CALIBRATION – the act of evaluating and adjusting the precision and accuracy of
measurement equipment using known values (standards).

CHAIN OF CUSTODY (COC) – to maintain the identity and integrity of a sample by

providing documentation of the control, transfer, analysis, and disposition of the sample.

CHECK STANDARD – a midpoint calibration standard analyzed concurrently with test

samples to confirm the stability of the instrument calibration. See CONTINUING
CALIBRATION VERIFICATION (CCV) STANDARD.

COEFFICIENT OF DETERMINATION – typically expressed as ‘r2,’ measures the

proportion of the variance (fluctuation) of one variable (y) that is predictable from the
other variable (x) such that 0 ≤ r2 ≤ 1, and denotes the strength of the linear association
between x and y.

COLLOCATED SAMPLE – a sample used to assess total precision (sampling and

analysis) which is located within a specified radius of the primary sampler. The
collocated sampler must be identical in configuration and operation to the primary
sampler. The collocated sample is processed identically to the primary sample.
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CONTINUING CALIBRATION VERIFICATION STANDARD – a midpoint calibration

standard analyzed concurrently with test samples to confirm the stability of the
instrument calibration. See CHECK STANDARD.

CONTROL CHART – a graphical plot of test results with respect to time or sequence of
measurement that may be used to show that the system monitored is within expected
limits, to signal systematic departures, and to identify inconsistencies in precision.

CONTROL LIMIT – the range of values shown on a control chart beyond which it is
highly improbable that a point could lie while the system remains in a state of statistical
control. Quality control parameters must not exceed this range for satisfactory method
performance.

CONTROL STANDARD – a material of known composition obtained (when possible)

from a source other than that of the primary calibration standards that is analyzed to
verify the calibration.

CORRECTIVE ACTION – an action taken to eliminate the causes of an existing non-

conformity or other undesirable situation and to prevent a recurrence.

CORRELATION COEFFICIENT – typically expressed as ‘r,’ it measures the linear

relationship between two variables, with a value range of -1 to 1. A value close to 1
indicates there is a strong positive linear correlation between two variables; that is,
when one variable increases so does the other. A value close to -1 indicates a negative
linear correlation; that is, when one variable increases the other decreases. A value
close to 0 indicates a non-linear, or random, correlation.

DATA QUALITY OBJECTIVES – performance and acceptance criteria that clarify study
objectives, define the appropriate type of data, and specify tolerable levels of potential
decision errors that will be used as the basis for establishing the quality and quantity of
data needed to support decisions. This includes completeness, method detection limit
(MDL), accuracy and precision.

DUPLICATE – two aliquots taken from and representative of the same sample or
product and carried through all steps of the sampling and analytical procedures in an
identical manner. Duplicate samples are used to assess variance of the total method
including sampling and analysis.

ENVIRONMENTAL CHAMBER – an enclosure with controlled temperature and

humidity. An environmental conditioning chamber is used to bring samples to a similar
state prior to analysis.
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ESTIMATED QUANTITATION LIMIT (EQL) - lowest concentration that can be reliably

achieved within specified limits of precision and accuracy during routine laboratory
operating conditions. In general, EQLs are approximately 5 to 10 times the MDL.

INSTRUMENT DETECTION LIMIT (IDL) – the smallest signal, or lowest concentration,

that can be distinguished from background noise by a particular instrument. The IDL
should always be below the MDL, and is not used for compliance data reporting, but
may be used for statistical data analysis and comparing the attributes of different
instruments.

INTERFERENCE – a substance that is present that can cause a systematic error in

measurement in the sample being analyzed. Examples: impurities in the
purging/carrier gas, elevated baselines from solvents, reagents, glassware, sampling
media, and other sample processing hardware that may cause misinterpretation of the
data.

INTERNAL STANDARD – internal standards are compounds which analytically behave

similarly to the target analytes. Internal standards are compounds not found in the
sample that are added to quantitate results, and correct for variability.

LIMIT OF QUANTITATION (LOQ) – the minimum concentration or amount of an analyte

that a method can measure with a specified degree of confidence. The LOQ is equal to
five times the standard deviation of the replicate analyses from the MDL
determination/verification. LOQ is analyte and instrument specific.

LABORATORY INFORMATION MANAGEMENT SYSTEM (LIMS) – a database used to

record and store sample information and analytical results as well as perform workflow
and data tracking and reporting.

METHOD DETECTION LIMIT – the minimum concentration of a substance that can be

measured by a single measurement and reported with 99 percent confidence that the
analyte concentration is greater than zero and statistically different from a blank. It is
determined from replicate analyses of samples containing a known concentration of the
analyte in a specified sample matrix, which may include the sampling media

NATIONAL INSTITUTE OF STANDARDS AND TECHNOLOGY (NIST) – an agency of

the U.S. Department of Commerce. The Material Measurement Laboratory is a
metrology laboratory within NIST that serves as the national reference laboratory for
measurements in the chemical, biological and material sciences. NIST supplies
industry, academia, government, and other users with Standard Reference Material
(SRM).
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PRECISION – the degree of mutual agreement characteristic of independent

measurements as the result of repeated application of the process under specified
conditions. The scatter of the values is a measure of the precision; the less scatter, the
higher the precision.

QUALITY ASSESSMENT – the overall system of activities whose purpose is to provide

assurance that the quality control activities are done effectively. It involves a continuing
evaluation of performance of the production system and the quality of the products
produced.

QUALITY ASSURANCE – a system of activities whose purpose is to provide a product

or service the assurance that it meets defined standards of quality at a stated level of
confidence. It consists of two separate but related activities, quality control and quality
assessment.

QUALITY CONTROL – the overall system of activities whose purpose is to control the
quality of a product or service so that it meets the needs of users. The aim is to provide
quality that is satisfactory, adequate, dependable, and economical.

REPLICATE – an additional analysis of the same sample or sample extract. The

sample extract used for replicate analyses must be chosen at random. Replicate
analyses results are used to evaluate analytical precision but not the precision of
sampling, preservation, or storage internal to the laboratory.

REPORTING LIMIT (RL) – a number which data is not typically reported below. The RL
may or may not be statistically determined, and may be established by regulatory
requirements or in conjunction with client or program needs. The RL is equivalent to or
greater than the LOQ.

SAMPLE CONDITIONING – to hold samples in an environmental chamber or

environmentally controlled room at specified temperature and humidity for a specified
time prior to analysis.

SAMPLE MEDIA – air sampling is done to capture a sample of the contaminants

present within the air. The container or substrate used to capture the air sample is
the sample media. Membrane filters made of cellulose, glass fiber, quartz fiber,
Teflon or polytetrafluoroethylene (PFTE), etc., sorbent tubes containing charcoal,
silica gel, tenax, XAD, etc., and containers such as flasks, canisters (summa
polished or silco lined), tedlar bags, etc. are all examples of sample media.

SPIKE – a quality control sample employed to evaluate the accuracy of a measurement.

The spike is prepared by adding a known amount of the target analyte(s) to an aliquot of
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the sample. The recovery of a spike provides an indication of the efficiency of the
analytical procedure. Spikes can be added at any point in the sampling and analytical
process such as field, laboratory, matrix, trip, etc.

STANDARD (calibration or control standard) – a substance or material with properties

believed to be traceable with sufficient accuracy to permit its use to evaluate the same
property of another. It is a solution or substance commonly prepared by the analyst to
establish a calibration curve or the analytical response function of an instrument.

STANDARD ADDITION (SA) – a method in which small increments of an analyte under

measurement are added to a sample under test to establish a response function, or to
determine by extrapolation the amount of the analyte originally present in the test
sample.

STANDARD DEVIATION – the amount of variability or dispersion around the mean. A

low standard deviation indicates that the data points tend to be very close to the mean;
high standard deviation indicates that the data points are spread out over a large range
of values.

STANDARD OPERATING PROCEDURE – a set of written instructions that document a

routine or repetitive activity. The development and use of SOPs are an integral part of a
successful quality system as it provides individuals with the information to perform a job
properly, and facilitates consistency in the quality and integrity of a product or end-
result.

STANDARD REFERENCE MATERIAL – certified materials with specific characteristics

or component content, used as calibration standards for measuring equipment and
procedures, quality control benchmarks for industrial processes, and experimental
control standards.

SURROGATE – a substance with properties that mimic the analyte of interest. It is

unlikely to be found in environmental samples and is added for quality control
purposes.

TRACEABILITY – the ability to trace the source of uncertainty of a measurement or a

measured value through an unbroken chain of comparisons.

VALIDATION – the process by which a sample, measurement method, or a piece of

data is deemed useful for a specified purpose.
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4.0 PROGRAM ROLES AND RESPONSIBILITIES

This section describes the roles and responsibilities for the review, validation, and
approval of all individual sample results and the corresponding QC results, hereafter
referred to as "data."

4.1 The laboratory technicians are responsible for:

4.1.1 Sample control

4.1.2 Shipment and receipt
4.1.3 Sample log-in and evaluation
4.1.4 Sample media preparation
4.1.5 Logbooks
4.1.6 Other laboratory support functions

4.2 The analyst generating the data is responsible for:

4.2.1 All QC checks as described in the SOPs

4.2.2 Initial data validation and raw data review
4.2.3 Data transfer to the database (e.g., LIMS)
4.2.4 Preparing the data report
4.2.5 Logbooks
4.2.6 Documenting any corrective actions
4.2.7 Peer review of data reports generated by other analysts
4.2.8 Documenting laboratory equipment and instrument maintenance
4.2.9 Performing duties of the laboratory technicians as needed

4.3 The QA/QC Officer is responsible for:

4.3.1 Data management oversight

4.3.2 Quality Control Manual (QCM)
4.3.3 QC report oversight
4.3.4 Method modification review
4.3.5 Method evaluations
4.3.6 SOP and logbook document management

4.4 The LIMS administrator is responsible for:

4.4.1 LIMS development and management

4.4.2 Analytical instrument to LIMS communication
4.4.3 Data security
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4.5 Management is to ensure the analyst has provided complete and accurate
data, and the report generated is correct prior to approval. Data must be
reviewed and approved by management before being made available to
clients. Management is responsible for reviewing logbooks.

4.6 Management designates staff to prepare QC reports. These reports shall

summarize QC activities associated with data for each reporting period (i.e.,
monthly, quarterly, annually). The following items are required for QC
reports:

4.6.1 Summary of QC sample results

4.6.2 QC anomalies and corrective actions
4.6.3 MDL determinations
4.6.4 Calibration range verifications
4.6.5 Audit findings and any actions taken as a result
4.6.6 Deviations from SOP
4.6.7 Method modifications
4.6.8 SOP revisions

4.7 Designated, trained staff submits ambient data to United States

Environmental Protection Agency (U.S. EPA) Air Quality System (AQS)
database after review/approval. Data reports generated by Special Analysis
Section (SAS) are submitted directly to clients after review/approval.

4.8 The annual QC report for all NLB laboratories is submitted by management to
the NLB Chief for review and approval. Once approved, the NLB Chief
provides a copy of the annual QC report to the Chief of the Quality
Management Branch (QMB).

4.9 DQOs should be reviewed by management to confirm that procedures and

criteria continue to meet the needs of the program and the clients.

4.10 The Monitoring and Laboratory Division (MLD) organization chart can be
accessed by following this link: http://www.arb.ca.gov/html/org/mld.pdf.

5.0 PERSONNEL TRAINING

This section describes the training and documentation requirements for laboratory staff.

5.1 Management is responsible for the implementation of staff training including

training assignments and oversight, training evaluation and verification, and
training documentation. Staff is responsible for completing training within the
specified timeframe, submitting training documentation, maintaining
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knowledge of procedures and methods performed, and providing in-house

training to staff as directed by management. Staff will not perform any
procedure, inspection, or method without supervision until all applicable
training has been completed and competency demonstrated; supervisor
approval is required. Staff training requirements include:

5.1.1 Familiarization with all work related documents, QCM, SOPs, work
instructions, manuals, and regulations
5.1.2 Documentation of educational qualifications and work experience
5.1.3 Observing demonstration of procedure or method by designated
trainer
5.1.4 Performance of procedure or method under observation of
designated trainer
5.1.5 Evaluation of procedure or method performance documented and
submitted to management
5.1.6 Repeat 5.1.3 through 5.1.5 until competency has been
demonstrated
5.1.7 Training records maintained by management

5.2 Staff performance for specific procedures or methods is verified by

measurement against a defined performance standard. These assessment
tools may include:

5.2.1 Written evaluation (e.g., training checklist)

5.2.2 Observation of procedure or method
5.2.3 Testing blind QC samples
5.2.4 Testing known or previously analyzed samples

5.3 Training verification documentation includes any of the following:

5.3.1 Completion of training checklists

5.3.2 Completion of procedure or method with supporting performance
evaluation such as results from QC samples (e.g., blind, double-
blind), duplicate testing, and/or sample re-analyses
5.3.3 Vendor training certificates
5.3.4 Safety meeting participation
5.3.5 Written evaluations
5.3.6 Acknowledgement of reading QCM, SOPs, or work instructions

5.4 Staff will be retrained and retraining verified whenever significant changes
occur in policies, values, goals, procedures, methods, processes,
instrumentation, or when staff have not performed the method on a routine
basis and as determined by management.
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5.5 Example Training Checklist:

Staff: Section:
Education:
Instrument Experience:
Vendor Training:
SOP Analyst Date Trainer Date Sup Date
MLD005
MLD068
SAS012
Comments:

6.0 STANDARDS AND STANDARD SOLUTIONS

NIST traceable materials, when available, must be the primary standard material to
which all working standards are referenced. NLB works with NIST on the development
and procurement of NIST standards. All reagents and chemicals must meet the
appropriate reagent grade as detailed in the method’s SOP. Dates of receipt for
chemicals must be noted on the container labels. In general, chemicals should not be
used or kept past the manufacturer's recommended date of expiration unless otherwise
approved by management. If chemical use is approved by management past the
expiration date, this information must be included in the QC Report.

6.1 Standard Solutions

Stock, standard, or neat solutions are concentrated solutions that are diluted
to make working solutions. They are to be made from chemicals of the
highest purity available (commercially prepared NIST certified or NIST
traceable standards are preferred).

6.1.1 All solutions prepared from liquid or solid standards in the

laboratory should be labeled to identify standard element(s) and/or
species, concentration level, preparation date, expiration date, and
the preparer's initials.

6.1.2 Stock solutions prepared by the manufacturer should be labeled

with the date the solutions were received by the laboratory and first
opened. The expiration dates should be noted for each solution.
Expiration dates of working standards must not exceed the
expiration dates of the stock solutions from which they were
prepared.
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6.1.3 All stock solutions and working standards must be stored per
manufacturer’s instructions (refrigerated, dark glass container, etc.)

6.2 Standard Gas Cylinders

Vendor supplied gas cylinders used for calibration of instruments should be

obtained from NIST, NIST traceable or verified within the laboratory against a
NIST standard. Where NIST or NIST traceable standards are not available,
other reference standards may be used to assign concentrations (for example
U.S. EPA protocol gas cylinders). Cylinders must adhere to the purity and
pressure requirements of the analysis, as detailed in the method’s SOP.

6.3 Control Standards

The control material should be from a source other than the SRM when
available. NIST traceability is preferred. Documentation should confirm the
control material is from a secondary source.

6.4 Calibration Weights

Calibration weights must be American Standards for Testing and Materials

International (ASTM International) Class 1 or Class S, and certified as
traceable to NIST mass standards. Weights must be stored and maintained
with absolute attention to following the handling instructions provided by the
manufacturer. If the weights are mishandled at any time, or if the weights
appear to be deteriorating due to age and normal wear, the weights must be
replaced. Weights must be verified by an outside source annually. Two sets
of weights are needed, one set as a working standard and one set as a
primary standard. The working standards are used during daily
measurements at routine intervals to verify the weighing session is within QC
acceptance criteria; the primary standards are used to check the calibration of
the analytical microbalance quarterly. Results of all annual verifications and
quarterly checks must be documented in the QC reports.

6.5 Reagents and Laboratory Water

All reagents used by laboratory must be the appropriate reagent grade for the
specific method. The source and purity of the reagent used must be clearly
identified in the method’s SOP.

The purified water (deionized or Nanopure) used by NLB must be of

Type I, as identified by ASTM International. Specifically, the resistance of the
deionized water must be greater than 16 megaohms as indicated by the
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continuous read output of the purifying system. A resistance log should be

maintained for each purification unit that includes resistance readings and
dates of cartridge replacement. The analyst is responsible for ensuring
proper maintenance, including filter replacements, are performed.

7.0 SAMPLING MEDIA

In general, the analyst must refer to the specific SOP guidelines for treatment,
conditioning, inspection, shipping, and overall handling requirements prior to beginning
any task concerning sampling media. Individual SOPs will describe acceptance testing
procedures for new media, cleanliness criteria for reusable media (i.e., canisters), and
indicators of contamination.

If the analyst notices that sampling media have experienced a change or possess a
previously unidentified condition, such as an inherent contamination, which could affect
the quality or integrity of the results, management must be notified immediately.
Management must evaluate the situation to determine if action is necessary when
corrective action is not specified in the SOP. If an action is deemed necessary,
management must verify that the appropriate action has been taken and documented
by the analyst.

Sample media storage times must be identified and documented for each media type. If
sample media stored beyond the specified storage times are analyzed, data must be
flagged appropriately and documented in the QC report.

8.0 EQUIPMENT, INSTRUMENTATION, AND ENVIRONMENTAL ROOMS

Equipment, instrumentation, apparatus, and materials shall meet or exceed the

requirements described in the SOP or as provided below for certain categories to
ensure good laboratory practices and minimize contamination.

Equipment and instrument maintenance shall occur as per SOPs, laboratory service
contracts, and manufacturer’s recommendations, and shall be recorded in a logbook.
The analyst is responsible for ensuring that the instruments are maintained and
calibrated according to the SOP and manufacturer’s recommendations.

8.1 Glassware

All laboratory glassware should be borosilicate Class A, unless an SOP

specifies otherwise. Any glassware which is chipped, cracked, becomes
permanently etched, or has degraded, shall be disposed in a container
marked "GLASS." Treatment and cleaning of glassware must follow
individual method requirements or an approved SOP.
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8.2 Pipettes and Other Measuring Devices

All electronic pipette units must be calibrated at least annually by an outside

vendor.

Automatic dispensing units, such as the Autoblock and other reagent

dispensers, should be calibrated according to manufacturer’s
recommendations.

8.3 Balances

All balances and microbalances must be calibrated at least annually. All

calibration and check masses must be the appropriate ASTM International
class (e.g., S, 1, etc.) and must be certified by an outside vendor at least
annually. Refer to Section 6.4 (Calibration Weights).

8.4 Mass Flow Controllers

All mass flow controllers must be calibrated or have calibration verified at

least annually against NIST traceable standards, where feasible, by an
outside vendor or by CARB’s Standards Laboratory.

8.5 Refrigerators, Freezers, and Ovens

All laboratory refrigerators, freezers, and ovens shall be of a size and material
suitable for their intended purpose. All laboratory refrigerators, freezers, and
ovens shall be used for laboratory purposes only (samples, standards,
sample media, etc.). No food for personal consumption is allowed in
laboratory refrigerators, freezers, and ovens. This equipment must be
maintained per manufacturer’s recommendations. Temperatures of
refrigerators, freezers, and ovens that contain samples or sample extracts
should be recorded at a frequency specified in the SOP. If the temperature is
out of range, management should be notified and corrective action should be
taken.

8.6 Environmentally Controlled Rooms and Chambers

Environmentally-controlled rooms and chambers must be constructed in

accordance with applicable regulations, methods, and/or guidance. All such
rooms and chambers must be of the appropriate size and materials, and
control systems must meet the prescribed standards.
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The analyst is responsible for verifying, recording, and ensuring the room or
chamber relative humidity (RH) and temperature are in accordance with U.S.
EPA or program requirements as specified in SOPs.

Equilibration malfunctions, discrepancies, and maintenance should be

recorded in the logbook.

9.0 ANALYTICAL METHODS

In general, the analytical methods used by NLB are: 1) developed within NLB, 2) ASTM
International, U.S. EPA, or National Institute of Occupational Safety and Health
(NIOSH) methods; or 3) other available methods. Acceptance testing is required for all
methods used by NLB as per section 9.3.

ASTM International, U.S. EPA, and NIOSH methods should be used whenever
possible. These methods have been validated following a collaborative test process
and only require the verification of laboratory performance prior to acceptance, as
described in section 9.3. Other analytical methods used by NLB must be validated and
accepted prior to laboratory implementation (sections 9.2 and 9.3).

In the event the laboratory performs a non-routine analysis, a complete description of

the analytical parameters must be included in the data report.

9.1 Method Development

Before developing a new method, establish the purpose for which the results
will be used, define the application, and scope of the method. The
acceptance criteria for the performance of the method need to be established
and may define or restrict the choice of techniques. Document all decisions
and activities related to method development.

9.1.1 Define the performance parameters and acceptance criteria.

9.1.2 Establish DQOs based on the quality of data required for the
program and the client.
9.1.3 Research available methods. Determine if there is an established
method that will meet the scope and DQO for the intended matrix or
if one can be modified to do so.
9.1.4 Evaluate safety hazards associated with the analyte, matrix,
reagents, etc., associated with the method. Determine if the safety
hazards pose an acceptable, manageable risk. If not, research if
this is a project that can be subcontracted to another experienced
laboratory.
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9.1.5 Select analytical technique. If the instrumentation or equipment

needed is not already available determine if purchasing it is
feasible.
9.1.6 Prepare cost proposals for management’s review and approval.
9.1.7 Order standards, testing materials, reagents, and supplies needed.
9.1.8 Conduct preliminary analyses and document all results and
observations.
9.1.9 Optimize method and document all procedures.
9.1.10 Perform stability studies. Determine sampling media stability,
sampling hold time, extraction hold time, analytical hold time, and
archive hold time for samples and extracts. Stability and hold time
studies should mimic the environmental conditions expected to be
encountered (temperature, sunlight, etc.).
9.1.11 Perform method validation as per section 9.2 and method
acceptance per section 9.3.

9.2 Method Validation

Method validation is the process of verifying that a method is fit for its
intended purpose (i.e., for use for solving a particular analytical problem or
identifying a particular analyte).

Analytical methods need to be validated or re-validated: 1) before their

introduction into routine use, and 2) whenever the conditions change (e.g., an
instrument with different characteristics or samples with a different matrix).

Validation will demonstrate that a laboratory procedure is robust, reliable, and

reproducible by personnel performing the test in that laboratory. A robust
method is one in which successful results are obtained a high percentage of
the time and few, if any, sample analyses need to be repeated. A reliable
method is one in which the obtained results are accurate and correctly reflect
the sample being tested. A reproducible method is one in which the same or
very similar results are obtained each time a sample is tested. All three
method qualities are important for techniques performed in laboratories.
(Taylor, John K., "Validation of Analytical Methods," Anal. Chem., 1983, Vol.
55, No. 6, pp. 600A-608A.)

Methods developed or modified by NLB must complete the validation criteria

given below. Management must approve the method validation findings
before method acceptance (9.3).

9.2.1 Obtain suitable reference material of known accuracy.

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9.2.2 Prepare standards over the desired concentration range, usually

extending from LOQ, EQL, etc. to expected high concentration of
the target analyte.
9.2.3 Determine instrument precision and accuracy. Instrument precision
is determined by replicate analyses of matrix-free test samples.
Instrument accuracy is determined by analysis of laboratory spikes.
9.2.4 Obtain test samples such as spiked media or SRM with known
concentrations that are similar in analyte concentration and sample
matrix.
9.2.5 Determine method precision by performing replicate analyses of
test samples including all sampling media and reagents specified in
the method.
9.2.6 Surrogates, additions of known compounds to evaluate analytical
efficiency, should be used only when the test matrix is not
adversely altered by such additions.
9.2.7 Field, trip, and laboratory blanks should be analyzed to evaluate the
matrix variations and the contamination possible due to sample
collection, transport, and laboratory preparation based on the
method requirements.
9.2.8 Stability must be determined for samples, standards, extracts to
determine hold times for extraction and analysis.

9.3 Method Acceptance

Prior to implementing NLB methods, management shall review the following:

9.3.1 All standards, reagents, sampling media, laboratory environmental

factors, and instrumental conditions are detailed in the method.
9.3.2 NIST standards, where available, are analyzed at least three times
at multiple concentration levels over the linear range, with a
correlation coefficient, r, of 0.98 or better. At a minimum, standard
concentration levels should be at the low, mid, and high points of
the linear range.
9.3.3 The analytical MDLs must be calculated and follow the equations
given in Section 11.0. A MDL is acceptable if it meets the data
quality objectives established by the client or regulatory program.
9.3.4 Verify laboratory precision and accuracy values were done correctly
if method development done in-house.
9.3.5 Confirm media background levels are less than the MDL.
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9.4 Method Development Documentation and Approval

9.4.1 Information and data supporting method development, validation,

and acceptance shall be summarized in a written report to
management.
9.4.2 The method development report shall be provided to QMB for
review and comment. The report shall include a final draft SOP.
9.4.3 After considering QMB’s comments, the method development
report is finalized and the associated SOP is approved by QMB.

9.5 Method and SOP Modifications

The review and approval process for method modification is provided in the
Northern Laboratory Branch Guidelines for Modifications to Methods and
Standard Operating Procedures (Appendix A).

10.0 STANDARD OPERATING PROCEDURES

An SOP is a document containing a set of detailed instructions for routine

methodologies followed by an organization. The development and use of SOPs provide
individuals with the information needed to perform a job properly and facilitate
consistency in the quality and integrity of the end product (e.g., data). Utilizing a
properly written SOP minimizes variation, promotes quality through consistent
implementation of a procedure, and improves comparability, credibility, and defensibility.

The SOP “Preparation of Northern Laboratory Branch’s Standard Operating

Procedures” (MLD076) documents the procedures to create and modify an SOP.

Sample analyses shall follow approved SOPs. Occasionally, deviations may be

necessary which shall require documentation and management approval prior to use.

Approved SOPs, and all prior revisions, must be stored and archived in Laboratory
Support Section (LSS). The effective dates of use must be clear for each SOP revision.
Management must verify that the SOPs are maintained and up-to-date.

A current list of CARB’s SOPs can be found at the following links:

http://www.arb.ca.gov/aaqm/sop/summary/summary.htm
http://www.arb.ca.gov/testmeth/cptm/sops.htm
http://www.arb.ca.gov/toxics/compwood/outreach/formaldehydesop.pdf

10.1 MLD076 documents all necessary elements for SOPs relating to any physical
or chemical analytical method. Some SOPs (e.g., administrative SOPs) may
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not require all elements and may be waived by management through the
SOP review and approval process.

10.2 SOP Changes

SOPs may be changed or updated as part of periodic SOP review or method

modification. All changes are documented in the SOP revision history. All
versions of SOPs are stored electronically on the NLB division drive.

10.2.1 SOP Review

SOPs should be reviewed on a periodic basis, but at least every

three years to ensure that the policy and procedures remain current
and appropriate.

10.2.2 Decimal Revision

Editorial corrections or administrative changes require the approval

by management. The approved changes are designated by the
"decimal" revision number (for example, Revision 1.0 replaced by
Revision 1.1).

10.2.3 Cardinal Revision

Method modifications shall follow the process described in the

Northern Laboratory Branch Guidelines for Modifications to
Methods and Standard Operating Procedures (Appendix A). The
approved modifications are designated by the "cardinal" revision
number (for example, Revision 1.0 replaced by Revision 2.0).

10.3 Procedural modifications or deviations to an approved SOP may be

necessary. In these cases, the changes to the SOP shall be approved by
management and documented. Management is responsible to communicate
SOP modifications and deviations to impacted staff.

10.3.1 One-time or temporary procedural modifications may not require a

SOP revision. The proposed change must include how the
modification will deviate from the SOP and what steps are taken to
ensure that data quality objectives, quality control, and quality
assurances are met. These modifications shall be documented in
the analytical report.
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10.3.2 Permanent modifications and deviations to SOPs will require a

formal addendum. The addendum will be incorporated in the SOP
at the next revision. Addendums and revised SOPs shall be
approved by management and retained by LSS.

10.3.3 All original signed hardcopy versions of SOPs and addendums will
be permanently archived in the NLB library maintained by LSS.
Electronically secure copies of the original signed SOPs and
addendums will be stored on the NLB shared drive.

11.0 ANALYTICAL QUANTITATION

Quantitation is an analytical procedure to accurately and precisely measure the

concentration of analytes in a sample. The MDL and LOQ are terms used to describe
sensitivity of analytical procedures. The general relationships between these limits, the
RL, and the EQL are shown in Figure 11.1.

Figure 11.1. General Analytical Quantitation Relationships

MDL/LOQ determinations and verifications follow the same procedures. MDL/LOQ

determinations are conducted when new methods are established, instruments are
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replaced, or other system changes occur. Subsequently, MDL/LOQ verifications should

be performed at least annually. As part of the verification, an LOQ is calculated and
compared to the RL.

MDLs and LOQs are analyte and instrument specific. A pooled MDL and LOQ
represents a collection of similar instruments for specific analytes.

Management approves MDL, LOQ, EQL, and RL determinations and verifications via
MDL data report packages (e.g., MDL calculations, run sequences, QC, etc.).

11.1 MDL Calculation

Unless specified differently in an SOP, the MDL should be calculated using

Equations (1), (2), (3), and (4).

Equation (1) MDL =t(n-1, 1-α=0.99) (s)

Equation (2) s= �s2

∑ni=1[xi -μ]2
Equation (3) s2 =
n-1

1
Equation (4) μ= n ∑ni=1 xi
Where:
n = number of replicates
t(n-1,1-α=0.99) = Student t-value at 99% one-tailed confidence level (1-α) for
n-1 degrees of freedom
s = standard deviation of the replicate analyses
s2 = variance of the replicate analyses
μ = mean of the replicate analyses
xi = value where i = 1 to n, is the analytical result in the final
laboratory instrument reporting units obtained from the
nth replicate

Use a minimum of seven replicates. When n = 7, t(6, 0.99) = 3.143. In this

case, the MDL is calculated as follows:
Equation (5) MDL = 3.143 (s)
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11.2 LOQ Calculation

The LOQ, the lower level concentration where measurements become

quantitatively meaningful, is calculated as:
Equation (6) LOQ=5 (s)

11.3 MDL Procedure

11.3.1 Calibrate with the same calibration range as for samples.

11.3.2 Estimate the MDL. In conjunction with the program’s DQO, an

estimated MDL is obtained by one or more of the following
methods:

11.3.2.1 Previously determined or verified MDL.

11.3.2.2 Concentration value that corresponds to an instrument
signal-to-noise ratio of no less than 2.5:1.
11.3.2.3 Instrument limitations.

11.3.3 Prepare an MDL spike in the appropriate matrix. An initial spike

concentration of one to five times the estimated MDL is
recommended. For methods with large numbers of analytes, one
standard may be chosen to represent a class or group of similar
analytes.

11.3.4 Analyze a minimum of seven replicates.

11.3.5 Determine the MDL using Equation 1.

11.3.6 MDL acceptance criteria:

11.3.6.1 MDL < spike concentration < 10 x MDL

11.3.7 Additional MDL criteria to consider:

11.3.7.1 MDL replicate spike recoveries should meet the DQO

specified for the method detailed in the SOP.

11.3.8 If MDL acceptance criteria is not met:

11.3.8.1 Prepare an MDL spike at a different concentration and

re-calculate the MDL.
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11.3.8.2 Repeat the MDL procedure until the MDL acceptance

criteria is met.
11.3.8.3 If the MDL acceptance criteria cannot be met, the MDL
obtained from the spike concentration that resulted in the
least deviation from the criteria may be used. This
situation must be documented and explained in the MDL
data package.

11.4 Pooled MDLs and LOQs

When multiple, similar instruments are used in a method, MDLs and LOQs
are established for each instrument and each analyte. The instrument with
the highest standard deviation of the replicate analyses (Equation 2) for each
analyte will be used to represent all of the instruments for the method. This
represents a pooled MDL and pooled LOQ and is calculated using Equation 1
and Equation 6, respectively.

11.5 Reporting Limit

11.5.1 The RL represents a point in which concentrations are typically not

reported below.

11.5.2 The RL should meet the following criteria:

11.5.2.1 RL is greater than or equal to the LOQ.

11.5.2.2 RL should be greater than or equal to the lowest
calibration standard.

11.5.3 Approaches to determine an RL may include one or more of the

following:

11.5.3.1 Background on matrix (i.e., blank study) and instrument

limitations.
11.5.3.2 Client and/or program needs.
11.5.3.3 Regulatory requirements.
11.5.3.4 Statistically determined.
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11.5.4 Once a method has an established RL, the RL should be verified

annually. During the annual MDL/LOQ verification procedure, the
LOQ is compared to the RL. The criteria are as follows:

11.5.4.1 If the RL is less than the LOQ, then the RL should be

raised to an appropriate limit.
11.5.4.2 If the RL is more than two times the LOQ, then
consideration should be given to lower the RL.
11.5.4.3
If neither of the above situations occur, then the RL may
remain unchanged.
11.6 Estimated Quantitation Limit

The EQL is used for specific programs in place of the RL and is

approximately 5 to10 times the MDL. The specific definition and use of EQLs
are defined in the program specific SOP.

11.7 Calibration

Multipoint calibrations should be performed on an annual, weekly, or daily

frequency. They must be performed prior to sample analysis. Linear and
non-linear calibrations may be used. Multipoint calibrations must have a
correlation coefficient, r, of '0.98' or greater.

Depending on DQOs and program needs, daily calibrations may be "single

point" or "multipoint" calibrations. Calibration standards should bracket the
majority of expected sample concentrations (i.e., analytical range).

Specific calibration requirements (e.g., calibration frequency, concentration

levels, linearity type, etc.) should be clearly outlined within each SOP.

11.8 Dilutions

Samples should be diluted when an analyte exceeds the highest calibration

standard by more than 10%. Typically, the individual sample is diluted so the
analyte in question is within the current method’s calibration curve. When
samples are diluted, the sample results and MDLs/LOQs are adjusted by the
dilution factor. RLs/EQLs are typically adjusted by the dilution factor as well
but may not be necessary for those programs where the RLs/EQLs are
determined by regulation and/or special projects and are orders of magnitude
greater than the corresponding LOQ.
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The analytical range may extend beyond the current calibration curve. This
approach must show the extended calibration curve is linear and be
documented and approved by management.

12.0 QUALITY CONTROL

This section describes common QC measures and corresponding corrective actions.

Method-specific SOPs may contain additional and/or more restrictive QC measures and
corrective actions.

12.1 Analytical Sequence

The sequence of analysis should be detailed in the SOP. The following is an

example of an analytical sequence with a maximum of ten samples between
control standards and check samples:

12.1.1 System Blank

12.1.2 Calibration
12.1.3 Control Standard
12.1.4 Samples (includes blanks and spikes where applicable)
12.1.5 Replicate/Duplicate
12.1.6 Check Standard (CCV or Control Standard as specified in SOP)

Steps 12.1.3-12.1.6 may be repeated for additional samples in a batch as

long as controls remain within specifications. Each set of samples shall be
bracketed by successful control or check standards.

12.2 Blanks

12.2.1 Laboratory Blanks

Laboratory blanks are used to monitor the laboratory preparation

and analysis systems for interferences and contamination from
glassware, reagents, sample manipulations and the general
laboratory environment. The individual SOPs shall describe the
preparation and analytical frequency of laboratory blanks.

System blanks are laboratory blanks used to verify that the

analytical system will not produce a result higher than the LOQ or
RL due to system contamination from high concentration samples
or laboratory sources. The system blank (reagent, gas, etc.) to be
used for each method is specified in the method SOP.
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12.2.2 Blank Corrective Action Criteria

If the blank result is less than the LOQ or RL, then no action should
be taken.
Background subtraction of blanks is allowed where specified in
method SOPs.

Where background correction is not specified in the SOP and the

blank result is greater than the LOQ or RL, the following apply:

12.2.2.1 When the sample results are at least ten times higher
than the blank result, no action is taken.

12.2.2.2 When the sample results are less than ten times higher
than the blank result, the analysis result should be
invalidated for those samples associated with the blank;
the cause shall be investigated and a blank and samples
may be re-extracted and analyzed, if sample is available.

12.2.3 Trip and Field Blanks

Trip and field blanks are used to assess contamination during

transport and handling of samples. Any trip or field blank result that
is greater than the LOQ or RL shall be verified by the analyst. The
results of the trip and field blanks shall be reported with the sample
results. The data user will determine if associated sample results
are impacted.

12.3 Control Standards and Control Charts

Control limits demonstrate statistical evidence that the analytical system is in

control and shall be determined for each analytical instrument.

When available, the control standards shall be prepared from a separate

source (different manufacturer or different lot) than the primary standard used
to prepare the calibration curve. Control standards should be analyzed
directly prior to the analysis of samples (see analytical sequence above).

The initial warning and control limits shall be set at ±8 and ±10 Percent
Difference (PD) respectively from the target value.
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([actual]-[target])
Equation (7) PD= [target]
x 100

Where:
[actual] = analyzed concentration of the control standard
[target] = target control value standard concentration

Once a minimum of 20 control standard results are obtained, the limits for
tolerance of the control results around the mean should be set as follows:

UCL [Upper Control Limit] = +3s of the Mean Value

UWL [Upper Warning Limit] = +2s of the Mean Value

Mean Value

LWL [Lower Warning Limit] = -2s of the Mean Value

LCL [Lower Control Limit] = -3s of the Mean Value

where "s" is the standard deviation of the measurement of the control

standard.

Figure 12.1 Example Control Chart

When adjustments to the control limits are needed, the changes must be
clearly documented and reviewed by management.
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In the event that the instrument method measurement capabilities greatly

exceed the sampling method capabilities for precision, the control limits
should be set such that the precision of the samples is not falsely
represented. Such a case is where the multiple analyses of a SRM, which
closely resembles an average sample matrix, yields an unrealistically low
standard deviation in comparison to anticipated actual sample deviation. The
DQOs should be carefully reviewed, and the control limits established to
reflect this. However, control limits should not exceed ±10 Percent Relative
Standard Deviation (% RSD) under these conditions. In such cases, an
assigned standard deviation should be back-calculated based on the
assigned % RSD, and used for establishing the control limits. Any limits set
by the analyst should be approved by management and should be
documented.
s
Equation (8) % RSD = |x� |
x 100

Where:
s = standard deviation
|x� | = absolute value of the mean

Control standard results shall be reviewed and plotted with each analytical
sequence. Should any analysis of a control standard yield a result which falls
outside the control limits, the analyst shall restart the analytical sequence. If
the control or check standard following a set of samples is outside the control
limit, then the sample results are invalid. Take action to bring the system
back into control and repeat the sample analyses. Each set of samples shall
be bracketed by successful control or check standards.

Control charts should be reviewed for trends at least quarterly. Three

consecutive control standards falling between the warning and control limits
require investigation and corrective action as follows:

12.3.1 Investigate the cause of the warning exceedance

12.3.2 Recommend corrective action
12.3.3 Notify management for approval
12.3.4 Take corrective action and document
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12.4 Replicate/Duplicate Analysis

A replicate sample analysis refers to the reanalysis of the same sample

extract. A duplicate sample analysis refers to the separate analysis of a
distinct extract or aliquot derived from the same sample.

At least one out of every ten samples is randomly designated as the replicate
or duplicate sample. In the case of LIMS generated sample list, LIMS defined
duplicates are generated for ten percent of total samples within the analytical
set.

An evaluation of the duplicate/replicate pairs shall be made with every sample

set using one of the equations below.

(Y-X)
Equation (9) RPD= (Y+X)⁄2
x 100

Where:
RPD = Relative Percent Difference
X = the sample result
Y = the duplicate/replicate result

The RPD may be taken as an absolute value.

Equation (10) AD= |(Y-X)|

AD = Absolute Difference

Duplicate/replicate results and the corresponding RPD or AD should be

documented. The duplicate/replicate acceptance criteria are specified in the
method SOPs. If the duplicate results do not meet specified QC criteria, the
samples in the associated batch should be re-analyzed, or invalidated if re-
analysis is not possible. Duplicate/replicate concentration values less than
five times the LOQ or RL may not be considered when evaluating for the RPD
criteria in accordance with regulatory or programmatic requirements.

12.5 Check Standard

Check standards (also referred to as CCV standard) are prepared from the
reference material used for calibration standards at a point within the
calibration curve. Check standards should be analyzed after a maximum of
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10 samples, at the end of the analytical run, and whenever the analysis
sequence is interrupted. The check standard acceptance criteria shall be
within + 20 percent of the expected value unless specified within the SOP. In
some cases, the analysis of the check standard may be replaced by the
analysis of the control standard.

If the control or check standard following a set of samples is outside

acceptable limits, the sample results are invalid. Take action to bring the
system back into control and repeat the sample analyses. Each set of
samples shall be bracketed by successful control or check standards.

12.6 Analytical Cleanliness Check for Sample Media (Contamination Check)

Sampling media must be checked for cleanliness prior to being sent to the
field for sampling. This includes canisters, filters, sorbent tubes, and any
other collection media. Background levels in the sampling media must be
below the method’s LOQ or RL. SOPs will describe the frequency (e.g., lot,
batch, etc.) of cleanliness checks.

12.7 Spikes

The laboratory may analyze various spikes consisting of laboratory, field, trip,
or matrix spikes. Spike recoveries provide information about laboratory
performance, sample handling, and matrix effects. Spike results are
documented and reported with sample results. Spike requirements and
recovery criteria are specified in the SOPs.

12.8 Standard Additions and Internal Standards

SA is a method to determine the amount of analyte in an unknown or in a

complex matrix that must behave similar to the target analyte. SA can be
applied to most analytical techniques and is used instead of a calibration
curve to solve a matrix effect problem. In SA, known quantities of analyte are
added to an unknown and the analyte concentration is determined from the
increase in instrumental signal.

An internal standard is a known amount of a compound, different from the

analyte, added to the unknown sample. Internal standards are used when the
detector response varies slightly from run to run because of hard to control
parameters. Even if the absolute response varies, as long as the relative
response of analyte and standard is the same, the analyte concentration can
be determined.
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12.9 Collocated Calculations

NLB analyzes collocated samples and only calculates RPD upon request
where both sample results are more than five times the LOQ or RL. If RPD is
outside acceptable limits for the method, results should be verified. If results
are correct, CARB’s Air Quality Surveillance Branch (AQSB) or local districts
are notified to investigate and perform corrective action as needed on
sampling equipment.

12.10 Audits

Performance and technical system audits are important in order to assess the
quality of the data generated. The analysis of performance audit materials
must follow the same procedures as the analysis of regular samples, where
possible. Audit samples are typically provided by LSS, QMB, and U.S. EPA.
Audit results are documented in LIMS.

13.0 SAMPLE MANAGEMENT

Sample management is the ability to effectively and efficiently get sample media to and
from the laboratory and field, while maintaining all regulatory and hold time
requirements, in addition to maintaining sample integrity and providing sample security
and tracking capabilities. Sample management includes: sample receipt, COC, sample
control, sample tracking, log-in, validation, storage, and archive. Refer to the
appropriate SOP for shipping, receiving, and sample handling requirements.

13.1 Sample Receipt

Samples are shipped and received multiple ways between field locations and
the laboratory. To ensure the samples are received by the appropriate entity,
documentation is required that clearly indicates the dates, times, and
individuals that have taken custody of the sample media.

13.1.1 All samples shall be received in the designated sample control

area/sample receiving room.

13.1.2 Samples shipped or delivered the following ways will be stamped or

notated with the date and time received by staff, then routed to the
specified sample receiving room or sample control location:

13.1.2.1. Via regular mail

13.1.2.2. Via stockroom pick-up or delivery by a shipping company
13.1.2.3. Via delivery in person
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13.1.3 All samples received shall be stored per the SOP in designated
locations in the laboratory (e.g., freezer, refrigerator, or dry
storage).

13.2 Chain of Custody/Sample Control

COC is an accurate written record that tracks the possession, transfer,

handling, and location of samples from sample media preparation to sample
collection, including sample receipt, to reporting. The COC is an important
function of sample control and an integral part of sample receipt.

All samples shall be accompanied by a properly completed COC. If not,

laboratory staff may not accept samples depending on the program. If
samples are accepted, they will be stored appropriately in the specified
sample receiving area but may not be processed until a completed COC is
received.

Laboratory staff shall sign and date the COC indicating the laboratory has
received the sample and is now responsible for sample control and custody.

All completed, signed, and dated COCs shall be stored and archived
appropriately according to program needs or requirements.

13.3 Sample Validation

Once a completed COC has been received and reviewed, the overall sample
quality and condition must be compared to the criteria required for validation
by regulatory program, SOP, and/or management. Sample validity status may
change while under laboratory control.

Laboratory staff shall contact site operators, or other appropriate staff, directly
when issues arise that require clarification of information to validate a sample
at log-in, when a sample is invalidated, or when a make-up sample is
recommended. This notification is performed as soon as possible, and the
issue is documented on the COC or sample report form.

13.4 Sample Login

A LIMS generated number or other unique identification number (barcode)

must be given to all samples prior to analysis or preparation. Pertinent
information from the COC is entered into LIMS during the login process.
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The LIMS number and/or barcode assigned to a sample must appear on all
associated documentation, such as the COC, sample report form, the sample
folder, LIMS, and any laboratory worksheet associated with the sample.

13.5 Sample Storage

Once the samples are logged into LIMS, the samples are stored under SOP-
specific conditions (e.g., ambient, refrigerator, freezer) in the appropriate
laboratory. Documentation regarding the storage and transfer of samples is
maintained in the laboratory and/or sample receiving room.

13.6 Sample Tracking

The sample transfer within the laboratories shall be recorded using sample
custody logbooks, COC, and/or LIMS, and shall include the date the samples
were transferred, the initials of the person handling the transfer, and the
location of the sample.

13.7 Archive, Storage, and Disposal

13.7.1 Samples and sample containers that are not consumed during
analysis shall be appropriately stored according to the SOP
requirements, returned to the client, or disposed of appropriately.

13.7.2 Sample documentation including COC, logbooks, sample tracking,

etc. should be maintained following CARB’s records retention policy
unless stricter requirements are specified in the SOP or by
regulation.

13.7.3 Samples and sample containers exceeding specified holding or

retention times may be disposed of properly with the approval of
management.

14.0 DATA MANAGEMENT

Data management describes the basic flow of analytical data from generation, review
(verification and validation), and reporting. Laboratory staff and management are all
integral parts of data management. The laboratory utilizes a LIMS database to perform
data management activities.
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14.1 Laboratory Information Management System

LIMS facilitates the recording, verification and validation, transmittal,

reduction, analysis, management, storage, retrieval, and reporting of
analytical data generated by the laboratory. LIMS is maintained by the LIMS
administrator.

LIMS administrator creates and/or modifies approved laboratory staff access

to LIMS; creates and modifies LIMS methods, data templates and transfers,
and data reports; and is able to modify data in LIMS.

All sample and analysis information shall be entered into LIMS or recorded in
bound or electronic notebooks. Changes to any data in LIMS must be made
by authorized individuals only. Management’s approval may be required.

14.2 LIMS Access

All users must be authorized by management to receive program access to

LIMS. Different privileges are given to authorized users depending on need.

Access may include:

14.2.1 Read-only
14.2.2 Data entry
14.2.3 Addition of test methods
14.2.4 Modification of preliminary data
14.2.5 Data transfer
14.2.6 Data reporting
14.2.7 Data upload
14.2.8 Data system administration

14.3 LIMS Generated Reports

LIMS can be accessed to generate many different report types. They include
worklists, data summaries of all varieties, and reformatted reports that can be
applied to other applications (e.g., upload to another database such as AQS).
Staff use worklists to schedule their sample analyses (e.g., sample hold
times, inventory, etc.). Summary reports range from output that displays
recently logged-in samples to a complete list of finalized data and results.
Staff can also open a LIMS generated file in Excel and perform further
calculations and formatting. Reports can be viewed on screen, sent to a
printer, or output to PDF, HTML, or Excel.
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14.4 Initial Data Assessment

Samples are analyzed and the instrument QC results are reviewed by the
analyst to decide if sample analysis is valid prior to transfer into LIMS.
Corrective action should be taken as needed when QC criteria are not met,
such as re-analysis, dilution, re-integration, etc.

Any sample result that has been invalidated must be reported as "invalid” or
“not analyzed,” and its respective reason documented.

All results reported as "not detected" must be associated with a reference

value, such as LOQ, EQL, or minimum reporting value.

Laboratory staff will contact site operators, or other appropriate staff, directly
when issues arise that require clarification of information to validate a sample
at log-in, when a sample is invalidated, or when a make-up sample is
recommended. This notification is performed as soon as possible, and the
issue is documented on the COC or sample report form according to
established laboratory procedures. If invalidated samples occur repeatedly
and are deemed by management to be indicative of a systemic issue,
management will utilize the Corrective Action Notification (CAN) process to
initiate a formal corrective action process in order to inform all responsible
and impacted parties; document the issue and resolution; and prevent
potential future data loss. If a CAN is deemed unnecessary, management will
document how the issue has been resolved and what other parties were
notified of the issue.

14.5 Data Transfer to LIMS

Data from the analytical system is transferred to LIMS manually or

electronically. Instrument to LIMS transfers should be verified by the analyst.

In management-approved special situations where LIMS transfer and storage

is not possible the data must be electronically stored in an appropriate file on
the NLB shared drive. All raw data should be archived appropriately.

14.5.1 Data Analysis Records

14.5.1.1 All raw data, calculations, observations, validation

information, and results generated by the analyst must be
placed in an appropriate computer file, bound or
electronic laboratory notebook, or other approved format.
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For bound notebooks, all entries must be initialed and

dated by the analyst.

14.5.1.2 Modifications to raw data, (e.g., re-integrations of

chromatographic peaks) must be documented. Original
data and modified data must be maintained for review.

14.5.1.3 All analysis hardcopies must be stored in an appropriate

filing system until archiving.

14.5.1.4 Any raw analytical data stored on a computer hard drive

should be routinely backed up. A backup copy of all
instrument software, including NLB developed
parameters, should be made after the initial
development.

14.5.1.5 An instrument maintenance logbook must be assigned to

each instrument. All calls for service, repair records,
reconfigurations, or changes to the instrument operating
parameters must be recorded, dated, and signed by the
analyst or instrument service representative. The
logbook must be kept with the instrument and be
available for inspection at any time.

14.6 Analytical Data Reports

Analytical data reports are generated by the analyst and submitted for
review/approval after initial data assessment and transfer to LIMS in order to
verify and validate the data. At a minimum, the following must be included in
the data package:

14.6.1 Method, program, or project name

14.6.2 Signature and date blocks (staff and management).
14.6.3 Timeframe or batch of analyses covered
14.6.4 Data with comments and flags
14.6.5 Copies of appropriate logbook pages (e.g., extraction logs)
14.6.6 Analytical run sequence
14.6.7 Calibrations
14.6.8 QC results
14.6.9 Control charts
14.6.10 Description of unusual occurrences with samples, analysis, and/or
data
14.6.11 Corrective actions taken
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14.6.12 Any deviations from approved SOP

14.7 Verification of LIMS Changes

LIMS is programmed by the LIMS administrator(s) to automatically verify and

validate data. Data outside QC criteria are highlighted for analyst, peer, and
management review, comment, and corrective action.

Requested changes to LIMS (e.g., QC criteria, calculations, etc.) must be

approved by management in writing. QC parameters may come from federal
and/or State regulations, program guidance documents, QCM, and/or SOPs.

LIMS programmed QC parameters are tested and reviewed by the LIMS

administrator(s) before placement into LIMS production. LIMS also utilizes an
audit trail function. Management is notified when updates have been
completed by the LIMS administrator.

14.8 Data Review and Approval

The data review and approval process consists of a series of checks to

ensure the analytical data generated by the laboratory and transferred to
LIMS meets all the method specific QC criteria. The multistep process
includes, at a minimum, analyst and peer review followed by management
review and approval prior to submittal to clients. All levels of review and
approval are initialed and dated on the cover page of the data package.

14.8.1 Analyst Review

The following items, when applicable, will be documented and

verified by the analyst that performed the analyses:

14.8.1.1 Extraction solvents and volumes

14.8.1.2 Instrument conditions
14.8.1.3 Analytical run conducted per SOP
14.8.1.4 Expiration dates of standards
14.8.1.5 Retention times
14.8.1.6 Integrations
14.8.1.7 Peak identifications
14.8.1.8 Analytical sequences
14.8.1.9 Environmental conditions
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14.8.1.10 QC (such as MDLs, duplicates, standards, blanks,

controls)
14.8.1.11 Data reduction and calculations
14.8.1.12 COC data login to LIMS
14.8.1.13 Raw data concentrations transferred to LIMS
14.8.1.14 Holding times
14.8.1.15 Calibrations
14.8.1.16 Parameters of SOP and QC manual are met
14.8.1.17 Anomalies and corrective actions are documented and
management notified, as necessary

14.8.2 Peer Review

The following items will be verified by a second analyst:

14.8.2.1 Data package completeness

14.8.2.2 Spot-check calculations
14.8.2.3 Check for documentation of unusual events
14.8.2.4 Corrective action review
14.8.2.5 Check for outliers
14.8.2.6 Analytical run sequence
14.8.2.7 Dilutions performed as necessary
14.8.2.8 QC (such as MDLs, duplicates, standards, blanks,
controls)
14.8.2.9 Expiration dates of standards
14.8.2.10 Reasons for invalid samples
14.8.2.11 Flags and comments
14.8.2.12 Parameters of SOP and QC manual are met

If necessary, data package will be returned to the analyst for edits or

clarification. After corrections are made the data package will be
returned to the peer reviewer for confirmation. Once peer review is
complete, the peer reviewer signs and/or initials, and dates the
analytical data package.

14.8.3 Management Review and Approval

The following will be reviewed by management prior to data

release:

14.8.3.1 Data package completeness

14.8.3.2 Spot-check calculations
14.8.3.3 Check for documentation of unusual events
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14.8.3.4 Corrective action review

14.8.3.5 Check for outliers
14.8.3.6 Analytical run sequence
14.8.3.7 QC (such as MDLs, duplicates, standards, blanks,
controls)
14.8.3.8 Expiration dates of standards
14.8.3.9 Reasons for invalid samples
14.8.3.10 Flags and comments
14.8.3.11 Check for analyst and peer review
14.8.3.12 Parameters of SOP and QC manual are met

If necessary, data package will be returned to the analyst for edits or

clarification. After corrections are made, the data package will be
returned to management for confirmation. Once review is complete,
management signs and/or initials and dates the analytical data
package.

14.9 Data Release and Reporting

After the review and approval process, sample results and related information
in LIMS are locked to ensure no changes are made without management
authorization. Data in LIMS can still be viewed (Read Only) by management
and staff.

Data are released in electronic and/or hardcopy form, depending on the

client’s request. Management-approved data reports may be sent to the
client (or the client representative) by management or assigned staff.

14.10 Amendment to Data

Finalized and approved data may be amended in LIMS per management

approval. After the request is approved, laboratory staff and management
must follow the data review and approval process. If changes to finalized
data are made, the client must be notified and sent a revised report. Data
may be amended for reasons such as CANs, Air Quality Data Actions
(AQDA), requests by clients (i.e., requests to exclude codes), etc.

14.11 Data Archive

All final hardcopy reports with the analyst review, peer review, and
management approval signatures shall be filed in a secure manner. Access
to hardcopy and LIMS files shall be limited to authorized individuals only.
Laboratory retention of hardcopy and electronic LIMS data files shall follow
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CARB or regulatory retention policies. Final archiving and/or destruction of all

data reports shall be approved by management.

14.12 Significant Figures and Rounding Rules

When a measured or calculated quantity is written down, some indication of

the precision of the measurement must be given. This is shown by
designating the number of significant figures in a result and gives an
indication of the confidence with which the number is known. The greater the
number of significant figures, the smaller the uncertainty and the greater the
precision in its measurement. Data should be rounded to the number of
figures consistent with the confidence that can be placed in it.

Unless defined by the client or regulatory program, rounding shall be deferred

until all calculations have been made. The final result shall contain no more
significant figures than the lowest number of significant figures (least precise)
of the values used in the calculations.

Example: 14.80 X 12.10 X 5.05 = 904.354000 = 904

4 sig figs X 4 sig figs X 3 sig figs = 3 sig figs

14.12.1 All nonzero digits are significant (i.e., 4.006, 12.012, and 10.070).
14.12.2 Zeros placed between nonzero digits are significant (i.e., 4.006,
12.012, and 10.070).
14.12.3 Zeros at the end of a number to the right of the decimal point are
significant (i.e., 10.070).
14.12.4 Zeros to the left of the first nonzero digit are not significant. They
simply locate the decimal point. (0.0002 has only one significant
figure, 0.000020 has two significant figures)
14.12.5 When rounding to correct the significant figures the rule is to
increase the final digit by one unit if the digit dropped is greater
than five and to leave the final digit unchanged if the digit dropped
is less than five. If the digit dropped is five, the final remaining digit
is increased by one unit if necessary to make it even otherwise it is
left unchanged.

Example: For 3 significant figures:

15.56 rounds off to 15.6
15.54 rounds off to 15.5
15.55 rounds off to 15.6
15.45 rounds off to 15.4
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15.0 QUALITY CONTROL REPORTS

Quality Control Reports are prepared by each section on an annual basis. The Quality
Control Report documents and summarizes the QC activities and measurements
associated with each analytical method. QC activities and criteria are outlined in this
document and specific method SOP. Quality Control Reports should contain a brief
description of each QC parameter as it pertains to the analytical methods and all
corrective actions taken during the inclusive time period.

Quality Control Reports should include:

15.1 Introduction
15.2 Blanks
15.3 Calibration and Standards
15.4 Controls
15.5 Replicates/Duplicates
15.6 Spikes
15.7 Limits of Detection and Limits of Quantitation
15.8 Instrument Cross-Checks
15.9 Sample Holding Time Checks
15.10 Confirmations
15.11 Crossover Compounds
15.12 Sample Collection Irregularities and Collocated Results
15.13 Instrument Maintenance and Modification Summary
15.14 Summary of Departures from Current Method and SOP
15.15 Audits and Round-Robins (Check Samples)

16.0 CONFIDENTIAL INFORMATION

NLB has established procedures under California Law for handling information that has
been designated as confidential, proprietary, or trade secrets. These procedures are
maintained by SAS.

All designated "CONFIDENTIAL INFORMATION" must be maintained in a locked file

cabinet in a secure area. Access to this file cabinet is subject to management approval.

17.0 HAZARDOUS MATERIAL AND WASTE MANAGEMENT

All laboratory activities involving the direct or indirect handling of hazardous material or
hazardous waste must comply with all federal, State, and local regulations to ensure the
safety and quality of the laboratory and the environment. All staff must be familiar with
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and comply with the MLD Chemical Hygiene Plan and receive required training. The
designated hazardous waste coordinator shall oversee all hazardous waste operations.

18.0 REFERENCES

18.1 Anderson, Robert L., Practical Statistics for Analytical Chemists, Van
Nostrand Reinhold Company Inc., 1987.

18.2 Taylor, John Keenan, Quality Assurance of Chemical Measurements, Lewis

Publishers, 1987

18.3 Wisconsin Department of Natural Resources Laboratory Certification

Program, “Analytical Detection Limit Guidance and Laboratory Guide for
Determining Method Detection Limits,” PUBL-TS-056-96, April 1996.

18.4 California Environmental Protection Agency, Air Resources Board, “Quality

Management Plan for Air Quality Monitoring,” July 2013.

18.5 California Environmental Protection Agency, Air Resources Board, “Chemical

Hygiene Plan,” July 2, 2002.

18.6 U.S. EPA Office of Air Quality Planning and Standards, Air Quality
Assessment Division, “QA Handbook for Air Pollution Measurement Systems,
Volume II, Ambient Air Quality Monitoring Program,” EPA-454/B-13-003, May
2013.
18.7 U.S. EPA Office of Environmental Information, “Guidance for Preparing
Standard Operating Procedures EPA QA/G-6,” EPA/600/B-07/001, April
2007.

18.8 California Air Resources Board, Northern Laboratory Branch, “Standard

Operating Procedure for Preparation of Northern Laboratory Branch’s
Standard Operating Procedures, MLD076, Revision 0.0,” July 18, 2017.
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19.0 REVISION HISTORY

Version Effective Date Primary Changes

1.0 1993 N/A
2.4 June 2001 Unknown
3.0 September 2015 Updates to improve data
quality and define
corrective actions; address
US EPA Technical System
Audit findings
3.0, August 18, 2016 Analytical Quantitation
Addendum A14 (Section 11.0) to align with
40 Code of Federal
Regulations (CFR)
Appendix B to Part 136,
Revision 1.11: clarified
initial spike concentration to
be one to five times the
estimated MDL; and MDL
criteria is “MDL < analyte
level < 10xMDL”
3.0, July 2, 2018 Analytical Quantitation
Addendum A-24 (Section 11.0): organized
for clarity; define LOQ to
equal five times the
standard deviation of the
replicate analyses from the
MDL
determination/verification;
and additional MDL
verification criteria.
4.0 September 17, 2018 Update Standard Operating
Procedures (Section 9.0),
and Control Standards and
Control Charts (Section
12.3).
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Appendix: Northern Laboratory Method Modification

Procedures
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