United Stales
Environmental Protection
Agency
Office of
Solid Waste and
Emergency Response
9240.1-32
EPA/540/R-96/016
PB96-963504
Solid Waste
Statement of Work for Low
Concentration Inorganic
Analytes in Water
ILC03.1
Draft Version
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9240.1-32
EPA/540/R-96/016
PB96-963504
DRAFT
STATEMENT OF WORK
FOR
LOW CONCENTRATION INORGANIC ANALYTES
IN WATER
ANALYTICAL SERVICES FOR SUFERFUND DOCUMENT NO. ILC03.1
U.S. ENVIRONMENTAL PROTECTION AGENCY
CONTRACT LABORATORY PROGRAM
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CONTENTS
EXHIBIT A; Summary of Requirements A-l
EXHIBIT B: Reporting and Deliverables Requirements B-l
EXHIBIT C: Tables ... ............ C-l
EXHIBIT D: Analytical Methods D-l
EXHIBIT E: Quality Assurance/Quality Control Requirements . E-l
EXHIBIT F: Chain-of-Custody, Document Control,
and Written Standard Operating Procedures .... F-l
EXHIBIT G: Glossary of Terms G-l
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EXHIBIT A: Summary of Requirements
SECTION I: General Requirements ........ A-3
SECTION II: Specific Requirements A-4
Part A - Task Performance A-4
Part B - Reporting A-8
Part C - Systems A-8
Part D - Functions and Operations A-9
SECTION III: Technical and Management Requirements ........... A-10
A-l ILC03.1
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CONTRACTOR OPERATED:
SAMPLE MANAGEMENT OFFICE
The Sample Management Office (SMO) is operated by the Contract Laboratory
Analytical Services Support (CLASS) contract awarded and administered by the
U.S. Environmental Protection Agency (EPA). Laboratory contractors are
advised that wherever in this document the words "Sample Management Office",
"SMO", "Contract Laboratory Analytical Services Support" or "CLASS" appear,
EPA is referring to those contractor employees. The contract is currently
held by DynCorp*Viar under Contract No. 68-D4-0104. Laboratory contractors
are also advised that DynCorp"Viar employees are not representatives or agents
of EPA. As such, DynCorp«Viar nor its employees, nor any successor
contractor, may change, waive, or interpret any terms and conditions in this
contract, including this document (ILC03.1). All such questions or inquiries
should be addressed to the responsible party within EPA.
QUALITY ASSURANCE TECHNICAL SUPPORT LABORATORY
The Quality Assurance Technical Support (QATS) Laboratory contract was awarded
and is administered by the U.S. Environmental Protection Agency (EPA).
Laboratory contractors are advised that wherever in this document the "Quality
Assurance Technical Support Laboratory" or "QATS" appear, EPA is referring to
those employees. The contract is currently held by ICF Kaiser Engineers, Inc.
(ICF), under Contract No. 68-D5-0002. Laboratory contractors are also advised
that ICF employees are not representatives or agents of EPA. As such, ICF nor
its employees, nor any successor contractor, may change, waive, or interpret
any terms and conditions in this contract, including this document (ILC03.1).
All such questions or inquiries should be addressed to the responsible party
within EPA.
A-2
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SECTION I: General Requirements
1. The data generated using the procedures in this Statement of Work (SOW),
with its associated quality control procedures, criteria, and documentation,
will be used for several purposes in the Environmental Protection Agency (EPA)
Superfund Program.
2. The data quality must meet the Office of Drinking Water (Safe Drinking
Water Act) Standards, including Maximum Contamination Levels (MCLs) for
drinking water and groundwater. In addition, the data will be used for
performing risk and health assessments in order to determine the
appropriateness of Superfund remedy options. The data will also be used in
public health assessments, where it is necessary to provide data to support a
proposed risk range of 10*' to 10"7 Cancer Risk Factors. Information may also
be used for Superfund enforcement and litigation and in cost recovery.
Finally, these data will be used to ascertain compliance with ambient water
quality criteria. Because of the multidimensional use of the data, and its
importance in meeting these goals, it is imperative that the data meet the
contract requirements.
3. Under this SOW, Contractor laboratories (herein called Contractor or
Laboratory) shall employ procedures specified here in the preparation and
analysis of low concentration water samples for the presence and quantitation
of 23 indicated elements, cyanide.
4. This Exhibit (A) summarizes the requirements, and Exhibits B-G present
specific information. Because of the low detection levels that are required
under this SOW, the Contractor shall exercise caution during the preparation,
analysis, and storage of the samples to prevent contamination. Following
sample analysis, the Contractor shall perform data reduction and shall report
analytical activities, sample data, and quality control documentation as
designated in Exhibit B.
5. The Contractor shall use proven instruments and techniques to identify and
measure the elements and inorganic species presented in the Target Analyte
List (TAL) (Exhibit C). The Contractor shall perform sample preparation and
analysis procedures as prescribed in Exhibit D, meeting specified sample
preservation and holding time requirements.
6. The Contractor shall adhere to the quality assurance/quality control
(QA/QC) protocol specified in Exhibit E for all samples analyzed under this
contract.
7. Exhibit F contains chain-of-custody and document control requirements that
the Contractor shall follow in processing samples and specifies requirements
for written laboratory standard operating procedures.
8. To ensure proper understanding of language utilized in this contract,
Exhibit G contains a glossary of terms. When a term is used in the text
without explanation, the glossary meaning shall be applicable. Glossary
definitions do not replace or take precedence over specific information
included in the SOW text.
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SECTION II: Specific Requirements
Part A - Task Performance
For each sample, the Contractor shall perform the following tasks;
Task I: Receive and Prepare Low Concentration Water Samples
1, Chain-of-Custody. The Contractor shall receive and maintain samples under
proper chain-of-custody and sample documentation procedures described in
Exhibit F. A sample consists of all components, contained inside appropriate
receptacles. Containers may be glass or plastic. More than one container may
be used for a single sample; individual containers may contain preservatives
for different analysis portions. All associated document control and
inventory procedures shall be developed and followed. Documentation, as
described therein, shall be required to show that all procedures are being
strictly followed. This documentation shall be reported as the Complete
Sample Delivery Group File (CSF) (see Exhibit B). The Contractor shall
establish and use appropriate procedures to handle confidential information
received from the Agency.
2. Sample Scheduling/Shipments. Sample shipments to the Contractor's
facility will be scheduled and coordinated by the EPA Contract Laboratory
Program (CLP) Sample Management Office (SMC). The Contractor shall
communicate with SMO personnel by telephone as necessary throughout the
process of sample scheduling, shipment, analysis, and data reporting, to
ensure that samples are properly processed.
2.1 Samples will routinely be shipped directly to the Contractor through a
delivery service. The Contractor shall be available to receive sample
shipments at any time the delivery service is operating, including
Saturdays and holidays. As necessary, the Contractor shall be responsible
for any handling or processing for the receipt of sample shipments,
including pick-up of samples at the nearest servicing airport, bus station,
or other carrier service within the Contractor's geographical area.
2.2 The Contractor shall accept all samples scheduled by SMO, provided
that the total number of samples received in any calendar month does not
exceed the monthly limitation expressed in the contract. Should the
Contractor elect to accept additional samples, the Contractor shall remain
bound by all contract requirements for analysis of those samples accepted.
2.3 If insufficient sample volume (less than the required amount) is
received to perform the analysis, the Contractor shall contact SMO to
apprise them of the problem. SMO will contact the Region for instructions.
The Region will either approve that no sample analysis be performed or will
require that a reduced volume be used for the sample analysis. No other
changes in the analysis will be permitted. SMO will notify the Contractor
of the Region's decision. The Contractor shall document the Region's
decision in the SDG narrative.
2.4 The Contractor shall be required to routinely return sample shipping
containers (i.e., coolers) to the appropriate sampling office within
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fourteen (14) calendar days following shipment receipt (see Clause entitled
Government Furnished Supplies and Materials}.
2.5 If there are problems with the samples (e.g., mixed media, containers
broken or leaking) or the sample documentation/paperwork (e.g., Traffic
Reports not with shipment, or sample and Traffic Report do not correspond),
the Contractor shall immediately notify SMO regarding any problems and/or
laboratory conditions that affect the timeliness of analyses and data
reporting. In particular, the Contractor shall immediately notify SMO
personnel in advance regarding sample data that will be delivered late and
shall specify the estimated delivery date. The Contractor shall document
all communications with SMO and/or the Regional representative(s) in the
SDG narrative.
3. All samples and blanks submitted to the Contractor should have measured
amounts of preservatives, i.e., 2 ml 1:1 HN03/L to pH < 2 as recorded on the
Traffic Report. Before sample preparation is initiated on a sample received
in shipment, the Contractor shall check the pH of the sample and note the pH
in the laboratory's preparation log. The laboratory shall verify that the pH
is <2 for the metals sample, and that the pH is > 12 for cyanide samples, as
appropriate. If the sample has not been properly preserved (i.e., the pH of
the metals samples is >2, and the pH of the cyanide samples is <12), the
Contractor shall immediately contact SMO. SMO will contact the Region from
which the samples were shipped for instructions on how to proceed. The Region
will either require that the pH be adjusted, and the analysis(es) be performed
or that the Contractor proceed with the analysis(es). SMO will notify the
Contractor of the Region's decision. The Contractor shall document the
Region's decision and list the EPA sample number for all affected samples in
the SDG narrative.
4. The Contractor shall prepare samples as described in Exhibit D. If
dissolved metals are required by the EPA Region, the Contractor shall follow
the instructions provided on the Traffic Report(s). If there are no
instructions on the Traffic Report(s), the Contractor shall digest the samples
designated as dissolved metals. If the Regional office indicates on the
Traffic Report(s) that a digestion is not to be performed when analyzing field
samples for dissolved metals, then a laboratory control sample (LCS) (Form IX)
is not required. Dissolved metals samples that are not digested shall be
matrix-matched to instrument calibration standards. Matrix matching shall be
applied without affecting the original sample volume by more than 10 percent.
5. The Contractor shall prepare and analyze samples within the maximum
holding time specified in Section II of Exhibit D even if these times are less
than the maximum data submission time allowed in this contract.
6. To more effectively monitor the temperature of the sample shipping cooler,
each USEPA Regional office may include a sample shipping cooler temperature
blank with each cooler shipped. The temperature blank will be clearly
labeled: USEPA COOLER TEMPERATURE INDICATOR.
6.1 When the USEPA Regional office supplies a cooler temperature indicator
bottle in the sample shipping cooler, the Contractor shall use the USEPA
supplied cooler temperature indicator bottle to determine the cooler
temperature. The temperature of the cooler shall be measured at the time of
sample receipt by the Contractor.
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6.2 The temperature of the sample shipping cooler shall be measured and
recorded immediately upon opening the cooler, and prior to unpacking the
samples or removing the packing material.
6.3 To determine the temperature of the cooler, the Contractor shall
locate the cooler temperature indicator bottle in the sample shipping
cooler, remove the cap and insert a calibrated thermometer into the cooler
temperature indicator bottle. Prior to recording the temperature, the
Contractor shall allow a minimum of 3 minutes, but not greater than 5
minutes for the thermometer to equilibrate with the liquid in the bottle.
At a minimum, the calibrated thermometer shall have a measurable range of 0
to 50 degrees Celsius.
6.4 If the temperature of the sample shipping cooler's temperature
indicator exceeds 10 degrees Celsius, the Contractor shall contact SMO and
inform them of the temperature deviation. SMO will contact the Region from
which the samples were shipped for instruction on how to proceed. The
Region will either require that no sample analysis(es) be performed or that
the Contractor proceed with the analysis(es). SMO will in turn notify the
Contractor of the Region's decision. The Contractor shall document the
Region's decision in the SDG narrative. Also, in the SDG narrative, the
Contractor shall list, by the USEPA sample number, all samples which were
shipped in a cooler which exceeded 10 degrees Celsius.
6.5 The Contractor shall record the temperature of the cooler on the DC-1
Form, under Remark #8 - Sample Conditions, and in the SDG narrative.
Task II: Analyze Samples for Identification and Quantitation of Specific
Inorganic Constituents
1. Aliquots and digestates prepared in Task I shall be analyzed by the
analytical procedures described in the methodologies given in Exhibit D. The
documentation that accompanies the sample(s) to the Contractor facility shall
indicate specific analytical requirements for that sample or set of samples.
2. Exhibit D contains instructions and references for preparation of samples
containing low concentrations of inorganics for inductively coupled plasma -
atomic emission spectroscopy (ICP), inductively coupled plasma - mass
spectrometry (ICP-MS), graphite furnace, flame, and cold vapor atomic
absorption (AA), and cyanide (CN) analyses. The identification and
quantitation of each analyte shall be accomplished using the appropriate
methods as specified by the following:
Analyte Approved Analytical Method
CN Manual and semiautomated
colorimetric
Hg Cold vapor AA
Sb, As, Se, Zn, V, Tl, Ag, Ni, ICP, ICP-MS, furnace AA.
Fe, Cu, Co, Cr, Cd, Be, Ba, A1
Mn, Pb
A-6
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Ca, Mg, K, Na
ICP, ICP-MS, flame AA, furnace AA
3, All samples shall initially be run undiluted {i.e., the final product of
the sample preparation procedure). When an analyte concentration exceeds the
calibrated or linear range, appropriate dilution {but not below the CRDL) and
reanalysis of the sample is required, as specified in Exhibit D. The
Contractor should maintain the same acid concentration in the diluted sample
as was present in the undiluted sample used for analysis.
4. For the purpose of this contract, a full sample analysis is defined as
analysis for all of the TAL constituents identified in Exhibit C in accordance
with the methods in Exhibit D, and performance of related QA/QC as specified
in Exhibit E. All QA/QC required sample analyses, including Duplicate sample,
spike sample, and Laboratory Control Sample (LCS) analyses are considered an
inherent part of this SOW and are included in the contract sample unit price.
Task III: Perform Required Quality Assurance/Quality Control Procedures
1. All specific QA/QC procedures prescribed in Exhibit E shall be strictly
adhered to by the Contractor. Records documenting the use of the protocol
shall be maintained in accordance with the document control procedures
prescribed in Exhibit F, and shall be reported in accordance with Exhibit B
requirements.
2. The Contractor shall establish and use on a continuing basis the QA/QC
procedures in Exhibit E. These procedures include the use of standard
reference materials at the required frequency where available at appropriate
concentrations, from EPA, the National Institute of Standards and Technology
or secondary standards traceable thereto, where available at appropriate
concentrations {i.e., standard solutions designed to ensure that operating
parameters of equipment and procedures, from sample receipt through
identification and quantitation, produce reliable data). Exhibit E specifies
the QA/QC procedures required.
3. The Contractor shall maintain a Quality Assurance Plan (QAP) as defined in
Exhibit E with the objective of providing sound analytical chemical
measurements. This program shall incorporate the QC procedures, any necessary
corrective action, and all documentation required during data collection as
well as the quality assessment measures performed by management to ensure
acceptable data production.
4. The Performance Evaluation Sample (PES) is an external laboratory QC
sample prepared by the Agency to assess, on the basis of Sample Delivery Group
{SDG), the baseline capability of the Contractor to perform the analytical
methods listed in Exhibit D.
4.1 The PES will be received from the Agency in ampules or as full volume
samples. If they are received in ampules, the Contractor will receive
instructions concerning the dilution procedure to bring the samples to full
volume prior to preparation and analysis.
4.2 The PES shall be prepared and analyzed concurrently with each SDG,
when available and provided by the Agency. The PES may be provided as a
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single-blind QC sample (i.e., the Contractor will know that the sample is a
PES, but will not know which analytes are in the PES or their
concentration) or as a double-blind QC sample (i.e., the Contractor will
receive a PES as a full volume sample which will appear to be an
environmental field sample).
4.3 The Contractor will prepare and analyze the PES according to
requirements listed in Exhibit D, and report the results according to the i
requirements in Exhibit B.
4.4 The Contractor will be responsible for correctly identifying and
quantifying the analytes included in the PES. The Agency will notify the
Contractor of unacceptable performance. Exhibit E defines acceptable
performance and describes the corrective action procedures required under
this contract.
5. The Laboratory Control Sample (LCS) is an internal laboratory QC sample
designed to assess, on a SDG-by-SDG basis, the baseline capability of the
Contractor to perform the analytical methods listed in Exhibit D. The
Contractor shall prepare and analyze an LCS once per SDG, concurrently with
samples in the SDG.
Part B - Reporting
1. EPA has provided the Contractor a format for the reporting of data
(Exhibit B). The Contractor shall be responsible for completing and returning
analysis data sheets in the format specified in this SOW and within the time
specified in the Contract Performance/Delivery Schedule (see Exhibit B).
2. Use of formats other than those designated by EPA will be deemed as
noncompliant. Such data are unacceptable. Resubmission in the specified
format at no additional cost to the government will be required.
3. Computer-generated forms may be submitted in the hard copy data package(s)
provided that the forms are in EXACT EPA FORMAT. This means that the order of
data elements is the same as on each EPA-required form, including form numbers
and titles, page numbers and header information, columns and lines.
Part C - Systems
1. The Contractor shall provide analytical equipment and technical expertise
for the analyses of TAL analytes at concentrations equal to or lower than the
contract required detection limits specified in Exhibit C. The Contractor
shall maintain, at a minimum, the following:
1.1 ICP emission spectrometer, with the capability to analyze metals
sequentially or simultaneously,
1.2 AA spectrometer equipped with graphite furnace, flame, and cold vapor
AA (or a specific mercury analyzer) analysis capabilities. Note: Deuterium
background may not meet all of the analytical requirements of this
contract.
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2. The Contractor shall maintain a complete system(s) applicable to the
determination of cyanide,
3. Analytical equipment and apparatus for the determination of analytes not
analyzed by the above instrumentation (e.g., microwave digestion units, hot
plates, a block digester, wet chemistry apparatus, spectrometers, etc.). In
addition, the following list of optional equipment may be used if the
instrumentation can meet the required CRDLs and QC requirements listed in
Exhibits C and E, respectively:
3.1 An ICP-MS with the capability to analyze metals.
Part 0 - Functions and Operations
1. The Contractor shall designate and utilize qualified key personnel to
perform the functions specified in this SOW.
2. EPA reserves the right to review personnel qualifications and experience.
3. The Contractor shall respond within 7 days to written requests from data
recipients for additional information or explanations that result from the
government's inspection activities, unless otherwise specified in the contract
(see Exhibit E for details on Government inspection activities)¦
4. The Contractor is required to retain unused sample volumes and used sample
containers for a period of 60 days after data submission.
5. Sample analyses will be scheduled by groups of samples, each defined as a
Case and identified by a unique EPA Case number assigned by SMO. A Case
signifies a group of samples collected at one site or geographical area over a
finite time period, and will include one or more field samples with associated
blanks. Samples may be shipped to the Contractor in a single shipment or
multiple shipments over a period of time, depending on the size of the Case.
A Case may consist of one or more SDG(s). An SDG is defined by the following,
whichever is most frequent:
Each Case of field samples received, or
Each 20 field samples within a Case, or
Each 7 calendar day period during which field samples in a Case are
received (said period beginning with the receipt of the first sample in the
SDG) .
5.1 Data for all samples in an SDG shall be submitted together, including
the PES, in one package and in the order specified in Exhibit B. The SDG
number is the EPA sample number of the first sample received in the SDG.
When several samples are received together in the first SDG shipment, the
SDG number is the lowest sample number (considering both alpha and numeric
designations) in the first group of samples received under the SDG. The
SDG number is reported on all data reporting forms. The SDG Receipt Date
is the day that the last sample in the SDG is received.
5.2 The Contractor is responsible for identifying each SDG as samples are
received, through proper sample documentation (see Exhibit B) and
communication with SMO personnel.
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6. Each sample, including the PES, received by the Contractor will be labeled
with an EPA sample number, and accompanied by a Traffic Report form bearing
the sample number and descriptive information regarding the sample. EPA field
sample numbers are six digits in length. If the Contractor receives a sample
number of any other length, the Contractor shall contact SMO immediately. The
Contractor shall complete and sign the Traffic Report, recording the date of
sample receipt and sample condition on receipt for each sample container. The
Contractor shall also follow the instructions given on the Traffic Report in
choosing the QC samples when such information is provided.
6.1 The Contractor shall submit signed copies of Traffic Reports for all
samples in an SDG to SMO within FIVE (5) WORKING days following receipt of
the last sample in the SDG. Traffic Reports shall be submitted in SDG sets
(i.e., all Traffic Reports for a SDG shall be clipped together) with an SDG
Cover Sheet containing information regarding the SDG, as specified in
Exhibit B.
7. EPA Case numbers (including SDG numbers) and EPA sample numbers shall be
used by the Contractor in identifying samples received under this contract
both verbally, in reports, and correspondence.
SECTION III: Technical and Management Requirements
1. Personnel - The Contractor shall have adequate personnel at all times
during the performance of the contract to ensure that EPA receives data that
meet the terms and conditions of the contract.
2. Instrumentation - The Contractor shall have sufficient inductively coupled
plasma (ICP) emission spectrometers with the capability to analyze metals
sequentially or simultaneously, atomic absorption (AA) spectrometers equipped
with graphite furnace, flame, and cold vapor AA (or specific mercury
analyzers) analysis capabilities or equivalent for the analysis of metals, and
analytical equipment/apparatus for analysis of cyanide as described in Exhibit
D to meet all the terms and conditions of the contract.
3. Facilities - The Contractor shall maintain a facility suitable for the
receipt, storage, analysis, and delivery of the product meeting the terms and
conditions of the contract.
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EXHIBIT B:
Reporting and Deliverables Requirements
SECTION I: Contract Reports and Deliverables Distribution B-l
SECTION II: Report Descriptions and Order of Data Deliverables B-4
Part A - Standard Operating Procedures (SOPs) and Quality Assurance Plan
(QAP) B-6
Part B - Sample Traffic Reports B-6
Part C - Sample Data Package B-7
Part D - Complete Sample Delivery Group (SDG) File (CSF) B-12
Part E - Quarterly and Annual Verification of Instrument Parameters , B-l3
Part F - Results of Laboratory Control Sample (LCS) B-14
Part G - Results of Performance Evaluation Sample (PES) B-14
SECTION III - Form Instruction Guide B-15
Part A - General Information and Header Information B-16
Part B - Cover Page [COVER PAGE - LCIN] . B-18
Part C - Comments Page [COMMENTS PAGE - LCIN] B-19
Part D - Analysis Data Sheet [FORM I - LCIN] B-19
Part E - Initial and Continuing Calibration Verification [FORM II -
HCIN] B-22
Part P - CRDL Standards [FORM III - LCIN] B-24
Part G - Linear Range Determination Standard (LRS) [FORM IV - LCIN]: . B-25
Part H - Blanks [FORM V - LCIN] B-27
Part I - ICP-AES AND ICP-MS Interference Check Sample [FORM VI - LCIN] B-28
Part J - Spike Sample Recovery [FORM VII - LCIN] B-31
Part X - Duplicates [FORM VIII - LCIN] B-32
Part L - Laboratory Control Sample [FORM IX - LCIN] B-34
Part M - Serial Dilution [FORM X - LCIN] B-35
Part N - Standard Addition Results [FORM XI - LCIN] B-37
Part O - Instrument Detection Limits (IDL) [FORM XII - LCIN] B-39
Part P - ICP-AES and ICP-MS Elemental Expression Factors (A) [FORM XIII
- LCIN] B-41
Part Q - ICP-AES and ICP-MS Elemental Expression Factors (B) [FORM XIV -
LCIN] B-42
Part R - ICP-MS Tuning and Response Factor Criteria [FORM XV - LCIN] . B-44
Part S - ICP-MS Internal Standards Relative Intensity Summary (A) [FORM
XVI - LCIN] B-46
Part T - Analysis Run Log (A) [FORM XVII - LCIN] B-48
Part V - Analysis Run Log (B) [FORM XVIII - LCIN] B-50
Part V - Standard Solutions Sources [FORM XIX - LCIN] B-52
Part w - Sample Log-In Sheet [FORM DC - 1] B-53
Part X - Document Inventory Sheet (FORM DC - 2) B-54
SECTION IV - Data Reporting Forms B-55
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SECTION I: Contract Reports and Deliverables Distribution
The following table reiterates the Contract reporting and deliverables
requirements specified in the Contract Schedule and specifies the distribution
that is required for each deliverable.
I
Item
[ No. | Delivery | Distributiont
|Copies| Schedule | (1) | (2) | (3)
I standard
I Operating
| Procedures
I
B. Sample Traffic
Reports
I **C. Sample Data
I Package
| ****d. Complete SDG
I File
*E, Quarterly/Annual
Verification
of Instrument
Parameters
*F. ICP-MS
Diskettes/Tapes
Lot
14 days after
receipt of last
sample in SDG
14 days after
receipt of last
sample in SDG**
Quarterly:
15th day of
January, April
July, October
Retain for 365
days after
submission; or
submit them
within 7 days
of written
request by APO
or EMSL-LV
X
60 days after
contract award,
and as required
in Exhibit E
5 working days after
receipt of last |
sample in Sample|
Delivery Group |
(SDG)*** ]
I (
As Directed
X
X
As directed
I I
Quality
Assurance
Plan
60 days after
contract award,
and as required
in Exhibit E
As directed
B-l
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tDistribution
(1) USEPA Contract Laboratory Program (CLP)
Sample Management Office (SMO 51
P. 0, Box 818
Alexandria, VA 22313
For overnight delivery service, use street address:
300 N. Lee Street, 5th Floor
Alexandria, VA 22314
1 The Sample Management Office (SMO) is a contractor-operated facility
operating under the CLASS contract.
(2) USEPA REGIONS: The CLP SMO, acting on behalf of the Administrative
Project Officer (APO), will provide the Contractor with the list of
addressees for the ten EPA Regions. SMO will provide the Contractor
with updated regional name and address lists as necessary throughout the
period of the contract and identify other client recipients on a case-
by-case basis.
(3) USEPA Contract Laboratory Program (CLP)
Quality Assurance Technical Support (QATS) Laboratory2
2700 Chandler Avenue, Building C
Las Vegas, NV 89120
Attn: Data Audit Staff
2 The Quality Assurance Technical Support (QATS) Laboratory is a
contractor-operated facility.
Footnotes:
# Contractor concurrent delivery to QATS may be required upon written
request by the Regional Technical Project Officer (TPO) or APO. The
Contractor shall retain a copy of the sample data package for 365 days
after final data acceptance of the reconciled data package, and submit
within seven (7) days after receipt of written request by the TPO or
APO.
* Also required in each Sample Data Package.
** Concurrent delivery of these items to all recipients is required.
*** A Sample Delivery Group (SDG) is a group of samples within a Case,
received over a period of 7 days or less and not exceeding 20 samples.
Data for all samples in the SDG are due concurrently. (See SOW Exhibit
A, paragraph I., for further description).
**** A Complete SDG File will contain the sample data package plus all of the
original documents described in Exhibit B under "Complete SDG File."
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The Complete SDG File must be delivered concurrently with the Sample
Data Package.
***** See Exhibit E for a more detailed description.
Note 1: Specific recipient names and addresses are subject to change during
the term of the contract. The APO will notify the Contractor in
writing of such changes when they occur.
Note 2: As specified in the Contract Schedule (Government Furnished Supplies
and Materials), unless otherwise instructed by the Contract
Laboratory Program (CLP) SMO, the Contractor shall dispose of unused
sample volume and used sample bottles or containers no earlier than
sixty (60) days following submission of analytical data. Sample
disposal and disposal of unused sample bottles or containers is the
responsibility of the Contractor and should be done in accordance
with all applicable laws and regulations governing the disposal of
such material.
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SECTION II: Report Descriptions and Order of Data Deliverables
1. The Contractor shall pro-vide reports and other deliverables as specified
in the Contract Performance and Delivery Schedule (see Contract Schedule),
The required content and form of each deliverable is described in this
Exhibit, All reports and documentation shall be:
Legible,
Clearly labeled and completed in accordance with instructions in this
Exhibit,
Arranged in the order specified in this Section,
Paginated in ascending order, and
Double-sided.
2. If submitted documentation does not conform to the above criteria, the
Contractor shall be required to resubmit such documentation with the
deficiency(ies) corrected, at no additional cost to the government.
3. Hold status may be applied by the APO due to any technical or
administrative contractual deficiency. During contract hold, samples may not
be scheduled with the Contractor. Reasons for contract hold include, but are
not limited to, PES results, laboratory Contract Compliance Screening (CCS)
results, laboratory audit results, laboratory instrument or personnel
deficiencies, and late data.
4. The Contractor must be prepared to receive the full monthly sample
contract requirement at the time of contract award.
5. When the Contractor is required to submit or resubmit data because of an
on-site laboratory evaluation, a CCS assessment, an APO or Technical Project
Officer (TPO) action, or a regional data reviewer's request, the data shall be
clearly marked "Additional Data," and shall be sent to the following
contractual data recipients:
Sample Management Office (SMO)
Client Region.
5.1 A cover letter shall be included that describes which data are being
delivered, to which EPA case(s) the data pertain, and who requested the data.
6. When the Contractor is required or requested to respond to CCS review by
SMO, the laboratory response shall be sent to the contractual data recipients
(SMO, and the client Region). Each response shall be accompanied by a color-
coded Cover Sheet (Laboratory Response to Results of Contract Compliance
Screening), which shall be provided in generic format by SMO.
7. Section IV of this Exhibit contains the required Inorganic Analysis Data
Reporting Forms in Agency-specified formats. Section III of this Exhibit
contains instructions for completing the data reporting forms that must be
provided to the Agency.
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8. Descriptions of the requirements for each deliverable item cited in the
Contract Performance and Delivery Schedule (see Contract Schedule) are
specified in Parts A-F of this Section. Items submitted concurrently shall be
arranged in the order listed. Additionally, the components of each
deliverable item shall be arranged in the order presented herein when the item
is submitted.
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Part A - Standard Operating Procedures (SOPs) and Quality Assurance Plan (QAP)
1. Submit updated SOPs and QAPs according to the instructions in Exhibit E.
Part B - Sample Traffic Reports
1. The original Sample Traffic Report page marked "Lab Copy for Return to
SMO," with laboratory receipt information and original Contractor signature,
shall be submitted for each sample in the SDG.
2. Traffic Reports (TRs) shall be submitted in Sample Delivery Group (SDG)
sets (i.e., TRs for all samples in an SDG shall be clipped together), with an
SDG Cover Sheet attached.
3. The SDG Cover Sheet shall contain the following items:
Laboratory name
Contract number
Sample Analysis Price - full sample price from contract.
Case Number
List of EPA sample numbers of all samples in the SDG, identifying the first
and last samples received, and their dates of receipt at the laboratory.
Note: When more than one sample is received in the first or last SDG shipment,
the "first" sample received is the lowest sample number (considering alpha and
numeric designations); the "last" sample received is the highest sample number
(considering both alpha and numeric designations).
4. Each TR shall be clearly marked with the SDG number, which is the sample
number of the first sample in the SDG (as described in the following
paragraph). This information shall be entered below "Lab Receipt Date" on the
TR. In addition, the TR for the last sample received in the SDG shall be
clearly marked "SDG - FINAL SAMPLE."
5. The EPA sample number of the first sample received in the SDG is the SDG
number. EPA field sample numbers contain six digits. If the Contractor
receives a sample number of any other length, the Contractor shall contact SMO
immediately. When more than one sample is received in the first SDG shipment,
the SDG number shall be the lowest sample number (considering alpha and
numeric designations) in the first group of samples received under the SDG.
(The SDG number is also reported on all data reporting forms. See Section
III, Form Instruction Guide.)
6. If samples are received at the laboratory with multisample Traffic Reports
(TRs), all the samples on one multisample TR may not be in the same SDG. In
this instance, the laboratory shall submit a copy of the TR with each SDG
cover sheet.
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Part c - Sample Data Package
1. The sample data package shall include data for analysis of all samples in
one SDG, including but not limited to analytical samples, field samples,
reanalyses, blanks, spikes, duplicates, Laboratory Control Samples (LCSs), and
Performance Evaluation Samples (PESs). The sample data package shall be
complete before submission. It shall be consecutively paginated in ascending
order, and shall include the following.
2. The Cover Page for the LC-Inorganic Analyses Data Package (COVER PAGE -
LCIN), shall include;
Laboratory name,
Laboratory code,
Contract number,
Case No.,
• SDG No.,
EPA sample numbers in alphanumeric order, showing EPA sample numbers
cross-referenced with laboratory ID numbers, and,
Completion of the statement on use of inductively coupled plasma (ICP)
background and elemental expression corrections for the samples.
2.1 The Cover Page shall contain the following statement, verbatim: "I
certify that this data package is in compliance with the terms and
conditions of the contract, both technically and for completeness, except
for the conditions detailed above. Release of the data contained in this
hard copy data package and in the computer-readable data submitted on
diskette has been authorized by the Laboratory Manager or the Manager's
designee, as verified by the following signature." This statement shall be
followed by the signature of the Laboratory Manager or the Manager's
designee with a typed line below it containing the signer's name, title,
and date of signature.
3. The Comments Page [COMMENTS PAGE - LCIN] shall include:
details of the problems- encountered in processing the samples in the
data package,
details of technical or administrative problems encountered,
corrective action taken, and
resolution of the problem.
The Contractor shall retain a copy of the Sample Data Package for 365 days
after final acceptance of the reconciled data package. After this time, the
Contractor may dispose of the package.
NOTE: The use of the terms "Comments Page" and "Case Narrative" are used
interchangeably in this document, when one or the other is used it is meant to
refer to the form ([COMMENTS PAGE - LCIN)) in Exhibit B, Section IV - Data
Report Forms.
4. Sample Data: Sample data shall be submitted with the Low Concentration
Inorganic Analysis Data Reporting Forms for all samples in the SDG, including
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the PES, arranged in increasing alphanumeric EPA Sample Number order, followed
by the QC analyses data, and Verification of Instrument Parameters forms, raw
data, and copies of the preparation logs.
4.1 Results — Low Concentration Inorganics Analysis Data Sheet [FORM I -
LCIN]:
4.1.1 Tabulated analytical results (identification and quantitation) of
the specified analytes (Exhibit C). The validation and release of these
results are authorized by a specific, signed statement on the Cover
Page. If the Laboratory Manager cannot verify all data reported for
each sample, he/she shall provide a detailed description of the problems
associated with the sample(s) on the Comments Page.
4.1.2 The quantitative values shall be reported in units of micrograms
per liter (ug/L) for all samples. No other units are acceptable.
Analytical results shall be reported to two significant figures if the
result value is less than 10; to three significant figures if the value
is greater than or equal to 10.
4.2 Quality Control Data
4.2.1 Initial and Continuing Calibration Verification [FORM II-LCIN]
4.2.2 Contract Required Detection Limit (CRDL) Standards [FORM III-
LCIN]
4.2.3 Linear Range Determination Standards [FORM IV-LCIN]
4.2.4 Blanks [FORM V-LCIN]
4.2.5 ICP-AES and ICP-MS Interference Check Sample Results [FORM VI-
LCIN]
4.2.6 Spike Sample Recovery (FORM VII-LCIN]
4.2.7 Duplicates [FORM VIII-LCIN]
4.2.8 Laboratory Control Sample [FORM IX-LCIN]
4.2.9 Serial Dilution [FORM X-LCIN]
4.2.10 Standard Addition Results [FORM XI-LCIN]
4.2.11 Instrument Detection Limits [FORM XII-LCIN]
4.2.12 ICP-AES and ICP-MS Elemental Expression (A) Factors [FORM XIII-
LCIN]
4.2.13 ICP-AES and ICP-MS Elemental Expression (B) Factors [FORM XIV-
LCIN]
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4.2,14 ICP-AES and ICP-MS Tuning and Response Factor Criteria [FORM XV-
LCIN] [FORM XVI-LCIN]
4.2.15 ICP-MS Internal Standards Relative Intensity Summary [FORM XVI-
LCIN]
4.2.16 Analysis Run Log (A) [FORM XVII-LCIN]
4.2.17 Analysis Run Log (B) [FORM XVIII-LCIN]
4.2.18 Standard Solutions Sources [FORM XIX-LCIN]
4.2.19 Sample Log-In Sheet [FORM DC-1]
4.2.20 Document Inventory Sheet [FORM DC-2]
4.3 Raw Data: For each reported value, the Contractor shall include in
the data package all raw data from the instrument used to obtain that value
and the QA/QC values reported (except for raw data for quarterly and annual
verifications of instrument parameters). Raw data shall contain all
instrument readouts used for the sample results, including those readouts
that may fall below the IDL. All instruments shall provide a legible hard
copy of the direct, real-time instrument readout (i.e., strip charts,
printer tapes, etc.). A photocopy or other accurate facsimile of the
direct instrument readout shall be included.
4.3.1 The order of raw data in the data package shall be: ICP-AES,
ICP-MS, flame atomic absorption (AA), graphite furnace AA (GFAA),
mercury, and cyanide.
4.3.2 All raw data shall include intensities or concentration for ICP-
AES, ICP-MS, absorbance or concentration for AA, and spectrophotometric
measurements.
4.3.3 Raw data shall be labeled with an EPA Sample Number and
appropriate codes, specified in Table B-l, to unequivocally identify
4.3.3.1 through 4.3.3.12.
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TABLE B-l CODES FOR LABELING DATA
Sample XXXXXX
Duplicate XXXXXXD
Matrix Spike XXXXXS
Serial Dilution XXXXXXL
Analytical (Post Digestion) Spike XXXXXXA
Method of Standard Additions:
Zero Addition XXXXXXO
First Addition XXXXXX1
Second Addition XXXXXX2
Third Addition XXXXXX3
Instrument Calibration Standards:
ICP-AES, ICP-MS, S or SO for blank standard
graphite furnace AA and Cyanide 0, S10,...etc.
Initial Calibration Verification ICV
Initial Calibration Blank ICB
Continuing Calibration Verification CCV
Continuing Calibration Blank CCB
Interference Check Samples:
Solution A ICSA
Solution AB ICSAB
CRDL Standard CRI
Laboratory Control Samples LCS
Preparation Blank PBW
Linear Range Analysis Standard LRS
Memory Test Solution MTS
Tuning Solution TS
1.1 When an analytical spike or MSA is performed on samples other than
field samples, the "A", "0", "1", "2" or "3" suffixes must be the last to
be added to the EPA Sample Number. For instance, an analytical spike of a
duplicate must be formatted "XXXXXXDA".
1.2 The numeric suffix that follows the "S" suffix for the standards
indicates the true value of the concentration of the standard in ug/L.
1.3 ICP calibration standards usually consist of several analytes at
different concentrations. Therefore, no numeric suffix can follow the ICP
calibration standards unless all the analytes in the standard are prepared
at the same concentrations. For instance, the blank for ICP must be
formatted "SO".
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4.3.3.1 Calibration standards, including source and preparation date.
4.3.3.2 Initial and continuing calibration blanks and preparation
blanks.
4.3.3.3 Initial and continuing calibration verification standards,
interference check samples, CRDL standards, LCS solutions, linear range
standards, tuning standards, memory test solutions, and serial dilution
samples.
4.3.3.4 Diluted and undiluted samples (by EPA Sample Number) and all
dilutions and volumes used to obtain the reported values. (If the
volumes and dilutions are consistent for all samples in a given SDG, a
general statement outlining these parameters may be reported in the SDG
Narrative).
4.3.3.5 Duplicates.
4.3.3.6 Spikes (indicating standard solutions used, final spike
concentrations, volumes involved). If spike information (source,
concentration, volume) is consistent for a given SDG, a general
statement outlining these parameters may be reported in the SDG
Narrative).
4.3.3.7 Instrument and background correction used, any instrument
adjustments, data corrections, or other apparent anomalies in the
measurement record, including all data voided or data not used to obtain
reported values and a brief written explanation in the SDG Narrative.
4.3.3.8 All information, for flame AA and furnace AA analysis, clearly
and sequentially identified in the raw data, including EPA Sample Number
and date of analysis, sample and analytical spike data, percent
recovery, coefficient of variation, full Method of Standard Additions
(MSA) data, MSA correlation coefficient, slope and y intercept of linear
fit, and final sample concentration (standard addition concentration).
4.3.3.9 All ICP-MS tuning and mass calibration data, in addition to all
internal standard results including the elements and concentration used.
4.3.3.10 Time and date of each analysis. Instrument run logs may be
submitted if they contain this information. If the instrument does not
automatically provide times of analysis, they shall be entered manually
on all raw data for initial and continuing calibration verification and
blanks, as well as on data for tuning solutions, CRDL standards,
interference check samples, and the linear range standard.
4.3.3.11 Integration times for all analyses.
4.4 Preparation Logs: Preparation Logs shall be submitted in the
following order: ICP-AES, ICP-MS, flame AA, graphite furnace AA, mercury,
and cyanide. These logs shall include:
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Preparation date,
Sample volume (initial and final),
Sufficient information to unequivocally identify which QC samples (i.e.,
laboratory control sample (LCS), preparation blank) correspond to each
batch prepared,
Comments describing any significant sample changes or reactions that
occurred during preparation, and
Report pH <2 or >12, as applicable.
5. The Contractor shall provide a copy of the Sample Traffic Report described
in Part B for all of the samples in the SDG. The Traffic Reports shall be
arranged in increasing alphanumeric EPA Sample Number order.
Part D - Complete Sample Delivery Group (SDG) File (CSF)
1. As specified in the Delivery Schedule, one CSF, including the original
Sample Data Package, shall be delivered to the Region concurrently with
delivery of a copy of the Sample Data Package to SMO. The contents of the CSF
will be numbered according to the specifications described in Section III and
IV of Exhibit B. The Document Inventory Sheet, Form DC-2, is contained in
Section IV. The CSF will contain all original documents where possible.
Copies will not be placed in the CSF unless the original documents are bound
in a logbook maintained by the laboratory. The CSF will contain all original
documents specified in Section III and IV, and Form DC-2 of Exhibit B of the
SOW.
2. The CSF will consist of the following original documents in addition to
the documents in the Sample Data Package.
2.1 Original Sample Data Package (See Exhibit 3, Section II, Part C)
2.2 A completed and signed Document Inventory Sheet (Form DC-2)
2.3 All original shipping documents including, but not limited to, the
following documents:
2.3.1 EPA Chain-of-Custody Record.
2.3.2 Airbills.
2.3.3 EPA (SMO) Traffic Reports.
2.3.4 Sample Tags (if present) sealed in plastic bags.
2.4 All original receiving documents including, but not limited to, the
following documents:
2.4.1 Form DC-1.
2.4.2 Other receiving forms or copies of receiving logbooks.
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2.4.3 SDG Cover Sheet.
2.5 All original laboratory records of sample transfer, preparation, and
analysis including, but not limited to, the following documents;
2.5.1 Original preparation and analysis forms or copies of preparation
and analysis logbook pages.
2.5.2 Internal sample and sample extract transfer chain-of-custody
records.
2.5.3 All instrument output, including strip charts from screening
activities.
2.6 All other original case-specific documents in the possession of the
laboratory including, but not limited to, the following documents;
2.6.1 Telephone contact logs.
2.6.2 Copies of personal logbook pages.
2.6.3 All handwritten Case-specific notes.
2.6.4 Any other Case-specific documents not covered by the above.
2.6.4.1 Note that all Case-related documentation may be used or
admitted as evidence in subsequent legal proceedings. Any other
Case-specific documents generated after the CSF is sent to EPA, as
well as copies that are altered in any fashion, are also deliverables
to EPA (original to the Region and a copy to SMO).
2.6.4.2 If the laboratory submits Case-specific documents to EPA
after submission of the CSF, the documents should be numbered as an
addendum to the CSF and a revised DC-2 Form should be submitted; or
the documents should be numbered as a new CSF and a new DC-2 Form
should be submitted to the Region only.
Part E - Quarterly and Annual Verification of Instrument Parameters
1. The Contractor shall perform and report quarterly verification of
instrument detection limits by methods specified in Exhibit E for each
instrument used under this contract. For the ICP-AES and ICP-MS
instrumentation, the Contractor shall also perform and report annually
elemental expression factors (including method of determination), elemental
expressions used, and integration times. Forms for quarterly and annual
verification of instrument parameters for the current year shall be submitted
in each SDG data package, on Forms XII and XIII as specified in Section III of
this Exhibit. Submission of quarterly and annual verification of instrument
parameters shall include the raw data used to determine those values reported.
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2. If the Contractor fails to adhere to the requirements listed in this
section, the Contractor may expect, but the Agency is not limited to, the
following actions:
reduction in the number of samples sent under the contract,
suspension of sample shipment to the Contractor,
ICP-MS tape audit (if appropriate),
data package audit,
on-site laboratory evaluation,
remedial performance evaluation sample, and/or
contract sanctions, such as a Cure Notice.
Part F - Results of Laboratory Control Sample (LCS)
1. Analytical results and QC for the method reference sample analysis, as
specified in Exhibit E, shall be tabulated on Form IX.
Part G - Results of Performance Evaluation Sample (PES)
1. Analytical results for the PES analysis, as specified in Exhibit E, shall
be tabulated on Form I.
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SECTION III - Form Instruction Guide
This section contains specific instructions for the completion of all required
Inorganic Data Reporting Forms. This section is organized into the following
Parts;
Part A - General Information and Header Information B-16
Part B - Cover Page [COVER PAGE - LCIN] B-18
Part C - Comments Page [COMMENTS PAGE - LCIN] B-19
Part D - Analysis Data Sheet [FORM I - LCIN] B-19
Part E - Initial and Continuing Calibration Verification [FORM II - HCIN] B-22
Part F - CRDL Standards [FORM III - LCIN] B-24
Part G - Linear Range Determination Standard (LRS) [FORM IV - LCIN]: . , B-25
Part H - Blanks [FORM V - LCIN] B-27
Part I - ICP-AES AND ICP-MS Interference Check Sample [FORM VI - LCIN] . B-28
Part J - Spike Sample Recovery [FORM VII - LCIN] B-31
Part K - Duplicates [FORM VIII - LCIN] B-32
Part L - Laboratory Control Sample [FORM IX - LCIN] B-34 -
Part M - Serial Dilution [FORM X - LCIN] B-35
Part N - Standard Addition Results [FORM XI - LCIN] B-37
Part 0 - Instrument Detection Limits (IDL) [FORM XII - LCIN] B-39
Part P - ICP-AES and ICP-MS Elemental Expression Factors (A) [FORM XIII -
LCIN] B-41
Part Q - ICP-AES and ICP-MS Elemental Expression Factors (B) [FORM XIV -
LCIN] B-42
Part R - ICP-MS Tuning and Response Factor Criteria [FORM XV - LCIN] . . B-44
Part S - ICP-MS Internal Standards Relative Intensity Summary (A) [FORM XVI
- LCIN] B-46
Part T - Analysis Run Log (A) [FORM XVII - LCIN] . B-48
Part U - Analysis Run Log (B) [FORM XVIII - LCIN] ............ B-50
Part V - Standard Solutions Sources [FORM XIX - LCIN] B-52
Part W - Sample Log-In Sheet [FORM DC - 1] B-53
Part X - Document Inventory Sheet (FORM DC - 2) B-54
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Fart A - General Information and Header Information
1. Values must be reported on the hard copy data reporting forms according to
the individual form instructions in this Section. Each form submitted must be
filled out completely for all analytes and samples before proceeding to the
next form of the same type. Multiple forms cannot be submitted in place of
one form if the information on those forms can be submitted on one form.
2. All typed characters that appear on the data reporting forms presented in
the contract (Exhibit B, Section IV) must be reproduced by the Contractor when
submitting data, and the format of the forms submitted must be identical to
that shown in the contract. No information may be added, deleted, or moved
from its specified position without prior written approval of the EPA
Administrative Project Officer (APQ). The names of the various fields and
analytes (i.e., "Lab Code," "Aluminum") must appear as they do on the forms in
the contract, including the options specified in the form.
3. Five pieces of information are common to the header sections of each data
reporting form. These are: Lab Name, Contract, Lab Code, Case No., and SDG
No. This information must be entered on every form and must match on all
forms.
3.1 "Lab Name" is the name chosen by the Contractor to identify the
laboratory. It may not exceed 25 characters.
3.2 "Contract" is the number of the EPA contract, including hyphens, under
which the analyses were performed.
3.3 "Lab Code" is an alphabetic code of up to 6 characters/ to identify
the laboratory. This code shall be assigned by the EPA at the time a
contract is awarded, and must not be modified by the Contractor, except at
the direction of EPA.
3.4 "Case No." is the EPA-assigned Case number (5 spaces maximum)
associated with the sample and reported on the Traffic Report (TR) .
3.5 "SDG No." is the EPA Sample Number of the first sample received in the
SDG. When several samples are received together in the first SDG shipment,
the SDG number must be the lowest alphanumeric sample number in the first
group of samples received under the SDG.
4. "EPA Sample No." is common to several of the forms.
4.1 This number appears in the upper right-hand corner of the form or at
the left column of a table summarizing data from a number of samples. When
"EPA Sample No." is entered into a triple-spaced box in the upper right-
hand corner of a form, it must be centered.
4.2 All field samples and quality control (QC) samples must be identified
with an EPA Sample Number. For field samples, the EPA Sample Number is the
unique identifying number given in the TR that accompanied that sample.
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The QC samples abbreviations listed in Table B-l must be used as
appropriate.
5. "Run No." refers to a number assigned to a collective sequential
analytical run which starts, ends, and encompasses all of the QA/QC relevant
to the analytical run from Exhibit E. A run number of 1 is assigned to the
chronologically oldest analytical run used to report data. A run number of 2
is associated with the next oldest analytical run, and so on.
6. A Form Suffix for each form must appear in the two-character space
provided after the form number in the bottom section of the form. The Form
Suffix is used to sequentially distinguish between different forms of the same
type (Form Number).
7. All the values substituted in the formulas given in the forms instructions
must be exactly those values reported on the form for which the formula
applies.
8. "EE" is the elemental expression used to obtain data for each analyte.
For ICP-AES and AA, the elemental expression identifies the wavelength used
and interference correction terms (if any). For 1CP-MS, the elemental
expression identifies the primary quantitation mass and isobaric interference
correction terms (if any). The actual elemental expressions are specified on
Form XIII and are assigned an individual identifying number (the "EE" number)
if more than one expression is specified for a given analyte.
8.1 Under "EE," enter the number of the elemental expression that was used
to derive the results for each analyte reported on the form. The "EE" is a
number assigned to each elemental expression when more than one elemental
expression is used to obtain data for an analyte in the SDG. An "EE"
number of 1 should be assigned to the most frequently used elemental
expression for a given analyte in the SDG. An "EE" number of 2 should be
assigned to the second most frequently used elemental expression, and so
on. If only one elemental expression is used to obtain data for an analyte
in the SDG, an "EE" number of 1 should be assigned to the elemental
expression. The "EE" number must be consistently applied to the elemental
expression it identifies for the entire SDG.
9. All results must be transcribed to Forms II-XIX from the raw data to the
specified number of decimal places that are described in Exhibit B. The raw
data result is to be rounded only when the number of figures in the raw data
result exceeds the maximum number of figures specified for that result entry
on that form. If there are not enough figures in the raw data result to enter
in the specified space for that result, then zeros must be used for decimal
places to the specified number of reporting decimals for that result for a
specific form. The following examples of floating decimal places are
provided:
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Raw Data Result
Specified Format
Correct Entry on Form
5.99653
95.99653
995.99653
9995.996
99995.9
999995.9
5.9
6.3
6.3
6.3
6.3
6.3
6.3
6.3
5.900
5.997
95.997
996.00
9996.0
99996.
invalid
Note: The specified format of 6.3 means that a maximum of 6 spaces may be
used to report the data, of which a maximum of 3 decimal places may be used.
10. To roundnumbers to the appropriate level of precision, observe the
following common rules. If the figure following those to be retained is less
than 5, drop it (round down). If the figure is greater than 5, drop it and
increase the last digit to be retained by 1 (round up). If the figure
following the last digit to be retained equals 5 and there are no digits to
the right of the 5 or all digits to the right of the 5 equal zero, then round
up if the digit to be retained is odd, or round down if that digit is even.
See also Rounding Rules entry in Glossary (Exhibit G).
11. Before evaluating a number for being in or out of control, round the
number using EPA rounding rules to the significance required. For instance,
the control limit for an ICV is plus or minus 10 percent of the true value. A
percent recovery value of 110.4 would be considered in control while a value
of 110.6 would be considered out of control. In addition, a value of 110.50
would be in control while a value of 110.51 would be out of control.
Part B - Cover Page [COVER PAGE - LCIN]: This form is used to list all field
samples, duplicates, spikes, and performance evaluation samples (PES) analyzed
within a SDG, and to provide certain analytical information. The form is
signed by the Laboratory Manager to authorize and release all data and
deliverables associated with the SDG.
1. Complete the header information according to the instructions in Part A
and as follows.
2. The "SOW No." is the EPA-designated number that indicates the SOW version
used for the data package being reported. For samples analyzed using this
SOW, enter "ILC03.1" for "SOW No."
3. Under "EPA Sample No.," enter the EPA Sample No. of each field sample,
(including spikes, duplicates, and the PES) to eight spaces, for the sample
analyzed within the SDG. Spikes must contain an "S" suffix and duplicates a
"D" suffix. These sample numbers must be listed on the form in ascending
alphanumeric order using the EBCDIC convention. Thus, if MAB123 is the lowest
(considering both alpha and numeric characters) EPA Sample No. within the SDG,
it would be entered in the first EPA Sample No. field. Samples would be
listed below it, in ascending sequence - MAB124, MAB125, MAC111, MA1111,
MA1111D, MA1111S, etc.
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4. All EPA Sample Nos. must be listed in ascending alphanumeric order,
continuing to additional Cover Pages if necessary.
5. Under "Lab Sample ID.," a Lab Sample ID. (to 10 spaces) may be entered for
each EPA Sample No. If a Lab Sample ID is entered, it must be entered
identically (for each EPA Sample No.) on all associated forms.
6. Enter "YES" or "NO" in answer to each of the two questions concerning ICP-
AES and ICP-MS corrections. Each question must be explicitly answered with a
"YES" or a "NO." The third question must be answered with a "YES" or "NO" if
the answer to the second question is "YES." It should be left blank if the
answer to the second question is "NO."
7. Each Cover Page original must be signed and dated by the Laboratory
Manager or the Manager's designee to authorize the release and verify the
contents of all data and deliverables associated with an SDG.
8. For "Name," enter the first and last name (to 25 spaces) of the person
whose signature appears on the Cover Page.
9. For "Date," enter the date (formatted MM/DD/YY) on which the Cover Page is
signed.
10. For "Title," enter the title (to 25 spaces) of the person whose signature
appears on the Cover Page.
Part c - Comments Page [COMMENTS PAGE - LCIN]: This form is used to enter
comments that are relevant to the analyses performed under the SDG as a whole.
1. Complete the header information according to the instructions in Part A,
Part B (as applicable), and as follows.
2. Comments should describe in detail any problems encountered in processing
the samples in the data package, any technical or administrative problems
encountered, the corrective actions taken, all communication with SMO and/or
the Regional representative(s), and the resolution of the problems.
3. Also included should be explanations detailing the rationale used for the
elemental expressions which differ from those recommended by this SOW. These
explanations should include the limitations of the elemental expressions, and
their applicability to the samples analyzed.
Part D - Analysis Data Sheet [FORM I - LCIN]: This form is used to tabulate
and report sample analysis results for target analytes (Exhibit C).
1. Complete the header information according to the instructions in Part A
and as follows.
2. "Lab Sample ID," is the laboratory sample ID of the EPA sample number
listed on the form if one was designated on the Cover Page.
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3. "Date Received" is the date (formatted MM/DD/YY) of sample receipt at the
laboratory, as recorded on the TR, i.e., the Validated Time of Sample Receipt
(VTSR).
4. "EE" is the elemental expression used to obtain data for each analyte.
For ICP-AES and AA, the elemental expression identifies the wavelength used
and interference correction terms (if any). For ICP-MS, the elemental
expression identifies the primary quantitation mass and isobaric interference
correction terms (if any). The actual elemental expressions are specified on
Form XIII and are assigned an individual identifying number (the "EE" number)
if more than one expression is specified for a given analyte. For each blank,
enter the concentration of each analyte (positive or negative) whose absolute
value exceeds the IDL.
4.1 Under "EE," enter the number of the elemental expression that was used
to derive the results for each analyte reported on the form. The "EE" is a
number assigned to each elemental expression when more than one elemental
expression is used to obtain data for an analyte in the SDG. An "EE"
number of 1 should be assigned to the most frequently used elemental
expression for a given analyte in the SDG. An "EE" number of 2 should be
assigned to the second most frequently used elemental expression, and so
on. If only one elemental expression is used to obtain data for an analyte
in the SDG, an "EE" number of 1 should be assigned to the elemental
expression. The "EE" number must be consistently applied to the elemental
expression it identifies for the entire SDG.
5. Under the column labeled "Concentration," enter for each analyte the value
of the result.
5.1 Analytical results must be reported to two significant figures if the
result value is less than 10; to three significant figures if the result
value is greater than or equal to 10.
5.1.1 Note: This requirement for reporting results to two or three
significant figures applies to Form I-LCIN only. Follow the specific
instructions for reporting all other results on required forms as
described in this exhibit.
6. Under the columns labeled "C," "Q," and "M," enter result qualifiers as
identified below. If additional qualifiers are used, their explicit
definitions must be included on the Cover Page in the Comments section.
6.1 C (Concentration) qualifier — Enter "U" if the reported value was
obtained from a reading that was less than the IDL. Use "B" if the value
is less than the CRDL and greater than or equal to the IDL. Leave blank if
greater than or equal to the CRDL.
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6.2 Q qualifier — Specified entries and their meanings are as follows:
C - CRDL Standard not within control limits.
E - The reported value is estimated because of the presence of an
interference.
M - Duplicate injection (exposure) precision not met.
N - Spiked sample recovery not within control limits.
S - The reported value was determined by the Method of Standard
Additions (MSA).
• W - Analytical spike recovery not witin control limits
Asterisk (*) - Duplicate analysis not within control limits.
Plus (+) - Correlation coefficient for the MSA is less than 0.995.
More than one of these qualifiers may be used in the Q column, except
that entering "E," "S," or "+" is mutually exclusive. No combination of
these qualifiers can appear in the same field for an analyte.
6.3 M (Method) qualifier — Enter:
"P" for ICP-AES when open beaker digestion is used
"M" for ICP-MS when open beaker digestion is used
"F" for graphite furnace AA when open beaker digestion is used
"A" for flame AA when open beaker digestion is used
"PM" for ICP-AES when microwave digestion is used
"MM" for ICP-MS when microwave digestion is used
"FM" for graphite furnace AA when microwave digestion is used
"AM" for flame AA when microwave digestion is used
"PB" for ICP-AES when block digestion is used
"MB" for ICP-MS when block digestion is used
"FB" for graphite furnace AA when block digestion is used
"AB" for flame AA when block digestion is used
• "CV" for Cold Vapor AA
"AV" for automated cold vapor AA
"AS" for semi-automated Spectrophotometric
"C" for manual spectrophotometric
"CA" for midi-distillation Spectrophotometric
"AC" for automated spectrophotometric
"NR" if the analyte is not required to be analyzed
" " if no results for the analyte appear on the form
6.4 A brief physical description of the sample before and after
preparation must be reported:
Color - red, blue, yellow, green, orange, violet, white, colorless,
brown, grey, or black
Clarity - clear, cloudy, or opaque
Viscosity - nonviscous or viscous
6.5 Under "Comments" note any significant changes that occur during sample
preparation i.e., emulsion formation, or sample-specific comments
concerning the analyte results.
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Part E - Initial and Continuing Calibration Verification [FORM II - HCIN]:
This form is used to report analyte recoveries from calibration solutions.
1. Complete the header information according to the instructions in Part A
and as follows.
2. "Run No.", refers to a number assigned to a collective sequential
analytical run which starts, ends, and encompasses all of the QA/QC relevant
to the analytical run from Exhibit E. A run number of 1 is assigned to the
chronologically oldest analytical run used to report data, A run number of 2
is associated with the next oldest analytical run, and so on.
3. "EE" is the elemental expression used to obtain data for each analyte.
For ICP-AES and AA, the elemental expression identifies the wavelength used
and interference correction terms (if any). For ICP-MS, the elemental
expression identifies the primary quantitation mass and isobaric interference
correction terms (if any). The actual elemental expressions are specified on
Form XIII and are assigned an individual identifying number (the "EE" number)
if more than one expression is specified for a given analyte.
3.1 Under "EE," enter the number of the elemental expression that was used
to derive the results for each analyte reported on the form. The "EE" is a
number assigned to each elemental expression when more than one elemental
expression is used to obtain data for an analyte in the SDG. An "EE"
number of 1 should be assigned to the most frequently used elemental
expression for a given analyte in the SDG. An "EE" number of 2 should be
assigned to the second most frequently used elemental expression, and so
on. If only one elemental expression is used to obtain data for an analyte
in the SDG, an "EE" number of 1 should be assigned to the elemental
expression. The "EE" number must be consistently applied to the elemental
expression it identifies for the entire SDG.
4. Three items are listed under "Initial Calibration."
4.1 Under "True," enter the value (in ug/L, to two decimal places) of the
concentration of each analyte in the Initial Calibration Verification
solution (ICV) . If an analysis was not performed on the analyte, leave the
field blank.
4.2 Under "Found," enter the value (in ug/L, to three decimal places), of
the concentration of each analyte measured in the ICV.
4.3 Under "%R," enter the value (to the nearest whole number) of the
percent recovery computed according to the following equation:
%R = FouDd (ICV) x 100
Tiue (ICV)
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where True(ICV) is the true concentration of the analyte in the ICV and
Found (ICV) is the found concentration of the analyte in the ICV".
5. "Continuing Calibration has three items:
5.1 Under "True," enter the value (in ug/L, to two decimal places) of the
concentration of each analyte in the Continuing Calibration Verification
solution (CCV) . If an analysis is not performed on the analyte, leave the
field blank.
5.2 Under "Found," enter the value (in ug/L, to three decimal places) of
the concentration of each analyte measured in the CCV.
5.2.1 Note that the form contains two "Found" columns. The column to
the left must contain values for the first CCV and the column to the
right must contain values for the second CCV. The column to the right
should be left blank if no second CCV was performed during the run.
5.2.2 If more than one Form II is required to report multiple CCVs,
then the column to the left on the second form must contain values for
the third CCV, the column to the right must contain values for the
fourth CCV, and so on.
5.3 Under "IR," enter the value (to the nearest whole number) of the
percent recovery computed according to the following equation:
%R - £°U2LCCCY) x 100
True (CCV)
where True(CCV) is the true concentration of each analyte, and Found(CCV) is
the found concentration of the analyte measured in the CCVs.
5,3.1 Note that the form contains two "Continuing Calibration %R"
columns. Entries to these columns must follow the sequence detailed
above for entries to the "Continuing Calibration Found" columns.
6. Under "M," enter the method used, as explained in Part D.
7. Under "Comments" give additional relevant information.
7.1 Note that the order of reporting ICVs and CCVs for each analyte must
follow the chronological order in which the standards were run, starting
with the first Form II and moving from the left to the right continuing to
additional Form lis as appropriate. For instance, the first ICV for all
analytes must be reported on the first Form II. In a run where three CCVs
were analyzed, the first CCV must be reported in the left CCV column on the
first Form II and the second CCV must be reported in the right column of
the same form. The third CCV must be reported in the left CCV column of
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the second Form II. On the second Form II, the ICV column and the right
CCV column must be left empty in this example. In the previous example, if
a second run for an analyte was needed, the ICV of that run must be
reported on a third Form II and the CCVs follow in the same fashion as
previously explained. Where more than one elemental expression is used for
an analyte in the SDG, all ICV and CCV results using "EE" number 1 must be
reported before proceeding to report the results from "EE" number 2, and so
on.
Part F - CRDL Standards [FORM III - LCIN]: This form is used to report
analyte recoveries from analyses of the CRDL Standards.
1. Complete the header information according to the instructions in Part A
and as follows.
2. "Run No.," refers to a number assigned to a collective sequential
analytical run which starts, ends, and encompasses all of the QA/QC relevant
to the analytical run from Exhibit E. A run number of 1 is assigned to the
chronologically oldest analytical run used to report data. A run number of 2
is associated with the next oldest analytical run, and so on.
3. "EE" is the elemental expression used to obtain data for each analyte.
For ICP-AES and AA, the elemental expression identifies the wavelength used
and interference correction terms (if any). For ICP-MS, the elemental
expression identifies the primary quantitation mass and isobaric interference
correction terms (if any). The actual elemental expressions are specified on
Form XIII and are assigned an individual identifying number (the "EE" number)
if more than one expression is specified for a given analyte.
3.1 Under "EE," enter the number of the elemental expression that was used
to derive the results for each analyte reported on the form. The "EE" is a
number assigned to each elemental expression when more than one elemental
expression is used to obtain data for an analyte in the SDG. An "EE"
number of 1 should be assigned to the most frequently used elemental
expression for a given analyte in the SDG. An "EE" number of 2 should be
assigned to the second most frequently used elemental expression, and so
on. If only one elemental expression is used to obtain data for an analyte
in the SDG, an "EE" number of 1 should be assigned to the elemental
expression. The "EE" number must be consistently applied to the elemental
expression it identifies for the entire SDG.
4. The "Initial" and "Final" columns contain several parts.
4.1 Under "Initial True," enter the value (in ug/L, to two decimal places)
of the concentration of each analyte in the CRDL Standard Source Solution
that was analyzed for analytical samples associated with the SDG.
4.2 Under "Initial Found," enter the value (in ug/L, to three decimal
places) of the concentration of each analyte measured in the CRDL Standard
Solution analyzed at the beginning of each run.
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4.3 Under "Final Found," enter the value (in ug/L, to three decimal
places) of the concentration of each analyte measured in the CRDL Standard
Solution analyzed at the end of each run,
4.4 Under "Initial %R" and "Final %R," enter the value (to the nearest
whole number) of the percent recovery computed according to the following
equation:
%r = CRDL Standard Found x jqq
CRDL Standard True
4.5 Note that for every initial solution reported there must be a final
one. However, the opposite is not true. If a CRDL Standard was required
to be analyzed in the middle of a run (to avoid exceeding the 8-h limit),
it must be reported in the "Final Found" section of this form.
5. Under "M," enter the method used, as explained in Part D.
5.1 If more CRDL standards analyses were required or analyses were
performed using more than one elemental expression per analyte, submit
additional Form Ills in the order explained in Part E as appropriate.
6. Under "Comments" give additional relevant information.
7. The order of reporting CRDL standards for each analyte must follow the
chronological order in which the standards were run starting with the first
Form III and continuing to the following Form Ills as appropriate. When
multiple elemental expressions are used for one analyte, all results using
"EE" number 1 must be reported before proceeding to report the results from
"EE" number 2, and so on.
Part G - Linear Range Determination Standard (LRS) [FORM IV - LCIN]: This
form is used to report the upper limit of the linear range of all analysis
systems and the analyte recoveries from analyses of the Linear Range
Determination Standards (LRS).
1. Complete the header information according to the instructions in Part A
and as follows.
2. "Run No.," refers to a number assigned to a collective sequential
analytical run which starts, ends, and encompasses all of the QA/QC relevant
to the analytical run from Exhibit E. A run number of 1 is assigned to the
chronologically oldest analytical run used to report data. A run number of 2
is associated with the next oldest analytical run, and so on.
3. "EE" is the elemental expression used to obtain data for each analyte.
For ICP-AES and AA, the elemental expression identifies the wavelength used
3-25
ILC03.1
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and interference correction terms (if any). For ICP-MS, the elemental
expression identifies the primary quantitation mass and isobaric interference
correction terms (if any). The actual elemental expressions are specified on
Form XIII and are assigned an individual identifying number (the "EE" number)
if more than one expression is specified for a given analyte.
3.1 Under "EE," enter the number of the elemental expression that was used
to derive the results for each analyte reported on the form. The "EE" is a
number assigned to each elemental expression when more than one elemental
expression is used to obtain data for an analyte in the SDG. An "EE"
number of 1 should be assigned to the most frequently used elemental
expression for a given analyte in the SDG. An "El" number of 2 should be
assigned to the second most frequently used elemental expression, and so
on. If only one elemental expression is used to obtain data for an analyte
in the SDG, an "EE" number of 1 should be assigned to the elemental
expression. The "EE" number must be consistently applied to the elemental
expression it identifies for the entire SDG.
4. The "Initial" and "Final" columns contain several parts.
4.1 Under "Initial True," enter the highest calibration standard used or
the value (in ug/L, to two decimal places) of the concentration of each
analyte in the LRS that was analyzed for analytical samples associated with
the SDG.
4.2 Under "Initial Found," enter the value {in ug/L, to three decimal
places) of the concentration of each analyte measured in the LRS analyzed.
4.3 Under "Final Found," if a second LRS was used enter the value (in
ug/L, to three decimal places) of the concentration of each analyte
measured in the LRS analyzed at the end of each run.
4.4 Under "Initial %R" and "Final %R," enter the value (to the nearest
whole number) of the percent recovery computed according to the following
equation:
%r - LRS Standard Found x 10Q
LRS Standard True
5. Under "M," enter the method of analysis (two characters maximum) for which
the elemental expressions listed on the form were made as follows:
• "P" for ICP-AES
• "M" for ICP-MS
"F" for graphite furnace AA
• "A" for flame AA
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6. If more LRS standards analyses were required or analyses were performed
using more than one elemental expression per analyte, submit additional Form
IVs in chronological order as explained in Part E as appropriate.
6.1 The order of reporting LRS standards for each analyte must follow the
chronological order in which the standards were run starting with the first
Form IV and continuing to the following Form IVs as appropriate. When
multiple elemental expressions are used for an analyte, all the results of
"EE" number 1 must be reported before proceeding to "EE" number 2, and so
on.
7. Under "Comments" give additional relevant information.
Part H - Blanks [FORM V - LCIN]: This form is used to report analyte
concentrations found in the Initial Calibration Blank (ICB), in Continuing
Calibration Blanks (CCB), and in the Preparation Blank (PB)*
1. Complete the header information according to the instructions in Part A
and as follows.
2. "Run No.," refers to a number assigned to a collective sequential
analytical run which starts, ends, and encompasses all of the QA/QC relevant
to the analytical run from Exhibit E. A run number of 1 is assigned to the
chronologically oldest analytical run used to report data. A run number of 2
is associated with the next oldest analytical run, and so on.
3. "EE" is the elemental expression used to obtain data for each analyte.
For ICP-AES and AA, the elemental expression identifies the wavelength used
and interference correction terms (if any). For ICP-MS, the elemental
expression identifies the primary quantitation mass and isobaric interference
correction terms (if any). The actual elemental expressions are specified on
Form XIII and are assigned an individual identifying number (the "EE" number)
if more than one expression is specified for a given analyte.
3.1 Under "EE," enter the number of the elemental expression that was used
to derive the results for each analyte reported on the form. The "EE" is a
number assigned to each elemental expression when more than one elemental
expression is used to obtain data for an analyte in the SDG. An "EE"
number of 1 should be assigned to the most frequently used elemental
expression for a given analyte in the SDG. An "EE" number of 2 should be
assigned to the second most frequently used elemental expression, and so
on. If only one elemental expression is used to obtain data for an analyte
in the SDG, an "EE" number of 1 should be assigned to the elemental
expression. The "EE" number must be consistently applied to the elemental
expression it identifies for the entire SDG.
4. Under "Initial Calib. Blank," enter the value (in ug/L, to three decimal
places) of the concentration of each analyte measured in the ICB.
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4.1 Under the "C" qualifier field, for any analyte, enter "U" if the
absolute value of the analyte in the blank is less than the IDL. Use "B"
if the value is less than the CRDL and greater than or equal to the IDL.
5. Under "Continuing Calibration Blank" several items are listed.
5.1 Under "Continuing Calibration Blank 1," enter the value (in ug/L, to
three decimal places) of the measured concentration of each analyte
detected in the first required CCB analyzed after the ICB.
5.2 Enter an appropriate qualifier, as explained for the "Initial Calib.
Blank," (4.1 above) to the "C" qualifier column immediately following the
"Continuing Calibration Blank 1" column.
5.3 If only two CCBs were analyzed, then leave the columns labeled "3"
blank. If an additional CCB was analyzed, complete the columns labeled
"3," in accordance with the instructions for the "Continuing Calibration
Blank 1" column. If more than three CCBs were analyzed, then complete
additional Form Vs as appropriate, following the chronological order in
which they were run.
6. Under "Prep. Blank," enter the value (in ug/L, to three decimal places) of
the measured concentration of each analyte in the Preparation Blank.
6.1 Enter any appropriate qualifier, as explained for the "Initial
Calibration Blank," (4.1 above) to the "C" qualifier column immediately
following the "Prep. Blank" column.
7. Under "M," enter the method used, as explained in Part D.
8. Under "Comments" give additional relevant information,
9. If more than one elemental expression is used for an analyte, submit
additional Form Vs as appropriate.
10. The order of reporting ICBs and CCBs for each analyte must follow the
chronological order in which the blanks were run starting with the first Form
V and moving from left to right and continuing to the following Form Vs as
explained in Part E. When multiple elemental expressions are used for the
analysis of one analyte, all the results of "EE" number 1 must be reported
before proceeding to "EE" number 2, and so on.
Part I - ICP-AES AND ICP-MS Interference Check Sample [FORM VI - LCIN]: This
form is used to report Interference Check Sample (ICS) results for each ICP-
AES or ICP-MS instrument used for each SDG.
1. Complete the header information according to the instructions in Part A
and as follows.
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2. For "Instrument ID Number," enter an identifier that uniquely identifies a
specific instrument within the Contractor laboratory. No two Instruments
within a laboratory may have the same Instrument ID Number.
3. The "Run No." found on many of the forms, refers to a number assigned to a
collective sequential analytical run which starts, ends, and encompasses all
of the QA/QC relevant to the analytical from Exhibit E. A run number of 1 is
assigned to the chronologically oldest analytical run used to report data. A
run number of 2 is associated with the next oldest analytical run, and so on.
4. "EE" is the elemental expression used to obtain data for each analyte.
For ICP-AES the elemental expression identifies the wavelength used and
interference correction terms (if any). For ICP-MS, the elemental expression
identifies the primary quantitation mass and isobaric interference correction
terms (if any). The actual elemental expressions are specified on Form XIII
and are assigned an individual identifying number (the "EE" number) if more
than one expression is specified for a given analyte.
4.1 Under "EE," enter the number of the elemental expression that was used
to derive the results for each analyte reported on the form. The "EE" is a
number assigned to each elemental expression when more than one elemental
expression is used to obtain data for an analyte in the SDG. An "EE"
number of 1 should be assigned to the most frequently used elemental
expression for a given analyte in the SDG. An "EE" number of 2 should be
assigned to the second most frequently used elemental expression, and so
on. If only one elemental expression is used to obtain data for an analyte
in the SDG, an "EE" number of 1 should be assigned to the elemental
expression. The "EE" number must be consistently applied to the elemental
expression it identifies for the entire SDG.
5. True and Found Values
5.1 For all found values of solutions A and AB, enter the concentration
{positive, negative, or zero) of each analyte not present in Solution A at
each elemental expression used for analysis by the instrument.
5.2 Under "True Sol. A," enter the true concentration (in ug/L, to two
decimal places) of each analyte analyzed by ICP that is present in Solution
A. A concentration of zero "0" must be entered for the analytes analyzed
by ICP-AES or ICP-MS that have no true value.
5.3 Under "True Sol. AB," enter the true concentration (in ug/L, to two
decimal places) of each analyte present in Solution AB. A concentration of
zero "0" must be entered for the analytes analyzed by ICP-AES or ICP-MS
that have no true value.
5.4 Under "Initial Found Sol. A," enter the value (in ug/L, to three
decimal places) of the measured concentration for each analyte analyzed by
ICP-AES or ICP-MS that resulted from the initial analysis of Solution A as
required in Exhibit E.
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5.5 Under "Initial Found Sol. AB," enter the value (in ug/L, to three
decimal places) of the measured concentration for each analyte analyzed by
ICP-AES or ICP-MS that resulted from the initial analysis of Solution AB as
required in Exhibit E.
5.6 For ICP-AES analysis under "Final Found Sol. A," enter the value (in
ug/L, to three decimal places) of the measured concentration which resulted
from the final analysis of Solution A as required in Exhibit E. ICP-MS
analysis does not require a final analysis.
5.7 For ICP-AES analysis under "Final Found Sol. AB," enter the value (in
ug/L, to three decimal places) of the measured concentration which resulted
from the final analysis of Solution AB as required in Exhibit E. ICP-MS
analysis does not require a final analysis.
5.8 Under "Initial Found %R" and "Final Found %R," enter the value (to the
nearest whole number) of the percent recovery computed according to the
following equation:
%r = Found Solution A or AB x ^
True Solution A or AB
5.8.1 Leave the field empty if the True Solution A or AB is equal to
zero.
5.9 Note that, except in the case of ICP-MS, for every initial solution
reported there must be a final one. However, the opposite is not true. If
an ICS was required to be analyzed in the middle of a run (to avoid
exceeding the 8-h limit), it must be reported in the "Final Found" section
of this form.
6. Under "M," enter the method of analysis (two characters maximum) for which
the elemental expressions listed on the form were made as follows,
• "P" for ICP-AES
• "M" for ICP-MS
"F" for graphite furnace AA
"A" for flame AA
7. Under "Comments" give additional relevant information.
8. If more ICS analyses were required, submit additional Form Vis as
appropriate. The order of reporting ICSs for each analyte must follow the
chronological order in which they were run, starting with the first Form VI
and continuing to the following Form Vis as appropriate. When multiple
elemental expressions are used for one analyte, all the results of "EE" number
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1 must be reported before proceeding to "EE" number 2, in the same manner as
described in Part E.
Part J - Spike Sample Recovery [FORM VII - LCINJ; This form is used to report
results for the matrix spike.
1. Complete the header information according to the instructions in Part A
and as follows.
2. In the "EPA Sample No." box, enter the EPA Sample Number (8 places
maximum) of the sample from which the spike results on this form were
obtained. The number must be centered in the box.
3. "EE" is the elemental expression used to obtain data for each analyte.
For ICP-AES and AA, the elemental expression identifies the wavelength used
and interference correction terms (if any). For ICP-MS, the elemental
expression identifies the primary quantitation mass and isobaric interference
correction terms (if any). The actual elemental expressions are specified on
Form XIII and are assigned an individual identifying number (the "EE" number)
if more than one expression is specified for a given analyte.
3.1 Under "EE," enter the number of the elemental expression that was used
to derive the results for each analyte reported on the form. The "EE" is a
number assigned to each elemental expression when more than one elemental
expression is used to obtain data for an analyte in the SDG. An "EE"
number of 1 should be assigned to the most frequently used elemental
expression for a given analyte in the SDG. An "EE" number of 2 should be
assigned to the second most frequently used elemental expression, and so
on. If only one elemental expression is used to obtain data for an analyte
in the SDG, an "EE" number of 1 should be assigned to the elemental
expression. The "EE" number must be consistently applied to the elemental
expression it identifies for the entire SDG.
4. Under "Sample Result (SR)," enter the value (in ug/L, to three decimal
places) of the measured concentration for each analyte in the sample (reported
in the EPA Sample No. box) on which the matrix spike was performed. Enter the
IDL value if the analyte was not detected. Enter any appropriate qualifier,
as explained in Part D, to the "C" qualifier column immediately following the
"Sample Result (SR)" column.
5. Under "Spiked Sample Result (SSR)," enter the value (in ug/L, to three
decimal places) of the measured concentration for each analyte in the matrix
spike sample. Enter the IDL value if the analyte was not detected. Enter any
appropriate qualifier, as explained in Part D, to the "C" qualifier column
immediately following the "Spiked Sample Result (SSR)" column.
6. Under "Spike Added (SA)," enter the value (in ug/L, to three decimal
places) of the concentration of each analyte added to the sample. If the
"Spike Added" concentration is specified in the contract, the value added and
reported must be that specific concentration in ug/L.
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7. Under "%R," enter the value (to the nearest whole number) of the percent
recovery for all spiked analytes computed according to the following equation:
*R
SSR
(SA + SR)
x 100
7.1 %R must be reported, whether it is negative, positive or zero.
7.2 A value of zero must be used for SSR or SR if the analyte value is
less than the IDL.
8. Under "Q," enter "N" if the Spike Recovery (%R) is out of the control
limits (75-125).
9. Under "M," enter method used as explained in Part D.
10. Under "Comments" give additional relevant information.
11. If different samples were used for spike sample analysis of different
analytes, additional Form VIIs must be submitted for each sample as
appropriate.
12. Use additional Form VIIs for each sample on which a required spike sample
analysis was performed. If multiple elemental expressions are used for an
analyte, the results of "EE" number 1 must be reported proceeding to "EE"
number 2, and so on.
Part K - Duplicates [FORM VIII - LCIN]: The duplicates form is used to report
results of duplicate analyses.
1. Complete the header information according to the instructions in Part A
and as follows.
2. In the "EPA Sample No." box, enter the EPA Sample Number (8 places
maximum} of the sample from which the duplicate results on this form were
obtained. The number must be centered in the box.
3. "EE" is the elemental expression used to obtain data for each analyte.
For ICP-AES and AA, the elemental expression identifies the wavelength used
and interference correction terms (if any). For ICP-MS, the elemental
expression identifies the primary quantitation mass and isobaric interference
correction terms (if any). The actual elemental expressions are specified on
Form XIII and are assigned an individual identifying number (the "EE" number)
if more than one expression is specified for a given analyte.
3.1 Under "EE," enter the number of the elemental expression that was used
to derive the results for each analyte reported or. the form. The "EE" is a
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number assigned to each elemental expression when more than one elemental
expression is used to obtain data for an analyte in the SDG. An "EE"
number of 1 should be assigned to the most frequently used elemental
expression for a given analyte in the SDG. An "EE" number of 2 should be
assigned to the second most frequently used elemental expression, and so
on. If only one elemental expression is used to obtain data for an analyte
in the SDG, an "EE" number of 1 should be assigned to the elemental
expression. The "EE" number must be consistently applied to the elemental
expression it identifies for the entire SDG.
4. Under "Control Limit," enter the numerical value of the CRDL (in ug/L, to
two decimal places) for the analyte if the sample or duplicate values were
less than 5 times the CRDL. If both the sample and duplicate values were less
than the CRDL or both were greater than or equal to 5 times the CRDL, leave
the field empty.
5. Under "Sample (S)," enter the original value (in ug/L, to three decimal
places) of the concentration of each analyte in the sample (reported in the
EPA Sample No. box) on which a duplicate analysis was performed. Enter the
IDL value if the analyte was not detected. Enter any appropriate qualifier,
as explained in Part D, to the "C" qualifier column immediately following the
"Sample (S)" column.
6. Under "Duplicate (D)," enter the value (in ug/L, to three decimal places)
of each analyte in the Duplicate sample (reported in the EPA Sample No. box).
Enter the IDL value if the analyte was not detected. Enter any appropriate
qualifier, as explained in Part D, to the "C" qualifier column immediately
following the "Duplicate (D)" column.
7. Under "RPD," enter the absolute value (to the nearest whole number) of the
Relative Percent Difference for all analytes detected above the CRDL in either
the sample or the duplicate, computed according to the following equation:
RPD = -1§—5Lx 100
m
7.1 A value of zero must be substituted for S or D if the analyte
concentration is less than the IDL in either one. If the analyte
concentration is less than the IDL in both S and D, leave the RPD field
blank.
8. Under "Q," enter if the duplicate analysis for the analyte is out of
control. If both sample and duplicate values are greater than or equal to 5
times the CRDL, then the RPD must be less than or equal to 20 percent to be in
control. If either sample or duplicate values are less than 5 times the CRDL,
then the absolute difference between the two values must be less than or equal
B-33
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to the CRDL to be in control. If both values are below the CRDL, then no
control limit is applicable,
9. Under "M," enter method used as explained in Part D.
10. Under "Comments" give additional relevant information.
11. Use additional Form VIIIs for each sample on which a required duplicate
sample analysis was performed. If multiple elemental expressions are used for
an analyte, the results of "EE" number 1 must be reported before proceeding to
"EE" number 2, and so on.
Part L - Laboratory Control Sample [FORM IK - LCIN]: This form is used to
report results for the Laboratory Control Sample.
1. Complete the header information according to the instructions in Part A
and as follows. If an analyte was not required to be analyzed then leave the
appropriate spaces blank.
2. "EE" is the elemental expression used to obtain data for each analyte.
For ICP-AES and AA, the elemental expression identifies the wavelength used
and interference correction terms (if any). For ICP-MS, the elemental
expression identifies the primary quantitation mass and isobaric interference
correction terms (if any). The actual elemental expressions are specified on
Form XIII and are assigned an individual identifying number (the "EE" number)
if more than one expression is specified for a given analyte.
2.1 Under "EE," enter the number of the elemental expression that was used
to derive the results for each analyte reported on the form. The "EE" is a
number assigned to each elemental expression when more than one elemental
expression is used to obtain data for an analyte in the SDG. An "EE"
number of 1 should be assigned to the most frequently used elemental
expression for a given analyte in the SDG. An "EE" number of 2 should be
assigned to the second most frequently used elemental expression, and so
on. If only one elemental expression is used to obtain data for an analyte
in the SDG, an "EE" number of 1 should be assigned to the elemental
expression. The "EE" number must be consistently applied to the elemental
expression it identifies for the entire SDG.
3. Under "Limits," enter the lower limit (in ug/L, to two decimal places) in
the left column, and the upper limit (in ug/L, to one decimal place) in the
right column for each analyte in the LCS Source solutions.
4. Under "True," enter the value (in ug/L, to two decimal places) of the
concentration of each analyte in the LCS Standard Source.
5. Under "Found," enter the measured concentration (in ug/L, to three decimal
places) of each analyte found in the LCS solutions. Enter the IDL value if
the analyte was not detected.
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6. Enter any appropriate qualifier as explained in Part D to the "C"
qualifier column immediately following the "Found" column.
7. Under "%R," enter the value of the percent recovery (to the nearest whole
number) computed according to the following equation:
„R , LCS Found x 1Q0
LCS True
7.1 If the analyte concentration is less than the IDL, a value of zero
must be substituted for the LCS found.
8. Under "M," enter method used as explained in Part D.
9. Under "Comments" give additional relevant information.
10., Submit additional Form IXs as appropriate, if more than one LCS was
required. If multiple elemental expressions are used for an analyte, the
results of "EE" number 1 must be reported before proceeding to "EE" number 2,
and so on.
Part M - Serial Dilution [FORM X - LCIN]: The Serial Dilution Form is used to
report results of serial dilution analyses.
1. Complete the header information according to the instructions in Part A
and as follows.
2. In the "EPA Sample No." box, enter the EPA Sample Number (8 places
maximum) of the sample from which the duplicate results on this form were
obtained.
3. "EE" is the elemental expression used to obtain data for each analyte.
For ICP-AES and AA, the elemental expression identifies the wavelength used
and interference correction terms (if any). For ICP-MS, the elemental
expression identifies the primary quantitation mass and isobaric interference
correction terms (if any). The actual elemental expressions are specified on
Form XIII and are assigned an individual identifying number (the "EE" number)
if more than one expression is specified for a given analyte.
3.1 Under "EE," enter the number of the elemental expression that was used
to derive the results for each analyte reported on the form. The "EE" is a
number assigned to each elemental expression when more than one elemental
expression is used to obtain data for an analyte in the SDG. An "EE"
number of 1 should be assigned to the most frequently used elemental
expression for a given analyte in the SDG. An "EE" number of 2 should be
assigned to the second most frequently used elemental expression, and so
on. If only one elemental expression is used to obtain data for an analyte
B-35
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in the SDG, an "EE" number of 1 should be assigned to the elemental
expression. The "EE" number must be consistently applied to the elemental
expression it identifies for the entire SDG.
4, Under "Initial Sample Result (I}," enter the value (in ug/L, to three
decimal places) of the measured concentration for each analyte in the
undiluted sample (reported in the EPA Sample No. box), which is within the
linear range of the instrument, on which a Serial Dilution analysis was
performed.
4.1 If the measured concentration of an analyte exceeds the linear range
of the instrument, leave the field blank.
4.2 Enter the IDL value if the analyte was not detected.
4.3 Enter any appropriate qualifier, as explained in Part D, to the "C"
qualifier column immediately following the "Initial Sample Result (I)"
column.
4.4 Note that the Initial Sample concentration for an analyte does not
have to equal the value for that analyte reported on Form I. The Initial
Sample Concentration is the value of the analyte concentration (uncorrected
for dilution) that is within the linear range of the instrument.
5, Under "Serial Dilution Result (S)," enter the measured concentration value
(in ug/L, to three decimal places) of each analyte in the serially diluted
sample (reported in the EPA Sample No. box) multiplied by 5.
5.1 If the measured concentration of an analyte exceeds the linear range
of the instrument, leave the field blank.
5.2 Enter the IDL value multiplied by five if the analyte was not
detected.
5.3 Enter any appropriate qualifier, as explained in Part D, to the "C"
qualifier column immediately following the "Serial Dilution Result (S)"
column.
5.4 Note that the Serial Dilution Result (S) is obtained by multiplying by
five the instrument measured value (in ug/L) of the serially diluted
sample. In addition, the "C" qualifier must be established based on the
instrument measured value of the serially diluted result, before correcting
it for the dilution. A value or "0" may be substituted for S if the
analyte concentration is less than the IDL.
6, Under "% Difference," enter the value (to the nearest whole number) of the
percent difference computed according to the following equation:
% Difference = I1 " S| x 100
I
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6.1 As mentioned in 5.4 above, a value of "0" must be substituted for S if
the analyte concentration is less than the IDL. If I is less than the IDL,
or I is blank, leave the "I Difference" field empty.
7. Under "Q," enter "E" if the % Difference value is greater than 10 percent
and the sample concentration of the undiluted sample is within the linear
range of the instrument and is greater than 20 times the CRDL.
8. Under "M," enter the method used as explained in Part D.
9. Under "Comments" give additional relevant information.
10. Use additional Form Xs for each sample on which a required serial
dilution analysis was performed. If multiple elemental expressions are used
for an analyte, the results of "EE" number 1 must be reported before
proceeding to "EE" number 2, and so on.
Part N - Standard Addition Results [FORM XI - LCIN]: This form is used to
report the results of samples analyzed using the Method of Standard Additions
(MSA) .
1. Complete the header information according to the instructions in Part A.
2. Under "EPA Sample No,," enter the EPA Sample Numbers (8 places maximum) of
all analytical samples analyzed using MSA. This includes reruns by MSA (if
the first MSA was out of control) as explained in Exhibit E.
2.1 A maximum of 32 standard addition results can be entered on this form.
If additional MSAs were required, submit additional Form XIs.
2.2. Standard addition results must be listed in ascending alphanumeric
order by EPA sample number using the EBCDIC convention. If more than one
analyte for a sample required MSA, then the standard addition results for
that sample must be listed in ascending alphabetic order by analyte. All
analyte results must be reported before proceeding to the analyte results
for the next sample number, continuing to the next Form XI if applicable.
If multiple elemental expressions are used for an analyte, the results of
"EE" number 1 must be reported before proceeding to "EE" number 2, and so
on.
3. Under "An," enter the chemical symbol (3 spaces maximum) for each analyte
for which MSA was required for each sample listed. The analytes must be
listed in ascending alphabetic order.
4. "EE" is the elemental expression used to obtain data for each analyte.
For ICP-AES and AA, the elemental expression identifies the wavelength used
and interference correction terms (if any). For ICP-MS, the elemental
expression identifies the primary quantitation mass and isobaric interference
correction terms (if any). The actual elemental expressions are specified on
Form XIII and are assigned an individual identifying number (the "EE" number)
if more than one expression is specified for a given analyte.
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4.1 Under "EE," enter the number of the elemental expression that was used
to derive the results for each analyte reported on the form. The "EE" is a
number assigned to each elemental expression when more than one elemental
expression is used to obtain data for an analyte in the SDG. An "EE"
number of 1 should be assigned to the most frequently used elemental
expression for a given analyte in the SDG. An "EE" number of 2 should be
assigned to the second most frequently used elemental expression, and so
on. If only one elemental expression is used to obtain data for an analyte
in the SDG, an "EE" number of 1 should be assigned to the elemental
expression. The "EE" number must be consistently applied to the elemental
expression it identifies for the entire SDG.
5. "Additions" has several items.
5.1 Under "Zero Found" (yj , enter the measured value in absorbance or
intensity units (to 3 decimal places) for the analyte before any addition
is performed.
5.2 Under "First Added" (x2), enter the concentration in ug/L (to 3
decimal places) of the analyte added to the first addition of the sample
analyzed by MSA.
5.3 Under "First Found" (y2), enter the measured value in absorbance or
intensity units (to 3 decimal places) for the sample solution spiked with
the first addition.
5.4 Under "Second Added" (x3), enter the concentration in ug/L (to 3
decimal places) of the analyte to the second addition of the sample
analyzed by MSA.
5.5 Under "Second Found" (y3), enter the measured value in absorbance or
intensity units (to 3 decimal places) for the sample solution spiked with
the second addition.
5.6 Under "Third Added" (x4), enter the concentration in ug/L (to 3
decimal places) of the analyte (excluding sample contribution) after the
third addition to the sample analyzed by MSA.
5.7 Under "Third Found" (y4), enter the measured value in absorbance or
intensity units (to 3 decimal places) for the analyte in the sample
solution spiked with the third addition.
5.8 Note that "Zero Found," "First Found," "Second Found," and "Third
Found" must have the same dilution factor.
6. Under "Final Cone.," enter the final analyte concentration (in ug/L, to 3
decimal places) in the sample as determined by MSA computed as follows, using
the ordinary least-squares regression line (unweighted):
where,
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ILC03.
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4 x £ xj x y, - £ xj x £y,
m
n=l
a-1
a=l
4 / 4 \2
2
4 x * Exi
n=l \n=l j
Xj
x2
Xj
X,
"First Added
"Second Added
"Third Added
y, = "Zero Found"
y2 = "First Found"
y3 = "Second Found"
y, = "Third Found"
and
1 m
7 « Ey, - T x 2>,
^ n=l ^
X 2^X:
n=l
then
Final Concentration =
m
7. Under "r," enter the correlation coefficient (to 3 decimal places)
computed as follows:
r =
4
4 x e
Xj X
a=l
4
'A
4 x Exi2
X
B=1
4
E
n=l
4
E:
n=l
4 / 4 \2
2
14
a T2
4 x Eft - E*
n=l \u=l ,
Note that the final concentration of an analyte does not have to equal the
value for that analyte which is reported on Form I for that sample.
8. Under "Q," enter "+" if r is less than 0.995. If r is greater than or
equal to 0.995, then leave the field empty.
9. Under "M," enter method used as explained in Part D.
Part o - Instrument Detection Limits -(IDL) [FORM XII - LCIN] : This form
documents the IDL for each instrument that the laboratory used to obtain data
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for the SDG. Only the instrument and elemental expressions used to generate
data for the SDG must be included,
1. Complete the header information according to the instructions in Part A
and as follows.
2. Enter the "Instrument ID Number" for the instrument used to produce data
for the SDG, and for which IDLs are being reported, as explained in Section K.
3. For "Method," enter the method of analysis as explained in Part D.
4. Enter the date (formatted MM/DD/YY) on which the IDL values were
determined. This date must not exceed any of the analysis dates for that
instrument in the SDG data package. Also, it must not precede them by more
than 3 calendar months.
5. "EE" is the elemental expression used to obtain data for each analyte.
For ICP-AES and AA, the elemental expression identifies the wavelength used
and interference correction terms (if any). For ICP-MS, the elemental
expression identifies the primary quantitation mass and isobaric interference
correction terms (if any). The actual elemental expressions are specified on
Form XIII and are assigned an individual identifying number (the "EE" number)
if more than one expression is specified for a given analyte.
5.1 Under "EE," enter the number of the elemental expression that was used
to derive the results for each analyte reported on the form. The "EE" is a
number assigned to each elemental expression when more than one elemental
expression is used to obtain data for an analyte in the SDG. An "EE"
number of 1 should be assigned to the most frequently used elemental
expression for a given analyte in the SDG. An "EE" number of 2 should be
assigned to the second most frequently used elemental expression, and so
on. If only one elemental expression is used to obtain data for an analyte
in the SDG, an "EE" number of 1 should be assigned to the elemental
expression. The "EE" number must be consistently applied to the elemental
expression it identifies for the entire SDG.
5.2 If multiple instruments are used for an analyte the IDLs for the
lowest numeric instrument must be reported before proceeding to the next
highest instrument. If multiple elemental expressions are used for an
analyte, the results of "EE" number 1 must be reported before proceeding to
"EE" number 2, and so on. After all "EE" numbers have been reported, then
additional instruments may be reported if they were used.
6. Under "Integ. Time," enter the integration time (in seconds, to two
decimal places) used for each measurement taken from each instrument.
7. Under "Background," enter the type of background correction used to obtain
furnace AA data. Enter "BS" for Smith Hieftje, "BD" for Deuterium Arc, or
"3Z" for Zeeman background correction. If ICP-MS was used, leave the field
blank.
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8. Under "CRDL," enter the Contract Required Detection Limit (in ug/L), as
established in Exhibit C.
9. Under "IDL," enter the Instrument Detection Limit (in ug/L) as determined
by the laboratory for each analyte analyzed by the instrument for which the ID
Number is listed on this form. IDLs must be reported to two significant
figures if the IDL value is less than 100 and to three significant figures for
values above or equal to 100.
10. Use the "Comments" section to indicate alternative wavelengths or masses
and the conditions under which they are used.
11. Use additional Form XIIs if more instruments, wavelengths, or elemental
expressions are used.
Part P - ICP-AES and ICP-MS Elemental Expression Factors (A) [FORM XIII -
LCIN]: This form documents for each ICP-AES and ICP-MS instrument the
elemental expression factors, for each analyte, applied by the Contractor to
obtain data for the SDG. Although the correction factors are determined
annually (every 12 calendar months), a copy of the results of the annual
elemental expression factors must be included with each SDG data package on
Form XIII.
1. Complete the header information according to instructions in Part A and as
follows.
2. Enter the "Instrument ID Number" for each ICP-AES, AA, and ICP-MS
instrument used to produce data for the SDG, as explained in Section H. If
more than one ICP instrument is used, submit additional Form XIIIs as
appropriate.
3. For "Method," enter the method of analysis (two characters maximum) for
which the elemental expressions listed on the form were made.
• "P" for ICP-AES
• "M" for ICP-MS
"F" for graphite furnace AA
"A" for flame AA ¦
4. Report the date (formatted as MM/DD/YY) on which these correction factors
were determined for use. This date must not exceed any of the analysis dates
reported for that instrument in the SDG data package. Also, it must not
precede them by more than 12 calendar months.
5. "EE" is the elemental expression used to obtain data for each analyte.
For ICP-AES and AA, the elemental expression identifies the wavelength used
and interference correction terms (if any). For ICP-MS, the elemental
expression identifies the primary quantitation mass and isobaric interference
correction terms (if any). The actual elemental expressions are specified on
Form XIII and are assigned an individual identifying number (the "EE" number)
if more than one expression is specified for a given analyte.
B-41
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5.1 Under "EE," enter the number of the elemental expression that was used
to derive the results for each analyte reported on the form. The "EE" is a
number assigned to each elemental expression when more than one elemental
expression is used to obtain data for an analyte in the SDG. An "EE"
number of 1 should be assigned to the most frequently used elemental
expression for a given analyte in the SDG. An "EE" number of 2 should be
assigned to the second most frequently used elemental expression, and so
on. If only one elemental expression is used to obtain data for an analyte
in the SDG, an "EE" number of 1 should be assigned to the elemental
expression. The "EE" number must be consistently applied to the elemental
expression it identifies for the entire SDG.
6. Under "Wavelength or Mass," list the wavelength (in nanometers, to two
decimal places) for ICP-AES instruments, or the mass-to-charge ratio (m/z, to
nominal unit mass) for ICP-MS instruments for each analyte analyzed.
6.1 If more than one mass-to-charge ratio is used in the elemental
expression to provide quantitation, then the mass-to-charge ratio entered
should be the analyte*s primary mass in the equation used for quantitation.
For example, if the elemental expression for the first selenium (EE)is Se =
(1.0000){m/z 78)—(0-1869)(m/z 76) then the mass reported should be 78.
6.2 If more than one elemental expression is used, submit additional Form
XIIIs as appropriate.
7. Under "EQM," enter the element symbol (for ICP-AES or AA) or the mass-to-
charge ratio (m/z., to the nominal mass unit) (for ICP-MS), which will be used
as a correction factor, for each correction that will be applied as part of
the elemental expression. If a correction term is not needed, then leave the
field blank.
8. Under "Factor," enter the correction factor (negative, positive, or zero,
to 5 significant places, 7 spaces maximum) associated with the EE number to
the left of the factor. If an "EOM" was not identified in the column to the
left, leave the field blank.
9. Under "IS," enter the element symbol of the internal standard used for the
analyte listed.
10. Under "ISEE" enter the "EE" number associated with the "IS." The "EE"
number is the same as that found on Form XIV.
11. Under "Comments" give additional relevant information.
12. Use additional Form XIIIs as appropriate if correction factors for more
than five analytes were applied. All correction factors for "EE" number 1
must be reported before proceeding to "EE" number 2 and so on.
Part Q - ICP-AES and ICP-MS Elemental Expression Factors (B) [FORM XIV -
LCIN]: This form documents for each ICP-AES and ICP-MS instrument the
elemental expression factors applied by the Contractor for internal standards
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when they are used to obtain data for the SDG. This form is required for all
ICP-MS analyses. Although the correction factors are determined annually
(every 12 calendar months}, a copy of the results of the annual elemental
expression factors must be included with each SDG data package on Form XIV
(B), if internal standards are used.
1. Complete the header information according to instructions in Part A and as
follows.
2. Enter the "Instrument ID Number" for each ICP-AES, AA, and ICP-MS
instrument used to produce data for the SDG, as explained in Section K. If
more than one ICP instrument is used, submit additional Form XIVs as
appropriate.
3. For "Method," enter the method of analysis (two characters maximum) for
which the elemental expressions listed on the form were made as follows,
• "P" for ICP-AES
. "M" for ICP-MS
"F" for graphite furnace AA
"A" for flame AA
4. Under "Analyte" enter the name of the internal standard or analyte being
described by the elemental expression.
5. Report the date (formatted as MM/DD/YY) on which these correction factors
were determined for use. This date must not exceed any of the analysis dates
reported for that instrument in the SDG data package. Also, it must not
precede them by more than 12 calendar months.
6. "EE" is the elemental expression used to obtain data for each analyte.
For ICP-AES the elemental expression identifies the wavelength used and
interference correction terms (if any). For ICP-MS, the elemental expression
identifies the primary quantitation mass and isobaric interference correction
terms (if any). The actual elemental expressions are specified on Form XIII
and are assigned an individual identifying number (the "EE" number) if more
than one expression is specified for a given analyte.
6.1 Under "EE," enter the number of the elemental expression that was used
to derive the results for each analyte reported on the form. The "EE" is a
number assigned to each elemental expression when more than one elemental
expression is used to obtain data for an analyte in the SDG. An "EE"
number of 1 should be assigned to the most frequently used elemental
expression for a given analyte in the' SDG. An "EE" number of 2 should be
assigned to the second most frequently used elemental expression, and so
on. If only one elemental expression is used to obtain data for an analyte
in the SDG, an "EE" number of 1 should be assigned to the elemental
expression. The "EE" number must be consistently applied to the elemental
expression it identifies for the entire SDG.
7. Under "Wavelength or Mass," list the wavelength (in nanometers, to two
decimal places) for ICP-AES or AA instruments, or the primary mass-to-charge
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ILC03.1
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ratio (m/z, to nominal unit mass) for ICP-MS instruments as explained in Part
P for each analyte analyzed.
7.1 If more than one mass-to-charge ratio is used in the elemental
expression to provide quantitation, then the mass-to-charge ratio entered
should be the analyte's primary mass in the equation used for quantitation.
For example, if the elemental expression for the first selenium EE is Se =
(1.0000)(m/z 78)—(0.1869)(m/z 76) then the mass reported should be 78. If
more than one elemental expression is used, submit additional Form XIVs as
appropriate.
8. Under "EOM," enter the element symbol (for ICP-AES or AA;) or the mass-to-
charge ratio (m/z, to the nominal mass unit) (for ICP-MS), which will be used
as a correction factor, for each correction that will be applied as part of
the elemental expression. If a correction term is not needed, then leave the
field blank.
9. Under "Factor," enter the correction factor (negative, positive or zero,
to five significant places, 7 spaces maximum) associated with the EOM to the
left of the factor. If an "EOM" was not identified in the column to the left,
leave the field blank.
10. Under "IS," enter the chemical symbol of the primary internal standard
used. The chemical symbols must be listed in ascending atomic number.
11. Under "Comments" give additional relevant information.
12. Use additional Form XIVs as appropriate additional correction factors
were applied. All correction factors for "EE" number 1 must be reported
before proceeding to "EE" number 2 and so on.
13. Report all internal standard elemental expressions that were used to
report analytical results under this contract.
Part R - ICP-MS Tuning and Response Factor Criteria [FORM XV - LCIN]: This
form is used for reporting tuning, response factor, and mass calibration
verification results for each ICP-MS run used to report data in the SDG.
1. Complete the header information according to the instructions in Part A
and as follows.
2. Enter the "Instrument ID Number" for the ICP-MS instrument used to produce
data on the form, as explained in Section H. A Form XV must be submitted for
each ICP-MS analysis run in the SDG.
3. For "Run No.," enter the run number (two spaces maximum) from which the
information on the form was taken. The run number is a sequential number for
each run in the SDG that identifies the different analytical runs that are
performed on the same instrument. The first run number for an instrument must
be 1, the second must be 2, and so on.
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4. For "Analysis Date," enter the date (formatted MM/DD/YY) of analysis of
the initial tuning solution from which the information on the form was taken.
5. "Analysis Times" has two items.
5.1 For "Analysis Times, Initial," enter the time (in military format -
HHMM) of analysis of the initial tuning solution from which the information
on this form was taken.
5.2 For "Analysis Times, Final," enter the time (in military format -
HHMM) of analysis of the final tuning solution from which the information
on this form was taken.
6. The remainder of the form contains three tables.
6.1 Tuning
6.1.1 Under "I Relative Abundance, Initial," enter the percent relative
abundance (to 2 decimal places) calculated from the intensities listed
under "Response Factor," for each of the isotopes listed, as a result of
analyzing the 100 ppb tuning solution (Table VII in Section C) at the
beginning of each ICP-MS run. The isotopes are listed in the first column
from the left in the Tuning Section of the Form.
6.1.2 Under "I Relative Abundance, Final," enter the percent relative
abundance (to 2 decimal places) calculated from the intensities listed
under "Response Factor," for each of the isotopes listed, as a result of
analyzing the 100 ppb tuning solution (Table VII in Section C) at the end
of each ICP-MS run. The isotopes are listed in the first column from the
left in the Tuning Section of the Form.
6.2 Response Factor (counts per second)
6.2.1 Under "RF,0- Response, Initial," enter the measured value of the
response (in counts per second, to the nearest whole number) in the 100 ppb
tuning solution (Table VII in Section C) analyzed at the beginning of each
ICP-MS run, for each mass-to-charge ratio listed in the first column from
the left in the Response Factor Section of the Form.
6.2.2 Under "RF10C Response, Final," enter the measured value of the
response (in counts per second, to the nearest whole number) in the 100 ppb
tuning solution (Table VII in Section C) analyzed at the end of each ICP-MS
run for each mass-to-charge ratio listed in the first column from the left
in the Response Factor Section of the Form.
6.3 Mass Calibration
6.3.1 Under "Observed Mass," enter the actual mass observed of each
analyte's peak center (to two decimal places) in the 100 ppb tuning
solution (Table VII in Section C) analyzed at the beginning of each ICP-MS
run for each mass-to-charge ratio listed in the first column from the left
in the Mass Calibration Section of the Form.
B-45
ILC03.1
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6.3.2 The values measured and reported in the Mass Calibration Section of
the Form must be within the control limits listed in the second column from
the left in each of the Sections.
7. Note that for every initial solution reported there must be a final one.
However, the opposite is not true. If a tuning solution was required to be
analyzed in the middle of a run (to avoid exceeding the 8-hour limit), it must
be reported in the "Final" section of this form.
8. If more tuning solutions analyses were required, submit additional Form
XVs reporting the runs for the lowest numeric instrument before proceeding to
the next lowest instrument.
9. The order of reporting the tuning solution results must follow the
chronological order in which the solutions were run starting with the first
Form XV and continuing to the following Form XV, as appropriate.
Part s - ICP-MS Internal Standards Relative Intensity Summary (A) [FORM XVI -
LCIN]: This form is used to report the relative internal standard intensity
levels during a run for ICP-MS. The relative intensity of each of the
internal standards in all analyses performed by ICP-MS must be reported on the
form.
1. A run is defined as the continuous totality of analyses performed by an
instrument throughout the sequence initiated by the first SOW-required
calibration standard and terminated by, and including, the continuing
calibration verification and blank following the last SOW-required analytical
sample.
2. All field samples and all QC analyses (including calibration standards,
ICVs, CCVs, ICBs, CCBs, MTS, CRIs, ICSs, LRSs, LCSs, PBs, duplicates, PE
Samples, and spikes) associated with the SDG must be reported on Form XVI.
The run must be continuous and inclusive of all analyses performed on the
particular instrument during the run.
3. Submit one Form XVI per run if no more than 32 analyses, including
instrument calibration, were analyzed in the run. If more than 32 analyses
were performed in the run, submit additional Form XVIs as appropriate. Each
new run must be started on the first line of Form XVI.
4. An identical number of Form XVIIs with ICP-MS methods and Form XVIs must
exist.
5. Complete the header information according to the instructions in Part A,
and as follows:
6. For "Instrument ID Number," enter the instrument ID number (12 spaces
maximum) which must be an identifier designated by the laboratory to uniquely
identify each instrument used to produce data which are required to be
reported in the SDG deliverable. If more than one ICP-MS instrument or run is
used, submit additional Form XVIs as appropriate. All runs for the lowest
B-46
ILC03.1
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alphanumeric instrument must be reported in ascending order before proceeding
to the runs for the next highest instrument.
7. For "Run No.,",enter the run number as explained in Part R,
8. For "Method," enter the method code (two characters maximum) as follows,
* "P" for ICP-AES
• "M" for ICP-MS
"F" for graphite furnace AA
"A" for flame AA
9. For "Start Time," enter the time (in military format - HHMM) that the
analysis run was started.
10. For "End Time," enter the date (in military format - HHMM} that the
analysis run was ended.
11. Under "EPA Sample No.," enter the EPA sample number of each analysis,
including all QC operations applicable to the SDG (formatted according to
Table B-l, Exhibit B). All EPA sample numbers must be listed in increasing
chronological (date and time) order of analysis, continuing to the next Form
XVI for the instrument run if applicable. The analysis date and time of other
analyses not associated with the SDG, but analyzed by the instrument in the
reported analytical run, must be reported. Those analyses must be identified
with the EPA Sample No. of "ZZZZZZ." Samples identified as "ZZZZZZ" need not
have intensities reported for internal standards.
12. Under "Time," enter the time (in military format - HHMM) at which each
analysis was performed.
12.1 For any particular ICP-MS run, the EPA Sample No. and time sequence
on Form XVI and XVII must be identical.
13. Under "Internal Standards %RI For:," enter the chemical symbol and
elemental expression number of the internal standard in the three-space
"Element" header field provided, to indicate the internal standard and
elemental expression for which the relative intensity of the internal
standards will be calculated in that column.
13.1 In the "Element" column, enter the internal standard relative
intensity (to the nearest whole number) the internal standard in the EPA
Sample No. for each sample analysis listed on the form (excluding
"ZZZZZZ"). The internal standard relative intensity (%RI) is calculated
using the following formula:
L
% RI = -2
lo
B-47
ILC03.1
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Where Ic is the intensity of the internal standard in the blank calibration
standard, and
IB is the intensity of internal standard in the EPA Sample No, in the
same units.
13.2 Under the "Q" column to the right of each "Element" column, enter an
"R" if the RI for a field sample, PES, duplicate, or spike is less than
0.30, If the percent relative intensity is greater than 0.30, leave the
field blank.
13.3 Columns of internal standard RI must be entered left to right
starting with the internal standards of the lower mass on the first Form
XVI and proceeding to the following Form XVI as appropriate. All Form XVIs
for the lowest numeric instrument must be reported in ascending order by
the run number, before proceeding to the next Form XVI,
Part T - Analysis Run Log (A) [FORM XVTI - LCIN] : This form is used to report
the sample analysis run log for ICP-AES, AA, and ICP-MS only. In addition,
the samples reported on this form must have been prepared in the same manner
using no pre-preparation dilution or concentration steps. The results
reported on Form I for the samples listed on this form for each analyte must
be obtained by multiplying each analyte's concentration (in ug/L) from the
instrument by the dilution factor listed on the form.
1. A run is defined as the continuous totality of analyses performed by an
instrument throughout the sequence initiated by, and including, the initial
and the final tuning solution, the first SOW-required calibration standard and
terminated by, and including, the continuing calibration verification and
blank following the last SOW-required analytical sample.
2. All field samples and all quality control analyses (including tuning
solutions, ICP serial dilutions, calibration standards, ICVs, CCVs, ICBs,
CCBs, MTS, CRIs, ICSs, LRSs, LCSs, PBs, duplicates, PE samples, and spikes)
associated with the SDG must be reported on Form XVII. The run must be
continuous and inclusive of all analyses performed on the particular
instrument during the run.
3. Submit one Form XVII per run if no more than 32 analyses, including
instrument calibration, were analyzed in the run. If more than 32 analyses
were performed in the run, submit additional Form XVIIs as appropriate.
4. Complete the header information according to the instructions in Part A,
and as follows.
5. For "Instrument ID Number," enter the instrument ID number (12 spaces
maximum) which must be an identifier designated by the laboratory to uniquely
identify each instrument used to produce data which are required to be
reported in the SDG deliverable. If more than one ICP-AES or ICP-MS
instrument is used, submit additional Form XVIIs as appropriate.
6. For "Run No.," enter the run number as explained in Part R.
B-4 8
ILC03.
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7. For "Method," enter the method code (two characters maximum) as follows,
• "P" for ICP-AES
• "M" for ICP-MS
"F" for graphite furnace AA
"A" for flame AA
8. For "Start Date," enter the date (formatted MM/DD/YY) on which the
analysis run was started.
9. For "End Date," enter the date (formatted MM/DD/YY) on which the analysis
run was ended.
10. Under "EPA Sample No.," enter the EPA sample number of each analysis,
including all QC operations applicable to the SDG (formatted according to
Table B-l, Exhibit B}. All EPA sample numbers must be listed in increasing
chronological (date and time) order of analysis, continuing to the next Form
XVII for the instrument run if applicable. The analysis date and time of
other analyses not associated with the SDG, but analyzed by the instrument in
the reported analytical run, must be reported. Those analyses must be
identified with the EPA Sample No. of "ZZZZZZ."
11. Under "Prep. Batch Number," enter the preparation batch number for each
sample and quality control sample preparation (including duplicates, spikes,
LCSs, PBs, and PE samples) that are reported on the Form. The preparation
batch number is used to link the sample analysis with the appropriate
preparation batch. It consists of an ordered combination of the date of
preparation (formatted MMDDYY), the hour of preparation (in military format -
HH), and the method of preparation. The preparation batch number must be
left-justified and may not have any blank spaces between its components. It
may not have more than one leading blank. Single digit hours and months must
be padded to the left with zeros. The following are examples of preparation
batch numbers:
Prep. Batch Number
Preparation
Hour
Date
Method
"11308915CV"
"11038915P "
"01Q29008F "
"12908F
15
15
8
invalid
12/25/92
12/25/92
01/01/93
CV
P
F
12. Under "Time," enter the time (in military format - HHMMj at which each
analysis was performed.
13. Under "D/F," note that for a particular sample a dilution factor (D/F) of
"1" must be entered if the preparation product was analyzed without adding any
further volume of dilutant or any other solutions to the sample or an aliquot
of that sample taken for preparation.
13.1 For solutions such as ICVs, ICSs, PESs, and LCSs, a dilution factor
must be entered if the supplied solution had to be diluted to a dilution
B-49
ILC03.1
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different from that specified by the instructions provided with the
solution. The dilution factor reported in such a case must be that which
would make the reported true values on the appropriate form for the
solution equal those that were provided with the solution. For example,
ICV-2(0887}, an UEPA solution, has a true value of 104.0 ug/L at a 20 fold
dilution. Not all required QC solution will be supplied by the USEPA. If
the solution is prepared at a 40-fold dilution, a dilution factor of "2"
must be entered on Form XVII and the uncorrected instrument reading is
compared to a true value of 52 ug/L. In this example, Form II will have a
true value of 104.0 regardless of the dilution used. The found value for
the ICV must be corrected for the dilution listed on Form XVII using the
following formula:
Found value on Form II = Instrument readout in ug/L x D/F
14. Under "Analytes," enter "X" in the column of the designated analyte to
indicate that the analyte value was used from the reported analysis to report
data on any of the forms in the SDG. Leave the column blank for each analyte
if the analysis was not used to report the particular analyte.
Part u - Analysis Run Log (B) [FORM XVIII - LCIN]: This form is used to
report the sample analysis run log for each instrument used for analysis in
the SDG. This includes ICP-AES and ICP-MS analysis runs where conditions for
reporting on Form XVII were not met. Form XVIII is analyte and method
specific.
1. A run is defined as the continuous totality of analyses performed by an
instrument throughout the sequence initiated by, and including, the initial
and the final tuning solution, the first SOW-required calibration standard and
terminated by, and including, the continuing calibration verification and
blank following the last SOW-required analytical sample.
2. All field samples and all QC analyses {including tuning solutions, serial
dilutions, calibration standards, ICVs, CCVs, ICBs, CCBs, MTS, CRIs, ICSs, LRS
s, LCSs, PBs, duplicates, PE Samples, matrix spikes, analytical spikes, and
each addition analyzed for MSA determination) associated with the SDG must be
reported on Form XVIII if they were not reported on Form XVII. The run must
be continuous and inclusive of all analyses performed on that instrument
during the run.
3. Submit one Form XVIII per run if no more than 32 analyses, including
instrument calibration, were analyzed in the run. If more than 32 analyses
were performed in the run, submit additional Form XVTIIs as appropriate.
4. Complete the header information according to the instructions in Part A,
and as follows.
5. For "Instrument ID Number," enter the instrument ID number (12 spaces
maximum) which must be an identifier designated by the laboratory to uniquely
B-50
ILC03.1
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identify each instrument used to produce data which are required to be
reported in the SDG deliverable. If more than one instrument is used, submit
additional Form XVIIIs as appropriate.
6. For "Run No.," enter the run number as explained in Part Q.
7. For "Method," enter the method code (two characters maximum) as follows,
• "P" for ICP-AES
• "M" for ICP-MS
"F" for graphite furnace AA
"A" for flame AA
8. For "Start Date," enter the date {formatted MM/DD/YY) on which the
analysis run was started.
9. For "Analyte," enter the analyte's chemical symbol (three spaces maximum)
for which the analysis run is being reported on the Form. Submit a Form XIX
for each analyte analyzed which was not reported on Form XVIII.
10. For "End Date," enter the date (formatted MM/DD/YY) on which the analysis
run was ended.
11. Under "EPA Sample No.," enter the EPA sample number of each analysis,
including all QC operations applicable to the SDG (formatted according to
Table B-l, Exhibit B). All EPA sample numbers must be listed in increasing
chronological (date and time) order of analysis, continuing to the next Form
XVIII for the instrument run if applicable. The analysis date and time of
other analyses not associated with the SDG, but analyzed by the instrument in
the reported analytical run, must be reported. Those analyses must be
identified with the EPA Sample No. of "ZZZZZZ."
12. Under "Prep. Batch Number," enter the preparation batch number as
explained in Part T.
13. Under "Int. Vol.," enter the initial volume (in milliliters, to the
nearest whole number) of each sample or aliquot of the sample taken for
preparation (distillation, digestion, etc.) for analysis by the method
indicated in the header section of the Form. This field must have a value for
each field sample listed.
14. Under "Fin. Vol.," enter the final volume (in milliliters, to the nearest
whole number) of the preparation for each sample prepared for analysis by the
method indicated in the header section of the Form. This field must have a
value for each field sample listed.
15. Under "Time," enter the time (in military format - HHMM) at which each
analysis was performed.
B-51
ILC03.1
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16. Under "D/F," enter the dilution factor (to two decimal places) by which
the final product of preparation procedure (digestate or distillate) needed to
be diluted for each analysis performed.
16.1 Note that for a particular sample, a dilution factor of "1" must be
entered if the preparation product was analyzed without adding any further
volume of dilutant or any other solution to the "Fin. Vol." of the sample
or an aliquot of that "Fin. Vol." listed for that sample on this form.
16.2 For solutions such as ICVs, ICSs, and LCSs, a dilution factor must be
entered if the supplied solution had to be diluted to a dilution different
from that specified by the instructions provided with the solution. The
dilution factor reported in such a case must be that which would make the
reported true values on the appropriate form for the solution equal those
that were provided with the solution. For example, ICV-2(0887), an USEPA
solution, has a true value of 104.0 ug/L at a 20 fold dilution. Not all
required QC solutions will be supplied by the USEPA. If the solution is
prepared at a 40-fold dilution, a dilution factor of "2" must be entered on
Form XVIII and the uncorrected instrument reading is compared to a true
value of 52 ug/L. In this example, Form II will have a true value of 104.0
regardless of the dilution used. The found value for the ICV must be
corrected for the dilution listed on Form XVIII using the following
formula:
Found value on Form II = Instrument readout in ug/L x D/F
17. Under "%R," enter the percent recovery (to two decimal places) for each
analytical spike analyzed. Leave the field blank if the analysis reported is
not an analytical spike. A IR of "-9999" must be entered for the analytical
spike if either the sample or the analytical spike result is greater than the
calibration range of the instrument.
18. Under "1RSD," enter the relative standard deviation of the replicate
exposures or injections for each analysis reported on this form.
Part V - Standard Solutions Sources [FORM XIX - LCIN]: This form is used to
report the source of each standard solution on an analyte-by-analyte basis
used for initial and continuing calibration verifications, CRDL, LRS, ICS, and
LCS standards used as a QC analysis in the SDG.
1. Complete the header information according to the instructions in Part A,
and as follows.
2. Under "ICV Standard Source," enter the initial calibration source (10
spaces maximum) for each analyte for which ICV results were reported on Form
II. Enter sufficient information in the available 12 spaces to unequivocally
identify the manufacturer and the solution used.
3. Under "CCV Standard Source," enter the continuing calibration source (10
spaces maximum) for each analyte for which CCV results were reported on Form
II, as described for the initial calibration source.
B-52
ILC03.
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4. Under "CRI Standard Source," enter the CRDL standard source (10 spaces
maximum) for each analyte for which CRDL standard results were reported on
Form III, as described for the initial calibration source.
5. Under "LRS Standard Source," enter the linear range analysis source (10
spaces maximum) for each analyte for which LRS standard results were reported
on Form IV, as described for the initial calibration source.
6. Under "ICS Standard Source," enter the ICP-AES and ICP-MS interference
source (10 spaces maximum) for each analyte for which ICS standard results
were reported on Form VI, as described for the initial calibration source.
7. Under "LCS Standard Source," enter the laboratory control sample source
{10 spaces maximum) for each analyte for which LCS standard results were
reported on Form IX, as described for the initial calibration source.
Part w - Sample Log-In Sheet [FORM DC - 1]: This form is used to document the
receipt and inspection of samples and containers. One original Form DC-1 is
required for each sample shipping container, e.g., cooler. If the samples in
a single-sample shipping container must be assigned to more than one SDG, the
original Form DC-1 shall be placed with the deliverables for the SDG of the
lowest Arabic number and a copy of Form DC-1 must be placed with the
deliverables for the other SDG(s). The copies should be identified as
"copy(ies)," and the location of the original should be noted on each copy.
1. Sign and date the airbill (if present). Examine the shipping container
and record in item 1 on Form DC-1 the presence/absence of custody seals and
their condition (i.e., intact, broken).
2. Record the custody seal numbers in item 2.
3. Open the container, remove the enclosed sample documentation, and record
the presence/absence of chain-of-custody record(s), SMO forms (i.e., traffic
reports, packing lists), and airbills or airbill stickers in items 3-5 on Form
DC-1. Specify if there is an airbill present or an airbill sticker in item 5
on Form DC-1. Record the airbill or sticker number in item 6.
4. Remove the samples from the shipping container(s), examine the samples and
the sample tags (if present), and record in items 7 and 8 on Form DC-1 the
condition of the sample bottles (i.e., intact, broken, leaking) and presence
or absence of sample tags.
5. Review the sample shipping documents and complete the header information
described in Part A, Compare the information recorded on all the documents
and samples and mark the appropriate answer in item 9 on Form DC-1.
6. If there are no problems observed during receipt, sign and date (include
time) Form DC-1, the chain-of-custody record, and Traffic Report, and write
the sample numbers on Form DC-1. Record the appropriate sample tags and
assigned laboratory numbers if applicable. The log-in date should be recorded
at the top of Form DC-1 and the date and time of cooler receipt at the
B-53
ILC03.1
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laboratory should be recorded in items 10 and 11. Cross out unused columns
and spaces.
7. If there are problems observed during receipt, contact SMO and document
the contact as well as resolution of the problem on a CLP Communication Log.
Following resolution, sign and date the forms as specified in the preceding
paragraph and note, where appropriate, the resolution of the problem.
8. Record the fraction designation {if appropriate) and the specific area
designation (e.g., refrigerator number) in the sample transfer block located
in the bottom left corner of Form DC-1. Sign and date the sample transfer
block.
Part X - Document Inventory Sheet (FORM DC - 2) : This form is used to record
the inventory of the Complete SDG File (CSF) documents which are sent to the
Region.
1. Organize all EPA-CSF documents as described in Exhibit B, Section II and
Section III.
2. Assemble the documents in the order specified on Form DC-2 and Section II
and III, and stamp each page with the consecutive number. (Do not number the
DC-2 form).
3. Inventory the CSF by reviewing the document numbers and recording page
numbers ranges in the column provided on the Form DC-2. If there are no
documents for a specific document type, enter an "NA" in the blank space.
4. Certain laboratory-specific documents related to the CSF may not fit into
a clearly defined category. The laboratory should review Form DC-2 to
determine if it is most appropriate to place the documents under No. 32, 33,
34, or 35. Category 35 should be used if there is no appropriate previous
category. These types of documents should be described or listed in the
blanks under each appropriate category.
B-54
ILC03.1
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SECTION IV - Data Reporting Forms
B-55 ILC03.1
-------
U.S. EPA - CLP
Low Concentration Inorganics
Cover Page
Lab Name: Contract:
Lab Code: Case No.: SDG No.:
SOW No.:
EPA Sample No. Lab Sample ID.
ICP-AES ICP-MS
Were ICP-AES and ICP-MS interelement corrections
applied? (Yes/No)
Were ICP and ICP-MS background corrections
applied? (Yes/No)
If yes, were raw data generated before
application of background corrections? (Yes/No)
I certify that this data package is in compliance with the terms and
conditions of the contract, both technically and for completeness, except
for the conditions detailed on the Comments Page. Release of the data
contained in this hard copy data package and in the computer-readable data
submitted on diskette has been authorized by the Laboratory Manager or the
Manager's designee, as verified by the following signature.
Signature: Name:
Date: Title:
COVER PAGE - LCIN 8/95
-------
U.S. EPA - CLP
Low Concentration Inorganics
Comments Page/Case Narrative
Lab Name: Contract:
Lab Code: Case No.: SDG No.: _
SOW No.:
Comments:
COMMENTS PAGE - LCIN
8/95
-------
U.S. EPA - CLP
Low Concentration Inorganics
Analysis Data Sheet
EPA Sample No
Lab Name:
Lab Code:
Contract:
Case No.:
SDG No.
Lab Sample ID:
Date Received:
Concentration Units: ug/L
[CAS No. | Analyte
|E|Concentration IC|
|E| I I
| 7429-
17440-
J7440-
1 7440-
1 7440-
| 7440-
17440-
1 7440-
| 7440-
17440-
|7439-
17439-
I7439-
17439-
1 7439-
1 7440-
17440-
| 7882-
I7440-
17440-
[7440-
| 7440-
17440-
•90-5_
•36-0*
38-2*
39-3*
•41-7^
43-9*
¦47-3"
70-2*
48-4*
50-8*
89-6*
92-1*
95-4*
96-5*
•97-6"
02-7*
02-0*
•49-2"
22-4*
23-5"
28-0*
62-2"
66-6*
|Aluminum_|_
|Antinony_|_
J Arsenic
|Barium |
J Beryllium|_
| Cadmium |
|Calcium |
| Chromium_|_
J Cobalt |_
| Copper |_
I Iron |_
| Lead [
JMagnesium!_
|Manganese|_
| Mercury |_
\ Potassium|_
I Nickel 1_
| Selenium_|_
J Silver |_
|Sodium |
j Thallium__ "
] Vanadi\am_I
I Zinc 1
I I
|Cyanide
[X|
|X|
I I
I I
I I
M
Before:
After:
Color
Clarity
Viscosity
Comments:
FORM I - LCIN
8/95
-------
U.S. EPA - CLP
Low Concentration Inorganics
Initial and Continuing Calibration Verification
Lab Name: Contract:
Lab Code: Case No.: SDG No.:
Run No.:
Concentration Units: ug/L
I I I
Continuing Calibration || |
I I I
Found %R Found %R ||M |
1 1 2 2|||
II I
| Aluminum_ | _ | | | | | | | | | 1 ]
|Antimony_I_| | | | | 1 | 1 I | |
I Arsenic 1_| I I I I I I I I i__l
I Barium |_| I | I I I I I t l_l
|Beryllium|_| | | | | | | | | | |
I Cadmium | | | I I I I 1 I I I I
I Calcium |_j | 1 | | | | | 1 | |
| Chromium_|_| | [ | | | | | I I I
| Cobalt | J | | | | | [ | I |_J
i Copper | J | | | | | | | | |_|
I Iron | J | I | | | | | | |_J
|Lead |_| I I i | | 1 I I |_|
IMagnesium|_| | | | I I | | | | |
(Manganese|_| | | | | | | | | | |
I Mercury |_| I I I I I I I I I I
I Nickel | J 1 1 | | | | | | |_|
I Potassium|_| | | | | | | ] | | |
I Selenium_|_| 1 | | | | | | | | I
I Silver |_| [ | I | | | | 1 | |
[ Sodium [ | | | | | j | | | ] |
I ThalliumJ_J | j | | | | | j | j
| Vanadium_|_| | j | | | | | | | |
I Zinc | J I | | | | 1 | | i_!
|Cyanide |_| | | | | | | | | |_|
I I I ! I I I I I I II I
| | |Initial Calibration!
| Analyte [El |
I |E| True Found %R | True
Comments:
FORM II - LCIN
8/95
-------
U.S. EPA - CLP
Low Concentration Inorganics
CRDL Standards
Lab Name:
Lab Code:
Run No.:
Case No.
Contract:
SDG No.
Concentration Units: ug/L
I 1 )
I Analyte |E|
I !E|
Initial
True Found
I Aluminum_J_| _
I Antimony_|_|_
I Arsenic |_|_
I Barium I I
| Beryllium!_|_
I Cadmium [ 1
I Calcium | |
|Chromium_|_|_
I Cobalt |_|_
I Copper |_|_
I Iron |_|_
I Lead |_|_
|Magnesium|_|_
I Manganese[_|_
I Mercury |_|
| Nickel |_f
IPotassiuml_[_
ISelenium_[_|_
I Silver |_[_
I Sodium | [
|ThalliumJ_|~
| Vanadium_|_|_
I Zinc [ |
%R
| Cyanide |_|
I I f
I I
Final | |
I I
Found IR |M I
I I
I I
I I
Comments:
FORM III - LCIN
8/95
-------
U.S. EPA - CLP
Low Concentration Inorganics
Linear Range Determination Standards (LRS)
Lab Name: Contract:
Lab Code: Case No.: SDG No.:
Run No,:
Concentration Units: ug/L
I I I
Analyte |E| Initial I Final
|E|
True Found %R | Found %R |M
I Aluminum_|_| | I I ] I I
|Antimony_|_J I I I ] I I
I Arsenic |_J I I I I I I
I Barium |_J | | I I I I
I Beryllium)__| I I I t 1 I
|Cadmium_J J I | | I I I
I Calcium |_| I 1 1 I I [
I Chromium_|_| | | I I I I
(Cobalt | J [ [ | | | I
[Copper |_| [ | | | | I
| Iron | J | | | | |_|
[Lead | J | | | | |_J
| Magnesium! _1 1 I I I 1 I
I Manganese |_[ 1 | | | | |
| Mercury |_| I I I I l_i
I Nickel | J | | | | i I
| Potassium|_| 1 | | | i |
| Selenium_l_l | | I I I I
I Silver |_| | 1 | | 1 I
I Sodium J_J | | | | | |
I Thallium_|_| [ | I | I I
| Vanadium_ | _ | | | | | | |
I Zinc || | || III
I Cyanide
Comments:
FORM IV - LCIN
8/95
-------
U.S. EPA - CLP
Low Concentration Inorganics
Blanks
Lab Name: Contract:
Lab Code: Case No.: , SDG No.:
Run No.:
Concentration Units: ug/L
I II I II II I
| Analyte |E| Initial | Continuing Calibration Blanks |[ Prep. || |
| |E| Calib. ( I| Blank |I |
| | | Blank C| 1 C 2 C 3 C|I C||M |
I IJ I I I I l__l
I AluminumJ J |_| |_| |_| |_| I |_i I I
|Antimony_|_I |_( l_l l_l IJ I l_l l_J
(Arsenic |_| |_| |_| |_| |_| I |_| I I
(Barium |_| |_l l_l ] J l_l I l_l I I
I Beryllium!_| l_l |_l |_l l_l 1 IJ I I
|Cadmium | | |_| |_| | J i_l I l_l I I
[Calcium | J |_| l_l_ IJ l_l I IJ I I
I ChromiumJ J |_| |_| |_| |_[ I |_| I I
I Cobalt IJ IJ | J |_| l_l I l_l l_l
|Copper |_| M l_l l_I j_l I l_l I I
I Iron | J | J | J I_l_ | J I | J l_l
I Lead |_| IJ IJ IJ IJ I I I l_l
|Magnesium|_| |_] |_J I_J_ l_l I IJ I I
I Manganese | _| |_| |_| |_| IJ I l_l I I
I Mercury |_| |_| IJ IJ IJ I |_| I I
1 Nickel | J IJ IJ i J IJ I IJ l_l
| Potassiuml J IJ IJ IJ IJ I IJ I I
| SeleniumJ J [J | J | J |J | | J | |
|Silver |_| |J |J |_| IJ I |J |_|
I Sodium | J IJ IJ IJ IJ I IJ l_l
IThalliumJ J M IJ IJ IJ I IJ !_!
| VanadiumJ J | J | J IJ |_| I IJ |_|
[Zinc | J | J | J | J | J | [ J |_|
(Cyanide | J II II IJ IJ I IJ I I
I I I I I I I I I I II I II I
Comments:
FORM ¥ - LCIN
8/95
-------
U.S. EPA - CLP
Low Concentration Inorganics
ICP and ICP-MS Interference Check Sample
Lab Name;
Lab Code:
Contract:
Instrument ID Number:
Case No.
SDG No.:
Run No.:
Concentration Units: ug/L
| Analyte |E| True
| |E t Sol. Sol.
I II A AB
|Aluminum_|_|_
|Antimony_|_|_
I Arsenic |__|_
|Barium j |
I Beryllium!_|_
|Cadmium 1 1
1 Calcium | |
| Chromium_|_|_
| Cobalt |_|
I Copper |_|_
II ron | _ | _
| Lead |_|
|Magnesium|_|_
I Manganese|
IMercury |_|_
I Nickel |_|_
I Potassium| _
| Selenium_|_|_
I Silver !_f
|Sodium | |
]Thallium_|_
1 Vanadium_|_
I Zinc |
Initial Found
Sol. Sol.
A AB
%R
I I
Final Found |
Sol. Sol. |
A AB %R |M
I I
Comments:
FORM VI - LCIN
8/95
-------
U.S. EPA - CLP
Low Concentration Inorganics
Spike Sample Recovery
EPA Sample No,
IE|Control| Sample |Spiked Sample I Spike | III
I I
Name: Contract: | |
Code: Case No.: SDG No.:
Concentration Units: ug/L
I n i i i i PI I
| |E|Control| Sample |Spiked Sample I Spike | III
| Analyte |E| Limit | Result (SR) | Result (SSR) |Added (SA) | %R |Q|M |
I II %R I C| C| I II I
I I 175-125 1 | | | I _|_|
I Aluminum | 175-125 | |_| [_| |_ |_| |
I Antimony I 175-125 j | J__ [_| | |_| |
I3eryllium|_|75-125 |
IChromium_|_175-125 |
| Iron | |75-125 |
I Selenium | |75-125 |
I Sodium |_|75-125 |
I Thallium | 175-125 |
| Vanadium_| _I 75-125 |
j Zinc | |75-125 |
I Cyanide | |75-125 |
Comments:
FORM VII - LCIN 8/95
-------
U.S. EPA - CLP
Low Concentration Inorganics
Duplicates
EPA Sample No.
Lab Name:
Lab Code:
Case No.:
Contract:
SDG No.
Concentration Units: ug/L
IE|Control[
Analyte |E| Limit | Sample (S)
I I I
| Aluminum_l_l_
| Antimony_j_!_
I Arsenic j_|_
I Barium 1 1
|Beryllium|_|_
I Cadmium [ [
|Calcium | |
I Chromium_J_|_
| Cobalt |_|_
I Copper ]_]_
I Iron |_i
I Lead |_f
IMagnesiuir. | _ | _
I Manganese|_|_
I Mercury |_|_
| Nickel |_|
| Potassium
|Selenium_
I Silver
I Sodium
]Thallium_
I Vanadium_
I Zinc
|Cyanide
I Duplicate (D) |
C| C|
J I
II II
I I
I 1
IJ
IJ
IJ
I I
I I
1 I
RPD
IQIM
I I
I _l_
u_
I I
l_l
l_l
l_l
l__l
I I
I I
I I
Comments:
FORM VIII - LCIN
8/95
-------
U.S. EPA - CLP
Low Concentration Inorganics
Laboratory Control Sample
Lab Name:
Lab Code:
Case No.
Contract:
SDG No.
Concentration Units: ug/L
I I
i EI Limits
Analyte |E|
| 1 Lower
Upper
|Muminum_|_|_
|Antimony_j_|_
I Arsenic |_|_
I Barium [ |
| Beryllium|_|~
I Cadmium | |
I Calcium 1 |
| Chromium_|_|_
| Cobalt |_|_
I Copper
| Iron !_]_
I Lead |_|_
| Magnesium) _|_
|Manganese|_|_
(Mercury |_|_
| Nickel )_|
| Potassium! _l
ISelenium_|_|
| Silver |_|
| Sodium |_f
|Thallium_|_r
I Vanadium_i_|
I Zinc [_)_
I Cyanide |_|_
True
Found
C %R |M I
I I
I I
I I
Comments:
FORM IX - LCIN
8/95
-------
U.S. EPA - CLP
Low Concentration Inorganics
Serial Dilution
EPA Sample
No.
Lab Name; Contract:
Lab Code: Case No.: SDG No.
Concentration Units: ug/L
IE|Initial Sample |Serial Dilution | % | |
Analyte |E| Result (I) | Result (S) |Difference|Q|M
II C| C| ||
|Aluminum_J_l |_| |_| I I _
|Antimony__|_| |_| [_| M.
I Arsenic |_| i_| |_| |_l_
| Barium | | j_| |_| |_J_
| Beryllium! _|_ |_| |_| |_|_
I Cadmium [ | |_| |_| |_|
| Calcium__|_| |_| |_| |_f
| Chromium_|_| | J |_| |_|
1 Cobalt | J 1J IJ l_f
I Copper | | !_! M M
I Iron ]_| |_| l_l l_l I
I Lead |_| | J |_| |J_|
| Magnesium | _| |_| |_| |_| |
I Manganese | _| |_| ]_| |_| I
I Mercury |_| |_| |_J |_| |
I Nickel |_| |_| |J l_l_l
I Potassium|_| |_| |_| |_| [
| Selenium_|_| |_| |_| |_| |
I Silver | J IJ M | _|__|
I Sodium |_| |_J 1_| |_| )
| Thallium_|_| | J |_| | J 1
| Vanadium_ [ _ | | _ | | _ | | _ | |
I Zinc |_| |_| [_| |_| |
| Cyanide |_| |_| |_| |_|_|
I I I I I I I I I I
Comments:
FORM X - LCIN
8/95
-------
U.S. EPA - CLP
Low Concentration Inorganics
Standard Addition Results
i Name: Contract:
i Code: Case No.: SDG No.:
Concentration Units: ug/L
j __ ADDITIONS j i M I
EPA I |E) Zero | First | Second | Third | | III
•ample IAn |E| I ] i 1 Final | 111
No. | | |Found |Added |Found|Added |Found|Added |Found I Cone. | r |Q]M |
I EPA I j E| Zero | First | Second | Third
I
I
I
FORM XI - LCIN 8/95
-------
Lab Name:
Lab Code:
U.S. EPA - CLP
Low Concentration Inorganics
Instrument Detection Limits
Contract:
Case No.:
SDG No.
Instrument ID Number:
Method:
Concentration Units: ug/L
|Aluminum_|_
i Antimony_|_
| Arsenic |
I Barium 1
I Beryllium|_
|Cadmium 1
|Calcium [
t Chromium_|_
I Cobalt |_
I Copper |_
I Iron |_
1 Lead |_
|Magnesium|_
|Manganese|_
[Mercury |_
(Nickel 1_
|Potassium|_
ISelenium_|_
I Silver |_
|Sodium |
|Thallium_|_
IVanadium_]_
I Zinc |_
|Cyanide [
Date:
1 I I I I
| | Integ. (Back- | |
Analyte |Elemental | Time |ground| CRDL | IDL
I Expression| (sec) | I !
I ( EE ) | | | |
Comments:
FORM XII - LCIN
8/95
-------
U.S. EPA - CLP
Low Concentration Inorganics
Elemental Expression Factors (A)
Lab Name:
Lab Code:
Case No.
Instrument ID Number:
Contract: _
SDG No.:
Method:
Date:
I I |Wave-
1
1 i
I I
1 1
| |
1 HI
I |E|Length
E I
1 E |
1 E |
1 E |
1 E |
1 I s I
I Analyte |E| or
0 |Factor
| 0 |Factor
I 0 |Factor
| 0 |Factor
| 0 j Factor
1 IS|E|
| | |Mass
1 1 1
M |
1
1 M |
1 !
1 M |
1 1
1 M I
1 1
1 M |
! 1
1 1 E|
1 1 I
I Aluminum | |
1
1 1
I f
1 1
1 1
1 1 1
! i 1
|Antimony 1 I
1
1 1
| I
1 1
1 I
I Arsenic
I Barium
|Beryllium
I Cadmium
I Calcium
IChromium_
I Cobalt
I Copper
I Iron
I Lead
|Magnesium|
IManganese
IMercury
I Nickel
I Potassium!
ISelenium_J
I Silver ]
I Sodium
I Thallium
I Vanadium
I Zinc
Comments:
FORM XIII - LCIN 8/95
-------
U.S. EPA - CLP
Low Concentration Inorganics
Elemental Expression Factors {B)
Lab Name:
Lab Code:
Contract:
Case No.:
Instrument ID Number:
SDG No.:
Method:
Date:
| jWave-
|E1 Length
Analyte ]E| or
I |Mass
I I
0 |Factor | 0 |Factor | 0 |Factor
MI | M | | M |
l_l
l_l
I I
!_l
I I
I I
Comments:
l_l
IJ
l_l
I I
I I
I I
I I
I I
I i
I I
I I
I I
I I
I I
1 I I
E| IE!
0 |Factor | 0
M| | M
Factor
IS |
I I
FORM XIV
LCIN
5/95
-------
U.S. EPA - CLP
Low Concentration Inorganics
ICP-MS Tuning and Response Factor Criteria
Lab Name;
Lab Code:
Instrument ID Number:
Analysis Date:
Contract:
Case No.
SDG No.:
Run No.:
Analysis Times: (Initial)
(Final)
Tuning
m/z
7Li/59Co_|_
59Co/59Co_|
115In/59Co_f
~205Tl/59Co f
Ion
Abundance
Criteria
(0.20 - 1.00)
'( 1.00 f
"(0.75 - 2.00)"
"(0.50 - 1.20)"
Relative Abundance
Initial
Final
Response Factor (counts per second)
m/z
7Li_
59Co_
_115In~
102Ru"
~205Tl~
Response
Factor
Criteria
( > 2,000 )
'{ >20,000 )"
"( >10,000 )"
'{ < 25 )"
( > 1,000 )
RF,
Initial
Response
Final
Mass Calibration
m/z
7Li_
5 9 Co
115In~
~2 05T1~
Acceptable
Mass Range
I ( 6.92
"| ( 58.83
"| (114.80
"l (204.87
7.12 )|
59.03
115.00
205.07
) I
) I
Observed Mass
FORM XV - LCIN
8/95
-------
U.S. EPA - CLP
Low Concentration Inorganics
ICP-MS Internal Standards Relative Intensity Summary (A)
Lab Name;
Lab Code:
Case No.
Instrument ID Number;
Start Time:
Contract:
SDG No.:
Run No.;
Method:
End Time:
Internal Standards %RI For:
I EPA
I Sample
| No.
Time I Element
IQ
Element |
IQ
]_l
1 1
Element | I Element
_ IQI _
IJ
I I
IJ
I I
IJ
LI
LI
IJ
I I
IJ
LI
I I
LI
LI
I I
1 I
I |Element | |
IQI _ IQI
I I I I
LI
l_l
LI
l_l
IJ
IJ
!J
I I
LI
LI
I I
LI
l_l
I 1
I I
IJ
I I
LI
IJ
LI
l_l
l_l
LI
LI
i_l
IJ
l_l
LI
LI
LI
IJ
Ll
I I
Ll
l_l
I I
FORM XVI - LCIN
8/95
-------
U.S. EPA - CLP
Low Concentration Inorganics
Analysis Run Log (A)
Lab Name:
Lab Code:
Case No.
Instrument ID Number:
Start Date:
Contract:
SDG No.:
Run No.
Method:
End Date:
| | ill Analytes
| EPA | Prep. I | |
| Sample | Batch |Time| D/F |A|S|A|B|B|C|C|C|C|C|F|P|M|M|H|N|K|S[A|N|T|V|
| No. | Number | | |l|b|s|a|e|d|a|r|o|u|e|b|g|n|g|i| |e|g|a|l| |
l_l_IJ J J J J J J J J J J J _l_!
UJJJJJJJJJJJJJJJJJJJJJ
IJ J J J J J J J J J J J J J J J J J J J J J
IJJJJJJJJJJJJJJJJJJJJJJ
IJJJJJJJJJJJJJJJJJJJJJJ
IJJJJJJJJJJJJJJJJJJJJJJ
IJJJJJJJJJJJJJJJJJJJJJJ
IJJJJJJJJJJJJJJJJJJJJJJ
IJJJJJJJJJJJJJJJJJJJJJJ
IJ J J J J J J J J J J J J J J J J J J J J J
IJ J J JJJ JJJ JJJ JJJ JJJJ JJJ
J_l J_l_l J_l J_l_l_l_l JJ_I J J_l
l_l_l_l_l_l_!_l_l_l_l_l_i_l_l_l_!_l_l_l_l_l_l
IJJJJJJJJJJJJJJJJJJJJJJ
IJJJJJJJJJJJJJJJJJJJJJJ
IJJJJJJJJJJJJJJJJJJJJJJ
l_l_l_l_l_l_l_l_l_l_l_l_l_l_l_l_l_l_l_l_l_l_l
l_l_l_l_l_l_l_l_l_l_l_l_l_l_l_l_l_l_l_l_l_!_l
l_LLI_l_l_l_l_l_i_l_l_l_l_l_l_l_l_l_l_t_l_l
l_U_l_IJJ J_IJ_U J J_l JJJ J_l J J J
l_l J_l_l J J J J_l J J J-I_l J JJJ_I J J_l
I _I_I_I_I_I_I_I_)_I_I_!_I_L1_I_I_J_I
I J_IJ_I_I_U_I_I_I J_I_IJ J_l J_l_l J JJ
IJ J J J J J J J J J J J J J J J J J J J J J
I JJJJJJJJJJJJJJJJJJJJJJ
IJJ J J J J J JJJ JJJ JJ JJJ JJJJ
l_l J_l_l J J_l J J J J J_l_l_l J J J_l_l_l_l
J_l J_l_l J J_I_I_U J_l JJ_I
i_i_i_i_i_i_i_i_i_i_i_i_i_i_i_i_i_i_i_i_i_i_i
I I I II I I I I M II M I I I 1 I ! II
FORM XVII - LCIN
8/95
-------
U.S. EPA - CLP
Low Concentration Inorganics
Analysis Run Log (3)
Lab Name:
Lab Code:
Case No.:
Contract:
SDG No.:
Instrument ID Number:
Start Date:
Retention Time Window:
Run No.:
Analyte:
Lower Limit:
Method:
End Date:
Upper Limit:
EPA | Prep.
Sample | Batch
No. I Number
Int. | Fin. | Time | D/F | %R | %RSD |Retention|
Vol. | Vol. II! I I Time |
FORM XVIII - LCIN
8/95
-------
U.S. EPA - CLP
Low Concentration Inorganics
Standard Solutions Sources
Lab Name:
Lab Code:
Case No.
Contract:
SDG No.
Analyte
I I
I Aluminum_|
| Antimony_|
I Arsenic |
I Barium |
I Beryllium!
I Cadmium 1
I Calcium [
| Chromiun._|
I Cobalt |
I Copper |
I Iron |
| Lead |
[Magnesium]
[Manganese|
[Mercury i
[Nickel |
1 Potassium]
| Selenium_|
I Silver |
I Sodium [
IThallium_|
I Vanadium_|
I Zinc |
|Cyanide |
ICV
Standard
Source
CCV
Standard
Source
CRI
Standard
Source
LRS
Standard
Source
ICS
Standard
Source
LCS |
Standard I
Source )
Comments:
FORM XIX - LCIN
8/95
-------
EXHIBIT C - Tables
TABLE I, - Inorganic Target Analyte List . C-l
TABLE II. - Initial and Continuing Calibration Verification, CRDL,
Standard Control Limits, and LCS Standard Control Limits for
Inorganic Analyses C-2
TABLE III. - Spiking Levels for Matrix Spike C-3
TABLE IV. - Interference Check Sample Components and Concentrations for
ICP and ICP/MS C-4
TABLE V. - Example of Analyte Concentration Equivalents (mg/L) Arising
from Interferents at the 100 mg/L Level for ICP/AES C-5
TABLE VI. - Tuning Solution For ICP/MS C-6
TABLE VII. - Tuning, Response Factor, and Mass Calibration Criteria for
ICP/MS C-6
TABLE VIII. - Memory Test Solution for ICP/MS C-l
TABLE IX. - Internal Standards That May Be Used in ICP/MS C-8
TABLE X. - Recommended Elemental Expressions for Isobaric Interferences
for ICP/MS C-8
TABLE XI. - Contributions of Concomitant Elements to Nearby Analytes for
ICP/MS When Resolution and Measurement Schemes Vary . C-9
TABLE XII. - Isobaric Molecular-Ion Interferences That Could Affect the
Analytes C-10
TABLE XIII. - Mass Choices for Elements That Must Be Monitored Either
During the Analytical Run or in a Separate Scan for ICP/MS .... C-12
-------
TABLE I. - Inorganic Target Analyte List
CRDL11,21
Analyte
(uq/L)
Aluminum
100
Antimony
5
Arsenic
2
Barium
20
Beryllium
1
Cadmium
1
Calcium
500
Chromium
5
Cobalt
5
Copper
5
Iron
100
Lead
2
Magnesium
500
Manganese
10
Mercury
0.2
Nickel
20
Potassium
750
Selenium
3
Silver
10
Sodium
500
Thallium
2
Vanadium
10
Einc
5
Cyanide
10
(1) toy analytical method specified in Exhibit D may be utilized, except for
mercury and cyanide, provided the documented instrument detection limits
(IDLs) meet the CRDL requirements. Higher detection limits may only be used
in the following circumstance:
If the sample concentration exceeds five times the detection limit of the
instrument or method in use, the value may be reported even though the IDL may
not equal the CRDL. This is illustrated in the example below:
For lead:
Method in use = ICP
IDL = 40
Sample concentration =220
CRDL = 2
The value of 220 may be reported even though the IDL is
greater than CRDL. The IDL must be documented as described
in Exhibit E.
(2) The CRDL is the IDL obtained in pure water that must be met using the
procedure in Exhibit E. The detection limits for samples may be considerably
higher depending on the sample matrix.
C-l
ILC03.1
-------
TA3LE II. - Initial and Continuing Calibration Verification, CRDL, Standard
Control Limits, and LCS Standard Control Limits for Inorganic Analyses
INITIAL AND CONTINUING CALIBRATION VERIFICATION LIMITS
% of True Value
Limit (EPA Set)
Analytical Method Inorganic Species Low High
ICP and AA Metals 90 110
ICP-MS Metals 90 110
Cold Vapor AA Mercury 80 120
Other Cyanide 85 115
CRDL STANDARD CONTROL LIMITS
Analytical Method
Inorganic Species
% of True Value
Limit {EPA Set)
Low High
ICP/OES and AA Metals 50 150
ICP/MS Metals 50 150
Cold Vapor AA Mercury 50 150
Other Cyanide 50 150
LCS STANDARD CONTROL LIMITS
The LCS Standard Control Limits are the same for all inorganic species. The
limits are 80 - 120.
C-2 ILC03.1
-------
TABLE III. - Spiking Levels for Matrix Spike
Element Water (ug/L)
Aluminum
*
Antimony-
200,2>
Arsenic
100<3'
Barium
500
Beryllium
50
Cadmium
50
Calcium
*
Chromium
200
Cobalt
200
Copper
200
Iron
1000
Lead
100
Magnesium
•*
Manganese
200
Nickel
200
Potassium
•ir
Selenium
50H)
Silver
50
Sodium
llr
Thallium
50
Vanadium
200
Zinc
500
Mercury
1
Cyanide
100
(1) The levels shown indicate concentrations added in the final digestate of
the spiked sample.
(2) The spike must be made with a solution containing antimony in the +5
oxidation state.
(3) The spike must be made with a solution containing arsenic in the +5
oxidation state.
(4) The spike must be made with a solution containing selenium in the +6
oxidation state.
*No spike required.
C-3
ILC03.1
-------
TABLE IV. - Interference Check Sample Components and Concentrations for ICP
and ICP/MS
Interference Solution A Solution AB
Component Concentration (mq/L) Concentration (mg/L)
Aluminum
100.0
100.0
Calcium
300.0
300.0
Iron
250.0
250.0
Magnesium
100.0
100.0
Sodium
250.0
250.0
Phosphorous
100.0
100.0
Potassium
100.0
100.0
Sulfur
100.0
100.0
Carbon
200.0
200.0
Chlorine
2121.5
2121.5
Molybenum
2.0
2.0
Titanium
2.0
2.0
Arsenic 0,0 0.100
Cadium 0.0 .100
Chromium 0.0 .200
Cobalt 0.0 0.200
Copper 0.0 .200
Manganese 0.0 ,200
Nickel 0.0 0.200
Selenium 0.0 0.100
Silver 0.0 .050
Vanadium 0.0 0.200
Zinc 0.0 0.100
Note: See Exhibit D, Part E, for additional information.
C-4
ILC03.1
-------
TABLE V. - Example of Analyte Concentration Equivalents (mg/L) Arising from
Interferents at the 100 mg/L Level for ICP/AES
Wavelength Interferent
Analyte
(nm)
A1
Ca
Cr
Cu
Fe Mg
Mn
Ni
Ti
V
A1
308.215
0.21
__
—
1.4
Sb
206.833
0.47
—
2.9
—
0.08
—
—
.25
0.45
As
193.696
1.3
—
0.44
—
—
—
—
—
1.1
Ba
455.403
—
—
—
—
—
—
—
—
—
Be
313.042
0.04
0.05
Bo
249.773
0.04
—
—
—
0.32
—
—
—
—
Cd
226.502
—
—
—
—
0.03
—
0.02
—
—
Ca
317.933
—
—
0.08
—
0.01 *
0.04
—
0.03
0.03
Cr
267.716
0.003
0.04
—
—
0.04
Co
228.616
—
—
0.03
—
0.005
—
0.03
0.15
—
Cu
324.754
—
—
—
—
0.003
—
—
0.05
0.02
Fe
259.940
0.12
—
—
—
Pb
220.353
0.17
—
—
—
—
—
—
—
—
Mg
279.079
—
•k
0.11
—
0.13
0.25
—
0.07
0.12
Mn
257.610
0.005
—
0.01
—
0.002 0.002
—
—
—
—
Mo
202.030
0.05
—
—
—
0.03
—
—
—
—
Ni
231.604
—
—
—
—
—
—
—
—
—
Se
196.026
0.23
—
—
—
0.09
—
—
—
—
Si
288.158
—
—
0. 07
—
—
—
—
—
0.01
Na
588.995
—
—
—
—
—
—
—
0.08
—
T1
190.864
0.30
—
—
—
—
—
—
—
—
V
292.402
—
—
0.05
—
0.005
—
—
0.02
—
Zn
213.856
—
—
—
0.14
—
—
0.29
—
—
Ames Laboratory, USDOE, Iowa State University, Ames, Iowa 50011.
* These reported interferences are probably due to contaminants and not true
spectral interference lines. When evaluating interferents, ultrapure reagents
should be used. Interferences that are found should be verified by examination
of the wavelength tables.
C-5 ILC03.1
-------
TABLE VI. - Tuning Solution For ICP/MS
(The tuning solution must consist of the following elements
at the stated concentrations.)
Concentration
Element (ug/L)
7Li
100
Co
100
In
100
T1
100
TABLE VTI.
- Tuning, Response
Factor, and Mass Calibration Criteria for ICP/MS
Tuning Criteria
m/z
Ion Abundance Criteria
7Li/59Co
{ 0.20 - 1.00 )
59Co/59Co
( 1.00 )
115ln/59Co
( 0.75 - 2.00 )
205T1/59CO
( 0.50 - 1.20 )
Response Factor Criteria
m/ 2
Response Factor Criteria
7 Li
( >20 counts per ppb )
59Co
( >200 counts per ppb )
115In
( >100 counts per ppb )
102Ru
{ <25 counts)
205T1
( > 10 counts per ppb )
• Mass
Calibration Criteria
m/ z
Exact Mass
7Li
( 6.92 - 7.12 }
59Co
( 58.83 - 59.03 )
115In
( 114.80 - 115.00 )
205T1
( 204.87 - 205.07 )
C-6 ILCC3.1
-------
TABLE VIII. - Memory Test Solution for ICP/MS
(The memory solution must consist of the following elements
at the stated concentrations)
Element Concentration (mg/L)
A1 500
Ca 500
Fe 500
Mg 500
Na 500
K 500
C 1000
CI 3600
Mo 10
P 500
S 500
Ti 10
Sb
As
Ba
Be
Cd
Cr
Co
Cu
Pb
Mn
Ni
Se
Ag
T
V
Zn
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
Note: See Exhibit D, Part E, and Exhibit E for further references to the
memory test solution.
C-7
ILC03.1
-------
TABLE IX. - Internal Standards That May Be Used in ICP/MS
Bismuth
Holmium
Indium
Rhodium
Scandium
'Lithium
Terbium
Yttrium
TABLE X. - Recommended Elemental Expressions for Isobaric Interferences for
ICP/MS
Element
Isobaric
Correction
Expression Proportional
to Elemental Concentration
A1
none
(1. 0000) (27M)
Sb
none
(1.0000) (:21M)
As
ArCl, Se
(1.0000) (75M) - (3.1278) (77M) + (1. 0177)
(78M)
Ba
none
(1. 0000) (135M)
Be
none
(1. 0000) (9M)
Cd
MoO, Sn
(1.0000) (114M) - (0. 0149) (U8M) - (1.6285
) (l08M)
Ca
none
(1.0000)("M)
Cr
none
(1.0000) (S2M)
Co
none
(1.0000) (S'M)
Cu
none
(1.0000) (65M)
Fe
none
(1.0000) (S,M)
Pb
none
(1. 0 0 0 0) (208M) + (1. 0000) (2"M) + ( 1.0000
) (20SM)
Mg
none
(1.0000) (26M)
Mn
none
(1.0000)(«M)
Ni
none
(1.0000) (60M)
Se
Ar2
(1.0000) (7eM) - (0. 1869) (76M)
Ag
none
(1.0000) (107M)
T1
none
(1. 0000) (205M)
V
CIO, Cr
(1.0000) (51M) - (3. 1081) (53M) + (0.3524)
(52M)
Zn
none
(1. 0 0 0 0) (66M)
*Li
Li(natural)
(1.0000) (6M)-(0.0813) (7M)
Sc
none
(1.0000) (,5M)
Y
none
(1.0000) (8*M)
Rh
none
(1.0000) (103M)
In
Sn
(1.0000) (ll5M) - (0 . 0149) (U8M)
Tb
none
(1.0000) (155M)
Ho
none
(1. 0 0 0 0) (165M)
Bi
none
(1.0 0 0 0) (209M)
M = the total ion count rate at the specified mass.
C-8
ILC03.1
-------
TABLE XI. - Contributions of Concomitant Elements to Nearby Analytes for
ICF/MS When Resolution and Measurement Schemes Vary
Concentrations listed are the approximate level (mg/L) measured
when the interferant is present at 100 mg/L.
Peak Width at 10% of the Peak Height
1. 0 amu 0. 8 amu
Interferent Integration Width Integration Width
Analyte Element 0.9 amu 0.3 amu 0. 9 amu 0.3 amu
121Sb
lzsSn
820
5
10
1
121Sb -
122Te
77
none
1
none
75As
74Se,
76Se
910
4
3
none
9Be
10B
1,200
12
9
1
u2Cd
U3In
1,700
8
10
none
n,Cd
ll5In
>5,000
150
180
18
u6Cd
u5In
30
none
5
none
52Cr
S1V
1.4
1.5
none
none
HCr
54 Fe
650
7
1
none
ssCo
58Ni,
60Ni
>1,500
6
2
none
63Cu
62Ni,
«Ni
190
1
none
none
63Cu
64Zn
4,000
14
9
none
wCu
HNi
1
1
none
none
6sCu
"Zn,
66Zn
>4,400
22
15
none
ZOSpjj
209Bi
140
14
57
none
"Mn
54 Fe,
56pe
900
8
4
none
58Ni
"Co
>3,000
96
75
7
««Ni
59Co
9
4
10
5
62Ni
63 Cu
>8,500
690
4,500
16
107Ag
106pdf
i°epd
>2,400
22
80
4
107Ag
l#6Cd,
108Cd
130
3
5
2
109Ag
108Pd,
u°pd
1,800
12
36
3
109Ag
10BCd,
U0Cd
1,600
10
37
3
51 v
"Cr
>2,100
45
410
1
64 Zn
65Cu,
63Cu
>7,800
57
410
2
mZn
S5Cu
2
none
3
2
C-9
ILC03.1
-------
TABLE XII. - Isobaric Molecular-Ion Interferences That Could Affect the
Analytes
Interferents
Analyte
Oxygen
Hydroxyl
Nitrogen
Chlorine
Sulfur
Carbon Other
l21Sb
PdO
AgN
AgC
123Sb
AgO
AgN
SrCl
ZrS
CdC
75As
CoO
NiOH
NiN
ArCl
CaS
CuC
l38Ba
SnO
SbOH
13,Ba
SbO
SnOH
MoCl
»«Ba
SnO
SnOH
SnC
13SBa
SnO
SnOH
MoCl
134 Ba
SnO
SnOH
SnN
MoCl
SnC
132Ba
SnO,
CdO
InOH
SnN
MoCl
MoS
SnC
130Ba
CdO
CdOH
SnN,
CdN
MoCl
MoS
SnC
9Be
luCd
MoO
MoOH
MoN
SeCl
SeS
112Cd
MoO,
ZrO
MoOH
MoN
SeCl, AsCI
SeS
MoC
mCd
MoO
MoOH
MoN
GeCl
ucCd
MoO,
ZrO
MoN,
ErN
GeCl, AsCl
SeS
MoC
113Cd
MoO
MoOH
SeCl, AsCl
ll6Cd
MoO
106Cd
ZrO
MoN,
ZrN
GeS
MoC,
ZrC
108Cd
MoO,
ZrO
ZrOH
MoN,
ZrN
GeCl
SeS, GeS
MoC,
ZrC
52Cr
ArO
CI OH
ArC
"Cr
CIO
ArOH
KN
NCI, OC1
KC
50Cr
SO
ArN
SO
ArC
Mo**
"Cr
CI OH
ArN,
CaN
CaC
59Co
CaO
CaOH
ScN
MgCl
AlS
TiC
Sn**
63 Cu
TiO,
P02
TiOH
TiN
SiCl, MgCl
PS
VC
ArN a
65Cu
TiO
TiOH
VN
SiCl
SS, S02H
CrC
208 pb
20«pb
207pb
J04pb
"Mn
KO
ArOH
KN
NaS
CaC
Cd"
202Hg
WO
200Hg
WO
WOH
WN
l99Hg
WO
WOH
201Hg
WOH
198Hg
WO
TaOH
WN
WC
2MHg
198Hg
WN
WC
S8Ni
CaO
KOH
CaN
NaCl
MgS
TiC
Cd**
Sn**
"Ni
CaO
CaOH
TiN
MgCl, NaCl
SiS
TiC
Sn**
"Ni
TiO
ScOH
TiN
AlCl, MgCl
SiS
TiC,
CrC Sn"
continued
C-10
ILC03.1
-------
TABLE XIII (cont'd)
Interferents
Analyte
Oxygen
Hydroxyl
Nitrogen
Chlorine
Sulfur
Carbon
Other
"Ni
ScO
CaOH
TiN
MgCl
SiS
TiC
Sn"*
64Ni
TiO
TiOH
TiN,
CrN
SiCl,
A1C1
ss
CrC
6t>Se
ZnO
CuOH
ZnN
ScCl,
CaCl
TiS
ZnC
78Se
NiO
NiOH
ZnN
CaCl,
KCl
TiS
ZnC
92Se
ZnO
CuOH
ZnN
TiCl,
ScCl
TiS, CrS
liSe
NiO
CoOH
NiN
KCl
CaS
ZnC
71Se
NiO
NiOH
CuN
CaCl,
ArCl
ScS
CuC
74Se
NiO
FeOH
NiN
C1C1,
KCl
CaS
NiC
107Ag
ZrO
ZrOH
GeCl
AsS
MoC
X09Ag
MoOH
MoN
GeCl
SeS
MoC
205T1
203^2
WOH
Sly
CIO
SOH
C1N
CIO,
C1N
FS
KC
50y
SO
ArN
ArC
Mo**
"En
TiO
TiOH
TiN,
CrN
SiCl,
A1C1
SS
CrC
66Zn
TiO
TiOH
CrN
PCI,
SiCl
SS
FeC
6SZn
CrO
VOH
FeN
PCI
ArS
FeC
Ba**
67Zn
VO
TiOH, Cr
CrN
SCI
CIS
MnC
Ba**
70Zn
FeO
CrOH
GeN
C1C1
ArS
NiC
Note: The information provided in this table does not indicate that all of
the described interferences need to be tested. However, the table can be
consulted for informational purposes if unusual samples are encountered.
C-ll
ILC03.1
-------
TABLE XIII. - Mass Choices for Elements That Must Be Monitored Either During
the Analytical Run or in a Separate Scan for ICP/MS
Mass Element of Interest
27 Aluminum
121, 123 Antimony
75 Arsenic
138, 137, 136, 135, 134, 132, 130 Barium
9 Beryllium
114, 112, 111, 110, 113, 116, 106, 108 Cadmium
42, 43, 44, 46, 48 Calcium
52,53,50,54 Chromium
59 Cobalt
63, 65 Copper
56, 54, 57, 58 Iron
208, 207, 206, 204 Lead
24, 25, 26 Magnesium
55 Manganese
202, 200, 199, 201 Mercury
58, 60, 62, 61, 64 Nickel
39 Potassium
80, 78, 82, 76, 77, 74 Selenium
107, 109 Silver
23 Sodium
205, 203 Thallium
51, 50 Vanadium
64, 66, 68, 67, 70 Zinc
83 Krypton
72 Germanium
139 Lanthanum
140 Cerium
129 Xenon
118 Tin
105 Palladium
47, £9 Titanium
125 Tellurium
69 Gallium
35, 37 Chlorine
98, 96, 92, 97, 94 Molybdenum
Note: Although the only masses that must be monitored are underlined, it is
strongly recommended that the other elements be monitored to indicate other
potential molecular interferences that could affect the data quality.
Boldface and underlined masses indicate the masses that should have the most
impact on data quality and the elemental equations used to collect the data.
Underlined masses must be monitored.
C-12
ILC03.1
-------
EXHIBIT D: Analytical Methods
D-l
ILC03.
-------
TABLE OP CONTENTS
EXHIBIT D: Analytical Methods D-l
SECTION I: Introduction D-3
SECTION II: Sample Preservation and Holding Times D-4
SECTION III: Sample Preparation . D-S
Part A - Sample Preparation D-5
Part B - Sample Preparation using Open-Vessel Block or Hot Plate
Digestion D-5
Part C - Sample Preparation using Closed-Vessel Microwave Oven
Digestion D-6
Part D - Distillation Procedures for CN Analysis in Water .... D-10
SECTION IV: Sample Analysis D-15
Part A - Reagents and Standards for Metals Analysis D-15
Part B - Inductively Coupled Plasma-Atomic Emission Spectrometric
Method D-l 9
Part C - Graphite Furnace and Flame Atomic Absorption Spectroscopy . D-25
Part D - Inductively Coupled Plasma - Mass Spectrometry ...... D-29
Part E - Mercury Analysis in Water D-39
Part F - Method for Total Cyanide Analysis in Water D-45
D-2
ILC03.1
-------
SECTION I: Introduction
Any analytical method specified in Exhibit D may be utilized as long as the
documented instrument or method detection limits meet the Contract Required
Detection Limits (CRDL) (Exhibit C, Tables I and II). Analytical methods with
higher detection limits may be used only if the sample concentration exceeds
five times the documented detection limit of the instrument or method.
Samples requiring dissolved metals analysis, will be filtered through a
0.45 jim. membrane filter and preserved in the field before the samples are
shipped to the laboratory. Instrument calibration standards must be matrix
matched (with respect to acid content) to the samples.
All samples must initially be run undiluted (i.e., original sample or final
product of sample preparation procedure). When an analyte concentration
exceeds the calibration or linear range, re-analysis for that analyte(s) is
required after appropriate dilution. Dilutions are prepared using reagent
water with the same acid content as the undiluted sample. The Contractor must
use the lowest dilution factor necessary to bring each analyte within its
valid analytical range (but not below the CRDL). If more than one dilution is
made to cover all analytes, the reported value must be from the sample result
with the smallest dilution that is in the linear range for the analyte. The
Contractor must submit proof that dilution was required to attain valid
results by submission of both diluted and undiluted sample measurements in the
raw data.
Labware must be acid cleaned according to the U.S. Environmental Protection
Agency (EPA) manual "Methods for Chemical Analysis of Water and Wastes" or an
equivalent procedure. Samples must be opened and digested in a hood. Stock
solutions for standards may be purchased or made up as specified in Section
IV, part A of Exhibit D. All sample dilutions shall be made with acidified
deionized water to maintain constant acid strength.
Before water sample preparation is initiated, the Contractor must check the pH
of all water samples, and note the pH in the sample preparation log and
Comments Page.
Unless otherwise instructed by the EPA Administrative Project Officer (APO),
all samples must be mixed thoroughly prior to aliquoting for analysis or
digestion.
Background corrections are required for all furnace atomic absorption (AA)
measurements.
All inductively coupled plasma - atomic emission spectroscopy (ICP-AES), and
inductively coupled plasma - mass spectrometry (ICP-MS) measurements shall
require a minimum of two complete replicate integrations. Integrations for
all samples and quality assurance measurements must be reported in the raw
data in concentration units; intensities are not acceptable. The average of
the integrations must be used for standardization, sample analysis, and for
reporting as specified in Exhibit B.
D-3
ILC03.1
-------
SECTION II: Sample Preservation and Holding Times
1.
Preservation of Water Samples
Measurement
Parameter
Container (1,2) Preservation (3)
Metals (4)
P, G
HN03 to pH <2
Cyanide (CN), total A
and amenable
to chlorination
0.6 g ascorbic acid (5)
NaOH to pH >12
Cool, maintain at
4°C (±2°C)
Footnotes:
(1) Polyethylene
-------
SECTION III: Sample Preparation
Before collecting samples, a decision must be made by the data user as to the
type of data desired, i.e., dissolved or total constituent analysis. This
information will be included on the traffic report and the following
preparation techniques shall be used for analysis under this contract.
All samples and standards (including Quality Assurance/Quality Control (QA/QC)
standards) must be matrix matched before analysis. Matrix matching must be
applied without affecting the original sample volume bv more than 10 percent.
Part A - Sample Preparation for "Dissolved" Metals Analysis
For the determination of dissolved constituents the sample must be filtered
through a 0.45 jim membrane filter and then preserved in the field. This will
be performed by the sampling team and recorded on the traffic report form.
Analysis performed on a sample so treated shall be reported as "dissolved"
concentrations.
Part B - Sample Preparation using Open-Vessel Block or Hot Plate Digestion
for "Total" Metals Analysis
1 Scope and Application
This method is an acid digestion procedure using a multi-position block
digester or hot plate to prepare water samples for analysis of "total"
metals by GFAA, flame AA, ICP, or ICP-MS.
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
2 Summary of Method
A HNOj/HCl mixture is added to a representative 100 mL portion of a water
sampleand heated for 2 h or until volume is reduced to between 25 and 50
mL. After cooling, the digestate is filtered and brought to a 100 mL final
volume.
3 Apparatus and Materials
3.1 MBlock digester (i.e., LABCONCO, AI Scientific, Lachat Questron), or
hotplate.
3.2 250 mL volumetric block digestion tubes, or 250 mL beakers equipped
with ribbed watchglasses.
D-5
ILC03.1
-------
3.3 Thermometer that covers a range of 0-200 °C.
3.4 Analytical balance capable of weighing to the nearest mg,
3.5 Whatman No. 42 filter paper or equivalent.
3.6 Polyethylene bottles, 125 mL or 250 mL.
4 Reagents
4.1 Reagent Water: Water used for preparing samples and reagents must meet
the specifications for ASTM Type II water (ASTM D1193).
4.2 Concentrated reagent grade nitric acid (HN0}) (sp gr. 1.41).
4.3 Concentrated reagent grade Hydrochloric Acid {sp gr. 1.19).
4.4 Reagent grade Hydrogen Peroxide (H202) (30%)
5 Digestion Procedure
Shake and transfer 100 mL of well-mixed sample to a 250 mL block
digester tube or a 250 mL beaker. Add 2.0 mL of (1+1) HN03 and 1.0 mL
(1+1) HC1 to the sample. If using beakers, cover with a ribbed
watchglass. Reflux at 95 °C for 2 hours or until the volume is
reduced to between 25 and 50 mL (see note 1), making certain that the
sample does not boil. Cool the sample and filter to remove insoluble
material. Adjust the sample volume to 100 mL with reagent water, mix
and transfer to a 125 mL plastic bottle (see note 2). The sample is
now ready for analysis. Concentrations so determined shall be
reported as "total."
6 Notes: 1) Monitor temperature with a thermometer placed in a
centrally located digestion vessel that contains 100 mL
of the appropriate digestion matrix.
2) Alternatively, the sample may be diluted to volume,
mixed, centrifuged or allowed to settle, then decanted
into a plastic storage bottle.
Part C - Sample Preparation using Closed-Vessel Microwave Oven Digestion for
"Total" Metals Analysis
1 Scope and Application
1.1 This method is an acid digestion procedure using microwave energy to
prepare water samples for analysis by GFAA, ICP, and/or ICP-MS for the
following metals:
D-6
ILC03.1
-------
Aluminum
Antimony
Arsenic
Barium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Beryllium
Cadmium
Calcium
Thallium
Vanadium
Zinc
2 Summary of Method
A representative 45 mL water sample is digested with 5 mL of concentrated
nitric acid for 20 min using microwave heating with a laboratory microwave
digestion oven. The sample is placed in a Teflon® PFA vessel (or Teflon®
liquid vessel) with 5 mL of concentrated nitric acid. The vessel is capped
and heated in the microwave digestion oven. After cooling, the digestate is
filtered if necessary and analyzed.
3 Apparatus and Materials (Microwave)
3.1 Microwave Digestion Oven - Use only laboratory-grade microwave
digestion ovens. It must be power programmable with a maximum power
rating of at least 600 watts. It must have a rotating sample
turntable to ensure uniform exposure to the microwave radiation.
3.2 Digestion Vessels - Use Teflon® or Teflon®-lined closed-system
microwave digestion vessels capable of withstanding pressures of at
least 100 psi. The vessels must be capable of controlled pressure
relief at the vessels maximum pressure rating.
4 Microwave Calibration Procedure
Microwave ovens which are controlled through a % power setting must be
calibrated in terms of the microwave energy absorbed by the sample vs. the
% power setting. The calibration function is not necessarily linear so
that a multi-point calibration must be performed over the range of
interest. Also the calibration function can vary from oven-to-oven so that
each oven must be calibrated. The calibration procedure is given below.
The microwave digestion oven shall be calibrated every six months, and the
calibration documented in the laboratory sample preparation log.
4.0.1 Warm-up and equilibrate the microwave oven by heating 1-2L water
at 100% power for 5 minutes.
4.0.2 Measure the power absorbed at % power settings of 30, 40, 50,
60, 70, 80, 90, 95, and 100. Perform each measurement in
triplicate. For each measurement, pour 1000 + 2 g of water into
a microwave transparent vessel, such as a teflon bottle.
Measure and record the initial temperature of the water to 0.1
°C (must be 24 ± 2°C). Place vessel into the microwave, start
D-7
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carousel, and turn on the exhaust fan. Set the time to 120 sec
and the power to the desired power setting (% power), and
irradiate vessel. Promptly remove the vessel, add a stir bar,
place on magnetic stirrer, and thermally equilibrate the water.
Measure and record to 0.1 °C the maximum temperature observed
within 30 seconds of removing the vessel from the oven.
Safety Note! Do not irradiate with stir bar in vessel. This can cause
electrical arcing.
4.0.3 The absorbed power is determined by the following relationship:
P = (K'Cp-M- LI)
t
P = the apparent power absorbed by the sample in watts (W)
K = 4.184; the conversion factor for thermochemical cal/sec to W
Cp = the heat capacity of water (cal* g "1* C"')
M = mass of the water sample in grams (g)
AT = the final temperature minus the initial temperature (°C)
t = the time in seconds
Using 2 min and 1000 g of distilled water, the calibration equation
simplifies to:
P = AT • 34.87
Plot the measured watts vs. % power setting for each data point.
Determine a calibration line for the linear portion of the calibration
plot. The line is used to determine the % power setting for the
actual watts specified in the protocol. If non-linearity is observed
over the range of interest, measure the power at additional power
settings to improve the accuracy of the calibration curve.
5 Microwave Vessel Cleaning Procedure
Clean new microwave digestion vessel by rinsing 3 times with reagent water,
immersing in a 1:1 HC1 cleaning bath for a minimum of 3 hours, rinsing 3
times with reagent water, immersing in a 1:1 HNO, cleaning bath for a
minimum of 3 hours, and rinsing 3 times with reagent water. Next, heat the
vessels for 96 hours at 200°C to anneal them prior to first use. The
vessels must be disassembled during annealing. The sealing surfaces (the
top of the vessel or its rim) must not be used to support the vessel during
annealing. Between digestions wash entire vessel in hot, soapy water
(nonphosphate detergent), rinse with 1:1 nitric acid, and rinse 3 times
with reagent water. If contamination is detected in the reagent blank, all
vessels must be recleaned.
6 Digestion Procedure
6.1 Measure the tare weight of the assembled digestion vessel. Add 45 mL
sample and 5.0 mL of concentrated HN03 to each digestion vessel. Cap
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and weigh the loaded vessel to 0.01 g. Place the loaded vessels into
the sample carousel and place the carousel into the microwave oven.
For ovens controlled through % power settings, the carousel must
contain 5 vessels. If fewer samples are being digested, use
additional reagent blanks to make up the difference. For ovens
controlled through temperature feedback, install the temperature probe
on one of the vessels.
6.2 Program the microwave digestion oven such that the samples are brought
to a temperature of 160+4°C in 10 minutes followed by a slow rise to
165-170°C during a second 10 minutes, for a total digestion time of 20
minutes. For microwave digestion ovens programmed in terms of %
Power, the correct settings must be determined for each type of
digestion vessel. For single wall digestion vessels by CEM
Corporation (120 psi limit) this corresponds to 10 minutes at 545
Watts followed by 10 minutes at 344 Watts. For lined, double wall
vessels digestion vessels by CEM Corporation (200 psi limit), this
corresponds to 10 minutes at 473 Watts followed by 10 minutes at 237
Watts.
6.3 Following the 20 minute digestion, cool the samples in the microwave
unit for 5 minutes with the exhaust fan ON. The samples and/or
carousel may then be removed from the microwave unit. Before opening
the vessels, let them cool until they are no longer hot to the touch.
After cooling, weigh the sample vessels to the nearest 0.01 gram and
calculate the % digestion loss.
% digestion loss = ——— x 100
(I - T)
I = Initial weight (vessel + sample + acid)
F = Final weight after digestion (vessel + sample + acid)
T = Tare weight of vessel
6.3.1 For samples with digestion losses less than 1%, shake well to
mix any condensate within the digestion vessel. Uncap vessel.
Filter or centrifuge to remove any particles. The digestate is
now ready for analysis. Results must be corrected for the
initial dilution (45 mL diluted to 50 mL).
6.3.2 Samples with digestion losses between 1 and 10%, the final
digestate volume must be determined so that the dilution factor
can be calculated. Shake well to mix any condensate within the
digestion vessel. Quantitatively transfer the digestate to a 50
mL volumetric flask and dilute to volume. Alternatively, the
density of the digestate can be measured at the final volume
calculated by:
FY
D
D-9 ILC03.1
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FV = Final volume
F = final weight after digestion (vessel + sample + acid)
T = vessel weight
D = density of digestate
The digestate is then filtered or centrifuged to remove
particulates and is ready for analysis. Results must be
corrected for dilution,
6.3.3 For samples with digestion losses greater than 10% The
digestion loss indicates that the vessel vented during
digestion, which can significantly effect the digestion
efficiency.
Part D - Distillation Procedures for CN Analysis in Water
Note: Oxidizing agents such as chlorine decompose most of the cyanide.
Test a drop of the sample with potassium iodide-starch test paper
(Kl-starch paper); a blue color indicates the need for treatment. If a
blue color is seen, add ascorbic acid, a few crystals at a time, until a
drop of sample produces no color on the indicator paper. Then add an
additional 0.6 g of ascorbic acid for each liter of sample volume.
Distillation can then proceed.
1 Full-Size Distillation Apparatus (Distillation Option A)
1.1 Place 500 mL of sample, or an aliquot diluted to 500 mL, in the 1
liter boiling flask containing a few boiling chips. Add 50 mL of
1.25N sodium hydroxide (Section 5.2.7 of Part F) to the absorbing tube
and dilute if necessary with reagent water to obtain an adequate depth
of liquid in the absorber. Add 10 mL of 1.25 N NaOH plus 40 mL of
water to the overflow trap (the trap is optional for added safety).
Connect the trap, boiling flask, condenser, and absorber in the train
and attach to a vacuum source. Note: For added safety, all
distillations should be performed in a hood.
1.2 Start a slow stream of air entering the boiling flask by adjusting the
vacuum source. Adjust the vacuum so that approximately one bubble of
air per second enters the boiling flask through the air inlet tube.
1.3 Temporarily disconnect the overflow trap and slowly add 25 mL
concentrated sulfuric acid to the sample flask through the air inlet
tube. Rinse the tube with reagent water and allow the airflow to mix
the flask contents for 3 minutes. Add 20 mL of magnesium chloride
solution (510 g MgCl2$H20 in 1 L reagent water) to the sample flask
through the air inlet and rinse the inlet tube with a stream of water.
Excessive foaming from samples containing surfactants may be quelled
by the addition of another 20 mL of magnesium chloride solution or
addition of Dow Corning 544 antifoam agent. Reconnect the overflow
trap and readjust the vacuum.
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1.4 Heat the solution to boiling, taking care to prevent the solution from
backing up and overflowing into the trap. Reflux for one hour. Turn
off heat and continue the airflow for at least 15 minutes. When the
boiling flask is cool, close the vacuum source and disconnect the
absorber tube.
1.5 Drain the solution from the absorber into a 250 mL volumetric flask.
Rinse the absorber tube using ASTM Type I water and add the washings
to the volumetric flask. Bring to volume using ASTM Type I water.
1.6 The samples are now ready for analysis. The samples must be analyzed
for cyanide within 12 days of receipt of the original samples, as
specified in Section II. If the initial sample volume was less than
500 mL, and had to be diluted to 500 mL prior to distillation, an
appropriate dilution factor must be included in the calculations of
the original sample concentration. The dilution factor must be
reported on Form XVIII.
2 Midi-Distillation Apparatus (Distillation Option B)
2.1 Pipet 50.0 mL of sample, or an aliquot diluted to 50.0 mL into the 100
mL distillation flask. Add 2 or 3 boiling chips.
Add 30 mL of 0.25 N NaOH (Section IV, Part F, 5.2.8) to the gas
absorbing tube. Add 50 mL of 0.25 N NaOH to the overflow trap (the
overflow trap is optional for added safety). Connect the overflow
trap, boiling flask, condenser, absorber and vacuum source, as
pictured in Figure 2.
2.2 Turn on the vacuum and adjust the gang (Whitney) valves to give a flow
of three bubbles of air per second from the impingers in each reaction
vessel.
2.3 After five minutes of vacuum flow, disconnect the overflow trap and
inject 5 mL of 1:1 (v/v) H-.SO, through the top air inlet tube of the
distillation head into the reaction vessel. Allow to mix for 5
minutes. The acid volume must be sufficient to bring the
sample/solution pH to below 2.0. Add 2 mL of magnesium chloride
solution (Section III, Part D, 1.3) through the top air inlet tube of
the distillation head into the reaction flask. Excessive foaming from
samples containing surfactants may be quelled by the addition of
another 2 mL of magnesium chloride solution or addition of Dow Corning
544 antifoam agent. Reconnect the overflow trap.
2.4 Turn on the heating block or heating mantles and set for 123-125 °C.
Heat the solution to boiling, taking care to prevent solution backup
by periodic adjustment of the vacuum.
2.5 After one and one half hours of refluxing, turn off the heat and
continue the vacuum for an additional 15 minutes. The flasks should
be cool after this time. After cooling, close off the vacuum at the
gang valve and drain the solution from the absorber into a 50.0 mL
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volumetric flask and bring to volume with 0.25 N NaOH washings of the
absorber tube.
2.6 Seal the receiving solutions and store them at 4 °C until analyzed.
The solutions must be analyzed for cyanide within 12 days of receipt
of the original samples, as specified in Section II. If the initial
sample volume was less than 50 mL, and had to be diluted to 50 mL
prior to distillation, an appropriate dilution factor must be included
in the calculation of the original sample concentration. The dilution
factor must be reported on Form XVIII.
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COOLNG
WATER
CONDENSER
INLET,/'
TUBE
DISTILLING
FLASK
SCREW
CLAMP
TO LOW
VACUUM
SOURCE
ABSORBER
-HEATER
Figure 1. Cyanide distillation apparatus
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CONNECTING
TUBING
ALLIHN
CONDENSER
AIR INLET
TUBE
SUCTION
GAS N
ABSORBER
ONE UTER
BOILING FLASK
Figure 2, Cyanide distillation apparatus
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SECTION IV: Sample Analysis
Part A - Reagents and Standards for Metals Analysis
1 Acid purity must be monitored. Analyte concentrations in the calibration
and reagent blanks must be less than the CRDLs.
1.1 Acetic acid, conc. (sp gr 1.06)
1.2 Hydrochloric acid, conc. (sp gr 1.19)
1.3 Hydrochloric acid (1+1) : Add 500 mL conc. HCl to 400 mL ASTM Type I
water and dilute to 1 liter.
1.4 Nitric acid, conc. (sp gr 1.41)
1.5 Nitric acid (1+1) : Add 500 mL conc. HN03 to 400 mL ASTM Type I water
and dilute to 1 liter.
2 Reagent Water - Water meeting requirements for ASTM Type II Water (ASTM
D1193). Prepare by passing distilled water or water purified by reverse
osmosis through a mixed bed of cation and anion exchange resins. Use
reagent water for the preparation of all reagents, calibration standards
and as dilution water. The concentration of each analyte in reagent water
must be less than the CRDL for the analyte.
3 Standard stock solutions may be purchased or prepared from ultrahigh-purity
grade chemicals or metals (99.99 to 99.999% pure). All salts must be dried
for 1 h at 105 °C, unless otherwise specified.
(CAUTION; Many metal salts are extremely toxic if inhaled or swallowed. Wash
hands thoroughly after handling.)
Typical stock solution preparation procedures are given below. Concentrations
are calculated based upon the weight of pure element added, or by using the
mole fraction and the weight of the metal salt added.
Metal
weight (mg)
Concentration (mg/L) =
volume (L)
Metal salts
weight (mg) x mole fraction
Concentration (mg/L) =
volume (L)
NOTE: The recommended amounts of the starting materials specified for the
following stock solutions are dependent upon the stoichiometry of the
starting materials. Actual assay values of the starting materials
should be used and the actual amounts corrected accordingly.
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3.1 Aluminum solution, stock, 1 mL = 100 ug A1: Dissolve 1.3903 g
A1 (N03)3"9H20 in 10 mL reagent water with 10 mL. HN03. Dilute to 1000
mL with reagent water.
3.2 Antimony solution, stock, 1 mL = 100 ug Sb: Dissolve 0.1197 g Sb20j in
5 mL reagent water containing 0.1233 g C406H6 {tartaric acid). Add 500
mL reagent water and 1 mL conc. HN03. Dilute to 1000 mL with reagent
water.
3 .3 Arsenic solution, stock, 1 mL = 100 ug As: Dissolve 0.1320 g of As203
in 100 mL of reagent water containing 0.45 g NH,0H. Acidify the
solution with 12 mL conc. HN03 and dilute to 1000 mL with reagent
water.
3.4 Barium solution, stock, 1 mL = 100 ug Ba.* Dissolve 0.1437 g BaC03 in
10 mL reagent water with 10 mL conc. HN03. After dissolution is
complete, warm the solution to degas. Dilute to 1000 mL with reagent
water.
3.5 Beryllium solution, stock, 1 mL = 100 ug Be: Do not dry. Dissolve
4.5086 g Be0(C2H302}6 in reagent water, add 10.0 mL conc. HN03 and
dilute to 1000 mL with reagent water.
3.6 Cadmium solution, stock, 1 mL = 100 ug Cd: Dissolve 0.1142 g CdO in a
minimum amount of (1+1) HN03. Heat to increase rate of dissolution.
Add 10.0 mL conc. HN03 and dilute to 1000 mL with reagent water.
3.7 Calcium solution, stock, 1 mL = 100 ug Ca: Suspend 0.2498 g CaC03
(dried at 180 °C for 1 h before weighing) in reagent water and
dissolve cautiously with a minimum amount of (1+1) HNO,. After
dissolution is complete, warm the solution to degas. Add 10.0 mL
conc. HNOj and dilute to 1000 mL with reagent water.
3.8 Chromium solution, stock, 1 mL = 100 ug Cr: Dissolve 0.2424 g of
(NH.)2Cr207 in reagent water. Reduce the chromium with a few drops of
hydrazine (NH2NH2), exhibited by the color change of the solution from
orange to green. When reduction is complete, acidify with 10 mL conc.
HN03 and dilute to 1000 mL with reagent water.
3.9 Cobalt solution, stock, 1 mL = 100 ug Co: Dissolve 0.1000 g of cobalt
metal in a minimum amount of (1+1) HN03. Add 10.0 mL conc. HN03 and
dilute to 1000 mL with reagent water.
3.10 Copper solution, stock, l mL = 100 ug Cu: Dissolve 0.1000 g Cu in a
minimum amount of (1+1) HN03. Add 10.0 mL conc. HNQ3 and dilute to
1000 mL with reagent water.
3.11 Iron solution, stock, 1 mL = 100 ug Fe: Dissolve 0.1000 g Fe in a
minimum amount of (1+1) HN03. Add 10.0 mL conc. HN03 and dilute to
1000 mL with reagent water.
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3.12 Lead solution, stock, 1 mL = 100 ug Pb: Dissolve 0.1599 g Pb(N03)2 in
a minimum amount of (1+1) HN03. Add 10.0 mL of conc. HNO, and dilute
to 1000 mL with reagent water.
3.13 Magnesium solution, stock, 1 mL = 100 ug Mg: Dissolve 0.1658 g MgO in
a minimum amount of (1+1) HN03. Add 10.0 mL conc. HN03 and dilute to
1000 mL with reagent water.
3.14 Manganese solution, stock, 1 mL = 100 ug Mn: Dissolve 0.3149 g of
Mn (C2H302) 2 in reagent water. Add 10.0 mL of conc. HN03 and dilute to
1000 mL with reagent water.
3.15 Mercury solution, stock, l mL = 100 ug Hg: Dissolve 0.1708 g mercury
(II) nitrate Hg(N03)2'(H20) in 75 mL of reagent water. Add 10 mL of
conc. HNOj and dilute to 1000 mL with reagent water.
3.16 Molybdenum solution, stock, 1 mL = 100 ug Mo: Dissolve 0.2043 g
(NH,)2Mo04 in reagent water. Dilute to 1000 mL with reagent water.
3.17 Nickel solution, stock, 1 mL = 100 ug Ni Dissolve 0.1000 g of nickel
metal in 10 mL hot conc. HN03, cool and dilute to 1,000 mL with
reagent water.
3.18 Potassium solution, stock, lmL = 100 ug K: Dissolve 0.1767 g K2C03 in
a minimum amount of (l + l)HNO,. After dissolution is complete, warm
the solution to degas. Add 10.0 mL conc. HN03 and dilute to 1,000 mL
with reagent water.
3.19 Selenium solution, stock, lmL = 100 jig Se: Do not dry. Dissolve
0.1727 g H2Se03 {actual assay 94.6%) in reagent water and dilute to
1,000 mL.
3.20 Silver solution, stock, 1 mL = 100 ug Ag: Dissolve 0.1575 g AgN03 in
100 mL of ASTM Type 1 water and 10 mL conc. HN03. Dilute to 1000 mL
with reagent water.
3.21 Sodium solution, stock, lmL = 100 fig Na: Dissolve 0.2305 g Na2C03 in a
minimum of (1+1) HN03, After dissolution is complete, warm the
solution to degas. Add 10.0 mL conc. HNO, and dilute to 1,000 mL
using reagent water.
3.22 Thallium solution, stock, 1 mL = 100 ug Tl: Dissolve 0.1303 g TlN03
in reagent water. Add 10.0 mL conc. HN03 and dilute to 1000 mL with
reagent water.
3.23 Titanium solution, stock, 1 mL = 100 ug Ti: Dissolve 0.4133 g
(NH,)2TiF6 in reagent water. Add 2 drops of conc. HF and dilute to
1000 mL with reagent water.
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3.24 Vanadium solution, stock, 1 mL = 100 ug V: Dissolve 0.2296 g NH4V03 in
a minimum amount of conc. HN03. Heat to increase rate of dissolution.
Add 10.0 mL conc. HN03 and dilute to 1000 mL with reagent water.
3.25 Zinc solution, stock, 1 mL = 100 ug Zn: Dissolve 0.1245 g ZnO in a
minimum amount of dilute HN03. Add 10.0 mL conc. HN03 and dilute to
1000 mL with reagent water.
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PART B - Inductively Coupled Plasma-Atomic Emission Spectrometric Method
1 Scope and Application
Table I {Exhibit C) lists target analytes and their Contract Required
Detection Limits (CRDLs). Method detection limits will be sample and matrix
dependent. Appropriate steps must be taken in all analyses to ensure that
potential interferences are taken into account,
2 Summary of Method
The method describes a technique for the simultaneous or sequential
multielement determination of trace elements in solution. The basis of the
method is the measurement of atomic emission by an optical spectroscopic
technique. The aerosol resulting from sample nebulization is transported to a
radio-frequency induced inductively coupled argon plasma (ICP) which produces
characteristic atomic-line emission spectra. The high temperatures in the
plasma atomize, ionize,and excite the analytes in the sample aerosol. As a
result, both the atomic and ionic emmision line spectra characteristic of the
analytes are produced. The spectra are dispersed by a grating spectrometer,
and the intensities of the lines are monitored by a detector or detectors
capable of responding to the incoming photons. The received signals are
processed using a computer system. Background correction measurements are
required to compensate for variable background contributions and must be made
adjacent to analyte lines during analysis. The position selected for the
background intensity measurement may be on either or both sides of the
analytical line, and must be determined by the complexity of the spectrum. The
position used must be free of spectral interference and reflect the same
change in background intensity as occurs at the analyte wavelength measured.
The possibility of additional interferences named in Item 3, below, should
also be recognized and appropriate corrections made.
Note: Background correction is not required when line broadening occurs.
Background correction under these conditions would actually degrade the
analytical result.
3 Interferences
Spectral, physical, and chemical interference effects may contribute to
inaccuracies in the determination of trace elements.
3.1 Spectral interferences can be categorized as:
Overlap of a spectral line from another element;
Unresolved overlap of molecular band spectra;
Background contribution from continuous or recombination
phenomena,* and
Background contribution from stray light from the line emission
of high concentration elements.
The first of these effects can be compensated for by measuring the
concentration of the interfering element and correcting for its
contribution to analyte. The second effect may require selection of
D-19
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an alternative wavelength (if available). The third and fourth
effects can usually be compensated for by using a background
correction point adjacent to the analyte line. Users of simultaneous
multielement instrumentation are responsible for verifying the absence
of spectral interferences from elements which may be present in a
sample but for which there are no analytical channels.
Table VI (Exhibit C) lists potential interferences which may be observed
at recommended wavelengths. These data are for information purposes only
and do not contain absolute values which would be applicable to a specific
laboratory. For the purposes of this contract, linear relations between
concentration and intensity of the analytes and the interferents are
assumed. The interference information, which was collected at the Ames
Laboratory, is expressed as analyte concentration equivalents, i.e., false
analyte concentrations arising from aspiration of 100 mg/L of the
interfering element.
As an example of using the data in Table VI, assume that arsenic (at
193.696 nm) is to be determined in a sample containing 10 mg/L of aluminum.
According to Table VI, Exhibit C, 100 mg/L of aluminum would yield a false
signal for arsenic equivalent to approximately 1.3 mg/L. Therefore, 10
mg/L of aluminum would result in a false signal for arsenic equivalent to
approximately 0.13 mg/L. The reader is cautioned that individual
analytical systems will exhibit different levels of interference from those
shown in Table VI, Exhibit C, and that the interference effects must be
evaluated on an individual basis. Only those interferents listed were
investigated, and the blank spaces in Table VI, Exhibit C, indicate that
measurable interferences were not observed from the listed interferent
concentrations with the instrumentation used.
3.2 Physical interferences are generally considered to be effects
associated with sample nebulization and transport processes. Changes
in viscosity and surface tension can cause significant inaccuracies,
especially in samples which may contain high dissolved solids and/or
acid concentrations. The use of a peristaltic pump may lessen these
interferences. If these types of interferences occur, they can be
reduced by diluting the sample, using internal standards, or by
employing the Method of Standard Additions.
3.3 High dissolved solids can result in salt buildup at the tip of the
nebulizer. This affects aerosol flow and causes instrumental drift.
Wetting the argon prior to nebulization, using a tip washer and sample
dilution have been used to control this problem. It has also been
reported that the use of mass flow controllers to control the argon
flow rate improves instrument performance.
3.4 Chemical interferences are characterized by molecular compound
formation, ionization effects, and solute vaporization effects.
Normally these effects are not pronounced using ICP-AES. If observed,
they can be minimized by careful selection of operating conditions
i.e. incident power, observation position, etc., by buffering the
sample, matrix matching, or standard addition procedures. These
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types of interferences can be highly dependent on matrix and the
specific analyte involved.
4 Apparatus
4.1 An Inductively Coupled Plasma-Atomic Emission Spectrometer requires:
Computer-controlled atomic emission spectrometer with background
correction.
Radio frequency generator.
Argon gas supply, welding grade or better.
^ Use of a mass-flow controller is recommnded.
Use of a peristaltic pump is recommended.
4 .2 Operational Requirements
4.2.1 System configuration
Because of the differences between various makes and models of
satisfactory instruments, no detailed operating instructions can be
provided. Instead, the analyst should follow the instructions
provided by the instrument's manufacturer. Sensitivity, instrument
detection limits {IDLs), precision, linear dynamic range, and
interference effects must be investigated and established for each
analyte line on that particular instrument. All measurements must be
within the instrument's linear range where correction factors are
valid.
It is the responsibility of the analyst to verify that the instrument
configuration and operating conditions used satisfy the analytical
requirement set forth in the SOW. It is also the analyst's
responsibility to maintain PC data confirming the instrument
performance and analytical results.
The raw data must include hard copies or computer-readable storage
media which can be readily examined by an EPA audit team. The raw
data must demonstrate the presence or absence of all spectral
interferences, including, but not limited to, those listed in Table VI
of Exhibit C. The raw data must demonstrate defendable background
correction points. This applies to simultaneous and sequential ICP
instruments. Sequential ICP data must demonstrate the ability to
select the correct peak from a spectrum in which nearby peaks from
interferents are present.
5 Reagents and Standards (See Section IV, Part A)
5.1 Matrix matching with the samples is mandatory for all blanks,
standards and QC samples. This avoids inaccurate concentrations from
being reported due to possible standard curve deviations.
5.2 Prepare mixed calibration standard solutions for ICP by combining
appropriate volumes of the stock solutions, (Section IV, Part A) , in
volumetric flasks. Add 2.0 mL of (1+1) HNO, and 1.0 mL of (1+1) HC1
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and dilute to 100 mL with ASTM Type I water. Prior to preparing the
mixed standards, each stock solution should be analyzed separately to
determine possible spectral interferences or the presence of
impurities. Care should be taken when preparing the mixed standards
to ensure that the elements are compatible and stable. Transfer the
mixed standard solutions to a clean teflon or polyethylene bottle for
storage. Fresh mixed standards should be prepared as needed with the
realization that concentration can change on aging. Calibration
standards must be initially verified using a QC sample, and monitored
weekly for stability.
Although not specifically required, some typical calibration standard
combinations are shown below:
Mixed standard solution I -- Manganese, beryllium, cadmium, lead,
silver, barium, copper, cobalt, nickel and zinc.
Mixed standard solution II -- Arsenic, selenium, chromium, thallium,
aluminum, calcium, magnesium, potassiom, sodium, and mercury.
Mixed standard solution III -- Antimony, vanadium, and iron.
NOTE; If the addition of silver to the recommended acid combination results
in precipitation, add 15 mL of ASTM Type I water and warm the flask until the
solution clears. Cool and dilute to 100 mL with reagent water. For this acid
combination the silver concentration should be limited to 2 mg/L. Silver
under these conditions is stable in a tap water matrix for 30 days. Higher
concentrations of silver require additional HC1.
5.3 Two types of blanks are required for ICP analysis: the calibration
blank which is used in establishing the analytical curve, and the
preparation blank which is used to evaluate possible contamination
resulting from the acids used during sample processing.
5.3.1 The calibration blank is prepared by diluting 2.0 mL of (1+1)
HNOj and 1.0 mL of (1+1) HC1 to 100 mL with reagent water.
Prepare sufficient quantity to be used to flush the system
between standards and samples.
5.3.2 The preparation blank must contain all of the reagents and at
the same volume as used in preparation of the samples.(see
Exhibit E).
5.4 The Interference Check Solution (ICS, Exhibit E) is prepared to
contain known concentrations of interfering elements. Its analysis
verifies that interferences at the levels present in the ICS are
corrected for by adequate inter-element and background corrections to
within a specified QC limit. The ICS can be prepared by the analyst
using certified stock solutions. Alternatively, it can be obtained
from the EPA or another certified distributor.
6 Procedure
6.1 Set up instrument with proper operating parameters established in
Section 4.2. The instrument must be allowed to become thermally
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stable before beginning. This warmup usually requires at least 30 min
of operation prior to calibration.
6.2 Initiate appropriate operating configuration of the computer.
6.3 Calibration and Sample Analysis
6.3.1 Profile and calibrate the instrument according to the
manufacturer's recommended procedures, using matrix-matched
mixed calibration standard solutions, such as those described in
5.1 and 5.2. Calibrate the instrument for the analytes of
interest using the calibration blank and at least a single
standard. Flush the system with the calibration blank between
each standard. Use the average intensity of multiple
integrations for both standardization and sample analysis. A
minimum of two replicate integrations are required. The raw
data must include the concentrations of the analytes in each
integration as well as the average.
6.3.2 During the sample run the system should be flushed with the
calibration blank solution between each analytical sample.
6.3.3 Dilute and reanalyze samples which exceed the established linear
range for an analyte.
7 Calculations
If dilutions were performed, the appropriate dilution factor must be applied
to sample concentrations. Appropriate concentration units must be specified
on the required forms. The quantitative values shall be reported in units of
micrograms per liter (ug/L) for aqueous samples. No other units are
acceptable.
8 Quality Control
8.1 QA/QC must be performed as specified in Exhibit E.
8.2 All QA/QC data must be submitted with each data package as specified
in Exhibit B.
8.3 The ICS is prepared to contain known concentrations of interfering
elements and its analysis will provide an adequate test of any
corrections performed. The ICS is used to verify that interferences
at the levels present in the ICS are corrected by the data system
within specified QC limits.
9 References
9.1 Annual Book of ASTM Standards, Part 31.
9.2 "Carcinogens - Working With Carcinogens," Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
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Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
9.3 Garbarino, J.R. and Taylor, H.E., "An Inductively-Coupled Plasma
Atomic Emission Spectrometric Method for Routine Water Quality
Testing," Applied Spectroscopy 33, No. 3(1979).
9.4 Handbook for Analytical Quality Control in Water and Wastewater
Laboratories, EPA-600/4-79-019.
9.5 "Inductively Coupled Plasma-Atomic Emission Spectrometric Method of
Trace Elements Analysis of Water and Waste", Method 200.7 modified by
CLP Inorganic Data/Protocol Review Committee; original method by
Theodore D. Martin, EMSL-Cincinnati.
9.6 "Methods for Chemical Analysis of Water and Wastes," EPA-600/4-79-020.
9.7 "OSHA Safety and Health Standards, General Industry," (29 CFR 1910),
Occupational Safety and Health Administration, OSHA 2206, (Revised,
January 1976).
9.8 "Safety in Academic Chemistry Laboratories, American Chemical Society
Publications, Committee on Chemical Safety, 3rd Edition, 1979.
9.9 Winefordner, J.D., "Trace Analysis: Spectroscopic Methods for
Elements," Chemical Analysis, Vol. 46, pp. 41-42.
9.10 Winge, R.K., V.J. Peterson, and V.A. Fassel, "Inductively Coupled
Plasma-Atomic Emission Spectroscopy Prominent Lines, 11 EPA-600/4-79-
017.
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Part C - Graphite Furnace and Flame Atomic Absorption Spectroscopy
1 Scope and Application
1.1 Graphite furnace atomic absorption (GFAA) procedures are applicable to
the determination of the target analytes in the water samples analyzed
under this contract. GFAA is characterized by its low instrument
detection limits (IDL), which are necessary to meet the CRDLs for many
of the target analytes. IDLs, sensitivity, and optimum ranges for
each analyte will vary with the specific instrument and operating
conditions. Typically GFAA is used only for the analysis of As, Pb,
Sb, Se, Tl, and in some cases Cd for which instrument detection limits
are typically less than 2 ppb.
1.2 Flame AAS procedures are applicable to the determination of the target
analytes in water samples analyzed under this contract. Flame AAS is
characterized by moderate IDLs (mid to high ppb). IDLs, sensitivity,
and optimum ranges for each analyte will vary with the specific
instrument and operating conditions. Generally, flame AAS analyses
are an alternative to ICP or ICP-MS analyses and are only used in
special circumstances (eg, catastrophic failure).
2 Summary of Method
2.1 GFAAS - A discrete [iL volume sample is placed in an electrically-
heated graphite furnace tube, which forms the measurement cell of an
atomic absorption spectrometer. Through a series of heating steps,
the sample is dried, ashed, and the elements in the sample atomized
directly in the furnace tube. A source lamp composed of the element
being analyzed directs a light beam through the furnace tube, into a
monochromator, and onto a detector, which measures the amount of light
passing through the tube. Any ground-state atoms of the element being
measured formed during the atomization step absorb some of the light
from the source lamp. Consequently, the intensity of the light
transmitted is inversely proportional to the concentration of the
element in the sample.
2.2 Flame AAS - The principle for flame AAS is the same as that described
for GFAAS with the exception that a flame burner replaces the graphite
furnace tube and samples are introduced into the flame by aspiration.
3 Interferences
3.1 The composition of the sample matrix can have a major effect on the
analysis. By modifying the sample matrix, either to remove
interferences or to stabilize the analyte, interferences can be
minimized. Examples are the addition of ammonium nitrate to remove
alkali chlorides or the addition of ammonium phosphate to prevent
cadmium volatilization. Both of these processes occur during the
charring step of the temperature program.
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Because gases and particulates are generated in the furnace during
atomization, they absorb some of the analytes's characteristic
radiation. This absorption if uncorrected would lead to an improper
quantitation. Therefore, the use of background correction is required
for GFAA.
Continuum background correction cannot correct for all types of
background interference. When it is not possible to sufficiently
compensate for the background interference, choose an alternative
wavelength, chemically separate the analyte from the interferant, or
use an alternate form of background correction, e.g., Zeeman
background correction.
Interferences from a smoke-producing sample matrix can sometimes be
reduced by extending the charring time at a higher temperature or
utilizing an ashing cycle in the presence of air. Care must be taken
to prevent loss of analyte.
3.2 Flame AAS - Chemical interferences are the most troublesome type of
interference in flame AAS and result from the analyte of interest
being bound to another element during atomization, and hence being
unavailable for "atomic" absorption. This type of interference can be
eliminated or minimized by using a hotter flame (eg, nitrous oxide-
acetylene instead of air-acetylene) or by adding a matrix modifier to
the sample.
Molecular absorption and light scattering caused by particles in the
flame can cause high background absorption, which results in a
positive bias in sample values. Background correction can correct for
this type of interference. Three common background correction
techniques that should provide adequate results are continuum-source,
Zeeman, and Smith-Hiefte.
4 Apparatus
4.1 Atomic absorption spectrophotometer: Single or raulti-channel, single
or double beam instrument equipped with flame burner and/or graphite
furnace cells, grating monochromator, photomultiplier detector,
adjustable slits, a wavelength range of 190 to 800 nm, background
correction, and data system.
4.2 4.2.1 Operational Requirements and System Configurations: Due to
differences between various makes and models of satisfactory
instruments, no detailed operating instructions can be provided.
Instead, the analyst should follow the instrument manufacturer's
instructions. Sensitivity, IDLs, precision, linear dynamic
range, and interference effects must be investigated and
established for each analyte on each instrument.
It is the responsibility of the analyst to verify that the instrument
configuration and operating conditions used satisfy the analytical
requirements set forth in this SOW. It is also the analyst's
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responsibility to maintain QC data confirming instrument performance and
analytical results.
The raw data must include hard copies or computer-readable storage media
which can be readily examined by an EPA audit team. The raw data must
demonstrate defendable choices of furnace temperature programs and matrix
modifiers.
5 Reagents and Standards (See Section IV, Part A)
5.1 Preparation of standards: Calibration standards are prepared by
diluting stock metal solutions to the appropriate concentration. The
acid content of the standards must match the acid content of the
samples. Prepare at least four calibration standards for each analyte
(blank, at the CRDL, and at two higher conentrations).
Digested samples - Prepare the standards by combining an appropriate
volume of stock solution with 2 iriL of (l+l) HN03 and 1 mL of (1+1) HC1
in a 100 mL volumetric flask and dilute to volume with reagent water.
If samples are prepared using the microwave digestion procedure,
prepare the standards by combining an appropriate volume of stock
solution with 10 mL of cone. HNO in a 100 mL volumetric flask and
dilute to volume with reagent water.
Undigested samples - Samples being analyzed for dissolved metals do
not require digestion. Prepare the standards such that the acid
content matches that of the samples.
5.2 Two types of blanks are required for GFAA analysis; the calibration
blank is used in establishing the analytical curve while the
preparation blank is used to evaluate possible contamination resulting
from the acids used in the sample processing.
The calibration blank is prepared as described in section 5.1 above. The
preparation blank is prepared as specified in Exhibit E.
6 Procedure
6.1 Set up the instrument following the instrument manufacturer's
instructions. The specific operating conditions (flame and furnace
parameters, lamp parameters, wavelength, etc) must be determined by
the operator to meet the required QA/QC requirements. The optimum
conditions will vary with each element and instrument. The specific
conditions must be documented in the instrument logbook and raw data.
For general conditions and notes for analyses by flame AAS or GFAAS,
consult the manufacturer's literature. General information is also
available in the references listed below.
"Test Methods for Evaluating Solid Waste", SW-846, U.S. EPA, Series
7000 Methods.
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"Standard Methods for the Examination of Water and Wastewater", APHA,
AWWA, WEF
"Methods for Chemical Analysis of Water and Wastes", EPA-600/4-79-020,
U.S. EPA
"Techniques of Water-Resources Investigations of the United States
Geological Survey, Methods for Determination of Inorganic Substances
in Water and Fluvial Sediments", Book 5, Chapter A1
6.2 Calibration and Sample Analysis
6.2.1 Calibrate the instrument according to the manufacturer's
recommended procedures, using at least 4 calibration standards.
One standard must be a blank and one must have a concentration
equal to the CRDL. The concentration of the other standards are
set by the operator to span the range of interest.
6.2.2 Following calibration, the samples and QC standards are analyzed
as described in Exhibit E.
7 Calculations
The measured concentration of an analyte must be corrected for all
dilutions performed as part the sample preparation and sample analysis.
The required reporting units for concentration are pg/L
8 Quality Control
QA/QC must be performed as specified in Exhibit E. Corrective action for
out-of-criteria QC results are also specified in Exhibit E.All QA/QC data
must be submitted with each data package as specified in Exhibit B.
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Part D - Inductively Coupled Plasma - Mass Spectrometry
1 Scope and Application
1.1 Metals for which this method is applicable are listed in Table I,
Exhibit C. Instrument detection limits (IDLs), sensitivities, and
linear ranges for these elements will vary with the matrices,
instrumentation, and operating conditions. Use of this method is
restricted to spectroscopists who are knowledgeable in the recognition
and the correction of spectral, chemical, and physical interferences
in ICP-MS. Experience requirement is 1 year on a commercially
available ICP-MS.
2 Summary of Method
2.1 The method describes the multielemental determination of analytes by
ICP-MS. The method measures ions produced by a radiofrequency
inductively coupled plasma. Analyte species originating in a liquid
are nebulized and the resulting aerosol transported by argon gas into
the plasma torch. The ions produced are entrained in the plasma gas
and by means of a water-cooled interface, introduced into a mass
spectrometer, capable of providing a resolution better than or equal
to 1 amu peak width at 10% of the peak height. The water-cooled
interface, consisting of tandem skimmers, is differentially pumped and
leads into the high vacuum chamber of the mass spectrometer. The ions
and ion clusters produced in the plasma are sorted according to their
mass-to-charge ratios and quantified with a detector. Interferences
must be assessed and valid corrections applied or the data flagged to
indicate problems. Use of the internal standard technique is required
to compensate for suppressions and enhancements caused by sample
matrices.
3 Interferences
3.1 Isobaric elemental interferences in ICP-MS are caused by isotopes of
different elements forming ions with the same nominal mass-to-charge
ratio (m/z) as the analyte of interest. A data system must be used
to evaluate and correct for these interferences when they are present.
This correction involves determining the signal for another isotope of
the interfering element and subtracting out the appropriate signal
from the isotope of interest. Data that is corrected must be noted in
the report along with the exact calculations used. Table XI, Exhibit
C, shows the analyte concentration measured when an interferent is
present at 100 mg/L. Commercial ICP-MS instruments nominally provide
unit resolution at 10% of the peak height. High ion currents at
adjacent masses may also contribute to ion signals at the mass of
interest. It should be noted that the information described in Table
XI, Exhibit C, was experimentally derived and the interferences which
are described occur from several different sources. One interference
is the effect of resolution on adjacent peaks. In a quadrupole mass
spectrometer, there is a larger effect at 1 amu less than the
interferant than at 1 amu greater than the interferant's mass due to
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the trapezoidal peak shape of the mass spectra. Another interference
which is observed is the formation of a hydride ion. Hydride ion
interferences only cause an interference at l amu greater than the
interferant's mass. These interferences are not necessarily linear,
and attempts must not be made to extrapolate the values to a
particular data set. The table has been included for its
informational content alone and does not contain quantitative values
which would be applicable to any particular laboratory.
3.2 Isobaric molecular and doubly charged ion interferences in ICP-MS are
caused by ions consisting of more than one atom or charge. Table XII,
Exhibit C, lists isobaric molecular-ion interferences which could
affect the analytes. It should be noted that many of these
interferences are extremely rare, but adverse effects on data quality
could occur if the individual constituents occurred in the sample at
sufficiently high concentrations. When the interferences cannot be
avoided by the use of another isotope with sufficient natural
abundance, corrections to the data must be applied. Corrections for
molecular-ion interferences may either be based upon the natural
isotope ratios of the molecular ion or by measuring the interference
which occurs when the interferant is present.
3.3 Physical interferences are effects associated with the sample
nebulization and transport processes as well as ion-transmission
efficiencies. Nebulization and transport processes are those in which
a matrix component causes a change in surface tension or viscosity in
a manner different from the standards used in performing calibration.
Internal standards have successfully been used to correct for these
interferences. Physical interferences resulting from changes to ion
transmission efficiencies are primarily suppressions, and lighter
elements are suppressed more than the heavier elements. They also
tend to be greater for matrix components with heavier atomic mass than
for matrix components with lighter atomic mass. Changes in matrix
composition therefore can also cause significant suppressions and
enhancements. Dissolved solids can deposit on the tip of a
pneumatic nebulizer and on the interface skimmers (reducing the
orifice size and therefore changing the ion transmission
efficiencies). Total dissolved solid levels below 0.2% (2000 ppm) have
been recommended to minimize solid deposition. Internal standards
must be affected to the same degree as the analyte to demonstrate that
they compensate for these interferences. A minimum of three internal
standards, listed in Table IX Exhibit C, bracketing the mass range,
must be used. When the intensity level of an internal standard is
less than 30% of the intensity of the first standard used during
calibration, the sample must be reanalyzed for the affected analytes
after performing a fivefold (1+4) dilution. Analyst Note: In the
performance of this method, it has been observed the use of new or
newly cleaned skimming cones result in large initial changes in the
ion transmission efficiencies. These changes result in a large
instrumental drift which can cause drift-sensitive quality assurance
parameters to exceed control limits. It has been found that by
conditioning the skimming cones by exposure to solutions (such as the
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ICS) which are similar to the samples analyzed, the changes in ion
transmission efficiencies will be mitigated. This conditioning
appears to form an oxide layer on the skimming cones which insulates
and therefore stabilizes the ion transmission efficiencies.
3.4 Memory interferences are effects which are dependant upon the relative
concentration differences between samples or standards which are
analyzed sequentially. Sample deposition on the sampler and skimmer
cones, spray chamber design, and the type of nebulizer used, affect
the extent to which memory interferences are present. To verify that
memory effects do not have an adverse impact on data quality, the
memory test must be performed on the tuned and calibrated instrument
before any analyses are performed. A multielement memory test
solution containing levels of analytes as specified in Table VIII,
Exhibit C, is aspirated into the system for a normal sample exposure
period. A rinse solution is then introduced, noting the time when the
uptake tube is switched to the blank solution. After the normal
routine rinse time has elapsed, begin a routine analysis of the
calibration blank. Inspect the resulting data to see if any analytes
are in excess of the CKDL. The memory test must be passed before any
samples are analyzed under this contract. If a memory problem does
exist (see Exhibit E) for a given analyte, increase the rinse time
until the system passes the memory test. If the increased rinse time
is not feasible from a sample throughput standpoint, a hardware change
may be necessary. An apparent memory problem may in fact be blank
contamination. This event may be determined by evaluating a second
blank analysis and noting the values.
4 Apparatus and Materials
4.1 Inductively Coupled Plasma - Mass Spectrometer.
4.1.1 System capable of providing resolution, less than or equal to
1.0 amu at 10% peak height from 6-253 amu with a data system
that allows corrections for isobaric interferences and the
application of the internal standard technique. Use of a mass-
flow controller for the nebulizer argon and a peristaltic pump
for the sample solution are recommended.
4.1.2 Argon gas supply: Welding grade or better.
4.2 Operational Requirements and System Configuration
Because of the differences between various makes and models of
instruments, no detailed operating instruction can be provided.
Instead, the analyst should follow instrument manufacturer's
instructions. The analyst must maintain QC data confirming instrument
performance and analytical results.
It is the responsibility of the analyst to verify that the instrument
configuration and operating conditions used satisfy the analytical
requirements set forth in the SOW. It is also the analyst's
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responsibility to maintain quality control data confirming instrument
performance and analytical results.
The raw data must include hard copies and computer-readable storage
media which can be readily examined by an EPA audit team. The raw
data must demonstrate defendable choices of instrument operating
conditions which minimize interferences such as oxides.
4.3 Precautions must be taken to protect a channel electron multiplier (if
present) from high ion currents. Channel electron multipliers suffer
from fatigue after being exposed to high ion currents. This fatigue
can last from several seconds to hours depending on the extent of
exposure. During this time period, response factors are constantly
changing. This fluctuation invalidates the calibration curve, causes
instability, and invalidates sample analyses. Samples run during such
periods are required to be rerun at no additional cost to the
government.
4.4 Sensitivity, IDL's, precision, linear dynamic range, and interference
effects must be established for each analyte on a particular
instrument. The analyst must maintain QC data confirming instrument
performance and analytical results.
5 Reagents and Standards {See Section IV, Part A.)
5.1 Target analyte levels in acids used in the preparation of standards
and for sample processing must be below the CRDLs for the purpose of a
study. Redistilled acids or ultraoure acids are recommended for use
with ICP-MS because of the high sensitivity of ICP-MS. Many more
molecular-ion interferences are observed for analytes when
hydrochloric and sulfuric acids are used, as demonstrated in Table
XII, Exhibit C. Because HC1 is added for stabilization, corrections
for the chloride molecular ion interferences must be applied to all
data generated.
5.2 Internal standards must be used to monitor and correct for changes
that occur from differences between standards and samples. [This
information must be clearly reported in the raw data.] The changes
for which internal standards correct are primarily -physical
interferences. A minimum of three internal standards must be present
in all standards and samples at identical levels by mixing the
internal standard into the solution prior to nebulization.
Additionally, if data is collected in a mode designed to extend the
linear dynamic range, either by using a different detector or by
changing voltages on the mass spectrometer components or detector,
then at least one internal standard must be present which is measured
in the dame mode that the samples were analyzed. Introduction may be
accomplished by using a second channel of the peristaltic pump to add
the internal standard to the uptake tube. If on-line addition is not
used then internal standard spiking may be performed by adding a
constant volume of internal standard concentrate to identical volumes
of the standards and prepared samples. One typical example is to
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measure out 10.0 mL of all standards and samples into individual
containers, then to add 0.100 mL of a 10 mg/L solution of the internal
standard to each of the containers. This procedure adds identical
amounts of the internal standard to each solution for analysis. The
concentrations of the analyte levels in the standards do not have to
be corrected for the dilution which occurs, because dilution of the
standards and samples is identical. Dilution of the sample by
internal standards should be kept to the minimum possible while still
maintaining the integrity of the sample analysis.
5.2.1 Bismuth internal standard solution, stock, ImL = 100 ug Bi:
Dissolve 0.1115 g Bi20, in a minimum amount of dilute HN03. Add
10 mL conc. HN03 and dilute to 1000 mL with ASTM Type I water.
5.2.2 Holmium internal standard solution, stock, 1 mL = 100 ug Ho:
Dissolve 0.1757 g Ho2 (C03) 2*5H20 in 10 mL ASTM Type I water and 10
mL HNOj. After dissolution is complete, warm the solution to
degas. Add 10 mL conc. HN03 and dilute to 1000 mL with ASTM
Type I water.
5.2.3 Indium internal standard solution, stock, 1 mL = 100 ug In:
Dissolve 0.1000 g indium metal in 10 mL conc. HN03. Dilute to
1000 mL with ASTM Type I water.
5.2.4 Lithium internal standard solution, stock, 1 mL = 100 ug sLi:
Dissolve 0.6312 g of 95 atom % enriched 'Li, Li2C03 in 10 ml of
ASTM Type I water and 10 mL HN03. After dissolution is
complete, warm the solution to degas. Add 10 mL HN03 and dilute
to 1 L with Type I water.
5.2.5 Rhodium internal standard solution, stock, 1 mL = 100 ug Rh:
Dissolve 0.3593 g ammonium hexachlororhodate (III) (NH4) 3RhCl6 in
10 mL ASTM Type I water. Add 100 mL conc. HC1 and dilute to
1000 mL with ASTM Type I water.
5.2.6 Scandium internal standard solution, stock, 1 mL = 100 ug Sc:
Dissolve 0.15343 g Sc203 in 10 mL (1+1) hot HN03. Add 5 ml conc.
HN03 and dilute to 1000 mL with ASTM Type I water.
5.2.7 Terbium internal standard solution, stock, 1 mL = 100 ug Tb:
Dissolve 0.1828 g Tb2 (C03) 3*5H20 in 10 mL (1+1) HN03. After
dissolution is complete, warm the solution to degas. Add 5 ml
conc. HN03 and dilute to 1000 mL with ASTM Type I water.
5.2.8 Yttrium internal standard solution, stock, 1 mL = 100 ug Y:
Dissolve 0.2316 g Y2 (C03) 3'3H20 in 10 mL (1+1) HNO,. Add 5 ml
conc. HN03 and dilute to 1000 mL with ASTM Type I water.
5.3 Mixed calibration standard solutions. Dilute the stock-standard
solutions to levels in the linear range for the instrument in a
solvent consisting of 1 percent (v/v) HN03 in ASTM Type I water along
with the selected concentration of internal standards such that there
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is an appropriate internal standard element for each of the analytes
(see Table IX, Exhibit C). Prior to preparing the mixed standards,
each stock solution must be analyzed separately to determine possible
spectral interferences or the presence of impurities. Care must be
taken when preparing the mixed standards that the elements are
compatible and stable. Transfer the mixed standard solutions to
freshly acid-cleaned teflon or polyethylene bottles for storage.
Fresh mixed standards must be prepared as needed with the realization
that concentrations can change on aging. Calibration standards must
be initially verified using a QC sample and monitored weekly for
stability. Although not specifically required, some typical
calibration standard combinations follow.
5.3.1 Mixed standard solution I -- manganese, beryllium, cadmium,
lead, silver, barium, copper, cobalt, nickel, and zinc.
5.3.2 Mixed standard solution II - arsenic, selenium, chromium,
thallium, aluminum, calcium, magnesium, potassium, sodium, and
mercury.
5.3.3 Mixed standard solution III -- antimony, vanadium, iron.
5.3.4 Mixed standard solution IV -- bismuth, holmium, indium, lithium,
scandium, yttrium, and terbium.
5.3.5 Mixed standard solution V -- rhodium.
Note: If the addition of silver to the recommended acid combination
results in an initial precipitation, add 15 mL of ASTM Type I water
and warm the flask until the solution clears. Cool and dilute to 100
mL with ASTM Type I water. For this acid combination the silver
concentration must be limited to 2 mg/L. Silver under these
conditions is stable in a tap water matrix for 30 days.
5.4 Three types of blanks are typically required for the analysis. The
calibration blank is used in establishing and monitoring the
calibration curve The preparation blank is used to monitor for
possible contamination resulting from the sample preparation
procedure. And the rinse blank is used to flush the system between all
samples and standards.
5.4.1 The calibration blank generally consists of 1 percent HN03 plus
0.5 percent HC1 (v/v) in ASTM Type I water along with the
selected concentration of internal standards such that there is
an appropriate internal standard element for each of the
analytes (see Table IX, Exhibit C).
5.4.2 The preparation blank must contain all the reagents in the same
volumes used for sample preparation. The preparation blank must
be carried through the complete procedure and contain the same
acid concentration in final solution as the sample solutions.
(See Exhibit E).
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5.4.3 The rinse blank consists of 2 percent HN03 (v/v) in ASTM Type I
water. Prepare a sufficient quantity to flush the system
between standards and samples.
5.5 The interference check solution(s) (ICS) is prepared to contain known
concentrations of interfering elements that will demonstrate the
magnitude of interferences and provide an adequate test of any
corrections. For example, the chloride concentration provides a means
to evaluate software corrections for chloride-related interferences
such as 3SC1"0* on S1v* and l0Ar35Cl* on "As*. Since the natural
abundance of 35C1 at 75.8 percent is 3.13 times the 37C1 abundance of
24.2 percent, the ion corrections can be calculated with adjustments
for isobaric contributions. Similarly, the iron in the ICS solutions
is used to demonstrate adequate resolution of the spectrometer for
manganese. Molybdenum serves to indicate oxide effects on cadmium
isotopes. The other components are present to evaluate the ability of
the measurement scheme to correct for various molecular-ion isobaric
interferences. The ICS solutions are detailed in Table IV, Exhibit C
and are used to verify that the interference levels are corrected by
the data system to within QC limits.
5.5.1 Stock solutions for preparing ICS solutions A and AB may be
obtained from EPA. Otherwise, refer to Table IV, Exhibit C.
The ICS solutions A and AB must be prepared weekly.
5.5.2 Mixed ICS solution I may be prepared by adding 2.781 g
A1 (N03) 3. 9H20, 1.499 g CaC03 (dried at 180°C for 1 h before
weighing), 0.500 g Fe, 0.332 g MgO, 1.153 g Na2C03, and 0.353 g
K2C03 to 25 mL of ASTM Type I water. Slowly add 100 mL of (1+1)
HN03. After dissolution is complete, warm the solution to
degas. Cool and dilute to 1000.0 mL with ASTM Type I water.
5.5.3 Mixed ICS solution II may be prepared by slowly adding 1.489 g
85% HjPO,, 1.275 g 96% H2SO., 23.589g 37% HC1, and 2.133 g citric
acid C607H8 to 100 mL of ASTM Type I water. Dilute to 1000.0 mL
with ASTM Type I water.
5.5.4 Mixed ICS solution III may be prepared by adding 2.500 mL of
silver stock solution; 5.00 mL each of arsenic stock solution,
cadmium stock solution,selenium stock solution, zinc stock
solution; 10.00 mL each of chromium stock solution, cobalt stock
solution, copper stock solution, manganese stock solution,
nickel stock solution, and vanadium stock solution, and 2.5 mL
of cadmium stock solution. Dilute to 100.00 mL with 2% HNO,.
5.5.5 ICS A may be prepared by adding 50.00 mL of mixed ICS solution
I, 2.0 mL each of titanium stock solution, and molybdenum stock
solution, and 25.00 mL of mixed ICS solution II. Dilute to
100.00 mL with ASTM Type I water. ICS solution A must be
prepared fresh weekly.
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5.5.6 ICS RB may be prepared by adding 50.00 mL of mixed ICS solution
I, 2.00 mL each of titanium stock solution and molybdenum stock
solution, 25.00 mL of mixed ICS solution II, and 2.00 mL of
mixed ICS solution III. Dilute to 100.00 mL with ASTM Type I
water. ICS solution AB must be prepared fresh weekly.
Procedure
6.1 Initiate the appropriate operating configuration of the instrument's
computer.
6.2 Set up the instrument with the proper operating parameters. The
instrument must be allowed to become thermally stable before
beginning. This warmup usually requires at least 30 minutes of
operation prior to calibration. This must be verified by running the
tuning solution (Table VI, Exhibit C) and obtaining at least four
integrations with relative standard deviations of less than 10% for
the analytes contained in the tuning solution.
6.3 Conduct mass calibration and resolution checks using the tuning
solution (100 ppb of the elements in Table VI, Exhibit C). The
recommended intensities and response factor criteria (see Table VII in
Exhibit C) are helpful when setting up the instruments but are not
required criteria. The mass calibration and resolution parameters
must meet the criteria specified in Table VII, Exhibit C.If mass
calibration exceeds these criteria, then the mass calibration must be
adjusted to the correct values. The resolution must also be verified
to be less than 1.0 amu full width at 10 percent peak height. The
tuning solution must be analyzed at the beginning of each run prior to
calibration and after mass calibration and resolution checks are
performed and end of each 8 h shift, or end of the analytical run,
whichever is more frequent, and pass the mass calibration and
resolution criteria.
6.3.1 Prior to analyzing any samples under this contract, all of the
samples must be screened for the presence of internal standards
• which might be indigenous to the samples. This screen is
performed by calibrating the instrument for each of the internal
standards using a single point calibration curve at the same
level which will be used during the normal analytical run.
After the screening calibration has been performed, then each
sample to be analyzed during the normal analytical run will be
introduced to the instrument without any internal standard
added, and all of the masses associated with the internal
standards will be scanned. The internal standard calibration
standard must be analyzed at the end of the screening run.
There is no additional quality assurance criteria associated
with the screening run. The data from the screening run must be
included in the raw data package and on Form XVII, no further
reporting requirements are needed.
D-36
ILC03.1
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6.4 Calibration and sample analysis
6.4.1 Calibrate the instrument for the analytes of interest using the
calibration blank and at least a single standard according to
the manufacturer1s recommended procedure for each detector
configuration used in analysis. Flush the system with the rinse
blank between each standard solution. Report each integration
during the calibration and sample analysis and use the average
of the multiple integrations for both standardization and sample
analysis. A minimum of two replicate integrations are required
for both calibration and sample analysis. The raw data must
include the concentrations of elements in each integration as
well as the average. Additionally, if different detector
configurations are used, the raw data must indicate which
detector configuration is being used.
NOTE: Some elements (such as Hg, W, and Mo) require extended flushing
times which need to be determined for each instrumental system. Run
Memory Test on solution in Table VIII, Exhibit C, to verify that
memory problems will not affect the data quality.
6.5 As a minimum, masses which would affect data quality must be monitored
to determine potential effects from matrix components on the analyte
peaks. This information will be used to assess data quality and, as a
minimum, must include the masses which are boldfaced and underlined,
listed in Table XIII, Exhibit C, for each element. These masses must
be monitored simultaneously in a separate scan, or at the same time
that quantification occurs. Failure to provide a scan which includes
all of the required masses will result in non-acceptance of the data
package, and the samples associated with the incomplete data must be
rerun at no cost to the government.
6.6 Flush the system with the rinse blank solution for at least IS sec
prior to the analysis of each sample. Aspirate each sample for at
least 15 sec before collecting data. Note: The delay times for the
rinse blank and the sample should be determined from the Memory Test.
6.7 Dilute and reanalyze samples that are more concentrated than the
linear range for an analyte.
7 Calculations
7.1 If dilutions were performed, the appropriate corrections must be
applied to the sample values.
7.2 Appropriate concentration units must be specified on the required
forms. The quantitative values shall be reported in units of
micrograms per liter (ug/L) for aqueous samples. No other units are
acceptable.
8 Quality Control
D-37
ILC03.1
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8.1 Quality control must be performed as specified in Exhibit E.
8.2 All QC data must be submitted with each data package as specified in
Exhibit B.
8.3 To obtain analyte data of known quality, it is necessary to measure
for more than the analytes of interest in order to know the required
interference corrections. If the concentrations of interference
sources (such a C, CI, Mo, Zr, W) are below the levels that show an
effect on the analyte level, uncorrected equations may be used
provided all QA/QC criteria are met. It should be noted that
monitoring the interference sources does not necessarily require
monitoring the interference itself, but that a molecular species may
be monitored to indicate the presence of the interference. The
monitored masses must include those elements whose oxygen, hydroxyl,
chlorine, nitrogen, carbon, and sulfur molecular ions which could
impact the analytes of interest. When an interference source is
present, the sample analytes impacted must be flagged to indicate the
presence of an interference on the analyte of interest. These tests
will enable the analyst to detect positive or negative interferences
which affect the accuracy of the reported values.
8.4 The interference check solution(s) {ICS} is prepared to contain known
concentrations of interfering elements and its analysis will provide
an adequate test of any corrections performed. The ICS is used to
verify that interferences at the levels present in the ICS are
corrected by the data system within specified QC limits.
References
9.1 Horlick, G., et al. Spectrochim. Acta 40B, 1S55 (1985).
9.2 Gray, A. L. Spectrochim. Acta 40B, 1525 (1985); 41B, 151 (1986).
9.3 Thompson, J. J., and R. W. Houk. Appl. Spect. 41, 801 (1987).
9.4 McLaren, J. W., et al. Anal. Chem. 57, 2907 (1985).
9.5 Lichte, F. E., et al. Anal. Chem. 59, 1150 (1987).
9.6 Tan, S. H., and G. Horlick, Appl. Spect. 40, 445 (1986).
9.7 Vaughan, M. A., and G. Horlick. Appl. Spect. 40, 434 (1986).
9.8 Beauchemin, D., et al. Spectrochim. Acta 42B, 467 (1987).
9.9 Houk, R. S., Anal. Chem. 58, 97A (1986).
D-38
ILC03.1
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Part E - Mercury Analysis in Water
1 Scope and Application
1.1 Organo-mercury compounds will not respond to the cold vapor atomic
absorption (AA) technique unless they are first broken down and
converted to mercuric ions. Potassium permanganate oxidizes many of
these compounds, but recent studies have shown that a number of
organic mercurials, including phenyl mercuric acetate and methyl
mercuric chloride, are only partially oxidized by this reagent.
Potassium persulfate has been found to give approximately 100 percent
recovery when used as the oxidant with these compounds. Therefore, a
persulfate oxidation step following the addition of the permanganate
has been included to insure that organo-mercury compounds, if present,
will be oxidized to the mercuric ion before measurement. Heating is
required for methyl mercuric chloride whether indigenous to, or spiked
into, a sample. For distilled water, heating is not necessary.
1.2 The range of the method may be changed through adjustment of
instrument operating parameters, sample dilution or changes in sample
size. Using a 100 mL sample, a detection limit of 0.2 ug Hg/L can be
achieved.
2 Summary of Method
2.1 The cold vapor AA procedure is a physical method based on the
absorption of radiation by atomic mercury vapor at 253.7 nm. Organic
mercury compounds are oxidized and the mercury is reduced to the
elemental state and aerated from solution in a closed system. The
mercury vapor passes through a cell positioned in the light path of an
AA spectrophotometer. Absorbance (peak height) is measured as a
function of mercury concentration and recorded in the usual manner.
3 Interferences
3.1 Possible interference from sulfide is eliminated by the addition of
potassium permanganate. Concentrations as high as 20 mg/L of sulfide
as sodium sulfide do not interfere with the recovery of added
inorganic mercury from distilled water.
3.2 Copper has also been reported to interfere; however, copper
concentrations as high as 10 mg/L had no effect on recovery of mercury
from spiked samples.
3.3 While the possibility of absorption from certain organic substances
actually being present in the sample does exist, EMSL-LV has not
encountered such samples. This fact is mentioned only to caution the
analyst of the possibility.
4 Apparatus
D-3 9
ILC03.1
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4.1 Atomic absorption Spectrophotometer: An AA unit equipped with a
heated cell suitable for presentation of mercury vapor.
It is the responsibility of the analyst to verify that the instrument
configuration and operating conditions satisfy the analytical
requirements set forth in this SOW, It is also the analyst's
responsibility to maintain QC data confirming instrument performance
and analytical result.
4.2 Hollow cathode, electrodeless discharge or low pressure mercury lamp.
4.3 Computer with software for controlling the spectrophotometer and
autosampler, for calculating analyte concentration and for applying
dilution and background correction factors.
4.4 Absorption cell: Standard spectrophotometer cells having quartz end
windows.
4.5 Air pump: Any peristaltic pump capable of delivering 1 liter of air
per min may be used.
4.6 Flowmeter; Capable of measuring an air flow of 1 liter per min.
4.7 Aeration tubing: A straight glass frit having a coarse porosity.
Additional tubing is used for passage of the mercury vapor from the
sample bottle to the absorption cell and then return.
4.8 Drying tube: 6 inch long x 3/4 inch diameter tube containing 20 g of
magnesium perchlorate.
4.9 Autoanalyzer system including:
Sampler with provisions for sample mixing.
Proportioning pump.
Mercury manifold.
High temperature heating bath with two distillation coils.
Vapor-liquid separator.
Reagents and Standards (See Part A)
5.1 Sulfuric acid, Cone: Reagent grade.
5.2 Nitric Acid, Cone: Reagent grade, of low mercury content.
5.3 Stannous sulfate or stannous chloride.
5.3.1 Stannous sulfate: Dissolve 11-g SnS04 in ASTM Type I water
containing 7 mL conc. H2SO, and dilute to 100 mL.
5.3.2 Stannous chloride: Dissolve 10-g SnCl2 in ASTM Type I water
containing 20 mL conc. HC1 and dilute to 100 mL.
D-40
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5.4 Sodium chloride-hydroxylamine sulfate solution: Dissolve 120-g NaCl
and 120-g (NH2OH) 2 -H2S04 in ASTM Type I water and dilute to 1L.
Note; A 10% hydroxvlamine hydrochloride solution may be substituted for
the hydroxylamine sulfate.
5.5 Potassium permanganate: Dissolve 50-g KMnO, in ASTM Type I water and
dilute to 1 L.
5.6 Potassium persulfate: Dissolve 50-g K2S208 in ASTM Type I water and
dilute to l L.
5.7 Mercury solutions
5.7.1 Stock mercury solution: Dissolve 0.1354-g mercuric chloride,
HgCl2, in 70 mL ASTM Type I water, add 1 mL conc. HN03 and dilute
to 100 mL. 1.00 mL = 1.00 mg Hg.
5.7.2 Standard mercury solutions: Prepare a series of standard
mercury solutions containing 0 to 5 fig Hg/L by appropriate
dilution of stock mercury solution with ASTM Type I water
containing 10 mL conc. HN03/L. Prepare standards daily.
5.8 Air Scrubber Solution: Mix equal volumes of 0.1 N potassium
permanganate and 10% sulfuric acid.
5.9 All blanks, standards, and QC samples must be matrix matched to the
samples being analyzed. This avoids inaccurate concentrations from
being reported due to possible standard curve deviations.
Procedure
6.1 Instrument Operation
6.1.1 Set wavelength to 253.7 nm.
6.1.2 Install absorption cell and align in light path to give maximum
transmission.
6.1.3 Connect associated equipment to absorption cell with glass or
vinyl plastic tubing. Turn on air and adjust flow rate to 2
L/min. Allow air to flow continuously.
6.2 Standardization
6.2.1 Transfer 100 mL of each of the 1.0, 2.0 and 5.0 pg/L Hg standard
solutions and a blank of 100 mL water to 250 mL erlenmeyer
flasks or BOD bottles.
6.2.2 Add 5 mL conc. HjSO, and 2.5 mL conc. HMO, to each flask.
D-41
ILC03.1
-------
6.2.3 Add 15 raL KMnO, solution to each flask and let stand at least 15
min.
6.2.4 Add 8 mL K2S2Oe solution to each flask and heat for 2 h in a
water bath at 95 °C. Cool to room temperature.
6.2.5 For analysis, add enough NaCl-hydroxylamine sulfate solution to
an individual flask to reduce excess KMnO,» then add 5 mL SnCl2
or SnSO, solution and immediately attach the flask to the
aeration apparatus.
6.2.6 As Hg is volatilized and carried into the absorption cell,
absorbance will increase to a maximum, when the recorder
returns to approximately basline, remove the flask and replace
with a flask of water. Flush the system between samples using
water until system returns to baseline.
6.2.7 Construct a calibration curve by plotting peak height versus fig
Hg. The correlation coefficient of the line should be at least
0.995.
6 .3 Analysis of Samples
6.3.1 Transfer 100 mL of sample, or a portion diluted to 100 mL,
containing not more than 5.0 jtg Hg/L to a reaction flask or BOD
bottle.
6.3.2 Treat the samples as in 6.2.2 through 6.2.5.
7 Calculations
7.1 Determine the peak height of the unknown from the chart and read the
mercury value from the standard curve.
7.2 Calculate the mercury concentration in the sample by the formula:
m HgfL = ug Hg in aliquot x — 10P° . -
volume of aliquot m mL
7.3 Appropriate concentration units must be specified on the required
forms. The quantitative values shall be reported in units of
micrograms per liter (ug/L) for aqueous samples; NO other units are
acceptable.
7.4 If dilutions were performed, the appropriate corrections must be
applied to the sample values.
8 Quality Control
8.1 QA/QC must be performed as specified in Exhibit E.
D-42
ILC03.1
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8.2 All QA/QC data must be submitted with each data package as specified
in Exhibit B.
D-43
ILC03.1
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AIR PUMP
DESICCANT
ABSORPTION
CELL
BUBBLER
SAMPLE SOLUTION
IN B 0 D BOTTLE
SCRUBBER CONTAINING
A MERCURY
ABSORBING MEDIA
Figure 3. Apparatus for Cold Vapor Mercury Determination
D-44
ILC03.1
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Part P - Method for Total Cyanide Analysis in Water
X Scope and Application
l.X This method is applicable to the determination of cyanide in low
concentration water samples.
X. 2 The manual spectrophotometry procedure is used for concentrations
below X000 iig/h of cyanide and is sensitive to about 5 ng/L.
X. 3 The working range of the semi-automated spectrophotometry method is S
to 200 pLa/L. Higher level samples must be diluted to fall within the
working range.
2 Summary of Method
2.1 The cyanide as hydrocyanic acid (HCN) is released from cyanide
complexes by means of a reflux-distillation operation and absorbed in
a scrubber solution containing sodium hydroxide. The cyanide ion in
the scrubber solution is then determined spectrophotometrically by a
manual measurement or semi-automated measurement.
2.2 In the spectrophotometric measurement the cyanide is converted to
cyanogen chloride (CNC1) by reaction with chloramine-T at a pH less
than 8. Low pH prevents hydrolysis of CNC1 to cyanate (CNO). After
the reaction is complete, color is formed on the addition of pyridine-
pyrazolone or pyridine-barbituric acid reagent. The absorbance is
read at 620 nm when using pyridine-pyrazolone or 578 nm for pyridine-
barbituric acid. To obtain colors of comparable intensity, it is
essential to have the same salt content in both the sample and the
standards.
3 Interferences
3.1 Interferences are eliminated or reduced by using the distillation
procedure described in Section III, Part D
3.2 Sulfides in a sample will be distilled and collected as H2S in the
scrubber solution and will adversely affect the spectrophotometric
procedure via direct competition with cyanide for the colorimetric
reagents. Thiocyanates can also decompose during distillation to give
sulfides. A test for sulfides in the scrubber solution must be
performed before proceeding with the analysis. After distillation and
dilution of the solution to volume, a drop, of the solution is placed
on lead acetate test paper. A dark color indicates the presence of
sulfides. If darkening is seen, treat 1M times the aliquot needed for
analysis with powdered cadmium carbonate. Yellow cadmium sulfide
precipitates if the scrubber solution contains sulfide. Repeat this
operation until a drop of the treated solution does not darken the
lead acetate test paper. Filter the solution through a dry filter
paper into a dry beaker, and from the filtrate measure the aliquot of
sample to be used for analysis. Avoid a large excess of cadmium
D-45
ILC03.X
-------
carbonate and a long contact time in order to minimize cyanide losses
by complexation or co-precipitation.
4 Apparatus
4.1 For the manual spectrophotometry method, use a spectrophotometer
suitable for measurements at 578 nm or 620 nm with a 1.0 cm cell or
larger.
4.2 For semi-automated spectrophotometric method:
4.2.1 Sampler
4.2.2 Pump
4.2.3 Cyanide Manifold
4.2.4 SCIC Spectrophotometer (or equivalent) with 15 mm flow cells and
570 nm filters
4.2.5 Data System
4.2.6 Glass or plastic tubes for the sampler
5 Reagents and Standards
5.1 Matrix matching with the samples is mandatory for all blanks,
standards, and QC samples to avoid inaccurate concentration values due
to differences in salt content and pH.
5.2 Preparation Reagents:
5.2.1 Cadmium carbonate, powdered
5.2.2 Stock cyanide solution: Dissolve 2.51 g of KCN and 2 g KOH in
1 L of reagent water (1 mL « 1000 ^g CN). Standardize by
titrating with 0.0192 N AgN03 using a few drops of Rhodanine
indicator. Note: The analyst should become familiar with the
yellow to brownish-pink end point of the titration and the
amount of indicator to be used before actually titrating the
samples. A 5 or 10 mL microburet may be conveniently used to
obtain a more precise titration.
5.2.3 Standard silver nitrate solution, 0,0192 N: Prepare by crushing
approximately 5 g AgNO, crystals and drying to constant weight
at 40 °C. Weigh 3.2S47 g of dried AgN03, dissolve in distilled
water, and dilute to 1 L using reagent water. 1 mL of this
solution will titrate approximately 1000 fig of CN.
5.2.4 Rhodanine indicator: Dissolve 20 mg of p-dimethyl-
aminobenzalrhodanine in 100 mL of acetone.
D-46
ILC03.1
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Standard cyanide solution, intermediate: Dilute 50.0 mL of
stock (5.2.2) to 1 L with reagent water (1 mL = 50 fig CN) .
Standard cyanide solution, working: Prepare fresh daily by
diluting 100.0 mL of intermediate cyanide solution (5.2.5) to 1
L with reagent water and store in a glass stoppered bottle (1
mL = 5.0 ug CN).
Sodium hydroxide solution, 1.25 N: Dissolve 50 g of NaOH in
reagent water and dilute to 1 L with reagent water.
Sodium hydroxide solution, 0.25 N: Dilute 200 ml of 1.25 N
NaOH (5.3.6) to 1 L with reagent water or dissolve 10 g of NaOH
in reagent water and dilute to 1 L with reagent water.
Note: All cyanide solutions should be stored in amber bottles in the
dark at 4 °C to prevent loss of cyanide through photodissociation.
5.2.9 Sodium dihydrogenphosphate, 1 M: Dissolve 138 g of NaH2P04^H20
in 1 L of reagent water. Refrigerate this solution until ready
to use. Bring to room temperature before using.
5.2.10 Chloramine-T solution: Dissolve 1.0 g of white, water-soluble
chloramine-T in 100 mL of reagent water and refrigerate until
ready to use. Bring to room temperature before using. Prepare
fresh weekly.
5.2.11 Color Reagent. One of the following may be used:
5.2.11.1 Pyridine-barbituric acid reagent: Place 15 g of
barbituric acid in a 250 mL volumetric flask and add
just enough reagent water to wash the sides of the
flask and wet the barbituric acid. Add 75 mL of
pyridine and mix. Add 15 mL of concentrated HC1 (sp
gr 1.19), mix, and cool to room temperature. Dilute
to 250 mL with reagent water and mix. This reagent
is stable for approximately six months if stored in
a cool, dark place.
5.2.11.2 Pyridine-pyrazolin-5-one solution:
3-Methy1-1-phenyl-2-pyrazolin-5-one
reagent, saturated solution: Add 0.25 g
of 3-methyl-1-phenyl-2-pyrazolin-5-one
to 50 mL of reagent water, heat to 60°C
with stirring. Cool to room
temperature.
3,3'Dimethyl-l,1'-diphenyl [4,4'-bi-2
pyrazolin]-5,5"dione (bispyrazolone):
Dissolve 0.01 g of bispyrazolone in 10
mL of pyridine.
D-47 ILC03.1
5.2.5
5.2.6
5.2.7
5.2.8
5.2.11.2.1
5.2.11.2.2
-------
5.2.11.2.3 Pour solution (5.2.11.2.1)through
nonacid-washed filter paper. Collect
the filtrate. Through the same filter
paper, pour solution (5.2.11.2.2)
collecting the filtrate in the same
container as filtrate from
(5.2.11.2.1). Mix until the filtrates
are homogeneous. The mixed reagent
develops a pink color that does not
affect the color production with
cyanide if used within 24 hours of
preparation.
5.2.12 Phosphate buffer: Dissolve 138 g of NaH2P04.H20 in reagent
water and dilute to 1 liter. Add 0.5 mL of Brij-35
(available from Technicon). Store at 4°C (±2°C).
Procedure
6.1 Standards and samples may be analyzed manually or by using a semi-
automated spectro-photometer. The semi-automated analysis should be
performed in accordance with manufacturer's guidelines.
6.1.1 Calibration: Prepare a minimum of three standards and a blank
by pipetting suitable volumes of standard solution into 100 mL
volumetric flasks. NOTE: One calibration standard must be at
the Contract Required Detection Limit (CRDL) of 10 /xg/L.
To each undistilled standard, add 50 mL of 0.25 N sodium
hydroxide, then add the appropriate amount of working standard
as suggested from the table below. At the time of calibration,
add the sodium phosphate, chloramine-T, and color reagent, then
dilute to 100 mL with reagent water. Record the absorbance of
each standard within the recommended development time for the
color reagent used. Standards must bracket the concentration of
the samples. If dilution of a high sample is required, use the
blank solution as a diluent. As an example, standard solutions
could be prepared as follows;
mL of Working Standard Cone. |ig/L CN
(1.0 mL = 5 ua CN) in 100 mL
0
Blank
0.1
5
0.2
10
0.5
25
1.0
50
to
o
100*
2.0
100
D-48
ILC03.1
-------
4.0
200
* standard suggested for distillation. Sodium phosphate, chloramine-
T, and color reagent are not added prior to distillation. After
distillation, the standard is analyzed as if it were a sample.
6.1.1.1 It is not imperative that all standards be distilled in
the same manner as the samples. At least one standard
{* mid-range) must be distilled and compared to similar
values on the curve to ensure that the distillation
technique is reliable. If the distilled standard does
not agree within +15% of the undistilled standards, the
operator should find and correct the cause of the
apparent error before proceeding.
6.1.1.2 Perform a linear regression of standard absorbance vs.
cyanide concentration in fig/L.
6.1.2 For sample analysis, withdraw 50.0 mL or less of the diluted
solution {treated for sulfides, if necessary) from the flask and
transfer to a 100.0 mL volumetric flask. Add 15.0 mL of sodium
phosphate solution and mix.
6.1.2.1 Pyridine-barbituric acid method: Add 2 mL of
chloramine-T solution and mix. After 1 to 2 min, add 5
mL of pyridine-barbituric acid solution and mix.
Dilute to mark with reagent water and mix again. Allow
8 min for color development, then read absorbance at
578 nm in a 1 cm cell within the next 7 minutes.
6.1.2.2 Pyridine-pyrazolone method: Add 0.5 mL of chloramine-T
solution and mix. After 1 to 2 min, add 5 mL of
pyridine-pyrazolone solution and mix. Dilute to mark
with reagent water and mix again. After 40 min, read
absorbance at 620 nm in a 1 cm cell. MOTE: More than
0.5 mL of chloramine-T will prevent the color from
developing with pyridine-pyrazolone.
7 Calculations
7.1 When the manual method is used in conjunction with a full-sized
distillation or midi-distillation, calculate the cyanide, in ng/L, in
the original sample as follows:
Vm Ffa
C=Cmx-x-^
S rn y y
s aa
D-49 ILC03.1
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where: C. = pig/L CN in the original sample,
e„ = n
-------
will cancel and the original sample concentration will be the same as
the measured sample concentration. If other than the recommended
volumes are used, actual values will have to be substituted in the
above equation,
7.2.1 If dilutions were performed, the appropriate corrections must be
applied to the sample values. The dilution factor used is
reported on Form XIV.
7.3 Appropriate concentration units must be specified on the required
forms. The quantitative values shall be reported in units of
micrograms per liter (/tg/L) for aqueous samples, no other units are
acceptable.
8 Quality Control
8.1 Quality control must be performed as specified in Exhibit E.
8.2 All QC data must be submitted with each data package as specified in
Exhibit B.
D-51
ILC03.1
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40/HR
2:1
SAMPLER
(0.12)
BLACK/BLACK
A10 1B7-6089
_—ocMUflu— mmutj
20 TC S TC
170-0103 01
A10
(1.00)
(0.42)
BUFFER
Tb F/C
Pump TUba
ORANGE/ORANGE
COLORIMETER
570 Bin
1S nm F/C
CHLOHAMINE-T
ORANGE/GREEN
(1.00) PYRKHNE-BARBITURtC ACID
(0.10) DISTILLED WATER
ORANGE/GREEN
Willi
(1.00) FROM F/C
GRAY/GRAY
To Sampltr -4-
(8.40) WASH
PURPLE/ORANGE
Figure 4. Cyanide Manifold
D-52
ILC03.1
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EXHIBIT S: Quality Assurance/Quality Control
SECTION I - General QA/QC Procedures and Definitions , E-l
SECTION II: Quality Assurance Program and Plan E-3
SECTION III - Standard Operating Procedures E-S
SECTION IV - Required QA/QC Operations E-ll
SECTION V - Contract Compliance Screening E-26
SECTION VI - Analytical Standard Requirements E-27
SECTION VII - Data Package Audits E-29
SECTION VIII - Performance Evaluation Samples E-30
SECTION IX - On-site Laboratory Evaluations E-32
ILC03.1
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SECTION I - General QA/QC Procedures and Definitions
1. The purpose of this document is to specify a uniform set of QA procedures
for the analysis of inorganic constituents of samples, documentation of
the methods used and its performance, and verification of the sample data
generated. The program will also assist laboratory personnel in recalling
and defending their actions under cross examination if required to present
court testimony in enforcement case litigation.
2. The primary function of the QA/QC program is to define procedures for
evaluating and documenting sampling and analytical methodologies, and for
data reduction and reporting. The objective is to provide a uniform basis
for sample handling, analysis, instrument and methods maintenance,
performance evaluation, and analytical data gathering and reporting.
Although it is impossible to address all analytical situations in one
document, the approach taken here is to define minimum requirements for
all major steps relevant to any inorganic analysis. In many instances
where methodologies are available, specific QC procedures are incorporated
into the method documentation (Exhibit D). Ideally, samples involved in
enforcement actions are analyzed only after the methods have met the
minimum performance and documentation requirements described in this
document.
3. The quality assurance/quality control (QA/QC) procedures defined herein
must be used by the Contractor when performing the methods specified in
Exhibit D. When additional QA/QC procedures are specified by the methods
in Exhibit D, the Contractor must also follow these procedures.
3.1 The cost of performing all QA/QC procedures specified in this
Statement of Work (SOW) is included in the price of performing the
bid lot. An exception is the analysis of duplicate, spike, and
performance evaluation samples (PES) which shall be considered
separate sample analyses.
4. The Contractor is required to participate in the Laboratory Audit Study
Program conducted by Environmental Protection Agency (EPA). The
Contractor must perform and report to Sample Management Office (SMO) and
the appropriate Region, as specified in Exhibit B, quarterly verification
of instrument detection limits (IDLs) by the method specified in Exhibit
D, for each instrument used to perform under this contract. All IDLs must
meet the Contract Required Detection Limits (CRDLs) specified in Exhibit C
(Table I). For inductively coupled plasma (ICP) methods, the Contractor
must also report, as specified in Exhibit B, all elemental expressions
used.
5. In this Exhibit, as well as other places within this SOW, the term
"analytical sample" is used when discussing the required frequency or
placement of certain QA/QC measurements. The term "analytical sample" is
defined in the glossary. Exhibit G. As the term is used, analytical
samples include all field samples and performance evaluation samples.
Matrix spikes, analytical/post-digestion spikes, duplicates, serial
dilutions, laboratory check samples (LCS), interference check solutions
(ICS), CRDL standards (CRI), preparation blanks, linear-range
determination standards (LRS), memory test solutions, and tuning solutions
are also included under this definition. Calibration verification
standards, i.e., initial calibration verification (ICV), initial
calibration blank (ICB), continuing calibration verification (CCV), and
continuing calibration blank (CCB) solutions are the only analyses in a
run that are not considered to be analytical samples. A "frequency of
10%" means once every 10 analytical samples. Note: Calibration
verification samples (ICVs and CCVs) and calibration verification blanks
(ICBs and CCBs) are not counted as analytical samples when determining 10%
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frequency.
In order for the QA/QC information to reflect the status of the samples
analyzed, all samples and their QA/QC analysis must be analyzed under the
same operating and procedural conditions.
6.1 If any QC measurement fails to meet contract criteria, the analytical
measurement may not be repeated prior to taking the appropriate
corrective action as specified in Exhibit E.
6.2 The Contractor must report all QC data in the exact format specified
in Exhibits B.
Standard laboratory practices for cleaning glassware and apparatus and for
using reagents, solvents, and gases must be adhered to by laboratory
personnel. For additional guidelines regarding these general laboratory
procedures, see Sections 4 and 5 of the Handbook for Analytical Quality
Control in Water and Wastewater Laboratories EPA-600/4-79-019, U.S.
Environmental Protection Agency Environmental Monitoring Systems
Laboratory, Cincinnati, Ohio, September 1982.
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SECTION II: Quality Assurance Program and Plan
Quality Assurance Program
The Contractor shall establish a Quality Assurance (QA) program with the
objective of providing sound analytical chemical measurements. This
program shall incorporate the QC procedures, any necessary corrective
action, all of the documentation required during data collections, and the
quality assessment measures performed by management to ensure acceptable
data production.
Quality Assurance Plan
2.1 As part of the QA program, the Contractor shall prepare a written
Quality Assurance Plan (QAP) which describes the procedures that are
implemented to achieve the following:
Maintain data integrity, validity, and useability.
Ensure that analytical measurement systems are maintained in an
acceptable state of stability and reproducibility.
Detect problems through data assessment and establish corrective
action procedures which keep the analytical process reliable.
Document all aspects of the measurement process in order to
provide data which are technically sound and legally defensible.
2.2 QAP Format - The QAP must present, in specific terms, the policies,
organization, objectives, functional guidelines, and specific quality
assurance (QA) and quality control (QC) activities designed to
achieve the data quality requirements of this contract. Where
applicable, Standard Operating Procedures (SOPs) pertaining to each
element shall be included or referenced as part of the QAP. The QAP
must be available during on-site laboratory evaluations and upon
written request by the Administration Project Officer (APO) or the
Technical Project Officer (TPO). The suggested format and contents
of the QAP are given in Figure E-l.
2.3 QAP Submission - During the contract solicitation process, the
Contractor is required to submit a QAP to the APO. Within sixty (60)
days after contract award, the Contractor shall mainatin on file a
revised QAP, fully compliant with the requirements of this contract.
The revised QAP is the official QAP under the contract. The revised
QAP must include changes resulting from:
The Contractor's internal review of their organization,
personnel, facility, equipment, policy and procedures.
The Contractor's implementation of the requirements of the
contract.
The Agency's review of the laboratory evaluation sample data,
bidder-supplied documentation.
Recommendations made during the preaward on-site laboratory
evaluation.
2.4 QAP Amendments - During the term of contract, the Contractor shall
revise and maintain on file, with all previous revision, an amended
QAP within 30 days of the following circumstances:
The Agency modifies the contract
The Agency notifies the Contractor of deficiencies in the QAP
document
The Agency notifies the Contractor of deficiencies resulting from
the Agency's review of the Contractor's performance
The Contractor identifies deficiencies resulting from their
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internal review of the QAP document
The Contractor's organization, personnel, facility, equipment,
policy or procedures change
The Contractor identifies deficiencies resulting from the
internal review of their organization, personnel, facility,
equipment, policy or procedures changes.
2.5 When the QAP is amended, all changes must be clearly marked with a
bar in the margin indicating where the change is found in the
document, or by highlighting the change by underlining, bold
printing, or using a different print font. The amended section pages
must have the date on which the changes were implemented.
2.6 QAP Archival - The Contractor shall maintain a master QAP which
incorporates the original QAP and all subsequent amendments. The
Contractor shall provide a copy of the master QAP or any of its
amendments to the designated recipients within 14 days of a request
by the TPO or APO.
Corrective Action - If a Contractor fails to adhere to the requirements
listed in this section, a Contractor may expect, but the Agency is not
limited to the following actions:
reduction in the number of samples sent under this contract
suspension of sample shipment to the Contractor
ICP-MS tape audit
data package audit
on-site laboratory evaluation
remedial performance evaluation sample
contract sanctions, such as a Cure Notice
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1. Organization and Personnel
1.1 QA Policy and Objectives
1.2 QA Management
1.2.1 Organization
1.2.2 Assignment of QA and QC Responsibilities
1.2.3 Reporting Relationships
1.2.4 QA Document Control Procedures
1.2.5 QA Program Assessment Procedures
1.3 Personnel
1.3.1 Resumes
1.3.2 Education and Experience Pertinent to this Contract
1.3.3 Training Program Completed
2. Facilities and Equipment
2.1 Instrumentation and Backup Alternatives
2.2 Maintenance Activities and Schedules
3. Document Control
3.1 Laboratory Notebook Policy
3.2 Sample Tracking/Custody Procedures
3.3 Logbook Maintenance and Archiving Procedures
3.4 Sample Delivery Group (SDG) File Organization, Preparation, and Review Procedures
3.5 Procedures for Preparation, Approval, Review, Revision, and Distribution of SOPs
3.6 Process for Revision of Technical or Documentation Procedures
4. Analytical Methodology
4.1 Calibration Procedures and Frequency
4.2 Sample Preparation Procedures
4.3 Sample Analysis Procedures
4.4 Standards Preparation Procedures
4.5 Decision Processes, Procedures, and Responsibility for Initiation of Corrective Action
5. Data Generation
5.1 Data Collection Procedures
5.2 Data Reduction Procedures
5.3 Data Validation Procedures
5.4 Data Reporting and Authorization Procedures
6. QA
6.1 Data QA
6.2 Systems/Internal Audits
6.3 Performance/External Audits
6.4 Corrective Action Procedures
6.5 QA Reporting Procedures
6.6 Responsibility Designation
7. QC
7.1 Solvent, Reagent, and Adsorbent Check Analysis
7.2 Reference Material Analysis
7.3 Internal QC Checks
7.4 Corrective Action and Determination of QC- Limit Procedures
7.5 Responsibility Designation
Figure E-l. Format and Content of QAP
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SECTION III - Standard Operating Procedures
To obtain reliable results, adherence to prescribed analytical methodology is
imperative. When an operation is performed on a repetitive basis,
reproducibility is best accomplished through the use of SOPs. As defined by
the EPA, an SOP is a document which provides directions for the step-by-step
execution of an operation, analysis, or action which is commonly accepted as
the method for performing certain routine or repetitive tasks.
SOPs prepared by the Contractor must be functional, i.e., clear,
comprehensive, up-to-date, and sufficiently detailed to permit duplication of
results by qualified analysts. They must be available at workstations, as
appropriate. SOPs must be reviewed regularly and updated when contract,
facility, or Contractor procedural modifications are made. Old revisions of
SOPs must be archived for future reference in usability or evidentiary
situations. Finally, SOPs must be subject to document control procedures
which preclude the use of outdated or inappropriate SOPs.
A complete set of SOPs must be available for inspection by the EPA during on-
site laboratory evaluations. All SOPs, as presented to the Agency, must
reflect activities as they are currently performed in the laboratory. During
on-site laboratory evaluations, laboratory personnel may be asked to
demonstrate the application of the SOPs.
The format for SOPs and a list of required SOPs are given in Parts A and B of
this Section. Part C of this Section describes the submission requirements
for SOPs.
PART A - SOP Format
The format for SOPs may vary depending upon the procedure for which they are
written. A general format and minimum requirements for SOPs is given in
Figure E-2. Overall, SOPs must be consistent with current EPA regulations,
guidelines, CLP contract requirements, and instrument manufacturers's
operating manuals. They also must describe the corrective measures and
feedback mechanisms used when analytical results do not meet the CLP protocol
QC requirement. Finally, they must require that sufficient data be recorded
(including operator observations and actions and instrument data) to document
the performance of all tasks required by CLP protocol and to validate all
results reported by the contractor.
1. Title page
2. Scope and application
3. Definitions
4. Procedures
5. Quality control (QC) limits
6. Corrective action procedures, including procedures for secondary
review of information being generated
7. Documentation description and example forms
8. Miscellaneous notes and precautions
9. References
Figure E-2. General SOP Format
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PART B - SOPS Required
The following SOPs are required by the Agency. Included with each are a list
of elements which should be included in the SOP.
1. Evidentiary SOP. A more detailed discussion of evidentiary SOPs required
chain-of-custody and document control are discussed in Exhibit F
2. Sample Receipt and Storage
Sample receipt and identification logbooks
Refrigerator temperature logbooks
Security precautions
3. Sample preparation
4. Glassware cleaning
5. Calibration of balances, etc.
Procedures
Frequency requirements
Preventative maintenance schedule and procedures
Acceptance criteria and corrective actions
Logbook maintenance authorization
6. Analytical procedures (for each analytical system)
Instrument performance specifications
Instrument operating procedures
Data acquisition system operation
Procedures when automatic quantitation algorithms are overridden
QC-required parameters
Analytical run/injection logbooks
Instrument error and editing flag descriptions and resulting
corrective actions
7. Maintenance activities (for each analytical system)
Preventative maintenance schedule and procedures
Corrective maintenance determinants and procedures
Maintenance authorization
8. Analytical standards
Standard coding/identification and inventory system
Standards preparation logbook(s)
Standard preparation procedures
Procedures for equivalency/traceability analyses and documentation
Purity logbook (primary standards and solvents)
Storage, replacement, and labeling requirements
QC and corrective action measures
9. Data reduction procedures
Data processing systems operation
Outlier identification methods
Identification of data requiring corrective action
Procedures for format and/or forms for each operation
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Documentation policy/procedures
Laboratory/analyst notebook policy, including review policy
Complete SDG file contents
Complete SDG File organization and assembly procedures, including
review policy
Document inventory procedures, including review policy
Data validation/self inspection procedures
Data flow and chain-of-command for data review
Procedures for measuring precision and accuracy
Evaluation parameters for identifying systematic errors
Procedures to ensure that hard copy and diskette deliverables are
complete and compliant with the requirements in SOW Exhibits B and H.
Procedures to ensure that hard copy deliverables are in agreement
with their comparable diskette deliverables.
Demonstration of internal QA inspection procedure (demonstrated by
supervisory sign-off on personal notebooks, internal laboratory
evaluation samples, etc.).
Frequency and type of internal audits {e.g., random, quarterly, spot
checks, perceived trouble areas).
Demonstration of problem identification-corrective actions and
resumption of analytical processing. Sequence resulting from
internal audit (i.e., QA feedback).
Documentation of audit reports, (internal and external), response,
corrective action, etc.
Data management and handling
Procedures for controlling and estimating data entry errors.
Procedures for reviewing changes to data and deliverables and
ensuring traceability of updates.
Lifecycle management procedures for testing, modifying and
implementing changes to existing computing systems including
hardware, software, and documentation or installing new systems.
Data base security, backup, and archival procedures including
recovery from system failures.
System maintenance procedures and response time.
Individual(s) responsible for system operation, maintenance, data
integrity, and security.
Specifications for staff training procedures.
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MOT C - SOPs Delivery Requirements
1. SOP Submission - During the contract solicitation process, the Contractor
is required to submit SOPs to the APO. Within sixty (60) days after
contract award, the Contractor shall maintain on file a revised SOP, fully
compliant with the requirements of this contract. The revised SOP is the
official SOP under the contract. The revised SOPs must include changes
resulting from:
The Contractor's internal review of their procedures.
The Contractor's implementation of the requirements of the contract.
The Agency's review of the laboratory evaluation sample data, bidder-
supplied documentation.
Recommendations made during the preaward on-site laboratory
evaluation.
2. SOP Revisions - During the term of contract, the Contractor must revise
SOPs within 30 days of the following circumstances:
The Agency modifies the contract and the modification affects an SOP
The Agency notifies the Contractor of deficiencies in the SOP
documentation
The Agency notifies the Contractor of deficiencies resulting from the
Agency's review of the Contractor's performance
The Contractor identifies deficiencies resulting from their internal
review of their SOP documentation
The Contractor's procedures change
The Contractor identifies deficiencies resulting from the internal
review of their procedures
2.1 When an SOP is amended, all changes must be clearly marked with a bar
in the margin indicating where the change is found in the document,
or by highlighting the change by underlining, bold printing, or using
a different print font. The amended section pages must have the date
on which the changes were implemented.
2.2 When the SOPs are amended or new SOPs are written, the Contractor
shall document in a letter to the TPO the reasons for the changes. An
alternate delivery schedule for the submittal of the letter may be
proposed by the Contractor, but it is the sole decision of the
Agency, represented either by the TPO or APO, to approve or
disapprove the alternate delivery schedule. If an alternate delivery
schedule is proposed, the Contractor shall describe in a letter to
the TPO, APO, and the Contracting Officer why he/she is unable to
meet the delivery schedule listed in this section. The TPO or APO
will not grant an extension of more than 30 days for amending or
writing new SOPs. The TPO or APO will not grant an extension of more
than 14 days for submission of the letter documenting the reasons for
the changes. The Contractor shall proceed and not assume that an
extension will be granted until so notified by the TPO and/or APO.
The Contractor shall send a complete set of current SOPs to the
designated recipients within 14 days of a request by the TPO or APO.
V
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Corrective Action - If a Contractor fails to adhere to the requirements
listed in this section, a Contractor may expect, but the Agency is not
limited to the following actions:
reduction in the number of samples sent under this contract
suspension of sample shipment to the Contractor
data package audit
on-site laboratory evaluation
remedial performance evaluation sample
contract sanctions, such as a Cure Notice
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SECTION IV - Required QA/QC Operations
This section outlines the minimum QA/QC operations necessary to satisfy the
analytical requirements of the contract. The following QA/QC operations must
be performed as described in this Exhibit:
Sample Analysis
Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) Tuning and Mass
Calibration
Instrument Calibration
ICV and CCV analysis
CRDL Standards (CRI/CRA) analysis
Linear Range Standard (LRS) Analysis
ICE, CCB, and PB Analyses
ICP and ICP-MS ICS Analyses
Matrix Spike Sample Analysis (S)
Duplicate Sample Analysis (D)
LCS Analysis
PES
Serial Dilution Analysis (L)
Internal Standards Evaluation for ICP-MS
Instrument Detection Limit (IDL) Determination
Elemental Expression for ICP and ICP-MS
Graphite Furnace Atomic Absorption (GFAA) QC Analysis
If a Contractor fails to adhere to the requirements listed in this section, a
Contractor may expect, but the Agency is not limited to the following actions:
reduction in the number of samples sent under this contract,
suspension of sample shipment to the Contractor,
ICP-MS data audit,
data package audit,
an on-site laboratory evaluation,
remedial performance evaluation sample, and/or
contract sanctions, such as a Cure Notice.
1, Sample Analysis
After sample preparation all samples must be analyzed initially without
any further dilution. If ICP or ICP-MS results are outside of the linear
range for the analyte, the sample must be diluted so that the
concentration is within the linear range. For results obtained by other
methods, if the concentration exceeds the calibrated range, the sample
must be diluted so that the concentration is within the calibrated range
of the instrument.
2. ICP-MS Tuning and Mass Calibration
2.1 Guidelines - Guidelines for mass calibration and tuning are given in
Exhibit D. Resolution and mass calibration must be performed for
each ICP-MS system, each time the instrument is set up. The
resolution and mass calibration must be verified immediately prior to
instrument calibration. The resolution and mass calibration must
also be verified at the end of each analytical run, or every 8 h,
whichever is more frequent. The tuning solution must be analyzed
after the final CCV/CCB in the run. The mass calibration and tuning
times as well as their verification times must be included in the raw
data.
2.2 Tuning Verification Solution - A 100-ppb solution of Li, Co, In, and
T1 must be used as a tuning verification solution. The intensities
and relative response ratios of the timing criteria are recommended
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in Table VII, Exhibit C.
2.3 Resolution and Mass Calibration Criteria - The resolution and mass
calibration criteria must be within the control limits in Table VII,
Exhibit C. If not, the analysis must be terminated, the problem must
be corrected, and all instrument results since the last compliant
mass calibration and resolution check must be rerun in a new
analytical run.
2.4 Mass Calibration and Resolution Check Reporting - The values for the
initial and subsequent mass calibrations and resolution check shall
be recorded on Form XV - LCIN for ICP-MS analyses, as indicated in
Exhibit B.
Instrument Calibration
3.1 Guidelines - Guidelines for instrumental calibration are given in EPA
600/4-79-0201 and Exhibit D. Calibrate all instruments according to
the instrument manufacturer's instructions or as specified in Exhibit
D. At least one blank and one standard must be used for ICP and
ICP-MS systems. All other systems must have a calibration standard
at the CRDL, a blank, and at least two other standards. Systems that
use nonlinear calibration curves must use at least three additional
standards that cover the upper and lower ranges of the curve.
Instruments must be calibrated daily or once every 24 h and each time
the instrument is set up. The date and time of instrument
calibration must be reported in the raw data.
3.2 Standards - Calibration standards must be prepared by diluting stock
solutions at the time of analysis, and must be discarded after use.
The date and time of the preparation and analysis of the standards
must be reported in the raw data. Calibration standards must be
prepared using the same matrix as the preparation blank.
3.3 Correlation Coefficient - Calibration curves with three or more
points must have a correlation coefficient of 0.995 or greater before
any analysis may be started. The correlation coefficient for each
calibration curve must be clearly documented and must be submitted
with the raw data.
Initial Calibration Verification (ICV)
4.1 Analysis - Immediately after calibration and prior to sample
analysis, an ICV must be analyzed to verify the accuracy of the
calibration. An ICV analysis is required for every analyte reported.
The analysis conditions for the ICV must be the same as those for the
analytical samples. If multiple sets of analytical conditions are
used to measure and report results for an analyte, the ICV must also
be measured and reported for each set of analytical conditions. For
each ICV analysis, a recovery is calculated by
ICV
%R = x 100
When the ICV recovery for an analyte exceeds the control limits
listed in Table III of Exhibit C, the analysis must be terminated,
the problem must be corrected, the instrument must be recalibrated,
and the calibration must be verified.
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4.2 Source - ICV solution(s) can be obtained from the EPA, a commercial
vendor, or prepared in-house. The source of the analytes in an ICV
solution must be independent of the source used for the calibration
standards, and the concentration of the analyte in the source
material must be certified. Finally, the concentration of an analyte
in the ICV should be in the mid-calibration range and different than
the calibration standard concentrations.
4.3 Cyanide - The ICV solution for cyanide also serves as the LCS and is
distilled prior to analysis. Furthermore, it must be distilled with
the batch of samples to be analyzed (i.e., for which it serves as the
LCS) .
4.4 Reporting - The true and measured concentrations for the ICV as well
as the percent recoveries must be recorded on Form II - LCIN for all
analytical systems, as indicated in Exhibit B.
Continuing Calibration Verification (CCV)
5.1 Analysis - A CCV solution must be analyzed periodically throughout an
analytical run to verify the stability of the calibration. The CCV
solution(s) must be analyzed at the beginning of an analytical run
(within 2 hours of the first analytical sample in the run), at the
end of the run (within 2 hours of the last analytical sample), and at
a minimum frequency of 10% or 2 hours during the run (whichever is
more frequent). A frequency of 10% corresponds to 10 analytical
samples between CCVs. A CCV analysis is required for every analyte
reported. The analysis conditions for the CCV must be the same as
those for the analytical samples. If multiple sets of analytical
conditions are used to measure and report results for an analyte, the
CCV must also be measured and reported for each set of analytical
conditions. For each CCV analysis, a recovery is calculated by
CCV
' measured 1QQ
CCV^
5.2 When the CCV recovery for an analyte exceeds the control limits
listed in Table II of Exhibit C, the analysis must be terminated, the
problem must be corrected, and the CCV must be reanalyzed. If the
reanalysis yields a CCV value within the specified control limits,
then the preceding 10 analytical samples or all analytical samples
analyzed since the last compliant CCV must be reanalyzed for the
analytes affected. Otherwise the instrument must be recalibrated,
the calibration must be verified, and the affected samples must be
reanalyzed in a new analytical run. If an affected analytical sample
is an instrument-related QC sample such as an ICS, CRI, or LRS, then
the problem must be corrected and the standards must be reanalyzed
within the 8-h limit for those standards. If not, all samples and QC
samples in the run must be reanalyzed.
5.3 Source - CCV solutions can be obtained from a commercial vendor or
prepared in-house. The concentration of the analyte in the source
material must be certified. The analyte concentrations in the CCV
standard must be at a concentration near the mid-point of the
calibrated range. Also, the same CCV standard must be used
throughout an analytical run.
5.4 Reporting - The true and measured concentrations for the CCV as well
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as the percent recoveries must be recorded on Form II - LCIN for all
analytical systems, as indicated in Exhibit B.
CRDL Standard (CRI/CRA)
6.1 Analysis - A standard with a concentration at or near the CRDL is
analyzed as part of an analytical run to verify the analysis accuracy
near the CRDL for all analytical systems. For ICP and ICP-MS
analyses, the standard is referred to as the CRI standard. For other
analyses, it is referred to as the CRA standard. The CRI and CRA
standards must be analyzed at the beginning (after the ICV) and end
of each analytical run, or a minimum of two times every 8 consecutive
hours, whichever is more frequent. A CRI or CRA analysis is required
for every analyte reported. The analysis conditions for the CRI/CRA
must be the same as those for the analytical samples. If multiple
sets of analytical conditions are used to measure and report results
for an analyte, the CRI/CRA must also be measured and reported for
each set of analytical conditions. For each CRI/CRA analysis, a
recovery is calculated by
CM/CRAmastnd inn
%R = — x 100
CM/CRAme
6.2 The CRI/CRA recovery for an analyte must be within the control limits
listed in Table II of Exhibit C. If the CRI/CRA at the beginning of
the analytical run is not within the control limits, the analysis
must be terminated, the problem must be corrected, and the instrument
must be recalibrated. All samples associated with non-compliant
CRI/CRA must be reanalyzed in a new analytical run. If the CRI/CRA
at the end of the run is not within the control limits, then all
sample results between the CRI/CRA standards must be flagged with a
"C" on Form I-LCIN in the Q qualifier column.
6.3 Source - The CRDL standard may be obtained from a commercial vendor
or prepared in-house. The concentration of the analyte in the source
material must be certified. The analyte concentrations in the CRI
standard must be twice the CRDL concentration while the analyte
concentrations in the CRA standard must be equal to the CRDL
concentrat ion.
6.4 Reporting - The true values, measured concentrations, and percent
recovery for the initial and subsequent CRDL standards for all
analysis systems must be recorded on Form III - LCIN, as indicated in
Exhibit B.
Linear Range Determination Standard (LRS)
7.1 Analysis - For ICP and ICP-MS analyses, the accuracy of analyses can
extend above the calibrated range. To verify the accuracy of
analyses above the calibrated range, a LRS standard can be analyzed
at the beginning (after the ICV) and end of each analytical run, or a
minimum of two times every 8 consecutive hours, whichever is more
frequent. A LRS analysis is required for every analyte reported with
a concentration above the calibrated range. The analysis conditions
for the LRS must be the same as those for the analytical samples. If
multiple sets of analytical conditions are used to measure and report
results for an analyte, the LRS must also be measured and reported
for each set of analytical conditions. For each LRS analysis, a
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recovery is calculated by
r jdc
%R = x 1Q0
IRSw
7.2 If the LRS recovery for an analyte is within 90-110%, sample results
up to the LRS concentration can be reported. If the recovery is not
within the control limits, sample results above the calibrated range
cannot be reported. Such samples would require dilution and
reanalysis.
7.3 Source - The LRS standard may be obtained from a commercial vendor or
prepared in-house. The concentration of the analyte in the source
material must be certified. The analyte concentrations in the LRS
standard is determined by the operator and is near the upper linear
range of the instrument (tinder the analytical conditions used).
7.4 Reporting - The true values, measured concentrations, and percent
recovery for the initial and subsequent LRS standards for all
analysis systems must be recorded on Form IV - LCIN, as indicated in
Exhibit B.
Calibration Blanks {ICV and CCV)
8.1 Analysis - Calibration blanks are analyzed as samples periodically
throughout an analytical run in order to verify the accuracy of the
calibration at a concentration of "0", to monitor the stability of
the calibration at a "0" concentration, and to check for carryover
between samples. The initial calibration blank (ICB) is analyzed
immediately after analyzing the ICV solution(s). Continuing
calibration blanks (CCB) must be analyzed after the LRS solution(s),
memory test solution (MTS), and every CCV solution. ICB and CCB
analyses are required for every analyte reported. The analysis
conditions for the ICB and CCBs must be the same as those for the
analytical samples. If multiple sets of analytical conditions are
used to measure and report results for an analyte, the ICB and CCBs
must also be measured and reported for each set of analytical
conditions. Analytical conditions include steps performed between
analyses, such as flushing, rinsing, and cleaning.
8.2 If the magnitude (absolute value) of an ICB or CCB for an analyte
exceeds its IDL, the result must be reported on Form V - LCIN. If
the absolute value of an ICB or CCB result exceeds the CRDL, analysis
must be terminated, the problem must be corrected, the instrument
must be recalibrated, and all analytical samples analyzed since the
last compliant ICB or CCB must be reanalyzed in a new analytical run.
If any of the affected analytical samples are instrument related QC
samples, such as ICS, CRI, LRS, or MTS, then the problem must be
corrected and the standards must be reanalyzed within the 8-hour
limit for those standards. If not, all samples and QC in the run
must be reanalyzed.
8.3 Source - Calibration blanks are prepared using the matrix solution of
the calibration standards,
8.4 Reporting - Results for the ICB and CCBs must be recorded on Form IV
- LCIN for all analytical systems, as indicated in Exhibit B.
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Preparation Blank (PB) Analyses
9.1 Analysis - A PB is prepared and analyzed with every SDG or batch of
samples prepared, whichever is more frequent. The results are used
to detect significant contamination from sample preparation.
9.2 If the PB concentration for an analyte is greater than the CRDL,
corrective action may be necessary. For samples associated with the
PB, results for the analyte may be reported if the concentration is
greater than 10 times the concentration measured in the PB or less
than the CRDL. Otherwise, the samples must be redigested and
reanalyzed for that analyte.
9.3 Source - At least one PB, consisting of reagent water (See Exhibit D,
Part IV Section 5.2), must be prepared and analyzed with every SDG,
or with each batch of samples prepared, whichever is more frequent.
9.4 If more than one PB is required for the same method, then the first
batch of samples is to be associated with PB 1, the second batch of
samples with PB 2, etc. Each data package must contain the results
of all PB analyses that are associated with the samples in that SDG.
9.5 Reporting - The values for PBs for all analysis systems must be
recorded on Form V - LCIN, as indicated in Exhibit B.
ICP and ICP-MS Interference Check Sample Analysis
10.1 Analysis - Inherent in ICP analyses are interelement correction
factors and spectral background corrections. Inherent in ICP-MS
analyses are interelement correction equations (also known as
elemental expressions). For ICP, to verify the accuracy of the
background correction points and interelement correction factors
and equations, two interference check samples (ICS) are analyzed
at the beginning and end of each analytical run, or every 8
hours, whichever is more frequent. For ICP-MS, the ICS solutions
must be analyzed once every 8 hours. The ICS samples are
identified as ICS-A, which contains only the common interferants,
and ICS-AB, which contains both the common interferants and
analytes. An ICS analysis is performed by analyzing the ICS-A
and ICS-AB solutions in sequence. The analysis conditions for
the ICS-A and ICS-AB must be the same as those for the analytical
samples. If multiple sets of analytical conditions are used to
measure and report results for an analyte, the ICS-A and ICS-AB
must also be measured and reported for each set of analytical
conditions.
Dilution of the ICS-A or ICS-AB solution prior to analysis is
only permitted if an analyte or interferant concentration exceeds
the linear range of the instrument. When dilution is necessary,
the dilution factor must be kept to a minimum. Results from the
diluted ICS analysis are only reported for the specific
analytes/interferants which required dilution. Results for the
other analytes/interferants must be reported from the undiluted
ICS analysis. When dilution is required, the ICS analysis
sequence must' be undiluted ICS-A, undiluted ICS-AB, diluted ICS-
A, diluted ICS-AB.
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For the analytes in the ICS-AB solution, a percent recovery is
calculated by
%R = ICS~AB"^d x 10Q
ICS-AB^
10.2 The absolute value of the analyte concentrations measured in the
ICS-A solution must not exceed the CRDL and the recovery of the
analytes in the ICS-AB solution must be within the limits of 80-
120%, inclusive. If the results are not within the control
limits, the analysis must be terminated, the problem must be
corrected, the instrument must be recalibrated, and the
analytical samples that followed the last compliant ICS analysis
(ICS-A and ICS-AB) must be reanalyzed.
10.3 Source - ICS solutions can be obtained from a commercial vendor,
or prepared in-house. The interferant and analyte concentrations
for ICS-A and ICS-AB are specified in Exhibit C, Table IV.
10.4 Reporting - The true values, measured concentrations, and percent
recoveries (ICS-AB only) for the initial and subsequent ICS
analyses must be recorded on Form VI - LCIN, as indicated in
Exhibit B.
11. Matrix Spike Sample Analysis
11.1 Preparation and Analysis - One matrix spike sample is prepared
and analyzed per method with each SDG or batch of samples
prepared, whichever is greater. If two or more methods are used
to determine and report a given analyte, then the matrix spike
sample must be analyzed by each method. A separate preparation
is only required if dictated by the analytical method. The
matrix spike sample analysis provides information about the
effect of the sample matrix on the preparation and measurement
methodology. To prepare a matrix spike sample, an aliquot of the
field sample is spiked, prior to digestion, with the analytes to
measured by the chosen analytical method. After spiking, the
sample is prepared and analyzed. The analyte concentrations
levels in the spike are specified in Exhibit C, Table III.
Unless otherwise specified by the documents shipped with the
samples, use the same field sample for both the matrix spike and
duplicate sample analysis. Samples identified as field blanks
must not be used for the matrix spike sample.
11.2 Recovery Calculation and Interpretation - A recovery is
calculated for each analyte added to the sample in the matrix
spike as follows;
ppp _ rrp
% Recovery = x 100
SA
Where SSR = analyte concentration in the matrix spike sample
SR = analyte concentration in the original sample
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SA = true analyte concentration added by the matrix spike
11.3 For SSR or SR which are less than the IDL, a value of "0" is used
to calculate the recovery. When the value of SR is less than 4
times the value of SA, the acceptance criteria for the matrix
spike recovery are 75-125%, inclusive. When the value of SR is
greater than 4 times the value of SA, there are currently no
defined acceptance criteria for the matrix spike recovery. If
the matrix spike recovery for an analyte is outside of the
acceptance criteria, the results for that analyte in all samples
associated with that matrix spike sample and determined by the
same analytical method must be flagged with the letter "N" on
Form 1- LCIN and VII - LCIN. If there is more than one matrix
spike sample per method per SDG and the recovery for one of them
is not within the control limits, all samples analyzed by the
same method in the SDG must be flagged.
11.4 Reporting - The results for the sample, matrix spike sample,
matrix spike added, and recovery shall be recorded on Form VII -
LCIN for all analysis systems, as indicated in Exhibit B.
12. Duplicate Sample Analysis
12.1 Preparation and Analysis - One duplicate sample is prepared and
analyzed with each SDG or batch of samples prepared, whichever is
greater. The duplicate sample analysis provides information
regarding the precision of the preparation and analysis
procedures. To prepare a duplicate sample, a duplicate aliquot
of the field sample is prepared and analyzed. If analyte
concentrations are determined and reported by more than one
method, duplicate results for that analyte must also be
determined and reported by both methods.
Unless otherwise specified by the documents shipped with the
samples, use the same field sample for both the matrix spike and
duplicate sample analysis. Samples identified as field blanks
must not be used for the duplicate sample.
12.2 Duplicate Precision Calculation and Interpretation - The
duplicate precision results are evaluated using either a simple
difference (delta) or relative percent difference (RPD),
depending upon the analyte concentration. The evaluation process
and calculations are summarized below.
SR
concentration
DR
concentration
Precision
Estimator
Control
Limit
SR > 5*CRDL
DR > 5*CRDL
RPD
20%
SR > 5*CRDL
SR 5 5*CRDL
5*CRDL 2 SR > CRDL
SR S 5*CRDL
DR £ 5*CRDL
DR > 5*CRDL
DR S 5*CRDL
5*CRDL 2 DR > CRDL
delta
± CRDL
SR S CRDL
DR S CRDL
none
none
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delta = SR - DR
% RPD = M.—M x 100
^SR + S£>j
Where SR = analyte concentration in the original sample
SD = analyte concentration in the duplicate sample
If the duplicate sample results for an analyte are outside the
control limits, the results for that analyte in samples associated
with that duplicate sample and analyzed by the same method must be
flagged with an '•*" on Form I - LCIN and Form VIII - LCIN. In the
instance where there is more than one duplicate sample per SDG, if
one duplicate result is not within the control limits, flag all
samples of the same method in the SDG.
12.3 Reporting - The results for the sample, duplicate sample, and RPD
(when appropriate) shall be recorded on Form VIII - LCIN for all
analysis systems, as indicated in Exhibit B.
Laboratory Control Sample {LCS) Analysis
13.1 Source - The LCS sample can be obtained from a commercial vendor,
or prepared in-house. If obtained commercially, the vendor must
certify the analyte concentrations against NIST-traceable
standards. If prepared in-house, the concentration of the
analyte in the source material must be certified against NIST-
traceable standards. The concentration of analytes in the LCS
must be between the CRDL and the upper linear range for the
method of analysis.
13.2 Preparation and Analysis - One LCS sample is prepared and
analyzed with each SDG or batch of samples prepared, whichever is
greater. The LCS sample analysis provides information regarding
the accuracy of the preparation and analysis procedures. The LCS
is prepared the same as a field sample. If analyte
concentrations are determined and reported by more than one
method, LCS results for that analyte must also be determined and
reported by both methods.
13.3 LCS Recovery Calculation and Interpretation - A recovery is
calculated for each analyte in the LCS as follows;
LCS
% Recovery = x 100
LC$tme
The default control limits for the LCS are 80-120%, inclusive.
These limits are used unless other limits are provided by the LCS
supplier. If the LCS results for an analyte are outside the
control limits, the problem must be corrected, and the samples
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associated with that LCS must be reprepared and reanalyzed for the
analyte in question.
13.4 Reporting - The true values, measured values, and percent recoveries
for the LCS must be recorded for all analytes on Form IX - LCIN, as
indicated in Exhibit B, Section II.
14. Performance Evaluation (PE) Sample Analysis
14.1 Source - PE samples are used by the EPA to monitor contractor
performance and are provided either single or double blind
samples. Single blind PE samples are provided to a contract lab as
a PE sample with unknown analytes and concentrations. Double blind
PE samples may be submitted unknown to a contract lab along with
routine field samples.
14.2 Preparation and Analysis - Single blind PE samples are prepared
according to the directions supplied with the samples. They are
analyzed as normal field samples. The Agency will notify the
Contractor of unacceptable performance. Unacceptable performance
for identification and quantification of analytes in the PES is
defined as a score of less than 75%. (See Exhibit E, Section VIII,
for additional details) .
14.3 Reporting - Results for PE samples are reported the same as field
samples.
15. Serial Dilution Analysis
15.1 Preparation and Analysis - In order to check for the presence of
matrix interferences during ICP and ICP-MS analyses, a serial
dilution analysis is performed. A serial dilution sample is
prepared by diluting an aliquot of prepared sample by a factor of
five (eg., diluting 10 mL of prepared sample to 50.0 mL) . The
diluent is reagent watr with the same acid content as the
calibration standards. One serial dilution sample is prepared and
analyzed with each SDG for both ICP and ICP-MS methods. If analyte
concentrations are determined and reported by both methods, then
results for serial dilution results must also be determined and
reported by both methods.
Unless otherwise specified by the documents shipped with the
samples, use the same field sample for the matrix spike, duplicate,
and serial dilution sample analysis. Samples identified as field
blanks must not be used for the duplicate sample.
15.2 Serial Dilution Recovery Calculation and Interpretation - For each
analyte in the serial dilution sample with a concentration at
least 20 times the IDL, a serial dilution recovery is calculated by
% Recovery = x 100
SR
where
SDR = concentration of the serial dilution
sample (corrected for dilution)
SR = concentration of the original sample
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The control limits for the serial dilution recovery are 90-110%,
inclusive. If the serial dilution recovery is outside the control
limits for an analyte, a chemical or physical interference effect
must be suspected and the results for that analyte in all samples
associated with that serial dilution sample must be flagged with an
"E" on Form X - LCIN and Form I - LCIN.
15.3 Reporting - The values for the original sample result, serial
dilution sample result, and percent recovery for all serial
dilution analyses must be recorded on Form X - LCIN, as indicated
in Exhibit B.
16. Internal Standards for ICP-MS
16.1 Preparation and Analysis - In order to correct for physical
interferences during ICP-MS analyses, a series of internal
standards are added to all samples (QC and field samples) prior to
analysis. A minimum of three internal standards, listed in Table
IX of Exhibit C, must be used, bracketing the mass range being
analyzed. Internal standards may be added manually to aliquots of
the samples being analyzed or automatically during analysis by
combining the sample stream and an internal standard stream prior
to aspiration.
16.2 Relative Intensity Calculation and Interpretation - The corrected
intensities for the internal standards in each sample are compared
to the corrected intensities for the internal standards in the " 0"
concentration calibration standard and a relative intensity (%RI)
calculated by
% RI = X 100
hrD-o
If the %RI for a given internal standard in a given sample is less
than 30%, a physical interference may be affecting the results. If
the %RI values for the surrounding QC samples (CCVs and CCBs) are
similar, the low %RI values are probably the result of a drop in
instrument sensitivity and may indicate that retuning and/or
cleaning is necessary. As long as the QC results are acceptable,
sample results are acceptable. If the %RI values for the
surrounding QC samples is significantly higher, the results for the
sample with a low %RI value are probably affected by matrix. The
sample must be reanalyzed after performing a 5-fold dilution. If
the %RI remains less than 30%, the sample results associated with
the low %RI value must be flagged with an "1" on Form XV and on
Form I - LCIN. If the affected sample is a matrix spike or
duplicate sample, the analytes affected must also be listed in the
Comment Section on the appropriate Forms VII - LCIN and VIII -
LCIN.
16.3 Reporting - The values for %RI must be reported for each ICP-MS
analysis on Form XVI - LCIN as indicated in Exhibit B.
17. Instrument Detection Limit (IDL) Determination
17.1 Frequency - IDLs must be determined for all analytes determined
under this contract and the IDL for each analyte must be determined
separately for each individual instrument. The IDLs for an
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instrument must be determined prior to its use on this contract as
described in Section 18.3 and must be updated quarterly thereafter
as described in Section 18.4. IDLs must also be determined as
described in Section 18.3 any time a change is made to an
instrument that will affect its IDLs.
17.2 Requirements - The CRDLs are specified in Table I of Exhibit C.
IDLs must be less than or equal to the CRDLs. If the IDL for a
given instrument exceeds the CRDL, only results from that
instrument greater than 5 times its IDL can be reported.
17.3 Initial Determination
17.3.1 Metals - Calibrate the instrument as performed on a routine
basis. Analyze, as unknown samples, 7 separate aliquots of the
calibration blank on three different days. The analysis
procedure must match that used for routine sample analysis.
Calculate the standard deviation for the 7 replicate values on
each day and a pooled standard deviation for all three days.
Si + si * s32
where Sp = pooled standard deviation
Sn = standard deviations for day l, day 2, and day 3
The IDL is defined as 3 times the pooled standard deviation, in
units of ng/h.
IDL = 2.61 x Sp
An IDL must be determined for each set of operating conditions
used to analyze samples. (This definition is based upon the
99% prediction interval for the measured concentration of a
blank sample. The multiplier has been rounded to one
significant figure).
17.3.2 Non-metals - The sample analyzed to estimate the IDL must
provide a realistic estimate of measurement variability at
concentrations near the detection limit. For the non-metal
analytes, depending upon the instrumentation and detection
system, this may or may not be possible with a calibration
blank. If possible, then the IDL for non-metal analytes is
determined as described for metals in Section 18.3.1. If not
possible, prepare a standard containing the analytes at
concentrations that are 1-3 times the estimated IDL. If an
estimated IDL is not known, use the CRDL as an estimate.
Substituting this standard for the calibration blank, determine
the IDL as described in Section 18.3.1.
17.4 Quarterly Update - Repeat the procedure described in 18.3 (Initial
Determination).
17.5 Reporting - The current IDLs must be reported on Form XII - LCIN,
and submitted with each data package, for each instrument used (and
each set of operating conditions) to produce data in the SDG, as
indicated in Exhibit B.
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18. Elemental Expressions for ICP-AES and ICP-MS
18.1 The ICP-AES and ICP-MS elemental expression factors must have been
determined within 3 months prior to beginning sample analyses under
this contract, and at least annually thereafter. Correction
factors for spectral and isobaric interferences must be determined
at all wavelengths and elemental expressions used for each analyte
reported using ICP-AES and ICP-MS. The correction factors must be
determined under the same instrument conditions used for sample
analysis. If the instrument was adjusted in any way that may
affect the interelement correction factors, the factors must be
redetermined and the results submitted for use.
18.2 Elemental expression factors must be determined annually. The
results of that determination must be reported on Form XIII - LCIN,
and submitted with each data package, for all ICP-AES and ICP-MS
parameters, for every instrument used to generate data in the SDG,
as indicated in Exhibit B.
18.3 Elemental expression factors for internal standards must be
reported on Form XIV - LCIN, and submitted with each data package
for all ICP-AES and ICP-MS parameters, for every instrument used to
generate data in the SDG, as indicated in Exhibit B.
19. GFAA QC Analyses
19.1 Because of the nature of GFAA techniques, the procedures summarized
in flowchart pictured in Figure E-3 are required for quantitation.
(These procedures do not replace those in Exhibit D of this SOW,
but supplement the guidance provided therein) . Each step in the
flowchart is described below;
[1] Prepare a post-digest analytical spike for every sample except the
calibration QC samples (ICV, ICB, CCV,CCB,CRA) and analyze along
with the unspiked sample. The required spiking concentrations are
listed below. The spiked sample can be prepared by the furnace AAS
instrument directly in the furnace tube or manually by the
operator. To prepare in an automated fashion using the instrument,
consult the operator's manual. To prepare manually, add a known
quantity of the analyte to an aliquot of the digested sample and
the same quantity of deionized water to another aliquot of the
digested sample. The volume of spiking solution must not exceed
10% of the sample aliquot volume.
Post-digest analytical spike concentration (ppb)
As
Pb
Se
T1
40
40
40
20
[2] The concentration of analyte in the spiked and unspiked samples
must fall within the calibrated range of the furnace AAS
instrument. If not, the sample must be diluted, re spiked, and
reanalyzed (refer to Step 8) . If the concentration is within the
calibrated range, the analytical spike recovery is calculated by
E-23
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%R - ssr-sr x 100
SA
The recovery is interpreted and corresponding action taken, as
described in Steps 3-8, with one exception. For the
preparation blank, the recovery must be within the window of
85-115%. If the PB analytical spike recovery is out of
control, the spiking solution must be verified by respiking and
rerunning the PB once. If the PB analytical spike recovery is
still out of the control limits, the problem must be corrected,
the PB respiked and all analytical samples associated with that
blank must be reanalyzed.
[3] If the analytical spike recovery is less than 40%, the sample must be
diluted, respiked, and reanalyzed once. If after dilution and
reanalysis, the analytical spike recovery is still less than 40%, the
result is reported down to the IDL and flagged with an "E" to indicate
matrix interference problems (refer to Step 8).
[4] If the analytical spike recovery is within the windows of 85-115%, the
results by direct quantification are "acceptable" and are reported down
to the IDL. If the recovery is not within the acceptance limits, the
analyst has the option of reanalyzing the sample and spike if this is
the first analysis.
[5] If the analytical spike recovery is outside of the windows 85-115% and
the sample concentration is less than half of the spike concentration,
the results are reported down to the IDL and flagged with a "W". The
"W" flag indicates that the analytical spike recovery is out-of-control
for unspecified reasons (eg, slight matrix problems or poor spiking
procedure). Because of the sample concentration, additional effort to
resolve the problem is not expected to result in a better number.
[6] If the analytical spike recovery is outside of the windows 85-115% and
the sample concentration is greater than half of the spike concentration
and greater than 20 times the CRDL, the sample is diluted, respiked, and
reanalyzed (refer to Step 8).
[7] If the analytical spike recovery is outside of the windows 85-115% and
the sample concentration is greater than half of the spike concentration
but less than 20 times the CRDL, the sample is quantified by the method
of standard additions (MSA). Samples for MSA analysis are prepared
manually by the operator. Alternatively, the MSA aliquots can be
prepared in an automated fashion by the furnace AAS instrument if it has
the capability. In either case, the following steps must be
incorporated into the MSA analysis.
[8] If called for by steps 2, 3, or 6, samples are diluted, respiked, and
reanalyzed. Generally, dilutions of 5-10 are acceptable. However,
analyst judgement may be used to perform other dilutions. However, the
sample must not be diluted so that the analyte is less than the CRDL.
If the sample is diluted below the CRDL, it must be reanalyzed using a
lower dilution factor, if possible.
E-24
hjco3.i
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Prepare and Analyze
Sample and One Spike
[1]
YES
Reanalyze sample
and spiked sample
[4c]
Dilute sample 5-10X,
respike, and reanalyze
[8]
Cone
~<. within calib.?
12]
YES
%R < 40%?
[3a]
85 < %R < 115?
4a]
irsttime
for this sample?
4b
Dilute sample 5-10X,
respike, and reanalyze
[S]
irst time
for this sample?
J3b]
YES
Quantify by MSA
[7a]
YES
YES [
YES
NO
-~< for this samp!
Report results down to
IDL.
Flag data with an "E*.
YES
Quantify from cal. curve.
Report down to IDL.
Report results down to
IDL.
Flag with a "W.
NO
Report MSA results.
Flag data withV
1
NO
Report MSA results.
Flag data with "S"
i"** t~* i a a r*i r\'
Figure E-3. GFAA QC Flow Diagram
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SECTION V - Contract Coirpliance Screening
Purpose
Contract Compliance Screening (CCS) is a contractual way for the Government
to inspect analytical data packages for adherence to contract requirements.
CCS results are used in conjunction with other information to measure overall
Contractor performance and to take appropriate actions to correct
deficiencies.
Description
CCS is performed by the SMO under the direction of EPA. Using a set of
standardized procedures sample data packages submitted by the Contractor are
evaluated against the technical and completeness requirements of the
contract. Copies of CCS results are mailed to contractor, regional client,
and QATS. The Agency may also generate a CCS trend report which summarizes
CCS results over a given period of time. The Agency may send the CCS trend
report to the lab or discuss it during an on-site laboratory evaluation.
Both the individual CCS reports and the trend report will identify any
contractor deficiencies. In either case, the Contractor must respond in
writing within 14 days of receiving the report(s) or the on-site laboratory
evaluation. The response must address the deficiencies and describe the
corresponding corrective action(s). An extension for responding of up to 14
days may be requested by the Contractor, but it is the sole decision of the
Agency, represented by the TPO or APO to approve or disapprove request. If
an extension is requested, the request must include a justification for the
delay. Any corrections to a data package must be sent to the regional
client, and SMO.
If required by the corrective action, any new or amended SOPs must be
submitted as required in Section IV of Exhibit E.
If the Contractor fails to adhere to the requirements listed in this section,
the Contractor may expect, but the Agency is not limited to the following
actions:
reduction in the number of samples sent under this contract,
suspension of sample shipment to the Contractor,
data package audit,
an on-site laboratory evaluation,
remedial performance evaluation sample, and/or
contract sanctions, such as a Cure Notice.
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SECTION VI - Analytical Standard Requirements
Source of Standards
The U.S. Environmental Protection Agency (EPA) does not supply analytical
reference standards for direct analytical measurements or for the purpose of
traceability. The contract laboratory is required to prepare in-house or
obtain commercially the standards necessary to successfully and accurately
perform the analyses required in this protocol.
1. l In-house Preparation of Stock Standard Solutions - Instructions for
preparing stock standards from high-purity reagent chemicals are given
in Exhibit D. After preparation, it is the responsibility of the
contract lab to verify the concentration of the stock standard
solutions. Verification can be performed using classical wet chemistry
or by analyzing against a certified standard from another source. If
a classical technique is used to set the standard concentration, the
relative precision of triplicate determinations must be less than 2%.
If analysis against a certified standard is used, the measured
concentration and theoretical concentration must agree within 2%. The
standard cannot be used until an acceptable verification is obtained
1.2 Commercially Obtained Stock Standard Solutions - Stock standard
solutions with certified analyte concentrations are readily available
from a number of private vendors. These standards can be used without
additional verification. However, the Contractor retains responsibility
for the quality of the commercially-obtained standards used for analyses
under this contract.
Documentat ion
It is the responsibility the contractor to maintain the documentation
demonstrating that the standards used for analysis conform to the
requirements previously listed. All data, whether produced by the
laboratory or supplied by a commercial vendor, must be maintained by the
laboratory and may be subject to review during on-site inspection
visits. The documentation which relates to the analytical results for
EPA data packages must be kept on file by the laboratory for 1 year.
2.1 Stock Standards - A standards logbook must be maintained to document the
preparation or receipt of stock standard solutions. For stock standards
prepared in-house, the logbook must fully document how and when the
standard was prepared and verified. For stock standards obtained
commercially, the logbook must include the standard source, date
received, date opened, and a copy of the certification (or reference to
its location). Stock standard solutions must be clearly labeled with
the analyte(s), concentration, dates (preparation or receipt/opened
dates), matrix (eg., acid type and concentration), logbook reference,
and initials of the preparer.
2.2 Working Standards - The preparation of working standards from the stock
standards must be documented in a logbook. It must contain how and when
each working standard was prepared (eg., stock standard identification,
volume of stock standard, final volume after dilution, diluent,
resultant concentration, etc.). The calculations for determining the
working standard concentration must be verified by a second person (as
indicated by their initials).
Stability of Standards
It is the responsibility of the contractor to maintain the quality of
their standards over time. Stock standards are generally stable for at
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least 6 months when stored properly. The concentration of an analyte
in commercially obtained stock standard is certified for a fixed time
period and the standard often has an "expiration date". All stock
standards older than 6 months or their expiration date must be
reverified prior to use.
EPA Auditing/Deficiency Reporting/Corrective Action
Upon request by the TPO or APO, the Contractor must submit the standards
documentation from the previous year (12 months). Documentation for
stock standards or working standards may be requested and must be
submitted within 14 days of the request.
The Agency may notify the Contractor of deficiencies in documentation
either by letter report or by discussing the deficiencies during an on-
site laboratory evaluation. In either case, the Contractor must respond
in writing within 14 days of receiving the report or the on-site
laboratory evaluation. The response must address the deficiencies and
describe the corresponding corrective action(s). An extension for
responding of up to 14 days may be requested by the Contractor, but it
is the sole decision of the Agency, represented by the TPO or APO to
approve or disapprove request. If an extension is requested, the
request must include a justification for the delay.
If required by the corrective action, any new or amended SOPs must be
submitted as required in Section IV of Exhibit E.
If the Contractor fails to adhere to the requirements listed in this
section, the Contractor may expect, but the Agency is not limited to the
following actions:
I reduction in the number of samples sent under this contract,
suspension of sample shipment to the Contractor,
data package audit,
an on-site laboratory evaluation,
remedial performance evaluation sample, and/or
contract sanctions, such as a Cure Notice.
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SECTION VII - Data Package Audits
Purpose of Audits
Data packages are audited by the Agency {or by a contractor under its
direction) for program and regional concerns. The audits are used to
assess the technical quality of the data, evaluate overall and
individual laboratory performance, and provide an in-depth review of
data packages with regard to QA/QC criteria. Additionally, this
independent monitoring of the data packages (outside of the CCS
screening) provides external review of the program QC requirements.
Description of Audits
Data packages are periodically selected from recently received cases and
evaluated for the technical quality of raw data, QC acceptability, and
adherence to contractual requirements. Audits are performed according
to established SOPs to ensure uniformity of the process. An audit
includes reviewing and comparing form data and raw data, verifying that
raw data is complete, checking calculations, and ensuring that all
contractual requirements are met. The data package is also compared to
the general lab information for contract compliance. For example, the
qualifications of the laboratory personnel involved with the case are
compared to the contract requirements and the raw data is reviewed to
and compared to what is expected from the current SOPs on file.
Audit Reports/Corrective Action
Upon completion of the data package audit, the Agency may send a copy
of the audit report to the Contractor or may discuss it with the
Contractor during an on-site laboratory evaluation. In either case, if
deficiencies are noted, the Contractor must respond in writing within
14 days of receiving the report or the on-site laboratory evaluation.
The response must address the deficiencies and describe the
corresponding corrective action(s). Copies of the response must be
submitted to the TPO, APO, and QATS. An extension for responding of up
to 14 days may be requested by the Contractor, but it is the sole
decision of the Agency, represented by the TPO or APO to approve or
disapprove request. If an extension is requested, the request must
include a justification for the delay.
If required by the corrective action, amy new or amended SOPs must be
submitted as required in Section IV of Exhibit E.
If the Contractor fails to adhere to the requirements listed in this
section, the Contractor may expect, but the Agency is not limited to the
following actions:
I reduction in the number of samples sent under this contract,
suspension of sample shipment to the Contractor,
data package audit,
an on-site laboratory evaluation,
remedial performance evaluation sample, and/or
contract sanctions, such as a Cure Notice.
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SECTION VIII - Performance Evaluation Samples
Purpose of PE Samples
As a means of measuring Contractor and method performance, Contractors
participate in Performance Evaluation (PE) studies conducted by the EPA.
As part of a PE study, a contractor analyzes a set of PE samples
following the same procedures used for routine samples. Results from
PE studies are used by the EPA to verify a Contractor's continuing
ability to produce acceptable analytical data. The results are also
used to assess the precision and accuracy of the analytical methods for
specific analytes.
Description of PE Samples
Quarterly, a Contractor will receive PE sample set consisting of up to
three water samples. The samples are generally shipped as concentrates
and must be diluted prior to use. Instructions are included with the
sample sets regarding any dilutions necessary. The laboratory is not
informed of the analytes in the PE samples nor their concentrations.
After any initial dilution, the PE samples are treated as field samples.
They must be prepared and analyzed and the results reported as specified
in this SOW, including the contract required turnaround time. All
contract-required QC must be met. The PE samples will be scored
following an established procedure. Analyte identification and
quantification as well as duplicate precision and matrix spike
recoveries are critical in calculating a performance score (0 to 100%).
The Agency will notify the Contractor of their performance score.
Performance Score
A Contractor's performance is evaluated based upon the score received
for the PE sample analyses. Depending upon the score, corrective action
must be taken.
3.1 Score > 90% - Most or all of the analytes in the PE samples have been
acceptably identified and quantified. The Contractor's performance is
acceptable. No corrective action is necessary.
3.2 90% > Score ;> 75 - Some of the analytes in the PE samples have been
misidentified or misquantified. The Contractor's performance is
acceptable but deficiencies exist. The Contractor must respond in
writing within 14 days of receiving the PE scoring report. The response
must address the deficiencies and describe the corresponding corrective
action(s). Copies of the response must be submitted to the TPO, APO,
and QATS. An extension for responding of up to 14 days may be requested
by the Contractor, but it is the sole decision of the Agency,
represented by the TPO or APO to approve or disapprove request. A
request for an extension must include a justification.
If required by the corrective action, any new or amended SOPs must be
submitted as required in Section IV of Exhibit E.
3.3 Score < 75% - Many of the analytes in the PE samples have been
misidentified or misquantified. The Contractor's performance is
unacceptable and major deficiencies exist. The National Program Office
considers that the Contractor has not demonstrated the capability of
meeting the contract requirements. The Contractor must respond in
writing within 14 days of receiving the PE scoring report. The response
must address the deficiencies and describe the corresponding corrective
action (s) . Copies of the response must be submitted to the TPO, APO,
and QATS. An extension for responding of up to 14 days may be requested
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by the Contractor, but it is the sole decision of the Agency,
represented by the TPO or APO to approve or disapprove the request. A
request for an extension must include a justification.
If required by the corrective action, any new or amended SOPs must be
submitted as required in Section IV of Exhibit E.
Upon receiving an unacceptable score, the Contractor shall be notified
by the TPO or APO concerning the consequence for their unacceptable
performance. A Contractor may expect, but the Agency is not limited to,
the following actions:
reduction in the number of samples sent under this contract
;| suspension of sample shipment to the Contractor
j : data package audit
i; an on-site laboratory evaluation
i; remedial performance evaluation sample
contract sanctions, such as a Cure Notice
A Contractor's prompt response demonstrating that corrective actions
have been taken to ensure the Contractor's capability to meet contract
requirements may facilitate continuation of full sample delivery.
Corrective Action
If the Contractor fails to adhere to the requirements listed in this
section, the Contractor may expect, but the Agency is not limited to the
following actions:
I reduction in the number of samples sent under this contract,
suspension of sample shipment to the Contractor,
data package audit,
an on-site laboratory evaluation,
remedial performance evaluation sample, and/or
contract sanctions, such as a Cure Notice.
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SECTION IX - On-site Laboratory Evaluations
Purpose and Frequency of On-site Laboratory Evaluations
On-site laboratory evaluations are carried out to monitor the
Contractor's ability to meet selected terms and conditions specified in
the contract. There are two separate categories of on-site evaluations;
Quality Assurance (QA) Evaluations and Evidentiary Audit Evaluations.
The frequency of on-site evaluations is dictated by a contract
laboratory's performance. The evaluations are performed by the
Administrative Project Officer (APO), Technical Project Officer (TPO),
or their authorized representative.
Description of On-site Laboratory Evaluations
2.1 QA Laboratory Evaluation - Prior to a QA evaluation, documentation
pertaining to performance of the Contractor is integrated into a profile
package for discussion during the evaluation. Items that may be
included are previous on-site evaluation reports, performance evaluation
sample scores, Regional reviews of data, Regional QA materials, data
audit reports, CCS reports, and data trend reports. During the on-site
evaluation, the audits will evaluate the entire operation used by the
Contractor to analyze samples under the contract, from sample receipt
to final sample disposition. As a minimum, the following items will be
inspected and evaluated:
Size and appearance of the facility
Quantity, age, availability, scheduled maintenance, and performance
of instrumentation
Availability, appropriateness, and utilization of the quality
assurance plan (QAP) and standard operating procedures (SOPs)
Staff qualifications, experience, and personnel training programs
Reagents, standards, and sample storage facilities
Standard preparation logbooks and raw data
Bench sheets and analytical logbook maintenance and review
Review of the Contractor's sample analysis/data package
inspection/data management procedures
2.2 Evidentiary Audit Evaluation - Agency auditors conduct on-site
laboratory evaluations to determine if laboratory policies and
procedures are in place to satisfy evidence handling requirements as
stated in Exhibit F. SOPs for sample receiving, sample storage, sample
identification, sample security, sample tracking (from receipt to
completion of analysis), and analytical project file organization and
assembly are reviewed for adequacy and completeness. Actual laboratory
records are examined to determine the accuracy of the SOPs (i.e., are
the SOPs being followed as written). Analytical project files are
reviewed to determine the accuracy of the document inventory,
completeness of the files, adequacy and accuracy of document numbering
system, traceability of sample activity, identification of activity
recorded on the documents, and error correction methods.
Audit Debriefing/Reporting/Contractor Response
The QA and evidentiary auditors discuss their findings with the APO
and/or TPO, then debrief the Contractor. During the debriefing, the
auditors present their findings to the Contractor and make
recommendations for any corrective actions necessary. Additionally, a
written audit reports that describes deficiencies found during the on-
site evaluation may be sent to the Contractor. The Contractor must
respond in writing within 14 days of receiving notification of
deficiencies, either during the on-site evaluation or in an on-site
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evaluation report. ' The response must address the deficiencies and
describe the corresponding corrective action(s). Copies of the response
must be submitted to the TPO, apo, and QATS. An extension for
responding of up to 14 days may be requested by the Contractor, but it
is the sole decision of the Agency, represented by the TPO or APO to
approve or disapprove the request. A request for an extension must
include a justification.
If required by the corrective action, any new or amended SOPs must be
submitted as required in Section IV of Exhibit E.
Corrective Action
If the Contractor fails to adhere to the requirements listed in this
section, the Contractor may expect, but the Agency is not limited to the
following actions:
reduction in the number of samples sent tinder this contract,
¦j suspension of sample shipment to the Contractor,
ill data package audit,
¦I; an on-site laboratory evaluation,
:: remedial performance evaluation sample, and/or
§ contract sanctions, such as a Cure Notice.
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EXHIBIT F - CHAIN-OF-CUSTODY, DOCUMENT CONTROL, AND STANDARD OPERATING PROCEDURES
1. Sample Chain-of-Custody
A sample is physical evidence collected from a facility or from the environment.
Controlling evidence is an essential part of the hazardous waste investigation
effort. To accomplish this, Contractors are required to develop and implement
the following sample identification, chain-of-custody, sample receiving, and
sample tracking procedures.
1.1 Sample Identification
To assure traceability of the samples while in the Contractor's possession,
the Contractor shall have procedures for maintaining identification of
samples throughout the laboratory. Each sample and sample preparation
container shall be labeled with the U.S. Environmental Protection Agency
{EPA) number or a unique laboratory identifier. If a unique laboratory
identifier is used, it shall be cross-referenced to the EPA number.
1.2 Chain-of-Custody Procedures
Because of the nature of the data being collected, the custody of EPA samples
must be traceable from the time the samples are collected until they are
introduced as evidence in legal proceedings. The Contractor shall have
procedures ensuring that EPA sample custody is maintained and documented. A
sample is under custody if:
It is in your possession, or
It is in your view after being in your possession, or
It was in your possession and you locked it up, or
It is in a designated secure area. (Secure areas shall be accessible only
to authorized personnel.)
1.3 Sample Receiving Procedures
1.3.1 The Contractor shall designate a sample custodian responsible for
receiving all samples.
1.3.2 The Contractor shall designate a representative to receive samples
in the event that the sample custodian is not available.
1.3.3 The condition of the shipping containers and sample bottles shall
be inspected upon receipt by the sample custodian or his/her
representative.
1.3.4 The condition of the custody seals (intact/not intact) shall be
inspected upon receipt by the sample custodian or his/her representative.
1.3.5 The sample custodian or his/her representative shall check for the
presence or absence of the following documents accompanying the sample
shipment:
• Airbills or airbill stickers
Custody seals
EPA custody records
EPA traffic reports or Special Analytical Services (3A3) packing lists
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Sample tags
1.3.6 The sample custodian or his/her representative shall sign and date
all forms (e.g., custody records, traffic reports or packing lists, and
airbills) accompanying the samples at the time of sample receipt.
1.3.7 The Contractor shall contact the Sample Management Office (SMO) to
resolve discrepancies and problems such as absent documents, conflicting
information, broken custody seals, and unsatisfactory sample condition
(e.g., leaking sample bottle).
1.3.8 The Contractor shall record the resolution of discrepancies and
problems on Telephone Contact Logs.
1.3.9 The following information shall be recorded on Form DC-1 (See
Exhibit B) by the sample custodian or his/her representative as samples
are received and inspected;
Condition of the shipping container
Presence or absence and condition of custody seals on shipping and/or
sample containers
Custody seal numbers, when present
Condition of the sample bottles
Presence or absence of airbills or airbill stickers
Airbill or airbill sticker numbers
Presence or absence of EPA custody records
Presence or absence of EPA traffic reports or SAS packing lists
Presence or absence of sample tags
Sample tag identification numbers cross-referenced to the EPA sample
numbers
Verification of agreement or non-agreement of information recorded on
shipping documents and sample containers
Problems or discrepancies
1.4 Sample Tracking Procedures
The Contractor shall maintain records documenting all phases of sample handling
from receipt to final analysis.
2. Document Control Procedures
The goal of the laboratory document control program is to assure that all
documents for a specified Sample Delivery Group (SDG) will be accounted for when
the project is completed. Accountable documents used by contract laboratories
shall include, but not be limited to, logbooks, chain-of-custody records, sample
work sheets, bench sheets, and other documents relating to the sample or sample
analyses. The following document control procedures have been established to
assure that all laboratory records are assembled and stored for delivery to EPA
or are available upon request from EPA prior to the delivery schedule.
2,1 Preprinted Laboratory Forms and Logbooks
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2.1.1 All documents produced by the Contractor which are directly related
to the preparation and analysis of EPA samples shall become the property
of the EPA and shall be placed in the complete SDG file (CSF) . All
observations and results recorded by the laboratory but not on preprinted
laboratory forms shall be entered into permanent laboratory logbooks.
When all data from a SDG is compiled, all original laboratory forms and
copies of all SDG-related logbook entries shall be included in the
documentation package.
2.1.2 The Contractor shall identify the activity recorded on all
laboratory documents which are directly related to the preparation and
analysis of EPA samples.
2.1.3 Pre-printed laboratory forms shall contain the name of the
laboratory and be dated (month/day/year) and signed by the person
responsible for performing the activity at the time an activity is
performed.
2.1.4 Logbook entries shall be dated (month/day/year) and signed by the
person responsible for performing the activity at the time an activity is
performed.
2.1.5 Logbook entries shall be in chronological order. Entries in
logbooks, with the exception of instrument run logs and extraction logs,
shall include only one SDG per page.
2.1.6 Pages in both bound and unbound logbooks shall be sequentially
numbered.
2.1.7 Instrument run logs shall be maintained so as to enable a
reconstruction of the run sequence of individual instruments. Because the
laboratory must provide copies of the instrument run logs to EPA, the
laboratory may exercise the option of using only laboratory or EPA sample
identification numbers in the logs for sample ID rather than government
agency or commercial client names to preserve the confidentiality of
commercial clients.
2.1.8 Corrections to supporting documents and raw data shall be made by
drawing a single line through the error and entering the correct
information. Corrections and additions to supporting documents and raw
data shall be dated and initialed. No information shall be obliterated or
rendered unreadable. All notations shall be recorded in ink. "Zs" shall
be placed in unused portions of documents.
2.2 Consistency of Documentation
The Contractor shall assign a document control officer responsible for the
organization and assembly of the CSF. All copies of laboratory documents
shall be complete and legible.
2.2.1 Original documents which include information relating to more than
one SDG shall be filed in the CSF of the lowest SDG number. The copy(s)
shall be placed in the other CSF(s) and the Contractor shall record the
following information on the copy(s) in red ink:
"COPY ORIGINAL IS PILED IN CSP __ "
The Contractor shall sign and date this" addition to the copy(s).
2.2.2 Before releasing analytical results, the document control officer
shall assemble and cross-check the information on samples tags, custody
records, lab bench sheets, personal and instrument logs, and other
relevant deliverables to ensure that data pertaining to each particular
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sample or sample delivery group is consistent throughout the CSF.
2.3 Document Numbering and Inventory Procedure
2.3.1 In order to provide document accountability of the completed
analysis records, each item in the CSF shall be inventoried and assigned
a serialized number as described in Exhibit B).
2.3.2 All documents relevant to each sample delivery group, including
logbook pages, bench sheets, mass spectra, chromatograms, screening
records, re-preparation records, re-analysis records, records of failed or
attempted analysis, custody records, library research results, etc. shall
be inventoried.
2.3.3 The Document Control Officer (DCO) shall be responsible for
ensuring that all documents generated are placed in the CSF for inventory
and are delivered to the appropriate EPA region or other receiver as
designated by EPA. The DCO shall place the sample tags in plastic bags in
the file.
2.3.4 Storage of EPA Files
The Contractor shall maintain EPA laboratory documents in a secure
location.
2.4 Shipment of Deliverables
The Contractor shall document shipment of deliverables packages to the
recipients. These shipments require custody seals on the containers placed
such that they cannot be opened without damaging or breaking the seal. The
Contractor shall document which deliverables were sent, to whom, the date,
and the method (carrier) used.
A copy of the transmittal letter for the CSF shall be sent to the NEIC/CEAT
and the SMO.
3. Specifications for Written Standard Operating Procedures
The Contractor shall have written standard operating procedures (SOPs) for
receipt of samples, maintenance of custody, sample identification, sample
storage, sample tracking, and assembly of completed data. An SOP is defined as
a written narrative stepwise description of laboratory operating procedures
including examples of laboratory documents. The SOPs shall accurately describe
the actual procedures used in the laboratory, and copies of the written SOPs
shall be available to the appropriate laboratory personnel. These procedures are
necessary to ensure that analytical data produced under this contract are
acceptable for use in EPA enforcement case preparation and litigation. The
Contractor's SOPs shall provide mechanisms and documentation to meet each of the
following specifications and shall be used by EPA as the basis for laboratory
evidence audits.
3.1 The Contractor shall have written SOPs describing the sample custodian's
duties and responsibilities.
3.2 The Contractor shall have written SOPs for receiving and logging in of
the samples. The procedures shall include but not be limited to documenting
the following information:
3.2.1 Presence or absence of EPA chain-of-custody forms
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3.2.2 Presence or absence of airbills or airbill stickers
3.2.3 Presence or absence of traffic reports or SAS packing lists
3.2.4 Presence or absence of custody seals on shipping and/or sample
containers and their condition
3.2.5 Custody seal numbers, when present
3.2.6 Airbill or airbill sticker numbers
3.2.7 Presence or absence of sample tags
3.2.8 Sample tag ID numbers
3.2.9 Condition of the shipping container
3.2.10 Condition of the sample bottles
3.2.11 Verification of agreement or non-agreement of information on
receiving documents and sample containers
3.2.12 Resolution of problems or discrepancies with the SMO
3.2.13 An explanation of any terms used by the laboratory to describe
sample condition upon receipt (e.g., good, fine, OK)
3.3 The Contractor shall have written SOPs for maintaining identification of
EPA samples throughout the laboratory.
3.3.1 If the Contractor assigns unique laboratory identifiers, written
SOPs shall include a description of the method used to assign the unique
laboratory identifier and shall include a description of the document used
to cross-reference the unique laboratory identifier to the EPA sample
number.
3.3.2 If the Contractor uses prefixes or suffixes in addition to sample
identification numbers, the written SOPs shall include their definitions.
3.4 The Contractor shall have written SOPs describing all storage areas for
samples in the laboratory. The SOPs shall include a list of authorized
personnel who have access or keys to secure storage areas.
3.5 The Contractor shall have written SOPs describing the method by which
the laboratory maintains samples under custody.
3.6 The Contractor shall have written SOPs describing the method by which
the laboratory maintains the security of any areas identified as secure.
3.7 The Contractor shall have written SOPs for tracking the work performed
on any particular samples. The tracking SOP shall include:
A description of the documents used to record sample receipt, sample
storage, sample transfers, sample preparations, and sample analyses.
A description of the documents used to record calibration and QA/QC
laboratory work.
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Examples of document formats and laboratory documents used in the sample
receipt, sample storage, sample transfer, and sample analyses.
A narrative step-wise description of how documents are used to track
samples.
3.8 The Contractor shall have written SOPs for organization and assembly of
all documents relating to each SDG. Documents shall be filed on a SDG-
specific basis. The procedures shall ensure that all documents including
logbook pages, sample tracking records, chromatographic charts, computer
printouts, raw data summaries, correspondence, and any other written
documents having reference to the SDG are compiled in one location for
submission to EPA. The written SOPs shall include:
A description of the numbering and inventory method.
• A description of the method used by the laboratory to verify consistency
and completeness of the CSF.
Procedures for the shipment of deliverables packages using custody seals.
4. Handling of Confidential Information
A Contractor conducting work under this contract may receive EPA-designated
confidential information from the agency. Confidential information must be
handled separately from other documentation developed under this contract. To
accomplish this, the following procedures for the handling of confidential
information have been established.
4.1 All confidential documents shall be under the supervision of a
designated document control officer (DCO).
4.2 Confidential Information
Any samples or information received with a request of confidentiality shall
be handled as "confidential." A separate locked file shall be maintained to
store this information and shall be segregated from other nonconfidential
information. Data generated from confidential samples shall be treated as
confidential. Upon receipt of confidential information, the DCO will log
these documents into a Confidential Inventory Log. The information will then
be available to authorized personnel but only after it has been signed out to
that person by the DCO. The documents shall be returned to the locked file
at the conclusion of each working day. Confidential information may not be
reproduced except upon approval by the EPA Administrative or Technical
Project Officer. The DCO will enter all copies into the document control
system described above. In addition, this information may not be disposed of
except upon approval by the EPA Administrative or Technical Project Officer.
The DCO shall remove and retain the cover page of any confidential
information disposed of for one year and shall keep a record on the
disposition in the Confidential Inventory Log.
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EXHIBIT G - GLOSSARY OF TERMS
ABSORBANCE A detector measurement of the decrease in incident light after it
passes through a sample.
ALIQUOT A measured portion of a field sample taken for analysis.
ANALYSIS DATE/TIME The date and military time (24 —h clock) of the introduction
of the sample, standard, or blank into the analysis system.
analyte The element or ion of interest.
ANALYTICAL SAMPLE Any solution or media, introduced into an instrument, on which
an analysis is performed (excluding instrument calibration, initial calibration
verification, initial calibration blank, continuing calibration verification, and
continuing calibration blank). Note the following are all defined as analytical
samples: undiluted and diluted samples (EPA and non-EPA), predigestion spike
samples, duplicate samples, serial dilution samples, analytical spike samples,
post digestion spike samples, interference check samples (ICS), Contract Required
Detection Limit (CRDL) standard for atomic absorption (CRA), CRDL standard for
Inductively Coupled Plasma (CRI), laboratory control sample (LCS), preparation
blank (PB), and linear range analysis sample (LRS).
ANALYTICAL SPIKE The post digestion spike. The addition of a known amount of
standard after digestion.
AUTOZERO Zeroing the instrument at the proper wavelength. It is equivalent to
running a standard blank with the absorbance set at zero.
AVERAGE INTENSITY The average of two different injections (exposures).
BACKGROUND CORRECTION A technique to compensate for variable background
contribution to the instrument signal in the determination of trace elements.
CALIBRATION The establishment of an analytical curve based on the absorbance,
emission intensity, or other measured characteristic of known standards. The
calibration standards must be prepared using the same type of acid or
concentration of acids as used in the sample preparation.
CALIBRATION BLANK A volume of ASTM Type I water acidified with the same acid
concentrations as is present in the samples.
CASE A finite, usually predetermined number of samples, collected over a given
time period from a particular site. Case numbers are assigned by the Sample
Management Office (SMO). A Case consists of one or more Sample Delivery Groups
(SDGs).
CONCENTRATION LEVEL (low or medium) For inorganics analysis, low or medium level
is defined by the appropriate designation checked by the sampler on the Traffic
Report (TR) .
CONTINUING CALIBRATION Analytical standard run every 10 analytical samples or
every 2 h, whichever is more frequent, to verify the calibration of the
analytical system.
CONTRACT REQUIRED detection LIMIT (crdl) Minimum level of detection acceptable
under the contract Statement of Work.
CONTROL LIMITS A range within which specified measurement results must fall to
be compliant. Control limits may be mandatory, requiring corrective action if
exceeded, or advisory, requiring that noncompliant data be flagged.
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CORRELATION COEFFICIENT A number (r) which indicates the degree of dependence
between two variables (e.g., concentration and absorbance). Two variables with
a high degree of dependence would produce a value for "r" which approaches ±1.
DAY - unless otherwise specified, day shall mean calendar day.
DIGESTION LOG An official record of the sample preparation (digestion).
DISSOLVED METALS Analyte elements which have not been digested prior to analysis.
DUPLICATE A second aliquot of a sample which has been treated in the same manner
as the original sample for the purpose of determining the precision of the
method.
FIELD BLANK Any sample submitted from the field identified as a blank.
FIELD SAMPLE A portion of material received to be analyzed that is contained in
single or multiple containers and identified by a unique EPA Sample Number.
GRAPHITE FURNACE ATOMIC ABSORPTION (GFAA) Atomic absorption which utilizes a
graphite cell for atomization and excitation.
HOLDING TIME The elapsed time expressed in days from the date of receipt of the
sample by the contractor until the date of its analysis:
Holding time = (sample analysis date - sample receipt date)
HYDRIDE MANIFOLD The area in which the acid borhydride solution and/or potassium
iodine solution mix before entering the nebulizer.
INDEPENDENT STANDARD A contractor-prepared standard solution that is composed
of analytes from a different source than those used in the standards for the
initial calibration.
INDUCTIVELY COUPLED PLASMA CICP) A technique for the simultaneous or sequential
multielement determination of elements in solution. The basis of the method is
the measurement of atomic emission by an optical spectroscopic technique.
Characteristic atomic line emission spectra are produced by excitation of the
sample in a radio-frequency inductively coupled plasma.
IN-HOUSE At the Contractor's facility.
injection Introduction of the analytical sample into the instrument excitation
system for the purpose of measuring absorbance, emission, or concentration of an
analyte. May also be referred to as exposure.
INSTRUMENT CALIBRATION Analysis of analytical standards for a series of
different specified concentrations; used to define the quantitative response,
linearity, and dynamic range of the instrument to target analytes.
INSTRUMENT DETECTION LIMIT (IDL) Determined by summing the standard deviations
obtained on 3 nonconsecutive days of 7 consecutive measurements of a standard
containing the analyte in reagent water at a concentration that is 3-5 times the
IDL.
INTERFERENCE CHECK STANDARD (ICS) A solution containing both interfering and
analyte elements of known concentrations that can be used to verify background
and interelement correction factors.
INTERFERENTS Substances which affect the analysis for the element of interest.
INTERNAL STANDARDS In-house compounds added at a known concentration.
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LABORATORY Synonymous with Contractor as used herein;
laboratory control SAMPLE (LCS) A control sample of known composition. Aqueous
laboratory control samples are analyzed using the same sample preparation,
reagents, and analytical methods employed for the EPA samples received.
LABORATORY RECEIPT DATE The date on which a sample is received at the
Contractor's facility, as recorded on the shipper's delivery receipt and sample
Traffic Report. Also referred to as VTSR (validated time of sample receipt).
LINEAR RANGE, LINEAR DYNAMIC RANGE The concentration range over which an
analytical curve remains linear as determined by the analysis of a standard
analyzed during an analytical run for which the standard is + 5% of the true
value.
MATRIX The predominant material of which the sample to be analyzed is composed.
For the purpose of this SOW, a sample matrix is water. Matrix is not synonymous
with phase (liquid or solid).
MATRIX MODIFIER Salts used in GFAA to lessen the effects of chemical
interferents, viscosity, and surface tension.
MATRIX SPIKE Aliquot of a sample fortified (spiked) with known quantities of
specific compounds and subjected to the entire analytical procedure Calculated
spike recoveries indicate the appropriateness of the method for the matrix.
METHOD OF STANDARD ADDITIONS (MSA) The addition of three increments of a
standard solution (spikes) to sample aliquots of the same size. Measurements are
made on the original and after each addition. The slope, x-intercept, and y-
intercept are determined by least-square analysis. The analyte concentration is
determined by the absolute value of the x- intercept. Ideally, the spike volume
is low relative to the sample volume (approximately 10% of the volume) . Standard
addition may counteract matrix interferences; it will not counteract spectral
interferences. Also referred to as Standard Addition.
PERFORMANCE EVALUATION (PE) SAMPLE A sample of unknown composition provided by
EPA for Contractor analysis. Used by EPA to evaluate Contractor performance.
PREPARATION BLANK (reagent blank, method blank) An analytical quality control
sample which is composed of distilled, deionized water and reagents. It is
carried through the entire analytical procedure (digested and analyzed).
PROTOCOL A compilation of the procedures to be followed with respect to sample
receipt and handling, analytical methods, data reporting and deliverables, and
document control. Used synonymously with Statement of Work (SOW).
RELATIVE standard deviation (RSD) The standard deviation as a percent of the
arithmetic mean.
ROUNDING RULES If the figure following those to be retained is less than 5, the
figure is dropped, and the retained figures are kept unchanged. As an example,
11.443 is rounded to 11.44.
If the figure following those to be retained is greater than 5, the
figure is dropped, and the last retained figure is raised by 1. As
an example, 11.446 is rounded to 11,45.
If the figure following those to be retained is 5, and if there are
no figures other than zeros beyond the five, the figure 5 is
dropped, and the last-place figure retained is increased by one if
it is an odd number or it is kept unchanged if an even number. As
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an example, 11.435 is rounded to 11.44, while 11.425 is rounded to
11.42.
If a series of multiple operations is to be performed (add,
subtract, divide, multiply), all figures are carried through the
calculations. Then the final answer is rounded to the proper number
of significant figures.
See Forms Instructions (Exhibit B) for exceptions.
run A continuous analytical sequence consisting of prepared samples and all
associated quality assurance measurements as required by the contract Statement
of Work.
SAMPLE DELIVERY GROUP (SDG) A unit within a sample Case that is used to identify
a group of samples for delivery. An SDG is a group of 20 or fewer samples within
a Case, received over a period of up to 7 calendar days. Data from all samples
in an SDG are.due concurrently. A Sample Delivery Group is defined by one of the
following, whichever occurs first:
Case; or
Each 20 samples within a Case; or
Each 7-day calendar period during which samples in a Case are
received, beginning with receipt of the first sample in the Case or
SDG.
SAMPLE NUMBER (EPA SAMPLE NUMBER) A unique identification number designated by
EPA for each sample. The EPA Sample Number is six digits in length and appears
on the sample Traffic Report which documents information on that sample.
SENSITIVITY The slope of the analytical curve (i.e., functional relationship
between instrument response and concentration).
SERIAL DILUTION The dilution of a sample by a factor of 5. When corrected by
the dilution factor, the diluted sample must agree with the original undiluted
sample within specified limits. Serial dilution may reflect the influence of
interferents.
STOCK SOLUTION A standard solution which can be diluted to derive other
standards.
SUSPENDED ELEMENTAL CONCENTRATION The fraction of elements in an untreated
sample which is retained by a 0.45 }im membrane filter.
TEN PERCENT FREQUENCY A frequency specification during an analytical sequence
allowing for no more than 10 analytical samples between required calibration
verification measurements, as specified by the contract Statement of Work.
TOTAL METALS Analyte elements which have been digested prior to analysis.
TRAFFIC REPORT (TR) An EPA sample identification form filled out by the sampler,
which accompanies the sample during shipment to the laboratory and which is used
for documenting sample condition and receipt by the laboratory.
G-4
ILC03.1
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