United States Office of Publication 9240.1 -30
Environmental Protection Solid Waste and EPA/540/R95/121 <
Agency Emergency Response PB95-963545
Superfund
&EPA USEPA CONTRACT
LABORATORY PROGRAM
Statement of Work for Inorganics
Analysis, Multi-media
Multi-concentation
ILMO 4.0
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ATTACHMENT A
USEPA CONTRACT LABORATORY PROGRAM
STATEMENT OF WORK
FOR
INORGANICS ANALYSIS
Multi-Media
Multi-Concentration
Document Number ILM04.0
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STATEMENT OF WORK
TABLE OF CONTENTS
EXHIBIT A: SUMMARY OF REQUIREMENTS
EXHIBIT B: REPORTING AND DELIVERABLES REQUIREMENTS
EXHIBIT C: INORGANIC TARGET ANALYTE LIST
EXHIBIT D: ANALYTICAL METHODS
EXHIBIT E: QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
EXHIBIT F: CHAIN-OF-CUSTODY, DOCUMENT CONTROL AND WRITTEN STANDARD OPERATING
PROCEDURES
EXHIBIT G: GLOSSARY OF TERMS
EXHIBIT H: DATA DICTIONARY AND FORMAT FOR DATA DELIVERABLES IN COMPUTER-
READABLE FORMAT
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EXHIBIT A
SUMMARY OF REQUIREMENTS
PAGE
SECTION I GENERAL REQUIREMENTS A-2
SECTION II SPECIFIC REQUIREMENTS A-4
SECTION III TECHNICAL AND MANAGEMENT REQUIREMENTS A-10
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CONTRACTOR OPERATED:
SAMPLE MANAGEMENT OFFICE
The Sample Management Office (SMO) is operated 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 (ILM04.0). 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 (ILM04.0).
All such questions or inquiries should be addressed to the responsible party
within EPA.
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SECTION I
GENERAL REQUIREMENTS
The Contractor shall employ procedures specified in this Statement of Work
(SOW) in the preparation and analysis of aqueous (water) and solid
(soil/sediment) samples for the presence and quantitation of 23 indicated
elements and cyanide.
The Contractor shall use proven instruments and techniques to identify and
measure the elements and inorganic species presented in the Target Analyte
List (Exhibit C). The Contractor shall perform sample preparation and
analysis procedures as prescribed in Exhibit D, meeting specified sample
preservation and holding time requirements.
If dissolved metals are requested by the EPA Regional offices, the Contractor
shall follow the instructions provided on the Traffic Report(s). If there are
no instructions on the Traffic Report, the Contractor shall digest the samples
designated as dissolved metals.
If the Regional office indicates on the Traffic Report that a digestion is not
to be performed when analyzing field samples for dissolved metals, then an
aqueous laboratory control sample (LCS) and a post-digestion (hardcopy Form SB
and diskette QC codes PDO and PDF) spike sample are not required.
The Contractor shall adhere to the quality assurance/quality control protocol
specified in Exhibit E for all samples analyzed under this contract.
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.
Exhibit F contains chain-of-custody and document control requirements which
the Contractor must follow in processing samples and specifies requirements
for written laboratory standard operating procedures.
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.
Exhibit H contains the Agency Standard implementation for reporting data
electronically.
The samples to be analyzed by the Contractor are from known or suspected
hazardous waste sites and, potentially, may contain hazardous inorganic and/or
organic materials at high concentration levels. The Contractor should be
aware of the potential hazards associated with the handling and analyses of
these samples. It is the Contractor's responsibility to take all necessary
measures to ensure the health and safety of its employees.
In addition, the Contractor must be aware of the importance of maintaining the
integrity of the data generated under the contract since the data are used to
make major decisions regarding public health and environmental welfare. The
data may also be used in litigation against Potentially Responsible Parties in
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the enforcement of Superfund legislation.
Prior to accepting any samples from the Agency, the Contractor shall have, in
house, the appropriate analytical and quality assurance standards for all
target analytes listed in Exhibit C.
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SECTION II
SPECIFIC REQUIREMENTS
A. FOR EACH SAMPLE, THE CONTRACTOR SHALL PERFORM THE FOLLOWING TASKS:
Task I; Receive and Prepare Hazardous Waste 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, perhaps more than one phase, contained inside
appropriate receptacles. More than one container may be used for a
single sample; individual containers may contain preservatives for
different analysis portions. Containers may be glass or plastic.
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 CLP Sample
Management Office (SMO). 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.
Samples will be routinely 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 within
the Contractor's geographical area.
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.
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.
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The Contractor shall be required to routinely return sample
shipping containers (i.e., coolers) to the appropriate sampling
office within fourteen (14) calendar days following shipment
receipt (see Clause entitled Government Furnished Supplies and
Materials).
If there are problems with the samples (e.g., mixed media,
containers broken or leaking) or 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.
3. The Contractor shall prepare and analyze samples within the maximum
holding times specified in Section II of Exhibit D even if these
times are less than the maximum data submission time allowed in
this contract.
4. The Contractor is advised that the samples received under this
contract are usually from known or suspected hazardous waste sites
and may contain high (greater than 15%) levels of organic and
inorganic materials of a potentially hazardous nature and of
unknown structure and concentration, and should be handled
throughout the analysis with appropriate caution. It is the
Contractor's responsibility to take all necessary measures to
ensure laboratory safety.
5. 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.
When the USEPA Regional office supplies a cooler temperature
indicator botrle 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.
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.
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.
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If the temperature of the sample shipping cooler's temperature
indicator exceeds 10 degrees Celsius, the Contractor shall contact
the Sample Management Office (SMO) and inform them of the
temperature deviation. The 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). The 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 fraction, the USEPA sample number, all samples which were
shipped in a cooler which exceeded 10 degrees Celsius.
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 Identity and Quantitation of Specific
Inorganic Constituents.
1. For each sample received, the Contractor may be required to perform
the analyses described in the following paragraphs 2., 3. and 4.
The documentation that accompanies the sample(s) to the Contractor
facility shall indicate specific analytical requirements for that
sample or set of samples.
The Contractor shall provide the required analytical expertise and
instrumentation for analysis of the Target Analyte List (TAL)
elements and cyanide equal to or lower than the detection limits
specified in Exhibit C. In exhibit D, EPA provides the Contractor
with the specific sample preparation techniques for water and
soil/sediment samples and the analytical procedures which must be
used. A schematic flow chart depicting the complete low level-
medium level inorganics analytical scheme is presented in Section I
of Exhibit D.
2. Exhibit D specifies the analytical procedures that must be
used. Exhibit D contains instructions and references for
preparation of samples containing low-to-medium
concentrations of inorganics for ICP analysis; flame,
graphite furnace and cold vapor AA analysis and cyanide
analysis. The identification and quantitation of
analytes other than cyanide shall be accomplished using the ICP or
AA methods specified in Exhibit D and shall achieve the Contract
Required Detection Limit (CRDL) specified in Exhibit C. Cyanide
shall be analyzed by the individual procedures specified in Exhibit
D.
3. All samples shall initially be run undiluted (i.e., the final
product of sample preparation procedure). When an analyte
concentration exceeds the calibrated or linear range, appropriate
dilution (but not below the CRDL) and reanalysis of the prepared
sample is required, as specified in Exhibit D.
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4. For the purpose of this contract, a full sample analysis is defined
as the analysis for ALL of the target constituents identified in
Exhibit C in accordance with the methods in Exhibit D and
performance of related QA/QC as specified In Exhibit E. Duplicate
sample, laboratory control sample, and spike sample analyses shall
each be considered a separate full sample analysis. All other
QA/QC requirements are considered an inherent part of this contract
Statement of Work 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 QA/QC
procedures including the daily or (as required) more frequent use
of standard reference solutions 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 quality control 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. Additional quality assurance and quality control shall be conducted
in the form of the analysis of laboratory performance evaluation
samples submitted to the laboratory by the Agency. The results of
all such quality control or laboratory evaluation samples may be
used as the basis for an equitable adjustment to reflect the
reduced value of the data to the Agency or rejection of the data
for: sample(s) within an SDG, a fraction (e.g., metals and/or
cyanide) within an SDG, and/or may be used as the basis for
contract action. "Compliant performance" is defined as that which
yields correct analyte identification and concentration values as
determined by the Agency, as well as meeting the contract
requirements for analysis (Exhibit D), quality assurance/quality
control (Exhibit E), data reporting and other deliverables
(Exhibits B and H), and sample custody, sample documentation and
standard operating procedure documentation (Exhibit F).
5. Laboratory Control Sample (LCS) - This standard solution is
designed to assure that the operating parameters of the analytical
instrumentation and analytical procedures from sample preparation
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through identification and quantitation produce reliable data. The
Contractor must analyze the LCS concurrently with the analysis of
the samples in the Sample Delivery Group (see Exhibit A, Part I).
B. EPA has provided to the Contractor formats for the reporting of data
(Exhibits B and H). The Contractor shall be responsible for completing
and returning analysis data sheets and submitting computer-readable data
on diskette in the format specified in this SOW and within the time
specified in the Contract Performance/Delivery Schedule (see Exhibit B).
1. Use of formats other than that designated by EPA will be deemed as
noncompliant. Such data are unacceptable. Resubmission in the
specified format at no additional cost to the government shall be
required.
2. Computer generated forms may be submitted in the hardcopy 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,
header information, columns and lines.
3. The data reported by the Contractor on the hardcopy data forms and
the associated computer-readable data submitted by the Contractor
on diskette shall contain identical information. If during
government inspection discrepancies are found, the Contractor shall
be required to resubmit either or both sets of data at no
additional cost to the Government. The resubmitted diskette and/or
hardcopy shall contain all of the initially correct information
previously submitted for all samples including, but not limited to,
the Laboratory Control Sample, standards, and blanks in the SDG in
addition to the corrections replacing the variables which were
incomplete or incorrect according to the requirements in the SOW.
C. The Contractor shall provide analytical equipment and technical expertise
for this contract as specified by the following:
1. Inductively coupled plasma (ICP) emission spectrometer with the
capability to analyze metals sequentially or simultaneously.
2. Atomic absorption (AA) spectrometer equipped with graphite furnace,
flame, and cold vapor AA (or a specific mercury analyzer) analysis
capabilities for the analysis of metals.
3. Analytical equipment/apparatus for analysis of cyanide as described
in Exhibit D.
D. The Contractor shall designate and utilize qualified key personnel to
perform rhe functions specified in this Statement of work. The EPA reserves
the right to review personnel qualifications and experience.
E. The Contractor shall respond (within seven 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).
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F. The Contractor is required to retain unused sample volume and used sample
containers for a period of 60 days after data submission. From time of
receipt until analysis, the Contractor shall maintain soil/sediment samples
at 4°C (±2°C).
G. 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 consists of one or more Sample
Delivery Groups (SDG). 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 14 calendar day period during which field samples in a Case are
received (seven calendar day period for 14-day data turnaround
contracts), said period begins with the receipt of the first sample
in the SDG.
Samples may be assigned to Sample Delivery Groups by matrix (i.e., all
soils in one SDG, all waters in another), at the discretion of the
laboratory. Such assignment shall be made at the time the samples are
received, and may not be made retroactively.
Data for all samples in an SDG shall be submitted together (in one
package) 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.
The Contractor is responsible for identifying each SDG as samples are
received, through proper sample documentation (see Exhibit B) and
communication with SMO personnel.
H. Each sample 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, 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.
The Contractor shall submit signed copies of Traffic Reports for all
samples in a Sample Delivery Group to SMO within FIVE (5) WORKING days
following receipt of the last sample in the SDG. Traffic Reports shall
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be submitted in SDG sets (i.e., all Traffic Reports for an SDG shall be
clipped together) with an SDG Cover Sheet containing information
regarding the Sample Delivery Group, as specified in Exhibit B.
I. 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 and in reports/correspondence.
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SECTION III
TECHNICAL AND MANAGEMENT REQUIREMENTS
I. TECHNICAL AND MANAGEMENT CAPABILITY
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.
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 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.
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
Page No.
SECTION I CONTRACT REPORTS/DELIVERABLES DISTRIBUTION B-2
SECTION II REPORT DESCRIPTIONS AND ORDER OF DATA DELIVERABLES .... B-5
SECTION III FORM INSTRUCTION GUIDE B-15
SECTION IV DATA REPORTING FORMS B-43
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Exhibit B Section I
SECTION 1
CONTRACT REPORTS/DELIVERABLES DISTRIBUTION
(For 35-Day Turnaround Contracts)
The following table reiterates the Contract reporting and deliverables
requirements specified in the Contract Schedule (Performance/Delivery
Schedule) and specifies the distribution that is required for each
deliverable.
NOTE: Specific recipient names and addresses are subject to change during the
term of the contract. The Administrative Project Officer will notify the
Contractor in writing of such changes when they occur.
TABLE 1
Item
No. of
Copies
Delivery Schedule
Distribution
(1) (2) (3)
A.
B.
C.
D.
E.
F.
G.
Standard
Operating
Procedures
Sample Traffic
Reports
Sample Data
Package"1"*"
Data in Computer
Readable
Format"1"*"
Results of
Inter comparison
Study/PE Sample
Analysis Study"1"1"
Complete SDG
Quarterly/
Annual
Verification of
Instrument
Parameters
60 days after
contract award,
and as required
in Exhibit E.
5 working days
after receipt of
last sample in
Sample Delivery
Group (SDG).**
35 days after
VTSR** of last
sample in SDG.
35 days after
VTSR of last
sample in SDG.
35 days after
VTSR of last
sample in SDG
35 days after
VTSR of last
sample in SDG.
Quarterly: 15th
day of January,
April, July,
October. Annual:
15th day of
January.
As Directed
X
B-2
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Exhibit B Section I
SECTION I
CONTRACT REPORTS/DELIVERABLES DISTRIBUTION
(For 14-Day Turnaround Contracts)
The following table reiterates the Contract reporting and deliverables
requirements specified in the Contract Schedule (Performance/Delivery
Schedule) and specifies the distribution that is required for each
deliverable.
NOTE: Specific recipient names and addresses are subject to change during the
term of the contract. The Administrative Project Officer will notify the
Contractor in writing of such changes when they occur.
TABLE 1
Distribution
Item
A. Standard
Operating
Procedures
No. of
Copies Delivery
Schedule
1 60 days after
contract award,
and as required
in Exhibit E.
(1) (2) (3)
As Directed
B. Sample Traffic
Reports
Sample Data
Package"1"1"
Data in Computer
Readable
Format"1"1"
5 working days
after receipt
of last sample
in Sample
Delivery Group
(SDG).**
14 days after
VTSR** of last
sample in SDG.
14 days after
VTSR of last
sample in SDG.
E. Results of
Intercomparison
Study/PE Sample
Analysis Study+H
*F. Complete SDG
File ++
Quarterly/
Annual
Verification of
Instrument
Parameters
14 days after
VSTR of last
sample in SDG.
14 days after
VTSR of last
sample in SDG.
Quarterly: 15th
day of January,
April, July,
October.
Annual: 15th
day of January.
B-2A
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Exhibit B Section I
Item
*H. Quality
No. of
Copies
1
Delivery
Schedule
60 days after
Distribution
(1) (2) (3)
As Directed
Assurance Plan contract award,
and as required
in Exhibit E.
Distribution:
(1) Sample Management Office (SMO) - CLASS Contractor
(2) Region-Client
(3) Quality Assurance Technical Support (QATS) Contractor
Note: 1 Contractor-concurrent delivery to QATS may be required upon request
by the APO. Retain for 365 days after data submission, and submit
within 7 days after receipt of written request by the APO.
Footnotes;
++ DELIVERABLES ARE TO BE REPORTED TOTAL AND COMPLETE. Concurrent delivery
is required. Delivery shall be made such that all designated recipients
receive the item on the same calendar day. This includes resubmission
of both the hardcopy and diskette. The date of delivery of the SDG, or
any sample within the SDG, is the date all samples have been delivered.
If the deliverables are due on a Saturday, Sunday or Federal holiday,
then they shall be delivered on the next business day. Deliverables
delivered after this time will be considered late.
* See Exhibit E for description. Time is cited in calendar days.
** VTSR (Validated Time of Sample Receipt) is the date of sample receipt at
the Contractor's facility, as recorded on the shipper's delivery receipt
and Sample Traffic Report. Sample Delivery Group (SDG) is a group of
samples within a Case, received over a period of 14 days or less (seven
days or less for 14-day data turnaround contracts) and not exceeding 20
samples. Data for all samples in the SDG are due concurrently. (See SOW
Exhibit A, for further description).
*** Complete SDG file will contain the original sample data package plus all
of the original documents described in Exhibit B of the Statement of
Work under Complete SDG File.
**** Also required in each Sample Data Package.
NOTE: As specified in the Contract Schedule (Government Furnished Supplies
and Materials), unless otherwise instructed by the CLP Sample Management
Office, the Contractor shall dispose of unused sample volume and used sample
bottles/containers no earlier than sixty (60) days following submission of
reconciled analytical data.
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Exhibit B Section I
No. of
Item Copies
*H. Quality 1
Delivery Schedule
60 days after
Distribution
(1) (2) (3)
As Directed
Assurance Plan contract award,
and as required
in Exhibit E.
Distribution:
(1) Sample Management Office (SMO) - CLASS Contractor
(2) Region-Client
(3) Quality Assurance Technical Support (QATS) Contractor
Note: 1 Contractor-concurrent delivery to QATS may be required upon request
by the APO. Retain for 365 days after data submission, and submit within
7 days after receipt of written request by the APO.
Footnotes:
++ DELIVERABLES ARE TO BE REPORTED TOTAL AND COMPLETE. Concurrent delivery
is required. Delivery shall be made such that all designated recipients
receive the item on the same calendar day. This includes resubmission
of both the hardcopy and diskette. The date of delivery of the SDG, or
any sample within the SDG, is the date all samples have been delivered.
If the deliverables are due on a Saturday, Sunday or Federal holiday,
then they shall be delivered on the next business day. Deliverables
delivered after this time will be considered late.
* See Exhibit E for description. Time is cited in calendar days.
** VTSR (Validated Time of Sample Receipt) is the date of sample receipt at
the Contractor's facility, as recorded on the shipper's delivery receipt
and Sample Traffic Report. Sample Delivery Group (SDG) is a group of
samples within a Case, received over a period of 14 days or less (seven
days or less for 14-day data turnaround contracts) and not exceeding 20
samples. Data for all samples in the SDG are due concurrently. (See SOW
Exhibit A, for further description).
*** Complete SDG file will contain the original sample data package plus all
of the original documents described in Exhibit B of the Statement of
Work under Complete SDG File.
**** Also required in each Sample Data Package.
NOTE: As specified in the Contract Schedule (Government Furnished Supplies
and Materials), unless otherwise instructed by the CLP Sample Management
Office, the Contractor shall dispose of unused sample volume and used sample
bottles/containers no earlier than sixty (60) days following submission of
reconciled analytical data.
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Exhibit B Section I
Distribution Addresses:
(1) USEPA Contract Laboratory Program (CLP)
Sample Management Office (SMO)1
P. O. Box 818
Alexandria, VA 22313
For overnight delivery service, use street address:
300 N. Lee Street
Alexandria, VA 22314
1 The Sample Management Office (SMO) is a contractor-operated facility
operating under the CLASS contract.
(2) USEPA REGIONS: The CLP Sample Management Office will provide the
Contractor with the list of addressees for the ten EPA Regions. SMO
will provide the Contractor with updated Regional address/name 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.
B-4 ILM04.0
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Exhibit B Section II
SECTION II
REPORT DESCRIPTIONS AND ORDER OF DATA DELIVERABLES
The Contractor laboratory shall provide reports and other deliverables as
specified in the Contract Performance/Delivery Schedule (see Contract
Schedule, Section F). The required content and form of each deliverable is
described in this Exhibit.
All reports and documentation SHALL BE as follows:
• Legible,
• Clearly labeled and completed in accordance with instructions in
this Exhibit,
• Arranged in increasing alphanumeric EPA sample number order,
• Paginated sequentially according to instructions in this Exhibit,
and
• Double-sided.
If submitted documentation does not conform to the above criteria, the
Contractor is required to resubmit such documentation with deficiency(ies)
corrected, at no additional cost to the government.
The Contractor shall be prepared to receive the full monthly sample contract
requirement at the time of contract award.
Whenever the Contractor is required to submit or resubmit data as a result of
an on-site laboratory evaluation or through an Administrative Project Officer
(APO)/Technical Project Officer (TPO) action, or through a Regional data
reviewer's request, the data shall be clearly marked as ADDITIONAL DATA and
shall be sent to the two contractual data recipients (SMO and Region). A
cover letter shall be included which describes what data is being delivered,
to which EPA Case(s) the data pertains, and who requested the data.
Whenever the Contractor is required to submit or resubmit data as a result of
Contract Compliance Screening (CCS) review by SMO, the data shall be sent to
the two contractual data recipients (SMO and Region), and in both instances
shall be accompanied by a color-coded COVER SHEET (Laboratory Response To
Results of Contract Compliance Screening) provided by SMO. Diskette
deliverables shall be submitted or resubmitted to SMO and the Region. Revised
DC-1 and DC-2 forms shall be resubmitted to SMO and the Region.
Section IV of this Exhibit contains the required Inorganic Analysis Data
Reporting Forms in Agency-specified formats; Section III of this Exhibit
contains instructions to the Contractor for properly completing all data
reporting forms to provide the Agency with all required data. Data elements
and field descriptors for reporting data in computer-readable format are
contained in Exhibit H.
B-5 ILM04.0
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Exhibit B Section II
Descriptions of the requirements for each deliverable item cited in the
Contract Performance/Delivery Schedule (see Contract Schedule, Section F) are
specified in parts A-G of this Section. Items submitted concurrently shall be
arranged in the order listed. Additionally, the components of each item shall
be arranged in the order presented herein when the item is submitted.
A. Quality Assurance Plan and Standard Operating Procedures
See Exhibits E and F for requirements.
B. Sample Traffic Reports
Original Sample Traffic Report page marked "Lab Copy for Return to SMO,"
with lab receipt information and signed with original Contractor
signature, shall be submitted for each sample in the Sample Delivery
Group.
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.
The SDG Cover Sheet shall contain the following items:
• Lab 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.
NOTE: When more than one sample is received in the first or last SDG
shipment, the "first" sample received would be the sample with the
lowest sample number (considering both alpha and numeric designations);
the "last" sample received would be the sample with the highest sample
number (considering both alpha and numeric designations).
In addition, each Traffic Report shall be clearly marked with the SDG
Number, the sample number of the first sample in the SDG (as described
in the following paragraph). This information shall be entered below
the Lab Receipt Date on the TR.
EPA field sample numbers are six digits in length. If the Contractor
receives sample numbers of any other length, contact SMO immediately.
The EPA sample number of the first sample received in the SDG is the SDG
number. When several samples are received together in the first SDG
shipment, the SDG number shall be the lowest sample number (considering
both 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.)
B-6 ILM04.0
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Exhibit B Section II
If samples are received at the laboratory with multi-sample Traffic
Reports (TRs), all the samples on one multi-sample TR may not
necessarily be in the same SDG. In this instance, the Contractor shall
make the appropriate number of photocopies of the TR, and submit one
copy with each SDG cover sheet.
C. Sample Data Package
The sample data package shall include data for analysis of all samples
in one Sample Delivery Group (SDG), including field and analytical
samples, reanalyses, blanks, spikes, duplicates, and laboratory control
samples. The sample data package shall be complete before submission,
shall be consecutively paginated {starting with page number one and
ending with the number of all pages in the package), and shall include
the following:
1. Cover Page for the Inorganic Analyses Data Package (COVER PAGE —
Inorganic Analyses Data Package), including: laboratory name;
laboratory code; contract number; Case No.; Sample Delivery Group
(SDG) No.; SAS Number (if appropriate); EPA sample numbers in
alphanumeric order showing EPA sample numbers cross-referenced
with lab ID numbers; comments, describing in detail any problems
encountered in processing the samples in the data package; and
completion of the statement on use of ICP background and
interelement corrections for the samples.
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, for other than the conditions detailed above.
Release of the data contained in this hardcopy 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
directly followed by the signature of the Laboratory Manager or
his designee with a typed line below it containing the signer's
name and title, and the date of signature.
In addition, on a separate piece of paper, the Contractor shall
also include any problems encountered, both technical and
administrative, the corrective action taken, and the resolution.
The Contractor shall retain a legible copy of the Sample Data
Package for 365 days after submission of the reconciled data
package. After this time, the Contractor may dispose of the
package.
2. Sample Data
Sample data shall be submitted with the Inorganic Analysis Data
Reporting Forms for all samples in the SDG, arranged in increasing
alphanumeric EPA sample number order, followed by the QC analyses
data, Quarterly Verification of Instrument Parameters forms, raw
data, and copies of the digestion and distillation logs.
B-7 ILM04.0
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Exhibit B Section II
a. Results — Inorganic Analysis Data Sheet [FORM I - IN]
Tabulated analytical results (identification and
quantitation) of the specified analytes (Exhibit C). The
validation and release of these results is 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 Cover Page.
Appropriate concentration units shall be specified and
entered on Form I. The quantitative values shall be
reported in units of micrograms per liter (ug/L) for
aqueous samples and milligrams per kilogram (mg/kg)
for solid samples. No other units are acceptable.
Results for solid samples shall be reported on a dry
weight basis. 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. Results for percent
solids shall be reported to one decimal place. The
preceding discussion concerning significant numbers
applies to Forms I and X only. For other Forms,
follow the instructions specific to those forms as
contained in this exhibit.
b. Quality Control Data
1) Initial and Continuing Calibration Verification [FORM
II (PART 1) - IN]
2) CRDL Standard for AA and ICP [FORM II (PART 2) - IN]
3) Blanks [FORM III - IN]
4) ICP Interference Check Sample [FORM IV - IN]
5) Spike Sample Recovery [FORM V (PART 1) - IN]
6) Post Digest Spike Sample Recovery [FORM V (PART 2) -
IN]
7) Duplicates [FORM VI - IN]
8) Laboratory Control Sample [FORM VII - IN]
9) Standard Addition Results [FORM VIII - IN]
10) ICP Serial Dilutions [FORM IX - IN]
11) Preparation Log [Form XIII - IN]
12) Analysis Run Log [Form XIV - IN]
B-8 ILM04.0
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Exhibit B Section II
c. Quarterly Verification of Instrument Parameters
1) Instrument Detection Limits (Quarterly) [FORM X - IN]
2) ICP Interelement Correction Factors (Annually) [FORM
XI (PART 1) - IN]
3) ICP Interelement Correction Factors (Annually) [FORM
XI (PART 2) - IN
4) ICP Linear Ranges (Quarterly) [FORM XII - IN]
(Note that copies of Quarterly Verification of Instrument
Parameters forms for the current quarter shall be submitted
with each data package.)
d. Raw Data
For each reported value, the Contractor shall include
in the data package all raw data used to obtain that
value. This applies to all required QA/QC
measurements, instrument standardization, as well as
all sample analysis results. This statement does not
apply to the Quarterly Verification of Instrument
Parameters submitted as a part of each data package.
Raw data shall contain all instrument readouts used
for the sample results. Each exposure or instrumental
reading shall be provided, including those readouts
that may fall below the IDL. All AA and ICP
instruments shall provide a legible hard copy of the
direct real-time instrument readout (i.e.,
stripcharts, printer tapes, etc.). A photocopy of the
instrument's direct sequential readout shall be
included. A hardcopy of the instrument's direct
instrument readout for cyanide shall be included if
the instrumentation has the capability.
The order of raw data in the data package shall be: ICP,
Flame AA, Furnace AA, Mercury, and Cyanide. All raw data
shall include concentration units for ICP and absorbances or
concentration units for flame AA, furnace AA, Mercury and
Cyanide. All flame and furnace AA data shall be grouped by
element.
Raw data shall be labeled with EPA sample number and
appropriate codes, shown in Table 2 following, to
unequivocally identify:
1) Calibration standards, including source and prep date.
2) Initial and continuing calibration blanks and
preparation blanks.
B-9 ILM04.0
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Exhibit B Section II
Table 2
Codes for Labelling Data
Sample
Sample not part of the SDG
Duplicate
Matrix Spike
Serial Dilution
Analytical Spike
Post Digestion/Distillation Spike
MSA:
Zero Addition
First Addition
Second Addition
Third Addition
Instrument Calibration Standards:
ICP
Atomic Absorption and Cyanide
Initial Calibration Verification
Initial Calibration Blank
Continuing Calibration Verification
Continuing Calibration Blank
Interference Check Samples:
Solution A
Solution AB
CRDL Standard for AA
CRDL Standard for ICP
Laboratory Control Samples:
Aqueous (Water)
Solid (Soil/Sediment)
Preparation Blank (Water)
Preparation Blank (Soil)
Linear Range Analysis Standard
xxxxxx
zzzzzz
XXXXXXD
xxxxxxs
XXXXXXL
XXXXXXA
XXXXXXA
xxxxxxo
XXXXXX1
XXXXXX2
XXXXXX3
S or SO for blank standard
SO, S10,...etc.
ICV
ICB
CCV
CCB
ICSA
ICSAB
CRA
CRT
LCSW
LCSS
PBW
PBS
LRS
Notes:
1. When an analytical spike or MSA is performed on samples other than field
samples, the "A", "0", "1", "2" or "3" suffixes shall be the last to be
added to the EPA Sample Number. For instance, an analytical spike of a
duplicate must be formatted "XXXXXXDA."
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.
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
shall be formatted "SO."
4. Use suffixes of "0", "1", "2", "3" as appropriate for samples identified
with ZZZZZZ on which MSA has been performed to indicate single
injections.
B-10
ILM04.0
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Exhibit B Section II
3) Initial and continuing calibration verification
standards, interference check samples, ICP serial
dilution samples, CRDL Standard for ICP and AA,
Laboratory Control Sample and post digestion spike.
4) Diluted and undiluted samples (by EPA sample number)
and all weights, dilutions and volumes used to obtain
the reported values. (If the volumes, weights and
dilutions are consistent for all samples in a given
SDG, a general statement outlining these parameters is
sufficient.)
5) Duplicates.
6) Spikes (indicating standard solutions used, final
spike concentrations, and volumes involved). If spike
information (source, concentration, volume) is
consistent for a given SDG, a general statement
outlining these parameters is sufficient.
7) Instrument used, any instrument adjustments, data
corrections or other apparent anomalies on the
measurement record, including all data voided or data
not used to obtain reported values and a brief written
explanation.
8) All information for furnace analysis clearly and
sequentially identified on the raw data, including EPA
sample number, sample and analytical spike data,
percent recovery, coefficient of variation, full MSA
data, MSA correlation coefficient, slope and
intercepts of linear fit, final sample concentration
(standard addition concentration), and type of
background correction used: BS for Smith-Heiftje, BD
for Deuterium Arc, or BZ for Zeeman.
9) Time and date of each analysis. Instrument run logs
can be submitted if they contain this information. If
the instrument does not automatically provide times of
analysis, these shall be manually entered on all raw
data for initial and continuing calibration
verification and blanks, as well as interference check
samples and the CRDL standard for ICP.
10) Integration times for AA analyses.
e. Digestion and Distillation Logs
Logs shall be submitted in the following order: digestion
logs for ICP, flame AA, furnace AA and mercury preparations,
followed by a copy of the distillation log for cyanide.
These logs shall include: (1) date, (2) sample weights and
volumes, (3) sufficient information to unequivocally
identify which QC samples (i.e., laboratory control sample,
preparation blank) correspond to each batch digested, (4)
B-ll ILM04.0
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Exhibit B Section II
comments describing any significant sample changes or
reactions which occur during preparation, and (5) indication
of pH <2 or >12, as applicable.
f. Properly completed Forms DC-1 and DC-2.
3. A copy of the Sample Traffic Reports submitted in Item B for all
of the samples in the SDG. The Traffic Reports shall be arranged
in increasing EPA Sample Number order, considering both alpha and
numeric designations. A legible photocopy of the SDG cover sheet
shall also be submitted.
D. Data in Computer Readable Form
The Contractor shall provide a computer-readable copy of the data for
all samples in the Sample Delivery Group, as specified in the Contract
Performance/Delivery Schedule. Computer-readable data deliverables
shall be submitted on an IBM or IBM-compatible, 5.25 inch floppy double-
sided, double density 360 K-byte or a high density 1.2 M-byte diskette
or on an IBM or IBM-compatible, 3.5 inch double-sided, double density
720 K-byte or a high density 1.44 M-byte diskette. The data shall be
recorded in ASCII, text file format, and shall adhere to the file,
record and field specifications listed in Exhibit H, Data Dictionary and
Format for Data Deliverables in Computer-Readable Format.
When submitted, diskettes shall be packaged and shipped in such a manner
that the diskette(s) cannot be bent or folded, and will not be exposed
to extreme heat or cold or any type of electromagnetic radiation. The
diskette(s) shall be included in the same shipment as the hardcopy data
and shall, at a minimum, be enclosed in a diskette mailer.
E. Results of Intercomparison/Performance Evaluation (PE) Sample Analyses
Tabulation of analytical results for Intercomparison/PE Sample analyses
include all requirements specified in items C. and D., above.
F. Complete SDG File (CSF)
As specified in the Delivery Schedule, one Complete SDG File (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 (delivery to QATS is only required upon written request). The
contents of the CSF shall be numbered according to the specifications
described in Sections III and IV of Exhibit B. The Document Inventory
Sheet, Form DC-2, is contained in Section IV.
The CSF shall contain all original documents where possible. No
photocopies of original documents shall be placed in the CSF unless the
original data was initially written in a bound notebook, maintained by
the Contractor, or the originals were previously submitted to the Agency
with another case/SDG in accordance with the requirements described in
Exhibit F. The CSF shall conrain all original documents specified in
Sections III and IV, and Form DC-2 of Exhibit B of the SOW.
B-12 ILM04.0
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Exhibit B Section II
The CSF shall consist of the following original documents in addition to
the documents in the Sample Data Package:
1. Original Sample Data Package
2. A completed and signed Document Inventory Sheet (Form DC-2)
3. All original shipping documents, including, but not limited to,
the following documents:
a. EPA Chain-of-Custody Record
b. Airbills
c. EPA (SMO) Traffic Reports
d. Sample Tags (if present) sealed in plastic bags.
4. All original receiving documents, including, but not limited to,
the following documents:
a. Form DC-1
b. Other receiving forms or copies of receiving logbooks.
c. SDG Cover Sheet
5. All original laboratory records of sample transfer, preparation,
and analysis, including, but not limited to, the following
documents:
a. Original preparation and analysis forms or copies of
preparation and analysis logbook pages.
b. Internal sample and sample digestate/distillate transfer
chain-of-custody records.
6. All other original case-specific documents in the possession of
the laboratory, including, but not limited to, the following
documents:
a. Telephone contact logs.
b. Copies of personal logbook pages.
c. All handwritten case-specific notes.
d. Any other case-specific documents not covered by the above.
NOTE: 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 copies to SMO and QATS).
B-13 ILM04.0
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Exhibit B Section II
If the laboratory does submit case-specific documents to EPA after
submission of the CSF, the documents shall be numbered as an
addendum to the CSF and a revised DC-2 form shall be submitted; or
the documents shall be numbered as a new CSF and a new DC-2 form
shall be submitted to the Regions only.
G. Quarterly and Annual Verification of Instrument Parameters
The Contractor shall perform and report quarterly verification of
instrument detection limits and linear range by the methods specified in
Exhibit E for each instrument used under this contract. For the ICP
instrumentation, the Contractor shall also perform and report annual
interelement correction factors (including method of determination),
wavelengths used and integration times. Forms for Quarterly and Annual
Verification of Instrument Parameters for the current quarter and year
shall be submitted in each SDG data package, using Forms X, XIA, XIB,
and XII. Submission of Quarterly/Annual Verification of Instrument
Parameters shall include the raw data used to determine those values
reported.
H. Corrective Action Procedures
If a Contractor fails to adhere to the requirements detailed in this
SOW, a Contractor may expect, but the Agency is not limited to the
following actions: reduction of numbers 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 (see Exhibit E
for additional details).
B-14 ILM04.0
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Exhibit B Section III
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:
A. General Information and Header Information
B. Cover Page — Inorganic Analyses Data Package [COVER PAGE - IN]
C. Inorganic Analysis Data Sheet [FORM I - IN]
D. Initial and Continuing Calibration Verification [FORM II (PART 1) - IN]
E. CRDL Standard for AA and ICP [FORM II (PART 2) - IN]
F. Blanks [FORM III - IN]
G. ICP Interference Check Sample [FORM IV - IN]
H. Spike Sample Recovery [FORM V (PART 1) - IN]
I. Post Digest Spike Sample Recovery [FORM V (PART 2) - IN]
J. Duplicates [FORM VI - IN]
^ -.
K. Laboratory Control Sample [FORM VII - IN]
L. Standard Addition Results [FORM VIII - IN]
M. ICP Serial Dilutions [FORM IX - IN]
N. Instrument Detection Limits (Quarterly) [FORM X - IN]
O. ICP Interelement Correction Factors (Annually) [FORM XI (PART 1) - IN]
P. ICP Interelement Correction Factors (Annually) [FORM XI (PART 2) - IN
Q. ICP Linear Ranges (Quarterly) [FORM XII - IN]
R. Preparation Log [Form XIII - IN]
S. Analysis Run Log [Form XIV - IN]
T. Sample Log-In Sheet [Form DC-1]
U. Document Inventory Sheet [Form DC-2]
B-15 ILM04.0
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Exhibit B Section III
A. General Information and Header Information
The data reporting forms presented in Section IV in this Exhibit have
been designed in conjunction with the computer-readable data format
specified in Exhibit H, Data Dictionary and Format for Data Deliverables
in Computer-Readable Format. The specific length of each variable for
computer-readable data transmission purposes is given in Exhibit H.
Information entered on these forms shall not exceed the size of the
field given on the form, including such laboratory-generated items as
Lab Name and Lab Sample ID.
Note that on the hardcopy forms (see Section IV), the space provided for
entries is greater in some instances than the length prescribed for the
variable as written to diskette (see Exhibit H). Greater space is
provided on the hardcopy forms for the sake of visual clarity.
Values shall be reported on the hardcopy forms according to the
individual form instructions in this section. Each form submitted shall
be filled out completely for all analytes before proceeding to the next
form of the same type. Do not submit multiple forms in place of one
form if the information on those forms can be submitted on one form.
All characters which appear on the data reporting forms presented in the
contract (Exhibit B, Section IV) shall be reproduced by the Contractor
when submitting data, and the format of the forms submitted shall 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. The names of the
various fields and analytes (i.e., "Lab Code," "Aluminum") shall appear
as they do on the forms in the contract, including the options specified
in the form (i.e., "Matrix (soil/water):" shall appear, not just
"Matrix").
All alphabetic entries made onto the forms by the Contractor shall be in
UPPERCASE letters (i.e., "LOW", not "Low" or "low"). If an entry does
not fill the entire blank space provided on the form, null characters
shall be used to remove the remaining underscores that comprise the
blank line. (See Exhibit H for additional instructions.) However, do
not remove the underscores or vertical bar characters that delineate
"boxes" on the forms.
Six pieces of information are common to the header sections of each data
reporting form. These are: Lab Name, Contract, Lab Code, Case No., SAS
No., and SDG No. This information shall be entered on every form and
shall match on all forms.
The "Lab Name" shall be the name chosen by the Contractor to identify
the laboratory. It may not exceed 25 characters.
The "Contract" is the number of the EPA contract under which the
analyses were performed.
The "Lab Code" is an alphabetic abbreviation of up to 6 characters,
assigned by EPA, to identify the laboratory and aid in data processing.
B-16 ILM04.0
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Exhibit B Section III
This lab code will be assigned by EPA at the time a contract is awarded,
and shall not be modified by the Contractor, except at the direction of
EPA.
The "Case No." is the SMO-assigned Case number (to 5 spaces) associated
with the sample, and reported on the Traffic Report.
The "SAS No." is the EPA-assigned number for analyses performed under
Special Analytical Services. If samples are to be analyzed under SAS
only, and reported on these forms, then enter SAS No. and leave Case No.
blank. If samples are analyzed according to this SOW (Routine
Analytical Services protocol) and have additional SAS requirements, list
both Case No. and SAS No. on all forms. If the analyses have no SAS
requirements, leave "SAS No." blank. (NOTE: Some samples in an SDG may
have a SAS No., while others do not.)
The "SDG No." is the Sample Delivery Group (SDG) number. 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 shall be the lowest sample number (considering both alpha and
numeric designations) in the first group of samples received under the
SDG.
The other information common to several of the forms is the "EPA Sample
No.". This number appears either in the upper righthand corner of the
form, or as the left column of a table summarizing data from a number of
samples. When "EPA Sample No." is entered into the triple-spaced box in
the upper righthand corner of a form, it shall be centered on the middle
line of the three lines that compose the box.
All samples, matrix spikes and duplicates shall be identified with an
EPA Sample Number. For samples, matrix spikes and duplicates, the EPA
Sample Number is the unique identifying number given in the Traffic
Report that accompanied that sample.
In order to facilitate data assessment, the sample suffixes listed in
Table 2 must be used.
Other pieces of information are common to many of the Data Reporting
Forms. These include: Matrix and Level.
For "Matrix", enter "SOIL" for soil/sediment samples, and enter "WATER"
for water samples. NOTE: The matrix must be spelled out.
Abbreviations such as "S" or "W" shall not be used.
For "Level", enter the determination of concentration level. Enter as
"LOW" or "MED", not "L" or "M".
Note: All results shall be transcribed to Forms II-XIV from the raw
data to the specified number of decimal places that are described in
Exhibits B and H. 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 for that form. If there are not
enough figures in the raw data result to enter in the specified space
B-17 ILM04.0
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Exhibit B Section III
for that result, then zeros shall be used for decimal places to the
specified number of reporting decimals for that result for a specific
form. The following examples are provided:
Raw Data Result
95
95
95
95
95
.99653
.99653
.99653
.996
.9
5
5
5
5
5
.4
.3
.2
.4
.4
(to
(to
(to
(to
(to
Specified Format Correct Entry on Form
four
decimal
places)
three decimal places)
two
four
four
decimal
decimal
decimal
places)
places)
places)
95
95
96
95
95
.9965
.997
.00
.9960
.9000
For rounding off numbers 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) .
Before evaluating a number for being in control or out of control of a
certain limit (other than the CRDL), the number evaluated shall be
rounded using EPA rounding rules to the significance reported for that
limit. For instance, the control limit for an ICV is plus or minus 10%
of the true value. A reported percent recovery value of 110.4 would be
considered in control while a reported value of 110.6 would be
considered out of control. In addition, a calculated value of 110.50
would be in control while a calculated value of 110.51 would be out of
control.
Cover Page - Inorganic Analyses Data Package [COVER PAGE-IN]
This form is used to list all samples analyzed within a Sample Delivery
Group, and to provide certain analytical information and general
comments. It is also the document which is signed by the Laboratory
Manager to authorize and release all data and deliverables associated
with the SDG.
Complete the header information according to the instructions in Part A.
For samples analyzed using this SOW, enter "ILM04.0" for SOW No.
Enter the EPA Sample No. (including spikes and duplicates) (to seven
spaces) of every sample analyzed within the SDG. Spikes shall contain
an "S" suffix and duplicates a "D" suffix. These sample numbers shall
be listed on the form in ascending alphanumeric order. 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, etc.
B-18 ILM04.0
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Exhibit B Section III
A maximum of twenty (20) sample numbers can be entered on this form.
Submit additional Cover Pages, as appropriate, if the total number of
samples, duplicates, and spikes in the SDG is greater than twenty (20).
A Lab Sample ID (to ten spaces) may be entered for each EPA Sample No.
If a Lab Sample ID is entered, it shall be entered identically (for each
EPA Sample No.) on all associated data.
Enter "YES" or "NO" in answer to each of the two questions concerning
ICP corrections. Each question shall be explicitly answered with a
"YES" or a "NO." The third question shall be answered with a "YES" or
"NO" if the answer to the second question is "YES." It shall be left
blank if the answer to the second question is "NO."
Under "Comments," enter any statements relevant to the analyses
performed under the SDG as a whole.
Each Cover Page shall be signed, in original, by the Laboratory Manager
or the Manager's designee and dated, to authorize the release and verify
the contents of all data and deliverables associated with an SDG.
C. Inorganic Analysis Data Sheet [FORM I-IN]
This form is used to tabulate and report sample analysis results for
target analytes (Exhibit C).
Complete the header information according to the instructions in Part A
and as follows.
"Date Received" is the date (formatted MM/DD/YY) of sample receipt at
the laboratory, as recorded on the Traffic Report, i.e., the Verified
Time of Sample Receipt (VTSR).
"% Solids" is the percent of solids on a weight/weight basis in the
sample as determined by drying the sample as specified in Exhibit D.
Report percent solids to one decimal place (i.e., 5.3%). If the percent
solids is not required because the sample is fully aqueous or less than
1% solids, then enter "0.0."
Enter the appropriate concentration units (UG/L for water or MG/KG dry
weight for soil). Entering "MG/KG" means "mg/Kg dry weight" on this
form.
Under the column labeled "Concentration," enter for each analyte either
the value of the result (if the concentration is greater than or equal
to the Instrument Detection Limit) or the Instrument Detection Limit for
the analyte corrected for any dilutions (if the concentration is less
than the Instrument Detection Limit). The concentration result shall be
reported to two significant figures if the result is less than 10; to
three significant figures if the value is greater than or equal to 10.
Under the columns labeled "C," "Q," and "M," enter result qualifiers as
identified below. If additional qualifiers are used, their explicit
definitions shall be included on the Cover Page in the Comments section.
B-19 ILM04.0
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Exhibit B Section III
FORM I-IN includes fields for three types of result qualifiers. These
qualifiers shall be completed as follows:
• C (Concentration) qualifier — Enter "B" if the reported value was
obtained from a reading that was less than the Contract Required
Detection Limit (CRDL) but greater than or equal to the Instrument
Detection Limit (IDL). If the analyte was analyzed for but not
detected, a "U" shall be entered.
• Q qualifier — Specified entries and their meanings are as
follows:
E - The reported value is estimated because of the presence of
interference. An explanatory note shall be included under
Comments on the Cover Page (if the problem applies to all
samples) or on the specific FORM I-IN (if it is an isolated
problem).
M - Duplicate injection 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 - Post-digestion spike for Furnace AA analysis is out of
control limits (85-115%), while sample absorbance is less
than 50% of spike absorbance. (See Exhibit E.)
* - Duplicate analysis not within control limits.
+ - Correlation coefficient for the MSA is less than 0.995.
Entering "S," "W," or "+" is mutually exclusive. No combination
of these qualifiers can appear in the same field for an analyte.
• M (Method) qualifier — Enter:
"P" for ICP
"A" for Flame AA
"F" for Furnace AA
"PM" for ICP when Microwave Digestion is used
"AM" for flame AA when Microwave Digestion is used
"FM" for Furnace AA when Microwave Digestion is used
"CV" for Manual Cold Vapor AA
"AV" for Automated Cold Vapor AA
"CA" for Midi-Distillation Spectrophotometric
"AS" for Semi-Automated Spectrophotometric
"C" for Manual Spectrophotometric
"T" for Titrimetric
" " where no data have been entered
"NR" if the analyte is not required to be analyzed.
B-20 ILM04.0
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Exhibit B Section III
A brief physical description of the sample, both before and after
digestion, shall be reported in the fields for color (before and after),
clarity (before and after), texture and artifacts. For water samples,
report color and clarity. For soil samples, report color, texture and
artifacts.
The following descriptive terms are recommended:
Color - red, blue, yellow, green, orange, violet, white,
colorless, brown, grey, black
Clarity - clear, cloudy, opaque
Texture - fine (powdery), medium (sand), coarse (large crystals
or rocks)
If artifacts are present, enter "YES" in the artifacts field and
describe the artifacts in the Comments field. If artifacts are not
present, leave this field blank.
Note any significant changes that occur during sample preparation (i.e.,
emulsion formation) in the Comments field. Enter any sample-specific
comments concerning the analyte results in the Comments field.
Initial and Continuing Calibration Verification [FORM II(PART 1)-IN]
This form is used to report analyte recoveries from calibration
solutions.
Complete the header information according to the instructions in Part A
and as follows.
Enter the Initial Calibration Source (12 spaces maximum) and the
Continuing Calibration Source (12 spaces maximum). Enter EPA as the
source of EPA standards. When additional EPA supplied solutions are
prepared in the future, the Contractor shall use the codes supplied with
those solutions for identification. If other sources were used, enter
sufficient information in the available 12 spaces to identify the
manufacturer and the solution used.
Use additional FORMS II(PART 1)-IN if more calibration sources were
used.
Under "Initial Calibration True," enter the value (in ug/L, to one
decimal place) of the concentration of each analyte in the Initial
Calibration Verification Solution.
Under "Initial Calibration Found," enter the most recent value (in ug/L,
to two decimal places), of the concentration of each analyte measured in
the Initial Calibration Verification Solution.
Under "Initial Calibration %R," enter the value (to one decimal place)
of the percent recovery computed according to the following equation:
B-21 ILM04.0
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Exhibit B Section III
EQ. 2.1
True (ICV)
Where, True(ICV) is the true concentration of the analyte in the Initial
Calibration Verification Solution and Found(ICV) is the found
concentration of the analyte in the Initial Calibration Verification
Solution.
The values used in equation 2.1 for True{ICV) and Found{ICV) shall be
exactly those reported on this form.
Under "Continuing Calibration True," enter the value (in ug/L, to one
decimal place) of the concentration of each analyte in the Continuing
Calibration Verification Solution.
Under "Continuing Calibration Found," enter the value (in ug/L, to two
decimal places) of the concentration of each analyte measured in the
Continuing Calibration Verification Solution.
Note that the form contains two "Continuing Calibration Found" columns.
The column to the left shall contain values for the first Continuing
Calibration Verification, and the column to the right shall contain
values for the second Continuing Calibration Verification. The column
to the right should be left blank if no second Continuing Calibration
Verification was performed.
If more than one FORM II(PART 1)-IN is required to report multiple
Continuing Calibration Verifications, then the column to the left on the
second form shall contain values for the third Continuing Calibration
Verification, the column to the right shall contain values for the
fourth Continuing Calibration Verification, and so on.
Under "Continuing Calibration %R," enter the value (to one decimal
place) of the percent recovery computed according to the following
equation:
EQ. 2.2
= Found (CCV]
True (CCV)
where, True(CCV) is the true concentration of each analyte, and
Found(CCV) is the found concentration of the analyte in the Continuing
Calibration Verification Solution.
The values used in equation 2.2 for True(CCV) and Found(CCV) shall be
exactly those reported on this form.
B-22 ILM04.0
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Exhibit B Section III
Note that the form contains two "Continuing Calibration %R" columns.
Entries to these columns shall follow the sequence detailed above for
entries to the "Continuing Calibration Found" columns.
Under "M," enter the method used or "NR," as explained in Part C.
If more than one wavelength is used to analyze an analyte, submit
additional FORMs II(PART 1)-IN as appropriate.
The order of reporting ICVs and CCVs for each analyte shall follow the
temporal order in which the standards were run starting with the first
Form IIA and moving from the left to the right continuing to the
following Form IIAs as appropriate. For instance, the first ICV for all
analytes shall be reported on the first Form IIA. In a run where three
CCVs were analyzed, the first CCV shall be reported in the left CCV
column on the first Form IIA and the second CCV shall be reported in the
right column of the same form. The third CCV shall be reported in the
left CCV column of the second Form IIA. On the second Form IIA, the ICV
column and the right CCV column shall be left empty in this example. In
the previous example, if a second run for an analyte was needed, the ICV
of that run shall be reported on a third Form IIA and the CCVs follow in
the same fashion as explained before. In the case where two wavelengths
are used for an analyte, all ICV and CCV results of one wavelength from
all runs shall be reported before proceeding to report the results of
the second wavelength used.
E. CRDL Standard for AA and ICP [FORM II(PART 2)-IN]
This form is used to report analyte recoveries from analyses of the CRDL
Standards for AA (CRA) and 2x the CRDL Standards for ICP (CRI).
Complete the header information according to the instructions in Part A
and as follows.
Enter the AA CRDL Standard Source (12 spaces maximum) and the ICP CRDL
Standard Source (12 spaces maximum), as explained in Part D.
Under "CRDL Standard for AA True," enter the value (in ug/L, to one
decimal place) of the concentration of each analyte in the CRDL Standard
Source Solution that was analyzed.
Under "CRDL Standard for AA Found," enter the value (in ug/L, to two
decimal places) of the concentration of each analyte measured in the
CRDL Standard Solution.
Under "CRDL Standard for AA %R," enter the value (to one decimal place)
of the percent recovery computed according to the following equation:
EQ. 2.3
%R = Found CRDL Standard for AA
True CRDL Standard for AA
B-23 ILM04.0
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Exhibit B Section III
Under "CRDL Standard for ICP Initial True," enter the value (to one
decimal place) of the concentration of each analyte in the CRDL Standard
Solution that was analyzed by ICP for analytical samples associated with
the SDG. Concentration units are ug/L.
Under "CRDL Standard for ICP Initial Found," enter the value (to two
decimal places) of the concentration of each analyte measured in the
CRDL Standard Solution analyzed at the beginning of each run.
Concentration units are ug/L.
Under "CRDL Standard for ICP, Initial %R, " enter the value (to one
decimal place) of the percent recovery computed according to the
following equation:
EQ. 2.4
D _ CRDL Standard for ICP Initial Found
CRDL Standard for ICP True
Under "CRDL Standard for ICP Final Found," enter the value (in ug/L, to
two decimal places) of the concentration of each analyte measured in the
CRDL Standard Solution analyzed at the end of each run.
Under "CRDL Standard for ICP Final %R," enter the value (to one decimal
place) of the percent recovery computed according to the following
equation:
EQ. 2.5
ar> CRDL Standard for ICP Final Found
CRDL Standard for ICP True
All %R values reported in equations 2.3, 2.4, and 2.5 shall be
calculated using the exact true and found values reported on this form.
Note that for every initial solution reported there must be a final one.
However, the opposite is not true. If a CRDL Standard for ICP (CRI) was
required to be analyzed in the middle of a run, it shall be reported in
the "Final Found" section of this form.
If more CRI or CRA analyses were required or analyses were performed
using more than one wavelength per analyte, submit additional FORMs
II(PART 2)-IN as appropriate.
The order of reporting CRAs and CRIs for each analyte shall follow the
temporal order in which the standards were run starting with the first
Form IIB and continuing to the following Form IIBs as appropriate. The
order of reporting CRA and CRI is independent with respect to each
other. When multiple wavelengths are used for one analyte, all the
results of one wavelength shall be reported before proceeding to the
next wavelength.
B-24 ILM04.0
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Exhibit B Section III
F. Blanks [FORM III-IN]
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).
Complete the header information according to the instructions in Part A
and as follows.
Enter "SOIL" or "WATER" as appropriate as the matrix of the Preparation
Blank. No abbreviations or other matrix descriptors may be used.
According to the matrix specified for the Preparation Blank, enter
"UG/L" (for water) or "MG/KG" (for soil) as the Preparation Blank
concentration units.
tinder "Initial Calib. Blank," enter the concentration (in ug/L, to one
decimal place) of each analyte in the most recent Initial Calibration
Blank.
Under the "C" qualifier field, for any analyte enter "B" if the absolute
value of the analyte concentration is less than the CRDL but greater
than or equal to the IDL. Enter "U" if the absolute value of the
analyte in the blank is less than the IDL.
Under "Continuing Calibration Blank 1," enter the concentration (in
ug/L, to one decimal place) of each analyte detected in the first
required Continuing Calibration Blank (CCB) analyzed after the Initial
Calibration Blank. Enter any appropriate qualifier, as explained for
the "Initial Calibration Blank," to the "C" qualifier column immediately
following the "Continuing Calibration Blank 1" column.
If only one Continuing Calibration Blank was analyzed, then leave the
columns labeled "2" and "3" blank. If up to three CCBs were analyzed,
complete the columns labeled "2" and "3," in accordance with the
instructions for the "Continuing Calibration Blank 1" column. If more
than three Continuing Calibration Blanks were analyzed, then complete
additional FORMs III-IN as appropriate.
Under "Preparation Blank," enter the concentration in ug/L (to three
decimal places) for a water blank or in mg/Kg (to three decimal places)
for a soil blank, of each analyte in the Preparation Blank. Enter any
appropriate qualifier, as explained for the "Initial Calibration Blank,"
to the "C" qualifier column immediately following the "Preparation
Blank" column.
For all blanks, enter the concentration of each analyte (positive or
negative) measured above the IDL or below the negative value of the IDL.
For example, arsenic has an IDL of 3 ug/L (CRDL for arsenic is 10 ug/L);
therefore, a CCB instrument reading of -6.2485 ug/L will be reported as
-6.2B, a CCB instrument reading of -2.4356 ug/L will be reported as
3.0U, a CCB instrument reading of 8.3586 ug/L will be reported as 8.4B,
and a CCB instrument reading of 2.1584 ug/L will be reported as 3.0U.
3-25 ILM04.0
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Exhibit B Section III
Under "M," enter the method used, as explained in Part C.
If more than one wavelength is used to analyze an analyte, submit
additional FORMs III-IN as appropriate.
The order of reporting ICBs and CCBs for each analyte shall follow the
temporal order in which the blanks were run starting with the first Form
III and moving from left to right and continuing to the following Form
Ills as explained in Part D. When multiple wavelengths are used for the
analysis of one analyte, all the results of one wavelength shall be
reported before proceeding to the next wavelength.
G. ICP Interference Check Sample [FORM IV-IN]
This form is used to report Interference Check Sample (ICS) results for
each ICP instrument used in Sample Delivery Group analyses.
Complete the header information according to the instructions in Part A
and as follows:
For "ICP ID Number," enter an identifier that uniquely identifies a
specific instrument within the Contractor laboratory. No two ICP
instruments within a laboratory may have the same ICP ID Number.
Enter "ICS Source" (12 spaces maximum) as explained in Part D. For EPA
solutions, include in the source name a number identifying it (e.g.,
EPA-LV87).
Under "True Sol. A," enter the true concentration (in ug/L, to the
nearest whole number) of each analyte present in Solution A.
Under "True Sol. AB," enter the true concentration (in ug/L, to the
nearest whole number) of each analyte present in Solution AB.
Under "Initial Found Sol. A," enter the concentration (in ug/L, to the
nearest whole number) of each analyte found in the initial analysis of
Solution A as required in Exhibit E.
Under "Initial Found Sol. AB," enter the concentration (in ug/L, to one
decimal place) of each analyte in the initial analysis of Solution AB as
required in Exhibit E.
Under "Initial Found %R," enter the value (to one decimal place) of the
percent recovery computed for true solution AB greater than zero
according to the following equation:
EQ. 2.6
Initial Found Solution AB
True Solution AB
x
Leave the field blank if true solution AB equals zero.
B-26 ILM04.0
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Exhibit B Section III
Under "Final Found Sol. A," enter the concentration (in ug/L, to the
nearest whole number) of _%ach analyte found in the final analysis of
Solution A as required in Exhibit E.
Under "Final Found Sol. AB," enter the concentration (in ug/L, to one
decimal place) of each analyte found in the final analysis of Solution
AB as required in Exhibit E.
For All Found values of solutions A and AB, enter the concentration
(positive, negative, or zero) of each analyte at each wavelength used
for analysis by ICP.
Under "Final Found %R," enter the value (to one decimal place) of the
percent recovery computed according to the following equation:
EQ. 2.7
„ _ Final Found Solution AB x
True Solution AB
All %R values reported shall be calculated using the exact true and
found values reported on this form.
Note that 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, it shall be reported in the "Final
Found" section of this form.
If more ICS analyses were required, submit additional FORMs IV-IN as
appropriate.
The order of reporting ICSs for each analyte shall follow the temporal
order in which the standards were run starting with the first Form IV
and continuing to the following Form IVs as appropriate. When multiple
wavelengths are used for one analyte, all the results of one wavelength
shall be reported before proceeding to the next wavelength.
H. Spike Sample Recovery [FORM V(PART 1)-IN]
This form is used to report results for the pre-digest spike.
Complete the header information according to the instructions in Part A
and as follows.
Indicate the appropriate matrix, level and concentration units (ug/L for
water and mg/Kg dry weight for soil) as explained in Parts A and C.
For "%Solids for Sample," enter the percent solids (as explained in Part
C) for the original sample of the EPA Sample Number reported on the
form. Note that this number must equal the one reported on Form I for
that sample.
B-27 ILM04.0
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Exhibit B Section III
In the "EPA Sample No." box, enter the EPA Sample Number (7 places
maximum) of the sample from which the spike results on this form were
obtained. The number shall be centered in the box.
Under "Control Limit %R," enter "75-125" if the spike added value was
greater than or equal to one-fourth of the sample result value. If not,
leave the field empty.
Under "Spiked Sample Result (SSR)," enter the measured value (to four
decimal places), in appropriate units, for each relevant analyte in the
matrix spike sample. Enter any appropriate qualifier, as explained in
Part C, to the "C" qualifier column immediately following the "Spiked
Sample Result (SSR)" column.
Under "Sample Result (SR)," enter the measured value (to four decimal
places) for each required analyte in the sample (reported in the EPA
Sample No. box) on which the matrix spike was performed. Enter any
appropriate qualifier, as explained in Part C, to the "C" qualifier
column immediately following the "Sample Result (SR)" column.
Under "Spike Added (SA)," enter the value (to two decimal places) for
the concentration of each analyte added to the sample. The same
concentration units shall be used for spiked sample results, unspiked
(original sample) results, and spike added sample results. If the
"spike added" concentration is specified in the contract, the value
added and reported shall be that specific concentration in appropriate
units, corrected for spiked sample weight and % solids (soils) or spiked
sample volume (waters).
Under "%R," enter the value (to one decimal place) of the percent
recovery for all spiked analytes computed according to the following
equation:
EQ. 2.8
""si— X 10°
%R shall be reported, whether it is negative, positive or zero.
The values for SSR, SR, and SA must be exactly those reported on this
form. A value of zero shall be used in calculations for SSR or SR if
the analyte value is less than the IDL.
Under "Q," enter "N" if the Spike Recovery (%R) is out of the control
limits (75-125) and the Spike Added (SA) is greater than or equal to
one-fourth of the Sample Result (SR) .
Under "M," enter the method used (as explained in Part C) or enter "NR1
if the analyte is not required in the spike.
B-28 ILM04.0
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Exhibit B Section III
If different samples were used for spike sample analysis of different
analytes, additional FORMs V(PART 1)-IN shall be submitted for each
sample as appropriate.
I. Post Digest Spike Sample Recovery [FORM V(PART 2)-IN]
This form is used to report results for the post-digest spike recovery
which is based upon the addition of a known quantity of analyte to an
aliquot of the digested sample.
Complete the header information according to the instructions in Part A
and as follows.
In the "EPA Sample No." box, enter the EPA Sample Number (7 spaces
maximum) of the sample from which the spike results on this form were
obtained. The number shall be centered in the box.
The "Control Limit %R" and "Q" fields shall be left blank until limits
are established by EPA. At that time, the Contractor will be informed
how to complete these fields.
Under "Spiked Sample Result (SSR)," enter the measured value (in ug/L,
to two decimal places) for each analyte in the post-digest spike sample.
Enter any appropriate qualifier, as explained in Part C, to the "C"
qualifier column immediately following the "Spiked Sample Result (SSR)"
column.
Under "Sample Result (SR)," enter the measured value (in ug/L, to two
decimal places) for the concentration of each analyte in the sample
(reported in the EPA Sample No. box) on which the spike was performed.
Enter any appropriate qualifier, as explained in Part C, to the "C"
qualifier column immediately following the "Sample Result (SR)" column.
Under "Spike Added (SA)," enter the value (in ug/L, to one decimal
place) for each analyte added to the sample. The same concentration
units shall be used for spiked sample results, unspiked (original
sample) results, and spike added sample results. If the spike added
concentration is specified in the contract, the value added and reported
shall be that specific concentration in appropriate units.
Under "%R," enter the value (to one decimal place) of the percent
recovery for all spiked analytes computed according to Equation 2.8 in
Part H.
%R shall be reported, whether it is negative, positive or zero.
The values for SSR, SR, and SA must be exactly those reported on this
form. A value of zero shall be substituted for SSR or SR if the analyte
value is less than the IDL.
Under "M, " enter the method used as explained in Part C, or enter "NR"
if the spike was not required.
B-29 ILM04.0
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Exhibit B Section III
If different samples were used for spike sample analysis of different
analytes, additional FORMs V(PART 1)-IN shall be submitted.
J. Duplicates [FORM VI-IN]
The duplicates form is used to report results of duplicate analyses.
Duplicate analyses are required for % solids values and all analyte
results.
Complete the header information according to the instructions in Part A
and as follows.
Indicate the appropriate matrix, level and concentration units (ug/L for
water and mg/Kg dry weight for soil) as explained in Parts A and C.
For "% Solids for Sample," enter the percent solids (as explained in
Part C) for the original sample of the EPA Sample Number reported on the
form. Note that this number must equal the one reported on Form I for
that sample.
For "% Solids for Duplicate," enter the percent solids (as explained in
Part C) for the duplicate sample of the EPA Sample Number reported on
the form.
In the "EPA Sample No." box, enter the EPA Sample Number (7 spaces
maximum) of the sample from which the duplicate sample results on this
form were obtained. The number shall be centered in the box.
Under "Control Limit," enter the CRDL (in appropriate units, ug/L for
water or mg/Kg dry weight basis compared to the original sample weight
and percent solids) for the analyte if the sample or duplicate values
were less than 5x CRDL and greater than or equal to the CRDL. If the
sample and duplicate values were greater than or equal to 5x CRDL, leave
the field empty.
Under Sample (S), enter the original measured value (to four decimal
places) for the concentration of each analyte in the sample (reported in
the EPA Sample No. box) on which a Duplicate analysis was performed.
Concentration units are those specified on the form. Enter any
appropriate qualifier, as explained in Part C, to the "C" qualifier
column immediately following the "Sample (S)" column.
Under Duplicate (D), enter the measured value (to four decimal places)
for each analyte in the Duplicate sample. Concentration units are those
specified on the form. Enter any appropriate qualifier, as explained in
Part C, to the "C" qualifier column immediately following the "Duplicate
(D)" column.
For solid samples, the concentration of the original sample shall be
computed using the weight and % solids of the original sample. The
concentration of the duplicate sample shall be computed using the weight
of the duplicate sample, but the % solids of the original sample.
B-30 ILM04.0
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Exhibit B Section III
Under RPD, enter the absolute value (to one decimal place) of the
Relative Percent Difference for all analytes detected above the IDL in
either the sample or the duplicate, computed according to the following
equation:
EQ. 2.9
S ~ D 100
(5 + D)/2
The values for S and D shall be exactly those reported on this form. A
value of zero shall 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
empty.
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 5x CRDL, then the RPD must be less than or equal to 20% to be in
control. If either sample or duplicate values are less than 5x CRDL,
then the absolute difference between the two values must be less than
the CRDL to be in control.
If both values are below the CRDL, then no control limit is applicable.
Under "M," enter method used as explained in Part C.
K. Laboratory Control Sample [FORM VII-IN]
This form is used to report results for the solid and aqueous Laboratory
Control Samples.
Complete the header information according to the instructions in Part A
and as follows.
For the Solid LCS Source (12 spaces maximum), enter the appropriate EPA
sample number if the EPA provided standard was used. Substitute an
appropriate number provided by the EPA for LCS solutions prepared in the
future. If other sources were used, identify the source as explained in
Part D. For the Aqueous LCS Source, enter the source name (12 spaces
maximum) as explained in Part D.
Under "Aqueous True," enter the value (in ug/L, to one decimal place) of
the concentration of each analyte in the Aqueous LCS Standard Source.
Under "Aqueous Found," enter the measured concentration (in ug/L, to two
decimal places) of each analyte found in the Aqueous LCS solution.
Under "Aqueous %R," enter the value of the percent recovery (to one
decimal place) computed according to the following equation:
B-31 ILM04.0
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Exhibit B Section III
EQ. 2.10
£„ _ Aqueous LCS Found
Aqueous LCS True
Under "Solid True," enter the value (in mg/Kg, to one decimal place) of
the concentration of each analyte in the Solid LCS Source.
Under "Solid Found," enter the measured value (in mg/Kg, to one decimal
place) of each analyte found in the Solid LCS solution.
Under "C," enter "B" or "U" or leave empty, to describe the found value
of the solid LCS as explained in Part C.
Under "Limits," enter the lower limit (in mg/Kg, to one decimal place)
in the left column, and the upper limit (in mg/Kg, to one decimal place)
in the right column, for each analyte in the Solid LCS Solution.
Under "Solid %R," enter the value of the percent recovery (to one
decimal place) computed according to the following equation:
EQ. 2.11
= Solid LCS Found x 100
Solid LCS True
The values for true and found aqueous and solid LCSs used in equations
2.10 and 2.11 shall be exactly those reported on this form. If the
analyte concentration is less than the IDL, a value of zero shall be
substituted for the solid LCS found.
Submit additional FORMs VII-IN as appropriate, if more than one aqueous
LCS or solid LCS was required.
L. Standard Addition Results [FORM VIII-IN]
This form is used to report the results of samples analyzed using the
Method of Standard Additions (MSA) for Furnace AA analysis.
Complete the header information according to the instructions in Part A.
Under "EPA Sample No.," enter the EPA Sample Numbers (7 spaces maximum)
of all analytical samples analyzed using the MSA. This includes reruns
by MSA (if the first MSA was out of control) as explained in Exhibit E.
Note that only field samples and duplicates may be reported on this
form, thus the EPA Sample Number usually has no suffix or a "D."
A maximum of 32 samples can be entered on this form. If additional
samples required MSA, submit additional FORMs VIII-IN. Samples shall be
listed in alphanumeric order per analyte, continuing to the next FORM
VIII-IN if applicable.
B-32 ILM04.0
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Exhibit B Section III
Under "An," enter the chemical symbol (2 spaces maximum) for each
analyte for which MSA was required for each sample listed. The analytes
shall be in alphabetical listing of the chemical symbols.
Results for different samples for each analyte shall be reported
sequentially, with the analytes ordered according to the alphabetical
listing of their chemical symbols. For instance, results for As
(arsenic) in samples MAA110, MAA111, and MAA112 would be reported in
sequence, followed by the result for Pb (lead) in MAA110, etc.
Under "O ADD ABS," enter the measured value in absorbance units (to
three decimal places) for the analyte before any addition is performed.
Under "1 ADD CON," enter the final concentration in ug/L (to two decimal
places) of the analyte (excluding sample contribution) after the first
addition to the sample analyzed by MSA.
Under "1 ADD ABS," enter the measured value (in the same units and
decimal places as "O ADD ABS") of the sample solution spiked with the
first addition.
Under "2 ADD CON," enter the final concentration in ug/L (to two decimal
places) of the analyte (excluding sample contribution) after the second
addition to the sample analyzed by MSA.
Under "2 ADD ABS," enter the measured value (in the same units and
decimal places as "O ADD ABS") of the sample solution spiked with the
second addition.
Under "3 ADD CON," enter the final concentration in ug/L (to two decimal
places) of the analyte (excluding sample contribution) after the third
addition to the sample analyzed by MSA.
Under "3 ADD ABS," enter the measured value (in the same units and
decimal places as "O ADD ABS") of the sample solution spiked with the
third addition.
Note that "O ADD ABS," "1 ADD ABS," "2 ADD ABS," and "3 ADD ABS" must
have the same dilution factor.
Under "Final Cone.," enter the final analyte concentration (in ug/L, to
one decimal place) in the sample as determined by MSA computed according
to the following formula:
EQ. 2.12
final Cone. = - (x-intercept)
Note that the final concentration of an analyte does not have to equal
the value for that analyte which is reported on FORM I-IN for that
sample.
B-33 ILM04.0
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Exhibit B Section III
Under "r," enter the correlation coefficient (to four decimal places)
that is obtained for the least squares regression line representing the
following points (x,y):(0.0, "0 ADD ABS"), ("1 ADD CON," "1 ADD ABS"),
("2 ADD CON," "2 ADD ABS"), ("3 ADD CON," "3 ADD ABS").
Note that the correlation coefficient shall be calculated using the
ordinary least squares linear regression (unweighted) according to the
following formula:
EQ. 2.13
r- &
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.
M. ICP Serial Dilutions [FORM IX-IN]
This form is used to report results for ICP serial dilution.
Complete the header information according to the instructions in Part A
and as follows.
In the "EPA Sample No." box, enter the EPA Sample Number (7 places
maximum) of the sample for which serial dilution analysis results on
this form were obtained. The number shall be centered in the box.
Under "Initial Sample Result (I)," enter the measured value (in ug/L, to
two decimal places) for each ICP analyte in the undiluted sample (for
the EPA sample number reported on this form). Enter any appropriate
qualifier, as explained in Part C, to the "C" qualifier column
immediately following the "Initial Sample Result (I)" column.
Note that the Initial Sample Concentration for an analyte does not have
to equal the value for that analyte reported on FORM I-IN for that
sample. It is the value of the analyte concentration (uncorrected for
dilution) that is within the linear range of the instrument.
Under "Serial Dilution Result (S)", enter the measured concentration
value (in ug/L, to two decimal places) for each ICP analyte in the
diluted sample. The value shall be adjusted for that dilution. Enter
any appropriate qualifier, as explained in Part B, to the "C" qualifier
column immediately following the "Serial Dilution Result (S)" column.
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 and that the "C" qualifier for the serial dilution shall be
established based on the serial dilution result before correcting it for
the dilution regardless of the value reported on the form.
Under "% Difference," enter the absolute value (to one decimal place) of
the percent difference in concentration of required analytes, between
B-34 ILM04.0
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Exhibit B Section III
the original sample and the diluted sample (adjusted for dilution)
according to the following formula:
EQ. 2.14
% Difference = [ J S [ x 100
The values for I and S used to calculate % Difference in equation 2.14
shall be exactly those reported on this form. A value of zero shall be
substituted for S if the analyte concentration is less than the IDL. If
the analyte concentration in (I) is less than the IDL concentration,
leave "% Difference" field empty.
Under "Q," enter "E" if the % Difference is greater than 10% and the
original sample concentration (reported on FORM I-IN) is greater than
50x the IDL reported on FORM X-IN.
Under "M," enter the method of analysis for each analyte as explained in
Part C.
N. Instrument Detection Limits (Quarterly) [FORM X-IN]
This form documents the Instrument Detection Limits for each instrument
that the laboratory used to obtain data for the Sample Delivery Group.
Only the instrument and wavelengths used to generate data for the SDG
shall be included.
Although the Instrument Detection Limits (IDLs) are determined quarterly
(i.e., January, April, July, October) a copy of the quarterly instrument
detection limits shall be included with each SDG data package on FORM(s)
X-IN.
Complete the header information according to the instructions in Part A
and as follows.
Enter the date (formatted MM/DD/YY) on which the IDL values were
obtained (or became effective).
Enter ICP ID Number, Flame AA ID Number, and Furnace AA ID Number (12
spaces maximum each). These ID Numbers are used to uniquely identify
each instrument that the laboratory uses to do CLP work.
Enter the Mercury instrument ID number in the Flame AA ID Number field.
Enter the Cyanide instrument ID number in the Flame AA ID Number field.
Under "Wavelength," enter the wavelength in nanometers (to two decimal
places) for each analyte for which an Instrument Detection Limit (IDL)
has been established and is listed in the IDL column. If more than one
wavelength is used for an analyte, use other FORMs X-IN as appropriate
to report the Instrument Detection Limit.
B-35 ILM04.0
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Exhibit B Section III
Under "Background," enter the type of background correction used to
obtain Furnace AA data. Enter "BS" for Smith Hieftje, "BD" for
Deuterium Arc, or "BZ" for Zeeman background correction.
Contract Required Detection Limits (in ug/L) as established in Exhibit
C, shall appear in the column headed "CRDL."
Under "IDL," enter the Instrument Detection Limit (ug/L, to one decimal
place) as determined by the laboratory for each analyte analyzed by the
instrument for which the ID Number is listed on this form. When
calculating IDL values, always round up to the appropriate significant
figure. This deviation from the EPA rounding rule is necessary to
prevent the reporting of detected values for results that fall in the
noise region of the calibration curve.
Under "M," enter the method of analysis used to determine the instrument
detection limit for each wavelength used. Use appropriate codes as
explained in Part C.
Use additional FORMs X-IN if more instruments and wavelengths are used.
Note that the date on this form shall not exceed the analysis dates in
the SDG data package or precede them by more than three months.
Use the Comments section to indicate alternative wavelengths and the
conditions under which they are used.
O. ICP Interelement Correction Factors (Annually) [FORM XI(PART 1)-IN]
This form documents for each ICP instrument the interelement correction
factors applied by the Contractor laboratory to obtain data for the
Sample Delivery Group.
Although the correction factors are determined annually (every twelve
calendar months), a copy of the results of the annual interelement
correction factors shall be included with each SDG data package on FORM
XI(PART 1)-IN, and FORM XI(PART 2)-IN as appropriate.
Complete the header information according to instructions in Part A and
as follows.
Enter the ICP ID Number (12 spaces maximum), which is a unique number
designated by the laboratory to identify each ICP instrument used to
produce data in the SDG package. If more than one ICP instrument is
used, submit additional FORMs XI(PART 1)-IN as appropriate.
Report the date (formatted as MM/DD/YY) on which these correction
factors were determined for use. This date shall not exceed the ICP
analysis dates in the SDG data package or precede them by more than
twelve calendar months.
Under "Wavelength," list the wavelength in nanometers (to two decimal
places) used for each ICP analyte. If more than one wavelength is used,
submit additional FORMS XI(PART 1)-IN or FORMs XI(PART 2)-IN, as
appropriate.
B-36 ILM04.0
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Exhibit B Section III
Under "Al," "Ca," "Fe," and "Mg" enter the correction factor (negative,
positive or zero, to seven decimal places, 10 spaces maximum) for each
ICP analyte. If correction factors for another analyte are applied, use
the empty column and list the analyte's chemical symbol in the blank
two-space header field provided for that column.
If corrections are not applied for an analyte, a zero shall be entered
for that analyte to indicate that the corrections were determined to be
zero. If correction factors are applied for more than one additional
analyte, use FORM XI(PART 2)-IN, as appropriate.
P. ICP Interelement Correction Factors (Annually) [FORM XI(PART 2)-IN, ]
This form is used if correction factors for analytes other than Al, Ca,
Fe, Mg, and one more analyte of the Contractor's choice were applied to
the analytes analyzed by ICP. Complete this form as for FORM XI(PART
1)-IN by listing the chemical symbol for additional analytes in the
heading of the empty columns in the two-space fields provided.
Columns of correction factors for additional analytes shall be entered
left to right starting on FORM XI(PART 1)-IN and proceeding to FORM
XI(PART 2)-IN, according to the alphabetical order of their chemical
symbols. Note that correction factors for Al, Ca, Fe, and Mo, are all
required and are to be listed first (as they appear on FORM XKPART 1)-
IN) .
Q. ICP Linear Ranges (Quarterly) [FORM XII-IN]
This form documents the quarterly linear range analysis for each ICP
instrument that the laboratory used to obtain data for the SDG.
Complete the header information according to the instructions in Part A
and as follows.
Enter rhe ICP ID Number (12 spaces maximum), which is a unique number
designated by the Contractor to identify each ICP instrument used to
produce data for the SDG. If more than one ICP instrument is used,
submit additional FORMS XII-IN as appropriate.
Report the date (formatted as MM/DD/YY) on which these linear ranges
were determined for use. This date shall not exceed the dates of
analysis by ICP in the SDG data package and shall not precede the
analysis dates by more than three calendar months.
Under "Integ. Time (Sec.)," enter the integration time (in seconds to
two decimal places) used for each measurement taken from the ICP
instrument.
Under "Concentration," enter the concentration (in ug/L) that is the
upper limit of the ICP instrument linear range as determined in Exhibit
E. Any measurement in the SDG data package at or below this
concentration is within the linear range. Any measurement above it is
out of the linear range, and thus, is an estimated value and shall be
diluted into the linear range.
B-37 ILM04.0
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Exhibit B Section III
Under "M," enter the method of analysis for each analyte as explained in
Part C.
If more instruments or analyte wavelengths are used, submit additional
FORMs XII-IN as appropriate.
R. Preparation Log [Form XIII-IN]
This Form is used to report the preparation run log.
All field samples and all quality control preparations (including
duplicates, matrix spikes, LCSs, PBs and repreparations) associated with
the SDG shall be reported on Form XIII.
Submit one Form XIII per batch, per method, if no more than thirty-two
preparations, including quality control preparations, were performed.
If more than thirty-two preparations per batch, per method, were
performed, then submit additional copies of Form XIII as appropriate.
Submit a separate Form XIII for each batch.
The order in which the Preparation Logs are submitted is very important.
Form XIII shall be organized by method, by batch. Later batches within
a method shall follow earlier ones. Each batch shall start on a
separate Form XIII.
Complete the header information according to the instructions in Part A,
and as follows:
For "Method," enter the method of analysis (two characters maximum) for
which the preparations listed on the Form were made. Use appropriate
method codes as specified in Part C.
Under "EPA Sample No.," enter the EPA Sample Number of each sample in
the SDG, and of all other preparations such as duplicates, matrix
spikes, LCSs, PBs, and repreparations (all formatted according to Table
2). All EPA Sample Numbers shall be listed in ascending alphanumeric
order, continuing to the next Form XIII if applicable.
Under "Preparation Date," enter the date (formatted MM/DD/YY) on which
each sample was prepared for analysis by the method indicated in the
header section of the Form.
Note that the date never changes on a single Form XIII because the form
shall be submitted per batch.
Under "Weight," enter the wet weight (in grams, to two decimal places)
of each soil sample prepared for analysis by the method indicated in the
header section of the Form. If the sample matrix is water, then leave
the field empty.
Under "Volume," enter the final volume (in mL, 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 shall
have a value for each sample listed.
B-38 ILM04.0
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Exhibit B Section III
S. Analysis Run Log [Form XIV-IN]
This Form is used to report the sample analysis run log.
A run is defined as the totality of analyses performed by an instrument
throughout the sequence initiated by, and including, the first SOW-
required calibration standard and terminated by, and including, the
continuing calibration verification and blank following the last SOW-
required analytical sample.
All field samples and all quality control analyses (including
calibration standards, ICVs, CCVs, ICBs, CCBs, CRAs, CRIs, ICSs, LRSs,
LCSs, PBs, duplicates, serial dilutions, pre-digestion spikes, post-
digestion spikes, analytical spikes, and each addition analyzed for the
method of standard addition determination) associated with the SDG shall
be reported on Form XIV. The run shall be continuous and inclusive of
all analyses performed on the particular instrument during the run.
Submit one Form XIV per run if no more than thirty-two (32) analyses,
including instrument calibration, were analyzed in the run. If more
than thirty-two analyses were performed in the run, submit additional
Forms XIV as appropriate.
The order in which the Analysis Run Logs are submitted is very
important. Form XIV shall be organized by method, by run. Later runs
within a method shall follow earlier ones. Each analytical run shall
start on a separate Form XIV. Therefore, instrument calibration shall
be the first entry on the form for each new run. In addition, the run
is considered to have ended if it is interrupted for any reason,
including termination for failing QC parameters.
Complete the header information according to the instructions in Part A,
and as follows:
For "Instrument ID Number," enter the instrument ID number (12 spaces
maximum) which shall 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
instrument is used, submit additional Forms XIV as appropriate.
For "Method," enter the method code (two characters maximum) according
to the specifications in Part C.
For "Start Date," enter the date (formatted MM/DD/YY) on which the
analysis run was started.
For "End Date," enter the date (formatted MM/DD/YY) on which the
analysis run was ended.
Under "EPA Sample No.," enter the EPA sample number of each analysis,
including all QC operations applicable to the SDG (formatted according
to Table 2). All EPA Sample Numbers shall be listed in increasing
temporal (date and time) order of analysis, continuing to the next Form
XIV for the instrument run if applicable. The analysis date and time of
B-39 ILM04.0
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Exhibit B Section III
other analyses not associated with the SDG, but analyzed by the
instrument in the reported analytical run, shall be reported. Those
analyses shall be identified with the EPA Sample No. of "ZZZZZZ."
Under "D/F," enter the dilution factor (to two decimal places) by which
the final digestate or distillate needed to be diluted for each analysis
to be performed. The dilution factor does not include the dilution
inherent in the preparation as specified by the preparation procedures
in Exhibit D.
The dilution factor is required for all entries on Form XIV.
Note that for a particular sample a dilution factor of "1" shall be
entered if the digestate or distillate was analyzed without adding any
further volume of dilutant or any other solutions to the "Volume" or an
aliquot of the "Volume" listed on Form XIII for that sample.
For EPA supplied solutions such as ICVs, ICSs, and LCSs, a dilution
factor shall 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 shall be that
which would make the reported true values on the appropriate form for
the solution equal those that were supplied with the solution by the
EPA. For instance, ICV-2(0887) has a true value of 104.0 ug/L at a 20
fold dilution. If the solution is prepared at a 40 fold dilution, a
dilution factor of "2" shall be entered on Form XIV 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 shall be corrected for the
dilution listed on Form XIV using the following formula:
EQ. 2.15
Found value on Form II = Instrument readout (ug/L) x D/F
Under "Time," enter the time (in military format - HHMM) at which each
analysis was performed. If an autosampler is used with equal analysis
time and intervals between analyses, then only the start time of the run
(the time of analysis of the first calibration standard) and end time of
the run (the time of analysis of the final CCV or CCB, whichever is
later) need to be reported.
Under "% R," enter the percent recovery (to one decimal place) for each
Furnace AA analytical spike analyzed. If the analytical spike was
performed on more than one analyte, use additional Forms XIV as
appropriate. Leave the "% R" field empty if the analysis reported is
not for an analytical spike. %R shall be recorded even if the result is
not used.
A %R value of "-9999.9" shall be entered for the analytical spike if
either the sample or analytical results are greater than the calibration
range of the instrument.
B-40 ILM04.0
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Exhibit B Section III
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 in the SDG. Leave the column empty for each analyte if the
analysis was not used to report the particular analyte.
Entering "X" appropriately is very important. The "X" is used to link
the samples with their related QC. It also links the dilution factor
with the appropriate result reported on Forms I-IX. For each analyte
result reported on any of the Forms I-IX, there shall be one, and only
one, properly identified entry on Form XIV for which an "X" is entered
in the column for that analyte.
T. Sample Log-In Sheet [Form DC-1]
This form is used to document the receipt and inspection of samples and
containers. One original of 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 Sample Delivery
Group, the original Form DC-1 shall be placed with the deliverables for
the Sample Delivery Group of the lowest Arabic number and a copy of Form
DC-1 shall be placed with the deliverables for the other Sample Delivery
Group(s). The copies should be identified as "copy(ies)," and the
location of the original should be noted on the copies.
Sign and date the airbill (if present). Examine the shipping container
and record the presence/absence of custody seals and their condition
(i.e., intact, broken) in item 1 on Form DC-1. Record the custody seal
numbers in item 2.
Open the container, remove the enclosed sample documentation, and record
the presence/absence of chain-of-custody record(s), EPA 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.
Remove the samples from the shipping container(s), examine the samples
and the sample tags (if present), and record the condition of the sample
bottles (i.e., intact, broken, leaking) and presence or absence of
sample tags in items 7 and 8 on Form DC-1.
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.
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 laboratory should be recorded in items 10 and 11.
Cross out unused columns and spaces.
B-41 ILM04.0
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Exhibit B Section III
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.
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.
U. 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.
Organize all EPA-CSF documents as described in Exhibit B, Section II and
Section III. Assemble the documents in the order specified on Form DC-2
and Section II, and stamp each page with the consecutive number. (Do
not number Form DC-2). Inventory the CSF by reviewing the document
numbers and recording page number ranges in the columns provided on Form
DC-2. If there are no documents for a specific document type, enter an
"NA" in the empty space.
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 them under Categories
29, 30, 31, or 32. Category 32 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.
If it is necessary to insert new or inadvertently omitted documents
prior to providing CSFs as first deliverables, the Contractor shall
follow these steps:
a. Number all documents to be inserted with the next sequential
numbers and file the inserts in their logical positions within the
CSF (e.g., file document 1000 between documents 6 and 7).
b. Identify where the inserts are filed in the CSF by recording the
document numbers and their locations under the "Other Records"
section of Form DC-2 (e.g., document 1000 is filed between 6 and
7).
B-42 ILM04.0
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SECTION IV
DATA REPORTING FORMS
B-43 ILM04.0
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U.S. EPA - CLP
COVER PAGE - INORGANIC ANALYSES DATA PACKAGE
Lab Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
SOW No.:
EPA Sample No. Lab Sample ID.
Were ICP interelement corrections applied? Yes/No
Were ICP background corrections applied? Yes/No
If yes-were raw data generated before
application of background corrections? Yes/No
Comments:
I certify that this data package is in compliance with the terms and
conditions of the contract, both technically and for completeness, for other
than the conditions detailed above. Release of the data contained in this
hardcopy 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.
S igna tur e: Name:
Date: Title:
COVER PAGE - IN ILM04
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U.S. EPA - CLP
Lab Name:
Lab Code:
INORGANIC ANALYSIS DATA SHEET
Contract:
SAS No.:
EPA SAMPLE NO.
Case No.:
SDG No.:
Matrix (soil/water):
Level (low/med):
% Solids:
Lab Sample ID;
Date Received:
Concentration Units (ug/L or mg/kg dry weight):
CAS No.
7429-90-5
7440-36-0
7440-38-2
7440-39-3
7440-41-7
7440-43-9
7440-70-2
7440-47-3
7440-48-4
7440-50-8
7439-89-6
7439-92-1
7439-95-4
7439-96-5
7439-97-6
7440-02-0
7440-09-7
7782-49-2
7440-22-4
7440-23-5
7440-28-0
7440-62-2
7440-66-6
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Concentration
C
Q
M
Color Before:
Color After:
Comments:
Clarity Before:
Clarity After:
Texture:
Artifacts:
FORM I - IN
ILM04.0
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U.S. EPA - CLP
2A
INITIAL AND CONTINUING CALIBRATION VERIFICATION
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.
Initial Calibration Source:
Continuing Calibration Source:
Concentration Units: ug/L
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Initial Calibration
True Found %R(1)
Continuing Calibration
True Found %R(1) Found %R(1)
M
—
—
—
—
—
—
(1) Control Limits: Mercury 80-120; Other Metals 90-110; Cyanide 85-115
FORM II (PART 1) - IN
ILM04.C
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U.S. EPA - CLP
2B
CRDL STANDARD FOR AA AND ICP
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
AA CRDL Standard Source:
ICP CRDL Standard Source:
Concentration Units: ug/L
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
CRDL Standard for AA
True Found %R
CRDL Standard for ICP
Initial Final
True Found %R Found %R
Control Limits: no limits have been established by EPA at this time
FORM II (PART 2) - IN
ILM04.0
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U.S. EPA - CLP
BLANKS
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.
Preparation Blank Matrix (soil/water):
Preparation Blank Concentration Units (ug/L or rag/kg):
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Initial
Calib.
Blank
(ug/L) C
Continuing Calibration
Blank (ug/L)
1 C 2 C 3 C
—
Prepa-
ration
Blank C
—
—
—
M
—
—
FORM III - IN
ILM04.0
-------
U.S. EPA - CLP
ICP INTERFERENCE CHECK SAMPLE
Lab Name:
Lab Code:
Case No. :
Contract:
SAS No . :
SDG No.
ICP ID Number:
ICS Source:
Concentration Units: ug/L
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
True
Sol. Sol.
A AB
Initial Found
Sol. Sol.
A AB %R
Final Found
Sol. Sol.
A AB %R
FORM IV - IN
ILM04.0
-------
U.S. EPA - CLP
Lab Name:
Lab Code:
5A
SPIKE SAMPLE RECOVERY
Contract:
Case No.:
SAS No.:
Matrix (soil/water):
% Solids for Sample:
EPA SAMPLE NC
SDG No.
Level (low/med)
Concentration Units (ug/L or mg/kg dry weight):
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Control
Limit
°.p
•SrC
Spiked Sample
Result (SSR)
C
Sample
Result (SR)
C
Spike
Added (SA)
%R
Q
M
Comments:
FORM V (PART 1) - IN
ILM04
-------
U.S. EPA - CLP
Lab Name:
Lab Code:
5B
POST DIGEST SPIKE SAMPLE RECOVERY
Contract:
EPA SAMPLE NO,
Case No.:
SAS No.:
SDG No.
Matrix (soil/water):
Level (low/med)
Concentration Units: ug/L
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Control
Limit
%R
Spiked Sample
Result (SSR)
C
Sample
Result (SR)
C
Spike
Added (SA)
%R
Q
M
Comments:
FORM V (PART 2) - IN
ILM04.0
-------
Lab Name:
Lab Code:
U.S. EPA - CLP
DUPLICATES
Contract:
EPA SAMPLE NC
Case No.:
SAS No.:
SDG No.
Matrix (soil/water):
% Solids for Sample:
Level (low/med)
% Solids for Duplicate:
Concentration Units (ug/L or mg/kg dry weight):
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Control
Limit
Sample (S)
C
Duplicate (D)
C
RPD
Q
M
FORM VI - IN
ILM04
-------
U.S. EPA - CLP
Lab Name:
Lab Code:
LABORATORY CONTROL SAMPLE
Contract:
SAS No.:
Case No.:
SDG No,
Solid LCS Source:
Aqueous LCS Source:
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Aqueous (ug/L)
True Found %R
Solid (mg/kg)
True Found C Limits %R
—
—
—
—
—
FORM VII - IN
ILM04.0
-------
U.S. EPA - CLP
Lab Name:
Code:
8
STANDARD ADDITION RESULTS
Contract:
Case No.: SAS No. :
SDG No.
Concentration Units: ug/L
EPA
Sample
No.
An
0 ADD
ABS
1 AI
CON
)D
ABS
2 AE
CON
)D
ABS
3 At
CON
)D
ABS
Final
Cone.
r
Q
FORM VIII - IN
ILM04.0
-------
U.S. EPA - CLP
EPA SAMPLE NO.
Lab Name:
Lab Code:
Case No.:
ICP SERIAL DILUTIONS
Contract:
SAS No.:
SDG No.:
Matrix (soil/water):
Level (low/med):
Concentration Units: ug/L
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Initial Sample
Result (I)
C
Serial
Dilution
Result (S)
C
%
Differ-
ence
Q
M
FORM IX - IN
ILM04.0
-------
U.S. EPA - CLP
10
INSTRUMENT DETECTION LIMITS (QUARTERLY)
Lab Name:
Lab Code:
Case No.:
ICP ID Number:
Flame AA ID Number:
Furnace AA ID Number:
Contract:
_SAS No. :
Date:
SDG No.:
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Wave-
length
(nm)
Back-
ground
CRDL
(ug/L)
200
60
10
200
5
5
5000
10
50
25
100
3
5000
15
0.2
40
5000
5
10
5000
10
50
20
10
IDL
(ug/L)
M
Comments:
FORM X - IN
ILM04
-------
U.S. EPA - CLP
11A
ICP INTERELEMENT CORRECTION FACTORS (ANNUALLY)
Lab Name:
Lab Code:
ICP ID Number:
Case No.:
Contract:
SAS No.:
Date:
SDG No.
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Wave-
length
(nm)
Ir
Al
iterelement
Ca
Correction
Fe
Factors foi
Mg
•» •
Comments:
FORM XI (PART 1) - IN
ILM04.0
-------
U.S. EPA - CLP
11B
ICP INTERELEMENT CORRECTION FACTORS (ANNUALLY)
Lab Name:
Lab Code:
Case No.
ICP ID Number:
Contract:
SAS No.:
Date:
SDG No.
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Wave-
length
(nm)
Ir
iterelement
Correction
Factors for
Comments:
FORM XI (PART 2) - IN
ILM04
-------
U.S. EPA - CLP
12
ICP LINEAR RANGES (QUARTERLY)
Lab Name:
Lab Code:
Case No.:
ICP ID Number:
Contract:
SAS No.:
Date:
SDG No.
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Integ.
Time
(Sec. )
Concentration
(ug/L)
M
—
^_^_
Comments:
FORM XI (PART 2) - IN
ILM04.0
-------
Lab Name:
Lab Code:
Method:
Case No.:
U.S. EPA - CLP
13
PREPARATION LOG
Contract:_
SAS No.:
SDG No.
EPA
Sample
No.
Preparation
Date
Weight
(gram)
Volume
(mL)
FORM XIII - IN
ILM04
-------
U.S. EPA - CLP
14
ANALYSIS RUN LOG
Lab Name:
Lab Code:
Case No.
Instrument ID Number:
Start Date:
Contract:
SAS No.:
Method: _
End Date:
SDG No.
EPA
Sample
No.
D/F
Time
% R
Analytes
A
L
S
B
A
S
B
A
B
E
C
D
C
A
C
R
C
O
C
U
F
E
P
B
M
G
M
N
H
G
N
I
K
S
E
A
G
N
A
T
L
V
Z
N
C
N
Form XIV - IN
ILM04.0
-------
EXHIBIT C
INORGANIC TARGET ANALYTE LIST
C-l ILM04.0
-------
INORGANIC TARGET ANALYTE LIST (TAL) - TABLE 1
Contract Required
19
Detection Limit^'^
Analyte (ug/L)
Aluminum 200
Antimony 60
Arsenic 10
Barium 200
Beryllium 5
Cadmium 5
Calcium 5000
Chromium 10
Cobalt 50
Copper 25
Iron 100
Lead 3
Magnesium 5000
Manganese 15
Mercury 0.2
Nickel 40
Potassium 5000
Selenium 5
Silver 10
Sodium 5000
Thallium 10
Vanadium 50
Zinc 20
Cyanide 10
(1) Subject to the restrictions specified in Exhibits D and E, any
analytical method specified in ILM04.0, Exhibit D may be utilized as
long as the documented instrument or method detection limits meet the
Contract Required Detection Limit (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 instrument or method detection limit may not equal the Contract
Required Detection Limit. This is illustrated in the example below:
For lead: Method in use = ICP
Instrument Detection Limit (IDL) = 40
Sample concentration = 220
Contract Required Detection Limit (CRDL) = 3
The value of 220 may be reported even though the instrument detection
limit is greater than CRDL. The instrument or method detection limit
must be documented as described in Exhibits B and E.
(2) The CRDLs are the minimum levels of detection acceptable under the
contract Statement of Work,
C-2 ILM04.0
-------
EXHIBIT D
ANALYTICAL METHODS
Page No.
SECTION I - INTRODUCTION D-l
Figure 1-Inorganics Methods Flow Chart D-3
SECTION II - SAMPLE PRESERVATION AND HOLDING TIMES D-4
Part A - Sample Preservation D-4
Part B - Holding Times D-4
SECTION III - SAMPLE PREPARATION D-5
Part A - Water Sample Preparation D-5
Part B - Soil/Sediment Sample Preparation D-5
Part C - Microwave Digestion Method D-8
Part D - Mercury and Cyanide Preparation D-14
SECTION IV - SAMPLE ANALYSIS D-15
Part A - Inductively Coupled Plasma-Atomic
Emission Spectrometric Method D-16
Part B - Atomic Absorption Methods, Furnace Technique . . . D-28
Part C - Atomic Absorption Methods, Flame Technique .... D-41
Part D - Cold Vapor Methods for Mercury Analysis D-46
Part E - Methods for Total Cyanide Analysis D-60
Part F - Percent Solids Determination Procedure D-84
ILM04.0
-------
Exhibit D Section I
SECTION I
INTRODUCTION
Inorganic Methods Flow Chart; Figure 1 outlines the general analytical scheme the
Contractor shall follow in performing analyses under this contract.
Permitted Methods; Any analytical method specified in Exhibit D may be used as long
as the documented instrument or method detection limits meet the Contract Required
Detection Limits (Exhibit C). 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.
Initial Run Undiluted; All samples must initially be run undiluted (i.e., final
product of the sample preparation procedure). When an analyte concentration exceeds
the calibrated or linear range (as appropriate), re-analysis for that analyte(s) is
required after appropriate dilution. The Contractor shall use the least dilution
necessary to bring the analyte(s) within the valid analytical range (but not below
the CRDL) and report the highest valid value for each analyte as measured from the
undiluted and diluted analyses. Unless the Contractor can submit proof that
dilution was required to obtain valid results, both diluted and undiluted sample
measurements must be contained in the raw data. ICP data showing a high
concentration for a particular analyte, combined with an analyte result that is
close to the middle range of the calibration curve in the diluted sample, constitute
sufficient proof that the sample had to initially be run diluted for that analyte on
a furnace AA instrument. All sample dilutions shall be made with deionized water
appropriately acidified to maintain constant acid strength.
Quality Assurance/Oualitv Control Measurements: The Contractor is reminded and
cautioned that Exhibit D is a compendium of required and/or permitted analytical
methods to be used in the performance of analyses under this contract. The quality
assurance/quality control procedures or measurements to be performed in association
with these methods or analyses are specified in Exhibit E. In the event references
to quality assurance measurements in any of the methods appear to be in conflict
with or to be less stringent than the requirements of Exhibit E, the requirements of
Exhibit E will prevail.
Raw Data Requirements: The Contractor is reminded and cautioned that the collection
and provision of raw data may or may not be referred to within the individual
methods of Exhibit D or the Quality Assurance Protocol of Exhibit E. The Raw Data
Deliverables requirements are specified in Exhibit B, Section II.C.2.d. Raw data
collected and provided in association with the performance of analyses under this
contract shall conform to the appropriate provisions of Exhibit B,
Glassware Cleaning: Lab glassware to be used in metals analysis must be acid
cleaned according to EPA's manual "Methods for Chemical Analysis of Water and
Wastes" or an equivalent procedure.
Standard Stock Solutions: Stock solutions to be used for preparing instrument or
method calibration standards may be purchased or prepared as described in the
individual methods of Exhibit D. All other solutions to be used for quality
assurance/quality control measurements shall conform to the specific requirements of
Exhibit E.
D-l ILM04.0
-------
Exhibit D Section I
Aqueous Sample pH Measurement; Before sample preparation is initiated on an aqueous
sample received in shipment, the Contractor shall check the pH of the sample and
note in a preparation log if the pH is <2 for a metals sample or if the pH is >12
for a cyanide sample. The Contractor shall not perform any pH adjustment action if
the sample has not been properly preserved. If the sample has not been properly
preserved, contact SMO before proceeding with the preparation and analysis for
further instructions.
Sample Mixing: Unless instructed otherwise by the EPA Administrative Project
Officer or Technical Project Officer, all samples shall be mixed thoroughly prior to
aliquoting for digestion. No specific procedure is provided herein for
homogenization of soil/sediment samples; however, an effort should be made to obtain
a representative aliquot.
Background Corrections: Background corrections are required for Flame AA
measurements below 350 nm and for all Furnace AA measurements. For ICP background
correction requirements, see Exhibit D Section IV, Part A, paragraph 2.0.
Replicate Injections/Exposures: Each furnace analysis requires a minimum of two
injections (burns), except for full method of standard addition (MSA). All ICP
measurements shall require a minimum of two replicate exposures. Appropriate hard
copy raw data for each exposure/injection shall be included in the data package in
accordance with Exhibit B, Section II, Part C, paragraph 2.d. The average of each
set of exposures/injections shall be used for standardization, sample analysis, and
reporting as specified in Exhibit D.
Dissolved Metals: If dissolved rnetals are requested by the EPA Regional offices, the
Contractor shall follow the instructions provided on the Traffic Report(s). If
there are no instructions on the Traffic Report, the Contractor shall digest the
samples designated as dissolved metals.
If the Regional office indicates on the Traffic Report that a digestion is not to be
performed when analyzing field samples for dissolved metals, then an aqueous
laboratory control sample (LCS) and a post-digestion (hardcopy Form 5B and diskette
QC codes PDO and PDF) spike sample are not required.
D-2 ILM04.0
-------
Exhibit D Section I
Figure 1
INORGANICS METHODS FLOW CHART
Field Sample
! Traffic Report or SMO |
| Specified Parameters |
i
i
Water
Matrix
Cyanide Acid Digestion
Analysis for Metals
in Water Analysis
| in Water
i
i
Soil /Sediment
Matrix
i
Acid Digestion |% Solids | Cyanide j
for Metals |Determin- [Analysis!
Analysis in j ation | in Soil/,
] Soil /Sediment i | | Sediment |
i
i
! Metals Anal. |
! ICP/AAS i
Data
|Metals Anal.
! ICP/AAS |
Reports
i
D-3
ILM04.0
-------
Exhibit D Section II
SECTION II
SAMPLE PRESERVATION AND HOLDING TIMES
A. SAMPLE PRESERVATION
1. Water Sample Preservation
Measurement
Parameter Container^) Preservative (
Metals P,G HNO3 to pH <2
Cyanide, total P,G 0.6g ascorbic
and amenable NaOH to pH >12
to chlorination Cool, maintain at 4°C(+2°C)
until analysis
FOOTNOTES:
(1) Polyethylene (P) or glass (G).
(2) Sample preservation is performed by the sampler immediately upon
sample collection.
(3) Only used in the presence of residual chlorine.
2. Soil/Sediment Sample Preservation
The preservation required for soil/sediment samples is maintenance at
4°C (+ 2°) until analysis.
B. HOLDING TIMES FOR WATER AND SOIL/SEDIMENT SAMPLES
Following are the maximum sample holding times allowable under this contract.
To be compliant with this contract, the Contractor shall analyze samples
within these times even if these times are less than the maximum data
submission times allowed in this contract.
No. of Days Following
Analyte Sample Receipt
by Contractor
Mercury 26 days
Metals (other than mercury) 180 days
Cyanide 12 days
D-4 ILM04.0
-------
Exhibit D Section III
SECTION III
SAMPLE PREPARATION
A. WATER SAMPLE PREPARATION
1. Acid Digestion Procedure for Furnace Atomic Absorption Analysis
Shake sample and transfer 100 mL of well-mixed sample to a 250-mL
heating vessel, add 1 mL of (1+1) HNO3 and 2 mL 30% H202 to the sample.
Cover with watch glass or similar cover and heat on a steam bath, hot
plate or equivalent heating source which is adjustable and capable of
maintaining a temperature of 92-95°C for 2 hours or until sample volume
is reduced to between 25 and 50 mL, making certain sample does not boil.
Cool sample and filter to remove insoluble material. (NOTE: In place of
filtering, the sample, after dilution and mixing, may be centrifuged or
allowed to settle by gravity overnight to remove insoluble material.)
Adjust sample volume to 100 mL with deionized distilled water. The
sample is now ready for analysis.
Concentrations so determined shall be reported as "total."
If Sb is to be determined by furnace AA, use the digestate prepared for
ICP/flame AA analysis.
2. Acid Digestion Procedure for ICP and Flame AA Analyses
Shake sample and transfer 100 mL of well-mixed sample to a 250-mL
heating vessel, add 2 mL of (1+1) HNO3 and 10 mL of (1+1) HC1 to the
sample. Cover with watch glass or similar cover and heat on a steam
bath, hot plate or equivalent heating source which is adjustable and
capable of maintaining a temperature of 92-95°C for 2 hours or until
sample volume is reduced to between 25 and 50 mL, making certain sample
does not boil. Cool sample and filter to remove insoluble material.
(NOTE: In place of filtering, the sample, after dilution and mixing, may
be centrifuged or allowed to settle by gravity overnight to remove
insoluble material.) Adjust sample volume to 100 mL with deionized
distilled water. The sample is now ready for analysis.
Concentrations so determined shall be reported as "total."
B. SOIL/SEDIMENT SAMPLE PREPARATION
1. Acid Digestion Procedure for ICP, Flame AA and Furnace AA Analyses
a. Scope and Application
This method is an acid digestion procedure used to prepare
sediments, sludges, and soil samples for analysis by flame or
furnace atomic absorption spectroscopy (AAS) or by inductively
coupled plasma spectroscopy (ICP). Samples prepared by this
method may be analyzed by AAS or ICP for the following metals:
D-5 ILM04.0
-------
Exhibit D Section III
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
b. Summary of Method
A representative 1 g (wet weight) sample is digested in nitric
acid and hydrogen peroxide. The digestate is then refluxed with
either nitric acid or hydrochloric acid. Hydrochloric acid is
used as the final reflux acid for the furnace AA analysis of Sb
and the Flame AA or ICP analysis of Al, As, Sb, Ba, Be, Ca, Cd,
Cr, Co, Cu, Fe, Pb, Mg, Mn, Ni, K, Se, Ag, Na, Tl, V and Zn.
Nitric acid is employed as the final reflux acid for the Furnace
AA analysis of As, Be, Cd, Cr, Co, Cu, Fe, Pb, Mn, Ni, Se, Ag, Tl,
V, and Zn. A separate sample shall be dried for a percent solids
determination (Section IV, Part F).
c. Apparatus and Materials
(1) 250 mL beaker or other appropriate vessel
(2) Watch glasses
(3) Thermometer that covers range of 0° to 200°C
(4) Whatman No. 42 filter paper or equivalent
d. Reagents
(1) ASTM Type II water (ASTM D1193): Water must be monitored.
(2) Concentrated nitric acid (sp. gr. 1.41)
(3) Concentrated hydrochloric acid (sp. gr. 1.19)
(4) Hydrogen Peroxide (30%)
e. Sample Preservation and Handling
Soil/sediment (nonaqueous) samples must be refrigerated at 4°C
(±2°) from receipt until analysis.
f. Procedure
(1) Mix the sample thoroughly to achieve homogeneity. For each
digestion procedure, weigh (to the nearest O.Olg) a 1.0 to
1.5 g porrion of sample and transfer to a beaker.
(2) Add 10 mL of 1:1 nitric acid (HN03), mix the slurry,
and cover with a watch glass. Heat the sample to
92-95°C and reflux for 10 minutes without boiling.
Allow the sample to cool, add 5 mL of concentrated HNO^,
D-6 ILM04.0
-------
Exhibit D Section III
replace the watch glass, as appropriate, and reflux for 30
minutes. Do not allow the volume to be reduced to less than
5 mL while maintaining a covering of solution over the
bottom of the heating vessel.
(3) After the second reflux step has been completed and the
sample has cooled, add 2 mL of Type II water and 3 mL of 30%
hydrogen peroxide (H2G>2). Return the heating vessel to the
hot plate or equivalent heating source for warming to start
the peroxide reaction. Care must be taken to ensure that
losses do not occur due to excessively vigorous
effervescence. Heat until effervescence subsides, and cool
the heating vessel.
(4) Continue to add 30% H2O2 in 1 mL aliquots with warming until
the effervescence is minimal or until the general sample
appearance is unchanged. (NOTE: Do not add more than a
total of 10 mL 30% H202-)
(5a) If the sample is being prepared for the furnace AA analysis
of Sb or the flame AA or ICP analysis of Al, As, Sb, Ba, Be,
Ca, Cd, Cr, Co, Cu, Fe, Pb, Mg, Mn, Ni, K, Se, Ag, Na, Tl,
V, and Zn, add 5 mL of 1:1 HCl and 10 mL of Type II water,
return the covered heating vessel to the hot plate or
equivalent heating source, and heat for an additional 10
minutes. After cooling, filter through Whatman No. 42
filter paper (or equivalent) and dilute to 100 mL with Type
II water. NOTE: In place of filtering, the sample (after
dilution and mixing) may be centrifuged or allowed to settle
by gravity overnight to remove insoluble material. The
diluted sample has an approximate acid concentration of 2.5%
(v/v) HCl and 5% (v/v) HNO3. Dilute the digestate 1:1 (200
mL final volume) with acidified water to maintain constant
acid strength. The sample is now ready for analysis.
(5b) If the sample is being prepared for the furnace analysis of
As, Be, Cd, Cr, Co, Cu, Fe, Pb, Mn, Ni, Se, Ag, Tl, V, and
Zn, continue heating the acid-peroxide digestate until the
volume has been reduced to approximately 2 mL, add 10 mL of
Type II water, and warm the mixture. After cooling, filter
through Whatman No. 42 filter paper (or equivalent) and
dilute the sample to 100 mL with Type II water (or
centrifuge the sample). NOTE: In place of filtering, the
sample (after dilution and mixing) may be centrifuged or
allowed to settle by gravity overnight to remove insoluble
material. The diluted digestate solution contains
approximately 2% (v/v) HNO3. Dilute the digestate 1:1 (200
mL final volume) with acidified water to maintain constant
acid strength. For analysis, withdraw aliquots of
appropriate volume, and add any required reagent or matrix
modifier. The sample is now ready for analysis.
g. Calculations
(1) A separate determination of percent solids must be performed
D-7 ILM04.0
-------
Exhibit D Section III
(Section IV, Part F).
(2) The concentrations determined in the digest are to be
reported on the basis of the dry weight of the sample.
Concentration (dry wt.) (mg/kg) = C x V
W x S
Where,
C = Concentration (mg/L)
V = Final volume in liters after sample
preparation
W = Weight in Kg of wet sample
S = % Solids/100
C. TOTAL METALS SAMPLE PREPARATION USING MICROWAVE DIGESTION
1. SCOPE AND APPLICATION
This method is an acid digestion procedure using microwave energy to prepare
water and soil samples for analysis by GFAA, ICP, or Flame AA for the
following metals:
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
NOTE: This microwave digestion method is not
appropriate for the quantitative recovery of Antimony
from soil and sediment samples.
2. SUMMARY OF METHOD
a. Water Sample Preparation
A representative 45 mL water sample is digested in 5 mL of concentrated
•n
nitric acid in a Teflon PFA vessel for 20 minutes using microwave
heating. The digestate is then filtered to remove insoluble material.
The sample may be centrifuged or allowed to settle by gravity overnight
to remove insoluble material.
b. Soil Sample Preparation
A representative 0.5 g (wet weight) sample is digested in 10 mL of
concentrated nitric acid in a TeflonR PFA vessel for 10 minutes using
microwave heating. The digestate is then filtered to remove insoluble
material. The sample may be centrifuged or allowed to settle by gravity
overnight to remove insoluble material. NOTE: This microwave digestion
method is not appropriate for the quantitative recovery of Antimony from
soil and sediment samples.
D-8 ILM04.0
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Exhibit D Section III
3. APPARATUS AND MATERIALS
a. Commercial kitchen or home-use microwave ovens shall not be used for the
digestion of samples under this contract. The oven cavity must be
corrosion resistant and well ventilated. All electronics must be
protected against corrosion for safe operation.
b. Microwave oven with programmable power settings up to at least 600
Watts.
c. The system must use PFA TeflonR digestion vessels (120 mL capacity)
capable of withstanding pressures of up to 110 +10 psi (7.5 +0.7 atm).
These vessels are capable of controlled pressure relief at pressures
exceeding 110 psi.
d. A rotating turntable must be used to ensure homogeneous distribution of
microwave radiation within the oven. The speed of the turntable must be
a minimum of 3 rpm.
e. Polymeric volumetric ware in plastic (Teflon** or polyethylene) 50 mL or
100 mL capacity.
f. Whatman No. 41 filter paper (or equivalent).
g. Disposable polypropylene filter funnel.
h. Analytical balance, 300 g capacity, and minimum +0.01 g.
i. Polyethylene bottles, 125 mL, with caps.
4. REAGENTS
a. ASTM Type II water (ASTM D1193): water must be monitored.
b. Sub-boiled, concentrated nitric acid (sp. gr. 1.41).
c. Concentrated hydrochloric acid (sp. gr. 1.19).
5. MICROWAVE CALIBRATION PROCEDURE
a. The calibration procedure is a critical step prior to the use of any
microwave unit. The microwave unit must be calibrated every six months.
The calibration data for each calibration must be available for review
during on-site audits. In order that absolute power settings may be
interchanged from one microwave unit to another, the actual delivered
power must be determined.
Calibration of a laboratory microwave unit depends on the type of
electronic system used by the manufacturer. If the unit has a
precise and accurate linear relationship between the output power and
the scale used in controlling the microwave unit, then the
calibration can be a two-point calibration at maximum and 40% power. If
the unit is not accurate or precise for some portion of the
controlling scale, then a multiple-point calibration is necessary. If
the unit power calibration needs a multiple-point calibration, then the
point where linearity begins must be identified. For example:
a calibration at 100, 99, 98, 97, 95, 90, 80, 70, 60, 50 and 40%
power settings can be applied and the data plotted. The non-linear
portion of the calibration curve can be excluded or restricted
in use. Each percent is equivalent to approximately 5.5-6 watts and
becomes the smallest unit of power that can be controlled. If 20 - 40
watts are contained from 99-100%, that portion of the microwave
D-9 ILM04.0
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Exhibit D Section III
calibration is not controllable by 3-7 times that of the linear portion
of the control scale and will prevent duplication of precise power
conditions specified in that portion of the power scale.
The power available for heating is evaluated so that the absolute power
setting (watts) may be compared from one microwave to another. This is
accomplished by measuring the temperature rise in 1 Kg of water exposed
to microwave radiation for a fixed period of time. The water is placed
in a TeflonR beaker (or a beaker that is made of some other material
that does not adsorb microwave energy) and stirred before measuring the
temperature. Glass beakers adsorb microwave energy and may not be used.
The initial temperature of the water must be between 19 and 25 °C. The
beaker is circulated continuously through the field for at least two (2)
minutes at full power. The beaker is removed from the microwave, the
water is stirred vigorously, and the final temperature is recorded. The
final reading is the maximum temperature reading after each energy
exposure. These measurements must be accurate to +. 0.1 °C and made
within 30 seconds of the end of heating. If more measurements are
needed, do not use the same water until it has cooled down to room
temperature. Otherwise, use a fresh water sample.
The absorbed power is determined by the following formula:
P = (K) (Cp) (m) (DT)
t
Where:
P = The apparent power absorbed by the sample in watts (joules per second),
K = The conversion factor for thermochemical calories per second to watts
(=4.184),
Cp = The heat capacity, thermal capacity, or specific heat (cal. g~1.°C~1) of
water (=1.0),
m = The mass of the sample in grams (g),
DT = the final temperature minus the initial temperature (°C), and
t = the time in seconds (s)
Using 2 minutes and 1 Kg of distilled water, the calibration equation
simplifies to:
P = (DT) (34.87).
The microwave user can now relate power in watts to the percent power setting
of the microwave.
D-10 ILM04.0
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Exhibit D Section III
6. CLEANING PROCEDURE
a. The initial cleaning of the PFA vessels;
(1) Prior to first use - new vessels must be annealed before they are used. A
pretreatment/cleaning procedure must be followed. This procedure calls for
heating the vessels for 96 hours at 200°C. The vessels must be disassembled
during annealing and the sealing surfaces (the top of the vessel or its rim)
must not be used to support the vessel during annealing.
(2) Rinse in ASTM Type I water.
(3) Immerse in 1:1 HCl for a minimum of 3 hours after the cleaning bath has
reached a temperature just below boiling.
(4) Rinse in ASTM Type I water.
(5) Immerse in 1:1 HNO3 for a minimum of 3 hours after the cleaning bath has
reached a temperature just below boiling.
(6) The vessels are then rinsed with copious amounts of ASTM Type I water prior to
use for any analyses under this contract.
b. Cleaning procedure between sample digestions
(1) Wash entire vessel in hot water using laboratory-grade nonphosphate detergent.
(2) Rinse with 1:1 nitric acid.
(3) Rinse three times with ASTM Type I water. If contaminants are found in the
preparation blank, it is mandatory that steps a(2) through a(6) be strictly
adhered to.
7. DIGESTION PROCEDURE
a. Water Sample Digestion Procedure
(1) A 45 mL aliquot of the sample is measured into TeflonR digestion vessels using
volumetric glassware.
(2) 5 mL of high purity concentrated HNO3 is added to the digestion vessels.
(3) The caps with the pressure release valves are placed on the vessels hand tight
and then tightened, using constant torque, to 12 ft./lbs. The weight of each
vessel is recorded to 0.02 g.
(4) Place 5 sample vessels in the carousel, evenly spaced around its periphery in
the microwave unit. Venting tubes connect each sample vessel with a
collection vessel. Each sample vessel is attached to a clean, double-ported
vessei to collect any sample expelled from the sample vessel in the event of
over pressurization. Assembly of the vessels into the carousel may be done
inside or outside the microwave.
(5) This procedure is energy balanced for five 45 mL water samples (each with 5 mL
of acid) to produce consistent conditions. When fewer than 5 samples are
D-ll ILM04.0
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Exhibit D Section III
digested, the remaining vessels must be filled with 45 mL of tap, DI or Type
II water and 5 mL of concentrated nitric acid.
Newer microwave ovens may be capable of higher power settings which may allow
a larger number of samples. If the analyst wishes to digest more than 5
samples at a time, the analyst may use different power settings as long as
they result in the same time temperature conditions defined in the power
programming for this method.
The initial temperature of the samples should be 24 + 1°C. The preparation
blank must have 45 mL of deionized water and the same amount (5 mL) of acid
that is added to the samples.
The microwave unit first-stage program must be set to give 545 watts for 10
minutes and the second-stage program to give 344 watts for 10 minutes. This
sequence brings the samples to 160 +4°C in ten minutes and permits a slow rise
to 165-170 °C during the second 10 minutes.
(6) Following the 20 minute program, the samples are left to cool in the microwave
unit for five minutes, with the exhaust fan ON. The samples and/or carousel
may then be removed from the microwave unit. Before opening the vessels, let
cool until they are no longer hot to the touch.
(7) After the sample vessel has cooled, weigh the sample vessel and compare to the
initial weight as reported in the preparation log. Any sample vessel
exhibiting a < 0.5 g loss must have any excess sample from the associated
collection vessel added to the original sample vessel before proceeding with
the sample preparation. Any sample vessel exhibiting a > 0.5 g loss must be
identified in the preparation log and the sample redigested.
(9) Sample Filtration:
The digested samples are shaken well to mix in any condensate within the
digestion vessel before being opened. The digestates are then filtered into
50 mL glass volumetric flasks through ultra-clean filter paper and diluted to
50 mL (if necessary). The samples are now ready for analysis. The sample
results must be corrected by a factor of 1.11 in order to report final
concentration values based on an initial volume of 45 mL. Concentrations so
determined shall be reported as "total."
b. Soil Sample Digestion Procedure
(1) Add a representative 0.5 +0.050 grams of sample to the TeflonR PFA vessel.
(2) Add 10 +0.1 mL of concentrated nitric acid. If a vigorous reaction occurs,
allow the reaction to stop before capping the vessel.
(3) Cap the vessel, then tighten' using constant torque to 12 ft/lbs, according to
the manufacturer's direction.
(4) Connect the sample vessel to the overflow vessel using TeflonR PFA tubing.
(5) Weigh the vessel assembly to the nearest O.Olg.
D-12 ILM04.0
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Exhibit D Section III
(6) Place sample vessels in groups of 2 sample vessels or 6 sample vessels in the
carousel, evenly spaced around its periphery in the microwave unit. If fewer
than the recommended number of samples are to be digested (i.e., 3 samples
plus 1 blank) then the remaining vessels must be filled with 10 mL of nitric
acid to achieve the full complement of vessels.
Each sample vessel must be attached to a clean, double-ported vessel to
collect any sample expelled from the sample vessel in the event of over
pressurization. Assembly of the vessels into the carousel may be done inside
or outside the microwave. Connect the overflow vessel to the center well of
the oven.
(7) The preparation blank must have 0.5 mL of deionized water and the same amount
(10 mL) of acid that is added to the samples. The preparation blank must
later be diluted to 50 mL in the same manner as the samples.
(8) Irradiate the 2 sample vessel group at 344 watts for 10 minutes, or the 6-
sample vessel group at 574 watts for 10 minutes.
This program brings the samples to 175°C in 5.5 minutes; the temperature
remains between 170-180°C for the balance of the 10 minute irradiation period.
The pressure should peak at less than 6 atm for most samples. The pressure
may exceed these limits in the case of high concentrations of carbonate or
organic compounds. In these cases, the pressure will be limited by the relief
pressure of the vessel to 7.5 +0.7 atm.
(9) Allow the vessels to cool for a minimum of five minutes before removing them
from the microwave unit, with exhaust fan ON. Allow the vessels to cool to
room temperature before opening. The vessels must be carefully vented and
uncapped in a fume hood.
(10) Weigh each vessel assembly. If the weight of acid plus the sample has
decreased by more than 10% from the original weight, discard the digests.
Determine the reason for the loss. Losses typically are attributed to use of
digestion time longer than ten minutes, using too large of a sample, or having
improper heating conditions. Once the source of the losses has been
corrected, prepare a new set of samples for digestion.
(11) Sample Filtration:
Shake the sample well to mix in any condensate within the digestion vessel
before being opened. Filter the digestion vessel into a 50 mL glass
volumetric flask through ultra-clean filter paper. Rinse the sample digestion
vessel, cap, connecting tube, and (if venting occurred) the overflow vessel
into the 50 mL glass flask. Dilute to 50 mL. The samples are now ready for
analysis. Concentrations so determined shall be reported as "total."
(12) Calculations:
The concentrations determined in the digest are to be reported on the basis of
the dry weight of the sample.
Concentration (dry wt.) (mg/Kg) = C x V
VI x S
D-13 ILM04.0
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Exhibit D Section III
Where
C = Concentration (mg/L)
V = Final volume in liters after sample
preparation
W = Weight in Kg of wet sample
S = % Solids/100
D. MERCURY AND CYANIDE PREPARATION
Refer to each specific method in this Exhibit for mercury and cyanide
preparations.
D-14 ILM04.0
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SECTION IV
SAMPLE ANALYSIS
PART A - INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION
SPECTROMETRIC METHOD
PART B - ATOMIC ABSORPTION METHODS, FURNACE TECHNIQUE
PART C - ATOMIC ABSORPTION METHODS, FLAME TECHNIQUE
PART D - COLD VAPOR METHODS FOR MERCURY ANALYSIS
PART E - METHODS FOR CYANIDE ANALYSIS
PART F - PERCENT SOLIDS DETERMINATION PROCEDURE
Page No.
D-16
D-28
D-41
D-46
D-60
D-84
D-15
ILM04.0
-------
Exhibit D ICP-AES
PART A - INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION SPECTROMETRIC METHOD
Method 200.7 CLP-M*
INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION SPECTROMETRIC METHOD
FOR TRACE ELEMENT ANALYSIS OF WATER AND WASTES
1. Scope and Application
1.1 Dissolved elements are determined in filtered and acidified samples.
Appropriate steps must be taken in all analyses to ensure that potential
interferences are taken into account. This is especially true when dissolved
solids exceed 1500 mg/L. (See 4.)
1.2 Total elements are determined after appropriate digestion procedures are
performed. Since digestion techniques increase the dissolved solids content
of the samples, appropriate steps must be taken to correct for potential
interference effects. (See 4.)
1.3 Table 1 lists elements along with recommended wavelengths and typical
estimated instrumental detection limits using conventional pneumatic
nebulization. Actual working detected limits are sample dependent and as the
sample matrix varies, these concentrations may also vary. In time, other
elements may be added as more information becomes available and as required.
1.4 Because of the differences between various makes and models of satisfactory
instruments, no detailed instrumental operating instructions can be provided.
Instead, the analyst is referred to the instructions provided by the
manufacturer of the particular instrument.
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. Samples are nebulized and the aerosol that is produced is
transported to the plasma torch where excitation occurs. Characteristic
atomic-line emission spectra are produced by a radio-frequency inductively
coupled plasma (ICP). The spectra are dispersed by a grating spectrometer and
the intensities of the lines are monitored by a photosensitive device. The
photocurrents from the photosensitive device are processed and controlled by a
computer system. A background correction technique is required to compensate
for variable background contribution to the determination of trace elements.
Background must be measured adjacent to analyte lines on samples during
analysis. The position selected for the background intensity measurement, on
either or both sides of the analytical line, will be determined by the
complexity of the spectrum adjacent to the analyte line. The position used
must be free of spectral interference and reflect the same change in
background intensity as occurs at the analyte wavelength measured. Background
correction is not required in cases of line broadening where a background
correction measurement would actually degrade the analytical result. The
CLP-M modified for the Contract Laboratory Program.
D-16 ILM04.0
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Exhibit D ICP-AES
possibility of additional interferences named in 4.1 (and tests for their
presence as described in 4.2) should also be recognized and appropriate
corrections made.
3. Safety
The toxicity or carcinogenicity of each reagent used in this method has not
been precisely defined; however, each chemical compound should be treated as a
potential health hazard. The laboratory is responsible for maintaining a
current awareness file of OSHA regulations regarding the safe handling of the
chemicals specified in this method. A reference file of material handling
data sheets should be made available to all personnel involved in the chemical
analysis.
4. Interferences
4.1 Several types of interference effects may contribute to inaccuracies in the
determination of trace elements. They can be summarized as follows:
4.1.1 Spectral interferences can be categorized as 1) overlap of a spectral
line from another element; 2) unresolved overlap of molecular band
spectra; 3) background contribution from continuous or recombination
phenomena; and 4) background contribution from stray light from the
line emission of high concentration elements. The first of these
effects can be compensated by utilizing a computer correction of the
raw data, requiring the monitoring and measurement of the interfering
element. The second effect may require selection of an alternate
wavelength. The third and fourth effects can usually be compensated
by a background correction adjacent to the analyte line. In addition,
users of simultaneous multi-element instrumentation must assume the
responsibility of verifying the absence of spectral interference from
an element that could occur in a sample but for which there is no
channel in the instrument array.
Listed in Table 2 are some interference effects for the recommended
wavelengths given in Table 1. The data in Table 2 are intended for
use only as a rudimentary guide for the indication of potential
spectral interferences. For this purpose, linear relations between
concentration and intensity for the analytes and the interferents can
be assumed. The interference information, which was collected at the
Ames Laboratory**, is expressed as analyte concentration equivalents
(i.e., false analyte concentrations) arising from 100 mg/L of the
interferent element.
The suggested use of this information is as follows: Assume that
arsenic (at 193.696 nm) is to be determined in a sample containing
approximately 10 mg/L of aluminum. According to Table 2, 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 other analytical systems may exhibit
somewhat different levels of interference than those shown in Table
**
Ames Laboratory, USDOE, Iowa State University, Ames, Iowa 50011.
D-17 ILM04.0
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Exhibit D ICP-AES
2, and that the interference effects must, be evaluated for each
individual system. Only those interferents listed were investigated
and the blank spaces in Table 2 indicate that measurable interferences
were not observed from the interferent concentrations listed in Table
3. Generally, interferences were discernible if they produced peaks
or background shifts corresponding to 2-5% of the peaks generated by
the analyte concentrations also listed in Table 3.
At present, information on the listed silver and potassium wavelengths
is not available but it has been reported that second order energy
from the magnesium 383.231 nm wavelength interferes with the listed
potassium line at 766.491 nm.
4.1.2 Physical interferences are generally considered to be effects
associated with the sample nebulization and transport processes. Such
properties as change 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
are operative, they must be reduced by dilution of the sample and/or
utilization of standard addition techniques. Another problem which
can occur from high dissolved solids is salt buildup at the tip of the
nebulizer. This affects aerosol flow rate causing instrumental drift.
Wetting the argon prior to nebulization, the use of a tip washer, or
sample dilution has been used to control this problem. Also, it has
been reported that better control of the argon flow rate improves
instrument performance. This is accomplished with the use of mass
flow controllers.
4.1.3 Chemical interferences are characterized by molecular compound
formation, ionization effects and solute vaporization effects.
Normally these effects are not pronounced with the ICP technique,
however, if observed they can be minimized by careful selection of
operating conditions (that is, incident power, observation position,
and so forth), by buffering of the sample, by matrix matching, and by
standard addition procedures. These types of interferences can be
highly dependent on matrix type and the specific analyte element.
4.2 Prior to reporting concentration data for the analyte elements, the Contractor
shall analyze and report the results of the ICP Serial Dilution Analysis. The
ICP Serial Dilution Analysis shall be performed on a sample from each group of
samples of a similar matrix type (i.e., water, soil) and concentration (i.e.,
low, medium) or for each Sample Delivery Group, whichever is more frequent.
Samples identified as field blanks cannot be used for Serial Dilution
Analysis.
If the analyte concentration is sufficiently high (minimally a factor of 50
above the instrumental detection limit in the original sample), the serial
dilution (a five fold dilution) shall then agree within 10% of the original
determination after correction for dilution. If the dilution analysis for one
or more analytes is not within 10%, a chemical or physical interference effect
must be suspected, and the data for all affected analytes in the samples
received associated with that serial dilution must be flagged with an "E" on
FORM IX-IN and FORM I-IN.
D-18 ILM04.0
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Exhibit D ICP-AES
5. Apparatus
5.1 Inductively Coupled Plasma-Atomic Emission Spectrometer.
5.1.1 Computer controlled atomic emission spectrometer with background
correction.
5.1.2 Radio frequency generator.
5.1.3 Argon gas supply, welding grade or better.
5.2 Operating conditions — 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
manufacturer of the particular instrument. Sensitivity, instrumental
detection limit, precision, linear dynamic range, and interference effects
must be investigated and established for each individual analyte line on that
particular instrument. All measurements must be within the instrument 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 requirements and to maintain quality control data
confirming instrument performance and analytical results.
6. Reagents and Standards
6.1 Acids used in the preparation of standards and for sample processing must be
ultra-high purity grade or equivalent. Redistilled acids are acceptable.
6.1.1 Acetic acid, cone. (sp gr 1.06).
6.1.2 Hydrochloric acid, cone. (sp gr 1.19).
6.1.3 Hydrochloric acid, (1+1): Add 500 mL cone. HC1 (sp gr 1.19) to 400
mL deionized, distilled water and dilute to 1 liter.
6.1.4 Nitric acid, cone. (sp gr 1.41).
6.1.5 Nitric acid, (1+1): Add 500 mL cone. HNO3 (sp gr 1.41) to 400 mL
deionized, distilled water and dilute to 1 liter.
6.2 Deionized, distilled water: Prepare by passing distilled water through a
mixed bed of cation and anion exchange resins. Use deionized, distilled water
for the preparation of all reagents and calibration standards and as dilution
water. The purity of this water must be equivalent to ASTM Type II reagent
water of Specification D 1193.
6.3 Standard stock solutions may be purchased or prepared from ultra high purity
grade chemicals or metals.
unless otherwise specified.
grade chemicals or metals. All salts must be dried for 1 hour at 105° C
D-19 ILM04.0
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Exhibit D ICP-AES
(CAUTION: Many metal salts are extremely toxic and may be fatal if swallowed.
Wash hands thoroughly after handling. ) Typical stock solution preparation
procedures follow:
6.3.1 Aluminum solution, stock, 1 rnL = 100 ug Al: Dissolved 0.100 g of
aluminum metal in an acid mixture of 4 mL of (1+1) HC1 and 1 mL of
cone. HNO3 in a beaker. Warm gently to effect solution. When
solution is complete, transfer quantitatively to a liter flask, add an
additional 10 mL of (1+1) HC1 and dilute to 1000 mL with deionized,
distilled water.
6.3.2 Antimony solution stock, 1 mL = 100 ug Sb: Dissolve 0.2669 g
K(SbO)C4H4O6 in deionized distilled water, add 10 mL (1+1) HC1 and
dilute to 1000 mL with deionized, distilled water.
6.3.3 Arsenic solution, stock, 1 mL = 100 ug As: Dissolve 0.1320 g of AS2<33
in 100 mL of deionized, distilled water containing 0.4 g NaOH.
Acidify the solution with 2 mL cone. HNO3 and dilute to 1,000 mL with
deionized, distilled water.
6.3.4 Barium solution, stock, 1 mL = 100 ug Ba: Dissolve 0.1516 g
(dried at 250°C for 2 hrs) in 10 mL deionized, distilled water with 1
mL (1+1) HC1. Add 10.0 mL (1+1) HC1 and dilute to 1,000 mL with
deionized, distilled water.
6.3.5 Beryllium solution, stock, 1 mL = 100 ug Be: Do not dry. Dissolve
1.966 g BeS04MH2O, in deionized, distilled water, add 10.0 mL cone.
HNO3 and dilute to 1,000 mL with deionized, distilled water.
6.3.6 Boron solution, stock, 1 mL = 100 ug B: Do not dry. Dissolve 0.5716
g anhydrous H3BO3 in deionized, distilled water and dilute to 1,000
mL. Use a reagent meeting ACS specifications, keep the bottle tightly
stoppered and store in a desiccator to prevent the entrance of
atmospheric moisture.
6.3.7 Cadmium solution, stock, 1 mL = 100 ug Cd: Dissolve 0.1142 g CdO in a
minimum amount of (1+1) HNO3 . Heat to increase rate of dissolution.
Add 10.0 mL cone. HNO3 and dilute to 1,000 mL with deionized,
distilled water.
6.3.8 Calcium solution, stock, 1 mL = 100 ug Ca: Suspend 0.2498 g CaCO-j
dried at 180°C for 1 h before weighing in deionized, distilled water
and dissolve cautiously with a minimum amount of (1+1) HNO3. Add
10.0 mL cone. HNO3 and dilute to 1,000 mL with deionized, distilled
water.
6.3.9 Chromium solution, stock, 1 mL = 100 ug Cr: Dissolve 0.1923 g of CrO3
in deionized, distilled water. When solution is complete acidify with
10 mL cone. HNO3 and dilute to 1,000 mL with deionized, distilled
water.
6.3.10 Cobalt solution stock, 1 mL = 100 ug Co: Dissolve 0.1000 g of cobalt
metal in a minimum amount of (1+1) HNO3 . Add 10.0 mL (1+1) HC1 and
dilute to 1,000 mL with deionized, distilled water.
D-20 ILM04.0
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Exhibit D ICP-AES
6.3.11 Copper solution, stock, 1 mL = 100 ug Cu: Dissolve 0.1252 g CuO in a
minimum amount of (1+1) HNO3 . Add 10.0 mL cone. HNO3 and dilute to
1,000 mL with deionized, distilled water.
6.3.12 Iron solution, stock, 1 mL = 100 ug Fe: Dissolve 0.1430 g Fe2O3 in a
warm mixture of 20 mL (1+1) HC1 and 2 mL of cone. HNO3 . Cool, add an
additional 5 mL of cone. HNO3 and dilute to 1,000 mL with deionized,
distilled water.
6.3.13 Lead solution, stock, 1 mL = 100 ug Pb: Dissolve 0.1599 g Pb(NO3)2 ^n
a minimum amount of (1+1) HNO3. Add 10.0 mL of cone. HNO3 and dilute
to 1,000 mL with deionized, distilled water.
6.3.14 Magnesium solution, stock, 1 mL = 100 ug Mg: Dissolve 0.1658 g MgO in
a minimum amount of (1+1) HNO3- Add 10.0 mL cone. HNO3 and dilute to
1,000 mL with deionized, distilled water.
6.3.15 Manganese solution, stock, 1 mL = 100 ug Mn: Dissolve 0.1000 g of
manganese metal in the acid mixture, 10 mL cone. HC1 and 1 mL cone.
HNO3, and dilute to 1,000 mL with deionized, distilled water.
6.3.16 Molybdenum solution, stock, 1 mL = 100 ug Mo: Dissolve 0.2043 g
in deionized, distilled water and dilute to 1,000 mL.
6.3.17 Nickel solution, stock, 1 mL = 100 ug Ni: Dissolve 0.1000 g of nickel
metal in 10 mL hot cone. HNO3, cool and dilute to 1,000 mL with
deionized, distilled water.
6.3.18 Potassium solution, stock, 1 mL = 100 ug K: Dissolve 0.1907 g KC1,
dried at 110°C, in deionized, distilled water. Dilute to 1,000 mL.
6.3.19 Selenium solution, stock, 1 mL = 100 ug Se: Do not dry. Dissolve
0.1727 g H2SeO3 (actual assay 94.6%) in deionized, distilled water and
dilute to 1,000 mL.
6.3.20 Silica solution, stock, 1 mL = 100 ug SiC^: Do not dry. Dissolve
0.4730 g Na2SiO3-9H2O in deionized, distilled water. Add 10.0 mL
cone. HNO3 and dilute to 1,000 mL with deionized, distilled water.
6.3.21 Silver solution, stock, 1 mL = 100 ug Ag: Dissolve 0.1575 g AgNO3 in
100 mL of deionized, distilled water and 10 mL cone. HNO3 . Dilute
to 1,000 mL with deionized, distilled water.
6.3.22 Sodium solution, stock, 1 mL = 100 ug Na: Dissolve 0.2542 g NaCl in
deionized, distilled water. Add 10.0 mL cone. HNO3 and dilute to
1,000 mL with deionized, distilled water.
6.3.23 Thallium solution, stock, 1 mL = 100 ug Tl: Dissolve 0.1303 g T1NO3
in deionized, distilled water. Add 10. 0 mL cone. HNO3 and dilute to
1,000 mL with deionized, distilled water.
D-21 ILM04.0
-------
Exhibit D ICP-AES
6.3.24 Vanadium solution, stock, 1 mL = 100 ug V: Dissolve 0.2297 NH4VO3 in
a minimum amount of cone. HNO3. Heat to increase rate of
dissolution. Add 10.0 mL cone. HNO3 and dilute to 1,000 mL with
deionized, distilled water.
6.3.25 Zinc solution, stock, 1 mL = 100 ug Zn: Dissolve 0.1245 g ZnO in a
minimum amount of dilute HN03. Add 10.0 mL cone. HNO3 and dilute to
1,000 mL with deionized, distilled water.
6.4 Mixed calibration standard solutions — Prepare mixed calibration standard
solutions by combining appropriate volumes of the stock solutions in
volumetric flasks. (See 6.4.1 thru 6.4.5.) Add 2 mL of (1+1) HNO3 and 10 mL
of (1+1) HC1 and dilute to 100 mL with deionized, distilled water. (See NOTE
in 6.4.5.) Prior to preparing the mixed standards, each stock solution should
be analyzed separately to determine possible spectral interference or the
presence of impurities. Care should be taken when preparing the mixed
standards that the elements are compatible and stable. Transfer the mixed
standard solutions to a FEP fluorocarbon or unused 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 quality control sample and monitored weekly
for stability (see 6.6.3). Although not specifically required, some typical
calibration standard combinations follow when using those specific wavelengths
listed in Table 1.
6.4.1 Mixed standard solution I — Manganese, beryllium, cadmium, lead, and
zinc.
6.4.2 Mixed standard solution II — Barium, copper, iron, vanadium, and
cobalt.
6.4.3 Mixed standard solution III — Molybdenum, silica, arsenic, and
selenium.
6.4.4 Mixed standard solution IV — Calcium, sodium, potassium, aluminum,
chromium and nickel.
6.4.5 Mixed standard solution V — Antimony, boron, magnesium, silver, and
thallium.
NOTE: If the addition of silver to the recommended acid combination
results in an initial precipitation, add 15 mL of deionized distilled
water and warm the flask until the solution clears. Cool and dilute
to 100 mL with deionized, distilled 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 HCl.
6.5 Two types of blanks are required for the analysis. The calibration blank (see
Exhibit E) is used in establishing the analytical curve while the reagent
blank (preparation blank, Exhibit E) is used to correct for possible
contamination resulting from varying amounts of the acids used in the sample
processing.
D-22 ILM04.0
-------
Exhibit D ICP-AES
6.5.1 The calibration blank is prepared by diluting 2 mL of (1+1) HNC>3 and
10 mL of (1+1) HC1 to 100 mL with deionized, distilled water. Prepare
a sufficient quantity to be used to flush the system between standards
and samples.
6.5.2 The reagent blank (or preparation blank - see Exhibit E) must contain
all the reagents and in the same volumes as used in the processing of
the samples. The reagent blank must be carried through the complete
procedure and contain the same acid concentration in the final
solution as the sample solution used for analysis.
6.6 In addition to the calibration standards, an instrument check standard, an
interference check sample and a quality control sample are also required for
the analyses (see Exhibit E).
6.6.1 The instrument check standard for continuing calibration verification
is prepared by the analyst by combining compatible elements at a
concentration equivalent to the mid-points of their respective
calibration curves.
6.6.2 The interference check sample is prepared by the analyst, or obtained
from EPA if available.
6.6.3 The quality control sample for the initial calibration verification
should be prepared in the same acid matrix as the calibration
standards and in accordance with the instructions provided by the
supplier.
7. Procedure
7.1 Set up instrument with proper operating parameters established in Section 5.2.
The instrument must be allowed to become thermally stable before beginning.
This usually requires at least 30 min. of operation prior to calibration.
7.2 Initiate appropriate operating configuration of computer.
7.3 Profile and calibrate instrument according to instrument manufacturer's
recommended procedures, using mixed calibration standard solutions such as
those described in Section 6.4. Flush the system with the calibration blank
(6.5.1) between each standard. (NOTE: For boron concentrations greater than
500 ug/L extended flush times of 1 to 2 minutes may be required.)
7.4 Begin the sample run flushing the system with the calibration blank solution
(6.5.1) between each sample. (See NOTE in 7.3.) Analyze the instrument check
standard (6.6.1) and the calibration blank (6.5.1) each 10 analytical samples.
7.5 A minimum of two replicate exposures is required for standardization and all
QC and sample analyses. The average result of the multiple exposures for the
standardization and all QC and sample analyses shall be used.
D-23 ILM04.0
-------
Exhibit D ICP-AES
8. Calculation
8.1 Reagent blanks (preparation blanks) shall be treated as specified in Exhibit
E.
8.2 If dilutions were performed, the appropriate factor shall be applied to sample
values.
8.3 Units shall be clearly specified.
9. Quality Control (Instrumental)
9.1 Quality control shall be performed as specified in Exhibit E.
D-24 ILM04.0
-------
Exhibit D ICP-AES
TABLE 1 - RECOMMENDED WAVELENGTHS AND ESTIMATED
INSTRUMENTAL DETECTION LIMITS
Element
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Potassium
Selenium
Silica (Si02)
Silver
Sodium
Thallium
Vanadium
Zinc
Wavelength, nm(l)
308.215
206.833
193.696
455.403
313.042
249.773
226.502
317.933
267.716
228.616
324.754
259.940
220.353
279.079
257.610
202.030
231.604
766.491
196.026
288.158
328.068
588.995
190.864
292.402
213.856
Estimated Detection
Limit, ug/L(2)
45
32
53
2
0.3
5
4
10
7
7
6
7
42
30
2
8
15
See ( 3 )
75
58
7
29
40
8
2
(1) The wavelengths listed are recommended because of their sensitivity and overall
acceptance. Other wavelengths may be substituted if they can provide the
needed sensitivity and are treated with the same corrective techniques for
spectral interference. (See 4.1.1.) The use of alternate wavelengths must be
reported (in nm) with the sample data.
(2) The estimated instrumental detection limits as shown are taken from
"Inductively Coupled Plasma-Atomic Emission Spectroscopy-Prominent Lines," EPA-
600/4-79-017. They are given as a guide for an instrumental limit. The actual
method detection limits are sample dependent and may vary as the sample matrix
varies.
(3) Highly dependent on operating conditions and plasma position.
D-25
ILM04.0
-------
TABLE 2. EXAMPLE OF ANALYTE CONCENTRATION EQUIVALENTS (MG/L) ARISING FROM
INTERFERENTS AT THE 100 MG/L LEVEL
Wavelength,
Analyte run
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
i
^ Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Selenium
Silicon
Sodium
Thallium
Vanadium
pj Zinc
- s
308.215
206.833
193.696
455.403
313.042
249.773
226.502
317.933
267.716
228.616
324.754
259.940
220.353
279.079
257.610
202.030
231.604
196.026
288.158
588.995
190.864
i
292.402
213.856
Interferent
Al Ca Cr Cu Fe Mg Mn Ni Ti
0.21
0.47 — 2.9 ~ 0.08 — ~ ~ .25
1.3 — 0.44
__ __ — — — — — — — — — — — — — —
0.04
0.04 — — • -- 0.32
0.03 — ~ 0.02
0.08 — 0.01 0.01 0.04 — 0.03
0.003 — 0.04
0.03 — 0.005 — — 0.03 0.15
0.003 — - -- — 0.05
0.12
0.17 — — —
0.02 0.11 ~ 0.13 — 0.25 — 0.07
0.005 — O.01 — O.002 O.002
0.05 — — -- 0.03
__ __ — — — — — — — — — — — — — —
0.23 — — — 0.09
0.07
0.08
0.30
0.05 -- 0.005 — ~ — 0.02
0.14 — — -- 0.29
V
1.4
0.45
1.1
—
0.05
•» V
—
0.03
0.04
—
0.02
_.
—
0.12
—
""
0.01
«. w
—
"••"
-------
Exhibit D ICP-AES
TABLE 3. INTERFERENT AND ANALYTE ELEMENTAL CONCENTRATIONS USED
FOR INTERFERENCE MEASUREMENTS IN TABLE 2
Analytes
Al
As
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Mg
Mn
Mo
Na
Ni
Pb
Sb
Se
Si
Tl
V
Zn
(mg/L)
10
10
10
1
1
1
10
1
1
1
1
1
1
10
10
10
10
10
10
1
10
1
10
Interf erents
Al
Ca
Cr
Cu
Fe
Mg
Mn
Ni
Ti
V
(mg/L)
1000
1000
200
200
1000
1000
200
200
200
200
D-27
ILM04.0
-------
PART B - ATOMIC ABSORPTION METHODS, FURNACE TECHNIQUE
Analvte/Method Page No.
.*
Antimony - Method 204.2 CLP-M D-29
Arsenic - Method 206.2 CLP-M D-30
Beryllium - Method 210.2 CLP-M D-32
Cadmium - Method 213.2 CLP-M D-33
Chromium - Method 218.2 CLP-M D-34
Lead - Method 239.2 CLP-M D-35
Selenium - Method 270.2 CLP-M D-37
Silver - Method 272.2 CLP-M D-39
Thallium - Method 279.2 CLP-M D-40
+From "Methods for Chemical Analysis of Water and Wastes" (EPA-600/4-79-020), Metals-
4, as modified for use in the Contract Laboratory Program.
*CLP-M modified for the Contract Laboratory Program.
D-28 ILM04.0
-------
Exhibit D Method 204.2
ANTIMONY
Method 204.2 CLP-M (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 20-300 ug/L
Approximate Detection Limit: 3 ug/L
Preparation of Standard Solution
1. Stock solution: Carefully weigh 2.7426 g of antimony potassium tartrate
(analytical reagent grade) and dissolve in deionized distilled water. Dilute
to 1 liter with deionized water. 1 mL = 1 mg Sb (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. These solutions are also to be used for "standard
additions."
3. The calibration standards must be prepared using the same type of acid and at
the same concentration as will result in the sample to be analyzed after sample
preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 800°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 217.6 nm
6. Operating parameters should be set as specified by the particular instrument
manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, continuous flow purge gas and
non-pyrolytic graphite and are to be used as guidelines only. Smaller size
furnace devices or those employing faster rates of atomization can be operated
using lower atomization temperatures for shorter time periods than the above
recommended settings.
2. The use of background correction is required.
3. Nitrogen may also be used as the purge gas.
4. If chloride concentration presents a matrix problem or causes a loss previous
to atomization, add an excess 5 mg of ammonium nitrate to the furnace and ash
using a ramp accessory or with incremental steps until the recommended ashing
temperature is reached.
5. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (see Exhibit E) .
6. If method of standard addition is required, follow the procedure given in
Exhibit E.
*CLP-M modified for the Contract Laboratory Program.
D-29 ILM04.0
-------
Exhibit D Method 206.2
ARSENIC
Method 206.2 CLP-M** (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L *
Approximate Detection Limit: 1 ug/L
Preparation of Standard Solution
1. Stock solution: Dissolve 1.320 g of arsenic trioxide, As2O3 (analytical reagent
grade) in 100 mL of deionized distilled water containing 4 g NaOH. Acidify the
solution with 20 mL cone. HNO3 and dilute to 1 liter. 1 mL = 1 mg As (1000
mg/1).
2. Nickel Nitrate Solution, 5%: Dissolve 24.780 g of ACS reagent grade
Ni(NO3)2"6H2O in deionized distilled water and make up to 100 mL.
3. Nickel Nitrate Solution, 1%: Dilute 20 mL of the 5% nickel nitrate to 100 mL
with deionized distilled water.
4. Working Arsenic Solution: Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. Withdraw appropriate aliguots of
the stock solution, and add 1 mL of cone. HNO3, 2 mL of 30% H202 and 2 mL of the
5% nickel nitrate solution. Dilute to 100 mL with deionized distilled water.
Sample Preparation
1. Add 100 uL of the 5% nickel nitrate solution to 5 mL of the digested sample. The
sample is now ready for injection into the furnace.
Note: Another matrix modifier may be substituted for nickel nitrate if
recommended by the instrument manufacturer. The matrix modifier used shall be
reported in the SDG Case Narrative.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 1100°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 193.7 nm
6. Operating parameters should be set as specified by the particular instrument
manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, purge gas interrupt and non-
pyrolytic graphite. Smaller size furnace devices or those employing faster rates
of atomization can be operated using lower atomization temperatures for shorter
time periods than the above recommended settings.
2. The use of background correction is required. Background correction made by the
deuterium arc method does not adequately compensate for high levels of certain
interferents (i.e., Al, Fe). If conditions occur where significant interference
CLP-M modified for the Contract Laboratory Program.
D-30 ILM04.0
-------
Exhibit D Method 206.2
is suspected, the lab must switch to an alternate wavelength or take other
appropriate actions to compensate for the interference effects.
3. For every sample analyzed, verification is necessary to determine that method of
standard addition is not required (see Exhibit E).
4. If method of standard addition is required, follow the procedure given in
Exhibit E.
5. The use of the Electrodeless Discharge Lamps (EDL) for the light source is
recommended.
D-31 ILM04.0
-------
Exhibit D Method 210.2
BERYLLIUM
Method 210.2 CLP-M* (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 1-30 ug/L
Approximate Detection Limit: 0.2 ug/L
Preparation of Standard Solution
1. Stock solution: Dissolve 11.6586 g of beryllium sulfate, BeSO4, in deionized
distilled water containing 2 mL concentrated nitric acid and dilute to 1 liter.
1 mL = 1 mg Be (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. These solutions are also to be used for "standard
additions."
3. The calibration standards must be prepared using the same type of acid and at
the same concentration as will result in the sample to be analyzed after sample
preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 1000°C.
3. Atomizing Time and Temp: 10 sec @ 2800°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 234.9 nm
6. Operating parameters should be set as specified by the particular instrument
manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, continuous flow purge gas and
non-pyrolytic graphite, and are to be used as guidelines only. Smaller size
furnace devices or those employing faster rates of atomization can be operated
using lower atomization temperatures for shorter time periods than the above
recommended settings.
2. The use of background correction is required.
3. Because of possible chemical interaction, nitrogen should not be used as a purge
gas.
4. For every sample analyzed, verification is necessary to determine that method of
standard addition is not required (see Exhibit E).
5. If method of standard addition is required, follow the procedure given in
Exhibit E.
CLP-M modified for the Contract Laboratory Program.
D-32 ILM04.0
-------
Exhibit D Method 213.2
CADMIUM
Method 213.2 CLP-M (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 0.5-10 ug/L
Approximate Detection Limit: 0.1 ug/L
Preparation of Standard Solution
1. Stock solution: Carefully weigh 2.282 g of cadmium sulfate, 3 CdSO4'8 H2O
(analytical reagent grade) and dissolve in deionized distilled water. Make up
to 1 liter with deionized distilled water. 1 mL = 1 mg Cd (1000 mg/L).
2. Ammonium Phosphate solution (40%): Dissolve 40 grams of ammonium phosphate,
(NH^^HPC^ (analytical reagent grade) in deionized distilled water and dilute to
100 mL.
3. Prepare dilutions of stock cadmium solution to be used as calibration standards
at the time of analysis. To each 100 mL of standard and sample alike add 2.0 mL
of the ammonium phosphate solution. The calibration standards must be prepared
using the same type of acid and at the same concentration as will result in the
sample to be analyzed after sample preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 500°C.
3. Atomizing Time and Temp: 10 sec @ 1900°C.
4 Purge Gas Atmosphere: Argon
5. Wavelength: 228.8 nm
6. Operating parameters should be set as specified by the particular instrument
manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, continuous flow purge gas and
non-pyrolytic graphite, and are to be used as guidelines only. Smaller size
furnace devices or those employing faster rates of atomization can be operated
using lower atomization temperatures for shorter time periods than the above
recommended settings.
2. The use of background correction is required.
3. Contamination from the work area is critical in cadmium analysis. Use pipette
tips which are free of cadmium.
4. For every sample analyzed, verification is necessary to determine that method of
standard addition is not required (see Exhibit E).
5. If method of standard addition is required, follow the procedure given, in
Exhibit E.
CLP-M modified for the Contract Laboratory Program.
D-33 ILM04.0
-------
Exhibit D Method 218.2
CHROMIUM
Method 218.2 CLP-M* (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L
Approximate Detection Limit: 1 ug/L
Preparation of Standard Solution
1. Stock solution: Prepare as described under Part C methods, AA Flame Technique.
2. Calcium Nitrate solution: Dissolve 11.8 grams of calcium nitrate, Ca(NO3)2*4H2O
(analytical reagent grade) in deionized distilled water and dilute to 100 mL. 1
mL = 20 mg Ca.
3. Prepare dilutions of the stock chromium solution to be used as calibration
standards at the time of analysis. The calibration standards must be prepared
using the same type of acid and at the same concentration as will result in the
sample to be analyzed after sample preparation. To each 100 mL of standard and
sample alike, add 1 mL of 30% ^2^2 an<^ ^ m^ °^ fc^e calci-um nitrate solution.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 1000°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 357.9 nm
6. Operating parameters should be set as specified by the particular instrument
manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin Elmer
HGA-2100, based on the use of a 20 uL injection, continuous flow purge gas and
non-pyrolytic graphite, and are to be used as guidelines only.
2. Hydrogen peroxide is added to the acidified solution to convert all chromium to
the trivalent state. Calcium is added to a level above 200 mg/L where its
suppressive effect becomes constant up to 1000 mg/L.
3. Background correction is required.
4. Nitrogen should not be used as a purge gas because of possible CN band
interference.
5. Pipette tips have been reported to be a possible source of contamination.
6. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (see Exhibit E).
7. If method of standard addition is required, follow the procedure given in
Exhibit E.
*CLP-M modified for the Contract Laboratory Program.
D-34 ILM04.0
-------
Exhibit D Method 239.2
LEAD
Method 239.2 CLP-M* (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L
Approximate Detection Limit: 1 ug/L
Preparation of Standard Solution
1. Stock solution: Carefully weigh 1.599 g of lead nitrate, Pb(NO:j)2 (analytical
reagent grade), and dissolve in deionized distilled water. When solution is
complete, acidify with 10 mL redistilled HNO3 and dilute to 1 Liter with
deionized distilled water. 1 mL = 1 mg Pb (lOOOmg/L).
2. Lanthanum Nitrate solution: Dissolve 58.64 g of ACS reagent grade La2O3 in 100
mL cone. HNO3 and dilute to 1000 mL with deionized distilled water. 1 mL = 50
mg La.
3. Working Lead solution: Prepare dilutions of stock lead solution to be used as
calibration standards at the time of analysis. The calibration standards must
be prepared using the same type of acid and at the same concentration as will
result in the sample to be analyzed after sample preparation. To each 100 mL of
diluted standard add 10 mL of the lanthanum nitrate solution.
Sample Preparation
1. To each 100 mL of prepared sample solution add 10 mL of the lanthanum nitrate
solution.
Note: Another matrix modifier may be substituted for lanthanum nitrate if
recommended by the instrument manufacturer. The matrix modifier used shall be
reported in the SDG Case Narrative.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 500°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 283.3 nm
6. Operating parameters should be set as specified by the particular instrument
manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, continuous flow purge gas and
non-pyrolytic graphite, and are ro be used as guidelines only. Smaller size
furnace devices or those employing faster rates of atomization can be operated
using lower atomization temperatures for shorter time periods than the above
recommended settings.
2. The use of background correction is required.
3. Greater sensitivity can be achieved using the 217.0 nm line, but the optimum
concentration range is reduced. The use of a lead electrodeless discharge lamp
at this lower wavelength has been found to be advantageous. Also a lower
atomization temperature (2400°C) may be preferred.
CLP-M modified for the Contract Laboratory Program.
D-35 ILM04.0
-------
Exhibit D Method 239.2
4. To suppress sulfate interference (up to 1500 ppm), lanthanum is added as the
nitrate to both samples and calibration standards. (Atomic Absorption
Newsletter Vol. 15, No. 3, p. 71, May-June 1976.)
5. Since glassware contamination is a severe problem in lead analysis, all
glassware should be cleaned immediately prior to use, and once cleaned, should
not be open to the atmosphere except when necessary.
6. For every sample analyzed, verification is necessary to determine that method of
standard addition is not required (see Exhibit E).
7. If method of standard addition is required, follow the procedure given in
Exhibit E.
D-36 ILM04.0
-------
Exhibit D Method 270.2
SELENIUM
Method 270.2 CLP-M (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L
Approximate Detection Limit: 2 ug/L
Preparation of Standard Solution
1. Stock Selenium solution: Dissolve 0.3453 g of selenous acid (actual assay 94.6%
I^SeC^) in deionized distilled water and make up to 200 mL. 1 mL = 1 mg
Se (1000 mg/L).
2. Nickel Nitrate solution, 5%: Dissolve 24.780 g of ACS reagent grade
Ni (N02 >2 • S^O in deionized distilled water and make up to 100 mL.
3. Nickel Nitrate solution, 1%: Dilute 20 mL of the 5% nickel nitrate to 100 mL
with deionized distilled water.
4. Working Selenium solution: Prepare dilutions of the stock solution to be used
as calibration standards at the time of analysis. The calibration standards
must be prepared using the same type of acid and at the same concentration as
will result in the sample to be analyzed after sample preparation. Withdraw
appropriate aliguots of the stock solution, and add 1 mL of cone. HNO3, 2 mL of
30% H2O2 and 2 mL of the 5% nickel nitrate solution. Dilute to 100 mL with
deionized distilled water.
Sample Preparation
1. Add 100 uL of the 5% nickel nitrate solution to 5 mL of the digested sample.
The sample is now ready for injection into the furnace.
Note: Another matrix modifier may be substituted for nickel nitrate if
recommended by the instrument manufacturer. The matrix modifier used shall be
reported in the SDG Case Narrative.
Instrument Parameters
1. Drying Time and Temp: 30 sec @ 125°C.
2. Charring Time and Temp: 30 sec @ 1200°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 196.0 nm
6. Operating parameters should be set as specified by the particular instrument
manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, purge gas interrupt and non-
pyrolytic graphite, and are to be used as guidelines only. Smaller size
furnace devices or those employing faster rates of atomization can be operated
using lower atomization temperatures for shorter time periods than the above
recommended settings.
2. The use of background correction is required. Background correction made by the
deuterium arc method does not adequately compensate for high levels of certain
interferents (i.e., Al, Fe). If conditions occur where significant interference
CLP-M modified for the Contract Laboratory Program.
D-37 ILM04.0
-------
Exhibit D Method 270.2
is suspected, the lab must switch to an alternate wavelength or take other
appropriate actions to compensate for the interference effects.
3. Selenium analysis suffers interference from chlorides (>800 mg/L) and sulfate
(>200 mg/L). For the analysis of industrial effluents and samples with
concentrations of sulfate from 200 to 2000 mg/L, both samples and standards
should be prepared to contain 1% nickel.
4. For every sample analyzed, verification is necessary to determine that method of
standard addition is not required (see Exhibit E).
5. If method of standard addition is required, follow the procedure given in
Exhibit E.
6. The use of the Electrodeless Discharge Lamp (EDL) for the light source is
recommended.
D-38 ILM04.0
-------
Exhibit D Method 272.2
SILVER
Method 272.2 CLP-M (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 1-25 ug/L
Approximate Detection Limit: 0.2 ug/L
Preparation of Standard Solution
1. Stock solution: Dissolve 1.575 g of AgNO3 (analytical reagent grade) in
deionized distilled water. Add 10 mL of concentrated HNOj and make up to 1
liter. 1 mL = 1 mg Ag (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. These solutions are also to be used for "standard
additions."
3. The calibration standards must be prepared using the same type of acid and at
the same concentration as will result in the sample to be analyzed after sample
preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 400°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 328.1 nm
6. Operating parameters should be set as specified by the particular instrument
manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, continuous flow purge gas and
non-pyrolytic graphite and are to be used as guidelines only. Smaller size
furnace devices or those employing faster rates of atomization can be operated
using lower atomization temperatures for shorter time periods than the above
recommended settings.
2. The use of background correction is required.
3. The use of halide acids should be avoided.
4. If absorption to container walls or formation of AgCl is suspected, see Exhibit
D, Part C, Atomic Absorption Methods, Flame Technique.
5. For every sample analyzed, verification is necessary to determine that method of
standard addition is not required (see Exhibit E).
6. If method of standard addition is required, follow the procedure given in
Exhibit E.
CLP-M modified for the Contract Laboratory Program.
D-39 ILM04.0
-------
Exhibit D Method 279.2
THALLIUM
Method 279.2 CLP-M* (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L
Approximate Detection Limit: 1 ug/L
Preparation of Standard Solution
1. Stock solution: Dissolve 1.303 g of thallium nitrate, TINO^ (analytical reagent
grade) in deionized distilled water. Add 10 mL of concentrated nitric acid and
dilute to 1 liter with deionized distilled water. 1 mL = 1 mg Tl (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. These solutions are also to be used for "standard
additions."
3. The calibration standards must be prepared using the same type of acid and at
the same concentration as will result in the sample to be analyzed after sample
preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 400°C.
3. Atomizing Time and Temp: 10 sec @ 2400°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 276.8 nm
6. Operating parameters should be set as specified by the particular instrument
manufacturer.
Notes
I. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, continuous flow purge gas and
non-pyrolytic graphite and are to be used as guidelines only. Smaller size
furnace devices or those employing faster rates of atomization can be operated
using lower atomization temperatures for shorter time periods than the above
recommended settings.
2. The use of background correction is required.
3. Nitrogen may also be used as the purge gas.
4. For every sample analyzed, verification is necessary to determine that method of
standard addition is not required (see Exhibit E) .
5. If method of standard addition is required, follow the procedure given in
Exhibit E.
*CLP-M modified for the Contract Laboratory Program.
D-40 ILM04.0
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PART C - ATOMIC ABSORPTION METHODS. FLAME TECHNIQUE*
Analvte/Method Page No.
Calcium - Method 215.1 CLP-M* D-42
Magnesium - Method 242.1 CLP-M D-43
Potassium - Method 258.1 CLP-M D-44
Sodium - Method 273.1 CLP-M D-45
+From "Interim Methods for the Sampling and Analysis of Priority Pollutants
in Sediments and Fish Tissue," USEPA EMSL, Cincinnati, Ohio, August 1977,
Revised October 1980, as modified for use in the Contract Laboratory
Program.
*CLP-M modified for the Contract Laboratory Program.
D-41 ILMO4.0
-------
Exhibit D Method 215.1
CALCIUM
Method 215.1 CLP-M* (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.2-7 mg/L using a wavelength of 422.7 nm
Sensitivity: 0.08 mg/L
Detection Limit: 0.01 mg/L
Preparation of Standard Solution
1. Stock Solution: Suspend 1.250 g of CaCC^ (analytical reagent grade), dried at
180°C for 1 hour before weighing, in deionized distilled water and dissolve
cautiously with a minimum of dilute HC1. Dilute to 1000 mL with deionized
distilled water. 1 mL = 0.5 mg Ca (500 mg/L).
2. Lanthanum chloride solution: Dissolve 29 g of La2O3, slowly and in small
portions, in 250 mL cone. HC1 (Caution: Reaction is violent) and dilute to
500 mL with deionized distilled water.
3. Prepare dilutions of the stock calcium solutions to be used as calibration
standards at the time of analysis. To each 10 mL of calibration standard and
sample alike add 1.0 mL of the lanthanum chloride solution, i.e., 20 mL of
standard or sample + 2 mL LaCl^ = 22 mL.
Instrumental Parameters (General)
1. Calcium hollow cathode lamp
2. Wavelength: 422.7 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Reducing
Notes
1. Phosphate, sulfate and aluminum interfere but are masked by the addition of
lanthanum. Because low calcium values result if the pH of the sample is above
1, both standards and samples are prepared in dilute hydrochloric acid
solution. Concentrations of magnesium greater than 1000 mg/L also cause low
calcium values. Concentrations of up to 500 mg/L each of sodium, potassium
and nitrate cause no interference.
2. Anionic chemical interferences can be expected if lanthanum is not used in
samples and standards.
3. The nitrous oxide-acetylene flame will provide two to five times greater
sensitivity and freedom from chemical inteferences. lonization interferences
should be controlled by adding a large amount of alkali to the sample and
standards. The analysis appears to be free from chemical suppressions in the
nitrous oxide-acetylene flame. (Atomic Absorption Newsletter 14, 29 [1975])
4. The 239.9 nm line may also be used. This line has a relative sensitivity of
120.
CLP-M modified for the Contract Laboratory Program.
D-42 ILMO4.0
-------
Exhibit D Method 242.1
MAGNESIUM
Method 242.1 CLP-M* (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.02-0.5 mg/L using a wavelength of 285.2 nm
Sensitivity: 0.007 mg/L
Detection Limit: 0.001 mg/L
Preparation of Standard Solution
1. Stock Solution: Dissolve 0.829 g of magnesium oxide, MgO (analytical reagent
grade), in 10 mL of redistilled HNO^ and dilute to 1 liter with deionized
distilled water. 1 mL = 0.50 mg Kg (500 mg/L).
2. Lanthanum chloride solution: Dissolve 29 g of La2C>3, slowly and in small
portions in 250 mL concentrated HC1 (Caution: Reaction is violent), and dilute
to 500 mL with deionized distilled water.
3. Prepare dilutions of the stock magnesium solution to be used as calibration
standards at the time of analysis. To each 10 mL volume of calibration
standard and sample alike add 1.0 mL of the lanthanum chloride solution, i.e.,
20 mL of standard or sample + 2 mL LaCl^ = 22 mL.
Instrumental Parameters (General)
1. Magnesium hollow cathode lamp
2. Wavelength: 285.2 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Notes
1. The interference caused by aluminum at concentrations greater than 2 mg/L is
masked by addition of lanthanum. Sodium, potassium and calcium cause no
interference at concentrations less than 400 mg/L.
2. The 202.5nm line may also be used. This line has a relative sensitivity of 25.
3. To cover the range of magnesium values normally observed in surface waters
(0.1-20 mg/L), it is suggested that either the 202.5 nm line be used or the
burner head be rotated. A 90° rotation of the burner head will produce
approximately one-eighth the normal sensitivity.
CLP-M modified for the Contract Laboratory Program.
D-43 ILM04.0
-------
Exhibit D Method 258.1
POTASSIUM
Method 258.1 CLP-M (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.1-2 mg/L using a wavelength of 766.5 nm
Sensitivity: 0.04 mg/L
Detection Limit: 0.01 mg/L
Preparation of Standard Solution
1. Stock Solution: Dissolve 0.1907 g of KC1 (analytical reagent grade), dried at
110°C, in deionized distilled water and make up to 1 liter. 1 mL = 0.10 mg K
(100 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. The calibration standards should be prepared using the
same type of acid and at the same concentration as will result in the sample to
be analyzed either directly or after processing.
Instrumental Parameters (General)
1. Potassium hollow cathode lamp
2. Wavelength: 766.5 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Slightly oxidizing
Notes
1. In air-acetylene or other high temperature flames (>2800°C), potassium can
experience partial ionization which indirectly affects absorption sensitivity.
The presence of other alkali salts in the sample can reduce this ionization and
thereby enhance analytical results. The ionization suppressive effect of
sodium is small if the ratio of Na to K is under 10. Any enhancement due to
sodium can be stabilized by adding excess sodium (1000 ug/mL) to both sample
and standard solutions. If more stringent control of ionization is required,
the addition of cesium should be considered. Reagent blanks must be analyzed
to correct for potassium impurities in the buffer zone.
2. The 404.4 nm line may also be used. This line has a relative sensitivity of
500.
3. To cover the range of potassium values normally observed in surface waters
(0.1-20 mg/L), it is suggested that the burner head be rotated. A 90° rotation
of the burner head provides approximately one-eighth the normal sensitivity.
CLP-M modified for the Contract Laboratory Program.
D-44 ILMO4.0
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Exhibit D Method 273.1
SODIUM
Method 273.1 CLP-M* (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.03-1 mg/L using a wavelength of 589.6 nm
Sensitivity: 0.015 mg/L
Detection Limit: 0.002 mg/L
Preparation of Standard Solutions
1. Stock Solution: Dissolve 2.542 g of NaCl (analytical reagent grade), dried at
140°C, in deionized distilled water and make up to 1 liter. 1 mL = 1 mg Na
(1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. The calibration standards should be prepared using the
same type of acid and at the same concentration as will result in the sample to
be analyzed either directly or after processing.
Instrumental Parameters (General)
1. Sodium hollow cathode lamp
2. Wavelength: 589.6 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Notes
1. The 330.2 nm resonance line of sodium, which has a relative sensitivity of 185,
provides a convenient way to avoid the need to dilute more concentrated
solutions of sodium.
2. Low-temperature flames increase sensitivity by reducing the extent of
ionization of this easily ionized metal. lonization may also be controlled by
adding potassium (1000 mg/L) to both standards and samples.
CLP-M modified for the Contract Laboratory Program.
D-45 ILMO4.0
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PART D - COLD VAPOR METHODS FOR MERCURY ANALYSIS
Method Page No.
Mercury Analysis in Water by Manual Cold Vapor Technique D-47
Method 245.1 CLP-M*
Mercury Analysis in Water by Automated Cold Vapor Technique D-52
Method 245.2 CLP-M
Mercury Analysis in Soil/Sediment by Manual Cold Vapor Technique D-56
Method 245.5 CLP-M
CLP-M modified for the Contract Laboratory Program.
D-46 ILM04.0
-------
Exhibit D Method 245.1
MERCURY ANALYSIS IN WATER BY MANUAL COLD VAPOR TECHNIQUE
MERCURY
Method 245.1 CLP-M* (Manual Cold Vapor Technique)
1. Scope and Application
1.1 In addition to inorganic forms of mercury, organic mercurials may also
be present. These organo-mercury compounds will not respond to the cold
vapor atomic absorption 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% recovery when used
as the oxidant with these compounds. Therefore, a persulfate oxidation
step following the addition of the permanganate has been included to
ensure that organo-mercury compounds, if present, will be oxidized to
the mercuric ion before measurement. A heat step is required for methyl
mercuric chloride when present in, or spiked to, a natural system.
1.2 The range of the method may be varied through instrument and/or recorder
expansion. Using a 100 mL sample, a detection limit of 0.2 ug Hg/L can
be achieved (see 10.1).
2. Summary of Method
2.1 The flameless AA procedure is a physical method based on the absorption
of radiation at 253.7 nm by mercury vapor. 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 atomic absorption
spectrophotometer. Absorbance (peak height) is measured as a function
of mercury concentration and recorded in the usual manner.
3. Sample Handling and Preservation
3.1 Until more conclusive data are obtained, samples are preserved by
acidification with nitric acid to a pH of 2 or lower immediately at the
time of collection (Exhibit D, Section II).
4. Interference
4.1 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 (Exhibit D, Section II).
4.2 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.
CLP-M modified for the Contract Laboratory Program.
D-47 ILM04.0
-------
Exhibit D Method 245.1
4.3 Sea waters, brines and industrial effluents high in chlorides require
additional permanganate (as much as 25 mL). During the oxidation step,
chlorides are converted to free chlorine which will also absorb
radiation at 253 nm. Care must be taken to assure that free chlorine is
absent before the mercury is reduced and swept into the cell. This may
be accomplished by using an excess of hydroxylamine sulfate reagent (25
mL). Both inorganic and organic mercury spikes have been quantitatively
recovered from the sea water using this technique.
5. Apparatus
5.1 Atomic Absorption Spectrophotometer: (See Note 1) Any atomic absorption
unit having an open sample presentation area in which to mount the
absorption cell is suitable. Instrument settings recommended by the
particular manufacturer should be followed.
NOTE 1: Instruments designed specifically for the measurement of
mercury using the cold vapor technique are commercially available and
may be substituted for the atomic absorption spectrophotometer.
5.2 Mercury Hollow Cathode Lamp: Westinghouse WL-22847, argon filled, or
equivalent.
5.3 Recorder: Any multi-range variable speed recorder that is compatible
with the UV detection system is suitable.
5.4 Absorption Cell: Standard spectrophotometer cells 10 cm long, having
quartz end windows may be used. Suitable cells may be constructed from
plexiglass tubing, 1" O.D. X 4-1/2". The ends are ground perpendicular
to the longitudinal axis and quartz windows (1" diameter X 1/16"
thickness) are cemented in place.
The cell is strapped to a burner for support and aligned in the light
beam by use of two 2" by 2" cards. One inch diameter holes are cut in
the middle of each card; the cards are then placed over each end of the
cell. The cell is then positioned and adjusted vertically and
horizontally to find the maximum transmittance.
5.5 Air Pump: Any peristaltic pump capable of delivering 1 liter of air per
minute may be used. A Masterflex pump with electronic speed control has
been found to be satisfactory.
5.6 Flowmeter: Capable of measuring an air flow of 1 liter per minute.
5.7 Aeration Tubing: A straight glass frit having a coarse porosity. Tygon
tubing is used for passage of the mercury vapor from the sample bottle
to the absorption cell and return.
5.8 Drying Tube: 6" X 3/4" diameter tube containing 20 g of magnesium
perchlorate (see Note 2).
NOTE 2: In place of the magnesium perchlorate drying tube, a small
reading lamp with 60W bulb may be used to prevent condensation of
moisture inside the cell. The lamp is positioned to shine on the
absorption cell maintaining the air temperature in the cell about 10°C
above ambient.
D-48 ILM04.0
-------
Exhibit D Method 245.1
6. Reagents
6.1 Sulfuric Acid, Cone: Reagent grade.
6.1.1 Sulfuric acid, 0.5 N: Dilute 14.0 mL of cone. sulfuric acid
to 1.0 liter.
6.2 Nitric Acid, Cone: Reagent grade of low mercury content (see Note 3).
NOTE 3: If a high reagent blank is obtained, it may be necessary to
distill the nitric acid.
6.3 Stannous Sulfate: Add 25 g stannous sulfate to 250 mL of 0.5 N sulfuric
acid. This mixture is a suspension and should be stirred continuously
during use. (Stannous chloride may be used in place of stannous
sulfate.)
6.4 Sodium Chloride-Hyroxylamine Sulfate Solution: Dissolve 12 g of sodium
chloride and 12 g of hydroxylamine sulfate in distilled water and dilute
to 100 mL. (Hydroxylamine hydrochloride may be used in place of
hydroxylamine sulfate.)
6.5 Potassium Permanganate (KMnO^): 5% solution, w/v. Dissolve 5 g of
potassium permanganate in 100 mL of distilled water.
6.6 Potassium Persulfate: 5% solution, w/v. Dissolve 5 g of potassium
persulfate in 100 mL of distilled water.
6.7 Stock Mercury Solution: Dissolve 0.1354 g of mercuric chloride in 75 mL
of distilled water. Add 10 mL of cone. nitric acid and adjust the
volume to 100.0 mL. 1 mL = 1 mg Hg.
6.8 Working Mercury Solution: Make successive dilutions of the stock
mercury solution to obtain a working standard containing 0.1 ug per mL.
This working standard and the dilutions of the stock mercury solution
should be prepared fresh daily. Acidity of the working standard should
be maintained at 0.15% nitric acid. This acid should be added to the
flask as needed before the addition of the aliquot.
7. Calibration
7.1 Transfer 0, 0.2, 0.5, 1.0, 5.0 and 10.0 mL aliquots of the working
mercury solution containing 0 to 1.0 ug of mercury to a series of 300 mL
BOD bottles. Add enough distilled water to each bottle to make a total
volume of 100 mL. Mix thoroughly and add 5 mL of cone. sulfuric acid
(6.1) and 2.5 mL of cone. nitric acid (6.2) to each bottle. Add 15 mL
of KMnO^ (6.5) solution to each bottle and allow to stand at least 15
minutes. Add 8 mL of potassium persulfate (6.6) to each bottle and heat
for 2 hours in a water bath maintained at 95°C. Alternatively, cover
the BOD bottles with foil and heat in an autoclave for 15 minutes at
120°C and 15 PSI. Cool and add & mL of sodium chloride-hydroxylamine
sulfate solution (6.4) to reduce the excess permanganate. When the
solution has been decolorized wait 30 seconds, add 5 mL of the stannous
sulfate solution (6.3) and immediately attach the bottle to the aeration
apparatus forming a closed system. At this point the sample is allowed
to stand quietly without manual agitation.
D-49 ILM04.0
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Exhibit D Method 245.1
The circulating pump, which has previously been adjusted to a rate of 1
liter per minute, is allowed to run continuously (see Note 4). The
absorbance will increase and reach maximum within 30 seconds. As soon
as the recorder pen levels off, approximately 1 minute, open the bypass
valve and continue the aeration until the absorbance returns to its
minimum value (see Note 5). Close the bypass valve, remove the stopper
and frit from the BOD bottle and continue the aeration. Proceed with
the standards and construct a standard curve by plotting peak height
versus micrograms of mercury.
NOTE 4: An open system where the mercury vapor is passed through the
absorption cell only once may be used instead of the closed system.
NOTE 5: Because of the toxic nature of mercury vapor precaution must be
taken to avoid its inhalation. Therefore, a bypass has been included in
the system to either vent the mercury vapor into an exhaust hood or pass
the vapor through some absorbing media, such as equal volumes of 0.1 M
KMnO4, and 10% H2SO4 or 0.25% iodine in a 3% a KI solution. A specially
treated charcoal that will adsorb mercury vapor is commercially
available.
8. Procedure
8.1 Transfer 100 mL, or an aliquot diluted to 100 mL, containing not more
than 1.0 ug of mercury, to a 300 mL BOD bottle. Add 5 mL of cone.
sulfuric acid (6.1) and 2.5 mL of cone. nitric acid (6.2) mixing after
each addition. Add 15 mL of potassium permanganate solution (6.5) to
each sample bottle (see Note 6). For sewage samples additional
permanganate may be required. Shake and add additional portions of
potassium permanganate solution, if necessary, until the purple color
persists for at least 15 minutes. Add 8 mL of potassium persulfate
(6.6) to each bottle and heat for 2 hours in a water bath at 95°C.
NOTE 6: The same amount of KMnO4 added to the samples should be present
in standards and blanks.
Cool and add 6 mL of sodium chloride-hydroxylamine sulfate (6.4) to
reduce the excess permanganate (see Note 7). Purge the headspace in the
BOD bottle for at least 1 minute and add 5 mL of stannous sulfate (6.3)
and immediately attach the bottle to the aeration apparatus. Continue
as described under Calibration.
NOTE 7: Add reductant in 6 mL increments until KMnO4 is completely
reduced.
9. Calculations
9.1 Determine the peak height of the unknown from the chart and read the
mercury value from the standard curve.
9.2 Calculate the mercury concentration in the sample by the formula:
ua Hg/L = "gtfg- c^ve r x 1000 M.
aliauot volume, mL 1 L
D-50 ILM04.0
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Exhibit D Method 245.1
10. Appendix
10.1 If additional sensitivity is required, a 200 mL sample with recorder
expansion may be used provided the instrument does not produce undue
noise. Using a Coleman MAS-50 with a drying tube of magnesium
perchlorate and a variable recorder, 2 mv was set to read full scale.
With these conditions, and distilled water solutions of mercuric
chloride at concentrations of 0.15, 0.10, 0.05 and 0.025 ug/L, the
standard deviations were +0.027, +0.0006, +0.01 and +0.004. Percent
recoveries at these levels were 107, 83, 84 and 96%, respectively.
10.2 Directions for the disposal of mercury-containing wastes are given in
ASTM Standards, Part 31, "Water," p. 349, Method D3223 (1976).
D-51 ILM04.0
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Exhibit D Method 245.2
MERCURY ANALYSIS IN WATER BY AUTOMATED COLD VAPOR TECHNIQUE
MERCURY
Method 245.2 CLP-M* (Automated Cold Vapor Technique)
1. Scope and Application
1.1 The working range is 0.2 to 20.0 ug Hg/L.
2. Summary of Method
2.1 The flameless AA procedure is a physical method based on the absorption
of radiation at 253.7 nm by mercury vapor. The mercury is reduced to
the elemental state and aerated from solution. The mercury vapor passes
through a cell positioned in the light path of an atomic absorption
spectrophotometer. Absorbance (peak height) is measured as a function
of mercury concentration and recorded in the usual manner.
2.2 In addition to inorganic forms of mercury, organic mercurials may also
be present. These organo-mercury compounds will not respond to the
flameless atomic absorption 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% recovery when used
as the oxidant with these compounds. Therefore, an automated persulfate
oxidation step following the automated addition of the permanganate has
been included to ensure that organo-mercury compounds, if present, will
be oxidized to the mercuric ion before measurement.
3. Sample Handling and Preservation
3.1 Until more conclusive data are obtained, samples are preserved by
acidification with nitric acid to a pH of 2 or lower immediately at the
time of collection (Exhibit D, Section II).
4. Interferences (see NOTE 1)
4.1 Some sea waters and waste-waters high in chlorides have shown a positive
interference, probably due to the formation of free chlorine.
4.2 Formation of a heavy precipitate, in some wastewaters and effluents, has
been reported upon addition of concentrated sulfuric acid. If this is
encountered, the problem sample cannot be analyzed by this method.
4.3 Samples containing solids must be blended and then mixed while being
sampled if total mercury values are to be reported.
NOTE 1: All of the above interferences can be overcome by use of the
Manual Mercury method.
"CLP-M modified for the Contract Laboratory Program.
D-52 ILM04.0
-------
Exhibit D Method 245.2
5. Apparatus
5.1 Technicon Auto Analyzer or equivalent instrumentation consisting of:
5.1.1 Sampler II with provision for sample mixing.
5.1.2 Manifold.
5.1.3 Proportioning Pump II or III.
5.1.4 High temperature heating bath with two distillation coils
(Technicon Part #116-0163) in series.
5.2 Vapor-liquid separator.
5.3 Absorption cell, 100 mm long, 10 mm diameter with quartz windows.
5.4 Atomic Absorption Spectrophotometer (see Note 2): Any atomic absorption
unit having an open sample presentation area in which to mount the
absorption cell is suitable. Instrument settings recommended by the
particular manufacturer should be followed.
NOTE 2: Instruments designed specifically for the measurement of
mercury using the cold vapor technique are commercially available and
may be substituted for the atomic absorption spectrophotometer.
5.5 Mercury Hollow Cathode Lamp: Westinghouse WL-22847, argon filled, or
equivalent.
5.6 Recorder: Any multi-range variable speed recorder that is compatible
with the UV detection system is suitable.
6. Reagents
6.1 Sulfuric Acid, Cone: Reagent grade
6.1.1 Sulfuric acid, 2 N: Dilute 56 mL of cone, sulfuric acid to 1
liter with distilled water.
6.1.2 Sulfuric acid, 10%: Dilute 100 mL cone. sulfuric acid to 1
liter with distilled water.
6.2 Nitric acid, Cone: Reagent grade of low mercury content.
6.2.1 Nitric Acid, 0.5% Wash Solution: Dilute 5 mL of cone. nitric
acid to 1 liter with distilled water.
6.3 Stannous Sulfate (See Note 3): Add 50 g stannous sulfate to 500 mL of 2
N sulfuric acid (6.1.1). This mixture is a suspension and should be
stirred continuously during use.
NOTE 3: Stannous chloride may be used in place of stannous sulfate.
D-53 ILM04.0
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Exhibit D Method 245.2
6.4 Sodium Chloride-Hydroxylamine Sulfate (See Note 4) Solution: Dissolve
30 g of sodium chloride and 30 g of hydroxylamine sulfate in distilled
water to 1 liter.
NOTE 4: Hydroxylamine hydrochloride may be used in place of
hydroxylamine sulfate.
6.5 Potassium Permanganate (KMnO^): 0.5% solution, w/v. Dissolve 5 g of
potassium permanganate in 1 liter of distilled water.
6.6 Potassium Permanganate, 0.1 N: Dissolve 3.16 g of potassium
permanganate in distilled water and dilute to 1 liter.
6.7 Potassium Persulfate: 0.5% solution, w/v. Dissolve 5 g of potassium
persulfate in 1 liter of distilled water.
6.8 Stock Mercury Solution: Dissolve 0.1354 g of mercuric chloride in 75 mL
of distilled water. Add 10 mL of cone, nitric acid and adjust the
volume to 100.0 mL. 1.0 mL = 1.0 mg Hg.
6.9 Working Mercury Solution: Make successive dilutions of the stock
mercury solution (6.8) to obtain a working standard containing 0.1 ug
per mL. This working standard and the dilutions of the stock mercury
solution should be prepared fresh daily. Acidity of the working
standard should be maintained at 0.15% nitric acid. This acid should be
added to the flask as needed before the addition of the aliquot. From
this solution, prepare standards containing 0.2, 0.5, 1.0, 2.0, 5.0,
10.0, 15.0 and 20.0 ug Hg/L.
6.10 Air Scrubber Solution: Mix equal volumes of 0.1 N potassium
permanganate (6.6) and 10% sulfuric acid (6.1.2).
7. Procedure (See Note 5)
7.1 Set up manifold.
7.2 Feeding all the reagents through the system with acid wash solution
(6.2.1) through the sample line, adjust heating bath to 105°C.
7.3 Turn on atomic absorption spectrophotometer, adjust instrument settings
as recommended by the manufacturer, align absorption cell in light path
for maximum nransmittance and place heat lamp directly over absorption
cell.
7.4 Arrange working mercury standards from 0.2 to 20.0 ug Hg/L in sampler
and start sampling. Complete loading of sample tray with unknown
samples.
7.6 After the analysis is complete, put all lines except the H2SO4 line in
distilled water to wash out system. After flushing, wash out the H2SO4
line. Also flush the coils in the high temperature heating bath by
pumping stannous sulfate (6.3) through the sample lines followed by
distilled water. This will prevent build-up of oxides of manganese.
NOTE 5: Because of the toxic nature of mercury vapor, precaution must
be taken to avoid its inhalation. Venting the mercury vapor into an
exhaust hood or passing the vapor through some absorbing media such as
0-54 ILM04.0
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Exhibit D Method 245.2
equal volumes of 0.1 N KMnO4(6.6) and 10% H2SO4 (6.1.2), or 0.25% iodine
in a 3% KI solution, is recommended. A specially treated charcoal that
will absorb mercury vapor is also available.
8. Calculations
8.1 Prepare a standard curve by plotting the peak height of processed
standards against true concentration values. Use a linear regression
equation to determine the concentration of field and QC samples by
comparing the peak height of the samples with the peak height of the
calibration standards.
8.2 If samples were diluted for analysis, multiply the results from the
linear regression by the diluition factor.
D-55 ILM04.0
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Exhibit D Method 245.5
MERCURY ANALYSIS IN SOIL/SEDIMENT BY MANUAL COLD VAPOR TECHNIQUE
MERCURY (in Sediments)
Method 245.5 CLP-M* (Manual Cold Vapor Technique)
1. Scope and Application
1.1 This procedure measures total mercury (organic and inorganic) in soils,
sediments, bottom deposits and sludge type materials.
1.2 The range of the method is 0.1 to 5 ug/g. The range may be extended
above or below the normal range by increasing or decreasing sample size
or through instrument and recorder control
2. Summary of Method
2.1 A weighed portion of the sample is acid digested for 2 minutes at 95°C,
followed by oxidation with potassium permanganate and potassium
persulfate. Mercury in the digested sample is then measured by the
conventional cold vapor technique.
2.2 An alternate digestion involving the use of an autoclave is described in
8.2.
3. Sample Handling and Preservation
3.1 Because of the extreme sensitivity of the analytical procedure and the
omnipresence of mercury, care must be taken to avoid extraneous
contamination. Sampling devices and sample containers should be
ascertained to be free of mercury; the sample should not be exposed to
any condition in the laboratory that may result in contact or air-borne
mercury contamination.
3.2 Refrigerate solid samples at 4°C (±2°) upon receipt until analysis (see
Exhibit D, Section II).
3.3 The sample should be analyzed without drying. A separate percent solids
determination is required (Part F).
4. Interferences
4.1 The same types of interferences that may occur in water samples are also
possible with sediments, i.e., sulfides, high copper, high chlorides,
etc.
4.2 Samples containing high concentrations of oxidizable organic materials,
as evidenced by high chemical oxygen demand values, may not be
completely oxidized by this procedure. When this occurs, the recovery
of organic mercury will be low. The problem can be eliminated by
reducing the weight of the original sample or by increasing the amount
of potassium persulfate (and consequently stannous chloride) used in the
digestion.
CLP-M modified for the Contract Laboratory Program.
D-56 ILM04.0
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Exhibit D Method 245.5
5. Apparatus
5.1 Atomic Absorption Spectrophotometer (see Note 1): Any atomic absorption
unit having an open sample presentation area in which to mount the
absorption cell is suitable. Instrument settings recommended by the
particular manufacturer should be followed.
NOTE 1: Instruments designed specifically for the measurement of
mercury using the cold vapor technique are commercially available and
may be substituted for the atomic absorption spectrophotometer.
5.2 Mercury Hollow Cathode Lamp: Westinghouse WL-22847, argon filled, or
equivalent.
5.3 Recorder: Any multi-range variable speed recorder that is compatible
with the UV detection system is suitable.
5.4 Absorption Cell: Standard spectrophotometer cells 10 cm long, having
quartz end windows, may be used. Suitable cells may be constructed from
pexiglass tubing, 1" O.D. X. 4-1/2". The ends are ground perpendicular
to the longitudinal axis and quartz windows (1" diameter X 1/16"
thickness) are cemented in place. Gas inlet and outlet ports (also of
plexiglass but 1/4" O.D.) are attached approximately 1/2" from each end.
The cell is strapped to a burner for support and aligned in the light
beam to give the maximum transmittance. Two 2" X 2" cards with one inch
diameter holes may be placed over each end of the cell to assist in
positioning the cell for maximum transmittance.
5.5 Air Pump: Any peristaltic pump capable of delivering 1 liter of air per
minute may be used. A Masterflex pump with electronic speed control has
been found to be satisfactory. (Regulated compressed air can be used in
an open one-pass system.)
5.6 Flowmeter: Capable of measuring an air flow of 1 liter per minute.
5.7 Aeration Tubing: Tygon tubing is used for passage of the mercury vapor
from the sample bottle to the absorption cell and return. Straight
glass tubing terminating in a coarse porous frit is used for sparging
air into the sample.
5.8 Drying Tube: 6" X 3/4" diameter tube containing 20 g of magnesium
perchlorate (see Note 2).
NOTE 2: In place of the magnesium perchlorate drying tube, a small
reading lamp with 60W bulb may be used to prevent condensation of
moisture inside the cell. The lamp is positioned to shine on the
absorption cell maintaining the air temperature in the cell about 10°C
above ambient.
6. Reagents
6.1 Sulfuric Acid, Cone: Reagent grade of low mercury content.
6.2 Nitric Acid, Cone: Reagent grade of low mercury content.
D-57 ILM04.0
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Exhibit D Method 245.5
6.3 Stannous Sulfate: Add 25 g stannous sulfate to 250 mL of 0.5 N sulfuric
acid (6.1). This mixture is a suspension and should be stirred
continuously during use.
6.4 Sodium Chloride-Hydroxylamine Sulfate (See Note 3) Solution: Dissolve
12 g of sodium chloride and 12 g of hydroxylamine sulfate in distilled
water and dilute to 100 mL.
NOTE 3: A 10% solution of stannous chloride may be substituted for
(6.3) and hydroxylamine hydrochloride may be used in place of
hydroxylamine sulfate in (6.4).
6.5 Potassium Permanganate (KMnO^): 5% solution, w/v. Dissolve 5 g of
potassium permanganate in 100 mL of distilled water
6.6 Potassium Persulfate: 5% solution, w/v. Dissolve 5 g of potassium
persulfate in 100 mL of distilled water.
6.7 Stock Mercury Solution: Dissolve 0.1354 g of mercuric chloride in 75 mL
of distilled water. Add 10 mL of cone. nitric acid and adjust the
volume to 100.0 mL. 1.0 = 1.0 mg Hg.
6.8 Working Mercury Solution: Make successive dilutions of the stock
mercury solution (6.7) to obtain a working standard containing 0.1
ug/mL. This working standard and the dilution of the stock mercury
solutions should be prepared fresh daily. Acidity of the working
standard should be maintained at 0.15% nitric acid. This acid should be
added to the flask as needed before the addition of the aliquot.
7. Calibration
7.1 Transfer 0, 0.2, 0.5, 1.0, 5.0 and 10 mL aliquots of the working mercury
solutions (6.8) containing 0 to 1.0 ug of mercury to a series of 300 mL
BOD bottles. Add enough distilled water to each bottle to make a total
volume of 10 mL. Add 5 mL of cone. B^SO^j (6.1) and 2.5 mL of cone.
HNO3 (6.2) and heat 2 minutes in a water bath at 95°C. Allow the sample
to cool and add 50 mL distilled water, 15 mL of KMnO^ solution (6.5) and
8 mL of potassium persulfate solution (6.6) to each bottle and return to
the water bath for 30 minutes. Cool and add 6 mL of sodium chloride-
hydroxylamine sulfate solution (6.4) to reduce the excess permanganate.
Add 50 mL of distilled water (final volume of distilled water = 100 mL).
Treating each bottle individually, add 5 mL of stannous sulfate solution
(6.3) and immediately attach the bottle to the aeration apparatus. At
this point the sample is allowed to stand quietly without manual
agitation. The circulating pump, which has previously been adjusted to
a rate of 1 liter per minute, is allowed to run continuously. The
absorbance, as exhibited either on the spectrophotometer or the
recorder, will increase and reach maximum within 30 seconds. As soon as
the recorder pen levels off, approximately 1 minute, open the bypass
valve and continue the aeration until the absorbance returns to its
minimum value (see Note 4). Close the bypass valve, remove the fritted
tubing from the BOD bottle and continue the aeration. Proceed with the
standards and construct a standard curve by plotting peak height versus
micrograms of mercury.
NOTE 4: Because of the toxic nature of mercury vapor, precaution must be
taken to avoid its inhalation. Therefore, a bypass has been included in the
D-58 ILM04.0
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Exhibit D Method 245.5
system to either vent the mercury vapor into an exhaust hood or pass the
vapor through some absorbing media, such as: a) equal volumes of 0.1 N KMnO4
and 10% HjSC^, or b) 0.25% iodine in a 3% KI solution. A specially treated
charcoal that will absorb mercury vapor is also commercially available.
8. Procedure
8.1 Weigh a representative 0.2 g portion of wet sample and place in the bottom of
a BOD bottle. Add enough distilled water to each sample to make a total
volume of 10 mL. Add 5 mL of cone. sulfuric acid (6.1) and 2.5 mL of cone.
nitric acid (6.2) mixing after each addition. Heat two minutes in a water
bath at 95°C. Cool, add 50 mL distilled water, 15 mL potassium permanganate
solution (6.5) and 8 mL of potassium persulfate solution (6.6) to each sample
bottle. Mix thoroughly and place in the water bath for 30 minutes at 95°C.
Cool and add 6 mL of sodium chloride-hydroxylamine sulfate (6.4) to reduce
the excess permanganate. Add 50 mL of distilled water (final volume of
distilled water = 100 mL). Treating each bottle individually, purge the head
space of the sample bottle for at least one minute and add 5 mL of stannous
sulfate (6.3) and immediately attach the bottle to the aeration apparatus.
Continue as described under 7.1.
8.2 An alternate digestion procedure employing an autoclave may also be used. In
this method 5 mL of cone. P^SO^ and 2 mL of cone. HNOj are added to the 0.2
g of sample. 5 mL of saturated KMnO^ solution and 8 mL of potassium
persulfate solution are added and the bottle is covered with a piece of
aluminum foil. The sample is autoclaved at 121°C and 15 PSI for 15 minutes.
Cool, make up to a volume of 100 mL with distilled water and add 6 mL of
sodium chloride-hydroxylamine sulfate solution (6.4) to reduce the excess
permanganate. Purge the headspace of the sample bottle for at least one
minute and continue as described under 7.1.
9. Calculations
9.1 Measure the peak height of the unknown from the chart and read the mercury
value from the standard curve.
9.2 Calculate the mercury concentration in the sample by the formula:
ug Hg/g = 7ug/L H%' curve x final vol. after prep. , L
alguot dry wt., g
9.3 Report mercury concentrations as described for aqueous mercury samples
converted to units of mg/kg. The sample result or the detection limit for
each sample must be corrected for sample weight and % solids before
reporting.
NOTE 5: ug/g is equivalent to mg/kg.
D-59 ILM04.0
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PART E - METHODS FOR TOTAL CYANIDE ANALYSIS
Method Page No,
Method for Total Cyanide Analysis in Water
Method 335.2 CLP-M* D-61
Method for Total Cyanide Analysis in Soil/Sediment
Method 335.2 CLP-M D-69
Method for Total Cyanide Analysis by Midi Distillation
Method 335.2 CLP-M D-77
CLP-M Modified for the Contract Laboratory Program.
D-60 ILM04.0
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Exhibit D Method 335.2
METHOD FOR TOTAL CYANIDE ANALYSIS IN WATER
CYANIDE, TOTAL (in Water)
Method 335.2 CLP-M (Titrimetric; Manual Spectrophotometric; Semi-Automated
Spectrophotometric)
1. Scope and Application
1.1 This method is applicable to the determination of cyanide in drinking, surface
and saline waters, and domestic and industrial wastes.
1.2 The titration procedure using silver nitrate with p-
dimethylaminobenzalrhodanine indicator is used for measuring concentrations of
cyanide exceeding 1 mg/L (0.25 mg/250 mL of absorbing liquid) (Option A,
8.2).
1.3 The manual colorimetric procedure is used for concentrations below 1 mg/L of
cyanide and is sensitive to about 0.01 mg/L (Option B, 8.3).
1.4 The working range of the semi-automated Spectrophotometric method is 0.020 to
0.200 mg/L. Higher level samples must be diluted to fall within the working
range (Option C, 8.4).
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
containing sodium hydroxide solution. The cyanide ion in the absorbing
solution is then determined by volumetric titration or colorimetrically.
2.2 In the colorimetric measurement, the cyanide is converted to cyanogen
chloride, CNC1, by reaction with chloramine-T at a pH less than 8 without
hydrolyzing to the cyanate. 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.
2.3 The titrimetric measurement uses a standard solution of silver nitrate to
titrate cyanide in the presence of a silver sensitive indicator.
3. Definitions
Cyanide is defined as cyanide ion and complex cyanides converted to
hydrocyanic acid (HCN) by reaction in a reflux system of a mineral acid in the
presence of magnesium ion.
4. Sample Handling and Preservation
4.1 All bottles must be thoroughly cleansed and rinsed to remove soluble material
from containers.
CLP-M Modified for rhe Contract Laboratory Program.
D-61 ILM04.0
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Exhibit D Method 335.2
4.2 Oxidizing agents such as chlorine decompose most of the cyanides. Test a drop
of the sample with potassium iodide-starch test paper (Kl-starch paper); a
blue color indicates the need for treatment. 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.
4.3 Samples are preserved with 2 mL of 10 N sodium hydroxide per liter of sample
(pH> 12) at the time of collection (Exhibit D, Section II).
4.4 Samples must be stored at 4°C(±2°C) and must be analyzed within the holding
time specified in Exhibit D, Section II.
5. Interferences
5.1 Interferences are eliminated or reduced by using the distillation procedure
described in 8.1.
5.2 Sulfides adversely affect the colorimetric and titration procedures. If a
drop of the distillate on lead acetate test paper indicates the presence of
sulfides, treat 25 mL more of the sample than that required for the cyanide
determination with powdered cadmium carbonate. Yellow cadmium sulfide
precipitates if the sample contains sulfide. Repeat this operation until a
drop of the treated sample 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 sample to be used for analysis. Avoid a large
excess of cadmium carbonate and a long contact time in order to minimize a
loss by complexation or occlusion of cyanide on the precipitated material.
Sulfides should be removed prior to preservation with sodium hydroxide as
described in 4.3.
5.3 The presence of surfactants may cause the sample to foam during refluxing. If
this occurs, the addition of an agent such as Dow Corning 544 antifoam agent
will prevent the foam from collecting in the condenser. Fatty acids will
distill and form soaps under alkaline titration conditions, making the end
point almost impossible to detect. When this occurs, one of the
spectrophotometrlc methods should be used.
6. Apparatus
6.1 Reflux distillation apparatus. The boiling flask should be of 1 liter size
with inlet tube and provision for condenser. The gas absorber may be a
Fisher-Milligan scrubber.
6.2 Microburet, 5.0 mL (for titration)
6.3 Spectrophotometer suitable for measurements at 578 nm or 620 nm with a 1.0 cm
cell or larger (for manual spectrophotometric method).
6.4 Technicon AA II system or equivalent instrumentation (for automated
spectrophotometric method) including:
6.4.1 Sampler
6.4.2 Pump III
D-62 ILM04.0
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Exhibit D Method 335.2
6.4.3 Cyanide manifold
6.4.4 SCIC colorimeter with 15 mm flowcells and 570 nm filters
6.4.5 Recorder
6.4.6 Data system (optional)
6.4.7 Glass or plastic tubes for the sampler
7. Reagents
7.1 Distillation and Preparation Reagents
7.1.1 Sodium hydroxide solution, 1.25 N: Dissolve 50 g of NaOH in distilled
water, and dilute to 1 liter with distilled water.
7.1.2 Cadmium carbonate: powdered
7.1.3 Ascorbic acid: crystals
7.1.4 Sulfuric acid: concentrated
7.1.5 Magnesium chloride solution: Weigh 510 g of MgCl2•6H2O into a 1000 mL
flask, dissolve, and dilute to 1 liter with distilled water.
7.2 Stock Standards and Titration Reagents
7.2.1 Stock cyanide solution: Dissolve 2.51 g of KCN and 2 g KOH in 1
liter of distilled water. Standardize with 0.0192 N AgNO3.
7.2.2 Standard cyanide solution, intermediate: Dilute 50.0 mL of stock (1
mL = 1 mg CM) to 1000 mL with distilled water.
7.2.3 Standard cyanide solution: Prepare fresh daily by diluting 100.0 mL
of intermediate cyanide solution to 1000 mL with distilled water and
store in a glass stoppered bottle. 1 mL = 5.0 ug CN (5.0 mg/L).
7.2.4 Standard silver nitrate solution, 0.0192 N: Prepare by crushing
approximately 5 g AgNO-^ crystals and drying to constant weight at
40°C. Weigh out 3.2647 g of dried AgNO3, dissolve in distilled
water, and dilute to 1000 mL (1 mL = 1 mg CN).
7.2.5 Rhodanine indicator: Dissolve 20 mg of p-dimethyl-
aminobenzalrhodanine in 100 mL of acetone.
7.2.6 Sodium hydroxide solution, 0.25 N: Dissolve 10 g of NaOH in
distilled water and dilute to 1 liter.
7.3 Manual Spectrophotometric Reagents
7.3.1 Sodium dihydrogenphosphate, 1 M: Dissolve 138 g of Naf^PC^-P^O in a
liter of distilled water. Refrigerate this solution.
D-63 ILM04.0
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Exhibit D Method 335.2
7.3.2 Chloramine-T solution: Dissolve 1.0 g of white, water soluble
chloramine-T in 100 mL of distilled water and refrigerate until ready
to use. Prepare fresh weekly.
7.3.3 Color Reagent-One of the following may be used:
7.3.3.1 Pyridine-barbituric acid reagent: Place 15 g of
barbituric acid in a 250 mL volumetric flask and add just
enough distilled water to wash the sides of the flask and
wet the barbituric acid. Add 75 mL of pyridine and mix.
Add 15 mL of HC1 (sp gr 1.19), mix, and cool to room
temperature. Dilute to 250 mL with distilled water and
mix. This reagent is stable for approximately six months
if stored in a cool, dark place.
7.3.3.2 Pyridine-pyrazolone solution:
7.3.3.2.1 3-Methyl-l-phenyl-2-pyrazolin-5-one reagent,
saturated solution: Add 0.25 g of 3-methyl-l-
phenyl-2-pyrazolin-5-one to 50 mL of distilled
water, heat to 60°C with stirring. Cool to
room temperature.
7.3.3.2.2 3,3'Dimethyl-1,1'-diphenyl [4,4'-bi-2
pyrazolin]-5,5'dione (bispyrazolone):
Dissolve 0.01 g of bispyrazolone in 10 mL of
pyridine.
7.3.3.2.3 Pour solution (7.3.3.2.1) through non-acid-
washed filter paper. Collect the filtrate.
Through the same filter paper pour solution
(7.3.3.2.2) collecting the filtrate in the
same container as filtrate from (7.3.3.2.1).
Mix until the filtrates are homogeneous. The
mixed reagent develops a pink color but this
does not affect the color production with
cyanide if used within 24 hours of
preparation.
7.4 Semi-Automated Spectrophotometric Reagents
7.4.1 Chloramine-T solution: Dissolve 0.40 g of chloramine-T in distilled
water and dilute to 100 mL. Prepare fresh daily.
7.4.2 Phosphate buffer: Dissolve 138 g of NaH2PO4-H2O in distilled water
and dilute to 1 liter. Add 0.5 mL of Brij-35 (available from
Technicon). Store at 4°C(±2°C).
7.4.3 Pyridine-barbituric acid solution: Transfer 15 g of barbituric acid
into a 1 liter volumetric flask. Add about 100 mL of distilled water
and swirl the flask. Add 74 mL of pyridine and mix. Add 15 mL of
concentrated HCl and mix. Dilute to about 900 mL with distilled water
and mix until the barbituric acid is dissolved. Dilute to 1 liter
with distilled water. Store at 4°C(±2°C).
D-64 ILM04.0
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Exhibit D Method 335.2
7.4.4 Sampler wash: Dissolve 10 g of NaOH in distilled water and dilute to
1 liter.
8. Procedure
8.1 Distillation
8.1.1 Place 500 mL of sample in the 1 liter boiling flask. Add 50 mL of
sodium hydroxide (7.1.1) to the absorbing tube and dilute if
necessary with distilled water to obtain an adequate depth of liquid
in the absorber. Connect the boiling flask, condenser, absorber and
trap in the train.
8.1.2 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.
NOTE: The bubble rate will not remain constant after the reagents
have been added and while heat is being applied to the flask. It will
be necessary to readjust the air rate occasionally to prevent the
solution in the boiling flask from backing up into the air inlet tube.
8.1.3 Slowly add 25 mL concentrated sulfuric acid (7.1.4) through the air
inlet tube. Rinse the tube with distilled water and allow the
airflow to mix the flask contents for 3 minutes. Pour 20 mL of
magnesium chloride solution (7.1.5) into the air inlet and wash down
with a stream of water.
8.1.4 Heat the solution to boiling, taking care to prevent the solution
from backing up into and overflowing from the air inlet tube. Reflux
for one hour. Turn off heat and continue the airflow for at least 15
minutes. After cooling the boiling flask, disconnect absorber and
close off the vacuum source.
8.1.5 Drain the solution from the absorber into a 250 mL volumetric flask
and bring up to volume with distilled water washings from the
absorber tube.
NOTE: The distillation procedure results in a 2x concentration of the
sample.
8.2 Titrimetric Determination (Option A)
8.2.1 If the sample contains more than 1 mg of CN, transfer the distillate,
or a suitable aliquot diluted to 250 mL, to a 500 mL Erlenmeyer
flask. Add 10-12 drops of the benzalrhodanine indicator.
8.2.2 Titrate with standard silver nitrate to the first change in color
from yellow to brownish-pink. Titrate a distilled water blank using
the same amount of sodium hydroxide and indicator as in the sample.
8.2.3 The analyst should familiarize himself with the 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.
D-65 ILM04.0
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Exhibit D Method 335.2
8.3 Manual Spectrophotometric Determination (Option B)
8.3.1 Withdraw 50 mL or less of the solution from the flask and transfer to
a 100 mL volumetric flask. If less than 50 mL is taken, dilute to 50
mL with 0.25 N sodium hydroxide solution (7.2.6). Add 15.0 mL of
sodium phosphate solution (7.3.1) and mix. The dilution factor must
be reported on Form XIV.
8.3.1.1 Pyridine-barbituric acid method: Add 2 mL of chloramine-T
(7.3.2) and mix. After 1 to 2 minutes, add 5 mL of
pyridine-barbituric acid solution (7.3.3.1) and mix.
Dilute to mark with distilled water and mix again. Allow
8 minutes for color development then read absorbance at
578 nm in a 1 cm cell within 15 minutes.
8.3.1.2 Pyridine-pyrazolone method: Add 0.5 mL of chloramine-T
(7.3.2) and mix. After 1 to 2 minutes, add 5 mL of
pyridine-pyrazolone solution (7.3.3.2) and mix. Dilute to
mark with distilled water and mix again. After 40
minutes, read absorbance at 620 nm in a 1 cm cell. NOTE:
More than 0.5 mL of chloramine-T will prevent the color
from developing with pyridine-pyrazolone.
8.3.2 Prepare a minimum of 3 standards and a blank by pipetting suitable
volumes of standard solution into 250 mL volumetric flasks. NOTE:
One calibration standard must be at the Contract Required Detection
Limit (CRDL). To each standard, add 50 mL of 1.25 N sodium hydroxide
and dilute to 250 mL with distilled water. The same method for color
development (i.e., pyridine-barbituric acid or pyridine-pyrazolone)
must be used for both the samples and standards. Standards must
bracket the concentration of the samples. If dilution is required,
use the blank solution.
As an example, standard solutions could be prepared as follows:
mL of Standard Solution Cone, ug CN
(1.0 = 5 uq CN) per 250 mL
0 Blank
0.5 2.5
1.0 5
5.0 25
10.0 50
15.0 75
20.0 100
8.3.2.1 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.
D-66 ILM04.0
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Exhibit D Method 335.2
8.3.2.2 Prepare a standard curve by plotting absorbance of
standard vs. cyanide concentrations (per 250 mL).
8.4 Semi-Automated Spectrophotometric Determination (Option C)
8.4.1 Set up the manifold. Pump the reagents through the system until a
steady baseline is obtained.
8.4.2 Calibration standards: Prepare a blank and at least three
calibration standards over the range of the analysis. One
calibration standard must be at the CRDL. For a working range of 0-
200 ug/L, the following standards may be used:
mL Standard Solution Concentration
(7.2.3) diluted to 1 liter uq CN/L
0
2.0
4.0
10.0
20.0
40.0
0
10
20
50
100
200
Add 10 g of NaOH to each standard. Store at 4°C(±2°C)
8.4.3 Place calibration standards, blanks, and control standards in the
sampler tray, followed by distilled samples, distilled duplicates,
distilled standards, distilled spikes, and distilled blanks.
8.4.4 When a steady reagent baseline is obtained and before starting the
sampler, adjust the baseline using the appropriate knob on the
colorimeter. Aspirate a calibration standard and adjust the STD CAL
dial on the colorimeter until the desired signal is obtained. Record
the STD CAL value. Re-establish the baseline and proceed to analyze
calibration standards, blanks, control standards, distilled samples,
and distilled QC audits.
9. Calculations
9.1 Using the titrimetric procedure, calculate concentration of CN as follows:
(A-B) 1,000 mL/L x 250 mL
CN, mg/L = mL orig. sample mL of aliquot titrated
WHERE: A = volume of AgNO-j for titration of sample
(1 mL = 1 mg Ag)
B - volume of AgNO3 for titration of blank
(1 mL = 1 mg Ag)
AND: 250 mL = distillate volume (See 8.1.5)
1000 mL = conversion mL to L
mL original sample (See 8.1.1)
mL of aliquot titrated (See 8.2.1)
D-67 ILM04.0
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Exhibit D Method 335.2
9.2 If the semi-automated method is used, measure the peak heights of the
calibration standards (visually or using a data system) and calculate a linear
regression equation. Apply the equation to the samples and QC audits to
determine the cyanide concentration in the distillates. To determine the
concentration of cyanide in the original sample, MULTIPLY THE RESULTS BY ONE-
HALF {since the original volume was 500 mL and the distillate volume was 250
mL). Also, correct for, and report on Form XIV, any dilutions which were made
before or after distillation.
The minimum concentration that can be reported from the calibration curve is
10 ug/L that corresponds to 5 ug/L in a sample that has been distilled.
9.3 If the manual spectrophotometric procedure is used, calculate the cyanide, in
ug/L, in the original sample as follows:
A x 1,000 mL/L
CN, ug/L B x
WHERE: A = ug CN read from standard curve (per 250 mL)
B = mL of original sample for distillation (See 8.1.1)
C = mL taken for colorimetric analysis (See 8.3.1)
AND: 50 mL = volume of original sample aliquot (See 8.3.1)
1000 mL/L = conversion mL to L
The minxmum value that can be substituted for A is 2.5 ug per 250 mL. That
yields a concentration of 5 ug/L in the distilled sample.
D-68 ILM04.0
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Exhibit D Method 335.2
METHOD FOR TOTAL CYANIDE ANALYSIS IN SOIL/SEDIMENT
CYANIDE, TOTAL (in Sediments)
Method 335.2 CLP-M* (Titrimetric; Manual Spectrophotometric;Semi-Automated
Spectrophotometric)
1. Scope and Application
1.1 This method is applicable to the determination of cyanide in sediments and
other solids.
1.2 The detection limit is dependent upon the weight of sample taken for analysis.
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 containing
sodium hydroxide solution. The cyanide ion in the absorbing solution is then
determined by volumetric titration or colorimetrically.
2.2 In the colorimetric measurement, the cyanide is converted to cyanogen
chloride, CNC1, by reaction with chloramine-T at a pH less than 8 without
hydrolyzing to the cyanate. 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 for 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.
2.3 The titrimetric measurement uses a standard solution of silver nitrate to
titrate cyanide in the presence of a silver sensitive indicator.
3. Definitions
3.1 Cyanide is defined as cyanide ion and complex cyanides converted to
hydrocyanic acid (HCN) by reaction in a reflux system of a mineral acid in the
presence of magnesium ion.
4. Sample Handling and Preservation
4.1 Samples must be stored at 4°C(±2°C) and must be analyzed within the holding
time specified in Exhibit D, Section II.
4.2 Samples are not dried prior to analysis. A separate percent solids
determination must be made in accordance with the procedure in Part F.
5. Interferences
5.1 Interferences are eliminated or reduced by using the distillation procedure
described in 8.1.
5.2 Sulfides adversely affect the colorimetric and titration procedures.
CLP-M Modified for the Contract Laboratory Program.
D-S9 ILM04.0
-------
Exhibit D Method 335.2
5.3 The presence of surfactants may cause the sample to foam during refluxing. If
this occurs, the addition of an agent such as 'DOW Corning 544 antifoam agent
will prevent the foam from collecting in the condenser. Fatty acids will
distill and form soaps under the alkaline titration conditions, making the end
point almost impossible to detect. When this occurs, one of the
spectrophotometric methods should be used.
6. Apparatus
6.1 Reflux distillation apparatus. The boiling flask should be of 1 liter size
with inlet tube and provision for condenser. The gas absorber may be a
Fisher-Milligan scrubber.
6.2 Microburet, 5.0 mL (for titration)
6.3 Spectrophotometer suitable for measurements at 578 nm or 620 nm with a 1.0 cm
cell or larger.
6.4 Technicon AA II system or equivalent instrumentation (for automated
spectrophotometric method) including:
6.4.1 Sampler
6.4.2 Pump III
6.4.3 Cyanide manifold
6.4.4 SCIC colorimeter with 15 mm flowcells and 570 nm filters
6.4.5 Recorder
6.4.6 Data system (optional)
6.4.7 Glass or plastic tubes for the sampler
7. Reagents
7.1 Distillation and Preparation Reagents
7.1.1 Sodium hydroxide solution, 1.25 N: Dissolve 50 g of NaOH in distilled
water, and dilute to 1 liter with distilled water.
7.1.2 Cadmium carbonate: powdered
7.1.3 Ascorbic acid: crystals
7.1.4 Sulfuric acid: concentrated
7.1.5 Magnesium chloride solution: Weigh 510 g of MgCl2'6H2O into a 1000
mL flask, dissolve and dilute to 1 liter with distilled water.
7.2 Stock Standards and Titration Reagents
7.2.1 Stock cyanide solution: Dissolve 2.51 g of KCN and 2 g of KOH in 1
liter of distilled water. Standardize with 0.0192 N AgNO3.
D-70 ILM04.0
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Exhibit D Method 335.2
7.2.2 Standard cyanide solution, intermediate: Dilute 50.0 mL of stock (1
mL = 1 mg CN) to 1000 mL with distilled water (1 mL = 50.0 ug).
7.2.3 Standard cyanide solution: Prepare fresh daily by diluting 100.0 mL
of intermediate cyanide solution to 1000 mL with distilled water and
store in a glass stoppered bottle. 1 mL = 5.0 ug CN (5.0 mg/L).
7.2.4 Standard silver nitrate solution, 0.0192 N: Prepare by crushing
approximately 5 g AgNO3 crystals and drying to constant weight at
40°C. Weigh out 3.2647 g of dried AgNO3, dissolve in distilled
water, and dilute to 1000 mL (1 mL = 1 mg CN).
7.2.5 Rhodanine indicator: Dissolve 20 mg of p-dimethyl-amino-
benzalrhodanine in 100 mL acetone.
7.3 Manual Spectrophotometric Reagents
7.3.1 Sodium dihydrogenphosphate, 1 M: Dissolve 138 g of NaH2PO4-H2O in 1
liter of distilled water. Refrigerate this solution.
7.3.2 Chloramine-T solution: Dissolve 1.0 g of white, water soluble
Chloramine-T in 100 mL of distilled water and refrigerate until ready
to use. Prepare fresh weekly.
7.3.3 Color reagent - One of the following may be used:
7.3.3.1 Pyridine-barbituric acid reagent: Place 15 g of
barbituric acid in a 250 mL volumetric flask and add just
enough distilled water to wash the sides of the flask and
wet the barbituric acid. Add 75 mL of pyridine and mix.
Add 15 mL of HC1 (sp gr 1.19), mix, and cool to room
temperature. Dilute to 250 mL with distilled water and
mix. This reagent is stable for approximately six months
if stored in a cool, dark place.
7.3.3.2 Pyridine-pyrazolone solution:
7.3.3.2.1 3-Methyl-l-phenyl-2-pyrazolin-5- one reagent,
saturated solution: Add 0.25 g of 3-methyl-l-
phenyl-2-pyrazolin-5-one to 50 mL of distilled
water, heat to 60°C with stirring. Cool to
room temperature.
7.3.3.2.2 3,3'Dimethyl-1,1'-diphenyl-[4,4'-bi-2-pyrazolin]-
5,5'dione (bispyrazolone): Dissolve 0.01 g of
bispyrazolone in 10 mL of pyridine.
7.3.3.2.3 Pour solution (7.3.3.2.1) through non-acid-
v;ashed filter paper. Collect the filtrate.
Through the same filter paper pour solution
(7.3.3.2.2) collecting the filtrate in the
same container as filtrate from (7.3.3.2.1).
Mix until the filtrates are homogeneous. The
mixed reagent develops a pink color but this
does not affect the color production with
D-71 ILM04.0
-------
Exhibit D Method 335.2
cyanide if used within 24 hours of
preparation.
7.4 Semi-Automated Spectrophotometric Reagents
7.4.1 Chloramine-T solution: Dissolve 0.40 g of chloramine-T in distilled
water and dilute to 100 mL. Prepare fresh daily.
7.4.2 Phosphate Buffer: Dissolve 138 g of NaH2PO4'H2O in distilled water
and dilute to 1 liter. Add 0.5 mL of Brij-35 (available from
Technicon). Store at 4°C.
7.4.3 Pyridine-barbituric acid solution: Transfer 15 g of barbituric acid
into a 1 liter volumetric flask. Add about 100 mL of distilled water
and swirl the flask. Add 74 mL of pyridine and mix. Add 15 mL of
cone. HC1 mix until the barbituric acid is dissolved. Dilute to 1
liter with distilled water. Store at 4°C.
7.4.4 Sampler Wash: Dissolve 10 g of NaOH in distilled water and dilute to
1 liter.
8. Procedure
8.1 Distillation
8.1.1 Accurately weigh a representative 1-5 g portion of wet sample and
transfer it to a boiling flask. Add 500 mL of distilled water.
Shake or stir the sample so that it is dispersed.
8.1.2 Add 50 mL of sodium hydroxide (7.1.1) to the absorbing tube and
dilute if necessary with distilled water to obtain an adequate depth
of liquid in the absorber. Connect the boiling flask, condenser,
absorber, and trap in the train.
8.1.3 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.
NOTE: The bubble rate will not remain constant after the reagents
have been added and while heat is being applied to the flask. It will
be necessary to readjust the air rate occasionally to prevent the
solution in the boiling flask from backing up into the air inlet tube.
8.1.4 Slowly add 25 mL of cone, sulfuric acid (7.1.4) through the air inlet
tube. Rinse the tube with distilled water and allow the airflow to
mix the flask contents for 3 minutes. Pour 20 mL of magnesium
chloride solution (7.1.5) into the air inlet and wash down with a
stream of water.
8.1.5 Heat the solution to boiling, taking care to prevent the solution
from backing up and overflowing into the air inlet tube. Reflux for
one hour. Turn off heat and continue the airflow for at least 15
minutes. After cooling the boiling flask, disconnect absorber and
close off the vacuum source.
D-72 ILM04.0
-------
Exhibit D Method 335.2
8.1.6 Drain the solution from the absorber into a 250 mL volumetric flask
and bring up to volume with distilled water washings from the
absorber tube.
NOTE: The distillation procedure results in a 2x concentration of the
sample.
8.2 Titrimetric Determination (Option A)
8.2.1 If the sample contains more than 1 mg of CN, transfer the distillate,
or a suitable aliquot diluted to 250 mL, to a 500 mL Erlenmeyer
flask. Add 10-12 drops of the benzalrhodanine indicator.
8.2.2 Titrate with standard silver nitrate to the first change in color
from yellow to brownish-pink. Titrate a distilled water blank using
the same amount of sodium hydroxide and indicator as in the sample.
8.2.3 The analyst should familiarize himself with the 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.
8.3 Manual Spectrophotometric Determination (Option B)
8.3.1 Withdraw 50 mL or less of the solution from the flask and transfer to
a 100 mL volumetric flask. If less than 50 mL is taken, dilute to 50
mL with 0.25 N sodium hydroxide solution (7.1.1). Add 15.0 mL of
sodium phosphate solution (7.3.1) and mix.
8.3.1.1 Pyridine-barbituric acid method: Add 2 mL of Chloramine-T
(7.3.2) and mix. After 1 to 2 minutes, add 5 mL of
pyridine-barbituric acid solution (7.3.3.1) and mix.
Dilute to mark with distilled water and mix again. Allow
8 minutes for color development then read absorbance at
578 nm in a 1 cm cell within 15 minutes.
8.3.1.2 Pyridine-pyrazolone method: Add 0.5 mL of chloramine-T
(7.3.2) and mix. After 1 to 2 minutes add 5 mL of
pyridine-pyrazolone solution (7.3.3.2) and mix. Dilute to
mark with distilled water and mix again. After 40
minutes, read absorbance at 620 nm in a 1 cm cell.
NOTE: More than 0.5 mL of chloramine-T will prevent the
color from developing with pyridine-pyrazolone.
8.3.2 Prepare a minimum of three standards and a blank by pipetting
suitable volumes of standard solution into 250 mL volumetric flasks.
NOTE: One calibration standard must be made at the CRDL. To each
standard add 50 mL of 1.25 N sodium hydroxide and dilute to 250 mL
with distilled water. The same method for color development (i.e.,
pyridine-barbituric acid or pyridine-pyrazolone) must be used for both
the samples and standards. Standards must bracket the concentrations
of the sample. If dilution is required, use the blank solution.
D-73 ILM04.0
-------
Exhibit D Method 335.2
As an example, standard solutions could be prepared as
follows:
mL of Standard Solution Cone, ug CN
(1.0 = 5 UQ CN) per 250 mL
0 Blank
0.5 2.5
1.0 5
5-0 25
10.0 50
15.0 75
20.0 100
8.3.2.1 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.
8.3.2.2 Prepare a standard curve by plotting absorbance of
standard vs. cyanide concentrations (per 250 mL).
8.4 Semi-Automated Spectrophotometric Determination (Option C)
8.4.1 Set up the manifold. Pump the reagents through the system until a
steady baseline is obtained.
8.4.2 Calibration standards: Prepare a blank and at least three
calibration standards over the range of the analysis. One
calibration standard must be at the CRDL. For a working range of 0-
200 ug/L, the following standards may be used:
mL Standard Solution Concentration
(7.2.3) diluted to 1 liter uq CN/L
0 0
2.0 10
4.0 20
10.0 50
20.0 100
40.0 200
Add 10 g of NaOH -co each standard. Store at 4°C(±2°C).
8.4.3 Place calibration standards, blanks, and control standards in the
sampler tray, followed by distilled samples, distilled duplicates,
distilled standards, distilled spikes, and distilled blanks.
8.4.4 When a steady reagent baseline is obtained and before starting the
sampler, adjust the baseline using the appropriate knob on the
colorimeter. Aspirate a calibration standard and adjust the STD CAL
D-74 ILM04.0
-------
Exhibit D Method 335.2
dial on the colorimeter until the desired signal is obtained. Record
the STD CAL value. Reestablish the baseline and proceed to analyze
calibration standards, blanks, control standards, distilled samples,
and distilled QC audits.
9. Calculations
9.1 A separate determination of percent solids must be performed (see Part F).
9.2 The concentration of cyanide in the sample is determined as follows.
9.2.1 (Titration)
(A - B) x 25° mL x 1000 g/kg
CN, mg/kg = mL aliquot titrated
c x %solids
100
WHERE: A = mL of AgNO3 for titration of sample
(1 mL = 1 mg Ag)
B = mL of AgNO-j for titration of blank
(1 mL = 1 mg Ag)
C = wet weight of original sample in g
(See 8.1.1)
AND: 250 mL = volume of distillate (See 8.1.6)
1000 g/kg = conversion factor g to kg
mL aliquot titrated (See 8.2.1)
% solids (see Part F)
9.2.2 (Manual Spectrophotometric)
a ... 50 mL
f\ Ji. -- — -----
CN, mg/kg = B_
c x % solids
100
WHERE: A = ug CN read from standard curve (per 250 mL)
B = mL of distillate taken for colorimetric
determination (8.3.1)
C = wet weight of original sample in g
(See 8.1.1)
The minimum value that can be substituted for A is 2.5 ug/250 mL.
That yields a concentration of 5 ug/L in the distilled sample.
AND: 50 mL = volume of standard taken for colorimetric
determination (See 8.3.1)
% solids (see Part F)
9.2.3 (Semi-Automated Spectrophotometric)
If the semi-automated method is used, measure the peak heights of
the calibration standards (visually or using a data system) and
calculate a linear regression equation. Apply the equation to the
D-75 ILM04.0
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Exhibit D Method 335.2
samples and QC audits to determine the cyanide concentration in
the distillates.
•»
A x .25
CN, mg/kg = C x % solids
100
WHERE: A = ug/L determined from standard curve
C = wet weight of original sample in g
(See 8.1.1)
AND: .25 = conversion factor for distillate final
volume (See 8.1.6)
% solids (see Part F)
The minimum value that can be substituted for A is 2.5 ug/250 mL.
D-76 ILM04.0
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Exhibit D Method 335.2
METHOD FOR TOTAL CYANIDE ANALYSIS BY MIDI DISTILLATION
CYANIDE, TOTAL (water and soils)
Method 335.2 CLP-M (Semi-automated Spectrophotometric)
1. Scope and Application
1.1 Cyanide determined by this method is defined as cyanide ion and complex
cyanides converted to hydrocyanic acid by reaction in a reflux system with
mineral acid in the presence of magnesium ion.
1.2 This method covers the determination of cyanide by midi distillation with a
semi-automated colorimetric analysis of the distillate.
1.3 The detection limit for the semi-automated colorimetric method is
approximately 10 ug/L.
2. Summary of Method
2.1 The cyanide as hydrocyanic acid (HCN) is released from cyanide complexes by
means of a midi reflux-distillation operation and absorbed in a scrubber
containing sodium hydroxide solution. The cyanide ion in the absorbing
solution is then determined colorimetrically.
2.2 In the colorimetric measurement, the cyanide is converted to cyanogen
chloride, CNC1, by reaction with chloramine-T at pH less than 8 without
hydrolysis to the cyanate. After the reaction is complete, color is formed on
the addition of pyridinebarbituric acid reagent. The absorbance is read at
580 nm. To obtain colors of comparable intensity, it is essential to have the
same salt content in both the samples and the standards.
3. Sample Handling and Preservation
3.1 All bottles must be thoroughly cleansed and rinsed to remove soluble materials
from containers.
3.2 Oxidizing agents such as chlorine decompose most cyanides. Test a drop of the
sample with potassium iodide-starch test paper (Kl-Starch paper); a blue color
indicates the need for treatment. Add ascorbic acid, a few crystals at a
time, until a drop of sample produces no color on the indicator paper. Then
add additional 0.6 g of ascorbic acid for each liter of sample volume.
3.3 Samples are preserved with 2 mL of 10 N sodium hydroxide per liter of sample
(pH > 12) at the time of collection.
3.4 Samples must be stored at 4°C(±2°C) and must be analyzed within the holding
time specified in Exhibit D, Section II.
4. Interferences
4.1 Interferences are eliminated or reduced by using the distillation procedure.
D-77 ILM04.0
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Exhibit D Method 335.2
4.2 Sulfides adversely affect the colorimetric procedures. If a drop of
distillate on lead acetate test paper indicates the presence of sulfides,
treat the sample with powdered cadmium carbonate. Yellow cadmium sulfide
precipitates if the sample contains sulfide. Repeat this operation until a
drop of the treated sample 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 sample to be used for analysis. Avoid a large
excess of cadmium carbonate and long contact time in order to minimize loss by
complexation or occlusion of cyanide on the precipitated material.
4.3 The presence of surfactants may cause the sample to foam during refluxing. If
this occurs, the addition of an agent such as Dow Corning 544 antifoaming
agent will prevent the foam from collecting in the condenser.
5. Apparatus
5.1 Midi reflux distillation apparatus,
5.2 Heating block - Capable of maintaining 125°C ±5°C.
5.3 Auto analyzer system with accessories:
5.3.1 Sampler
5.3.2 Pump
5.3.3 Cyanide cartridge
5.3.4 Colorimeter with 50 mm flowcells and 580 nm filter
5.3.5 Chart recorder or data system.
5.4 Assorted volumetric glassware, pipets, and micropipets.
6. Reagents
6.1 Distillation and Preparation Reagents
6.1.1 Sodium hydroxide absorbing solution and sample wash solution, 0.25 N:
Dissolve 10.0 g NaOH in ASTM Type II water and dilute to one liter.
6.1.2 Magnesium chloride solution, 51% (w/v): Dissolve 510 g of MgCl2'6H2O
in ASTM Type II water and dilute to one liter.
6.1.3 Sulfuric acid, 50% (v/v): Carefully add a portion of concentrated
H2SO4 to an equal portion of ASTM Type II water.
6.1.4 Sodium hydroxide solution, 1.25 N: Dissolve 50 g of NaOH in ASTM
Type II water and dilute to one liter.
D-78 ILM04.0
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Exhibit D Method 335.2
6.2 Standards
6.2.1 Stock cyanide solution, 1000 mg/L CN: Dissolve 2.51 g of KCN and 2.0
g KOH in ASTM Type II water and dilute one liter. Standardize with
0.0192 N AgNO3.
6.2.2 Intermediate cyanide standard solution, 10 mg/L CN: Dilute 1.0 mL of
stock cyanide solution (6.2.1) plus 20 mL of 1.25 N NaOH solution
(6.1.4) to 100 mL with ASTM Type II water. Prepare this solution at
time of analysis.
6.2.3 Rhodamine indicator: Dissolve 20 mg of p-dimethylamino-benzal-
rhodamine in 100 mL acetone.
6.2.4 Silver nitrate solution, 0.0192 N: Prepare by crushing approximately
5 g AgNO3 crystals and drying to a constant weight at 104°C. Weigh
out 3.2647 g of dried AgNO^ and dissolve in ASTM Type II water.
Dilute to one liter ( 1 mL corresponds to 1 mg CN) .
6.2.5 Potassium chromate indicator solution: Dissolve 50 g I^CRC^ in
sufficient ASTM Type II water. Add silver nitrate solution until a
definite red precipitate is formed. Let stand for at least 12 hours,
filter, and dilute to one liter with ASTM Type II water.
6.2.6 Primary standard sodium chloride, 0.0141 N: Dissolve 824.1 mg NaCl
(NBS-dried 20 minutes at 104°C) in ASTM Type II water and dilute to
one liter.
6.2.7 Sodium hydroxide solution, 0.1 N: Dissolve 4 g of NaOH in ASTM Type
II water and dilute to one liter,
6.3 Semi-Automated Spectrophotometric Reagents
6.3.1 Phosphate buffer solution, 1 M: Dissolve 138 g of Na^PC^-I^O in
ASTM Type II water and dilute to one liter. Add 0.5 mL of Brij-35
(available from Technicon) . Store at 4°C.
6.3.2 Chloramine-T solution, 0.4% (w/v) : Dissolve 0.4 g of chloramine-T in
ASTM Type II water and dilute to 100 mL. Prepare fresh at time of
analysis .
6.3.3 Color reagent solution, pyridine barbituric acid color reagent
solution: Prepare this solution in the hood. Transfer 15 g of
barbituric acid into a one liter Erlenmeyer flask. Add about 100 mL
of ASTM Type II water and swirl the flask to mix. Add 75 mL of
pyridine and 15 mL concentrated HC1 and mix until all the barbituric
acid is dissolved. Dilute to one liter with ASTM Type II water and
store at 4°C.
D-79 ILM04.0
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Exhibit D Method 335.2
7. Procedure
7.1 Distillation
7.1.1 The procedure described here utilizes a midi distillation apparatus
and requires a sample aliquot of 50 mL or less for aqueous samples
and one gram for solid materials. NOTE: All samples must initially
be run undiluted (i.e., aqueous samples must first be run with a 50
mL aliquot and solid samples using a one gram sample). When the
cyanide concentration exceeds the highest calibration standard,
appropriate dilution (but not below the CRDL) and reanalysis of the
sample are required. The dilution factor must be reported on Form
XIV.
7.1.2 For aqueous samples: Pipet 50 mL of sample, or an aliquot diluted to
50 mL, into the distillation flask along with 2 or 3 boiling chips.
7.1.3 For solid samples: Weigh 1.0 g of sample (to the nearest 0.01 g)
into the distillation flask and dilute to 50 mL with ASTM Type II
water. Add 2 or 3 boiling chips.
7.1.4 Add 50 mL of 0.25 N NaOH (6.1.1) to the gas absorbing impinger.
7.1.5 Connect the boiling flask, condenser, and absorber in the train. The
excess cyanide trap contains 0.5 N NaOH.
7.1.6 Turn on the vacuum and adjust the gang (Whitney) values to give a
flow of three bubbles per second from the impingers in each reaction
vessel.
7.1.7 After five minutes of vacuum flow, inject 5 mL of 50% (v/v) E^SO^
(6.1.3) through the top air inlet tube of the distillation head into
the reaction vessel. Allow to mix for 5 minutes. NOTE: The acid
volume must be sufficient to bring the sample/solution pH to below
2.0.
7.1.8 Add 2 mL of magnesium chloride solution (6.1.2) 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.
7.1.9 Turn on the heating block and set for 123-125°C. Heat the solution
to boiling, taking care to prevent solution backup by periodic
adjustment of the vacuum flow.
7.1.10 After one and a half hours of refluxing, turn off the heat and
continue the vacuum for an additional 15 minutes. The flasks should
be cool at this time.
7.1.11 After cooling, close off the vacuum at the gang valve and remove the
absorber. Seal the receiving solutions and store them at 4°C until
analyzed. The solutions must be analyzed for cyanide within the 12
day holding time specified in Section II.
D-80 ILM04.0
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Exhibit D Method 335.2
7.2 Semi-Automated Spectrophotometric Determination
7.2.1 Operating conditions: Because of the difference between various
makes and models of satisfactory instruments, no detailed operating
instructions can be provided. The analyst should follow the
instructions provided by the manufacturer of the particular
instrument. It is the responsibility of the analyst to verify that
the instrument configuration and operating conditions used satisfy
the analytical requirements and to maintain quality control data
confirming instrument performance and analytical results.
The following general procedure applies to most semi-automated
colorimeters. Set up the manifold and complete system per
manufacturer's instructions. Allow the colorimeter and recorder to
warm up for at least 30 minutes prior to use. Establish a steady
reagent baseline, feeding ASTM Type II water through the sample line
and appropriate reagents (6.3) through reagent lines. Adjust the
baseline using the appropriate control on the colorimeter.
7.2.2 Prepare a minimum of 3 standards and a blank by pipetting suitable
volumes of standard solution into 50 mL volumetric flasks. NOTE:
One calibration standard must be at the Contract Required Detection
Limit (CRDL).
As an example, standard solutions could be prepared as follows:
Total ug CN
standard solution mL 10 mq/L CN mL 0.05 N NaOH
0.00 0.000 20
0.10 0.010 20
0.25 0.025 20
0.50 0.050 20
1.00 0.100 20
2.00 0.200 20
5.00 0.500 20
10.00 1.000 20
7.2.2.1 Dilute standards to 50 mL using ASTM Type II water. 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 for each SDG to ensure the distillation technique is
reliable. If the distilled standard does not agree within
+15% of the undistilled standards, the operator must find
and correct the cause of the error before proceeding.
7.2.3 Aspirate the highest calibration standard and adjust the colorimeter
until the desired (maximum) signal-range is obtained.
7.2.4 Place calibration standards, blanks, and control standards in the
sampler tray, followed by distilled samples, distilled duplicates,
distilled standards, distilled spikes, and distilled blanks.
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Exhibit D Method 335.2
7.2.5 Switch sample line from the ASTM Type II water to sampler, set the
appropriate sampling rate and begin the analysis.
8. Calculations
8.1 Calculations for Semi-automated Colorimetric Determination
8.1.1 Prepare a standard curve by plotting absorbance (peak heights,
determined visually or using a data system) of standards (y) versus
cyanide concentration values (total ug CN/L) (x). Perform a linear
regression analysis.
8.1.2 Multiply all distilled values by the standardization value to correct
for the stock cyanide solution not being exactly 1000 mg/L (See
6.2.1) .
8.1.3 Using the regression analysis equation, calculate sample receiving
solution concentrations from the calibration curve.
8.1.4 Calculate the cyanide of aqueous samples in ug/L of original sample,
as follows:
A x D x F
CN, ug/L = B
where: A = ug/L CN of sample from regression analysis
B = Liter of original sample for distillation (0.050 L)
(See 7.1.2)
D = any dilution factor necessary to bracket sample
value within standard values
F = sample receiving solution volume (0.050 L)
The minimum value that can be substituted for A is 10 ug/L.
8.1.5 Calculate the cyanide of solid samples in mg/kg of original sample,
as follows:
8.1.5.1 A separate determination of percent solids must be
performed (See Part F).
8.1.5.2 The concentration of cyanide in the sample is determined
as follows:
A x D x F
CN, mg/kg = B x E
where: A = ug/L CN of sample from regression analysis
curve
B = wet weight of original sample in g (See
7.1.3)
D = any dilution factor necessary to bracket
sample value within standard values
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Exhibit D Method 335.2
E = % solids (See Part F)/100.
F = sample receiving solution volume (0.050 L)
The minimum value that can be substituted for A is 10 ug/L.
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Exhibit D Part F
PART F - PERCENT SOLIDS DETERMINATION PROCEDURE
1. Immediately following the weighing of the sample to be processed for analysis
(see section III, Part B- Soil/Sediment Sample Preparation), add 5-10 g of
sample to a tared weighing dish. Weigh and record the weight to the nearest
0.01 g.
2. Place weighing dish plus sample, with the cover tipped to allow for moisture
escape, in a drying oven maintained at 103-105°C. Sample handling and drying
should be conducted in a well-ventilated area.
3. Dry the sample overnight (12-24 hours) but no longer than 24 hours. If dried
less than 12 hours, it must be documented that constant weight was attained.
Remove the sample from the oven and cool in a dessicator with the weighing
dish cover in place before weighing. Weigh and record weight to nearest 0.01
g. Do not analyze the dried sample.
4. Duplicate percent solids determinations are required at the same frequency as
are other analytical determinations. Duplicate results are to be recorded on
FORM VI-IN.
5. For the duplicate percent solids determination, designate one sample aliquot
as the "original" sample and the other aliquot as the "duplicate" sample.
Calculate dry weight using the results of the "original" sample aliquot.
6. Calculate percent solids by the formula below. The value thus obtained will
be reported on the appropriate FORM I-IN and, where applicable, FORM VI-IN .
This value will be used for calculating analytical concentration on a dry
weight basis.
% Solids = Sample Dry Weight x 100
Sample Wet Weight
For the purpose of paragraph 3, drying time is defined as the elapsed time in the
oven; thus raw data must record time in and out of the oven to document the 12 hour
drying time minimum. In the event it is necessary to demonstrate the attainment of
constant weight, data must be recorded for a minimum of two repetitive
weigh/dry/dessicate/weigh cycles with a minimum of 1 hour drying time in each cycle.
Constant weight would be defined as a loss in weight of no greater than 0.01 g
between the start weight and final weight of the last cycle.
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EXHIBIT E
QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
Page No.
SECTION I - GENERAL QA/QC PRACTICES E-2
SECTION II - SPECIFIC QA/QC PROCEDURES E-3
SECTION III - QUALITY ASSURANCE PLAN E-5
SECTION IV - STANDARD OPERATING PROCEDURES E-9
SECTION V - REQUIRED QA/QC OPERATIONS E-15
SECTION VI - CONTRACT COMPLIANCE SCREENING E-32
SECTION VII - ANALYTICAL STANDARD REQUIREMENTS E-33
SECTION VIII - DATA PACKAGE AUDITS E-38
SECTION IX - PERFORMANCE EVALUATION SAMPLES E-40
SECTION X - ON-SITE LABORATORY EVALUATIONS E-43
SECTION XI - DATA MANAGEMENT E-46
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SECTION I
GENERAL QA/QC PRACTICES
Standard laboratory practices for laboratory cleanliness as applied to
glassware and apparatus shall be adhered to. Laboratory practices with regard
to reagents, solvents, and gases shall also be adhered to. 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. EPA Environmental Monitoring Systems
Laboratory, Cincinnati, Ohio, September 1982.
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SECTION II
SPECIFIC QA/QC PROCEDURES
The quality assurance/quality control (QA/QC) procedures defined herein shall
be used by the Contractor when performing the methods specified in Exhibit D.
When additional QA/QC procedures are specified in the methods in Exhibit D,
the Contractor shall also follow these procedures. NOTE: The cost of
performing all QA/QC procedures specified in this Statement of Work are
included in the price of performing the bid lot, except for duplicate, spike,
and laboratory control sample analyses, which shall be considered separate
sample analyses.
The purpose of this document is to provide a uniform set of procedures for the
analysis of inorganic constituents of samples, documentation of methods and
their 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.
The primary function of the QA/QC program is the definition of procedures for
the evaluation and documentation of sampling and analytical methodologies and
the reduction and reporting of data. The objective is to provide a uniform
basis for sample collection and handling, 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 quality control 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.
The Contractor is required to participate in the Laboratory Audit and
Intercomparison Study Program run by USEPA. The Contractor can expect to
analyze at least two samples per calendar quarter during the contract period.
The Contractor shall perform and report to SMO and the Technical Project
Officer (TPO) as specified in Exhibit B quarterly verification of instrument
detection limits (IDL) by the method specified in Exhibit E, by type and model
for each instrument used on this contract. All the IDLs shall meet the CRDLs
specified in Exhibit C. For ICP methods, the Contractor shall also report, as
specified in Exhibit B, linearity range verification, all interelement
correction factors, wavelengths used, and integration times.
In this Exhibit, as well as other places within this Statement of Work, the
term "analytical sample" is used in 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 sample
includes all field samples, including Performance Evaluation samples, received
from an external source, but it also includes all required QA/QC samples
(matrix spikes, analytical/post-digestion spikes, duplicates, serial
dilutions, LCS, ICS, CRDL standards, preparation blanks and linear range
analyses) except those directly related to instrument calibration or
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calibration verification (calibration standards, ICV/ICB, CCV/CCB). A
"frequency of 10%" means once every 10 analytical samples. Note: Calibration
verification samples (ICV/CCV) and calibration verification blanks (ICB/CCB)
are not counted as analytical samples when determining 10% frequency.
In order for the QA/QC information to reflect the status of the samples
analyzed, all samples and their QA/QC analysis shall be analyzed under the
same operating and procedural conditions.
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.
The Contractor shall report all QC data in the exact format specified in
Exhibits B and H.
Sensitivity, instrumental detection limits (IDLs), precision, linear dynamic
range and interference effects shall be established for each analyte on a
particular instrument. All reported measurements shall be within the
instrumental linear ranges. The analyst shall maintain quality control data
confirming instrument performance and analytical results.
In addition, the Contractor shall establish a quality assurance program with
the objective of providing sound analytical chemical measurements. This
program shall incorporate the quality control 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.
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SECTION III
QUALITY ASSURANCE PLAN
Introduction:
The QAP shall present, in specific terms, the policies, organization,
objectives, functional guidelines, and specific QA and QC activities designed
to achieve the data quality requirements in this contract. Where applicable,
SOPs pertaining to each element shall be included or referenced as part of the
QAP. The QAP shall be paginated consecutively in ascending order. Additional
information relevant to the preparation of a QAP can be found in Agency and
American Society for Testing and Materials publications.
As evidence of such a 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, and
Document all aspects of the measurement process in order to
provide data which are technically sound and legally defensible.
The QAP shall be available during on-site laboratory evaluation and shall be
submitted within 7 days of written request by the APO and/or TPO. The elements
of the QAP are listed in the following outline.
A. Organization and Personnel
1. QA Policy and Objectives
2. QA Management
a. Organization
b. Assignment of QC and QA Responsibilities
c. Reporting Relationships
d. QA Document Control Procedures
e. QA Program Assessment Procedures
3. Personnel
a. Resumes
b. Education and Experience Pertinent to this Contract
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c. Training Progress
B. Facilities and Equipment
1. Instrumentation and Backup Alternatives
2. Maintenance Activities and Schedules
C. Document Control
1. Laboratory Notebook Policy
2. Sample Tracking/Custody Procedures
3. Logbook Maintenance and Archiving Procedures
4. SDG File Organization, Preparation and Review Procedures
5. Procedures for Preparation, Approval, Review, Revision, and
Distribution of SOPs
6. Process for Revision of Technical or Documentation Procedures
D. Analytical Methodology
1. Calibration Procedures and Frequency
2. Sample Preparation Procedures
3. Sample Analysis Procedures
4. Standards Preparation Procedures
5. Decision Processes, Procedures, and Responsibility for Initiation
of Corrective Action
E. Data Generation
1. Data Collection Procedures
2. Data Reduction Procedures
3. Data Validation Procedures
4. Data Reporting and Authorization Procedures
F. Quality Assurance
1. Data Quality Assurance
2. Systems/Internal Audits
3. Performance/External Audits
4. Corrective Action Procedures
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5. Quality Assurance Reporting Procedures
6. Responsibility Designation
G. Quality Control
1. Solvent, Reagent and Adsorbent Check Analysis
2. Reference Material Analysis
3. Internal Quality Control Checks
4. Corrective Action and Determination of QC Limit Procedures
5. Responsibility Designation
Updating and Submitting the QAP:
Initial Submission: During the contract solicitation process, the Contractor
is required to submit their QAP to the Administrative Project Officer (APO).
Within sixty (60) days after contract award, the Contractor shall maintain on
file a revised QAP, fully compliant with the requirements of this contract.
The revised QAP will become the official QAP under the contract and may be
used during legal proceedings. The Contractor shall maintain the QAP on file
at the Contractor's facility for the term of the contract. Both the initial
submission and the revised QAP shall be paginated consecutively in ascending
order. The revised QAP shall include:
1) Changes resulting from A) the Contractor's internal review of
their organization, personnel, facility, equipment, policy and
procedures and B) the Contractor's implementation of the
requirements of the contract; and
2) Changes resulting from the Agency's review of the laboratory
evaluation sample data, bidder supplied documentation, and
recommendations made during the preaward on-site laboratory
evaluation.
Subsequent Updates and Submissions: During the term of contract, the
Contractor shall amend the QAP when the following circumstances occur:
1) The Agency modifies the contract,
2) The Agency notifies the Contractor of deficiencies in the QAP
document,
3) The Agency notifies the Contractor of deficiencies resulting from
the Agency's review of the Contractor's performance,
4) The Contractor identifies deficiencies resulting from their
internal review of their QAP document,
5) The Contractor's organization, personnel, facility, equipment,
policy or procedures change, or
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6) The Contractor identifies deficiencies resulting from the internal
review of their organization, personnel, facility, equipment,
policy or procedures changes.
The Contractor shall amend the QAP within 30 days of when the circumstances
listed above result in a discrepancy between what was previously described in
the QAP and what is presently occurring at the Contractor's facility.
When the QAP is amended, all changes in the QAP shall be clearly marked (e.g.,
a bar in the margin indicating where the change is found in the document, or
highlighting the change by underlining the change, bold printing the change,
or using a different print font). The amended section pages shall have the
date on which the changes were implemented. The Contractor shall incorporate
all amendments to the current QAP document. The Contractor shall archive all
amendments to the QAP document for future reference by the Agency.
The Contractor shall send a copy of the current QAP document within 7 days of
a written request by the Administrative Project Officer (APO) and/or Technical
Project Officer (TPO) as directed.
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 numbers 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 IV
STANDARD OPERATING PROCEDURES
Introduction:
In order to obtain reliable results, adherence to prescribed analytical
methodology is imperative. In any operation that is performed on a repetitive
basis, reproducibility is best accomplished through the use of Standard
Operating Procedures (SOPs). As defined by the EPA, an SOP is a written
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 shall be functional (i.e., clear,
comprehensive, up-to-date, and sufficiently detailed to permit duplication of
results by qualified analysts). The SOPs shall be paginated consecutively in
ascending order.
All SOPs shall reflect activities as they are currently performed in the
laboratory. In addition, all SOPs shall be:
Consistent with current EPA regulations, guidelines, and the CLP
contract's requirements.
Consistent with instruments manufacturers' specific instruction
manuals.
Available to the EPA during an on-site laboratory evaluation. A
complete set of SOPs shall be bound together and available for
inspection at such evaluations. During on-site laboratory
evaluations, laboratory personnel may be asked to demonstrate the
application of the SOPs.
Available to the APO and/or TPO within 7 days of a written
request.
Capable of providing for the development of documentation that is
sufficiently complete to record the performance of all tasks
required by the protocol.
Capable of demonstrating the validity of data reported by the
Contractor and explain the cause of missing or inconsistent
results.
Capable of describing the corrective measures and feedback
mechanism utilized when analytical results do not meet protocol
requirements.
Reviewed regularly and updated as necessary when contract,
facility, or Contractor procedural modifications are made.
Archived for future reference in usability or evidentiary
situations.
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Available at specific work stations as appropriate.
Subject to a document control procedure which precludes the use of
outdated or inappropriate SOPs.
SOP Format:
The format for SOPs may vary depending upon the kind of activity for which
they are prepared, however, at a minimum, the following sections shall be
included:
Title Page
Scope and Application
Definitions
Procedures
QC Limits
Corrective Action Procedures, Including Procedures for Secondary
Review of Information Being Generated
Documentation Description and Example Forms
Miscellaneous Notes and Precautions
References
SOPs Required:
The Contractor shall maintain the following SOPs:
1. Evidentiary SOP
Evidentiary SOPs for required chain-of-custody and document control are
discussed in Exhibit F.
2. Sample Receipt and Storage
a. Sample receipt and identification logbooks
b. Refrigerator temperature logbooks
c. Security precautions
3. Sample preparation
4. Glassware cleaning
5. Calibration (Balances, etc.)
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a. Procedures
b. Frequency requirements
c. Preventative maintenance schedule and procedures
d. Acceptance criteria and corrective actions
e. Logbook maintenance authorization
6. Analytical procedures (for each analytical system)
a. Instrument performance specifications
b. Instrument operating procedures
c. Data acquisition system operation
d. Procedures when automatic quantitation algorithms are overridden
e. QC required parameters
f. Analytical run/injection logbooks
g. Instrument error and editing flag descriptions and resulting
corrective actions
7. Maintenance activities (for each analytical system)
a. Preventative maintenance schedule and procedures
b. Corrective maintenance determinants and procedures
c. Maintenance authorization
8. Analytical standards
a. Standard coding/identification and inventory system
b. Standards preparation logbook(s)
c. Standard preparation procedures
d. Procedures for equivalency/traceability analyses and documentation
e. Purity logbook (primary standards and solvents)
f. Storage, replacement, and labelling requirements
g. QC and corrective action measures
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9. Data reduction procedures
a. Data processing systems operation
b. Outlier identification methods
c. Identification of data requiring corrective action
d. Procedures for format and/or forms for each operation
10. Documentation policy/procedures
a. Laboratory/analyst's notebook policy, including review policy
b. Complete SDG File contents
c. Complete SDG File organization and assembly procedures, including
review policy
d. Document inventory procedures, including review policy
11. Data validation/self inspection procedures
a. Data flow and chain-of-corrunand for data review
b. Procedures for measuring precision and accuracy
c. Evaluation parameters for identifying systematic errors
d. Procedures to assure that hardcopy and diskette deliverables are
complete and compliant with the requirements in SOW Exhibits B and
H.
e. Procedures to assure that hardcopy deliverables are in agreement
with their comparable diskette deliverables.
f. Demonstration of internal QA inspection procedure (demonstrated by
supervisory sign-off on personal notebooks, internal laboratory
evaluation samples, etc.).
g. Frequency and type of internal audits (e.g., random, quarterly,
spot checks, perceived trouble areas).
h. Demonstration of problem identification-corrective actions and
resumption of analytical processing. Sequence resulting from
internal audit (i.e., QA feedback).
i. Documentation of audit reports (internal and external), response,
corrective action, etc.
12. Data management and handling
a. Procedures for controlling and estimating data entry errors.
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b. Procedures for reviewing changes to data and deliverables and
ensuring traceability of updates.
c. Lifecycle management procedures for testing, modifying and
implementing changes to existing computing systems including
hardware, software, and documentation or installing new systems.
d. Database security, backup and archival procedures including
recovery from system failures.
e. System maintenance procedures and response time.
f. Individuals(s) responsible for system operation, maintenance, data
integrity and security.
g. Specifications for staff training procedures.
Updating and Submitting the SOPs:
Initial Submission: During the contract solicitation process, the Contractor
is required to submit their SOPs to the Administrative Project Officer (APO).
Within sixty (60) days after contract award, the Contractor shall maintain on
file a complete revised set of SOPs, fully compliant with the requirements of
this contract. The revised SOPs will become the official SOPs under the
contract and may be used during legal proceedings. The Contractor shall
maintain the complete set of SOPs on file at the Contractor's facility for the
term of the contract. Both the initial submission of SOPs and the revised
SOPs shall be paginated consecutively in ascending order. The revised SOPs
shall include:
1) Changes resulting from A) the Contractor's internal review of
their procedures and B) the Contractor's implementation of the
requirements of the contract; and
2) Changes resulting from the Agency's review of the laboratory
evaluation sample data, bidder supplied documentation, and
recommendations made during the preaward on-site laboratory
evaluation.
Subsequent Updates and Submissions: During the term of contract, the
Contractor shall amend the SOPs when the following circumstances occur:
1) The Agency modifies the contract,
2) The Agency notifies the Contractor of deficiencies in their SOPs
documentation,
3) The Agency notifies the Contractor of deficiencies resulting from
the Agency's review of the Contractor's performance,
4) The Contractor's procedures change,
5) The Contractor identifies deficiencies resulting from the internal
review of their SOPs documentation, or
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6) The Contractor identifies deficiencies resulting from the internal
review of their procedures.
Existing SOPs shall be amended or new SOPs shall be written within 30 days of
when the circumstances listed above result in a discrepancy between what was
previously described in the SOPs and what is presently occurring at the
Contractor's facility. All changes in the SOPs shall be clearly marked (e.g.,
a bar in the margin indicating where the change is in the document, or
highlighting the change by underlining the change, bold printing the change,
or using a different print font). The amended/new SOPs shall have the date on
which the changes were implemented.
When existing SOPs are amended or new SOPs are written, the Contractor shall
document the reasons for the changes, and maintain the amended SOPs or new
SOPs on file. Documentation of the reasons for the changes shall be
maintained on file with the amended SOPs or new SOPs.
The Contractor shall send a complete set of current SOPs within 7 days of a
written request by the Administrative Project Officer and/or Technical Project
Officer as directed.
Documentation of the reasons for changes to the SOPs shall also be submitted
along with the SOPs. An alternate delivery schedule for submitting the letter
and amended/new SOPs may be proposed by the Contractor, but it is the sole
decision of the Agency, represented either by the Technical Project Officer or
Administrative Project Officer, to approve or disapprove the alternate
delivery schedule. If an alternate delivery schedule is proposed, the
Contractor shall describe in a letter to the Technical Project Officer,
Administrative Project Officer, and the Contracting Officer why he/she is
unable to meet the delivery schedule listed in this section. The Technical
Project Officer/Administrative Project Officer will not grant an extension for
greater than 30 days for amending/writing new SOPs. The Technical Project
Officer/Administrative Project Officer will not grant an extension for greater
than 14 days for submission of the letter documenting the reasons for the
changes and for submitting amended/new SOPs. The Contractor shall proceed and
not assume that an extension will be granted until so notified by the
Technical Project Officer and/or the Administrative Project Officer.
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, and/or contract sanctions,
such as a Cure Notice.
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SECTION V
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 shall
be performed as described in this Exhibit:
1. Instrument Calibration
2. Initial Calibration Verification (ICV) and Continuing Calibration
Verification (CCV)
3. CRDL Standards for AA (CRA) and ICP (CRI)
4. Initial Calibration Blank (ICB), Continuing Calibration Blank
(CCB), and Preparation Blank (PB) Analyses
5. ICP Interference Check Sample (ICS) Analyses
6. Spike Sample Analysis (S)
7. Duplicate Sample Analysis (D)
8. Laboratory Control Sample (LCS) Analysis
9. ICP Serial Dilution Analysis (L)
10. Instrument Detection Limit (IDL) Determination
11. Interelement Corrections for ICP (ICP)
12. Linear Range Analysis (LRA)
13. Furnace AA QC Analyses
1. Instrument Calibration
Guidelines for instrumental calibration are given in EPA 600/4-79-020
and/or Exhibit D. Instruments shall be calibrated daily or once every 24
hours and each time the instrument is set up. The instrument
standardization date and time shall be included in the raw data.
For atomic absorption systems, calibration standards are prepared by
diluting the stock metal solutions at the time of analysis. Date and
time of preparation and analysis shall be given in the raw data.
Calibration standards shall be prepared fresh daily or each time an
analysis is to be made and discarded after use. For atomic absorption
systems, prepare a blank and at least three calibration standards in
graduated amounts in the appropriate range. One atomic absorption
calibration standard shall be at the CRDL. The calibration standards
shall be prepared using the same type of acid or combination of acids
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and at the same concentration as will result in the samples following
sample preparation.
Beginning with the blank, aspirate or inject the standards and record
the readings. If the AA instrument configuration prevents the required
4-point calibration, calibrate according to instrument manufacturer's
recommendations, and analyze the remaining required standards
immediately after calibration. Results for these standards shall be
within 5% of the true value. Each standards concentration and the
calculations to show that the 5% criterion has been met shall be given
in the raw data. If the values do not fall within this range,
recalibration is necessary.
The 5% criterion does not apply to the atomic absorption calibration
standard at the CRDL.
Calibration standards for AA procedures shall be prepared as described
in Exhibit D.
Baseline correction is acceptable as long as it is performed after every
sample or after the continuing calibration verification and blank check;
resloping is acceptable as long as it is immediately preceded and
immediately followed by a compliant CCV and CCB. For cyanide and
mercury, follow the calibration procedures outlined in Exhibit D. One
cyanide and mercury calibration standard shall be at the CRDL. For ICP
systems, calibrate the instrument according to instrument manufacturer's
recommended procedures. At least two standards shall be used for ICP
calibration. One of the standards shall be a blank.
2. Initial Calibration Verification (ICV) and Continuing Calibration
Verification (CCV)
a. Initial Calibration Verification (ICV)
Immediately after each of the ICP, AA and cyanide systems have
been calibrated, the accuracy of the initial calibration shall be
verified and documented for every analyte by the analysis of the
Initial Calibration Verification Solution(s) at each wavelength
used for analysis. When measurements exceed the control limits of
Table 1-Initial and Continuing Calibration Verification Control
Limits for Inorganic Analyses (in Exhibit E), the analysis shall
be terminated, the problem corrected, the instrument recalibrated,
and the calibration reverified.
If the Initial Calibration Verification Solution(s) is not
available from EPA, or where a certified solution of an analyte is
not available from any source, analyses shall be conducted on an
independent standard at a concentration other than that used for
instrument calibration, but within the calibration range. An
independent standard is defined as a standard composed of the
analytes from a different source than those used in the standards
for the instrument calibration.
For ICP, the Initial Calibration Verification Solution(s) shall be
run at each wavelength used for analysis. For CN, the initial
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calibration verification standard shall be distilled. This means
that an ICV must be distilled with each batch of samples analyzed
and that the samples distilled with an ICV must be analyzed with
that particular ICV. For aqueous CN samples, the ICV for CN also
serves as the Laboratory Control Sample (LCS), and it must be
distilled and analyzed as described above. A separate LCS is
required for soil CN samples. The values for the initial and
subsequent continuing calibration verification shall be recorded
on FORM II-IN for ICP, AA, and cyanide analyses, as indicated.
b. Continuing Calibration Verification (CCV)
To ensure calibration accuracy during each analysis run, one of
the following standards is to be used for continuing calibration
verification and shall be analyzed and reported for every
wavelength used for the analysis of each analyte, at a frequency
of 10% or every 2 hours during an analysis run, whichever is more
frequent. The standard shall also be analyzed and reported for
every wavelength used for analysis at the beginning of the run and
after the last analytical sample. The analyte concentrations in
the continuing calibration standard shall be different than the
concentration used for the initial calibration verification and
shall be one of the following solutions at or near the mid-range
levels of the calibration curve:
1. EPA Solutions
2. NIST Standards
3. A Contractor-prepared standard solution
The same continuing calibration standard shall be used throughout
the analysis runs for a Case of samples received.
Each CCV analyzed shall reflect the conditions of analysis of all
associated analytical samples (the preceding 10 analytical samples
or the preceding analytical samples up to the previous CCV). The
duration of analysis, rinses and other related operations that may
affect the CCV measured result may not be applied to the CCV to a
greater extent than the extent applied to the associated
analytical samples. For instance, the difference in time between
a CCV analysis and the blank immediately following it as well as
the difference in time between the CCV and the analytical sample
immediately preceding it may not exceed the lowest difference in
time between any two consecutive analytical samples associated
with the CCV.
If the deviation of the continuing calibration verification is
greater than the control limits specified in Table 1-Initial and
Continuing Calibration Verification Control Limits for Inorganic
Analyses, the analysis shall be stopped, the problem corrected,
the instrument must be recalibrated, the calibration verified and
the reanalysis of preceding 10 analytical samples or all
analytical samples analyzed since the last compliant calibration
verification shall be performed for the analytes affected.
E-17 ILM04.0
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Information regarding the continuing verification of calibration
shall be recorded on FORM II-IN for ICP, AA and cyanide as
indicated.
TABLE 1. INITIAL AND CONTINUING CALIBRATION VERIFICATION
CONTROL LIMITS FOR INORGANIC ANALYSES
% of True Value (EPA Set)
Analytical Method
ICP/AA
Cold Vapor AA
Other
Inorganic Species
Metals
Mercury
Cyanide
Low Limit
90
80
85
High Limit
110
120
115
3. CRDL Standards for ICP (CRI) and AA (CRA)
To verify linearity near the CRDL for ICP analysis, the Contractor shall
analyze an ICP standard (CRI) at two times the CRDL or two times the
IDL, whichever is greater, at the beginning and end of each sample
analysis run, immediately preceding the Interference Check Sample (ICS)
analyses, but not before the Initial Calibration Verification. In
addition, the Contractor shall analyze and report the results for the
CRI at a frequency of not greater than 20 analytical samples per
analysis run. These analyses of the CRI sample shall be immediately
followed by the ICS analyses. (That is, the analytical run sequence
shall be CRI, ICSA, ICSAB, CCV and CCB, in that order). This CRI
standard shall be run by ICP for every wavelength used for analysis,
except those for Al, Ba, Ca, Fe, Mg, Na and K.
To verify linearity near the CRDL for furnace AA, flame AA, and cold
vapor AA analyses, the Contractor shall analyze an AA standard (CRA) at
the CRDL or the IDL, whichever is greater, at the beginning of each
sample analysis run, but not before the Initial Calibration
Verification.
Note: Manual and automated cold vapor AA CRA analysis for mercury are
required and the results and %R are to be reported on Form II(PART 2)-
IN. No specific acceptance criteria have been established by the Agency
for the two standards at this time.
4. Initial Calibration Blank (ICB), Continuing Calibration Blank (CCB), and
Preparation Blank (PB) Analyses
a. Initial Calibration Blank (ICB) and Continuing Calibration Blank
(CCB) Analyses
A calibration blank shall be analyzed at each wavelength used for
analysis immediately after every initial and continuing
calibration verification, at a frequency of 10% or every 2 hours
defined in Exhibit G, CRI is an analytical sample.
E-18 ILM04.0
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during the run, whichever is more frequent. The blank shall be
analyzed at the beginning of the run and after the last
analytical sample. Note: A CCB shall be run after the last CCV
that was run after the last analytical sample of the run. The
results for the calibration blanks shall be recorded on FORM III-
IN for ICP, AA and cyanide analyses, as indicated. If the
magnitude (absolute value) of the calibration blank result equals
or exceeds the IDL, the result shall be reported as specified in
Exhibit B. If the absolute value blank result exceeds the CRDL
(Exhibit C), terminate the analysis, correct the problem,
recalibrate, verify the calibration and reanalyze the preceding 10
analytical samples or all analytical samples analyzed since the
last compliant calibration blank.
b. Preparation Blank (PB) Analysis
At least one preparation blank (or reagent blank), consisting of
deionized, distilled water processed through each sample
preparation and analysis procedure (See Exhibit D, Section III),
shall be prepared and analyzed with every Sample Delivery Group,
or with each batch2 of samples digested, whichever is more
frequent.
The first batch of samples in an SDG is to be assigned to
preparation blank one, the second batch of samples to preparation
blank two, etc. (see FORM III-IN). Each data package shall
contain the results of all the preparation blank analyses
associated with the samples in that SDG.
This blank is to be reported for each SDG and used in all analyses
to ascertain whether sample concentrations reflect contamination
in the following manner:
1) If the absolute value of the concentration of the blank is
less than or equal to the Contract Required Detection Limit
(Exhibit C), no correction of sample results is performed.
2) If any analyte concentration in the blank is above the CRDL
the lowest concentration of that analyte in the associated
samples shall be greater than or equal to lOx the blank
concentration. Otherwise, all samples associated with the
blank with the analyte's concentration less than lOx the
blank concentration and above the CRDL, shall be redigested
and reanalyzed for that analyte (except for an identified
aqueous soil field blank). The sample concentration is not
to be corrected for the blank value.
3) If the concentration of the blank is below the negative
CRDL, then all samples reported below lOx CRDL associated
with the blank shall be redigested and reanalyzed.
•A group of samples prepared at the same time.
E-19 ILM04.0
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The values for the preparation blank shall be recorded in ug/L for
aqueous samples and in mg/Kg for solid samples on FORM III-IN for
ICP, AA, and cyanide analyses.
5. ICP Interference Check Sample (ICS) Analysis
To verify interelement and background correction factors, the Contractor
shall analyze and report the results for the ICP Interference Check
Samples at the beginning and end of each analysis run, but not before
the Initial Calibration Verification. In addition, the Contractor shall
analyze and report the results for the ICP Interference Check Sample at
a frequency of not greater than 20 analytical samples3 per analysis
run. These analyses of the Interference Check Samples shall be
immediately followed by the analysis of a CCV/CCB pair. The ICP
Interference Check Samples shall be obtained from EPA if available and
analyzed according to the instructions supplied with the ICS.
The Interference Check Samples consist of two solutions: Solution A and
Solution AB. Solution A consists of the interferents, and Solution AB
consists of the analytes mixed with the interferents. An ICS analysis
consists of analyzing both solutions consecutively (starting with
Solution A) for all wavelengths used for each analyte reported by ICP.
The analytical results for those target analytes with CRDLs < 10 ug/L
shall fall within + 2x CRDL of the analyte's true value (the true value
shall be zero unless otherwise stated) in the ICS Solution A (ICSA).
For example, if the analysis result(s) for Arsenic (CRDL = 10 ug/L, ICSA
true value = 0 ug/L) in the ICSA analysis during the run is + 19 ug/L,
then the analytical result for Arsenic falls within the + 2x CRDL window
for Arsenic in the ICSA. If the Contractor cannot obtain results that
fall within the ± 2x CRDL window (for analytes with a CRDL < lOug/L),
then the Contractor shall use an alternate method (e.g., GFAA) to
quantitate results for the affected analyte(s) for samples analyzed
since the last good ICSA. For the analytes with CRDLs < 10 ug/L, the
ICSA results shall be reported from an undiluted sample analysis. Also,
the Contractor shall not dilute the Interference Check Samples more than
is necessary to meet the linear range values of the instrument.
Results for the ICP analyses of Solution AB during the analytical runs
shall fall within the control limit of +20% of the true value for the
analytes included in the Interference Check Samples. If not, terminate
the analysis, correct the problem, recalibrate the instrument, and
reanalyze the analytical samples analyzed since the last good ICS. This
+ 20% window does not apply when the IDL exceeds the CRDL for the
analytes As, Pb, Se, Tl (see Exhibit C, Table 1, Footnote 1). If true
values for analytes contained in the ICS and analyzed by ICP are not
supplied with the ICS, the mean shall be determined by initially
analyzing the ICS at least five times repetitively for the particular
analytes. This mean determination shall be made during an analytical run
where the results for the previously supplied EPA ICS met all contract
specifications. Additionally, the result of this initial mean
3As defined in Exhibit G, ICSA and ICSAB are analytical samples.
E-20 ILM04.0
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determination is to be used as the true value for the lifetime of that
solution (i.e., until the solution is exhausted).
If the ICP Interference Check Sample is not available from EPA,
independent ICP Check Samples shall be prepared with interferent and
analyte concentrations at the levels specified in Table 2-Interferent
and Analyte Elemental Concentrations Used for ICP Interference Check
Sample. The mean value and standard deviation shall be established by
initially analyzing the Check Samples at least five times repetitively
for each parameter on FORM IV-IN. Results shall fall within the control
limit of +20% of the established mean value. The mean and standard
deviation shall be reported in the raw data. Results from the
Interference Check Sample analyses shall be recorded on FORM IV-IN for
all ICP parameters.
TABLE 2. INTERFERENT AND ANALYTE ELEMENTAL CONCENTRATIONS USED FOR ICP
INTERFERENCE CHECK SAMPLE
Analytes
Ag
As
Ba
Be
Cd
Co
Cr
Cu
Mn
Ni
Pb
Sb
Se
Tl
V
Zn
(mg/L) Interferents
0.2 Al
0.1 Ca
0.5 Fe
0.5 Mg
1.0
0.5
0.5
0.5
0.5
1.0
0.05
0.6
0.05
0.1
0.5
1.0
(mg/L)
500
500
200
500
6. Spike Sample Analysis (S)
The spike sample analysis is designed to provide information about the
effect of the sample matrix on the digestion and/or measurement
methodology. If a digestion is performed, the spike is added before the
digestion (i.e., prior to the addition of other reagents) and prior to
any distillation steps (i.e., CN-). At least one spike sample analysis
(matrix spike) shall be performed on each group of samples of a similar
matrix type (i.e., water, soil) and concentration (i.e., low, medium) or
for each Sample Delivery Group.
EPA may require additional spike sample analysis, upon Administrative
Project Officer request, for which the Contractor will be paid.
E-21 ILM04.0
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If the spike analysis is performed on the same sample that is chosen for
the duplicate sample analysis, spike calculations shall be performed
using the results of the sample designated as the "original sample" (see
section 7, Duplicate Sample Analysis). The average of the duplicate
results cannot be used for the purpose of determining percent recovery.
Samples identified as field blanks cannot be used for spiked sample
analysis. EPA may require that a specific sample be used for the spike
sample analysis.
The analyte spike shall be added in the amount given in Table 3-Spiking
Levels for Spike Sample Analysis, for each element analyzed. Note: See
Table 3 footnotes for concentration levels and applications. If two
analytical methods are used to obtain the reported values for the same
element within a Sample Delivery Group (i.e., ICP, GFAA), spike samples
shall be run by each method used.
If the spike recovery is not at or within the limits of 75-125%, the
data of all samples received associated with that spike sample and
determined by the same analytical method shall be flagged with the
letter "N" on FORMs I-IN and V-IN. An exception to this rule is granted
in situations where the sample concentration exceeds the spike
concentration by a factor of four or more. In such an event, the data
shall be reported unflagged even if the percent recovery does not meet
the 75-125% recovery criteria.
For flame AA, ICP, and CN analyses, when the pre-digestion/pre-
distillation spike recovery falls outside the control limits and the
sample result does not exceed 4x the spike added, a post-digestion/post-
distillation spike shall be performed for those elements that do not
meet the specified criteria (exception: Ag) . Spike the unspiked aliquot
of the sample at 2x the indigenous level or 2x CRDL, whichever is
greater. Results of the post-digestion/post-distillation spike shall
be reported on FORM V(PART 2) -IN. Note: No post digest spike is
required for Hg.
In the instance where there is more than one spike sample per matrix and
concentration per method per SDG, if one spike sample recovery is not
within contract criteria, flag all the samples of the same matrix,
level, and method in the SDG. Individual component percent recoveries
(%R) are calculated as follows:
% Recovery = SSR~ SR x 100
Where, SSR = Spiked Sample Result
SR = Sample Result
SA = Spike Added
When sample concentration is less than the instrument detection limit,
use SR = 0 only for purposes of calculating % Recovery. The spike
sample results, sample results and % Recovery (positive or negative)
shall be reported on FORM V-IN for ICP, AA and cyanide analyses, as
indicated.
E-22 ILM04.0
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The units for reporting spike sample results will be identical to those
used for reporting sample results in FORM I-IN (i.e., ug/L for aqueous
and mg/Kg dry weight basis for solid).
TABLE 3. SPIKING LEVELS FOR SPIKE SAMPLE ANALYSIS
Element
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
For
Water
(ug/L)
2,000
500
2,000
2,000
50
50
*
200
500
250
1,000
500
*
500
500
*
2,000
50
*
2,000
500
500
ICP/AA For Furnace Other <1)<2)
AA(4>
Soil*2' Water Soil^2)
(mg/Kg) (ug/L) (mg/Kg)
*
100 100 20
400 40 8
400
10
10 5 1
*
40
100
50
*
100 20 4
*
100
1
100
*
400 10 2
10
*
400 50 10
100
100
100 ug/L<3>
No spike required. NOTE: Elements without spike levels, and not
designated with an asterisk, shall be spiked at appropriate levels.
^•Specified spiking levels are for both water and soil/sediment matrices.
Reporting units are ug/L and mg/kg respectively.
levels shown indicate concentrations in the final solution of the
spiked sample (100 mL for mercury and 200 mL for all other metals) when
the wet weight of 1 gram (for ICP, Furnace AA, and Flame AA) , or 0.2
grams (for mercury), of sample is taken for analysis. Adjustment shall
be made to maintain these spiking levels when the weight of sample taken
deviates by more than 10% of these values. Appropriate adjustment shall
E-23
ILM04.0
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be made for microwave digestion procedures where 0.5 grams of sample or
50.0 mL (45.0 mL of sample plus 5.0 mL of acid) of aqueous sample are
required for analysis.
3The level shown indicates the cyanide concentration in the final sample
solution prepared for analysis (i.e., post-distillation). The final
volume of the sample after distillation shall be the basis for the
amount of cyanide to be added as the spike. For instance, the full
volume distillation procedure will require addition of 25 ug cyanide to
the sample prior to distillation (based on the final distillate volume
of 250 mL) to meet the specified spiking level; and the midi
distillation procedure requires the addition of 5 ug of cyanide to the
sample prior to distillation (based on the final distillate volume of 50
mL) .
For soil samples, the final sample solution prepared for analysis (i.e.,
the distillate) must contain cyanide spiked at a concentration of 100
ug/L regardless of the distillation procedure employed or the amount of
sample used for distillation. Use the final sample volume after
distillation as the basis for the amount of cyanide to add as the spike.
The units for reporting soil/solid sample cyanide results shall be
mg/kg. To convert from ug/L to mg/kg, use the equation below:
mg/kg = ug/L x final distillate volume (L) - -
sample weight (g)
4If the Contractor uses an Inductively Coupled Plasma (ICP) spectrometer
to analyze field samples for those elements (e.g., Arsenic, Lead,
Selenium, and/or Thallium) traditionally analyzed by the Graphite
Furnace Atomic Absorption (GFAA) spectrometer, the spiking
concentrations shown for furnace AA analyses (Table 3, above) shall also
apply to the ICP analysis for those elements, provided the ICP IDLs for
those elements do not exceed the CRDL. Otherwise, those elements shall
be spiked at the ICP levels specified in Table 3. However, before any
field samples are analyzed under this contract, the instrument detection
limits (in ug/L) shall be determined for each instrument used, within
thirty (30) days of the start of contract analyses and at least
quarterly (i.e., January, April, July, October), and shall meet the
Contract Required Detection Limits (CRDLs) specified in Exhibit C, Page
C-l, Table 1. For additional information concerning the instrument
detection limit determination see Exhibit E, Section V, item 10 -
Instrument Detection Limit (IDL) Determination.
7. Duplicate Sample Analysis (D)
One duplicate sample shall be analyzed from each group of samples of a
similar matrix type (i.e., water, soil) and concentration (i.e., low,
medium) or for each Sample Delivery Group. Duplicates cannot be
averaged for reporting on FORM I-IN.
may require additional duplicate sample analyses, upon
AdministrativeProject Officer request, for which the Contractor will be paid.
E-24 ILM04.0
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Duplicate sample analyses are required for percent solids. Samples
identified as field blanks cannot be used for duplicate sample analysis.
EPA may require that a specific sample be used for duplicate sample
analysis. If two analytical methods are used to obtain the reported
values for the same element for a Sample Delivery Group (i.e., ICP,
GFAA) , duplicate samples shall be run by each method used. The relative
percent differences (RPD) for each component are calculated as follows:
*PD -
Where, RPD = Relative Percent Difference
S = First Sample Value (original)
D = Second Sample Value (duplicate)
The results of the duplicate sample analyses shall be reported on FORM
VI-IN in ug/L for aqueous samples and mg/Kg dry weight basis for solid
original and duplicate samples. A control limit of 20% for RPD shall be
used for original and duplicate sample values greater than or equal to
5x CRDL (Exhibit C) . A control limit of (+) the CRDL shall be used if
either the sample or duplicate value is less than 5x CRDL, and the
absolute value of the control limit (CRDL) shall be entered in the
"Control Limit" column on FORM VI-IN.
If one result is above the 5x CRDL level and the other is below, use the
± CRDL criteria. If both sample values are less than the IDL, the RPD
is not calculated on FORM VI-IN. For solid sample or duplicate results
< 5x CRDL, enter the absolute value of the CRDL, corrected for sample
weight and percent solids, in the "Control Limit" column. If the
duplicate sample results are outside the control limits, flag all the
data for samples received associated with that duplicate sample with an
"*" on FORMs I-IN and VI-IN. In the instance where there is more than
one duplicate sample per SDG, if one duplicate result is not within
contract criteria, flag all samples of the same matrix, concentration,
and method in the SDG. The percent difference data will be used by EPA
to evaluate the long-term precision of the methods for each parameter.
Specific control limits for each element will be added to FORM VI-IN at
a later date based on these precision results.
8. Laboratory Control Sample (LCS) Analysis
Aqueous and solid Laboratory Control Samples (LCS) shall be analyzed for
each analyte using the same sample preparations, analytical methods and
QA/QC procedures employed for the EPA samples received. The aqueous LCS
solution must be obtained from EPA (if unavailable, the Initial
Calibration Verification Solutions may be used) . One aqueous LCS must
be prepared and analyzed for every group of aqueous samples in a Sample
Delivery Group, or for each batch of aqueous samples digested, whichever
is more frequent. An aqueous LCS is not required for mercury. For
cyanide, a distilled ICV is used as the LCS (see Exhibit E, Section V,
item 2) .
The EPA-provided solid LCS shall be prepared and analyzed using each of
the procedures applied to the solid samples received (exception:
E-25 ILM04.0
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percent solids determination not required). If the EPA solid LCS is
unavailable, other EPA Quality Assurance Check samples or other
certified materials may be used. One solid LCS shall be prepared and
analyzed for every group of solid samples in a Sample Delivery Group, or
for each batch of samples digested and/or distilled, whichever is more
frequent.
All LCS results and percent recovery (%R) will be reported on FORM VII-
IN. If the percent recovery for the aqueous LCS falls outside the
control limits of 80-120% (exception: Ag and Sb), the analyses shall be
terminated, the problem corrected, and the samples associated with that
LCS redigested and reanalyzed.
If the results for the solid LCS fall outside the control limits
established by EPA, the analyses shall be terminated, the problem
corrected, and the samples associated with that LCS redigested and
reanalyzed.
9. ICP Serial Dilution Analysis (L)
Prior to reporting concentration data for the analyte elements, the
Contractor shall analyze and report the results of the ICP Serial
Dilution Analysis. The ICP Serial Dilution Analysis shall be performed
on a sample from each group of samples of a similar matrix type (i.e.,
water, soil) and concentration (i.e., low, medium) or for each Sample
Delivery Group, whichever is more frequent. Samples identified as field
blanks cannot be used for Serial Dilution Analysis.
If the analyte concentration is sufficiently high (minimally a factor of
50 above the instrumental detection limit in the original sample), the
serial dilution (a five fold dilution) must then agree within 10% of the
original determination after correction for dilution. If the dilution
analysis for one or more analytes is not at or within 10%, a chemical or
physical interference effect must be suspected, and the data for all
affected analytes in the samples received associated with that serial
dilution shall be flagged with an "E" on FORM IX-IN and FORM I-IN.
The percent differences for each component are calculated as follows:
% Difference = [ J ~ S [ x 100
where, I = Initial Sample Result
S = Serial Dilution Result (Instrument Reading x 5)
In the instance where there is more than one serial dilution per SDG, if
one serial dilution result is not within contract criteria, flag all the
samples of the same matrix and concentration in the Sample Delivery
Group. Serial dilution results and "E" flags shall be reported on FORM
IX-IN.
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10. Instrument Detection Limit (IDL) Determination
Before any field samples are analyzed under this contract, the
instrument detection limits (in ug/L) shall be determined for each
instrument used, within 30 days of the start of contract analyses and at
least quarterly (i.e., January, April, July, October), and shall meet
the levels specified in Exhibit C.
The Instrument Detection Limits (in ug/L) shall be determined by
multiplying by 3, the average of the standard deviations obtained on
three nonconsecutive days (e.g., Monday, Wednesday and Friday) from the
analysis of a standard solution (each analyte in reagent water) at a
concentration 3x-5x the instrument manufacturer's suggested IDL, with
seven consecutive measurements per day. Each measurement shall be
performed as though it were a separate analytical sample (i.e., each
measurement shall be followed by a rinse and/or any other procedure
normally performed between the analysis of separate samples). IDLs
shall be determined and reported for each wavelength used in the
analysis of the samples. In addition, IDLs shall be reported on Form X-
IN for each instrument used in reporting results for an SDG and shall be
submitted with each data package.
The quarterly determined IDL for an instrument shall always be used as
the IDL for that instrument during that quarter. If the instrument is
adjusted in any way that may affect the IDL, the IDL for that instrument
shall be redetermined and the results submitted for use as the
established IDL for that instrument for the remainder of the quarter.
11. Interelement Corrections for ICP
Before any field samples are analyzed under this contract, the ICP
interelement correction factors shall be determined prior to the start
of contract analyses and at least annually thereafter. Correction
factors for spectral interference due to Al, Ca, Fe, and Mg shall be
determined for all ICP instruments at all wavelengths used for each
analyte reported by ICP. Correction factors for spectral interference
due to analytes other than Al, Ca, Fe, and Mg, shall be reported if they
were applied.
If the instrument was adjusted in any way that may affect the ICP
interelement correction factors, the factors shall be redetermined and
the results submitted for use. In addition, all data used for the
determination of the interelement correction factors shall be available
to the USEPA during an on-site laboratory evaluation. Results from
interelement correction factors determination shall be reported on FORM
XI(PART 1)-IN, and FORM XI(PART 2)-IN for all ICP parameters.
12. Linear Range Analysis (LRA)
For all ICP analyses, a linear range verification check standard shall
be analyzed and reported quarterly (i.e., January, April, July, October)
for each element on FORM XII-IN. The standard shall be analyzed during
a routine analytical run performed under this contract. The
analytically determined concentration of this standard shall be within
E-27 ILM04.0
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5% of the true value. This concentration is the upper limit of the ICP
linear range beyond which results cannot be reported under this contract
without dilution of the analytical sample.
13. Furnace Atomic Absorption (AA) QC Analyses
Because of the nature of the Furnace AA technique, the special
procedures summarized in Figure 1-Furnace AA Analysis Scheme ("MSA
Tree") will be required for quantitation. (These procedures do not
replace those in Exhibit D of this SOW, but supplement the guidance
provided therein.)
a. All furnace analyses shall fall within the calibration range. In
addition, all analyses, except during full methods of standard
addition (MSA), will require duplicate injections. The absorbance
or concentration of each injection shall be reported in the raw
data as well as the average absorbance or concentration values and
the relative standard deviation (RSD) or coefficient of variation
(CV). Average concentration values are used for reporting
purposes. The Contractor shall be consistent per method and SDG
in choosing absorbance or concentration to evaluate which route is
to be followed in the MSA Tree. The Contractor shall also
indicate which of the two is being used if both absorbance and
concentration are reported in the raw data. For MSA analysis, the
absorbance of each injection shall be included in the raw data. A
maximum of 10 full sample analyses to a maximum 20 injections may
be performed between each consecutive calibration verifications
and blanks. For concentrations greater than CRDL, the duplicate
injection readings must agree within 20% RSD or CV, or the
analytical sample shall be rerun once (i.e., two additional
burns). If the readings are still out, flag the value reported on
FORM I-IN with an "M". The "M" flag is required for the
analytical spike as well as the sample. If the analytical spike
for a sample requires an "M" flag, the flag shall be reported on
FORM I-IN for that sample.
E-28 ILM04.0
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FIGURE 1. FURNACE ATOMIC ABSORPTION ANALYSIS SCHEME
Prepare and Analyze
Sample and One Spike
(2XCRDL)
(Double Injections Required)
Analyses Within
Calibration Range
YES
Recovery of Spike
Less Than 40*
NO
Sample Absorbance ot
Concentration Less Hian
50% of "Spike"
NO
Spike Recovery
Less Than 85% or
Greater Than 115%
YES
Quantitate by MSA with 3
Spikes at 50, 100 & 150% of
Sample Concentration
(Only Single Injections Required)
Correlation Coefficient Less
Than 0.995
NO
Flag Data with *S*
NO
If YES, Repeat Only ONCE
ffStfllYES
NO
YES
Spike Recovery Less Than
85% or Greater than 115%
YES
NO
Dilute Sample and Spike
If YES, Repeat Only ONCE
If Still YES
Flag Data with an "E"
Report Results Down to BDL
Report Results down to tt>L.
Flag wittia"W*
Quantitate from Calibration
Carve and Report Down to
IDL
Flag Data with a *+"
E-29
ILM04.0
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b. All furnace analyses for each analytical sample, including those
requiring an "M" flag, will require at least an analytical spike to
determine if the MSA will be required for quantitation. The analytical
spike will be required to be at a concentration (in the sample) 2x
CRDL (except for lead which must be at 20 ug/L). This requirement for
an analytical spike will include the LCS and the preparation blank.
(The LCS shall be quantitated from the calibration curve and corrective
action, if needed, taken accordingly. MSA is not to be performed on
the LCS or preparation blank, regardless of spike recovery results.) If
the preparation blank analytical spike recovery is out of control (85-
115%), the spiking solution shall be verified by respiking and rerunning
the preparation blank once. If the preparation blank analytical spike
recovery is still out of control, correct the problem and reanalyze all
analytical samples associated with that blank. An analytical spike
shall not be performed on the matrix spike sample.
The analytical spike of a sample shall be run immediately after
that sample. The percent recovery (%R) of the spike, calculated
by the same formula as Spike Sample Analyses (see item 6, this
section), will then determine how the sample will be quantitated,
as follows:
1) If the spike recovery is less than 40%, the sample shall be
diluted and rerun with another spike. Dilute the sample by
a factor of 5 to 10 and rerun. This step shall only be
performed once. If after the dilution the spike recovery is
still <40%, report data and flag with an "E" to indicate
interference problems.
2) If the spike recovery is greater than or equal to 40% and
the sample absorbance or concentration is less than 50% of
the "spike"7, report the sample results to the IDL. If the
spike recovery is less than 85% or greater than 115%, flag
the result with a "W".
3) If the sample absorbance or concentration is greater than or
equal to 50% of the "spike"7 and the spike recovery is at or
between 85% and 115%, the sample shall be quantitated
directly from the calibration curve and reported down to the
IDL.
4) If the sample absorbance or concentration is greater than or
equal to 50% of the "spike"7 and the spike recovery is less
^Analytical spikes are furnace spikes to be prepared prior to analysis,
but after digestion (if performed), by adding a known quantity of the analyte
to an aliquot of the sample. The unspiked sample aliquot shall be compensated
for any volume change in the spike samples by the addition of deionized water
to the unspiked sample aliquot. The volume of the spiking solution added
shall not exceed 10% of the analytical sample volume; this requirement also
applies to MSA spikes.
7"Spike" is defined as [absorbance or concentration of spike sample]
minus [absorbance or concentration of the sample].
E-30 ILM04.0
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than 85% or greater than 115%, the sample shall be
quantitated by MSA.
c. The following procedures will be incorporated into MSA analyses.
1) Data from MSA calculations shall be within the linear range
as determined by the calibration curve generated at the
beginning of the analytical run.
2) The sample and three spikes shall be analyzed consecutively
(MSO, MSI, MS2, MS3) for MSA quantitation (the "initial"
spike run data are specifically excluded from use in the MSA
quantitation). Only single injections shall be performed
for MSA quantitation.
Each full MSA counts as two analytical samples towards
determining 10% QC frequency (i.e., five full MSAs can be
performed between calibration verifications).
3) For analytical runs containing only MSAs, single injections
can be used for QC samples during that run. For instruments
that operate in an MSA mode only, MSA can be used to
determine QC samples during that run.
4) Spikes shall be prepared such that:
a) Spike 1 is approximately 50% of the sample
concentration.
b) Spike 2 is approximately 100% of the sample
concentration.
c) Spike 3 is approximately 150% of the sample
concentration.
5) The data for each MSA analysis shall be clearly identified
in the raw data documentation (using added concentration as
the x-variable and absorbance as the y-variable) along with
the slope, x-intercept, y-intercept and correlation
coefficient (r) for the least squares fit of the data. The
results shall be reported on FORM VIII-IN. Reported values
obtained by MSA shall be flagged on the data sheet (FORM I-
IN) with the letter "S" if the correlation coefficient is
greater than or equal to 0.995.
6) If the correlation coefficient (r) for a particular analysis
is less than 0.995, the MSA analysis shall be repeated once.
If the correlation coefficient is still less than 0.995,
report the results on FORM I-IN from the run with the best
"r" and flag the result with a "+" on FORM VIII-IN and FORM
I-IN.
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SECTION VI
CONTRACT COMPLIANCE SCREENING
Contract Compliance Screening (CCS) is one aspect of the Government's
contractual right of inspection of analytical data. CCS examines the
Contractor's adherence to the contract requirements based on the sample data
package delivered to the Agency.
CCS is performed by the Sample Management Office (SMO) under the direction of
the EPA. To assure a uniform review, a set of standardized procedures has
been developed to evaluate the sample data package submitted by a Contractor
against the technical and completeness requirements of the contract.
CCS results are mailed to the Contractor and all other data recipients. The
Contractor has a period of time to correct deficiencies. The Contractor shall
send all corrections to the Regional Client and SMO/CLAS.
CCS results are used in conjunction with other information to measure overall
Contractor performance and to take appropriate actions to correct deficiencies
in performance.
The Agency may generate a CCS trend report which summarizes CCS results over a
given period of time. The Agency may send the CCS trend report or discuss the
CCS trend report during an on-site laboratory evaluation. In a detailed
letter to the Technical Project Officer and Administrative Project Officer,
the Contractor shall address the deficiencies and the subsequent corrective
action implemented by the Contractor to correct the deficiencies within 14
days of receipt of the report or the on-site laboratory evaluation. An
alternate delivery schedule may be proposed by the Contractor, but it is the
sole decision of the Agency, represented by the Technical Project Officer or
Administrative Project Officer, to approve or disapprove the alternate
delivery schedule. If an alternate delivery schedule is proposed, the
Contractor shall describe in a letter to the Technical Project officer,
Administrative Project Officer, and Contracting Officer why he/she is unable
to meet the delivery schedule listed in this section. The Technical Project
Officer will not grant an extension for greater than 14 days for the
Contractor's response to the CCS trend report. The Contrcator shall proceed
and not assume that an extension will be granted until so notified by the TPO
and/or APO.
If new SOPs are required to be written, or if existing SOPs are required to be
rewritten or amended because of deficiencies and subsequent corrective action
implemented by the Contractor, the Contractor shall write/amend the SOPs per
the requirements listed in Exhibit E, Section IV.
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, data package audit, an on-
site laboratory evaluation, a remedial performance evaluation sample, and/or
contract sanctions, such as a Cure Notice.
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SECTION VII
ANALYTICAL STANDARD REQUIREMENTS
The U.S. Environmental Protection Agency may be unable to supply analytical
reference standards either for direct analytical measurements or for the
purpose of traceability. In these cases, all contract laboratories will be
required to prepare from materials or purchase from private chemical supply
houses those standards necessary to successfully and accurately perform the
analyses required in this protocol.
A. Preparation of Chemical Standards from the Neat High Purity Bulk
Material
If the laboratory cannot obtain analytical reference data from the U.S.
EPA, the laboratory may prepare their own chemical standards.
Laboratories shall obtain the highest purity possible when purchasing
chemical standards; standards purchased at less than 97% purity shall be
documented as to why a higher purity could not be obtained.
1. If required by the manufacturer, the chemical standards shall be
kept refrigerated when not being used in the preparation of
standard solutions. Proper storage of chemicals is essential in
order to safeguard them from decomposition.
2. The purity of a compound can sometimes be misrepresented by a
chemical supply house. Since knowledge of purity is needed to
calculate the concentration of solute in a solution standard, it
is the contract laboratory's responsibility to have analytical
documentation ascertaining that the purity of each compound is
correctly stated. Purity confirmation, when performed, should use
appropriate techniques. Use of two or more independent methods is
recommended. The correction factor for impurity when weighing
neat materials in the preparation of solution standards is:
Equation I
weight of impure compound = we^ht of pure compound
(percent purityj100)
where "weight of pure compound" is that required to prepare a
specific volume of a solution standard of a specified
concentration.
3. Mis-identification of compounds occasionally occurs and it is
possible that a mislabeled compound may be received from a
chemical supply house. It is the contract laboratory's
responsibility to have analytical documentation ascertaining that
all compounds used in the preparation of solution standards are
correctly identified.
4. Log notebooks are to be kept for all weighing and dilutions. All
subsequent dilutions from the primary standard and the
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calculations for determining their concentrations are to be
recorded and verified by a second person. All solution standards
are to be refrigerated, if required, when not in use. All
solution standards are to be clearly labeled as to the identity of
the analyte or analytes, concentration, date prepared, solvent,
and initials of the preparer.
B. Purchase of chemical standards already in solution
1. Solutions of analytical reference standards can be purchased by
Contractors provided they meet the following criteria:
Laboratories shall maintain documentation of the purity
confirmation of the material to verify the integrity of the
standard solutions they purchase.
2. The Contractor shall purchase standards for which the quality is
demonstrated statistically and analytically by a method of the
supplier's choice. One way this can be demonstrated is to prepare
and analyze three solutions; a high standard, a low standard, and
a standard at the target concentration (see parts a and b below).
The supplier must then demonstrate that the analytical results for
the high standard and low standard are consistent with the
difference in theoretical concentrations. This is done by the
Student's t-test in part "d". If this is achieved, the supplier
must then demonstrate that the concentration of the target
standard lies midway between the concentrations of the low and
high standards. This is done by the Student's t-test in part e.
Thus the standard is certified to be within 10 percent of the
target concentration.
If the procedure above is used, the supplier must document that
the following have been achieved:
a. Two solutions of identical concentration shall be prepared
independently from neat materials. An aliquot of the first
solution shall be diluted to the intended concentration (the
"target standard"). One aliquot is taken from the second
solution and diluted to a concentration ten percent greater
than the target standard. This is called the "high
standard". One further aliquot is taken from the second
solution and diluted to a concentration 10 percent less than
the target standard. This is called the "low standard".
b. Six replicate analyses of each standard (a total of 18
analyses) shall be performed in the following sequence: low
standard, target standard, high standard, low standard,
target standard, high standard, —
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c. The mean and variance of the six results for each solution
shall be calculated.
Equation 2
MEAN= n + r. + r.m + r.+ r.
Equation 3
VARIANCE =
The values
2, 3/
analyses of each standard.
represent the results of the six
The means of the low, target,
and high standards are designated M-^, M2, and M^,
respectively. The variances of the low, target, and high
standards are designated Vj_, V2, and V3, respectively.
Additionally, a pooled variance, V_, is calculated.
Equation 4
_,
v =
vp
0.81
1.21
If the square root of V_ is less than one percent of M2,
then M22 /10,000 is to be used as the value of
subsequent calculations.
Vp in all
d. The test statistic shall be calculated:
Equation 5
TEST STATISTIC =
1.1
0.9
If the test statistic exceeds 2.13, then the supplier has
failed to demonstrate a twenty percent difference between
the high and low standards. In such a case, the standards
are not acceptable.
E-35
ILM04.0
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The test statistic shall be calculated:
Equation 6
TEST STATISTIC ~ v ••••»/ v 2 . 2
If the test statistic exceeds 2.13, the supplier has failed
to demonstrate that the target standard concentration is
midway between the high and low standards. In such a case,
the standards are not acceptable.
f. The 95 percent confidence intervals for the mean result of
each standard shall be calculated:
Equation 7
\o.s
(VY
Interval for Low Standard = M^ ± 2.13 \~/\
V 6 )
Equation 8
(v^°'s
Interval for Target Standard = M2 ± 2.13 -^
Equation 9
/VY5'5
Interval for High Standard = M3 ± 2.13 -^
These intervals shall not overlap. If overlap is observed,
then the supplier has failed to demonstrate the ability to
discriminate the 10 percent difference in concentrations.
In such a case, the standards are not acceptable. In any
event, the laboratory is responsible for the quality of the
standards employed for analyses under this contract.
Requesting Standards From the EPA Standards Repository
Solutions of analytical reference materials can be ordered from the U.S.
EPA chemical Standards Repository, depending on availability. The
Contractor can place an order for standards only after demonstrating
that these standards are not available from commercial vendors either in
solution or as a neat material.
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D. Documentation of the Verification and Preparation of Chemical Standards
It is the responsibility of each laboratory to maintain the necessary
documentation to show that the chemical standards they have used in the
performance of CLP analysis conform to the requirements previously
listed. Weighing logbooks, calculations, raw data, etc., whether
produced by the laboratory or purchased from chemical supply houses,
shall be maintained by the laboratory and may be subject to review
during on-site inspection visits. In those cases where the
documentation is supportive of the analytical results of data packages
sent to EPA, such documentation is to be kept on file by the
laboratories for a period of one year.
Upon request by the Technical Project Officer or Administrative Project
Officer, the Contractor shall submit their most recent previous year's
documentation (12 months) for the verification and preparation of
chemical standards within 14 days of the receipt of request to the
recipients he/she designates.
The Agency may generate a report discussing deficiencies in the
Contractor's documentation for the verification and preparation of
chemical standards or may discuss the deficiencies during an on-site
laboratory evaluation. In a detailed letter to the Technical Project
Officer, Administrative Project Officer, and EMSL/LV, the Contractor
shall address the deficiencies and the subsequent corrective action
implemented by the Contractor to correct the deficiencies within 14 days
of receipt of the report or the on-site laboratory evaluation. An
alternate delivery schedule may be proposed by the Contractor, but it is
the sole decision of the Agency, represented either by the Technical
Project Officer or Administrative Project Officer, to approve or
disapprove the alternate delivery schedule. If an alternate delivery
schedule is proposed, the Contractor shall describe in a letter to the
Technical Project Officer, Administrative Project Officer, and the
Contracting Officer why he/she is unable to meet the delivery schedule
listed in this section. The Technical Project Officer/Administrative
Project Officer will not grant an extension for greater than 14 days for
the Contractor's response letter to the standards documentation report.
The Contractor shall proceed and not assume that an extension will be
granted until so notified by the TPO and/or APO.
If new SOPs are required to be written, or if existing SOPs are
required to be rewritten or amended because of deficiencies and
subsequent corrective action implemented by the Contractor, the
Contractor shall write/amend the SOPs per the requirements listed in
Exhibit E, Section IV.
If the 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 the
contract, suspension of sample shipment to Contractor, data package
audit, an on-site laboratory evaluation, a remedial laboratory
evaluation sample, and/or contract sanctions, such as a Cure Notice.
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SECTION VIII
DATA PACKAGE AUDITS
Data package audits are performed by the Agency for program overview and
specific Regional concerns. Standardized procedures have been established to
assure uniformity of the auditing process. Data packages are periodically
selected from recently received Cases. They are evaluated for the technical
quality of hardcopy raw data, quality assurance, and the adherence to
contractual requirements. This function provides external monitoring of
program QC requirements.
Data package audits are used to assess the technical quality of the data and
evaluate overall laboratory performance. Audits provide the Agency with an
in-depth inspection and evaluation of the Case data package with regard to
achieving QA/QC acceptability. A thorough review of the raw data is completed
including: all instrument readouts used for the sample results, instrument
printouts, and other documentation for deviations from the contractual
requirements, a check for transcription and calculation errors, a review of
the qualifications of the laboratory personnel involved with the Case, and a
review of all current SOPs on file.
Responding to the Data Package Audit Report:
After completion of the data package audit, the Agency may send a copy of the
data package audit report to the Contractor or may discuss the data package
audit report on an on-site laboratory evaluation. In a detailed letter to the
Technical Project Officer, Administrative Project Officer, and the EPA
designated recipient, the Contractor shall discuss the corrective actions
implemented to resolve the deficiencies listed in the data package audit
report within 14 days of receipt of the report. An alternate delivery
schedule may be proposed by the Contractor, but it is the sole decision of the
Agency, represented either by the Technical Project Officer or Administrative
Project Officer, to approve or disapprove the alternate delivery schedule. If
an alternate delivery schedule is proposed, the Contractor shall describe in a
letter to the Technical Project Officer, Administrative Project Officer, and
the Contracting Officer why he/she is unable to meet the delivery schedule
listed in this section. The Technical Project Officer/Administrative Project
Officer will not grant an extension for greater than 14 days for the
Contractor's response letter to the data package report. The Contractor shall
proceed and not assume that an extension will be granted until so notified by
the TPO and/or APO.
If new SOPs are required to be written, or if existing SOPs are required to be
rewritten or amended because of deficiencies and subsequent corrective action
implemented by the Contractor, the Contractor shall write/amend the SOPs per
the requirements listed in Exhibit E, Section IV.
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 under the contract,
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suspension of sample shipment to the Contractor, an on-site laboratory
evaluation, data package audit, remedial performance evaluation sample, and/or
contract sanctions, such as a Cure Notice.
Regional Data Review:
Contractor data are generated to meet the specific needs of the EPA Regions.
In order to verify the useability of data for the intended purpose, each
Region reviews data from the perspective of the end user, based on functional
guidelines for data review which have been developed jointly by the Regions
and the National Program Office. Each Region uses these guidelines as the
basis for data evaluation. Individual Regions may augment the basic guideline
review process with additional review based on Region-specific or site-
specific concerns. Regional reviews, like the sites under investigation, vary
based on the nature of the problem under investigation and the Regional
response appropriate to the specific circumstances.
Regional data reviews, relating usability of the data to a specific site, are
part of the collective assessment process. They complement the review done at
the Sample Management Office, which is designed to identify contractual
discrepancies. These individual evaluations are integrated into collective
review that is necessary for Program and Contractor administration and
management and may be used to take appropriate action to correct deficiencies
in the Contractor's performance.
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SECTION IX
PERFORMANCE EVALUATION SAMPLES
Although intralaboratory QC may demonstrate Contractor and method performance
that can be tracked over time, an external performance evaluation program is
an essential feature of a QA program. As a means of measuring Contractor and
method performance, Contractors participate in interlaboratory comparison
studies conducted by the EPA. Results from the analysis of these performance
evaluation samples (PES) will be used by the EPA to verify the 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.
Sample sets may be provided to participating Contractors as frequently as on
an SDG-by-SDG basis as a recognizable QC sample of known composition; as a
recognizable QC sample of unknown composition; or not recognizable as a QC
material. The laboratory evaluation samples may be sent either by the
Regional client or the National Program Office. The results of all such
quality control samples may be used as the basis for rejection of data for:
sample(s) within an SDG, a fraction (e.g., metals and/or cyanide) within an
SDG or the entire SDG, and/or may be used as the basis for contract action.
The Contractor shall analyze the samples and return the data package and all
raw data within the contract required turnaround time.
In addition to PES preparation and analysis, 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.
Contractors are required to analyze the samples and return the data package
and all raw data within the contract required turnaround time.
A Contractor's results on the laboratory evaluation samples will determine the
Contractor's performance as follows:
1. Acceptable, No Response Required (Score greater than or equal to 90
percent):
Data meets most or all of the scoring criteria. No response is
required.
2. Acceptable, Response Explaining Deficiency(iesj Required (Score greater
than or equal to 75 percent but less than 90 percent):
Deficiencies exist in the Contractor's performance.
Within 14 days of receipt of notification from EPA, the Contractor shall
describe the deficiency(ies) and the action(s) taken to correct the
deficiency(ies) in a letter to the Administrative Project Officer, the
Technical Project Officer and the EPA designated recipient.
An alternate delivery schedule may be proposed by the Contractor, but it
is the sole decision of the Agency, represented either by the Technical
Project Officer or Administrative Project Officer, to approve or
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disapprove the alternate delivery schedule. If an alternate delivery
schedule is proposed, the Contractor shall describe in a letter to the
Technical Project Officer, Administrative Project Officer, and the
Contracting Officer why he/she is unable to meet the delivery schedule
listed in this section. The Technical Project Officer/Administrative
Project Officer will not grant an extension for greater than 14 days for
the Contractor's response letter to the laboratory evaluation sample
report. The Contractor shall proceed and not assume that an extension
will be granted until so notified by the TPO and/or APO.
If new SOPs are required to be written or if existing SOPs are required
to be rewritten or amended because of deficiencies and subsequent
corrective action implemented by the Contractor, the Contractor shall
write/amend the SOPs per the requirements listed in Exhibit E, Section
IV.
3. Unacceptable Performance, Response Explaining Deficiency(ies) Required
(Score less than 75 percent):
Deficiencies exist in the Contractor's performance to the extent that
the National Program Office has determined that the Contractor has not
demonstrated the capability to meet the contract requirements.
Within 14 days of receipt of notification from EPA, the Contractor shall
describe the deficiency(ies) and the action(s) taken to correct the
deficiency(ies) in a letter to the Administrative Project Officer, the
Technical Project Officer and the EPA designated recipient.
An alternate delivery schedule may be proposed by the Contractor, but it
is the sole decision of the Agency, represented either by the Technical
Project Officer or Administrative Project Officer, to approve or
disapprove the alternate delivery schedule. If an alternate delivery
schedule is proposed, the Contractor shall describe in a letter to the
Technical Project Officer, Administrative Project officer, and the
Contracting Officer why he/she is unable to meet the delivery schedule
listed in this section. The Technical Project Officer/Administrative
Project Officer will not grant an extension for greater than 14 days for
the Contractor's response letter to the performance evaluation sample
report. The Contractor shall proceed and not assume that an extension
will be granted until so notified by the TPO and/or APO.
If new SOPs are required to be written, or if existing SOPs are required
to be rewritten or amended because of deficiencies and subsequent
corrective action implemented by the Contractor, the Contractor shall
write/amend the SOPs per the requirements listed in Exhibit E, Section
IV.
The Contractor shall be notified by the Technical Project Officer or
Administrative Project Officer concerning the remedy 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 the contract, suspension of sample shipment to the
Contractor, an on-site laboratory evaluation, data package audit,
remedial performance evaluation sample, and/or a contract sanction, such
as a Cure Notice.
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Note: 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.
If the 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 the
contract, suspension of sample shipment to the Contractor, an on-site
laboratory evaluation, data package audit, a remedial laboratory
evaluation sample and/or contract sanctions, such as a Cure Notice.
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SECTION X
OS-SITE LABORATORY EVALUATIONS
At a frequency dictated by a contract laboratory's performance, the
Administrative Project Officer, Technical Project Officer or their authorized
representative will conduct an on-site laboratory evaluation. On-site
laboratory evaluations are carried out to monitor the Contractor's ability to
meet selected terms and conditions specified in the contract. The evaluation
process incorporates two separate categories: Quality Assurance Evaluation
and an Evidentiary Audit.
A. Quality Assurance On-Site Evaluation
Quality assurance evaluators inspect the Contractor's facilities to
verify the adequacy and maintenance of instrumentation, the continuity,
experience and education of personnel, and the acceptable performance of
analytical and QC procedures. The Contractor should expect that items
to be monitored will include, but not be limited to, the following:
Size and appearance of the facility
Quantity, age,, availability, scheduled maintenance and
performance of instrumentation
Availability, appropriateness, and utilization of the QAP
and 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
Prior to an on-site evaluation, various documentation pertaining to
performance of the specific Contractor is integrated in a profile
package for discussion during the evaluation. Items that may be
included are previous on-site reports, performance evaluation sample
scores, Regional review of data, Regional QA materials, data audit
reports, results of CCS, and data trend reports.
B. Evidentiary Audit
Evidence auditors conduct an on-site laboratory evaluation to determine
if laboratory policies and procedures are in place to satisfy evidence
handling requirements as stated in Exhibit F. The evidence audit is
comprised of the following three activities:
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1. Procedural Audit
The procedural audit consists of review and examination of actual
standard operating procedures and accompanying documentation for
the following laboratory operations: sample receiving, sample
storage, sample identification, sample security, sample tracking
(from receipt to completion of analysis) and analytical project
file organization and assembly.
2. Written SOPs Audit
The written SOPs audit consists of review and examination of the
written SOPs to determine if they are accurate and complete for
the following laboratory operations: sample receiving, sample
storage, sample identification, sample security, sample tracking
(from receipt to completion of analysis) and analytical project
file organization and assembly.
3. Analytical Project File Evidence Audit
The analytical project file evidence audit consists of review and
examination of the analytical project file documentation. The
auditors review the files to determine:
The accuracy of the document inventory
The completeness of the file
The adequacy and accuracy of the document numbering
system
Traceability of sample activity
• Identification of activity recorded on the documents
Error correction methods
C. Discussion of the On-Site Team's Findings
The quality assurance and evidentiary auditors discuss their findings
with the Administrative Project Officer/Technical Project Officer prior
to debriefing the Contractor. During the debriefing, the auditors
present their findings and recommendations for corrective actions
necessary to the Contractor personnel.
D. Corrective Action Reports For Follow-Through to Quality Assurance and
Evidentiary Audit Reports
On-site laboratory evaluation;
Following an on-site laboratory evaluation, quality assurance and/or
evidentiary audit reports which discuss deficiencies found during the
on-site evaluation may be sent to the Contractor. In a detailed letter,
the Contractor shall discuss the corrective actions implemented to
resolve the deficiencies discussed during the on-site evaluation and
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discussed in the report(s) to the Technical Project Officer and
Administrative Project Officer within 14 days of receipt of the report.
An alternate delivery schedule may be proposed by the Contractor, but it
is the sole decision of the Agency, represented either by the Technical
Project Officer or Administrative Project Officer, to approve or
disapprove the alternate delivery schedule. If an alternate delivery
schedule is proposed, the Contractor shall describe in a letter to the
Technical Project Officer, Administrative Project Officer, and the
Contracting officer why he/she is unable to meet the delivery schedule
listed in this section. The Technical Project Officer/Administrative
Project Officer will not grant an extension for greater than 14 days for
the Contractor's response letter to the quality assurance and
evidentiary audit report. The Contractor shall proceed and not assume
that an extension will be granted until so notified by the TPO and/or
APO.
If new SOPs are required to be written, or if existing SOPS are required
to be rewritten or amended because of the deficiencies and the
subsequent corrective action implemented by the Contractor, the
Contractor shall write/amend the SOPs per the requirements listed in
Exhibit E, Section IV.
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 under the contract,
suspension of sample shipment to the Contractor, an on-site laboratory
evaluation, data package audit, a remedial performance evaluation sample,
and/or contract sanctions, such as a Cure Notice.
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SECTION XI
DATA MANAGEMENT
Data management procedures are defined as procedures specifying the
acquisition or entry, update, correction, deletion, storage and security of
computer readable data and files. These procedures shall be in written form
and contain a clear definition for all databases and files used to generate or
resubmit deliverables. Key areas of concern include: system organization
(including personnel and security), documentation operations, traceability and
quality control.
Data manually entered from hard-copy shall be quality controlled and the error
rates estimated. Systems should prevent entry of incorrect or out-of-range
data and alert data entry personnel of errors. In addition, data entry error
rates shall be estimated and recorded on a monthly basis by reentering a
statistical sample of the data entered and calculating discrepancy rates by
data element.
The record of changes in the form of corrections and updates to data
originally generated, submitted, and/or resubmitted shall be documented to
allow traceablilty of updates. Documentation shall include the following for
each change:
Justification or rationale for the change.
Initials of the person making the change or changes. Data changes
shall be implemented and reviewed by a person or group independent
of the source generating the deliverable.
Change documentation shall be retained according to the schedule
of the original deliverable.
Resubmitted diskettes or other deliverables shall be reinspected
as a part of the laboratory's internal inspection process prior to
resubmission. The entire deliverable, not just the changes, shall
be inspected.
The Laboratory Manager shall approve changes to originally
submitted deliverables.
Documentation of data changes may be requested by laboratory
auditors.
Lifecycle management procedures shall be applied to computer software systems
developed by the laboratory to be used to generate and edit contract
deliverables. Such systems shall be thoroughly tested and documented prior to
utilization.
A software test and acceptance plan including test requirements,
test results and acceptance criteria shall be developed, followed,
and available in written form.
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System changes shall not be made directly to production systems
generating deliverables. Changes shall be made first to a
development system and tested prior to implementation.
• Each version of the production system will be given an
identification number, date of installation, and date of last
operation and will be archived.
System and operations documentation shall be developed and
maintained for each system. Documentation shall include a user's
manual and an operations and maintenance manual.
Individual(s) responsible for the following functions shall be identified:
• System operation and maintenance including documentation and
training.
Database integrity, including data entry, data updating and
quality control.
Data and system security, backup and archiving.
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EXHIBIT F
CHAIN-OF-CUSTODY, DOCUMENT CONTROL,
AND WRITTEN STANDARD OPERATING PROCEDURES
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1. INTRODUCTION
1.1 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 ensure that EPA's sample data and
records supporting sample-related activities are admissible and have
weight as evidence in future litigation, Contractors are required to
maintain EPA samples under chain-of-custody and to account for all
samples and supporting records of sample handling, preparation, and
analysis. Contractors shall maintain sample identity, sample custody,
and all sample-related records according to the requirements in this
exhibit.
1.2 The purposes of the evidence requirements include:
Ensuring traceability of samples while in possession of the
Contractor.
Ensuring custody of samples while in possession of the
Contractor.
Ensuring the integrity of sample identity while in possession of
the Contractor.
Ensuring sample-related activities are recorded on documents or
in other formats for EPA sample receipt, storage, preparation,
analysis, and disposal.
Ensuring all laboratory records for each specified Sample
Delivery Group will be accounted for when the project is
completed.
Ensuring that all laboratory records directly related to EPA
samples are assembled and delivered to EPA or, prior to delivery,
are available upon EPA's request.
2. Standard Operating Procedures
The Contractor shall implement the following standard operating
procedures for sample receiving, sample identification, sample security,
sample storage, sample tracking and document control, computer-resident
sample data control, and Complete Sample Delivery Group File
organization and assembly to ensure accountability of EPA sample chain-
of-custody as well as control of all EPA sample-related records.
2.1 Sample Receiving
2.1.1 The Contractor shall designate a sample custodian responsible for
receiving EPA samples.
2.1.2 The Contractor shall designate a representative to receive EPA
samples in the event that the sample custodian is not available.
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2.1.3 Upon receipt, the condition of shipping containers and sample
containers shall be inspected and recorded on Form DC-1 by the
sample custodian or his/her representative.
2.1.4 Upon receipt, the condition of the custody seals (intact/broken)
shall be inspected and recorded on Form DC-1 by the sample
custodian or his/her representative.
2.1.5 The sample custodian or his/her representative shall verify and
record on Form DC-1 the presence or absence of the following
documents accompanying the sample shipment:
Custody seals,
Chain-of-custody records,
Traffic reports or packing lists,
Airbills or airbill stickers, and
Sample tags.
2.1.6 The sample custodian or his/her representative shall verify and
record on Form DC-1 the agreement or disagreement of information
recorded on all documents received with samples and information
recorded on sample containers.
2.1.7 The sample custodian or his/her representative shall record the
following information on Form DC-1 as samples are received and
inspected:
Custody seal numbers when present,
Airbill or airbill sticker numbers,
• Sample tags listed/not listed on chain-of-custody records,
Date of receipt,
Time of receipt,
EPA sample numbers,
Sample tag numbers,
Assigned laboratory numbers,
Samples delivered by hand, and
Problems and discrepancies.
2.1.8 The sample custodian or his/her representative shall sign, date,
and record the time on all accompanying forms, when applicable,
at the time of sample receipt (for example, chain-of-custody
records, traffic reports or packing lists, and airbills).
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Note: Initials are not acceptable.
2.1.9 The Contractor shall contact the Sample Management Office (SMO)
to resolve problems and discrepancies including, but not limited
to, absent documents, conflicting information, absent or broken
custody seals, and unsatisfactory sample condition (for example,
leaking sample container).
2.1.10 The Contractor shall record resolution of problems and
discrepancies by SMO.
2.2 Sample Identification
2.2.1 The Contractor shall maintain the identity of EPA samples and
prepared samples (including extracted samples, digested samples,
and distilled samples) throughout the laboratory.
2.2.2 Each sample and sample preparation container shall be labeled
with the EPA number or a unique laboratory sample identification
number.
J:
2.3 Sample Security
2.3.1 The Contractor shall demonstrate that EPA sample custody is
maintained from receiving through retention or disposal. A
sample is in custody if:
It is in your possession, or
It is in your view after being in your possession, or
It is locked in a secure area after being in your
possession, or
It is in a designated secure area. (Secure areas shall be
accessible only to authorized personnel.)
2.3.2 The Contractor shall demonstrate security of designated secure
areas.
2.4 Sample Storage
The Contractor shall designate storage areas for EPA samples and
prepared samples.
2.5 Sample Tracking and Document Control
2.5.1 The Contractor shall record all activities performed on EPA
samples.
2.5.2 Titles which identify the activities recorded shall be printed on
each page of all laboratory documents. (Activities include, but
are not limited to, sample receipt, sample storage, sample
preparation, and sample analysis.) When a document is a record
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of analysis, the instrument type and parameter group (for
example, ICP-Metals) shall be included in the title.
2.5.3 When columns are used to organize information recorded on
laboratory documents, the information recorded in the columns
shall be identified in a column heading.
2.5.4 Reviewers' signatures shall be identified on laboratory documents
when reviews are conducted.
Note: Individuals recording review comments on computer-
generated raw data are not required to be identified unless the
written comments address data validity.
2.5.5 The laboratory name shall be identified on preprinted laboratory
documents.
2.5.6 Each laboratory document entry shall be dated with the
month/day/year (for example, 01/01/90) and signed (or initialed)
by the individual(s) responsible for performing the recorded
activity at the time the activity is recorded.
2.5.7 Notations on laboratory documents shall be recorded in ink.
2.5.8 Corrections to laboratory documents and raw data shall be made by
drawing single lines through the errors and entering the correct
information. Information shall not be obliterated or rendered
unreadable. Corrections and additions to information shall be
signed (or initialed) and dated.
2.5.9 Unused portions of laboratory documents shall be lined-out.
2.5.10 Pages in bound and unbound logbooks shall be sequentially
numbered.
2.5.11 Instrument-specific run logs shall be maintained to enable the
reconstruction of run sequences.
2.5.12 Logbook entries shall be in chronological order.
2.5.13 Logbook entries shall include only one Sample Delivery Group
(SDG) per page, except in the events where SDGs "share" QC
samples (for example, instrument run logs and extraction logs).
2.5.14 Information inserted into laboratory documents shall be affixed
permanently in place. The individual responsible for inserting
information shall sign and date across the insert and logbook
page at the time information is inserted.
2.5.15 The Contractor shall document disposal or retention of EPA
samples, remaining portions of samples, and prepared samples.
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2.6 Computer-Resident Sample Data Control
2.6.1 Contractor personnel responsible for original data entry shall be
identified at the time of data input.
2.6.2 The Contractor shall make changes to electronic data in a manner
which ensures that the original data entry is preserved, the
editor is identified, and the revision date is recorded.
2.6.3 The Contractor shall routinely verify the accuracy of manually
entered data, electronically entered data, and data acquired from
instruments.
2.6.4 The Contractor shall routinely verify documents produced by the
electronic data collection system to ensure accuracy of the
information reported.
2.6.5 The Contractor shall ensure that the electronic data collection
system is secure.
The electronic data collection system shall be maintained in
a secure location.
Access to the electronic data collection system functions
shall be limited to authorized personnel through utilization
of software security techniques (for example, log-ons or
restricted passwords).
Electronic data collection systems shall be protected from
the introduction of external programs or software (for
example, viruses).
2.6.6 The Contractor shall designate archive storage areas for
electronic data and the software required to access the data.
2.6.7 The Contractor shall designate an individual responsible for
maintaining archives of electronic data including the software.
2.6.8 The Contractor shall maintain the archives of electronic data and
necessary software in a secure location. (Secure areas shall be
accessible only to authorized personnel.)
2.7 Complete Sample Delivery Group File Organization and Assembly
2.7.1 The Contractor shall designate a document control officer
responsible for the organization and assembly of the Complete SDG
File (CSF).
2.7.2 The Contractor shall designate a representative responsible for
the organization and assembly of the CSF in the event that the
document control officer is not available.
2.7.3 The Contractor shall maintain documents relating to the CSF in a
secure location.
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2.7.4 All original laboratory forms and copies of SDG-related logbook
pages shall be included in the CSF.
2.7.5 Copies of laboratory documents in the CSF shall be photocopied in
a manner to provide complete and legible replicates.
2.7.6 Documents relevant to each SDG including, but not limited to, the
following shall be included in the CSF:
logbook pages, • re-analysis records,
benchsheets, • records of failed or attempted
screening analysis,
records, • custody records,
preparation • sample tracking records,
records, • raw data summaries,
re-preparation • computer printouts,
records, • correspondence,
analytical • FAX originals,
records, • library search results, and
other.
2.7.7 The document control officer or his/her representative shall
ensure that sample tags are encased in clear plastic bags before
placing them in the CSF.
2.7.8 CSF documents shall be organized and assembled on an SDG-specific
basis.
2.7.9 Original documents which include information relating to more
than one SDG (for example, chain-of-custody records, traffic
reports, calibration logs) shall be filed in the CSF of the
lowest SDG number, and copies of these originals shall be placed
in the other CSF(s). The document control officer or his/her
representative shall record the following statement on the copies
in dark ink;
COPY
ORIGINAL DOCUMENTS ARE INCLUDED IN CSF
Signature
Date
2.7.10 All CSFs shall be submitted with a completed Form DC-2. All
resubmitted CSFs shall be submitted with a new or revised Form
DC-2.
2.7.11 Each item in the CSF and resubmitted CSFs shall be inventoried
and assembled in the order specified on Form DC-2. Each page of
the CSF shall be stamped with a sequential number. Page number
ranges shall be recorded in the columns provided on Form DC-2.
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Intentional gaps in the page numbering sequence shall be recorded
in the "Comments" section on Form DC-2. When inserting new or
inadvertently omitted documents, the Contractor shall identify
them with unique accountable numbers. The unique accountable
numbers and the locations of the documents shall be recorded in
the "Other Records" sectioft on Form DC-2.
2.7.12 Before shipping each CSF, the document control officer or his/her
representative shall verify the agreement of information recorded
on all documentation and ensure that the information is
consistent and the CSF is complete.
2.7.13 The document control officer or his/her representative shall
document the shipment of deliverable packages including what was
sent, to whom, the date, and the carrier used.
2.7.14 Shipments of deliverable packages, including resubmittals, shall
be sealed with custody seals by the document control officer or
his/her representative in a manner such that opening the packages
would break the seals.
2.7.15 Custody seals shall be signed and dated by the document control
officer or his/her representative when sealing deliverable
packages.
3. WRITTEN STANDARD OPERATING PROCEDURES
The Contractor shall develop and implement the following written
standard operating procedures (SOPs) for sample receiving, sample
identification, sample security, sample storage, sample tracking and
document control, computer-resident sample data control, and CSF file
organization and assembly to ensure accountability for EPA sample chain-
of-custody and control of all EPA sample-related records.
3.1 Sample Receiving
3.1.1 The Contractor shall have written SOPs for sample receiving which
accurately reflect the procedures used by the laboratory.
3.1.2 The written SOPs for sample receiving shall ensure that the
procedures listed below are in use at the laboratory.
The condition of shipping containers and sample containers
are inspected and recorded on Form DC-1 upon receipt by the
sample custodian or his/her representative.
The condition of custody seals are inspected and recorded on
Form DC-1 upon receipt by the sample custodian or his/her
representative.
The presence or absence of the following documents
accompanying the sample shipment is verified and recorded on
Form DC-1 by the sample custodian or his/her representative:
Custody seals,
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Chain-of-custody records,
Traffic reports or packing lists,
Airbills or airbill stickers, and
— Sample tags.
The agreement or disagreement of information recorded on
shipping documents with information recorded on sample
containers is verified and recorded on Form DC-1 by the
sample custodian or his/her representative.
The following information is recorded on Form DC-1 by the
sample custodian or his/her representative as samples are
received and inspected:
Custody seal numbers when present,
Airbill or airbill sticker numbers,
Sample tag numbers listed/not listed on chain-of-
custody records,
— Date of receipt,
Time of receipt,
EPA sample numbers.
Sample tag numbers,
Assigned laboratory numbers,
— Samples delivered by hand, and
Problems and discrepancies.
All accompanying forms are signed, dated, and the time is
recorded, when applicable, at the time of sample receipt
(for example, chain-of-custody records, traffic reports or
packing lists, and airbills) by the sample custodian or
his/her representative.
SMO is contacted to resolve problems and discrepancies
including, but not limited to, absent documents, conflicting
information, absent or broken custody seals, and
unsatisfactory sample condition (for example, leaking sample
container).
The resolution of problems and discrepancies by SMO is
recorded.
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3.2 Sample Identification
3.2.1 The Contractor shall have written SOPs for sample identification
which accurately reflect the procedures used by the laboratory.
3.2.2 The written SOPs for sample identification shall ensure that the
procedures listed below are in use at the laboratory.
The identity of EPA samples and prepared samples is
maintained throughout the laboratory:
When the Contractor assigns unique laboratory sample
identification numbers, the written SOPs shall include
a description of the procedure used to assign these
numbers,
When the Contractor uses prefixes or suffixes in
addition to laboratory sample identification numbers,
the written SOPs shall include their definitions, and
When the Contractor uses methods to uniquely identify
fractions/parameter groups and matrix type, the
written SOPs shall include a description of these
methods.
Each sample and sample preparation container is labeled with
the SMO number or a unique laboratory sample identification
number.
3.3 Sample Security
3.3.1 The Contractor shall have written SOPs for sample security which
accurately reflect the procedures used by the laboratory.
3.3.2 The written SOPs for sample security shall include the items
listed below.
• Procedures which ensure the following:
— Sample custody is maintained, and
The security of designated secure areas is maintained.
• A list of authorized personnel who have access to locked
storage areas.
3.4 Sample Storage
3.4.1 The Contractor shall have written SOPs for sample storage which
accurately reflect the procedures used by the laboratory.
3.4.2 The written SOPs for sample storage shall describe locations,
contents, and identities of all storage areas for EPA samples and
prepared samples in the laboratory.
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3.5 Sample Tracking and Document Control
3.5.1 The Contractor shall have written SOPs for sample tracking and
document control which accurately reflect the procedures used by
the laboratory.
3.5.2 The written SOPs for sample tracking and document control shall
include the items listed below.
Examples of all laboratory documents used during sample
receiving, sample storage, sample transfer, sample analyses,
CSF organization and assembly, and sample retention or
disposal.
Procedures which ensure the following:
All activities performed on EPA samples are recorded;
Titles which identify the activities recorded are
printed on each page of all laboratory documents;
— Information recorded in columns is identified with
column headings;
Reviewers' signatures are identified on laboratory
documents;
The laboratory name is included on preprinted
laboratory documents;
Laboratory document entries are signed and dated with
the month/day/year (for example, 01/01/90);
Entries on all laboratory documents are recorded in
ink;
Corrections and additions to laboratory documents are
made by drawing single lines through the errors,
entering the correct information, and initialing and
dating the new information;
— Unused portions of laboratory documents are lined-out;
— Pages in bound and unbound logbooks are sequentially
numbered;
Instrument-specific run logs are maintained to enable
the reconstruction of run sequences;
— Logbook entries are recorded in chronological order;
— Entries are recorded for only one SDG on a page,
except in the event where SDGs "share" QC samples (for
example, instrument run logs and extraction logs);
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— Information inserted in laboratory documents is
affixed permanently, signed or initialled, and dated
across the insert; and
— The retention or disposal of EPA samples, remaining
portions of samples, and prepared samples is
documented.
3.6 Computer-Resident Sample Data Control
3.6.1 The Contractor shall have written SOPs for computer-resident
sample data control which accurately reflect the procedures used
by the laboratory.
3.6.2 The written SOPs for computer-resident sample data control shall
include the items listed below.
• Procedures which ensure the following:
— Contractor personnel responsible for original data
entry are identified;
Changes to electronic data are made such that the
original data entry is preserved, the editor is
identified, and the revision date is recorded;
The accuracy of manually entered data, electronically
entered data, and data acquired from instruments is
verified;
— Report documents produced by the electronic data
collection system are routinely verified to ensure the
accuracy of the information reported;
Electronic data collection system security is
maintained; and
Archives of electronic data and accompanying software
are maintained in a secure location.
Descriptions of archive storage areas for the electronic
data and the software required to access data archives.
A list of authorized personnel who have access to electronic
data collection system functions and to archived data.
3.7 CSF Organization and Assembly
3.7.1 The Contractor shall have written SOPs for CSF organization and
assembly which accurately reflect the procedures used by the
laboratory.
3.7.2 The written SOPs for CSF organization and assembly shall ensure
that the procedures listed below are in use at the laboratory.
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Documents relating to the CSF are maintained in a secure
location.
All original laboratory forms and copies of SDG-related
logbook pages are included in the CSF.
Laboratory documents are photocopied in a manner to provide
complete and legible replicates.
All documents relevant to each SDG are included in the CSF.
Sample tags are encased in clear plastic bags by the
document control officer or his/her representative before
placing them in the CSF.
The CSF is organized and assembled on an SDG-specific basis.
Original documents which contain information relating to
more than one SDG are filed in the CSF of the lowest SDG and
copies are referenced to originals in the event that an
original document contains information relating to more than
one SDG.
Each CSF is submitted with a completed Form DC-2, and
resubmitted CSFs are submitted with a new or revised Form
DC-2.
Each page of the CSF is stamped with a sequential number and
the page number ranges are recorded in the columns provided
on Form DC-2. Intentional gaps in the page numbering
sequence are recorded in the "Comments Section" of Form DC-
2. Inserted documents are recorded in the "Other Records"
section of Form DC-2.
Consistency and completeness of the CSF are verified by the
document control officer or his/her representative.
Shipments of deliverable packages are documented by the
document control officer or his/her representative.
Deliverable packages are shipped by the document control
officer or his/her representative using custody seals in a
manner such that opening the packages would break the seals.
Custody seals are signed and dated by the document control
officer or his/her representative before placing them on
deliverable packages.
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EXHIBIT G
GLOSSARY OF TERMS
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GLOSSARY OF TERMS
ABSORBANCE - a measure of the decrease in incident light passing through a sample
into the detector. It is defined mathematically as:
, = I (solvent) = , lo
I(solution) a J
Where, I = radiation intensity
ALIQUOT - a measured portion of a field sample taken for analysis.
ANALYSIS DATE/TIME - the date and military time (24-hour clock) of the
introduction of the sample, standard, or blank into the analysis system.
ANALYTE - the element or ion an analysis seeks to determine; the element 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), CRDL standard for
AA (CRA), CRDL standard for ICP (CRI), laboratory control sample (LCS),
preparation blank (PB) and linear range analysis sample (LRS).
ANALYTICAL SPIKE - the furnace spike at 2X CRDL or 20 ppb for lead added prior
to analysis and after digestion, if digestion is required.
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.
BATCH - a group of samples prepared at the same time in the same location using
the same method.
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 acidified deionized/distilled water.
CALIBRATION STANDARDS - a series of known standard solutions used by the analyst
for calibration of the instrument (i.e., preparation of the analytical curve).
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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. A Case consists of one or more Sample Delivery Groups.
COEFFICIENT OF VARIATION (CV) - the standard deviation as a percent of the
arithmetic mean.
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.
CONTINUING CALIBRATION - analytical standard run every 10 analytical samples or
every 2 hours, 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.
CORRELATION COEFFICIENT - a number (r) which indicates the degree of dependence
between two variables (concentration - absorbance). The more dependent they are
the closer the value to one. Determined on the basis of the least squares line.
DAY - unless otherwise specified, day shall mean calendar day.
DIGESTION LOG - an official record of the sample preparation (digestion).
DISSOLVED METALS - analyte elements in an aqueous sample which will pass through
a 0.45 urn filter.
DRY WEIGHT - the weight of a sample based on percent solids. The weight after
drying in an oven.
DUPLICATE - a second aliquot of a sample that is treated the same as the original
sample in order to determine the precision of the method.
FIELD BLANK - this is any sample that is submitted from the field and is
identified as a blank. This includes trip blanks, rinsates, equipment blanks,
etc.
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.
FLAME ATOMIC ABSORPTION (AA) - atomic absorption which utilizes flame for
excitation.
GRAPHITE FURNACE ATOMIC ABSORPTION (GFAA) - atomic absorption which utilizes a
graphite cell for excitation.
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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)
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 (ICP) - a technique for the simultaneous or sequential
multi-element 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 multiplying by three the
standard deviation obtained for the analysis of a standard solution (each analyte
in reagent water) at a concentration of 3x-5x IDL on three nonconsecutive days
with seven consecutive measurements per day.
INSTRUMENT CHECK SAMPLE - a solution containing both interfering and analyte
elements of known concentration that can be used to verify background and
interelement correction factors.
INSTRUMENT CHECK STANDARD - a multi-element standard of known concentrations
prepared by the analyst to monitor and verify instrument performance on a daily
basis.
INTERFERENTS - substances which affect the analysis for the element of interest.
INTERNAL STANDARDS - in-house compounds added at a known concentration.
LABORATORY - synonymous with Contractor as used herein.
LABORATORY CONTROL SAMPLE (LCS) - a control sample of known composition. Aqueous
and solid 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 the ICP
analytical curve remains linear.
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MATRIX - the predominant material of which the sample to be analyzed is
composed. For the purpose of this SOW, a sample matrix is either water or
soil/sediment. Matrix is not synonymous with phase (liquid or solid).
MATRIX MODIFIER - salts used in AA to lessen the effects of chemical
interferents, viscosity, and surface tension.
MATRIX SPIKE - aliquot of a sample (water or soil) fortified (spiked) with known
quantities of specific compounds and subjected to the entire analytical procedure
in order to indicate the appropriateness of the method for the matrix by
measuring recovery.
METHOD OF STANDARD ADDITIONS (MSA) - the addition of 3 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 effects; it will not counteract spectral effects. Also
referred to as Standard Addition.
PERCENT SOLIDS - the proportion of solid in a soil sample determined by drying
an aliquot of the sample.
PERFORMANCE EVALUATION (PE) SAMPLE - a sample of known composition provided by
EPA for Contractor analysis. Used by EPA to evaluate Contractor performance.
POST-DIGESTION SPIKE - the addition of a known amount of standard after
digestion.
PREPARATION BLANK (reagent blank, method blank) - an analytical control that
contains distilled, deionized water and reagents, which is carried through the
entire analytical procedure (digested and analyzed). An aqueous method blank is
treated with the same reagents as a sample with a water matrix; a solid method
blank is treated with the same reagents as a soil sample.
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).
QUALITY CONTROL SAMPLE - a solution obtained from an outside source having known
concentration values to be used to verify the calibration standards.
REAGENT BLANK - a volume of deionized, distilled water containing the same acid
matrix as the calibration standards carried through the entire analytical scheme.
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 off 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 off to 11.45.
G-5 ILM04.0
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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 an example, 11.435 is rounded off to 11.44,
while 11.425 is rounded off 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 14 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 14-day calendar period during which samples in a Case are
received, beginning with receipt of the first sample in the Case or
SDG (seven calendar day period for 14-day data turnaround
contracts).
Samples may be assigned to Sample Delivery Groups by matrix (i.e., all
soils in one SDG, all waters in another), at the discretion of the laboratory.
SAMPLE NUMBER (EPA SAMPLE NUMBER) - a unique identification number
designated by EPA for each sample. The EPA Sample Number appears on the sample
Traffic Report which documents information on that sample.
SENSITIVITY - the slope of the analytical curve, i.e., functional relationship
between emission intensity and concentration.
SERIAL DILUTION - the dilution of a. sample by a factor of five. 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.
SOIL - synonymous with soil/sediment or sediment as used herein.
STOCK SOLUTION - a standard solution which can be diluted to derive other
standards.
SUSPENDED - those elements which are retained by a 0.45 um membrane filter.
TOTAL METALS - analyte elements which have been digested prior to analysis.
G-6 ILM04.0
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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.
VALIDATED TIME OF SAMPLE RECEIPT (VTSR) - 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.
WET WEIGHT - the weight of a sample aliquot including moisture (undried).
10% 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.
G-7 ILM04.0
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EXHIBIT H
DATA DICTIONARY AND FORMAT FOR DATA
DELIVERABLES IN COMPUTER-READABLE FORMAT
H-l ILM04.0
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AGENCY STANDARD IMPLEMENTATION FOR INORGANICS ILM04.0
1. Format Characteristics
1.1 This constitutes an implementation of the EPA Agency Standard for
Electronic Data Transmission based upon analytical results and ancillary
information required by the contract. All data generated by a single
analysis are grouped together, and the groups are aggregated to produce
files that report data from an SDG. Because this implementation is only
a subset of the Agency Standard, some fields have been replaced by
delimiters as place holders for non-CLP data elements.
1.2 This implementation includes detailed specifications for the required
format of each record. The position in the record where each field is
to be contained relevant to other fields is specified, as well as the
maximum length of the field. Each field's required contents are
specified as literal (contained in quotes), which must appear exactly as
shown (without quotes), or as a variable for which format and/or
descriptions are listed in the format/contents column. Options and
examples are listed for most fields. For fields where more than three
options are available, a list and description of options are supplied
following the record descriptions. Fields are separated from each other
by the delimiter "j" (ASCII 124). Fields that do not contain data
should be zero length with the delimiter as place holder.
1.3 Numeric fields may contain numeric digits, a decimal place, and a
leading minus sign. A positive sign is assumed if no negative sign is
entered in a numeric field and must not be entered into any numeric
field.
Requirements for significant figures and number of decimal places are
specified in Exhibit B. The numeric field lengths are specified such
that all possible numeric values can be written to the file. The size
of the numeric field indicates the maximum number of digits, decimal,
and negative sign, if appropriate, that can appear in the field at the
same time. Therefore, the number reported may need to be rounded (using
EPA Rounding Rules) to fit into the field. The rounding must maintain
the greatest significance possible providing the field length
limitation. In addition, the rounded number that appears on the form,
and therefore the field in the diskette file, must be used in any
calculation that may result in other numbers reported on the same form
or other forms in the SDG. Field lengths should only be as long as
necessary to contain the data; packing with blanks is not allowed.
2. Record Types
2.1 The Agency Standard consists of variable length ASCII records. Maximum
field length specifications match the reporting requirements in Exhibit
B. The last two bytes of each record must contain "carriage return" and
"line feed", respectively.
2.2 There are four groups of record types in the reporting format, as shown
in this section. Detailed record formats follow.
H-2 ILM04.0
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Type Type ID Contents
Run Header 10 Information pertinent to a group of samples
processed in a continuous sequence; usually
several per SDG
Sample Header 20 Sample identifying, qualifying, and linking
information
Results Record 30 Analyte results and qualifications
Comments Record 90 Free form comments
2.3 All record types given are mandatory. Type 10, representing the
analytical run, contains the instrument and run IDs which act as an
identifying label for the run. All 10, 20, 30, and 90 series records
following that record pertain to the same analytical run. Type 20,
representing the sample, contains the EPA Sample ID which acts as an
identifying label for the sample. The QC code indicates whether the
data is from an environmental sample, calibration, or QC sample. All
20, 30, and 90 series records following that record pertain to the same
sample. Type 30, representing an individual analyte, contains an
identifier to identify the analyte. All 30 series records following
that record pertain to the same analyte.
3. Production Runs
A production run represents a "group" or "batch" of samples that are
processed in a continuous sequence under relatively stable conditions.
Specifically:
Calibration - All samples in a run use the same initial calibration
data.
Method - Constant.
Instrument conditions - Constant throughout a run. Results obtained on
different instruments cannot be combined in one run.
Thus, each separate group of analyses on each instrument will consist of
a separate production run, and must be reported in a separate file.
The run numbers in an SDG must be unique; that is, there shall only be
one Run Number "1", only one Run Number "2", etc. in an SDG.
In addition, later runs within a method for an analyte shall have a
higher run number than earlier ones. For example, if arsenic is
quantitated by the GFAA method on 01/01/94 beginning at 12:02 and
arsenic is later quantitated by the GFAA method on 01/01/94 beginning at
18:06, then the run beginning at 12:02 shall have a lower run number
than the run beginning at 18:06.
Example of the Sequence of Record Types in a Production Run
10 Contains run header information. Occurs once per run.
16 Contains additional run header information. Occurs once per run.
H-3 ILM04.0
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20 Acts as a header for the following instrument parameter
information. Occurs once per run with EPA Sample Number equal to
"IDL". Analysis year, analysis month, analysis day equal the
year, month and day the IDLs were computed. Analyte count equals
the number of the type 30 records that follow.
30 Contains only the Analyte CAS Number, IDL Label and
IDL. Occurs once for each analyte used in the run.
30
30
30
20 Acts as a header for the following instrument parameter
information. Occurs once per run with EPA Sample Number equal to
"LRV". Analysis year, analysis month, analysis day equal the
year, month and day the linear ranges were computed. Analyte
count equals the number of type 30, 32 and 34 groups that follow.
30 Contains only the Analyte CAS Number and the Analyte
Identifier. Occurs once for each analyte used in the
run.
32 Contains integration time information for the
preceding analyte on the type 30 record.
34 Contains the CRDL and Linear Range information for the
preceding analyte on the type 30 record. There are as
many consecutive type 34 records as there are
different wavelengths used for the analyte identified
on preceding type 30.
30
32
34
20 Acts as a header for the following instrument parameter
information. Occurs once per run with EPA Sample Number equal to
"BCD". Analysis year, analysis month, analysis day equal the
year, month and day the background correction factors were
computed. Analyte count equals the number of the type 30 and 35
groups that follow.
30 Contains only the Analyte CAS Number. Occurs once for
each analyte used in the run.
35 Contains the background and interelement correction
information for the preceding analyte on the type 30
record. There are as many consecutive type 35 records
as there are interelement correction factors for the
analyte identified on preceding type 30.
H-4 ILM04.0
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30
35
20 Contains header information for sample and QC data.
21 Contains additional information for analytical and instrument QC
samples. Will always be preceded by a type 20 record.
22 Contains additional information for analytical samples. Will
usually follow type 21 record.
30 Contains the sample level concentration, true or added
value and QC value for each analyte. Occurs once for
each analytical result for the EPA Sample Number of
the previous type 20 record.
31 Reports any instrumental data necessary to obtain the
result reported on the previous type 30 record. Will
always be preceded by a type 30 record. Occurs once
per type 30 record.
30 Values for the next analyte wavelength being measured.
31 Values for the next analyte wavelength being measured.
30
31
Type 30-31 record sequence continues as many times as the value of
the ANALYTE COUNT on the previous type 20 record.
20 Next Sample Header record - The following applies to the next
sample data.
21
22
30
31
30
31 etc.
20
21
22
30
H-5 ILM04.0
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31 etc.
4. Record Sequence
4.1 A Run Header (type 10) record must be present as the first record in the
file (run). Further occurrences of the type 10 record in the file are
not allowed.
A type 16 record must immediately follow the type 10 record. Further
occurrences of the type 16 record in the file are not allowed.
The first three type 20 records are headers for the run-wide instrument
parameters.
The first type 20 record (followed by type 30 record[s] only) is a
header for the quarterly determined and other instrument detection limit
values (IDL) and must immediately follow the type 16 record.
The second type 20 record (of the type 30, 32, 34 group) Ls a. header for
the linear range values (LRV) and must immediately follow the last type
30 record that pertains to the instrument detection limit values. The
linear range values for all methods except the ICP method are the
analytically determined concentrations of the highest instrument
calibration standards that are used in the generation of the calibration
curve at the beginning of every run. The linear range values for the
ICP method are the quarterly determined values that are reported on Form
XII of the hardcopy.
The third type 20 record is a header for the ICP and GFAA background
correction data (BCD) and must immediately follow the last type 34
record that pertains to the linear range values. This third type 20
record (of the type 30, 35 group) is not required for methods AV, CV,
CA, AS and C (that is, mercury and cyanide analyses).
These are the only occurrences of the type 20 records that do not relate
to actual analyses in the run I Therefore, the only fields that are not
blank in these occurrences of the type 20 record are the RECORD TYPE
("20"); EPA SAMPLE NUMBER ("IDL", "LRV" and "BCD"); Analysis Year/Year
Computed, Analysis Month/Month Computed, Analysis Day/Day Computed
("YY", "MM", "DD"); and ANALYTE COUNT.
A minimum of one type 30 record must immediately follow the first type
20 record, and the total number of type 30 records must be equivalent to
the ANALYTE COUNT on this type 20 record.
A minimum of one group of type 30, 32 and 34 records must immediately
follow the second type 20 record. The information in each group must
pertain to one and only one analyte. The number of groups must be
equivalent to the ANALYTE COUNT on the second type 20 record.
A minimum of one group of type 30 and 35 records must immediately follow
the third type 20 record for background correction data (if required).
The information in each group must pertain to one and only one analyte.
The number of groups must be equivalent to the ANALYTE COUNT on the
third type 20 record.
H-6 ILM04.0
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The type 20 record that relates to the analysis of the first instrument
calibration standard must immediately follow the last type 30, 35 group
for methods ICP and GFAA, or the last type 30, 32, 34 group for the
methods for mercury and cyanide analyses. After the appearance of this
type 20 record in the file, further occurrences of the type 32, 34 and
35 records in that file are not allowed.
4.2 Each environmental sample, calibration, or quality control sample is
represented by a group composed of type 20, 21, and 22 records, which
hold sample level identifying information, followed by a minimum of one
group composed of type 30 and 31 records for each analyte's wavelength.
The type 20 record holds a count for the number of analyte wavelengths
being used to determine results. The ANALYTE COUNTER must have a value
equivalent to the number of type 30 groups associated with each type 20
record.
Except for the first three type 20 records for methods ICP and GFAA, and
the first two type 20 records for the methods for mercury and cyanide
analyses, all type 20 records should occur in the order of sample
analysis.
4.3 Type 90 comment records may be defined to occupy any position except
before the type 10 (header) record. Comments pertaining to the whole
run such as ones on Cover Page must appear before the first type 20
record. Comments pertaining to a particular sample such as ones on
Form I must appear after the type 20 record for that sample, but before
the first type 30 record associated with that sample. Comments
pertaining to a particular analyte or wavelength must appear after the
type 30 record of that wavelength, but before the type 30 record of the
following wavelength.
4.4 The type 92 record which contains the sample associated data that is
reported at the bottom of Form I must appear anywhere after the type 22
record for that EPA FIELD SAMPLE, but before the type 20 record of the
next sample.
H-7 ILM04.0
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5. File/Record Integrity
All record types must contain the following check fields to ensure file
and record integrity:
Record
Position
Field
Length Contents
Remarks
First Field
Record type or identifier "10" or as appropriate
Last Field
Record sequence number
Record checksum
Contains CR and LF
00000-99999, repeated as
necessary
Four hexadecimal
digits1
6. Dates and Times
Date or time-of-day information consists of successive groups of two
decimal digits, each separated by delimiters. Dates are given in the
order YY MM DD, and times as HH MM. All hours must be given as 00 to 23
using a 24 hour clock and must be local time.
1 - Multiplejyglume Data
There is no requirement under this format that all the data from an
entire SDG fit onto a single diskette. However, each single production
run must fit onto a single diskette if possible. If that is not
possible, then it is necessary that all files start with a type 10
record, and that the multiple type 10 records for each file of the same
production run be identical. Information for a single sample may not
be split between files.
8. Deliverable
8.1 The file or files must be submitted on a 5-1/4 inch floppy diskette,
which may be either a double-sided, double-density, 360 K-byte or a high
capacity 1.2 M-byte, or 3.5 inch double-sided, double-density 720 K-byte
or 1.44 M-byte, diskette. The diskette must be formatted and recorded
using the MS-DOS Operating System. The diskette or diskettes must
contain all information relevant to one and only one SDG, and must
accompany the hardcopy package for the SDG submitted to the Sample
Management Office (see Exhibit B). Information on the diskette or
diskettes must correspond exactly with information submitted in the
hardcopy data package and on the hardcopy data package forms. Blank or
unused records should not be included on the diskettes.
checksum is defined to be the sum of the ASCII representation of the
data on the record up to the Record Sequence Number plus the checksum of the
previous record. The sum is taken modulo 65536 (216) and represented as four (4)
hexadecimal digits.
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8.2 Each diskette must be identified with an external label containing (in
this order) the following information:
Disk Density
File Name(s)
Laboratory Name (optional)
Laboratory Code
Case Number (where applicable)
SAS Number (where applicable)
Contract Number
The format for the File Name(s) must be XXXXXX.I01 to XXXXXX.I99
where XXXXXX is the SDG identifier, I designates inorganics, and
01 through 99 the file number.
Dimensions of the label must be in the range 4-3/4" to 5" long by 1 1/4"
to 1 1/2" wide for 5 1/4 inch floppy diskette; and 2" to 2 1/4" long by
2 1/8" to 2 3/8" wide for 3.5 inch IBM-compatible diskette.
H-9 ILM04.0
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9.
Record Listing
Following is a listing of every record type required to report data from
a single SDG.
FORMAT OF THE PRODUCTION RUN FIRST HEADER RECORD (TYPE 10)
MAXIMUM
LENGTH
2
1
2
1
2
1
2
1
2
1
2
1
5
1
8
1
3
1
6
4
11
1
10
2
25
1
2
1
5
4
CONTENTS
RECORD TYPE
Delimiter
ANALYSIS START YEAR
Delimiter
ANALYSIS START MONTH
Delimiter
ANALYSIS START DAY
Delimiter
ANALYSIS START HOUR
Delimiter
ANALYSIS START MINUTE
Delimiter
METHOD TYPE
Delimiter
METHOD NUMBER
Delimiter
MANAGER'S INITIALS
Delimiter
LAB CODE
Delimiter
CONTRACT NUMBER
Delimiter
INSTRUMENT ID
Delimiter
LABORATORY NAME
Delimiter
RUN NUMBER
Delimiter
RECORD SEQUENCE NUMBER
CHECKSUM
FORMAT/CONTENTS
"10'
i
i
YY
i
MM
i
t
DD
i
i
HH
i
i
MM
i
i
CHARACTER"
"ILM04.0" (SOW)
CHARACTER
CHARACTER
i i i i
i i i i
CHARACTER
i
i
CHARACTER
i i
i i
CHARACTER
NUMERIC0
i
i
NUMERIC
CHARACTER
^Method Types are
"P" for ICP
"A" for Flame AA
"F" for Furnace AA
"PM" for ICP when Microwave Digestion is used
"AM" for Flame AA when Microwave Digestion is used
"FM" for Furnace AA when Microwave Digestion is used
"CV" for Manual Cold Vapor AA
"AV" for Automated Cold Vapor AA
"CA" for Midi-Distillation Spectrophotometric
"AS" for Semi-Automated Spectrophotometric
"C" for Manual Spectrophotometric
"T" for Titrimetric
3Run number values are 01 through 99. Each production run will be assigned
a unique Run Number. Run Numbers are to be assigned sequentially beginning with
01 and will equal the number of production runs.
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FORMAT OF THE PRODUCTION RUN SECOND HEADER RECORD (TYPE 16)
MAXIMUM
LENGTH
CONTENTS
FORMAT/CONTENTS
2
1
2
1
2
1
2
1
2
1
2
1
1
1
1
1
1
1
1
1
5
4
RECORD TYPE
Delimiter
ANALYSIS END YEAR
Delimiter
ANALYSIS END MONTH
Delimiter
ANALYSIS END DAY
Delimiter
ANALYSIS END HOUR
Delimiter
ANALYSIS END MINUTE
Delimiter
AUTO-SAMPLER USED
Delimiter
INTERELEMENT CORRECTIONS APPLIED
Delimiter
BACKGROUND CORRECTIONS APPLIED
Delimiter
RAW DATA GENERATED
Delimiter
RECORD SEQUENCE NUMBER
CHECKSUM
"16'
YY
i
i
MM
i
i
DD
i
i
HH
i
MM
i
"Y" or "N"
Y" or "N"5
•Y" or "N
..5
Y" or "N" or "
NUMERIC
CHARACTER
4Enter "Y" if an auto-sampler is used with equal time and intervals between
analysis.
These are the answers to the first two questions on the Cover Page. "Y"
equals "YES", and "N" equals "NO".
°This is the answer to the third question on the Cover Page. "Y" equals
"YES", "B" equals BLANK and "N" equals "NO".
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FORMAT FOR THE MANDATORY SAMPLE HEADER DATA RECORD (TYPE 201
MAXIMUM
LENGTH
CONTENTS
FORMAT/CONTENTS
2
1
2
1
12
1
5
1
3
1
3
1
5
1
6
1
2
1
2
1
2
1
2
1
2
2
2
1
5
1
3
1
5
4
RECORD TYPE
Delimiter
REGION
Delimiter
EPA SAMPLE NUMBER
Delimiter
MATRIX
Delimiter
QC CODE
Delimiter
SAMPLE QUALIFIER
Delimiter
CASE NUMBER
Delimiter
SDG NUMBER
Delimiter
ANALYSIS YEAR/YEAR COMPUTED
Delimiter
ANALYSIS MONTH/MONTH COMPUTED
Delimiter
ANALYSIS DAY/DAY COMPUTED
Delimiter
ANALYSIS HOUR
Delimiter
ANALYSIS MINUTE
Delimiter
SAMPLE WT/VOL UNITS
Delimiter
SAMPLE WT/VOL
Delimiter
ANALYTE COUNT
Delimiter
RECORD SEQUENCE NUMBER
CHECKSUM
"20"
i
NUMERIC
CHARACTER'
CHARACTER*
i
i
CHARACTER
i
CHARACTER5
i
CHARACTER
CHARACTER
i
YY
i
MM
DD
i
i
HH
i
i
MM
I
I
NUMERIC
11
NUMERIC
i
NUMERIC
CHARACTER
7EPA Sample Number as appears on Form XIV except for the first three type
20 records. The first type 20 record must have an EPA Sample Number of "IDL";
the second, an EPA sample number of "LRV"; the third, an EPA sample number of
"BCD".
8For matrix, "1" equals "WATER", and "F" equals "SOIL".
9"REJ" sample qualifier is for the unacceptable (one of the two) MSA
results; this sample qualifier appears on the type 20 record containing the zero
(0) addition EPA Sample Number (XXXXXXO) .
10..Q,,
grams, and "ML" equals milliliters.
11This is the size of the sample at the beginning of the digestion
procedure.
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SAMPLE QC CODES LISTING FOR TYPE 20
NOTE: These QC codes appear in the QC code fields on type 20 records. They
are used to indicate the type of data that is being reported.
2CC
LCB
LIB
Name
LRB LABORATORY (REAGENT)
BLANK
LABORATORY CALIBRATION
BLANK
Definition
The Preparation or Method Blank
(See Exhibit G).
The Continuing Calibration Blank (CCB)
(See Exhibit G).
LABORATORY INITIAL BLANK The Initial Calibration Blank (ICB)
(See Exhibit G).
LCM LABORATORY CONTROL
SOLUTION
The Laboratory Control Sample (LCS)
(See Exhibit G).
LD1 LABORATORY DUPLICATE
FIRST MEMBER
LD2 LABORATORY DUPLICATE
SECOND MEMBER
This is the same as the Sample Result "(S)"
that is reported on the Duplicate Form of
hardcopy (Form VI).
This is the second aliquot and is identified
as "D" on the Duplicate Form of hardcopy
(Form VI).
LVM LABORATORY CALIBRATION
VERIFICATION SOLUTION
LVC LABORATORY CONTINUING
CALIBRATION VERIFICATION
These values are identified as "Initial
Calibration Verification" (ICV) on Form II
(Part 1).
These values are identified as "Continuing
Calibration Verification" (CCV) on Form II
(Part 1).
LSO LABORATORY SPIKED SAMPLE These values are identified as "Sample Result
BACKGROUND (ORIGINAL) (SR)" on the "Spike Sample Recovery" Form of
VALUES hardcopy (Form V (Part 1)).
LSF LABORATORY SPIKED SAMPLE- These are the "Spiked Sample Result (SSR)"
FINAL VALUES values on the "Spike Sample Recovery" Form of
hardcopy (Form V (Part 1)).
LDO
LDF
LABORATORY DILUTED SAMPLE These values are the "Initial Sample Result
BACKGROUND (I)" values on the "Serial Dilution" Form of
(ORIGINAL) VALUES hardcopy (Form IX).
LABORATORY DILUTED
SAMPLE - FINAL VALUES
These are the "Serial Dilution Result(S)"
values on the "Serial Dilution" Form of
hardcopy (Form IX).
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SAMPLE PC CODES LISTING FOR TYPE 20
Name
Definition
MSO STANDARD ADDITION
RESULTS ORIGINAL VALUE
This value is identified as "0 ADD"
on "Standard Addition Results", Form VIII.
MSI STANDARD ADDITION
RESULTS FIRST
ADDITION
This value is identified as "1 ADD"
on "Standard Addition Results", Form VIII.
MS2 STANDARD ADDITION
RESULTS SECOND
ADDITION
MS3 STANDARD ADDITION
RESULTS THIRD
ADDITION
This value is identified as "2 ADD"
on "Standard Addition Results", Form VIII.
This value is identified as "3 ADD"
on "Standard Addition Results", Form VIII.
PDO POST-DIGESTION SPIKE
BACKGROUND (ORIGINAL)
VALUES
PDF POST-DIGESTION
SPIKE BACKGROUND
(FINAL) VALUES
This value is identified as "Sample Result'
(SR) on the "Post Digest Spike Sample
Recovery", Form V (Part 2).
This value is identified as "Spiked Sample
Result" (SSR) on the "Post Digest Spike
Sample Recovery", Form V (Part 2).
LPC CRDL STANDARD
LII LABORATORY INTERFERENCE
CHECK SOLUTION (INITIAL)
LIF LABORATORY INTERFERENCE
CHECK SOLUTION (FINAL)
Laboratory Performance Check Solution for
ICP (CRI) and Graphite Furnace (CRA).
The results of this solution analysis are
reported on the "interference Check Sample"
(ICS), Form IV.
The results of this solution analysis are
reported on the "Interference Check Sample"
(ICS), Form IV.
FRB FIELD BLANK
This is any sample that is submitted from
the field and is identified as a blank. This
includes trip blanks, rinsates, eguipment
blanks, etc.
H-14
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FORMAT OF THE SAMPLE HEADER RECORD (TYPE 21)
MAXIMUM
2
2
3
3
6
1
14
1
2
1
2
1
2
2
2
1
2
1
2
1
9
1
8
1
2
1
5
4
CONTENTS
RECORD TYPE
Delimiter
LEVEL
Delimiter
SAS NUMBER
Delimiter
LAB SAMPLE ID
Delimiter
PREPARATION YEAR
Delimiter
PREPARATION MONTH
Delimiter
PREPARATION DAY
Delimiter
YEAR RECEIVED
Delimiter
MONTH RECEIVED
Delimiter
DAY RECEIVED
Delimiter
SOLUTION SOURCE
Delimiter
INJECTION/ALIQUOT VOLUME
Delimiter
PREPARATION START HOUR
Delimiter
RECORD SEQUENCE NUMBER
CHECKSUM
FORMAT/CONTENTS
'21'
i i
i i
"LOW"/"MED"
i i i
i i i
CHARACTER
i
CHARACTER
i
YY
i
MM
i
i
DD
i i
i i
YY
i
i
MM
i
i
DD
i
i
CHARACTER
i
i
NUMERIC
i
i
12
13
14
HH
i
i
NUMERIC
CHARACTER
This is the source of the solutions that is reported on Forms IIA, IIB,
IV and VII of the hardcopy (ICV, CCV, CRI, CRA, ICS, and LCS).
13This is the portion of the sample that is injected into the instrument
excitation system for the purpose of measuring the absorbance, emission or
concentration of an analyte.
It is used to
is the hour at which the preparation is started.
differentiate between different batches on the same day.
H-15
ILM04.0
-------
FORMAT OF THE ASSOCIATED INJECTION AND COUNTER RECORD (TYPE 22V
MAXIMUM
LENGTH CONTENTS FORMAT/CONTENTS
2 RECORD TYPE "22"
10 Delimiter ! ! ! ! ! ! ! ! ! !
8 FINAL VOLUME NUMERIC15
1 Delimiter j
8 DILUTION FACTOR NUMERIC
3 Delimiter j i{
5 PERCENT SOLIDS NUMERIC
1 Delimiter |
5 RECORD SEQUENCE NUMBER NUMERIC
4 CHECKSUM CHARACTER
15This is the final volume that is currently reported on Form XIII of the
hardcopy.
H-16 ILM04.0
-------
FORMAT OF THE RESULTS DATA RECORD (TYPE 30)
MAXIMUM
LENGTH
CONTENTS
FORMAT/CONTENTS
2
1
1
1
9
2
5
1
3
1
15
1
1
1
10
1
1
1
10
1
1
1
10
1
1
1
10
1
1
1
10
1
10
1
1
1
1
1
10
1
1
1
10
1
1
1
10
1
1
1
5
4
RECORD TYPE
Delimiter
ANALYTE IDENTIFIER
Delimiter
ANALYTE CAS NUMBER
Delimiter
CONCENTRATION UNITS
Delimiter
CONCENTRATION QUALIFIER
Delimiter
CONCENTRATION
Delimiter
VALUE DESCRIPTOR
Delimiter
AMOUNT ADDED OR TRUE VALUE
Delimiter
QC VALUE DESCRIPTOR, P
Delimiter
QC VALUE
Delimiter
QC VALUE DESCRIPTOR, C
Delimiter
QC VALUE
Delimiter
QC VALUE DESCRIPTOR, L
Delimiter
QC VALUE
Delimiter
MATRIX SPIKE QC LIMIT QUALIFIER
Delimiter
QC LOWER LIMIT
Delimiter
QC UPPER LIMIT
Delimiter
QC LIMIT QUALIFIER
Delimiter
IDL LABEL
Delimiter
IDL
Delimiter
RAW DATA AVERAGE QUALIFIER
Delimiter
RAW DATA AVERAGE
Delimiter
RAW DATA %RSD QUALIFIER
Delimiter
RAW DATA %RSD
Delimiter
"MSA-TREE" QUALIFIER
Delimiter
RECORD SEQUENCE NO.
CHECKSUM
301
11C " /f< T "
I
I
CHARACTER
"UG/L"/"MG/KG"
17
CHARACTER
NUMERIC18'19'20
*' ? /
" **"
NUMERIC
i
it p it 2 2
i
i
NUMERIC
' 22
" O "
NUMERIC
.,Lt,22
i
i
NUMERIC
ii 2 3
I
I
NUMERIC
i
i
NUMERIC
i
,24
24
r"/"E
,.25
"U"
NUMERIC
,26
I
•U"/"B"/"L"27
NUMERIC
28
"M"/BLANK29
i
i
NUMERIC
i
"+"/"E"/"W"/BLANK30
i
i
NUMERIC
CHARACTER
H-17
ILM04.0
-------
FORMAT OF THE RESULTS DATA RECORD (TYPE 30) FOOTNOTES
16 ,,c,, ^CAS Registry Number) is used for all analytes except cyanide. "I"
is used for cyanide.
17 "BDL" means below detection limit.
"NSQ" means there is not sufficient quantity to analyze sample according
to the protocol.
"NAI" not analyzed due to interference, "NAR" no analysis result
required.
"LTC" means less than the CRDL but greater than or equal to the IDL.
"FQC" means failed quality control criteria.
"GTL" means greater than the linear range.
"RIN" means that the analysis result was not used to report data in the
SDG. The results are reported from a later reanalysis of the same
sample aliquot.
"REX" means that the analysis result was not used to report data in the
SDG. The results are reported from a later reanalysis of a
repreparation of the same sample.
Note that, except for "NAR", none of these codes relieves the Contractor
from reporting a valid result. They only explain why or if the result
is qualified.
° The GFAA analytical or post-digestion spike sample result (SSR) must
always be reported in ug/L; do not convert from ug/L to mg/Kg for soil
samples. In addition, the GFAA post-digestion SSR shall not be
corrected for dilutions.
19 EPA FIELD SAMPLES (Form I equivalents) that do not have QC codes shall
have their analytes1 results reported to four decimal places. Also,
results for samples that carry the QC codes MSO and FRB shall be
reported to four decimal places.
•y n
Follow the instructions for the reporting of data in Exhibit B in
reporting results for samples with QC codes. For example, the LD2 QC
code sample results shall be reported to four decimal places because the
duplicate result on Form VI has to be reported to four decimal places.
Refer to pages H-13 and H-14 for QC codes and definitions.
21 ,,T,, stands for a true value of the solution. This includes the
concentration of all (ICP as well) instrument calibration standards.
"F" stands for an added concentration to a sample such as a pre- or
post-digestion spike, or MSA additions.
22 i.p,. eguais percent recovery (%R), percent difference (%D), or relative
percent difference (RPD), "C" equals MSA correlation coefficient, and
"L" equals control limit for duplicates. For GFAA analysis, the EPA
duplicate sample number with the "D" suffix should contain the RPD
value, and the EPA duplicate sample number with the "DA" suffix should
contain the post-digestion spike sample %R value.
H-18 ILM04.0
-------
23 .,N., is the qualifier that is used on Form V (Part 1) of the hardcopy to
indicate that the matrix or pre-digestion spike sample recovery for an
analyte is not within the specified control limits.
24 These are the limits for the spike sample recovery (Form VA), the
ICV/CCV (Form IIA), the CRA/CRI (Form IIB), the ICSAB (Form IV), the LCS
(Form VII), and the GFAA post-digestion spike recovery.
25 11*1, ^g tne qualifier that is used on Form VI of the hardcopy to indicate
that the duplicate sample analysis for an analyte is out of control, and
"E" is the qualifier that is used on Form IX of the hardcopy to indicate
that the ICP serial dilution analysis results are estimated because of
the existence of significant physical or chemical interferences. The
"*" qualifier should be entered on the type 30 record of the EPA sample
number with the "D" suffix; that is, on either the LD2 or MSO (when
duplicate result is quantitated by MSA) QC code type 30 record.
26 The IDL must be reported to one decimal place.
27 "U" means less than the IDL, "B" means less than the CRDL and greater
than or equal to the IDL, "L" means greater than the linear range.
28 The average value of the replicate injections or exposures are reported
in this field. The average values for mercury and cyanide analyses are
also reported in this field.
Exception: For MSA analysis, the single injection absorbance values are
reported only in the "First Instrument Value" field of the type 31
record; do not report raw data average values for the single injection
MSAs in the "Raw Data Average" field of the type 30 record. The "Raw
Data Average" field of MSO QC code shall contain the value of the MSA
minus x-intercept; this value is also reported in the "Final Cone."
column of Form VIII of the hardcopy.
29 -M" is the qualifier that is used to indicate that the replicate
injection readings of the GFAA sample analysis do not agree within 20%
relative standard deviation (RSD) or coefficient of variation (CV) for
analytical samples.
30 ,, + 1, indicates that the MSA correlation coefficient is less than 0.995,
"E" indicates that the GFAA post-digestion spike sample recovery (after
dilution) is less than 40%, and "W" indicates that the GFAA post-
digestion spike recovery is not within the recovery limits of 85-115%
when three times the sample result is less than the spike sample result.
H-19 ILM04.0
-------
FORMAT FOR THE INSTRUMENTAL DATA READOUT (TYPE 31)
MAXIMUM
LENC
2
1
1
1
1
2
8
1
10
2
10
2
10
2
10
2
10
1
5
4
CONTENTS
RECORD TYPE
Delimiter
TYPE OF DATA
Delimiter
TYPE OF VALUE
Delimiter
ANALYTE WAVELENGTH
Delimiter
FIRST INSTRUMENT VALUE
Delimiter
SECOND INSTRUMENT VALUE
Delimiter
THIRD INSTRUMENT VALUE
Delimiter
FOURTH INSTRUMENT VALUE
Delimiter
FIFTH INSTRUMENT VALUE
Delimiter
RECORD SEQUENCE NUMBER
CHECKSUM
FORMAT/CONTENTS
•31'
"W
,31
32
CHARACTER
NUMERIC (TO 2 DECIMAL PLACES)
NUMERIC33'34
NUMERIC
33
i i
i i
NUMERIC
33
33
33
NUMERIC
i i
i i
NUMERIC
i
i
NUMERIC
CHARACTER
" equals wavelength.
32"
C" equals concentration in ug/L, "T" equals concentration in ug/250 ml,
"F" equals concentration in ug/50 ml, "B" equals absorbance, "I" equals
intensity, "A" equals peak area in cm square, and "H" equals peak height in cm.
This is used to report data for method analyses that require replicate
injections or exposures. If a single instrument measurement is used, then enter
it in the first instrument value field, and leave the other four fields empty.
If two instrument measurements are used, then enter them in the first and second
instrument value fields in the order of their analyses, and leave the other three
fields empty; etc.
^GFAA MSA analyses are single injections only. The EPA samples have the
suffixes 0, 1, 2, and 3 (MAX123DO, MAX123D1, MAX123D2, MAX123D3), and their
respective QC codes are MSO, MSI, MS2, and MS3. The absorbances for the four
additions (zero, first, second, and third) shall be reported in this field, the
first instrument value field. The -(x- intercept) concentration, which is also
reported on the hardcopy of Form VIII in the "Final Cone" column, shall be
reported in the "Raw Data Average" field of the MSO QC code type 30 record.
Therefore, do not report raw data averages (in the "Raw Data Average" field) for
the MSA single injections on any of the four type 30 records. The absorbances
of all four single injections shall only be reported in their respective type 31
record "First Instrument Value" fields. The MSA final concentration corrected
for volume, sample weight, % solids, and dilution shall be reported in the
"CONCENTRATION " field of the MSO QC code type 30 record.
H-20
ILM04.0
-------
FORMAT OF THE AUXILIARY DATA RECORD (TYPE 321
MAXIMUM
LENGTH CONTENTS FORMAT/CONTENTS
2 RECORD TYPE "32"
10 Delimiter ! i ! i ! ! ! ! i !
2 INTEGRATION TIME CODE "IT"
1 Delimiter j
10 INTEGRATION TIME IN SECONDS
4 Delimiter j j j j
5 RECORD SEQUENCE NUMBER NUMERIC
4 CHECKSUM CHARACTER
H-21 ILM04.0
-------
FORMAT OF THE QC LIMIT RECORD fTYPE 341
MAXIMUM
LENGTH
CONTENTS
FORMAT/CONTENTS
2
4
8
1
10
1
10
6
5
4
RECORD TYPE
Delimiter
ANALYTE WAVELENGTH
Delimiter
CRDL
Delimiter
LINEAR RANGE VALUE
Delimiter
RECORD SEQUENCE NO.
CHECKSUM
"34"
i i i i
i i i i
NUMERIC (TO 2 DECIMAL PLACES)
NUMERIC
i
i
NUMERIC
i i i i t i
i i i i i i
NUMERIC
CHARACTER
H-22
ILM04.0
-------
FORMAT OF THE CORRECTION DATA RECORD (TYPE 35)
MAXIMUM
3TH CONTENTS FORMAT/CONTENTS
2 RECORD TYPE "35"
1 Delimiter i
3 TYPE OF CORRECTION "ICP"/"BG"35
1 Delimiter !
5 TYPE OF BACKGROUND "BS"/"BD"/1'B2"
4 Delimiter }\\\
9 CAS NUMBER OF INTERFERING ANALYTE CHARACTER
1 Delimiter i
8 ANALYTE WAVELENGTH NUMERIC (TO 2 DECIMAL PLACES)
1 Delimiter '
10 CORRECTION FACTOR NUMERIC
1 Delimiter i
5 RECORD SEQUENCE NO. NUMERIC
4 CHECKSUM CHARACTER
35"ICP" indicates interelement correction, while "BG" indicates a background
correction.
H-23 ILM04.0
-------
FORMAT OF THE COMMENT RECORD (TYPE 90)
MAXIMUM
LENGTH CONTENTS FORMAT/CONTENTS
2 RECORD TYPE "90"
1 Delimiter j
67 ANY COMMENT CHARACTER
1 Delimiter j
5 RECORD SEQUENCE NUMBER NUMERIC
4 CHECKSUM CHARACTER
H-24 ILM04.0
-------
FORMAT OF THE SAMPLE ASSOCIATED DATA RECORD (TYPE 92)
MAXIMUM
LENGTH CONTENTS FORMAT/CONTENTS
2 RECORD TYPE "92"
1 Delimiter {
9 COLOR BEFORE CHARACTER
1 Delimiter j
9 COLOR AFTER CHARACTER
1 Delimiter !
6 CLARITY BEFORE CHARACTER
1 Delimiter j
6 CLARITY AFTER CHARACTER
1 Delimiter J
6 TEXTURE CHARACTER
1 Delimiter j
3 ARTIFACTS "YES"/BLANK
1 Delimiter |
5 RECORD SEQUENCE NUMBER NUMERIC
4 CHECKSUM CHARACTER
H-25 ILM04.0
-------
APPENDIX A — FORMAT OF RECORDS FOR SPECIFIC USES
DISCLAIMER
The USEPA does not warrant or guarantee the completeness and/or accuracy of
the representative examples of record type uses provided in this appendix.
This appendix serves as an example for the usage of record types and in no way
redefines or supersedes the specifications or requirements stated in Exhibits
A through H of ILM04.0.
H-26 ILM04.0
-------
Appendix A — Format of Records for Specific Uses
Table of Contents
Section Page
1.0 ICP 28
1.1 START OF AN ICP RUN WITH RECORD TYPES 10 & 16 AND THE FIRST
THREE TYPE 20 RECORDS 28
1.2 ICP INSTRUMENT CALIBRATION STANDARDS, SO AND S 29
1.3 SPIKE SAMPLE RECOVERY, DUPLICATES, AND SERIAL DILUTIONS
PERFORMED ON THE SAME SAMPLE (QC CODES LSO & LSF, LD1 & LD2,
LDO & LDF) 29
2.0 GFAA 32
2.1 START OF A GFAA RUN WITH RECORD TYPES 10 & 16 AND THE FIRST
THREE TYPE 20 RECORDS 32
2.2 INSTRUMENT CALIBRATION STANDARDS
BLANK (SO) & THREE OTHER STANDARDS 33
2.3 ANALYSIS OF A FIELD BLANK SAMPLE
SAMPLE & ITS ANALYTICAL SPIKE SAMPLE WITH QC CODE FRB .... 34
2.4 SPIKE SAMPLE RECOVERY & DUPLICATES PERFORMED ON THE SAME
SAMPLE (QC CODES LSO & LSF, AND LD1 & LD2) 34
2.5 DUPLICATES, WITH THE RESULT OF THE DUPLICATE SAMPLE
QUANTITATED BY THE MSA (QC CODES LD1, LD2, MSO, MSI, MS2,
MS3) 35
3.0 MERCURY (CVAA OR AVAA) 37
3.1 START OF A MERCURY RUN WITH RECORD TYPES 10 & 16 AND THE
FIRST TWO TYPE 20 RECORDS 37
3.2 MERCURY INSTRUMENT CALIBRATION STANDARDS
BLANK (SO) AND FOUR OTHER STANDARDS -. . . . 37
3.3 SPIKE SAMPLE RECOVERY & DUPLICATES PERFORMED ON DIFFERENT
SAMPLES (QC CODES LSO & LSF, AND LD1 & LD2) 38
3.4 SPIKE SAMPLE RECOVERY & DUPLICATES PERFORMED ON THE SAME
SAMPLE (QC CODES LSO & LSF, AND LD1 & LD2) 38
3.5 INITIAL CALIBRATION VERIFICATION (ICV) WITH LVM QC CODE ... 39
3.6 LABORATORY CONTROL SAMPLE (SOLID) WITH LCM QC CODE 39
4.0 CYANIDE (CA, AS, C, T) 40
4.1 START OF A CYANIDE RUN WITH RECORD TYPES 10 & 16 AND THE
FIRST TWO TYPE 20 RECORDS 40
4.2 CYANIDE INSTRUMENT CALIBRATION STANDARDS
BLANK (SO) AND FIVE OTHER STANDARDS 40
4.3 PREPARATION BLANK (SOIL) WITH LRB QC CODE 41
4.4 LABORATORY CONTROL SAMPLE (SOIL) WITH LCM QC CODE 41
4.5 CONTINUING CALIBRATION VERIFICATION (CCV) WITH LVC QC CODE . 41
4.6 SPIKE SAMPLE RECOVERY & DUPLICATES PERFORMED ON THE SAME
SAMPLE (QC CODES LSO & LSF, AND LD1 & LD2) 41
H-27 ILM04.0
-------
1.0 ICP
1.1 START OF AN ICP RUN WITH RECORD TYPES 10 &
20 RECORDS
16 AND THE FIRST THREE TYPE
10 i 93 i 09 ! 17 i 09 ! 06 j P j ILM04.0 | ABC! TESLAB j ', | | 68-D2-0039 j P2 |
[TEST LABS INC. j 2 1 000001879
16 1 93 i 09 i 17 i 12 ! 03 ! Y ! Y j Y ! N 1 000012114
20U1IDLJ J! 1J193107
30 1C! 7440-22-4! ! ! i i
30 !<
:,' 7429-90-5! ! i ! !
30 iCj 7440-39-3', !!!!
30 1C{ 7440-41-7} 1 1 ! |
20 1 IjLRVj ! i 1 1 193 107
30 {<
32}
34!
30j<
32j
34!
30 j(
321
34!
30 !<
32!
34!
:( 7440-22-4! ! 1 1 !
i i i i i i i i -prr. i c nn
llllllilJ.J.,3. UU
! J328.001101400C
3! 7429-90-5! ! i ! J
i i i i i i i i Trni c nn
IIIMIII-1--*-!5 •U(J
i ! 308. 20 ',200! IOC
:| 7440-39-3J HI!
!!!!!!! JITJS.OO
1 [493. 40 1200! IOC
: 17440-41-7,' ! 1 | j
i i i i i i i i TT ' R nn
1 1 1 1 1 1 1 1 •!• •!• 1 = • uu
151!!!
1 1 1 1 1 1
1 1 1 1 1 1
i 1 1 1 1 1
1 1 1 1 1 1
1 1 1 1 1 1
i 1 1 1 1 1
1 1 1 1 1 1
1 1 1 1 1 1
1 c I I 1 I
•••-> 1 1 1 1
till
1 1 1 1
iooo:
>o ill!
! ! ! !
looo:
DOOOOI j
! ! ! !
iooo:
DOOO! 1 !
! ! ! !
041000044B9D
! i JU(3.41 [Hi (000055996
i 1 1UJ22.8J 1 1 ( i (0000667D1
1 1 !U(1.0! ! ( ! ( (0000775CB
( ( ! u j o . 4 ! ! l ! ( ! oooossscs
0410002356C2
t 1 I 1 1 I 1 t 1 1 *J U\J ^ 4r O OU J.
256CDA
000267591
i i i i i i i i t i nnn^*7RO7in
\\\\\\\\\\ UUU^ /O^fUJ
288BB6
1 J0002994FB
i i t i i i i i i i nnmnaoi i
I 1 1 1 1 1 1 1 1 1 UUUJUA^J-J.
J1AB1A
{00032B436
1 ! ! 1 j j ! ! 1 J00033C149
i 00034CA52
1 [313. 0015(25000 i ( ( (00035D2DA
20|ijBCD| ji!!!93i07|oiS!!!!
^n i p ' IAACI— oo— A ' i i i i i i i i i i i i
JU,<_, / ' TA^Q— on— c, i i i i i i i i i i i i i
'1 'c*^' 3U O | | | | | | | | | | | | |
35 i ICP 1 [ j ! 1 7439-96-5 1 257 . 60
35 1 ICP 1 ! 1 1 ! 7440-62-2 1 292 . 40
30 !(
0. 0002200 J00081B6F4
1111111111 nnnR9ridi n
1 1 1 1 1 1 1 1 1 1 UUUO^^1J.U
0 . 0004900 ! 00083CE72
-0 . 0419200 ! 00084D8EF
*• ' 7/iAn— "3Q— *3 j i i t i i i i i i i i i i i i i i i i i i i i nnnR^T?fin^
- i /ttu ja j , , , | | | | , , | | , , , | , | | | , | , | , uuuesiious
35 ! ICP | 1 ! j ,' 7439-96-5 j 257 . 60 j 0 . 0000600 j 00086F060
30 1C
i 1 iA.A.r\—A'\ —1 1 1 1 1 1 1 t 1 1 1 1 1 1
-i /44U-4J.- / i i t i i i i i i i i i i
i i i i i i i i i i nnnfiTCTiT^
i i i i i i i i i |UUUH /eu /J
35 {ICP! ! i ! (7440-50-8! 324. 70 10. 0046200 10008914D1
351ICPJ ! j ! j 7439-96-5J 257. 60 j 0.0015400 { 000901F30
H-28
ILM04.0
-------
1.2 ICP INSTRUMENT CALIBRATION STANDARDS, SO AND S
1.3
20!liSO{l! ! !205961MAX123!93!09!17!09!06! j
21! i ! 1 ! {STDBj ! 1 { i 1 { {TESLAB! { J00129DD31
22 1 ! ! ! ! ! ! ! 1 ! 1 1 . oo { ! i j 00130E598
30 !C[ 7440-22-4', \ \ \ iTjO.Ol 1 j j \
31|WiIi i328.OOjO.0304! JO. 0374
30!c!7429-90-5! j 1 j ITJO.O! | j { j
31JWJI! !308.20!0.0104j {0.0136
30 1 C 1 7440-39-3 !iii|TiO.Oi!iiJ
31SWJI! 1493.401-0.0002! iO.OOOS
30 JC{ 7440-41-7! ! ! ! iT|O.Oi \\\\
31|W|Ii J313.00!0.0006! JO. 0002
20 ! 1 ! S i 1 { ! { 20596 i MAX123 1 93 j 09
i
1 1 1 iTjl 3 4 1
0.0400! ! ! !
! ! 1 iu{22.8
o.oi20!!!!
1 1 1 1 TT 1 i n 1
1 1 1 1 U | J..U|
lo.ooooi i i
1 1 1 1 TT 1 n A I
1 1 1 1 V I U«*|
0.0004! ! i !
17! 09 lllj ! 1
21! [ ! ! i ISTDII j j j \ \ \ \ TESLAB! ! 1002073CD5
22 ! ! ! I I ! ! 1 I I 1 1 • 00 1 i 1 1 00208453C
30JCJ7440-39-3J 1 { [ iTiSOOOj 1 J [
31JWJI1 j 493.40J 1.9540J {1.9610
30 i C ! 7440-41-7 j | { j { T { 1000 j j { {
31{WiI{ !313.00!0.8384! JO. 8378
30 {C{ 7440-43-9! ! ! ! iTjSOOOj j ! !
31{W{l! i 226. 50 j 1.9460J {1.9510
30 [Cl 7440-48-4! { j 1 JTJSOOO! j { i
31|Wjl! J228. 6010. 9924! JO. 9910
i i i i i n 1 1 o
1 1 1 1 | U i -L.U
1.9660! 1 ! !
i t i i i n i o A
i i r i i U i u.4
0.8440J i 1 1
1 1 1 1 1 TT 1 1 C.
I i i I i U | .L. S>
1.9684! ! 1 !
I I I I I TT 1 -| r
1 1 1 1 | U i J..3
i.ooio! j ! !
1 104100128D199
10.0359J ! ! {00131F8F5
! 001320305
! {0.0120! j ! 1001331697
{001342137
{0.0000! { { {00135348D
{ {001363EA4
10.0004{ 1 { {0013751FA
1001385C04
{04{00206314E
! [1.9603! [ ! 1002139157
J002149B6E
1 {0.8401! { { J00215ADE2
100216B7EC
i 11.9951! j 1 [00219E77D
100220F18F
1 J0.9948! i ! 1002210410
(002220E25
SPIKE SAMPLE RECOVERY, DUPLICATES, AND SERIAL DILUTIONS PERFORMED ON THE
SAME SAMPLE (QC CODES LSO Si LSF, LD1 & LD2, LDO & LDF)
20!1!MAX123!F!LSO!!20596JMAX123|93j09j17\11!09j}G\1.05|08{01568C5FD
21{{LOW{{{!S308233-01J93!09!14!{93!08}24!!18J01569D451
22', ! j ! j 1 ! ! ! !200!l.00j ! J91.5!01570DE17
90!STONES j 01571E154
92)GREY!GREY!!1MEDIUMjYES101572EA43
30JCJ7440-22-4! [MG/KG[BDL!0.7078j !!!!!!!!!!{ |U{3.4{Uj1.1600j i j j01573FD12
311WJCJJ328.00i4.2000!!0.5500i [-1.2800!|j!{0157409A5
301CJ7429-90-5! {MG/KG{NAR{ 6227. 0101 { { { ! 1 1 1 ! ! 1 1 ! |U!22.8| [29913.0000! j j
[015751DCD
31!WJC!J308.20J29992.0000! ]29654.0000{{30093.0000{{ | j{015762CAO
30iC[7440-39-3! JMG/KG1LTC!21.9349| !!!!!!!!!!! lUj1.0|B\105.3700\ \ }
[01577400C
31!W!CJ J493.40(107.2400J 1101.6400! 1107.2400! 1 1 1J015784DA6
30JC!7440-41-7! JMG/KG!LTCj0.3102i j } i j | } \ \} } \ {U|0.4jB11.4900\ \ \ J01579606A
H-29 ILM04.0
-------
31[WlCl [313.00[1.49001 |1.4900l 11.4900J1i i{015806CD9
301C1 7440-70-2! iMG/KGjNARl 682.2795 [ [ [ 1 [ i 1 1 [ 1 1 1 iUl35.7iB',
10158180EE
311W1C1, ',317.90J3289.9000', [3259.60001 [3283.10001 1 i \ {01582
30 ,'Ci 7440-43-9! jMG/KGlBDLj0.3123[ U!!!l! j 1 [UlLSiUl-O.
[01583A22B
31[W[C!1226.501-0.7600110.8300!1-0.7500J [101584AEF6
31[W[C!1226.501-0.7600110.8300J 1-0.7500
30 [C,1 7440-48-41 IMG/KGlLTCj 3.41611 ! [ ! ! 1 [
[01585C1F7
*\ + I •• * I «* I \ f\ f\ f\ r r\ \ *i A r* ~> r*r\ t I + ^ n A r\ r\ \ I ^ ^* *^ r- r\
[17
! 24
! J01584AEF6
i ! [Uj 1.5 JB! 16.4100J i j
i i J01586CFOC
Ull.81 J37.18001 1 i 101587E103
! 1 101588EE1F
111091 [G[1.05',08l016094756
1[810161055AA
1 1 !U',3.4!Ujl. 16001 1 1 101573FD12
10157409A5
11U122.81J29913.0000!1|
14001 1101.6400! 1107.2400,' j ,' 1 J015784DA6
^.v, ,^v-*+-, , [ MG/KG jLTCi 0.31021 ! [ [ i i 1 1 i 1 [ [ JU | 0.4 j B j 1.4900 i
IjWlCj 1313.OOjl.4900! ,'1.49001 J1.4900J 1 1 j J015806CD9
30 1C! 7440-70-2! 1MG/KGJLTCJ 682 .2795 { i i 1 1 ! 1 1 i 1 1 1 JUJ 35. 7 JB ,'3277
101577400C
311W1CJ 1493.401107.24001 1101.6400! 1
30 1C! 7440-41-7J j MG/KG JLTCJ 0.3102 1 ', [
31JWJC1 1313.0011.4900! ,'1.49001 !l-49
301C17440-70-2[ j MG/KG j LTC j 682.
10158180EE
J1.4900J1 1j J015806CD9
2795IIIII1IMIIIIUI35 7'B1
!101579606A
30 1C! 7440-70-2! 1MG/KGJLTCJ 682 .2795 j i i ! 1 ! 1 1 i 1 1 1 JUJ 35. 7 ,'B ,'3277. 5000
10158180EE
31JWJC! J317.9013289.90OO ,' J3259.6000J ,'3283.1000} [ [ 1 J015828F39
30',C!7440-43-9j | MG/KG [ BDL [ 0. 3123 i 1 1 ! ! 1 1 1 ! 11 i Uj 1. 5 1 U[ -0.2200 j i 1
[01583A22B
311W1C1 [226.50J-0.7600,' ,'0.8300! J-0.7500! 1 [ [01584AEF6
30JC17440-48-4! [MG/KGlLTCj3.41611 i |i i|i j! ! i \U\1.5|B|16.4100!} \
J01585C1F7
311WJC! J228.60114.73001 ,'16.7400 J17.7500,' 11[01586CFOC
lf\ls*\'-lAAr\— A **l *5 I I irs*! /-rm I I *•» "7 o r» o f I ( I I I f I I I 1 TY I 1 ft I I *s *? tor*rtllll^^r-rt*^
[01585C1F7
31|W|C! J228.60114.73001 ,'16.7400
30[Cl7440-47-3J\MG/KG[ [7.7398jj
31,'WlCj 1267.70!39.6500[ J36.8600
20[l[MAX123[F[LDOl120596[MAX123
21j[LOW!i!!S308233-01!93109!141
22[! i [ i i ! [i 120011.001i{91.5J016!
30[C[7440-22-41 !UG/L j BDL13.401!
J17.7500,' 11101586CFOC
1 1 [ ! i 1 1 1 i Ull.8! 137.1800!1 1 101587E103
',35.0200! [1101588EE1F
93 i 09117111109{{G11.05103101650C630
93 108',24! [ 18J01651D484
01652DE4A
i !
i i 1!lUl3.4iUjl.1600!1 1 101655FC98
H-30
ILM04.0
-------
31iW|G!|328.OOJ4.2000!J0.5500! j-1.28001}j j 101656092B
30 1C! 7429-90-5! JUG/L,' [29913.00! !!!!!!!!!!! JU122.8! [29913.0000! ! !
,'016571009
31JWJC1, ! 308.20[29992.0000! [29654.0000! j 30093.0000! ! i 1 [016582ADC
30[C[ 7440-39-3,1 {UG/LiLTCJ 105.37 i !!!!!!!![!! JUJ l.OjBi 105.3700} ! !
[016593DCE
311WJC!J493.40S107.2400!{101.6400!{107.2400!{{!!016604B68
J016913BCF
9600!!!J0169466BE
8!131511.0000!!!
79641
!119.6100!!!
[016968784
3l!w!d [308.20!31993.0000! ,'31313.0000! 131226.0000! i ! | {016979641
30!C[7440-39-3J iMG/KGJLTCi25.1387j \ \P113.6! ! j jj | ! | \U\1.0[Bj119.610
J01698AAC5
311WJC,'(493.401121.4600! 1118.9300!J118.43001 1 1i J01699B86C
30 ICj 7440-41-7! !MG/KG}LTCi 0.3153 ! \ [PI1.6J !!!!,','! ,'U,' 0. 4 j B\ 1. 5000 [ \ \
J01700CC13
3l!W{Ci J313.OOjl.5000', jl.5000! 11.5000! J j j 101701D86A
30 JCJ 7440-70-2! ,'MG/KGJLTC,' 676. 6709 | i !P{0.8! !!!!!!! \V\ 35.7 }B 1 3219.6
[01702ED66
— ii • ~ — it / i — — _,_.___._., | t j _ |_._-j | | | | | | | | _. | _•_._, ,_.,___
J01702ED66
SljWiCl J317.90J3256.5000J (3214.5000! ,'3187.8000! i i 1 J01703FBA7
30 \C\ 7440-43-9! JMG/KGJBDL \ 0.3153 j ',', !',!!!!!! 1 [Uj 1.5 JUj -0.9400 \ j !
1017040EA5
31|W[C[ [226.50[-0.3300[ 1-0.7400! [-1.7400! 1 ! ! ',017051896
30 1C1, 7440-48-4', jMG/KGlLTC \ 3 .8714! \ \P\12.5\ }} \ \ \ \ \ \U\ l.S\B\18.42\
J017062FB8
4200J!i
0200!!i
J017062FB8
31JWJC![228.60[19.7600!J18.7500!j16.7400}j!!1017073CD6
30!Cj7440-47-3]iMG/KGJ[10.7230! j!P]32.3!\!L!2.1j!j!*!U|1.8i(51.
J01700CC13
311WJC! ', 267.70j 50.8900 j |51.3700] [50.8000! ,' 1 j [017095D18
20 ! 1 i MAX123S ! F 1LSF ! j 20596 1MAX123 j 93 j 09 j 17 j 11 [ 14 ! ,' G! 1. 01 \ 08 \ 01730BE3(
21! JLOW!!!!S308233-03!93[09!14!!93!08l24[{J8101731CC90
22', ! ! i i i ! ! ! [200! 1.00', ', J91.5101732D656
30jCi7440-22-4!JMG/KG!j10.7212jFj10.82|P!99.1!!!!![7511251{Uj3.4!
149.54 00!!! J01733EBC7
3l!WiCJ1328.OOJ48.8400!J49.2000![50.5900![!! J01734F8DC
30JCJ7429-90-5!JMG/KGJNAR!6859.92531F!0.001 !!!!!!!!! !u!22.8l 131698.(
-------
30 JCJ 7440-70-2! iMG/KGjNAR! 775.1772 \F\ 0.00 ! !!!!,'!!!! ! U,1 35. 7 } B ! 3581.91
!J017417903
311WJC,' 1317.90J3572.0000! J3586.4000J 13587.4000! | | i J01742874B
30 1C! 7440-43-9! {MG/KG! j 10.4290JF! 10.82 JP,1 96.4j J ! j \ j75 ! 125j {U{1.5j
!48.1900!i1J017439CC6
31!W,'C! [226.50{47.5200! !48.5300j j48.5200! i i ! 101744A9DC
30!Cj7440-48-4J!MG/KG!J109.8523\F\108.21!P|98.4!!j{!{75J125!jUll.5!
j507.6000!! i J01745BFF2
31{W!C! ,'228.601505.2500| J508.2700} 1509.2800! i ! ', 101746CDA1
30 JC1, 7440-47-3! !MG/KG! \ 52 . 0002 j F | 43.28 ,' P\ 102. 3 J j | \ \ 175J125! iUil.Sj
! 240.2800! ! i '.01747E369
31{W!C!!267.70!239.3500j J240.2800!{241.20001\\\101748F10C
20J1JMAX123LJF1LDF! j 20596 [MAX123 ! 93 \ 09 \ 17 ', 11117 | j j \ 03 J017696573
21 j iLOWj ,' i JS308233-04! | j { j 93 \ 08 | 24 | j J J 017707255
22!1!!!!!!!!15.00!jJ91.5!017717B8D
30 |Cj 7440-22-4! JUG/LJ BDL! 17 .OOj ! 1 1 1 1 ! ! 1 ! ! ! iU',3.4iUi 0.6100 1 j i 1017728DDF
3l!W}C! i 328.00|1.4500| ,'-0.3800! {0.7800! { j { 1017739A7B
301CJ7429-90-5!JUG/LJ{25575.50!!|Pil4.5{!!!!!!!EJU!22.8!{5115.1000}{{
{01774AE69
31JWJC! [308.20{5038.6000!j5126.4000}{5180.3000) j j {j01775BCAC
30 JC! 7440-39-3! {UG/L{LTC{ 111.30{ i {PJ5.6! !{{{{{} {U{ 1.0 ,'B [22.2600 i \ \
J01776DOAA
31JWJC!J493.40J22.2600![22.7700!{21.7500!{j{101777DDB9
2.0 GFAA
2.1 START OF A GFAA RUN WITH RECORD TYPES 10 & 16 AND THE FIRST THREE TYPE
20 RECORDS
10j93!09!22!ll!38!FjILM04.0iABC!TESLABj!1{68-D2-0039{F2j
STEST LABS INC.I3loooooi860
16!93!09!22!l6j07iY!1 i J000011FFF
H-32 ILM04.0
-------
20|liIDL[ [j [[ |93[07[15! [[ !j J11000044A4C
301C1, 7439-92-1! i i ! i i i i! ! i i i i i!!Uj1.4||| j | J00005584F
20iliLRVl ! i i 1 ',93 109', 22! 1 1 1 1 11J0000665FC
-~^>-l-^»->q_q9_1lll||lllllllllllllllllll«
•3 y^ -J- I I I I I I I I I I I I I I I 1 I I I I I I I
i
34| i i I283.30J3J100J j j j | J 000098447
20|i!BCD! i ! ! j {93! 09| 22! ! ! ! ! ji! 000109102
in ' r ' 74TQ— Q9 — 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 nnm i oi?T?n
JU,L, tijy-y^-j. i i i i i i i i i i i i i i i i i i i i i i i i uuuiiy.fc,ED
35|BGiBSi i j j i ', 100012A4CF
2.2 INSTRUMENT CALIBRATION STANDARDS
BLANK (SO) & THREE OTHER STANDARDS
| ,' I1J00013B309
BLANK (SO) & THREE OTHER STANDARDS
20iljSO|l! i !20596jMAX123i93!09j22!ll!38,' | ,' I
21 ,' j ! ! ! I 0 PPB i i i ! j i i i TESLAB \ j j 00014BEA6
22 j ! i i i i i j i ! ! 1 . 00 j ! i j 00015C70D
30JC17439-92-1J | | | ITJO.OJ j J | | | j \ \ \ |U| 1.4 iUj 0.0000 \ \ \ S00016DA71
31JWIBJ |283.30!0.0000i (0.0000! \\\\\ [00017E483
|MAX123!93!09i22ill!42! \ \ [1100018F2BB
! i i ! TESLAB j i j oooi9FE5B
20 |1| S3 [I! j !20596|MAX123!93!09i22ill!42! \ \ [1
21 j i ! ! ! ! 3 PPB i i i ! ! i i ! TESLAB j i j oooi9FE5B
22 ! ,' i i ,' ,' i ! ! J [ 1 . 00 i ! i [ 0002006C2
30 !ci 7439-92-1 i | \ \ !TJ3.0| \ \ \ \ \ \ j | i IU11.4J 10.
31JWJB! |283. 30,'0. 0290J J0.0270! | | | j J J00022231
-- . . .0280J j j |000211903
JWJB! |283. 30,'0. 0290J J0.0270! | | | j J J000222318
!MAX123[93!09j22!lli47![[[1[000233187
! ! ! ! TESLAB1, i 1000243D59
2011JS50!!! j!20596!MAX123[93!09j22!lli47! [ [
21J! [ [! i BO PPB !!!!!!!! TESLAB ', 11000243059
ooiiiiitiiiii-i nnii'i nnn^^Acrri
" I I I I J..UU| i i i UUU^b^S^U
30iC[7439-92-li ! [ i JTJ50.0| !!!!!!!!! !Uil.4i 10.2765', ! 1 1000265897
31!W',B! [283.30',0.2760! J0.2770J i ! [ i i 10002762DE
20jl[S100|l! i {20596JMAX123193109122 111 151!\ \ 11J000287174
21} i 1 ! ! J100 PPB[ i i j ,' i i [ TESLAB j | [000297072
22!i i i!!!!!!ii.oo!i i10003085D9
30JC17439-92-1!!j \ JTJ100.0![[jjjjj j \ [U|1.4[JO.50351 j[[00031993'
31JWJBJ!283.30[0.5050!J0.5020!\\\\\ 100032A3A7
H-33 ILM04.0
-------
2.3 ANALYSIS OF A FIELD BLANK SAMPLE
00092D8C5
SAMPLE & ITS ANALYTICAL SPIKE SAMPLE WITH QC CODE FRB
20!1jMAX124{1{FRB{{20596 JMAX123\93 i 09!22!12 i 58!!ML j100 i1!
21{iLOWi[!JS308233-05!93[09114!J931081201118100093E714
22{j j 1j 1 1{11100J1.00! i10.0100094FODE
92 [ COLORLESS i COLORLESS i CLEAR,' CLEAR { ! ! 00096FEOO
30{C!7440-28-0!lUG/LjBDL13.0000ii i i i ! ! i ! i ! i |Uj3.0JUJO.4630|{235.19j
J0009711EC
31{W{C{ !276.80{1.2330{{-0.3070J j j \ \ \ ,'000981063
20il!MAX124AjliFRBi!20596JMAX123{93{09{22!13|03j||i1j000992CE7
21!{LOW!!{JS308233-05!{{|j93j08[20J {j\0010039C4
22 ,' i i i ! ,' ! i 1 ! i 1.00 j i i 0.0 i 0010142FC
30iC!7440-28-Oj jUG/Ll i 20.9380 | F { 20.00 | P \ 104. 7 | j ,' j | [851115! 1UJ3.0!
(20.9380!J3.3700!J001025A7B
31,'WJC! ! 276.80J21.4370J 120.4390', ! 1 \ \ \ {001036635
2.4 SPIKE SAMPLE RECOVERY & DUPLICATES PERFORMED ON THE SAME SAMPLE (QC
CODES LSO & LSF, AND LD1 & LD2)
NOTE: SAMPLE MAX123A CAN HAVE EITHER QC CODE LSO OR LD1
20 j 1 {MAX123 {F ! LSO j { 20596 ! MAX123 ! 93 | 09 | 22 ,' 12 ,' 40 j \ G \ 1. 00} 1 j 00094E6D2
21! ! LOW} { { {S308233-01,'93!09!14! 193J08124! i 18100095F526
22{ !!!!!! j ! I200il.00i1!91.5i00096FEEC
30 JCJ 7782-49-2! {MG/KG{BDL{ 0.8087 { !!!!!!,'!!!! 1 Uj 3 . 7 \U\ 1. 5305 1 1161.381
[000991F6C
311WJCJ 1196.OOJ3.2770! j-0.21601!! ! ! i J001002AE5
20!1}MAX123!F{LD1{ j 20596{MAX123{93{09 j 22 {12{40 | j G!1.0011{001013BFE
21J1LOW{{!iS308233-01i93j09{14{!93J08{24{{{8{001024A52
221 1 I !! i ! ! i {200{1.00{ ! !91.5!001035418
30JC,1 7782-49-2J JMG/KGJBDL|0.8087j i !!!!!! i !! 1 JUJ3.7[Uj1.5305 ! {161.38!
{001067498
31{W{C{ {196.00!3.2770{ {-0.2160J \ \ \ \ J j001002AE5
20!ljMAX123A{F!LDl{!20596[MAX123{93!09{22!12\45!j![11001089061
21!{LOW!!{{S308233-01![j\!93!08{24!1\ J001099D43
22 i {!! {{j j {!! i. oo j! {91.5 {OOHOA677
30{Ci7782-49-2i jUG/Ll \10.2050|F!10.00{Pj102.0{|J J |j85j115}}U\3.7j
J10.2050!{8.1000!J00111BE28
31,'WJC! ,'196.OOjlO.7890} J9.6210! ',!!!! 100112C9B2
H-34 ILM04.0
-------
20!11MAX123D{F jLD2}120596 jMAX123 j93109|22 j12 i 50 jjG i1.00 j1j001479AOE
21j|LOW!![1S308233-02J93J09114J!93[08!24}j18J00148A862
22! !!!!!!! j !200,'1.00j ! [90.9|00149B22B
30JC17782-49-2! {MG/KGJLTC!0.8509 | j JPJ200.0J |||| i! i JUJ3.7IBJ3.8930j
11.01721{001SOC661
311W1C! 1196.OOJ3.9210,' |3.8650i | ! j j ! {00151D1F9
20
-
22! ! ! ! ! ! ! ! ! ! 200 i i.ooj | {9i.s! 001594403
SO'.Cj 7782-49-2! IMG/KG) 1 1. 9178 | F| 2 . 16 |P i 88. 8 j ! | j j !75!125! |U|3.7! 18.
! 3. 2000J 1001605B08
SlJWjCj il96.00j8.6610! [9.0620! ! ! ! i ! 5001616692
!liMAX123DA!FiLD2!j20596JMAX123j93j09122j12\55ij!11J00152E28C
21! lLOWj ! j JS308233-02! ! ,' J j 93 JOS [24! i i J00153EF6E
22!!1 i i i i!! j ll.OOj1J91.5J00154F8A2
301CJ7782-49-2J |UG/Li i 13.5660 i F110.00 j P j 96.7 | ! j | \ |85ill5| |Ui3.7! ,'13.566!
!1.0320!1001550FDF
i J196.00113.6650J [13.4670!i J \ \ \ J001561B3F
001572CC1
8615!
2.5 DUPLICATES, WITH THE RESULT OF THE DUPLICATE SAMPLE QUANTITATED BY THE
MSA (QC CODES LD1, LD2, MSO, MSI, MS2, MS3)
NOTE: WHEN THE RESULT OF THE DUPLICATE SAMPLE IS QUANTITATED BY THE
MSA, THE DATA FOR THE RPD, THE CONTROL LIMIT (CRDL), AND THE * QC LIMIT
QUALIFIER ARE ENTERED ON THE MSO TYPE 30 RECORD. THAT IS, DATA FOR THE
DUPLICATE ANALYSIS THAT ARE ENTERED ON FORM VI MUST BE ENTERED ON THE
TYPE 30 RECORD OF THE EPA SAMPLE NUMBER THAT HAS THE 'DO1 SUFFIX (E.G.,
MAX123DO)
20 i 1 ! MAX123 ! F | LD1 1 1 20596 [MAX123 j 93 j 09 j 22 \ 12 j 40 j j G j 1 . 00 j 1 j 00135FD7E
21j '.LOWj ! j |S308233-Ol!93!09!l4| J93J08J24! | J8|001360BD2
22! ! ! ! i i ! ! i 1200J1.00! j |91.5i001371598
30 JC! 7440-38-2! ,'MG/KGj J4.7259J ! ', ! i | ! i j i ! ! JU12.7J [21. 6210! |0.0000!
!0014034CA
SliWjC! i 197. 20J21. 6210J J21.6210! ! } i j j [001414075
20iliMAX123AiFiLDl! ! 20596 JMAX123 | 93 | 09 j 22 | 12 ! 45 j | J !li0014250C2
21! [LOW! ! j !S308233-01j j ! j J93J08124! ! j J001435DA4
22j ! j !!!!!!! il.OOj ! |91.5i0014466D8
301CJ7440-38-2! lUG/Lj } 44.2020 \F\ 20. 00 |P J 112 . 9 ! | j | j j 85 j 115 j IUJ2.7!
J44.2020J [2.7700J 1001457E51
31|WiC! J197.20J45.0690! J43.3350J \ ( \ \ j J001468AOE
H-35 ILM04.0
-------
20!1!MAX123D!F!LD2', \ 20596 JMAX123 ! 93 109 i 22 j 12 | 50 \ \G\ 1.00 ! 1J001479B61
21!! LOW [ i i j S308233-02 i 93 ! 09 \ 14 j ', 93 j 08 ! 24', ! i 8 | 00148A9B5
22! I!!!!!! ! ! 200Jl.OOj !!91.5|00149B37E
30JCJ7440-38-2J [MG/KG|RINi5.8114i !!!!!!!!!!! JUJ2.7J J26.5870!jl.5100!
J00150C77C
31JW1C! {197.20(26.8700! J26.3040! !!!!,' J00151D335
20,'l!MAXl23DA!FiLD2j J 20596 JMAX123 j 93 \ 09 \ 22 j 12 | 55 j j [ !l!00152E3C8
21! iLOWj ! j JS308233-02! j ! i j 93 ', 08 ! 24 \ \ \ !00153FOAA
22! [ i !',!!!!! !l.00| ! J91.5|00154F9DE
30JC|7440-38-2! [UG/LlRINj49.9655jF{20.00JP1116.9jj| J| J85|115i X2.7!
[49.9655!!2.6500[[001551279
311W1C! [197.20!49.0290[ [50.9020! ',!!!! [001561E34
20!1i MAX123DO|F jMSO j |20596|MAX123 j93109 J22113{00 J!G11.00 J1100270330F
21! !LOW! ! [ !S308233-02!93!09!14,' \ 93 j 08 ,'24,' ,' J8J002714163
22{ ! ! ! ! ! ! ! i ,'200!2.50i ! |91.5|002724B2A
30!C!7440-38-2!iMG/KGj!7.8142JF}0.0\P\49.3|C\0.9958JL!2.2jj\!*!Ul2.7!
J14.3J j j J002735F59
311W1B] il97.20jO.0550! !!![!!! ',002746977
i 13 ', 03 ! ! G! 1.00 j 1! 002757B10
!ft! nr>976RQfi4
!i!i!!200|2.50j !{91.5J00277932B
440-38-2J ! i ! IFJIO.OJ ! { i { ,' | | i | !U|2.7i ,' | j j J00278A230
| J197.20jO.0810! | j ,' ! | { j .'00279AC4D
002768964
20 j 1JMAX123D2 j F JMS2 j \ 20596 JMAX123 [ 93 [ 09 j 22 j 13 j 06 j \ G \ 1.00', 1 \ 00280BDEB
21! SLOW)!!|S308233-02|93!09!14![93J08I24!|J8J00281CC3F
22! i !!!!!!! !200j2.50i ! !91.5[00282D606
30 j C j 7440-38-2 , | ', ' | F [ 20. 0 | ' ] ' | ] , , | | | U | 2 . 7 , | ' ' ] j 00278A230
31SWJBJ [197.20J0.1240J i ! ! ! ! j j J00284EF27
20!1!MAX123D3\F\MS3| |20596 jMAX123{93\09{22113|09 j j G\1.00\110028500C1
21| iLOWj ! ! !S308233-02!93!09{14J ,'93!08!24! | !8J002860F15
22,' ! i ! ! ! ' ! ! ! 200) 2. 50! ! !91.5|0028718DC
30}C j 7440-38-2} \}}\F!30.0!j j j j [ ! j \ \ \U!2.7 \ \ \\ \\00278A230
31JWJBJJ197.2010.1600!!!!!!!!!0028931FE
H-36 ILM04.0
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3.0
3.1
3.2
MERCURY (CVAA OR AVAA)
START OF A MERCURY RUN WITH RECORD TYPES 10 & 16 AND THE FIRST TWO TYPE
20 RECORDS
10 ', 93 i 09 j 09 ! 08 j 44 j CV i ILM04 . 0 ', ABC ', TESLAB i j j j 68-D2-0039 j M3 !
JTEST LABS INC. J 16 j 0000018F7
16 ! 93 i 09 i 09 i 14 ! 34 j N i ! i ,' 000012099
20 j 1 j IDL ! j i ! ,' i 93 i 07 j 15 J j j j j j 1 j 000044AEB
30jC| 7439-97-6,' j | j | j | | | ! j ,',' j j j !U,'0.1{ j | \ \ |0000558F4
20J11LRV! j j i ! J93J09J09J | j i \ \ 1 ! 0000666A6
^n ' r ' 74.T5— QT— fi ' i i i i i i i i i i i i i i i i i i i i i i innnn77ir|R
ju,^| t<*3y— y /— to, i i i i i i i i i i i i i i i i i i i i i i |UUUU//JCB
•30 i i i i i i i i i i i i i i i nnnnsTnno
34 , i i i i i i i i i i i i i |UUUUO/UUZ
34| i i 1253.70J0.2J5! \ \ \ [ [000098520
MERCURY INSTRUMENT CALIBRATION STANDARDS
BLANK (SO) AND FOUR OTHER STANDARDS
20I1JSOJ1! ! !20596!MAX123!93!09!09!08!44! | ! !1J00010936F
2i| j j j ! jo PPBJ !!!!!! ITESLABJ i !oooii9FOc
22! !!!!!!!!! li.oo! \ j !oooi2A773
30JC17439-97-6! j j i !T!0.0,' j | \ j j j j j | ,'Uj 0. 1 JUJ 0.0122 | | \ |00013BAD9
31JWJCJ J253.70J0.0122! | | | | | | | | 00014C4EC
1987 i | | J00018FB5E
20 11 i SO. 2 ', 1! i i 20596 j MAX123 i 93 j 09 i 09 i 081 48 1 \ \ \ 1 j 00015D392
21j i i i ! |0.2 PPBj j i ! j i ', i TESLAB i ', 100016DF8F
22 i ! j ! i i i ! ! ! !1.00! ! i i 00017E7F6
30jc!7439-97-6!j!i!Tio.2!!l!!i!!!i!u!o.iiB!o.
31JW!C|J253.7010.1987J!!!!!!!1000190571
20J11S1.0J1J !!20596|MAX123!93i09!09!08!53i j 1!l!000201412
2i|! i i 11i-o PPBJ !!!!!!!TESLAB!!!ooo2i200E
221 1 1 i 1 1 ! 1 1 1 11.00! 1 1 J000222875
30iCl7439-97-6i1 ! 1 jTll.Oi Hi!!!!!! iUjO.l! jl.0128! ! ! J000233BDC
31JW1C! |253.70!1.0128! | ', ', ', \ \ \ 10002445EF
20!ljS2.0!l!!120596!MAX123J93J09!09
O1 I I I I I I o n DI3T3 I I I t I I I I TTTOT aR ' ' ' nnfiOfifiHQO
* •!• I I I I I I * • u era I I I I I I I I l&oLiAB ( | ( UUU^DOUS^
•)•) i i i i i i i i i i 11 on i i i i nnn97fiRi«>Q
*•*• i i i i i i i i i i |J..uU| | | |UUU^/oorr
30jC|7439-97-6! 1 1 \ iT|2.0! | j j ,' j j 1 j j iU.'O.li 1
31!W!C![253.70)2.0055!j \ \ \ \ \ \ [000298674
J08J57! j i [11000255495
o ccnnn
.0055!i11000287C61
H-37
ILM04.0
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20J1JS5.0J1S i !20596jMAX123!93|09|09!09!01!| j 11J000309513
211 j i ! | |5.0 PPBj i !! i j i JTESLABJ j J00031A113
22 i !j ! ! ! i i ! ! i1.00 i! j !00032A97A
30|C|7439-97-6! j{|!T{5.0j i !!!!i i|!\V\0.1\ (4.9952!j ! |00032
31JWJC! j 253.70 ',4.9952 j j j | j \ \ \ J00034C6F8
3.3 SPIKE SAMPLE RECOVERY & DUPLICATES PERFORMED ON DIFFERENT SAMPLES (QC
CODES LSO & LSF, AND LD1 & LD2)
.2011J002106798
10021175EF
',002295343
20illMAX123jFjLSO! j 20596 JMAX123 j 93 i 09 j 09 ', 13 j 20 j |G|0.:
21! {LOW,1 i ! JS308233-01J93!09!08! i93j08!24i i 1810021175I
22{!! ! i j{ !! ilOOjl.OOj j|91.5|002127PB4
30JCJ7439-97-6! JMG/KGjBDL{0.0546j !!!!!!!!!!! !UjO.11Uj0.0349| | j j002159ECO
31iW|Ci !253.70!0.0349j !!!!!!! [00216A8E3
20il|MAX123S!FiLSFi|20596[MAX123j93J09j09J13i25j!Gj0.20!liC
21]SLOW!!!JS308233-03J93!09|08J!93!08!24!jJ810023061A2
22', ! ! ! ! ! ! ! i ilOOjl.OOj ! {91.5J002316B67
301C17439-97-6! JMG/KGJ|0.5664jF!0.55|Pj103.0j \\\\ I75J125! !U{0.1{ {1.03661
,' [ .'00232807A
31{WJC! {253.70{1.0366{ ,'!!,'!!! 1002338A9D
20 {1 j MAX126 ', F {LD1 { { 20596 {MAX123 { 93 { 09 { 09 {13 { 30 { {G i 0.22 {1 { 00217B9F5
21j JLOWJ ! ! |S308233-06!93!09i08! ',93 {08)24! { !8!00218C84C
22,'!!!,'!! j! !ioo|i.oo! {!85.6{002190211
30JCJ7439-97-6!{MG/KG{{1.3685{ !!!!!!!!!!!|Ui0.1{J2.5771J|JJ00222F11D
31SWJC!!253.70[2.577l!{{{{{{|[00223FB40
20!l!MAXl26D!F!LD2j{20596JMAX123{93{09j09|13j35{IGJO
21! (LOW! ! ! !S308233-07!93!09!08i !93j08i24i j J8J002251A:
22[ !!!!!!!! {100{1.00{{!85.l!0022624BC
30[C!7439-97-6! JMG/KG \ BDL { 0. 0556 { { [PJ200.0! J [L{0.11{ { { { * !U{ 0. 1 j U,'0. 0278 {
! j1002273795
31JWJC! J253.70jO.0278! {{{{{{{ [0022841B9
3.4 SPIKE SAMPLE RECOVERY & DUPLICATES PERFORMED ON THE SAME SAMPLE (QC
CODES LSO & LSF, AND LD1 & LD2)
20{1{MAX126{F jLSO{j 20596{MAX123{93{09 J 09{16{101{G J0.20{1{002106798
21j !LOWj i ! jS308233-06!93!09!08j [93 {08! 24,' \ !8!0021175EF
22j 1! ! ! ii i i !100{1.00{ 1{91.5{002127FB4
30JCJ7439-97-6! jMG/KGl J0.6429! {{{{{{{!{{ i iU{0.1{ J1.1765J { j [002159ECO
31JWJC!{253.70jl.1765!!!!!!!!J00216A8E3
21{1{002240C9D
002251AF4
H-38 ILM04.0
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20 i1!MAX126 j F j LD1j|20596 jMAX123 J 93|09!09116 j10 jjG j 0.20{1100217B9F5
21j ILOWJ!j iS308233-06|93|09!08!i93j08|24i|S8J00218C84C
22j i i i i i j!!!100|i.oo!!!91.5{002190211
30JCJ7439-97-6! JMG/KGJ JO.6429! !!!!!!!!!!!!U!0.1! 11.1765!i ! I002159ECO
3l!WlC|J253.7011.1765J!!!!!!!J00223FB40
20 [ 1 j MAX126D ! F! LD2 ! ! 20596 |MAX123 i 93 | 09 j 09 i 16 ', 15 \ \ G \ 0.21', 1', 002240C9D
21! [LOW! ! ! !S308233-07!93i09!08i [93',08! 24! ! J81002251AF4
22! !!!!'! ! i ',10011.00! ! !90.910022624BC
30JCJ7439-97-6! JMG/KGJ ,'0.2231i j JPJ97.0! j iLjO.ll! { j !*!Uj0.1i [0.4286! i i
J002273795
31!W!C!J253.70|0.4286!!!!!!!!J0022841B9
20!liMAX126SlF!LSFi!20596JMAX123j93|09j09!16|20!JGJ0.20!1j00229534B
21!ILOWJ ! ! !S308233-08!93!09,'08! !93!08J24! | [8J0023061A2
22[ ! ! ! j j ! ! ! ,'lOOll.OOj i J91.5!002316B67
30JCJ7439-97-6!JMG/KG!JO.9710jF|0.55|Pj59.7j|!j!N!75!l25j!U|0.1i|1.7769|
! !J00232807A
31JWJC! !253.70il.7769J i j j | ! | i |002338A9D
3.5 INITIAL CALIBRATION VERIFICATION (ICV) WITH LVM O.C CODE
20!ljICV!l!LVMi J20596JMAX123!93!09J09J09S06! i j S1J00035D687
21!1 i ! i !ICV-5| !!{!!!!ICF(0791)| ! 100036E25E
22 i i i ! ! ! j ', j ', i 2.00 i ', { ', 00037EAC6
30 }C{ 7439-97-6! JUG/LJ ! 4. 91JTJ 4. 9 JP j 100.2 j j j ! j ! 80.0 [120.0! JUJ0.1,1 J2.4559J
! ! !00038FFDO
31SWJCJ J253.7012.4559! !!!!!!! J0003909FC
3.6 LABORATORY CONTROL SAMPLE (SOLID) WITH LCM QC CODE
20[liLCSS!F!LCM! ', 20596 JMAX123 j 93 | 09 j 09 ! 12 j 24 j j G| 0. 20 11! 001256DBA
21', ii'i !LCSHG!93!09!08! \ \ \ lQAL-0287! 18J001267B1B
22j i! i i i j ! j jlOOjlO.OOj j1 J001278443
301CJ7439-97-6! [MG/KGl i 13. 9 1 T 112.7 j P j 109.4 1 | | ! | !8.5!l7.0i |Uj0.l! ',2.7719!
1 1J00128996D
311WJC1, ',253.70J2.7719', !!!!!!! 100129A39A
H-39 ILM04.0
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4.0 CYANIDE (CA, AS, C, T)
4.1 START OF A CYANIDE RUN WITH RECORD TYPES 10 & 16 AND THE FIRST TWO TYPE
20 RECORDS
10193109 j 01i14 i 09 i CA!ILM04.01 ABC\TESLAB111168-D2-0039 i Cli
JTEST LABS INC.17j00000189C
16193J091011151031Y1j j1000012033
4.2
20111IDL1111j |91!10|15i
IT I I
i J. , |
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 i IT T>V i i i i i '
| a. | .L.KV i i i i i i
1111111111
I I I I I I I I I I
34! ! 1 1620.001101400! 1 ,' 1
i!!i1i 000044A74
10.01 1 j!110000556DC
i i j111000066486
1 1 1 1 {000076FDA
000087917
1000098169
CYANIDE INSTRUMENT CALIBRATION STANDARDS
BLANK (SO) AND FIVE OTHER STANDARDS
109!1\ J11000108FA1
000119B3E
20|l!SOil!!1205961MAX123193109101114!
21! i 1 i i 10 PPBj i 1i 1 1 j 1TESLAB! i J000119B
221 11 HI! 1 i 111.001! 1 100012A3A5
30',l! i i j ! ITJO.O! 1 i j i j 1 ! ! 1 JU110.OJU10.3543! ' i J00013B48B
31{WiCi1620.0010.3543!ill!!!!100014BD34
20!liSlO|l! i !20596!MAX123j93!09!01114!lOj ,' ,' J1100015CB95
211 1 1 i i110 PPB! i ! 1 1 ! 1 i TESLAB1 i 100016D763
22l!!!jjj!jjjl.00 111!00017DFCA
30!l! {1i i ITJIO.O! i i 1 1 i 1 i1j iUllO.Oj111.1700! ! ! J00018FOD2
31,'WiCl j 620.00 jll. 1700{ j ', i i ', ', | 100019F97B
2011i S40 i1j j !205961MAX123 j 93 J 09!01i14!11i | | j110002007EO
21! i ! ! ! 140 PPBl 111!,1! ! TESLAB j 1 J0002113B1
i |38.4000i [ ,' J000232D23
0002435CC
on i T i i i i i i «> i An n' ' ' ' ' ' i ' ' ' ' IT ' i n n ' '
•3U i -i i i i i i | i. i 4U. U | i | | i | | i i | |U|1U.U| i
31JW1C11620.OOJ38.4000! 11 !i i 1 1i0002
20111S10011J1 i20596[MAX123193109101114112111{1J00025445F
211i l i ilioo ppBj1i!1111TESLAB!1looo26505D
22! i Hi!! l !!!i.oo!',i!ooo27S8C4
3011! Hi! ITJIOO.01 1 ! 1 i 1 i 1 1 i iUllO.O,1 ,'99.74001 J i 1 000232D23
31iWJCi J620.00199.7400! 1 i [111 i [0002972A5
H-40
ILM04.0
-------
>! ! ! il',000308139
20!l!S200!li!j20596|MAX123|93!09!01il4jl2!
21!!!!'1200 PPBJ j!!!!!JTESLABJ j !000318D38
22! i ! ! i ! ! ! ! i 11.00!j j{00032959F
30JI! i ! i i !T{200.0! !!',!!!!!! iUjlO.Oj J201.3000j j j |00033A6D8
31|W|Ci i620.00{201.3000! !!!!!!! !00034AF81
20!l!S400jli! !20596jMAX123!93i09!Ol!l4!l3j j j 11J00035BE18
21!i ii!!400 PPB|!!!!!!ITESLABJ !S00036CA19
22J i i i i i i i i ! il.OOi i!J00037D280
30',I! i i ! ! JTJ400.0! i i i i ! j i i ! JUilO.O! |399.5000i ! ! {00038E3BB
3l!W[Ci J620.00J399.5000! i j j ! j j | J00039EC64
4.3 PREPARATION BLANK (SOIL) WITH LRB QC CODE
20!l!PBS!F!LRB!!20596!MAX123!93J09}01!14!23| jGi1.00|1\000928FAO
21{ ! ! ! ! 1PBJ93S08S30! [ { ', ! { !8[000939A40
22 i ! ! i i i i!! i 50!1.00!!!100094A30C
30ji|j JMG/KG|BDL!o.sooi!!!!!!!!!!!!u',io.oiu!-o.ii30!j j1000953433
3l!W!C| J620.00j-0.1130! !!!!!!! |00096BE6F
4.4 LABORATORY CONTROL SAMPLE (SOIL) WITH LCM QC CODE
20 ! 1! LCSS ! F ! LCM { ! 20596 j MAX123 | 93 { 09 | 01 j 14 | 24 | | G 11.00 ', 1 j 00097CF4D
21j! !! ! !LCSCN!93!08!30}j | j iQAL-0689j !8|00098DCBO
22! !j i i !!!! |50il.OOi i j!00099E57C
30JI! i JMG/KG! !5.0!T!5.6!P!89.3iiJ!!!4.3i6.9!!U!lO.Oj j100.0933}|j
31,'wjci j620.oo|ioo.o933!!!!!!!! ',001010315
4.5 CONTINUING CALIBRATION VERIFICATION (CCV) WITH LVC QC CODE
20!ljCCV|l!LVCi!20596!MAX123!93J09!01!14!30!\\ J1J0015045A3
21!!!i !!200 PPB!i \\\\\[TESLABJ j iooisi5iA2
22j ! ! ! ! 1 1!! ! ,1.00! j !J001525A09
30jli ! lUG/Lj !188.48!T!200.0!Pi94.2! \ \ \ \ i85.0ill5.0| XlO.Oj [188.4772
!001536E87
31JWJC! j620.00|188.4772! !!!!!!! {001547916
4.6 SPIKE SAMPLE RECOVERY & DUPLICATES PERFORMED ON THE SAME SAMPLE (QC
CODES LSO & LSF, AND LD1 & LD2)
20 ', 1JMAX123 ! F j LSO \ \ 20596 JMAX123 i 93 } 09 j 01! 14 j 35 | JG {1. 07 ! 1 i 001955D8E
21!! LOW!!j!S308233-01J93!08!30! i93!08j24j j J8J001966BDF
22!!I!!!!!!!so;i.ooj!j9i.5i001977573
H-41 ILM04.0
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30|Ii i JMG/KGJBDLJ 0.5107 | !!!!!!!!,'!! X10.OiUj-0.352l! J ! J002009309
31JWJC! !620.OOj-0.3521! !',!!!!! ,'002019D4B
20jliMAX123iFjLDl|J20596JMAX123|93!09J01j14|35j|Gi1.07|1|00202AE62
21| iLOWj i !iS308233-01j93j08j30i J93|08j24i jI8J00203BCB3
22j j i!!j i j1{50J1.00!i|91.5!00204C64C
30|i!JIMG/KGJBDLio.5107!i!!!!!!!1j!iujio.ojul-o.352i!ji100207E3DD
31JWJC1j620.001-0.3521J!'!!!!!100208EE1F
20 11JMAX123D IF ,'LD2 1 i 20596 JMAX123 j 93 |09 J 01 i 14 j 36 [ JGJ1.05 \ 1 \ 00209FF7A
211 ILOWJ J !1S308233-02J93108130!193J08J241 i J8!002100DCB
22! ! ! ! ! ! i i!15011.00! 1190.9J002111767
30!H i1KG/KGIBDL!0.5204! ! ! 1 ! ! 1 ! I ! ! !IUjlO.OjUj-0.63951 !!10021228D6
311W1CJ1620.OOj-0.6395!j11i11i[002133324
20111MAX123SJF1LSF1[20596[MAX123[93J09!01114J37j[Gl1.01Jlj0021444AD
21! ILOWJ! i!S308233-03!93!08!30i J93108J24! !!8{0021552FE
22j !i i ! ! i 1 ! 150J2.00!1191.51002165C98
30il! i IMG/KG! i25.8410jFj27.05iPi95.5i i i j 1 S75J125! iUllO.O! 1238.8096,' J {
10021770CO
31JW1C! j620.00J238.8096! !!!!!!! J002187B4E
H-42 ILM04.0
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