USEPA CONTRACT LABORATORY PROGRAM
STATEMENT OF WORK
FOR
INORGANIC ANALYSIS
Multi-Media, Multi-Concentration
ILM05.2
December 2001
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54OR01504
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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 WITH CONTRACT REQUIRED QUANTITATION
LIMITS
EXHIBIT D: ANALYTICAL METHODS
EXHIBIT E: CONTRACT LABORATORY PROGRAM QUALITY ASSURANCE MONITORING PLAN
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
APPENDIX A: FORMAT OF RECORDS FOR SPECIFIC USES
APPENDIX B: MODIFIED ANALYSIS
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EXHIBIT A
SUMMARY OF REQUIREMENTS
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Exhibit A - Summary of Requirements
Table of Contents
Section Page
1.0 PURPOSE 5
t
2.0 DESCRIPTION OF SERVICE 5
3.0 DATA USES 5
4.0 SUMMARY OF REQUIREMENTS 5
4.1 Introduction to the Inorganic Statement of Work 5
4.2 Overview of Major Task Areas 6
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Exhibit A Sections 1-4
Purpose
1.0 PURPOSE
The purpose of the multi-media, multi-concentration inorganic analytical
service is to provide analytical data for use by the U.S. Environmental
Protection Agency (USEPA) in support of the investigation and clean-up
activities under the Comprehensive Environmental Response, Compensation,
and Liability Act of 1980 (CERCLA) and the Superfund Amendments and
Reauthorization Act of 1986 (SARA). Other USEPA Program Offices that
have similar analytical data needs also use this service.
2.0 DESCRIPTION OF SERVICE
The inorganic analytical service provides a contractual framework for
laboratories. This framework applies USEPA Contract Laboratory Program
(CLP) analytical methods for the isolation, detection, and quantitative
measurement of 23 metals (including mercury) and cyanide in water/
aqueous and/or soil/sediment samples. The analytical service contract
provides specific contractual requirements by which USEPA will evaluate
the data.
3.0 DATA USES
This analytical service contract provides data which USEPA uses for a
variety of purposes, such as: determining the nature and extent of
contamination at a hazardous waste site, assessing priorities for
response based on risks to human health and the environment, determining
appropriate cleanup actions, and determining when remedial actions are
complete. The data may be used in all stages in the investigation of
hazardous waste sites, including: site inspections, Hazard Ranking
System (HRS) scoring, remedial investigation/feasibility studies,
remedial design, treatability studies, and removal actions.
The data may also be used in litigation against Potentially Responsible
Parties in the enforcement of Superfund legislation. As a result, the
Contractor must be aware of the importance of maintaining the integrity
of the data generated under this contract, since it is used to make
major decisions regarding public health and environmental welfare. The
Contractor may be required to appear and testify to the accuracy and/or
validity of the data generated.
4.0 SUMMARY OF REQUIREMENTS
4.1 Introduction to the Inorganic Statement of Work
The Statement of Work (SOW) is comprised of eight exhibits and two
appendices. Exhibit A provides an overview of the SOW and its general
requirements. Exhibit B contains a description of the reporting and
deliverables requirements, in addition to the data reporting forms and
instructions. Exhibit C specifies the Inorganic Target Analyte List
(TAL) for this SOW with the Contract Required Quantitation Limits
(CRQLs) for the sample matrices. Exhibit D details the required
analytical procedures to be used with this SOW and resulting contracts.
Exhibit E provides descriptions of required Quality Assurance/Quality
Control (QA/QC), Standard Operating Procedures (SOPs), QA/QC
performance, and the reporting of data. Exhibit F contains chain-of-
custody and sample documentation requirements. To ensure proper
understanding of the terms utilized in this SOW, a glossary can be found
in Exhibit G. When a term is used in the text without explanation, the
glossary meaning shall be applicable. Specifications for reporting data
in computer-readable format appear in Exhibit H. Appendix A provides
examples of the data format requirements specified in Exhibit H.
Appendix B contains a description of the requirements for performing
A-5 ILM05.2
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Exhibit A Section 4
Summary of Requirements (Con't)
modified analyses, as well as the analytical procedure for Graphite
Furnace Atomic Absorption (GFAA).
4.2 Overview of Major Task Areas
For each sample, the Contractor shall perform the tasks described in
each section. Specific requirements for each task are detailed in the
exhibits referenced in the following sections.
4.2.1 Task I: Sample Receiving, Storage, and Disposal
4.2.1.1 Chain-of-Custody
The Contractor shall receive and maintain samples under proper
chain-of-custody. All associated document control and inventory
procedures shall be developed and followed. Documentation
described herein shall be required to show that all procedures are
strictly followed. This documentation shall be reported as the
Complete Sample Delivery Group (SDG) File (CSF) (see Exhibit B).
The Contractor shall establish and use appropriate procedures to
safeguard confidential information received from USEPA.
4.2.1.2 Sample Scheduling/Shipments
Sample shipments to the Contractor's facility will be scheduled
and coordinated by the Contract Laboratory Program (CLP) Sample
Management Office (SMO). USEPA may request analyses that include
all or a subset of the Inorganic Target Analytes listed in Exhibit
C. 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.
4.2.1.2.1 Samples will be shipped routinely to the Contractor through an
overnight delivery service. However, as necessary, the
Contractor shall be responsible for any handling or processing
of the receipt of sample shipments. This includes the pick-up
of samples at the nearest servicing airport, bus station, or
other carrier within the Contractor's geographical area. The
Contractor shall be available to receive and process sample
shipments at any time the delivery service is operating,
including Saturdays, to ensure that short sample analysis time
requirements can be met.
4.2.1.2.2 If there are problems with the samples (e.g., mixed media,
containers broken or leaking) or sample documentation and
paperwork (e.g., Traffic Reports/Chain of Custody Records not
with shipment, sample and Traffic Report/Chain of Custody
Record do not correspond), the Contractor shall immediately
contact SMO for resolution. The Contractor shall immediately
notify SMO and the USEPA Regional CLP Project Officer (CLP PO)
regarding any problems and laboratory conditions that affect
the timeliness of analyses and data reporting. In particular,
the Contractor shall immediately notify SMO personnel and the
USEPA Regional CLP PO in advance regarding sample data that
will be delivered late and shall specify the estimated delivery
date.
4.2.1.2.3 To monitor the temperature of the sample shipping cooler more
effectively, 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
ILM05.2 A-6
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Exhibit A Section 4
Summary of Requirements (Con't)
TEMPERATURE INDICATOR. The Contractor shall record the
presence or absence of the cooler temperature indicator bottle
on Form DC-1, Item 8 - Cooler Temperature Indicator Bottle (see
Exhibit B).
4.2.1.2.3.1 When the USEPA Regional Office supplies a cooler temperature
indicator bottle in the sample shipping cooler, the
Contractor shall use the USEPA supplied cooler temperature
indicator bottle to determine the cooler temperature. The
temperature of the cooler shall be measured at the time of
sample receipt by the Contractor.
4.2.1.2.3.2 The temperature of the sample shipping cooler shall be
measured and recorded immediately upon opening the cooler.
4.2.1.2.3.3 To determine the temperature of the cooler: the Contractor
shall locate the cooler temperature indicator bottle in the
sample shipping cooler, remove the cap, and insert a
calibrated thermometer into the cooler temperature indicator
bottle. Prior to recording the temperature, the Contractor
shall allow a minimum of 3 minutes, but not greater than 5
minutes, for the thermometer to equilibrate with the liquid
in the bottle. At a minimum, the calibrated thermometer
(ą1°C) shall have a measurable range of 0-50°C. Other
devices which can measure temperature may be used if they
can be calibrated to ą1°C and have a range of 0-50°C. If a
temperature indicator bottle is not present in the cooler,
an alternative means of determining cooler temperature shall
be used. Under no circumstances shall a thermometer or any
other device be inserted into a sample bottle for the
purpose of determining cooler temperature. The Contractor
shall contact SMO and inform them that a temperature
indicator bottle was not present in the cooler. The
- Contractor shall document the alternative technique used to
determine cooler temperature in the SDG Narrative.
4.2.1.2.3.4 If the temperature of the sample shipping cooler's
temperature indicator exceeds 10°C, the Contractor shall
contact SMO and inform them of the temperature deviation.
SMO will contact the Region from which the samples were
shipped for instruction on how to proceed. The Region will
either require that no sample analysis(es) be performed or
that the Contractor proceed with the analysis(es). SMO will
in turn notify the Contractor of the Region's decision. The
Contractor shall document the Region's decision and the EPA
sample numbers of all samples for which temperatures
exceeded 10°C in the SDG Narrative.
4.2.1.2.3.5 The Contractor shall record the temperature of the cooler on
Form DC-1, under Item 9 - Cooler Temperature, and in the SDG
Narrative (see Exhibit B).
4.2.1.2.4 The Contractor is required to retain unused sample volume, used
sample containers, and empty sample bottle containers for a
period of 60 days after data submission. From time of receipt
until analysis, the Contractor shall maintain all water/ao^jeous
(preserved and unpreserved) and/or soil/sediment samples at 4°C
(ą2°C) (see Exhibit B).
4.2.1.2.5 The Contractor shall be required to routinely return sample
shipping containers (e.g., coolers) to the appropriate sampling
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Exhibit A Section 4
Summary of Requirements (Con't)
office within 14 calendar days following shipment receipt (see
contract, Section G titled, "Government Furnished Samples").
4.2.1.2.6 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.
4.2.1.2.6.1 A Case consists of one or more SDGs. An SDG is defined by
the following, whichever is most frequent:
Each Case of field samples received, or
Each 20 field samples [excluding Performance
Evaluation (PE) samples] within a Case, or
Each 7 calendar day period (3 calendar day period for
7 day turnaround) during which field samples in a Case
are received (said period beginning with the receipt
of the first sample in the SDG).
In addition, all samples and/or sample fractions
assigned to an SDG must have been scheduled under the
same contractual turnaround time. Preliminary Results
have no impact on defining the SDG.
4.2.1.2.6.2 Samples may be assigned to SDGs by matrix (i.e., all soils
in one SDG, all waters in another), at the discretion of the
laboratory. However, PE samples received within a Case
shall be assigned to an SDG containing field samples for
that Case. Such assignment shall be made at the time the
samples are received, and shall not be made retroactively.
4.2.1.2.6.3 Each sample received by the Contractor will be labeled with
an EPA sample number, and accompanied by a Traffic
Report/Chain of Custody Record bearing the sample number and
descriptive information regarding the sample. EPA sample
numbers are six digits in length. If the Contractor
receives a sample number of any other length, the Contractor
shall contact SMO immediately. The Contractor shall
complete and sign the Traffic Report/Chain of Custody
Record, 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/Chain of Custody Record in choosing the
Quality Control (PC) samples when such information is
provided. If no QC sample is designated on the Traffic
Report/Chain of Custody Record, the Contractor shall select
a sample and notify SMO for Regional acceptance. SMO shall
contact the Region for confirmation immediately after
notification.
4.2.1.2.6.4 The Contractor shall submit signed copies of Traffic
Reports/Chain of Custody Records for all samples in a SDG to
SMO within three working days following receipt of the last
sample in the SDG. Faxed copies of Traffic Reports/Chain of
Custody Records do not meet this requirement. Traffic
Reports/Chain of Custody Records shall be submitted in SDG
ILM05.2 A-8
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Exhibit A Section 4
Summary of Requirements (Con't)
sets (i.e., all Traffic Reports/Chain of Custody Records for
a SDG shall be clipped together) with an SDG Cover Sheet
containing information regarding the SDG, as specified in
Exhibit B.
4.2.1.2.6.5 EPA Case numbers, 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.
4.2.1.3 Modified Analysis
The Contractor may be requested by USEPA to perform modified
analyses. These modifications will be within the scope of this
SOW and may include, but are not limited to, analysis of
additional analytes and/or lower quantitation limits. These
requests will be made by the USEPA Regional CLP PO, USEPA OERR
Analytical Operations/Data Quality Center (AOC) Inorganic Program
Manager (PM), and Contracting Officer (CO) in writing, prior to
sample scheduling. If the Contractor voluntarily elects to
perform these modified analyses, these analyses will be performed
with no increase in per sample price. All contract requirements
specified in the SOW/Specifications will remain in effect unless
the USEPA CO provides written approval for the modification (s) and
a waiver for associated defects. The USEPA CO approval must be
obtained prior to sample scheduling.
4.2.2 Task II: Sample Preparation and Analysis
4.2.2.1 Overview
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.
4.2.2.2 The Contractor shall prepare and analyze samples as described in
Exhibit D. Sample preparation methods shall remain consistent for
all samples analyzed within a Case. Prior to sample analysis, the
Contractor shall review the Traffic Report/Chain of Custody Record
for any special sample analysis instructions. Anomalies that
occur during sample analysis shall be reported to SMO and the
USEPA Regional CLP PO immediately.
The Contractor shall collectively review all analytical results
associated with a sample. This includes undiluted, diluted,
serial dilution, and interference results. The Contractor shall
report any significant anomalies between these results in the SDG
Narrative indicating possible matrix interferences.
4.2.2.3 Quality Assurance/Quality Control Procedures
4.2.2.3.1 The Contractor shall strictly adhere to all specific QA/QC
procedures prescribed in Exhibits D and E. 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 Exhibits B and H.
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Exhibit A Section 4
Summary of Requirements (Con't)
4.2.2.3.2 The Contractor shall maintain a Quality Assurance Management
Plan (QAP) with the objective of providing sound analytical
chemical measurements. This program shall incorporate the QC
procedures, any necessary corrective action, and all
documentation required during data collection as well as the
quality assessment measures performed by management to ensure
acceptable data production.
4.2.2.3.3 Additional QC shall be conducted in the form of the analysis of
laboratory PE samples submitted to the laboratory by USEPA.
Unacceptable results of all such QC or laboratory- PE samples
may be used as the basis for an equitable adjustment to reflect
the reduced value of the data to USEPA o.r_rejection of the data
for specific analyte(s) within an SDG or the entire SDG. Also,
unacceptable results 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 USEPA, as well as meeting the contract
requirements for analysis (Exhibit D); QA/QC (Exhibit E); data
reporting and other deliverables (Exhibits B and H); and sample
custody, sample documentation, and SOP documentation (Exhibit
F) .
4.2.3 Task III: Sample Reporting
4.2.3.1 USEPA has provided to the Contractor formats for the reporting of
data (Exhibits B and H). The Contractor shall be responsible for
completing and submitting analysis data sheets, computer-readable
data on diskette (or via an alternate means of electronic
transmission approved in advance by USEPA) in a format specified
in this SOW and within the time specified in Exhibit B, Section
1.1.
4.2.3.2 Use of formats other than those designated by USEPA (see Exhibits
B and H) will be deemed as noncompliant. Such data are
unacceptable. Resubmission in the specified format at no
additional cost to the Government shall be required.
4.2.3.3 Computer generated forms may be submitted in the hardcopy Sample
Data Package (s) provided that the forms are in exact USEPA format.
This means that the order of data elements is the same as on each
USEPA required form, including form numbers and titles, page
numbers, and header information.
4.2.3.4 The data reported by the Contractor on the hardcopy data forms and
the associated computer-readable data submitted by the Contractor
on diskette (or via an alternate means of electronic transmission,
if approved in advance by USEPA) shall contain identical
information. If discrepancies are found during Government
inspection, the Contractor shall be required to resubmit either
the hardcopy forms or the computer-readable data, or both sets of
data, at no additional cost to USEPA.
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EXHIBIT B
REPORTING AND DELIVERABLES REQUIREMENTS
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Exhibit B - REPORTING AND DELIVERABLES REQUIREMENTS
Table of Contents
Section Page
1.0 CONTRACT REPORTS/DELIVERABLES DISTRIBUTION 5
1.1 Report Deliverable Schedule 5
1.2 Distribution 8
2.0 REPORTING REQUIREMENTS AND ORDER OF DATA DELIVERABLES 9
2.1 Introduction 9
2.2 Resubmission of Data 9
2.3 Quality Assurance (QA) Management Plan and
Standard Operating Procedures (SOPs) 10
2.4 Sample Traffic Reports/Chain of Custody Records 10
2.5 Sample Data Package 11
2.6 Complete SDG File (CSF ) 16
2.7 Data in Computer-Readable Format 17
2.8 Results of the Intercomparison and Performance
Evaluation (PE) Sample Analyse s 18
2.9 Preliminary Results 18
2.10 Quarterly Verification of Linear Ranges and Interelement
Correction Factors and Annual Verification of MDLs 18
2.11 Electronic Instrument Data 19
2.12 Corrective Action Procedures 19
3.0 FORM INSTRUCTIONS 20
3.1 Introduction 20
3.2 General Information 20
3.3 Header Information 20
3.4 Inorganic Forms 22
3.5 Sample Log-In Sheet [Form DC-1] 46
3.6 Full Inorganics Complete SDG File (CSF) Inventory
Sheet [Form DC-2] 48
4.0 DATA REPORTING FORMS 49
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Exhibit B Section 1
Contract Reports/Deliverables Distribution
1.0 CONTRACT REPORTS/DELIVERABLES DISTRIBUTION
1.1 Report Deliverable Schedule
The following table reiterates the contract reporting and deliverables
requirements and specifies the distribution that is required for each
deliverable. The turnaround times for Items B through E are 7, 14, or
21 days.
NOTE: Specific recipient names and addresses are subject to change
during the term of the contract. The USEPA Office of Emergency and
Remedial Response (OERR) Analytical Operations/Data Quality Center (AOC)
Inorganic Program Manager (AOC PM) will notify the Contractor in writing
of such changes when they occur.
TABLE 1
Item
A.
B.2
C.2
D.2
E.2'3
F.Ť
G.5'6
Sample Traffic
Reports /Chain of
Custody Records
Sample Data Package
Data in Computer-
Readable Format
Results of
Intercomparison
Study /PE Sample
Analysis Study
Complete SDG File
(CSF)B
Preliminary Results
Quarterly
Verification of
ICP-AES/ICP-MS
Linear Ranges and
ICP-AES
Interelement
Correction Factors
Annual Verification
of Method Detection
Limits (MDLs)
No. of
Copies*
1
1
1
1
1
1
1
1
Delivery Schedule
3 working days after
receipt of last sample
in Sample Delivery
Group (SDG) -1
XXC days after
Validated Time of
Sample Receipt (VTSR)1
of last sample in SDG.
XXC days after VTSR of
last sample in SDG.
XXC days after VTSR of
last sample in SDG.
XXC days after VTSR of
last sample in SDG.
Within 72 hours after
receipt of each sample
at laboratory, if
requested.
Quarterly: 15th day of
January, April, July,
and October.
Annually: 15th day of
January.
Distribution
o
2
co
X
X
X
X
X
X
X
Region
X
X
X
o
O
0,
a,
u
X
X
to
H
a
X
X
X
B-5
ILM05.2
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Exhibit B Section 1
Contract Reports/Deliverables Distribution (Con't)
TABLE 1 (Con't)
Item
H.6'7
I.6'7
J.
Standard Operating
Procedures (SOPs)
Quality Assurance
Management Plan
(QAP)
Electronic
Instrument Data
No. of
Copies*
1
1
Lot
Delivery Schedule
Revise within 30 days
after contract award
and receipt of USEPA
comments .
Submit within 7 days
of receipt of written
request to recipients
as directed. (See
Exhibit E, Section 6)
Submit within 14 days
of amended SOP(s) as
directed in Exhibit E,
Section 6.4.
Revise within 30 days
after contract award
and receipt of USEPA
comments .
Submit within 7 days
of receipt of written
request to recipients
as directed. (See
Exhibit E, Section 5)
Submit within 14 days
of amended QAP as
directed in Exhibit E,
Section 5.3.
Retain for 3 years
after data submission.
Submit within 7 days
after receipt of
written request by the
USEPA Regional CLP PO.
(See Exhibit E,
Section 13)
Distribution
Q
c o
O CU
H CO
O 0i Cu E-i
S Q) ťJ <
c/j os o a
As Directed
Amended SOPs
distributed to
CLP PO and QATS
As Directed
Amended QAP
distributed to
CLP PO and QATS
As Directed
ILM05.2
B-6
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Exhibit B Section 1
Contract Reports/Deliverables Distribution (Con't)
Footnotes:
AThe number of copies specified is the number of copies required to be
delivered to each recipient.
Contractor-concurrent delivery to USEPA's designated recipient [e.g.,
Quality Assurance Technical Support (QATS)] may be required upon request by
the USEPA OERR Analytical Operations/Data Quality Center (AOC) Inorganic
Program Manager (AOC PM). Retain for 365 days after data submission, and
submit as directed within 7 days after receipt of written request by the USEPA
AOC PM.
cThe number of days associated with these elements will be provided in
the associated laboratory contract document and will also be provided at the
time of sample scheduling by the Sample Management Office (SMO) Contractor.
"The CLP PO is the USEPA Regional Contract Laboratory Program (CLP)
Project Officer (CLP PO) designated on the contract.
Validated Time of Sample Receipt (VTSR) is the date of sample receipt
at the Contractor's facility, as recorded on the shipper's delivery receipt
and sample Traffic Report/Chain of Custody Record. Sample Delivery Group
(SDG) is a group of samples within a Case, received over a period of 7 days or
less with the same laboratory turnaround and not exceeding 20 samples
[excluding Performance Evaluation (PE) samples]. Data for all samples in the
SDG are due concurrently. The date of delivery of the SDG or any samples
within the SDG is the date that the last sample in the SDG is received. See
Exhibit A for further description.
2DELIVERABLES 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 electronic deliverable. 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 received after this time will be considered late.
'Complete SDG File (CSF) will contain the original Sample Data Package
plus all of the original documents described in Exhibit B, Section 2.6.
4If required at the time of sample scheduling, the Contractor shall
provide Preliminary Results, consisting of all Form Is (see Exhibit B,
Section 2.9). Facsimile or electronic transmittal is required as requested by
the Region. Electronic transmittals shall be transmitted as WordPerfect, MS
Word, PDF, or other USEPA-approved formats. The Contractor will be notified
of the format, fax numbers, or email address(es) at the time of sample
scheduling. Sample Traffic Reports/Chain of Custody Records and SDG Cover
Sheets shall be submitted with the Preliminary Results. The Contractor shall
document all communication in a telephone log.
Preliminary Results Delivery Schedule:
If a sample requiring Preliminary Results arrives before 5 p.m., the
Preliminary Results are due within the required turnaround time. If a sample
requiring Preliminary Results is received after 5 p.m., the Preliminary
Results are due within the required turnaround time beginning at 8 a.m. the
following day.
5Also required in each Sample Data Package.
6See Exhibit E for description. Time is cited in calendar days.
B-7 ILM05.2
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Exhibit B Section 1
Contract Reports/Deliverables Distribution (Con't)
Footnotes (Con't):
7The Contractor shall deliver both hardcopy and electronic (i.e.,
diskette) copies of the Standard Operating Procedures (SOPs) and Quality
Assurance Management Plan (QAP).
1.2 Distribution
The following addresses correspond to the "Distribution" column in
Exhibit B, Section 1.1, Table 1.
SMO: USEPA Contract Laboratory Program .(CLP)
Sample Management Office (SMO) x
2000 Edmund Halley Drive
Reston, VA 20191-3400
Region: USEPA REGIONS: SMO will provide the Contractor with the list
of addressees for data delivery for the 10 USEPA 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.
USEPA Regional CLP Project Officer (CLP PO):
SMO will provide the Contractor with the list of addresses
for the USEPA Regional CLP POs. SMO will provide the
Contractor with updated name/address lists as necessary
throughout the period of the contract.
QATS: USEPA Contract Laboratory Program (CLP)
Quality Assurance Technical Support (QATS) Laboratory2
2700 Chandler Avenue, Building C
Las Vegas, NV 89120
Attn: Data Audit Staff
In addition, the mailing and delivery addresses for the USEPA AOC
Inorganic Program Manager (AOC PM) are:
Mailing Address: USEPA OERR Analytical Operations/
Data Quality Center
Ariel Rios Building (5204G)
1200 Pennsylvania Avenue, N.W.
Washington, DC 20460
Attn: CLP Inorganic Program Manager
Fed-Ex/Overnight USEPA OERR Analytical Operations/
Delivery: Data Quality Center
1235 Jefferson Davis Highway
Crystal Gateway I, 12th Floor
Arlington, VA 22202
Attn: CLP Inorganic Program Manager
1The SMO is a Contractor-operated facility operating under the SMO
contract awarded and administered by USEPA.
2The QATS laboratory is a Contractor-operated facility operating under
the QATS contract awarded and administered by USEPA.
ILM05.2 B-8
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Exhibit B Section 2
Reporting Requirements and Order of Data Deliverables
2.0 REPORTING REQUIREMENTS AND ORDER OF DATA DELIVERABLES
2.1 Introduction
The Contractor shall provide reports and other deliverables as specified
in Exhibit B, Section 1.1. The required content and form of each
deliverable is described in this exhibit. All reports and documentation
shall be:
;I! Legible;
111 Clearly labeled and completed in accordance with instructions in this
exhibit;
:*' Arranged in the order specified in this section;
=" Paginated sequentially according to instructions in this exhibit; and
=" Double-sided.
NOTE: Complete Sample Delivery Group (SDG) Files (CSFs) need not be
double-sided. (The CSF is composed of original documents.) However,
Sample Data Packages delivered to the USEPA Contract Laboratory Program
(CLP) Sample Management Office (SMO) and the Region, [and USEPA
designated recipients, e.g., Quality Assurance Technical Support (QATS),
upon written request] must be double-sided.
2.1.1 The Contractor shall use EPA Case numbers, SDG numbers, and EPA
sample numbers to identify samples received under this contract, both
verbally and in reports and correspondence. The contract number
shall be specified in all correspondence.
2.1.2 Section 4 of this exhibit contains the required Data Reporting Forms
in Agency-specified format. Section 3 of this Exhibit contains
instructions to the Contractor for properly completing all data
reporting forms to provide USEPA with all required data. Data
elements and field descriptors for reporting data in computer-
readable format are contained in Exhibit H.
2.2 Resubmission of Data
If submitted documentation does not conform to the above criteria, the
Contractor is required to resubmit such documentation with
deficiency(ies) corrected within 4 business days, at no additional cost
to USEPA.
Ť
2.2.1 Whenever the Contractor is required to submit or resubmit data as a
result of an on-site laboratory evaluation, through the USEPA
Regional CLP Project Officer (CLP PO) action, or through a Regional
data reviewer's request, the data shall be clearly marked as
"Additional Data" and shall be sent to both contractual data
recipients (SMO and Region) and to USEPA's designated recipient
(e.g., QATS) when a written request for the Sample Data Package has
been made. A cover letter shall be included which describes what
data is being delivered, to which USEPA Case(s) the data pertains,
and who requested the data .
2.2.2 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 to USEPA's designated recipient (e.g., QATS) when a written
request for the Sample Data Package has been made. In all instances,
the Contractor shall include a color-coded cover sheet (Laboratory
B-9 ILM05.2
-------
Exhibit B Section 2
Reporting Requirements and Order of Data Deliverables (Con't)
Response to Results of Contract Compliance Screening) provided by
SMO. Electronic 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.
2.3 Quality Assurance (QA) Management Plan and Standard Operating Procedures
(SOPs)
The Contractor shall adhere to the requirements in Exhibits E and F.
2.4 Sample Traffic Reports/Chain of Custody Records
Each sample received by the Contractor will be labeled with an EPA
sample number and will be accompanied by a Sample Traffic Report/Chain
of Custody Record bearing the sample number and descriptive information
regarding the sample. The current CLP Traffic Report is the "Inorganic
Traffic Report & Chain of Custody Record". The CLP Traffic Report/Chain
of Custody Record is one form divided into two sections: the Traffic
Report section which consists of everything above the Chain of Custody
Record section, and the bottom section which is the Chain of Custody
Record. The Contractor shall complete the CLP Traffic Report/Chain of
Custody Record (marked "Lab Copy for Return to SMO"), recording the date
of sample receipt, verifying the number of samples, and signing the CLP
Traffic Report/Chain of Custody Record.
Upon receipt, the Contractor shall sign for receipt of samples.. The
laboratory signature box is located at the bottom of the CLP Traffic
Report/Chain of Custody Record in the Chain of Custody Record section.
The laboratory sample custodian or designated recipient opening and
verifying the contents of the cooler shall then verify receipt of all
samples identified within the CLP Traffic Report section and sign and
date the signature box located in the upper half of the CLP Traffic
Report/Chain of Custody Record. If a non-CLP Traffic Report/Chain of
Custody Record is submitted with the samples, for example a Regional
Traffic Report/Chain of Custody Record, then the Contractor shall (1)
sign and date receipt of the samples to maintain the chain-of-custody
and (2) the sample custodian or designated recipient shall sign and date
the Traffic Report/Chain of Custody Record to verify sample information.
The Contractor shall also enter the Sample Delivery Group (SDG) number.
Case number, and the laboratory contract number on the CLP Traffic
Report/Chain of Custody Record, in the appropriate boxes. 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. Under no circumstances should any SDG number be replicated
within a Case. If necessary, select an alternative sample number for
the SDG number. The SDG number is also reported on all data reporting
forms (see Exhibit B, Section 3 - Form Instructions). If the laboratory
is requested to transfer samples to another facility, the Contractor
shall date and enter the name of the facility to where the samples will
be transferred on the CLP Traffic Report/Chain of Custody Record.
2.4.1 The Contractor shall submit Traffic Reports/Chain of Custody Records
in SDG sets (i.e.. Traffic Reports/Chain of Custody Records for all
samples in an SDG shall be clipped together), with an SDG Coyer Sheet
attached. The SDG Cover Sheet shall contain the following items:
ILM05.2 B-10
-------
Exhibit B Section 2
Reporting Requirements and Order of Data Deliverables (Con't)
* Laboratory name;
*= Contract number;
^ Sample analysis price (full sample price from the contract);
ť Case number; and
* List of EPA sample numbers of all samples in the SDG, identifying
the first and last samples received, and their Laboratory Receipt
Dates (LRDs).
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).
2.4.2 EPA field sample numbers are six digits in length and continuous
(without spaces or hyphens). If the Contractor receives sample
numbers of any other length, the Contractor shall contact SMO
immediately. The original Sample Traffic Report/Chain of Custody
Record page marked "Lab Copy for Return to SMO", with laboratory
receipt information and signed with original Contractor signature,
shall be submitted for each sample in the SDG.
2.4.3 - If samples are received at the laboratory with multi-sample Traffic
Reports/Chain of Custody Records, all the samples on one multi-sample
. . Traffic Report/Chain of Custody Record may not necessarily be in the
same SDG. In this instance, the Contractor shall make the
appropriate number of photocopies of the Traffic Report/Chain of
1 Custody Record, and submit one copy with each SDG Cover Sheet.
2.5 Sample Data Package
The Sample Data Package shall include data for analysis of all samples
in one SDG, including field and analytical samples, blanks, spikes,
duplicates, and Laboratory Control Samples (LCSs). The Sample Data
Package shall be complete before submission, and shall be consecutively
paginated (starting with page number one and ending with the number of
all pages in the package). The Sample Data Package shall include the
following:
2.5.1 Cover Documentation
2.5.1.1 Cover Page for the inorganic analyses Data Package shall include:
laboratory name; laboratory code; contract number; Case number;
SDG number; Non-Routine Analytical Service (NRAS) number (if
appropriate); EPA sample numbers in alphanumeric order showing EPA
sample numbers cross-referenced with laboratory Sample ID numbers;
and completion of the questions on use of background and
interelement corrections for the samples.
2.5.1.1.1 The Cover Page shall contain the following statement, verbatim:
"I certify that this Sample 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 Sample Data
Package and in the computer-readable data submitted on diskette
(or via an alternate means of electronic transmission, if
approved in advance by USEPA) has been authorized by the
Laboratory Manager or the Manager's designee, as verified by
B-ll ILM05.2
-------
Exhibit B Section 2
Reporting Requirements and Order of Data Deliverables (Con't)
the following signature." This statement shall be directly
followed by the signature of the Laboratory Manager or designee
with typed lines containing the signer's name and title, and
the date of signature.
2.5.1.2 SDG Narrative. This document shall be clearly labeled "SDG
Narrative" and shall contain: laboratory name. Case number, SDG
number, contract number, and detailed documentation of any Quality
Control (QC), sample, shipment, and/or analytical problems
encountered in processing the samples reported in the Sample Data
Package. The Contractor shall include any technical and
administrative problems encountered and the resolution or
corrective actions taken. This includes documenting the
alternative technique used to determine cooler temperature if a
temperature indicator bottle is not present in the cooler. The
Contractor shall also provide, in the SDG Narrative, sufficient
information, including equations or curves (at least one equation
or curve per method), to allow the recalculation of sample results
from raw instrument output. The Contractor shall also include a
discussion of any flexibility Statement of Work (SOW)
modification. This includes attaching a copy of the USEPA
approved modification form to the SDG Narrative. Additionally the
Contractor shall also identify and explain any differences which
exist between the Form Is and supporting documentation provided in
the data package and those previously provided as Preliminary
Results.
2.5.1.3 Sample Log-In Sheet [Form DC-1]
2.5.1.4 Full Inorganics Complete SDG File (CSF) Inventory Sheet [Form DC-
2]
2.5.2 Sample Data
Sample data shall be submitted with the inorganic analysis data
reporting forms for all samples in the SDG. Data should be arranged
in increasing alphanumeric EPA sample number order, followed by the
QC analyses data, quarterly and annual verification of method and
instrument parameters forms, raw data, and copies of the digestion
and distillation logs.
2.5.2.1 Inorganic Analysis Data Sheet [Form IA-IN and Form IB-IN].
Tabulated analytical results of the requested analytes shall be
included. The validation and release of these results is
authorized by a specific signed statement on the Cover Page. In
the event that the laboratory cannot verify all data reported for
each sample, the Laboratory Manager shall provide a detailed
description of the problems associated with the sample(s) in the
SDG Narrative.
2.5.2.1.1 Appropriate concentration units shall be specified and entered
on Forms IA-IN and IB-IN. The quantitative values shall be
reported in units of micrograms per Liter (UG/L) for water
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 and 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 IA-
IN, IB-IN, and IX-IN only. For other forms, follow the
ILM05.2 B-12
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Exhibit B Section 2
Reporting Requirements and Order of Data Deliverables (Con't)
instructions specific to those forms as discussed in this
exhibit.
2.5.2.2 Quality Control (QC) Data
2.5.2.2.1 The QC summary for inorganic analysis shall contain the forms
listed below.
NOTE: If more than one form is necessary, duplicate forms must
be arranged in chronological order.
2.5.2.2.1.1 Initial and Continuing Calibration Verification [Form IIA-
IN]
2.5.2.2.1.2 CRQL Check Standard [Form IIB-IN]
2.5.2.2.1.3 Blanks [Form III-IN]
2.5.2.2.1.4 ICP-AES Interference Check Sample [Form IVA-IN]
2.5.2.2.1.5 ICP-MS Interference Check Sample [Form IVB-IN]
2.5.2.2.1.6 Matrix Spike Sample Recovery [Form VA-IN]
2.5.2.2.1.7 Post-Digestion Spike Sample Recovery [Form VB-IN]
2.5.2.2.1.8 Duplicates [Form VI-IN]
2.5.2.2.1.9 Laboratory Control Sample [Form VII-IN]
2.5.2.2.1.10 ICP-AES and ICP-MS Serial Dilutions [Form VIII-IN]
2.5.2.2.1.11 Method Detection Limits (Annually) [Form IX-IN]
2.5.2.2.1.12 ICP-AES Interelement Correction Factors (Quarterly)
- [Form XA-IN]
2.5.2.2.1.13 ICP-AES Interelement Correction Factors (Quarterly)
[Form XB-IN]
2.5.2.2.1.14 ICP-AES and ICP-MS Linear Ranges (Quarterly) [Form XI-IN]
2.5.2.2.1.15 Preparation Log [Form XII-IN]
2.5.2.2.1.16 Analysis Run Log [Form XIII-IN]
2.5.2.2.1.17 ICP-MS Tune [Form XIV-IN]
2.5.2.2.1.18 ICP-MS Internal Standards Relative Intensity Summary [Form
XV-IN]
2.5.2.3 Raw Data
For each reported value, the Contractor shall include in the
Sample 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 and annual verification
of method and instrument parameters submitted as a part of each
Sample Data Package. When analysis of the ICP-AES or ICP-MS
target analytes listed in Exhibit C of this SOW (or any subset or
additional analytes) is requested, the raw data shall include, for
all samples, not only the results for the requested analyte(s),
B-13 ILM05.2
-------
Exhibit B Section 2
Reporting Requirements and Order of Data Deliverables (Con't)
but also those for all the interferents (Exhibit D/ICP-AES, Table
1, or Exhibit D/ICP-MS, Section 7.2.4.4.1, as appropriate). The
raw data shall also contain the results of any other analyte(s)
which have been determined to interfere with the requested
analytes(s).
2.5.2.3.1 Raw data shall contain all instrument readouts and data
pertinent to the reconstruction of the analysis and results
(e.g., Batch Sheets) used for the sample results. Each
exposure or instrumental reading shall be provided, including
those readouts that may fall below the Method Detection Limit
(MDL). Raw data shall not be corrected for dilutions or volume
adjustments. All Atomic Absorption (AA), Inductively Coupled
Plasma - Atomic Emission Spectrometer (ICP-AES), and
Inductively Coupled Plasma - Mass Spectrometry (ICP-MS)
instruments shall provide a legible hardcopy of the direct
real-time instrument readout (i.e., strip charts, printer
tapes, etc.) or a printout of the unedited instrument data
output file. A photocopy of the instrument's direct sequential
readout shall be included. A hardcopy of the instrument's
direct readout shall be included for cyanide if the
instrumentation has the capability.
2.5.2.3.2 The order of raw data in the Sample Data Package for inorganic
analyses shall be: ICP-AES, Graphite Furnace Atomic Absorption
(GFAA), ICP-MS, Mercury, and Cyanide. All raw data shall
include concentration units for ICP, and absorbances or
concentration units for Mercury and Cyanide.
2.5.2.3.3 The ICP-MS raw data shall also contain the turbidity
measurements results [in Nephelolometric Turbidity Units (NTU)]
for the field samples.
2.5.2.3.4 Corrections to the laboratory data reporting forms 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.
2.5.2.3.5 Raw data shall be labeled with EPA sample numbers and
appropriate codes, shown in Exhibit B, Table 2 - Codes for
Labeling Data, following, to unequivocally identify:
lx: Calibration standards, including source and preparation
date. Standard preparation logbooks can be submitted if
they contain this information;
^ Initial and Continuing Calibration Blanks (ICBs/CCBs) and
Preparation Blanks (PBs);
"= Initial and Continuing Calibration Verification (ICV/CCV)
standards, Interference Check Samples (ICSs), serial
dilution samples, Contract Required Quantitation Limit
(CRQL) Check Standard (CRI), LCS, and post digestion spike;
00 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);
<* Duplicates;
ILM05.2 B-14
-------
Exhibit B Section 2
Reporting Requirements and Order of Data Deliverables (Con't)
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;
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; and
Time and date of each analysis. Instrument run logs can
also be submitted if they contain time and date of
analysis. If the instrument does not automatically provide
times of analysis, these shall be manually entered on all
raw data (e.g., ICV/CCV, blanks, and the CRQL Check
Standard).
Table 2
Codes for Labeling Data 1-2-3
Sample
Sample Not Part of the SDG
Duplicate
Matrix Spike
Serial Dilution
Analytical Spike/Post
Digestion/Distillation Spike
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
CRQL Check Standard
Laboratory Control Samples:
Aqueous (Water)
Solid (Soil/Sediment)
Preparation Blank (Water)
Preparation Blank (Soil)
Linear Range Analysis Standard
Baseline Correction
Reslope
Cyanide Mid-Range Standard
ICP-MS Tune Check
XXXXXX
ZZZZZZ
XXXXXXD
xxxxxxs
XXXXXXL
XXXXXXA
S or SO for blank standard
SO, S10,...etc.
ICV##
ICB##
CCVff
CCBff
ICSAff
ICSABtt
CRI##
LCSW#f
LCSSff
PBW##
PBSf#
LRSf#
BASELINEff
RESLOPEf*
MIDRANGE##
TUNE##
B-15
ILM05.2
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Exhibit B Section 2
Reporting Requirements and Order of Data Deliverables (Con't)
lThe numeric suffix that follows the "S" suffix for the standards
indicates the true value of the concentration of the standard in ug/L.
2ICP-AES and ICP-MS 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".
3The EPA sample number shall be unique for each ICV, ICB, CCV, CCB,
ICSA, ICSAB, CRI, LCSW, LCSS, PBW, PBS, LRS, BASELINE, RESLOPE, MIDRANGE, and
TUNE within an analysis or preparation method, within an SDG. The Contractor
shall achieve this by replacing the two-character terminator (##) of the
identifier with one or two characters, numbers, or a combination of both.
2.5.2.4 Digestion and Distillation Logs. The following logs shall be
submitted as appropriate for each preparation procedure: digestion
logs for ICP-AES, ICP-MS, mercury preparations, and cyanide.
These logs shall include: (1) date; (2) sample weights and
volumes, with initial sample weight/volume and final volume
clearly indicated; (3) sufficient information to unequivocally
identify which QC samples (i.e., LCS, PB) correspond to each batch
digested; (4) comments describing any significant sample changes
or reactions which occur during preparation shall be entered in
the log and noted in the SDG Narrative; (5) indication of pH less
than 2 or greater than 12, as applicable; and (6) identification
of the sample preparer(s) [signature(s)].
2.5.3 A copy of the Sample Traffic Reports/Chain of Custody Records
submitted in Exhibit B, Section 2.4, for all of the samples in the
SDG. The Traffic Reports/Chain of Custody Records 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.
2.6 Complete SDG File (CSF)
As specified in the Delivery Schedule, one CSF (including the original
Sample Data Package) shall be delivered to the Region concurrently with
the delivery of a copy of the Sample Data Package to SMO. Delivery to
USEPA's designated recipient (e.g., QATS) is only required upon written
request.
2.6.1 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 USEPA with another Case/SDG in accordance with the
requirements described in Exhibit F. The CSF shall contain all
original documents and be numbered according to the specifications in
Exhibit B, Sections 3 and 4, and Form DC-2.
2.6.2 The CSF shall consist of the following original documents in addition
to the documents in the Sample Data Package.
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 USEPA, as well as copies
that are altered in any fashion, are also deliverables to USEPA.
Send the original to the Region and a copy to SMO. Send to USEPA's
designated recipient (e.g., QATS) only upon written request.
ILM05.2 B-16
-------
Exhibit B Section 2
Reporting Requirements and Order of Data Deliverables (Con't)
2.6.2.1 Original Sample Data Package
2.6.2.2 A completed and signed Full Inorganics Complete SDG File (CSF)
Inventory Sheet [Form DC-2]
2.6.2.3 All original shipping documents, including, but not limited to,
the following documents:
'*= USEPA Sample Traffic Reports/Chain of Custody Records
"= Airbills (if an airbill is not received, include a hardcopy
receipt requested from the shipping company or a printout of
the shipping company's electronic tracking information); and
'Ť= Sample Tags (if present) sealed in plastic bags.
2.6.2.4 All original receiving documents, including, but not limited to,
the following documents:
" Form DC-1;
^ Other receiving forms or copies of receiving logbooks; and
Ť SDG Cover Sheet.
2.6.2.5 All original laboratory records of sample transfer, preparation,
and analysis, including, but not limited to, the following
documents:
=*= Original preparation and analysis forms or copies of
preparation and analysis logbook pages; and
^ Internal sample and sample digestate and distillate transfer
Chain of Custody Records.
2.6.2.6 All other original SDG-specific documents in the possession of the
laboratory, including, but not limited to, the following
documents:
=" Telephone contact logs;
-*= Copies of personal logbook pages;
'x: All handwritten SDG-specific notes; and
:x: Any other SDG-specific documents not covered by the above.
2.6.3 If the Contractor does submit SDG-specific documents to USEPA after
submission of the CSF, the documents shall be numbered as an addendum
to the CSF and a revised Form DC-2 shall be submitted; or the
documents shall be numbered as a new CSF and a new Form DC-2 shall be
submitted to the Region only.
2.6.4 The Contractor shall retain a legible electronic (PDF) or hard copy
of the CSF for 365 days after submission of the reconciled data
package. After this time, the Contractor may dispose of the package.
2.7 Data in Computer-Readable Format
The Contractor shall provide a computer-readable copy for all samples in
the SDG, as specified in Exhibit H, and delivered as specified in
Exhibit B, Section 1.1. Computer-readable data deliverables shall be
submitted on DOS formatted 3.5-inch high density 1.44 MB diskette (s) (or
B-17 ILM05.2
-------
Exhibit B Section 2
Reporting Requirements and Order of Data Deliverables (Con't)
via an alternate means of electronic transmission, if approved in
advance by USEPA).
2.7.1 When submitted, diskette(s) 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/cold or any type of electromagnetic
radiation. The diskette(s) shall be included in the same shipment as
the hardcopy data, and, at a minimum, be enclosed in a diskette
mailer.
2.7.2 The data shall be recorded in the file format and adhere to the file,
record, and field specifications listed in Exhibit H, "Data
Dictionary and Format for Data Deliverables in Computer-Readable
Format".
2.8 Results of the Intercomparison and Performance Evaluation (PE) Sample
Analyses
Tabulation of analytical results for intercomparison/PE sample analyses
includes all requirements specified in Exhibit B, Sections 2.5 and 2.7.
2.9 Preliminary Results
The Form Is data results (including all appropriate qualifiers and
flags) shall be submitted for all samples in one SDG of a Case. Sample
analysis shall follow all requirements stipulated in Exhibit D. The
Contractor shall clearly identify the Preliminary Results by labeling
each Form I as "Preliminary Results" under the form title (e.g., under
Inorganic Analysis Data Sheet). The Contractor shall also include a
disclaimer in the "Comments" field on all Form Is stating that the "Data
results contained on this Form I are for scanning purposes only, and may
not have been validated for CLP criteria." Sample Traffic Reports/Chain
of Custody Records and SDG Cover Sheets shall be submitted with the
Preliminary Results.
2.9.1 The Contractor shall submit'the Cover Page following the
specifications in Exhibit B, Sections 2.5.1 and 3.4.1. The Cover
Page shall be clearly labeled to indicate that the data being
reported are Preliminary Results. The Cover Page shall contain the
following statement, verbatim : "I certify that these Preliminary
Results are 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 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 designee with typed lines containing the
signer's name and title, and the date of signature.
2.10 Quarterly Verification of Linear Ranges and Interelement Correction
Factors and Annual Verification of MDLs
The Contractor shall perform and report quarterly verification of
instrument linear range and annual verification of MDLs by the methods
specified in Exhibit D for each instrument used under this contract.
The Contractor shall also perform and report quarterly ICP-AES
interelement correction factors (including method of determination),
wavelengths used, and integration times. Forms reporting results for
quarterly and annual verification of method and instrument parameters
for the current quarter and year shall be submitted in each Sample Data
Package, using Inorganic Forms IX, XA, XB, and XI. Submission of the
quarterly and annual verification of method and instrument parameters
shall include the raw data used to determine the values reported.
ILM05.2 B-18
-------
Exhibit B Section 2
Reporting Requirements and Order of Data Deliverables (Con't)
2.11 Electronic Instrument Data
The Contractor shall adhere to the requirements in Exhibit E.
2.12 Corrective Action Procedures
If the Contractor fails to adhere to the requirements detailed in this
SOW, the Contractor will be in noncompliance with the contract and may
be subjected to sanctions as described in the contract.
B-19 ILM05.2
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Exhibit B Section 3
Form Instructions
3.0 FORM INSTRUCTIONS
3.1 Introduction
This section contains specific instructions for the completion of all
required Inorganic Data Reporting Forms.
3.2 General Information
Values shall be reported on the hardcopy forms according to the
respective 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 if the information
on those forms can be submitted on one form.
3.2.1 The data reporting forms discussed in Exhibit B, Section 3.4, and
presented in Exhibit B, Section 4.0, have been designed in
conjunction with the computer-readable data formats 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: On the hardcopy forms, the space provided for entries is
greater in some instances than the length prescribed for the variable
as written to the electronic deliverable (see Exhibit H). Greater
space is provided on the hardcopy forms for the sake of visual
clarity.
3.2.2 All characters which appear on the data reporting forms presented in
the contract 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 USEPA Regional Contract Laboratory Program Project Officer (CLP
PO) or the USEPA OERR Analytical Operations/Data Quality Center (AOC)
Inorganic Program Manager (AOC PM). The names of 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").
3.2.3 Alphabetic entries made onto the forms by the Contractor shall be in
ALL 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.
3.3 Header Information
Six pieces of information are common to the header sections of each data
reporting form. These are: Laboratory Name, Contract, Laboratory Code,
Case number, Non-Routine Analytical Services (NRAS) number, and Sample
Delivery Group (SDG) number. Except as noted for NRAS number, this
information shall be entered on every form and shall match on all forms.
3.3.1 Laboratory Name. The "Lab Name" shall be the name chosen by the
Contractor to identify the laboratory. It may not exceed 25
characters.
ILM05.2 B-20
-------
Exhibit B Section 3
Form Instructions (Con't)
3.3.2 Contract. The "Contract" is the number of the USEPA contract under
which the analyses were performed.
3.3.3 Laboratory Code. The "Lab Code" is an alphabetic abbreviation of up
to six characters, assigned by USEPA, to identify the laboratory and
aid in data processing. This laboratory code will be assigned by
USEPA at the time a contract is awarded. The laboratory code shall
not be modified by the Contractor, except at the direction of USEPA.
If a change of name or ownership occurs at the laboratory, the
laboratory code will remain the same until the Contractor is directed
by USEPA to use another laboratory code.
3.3.4 Case Number. The "Case No." is the SMO-assigned Case number (to five
characters) associated with the sample, and reported on the Traffic
Report/Chain of Custody Record.
3.3.5 NRAS Number. The "NRAS No." is the USEPA assigned number for
analyses performed under Non-Routine Analytical Services (NRAS). If
samples are to be analyzed under NRAS only, and reported on these
forms, then enter the NRAS number and leave the Case number blank.
If samples are analyzed according to the Routine Analytical Services
(RAS) protocol and have additional NRAS requirements, list both the
Case number and NRAS number on all forms. If the analyses have no
NRAS requirements, leave the "NRAS No." field blank.
3.3.6 SDG Number. 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, except when this would cause duplication. 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. If fractions of the same field samples are scheduled under
different turnaround times, thus creating separate SDGs containing
the same sample numbers, a different sample number shall be utilized
in the assignment of the SDG number for each SDG. If a situation
arises where there are an insufficient number of samples for
assignment of SDG numbers, the contractor shall contact SMO for the
* assignment of a SDG number.
3.3.7 Sample Number. The "EPA Sample No." appears either in the header
information of the form or as the left column of a table summarizing
data from a number of samples. When an EPA sample number is entered
in the triple-spaced box in the upper right-hand corner of a form, it
shall be centered on the middle line of the three lines that form the
box.
3.3.7.1 All samples, matrix spikes, post digestion/distillation spikes,
duplicates, and serial dilutions shall be identified with an EPA
sample number. For samples, an EPA sample number is the unique
identifying number given in the Traffic Report/Chain of Custody
Record that accompanied that sample. In order to facilitate data
assessment, the sample suffixes listed in Exhibit B, Table 2 -
Codes for Labeling Data, must be used.
3.3.8 Other Common Fields. 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 "WATER"
for water samples.
NOTE: The matrix must be spelled out. Abbreviations such as "S"
or "W" shall not be used.
B-21 ILM05.2
-------
Exhibit B Section 3
Form Instructions - '
Cover Page
'" For "Level", enter the determination of concentration level.
Enter as "LOW" or "MED", not "L" or "M".
3.3.9 Rounding Rule. For rounding off numbers to the appropriate level of
precision, observe the following common rules. If the figure
following those to be retained is greater than or equal to 5, round
up; otherwise round down. Also see "Rounding Rules" in Exhibit G.
3.3.9.1 Before evaluating a number for being in control or out of control
of a certain limit [other than the Contract Required Quantitation
Limit (CRQL)], the number evaluated shall be rounded using the
above rounding rules to the significance reported for that limit.
For example, the control limit for an Initial Calibration
Verification is plus or minus 10% of the true value. Then a
calculated percent recovery of 110.46 shall be reported on
Form IIA-IN as 110, which is within the control limits of 90-110.
On the other hand, a calculated percent recovery of 110.50 shall
be reported on Form IIA-IN as 111, which is not within the 90-110
percent control limits.
NOTE: All results shall be transcribed to Inorganic Forms IIA-IN
through XV-IN 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 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
three
decimal
decimal
places)
places)
two decimal places)
four
four
decimal
decimal
places)
places)
95.
95.
96.
95.
95.
9965
997
00
9960
9000
3.4 Inorganic Forms
3.4.1 Cover Page - [COVER PAGE]
3.4.1.1 Purpose. This form is used to list all samples analyzed within an
SDG and provide certain analytical information and general
comments. It is also the document that is signed by the
Laboratory Manager to authorize and release all data and
deliverables associated with the SDG.
3.4.1.2 Instructions. Complete the header information according to the
instructions in Exhibit B, Section 3.3. Complete the remainder of
the form using the following instructions.
3.4.1.2.1 For samples analyzed using this Statement of Work (SOW), enter
"ILM05.2" for the SOW Number.
3.4.1.2.2 Enter an EPA sample number 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
ILM05.2 B-22
-------
Exhibit B Section 3
Form Instructions
Forms IA-IN and IB-IN
both alpha and numeric characters) EPA sample number within the
SDG, it would be entered in the first EPA sample number field.
Samples would be listed below it, in ascending sequence -
MAB124, MAB125, MAC111, MA1111, MA1111D, etc.
3.4.1.2.3 A maximum of 20 field sample numbers (excluding PE samples) 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 22.
3.4.1.2.4 A Laboratory Sample ID (to ten spaces) may be entered for each
EPA sample number. If a Laboratory Sample ID is entered, it
shall be entered identically (for each EPA sample number) on
all associated data.
3.4.1.2.5 Enter "YES" or "NO" in answer to each of the two questions
concerning Inductively Coupled Plasma - Atomic Emission
Spectrometer (ICP-AES) and Inductively Coupled Plasma - Mass
Spectrometry (ICP-MS) 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".
3.4.1.2.6 Under "Comments", enter any statements relevant to the analyses
performed under the SDG as a whole.
3.4.1.2.7 Each Cover Page shall be signed and dated, in original, by the
Laboratory Manager or the Manager's designee to authorize the
release and verify the contents of all data and deliverables
associated with an SDG.
3.4.2 Inorganic Analysis Data Sheet [Forms IA-IN and IB-IN]
3.4.2.1 Purpose. These forms are used to tabulate and report sample
analysis results for inorganic target analytes (see Exhibit C).
3.4.2.2 Instructions. Complete the header information according to the
instructions in Exhibit B, Section 3.3. Complete the remainder of
the form using the following instructions.
3.4.2.2.1 "Date Received" is the date (formatted MM/DD/YYYY) of sample
receipt at the laboratory, as recorded on the Traffic
Report/Chain of Custody Record [i.e., the Validated Time of
Sample Receipt (VTSR)].
3.4.2.2.2 "% Solids" is the percent of solids on a weight-by-weight basis
in the sample which is determined by drying the sample as
specified in Exhibit D - Introduction to Analytical Methods,
Section 1.6. 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 is less than 1% solid, then enter
"0.0".
3.4.2.2.3 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.
3.4.2.2.4 Under the column labeled "Concentration", enter for each
analyte, the value of the result [if the concentration is
greater than or equal to the Method Detection Limit (MDL)]
corrected for any dilutions; or, enter the CRQL for the
B-23 ILM05.2
-------
Exhibit B Section 3
Form Instructions
Forms IA-IN and IB-IN (Con't)
analyte, adjusted if necessary and corrected for any dilutions,
if the concentration is less than the MDL. The concentration
result shall be reported to two significant figures if the
result is less than 10 or three significant figures if the
value is greater than or equal to 10.
3.4.2.2.5 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.
Forms IA-IN and IB-IN include fields for three types of result
qualifiers. These qualifiers shall be completed as follows:
3.4.2.2.5.1 C (Concentration) Qualifier. Enter "J" if the reported
value was obtained from a reading that was less than the
CRQL but greater than or equal to the MDL. If the reading
was less than the MDL, a "U" shall be entered.
The MDL obtained for a given preparation method, analysis
method, and instrument shall be used for qualification of
the results for samples associated with that preparation
method, analysis method, and instrument. Serial dilution
and post-digestion spike results shall be qualified using
the MDL and CRQL values utilized for the corresponding field
sample.
All three values (i.e., the instrument reading, CRQL, and
MDL) shall be converted to the same units prior to
determining the appropriate C (Concentration) Qualifier.
NOTE: The water CRQL (in ug/L) and the MDL obtained from
direct analysis (Preparation Method "NP1") for a given
analysis method and instrument shall be used to qualify the
results of samples and instrument QC standards that are not
taken through a preparation procedure [e.g., ICP-MS samples
with turbidity less than 1 Nephelolometric Turbidity Unit
(NTU), ICB, CCB, and CRI for ICP-AES].
3.4.2.2.5.2 Q Qualifier. Specified entries and their meanings are as
follows:
E: The reported value is estimated due to 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 IA-IN or Form IB-IN (if it
is an isolated problem).
N: Spiked sample recovery not within control limits.
*: Duplicate analysis not within control limits.
D: The reported value is from a dilution.
ILM05.2 B-24
-------
Exhibit B Section 3
Form Instructions
Form IIA-IN
3.4.2.2.5.3 M (Analysis Method) Qualifier. Specified entries and their
meanings are as follows:
P: ICP-AES
MS: ICP-MS
CV: Manual Cold Vapor Atomic Absorption (AA)
AV: Automated Cold Vapor AA
AS: Semi-Automated Spectrophotometric
C: Manual Spectrophotometric
" ": Where no data have been entered
NR: If the analyte is not required to be analyzed
3.4.2.2.6 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, and black;
a> Clarity - clear, cloudy, and opaque; and
= Texture - fine (powdery), medium (sand), and 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. Also document raw instrument results that
are less than minus two times the CRQL (-2xCRQL) in the
"Comments" field and in the Sample Delivery Group (SDG)
Narrative.
3.4.2.2.7 If more than two additional analytes were requested, submit
Form IB-IN as appropriate.
3.4.3 Initial (ICV) and Continuing Calibration Verification (CCV) [Form
IIA-IN]
3.4.3.1 Purpose. This form is used to report analyte recoveries from
calibration verification solutions.
3.4.3.2 Instructions. Complete the header information according to the
instructions in Exhibit B, Section 3.3. Complete the remainder of
the form using the following instructions.
3.4.3.2.1 Enter the ICV Source (12 characters maximum) and the CCV Source
(12 characters maximum). Enter sufficient information in the
available 12 spaces to identify the manufacturer and the
solution used.
Use additional Form(s) IIA-IN if more calibration verification
sources were used.
3.4.3.2.2 Under "Initial Calibration Verification True", enter the value
[in micrograms per Liter (ug/L), to one decimal place] of the
concentration of each analyte in the ICV Solution.
B-25 ILM05.2
-------
Exhibit B Section 3
Form Instructions
Form IIA-IN (Con't)
3.4.3.2.3 Under "Initial Calibration Verification Found", enter the most
recent value (in ug/L, to two decimal places), of the
concentration of each analyte measured in the ICV Solution.
3.4.3.2.4 Under "Initial Calibration Verification %R", enter the value
(to the nearest whole number) of the percent recovery computed
according to the following equation:
EQ. 1 ICV Percent Recovery
Found (IC\
True(ICV)
%R = FOUnd(ICV) x 100
WHERE, "True (ICV)" is the true concentration of the analyte in
the ICV Solution and "Found(ICV)" is the found concentration of
the analyte in the ICV Solution.
The values used in EQ. 1 for "True(ICV)" and "Found(ICV)" shall
be exactly those reported on this form.
3.4.3.2.5 Under "Continuing Calibration Verification True", enter the
value (in ug/L, to one decimal place) of the concentration of
each analyte in the CCV Solution.
3.4.3.2.6 Under "Continuing Calibration Verification Found", enter the
value (in ug/L, to two decimal places) of the concentration of
each analyte measured in the CCV Solution.
NOTE: The form contains two "Continuing Calibration
Verification Found" columns. The column to the left shall
contain values for the first CCV, and the column to the right
shall contain values for the second CCV.
3.4.3.2.7 If more than one Form IIA-IN is required to report multiple
CCVs, then the column to the left on the second form shall
contain values for the third CCV, the column to the right shall
contain values for the fourth CCV, and so on.
3.4.3.2.8 Under "Continuing Calibration Verification %R", enter the value
(to the nearest whole number) of the percent recovery computed
according to the following equation:
EQ. 2 CCV Percent Recovery
Found(CC
True(CCV)
%R = FQUnd(CCV) x 100
WHERE, "True(CCV)" is the true concentration of each analyte,
and "Found(CCV)" is the found concentration of the analyte in
the CCV Solution.
The values used in EQ. 2 for "True(CCV)" and "Found(CCV)" shall
be exactly those reported on this form.
NOTE: The form contains two "Continuing Calibration
Verification %R" columns. Entries to these columns shall
follow the sequence detailed above for entries to the
"Continuing Calibration Verification Found" columns.
ILM05.2 B-26
-------
Exhibit B Section 3
Form Instructions
Form IIB-IN
3.4.3.2.9 Under "M", enter the method used or "NR", as explained in
Exhibit B, Section 3.4.2.2.5.3.
3.4.3.2.10 If more than one wavelength/mass is used to analyze an analyte,
submit additional Form(s) IIA-IN as appropriate.
3.4.3.2.11 The order of reporting ICVs and CCVs for each analyte shall
follow the chronological order in which the standards were run.
Start with the first Form IIA-IN and move from the left to the
right, continuing to the following Form IIA-INs as appropriate.
For instance, the first ICV for all analytes shall be reported
on the first Form IIA-IN. In a run where three CCVs were
analyzed, the first CCV shall be reported in the left CCV
column on the first Form IIA-IN 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-IN. On the second Form IIA-IN, 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-IN
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.
3.4.4 CRQL Check Standard [Form IIB-IN]
3.4.4.1 Purpose. This form is used to report analyte recoveries from
analyses of the CRQL Check Standards (CRIs).
3.4.4.2 Instructions. Complete the header information according to the
instructions in Exhibit B, Section 3.3. Complete the remainder of
the form using the following instructions.
3.4.4.2.1 Enter the CRQL Check Standard Source (12 characters maximum) as
explained in Exhibit B, Section 3.4.3.2.1.
3.4.4.2.2 Under "CRQL Check Standard True", enter the value (in ug/L, to
one decimal place) of the concentration of each analyte in the
CRQL Check Standard that was analyzed for analytical samples
associated with the SDG.
3.4.4.2.3 Under "CRQL Check Standard Initial Found", enter the value (in
ug/L, to two decimal places) of the concentration of each
analyte measured in the CRQL Check Standard analyzed at the
beginning of each run. Concentration units are ug/L. If
applicable, enter the concentration qualifier "J" or "U" after
the concentration (e.g., 1.96J for Lead), as specified in
Exhibit B, Section 3.4.2.2.5.1.
3.4.4.2.4 Under "CRQL Check Standard Initial %R", enter the value (to the
nearest whole number) of the percent recovery computed
according to the following equation:
EQ. 3 CRQL Check Standard Initial Percent Recovery
CRQL Check Standard Initial Found
CRQL Check Standard True
1UU
B-27 ILM05.2
-------
Exhibit B Section 3
Form Instructions
Form III-IN
3.4.4.2.5 Under "CRQL Check Standard Final Found", enter the value (in
ug/L, to two decimal places) of the concentration of each
analyte measured in the CRQL Check Standard analyzed at the end
of each run. If applicable, enter the concentration qualifier
"J" or "U" after the concentration (e.g., 1.96J for Lead), as
specified in Exhibit B, Section 3.4.2.2.5.1.
3.4.4.2.6 Under "CRQL Check Standard Final %R", enter the value (to the
nearest whole number) of the percent recovery computed
according to the following equation:
EQ. 4 CRQL Check Standard Final Percent Recovery
_ CRQL Check Standard Final Found x
CRQL Check Standard True
3.4.4.2.7 All percent recovery values reported in EQs. 3 and 4 shall be
calculated using the exact true and found values reported on
this form.
NOTE: For every initial solution reported there must be a final
one. However, the opposite is not true. If a CRQL Check
Standard was required to be analyzed in the middle of a run, it
shall be reported in the "Final Found" section of this form.
3.4.4.2.8 If more CRI analyses were required or analyses were performed
using more than one wavelength per analyte, submit additional
Form(s) IIB-IN as appropriate.
3.4.4.2.9 The order of reporting CRIs for each analyte shall follow the
chronological order in which the standards were run starting
with the first Form IIB-IN and continuing to the following
Forms IIB-IN 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.
3.4.5 Blanks [Form III-IN]
3.4.5.1 Purpose. This form is used to report analyte concentrations found
in the Initial Calibration Blank (ICB), Continuing Calibration
Blanks (CCB), and the Preparation Blank (PB).
3.4.5.2 Instructions. Complete the header information according to the
instructions in Exhibit B, Section 3.3. Complete the remainder of
the form using the following instructions.
3.4.5.2.1 Enter "SOIL" or "WATER" as appropriate as the matrix of the PB.
No abbreviations or other matrix descriptors may be used.
3.4.5.2.2 According to the matrix specified for the PB, enter the PB
concentration units as "UG/L" for water.or "MG/KG" for soil.
3.4.5.2.3 Under "Initial Calibration Blank", enter the concentration (in
ug/L, to one decimal place) of each analyte in the most recent
ICB, as described in Exhibit B, Section 3.4.5.2.8, below.
3.4.5.2.4 For each calibration blank associated with a given method and
instrument, enter "J" under the "C" qualifier field on Form
III-IN if the absolute value of the analyte concentration is
less than the CRQL for water but greater than or equal to the
ILM05.2 B-28
-------
Exhibit B Section 3
Form Instructions
Form III-IN (Con't)
MDL that was obtained from direct analysis (Preparation Method
"NP1") using that method and instrument.
For prepared calibration blanks (e.g., mercury), the CRQL for
water and the MDL for the preparation method, analysis, and
instrument shall be used.
Enter "U" if the absolute value of the analyte in the blank is
less than the MDL obtained from direct analysis or the
preparation method.
3.4.5.2.5 Under "Continuing Calibration Blank 1", enter the concentration
(in ug/L, to one decimal place) of each analyte detected in the
first required CCB analyzed after the ICB, as described in
Exhibit B, Section 3.4.5.2.8, below. Enter any appropriate
qualifier, as explained for the "Initial Calibration Blank", to
the "C" qualifier column immediately following the "Continuing
Calibration Blank 1" column.
3.4.5.2.6 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
CCBs were analyzed, then complete additional Form(s) III-IN as
appropriate.
3.4.5.2.7 Under "Preparation Blank", enter the concentration in ug/L (to
three decimal places) for a water blank, or mg/kg (to three
decimal places) for a soil blank, of each analyte in the PB, as
described in Exhibit B, Section 3.4.5.2.8, below. Evaluate the
absolute value of the analyte concentration to determine the
appropriate concentration qualifier, as explained in Exhibit B,
Section 3.4.2.2.5.1, and enter the qualifier in the "C" column
immediately following the "Preparation Blank" column.
3.4.5.2.8 For all blanks, enter the concentration (positive or negative)
for each analyte, if the absolute value of the concentration is
greater than or equal to the appropriate MDL. Enter the CRQL
value for the analyte, if the absolute value of the
concentration is less than the appropriate MDL.
For example, arsenic has a MDL of 3 ug/L for Preparation Method
"NP1" [CRQL for arsenic is 15 ug/L (water)]. Therefore, a CCB
instrument reading of -4.2485 ug/L will be reported as -4.2J; a
CCB instrument reading of -2.4356 ug/L will be reported as
15.OU; a CCB instrument reading of 4.3586 ug/L will be reported
as 4.4J; and a CCB instrument reading of 2.1584 ug/L will be
reported as 15.OU.
3.4.5.2.9 Under "M", enter the method used, as explained in Exhibit B,
Section 3.4.2.2.5.3.
3.4.5.2.10 If more than one wavelength/mass is used to analyze an analyte,
submit additional Form(s) III-IN as appropriate.
3.4.5.2.11 The order of reporting ICBs and CCBs for each analyte shall
follow the chronological order in which the blanks were run
starting with the first Form III-IN and moving from left to
right and continuing to additional Forms III-IN. 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.
B-29 ILM05.2
-------
Exhibit B Section 3
Form Instructions
Forms IVA-IN and IVB-IN
3.4.6 ICP-AES and ICP-MS Interference Check Sample (ICS) [Forms IVA-IN and
IVB-IN]
3.4.6.1 Purpose. These forms are used to report ICS results for each ICP-
AES or ICP-MS instrument used in SDG analyses.
3.4.6.2 Instructions. Complete the header information according to the
instructions in Exhibit B, Section 3.3. Complete the remainder of
the form using the following instructions. The instructions for
Forms IVA-IN and IVB-IN are identical except where specified.
3.4.6.2.1 For "ICP Instrument ID", 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 Instrument ID.
3.4.6.2.2 Enter "ICS Source" (12 characters maximum) as explained in
Exhibit B, Section 3.4.3.2.1. For USEPA solutions, include in
the source name a number identifying it (e.g., EPA-LV87) .
3.4.6.2.3 Under "True Sol. A", enter the true concentration (in ug/L, to
the nearest whole number) of each analyte present in Solution
A. Enter "0" for each analyte with no specified true value in
Solution A.
3.4.6.2.4 Under "True Sol. AB", enter the true concentration (in ug/L, to
the nearest whole number) of each analyte present in Solution
AB. Enter "0" for each analyte with no specified true value in
Solution AB.
3.4.6.2.5 Under "Initial Found Sol. A" on Form IVA-IN (ICP-AES), and
"Found Sol. A" on Form IVB-IN (ICP-MS), enter the concentration
(positive, negative, or zero, in ug/L, to the nearest whole
number) of each analyte and interferent in the initial analysis
of Solution A as required in Exhibit D.
3.4.6.2.6 Under "Initial Found Sol. A %R" on Form IVA-IN (ICP-AES), and
"Found Sol. A %R" on Form IVB-IN (ICP-MS), enter the value (to
the nearest whole number) of the percent recovery computed for
true Solution A greater than zero according to the following
equation:
EQ. 5 Initial Found Sol. A Percent Recovery
_ _ Initial Found Solution A
True Solution A
inn
x J.UU
Leave the field blank if "True Solution A" equals zero.
3.4.6.2.7 Under "Initial Found Sol. AB" on Form IVA-IN (ICP-AES), and
"Found Sol. AB" on Form IVB-IN (ICP-MS), enter the
concentration (positive, negative, or zero, in ug/L, to one
decimal place) of each analyte and interferent in the initial
analysis of Solution AB as required in Exhibit D.
ILM05.2 B-30
-------
Exhibit B Section 3
Forms Instructions
Forms IVA-IN and IVB-IN (Con't)
3.4.6.2.8 Under "Initial Found Sol. AB %R" on Form IVA-IN (ICP-AES), and
"Found Sol. AB %R" on Form IVB-IN (ICP-MS) , enter the value (to
the nearest whole number) of the percent recovery computed for
True Solution AB greater than zero according to the following
equation:
EQ. 6 Initial Found Sol. AB Percent Recovery
_ Initial Found Solution AB x QQ
True Solution AB
Leave the field blank if "True Solution AB" equals zero.
3.4.6.2.9 Under "Final Found Sol. A", enter the concentration (positive,
negative, or zero, in ug/L, to the nearest whole number) of
each analyte and interferent in the final analysis of Solution
A as required in Exhibit D. ICP-MS analysis (Form IVB-IN) does
not require a final analysis.
3.4.6.2.10 Under "Final Found Sol. A %R" enter the value (to the nearest
whole number) of the percent recovery computed for true
Solution A greater than zero according to the following
equation:
EQ. 7 Final Found Sol. A Percent Recovery
Final Found Solution A
True Solution A
.. ._
Ť .L U U
Leave the field blank if "True Solution A" equals zero.
3.4.6.2.11 Under "Final Found Sol. AB", enter the concentration (positive,
negative, or zero, in ug/L, to one decimal place) of each
analyte and interferent in the final analysis of Solution AB as
required in Exhibit D. ICP-MS analysis (Form IVB-IN) does not
require a final analysis.
3.4.6.2.12 For all found values of Solutions A and AB, enter the
concentration (positive, negative, or zero) of each analyte and
interferent at each wavelength used for analysis by ICP.
3.4.6.2.13 Under "Final Found Sol. AB %R", enter the value (to the nearest
whole number) of the percent recovery computed for true
Solution AB greater than zero according to the following
equation:
EQ. 8 Final Found Sol. AB Percent Recovery
Final Found Solution AB
True Solution AB
1f.ri
J.UU
Leave the field empty if "True Solution AB" equals zero.
All percent recovery values reported shall be calculated using
the exact true and found values reported on this form.
NOTE: For ICP-AES (Form IVA-IN), for every initial solution
reported there must be a final solution reported. However, the
opposite is not true. If an ICS was required to be analyzed in
B-31 ILM05.2
-------
Exhibit B Section 3
Form Instructions
Form VA-IN
the middle of a run, it shall be reported in the "Final Found"
section of this form.
3.4.6.2.14 If more ICS analyses were required, submit additional Form(s)
IVA-IN and/or IVB-IN as appropriate.
3.4.6.2.15 The order of reporting ICSs for each analyte shall follow the
chronological order in which the standards were run, starting
with the first Form IVA-IN and/or IVB-IN and continuing to the
following Forms IV-IN as appropriate. When multiple
wavelengths/masses are used for one analyte, all the results of
one wavelength/mass shall be reported before proceeding to the
next wavelength/mass.
3.4.7 Matrix Spike Sample Recovery [Form VA-IN]
3.4.7.1 Purpose. This form is used to report results for the pre-digest
spike.
3.4.7.2 Instructions. Complete the header information according to the
instructions in Exhibit B, Section 3.3. Complete the remainder of
the form using the following instructions.
3.4.7.2.1 Indicate the appropriate matrix, level, and concentration units
(ug/L for water and mg/kg dry weight for soil) as explained in
Exhibit B, Sections 2.5.2.1.1 and 3.3.8.
3.4.7.2.2 For "% Solids for Sample", enter the percent solids (see
Exhibit B, Section 3.4.2.2.2) for the original sample of EPA
sample number reported on the form. Note that this number must
equal the one reported on Form IA-IN for that sample.
3.4.7.2.3 In the "EPA Sample No." box, enter an 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.
3.4.7.2.4 Under "Control Limit %R", enter "75-125" if the sample result
is less than or equal to four times the spike added value. If
the sample result is greater than four times the Spike Added
(SA) value, leave this field empty.
3.4.7.2.5 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 concentration qualifier, as explained in Exhibit B,
Section 3.4.2.2.5.1, to the "C" qualifier column immediately
following the "Spiked Sample Result (SSR)" column.
3.4.7.2.6 Under "Sample Result (SR)", enter the measured value (to four
decimal places) for each required analyte in the sample
(reported in "EPA Sample No." box) on which the matrix spike
was performed. Enter any appropriate concentration qualifier,
as explained in Exhibit B, Section 3.4.2.2.5.1, to the "C"
qualifier column immediately following the "Sample Result (SR)"
column.
3.4.7.2.7 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 "SSR",
"SR", and "SA". If the "Spike Added" concentration is
specified in the contract, the value added and reported shall
ILM05.2 B-32
-------
Exhibit B Section 3
Form Instructions
Form VB-IN
be the specific concentration in appropriate units, corrected
for spiked sample weight and percent solids (soils) or spiked
sample volume (waters).
3.4.7.2.8 Under "%R", enter the value (to the nearest whole number) of
the percent recovery for all spiked analytes computed according
to the following equation:
EQ. 9 Spike Percent Recovery
%R = SSR - SR x 100
SA
Percent recovery 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 MDL.
3.4.7.2.9 Under "Q", enter "N" if the Spike Recovery (%R) is out of the
control limits (75-125) and the Sample Result (SR) is less than
or equal to four times the SA.
3.4.7.2.10 Under "M", enter the method used (as explained in Exhibit B,
Section 3.4.2.2.5.3) or enter "NR" if the analyte is not
required in the spike.
3.4.7.2.11 If different samples were used for spike sample analysis of
different analytes, additional Form(s) VA-IN shall be submitted
for each sample as appropriate.
3.4.8 Post-Digestion Spike Sample Recovery [Form VB-IN]
3.4.8.1 Purpose. 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.
3.4.8.2 Instructions. Complete the header information according to the
instructions in Exhibit B, Section 3.3. Complete the remainder of
the form using the following instructions.
3.4.8.2.1 In the "EPA Sample No." box, enter an EPA sample number (seven
characters maximum) of the sample from which the spike results
on this form were obtained. The number shall be centered in
the box.
3.4.8.2.2 The "Control Limit %R" and "Q" fields shall be left blank until
limits are established by USEPA. At that time, the Contractor
will be informed how to complete these fields.
3.4.8.2.3 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 concentration
qualifier, as explained in Exhibit B, Section 3.4.2.2.5.1, to
the "C" qualifier column immediately following the "Spiked
Sample Result (SSR)" column.
3.4.8.2.4 Under "Sample Result (SR)", enter the measured value (in ug/L,
to two decimal places) for the concentration of each analyte in
B-33 ILM05.2
-------
Exhibit B Section 3
Form Instructions
Form VI-IN
the sample (reported in "EPA Sample No." box) on which the
spike was performed. Enter any appropriate concentration
qualifier, as explained in Exhibit B, Section 3.4.2.2.5.1, to
the "C" qualifier column immediately following the "Sample
Result (SR)" column.
3.4.8.2.5 Under "Spike Added (SA)", enter the value (in ug/L, to one
decimal place) for each analyte added to the sample. If the SA
concentration is specified in the contract, the value added and
reported shall be that specific concentration in appropriate
units.
3.4.8.2.6 Under "%R", enter the value (to the nearest whole number) of
the percent recovery for all spiked analytes computed according
to EQ. 9 in Exhibit B, Section 3.4.7.2.8. Percent recovery
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 MDL.
3.4.8.2.7 Under "M", enter the method used as explained in Exhibit B,
Section 3.4.2.2.5.3, or enter "NR" if the spike was not
required.
3.4.8.2.8 If different samples were used for spike sample analysis of
different analytes, additional Form(s) VB-IN shall be
submitted.
3.4.9 Duplicates [Form VI-IN]
3.4.9.1 Purpose. The duplicates form is used to report results of
duplicate analyses. Duplicate analyses are required for percent
solids values and all analyte results.
3.4.9.2 Complete the header information according to the instructions in
Exhibit B, Section 3.3. Complete the remainder of the form using
the following instructions.
3.4.9.2.1 Indicate the appropriate matrix, level, and concentration units
(ug/L for water and mg/kg dry weight for soil) as explained in
Exhibit B, Sections 2.5.2.1.1 and 3.3.8.
3.4.9.2.2 For "% Solids for Sample", enter the percent solids (as
explained in Exhibit B, Section 3.4.2.2.2) for the original
sample of the EPA sample number reported on the form. Note
that this number must equal the one reported on Form IA-IN for
that sample.
3.4.9.2.3 For "% Solids for Duplicate", enter the percent solids (as
explained in Exhibit B, Section 3.4.2.2.2) for the duplicate
sample of the EPA sample number reported on the form.
3.4.9.2.4 In the "EPA Sample No." box, enter EPA sample number (seven
characters maximum) of the sample from which the duplicate
sample results on this form were obtained. The number shall be
centered in the box.
3.4.9.2.5 Under "Control Limit", enter the CRQL (in appropriate units,
ug/L for water or mg/kg dry weight basis corrected for the
original sample weight and percent solids) for the analyte if
either the sample or duplicate value was less than 5 times the
CRQL. If the sample and duplicate values were greater than or
ILM05.2 B-34
-------
Exhibit B Section 3
Form Instructions
Form VII-IN
equal to 5 times the CRQL, or if the sample and duplicate
values were less than the CRQL, leave the field empty.
3.4.9.2.6 Under "Sample (S)", enter the original measured value (to four
decimal places) for the concentration of each analyte in the
sample (reported in "EPA Sample No." box) on which a duplicate
analysis was performed. Concentration units are those
specified on the form. Enter any appropriate concentration
. qualifier, as explained in Exhibit B, Section 3.4.2.2.5.1, to
the "C" qualifier column immediately following the "Sample (S)"
column.
3.4.9.2.7 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 concentration qualifier, as explained in Exhibit B,
Section 3.4.2.2.5.1, to the "C" qualifier column immediately
following the "Duplicate (D)" column.
3.4.9.2.8 For solid samples, the concentration of the original sample
shall be computed using the weight and percent solids of the
original sample. The concentration of the duplicate sample
shall be computed using the weight of the duplicate sample, but
the percent solids of the original sample.
3.4.9.2.9 Under "RPD", enter the absolute value (to the nearest whole
number) of the Relative Percent Difference (RPD) for all
analytes detected above the MDL in either the sample or the
duplicate, computed according to the following equation:
EQ. 10 Duplicate Sample Relative Percent Difference
RPD = I S " D I x 100
(S + 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 MDL in either
one. If the analyte concentration is less than the MDL in both
"S" and "D", leave the "RPD" field empty.
3.4.9.2.10 Under "Q", enter "*" if the duplicate analysis for the analyte
is out of control. If both sample and duplicate values are
greater than or equal to 5 times the CRQL, then the RPD must be
less than or equal to 20% to be in control. If either the
sample or duplicate value is less than 5 times the CRQL, then
the absolute difference between the sample and duplicate values
shall be less than the CRQL to be in control.
3.4.9.2.11 If both values are below the CRQL, then no control limit is
applicable.
3.4.9.2.12 Under "M", enter method used as explained in Exhibit B, Section
3.4.2.2.5.3.
3.4.10 Laboratory Control Sample [Form VII-IN]
3.4.10.1 Purpose. This form is used to report results for the solid and
aqueous LCSs.
B-35 ILM05.2
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Exhibit B Section 3
Form Instructions
Form VII-IN (Con't)
3.4.10.2 Instructions. Complete the header information according to the
instructions in Exhibit B, Section 3.3. Complete the remainder of
the form using the following instructions.
3.4.10.2.1 For the Solid LCS Source (12 characters maximum), enter the
appropriate EPA sample number if EPA provided standard was
used. Substitute an appropriate number provided by EPA for LCS
solutions prepared in the future. If other sources were used,
identify the source. For the aqueous LCS Source, enter the
source name (12 characters maximum) as explained in Exhibit B,
Section 3.4.3.2.1.
3.4.10.2.2 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.
3.4.10.2.3 Under "Aqueous Found", enter the measured concentration (in
ug/L, to two decimal places) of each analyte found in the
Aqueous LCS solution.
3.4.10.2.4 Under "Aqueous %R", enter the value of the percent recovery (to
the nearest whole number) computed according to the following
equation:
EQ. 11 Aqueous LCS Percent Recovery
Aqueous LCS Found
%R
Aqueous LCS True
3.4.10.2.5 Under "Solid True", enter the value (in mg/kg, to one decimal
place) of the concentration of each analyte in the solid LCS
Source.
3.4.10.2.6 Under "Solid Found", enter the measured value (in mg/kg, to one
decimal place) of each analyte found in the solid LCS solution.
3.4.10.2.7 Under "C", enter "J" or "U" or leave empty, to describe the
found value of the solid LCS as explained in Exhibit B, Section
3.4.2.2.5.1.
3.4.10.2.8 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.
3.4.10.2.9 Under "Solid %R", enter the value of the percent recovery (to
the nearest whole number) computed according to the following
equation:
EQ. 12 Solid LCS Percent Recovery
Solid LCS Found
%R
Solid LCS True
3.4.10.2.10 The values for true and found aqueous and solid LCSs used in
EQs. 11 and 12 shall be exactly those reported on this form.
If the analyte concentration is less than the MDL, a value of
zero shall be substituted for the aqueous and solid LCS found.
ILM05.2 B-36
-------
Exhibit B -- Section 3
Form Instructions
Form VIII-IN
3.4.10.2.11 Submit additional Form(s) VII-IN as appropriate if more than
one aqueous LCS or solid LCS was required.
3.4.11 ICP-AES and ICP-MS Serial Dilutions [Form VIII-IN]
3.4.11.1 Purpose. This form is used to report results for ICP-AES and ICP-
MS serial dilutions.
3.4.11.2 Instructions. Complete the header information according to the
instructions in Exhibit B, Section 3.3. Complete the remainder of
the form using the following instructions.
3.4.11.2.1 In the "EPA Sample No." box, enter 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.
3.4.11.2.2 Under "Initial Sample Result (I)", enter the instrument
measured value (in ug/L to two decimal places) for each ICP
analyte. This value shall not be corrected for any dilution.
Enter any appropriate concentration qualifier, as explained in
Exhibit B, Section 3.4.2.2.5.1, to the "C" qualifier column
immediately following the "Initial Sample Result (I)" column.
NOTE: The initial sample concentration for an analyte does not
have to equal the value for that analyte reported on Form IA-IN
for that sample. It is the value of the analyte's instrument
measured value (uncorrected for dilution) that is within the
linear range of the instrument.
3.4.11.2.3 Under "Serial Dilution Result (S)", enter the instrument
measured value corrected for a five-fold dilution (in ug/L to
two decimal places) for each ICP analyte in the diluted sample.
Enter any appropriate concentration qualifier, as explained in
Exhibit B, Section 3.4.2.2.5.1, to the "C" qualifier column
immediately following the "Serial Dilution Result (S)" column.
NOTE: The "Serial Dilution Result (S)" is obtained by
multiplying by five the instrument measured value (in ug/L) of
the serially diluted sample. The "C" qualifier for the serial
dilution shall be established based on the serial dilution
result before correcting it for the five-fold dilution
regardless of the value reported on Form VIII-IN.
For example, if the instrument readout value for the "Initial
Sample Result (I)" for silver in a two-fold diluted sample
MAX123 is 1164.36 ug/L, and the instrument readout value for
the "Serial Dilution Result (S)" for silver in a ten-fold
diluted sample MAX123 (MAX123L) is 241.67 ug/L, then the
concentration reported for silver in the "Initial Sample Result
(I)" column will be 1164.36 ug/L (not 2 times the instrument
readout value which equals 2328.72 ug/L), and the concentration
reported for silver in the "Serial Dilution Result (S)" column
will be five times the instrument readout value which equals
1208.35 ug/L (not 10 times the instrument readout value which
equals 2416.70 ug/L).
B-37 ILM05.2
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Exhibit B Section 3
Form Instructions
Form IX-IN
3.4.11.2.4 Under "% Difference", enter the absolute value (to the nearest
whole number) of the percent difference in concentration of
required analytes, between the original sample and the diluted
sample (adjusted for dilution) according to the following
formula:
EQ. 13 Serial Dilution Percent Difference
I T _ q I
% Difference = *-ą fj
The values for "I" and "S" used to calculate percent difference
in EQ. 13 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 MDL. If the analyte
concentration in (I) is less than the MDL concentration, leave
the "% Difference" field empty.
3.4.11.2.5 Under "Q", enter "E" if the percent difference is greater than
10% and the original sample concentration (reported on Form IA-
IN) is greater than 50 times the MDL reported on Form IX-IN.
3.4.11.2.6 Under "M", enter the method of analysis for each analyte as
explained in Exhibit B, Section 3.4.2.2.5.3.
3.4.12 Method Detection Limits (Annually) [Form IX-IN]
3.4.12.1 Purpose. This form documents the Method Detection Limits (MDLs)
for each preparation method and instrument that the Contractor
used to obtain data for the SDG. Only the methods, instruments,
and wavelengths used to generate data for the SDG shall be
included. The Contractor shall also report MDLs, obtained from
direct analysis, for each instrument used to obtain data for the
SDG. The MDLs obtained from direct analysis shall be used in the
qualification of data associated with samples and instrument QC
standards that are hot taken through a preparation procedure.
Although the MDLs are determined annually, a copy of the annual
MDLs shall be included with each Sample Data Package on Forms IX-
IN.
3.4.12.2 Instructions. Complete the header information according to the
instructions in Exhibit B, Section 3.3. Complete the remainder of
the form using the following instructions.
3.4.12.2.1 Enter the Analysis Method qualifier as specified in Exhibit B,
Section 3.4.2.2.5.3, in the "Instrument Type" field.
3.4.12.2.2 Enter the Instrument ID in the "Instrument ID" field (12
characters maximum). These instrument IDs are used to uniquely
identify each instrument that the laboratory used to perform
the analysis.
3.4.12.2.3 Enter the date (formatted MM/DD/YYYY) on which the MDL analysis
was performed in the "Date" field.
ILM05.2 B-38
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Exhibit B Section 3
Form Instructions
Form IX-IN (Con't)
3.4.12.2.4 For "Preparation Method", enter the method of preparation
(three characters maximum) for which the MDLs listed on Form
IX-IN were established. Use appropriate sample preparation
codes as specified below:
HW1: Hotplate/Block digestion for ICP-AES analysis of water
samples.
HW2: Hotplate/Block digestion for ICP-MS analysis of water
samples.
MW1: Microwave digestion for ICP-AES analysis of water
samples.
MW2: Microwave digestion for ICP-AES analysis of water
samples.
HS1: Hotplate/Block digestion for ICP-AES analysis of soil
samples.
HS2: Hotplate/Block digestion for ICP-AES analysis of soil
samples.
MSI: Microwave digestion for ICP-AES analysis of soil samples.
CW1: Preparation for the Manual Cold Vapor AA analysis of
water samples.
CS1: Preparation for the Manual Cold Vapor AA analysis of soil
samples.
CW2: Preparation for the Automated Cold Vapor AA analysis of
water samples.
DW1: Distillation for the manual and semi-automated spectro-
photometric analysis of water samples.
DW2: Midi-distillation for the semi-automated spectro-
photometric analysis of water samples.
DS1: Distillation for the manual and semi-automated spectro-
photometric analysis of soil samples.
DS2: Midi-distillation for the semi-automated spectro-
photometric analysis of soil samples.
NP1: No preparation.
3.4.12.2.5 Enter the concentration units (UG/L for water or MG/KG wet
weight for soil) for the results reported on Form IX-IN in the
"Concentration Units" field. Enter "UG/L" for MDL results
obtained from direct analysis (Preparation Method "NP1").
3.4.12.2.6 Under "Wavelength/Mass", enter the wavelength in nanometers
(nm) to two decimal places or the mass in atomic mass units
(amu) to two decimal places for each analyte for which an MDL
has been established and is listed in the MDL column. If more
than one wavelength or mass is used for an -analyte, use
additional Form(s) IX-IN as appropriate to report the MDL.
3.4.12.2.7 Contract Required Quantitation Limits (in ug/L for water and
mg/kg for soil) as established in Exhibit C, shall be reported
in the column headed "CRQL". The CRQL shall be reported in
ug/L on Form(s) IX-IN associated with Preparation Method "NP1".
3.4.12.2.8 Under "MDL", enter the MDL (in ug/L for water and direct
analysis, or mg/kg for soil, to two significant figures for
values less than 10, and three significant figures for values
greater than or equal to 10) as determined by the Contractor
for each analyte analyzed by the instrument for which the ID is
listed on this form. When calculating MDL values, always round
up to the appropriate significant figure (e.g., 14.81 rounds to
14.9 and 146.6 rounds to 147). This deviation from the
rounding rule is necessary to prevent the reporting of detected
values for results that fall in the noise region of the
calibration curve.
B-39 ILM05.2
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Exhibit B Section 3
Form Instructions
Form XA-IN
NOTE: Zeros used to set the decimal point in a number less than
one are not significant but all trailing zeros are significant.
For example, a calculated MDL value of 0.074 ug/L will be
reported as 0.074 and a calculated MDL value of 0.1 or 0.08
will be reported as 0.10 and 0.080, respectively.
3.4.12.2.9 Use additional Form(s) IX-IN if more preparation methods,
instruments and wavelengths or masses are used. Note that the
date on this form shall not exceed the analysis dates in the
Sample Data Package or precede them by more than twelve months.
3.4.12.2.10 Use the "Comments" section to indicate alternative wavelengths
and the conditions under which they are used.
3.4.13 ICP-AES Interelement Correction Factors (Quarterly) [Form XA-IN]
3.4.13.1 Purpose. This form documents for each ICP-AES instrument the
interelement correction factors applied by the Contractor to
obtain data for the SDG. Although the correction factors are
determined quarterly, a copy of the results of the quarterly
interelement correction factors shall be included with each Sample
Data Package on Form XA-IN and Form XB-IN as appropriate.
3.4.13.2 Instructions. Complete the header information according to
instructions in Exhibit B, Section 3.3. Complete the remainder of
the form using the following instructions.
3.4.13.2.1 Enter the ICP-AES Instrument ID (12 characters maximum), which
is a unique number designated by the Contractor to identify
each ICP-AES instrument used to produce data in the Sample Data
Package. If more than one ICP-AES instrument is used, submit
additional Form(s) XA-IN as appropriate.
3.4.13.2.2 Report the date (formatted as MM/DD/YYYY) on which these
correction factors were determined for use. This date shall
not exceed the ICP-AES analysis dates in the Sample Data
Package or precede them by more than three calendar months.
3.4.13.2.3 Under "Wavelength", list the wavelength in nm (to two decimal
places) used for each ICP-AES analyte. If more than one
wavelength is used, submit additional Form(s) XA-IN or Form(s)
XB-IN as appropriate.
3.4.13.2.4 Under "Al", "Ca", "Fe", and "Mg", enter the correction factor
(negative, positive or zero, to seven decimal places, 10
characters maximum) for each ICP-AES analyte. Correction
factors for one other analyte shall be reported using the empty
column and listing the analyte's chemical symbol in the blank
two-space header field provided for that column.
3.4.13.2.5 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. Correction factors for more than one
additional analyte shall be reported using Form XB-IN.
NOTE: Correction factors for Al, Ca, Fe, and Mg are all
required and are to be listed first (as they appear on Form XA-
IN) .
ILM05.2 B-40
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Exhibit BSection 3
Form Instructions
Form XB-IN, XI-IN, and XII-IN
3.4.14 ICP-AES Interelement Correction Factors (Quarterly) [Form XB-IN]
3.4.14.1 Purpose. 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-
AES.
3.4.14.2 Instructions. Complete this form following the instructions for
Form XA-IN (see Exhibit B, Section 3.4.13) by listing the chemical
symbol for additional analytes in the heading of the empty columns
in the two-space fields provided.
3.4.14.2.1 Columns of correction factors for additional analytes shall be
entered left to right starting on Form XA-IN and proceeding to
Form XB-IN, according to the alphabetical order of their
chemical symbols.
3.4.15 ICP-AES and ICP-MS Linear Ranges (Quarterly) [Form XI-IN]
3.4.15.1 Purpose. This form documents the quarterly linear range analysis
for each ICP instrument that the Contractor used to obtain data
for the SDG.
3.4.15.2 Instructions. Complete the header information according to the
instructions in Exhibit B, Section 3.3. Complete the remainder of
the form using the following instructions.
3.4.15.2.1 Enter the ICP Instrument ID (12 characters 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 Form(s) XI-IN as
appropriate.
3.4.15.2.2 Report the date (formatted as MM/DD/YYYY) on which these linear
,< ranges were analyzed. This date shall not exceed the dates of
analysis by ICP in the Sample Data Package and shall not
precede the analysis dates by more than three calendar months.
3.4.15.2.3 Under "Integ. Time (Sec.)", enter the integration time (in
seconds to two decimal places) used for each measurement taken
from the ICP instrument.
3.4.15.2.4 Under "Concentration", enter the concentration (in ug/L) that
is the upper limit of the ICP instrument linear range as
determined in Exhibit D. Any measurement above it is out of
the linear range, and thus, is an estimated value and shall be
diluted into the linear range.
3.4.15.2.5 Under "M", enter the method of analysis for each analyte as
explained in Exhibit B, Section 3.4.2.2.5.3.
3.4.15.2.6 If more instruments or analyte wavelengths/masses are used,
submit additional Form(s) XI-IN as appropriate.
3.4.16 Preparation Log [Form XII-IN]
3.4.16.1 Purpose. This form is used to report the preparation run log.
3.4.16.1.1 All field samples and all Quality Control (QC) preparations
(including duplicates, matrix spikes, LCSs, PBs, and re-
preparations) associated with the SDG shall be reported on
Form XII-IN.
B-41 ILM05.2
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Exhibit B -- Section 3
Form Instructions
Form XIII-IN
3.4.16.1.2 Submit one Form XII-IN per batch, per method, if no more than
thirty-two preparations, including QC preparations, were
performed. If more than 32 preparations per batch, per method,
were performed, then submit additional copies of Form XII-IN as
appropriate. Submit a separate Form XII-IN for each batch.
3.4.16.1.3 The order in which the Preparation Logs are submitted is very
important. Form XII-IN shall be organized by method, by batch.
Later batches within a method shall follow earlier ones. Each
batch shall start on a separate Form XII-IN.
3.4.16.2 Instructions. Complete the header information according to the
instructions in Exhibit B, Section 3.3. Complete the remainder of
the form using the following instructions.
3.4.16.2.1 For "Preparation Method", enter the method of preparation
(three characters maximum) for which the preparations listed on
Form XII-IN were made, as specified in Exhibit B, Section
3.4.12.2.4.
3.4.16.2.2 Under "EPA Sample No.", enter EPA sample number of each sample
in the SDG, and of all other preparations such as duplicates,
matrix spikes, LCSs, PBs, and re-preparations (all formatted
according to Exhibit B, Table 2). All EPA sample numbers shall
be listed in ascending alphanumeric order, continuing to the
next Form XII-IN if applicable.
3.4.16.2.3 Under "Preparation Date", enter the date (formatted MM/DD/YYYY)
on which each sample was prepared for analysis by the method
indicated in the header section of the form.
NOTE: The date never changes on a single Form XII-IN because
the form shall be submitted per batch.
3.4.16.2.4 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.
3.4.16.2.5 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.
3.4.17 Analysis Run Log [Form XIII-IN]
3.4.17.1 Purpose. This form is used to report the sample analysis run log.
3.4.17.1.1 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 or tune standard,
and terminated by, and including, the CCV and CCB following the
last SOW-required analytical sample.
3.4.17.1.2 All field samples and all QC analyses (including tunes,
calibration standards, ICVs, CCVs, ICBs, CCBs, CRIs, ICSs,
LRSs, LCSs, PBs, duplicates, serial dilutions, matrix spikes,
and post-digestion/distillation spikes) associated with the SDG
shall be reported on Form XIII-IN. The run shall be continuous
and inclusive of all analyses performed on the particular
instrument during the run.
ILM05.2 B-42
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Exhibit B Section 3
Form Instructions
Form XIII-IN (Con't)
3.4.17.1.3 Submit one Form XIII-IN 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 Form(s) XIII-IN as appropriate.
3.4.17.1.4 The order in which the Analysis Run Logs are submitted is very
important. Form XIII-IN shall be organized by method, and by
run. Later runs within a method shall follow earlier ones.
Each analytical run shall start on a separate Form XIII-IN.
Therefore, instrument calibration or tune 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.
3.4.17.2 Instructions. Complete the header information according to the
instructions in Exhibit B, Section 3.3. Complete the remainder of
the form using the following instructions.
3.4.17.2.1 For "Instrument ID", enter the Instrument ID (12 characters
maximum) which shall be an identifier designated by the
Contractor 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 Form(s)
XIII-IN as appropriate. The Instrument ID shall exactly match
that reported on Forms IVA, IVB, IX, XA, XB, XI, XIV, and XV.
3.4.17.2.2 For "Analysis Method", enter the method code (two characters
maximum) according to the specifications in Exhibit B, Section
3.4.2.2.5.3.
3.4.17.2.3 For "Start Date", enter the date (formatted MM/DD/YYYY) on
which the analysis run was started.
3.4.17.2.4 For "End Date", enter the date (formatted MM/DD/YYYY) on which
the analysis run was ended.
3.4.17.2.5 Under "EPA Sample No.", enter EPA sample number of each
analysis, including all QC operations applicable to the SDG
(formatted according to Exhibit B, Table 2). All EPA sample
numbers shall be listed in increasing chronological (date and
time) order of analysis, continuing to the next Form XIII-IN
for the instrument run, if applicable. The analysis date and
time of other analyses not associated with the SDG, but
analyzed by the instrument in the reported analytical run,
shall be reported. Those analyses shall be identified with EPA
sample number of "ZZZZZZ".
3.4.17.2.6 Under "D/F", enter the dilution factor (to two significant
figures) 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.
3.4.17.2.7 The dilution factor is required for all entries on Form XIII-
IN.
NOTE: For a particular sample a dilution factor of "1.0" 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 XII-
IN for that sample.
B-43 ILM05.2
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Exhibit B Section 3
Form Instructions
Form XIV-IN
3.4.17.2.8 For USEPA 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
USEPA. 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 "2.0" shall be entered
on Form XIII-IN and the uncorrected instrument reading is
compared to a true value of 52 ug/L. In this example. Form
IIA-IN 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 XIII-IN using the following
formula:
EQ. 14 ICV/CCV Correction for Dilution
Found value on Form II = Instrument readout (ug/L) x D/F
3.4.17.2.9 Under "Time", enter the time (in military format - HHMM) at
which each analysis was performed.
3.4.17.2.10 Under "Analytes", enter WX" 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.
3.4.17.2.11 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
Inorganic Forms I-VIII. For each analyte result reported on
any of the Forms I-VIII, there shall be one, and only one,
properly identified entry on Form XIII-IN for which an "X" is
entered in the column for that analyte.
3.4.17.2.12 If, on Form XIII-IN, an "X" is entered in the column for an
analyte for a field sample associated with a dilution factor
greater than 1.0, flag the data for that analyte with a "D" on
the appropriate Form IA-IN or Form IB-IN.
3.4.18 ICP-MS Tune [Form XIV-IN]
3.4.18.1 Purpose. This form is used to report the tuning results for each
ICP-MS instrument used in SDG analyses.
3.4.18.2 Instructions. Complete the header information according to the
instructions in Exhibit B, Section 3.3. Complete the remainder of
the form using the following instructions.
3.4.18.2.1 For "ICP-MS Instrument ID", enter an identifier that uniquely
identifies a specific instrument within the Contractor
laboratory. No two ICP-MS instruments within a laboratory may
have the same ICP-MS Instrument ID.
3.4.18.2.2 Report the date (formatted as MM/DD/YYYY) on which the ICP-MS
tune was performed. This date shall not exceed the dates of
analysis by ICP-MS in the Sample Data Package.
ILM05.2 B-44
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Exhibit B -- Section 3
Form Instructions
Form XV-IN
3.4.18.2.3 For "Avg. Measured Mass (amu)", enter the average mass
calculated from the five tune analyses ' (in atomic mass units,
to two decimals places) measured for that isotope.
3.4.18.2.4 For "Avg. Peak Width at 5% Peak Height (amu)" enter the average
peak width calculated from the analysis (in1 atomic mass units,
to two decimal places) at 5% of the peak height.
3.4.18.2.5 For "%RSD", enter percent Relative Standard Deviation of the
absolute signals (intensities) for each isotope calculated from
the five tune analyses.
3.4.19 ICP-MS Internal Standards Relative Intensity Summary [Form XV-IN]
3.4.19.1 Purpose. This form is used to report the relative internal
standard intensity levels during a run for ICP-MS. The relative
intensity of each of the internal standards in all analyses
performed by ICP-MS must be reported on the form. If more than
one ICP-MS instrument or run is used, submit additional Form(s)
XV-IN as appropriate. All runs for the lowest alphanumeric
instrument must be reported in ascending order before proceeding
to the runs for the next highest instrument.
3.4.19.2 Instructions. Complete the header information according to the
instructions in Exhibit B, Section 3.3. Complete the remainder of
the form using the following instructions.
3.4.19.2.1 For "ICP-MS Instrument ID", enter an identifier that uniquely
identifies a specific instrument within the Contractor
laboratory. No two ICP-MS instruments within a laboratory may
have the same ICP-MS Instrument ID.
3.4.19.2.2 For "Start Date", enter the date (formatted MM/DD/YYYY) on
which the analysis run was started.
3.4.19.2.3 For "End Date", enter the date (formatted MM/DD/YYYY) on which
the analysis run was ended.
3.4.19.2.4 Under "EPA Sample No.", enter EPA sample number of each
analysis, including all QC operations applicable to the SDG.
All EPA sample numbers must be listed in increasing
chronological (date and time) order of analysis, continuing to
the next Form XV for the instrument run, if applicable. The
order must agree with the order reported on Form XIII-IN for
that run. The analysis date and time of other analyses not
associated with the SDG, but analyzed by the instrument in the
reported analytical run, must be reported. Those analyses must
be identified with EPA sample number of "ZZZZZZ." Samples
identified as "ZZZZZZ" need not have intensities reported for
internal standards.
3.4.19.2.5 Under "Time", enter the time (in military format - HHMM) at
which each analysis was performed.
3.4.19.2.6 Under "Internal Standards %RI for:", enter the chemical symbol
and elemental expression number of the internal standard in the
"Element" header field provided to indicate the internal
standard and elemental expression for which the Relative
Intensity (RI) of the internal standards will be calculated in
that column.
B-45 ILM05.2
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Exhibit B Section 3
Form Instructions
Form DC-1
3.4.19.2.6.1 In the "Element" column, enter the internal standard
relative intensity (to the nearest whole number) of the
internal standard for each sample analysis listed on the
form (excluding "ZZZZZZ"). The internal standard relative
intensity (%RI) is calculated using the following formula:
EQ. 15 Internal Standard Percent Relative Intensity
% RI = 'x 100
O
WHERE, "I0" is the intensity of the internal standard in the
blank calibration standard and "In" is the intensity of the
internal standard in EPA sample number in the same units.
3.4.19.2.7 Under the "Q" column to the right of each "Element" column,
enter an "R" if the %RI for a field sample, PE, duplicate, or
spike is less than 60 or greater than 125; otherwise leave the
field blank.
3.4.19.2.8 Columns of internal standard RI must be entered left to right
starting with the internal standards of the lower mass on the
first Form XV-IN and proceeding to the following Form XV-IN as
appropriate. All Forms XV-IN for the lowest numeric instrument
must be reported in ascending order by the run number before
proceeding to the next Form XV.
3.4.19.3 All field samples and all QC samples (including calibration
standards, ICVs, CCVs, ICBs, CCBs, CRIs, ICSs, LCS, PB, serial
dilutions, duplicates, PE samples, and spikes) associated with the
SDG must be reported on Form XV-IN. The run must be continuous
and inclusive of all analyses performed on the particular
instrument during the run.
3.4.19.4 Submit one Form XV-IN per run if no more than 32 analyses,
including instrument calibration, were analyzed in the run. If
more than 32 analyses were performed in the run, submit additional
Form(s) XV-IN as appropriate. Each new run must be started on the
first line of Form XV-IN.
3.5 Sample Log-In Sheet [Form DC-1]
3.5.1 Purpose. This form is used to document the receipt and inspection of
samples and containers. At least one original Form DC-1 is required
for each sample shipping container (e.g., cooler). If the samples in
a single sample shipping container must be assigned to more than one
SDG, the original Form DC-1 shall be placed with the deliverables for
the SDG of the lowest alpha-numeric number and a copy of Form DC-1
shall be placed with the deliverables for the other SDG(s). The
copies should be identified as "copy(ies)", and the location of the
original should be noted on the copies.
3.5.2 Instructions
3.5.2.1 Sign and date the airbill. (If an airbill is not received,
include a hardcopy receipt requested from the shipping company or
a printout of the shipping company's electronic tracking
information).
ILM05.2 B-46
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Exhibit B Section 3
Form Instructions
Form DC-1 (Con* t)
3.5.2.2 Examine the shipping container and record the presence/absence of
custody seals and their condition (i.e., intact, broken) in
Item 1.
3.5.2.3 Record the custody seal numbers in Item 2.
3.5.2.4 Open the container, remove the enclosed sample documentation, and
record the presence/absence of USEPA forms (i.e., Traffic
Reports/Chain of Custody Records, packing lists) and airbills or
airbill stickers in Items 3 and 4. Specify if there is an airbill
present or an airbill sticker in Item 4. Record the airbill or
sticker number in Item 5.
3.5.2.5 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 6 and 7.
3.5.2.6 Record the presence or absence of a cooler temperature indicator
bottle in Item 8.
3.5.2.7 Record the cooler temperature in Item 9.
3.5.2.8 Review the sample shipping documents and compare the information
recorded on all the documents and samples and mark the appropriate
answer in Item 10.
3.5.2.9 The log-in date should be recorded at the top of Form DC-1; record
the date and time of cooler receipt at the laboratory in Items 11
and 12.
3.5.2.KLO If there are no problems observed during receipt, sign and date
(include the time) Form DC-1 and Traffic Report/Chain of Custody
Record, and write the sample numbers in the "EPA Sample No."
column.
3.5.2.11 Record the pH for all aqueous samples received.
3.5.2.12 Record the appropriate sample tags and assigned laboratory
numbers, if applicable.
3.5.2.13 Any comments should be made in the "Remarks" column.
3.5.2.14 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.
3.5.2.15 For Items 1, 3, 4, 6, 7, 8 and 10, circle the appropriate
response. Responses can be underlined if this form is completed
by automated equipment. Unused columns and spaces shall be
crossed out, initialed, and dated.
3.5.2.16 If there are problems observed during receipt (including samples
that have not been preserved to the proper pH) or an answer marked
with an asterisk (e.g., "absent*") was circled, 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.
B-47 ILM05.2
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Exhibit B Section 3
Form Instructions
Form DC-2
3.6 Full Inorganics Complete SDG File (CSF) Inventory Sheet [Form DC-2]
3.6.1 Purpose. The CSF Inventory Sheet is used to record both the
inventory of Complete SDG File (CSF) documents and the number of
documents in the original Sample Data Package which is sent to the
USEPA Region.
3.6.2 Instructions
3.6.2.1 Organize all EPA-CSF documents as described in Exhibit B, Sections
2 and 3. Assemble the documents in Exhibit B, Section 2 in the
order specified on Form DC-2, 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. The Contractor shall verify
and record in the "Comments" section on Form DC-2 all intentional
gaps in the page numbering sequence (for example, "page numbers
not used, XXXX-XXXX, XXXX-XXXX"). If there are no documents for a
specific document type, enter an "NA" in the empty space.
3.6.2.2 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 33, 34, 35, or 36. Category 36 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.
3.6.2.3 If it is necessary to insert new or inadvertently omitted
documents, the Contractor shall follow these steps:
- 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).
Ť= 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).
ILM05.2 B-48
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Exhibit B -- Section 4
Data Reporting Forms
4.0 DATA REPORTING FORMS
The data reporting forms are shown on the following pages.
B-49 ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
-------
EXHIBIT B
INORGANIC FORMS
ILM05.2
-------
USEPA - CLP
COVER PAGE
Lab Name: Contract:
Lab Code: Case No.: NRAS No.: SDG No.:
SOW No.:
EPA Sample No. Lab Sample ID
ICP-AES ICP-MS
Were ICP-AES and ICP-MS interelement (Yes/No)
corrections applied?
Were ICP-AES and ICP-MS background corrections (Yes/No)
applied?
If yes, were raw data generated before (Yes/No)
application of background corrections?
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
(or via an alternate means of electronic transmission, if approved in advance
by USEPA) has been authorized by the Laboratory Manager or the Manager's
designee, as verified by the following signature.
Signature: Name:
Date: Title:
COVER PAGE ILM05.2
-------
USEPA - CLP
1A-IN
INORGANIC ANALYSIS DATA SHEET
SPA SAMPLE NO.
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS No.:
SDG No.:
Matrix: (soil/water)
Level: (low/med)
% Solids:
Lab Sample ID:
Date Received:
Concentration Units
or
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
57-12-5
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 IA-IN
ILM05.2
-------
USEPA - CLP
1B-IN
INORGANIC ANALYSIS DATA SHEET
EPA SAMPLE NO.
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS No.:
SDG No.:
Matrix: (soil/water)
Level: (low/med)
% Solids:
Lab Sample ID:
Date Received:
Concentration Units ( BBMl or
dry weight):
Color Be
Color Af
Comments
CAS No.
Analyte
Concentration
C
Q
M
fore: Clarity Before: Texture:
ter: Clarity After: Artifacts:
FORM IB-IN
ILM05.2
-------
USEPA - CLP
2 A-IN
INITIAL AND CONTINUING CALIBRATION VERIFICATION
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS No.:
SDG No.:
Initial Calibration Verification Source:
Continuing Calibration Verification Source:
Concentration Units: ug/L
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magne si-urn
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Initial Calibration
Verification
True
Found
%R(D
Continuing Calibration Verification
True
Found
%R(D
Found
%R(D
M
(1) Control Limits: Mercury 80-120; Other Metals 90-110; Cyanide 85-115
FORM IIA-IN
ILM05.2
-------
USEPA - CLP
2B-IN
CRQL CHECK STANDARD
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS No.:
SDG No.
CRQL Check Standard Source:
Concentration Units: ug/L
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
CRQL Check Standard
Initial Final
True
Found*
%R(D
Found*
%R(D
(1) Control Limits: 70-130 with the following exceptions:
ICP-AES - Antimony, Lead, and Thallium: 50-150.
ICP-MS - Cobalt, Manganese, and Zinc: 50-150.
* If applicable, enter the concentration qualifier "J" or
concentration in these columns (e.g., 0.20U for Mercury).
"U" after the
FORM IIB-IN
ILM05.2
-------
USEPA - CLP
3-IN
BLANKS
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS 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
Calibration
Blank (ug/L)
C
Continuing Calibration
Blank (ug/L)
1
C
2
C
3
C
Preparation
Blank
C
M
FORM III-IN
ILM05.2
-------
USEPA - CLP
4A-IN
ICP-AES INTERFERENCE CHECK SAMPLE
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS No.:
SDG No.:
ICP-AES Instrument ID:
ICS Source:
Concentration Units: ug/L
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
True
Sol. Sol.
A AB
Initial Found
Sol. Sol.
A %R .AB %R
Final Found
Sol. Sol.
A %R AB %R
FORM IVA-IN
ILM05.2
-------
USEPA - CLP
43-IN
ICP-MS INTERFERENCE CHECK SAMPLE
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS No.:
SDG No.:
ICP-MS Instrument ID:
ICS Source:
Concentration Units: ug/L
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Carbon
Chloride
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Phosphorus
Potassium
Selenium
Silver
Sodium
Sulfur
Thallium
Titanium
Vanadium
Zinc
True
Sol. Sol.
A AB
Found
Sol. Sol.
A %R AB %R
FORM IVB-IN
ILM05.2
-------
USEPA - CLP
5A-IN
MATRIX SPIKE SAMPLE RECOVERY
EPA SAMPLE NO.
Lab Name:
Lab Code:
Contract,:
Case No.:
NRAS No.:
Matrix: (soil/water)
% Solids for Sample:
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
%R
Spiked Sample
Result (SSR)
C
Sample
Result (SR)
C
Spike
Added (SA)
%R
Q
M
Comments:
FORM VA-IN
ILM05.2
-------
USEPA - CLP
5B-IN
POST-DIGESTION SPIKE SAMPLE RECOVERY
EPA SAMPLE NO.
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS 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
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
v ^
Control
Limit
%R
_
..
Spiked Sample
Result (SSR)
C
Sample
Result (SR)
C
.
Spike
Added (SA)
%R
Q
M
Comments:
FORM VB-IN
ILM05.2
-------
USEPA - CLP
Lab Name:
Lab Code:
Case No.:
6-IN
DUPLICATES
Contract: _
NRAS No.:
EPA SAMPLE 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
ILM05.2
-------
USEPA - CLP
7-IN
LABORATORY CONTROL SAMPLE
Lab Name:
Lab Code:
Contract:
Case No. :
NRAS 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
ILM05.2
-------
USEPA - CLP
8-IN
ICP-AES and ICP-MS SERIAL DILUTIONS
EPA SAMPLE NO.
Lab Name:
Lab Code:
Contract:
Case No.
Matrix: (soil/water)
NRAS No.:
SDG No.:
Level: (low/med)
Concentration Units: ug/L
Analyte |
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Initial Sampl
Result (I)
e
C
Serial
Dilution
Result (S)
C
%
Difference
Q
M
FORM VIII-IN
ILM05.2
-------
USEPA - CLP
9-IN
METHOD DETECTION LIMITS (ANNUALLY)
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS No.:
Instrument Type:
Instrument ID:
SDG No.
Date:
Preparation Method:
Concentration Units (ug/L or mg/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
Wavelength
/Mass
CRQL
MDL
Comments:
FORM IX-IN
ILM05.2
-------
USEPA - CLP
10A-IN
ICP-AES INTERELEMENT CORRECTION FACTORS (QUARTERLY)
Lab Name:
Lab Code:
Contract:
Case No.:
ICP-AES Instrument ID:
NRAS No.:
Date:
SDG No.
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Wave-
length
(nm)
Interelement Correction Factors for:
Al Ca Fe Mq
Comments:
FORM XA-IN
ILM05.2
-------
USEPA - CLP
10B-IN
ICP-AES INTERELEMENT CORRECTION FACTORS (QUARTERLY)
Lab Name:
Lab Code:
Contract:
Case No.:
ICP-AES Instrument ID:
NRAS No.:
Date:
SDG No.
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Wave-
length
(nm)
Interelement Correction Factors for:
>
Comments:
FORM XB-IN
ILM05.2
-------
USEPA - CLP
11-IN
ICP-AES and ICP-MS LINEAR RANGES (QUARTERLY)
Lab Name:
Lab Code:
Case No.:
ICP Instrument ID:
Contract:
NRAS No.:
Date:
SDG No.
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Integ.
Time
(Sec.)
Concentration
(ug/L)
M
Comments:
FORM XI-IN
ILM05.2
-------
USEPA - CLP
12-IN
PREPARATION LOG
Lab Name: Contract:
Lab Code: Case No.: NRAS No.: SDG No.:
Preparation Method:
EPA
Sample
No.
Preparation
Date
>
Weight
(gram)
Volume
(mL)
FORM XII-IN
ILM05.2
-------
USEPA - CLP
13-IN
ANALYSIS RUN LOG
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS No.:
SDG No.
Instrument ID:
Start Date:
Analysis Method:
End Date:
EPA
Sample
No.
D/F
Time
A
L
S
B
A
S
B
A
B
E
C
D
C
A
C
R
C
O
C
U
F
E
Ar
P
B
ial:
M
G
/te.
M
N
3
H
G
N
I
K
S
E
A
G
N
A
T
L
V
Z
N
C
N
FORM XIII-IN
ILM05.2
-------
USEPA - CLP
14-IN
ICP-MS Tune
Lab Name:
Lab Code:
Case No.:
ICP-MS Instrument ID:
Contract:
NRAS No.:
SDG No.
Date:
Element - Mass
Be - 9
Mg - 24
Mg - 25
Mg - 26
Co - 59
In - 113
In - 115
Pb - 206
Pb - 207
Pb - 208
Avg. Measured Mass (amu)
Avg. Peak Width at
5% Peak Height (amu)
%RSD
Comments:
FORM XIV-IN
ILM05.2
-------
USEPA - CLP
15-IN
ICP-MS Internal Standards Relative Intensity Summary
Lab Name:
Lab Code:
Case No.:
ICP-MS Instrument ID:
Contract:
NRAS No.:
Start Date:
SDG No.: _
End Date:
EPA Sample
No.
Time
Internal Standards %RI For:
Element
Q
Element
Q
Element
Q
Element
Q
Element
Q
FORM XV-IN
ILM05.2
-------
SAMPLE LOG-IN SHEET
Lab Name
Received By (Print Name)
Page of
Log-in Date
Received By (Signature)
Case Number
Remarks :
1. Custody Seal(s)
2. Custody Seal Nos.
Present /Absent*
Intact /Broken
3. Traffic Present/Absent*
Reports/Chain of
Custody Records or
Packing Lists
4. Airbill
5. Airbill No.
6. Sample Tags
Airbill/Sticker
Present /Absent*
Present /Absent*
Sample Tag Numbers Listed/Not
Listed on
Traffic
Report/Chain of
Custody Record
7 . Sample Condition
Intact/Broken*/
Leaking
8. Cooler Temperature Present/Absent*
Indicator Bottle
9. Cooler Temperature
10. Does information
on Traffic
Reports/Chain of
Custody Records
and sample tags
agree9
11. Date Received at
Lab
12 . Time Received
Yes/No*
Sample Transfer
Fraction
Area #
By
On
Fraction
Area f
By
On
Sample Delivery Group No.
EPA
Sample #
Aqueous
Sample pH
Corresponding
Sample Tag *
Assigned
Lab 1
NRAS Number
Remarks :
Condition of
Sample
Shipment, etc.
* Contact SMO and attach record of resolution
Reviewed By
Date
Logbook No.
Logbook Page No.
FORM DC-1
ILM05.2
-------
FULL INORGANICS COMPLETE SDG FILE (CSF) INVENTORY SHEET
LABORATORY NAME
CITY/STATE
CASE NO. SDG NO.
SDG NOs. TO FOLLOW
NRAS NO.
CONTRACT NO.
SOW NO.
All documents delivered in the Complete SDG File must be original documents
where possible. (Reference - Exhibit B Section 2.6)
PAGE NOs. CHECK
FROM TO LAB REGION
1. Inventory Sheet (DC-2) (Do not number)
2. Sample Log-In Sheet (DC-1)
3. Traffic Report/Chain of Custody Record
4. Cover Page
5. SDG Narrative ,
Inorganic Analysis
6. Data Sheet (Form I-IN)
7. Initial & Continuing Calibration
- Verification (Form IIA-IN)
8. CRQL Standard
(Form IIB-IN)
9. Blanks (Form III-IN)
10. ICP-AES Interference Check Sample
(Form IVA-IN) '
11. ICP-MS Interference Check Sample
(Form IVB-IN)
12. Matrix Spike Sample Recovery
(Form VA-IN)
13. Post-Digestion Spike Sample Recovery
(Form VB-IN)
14. Duplicates (Form VI-IN)
15. Laboratory Control Sample
(Form VII-IN)
16. ICP-AES and ICP-MS Serial Dilutions
(Form VIII-IN)
17. Method Detection Limits (Annually)
(Form IX-IN)
18. ICP-AES Interelement Correction
Factors (Quarterly) (Form XA-IN)
19. ICP-AES Interelement Correction
Factors (Quarterly) (Form XB-IN)
20. ICP-AES and ICP-MS Linear Ranges
(Quarterly) (Form XI-IN)
21. Preparation Log (Form XII-IN)
22. Analysis Run Log (Form XIII-IN)
FORM DC-2-1 . ILM05.2
-------
PAGE NOs. CHECK
FROM TO LAB
23. ICP-MS Tune (Form XIV-IN)
24. ICP-MS Internal Standards Relative
Intensity Summary (Form XV-IN)
25. ICP-AES Raw Data
26. GFAA Raw Data (If Applicable)
27. ICP-MS Raw Data
28. Mercury Raw Data
29. Cyanide Raw Data
30. Preparation Logs Raw Data
31. Percent Solids Determination Log
32. USEPA Shipping/Receiving Documents
Airbill (No. of Shipments )
Sample Tags
Sample Log-In Sheet (Lab) '
33. Misc. Shipping/Receiving Records
(list all individual records)
Telephone Logs
34. Internal Lab Sample Transfer Records &
Tracking Sheets (describe or list)
35. Internal Original Sample Prep &
Analysis Records (describe or list)
Prep Records
Analysis Records
Description
36. Other Records (describe or list)
Telephone Communications Log
37. Comments:
Completed by:
(CLP Lab)
(Signature) (Print Name & Title) (Date)
Audited by:
(USEPA)
(Signature) (Print Name & Title) (Date)
FORM DC-2-2 ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
-------
EXHIBIT C
INORGANIC TARGET ANALYTE LIST
WITH CONTRACT REQUIRED
QUANTITATION LIMITS
C-l ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
ILM05.2 C-2
-------
EXHIBIT C - INORGANIC TARGET ANALYTE LIST WITH CONTRACT
REQUIRED QUANTITATION LIMITS
Table of Contents
Section Page
1.0 INORGANIC TARGET ANALYTE LIST AND CONTRACT REQUIRED
QUANTITATION LIMITS (CRQLs ) 5
C-3 ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
ILM05.2 C-4
-------
Exhibit C Section 1
Inorganic Target Analyte List and CRQLs
1.0 INORGANIC TARGET ANALYTE LIST AND CONTRACT REQUIRED QUANTITATION LIMITS
(CRQLs)
ICP-AES CRQL
Analyte CAS Number for Water1'2'3'4
(pg/L)
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
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
57-12-5
200
60
15
200
5
5
5000
10
50
25
100
10
5000
15
0.2
40
5000
35
10
5000
25
50
60
10
ICP-AES CRQL
for Soil1'2'3-"'5
(mg/kg)
40
12
3
40
1
1
1000
2
10
5
20
2
1000
3
0.1
8
1000
7
2
1000
5
10
12
1
ICP-MS CRQL
for Water1-2'4
(ug/L)
30
2
1
10
1
1
2
0.5
2
1
0.5
1
5
1
1
1
1
""
1The CRQLs are the minimum levels of quantitation acceptable under the
contract Statement of Work (SOW).
2Subject to the restrictions specified in Exhibit D, any analytical
method specified in ILM05.2 Exhibit D may be utilized as long as the
documented Method Detection Limits (MDLs) are less than one-half the CRQLs.
3Mercury is analyzed by cold vapor atomic absorption. Cyanide is
analyzed by colorimetry/spectrophotometry.
4Changes to the Inorganic Target Analyte List (TAL) (e.g., adding an
additional analyte) or CRQLs may be requested under the flexibility clause in
the contract.
5The CRQLs for soil are based on 100% solids and on the exact weights
and volumes specified in Exhibit D. Samples with less than 100% solids may
have CRQLs greater than those listed in the table above.
C-5
ILM05.2
-------
EXHIBIT D
INTRODUCTION TO ANALYTICAL METHODS
D-1/Introduction ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
ILM05.2 D-2/Introduction
-------
Exhibit D - Analytical Methods
Table of Contents
Section Page
1.0 INTRODUCTION 5
1.1 Inorganic Methods Flow Chart 5
1.2 Figure 1 - Inorganic Methods Flow Char t 6
1.3 Glassware Cleaning 6
1.4 Standard Stock Solutions 6
1.5 Verification of Aqueous Sample Preservatio n 6
1.6 Percent Solids Determination Procedure 7
1.7 Insufficient Sample Volume 8
1.8 Sample Mixing 8
1.9 Undiluted Analysis 8
1.10 Dissolved Metals 9
1.11 Replicate Exposure 9
1.12 Raw Data Requirement s 9
1.13 Quality Control Sample s 9
1.14 Safety 9
1.15 Pollution Prevention 10
1.16 Waste Management 10
Part A - Analytical Methods for Inductively Coupled Plasma - Atomic Emission
Spectroscopy
Part B - Analytical Methods for Inductively Coupled Plasma - Mass Spectrometry
Part C - Analytical Methods for Cold Vapor Mercury Analysis
Part D - Analytical Methods for Total Cyanide Analysis
D-3/Introduction ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
ILM05.2 D-4/Introduction
-------
Exhibit D Section 1
Introduction
1.0 INTRODUCTION
The inorganic analytical service provides a contractual framework for
laboratories. This.framework applies USEPA Contract Laboratory Program
(CLP) analytical methods for the isolation, detection, and quantitative
measurement of 23 metals (including mercury) and cyanide in water/
aqueous and/or soil/sediment samples.
The analytical methods that follow are designed to analyze water and
sediment/soil from hazardous waste sites for the presence of inorganic
analytes contained on the Inorganic Target Analyte List (TAL) (see
Exhibit C). The inorganic methods include alternative analysis
procedures for some analytes, multiple preparation procedures, and
Quality Control (QC) requirements. Analytical techniques in the
inorganic methodologies include Inductively Coupled Plasma - Atomic
Emission Spectroscopy (ICP-AES), Inductively Coupled Plasma - Mass
Spectroscopy (ICP-MS), Cold Vapor Atomic Absorption Spectroscopy, and
Spectrophotometry. Graphite Furnace Atomic Absorption (GFAA) may be
requested by the flexibility clause in the contract.
1.1 Inorganic Methods Flow Chart
Figure 1 outlines the general analytical scheme the Contractor shall
follow in performing standard trace metals and cyanide analyses under
this contract.
D-5/Introduction ILM05.2
-------
Exhibit D Section 1
Introduction (Con't)
1.2 Figure 1 - Inorganic Methods Flow Chart
Field Sample
Traffic Report or SMO
Specified Parameters
Water/Aqueous Soil/Sediment
Matrix Matrix
Acid Digestions
for Metals
Analysis
in Water
Metals Analysis
ICP-AES/ICP-MS/CVAA
Acid Digestions
for Metals
Analysis in
Soil/Sediment
Metals Analysis
ICP-AES/CVAA
Data Reports
1.3 Glassware Cleaning
Lab glassware to be used within the metals analysis must be acid cleaned
according to USEPA's manual, Methods for Chemical Analysis of Water and
Wastes or an equivalent procedure. An electronic version can be found
via USEPA's National Environmental Publications Internet Site (NEPIS) at
http://www.epa.gov/cincl.
1.4 Standard Stock Solutions
Stock solutions to be used for preparing instrument or method standards
may be purchased or prepared as described in the individual methods of
Exhibit D, Section "7 (Reagents and Standards) .
1.5 Verification of Aqueous Sample Preservation
1.5.1 At the time of sample receipt, the Contractor shall check the pH of
the sample and note in a preparation log if the pH is less than 2 for
metals. In addition, it should be noted if the pH is greater than 12
for a cyanide sample. Unless instructed bV the USEPA Regional CLP
Project Officer (CLP PO), 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 Sample Management
ILM05.2
D-6/Introduction
-------
Exhibit D Section 1
Introduction (Con't)
Office (SMO) for further instructions before proceeding with the
preparation and analysis. The Contractor may adjust the pH of a
sample for metals if SMO provides written documentation to the
Contractor from the USEPA Regional CLP PO or USEPA OERR Analytical
Operations/Data Quality Center (AOC) Inorganic Program Manager (AOC
PM) authorizing the adjustment.
1.5.2 Before preparation is initiated for an aqueous cyanide sample, the
Contractor shall test for the presence of sulfides and oxidizing
agents (e.g., residual chlorine). The test for sulfides shall be
performed by placing a drop of the sample on a strip of lead acetate
paper (which has been pre-moistened with pH 4 acetate buffer
solution). If the test strip turns black, the Contractor shall treat
the total volume of sample with powdered cadmium carbonate or lead
carbonate. Yellow cadmium sulfide precipitates when the sample
contains sulfide. This operation shall be repeated until a drop of
the treated sample solution does not darken the lead acetate test
paper. The solution shall be filtered through a dry filter paper
into a dry beaker, and the volume of sample to be used for analysis
shall be measured from the filtrate. It is recommended that the
Contractor 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. The test for oxidizing
agents shall be performed by placing a drop of the sample on a strip
of potassium iodide - starch test paper (KI - starch paper). If the
test strip turns blue, the Contractor shall contact SMO for further
instructions from the Region before proceeding with sample
preparation and analysis. The Contractor shall document the presence
of sulfides or oxidizing agents in the Sample Delivery Group (SDG)
Narrative.
1.6 Percent Solids Determination Procedure
1.6.1 Immediately following the weighing of the sample to be processed for
analysis, add 5-10 g of sample to a tared weighing dish. Weigh and
record the weight to the nearest 0.01 g.
1.6.2 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.
1.6.3 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.1 Remove the sample from the oven and cool in a
desiccator with the weighing dish cover in place before weighing.
Weigh and record weight to nearest 0.01 g. Do not analyze the dried
sample.
1.6.4 Duplicate percent solids determinations are required at the same
frequency as other analytical determinations. Duplicate results are
to be recorded on Form VI-IN.
*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/desiccate/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.
D-7/Introduction ILM05.2
-------
Exhibit D Section 1
Introduction (Con't)
1.6.5 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.
1.6.6 Calculate percent solids by the formula below. The value thus
obtained will be reported on the appropriate Forms I and, where
applicable, Forms VA-IN and VI-IN. This value will be used for
calculating analytical concentration on a dry weight basis.
EQ. 1 Percent Solids
, . , Sample Dry Weight ,__
%.Solids = x 100
Sample Wet Weight
1.6.7 If the sample contains less than 50% solids, the Contractor shall
notify SMO immediately of the samples impacted. After notification
to SMO, the Contractor shall proceed with sample analysis and
document the issue in the SDG Narrative.
1.7 Insufficient Sample Volume
If insufficient sample volume (less than the required amount) is
received to perform the analysis, the Contractor shall contact the SMO
to apprise them of the problem. SMO will contract 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.
1.8 Sample Mixing
Unless instructed otherwise by the USEPA Regional CLP PO, all samples
shall be mixed thoroughly prior to aliquoting for digestion. There is
no specific procedure provided herein for homogenization of soil/
sediment samples; however, an effort should be made to obtain a
representative aliquot.
1.9 Undiluted Analysis
1.9.1 All samples shall be run undiluted for multi-analyte analysis (i.e.,
the final product of the sample preparation procedure) unless-the
dilution adjusted detection limits for all analytes are below the
CRQL. When an analyte concentration exceeds the calibrated or linear
range, appropriate dilution (but not below the CRQL) and re-analysis
is required. The Contractor shall use the least dilution necessary
to bring the analyte(s) instrument reading within the upper half of
the calibrated or linear range 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.
1.9.2 For single analyte analysis, a diluted sample analysis may be the
only sample analysis performed if the analyte's instrument result is
in the upper half of the calibration range. An undiluted sample
analysis does not have to be performed in this case. The sample and
its associated matrix spike and duplicate shall initially be run at
the same dilution.
ILM05.2 D-8/Introduction
-------
Exhibit D Section 1
Introduction (Con't)
1.9.3 All sample dilutions shall be made with reagent water appropriately
acidified (except for cyanide) to maintain constant acid strength.
1.10 Dissolved Metals
1.10.1 If dissolved metals are requested by USEPA Regional Offices, the
Contractor shall follow the instructions provided on the Traffic
Report(s)/Chain of Custody Record(s). If there are no instructions
on the Traffic Report/Chain of Custody Record, the Contractor shall
digest the samples designated as dissolved metals.
1.10.2 If the Regional Office indicates on the Traffic Report/Chain of
Custody Record that a digestion is not to be performed when analyzing
field samples for dissolved metals, then a aqueous Laboratory Control
Sample (LCSW) and a post-digestion spike sample (hardcopy Form VB-IN
and diskette QC codes PDO and PDF) are not required.
1.11 Replicate Exposure
If the Contractor analyzes samples using multiple injections or
exposures, the Contractor must use the data obtained from all injections
or exposures to calculate the final sample result even if more than the
minimum number of injections or exposures are taken.
1.12 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 (QA) protocol
of Exhibit E. The raw data deliverable requirements are specified in
Exhibit B, Section 2.5.2.3. Raw data collected and provided in
association with the performance of analyses under this contract shall
conform to the appropriate provisions of Exhibit B.
1.13 Quality Control Samples
If the Sampler designated two (or more) samples as QC for the same
matrix, and the QC samples are not specifically labeled with the
analysis they are to be used for (dissolved metals and total metals),
then the Contractor is to contact SMO to report the issue. SMO shall
then contact the Region and notify the Contractor of the Regional
decision.
1.14 Safety
The toxicity or carcinogenicity of each reagent used in this SOW has not
been precisely defined; however, each chemical compound should be
treated as a potential health hazard. From this viewpoint, exposure to
these chemicals must be' reduced to the lowest possible level by whatever
means available. The laboratory is responsible for maintaining a
current awareness file of Occupational Safety and Health Administration
(OSHA) regulations regarding the safe handling of chemicals specified in
this method. A reference file of material handling data sheets should
also be made available to all personnel involved in the chemical
analysis.
D-9/Introduction ILM05.2
-------
Exhibit D Section 1
Introduction (Con't)
1.15 Pollution Prevention
1.15.1 Pollution prevention encompasses any technique that reduces or
eliminates the quantity or toxicity of waste at the point of
generation. Numerous opportunities for pollution prevention exist in
laboratory operation. USEPA has established a preferred hierarchy of
environmental management techniques that places pollution prevention
as the management option of first choice. Whenever feasible,
laboratory personnel should use pollution prevention techniques to
address their waste generation. When wastes cannot be feasibly
reduced at the source, USEPA recommends recycling as the next best
option.
1.15.2 For information about pollution prevention that may be applicable to
laboratories and research institutions consult "Less is Better:
Laboratory Chemical Management for Waste Reduction," available from
the American Chemical Society's Department of Government Relations
and Science Policy, 1155 16th Street, N.W., Washington D.C., 20036,
(202) 872-4477.
1.16 Waste Management
USEPA requires that laboratory waste management practices be conducted
consistent with all applicable rules and regulations. USEPA urges
laboratories to protect the air, water, and land by minimizing and
controlling all releases from hoods and bench operations, complying with
the letter and spirit of any sewer discharge permits and regulations,
and by complying with all solid and hazardous waste regulations,
particularly the hazardous waste identification rules and land disposal
restrictions. For further information on waste management consult "The
Waste Management Manual for Laboratory Personnel", available from the
American Chemical Society at the address listed in Section 1.15.2.
ILM05.2 D-10/Intr'oduction
-------
EXHIBIT D - PART A
ANALYTICAL METHODS
FOR
INDUCTIVELY COUPLED PLASMA -
ATOMIC EMISSION SPECTROSCOPY
D-1/ICP-AES ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
ILM05.2 D-2/ICP-AES
-------
Exhibit D - Analytical Methods for ICP-AES
Table of Contents
Section Page
1.0 SCOPE AND.APPLICATION 5
2.0 SUMMARY OF METHOD 5
3.0 DEFINITIONS 5
4.0 INTERFERENCES 6
4.1 Spectral Interferences 6
4.2 Physical Interferences 6
4.3 Chemical Interferences 6
5.0 SAFETY 7
6.0 EQUIPMENT AND SUPPLIES 7
6.1 Glassware/Labware 7
6.2 Inductively Coupled Plasma - Atomic Emission Spectrometer
(ICP-AES) 7
7.0 REAGENTS AND STANDARDS 8
7.1 Reagents 8
7.2 Standards 8
8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE 12
8.1 Sample Collection and Preservation 12
8.2 Procedures for Sample Storage 12
8.3 Procedure for Sample Digestate Storage 12
8.4 Contract Required Holding Time 12
9.0 CALIBRATION AND STANDARDIZATION 13
9.1 Instrument Operating Parameters 13
9.2 Microwave Calibration Procedure 13
9.3 Inductively Coupled Plasma - Atomic Emission Spectrometer
(ICP-AES) Instrument Calibration Procedure 14
9.4 Initial Calibration Verification (ICV) 14
9.5 Continuing Calibration Verification (CCV ) 15
9.6 Initial and Continuing Calibration Blank (ICB/CCB) 15
10.0 PROCEDURE 16
10.1 Sample Preparation 16
10.2 Microwave Digestion Cleaning Procedure 21
10.3 Sample Analysis 21
11.0 DATA ANALYSIS AND CALCULATIONS 23
11.1 Water/Aqueous Sample Calculation 23
11.2 Soil Sample Calculation 23
11.3 Adjusted Method Detection Limit (MDL)/Adjusted Contract
Required Quantitation Limit (CRQL) Calculation 23
12.0 QUALITY CONTROL (QC) 25
12.1 Initial Calibration Verification (ICV) 25
12.2 Continuing Calibration Verification (CCV ) 25
12.3 Contract Required Quantitation Limit (CRQL) Check
Standard (CRI) 25
12.4 Blank Analyses 25
12.5 Interference Check Sample (ICS) 27
12.6 Spike Sample Analysi s 28
12.7 Duplicate Sample Analysi s 29
12.8 Laboratory Control Sample (LCS) Analysis 30
D-3/ICP-AES ILM05.2
-------
Exhibit D - Analytical Methods for ICP-AES
Table of Contents (Con't)
Section Page
12.9 ICP-AES Serial Dilution Analysis 30
12.10 Method Detection Limit (MDL) Determination 31
12.11 Interelement Corrections 32
12.12 Linear Range Analysis Standard (LRS) 32
13.0 METHOD PERFORMANCE 33
14.0 POLLUTION PREVENTION 33
15.0 WASTE MANAGEMENT 33
16.0 REFERENCES 33
17.0 TABLES/DIAGRAMS/FLOWCHARTS 34
TABLE 1: Interferent and Analyte Elemental Concentrations
Used for ICP-AES Interference Check Sample (ICS) .... 34
TABLE 2: Spiking Levels for Spike Sample Analysis 35
ILM05.2 D-4/ICP-AES
-------
Exhibit D (ICP-AES) Sections 1-3
Scope and Application
1.0 SCOPE AND APPLICATION
The following method is an inductively coupled atomic plasma-atomic
emission spectroscopy procedure that is used to analyze water, sediment,
sludge, and soil samples taken from hazardous waste sites. All metals
(except mercury) which are contained in the Inorganic Target Analyte
List (TAL) in Exhibit C are quantitated by this Inductively Coupled
Plasma - Atomic Emission Spectroscopy (ICP-AES) method.
2.0 SUMMARY OF METHOD
Water and soil samples are treated with acids and heat or microwave
energy to solubilize the metals present. These digestates are then
analyzed for trace metals by an atomic emission optical spectroscopic
technique. Samples are nebulized and the aerosol that is produced is
transported to a plasma torch where excitation occurs. Characteristic
atomic-line emission spectra are produced by a radio-frequency
inductively coupled plasma. The spectra are dispersed and the
intensities of the lines are monitored by a photosensitive device. The
signals from the photosensitive device are processed by a computer. A
background correction technique is required to compensate for variable
background contribution to the spectra 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.
3.0 DEFINITIONS
See Exhibit G for a complete list of definitions.
D-5/ICP-AES
ILM05.2
-------
Exhibit D (ICP-AES) Section 4
Interferences
4.0 INTERFERENCES
Several types of interference effects may contribute to inaccuracies in
the determination of trace elements in water and soil/sediments. To
prevent this, 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 milligrams per Liter (mg/L) and
when total elements are determined after the appropriate digestion
procedures are performed. Several types of interferences are summarized
below:
4.1 Spectral Interferences
Spectral interferences can be categorized as: overlap of a spectral line
from another element, unresolved overlap of molecular band spectra,
background contribution from continuous or recombination phenomena,
and/or 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. This
would require 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.
4.2 Physical Interferences
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
minimize these interferences. If these types of interferences are
present, they must be reduced by dilution of the sample.
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.
4.3 Chemical Interferences
Chemical interferences are characterized by molecular compound
formation, ionization effects and solute vaporization effects. Normally
these effects are not pronounced with the Inductively Coupled Plasma -
Atomic Emission Spectrometer (ICP-AES) 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, and by matrix matching. These types of interferences can be
highly dependent on matrix type and the specific analyte element.
ILM05.2 D-6/ICP-AES
-------
Exhibit D (ICP-AES) Sections 5 & 6
Safety
5.0 SAFETY
See Section 1.14 in Exhibit D - Introduction to Analytical Methods.
6.0 EQUIPMENT AND SUPPLIES
Brand names, suppliers, and part numbers are for illustrative purposes
only. No endorsement is implied. Equivalent performance may be
achieved using equipment and supplies other than those specified here,
however, a demonstration of equivalent performance meeting the
requirements of this Statement of Work (SOW) is the responsibility of
the Contractor. The Contractor shall document any use of alternate
equipment or supplies in the Sample Delivery Group (SDG) Narrative.
6.1 Glassware/Labware
6.1.1 250 milliliter (mL) beaker or other appropriate vessel
6.1.2 Watch glasses
6.1.3 Funnels
6.1.4 Graduated cylinders
6.1.5 Various volumetric flasks (Type A)
6.1.6 Thermometer that covers a range of 0-200°C
6.1.7 Whatman No. 42 filter paper or equivalent
6.1.8 Hot plate, block digester, or other heating source
6.1.9 Equipment and supplies for microwave digestion
6.1.9.1 Whatman No. 41 filter paper (or equivalent)
6.1.9.2 Disposable polypropylene filter funnel
6.1.9.3 Polyethylene bottles, 125 mL, with caps
6.1.9.4 Microwave oven with programmable power settings up to at least 600
watts.
6.1.9.5 The system must use PTFE PFA digestion vessels (120 mL capacity)
capable of withstanding pressure of up to 110 (ą10) pounds per
square inch (psi) [7.5 (ą0.7 atm)]. These vessels are capable of
controlled pressure relief at pressures exceeding 110 psi.
6.1.9.6 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 revolutions per minute (rpm).
6.1.10 Balances - Analytical Balance, 300 gram (g) capacity, and minimum
ą0.01 g.
6.2 Inductively Coupled Plasma - Atomic Emission Spectrometer (ICP-AES)
consisting of a computer controlled atomic emission spectrometer with
background correction, a radio frequency generator, and a supply of
Argon gas, welding grade or better.
D-7/ICP-AES ILM05.2
-------
Exhibit D (ICP-AES) Section 7
Reagents and Standards
7.0 REAGENTS AND STANDARDS
7.1 Reagents
Acids used in the preparation of standards and for sample processing
must be ultra-high purity grade or equivalent. (Redistilled acids are
acceptable.)
7.1.1 Reagent water - The purity of this water must be equivalent to ASTM
Type II water (ASTM D1193-77). Use this preparation for all
reagents, standards, and dilutions of solutions.
7.1.2 Acetic acid - Concentrated (specific gravity 1.06).
7.1.3 Hydrochloric acid - Concentrated (specific gravity 1.19).
7.1.4 Hydrochloric acid, (1+1) - Add 500 milliliters (mL) cone. HC1
(specific gravity 1.19) to 400 mL reagent water and dilute to 1 Liter
(L) .
7.1.5 Nitric acid - Concentrated (specific gravity 1.41).
7.1.6 Nitric acid, (1+1) - Add 500 mL cone. HNO 3 (specific gravity 1.41) to
400 mL reagent water and dilute to 1 L.
7.1.7 Hydrogen peroxide (30%)
7.1.8 Nitric acid, 5% (v/v) - Add 50 mL cone. HNO3 to 500 mL reagent water;
dilute to 1 L.
7.2 Standards
7.2.1 Introduction
The Contractor must provide all standards to be used with this
contract. These standards may be used only after they have been
certified according to the procedure in Exhibit E, Section 8.0. The
Contractor must be able to verify that the standards-are certified.
Manufacturer's certificates of analysis must be retained by the
Contractor and presented upon request.
7.2.2 Stock Standard Solutions
7.2.2.1 Stock standard solutions may be purchased or prepared from ultra
high purity grade chemicals or metals. All salts must be dried
for 1 hour at 105°C unless otherwise specified.
(CAUTION : Many metal salts are extremely toxic and may be fatal if
swallowed. Wash hands thoroughly after handling) Typical stock
solution preparation procedures follow.
7.2.2.2 Aluminum solution, stock (1 mL = 100 ug Al) - Dissolve 0.100 grams
(g) of aluminum metal in an acid mixture of 4 mL of (1+1) HC1 and
1 mL of cone. HN03 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 reagent water.
7.2.2.3 Antimony solution, stock (1 mL = 100 pg Sb) - Dissolve 0.2669 g
K(SbO)C4H406 in reagent water, add 10 mL (1+1) HC1 and dilute to
1000 mL with reagent water.
ILM05.2 D-8/ICP-AES
-------
Exhibit D (ICP-AES) Section 7
Reagents and Standards (Con't)
7.2.2.4 Arsenic solution, stock (1 mL = 100 pg As) - Dissolve 0.1320 g of
As2O3 in 100 mL of reagent water containing 0.4 g NaOH. Acidify
the solution with 2 mL cone. HN03 and dilute to 1000 mL with
reagent water.
7.2.2.5 Barium solution, stock (1 mL = 100 pg Ba) - Dissolve 0.1516 g
BaCl2 (dried at 250°C for 2 hours) in 10 mL reagent water with 1
mL (1+1) HC1. Add 10.0 mL (1+1) HC1 and dilute to 1000 mL with
reagent water.
7.2.2.6 Beryllium solution, stock (1 mL = 100 ug Be) - Do not dry.
Dissolve 1.966 grams (g) BeSO 4 =* 4H20, in reagent water, add 10.0
mL cone. HN03 and dilute to 1000 mL with reagent water.
7.2.2.7 Cadmium solution, stock (1 mL = 100 ug Cd) - Dissolve 0.1142 g CdO
in a minimum amount of (1+1) HN03 . Heat to increase rate of
dissolution. Add 10.0 mL cone. HNO3 and dilute to 1000 mL with
reagent water.
7.2.2.8 Calcium solution, stock (1 mL = 100 ug Ca) - Suspend 0.2498 g
CaCO3 dried at 180°C for 1 hour before weighing in reagent water
and dissolve cautiously with a minimum amount of (1+1) HNO 3. Add
10.0 mL cone. HN03 and dilute to 1000 mL with reagent water.
7.2.2.9 Chromium solution, stock (1 mL = 100 pg Cr) - Dissolve 0.1923 g of
Cr03 in reagent water. When solution is complete acidify with 10
mL cone. HNO3 and dilute to 1000 mL with reagent water.
7.2.2.10 Cobalt solution, stock (1 mL = 100 pg Co) - Dissolve 0.1000 g of
cobalt metal in a minimum amount of (1+1) HNO 3. Add 10.0 mL (1+1)
HC1 and dilute to 1000 mL with reagent water.
7.2.2.11 Copper solution, stock (1 mL = 100 pg Cu) - Dissolve 0.1252 g CuO
in a minimum amount of (1+1) HN03 . Add 10.0 mL cone. HN03 and
dilute to 1000 mL with reagent water.
7.2.2.12 Iron solution, stock (1 mL = 100 pg Fe) - Dissolve 0.1430 g Fe203
in a warm mixture of 20 mL (1+1) HC1 and 2 mL of cone. HNO 3.
Cool, add an additional 5 mL of cone. HNO 3 and dilute to 1000 mL
with reagent water.
7.2.2.13 Lead solution, stock (1 mL = 100 pg Pb) - Dissolve 0.1599 g
Pb(NO3)2 in a minimum amount of (1+1) HN03. Add 10.0 mL of cone.
HN03 and dilute to 1000 mL with reagent water.
7.2.2.14 Magnesium solution, stock (1 mL = 100 pg Mg) - Dissolve 0.1658 g
MgO in a minimum amount of (1+1) HNO 3. Add 10.0 mL cone. HN03 and
dilute to 1000 mL with reagent water.
7.2.2.15 Manganese solution, stock (1 mL = 100 pg Mn) - Dissolve 0.1000 g
of manganese metal in the acid mixture, 10 mL cone. HC1 and 1 mL
cone. HN03, and dilute to 1000 mL with reagent water.
7.2.2.16 Nickel solution, stock (1 mL = 100 pg Ni) - Dissolve 0.1000 g of
nickel metal in 10 mL hot cone. HN03 , cool and dilute to 1000 mL
with reagent water.
7.2.2.17 Potassium solution, stock (1 mL = 100 pg K) - Dissolve 0.1907 g
KC1, dried at 110°C, in reagent water. Dilute to 1000 mL.
D-9/ICP-AES ILM05.2
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Exhibit D (ICP-AES) Section 7
Reagents and Standards (Con't)
7.2.2.18 Selenium solution, stock (1 mL = 100 ug Se) - Do not dry.
Dissolve 0.1727 g H2Se03 (actual assay 94.6%) in reagent water and
dilute to 1000 mL.
7.2.2.19 Silver solution, stock (1 mL = 100 ug Ag) - Dissolve 0.1575 g
AgN03 in 100 mL of reagent water and 10 mL cone. HNO 3. Dilute to
1000 mL with reagent water.
7.2.2.20 Sodium solution, stock (1 mL = 100 ug Na) - Dissolve 0.2542 g NaCl
in reagent water. Add 10.0 mL cone. HNO 3 and dilute to 1000 mL
with reagent water.
7.2.2.21 Thallium solution, stock (1 mL = 100 ug Tl) - Dissolve 0.1303 g
T1NO3 in reagent water. Add 10.0 mL cone. HNO3 and dilute to 1000
mL with reagent water.
7.2.2.22 Vanadium solution, stock (1 mL = 100 ug V) - Dissolve 0.2297
NH,V03 in a minimum amount of cone. HN03. Heat to increase rate of
dissolution. Add 10.0 mL cone. HN03 and dilute to 1000 mL with
reagent water.
7.2.2.23 Zinc solution, stock (1 mL = 100 ug Zn) - Dissolve 0.1245 g ZnO in
a minimum amount of dilute HNO 3. Add 10.0 mL cone. HNO3 and
dilute to 1000 mL with reagent water.
7.2.3 Secondary Dilution Standards
7.2.3.1 Mixed Secondary Dilution Standards
Prepare mixed secondary dilution standard solutions by diluting
the appropriate volumes of stock standards with acidified reagent
water to obtain the final volume. Mixed secondary dilution
standard solutions may be purchased. The purchased standards
shall meet the requirements in Section 7.2.1.
7.2.4 Working Standards
7.2.4.1 The calibration blank is prepared by diluting 2 mL of (1+1) HNO3
and 10 mL of (1+1) HC1 to 100 mL with reagent water. Prepare a
sufficient quantity to be used to flush the system between
standards and samples.
7.2.4.2 Contract Required Quantitation Limit (CRQL) Check Standard (CRI)
The concentration of the analytes in the CRI shall be at the
respective CRQLs. Information regarding the"CRI shall be reported
on Form IIB-IN.
7.2.4.3 Interference Check Sample (ICS) Solution
The ICS consists of two solutions: Solution A (ICSA) and Solution
AB (ICSAB). ICSA consists of the interferents and ICSAB consists
of the analytes mixed with the interferents.
7.2.4.4 Method Detection Limit (MDL) Solution
The MDL solution shall be at a concentration of 3 to 5 times the
expected MDL.
ILM05.2 D-10/ICP-AES
-------
Exhibit D (ICP-AES) Section 7
Reagents and Standards (Con't)
7.2.4.5 Mixed Calibration Standard Solutions
7.2.4.5.1 Prepare mixed calibration standard solutions by combining
appropriate volumes of the stock solutions in volumetric flasks
(see Sections 7.2.4.5.2 through 7.2.4.5.7). Add 2 mL of (1+1)
HNO3 and 10 mL of (1+1) HC1 and dilute to 100 mL with reagent
water (see Note in Section 7.2.4.5.6). 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 with aging. Although
not specifically required, some typical calibration standard
combinations follow.
7.2.4.5.2 Mixed standard solution I - manganese, beryllium, cadmium,
lead, and zinc.
7.2.4.5.3 Mixed standard solution II - barium, copper, iron, vanadium,
and cobalt.
7.2.4.5.4 Mixed standard solution III - arsenic and selenium.
7.2.4.5.5 Mixed standard solution IV - calcium, sodium, potassium,
aluminum, chromium, and nickel.
7.2.4.5.6 Mixed standard solution V - antimony, magnesium, silver and
thallium.
NOTE: If the addition of silver to the recommended acid
combination results in an initial precipitation, add 15 mL of
reagent water and warm the flask until the solution clears.
Cool and dilute to 100 mL with reagent water. For this acid
combination, the silver concentration should be limited to 2
milligrams per Liter (mg/L). Silver under these conditions is
stable in a tap water matrix for 30 days. Higher
concentrations of silver require additional HC1.
7.2.4.5.7 Protect all standards from light. Samples, sample digestates,
and standards must be stored separately.
D-11/ICP-AES ILM05.2
-------
Exhibit D (ICP-AES) Section 8
Sample Collection, Preservation, and Storage
8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE
8.1 Sample Collection and Preservation
All samples must be collected in glass or polyethylene containers.
Water/aqueous samples must be preserved with nitric acid to pH less than
2 immediately after collection. All samples must be iced or
refrigerated at 4°C (ą2°C) from the time of collection until digestion.
8.1.1 Dissolved Metals
For the determination of dissolved metals, the sample must be
filtered through a 0.45 micrometer (urn) pore diameter membrane filter
at the time of collection or as soon as possible. Use a portion of
the sample to rinse the filter flask, discard this portion, and
collect the required volume of filtrate. Preserve the filtrate with
nitric acid to pH less than 2 immediately after filtration.
8.2 Procedures for Sample Storage
The samples must be protected from light and refrigerated at 4°C (+2°C)
from the time of receipt until 60 days after delivery of a complete,
reconciled data package to USEPA. After 60 days the samples may be
disposed of in a manner that complies with all applicable regulations.
8.3 Procedure for Sample Digestate Storage
Sample digestates must be stored until 365 days after delivery of a
complete, reconciled data package to USEPA.
8.4 Contract Required Holding Time
The maximum holding time for metals is 180 days from Validated Time of
Sample Receipt (VTSR).
ILM05.2 D-12/ICP-AES
-------
Exhibit D (ICP-AES) Section 9
Calibration and Standardization
9.0 CALIBRATION AND STANDARDIZATION
9.1 Instrument Operating Parameters
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. The Method Detection
Limit (MDL), 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 (QC) data confirming
instrument performance and analytical results.
9.2 Microwave Calibration Procedure
9.2.1 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 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.
9.2.2 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
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.
9.2.3 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 kilogram
(kg) of water exposed to microwave radiation for a fixed period of
time. The water is placed in a PTFE beaker (or a beaker that is made
of some other material that does not absorb microwave energy) and
stirred before measuring the temperature. Glass beakers absorb
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 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 ą0.1°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.
D-13/ICP-AES ILM05.2
-------
Exhibit D (ICP-AES) Section 9
Calibration and Standardization (Con't)
The absorbed power is determined by the following formula:
EQ. 1 Absorbed Power
(K) (CJ (m) (DT)
p = Ł
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).
t = The time in seconds (s) .
Using 2 minutes and 1 kg of reagent 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.
9.3 Inductively Coupled Plasma - Atomic Emission Spectrometer (ICP-AES)
Instrument Calibration Procedure
9.3.1 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.
9.3.2 The calibration standards shall be prepared as in Section 7.2.4.5.
9.3.3 Calibrate the ICP-AES instruments according to instrument
manufacturer's recommended procedures. At least two standards shall
be used for ICP-AES calibration. One of the standards shall be a
blank.
9.3.4 Any changes or corrections to the analytical system shall be followed
by recalibration.
9.4 Initial Calibration Verification (ICV)
9.4.1 Immediately after each of the ICP-AES systems have been calibrated,
the accuracy of the initial calibration shall be verified and
documented for every analyte by the analysis of the ICV solution (s)
at each wavelength used.
9.4.2 Only if the ICV solution(s) is (are) not available from USEPA, or
where a certified solution of an analyte is not available from any
source, analyses shall be conducted on an independent standard at a
ILM05.2 D-14/ICP-AES
-------
Exhibit D (ICP-AES) Section 9
Calibration and Standardization (Con't)
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.
9.4.3 The ICV solution(s) shall be run at each wavelength used for
analysis. The values for the ICV shall be reported on Form IIA-IN.
9.5 Continuing Calibration Verification (CCV)
9.5.1 To ensure calibration accuracy during each analysis run, one of the
following standards is to be used for the CCV 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 CCV standard shall be different than the
concentration used for the ICV and shall be one of the following
solutions at or near one-half of the calibration standard:
^ USEPA Solutions
" NIST Standards
'" A Contractor-prepared standard solution
The same CCV standard shall be used throughout the analysis runs for
a Sample Delivery Group (SDG) of samples received.
9.5.2 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.
9.5.3 Information regarding the CCV shall be reported on Form IIA-IN.
9.6 Initial and Continuing Calibration Blank (ICB/CCB)
A calibration blank shall be analyzed at each wavelength used for
analysis immediately after every ICV and CCV, at a frequency of 10% or
every 2 hours 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 analyzed immediately after the last CCV, and the
last CCV shall be analyzed immediately after the last analytical sample
of the run. The results for the calibration blanks shall be reported on
Form III-IN.
D-15/ICP-AES ILM05.2
-------
Exhibit D (ICP-AES) Section 10
Procedure
10.0 PROCEDURE
10.1 Sample Preparation
10.1.1 If insufficient sample amount (less than 90% of the required amount)
is received to perform the analyses, the Contractor shall contact the
Sample Management Office (SMO) to inform them of the problem. SMO
will contact the Region for instructions. The Region will either
require that no sample analyses be performed or will require that a
reduced volume be used for the sample analysis. No other changes in
the analyses will be permitted. The Contractor shall document the
Region's decision in the Sample Delivery Group (SDG) Narrative.
10.1.2 If multiphase samples (e.g., two-phase liquid sample, oily
sludge/sandy soil sample) are received by the Contractor, the
Contractor shall contact SMO to apprise them of the type of sample
received. SMO will contact the Region. If all phases of the sample
are amenable to analysis, the Region may require the Contractor to do
any of the following:
30 Mix the sample and analyze an aliquot from the homogenized
sample.
30 Separate the phases of the sample and analyze one or more of
the phases, separately. SMO will provide EPA sample numbers
for the additional phases, if required.
00 Do not analyze the sample.
10.1.2.1 If all of the phases are not amenable to analysis (i.e., outside
scope), the Region may require the Contractor to do any of the
following:
:x: Separate the phases and analyze the phase (s) that is (are)
amenable to analysis. SMO will provide EPA sample numbers
for the additional phases, if required.
*> DO not analyze the sample.
10.1.2.2 No other changes in the analyses will be permitted. The
Contractor shall document the Region's decision in the SDG
Narrative.
10.1.3 Water/Aqueous Sample Preparation
10.1.3.1 Preparation Method/Code (HW1) (USEPA Method 200.7, December 1982)
Shake sample and transfer 50-100 milliliter (mL) of well-mixed
sample to a 250 mL heating vessel, add 2 mL of (1+1) HNO 3 and 10
mL of (1+1) HC1 to the sample. Cover with watch glass or similar
cover and heat on a hot plate, block digester, 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 50-100 mL with reagent water. The sample
is now ready for analysis. Concentrations so determined shall be
ILM05.2 D-16/ICP-AES
-------
Exhibit D (ICP-AES) Section 10
Procedure (Con't)
reported as "total". If volumes less than 100 mL are used, all
other reagents shall be reduced appropriately (e.g., if 50 mL is
used, reduce reagent volumes by one-half). The final volume of
the digestate must equal the initial volume of the sample aliquot.
10.1.3.2 Preparation Method/Code (MW1) (USEPA SW-846 Method 3015)
10.1.3.2.1 A 45 mL aliquot of the sample is measured into PTFE digestion
vessels.
10.1.3.2.2 5 mL of high purity concentrated HN03 is added to the digestion
vessels.
10.1.3.2.3 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 gram (g).
10.1.3.2.4 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 overflow 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.
10.1.3.2.5 This procedure is energy balanced for five 45 mL water samples
(each with 5 mL of acid) to produce consistent conditions.
When fewer than five samples are digested, the remaining
vessels must be filled with 45 mL of tap, deionized, or reagent
water and 5 mL of concentrated nitric acid.
10.1.3.2.6 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.
10.1.3.2.7 The initial temperature of the samples should be 24°C (ą1°C).
The Preparation Blank (PB) must have 45 mL of deionized water
and the same amount (5 mL) of acid that is added to the
samples.
10.1.3.2.8 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°C (ą4°C) in 10 minutes and permits a slow rise to 165-170°C
during the second 10 minutes.
10.1.3.2.9 Following the 20 minute program, the samples are left to cool
in the microwave unit for 5 minutes, with the exhaust fan on.
The samples and/or carousel may then be removed from the
microwave unit. Before opening the vessels, let cool until
they are no longer hot to the touch.
10.1.3.2.10 After the sample vessel has cooled, weigh the sample vessel and
compare to the initial weight as reported on the preparation
log. Any sample vessel exhibiting a less than or equal to
0.5 g loss into the overflow vessel must have any excess sample
from the associated collection vessel added to the original
sample vessel before proceeding with the sample preparation.
D-17/ICP-AES ILM05.2
-------
Exhibit D (ICP-AES) Section 10
Procedure (Con't)
Any sample vessel exhibiting a greater than 0.5 g loss must be
identified in the preparation log and the sample redigested.
10.1.3.2.11 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 Whatman No. 41 (or equivalent) 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".
10.1.3.3 Preparation Method/Code (MW2) (ASTM Standard D4309-91)
10.1.3.3.1 A 50 mL aliquot of the sample is measured into PTFE digestion
vessels.
10.1.3.3.2 3mLof high purity concentrated HN03 and 2 mL of concentrated
HC1 is added to the digestion vessels.
10.1.3.3.3 Proceed as in Preparation Method/Code "MW1", Sections
10.1.3.2.3 through 10.1.3.2.11.
10.1.3.3.4 Sample Filtration - The digested samples are shaken well to mix
in any condensate within the digestion vessel before being
opened. If necessary, the digestates are then filtered through
filter paper and diluted to 55 mL. The samples are now ready
for analysis. The sample results must be corrected by a factor
of 1.1 in order to report final concentration values based on
an initial volume of 50 mL. Concentrations so determined shall
be reported as "total".
10.1.4 Soil/Sediment Sample Preparation
10.1.4.1 Preparation Method/Code (HS1) (USEPA Method 200.7, December 1982)
10.1.4.1.1 Mix the sample thoroughly to achieve homogeneity. For each
digestion procedure, weigh (to the nearest 0.01 g) a 1.0 to
1.5 g portion of sample and transfer to a beaker.
10.1.4.1.2 Add 10 mL of 1:1 nitric acidJ (HNO 3), mix the slurry, and cover
with a watch glass. Heat the sample to 92-95°C on hot plate or
block digester, and reflux for 10 minutes without boiling.
Allow the sample to cool, add 5 mL of concentrated HNO3,
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.
10.1.4.1.3 After the second reflux step has been completed and the sample
has cooled, add 2 mL of reagent water and 3 mL of 30% hydrogen
peroxide (H202) . Return the heating vessel to the heat 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.
ILM05.2 D-18/ICP-AES
-------
Exhibit D (ICP-AES) Section 10
Procedure (Con't)
Continue to add 30% H202 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% H2 02.
10.1.4.1.4 Add 5 mL of 1:1 HC1 and 10 mL of reagent water, return the
covered heating vessel to the heat 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
reagent 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.
Dilute the digestate 1:1 (200 mL final volume) with acidified
water [prepared by diluting 2 mL of (1+1) HN03 and 10 mL of
(1+1) HC1 to 100 mL] to maintain constant acid strength. The
sample is now ready for analysis.
10.1.4.2 Preparation Method/Code (HS2) (USEPA SW-846 Method 3050B)
10.1.4.2.1 Mix the sample thoroughly to achieve homogeneity. For each
digestion procedure, weigh (to the nearest 0.01 g) a 1.0 to 2.0
g portion of sample and transfer to a beaker.
10.1.4.2.2 Add 10 mL of 1:1 nitric acid (HNO 3) , mix the slurry, and cover
with a watch glass. Heat the sample to 92-95°C on hot plate,
block digester, or equivalent heating source, and reflux for 10
minutes without boiling. Allow the sample to cool, add 5 mL of
concentrated HN03, 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. Add an additional 5 mL of
concentrated HN03 and reflux. Repeat this step until sample
oxidation is complete (no brown fumes generated).
10.1.4.2.3 After the reflux steps have been completed and the sample has
cooled, add 2 mL of reagent water and 3 mL of 30% hydrogen
peroxide (H202). Return the heating vessel to the heat 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.
10.1.4.2.4 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% H2 02.
10.1.4.2.5 Add 10 mL of concentrated HC1 and return the covered heating
vessel to the heat 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 reagent 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 sample is now ready for analysis.
D-19/ICP-AES ILM05.2
-------
Exhibit D (ICP-AES) Section 10
Procedure (Con't)
10.1.4.3 Preparation Method/Code (MSI) (USEPA SW-846 Method 3051)
10.1.4.3.1 Add a representative 0.50 g (ą0.01 g) of sample to the PTFE PFA
vessel.
10.1.4.3.2 Add 10 mL of concentrated nitric acid. If a vigorous reaction
occurs, allow the reaction to stop before capping the vessel.
10.1.4.3.3 Cap the vessel, then tighten using constant torque to 12
ft/lbs, according to the manufacturer's direction.
10.1.4.3.4 Connect the sample vessel to the overflow vessel using PTFE PFA
tubing.
10.1.4.3.5 Weigh the vessel assembly to the nearest 0.01 g.
10.1.4.3.6 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.
10.1.4.3.7 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.
10.1.4.3.8 The PB must have 0.5 mL of reagent water and the same amount
(10 mL) of acid that is added to the samples. The PB must
later be diluted to 50 mL in the same manner as the samples.
10.1.4.3.9 Irradiate the 2 sample vessel group at 344 watts for 10
minutes, or the 6-sample vessel group at 574 watts for 10
minutes.
10.1.4.3.10 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 atmospheres (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
(ą0.7 atm).
10.1.4.3.11 Allow the vessels to cool for a minimum of 5 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.
10.1.4.3.12 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.
10.1.4.3.13 Sample Filtration: Shake the sample well to mix in any
condensate within the digestion vessel before being opened.
ILM05.2 D-20/ICP-AES
-------
Exhibit D (ICP-AES) Section 10
Procedure (Con't)
Filter the digestion vessel into a 50 mL glass volumetric flask
through 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".
10.1.5 Non-Prepared Samples
10.1.5.1 Preparation Method/Code (NP1)
10.1.5.1.1 This code shall be used to report samples that are not digested
prior to analysis (e.g., dissolved metal samples that the
Contractor was instructed not to digest).
10.1.5.1.2 This Preparation Method/Code shall also be used to report the
non-prepared Method Detection Limit (MDL). The concentration
of this MDL shall be used to determine the appropriate
concentration qualifier for the results of non-prepared samples
and instrument Quality Control (QC) analyses.
10.2 Microwave Digestion Cleaning Procedure
10.2.1 Initial Cleaning of the PTFE PFA Digestion Vessels
10.2.1.1 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.
10.2.1.2 Rinse in reagent water.
10.2.1.3 Immerse in 1:1 HC1 for a minimum of 3 hours after the cleaning
bath has reached a temperature just below boiling.
10.2.1.4 Rinse in reagent water.
10.2.1.5 Immerse in 1:1 HN03 for a minimum of 3 hours after the cleaning
bath has reached a temperature just below boiling.
10.2.1.6 The vessels are then rinsed with copious amounts of reagent water
prior to use for any analyses under this contract.
10.2.2 Cleaning Procedure between Sample Digestions
10.2.2.1 Wash entire vessel in hot water using laboratory-grade non-phos-
phate detergent.
10.2.2.2 Rinse with 1:1 nitric acid.
10.2.2.3 Rinse 3 times with reagent water.
10.3 Sample Analysis
10.3.1 Set up the instrument with proper operating parameters established in
Section 9.1. The instrument must be allowed to become thermally
stable before beginning. This usually requires at least 30 minutes
of operation prior to calibration.
10.3.2 Initiate appropriate operating configuration of computer.
D-21/ICP-AES ILM05.2
-------
Exhibit D (ICP-AES) Section 10
Procedure (Con't)
10.3.3 Profile and calibrate instrument according to instrument
manufacturer's recommended procedures, using mixed calibration
standard solutions such as those described in Section 7.2.4.5.1.
10.3.4 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.
ILM05.2 D-22/ICP-AES
-------
Exhibit D (ICP-AES) Section 11
Data Analysis and Calculations
11.0 DATA ANALYSIS AND CALCULATIONS
11.1 Water/Aqueous Sample Calculation
The concentrations determined in the digestate are to be reported in
units of microgram per Liter (pg/L):
EQ. 2 Aqueous Sample Concentration
V
Concentration (pg/L) = C x - x DF
WHERE, C = Instrument value in pg/L
VŁ = Final digestion volume (mL)
Vt = Initial digestion volume (mL)
DF = Dilution Factor
11.2 Soil Sample Calculation
The concentrations determined in the digestate are to be reported on the
basis of the dry weight of the sample, in units of milligrams per
kilogram (mg/kg):
EQ. 3 Soil Sample Concentration
C x V
Concentration (dry wt.) (mg/kg) = x DF
W x S
WHERE, C = Concentration (mg/L)
V = Final sample volume in Liters (L)
W = Wet sample weight (kg)
S = % Solids/100 (see Exhibit D - Introduction to
Analytical Methods, Section 1.6).
DF = Dilution Factor
11.3 Adjusted Method Detection Limit (MDL)/Adjusted Contract Required
Quantitation Limit (CRQL) Calculation
To calculate the adjusted MDL or adjusted CRQL for water/aqueous
samples, substitute the value of the MDL (pg/L) or CRQL (pg/L) into the
"C" term in Equation 2 above.
Calculate the adjusted MDL or adjusted CRQL for soil samples as follows:
D-23/ICP-AES ILM05.2
-------
Exhibit D (ICP-AES) Section 11
Data Analysis and Calculations (Con't)
EQ. 4 Adjusted Soil MDL/Adjusted Soil CRQL Concentration
W V i
Adjusted Concentration (dry wt.) (mg/kg) = Cx x x xDF
WR VM s
WHERE, C = MDL or CRQL concentration (mg/kg)
WM = Minimum method required wet sample weight (g)
WR = Reported wet sample weight (g)
VM = Method required final sample volume (mL)
VR = Reported final sample volume (mL)
S = % Solids/100 (see Exhibit D - Introduction to
Analytical Methods, Section 1.6).
DF = Sample Dilution Factor
ILM05.2 D-24/ICP-AES
-------
Exhibit D (ICP-AES) Section 12
Quality Control
12.0 QUALITY CONTROL (QC)
12.1 Initial Calibration Verification (ICV)
The ICV standard shall be prepared in the same acid matrix as the
calibration standards and in accordance with the instructions provided
by the supplier. If measurements exceed the control limits of 90% (low)
and 110% (high), the analysis shall be terminated, the problem
corrected, the instrument recalibrated, and the calibration reverified.
Information regarding the ICV shall be reported on Form IIA-IN.
12.2 Continuing Calibration Verification (CCV)
The CCV standard shall be prepared by combining compatible elements at a
concentration equivalent to the mid-points of their respective
calibration curves. If the deviation of the CCV is greater than the
control limits specified of 90% (low) and 110% (high), the analysis
shall be stopped, the problem corrected, the instrument recalibrated,
the calibration verified, and the re-analysis of preceding 10 analytical
samples or all analytical samples analyzed since the last compliant
calibration verification shall be performed for the analytes affected.
Information regarding the CCV shall be reported on Form IIA-IN.
12.3 Contract Required Quantitation Limit (CRQL) Check Standard (CRI)
12.3.1 To verify linearity near the CRQL, a standard at the CRQL (CRI) shall
be prepared, -in the same acid matrix as the calibration standards,
and analyzed at the beginning and end of each sample analysis run,
immediately preceding the Interference Check Sample (ICS) analyses,
but not before the ICV. In addition, the Contractor shall analyze
the CRI at a frequency of not less than once per 20 analytical
samples1 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, ICS Solution A (ICSA), ICS Solution AB
(ICSAB), CCV and Continuing Calibration Blank (CCB), in that order].
12.3.2 The CRI shall be run for every wavelength used for analysis, except
those for Al, Ba, Ca, Fe, Mg, Na, and K. Information regarding the
CRI shall be reported on Form IIB-IN.
12.3.3 If the percent recovery of the CRI falls outside the control limits
of 70-130% (50-150% for antimony, lead, and thallium) for one or more
analytes, the CRI shall be re-analyzed immediately for those analytes
only. If the results of the re-analysis for those analytes fall
within the control limits, no further corrective action is required.
If the results of the re-analysis for those analytes do not fall
within the control limits, the analysis shall be terminated, the
problem corrected, the instrument recalibrated, the CRI analyzed, and
the samples associated with the CRI re-analyzed.
12.4 Blank Analyses
There are two different types of blanks required by this method. The
calibration blank is used in establishing the analytical curve while the
Preparation Blank is used to monitor for possible contamination.
1As defined in Exhibit G, CRI is an analytical sample.
D-25/ICP-AES
ILM05.2
-------
Exhibit D (ICP-AES) Section 12
Quality Control (Con't)
12.4.1 Initial and Continuing Calibration Blank (ICB/CCB)
The ICB and CCB are prepared with acids and reagent water. If the
absolute value of the calibration blank (ICB/CCB) result exceeds the
CRQL (see Exhibit C), the analysis shall be terminated, the problem
corrected, the instrument recalibrated, the calibration verified, and
re-analysis of the preceding 10 analytical samples or all analytical
samples analyzed since the last compliant calibration blank shall be
performed for the elements affected.
12.4.2 Preparation Blank (PB)
12.4.2.1 The PB shall contain all the reagents and in the same volumes as
used in processing the samples. The PB shall be carried through
the complete procedure and contain the same acid concentration in
the final solution as the sample solution used for analysis.
12.4.2.2 At least one PB, consisting of reagent water processed through
each sample preparation and analysis procedure (see Section 10),
shall be prepared and analyzed with every Sample Delivery Group
(SDG), or with each batch 2 of samples digested, whichever is more
frequent.
12.4.2.3 The first batch of samples in an SDG is to be assigned to
Preparation Blank one, the second batch to Preparation Blank two,
etc. (see Form III-IN). Each Sample Data Package shall contain
the results of all PB analyses associated with the samples in that
SDG.
12.4.2.4 The PB is to be reported for each SDG and used in all analyses to
ascertain whether sample concentrations reflect contamination in
the following manner:
12.4.2.4.1 If the absolute value of the concentration of the blank is less
than or equal to the CRQL (see Exhibit C), no further action is
required.
12.4.2.4.2 If any analyte concentration in the blank is above the CRQL,
the lowest concentration of that analyte in the associated
samples shall be greater than or equal to 10 times the blank
concentration. Otherwise, all samples associated with the
blank, with the analyte concentration less than 10 times the
blank concentration and above the CRQL, shall be redigested and
re-analyzed with appropriate new Quality Control (QC) for that
analyte. The only exception to this shall be an identified
field blank. The sample concentration is not to be corrected
for the blank value.
12.4.2.4.3 If the concentration of the blank is below the negative CRQL,
then all samples reported below 10 times the CRQL associated
with the blank, shall be redigested and re-analyzed with
appropriate new QC.
12.4.2.4.4 The values for the PB shall be reported on Form III-IN.
2A group of samples prepared at the same time.
ILM05.2 D-26/ICP-AES
-------
Exhibit D (ICP-AES) ~ Section 12
Quality Control (Con't)
12.5 Interference Check Sample (ICS)
12.5.1 The ICS is prepared by the analyst or obtained from USEPA, if
available.
12.5.2 To verify interelement and background correction factors, the
Contractor shall analyze and report the results for the ICS, for all
elements on the Target Analyte List (TAL) and for all interferents
(target and non-target), at the beginning and end of each analysis
run, but not before the ICV. In addition, the Contractor shall
analyze and report the results for the ICS at a frequency of not less
than once per 20 analytical samples3 per analysis run. These
analyses of the ICS shall be immediately followed by the analysis of
a CCV/CCB pair. The ICS solutions shall be obtained from USEPA, if
available, and analyzed according to the instructions supplied with
the ICS. The Contractor shall not dilute the ICS more than is
necessary to meet the linear range values of the instrument.
12.5.3 The ICS consists 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.
12.5.4 The analytical results of ICS Solution A (ICSA) shall fall within the
control limit of ą2 times the CRQL of the analyte's true value or
ą20% of the analyte's true value, whichever is greater (the true
value shall be zero unless otherwise stated) in the ICSA. For
example, if the analysis result (s) for Arsenic (CRQL = 15 ug/L, ICSA
true value = 0 ug/L) in the,ICSA analysis during the run is 29 ug/L,
then the analytical result for Arsenic falls within the ą2 times the
CRQL window for Arsenic in the ICSA. If the analytical results of
the ICSA do not fall within the control limits, the analysis shall be
terminated, the problem corrected, the instrument recalibrated, and
re-analysis of the analytical samples analyzed since the last
compliant ICSA shall be performed. For analytes with CRQLs less than
5000 ug/L, the ICSA results shall be reported from an undiluted
sample analysis.
12.5.5 Results for the ICS Solution AB (ICSAB) during the analytical runs
shall fall within the control limit of ą2 times the CRQL of the true
value or ą20% of the true value, whichever is greater, for the
analytes included in the ICSAB. If the analytical results of the
ICSA do not fall within the control limits, the analysis shall be
terminated, the problem corrected, the instrument recalibrated, and
re-analysis of the analytical samples analyzed since the last
compliant ICSAB shall be performed.
NOTE: The control limits and concentrations for the ICSAB are being
monitored. These may be adjusted to provide greater control of
interferences.
12.5.6 If true values for analytes contained in the ICS are not supplied
with the solutions, 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 ICS met all
contract specifications. Additionally, the results of this initial
mean determination shall be used as the true value for the lifetime
of that solution (i.e., until the solution is exhausted). Only if
3As defined in Exhibit G, ICSA and ICSAB are analytical samples.
D-27/ICP-AES ILM05.2
-------
Exhibit D (ICP-AES) Section 12
Quality Control (Con't)
the' ICS solutions are not available from USEPA, independent Check
Samples shall be prepared with interferent and analyte concentrations
at the levels specified in Table 1 - Interferent and Analyte
Elemental Concentrations Used for ICP-AES Interference Check Sample
(ICS). 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 IVA-IN. Results shall fall
within the control limit of ą2 times the CRQL of the established mean
value or ą20% of the established mean value, whichever is greater.
The mean and standard deviation shall be reported in the raw data.
Results from the ICS analyses shall be reported on Form IVA-IN for
all Inductively Coupled Plasma - Atomic Emission Spectroscopy (ICP-
AES) analytes.
12.6 Spike Sample Analysis
12.6.1 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). 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) or
for each SDG.4
12.6.2 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 12.7). The average of the duplicate results
cannot be used for the purpose of determining percent recovery.
Samples identified as field blanks and Performance Evaluation (PE)
samples shall not be used for spiked sample analysis. USEPA may
require that a specific sample be used for the spike sample analysis.
12.6.3 The analyte spike shall be added in the amount given in Table 2 -
Spiking Levels for Spike Sample Analysis, for each element analyzed.
NOTE: See Table 2 footnotes for concentration levels and
applications.
12.6.4 If the spike recovery is not at or within the limits of 75-125%, the
data of all samples received and associated with that spike sample
shall be flagged with the letter "N" on Forms IA/IB-IN and VA-IN. An
exception to this rule is granted when the sample concentration
exceeds the spike added 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.
12.6.5 When the matrix spike recovery falls outside the control limits and
the sample result does not exceed four times the spike added, a post-
digestion spike shall be performed for those elements that do not
meet the specified criteria (exception: Ag). Note that if a post-
digestion spike analysis is required for an analyte, the same EPA
sample that was used for the matrix spike analysis shall be used for
the post-digestion spike analysis. Spike the unspiked aliquot of the
sample at two times the indigenous level or two times the CRQL,
whichever is greater. Results of the post-digestion spike shall be
reported on Form VB-IN.
4USEPA may require additional spike sample analyses, upon USEPA Regional
CLP Project Officer (CLP PO) request.
ILM05.2 D-28/ICP-AES
-------
Exhibit D (ICP-AES) Section 12
Quality Control (Con't)
12.6.6 In the instance where there is more than one spike sample per matrix
per SDG, if one spike sample recovery is not within contract
criteria, flag all the samples of the same matrix and method in the
SDG. Individual component percent recoveries are calculated as
follows:
EQ. 5 Spike Percent Recovery
% Recovery = SSR " SR x 100
SA
WHERE, SSR = Spiked Sample Result
SR - = Sample Result
SA = Spike Added
12.6.7 When sample concentration is less than the Method Detection Limit
(MDL), use SR = 0 only for purposes of calculating percent recovery.
The Spike Sample Results (SSRs), Sample Results (SRs), Spike Added
(SA), and percent recovery (positive or negative) shall be reported
on Form VA-IN.
12.6.8 The units used for reporting SSRs will be identical to those used for
reporting sample results on Form IA-IN.
12.7 Duplicate Sample Analysis
12.7.1 One duplicate sample shall be analyzed from each group of samples of
a similar matrix type (i.e., water, soil) or for each SDG. 5
Duplicates cannot be averaged for reporting on Form IA-IN.
12.7.2 Duplicate sample analyses are required for percent solids. Samples
identified as field blanks and PE samples shall not be used for
duplicate sample analysis. USEPA may require that a specific sample
be used for duplicate sample analysis. The Relative Percent
Difference (RPD) for each component is calculated as follows:
EQ. 6 Duplicate Sample Relative Percent Difference
RPD = I S ~ D I x 100
(S+D)/2
WHERE, RPD = Relative Percent Difference
S = Sample Result (original)
D = Duplicate Result
12.7.3 The results of the duplicate sample analyses shall be reported on
Form VI-IN. A control limit of 20% for RPD shall be used for
original and duplicate sample values greater than or equal to five
times the CRQL (see Exhibit C). A control limit of the CRQL value
shall be entered in the "Control Limit" column on Form VI-IN if
either the sample or duplicate value is less than five times the
CRQL. If the sample and duplicate values are greater than or equal
5USEPA may require additional duplicate sample analyses, upon USEPA
Regional CLP PO request.
D-29/ICP-AES ILM05.2
-------
Exhibit D (ICP-AES) Section 12
Quality Control (Con't)
to five times the CRQL, or if the sample and duplicate values are
less than the CRQL, the "Control Limit" field is left empty.
12.7.4 If one result is above five times the CRQL level and the other is
below, use the CRQL criteria to determine if the duplicate analysis
is in control. If both sample and duplicate values are less than the
MDL, the RPD is not calculated on Form VI-IN. For solid sample or
solid duplicate results less than five times the CRQL, enter the
value of the CRQL, corrected for sample weight and percent solids,
(i.e., original, not duplicate 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 IA/IB-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 in the SDG. The
percent difference data will be used by USEPA to evaluate the long-
term precision of the methods for each element. Specific control
limits for each element will be added to Form VI-IN at a later date
based on these precision results.
12.8 Laboratory Control Sample (LCS) Analysis
12.8.1 Water/aqueous and solid LCS shall be analyzed for each analyte using
the same sample preparations, analytical methods, and Quality
Assurance/Quality Control (QA/QC) procedures employed for the EPA
samples received.
12.8.1.1 The aqueous LCS solution (LCSW) shall be obtained from USEPA [if
unavailable, the ICV solution(s) may be used]. One LCSW shall be
prepared and analyzed for every group of aqueous samples in a SDG,
or for each batch of aqueous samples digested, whichever is more
frequent.
12.8.1.2 The USEPA provided solid LCS (LCSS) shall be prepared and analyzed
using each of the procedures applied to the solid samples received
(exception: percent solids determination not required). If the
USEPA LCSS is unavailable, other USEPA QC Check Samples or other
certified materials may be used. The control limits for these
materials and samples must be documented. One LCSS shall be
prepared and analyzed for every group of solid samples in a SDG,
or for each batch of samples digested, whichever is more frequent.
12.8.2 All LCS and percent recovery results shall be reported on Form VII-
IN. If the percent recovery for the LCSW 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 LCSW redigested and re-analyzed with appropriate new QC.
12.8.3 If the results for the LCSS fall outside the control limits
established by USEPA, the analyses shall be terminated, the problem
corrected, and the samples associated with that LCSS redigested and
re-analyzed with appropriate new QC.
12.9 ICP-AES Serial Dilution Analysis
12.9.1 Prior to reporting concentration data for the analyte elements, the
Contractor shall analyze and report the results of the ICP-AES serial
dilution analysis. The ICP-AES serial dilution analysis shall be
performed on a sample from each group of samples of a similar matrix
type (i.e., water, soil) or for each SDG, whichever is more frequent.
ILM05.2 D-30/ICP-AES
-------
Exhibit D (ICP-AES) Section 12
Quality Control (Con't)
Samples identified as field blanks and PE samples shall not be used
for serial dilution analysis.
12.9.2 If the analyte concentration is sufficiently high (minimally a factor
of 50 above the MDL 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 a control limit of
10%, a chemical or physical interference effect must be suspected,
and the data for all affected analytes in the samples received and
associated with that serial dilution must be flagged with an "E" on
Form VIII-IN and Forms IA/IB-IN.
12.9.3,, The percent differences for each component are calculated as follows:
EQ. 7 Serial Dilution Percent Differences
I I - S I
% Difference = J-=- ^-1 x 100
WHERE, I = Initial Sample Result (Instrument reading)
S = Serial Dilution Result (Instrument reading x5)
12.9.4 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 in the SDG. Serial dilution
results and "E" flags shall be reported on Form VIII-IN.
12.10 Method Detection Limit (MDL) Determination
12.10.1 Before any field samples are analyzed under this contract, the MDLs
shall be determined for non-prepared analyses (Preparation
Method/Code "NP1"), each digestion procedure and instrument used,
prior to the start of contract analyses, and annually thereafter, and
shall meet the levels specified in Exhibit C.
An MDL study shall be performed after major instrument maintenance,
or changes in instrumentation or instrumental conditions to verify
the current sensitivity of the analysis.
12.10.1.1 To determine the MDLs, the Contractor shall run MDL studies
following the procedures given in 40 CFR, Part 136. The
Contractor shall prepare the MDL samples by each digestion
procedure used and shall analyze these samples on each instrument
used. The Contractor shall also analyze the non-prepared MDL
samples on each instrument used.
12.10.1.2 The determined concentration of the MDL shall be less than half
the concentration of the CRQL listed in Exhibit C.
12.10.1.3 The concentration of the non-prepared MDL (Preparation Method/Code
"NP1") shall be used to determine the appropriate concentration
qualifier for the results of non-prepared samples and instrument
QC analyses.
12.10.1.4 The results of the MDL determination studies shall be forwarded to
the USEPA Regional CLP PO, Sample Management Office (SMO)", and
Quality Assurance Technical Support (QATS).
12.10.1.5 The MDL results shall be reported on Form IX-IN.
D-31/ICP-AES ILM05.2
-------
Exhibit D (ICP-AES) Section 12
Quality Control (Con't)
12.11 Interelement Corrections
12.11.1 Before any field samples are analyzed under this contract, the
interelement correction factors shall be determined prior to the
start of contract analyses and at least quarterly thereafter.
Correction factors for spectral interference due to Al, Ca, Fe, and
Mg shall be determined for all ICP-AES instruments at all wavelengths
used for each analyte reported by ICP-AES. Interelement correction
factors shall also be reported for any other elements (including
those on the TAL) that have been determined to interfere with the
requested target analyte(s).
NOTE: Depending on sample matrix and interferences, it may be
necessary to analyze interelement correction factors at a frequency
greater than quarterly and/or at multiple concentrations comparable
to the sample interferent levels.
12.11.2 If the instrument was adjusted in any way that may affect the ICP-AES
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 XA-IN and Form XB-IN for all ICP-AES analytes.
12.12 Linear Range Analysis Standard (LRS)
12.12.1 A linear range verification check standard shall be analyzed and ,
reported quarterly (i.e., January, April, July and October) for each
element on Form XI-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 5% of the true value. This concentration is the upper limit
of the ICP-AES linear range beyond which results cannot be reported
under this contract without dilution of the analytical sample.
ILM05.2 D-32/ICP-AES
-------
Exhibit D (ICP-AES) Sections 13-16
Method Performance
13.0 METHOD PERFORMANCE
Not applicable.
14.0 POLLUTION PREVENTION
See Section 1.15 in Exhibit D - Introduction to Analytical Methods.
15.0 WASTE MANAGEMENT
See Section 1.16 in Exhibit D - Introduction to Analytical Methods.
16.0 REFERENCES
16.1 US Environmental Protection Agency. Methods for Chemical Analysis of
Water and Wastes. Method 200.7. December 1982.
16.2 US Environmental Protection Agency. Test Methods for Evaluating Solid
Waste, Physical/Chemical Methods (SW-846). Method 3050B. Third Edition,
Update III. December 1996.
16.3 American Society for Testing and Materials. Standard Practice for Sample
Digestion Using Closed Vessel Microwave Heating Technique for the
Determination of Total Recoverable Metals in Water. D4309-91. October
1991.
16.4 US Government Printing Office. 40 Code of Federal Regulations, Part 136,
Section 1, Appendix B.
16.5 US Environmental Protection Agency. Test Methods for Evaluating Solid
Waste, Physical/Chemical Methods (SW-846). Method 3015. Third Edition,
Update II. September 1994.
16.6 US Environmental Protection Agency. Test Methods for Evaluating Solid
Waste, Physical/Chemical Methods (SW-846). Method 3051. Third Edition,
Update II. September 1994.
D-33/ICP-AES ILM05.2
-------
Exhibit D (ICP-AES) Section 17
Tables/Diagrams/Flowcharts
17.0 TABLES/DIAGRAMS/FLOWCHARTS
TABLE 1: Interferent and Analyte Elemental Concentrations Used for
ICP-AES Interference Check Sample (ICS)
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)
250
250
100
250
NOTE: ICS Solution A (ICSA) contains the interferents at the indicated
concentrations. The ICSA may be analyzed at twice the concentration
indicated when interferences are present at higher concentrations in the
sample. ICS Solution AB (ICSAB) contains all of the analytes and
interferents listed above at the indicated concentrations.
ILM05.2 D-34/ICP-AES
-------
Exhibit D (ICP-AES) Section 17
Tables/Diagrams/Flowcharts (Con't)
TABLE 2: Spiking Levels for Spike Sample Analysis
Element
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Water
(ug/L)
2,000
100
40
2,000
50
50
*
200
500
250
1,000
20
Soil'1'
(mg/kg)
*
20
8
400
10
10
*
40
100
50
*
4
Element
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Water
(ug/L)
*
500
500
*
50
50
*
50
500
500
Soil'1'
(mg/kg)
*
100
100
*
10
10
*
10
100
100
*No spike required. NOTE: Elements without spike levels, and not
designated with an asterisk, shall be spiked at appropriate levels.
JThe levels shown indicate concentrations in the spike sample when the
wet weight of 1 gram 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 be made for
microwave digestion procedures where 0.5 grams of sample or 50 mL (45 mL of
sample plus 5 mL of acid) or 55 mL (50 mL of sample plus 5 mL of acid) of
aqueous sample are required for analysis.
EQ. 8 Spiking Level Adjustment
mg/kg = pg/L x
fi'nal volume (L)
sample weight (g)
D-35/ICP-AES
ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
-------
EXHIBIT D - PART B
ANALYTICAL METHODS
FOR
INDUCTIVELY COUPLED PLASMA -
MASS SPECTROMETRY
D-1/ICP-MS ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
ILM05.2 D-2/ICP-MS
-------
Exhibit D - Analytical Methods for ICP-MS
Table of Contents
Section Page
1.0 SCOPE AND APPLICATION 5
2.0 SUMMARY OF METHOD 5
3.0 DEFINITIONS 5
4.0 INTERFERENCES 6
4.1 Isobaric Elemental Interferences 6
4.2 Abundance Sensitivit y 6
4.3 Isobaric Polyatomic Ion Interference s 6
4.4 Physical Interferences 6
4.5 Memory Interferences 7
5.0 SAFETY 7
6.0 EQUIPMENT AND SUPPLIES 8
6.1 Glassware/Labware 8
6.2 Inductively Coupled Plasma Mass Spectrometer (ICP-MS) 8
7.0 REAGENTS AND STANDARDS 9
7.1 Reagents ' 9
7.2 Standards 9
7.3 Blanks 13
8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE 14
8.1 Sample Collection and Preservation 14
8.2 Procedures for Sample Storage 14
8.3 Procedure for Sample Digestate Storage 14
8.4 Contract Required Holding Time 14
9.0 CALIBRATION AND STANDARDIZATION 15
9.1 Instrument Operating Parameters 15
9.2 Inductively Coupled Plasma - Mass Spectrometry (ICP-MS)
Instrument Calibration Procedure 15
9.3 Initial.Calibration Verification (ICV) 16
9.4 Continuing Calibration Verification (CCV ) 16
9.5 Initial and Continuing Calibration Blank (ICB/CCB) 17
10.0 PROCEDURE 17
10.1 Sample Preparation 17
10.2 Sample Analysis 18
11.0 DATA ANALYSIS AND CALCULATIONS 20
11.1 Recommended Elemental Equations 20
11.2 Data Value Corrections 20
11.3 Multiple Monitored Isotopes 20
11.4 Direct Analysis 20
11.5 Prepared Sample Analysis 20
11.6 Adjusted Method Detection Limit (MDL)/Adjusted Contract
Required Quantitation Limit (CRQL) Calculation 21
12.0 QUALITY CONTROL (QC) 21
12.1 Tune Standard 21
12.2 Initial Calibration Verification (ICV) 21
12.3 Continuing Calibration Verification (CCV ) 21
12.4 Contract Required Quantitation Limit (CRQL) Check Standard
(CRI) 21
12.5 Blank Analyses 22
12.6 Interference Check Sample (ICS) 23
D-3/ICP-MS ILM05.2
-------
Exhibit D - Analytical Methods for ICP-MS
Table of Contents (Con't)
Section , Page
12.7 Spike Sample Analysi s 24
12.8 Duplicate Sample Analysi s 25
12.9 Laboratory Control Sample (LCS) Analysis 26
12.10 ICP-MS Serial Dilution Analysis ' 26
12.11 Internal Standards 26
12.12 Method Detection Limit (MDL) Determination .- 27
12.13 Linear Dynamic Range (LDR) 27
13.0 METHOD PERFORMANCE 28
14.0 POLLUTION PREVENTION 28
15.0 WASTE MANAGEMENT 28
16.0 REFERENCES 28
17.0 TABLES/DIAGRAMS/FLOWCHARTS 29
Table 1. Isobaric Molecular-Ion Interferences 29
Table 2. Mass Choices for Elements that Must Be Monitored
During the Analytical Run 32
Table 3. Recommended Elemental Expressions for Isobaric
Interferences 33
Table 4, Internal Standards 34
Table 5. Spiking Levels for Spike Sample Analysis 34
ILM05.2 D-4/ICP-MS
-------
Exhibit D (ICP-MS) Sections 1-3
Scope and Application
1.0 SCOPE AND APPLICATION
This method provides procedures for 'the use of Inductively Coupled
Plasma - Mass Spectrometry (ICP-MS) to determine the concentration of
dissolved and total recoverable elements in water/aqueous samples taken
from hazardous waste sites. This method is applicable to all metals in
the Target Analyte List (TAL) for ICP-MS in Exhibit C.
2.0 SUMMARY OF METHOD
This method describes the multi-element determination of trace elements
by Inductively Coupled Plasma - Mass Spectrometry (ICP-MS). Sample
material in solution is introduced by nebulization into a radio
frequency plasma where energy transfer processes cause desolvation,
atomization, and ionization. The ions are extracted from the plasma
through a differentially pumped vacuum interface and separated on the
basis of their mass-to-charge ratio. The separated ions are detected
and the ion information processed by a data handling system.
Interferences related to the technique must be recognized and corrected.
Such corrections may include compensation for isobaric elemental
interferences and interferences from polyatomic ions derived from plasma
gas, reagents, or sample matrix. Instrumental drift, as well as
suppressions or enhancements of instrument response, must be corrected
for the use of internal standards.
3.0 DEFINITIONS
See Exhibit G for a complete list of definitions.
D-5/ICP-MS
ILM05.2
-------
Exhibit D (ICP-MS) Section 4
Interferences
4.0 INTERFERENCES '
Several types of interferences may cause inaccuracies in the
determination of trace elements by Inductively Coupled Plasma - Mass
Spectrometry (ICP-MS). To prevent this, appropriate steps must be taken
in all analyses to ensure that potential interferences are taken into
account. Possible interferences are in Sections 4.1 through 4.5.
4.1 Isobaric Elemental Interferences
Isobaric Elemental Interferences are caused by isotopes of different
elements which form singly or doubly charged ions of the same nominal
mass-to-charge ratio, and which cannot be resolved by the mass
spectrometer. All elements determined by this method have, at minimum,
one isotope free of isobaric elemental interference. Of the analytical
isotopes recommended for use with this method, only selenium-82
(krypton) has an isobaric elemental interference. If alternative
analytical isotopes having higher natural abundances are selected, in
order to achieve greater sensitivity, an isobaric interference may
occur. All data obtained under such conditions must be corrected by
measuring the signal from another isotope of the interfering element and
subtracting the appropriate signal ratio from the isotope of interest.
A record of this correction process should be included with the report
of the data. It should be noted that such corrections will only be as
accurate as the accuracy of the isotope ratio used in the elemental
equation for data calculations. Relevant isotope ratios should be
established prior to the application of any corrections.
4.2 Abundance Sensitivity
Abundance Sensitivity is a property defining the degree to which the
wings of a mass peak contribute to adjacent masses. The abundance
sensitivity is affected by ion energy and mass filter operating
pressure. Wing overlap interferences may result when a small ion peak
is being measured adjacent to a large one. The potential for these
interferences should be recognized and the spectrometer resolution
should be adjusted to minimize.
4.3 Isobaric Polyatomic Ion Interferences
These are caused by ions consisting of more than one atom which have the
same nominal mass-to-charge ratio as the isotope of interest, and which
cannot be resolved by the mass spectrometer. These ions are commonly
formed in the plasma or interface system from support gases or sample
components. Most of the common interferences have been identified and
are listed in Table 1 - Isobaric Molecular-Ion Interferences, with the
target analytes affected. Such interferences must be recognized, and
when they cannot be avoided by the selection of alternative analytical
isotopes, appropriate corrections must be made to the data. Equations
for the correction of data should be established at the time of the
analytical run sequence, since the polyatomic ion interferences will be
highly dependent on the sample matrix and chosen instrument conditions.
4.4 Physical Interferences
These are associated with the physical processes which govern the
transport of the sample into the plasma, sample conversion processes in
the plasma, and the transmission of ions through the plasma-mass
spectrometer interface. These interferences may result in differences
between instrument responses for the sample and the calibration
standards. Physical interferences may occur in the transfer of solution
to the nebulizer (e.g., viscosity effects), at the point of aerosol
formation and transport to the plasma (e.g., surface tension), or during
ILM05.2 D-6/ICP-MS
-------
Exhibit D (ICP-MS) Sections 4 & 5
Safety
the excitation and ionization processes within the plasma itself. High
.levels of dissolved solids in the sample may contribute to deposits of
material on the extraction and/or skimmer cones. Deposits can reduce
the effective diameter of the orifices and therefore ion transmission.
Dissolved solid levels not exceeding 0.2% (w/v) have been recommended to
reduce such effects. Internal standardization may be effectively used
to compensate for many physical interference effects. Internal
standards ideally should have similar analytical behavior to the
elements being determined.
4.5 Memory Interferences
Memory Interferences result when isotopes of elements in a previous
sample contribute to the signals measured in a new sample. Memory
effects, or carryover, can result from sample deposition on the sampler
and skimmer cones, as well as from the buildup of sample material in the
plasma torch and spray chamber. The site where these effects occur is
dependent on the element and can be minimized by flushing the system
with a rinse blank between samples (see Section 7.3.3). The possibility
of memory interferences should be recognized within an analytical run
and suitable rinse times should be used to reduce them. The rinse times
necessary for a particular element should be estimated prior to
analysis. This may be achieved by aspirating a standard, containing the
elements corresponding to ten times the upper end of the linear range
for a normal sample analysis period, followed by analysis of the rinse
blank at designated intervals. The length of time required to reduce
analyte signals to within a factor of ten of the Method Detection Limit
(MDL) should be noted. Memory interferences may also be assessed within
an analytical run by using a minimum of three replicate integrations for
data acquisition. If the integrated signal values drop consecutively,
the analyst should be alerted to the possibility of a memory effect, and
should examine the analyte concentration in the previous sample to
identify if it was high. If a memory interference is suspected, the
sample should be re-analyzed after a long rinse period.
5.0 SAFETY
See Section 1.14 in Exhibit D - Introduction to Analytical Methods.
D-7/ICP-MS ILM05.2
-------
Exhibit D (ICP.-MS) Section 6
Equipment and Supplies
6.0 EQUIPMENT AND SUPPLIES
Brand names, suppliers, and part numbers are for illustrative purposes
only. No endorsement is implied. Equivalent performance may be
achieved using equipment and supplies other than those specified here,
however, a demonstration of equivalent performance meeting the
requirements of this Statement of Work (SOW) is the responsibility of
the Contractor. The Contractor shall document any use of alternate
equipment or supplies in the Sample Delivery Group (SDG) Narrative.
6.1 Glassware/Labware
6.1.1 250 milliliter (mL) beaker or other appropriate vessel
6.1.2 Watch glasses
6.1.3 Funnels
6.1.4 Graduated cylinders
6.1.5 Various volumetric flasks (Type A)
6.1.6 Thermometer that covers range of 0-200°C
6.1.7 Whatman No. 42 filter paper or equivalent
6.1.8 Hot plate, block digester, or other heating source capable of
maintaining 92-95°C.
6.1.9 Balances - Analytical Balance, 300 gram (g) capacity, and minimum
ą0.1 milligram (mg).
6.2 Inductively Coupled Plasma Mass Spectrometer (ICP-MS) consisting of:
=" An instrument capable of scanning the mass range 5-250 atomic mass
unit (amu) with a minimum resolution capability of 1 amu peak
width at 5% peak height and either a conventional or extended
dynamic range detector.
:" A radio-frequency generator compliant with Federal Communications
Commission (FCC) regulations.
A high purity (99.99%) argon gas supply.
:xl A variable speed peristaltic pump to deliver sample solution to
the nebulizer.
A mass-flow controller on the nebulizer gas supply is required.
ILM05.2 D-8/ICP-MS
-------
Exhibit D (ICP-MS) -- Section 7
Reagents and Standards
7.0 REAGENTS AND STANDARDS
7.1 Reagents
Reagents may contain elemental impurities that might affect the
integrity of analytical data. Owing to the high sensitivity of
Inductively Coupled Plasma - Mass Spectrometry (ICP-MS), high-purity
reagents should be used whenever possible. All acids used must be of
ultra high-purity grade. Suitable acids are available from a number of
manufacturers or may be prepared by sub-boiling distillation. Nitric
acid is preferred for ICP-MS in order to minimize polyatomic ion
interferences. Several polyatomic ion interferences result when
hydrochloric acid (HCl) is used, however, it should be noted that HC1 is
required to maintain stability in solutions containing antimony and
silver. When HCl is used, corrections for the chloride polyatomic ion
interferences must be applied to all data.
7.1.1 Reagent Water - The purity of this water must be equivalent to ASTM
Type II water (ASTM D1193-77). Use this preparation for all
reagents, standards, and dilutions of solutions.
7.1.2 Nitric Acid - Concentrated (specific gravity 1.41).
7.1.3 Nitric acid (1+1) - Add 500 milliliters (mL) cone. HNO3 to 400 mL of
reagent water and dilute to 1 Liter (L).
7.1.4 Nitric acid (1+9) - Add 100 mL cone, nitric acid to 400 mL of reagent
water and dilute to 1 L.
7.1.5 Hydrochloric acid - Concentrated (specific gravity 1.19).
7.1.6 Hydrochloric acid (1+1) - Add 500 mL cone. HCl to 400 mL of reagent
water and dilute to 1 L.
7.1.7 Hydrochloric acid (HCl) (1+4) - Add 200 mL cone. HCl to 400 mL
reagent water and dilute to 1 L.
7.1.8 Ammonium hydroxide - Concentrated (specific gravity 0.902).
7.1.9 Tartaric acid - (CASRN 87-69-4).
7.2 Standards
7.2.1 Introduction
The Contractor must provide all standards to be used with this
contract. These standards may be used only after they have been
certified according to the procedure in Exhibit E, Section 8.0. The
Contractor must be able to verify that the standards are certified.
Manufacturer's certificates of analysis must be retained by the
Contractor and presented upon request.
7.2.2 Stock Standard Solutions
7.2.2.1 Stock standard solutions may be purchased from a reputable
commercial source or prepared from ultra high-purity grade
chemicals or metals (99.99-99.999% pure). All salts should be
dried for 1 hour at 105°C unless otherwise specified. Stock
solutions should be stored in Fluorinated Ethylene Propylene (FEP)
fluorocarbon bottles. Note that some metals, particularly those
which form surface oxides, require cleaning prior to being
weighed. This may be achieved by pickling the surface of the
metal in acid. An amount in excess of the desired weight should
D-9/ICP-MS
ILM05.2
-------
Exhibit D (ICP-MS) Section 7
Reagents and Standards (Con't)
be pickled repeatedly, rinsed with water, dried and weighed until
the desired weight is achieved.
7.2.2.2 Aluminum solution, stock [1 mL = 1000 micrograms (pg) Al] - Pickle
aluminum metal in warm (1+1) HC1 to an exact weight of 0.100 g.
Dissolve in 10 mL cone. HC1 and 2 mL cone, nitric acid, heating to
effect solution. Continue heating until the volume is reduced to
4 mL. Cool and add 4 mLs of reagent water. Heat until volume is
reduced to 2 mL. Cool and dilute to 100 mL with reagent water.
7.2.2.3 Antimony solution, stock (1 mL = 1000 ug Sb) - Dissolve 0.100 g
antimony powder in 2 mL (1+1) nitric acid and 0.5 mL cone. HC1,
heating to effect solution. Cool, add 20 mL reagent water and
0.15 g tartaric acid. Warm the solution to dissolve the white
precipitate. Cool and dilute to 100 mL with reagent water.
7.2.2.4 Arsenic solution, stock (1 mL = 1000 ug As) - Dissolve 0.1320 g
As203 in a mixture of 50 mL reagent water and 1 mL cone, ammonium
hydroxide. Heat gently to dissolve. Cool and acidify solution
with 2 mL cone, nitric acid. Dilute to 100 mL with reagent water.
7.2.2.5 Barium solution, stock (1 mL = 1000 ug Ba) - Dissolve 0.1437 g
BaC03 in a solution mixture of 10 mL reagent water and 2 mL cone.
nitric acid. Heat and stir to effect solution and degassing.
Dilute to 100 mL with reagent water.
7.2.2.6 Beryllium solution, stock (1 mL = 1000 ug Be) - Dissolve 1.965 g
BeSO4:l"4H2O (DO NOT DRY) in 50 mL reagent water. Add 1 mL cone.
nitric acid. Dilute to 100 mL with reagent water.
7.2.2.7 Bismuth solution, stock (1 mL = 1000 ug Bi) - Dissolve 0.1115 g
Bi2O3 in 5 mL cone, nitric acid. Heat to effect solution. Cool
and dilute to 100 mL with reagent water.
7.2.2.8 Cadmium solution, stock (1 mL = 1000 ug Cd) - Pickle cadmium metal
in (1+9) nitric acid to an exact weight of 0.100 g. Dissolve in 5
mL (1+1) nitric acid, heating to effect solution. Cool and dilute
to 100 mL with reagent water.
7.2.2.9 Chromium solution, stock (1 mL = 1000 ug Cr) - Dissolve 0.1923 g
CrO3 in a solution mixture of 10 mL reagent water and 1 mL cone.
nitric acid. Dilute to 100 mL with reagent water.
7.2.2.10 Cobalt solution, stock (1 mL = 1000 ug Co) - Pickle cobalt metal
in (1+9) nitric acid to an exact weight of 0.100 g. Dissolve in 5
mL (1+1) nitric acid, heating to effect solution. Cool and dilute
to 100 mL with reagent water.
7.2.2.11 Copper solution, stock (1 mL = 1000 pg Cu) - Pickle copper metal
in (1+9) nitric acid to an exact weight of 0.100 g. Dissolve in 5
mL (1+1) nitric acid, heating to effect solution. Cool and dilute
to 100 mL with reagent water.
7.2.2.12 Indium solution, stock (1 mL = 1000 pg In) - Pickle indium metal
in (1+1) nitric acid to an exact weight of 0.100 g. Dissolve in
10 mL (1+1) nitric acid, heating to effect solution. Cool and
dilute to 100 mL with reagent water.
7.2.2.13 Lead solution, stock (1 mL = 1000 pg Pb) - Dissolve 0.1599 g PbNO3
in 5 mL (1+1) nitric acid. Dilute to 100 mL with reagent water.
ILM05.2 D-10/ICP-MS
-------
Exhibit D (ICP-MS) Section 7
Reagents and Standards (Con't)
7.2.2.14 Magnesium solution, stock (1 mL = 1000 pg Mg) - Dissolve 0.1658 g
MgO in 10 mL (1+1) nitric acid, heating to effect solution. Cool
and dilute to 100 mL with reagent water.
7.2.2.15 Manganese solution, stock (1 mL = 1000 ug Mn) - Pickle manganese
flake in (1+9) nitric acid to an exact weight of 0.100 g.
Dissolve in 5 mL (1+1) nitric acid, heating to effect solution.
Cool and dilute to 100 mL with reagent water.
7.2.2.16 Nickel solution, stock (1 mL = 1000 ug Ni) - Dissolve 0.100 g
nickel powder in 5 mL cone, nitric acid, heating to effect
solution. Cool and dilute to 100 mL with reagent water.
7.2.2.17 Scandium solution, stock (1 mL = 1000 ug Sc) - Dissolve 0.1534
Sc2O3 in 5 mL (1+1) nitric acid, heating to effect solution. Cool
and dilute to 100 mL with reagent water.
7.2.2.18 Selenium solution, stock (1 mL = 1000 ug Se) - Dissolve 0.1405 g
SeO2 in 20 mL reagent water and dilute to 100 mL with reagent
water.
7.2.2.19 Silver solution, stock (1 mL = 1000 ug Ag) - Dissolve 0.100 g
silver metal in 5 mL (1+1) nitric acid, heating to effect
solution. Cool and dilute to 100 mL with reagent water. Protect
from the light.
7.2.2.20 Terbium solution, stock (1 mL = 1000 pg Tb) - Dissolve 0.1176 g
Tb4O7 in 5 mL cone, nitric acid, heating to effect solution. Cool
and dilute to 100 mL with reagent water.
7.2.2.21 Thallium solution, stock (1 mL = 1000 pg Tl) - Dissolve 0.1303 g
T1N03 in a solution mixture of 10 mL reagent water and 1 mL cone.
nitric acid. Dilute to 100 mL with reagent water.
7.2.2.22 Vanadium solution, stock (1 mL = 1000 pg V) - Pickle vanadium
metal in (1+9) nitric acid to an exact weight of 0.100 g.
Dissolve in 5 mL (1+1) nitric acid, heating to effect solution.
Cool and dilute to 100 mL with reagent water.
7.2.2.23 Yttrium solution, stock (1 mL = 1000 pg Y) - Dissolve 0.1270 g
Y2O3 in 5 mL (1+1) nitric acid, heating to effect solution. Cool
and dilute to 100 mL with reagent water.
7.2.2.24 Zinc solution, stock (1 mL = 1000 pg Zn) - Pickle zinc metal in
(1+9) nitric acid to an exact weight of 0.100 g. Dissolve in 5 mL
(1+1) nitric acid, heating to effect solution. Cool and dilute to
100 mL with reagent water.
7.2.3 Secondary Dilution Standards
Prepare mixed secondary dilution standard solutions by diluting the
appropriate volumes of stock standards with acidified reagent water
to obtain the final volume. Originating stock standards should be
checked for the presence of impurities which might influence the
accuracy of the standard. Freshly prepared standards should be
transferred to acid-cleaned, not previously used, FEP fluorocarbon
bottles for storage and monitored periodically for stability. Mixed
secondary dilution standard solutions may be purchased. The
purchased standards shall meet the requirements in Section 7.2.1.
D-11/ICP-MS ILM05.2
-------
Exhibit D (ICP-MS) Section 7
Reagents and Standards (Con't)
7.2.4 Working Standards
7.2.4.1 Mixed Calibration Standard Solutions
Care must be taken in the preparation of mixed calibration
standards to ensure that the elements are compatible and stable.
Fresh calibration standards should be prepared from mixed standard
solutions every two weeks or as needed. Dilute the mixed
standards to levels appropriate to the operating range of the
instrument using reagent water containing 1% (v/v) nitric acid.
The element concentrations in the calibration standards should be
sufficiently high to produce good measurement precision and to
accurately define the slope of the response curve. If the direct
addition procedure is being used, add internal standards.
7.2.4.2 Internal Standard Solution
Prepare mixed standard by diluting 10 mL each of the chosen
element's stock standards to 100 mL with reagent water. Use this
solution for additions to blanks, calibration standards, and
samples, or dilute by an appropriate amount using 1% (v/v) nitric
acid if the internal standards are being added by a peristaltic
pump.
7.2.4.3 Tuning Solution
This solution is used for instrument tuning and mass calibration
prior to analysis. Prepare mixed standard by diluting beryllium,
magnesium, cobalt, indium, and lead stock standards to 100 pg/L
with 1% (v/v) nitric acid. Do not add internal standard to this
solution.
7.2.4.4 Interference Check Sample (ICS)
The ICS consists of two solutions: Solution A (ICSA) and Solution
AB (ICSAB). ICSA consists of the interferents and ICSAB consists
of the analytes mixed with the interferents. If the direct
addition procedure is being used, add internal standards.
7.2.4.4.1 Solution A - Contains 100 milligrams per Liter (mg/L) of
aluminum, calcium, iron, magnesium, potassium, sodium,
phosphorus (as orthophosphate), sulfur (as sulfate), 200 mg/L
carbon, 1000 mg/L chloride, and 2 mg/L molybdenum and titanium.
7.2.4.4.2 Solution AB - Contains all of the elements in Solution A plus
all target analytes at a concentration of 20 ug/L.
7.2.4.5 Contract Required Quantitation Limit (CRQL) Check Standard (CRI)
The concentrations of the analytes in the CRI shall be at the
CRQL. Information regarding the CRI shall be reported on Form
IIB-IN.
7.2.4.6 Method Detection Limit (MDL) Solution
The MDL solution shall be at a concentration of 3 to 5 times the
expected MDL.
ILM05.2 D-12/ICP-MS
-------
Exhibit D (ICP-MS) Section 7
Reagents and Standards (Con't)
7.3 Blanks
Three types of blanks are required for this method. A calibration blank
is used to establish the analytical calibration curve, the Preparation
Blank (PB) (see Section 12.5.2) is used to assess possible contamination
from the sample preparation procedure and to assess spectral background,
and the rinse blank is used to flush the instrument between samples in
order to reduce memory interferences.
7.3.1 Calibration Blank - Consists of 1% (v/v) nitric acid in reagent
water. If the direct addition procedure is being used, add internal
standards.
7.3.2 Preparation Blank - Must contain all the reagents in the same volumes
as used in preparing the samples. The PB must be carried through the
complete procedure and contain the same acid concentration in the
final solution as the sample solution used for analysis.
7.3.3 Rinse Blank - Consists of 2% (v/v) nitric acid in reagent water.
D-13/ICP-MS ILM05.2
-------
Exhibit D (ICP-MS) Section 8
Sample Collection, Preservation, and Storage
8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE
8.1 Sample Collection and Preservation
All samples must be collected in glass or polyethylene containers.
Water/aqueous samples must be preserved with nitric acid to pH less than
2 immediately after collection. All samples must be iced or
refrigerated at 4°C (ą2°C) from the time of collection until digestion.
8.1.1 Dissolved Metals
For the determination of dissolved metals, the sample must be
filtered through a 0.45 micrometer ( ^n) pore diameter membrane
filter at the time of collection or as soon as possible. Use a
portion of the sample to rinse the filter flask, discard this
portion, and collect the required volume of filtrate. Preserve the
filtrate with nitric acid to pH less than 2 immediately after
filtration.
8.2 Procedures for Sample Storage
The samples must be protected from light and refrigerated at 4°C (ą2°C)
from the time of receipt until 60 days after the delivery of a complete,
reconciled data package to USEPA. After 60 days the samples may be
disposed of in a manner that complies with all applicable regulations.
8.3 Procedure for Sample Digestate Storage
Sample digestates must be stored until 365 days after delivery of a
complete, reconciled data package to USEPA.
8.4 Contract Required Holding Time
The maximum holding time for metals is 180 days from Validated Time of
Sample Receipt (VTSR).
ILM05.2 D-14/ICP-MS
-------
Exhibit D (ICP-MS) Section 9
Calibration and Standardization
9.0 CALIBRATION AND STANDARDIZATION
9.1 Instrument Operating Parameters
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. The Method Detection
Limit (MDL), precision, linear dynamic range, and interference effects
must be investigated and established for each individual element on that
particular instrument. All measurements must be within the operational
range of the instrument where corrections 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 (QC) data confirming
instrument performance and analytical results.
9.2 Inductively Coupled Plasma - Mass Spectrometry (ICP-MS) Instrument
Calibration Procedure
9.2.1 Precalibration routine - The following precalibration routine must be
completed prior to calibrating the instrument.
Set up the instrument with proper operating parameters established in
Section 9.1. The instrument must be allowed to become stable prior
to calibration. Conduct any necessary mass calibration and
resolution routines to bring peak width within 0.75 atomic mass unit
(amu) at 5% peak height and adjust mass calibration to within 0.1 amu
over the range of 6 to 210 amu.
Demonstrate instrument stability and precision by analyzing the
tuning solution a minimum of five times consecutively. The percent
relative standard deviation of the absolute signals for all analytes
in the tuning solution must be less than 5%.
9.2.2 Internal Standardization
Internal standardization must be used in all analyses to correct the
instrument drift and physical interferences. A list of acceptable
internal standards is provided in Table 4 - Internal Standards. For
full range mass scans, a minimum of three internal standards shall be
used. The masses of the internal standards shall bracket the masses
of the analyte. Internal standards shall be present in all samples,
standards, and blanks at identical levels. This may be achieved by
directly adding an aliquot of the internal standards solution to each
sample, standard, and blank, or by mixing with the sample solution
prior to nebulization using a second channel of the peristaltic pump
and mixing coil. The concentration of the internal standard should
be sufficiently high for good precision and to minimize the
possibility of correction errors if the internal standard is
naturally present in the sample. Depending on the sensitivity of the
instrument, a concentration range of 20 ug/L to 200 ug/L of each
internal standard is recommended. Internal standards should be added
to samples, standards, and blanks in a similar manner, in order for
dilution effects to be disregarded.
9.2.3 Calibration
Instruments shall be calibrated daily, once every 24 hours, or each
time the instrument is set up. The instrument standardization date
and time shall be included in the raw data. Calibration standards
shall be prepared as in Section 7.2.4.1. Calibrate the instrument
with at least two standards, one of which must be a blank standard.
D-15/ICP-MS
ILM05.2
-------
Exhibit D (ICP-MS) Section 9
Calibration and Standardization (Con't)
A minimum of three replicate integrations are required for data
acquisition. Use the average of the integrations for instrument
calibration and data reporting.
NOTE: Any changes or corrections to the analytical system shall be
followed by recalibration.
9.3 Initial Calibration Verification (ICV)
9.3.1 Immediately after each instrument has been calibrated, the accuracy
of the initial calibration shall be verified and documented for every
analyte by the analysis of the ICV solution (s) for each mass used to
report final results.
9.3.2 Only if the ICV solution(s) is (are) not available from USEPA, 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 other
than those used in the standards for instrument calibration.
9.3.3 The ICV solution (s) shall be run at each mass used for reporting
final results. The values for the ICV shall be reported on Form IIA-
IN.
9.4 Continuing Calibration Verification (CCV)
9.4.1 To ensure calibration" accuracy during each analysis run, one of the
following standards shall be used for the CCV for each mass used for
reporting final results for each element, 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 each mass used
for reporting final results for each element at the beginning of the
run and after the last analytical sample. The analyte concentrations
in the CCV standard(s) shall be different from the concentrations for
the ICV and shall be one of the following solutions at or near one-
half of the calibration standard:
<*: USEPA Solutions
Ť= NIST Standards
11 A Contractor-prepared standard solution
The same CCV standard shall be used throughout the analysis runs for
a Sample Delivery Group (SDG) of samples received.
9.4.2 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 which 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.
9.4.3 Information regarding the CCV shall be reported on Form IIA-IN.
ILM05.2 D-16/ICP-MS
-------
Exhibit D (ICP-MS) Sections 9 & 10
Procedure
9.5 Initial and Continuing Calibration Blank (ICB/CCB)
A calibration blank shall be analyzed for each mass used for reporting
final results for each element immediately after every ICV and CCV, at a
frequency of 10% or every 2 hours 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 analyzed immediately after the last CCV, and the
last CCV shall be analyzed immediately after the last analytical sample
of the run. The results of the calibration blanks shall be reported on
Form III-IN.
10.0 PROCEDURE
10.1 Sample Preparation
10.1.1 If insufficient sample amount (less than 90% of the required amount)
is received to perform the analyses, the Contractor shall contact the
Sample Management Office (SMO) to inform them of the problem. SMO
will contact the Region for instructions. The Region will either
require 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. The Contractor shall document the
Region's decision in the Sample Delivery Group (SDG) Narrative.
10.1.2 If multiphase samples (e.g., two-phase liquid sample, oily
sludge/sandy soil sample) are received by the Contractor, the
Contractor shall contact SMO to apprise them of the type of sample
received. SMO will contact the Region. If all phases of the sample
are amenable to analysis, the Region may require the Contractor to do
any of the following:
: Mix the sample and analyze an aliquot from the homogenized
sample.
Separate the phases of the sample and analyze one or more of
the phases, separately. SMO will provide EPA sample numbers
for the additional phases, if required.
Do not analyze the sample.
10.1.2.1 If all of the phases are not amenable to analysis (i.e., outside
scope), the Region may require the Contractor to do any of the
following:
^ Separate the phases and analyze the phase(s) that is (are)
amenable to analysis. SMO will provide EPA sample numbers
for the additional phases, if required.
:J[: Do not analyze the sample.
10.1.2.2 No other changes in the analyses will be permitted. The
Contractor shall document the Region's decision in the SDG
Narrative.
10.1.3 Sample Preparation Procedures
10.1.3.1 Direct Analyses - Preparation Method/Code (NP1)
10.1.3.1.1 For the analysis of dissolved analytes in water samples,
transfer 20 milliliters (mL) of the filtered, acid-preserved
sample to a clean, closeable container such as a centrifuge
D-17/ICP-MS ILM05.2
-------
Exhibit D (ICP-MS) Section 10
Procedure (Con't)
tube. Add sufficient (1+1) nitric acid to make the sample 1%
(v/v) acid. If the direct addition procedure is being used,
add internal standards, close the container and mix. The
sample is now ready for analysis. If a precipitate is formed
during acidification, transport, or storage, sample digestion
is required as described in Section 10.1.3.2.
10.1.3.1.2 This Preparation Method/Code shall also be used to report the
direct analysis Method Detection Limit (MDL). The
concentration of this MDL shall be used to determine the
appropriate concentration qualifier for the results of non-
prepared samples and instrument Quality Control (QC) analyses.
10.1.3.1.3 Prior to the analysis of aqueous samples for total recoverable
analytes (excluding CLP Quarterly Blind (QB) samples),
determine the turbidity and report the results of these
measurements, in Nephelolometric Turbidity Units (NTU), in the
raw data. If the turbidity is less than 1 NTU, direct analysis
of the sample shall be performed using the procedure in Section
10.1.3.1.1. If the turbidity is greater than or equal to 1
NTU, digest the sample as follows:
10.1.3.2 Preparation Method/Code (HW2)
Shake and transfer a 100 mL aliquot of the sample to a 250 mL
heating vessel, add 2 mL (1+1) nitric acid and 1 mL of (1+1)
hydrochloric acid (HC1) to the sample. Cover with a ribbed watch'
glass and heat on either a hot plate, block digester, or
equivalent heating source which is adjustable and capable of
maintaining a temperature of 92-95°C for 2 hours, or until the
sample volume is reduced to about 20 mL (DO NOT BOIL). Cover with
a watch glass to prevent additional evaporation and reflux for 30
minutes. Cool sample, transfer to a 50 mL volumetric flask, and
adjust sample volume to 50 mL with reagent water. Mix and allow
any solids present to settle by gravity overnight or centrifuge
(if after settling or centrifuging, the sample contains suspended
solids, a portion of the sample may be filtered prior to
analysis).
10.1.3.2.1 Prior to analysis, adjust the chloride concentration by
pipetting 20 mL of the digestate into a 50 mL volumetric flask
and dilute to volume with reagent water and mix. If the direct
addition method is being used, add internal standards and mix.
The sample is now ready for analysis.
10.2 Sample Analysis
10.2.1 For every new or unusual matrix, it is highly recommended that a
semi-quantitative analysis be carried out to screen for high element
concentrations. Information gained from this may be used to prevent
potential damage to the detector during sample analysis and to
identify elements which may be higher than the linear range. Matrix
screening may be carried out by diluting the sample by a factor of
500 and analyzing in semi-quantitative mode. The sample should also
be screened for background levels of all elements chosen for use as
internal standards in order to prevent bias in the calculation of
analytical data.
10.2.2 Initiate instrument operating configuration. Tune and calibrate the
instrument for the analytes of interest. Establish instrument
software run procedures for quantitative analysis. For all sample
analyses, a minimum of three replicate integrations are required for
ILM05.2 D-18/ICP-MS
-------
Exhibit D (ICP-MS) Section 10
Procedure (Con't)
data acquisition. Use the average of the integrations for data
reporting.
10.2.3 The rinse blank should be used to flush the system between samples.
Allow sufficient time to remove traces of the previous sample or a
minimum of one minute. Samples should be aspirated for a sufficient
period of time to obtain a stable response prior to the collection of
data.
10.2.4 Samples having concentrations higher than the established linear
dynamic range should be diluted into range and re-analyzed. The
sample should first be analyzed for the trace elements, protecting
the detector from the high concentration elements, if necessary, by
the selection of appropriate scanning windows. The sample should
then be diluted for the determination of the remaining elements.
Alternatively, the dynamic range may be adjusted by selecting an
alternative isotope of lower natural abundance, provided QC data for
that isotope have been established. The dynamic range must not be
adjusted by altering instrument conditions to an uncharacterized
state.
10.2.5 All masses which might affect data quality must be monitored during
the analytical run. At a minimum, those masses prescribed in Table 2
- Mass Choices for Elements that Must Be Monitored During the
Analytical Run, must be monitored in the same scan that is used for
the collection of the data. This information should be used to
correct the data for identified interferences.
10.2.6 During the analysis of samples, the laboratory must comply with the
required QC described in Section 12. For the determination of
dissolved analytes or the direct analysis of aqueous samples with
turbidity less than 1 NTU, the Preparation Blank (PB) and Laboratory
Control Sample (LCS) are not required.
D-19/ICP-MS ILM05.2
-------
Exhibit D (ICP-MS) Section 11
Data Analysis and Calculations
11.0 DATA ANALYSIS AND CALCULATIONS
11.1 Recommended Elemental Equations
Elemental expressions recommended for sample data calculations are
listed in Table 3 - Recommended Elemental Expressions for Isobaric
Interferences. Do not report element concentrations below the
determined Method Detection Limit (MDL).
11.2 Data Value Corrections
'Data values should be corrected for instrument drift or sample matrix
induced interferences by the application of internal standardization.
Corrections for characterized spectral interferences should be applied
to the data. Chloride interference corrections should be made on all
samples, regardless of the addition of hydrochloric acid (HC1), as the
chloride ion is a common constituent of environmental samples.
11.3 Multiple Monitored Isotopes
If an element has more than one monitored isotope, examination of the
concentration calculated for each isotope or the isotope ratios will
provide useful information in detecting a possible spectral
interference. Consideration should therefore be given to both primary
and secondary isotopes in the evaluation of sample concentration. In
some cases, secondary isotopes may be less sensitive or more prone to
interferences than the primary recommended isotopes, therefore
differences between the results do not neces_sarily indicate a problem
with data calculated for the primary isotopes.
11.4 Direct Analysis
EQ. 1 Non-Prepared Sample Concentration
Concentration (ug/L)= C x DF
WHERE, C = Instrument value in ug/L. (The average of all
replicate integrations).
DF = Dilution Factor
11.5 Prepared Sample Analysis
EQ. 2 Prepared Sample Concentration
V V
Concentration (yg/L) = C x x - x DF
WHERE, C = Instrument value in pg/L (The average of all
replicate integrations).
Vf = Final digestion volume (50 mL)
Y! = Initial digestion volume (100 mL)
DF = Dilution Factor
ILM05.2 D-20/ICP-MS
-------
Exhibit D (ICP-MS) Sections 11 & 12
Quality Control
11.6 Adjusted Method Detection Limit (MDL)/Adjusted Contract Required
Quantitation Limit (CRQL) Calculation
To calculate the adjusted CRQL or adjusted MDL, multiply the value of
the CRQL (pg/L) or MDL (ug/L) by the sample dilution factor.'
12.0 QUALITY CONTROL (QC)
12.1 Tune Standard
The Tune Standard shall be prepared in the same acid matrix as the
calibration standards and analyzed at least 5 times consecutively. If
the peak width at 5% peak height is not within 0.75 atomic mass units
(amu) for each isotope, the mass calibration is not within 0.1 amu over
the range of 6 to 210 amu, or the percent Relative Standard Deviation
(%RSD)of the absolute signals of the analytes exceeds 5%, the analysis
shall be terminated, the problem corrected, and the instrument re-tuned.
All sample results reported must be associated with an instrument tune
that meets these requirements.
12.2 Initial Calibration Verification (ICV)
The ICV Standard shall be prepared in the same acid matrix as the
calibration standards and in accordance with the instructions provided
by the supplier. If measurements exceed the control limits of 90% (low)
and 110% (high), the analysis shall be terminated, the problem
corrected, the instrument recalibrated, and the calibration reverified.
Information regarding the ICV shall be reported on Form IIA-IN.
12.3 Continuing Calibration Verification (CCV)
The CCV standard shall be prepared by combining compatible elements at a
concentration equivalent to the mid-points of their respective
calibration curves. If the deviation of the CCV is greater than the
specified control limits of 90% (low) and 110% (high), the analysis
shall be stopped, the problem corrected, the instrument recalibrated,
the calibration verified, and re-analysis of the preceding 10 analytical
samples or all analytical samples analyzed since the last compliant
calibration verification shall be performed for the elements affected.
Information regarding the CCV shall be reported on Form IIA-IN.
12.4 Contract Required Quantitation Limit (CRQL) Check Standard (CRI)
12.4.1 To verify linearity near the CRQL, a standard at the CRQL (CRI) shall
be prepared, in the same acid matrix as the calibration standards,
and analyzed at the beginning and end of each sample analysis run,
but not before the ICV. In addition, the contractor shall analyze
the CRI at a frequency of not less than once per 20 analytical
samples1 per analysis run. The initial analysis of the CRI shall be
immediately followed by the Interference Check Samples (ICS)
analyses.
12.4.2 The CRI shall be run for every required isotope used for the analysis
of all Inductively Coupled Plasma - Mass Spectrometry (ICP-MS)
analytes. Information regarding the CRI shall be reported on Form
IIB-IN.
12.4.3 If the percent recovery of the CRI falls outside the control limits
of 70-130% (50-150% for cobalt, manganese, and zinc) for one or more
analytes, the CRI shall be re-analyzed immediately for those analytes
1As defined in Exhibit G, CRI is an analytical sample.
D-21/ICP-MS ILM05.2
-------
Exhibit D (ICP-MS) Section 12
Quality Control (Con't)
only. If the results of the re-analysis for those analytes fall
within the control limits, no further corrective action is required.
If the results of the re-analysis for those analytes do not fall
within the control limits, the analysis shall be terminated, the
problem corrected, the instrument recalibrated, the CRI analyzed, and
the samples associated with the CRI re-analyzed.
12.5 Blank Analyses
There are two different types of blanks required by this method. The
calibration blank is used in establishing the analytical curve while the
preparation blank is used to monitor for possible contamination.
12.5.1 Initial and Continuing Calibration Blank (ICB/CCB)
The ICB and CCB are prepared with acid and reagent water. If the
absolute value of the calibration blank (ICB/CCB) result exceeds the
CRQL (see Exhibit C), the analysis shall be terminated, the problem
corrected, the instrument recalibrated, the calibration verified, and
re-analysis of the preceding 10 analytical samples or all analytical
samples analyzed since the last compliant calibration blank shall be
performed for the elements affected.
12.5.2 Preparation Blank (PB)
12.5.2.1 The PB shall contain all the reagents and in the same volumes as
used in processing the samples. The PB shall be carried through
the complete procedure and contain the same acid concentration in
the final solution as the sample solution used for analysis.
12.5.2.2 At least one PB, consisting of reagent water processed through
each sample preparation and analysis procedure (see Section 10),
shall be prepared and analyzed with every Sample Delivery Group
(SDG), or with each batch 2 of samples digested, whichever is more
frequent.
12.5.2.3 The first batch of samples in an SDG is to be assigned to
Preparation Blank one, the second batch to Preparation Blank two,
etc. (see Form III-IN). Each Sample Data Package shall contain
the results of all PB analyses associated with the samples in that
SDG.
12.5.2.4 The PB is to be reported for each SDG and used in all analyses to
ascertain whether sample concentrations reflect contamination in
the following manner:
12.5.2.4.1 If the absolute value of the concentration of the blank is less
than or equal to the CRQL (see Exhibit C), no further action is
required.
12.5.2.4.2 If the analyte concentration in the blank is above the CRQL,
the lowest concentration of that analyte in the associated
samples shall be greater than or equal to 10 times the blank
concentration. Otherwise, all samples, associated with the
blank, with the analyte concentration less than 10 times the
blank concentration and above the CRQL, shall be redigested and
re-analyzed with appropriate new Quality Control (QC) for that
analyte. The only exception to this shall be an identified
field blank. The sample concentration is not to be corrected
for the blank value.
2A group of samples prepared at the same time.
ILM05.2 D-22/ICP-MS
-------
Exhibit D (ICP-MS) Section 12
Quality Control (Con't)
12.5.2.4.3 If the concentration of the blank is below the negative CRQL,
then all samples reported below 10 times the CRQL associated
with the blank, shall be redigested and re-analyzed with
appropriate new QC.
12.5.2.4.4 The values for the PB shall be reported on Form III-IN.
12.6 Interference Check Sample (ICS)
12.6.1 The ICS is prepared by the analyst "or obtained from USEPA, if
available.
12.6.2 To verify corrections for elemental and polyatomic isobaric
interferences, the Contractor shall analyze and report the results
for the ICS for all elements on the Target Analyte List (TAL) and for
all interferents (target and non-target), at the beginning of each
analysis run, but not before the ICV. This analysis of the ICS shall
be immediately followed by analysis of a CCV/CCB pair. The ICS
solutions shall be obtained from USEPA, if available, and analyzed
according to instructions supplied with the ICS. The Contractor
shall not dilute the ICS (for the higher concentration elements) more
than is necessary to meet the linear range values of the instrument.
12.6.3 The ICS consists 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.
12.6.4 The analytical results of ICS Solution A (ICSA) shall fall within the
control limit of ą3 times the CRQL of the analyte's true value or
ą20% of the analyte's true value (the true value shall be zero unless
otherwise stated) in the ICSA, whichever is greater. If not, the
analysis shall be terminated, the problem corrected, the instrument
recalibrated, and re-analysis of the analytical samples analyzed
since the last compliant ICSA shall be performed. The ICSA results
for these analytes shall be reported from an undiluted sample
analysis.
12.6.5 Results for the ICS Solution AB (ICSAB) during the analytical runs
shall fall within the control limit of ą3 times the CRQL of the true
value or ą20% of the true value, whichever is greater, for the
analytes included in the ICSAB. If not, the analysis shall be
terminated, the problem corrected, the instrument recalibrated, and
re-analysis of the analytical samples analyzed since the last
compliant ICSAB shall be performed.
NOTE: The control limits and concentrations for the ICSAB are being
monitored. These may be adjusted to provide greater control of
interferences.
12.6.6 If true values for analytes contained in the ICS are not supplied
with the solutions, 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 a previously supplied ICS met all contract
specifications. Additionally, the results of this initial mean
determination shall be used as the true value for the lifetime of
that solution (i.e., until the solution is exhausted). Only if the
ICS solutions are not available from USEPA, independent Check Samples
shall be prepared with interferent and analyte concentrations at the
levels specified in Sections 7.2.4.4.1 and 7.2.4.4.2. The mean value
and standard deviation shall be established by initially analyzing
D-23/ICP-MS ILM05.2
-------
Exhibit D (ICP-MS) Section 12
Quality Control (Con't)
the Check Samples at least five times repetitively for each analyte
listed on Form IVB-IN. Results shall fall within the control limit
of ą3 times the CRQL of the established mean value or ą20% of the
established mean value, whichever is greater. The mean and standard
deviation shall be reported in the raw data. Results from the ICS
analyses shall be reported on Form IVB-IN for all ICP-MS parameters.
12.7 Spike Sample Analysis
12.7.1 The spike sample analysis is designed to provide information about
the effect of 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). At
least one spike sample analysis (matrix spike) shall be performed for
each SDG3.
12.7.2 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 "original
sample" (see Section 12.8). The average of the duplicate results
cannot be used for the purpose of determining percent recovery.
Samples identified as field blanks and Performance Evaluation (PE)
samples shall not be used for spiked sample analysis. USEPA may
require that a specific sample be used for the spike sample analysis.
12.7.3 The analyte spike shall be added in the amount given in Table 5 -
Spiking Levels for Spike Sample Analysis, for each element analyzed.
12.7.4 If the spike recovery is not at or within the limits of 75-125%, the
data for all samples received and associated with that spike sample
and shall be flagged with the letter WN" on Forms IA/IB-IN and VA-IN.
An exception to this rule is granted when the sample concentration
exceeds the Spike Added (SA) 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.
12.7.5 When the matrix spike recovery falls outside the control limits and
the sample result does not exceed four times the spike added, a post-
digestion spike shall be performed for those elements that do not
meet the specified criteria. Note that if a post-digestion spike
analysis is required for an analyte, the same EPA sample that was
used for the matrix spike shall be used for the post-digestion spike
analysis. Spike an unspiked aliquot of the digestate at two times
the indigenous level or two times the CRQL, whichever is greater.
Results of the post-digestion spike shall be reported on Form VB-IN.
12.7.6 In the instance where there is more than one spike sample per matrix
per SDG, if one spike sample recovery is not within contract
criteria, flag all the samples in the SDG. Individual component
percent recoveries are calculated as follows:
EQ. 3 Spike Percent Recovery
%Recovery = SSR " SR x 100
* SA
3USEPA may require additional spike sample analyses, upon USEPA Regional
CLP Project Officer (CLP PO) request.
ILM05.2 D-24/ICP-MS
-------
Exhibit D (ICP-MS) Section 12
Quality Control (Con't)
WHERE, SSR = Spike Sample Result
SR = Sample Result
SA = Spike Added
12.7.7 When sample concentration is less than the Method Detection Limit
(MDL), use SR = 0 only for purposes of calculating percent recovery.
The Spike Sample Results (SSRs), Sample Results (SRs), Spike Added
(SA), and percent recovery (positive or negative) shall be reported
on Form VA-IN.
12.7.8 The units used for reporting SSRs will be identical to those used for
reporting sample results on Form IA-IN.
12.8 Duplicate Sample Analysis
12.8.1 One duplicate sample shall be analyzed for each SDG4. Duplicates
cannot be averaged for reporting on Form IA-IN.
12.8.2 Samples identified as field blanks and PE samples shall not be used
for duplicate sample analysis. USEPA may require that a specific
sample be used for duplicate sample analysis. The Relative Percent
Difference (RPD) for each analyte is calculated as follows:
EQ. 4 Duplicate Sample Relative Percent Difference
RPD = I S " D I x 100
(S+D)/2
WHERE, RPD = Relative Percent Difference
S = Sample Result (original)
D = Duplicate Result
12.8.3 The results of the duplicate sample analyses shall be reported on
Form VI-IN. A control limit of 20% for RPD shall be used for
original and duplicate sample values greater than or equal to five
times the CRQL (see Exhibit C). A control limit equal to the CRQL
shall be entered in the "Control Limit" column on Form VI-IN if
either the sample or duplicate value is less than five times the
CRQL. If the sample and duplicate values are greater than or equal
to five times the CRQL, or if the sample and duplicate values are
less than the CRQL, the "Control Limit" field is left empty.
12.8.4 If one result is above five times the CRQL level and the other is
below, use the CRQL criteria to determine if the duplicate analysis
is in control. If both sample and duplicate values are less than the
MDL, the RPD is not calculated on Form VI-IN. 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 IA/IB-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 in the SDG. The percent
4USEPA may require additional duplicate sample analyses, upon USEPA
Regional CLP PO request.
D-25/ICP-MS ILM05.2
-------
Exhibit D (ICP-MS) Section 12
Quality Control (Con't)
difference data will be used by USEPA to evaluate the long-term
precision of the methods for each element. Specific control limits
for each element may be added to Form VI-IN at a later date based on
these precision results.
12.9 Laboratory Control Sample (LCS) Analysis
12.9.1 A water/aqueous LCS (LCSW) shall be analyzed for each analyte using
the same sample preparations, analytical methods, and Quality
Assurance/Quality Control (QA/QC) procedures employed for USEPA
samples received.
12.9.2 The LCSW solution must be obtained from USEPA (if unavailable, the
ICV solution(s) may be used). One aqueous LCS shall be prepared and
analyzed for each group of samples in an SDG, or for each batch of
samples digested, whichever is more frequent.
12.9.3 All LCSW and percent recovery results shall be reported on Form VII-
IN. If the percent recovery for the LCSW falls outside the control
limits of 80-120%, the analyses shall be terminated, the problem
corrected, and the samples associated with that LCSW redigested and
re-analyzed with appropriate new QC.
12.10 ICP-MS Serial Dilution Analysis
12.10.1 Prior to reporting concentration data for the analyte elements, the
Contractor shall analyze and report the results of the ICP-MS serial
dilution analysis. The ICP-MS serial dilution analysis shall be
performed on a sample from each SDG. Samples identified as field
blanks and PE samples shall not be used for serial dilution analysis.
12.10.2 If the analyte concentration is sufficiently high (minimally a factor
of 50 above the MDL 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 a control limit of
10%, and the internal standards in the original sample met the
contract criteria, an interference effect must be suspected, and the
data for all affected analytes in the samples received and associated
with that serial dilution must be flagged with an "E" on Forms IA/IB-
IN and VIII-IN.
12.10.3 The percent differences for each component are calculated as follows:
EQ. 5 Serial Dilution Percent Difference
I T _ O I
% Difference = -L^ ^-1 x 100
WHERE, I = Initial Sample Result (Instrument Reading)
S = Serial Dilution Result (Instrument Reading x5)
12.10.4 In the instance where there is more than one serial dilution per SDG,
if one serial dilution result is not within the contract criteria,
flag all samples in the SDG. Serial dilution results and "E" flags
shall be reported on Form VIII-IN.
12.11 Internal Standards
12.11.1 The analyst shall monitor the responses from the internal standards
throughout the sample set being analyzed. Ratios of the internal
ILM05.2 D-26/ICP-MS
-------
Exhibit D (ICP-MS) Section 12
Quality Control (Con't)
standard responses between isotopes should also be routinely
monitored. This information may be used to correct potential
problems caused by mass dependent drift, errors incurred in adding
the internal standards or increases in the concentrations of
individual internal standards caused by background contributions from
the sample. The absolute response of any one internal standard must
not deviate more than 60-125% of the original response in the
calibration blank. If deviations greater than these are observed,
the laboratory shall monitor the calibration blank internal standard
responses by re-analyzing the calibration blank. If these are within
the limits, the original sample shall be diluted by a factor of two,
internal standards added, and the sample re-analyzed. If the
internal standard responses for the calibration blank are not within
the limits, terminate the analysis, correct the problem, recalibrate,
verify the calibration and re-analyze all analytical samples analyzed
since the last compliant calibration blank. If the internal standard
responses.for the diluted sample analysis are not within the limits,
note this in the SDG Narrative.
12.12 Method Detection Limit (MDL) Determination
12.12.1 Before any field samples are analyzed under this contract, the MDLs
shall be determined for each instrument used, prior to the start of
contract analyses, and annually thereafter, and shall meet the levels
specified in Exhibit C.
An MDL study shall be performed after major instrument maintenance,
or changes in instrumentation or instrumental conditions to verify
the current sensitivity of the analysis.
12.12.2 To determine the MDLs, the Contractor shall run MDL studies following
the procedures given in 40 CFR, Part 136. The Contractor shall
prepare the MDL samples by each digestion procedure used and shall
analyze these samples on each instrument used. The Contractor shall
also analyze non-prepared MDL samples on each instrument used.
12.12.3 The determined concentration of the MDL shall be less than half the
concentration of the CRQL listed in Exhibit C.
12.12.4 The direct analysis MDL (Preparation Method/Code "NP1") shall be used
to determine the appropriate concentration qualifier for the results
of instrument QC.
12.12.5 The results of the MDL determination studies shall be forwarded to
the USEPA Regional CLP PO, Sample Management Office (SMO), and
Quality Assurance Technical Support (QATS).
12.12.6 The MDL results shall be reported on Form IX-IN.
12.13 Linear Dynamic Range (LDR)
12.13.1 Before any field samples are analyzed under this contract, the upper
limit of the linear calibration range shall be established for each
analyte by determining the signal responses from a minimum of three
different concentration standards, one of which is close to the upper
limit of the linear range. The linear calibration range used for the
analysis of samples shall be determined from the resulting data. The
upper LDR limit shall be an observed signal no more than 10% below
the level extrapolated from lower standards. Determined sample
analyte concentrations that are greater than 90% of the determined
upper LDR limit must be diluted and re-analyzed. The LDRs must be
verified whenever a change in instrument hardware operating
D-27/ICP-MS ILM05.2
-------
Exhibit D (ICP-MS) Sections 13-16
Method Performance
conditions indicate they should be redetermined, or verified
quarterly.
13.0 METHOD PERFORMANCE
Not applicable.
14.0 POLLUTION PREVENTION
See Section 1.15 in Exhibit D - Introduction to Analytical Methods.
15.0 WASTE MANAGEMENT
See Section 1.16 in Exhibit D - Introduction to Analytical Methods.
16.0 REFERENCES
16.1 US Environmental Protection Agency. Determination of Trace Elements in
Waters and Wastes by Inductively Coupled Plasma - Mass Spectrometry.
Method 200.8. Revision 5.4. 1994.
(
16.2 US Environmental Protection Agency. Test Methods for Evaluating Solid
Waste, Physical/Chemical Methods (SW-846). Method 6020A. Third Edition,
Update IV-A. 1986.
16.3 US Government Printing Office. 40 Code of Federal Regulations, Part 136,
Section 1, Appendix B.
ILM05.2 D-28/ICP-MS
-------
Exhibit D (ICP-MS) - Section \1
Tables/Diagrams/Flowcharts
17.0 TABLES/DIAGRAMS/FLOWCHARTS
Table 1. Isobaric Molecular-Ion Interferences
Analyte
121Sb
123Sb
75As
138Ba
l37Ba
136Ba
l35Ba
134Ba
132Ba
l30Ba
9Be
u/1Cd
ll2Cd
lllCd
110Cd
113Cd
116Cd
106Cd
108Cd
52Cr
53Cr
5oCr
54Cr
59Co
63Cu
65Cu
208pb
206pb
Oxygen
PdO
AgO
CoO
SnO
SbO
SnO
SnO
SnO
SnO,
CdO
CdO
MoO
MoO,
ZrO
MoO
MoO,
ZrO
MoO
MoO
ZrO
MoO,
ZrO
ArO
CIO
SO
CaO
TiO, P02
TiO
Hydroxyl
NiOH
SbOH
SnOH
SnOH
SnOH
SnOH
InOH
CdOH
MoOH
MoOH
MoOH
MoOH
ZrOH
C10H
ArOH
C10H
CaOH
TiOH
TiOH
Nitrogen
AgN
AgN
NiN
SnN
SnN
SnN, CdN
MoN
MoN
MoN
MoN, ZrN
MoN, ZrN
MoN, ZrN
KN
ArN
ArN, CaN
ScN
TiN
VN
Chlorine
SrCl
ArCl
MoCl
MoCl
MoCl
MoCl
MoCl
SeCl
SeCl, AsCl
GeCl
GeCl, AsCl
SeCl, AsCl
GeCl
NCI, OC1
MgCl
SiCl, MgCl
SiCl
Sulfur
ZrS
CaS
MoS
MoS
SeS
SeS
SeS
GeS
SeS, GeS
SO
A1S
PS
S2, SO2H
Carbon
AgC
CdC
CuC
SnC
SnC
SnC
SnC
MoC
MoC
MoC, ZrC
yioC, ZrC
ArC
KC
ArC
CaC
TiC
VC
CrC
Other
Mo++
Sn++
ArNa
D-29/ICP-MS
ILM05.2
-------
Exhibit D (ICP-MS) Section 17
Tables/Diagrams/Flowcharts (Con't)
Table 1.
Isobaric Molecular-Ion Interferences (Con't)
Analyte
207 Pb
204 Pb
55Mn
202Hg
200Hg
l"Hg
201Hg
198Hg
204Hg
196Hg
58Ni
60Ni
62Ni
61Ni
64Ni
80Se
78Se
82Se
76Se
"Se
74Se
107Ag
109Ag
205rŁ.^
203T1
51V
50V
64Zn
66Zn
68Zn
Oxygen
KO
WO
WO
WO
WO
CaO
CaO
TiO
ScO
TiO
ZnO
NiO
ZnO
NiO
NiO
NiO
ZrO
CIO
SO
TiO
TiO
CrO
Hydroxyl
ArOH
WOH
WOH
WOH
TaOH
KOH
CaOH
ScOH
CaOH
TiOH
CuOH
NiOH
CuOH
CoOH
NiOH
FeOH
ZrOH
MoOH
WOH
SOH
TiOH
TiOH
VOH
Nitrogen
KN
WN
WN
WN
CaN
TiN
TiN
TiN
TiN, CrN
ZnN
ZnN
ZnN
NiN
CuN
NiN
MoN
C1N
ArN
TiN, CrN
CrN
FeN
Chlorine
NaCl
MgCl, NaCl
A1C1, MgCl
MgCl
SiCl, A1C1
ScCl, CaCl
CaCl, KC1
TiCl, ScCl
KC1
CaCl, ArCl
C12, KC1
GeCl
GeCl
CIO, C1N
SiCl, A1C1
PCI, SiCl
PCI
Sulfur
NaS
MgS
SiS
SiS
SiS
S 2
ris
TiS
IiS, CrS
CaS
ScS
CaS
AsS
SeS
FS
S 2
S2
ArS
Carbon
CaC
we
we
TiC
TiC
TiC, CrC
TiC
CrC
ZnC
ZnC
ZnC
CuC
NiC
MoC
MoC
KC
ArC
CrC
FeC
FeC
Other
Cd++
Cd*+, Sn++
Sn t+
3n ++
Sn++
Mo++
Ba++
ILM05.2
D-30/ICP-MS
-------
Exhibit D (ICP-MS) Section 17
Tables/Diagrams/Flowcharts (Con't)
Table 1.
Isobaric Molecular-Ion Interferences (Con't)
Analyte
"Zn
70Zn
Oxygen
VO
FeO
Hydroxyl | Nitrogen | Chlorine
TiOH
CrOH
CrN
GeN
SCI
C12
Sulfur
CIS
ArS
Carbon
MnC
NiC
Other
Ba++
NOTE: The information provided in this table does not indicate that all of the
described interferences need to be tested. However, this table can be
consulted if unusual samples are encountered.
D-31/ICP-MS
ILM05.2
-------
Exhibit D (ICP-MS) - Section 17
Tables/Diagrams/Flowcharts (Con't)
Table 2. Mass Choices for Elements that Must Be Monitored
During the Analytical Run
Mass
27.
121
15.
134,
135, 136, 137
1
111.
12,
114
53
59
63,
206,
21,
65
207. 208
25_, 26.
55
60.,
77,
107,
203,
61, 62
78, 80, 82.
109
205
51
66,
67, 68
Element of Interest
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium
Cobalt
Copper
Lead
Magnesium
Manganese
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
NOTE: Underlined isotopes are preferred for measurements. Where possible,
alternative isotopes are indicated. Those isotopes not listed shall not be
used as a primary isotope for measurement, although they may be monitored for
interference corrections if necessary.
ILM05.2
D-32/ICP-MS
-------
Exhibit D (ICP-MS) Section 17
Tables/Diagrams/Flowcharts (Con't)
Table 3. Recommended Elemental Expressions for Isobaric Interferences
Element
Al
Sb
As
Ba
Be
Cd
Cr
Co
Cu
Pb
Mg
Mn
Ni
Se
Ag
Tl
V
Zn
Sc
Y
Rh
In
Tb
Ho
Bi
Isobaric
Correction
none
none
ArCl, Se
none
none
MoO, Pd
none
none
none
none
none
none
none
none
none
none
CIO, Cr
none
none
none
none
Sn
none
none
none
Expression Proportional to Elemental
Concentration
(1.0000) (27C)
(1.0000) (121C)
(1.0000) ( 75C) - (3.127) [("C) - (0.815) (82C)]
(1.0000) (137C)
(1.0000) (9C)
(1.000) ( 11LC) - (1.073) [ (108C) - (0.712) (106C) ]
(1.0000) (52C)
(1.0000) (59C)
(1.0000) (63C)
(1.0000) (206C) + (1.0000) (207C) + (1.0000) (208C)
(1.0000) (25C)
(1.0000) (55C)
(1.0000) (60C)
(1.0000) (78C)
(1.0000) (107C)
(1.0000) (205C)
(1.0000) (S1C) - (3.127) [ (53C) - (0.113) (" C) ]
(1.0000) (66C)
(1.0000) (45C)
(1.0000) (89C)
(1.0000) (103C)
(1.0000) (115C) - (0.0140) (118C)
(1.0000) (159C)
(1.0000) (165C)
(1.0000) (209C)
C - Calibration blank subtracted counts at specified mass
The coefficients in correction equations were calculated using natural
isotopic abundances, and assuming zero instrumental fractionation. For each
particular instrument these coefficients must be determined experimentally.
The correction equations shall not be applied if appropriate interference
check sample measurement demonstrates absence of interference above the CRQL.
D-33/ICP-MS
ILM05.2
-------
Exhibit D (ICP-MS) - Section 17
Tables/Diagrams/Flowcharts (Con't)
Table 4.
Internal Standards (must use at least three)
Internal Standard
Lithium
Scandium
Yttrium
Rhodium
Indium
Terbium
Holmium
Lutetium
Bismuth
Mass
6
45
89
103
115
159
165
175
209
CAS Number
7439-93-2
7440-20-2
7440-65-5
7440-16-6
7440-74-6
7440-27-9
7440-60-0
7439-94-3
7440-69-9
NOTE: Use of Li6 requires enriched standard.
Table 5.
Spiking Levels for Spike Sampl"e Analysis
Analyte
Al
Sb
As
Ba
Be
Cd
Cr
Co
Cu
Pb
Mn
Ni
Se
Ag
Tl
V
Zn
Spike (ug/L)
2000
100
40
2000
50
50
200
500
250
20
500
500
10
50
50
500
500
ILM05.2
D-34/ICP-MS
-------
EXHIBIT D - PART C
ANALYTICAL METHODS
FOR
COLD VAPOR MERCURY ANALYSIS
D-1/Mercury ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
ILM05.2 D-2/Mercury
-------
Exhibit D - Analytical Methods for Cold Vapor Mercury Analysis
Table of Contents
Section Page
1.0 SCOPE AND APPLICATION 5
2.0 SUMMARY OF METHOD 5
2.1 Water by Automated and Manual Techniques 5
2.2 Soil/Sediment by Manual Technique 5
3.0 DEFINITIONS 6
4.0 INTERFERENCES 6
4.1 Water 6
4.2 Soil/Sediment 6
5.0 SAFETY 7
6.0 EQUIPMENT AND SUPPLIES 7
6.1 General Information for Water and Soils (Automated and
Manual Techniques) 7
6.2 Water by Automated Technique 7
6.3 Water and Soil/Sediment by Manual Techniqu e 7
7.0 REAGENTS AND STANDARDS 8
7.1 Reagents 8
7.2 Standards 9
8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE 10
8.1 Sample Collection and Preservation 10
8.2 Procedure for Sample Storage 10
8.3 Contract Required Holding Time 10
9.0 CALIBRATION AND STANDARDIZATION 11
9.1 Cold Vapor Atomic Absorption (AA) Instrument
Calibration Procedure 11
9.2 Initial Calibration Verification (ICV) 11
9.3 Continuing Calibration Verification (CCV ) 11
9.4 Initial and Continuing Calibration Blank (ICB/CCB) 12
10.0 PROCEDURE 13
10.1 Sample Preparation 13
10.2 Sample Analysis 15
11.0 DATA ANALYSIS AND CALCULATIONS 17
11.1 Water/Aqueous by Automated Technique 17
11.2 Water/Aqueous by Manual Technique 17
11.3 Soil by Manual Technique 17
11.4 Adjusted Method Detection Limit (MDL)/Adjusted Contract
Required Quantitation Limit (CRQL) Calculation 17
12.0 QUALITY CONTROL 19
12.1 Initial Calibration Verification (ICV) 19
12.2 Continuing Calibration Verification (CCV ) 19
12.3 Contract Required Quantitation Limit (CRQL) Check
Standard (CRI) 19
12.4 Blank Analyses 19
12.5 Spike Sample Analysi s 20
12.6 Duplicate Sample Analysi s 21
12.7 Laboratory Control Sample (LCS) Analysis 22
12.8 Method Detection Limit (MDL) Determination 23
13.0 METHOD PERFORMANCE 24
D-3/Mercury ILM05.2
-------
Exhibit D - Analytical Methods for Cold Vapor Mercury Analysis
Table of Contents (Con't)
Section Page
14.0 POLLUTION PREVENTION 24
15.0 WASTE MANAGEMENT 24
16.0 REFERENCES 24
17.0 TABLES/DIAGRAMS/FLOWCHARTS 24
ILM05.2 D-4/Mercury
-------
Exhibit D (Mercury) Sections 1 & 2
Scope and Application
1.0
SCOPE AND APPLICATION
The analytical method that follows is designed to analyze water,
sediment, sludge, and soil samples taken from hazardous waste sites
using a cold vapor technique with Atomic Absorption (AA) for total
mercury.
In addition to inorganic forms of mercury, organic mercurials may also
be present. These organo-mercury compounds will not respond to the cold
vapor AA technique unless they are first broken down and converted to
mercuric ions. Potassium permanganate oxidizes many of these compounds,
but 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.
The range of the method may be varied through instrument and/or recorder
expansion. Using a 100 milliliters (mL) sample, a detection limit of
less than 0.1 micrograms per Liter (pg/L) can be achieved.
The range of the method for soil/sediments is 0.05 milligrams per
kilogram (mg/kg) to 5 mg/kg. The range may be extended above or below
the normal range by increasing or decreasing sample size or through
instrument and recorder control.
2.0 SUMMARY OF METHOD
2.1 Water by Automated and Manual Techniques
This is a physical method based on the absorption of radiation at 253.7
nanometers (nm) by mercury vapor. Free mercury atoms can exist at room
temperature; therefore, mercury can be measured by Atomic Absorption
(AA) without a heated sample cell. Organic compounds are oxidized, and
in the cold vapor mercury technique, mercury is chemically reduced to
the free atomic state by reacting the sample with a strong reducing
agent like stannous chloride or sodium borohydride in a closed reaction
vessel. The volatile free mercury is then driven from the reaction
flask by bubbling air through the solution. Mercury atoms are carried
in the air stream through tubing connected to an absorption cell, which
is placed in the light path of the AA spectrophotometer. Sometimes the
cell is heated slightly to avoid water condensation; otherwise the cell
is completely unheated. As the mercury atoms pass into the sampling
cell, measured absorbance rises indicating the increasing concentration
of mercury atoms in the light path. Some systems allow the mercury
vapor to pass from the absorption tube to waste, in which case the
absorption peaks and then falls as the mercury is depleted. The highest
absorbance observed during the measurement will be taken as the
analytical signal.
2.2 Soil/Sediment by Manual Technique
2.2.1 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.
2.2.2 An alternate digestion involving the use of an autoclave is described
in Section 10.1.4.2.1.2.
D-5/Mercury
ILM05.2
-------
Exhibit D (Mercury) Sections 3 & 4
Definitions
3.0 DEFINITIONS
See Exhibit G for a complete list of definitions.
4.0 INTERFERENCES
4.1 Water
4.1.1 Some sea waters and wastewaters high in chlorides have shown a
positive interference, and require additional permanganate [as much
as 25 milliliters (mL)]. During the oxidation step, chlorides are
converted to free chlorine which will also absorb radiation at 253
nanometers (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.
4.1.2 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.
4.1.3 Possible interference from sulfide is eliminated by the addition of
potassium permanganate. Concentrations as high as 20 milligram per
Liter (mg/L) of sulfide as sodium sulfide do not interfere with the
recovery of added inorganic mercury from reagent water.
4.1.4 Copper has also been reported to interfere; however, copper
concentrations as high as 10 mg/L have no effect on recovery of
mercury from spiked samples.
4.1.5 Samples containing solids must be blended and then mixed while being
sampled if total mercury values are to be reported.
4.2 Soil/Sediment
4.2.1 The same types of interferences that may occur in water samples are
also possible with sediments (i.e., sulfides, high copper, high
chlorides, etc.).
4.2.2 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.
ILM05.2 D-6/Mercury
-------
Exhibit D (Mercury) Sections 5 & 6
Safety
5.0 SAFETY
See Section 1.14 in Exhibit D - Introduction to Analytical Methods.
6.0 EQUIPMENT AND SUPPLIES
Brand names, suppliers, and part numbers are for illustrative purposes
only. No endorsement is implied. Equivalent performance may be
achieved using equipment and supplies other than those specified here,
however, a demonstration of equivalent performance meeting the
requirements of this Statement of Work (SOW) is the responsibility of
the Contractor. The Contractor shall document any use of alternate
equipment or supplies in the Sample Delivery Group (SDG) Narrative.
6.1 General Information for Water and Soils (Automated and Manual
Techniques)
6.1.1 Atomic Absorption (AA) Spectrophotometer - Any AA 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: Instruments designed specifically for the measurement of
mercury using the cold vapor technique are commercially available and
may be substituted for the AA spectrophotometer.
NOTE: All cold vapor mercury analyzers shall be equipped with all
manufactured required equipment (i.e., dryers) to ensure that the
specified CRQLs are met.
6.1.2 Mercury Hollow Cathode Lamp
6.1.3<'-* Recorder - Any multi-range variable speed recorder that is compatible
with the UV detection system is suitable.
6.2 Water by Automated Technique
6.2.1 Automated Analyzer instrumentation consisting of:
6.2.1.1 Sampler with provision for sample mixing
6.2.1.2 Manifold
6.2.1.3 Proportioning Pump(s)
6.2.1.4 High temperature heating bath with distillation coil(s)
6.2.1.5 Vapor-liquid separator
6.2.1.6 Absorption cell with quartz windows
6.3 Water and Soil/Sediment by Manual Technique
6.3.1 Absorption Cell - Standard spectrophotometer cells
6.3.2 Air Pump - Any device capable of delivering 1 Liter' (L) of air per
minute may be used.
6.3.3 Flowmeter - Capable of measuring an air flow of 1 L per minute.
6.3.4 Aeration Tubing - Tygon tubing is used for transporting the mercury
vapor from the sample bottle to the absorption cell and for its
return.
D-7/Mercury -, ILM05.2
-------
Exhibit D (Mercury) Sections 6 & 1
Reagents and Standards
6.3.4.1 Straight glass tubing terminating in a coarse porous frit is used
for sparging air into the sample.
6.3.5 Drying Tube - 6" X 3/4" diameter tube containing 20 grams (g) of
magnesium perchlorate.
NOTE: In place of the magnesium perchlorate drying tube, a small
reading lamp with a 60-watt 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 temperature.
7.0 REAGENTS AND STANDARDS
7.1 Reagents
7.1.1 Water by Automated Technique
7.1.1.1 Reagent Water - The purity of this water must be equivalent to
ASTM Type II water (ASTM D1193-77). Use this preparation for all
reagents, standards, and dilutions of solutions.
7.1.1.2 Sulfuric acid, concentrated - Reagent grade.
7.1.1.2.1 Sulfuric acid, 2N - Dilute 56 milliliters (mL) of concentrated
sulfuric acid to 1 Liter (L) with reagent water.
7.1.1.2.2 Sulfuric acid, 10% - Dilute 100 mL concentrated sulfuric acid
to 1 L with reagent water.
7.1.1.3 Nitric acid, concentrated - Reagent grade of low mercury content.
Nitric acid, 0.5% wash solution - Dilute 5 mL of concentrated
nitric acid to 1 L with reagent water.
7.1.1.4 Stannous sulfate - Add 50 grams (g) stannous sulfate to 500 mL of
2N sulfuric acid (see Section 7.1.1.2.1). This mixture is a
suspension and should be stirred continuously during use.
NOTE: Stannous chloride may be used in place of stannous sulfate.
7.1.1.5 Sodium chloride-hydroxylamine sulfate solution - Dissolve 30 g of
sodium chloride and 30 g of hydroxylamine sulfate in reagent water
to 1 L.
NOTE: Hydroxylamine hydrochloride may be used in place of
hydroxylamine sulfate.
7.1.1.6 Potassium permanganate (KMnO4) - 0.5% solution, w/v. Dissolve 5 g
of potassium permanganate in 1 L of reagent water.
7.1.1.7 Potassium permanganate, 0.1N - Dissolve 3.16 g of potassium
permanganate in reagent water and dilute to 1 L.
7.1.1.8 Potassium persulfate - 0.5% solution, w/v. Dissolve 5 g of
potassium persulfate in 1 L of reagent water.
7.1.1.9 Air scrubber solution - Mix equal volumes of 0.1N potassium
permanganate (see Section 7.1.1.6) and 10% sulfuric acid (see
Section 7.1.1.2.2).
ILM05.2 D-8/Mercury
-------
Exhibit D (Mercury) Section 7
Reagents and Standards (Con't)
7.1.2 Water and Soil/Sediment by Manual Technique
7.1.2.1 Reagent water - The purity of this water must be equivalent to
ASTM Type II water (ASTM Dl193-77). Use this preparation for all
reagents, standards, and dilutions of solutions.
7.1.2.2 Sulfuric acid, concentrated - Reagent grade.
7.1.2.2.1 Sulfuric acid, 0.5N - Dilute 14.0 mL of concentrated sulfuric
acid to 1 L. (Water technique only.)
7.1.2.3 Nitric acid, concentrated - Reagent grade of low mercury content.
If a high Preparation Blank (PB) is obtained, it may be necessary
to distill the nitric acid. .
7.1.2.4 Stannous sulfate - Add 25 g stannous sulfate to 250 mL of 0.5N
sulfuric acid. This mixture is a suspension and should be stirred
continuously during use.
NOTE: Stannous chloride may be used in place of stannous sulfate.
7.1.2.5 Sodium chloride-hydroxylamine sulfate solution - Dissolve 12 g of
sodium chloride and 12 g of hydroxylamine sulfate in reagent water
and dilute to 100 mL.
NOTE: Hydroxylamine hydrochloride may be used in place of
hydroxylamine sulfate.
7.1.2.6 Potassium permanganate (KMn04) - 5% solution, w/v. Dissolve 5 g
of potassium permanganate in 100 mL of reagent water.
7.1.2.7, Potassium persulfate - 5% solution, w/v. Dissolve 5 g of
'-'- potassium persulfate in 100 mL of reagent water.
7.2 Standards
7.2.1 Introduction
The Contractor must provide all standards to be used with this
contract. These standards may be used only after they have been
certified according to the procedure in Exhibit E, Section 8.0. The
Contractor must be able to verify that the standards are certified.
Manufacturer's certificates of analysis must be retained by the
Contractor and presented upon request.
7.2.1.1 Stock standard solutions may be purchased or prepared from ultra
high purity grade chemicals or metals.
7.2.1.2 Stock mercury solution - Dissolve 0.1354 g of mercuric chloride in
75 mL of reagent water. Add 10 mL of concentrated nitric acid and
adjust the volume to 100.0 mL [1.0 mL = 1.0 milligram (ing) Hg] .
7.2.1.3 Working mercury solution - Make successive dilutions of the stock
mercury solution (see Section 7.2.1.2) to obtain a working
standard containing 0.1 micrograms (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.
D-9/Mercury ILM05.2
-------
Exhibit D (Mercury) Sections 7 & 8
Sample Collection, Preservation, and Storage
7.2.2 Working Standards
7.2.2.1 Contract Required Quantitation Limit (CRQL) Check Standard (CRI)
The concentration of the CRI for mercury shall be at the CRQL.
Information regarding the CRI shall be reported on Form IIB-IN.
7.2.2.2 Method Detection Limit (MDL) Solution
The MDL solution shall be at a concentration of 3 to 5 times the
expected MDL.
8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE
8 .1 Sample Collection and Preservation
All samples must be collected in glass or polyethylene containers.
Water/aqueous samples must be preserved with nitric acid to pH less than
2 immediately after collection. All samples must be iced or
refrigerated at 4°C (ą2°C) from the time of collection until digestion.
8.1.1 Dissolved Metals
For the determination of dissolved metals, the sample must be
filtered through a 0.45 micrometer (urn) pore diameter membrane filter
at the time of collection or as soon as possible. Use a portion of
the sample to rinse the filter flask, discard this portion, and
collect the required volume of filtrate. Preserve the filtrate with
nitric acid to pH less than 2 immediately after filtration.
8.2 Procedure for Sample Storage
The samples must be protected from light and refrigerated at 4°C (ą2°C)
from the time of receipt until 60 days after delivery of a complete,
reconciled data package to USEPA. After 60 days the samples may be
disposed of in a manner that complies with all applicable regulations.
8.3 Contract Required Holding Time
The maximum holding time for mercury is 26 days from Validated Time of
Sample Receipt (VTSR).
ILM05.2 D-10/Mercury
-------
Exhibit D (Mercury) Section 9
Calibration and Standardization
9.0 CALIBRATION AND STANDARDIZATION
9.1 Cold Vapor Atomic Absorption (AA) Instrument Calibration Procedure
9.1.1 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.
9.1.2 The date and time of preparation and analysis shall be given in the
raw data.
9.1.3 Calibration standards shall be prepared fresh with each preparation
batch. Prepare a minimum of five calibration standards (which
includes a blank) in graduated amounts in the appropriate range. One
of the standards must be at the Contract Required Quantitation Limit
(CRQL).
9.1.4 Aspirate the standards and record the readings. Results for these
standards shall be within 5% of the true value. Each standard
concentration and the calculations to show that the 5% criteria has
been met shall be given in the raw data. If the values do not fall
within this range, recalibration is necessary. The 5% criteria does
not apply to the calibration standard at the CRQL. The acceptance
criteria for the initial calibration curve is a correlation
coefficient more than or equal to 0.995.
9.1.5 Baseline correction is acceptable as long as it is performed after
every sample or after the Continuing Calibration Verification (CCV)
and Blank (CCB) check. Resloping is acceptable as long as it is
immediately preceded and immediately followed by a compliant CCV and
CCB.
9.2 "^Initial Calibration Verification (ICV)
9.2.1 Immediately after the AA system has been calibrated, the accuracy of
the initial calibration shall be verified and documented for mercury
by the analysis of the ICV solution at the wavelength used for
analysis.
9.2.2 Only if the ICV solution is not available from USEPA, or where a
certified solution of the 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 analyte from a different source than that
used in the standards for the instrument calibration. The value for
the ICV shall be reported on Form IIA-IN.
9.3 Continuing Calibration Verification (CCV)
9.3.1 To ensure calibration accuracy during each analysis run, one of the
following standards is to be used for the CCV and shall be analyzed
and reported 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 at the beginning of the run and after the last
analytical sample. The analyte concentration in the CCV standard
shall be different than the concentration used for the ICV and shall
be one of the following solutions at or near the mid-range level of
the calibration curve:
D-ll/Mercury
ILM05.2
-------
Exhibit D (Mercury) Section 9
Calibration and Standardization (Con't)
^ USEPA Solutions
ť NIST Standards
'*: A Contractor-prepared standard solution
The same CCV standard shall be used throughout the analysis runs for
a Sample Delivery Group (SDG) of samples received.
9.3.2 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.
9.3.3 Information regarding the CCV shall be reported on Form IIA-IN.
9.4 Initial and Continuing Calibration Blank (ICB/CCB)
A calibration blank shall be analyzed at each wavelength used for
analysis immediately after every ICV and CCV, at a frequency of 10% or
every 2 hours 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 analyzed immediately after the last CCV, and the
last CCV shall be analyzed immediately after the last analytical sample
of the run. The results for the calibration blanks shall be reported on
Form III-IN.
ILM05.2 D-12/Mercury
-------
Exhibit D (Mercury) Section 10
Procedure
10.0 PROCEDURE
10.1 Sample Preparation
10.1.1 If insufficient sample amount (less than 90% of the required amount)
is received to perform the analyses, the Contractor shall contact the
Sample Management Office (SMO) to inform them of the problem. SMO
will contact the Region for instructions. The Region will either
require that no sample analyses be performed or will require that a
reduced volume be used for the sample analysis. No other changes in
the analyses will be permitted. The Contractor shall document the
Region's decision in the Sample Delivery Group (SDG) Narrative.
10.1.2 If multiphase samples (e.g., two-phase liquid sample, oily
sludge/sandy soil sample) are received by the Contractor, the
Contractor shall contact SMO to apprise them of the type of sample
received. SMO will contact the Region. If all phases of the sample
are amenable to analysis, the Region may require the Contractor to do
any of the following:
:*: Mix the sample and analyze an aliquot from the homogenized
sample.
== Separate the phases of the sample, and analyze one or more of
the phases separately. SMO will provide EPA sample numbers for
the additional phases, if required.
:i: Do not analyze the sample.
10.1.2.1 If all of the phases are not amenable to analysis (i.e., outside
the scope), the Region may require the Contractor to do any of the
following:
:x' Separate the phases and analyze the phase (s) that is (are)
amenable to analysis. SMO will provide EPA sample numbers
for the additional phases, if required.
'*' Do not analyze the sample.
10.1.2.2 No other changes in the analyses will be permitted. The
Contractor shall document the Region's decision in the SDG
Narrative.
10.1.3 Water Preparation of Standards and Samples (Manual Technique)
10.1.3.1 Standards Preparation
10.1.3.1.1 Transfer aliquots of the working mercury solution to a series
of 300 milliliters (mL) BOD bottles. Add enough reagent water
to each bottle to make a total volume of 100 mL.
10.1.3.1.2 Mix thoroughly and add 5 mL of concentrated sulfuric acid (see
Section 7.1.2.2) and 2.5 mL of concentrated nitric acid (see
Section 7.1.2.3) to each bottle. Add 15 mL of KMnO 4 (see
Section 7.1.2.6) solution to each bottle and allow to stand at
least 15 minutes. Add 8 mL of potassium persulfate (see
Section 7.1.2.7) to each bottle and heat for 2 hours in a water
bath maintained at 95°C. (If an autoclave is employed, cover
the BOD bottles with foil and heat in the autoclave for 15
minutes at 120°C and 15 PSI instead of heating for 2 hours in a
waterbath at 95°C). Cool and add 6 mL of sodium chloride-
hydroxylamine sulfate solution (see Section 7.1.2.5) to reduce
the excess permanganate. When the solution has been
D-13/Mercury ILM05.2
-------
Exhibit D (Mercury) Section 10
Procedure (Con't)
decolorized, wait 30 seconds, add 5 mL of the stannous sulfate
solution (see Section 7.1.2.4) and immediately attach the
bottle to the aeration apparatus to form a closed system. At
this point the sample is allowed to stand quietly without
manual agitation.
10.1.3.1.3 The circulating pump, which has previously been adjusted to a
rate of 1 Liter (L) per minute, is allowed to run continuously
(see Note 1). The absorbance will increase and reach maximum
within 30 seconds. As soon as the response levels off, open
the bypass valve and continue the aeration until the absorbance
returns to its minimum value (see Note 2) . 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 instrument response at
253 nanometers (nm) versus micrograms (ug) of mercury.
NOTE 1: An open system where the mercury vapor is passed
through the absorption cell only once may be used instead of
the closed system.
NOTE 2: 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% H2S04 or 0.25% iodine in a 3% KI solution. A specially
treated charcoal that will adsorb mercury vapor is commercially
available.
10.1.3.2 Sample Preparation
10.1.3.2.1 Preparation Method/Code (CW1)
10.1.3.2.1.1 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 and
continue as described in Section 10.1.3.1.2.
NOTE: The same amount of KMn04 added to the samples should
be present in standards and blanks.
10.1.3.2.1.2 Cool and add 6 mL of sodium chloride-hydroxylamine sulfate
(see Section 7.1.2.5) to reduce the excess permanganate.
Purge the headspace in the BOD bottle for at least 1 minute
and add 5 mL of stannous sulfate (see Section 7.1.2.4) and
immediately attach the bottle to the aeration apparatus.
NOTE: Add reductant in 6 mL increments until KMnO 4 is
completely reduced (until the color is no longer purple).
10.1.4 Soil/Sediment Preparation of Standards and Samples (Manual)
10.1.4.1 Standards Preparation
10.1.4.1.1 Transfer aliquots of the working mercury solutions (see Section
7.2.1.3) to a series of 300 mL BOD bottles. Add enough reagent
water to each bottle to make a total volume of 10 mL.
10.1.4.1.2 Add 5 mL of concentrated H2SO4 (see Section 7.1.2.2) and 2.5 mL
of concentrated HN03 (see Section 7.1.2.3) and heat 2 minutes
in a water bath at 95°C. Allow the sample to cool and add 50
mL reagent water, 15 mL of KMn04 solution (see Section 7.1.2.6)
and 8 mL of potassium persulfate solution (see Section 7.1.2.7)
ILM05.2 ) D-14/Mercury
-------
Exhibit D (Mercury) Section 10
Procedure (Con't)
to each bottle and return to the water bath for 30 minutes.
Cool and add 6 mL of sodium chloride-hydroxylamine sulfate
solution (see Section 7.1.2.5) to reduce the excess
permanganate. Add 50 mL of reagent water (final volume of
reagent water = 100 mL). Treating each bottle individually,
add 5 mL of stannous sulfate solution (see Section 7.1.2.4) and
immediately attach the bottle to the aeration apparatus. At
this point the sample is allowed to stand quietly without
manual agitation. If an autoclave is used, the standards shall
be prepared in the same way as the samples (see Section
10.1.4.2.1.2).
10.1.4.1.3 The circulating pump, which has previously been adjusted to a
rate of 1 L 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 response levels off, open the bypass valve and
continue the aeration until the absorbance returns to its
minimum value. 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 ug of mercury.
10.1.4.2 Sample Preparation
10.1.4.2.1 Preparation Method/Code (CS1)
10.1.4.2.1.1 Weigh a representative 0.20 g (ą0.01 g) portion of wet
sample and place in the bottom of a BOD bottle. Add enough
reagent water to each sample to make a total volume of 10
mL. Continue as described in Section 10.1.4.1.2.
10.1.4.2.1.2 If an autoclave is used, add 5 mL of concentrated H 2S04 and
2 mL of concentrated HN03 to the 0.20 g (ą0.01 g) of
sample. Add 5 mL of saturated KMn04 solution and 8 mL of
potassium persulfate solution and cover with a piece of
aluminum foil. The sample is autoclaved at 120°C and 15 PSI
for 15 minutes. Cool, make up to a volume of 100 mL with
reagent water, and add 6 mL of sodium chloride-hydroxylamine
sulfate solution (see Section 7.1.2.5) to reduce the excess
permanganate. Purge the headspace of the sample bottle for
at least one minute and continue as described under Section
10.1.4.1.2.
10.1.5 Preparation of Standards for Automated Cold Vapor Analysis Technique
(Analysis Method - AV)
10.1.5.1 Standards Preparation
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. From this
solution, prepare standards.
10.2 Sample Analysis
10.2.1 Set up instrument with proper operating parameters.
10.2.2 Profile and calibrate instrument according to instrument
manufacturer's recommended procedures, using calibration standard
D-15/Mercury ILM05.2
-------
Exhibit D (Mercury) Section 10
Procedure (Con't)
solutions mentioned in Section 9.1. Samples prepared by a certain
method must be analyzed with calibration and QC standards prepared by
the same method. Therefore, only one Preparation Method/Code can be
associated with each run.
10.2.3 Analyze the Continuing Calibration Verification (CCV) instrument
check standard and the Continuing Calibration Blank (CCB) after every
10 analytical samples.
10.2.4 Analysis of Water/Aqueous Samples by the Automated Cold Vapor
Technique (AV) Preparation Method/Code (CW2)
10.2.4.1 Set up manifold.
10.2.4.2 Feed all the reagents through the system with acid wash solution
(see Section 7.1.1.3) through the sample line, adjusting the
heating bath to 105°C.
10.2.4.3 Turn on the Atomic Absorption (AA) Spectrophotometer, adjust
instrument settings as recommended by the manufacturer, align
absorption cell in light path for maximum transmittance and place
heat lamp directly over absorption cell.
10.2.4.4 Arrange working mercury standards in sampler and start sampling.
Complete loading of sample tray with unknown samples.
10.2.4.5 After the analysis is complete, put all lines except the H 2SOt
line in reagent water to wash out system. After flushing, wash
out the H2S04 line. Also flush the coils in the high temperature
heating bath by pumping stannous sulfate (see Section 7.1.1.4)
through the sample lines followed by reagent water. This will
prevent build-up of oxides of manganese.
ILM05.2 D-16/Mercury
-------
Exhibit D (Mercury) Section 11
Data Analysis and Calculations
11.0 DATA ANALYSIS AND CALCULATIONS
11.1 Water/Aqueous by Automated Technique
11.1.1 Prepare a standard curve by plotting the instrumental response of
processed standards against true concentration values. Use a linear
regression equation to determine the concentration of field and
Quality Control (QC) samples.
11.1.2 If samples were diluted for analysis, multiply the results from the
linear regression by the dilution factor.
11.2 Water/Aqueous by Manual Technique
11.2.1 Determine the instrumental response of the unknown and determine the
mercury value from the standard curve.
11.2.2 Calculate the mercury concentration in the sample by the formula:
EQ. 1 Aqueous Sample Concentration (Manual)
Hg Concentration (pg/L) = ug Hg, curve x 1000 mL
aliquot volume, mL 1 L
11.3 Soil by Manual Technique
11.3.1 Measure the instrumental response of the unknown and determine the
mercury value from the standard curve.
11.3.2 Calculate the mercury concentration in the sample by the formula:
EQ. 2 Soil Sample Concentration (Manual)
Hg Concentration (mg/kg) = Hg pg/g = x (0.1L)
W X S
WHERE, C = Concentration from curve (ug/L)
W = Wet sample weight (g)
S = % Solids/100 (see Exhibit D - Introduction to
Analytical Methods, Section 1.6).
11.4 Adjusted Method Detection Limit (MDL)/Adjusted Contract Required
Quantitation Limit (CRQL) Calculation
To calculate the adjusted MDL or adjusted CRQL for water/aqueous
samples, multiply the value of the MDL (pg/L) or CRQL (ug/L) by the
Dilution Factor. Calculate the adjusted MDL or adjusted CRQL for soil
samples as follows:
D-17/Mercury ILM05.2
-------
Exhibit D (Mercury) Section 11
Data Analysis and Calculations (Con't)
EQ. 3 Adjusted Soil MDL/Adjusted Soil CRQL Concentration
W i
Adjusted Concentration (dry wt.) (mg/kg) = C x x x DF
WR S
WHERE, C = MDL or CRQL concentration (mg/kg)
WM = Method required wet sample weight (g)
WR = Reported wet sample weight (g)
S = % Solids/100 (see Exhibit D - Introduction to
Analytical Methods, Section 1.6).
DF = Dilution Factor
ILM05.2
D-18/Mercury
-------
Exhibit D (Mercury) Section 12
Quality Control
12.0 QUALITY CONTROL
12.1 Initial Calibration Verification (ICV)
The ICV Standard shall be prepared in the same acid matrix as the
samples and carried through the entire preparation and analysis
procedure. If measurements exceed the control limits of 80% (low) and
120% (high), the analysis shall be terminated, the problem corrected,
the instrument recalibrated, and the calibration reverified.
Information regarding the ICV shall be reported on Form IIA-IN.
12.2 Continuing Calibration Verification (CCV)
The CCV Standard shall be prepared by the analyst at a concentration
equivalent to the mid-point of the calibration curve and carried through
the entire preparation and analysis procedure. If the deviation of the
CCV is greater than the control limits of 80% (low) and 120% (high), the
analysis shall be stopped, the problem corrected, the instrument
recalibrated, the calibration verified, and re-analysis of the preceding
10 analytical samples or all analytical samples analyzed since the last
compliant calibration verification shall be performed. Information
regarding the CCV shall be reported on Form IIA-IN.
12.3 Contract Required Quantitation Limit (CRQL) Check Standard (CRI)
12.3.1 To verify linearity near the CRQL, the Contractor shall analyze a CRI
at the beginning and end of each sample analysis run, but not before
the ICV. In addition, the Contractor shall analyze and report the
results for the CRI at a frequency of not less than once per 20
analytical samples1 per analysis run. The CRI analysis shall be run
immediately followed by the CCV and Continuing Calibration Blank
(CCB) analyses. The CRI shall be prepared by spiking an aliquot of
reagent water with mercury at the CRQL. The CRI shall be taken
through the same process used to digest and analyze the associated
samples.
12.3.2 CRI and percent recovery results shall be reported on Form IIB-IN.
If the percent recovery falls outside the control limits of 70-130%,
the CRI shall be re-analyzed immediately. If the result of the re-
analysis falls within the control limits, no further corrective
action is required. If the result of the re-analysis does not fall
within the control limits, the analysis shall be terminated, the
problem corrected, the instrument recalibrated, or the CRI and ,
associated samples redigested and analyzed.
12.4 Blank Analyses
There are two different types of blanks required by this method. The
calibration blank is used in establishing the analytical curve while the
preparation blank is used to monitor for possible contamination.
12.4.1 Initial and Continuing Calibration Blank (ICB/CCB)
The ICB and CCB are prepared with acids and reagent water and carried
through the entire preparation and analysis procedure. If the
absolute value of the calibration blank (ICB/CCB) result exceeds the
CRQL (see Exhibit C), the analysis shall be terminated, the problem
corrected, the instrument recalibrated, the calibration verified, and
re-analysis of the preceding 10 analytical samples or all analytical
1As defined in Exhibit G, CRI is an analytical sample.
D-19/Mercury
ILM05.2
-------
Exhibit D (Mercury) Section 12
Quality Control (Con't)
samples analyzed since the last compliant calibration blank shall be
performed.
12.4.2 Preparation Blank (PB)
12.4.2.1 The PB shall contain all the reagents and in the same volumes as
used in processing the samples. The PB shall be carried through
the complete procedure and contain the same acid concentration in
the final solution as the sample solution used for analysis.
12.4.2.2 At least one PB, consisting of reagent water processed through
each sample preparation and analysis procedure (see Section 10),
shall be prepared and analyzed with every Sample Delivery Group
(SDG), or with each batch * of samples digested, whichever is more
frequent.
12.4.2.3 The first batch of samples in an SDG is to be assigned to
Preparation Blank one, the second batch to Preparation Blank two,
etc. (see Form III-IN). Each Sample Data Package shall contain
the results of all PB analyses associated with the samples in that
SDG.
12.4.2.4 The PB is to be reported for each SDG and used in all analyses to
ascertain whether sample concentrations reflect contamination in
the following manner:
12.4.2.4.1 If the absolute value of the concentration of the blank is less
than or equal to the CRQL (see Exhibit C), no further action is
required.
12.4.2.4.2 If the analyte concentration in the blank is above the CRQL,
the lowest concentration of the analyte in the associated
samples shall be greater than or equal to 10 times the blank
concentration. Otherwise, all samples associated with that
blank, with the analyte concentration less than 10 times the
blank concentration and above the CRQL, shall be redigested and
re-analyzed with appropriate new Quality Control (QC). The
only exception to this shall be an identified field blank. The
sample concentration is not to be corrected for the blank
value.
12.4.2.4.3 If the concentration of the blank is below the negative CRQL,
then all samples reported below 10 times the CRQL and
associated with the blank shall be redigested and re-analyzed
with appropriate new QC.
12.4.2.4.4 The values for the PB shall be reported on Form III-IN.
12.5 Spike Sample Analysis
12.5.1 The spike sample analysis is designed to provide information about
the effect of the sample matrix on the digestion and/or measurement
methodology. The spike is added before the digestion (i.e., prior to
the addition of other reagents). 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) or for each SDG. 3 The sample
2A group of samples prepared at the same time.
3USEPA may require additional spike sample analyses, upon USEPA Regional
CLP Project Officer (CLP PO) request.
ILM05.2 D-20/Mercury
-------
Exhibit D (Mercury) Section 12
Quality Control (Con't)
and its associated spike sample shall initially be run at the same
dilution.
12.5.2 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 12.6). The average of the duplicate results
cannot be used for the purpose of determining percent recovery.
Samples identified as field blanks and Performance Evaluation (PE)
samples shall not be used for spiked sample analysis. USEPA may
require that a specific sample be used for the spike sample analysis.
12.5.3 The analyte spike shall be added at 1 ug/L (water) or 0.5 mg/kg
(soil). Adjustment shall be made to maintain these spiking levels
when the weight of sample taken deviates by more than 10% of these
values.
12.5.4 If the spike recovery is not at or within the limits of 75-125%, the
data of all samples received and associated with that spike sample
and determined by the same analytical method shall be flagged with
the letter "N" on Forms IA-IN and VA-IN. An exception to this rule
is granted when the sample concentration exceeds the spike added
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.
12.5.5 In the instance where there is more than one spike sample per matrix,
per method, per SDG, and one spike sample recovery is not within
contract criteria, flag all the samples of the same matrix and method
in the SDG. Individual component percent recoveries (%R) are
calculated as follows:
EQ. 4 Spike Percent Recovery
% Recovery = SSR " SR x 100
SA
WHERE, SSR = Spiked Sample Result
SR = Sample Result
SA = Spike Added
12.5.6 When sample concentration is less than the Method Detection Limit
(MDL), use SR = 0 only for purposes of calculating percent recovery.
The Spike Sample Results (SSRs), Sample Results (SRs), Spike Added
(SA), and percent recovery (positive or negative) shall be reported
on Form VA-IN.
12.5.7 The units used for reporting SSRs will be identical to those used for
reporting sample results on Form IA-IN.
12.6 Duplicate Sample Analysis
12.6.1 One duplicate sample shall be analyzed from each group of samples of
a similar matrix type (i.e., water, soil) or for each SDG. 4
Duplicates cannot be averaged for reporting on Form IA-IN. The
4USEPA may require additional duplicate sample analyses, upon USEPA
Regional CLP PO request.
D-21/Mercury ILM05.2
-------
Exhibit D (Mercury) Section 12
Quality Control (Con't)
'sample and its associated duplicate sample shall initially be run at
the same dilution.
12.6.2 Duplicate sample analyses are required for percent solids. Samples
identified as field blanks and PE samples shall not be used for
duplicate sample analysis. USEPA may require that a specific sample
be used for duplicate sample analysis. The Relative Percent
Difference (RPD) is calculated as follows:
EQ. 5 Duplicate Sample Relative Percent Difference
RPD = 'S " DI x 100
(S+D)/2
WHERE, RPD = Relative Percent Difference
S = Sample Result (original)
D = Duplicate Result
1=2.6.3 The results of the duplicate sample analyses shall be reported on
Form VI-IN. A control limit of 20% for RPD shall be used for
original and duplicate sample values greater than or equal to five
times the CRQL (see Exhibit C). A control limit of the CRQL value
shall be entered in the "Control Limit" column on Form VI-IN if
either the sample or duplicate value is less than five times the
CRQL. If the sample and duplicate values are greater than or equal
to five times the CRQL, or if the sample and duplicate values are
less than the CRQL, the "Control Limit" field is left empty.
12.6.4 If one result is above five times the CRQL level and the other is
below, use the CRQL criteria to determine if the duplicate analysis
is in control. If both sample and duplicate values are less than the
MDL, the RPD is not calculated on Form VI-IN. For solid sample or
solid duplicate results less than five times the CRQL, enter the
value of the CRQL, corrected for sample weight and percent solids
(i.e., original, not duplicate 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 IA-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 and method in the SDG. The
percent difference data will be used by USEPA to evaluate the long-
term precision of the method. Specific control limits for each
element will be added to Form VI-IN at a later date based on these
precision results.
12.7 Laboratory Control Sample (LCS) Analysis
12.7.1 A solid LCS (LCSS) shall be analyzed using the same sample
preparations, analytical methods, and Quality Assurance (QA)/QC
procedures employed for the EPA samples received.
12.7.2 The USEPA provided LCSS shall be prepared and analyzed using the
procedures applied to the solid samples received (exception: percent
solids determination not required). If the USEPA LCSS is
unavailable, other USEPA QC Check samples or other certified
materials may be used. In such a case, control limits for the LCSS
must be documented and provided. One LCSS shall be prepared and
ILM05.2 D-22/Mercury
-------
Exhibit D (Mercury) Section 12
Quality Control (Con't)
analyzed for every group of solid samples in a SDG, or for each batch
of samples digested, whichever is more frequent.
12.7.3 All LCSS and percent recovery results will be reported on Form VII-
IN. If the results for the LCSS fall outside the control limits
established by USEPA, the analyses shall be terminated, the problem
corrected, and the samples associated with that LCSS redigested and
re-analyzed with appropriate new QC.
12.8 Method Detection Limit (MDL) Determination
12.8.1 Before any field samples are analyzed under this contract, the MDLs
shall be determined for each digestion procedure and instrument used,
prior to the start of contract analyses, and annually thereafter, and
shall meet the levels specified in Exhibit C.
An MDL study shall be performed after major instrument maintenance,
or changes in instrumentation or instrumental conditions, to verify
the current sensitivity of the analysis.
12.8.2 To determine the MDLs, the Contractor shall run MDL studies following
the procedures given in 40 CFR, Part 136. The Contractor shall
prepare the MDL samples by each digestion procedure used and shall
analyze these samples on each instrument used.
12.8.3 The determined concentration of the MDL shall be less than half the
concentration of the CRQL listed in Exhibit C.
12.8.4 The results of the MDL determination studies shall be forwarded to
the USEPA Regional CLP PO, Sample Management Office (SMO), and
Quality Assurance Technical Support (QATS).
12.8.5 The MDL results shall be reported on Form IX-IN.
D-23/Mercury ILM05.2
-------
Exhibit D (Mercury) Sections 13-17
Method Performance
13.0 METHOD PERFORMANCE
Not applicable.
14.0 POLLUTION PREVENTION
See Section 1.15 in Exhibit D - Introduction to Analytical Methods.
15.0 WASTE MANAGEMENT
See Section 1.16 in Exhibit D - Introduction to Analytical Methods.
16.0 REFERENCES
16.1 US Environmental Protection Agency. Methods for Chemical Analysis of
Water and Wastes. Method 245.1. 1974.
16.2 US Environmental Protection Agency. Methods for Chemical Analysis of
Water and Wastes. Method 245.2. 1974.
16.3 US Environmental Protection Agency. Methods for Chemical Analysis of
Water and Wastes. Method 245.5. 1974.
16.4 US Government Printing Office. 40 Code of Federal Regulations, Part 136,
Section 1, Appendix B.
17.0 TABLES/DIAGRAMS/FLOWCHARTS
Not applicable.
ILM05.2 D-24/Mercury
-------
EXHIBIT D - PART D
ANALYTICAL METHODS
FOR
TOTAL CYANIDE ANALYSIS
D-1/Cyanide ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
ILM05.2 D-2/Cyanide
-------
Exhibit D - Analytical Methods for Total Cyanide Analysis
Table of Contents
Section Page
1.0 SCOPE AND APPLICATION 5
2.0 SUMMARY OF METHOD 5
2.1 Waters and Soils 5
3.0 DEFINITIONS 5
4.0 INTERFERENCES 6
4.1 Sulfides 6
4.2 Surfactants 6
4.3 Oxidizing Agents 6
5.0 SAFETY 6
6.0 EQUIPMENT AND SUPPLIES 7
6.1 Conventional Distillation of Water and Soils 7
6.2 Midi Distillation of Water and Soils 7
7.0 REAGENTS AND STANDARDS 8
7.1 Reagents 8
7.2 Standards 9
8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE 11
8.1 Sample Collection and Preservation 11
8.2 Procedure for Sample Storage 11
8.3 Contract Required Holding Time 11
9.0 CALIBRATION AND STANDARDIZATION 12
9.1 Instrument Operating Parameters 12
9.2 General Procedure 12
9.3 Spectrophotometric Instrument Calibration Procedure 12
9.4 Initial Calibration Verification (ICV) 12
9.5 Continuing Calibration Verification (CCV ) 13
9.6 Initial and Continuing Calibration Blank (ICB/CCB) 13
10.0 PROCEDURE 14
10.1 Sample Preparation 14
10.2 Water and Soil Preparation of Standards and Samples 15
10.3 Sample Analysis 19
11.0 DATA ANALYSIS AND CALCULATIONS 20
11.1 Water/Aqueous Sample Calculation 20
,11.2 Soil Sample Calculatio n 20
11.3 Calculations for Midi Distillation of Waters and Soils .... 21
11.4 Adjusted Method Detection Limit (MDL)/Adjusted Contract
Required Quantitation Limit (CRQL) Calculation 22
12.0 QUALITY CONTROL (QC) 24
12.1 Initial Calibration Verification (ICV) 24
12.2 Continuing Calibration Verification (CCV ) 24
12.3 Contract Required Quantitation Limit (CRQL) Check
Standard (CRI) 24
12.4 Blank Analyses 24
12.5 Spike Sample Analysi s 25
12.6 Duplicate Sample Analysi s 27
12.7 Laboratory Control Sample (LCS) Analysis 28
12.8 Method Detection Limit (MDL) Determination 28
D-3/Cyanide ILM05.2
-------
Exhibit D - Analytical Methods for Total Cyanide Analysis
Table of Contents (Con't)
Section Page
13.0 METHOD PERFORMANCE 29
14.0 POLLUTION PREVENTION 29
15.0 WASTE MANAGEMENT 29
16.0 REFERENCES 29
17.0 TABLES/DIAGRAMS/FLOWCHARTS 29
ILM05.2 D-4/Cyanide
-------
1.0
Exhibit D (Cyanide) Sections 1-3
Scope and Application
SCOPE AND APPLICATION
The analytical method that follows is designed to analyze various water
types, sediment, sludge, and soil samples taken from hazardous waste
sites, for total cyanide.
This analytical method includes the use of acid and heat to remove
cyanide from the sample.
2.0 SUMMARY OF METHOD
2.1 Waters and Soils
2.1.1 The cyanide as hydrocyanic acid (HCN) is released from cyanide
complexes by means of a reflux-distillation and absorbed in a
scrubber containing sodium hydroxide solution. The cyanide ion in
the absorbing solution is then determined colorimetrically.
2.1.2 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-barbituric acid reagent.
The absorbance is read between 570 and 580 nanometers (nm). To
obtain colors of comparable intensity, it is essential to have the
same salt content in both the sample and the standards.
3.0 DEFINITIONS
See Exhibit G for a complete list of definitions.
D-5/Cyanide
ILM05.2
-------
Exhibit D (Cyanide) Sections 4 & 5
Interferences
4.0 INTERFERENCES
Interferences are eliminated or reduced by using the distillation
procedure.
4.1 Sulfides
Sulfides adversely affect the colorimetric procedure. The sample should
be tested in the field for the presence of sulfides as described in
Section 8.1.1.
4.2 Surfactants
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.
4.3 Oxidizing Agents
Oxidizing agents such as chlorine decompose most of the cyanides. The
sample should be tested in the field for the presence of oxidizing
agents as described in Section 8.1.1.
5.0 SAFETY
See Section 1.14 in Exhibit D - Introduction to Analytical Methods.
ILM05.2 D-6/Cyanide
-------
Exhibit D (Cyanide) Section 6
Equipment and Supplies
6.0 EQUIPMENT AND SUPPLIES
Brand names, suppliers, and part numbers are for illustrative purposes
only. No endorsement is implied. Equivalent performance may be
achieved using equipment and supplies other than those specified here,
however, a demonstration of equivalent performance meeting the
requirements of this Statement of Work (SOW) is the responsibility of
the Contractor. The Contractor shall document any use of alternate
equipment or supplies in the Sample Delivery Group (SDG) Narrative.
6.1 Conventional Distillation of Water and Soils
6.1.1 Reflux distillation apparatus. The boiling flask should be of 1
Liter (L) size with an inlet tube and provision for condenser. The
gas absorber may be a Fisher-Milligan scrubber.
6.1.2 Spectrophotometer suitable for measurements between 570 and 580
nanometers (nm) with a 1.0 centimeter (cm) cell or larger (for manual
spectrophotometric method).
6.1.3 Automated analyzer instrumentation (for automated spectrophotometric
method) including:
6.1.3.1 Sampler
6.1.3.2 Pump
6.1.3.3 Cyanide manifold
6.1.3.4 Colorimeter with 15 millimeters (mm) flowcells and 580 nm filters
6.1.3.5 Recorder
6.1.3.6 Data system (optional)
6.1.3.7 Glass or plastic tubes for the sampler
6.2 Midi Distillation of Water and Soils
6.2.1 Midi reflux distillation apparatus
6.2.2 Heating block - Capable of maintaining 125°C (ą5°C).
6.2.3 Auto analyzer system with accessories:
6.2.3.1 Sampler
6.2.3.2 Pump
6.2.3.3 Cyanide cartridge
6.2.3.4 Colorimeter with 50 mm flowcells and 580 nm filter
6.2.3.5 Chart recorder or data system
6.2.4 Assorted volumetric glassware, pipets, and micropipets
D-7/Cyanide ILM05.2
-------
Exhibit D (Cyanide) - Section 7
Reagents and Standards
7.0 REAGENTS AND STANDARDS
7.1 Reagents
7.1.1 Reagent water - The purity of this water must be equivalent to ASTM
Type II water (ASTM D1193-77). Use this preparation for all
reagents, standards, and dilutions of solutions.
7.1.2 Conventional Distillation and Preparation Reagents of Water and Soils
7.1.2.1 Sodium hydroxide solution, 1.25N - Dissolve 50 grams (g) of NaOH
in reagent water, and dilute to 1 Liter (L) with reagent water.
(Same Distillation and Preparation Reagent for Midi Distillation
of Water and Soils.)
7.1.2.2 Cadmium carbonate - Powdered
7.1.2.3 Ascorbic acid - Crystals
7.1.2.4 Sulfuric acid - Concentrated
7.1.2.5 Hydrochloric acid (HC1) - Concentrated (specific gravity 1.19).
7.1.2.6 Magnesium chloride solution - Weigh 510 g of MgCl2 6H20 into a
1000 milliliter (mL) flask, dissolve, and dilute to 1 L with
reagent water. (Same Distillation and Preparation Reagent for
Midi Distillation of Water and Soils.)
7.1.3 Midi Distillation and Preparation Reagents of Water and Soils
7.1.3.1 Sodium hydroxide absorbing solution and sample wash solution,
0.25N - Dissolve 10.0 g NaOH in reagent water and dilute to 1 L.
7.1.3.2 Sulfuric acid, 50% (v/v) - Carefully add a portion of concentrated
H2S04 to an equal portion of reagent water.
7.1.4 Manual Spectrophotometric Reagents for Water and Soils
7.1.4.1 Acetate Buffer - Dissolve 410 g of NaC 2H302 3H20 in 500 mL of
reagent water. Add sufficient glacial acetic acid to adjust pH to
4.5 (approximately 500 mL).
7.1.4.2 Chloramine-T solution - Dissolve 1.0 g of white, water soluble
chloramine-T in 100 mL of reagent water and refrigerate until
ready to use. Prepare fresh weekly.
7.1.4.3 Color Reagent
7.1.4.3.1 Pyridine-barbituric acid reagent - Place 15 g of barbituric
acid in a 250 mL volumetric flask and add just enough reagent
water to wash the sides of the flask and wet the barbituric
acid. Add 75 mL of pyridine and mix. Add 15 mL of HC1
(specific gravity 1.19), mix, and cool to room temperature.
Dilute to 250 mL with reagent water and mix. This reagent is
stable for approximately six months if stored in a cool, dark
place.
7.1.5 Semi-Automated Spectrophotometric Reagents for Conventional and Midi
Distillation of Water and Soils
7.1.5.1 Chloramine-T solution - Dissolve 0.40 g of chloramine-T in reagent
water and dilute to 100 mL. Prepare fresh daily.
ILM05.2 D-8/Cyanide
-------
Exhibit D (Cyanide) - Section 7
Reagents and Standards (Con't)
7.1.5.2 Acetate Buffer - Dissolve 410 g of NaC 2H3O2 3H20 in 500 mL of
reagent water. Add sufficient glacial acetic acid to adjust pH to
4.5 (approximately 500 mL).
7.1.5.3 Pyridine-barbituric acid solution - Transfer 15 g of barbituric
acid into a 1 liter volumetric flask. Add about 100 mL of reagent
water and swirl the flask. Add 75 mL of pyridine and mix. Add 15
mL of concentrated HC1 and mix. Dilute to about 900 mL with
reagent water and mix until the barbituric acid is dissolved.
Dilute to 1 L with reagent water. Store at 4°C (ą2°C).
7.1.5.4 Sampler wash - Dissolve 10 g of NaOH in reagent water and dilute
to 1 L. (For conventional distillation of water and soils only.)
7.2 Standards
7.2.1 Introduction
The Contractor must provide all standards to be used with this
contract. These standards may be used only after they have been
certified according to the procedure in Exhibit E, Section 8.0. The
Contractor must be able to verify that the standards are certified.
Manufacturer's certificates of analysis must be retained by the
Contractor and presented upon request.
7.2.2 Stock Standard Solutions
7.2.2.1 Stock Standard Reagents for Water and Soils
7.2.2.1.1 Stock cyanide solution - Dissolve 2.51 g of KCN and 2 g KOH in
1 L of reagent water. Standardize with 0.0192N AgN03.
7.2.2.1.2 Standard cyanide solution, intermediate - Dilute 50.0 mL of
stock (1 mL = 1 milligram (mg) CN) to 1000 mL with reagent
water.
7.2.2.1.3 Standard cyanide solution - Prepare fresh daily by diluting 100
mL of intermediate cyanide solution to 1000 mL with reagent
water and store in a glass stoppered bottle. 1 mL = 5.0
micrograms (pg) CN [5.0 milligrams per Liter (mg/L)].
7.2.2.1.4 Sodium hydroxide solution, 0.25N - Dissolve 10 g of NaOH in
reagent water and dilute to 1 L.
7.2.2.2 Stock Standard Reagents for Midi Distillation of Water and Soils
7.2.2.2.1 Stock cyanide solution, 1000 mg/L CN - Dissolve 2.51 g of KCN
and 2.0 g KOH in reagent water and dilute 1 L. Standardize
with 0.0192N AgN03.
7.2.2.2.2 Intermediate cyanide standard solution, 10 mg/L CN - Dilute 1.0
mL of stock cyanide solution (see Section 7.2.2.2.1) plus 20 mL
of 1.25N NaOH solution (see Section 7.1.2.1) to 100 mL with
reagent water. Prepare this solution at time of analysis.
7.2.2.2.3 Sodium hydroxide solution, 0.IN - Dissolve 4 g of NaOH in
reagent water and dilute to 1 L.
D-9/Cyanide ILM05.2
-------
Exhibit D (Cyanide) - Section 7
Reagents and Standards (Con't)
7.2.3 Secondary Dilution Standards
7.2.3.1 Secondary Dilution Standards
Prepare secondary dilution standard solutions by diluting the
appropriate volumes of stock standards with 0.25N NaOH. The final
concentration of NaOH'in all standards should be 0.25N.
7.2.4 Working Standards
7.2.4.1 Method Detection Limit (MDL) Solution
7.2.4.1.1 The MDL solution shall be at a concentration of 3 to 5 times
the expected MDL.
7.2.4.2 Contract Required Quantitation Limit (CRQL) Check Standard (CRI)
7.2.4.2.1 The concentration of the CRI for cyanide shall be at the CRQL.
Information regarding the CRI shall be reported on Form IIB-IN.
ILM05.2 D-10/Cyanide
-------
Exhibit D (Cyanide) Section 8
Sample Collection, Preservation, and Storage
8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE
8.1 Sample Collection and Preservation
8.1.1 Water Sample Preservation
Collection of total cyanide must be in polyethylene or glass
containers. The sample must be tested for sulfides and oxidizing
agents, and preserved by the sampler immediately upon sample
collection. Place a drop of the sample on lead acetate test paper
(which has been pre-moistened with pH 4 acetate buffer solution) to
detect the presence of sulfides. If sulfides are present (test strip
turns black), the sample volume required for the cyanide
determination should be increased by 25 milliliters (mL). The total
volume of sample should then be treated with powdered cadmium
carbonate or lead 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. If no sulfides are present,
test for the presence of oxidizing agents by placing a drop of the
sample on a strip of potassium iodide - starch test paper (KI -
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
gram (g) of ascorbic acid for each liter of sample volume. Preserve
the sample with NaOH to pH greater than 12 and maintain at 4°C (ą2°C)
until distillation,
8.1.2 Soil/Sediment Sample Preservation
Samples shall be kept at 4°C (ą2°C) from the time of collection until
distillation.
8.2 Procedure for Sample Storage
8.2.1 The samples must be protected from light and refrigerated at 4°C
(ą2°C) from the time of receipt until 60 days after delivery of a
complete, reconciled data package to the USEPA. After 60 days the
samples may be disposed of in a manner that complies with all
applicable regulations.
8.2.2 The samples must be stored in an atmosphere demonstrated to be free
of all potential contaminants.
8.2.3 Samples, sample distillates, and standards must be stored separately.
8.3 Contract Required Holding Time
The maximum sample holding time for cyanide is 12 days from Validated
Time of Sample Receipt (VTSR).
D-11/Cyanide ILM05.2
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Exhibit D (Cyanide) Section 9
Calibration and Standardization
9.0 CALIBRATION AND STANDARDIZATION
9.1 Instrument Operating Parameters
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 (QC) data confirming instrument performance and
analytical results.
9.2 General Procedure
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 reagent water through the sample line and appropriate
reagents (see Section 7.1.5) through reagent lines. Adjust the baseline
using the appropriate control on the colorimeter. Prepare a standard
curve by plotting absorbance of standard vs. cyanide concentrations [per
250 milliliter (mL)].
9.3 Spectrophotometric Instrument Calibration Procedure
9.3.1 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.
9.3.2 The date and time of preparation and analysis shall be given in the
raw data.
9.3.3 Calibration standards shall be prepared fresh daily or each time an
analysis is to be made and discarded after use. Prepare a blank and
at least three calibration standards in graduated amounts in the
appropriate range. One of the calibration standards shall be at the
Contract Required Quantitation Limit (CRQL). The acceptance criteria
for the initial calibration curve is a correlation coefficient
greater than or equal to 0.995.
9.3.4 Any changes or corrections to the analytical system shall be followed
by recalibration.
9.4 Initial Calibration Verification (ICV)
9.4.1 Immediately after each cyanide system has been calibrated, the
accuracy of the initial calibration shall be verified and documented
for cyanide by the analysis of the ICV Solution at the wavelength
used for analysis.
9.4.2 Only if the ICV Solution is not available from USEPA, or where a
certified solution of the 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.
ILM05.2 D-12/Cyanide
-------
Exhibit D (Cyanide) Section 9
Calibration and Standardization (Con't)
9.4.3 The ICV 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.
9.4.4 The value for the ICV shall be reported on Form IIA-IN.
9.5 Continuing Calibration Verification (CCV)
9.5.1 To ensure calibration accuracy during each analysis run, one of the
following standards is to be used for the CCV and shall be analyzed
and reported 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 at the beginning of the run and after the last
analytical sample. The analyte concentration in the CCV standard
shall be different than the concentration used for the ICV and shall
be one of the following solutions at or near the mid-range level of
the calibration curve:
=*= USEPA Solutions
:i: NIST Standards
= A Contractor-prepared standard solution
The same CCV standard shall be used throughout the analysis runs for
a Sample Delivery Group (SDG) of samples received.
9.5.2 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.
9.5.3 Information regarding the CCV shall be reported on Form IIA-IN.
9.6 Initial and Continuing Calibration Blank (ICB/CCB)
A calibration blank shall be analyzed at the wavelength used for
analysis immediately after every ICV and CCV, at a frequency of 10% or
every 2 hours 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 analyzed immediately after the last CCV, and the
last CCV shall be analyzed immediately after the last analytical sample
of the run. The results for the calibration blanks shall be reported on
Form III-IN.
D-13/Cyanide ILM05.2
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Exhibit D (Cyanide) Section 10
Procedure
10.0 PROCEDURE
10.1 Sample Preparation
10.1.1 If insufficient sample amount (less than 90%, of the required amount)
is received to perform the analyses, the Contractor shall contact
Sample Management Office (SMO) to inform them of the problem. SMO
will contact the Region for instructions. The Region will either
require that no sample analyses be performed or will require that a
reduced volume be used for the sample analysis. No other changes in
the analyses will be permitted. The Contractor shall document the
Region's decision in the Sample Delivery Group (SDG) Narrative.
10.1.2 If multiphase samples (e.g., two-phase liquid sample, oily
sludge/sandy soil sample) are received by the Contractor, the
Contractor shall contact SMO to apprise them of the type of sample
received. SMO will contact the Region. If all phases of the sample
are amenable to analysis, the Region may require the Contractor to do
any of the following:
:i: Mix the sample and analyze an aliquot from the homogenized
sample.
=*= Separate the phases of the sample, and analyze one or more of
the phases separately. SMO will provide EPA sample numbers for
the additional phases, if required.
1X3 Do not analyze the sample.
10.1.2.1 If all of the phases are not amenable to analysis (i.e., outside
scope), the Region may require the Contractor to do any of the
following:
^ Separate the phases and analyze the phase(s) that is (are)
amenable to analysis. SMO will provide EPA sample numbers
for the additional phases, if required.
:*: Do not analyze the sample.
10.1.2.2 No other changes in the analyses will be permitted. The
Contractor shall document the Region's decision in the SDG
Narrative.
10.1.3 Soil samples are not dried prior to analysis. A separate percent
solids determination must be made in accordance with the procedure in
Exhibit D - Introduction to Analytical Methods, Section 1.6.
10.1.4 Before preparation is initiated for an aqueous sample, the Contractor
shall test for the presence of sulfides and oxidizing agents (e.g.,
residual chlorine). The test for sulfides shall be performed by
placing a drop of the sample on a strip of lead acetate paper (which
has been pre-moistened with pH 4 acetate buffer solution). If the
test strip turns black, the Contractor shall treat the total volume
of sample with powdered cadmium carbonate or lead carbonate. Yellow
cadmium sulfide precipitates when the sample contains sulfide. This
operation shall be repeated until a drop of the treated sample
solution does not darken the lead acetate test paper. The solution
shall be filtered through a dry filter paper into a dry beaker, and
the volume of sample to be used for analysis shall be measured from
the filtrate. It is recommended that the Contractor 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
ILM05.2 D-14/Cyanide
-------
Exhibit D (Cyanide) Section 10
Procedure (Con't)
precipitated material. The test for oxidizing agents shall be
performed by placing a drop of the sample on a strip of potassium
iodide - starch test paper (KI - starch paper). If the test strip
turns blue, the Contractor shall contact SMO for further instructions
from the Region before proceeding with sample preparation and
analysis. The Contractor shall document the presence of sulfides or
oxidizing agents in the SDG Narrative.
10.2 Water and Soil Preparation of Standards and Samples
10.2.1 Standards Preparation
10.2.1.1 It is not imperative that all standards be distilled in the same
manner as the samples. At least one standard (mid-range) must be
distilled and compared to similar values on the curve to ensure
that the distillation technique is reliable. If the distilled
standard does not agree within ą15% of the undistilled standards,
the operator shall find and correct the cause of the apparent
error before proceeding.
10.2.1.2 Standards for Manual Spectrophotometric Analysis of Water and Soil
Samples
Prepare a minimum of three standards and a blank by pipetting
suitable volumes of standard solution into 250 milliliter (mL)
volumetric flasks.
NOTE: The concentration of one of the calibration standards shall
be at the Contract Required Quantitation Limit (CRQL).
To each standard, add 50 mL of 1.25N NaOH and dilute to 250 mL
with reagent 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.
10.2.1.3 Standards for Semi-Automated Spectrophotometric Analysis of Water
and Soil Samples
Calibration standards - Prepare a blank and at least three
calibration standards over the range of the analysis by pipetting
suitable volumes of standard solution into volumetric flasks. One
calibration standard must be at the CRQL. Add NaOH to each
standard to bring the concentration of NaOH to 10 grams per Liter
(g/L). Store at 4°C (ą2°C).
10.2.1.4 Standards for Midi Distillation Preparation and Semi-Automated
Spectrophotometric Analysis of Water and Soil Samples
Prepare a minimum of three standards and a blank by pipetting
suitable volumes of standard solution into 50 mL volumetric
flasks. Dilute standards to 50 mL with 0.25N NaOH.
NOTE: One calibration standard must be at the CRQL.
10.2.2 Water Samples Preparation (Distillation)
10.2.2.1 Preparation Method/Code (DW1)
10.2.2.1.1 Place 500 mL of sample in the 1 liter boiling flask. Add 50 mL
of NaOH solution (see Section 7.1.2.1) to the absorbing tube
D-15/Cyanide ILM05.2
-------
Exhibit D (Cyanide) Section 10
Procedure (Con't)
and dilute if necessary with reagent water to obtain an
adequate depth of liquid in the absorber. Connect the boiling
flask, condenser, absorber and trap in the train.
10.2.2.1.2 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 re-adjust the air rate
occasionally to prevent the solution in the boiling flask from
backing up into the air inlet tube.
10.2.2.1.3 Slowly add 25 mL concentrated sulfuric acid (H2 S04) (see
Section 7.1.2.4) through the air inlet tube. Rinse the tube
with reagent water and allow the airflow to mix the flask
contents for three minutes. Pour 20 mL of magnesium chloride
solution (see Section 7.1.2.6) into the air inlet and wash down
with a stream of water.
10.2.2.1.4 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.
10.2.2.1.5 Drain the solution from the absorber into a 250 mL volumetric
flask and bring up to volume with reagent water washings from
the absorber tube.
NOTE: The distillation procedure results in a two-fold
concentration of the sample.
10.2.3 Water Samples Preparation (Midi-Distillation)
10.2.3.1 Preparation Method/Code (DW2)
10.2.3.1.1 The procedure described here utilizes a midi distillation
apparatus and requires a sample aliquot of 50 mL or less for
aqueous samples.
10.2.3.1.2 Pipet 50 mL of sample, or an aliquot diluted to 50 mL, into the
distillation flask along with 2 or 3 boiling chips.
10.2.3.1.3 Add 50 mL of 0.25N NaOH (see Section 7.1.3.1) to the gas
absorbing impinger.
10.2.3.1.4 Connect the boiling flask, condenser, and absorber in the
train. The excess cyanide trap contains 0.5N NaOH.
10.2.3.1.5 Turn on the vacuum and adjust the gang (Whitney) valves to give
a flow of three bubbles per second from the impingers in each
reaction vessel.
10.2.3.1.6 After five minutes of vacuum flow, inject 5 mL of 50% (v/v)
H2S04 (see Section 7.1.3.2) through the top air inlet tube of
the distillation head into the reaction vessel. Allow to mix
for 5 minutes.
ILM05.2 D-16/Cyanide
-------
Exhibit D (Cyanide) Section 10
Procedure (Con't)
NOTE: The acid volume must be sufficient to bring the
sample/solution pH to below 2.0.
10.2.3.1.7 Add 2 mL of magnesium chloride solution (see Section 7.1.2.6)
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 either another 2
mL of magnesium chloride solution or a few drops of a
commercially available anti-foam agent. The Contractor shall
document the addition of magnesium chloride solution or anti-
foam agent in the SDG Narrative.
10.2.3.1.8 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.
10.2.3.1.9 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.
10.2.3.1.10 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
8.3.
10.2.4 Soil Samples Preparation
10.2.4.1 Preparation Method/Code (DS1) (Distillation)
10.2.4.1.1 Accurately weigh a representative 1-5 gram (g) portion of wet
sample and transfer it to a boiling flask. Add 500 mL of
reagent water'. Shake or stir the sample so that it is
dispersed.
10.2.4.1.2 Add 50 mL of NaOH solution (see Section 7.1.2.1) to the
absorbing tube and dilute if necessary with re'agent water to
obtain an adequate depth of liquid in the absorber. Connect
the boiling flask, condenser, absorber, and trap in the train.
10.2.4.1.3 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 re-adjust the air rate
occasionally to prevent the solution in the boiling flask from
backing up into the air inlet tube.
10.2.4.1.4 Slowly add 25 mL of concentrated H 2SO4 (see Section 7.1.2.4)
through the air inlet tube. Rinse the tube with reagent water
and allow the airflow to mix the flask contents for 3 minutes.
Pour 20 mL of magnesium chloride solution (see Section 7.1.2.6)
into the air inlet and wash down with a stream of water.
10.2.4.1.5 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-17/Cyanide ILM05.2
-------
Exhibit D (Cyanide) Section 10
Procedure (Con't)
10.2.4.1.6 Drain the solution from the absorber into a 250 mL.volumetric
flask and bring up ,to volume with reagent water washings from
the absorber tube.
10.2.4.2 Preparation Method/Code (DS2) (Midi-Distillation)
10.2.4.2.1 The procedure described here utilizes a midi distillation
apparatus and requires a sample aliquot of 1 gram for solid
materials.
10.2.4.2.2 Weigh 1.0 g of sample (to the nearest 0.01 g) into the
distillation flask and dilute to 50 mL with reagent water. Add
2 or 3 boiling chips.
10.2.4.2.3 Add 50 mL of 0.25N NaOH (see Section 7.1.3.1) to the gas
absorbing impinger.
10.2.4.2.4 Connect the boiling flask, condenser, and absorber in the
train. The excess cyanide trap contains 0.5N NaOH.
10.2.4.2.5 Turn on the vacuum and adjust the gang (Whitney) valves to give
a flow of three bubbles per second from the impingers in each
reaction vessel.
10.2.4.2.6 After five minutes of vacuum flow, inject 5 mL of 50% (v/v)
H2SO4 (see Section 7.1.3.2) 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.
10.2.4.2.7 Add 2 mL of magnesium chloride solution (see Section 7.1.2.6)
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 either another 2
mL of magnesium chloride solution or a few drops of a
commercially available anti-foam agent. The Contractor shall
document the addition of magnesium chloride solution or anti-
foam agent in the SDG Narrative.
10.2.4.2.8 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.
10.2.4.2.9 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.
10.2.4.2.10 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 8.3.
10.2.5 Non-Distilled Analyses
10.2.5.1 Preparation Method/Code (NP1)
10.2.5.1.1 This code shall be used to report samples that are not
distilled prior to analysis.
ILM05'.2 D-18/Cyanide
-------
Exhibit D (Cyanide) Section 10
Procedure (Con't)
10.2.5.1.2 This Preparation Method/Code shall also be used to report the
non-distilled Method Detection Limit (MDL). The concentration
of this MDL shall be used to determine the appropriate
concentration qualifier for the results of instrument QC
analyses [except the distilled Initial Calibration Verification
(ICV)].
10.3 Sample Analysis
10.3.1 Manual Spectrophotometric Determination
10.3.1.1 Allow all standards and samples to come to ambient room
temperature prior to analysis. 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 0.25N sodium
hydroxide solution (see Section 7.1.3.1). Add 1.0 mL of acetate
buffer (see Section 7.1.4.1) and mix. The dilution factor must be
reported on Form XIII-IN.
10.3.1.2 Add 2 mL of chloramine-T (see Section 7.1.4.2) and mix. After 1
to 2 minutes, add 5 mL of pyridine-barbituric acid solution (see
Section 7.1.4.3.1) and mix. Dilute to mark with reagent water and
mix again. Allow 8 minutes for color development then read
absorbance between 570 and 580 nanometers (nm) in a 1 centimeter
(cm) cell within 15 minutes.
10.3.2 Semi-Automated Spectrophotometric Determination of Distillates
10.3.2.1 Set up the manifold. Pump the reagents through the system until a
steady baseline is obtained.
10.3.2.2 Place calibration standards, blanks, and control standards in the
sampler tray, followed by distilled samples, distilled duplicates,
distilled standards, distilled spikes, and distilled blanks.
Allow all standards and samples to come to ambient room
temperature prior to analysis.
10.3.2.3 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
colorimeter until the desired signal is obtained. Establish the
baseline and proceed to analyze calibration standards, blanks,
control standards, distilled samples, and distilled Quality
Control (QC) samples.
D-19/Cyanide ILM05.2
-------
Exhibit D (Cyanide) Section 11
Data Analysis and Calculations
11.0 DATA ANALYSIS AND CALCULATIONS
11.1 Water/Aqueous Sample Calculation
11.1.1 For semi-automated colorimetric determination (Non-Midi-
Distillation) , measure the instrument response of the calibration
standards and calculate a linear regression equation. Apply the
equation to the samples and Quality Control (QC) samples 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 milliliter (mL) and
the distillate volume was 250 mL). Also correct for, and report on
Form XIII-IN, any dilutions which were made before or after
distillation.
11.1.2 For manual colorimetric determination, calculate the cyanide, in
micrograms per Liter (ug/L), in the original sample as follows:
EQ. 1 Aqueous Sample Concentration (Manual)
^ _. /T. A x 1000 mL/L 50 mL
CN Concentration (ug/L) = x
B C
WHERE,
A = pg CN read from standard curve (per 250 mL)
B = mL of original sample for distillation (see Section
10.2.2.1.1)
C = mL taken for colorimetric analysis (see Section
10.3.1.1)
50 mL = volume of original sample aliquot (see Section
10.3.1.1)
1000 mL/L = conversion mL to L
The minimum value that can be substituted for A is the Method
Detection Limit (MDL) value adjusted for volume.
11.2 Soil Sample Calculation
11.2.1 A separate determination of percent solids must be performed (see
Exhibit D - Introduction to Analytical Methods, Section 1.6).
11.2.2 The concentration of cyanide in the sample is determined as follows:
11.2.2.1 Manual Spectrophotometric
EQ. 2 Soil Sample Concentration (Manual)
CN Concentration (mg/kg) =
50 mL
A x
% solids
100
ILM05.2 D-20/Cyanide
-------
WHERE,
A
B
50 mL
% solids =
Exhibit D (Cyanide) Section 11
Data Analysis and Calculations (Can't)
pg CN read from standard curve (per 250 mL).
mL of distillate taken for colorimetric
determination (see Section 10.3.1.1).
wet weight of original sample in g (see Section
10.2.4.1.1).
standard volume taken for colorimetric
determination (see Section 10.3.1.1)
percent solids (see Exhibit D - Introduction to
Analytical Methods, Section 1.6).
11.2.2.2 Semi-Automated Spectrophotometric for Non-Midi-Distillates
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.
EQ. 3 Soil Sample Concentration (Semi-automated)
A x .25
CN Concentration (mg/kg)
C x
% solids
100
WHERE,
A
C
.25
% solids
pg/L determined from standard curve.
wet weight of original sample in g (see Section
10.2.4.1.1) .
conversion factor for distillate final volume
(see Section 10.2.4.1.6).
percent solids (see Exhibit D - Introduction to
Analytical Methods, Section 1.6).
The minimum value that can be substituted for A is the MDL value.
11.3 Calculations for Midi Distillation of Waters and Soils
11.3.1 Calculations for Semi-automated Colorimetric Determination
11.3.1.1 Prepare a standard curve by plotting absorbance (peak heights,
determined visually or using a data system) of standards (y)
versus cyanide concentration values (total pg CN/L) (x). Perform
a linear regression analysis.
11.3.1.2 Multiply all distilled values by the standardization value to
correct for the stock cyanide solution not being exactly 1000
milligrams per Liter (mg/L) (see Section 7.2.2.2.1).
11.3.1.3 Using the regression analysis equation, calculate sample receiving
solution concentrations from the calibration curve.
11.3.1.4 Calculate the cyanide of aqueous samples in pg/L of original
sample, as follows:
D-21/Cyanide
ILM05.2
-------
Exhibit D (Cyanide) Section 11
Data Analysis and Calculations (Con't)
EQ. 4 Aqueous Sample Concentration (Midi)
A x D x F
CN Concentration (pg/L) =
B
WHERE,
A = ug/L CN of sample from regression analysis
B = volume of original sample for distillation (0.050 L)
(see Section 10.2.3.1.2)
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 the MDL value.
11.3.1.5 Calculate the cyanide of solid samples in mg/kg of original
sample, as follows:
11.3.1.5.1 A separate determination of percent solids must be performed
(see Exhibit D - Introduction to Analytical Methods, Section
1.6).
11.3.1.5.2 The concentration of cyanide in the sample is determined as
follows:
EQ. 5 Soil Sample Concentration (Midi)
A x D x F
CN Concentration (mg/kg) =
B x E
WHERE,
A = pg/L CN of sample from regression analysis curve
B = wet weight of original sample (see Section
10.2.4.2.2)
D = any dilution factor necessary to bracket sample
value within standard values
E % solids/100 (see Exhibit D - Introduction to
Analytical Methods, Section 1.6)
F = sample receiving solution volume (0.050 L)
The minimum value that can be substituted for A is the MDL
value.
11.4 Adjusted Method Detection Limit (MDL)/Adjusted Contract Required
Quantitation Limit (CRQL) Calculation
To calculate the adjusted aqueous MDL or adjusted aqueous CRQL for the
manual colorimetric method, multiply the MDL (pg/L) or CRQL (pg/L) by
0.25 and substitute the result for the "A" term in Equation 1. To
calculate the adjusted aqueous MDL or adjusted aqueous CRQL for all
other methods, follow the instructions in Section 11.1.1 or substitute
ILM05.2 D-22/Cyanide
-------
Exhibit D (Cyanide) Section 11
Data Analysis and Calculations (Con't)
the MDL (pg/L) or CRQL (pg/L) for the "A" term in Equation 4, as
appropriate.
The adjusted soil MDL or adjusted soil CRQL for all methods shall be
calculated as follows:
EQ. 6 Adjusted Soil MDL/Adjusted Soil CRQL Concentration
W 1
Adjusted Concentration (mg/kg) = C x x
WR S
WHERE, C = MDL or CRQL concentration (mg/kg)
WM = minimum method required wet sample weight (g)
WR = reported wet sample weight (g)
S = % Solids/100 (see Exhibit D - Introduction to
Analytical Methods, Section 1.6).
For the midi-distillation, multiply the adjusted concentration value
(mg/kg) obtained in Equation 6 by any applicable dilution factor.
D-23/Cyanide ILM05.2
-------
Exhibit D (Cyanide) Section 12
Quality Control
12.0 QUALITY CONTROL (QC)
12.1 Initial Calibration Verification (ICV)
The ICV standard shall be prepared in the same matrix as the calibration
standards and in accordance with the instructions provided by the
supplier. The ICV standard shall be distilled. If measurements exceed
the control limits of 85% (low) and 115% (high), the analysis shall be
terminated, the problem corrected, the instrument recalibrated, and the
calibration reverified. Information regarding the ICV shall be reported
on Form IIA-IN.
12.2 Continuing Calibration Verification (CCV)
The CCV standard shall be prepared by the analyst at a concentration
equivalent to the mid-point of the calibration curve. If the deviation
of the CCV is greater than the control limits of 85% (low) and 115%
(high), the analysis shall be stopped, the problem corrected, the
instrument recalibrated, the calibration verified, and re-analysis of
the preceding 10 analytical samples or all analytical samples analyzed
since the last compliant calibration verification shall be performed.
Information regarding the CCV shall be reported on Form IIA-IN.
12.3 Contract Required Quantitation Limit (CRQL) Check Standard (CRI)
12.3.1 To verify linearity near the CRQL, a standard at the CRQL (CRI) shall
be prepared, in the same matrix as the calibration standards, and
analyzed at the beginning and at the end of each sample analysis run,
but not before the ICV. In addition, the Contractor shall analyze
the CRI at a frequency of not less than once per 20 analytical
samples1 per analysis run. The CRI analysis shall be run immediately
followed by the CCV and Continuing Calibration Blank (CCB) analyses.
The CRI shall be prepared by spiking an aliquot of reagent water with
cyanide to yield a concentration in the final solution equal to the
CRQL.
12.3.2 CRI and percent recovery results shall be reported on Form IIB-IN.
If the percent recovery falls outside the control limits of 70-130%,
the CRI shall be re-analyzed immediately. If the result of the re-
analysis falls within the control limits, no further corrective
action is required. If the result of the re-analysis does not fall
within the control limits, the analysis shall be terminated, the
problem corrected, the instrument recalibrated, the CRI analyzed, and
the samples associated with the CRI re-analyzed.
12.4 Blank Analyses
There are two different types of blanks required by this method. The
calibration blank is used in establishing the analytical curve while the
preparation blank is used to monitor for possible contamination.
12.4.1 Initial and Continuing Calibration Blank (ICB/CCB)
The ICB and CCB are prepared with reagents and reagent water. If the
absolute value of the calibration blank (ICB/CCB) result exceeds the
CRQL (see Exhibit C), the analysis shall be terminated, the problem
corrected, the instrument recalibrated, the calibration verified, and
re-analysis of the preceding 10 analytical samples or all analytical
'As defined in Exhibit G, CRI is an analytical sample.
ILM05.2 D-24/Cyanide
-------
Exhibit D (Cyanide) Section 12
Quality Control (Con't)
samples analyzed since the last compliant calibration blank shall be
performed.
12.4.2 Preparation Blank (PB)
12.4.2.1 The PB shall contain all the reagents and in the same volumes as
used in processing the samples. The PB shall be carried through
the complete procedure and contain the same concentration in the
final solution as the sample solution used for analysis.
12.4.2.2 At least one PB, consisting of reagent water processed through
each sample preparation and analysis procedure (see Section 10),
shall be prepared and analyzed with every Sample Delivery Group
(SDG), or with each batch 2 of samples distilled, whichever is more
frequent.
12.4.2.3 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 Sample Data Package shall
contain the results of all the PB analyses associated with the
samples in that SDG.
12.4.2.4 The PB is to be reported for each SDG and used in all analyses to
ascertain whether sample concentrations reflect contamination in
the following manner:
12.4.2.4.1 If the absolute value of the concentration of the blank is less
than or equal to the CRQL (see Exhibit C), no further action is
required.
12.4.2.4.2 If the analyte concentration in the blank is above the CRQL,
the lowest concentration of the analyte in the associated
samples shall be greater than or equal to 10 times the blank
concentration. Otherwise, all samples associated with the
blank, with the analyte concentration less than 10 times the
blank concentration and above the CRQL, shall be redistilled
and re-analyzed with appropriate new QC. The only exception to
this shall be an identified field blank. The sample
concentration is not to be corrected for the blank value.
12.4.2.4.3 If the concentration of the blank is below the negative CRQL,
then all samples associated with the blank and reported below
10 times CRQL shall be reprepared and re-analyzed with
appropriate new QC.
The values for the preparation blank shall be reported on Form
III-IN.
12.5 Spike Sample Analysis
12.5.1 The spike sample analysis is designed to provide information about
the effect of the sample matrix on the distillation and/or
measurement methodology. The spike is added prior to any
distillation steps. At least one spike sample analysis (matrix
spike) shall be performed on each group of samples of a similar
2A group of samples prepared at the same time.
, D-25/Cyanide ILM05.2
-------
Exhibit D (Cyanide) Section 12
Quality Control (Con't)
matrix type (i.e., water, soil) or for each SDG. 3 The sample and its
associated spike sample shall initially be run at the same dilution.
12.5.2 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 12.6). The average of the duplicate results
cannot be used for the purpose of determining percent recovery.
Samples identified as field blanks and Performance Evaluation (PE)
samples shall not be used for spiked sample analysis. USEPA may
require that a specific sample be used for the spike sample analysis.
12.5.3 The analyte spiking solution shall be added to yield a final
concentration of 100 pg/L 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
milliliter (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).
12.5.3.1 For soil samples, the final sample solution prepared for analysis
(i.e., the distillate) shall contain cyanide spiked at a
concentration of 100 ug/L regardless of the distillation procedure
employed, or the amount of sample used for distillation. The
final sample volume after distillation shall be used as the basis
for the amount of cyanide to add as the spike. The units for
reporting soil sample cyanide results shall be mg/kg. To convert
from pg/L to mg/kg, the equation below shall be used:
-1
EQ. 7 Conversion to mg/kg
final distillate volume (L)
mg/kg = ug/L x
sample weight (g)
12.5.4 If the spike recovery is not at or within the limits of 75-125%, the
data of all samples received and associated with that spike sample
and determined by the same analytical method shall be flagged with
the letter "N" on Forms IA-IN and VA-IN. An exception to this rule
is granted when the sample concentration exceeds the spike added
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.
12.5.5 When the matrix spike recovery falls outside the control limits and
the sample result does not exceed 4 times the spike added, a post-
distillation spike shall be performed. Note that if a post-
distillation spike analysis is required, the same USEPA sample that
was used for the matrix spike analysis shall be used for the post
digestion spike analysis. Spike the unspiked aliquot of the sample
at 2 times the indigenous level or 2 times CRQL, whichever is
greater. Results of the post-distillation spike shall be reported on
Form VB-IN.
3USEPA may require additional spike sample analyses, upon USEPA Regional
CLP Project Officer (CLP PO) request.
ILM05.2 D-26/Cyanide
-------
Exhibit D (Cyanide) Section 12
Quality Control (Con't)
12.5.6 In the instance where there is more than one spike sample per matrix,
per method, per SDG, if one spike sample recovery is not within
contract criteria, flag all the samples of the same matrix and method
in the SDG. Individual component percent recoveries are calculated
as follows:
EQ. 8 Spike Percent Recovery
% Recovery = SSR " SR x 100
SA
WHERE,
1
SSR = Spiked Sample Result
SR = Sample Result
SA = Spike Added
12.5.7 When the sample concentration is less than the Method Detection Limit
(MDL), use SR = 0 only for purposes of calculating percent recovery.
The Spike Sample Results (SSRs), Sample Results (SRs), Spike Added
(SA), and percent recovery (positive or negative) shall be reported
on Form VA-IN.
12.5.8 The units used for reporting spike sample results will be identical
to those used for reporting sample results on Form IA-IN.
12.6 Duplicate Sample Analysis
12.6.1 One duplicate sample shall be analyzed from each group of samples of
a similar matrix type (i.e., water, soil) or for each SDG. 4
Duplicates cannot be averaged for reporting on Form IA-IN. The
sample and its associated duplicate sample shall initially be run at
the same dilution.
12.6.2 Duplicate sample analyses are required for percent solids. Samples
identified as field blanks and PE samples shall not be used for
duplicate sample analysis. USEPA may require that a specific sample
be used for duplicate sample analysis. The Relative Percent
Difference (RPD) is calculated as follows:
EQ. 9 Duplicate Sample Relative Percent Difference
RPD = I S " D I x 100
(S+D)/2
WHERE,
RPD = Relative Percent Difference
S = Sample Result (original)
D = Duplicate Result
12.6.3 The results of the duplicate sample analyses shall be reported on
Form VI-IN. A control limit of 20% for RPD shall be used for
4USEPA may require additional duplicate sample analyses, upon USEPA
Regional CLP PO request.
D-27/Cyanide ILM05.2
-------
Exhibit D (Cyanide) Section 12
Quality Control (Con't)
original and duplicate sample values greater than or equal to five
times the CRQL (see Exhibit C). A control limit of the CRQL value
shall be entered in the "Control Limit" column on Form VI-IN if
either the sample or duplicate value is less than five times the
CRQL. If the sample and duplicate values are greater than or equal
to five times the CRQL, or if the sample and duplicate values are
less than the CRQL, the "Control Limit" field is left empty.
12.6.4 If one result is above five times the CRQL level and the other is
below, use the CRQL criteria to determine if the duplicate analysis
is in control. If both sample and duplicate values are less than the
MDL, the RPD is not calculated on Form VI-IN. For solid sample or
solid duplicate results less than five times the CRQL, enter the
value of the CRQL, corrected for sample weight and percent solids,
(i.e., original, not duplicate 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
and associated with that duplicate sample with an "*" on Forms IA-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 and method in the SDG.
The percent difference' data will be used by USEPA to evaluate the
long-term precision of the method. Specific control limits for each
element will be added to Form VI-IN at a later date based on the
precision results.
12.7 Laboratory Control Sample (LCS) Analysis
12.7.1 A solid LCS (LCSS) shall be analyzed using the same sample
preparations, analytical methods, and Quality Assurance (QA)/QC
procedures employed for the EPA samples received. For cyanide, a
distilled ICV shall be used as the aqueous LCS (LCSW).
12.7.2 The USEPA provided LCSS shall be prepared and analyzed using each of
the procedures applied to the solid samples received (exception:
percent solids determination not required). If the USEPA LCSS is
unavailable, other USEPA QC Check samples or other certified
materials may be used. In such a case, the control limits for LCSS
must be documented and provided. One LCSS shall be prepared and
analyzed for every group of solid samples in a SDG, or for each batch
of samples distilled, whichever is more frequent.
12.7.3 All LCSS and percent recovery results will be reported on Form VII-
IN. If the results for the LCSS fall outside the control limits
established by USEPA, the analyses shall be terminated, the problem
corrected, and the samples associated with that LCSS reprepared and
re-analyzed with appropriate new QC.
12.8 Method Detection Limit (MDL) Determination
12.8.1 Before any field samples are analyzed under this contract, the MDLs
shall be determined for non-distilled analyses (Preparation
Method/Code "NP1") and for each distillation procedure and instrument
used, prior to the start of the contract analyses, and annually
thereafter, and shall meet the levels specified in Exhibit C.
An MDL study shall be performed after major instrument maintenance,
or changes in instrumentation or instrumental conditions to verify
the current sensitivity of the analysis.
12.8.2 To determine the MDLs, the Contractor shall run MDL studies following
the procedures given in 40 CFR, Part 136. The Contractor shall
ILM05.2 D-28/Cyanide
-------
Exhibit D (Cyanide) Sections 12-17
Method Performance
prepare the MDL samples by each distillation procedure used and shall
analyze these samples on each instrument used. The Contractor shall
also analyze the non-distilled MDL samples on each instrument used.
12.8.3 The determined concentration of the MDL shall be less than half the
concentration of the CRQL listed in Exhibit C.
12.8.4 The non-distilled MDL (Preparation Method/Code "NP1") shall be used
to determine the appropriate concentration qualifier for the results
of instrument QC analyses (except the distilled ICV).
12.8.5 The results of the MDL determination study shall be forwarded to the
USEPA Regional CLP PO, Sample Management Office (SMO), and Quality
Assurance Technical Support (QATS).
12.8.6 The MDL results shall be reported on Form IX-IN.
13.0 METHOD PERFORMANCE
Not applicable.
14.0 POLLUTION PREVENTION
See Section 1.15 in Exhibit D - Introduction to Analytical Methods.
15.0 WASTE MANAGEMENT
See Section 1.16 in Exhibit D - Introduction to Analytical Methods.
16.0 REFERENCES
16.1 US Environmental Protection Agency. Methods for Chemical Analysis of
Water and Wastes. Method 335.2. 1980.
16.2 American Water Works Association/American Public Health
Association/Water Environment Federation. Standard Methods for the
'^Examination of Water and Wastewater. Method 4500. 18th Edition.
16.3 US Government Printing Office. 40 Code of Federal Regulations, Part 136,
Section 1, Appendix B.
17.0 TABLES/DIAGRAMS/FLOWCHARTS
Not applicable.
D-29/Cyanide ILM05.2
-------
EXHIBIT E
CONTRACT LABORATORY PROGRAM QUALITY ASSURANCE MONITORING PLAN
E-l ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
ILM05.2 E-2
-------
Exhibit E - Contract Laboratory Program Quality Assurance Monitoring Plan
Table of Contents
Section Page
1.0 OVERVIEW 5
1.1 Quality Assurance/Quality Control (QA/QC) Activities 5
1.2 Incentives/Sanctions 5
2.0 INTRODUCTION 6
2.1 Quality Assurance/Quality Control (QA/QC) Program Components . 6
3.0 GENERAL QUALITY ASSURANCE/QUALITY CONTROL (QA/QC) REQUIREMENTS ... 7
4.0 SPECIFIC QUALITY ASSURANCE/QUALITY CONTROL (QA/QC)
MONITORING PROCEDURES 8
4.1 Purpose 8
4.2 Laboratory Audit and Intercomparison Study Program 8
4.3 Annual Verification of Method Detection Limits (MDLs) 8
4.4 Quarterly Verification of Linear Ranges/Interelement
Correction Factors 9
4.5 Quality Assurance/Quality Control Measurements 9
5.0 QUALITY ASSURANCE MANAGEMENT PLAN 10
5.1 Introduction 10
5.2 Required Elements of a Quality Assurance Management Plan ... 10
5.3 Updating and Submitting the Quality Assurance
Management Plan 12
5.4 Incentives/Sanctions 13
6.0 STANDARD OPERATING PERFORMANCE STANDARDS 14
6.1 Introduction 14
6.2 Format 15
6.3 Required SOPs 15
6.4 Updating and Submitting SOP Requirements 18
6.5 Incentives/Sanctions 19
7.0 CONTRACT COMPLIANCE SCREENING (CCS) PERFORMANCE STANDARDS 20
7.1 Overview 20
7.2 CCS Results 20
7.3 CCS Trend Report 20
7.4 Incentives/Sanctions 20
8.0 ANALYTICAL PERFORMANCE STANDARDS REQUIREMENT S 21
8.1 Overview 21
8.2 Preparation of Chemical Standards from the Neat
High Purity Bulk Materia 1 21
8.3 Purchase of Chemical Standards Already in Solution 21
8.4 Requesting Standards from the USEPA Standards
Repository 24
8.5 Documentation of the Verification and
Preparation of Chemical Standards 24
8.6 Incentives/Sanctions 25
9.0 DATA PACKAGE MONITORING AUDITS 26
9.1 Overview 26
9.2 Responding to the Data Package Audit Repor t 26
9.3 Incentives/Sanctions 26
10.0 REGIONAL DATA REVIEW MONITORING 27
10.1 Overview 27
E-3 ILM05.2
-------
Exhibit E - Contract Laboratory Program Quality Assurance Monitoring Plan
Table of Contents (Con't)
Section Page
11.0 QUALITY ASSURANCE (QA) PROFICIENCY MONITORIN G 28
11.1 Performance Evaluation (PE) Samples 28
11.2 Quarterly Blind (QB) Audits 28
11.3 Incentives/Sanctions 30
12.0 ON-SITE LABORATORY QUALITY ASSURANCE (QA) MONITORING EVALUATIONS . . 31
12.1 Overview 31
12.2 Quality Assurance On-Site Evaluation 31
12.3 Evidentiary Audit 31
12.4 Discussion of the On-Site Team's Finding s 32
12.5 Incentives/Sanctions 32
13.0 ELECTRONIC DATA QUALITY ASSURANCE (QA) MONITORING AUDITS 33
13.1 Overview 33
13.2 Submission of the Instrument Electronic Data 35
13.3 Responding to the Electronic Data Audit Report 35
13.4 Incentives/Sanctions 35
14.0 DATA MANAGEMENT PERFORMANCE REQUIREMENTS 36
14.1 Overview 36
14.2 Documenting Data Changes 36
14.3 Lifecycle Management Procedures 36
14.4 Personnel Responsibilities 37
15.0 TABLES 38
TABLE 1. Contract Laboratory Program Quality Assurance
Monitoring Plan 38
ILM05.2 E-4
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Exhibit E Section 1
Overview
1.0 OVERVIEW
Quality Assurance (QA) and Quality Control (QC) are integral parts of
the U.S. Environmental Protection Agency's (USEPA's) Contract Laboratory
Program (CLP). The QA process consists of management review and
oversight at the planning, implementation, and completion stages of the
environmental data collection activity, and ensures that data provided
are of the quality required. The QC process includes those activities
required during data collection to produce the data quality desired and
to document the quality of the collected data.
1.1 Quality Assurance/Quality Control (QA/QC) Activities
During the planning of an environmental data collection program, QA
activities focus on defining data quality criteria and designing a QC
system to measure the quality of data being generated. During the
implementation of the data collection effort, QA activities ensure that
the QC system is functioning effectively, and that the deficiencies
uncovered by the QC system are corrected. After environmental data are
collected, QA activities focus on assessing the quality of data obtained
to determine its suitability to support enforcement or remedial
decisions.
1.1.1 This exhibit describes the overall QA/QC operations and the processes
by which the CLP meets the QA/QC objectives defined above. This
contract requires a variety of QA/QC activities. These contract
requirements are the minimum QC operations necessary to satisfy the
analytical requirements associated with the determination of the
different method analytes. These QC operations are designed to
facilitate laboratory comparison by providing USEPA with comparable
data from all Contractors. These requirements do not release the
analytical Contractor from maintaining their own QC checks on method
and instrument performance.
1.2 Incentives/Sanctions
The Contractor may anticipate incentives by consistently providing the
following: (1) high quality, technically sound data as stipulated by the
ILM05.2 contract; (2) on-time or early delivery of the Sample Delivery
Group (SDG) Cover Sheet; (3) above average Quarterly Blind (QB)
Performance Evaluation (PE) sample scores; (4) diskettes that pass the
initial Contract Compliance Screening (CCS) acceptance criteria; and (5)
SDGs delivered on-time. Samples are distributed routinely to
Contractors based on the quality of work performed, as measured by the
Performance Scheduling Algorithm (PSA) (see Section G of the contract
for details). A Contractor that consistently meets the contract
performance requirements as highlighted above, will earn a higher PSA
score, thereby increasing the likelihood of receiving samples for
analyses. If the Contractor fails to meet the requirements set forth in
this Statement of Work (SOW) or elsewhere in the contract, USEPA may
take, but is not limited to, the following actions (see Section E of the
contract for details): reduction in the number of samples sent under the
contract; suspension of sample shipments; data package audit(s);
electronic data audit(s); on-site laboratory evaluation(s); and/or
remedial PE sample(s).
E-5 ILM05.2
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Exhibit E Section 2
Introduction
2.0 INTRODUCTION
Appropriate use of data generated under the large range of analytical
conditions encountered in environmental analyses requires reliance on
the Quality Control (QC) procedures and criteria incorporated into the
ILM05.2 Statement of Work (SOW).
The data acquired from QC procedures are used to estimate and evaluate
the information content of analytical results and to determine the
necessity for, or the effect of, corrective action procedures. The
parameters used to estimate information content include precision,
accuracy, detection limit, and other quantitative and qualitative
indicators. In addition, QC procedures give an overview of the
activities required in an integrated program to generate data of known
and documented quality required to meet defined objectives.
2.1 Quality Assurance/Quality Control (QA/QC) Program Components
2.1.1 The Contractor's QA/QC program shall include (1) internal QC criteria
that demonstrate compliant levels of performance, as determined by QA
review, as well as (2) external review of data and procedures
accomplished by the monitoring activities of the USEPA OERR
Analytical Operations/Data Quality Center (AOC), Regional Data Users,
Sample Management Office (SMO), and the Quality Assurance Technical
Support (QATS) Laboratory. Each external review accomplishes a
different purpose. These reviews are described in specific sections
of this exhibit. Laboratory evaluation samples, electronic data
audits, and data packages provide an external QA reference for the
program. A Contractor on-site evaluation system is also part of the
external QA monitoring. A feedback loop provides the results of the
various review functions to the Contractors through direct
communications with the USEPA Regional Contract Laboratory Program
Project Officer (CLP PO) and the USEPA OERR AOC Inorganic Program
Manager (AOC PM).
2.1.2 This exhibit does not provide specific instructions for constructing
QA Management Plans, QC systems, or a QA organization. It is,
however, an explanation of the QA/QC requirements of CLP. It
outlines minimum standards for QA/QC programs. It also includes
specific items that are required in a Quality Assurance Management
Plan (QAP) and by the QA/QC documentation detailed in this contract.
Delivery of this documentation provides USEPA with a complete data
package which will stand alone, and limits the need for contact with
the Contractor or with an analyst, at a later date, if some aspect of
the analysis is questioned.
2.1.3 In order to assure that the product delivered by the Contractor meets
the requirements of the contract, and to improve interlaboratory data
comparison, the Contractor shall:
=" Prepare, and adhere to, a written approved QAP, as defined in
Exhibit E, Section 5;
:x- Prepare and adhere to, Standard Operating Procedures (SOPs) as
described in Exhibit E, Section 6;
'* Adhere to the analytical methods in Exhibit D and associated QC
requirements specified within Exhibit E;
'*' Verify and document analytical standards and retain
documentation of the purity of neat materials, as well as, the
ILM05.2 E-6
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Exhibit E Sections 2 & 3
General QA/QC Requirements
purity and accuracy of solutions obtained from private chemical
supply houses;
* Submit all raw data and required documentation for Regional
review;
*= Submit results of all analyzed laboratory evaluation samples,
and adhere to corrective action procedures;
* Submit, upon request, instrument data tapes and applicable
documentation for tape audits, including a copy of the Sample
Data Package;
'*' Submit to on-site laboratory evaluations, and adhere to
corrective action procedures; and
ť Submit all original documentation generated during sample
analyses for USEPA review.
3.0 GENERAL QUALITY ASSURANCE/QUALITY CONTROL (QA/QC) REQUIREMENTS
The Contractor shall adhere to USEPA's Good Laboratory Practices for
laboratory cleanliness with regard to glassware and apparatus. The
Contractor shall also adhere to good laboratory practices with regard to
reagents, solvents, and gases. For additional guidelines regarding
these general laboratory procedures, see the Handbook for Analytical
Quality Control in Water and Wastewater Laboratories USEPA-600/4-79-019.
USEPA Environmental Monitoring Systems Laboratory, Cincinnati, Ohio,
September 1982.
E-7 ILM05.2
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Exhibit E Section 4
Specific QA/QC Monitoring Procedures
4.0 SPECIFIC QUALITY ASSURANCE/QUALITY CONTROL (QA/QC) MONITORING PROCEDURES
4.1 Purpose
4.1.1 The purpose of this document is to provide (1) a uniform set of
procedures for the analysis of inorganic constituents of samples, (2)
documentation of methods and their performance, and (3) verification
of the sample data generated. Although it is impossible to address
every analytical situation in one document, this exhibit defines the
minimum requirements for each major step relevant to any inorganic
analysis.
4.1.2 The primary function of the Contract Laboratory Program (CLP) QA/QC
program is the definition of procedures for the evaluation and
documentation of analytical methodologies and the reduction and
reporting of data. The location and summary of the QA/QC performance
based contracting methods can be found in Exhibit E, Section 15,
Table 1 - Contract Laboratory Program Quality Assurance Monitoring
Plan. The objective is to provide a uniform basis for sample
handling, instrument and methods maintenance, performance evaluation,
and analytical data gathering and reporting. In many instances where
methodologies are available, specific QC procedures are incorporated
into the method documentation (see Exhibit D).
4.1.3 The QA/QC procedures defined herein shall be used by the Contractor
when performing the methods specified in Exhibit D. When QA/QC
procedures are specified in Exhibit D, the Contractor shall follow
those procedures, in addition to procedures specified here.
4.2 Laboratory Audit and Intercomparison Study Program
The Contractor is required to participate in the Laboratory Audit and
Intercomparison Study Program run by USEPA. The Contractor shall be
required to analyze at least one Quarterly Blind (QB) sample per
calendar quarter during the contract period for inorganics.
4.3 Annual Verification of Method Detection Limits (MDLs)
The Contractor shall perform and report annual verification of MDLs by
the method specified in Exhibit D, by type, matrix, and model for each
instrument used on this contract, to Sample Management Office (SMO),
Quality Assurance Technical Support (QATS), and the USEPA Regional
Contract Laboratory Program Project Officer (CLP PO) as specified in
Exhibit B. All the MDLs shall meet the requirements specified in
Exhibit C.
ILM05.2 E-8
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Exhibit E Section 4
Specific QA/QC Monitoring Procedures (Con't)
4.4 Quarterly Verification of Linear Ranges/Interelement Correction Factors
The Contractor shall perform and report quarterly verification of linear
ranges by the method specified in Exhibit D, by type and model for each
instrument used on this contract, to SMO, QATS, and the USEPA Regional
CLP PO as specified in Exhibit B. The Contractor shall also report, as
specified in Exhibit B, integration times. For Inductively Coupled
Plasma - Atomic Emission Spectroscopy (ICP-AES) methods, the Contractor
shall also report, as specified in Exhibit B, wavelengths used and all
interelement correction factors.
4.5 Quality Assurance/Quality Control Measurements
4.5.1 In this Exhibit, as well as other places within this Statement of
Work (SOW), the term "analytical sample" discusses the required
frequency or placement of certain QA/QC measurements. The term
"analytical sample" is defined in the glossary, Exhibit G.
4.5.2 In order for the QA/QC information to reflect the status of the
samples analyzed, all samples and their associated QA/QC analysis
shall be analyzed under the same operating and procedural conditions.
4.5.3 If any QC measurement fails to meet contract criteria, the analytical
measurement must not be repeated prior totaking the appropriate
corrective action as specified in Exhibit D. The exception is the
CRI analysis, which may be re-analyzed once before corrective action
is necessary.
4.5.4 The Contractor shall report all QC data in the exact format specified
in Exhibits B and H.
4.5.5 MDLs, 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 Contractor shall maintain QC data confirming instrument
performance and analytical results.
E-9 ILM05.2
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Exhibit E Section 5
QA Management Plan
5.0 QUALITY ASSURANCE MANAGEMENT PLAN (QAP)
5.1 Introduction
The Contractor shall establish a Quality Assurance (QA) program with the
objective of providing sound .analytical chemical measurements. This
program shall incorporate the Quality Control (QC) procedures, any
necessary corrective action, all documentation required during data
collection, and the quality assessment measures performed by management
to ensure acceptable data production. The Contractor shall follow the
USEPA EPA Requirements for Quality Management Plans (EPA QA/R-2). An
electronic version can be found at http://www.epa.gov/qualityl/
qa_docs.html.
5.1.1 The Contractor shall prepare a written QAP which describes the
procedures that are implemented to achieve the following:
30 Maintain data integrity, validity, and usability;
:x: Ensure that analytical measurement systems are maintained in an
acceptable state of stability and reproducibility;
00 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.
5.1.2 The QAP must present, in specific terms, the policies, organization,
objectives, functional guidelines, and specific QA/QC activities
designed to achieve the data quality requirements in this contract.
Standard Operating Procedures (SOPs) pertaining to each element shall
be included or referenced as part of the QAP. The QAP shall be
paginated consecutively in ascending order. The QAP shall be
available during on-site laboratory evaluations and shall be
submitted to the designee within 7 days of written request by the
USEPA Regional Contract Laboratory Program Project Officer (CLP PO)
or the USEPA OERR Analytical Operations/Data Quality Center (AOC)
Inorganic Program Manager (AOC PM). Additional information relevant
to the preparation of a QAP can be found in USEPA and ASTM
publications.
5.2 Required Elements of a Quality Assurance Management Plan
The required elements of a laboratory's QAP are outlined in this
section. This outline shall be used as a framework for developing the
QAP.
A. Organization and Personnel
1. QA Policy and Objectives (the mission and quality policy of the
organization)
2. QA Management (the specific roles, authorities, and
responsibilities of management and staff with respect to QA and
QC activities)
a. Organization
b. Assignment of QA/QC Responsibilities
ILM05.2 E-10
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Exhibit E Section 5
QA Management Plan (Con't)
c. Reporting Relationships (the means by which effective
communications with personnel actually performing the work are
assured)
d. QA Document Control Procedures
e. QA Program Assessment Procedures (the process used to plan,
implement, and assess the work performed)
3. Personnel
a. Resumes
b. Education and Experience Pertinent to this Contract
c. Training Records and 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. Sample Delivery Group (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
E-ll ILM05.2
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Exhibit E Section 5
QA Management Plan (Con't)
F. Quality Assurance (the process which measures the effectiveness of
QA will be established and how frequently effectiveness will be
measured)
1. Data Quality Assurance
2. Systems/Internal Audits
3. Performance/External Audits
4. Corrective Action Procedures (the continual improvement based on
lessons learned from previous experience)
5. QA Reporting Procedures
6. Responsibility Designation
G. Quality Control
1. Solvent, Reagent, and Adsorbent Check Analysis
2. Reference Material Analysis
3. Internal QC Checks
4. Corrective Action and Determination of QC Limit Procedures
5. Responsibility Designation
5.3 Updating and Submitting the Quality Assurance Management Plan
5.3.1 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:
^ Changes resulting from (1) the Contractor's internal review of
their organization, personnel, facility, equipment, policy and
procedures, and (2) the Contractor's implementation of .the
requirements of the contract, and
=* Changes resulting from USEPA' s review of the laboratory
evaluation sample data, bidder supplied documentation, and
recommendations made during the pre-award on-site laboratory
evaluation.
5.3.1.1 The Contractor shall send a copy of the latest version of the QAP
within 7 days of a request from a USEPA Regional CLP PO or the
USEPA OERR AOC PM. The request will designate the recipients.
5.3.2 Subsequent Updates and Submissions. During the term of the contract,
the Contractor shall amend the QAP when the following circumstances
occur:
* USEPA modifies the technical requirements of the Statement of
Work (SOW) or contract;
* USEPA notifies the Contractor' of deficiencies in the QAP
document;
ILM05.2 E-12
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Exhibit E Section 5
QA Management Plan (Con't)
^ USEPA notifies the Contractor of deficiencies resulting from
USEPA's review of the Contractor's performance;
:x: The Contractor's organization, personnel, facility, equipment,
policy, or procedures change; or
*= The Contractor identifies deficiencies resulting from the
internal review of their organization, personnel, facility,
equipment, policy, or procedures changes.
5.3.2.1 The Contractor shall amend the QAP within 14 days of when the
circumstances listed in Exhibit E, Section 5.3, 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, highlighting the change by underlining the change,
bold printing the change, or using a different print font) and a
copy is sent to the USEPA Regional CLP PO and Quality Assurance
Technical Support (QATS). The amended section pages shall have-
the date on which the changes were implemented. The Contractor
shall incorporate all amendments to the latest version of the QAP
document. The Contractor shall archive all amendments to the QAP
document for future reference by USEPA.
5.4 Incentives/Sanctions
The Contractor shall amend the QAP as specified within this section.
The QAP describes the policies and procedures for ensuring that work
processes, products, or services satisfy expectations or specifications
in ILM05.2. Failure to comply with the requirements of this section may
result in sanctions as described in the contract.
E-13 ILM05.2
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Exhibit E Section 6
Standard Operating Performance Standards
6.0 STANDARD OPERATING PERFORMANCE STANDARDS
6.1 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 USEPA, 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
N tasks. The Contractor shall follow the USEPA Guidance for the
Preparation of Standard Operating Procedures (SOPs) for Quality-Related
Documents (EPA QA/G-6). An electronic version can be found at
http://www.epa.gov/qualityl/qa_docs.html.
6.1.1 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.
6.1.2 All SOPs shall reflect Contractor activities as they are currently
performed in the laboratory. In addition, all SOPs shall be:
'** Consistent with current USEPA regulations, guidelines, and the
Contract Laboratory Program (CLP) ILM05.2 contract requirements.
'^ Consistent with instrument (s) manufacturer's specific instruction
manuals.
:*' Available to USEPA 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 shall demonstrate the
application of the SOPs if requested.
:x: Available to the designated recipients within 7 days, upon
request by the USEPA Regional CLP Project Officer (CLP PO) or the
USEPA OERR Analytical Operations/Data Quality Center (AOC)
Inorganic Program Manager (AOC PM).
^ 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.
:x: 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.
:*" Available at specific work stations as appropriate.
ILM05.2 E-14
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Exhibit E Section 6
Standard Operating Performance Standards (Con't)
* Subject to a document control procedure which precludes the use
of outdated or inappropriate SOPs.
* Reviewed and signed by all Contractor personnel performing
actions identified in the SOP.
6.2 Format
The format for SOPs may vary depending upon the type of activity for
which they are prepared; however, at a minimum, the following sections
shall be included:
=" Title page;
:xl Document Control;
'*> Scope and Applicability;
'** Summary of Method;
:ť Definitions (acronyms, abbreviations, and specialized forms used in
the SOP);
=" Health & Safety;
;*' Personnel Qualifications;
*" Interferences;
=*> Apparatus & Materials (list or specify; note also designated
locations where found);
'" Handling & Preservation;
^ Instrument or Method Calibration;
-!3tl Sample Preparation and Analysis;
00 Data Calculations;
'**> Quality Control (QC) limits;
111 Corrective action procedures, including procedures for secondary
review of information being generated;
=*> Data Management and Records Management;
:xl Miscellaneous notes and precautions; and
111 References.
6.3 Required SOPs
The Contractor shall maintain the following SOPs:
6.3.1 Evidentiary SOPs for required chain-of-custody and document control
are discussed in Exhibit F.
E-15 ILM05.2
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Exhibit E Section 6
Standard Operating Performance Standards (Con't)
6.3.2 Sample Receipt and Storage
!M! Sample receipt and identification logbooks,
'*> Refrigerator temperature logbooks, and
^ Security precautions.
6.3.3 Sample Preparation
6.3.3.1 Metals
6.3.3.2 Cyanide
6.3.4 Glassware Cleaning
6.3.5 Calibration (Balances, etc.)
-JC Procedures;
:*: Frequency requirements;
^ Preventative maintenance schedule and procedures;
00 Acceptance criteria and corrective actions; and
'"' Logbook maintenance authorization.
6.3.6 Analytical Procedures (for each analytical system)
!M! Instrument performance specifications;
:x: Instrument operating procedures;
00 Data acquisition system operation;
:M: Procedures when automatic quantitation algorithms are overridden;
*' QC required parameters;
- Analytical run/injection logbooks; and
:m- Instrument error and editing flag descriptions and resulting
corrective actions.
6.3.7 Maintenance Activities (for each analytical system)
'*' Preventative maintenance schedule and procedures,
:*! Corrective maintenance determinants and procedures, and
'^ Maintenance authorization.
6.3.8 Analytical Standards
"= Standard coding/identification and inventory system;
^ Standards preparation logbook(s);
'*" Standard preparation procedures;
ILM05.2 E-16
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Exhibit.E Section 6
Standard Operating Performance Standards (Con't)
^ Procedures for equivalency/traceability analyses and
documentation;
* Purity logbook (primary standards and solvents) ;
* Storage, replacement, and labeling requirements; and
^ QC and corrective action measures.
6.3.9 Data Reduction Procedures
^ Data processing systems operation;
* Outlier identification methods;
*: Identification of data requiring corrective action; and
* Procedures for format and/or forms for each operation.
6.3.10 Documentation Policy/Procedures
^ Contractor/analyst's notebook policy, including review policy;
=*= Complete Sample Delivery Group (SDG) File (CSF) contents;
:*: Complete SDG File organization and assembly procedures, including
review policy; and
^ Document inventory procedures, including review policy.
6.3.11 Data Validation/Self-Inspection Procedures
:*! Data flow and chain-of-command for data review;
^ Procedures for measuring precision and accuracy;
*' Evaluation parameters for identifying systematic errors;
^ Procedures to assure that hardcopy and electronic deliverables
are complete and compliant with the requirements in the Statement
of Work (SOW) Exhibits B and H;
'*' Procedures to assure that hardcopy deliverables are in agreement
with their comparable electronic deliverables;
^ Demonstration of internal Quality Assurance (QA) inspection
procedure (demonstrated by supervisory sign-off on personal
notebooks, internal laboratory evaluation samples, etc.);
'M: Frequency and type of internal audits (e.g., random, quarterly,
spot checks, perceived trouble areas);
*= Demonstration of problem identification, corrective actions, and
resumption of analytical processing. Sequence resulting from
internal audit (i.e., QA feedback); and
-*- Documentation of audit reports (internal and external), response,
corrective action, etc.
E-17 ILM05.2
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Exhibit E Section 6
Standard Operating Performance Standards (Con't)
6.3.12 Data Management and Handling
x: Procedures for controlling and estimating data entry errors;
^ Procedures for reviewing changes to data and deliverables and
ensuring traceability of updates;
" Lifecycle management procedures for testing, modifying, and
implementing changes to existing computing systems including
hardware, software, and documentation or installing new systems;
^ Database security, backup, and archival procedures including
recovery from system failures;
*: System maintenance procedures and response time;
=* Individual(s) responsible for system operation, maintenance, data
integrity, and security; and
x: Specifications for staff training procedures.
6.4 Updating and Submitting SOP Requirements
6.4.1 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 and the revised
SOPs shall be paginated consecutively in ascending order. The
revised SOPs shall include:
:*: Changes resulting from (1) the Contractor's internal review of
their procedures and (2) the Contractor's implementation of the
requirements of the contract, and
'-*1 Changes resulting from USEPA' s review of the laboratory
evaluation sample data, bidder supplied documentation, and
recommendations made during the pre-award on-site laboratory
evaluation.
6.4.1.1 The Contractor shall send a complete set of the latest version of
SOPs or individually requested SOPs within 7 days of a request
from an USEPA Regional CLP PO or the USEPA OERR AOC PM. The
request will designate the recipients.
6.4.2 Subsequent Updates and Submissions. During the term of the contract,
the Contractor shall amend the SOPs when the following circumstances
occur:
:Ť USEPA modifies the technical requirements of the SOW or contract;
ť= USEPA notifies the Contractor of deficiencies in the SOP
documentation;
:x: USEPA notifies the Contractor of deficiencies resulting from
USEPA's review of the Contractor's performance;
^ The Contractor's procedures change;
^ The Contractor identifies deficiencies resulting from the
internal review of the SOP documentation; or
ILM05.2 E-18
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Exhibit E Section 6
Standard Operating Performance Standards (Con't)
^ The Contractor identifies deficiencies resulting from the
internal review of their procedures.
6.4.2.1 Existing SOPs shall be amended or new SOPs shall be written within
14 days of when the circumstances listed in Exnibit E, Section
6.4, 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, highlighting the change by underlining the change, bold
printing the change, or using a different print font) and a copy
is sent to the USEPA Regional CLP PO and Quality Assurance
Technical Support (QATS). The amended/new SOPs shall have the
date on which the changes were implemented.
6.4.2.2 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.
6.4.2.3 Documentation of the reason(s) for changes to the SOPs shall also
be submitted along with the SOPs.
6.5 Incentives/Sanctions
The Contractor shall amend SOPs as specified within this section. The
.SOPs specify analytical procedures in greater detail than appear in
Exhibit D. Adherence to these requirements will ensure that the
procedure is conducted in a standard, reliable, and reproducible process
-described in ILM05.2. Failure to comply with the requirements specified
herein may result in sanctions as described in the contract.
E-19 ILM05.2
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Exhibit E Section 7
Contract Compliance Screening Performance Standards
7.0 CONTRACT COMPLIANCE SCREENING (CCS) PERFORMANCE STANDARDS
7.1 Overview
7.1.1 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
USEPA.
7.1.2 CCS is performed by the Sample Management Office (SMO) under the
direction of USEPA. 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. USEPA reserves the right
to add and/or delete individual checks.
7.2 CCS Results
CCS results are distributed to the Contractor and other data recipients.
The Contractor has 4 business days to correct deficiencies and shall
send all corrections to the Regional client and SMO. CCS results are
used in conjunction with other information to measure overall Contractor
performance and to take appropriate actions to correct deficiencies in
performance.
7.3 CCS Trend Report
USEPA will periodically generate a CCS trend report which summarizes CCS
results over a given period of time. USEPA will send the CCS trend
report or discuss the CCS trend report during an on-site laboratory
evaluation. In a detailed letter to the USEPA Regional Contract
Laboratory Program Project Officer (CLP PO) and USEPA Contracting
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.
7.4 Incentives/Sanctions
7.4.1 If new Standard Operating Procedures (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 6.
7.4.2 The Contractor shall correct deficiencies and resubmit the data
within 4 business days, as specified within this section.
Resubmission and correction of the data will ensure that the end user
is reviewing contractually compliant data described in ILM05.2.
Correct resubmission of the data may also result in a reduction in
overall sanctions. Specific details on incentives can be found in
the contract. If the Contractor fails to adhere to the requirements
listed in this section, the Contractor will be in noncompliance with
the contract and may be subjected to sanctions as described in the
contract.
'ILM05.2 E-20
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Exhibit E ' Section 8
Analytical Performance Standards Requirements
8.0 ANALYTICAL PERFORMANCE STANDARDS REQUIREMENTS
8.1 Overview
USEPA will not supply analytical reference standards either for direct
analytical measurements or for the purpose of traceability. All
contract laboratories shall 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.
8.2 Preparation of Chemical Standards from the Neat High Purity Bulk
Material
8.2.1 If the laboratory cannot obtain analytical reference standards, 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.
8.2.2 The chemical standards shall be kept at manufacturer recommended
conditions when not being used in the preparation of standard
solutions. Proper storage of chemicals is essential in order to
safeguard them from decomposition.
8.2.3 The Contractor shall be responsible for having analytical
documentation proving the purity of each compound as stated. Purity
confirmation, when performed, shall 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:
EQ. 1 Weight of Impure Compound
. . . _ . , weight of pure compound
weight of impure compound = -^
(percent purity/100)
where "weight of pure compound" is that required to prepare a
specific volume of a solution standard of a specified concentration.
8.2.4 The Contractor is responsible for obtaining analytical documentation
proving that all compounds used in the preparation of solution
standards are correctly identified.
8.2.5 Logbooks shall be kept for all weighing and dilutions. All
subsequent dilutions from the primary standard and the calculations
for determining their concentrations shall be recorded and verified
by a second person. All solution standards shall be refrigerated, if
required, when not in use. All solution standards shall be clearly
labeled as to the identity of the analyte or analytes, the standard
ID number of the solution, concentration, date prepared, solvent,
expiration date of the solution, special storage requirements (if
any), and initials of the preparer.
8.3 Purchase of Chemical Standards Already in Solution
Solutions of analytical reference standards can be purchased by
Contractors provided the solutions meet the following criteria.
E-21 ILM05.2
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Exhibit E Section 8
Analytical Performance Standards Requirements (Con't)
8.3.1 Reference standards shall be accompanied by documentation of the
purity confirmation of the material to verify the integrity of the
standard solutions.
8.3.2 The quality of reference standards purchased shall be 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 Sections 8.3.2.1 and 8.3.2.2"). 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
Section 8.3.2.4. 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 Section 8.3.2.5. Thus, the standard
is certified to be within 10% of the target concentration using the
equations in Section 8.3.2.6. If the procedure above is used, the
supplier must document that the following have been achieved.
8.3.2.1 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 10% 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% less than the target standard. This is called
the "low standard".
8.3.2.2 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; etc.
8.3.2.3 The mean and variance of the six results for each solution shall
be calculated:
EQ. 2 Mean
MEAN =
Y3 + Y4
Y5 +
EQ. 3 Variance
Y,2 + Y,2 + Y,2 + Y 2 + Y 2 + Y 2 - 6 (MEAN)2
VARIANCE = -i ? 1 *- 5 S
The values Ylf Y2, Y3, ..., represent the results of the six
analyses of each standard. The means of the low, target, and high
standards are designated M lt M2, and M3, respectively. The
variances of the low, target, and high standards are designated
Vj, V2, and V3, respectively. Additionally, a pooled variance, V p,
is calculated.
ILM05.2
E-22
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Exhibit E Section 8
Analytical Performance Standards Requirements (Con't)
EQ. 4 Pooled Variance
V V
3
3
= 0-81 2 1.21
If the square root of Vp is less than one percent of M2, then
M22/10,000 is to be used as the value of Vp in all subsequent
calculations.
8.3.2.4 The test statistic shall be calculated:
EQ. 5 Low and High Standard Test Statistic
TEST STATISTIC =
M3 Ml
1.1 0.9
VP
If the test statistic exceeds 2.13, then the supplier has failed
to demonstrate a 20% difference between the high and low
standards. In such a case, the standards are not acceptable.
8.3.2.5 The test statistic shall be calculated:
EQ. 6 Target Standard Test Statistic
M, ^ f M3
TEST STATISTIC = > --, ť 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.
8.3.2.6 The 95% confidence intervals for the mean result of each standard
shall be calculated:
EQ. 7 Low Standard Interval
, v.
Interval for Low Standard = M, ą 2.13 | Ł
6
EQ. 8 Target Standard Interval
Interval for Target Standard = M2 ą 2.13 -
E-23 ILM05.2
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Exhibit E Section 8
Analytical Performance Standards Requirements (Con't)
EQ. 9 High Standard Interval
n
Interval for High Standard = M3 ą 2.13 -j-
8.3.2.6.1 These intervals shall not overlap. If overlap is observed,
then the supplier has failed to demonstrate the ability to
discriminate the 10% difference in concentrations. In such a
case, the standards are not acceptable.
8.3.2.6.2 In any event, the Contractor is responsible for the quality of
the standards employed for analyses under this contract.
8.4 Requesting Standards from the USEPA Standards Repository
Solutions of analytical reference materials can be ordered from the
USEPA Chemical Standards Repository, depending on availability. The
Contractor may 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.
8.5 Documentation of the Verification and Preparation of Chemical Standards
It is the responsibility of the Contractor to maintain the necessary
documentation to show that the chemical standards it has used in the
performance of Contract Laboratory Program (CLP) analysis conform to the
requirements previously listed.
8.5.1 Weighing logbooks, calculations, raw data, etc., whether produced by
the Contractor or purchased from chemical supply houses, shall be
maintained by the Contractor 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 USEPA,
such documentation is to be kept on file by the Contractor for a
period of one year.
8.5.2 Upon request by the USEPA Regional CLP Project Officer (CLP PO), 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
designated recipients.
8.5.3 USEPA will periodically generate a report discussing deficiencies in
the Contractor's documentation for the verification and preparation
of chemical standards. USEPA will send the report or discuss the
deficiencies during an on-site laboratory evaluation. In a detailed
letter to the USEPA Regional CLP PO and CLP Quality Assurance
Coordinator, 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.
8.5.4 If new Standard Operating Procedures (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 6.
ILM05.2 E-24
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Exhibit E Section 8
Analytical Performance Standards Requirements (Con't)
8.6 Incentives/Sanctions
The Contractor shall obtain the highest purity possible when purchasing
chemical standards specified within this section. The use of high
purity standards will ensure a more accurate identification and
quantitation of analytes described in the ILM05.2 Statement of Work
(SOW). Failure to meet the requirements set forth in this section may
result in sanctions as described in the contract.
E-25 ILM05.2
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Exhibit E Section 9
Data Package Monitoring Audits
9.0 DATA PACKAGE MONITORING AUDITS
9.1 Overview
Data package audits are performed by USEPA 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 (QA), and adherence to contractual requirements. This
function provides external monitoring of program Quality Control (QC)
requirements. Data package audits are used to assess the technical
quality of the data and evaluate overall laboratory performance. Audits
provide USEPA 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 the
latest version of all Standard Operating Procedures (SOPs) on file.
9.2 Responding to the Data Package Audit Report
9.2.1 After completion of the data package audit, USEPA will send a copy of
the data package audit report to the Contractor or discuss the data
package audit report on an on-site laboratory evaluation. In a
detailed letter to the USEPA Regional Contract Laboratory Program
Project Officer (CLP PO) and the USEPA 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.
9.2.2 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 6.
9.3 Incentives/Sanctions
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 comments from USEPA, as specified within this
section. The data package audits ensure that the policies and
procedures identified in this Statement of Work (SOW) meet the
requirements of this contract. If the Contractor fails to adhere to the
requirements listed in this section, the Contractor will be in
noncompliance with the contract and may be subjected to sanctions as
described in the contract.
ILM05.2 E-26
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Exhibit E Section 10
Regional Data Review Monitoring
10.0 REGIONAL DATA REVIEW MONITORING
10.1 Overview
Contractor data are generated to meet the specific needs of USEPA
Regions. In order to verify the usability 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 USEPA OERR Analytical Operations/Data
Quality Center (AOC). 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.
10.1.1 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 (SMO),< which is
designed to identify contractual discrepancies, and the review done
by the USEPA OERR AOC, which is designed to evaluate Contractor and
method performance.
E-27
ILM05.2
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Exhibit E Section 11
QA Proficiency Monitoring
11.0 QUALITY ASSURANCE (QA) PROFICIENCY MONITORING
As a means of measuring and evaluating both the Contractor's and the
method's analytical performance, the Contractor shall participate in
USEPA's Proficiency Testing Program. USEPA's Proficiency Testing
Program involves the analysis of Case specific Performance Evaluation
(PE) samples and Quarterly Blind (QB) Audits. The Contractor's
analytical PE samples and QB results will be used by USEPA to assess and
verify the Contractor's continuing ability to produce acceptable
analytical data in accordance with the contractual requirements. The
Contractor shall receive a passing score of 75% to be in compliance with
the contract.
11.1 Performance Evaluation (PE) Samples
11.1.1 The PE sample(s) may be scheduled with the Contractor as frequently
as on a Sample Delivery Group (SDG)-by-SDG basis. The PE samples may
be sent either by the Regional client or the USEPA OERR Analytical
Operations/Data Quality Center (AOC). PE samples assist USEPA in
monitoring Contractor performance.
11.1.2 PE samples will be provided as either single-blinds (recognizable as
a PE sample but of unknown composition), or as double-blinds (not
recognizable as a PE sample and of unknown composition). The
Contractor will not be informed of either the analytes/parameters or
the concentrations in the PE samples.
11.1.3 The Contractor may receive the PE samples as either full volume
samples or ampulated/bottled concentrates from USEPA or a designated
USEPA Contractor. The PE samples shall come with instructions
concerning the unique preparation procedures, if any, required to
reconstitute the PE samples (i.e., the required dilution of the PE
sample concentrate)-. PE samples are to be digested and analyzed with
the rest of the routine samples in the SDG. The Contractor shall
prepare and analyze the PE sample using the procedure described in
the sample preparation and method analysis sections of Exhibit D.
All contract required Quality Control (QC) shall be met. The PE
sample results are to be submitted in the SDG deliverable package per
normal reporting procedures detailed in Exhibit B.
11.1.4 In addition to PE sample preparation and analysis, the Contractor
shall be responsible for correctly identifying and quantitating the
analytes included in each PE sample. When PE sample results are
received by USEPA, the PE sample results will be evaluated for
correct analytical identification and quantitation. The PE sample
evaluation will be provided to the Contractor via coded evaluation
sheets, by analyte. USEPA will notify the Contractor of unacceptable
performance.
11.2 Quarterly Blind (QB) Audits
11.2.1 A QB Audit is a unique analytical Case containing only PE samples
(i.e., referred to as QB samples). The QB samples will be scheduled
by the USEPA OERR AOC through the Sample Management Office (SMO). QB
samples assist USEPA in monitoring Contractor performance.
11.2.2 QB samples will be provided as single-blinds (recognizable as a PE
sample but of unknown composition). The Contractor will not be
informed of either the analytes or the concentrations in the PE
samples.
ILM05.2 E-28
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Exhibit E -- Section 11
QA Proficiency Monitoring (Con't)
11.2.3 The Contractor may receive the QB samples as either full volume
samples or ampulated/bottled concentrates from USEPA or a designated
USEPA Contractor. The QB samples shall come with instructions
concerning the unique preparation procedures, if any, required to
reconstitute the QB samples (i.e., the required dilution of the QB
sample concentrate). The Contractor shall prepare and analyze the QB
samples using the procedure described in the sample preparation and
method analysis sections of Exhibit D. All contract required QC
shall be met, including spike and duplicate analyses. The QB sample
results are to be submitted in the SDG deliverable package per normal
reporting procedures detailed in Exhibit B.
11.2.4 In addition to QB sample preparation and analysis, the Contractor
shall be responsible for correctly identifying and quantitating the
analytes included in each QB sample. When QB sample results are
received by USEPA, the QB sample results will be scored for correct
analytical identification and quantitation. The QB sample scoring
will be provided to the Contractor via coded evaluation sheets, by
analyte. USEPA will notify the Contractor of unacceptable
performance. The Contractor's QB sample performance will be assessed
into one of the following three categories:
i
11.2.4.1 Acceptable, No Response Required: Score greater than or equal to
90%. The data meets most or all of the scoring criteria. No
response is required.
11.2.4.2 Acceptable, Response Explaining Deficiencies Required: Score
greater than or equal to 75%, but less than 90%. Deficiencies
exist in the Contractor's performance. Corrective action response
required.
11.2.4.3 Unacceptable Performance, Response Explaining Deficiencies
Required: Score less than 75%. Corrective action response
required.
11.2.5 In the case of Section 11.2.4.2 or 11.2.4.3, the Contractor shall
describe the deficiency(ies) and the action (s) taken in a corrective
action letter to the USEPA Contracting Officer, USEPA Regional
Contract Laboratory Program Project Officer (CLP PO), and CLP Quality
Assurance (QA) Coordinator within 14 days of receipt of notification
from USEPA.
11.2.6 In the case of Section 11.2.,4.2 or 11.2.4.3, if new Standard
Operating Procedures (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 6.
11.2.7 The Contractor shall be notified by the USEPA Contracting Officer
concerning agreement or disagreement with the proposed remedy for
unacceptable performance.
11.2.8 A Remedial QB Audit is a unique analytical Case containing only QB
samples. A Remedial QB Audit may be scheduled by the USEPA OERR AOC
with the Contractor(s) for any of the following reasons: unacceptable
PE sample performance, unacceptable QB sample performance, and/or
major change in the laboratory (e.g., relocation, new owner, or high
turn-over of key personnel). Sections 11.2.2 through 11.2.7 apply to
the Remedial QB Audit process.
E-29 ILM05.2
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Exhibit E -- Section 11
QA Proficiency Monitoring (Con't)
11.3 Incentives/Sanctions
The Contractor shall analyze PE and QB samples with acceptable
analytical results in accordance with the contractual requirements as
described in this section. If the Contractor fails to adhere to the
requirements listed in this section, the Contractor will be in
noncompliance with the contract and may be subjected to sanctions as
described in the contract.
ILM05.2 E-30
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Exhibit E Section 12
On-Site Laboratory QA Monitoring Evaluations
12.0 ON-SITE LABORATORY QUALITY ASSURANCE (QA) MONITORING EVALUATIONS
12.1 Overview
The USEPA Regional Contract Laboratory Program Project Officer (CLP PO)
or the USEPA Contracting Officer's 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 (QA)
Evaluation and Evidentiary Audit.
12.2 Quality Assurance On-Site Evaluation
QA 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
Quality Control (QC) procedures for adherence to the contract
requirements.
12.2.1 The Contractor shall expect that items to be monitored will include,
but are not limited to, the following:
^ Size, cleanliness, and organization of the facility;
'x: Quantity, age, availability, scheduled maintenance, and
performance of instrumentation;
=" Availability, appropriateness, and utilization of the Quality
Assurance Management Plan (QAP) and Standard Operating Procedures
(SOPs);
<* Staff qualifications, experience, and personnel training
programs;
=*= Analysis of Performance Evaluation (PE) sample (s) ;
*: Reagents, standards, and sample storage facilities;
"= Standard preparation logbooks and raw data;
^ Bench sheets and analytical' logbook maintenance and review; and
:i: Review of the Contractor' s sample analysis/data package
inspection/data management procedures.
12.2.2 Prior to an on-site evaluation, various documentation pertaining to
performance of the specific Contractor is integrated into a profile
package for discussion during the evaluation. Items that may be
included are: previous on-site reports; Quarterly Blind (QB) and/or
PE sample scores results; Regional review of data; Contractor
performance information provided by the Region; data audit reports;
results of Contract Compliance Screening (CCS); and data trend
reports.
12.3 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
comprises a procedural audit, an audit of written SOPs, and an audit of
analytical project file documentation.
E-31 ILM05.2
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Exhibit E Section 12
On-Site Laboratory QA Monitoring Evaluations (Con't)
12.3.1 Procedural Audit. The Contractor shall perform analysis of PE
sample(s) in the presence of the USEPA designated team during the
procedural audit. The procedural audit will be comprised of
everything from 'sample receipt to data package assembly and
completion. This includes the review and examination of actual SOPs
and accompanying documentation for the following laboratory
operations: sample receiving, sample storage, sample identification,
sample security, sample tracking (from receipt to completion of
analysis), analytical project file organization and assembly, and
proper disposal of samples and cogenerated wastes.
12.3.2 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.
12.3.3 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;
"M: 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; and
* Error correction methods.
12.4 Discussion of the On-Site Team's Findings
The QA and evidentiary auditors discuss their findings with the USEPA
Regional CLP PO prior to debriefing the Contractor. During the
debriefing, the auditors present their findings and recommendations for
corrective actions necessary to the Contractor personnel. A report
which discusses deficiencies found during the on-site audit will be sent
to the Contractor to provide further clarification of findings. In a
detailed letter to the USEPA Regional CLP PO and CLP Quality Assurance
Coordinator, the Contractor shall discuss the deficiencies and the
subsequent corrective actions implemented by the Contractor to resolve
the deficiencies within 14 days of receipt of report or the on-site
laboratory evaluation.
12.4.1 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 6.
12.5 Incentives/Sanctions
The Contractor shall submit to on-site evaluations, as specified within
this section. The on-site evaluations ensure that the policies and
procedures identified in this Statement of Work (SOW) meet the
requirements of this contract. If the Contractor fails to adhere to the
requirements listed in this section, the Contractor will be in
ILM05.2 E-32
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Exhibit E Sections 12 & 13
Electronic Data QA Monitoring Audits
noncompliance with the contract and may be subjected to sanctions as
described in the contract.
13.0 ELECTRONIC DATA QUALITY ASSURANCE (QA) MONITORING AUDITS
13.1 Overview
Periodically, USEPA requests the instrument electronic data from
Contractors for a specific Case in order to accomplish electronic data
audits. Generally, electronic data submissions and audits are requested
for the following reasons.
Program overview;
*' Indication of data quality problems;
1X3 Support for on-site audits; and
=" Specific Regional requests.
13.1.1 Depending upon the reason for an audit, the instrument electronic
data from a recent Case, a specific Case, or a laboratory evaluation
sample may be requested. Electronic data audits provide a mechanism
to assess adherence to contractual requirements and to ensure the
consistency of data reported on the hardcopy/electronic deliverables
with that generated on analytical instruments. This function
provides external monitoring of Program Quality Control (QC)
requirements and checks adherence of the Contractor to internal
Quality Assurance (QA) procedures. In addition, electronic data
audits enable USEPA to evaluate the utility, precision, and accuracy
of the analytical methods.
13.1.2 The Contractor shall store all raw and processed electronic
analytical data in the appropriate instrument manufacturer's format,
uncompressed, and with no security codes. The data shall include all
necessary data files for a complete reconstruction of the previously
submitted hardcopy and electronic deliverable data package. All
associated raw data files in the instrument manufacturer proprietary
software format must be submitted if those files contain data or
instrumental parameters regarding any analysis and or correction
applied to an instrument or analytical result. This instrument
electronic data shall include data for all samples and all QC
samples, including but not limited to: blanks, matrix spikes, post-
digestion spikes, analytical spikes, duplicates, serial dilutions,
Laboratory Control Samples (LCSs), Contract Required Quantitation
Limits (CRQL) Check Standards (CRIs), Interference Check Samples
(ICSs), tunes, initial calibrations and verifications, and Continuing
Calibration Verifications (CCVs). In addition, the Contractor shall
supply raw data for the Method Detection Limit (MDL) studies and
Linear Range Analyses (LRS) which are used to set the MDL and LRV
values for the year/quarter in which the Sample Delivery Group (SDG)
was analyzed. The Contractor shall maintain a reference logbook of
data files of EPA sample number, calibration data, standards, blanks,
spikes, and duplicates. The logbook shall include EPA sample
numbers, identified by Case and SDG.
13.1.3 The Contractor is required to retain the instrument electronic data
for three years after submission of the reconciled Complete SDG File.
Electronic media shipped to the USEPA designated recipient must be
fully usable by the recipient. Diskettes must be 3.5 inch, high
density, 1.44 MB MS/DOS formatted and tapes must be either 4 mm or 8
mm. Alternative means for delivery of electronic data may be utilized
E-33 . ILM05.2
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Exhibit E Section 13
Electronic Data QA Monitoring Audits (Con't)
by the Contractor upon prior written approval by USEPA. When
submitting electronic instrument data to USEPA, the following
materials shall be delivered in response to the request.
13.1.3.1 All as'sociated raw data files for all analytical samples and all
QC samples. For example, files for ICP should include raw
intensities and mercury and cyanide files should include raw
absorbances or integrated areas.
13.1.3.2 All processed data files and quantitation output files associated
with the raw data files described in Section 13.1.3.1.
13.1.3.3 All associated identification and calculation files used to
generate the data submitted in the data package. This includes,
but is not limited to, result files, acquisition files,
calibration files, and method files.
13.1.3.4 All Contractor-generated Inductively Coupled Plasma - Atomic
Emission Spectrophotometer (ICP-AES)/ICP - Mass Spectrophotometer
(ICP-MS) interference correction files must be submitted.
13.1.3.5 A copy of the Contractor's reference logbook relating data files
to EPA sample number, calibration data, standards, blanks, spikes,
and duplicates. The logbook shall include EPA sample numbers and
laboratory file identifiers for all samples, blanks, and
standards, identified by Case and SDG.
13.1.3.6 A printout of the directory of all files in each directory,
including all subdirectories and the files contained therein.
13.1.3.7 A copy (hardcopy) of the completed Sample Data Package.
13.1.3.8 A statement attesting to the completeness of the electronic
instrument data submission, signed and dated by the Contractor's
laboratory manager. The Contractor shall also provide a statement
attesting that the data reported have not been altered in any way.
These statements shall be part of a Cover Sheet that includes the
following information relevant to the data submission:
5X3 Contractor name;
=* Date of submission;
!ť: Case number;
ť SDG number;
:x: Instrument make and model number for each instrument;
:x: Instrument operating.software name and version number;
-*1 Data software name and version used for acquisition, re-
quantitation, and hardcopy/report generation;
:l- Data system computer;
* System operating software;
^ Data system network;
'x: Data backup software;
ILM05.2 E-34
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Exhibit E Section 13
Electronic Data QA Monitoring Audits (Con't)
*= Data backup hardware;
:m: Media type and volume of data (in MB) backed up; and
'^ Names and telephone numbers of two Contractor contacts for
further information regarding the submission.
13.2 Submission of the Instrument Electronic Data
Upon request of the USEPA Regional Contract Laboratory Program Project
Officer (CLP PO), the Contractor shall send the required instrument
electronic data and all necessary documentation to the USEPA designated
recipient [e.g., Quality Assurance Technical Support (QATS)] within 7
days of notification.
NOTE: The instrument electronic data shall be shipped according to the
procedures in Exhibit F.
13.3 Responding to the Electronic Data Audit Report
After completion of the electronic data audit, USEPA will send a copy of
the electronic data audit report to the Contractor or may discuss the
electronic data audit report at an on-site laboratory evaluation. In a
detailed letter to the USEPA Regional CLP PO, the Contractor shall
discuss the corrective actions implemented to resolve the deficiencies
listed in the electronic data audit report within 14 days of receipt of
the report or the on-site laboratory evaluation.
13.3.1 If new Standard Operating Procedures (SOPs) are required to be written
or SOPs are required to be amended because of the deficiencies and the
- subsequent corrective action implemented by the Contractor, the
Contractor shall write/amend and submit the SOPs per the requirements
.' listed in Exhibit E, Section 6.
13.4 Incentives/Sanctions
/The Contractor shall submit to electronic data audits and adhere to the
requirements specified in this section. Resubmission and correction of
electronic data will ensure that the end user is reviewing contractually
compliant data described in the ILM05.2 contract. If the Contractor
fails to adhere to the requirements listed in this section, the
Contractor will be in noncompliance with the contract and may be
subjected to sanctions as described in the contract.
E-35 ILM05.2
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Exhibit E Section 14
Data Management Performance Requirements
14.0 DATA MANAGEMENT PERFORMANCE REQUIREMENTS
14.1 Overview
14.1.1 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 (QC).
14.1.2 Data manually entered from hardcopy shall be subject to QC checks 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 re-entering a statistical sample of the data entered
and calculating discrepancy rates by data element.
14.2 Documenting Data Changes
The record of changes in the form of corrections and updates to data
originally generated, submitted, and/or resubmitted shall be documented
to allow traceability of updates. Documentation shall include the
following for each change.
-JU Justification or rationale for the change.
1X3 Initials of the person making the change (s). Data changes shall be
implemented and reviewed by a person or group independent of the
source generating the deliverable.
^ Documentation of changes shall be retained according to the schedule
of the original deliverable.
!*' Resubmitted diskettes or other deliverables shall be re-inspected 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.
14.3 Lifecycle Management Procedures
Lifecycle management procedures shall be applied to computer software
systems developed by the Contractor to be used to generate and edit
contract deliverables. Such systems shall be thoroughly tested and
documented prior to utilization.
14.3.1 A software test and acceptance plan including test requirements, test
results and acceptance criteria shall be developed, followed, and
available in written form.
14.3.2 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.
ILM05.2 E-36
-------
Exhibit E Section 14
Data Management Performance Requirements (Con't)
14.3.3 Each version of the production system will be given an identification
number, date of installation, and date of last operation and will be
archived.
14.3.4 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.
14.3.5 This documentation shall be available for on-site review and/or upon
written request by the USEPA Regional Contract Laboratory Program
Project Officer (CLP PO) or the USEPA OERR Analytical Operations/Data
Quality Center (AOC) Inorganic Program Manager (AOC PM).
14.4 Personnel Responsibilities
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 QC.
Data and system security, backup and archiving.
E-37 ILM05.2
-------
Exhibit E Section 15
Tables
15.0 TABLES
TABLE 1. Contract Laboratory Program Quality Assurance Monitoring Plan
Exhibit A:
Summary of
Requirements
Exhibit B: Reporting
and Deliverables
Requirements
Exhibit C: Inorganic
Target Analyte List
with Contract
Required
Quantitation Limits
Exhibit D:
Analytical Methods
Exhibit E: Contract
Laboratory Program
Quality Assurance
Monitoring Plan
Summary of Program
Requirements
Reporting and
Deliverable
Requirements
Target Analyte List
with Contract
Required
Quantitation Limits
ICP-AES requirements
are outlined in
Exhibit D, Part A,
Sections 1.0 through
8.0, 14.0, and 15.0.
ICP-MS requirements
are outlined in
Exhibit D, Part B,
Sections 1 . 0 through
8.0, 14.0, and 15.0.
Mercury requirements
are outlined in
Exhibit D, Part C,
Sections 1 . 0 through
8.0, 14.0 and 15.0.
Cyanide requirements
are outlined in
Exhibit D, Part D,
Sections 1 . 0 through
8.0, 14.0, and 15.0.
General QA/QC
Requirements
Performance
standards are
summarized in
Exhibit A, Sections
1 . 0 through 4.0.
Performance
standards are
outlined in Exhibit
B, Sections 1.. 0
through 4.0.
Performance
standards are
outlined in Exhibit
C, Section 1.0.
Performance
standards are
outlined in Exhibit
D, Part A, Sections
9.0 through 11.0.
Performance
standards are
outlined in Exhibit
D, Part B, Sections
9.0 through 11.0.
Performance
standards are
outlined in Exhibit
D, Part C, Sections
9.0 through 11.0.
Performance
standards are
outlined in Exhibit
D, Part D, Sections
9.0 through 11.0.
As outlined in
Exhibit D, Quality
Control sections.
QA monitoring plan
is outlined in
Exhibit E.
CCS in Exhibit E,
Section 7.0, and
CADRE will be used
to monitor reporting
electronic
deliverables.
QA monitoring plan
is outlined in
Exhibit E.
QA monitoring plan
is outlined in
Exhibit D, Part A,
Section 12.0, and
Exhibit E.
QA monitoring plan
is outlined in
Exhibit D, Part B,
Section 12.0, and
Exhibit E.
QA monitoring plan
is outlined in
Exhibit D, Part C,
Section 12.0, and
Exhibit E.
QA monitoring plan
is outlined in
Exhibit D, Part D,
Section 12.0, and
Exhibit E.
QA Management Plan
is outlined in
Exhibit E, Section
5.0.
ILM05.2
E-38
-------
Exhibit E Section 15
Tables (Con't)
TABLE 1. Contract Laboratory Program Quality Assurance Monitoring Plan (Con't)
Exhibit E: Contract
Laboratory Program
Quality Assurance
Monitoring Plan
(Con't)
Quality Assurance
Management Plan
As outlined in
Exhibit E, Sections
5.1.1 and 5.1.2, a
written QA
Management Plan
shall be used to
ensure acceptable
data production of
known and documented
quality.
USEPA will review
and approve the QA
Management Plan.
Standard Operating
Procedures
Performance
standards are
outlined in Exhibit
E, Sections 6.0
through 6.4, and
must be performed as
stated.
SOPs will be
reviewed by USEPA
during Pre-Award,
on-site audits,
after modifications
are made and
randomly, as deemed
appropriate.
Contract Compliance
Screening
Performance
standards are
outlined in Section
E.2 of the ILM05.2
IFB and must be
performed as stated.
The sample data
package will be
evaluated against
the technical and
completeness
requirements of the
contract.
Analytical Standards
Performance
standards are
outlined in Exhibit
E, Sections 8.0
through 8.5, and
must be performed as
stated.
Randomly, USEPA will
review analytical
standards
verification and
preparation
documentation, as
deemed appropriate.
Data Package Audits
Performance
standards are
outlined in Exhibit
E, Sections 9.0
through 9.2.
Data package audits
are performed by
USEPA to evaluate
technical quality of
the hardcopy raw
data, QA, and
adherence to
contractual
requirements.
Regional Data Review
Analytical data is
reviewed by each
Region from the
perspective of the
end user to
determine the
usability of the
data, as outlined in
Exhibit E, Section
10.0.
Regional validation
and/or CADRE reports
are generated for
all data packages.
E-39
ILM05.2
-------
Exhibit E Section 15
Tables (Con't)
TABLE 1. Contract Laboratory Program Quality Assurance Monitoring Plan (Con't)
Exhibit E: Contract
Laboratory Program
Quality Assurance
Monitoring Plan
(Con't)
Exhibit F: Chain-of-
Custody, Document
Control and Written
Standard Operating
Procedures
Exhibit G: Glossary
of Terms
Proficiency Testing
On-Site Laboratory
Evaluations
Electronic Data
Audits
Data Management
Standard Operating
Procedures
Written Standard
Operating Procedures
Glossary of Terms
Performance
standards are
outlined in Exhibit
E, Sections 11.0
through 11.2, and
must be performed as
stated.
Performance
standards are
outlined in Exhibit
E, Sections 12.0
through 12.4.
Performance
standards are
outlined in Exhibit
E, Sections 13.0
through 13.3.
Performance
standards are
outlined in Exhibit
E, Sections 14.0
through 14.4, and
must be performed as
stated.
Performance
standards are
outlined in Exhibit
F, Sections 2.0
through 2.7.
Performance
standards are
outlined in Exhibit
F, Sections 3.0
through 3.7.
Contractors shall
adhere to
interpretation of
SOW terms as defined
within Exhibit G.
Acceptable QB scores
will assist in
monitoring
contractor
performance as
defined in Exhibit
E, Sections 11.2.4.1
through 11.2.4.3,
and 11.2.8.
USEPA will evaluate
the results from
quality assurance
and evidentiary on-
site audits as
defined in Exhibit
E, Sections 12.2.1
through 12.3.3, to
assist in monitoring
the contractor.
CCS in Exhibit E,
Section 7.0, will be
used to monitor
electronic
deliverables .
USEPA will monitor
data management
practices during
quality assurance
and evidentiary on-
site audits.
SOPs will be
reviewed by USEPA
during Pre-Award,
on-site audits,
after modifications
are made, and
randomly as deemed
appropriate .
SOPs will be
reviewed by USEPA
during Pre-Award,
on-site audits,
after modifications
are made, and
randomly as deemed
appropriate.
N/A
ILM05.2
E-40
-------
Exhibit E Section 15
Tables (Con't)
TABLE 1. Contract Laboratory Program Quality Assurance Monitoring Plan (Con't)
Exhibit H:
Data Dictionary and
Format for Data
Deliverables in
Computer-Readable
Format
Data Dictionary and
Format
Performance
standards are
outlined in Exhibit
H and Appendix A.
CCS in Exhibit E,
Section 7.0, will be
used to monitor
electronic
deliverables.
Appendix B:
Analysis
Modified
GFAA requirements
are outlined in
Appendix B, Sections
1.0 through 8.0,
14.0, and 15.0.
Performance
standards are
outlined in Appendix
B, Sections 9.0
through 11.0.
QA monitoring plan
is outlined in
Appendix B, Section
12.0, and Exhibit E.
E-41
ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
-------
EXHIBIT F
CHAIN-OF-CUSTODY, DOCUMENT CONTROL
AND WRITTEN STANDARD OPERATING PROCEDURES
F-l ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
ILM05.2 F-2
-------
Exhibit F - Chain-of-Custody, Document Control and
Written Standard Operating Procedures
Table of Contents
Section Page
1.0 INTRODUCTION 5
1.1 Purpose of Evidence Requirements 5
2.0 STANDARD OPERATING PROCEDURES 6
2.1 Sample Receiving 6
2.2 Sample Identification 7
2.3 Sample Security 7
2.4 Sample Storage 7
2.5 Sample Tracking and Document Control 8
2.6 Computer-Resident Sample Data Contro 1 9
2.7 Complete SDG File (CSF) Organization and Assembly 9
3.0 WRITTEN STANDARD OPERATING PROCEDURES 11
3.1 Sample Receiving 11
3.2 Sample Identification 12
3.3 Sample Security .' 13
3.4 Sample Storage 13
3.5 Sample Tracking and Document Control 13
3.6 Computer-Resident Sample Data Contro 1 14
3.7 CSF Organization and Assembly 15
F-3 ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
ILM05.2 F-4
-------
Exhibit F Section 1
Introduction
1.0 INTRODUCTION
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 U.S. Environmental
Protection Agency's (USEPA's) sample data and records supporting sample-
related activities are admissible and have weight as evidence in future
litigation. Contractors are required to maintain USEPA 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.
1.1 Purpose of Evidence Requirements
The purpose 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;
:xl Ensuring the integrity of sample identity while in possession of the
Contractor;
'-*1 Ensuring sample-related activities are recorded on documents or in
other formats for USEPA 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; and
!in Ensuring that all laboratory records directly related to USEPA
samples are assembled and delivered to USEPA or, prior to delivery,
are available upon USEPA's request.
F-5 ILM05.2
-------
Exhibit F Section 2
Standard Operating Procedures
2.0 STANDARD OPERATING PROCEDURES
The Contractor shall implement the following Standard Operating
Procedures (SOPs) for sample receiving, sample identification, sample
security, sample storage, sample tracking and document control,
computer-resident sample data control, and Complete Sample Delivery
Group (SDG) File (CSF) organization and assembly to ensure
accountability of USEPA sample chain-of-custody as well as control of
all USEPA sample-related records.
2.1 Sample Receiving
2.1.1 The Contractor shall designate a sample custodian responsible for
receiving USEPA samples.
2.1.2 The Contractor shall designate a representative to receive USEPA
samples in the event that the sample custodian is not available.
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 a designated 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 a designated representative.
2.1.5 The sample custodian or a designated 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.
2.1.6 The sample custodian or a designated representative shall verify and
record the following information on Form DC-1 as samples are received
and inspected:
**> Presence or absence and condition of custody seals on shipping
-, and/or sample containers;
:x: Custody seal numbers when present;
'x* Presence or absence of Traffic Reports/Chain of Custody Records or
Packing Lists;
:i: Presence or absence of airbills or airbill stickers;
:x: Airbill or airbill sticker numbers;
1X3 Presence or absence of sample tags;
:*: Sample tags listed/not listed on Traffic Reports/Chain of Custody
Records;
00 Condition of the sample bottles;
^ Presence or absence of cooler temperature indicator bottle;
:*: Cooler temperature;
^ Date of receipt;
:l: Time of receipt;
'*' EPA sample numbers;
ILM05.2 F-6
-------
Exhibit F Section 2
Standard Operating Procedures (Con't)
'*= pH of all aqueous samples;
'x* Sample tag numbers;
:*: Assigned laboratory numbers;
>
"= Remarks regarding condition of sample shipment, etc.;
<** Samples delivered by hand; and
:i: Problems and discrepancies.
2.1.7 The sample custodian or a designated representative shall sign, date,
and record the time on all accompanying forms, when applicable, at
the time of sample receipt (e.g.. Traffic Reports/Chain of Custody
Records or packing lists, and airbills).
NOTE: Initials are not acceptable.
2.1.8 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; insufficient sample volume; unsatisfactory sample condition
(e.g., leaking sample container); and samples not preserved to the
proper pH.
2.1.9 The Contractor shall record the resolution of all problems and
discrepancies communicated through SMO.
2.2 Sample Identification
2.2.1 The Contractor shall maintain the identity of USEPA 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 sample number or a unique laboratory sample identification
number.
2.3 Sample Security
2.3.1 The Contractor shall demonstrate that USEPA sample custody is
maintained from receiving through retention or disposal. A sample is
in custody if:
:x: It is in your possession; or
=" It is in your view after being in your possession; or
:i: 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 USEPA samples and
prepared samples.
F-7 ILM05.2
-------
Exhibit F Section 2
Standard Operating Procedures (Con't)
2.5 Sample Tracking and Document Control
2.5.1 The Contractor shall record all activities performed on USEPA
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 of analysis, the
instrument type and parameter group [e.g., ICP-AES (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
(e.g., 01/01/1999) and signed 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 data reporting forms 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 SDG per page, except in the
events where SDGs "share" Quality Control (QC) samples (e.g.,
instrument run logs and extraction logs).
2.5.14 Each page in bound and unbound logbooks shall be dated
(month/day/year) and signed (no initials) at the bottom by the
individual recording the activity (if a single entry is made on a
page) or by the last individual recording information on the page (if
multiple entries are on the same page).
2.5.15 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.
ILM05.2 F-E
-------
Exhibit F Section 2
Standard Operating Procedures (Con't)
2.5.16 The Contractor shall document disposal or retention of USEPA samples,
remaining portions of samples, and prepared samples.
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.
2.6.5.1 The electronic data collection system shall be maintained in a
secure location.
2.6.5.2 Access to the electronic data collection system functions shall be
limited to authorized personnel through utilization of software
security techniques (e.g., log-ons or restricted passwords).
2.6.5.3 Electronic data collection systems shall be protected from the
introduction of external programs or software (e.g., 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 SDG File (CSF) Organization and Assembly
2.7.1 The Contractor shall designate a document control officer responsible
for the organization and assembly of the 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.
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.
F-9 ILM05.2
-------
Exhibit F Section 2
Standard Operating Procedures (Con't)
2.7.6
2.7.7
2.7.8
2.7.!
Documents relevant to each SDG including, but not limited to, the
following shall be included in the CSF:
logbook pages;
bench sheets;
screening records;
preparation records;
repreparation records;
analytical records;
re-analysis records;
records of failed or
attempted analysis;
custody records;
sample tracking records;
raw data summaries;
computer printouts;
correspondence;
FAX originals;
library search results; and
other.
The document control officer or a designated' representative shall
ensure that sample tags are encased in clear plastic bags before
placing them in the CSF.
CSF documents shall be organized and assembled on an SDG-specific
basis.
Original documents which include information relating to more than
one SDG (e.g., Traffic Reports/Chain of Custody Records,- 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 a designated representative shall record the
following statement on the copies in (indelible) 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. 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" section on Form
DC-2.
2.7.12 Before shipping each CSF, the document control officer or a
designated 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 a designated 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 a
ILM05.2
F-10
-------
Exhibit F Sections 2 & 3
Written Standard Operating Procedures
designated 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 a designated representative when sealing deliverable
packages.
3.0 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 Complete
Sample Delivery Group (SDG) File (CSF) organization and assembly to
ensure accountability for USEPA sample chain-of-custody and control of
all USEPA 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.
3.1.2.1 The condition of shipping containers and sample containers are
inspected and recorded on Form DC-1 upon receipt by the sample
custodian or a designated representative.
3.1.2.2 The condition of custody seals are inspected and recorded on Form
DC-1 upon receipt by the sample custodian or a designated
representative.
3.1.2.3 The presence or absence of the following documents/items
accompanying the sample shipment is verified and recorded on Form
DC-1 by the sample custodian or a designated representative:
00 Custody seals;
!*: Traffic Reports/Chain of Custody Records or Packing Lists;
"= Airbills or airbill stickers;
:*: Sample tags; and
:x: Cooler temperature indicator bottle.
3.1.2.4 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 a
designated representative.
3.1.2.5 The following information is recorded on Form DC-1 by the sample
custodian or a designated representative as samples are received
and inspected:
:x: Custody seal numbers, when present;
^ Airbill or airbill sticker numbers;
:*: Sample tag numbers listed/not listed on Traffic Reports/Chain
of Custody Records;
F-ll ILM05.2
-------
Exhibit F Section 3
Written Standard Operating Procedures (Con't)
30 Condition of sample bottles;
1X2 Cooler temperature;
:x: Date of receipt;
=** Time of receipt;
<*> EPA sample numbers;
!M! pH of all aqueous samples;
= Sample tag numbers;
=*= Assigned laboratory numbers;
!x: Remarks regarding condition of sample shipment, etc.;
00 Samples delivered by hand; and
'** Problems and discrepancies.
3.1.2.6 All accompanying forms are signed, dated, and the time is
recorded, when applicable, at the time of sample receipt (e.g.,
Traffic Reports/Chain of Custody Records or packing lists, and
airbills) by the sample custodian or a designated representative.
3.1.2.7 The Sample Management Office (SMO) is contacted to resolve
problems and discrepancies including, but not limited to: absent
documents; conflicting information; absent or broken custody
seals; insufficient sample volume; unsatisfactory sample condition
(e.g., leaking sample container); and samples not preserved to the
proper pH.
3.1.2.8 The resolution of all problems and discrepancies communicated
through SMO is recorded.
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.
3.2.2.1 The identity of USEPA 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;
The Contractor uses prefixes or suffixes in addition to
laboratory sample identification numbers, the written SOPs
shall include their definitions; and
'*' The Contractor uses methods to uniquely identify
fractions/parameter groups and matrix type, the written SOPs
shall include a description of these methods.
3.2.2.2 Each sample and sample preparation container is labeled with the
SMO number or a unique laboratory sample identification number.
ILM05.2 F-12
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Exhibit F Section 3
Written Standard Operating Procedures (Con't)
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.
3.3.2.1 Procedures which ensure the following:
:i: Sample custody is maintained; and
=* The security of designated secure areas is maintained.
3.3.2.2 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 USEPA samples and
prepared samples in the laboratory.
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.
3.5.2.1 Examples of all laboratory documents used during sample receiving,
sample storage, sample transfer, sample analyses, CSF organization
and assembly, and sample retention or disposal.
3.5.2.2 Procedures which ensure the following:
=*= All activities performed on USEPA samples are recorded;
:x: Titles which identify the activities recorded are printed on
each page of all laboratory documents;
'* Information recorded in columns is identified with column
headings;
;x: Reviewers' signatures are identified on laboratory documents;
^ The laboratory name is included on preprinted laboratory
documents;
00 Laboratory document entries are signed and dated with the
month/day/year (e.g., 01/01/1999);
'* 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;
F-13 ILM05.2
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Exhibit F Section 3
Written Standard Operating Procedures (Con't)
a! Unused portions of laboratory documents are lined-out;
=" Pages in bound and unbound logbooks are sequentially numbered;
!X! 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" Quality Control (QC) samples (e.g.,
instrument run logs and extraction logs);
=* Each page in bound and unbound logbooks shall be dated
(month/day/year) and signed (no initials) at the bottom by the
individual recording the activity (if a single entry is made on
a page) or by the last individual recording information on the
page (if multiple entries are on the same page);
== Information inserted in laboratory documents is affixed
permanently, signed, and dated across the insert; and
:*: The retention or disposal of USEPA 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.
i
3.6.2.1 Procedures which ensure the following:
'*= Contractor personnel responsible for original data entry are
identified;
:x: Changes to electronic data are made such that the original data
entry is preserved, the editor is identified, and the revision
date is recorded;
:M: 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;
:I: Electronic data collection system security is maintained;
a3 Archives of electronic data and accompanying software are
maintained in a secure location; and
:*! Off-site backup and storage of electronic data is maintained.
3.6.2.2 Descriptions of archive storage areas for the electronic data and
the software required to access data archives.
3.6.2.3 A list of authorized personnel who have access to electronic data
collection system functions and to archived data.
ILM05.2 F-14
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Exhibit F Section 3
Written Standard Operating Procedures (Con't)
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.
* 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.
00 All documents relevant to each SDG are included in the CSF.
'x* Sample tags are encased in clear plastic bags by the document
control officer or a designated 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.
=ť Each CSF is submitted with a completed Form DC-2, and resubmitted
CSFs are submitted with a new or revised Form DC-2.
:l! 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 a designated representative.
:*: Shipments of deliverable packages are documented by the document
control officer or a designated representative.
" Deliverable packages are shipped by the document control, officer
or a designated representative using custody seals in a manner
such that opening the packages would break the seals.
:i: Custody seals are signed and dated by the document control officer
or a designated representative before placing them on deliverable
packages.
F-15 ILM05.2
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EXHIBIT G
GLOSSARY OF TERMS
6-1 ILM05.2
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ILM05.2 G-2
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Exhibit G -- Glossary of Terms
ABSORBANCE - A measure of the decrease in incident light passing through a
sample into a detector. It is defined mathematically as:
Absorbance
A = -log
lo
WHERE,
I = Radiation intensity of a sample.
IB = Radiation intensity of a blank.
ALIQUOT - A measured portion of a field sample, standard, or solution taken
for sample preparation and/or 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 (ICV), initial calibration blank (ICB), continuing
calibration verification (CCV), continuing calibration blank (CCB), and tunes.
Note the following are all defined as analytical samples: undiluted and
diluted samples (USEPA and non-USEPA), matrix spike samples, duplicate
samples, serial dilution samples, analytical spike samples, post-digestion
spike samples. Interference Check Samples (ICSs), Contract Required
Quantitation Limit (CRQL) Check Standards (CRIs), Laboratory Control Samples
(LCSs), Performance Evaluation (PE) samples, Preparation Blanks (PBs), and
Linear Range Samples (LRSs).
ANALYTICAL SEQUENCE - The actual instrumental analysis of the samples from the
time of instrument calibration through the analysis of the final CCV or CCB.
All sample analyses during the analytical sequence are subject to the QC
protocols set forth in Exhibits D and E of this contract unless otherwise
specified in the individual methods.
ANALYTICAL SPIKE - A spike that is fortified just prior to analysis by adding
a known quantity of the analyte to an aliquot of the prepared sample.
ASTM - American Society for Testing and Materials. A developer and provider
of voluntary consensus standards.
AUTOZERO - Zeroing the instrument at the proper wavelength. It is equivalent
to running a standard blank with the absorbance set at zero.
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.
BLANK - An analytical sample designed to assess specific sources of
contamination. See individual definitions for types of blanks.
CALIBRATION - The establishment of an analytical curve based on the
absorbance, emission intensity, or other measured characteristic of known
G-3 ILM05.2
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Exhibit G Glossary of Terms (Con't)
standards. The calibration standards must be prepared using the same type of
reagents or concentration of acids as used in the sample preparation.
CALIBRATION BLANK - A blank solution containing all of the reagents and in the
same concentration as those used in the analytical sample preparation. This
blank is not subjected to the preparation method.
CALIBRATION STANDARDS - A series of known standard solutions used by the
analyst for calibration of the instrument (i.e., preparation of the analytical
curve). The solutions may or may not be subjected to the preparation method
but contain the same matrix (i.e., the same amount of reagents and/or
preservatives) as the sample preparations to be analyzed.
CASE - A finite, usually predetermined number of samples collected over a
given time period from a particular site. Case numbers are assigned by the
Sample Management Office (SMO). A Case consists of one or more Sample
Delivery Groups (SDGs).
CONCENTRATION LEVEL (low or medium) - For inorganics analysis, low or medium
level is defined by the appropriate designation by the sampler on the Traffic
Report/Chain of Custody Record.
CONTAMINATION - A component of a sample or an extract that is not
representative of the environmental source of the sample. Contamination may
stem from other samples, sampling equipment, while in transit, from laboratory
reagents laboratory environment, or analytical instruments.
CONTINUING CALIBRATION VERIFICATION (CCV) - A single parameter or multi-
parameter standard solution prepared by the analyst and used to verify the
stability of the instrument calibration with time, and the instrument
performance during the analysis of samples. The CCV can be one of the
calibration standards. However, all parameters being measured by the
particular system must be represented in this standard and the standard must
have the same matrix (i.e., the same amount of reagents and/or preservatives)
as the samples. The CCV should have a concentration in the middle of the
calibration range and shall be run every 10 analytical samples or every 2
hours, whichever is more frequent.
CONTRACT COMPLIANCE SCREENING (CCS) - A screening of electronic and hardcopy
data deliverables for completeness and compliance with the contract. This
screening is done under USEPA direction by the SMO Contractor.
CONTRACT LABORATORY PROGRAM (CLP) - Supports the USEPA's Superfund effort by
providing a range of state-of-the-art chemical analytical services of known
quality. This program is directed by the Analytical Operations/Data Quality
Center (AOC) of the Office of Emergency and Remedial Response (OERR) of USEPA.
CONTRACT REQUIRED QUANTITATION LIMIT (CRQL) - Minimum level of quantitation
acceptable under the contract Statement of Work (SOW).
CONTRACT REQUIRED QUANTITATION LIMIT (CRQL) CHECK STANDARD (CRI) - A single
parameter or multi-parameter standard solution prepared at the CRQL and used
to verify the instrument calibration at low levels.
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.
CYANIDE (Total) - 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.
ILM05.2 G-4
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Exhibit G Glossary of Terms (Con't)
DATE - MM/DD/YYYY - Where MM = 01 for January, 02 for February, ... 12 for
December; DD = 01 to 31; YYYY = 1998, 1999, 2000, 2001, etc.
DAY - Unless otherwise specified, day shall mean calendar day.
DIGESTION LOG - An official record of the sample preparation (digestion).
DIRECT ANALYSIS - Analysis of a sample, standard, or blank that has not been
taken through a preparation procedure (digestion or distillation).
DISSOLVED METALS - Analyte elements in a water/aqueous sample which will pass
through a 0.45 micrometer (um) 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 QC - Any Quality Control sample submitted from the field to the
laboratory. Examples include, but are not limited to: field blanks, field
duplicates, and field spikes.
FIELD SAMPLE - A portion of material received to be analyzed that is contained
in single or multiple containers and identified by a unique EPA sample number.
GRAPHITE FURNACE ATOMIC ABSORPTION (GFAA) - A technique for the determination
of analytes in which a sample aliquot is injected into a hollow graphite tube,
which is then heated to atomize the analyte. The vapor absorbs light at
wavelengths characteristic of the element(s) atoms present.
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 calibration.
INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION SPECTROSCOPY (ICP-AES) - 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.
INDUCTIVELY COUPLED PLASMA-MASS SPECTROSCOPY (ICP-MS) - A technique for the
multi-element determination of elements in solution. The basis of the
technique is the detection of atomic ions produced by an ICP and sorted by
mass/charge ratio.
IN-HOUSE - At the Contractor's facility.
INITIAL 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.
G-5 ILM05.2
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Exhibit G Glossary of Terms (Con't)
INITIAL CALIBRATION VERIFICATION (ICV) - Solution(s) prepared from stock
standard solutions, metals or salts obtained from a source separate from that
utilized to prepare the calibration standards. The ICV is used to verify the
concentration of the calibration standards and the adequacy of the instrument
calibration. The ICV should be traceable to NIST or other certified standard
sources when USEPA ICV solutions are not available.
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 .
INSUFFICIENT QUANTITY - When there is not enough volume (water/aqueous sample)
or weight (soil/sediment) to perform any of the required operations: sample
analysis, percent solids, etc. Exhibit D provides guidance for addressing
this problem.
INTERFERENCE CHECK SAMPLE - A solution containing both interfering and analyte
elements of known concentration that can be used to verify background and
interelement correction factors.
INTERFERENTS - Substances which affect the analysis for the element of
interest.
INTERNAL STANDARD - A non-target element added to a sample at a known
concentration after preparation but prior to analysis. Instrument responses
to internal standards are monitored as a means of assessing overall instrument
performance.
LABORATORY - Synonymous with Contractor as used herein.
LABORATORY CONTROL SAMPLE (LCS) - A control sample of known composition.
Laboratory control samples are analyzed using the same sample preparation,
reagents, and analytical methods employed for the USEPA 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/Chain of Custody Record. Also referred to as VTSR
(Validated Time of Sample Receipt).
LINEAR RANGE, LINEAR DYNAMIC RANGE - The concentration range over which the
instrument response remains linear.
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/
aqueous or soil/sediment. Matrix is not synonymous with phase (liquid or
solid).
MATRIX EFFECT - In general, the effect of particular matrix constituents.
MATRIX SPIKE - Aliquot of a sample (water/aqueous 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 DETECTION LIMIT (MDL) - The concentration of a target parameter that,
when a sample is processed through the complete method, produces a signal with
99 percent probability that it is different from the blank. For 7 replicates
of the sample, the mean value must be 3.14s above the blank, where "s" is the
standard deviation of the 7 replicates.
NARRATIVE (SDG Narrative) - Portion of the data package which includes
laboratory, contract, Case, sample number identification, and descriptive
documentation of any problems encountered in processing the samples, along
ILM05.2 G-6
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Exhibit G Glossary of Terms (Con't)
with corrective action taken and problem resolution. Complete SDG Narrative
specifications are included in Exhibit B.
PERCENT DIFFERENCE (%D) - As used in this SOW and elsewhere to compare two
values. The difference between the two values divided by one of the values.
PERCENT SOLIDS (%S) - 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
USEPA for Contractor analysis. Used by USEPA to evaluate Contractor
performance.
PREPARATION BLANK - An analytical control that contains reagent water and
reagents, which is carried through the entire preparation and analytical
procedure.
PREPARATION LOG - An official record of the sample preparation (digestion or
distillation).
QUALITY ASSURANCE TECHNICAL SUPPORT (QATS) LABORATORY - A Contractor-operated
facility operated under the QATS contract, awarded and administered by USEPA.
REAGENT WATER - The purity of this water must be equivalent to ASTM Type II
reagent water of Specification D1193-77, "Standard Specification for Reagent
Water".
RELATIVE PERCENT DIFFERENCE (RPD) - As used in this SOW and elsewhere to
compare two values, the relative percent difference is based on the mean of
the two values, and is reported as an absolute value, i.e., always expressed
as a positive number or zero.
REPRESENTATIVE - Alternate or designee who has the knowledge and authority to
perform a specific task.
ROUNDING RULES - If the figure is greater than or equal to 5, round up,
otherwise round down. As an example, 11.443 is rounded down to 11.44 and
11.455 is rounded up to 11.46. 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 (QA) measurements as required by the contract
SOW. A run begins with the instrument calibration and is to be completed
within a 24-hour period.
SAMPLE - A portion of material to be analyzed that is contained in single or
multiple containers and identified by a unique sample number.
SAMPLE DELIVERY GROUP (SDG) - A unit within a sample Case that is used to
identify a group of samples for delivery. An SDG is defined by the following,
whichever is most frequent:
"= Each Case of field samples received, or
Each 20 field samples [excluding Performance Evaluation (PE) samples]
within a Case, or
"= Each 7 calendar day period (3 calendar day period for 7 day turnaround)
during which field samples in a Case are received (said period beginning
with the receipt of the first sample in the SDG).
G-7 ILM05.2
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Exhibit G Glossary of Terms (Con't)
IX! In addition, all samples and/or sample fractions assigned to an SDG must
have been scheduled under the same contractual turnaround time.
Preliminary Results have no impact on defining the SDG.
Samples may be assigned to SDGs by matrix (i.e., all soil samples in one SDG,
all water samples in another) at the discretion of the laboratory.
SAMPLE MANAGEMENT OFFICE (SMO) - A Contractor-operated facility operated under
the SMO contract, awarded and administered by USEPA.
SAMPLE NUMBER (EPA SAMPLE NUMBER) - A unique identification number
designated by USEPA for each sample. The EPA sample number appears on the
sample Traffic Report/Chain of Custody Record which documents information on
that sample.
SENSITIVITY - The slope of the analytical curve (i.e., functional relationship
between instrument response and concentration).
SERIAL DILUTION - The dilution of a sample by a factor of 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.
SOP - Standard Operating Procedure.
SOW - Statement of Work.
STANDARD ANALYSIS - An analytical determination made with known quantities of
target analytes.
STOCK SOLUTION - A standard solution which can be diluted to derive other
standards.
TARGET ANALYTE LIST (TAL) - A list of Inorganic Analytes (metals and cyanide)
as designated in Exhibit C.
TIME - When required to record time on any deliverable item, time shall be
expressed as Military Time [i.e., a 24-hour clock (0000-2359)].
TRAFFIC REPORT/CHAIN OF CUSTODY RECORD (TR/COC) - An USEPA sample
identification form filled out by the sampler, which accompanies the sample
during shipment to the laboratory and is used for documenting sample identity,
sample chain-of-custody, and sample receipt by the laboratory.
TUNE - Analysis of a solution containing a range of isotope masses to
establish ICP-MS accuracy, resolution, and precision prior to calibration.
USEPA OERR AOC INORGANIC PROGRAM MANAGER (AOC PM) - The USEPA, OERR AOC
Official who manages the CLP Inorganic Program.
USEPA REGIONAL CLP PROJECT OFFICER (CLP PO) - The Regional USEPA official
responsible for monitoring laboratory performance and/or requesting analytical
data or services from a CLP 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/Chain of Custody Record.
WET WEI'GHT - The weight of a sample aliquot including moisture (undried).
ILM05.2 G-8
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Exhibit G Glossary of Terms (Con't)
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 SOW.
G-9 ILM05.2
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EXHIBIT H
DATA DICTIONARY AND FORMAT
FOR DATA DELIVERABLES IN
COMPUTER-READABLE FORMAT
H-l ILM05.2
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ILM05.2 H-2
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Exhibit H - Data Dictionary and Format for Data Deliverables
in Computer-Readable Format
Table of Contents
Section Page
1.0 USEPA AGENCY STANDARD IMPLEMENTATION 5
1.1 Format Characteristics 5
2.0 RECORD TYPES 7
2.1 Specifications 7
3.0 PRODUCTION RUNS 8
3.1 Specifications 8
3.2 Example 8
4.0 RECORD SEQUENCE 11
4.1 Specifications 11
5.0 FILE/RECORD INTEGRITY 13
6.0 DATES AND TIMES 13
7.0 MULTIPLE VOLUME DATA 13
8.0 DELIVERABLE 14
8.1 Requirements 14
9.0 RECORD LISTING 15
9.1 Production Run First Header Record (Type 10) 15
9.2 Production Run Second Header Record (Type 16) 16
9.3 Mandatory Sample Header Data Record (Type 20 ) 17
9.4 Sample Header Record (Type 21) 22
9.5 Associated Injection and Counter Record (Type 22) 24
9.6 Results Data Record (Type 30) 25
9.7 Instrumental Data Readout (Type 31) 28
9.8 Auxiliary Data Record (Type 32) 29
9.9 QC Limit Record (Type 34 ) 30
9.10 Correction Data Record (Type 35) 31
9.11 Comment Record (Type 90) 32
9.12 Sample Associated Data Record (Type 92 ) 33
H-3 ILM05.2
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ILM05.2 H-4
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Exhibit H Section 1
USEPA Agency Standard Implementation
1.0 USEPA AGENCY STANDARD IMPLEMENTATION
1.1 Format Characteristics
The following constitutes an implementation of the USEPA 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 a Sample Delivery Group (SDG).
Because this implementation is only a subset of the USEPA Agency
Standard, some fields have been replaced by delimiters as place holders
for non-Contract Laboratory Program (CLP) data elements.
1.1.1 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 "|" (ASCII 124). Fields that do not
contain data should be zero length or a blank field (empty with no
space or additional delimiters between the delimiters before and
after the field) with the delimiter as a place holder. For the
purposes of Section 9 of this Exhibit, wherever "blank" is given as
an option under the "Format/Contents" column, it refers to a blank
field as explained above.
1.1.2 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. Values that exceed the maximum length allowed shall
be reported to the maximum possible, maintaining the specified
decimal place and maximum field length restrictions.
1.1.3 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,
including a decimal place 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 rounding rules described in Exhibit B)
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.
1.1.4 USEPA is currently developing a data delivery strategy that may be
used as an alternative to the requirements stated in Exhibit H. This
strategy's intent is to provide a neutral data delivery structure to
the Contractor that will further facilitate the exchange of
analytical information generated under this analytical protocol. The
proposed strategy is intended to accommodate laboratories that
generate data transmission files under multiple data formats. Upon
implementation of this alternate electronic data delivery strategy by
the USEPA and prior to submission of data in alternate'format(s), the
H-5 ILM05.2
-------
Exhibit H Section 1
USEPA Agency Standard Implementation (Con't)
Contractor must first demonstrate its ability to provide electronic
data as stated in this Exhibit H and obtain written permission from
the USEPA for the submission of data in alternate format(s). The
Contractor will receive a written response to its request within 90
calendar days. However, until the implementation of this alternate
electronic data delivery strategy by the USEPA, all electronic data
deliverables must be provided as specified in this Exhibit H.
ILM05.2 H-6
-------
Exhibit H Section 2
Record Types
2.0 RECORD TYPES
2.1 Specifications
The USEPA 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.
2.1.1 This implementation consists of twelve record types that can be
summarized in four groups, designated by the first record type in
each group:
Type
Run Header
Sample Header
Results Record
Comments Record
Type ID Contents
10 Information pertinent to a group of
samples processed in a continuous
sequence; usually several per SDG
20 Sample identifying, qualifying, and
linking information
30 Analyte results and qualifications
90 Free form comments
2.1.2 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.
H-7
ILM05.2
-------
Exhibit H Section 3
Production Runs
3.0 PRODUCTION RUNS
3.1 Specifications
A production run represents a "group" or "batch" of samples that are
processed in a continuous sequence under relatively stable conditions.
Specifically:
3.1.1 Calibration - All samples in a run use the same initial calibration
data. For mercury analyses, samples prepared by a certain method
must be analyzed with calibration and QC standards prepared by the
same method. Therefore, all samples, calibration standards, and QC
standards in a run must be associated with the same Preparation Code
(Type 21 record).
3.1.2 Method number - Constant throughout a run.
3.1.3 Instrument conditions - Constant throughout a run. Results obtained
on different instruments cannot be combined in one run.
3.1.4 Thus, each separate group of analyses on each instrument will consist
of a separate production run, and must be reported in a separate
file.
3.1.5 The run numbers in a Sample Delivery Group (SDG) must be unique; that
is, there shall only be one Run Number "1", only one Run Number "2",
etc. in an SDG.
3.1.6 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 Inductively Coupled Plasma - Atomic Emission
Spectroscopy (ICP-AES) method on 01/01/1999 beginning at 12:02 and
arsenic is later quantitated by the ICP-AES method on 01/01/1999
beginning at 18:06, then the run beginning at 12:02 shall have a
lower run number than the run beginning at 18:06.
3.2 Example
The following is an 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.
20 Acts as a header for the following method and instrument parameters
information. Occurs at least once per run with EPA sample number
equal to "MDL". Analysis year, analysis month, analysis day equal
the year, month and day the Method Detection Limit (MDL) was
computed. Analyte count equals the number of the Type 30 records
that follow.
21 Contains the Preparation Code (field 15) and the
Preparation Date (fields #8, 9, 10) for the MDL. Occurs
at least once per run with each Type 21 record preceded by
the relevant Type 20 record and immediately followed by
its related Type 30 record(s).
30 Contains the Analyte Identifier "C" (field #2), the
Analyte CAS Number (field #3), the MDL Label "U" (field
#20), and the MDL (field #21). Occurs once for each
analyte used in the run.
ILM05.2 H-8
-------
Exhibit H Section 3
Production Runs (Con't)
20
21
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 Contract Required Quantitation Limit (CRQL)
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 or masses 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 and the Analyte
Identifier. 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.
20
21
22
30
35
Contains header information for sample and QC data.
Contains additional information for analytical and instrument QC
samples. Will always be preceded by a Type 20 record.
Contains additional information for analytical samples.
usually follow a Type 21 record.
Will
30 Contains the sample level concentration, true or added
value and QC value for each analyte. Occurs once for
H-9
ILM05.2
-------
Exhibit H Section 3
Production Runs (Con't)
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 or 31 record. For
Inductively Couple Plasma - Mass Spectrometry (ICP-MS),
there are as many Type 31 records as there are isotopes
for the analyte identified on the preceding Type 30
record.
30 Values for the next analyte being measured.
31 Values for the next analyte 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
31 etc.
ILM05.2 H-10
-------
Exhibit H Section 4
Record Sequence
4.0 RECORD SEQUENCE
4.1 Specifications
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.
4.1.1 A Type 16 record must immediately follow the Type 10 record. Further
occurrences of the Type 16 record in the file are not allowed.
4.1.2 The first Type 20 records with EPA sample numbers MDL, LRV, and BCD
are headers for the run-wide method and instrument parameters.
4.1.3 The first Type 20 record of the Type 21, 30 group is a header for the
annually determined Method Detection Limits (MDLs) and must
immediately follow the Type 16 record. A Type 20 record of the Type
21, 30 group must be present for each MDL reported in the run. For
ICP-AES, ICP-MS, and cyanide analyses, an MDL associated with
Preparation Code "NP1" must be present in each run. This MDL shall
be used in the qualification of the data reported for non-prepared
samples and instrument QC analyses (except the distilled Initial
Calibration Verification (ICV) standard for cyanide).
4.1.4 The next Type 20 record of the Type 30, 32, 34 group is a header for
the Linear Range Values (LRVs) and must immediately follow the last
Type 30 record of the Type 21, 30 group that pertains to the MDL.
The linear range values for all methods except the Inductively
Coupled Plasma - Atomic Emission Spectroscopy (ICP-AES) and
Inductively Coupled Plasma - Mass Spectrometry (ICP-MS) methods 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-AES and ICP-MS methods are the quarterly
determined values that are reported on Form XI-IN of the hardcopy.
4.1.5 The next Type 20 record of the Type 30, 35 group is a header for the
ICP-AES Background Correction Data (BCD) and must immediately follow
the last Type 34 record of the Type 30, 32, 34 group that pertains to
the linear range values. This Type 20 record is not required for
methods MS, AV, CV, CA, AS and C (i.e., ICP-MS, mercury, and cyanide
analyses).
4.1.6 These are the only occurrences of the Type 20 records that do not
relate to actual analyses in the run. Therefore, the only fields
that are not blank in these occurrences of the Type 20 record are the
RECORD TYPE ("20"); EPA SAMPLE NUMBER ("MDL", "LRV" and "BCD");
Analysis Year/Year Computed, Analysis Month/Month Computed, Analysis
Day/Day Computed ("YYYY", "MM", "DD"); and ANALYTE COUNT.
4.1.7 A minimum of one Type 30 record must immediately follow the Type 21
record of the Type 21, 30 group with EPA sample number MDL, and the
total number of Type 30 records must be equivalent to the ANALYTE
COUNT on the Type 20 record.
4.1.8 A minimum of one Type 30, 32, 34 group with EPA sample number LRV
must immediately follow the Type 20 record which is preceded by the
last Type 30 record of the final Type 21, 30 group. The information
in each Type 30, 32, 34 group must pertain to one and only one
analyte. The number of Type 30, 32, 34 groups must be equivalent to
the ANALYTE COUNT on the Type 20 record.
H-ll ILM05.2
-------
Exhibit H Section 4
Record Sequence (Con't)
4.1.9 A minimum of one Type 30, 35 group with EPA sample number BCD must
immediately follow the Type 20 record for background correction data
(if required). This Type 20 is preceded by the last Type 34 record
of the final Type 30, 32, 34 group. The information in each Type 30,
35 group must pertain to one and only one analyte. The number of
Type 30, 35 groups must be equivalent to the ANALYTE COUNT on the
Type 20 record.
4.1.10 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 ICP-AES, or the last Type 30, 32, 34 group for
mercury and cyanide analyses. For ICP-MS, the Type 20 record for the
first instrument tune standard analysis must immediately follow the
last Type 30, 32, 34 group and the Type 20 record for the first
instrument calibration standard must immediately follow the last 30,
31 group from the last tune standard analyzed. After the appearance
of these Type 20 records in the file, further occurrences of the Type
32, 34 and 35 records in that file are not allowed.
4.1.11 Each environmental sample, calibration, or Quality Control (QC)
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. The Type 20 record holds a count for the number of analytes
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.
4.1.12 Except for the first Type 20 records (EPA sample numbers MDL, LRV,
BCD) for method ICP-AES and the first two Type 20 records (EPA sample
numbers MDL, LRV) for the methods for ICP-MS, mercury and cyanide
analyses, all Type 20 records should occur in the order of sample
analysis.
4.1.13 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
Forms IA-IN and IB-IN 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 must appear
after the Type 30 record of that analyte, but before the Type 30
record of the following analyte.
4.1.14 The Type 92 record which contains the sample associated data that is
reported at the bottom of Forms IA-IN and IB-IN must appear anywhere
after the Type 22 record for that EPA Field Sample, but before the
Type 20 record of the next sample.
ILM05.2 H-12
-------
Exhibit H Sections 5-7
File/Record Integrity
5.0 FILE/RECORD INTEGRITY
All record types must contain the following check fields to ensure file.
and record integrity:
Remarks
"10" or as appropriate
Record Field Field
Position Length Contents
First Field 2 Record type or
identifier
Last Field. 5 Record sequence number 00000-99999, repeated
as necessary
4 Record checksum1 Four hexadecimal
digits
2 Must contain CR and LF
6.0 DATES AND TIMES
Date or time-of-day information consists of successive groups of digits/
each separated by delimiters. Dates are given in the order YYYY 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. All days shall be given as 01 to 31. All
months shall be given as 01 to 12 (e.g., 01 is January, 02 is February).
7.0 MULTIPLE VOLUME DATA
There is no requirement under this format that all the data from an
entire Sample Delivery Group (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.
lThe checksum is the sum of the ASCII representation of the data on the
record up to the Record Sequence Number (not including the Record Sequence
Number), plus the checksum of the previous record. The sum is taken modulo
65536 (216) and is represented as four hexadecimal digits (i.e., the remainder
of the sum divided by 65536 represented as four hexadecimal digits).
H-13
ILM05.2
-------
Exhibit H Section 8
Deliverable
8.0 DELIVERABLE
8.1 Requirements
The file shall be submitted on IBM-compatible, 3.5 inch, high density
1.44 MB diskettes. The diskettes shall be formatted and recorded using
DOS/Windows Operating Systems. The diskettes shall contain all
information relevant to one and only one Sample Delivery Group (SDG).
An alternative means of electronic transmission may be utilized if
approved in advance by USEPA.
8.1.1 USEPA Agency Standard data from an entire SDG may not fit onto a
single diskette. If a single production run is being split onto
multiple diskettes, then all files shall start with a Type 10 record,
and the multiple Type 10 records for each file of the same production
run shall be identical. Do not split the data from a single sample
onto multiple diskettes.
8.1.2 Information on the diskette must correspond to information submitted
in the hardcopy raw data package and on the hardcopy raw data package
forms. Unused records shall not be included on the diskettes. If
the information submitted in the hardcopy data package forms is
changed, the information in the electronic file (e.g., diskette)
shall be changed accordingly, and a complete electronic deliverable
containing all the information for the SDG shall be resubmitted along
with the hardcopy at no additional cost to USEPA.
8.1.3 Each diskette shall be identified with an external label containing
(in this order) the following information:
Disk Density
File Name(s)
Laboratory Name (optional)
Laboratory Code
Contract Number
Case Number/SDG
NRAS Number (where applicable)
Initial Submission or Resubmission (as applicable) and Date
8.1.4 The format for File Name shall be XXXXXX.I01 to XXXXXX.I99, where
XXXXXX is the SDG identifier, I designates inorganics, and 01 through
99 is the file number.
8.1.5 Dimensions of the label must be in the range of 2-1/2" to 2-3/4" long
by 2" to 2-1/8" wide for a 3-1/2" diskette.
ILM05.2 H-14
-------
Exhibit H Section 9
Record Listing
9.0
RECORD LISTING
The following section provides information for the usage of each of the,
record types. Where specified, labels indicate the nature of the
value(s) that follow on that record. If the value(s) will not be
reported, the label shall be omitted. Listed below is every record type
required to report data from a single Sample Delivery Group (SDG).
9.1 Production Run First Header Record (Type 10)
Use: Each production run will start with a Record Type 10.
MAXIMUM LENGTH
2
1
4
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
YYYY
I
MM
I
DD
I
HH
I
MM
I
CHARACTER 2
I
"ILM05.2" (SOW)
I
CHARACTER
I
CHARACTER
I I I I
CHARACTER
I
CHARACTER
I I
CHARACTER
I
NUMERIC 3
I
NUMERIC
CHARACTER
2Analysis Method Types are:
"P" for ICP-AES
"MS" for ICP-MS
"CV" for Manual Cold Vapor AA
"AV" for Automated Cold Vapor AA
"AS" for Semi-Automated Spectrophotometric
"C" for Manual Spectrophotometric
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.
H-15
ILM05.2
-------
Exhibit H Section 9
Record Listing (Con't)
9.2 Production Run Second Header Record (Type 16)
MAXIMUM LENGTH
2
I
4
1
2
I
2
1
2
1
2
1
1
1
1
1
1
1
1
1
5
4
CONTENTS
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
FORMAT/CONTENTS
"16"
1
YYYY
1
MM
1
DD
1
HH
1
MM
1
"Y" or "N" 4
1
"Y" or "N" 5
1
"Y" or "N" 5
1
"Y" or "N" or "B'
1
NUMERIC
CHARACTER
4Enter "Y" if an auto-sampler is used with equal time and intervals
between analysis.
5These are the answers to the first two questions on the Cover Page of
the hardcopy deliverable. "Y" equals "YES", and "N" equals "NO".
6This is the answer to the third question on the Cover Page of the
hardcopy deliverable. "Y" equals "YES", "B" equals BLANK, and "N" equals
"NO".
ILM05.2
H-16
-------
9.3 Mandatory Sample Header Data Record (Type 20)
MAXIMUM LENGTH
2
1
2
1
12
1
5
1
3
1
3
1
5
1
6
1
4
1
2
1
2
1
2
1
2
2
2
1
5
1
3
1
5
4
CONTENTS
RECORD
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
Exhibit H Section 9
Record Listing (Con't)
FORMAT/CONTENTS
"20"
I
NUMERIC
I
CHARACTER 7
CHARACTER8
I
CHARACTER
I
CHARACTER
I
CHARACTER
I
CHARACTER
I
YYYY
I
MM
I
DD
I
HH
I
MM
II
"G"/"ML"'
I
NUMERIC10
I
NUMERIC
I
NUMERIC
CHARACTER
7EPA Sample Number as it appears on Form XIII-IN of the hardcopy
deliverable except for the first Type 20 records. The first Type 20 record
must have an EPA sample number of "MDL"; after all Type 20 records with an EPA
sample number of "MDL", the next Type 20 record must have an EPA sample number
of "LRV"; for ICP-AES, the Type 20 record following the "LRV" must have an EPA
sample number of "BCD".
"For matrix, "1" equals "WATER" and "F" equals "SOIL". A matrix
identifier ("1" or "F") is required for all EPA sample numbers except "BCD".
9"G" equals grams and "ML" equals milliliters.
10This is the size of the sample at the beginning of the digestion
procedure.
H-17
ILM05.2
-------
Exhibit H Section 9
Record Listing (Con't)
9.3.1 SAMPLE QC CODES LISTING FOR TYPE 20
NOTE: These QC codes appear in the QC code field on the Type 20
record (R20F5). They are used to indicate the type of data that is
being reported.
QCC Name
LRB LABORATORY (REAGENT)
BLANK
LCB LABORATORY CALIBRATION BLANK
LIB LABORATORY INITIAL BLANK
Definition
The Preparation Blank (see
Exhibit G).
The Continuing Calibration Blank
(CCB) (see Exhibit G).
The Initial Calibration Blank
(ICB) (see Exhibit G).
LCM LABORATORY CONTROL
SOLUTION
The Laboratory Control Sample
(LCS) (see Exhibit G).
LD2 LABORATORY DUPLICATE
SECOND MEMBER
This is the second aliquot and
is identified as "D" on Form VI-
IN of the hardcopy.
LVM LABORATORY CALIBRATION
VERIFICATION SOLUTION
LVC LABORATORY CONTINUING
CALIBRATION VERIFICATION
LVD LABORATORY DISTILLED
VERIFICATION SOLUTION
These values are identified as
"Initial Calibration
Verification" (ICV) on Form IIA-
IN of hardcopy.
These values are identified as
"Continuing Calibration
Verification" (CCV) on Form IIA-
IN of hardcopy.
These values are the "distilled
ICV" results for cyanide. Refer
to Exhibit D, Section 12.7.1 for
cyanide.
LSF LABORATORY SPIKED SAMPLE -
FINAL VALUES
These are the "Spiked Sample
Result (SSR)" values of Form VA-
IN of hardcopy.
LDO LABORATORY DILUTED SAMPLE
BACKGROUND (ORIGINAL) VALUES
LDF LABORATORY DILUTED SAMPLE -
FINAL VALUES
These values are the "Initial
Sample Result (I)" values on
Form VIII-IN of hardcopy.
These are the "Serial Dilution
Result(S)" values Form VIII-IN
of hardcopy.
ILM05.2
H-18
-------
Exhibit H Section 9
Record Listing (Con't)
PDO POST-DIGESTION SPIKE
BACKGROUND (ORIGINAL) VALUES
PDF POST-DIGESTION SPIKE
BACKGROUND (FINAL) VALUES
This value is identified as
"Sample Result" (SR) on Form VB-
IN of hardcopy.
This value is identified as
"Spiked Sample Result" (SSR)
Form VB-IN of hardcopy.
on
LPC
CRQL CHECK STANDARD
LSA
LSB
LTS
LABORATORY INTERFERENCE CHECK
SOLUTION A
LABORATORY INTERFERENCE CHECK
SOLUTION AB
LABORATORY TUNE SAMPLE
Laboratory Performance Check
Solution for analysis methods P,
MS, CV, AV, AS, and C (EPA
sample number is CRI##). These
results are reported on Form
IIB-IN of hardcopy.
The results of this solution
analysis (EPA sample number is
ICSAlf) are reported on Forms
IVA and IVB-IN of hardcopy.
The results of this solution
analysis (EPA sample number is
ICSABlt) are reported on Forms
IVA and IVB-IN of hardcopy.
The results of these solution
analyses are reported on Form
XIV-IN of hardcopy.
FRB
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.
FRM PERFORMANCE EVALUATION (PE)
SAMPLE
FLD FIELD SAMPLE
ZZQ NON-SDG SAMPLE
This is a sample of known
composition provided by USEPA
for Contractor analysis and is
used to evaluate Contractor
performance.
This is the sample that is
identified by a unique EPA
sample number on the Traffic
Report/Chain of Custody Record.
This is any sample that is
analyzed and is not part of the
SDG (EPA sample number is
ZZZZZZ).
STB
CALIBRATION STANDARD
This is the instrument
calibration Blank Standard
sample number is SO).
(EPA
H-19
ILM05.2
-------
Exhibit H Section 9
Record Listing (Con't)
STC CALIBRATION STANDARD
STD CALIBRATION STANDARD
This is the instrument
calibration CRQL Standard (EPA
sample number is Sx where x is
the CRQL value of the analyte).
This is the instrument
calibration standard other than
the Blank Standard or the CRQL
Standard (EPA sample number is
S) .
STM
MIORANGE STANDARD
STR
RESLOPE SAMPLE
STL
BASELINE SAMPLE
This is the distilled cyanide
Mid-range Standard (EPA sample
number is MIDRANGE##). Refer to
Exhibit D, Section 10.2.1.1, for
cyanide.
This is the resloping that is
permitted for mercury analysis
(EPA sample number is
RESLOPE**). Refer to Exhibit D,
Section 9.1.5, for mercury.
This is the baseline correction
that is permitted for mercury
analysis (EPA sample number is .
BASELINE**). Refer to Exhibit
D, Section 9.1.5, for mercury.
MDQ
LRQ
METHOD DETECTION LIMIT
LINEAR RANGE VALUE
BCQ
BACKGROUND CORRECTION
These are the annually
determined analyte detection
limits that are reported on Form
IX-IN of hardcopy. (EPA sample
number is MDL).
These are the quarterly
determined values for ICP-AES
and ICP-MS methods that are
reported on Form XI-IN of
hardcopy. For all other
methods, these 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. (EPA
sample number is LRV).
These are the ICP-AES annually
determined interelement
correction factors that are
reported on Forms XA and XB-IN
of hardcopy. (EPA sample number
is BCD).
NOTE: All field samples that are reported on the Traffic Report/Chain
of Custody Record shall contain the QC code "FLD" in Record Type 20
ILM05.2
H-20
-------
Exhibit H Section 9
Record Listing (Con't)
Field Number 5 (R20F5) except when "FLD" is superseded by "FRB"
(Field Blank Sample), "FRM" (PE Sample).
For Matrix Spike and Duplicate sample analysis (Forms VA-IN and VI-IN
of hardcopy), the "Sample" result shall contain the QC code "FLD" in
R20F5, the "Spiked Sample Result" shall contain the QC Code "LSF" in
R20F5, and the "Duplicate" result shall contain the QC code "LD2" in
R20F5.
H-21 ILM05.2
-------
Exhibit H Section 9
Record Listing (Con't)
9.4 Sample Header Record (Type 21)
MAXIMUM LENGTH
2
2
3
2
3
1
6
1
14
1
4
1
2
1
2
2
4
1
2
CONTENTS
RECORD TYPE
Delimiter
LEVEL
Delimiter
PREPARATION CODE
Delimiter
NRAS NUMBER
Delimiter
LAB SAMPLE ID
Delimiter
PREPARATION YEAR
Delimiter
PREPARATION MONTH
Delimiter
PREPARATION DAY
Delimiter
YEAR RECEIVED
Delimiter
MONTH RECEIVED
FORMAT/CONTENTS
"21"
I I
"LOW"/"MED"
I I
CHARACTER11
I
CHARACTER
I
CHARACTER
I
YYYY
MM
I
DD
I I
YYYY
I
MM
"Preparation Codes: A Preparation Code is required for all EPA sample
numbers except "LRV", "BCD", and "TUNE##".
"HW1" - Hotplate/Block digestion for ICP-AES analysis of water samples.
"HW2" - Hotplate/Block digestion for ICP-MS analysis of water samples.
"MW1" - Microwave digestion for ICP-AES analysis of water samples.
"MW2" - Microwave^digestion for ICP-AES analysis of water samples.
"HS1" - Hotplate/Block digestion for ICP-AES analysis of soil samples.
"HS2" - Hotplate/Block digestion for ICP-AES analysis of soil samples.
"MSI" - Microwave digestion for ICP-AES analysis of soil samples.
"CW1" - Preparation for the Manual Cold Vapor AA analysis of water samples.
"CS1" - Preparation for the Manual Cold Vapor AA analysis of soil samples.
"CW2" - Preparation for the Automated Cold Vapor analysis of water samples.
"DW1" - Distillation for the manual and semi-automated spectrophotometric
analysis of water samples.
"DW2" - Midi-distillation for the semi-automated spectrophotometric analysis
of water samples.
"DS1" - Distillation for the manual and semi-automated spectrophotometric
analysis of soil samples.
"DS2" - Midi-distillation for the semi-automated spectrophotometric analysis
of soil samples.
"NP1" - No preparation.
ILM05.2
H-22
-------
Sample Header Record (Type 21)
-------
Exhibit H Section 9
Record Listing (Con't)
9.5 Associated Injection and Counter Record (Type 22)
MAXIMUM LENGTH CONTENTS FORMAT/CONTENTS
2 RECORD TYPE "22"
8 Delimiter I I I I I I I I
5 VOLUME ADJUSTMENT FACTOR NUMERIC15
2 Delimiter I |
8 FINAL VOLUME NUMERIC16
1 Delimiter I
8 DILUTION FACTOR NUMERIC
3 Delimiter I | |
5 PERCENT SOLIDS NUMERIC
1 Delimiter I
5 RECORD SEQUENCE NUMBER NUMERIC
4 CHECKSUM CHARACTER
15This field is used to report any additional volume adjustments in the
preparation method. As an example, the factor of 1.25 that results from the
chloride interference volume adjustment in Preparation Method/Code HW2.
16This is the final volume that is currently reported on Form XII-IN of
the hardcopy.
ILM05.2 H-24
-------
9.6 Results Data Record (Type 30)
MAXIMUM LENGTH
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
10
1
1
1
1
1
10
2
15
1
10
1
5
4
CONTENTS
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, L
Delimiter
QC VALUE
Delimiter
MATRIX SPIKE QC LIMIT QUALIFIER
Delimiter
QC LOWER LIMIT
Delimiter
QC UPPER LIMIT
Delimiter
QC LIMIT QUALIFIER
Delimiter
MDL LABEL
Delimiter
MDL
Delimiter
RAW DATA AVERAGE
Delimiter
RAW DATA %RSD
Delimiter
RECORD SEQUENCE NO.
CHECKSUM
Exhibit H Section 9
Record Listing (Con't)
FORMAT/CONTENTS
"30"
CHARACTER18
1 1
CHARACTER19
I
NUMERIC20'21
I
Ť m n I \\ pi // 2 2
I
NUMERIC
NUMERIC
I I I
NUMERIC
I
I
NUMERIC "
I
NUMERIC "
I
\\ it tr / \\Tjirr26
I
"U"
I
NUMERIC 27
I I
NUMERIC28
I I
NUMERIC
I I
NUMERIC
CHARACTER
H-25
ILM05.2
-------
Exhibit H Section 9
Record Listing (Con't)
FORMAT OF THE RESULTS DATA RECORD (TYPE 30) FOOTNOTES
17"C" (CAS Registry Number) is used for all metals and cyanide.
18The CAS Numbers for metals and cyanide are in Exhibit B, Form IA-IN,
and Table 1 - Inorganic Target Analyte List and Contract Required Quantitation
Limits (CRQLs), in Exhibit C. NOTE: The CAS Numbers for the ICS non-target
interferents are as follows: carbon (7440-44-0); chlorine (7782-50-5);
molybdenum (7439-98-7); phosphorus (7723-14-0); sulfur (7704-34-9), and
titanium (7440-32-6).
19"BDL" means below detection limit.
"NSQ" means there is not sufficient quantity to prepare sample according
specification in Exhibit D; therefore, a smaller sample size is used.
"NAR" means no analysis result required.
"LTC" means less than the CRQL but greater than or equal to the MDL.
"FQC" means failed Quality Control (QC) criteria.
"GTL" means greater than the linear range. The result is reported from a re-
analysis at an appropriate dilution.
"RIN" means that the analysis result was not used to report data in the SDG.
The result is reported from a later re-analysis of the same sample aliquot.
"REX" means that the analysis result was not used to report data in the SDG.
The result is reported from a later re-analysis of a repreparation of the same
sample.
Note that, except for WNAR", none of these codes relieves the Contractor from
reporting a valid result. They only explain why or if the result is
qualified.
20EPA Field Samples reported on Traffic Report/Chain of Custody Record
(QC codes FLD, FRB, FRM) shall have their analytes' results reported to four
decimal places.
^ 21Follow 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
results on Form VI-IN have to be reported to four decimal places. Refer to
Section 9.3.1 for QC codes and definitions.
22"T" stands for an analyte's true value in a solution. This includes
the concentration of all Instrument Calibration Standards for ALL methods of
analysis. "F" stands for an added concentration to a sample such as a pre- or
post-digestion spike.
23Ťpť equals Percent Recovery (%R), Percent Difference (%D), Relative
Percent Difference (RPD), Percent Relative Standard Deviation (%RSD), Percent
Relative Intensity (%RI), or correlation coefficient. "L" equals control
limit for duplicates. The matrix spike sample %R shall be entered on the Type
30 record of the EPA sample number with the "S" suffix (QC code=LSF). The
post digest spike sample %R shall be entered on the T.ype 30 record of the EPA
sample number with the "A" suffix (QC code=PDF). The RPD and the control
limit for duplicates shall be entered on the Type 30 record of the EPA sample
number with the "D" suffix (QC code=LD2). The ICP serial dilutions %D shall
be entered on the Type 30 record of the EPA sample number with the "L" suffix
(QC code=LDF). The average %RSD for ICP-MS tune analyses shall be entered on
the Type 30 record of the last EPA sample number "TUNE#f" (QC code=LTS) in
each run. The %RI for ICP-MS internal standards shall be entered on the Type
30 record of all EPA samples numbers (except "TUNEf#", "ZZZZZZ", "MDL", and
"LRV"). The correlation coefficient for the calibration for mercury and
ILM05.2 H-26
-------
Exhibit H Section 9
Record Listing (Con't)
cyanide analyses shall be reported on the Type 30 record of the EPA sample
number associated with the final standard analyzed in the calibration curve
(immediately preceding the ICV).
2<"N" is the qualifier that is used on Form VA-IN of the hardcopy to
indicate that the matrix or pre-digestion spike sample recovery for an analyte
is not within the specified control limits. The "N" qualifier shall be
entered on the Type 30 record of the EPA sample number with the WS" suffix (QC
code=LSF).
"These are the control limits for the ICV/CCV percent recovery (%R) on
Form IIA-IN, the CRI %R on Form IIB-IN, the ICSA/ICSAB %R on Forms IVA and
IVB-IN, the matrix spike %R on Form VA-IN, and the LCSW %R and the LCSS upper
and lower limits on Form VII-IN. The QC upper and lower limits for the Spike
Sample Recovery shall be entered on the Type 30 record of the EPA sample
number with the "S" suffix (QC code=LSF).
26Ť*Ť is tne qualifier that is used on Form VI-IN 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 VIII-IN 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 (QC code=LD2) The "E" qualifier shall be entered on the
Type 30 record of the EPA sample number with the "L" suffix (QC code-LDF).
"The MDL shall be reported to 2 significant figures for values less
than 10 and to 3 significant figures for values greater than or equal to 10.
MDLs shall be reported in UG/L for water samples, ICV, ICB, CCV, CCB, CRI,
ICSA, ICSAB and MIDRANGE (for cyanide), and any other samples with
concentration results reported in "UG/L". MDLs shall be reported in MG/KG for
soil samples.
28The 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. In addition, the raw data average value
shall always be reported in units of UG/L to a minimum of four decimal places,
regardless of the units the instrument readings are reported in, on record
Type 31. The raw data average value shall not be corrected for dilutions or
volume adjustments.
For Instrument Calibration Standards analyses and Instrument Tune Standards
analyses, the raw data average is not required to be reported.
H-27 ILM05.2
-------
Exhibit H Section 9
Record Listing (Con't)
9.7 . Instrumental Data Readout (Type 31)
MAXIMUM LENGTH CONTENTS FORMAT/CONTENTS
2 RECORD TYPE "31"
1 Delimiter I
1 TYPE OF DATA "W"/"M"29
1 Delimiter I
1 TYPE OF VALUE CHARACTER30
2 Delimiter I|
8 ANALYTE WAVELENGTH/MASS NUMERIC (TO 2 DECIMAL PLACES)
1 Delimiter I
15 FIRST INSTRUMENT VALUE NUMERIC 31
2 Delimiter I |
15 SECOND INSTRUMENT VALUE NUMERIC 31
2 Delimiter I |
15 THIRD INSTRUMENT VALUE NUMERIC 3l
2 Delimiter I|
15 FOURTH INSTRUMENT VALUE NUMERIC 31
2 Delimiter I|
15 FIFTH INSTRUMENT VALUE NUMERIC 31
1 Delimiter I
5 RECORD SEQUENCE NUMBER NUMERIC
4 CHECKSUM CHARACTER
29"
"W" equals wavelength, "M" equals mass.
30"C" equals concentration in ug/L, "B" equals absorbance, "I" equals
intensity (counts per second or equivalent) .
31Used 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. In addition, the instrument values shall
be reported to a minimum of four decimal places.
ILM05.2 H-28
-------
9.8 Auxiliary Data Record (Type 32)
MAXIMUM LENGTH
2
10
2
1
10
4
5
4
CONTENTS
RECORD TYPE
Delimiter
INTEGRATION TIME CODE
Delimiter
INTEGRATION TIME
Delimiter
RECORD SEQUENCE NUMBER
CHECKSUM
Exhibit H Section 9
Record Listing (Con't)
FORMAT/CONTENTS
"32"
I I I I I II III
WT m tt
I
IN SECONDS
I I I I
NUMERIC
CHARACTER
H-29
ILM05.2
-------
Exhibit H Section 9
Record Listing (Con't)
9.9 QC Limit Record (Type 34)
MAXIMUM LENGTH
2
4
8
I
10
1
10
6
5
4
CONTENTS
RECORD TYPE
Delimiter
ANALYTE WAVELENGTH OR MASS
Delimiter
CRQL
Delimiter
LINEAR RANGE VALUE
Delimiter
RECORD SEQUENCE NO.
CHECKSUM
FORMAT/CONTENTS
"34"
I I I I
NUMERIC (TO 2 DECIMAL
PLACES)
I
NUMERIC
I
NUMERIC
I I I I I I
NUMERIC
CHARACTER
ILM05.2
H-30
-------
Exhibit H Section 9
Record Listing (Con't)
9.10 Correction Data Record (Type 35)
MAXIMUM LENGTH CONTENTS FORMAT/CONTENTS
2 RECORD TYPE "35"
1 Delimiter I
3 TYPE OF CORRECTION "ICP"
1 Delimiter I I I I I
9 CAS NUMBER OF INTERFERING ANALYTE CHARACTER
1 Delimiter I
8 ANALYTE WAVELENGTH NUMERIC (TO 2 DECIMAL
PLACES)
1 . Delimiter I
10 CORRECTION FACTOR NUMERIC
1 Delimiter I
5 RECORD SEQUENCE NO. NUMERIC
4 CHECKSUM CHARACTER
H-31 ILM05.2
-------
Exhibit H Section 9
Record Listing (Con't)
9.11 Comment Record (Type 90)
MAXIMUM LENGTH CONTENTS FORMAT/CONTENTS
2 RECORD TYPE "90"
1 Delimiter I
67 ANY COMMENT CHARACTER
1 Delimiter |
5 RECORD SEQUENCE NUMBER NUMERIC
4 CHECKSUM CHARACTER
ILM05.2 H-32
-------
9.12 Sample Associated Data Record (Type 92)
MAXIMUM LENGTH
2
1
9
1
9
1
6
1
6
1
6
1
3
1
5
4
CONTENTS
RECORD TYPE
Delimiter
COLOR BEFORE
Delimiter
COLOR AFTER
Delimiter
CLARITY BEFORE
Delimiter
CLARITY AFTER
Delimiter
TEXTURE
Delimiter
ARTIFACTS
Delimiter
RECORD SEQUENCE NUMBER
CHECKSUM-
Exhibit H Section 9
Record Listing (Con't)
FORMAT/CONTENTS
Ť Q O "
CHARACTER
I
CHARACTER
CHARACTER
CHARACTER
CHARACTER
"YES"/BLANK
I
NUMERIC
CHARACTER
H-33
ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
-------
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 ILM05.2.
Appendix A-l ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
ILM05.2 Appendix A-2
-------
Appendix A Format of Records for Specific Uses
Table of Contents
Section Page
1.0 ICP 5
1.1 ICP-AES 5
1.2 ICP-MS 7
2.0 MERCURY 10
2.1 Start of a Mercury Run for Water Samples with Record Types 10
and 16 and the First Type 20 Records 10
2.2 Mercury Instrument Calibration Standards: Blank (SO) and
Four Other Standards 10
2.3 Spike Sample Recovery and Duplicates Performed on Different
Samples (QC Codes FLD, LSF, FLD, LD2) 11
2.4 Duplicates and Spike Sample Recovery Performed on the Same
Sample (QC Codes FLD, LD2, LSF ) 11
2.5 Initial Calibration Verification (ICV) with LVM QC Code 12
2.6 Laboratory Control Sample (Solid) with LCM QC Code 12
3.0 CYANIDE 12
3.1 Start of a Cyanide Run with Record Types 10 and 16 and the
First Type 20 Records 12
3.2 Cyanide Instrument Calibration Standards: Blank (SO) and Five
Other Standards 12*
3.3 Preparation Blank (Soil) with LRB QC Code 13
3.4 Laboratory Control Sample (Soil) with LCM QC Code 13
3.5 Continuing Calibration Verification (CCV) with LVC QC Code 13
3.6 Spike Sample Recovery and Post Distillation Spike Sample Recovery
Performed on the Same Sample (QC Codes FLD, PDO, LSF, PDF) 13
Appendix A-3 ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
ILM05.2 Appendix A-4
-------
Appendix A
Format of Records for Specific Uses
1.0 ICP
1.1
ICP-AES
1.1.1 Start of an ICP-AES Run with Record Types 10 and 16 and the First Type 20 Records
10|1999|09|17|09|06|P|ILM05.2|ABC|TESLAB||||68-D2-0039|P2||TEST LABSINC.|2|000001879
16|1999|09|17|12|03|Y|Y|Y|N|000012114
20|1|MDL|1|MDQ|
21| | | INP1I I I I I I I I I I I I
30|C|7440-22-4|IUG/L?
30|C|7429-90-5||UG/L|
30ICI7440-39-3I|UG/L|
30|C|7440-41-7||UG/L|
1999|07|15| | | |
I000053CD5
I I
I I I
I I
I I
20|1|MDL|1|MDQ| | | 11999 I 07
21| I | IHW1I| |1999|07|15| I I
30|C|7440-22-4| |UG/L| I I I I
30|C|7429-90-5| |UG/L|I I I I
30|C|7440-39-3| |UG/L| I I I I
30|C|7440-41-7| |UG/L| I I I I
20|1|MDL|F|MDQ||||1999)07
21) | | |HS1| | |1999|07|15| I I
30|C|7440-22-4||MG/KG||||
30|C|7429-90-5||MG/KG||||
30|C|7440-39-3|IMG/KGII|I
30|C|7440-41-7||MG/KG||||
20)1)
30|C|
32) | |
34) | |
30|C|
32) | |
34| | |
30|C|
32) | |
34) | |
30|C|
32) | |
34) | |
LRV) 1
7440-
Mill
1328.
7429-
HIM
1308.
7440-
I I II I
1493.
7440-
Mill
1313.
ILRQIiii1999)07
22-4) |I | I I I
I|IT|5.00||
00 |5|40000|
90-51 I I I I I I
IIITI5.00I
201200110000001
39-31 |I I II I
IIITI5.00I|
40|20|100000|I
41-7| MUM
IIITI5.00II
00121250001
I I I
16
II
I I
I I
I I
I I
15
I I
I000256CDA
I I
I000288BB6
|04|000044B9D
I |U|3.1| Mil 1000065996
I|U|21.8| MMI0000767D1
IIUI11.5I||||I0000875CB
I|U|1.1|||||I0000983C5
||04|0000104B9D
00|0000113CD5
I I IUI3.4I|| || 10000125996
I I |U|22.8| | | I II00001367D1
I||U|12.5|||||I00001475CB
I||U|2.1||||II00001583C5
I|04|000164B9D
OOI00017A212
| | |IUI0.82II I I II00018C248
| | ||U|4.8| |||II00019B321
IIIIUI3.1IMM I00020CE75
|| ||U|0.42|| II II00021A21B
I|04|0002356C2
II II I I0002463D1
000267591
I I I I0002782AD
I00031AB1A
I0002994FB
I I I I I I00030A211
I00032B436
Ml I I I I I I I I I I I I00033C149
I00034CA52
I I I I00035D2DA
20|1|BCD| IBCQI | ||1999|07|01| Mil I 04|0007894FB
30|C|7440-22-4| I I I I I IM II I I I I I I II II I I I00079A20A
35IICPI || | 17439-89-61259.90|-0.0002500 I00080AC9B
35|ICP||||17439-96-5)257.6010.0002200|00081B6F4
30|C|7429-90-5| I I I I I I I I I I I I I I II I II I II I00082C410
35|ICP| | | | |7439-96-5|257.60|0.0004900 I00083CE72
35|ICP|||||7440-62-2|292.40|-0.0419200|00084D8EF
30ICI7440-39-3I I I I I I II I I I I IIM I I I I I I I I00085E605
35|ICP.| | | | |7439-96-5|257. 60|0. 0000600 I 00086F060
30|C|7440-41-7| I I I I I I II II II I I I I II I I II I00087FD73
35|ICP|||||7440-50-8|324.70)0.0046200(000891401
35|ICP| | | | |7439-96-5|257.60|0.0015400 I000901F30
1.1.2 ICP-AES Instrument Calibration Standards, SO and S
20|1|HH|1|STB||20596|MAX123|1999|09|17|09|06||||04|00128D199
21| | | INP1I |STDB11999|09117| | | | |TESLAB| | | I00129DD31
22| | | | | | | | | | |1.0| | | I00130E598
Appendix A-5
ILM05.2
-------
Appendix A
Format of Records for Specific Uses (Con't)
30 | C| 7440-22-4 | III|T|0.0||||||!||||U|3.1||||| (00131F8F5
31|W|I| |328.00|0.0304| |0. 03741 |0. 04001
30|C|7429-90-5| I|||T|0.0|||||||||||U|21
31 | W|I| |308.20|0.0104| | 0.01361 10.01201 |
30|C|7440-39-3| I I I |T|0.0| I I I I I I I I I |U|11
31|W|I| |493. 401-0. 00021 |0. 00021 |0. 00001
30|C|7440-41-7| | | | |T|0.0| I I I I I I I | | |U|1.1| III! I0013751FA
31 1 W|I| 1313.0010.00061 | 0.00021 | 0.00041 | | | I001385C04
| 1001320305
8||||| 1001331697
| 1001342137
5| I | | | I00135348D
| | I001363EA4
20|1|H|1|STD| I 20596 | MAX123 1 1999 | 09 1 17 | 09 |
21| | | INP1I |STD1|1999|09|17| | | | |TESLAB| I | (
22| | | | | | | | | | ll.OU | I00208453C
11) I I |04|00206314E
002073CD5
I I II 1002139157
002149B6E
8)1)11 (00215ADE2
I00216B7EC
5|| | I I I00219E77D
I00220F18F
I I I I I 1002210410
I002220E25
1.1.3 Duplicates, Spike Sample Recovery, and Serial Dilutions Performed on the Same Field Sample
(QC Codes FLD, LDO, LD2, LSF, LDF)
30|C|7440-22-4| | | | |T|5000| I I I I
31|W|I| 1328.0011.9540) | 1.96101
30|C|7429-90-5| | | | |T|1000| III)
31) W|I| 1308.2010.8384) | 0.8378)
30|C|7440-39-3| I | | |T|5000| Mil
31) W|I| 1493.40(1.9460) | 1.9510)
30|C|7440-41-7| | | | |T|5000| MM
31| W|I| 1313.00)0.9924) 10.9910)
1 1 1 1 |U|3.1
1.9660) | I |
1 II 1 IUI21.
0.8440) | | |
1 IMIUIll.
1.9684) | | |
MM IUI1.1
1.0010) | I I
20|1|MAX123|F| OW) |20596IMAX12311999|09117111109||G|1.05 I 08|01568C5FD
21|ILOWIIHS1IIS308233-01I1999I09I14)|1999|08|24|||08)30|01569D451
22)||||||||1200)1.01||91.5|01570DE17
90|STONES)01571E154
92|GREY|GREY| | |MEDIUM)YES I01572EA43
30|C|7440-22-4| |MG/KG|BDL|2.0817| I II I I I I I I I I |U|0.82||1.15671 ||(01573FD12
31|W|C||328.00|4.2000|10.5500)1-1.2800)|||I0157409A5
30ICI7429-90-5) IMG/KG)16227.0101)I I I I IMI I II|U|4.8| 129913.00001 I II015751DCD
31|W|C|(308.20129992.0000)129654.00001130093.00001|||I015762CAO
30|C|7440-39-3||MG/KG|LTC|21.9349| I I I IM MI I I |U|3.1|1105.37001||I01577400C
31|W|C|1493.40)107.2400)1101.6400)|107.23001|||(015784DA6
30|C|7440-41-7| |MG/KG|BDL11.0409| I I I I I I I I I I I |U|0.42| 11.4900) I II01579606A
31|W|C||313.00|1.4900|(1.4900111.49001|||I015806CD9
20|1|MAX123|F| BUS I I 20596 IMAX123 11999 I 09 117 1111 09 I |G| 1.05 | 08 | 01650C630
21|ILOWj|HS1||3308233-01)1999|09|14|11999)08)24)||08|30|01651D484
I|IIUI3.9I11.15671||I01655FC98
I I|I01656092B
I | ||U|23.1|129913.00001 I II016571C09
30093.0000)|||I016582ADC
I I I I|U|14.9| 1105.37001|II016593DCE
2300)I||I016604B68
I I |U|2.0|11.4900) I I I01579606A
I|I015806CD9
22||M II I I I |200|1.0|||91.5|01652DE4A
30|C|7440-22-4||UG/L|BDL|10.00 I I M II I I
31|W|C|1328.00)4.2000)10.5500)1-1.2800
30ICI7429-90-5) IUG/L)129913.00)I I I I I I I
31|W|C|1308.20129992.0000)129654.0000)
30|C|7440-39-3||UG/L|LTC|105.37|||||||
31|W|C|1493.40)107.2400)1101.6400)|107
30|C|7440-41-7| |UG/L|BDL|5.00| I I I I I I I I
31|W|C|1313.00)1.4900)|1.49001|1.49001
20|1|MAX123D|F| QBE I |20596IMAX12311999|091171111111|G|1.04|08|016913BCF
21)ILOW) I HSU|S308233-02|1999|09|14| 11999)08)24)I|08 I 30|016924A23
22)I I I I I I I I 1200)1.0)||90.9|0169353EC
30|C|7440-22-4||MG/KG|BDL|2.1017| I I MII I I II IIUI0.82)10.9600)| |I0169466BE
31|W|C|1328.00)1.6400)11.6300)1-0.3900)|||1016957356
30 1C|7429-90-5|IMG/KG)16622.74061 ||P|6.2||||IMIIU|4.8|131511.0000) ||1016968784
31|W|C|1308.20)31993.0000)131313.0000)131227.0000)|||1016979641
30|C|7440-39-3||MG/KG|LTC|25.1387| | |P|13.6|I I I I I I IIU|3.11 1119.6100) ||I01698AAC5
31|W|C| 1493.40)121.4600)1118.9300)1118.4400) I I I I01699B86C
30|C|7440-41-7||MG/KG|BDL|1.0509 I I I I I I I I II I I |U|0.42|11.5000)I II01700CC13
31|W|C|1313.00)1.5000)11.5000)|1.50001|||I01701D86A
ILM05.2
Appendix A-6
-------
1.2
Appendix A
Format of Records for Specific Uses (Con't)
F| OSS\ | 20596 | MAX123 1 1999 | 09 1 17 1 11 1 14 | | G 1 1 . 01 1 08 | 01730BE3C
. |S308233-03|1999|09|14| 1 1999 | 08 | 24 | | | 08 I 30 | 01731CC90
20011.01 | |91.5|01732D656
!-4| IMG/KG | |10.7212|F|10.82|P|99| | | | | |75|125| |U|0.82| |49.5400| | | (01733EBC7
00148.84001 149.20001 |50. 58001 | | | (01734F8DC
-5| |MG/KG|NAR|6859.9253| I I I I I I I I I I I |U|4.8| 131698.00001 | | I017350E27
20131578.0000) 131766.00001 131750.00001 I I I I017361CF1
'-3| IMG/KGI |326.3539|F|432.83|P|70| | | | |N|75|125| |U|3.1| 11508. 00001
4011524.00001 11504.40001 11495. 60001 | | | (017384171
-7| IMG/KGI |10.4290|F|10.82|P|96| MM |75|125| IUI0.42I 148.19001 | | I0173956E4
00148.19001 |48.2000| | 4 8. 18001 | | | I0174063EB
20|1|MAX123S
21||LOW||HS1
22| | | | | | |
30|C|7440-22
31|W|C|1328.
30|C|7429-90
31|W|C|1308.
30|C|7440-39
31|W|C||493.
30|C|7440-41
31|W|C||313.
20|1|MAX123L|F| nHi| | 20596 IMAX123 11999 | 09 117 111117 |
21)|LOW|||(S308233-04I||||1999|08|24||||(017707255
22| | | I I I I I I I 15.01 | |91.5|017717B8D
|UG/L|BDL|50.00| I II II I IIII
1.45001 (-0.38001 (0.76001 I |
(UG/LI(25575.501 | (PI15II I |
5038.60001(5126.4000115180
|UG/L|LTC|111.30| I IP|6| | | |
22.2600|122.77001(21.75001
|UG/L|BDL|25.00| I I I I I I I I I I
017373339
(08(017696573
30)0)7440-22-4
31|W|C|1328.00
30|C|7429-90-5
31|W|C|(308.20
30|C|7440-39-3
31|W|C|(493.40
30ICI7440-41-7
I017728DDF
|U|3.9| (0.61001
(017739A7B
I I (EIUI23.1I 15115.10001 I I I01774AE69
3000| | | | (01775BCAC
I I I |U|14.9| 122.26001 I I (01776DOAA
I | I01777DDB9
|U|2.0| 10.30001 | | (0173956E4
31|W|C|(313.00(0.19001|0.20001|0.51|||I(0174063EB
ICP-MS
1.2.1 Start of an ICP-MS Run with Record Types 10 and 16 and the First Type 20 Records
10(1999(09117|09|06|MS|ILM05.2|ABC|TESLAB||||68-D2-0039|P2|(TEST LABSINC.(2(000001879
1611999|09 117112|03|Y|Y|YIN I 000012114
20|1|MDL|1|MDQ| | | 1 1999
21| | I INP1I | I | | | I | I (I I
30|C|7440-22-4| (UG/LI
30|C|7429-90-5| IUG/LI
30|C|7440-39-3| IUG/LI
30|C|7440-41-7| IUG/LI
| 07 1 15 | | | I
(00005DD31
MINIMI
II I I Ml II
III III III
IIIIMIII
20|1|MDL|1|MDQ| I I |1999 I 07115 I I I
211| I |HW2| I |1999|07|15|I I I I I(09
30|C|7440-22-4||UG/L|I I I I I I I I I I
30ICI7429-90-5I |UG/L| I I I I I I I II I
30|C|7440-39-3| |UG/L|I IM I II I I I
30|C|7440-41-7| |UG/L|I I II I I I I II
20|1|LRV|
30|C|7440
32 | |
34) |
30|C
32||
34| |
30|C
32||
34| |
30|C
32 | |
34| |
I I04I000044B9D
I| IUI0.40)I I I|1000065996
|||U|12.8|||||I0000767D1
I||U|3.0|||||I0000875CB
|||U|0.44|||||I0000983C5
I|04|000044B9D
OOI00005DD31
I | |U|0.41| |II I 1000065996
I|IUI13.8)1)11I0000767D1
I | |U|4.0| Mil I0000875CB
I||U|0.43|||||I0000983C5
|107
7429
|| | |
|27.
7440
| | | |
|137
7440
| || |
1111
1|LRQ| | I 11999 I 07)15 I I I I I 04 | 0002356C2
-22-4| I M I I I I M M I I I I I I M II I0002463D1
IT | 5 . 00 | | | | 000256CDA
.00|5|40000| MM 1000267591
-90-51 I I I I I II I I II II M I I I II I I I0002782AD
| | |IT|5.00| | M000288BB6
00|200|1000000| MM I0002994FB
-39-3) I I I I I I I I I I II I II II II I II I00030A211
|| IITI5.00I | | I00031AB1A
.00|20|100000| I I I I I00032B436
-41-71 I I I I I I I I I I I I II I I I I I M I I00033C149
|| | IT | 5 . 00 | I II 00034CA52
.0012)25000) I I I I I00035D2DA
1.2.2 ICP-MS Instrument Tune and Calibration Standards, SO and S
20|3|TUNEA1|1|LTS| | 26791 IMCSBOO 1 1999 | 02 I 06 I 20 | 00 | | | |5|000917DD7
Appendix A-7
ILM05.2
-------
Appendix A
Format of Records for Specific Uses (Con't)
21| | | | | ITUNE1I I I I 1 I I ITESLABI I I I000917DD8
22)||||||||||1.0|||I000917DD9
30ICI7440-41-7I | | | |T|100| I I I I I I I I I I
31|M|I|19.0111000001110000011100000
30|C|7439-95-4| ||||T|100|I I I I I I I I I
31|M|I||23.99|79000||79000||790001
31|M|I|124.991100001|10000||100001
31|M|I|125.981110001|110001|110001
30|C|7440-48-4| | | | |T|100| I II I I I | I |
31|M|I||58.93|100000||100000|1100000
30|C|7440-74-6|I I I |T|100|I I I II I I I I
31|M|I||112.90|4000||40001|4000|||
31|M|I|1114.90(960001|960001|96000)
30|C|7439-92-l| | |||T|100|I I I I I I I I I I
31|M|I||205.97|24000||24000||24000|
31|M|11 |206.98|22000|1220001 I 220001
31|M|I|1207.981520001|52000||52000|
I I I I000917DEO
II000917DE1
I||I000914DE2
000917DE3
000917DE4
000917DE5
I I I I000917DE6
I II000917DE7
I | |I000917DE8
000917DE9
I000917DFO
| | |I000917DF1
I000917DF2
I000917DF3
I000917DF4
20|3|TUNEA2|1|LTS| | 26791 (MCSBOO | 1999 | 02 | 06 | 20 | 10 |
211 1 1 1 1 |TUNE2| 1 1 1 1 1 1 ITESLABI 1 1 1000917008
22) I I II I I I I I 11-01 I I I000917DD9
30 |C| 7440-41-7 | I I I |T| 100 | | | I I I I I I I I I
31|M|I| |9.01|100000| 1 100000 I 1 1000001
30|C|7439-95-4| | | | |T|100| I I I I I I I I I I I
31|M|I| |23.99|79000| |79000| |79000| |
31|M|I| 124.99110000) 1100001 |10000| I
31 1 M| 1 1 125.98111000) 1 110001 1 11000 I I
30|C|7440-48-4| | | | |T|100| I I I I I I I I I I
31|M|I| |58.93|100000| (1000001 (100000
30ICI7440-74-6I I I I I T 1 100 | | | I I I I I I I I
31|M|I| (112.90(40001 (40001 (4000) | | |
31|M|I| (114.90(960001 (960001 (960001
30|C|7439-92-l| | | | |T|100| I I I I I I I I I I
31|M|I| 1205.97)240001 (240001 124000)
31 1 M| 1 1 1206.98(22000) | 22000) 1 22000)
31|M|I| 1207.98)52000) 152000) 152000)
|5|000917DD7
1000001||I000917DEO
II000917DE1
I||(000914DE2
000917DE3
000917DE4
000917DE5
100000)||I000917DE6
I | I000917DE7
I | | I000917DE8
000917DE9
I000917DFO
I|II000917DF1
(000917DF2
(000917DF3
(000917DF4
20|3|TUNEA3111LTS| |26791(MCSBOO11999|02|06|20
2ii11111TUNES1111111ITESLABI11iooo9i7DD8
22|I I I I I I I I I|1.0| I I(000917DD9
30|C|7440-41-7| | | | |T|100| I I I I I I | | | I I
31|M|I|19.01(1000001(1000001|100000|
30|C|7439-95-4| | | ||T|100| I I I I I I I M
31|M|I|123.99)79000)179000)179000)
31|M|I||24.99|10000||10000)(100001
31|M|I|125.98)110001(110001(11000)
30|C|7440-48-4|I I I IT)100 I|I I I I I|||
311M|11 (58.93(1000001(1000001(100000
30|C|7440-74-6|| | | |T|100|| II II I I I
31|M|I||112.90|4000|(4000)(4000)|
31|M|I|(114.90(960001(960001(96000
30|C|7439-92-l|| |I|T|100|I I I I I I I I I
31|M|I||205.97|24000||240001124000
31|M|I|(206.98(220001|22000|[22000
31|M|I|1207.9815200011520001(52000
| 20 |
|5|000917DD7
|||(000917DEO
I(000917DE1
I||I000914DE2
000917DE3
000917DE4
000917DE5
| | I000917DE6
I I000917DE7
I | (000917DE8
000917DE9
000917DFO
| | (000917DF1
000917DF2
000917DF3
000917DF4
20|3|TUNEA4|1|LTS| | 26791 IMCSBOO 1 1999 I 02 | 06 | 20 | 30 | | | |
21)111(1 TUNE 4 | | | | | | | | TESLAB I M I 000917DD8
22| | I I I I I I I I 11-01 | | I000917DD9
30ICI7440-41-7) | | | |T|100| I I I I I I I I I I I I I I I I I000917DEO
31 1 M| 1 1 |9.01|100000| (1000001 (1000001 I I I I000917DE1
30|C|7439-95-4| I I I I T 1 100 | | I I I I I I I I I I I I I I I I000914DE2
5|000917DD7
ILM05.2
Appendix A-8
-------
Appendix A
Format of Records for Specific Uses (Con't)
31|M|I||23.99|79000||79000||79000|
31|M|I| 124.99110000] 110000| I 100001
31|M|I|125.98|110001|11000||110001
30 1C|7440-48-41 I I I |T|100| | | | | I I I ||
31|M|I|158.9311000001|100000|1100000
30|C|7440-74-6 I I I I IT1100| | | I I I I I I I I
31|M|I|1112.90140001|40001|4000||||
31|M|I|1114.901960001|96000||960001
30|C|7439-92-l| || | |T|100| I I I I I I I I I I
31|M|I| 1205.971240001|240001 I 240001
31|M|I|1206.98(220001|220001|220001
31|M|I|1207.9815200011520001(520001
000917DE3
000917DE4
000917DE5
I I I I000917DE6
I I I000917DE7
I I I I000917DE8
000917DE9
I000917DFO
I I | I000917DF1
I000917DF2
I000917DF3
I000917DF4
20131TUNEA5|1|LTS||26791IMCSBOO|1999|02|06|20|40
21||||||TUNESi||||||ITESLABI||I000917DD8
22| I I I I I I I I I 11.01 I I(000917DD9
30|C|7440-41-7| || | |T|100|P|0.0| | | | | |
31|M|I|(9.01(1000001(1000001(1000001
30|C|7439-95-4| | | | |T1100|P|0.0| | | |
31|M|I||23.99|79000|1790001(79000)
31|M|I||24.99|10000||10000||10000|
31|M|I|(25.98(110001(110001|110001
30|CI 7440-48-4| || | IT1100|P|0.0| | I I
31|M|I|(58.931100000)1100000)1100000
30 |C| 74-40-74-6) | | | |T| 100 |P| 0. 0 | I I I
31|M|I| (112.90(40001 140001 14000 I I |
31|M|I|(114.90(960001(960001(96000
30 1C|7439-92-11 |1 | |T1100|P|0.0| | I I
31|M|I|(205.97(240001|24000|(24000
31|M|I|1206.98)22000)(22000)(22000
31|M|I|(207.98(520001(520001(52000
|I|5|000917DD7
I I I I I I I I000917DEO
II000917DE1
| | | | | || (000914DE2
000917DE3
000917DE4
000917DE5
I I I I I I I I000917DE6
I | I000917DE7
|||||||I000917DE8
000917DE9
(000917DFO
I I I I | I I I000917DF1
I000917DF2
I000917DF3
I000917DF4
09(061 | | (04I00128D199
I I00129DD31
40) | | | | I00131F8F5
I | (001320305
20(11811II STB||20596|MAX12311999|09117
211 | I INP1I |STDB11999|09 117| | I | ITESLABI
22|| I I I I I I I I U-OI I I I00130E598
30|C|7440-22-4|||I|T|0.0|||||||||||U|0
31|M|I|(107.00(0.03041|0.0374||0.0400|
30|C|7429-90-5| I I I |T|0.0|I I I I I I I I I |U|12.8| MM 1001331697
311M|11 |27.00|0.0104| 10.01361 I 0.01201 | | | (001342137
30|C|7440-39-3| I I I IT|0.0| | | | I I I I I I |U|3.0| MM (00135348D
31|M|I| 1137.001-0.0002) 10.0002) (0.00001 I I | I001363EA4
30|C|7440-41-7|||||T|0.0||(IIIIIIIIU|0.44|||||(0013751FA
31|M|11 (111.0010.0006110.00021 10.0004) | | | (001385C04
_|1|STD||20596|MAX123|1999|09|17|
(NP1I |STD1|1999|09)17| |I I (TESLABI
I I I I I (1.01 | | I00208453C
20(11
211 I I
22|
30|C|7440-22-4| || | |T|5000| (III I I I I|U|0
31|M|I|(107.00(1.95401(1.96101 1.96601|
30|C|7429-90-5 I 1 I I |T|10001 (III I I I I|U|
311M|11 (27.00(0.83841(0.8378) 10.8440) | |
30|C|7440-39-3| |1 | |T|5000| I I I I I I I I(U|
31|M|I|1136.0011.94601(1.95101 1.96841||1
30|C|7440-41-7| | | | |T|5000| MM I I I I(U|
31|M|
09|11| | | (04I00206314E
I | (002073CD5
|111.00|0.9924|(0.9910)
1-00101 I I I I
401 | | | | (002139157
| (002149B6E
12.81 | I I | I00215ADE2
| I00216B7EC
3.0| | I | | I00219E77D
(00220F18F
0.441 | | I I 1002210410
002220E25
1.2.3 Field Samples
| I 20596 IMAX123 11999 | 09 117 | 09 | 06 I I ML 1100 | 04 | 00128D199
21||||HW2||S308233-01|1999|09|17||1999|09|16|TESLAB||09|30|00129DD31
22| | | | | I I 11.25) 150)1.0) I IO.OI00130E598
30ICI7440-22-4) |UG/L|LTC|0.6625| I I I I I I I I I I I |U|0.41| 10.53001 I| (00131F8F5
Appendix A-9
ILM05.2
-------
Appendix A
Format of Records for Specific Uses
(Con't)
(001320305
IUI13.8)145.1000)I I (001331697
I I 1001342137
I IUI4.0)(8.80001||I00135348D
(001363EA4
I|U|0.43|(0.32101||I0013751FA
I001385C04
I 20596IMAX12311999 I 09 117|09|06||ML|20|04|00128D199
21)| | INP1I|S308234-01|1999|09|17|11999)09 116|TESLAB||09|30|00129DD31
22|||||||||(20)1.0)|(O.OI00130E598
31|M|I||107.00|0.5300||0.5300110.53001
30|C|7429-90-5||UG/L|156.37501 I I I I I I I I
31|M|I||27.00|45.1000||45.10001|45.10001
30|C|7440-39-3||UG/L| 111.00001 I I I I I I I I
31|M|I||137.00|8.8000|18.8000)|8. 80001
30|C|7440-41-7| |UG/LIBDL|1.000| I I M I I I
31|M|I||111.00|0.3210||0.3210|(0.32101
30|C|7440-22-4|(UG/DLTC | 0. 5300 |Mill) I
31|M|I|(107.00(0.5300)fo.5300)10.5300)
30|C|7429-90-5|IUG/L)(45.1000111(11(11
31|M|I|(27.00(45.1000)(45.1000)145.1000)
30|C|7440-39-3||UG/LILTC|8.8000|I I I I I I
31|M|I|(137.00(8.8000118.8000)18.8000)
30|C|7440-41-7| |UG/L|BDL|1.000| I I I I I I I
31|M|I|1111.0010.3210110.3210110.32101
I | |U|0.40| (0.53001
(001320305
|U|12.8| (45.10001 |
I | (001342137
I I |U|3.0| (8.8000) |
I001363EA4
I IUI0.44I 10.3210) |
I001385C04
| (00131F8F5
(001331697
I00135348D
I0013751FA
2.0 MERCURY
2.1
Start of a Mercury Run for Water Samples with Record Types 10 and 16 and the First Type 20
Records
10|1999|09|09|08|44|CV|ILM05.2|ABC|TESLAB||||68-D2-0039|M3|(TEST LABS INC.|6(0000018F7
16|1999|09|09|14(34|N|||1000012099
20|1|MDL|1|MDQ||||1999|07|15|
21)|||CW1||11999107(15(1 I III I
30ICI7439-97-6)|UG/L|I I I I II II
I | ) UI000044AEB
(000053CD5
I I I I(UI0.042)|||
I (0000658F4
20|1|LRV|1|LRQ| I I(1999)09|09|
30|C|7439-97-6|I I I I I I I I I I I I I I
32)|||||||||||||(000087D02
34|||(253.70(0.2(51 I I II I00009852D
|1|0000666A6
|| I II0000773CB
2.1.1 Start of a Mercury Run for Soil Samples with Record Types 10 and 16 and the First Type 20
Records
10|1999|09|09|08|44|CV|ILM05.2|ABC|TESLAB||||68-D2-0039|M3|(TEST LABS INC.|6|0000018F7
1611999 I 09|09 114|34|N|I I 1000012099
20|1|MDL|F|MDQ| || |1999|07|16|I I I I |1|000074AEB
21| || |CS1| | |1999|07|16|((III I 09|00|000083CD5
30|C|7439-97-6|IMG/KG I I I I I I I I I I I I I I |U|0.00921 I II I(0000958F4
20|1|LRV|1|LRQ| I I (1999(09(091 I I I I UI0001066A6
30|C|7439-97-6|I I I I I I I I I I I I I I I I I I I I I I (0001173CB
32| || I I| I| | | | | | |I000127D02
34) ||(253.70(0.2(51 I I I II00013852D
2.2 Mercury Instrument Calibration Standards: Blank (SO) and Four Other Standards
20|l|aS|l|STB||20596IMAX12311999 I 09 I 09 I 08 I 44||IUI00010936F
21| || |CS1||OPPB11999 I 09 I 09| ||| |TESLAB| |07|00 I000119FOC
22| || || | | | | | (1.01 | |I00012A773
30|C|7439-97-6| ||| |T|0.0| I I I I I I I I I |U|0.018|10.01221 I|I00013BAD9
31|W|C| 1253.70)0.0122)I I I I I I II00014C4EC
20|1|S0.2|1|STC||20596IMAX123|1999|09|09|08|48|||(1(000150392
21| |||CS1| |0.2PPB|1999|09|09|I I I(TESLAB)I 07|00|00016DF8F
22)|I)||||||11.0)||I00017E7F6
ILM05.2
Appendix A-10
-------
Appendix A
Format of Records for Specific Uses (Con't)
30|C|7439-97-6| I I | |T|0.2| I I I I I I I I I |U|0.018| |0. 08961 | | I00018FB5E
31|W|C| |253.70|0.0896| I I I I I I I 1000190571
| 20596 | MAX123 1 1999 I 09 | 09 | 08 | 53 | | | |1|000201412
21| | | |CS1| |1.0PPB|1999|09|09| I I | |TESLAB| | 07 | 00 | 00021200E
22| | | | | | | | | | |1.0| | | 1000222875
30|C|7439-97-6| | | | |T|1.0| I I I I I I I I I |U|0.018| |1. 01281 | | I000233BDC
31|W|C| 1253.7011.01281 I I I I I I I I0002445EF
|20596|MAX123|1999|09|09|08|57| | | |1|000255495
21| | | |CS1| | 2. OPPB 1 1999 | 09 | 09 | I I I |TESLAB| | 07 | 00 | 000266092
22| | | | | | | | | | |1.0| | | I0002768F9
30|C|7439-97-6| I I I |T|2.0| I I I I I I I I I |U|0.018| |2. 00551 | | I000287C61
31IWICI 1253.7012.0055) I I I I I I I 1000298674
20]1|^E|1|STD| | 20596 | MAX123 1 1999 | 09 | 09 | 09 I 01 1 | | |1|000309513
21| | | |CS1| | 5. OPPB | 1999 | 09 | 09 | | | | |TESLAB| | 07 | 00 | 00031A113
22| | | | | | | | | | |1.0| | | I00032A97A
30 |C| 7439-97-6 | | | | | T | 5 . 0 I P | 0. 9997 | | | | | | | | |U| 0 . 018 | | 4. 99521 | | I00033BCE5
31|W|C| | 253. 70 | 4. 9952 | I I I I! I I I00034C6F8
2.3 Spike Sample Recovery and Duplicates Performed on Different Samples
(QC Codes FLD, LSF, FLD, LD2)
20|1|MAX123|F| OM| | 20596 IMAX123 1 1999 | 09 | 09 1 13 I 20 | I G| 0 .20 1 1 1 002106798
21| | LOW | |CS1| |S308233-01|1999|09|09| |1999|08|24| | | 07 | 00 I 0021175EF
22| | | | | | | | | 110011.01 | I91.5I002127FB4
30|C|7439-97-6| |MG/KG|BDL| 0 . 1093 | I I I I I I I I I I I |U|0. 00921 |0.0049| | | I002159ECO
31|W|C| |253.70|0.0049| I I I I I I I I00216A8E3
20|1|MAX123S|F| DH3I | 20596 IMAX123 1 1999 | 09 | 09 1 13 I 25 I I G| 0.20 1 1 1 00229534B
21| | LOW | |CS1| |S308233-03|1999|09|09| |1999|08|24| | | 07 | 00 | 0023061A2
22| | | | | | | | | |100|1.0| | |91.5|002316B67
30 |C| 7439-97-6 | IMG/KG | | 0. 5664 I F| 0 . 55 | P| 103 | MM | 75 1 125 I I U| 0.00921 1 1.03661 | | I00232807A
31|W|C| |253.70|1.0366| II II | | | I002338A9D
20|1|MAX126|F| 9*31 | 20596 | MAX123 1 1999 | 09 | 09 1 13 | 30 | | G| 0.20 1 1 1 00217B9F5
21| | LOW | |CS1| |S308233-06|1999|09|09| 1 1999 | 08 I 24 | | | 07 | 00 | 00218C84C
22 M M M I I I |100|1.0| | |85.6|00219D211
30|C|7439-97-6| |MG/KG| 11.50531 M M M M M I |U|0. 00921 |2.5771| | | I00222F11D
31|W|C| |253.70|2.5771| M M M I I00223FB40
20|1|MAX126D|F| BOB | | 20596 IMAX123 1 1999 | 09 | 09 1 13 | 35 I I G| 0.20 1 1 1 002240C9D
21| | LOW | |CS1| |S308233-07|1999|09|09| |1999|08|24M I 07 | 00 | 002251AF4
22M M M M I 110011.01 | | 85.1 1 0022624BC
30 |C| 7439-97-61 IMG/KG |BDL| 0 . 1175 | | |P|200| | |L| 0.0383 I | | |*|U| 0.0092| 10.0028 I | | 1002273795
31|W|C| |253.70|0.0028| M M M I I0022841B9
2.4 Duplicates and Spike Sample Recovery Performed on the Same Sample
(QC Codes FLD, LD2, LSF)
20|1|MAX126|F| fffl!| | 20596 IMAX123 1 1999 | 09 | 09 1 16 1 10 | | G| 0 .20 1 1 1 002106798
211 ILOWI |CS1| |S308233-06|1999|09|09| |1999|08|24| | | 07 | 00 I 0021175EF
22 M M M M M 100 1 1 . 0 M I 91 . 5 | 002127FB4
30|C|7439-97-6| |MG/KG| 10.64291 M I M M M M |U|0. 00921 |1. 17651 | | I002159ECO
31|W|C| | 253. 70 | 1.1765 | M M M I I00216A8E3
20|1|MAX126D|F| GEB I | 20596 IMAX123 1 1999 | 09 | 09 1 16 1 15 | |G| 0 . 20 1 1 1 002240C9D
211 ILOW) |CS1| |S308233-07|1999|09|09| |1999|08|24| | | 07 | 00 | 002251AF4
22|||MIIIII100|1.0||| 90. 9 | 0022624BC
30 |C | 7439-97-6 | IMG/KG | | 0.23421 | | P | 94 || | L | 0 . 0364 I | | |*|U| 0.00921 | 0.42861 | | 1002273795
31|W|C| | 253. 70 | 0.4286 | I M I I I I I0022841B9
Appendix A- 11 ILM05.2
-------
Appendix A
Format of Records for Specific Uses (Con't)
20|1|MAX126S|F| BHS| |20596IMAX12311999|09|09116|20 I IGI 0.2011100229534B
21||LOW||CS1||S308233-08|1999|09|09||1999|08|24|||07|00|0023061A2
22|||||||||110011.01|I91.5I002316B67
30 1C I 7439-97-6||MG/KG||0.9710|F|0.55|PI 60|||||N|751125 I|U|0.0092111.7769|||I00232807A
31|W|C|1253.7011.77691 I I I I I I II002338A9D
2.5 Initial Calibration Verification (ICV) with LVM QC Code
20|l|ICVlA|l|iIBB51| | 20596 IMAX123 11999 | 09 | 09 | 09 | 06 | | | |1|00035D687
21||||CS1||ICV-5|1999|09|09|||07|00|ICF(0791)||07|00|00036E25E
22||I||||||||2.0|||I00037EAC6
30|C|7439-97-6||UG/L|| 4.91|T|4.9|P|100 |I I I I |80.01120.01|U|0.018|12.45591 I I I00038FFDO
31|W|C||253.70|2.4559|I I I I I I II0003909FC
2.6 Laboratory Control Sample (Solid) with LCM QC Code
20|1|LCSSC3|F| OSS\ I 20596IMAX12311999 I 09|09112 I 24| |G|0.20111001256DBA
21||||CS1||LCSHG|1999|09|09|||||QAL-0287||07|00|001267B1B
22||||I||||110011.01||1001278443 ,
30|C|7439-97-61|MG/KG||4.6|T|4.2|P|110||||||2.8|6.0||U|0.0092||9.20001||I00128996D
31|W|C| |253.70|2.7719| I I I I I I I I00129A39A
3.0 CYANIDE
3.1 Start of a Cyanide Run with Record Types 10 and 16 and the First Type 20 Records
10|1999|09|01|14|09|AS|ILM05.2|ABC|TESLAB| | | |68-D2-0039|C11 I TEST LABS INC.|7|00000189C
1611999|09 I 01115|03|Y|||1000012033
20|1|MDL|1|MDQ| |||1999|07|15| I I I I|1|000044A74
21|||INP1I||1999|07|15|||||||10|30|000053CD5
30ICI57-12-5IIUG/LII I I I I I I I I I I I I IU11.7||||||0000656DC
20|1|MDL|1|MDQ|| ||1999|07|15|I I I I|1|000044A74
211|| |OW11 |11999|07115||||||110|30 I000053CD5
30|C|57-12-5|IUG/LII I I I I I I I I I I I I |U|1.8| I I I I I0000656DC
20|1|MDL|F|MDQ|I||1999|07|16|MM|1|000044A74
21||| |DS2| | |1999|07|16|IM MI 07|45|000053CD5
30ICI57-12-5I (MG/KGI I I I I I M I I I I I I |U|0.092| MM I0000656DC
20|1|LRV|1|LRQ| I I|1999|09|01| MM 11)000066486
30|C|57-12-5| M M M M M M M M M M M I000076FDA
32M I I I I I I I |IT|45.00| | | 1000087917
34| | ! 1620.00110(4001 MM 1000098169
3.2 Cyanide Instrument Calibration Standards: Blank (SO) and Five Other Standards
20|1|SH|1|STB||20596IMAX12311999|09|01114|09|I I 111000108FA1
21 M I INPII | OPPBI M M 11 ITESLABI 11 |OOOH9B3E
22M M M M M ll.OM I I00012A3A5
30|C|57-12-5|||||T|0.0|||||||||||U|1.7||0.35431||I00013B48B
31|W|C||620.00|0.3543|M M MII00014BD34
20|l|Smil|STC||20596 IMAX12311999|09|01114110MI UI00015CB95
21M I INPII I10PPBI I I I M I ITESLABI I I I00016D763
22| M I I I II M 11-01||I00017DFCA
30|C|57-12-5| | | | ITI10.0I I I I M I I I I |U|1.7| 111.17001 | | I00018FOD2
31|W|C| |620.00|11.1700|IMI I I I(00019F97B
20|1|SEH|1|STD||20596 IMAX12311999|09|011141111| | |1|0002007EO
21M iINPII14OPPBI111111ITESLABI111000211331
22||M|| M I I|1.0|I II000221C18
ILM05.2 Appendix A-12
-------
Appendix A
Format of Records for Specific Uses (Con't)
30 |C| 57-12-5 | ||||T|40.0|||||||||||U|1.7| | 38. 40001 | | I000232D23
31|W|C| |620.00|38.4000| I I I I M I I0002435CC
20| 1| am 11 1 STD | I 20596 | MAX123 1 1999 | 09 | 01 1 14 1 12 | | | UI00025445F
211 | | INPII IIOOPPBI i i i | | | ITESLABI i i I00026505D
22| I I I I I I I I I 11.01 I I I0002758C4
30 |C| 57-12-5 I I I I IT| 100.01 | | | | | | | | I IU |1.7| | 99. 7400) | | | 000232D23
31 | W|C| |620.00|99.7400| | I | | | | I I0002972A5
20|1|EBBEI|1|STD| | 20596 | MAX123 1 1999 | 09 I 01 1 14 1 12 | | | |1|000308139
211 1 1 INPII I200PPB) 1 1 1 1 1 1 ITESLABI 1 1 IOOOSISDSS
22| | | I I II I I I 11.01 | | I00032959F
30|C|57-12-5| | | | |T|200.0| I I I I I I I I I I U 1 1 . 7 | |201.3000| | | | 00033A6D8
31|W|C| |620.00|201.3000| I I I I I I I I00034AF81
20|1|^EE|1|STD| | 20596 IMAX123 1 1999 | 09 | 01 1 14 1 13 I I | |1|00035BE18
211 i i INPII 1400 PPBI i i i i i i ITESLABI i i I00036CA19
22| I I I I I I I I I 11.01 I I I00037D280
30 |C | 57-12-5 | I I I |T| 400. 0| P| 1.0000 I ||||III|U|1.7| | 399. 50001 | | | 00038E3BB
31|W|C| |620.00|399.5000| I I I I I I I I00039EC64
3.3 Preparation Blank (Soil) with LRB QC Code
20|1|PBSD1|F|BSB| I 20596 (MAX123 1 1999 | 09 | 01 1 14 | 23 | |G| 1 . 00 1 1 1 000928FAO
21| | | |DS2| | PB 1 1999 | 08 | 30 | Mill I 08 | 30 | 000939A40
221 I | | | | | | | 15011.01 | | I00094A30C
30|C|57-12-5| |MG/KG|BDL|1.0000| I I I I I I I I I I I |U|0.092| | -0.00301 I I I 00095B433
31|W|C| | 620. 00 | -0.0030 | I I I I I I I I00096BE6F
3.4 Laboratory Control Sample (Soil) with LCM QC Code
20| HLCSSD1 |F| BSBI | 20596 IMAX123 | 1999|09|01|14|24| |G| 1.00| H00097CF4D
21| | | |DS2| |LCSCN|1999|08|30| | I I IQAL-06891 | 08 I 30 | 00098DCBO
22| | | | | | | | | 150)1.0) | | I00099E57C
30 | C| 57-12-5 | IMG/KG | |5.0|T|5.6|P|89||||||4.3|6.9||O|0.092| 1 100. 09331 | | I00100F89B
31|W|C| |620.00|100.0933| I I I I I I I 1001010315
3.5 Continuing Calibration Verification (CCV) with LVC QC Code
20|l|CCVll|l|flHS| | 20596 | MAX123 1 1999 | 09 | 01 1 14 | 30 | | | |1|0015045A3
211 1 1 INPII 1200 PPBI i M 1 1 1 ITESLABI 1 1 iooisi5iA2
22| I I I I I I I I I 11.01 I I I001525A09
30 |C| 57-12-5 | IUG/LI 1 188 . 48 | T | 200 . 0 I P I 94 | | I I I | 85. 0 1 115.01 |U| 1.7 | 1 188. 47721 | | I001536E87
31|W|C| 1620.00)188.47721 I I I I I I I 1001547916
3.6 Spike Sample Recovery and Post Distillation Spike Sample Recovery Performed on the Same
Sample (QC Codes FLD, PDO, LSF, PDF)
20|1|MAX123|F| OTWI | 20596 IMAX123 I 1999 | 09 I 01 1 14 | 35 | |G| 1 . 06 | 1 1 001955D8E
21| |LOW| |DS2| |S308233-01|1999|08|30| |1999|08|24| | | 08 | 30 | 001966BDF
22| | | | | | | | | I50|1.0| | |71.0|001977578
30|C|57-12-5| |MG/KG|LTC|0.2952| I I I I I I I I I I I |U|0.092| |4. 44411 | | 1002009309
31 |W|C | | 620.00 | 4. 4441| | | | | I I I I002019D4B
20|1|MAX123|F| S3S| | 20596 IMAX123 1 1999 I 09 I 01 1 14 | 35 | | G| 1 . 06 1 1 1 00202AE62
21| | LOW | |DS2| |S308233-01|1999|08|30| |1999|08|24| | | 08 | 30 | 00203BCB3
22| | | | I I I I I I50|1.0| | |71.0|00204C64C
30ICI57-12-5I |UG/L|LTC|4.44| I I I I I I I I I I I IUI1.4I |4. 44411 | | | 00207E3DD
31|W|C| |620. 00|4.4441| I I I I I I I I 00208EE1F
20|1|MAX123S|F| 0331 | 20596 IMAX123 | 1999 I 09 I 01 1 14 | 36 | | G| 1 .02 1 1 1 00209FF7A
21| | LOW | |DS2| |S308233-02|1999|08|30| |1999|08|24| | | 08 | 30 | 002100DCB
22) | | | | | | | | I50|1.0| | |71.0|002111767
Appendix A-13 ILM05.2
-------
Appendix A
Format of Records for Specific Uses (Con't)
30|C|57-12-51 IMG/KG||4.6341|F|6.90|P|63|| || |N|75|125| |U|0.0921167.1210 I I||0021228D6
31|W|C||620.00|67.1210|I I I I I I I 1002133324
20|1|MAX123A|F| 13331 | 20596IMAX12311999 I 09|01114|37||G|1.061110021444AD
21||LOW|| ||S308233-03|1999|08|30||1999|08|24| I I II0021552FE
22| | | | ||| || 15011.01 I|71.0|002165C98
30|C|57-12-5| IOG/LI|21.23|Ft 20.0 IP|84||I I I|| ||U11.4||21.2279|||I0021770CO
31|W|C||620.00|21.2279|I I I I II I I002187B4E
ILM05.2 Appendix A-14
-------
APPENDIX B - Modified Analysis
Appendix B-l ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
ILM05.2 Appendix B-2
-------
Appendix B - Modified Analysis
Table of Contents
Section page
1.0 SCOPE AND APPLICATION 5
2.0 SUMMARY OF METHOD 5
3.0 DEFINITIONS 5
4.0 INTERFERENCES 6
4.1 Spectral Interferences 6
4.2 Nonspectral Interference s 7
5.0 SAFETY 7
6.0 EQUIPMENT AND SUPPLIES 8
6.1 Glassware/Labware 8
6.2 Atomic Absorption Spectrophotometer 8
7.0 REAGENTS AND STANDARDS 9
7.1 Reagents 9
7.2 Standards 9
8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE 11
8.1 Sample Collection and Preservation 11
8.2 Procedure for Sample Storage 11
8.3 Procedure for Sample Digestate Storage 11
8.4 Contract Required Holding Time 11
9.0 CALIBRATION AND STANDARDIZATION 12
9.1 Instrument Operating Conditions 12
9.2 Graphite Furnace Atomic Absorption (GFAA) Instrument
Calibration Procedur e 12
10.0 PROCEDURE 13
10.1 Sample Preparation 13
10.2 Sample Analysis 14
11.0 DATA ANALYSIS AND CALCULATIONS 16
11.1 Water/Aqueous Sample Calculation 16
11.2 Soil Sample Calculatio n 16
11.3 Corrections For Sample Dilutions 17
12.0 QUALITY CONTROL 17
13.0 METHOD PERFORMANCE 17
14.0 POLLUTION PREVENTION 17
15.0 WASTE MANAGEMENT 17
16.0 REFERENCES 17
17.0 TABLES/DIAGRAMS/FLOWCHARTS 17
Appendix B-3 ILM05.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
ILM05.2 Appendix B-4
-------
Appendix B Sections 1-3
Scope and Application
MODIFIED ANALYSIS
The Contractor may be requested by USEPA to perform modified analyses. These
modifications will be within the scope of this SOW and may include, but are
not limited to, analysis of additional analytes and/or lower quantitation
limits. These requests will be made by the USEPA Regional CLP Project Officer
(CLP PO), USEPA OERR Analytical Operations/Data Quality Center (AOC) Inorganic
Program Manager (PM), and USEPA Contracting Officer (CO) in writing, prior to
sample scheduling. If the Contractor voluntarily elects to perform these
modified analyses, these analyses will be performed with no increase in per
sample price. All contract requirements specified in the SOW/Specifications
will remain in effect unless the USEPA CO provides written approval for the
modification(s) and a waiver for associated defects. The USEPA CO approval
must be obtained prior to sample scheduling.
GRAPHITE FURNACE ATOMIC ABSORPTION METHOD
1.0 SCOPE AND APPLICATION
This method is a graphite furnace atomic absorption spectroscopy
procedure that is used to analyze water, sediment, sludge, and soil
samples taken from hazardous waste sites. The following metals:
arsenic, lead, selenium, and thallium that are contained in the Target
Analyte List (TAL) in Exhibit C may be quantitated by the Graphite
Furnace Atomic Absorption (GFAA) method.
2.0 SUMMARY OF METHOD
Water and soil samples are treated with acids and heat to solubilize the
metals present. These digestates are then analyzed for trace metals by
the Graphite Furnace Atomic Absorption (GFAA) spectroscopic technique.
In this technique, a tube of graphite is located in the sample
compartment of the Atomic Absorption (AA) spectrometer, with the light
passing through it. A small volume of sample solution is quantitatively
placed into the tube, normally through a sample injection hole located
in the center of the tube wall. The tube is heated through a programmed
temperature sequence until finally the analyte present in the sample is
dissociated into atoms and atomic absorption occurs.
3.0 DEFINITIONS
See Exhibit G for a complete list of definitions.
Appendix B-5 ILM05.2
-------
Appendix B Section 4
Interferences
4.0 INTERFERENCES
Several types of interference effects may contribute to inaccuracies in
the determination of trace elements in water and soil/sediments.
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 milligrams per Liter (mg/L). In addition,
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.
Interferences from the Graphite Furnace Atomic Absorption (GFAA)
technique can be divided into two broad categories, spectral and
nonspectral interferences. Spectral interferences are those resulting
from light absorption by molecules or by atoms other than those of the
analyte element; that is, spectral interference exists if the atomic
absorption profile of an element overlaps the emission line of another.
Nonspectral interferences are those which affect the production or
availability of analyte atoms which create the measured atomic
absorption.
4.1 Spectral Interferences
4.1.1 Emission Interference - this interference arises when the intense
light emitted by the hot graphite tube reaches the instrument's light
detector, the Photomultiplier Tube (PMT). This problem is manifested
by increased signal variability (noise) which degrades analytical
performance. In severe circumstances, emission interference may
temporarily blind the PMT, resulting in erratic, meaningless readings
at atomization.
4.1.2 Background Absorption - this is the most severe spectral
interference encountered with graphite furnace analyses. Background
absorption is a nonspecific attenuation of light at the analyte
wavelength caused by matrix components in the sample. Unlike atomic
absorption, background absorption is broad band, sometimes covering
tens or even hundreds of nanometers. This broad band absorption
normally is due to molecular absorption or light scattering caused by
undissociated sample matrix components in the light path at
atomization. Since background absorption is broad band, the chance
of overlap with a desired analyte wavelength is significant.
4.1.3 Emission interference is controlled by primarily by spectrometer
optical design. Techniques for controlling and reducing background
absorption include matrix modification (sample treatment) and optical
background correction. Through matrix modification, a reagent or
"matrix modifier" is added to the sample or standard. The matrix
modifier is selected to generate either an increased matrix
volatility or decreased analyte volatility. One type of background
correction, Zeeman, can correct for higher and more spectrally
complicated background absorption and provide more precise and
accurate analytical results. Zeeman background correction uses the
principle that the electronic energy levels of an atom placed in a
strong magnetic field are changed thereby changing the atomic
spectra; the spectral nature of background absorption, on the other
hand is unaffected by a magnetic field.
ILM05.2 Appendix B-6
-------
Appendix B Sections 4 & 5
Safety
4.2 Nonspectral Interferences
In order for atomic absorption to occur, free atoms of the analyte
element must be present in the spectrometer light path. Nonspectral
interferences result when diverse components in the sample matrix
inhibit the formation of free analyte atoms. An often used approach to
compensate for nonspectral interferences is known as the "Method of
Standard Additions".
5.0 SAFETY
See Sectioq 1.14 in Exhibit D - Introduction to Analytical Methods.
Appendix B-7 ILM05.2
-------
Appendix B Section 6
Equipment and Supplies
6.0 EQUIPMENT AND SUPPLIES
Brand names, suppliers, and part numbers are for illustrative purposes
only. No endorsement is implied. Equivalent performance may be
achieved using equipment and supplies other than those specified here,
however, a demonstration of equivalent performance meeting the
requirements of this Statement of Work (SOW) is the responsibility of
the Contractor. The Contractor shall document any use of alternate
equipment or supplies in the Sample Delivery Group (SDG) Narrative.
6.1 Glassware/Labware
6.1.1 250 milliliter (mL) beaker or other appropriate vessel
6.1.2 Watch glasses
6.1.3 Funnels
6.1.4 Graduated cylinders
6.1.5 Various volumetric flasks (Type A)
6.1.6 Thermometer that covers a range of 0-200°C
6.1.7 Whatman No. 42 filter paper or equivalent
6.1.8 Hot plate, block digester, or other heating source capable of
maintaining 92-95°C
6.1.9 Balances - Analytical Balance, 300 gram (g) capacity, and minimum
ą0.01 g.
6.2 Atomic Absorption Spectrophotometer - with graphite furnace atomizer
and background correction. Hollow Cathode Lamp (HCL) and/or
Electrodeless Discharge Lamp (EDL)."
ILM05.2 Appendix B-8
-------
Appendix B Section 7
Reagents and Standards
7.0 REAGENTS AND STANDARDS
7.1 Reagents
Acids used in the preparation of standards and for sample processing
must be ultra-high purity grade or equivalent. (Redistilled acids are
acceptable.)
7.1.1 Reagent water - The purity of this water must be equivalent to ASTM
Type II water (ASTM D1193-77). Use this preparation for all
reagents, standards, and dilutions of solutions.
7.1.2 Nitric acid - Concentrated (specific gravity 1.41).
7.1.3 Nitric acid, 5% (v/v) - Add 50 milliliters (mL) cone. HNO 3 to 500 mL
reagent water; dilute to 1 Liter (L).
7.1.4 Hydrochloric acid - Concentrated (specific gravity 1.19).
7.1.5 Hydrogen peroxide (30%)
7.1.6 Matrix Modifiers
7.1.6.1 Ammonium Phosphate solution (40%): Dissolve 40 grams (g) of
ammonium phosphate, (NH4)2PO4 (analytical reagent grade) in reagent
water and dilute to 100 mL.
7.1.6.2 Calcium Nitrate solution: Dissolve 11.8 g of calcium nitrate,
Ca(N03)2 =ť 4H2O (analytical reagent grade) in reagent water and
dilute to 100 mL. 1 mL - 20 mg Ca.
7.1.6.3 Lanthanum Nitrate solution: Dissolve 58.64 g of American Chemical
Society (ACS) reagent grade 2. La2 O3 in 100 mL cone. HNO3 and
dilute to 1000 mL with reagent water. 1 mL = 50 mg La.
7.1.6.4 Nickel Nitrate solution, 5%: Dissolve 24.780 g of ACS reagent
grade Ni(NO3)2 '*' 6H20 in reagent water and make up to 100 mL.
7.1.6.5 Nickel Nitrate solution, 1%: Dilute 20 mL of the 5% nickel nitrate
to 100 mL with reagent water.
7.2 Standards
7.2.1 Introduction
The Contractor must provide all standards to be used with this
contract. These standards may be used only after they have been
certified according to the procedure in Exhibit E, Section 8.0. The
Contractor must be able to verify that the standards are certified.
Manufacturer's certificates of analysis must be retained by the
Contractor and presented upon request.
7.2.2 Stock Standard Solutions
7.2.2.1 Stock standard solutions may be purchased or prepared from ultra
high purity grade chemicals or metals. All salts must be dried
for 1 hour at 105"C unless otherwise specified.
(CAUTION; Many metal salts are extremely toxic and may be fatal if
swallowed. Wash hands thoroughly after handling.) Typical stock
solution preparation procedures follow.
Appendix B-9 ILM05.2
-------
Appendix B Section 7
Reagents and Standards (Con't)
7.2.2.2 Arsenic solution, stock [1 mL = 1 mg As (1000 mg/1)] - Dissolve
1.320 g of As2O3 in 100 mL of reagent water containing 0.4 g NaOH.
Acidify the solution with 20 mL cone. HNO 3 and dilute to 1 L.
7.2.2.3 Lead solution, stock [1 mL = 1 mg Pb (1000 mg/L)] - Dissolve 1.599
g of Pb(NO3)2 in reagent water. When solution is complete,
acidify with 10 mL of cone. HNO 3 and dilute to 1 L with reagent
water.
7.2.2.4 Selenium solution, stock [1 mL = 1 mg Se (1000 mg/L)] - Dissolve
0.3453 g of H2Se03 (actual assay 94.6%) in reagent water and make
up to 2.00 mL.
7.2.2.5 Thallium solution stock [1 mL - 1 mg Tl (1000 mg/L)] - Dissolve
1.303 g of T1N03 in reagent water. Add 10 mL of cone, nitric acid
and dilute to 1 L with reagent water.
7.2.3 Working Standards
7.2.3.1 Secondary Dilution Standards
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". 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.
7.2.3.2 Calibration Blank
Prepared by diluting 1 mL of (1+1) HNO 3 and 2 mL 30% H202 to 100 mL
with reagent water.
ILM05.2 Appendix B-10
-------
Appendix B Section 8
Sample Collection, Preservation, and Storage
8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE
8.1 Sample Collection and Preservation
All samples must be collected in glass or polyethylene containers.
Water/aqueous samples must be preserved with nitric acid to pH less than
2 immediately after collection. All samples must be iced or
refrigerated at 4"C (ą2"C) from the time of collection until digestion.
8.1.1 Dissolved Metals
For the"determination of dissolved metals, the sample must be
filtered through a 0.45 micrometer (pm) pore diameter membrane filter
at the time of collection or as soon as possible. Use a portion of
the sample to rinse the filter flask, discard this portion, and
collect the required volume of filtrate. Preserve the filtrate with
nitric acid to pH less than 2 immediately after filtration.
8.2 Procedure for Sample Storage
The samples must be protected from light and refrigerated at 4"C (ą2°C)
from the time of receipt until 60 days after delivery of a complete,
reconciled data package to USEPA. After 60 days the samples may be
disposed of in a manner that complies with all applicable regulations.
8.3 Procedure for Sample Digestate Storage
Sample digestates must be stored until 365 days after delivery of a
complete, reconciled data package to USEPA.
8.4 Contract Required Holding Time
The maximum holding time for metals is 180 days from Validated Time of
Sample Receipt (VTSR).
Appendix B-ll ILM05.2
-------
Appendix B Section 9
Calibration and Standardization
9.0 CALIBRATION AND STANDARDIZATION
9.1 Instrument 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. The Method Detection
Limit (MDL), precision, and interference effects must be investigated
and established for each individual analyte line on that particular
instrument. All measurements must be within the instrument calibrated
range. 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 (QC) data
confirming instrument performance and analytical results.
9.2 Graphite Furnace Atomic Absorption (GFAA) Instrument Calibration
Procedure
9.2.1 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.
9.2.2 Calibration standards shall be prepared fresh daily or each time an
analysis is to be made and discarded after use. 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 CRQL. The calibration standards shall be prepared using
the same type of acid or combination of acids and at the same
concentration as will result in the samples following sample
preparation.
9.2.3 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.
ILM05.2 Appendix B-12
-------
Appendix B Section 10
Procedure
10.0 PROCEDURE
10.1 Sample Preparation
10.1.1 If insufficient sample amount (less than 90% of the required amount)
is received to perform the analyses, the Contractor shall contact
Sample Management Office (SMO) to inform them of the problem. SMO
will contact the Region for instructions. The Region will either
require that no sample analyses be performed or will require that a
reduced volume be used for the sample analysis. No other changes in
the analyses will be permitted. The Contractor shall document the
Region's decision in the Sample Delivery Group (SDG) Narrative.
10.1.2 If multiphase samples (e.g., two-phase liquid sample, oily
sludge/sandy soil sample) are received by the Contractor, the
Contractor shall contact SMO to apprise them of the type of sample
received. SMO will contact the Region. If all phases of the sample
are amenable to analysis, the Region may require the Contractor to do
any of the following:
00 Mix the sample and analyze an aliquot from the homogenized
sample.
'-*1 Separate the phases of the sample and analyze one or more of
the phases, separately. SMO will provide EPA sample numbers
for the additional phases, if required.
=*= Do not analyze the sample.
10.'1.2.1 If all of the phases are not amenable to analysis (i.e., outside
scope), the Region may require the Contractor to do any of the
following:
'*' Separate the phases and analyze the phase (s) that is (are)
amenable to analysis. SMO will provide EPA sample numbers
for the additional phases, if required.
'** Do not analyze the sample.
10.1.2.2 No other changes in the analyses will be permitted. The
Contractor shall document the Region's decision in the SDG
Narrative.
10.1.3 Water/Aqueous Sample Preparation
10.1.3.1 Shake sample and transfer 50-100 mL of well-mixed sample to a 250
mL heating vessel, add 1 milliliter (mL) of (1+1) HNO 3 and 2 mL of
30% H202 to the sample. Cover with watch glass or similar cover
and heat on a hot plate, block digester, 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 50-100 mL with reagent water. The sample
is now ready for analysis. Concentrations so determined shall be
reported as "total". If volumes less than 100 mL are used, all
other reagents shall be reduced appropriately (e.g., if 50 mL is
Appendix B-13 ILM05.2
-------
Appendix B Section 10
Procedure (Con't)
used, reduce reagent volumes by one-half). The final volume of
the digestate must equal the initial volume of the sample aliquot.
10.1.4 Soil/Sediment Sample Preparation
10.1.4.1 A representative 1.0 gram (g) (wet weight) sample is digested in
nitric acid and hydrogen peroxide. The digestate is then refluxed
with either nitric acid or hydrochloric acid. Nitric acid is
employed as the final reflux acid for the Graphite Furnace Atomic
Absorption (GFAA) analysis of As, Pb, Se, and Tl. A separate
sample shall be dried for a percent solids determination.
10.1.4.2 Mix the sample thoroughly to achieve homogeneity. For each
digestion procedure, weigh (to the nearest 0.01 g) a 1.0 to 1.5 g
portion of sample and transfer to a beaker.
10.1.4.3 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 on hot plate or
block digester, and reflux for 10 minutes without boiling. Allow
the sample to cool, add 5 mL of concentrated HNO 3, 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.
10.1.4.4 After the second reflux step has been completed and the sample has
cooled, add 2 mL of reagent water and 3 mL of 30% hydrogen
peroxide (H2O2) . Return the heating vessel to the heat 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
heat vessel.
Continue to add 30% H 202 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% H 202.
10.1.4.5 If the sample is being prepared for the GFAA analysis of As, Pb,
Se, and Tl, continue heating the acid-peroxide digestate until the
volume has been reduced to approximately 2 mL, add 10 mL of
reagent water, and warm the mixture. After cooling, filter
through Whatman No. 42 filter paper (or equivalent) and dilute to
100 mL with reagent 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.
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.
10.2 Sample Analysis
10.2.1 Set up instrument with proper operating parameters established in
Section 9.1.
10.2.2 Profile and calibrate instrument according to instrument
manufacturer's recommended procedures, using calibration standard
solutions.
ILM05.2 Appendix B-14
-------
Appendix B Section 10
Procedure (Con't)
10.2.3 Instrument Parameters - Suggested Conditions
10.2.3.1 Arsenic
10.2.3.1.1 Wavelength: 193.7 run
10.2.3.1.2 Operating parameters should be set as specified by the
particular instrument manufacturer.
10.2.3.1.3 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 is
suspected, the laboratory must switch to an alternate
wavelength or take other appropriate actions to compensate for
the interference effects.
10.2.3.1.4 The use of the Electrodeless Discharge Lamps (EDLs) for the
light source is recommended.
10.2.3.2 Lead
10.2.3.2.1 Wavelength: 283.3 nm
10.2.3.2.2 Operating parameters should be set as specified by the
particular instrument manufacturer.
10.2.3.2.3 The use of background correction is required.
10.2.3.2.4 Greater sensitivity can be achieved using the 217.0 nm line,
but the optimum concentration range is reduced. The use of an
EDL at this lower wavelength has been found to be advantageous.
Also a lower atomization temperature (2400°C) may be preferred.
10.2.3.2.5 To suppress sulfate interference (up to 1500 ppm), lanthanum is
added as the nitrate to both samples and calibration standards.
10.2.3.2.6 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.
10.2.3.3 Selenium
10.2.3.3.1 Wavelength: 196.0 nm
10.2.3.3.2 Operating parameters should be set as specified by the
particular instrument manufacturer.
10.2.3.3.3 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.
10.2.3.3.4 The use of the EDL for the light source is recommended.
10.2.3.4 Thallium
10.2.3.4.1 Wavelength: 276.8 nm
Appendix B-15 ILM05.2
-------
Appendix B Sections 10 & 11
Data Analysis and Calculations
10.2.3.4.2 Operating parameters should be set as specified by the
particular instrument manufacturer.
10.2.3.4.3 The use of background correction is required.
10.2.3.4.4 Nitrogen may also be used as the purge gas.
11.0 DATA ANALYSIS AND CALCULATIONS
11.1 Water/Aqueous Sample Calculation
The concentrations determined in the digestate are to be reported in
units of microgram per Liter ( :
EQ. 1 Aqueous Sample Concentration
Vf
Concentration = C x -
WHERE, C = Instrument value in ug/L
VŁ = Final digestion volume
Vt = Initial digestion volume
11.2 Soil Sample Calculation
The concentrations determined in the digestate are to be reported on the
basis of the dry weight of the sample, in units of milligram per
kilogram (mg/kg):
EQ. 2 Soil Sample Concentration
Concentration (drywt.) (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 (see Exhibit D - Introduction to
Analytical Methods, Section 1.6).
ILM05.2
Appendix B-16
-------
Appendix B Sections 11-17
Quality Control
11.3 Corrections For Sample Dilutions
If dilutions were performed, the appropriate factor shall be applied to
the sample values as follows:
EQ. 3 Correction for Dilution
C (ug/L) = Cl x DF
WHERE, C = Concentration of analyte in sample
Cą = Instrument value concentration
DF = Dilution Factor
12.0 QUALITY CONTROL
For specific Quality Control (QC) requirements, the Contractor shall
follow the instructions provided by the USEPA Region requesting the
analysis.
13.0 METHOD PERFORMANCE
Not applicable.
14.0 POLLUTION PREVENTION
See Section 1.15 in Exhibit D - Introduction to Analytical Methods.
15.0 WASTE MANAGEMENT
See Section 1.16 in Exhibit D - Introduction to Analytical Methods.
16.0 REFERENCES
16.1 US Environmental Protection Agency. Methods for Chemical Analysis of
Water and Wastes. Method 206.2. March 1983.
16.2 US Environmental Protection Agency. Methods for Chemical Analysis of
Water and Wastes. Method 239.2. March 1983.
16.3 US Environmental Protection Agency. Methods for Chemical Analysis of
Water and Wastes. Method 270.2. March 1983.
16.4 US Environmental Protection Agency. Methods for Chemical Analysis of
Water and Wastes. Method 279.2. March 1983.
17.0 TABLES/DIAGRAMS/FLOWCHARTS
Not applicable.
Appendix B-17 ILM05.2
-------
EXHIBIT B
INORGANIC FORMS
ILM05.2
-------
USEPA - CLP
COVER PAGE
Lab Name: Contract:
Lab Code: Case No. : NRAS No. : SDG No. :
SOW No.:
EPA Sample No. Lab Sample ID
ICP-AES ICP-MS
Were ICP-AES and ICP-MS interelement (Yes/No)
corrections applied?
Were ICP-AES and ICP-MS background corrections (Yes/No)
applied?
If yes, were raw data generated before (Yes/No)
application of background corrections?
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
(or via an alternate means of electronic transmission, if approved in advance
by USEPA) has been authorized by the Laboratory Manager or the Manager's
designee, as verified by the following signature.
Signature: Name:
Date: Title:
COVER PAGE ILM05.2
-------
USEPA - CLP
1A-IN
INORGANIC ANALYSIS DATA SHEET
EPA SAMPLE NO.
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS 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
57-12-5
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:
Comment s:
Clarity Before:
Clarity After:
Texture:
Artifacts:
FORM IA-IN
ILM05.2
-------
Lab Name:
Lab Code:
USEPA - CLP
IB-IN
INORGANIC ANALYSIS DATA SHEET
Contract:
Case No. -.
Matrix: (soil/water)
Level: (low/med)
% Solids:
NRAS No.:
Lab Sample ID:
Date Received:
EPA SAMPLE NO.
SDG No.:
Concentr
Color Be
Color Af
Comments
ation Units (ug/L or mg/kg dry weight]
CAS No.
Analyte
Cone ent rat i on
.
C
Q
M
fore : Claritv Before : Texture :
ter: Clarity After: Artifacts:
FORM IB-IN
ILM05.2
-------
USEPA - CLP
2 A-IN
INITIAL AND CONTINUING CALIBRATION VERIFICATION
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS No.:
SDG No.:
Initial Calibration Verification Source:
Continuing Calibration Verification 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
Verification
True
Found
%R(D
Continuing Calibration Verification
True
Found
%R(D
Found
%R(1)
M
(1) Control Limits: Mercury 80-120; Other Metals 90-110; Cyanide 85-115
FORM IIA-IN
ILM05.2
-------
USEPA - CLP
2B-IN
CRQL CHECK STANDARD
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS No.:
SDG No.
CRQL Check 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
Cyanide
CRQL Check Standard
Initial Final
True
Found*
%R(1)
Found*
%R(1)
(1) Control Limits: 70-130 with the following exceptions:
ICP-AES - Antimony, Lead, and Thallium: 50-150.
ICP-MS - Cobalt, Manganese, and Zinc: 50-150.
* If applicable, enter the concentration qualifier "J" or "U" after the
concentration in these columns (e.g., 0.20U for Mercury).
FORM IIB-IN
ILM05.2
-------
USEPA - CLP
3-IN
BLANKS
Lab Name:
Lab Code:
Contract:
Case No,:
NRAS No.:
SDG No.
Preparation Blank Matrix (soil/water):
Preparation Blank Concentration Units (ug/L or mg/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
Calibration
Blank (ug/L)
C
Continuing Calibration
Blank (ug/L)
1
C
2
C
3
C
Preparation
Blank
C
M
FORM III-IN
ILM05.2
-------
USEPA - CLP
ICP-AES
4 A-IN
INTERFERENCE CHECK SAMPLE
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS No.:
SDG No.:
ICP-AES Instrument ID:
ICS Source:
Concentration Units: ug/L
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
True
Sol. Sol.
A AB
Initial Found
Sol. Sol.
A %R AB %R
Final Found
Sol. Sol.
A %R AB %R
FORM IVA-IN
ILM05.2
-------
USEPA - CLP
4B-IN
ICP-MS INTERFERENCE CHECK SAMPLE
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS NO.:
SDG No.:
ICP-MS Instrument ID:
ICS Source:
Concentration Units: ug/L
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Carbon
Chloride
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Phosphorus
Potassium
Selenium
Silver
Sodium
Sulfur
Thallium
Titanium
Vanadium
Zinc
True
Sol. Sol.
A AB
Found
Sol . Sol .
A %R AB %R
FORM IVB-IN
ILM05.2
-------
Lab Name:
Lab Code:
USEPA - CLP
5A-IN
MATRIX SPIKE SAMPLE RECOVERY
Contract:
EPA SAMPLE NO.
Case No.:
NRAS No.:
SDG NO.:
Matrix: (soil/water)
% Solids for Sample:
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
%R
Spiked Sample
Result (SSR)
C
Sample
Result (SR)
C
Spike
Added (SA)
%R
Q
M
Comments:
FORM VA-IN
ILM05.2
-------
USEPA - CLP
5B-IN
POST-DIGESTION SPIKE SAMPLE RECOVERY
EPA SAMPLE NO.
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS 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
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Control
Limit
l_ %R
Spiked Sample
Result (SSR)
C
Sample
Result (SR)
C
Spike
Added (SA)
%R
Q
M
Comment s:
FORM VB-IN
ILM05.2
-------
USEPA - CLP
Lab Name:
Lab Code:
Case No.:
6-IN
DUPLICATES
Contract:
NRAS No.:
EPA SAMPLE NO.
SDG NO.:
Matrix: (soil/water)
% Solids for Sample:
Leve1: (1ow/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
ILM05.2
-------
USEPA - CLP
7-IN
LABORATORY CONTROL SAMPLE
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS No.:
SDG No.
Solid LCS Source:
Aqueous LCS Source:
Analyte
Aluminum
Ant imony
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
ILM05.2
-------
USEPA - CLP
Lab Name:
Lab Code:
8-IN
ICP-AES and ICP-MS SERIAL DILUTIONS
Contract:
EPA SAMPLE NO.
Case No.
Matrix: (soil/water)
NRAS No.:
SDG No.:
Level: (low/med)
Concentration Units: ug/L
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Initial Sample
Result (I)
C
Serial
Dilution
Result (S)
C
%
Difference
Q
M
FORM VIII-IN
ILM05.2
-------
USEPA - CLP
9-IN
METHOD DETECTION LIMITS (ANNUALLY)
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS No.:
Instrument Type:
Instrument ID:
SDG No.
Date:
Preparation Method:
Concentration Units (ug/L or mg/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
Wavelength
/Mass
CRQL
MDL
Comments:
FORM IX-IN
ILM05.2
-------
USEPA - CLP
10A-IN
ICP-AES INTERELEMENT CORRECTION FACTORS (QUARTERLY)
Lab Name:
Lab Code:
Contract:
Case No.:
ICP-AES Instrument ID:
NRAS No.:
Date:
SDG NO.
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Wave-
length
(nm)
Interelement Correction Factors for:
Al Ca Fe Mg
Comments:
FORM XA-IN
ILM05.2
-------
USEPA - CLP
10B-IN
ICP-AES INTERELEMENT CORRECTION FACTORS (QUARTERLY)
Lab Name:
Lab Code:
Contract:
Case No.:
ICP-AES Instrument ID:
NRAS No.:
Date :
SDG No.
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Wave-
length
(nm)
Interelement Correction Factors for:
Comments:
FORM XB-IN
ILM05.2
-------
USEPA - CLP
11-IN
ICP-AES and ICP-MS LINEAR RANGES (QUARTERLY)
Lab Name:
Lab Code:
Case No.:
ICP Instrument ID:
Contract:
NRAS No.:
Date .-
SDG No.
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Integ.
Time
(Sec.)
Concentration
(ug/L)
M
Comments:
FORM XI-IN
ILM05.2
-------
USEPA - CLP
12-IN
PREPARATION LOG
Lab Name :
Lab Code : C
Preparation Method:
EPA
Sample
No.
'ase No. : N
Preparation
Date
Contract :
RAS No . :
Weight
(gram)
SDG No . :
Volume
(mL)
FORM XII-IN
ILM05.2
-------
USEPA - CLP
13-IN
ANALYSIS RUN LOG
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS No.:
SDG NO.
Instrument ID:
Start Date:
Analysis Method:
End Date:
EPA
Sample
No.
D/F
Time
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 XIII-IN
ILM05.2
-------
USEPA - CLP
14-IN
TCP-MS Tune
Lab Name:
Lab Code:
Case No.:
ICP-MS Instrument ID:
Contract:
NRAS No.:
SDG NO.
Date:
Element - Mass
Be - 9
Mg - 24
Mg - 25
Mg - 26
Co - 59
In - 113
In - 115
Pb - 206
Pb - 207
Pb - 208
Avg. Measured Mass (amu)
Avg. Peak Width at
5% Peak Height (amu)
%RSD
Comments:
FORM XIV-IN
ILM05.2
-------
USEPA - CLP
15-IN
ICP-MS Internal Standards Relative Intensity Summary
Lab Name:
Lab Code:
Contract:
Case No.:
NRAS No.:
ICP-MS Instrument ID:
Start Date:
SDG No.: _
End Date:
EPA Sample
No.
Time
Internal Standards %RI For:
Element
Q
Element
Q
Element
Q
Element
Q
Element
Q
FORM XV-IN
ILM05.2
-------
SAMPLE LOG-IN SHEET
ab Name
eceived By (Print Name)
Page of
Log- in Date
eceived By (Signature)
ase Number
emarks :
. Custody Seal(s)
. Custody Seal Nos .
Present /Absent*
Intact /Broken
. Traffic Present/Absent*
Reports /Chain of
Custody Records or
Packing Lists
. Airbill
. Airbill No.
Sample Tags
Airbill/Sticker
Present /Absent*
Present /Absent*
Sample Tag Numbers Listed/Not
Listed on
Traffic
Report /Chain of
Custody Record
Sample Condition
Intact /Broken*/
Leaking
. Cooler Temperature Present/Absent*
Indicator Bottle
Cooler Temperature
0. Does information
on Traffic
Reports/Chain of
Custody Records
and sample tags
agree?
1 . Date Received at
Lab
2 . Time Received
Yes/No*
Sample Transfer
raction
rea #
y
n
Fraction
Area #
By
On
Sample Delivery Group No.
EPA
Sample #
Aqueous
Sample pH
Cor re spending
Sample Tag #
Assigned
Lab S
NRAS Number
Remarks :
Condition of
Sample
Shipment, etc.
Contact SMO and attach record of resolution
eviewed By
ate
Logbook No.
Logbook Page No.
FORM DC-I
ILM05.2
-------
FULL INORGANICS COMPLETE SDG FILE (CSF) INVENTORY SHEET
LABORATORY NAME
CITY/STATE
CASE NO. SDG NO.
SDG NOs. TO FOLLOW
NRAS NO.
CONTRACT NO.
SOW NO.
All documents delivered in the Complete SDG File must be original documents
where possible. (Reference - Exhibit B Section 2.6)
PAGE NOs. CHECK
FROM TO LAB REGION
1. Inventory Sheet (DC-2) (Do not number)
2. Sample Log-In Sheet (DC-1)
3. Traffic Report/Chain of Custody Record
4. Cover Page
5. SDG Narrative
Inorganic Analysis
6. Data Sheet (Form I-IN)
7. Initial & Continuing Calibration
Verification (Form IIA-IN)
8. CRQL Standard
(Form IIB-IN)
9. Blanks (Form III-IN)
10. ICP-AES Interference Check Sample
(Form IVA-IN)
11. ICP-MS Interference Check Sample
(Form IVB-IN)
12. Matrix Spike Sample Recovery
(Form VA-IN)
13. Post-Digestion Spike Sample Recovery
(Form VB-IN)
14. Duplicates (Form VI-IN)
15. Laboratory Control Sample
(Form VII-IN)
16. ICP-AES and ICP-MS Serial Dilutions
(Form VIII-IN)
17. Method Detection Limits (Annually)
(Form IX-IN)
18. ICP-AES Interelement Correction
Factors (Quarterly) (Form XA-IN)
19. ICP-AES Interelement Correction
Factors (Quarterly) (Form XB-IN)
20. ICP-AES and ICP-MS Linear Ranges
(Quarterly) (Form XI-IN)
21. Preparation Log (Form XII-IN)
22. Analysis Run Log (Form XIII-IN)
FORM DC-2-1 ILM05.2
-------
PAGE NOs. CHECK
FROM TO LAB REGION
23. ICP-MS Tune (Form XIV-IN)
24. ICP-MS Internal Standards Relative
Intensity Summary (Form XV-IN)
25. ICP-AES Raw Data
26. GFAA Raw Data (If Applicable)
27. ICP-MS Raw Data
28. Mercury Raw Data
29. Cyanide Raw Data
30. Preparation Logs Raw Data
31. Percent Solids Determination Log
32. USEPA Shipping/Receiving Documents
Airbill (No. of Shipments )
Sample Tags
Sample Log-In Sheet (Lab)
33. Misc. Shipping/Receiving Records
(list all individual records)
Telephone Logs
34. Internal Lab Sample Transfer Records &
Tracking Sheets (describe or list)
35. Internal Original Sample Prep &
Analysis Records (describe or list)
Prep Records
Analysis Records
Description
36. Other Records (describe or list)
Telephone Communications Log
37. Comments:
Completed by:
(CLP Lab)
(Signature) (Print Name & Title) (Date)
Audited by:
(USEPA)
(Signature) (Print Name & Title) (Date)
FORM DC-2-2 ILM05.2
------- |