USEPA CONTRACT LABORATORY PROGRAM
STATEMENT OF WORK •
FOR '
ANALYSIS OF
LOW CONCENTRATION ORGANIC
OLC03.2
December 2000
-------
540R005O6
STATEMENT OF WORK
TABLE OF CONTENTS
EXHIBIT A: SUMMARY OF REQUIREMENTS
EXHIBIT B: REPORTING AND DELIVERABLES REQUIREMENTS
EXHIBIT C: TARGET COMPOUND LIST AND CONTRACT REQUIRED QUANTITATION LIMITS
EXHIBIT D: ANALYTICAL METHODS
EXHIBIT E: QUALITY ASSURANCE/QUALITY CONTROL PROCEDURES AND REQUIREMENTS
EXHIBIT F: CHAIN-OF-CUSTODY, DOCUMENT CONTROL, AND WRITTEN STANDARD OPERATING
PROCEDURES
EXHIBIT G: GLOSSARY OF TERMS
EXHIBIT H: DATA DICTIONARY AND FORMAT FOR DATA DELIVERABLES IN COMPUTER-
READABLE FORMAT
OLC03.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
OLC03.2
-------
EXHIBIT A
SUMMARY OF REQUIREMENTS
A-l OLC03.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
OLC03.2 A-2
-------
Exhibit A - Summary of Requirements
Table of Contents
Section Page
1.0 PURPOSE 5
2.0 DESCRIPTION OF SERVICE 5
3.0 DATA USES 5
4 .0 SUMMARY OF REQUIREMENTS • 5
4.1 Introduction to the Organic Low Concentration
Statement of Work 5
4.2 Overview of Major Task Areas 6
4.3 Technical and Management Capability • 13
A-3 OLC03.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
OLC03.2 A-4
-------
Exhibit A -- Sections 1-4
Purpose
1.0 PURPOSE
The purpose of the Low Concentration (Water) Organic 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 organic analytical service provides a contractual framework for
laboratories to apply USEPA Contract Laboratory Program (CLP) analytical
methods for the isolation, detection, and quantitative measurement of 50
volatile, 65 semivolatile, and 28 pesticide/Aroclor target compounds in
water samples. The analytical service provides the methods to be used
and the specific contractual requirements by which USEPA will evaluate
the data. This service uses Gas Chromatography/Mass Spectrometry
(GC/MS) and Gas Chromatography/Electron Capture Detector (GC/ECD)
methods to analyze the target compounds.
3.0 DATA USES
This analytical service 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 clean-up
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. In addition, this service
provides data that are available for use in Superfund enforcement/
litigation activities.
4.0 SUMMARY OF REQUIREMENTS
4.1 Introduction to the Organic Low Concentration Statement of Work
This Statement of Work (SOW) is designed as part of the documentation
for a contract between USEPA and a commercial laboratory performing
analyses in support of USEPA Superfund programs. The SOW is comprised
of eight exhibits. 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 Organic Target Compound list
for this SOW with the contract required quantitation limits for the
sample matrix. 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 which the Contractor shall follow. To ensure
proper understanding of the terms utilized in this SOW, a glossary can
A-5 OLC03.2
-------
Exhibit A -- Section 4
Summary of Requirements (Con't)
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.
4.2 Overview of Maj or 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.
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 File (CSF) (Exhibit B). The
Contractor shall establish and use appropriate procedures to
handle 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). 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 sample shipments at
any time the delivery service is operating, including
Saturdays.
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 (TRs) not with shipment,
sample and TR do not correspond], the Contractor shall
immediately contact SMO for resolution. The Contractor shall
immediately notify SMO regarding any problems and laboratory-
conditions that affect the timeliness of analyses and data
reporting. In particular, the Contractor shall immediately
notify SMO personnel in advance regarding sample data that will
be delivered late and shall specify the estimated delivery
date.
OLC03.2 A-6
-------
Exhibit A -- Section 4
Summary of Requirements (Con't)
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
TEMPERATURE INDICATOR. The Contractor shall record the
presence or absence of the cooler temperature indicator bottle
on Form DC-1, Item 9.
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,
and prior to unpacking the samples or removing the packing
material.
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
. .:r. •'-<'- in the bottle. At a minimum, the calibrated thermometer
: •<•:• •':*.'-• (±1°C) shall have a measurable range of 0-50°C. Other
•:•:>, *'.. devices which can measure temperature may be used if they
-;.: Ki can be calibrated to ±1°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 Sample Delivery Group
(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.
A-7 OLC03.2
-------
Exhibit A -- Section 4
Summary of Requirements (Con't)
4.2.1.2.3.5 The Contractor shall record the temperature of the cooler on
Form DC-1, under Item 10 - Cooler Temperature, and in the
SDG Narrative.
4.2.1.2.4 The Contractor shall accept all samples scheduled by SMO,
provided that the total number of samples received in any
calendar month does not exceed the monthly limitation expressed
in the contract. Should the Contractor elect to accept
additional samples, the Contractor shall remain bound by all
contract requirements for analysis of those samples accepted.
4.2.1.2.5 The Contractor is required to retain unused sample volume and
partially used sample volume in original sample containers for
a period of 60 days after data submission. From time of
receipt until analysis, the Contractor shall maintain all water
(preserved and unpreserved) samples at 4°C (±2°C).
4.2.1.2.6 The Contractor shall be required to routinely return sample
shipping containers (e.g., coolers) to the appropriate sampling
office within 14 calendar days following shipment receipt (see
clause titled, "Government Furnished Supplies and Materials").
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 Project Officer
(CLP PO), USEPA OERR Analytical Operations/Data Quality Center
(AOC) Organic Program Manager, 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 percent) 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 Sample analyses will be scheduled by groups of samples, each
defined as a Case and identified by a unique USEPA Case number
assigned by SMO. A Case signifies a group of samples collected at
OLC03.2 A-8
-------
Exhibit A -- Section 4
Summary of Requirements (Con't)
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.
4.2.2.2.1 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 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
impaqt on defining the SDG.
4.2.2.2.2 Samples shall be assigned to SDGs at the time the samples are
received, and shall not be assigned retroactively. However, PE
•"-' samples received within a Case shall be assigned to an SDG
-'••>• containing field samples for that Case.
4.2.2.2^3 Each sample received by the Contractor will be labeled with an
ip- EPA sample number, and accompanied by a TR bearing the sample
-•'-*' number and descriptive information regarding the sample. The
s- Contractor shall complete and sign the TR, recording the date
of sample receipt and sample condition on receipt for each
sample container.
4.2.2.2.4 The Contractor shall submit signed copies of TRs for all
samples in an SDG to SMO within three working days following
receipt of the last sample in the SDG. Faxed copies of TRs do
not meet this requirement. TRs shall be submitted in SDG sets
(i.e., all TRs for an SDG shall be clipped together) with an
SDG Cover Sheet containing information regarding the SDG, as
specified in Exhibit B.
4.2.2.2.5 USEPA 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.
4.2.2.3 If insufficient sample volume (less than the required amount) is
received to perform the analysis, the Contractor shall contact SMO
to apprise them of the problem. SMO will contact the Region for
instructions. The Region will either approve that no sample
analysis be performed, or 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
A-9 OLC03.2
-------
Exhibit A -- Section 4
Summary of Requirements (Con't)
decision. The Contractor shall document the Region's decision in
the SDG Narrative.
4.2.2.4 Analytical Techniques: The Target Compounds listed in Exhibit C
shall be identified, as described in the methodologies given in
Exhibit D. Automated computer programs may be used to facilitate
the identification of compounds.
4.2.2.5 Preparation Techniques. The Contractor will prepare samples as
described in Exhibit D. For semivolatile and pesticide/Aroclor
samples, an aliquot is extracted with a solvent and concentrated.
The concentrated extract is subjected to cleanup procedures and
then analyzed by Gas Chromatography/Mass Spectrometry (GC/MS) for
semivolatile or Gas Chromatography/Electron Capture Detector
(GC/ECD) for the pesticide/Aroclor target compounds listed in
Exhibit C. For volatile samples, an aliquot is purged with an
inert gas, trapped on a solid sorbent, and then desorbed onto the
GC/MS for analysis of the target compounds listed in Exhibit C.
4.2.2.6 Qualitative Verification of Compounds. The volatile and
semivolatile compounds identified by GC/MS techniques shall be
verified by an analyst competent in the interpretation of mass
spectra by comparison of the suspect mass spectrum to the mass
spectrum of a standard of the suspected compound. This procedure
requires the use of multiple internal standards.
4.2.2.6.1 If a compound initially identified by GC/MS techniques cannot
be verified, but in the technical judgment of the mass spectral
interpretation specialist the identification is correct, then
the Contractor shall report that identification and proceed
with quantitation.
4.2.2.6.2 The pesticide/Aroclor compounds identified by GC/ECD techniques
shall be verified by an analyst competent in the interpretation
of gas chromatograms and by comparison of the retention times
of the suspected unknowns with the retention times of
respective standards of the suspected compounds. Compounds
shall also be confirmed by GC/MS techniques if the compounds
are of sufficient concentration to be detected by the GC/MS.
4.2.2.7 Quantitation of Verified Compounds. The Contractor shall
quantitate components identified by GC/MS techniques by the
internal standard method stipulated in Exhibit D. Where multiple
internal standards are required by USEPA, the Contractor shall
perform quantitation utilizing the internal standards specified in
Exhibit D. The Contractor shall quantitate components analyzed by
GC/ECD techniques by the external standard method stipulated in
Exhibit D. The Contractor shall also perform an initial
calibration, verify its linearity, determine the breakdown of
labile components, and determine calibration factors for all
standards analyzed by GC/ECD techniques as described in Exhibit D.
4.2.2.8 Tentative Identification of Non-Target Sample Components. For
each analysis of a sample, the Contractor shall conduct mass
spectral library searches to determine tentative compound
OLC03.2 . A-10
-------
Exhibit A -- Section 4
Summary of Requirements (Con't)
identifications as follows: For each volatile sample, the
Contractor shall conduct a search to determine the possible
identity of up to 30 organic compounds of greatest concentration
which are not deuterated monitoring compounds or internal
standards and are not listed in Exhibit C under volatiles or
semivolatiles. For each semivolatile sample, the Contractor shall
conduct a search to determine the possible identification of up to
30 organic compounds of greatest concentration which are not
surrogates or internal standards and are not listed in Exhibit C
under volatiles or semivolatiles. In performing searches, the
NIST/EPA/NIH (May 1992 release or later) and/or Wiley (1991
release or later), or equivalent, mass spectral library shall be
used.
NOTE: Substances with responses less than 10 percent of the
nearest internal standard are not required to be searched in this
fashion.
4.2.2.9 Quality Assurance/Quality Control (QA/QC) Procedures
4.2.2.9.1 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.
4.2.2F9-. 2 The Contractor shall maintain a Quality Assurance 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.
4.2.2.9.3 Additional QC shall be conducted in the form of the analysis of
Performance Evaluation samples submitted to the laboratory by
USEPA. Unacceptable results of all such QC or Performance
Evaluation samples may be used as the basis for an equitable
adjustment to reflect the reduced value of the data to USEPA or
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 Standard Operating Procedure (SOP) documentation (Exhibit
F). As an alternative to data rejection, USEPA may require re-
analysis of non-compliant samples. Re-analysis will be
performed by the Contractor at no additional cost to USEPA,
unless it is determined that the Performance Evaluation
sample(s) was defective.
A-ll OLC03.2
-------
Exhibit A -- Section 4
Summary of Requirements (Con't)
4.2.3 Task III: Sample Reporting and Resubmission of Data
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 and 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 will be deemed
as non-compliant. Such data are unacceptable. Resubmission in
the specified format, at no additional cost to USEPA, 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 If the submitted data package does not conform to the specified
contractual or technical criteria, the Contractor will be required
to resubmit the data package with all deficiencies corrected at
its own expense. The Contractor will respond within seven days to
requests for additional information or explanations that result
from the Government's inspection activities. If the Contractor is
required to submit or resubmit data as a result of a Regional
request, the data shall be clearly marked as ADDITIONAL DATA. The
Contractor shall include a cover letter which describes which data
are-being delivered, to which USEPA project the data pertain, and
who requested the data. Any and all resubmissions must be in
accordance with the documentation requirements of this SOW.
4.2.3.5 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 corrected hardcopy forms or the corrected computer-readable
data, or both sets of corrected data, at no additional cost to
USEPA.
4.2.3.6 In addition, 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 data may also be
used in litigation against Potentially Responsible Parties (PRPs)
in the enforcement of Superfund legislation.
OLC03.2 A-12
-------
Exhibit A -- Section 4
Summary of Requirements (Con't)
4.3 Technical and Management Capability
4.3.1 Personnel
The Contractor shall have adequate personnel at all times during the
performance of the contract to ensure that USEPA receives data that
meet the terms and conditions of the contract.
4.3.2 Instrumentation
The Contractor shall have a sufficient Gas Chromatograph/Electron
Capture/Data System (GC/ECD/DS), Gas Chromatograph/Mass
Spectrometer/Data System (GC/MS/DS), including magnetic tape storage
devices to meet all the terms and conditions of the contract.
4.3.3 Facilities.
The Contractor shall maintain a facility suitable for the receipt,
storage, analysis of the samples, and delivery of the product meeting
the terms and conditions of the contract.
A-13
OLC03.2
-------
EXHIBIT B
REPORTING AND DELIVERABLES REQUIREMENTS
B-l OLC03.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
OLC03.2 B-2
-------
Exhibit B - Reporting and Deliverable Requirements
Table of Contents
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 .• 10
2.1 Introduction 10
2.2 Resubmission of Data 10
2.3 Quality Assurance Plan (QAP) and Standard
Operating Procedures 11
2.4 Sample Traffic Reports 11
2.5 Sample Data Package 12
2.6 Complete SDG File 25
2.7 Data in Computer-Readable Format 26
2.8 Preliminary Results 26
2.9 GC/MS and GC/ECD Tapes 27
2.10 Extracts 27
3.0 FORM INSTRUCTIONS 28
3.1 Introduction 28
3.2 General Information 28
3.3 Header Information ...... 29
3.4 Organic Analysis Data Sheet (Form I, All Fractions) 33
3.5 Organic Analysis Data Sheet: Tentatively Identified Compounds
(Form I LCV-TIC and Form I LCSV-TIC) 36
3.6 Deuterated Monitoring Compound (DMC) Recovery
(Form II LCV-1, LCV-2 and Form II LCSV-1, LCSV-2) 37
3.7 Surrogate Recovery (Form II LCP) 38
3.8 Matrix Spike/Matrix Spike Duplicate Recovery
(Form III, All Fractions, LCV, LCSV, LCP-1) 39
3.9 Method Blank Summary (Form IV, All.Fractions) 41
3.10 GC/MS Instrument Performance Check
(Form V LCV and Form V LCSV) • 42
3.11 GC/MS Initial Calibration Data (Form VI LCV-1, LCV-2,
LCV-3 and Form VI LCSV-1, LCSV-2, LCSV-3) 43
3.12 GC/EC Initial Calibration Data (Form VI LCP-1, LCP-2, LCP-3) 43
3.13 GC/MS Continuing Calibration Data (Form VII LCV-1,
LCV-2, LCV-3 and Form VII LCSV-1, LCSV-2, LCSV-3) ... 46
3.14 GC/ECD Calibration Verification Summary
(Form VII, LCP-1, LCP-2) 46
3.15 Internal Standard Area and RT Summary
(Form VIII LCV and Form VIII LCSV-1, LCSV-2) 47
3.16 Pesticide Analytical Sequence (Form VIII LCP) 49
3.17 Pesticide Cleanup Summary (Form IX, LCP) 50
3.18 Pesticide/Aroclor Identification (Form X, LCP-1, LCP-2) 51
3.19 Sample Log-In Sheet (Form DC-1) . 52
3.20 Complete SDG File (CSF) Inventory Sheet (Form DC-2) 53
4.0 DATA REPORTING FORMS 54
B-3 OLC03.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
OLC03.2 B-4
-------
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 deliverable requirements specified in the
Contract Schedule (Performance/Delivery Schedule) and specifies the
distribution that is required for each deliverable. The turnaround
times for items B through E listed below are 7, 14, and 21 days.
NOTE: Specific recipient names and addresses are subject to change
during the term of the contract. The USEPA Analytical Operations/Data
Quality Center (AOC) Organic Program Manager will notify the Contractor
in writing of such changes when they occur.
Table 1
Distribution
s
NO. of i s*.
CQ fX
Item Copies* Delivery Schedule
A.2 Sample Traffic 1 3 working days X
Reports ' after receipt of
last sample in
Sample Delivery
Group (SDG)-1
B.2 Sample Data 1 XXB days after X
Package0 receipt of last
sample in SDG.
N
C.2 Data in 1 XXs days after X X
Computer- receipt of last
Readable sample in SDG.
Format
D.2- 3 Complete SDG 1 XXB days after X
File receipt of last
sample in SDG.
E.5 Preliminary 1 Within 48 hours X X
Results (VOA after receipt of
Analyses) each sample at
laboratory, if .
requested.
Preliminary 1 Within 72 hours X X
Results (SV after receipt of
and Pest each sample at
Analyses) laboratory, if
requested.
B-5 OLC03.2
-------
Exhibit B -- Section 1
Contract Reports/Deliverables Distribution (Con't)
Distribution
Item
No. of
Copies
Delivery
Schedule
o
§
-H
Ol
0)
PS
Standard
Operating
Procedures--
Technical and
Evidentiary
Revise within 60
days after
contract award.
Submit within 7
days of receipt
of written
request to
recipients as
directed.
As directed
Quality
Assurance Plan
Revise within 60
days after
contract award.
GC/MS and
GC/ECD Tapes.
Lot
Submit within 7
days of receipt
of written
request to
recipients as
directed.
Retain for 3
years after data
submission.
As directed
As directed
Extracts
Lot
Submit within 7
days after
receipt of
written request
by CLP PO.
Retain for 365
days after data
submission.
As directed
J.e
Method
Detection Limit
Study
Submit within 7
days after
receipt of
written request
by CLP PO or
SMO, at USEPA's
direction.
Submit to USEPA
within 7 days
after receipt of
written request
by CLP PO or
SMO, at USEPA's
discretion.
As directed
OLC03.2
B-6
-------
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.
BThe 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 the sample scheduling by the Sample Management Office (SMO)
Contractor.
Contractor-concurrent delivery to USEPA designated recipient (e.g.,
QATS) may be required upon request by the CLP PO. Retain for 365 days after
data submission, and submit as directed within 7 days after receipt of written
request by the CLP PO.
*A Sample Delivery Group (SDG) is a group of samples within a Case,
received over a period of 7 days or less, not exceeding 20 samples, (excluding
PE samples) and scheduled under the same contractual turnaround (Preliminary
Results have no impact on defining the SDGs). 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
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 delivered after
this time will be considered late.
3Complete SDG File will contain the original Sample Data Package plus all
of the original documents described under Section 2.6.
4See Exhibit E and Exhibit F for a more detailed description.
5If requested at the time of sample scheduling, the Contractor shall
provide Preliminary Results, consisting of Form I and Form I TIC analytical
results, by fraction, for field and QC sample analyses via telefacsimile
(fax). The Contractor may submit Preliminary Results in electronic format
after obtaining permission from USEPA. The Contractor will be notified of the
fax number or E-mail address at the time of sample scheduling. Sample Traffic
Reports (TRs) and SDG cover sheets shall be submitted with the Preliminary
Results. The Contractor shall contact SMO after confirming transmission. The
Contractor shall document all communication in a telephone contact log.
6Method Detection Limit Study is performed annually or for each new
instrument, whichever is more frequent. The information should be available
on file and provided to USEPA within 7 days after the receipt of a written
request.
Preliminary Results Delivery Schedule:
If the sample arrives before 5 p.m., the Preliminary Results for that
sample are due within the required turnaround time. If the sample is
received after 5 p.m., the Preliminary Results for that sample are due
within the required turnaround time beginning at 8 a.m. the following
day. DELIVERABLES ARE TO BE REPORTED TOTAL AND COMPLETE. Concurrent
B-7 OLC03.2
-------
Exhibit B -- Section 1
Contract Reports/Deliverables Distribution (Con't)
Footnotes (Con't):
delivery is required. Delivery shall be made such that all designated
recipients receive the item on the same calendar day. If the
deliverables are due on a Saturday, Sunday, or Federal holiday, then they
shall be delivered on the next business day. Deliverables delivered
after this time will be considered late.
NOTE: As specified in the Contract Schedule (Government Furnished
Supplies and Materials), unless otherwise instructed by the CLP SMO based
on a Regional decision, the Contractor shall dispose of unused sample
volume and used sample bottles/containers no earlier than sixty days
following submission of the reconciled Complete SDG File. Sample
disposal and disposal of unused sample bottles/containers is the
responsibility of the Contractor, and should be done in accordance with
all applicable laws and regulations governing disposal of such materials.
1.2 Distribution
The following addresses correspond to the "Distribution" column in the
tables in Sections 1.1.
SMO: USEPA Contract Laboratory Program
Sample Management Office (SMO}1
2000 Edmund Halley Dr.
Reston, VA 20191-3436
Region: USEPA Region: The SMO will provide the Contractor with the
list of addresses 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 AOC Organic Program Manager:
Mailing Address: USEPA OERR Analytical Operations/
Data Quality Center
Ariel Rios Building (5204G)
1200 Pennsylvania Avenue, N.W.
Washington, DC 20469
Attn: CLP Organic 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 Organic Program Manager
JThe Sample Management Office (SMO) is a contractor-operated facility
operating under the CLASS contract awarded and administered by USEPA.
OLC03.2 B-8
-------
Exhibit B -- Section 1
Contract Reports/Deliverables Distribution (Con't)
USEPA Regional CLP Project Officer (CLP PO):
SMO will provide the Contractor with the list of addresses for
the 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
2The Quality Assurance Technical Support (QATS) Laboratory is a
contractor operated facility operating under the QATS contract awarded and
administered by the USEPA.
B-9 OLC03.2
-------
Exhibit B -- Section 2
Reporting Requirements/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 the Contract Schedule (Performance/Delivery Schedule). The required
content and form of each deliverable is described in this exhibit. All
reports and documentation must be:
• Legible;
• Clearly labeled and completed in accordance with instructions in
this exhibit;
• Arranged in the order specified in this section;
• Paginated consecutively in ascending order starting from the Sample
Delivery Group (SDG) Narrative;
• Copies must be legible and double-sided; and
• Information reported on the forms listed in Exhibit B (excluding the
Sample Log-in Sheet [DC-1] and the Complete SDG File (CSF) Inventory
Sheet [DC-2]) must be either typewritten or computer-generated.
Handwritten corrections of the information must be legible, signed,
and dated.
NOTE: Complete SDG files need not be double-sided. (The CSF is composed
of original documents.) However, Sample Data Packages delivered to
Sample Management Office (SMO) must be double-sided.
2.1.1 Requirements for each deliverable item cited in the Contract Schedule
(Contract Performance/Delivery Schedule) are specified in Sections
2.3 to 2.9. Prior to submission, the Contractor shall.arrange items
and the components of each item in the order listed in these
sections.
2.1.2 The Contractor shall use USEPA Case numbers (including SDG numbers)
and EPA sample numbers to identify samples received under this
contract, both verbally and in reports/correspondence. The contract
number shall be specified in all correspondence.
2.2 Resubmission of Data
If submitted documentation does not conform to the above criteria, the
Contractor shall resubmit such documentation with deficiency(ies)
corrected, at no additional cost to USEPA.
2.2.1 The Contractor shall respond within seven days to written requests
from data recipients for additional information or explanations that
result from the Government's inspection activities, unless otherwise
specified in the contract.
2.2.2 Whenever the Contractor is required to submit or resubmit data as a
result of an on-site laboratory evaluation, or through a Contract
Laboratory Program Project Office (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 the Region; to USEPA designated recipient, upon written •
request). The Contractor shall include a cover letter which
describes which data are being delivered, to which USEPA Case(s) the
data pertain, and who requested the data.
OLC03.2 B-10
-------
Exhibit B -- Section 2
Reporting Requirements/Order of Data Deliverables (Con't)
2.2.3 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 both contractual data recipients (SMO and the
Region; to the USEPA 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 Response to Results of Contract Compliance Screening)
provided by SMO.
2.3 Quality Assurance Plan (QAP) and Standard Operating Procedures (SOPs)
The Contractor shall adhere to the requirements in Exhibits E and F.
2.4 Sample Traffic Reports (TRs)
Each sample received by the Contractor will be labeled with a EPA sample
number, and will be accompanied by a Sample TR bearing the sample number
and descriptive information regarding the sample. The Contractor shall
complete the TR (marked "Lab Copy for Return to SMO"), recording the
date of sample receipt and sample condition upon receipt for each
container, and shall sign the TR. Information shall be recorded for
each sample in the SDG.
2.4.1 The Contractor shall submit TRs in^SDG sets (i.e., TRs for all
samples in an SDG shall be clipped together), with an SDG cover sheet
attached. The SDG cover sheet shall contain the following items:
• Laboratory name;
• Contract number;
• Sample analysis price (full sample price from the contract);
• Case number; and
• List of EPA sample numbers of all samples in the SDG, identifying
the first and last samples received, and their dates of receipt
(LRDs).
NOTE: When more than one sample is received in the first or last SDG
shipment, the "first" sample received would be the lowest sample
number (considering both alpha and numeric designations); the "last"
sample received would be the highest sample number (considering both
alpha and numeric designations).
2.4.2 Each TR shall be clearly marked with the SDG number, entered below
the laboratory receipt date on the TR. The TR for the last sample
received in the SDG shall be clearly marked "SDG--FINAL SAMPLE". The
SDG number is the EPA sample number of the first sample received in
the SDG. When several samples are received together in the first SDG
shipment, the SDG number shall be the lowest sample number
(considering both alpha and numeric designations) in the first group
of samples received under the SDG.
2.4.3 If samples are received at the laboratory with multi-sample TRs, all
the samples on one multi-sample TR may not necessarily be in the same
SDG. In this instance, the Contractor shall make the appropriate
number of photocopies of the TR, and submit one copy with each SDG
cover sheet.
B-ll OLC03.2
-------
Exhibit B -- Section 2
Reporting Requirements/Order of Data Deliverables (Con't)
2 .5 Sample Data Package
The Sample Data Package is divided into the five major units described
in this section. The last three units are each specific to an
analytical fraction (volatiles, semivolatiles, and pesticides/Aroclors).
If the analysis of a fraction is not required, then that
fraction-specific unit is not required as a deliverable. The Sample
Data Package shall include data for the analyses of all samples in one
SDG, including field samples, dilutions, re-analyses, blanks. Laboratory
Control Samples, and any requested Matrix Spike/Matrix Spike
Duplicate(s) (MS/MSD). The Contractor shall retain a copy of the CSF
for 365 days after final acceptance of data. After this time, the
Contractor may dispose of the package.
2.5.1 SDG Narrative. This document shall be clearly labeled "SDG
Narrative" and shall contain: laboratory name; Case number,- EPA
sample numbers in the SDG, differentiating between initial analyses
and re-analyses,- SDG number; Contract number,- and detailed
documentation of any quality control, sample, shipment and/or
analytical problems encountered in processing the samples reported in
the data package. The Contractor shall include any technical and
administrative problems encountered, the corrective actions taken,
the resolution, and an explanation for all flagged edits (e.g.,
manual edits) on quantitation lists. 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 SOW modification. This includes
attaching a copy of the 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.
All Gas Chromatograph (GC) columns used for analysis shall be
documented here, by fraction. List the GC column identification--
brand name, the internal diameter, in millimeters (mm), and the
length, in meters, packing/coating material and film thickness. The
trap used for volatile analysis shall be described here. List trap
name, when denoted by manufacturer, its composition [packing
material/brand name, amount of packing material, in length,
centimeters (cm)]. All tentatively identified (semi-volatile)
alkanes and their estimated concentrations are to be reported here.
The EPA sample number, the CAS number, when available, the alkane
compound (or series) name, and its estimated concentration shall be
provided in tabular format. The Contractor shall document in the SDG
Narrative all instances of manual integration. The SDG Narrative
shall contain the following statement, verbatim: "I certify that this
data package is in compliance with the terms and conditions of the
contract, both technically and for completeness, for other than the
conditions detailed above. Release of the data contained in this
hardcopy data package and in the computer-readable data submitted on
diskette has been authorized by the laboratory manager or his/her
designee, as verified by the following signature." This statement .
shall be directly followed by an original signature of the laboratory
manager or their designee with a typed line below it containing the
signer's name and title, and the date of signature.
OLC03.2 B-12
-------
Exhibit B -- Section 2
Reporting Requirements/Order of Data Deliverables (Con't)
2.5.1.1 The samples analyzed under this contract should not exhibit a
matrix effect which would prevent the Contractor from meeting the
requirements of the contract. Sample re-extraction/re-analyses
performed as a result of suspected matrix interferences beyond the
scope of the method will be reviewed on a case-by-case basis for
payment purposes by the CLP PO. Send or telefax to the CLP PO a
copy of the SDG Narrative (include your contract number), a
description of the situation and the requested CLP PO action,
either prior or concurrent with the delivery of the Sample Data
Package.
2.5.1.2 The Contractor shall list the pH determined for each water sample
submitted for volatiles analysis. This information may appear as
a simple list or table in the SDG Narrative. The purpose of this
pH determination is to ensure that all water volatiles samples
were acidified in the field. No pH adjustment is to be performed
. by the Contractor on water samples for volatiles analysis.
2.5.2 Traffic Reports. The Contractor shall include a copy of the TRs
submitted in Section 2.4 for all of the samples in:the SDG. The TRs
shall be arranged in increasing EPA sample number order, considering
both letters and numbers. Copies of the SDG cover sheet are to be
included with the copies of the TRs. (See Section 2.4 for more
detail on reporting requirements for TRs.) In the case of multi-
sample TRs, the Contractor shall make the appropriate number of
photocopies of the TR so that a copy is submitted with each
applicable data package. In addition, in any instance where samples
from more than one multi-sample TR are in the same data package, the
Contractor shall submit a copy of the SDG cover sheet with copies of
the TRs.
2.5.3 Volatiles Data
2.5.3.1 Volatiles QC Summary
2.5.3.1.1 Deuterated Monitoring Compound Recovery (Form II LCV-1, LCV-2).
2.5.3.1.2 Matrix Spike/Matrix Spike Duplicate Recovery (Form III LCV).
This data shall be provided upon Region's request.
2.5.3.1.3 Method Blank Summary (Form IV LCV): If more than a single form
is necessary, forms shall be arranged in chronological order by
date of analysis of the blank, by instrument.
2.5.3.1.4 GC/MS instrument performance check (Form V LCV): If more than a
single form is necessary, forms shall be arranged in
chronological order, by instrument.
2.5.3.1.5 Internal Standard Area and RT Summary (Form VIII LCV): If more
than a single form is necessary, forms shall be arranged in
chronological order, by instrument.
2.5.3.2 Volatiles Sample Data. Sample data, including dilutions, and re-
analyses data, shall be arranged in packets with the Organic
Analysis Data Sheet (Form I LCV-1, LCV-2, including Form I LCV-
TIC), followed by the raw data for volatile samples. These sample
packets shall be placed in increasing EPA sample number order,
considering both letters and numbers.
2.5.3.2.1 Target Compound Results, Organic Analysis Data Sheet (Form I
LCV-1, LCV-2). Tabulated results (identification and
quantitation) of the specified target compounds (Exhibit C,
B-13 OLC03.2
-------
Exhibit B -- Section 2
Reporting Requirements/Order of Data Deliverables (Con't)
Volatiles) shall be included. The validation and release of
these results are authorized by a specific, signed statement in
the SDG Narrative (Section 2.5.1). In the event that the
laboratory manager cannot verify all data reported for each
sample, the laboratory manager shall provide a detailed
description of the problems associated with the sample in the
SDG Narrative.
2.5.3.2.2 Tentatively Identified Compounds (Form I LCV-TIC). Form I
LCV-TIC.is the tabulated list of the highest probable match for
up to 30 organic compounds that are not deuterated monitoring
compounds or internal standard compounds and are not listed in
Exhibit C. It includes the Chemical Abstracts Service (CAS)
registry number (if applicable), tentative identification, and
estimated concentration. This form shall be included even if
no compounds are found. If no compounds are found, indicate
this on the form by entering "0" in the field for "Number
Found".
2.5.3.2.3 .Reconstructed Total Ion Chromatograms (for each sample or
sample extract, including dilutions and re-analyses).
Reconstructed ion chromatograms shall be normalized to the
largest nonsolvent component and shall contain the following
. header information:
• EPA sample number;
• Date and time of analysis;
»
• GC/MS instrument identifier;
• Lab file identifier, and
• Analyst ID.
2.5.3.2.3.1 Internal standards and deuterated monitoring compounds shall
be labeled with the names of compounds, either directly out
from the peak or on a printout of retention times, if
retention times (or scan numbers) are printed above the
peak.
2.5.3.2.3.2 If automated data system procedures are used for preliminary
identification and/or quantitation of the target compounds,
the complete data system report shall be included in all
Sample Data Packages, in addition to the reconstructed ion
chromatogram. The complete data system report shall include
all of the information listed below. For laboratories which
do not use the automated data system procedures, a
laboratory "raw data sheet" containing the following
information shall be included in the'Sample Data Package, in
addition to the chromatogram:
• EPA sample number;
• Date and time of analysis;
• Retention time or scan number of identified target
compounds;
• Ion used for quantitation with measured area;
• Copy of area table from data system;
OLC03.2 B-14
-------
Exhibit B -- Section 2
Reporting Requirements/Order of Data Deliverables (Con't)
• GC/MS instrument identifier;
• Lab file identifier; and
• Analyst ID.
2.5.3.2.3.3 In all instances where the data system report has been
• edited, or where manual integration or quantitation has been
performed, the GC/MS operator shall identify such edits or
manual procedures by initialing and dating the changes made
to the report, and shall include the integration scan range.
In addition, a hardcopy printout of the Extracted Ion
Current Profile (EICP) of the quantitation ion displaying
the manual integration shall be included in the raw data.
This applies to all compounds listed in Exhibit C
(Volatiles), internal standards and deuterated monitoring
compounds.
• EICPs displaying each manual integration.
2.5.3.2.4 Other Required Information. For each sample, by each compound
identified, the following items shall be included in the data
package.
• Copies of raw spectra and copies of background-subtracted
mass spectra of target compounds listed in Exhibit C
(Volatiles) 4,that are identified in the sample and
corresponding background-subtracted target compound
standard mass spectra. Spectra shall be labeled with EPA
sample number, lab file identifier, date and time of
analysis, and GC/MS instrument identifier. Compound names
shall be clearly marked on all spectra.
• Copies of mass spectra of non-deuterated monitoring/non-
internal standard organic compounds not listed in Exhibit C
with associated best-match spectra (minimum of one, maximum
of three best matches). Spectra shall be labeled with EPA
sample number, lab file identifier, date and time of
analysis, and GC/MS instrument identifier. Compound names
shall be clearly marked on all spectra.
2.5.3.3 Volatiles Standards Data
2.5.3.3.1 Initial calibration data (Form VI LCV-1, LCV-2, LCV-3) shall be
included in order by instrument, if more than one instrument is
used.
• Volatile standard(s) reconstructed ion chromatograms and
quantitation reports for the initial (five-point)
calibration, labeled as in Section 2.5.3.2.3. Spectra are
not required.
• All initial calibration data that pertain to samples in the
data package shall be included, regardless of when it was
performed and for which Case. When more than one initial
calibration is performed, the data shall be in
chronological order, by instrument.
• EICPs displaying each manual integration.
B-15 "OLC03.2
-------
Exhibit B -- Section 2
Reporting Requirements/Order of Data Deliverables (Con't)
2.5.3.3.2 Continuing calibration data (Form VII LCV-1, LCV-2, LCV-3)
shall be included in order by instrument, if more than one
instrument is used.
• Volatile standard(s) reconstructed ion chromatograms and
quantitation reports for all continuing (12-hour)
calibrations, labeled as in Section 2.5.3.2.3. Spectra are
not required.
• 'When more than one continuing calibration is performed,
forms shall be in chronological order, by instrument.
• EICPs displaying each manual integration.
2.5.3.3.3 In all instances where the data system report has been edited,
or where manual integration or quantitation has been performed,
the GC/MS operator shall identify such edits or manual
procedures by initialing and dating the changes made to the
report, and shall include the integration scan range. In
addition, a hardcopy printout of the EICP of the quantitation
ion displaying the manual integration shall be included in the
raw data. This applies to all compounds listed in Exhibit C
(Volatiles), internal standards and deuterated monitoring
compounds.
2.5.3.4 Volatiles Raw QC Data
2.5.3.4.1 4-Bromofluorobenzene (BFB) data shall be arranged in
chronological order by instrument for each 12-hour period, for
each GC/MS system utilized.
• Bar graph spectrum, labeled as in Section 2.5.3.2.4.
• Mass listing, labeled as in Section 2.5.3.2.4.
• Reconstructed total ion chromatogram, labeled as in Section
2.5.3.2.3.
2.5.3.4.2 Blank data shall be arranged by type of blank (method, storage,
instrument) and shall be in chronological order by instrument.
NOTE: This order is different from that used for samples.
• Tabulated results (Form I LCV-1, LCV-2).
• Tentatively identified compounds (Form I LCV-TIC) even if
none are found.
• Reconstructed ion chromatogram(s) and quantitation
report(s), labeled as in Section 2.5.3.2.3.
• Target compound spectra with laboratory-generated standard
spectra, labeled as in Section 2.5.3.2.4. Data systems
which are incapable of dual display shall provide spectra
in the following order:
Raw target compound spectra.
Enhanced or background-subtracted spectra.
Laboratory-generated standard spectra.
OLC03.2 , B-16
-------
Exhibit B -- Section 2
Reporting Requirements/Order of Data Deliverables (Con't)
GC/MS library search spectra for tentatively identified
compounds, labeled as in Section 2.5.3.2.4.
Quantitation/calculation of tentatively identified compound
concentrations.
2.5.3.4.3 Volatiles Matrix Spike Data
• Tabulated results (Form I LCV-l, LCV-2) of target
compounds. Form I LCV-TIC is not required.
• Reconstructed ion chromatogram(s) and quantitation
report(s), labeled as in Section 2.5.3.2.3. Spectra are
not required.
2.5.3.4.4' Volatiles Matrix Spike Duplicate Data
• Tabulated results (Form I LCV-l., LCV-2) of target
compounds. Form I LCV-TIC is not required.
• Reconstructed ion chromatogram(s) and quantitation
report(s), labeled as in Section 2.5.3.2.3. Spectra are
not required.
2.5.4 Semivolatiles Data
/•
2.5.4.1 Semivolatiles QC Summary
2.5.4.1.1 Deuterated Monitoring Compound Recovery (Form II LCSV-1, LCSV-2) .
.2.5.4.1.2 Matrix Spike/Matrix Spike Duplicate Recovery (Form III LCSV):
This data shall be provided upon Region's request.
2.5.4.1.3 Method Blank Summary (Form IV LCSV): If more than a single form
is necessary, forms shall be arranged in chronological order by
date of analysis of the blank, by instrument.
2.5.4.1.4 GC/MS Instrument Performance Check (Form V LCSV): If more than
a single form is necessary, forms shall be arranged in
chronological order, by instrument.
2.5.4.1.5 Internal Standard Area and RT Summary (Form VIII LCSV): If more
than a single form is necessary, forms shall be arranged in
chronological order, by instrument.
2.5.4.2 Semivolatiles Sample Data. Sample data, including dilutions and
re-analysis samples, shall be arranged in packets with the Organic
Analysis Data Sheet (Form I LCSV-1, LCSV-2, including Form I
LCSV-TIC), followed by the raw data for semivolatile samples.
These sample packets shall be placed in increasing EPA sample
number order, considering both letters and numbers.
2.5.4.2.1 Target Compound Results, Organic Analysis Data Sheet (Form I
LCSV-1, LCSV-2). Tabulated results (identification and
quantitation) of the specified target compounds (Exhibit C,
Semivolatiles) shall be included. The validation and release
of these results are authorized by a specific, signed statement
in the SDG Narrative (Section 2.5.1). In the event that the
laboratory manager cannot verify all data reported for each
sample, the laboratory manager shall provide a detailed
B-17 OLC03.2
-------
Exhibit B -- Section 2
Reporting Requirements/Order of Data Deliverables (Con't)
description of the problems associated with the sample in the
SDG Narrative.
2.5.4.2.2 _Tentatively Identified Compounds (Form I LCSV-TIC). Form I
LCSV-TIC is the tabulated list of the highest probable match
for up to 30 organic compounds that are not deuterated
monitoring compounds, or internal standard organic compounds
and are not listed in Exhibit C (Volatiles, Semivolatiles). It
includes the CAS registry number (if applicable), tentative
identification, and estimated concentration. This form shall
be included even if no compounds are found. If no compounds
are found, indicate this on the form by entering "0" in the
field for "Number TICs found."
2.5.4.2.3 Reconstructed Total Ion Chromatograms (for each sample,
including dilutions and re-analyses). Reconstructed ion
Chromatograms shall be normalized to the largest nonsolvent
component and shall contain the following header information:
• EPA sample number;
• Date and time of analysis;
• GC/MS instrument identifier;
• Lab file identifier; and
• Analyst ID.
2.5.4.2.3.1 Internal standards and deuterated monitoring compounds shall
be labeled with the names of compounds, either directly out
from the peak or on a printout of retention times if
retention times (or scan numbers) are printed over the peak.
2.5.4.2.3.2 If automated data system procedures are used for preliminary
identification and/or quantitation of the target compounds,
the complete data system report shall' be included in all
Sample Data Packages, in addition to the reconstructed ion'
chromatogram. The complete data system report shall include
all of the information listed below. For laboratories which
do not use the automated data system procedures, a
laboratory "raw data sheet" containing the following
information shall be included in the Sample Data Package, in
addition to the chromatogram:
• EPA sample number;
• Date and time of analysis,-
• Retention time or scan number of identified target
compounds;
• Ion used for quantitation with measured area;
• Copy of area table from data system;
• GC/MS instrument identifier;
• Lab file identifier; arid
• Analyst ID.
OLC03.2 B-18
-------
Exhibit B -- Section 2
Reporting Requirements/Order of Data Deliverables (Con't)
2.5.4.2.3.3 In all instances where the data system report has been
edited, or where manual integration or quantitation has been
performed, the GC/MS operator shall identify such edits or
manual procedures by initialing and dating the changes made
to the report, and shall include the integration scan range.
In addition, a hardcopy printout of the EICP of the
quantitation ion displaying the manual integration shall be
included in the raw data. This applies to all compounds
listed in Exhibit C (Semivolatiles), internal standards and
deuterated monitoring compounds.
• EICPs displaying each manual integration.
2.5.4.2.4 Other Required Information. For each sample, by each compound
identified, the following shall be included in the data
package.
• Copies of raw spectra and copies of background-subtracted
mass spectra of target compounds listed in Exhibit C
(Semivolatiles) that are identified in the sample and
corresponding background-subtracted target compound
standard mass spectra. Spectra shall be labeled with EPA-
sample number, lab file identifier, and date and time of
analysis, and GC/MS instrument identifier compound names
shall be clearly marked on all spectra.
• Copies of mass spectra of non-deuterated monitoring
compounds/non-internal standard organic compounds not
listed in Exhibit C (Volatiles and Semivolatiles) with
associated best-match spectra (minimum of- one, maximum of
three best matches). This includes the mass spectra for
tentatively identified alkanes. Spectra shall be labeled
with EPA sample-number, lab file identifier, and date and
time of analysis, and GC/MS instrument identifier compound
names shall be clearly marked on all spectra.
2.5.4.3 Semivolatiles Standards Data
2.5.4.3.1 Initial calibration data (Form VI LCSV-1, LCSV-2, LCSV-3) shall
be included in order by instrument, if more than one instrument
is used.
• Semivolatile standard(s), reconstructed ion chromatograms,
and quantitation reports for the initial (five-point)
calibration, labeled as in Section 2.5.4.2.3. Spectra are
not required.
• All initial calibration data that pertain to samples in the
data package shall be included, regardless of when it was
performed and for which Case. When more than one initial
calibration is performed, the data shall be in
chronological order, by instrument.
• EICPs displaying each manual integration.
2.5.4.3.2 Continuing calibration data (Form VII LCSV-1, LCSV-2, LCSV-3)
shall be included in order by instrument, if more than one
instrument used.
• Semivolatile standard(s) reconstructed ion chromatograms
and quantitation reports for all continuing (12-hour)
B-19 OLC03.2
-------
Exhibit B -- Section 2
Reporting Requirements/Order of Data Deliverables (Con't)
calibrations, labeled as in Section 2.5.4.2.3. Spectra are
not required.
• When more than one continuing calibration is performed,
forms shall be in chronological order, by instrument.
• EICPs displaying each manual integration.
2.5.4.3.3 In all instances where the data system report has been edited,
or where manual integration or guantitation has been performed,
• the GC/MS operator shall identify such edits or manual
procedures by initialing and dating the changes made to the
report, and shall include the integration scan range. In
addition, a hardcopy printout of the EICP of the quantitation
ion displaying the manual integration shall be included in the
raw data. This applies to all compounds listed in Exhibit C
(Semivolatiles), internal standards, and deuterated monitoring
compounds.
2.5.4.4 Semivolatiles Raw QC Data
2.5.4.4.1 Decafluorotriphenylphosphine (DFTPP) data shall be arranged in
chronological order by instrument for each 12-hour period, for
each GC/MS system utilized.
• Bar graph spectrum, labeled as in Section 2.5.4.2.4.
• Mass listing, labeled as in Section 2.5.4.2.4.
fO. • Reconstructed total ion chromatogram, labeled as in Section
2.5.4.2.3.
2.5.4.4::'2 Blank data shall be included in chronological order by
••; extraction date.
NOTE: This order is different from that used for samples.
• Tabulated results (Form I LCSV-1, LCSV-2).
• Tentatively identified compounds (Form I LCSV-TIC) even if
none are found.
• Reconstructed ion chromatogram(s) and quantitation
report(s), labeled as in Section 2.5.4.2.3.
• Target compound spectra with laboratory-generated standard
spectra, labeled as in Section 2.5.4.2.4. Data systems
which are incapable of dual display shall provide spectra
in the following order:
Raw target compound spectra.
Enhanced or background-subtracted spectra.
Laboratory-generated standard spectra.
• GC/MS library search spectra for tentatively identified
compounds, labeled as in Section 2.5.4.2.4.
• Quantitation/calculation of tentatively identified compound
concentrations.
OLC03.2 B-20
-------
Exhibit B -- Section 2
Reporting Requirements/Order of Data Deliverables (Con't)
2.5.4.4.3 Semivolatiles Matrix Spike Data
• Tabulated results (Form I LCSV-1, LCSV-2) of target
compounds. Form I LCSV-TIC is not required.
• Reconstructed ion chromatogram(s) and quantitatioh
report(s), labeled as in Section 2.5.4.2.3. Spectra are
not required.
2.5.4.4.4 Semivolatiles Matrix Spike Duplicate Data
• Tabulated results (Form I LCSV-l, LCSV-2) of target
compounds. Form I LSV-TIC is not required.
• Reconstructed ion chromatogram(s) and quantitation
report(s), labeled as in Section 2.5.4.2.3. Spectra are
not required.
2.5.5 Pesticide/Aroclor Data
2.5.5.1 Pesticide/Aroclor QC Summary
2.5.5.1.1 Surrogate Percent Recovery Summary (Form II LCP).
2.5.5.1.2 Matrix Spike/Matrix Spike Duplicate Recovery (Form III LCP-l):
This data shall be provided upon Region's request.
2.5.5.1.3 Laboratory Control Sample Recovery (Form III LCP-2).
2.5.5.1.4 Method Blank Summary (Form IV LCP): If more than a single form
is necessary, forms shall be arranged in chronological order by
date of analysis of the blank.
2.5.5.2 Pesticide/Aroclor Sample Data. Sample data including dilutions
and re-analyses shall be arranged in packets with the Organic
Analysis Data Sheet (Form I LCP) and the raw data for pesticide
samples. These sample packets should then be placed in increasing
.EPA sample number order, considering both letters and numbers.
2.5.5.2.1 Target Compound Results, Organic Analysis Data Sheet (Form I
LCP). Tabulated results (identification and quantitation) of
the specified target compounds (Exhibit C, Pesticides/Aroclors)
shall be included. The validation and release of these results
is authorized by a specific, signed statement in the SDG
Narrative (see Section 2.5.1). In the event that the
laboratory manager cannot verify all data reported for each
sample, the laboratory manager shall provide a detailed
description of the problems associated with the sample in the
SDG Narrative.
2.5.5.2.2 Copies of Pesticide Chromatograms. Positively identified
(identified according to the criteria in Exhibit D Pesticides
and Aroclors) compounds for each column shall be labeled with
the names of compounds, either directly out from the peak on
the chromatogram, or on a printout of retention times on the
data system printout if retention times are printed over the
peak on the chromatogram. All chromatograms shall meet the
acceptance criteria in Exhibit D Pesticides and Aroclors, and
shall be labeled with the following information:
• EPA sample number,-
• Volume injected (uL) ,-
B-21 OLC03.2
-------
Exhibit B -- Section 2
Reporting Requirements/Order of Data Deliverables (Con't)
• Date and time of injection;
• GC column identifier (by stationary phase and internal
diameter);
• GC instrument identifier; and
• Scaling factor.
2.5.5.2.3 Copies of pesticide chromatograms from the second GC column
shall be included and labeled as in Section 2.5.5.2.2.
2.5.5.2.4 Data System Printout. A printout of retention time and
corresponding peak height or peak area shall accompany each
chromatogram. The printout shall be labeled with the EPA
sample number. In all instances where the data system report
has been edited, or where manual integration or quantitation
has been performed, the GC/ECD operator must identify such
edits or manual procedures by initialing and dating the changes
made to the report, and shall include the integration time
range.
2.5.5.2.5 All manual work sheets shall be included in the Sample Data
Package.
2.5.5.3 Pesticide/Aroclor Standards Data
2.5.5^.3.1 Initial Calibration of Single Component Analytes (Form VI LCP-
•:'r 1, LCP-2) : for all GC columns, all instruments, in
chronological order by GC column and instrument.
2.5.5';;3.2 Initial Calibration of Multicomponent Analytes (Form VI LCP-3) :
-~ for all GC columns, all instruments, in chronological order by
::: GC column and instrument.
2.5.5-.3.3 Analyte Resolution Summary (Form VI LCP-4): for all GC columns
and instruments, in chronological order by GC column and
instrument.
2.5.5.3.4 Performance Evaluation Mixture (Form VI LCP-5): for all GC
columns and instruments, in chronological order by GC column
and instrument.
2.5.5.3.5 Individual Standard Mixture A (Form VI LCP-6)-. for all GC
columns and instruments, in chronological order by GC column
and instrument.
2.5.5.3.6 Individual Standard Mixture B (Form VI LCP-7): for all GC
columns and instruments, in chronological order by GC column
and instrument.
2.5.5.3.7 Calibration Verification Summary (Form VII LCP-1): for all
performance evaluation mixtures and instrument blanks, on all
GC columns and instruments, in chronological order by GC column
and instrument. Report for each associated instrument blank.
2.5.5.3.8 Calibration Verification Summary (Form VII LCP-2): for all mid-
point concentrations of Individual Standard Mixtures A and B
and reported for all instrument blanks used for calibration
verification, on all GC columns and instruments, in
chronological order by GC column and instrument.
OLC03.2 B-22
-------
Exhibit B -- Section 2
Reporting Requirements/Order of Data Deliverables (Con't)
2.5.5.3.9 Analytical Sequence (Form VIII LCP): for all GC columns and
instruments, in chronological order by GC column and
instrument.
2.5.5.3.10 Florisil Cartridge Check (Form IX LCP): for all lots of
cartridges used to process samples in the SDG.
2.5.5.3.11 Pesticide Identification Summary for Single Component Analytes
(Form X LCP-1): for all samples with positively identified
single component analytes, in order by increasing EPA sample
number.
2.5.5.3.12 Pesticide Identification Summary for Multicomponent Analytes
(Form X LCP-2): for all samples with positively identified
. multicomponent analytes, in order by increasing EPA sample
number.
2.5.5.3.13 Chromatograms and data system printouts shall be included for
all standards including the following:
• Resolution check mixture;
• Performance evaluation mixtures, all;
• Individual Standard Mixture A, at three concentrations,
each initial calibration;
• Individual Standard Mixture B, at three concentrations,
each initial calibration; ,
• All multicomponent analytes (toxaphene and Aroclors), each
initial calibration;
• All mid-point concentrations of Individual Standard
Mixtures A and B used for calibration verification; and
• All multicomponent analyte standards analyzed for
confirmation.
2.5.5.3.14 A printout of retention time and corresponding peak height or
peak area shall accompany each chromatogram. The printout
• shall be labeled with the EPA sample number. In addition, all
chromatograms shall meet the acceptance criteria in Exhibit D
Pesticides and Aroclors, and shall be labeled with the
following:
• EPA sample number for the standard, e.g., INDA, INDB, etc.
(See Section 3.3.7.6 for details);
• Labels of all standard peaks for all individual compounds
either directly out from the peak on the chromatogram or on
the printout of retention times on the data system printout
if retention times are printed over the peak on the
chromatogram;
• Total nanograms injected for each standard. When total
nanograms injected appear on the printout, it is not
necessary to include them on the chromatogram;
• Date and time of injection;
B-23 OLC03.2
-------
Exhibit B -- Section 2
Reporting Requirements/Order of Data Deliverables (Con't)
• GC column identifier (by stationary phase and internal
diameter);
• GC instrument identifier; and
• Scaling factor.
NOTE:.In all instances where the data system report has been
edited, or where manual integration or quantitation has been
performed, the GC/EC operator must identify such edits or
manual procedures by initialing and dating the changes made to
the report, and shall include the integration time range.
2.5.5.4 Pesticide/Aroclor Raw QC Data
2.5.5.4.1 Blank data shall be arranged by type of blank (method,
instrument, sulfur cleanup) and shall be in chronological order
by instrument.
NOTE: This order is different from that used for samples.
• Tabulated results (Form I LCP).
• Chromatogram(s) and data system printout(s) (GC) for each
GC column and instrument used for analysis, labeled as in
Sections 2.5.5.2.2 and 2.5.5.2.4.
2.5.5.4.2 Laboratory Control Sample Data
• Tabulated results (Form I LCP) of target compounds.
• Chromatogram(s) and data system printout(s) (GC), labeled
as in Sections 2.5.5.2.2 and 2.5.5.2.4 and for both columns
;-" as in Section 2.5.5.2.3.
2.5.5.4.3 Pesticides Matrix Spike '
• Tabulate results (Form I LCP) of target compounds.
• Chromatogram(s) and data system printout(s) (GC), labeled
as in Section 2.5.5.2.2 and 2.5.5.2.4 and for both columns
as in Section 2.5.5.2.3.
2.5.5.4.4 Pesticides Matrix Spike Duplicate Data
• Tabulate results (Form I LCP) of target compounds.
• Chromatogram(s) and data system printout(s) (GC), labeled
as in Section 2.5.5.2.2 and 2.5.5.2.4 and for both columns
as in Section 2.5.5.2.3.
2.5.5.5 Raw Florisil Data. The chromatogram and data system report(s)
shall be arranged in chronological order by Florisil cartridge
performance check analyses.
• Chromatograms and data system reports labeled as specified in
Sections 2.5.5.2.2 and 2.5.5.2.4 for the florisil cartridge
performance check analyses.
• Chromatograms and data system reports for standard analyses
used to quantify compounds in the Florisil cartridge
performance check analysis, labeled as specified in Section
OLC03.2 B-24
-------
Exhibit B -- Section 2
Reporting Requirements/Order of Data Deliverables (Con't)
2.5.5.3.14 (i.e., Individual Standard Mixture A and Individual
Standard Mixture B and the 2,4,5 Trichlorophenol solution).
2.6 Complete SDG File (CSF)
As specified in Section 1, the Contractor shall deliver one Complete SDG
File (CSF) including the original Sample Data Package to the Region
concurrently with delivery of the Sample Data Package to SMO. (Delivery
to a USEPA designated recipient is only required upon written request.)
2.6.1 The CSF will contain all original documentssas specified in Section 3
and Exhibit F, and in Form DC-2 (see Section 4). No photocopies of
original documents will 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 contents of the CSF shall be numbered according to
the specifications described in Section 3.20.
2.6.2 The CSF will consist of the following original documents in addition
to the documents in the Sample Data Package.
NOTE: All SDG-related documentation may be used or admitted as
evidence in subsequent legal proceedings. Any other SDG-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.'
(Deliver the original to the Region and a copy to SMO. Delivery to a
USEPA-designated recipient is only upon written request.)
2.6.2.1 The original Sample Data Package.
2.6*2.2 A completed and signed document inventory sheet (Form DC-2).
2.6.2.3 All original shipping documents including, but not limited to, the
following documents:
• USEPA Chain-of-Custody Record;
• 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);
• USEPA TRs; and
• 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
• SDG cover sheet.
2.6.2.5 All original laboratory records, not already submitted in the
Sample Data Package, 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;
B-25 OLC03.2
-------
Exhibit B .-- Section 2
Reporting Requirements/Order of Data Deliverables (Con't)
• Internal sample and sample extract transfer chain-of-custody
records;
• Screening, records; and
• All instrument output, including strip charts from screening
activities.
2.6.2.6 All other original SDG-specific documents in the possession of the
Contractor including, but not limited to, the following documents:
• Telephone contact logs;
• Copies of personal logbook pages;
• All handwritten SDG-specific notes; and
• 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 should be identified with unique
accountable numbers, a revised Form DC-2 should be submitted, and the
unique accountable numbers and the'locations of the documents in the
CSF should be recorded in the "Other Records" section on the revised
Form DC-2. Alternatively, the Contractor may number the newly
submitted SDG-specific documents to USEPA as a new CSF and submit a
new Form DC-2. The revised Form DC-2 or new Form DC-2 should be
submitted to the USEPA Regions only.
2.7 /Data in Computer-Readable Format
5The Contractor shall provide a computer-readable copy of the data on
data reporting Forms I-X for all samples in the SDG.as specified in
^Exhibit H, and delivered as specified in the Contract Schedule (Contract
-Performance/Delivery Schedule). Computer-readable data deliverables
shall be submitted on IBM or IBM-compatible, 3.5-inch high-density 1.44
tMB diskette (or via an alternate means of electronic transmission
approved in advance by the USEPA) .
2.7.1 When submitted, the 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 or cold or any type of electromagnetic
radiation. The diskette(s) shall be included in the same shipment as
the hardcopy data and shall, at a minimum, be enclosed in a diskette
mailer. The diskette(s) shall be labeled as specified in Exhibit H,
Section 8.4.
2.7.2 The data shall be recorded in ASCII, text file format, and shall
adhere to the file, record, and field specifications listed in
Exhibit H.
2.8 Preliminary Results
The Form I data results shall be submitted for all samples in one SDG of
a Case. This includes tabulated target compound results (Form I) for
the volatile, semivolatile, and pesticide fractions, and tentatively
identified compounds (Form I TIC) for the volatile and semivolatile
fractions. The Contractor shall clearly identify the Preliminary
Results by labeling each Form I and Form I TIC as"Preliminary Results"
under each form title (e.g., under Volatile Organics Analysis Data
Sheet, Volatile Organics Analysis Data Sheet Tentatively Identified
Compounds).
OLC03.2 ' B-26
-------
Exhibit B -- Section 2
Reporting Requirements/Order of Data Deliverables (Con't)
2.8.1 The Contractor shall also include a disclaimer at the bottom of all
Form Is stating that the "Data results contained on this Form I are
for scanning purposes only and may not have been validated fro CLP
criteria." . •
2.8.2 Sample Traffic Reports and SDG Cover Sheets shall be submitted with
the Preliminary Results.
2.9 GC/MS and GC/ECD Tapes
The Contractor shall adhere to the requirements in Section 13 of
Exhibit E.
2.10 Extracts
The Contractor shall preserve sample extracts at 4°C (±2°C) in
bottles/vials with PTFE-lined septa. Extract bottles/vials shall be
labeled with EPA sample number, Case number, and SDG number. The
Contractor shall maintain a logbook of stored extracts, listing EPA
sample numbers and associated Case and SDG numbers. The Contractor
shall retain extracts for 365 days following submission of the
reconciled complete Sample Data Package. During that time, the
Contractor shall submit extracts and associated logbook pages within
seven days following receipt of a written request from the CLP PO.
B-27 OLC03.2
-------
Exhibit B -- Section 3
Form Instructions
3 . 0 FORM INSTRUCTIONS
3 .1 Introduction
This section includes specific instructions for completing the data
reporting forms required under this contract. Each of the forms is
specific to a given fraction (volatile, semivolatile, or
pesticide/Aroclor). The Contractor shall submit only those forms
pertaining to the fractions analyzed for a given sample(s). For
instance, if a sample is scheduled for volatiles analysis only, the
Contractor shall provide only forms for the volatile fraction.
3.2 General Information
The Contractor shall report values on the hardcopy forms according to
the individual form instructions in this section. For instance, all
results for concentrations of target compounds shall be reported to two
significant figures. Values that exceed the maximum length allowed
shall be reported to the maximum possible, maintaining the specified
significance.
3.2.1 The data reporting forms presented in Section 4 have been designed in
conjunction with the computer-readable data format specified in
Exhibit H. The specific length of each variable for
computer-readable data transmission purposes is also 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 identifier.
NOTE: The space provided for entries on the hardcopy forms (Section
4) 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 visual clarity.
3.2.2 When submitting data, the Contractor shall reproduce all characters
that appear on the data reporting forms in Section 4. 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 from the Contract Laboratory
Program Project Officer (CLP PO). The names of the various fields
and compounds (e.g., "Lab Code," "Chloromethane") shall appear as
they do on the forms in the contract. For items appearing on the
uncompleted forms (Section 4), the use of uppercase and lowercase
letters is optional.
3.2.3 Alphabetical entries made on the forms by the Contractor shall be in
ALL UPPERCASE letters (e.g., "ABCDE", not "Abcde" or "abcde"). 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. However, the Contractor shall not remove
the underscores or vertical bars that delineate "boxes" on the forms.
The only exception would be those underscores at the bottom of a
"box" that are intended as a data entry line. (For instance, on Form
2LCV, line 30, if data is entered on line 30, it will replace the
underscores.)
OLC03.2 B-28
-------
Exhibit B -- Section 3
Form Instructions (Con't)
3.3 Header Information
Six pieces of information are common to the header section of each data
reporting form: lab name, contract, lab code, Case number. Client number
and Sample Delivery Group (SDG) number. Except as noted for Client
number, this information shall be entered on every form and shall match
on every form.
3.3.1 Lab Name. The lab name shall be the name chosen by the Contractor to
identify its laboratory. It shall not exceed 25 characters.
3.3.2 Contract. Contract refers to the number of the USEPA contract under
which the analyses were performed.
3.3.3 Lab Code. -The lab code is an alphabetical abbreviation of up to six
letters, as assigned bv USEPA. to identify the laboratory and aid in
data processing. This lab code will be assigned by USEPA at the time
a contract is awarded, and 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 lab code will remain the same until the
Contractor is directed by USEPA to use another lab code.
3.3.4 Case Number. The Case number is the USEPA-assigned Case number
associated with the sample. This number is reported on the Traffic
Report (TR).
3.3.5 Client Number. The Client number is a unique number identifying the
client and the project. This number may be 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 as "Client No." 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 "Client No."
field blank.
NOTE: Some samples in an SDG may have a Client Number where as other
may not.
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 SDG's 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 an SDG number.
3.3.7 Sample Number. This number appears either in the upper right-hand
corner of the form, or as the left column of a table summarizing data
from a number of samples. When the EPA sample number is entered in
the triple-spaced box in the upper right-hand corner of Form I, Form
IV, or Form X, it should be entered on the middle line of the three
lines that comprise the box.
B-29 OLC03.2
-------
Exhibit B -- Section 3
Form Instructions (Con't)
3.3.7.1 The Contractor shall identify all samples, including dilutions and
re-analyses, Laboratory Control Samples, requested Matrix
Spike/Matrix Spike Duplicate(s) (MS/MSD) (as described in Section
3.3.7.4), blanks, and standards with an EPA sample number. For
field samples, the EPA sample number is the five digit unique
identifying number given in the TR that accompanied that sample.
In order to facilitate data assessment, the Contractor shall use
the following sample suffixes:
XXXXX = EPA sample number
XXXXXMS =. Matrix spike sample
XXXXXMSD = Matrix spike duplicate sample
XXXXXRE = Re-extracted and re-analyzed sample
XXXXXDL = Sample analyzed at a dilution
XXXXXDL2 = Sample analyzed at a secondary dilution
XXXXXDL3 = Sample analyzed at a third dilution
NOTE: The Region may approve up to one additional dilution be
performed beyond the one dilution for volatiles and semivolatiles
and two dilutions for pesticides specified in Exhibit D. The
approval of the additional dilution by the Region must be
documented in the SDG Narrative and include the Telephone Record
Conversation between SMO and the Contractor communicating USEPA's
decision.
3.3..7.2 There may be instances when all samples analyzed must be listed 'on
• •:.. the form, regardless of whether or not they are part of the SDG
„:':. . being reported (e.g.. Form VIII LCP).. In these instances, use
•;-.. ZZZZZ as the EPA sample number for any sample analysis not
:..x associated with the SDG being reported.
.3'
3.3;.,7.3 For blanks, the Contractor shall use the following identification
scheme for the EPA sample number:
• Volatile method blanks shall be identified as VBLK##;
• Volatile instrument blanks shall be identified as VIBLK##;
• Volatile storage blanks shall be identified as VHBLK##;
• Semivolatile method blanks shall be identified as SBLK##;
• Pesticide/Aroclor method blanks and/or sulfur cleanup blanks
shall be identified as PBLK##; and
• Pesticide/Aroclor instrument blanks shall be identified as
PIBLK##.
3.3.7.3.1 The EPA sample number shall be unique for each blank within an
SDG. Within a fraction, the Contractor shall achieve this by
replacing the two-character terminator (##) of the identifier
with one or two characters or numbers, or a combination of
both. For example, possible identifiers for volatile blanks
would be VBLK1, VBLK2, VBLKA1, VBLKB2, VBLK10, VBLKAB, etc.
3.3.7.3.2 If the method blank is analyzed on multiple instruments, then
an additional two-character suffix shall be added to make the
blank EPA sample number unique.
OLC03.2 B-30
-------
Exhibit B -- Section 3
Form Instructions (Con't)
3.3.7.4 The EPA sample number shall be unique for each Laboratory Control
Sample within an SDG. The EPA sample number for a Laboratory
Control Sample must be PLCS##.
Where:
P = fraction (P for pesticides/Aroclors)
LCS = indicates a Laboratory Control Sample
## = suffix consisting of characters or numbers or both that
makes the EPA sample number for the LCS unique in the
SDG.
(1) = When reporting results on Form I, a "(1)" is appended on
to the sample number to indicate that the results are
from Gas Chromatograph (GC) column(l) [e.g., PLCSOl(l) ].
(2) = When reporting results on Form I, a "(2)" is appended on
to the sample number to indicate that the results are
from GC column(2) [e.g., PLCSOK2) ].
3.3.7.5 Volatile and semivolatile standards shall be identified as
FSTD***##.
Where:
F = Fraction code (V for volatiles; S for semivolatiles)
STD = Standard (
*** = Concentration of volatile standards in ug/L (e.g., 0.5,
001, 005, 010, and 025) or the amount injected in ng for
semivolatile standards (e.g., 005, 010, 020, 050, and
080)
## = One or two characters, numbers, or combinations of both
to create a unique EPA sample number within an SDG.
3.3.7.6 The Contractor shall use the following scheme to identify
pesticide/Aroclor standards:
EPA Sample Number
Individual Mix A (low point) INDAL##
Individual Mix A (mid-point) INDAM##
Individual Mix A (high point) INDAH##
Individual Mix B (low point) INDBL##
Individual Mix B (mid-point) INDBMi#
Individual Mix B (high point) ' INDBH##
Resolution Check RESC##
Performance Evaluation Mixture PEM##
Toxaphene TOXAPH##
Aroclor 1016 AR1016##
Aroclor 1221 AR1221##
Aroclor 1232 AR1232##
Aroclor 1242 AR1242##
Aroclor 1248 AR1248##
B-31 OLC03.2
-------
Exhibit B -- Section 3
Form Instructions (Con't)
Name EPA Sample Number
Aroclor 1254 AR1254##
Aroclor .1260 AR1260##
Aroclor 1016/1260 Mix AR1660##
The Contractor shall replace the two-character terminator (##) of
the identifier with one or two characters or numbers, or a
combination of both, to create a unique EPA sample number within
an SDG.
3.3.7.6.1 If the standards are injected onto both GC columns on the same
instrument simultaneously, the same EPA sample number may be
used for reporting data for the standards for both columns. If
simultaneous injections are not made, then the same number
shall not be used.
3.3.7.7 The EPA sample number for florisil shall be FLO###«#####, where
######### is the florisil cartridge lot number. If the florisil
cartridge lot number is more than nine characters, truncate at the
ninth character.
3.3.8 Other Common Fields. Several other pieces of information are common
to many of the data reporting forms. These include purge
volume/sample volume, lab sample identifier, lab file identifier,
instrument ID, and page _ of _.
3.3.8.1 "Purge Volume" or "Sample Volume" is the total volume of water
that was purged or extracted, in milliliters (mL).
P.
3.3.8.'2 The lab sample identifier is a unique laboratory-generated
-,i internal identifier pertaining to a particular analysis. The
Contractor can enter up to 12 alpha-numeric characters in the "Lab
Sample ID" field. The Contractor may use the EPA sample number as
-•" the lab sample identifier.
3.3.8.3 The lab file identifier is the unique laboratory-generated name of
the GC/MS data system file containing information pertaining to a
particular analysis. The Contractor can enter up to 14
alpha-numeric characters in the "Lab File ID" field.
3.3.8.4 The "Instrument ID" field is common to the forms containing
calibration data. The identifier used by the Contractor shall
include some indication of the manufacturer and/or model of the
instrument, and shall contain additional characters that
differentiate between all instruments of the same type in the
laboratory.
3.3.8.5 The GC column identifier, and inner diameter are common to many of
the reporting forms for the volatile and pesticide fractions. In
addition, column length is entered on the volatile reporting
forms. Under "GC Column", enter the column identification as
denoted by the manufacturer. Enter the inner diameter in the "ID"
field in millimeters (mm) (to two decimal places), and the column
length in the "Length" field in m (in whole numbers).
3.3.8.6 Forms II, III, IV, V, VIII, IX, and X contain a field labeled
"page _ of _" in the bottom lefthand corner. If the number of
entries required on any of these forms exceeds the available
space, continue entries on another copy of the same
fraction-specific form, duplicating all header information. If a
second page is required, number the pages consecutively (i.e.,
OLC03.2 B-32
-------
Exhibit B -- Section 3
Form Instructions
Form Is
"page 1 of 2" and "page 2 of 2"). If a second page is not
required, number the page "page 1 of 1."
NOTE: These forms are fraction-specific. For'example, Form II LCV
and Form II LCSV are for different data. Therefore, do not number
the pages of all three versions of Form II as "1 of 6," "2 of 6,"
etc. Number only pages corresponding to the fraction-specific
form.
3.3.9 Rounding Rule. For rounding off numbers to the appropriate level of
precision, the Contractor shall follow these rules. If the figure
following those to be retained is less than 5, drop it (round down).
If the figure is greater than or equal to 5, drop it and increase the
last digit to be retained by 1 (round up).
3.4 Organic Analysis Data Sheet (Form I, All Fractions)
3.4.1 Purpose. This form is used for tabulating and reporting sample
analysis, including dilutions, re-analysis, blank, Laboratory Control
Sample for target compounds and requested MS/MSD. .If all fractions
are not requested for analysis, only the pages for the fractions
required shall be submitted. For example, if only volatiles analysis
is requested, Form I LCV-1, LCV-2 and Form I LCV-TIC shall be
submitted. If only the pesticide/Aroclor fraction is requested for
analysis. Form I LCP shall be submitted. Furthermore, pesticide
instrument blanks (PIBLKs) shall be reported on a per column/per
analysis basis on Form I LCP. Each PIBLK shall be named with a
unique EPA sample number. Also, the Laboratory Control Sample and
the MS/MSD shall be reported on a per column basis. Distinguish
between GC column(1) and GC column (2) results by appending a- suffix
n(l)n for GC column(l) and "(2)" for GC column(2).
3.4.2 Instructions. Complete the header information according to the
instructions in Section 3.3. Complete the remainder of the form
using the following instructions.
3.4.2.1 Enter the date of sample receipt at the laboratory, as noted on
the TR (i.e., the VTSR), in the "Date Received" field. The date
shall be entered as MM/DD/YYYY.
3.4.2.2 Complete the "Date Extracted" and "Date Analyzed" fields in the
same format (MM/DD/YYYY). For the continuous liquid-liquid
extraction procedures, enter the date that the procedure was
started in the "Date Extracted" field. If separatory funnel
(pesticides only) was used, enter the date the procedure was
completed in the "Date Extracted" field. For pesticide/Aroclor
samples, enter the date of the first GC analysis performed in the
"Date Analyzed" field. The date of sample receipt will be
compared with the extraction and analysis dates of each fraction
to ensure that contract holding times were not exceeded.
3.4.2.3 For volatiles on Form I LCV-1 and LCV-2, enter the GC column
identifier in the "GC Column" field, the internal diameter in mm,
to two decimal places in the "ID" field, and the length in meters
(m), as a whole number, as described in Section 3.3.
3.4.2.4 For pesticides/Aroclors, enter the method .of extraction in the
"Extraction" field on Form I LCP as "SEPF" for separatory funnel,
or "CONT" for continuous liquid-liquid extraction.
B-33 OLC03.2
-------
Exhibit B -- Section 3
Form Instructions
Form Is (Con't)
3.4.2.5 For semivolatiles and pesticides/Aroclors, enter the actual volume
of'the most concentrated sample extract, in microliters (uL) , in
the "Concentrated Extract Volume" field on Form I LCSV-1, LCSV-2
or LCP. For semivolatiles, this volume will typically be 1,000
uL. For pesticides/Aroclors, the volume of the most concentrated
extract will typically be 2,000 uL. If a dilution of the sample
extract is made in a subsequent analysis, this volume will remain
the same, but the dilution factor will change.
3.4.2.6 For semivolatiles and pesticides/Aroclors, enter the volume of the
sample extract injected into the GC in the "Injection Volume"
field on Form I LCSV-1, LCSV-2 or LCP. Report this volume in
microliters (uL) to one decimal place (e.g., 1.0 uL) .
3.4.2.7 If pesticides/Aroclors are analyzed using two GC columns connected
to a single injection port, enter the amount of half the volume in
the syringe in the "Injection Volume" field (i.e., assume that .the
extract injected is evenly divided between the two columns).
3.4.2.8 If a sample or sample extract has been diluted for analysis, enter
the dilution factor as a single number (e.g., enter 100.0 for a 1
to 100 dilution of the sample) in the "Dilution Factor" field.
The dilution factor shall not be entered as a fraction. If a
sample was not diluted, enter 1.0. Report dilution factors to one
decimal place.
3.4.2.9 If sulfur cleanup is employed, enter Y in the "Sulfur Cleanup"
field; if not, enter N on Form I LCP.
3.4.2.10 For positively identified target compounds, the Contractor shall
report the concentrations as uncorrected for blank contaminants.
3.4.2.:il Report all analytical results to two significant figures.
3.4.2.12 Under the column labeled "Q" for qualifier, flag each result with
the specific data reporting qualifiers listed below. When
reporting results to USEPA, the Contractor shall use these
contract-specific qualifiers. The Contractor shall not modify the
qualifiers. Up to five qualifiers may be reported on Form I for
each compound. The Contractor is encouraged to use additional
flags or footnotes (see the X qualifier).
The USEPA-defined qualifiers to be used are:-
U: This flag indicates the compound was analyzed for but not
detected. The Contract Required Quantitation Limit (CRQL) shall
be adjusted according to the equation listed in Exhibit D. CRQLs
are listed in Exhibit C.
J: This flag indicates an estimated value. This flag is used (1)
when estimating a concentration for tentatively identified
compounds where a 1:1 response is assumed, (2) when the mass
spectral and retention time data indicate the presence of a
compound that meets the volatile and semivolatile GC/MS
identification criteria, and the result is less than the CRQL but
greater than zero, and (3) when the retention time data indicate
the presence of a compound that meets the identification criteria
for a pesticide and/or an Aroclor, and the result is less than the
CRQL but greater than zero. For example, if the sample
quantitation limit is 5.0 ug/L, but a concentration of 3.0 ug/L is
calculated, report it as 3.0J.
OLC03.2 B-34
-------
Exhibit B -- Section 3
Form Instructions
Form Is (Con't)
NOTE: The J flag is not used and the compound is not reported as
being identified for pesticide/Aroclor results less than the CRQL
if the pesticide residue analysis expert determines that the peaks
used for compound identification resulted from instrument noise or
other interferences (column bleed, solvent contamination, etc.).
N: This flag indicates presumptive evidence of a compound. This
flag is only used for Tentatively Identified Compounds (TICs),
where the identification is based on a mass spectral library
search. It is applied to all TIC results. For generic
characterization of a TIC, such as chlorinated hydrocarbon, the N
flag is not used.
P: This flag is used for a pesticide/Aroclor target analyte when
there is greater than 25% difference for detected concentrations
between the two GC columns (see Form X). The lower of the two
values is reported on Form I and flagged with a P. The P flag is
not used unless a compound is identified on both columns.
C: This flag is not used under this contract, but it is reserved
for USEPA use.
B: This flag is used when the analyte is found in the associated
blank as well as in the sample. It indicates probable blank
contamination and warns the data user to take appropriate action.
This flag shall be used for a TIC as well as for a positively
identified target compound.
The combination of flags BU or UB is expressly prohibited. Blank
contaminants are flagged B only when they are detected in the
sample.
E: This flag identifies compounds whose concentrations exceed the
upper level of the calibration range of the instrument for that
specific analysis. If one or more compounds have a concentration
greater than the upper level of the calibration range, the sample
or extract shall be diluted and re-analyzed according to the
specifications in Exhibit D; exceptions are also noted in Exhibit
D. All such compounds with concentrations greater than the upper
level of the calibration range shall have the concentrations
flagged with an E on Form I for the original analysis. The
results of both analyses shall be reported on separate copies of
Form I. The Form I for the diluted sample shall have for the
volatile and semivolatile dilutions "DL" or ("DL2", when this
additional dilution was approved by the Region) and for the
pesticides dilution "DL" or "DL2" (or "DL3", when approved by the
Region) suffix appended to the sample number.
NOTE: For total xylenes, where three isomers are quantified as two
peaks, the calibration range of each peak shall be considered
separately. For example, a diluted analysis is not required for
total xylenes unless the concentration of the peak representing
the single Isomer exceeds 25 ug/L or the peak representing the two
co-eluting isomers on that GC column exceeds 50 ug/L.
D: This flag is used for all compounds identified in an analysis
as diluted. If a sample or extract is re-analyzed with a
dilution factor greater than 1, for example, when the
concentration of the analyte exceeds the upper calibration range,
the "DL", "DL2" or "DL3" suffix is appended to the sample number
on Form I for the more diluted sample, and all reported
B-35 OLC03.2
-------
Exhibit B -- Section 3
Form Instructions
Form I LCV-TIC and LCSV-TIC
concentrations on that Form I are flagged with the D flag. This
flag alerts data users that any discrepancies between the reported
concentrations may be due to dilution of the sample or extract.
NOTE 1: The D flag is not applied to compounds which are not
detected in the sample analysis, i.e., compounds reported with the
CRQL and the U flag.
NOTE 2: Separate Form Is are required for reporting the original
analysis (EPA Sample No. XXXXX) and the more diluted sample
analyses, i.e., the results from these analyses cannot be combined
on a single Form I.
A: This flag indicates that a Tentatively Identified Compound
(TIC) is a suspected aldol-condensation product.
X:Other specific flags may be required to properly define the
results. If used, the flags shall be fully described in the SDG
Narrative. Begin by using X. If more than one flag is required,
use Y and Z as needed. If more than five qualifiers are required
for a sample result, use the X flag to represent a combination of
several flags. For instance, the X flag might combine the B and D
flags for some samples. The laboratory-defined flags are limited
to X, Y, and Z.
3.5 Organic Analysis Data Sheet: Tentatively Identified Compounds
; (Form I LCV-TIC and Form I LCSV-TIC)
3.5.1:'i's Purpose. These forms are used to report analysis results for non-
:i'•-• target compounds (e.g., compounds not listed in Exhibit C) , excluding
deuterated monitoring compounds and internal standards. See Exhibit
D for instructions on identification and quantitation. The
••'iP Contractor shall submit Form I LCV-TIC or LCSV-TIC for every
•aii analysis, including required dilutions and re-analyses, and blanks,
even if no TICs are found.
.s
3.5.2 Instructions. Complete the header information according to the
instructions in Section 3.3. Complete the remainder of the form
using the following instructions in addition to the instructions in
Section 3.4.
3.5.2.1 Report all TICs including CAS number (if applicable), compound
name, retention time, and the estimated concentration as
uncorrected for blank contaminants. Report all analytical results'
to two significant figures. (Criteria for reporting TICs are
given in Exhibit D, Section 11). Retention time shall be reported
in minutes and decimal minutes, not seconds or minutes:seconds.
3.5.2.2 Total the number of TICs found, and enter this number in the
"Number TICs found" field. If no TICs were found, enter 0 (zero).
3.5.2.3 If the name of a compound exceeds the 28 spaces in the TIC column,
truncate the name to 28 characters. If the compound is an
unknown, restrict the description to no more than 28 characters
(e.g., unknown hydrocarbon).
OLC03.2 B-36
-------
Exhibit B -- Section 3
Form Instructions
Form II LCVs and LCSVs
3.6 Deuterated Monitoring Compound (DMC) Recovery (Form II LCV-1, LCV-2 and
Form II LCSV-1, LCSV-2)
3.6.1 Purpose. For volatiles and semivolatiles, Form II LCV-1, LCV-2 and
Form II LCSV-1, LCSV-2 are used to report the recoveries of the DMCs
added to each volatile and semivolatile sample, including dilutions,
re-analyses, blanks and requested MS/MSD. The DMCs are used to
monitor the performance of the purge and trap for volatiles, the
extraction and injection for semivolatiles, and the GC/MS system as a
whole.
3.6.2 Instructions. Complete the header information according to the
instructions in Section 3.3.
3.6.2.1 For each volatile DMC listed in Table 2 and each semivolatile DMC
listed in Table 3, report the percent recovery to the nearest
whole percentage point, and to the number of significant figures
given by the QC limits at the bottom of the form.
Table 2
Volatile Deuterated Monitoring Compounds
Volatile Deuterated
Monitoring Compounds
VDMC1
VDMC2
VDMC3
VDMC4
VDMC5
VDMC6
VDMC7
VDMC8
VDMC9
VDMC10
VDMC11
VDMC12
VDMC13
VDMC14
Vinyl Chloride-d3
Chloroethane-d5
1 , 1 - Dichl oroethene - d2
2 -Butanone-d5
Chloroform-d
1 , 2 -Dichloroethane-d4
Benzene-d6
1, 2-Dichloropropane-d6
Toluene -d8
trans-l,3-Dichloropropene-d4
2-Hexanone-d5
Bromoform-d
1, l,2,2-Tetrachloroethane-d2
1, 2-Dichlorobenzene-d4
CAS Number
6745-35-3
19199-91-8
22280-73-5
24313-50-6
865-49-6
17060-07-0
1076-43-3
93952-08-0
2037-26-5
93951-86-1
4840-82-8
2909-52-6
33685-54-0
2199-69-1
B-37
OLC03.2
-------
Exhibit B — Section 3
Form Instructions
Form II LCP
Table 3
Semivolatile Deuterated Monitoring Compounds
Semivolatile Deuterated
Monitoring Compounds
SDMC1
SDMC2
SDMC2
SDMC4
SDMC5
SDMC6
SDMC7
SDMC8
SDMC9
SDMC10
SDMC11
SDMC12
SDMC13
SDMC14
SDMC15
SDMG16
Phenol -d5
bis- (2-Chloroethyl)ether-d8
2-Chlorophenol-d4
4-Methylphenol-d8
Nitrobenzene-dS
2-Nitrophenol-d4
2 , 4 -Dichlorophenol -d3
4-Chloroaniline-d4
Dimethylphthalate - d6
Acenaphthyl ene - d8
4 -Nitrophenol -d4
Fluorene-dlO
4 , 6-Dinitro-methylphenol-d2
Anthracene- dlO
Pyrene-dlO
Benzo (a) pyrene-d!2
CAS Number
4165-62-2
93952-02-4
93951-73-6
190780-66-6
4165-60-0
93951-78-1
93951-74-7
191656-33-4
85448-30-2
93951-97-4
93951-79-2
81103-79-9
93951-76-9
1719-06-8
1718-52-1
63466-71-7
3.6.2.2 Flag each DMC recovery outside the QC limits with an asterisk (*).
The asterisk shall be placed in the last space in each appropriate
column, under the "#" symbol.
3.6.2.3 In the "TOT OUT" column, total the number of DMC recoveries that
were outside the QC limits for each sample. If no DMCs were
outside the limits, enter 0 (zero).
3.6.2.4 If the sample is a dilution and the deuterated monitoring
compounds (DMCs) are outside the acceptance window, enter the
calculated recovery and flag the DMC recoveries with a D in the
column under the "#" symbol. Do not include recoveries flagged
with a D in the total number of recoveries for each sample outside
the QC limits.
3.6.2.5 Number all pages as described in Section 3.3.
3.7 Surrogate Recovery (Form II LCP)
3;7.1 Purpose. Form II LCP is used to report the recoveries of the
surrogate compounds added to each pesticide/Aroclor sample, blank.
Laboratory Control Sample and requested MS/MSD.
OLC03.2
B-38
-------
Exhibit B — Section 3
Form Instructions
Form III LCV, LCSV, LCP-1
3.7.2 Instructions. Complete the header information according to the
instructions in Section 3.3. Complete the remainder of the form
using the following instructions.
3.7.2.1 For each surrogate listed in Table 4, report the percent recovery
to the nearest whole percentage point.
3.7.2.2 Flag each surrogate recovery outside the QC limits with an
asterisk (*). The asterisk shall be placed in the last space in
each appropriate column, under the "#" symbol.
3.7.2.3 In the "TOT OUT" column, total the number of surrogate recoveries
that were outside the QC limits for each sample. If no surrogates
were outside the limits, enter 0 (zero).
3.7.2.4 If the samples is a dilution and the surrogates-are outside the
acceptance window in any analysis, enter the calculated recovery,
and flag the surrogate recoveries with a D in the column under the
"#" symbol. Do not include results flagged with a D in the total
number of recoveries for each sample outside the QC limits.
3.7.2.5 The pesticide surrogate recoveries shall be reported from each GC
column used for the analyses. Therefore, identify each GC column
at the top of Form II LCP, entering the stationary phase in the
"GC Column" field, and the internal diameter of the column in mm
in the "ID" field.
3.7.2.6 The assignment of columns as "1" and "2" is left to the discretion
of the Contractor when the analyses are performed by simultaneous
injection into a GC containing two columns. If so analyzed, the
assignment of "GC Column 1" and "GC Column 2" shall be consistent
across all the reporting forms. If the analysis is not performed
by simultaneous injection, then the assignment of GC column number
shall be based on the chronological order of the two analyses.
3.7.2.7 Number all pages as described in Section 3.3.
Table 4
Pesticide Surrogates
Pesticide Surrogates CAS Number
Decachlorobiphenyl (DCB) 2051-24-3
Tetrachloro-m-xylene (TCX) 877-09-8
3.8 Matrix Spike/Matrix Spike Duplicate Recovery (Form III, All Fractions,
LCV, LCSV, LCP-1)
3.8.1 Matrix Spike/Matrix Spike Duplicate Recovery and Laboratory Control
Sample Recovery
3.8.1.1 Purpose. This form is used to report the results of the analyses
of MS/MSD. This form should only be submitted if the analysis of
MS/MSD samples have been requested by the Region. Complete Form
III LCP-1 for each GC column used for analysis.
3.8.1.2 Instructions. Complete the header information according to the
instructions in Section 3.3; Include the EPA sample number for
the matrix spike, without the suffixes MS or MSD. Complete the
remainder of the form using the following instructions. For each
B-39 OLC03.2
-------
Exhibit B — Section 3
Form Instructions
Form III LCP-2
Form III LCP-1 enter the Instrument ID, the stationary phase in
the "GC Column" field, and the internal diameter of the column in
mm in-the "ID" field- The order of reporting is not important but
must be consistent with Form X.
3.8.1.2.1 In the first table under the "SPIKE ADDED" column, enter the
amount of spike added in ug/L for each analyte..
3.8.1.2.2 Enter the sample concentration in the next column of each spike
compound detected in the original sample. If a spike compound
was not detected during the analysis of the original sample,
enter the sample result as 0 (zero).
3.8.1.2.3 In the "MS CONCENTRATION" column, enter the actual
concentration of each spike compound detected in the matrix
spike aliquot.
3.8.1.2.4 Calculate the percent recovery of each spike compound in the
matrix spike aliquot to the nearest whole percent, according to
Exhibit D. Enter the percent recovery in the "MS % REC"
column.
3.8.. 1.2.5 Flag all percent recoveries outside the QC limits with an
asterisk (*). The asterisk shall be placed in the last space
of the "MS % REC" column, under the "#" symbol.
3.8.1.2.6 Follow Sections 3.8.1.2.1 through 3.8.1.2.5 to complete the
*;•• lower table, using the results of the analysis of the MSD
~& aliquot.
•'0-
3.8.1.-2-.7 Calculate the relative percent difference (RPD) between the
•St'• matrix spike recovery and the matrix spike duplicate recovery,
'£' and enter this value in the "RPD" column. Report the RPD to
«»• the nearest whole percent.
3.8.1.2.8 Compare the RPDs to the QC limits given on the form, and flag
each RPD outside the QC limits with an asterisk (*) in the last
space of the "RPD" column, under the "#" symbol.
3.8.1.2.9 Summarize the values outside the QC limits at the bottom of the
page. No further action is required by the Contractor.
3.8.2 Laboratory Control Sample Recovery (Form III LCP-2)
3.8.2.1 Purpose. Form III LCP-2 is used to report the results of the
analyses of the Laboratory Control Samples.
3.8.2.2 Instructions. Complete the header information according to the
instructions in Section 3.3. Complete the remainder of the form
using the following instructions.
3.8.2.2.1 If the LCS solution is purchased by the Contractor from a third
party, report the identification number used by the third party
to identify the LCS lot, if available. If the LCS solution was
prepared in-house, leave this entry blank.
3.8.2.2.2 The "LCS Aliquot" is the volume in microliters (uL) of LCS
spiking solution that was added to reagent water before
extraction.
OLC03.2 B-40
-------
Exhibit B -- Section 3
Form Instructions
Form IVs
3.8.2.2.3 The LCS is reported for each GC column. Enter the Instrument
ID,' GC column, and internal diameter (ID) for both GC columns.
The order of reporting is not important, but must be consistent
with the information reported on Form X. If simultaneous
injections are not made, the "Date Analyzed" is the earlier
date of the two LCS analyses. The dates should be entered in
MM/DD/YYYY format.
3.8.2.2.4 In the box (upper for Pesticides) in Form III, under "AMOUNT
ADDED", enter the amount in nanograms (ng) of each analyte
added to the sample. Under "AMOUNT RECOVERED", enter the
amount in ng of each analyte in the sample calculated from
analysis. Calculate the percent recovery of each compound in
the sample to the nearest whole percent, according to Exhibit
D, and enter under "% REC". Flag all percent recoveries which
do not meet the contract requirements with an asterisk (*).
The asterisk must be placed in the last space of the percent
recovery column, under the "#" symbol.
3.8.2.2.5 Complete the lower box according to the instructions in Section
3.8.2.2.4.
3.8.2.2.6 Summarize the values outside the QC limits at the bottom of the
page.
NOTE: This means the results for both columns.
3.9 Method Blank Summary (Form IV, All Fractions)
3.9.1 Purpose. This form summarizes the samples associated with each
method blank analysis. The Contractor shall submit the appropriate
Form IV for each blank.
3.9.2 Instructions. Complete the header information according to the
instructions in Section 3.3. The EPA sample number entered in the
upper right-hand corner shall be the same number entered on Form I
for the blank. Complete the remainder of the form using the
following instructions.
3.9.2.1 Complete the following fields: "Instrument ID", "Date Analyzed",
and "Time Analyzed". Dates shall be entered as MM/DD/YYYY. The
time shall be reported in military time.
3.9.2.2 Pesticide/Aroclor contaminants shall meet the identification '
criteria requiring analysis of the blank on two different GC
columns (see Exhibit D PEST). Enter the date, time, and
instrument ID of both analyses of the blank on the pesticide
method blank summary (Form IV LCP). The information on the two
analyses is differentiated as Date Analyzed (1), Date Analyzed
(2), etc. 'If the analyses were run simultaneously, the order of
reporting is not important, but shall be consistent with the
information reported on all other pesticide forms. Otherwise,
Date Analyzed (1) shall indicate the analysis on column 1, and
Date Analyzed (2) shall indicate the analysis on column 2.
3.9.2.3 For pesticide/Aroclor blanks, enter the method of extraction as
"SEPF" for separatory funnel, or "CONT" for continuous liquid-
liquid extraction on Form IV LCP.
3.9.2.4 Identify the GC column, internal diameter, and length in the
appropriate fields, as indicated in Section 3.3.
B-41 OLC03.2
-------
Exhibit B -- Section 3
Form Instructions
Form V LCV and LCSV
3.9.2.5 For semivolatile and pesticide/Aroclor method blanks, enter the
date of extraction of the blank on Form IV LCSV or LCP.
3.9.2.6 If the samples associated with pesticide/Aroclor blank are
subjected to sulfur cleanup, then the blank shall also be
subjected to sulfur cleanup. If sulfur cleanup is employed, enter
Y in the "Sulfur Cleanup" field; if not, enter N on Form IV LCP.
If only some of the samples associated with the method blank are
subjected to sulfur cleanup, a separate sulfur cleanup blank is
required (see Exhibit D PEST). If a separate sulfur cleanup blank
is prepared, complete one version of Form IV.associating all the
samples with the method blank, and a second version of Form IV
listing only those samples associated with the separate sulfur
cleanup blank.
NOTE: Subjecting all samples associated with a method blank to
sulfur cleanup avoids the need for two forms.
3.9.2.7 For all three fractions, as appropriate, summarize the samples
associated with a given method blank in the table, entering the
EPA sample number and lab sample identifier. For volatiles, enter
the lab file identifier and the time of analysis of each sample.
For semivolatiles, enter the lab file identifier and date of
analysis. For pesticides/Aroclors, enter the dates of both
analyses as Date Analyzed (1) and Date Analyzed (2), as discussed
previously.
3.9.2.8 Number all pages as described in Section 3.3.
3.10 ;;GC/MS Instrument Performance Check (Form V LCV and Form V LCSV)
3.10.1 Purpose. This form is used to report the results of the GC/MS
instrument performance check for the volatile and semivolatile
~.l' fractions and to summarize the date and time of analyses of samples,
.i including dilutions and re-analyses, standards, blanks, and requested
"•! MS/MSD associated with each analysis of the instrument performance
check solution.
3.10.2 Instructions. Complete the header information according to the
instructions in Section 3.3. Complete the remainder of the form
using the following instructions.
3.10.2.1 Enter the date and time of injection of the instrument performance
check solution (BFB for volatiles--CAS Number 460004, DFTPP for
semivolatiles--CAS Number 5074715). The date shall be entered as
MM/DD/YYYY. The time shall be reported as military time.
3.10.2.2 For volatiles, identify the GC column, internal diameter, and
column length on Form V LCV, as described in Section 3.3.
3.10.2.3 For each ion listed on the form, enter the percent relative
abundance in the right-hand column of the first table. Report
relative abundances to the number of significant figures given for
each ion in the ion abundance criteria column.
NOTE: For both BFB and DFTPP, one or more of the high mass ions
may exceed the abundance of the ion listed on the form as the
nominal base peak, m/z 95 for BFB and m/z 198 for DFTPP. Despite
this possibility, all ion abundances shall be normalized to the
nominal base peaks listed on Form V (see Exhibits D).
OLC03.2 B-42
-------
Exhibit B -- Section 3
Form Instructions
Form VI LCVs, LCSVs, and LCPs
3.10.2.4 All relative abundances shall be reported as a number. If the
relative abundance is zero, enter 0 (zero), not a dash or other
non-numeric character. Where parentheses appear, compute the
percentage of the ion abundance of the mass given in the
appropriate footnote, and enter that value in the parentheses.
3.10.2.5 In the lower table, list all samples, including dilutions, re-
analyses, standards, blanks and requested MS/MSD analyzed under
that instrument performance check in chronological order, by time
of analysis (in military time). Refer to Section 3.3.7 for
specific instructions for identifying standards and blanks.
3.10.2.6 Complete the following fields for all standards, samples,
including dilutions, re-analyses, and blanks: "EPA Sample No.",
"Lab Sample ID", "Lab File ID", "Date Analyzed", and "Time
Analyzed".
3.10.2.7 Number all pages as described in Section 3.3.
3.11 GC/MS Initial Calibration Data (Form VI LCV-1, LCV-2, LCV-3 and Form VI
LCSV-1, LCSV-2, LCSV-3)
3.11.1 Purpose. After a GC/MS system has undergone an initial five-point
calibration at the specific concentration levels described in Exhibit
D, and after all initial calibration criteria have been met, the
Contractor shall complete and submit this form for each volatile or
semivolatile target compound initial calibration performed which is
relevant to the samples, including dilutions, re-analyses, and blanks
in the SDG, regardless of when that.calibration was performed.
3.11.2 Instructions. Complete the header information according to the .
instructions in Section 3.3. Enter the Case number and SDG number
for the current data package, regardless of the original Case for
which the initial calibration was performed. . Complete the remainder
of the form using the following instructions.
3.11.2.1 Enter the date(s) of the calibration. If the calendar date
changes during the calibration procedure, the inclusive dates
shall be recorded. Dates shall be entered as MM/DD/YYYY.
3.11.2.2 Enter the injection times of the first and last of the standards
analyzed in the "Calibration Times" field. Times shall be
reported in military time.
3.11.2.3 Enter the lab file identifier for each of the five calibration
standards injected. Complete the response factor data for the
five calibration points, and then calculate and report the average
Relative Response Factor (RRF) for all target compounds.
3.11.2.4 For volatiles and semivolatiles, report the RRFs for the
deuterated monitoring compounds in the calibration standards. The
Contractor shall report the Relative Standard Deviation (%RSD) for
all compounds. See Exhibit D for equations.
3.12 GC/EC Initial Calibration Data (Form VI LCP-1, LCP-2, LCP-3)
3.12.1 Purpose. The initial calibration of pesticides/Aroclors involves the
determination of retention times, retention time windows, and
calibration factors. For single component pesticide target
compounds, these data are calculated from the analyses of the
Individual Standard Mixtures A and B at three different concentration
B-43 OLC03.2
-------
Exhibit B — Section 3
Form Instructions
Form VI LCPs (Con't)
levels. For the multicomponent target compounds, these data are
calculated from a single point calibration.
3.12.2 Instructions. Complete one Form VI for each GC column used for the
three analyses of Individual Standard Mixture A (low-point, mid-
point, and high-point) and the three analyses of Individual Standard
Mixture B during an initial calibration. Complete the header
information according to the instructions in Section 3.3. Complete
the remainder of the form using the following instructions.
3.12.2.1 • In the "Level (x low)" field/ enter the concentration of the low-
point, mid-point, and high-point calibration standards as a
multiplier of the low-point. Therefore, for the low-point, enter
"1.0." The concentration of the mid-point standard is specified
in Exhibit D as four times the low-point; therefore, enter "4.0."
The high-point standard shall be at least 16 times the low-point,
but may be higher, if that value lies within the linear range of
the instrument, as specified in Exhibit D. Therefore, enter the
appropriate multiplier to the high-point standard concentration to
one decimal place.
3.12.2.2 Identify the GC column and internal diameter (in mm) in the
appropriate fields.
3.12.2.3 Enter the dates of analysis of the first and last of the six
standards on each form in the "Date(s) Analyzed" field. Dates
shall be entered as MM/DD/YYYY.
3.12.2.-4 For each standard analyzed, enter the retention time of each
applicable analyte in minutes and decimal minutes, under the
'""•' appropriate concentration level in the "RT OF STANDARDS" column on
-> Form VI LCP-1.
3.12.2/5 Calculate the mean retention time of each analyte from the three
individual mixtures, and report it in the "MEAN RT" column on Form
VI LCP-1.
3.12.2.6 Calculate the retention time window for each analyte using the
specifications in Exhibit D, and enter the lower limit of the
window in the "RT WINDOW" column under "FROM," and the upper limit
of the window under "TO" on Form VI LCP-1. The retention times of
the surrogates are reported from the analyses of Individual
Mixture A and the windows are only required to be calculated for
Individual Mixture A.
3.12.2.7 For the six analyses of the Individual Standard Mixtures, the
Contractor shall also complete the calibration factor data on Form
VI LCP-2. Prepare one form for each instrument and GC column
used. Enter the calibration factor for each compound in each of
the standards. Calculate and enter a mean calibration factor and
a relative standard deviation (%RSD). As with surrogate retention
times, the surrogate calibration factors are only required from
Individual Mixture A analyses.
3.12.2.8 For the multicomponent target compounds, the retention times,
retention time windows, and calibration factors shall be reported
in a similar fashion for each single point calibration standard.
For each multicomponent compound, the Contractor shall select at
least three peaks from each analyte, according to the
specifications in Exhibit D. The retention time and calibration
factor data apply to each peak. Complete one version of Form VI
OLC03.2 B-44
-------
Exhibit B -- Section 3
Form Instructions
Form VI LCPs (Con't)
LCP-3 for each GC column, for each initial calibration that
applies to samples in the data package.
3.12.3 Form VI (LCP-4) is also used to report the results of analysis of the
Resolution Check Solution that shall begin each pesticide/Aroclor <
initial calibration sequence. The Contractor shall submit one Form
VI LCP-4 for both GC columns.
3.12.3.1 Complete the header information as described in Section 3.3.
Using the same assignment of first and second GC columns made for
Form IV, enter the GC column identifier, internal diameter, and
date and time of analysis. Enter the EPA sample number for the
Resolution Check Standard. If simultaneous injections on a single
GC are used, the EPA sample number may be the same for both
Resolution Check Standards. If simultaneous injections are not
used, use different suffixes to identify the standards. Complete
the remainder of the form using the following instructions.
3.12.3.2 List each analyte, in retention time order, including both
surrogate compounds. Thus, the order of analytes in the two boxes
on this form will be different due to the dissimilarity of the
stationary phases of the two GC columns used. Enter the name of
each target analyte in the Resolution Check Mixture as it appears
on Form I LCP. Spell out the names of the surrogates as they
appear on Form II LCP-2.
3.12.3.3 Enter the retention time of each analyte from the analysis in the
11RT" column.
3.12.3.4 Calculate the resolution between each pair of analytes. Enter the
resolution between the first and second peaks on the line for the
first analyte listed in the box. Enter the resolution between the
second and third peaks on the line for the second analyte, and so
on, until the resolutions of all possible pairs of adjacent
analytes have been entered.
NOTE: Only eight of the nine resolution fields will be filled.
3.12.4 Form VI (LCP-5, LCP-6 and LCP-7 for each PEM, initial mid-level
calibration mixture A, and initial mid-level calibration mixture B,
respectively) shall be used to report the percent resolution between
each pair of analytes according to the definition in Exhibit D
Pesticides and Aroclors.
NOTE: These forms shall also be used to report all percent resolution
data for the PEM and midpoint concentration Individual Mixtures A and
B analyzed as part of calibration verification (Exhibit D/PEST,
Section 9.3).
3.12.4.1 Complete the header information as described in Section 3.3.
Using the same assignment of first and second GC columns made for
Form IV, enter the GC column identifier, internal diameter, and
date and time of analysis. Enter the EPA sample number for the
respective standards. If simultaneous injections are not used,
use different suffixes to identify the standards. Complete the
remainder of the form using the following instructions.
3.12.4.2 List each analyte, in retention time order, including both
surrogate compounds. Thus, the order of analytes in the two boxes
on this form will be different due to the dissimilarity of the
stationary phases of the two GC columns used. Enter the name of
B-45 OLC03.2
-------
Exhibit B — Section 3
Form Instructions
Form VII LCVs, LCSVs and LCPs
each target analyte in the standard as it appears on Form I LCP.
Spell out the names of the surrogates as they appear on Form II
LCP-2.
3.12.4.3 Enter the retention time of each analyte from the analysis in the
"RT" column.
3.12.4.4 Calculate the resolution between each pair of analytes. Enter the
resolution between the first and second peaks on the line for the
first analyte listed in the box. Enter the resolution between the
second and 'third peaks on the line for the second analyte, and so
on, until the resolutions of all possible pairs of adjacent
analytes have been entered.
NOTE: The last resolution field will be left blank in each table.
3.13 GC/MS Continuing Calibration Data (Form VII LCV-1, LCV-2, LCV-3 and Form
VII LCSV-1, LCSV-2, LCSV-3)
3.13.1 Purpose. For volatiles and semivolatiles, this form is used to
report the calibration of the GC/MS system by the analysis of
specific calibration standards. Form VII is required for each 12-
hour time period for both volatile and semivolatile target compound
analyses. The Contractor shall analyze calibration standards and
meet all criteria outlined in Exhibit D for the minimum Relative
Response Factors (RRF)and maximum percent difference between initial
and continuing calibrations.
3.13.2 Instructions. Complete the header information according to the
'«'?* instructions in Section 3.3. .Complete the remainder of the form
-'•' using the following instructions.
3.13.2-:'-i Enter the date and time of the continuing calibration and the
-'•"-• dates and times of the initial calibration (give inclusive dates
if the initial calibration is performed over more than one date).
Dates shall be entered as MM/DD/YYYY. Times shall be reported in
military time.
3.13.2.2 Using the appropriate initial calibration (volatile or
semivolatile), enter the average RRF for each target compound and
each deuterated monitoring compound for volatiles and
semivolatiles.
3.13.2.3 Report the RRF (RRF5 for Volatiles and RRF20 for Semivolatiles)
from the continuing calibration standard analysis.
3.13.2.4 Calculate the percent difference (%D) for all compounds. See
Exhibit D for equation. If the %D is greater than 999.9, report
as 999.9. If the %D is less than -99.9, report as -99.9.
3.14 GC/ECD Calibration Verification Summary (Form VII, LCP-1, LCP-2)
3.14.1 Purpose. Form VII is used to report the results of the Performance
Evaluation Mixtures (PEMs) and the mid-point concentrations of
Individual Standard Mixtures A and B that, along with the PEM,
bracket each 12-hour period of sample analyses. The Contractor shall
submit Form VII LCP-1 for each 12-hour sequence analyzed. Form VII
LCP-2 shall be completed each time the Individual Standard Mixtures
are analyzed, for each GC column used.
OLC03.2 B-46
-------
Exhibit B -- Section 3
Form Instructions
Form VIII LCV and LCSVs
3.14.2 Instructions. Complete Form VII LCP-1 and LCP-2 for each standard
reported on Form VIII LCP. Complete the header information according
to the instructions in Section 3.3. Complete the remainder of the
form using the following instructions.
FORM VII LCP-1
3.14.2.1 Enter the date(s) of the initial calibration(s). Give inclusive
dates if the initial calibration is performed over more than one
day. Dates shall be entered as MM/DD/YYYY.
3.14.2.2 Identify the GC column and internal diameter in the appropriate
fields.
3.14.2.3 On Form VII LCP-1, enter the EPA sample number, lab sample
identifier and date and time of analysis for the instrument blank
that preceded the 12-hour sequence (PIBLK). For the PEM that
initiated or terminated the 12-hour sequence (PEM), enter the EPA
sample number, lab sample identifier, and date and time of
analysis.
3.14.2.4 When reporting data for the PEM at the beginning of the initial
calibration sequence, leave the "EPA Sample No.", "Lab Sample ID",
"Date Analyzed", and "Time Analyzed" fields blank for the
instrument blank (PIBLK), when no instrument blank is analyzed
before the PEM. When reporting all other PEM analyses, the
instrument blank fields shall be completed.
3.14.2.5 In the table, report the retention time for each analyte in the
PEM as well as the retention time'windows.
3.14.2.6 For each analyte in the PEM, enter the amount of the analyte found
in the PEM, in ng to three decimal places, in the "CALC AMOUNT"
column.
3.14.2.7 - Enter the nominal amount (amount added) of each analyte in the PEM
in ng to three decimal places in the "NOM AMOUNT" column.
3.14.2.8 Calculate the percent difference between the calculated amount and
nominal amount for each analyte according to Exhibit D. Report
the values in the "%D" column. If the %D is greater than 999.9,
report as 999.9. If the %D is less than -99.9, report as -99.9.
1
3.14.2.9 Calculate the percent breakdown for endrin and 4,4'-DDT and the
combined percent breakdown in the PEM according to Exhibit D.
Enter the values for the breakdown of endrin and 4,4"-DDT in their
respective fields immediately under the table.
FORM VII LCP-2
3.14.2.10 The upper table on Form VII LCP-2 contains the retention time and
amount data for Individual Standard Mixture A compounds. The
lower table contains the data for Mixture B. Complete the form
using the instructions in Sections 3.14.2.1 through 3.14.2.8 for
Form VII LCP-1.
3.15 Internal Standard Area and RT Summary (Form VIII LCV and Form VIII LCSV-
1, LCSV-2)
3.15.1 Purpose. This form is used to summarize the peak areas and retention
times of the internal standards added to the initial calibration
B-47 OLC03.2
-------
Exhibit B — Section 3
Form Instructions
Form VIII LCV and LCSVs (Con't)
standards, continuing calibration standards and all volatile and
semivolatile samples, including dilutions, re-analyses, and blanks.
The data are used to determine when changes in internal standard
responses will adversely affect quantitation of target compounds.
This form shall be completed each time an initial calibration and
continuing calibration is performed, or when samples are analyzed
under the same GC/MS instrument performance check as an initial
calibration.
3.15.2 Instructions. Complete the header information according to Section
3.3. Complete the remainder of the form using the following
instructions. If samples are analyzed immediately following an
initial calibration, before another instrument performance check and
a continuing calibration, Form VIII shall be completed on the basis
of the internal standard areas of the 5 ug/L initial calibration
standard for volatiles, and the 20 ng initial calibration standard
for semivolatiles. Use the date and time of analysis of this
standard and the lab file identifier and areas in place of those of a
continuing calibration standard.
3.15.2.1 Enter the date and time of analysis of the continuing calibration
standard. The date shall be entered as MM/DD/YYYY. The time
shall be reported in military time.
3.15.2.2 For volatiles, enter the GC column identifier, internal diameter,
and length as directed in Section 3.3.
3.15.2.3 From the results of the analysis of the continuing calibration
••''?'' standard, enter the area measured for each internal standard and
••'•" its retention time (in decimal minutes) under the appropriate
column in the "12 HOUR STD" row.
t: •«.;*•
3.15.2-/4 For each internal standard listed in Tables 5 and 6, calculate the
upper limit of the area and the lower limit of the area from the
internal standard area. For FORM VIII LCV, calculate the upper
limit of the area as the area of the particular internal standard
plus 40 percent of its area (i.e., 1.4 times the area in the "12
HOUR STD" field), and the lower limit of the area as the area of
the internal standard minus 40 percent of its area (i.e., 0.6
times the area in the "12 HOUR STD" field). For FORMS VIII LCSV-1
and VIII LCSV-2, calculate the upper limit of the area as the area
of the particular internal standard plus 100 percent of its area
(i.e., two times the area in the "12 HOUR STD" field), and the
lower limit of the area as the area of the internal standard minus
50 percent of its area (i.e., 0.5 times the area in the "12 HOUR
STD" field). Report these values in the "UPPER LIMIT" and "LOWER
LIMIT" rows, respectively. Calculate the upper limit of the
retention time and the lower limit of the retention time. The
upper limit of the retention time is calculated by adding 0.33
minutes to the retention time of the internal standard and the
lower limit of the retention time is the retention time of the
internal standard minus 0.33 minutes. Report these values in the
"UPPER LIMIT" and "LOWER LIMIT" rows in the applicable RT columns.
3.15.2.5 For each sample, including dilutions, re-analyses, blanks, and
requested MS/MSD analyzed under a given continuing calibration,
enter the EPA sample number and the area measured for each
internal standard and its retention time. If the internal
standard area is outside the upper or lower limits calculated in
Section 3.15.2.4, flag that area with an asterisk (*). The
asterisk shall be placed in the far right-hand space of the box
OLC03.2 B-48
-------
Exhibit B -- Section 3
Form Instructions
Form VIII LCP
for each internal standard area, directly under the "#" symbol.
Similarly, flag the retention time of any internal standard that
is outside the limits with an asterisk.
3.15.2.6 Number all pages as described in Section 3.3.
Table 5
Volatile Internal Standards
Volatile Internal Standards CAS Number
IS1: Chlorobenzene-d5 (CBZ) 3114-55-4
IS2: 1,4-Difluorobenzene (DFB) 540-36-3
IS3: l,4-Dichlorobenzene-d4 (DCB) 3855-82-1
Table 6
Semi-volatile Internal Standards
Semivolatile Internal Standards CAS Number
IS1:
IS2:
IS3:
IS4:
IS5:
IS6:
l,4-Dichlorobenzene-d4 (DCB)
Naphthalene-dS (NPT)
Acenaphthene-dlO (ANT)
Phenanthrene-dlO (PHN)
Chrysene-dl2 (CRY)
Perylene-dl2 (PRY)
3855-82-1
1146-65-2
15067-26-2
1517-22-2
1719-03-5
1520-96-3
3.16 Pesticide Analytical Sequence (Form VIII LCP)
3.16.1 Purpose. This form is used to report the analytical sequence for
pesticide analysis. At least one form is required for each GC column
used for pesticide/Aroclor analyses.
3.16.2 Instructions. Complete the header information according to the
instructions in Section 3.3. Complete the remainder of the form
using the following instructions.
3.16.2.1 Enter the date(s) of the initial calibration. Give inclusive
dates if the initial calibration is performed over more than one
day. Dates shall be entered as MM/DD/YYYY.
3.16.2.2 Identify the GC column and internal diameter in the appropriate
fields.
3.16.2.3 At the top of the table, report the mean retention time for
tetrachloro-m-xylene (TCX) and decachlorobiphenyl (DCB) calculated
from the initial calibration sequence (from INDA).
3.16.2.4 For every analysis associated with a particular analytical
sequence starting with the initial calibration, enter the EPA
sample number, lab sample identifier, and date and time of
analysis. Each sample analyzed as part of the sequence shall be
reported on Form VIII LCP even if it is not associated with the
SDG. The Contractor shall use ZZZZZ as the EPA sample number to-
B-49 OLC03.2
-------
Exhibit B -- Section 3
Form Instructions
Form IX LCP
distinguish all samples that are not part of the SDG being
reported.
3.16.2.5 Report the retention time of the surrogates for each analysis in
the "TCX RT" and "DCB RT" columns. All sample analyses shall be
bracketed by acceptable analyses of instrument blanks, a PEM, and
Individual Standard Mixtures A and B. Given the fact that the
initial calibration may remain valid for some time (Exhibit D), it
is only necessary to report the data from 12-hour periods when
samples, dilutions, re-analyses, Laboratory Control Samples,
requested MS/MSD, blanks, or multicomponent standard analytes for
the 72-hour confirmation requirement in an SDG were analyzed. The
Contractor shall submit Form VIII for the initial calibration
sequence and forms that include the PEMs and Individual Standard
Mixtures that bracket any and all samples in the SDG. While the
data for time periods between the initial calibration and samples
in the SDG are not a routine deliverable, the data shall be
available as requested (e.g., at on-site evaluations). Non-USEPA
samples shall be numbered ZZZZZ.
3.16.2.6 Flag all those values which do not meet the contract requirements
by entering an asterisk (*) in the "RT" column, under the "#"
symbol. If the retention time cannot be calculated due to
interfering peaks, leave the "RT" column blank for that surrogate,
enter an asterisk in the last column, and document the problem in
the SDG Narrative.
3.16.2:7 If more than a single copy of Form VIII LCP is required, enter the
•'•• same header information on all subsequent pages for that GC column
v. and instrument, and number each page as described in Section 3.3.
3.17 Pesticide Cleanup Summary (Form IX, LCP)
3.17.1^ Purpose. Form IX LCP is used to report the results of the check of
the Florisil cartridges used to process all sample extracts and to
associate the lot of cartridges with particular sample results so
that problems with a particular cartridge lot may be tracked across
all associated samples.
3.17.2 Instructions. Complete the header information according to the
instructions in Section 3.3. Enter the Case number and SDG number
for the current data package, regardless of the original Case for
which the cartridge check was performed. Complete the remainder of
the form using the following instructions.
3.17.2.1 Enter the Florisil cartridge lot number.
3.17.2.2 Enter the date the Florisil cartridge check solution was analyzed
in the "Date of Analysis" field. The date shall be entered as
MM/DD/YYYY.
3.17.2.3 Complete the "GC Column" and "ID" fields for the two GC columns
used to analyze the samples, including blanks, re-analyses.
Laboratory Control Samples, and requested MS/MSD. Report all
results from either GC Column 1 or GC Column 2.
3.17.2.4 In the first table, enter the amount of spike added and spike
recovered in ng for each analyte.
3.17.2.5 Calculate the percent recovery to the nearest whole percent, and
enter the number in the "% REC" field. Flag each spike recovery
OLC03.2 B-50
-------
Exhibit B — Section 3
Form Instructions
Form X LCPs
outside the QC limits (shown on the form) with an asterisk (*).
The asterisk shall be placed in the last space in the "% REC"
column, under the "#" symbol.
3.17.2.6 In the second table, complete the "EPA Sample No.," the "Lab
Sample ID," and "Date Analyzed" fields for each sample and blank
that were cleaned up using this lot of Florisil cartridges.
3.17.2.7 Number the pages as described in Section 3.3.
3.18 Pesticide/Aroclor Identification (Form X, LCP-1, LCP-2)
3.18.1 Purpose. This form summarizes the quantitations of all target
pesticides/Aroclors detected in a given sample. It reports the
retention times of the compound on both columns on which it was
analyzed, as well as the retention time windows of the standard for
that compound on both of these columns. In addition, it is used to
report the concentration determined from each GC column, and the
percent difference between the two quantitative results. Separate
forms are used for single component analytes and multicomponent
analytes.
Form X is required for each sample, including dilutions, re-analyses,
blanks. Laboratory Control Samples and requested MS/MSD in which
compounds listed in Exhibit C (Pesticides/Aroclors) are reported on
Form I. Do not generate a Form X for pesticide instrument blanks.
3.18.2 Instructions. Complete the header information according to the
instructions in Section 3.3. Complete the remainder of the form
using the following instructions.
3.18.2.1 Enter the date(s) of analysis. Dates shall be entered as
MM/DD/YYYY.
3.18.2.2 Enter the GC column and internal diameter for each of the two
columns.
3.18.2.3 For each single component pesticide positively identified, enter
the name of the compound in the "ANALYTE" column as it appears on
Form I..
3.18.2.4 Enter the retention times on each column of the compounds detected
in the sample next to the appropriate column designation (1 or 2).
3.18.2.5 Enter the retention time windows on each column from the initial
calibration standard. These data shall correspond with those on
Form VI and shall be entered in a similar manner. The lower value
is entered under the "FROM" column, the upper value under the "TO"
column.
3.18.2.6 Enter the concentration calculated from each GC column under the
"CONCENTRATION" column. Although the units are the same as those
used on Form I, do not enter any units on Form X.
3.18.2.7 Calculate the percent difference between the concentrations
entered on this form, using the equation found in Exhibit D, and
report it to a tenth of a percent in the "%D" column. If %D is
greater that 999.9, report it as 999.9.
3.18.2.8 The lower of the two concentrations is reported on Form I for each
pesticide compound. The lower concentration is used because, if
B-51 OLC03.2
-------
Exhibit B — Section 3
Form Instructions
Form DC-1
present, coeluting interferences are likely to increase the
calculated concentration of any target compound. If the percent
difference between the calculated concentrations is greater than
25.0 percent, flag the concentration on Form I, as described
previously. This will alert the data user to the potential
problems in quantitating this analyte.
3.18.2.9 If more pesticide compounds are identified in an individual sample
than can be reported on one Form X, complete as many additional
copies of Form X as necessary, duplicating all header information
and numbering the pages as described in Section 3.3.
3.18.2.10 Report multicomponent analytes detected in samples on Form X LCP-
2. Complete the header information and GC column fields as
described above. For multicomponent analytes, it is necessary to
report the retention time and concentration of each peak chosen
for quantitation in the target analyte in a fashion similar to-
that for single component pesticides. The concentrations of all
peaks quantitated (three are required, up to five may be used) are
averaged to determine the mean concentration. Report the lower of
the two mean concentrations on Form I. Flag this value if the
mean concentrations from the two GC columns differ by more than 25
percent, as described previously.
3.18.2.11 If more multicomponent compounds are identified in an individual
sample than can be reported on one Form X, complete as many
additional copies of Form X as necessary, duplicating all header
•;¥ information and numbering the pages as described in Section 3.3.
3.19 'Sample Log-In Sheet (Form DC-1)
3.19.lK:- Purpose. This form is used to document the receipt and inspection of
sample containers and samples. One original of Form DC-1 is required
for each sample shipping container (only the hardcopy form is
V required). If the samples in a single sample shipping container are
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 SDGs. The copies shall be identified as "copyties)", and the
location of the original shall be noted on the copies.
3.19.2 Instructions
3.19.2.1 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).
3.19.2.2 Complete the header information on the form, including the log-in
date.
3.19.2.3 Examine the shipping container and record the presence/absence of
custody seals and their condition (e.g., intact, broken) in item
1.
3.19.2.4 Record the custody seal numbers in item 2.
3.19.2.5 Open the container, remove the enclosed sample documentation, and
record the presence/absence of chain-of-custody record(s), SMO
forms (e.g., TRs, Packing Lists), and airbills or airbill stickers
in items 3-5. Specify if there is an airbill present or an
OLC03.2 B-52
-------
Exhibit B -- Section 3
Form Instructions
Form DC-2
airbill sticker in item 5. Record the airbill or sticker number
in item 6.
3.19.2.6 Remove the samples from the shipping container(s), examine the
samples and the sample tags (if present), and record the condition
of the sample bottles (e.g., intact, broken, leaking) and presence
or absence of sample tags in items 7 and 8.
3.19.2.7 Record the presence of the cooler temperature indicator bottle in
item 9 and cooler temperature in item 10.
3.19.2.8 Review the sample shipping documents and compare the information
recorded on all the documents and samples and circle the
appropriate answer in item 11.
3.19.2.9 Record the date and time of cooler receipt at the laboratory in
items 12 and 13.
3.19.2.10 If there are no problems observed during receipt, sign and date
(include the time) Form DC-1, the Chain-of-Custody record, and the
TR, and write the sample numbers on Form DC-1 in the "EPA Sample
#" column.
3.19.2.11 Record the appropriate sample tags and assigned laboratory
numbers, if applicable.
3.19.2.12 Any comments should be made in the "Remarks" column.
3.19.2.13 Record the fraction designation (if appropriate) and the specific
area designation (e.g., refrigerator number) in the "Sample
Transfer" block. Sign and date the "Sample Transfer" block.
3.19.2.14 Cross out unused columns and spaces. Initial and date all cross
outs.
3.19.2.15 If there are problems observed during receipt 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
and note, where appropriate, the resolution of the problem.
3.20 Complete SDG File (CSF) Inventory Sheet (Form DC-2)
3.20.1 Purpose. Form DC-2 is used to record both the CSF documents and the
number of documents in the original Sample Data Package sent to the
USEPA Region.
3.20.2 Instructions
3.20.2.1 Organize all USEPA CSF documents as described in Section "2.6.
Assemble the documents in the order specified on Form DC-2 and
Section 2.6, and stamp each page with a consecutive number;
however, 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 (e.g., "page numbers not used, XXXX
- XXXX, YYYY - YYYY. if there are no documents for a specific
document type, enter an "NA" in the empty space.
B-53 OLC03.2
-------
Exhibit_B -- Sections 3 & 4
Data Reporting Forms
3.20.2.2 Certain laboratory-specific documents related to the CSF may not
fit into a clearly defined category. The Contractor shall review
Form DC-2 to determine if it is most appropriate to place them
under categories 7, 8, 9, or 10. Category 10 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 on Form DC-2.
3.20.2.3 If it is necessary to insert new or inadvertently omitted
documents, the Contractor shall identify the documents with unique
accountable numbers and record the unique accountable numbers and
the locations of the documents in the CSF (in the "Other Records"
section on Form DC-2).
4.0 DATA REPORTING FORMS
The data reporting forms are shown on the following pages.
OLC03.2 B-54
-------
Lab Name:
Lab Code:
Lab Sample ID:
Lab File ID: _
Purge Volume:
GC Column:
1LCA
LOW CONCENTRATION WATER VOLATILE ORGANICS ANALYSIS
DATA SHEET
Contract:
Case No.:
Client No.:
SDG NO.:
.(ML)
ID:
.(MM)
Date Received:
Date Analyzed:
EPA SAMPLE NO.
Dilution Factor:
Length: (M)
CAS NO.
75-71-8
74-87-3
75-01-4
74-83-9
75-00-3
75-69-4
75-35-4
76-13-1
67-64-1
75-15-0
79-20-9
75-09-2
156-60-5
1634-04-4
75-34-3
156-59-2
78-93-3
74-97-5
67-66-3
71-55-6
110-82-7
56-23-5
71-43-2
107-06-2
COMPOUND
Dichlorodifluoromethane
Chloromethane
Vinyl Chloride
Bromomethane
Chi oroethane
Trichlorofluoromethane
1, 1-Dichloroethene
1,1, 2-Trichloro-l,2, 2-trif luoroethane
Acetone
Carbon Disulfide
Methyl Acetate
Methylene Chloride
trans -1,2 -Dichloroethene
Methyl tert -Butyl Ether
1 , 1 -Dichl oroethane
cis- 1,2 -Dichloroethene
2 -Butanone
Bromochloromethane
Chloroform
1 , 1 , l-Trichloroethane
Cyclohexane
Carbon Tetrachloride
Benzene
1 , 2 -Dichloroethane
CONCENTRATION UNITS:
(UG/L)
Q
FORM I LCV-1
OLC03.2
-------
Lab Name:
Lab Code:
Lab Sample ID:
Lab File ID: _
Purge Volume:
GC Column:
1LCB
LOW CONCENTRATION WATER VOLATILE ORGANICS ANALYSIS
DATA SHEET
Case No.:
.(ML)
ID:
Contract:
Client No.:
SDG No.:
Date Received:
Date Analyzed:
.(MM)
EPA SAMPLE NO.
Dilution Factor:
Length: (M)
CAS NO.
79-01-6
108-87-2
78-87-5
75-27-4
10061-01-5
108-10-1
108-88-3
10061-02-6
79-00-5
127-18-4
591-78-6
124-48-1
106-93-4
108-90-7
100-41-4
1330-20-7
100-42-5
75-25-2
98-82-8
79-34-5
541-73-1
106-46-7
95-50-1
96-12-8
120-82-1
87-61-6
COMPOUND
Trichloroethene
Me t hy 1 eye 1 ohexane
1 , 2 -Dichloropropane
Bromodichloromethane
cis-1, 3-Dichloropropene
4 -Methyl - 2 -pentanone
Toluene
trans -1, 3-Dichloropropene
1,1,2 -Trichloroethane
Tetrachloroethene
2 -Hexanone
Dibromochloromethane
1 , 2 -Dibromoethane
Chlorobenzene
Ethylbenzene
Xylene (total)
Styrene
Bromoform
Isopropylbenzene
1,1,2,2 -Tetrachloroethane
1, 3-Dichlorobenzene
i
1 , 4 -Dichlorobenzene
1, 2-Dichlorobenzene
1 , 2 -Dibromo-3 -chloropropane
1,2,4 -Trichlorobenzene
1,2,3 -Trichlorobenzene
CONCENTRATION UNITS:
(UG/L)
Q
FORM I LCV-2
OLC03.2
-------
1LCC
LOW CONCENTRATION WATER SEMIVOLATILE ORGANICS
ANALYSIS DATA SHEET
EPA SAMPLE NO.
Lab Name:
Lab Code:
Contract:
Case No.:
Client No.:
SDG No.:
Lab Sample ID:
Lab File ID:
Sample Volume:
(ML)
Date Received: .
Date Extracted:
Date Analyzed:
Concentrated Extract Volume:
Injection Volume: (UL)
(UL)
Dilution Factor:
CAS NO.
100-52-7
108-95-2
111-44-4
95-57-8
95-48-7
108-60-1
98-86-2
106-44-5
621-64-7
67-72-1
98-95-3
78-59-1
88-75-5
105-67-9
111-91-1
120-83-2
91-20-3
106-47-8
87-68-3
105-60-2
59-50-7
91-57-6
77-47-4
88-06-2
95-95-4
92-52-4
91-58-7
88-74-4
131-11-3
606-20-2
208-96-8
99-09-2
83-32-9
COMPOUND
Benzaldehyde
Phenol
bis (2-Chloroethyl) ether
2-Chlorophenol
2 -Methylphenol
2,2' -oxybis (1-Chloropropane)
Acetophenone
4 -Methylphenol
N-Nitroso-di-n-propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2 -Nitrophenol
2 , 4 -Dimethylphenol
bis (2-Chloroethoxy) methane
2 , 4 -Dichlorophenol
Naphthalene
4-Chloroaniline
Hexachlorobutadiene
Caprolactam
4 -Chloro- 3 -methylphenol
2 -Methylnaphthalene
Hexachlorocyclopentadiene
2,4, 6-Trichlorophenol
2 , 4 , 5-Trichlorophenol
1,1' -Biphenyl
2 -Chloronaphthalene
2-Nitroaniline
Dimethylphthalate
2 , 6 -Dinitrotoluene
Acenaphthylene
3-Nitroaniline
Acenaphthene
CONCENTRATION UNITS :
(UG/L)
Q
*
FORM I LCSV-1
OLC03.2
-------
1LCD
LOW CONCENTRATION WATER SEMIVOLATILE ORGANICS ANALYSIS
DATA SHEET
EPA SAMPLE NO.
Lab Name:
Lab Code:
Contract:
Case No.:
Client No.:
SDG No.:
Lab Sample ID:
Lab File ID:
Sample Volume:
(ML)
Date Received:
Date Extracted:
Date Analyzed:
Concentrated Extract Volume:
Injection Volume: (UL)
(UL)
Dilution Factor:
CAS NO.
51-28-5
100-02-7
132-64-9
121-14-2
84-66-2
86-73-7
7005-72-3
100-01-6
534-52-1
86-30-6
95-94-3
101-55-3
118-74-1
1912-24-9
87-86-5
85-01-8
120-12-7
84-74-2
206-44-0
129-00-0
85-68-7
91-94-1
56-55-3
218-01-9
117-81-7
117-84-0
205-99-2
207-08-9
50-32-8
193-39-5
53-70-3
191-24-2
COMPOUND
2 , 4 -Dinitrophenol
4 -Nitrophenol
Dibenzofuran
2 , 4 -Dinitrotoluene
Diethylphthalate
Fluorene
4 -Chlorophenyl -phenylether
4-Nitroaniline
4, 6-Dinitro-2-methylphenol
N-Nitrosodiphenylamine (1)
1,2,4,5 Tetrachlorobenzene
4 -Bromophenyl -phenylether
Hexachlorobenzene
Atrazine
Pentachlorophenol
Phenanthrene
Anthracene
Di -n-butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalat'e
3,3' -Dichlorobenzidine
Benzo (a) anthracene
Chrysene
bis (2-Ethylhexyl)phthalate
Di -n-octylphthalate
Benzo (b) f luoranthene
Benzo (k) fluoranthene
Benzo (a) pyrene
Indeno ( 1 , 2 , 3 -cd) pyrene
Dibenzo (a , h) anthracene
Benzo (g , h , i ) perylene
CONCENTRATION UNITS:
(UG/L)
Q
(1) Cannot be separated from Diphenylamine
FORM I LCSV-2
OLC03.2
-------
1LCE
LOW CONCENTRATION WATER PESTICIDE ORGANICS ANALYSIS
DATA SHEET
EPA SAMPLE NO.
Lab Name:
Lab Code:
Contract:
Case No.:
Client No.:
SDG No.:
Lab Sample ID:
Sample Volume:
(ML)
Concentrated Extract Volume:
Injection Volume: (UL)
Sulfur Cleanup: (Y/N)
(UL)
Date Received:
Date Extracted:
Date Analyzed:
Dilution Factor:
Extraction: (Sepf/Cont)
CAS NO.
319-84-6
319-85-7
319-86-8
58-89-9
76-44-8
309-00-2
1024-57-3
959-98-8
60-57-1
72-55-9
72-20-8
33213-65-9
72-54-8
1031-07-8
50-29-3
72-43-5
53494-70-5
7421-93-4
5103-71-9
5103-74-2
8001-35-2
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
COMPOUND
alpha-BHC
beta-BHC
delta-BHC
gamma -BHC (Lindane)
Heptachlor
Aldrin
Heptachlor epoxide
Endosulfan I
Dieldrin
4,4' -DDE
Endrin
Endosulfan II
4,4' -ODD
Endosulfan sulfate
4,4' -DDT
Methoxychlor
Endrin ketone
Endrin aldehyde
alpha-Chl or dane
gamma - Chi ordane
Toxaphene
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
CONCENTRATION UNITS:
(UG/L)
Q
FORM I LCP
OLC03.2
-------
1LCF
LOW CONCENTRATION VJATER VOLATILE ORGANICS ANALYSIS
DATA SHEET TENTATIVELY IDENTIFIED COMPOUNDS
EPA SAMPLE NO.
Lab Name:
Lab Code:
Contract:
Case No.:
Client No.:
SDG No.:
Lab Sample ID:
Lab File ID: _
Purge Volume:
GC Column:
Date Received:
Date Analyzed:
(ML)
ID:
Dilution Factor:
(MM) Length: (M)
Number TICs found:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
CAS NT7MBER
COMPOUND NAME
RT
EST. CONC.
(UG/L)
O
FORM I LCV-TIC
OLC03.2
-------
1LCG
LOW CONCENTRATION WATER SEMIVOLATILE ORGANICS ANALYSIS
DATA SHEET TENTATIVELY IDENTIFIED COMPOUNDS
EPA SAMPLE NO.
Lab Name:
Lab Code:
Contract:
Case No.:
Client No.:
SDG No.:
Lab Sample ID:
Lab File ID:
Sample Volume:
(ML)
Date Received:
Date Extracted:
Date Analyzed:
Concentrated Extract Volume:
Injection Volume:
Number TICs found:
(UL)
Dilution Factor:
(UL)
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
CAS NUMBER
COMPOUND NAME
RT
EST. CONC.
(UG/L)
0
FORM I LCSV-TIC
OLC03.2
-------
2LCA
LOW CONCENTRATION WATER VOLATILE DEUTERATED MONITORING COMPOUND RECOVERY
Lab Name:
Lab Code:.
Contract:
Case No.:
Client No.:
SDG No.:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
SAMPLE NO.
VDMC1
(VCL) #
VDMC2
(CLA) #
VDMC3
(DCE) #
VDMC4
(BUT) #
VDMC5
(CLF) #
VDMC6
(DCA) #
VDMC7
(BEN) #
VDMC1 (VCL)
VDMC2 (CLA)
VDMC3 (DCE)
VDMC4 (BUT)
VDMC5 (CLF)
VDMC6 (DCA)
VDMC7 (BEN)
= Vinyl Chloride-d3
= Chloroethane-d5
= l,l-Dichloroethene-d2
= 2-Butanone-d5
= Chloroform-d
= l,2-Dichloroethane-d4
= Benzene-d6
PC LIMITS
(49-138)
(60-126)
(65-130)
(42-171)
(80-123)
(78-129)
(78-121)
# Column to be used to flag recovery values
* Values outside of contract required QC limits
Page of
FORM II LCV-1
OLC03.2
-------
2LCB
• LOW CONCENTRATION WATER VOLATILE DEUTERATED MONITORING COMPOUND RECOVERY
Lab Name:
Lab Code:
Contract:
Case No.:
Client No.:
SDG No.:
01
02
03
04
05
06
07
08
09
10
LI
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
SAMPLE NO.
VDMC8
(DPA) #
VDMC9
(TOD #
VDMC10
(TOP) #
VDMC11
(HEX) #
VDMC12
(BRF). #
VDMC13
(TCA) #
VDMC14
(DCZ) #
TOT
OUT
VDMC8 (DPA) = l,2-Dichloropropane-d6
VDMC9 (TOL) = Toluene-d8
VDMC10 (TDP) = trans-l,3-Dichloropropene-d4
VDMC11 (HEX) = 2-Hexanone-d5
VDMC12 (BRF) . = Bromoform-d
VDMC13 (TCA) = l,l,2,2-Tetrachloroethane-d2
VDMC14 (DCZ) = l,2-Dichlorobenzene-d4
PC LIMITS
(84-123)
(77-120)
(80-128)
(37-169)
(76-135)
(75-131)
(50-150)
Column to be used to flag recovery values
Values outside of contract required QC limits
Page of
FORM II LCV-2
OLC03.2
-------
2LCC
LOW CONCENTRATION WATER SEMIVOLATILE OBLITERATED MONITORING COMPOUND RECOVERY
Lab Name:
Lab Code:
Contract:
Case No.:
Client No. -.
SDG No.:
01
02
03
04
05
06
07
08
09
LO
LI
12
13
L4
L5
L6
17
18
L9
20
21
22
23
24
25
26
27
28
29
30
EPA
SAMPLE NO.
SDMCl"
(PHL) #
SDMC2
(BCE) #
SDMC3
(2CP) #
•
SDMC4
(4MP) #
SDMC5'
(NBZ) #
SDMC6
(2NP) #
SDMC7
(DCP) #
SDMC8
(4CA) #
PC LIMITS
SDMC1 (PHL) = Phenol-d5 (10-110)
SDMC2 (BCE) = bis-(2-Chloroethyl)ether-d8 (41-94)
SDMC3 (2CP) = 2-Chlorophenol-d4 (33-110)
SDMC4 (4MP) = 4-Methylphenol-d8 (38-95)
SDMC5 (NBZ) = Nitrobenzene-d5 (35-114)
SDMC6 (2NP) = 2-Nitrophenol-d4 (40-106)
SDMC7 (DCP) = 2,4-Dichlorophenol-d3 (42-98)
SDMC8 (4CA) '= 4-Chloroaniline-d4 (8-70)
# Column to be used to flag recovery values
* Values outside of contract required QC limits
D DMC diluted out
Page of
FORM II LCSV-1
OLC03.2
-------
2 LCD
LOW CONCENTRATION WATER SEMIVOLATILE DEUTERATED MONITORING COMPOUND RECOVERY •
Lab Name:
Lab Code:
Contract:
Case No.:
Client No.:
SDG No.:
)1
)2
)3
14
)5
)6
)7
)8
19
LO
LI
L2
L3
L4
L5
L6
L7
L8
L9
>0
!1
22
23
24
25
>e
27
28
29
30
EPA
SAMPLE NO.
SDMC9
(DMP) #
SDMC10
(ACY) #
SDMC11
(4NP) #
SDMC12
(FLR) #
SDMC13
(NMP) #
SDMC14
(ANC)#
SDMC15
(PYR) #
SDMC16
(BAP) #
TOT
OUT
SDMC9 (DMP) = Dimethylphthalate-d6
SDMCIO(ACY) = Acenaphthylene-d8
SDMC1K4NP) = 4-Nitrophenol-d4
SDMC12(FLR) = Fluorene-dlO
SDMC13(NMP) = 4,6-Dinitro-methylphenol-d2
SDMC14(ANC) = Anthracene-dlO
SDMC15(PYR) = Pyrene-dlO
SDMC16(BAP) = Benzo(a)pyrene-dl2
PC LIMITS
(62-102)
(49-98)
(9-181)
(50-97)
(53-153)
(55-116)
(47-114)
(54-120)
Column to be used to flag recovery values .
Values outside of contract required QC limits
DMC diluted out
Page of
FORM II LCSV-2
OLC03.2
-------
2LCE
LOW CONCENTRATION WATER PESTICIDE SURROGATE RECOVERY
Lab Name :
Lab Code :
GC Column (1) :
Case No. :
ID: IVtt-
Contract :
Client No. :
(MM) GC Column (2) :
SDG No.:
ID:
(MM)
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
SAMPLE NO.
TCX 1
%REC #
TCX 2
%REC #
DCB 1
%REC #
DCB 2
%REC #
OTHER
(1)
OTHER
(2)
TOT
OUT
TCX = Tetrachloro-m-xylene
DCB = Decachlorobiphenyl
# Column to be used to flag recovery values
* Values outside of QC limits
D Surrogate diluted out
PC I.IMITS
(30-150)
(30-150)
Page of
FORM II LCP
OLC03.2
-------
3LCA
LOW CONCENTRATION WATER VOLATILE
MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Lab Name:
Lab Code:
Case No.:
Contract:
Client No.:
SDG No.
Matrix Spike - EPA Sample No.:
COMPOUND
1, 1-Dichloroethene
.Benzene
Trichloroethene
Toluene
Chlorobenzene
SPIKE
ADDED
(UG/L)
SAMPLE
CONCENTRATION
(UG/L)
MS
CONCENTRATION
(UG/L)
MS
%
REC #
QC
LIMITS
REC.
61-145
76-127
71-120
76-125
75-130
COMPOUND
1 , 1 -Dichloroethene
Benzene
Trichloroethene
Toluene
Chlorobenzene
SPIKE
ADDED
(UG/L)
MSD
CONCENTRATION
(UG/L)
MSD
% .
REC #
RPD #
QC
RPD
*14 .
11
14
13
13
LIMITS
REC.
61-145
76-127
71-120
76-125
75-130
# Column to be used to flag recovery and RPD values with an asterisk
* Values outside of QC limits
RPD: out of outside limits
Spike Recovery: out of outside limits
COMMENTS:
FORM III LCV
OLC03.2
-------
3LCB
LOW CONCENTRATION WATER SEMIVOLATILE
MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Lab Name:
Lab Code:
Case No.:
Matrix Spike - EPA Sample No.:
Contract:
Client No.:
SDG No.
COMPOUND
Phenol
2 - Chlorophenol
N-Nitroso-di-n-prop. (1)
4 -Chloro-3 -methylphenol
Acenaphthene
4 -Nitrophenol
2 , 4 -Dinitrotoluene
Pentachlorophenol
Pyrene
SPIKE
ADDED
(UG/L)
SAMPLE
CONCENTRATION
(UG/L)
/
MS
CONCENTRATION
(UG/L)
MS
%
REC #
QC
LIMITS
REC.
12-110
27-123
41-116
23-97
46-118
10-80
24-96
9-103
26-127
COMPOUND
Phenol
2 -Chlorophenol
N-Nitroso-di-n-prop. (1)
4 - Chloro-3 -methylphenol
Acenaphthene
4 -Nitrophenol
2 , 4 -Dinitrotoluene
Pentachlorophenol
Pyrene
SPIKE
ADDED
(UG/L)
MSD
CONCENTRATION
.(UG/L)
MSD
%
REC #
RPD #
QC L
RPD
42
40
38
42
31
50
38
50
31
IMITS
REC.
12-110
27-123
41-116
23-97
46-118
10-80
24-96
9-103
26-127
(1) N-Nitroso-di-n-propylamine
# Column to be used to flag recovery and RPD values with an asterisk
* Values outside of QC limits
out of
RPD:
Spike Recovery:
COMMENTS:
outside limits
out of outside limits
FORM III LCSV
OLC03.1
-------
3LCC
LOW CONCENTRATION WATER PESTICIDE
MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Lab Name:
Lab Code:
Matrix Spike -
Instrument ID :
Contract :
Case No.: Client No.: SDG No.:
EPA Sample No. :
GC Column: ID:
(mm)
COMPOUND
gamma-BHC
(Lindane)
Heptachlor
Aldrin
Dieldrin
Endrin
4,4 ' -DDT
SPIKE
ADDED .
(UG/L)
SAMPLE
CONCENTRATION
(UG/L)
MS
CONCENTRATION
(UG/L)
MS
%
REC #
QC
LIMITS
REC.
56-123
40-131
40-120
52-126
56-121
38-127 .
COMPOUND
gamma-BHC (Lindane)
Heptachlor
Aldrin
Dieldrin
Endrin
4,4' -DDT
SPIKE
ADDED
(UG/L)
MSD
CONCENTRATION
(UG/L)
MSD
%
REC #
RPD #
QC
RPD
15
20
22
18
21
27
LIMITS
REC.
56-123
40-131
40-120
52-126
56-121
38-127
# Column to be used to flag recovery and RPD values with an asterisk
* Values outside of QC limits
RPD: out of outside limits
Spike Recovery: out of outside limits
COMMENTS:
Page of
FORM III LCP-1
OLC03.2
-------
3 LCD
LOW CONCENTRATION WATER PESTICIDE LAB CONTROL
SAMPLE RECOVERY
EPA SAMPLE NO.
Lab Name:
Lab Code:
Contract:
Case No.:
Client No.
SDG No.:
Lab Sample ID:
LCS Aliquot: _
LCS Lot No.:
.(UL)
Concentrated Extract Volume:
Injection Volume: (UL)
.(UL)
Date Extracted:
Date Analyzed:
Sulfur Cleanup: (Y/N)
Instrument ID (1):
Dilution Factor:
GC Column (1):
ID:
.(MM)
COMPOUND
gamma- BHC (Lindane)
Heptachlor epoxide
Dieldrin
4,4' -DDE
Endrin
Endosulfan sulfate
gamma - Chi ordane
AMOUNT ADDED
(NG)
AMOUNT RECOVERED
(NG)
%REC #
QC LIMITS
50-120
50-150
.30-130
50-150
50-120
50-120
30-130
Instrument ID (2):
GC Column (2):
ID:
(MM)
COMPOUND
gamma -BHC (Lindane)
Heptachlor epoxide
Dieldrin
4,4' -DDE
Endrin
Endosulfan sulfate
gamma - Chi ordane
AMOUNT ADDED
(NG)
AMOUNT RECOVERED
(NG)
%REC #
QC LIMITS
50-120
50-150
30-130
50-150
50-120
50-120
30-130
# Column to be used to flag recovery values with an asterisk
* Values outside of QC limits
LCS Recovery: _
outside limits out of
total.
FORM III LCP-2
OLC03.2
-------
Lab Name:
Lab Code:
Lab Sample ID:
Lab File ID:
Instrument ID:
GC Column:
COMMENTS:
Page of
4LCA
LOW CONCENTRATION WATER
VOLATILE METHOD BLANK SUMMARY
EPA SAMPLE NO.
Contract:
Case No.:
Client No.:
SDG No.:
Date Analyzed:
Time Analyzed:
ID:
(MM)
Length:
.(M)
THIS METHOD BLANK APPLIES TO THE FOLLOWING SAMPLE ANALYSES:-
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
SAMPLE NO.
LAB
SAMPLE ID
'LAB
FILE ID
TIME
ANALYZED
FORM IV LCV
OLC03.1
-------
Lab Name:
Lab Code:
4LCB
LOW CONCENTRATION WATER
SEMIVOLATILE METHOD BLANK SUMMARY
EPA SAMPLE NO.
"Contract:
Case No. : Client No. : SDG No. :
Lab Sample ID: Date Extracted:
Lab File ID: Date Analyzed:
Instrument ID: Time Analyzed:
THIS METHOD BLANK APPLIES TO THE FOLLOWING ANALYSES:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
SAMPLE NO.
LAB
SAMPLE ID
LAB
FILE ID
DATE
ANALYZED
COMMENTS:
Page of
FORM IV LCSV
OLC03.2
-------
4LCC
LOW CONCENTRATION WATER
PESTICIDE METHOD BLANK SUMMARY
EPA SAMPLE NO.
Lab Name:
Lab Code:
Contract:
Case No.:
Client No.:
SDG No.:
Date Extracted:
Lab Sample ID:
Date Analyzed (1) :
Time Analyzed (1) :
Instrument ID (1):
GC Column (1):
ID:
Sulfur Cleanup: (Y/N)
Date Analyzed (2):
Time Analyzed (2):
Instrument ID (2):
.(MM) GC Column (2) : ID: (MM)
Extraction (Sepf/Cont):
THIS METHOD BLANK APPLIES TO THE FOLLOWING SAMPLE ANALYSES:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
EPA
SAMPLE NO.
LAB
SAMPLE ID
DATE
ANALYZED 1
DATE
ANALYZED 2
COMMENTS:
Page of
FORM IV LCP
OLC03.2
-------
5LCA
LOW CONCENTRATION WATER VOLATILE ORGANIC INSTRUMENT PERFORMANCE CHECK
BROMOFLUOROBENZENE (BFB)
Lab Name:
Lab_Code:.
Contract:
_Case_No.._:__
Client_No_._:_
Lab File ID:
Instrument ID:
GC Column: .
ID:
.(MM)
BFB Injection Date:
BFB Injection Time:
Column Length:
m/e
50
75
95
96
173
174
175
176
177
ION ABUNDANCE CRITERIA
8.0 - 40.0% of mass 95
30.0 - 66.0% of mass 95
Base peak, 100% relative abundance
5.0 - 9.0% of mass 95
Less than 2.0% of mass 174
50.0 - 120.0% of mass 95
4.0 - 9.0 % of mass 174
93.0 - 101.0% of mass 174
5.0 - 9.0% of mass 176
% RELATIVE
ABUNDANCE
( )1
( )1
( )1
( )2
1-Value is % mass 174
2-Value is % mass 176
THIS CHECK APPLIES TO THE FOLLOWING SAMPLES, BLANKS, AND STANDARDS:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
EPA
SAMPLE NO.
LAB
SAMPLE ID
LAB
FILE ID
DATE
ANALYZED
TIME
ANALYZED
•
Page of
FORM V LCV
OLC03.2
-------
5LCB
LOW CONCENTRATION WATER SEMIVOLATILE ORGANIC INSTRUMENT PERFORMANCE CHECK
DECAFLUOROTRIPHENYLPHOSPHINE (DFTPP)
Lab Name:
Lab Code:
Contract:
Case No.:
Client No.:
SDG No.:
Lab File ID:
Instrument ID:
DFTPP Injection Date:
DFTPP Inj ection Time:
m/e
51
68
69
70
127
197
198
199
275
365
441
442
443
ION ABUNDANCE CRITERIA
30.0- 80.0% of mass 198
Less than 2.0% of mass 69
Mass 69 relative abundance
Less than 2.0% of mass 69
25.0 - 75.0% of mass 198
Less than 1.0% of mass 198
Base Peak, 100% relative abundance
5.0 to 9.0% of mass 198
10.0- 30.0% of mass 198
Greater than 0.75% of mass 198
Present, but less than mass 443
40.0 - 110.0% of mass 198
15.0 - 24.0% of mass 442
% RELATIVE ABUNDANCE
( )1
( )1
( )2
1-Value is % mass 69
2-Value is % mass 442
THIS CHECK APPLIES TO THE FOLLOWING SAMPLES, BLANKS, AND STANDARDS:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
EPA
SAMPLE NO.
"•
LAB
SAMPLE ID
LAB
FILE ID
DATE
ANALYZED
TIME
ANALYZED
Page of
FORM V LCSV
OLC03.2
-------
6LCA
LOW CONCENTRATION WATER VOLATILE ORGANICS INITIAL CALIBRATION DATA
Lab Name:
Lab Code:
Instrument ID:
GC Column:
Case No.:
ID:
Calibration Date(s):
Calibration Times:
(MM) Length:
Contract:
Client No.:
SDG No.
(M)
LAB FILE ID: RRFO . 5
RRF5 = RRF
COMPOUND
Dichlorodifluoromethane
Chloromethane
Vinyl Chloride *
Bromomethane *
Chloroethane
Trichlorof luoromethane
1, 1-Dichloroethene *
1, 1,2-Trichloro-
1,2 , 2-trif luoroethane
Acetone
Carbon Disulfide
Methyl Acetate
Methylene Chloride
trans -1,2 -Dichloroethene
Methyl tert -Butyl Ether
1 , 1 -Dichloroethane *
cis- 1,2 -Dichloroethene
2-Butanone
Bromochloromethane *
Chloroform *
1,1,1-Trichloroethane *
Cyclohexane
Carbon Tetrachloride *
Benzene *
1 , 2 -Dichloroethane *
Trichloroethene *
Me t hy 1 eye 1 ohexane
10
RRFO. 5
RRF1
RRF5
RRF1
RRF25
RRF10
=
=
RRF25
RRF
%
RSD
*
*
*
*
*
*
*
*
*
*
*
*Compounds with required minimum RRF and maximum %RSD values.
All other compounds must meet a minimum RRF of 0.010.
FORM VI LCV-1
OLC03.2
-------
6LCB
LOW CONCENTRATION WATER VOLATILE ORGANICS INITIAL CALIBRATION DATA
Lab Name :
Lab Code:
Instrument ID :
GC Column:
Contract :
Case No. : Client No. : _...
Calibration Date(s) :
Calibration Times:
ID: (MM) Lenath:
SDG No. :
(M)
LAB FILE ID: RRF0.5
RRF5 - RRF10
COMPOUND
1 , 2 -Dichloropropane
Bromodichloromethane *
cis-l,3-Dichloropropene *
4 -Methyl - 2 -pentanone
Toluene *
trans-l,3-Dichloropropene *
1, 1, 2-Trichloroethane *
Tetrachloroethene *
2-Hexanone
Dibromochloromethane *
1 , 2 -Dibromoethane *
Chlorobenzene *
Ethylbenzene - *
Xylene (total) *
Styrene *
Bromoform *
I sopropylbenzene
1,1,2,2 -Tetrachloroethane *
1 , 3 -Dichlorobenzene *
1 , 4 -Dichlorobenzene *
1 , 2 -Dichlorobenzene *
l,2-Dibromo-3-chloropropane
1,2,4 -Tri chlorobenzene *
1,2,3 -Trichlorobenzene *
RRF0.5
RRF1
RRF5
j
RRF1
RRF25 =
RRF10
=
RRF25
RRF
%
RSD
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*Compounds with required minimum RRF and maximum %RSD values.
All other compounds must meet a minimum RRF of 0.010.
FORM VI LCV-2
OLC03.2
-------
6LCC
LOW CONCENTRATION WATER VOLATILE ORGANICS INITIAL CALIBRATION DATA
Lab Name:
Lab Code:
Instrument ID:
GC Column:
Contract:
Case No.:
Client No.:
ID:
Calibration Date(s):
Calibration Times:
(MM) Length:
SDG NO.:
.(M)
LAB FILE ID: RRF0.5 = RRF1
RRF5 - ' RRF10 - RRF25 -
COMPOUND
Vinyl chloride-d3
Chloroethane-d5
1, l-Dichloroethene-d2
2 - Butanone - d5
Chloroform-d
1, 2-Dichloroethane-d4
Benzene-d6
1 , 2 -Dichloropropane-d6
Jpluene-d8
.. trans -1,3-Dichl oropropene - d4
, 2 _- Hexanone - d5
,Bromoform-d
, i, 1 , 2 , 2-Tetrachloroethane-d2
1, 2-Dichlorobenzene-d4
RRF0.5
RRF1
RRF5
RRF10
RRF25
•
RRF
%
RSD
*Compounds with required minimum RRF and maximum %RSD values.
All other compounds must meet a minimum RRF of 0.010.
FORM VI LCV-3
OLC03.2
-------
6 LCD
LOW CONCENTRATION WATER SEMIVOLATILE ORGANICS INITIAL CALIBRATION DATA
Lab Name:
Lab Code:
Contract:
Case No.:
Client No.:
SDG No.:
Instrument ID:
Calibration Date(s):
Calibration Times:
LAB FILE ID: RRF5
RRF20 = RRF50
COMPOUND
Benzaldehyde
Phenol *
bis- (2-Chloroethyl) ether *
2-Chlorophenol *
2-Methylphenol *
2,2' -oxybis (1-Chloropropane)
Acetophenone
4 -Methylphenol *
N-Nitroso-di-n-propylamine • *
Hexachloroethane *
Nitrobenzene *
Isophorone *
2-Nitrophenol *
2 , 4 -Dimethylphenol *
bis (2-Chloroethoxy)methane *
2,4-Dichlorophenol *
Naphthalene *
4-Chloroaniline
Hexachlorobutadiene
Caprolactam
4-Chloro-3-methylphenol *
2-Methylnaphthalene *
Hexachlorocyclopentadiene
2,4,6 -Trichlorophenol *
2,4,5-Trichlorophenol *
1,1' -Biphenyl
2-Chloronaphthalene *
2-Nitroaniline
Dimethylphthalate
2 , 6 -Dinitrotoluene *
Acenaphthylene *
3 -Nitroaniline
Acenaphthene *
2 , 4 -Dinitrophenol
4 -Nitrophenol
Dibenzofuran *
_
RRF5
RRF10
RRF20
RRF10
RRF80
RRF50
_
RRF80
RRF
%
RSD
*
*
*
*
*
*
*
it
if
*
*
• *
. *
*
*
*
*
+
*
*
*
*
*
* Compounds with required minimum RRF and maximum %RSD values.
All other compounds must meet a minimum RRF of 0.010.
FORM VI LCSV-2
OLC03.2
-------
6LCE
LOW CONCENTRATION WATER SEMIVOLATILE ORGANICS INITIAL CALIBRATION DATA
Lab Name:
Lab Code:
Contract:
Case No.:
Client No.:
SDG No.:
Instrument ID:
Calibration Date(s):
Calibration Times:
LAB FILE ID: RRF5
RRF20 = RRF50
COMPOUND
2,4-Dinitrotoluene *
Diethylphthalate
Fluorene *
4-Chlorophenyl-phenylether *
4-Nitroaniline
4, 6-Dinitro-2-methylphenol
N-Nitrosodiphenylamine (1)
1,2,4,5 Tetrachlorobenzene
4-Bromophenyl-phenylether *
Hexachlorobenzene *
Atrazine
Pentachlorophenol *
Phenanthrene . *
Anthracene *
Di-n^butylphthalate
Fluoranthene *
Pyrene *
Butylbenzylphthalate
3,3' -fiichlorobenzidine
Benzo (a) anthracene *
Chrysene *
bis (2-Ethylhexyl)phthalate
Di-n-octylphthalate
Benzo (b) fluoranthene *
Benzo ( k ) f luoranthene *
Benzo ( a ) pyrene *
Indenod, 2, 3-cd)pyrene *
Dibenzo (a, h) anthracene *
Benzo (g, h, i)perylene *
_
=
RRF5
RRF10
RRF20
RRF10
RRF80
RRF50
__
=
RRF80
RRF
%
RSD
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
(1) Cannot be separated from Diphenylamine
* Compounds with required minimum RRF and maximum %RSD values.
All other compounds must meet a minimum RRF of 0.010.
FORM VI LCSV-2
OLC03.2
-------
6LCF
LOW CONCENTRATION WATER SEMIVOLATILE ORGANICS INITIAL CALIBRATION DATA
Lab Name:
Lab Code:
Instrument ID:
Contract:
Case No.:
Client No.:
SDG No.:
Calibration Date(s):
Calibration Times:
LAB FILE ID: R
RRF20 = R
COMPOUND
Phenol -d5
bis- (2-Chloroethyl) ether-
d8
2-Chlorophenol-d4
4 -Methylphenol - d8
Nitrobenzene-d5
2-Nitrophenol-d4
2,4-Dichlorophenol-d3
"4-Chloroaniline-d4
Dimethylphthalate-d6
Acenaphthylene - d8
4 - Ni t ropheno 1 - d4
Fluorene-dlO
4 , 6-Dinitro-methylphenol-
d2
Anthracene-dlO
Pyrene-dlO
Benzo (a) pyrene-d!2
RF5
RF50
RRF5
X
=
RRF10
RRF20
RRF10
RRF80
RRF50
_
-
RRF80
RRF
%
RSD
FORM VI LCSV-3
OLC03.2
-------
6LCG
LOW CONCENTRATION WATER PESTICIDE
INITIAL CALIBRATION OF SINGLE COMPONENT ANALYTES
Lab Name:
Lab Code:
Instrument ID:
GC Column:
Case No.:
Contract:
Client No.:
mid
Level (x low): low
ID: (MM) Date(s) Analyzed:
SDG No.:
high
COMPOUND
alpha-BHC
beta-BHC
delta-BHC
gamma -BHC (Lindane)
Heptachlor
Aldrin
Heptachlor epoxide
Endosulfan I
Dieldrin
4,4' -DDE
Endrin '
Endosulfan II
4,4' -DDD
Endosulfan sulfate
4,4' -DDT
Methoxychlor
Endrin ketone
Endrin aldehyde
alpha - Chi ordane
gamma - Chi ordane
Tetrachloro-m-xylene
Decachlorobiphenyl
RT
LOW
OF STANDAF
MID
JDS
HIGH
MEAN
RT
RT W
FROM
ENDOW
TO
* Surrogate retention times are measured from Standard Mix A analyses.
Retention time windows are ±0.05 minutes for all compounds that elute before
Heptachlor expoxide, ±0.07 minutes for all other compounds, except ±0.10
minutes for Decachlorobiphenyl.
FORM VI LCP-1
OLC03.2
-------
6LCH
LOW CONCENTRATION WATER PESTICIDE
INITIAL CALIBRATION OF SINGLE COMPONENT ANALYTES
Lab Name:
Lab Code:
Instrument ID:
GC Column:
Contract:
Case No.:
Client No.:
mid
Level (x low): low '
ID: (MM) Date(s) Analyzed:
SDG NO.:
high
COMPOUND
alpha-BHC
beta-BHC
delta-BHC
gamma -BHC (Lindane)
Heptachlor
Aldrin
Heptachlor epoxide
Endosulfan I
Dieldrin
4,4' -DDE
Endrin
Endosulfan II
4,4' -DDD
Endosulfan sulfate
4,4' -DDT
Methoxychlor
Endrin ketone
Endrin aldehyde
alpha-Chlordane •
gamma - Chi or dane
Tetrachloro-m-xylene
Dec achlorobiphenyl
LOW
CALIBRATIC
MID
)N FACTORS
HIGH
MEAN
%RSD
* Surrogate calibration factors are measured from Standard Mix A analyses.
FORM VI LCP-2
OLC03.2
-------
6LCI
LOW CONCENTRATION WATER PESTICIDE
INITIAL CALIBRATION OF MULTICOMPONENT ANALYTES
Lab Name:
Lab Code:
Contract:
Case No.:
Client No.:
SDG No.:
Instrument ID:
GC Column:
Date(s) Analyzed:
ID: (MM)
COMPOUND
Toxaphene
Aroclor 1016
Aroclor 1221
'.'Aroclor 1232
•f. f
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
AMOUNT
(NG)
PEAK1
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
RT
i
RT WI
FROM
NDOW
TO
CALIBRATION
FACTOR
N
*At least 3 peaks for each column are required for identification of
multicomponent analytes.
FORM VI LCP-3
OLC03.2
-------
6LCJ
LOW CONCENTRATION WATER PESTICIDE ANALYTE RESOLUTION SUMMARY
Lab Name:
Lab Code:
Case No.
Contract:
Client No.:
SDG No.
GC Column (1) .-
ID:
EPA Sample No. (RESC##):
Date Analyzed (1): .
.(MM)
Instrument ID (1):
Lab Sample ID (1):
Time Analyzed (1):
01
02
03
04
05
06
07
08
09
ANALYTE
RT
RESOLUTION
mn (2): ID: (MM) Instrument ID (2):
pie No. (RESC«#) : Lab Samole ID (2) :
alyze
01
02
03
04
05
06
07
08
09
sd (2) : -Time Analyzed (2) :
ANALYTE
RT
RESOLUTION
(%)
\,
FORM VI LCP-4
OLC03.2
-------
6LCK
LOW CONCENTRATION WATER PERFORMANCE EVALUATION MIXTURE (PEM)
Lab >
Lab C
GC Cc
EPA £
Date
lame:
:ode:
Contract :
Case No. : Client No. : SDG No. :
jlumn (1) : ID: (MM) Instrument ID (1) :
3amp]
Anal
01
02
03
04
05
06
07
08
e No. (PEMttft) : Lab Santole ID (1) :
vzed (1) : Time Analyzed (1) :
ANALYTE
RT
RESOLUTION
(%)
Dlumr
Sampl
Anal
•'
01
02
03
04
05
06
07
08
L (2) : ID: (MM) Instri
e No. (PEM##) : Lab S<
yzed (2) : Time ;
ANALYTE
ament ID (2) :
ample ID (2) :
Analyzed (2) :
'RT
RESOLUTION
(%)
FORM VI LCP-5
OLC03.2
-------
6LCL
LOW CONCENTRATION WATER INDIVIDUAL STANDARD MIXTURE A (INDA)
Lab Name:
Lab Code:
Case No.:
GC Column (1) :
ID:
EPA Sample No. (INDAM##):
Date Analyzed (1):
Contract:
Client No.:
.(MM)
Instrument ID (1):
Lab Sample ID (1):
Time Analyzed (1):
SDG No.
01
02
03
04
05
06
07
08
09
10
11
ANALYTE
•
RT
RESOLUTION
Dlumn
3ampl
Anal
01
02
03
04
05
06
07
08
09
10
11
(2) : ID: (MM) Instn.
e NO. (INDAM##) : ' Lab Sc
vzed (2) : Time 1
ANALYTE
iment ID (2) :
imple ID (2) :
taalyzed (2) :
RT
RESOLUTION
(%)
FORM VI LCP-6
OLC03.2
-------
6LCM
LOW CONCENTRATION WATER INDIVIDUAL STANDARD MIXTURE B (INDB)
Lab Name:
Lab Code:
Contract:
Case No.:
Client No.:
GC Column (1):
ID:
.(MM)
EPA Sample No. (INDBM##):
Date Analyzed (1):
Instrument ID (1):
Lab Sample ID (1):
Time Analyzed (1):
SDG No.
01
02
03
04
05
06
07
08
09
•10
-11
-12
,..13
ANALYTE
RT
RESOLUTION
•
GC Column (2) :
ID:
EPA Sample No. (INDBMtti):
Date .Analyzed. (2) :
.(MM)
Instrument ID (2):
Lab Sample ID (2):
Time Analyzed (2):
01
02
03
04
05
06
07
08
09
10
11
12
13
ANALYTE
RT
RESOLUTION
FORM VI LCP-7
OLC03.2
-------
7LCA
LOW CONCENTRATION WATER VOLATILE CONTINUING CALIBRATION CHECK
Lab Name:
Lab Code:
Contract:
Case No.:
Client No.:
SDG No.
Instrument ID:
Lab File ID:
Calibration Date:
Time:
EPA Sample No.(VSTD005##):
GC Column: ID:
.(MM)
Init. Calib. Date(s):
Init. Calib. Times:
Length: (M)
COMPOUND
Dichlorodifluoromethane
Chloromethane
Vinyl Chloride
Bromomethane
Chloroethane
Trichlorofluoromethane
1 , 1 -Dichloroethene
l,l,2-Trichloro-l,2,2-trifluoroethane
Acetone
Carbon Disulfide
Methyl Acetate
Methylene Chloride
trans-l, 2 -Dichloroethene
Methyl tert -Butyl Ether
1, 1-Dichloroethane
cis -1,2 -Dichloroethene
2-Butanone
Bromochloromethane
Chloroform
1,1, 1-Trichloroethane
Cyclohexane
Carbon Tetrachloride
Benzene
1 , 2 -Dichloroethane
Trichlor.oethene
Methyl cyclohexane
RRF
RRF5
MIN
RRF
0.100
0.100
0.100
0.200
0.050
0.200
0.100
0.100
0.400
0.100
0.300
%D
MAX
%D
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
All other compounds must meet a minimum RRF of 0.010.
FORM VII LCV-1
OLC03.2
-------
7LCB
LOW CONCENTRATION WATER VOLATILE CONTINUING CALIBRATION CHECK
Lab Name:
Lab Code:
Instrument ID:
Lab File ID:
Contract:
Case No.:
Client No.:
SDG No.
EPA Sample No.(VSTD005##):
GC Column: ID:.
Calibration Date:
Time:
.(MM)
Init. Calib. Date(s):
Init. Calib. Times:
Length:
(M)
COMPOUND
1 , 2 -Dichloropropane
Bromodichloromethane
cis-1, 3-Dichloropropene
4 -Methyl - 2 -pentanone
Toluene
trans -1 , 3 -Dichloropropene
1,1, 2-Trichloroethane
Tetrachloroethene
2-Hexanone
Dibromochloromethane
1 , 2 -Dibromoethane
•H i-i -
Chlqrobenzene
Ethylbenzene
Xylene (total)
Styrene
Bromof orm
I sopropylbenzene
1,1,2,2 -Tetrachloroethane
1 , 3 -Dichlorobenzene
1 , 4 -Dichlorobenzene
1 , 2 -Dichlorobenzene
1, 2-Dibromo-3-chloropropane
1,2 , 4-Trichlorobenzene
1,2,3 -Trichlorobenzene
RRF '
RRF5
MIN
RRF
0.200
0.200
0.400
0.100
0.100
0.100
0.100
0.100
0.500
0.100
0.300
0.300
0.050
0.100
0.400
0.400
0.400
0.200
0.200
%D
MAX -
%D
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
All other compounds must meet a minimum RRF of 0.010.
FORM VII LCV-2
OLC03.2
-------
7LCC
LOW CONCENTRATION WATER VOLATILE .CONTINUING CALIBRATION CHECK
Lab Name:
Lab Code:
Instrument ID:
Lab File ID:
Contract:
Case No.:
Client No.:
SDG No.
EPA Sample No.(VSTD005##):
GC Column: ID:
Calibration Date:
Time:
.(MM)
Init. Calib. Date(s):
Init. Calib. Times:
Length: (M)
COMPOUND
Vinyl Chloride-d3
Chloroethane-d5
1 , l-Dichloroethene-d2
2-Butanone-d5
Chloroform-d
1 ; 2-Dichloroethane-d4
Benzene -d6
1 , 2-Dichloropropane-d6
Toluene -d8
trans- 1, 3-Dichloropropene-d4
2-Hexanone-d5 >•
Bromoform-d
1, l,2,2-Tetrachloroethane-d2
1 , 2 -Dichlorobenzene-d4
RRF
-
-
RRF5
MIN
RRF
%D
MAX
%D
FORM VII LCV-3
OLC03.2
-------
7LCD
LOW CONCENTRATION WATER SEMIVOLATILE CONTINUING CALIBRATION CHECK
Lab Name:
Lab Code:
Contract:
Case No.:
Client No.:
SDG No.:
Instrument ID:
Lab File ID:
Calibration Date:
Time:
EPA Sample No.(SSTD020##):
GC Column: ID:
Init. Calib. Date(s):.
Init. Calib. Times:
.(MM)
COMPOUND
Benzaldehyde
Phenol
bis- (2-Chloroethyl)ether
2 - Chlorophenol
2 -Methylphenol
2,2' -oxybis (1-Chloropropane)
Acetophenone
4 -Methylphenol
N-Nitroso-di-n-propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2 -NiCrophenol
2 , 4 -Dimethylphenol
bis (2-Chloroethoxy) methane
2 , 4 -Dichlorophenol
Naphthalene
4-Chloroaniline
Hexachlorobutadiene
Caprolactam
4 - Chloro- 3 -methylphenol
2 -Methylnaphthalene
Hexachlorocyclopentadiene
2,4, 6-Trichlorophenol
2 , 4 , 5-Trichlorophenol
1,1' -Biphenyl •
2-Chloronaphthalene
2-Nitroaniline
Dimethylphthalate
2 , 6 -Dinitrotoluene
Acenaphthylene
3 -Nitroaniline
Acenaphthene
2 , 4 -Dinitrophenol
4 -Nitrophenol
Dibenzofuran
RRF
RRF20
MIN
RRF
0.800
0.700
0.800
0.700
0.600
0.500
0.300
0.200
0.400
0.100
0.200
0.300
0.200
0.700
0.200
0.400
0.200
0.200
0.800
0.200
0.900
0.900
0.800
%D
MAX
%D
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
30.0
30.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
All other compounds must meet a minimum RRF of 0.010.
FORM VII LCSV-1
OLC03.2
-------
7LCE
LOW CONCENTRATION WATER SEMIVOLATILE CONTINUING CALIBRATION CHECK
Lab Name:
Lab Code:
Contract:
Case No.:
Client No.:
SDG No.:
Instrument ID:
Lab File ID:
Calibration Date:
Time:
EPA Sample No,(SSTD020##):
GC Column: ID:
Init. Calib. Date(s):
Init. Calib. Times:
.(MM)
COMPOUND
2 , 4 -Dinitrotoluene
Diethylphthalate
Fluorene
4 - Chlorophenyl -phenylether
4-Nitroaniline
4 , 6 -Dinitro-2 -methylphenol
N-Nitrosodiphenylamine (1)
1,2,4,5 Tetrachlorobenzene
4 -Bromophenyl -phenylether
Hexachlorobenzene
Atrazine
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
3,3' -Dichlorobenzidine
Benzo (a) anthracene
Chrysene
bis (2-Ethylhexyl)phthalate
Di-n-octylphthalate
Benzo (b) fluoranthene
Benzo (k) fluoranthene
Benzo (a) pyrene
Indeno ( 1 , 2 , 3 - cd ) pyrene
Dibenzo (a, h) anthracene
Benzo (g , h , i ) perylene
RRF
RRF20
MIN
RRF
0.200
0.900
0.400
0.100
0.100
0.050
0.700
0.700
0.600
0.600
0.800
0.700
0.700
0.700
0.700
0.500
0.400
0.500
%D
MAX
%D
30.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
(1) Cannot be separated from Diphenylamine
All other compounds must meet a minimum RRF of 0.010.
FORM VII LCSV-2
OLC03.2
-------
,7LCF
LOW CONCENTRATION WATER SEMIVOLATILE CONTINUING CALIBRATION CHECK
Lab Name:
Lab Code:
Contract:
Case No.:
Client No.:
SDG No.:
Instrument ID:
Lab File ID:
Calibration Date:
Time:
EPA Sample No.(SSTD020##):
GC Column: ID:
Init. Calib. Date(s):
Init. Calib. Times:
.(MM)
COMPOUND
Phenol -d5
bis- (2-Chloroethyl)ether-d8
2 - Chlorophenol - d4
4 -Methylphenol -d8
Nitrobenzene-d5
2-Nitrophenol-d4
2,4-Dichlorophenol-d3
4-Chloroaniline-d4
Dimethylphthalate-d6
Acenaphthyl ene - d8
4 -Nitrophenol-d4
Fluorene-dlO
4, 6-Dinitro-methylphenol-d2
Anthracene-dlO
Pyrene-dlO
Benzo (a) pyrene-d!2
RRF
RRF20
MIN
RRF
%D
MAX
%D
FORM VII LCSV-3
OLC03.2
-------
7LCG
LOW CONCENTRATION WATER PESTICIDE CALIBRATION VERIFICATION SUMMARY
Lab Name:
Lab Code:
GC Column:
Contract:
Case No.
Client No.:
SDG No.:
ID:
EPA Sample No. (PIBLK##):
Lab Sample ID (PIBLK):
EPA Sample No. (PEM##): _
Lab Sample ID (PEM):
.(MM) Init. Calib. Date(s):
.__ Date Analyzed:
Time Analyzed:
Date Analyzed:
Time Analyzed:
PEM
COMPOUND
alpha-BHC
beta-BHC
gamma -BHC (Lindane)
Endrin
4,4' -DDT
Methoxychlor
RT
RT W]
FROM
[NDOW
TO
CALC
AMOUNT
(NG)
NOM
AMOUNT
(NG)
%D
4,4'-DDT % Breakdown (1)
Combined % Breakdown (1)
Endrin % breakdown (1) :_
FORM VII LCP-1
OLC03.2
-------
7LCH
LOW CONCENTRATION WATER PESTICIDE CALIBRATION VERIFICATION SUMMARY
Lab Name:
Lab Code:
GC Column:
Contract:
Case No.:
Client No.:
SDG No.:
ID:
EPA Sample No. (PIBLK##):
Lab Sample ID (PIBLK):
EPA Sample No. (INDAM##):
Lab Sample ID (INDA):
.(MM) Init. Calib. Date(s):
Date Analyzed:
Time Analyzed:
Date Analyzed:
Time Analyzed:
INDIVIDUAL MIX A
COMPOUND
alpha-BHC
gamma-BHC (Lindane)
Heptachlor
Endosulfan I
Dieldrin
Endrin.
4,4' -ODD
4,4' -DDT
Methoxychlor
Tetrachloro-m-xylene
Decachlorobiphenyl
RT
RT W]
FROM
[NDOW
TO
CALC
AMOUNT
(NG)
NOM
AMOUNT
(NG)
%D
EPA Sample No. (INDBM##)
Lab Sample ID (INDB): _
Date Analyzed:
Time Analyzed:
INDIVIDUAL MIX B
COMPOUND
beta-BHC
delta-BHC
Aldrin
Heptachlor epoxide
4,4' -DDE
Endosulfan II
Endosulfan sulfate
Endrin ketone
Endrin aldehyde
alpha - Chi ordane
gamma - Chi ordane
Tetrachloro-m-xylene
Decachlorobiphenyl
RT
RT W
FROM
INDOW
TO
CALC
AMOUNT
(NG)
NOM
AMOUNT
(NG)
%D
FORM VII LCP-2
OLC03.2
-------
8LCA
LOW CONCENTRATION WATER VOLATILE INTERNAL STANDARD AREA AND RT SUMMARY
Lab Name:
Lab Code : Case No . :
EPA Sample No. (VSTD005##) :
Lab File ID (Standard) :
Instrument ID:
GC Column: ID:
Contract :
Client No. : SDG No. :
Date Analyzed:
Time Analyzed:
(MM) Lenqth: (M)
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
-
12 HOUR STD
UPPER LIMIT
LOWER LIMIT
EPA SAMPLE NO.
IS1 (CBZ)
AREA #
RT fl
IS2 (DFB)
AREA fl
.
RT #
IS3 (DCB)
AREA #
RT #
IS1 (CBZ) = Chlorobenzene-d5
IS2 (DFB) = 1,4-Difluorobenzene
IS3 (DCB) = l,4-Dichloroberizene-d4
AREA UPPER LIMIT = +40% of internal standard area
AREA LOWER LIMIT = -40% of internal standard area
RT UPPER LIMIT = +0.33 minutes of internal standard RT
RT LOWER LIMIT = -0.33 minutes of internal standard RT
# Column used to flag values outside QC limits with an asterisk.
* Values outside of QC limits
Page of
FORM VIII LCV
OLC03.2
-------
8LCB
LOW CONCENTRATION WATER SEMIVOLATILE INTERNAL STANDARD AREA AND RT SUMMARY
Lab Name :
Lab Code : Case No . :
EPA Sample No. (SSTD020«#) :
Lab File ID (Standard) :
Instrument ID :
Contract :
Client No. :
Date Analyzed:
Time Analyzed:
GC Column:
SDG No. :
ID: (MM)
01
02
03
04
05
06
07
08
09
LO
11
12
13
14
15
16
17
18
19
20
21
22
12 HOUR STD
UPPER LIMIT
LOWER LIMIT
EPA SAMPLE NO.
""• •
• ••off
-•"
~-.r
-.
^
IS1 (DCB)
AREA #
RT #
IS2 (NPT)
AREA fl
RT #
IS3 (ANT)
AREA #
RT #
IS1 (DCB) = l,4-Dichlorobenzene-d4
IS2 (NPT) = Naphthalene-d8
IS3 (ANT) = Acenaphthene-dlO
AREA UPPER LIMIT = +100% of internal standard area
AREA LOWER LIMIT = -50% of internal standard area
RT UPPER LIMIT = +0.33 minutes of internal standard RT
RT LOWER LIMIT = -0.33 minutes of internal standard RT
# Column used to flag values outside QC limits with an asterisk.
* Values outside of QC limits
Page of
FORM VIII LCSV-l
OLC03.2
-------
8LCC
LOW CONCENTRATION WATER SEMIVOLATILE INTERNAL STANDARD AREA' AND RT SUMMARY
Lab Name:
Lab Code : Case No . :
EPA Sample No. (SSTD020##) :
Lab File ID (Standard) :
Instrument ID:
Contract :
Client No. :
Date Analyzed:
Time Analyzed:
GC Column:
SDG No . :
ID: (MM)
01
02
03
04
05
06
07
08
09
10
11
12
L3
14
15
16
17
18
19
20
21
22
12 HOUR STD
UPPER LIMIT
LOWER LIMIT
EPA SAMPLE NO.
IS4 (PHN)
AREA #
RT #
IS5 (CRY)
AREA #
RT #
IS6 (PRY)
AREA #
RT #
IS4 (PHN) = Phenanthrene-dlO
IS5 (CRY) = Chrysene-dl2
IS6 (PRY) = Perylene-dl2
AREA UPPER LIMIT = +100% of internal standard area
AREA LOWER LIMIT = -50% of internal standard area
RT UPPER LIMIT = +0.33 minutes of internal standard RT
RT LOWER LIMIT = -0.33 minutes of internal standard RT
# Column used to flag values outside QC limits with an asterisk.
* Values outside of QC limits
Page of
FORM VIII LCSV-2
OLC03.2
-------
8LCD
LOW CONCENTRATION WATER PESTICIDE ANALYTICAL SEQUENCE
Lab Name:
Lab Code :
GC Column:
Contract :
Case No. : Client No. :
ID: (MM) Init. Calib. Date(s):
SDG No . :
Instrument ID:
THE ANALYTICAL SEQUENCE OF SAMPLES, BLANKS, AND STANDARDS IS GIVEN BELOW:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
MEAN SURROGATE RT FROM INITIAL CALIBRATION
TCX : DCB :
EPA
SAMPLE NO.
.....
......
LAB
SAMPLE ID
DATE
ANALYZED
v
TIME
ANALYZED
TCX
RT #
DCB
RT #
TCX = Tetrachloro-m-xylene
DCB = Decachlorobiphenyl
QC LIMITS
(±0.05 MINUTES)
(±0.10 MINUTES)
# Column used to flag retention time values with an asterisk.
* Values outside of QC limits.
Page of
FORM VIII LCP
OLC03.2
-------
9LCA
LOW CONCENTRATION WATER PESTICIDE FLORISIL CARTRIDGE CHECK
Lab Name:
Lab Code:
Case No.:
Florisil Cartridge Lot Number:
GC Column (1) : ID:.
(MM)
Contract:
Client No.:
SDG No.:
Date of Analysis:
GC Column(2):
.(MM)
COMPOUND
alpha -BHC
qamma-BHC (Lindane)
Heptachlor
Endosulfan I
Dieldrin
Endrin
4,4' -ODD
4,4' -DDT
Methoxychlor
Tetrachloro-m-xylene
Decachlorobiphenyl
2 , 4 , 5-Trichlorophenol
SPIKE
ADDED
(NG)
SPIKE
RECOVERED
(NG)
%
REC #
QC
LIMITS
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
<5
# Column to be used to flag recovery with an asterisk.
* Values outside of QC limits.
THIS CARTRIDGE LOT APPLIES TO THE FOLLOWING SAMPLES,
LABORATORY CONTROL SAMPLES, AND BLANKS:
01
02
03
• 04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
EPA
SAMPLE NO.
LAB
SAMPLE ID
DATE
ANALYZED 1
DATE
ANALYZED 2
Page of
FORM IX LCP
OLC03.2
-------
Lab Name:
Lab Code:
Lab Sample ID:
Instrument ID (1):
GC Column:(1):
10LCA
LOW CONCENTRATION WATER PESTICIDE IDENTIFICATION
SUMMARY FOR SINGLE COMPONENT ANALYTES
EPA SAMPLE NO.
Case No.:
ID:
Contract:
Client No.:
.(MM)
Date(s) Analyzed:
Instrument ID (2) :
GC Column:(2):
SDG No.:
.(MM)
ANALYTE
'_.•
COL
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
RT
RT WI
FROM'
NDOW
TO
CONCENTRATION
%D
Page of
FORM X LCP-1
OLC03.2
-------
10LCB
LOW CONCENTRATION WATER PESTICIDE IDENTIFICATION
SUMMARY FOR MULTICOMPONENT ANALYTES
EPA SAMPLE NO.
Lab Name:
Lab Code:
Contract:
Case No.:
Client No.:
SDG No.:
Lab Sample ID:
Instrument ID (1)
GC Column:(1):
ID:
Date(s) Analyzed:
Instrument ID (2)
.(MM) GC Column:(2):
ID:
.(MM)
ANALYTE
COLUMN 1
COLUMN 2
COLUMN 1
COLUMN 2
COLUMN 1
COLUMN 2
PEAK
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
RT
RT WI
FROM
NDOW
TO
CONCENTRATION
MEAN
CONCENTRATION
%D
At least 3 peaks for each column are required for identification of
multicomponent analytes.
Page of '
FORM X LCP-2
OLC03.2
-------
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.
3 . Chain of Custody
Records
4 . Traffic Reports
or Packing Lists
5. Airbill
6. Airbill No.
7 . Sample Tags
Sample Tag Nos .
8 . Sample Condition
9 . Cooler
' Temperature
Indicator Bottle
10. Cooler
Temperature
11. Does
information on
custody
records ,
traffic
reports,
and sample tags
agree?
12 . Date Received
at Lab
13 . Time Received
Present /Absent*
Intact /Broken
Present /Absent*
Present /Absent*
Airbill/Sticker
Present/Absent*
Present /Absent*
Listed/Not
Listed on Chain-
of- Custody
Intact /Broken* /
Leaking
Present /Absent*
Yes /No*
Sample Transfer
Fraction
Area #
By . .
On
Fraction
Area #
By
On
Sample Delivery Group No.
EPA
Sample #
Corresponding
Sample
Tag 8
Assigned
Lab #
Client 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
OLC03.2
-------
LOW CONCENTRATION WATER ORGANICS COMPLETE SDG FILE (CSF) INVENTORY SHEET
LABORATORY NAME
CITY/STATE
CASE NO. SDG NO.
SDG NOS. TO FOLLOW
CLIENT NO.
CONTRACT NO.
SOW NO.
All documents delivered in the Complete SDG File must be original documents where possible.
PAGE NOs CHECK
FROM TO LAB EPA
1. Inventory Sheet (Form DC-2) (Do Not Number)
2. SDG Case Narrative
3. SDG Cover Sheet/Traffic Report
4. Volatiles Data
a. QC Summary
Deuterated Monitoring Compound Recovery (Form II LCV)
Matrix Spike/Matrix Spike Duplicate Recovery
(Form III LCV) (if Region requests)
Method Blank Summary (Form IV LCV)
GC/MS Instrument Performance Check (Form V LCV)
Internal Standard Area and RT Summary (Form VIII LCV)
b. Sample Data
TCL Results - (Form I LCV-1, LCV-2)
Tentatively Identified Compounds (Form I LCV-TIC)
Reconstructed Total Ion Chromatograms (RIC) for each sample
For each sample:
Raw Spectra and background-subtracted mass
spectra of target compounds identified
Quantitation reports
Mass Spectra of all reported TICs with three
best library matches
c. Standards Data (All Instruments)
Initial Calibration Data (Form VI LCV-1, LCV-2, LCV-3)
RICs and Quantitation Reports for all Standards
Continuing Calibration Data (Form VII LCV-1, LCV-2, LCV-3)
RICs and Quantitation Reports for all Standards
d. Raw QC Data
BFB
Blank Data
Matrix Spike/Matrix Spike Duplicate Data
(if Region requests)
FORM DC-2-1 OLC03.2
-------
LOW CONCENTRATION WATER ORGANICS COMPLETE SDG FILE (CSF) INVENTORY SHEET (Con't)
CASE NO.
SDG NO.
SDG NOS. TO FOLLOW
CLIENT NO.
PAGE NOs
FROM TO
CHECK
LAB EPA
5. Semivolatiles Data
a. QC Summary
Deuterated Monitoring Compound (Form II LCSV)
MS/MSD Summary (Form III LCSV) (if Region requests)
Method Blank Summary (Form IV LCSV)
GC/MS Instrument Performance Check (Form V LCSV)
Internal Standard Area and RT Summary (Form VIII LCSV)
b. Sample Data
TCL Results - (Form I LCSV-1, LCSV-2)
Tentatively Identified Compounds (Form I LCSV-TIC)
Reconstructed Total Ion Chromatograms (RIC) for each sample
For each sample:
Raw Spectra and background-subtracted mass
spectra of target compounds
Quantitation reports
Mass Spectra of TICs with three best library matches
c. Standards,; Data (All Instruments)
Initial Calibration Data (Form VI LCSV-1, LCSV-2, LCSV-3)
RICs and Quantitation Reports for all Standards
Continuing Calibration Data (Form VII LCSV-1, LCSV-2, LCSV-3)
RICs and Quantitation Reports for all Standards
d. Raw QC Data
DFTPP
Blank Data
Matrix Spike/Matrix Spike Duplicate Data (if Region requests)
6. Pesticides Data
a. QC Summary
Surrogate Percent Recovery Summary (Form II LCP)
MS/MSD Duplicate Summary (Form III LCP-1) (if Region requests)
Laboratory Control Sample Recovery (Form III LCP-2)
Method Blank Summary (Form IV LCP)
b. Sample Data
TCL Results - Organic Analysis Data Sheet (Form I LCP)
Chromatograms (Primary Column)
Clnromatograms from second GC column confirmation
GC Integration report or data system printout
Manual work sheets
FORM DC-2-2
OLC03.2
-------
LOW CONCENTRATION WATER ORGANICS COMPLETE SDG FILE (CSF) INVENTORY SHEET (Con't)
CASE NO.
SDG NO.
SDG NOS. TO FOLLOW
CLIENT NO.
PAGE NOS
FROM TO
CHECK
LAB EPA
6. Pesticides Data (Con't)
c. Standards Data
Initial Calibration of Single Component Analytes
(Form VI LCP-1 and LCP-2)
Initial Calibration of Multicomponent Analytes (Form VI LCP-3)
Analyte Resolution Summary (Form VI LCP-4)
Performance Evaluation Mixture (Form VI LCP-5)
Individual Standard Mixture A (Form VI LCP-6)
Individual Standard Mixture B (Form VI LCP-7)
Calibration Verification Summary (Form VII LCP-1)
Calibration Verification Summary (Form VII LCP-2)
Analytical Sequence (Form VIII LCP)
Florisil Cartridge Check (Form IX LCP)
Pesticide Identification Summary for Single
Component Analytes (Form X LCP-1)
Pesticide Identification Summary for
Multicomponent Analytes (Form X LCP-2)
Chromatograms and data system printouts
A printout of retention times and corresponding peak
areas or peak heights
Raw QC Data
Blank Data
Matrix Spike/Matrix Spike Duplicate Data (if Region requests)
Laboratory Control Sample Data
e. Raw Florisil Data
7. Miscellaneous Data
Original preparation and analysis forms or copies
of preparation and analysis logbook pages
Internal sample and sample extract transfer
chain-of-custody records
Screening records
All instrument output, including strip charts
from screening activities (describe or list)
FORM DC-2-3
OLC03.2
-------
LOW CONCENTRATION WATER ORQANICS COMPLETE SDG FILE (CSF) INVENTORY SHEET (Con't)
CASE NO.
SDG NO.
SDG NOS. TO FOLLOW
•CLIENT NO.
PAGE NOs
FROM TO
CHECK
LAB EPA
8. EPA Shipping/Receiving Documents
Airbills (No. of shipments )
Chain-of-Custody Records
Sample Tags
Sample Log-in Sheet (Lab & DC1)
Miscellaneous Shipping/Receiving Records (describe or list)
9. Internal Lab Sample Transfer Records and Tracking Sheets
(describe or list)
10 . Other- Records
(describe or list)
Telephone Communication Log
11. Comments;
Completed by:
(CLP Lab)
(Signature)
(Printed Name/Title)
(Date)
Verified by:
(CLP Lab)
(Signature)
(Printed Name/Title)
Audited by:
(EPA)
(Signature)
(Printed Name/Title)'
(Date)
FORM DC-2-4
OLC03.2
-------
EXHIBIT C
TARGET COMPOUND LIST AND
CONTRACT REQUIRED QUANTITATION LIMITS
NOTE: Specific quantitation limits are highly matrix-dependent. The
quantitation limits listed herein are provided for guidance and may not
always be achievable.
The CRQL values listed on the following pages are.based on the analysis
of samples according to the specifications given in Exhibit D.
C-l OLC03.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
OLC03.2 C-2
-------
Exhibit C - Target Compound List and Contract Required Quantitation Limits
Table of Contents
Page
1.0 VOLATILES TARGET COMPOUND LIST AND CONTRACT REQUIRED
QUANTITATION LIMITS 5
2.0 SEMIVOLATILES TARGET COMPOUND LIST AND CONTRACT REQUIRED
QUANTITATION LIMITS . . 7
3 .0 PESTICIDES/AROCLORS TARGET COMPOUND LIST AND CONTRACT
REQUIRED QUANTITATION LIMITS . . .... 9
C-3 OLC03.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
OLC03.2 C-4
-------
1.0
Exhibit C -- Section 1
Volatiles (VGA)
VOLATILES TARGET COMPOUND LIST AND CONTRACT REQUIRED
QUANTITATION LIMITS
Ouantitation Limits
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
Volatiles
Dichlorodifluoromethane
Chi oromethane
Vinyl Chloride
Brotnomethane
Chloroethane
Trichlorofluoromethane
1 , 1 -Dichloroethene
1,1,2-Trichloro-
1,2 , 2-trif luoroethane
Acetone
Carbon Disulfide
Methyl Acetate
Methylene Chloride
trans-1, 2 -Dichloroethene
Methyl tert -Butyl Ether
1 , 1 -Dichloroethane
cis-1, 2 -Dichloroethene
2-Butanone
Bromochloromethane
Chloroform
1,1, 1-Trichloroethane
Cyclohexane
Carbon Tetrachloride
Benzene
1 , 2 -Dichloroethane
Trichloroethene
Me t hy 1 eye 1 ohexane
1 , 2 -Dichloropropane
Bromodichloromethane
cis - 1 , 3 -Dichloropropene
4 -Methyl -2 -pentanone
Toluene
trans-1, 3 -Dichloropropene
1,1,2 -Trichloroethane
Tetrachloroethene
2-Hexanone
Dibromochloromethane
1 , 2 -Dibromoethane
Chlorobenzene
CAS Number
75-71-8
74-87-3
75-01-4
74-83-9
75-00-3
75-69-4
75-35-4
76-13-1
67-64-1
75-15-0
79-20-9
75-09-2
156-60-5
1634-04-4
75-34-3
156-59-2
78-93-3
74-97-5
67-66-3
71-55-6
110-82-7
56-23-5
71-43-2
107-06-2
79-01-6
108-87-2
78-87-5
75-27-4
10061-01-5
108-10-1
108-88-3
10061-02-6
79-00-5
127-18-4
591-78-6
124-48-1
106-93-4
108-90-7
Water
ug/L
0.50 .
0.50
0.50
0.50
0.50
0.50
0.50
0.50
5.0
0.50
0.50
0.50
0.50
, 0.50
0.50
0.50
5.0
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
5.0
0.50
0.50
0.50
0.50
5.0
0.50
0.50
0.50
C-5
OLC03.2
-------
Exhibit C -- Section 1
Volatiles (VOA) (Con't)
1.0
VOLATILE TARGET COMPOUND LIST AND CONTRACT REQUIRED
QUANTITATION LIMITS (Con't)
Ouantitation Limits
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
Volatiles
Ethylbenzene
Xylenes (total)
Styrene
Bromoform
I sopropylbenzene
1,1,2,2 -Tetrachloroethane
i , 3 -Dichlorobenzene
1 , 4 -Dichlorobenzene
1 , 2 -Dichlorobenzene
1 , 2 -Dibromo- 3 -chloropropane
1,2,4 -Trichlorobenzene
1,2,3 -Trichlorobenzene
CAS Number
100-41-4
1330-20-7
100-42-5
75-25-2
98-82-8
79-34-5
541-73-1
106-46-7
95-50-1
96-12-8
120-82-1
87-61-6
Water
0,
0,
0,
0,
0,
0,
0,
0,
0.
0,
0,
0,
.50
.50
.50
.50
.50
.50
.50
.50
.50
.50
.50
.50
OLC03.2
C-6
-------
Exhibit C -- Section 2
Semivolatiles (SVGA)
2.0
SEMIVOLATILES TARGET COMPOUND LIST AND CONTRACT REQUIRED
QUANTITATION LIMITS
Ouantitation Limits
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
Semivolatiles
Benzaldehyde
Phenol
bis- (2-Chloroethyl) ether
2 - Chlorophenol
2 -Methylphenol
2,2' -oxybis (1-Chloropropane) l
Acetophenone
4 -Methylphenol
N-Nitroso-di-n-propylamine
Hexachl oroethane
Nitrobenzene
Isophorone
2 -Nitrophenol
2 , 4 -Dimethylphenol
bis (2-Chloroethoxy)methane
2 , 4 -Dichlorophenol
Naphthalene
4-Chloroaniline
Hexachlorobutadiene
Caprolactam
4 -Chloro- 3 -methylphenol
2 -Methylnaphthalene
Hexachlorocyclopentadiene
2,4, 6-Trichlorophenol
2,4,5 -Tr ichlorophenol
1,1' -Biphenyl
2 - Chloronaphthalene
2-Nitroaniline
Dimethylphthalate
2, 6-Dinitrotoluene
Acenaphthylene
3-Nitroaniline
Acenaphthene
2 , 4 -Dinitrophenol
CAS
Number
100-52-7
108-95-2
111-44-4
95-57-8
95-48-7
108-60-1
98-86-2
106-44-5
621-64-7
67-72-1
98-95-3
78-59-1
88-75-5
105-67-9
111-91-1
120-83-2
91-20-3
106-47-8
87-68-3
105-60-2
59-50-7
91-57-6
77-47-4
88-06-2
95-95-4
92-52-4
91-58-7
88-74-4
131-11-3
606-20-2
208-96-8
99-09-2
83-32-9
51-28-5
Water
• g/L
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0.
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
20
5.0
5.0
20
5.0
5.0
5.0
20
5.0
20
Previously known by the name bis(2-Chloroisopropyl)ether.
C-7
OLC03.2
-------
Exhibit C -- Section 2
Semivolatiles (SVOA) (Con't)
2.0
SEMIVOLATILES TARGET COMPOUND LIST AND CONTRACT REQUIRED
QUANTITATION LIMITS (Con't)
Ouantitation Limits
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
105.
106.
107.
108.
109.
110.
111.
112.
113.
114.
115.
Semivolatiles
4-Nitrophenol
Dibenzofuran
2 , 4 -Dinitrotoluene
Diethylphthalate
Fluorene
4 - Chlorophenyl -phenylether
4 -Nitroaniline
4, 6-Dinitro-2-methylphenol
N-Nitrosodiphenylamine
1,2,4,5 Tetrachlorobenzene
4 -Bromophenyl -phenylether
Hexachlorobenzene
Atrazine
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
3,3' -Dichlorobenzidine
Benzo (a) anthracene
Chrysene
bis(2-Ethylhexyl)phthalate ,
Di-n-octylphthalate
Benzo (b) fluoranthene
Benzo (k) fluoranthene
Benzo (a) pyrene
Indeno ( 1 , 2 , 3 - cd ) pyrene
Dibenzo (a, h) anthracene
Benzo (g, h, i) perylene
CAS
Number
100-02-7
132-64-9
121-14-2
84-66-2
86-73-7
7005-72-3
100-01-6
534-52-1
86-30-6
95-94-3
101-55-3
118-74-1
1912-24-9
87-86-5
85-01-8
120-12-7
84-74-2
206-44-0
129-00-0
85-68-7
91-94-1
56-55-3
218-01-9
117-81-7
117-84-0
205-99-2
207-08-9
50-32-8
193-39-5
53-70-3
191-24-2
Water
•g/L
20
5.0
5.0
5.0
5.0
5.0
20
20
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
OLC03.2
C-8
-------
3.0
Exhibit C - Section 3
Pesticides/Aroclors (PEST/ARO)
PESTICIDES/AROCLORS TARGET COMPOUND LIST AND CONTRACT
REQUIRED QUANTITATION LIMITS
Ouantitation Limits
116.
117.
118.
119.
120.
121.
122.
123.
124.
125.
126.
127.
128.
129.
130.
131.
132.
133.
134.
135.
136.
137.
138.
139.
140.
141.
142.
143.
Pesticides/Aroclors
alpha -BHC
beta-BHC
delta-BHC
gamma-BHC (Lindane)
Heptachlor
Aldrin
Heptachlor epoxide2
Endosulfan I
Dieldrin
4,4' -DDE
Endrin
Endosulfan II
4,4' -ODD
Endosulfan sulfate
4,4' -DDT
Methoxychlor
Endrin ketone
Endrin aldehyde
alpha - Chi ordane
gamma - Chlordane
Toxaphene
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
CAS Number
319-84-6
319-85-7
319-86-8
58-89-9
76-44-8
309-00-2
1024-57-3
959-98-8
60-57-1
72-55-9
72-20-8
33213-65-9
72-54-8
1031-07-8
50-29-3
72-43-5
53494-70-5
7421-93-4
5103-71-9
5103-74-2
8001-35-2
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
Water
• g/L
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.10
0.02
0.02
0.01
0.01
1.0
0.20
0.40
0.20
0.20
0.20
0.20
0.20
2Only the exo-epoxy isomer (isomer B) of heptachlor epoxide is reported
on the data reporting forms (Exhibit B).
C-9
OLC03.2
-------
EXHIBIT D
METHOD FOR THE ANALYSIS OF LOW CONCENTRATION WATER FOR
VOLATILE (PURGEABLE) ORGANIC COMPOUNDS
D-l/VOA OLC03.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
OLC03.2 D-2/VOA
-------
Exhibit D -- Analytical Methods for Volatiles
Table of Contents
Page
1.0 SCOPE AND APPLICATION 5
2.0 SUMMARY OF METHOD 6
3.0 DEFINITIONS 6
4.0 INTERFERENCES 7
5 .0 SAFETY 8
6.0 EQUIPMENT AND SUPPLIES 9
6.1 Glassware 9
6.2 pH Paper 9
6.3 Balances 9
6.4 Purge and Trap Device ' . . 9
6.5 Gas Chromatograph/Mass Spectrometer (GC/MS) System . . . . ; 11
7.0 REAGENTS AND STANDARDS 15
7.1 Reagents 15
7.2 Standards 15
8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE 20
.8.1 Sample Collection and Preservation 20
8.2 Procedure for Sample Storage 20
8.3 Temperature Records for Sample Storage 20
8.4 Contract Required Holding Times 21
9.0 CALIBRATION AND STANDARDIZATION ' 21
9.1 Instrument Operating Conditions 21
9.2 Instrument Performance Check -- 4-Bromofluorobenzene (BFB) 23
9.3 Initial Calibration 24
9.4 Continuing Calibration 28
10.0 SAMPLE ANALYSIS 31
10.1 Summary of Sample Analysis 31
10.2 Procedure for Sample Analysis 31
11.0 DATA ANALYSIS AND CALCULATIONS 35
11.1 Qualitative Identification of Target Compounds 35
11.2 Qualitative Identification of Non-Target Compounds 36
11.3 Calculations 38
11.4 Technical Acceptance Criteria for Sample Analysis 41
11.5 Corrective Action for Sample Analysis 42
12.0 QUALITY CONTROL (QC) 44
12.1 Blank Analyses 44
12.2 Matrix Spike/Matrix Spike Duplicate (MS/MSD) 47
12.3 Method Detection Limit (MDL) Determination ' 49
D-3/VOA OLC03.2
-------
Exhibit D -- Analytical Methods for Volatiles
Table of Contents (Continued)
Page
13.0 METHOD PERFORMANCE : 51
14.0 POLLUTION PREVENTION 51
15.0 WASTE MANAGEMENT 51
16.0 REFERENCES 51
17.0 TABLES/DIAGRAMS/FLOWCHARTS ..." 52
OLC03.2 D-4/VOA
-------
1.0
exhibit D Volatiies -- Section 1
Scope and Application
SCOPE AND APPLICATION
1.1 The analytical method that follows is designed to analyze water samples
containing low concentrations of the volatile compounds listed in the
Target Compound List (TCL) in Exhibit C. The majority of the samples
are expected to be obtained from drinking water and well/ground water
type sources around Superfund sites. The method is based on EPA Method
524.2 and the volatile method contained in the Contract Laboratory
Program (CLP) Statement of Work (SOW), "Organic Analysis, Multi-Media,
Multi-Concentration". The sample preparation and analysis procedures
included in this method are based on purge and trap Gas
Chromatograph/Mass Spectrometer (GC/MS) techniques.1
1.2 Dichlorodifluoromethane, Trichlorofluoromethane, l,l,2-Trichloro-l,2,2T
trifluoroethane, Methyl Acetate, 1,2,3-Trichlorobenzene, Methyl tert-
butyl ether, Cyclohexane, Methylcyclohexane, and Isopropylbenzene have
been added to the TCL.
1.3 Problems that have been associated with the following compounds analyzed
by this method include:
• Chloromethane, vinyl chloride, bromotnethane, and chloroethane may
display peak broadening if the compounds are not delivered to the GC
column in a tight band.
• Acetone, hexanone, 2-butanone, and 4-methyl-2-pentanone have poor
purge efficiencies.
• 1,1,1-Trichloroethane and all of the dichloroethanes may
dehydrohalogenate during storage or analysis.
• Tetrachloroethane and 1,1-dichloroethane may be degraded by
contaminated transfer lines in purge and trap systems and/or active
sites in trapping materials.
• Chloromethane may be lost if the purge flow is too fast.
• Bromoform is one of the compounds most likely to be adversely
affected by cold spots and/or active sites in the transfer lines.
Response of its quantitation ion (m/z 173) is directly affected by
the tuning of 4-Bromofluorobenzene (BFB) at ions m/z 174/176.
Increasing the m/z 174/176 ratio within the specified Quality
Control (QC) limits may improve bromoform response.
• Due to the lower quantitation limits required by this method, extra
caution must be exercised when identifying compounds.
'•This analytical method includes the use of Deuterated Monitoring
Compounds (DMC) for precision and accuracy assessment.
D-5/VOA
OLC03.2
-------
Exhibit D Volatiles — Sections 2 & 3
Summary of Method
2.0 SUMMARY OF METHOD
2.1 An inert gas is bubbled through a 25 milliliter (tnL) sample contained in
a specially designed purging chamber at ambient temperature causing the
purgeables to be transferred from the water/aqueous phase to the vapor
phase. The vapor is swept through a sorbent column where the purgeables
are trapped. After purging is completed, the sorbent column is heated
and backflushed with the inert gas to desorb the purgeables onto a Gas
Chromatograph (GC) wide-bore capillary column. The GC is temperature
programmed to separate the purgeables, which are then detected with a
Mass Spectrometer (MS).
2.2 Deuterated Monitoring Compounds (DMCs) and internal standards are added
to all samples and blanks. The target compounds and DMCs are identified
in the samples and blanks by analyzing standards that contain all target
compounds, DMCs, and internal standards under the same conditions and
comparing resultant mass spectra and GC retention times. A Relative
Response Factor (RRF) is established for each target compound and DMC
during the initial and continuing calibrations. The mass spectra
response from the Extracted Ion Current Profile (EICP) for the primary
quantitation ion produced by that compound is compared to the mass
spectra response for the primary quantitation ion produced by the
associated internal standard compound. Each identified target compound
and DMC is quantitated by comparing the instrument response for the
compound in the sample or blank with the instrument response of the
associated internal standard, while taking into account the RRF from the
most recent mid-point calibration, the sample volume, and any sample
dilutions.
2.3 Non-target compounds are identified by comparing the resultant mass
spectra from the non-target compounds to mass spectra contained in the
NIST/EPA/NIH (May 1992 release or later) and/or Wiley (1991 release or
later) or equivalent mass spectral library. Non-target compounds are
quantitated by comparing the mass spectra response from the total ion
chromatograms to the mass spectra response of the nearest internal
standard compound. A RRF of 1 is assumed.
3.0 DEFINITIONS
See Exhibit G for a complete list of definitions.
OLC03.2 D-6/VOA
-------
Exhibit D Volatiles -- Section 4
Interferences
4 .0 INTERFERENCES
4.1 Method interference may be caused by impurities in the purge gas,
organic compounds out-'gassing from the plumbing ahead of the trap, and "
solvent vapors in the laboratory. The analytical system must be
demonstrated to be free from contamination under the conditions of the
analysis by running laboratory method and instrument blanks as described
in Section 12. The use of non-polytetrafluorbethylene (PTFE) tubing,
non-PTFE thread sealants, or flow controllers with rubber components in
the purging device should be avoided.
4.2 Samples can be contaminated by diffusion of purgeable organics
(particularly methylene chloride, fluorocarbons, and other common
laboratory solvents) through the septum seal into the sample during
storage and handling. Therefore, these samples must be stored
separately from other laboratory samples and standards and must be
analyzed in a room whose atmosphere is demonstrated to be free of all
potential contaminants which will interfere with the analysis.
4.3 Contamination by carryover can occur whenever high level and low level
samples are sequentially analyzed. To reduce carryover, the purging
device and sampling syringe must be rinsed with reagent water between
sample analyses. Whenever an unusually concentrated sample is
encountered, it must either be followed by analysis of an instrument
blank, or the next sample must be closely monitored to check for cross
contamination. For samples containing large amounts of water-soluble
materials, suspended solids, high boiling compounds, or high purgeable
levels, it may be necessary to wash out the purging device with a
detergent solution between analyses, rinse it with distilled water, and
then dry it in an oven-at 105°C. The trap and other parts of the system
are also subject to contamination; therefore, frequent bakeout and
purging of the entire system may be required.
4.4 The laboratory where volatile analysis is performed should be completely
free of solvents.
D-7/VOA OLC03.2
-------
Exhibit D Volatiles -- Section 5
Safety
5.0 SAFETY
5.1 The toxicity or carcinogenicity of each reagent used in this method has
not been precisely defined; however, each chemical compound should be
treated as a potential health hazard. 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 OSHA regulations regarding the safe handling
of the chemicals specified in this method. A reference file of material
data handling sheets should also be made available to all personnel
involved in the chemical analysis.
5.2 The following analytes covered by this method have been tentatively
classified as known or suspected, human or mammalian carcinogens:
benzene; carbon tetrachloride; chloroform; and vinyl chloride. Primary
standards of these toxic compounds should be prepared in a hood. A
NIOSH/MESA-approved toxic gas respirator should be worn when the analyst
handles high concentrations of these toxic compounds.
OLC03.2 D-8/VOA
-------
Exhibit D Volatiles -- Section 6
Equipment and Supplies
6.0
6.1
6.1.1
6.1.2
6.1.3
6.1.4
6.1.5
6.1.6
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,
but demonstration of equivalent performance meeting the requirements of
the 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.
Glassware
Syringes - 25 milliliters (mL), gas-tight with shut-off valve. Micro
syringes - 10 microliters (• L) and larger, 0.006 inch (0.15 mm) ID
needle.
Syringe Valve - two-way, with Luer ends (three each), if applicable
to the purging device.
Pasteur Pipets - disposable.
Vials and Caps - assorted sizes.
Volumetric Flasks, class A with ground-glass stoppers.
Bottles - 15 mL, screw-cap, with PTFE cap liner.
6.2 pH Paper - wide range
6.3 Balances
Balances must be analytical and capable of accurately weighing ±0.0001
g. The balance must be calibrated witH class S weights or known
reference weights once per'each 12-hour work shift. The balance must be
calibrated with class S weights at a minimum of once per month. The
balance must also be annually checked by a certified technician.
6 .4 Purge and Trap Device
The purge and trap device consists of three separate pieces of
equipment: the sample purge chamber, trap, and the desorber. Several
complete devices are now commercially available.
6.4.1 The sample purge chamber must be designed to accept 25 mL samples
with a water column at least 10 centimeters (cm) deep. The gaseous
head space between the water column and the trap must have a total
volume of less than 15 mL. The purge gas must pass through the water
column as finely divided bubbles, each with a diameter of less than 3
millimeters (mm) at the origin. The purge gas must be introduced no
more than 5 mm from the base of the water column.
6.4.2 The trap must be at least 25 cm long and have an inside diameter of
at least 0.105 inch (2.667 mm). The trap must be packed to contain
the following minimum lengths of absorbents: (starting from inlet)
0.5 cm silanized glass wool, 1 cm methyl silicone, 8 cm of 2,6-
D-9/VOA
OLC03.2
-------
Exhibit D Volatiles -- Section 6
Equipment and Supplies (Con't)
diphenylene oxide polymer (Tenax-GC, 60/80 mesh),8 cm of silica gel
(Davison Chemical, 35/60 mesh, grade 15 or equivalent), 7 cm of
coconut charcoal (prepare from Barnebey Cheney, CA-580-26, or
equivalent, by crushing through 26 mesh screen), and 0.5 cm silanized
glass wool. A description of the trap used for analysis shall be
provided in the SDG Narrative.
6.4.3 The desorber must be capable of rapidly heating the trap to 180°C.
The polymer section of the trap should not be heated higher than
180°C and the remaining sections should not exceed 220°C during
bakeout mode.
6.4.4 Trap Packing
6.4.4.1 2,6-Diphenylene oxide polymer, 60/80 mesh chromatographic grade
(Tenax GC or equivalent).
6.4.4.2 Methyl silicone packing, 3.0 percent OV-l on Chromosorb W, 60/80
mesh (or equivalent).
6.4.4.3 Silica gel, 35/60 mesh, Davison, grade 15 (or equivalent).
6.4.4.4 Coconut charcoal (prepare from Barnebey Cheney, CA-580-26, or
equivalent, by crushing through 26 mesh screen).
6.4.4.5 Alternate sorbent traps may be used if:
• The trap packing materials do not introduce contaminants which
interfere with identification and quantitation of the
compounds listed in Exhibit C (Volatiles);
• The analytical results generated using the trap meet the
initial and continuing calibration technical acceptance
criteria listed in the SOW and the Contract Required
Quantitation Limits (CRQLs) listed in Exhibit C (Volatiles);
or
• The trap can accept up to 1000 nanograms (ng) of each compound
listed in Exhibit C (Volatiles) without becoming overloaded.
6.4.4.5.1 The alternate trap must be designed to optimize performance.
Follow the manufacturer's instructions for the use of its
product. Before use of any trap other than the one specified
in Section 6.4.2, the Contractor must first meet the criteria
listed in Section 6.4.4.5. Once this has been demonstrated,
the Contractor must document its use in each SDG Narrative by
specifying the trap composition (packing material/brand name,
amount of packing material). Other sorbent traps include, but
are not limited to, Tenax/Silica Gel/Carbon Trap from EPA
Method 524.2, Tenax - GC/Graphpac-D Trap (Alltech) or .
equivalent, and Vocarb 4000 Trap (Supelco) or equivalent.
6.4.4.5.2 The Contractor must maintain documentation that the alternate
trap meets the criteria listed in Section 6.4.4.5. The minimum
documentation requirements are as follows:
OLC03.2 D-10/VOA
-------
Exhibit D Volatiles -- Section 6
Equipment and Supplies (Con't)
6.4.4.5.2.1 Manufacturer-provided information concerning the performance
characteristics of the trap.
6.4.4.5.2.2 Reconstructed ion chromatograms and data system reports
generated on the Contractor's GC/MS used for CLP analyses:
• From instrument blank analyses which demonstrate that
there are no contaminants which interfere with the
volatile analysis when using the alternate trap; and
• From initial and continuing calibration standards
analyzed using the trap specified in Section 6.4.4.
6.4.4.5.2.3 Based on Contractor-generated data described above, the
Contractor must complete a written comparison/review, which
has been signed by the Laboratory Manager, certifying that:
• The alternate trap performance meets the technical
acceptance criteria listed in Sections 9.3.5 and 9.4.5;
• The low point initial calibration standard analysis has
adequate sensitivity to meet the volatile CRQLs,-
• The high point initial calibration standard analysis was
not overloaded; and
• The alternate trap materials do not introduce
contaminants which interfere with the identification
and/or quantitation of the compounds listed in Exhibit C
(Volatiles).
6.4.4.5.2.4 The documentation must be made available to USEPA during on-
site laboratory evaluations or sent to USEPA upon request of
the USEPA CLP Project Officer (CLP PO) or the Organic
Program Manager at the Analytical Operations/Data Quality
Center (AOC).
6.4.5 The purge and trap apparatus may be assembled as a separate unit or
be an integral unit coupled with a Gas Chromatograph (GC).
6.5 Gas Chromatograph/Mass Spectrometer (GC/MS) System
6.5.1 Gas Chromatograph - The GC system must be capable of temperature
programming and have a flow controller that maintains a constant
column flow rate throughout desorption and temperature program
operations. The system must include or be interfaced to a purge and
trap system as specified in Section 6.4 and have all required
accessories including syringes, analytical columns, and gases. All
GC carrier gas lines must be constructed from stainless steel or
copper tubing. Non-polytetrafluoroethylene (PTFE) thread sealants,
or flow controllers with rubber components, are not to be used. The
column oven must be cooled to 10°C if adequate separation of gaseous
compounds is not achieved (Section 9.1.2.3); therefore, a subambient
oven controller is required.
D-ll/VOA OLC03.2
-------
Exhibit D Volatiles -- Section 6
Equipment and Supplies (Con't)
6.5.2 Gas Chromatography Columns
A description of the column used for analysis shall be provided in
the SDG Narrative.
6.5.2.1 Minimum length 30 m x 0.53 mm ID VOCOL (Supelco) or equivalent
fused silica widebore capillary column with 3 micrometers (vim)
film thickness.
6.5.2.2 Minimum length 30 m x 0.53 mm ID DB-624 (J & W Scientific) or
equivalent fused silica widebore capillary column with 3 urn film
thickness.
6.5.2.3 Minimum length 30 m x 0.53 mm ID AT-624 (Alltech) or equivalent
fused silica widebore capillary column with 3 urn film thickness.
6.5.2.4 Minimum length 30 m x 0.53 mm ID HP-624 (Hewlett-Packard) or
equivalent fused silica widebore capillary column with 3 um film
thickness.
6.5.2.5 Minimum length 30 m x 0.53 mm ID RTx-624 (Restek) or equivalent
fused silica widebore capillary column with 3 vim film thickness.
6.5.2.6 Minimum length 30 m x 0.53 mm ID BPX-624 (SGE) or equivalent fused
silica widebore capillary column with 3 um film thickness.
6.5.2.7 Minimum length 30 m x 0.53 mm ID CP-Sil 13CB (Chrompack) or
equivalent fused silica widebore capillary column with 3 vim film
thickness.
6.5.3 A capillary column is considered equivalent if:
• The column does not introduce contaminants which interfere with
the identification and quantitation of the compounds listed in
Exhibit C (Volatiles);
• The analytical results generated using the column meet the
initial and continuing calibration technical acceptance criteria
listed in the SOW, and the CRQLs listed in Exhibit C (Volatiles);
• The column can accept up to 1000 ng of each compound listed in
Exhibit C (Volatiles) without becoming overloaded; and
• The column provides equal or better resolution of the compounds
listed in Exhibit C (Volatiles) than the columns listed in
Section 6.5.2.
6.5.3.1 As applicable, follow the manufacturer's instructions for use of
its product.
6.5.3.2 The Contractor must maintain documentation that the column met the
criteria in Section 6.5.3. The minimum documentation is as
follows:
OLC03.2 D-12/VOA
-------
Exhibit D Volatiles -- Section 6
Equipment and Supplies (Con't)
6.5.3.2.1 Manufacturer provided information concerning the performance
characteristics of the column.
6.5.3.2.2 Reconstructed ion chromatograms and data system reports
generated on the GC/MS used for the CLP analyses:
• From instrument blanks which demonstrate that there are no
contaminants which interfere with the volatile analysis
when using the column; and
• From initial and continuing calibration standards analyzed
using the alternate column.
6.5.3.5 Based on the Contractor-generated data described above, the
Contractor shall complete a written comparison/review, signed by
the Laboratory Manager, certifying that:
• The alternate column performance meets the technical
acceptance criteria in Sections 9.3.5 and 9.4.5;
• The low point initial calibration standard analysis has
adequate sensitivity to meet the volatile CRQLs;
• The high point initial calibration standard analysis was not
overloaded; and
• The column does not introduce contaminants which interfere
with the identification and/or quantitation of compounds
listed in Exhibit C (Volatiles).
6.5.3.6 The documentation must be made available to USEPA during on-site
laboratory evaluations or sent to USEPA upon request of the CLP PO
or the Organic Program Manager at the AOC.
6.5.4 PACKED COLUMNS CANNOT BE USED.
6.5.5 Mass Spectrometer (MS) - The MS must be capable of scanning from 35
to 300 atomic mass unit (amu) every 2 seconds or less, utilizing 70
volts (nominal) electron energy in the electron impact ionization
mode and producing a mass spectrum which meets all the 4-Bromo-
fluorobenzene (BFB) GC/MS performance check technical acceptance
criteria in Table D-l when 50 ng of BFB are injected through the GC
inlet. .
NOTE: To ensure sufficient precision of mass spectral data, the MS
scan rate must allow acquisition of at least five spectra while a
sample compound elutes from the GC. The purge and trap GC/MS system
must be in a room whose atmosphere is demonstrated to be free of all
potential contaminants which will interfere with the analysis. The
instrument must be vented to outside the facility or to a trapping
system which prevents the release of contaminants into the instrument
room.
6.5.6 GC/MS Interface - Any GC/MS interface may be used that gives
acceptable calibration points at 25 ng or less per injection for each
D-13/VGA OLC03.2
-------
Exhibit D Volatiles -- Section 6
Equipment and Supplies (Con't)
of the purgeable target compounds and deuterated monitoring compounds
and achieves all acceptable performance criteria. GC/MS interfaces
constructed of all-glass or glass-lined materials are recommended.
Glass can be deactivated by silanizing with dichlorodimethylsilane.
6.5.7 Data System - A computer system must be interfaced to the MS that
allows the continuous acquisition and storage on machine-readable
media of all mass spectra obtained throughout the duration of the
chromatographic program. The computer must have software that allows
searching of any GC/MS data file for ions of a specified mass and
plotting such ion abundances versus time or scan number. This type
of plot is defined as an Extracted Ion Current Profile (EICP).
Software must also be available that allows integrating the abundance
in any EICP between specified time or scan number limits. Also, for
the non-target compounds, software must be available that allows
comparing sample spectra against reference library spectra. The
NIST/EPA/NIH (May 1992 release or later) and/or Wiley (1991 release
or later) or equivalent mass spectral library shall be used as the
reference library. The data system must be capable of flagging all
data files that have been edited manually by laboratory personnel.
6.5.8 Magnetic-Tape Storage Device - Capable of recording data and must be.
suitable for long-term, off-line storage.
OLC03.2 D-14/VOA
-------
Exhibit D Volatiles -- Section 7
Reagents and Standards
7.0
REAGENTS AND STANDARDS
7.1 Reagents
Reagents shall be dated with the receipt date and used on a first-in,
first-out basis. The purity of the reagents shall be verified before
use.
7.1.1 Reagent water - Reagent water is defined as water in which no
purgeable target compound is observed at or above the Contract
Required Quantitation Limit (CRQL) listed in Exhibit C for that
compound and in which no non-target compound is observed at or above
2.0 micrograms per liter (ug/L).
7.1.1.1 Reagent water may be generated by passing tap water through a
carbon filter bed containing about 453 g (1 Ib.) of activated
carbon (Calgon Corp., Filtrasorb-300, or equivalent).
7.1.1.2 Reagent water may be generated using a water purification system
(Millipore Super-Q or equivalent).
7.1.1.3 Reagent water may be prepared by boiling water for 15 minutes.
Subsequently, while maintaining the temperature at 90°C, bubble a
contaminant-free inert gas through the water for one hour. While
still hot, transfer the water to a narrow-mouth screw-cap bottle,
seal with a PTFE-lined septum, and cap.
7.1.2 Methanol - HPLC quality or equivalent -- Each lot of methanol used
for analysis under this contract must be purged with nitrogen and
must be demonstrated to be free of contaminants that interfere with
the measurement of purgeable compounds listed in Exhibit C.
7.2 Standards
7.2.1
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. 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.
Stock Standard Solutions
Stock standard solutions may be purchased or may be prepared in
methanol from pure standard materials.
7.2.1.1 Prepare stock standard solutions by placing about 9.8 milliliters
(mL) of methanol into a 10.0 tnL ground-glass stoppered volumetric
flask. Allow the flask to stand, unstoppered, for about 10
minutes or until all alcohol wetted surfaces have dried. Weigh
the flask to the nearest 0.1 mg.
7.2.1.2 Add the assayed reference material as described below.
7.2.1.2.1 If the compound is a liquid, use a 100 microliters (uL) syringe
to immediately add two or more drops of assayed reference
D-15/VOA
OLC03.2
-------
Exhibit D Volatiles -- Section 7
Reagents and Standard (Con't)
.material to the flask, then reweigh. The liquid must fall
directly into the alcohol without contacting the neck of the
flask.
7.2.1.2.2 If the compound is a gas at room temperature, fill a 5 mL
valved gas-tight syringe with the reference standard to the 5.0
mL mark. Lower the needle to S millimeters (mm) above the
methanol meniscus. Slowly introduce the reference standard
above the surface of the liquid. The gas will rapidly dissolve
in the methanol. This may also be accomplished by using a
lecture bottle equipped with a Hamilton Lecture Bottle Septum
(#86600) . Attach PTFE tubing to the side-arm relief valve and
direct a gentle stream of the reference standard into the
methanol meniscus.
7.2.1.3 Reweigh, dilute to volume, stopper, then mix by inverting the
flask several times. For non-gaseous compounds, calculate the
concentration in ug/uL from the net gain in weight. When compound
purity is assayed to be 97 percent or greater, the weight may be
used without correction to calculate the concentration of the
stock standard. If the compound purity is assayed to be less than
97 percent, the weight must be corrected when calculating the
concentration of the stock solution. For gaseous compounds,
calculate the concentration in ug/uL using the Ideal.Gas Law,
taking into account the temperature and pressure conditions within
the laboratory.
7.2.1.4 Prepare fresh stock standards every two months for gases or for
reactive compounds such as styrene. All other stock standards for
non-gases/non-reactive purgeable compounds must be replaced after
six months, or sooner if standard has degraded or evaporated.
7.2.2 Secondary Dilution Standards
7.2.2.1 Using stock standard solutions, prepare secondary dilution
standards in methanol that contain the compounds of interest,
either singly or mixed together. Secondary dilution standard
solutions should be prepared at concentrations that can be easily
diluted to prepare working standard solutions.
7.2.2.2 Prepare fresh secondary dilution standards for gases and for
reactive compounds, such as styrene, every month or sooner if-
standard has degraded or evaporated. Secondary dilution standards
for the other purgeable compounds must be replaced after six
months, or sooner if standard has degraded or evaporated.
7.2.3 Working Standards
7.2.3.1 Instrument Performance Check Solution (4-Bromofluorobenzene)
Prepare a 25 nanograms per microliter (ng/uL) solution of 4-Bromo-
fluorobenzene (BFB) in methanol. Prepare fresh BFB solution every
six months, or sooner if the solution has degraded or evaporated.
OLC03.2 D-16/VOA
-------
Exhibit D Volatiles -- Section 7
Reagents and Standard (Con't)
NOTE: The 25 ng/uL concentration is used with a 2 uL injection
volume. The laboratory may prepare a 50 ng/uL solution of BFB if
a 1 uL injection volume is used.
7.2.3.2 Calibration Standard Solution
Prepare the working calibration standard solution containing all
of the purgeable target compounds in methanol (Exhibit C). The
concentration of the non-ketone target compounds and the
associated Deuterated Monitoring Compounds (DMCs) must be 2.5
ug/mL in the standard (i.e., final concentration). The
concentration of the ketones (acetone, butanone, 2-hexanone,
4-methyl-2-pentanone) and their associated DMCs must be 12.5 ug/mL
in the standard (i.e., final concentration). Prepare fresh
working calibration standard solutions weekly, or sooner if
solutions have degraded or evaporated.
7.2.3.3 Internal Standard Spiking Solution
Prepare an internal standard spiking solution containing
l,4-dichlorobenzene-d4, chlorobenzene-d5, and 1,4-difluorobenzene
in methanol at the concentration of 12.5 ug/mL for each internal
standard. Add 10 uL of this spiking solution into 25.0 mL of
samples, blanks, requested Matrix Spike/Matrix Spike. Duplicate(s)
(MS/MSD), and calibration standards for a concentration of 5.0
ug/L. Prepare fresh spiking solution weekly, or sooner if the
solution has degraded or evaporated.
7.2.3.4 Deuterated Monitoring Compound (DMC) Spiking Solution
Prepare a DMC spiking solution in methanol containing the
compounds listed below at the following concentrations:
Concentration
Compound ug/mL
Vinyl Chloride-d3 12.5
Chloroethane-d5 12.5
l,l-Dichloroethene-d2 12.5
2-Butanone-d5 12.5
Chlorof orm-d 12 .5
l,2-Dichloroethane-d4 12.5
Benzene-d6 12.5
1,2-Dichloropropane-d6 12.5
Toluene-d8 12.5
trans-l,3-Dichloropropene-d4 12.5
2-Hexanone-d5 • 12.5
Bromoform-d 12.5
l,l,2,2-Tetrachloroethane-d2 12.5
l,2-Dichlorobenzene-d4 12.5
Add 10 uL of this spiking solution into 25 mL of sample, and blank
for a concentration of 5.0 ug/L. The DMC spiking solution is
added to the working calibration standards so it is not to be
added again when aqueous calibration standards are prepared.
D-17/VOA OLC03.2
-------
Exhibit D Volatiles -- Section 7
Reagents and Standard (Con't)
Prepare fresh spiking solution weekly, or sooner if the solution
has degraded or evaporated.
7.2.3.5 Matrix Spiking Solution
Prepare a spiking solution in methanol that contains the following
compounds at a-concentration of 12.5 ug/mL; 1,1-Dichloroethene,
Trichloroethene, Chlorobenzene, Toluene, and Benzene. Prepare
fresh spiking solution weekly, or sooner, if the solution has
degraded or evaporated.
7.2.3.6 Aqueous Calibration Standard Solutions -- Initial and Continuing
7.2.3.6.1 Prepare five aqueous initial calibration standard solutions
containing all of the purgeable target compounds and the DMCs
at the following levels: all non-ketone target compounds and
non-ketone DMCs at 0.50, 1.0, 5.0, 10, and 25 ug/L; all ketones
and their associated DMCs at 5.0, 10, 25, 50 and 125 ug/L. It
is required that all three xylene isomers (o-, p-, and m-
xylene) be present in the calibration standards at
concentrations of each isomer equal to that of the other target
compounds (i.e., 0.50, 1.0, 5.0, 10, and 25 ug/L). The
internal standards are added to each calibration standard
according to the procedure in Section 9.3.3.4.
7.2.3.6.2 Aqueous calibration standards may be prepared in a volumetric
flask or in the syringe used to inject the standard into the
purging device.
7.2.3.6.2.1 Volumetric .flask - Add an appropriate volume of working
calibration standard solution to an aliquot of reagent water
in a volumetric flask. Use a microsyringe and rapidly
inject the alcohol standard into the expanded area of the
filled volumetric flask. Remove the needle as quickly as
possible after injection. Bring to volume. Mix by
inverting the flask three times only. Discard the contents
contained in the head of the flask.
7.2.3.6.2.2 Syringe - Remove the plunger from a 25 mL syringe and close
the syringe valve. Pour reagent water into the syringe
barrel to just short of overflowing. Replace the syringe
plunger and compress the water. Invert the syringe, open
the syringe valve, and vent any residual air. Adjust the
water volume to 25.0 mL minus the amount of calibration
standard to be added. Withdraw the plunger slightly and add
an appropriate volume of working calibration standard
through the valve bore of the syringe. Close the valve and
invert three times.
7.2.3.6.3 The 5.0 ug/L (25 ug/L for ketones) aqueous calibration standard
solution is the continuing calibration standard.
7.2.3.6.4 The methanol contained in each of the aqueous calibration
standards must not exceed 1 percent by volume. •
OLC03.2 D-18/VOA
-------
Exhibit D Volatiles -- Section 7
Reagents and Standard (Con't)
7.2.4 Ampulated Standard Extracts
Standard solutions purchased from a chemical supply house as
ampulated extracts in glass vials may be retained and used until the
expiration date provided by the manufacturer. If no manufacturer's
expiration date is provided, the standard solutions as ampulated
extracts may be retained and used for 2 years from the preparation
date. Standard solutions prepared by the Contractor which are
immediately ampulated in glass vials may be retained for 2 years from
preparation date. Upon breaking the glass seal, the expiration times
listed in Sections 7.2.1 to 7.2.3 will apply. The Contractor is
responsible for assuring that the integrity of the standards has not
degraded (Section 7.2.5.5).
7.2.5 Storage of Standards
7.2.5.1 Store the stock standards in PTFE-sealed screw-cap bottles with
zero headspace at -10°C to -20°C, and protect the standards from
light. Once one of the bottles containing the stock standard
solution has been opened, it may be used for no longer than one
week.
7.2.5.2 Store secondary dilution standards in PTFE-sealed screw-cap
bottles with minimal headspace at -10°C to -20°C. Protect the
standards from light. The secondary dilution standards must be
checked frequently for signs of degradation or evaporation,
especially just prior to preparing the working calibration
standards from them.
7.2.5.3 Aqueous standards may be stored up to 24 hours if held.in PTFE-
sealed screw-cap vials with zero headspace at 4°C (±2°C), and
protect, the standards from light. If not so stored, they must be
discarded after one hour unless they are set up to be purged by an
autosampler. When using an autosampler, the standards may be kept
up to 12 hours in purge tubes connected via the autosampler to the
purge and trap device.
7.2.5.4 Purgeable standards must be stored separately from other
standards.
7.2.5.5 The Contractor is responsible for maintaining the integrity of
standard solutions and verifying prior to use. This means that
standards must be brought to room temperature prior to use,
checked for losses, and checked that all components have remained
in the solution.
7.2.6 Temperature Records for Storage of Standards
7.2.6.1 The temperature of all standard storage refrigerators/freezers
shall be recorded daily.
7.2.6.2 Temperature excursions shall be noted and appropriate corrective
actions shall be taken to correct problems, when required.
D-19/VOA OLC03.2
-------
Exhibit D Volatiles -- Sections 7 & 8
Sample Collection, Preservation, and Storage
7.2.6.3 Corrective action Standard Operating Rrocedures (SOPs) shall be
posted on the refrigerators.
8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE
8.1 Sample Collection and Preservation
8.1.1 Water samples may be collected in glass containers having a total
volume of at least 40 milliliters (mL) with a PTFE-lined septum and
an open top screw-cap. Headspace should be avoided. The specific
requirements for site sample collection are outlined by the Region.
8.1.2 The containers must be filled in such a manner that no air bubbles
pass through the sample as the container is being filled. Seal the
vial so that no air bubbles are entrapped in it.
8.1.3 Water samples are preserved to a pH of 2 at the time of collection.
8.1.4 All samples must be iced or refrigerated at 4°C (±2°C) from the time
of collection until analysis.
8.2 Procedure for Sample Storage
8.2.1 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
reconciled, complete sample data package to 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 and in a refrigerator used only for
storage of volatile samples received under this contract.
8.2.3 All volatile samples in an SDG must be stored together in the same
refrigerator.
8.2.4 Storage blanks shall be stored with samples until all samples within
an SDG are analyzed.
8.2.5 Samples, sample extracts, and standards must be stored separately.
8.2.6 Volatile standards must be stored separately from semivolatile and
pesticide/Aroclor standards.
8 .3 Temperature Records for Sample Storage
8.3.1 The temperature of all sample storage refrigerators shall be recorded
daily.
8.3.2 Temperature excursions shall be noted and appropriate corrective
actions shall be taken to correct problems, when required.
8.3.3 Corrective action Standard Operating Procedures (SOPs) shall be
posted on the refrigerators.
OLC03.2 D-20/VOA
-------
exhibit D Voiatiles -- Sections 8 & 9
Calibration and Standardization
8.4 Contract Required Holding Times
Analysis of water samples must be completed within 10 days of Validated
Time of Sample Receipt (VTSR). As part of USEPA's Quality Assurance
(QA) program, USEPA may provide Performance Evaluation (PE) Samples as
standard extracts which the Contractor is required to prepare per the
instructions provided by USEPA. PE samples must be prepared and
analyzed concurrently with the samples in the SDG. The contract-
required 10-day holding time does not apply to PE Samples received as
standard extracts.
9.0 CALIBRATION AND STANDARDIZATION
9.1 Instrument Operating Conditions
9.1.1 Purge and Trap
9.1.1.1 The following are the recommended purge and trap analytical
conditions. The conditions are recommended unless otherwise
noted:
Purge Conditions
Purge Gas:
Purge Time:
Purge Flow Rate:
Purge Temperature:
Helium or Nitrogen
11.0 ±0.1 minute
25-40 mL/minute
Ambient temperature (required)
Desorb Conditions
Desorb Temperature:
Desorb Flow Rate:
Desorb Time:
180°C
15 mL/minute
4.0 ±0.1 minute
Trap Reconditioning Conditions
Reconditioning Temperature:
Reconditioning Time:
180°C
7.0 ±0.1 minute (minimum). A
longer time may be required to
bake-contamination or water
from the system.
9.1.1.2 Before initial use, condition the trap overnight at 180°C by
backflushing with at least 20 milliliters (mL)/minute flow of
inert gas. Do not vent the trap effluent onto the analytical
column. Prior to daily use, condition the trap by heating at
180°C for 10 minutes while backflushing. The trap may be vented
to the analytical column during daily conditioning; however, the
column must be run through the temperature program prior to the
analysis of samples and blanks.
9.1.1.3 Optimize purge and trap conditions for sensitivity and to minimize
cross-contamination between samples. Once optimized, the same
D-21/VOA
OLC03.2
-------
Exhibit D Volatiles -- Section 9
Calibration and Standardization (Con't)
purge and trap conditions must be used for the analysis of all
standards, samples, and blanks.
9.1.1.4 A moisture reduction/water management system may be used to
improve the chromatographic performance by controlling moisture or
water if:
• The system does not introduce contaminants which.interfere
with identification and quantitation of compounds listed in
Exhibit C (Volatiles) ,
• The analytical results generated when using the moisture
reduction/water management system meet the initial and
continuing calibration technical acceptance criteria listed in
the Statement of Work (SOW) and the Contract Required
Quantitation Limits (CRQLs) listed.in Exhibit C (Volatiles);
• All calibration standards, samples, and blanks are analyzed
under the same conditions; and
• The Contractor performs acceptably on the Performance
Evaluation Samples using this system.
9.1.2 Gas Chromatograph (GC)
9.1.2.1 The following are the recommended GC analytical conditions. The
conditions are recommended unless otherwise noted:
Capillary Columns
Carrier Gas: Helium
Flow Rate: 15 mL/minute
Initial Temperature: 10°C
Initial Hold Time: 1.0 - 5.0 (±0.1) minutes
Ramp Rate: 6°C/minute
Final Temperature: 160°C
Final Hold Time: Until three minutes after all
compounds listed in Exhibit C
(Volatiles) elute (required)
9.1.2.2 Optimize GC conditions for analyte separation and sensitivity.
Once optimized, the same GC conditions must be used for the
analysis of all standards, samples,.and blanks.
9.1.2.3 If the gaseous compounds chloromethane, bromomethane, vinyl
chloride, and chloroethane fail to exhibit narrow, symmetrical
peak shape, are not separated from the solvent front, or are not .
resolved greater than 90.0 percent from each other, then a
subambient oven controller must be used, and the initial
temperature must be less than or equal to 10°C.
OLC03.2 D-22/VOA
-------
Exhibit D Volatiles -- Section 9
•Calibration and Standardization (Con't)
9.1.3 Mass Spectrometer (MS)
The following are the required MS analytical conditions:
Electron Energy: 70 volts (nominal)
Mass Range: 35-300 amu
lonization Mode: El
Scan Time: To give at least five scans per peak, not
to exceed 2 seconds per scan for capillary
column.
9.2 Instrument Performance Check -- 4-Bromofluorobenzene (BFB)
9.2.1 Summary of Instrument Performance Check
9.2.1.1 The GC/MS system must be tuned to meet the manufacturer's
specifications, using a suitable calibrant such as perfluoro-tri-
n-butylamine (FC-43) or perfluorokerosene (PFK). The mass
calibration and resolution of the GC/MS system are verified by the
analysis of the instrument performance check solution (Section
7.2.3.1) .
9.2.1.2 Prior to the analysis of any samples, blanks, or calibration
standards, the Contractor must establish that the GC/MS system
meets the mass spectral ion^ abundance criteria for the instrument
performance check solution containing BFB.
9.2.2 Frequency of Instrument Performance Check ,
The instrument performance check solution must be injected once at
the beginning of each 12-hour period, during which samples, blanks or
standards are to be analyzed. The 12-hour time period for GC/MS
performance check, calibration standards (initial or continuing
calibration), blank, and sample analysis begins at the moment of
injection of the BFB analysis that the laboratory submits as
documentation of a compliant instrument performance check. The time
period ends after 12 hours have elapsed according to the system
clock.
9.2.3 Procedure for Instrument Performance Check
The analysis of the instrument performance check solution may be
performed as follows:
• As an injection of up to 50 nanograms (ng) of BFB into the GC/MS
(Section 7.2.3.1); or
• By adding 50 ng of BFB to a calibration standard (Section
7.2.3.2) and analyzing the calibration standard.
D-23/VOA OLC03.2
-------
Exhibit D Volatiles -- Section 9
Calibration and Standardization (Con't)
9.2.4 Technical Acceptance Criteria for Instrument Performance Check
9.2.4.1 The mass spectrum of BFB must be acquired in the following manner.
Three scans (the peak apex scan and the scan immediately preceding
and the scan immediately following the apex) are acquired and
averaged. Background subtraction is required, and must be
accomplished using a single scan no more than 20 scans prior to
the beginning of the elution of BFB. Do not background subtract
part of the BFB peak.
NOTE: All subsequent standards, samples, and blanks associated
with a BFB analysis must use identical MS instrument conditions.
9.2.4.2 The analysis of the instrument performance check solution must
meet the ion abundance criteria given in Table D-l.
9.2.5 Corrective Action for Instrument Performance Check
9.2.5.1 If the BFB technical acceptance criteria are not met, retune the
GC/MS system. It may also be necessary to clean the ion source,
clean the quadrupole rods, or take other corrective actions to
achieve the technical acceptance criteria.
9.2.5.2 BFB technical acceptance criteria must be met before any
standards, samples, or required.blanks are analyzed. Any samples
or required blanks analyzed when tuning technical acceptance
criteria have not been met will require re-analysis at no
additional cost to USEPA.
9.3 Initial Calibration
9.3.1 Summary of Initial Calibration
Prior to the analysis of samples and required blanks and after the
instrument performance check technical acceptance criteria have been
met, each GC/MS system must be calibrated at a minimum of five '
concentrations to determine instrument sensitivity and the linearity
of GC/MS response for the purgeable target and Deuterated Monitoring
Compounds (DMCs).
9.3.2 Frequency of Initial Calibration
9.3.2.1 Each GC/MS system must be calibrated upon award of the contract,
whenever the Contractor takes corrective action which may change
or affect the initial calibration criteria (i.e., ion source
cleaning or repair, column replacement, etc.), or if the
continuing calibration technical acceptance criteria have not been
met.
9.3.2.2 If time remains in the 12-hour time period after meeting the
technical acceptance criteria for the initial calibration, samples
and blanks may be analyzed. It is .not necessary to analyze a
continuing calibration standard if the initial calibration
standard that is the same concentration as the continuing
' calibration'standard meets the continuing calibration technical
OLC03.2 D-24/VOA
-------
exhibit D Volatiles -- Section 9
Calibration and Standardization (Con't)
acceptance criteria. A method blank is required. Quantitate all
samples and blank results against the initial calibration standard
that is the same concentration as the continuing calibration
standard. Compare Quality Control (QC) criteria such as internal
standard area response change and retention time shift to the
initial calibration standard that is the same concentration as the
continuing calibration standard.
9.3.3 Procedure for Initial Calibration
9.3.3.1 Assemble a purge and trap device that meets the specifications in
Section 6.4. Condition the device as described in Section 9.1.1.
9.3.3.2 Connect the purge and trap device to the GC. The GC must be
operated using temperature and flow rate parameters equivalent to
those in Section 9.1.2.
9.3.3.3 All samples, blanks, and standard/spiking solutions must be
allowed to warm to ambient temperature (approximately 1 hour)
before analysis.
9.3.3.4 Add 10 microliters (pL) of the internal standard solution (Section
7.2.3.3) to each aqueous standard containing the DMCs for a
concentration of 5 micrograms per liter (ug/L) at time of purge.
Analyze each calibration standard according to Section 10.2.
9.3.4 Calculations for Initial Calibration
Calculating the Relative Response Factor (RRF) of the xylenes
requires special attention. On capillary columns, the — and p-xylene
isomers coelute. Therefore, when calculating the relative response
factor in the equation below, use the area response (Ax) and . >
concentration (Cx) of the peak from o-xylene.
9.3.4.1 Calculate RRF for each purgeable target compound and DMC using
Equation 1. See Table D-3 to associate purgeable target compounds
and DMCs with the proper internal standard. See Table D-4 for
primary quantitation ions to be used for each purgeable target
compound, DMC, and internal standard compound.
NOTE: Unless otherwise stated the area response is that of the
primary quantitation ion.
D-25/VOA OLC03.2
-------
Exhibit D Volatiles -- Section 9
Calibration and Standardization (Con't)
EQ. 1
MT- _^L« fii
Where:
AX = Area of the characteristic ion (EICP) for the compound to
be measured (Table D-4).
Ais = Area of the characteristic ion (EICP) for the specific
internal standard (Tables D-3 and D-4).
Cis = Concentration of the internal standard.
Cx = Concentration of the compound to be measured.
• • •
9.3.4.2 The mean Relative Response Factor (RRF) must be calculated for all
compounds.
9.3.4.3 Calculate the Percent Relative Standard Deviation (%RSD) of RRF
values for each purgeable target and DMC over the initial
calibration range using Equation 2 in conjunction with Equation 3.
EQ. 2
SD__
J?* » 100
x
Where:
SDRRF = Standard deviation of initial calibration relative
response factors (per compound). From EQ. 3.
• = Mean value of the initial calibration relative response
factors (per compound).
9.3.4.4 Equation 3 is the general formula for Standard Deviation (SD) for
a statistically small set of values.
EQ. 3
n - 1
Where:
Xi = Each individual value used to calculate the mean.
• = The mean of n values.
n = Total number of values.
OLC03.2 D-26/VOA
-------
Exhibit D Volatiles -- Section 9
Calibration and Standardization (Con't)
9.3.4.5 Equation 4 is the general formula for the mean of a set of values.
EQ. 4
*^
X.
Where:
xi = Value.
• = Mean value.
n = Number of values.
9..3.5 Technical Acceptance Criteria For Initial Calibration
9.3.5.1 All initial calibration standards must be analyzed at the
concentration levels described in Section 7.2.3.6.1, and at the
frequency described in Section 9.3.2 on a GC/MS system meeting the
BFB technical acceptance criteria (Section 9.2.4).
9.3.5.2 Excluding those ions in the solvent front, no quantitation ion may
saturate the detector. Consult the instrument manufacturer's
instrument operating manual to determine how saturation is
indicated for your instrument.
9.3.5.3 The RRF at each calibration concentration for each purgeable
target and DMC that has a required minimum relative response
factor value must be greater than or equal to the compound's
minimum acceptable relative response factor listed in Table D-2.
9.3.5.4- The %RSD for each target or DMC listed in Table D-2 must be less
than or equal to that value listed.
9.3.5.5 Up to two compounds may fail the criteria listed in Sections
9.3.5.3 and 9.3.5.4 and still meet the minimum RRF and %RSD
requirements. However, these compounds must have a minimum RRF
greater than or equal to 0.010, and the %RSD must be less than or
equal to 40.0 percent.
9.3.6 Corrective Action for Initial Calibration
9.3.6.1 If the initial calibration technical acceptance, criteria are not
met, inspect the system for problems. It may be necessary to
clean the ion source, change the column, service the purge and
trap device, or take other corrective actions to achieve the
technical acceptance criteria.
9.3.6.2 Initial calibration technical acceptance criteria MUST be met
before any samples or required blanks are analyzed. Any samples
D-27/VOA . OLC03.2
-------
Exhiibit D Volatiles -- Section 9
Calibration and Standardization (Con't)
or required blanks analyzed when initial calibration technical
acceptance criteria have not been met will require re-analysis at
no additional cost to USEPA..
9.4 Continuing Calibration
9.4.1 Summary of Continuing Calibration
Prior to the analysis of samples and required blanks and after BFB
and initial calibration technical acceptance criteria have been met,
each GC/MS system must be routinely checked by analyzing a continuing
calibration standard containing all the purgeable target and DMCs and
internal standards to ensure that the instrument continues to meet
the instrument sensitivity and linearity requirements of the SOW.
9.4.2 Frequency of Continuing Calibration
9.4.2.1 A check of the calibration curve must be performed once per every
12-hour time period of operation. The 12-hour time period begins
with the injection of BFB.
9.4.2.2 If time remains in the 12-hour time period after meeting the
technical acceptance criteria for the initial calibration, samples
and blanks may be analyzed. It is not necessary to analyze a
continuing calibration standard, if the initial calibration
standard that is the same concentration as the continuing
calibration standard meets the continuing calibration technical
acceptance criteria. A method blank is required. Quantitate all
sample and blank results against the initial calibration standard
that is the same concentration as the continuing calibration
standard (5.0 ug/L for non-ketones, 25 ug/L for ketones).
If time does not remain in the 12-hour period beginning with the
injection of the instrument performance check solution, a new
injection of the instrument performance check solution must be
made. If the new injection meets the ion abundance criteria for
BFB, then a continuing calibration standard may be injected.
9.4.3 Procedure for Continuing Calibration
9.4.3.1 Set up the purge and trap GC/MS system per the requirements in
Section 9.1.
9.4.3.2. All samples, required blanks, and standard/spiking solutions must
be allowed to warm to ambient temperature (approximately 1 hour)
before analysis.
9.4.3.3 Add 10 uL of internal standard spiking solution (prepared as
described in Section 7.2.3:3 to the 25 mL syringe or volumetric
flask containing the continuing calibration standard in Section
7.2.3.6.3). Analyze the continuing calibration standard,
according to Section 10.2.
OLC03.2 D-28/VOA
-------
Exhibit D Voiatiles -- Section 9
Calibration and Standardization (Con't)
9.4.4 Calculations for Continuing Calibration
9.4.4.1 Calculate a RRF for each target and DMC according to Section
' 9:3~. 4.1.' - ' ~ - ~
9.4.4.2 Calculate the percent difference between the continuing
calibration RRF and the most recent initial calibration mean RRF
for each purgeable target and DMC using Equation 5.
EQ. 5
RRT - 1ESP7
IDilteeeaee • ' * - 100
Where:
RRFC = Relative response factor from current continuing
calibration standard.
Mean relative response factor from the most recent
• 1?RFi = initial calibration.
9.4.5 Technical Acceptance Criteria for Continuing Calibration
9.4.5.1 The concentration of the volatile organic target and deuterated
monitoring compounds in the continuing calibration standard must
be 5.0 ug/L for non-ketones and 25 ug/L for ketones. The
continuing calibration standard must be analyzed at the frequency
described in Section 9.4.2 on a GC/MS system meeting the BFB
(Section 9.2.4) and the initial calibration (Section 9.3.5)
technical acceptance criteria.
9.4.5.2 The RRF for each purgeable target and DMC that has a required
minimum RRF value must be greater than or equal to the compound's
minimum acceptable RRF listed in Table D-2.
9.4.5.3 The RRF percent difference for each purgeable target and DMC
listed in Table D-2 must be less than or equal to that value
listed.
9.4.5.4 Up to two compounds may fail the requirements listed in Sections
9.4.5.2 and 9.4.5.3 and still meet the minimum RRF criteria and
percent difference criteria. However, these compounds must have a
minimum RRF greater than or equal to 0.010 and the percent
difference must be within the inclusive range of ±40.0 percent.
9.4.5.5 Excluding those ions in the solvent front, no quantitation ion may
saturate the detector. Consult the manufacturer's instrument
operating manual to determine how saturation is indicated for your
instrument.
D-29/VOA OLC03.2
-------
Exhibit D Volatiles -- Section 9
Calibration and Standardization (Con't)
9.4.6 Corrective Action for Continuing Calibration
9.4.6.1 If the continuing calibration technical acceptance criteria are
not met, recalibrate the GC/MS instrument according to Section
9.3. It may be necessary to clean the ion source, change the
column, or take other corrective actions to achieve the continuing
calibration technical acceptance criteria.
9.4.6.2 Continuing calibration technical acceptance criteria MUST be met
before any samples or required blanks are analyzed. Any samples
or required blanks analyzed when continuing calibration technical
acceptance criteria have not been met will require re-analysis at
no additional cost to USEPA.
OLC03.2 D-30/VOA
-------
Exhibit D Volatiies -- Section 10
Sample Analysis
10.0 SAMPLE ANALYSIS
10.1 Summary of Sample Analysis
10.1.1 This method is designed for analysis of samples that contain low
concentrations of the target compounds listed in Exhibit C. It is
expected that the samples will come from drinking water and
well/ground water type sources around Superfund sites. If, upon
inspection of a sample, the Contractor suspects that the sample is
not amenable to this method, contact Sample Management Office (SMO).
SMO will contact the Region for instructions.
10.1.2 Prior to the analysis of samples, establish the appropriate purge and
trap Gas Chromatograph/Mass Spectrometer (GC/MS) operating
conditions, as outlined in Section 9.1, analyze the instrument
performance check solution (Section 9.2), and calibrate the GC/MS
system according to Sections 9.3 through 9.4.6. Also prior to sample
analysis, a method blank must be analyzed that meets blank technical
acceptance criteria in Section 12.1.5. All samples, required blanks,
and standard/spiking solutions must be allowed to warm to ambient
temperature (approximately 1 hour) before analysis. All samples,
required blanks, and calibration standards must be analyzed under the
same instrument conditions.
10.1.3 If insufficient sample volume (less than 90 percent of the required
amount) is received to perfprm the analyses, the Contractor shall
contact SMO to apprise 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 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.
10.2 Procedure for Sample Analysis
10.2.1 Remove the plunger from a 25 milliliters (mL) syringe that has a
closed syringe valve attached. Open the sample or standard container
which has been allowed to come to ambient temperature, and carefully
pour the sample into the syringe barrel to just short of overflowing.
Replace the syringe plunger and compress the sample. Invert the
syringe, open the syringe valve, and vent any residual air while
adjusting the sample volume to 25.0 mL. This process of taking an
aliquot destroys the validity of the sample for future analysis,
unless the excess sample is immediately transferred to a smaller vial
with zero headspace and stored at 4°C (±2°C).
10.2.2 Once the sample aliquots have been taken from the VOA vial, the pH of
the water sample must be determined. The purpose of the pH
determination is to ensure that all VOA samples were acidified in the
field. Test the pH by placing one or two drops of sample on the pH
paper (do not add pH paper to the vial). Record the pH of each
sample and report these data in the SDG Narrative, following the
instructions in Exhibit B. No pH adjustment is to be performed by
the Contractor.
D-31/VOA
OLC03.2
-------
Exhibit D Volatiles -- Section 10
Sample Analysis (Con't)
Add 10.0 microliters (uL) of the internal standard spiking solution
and 10.0 uL of the Deuterated Monitoring Compound (DMC) standard
solution through the valve bore of the syringe, then close the valve.
Invert the syringe three times.
10.2.3 Attach the valve assembly on the syringe to the valve on the sample
purger. Open the valves and inject the sample into the purging
chamber.
10.2.4 Close both valves and purge the sample for 11.0 (±0.1) minutes at
ambient temperature.
10.2.5 Sample Desorption - After the 11-minute purge, attach the trap to
the GC, adjust the purge and trap system to the desorb mode, initiate
the temperature program sequence of the GC and start data
acquisition. Introduce the trapped material to the GC column by
rapidly heating the trap to 180°C while backflushing the trap with
inert gas at 15 mL/min for 4.0 ±0.1 min. While the trapped material
is being introduced into the GC, empty the sample purger and rinse it
with reagent water. For samples containing large amounts of water-
soluble materials, suspended solids, high boiling compounds, or high
purgeable levels, it may be necessary tp wash out the sample purger
with a detergent solution, rinse it with reagent water, and then dry
it in an oven at 105°C.
10.2.6 Trap Reconditioning - After desorbing the sample, recondition the
trap for a minimum of 7.0 ±0.1 min at 180°C by returning the purge
and trap system to purge mode.
10.2.7 Gas Chromatograohv - Hold the column temperature at 10°C for 1.0 to
5.0 min, then program at 6°C/min to 160°C and hold until three
minutes after all target volatile compounds have eluted.
NOTE: Once an initial hold time has been chosen and the GC operating
conditions optimized, the same GC condition must be used for the
analysis.
10.2.8 Termination of Data Acquisition - Three minutes after all the
purgeable target compounds have eluted from the GC, terminate the MS
data acquisition and store data files on the data system storage
device. Use appropriate data output software to display full range
mass spectra and appropriate Extracted Ion Current Profiles (EICPs).
10.2.9 Dilutions
10.2.9.1 An original undiluted analysis must be made and results reported
for all samples. If the on-column concentration of any target
compound in any sample exceeds the initial calibration range, a
new aliquot of that sample must be diluted and purged. Guidance
for performing dilutions and exceptions to this requirement are
given in Sections 10.2.9.2 through 10.2.9.8.
NOTE 1: If the laboratory has evidence or highly suspects, because
of sample color or other physical property, that a sample may
contain high concentrations of either target or non-target
OLC03.2 D-32/VOA
-------
Exhibit D Volatiles -- Section 10
Sample Analysis (Con't)
compounds, then SMO shall be contacted immediately. SMO will seek
regional recommendations for diluted analysis.
NOTE 2: Secondary ion quantitation is only allowed when there are
sample interferences with the primary quantitation ion, not when
saturation occurs. If secondary ion quantitation is used,
calculate a Relative Response Factor (RRF) using the area response
(EICP) from the most intense secondary ion which is free of sample
interferences, and document the reasons in the SDG Narrative.
10.2.9.2 Use the results of the original analysis to determine the
approximate dilution factor required to get the largest analyte
peak within the initial calibration range.
10.2.9.3 The dilution factor chosen should keep the concentration of the
volatile target compounds that required dilution in the upper half
of the initial calibration range.
10.2.9.4 All dilutions must be made just prior to GC/MS analysis of the
sample. Until the diluted sample is in a gas-tight syringe, all
steps in the dilution procedure must be performed without delay.
10.2.9.5 Samples may be diluted in a volumetric flask or in a 25 mL
"Luerlock" syringe.
..10.2.9.6 To dilute the sample in a volumetric flask, use the following
procedure:
•r i .
10.2.9.6.1 Select the volumetric flask that will allow for necessary
'-"• dilution (25 mL to 100 mL) .
:l'0.2.9.6.2 Calculate the approximate volume of reagent water which will be
added to the volumetric flask selected and add slightly less
than this quantity of reagent water to the flask.
10.2.9.6.3 Inject the proper sample aliquot from a syringe into the
volumetric flask. Only aliquots of 1 mL increments are
permitted. Dilute the aliquot to the mark with reagent water.
Cap the flask and invert it three times.
10.2.9.6.4 Fill a 25 mL syringe with the diluted sample and analyze
according to Section 10.2.
10.2.9.7 To dilute the sample in a 25 mL syringe, use the following
procedure:
10.2.9.7.1 Calculate the volume of the reagent water necessary for the
dilution. The final volume of the diluted sample should be 25
mL.
10.2.9.7.2 Close the syringe valve, remove the plunger from the syringe
barrel, and pour reagent water into the syringe barrel to just
short of overflowing.
D-33/VOA OLC03.2
-------
Exhibit D Volatiles -- Section 10
Sample Analysis (Con't)
'10.2.9.7.3 Replace the syringe plunger and compress the water.
10.2.9.7.4 Invert the syringe, open the syringe valve, and vent any
residual air. Adjust the water volume to the desired amount.
10.2.9.7.5 Adjust the plunger to the 25 tnL mark to accommodate the sample
aliquot. Inject the proper aliquot of sample from another
syringe through the valve bore of the 25 mL syringe. Close the
valve and invert three times. Analyze according to Section
10.2.
10.2.9.8 For total xylenes where three isomers are quantified as two peaks,
the calibration of each peak should be considered separately,
e.g., a diluted analysis is not required for total xylenes unless
the concentration of the peak representing the single isomer
exceeds 25 micrograms per liter (ug/L) on-column, or the peak
representing the two co-eluting isomers exceeds 50 ug/L on-column.
OLC03.2 D-34/VOA
-------
Exhibit D Volatiles -- Section 11
Data Analysis and Calculations
11.0 DATA ANALYSIS AND CALCULATIONS
11.1 Qualitative Identification of Target Compounds
11.1.1 The compounds listed in the Target Compound List (TCL), Exhibit C
(Volatiles), shall be identified by an analyst competent in the
interpretation of mass spectra by comparison of the sample mass
spectrum to the mass spectrum.of a standard of the suspected
compound. Two criteria must be satisfied to verify the
identifications:
• Elution of the sample component at the same Gas Chromatograph
(GO Relative Retention Time (RRT) as the standard component; and
• Correspondence of the sample component and calibration standard
component mass spectra.
•11.1.2 For establishing correspondence of the GC RRT, the sample component
RRT must be within ±0.06 RRT units of the RRT of the standard
component. For reference, the standard must be run in the same 12-
hour time period as the sample. If samples are analyzed during the
12-hour time period as the initial calibration, use the RRT values
from the 5 micrograms per liter (ug/L) standard. If co-elution of
interfering compounds prohibits accurate assignment of the sample
component RRT from the total ion chromatogram, then the RRT should be
assigned using the Extracted Ion Current Profile (EICP) for ions
unique to the component of interest.
11.1.3 For comparison of standard and sample component mass spectra, mass
\ spectra obtained on the Contractor's GC/MS are required. Once
obtained, these standard spectra may be used for identification
purposes, only if the Contractor's GC/MS meets the daily instrument
performance requirements for 4-Bromofluorobenzene (BFB). These
standard spectra may be obtained from the standard analysis that was
also used to obtain the RRTs.
11.1.4 The guidelines for qualitative verification by comparison of mass
spectra are as follows:
11,. 1.4.1 All ions present in the standard mass spectra at a relative
intensity greater than 10 percent (most abundant ion in the
spectrum equals 100 percent) must be present in the sample
spectrum.
11.1.4.2 The relative intensities of ions specified in Section 11.1.4.1
must agree within ±20 percent between the standard and sample
spectra. (Example: For an ion with an abundance of 50 percent in
the standard spectra, the corresponding sample abundance must be
between 30 and 70 percent.)
11.1.4.3 Ions greater than 10 percent in the sample spectrum but not
present in the standard spectrum must be considered and accounted
for by the analyst making the comparison. The verification
process should favor false positives. All compounds meeting the
identification criteria must be reported with their spectra. For
D-35/VOA
OLC03.2
-------
Exhibit D Volatiles -- Section 11
Data Analysis and Calculations (Con't)
all compounds below the Contract Required Quantitation Limit
(CRQL), report the actual value followed by a "J" (e.g., "0.3J").
11.1.4.4 If a compound cannot be verified by all of the spectral
identification criteria listed in Section 11.1.4, but in the
technical judgment of the mass spectral interpretation specialist,
the identification is correct, then the Contractor shall report
that identification and proceed with quantitation.
11.2 Qualitative Identification of Non-Target Compounds
11.2.1 A library search shall be executed for non-target sample components
for the purpose of tentative identification. The NIST/EPA/NIH (May
1992 release or later) and/or Wiley (1991 release or later) or
equivalent mass spectral library, shall be used as the reference
library.
11.2.2 Up to 30 organic compounds of greatest apparent concentration not
listed in Exhibit C for the volatile or semivolatile organic
fraction, excluding the Deuterated Monitoring Compounds (DMCs) and
internal standard compounds, shall be tentatively identified via a
forward search of the NIST/EPA/NIH (May 1992 release or later) and/or
Wiley (1991 release or later), or equivalent mass spectral library.
The following are not to be reported:
• Compounds with a response of less than 10 percent of the internal
standard (as determined by inspection of the peak areas or
heights);
• Compounds which elute earlier than 30 seconds before the first
purgeable compound listed in Exhibit C (Volatiles) or three
minutes after the last purgeable compound listed in Exhibit C
(Volatiles) are not required to be searched in this fashion;
• Carbon dioxide; and
• Semivolatile TCL compounds listed in Exhibit C.
Only after visual comparison of sample spectra with the nearest
library searches will the mass spectral interpretation specialist
assign a tentative identification.
NOTE: Computer-generated library search routines must not use
normalizations which would misrepresent the library or unknown
spectra when compared to each other.
11.2.3 Up to 20 peaks of greatest apparent concentration (as determined by
inspection of peak areas or heights) that are suspected to be
straight-chain, branched, or cyclic alkanes, alone or part of an
alkane series, shall be library searched. Documentation for the
tentative identification must be supplied. Alkanes are not counted
as part of the 30 organic compounds described in Section 11.2.2.
OLC03.2 D-36/VOA
-------
Exhibit D Volatiles -- Section 11
Data Analysis and Calculations (Con't)
11.2.4 Guidelines for making tentative identification:
11.2.4.1 All major ions present in the reference mass spectrum at a
relative intensity greater than 10 percent' "(most 'abundant'ion in
the spectrum equals 100 percent) must be present in the sample
spectrum.
11.2.4.2 The relative intensities of the major ions specified in Section
11.2.4.1 must agree within ±20 percent between the reference and
sample spectra. (Example: For an ion with an abundance of 50
percent in the reference spectrum, the corresponding sample ion
abundance must be between 30 and 70 percent.).
11.2.4.3 Molecular ions present in the reference spectrum should be present
in the sample spectrum.
11.2.4.4 Ions present in the sample spectrum but not in the reference
spectrum should be reviewed for possible background contamination
or presence of coeluting compounds.
11.2.4.5 Ions present in the reference spectrum but not in the sample
spectrum should be reviewed for possible subtraction from the
',;•-• sample spectrum because of background contamination or coeluting
compounds. Data system library reduction programs can sometimes
create these discrepancies.
11.2.4.6 Non-target compounds receiving a library search match of 85
percent or higher should be considered a "probable match". The
compound should be reported unless the mass spectral
interpretation specialist feels there is just evidence not to
report the compound as identified by the library search program.
~i~ The lab should include in the Sample Delivery Group (SDG)
Narrative the justification for not reporting a compound as listed
by the search program.
11.2.4.7 If the library search produces more than one compound at or above
85 percent, report the compound with the highest percent match
(report first compound if percent match is the same for two or
more compounds), unless the mass spectral interpretation
specialist feels that the highest match compound should not be
reported, or another compound with a lower match should be
reported. The lab should include in the SDG Narrative the
justification for not reporting the compound with the highest
spectral match.
11.2.4.8 If the library search produces a series of obvious isomer
compounds with library search matches greater than 85 percent
(e.g., tetramethyl naphthalenes), the compound with the highest
library search percent match should be reported (or first compound
if library search matches are the same). A note should be placed
in the SDG Narrative indicating the exact isomer configuration, as
reported, may not be accurate.
11.2.4.9 If the library search produces no matches at or above 85 percent
and in the technical judgement of the mass spectral interpretation
D-37/VOA OLC03.2
-------
Exhibit D Volatiles -- Section 11
Data Analysis and Calculations (Con't)
specialist, no valid tentative identification can be made, the
compound should be reported as unknown. The mass spectral
specialist should give additional classification of the unknown
compound, if possible (e.g., unknown aromatic, unknown
hydrocarbon, unknown acid type, unknown chlorinated compound). If
probable molecular weights can be distinguished, include them.
11.2.4.10 Straight-chain, branched, or cyclic alkanes are not to be reported
as tentatively identified compounds on Form I LCV-TIC. When the
above alkanes are tentatively identified, the concentration(s) are
to be estimated as described in Section 11.3.2 and reported in the
SPG Narrative as alkanes. bv class (i.e., straight-chain,
branched, or cyclic, as a series, as applicable).
11.3 Calculations
11.3.1 Target Compounds
11.3.1.1 Target compounds identified shall be quantified by the internal
standard method using Equation 6. The internal standard used
shall be that which is assigned in Table D-3. The Relative
Response Factor (RRF) from the continuing calibration standard is
used to calculate the concentration in the sample. When a target
compound concentration is below its CRQL but the spectra meets the
identification criteria, report the concentration with a "J". For
example, if the CRQL is 0.50 ug/L and a concentration of 0.30 ug/L
is calculated, report as "0.30 J". Report ALL sample
concentration data as UNCORRECTED for blanks.
EQ. 6 .
in ug/L -
Where:
AX = Area of the characteristic ion (EICP) for the compound
to be measured. The primary quantitation ions for the
target compounds, internal standards, and the DMCs are
listed in Table D-4.
Ais = Area of the characteristic ion (EICP) for the internal
standard. The target compounds are listed witli their
associated internal standards in Table D-3.
Is = Amount of internal standard added in nanograms (ng).
RRF = The relative response factor from the continuing
calibration standard.
V0 = Total volume of water purged, in milliliters (mL).
OLC03.2 D-38/VOA
-------
Exhibit D Volatiles -- Section 11
Data Analysis and Calculations (Con't)
Df = Dilution factor. The dilution factor for analysis of
water samples for volatiles by this method is defined
as the ratio of the number of milliliters (mL) of water
purged (i.e., V0 above) to the number of mL of the
original water sample used for purging. For example,
if 5.0 mL of sample is diluted to 25.0 mL with reagent
water and purged, Df=25.0 mL/5 mL = 5.0. If no
dilution is performed, Df =1.0.
11.3.1.2 Xylenes (o-, m-, and p- isomers) are to be reported as xylenes
(total). Because - and p-xylene isomers coelute on capillary
columns, special attention must be given to the quantitation of
the xylenes. The RRF determined in Section 9.4.4.1, is based on
the peak that represents the single isomer on the GC column (o-
xylene on capillary columns). In quantitating sample
concentrations, use the areas on both peaks and the RRF. The
areas of the two peaks may be summed and the concentration
determined, or the concentration represented by each of the two
peaks may be determined separately and then summed.
11.3.1.3 The stereoisomers, trans-l,2-dichloroethene, and cis-
^; 1,2-dichloroethene, are to be reported separately.
11.3.1.4 The requirements listed in Sections 11.3.1.5 and 11.3.1.6 apply to
all standards, samples, and blanks.
11.3.1.5 It is expected that situations will arise where the automated
quantitation procedures in the GC/MS software provide
inappropriate quantitation. This normally occurs when there is
compound co-elution, baseline noise, or matrix interferences. In
these circumstances the Contractor must perform a manual
quantitation. Manual quantitations are performed by integrating
the area of the quantitation ion of the compound. This
integration shall only include the area attributable to the
specific TCL, deuterated monitoring, or internal standard
compound. The area integrated shall not include baseline
background noise. The area integrated shall not extend past the
point where the sides of the peak intersect with the baseline
noise. Manual integration is not to be used solely to meet QC
criteria, nor is it to be used as a substitute for corrective
action on the chromatographic system. Any instances of manual
integration must be documented in the SDG Narrative.
11.3.1.6 In all instances where the data system report has been edited, or
where manual integration or quantitation has been performed, the
GC/MS operator must identify such edits or manual procedures by
initialing and dating the changes made to the report, and shall
include the integration scan range. In addition, a hardcopy
printout of the EICP of the quantitation ion displaying the manual
integration shall be included in the raw data. This applies to
all compounds listed in Exhibit C (Volatiles), internal standard,
and DMCs.
D-39/VOA OLC03.2
-------
Exhibit D Volatiles -- Section 11
Data Analysis and Calculations (Con't)
11.3.2 Non-Target Compounds
11.3.2.1 An estimated concentration for non-target compounds tentatively
identified shall be determined by the internal standard method.
For quantitation, the nearest internal standard free of
interferences shall be used.
11.3.2.2 Equation 6 is also used for calculating non-target compound
concentrations. Total area counts (or peak heights) from the
total Reconstructed Ion Chromatograms (RICs) are to be used for
both the non-target compound to be measured (AX) and the internal
standard (Ais) . A RRF of 1.0 is to be assumed. The value from
this quantitation shall be qualified by a "J" (estimate due to
lack of a compound-specific relative response factor), and "N"
(presumptive evidence of presence), indicating the qualitative and
quantitative uncertainties associated with this non-target
compound. 'An estimated concentration must be calculated for all
tentatively identified compounds as well as those identified as
unknowns.
11.3.3 CRQL Calculation
. Calculate the adjusted CRQL for volatiles by using Equation 7.
EQ. 7
Adjusted Comtrnct. ve
CRQL CKQU, ~
Where:
Contract CRQL = Exact CRQL values in Exhibit C of the SOW.
V0 = Total volume of water purged in milliliters.
• NOTE: Must not exceed the contract sample volume.
Vc = Contract sample volume in milliliters (25 mL).
Df = Same as EQ. 6.
NOTE: If the adjusted CRQL is less than the CRQL listed in Exhibit C
(Volatiles), report the CRQL listed in Exhibit C (Volatiles).
11.3.4 Deuterated Monitoring Compound Recoveries
11.3.4.1 Calculate the concentration of each DMC using the same equation as
used for target compounds (Equation 6).
11.3.4.2 Calculate the recovery of each DMC in all samples and blanks using
Equation 8. Report the recoveries on appropriate forms.
OLC03.2 D-40/VOA
-------
Exhibit D Volatiles -- Section 11
Data Analysis and Calculations (Con't)
EQ. 8
Percent Recover? - —- * 100
Where:
/•
Qd = Concentration or amount determined by analysis.
Qa = Concentration or amount added to sample/blank.
11.3.5 Internal Standard Responses and Retention Times
Internal standard responses and retention times in all samples and
blanks must be evaluated during or immediately after data
acquisition. Compare the sample/blank internal standard responses
and retention times to the continuing calibration internal standard
responses and retention times. For samples and blanks analyzed
during the same 12-hour time period as the initial calibration
standards, compare the internal standard responses and retention
times against the 5 ug/L calibration standard. The EICP of the
internal standards must be monitored arid evaluated for each sample
, and blank.
11.4 Technical Acceptance Criteria for Sample Analysis
11.4.1 The sample must be analyzed on a GC/MS system meeting the BFB,
initial calibration, continuing calibration, and blank technical
acceptance criteria.
11.4.2 The sample and any required dilution must be analyzed within the
contract holding time.
11.4.3 The sample must have an associated method blank meeting the blank
technical acceptance criteria.
11.4.4 The percent recovery of each of the DMCs in the sample must be within
the acceptance windows in Table D-5. Up to three DMCs per sample may
fail to meet the recovery limits listed in Table D-5.
11.4.5 The EICP area for each of the internal standards in the sample must
be within the inclusive range of ±40.0 percent of its response in the
most recent continuing calibration standard analysis.
11.4.6 The retention time shift for each of the internal standards in the
sample must be within ±0.33 minutes (20.0 seconds) of its retention
time in the most recent continuing calibration standard analysis.
11.4.7 The RRT of each of the DMCs in the sample must be within ±0.06 RRT
units of its relative retention time in the most recent continuing •
calibration standard analysis.
D-41/VOA OLC03.2
-------
Exhibit D Volatiles'-- Section 11
Data Analysis and Calculations (Con't)
11.4.8 Excluding those ions in the solvent front, no ion may saturate the
detector. No target compound concentration may exceed the upper
limit of the initial calibration range unless a more dilute aliquot
of the sample is also analyzed according to the procedures in Section
10.2.9.
11.4.9 The Contractor must demonstrate that there is no carryover from a
contaminated sample before data from subsequent analyses may be
submitted. After a sample that contains a target compound at a level
exceeding the initial calibration range, or a non-target compound at
a concentration greater than 100 ug/L, or saturated ions from a
compound (excluding the compound peaks in the solvent front), the
Contractor must either:
11.4.9.1 Analyze an instrument blank immediately after the contaminated
sample. If an autosampler is used, an instrument blank must also
be analyzed using the same purge inlet that was used for the
contaminated sample. The. instrument blanks must meet the
technical acceptance criteria for blank analysis (Section 12.1.5);
or
11.4.9.2 Monitor the analyzed sample immediately after the contaminated
sample for all the compounds that were in the contaminated sample
and that exceeded the limits above. The maximum carryover
criteria are as follows: the sample must not contain a concen-
tration above the CRQL for the target compounds, or above 2 ug/L
for the non-target compounds that exceeded the limits in the
contaminated sample. If an autosampler is used, the next sample
analyzed using the same purge inlet that was used for the
contaminated sample must also meet the maximum carryover criteria.
11.5 Corrective Action for Sample Analysis
11.5.1 Sample technical acceptance criteria must be met before data are
reported. Samples contaminated from laboratory sources or any
samples not meeting the sample technical acceptance criteria will
require re-analysis at no additional cost to USEPA.
11.5.2 Corrective actions for failure to meet instrument performance checks,
initial calibration, continuing calibration, and method blanks must
be completed before the analysis of samples.
11.5.3 If the technical acceptance criteria for any of the internal
standards and DMCs are not met, check calculations, internal standard
and DMC spiking solutions, and instrument performance. It may be
necessary to bake-out the system to remove the water from the purge
and trap transfer lines, to recalibrate the instrument, or take other
corrective action procedures to meet the technical acceptance
criteria.
11.5.4 Sample reruns performed as a result of suspected matrix interference
beyond the scope of the method will be evaluated on a case-by-case
basis for payment purposes by the USEPA Contract Laboratory Program
Project Officer (CLP PO). Send a copy of the SDG Narrative
OLC03.2 D-42/VOA
-------
Exhibit D Volatiies -- Section 11
Data Analysis and Calculations (Con't)
(including your contract number), a description of the situation, and
the requested action to the CLP PO.
11.5.5 If the contractor needs to analyze more than one (1) sample dilution
other than the original analysis to have all the target compounds
within the initial calibration range, contact Sample Management
Office (SMO). SMO will contact the Region for instruction.
11.5.6 All samples to be reported to USEPA must meet the maximum carryover
criteria in Section 11.4.9. If any sample fails to meet these
criteria, each subsequent analysis must be checked for cross
contamination. The analytical system is considered contaminated
until a sample has been analyzed that meets the maximum carryover
criteria or an instrument blank has been analyzed that meets the
technical acceptance criteria for blanks.
D-43/VOA OLC03.2
-------
Exhibit D Volatiles -- Section 12
Quality Control
12.0 QUALITY CONTROL (QC)
12.1 Blank Analyses
12.1.1 Summary of Blank Analyses
There are three different types of blanks required by this method.
12.1.1.1 Method Blank - 25 milliliters (mL) of reagent water spiked with
10.0 microliters (uL) internal standard solution and 10.0 uL
Deuterated Monitoring Compound (DMC) solution, and carried through
the entire analytical procedure. The purpose of the method blank
is to determine the levels of contamination associated with
processing and analysis of samples.
12.1.1.2 Storage Blank - Upon receipt of the first samples in a Sample
Delivery Group (SDG), two 40 mL screw cap VOA vials with a
PTFE-faced silicons septum are filled with reagent water (80 mL
total). The vials are stored with the samples in the SDG under
the same conditions. A 25.0 mL aliquot of this reagent water is
spiked with a 10.0 uL internal standard solution and 10.0 uL of
DMC solution and analyzed after all samples in the SDG have been
analyzed. The storage blank indicates whether contamination may
have occurred during storage of samples.
12.1.1.3 Instrument Blank - 25 mL of reagent water spiked with 10.0 uL of
internal standard solution and 10.0 uL of DMC solution and carried
through the entire analytical procedure. Instrument blanks are
analyzed after a sample/dilution which contains a target compound
at a concentration greater than 25 micrograms per liter (ug/L)
(ketones 125 ug/L), or a non-target compound at a concentration
greater than 100 ug/L or saturated ions from a compound (excluding
the compound peaks in the solvent front). The results from
. instrument blank analysis indicate whether there is contamination
from a previous sample.
12.1.2 Frequency of Blank Analyses
12.1.2.1 The method blank must be analyzed at least once during every 12-
hour time period on each Gas Chromatograph/Mass Spectrometer
. (GC/MS) system used for volatile analysis (see Section 9.2.2 for
the definition of the 12-hour time period).
12.1.2.2 The method blank must be analyzed after the continuing calibration
standard and before any samples or storage blanks are analyzed.
The method blank must be analyzed after the initial calibration
sequence if samples are analyzed before the 12-hour time period
expires. A method blank must be analyzed in each 12-hour time
period in which samples (including dilutions) and storage blanks
from an SDG are analyzed.
12.1.2.3 A minimum of one storage blank must be analyzed per SDG, after all
samples for the SDG have been analyzed, unless the SDG contains
only ampulated Performance Evaluation (PE) samples. Analysis of a
OLC03.2 D-44/VOA
-------
Exhibit D Voiatiies -- Section 12
Quality Control (Con't)
storage blank is not required for SDGs that contain only ampulated
PE samples.
12.1.2.4 The Contractor must demonstrate that there is no carryover from
contaminated samples before data from subsequent analyses may be
used. Samples may contain target compounds at levels exceeding
the initial calibration range or non-target compounds at
concentrations greater than 100 ug/L, or ions from a compound that
saturate the detector (excluding the compound peaks in the solvent
front). An instrument blank must be analyzed immediately after
the contaminated sample (also in the same purge inlet if an
autosampler is used)', or a sample that meets the maximum carryover
criteria in Section 11.4.9 must be analyzed. For these purposes,
if the instrument blank meets the technical acceptance criteria
for blank analysis or the sample meets the maximum carryover
criteria, the system is considered to be uncontaminated. If the
instrument blank or sample does not meet the criteria (i.e.,
contaminated), the system must be decontaminated. Until an
instrument blank meets the blank technical acceptance criteria or
a sample meets the maximum carryover criteria, any samples
analyzed since the original contaminated sample will require re-
analysis at no additional expense to USEPA.
NOTE: Only the instrument blank which demonstrates that there was
no carryover from the previous sample or the instrument blank that
demonstrates that the system is clean (Section 12.1.5.7) must be
•?.•:• reported. Instrument blanks analyzed during the instrument
>-" decontamination process which exceed the requirements listed in
Section 11.4.9 do not need to be reported.
T
12.1.3 '%•' Procedure for Blank Analyses
12.1.3.1 Spike 25 mL of reagent water with 10.0 uL of the internal standard
solution (Section 7.2.3.3), and 10.0 uL of the DMC solution
(Section 7.2.3.4).
12.1.3.2 Prepare and analyze the blanks as described in Section 10.2.
12.1.4 Calculations for Blank Analyses
Perform data analysis and calculations according to Section 11.
12.1.5 Technical Acceptance Criteria for Blank Analyses
12.1.5.1 All blanks must be analyzed on a GC/MS system meeting the 4-Bromo-
fluorobenzene (BFB), initial calibration, and continuing
calibration technical acceptance criteria, and at the frequency
described in Section 12.1.2.
12.1.5.2 The storage blank must be analyzed on a GC/MS system that also
meets the technical acceptance criteria for the method blank.
12.1.5.3 The percent recovery of each of the DMCs in the blank must be
within the acceptance windows in Table D-5.
D-45/VOA OLC03.2
-------
Exhibit D Volatiles -- Section 12
Quality Control (Con't)
12.1.5.4 The EICP area for each of the internal standards in the blank must
be within the inclusive range of ±40.0 percent of its response in
the most recent continuing calibration standard analysis.
12.1.5.5 The retention time shift.for each of the internal standards in the
blank must be within ±0.33 minutes (20.0 seconds) of its retention
time in the most recent continuing calibration standard analysis.
12.1.5.6 The Relative Retention Time (RRT) of each of the DMCs in the blank
must be within ±0.06 RRT units of its relative retention time in
the most recent continuing calibration standard analysis.
12.1.5.7 The concentration of each target compound found in the storage and
method blanks must be less than its CRQL listed in Exhibit C
(Volatiles), except for methylene chloride and cyclohexane which
must be less than 10 times their respective CRQLs, and acetone and
2-butanone, which must be less than two times their respective
CRQLs. The concentration of each target compound in the
instrument blank must be less than its CRQL listed in Exhibit C
(Volatiles). The concentration of non-target compounds-in all
blanks must be less than 2.0 ug/L.
12 .1.6 Corrective Action for Blank Analyses
12.1.6.1 It is the Contractor's responsibility to ensure that method
interferences caused by contaminants in solvents, reagents,
glassware, laboratory air, and other sample storage and processing
hardware that lead to discrete artifacts and/or elevated baselines
in gas chromatograms, be eliminated. If a Contractor's blanks
exceed the criteria in Section 12.1.5.7, the Contractor must
consider the analytical system to be out of control. The source
of the contamination must be investigated and appropriate
corrective measures MUST be taken and documented before further
sample analysis proceeds.
12.1.6.2 Any method blank or instrument blank that fails to meet the
technical acceptance criteria must be re-analyzed at no additional
cost to USEPA. Further, all samples processed within the 12-hour
time period with a method blank or instrument blank that does not
meet the blank technical acceptance criteria will require re-
analysis at no additional cost to USEPA.
12.1.6.3 If the storage blank does not meet the technical acceptance
criteria for blank analyses in Sections 12.1.5.1 to 12.1.5.6,
correct system problems and re-analyze the storage blank. If the
storage blank does not meet the criteria in Section 12.1.5.7, re-
analyze the blank to determine whether the contamination occurred
during storage or during analyses. If upon re-analysis, the
storage blank meets the criteria in Section 12.1.5.7, the problem
occurred during the analysis and the re-analyzed storage blank
results must be reported. If upon re-analysis the storage blank
did not meet the criteria in Section 12.1.5.7, the problem
occurred during storage. The laboratory manager or.his/her
designee must address the problem in the SDG Narrative and discuss
the corrective actions implemented to prevent future occurrences.
OLC03.2 D-46/VOA
-------
Exhibit D Volatiles -- Section 12
Quality Control (Con't)
NOTE: A copy of the storage blank data must be retained by the
Contractor and be made available for inspection during on-site
laboratory evaluations.
12.2 Matrix Spike/Matrix Spike Duplicate (MS/MSD)
12.2.1 Summary of MS/MSD
In order to evaluate the effects of the sample matrix on the method
used for volatile analysis, USEPA has prescribed a mixture of
volatile target compounds to be spiked into two aliquots of a sample,
and analyzed in accordance with the appropriate method, upon request.
12.2.2 Frequency of MS/MSD
12.2.2.1 A MS/MSD shall only be analyzed if requested by the Region
(through the Sample Management Office (SMO)) or specified on the
Traffic Report (TR). If requested, a matrix spike and a matrix
spike duplicate must be performed for each group of 20 field
samples in an SDG, or each SDG, whichever is most frequent.
12.2.2.2 As part of USEPA's Quality Assurance (QA)/Quality Control (QC)
program, water rinsate samples and/or field/trip blanks (field QC)
may be delivered to a laboratory for analysis. The Contractor
shall not perform MS/MSD analysis on any of the field QC samples.
12.i'2.2.3 If the USEPA Region requesting MS/MSD designates a sample to be
'-"' used as an MS/MSD, then that sample must be used. If there is
-"- insufficient sample, less than the required amount, remaining to
* perform an MS/MSD, then the Contractor shall choose another sample
~- to perform an MS/MSD analysis. At the time the selection is made,
' the Contractor shall notify the Region (through SMO) that
insufficient sample was received and identify the USEPA sample
selected for the MS/MSD analysis. The rationale for the choice of
a sample other than the one designated by the Region shall be
documented in the SDG Narrative.
12.2.2.4 If there is insufficient sample remaining in any of the samples in
an SDG to perform an MS/MSD, then the Contractor shall immediately
contact SMO to inform them of the problem. SMO will contact the
Region for instructions. The Region will either approve that no
MS/MSD is.required, or require that a reduced sample aliquot be
used for the MS/MSD analysis. SMO will notify the Contractor of
the resolution. The Contractor shall document the decision in the
SDG Narrative.
12.2.2.5 If it appears that the Region has requested MS/MSD analysis at a
greater frequency than specified in Section 12.2.2.1, the
Contractor shall contact SMO. SMO will contact the Region to
determine which samples should have an MS/MSD performed on them.
SMO will notify the Contractor of the Region's decision. The
Contractor shall document the decision in the SDG Narrative. If
this procedure is not followed, the Contractor will not be paid
for MS/MSD analysis performed at a greater frequency than required
by the contract.
D-47/VOA OLC03.2
-------
Exhibit D Volatiles -- Section 12
Quality Control (Con't)
12.2.2.6 When a Contractor receives only Performance Evaluation (PE)
sample(s), no MS/MSD shall be performed within that SDG.
12.2.2.7 When a Contractor receives a PE sample as part of a larger SDG, a
sample other than the PE sample must be chosen for the requested
MS/MSD analysis when the Region did not designate samples to be
used for this purpose.
12.2.3 Procedure for Preparing MS/MSD
12.2.3.1 To prepare MS/MSD samples, add 10 uL of the matrix spike solution
(Section 7.2.3.5) to each of the 25 mL aliquots of the sample
chosen for spiking. Process samples according to Section 10.2.
Disregarding any dilutions, this is equivalent to a concentration
of 5 ug/L of each matrix spike compound.
12.2.3.2 MS/MSD samples must be analyzed at the same concentration as the
most concentrated aliquot for which the original sample results
will be reported. Sample dilutions must be performed in
accordance with Section 10.2.9. Do not further dilute MS/MSD
samples to get either spiked or non-spiked analytes within
calibration-range.
12.2.4 Calculations for MS/MSD
12.2.4.1 Calculate the concentrations of the matrix spike compounds using
the same equations as used for target -compounds (Equation 6) .
Calculate the recovery of each matrix spike compound as follows:
EQ. 9
Hurrlx Spike Recovery • SSR " SR x 100
Where:
SSR = Spiked sample result.
SR = Sample result.
SA = Spike added.
12.2.4.2 Calculate the Relative Percent Difference (RPD) of the recoveries
of each compound in the MS/MSD as follows:
EQ. 10
100
OLC03.2 D-48/VOA
-------
Exhibit D Volatiies -- Section 12
.Quality Control (Con't)
Where:
MSR = Matrix spike recovery.
MSDR = Matrix spike duplicate recovery.
12.2.5 Technical Acceptance Criteria for MS/MSD
12.2.5.1 If requested, all MS/MSD must be prepared and .analyzed at the
frequency described in Section 12.2.2. All MS/MSDs must be
analyzed on a GC/MS system meeting the BFB, initial and continuing
calibration technical acceptance criteria, and the blank technical
acceptance criteria.
12.2.5.2 The MS/MSD must be analyzed within the contract holding time.
12.2.5.3 The retention time shift for each of the internal standards in the
MS/MSD must be within ±0.33 minutes (20 seconds) of its retention
. time in the most recent continuing calibration standard analysis.
12.2.5.4 The limits for matrix spike compound recovery and RPD are given in
Table D-6. As these limits are only advisory, no further action
by the laboratory is required. However, frequent failures to meet
the limits for recovery or RPD warrant investigation by the
laboratory, and may result in questions from USEPA.
12.2.5V5 The relative retention time for the DMCs must be within ±0.06 RRT
*"" units of its standard retention time in the Continuing Calibration
Standard.
12.2.6 Corrective Action for MS/MSD
Any MS/MSD that does not meet the technical acceptance criteria in
Sections 12.2.5.1 through 12.2.5.3 must be re-analyzed at no
additional cost to USEPA.
12.3 Method Detection Limit (MDL) Determination
12.3.1 Before any field samples are analyzed under this contract, the MDL
for each volatile target compound shall be determined on each
instrument used for analysis. The MDLs must be verified annually
thereafter (see Section 12.3.2 for MDL verification procedures),
until the contract expires or is terminated, or after major
instrument maintenance. Major instrument maintenance includes, but
is not limited to cleaning or replacement of the mass spectrometer
source, mass filters (e.g., quadrupole, ion trap, etc.), or electron
multiplier (or similar device), replacement of gas chromatographic
column, and replacement or overhaul of the purge and trap device.
12.3.2 To determine the MDLs, the Contractor shall run an MDL study
following the procedures specified in 40 CFR Part 136. The
Contractor shall analyze the MDL samples on each instrument used for
field sample analyses. MDL verification is achieved by analyzing a
single reagent water blank spiked with each volatile target compound
D-49/VOA OLC03.2
-------
Exhibit D Volatiles -- Section 12
Quality Control (Con't)
at a concentration equal to two times the analytical determined MDL.
The resulting mass spectra of each target compound must meet the
qualitative identification criteria outlined in Sections 11.1.1
through 11.1.4.3
12.3.3 The determined concentration of the MDL must be less than the CRQL.
12.3.4 All documentation for the MDL studies shall be maintained at the
laboratory and provided to USEPA upon written request.
OLC03.2 D-50/VOA
-------
Exhibit D Volatiies -- Sections 13 - 16
Method Performance
13.0 METHOD PERFORMANCE
Not applicable.
14.0 POLLUTION PREVENTION
14.1 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 feasibility reduced at the source, USEPA
recommends recycling as the next best option.
14.2 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.
15.0 WASTE MANAGEMENT
15.1 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 hpods 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 14.2.
16.0 REFERENCES
Not applicable.
D-51/VOA OLC03.2
-------
Exhibit D Volatiles -- Section 17
Tables/Diagrams/Flowcharts
17.0 TABLES/DIAGRAMS/FLOWCHARTS
TABLE D-l BFB KEY IONS AND ABUNDANCE CRITERIA
Mass Ion Abundance Criteria
50 8.0-40.0 percent of mass 95
75 30.0-66.0 percent of mass 95
95 base peak, 100 percent relative abundance
96 5.0-9.0 percent of mass 95 (see note)
173 less than 2.0 percent of mass 174
174 50.0 - 120.0 percent of mass 95
175 4.0 - 9.0 percent of mass 174
176 93.0 - 101.0 percent of mass 174
177 . 5.0-9.0 percent of mass 176
NOTE: All ion abundances must be normalized to m/z 95, the nominal
base peak, even though the ion abundance of m/z 174 may be up to 120
percent that of m/z 95.
OLC03.2 D-52/VOA
-------
Exhibit D Volatiles - Section 17
Tables/Diagrams/Flowcharts (Con't)
TABLE D-2
TECHNICAL ACCEPTANCE CRITERIA FOR INITIAL AND CONTINUING
CALIBRATION FOR VOLATILE ORGANIC COMPOUNDS
Volatile
Compound
Dichlorodifluoromethane
Chloromethane
Vinyl chloride
Bromomethane
Chloroethane
Trichlorofluoromethane
1 , 1-Dichloroethene
1, l,2-Trichloro-l,2, 2-trif luoroethane
Acetone
Carbon disulfide
Methyl Acetate
Methylene chloride
trans-1, 2-Dichloroethene
Methyl tert -Butyl Ether
1, 1-Dichloroethane
cis-1, 2-Dichloroethene
2-Butanone
Bromochloromethane
Chloroform
1,1, 1-Trichloroethane
Cyclohexane
Carbon tetrachloride
Benzene
1 , 2 -Dichloroethane
Trichloroethene
Methyl cyclohexane
1 , 2 -Dichloropropane
Bromodichloromethane
cis-1, 3-Dichloropropene
4 -Methyl - 2 -pent anone
Toluene
trans-l , 3 -Dichloropropene
1,1,2-Trichloroethane
Tetrachlofoethene
2-Hexanone
Dibromochloromethane
1 , 2 -Dibromoethane
Chlorobenzene
Ethylbenzene
Xylene (total)
Styrene
Bromoform
I sopropy Ibenzene
Minimum
RRF
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
010
010
100
100
010
010
100
010
010
010
010
010
010
010
200
010
010
050
200
100
010
100
400
100
300
010
010
200
200
010
400
100
100
100
010
100
100
500
100
300
300
050
010
Maximum
%RSD
none
none
30.0
30.0
none
none
30.0
none
none
none
none
none
none
none
30.0
none
none
30.0
30.0
30.0
none
30.0
30.0
30.0
30.0
none
none
30.0
30.0
none
30.0
30.0
30.0
30.0
none
30.0
30.0
30.0
30.0
30.0
30.0
30.0
none
Maximum
%Diff
none
none
±30.0
±30.0
none
none
±30.0
none
none
none
none
none
none
none
±30.0
none
none
±30.0
±30.0
±30.0
none
±30. .0
±30.0
±30.0
±30.0
none
none
±30.0
±30.0
none
±30.0
±30.0
±30.0
±30.0
none
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
±30.0
none
D-53/VOA
OLC03.2
-------
Exhibit D Volatiles - Section 17
Tables/Diagrams/Flowcharts (Con't)
TABLE D-2
TECHNICAL ACCEPTANCE CRITERIA FOR INITIAL AND CONTINUING
CALIBRATION FOR VOLATILE ORGANIC COMPOUNDS (Con't)
Volatile
Compound
1,1,2,2 -Tetrachloroethane
1 , 3 -Dichlorobenzene
1 , 4 -Dichlorobenzene
1 , 2 -Dichlorobenzene
1, 2-Dibromo-3-chloropropane
1 , 2 , 4-Trichlorobenzene
1,2,3 -Trichlorobenzene
DEUTERATED
Vinyl Chloride-d3
Chloroethane-d5
1, l-Dichloroethene-d2
2-Butanone-d5
Chloroform-d
1 , 2 -Dichloroethane-d4
Benzene-d6
1 , 2 -Dichloropropane-d6
Toluene-d8
trans-1, 3-Dichloropropene-d4
2-Hexanone-d5
Bromoform-d
1, l,2,2-Tetrachloroethane-d2
l,2-Dichlorobenzene-d4
Minimum
RRF.
0.100
0.400
0.400.
0.400
0.010
0.200
0.200
MONITORING COMPOUNDS
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
Maximum
%RSD
30.0
30.0
30.0
30.0
none
30.0
30.0
none
none
none
none
none
none
none
none
none
none
none
none
none
none
Maximum
%Diff
±30.0
±30.0
±30.0
±30.0
none
±30.0
±30.0
none
none
none
none
none
none
none
none
none
none
none
. none
none
none
OLC03.2
D-54/VOA
-------
Exhibit D Volatiles -- Section 17
Tables/Diagrams/Flowcharts (Con't)
TABLE D-3
VOLATILE TARGET COMPOUNDS AND DEUTERATED MONITORING COMPOUND (DMC)
WITH CORRESPONDING INTERNAL STANDARDS•FOR QUANTITATION
1,4-Difluorobenzene
Chlorobenzene-d5
1,4-Dichlorobenzene-d4
Dichlorodi fluoromethane
Chloromethane
Vinyl Chloride
Bromomethane
Chloroethane
Trichlorofluoromethane
1,1-Dichloroethene
1,1,2-Trichloro-1,2,2-
trifluoroethane
Acetone
Carbon Disulfide
Methyl Acetate
Bromochloromethane
Methylene Chloride
trans-1,2-Dichloroethene
Methyl tert-Butyl Ether
1,1-Dichl oroe'thane
cis-1,2-Dichloroethene
2-Butanone
Chloroform
1,2-Dichloroethane
Vinyl Chloride-d3 (DMC)
Chloroethane-d5 (DMC)
l,l-Dichloroethene-d2 (DMC)
2-Butanone-d5 (DMC)
Chlorofortn-d (DMC)
1,1,1-Trichloroethane
Cyclohexane
Carbon Tetrachloride
Benzene
Trichloroethene
Methy1eye1ohexane
1,2-Dichloropropane
Bromodi chloromethane
cis-1,3-Dichloropropene
4-Methyl-2-pent anone
Toluene
trans-1,3-Dichloropropene
1,1,2-Trichloroethane
Tetrachloroethene
2-Hexanone
Dibromochlbromethane
1,2-Dibromoethane
Chlorobenzene
Ethylbenzene
Xylenes (total)
Styrene
Isopropylbenzene
1,1,2,2-Tetrachloroethane
Benzene-d6 (DMC)
1,2-Dichloropropane-
d6 (DMC)
Bromoform
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
1,2-Dibromo-3-chloropropane
1,2,4-Trichlorobenzene
1,2,3-Trichlorobenzene
l,2-Dichlorobenzene-d4 (DMC)
Bromoform-d (DMC)
l,2-Dichloroethane-d4 (DMC)
trans-1,3-Dichloropropene-
d4 (DMC)
Toluene-d8 (DMC)
2 -Hexanone-d5 (DMC)
1,1,2,2-Tetrachloroethane-
d2 (DMC)
D-55/VOA
OLC03.2
-------
Exhibit D Volatiles -- Section 17
Tables/Diagrams/Flowcharts (Con't)
TABLE D-4
CHARACTERISTIC IONS FOR VOLATILE TARGET COMPOUNDS
Target Compound
Dichlorodifluoromethane
Chloromethane
Vinyl chloride
Bromomethane
Chloroethane
Trichlorofluoromethane
1 , 1 -Dichloroethene
1, 1, 2-Trichloro-l, 2, 2-trif luoroethane
Acetone
Carbon disulfide
Methyl Acetate
Methylene chloride
trans-l, 2 -Dichloroethene
Methyl tert -Butyl Ether
1 , 1-Dichloroethane
cis - 1 , 2 -Dichloroethene
2 -Butanone
Chloroform
Bromochl o rome thane
1,1, 1-Trichloroethane
Cyclohexane
Carbon Tetrachloride
Benzene
1 , 2-Dichloroethane
Trichloroethene
Methyl cyclohexane
1 , 2 -Dichloropropane
Bromodichloromethane
cis-1, 3 -Dichloropropene
4 -Methyl -.2 -pentanone
Toluene
trans-l , 3 -Dichloropropene
1,1, 2-Trichloroethane
Tetrachloroethene
2 -Hexanone
Dibromochloromethane
1 , 2 -Dibromoethane '
Chlorobenzene
Ethylbenzene
Xylene (total)
Styrene
Bromoform
*m/z 43 is used for quantitation of 2-Butanone,
Primary
Quantitation Secondary
. Ion Ion(s)
85
50
62
94
64
101
96
101
43
76
43
84
96 .
73
63
96
43*
83
128
97
56
117
78
62
95
83
63
83
75
43
91
75
97
164
43
129
107
112
91
106
104
173
but m/z 72 must
87
52
64
96
66
103
61, 63
85, 151
58
78
74
49, 86
61, 98
43, 57
65, 83
61, 98
72
85
49, 130,
99, 61
69, 84
119
-
98
97, 132,
55, 98 -
112
85, 127
77
58, 100
92
77
83, 85,
132, 134
129, 131
58, 57,
127
109, 188
77, 114
106
91
78
175, 254
be present for .
51
130
99,
, 166
100
positive identification.
OLC03.2
D-56/VOA
-------
Exhibit D Volatiles -- Section 17
Tables/Diagrams/Flowcharts (Con't)
TABLE D-4
CHARACTERISTIC IONS FOR VOLATILE TARGET COMPOUNDS (Con't)
Analyte
Isopropylbenzene
1,1,2 , 2-Tetrachloroethane
1 , 3 -Dichlorobenzene
1 , 4 -Dichlorobenzene
1 , 2 -Dichlorobenzene
1 , 2 -Dibromo-3 -Chloropropane
1,2,4 -Trichlorobenzene
1,2,3 -Trichlorobenzene
Deuterated Monitoring Compounds
Vinyl Chloride-d3
Chloroethane-d5
1, l-Dichloroethene-d2
2 - But anone - d5
Chloroform-d
1, 2-Dichloroethane-d4
Benzene-d6
1 , 2 -Dichloropropane-d6
Toluene-d8
t rans -1,3-Dichl orqpir opene - d4
2 - Hexanone - d5
Bromoform-d
1,1,2,2 -Tetrachloroethane-d2
1, 2-Dichlorobenzene-d4
Internal Standards
1 , 4 -Dichlorobenzene-d4
1 , 4 -Dif luorobenzene
Chlorobenzene-d5
Primary
Quantitation Secondary
Ion Ion(s)
105 120, 77
83 85, 131
146 111, 148
146 111, 148
146 111, 148
75 157, 155
180 182, 145
180 182, 145
65 67
69 71, 51
63 98, 65
46 77
84 86, 47, 49
65 67, 51
84 82, 54, 52
67 65, 46, 42
98 100, 42
79 . 81, 42
63 46
.174 . 172
84 86
152 150
152 115, 150
114 63, 88
117 82, 119
D-57/VOA
OLC03.2
-------
Exhibit D Volatiles -- Section 17
Tables/Diagrams/Flowcharts (Con't)
TABLE D-5 .
DEUTERATED MONITORING COMPOUND RECOVERY LIMITS
Compound
Percent
Recovery Limits
Vinyl Chloride-d3
Chioroethane-d5
1,l-Dichloroethene-d2
2-Butanone-d5
Chi oro f orm- d
1,2-Dichloroethane-d4
Benzene-d6
1,2-Dichloropropane-d6
Toluene-d8
trans-1,3-Dichloropropene-d4
2-Hexanone-d5
Bromoform-d
1,1,2,2-Tetrachloroethane-d2
1,2-Dichlorobenzene-d4
49-138
60-126.
65-130
42-171
80-123
78-129
78-121
84-123
77-120
80-128
37-169
76-135
75-131
50-150
NOTE: The recovery limits for any of the compounds listed above may
be expanded at any time during the period of performance if USEPA
determines that the limits are too restrictive.
TABLE D-6
MATRIX SPIKE RECOVERY AND
RELATIVE PERCENT DIFFERENCE LIMITS
Compound
% Recovery
RPD
1 , 1 -Dichloroethene
Benzene
Trichloroethene
Toluene
Chlorobenzene
61-145
76-127
71-120
76-125
75-130
14
11
14
13
13
OLC03.2
D-58/VOA
-------
EXHIBIT D
METHOD FOR THE ANALYSIS OF LOW CONCENTRATION WATER FOR
SEMIVOLATILE ORGANIC COMPOUNDS
D-l/SV OLC03.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
OLC03.2 D-2/SV
-------
Exhibit D -- Analytical Methods for Setnivolatiles
Table of Contents
Section • Page
1.0 SCOPE AND APPLICATION • 5
2.0 SUMMARY OF METHOD 6
3.0 DEFINITIONS 6
4.0 INTERFERENCES 7
5.0 SAFETY 7
6.0 EQUIPMENT AND SUPPLIES 8
6.1 Glassware 8
6.2 Gases 8
6.3 Gas-line Tubing . 8
6.4 Silicon Carbide Boiling Chips 8
6.5 Water Bath 8
6.6 Balance 8
6.7 Nitrogen Evaporation Device 9
6.8 pH Meter 9
6.9 pH Paper 9
6.10 Gas Chromatograph/Mass Spectrometer (GC/MS) 9
7.0 REAGENTS AND STANDARDS 12
7.1 Reagents 12
7.2 Standards 12
8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE 16
8.1 Sample Collection and Preservation 16
.8.2 Procedure for Sample Storage 16
8.3 Procedure for Sample Extract Storage 16
8.4 Records for Sample and Sample Extract Storage 16
8.5 Contract Required Holding Times 16
9.0 CALIBRATION AND STANDARDIZATION 17
9.1 Instrument Operating Conditions 17
9.2 Instrument Performance Check (DFTPP) 17
9.3 Initial Calibration 18
9.4 Continuing Calibration 21
10.0 PROCEDURE 24
10.1 Sample Preparation '24
10.2 Instrument Analysis of Sample 27
11.0 DATA ANALYSIS AND CALCULATIONS 29
11.1 Qualitative Identification of Target Compounds 29
11.2 Qualitative Identification of Non-Target Compounds 30
11.3 Calculations for Target Compounds 31
11.4 Calculations for Non-Target Compounds . . .' 34
11.5 Calculations for Deuterated Monitoring Compounds (DMCs) 34
11.6 Technical Acceptance Criteria for Sample Analysis : . . 34
11.7 Corrective Action for Sample Analysis . 35
12.0 QUALITY CONTROL 36
12.1 Method Blank 36
12.2 Matrix Spike/Matrix Spike Duplicate (MS/MSD) 37
12.3 Method Detection Limit (MDL) Determination ' 40
D-3/SV OLC03.2
-------
Exhibit D -- Analytical Methods for Semivolatiles
Table of Contents (Continued)
Page
13.0 METHOD PERFORMANCE 41
14.0 POLLUTION PREVENTION .41
15.0 WASTE MANAGEMENT 41
16.0 REFERENCES 41
17.0 TABLES/DIAGRAMS/FLOWCHARTS 42
OLC03.2 ' D-4/SV
-------
Exhibit D Semivolatiles -- Section 1
Scope and Application
1.0 SCOPE AND APPLICATION
1.1 The analytical method that follows is designed to analyze water samples
containing low concentrations of the semivolatile compounds listed on
the Target Compound List (TCL) in Exhibit C. The majority of the
samples are expected to be from drinking water and well/ground
water/aqueous type sources around Superfund sites. The method is based
upon the semivolatile method contained in the Contract Laboratory
Program (CLP) Statement of Work, "Organic Analysis, Multi-Media, Multi-
Concentration Analyses". The analytical method includes the use of
Deuterated Monitoring Compounds (DMC) for precision and accuracy
assessment.
1.2 Benzaldehyde, Acetophenone, Caprolactam, 1,1'-Biphenyl, Atrazine, and
1,2,4,5-Tetrachlorobenzene have been added to the TCL.
1.3 Problems have been associated with the following compounds analyzed by
this method:
• 3,3'-Dichlorobenzidine and 4-chloroaniline may be subject to
oxidative losses during solvent concentration.
• Hexachlorocyclopentadiene is subject to thermal decomposition in the
inlet of the Gas Chromatograph (GC), chemical reactions in acetone
solution, and photochemical decomposition.
• N-nitrosodiphenylamine decomposes in the gas chromatographic inlet
forming diphenylamine and, consequently, may be detected as
diphenylamine.
• Due to the lower quantitation limits required by this method, extra
caution must be exercised when identifying compounds.
D-5/SV OLC03.2
-------
'Exhibit D Semivolatiles -- Sections 2 & 3
Summary of Method
2.0 SUMMARY OF METHOD
2.1 A one liter aliquot of sample is acidified to pH 2.0 and extracted with
methylene chloride using a- continuous liquid-liquid extractor.
Separator/ funnel extraction is not permitted. The methylene chloride
extract is dried with sodium sulfate and concentrated to a volume of 1.0
milliliter (mL). The extract is injected onto a Gas Chromatograph (GC)
capillary column. The GC is temperature programmed to separate the
semivolatile compounds, which are then detected with a Mass Spectrometer
(MS) .
2.2 Deuterated Monitoring Compounds (DMCs) and internal standards are added
to all samples, standards, requested Matrix Spike/Matrix Spike
Duplicate(s) (MS/MSD) and blanks. The target compounds and DMCs are
identified in the samples and blanks by analyzing standards that contain
all target compounds, DMCs, and internal standards under the same
conditions and comparing resultant mass spectra and GC retention times.
A Relative Response Factor (RRF) is established for each target compound
and DMC during the initial and continuing calibrations by comparing the
mass spectra response from the Extracted Ion Current Profile (EICP) for
the primary quantitation ion produced by that compound to the mass
spectra response for the primary quantitation ion produced by the
associated internal standard compound. Each identified target compound
and DMC is quantitated by comparing the instrument response for the
compound in the sample, standard, requested MS/MSD or blank with the
instrument response of the associated internal standard, while taking
into account the RRF from the most recent mid-point calibration, the
sample volume, and any sample dilutions.
2.3 Non-target compounds are identified by comparing the resultant mass
spectra from the non-target compounds to mass spectra contained in the
NIST/EPA/NIH (May 1992 release or later) and/or Wiley (1991 release or
later) or equivalent mass spectral library. Non-target compounds are
quantitated by comparing the mass spectra response from the
Reconstructed Ion Chromatogram (RIC) for the non-target compound peaks
to the mass spectra response produced by the nearest internal standard.
An RRF of 1 is assumed.
3.0 DEFINITIONS
See Exhibit G for a complete list of definitions.
OLC03.2 D-6/SV
-------
Exhibit D Semivolatiles -- Sections 4 & 5
Interferences
4 .0 INTERFERENCES
Contaminants in solvents, reagents, glassware, and other sample
processing hardware may cause method interferences such as discrete
artifacts and/or elevated baselines in the Reconstructed Ion
Chromatogram (RIC) profiles. All of these materials must be routinely
demonstrated to be free from interferences under the conditions of the
analysis by running laboratory method blanks. Matrix interferences may
be caused by contaminants that are coextracted from the sample. The
extent of matrix interferences will vary considerably from source to
source.
5.0 SAFETY
The toxicity or carcinogenicity of each reagent used in this method has
not been precisely determined; however, each chemical should be treated
as a potential health hazard. Exposure to these reagents should be
reduced to the lowest possible level. The laboratory is responsible for
maintaining a current awareness file of OSHA regulations regarding the
safe handling of the chemicals specified in this method. A reference
file of data handling sheets should be made available to all personnel
involved in these analyses. Specifically, concentrated sulfuric acid
presents some hazards and is moderately toxic and extremely irritating
to skin and mucous membranes. Use these reagents in a fume hood
whenever possible and if eye or skin contact occurs flush with large
3 volumes of water. Always wear safety glasses or a shield for eye
protection, protective clothing, and observe proper mixing when working
with these reagents.
D-7/SV OLC03.2
-------
Exhibit D Semivolatiles -- Section 6
Equipment and Supplies
6.0 EQUIPMENT AND SUPPLIES
Brand names, suppliers, catalog 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, but demonstration of equivalent performance meeting the
requirements of this Statement of Work is the responsibility of the
Contractor. The Contractor shall document any use of alternate
equipment or supplies in the SDG Narrative.
6.1 Glassware
6.1.1 Continuous liquid-liquid extractors - Equipped with PTFE or glass
connecting joints and stopcocks requiring no lubrication
(Hershberg-Wolf Extractor-Ace Glass Company, Vineland, NJ, P/N
6841-10 or equivalent) or Hydrophobia Membrane-based Extractor
(Accelerated One Step™ Extractor, Corning series 3195 or
equivalent).
6.1.2 Drying column - 19 millimeter (mm) ID chromatographic column with
coarse frit (substitution of a small pad of Pyrex pre-extracted glass
wool for the frit will prevent cross contamination of sample
extracts).
6.1.3 Kuderna-Danish Apparatus
6.1.3.1 Concentrator tube - Kuderna-Danish, 10 milliliter (mL), graduated
(Kontes, Vineland, NJ, K-570050-1025 or equivalent).
6.1.3.2 Evaporation flask - Kuderna-Danish, 500 mL (Kontes K-570001 -0500
or equivalent). Attach to concentrator tube with springs.
6.1.3.3 Snyder column - Kuderna-Danish, Three-ball macro (Kontes K-50300-
0121 or equivalent).
6.1.3.4 Snyder column - Kuderna-Danish, Two-ball micro (Kontes K-569001-
0219 or equivalent).
6.1.4 Vials - Amber glass, 2 mL capacity with PTFE-lined screw-cap.
6.1.5 Syringes - 0.2mL, O.SmL, 10 mL volumes with Luerlock.
6.1.6 Micro-syringes - 10 microliter (uL) and larger, 0.006 inch (0.15 mm)
ID needle.
6.2 Gases - Helium, Nitrogen, ultra pure grade.
6.3 Gas-line Tubing - Stainless steel or copper tubing.
6.4 Silicon Carbide Boiling Chips - Approximately 10/40 mesh. Heat to 400°C
for 30 minutes or Soxhlet extract with methylene chloride. PTFE boiling
chips solvent rinsed prior to use are acceptable.
6.5 Water Bath - Heated, with concentric ring cover, capable of temperature
control. To prevent the release of solvent fumes into the laboratory,
the bath must be used in a hood.
6.6 Balance - Analytical, capable of accurately weighing ±0.0001 grams (g).
The balances must be calibrated with class S weights or known reference
weights once per each 12-hour workshift. The balances must be
calibrated with class S weights at a minimum of once a month. The
balances must also be annually checked by a certified technician.
.OLC03.2 . D-8/SV
-------
Exhibit D Semivolatiles -- Section 6
Equipment and Supplies (Con't)
6.7 Nitrogen Evaporation Device - Equipped with a water bath that can be
maintained at 35°C to 40°C. To prevent the release of solvent fumes
into the laboratory, the nitrogen evaporation device must be used in a
hood. The N-Evap by Organomation Associates, Inc. South Berlin, MA (or
equivalent) is suitable.
6.8 pH Meter - With a combination glass electrode, calibrated according to
manufacturer's instructions. The pH meter shall be calibrated before
each use.
6.9 pH Paper - Including narrow range capable of measuring a pH of 2.
6.10 Gas Chromatograph/Mass Spectrometer (GC/MS)
6.10.1 Gas Chromatograph - The gas chromatograph system must be capable of
temperature programming and have a flow controller that maintains a
constant column flow.rate throughout the temperature program. The
system must be suitable for splitless injection and have all required
accessories including syringes, analytical columns, and gases. All
GC carrier gas lines must be constructed from stainless steel or
copper tubing. Non-polytetrafluoroethylene (PTFE) thread sealants,
or flow controllers with rubber components are not to be used.
6.10.2 Gas Chromatography Column - Minimum length 30 meters (m) x 0.25
millimeter (mm) ID (or 0.32 mm) bonded-phase silicon coated fused
silica capillary column DB-5 (J&W Scientific); RTx-5 (Restek); SPB-5
(Supelco); AT-5 (Alltech); HP-5 (Hewlett-Packard); CP-Sil 8CB
(Chrompack); 007-2 (Quadrex); BP-5 (SGE); or equivalent. Note that
this is a minimum requirement for column length. Longer columns may
•••* be used. Although a film thickness of 1.0 micron is recommended
~ because of its larger capacity, a film thickness of 0.25 micron may
be used. A description of the GC column used for analysis shall be
3? provided in the SDG Narrative.
6.10.2.1 A capillary column is considered equivalent if:
• The column does not introduce contaminants which interfere
with the identification and quantitation of the compounds
listed in Exhibit C (Semivolatiles).
• The analytical results generated using the column meet the
initial and continuing calibration technical acceptance
criteria listed in the SOW, and the Contract Required
Quantitation Limits (CRQLs) listed in Exhibit C
(Semivolatiles).
• The column can accept up to 120 nanograms (ng) of each
compound listed in Exhibit C (Semivolatiles) without becoming
overloaded.
• The column provides equal or better resolution of the
compounds listed in Exhibit C (Semivolatiles) than the columns
listed in Section 6.10.2.
6.10.2.2 As applicable, follow manufacturer's instructions for use of its
product.
6.10.2.3 The Contractor must maintain .documentation that the alternate
column met the criteria in Section 6.10.2.1. The minimum
documentation is as follows:
D-9/SV OLC03.2
-------
Exhibit D Semivolatiles -- Section 6
Equipment and Supplies (Con't)
6.10.2.3.1 Manufacturer provided information concerning the performance
characteristics of the column.
6.10.2.3.2 Reconstructed Ion Chromatograms (RICs) and data system reports
generated on the GC/MS used for CLP analyses:
• From blanks which demonstrate that there are no
contaminants which interfere with the semivolatile analysis
when using the alternate column;
• For initial calibration standards analyzed using the
alternate column,-
• For continuing calibration standards analyzed using the
alternate column.
6.10.2.4 Based on the Contractor generated data described in Section
6.10.2.3.2, the Contractor must complete a written comparison and
review signed by the Laboratory Manager certifying that:
• The column performance meets the technical acceptance criteria
in Sections 9.3.5 and 9.4.5.
• The low point initial calibration standard analysis has
adequate sensitivity to meet the semivolatile CRQLs.
• The high point initial calibration standard analysis was not
overloaded.
• The column does not introduce contaminants which interfere
with the identification and/or quantitation of compounds
listed in Exhibit C (Semivolatiles).
6.10.2.5 The documentation must be made available to USEPA during on-site
laboratory evaluations or sent to USEPA upon request of the
Contract Laboratory Program Project Officer (CLP PO) or the
Organic Program Manager at Analytical Operations/Data Quality
Center (AOC).
6.10.2.6 PACKED COLUMNS CANNOT BE USED.
6.10.3 Mass Spectrometer - The mass spectrometer must be capable of scanning
from 35 to 500 atomic mass units (amu) every 1 second or less,
utilizing 70 volts (nominal) electron energy in the electron impact
ionization mode and producing a mass spectrum which meets all the
decafluorotriphenylphosphine (DFTPP) GC/MS performance check
technical acceptance criteria (Table D-l) when 50 ng of DFTPP is
injected through the GC inlet. To ensure sufficient precision of
mass spectral data, the MS scan rate must allow acquisition of at
least five spectra while a sample compound elutes from the GC. The
GC/MS system must be in a room whose atmosphere is demonstrated to be
free of all potential contaminants which will interfere with the
analysis. The instrument must be vented outside the facility or to a
trapping system which prevents the release of contaminants into the
instrument room.
6.10.4 GC/MS interface - any GC/MS interface which provides acceptable
sensitivity at CRQLs. GC/MS interfaces constructed of all-glass or
glass-lined materials are recommended. Glass can be deactivated by
silanizing with dichlorodimethylsilane.
OLC03.2 D-10/SV
-------
Exhibit D Semivoiatiies -- Section 6
Equipment and Supplies (Con't)
6.10.5 Data system - a computer system must be interfaced to the mass
spectrometer that allows the continuous acquisition and storage on
machine-readable media, of all mass spectra obtained throughout the
duration of the chromatographic program. The computer must have
software that allows searching any GC/MS data file for ions of a
specified mass and plotting such ion abundance versus time or scan
number. This type of plot is defined as an Extracted Ion Current
Profile (EICP). Software must also be available that allows
integrating the abundance in any EICP between specified time or scan
number limits. Also, for the non-target compounds, software must be
available that allows for the comparison of sample spectra against
reference library spectra. The NIST/EPA/NIH (May 1992 release or
later) and/or Wiley (1991 release or later), or equivalent mass
spectral library shall be used as the reference library. The
operational data system must be able to flag all data files that have
been edited manually by laboratory personnel.
6.10.6 Magnetic tape storage device - must be capable of recording data and
suitable for long-term, off-line storage of GC/MS data.
D-ll/SV OLC03.2
-------
Exhibit D Semivolatiles -- Section 7
Reagents, and Standards
7.0 REAGENTS AND STANDARDS
7.1 Reagents
Reagents shall be dated with the receipt date and used on a first-in,
first-out basis. The purity of the reagents shall be verified before
use.
7.1.1 Reagent water - defined as water in which no semivolatile target
compound is observed at or above the Contract Required Quantitation
Limit (CRQL) listed in Exhibit C for that compound and in which no
non-target compound is observed at or above 10 micrograms per liter
(ug/L).
7.1.1.1 Reagent water may be generated by passing tap water through a
carbon filter bed containing about 453 grams (g) (1 Ib) of
activated carbon (Calgon Corp., Filtrasorb-300 or equivalent).
7.1.1.2 Reagent water may be generated using a water purification system
(Millipore Super-Q or equivalent).
7.1.2 Solvents - Acetone, methanol, methylene chloride, isooctane, 2-
propanol, toluene. Pesticide quality or equivalent 1
7.1.3 Sodium sulfate - (ACS) Granular or powdered, anhydrous (J.T. Baker
anhydrous powder, catalog #73898, J.T. Baker anhydrous granular
#3375, or equivalent). Purify by heating at 400°C for four hours in
a shallow tray, cool in a desiccator, and store in a glass bottle.
CAUTION: An open container of sodium sulfate may become contaminated
during storage in laboratory.
7.1.4 Sulfuric acid solution (1:1) - slowly add 50 milliliters (mL) of
concentrated H2SO4 (Sp. Gr. 1.84; 36N) to 50 mL of reagent water.
7.2 Standards
The Contractor must provide all standard solutions to be used with this
contract. These standards may be used only after they have been
certified according to the procedure in Exhibit E. 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 Stock Standard Solutions
Stock standard solutions may be purchased or prepared using the
following procedure.
7.2.1.1 Accurately weigh about 0.0100 g of pure material. Dissolve the
material in methylene chloride or another suitable solvent and
dilute to volume in a 10 mL volumetric flask. Larger volumes may
be used at the convenience of the analyst.
7.2.1.2 When compound purity is assayed to be 97 percent or greater, the
weight may be used without correction to calculate the
concentration of the stock solution. If the compound purity is
assayed to be less than 97 percent, the weight must be corrected
when calculating the concentration of the stock solution.
7.2.1.3 Fresh stock standards must be prepared once every twelve months,
or sooner, if standards have degraded or concentrated. Stock
standards must be checked for signs of degradation or
OLC03.2 D-12/SV
-------
Exhibit D Semivolatiles -- Section 7
Reagents and Standards (Con't)
concentration just prior to preparing secondary dilution and
working standards from them.
7.2.2 Secondary Dilution Standards
7.2.2.1 Using stock standards, prepare secondary dilution standards in
methylene chloride that contain the compounds of interest either
singly or mixed together.
7.2.2.2 Fresh secondary dilution standards must be prepared once every
twelve months, or sooner, if standards have degraded.or
concentrated. Secondary dilution standards must be checked for
signs of degradation or concentration just prior to preparing
working standards from them.
7.2.3 Working Standards
7.2.3.1 Deuterated Monitoring Compound (DMC) Standard Spiking Solution
7.2.3.1.1 Prepare a DMC standard spiking solution that contains the
following compounds at concentrations shown in methanol:
Concentration
DMC * g/mL
Phenol-d5 40
bis-(2-Chloroethyl)ether-d8 40
2-Chlorophenol-d4 40
4-Methylphenol-d8 40
Nitrobenzene-d5 40
2-Nitrophenol-d4 40
2,4-Dichlorophenol-d3 40
•~ • 4-Chloroaniline-d4 40 .
Vu Dimethylphthalate-d6 40
Acenaphthylene-d8 40
4-Nitrophenol-d4 40
Fluorene-dlO 40
**-. 4,6-Dinitro-methylphenol-d2 40
Anthracene-dlO 40
Pyrene-dlO 40
Benzo(a)pyrene-dl2 40
7.2.3.1.2 DMC standards are added to all samples, blanks, requested
Matrix Spike/Matrix Spike Duplicate(s) (MS/MSD), and
calibration solutions. The DMC standard spiking solution must
be prepared every twelve months or sooner if the solution has
degraded or concentrated.
7.2.3.2 Matrix Spiking Solution
7.2.3.2.1 The matrix spiking solution consists of the following:
Bases/Neutrals Acids
Acenaphthene Pentachlorophenol
2,4-Dinitrotoluene Phenol
Pyrene 2-Chlorophenol
N-Nitroso-di-n-propylamine 4-Chloro-3-methylphenol
4-Nitrophenol
7.2.3.2.2 Prepare a spiking solution that contains'each of the
base/neutral compounds above at 20 micrograms per milliliter
(• g/mL) in methanol and the acid compounds at 80 • g/mL in
methanol.
D-13/SV OLC03.2
-------
Exhibit D Semivolatiles -- Section 7
Reagents and Standards (Con't)
7.2.3.2.3 The matrix spiking solution must be prepared every twelve
months or sooner if the solution has degraded or concentrated.
7.2.3.3 Instrument Performance Check Solution--DFTPP
Prepare a 50 nanograms per microliter (ng/uL) solution of
decafluorotriphenylphosphine (DFTPP) in methylene chloride. The
DFTPP solution must be prepared fresh once every twelve months or
sooner if the solution has degraded or concentrated.
7.2.3.4 Initial and Continuing Calibration Solutions
7.2.3.4.1 Five initial calibration standard solutions are required for
all target compounds and DMCs. Standard concentrations of 5,
10, 20, 50, and 80 ng/uL are required for the DMCs and all but
seven of the target compounds. The seven compounds: 2,4-
dinitrophenol, 2,4,5-trichlorophenol, 2-nitroaniline, 3-
nitroaniline, 4-nitroaniline, 4-nitrophenol, and 4,6-dinitro-2-
methylphenol require calibration at 20, 50, 80, 100, and 120
ng/uL.
7.2.3.4.2 To prepare a calibration standard solution, add an appropriate
volume of secondary dilution standard to methylene chloride in
a volumetric flask. Dilute to volume with methylene chloride.
7.2.3.4.3 The 20 ng/uL initial calibration solution (80 ng/uL for the
seven compounds listed in Section 7.2.3.4.1) is the continuing
calibration solution.
7.2.3.4.4 The five initial calibration solutions must be prepared fresh
before use. The continuing calibration standard solution must
be prepared weekly or sooner if the solution has degraded or
concentrated.
7.2.3.5 Internal Standard Spiking Solution
7.2.3.5.1 Prepare an internal standard spiking solution in methylene
chloride or another suitable solvent that contains 1,4
dichlorobenzene-di, naphthalene-d8, acenaphthene-d10,
phenanthrene-d10, chrysene-d12, and perylene-d^ at 2000 ng/uL.
It may be necessary to use 5 to 10 percent toluene in this
solution and a few minutes of ultrasonic mixing in order to
dissolve all the constituents.
NOTE: For automated systems using an injection volume of less
than 10 uL, the internal standard solution may need to be
prepared at a different concentration.
7.2.3.5.2 The internal standard spiking solution must be prepared every
twelve months or sooner if the solution has degraded or
concentrated.
7.2.4 Ampulated Standard Extracts
Standard solutions purchased from a chemical supply house as
ampulated extracts in glass vials may be retained and used until the
expiration date provided by the manufacturer. If no manufacturer's
expiration date is provided, the standard solutions as ampulated
extracts may be retained and used for 2 years from the preparation
date. Standard solutions prepared by the Contractor which are
immediately ampulated in glass vials may be retained for 2 years from
preparation date. Upon breaking the glass seal, the expiration times
OLC03.2 D-14/SV
-------
Exhibit D Setnivoiatiies -- Section 7
Reagents and Standards (Con't)
listed in Sections 7.2.1 to 7.2.3.5 will apply. The Contractor is
responsible for assuring that the integrity of the standards has not
degraded (Section 7.2.5.5).
7.2.5 Storage of Standard Solutions
7.2.5.1 Store the stock and secondary standard solutions at 4°C (±2°C) in
PTFE-lined screw-cap amber bottles.
7.2.5.2 Store the working standard solutions at 4°C (±2°C) in PTFE-lined
screw-cap amber bottles.
7.2.5.3 Protect all standards from light.
7.2.5.4 Samples, sample extracts, and standards must'be stored separately.
7.2.5.5 The Contractor is responsible for maintaining the integrity of
standard solutions and verifying prior to use. Storage of
standard solutions in the freezer may cause some compounds to
precipitate. This means at the minimum, the standards must be
brought to room temperature prior to use, checked for losses, and
checked that all components have remained in solution. Additional
steps may be necessary to ensure all components are in solution.
7.2.6 Temperature Records for Storage of Standards
7.2.6.1 The temperature of all standard storage refrigerators shall be
recorded daily.
7.2.6.2," Temperature excursions shall be noted and appropriate corrective
is- actions shall be taken to correct problems, when required.
.&•
7.2.6.3. Corrective action Standard Operating Procedures (SOPs) shall be
posted on the refrigerators.
D-15/SV OLC03.2
-------
Exhibit D Semivolatiles -- Section 8
Sample Collection, Preservation and Storage
8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE
8.1 Sample Collection and Preservation
8.1.1 Water samples may be collected in 1 liter (L) (or 1 quart) amber
glass containers and fitted with screw-caps lined with PTFE. If
amber containers are not available, the samples should be protected
from light. The specific requirements for site sample collection are
outlined by the Region.
8.1.2 All samples must be iced or refrigerated at 4°C (±2°C) from the time
of collection until extraction.
8.2 Procedure for Sample Storage
8.2.1 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.
8.2.2 The samples must be stored in an atmosphere demonstrated to be free
of all potential contaminants.
8.3 Procedure for Sample Extract Storage
8.3.1 Sample extracts must be protected from light and stored at less than
4°C (±2°C) until 365 days after delivery of a reconciled, complete
data package to USEPA.
8.3.2 Samples, sample extracts, and standards must be stored separately.
8.4 Records for Sample and Sample Extract Storage
8.4.1 The temperature of all sample and sample extract storage
refrigerators shall be recorded daily.
8.4.2 Temperature excursions shall be noted and appropriate corrective
actions shall be taken to correct problems, when required.
8.4.3 Corrective action SOPs shall be posted on the refrigerators.
8.5 Contract Required Holding Times
8.5.1 Extraction of water samples by continuous liquid-liquid procedures
shall be started within 5 days of Validated Time of Sample Receipt
(VTSR) .
NOTE: Separatory funnel extraction procedures are not permitted.
8.5.2 As part of USEPA1s QA program, USEPA may provide Performance
Evaluation (PE) samples as standard extracts which the Contractor is
required to prepare per the instructions provided by USEPA. PE
samples must be 'extracted and analyzed concurrently with the samples
in the SDG. The extraction holding time (5 days after VTSR) does not
apply to PE samples received as standard extracts.
8.5.3 Extracts of water samples must be analyzed within 40 days following
extraction.
OLC03.2 ' D-16/SV
-------
Exhibit D Semivolatiles -- Section 9
Calibration and Standardization
9.0 CALIBRATION AND STANDARDIZATION
9.1 Instrument Operating Conditions
9.1.1 Gas Chromatograph (GC)
9.1.1.1 The following are the gas chromatographic analytical conditions.
The conditions are recommended unless otherwise noted.
Initial Column Temperature Hold 40°C for 4 minutes
Column Temperature Program 40-270°C at 10°C/min.
Final Column Temperature Hold 270°C for 3 minutes after all
compounds listed in Exhibit C
(Semivolatiles) have eluted
(required)
Injector Temperature 250-300°C
Transfer Line Temperature 250-300°C
Source Temperature ' According to manufacturer's
specifications
Injector Grob-type, splitless
Sample Volume 1 • L
Carrier Gas Helium at 30 cm/sec
9.1.1.2 Optimize GC conditions for analyte separation and sensitivity.
Once optimized, the same GC conditions must be used for the
analysis of all standards, samples, blanks, matrix spikes, and
matrix spike duplicates, if required.
9.1.2 Mass Spectrometer (MS)
The following are the required mass spectrometer analytical
''••' .conditions:
Electron Energy 70 volts (nominal)
Mass Range 35 to 500 amu
Scan Time Not to exceed 1 second per scan
lonization Mode El
9.2 Instrument Performance Check (DFTPP)
9.2.1 Summary of Instrument Performance Check
The GC/MS system must be tuned to meet the manufacturer's
specifications, using a suitable calibrant such as perfluoro-tri-n-
butylamine (FC-43) or perfluorokerosene (PFK). The mass calibration
and resolution of the GC/MS system are verified by the analysis of
the instrument performance check solution (Section 7.2'.3.3). Prior
to the analysis of any samples (including requested Matrix
Spike/Matrix Spike Duplicate (MS/MSD) and PE Samples) blanks and
calibration standards, the Contractor must establish that the GC/MS
system meets the mass spectral ion abundance criteria for the
instrument performance check solution containing decafluoro-
triphenylphosphine (DFTPP).
9.2.2 Frequency of Instrument Performance Check
9.2.2.1 The instrument performance check solution must be analyzed once at
the beginning of each 12-hour period during which samples, blanks
or standards are analyzed.
D-17/SV OLC03.2
-------
Exhibit D Semivolatiles -- Section 9
Calibration and Standardization (Con't)
9.2.2.2 The 12-hour time period for a instrument performance check and
standards calibration (initial or continuing calibration criteria)
begins at the moment of injection of the DFTPP analysis that the
laboratory submits as documentation of a compliant instrument
performance check. The time period ends after 12-hours have
elapsed according to the system clock.
9.2.3 Procedure for Instrument Performance Check
The analysis of the instrument performance check solution may be
performed as an injection of up to 50 nanograms (ng) of DFTPP into
the GC/MS or by adding 50 ng of DFTPP to a calibration standard
(Section 7.2.3.4.3) and analyzing the calibration standard.
9.2.4 Technical Acceptance Criteria for Instrument Performance Check
9.2.4.1 The GC/MS system must be tuned at the frequency described in
Section 9.2.2.
9.2.4.2 The abundance criteria listed in Table D-l must be met for a 50 ng
injection of DFTPP. The mass spectrum of DFTPP must be acquired
in the following manner: three scans (the peak apex scan and the
scans immediately preceding and following the apex) are acquired
and averaged. Background subtraction is required, and must be
accomplished using a single scan acquired no more than.20 scans
prior to the beginning of the elution of DFTPP. Do not subtract
part of the DFTPP peak.
NOTE: All subsequent standards, samples, and 'blanks associated
with a DFTPP analysis must use the identical mass spectrometer
instrument conditions.
9.2.5 Corrective Action for Instrument Performance Check
9.2.5.1 If the GC/MS performance check technical acceptance criteria are
not met, re-tune the GC/MS system. It may be necessary to clean
the ion source, clean quadrupoles, or take other actions to
achieve the technical acceptance criteria.
9.2.5.2 GC/MS performance check technical acceptance criteria MUST be met
before any standards, samples, and required blanks are analyzed.
Any standards, samples, and required blanks analyzed when GC/MS
performance check technical acceptance criteria have not been met
will require re-analysis at no additional cost to USEPA.
9.3 Initial Calibration
9.3.1 Summary of Initial Calibration
Prior to the analysis of samples and required blanks and after GC/MS
performance check technical acceptance criteria have been met, each
GC/MS system must be initially calibrated at a minimum of five
concentrations (Section 7.2.3.4) to determine instrument sensitivity
and the linearity of GC/MS response- for the semivolatile target and
Deuterated Monitoring Compounds (DMCs).
9.3.2 Frequency of Initial Calibration
9.3.2.1 Each GC/MS system must be initially calibrated upon award of the
contract, whenever the Contractor takes corrective action which
may change or affect the initial calibration criteria (e.g., ion
source cleaning or repair, column replacement, etc.'), or if the
OLC03.2 D-18/SV
-------
Exhibit D Semivolatiles -- Section 9
Calibration and Standardization (Con't)
continuing calibration technical acceptance criteria have not been
met.
9.3.2.2 If time still remains in the 12-hour time period after meeting the
technical acceptance criteria for the initial calibration, samples
and blanks may be analyzed. It is not necessary to analyze a
continuing calibration standard within this 12-hour time period,
if the initial calibration standard that is the same concentration
as the continuing calibration standard meets the continuing
calibration technical acceptance criteria. Quantitate all sample
and blank results against the initial calibration standard that is
the same concentration as the continuing calibration standard
(Section 7.2.3.4.3). Compare quality control criteria such as
internal standard area response change and retention time shift to
the initial calibration standard that is the same concentration as
the continuing calibration standard.
9.3.3 Procedure for Initial Calibration
9.3.3.1 Set-up .the GC/MS system per the requirements of Section 9.1.
9.3.3.2 All standard/spiking solutions must be allowed to warm to ambient
temperature (approximately 1 hour) before preparation or analysis.
9.3.3.3 Prepare five calibration standards containing all the semivolatile
target and DMCs at the concentrations described in Section
7.2.3.4.1.
9.3.3.4 Add 10 microliters (uL) of the internal standard spiking solution
•* (Section 7.2.3.5) to 1.0 milliliters (mL) of each of the five
calibration standards for a concentration of 2.0 nanograms per
microliter (ng/uL) for each internal standard compound.
9.3.3.5 Tune the GC/MS system to meet the technical acceptance criteria in
-?" Section 9.2.4 for DFTPP.
9.3.3/6 Analyze each calibration standard by injecting 1.0 uL of standard.
9.3.4 Calculations for Initial Calibrations
9.3.4.1 Calculate Relative Response Factors (RRF) for each semivolatile
target compound and DMC using Equation 1. See Table D-2 to
associate semivolatile target and deuterated monitoring compounds
with the proper internal standard. See Table D-3 for primary
quantitation ions to be used for each semivolatile target
compound, DMC, and internal standard.
NOTE: Unless otherwise stated the area response is that of the
primary quantitation ion.
EQ. 1
c.
D-19/SV OLC03.2
-------
Exhibit D Semivolatiles -- Section 9
Calibration and Standardization (Con't)
Where:
AX = Area of the characteristic ion for the compound to be
measured.
Ais = Area of the characteristic ion for the specific internal
standard (Table D-2).
Cls = Amount of the internal standard injected (ug).
Cx = Amount of the compound to be measured injected (ug).
9.3.4.2 Calculate the mean Relative Response Factor for each compound
using Equation 2.
EQ. 2
X-
Where:
Xi = Each individual value.
• = The mean of n values.
n = The total number of values.
9.3.4.3 Calculate the percent relative standard deviation (%RSD) of
Relative Response Factor (RRF) values for each semivolatile target
compound and DMC over the initial calibration range using Equation
3 in conjunction with.Equation 4.
EQ. 3
- (Standard Peviation> ,
Hean
Where:
%RSD = Percent relative standard deviation.
9.3.4.4 Equation 4 is the general formula for standard deviation for a
statistically small set of values.
EQ. 4
Staadard Deviation -
n-1
OLC03.2 D-20/SV
-------
Exhibit D Semivolatiles -- Section 9
Calibration and Standardization (Con't)
Where:
Xi, • and n are as defined in Equation 2.
9.3.5 Technical Acceptance•Criteria for Initial Calibration
9.3.5.1 All initial calibration standards must be analyzed at the
concentration levels described in Section 7.2.3.4.1 and at the
frequency described in Section 9.3.2 on a GC/MS system meeting the
DFTPP technical acceptance criteria.
9.3.5.2 The relative response factor (RRFi) at each calibration
concentration for each semivolatile target compound and DMC must
be greater than or equal to the compound's minimum acceptable
relative response factor listed in Table D-4.
9.3.5.3 The %RSD over the initial calibration range for relative response
factor for each semivolatile target compound that has a required
%RSD must be less than or equal to the %RSD listed in Table D-4.
9.3.5.4 Up to four compounds may fail the criteria listed in Sections
9.3.5.2 and 9.3.5.3 and still meet the minimum RRF and %RSD
requirements. However, these four compounds must have a minimum
RRF greater than 0.010 and %RSD less than or equal to 40.0%.
9.3.5.5 Excluding those ions in the solvent front, no quantitation ion may
saturate the detector. Consult the manufacturer's instrument
manual to determine how saturation is indicated for your
instrument.
9.3.6 Corrective Action for Initial Calibrations
9.3.6.1. If-the technical acceptance criteria for initial calibration are
..-, not met, inspect the system for problems. It may be necessary to
clean the ion source, change the column, or take other corrective
actions to achieve the technical acceptance criteria.
9.3.6.2 Initial calibration technical acceptance criteria MUST be met
before any samples or required blanks are analyzed. Any samples
or required blanks analyzed when initial calibration technical
acceptance criteria have not been met will require re-analysis at
no additional cost to USEPA.
9.4 Continuing Calibration
9.4.1 Summary of Continuing Calibration
Prior to the analysis of samples and required blanks and after GC/MS
performance check technical acceptance criteria and initial
calibration technical acceptance criteria have been met, each GC/MS
system must be routinely checked by analyzing a continuing
calibration standard to ensure that the instrument continues to meet
the instrument sensitivity and linearity requirements of the method.
The continuing calibration standard contains all the semivolatile
target compounds, DMCs, and internal standards.
9.4.2 Frequency of Continuing Calibration
9.4.2.1 Each GC/MS used for analysis must be calibrated once every twelve
(12) hour time period of operation. The 12-hour time period
begins with the injection of DFTPP.
D-21/SV OLC03.2
-------
Exhibit D Semivolatiles -- Section 9
Calibration and Standardization (Con't)
9.4.2.2 If time still remains in the 12-hour time period after meeting the
technical acceptance criteria for the initial calibration, samples
and blanks may be analyzed. It is not necessary to analyze a
continuing calibration standard within this 12-hour time period,
if the initial calibration standard that is the same concentration
as the continuing calibration standard meets the continuing
calibration technical acceptance criteria. Quantitate all sample
and blank results against the 20 ng/uL (80 ng/uL for the seven
compounds listed in Section 7.2.3.4.1) calibration standard.
9.4.3 Procedure for Continuing Calibration
9.4.3.1 All standard/spiking solutions must be allowed to warm to ambient
temperature (approximately 1 hour) before preparation or analysis.
9.4.3.2 Add 10 uL of the internal standard solution (Section 7.2.3.5) to
1.0 mL of the continuing calibration standard (Section 7.2.3.4.3)
for a concentration of 20 ng/uL for each internal standard
compound.
9.4.3.3 Analyze the continuing calibration standard by injecting 1.0 uL of
standard.
9.4.4 Calculations for Continuing Calibration
9.4.4.1 Calculate a RRF for each send/volatile target compound and DMC
using Equation 1 for the primary characteristic ions found in
Table D-3.
9.4.4.2 Calculate the percent difference between the mean relative
response factor from the most recent initial calibration and the
continuing calibration relative response factor for each
semivolatile target compound and DMC using Equation 5. For
internal standards, use the primary ions listed in Table D-3
unless interferences are present. . If interferences prevent the
use of the primary ion for a given internal standard, use the
secondary ion(s) listed in Table D-3.
EQ. 5
Where:
Mean relative response factor from the most recent
RRFi = initial calibration meeting technical acceptance
criteria.
RRFC = Relative response factor from continuing calibration
standard.
9.4.5 Technical Acceptance Criteria for Continuing Calibration
9.4.5.1 The continuing calibration standard must be analyzed at the 20
ng/uL (80 ng/uL for the seven compounds listed in 7.2.3.4.1)
concentration level, and at the frequency described in Section
9.4.2, on a GC/MS system meeting the DFTPP and the initial
calibration technical acceptance criteria.
OLC03.2 D-22/SV
-------
Exhibit D Semivolatiles -- Section 9
Calibration and Standardization (Con't)
9.4.5.2 The relative response factor for each semivolatile target compound
and DMC must be greater than or equal to the compound's minimum
acceptable relative response factor listed in Table D-4.
9.4.5.3 The relative response factor percent difference for each
semivolatile target compound that has a percent difference
criteria must be within the inclusive range listed in Table D-4.
9.4.5.4 Up to four compounds may fail the requirements listed in Sections
9.4.5.2 and 9.4.5.3 and still meet the minimum relative response
factor and percent difference criteria. However, these compounds
must have a minimum relative response factor greater than or equal
to 0.010 and the percent difference must be within the inclusive
range of ±40%.
9.4.5.6 Excluding those ions in the solvent front, no quantitation ion may
saturate the detector. Consult the manufacturer's instrument
operating manual to determine how saturation is indicated for your
instrument.
9.4.6 Corrective Action for Continuing Calibration
9.4.6.1 If the continuing calibration technical acceptance criteria are
not met, recalibrate the GC/MS instrument according to Section
9.3.3. It may be necessary to clean the ion source, change the
column, or take other corrective actions to achieve the technical
acceptance criteria.
9.4.6.2 Continuing calibration technical acceptance criteria MUST be met
before any samples (including requested MS/MSD) or required blanks
'-•'•?•• are analyzed. Any samples or required blanks analyzed when
•^- continuing calibration criteria have not been met will require re-
'-?..-' analysis at no additional cost to USEPA.
D-23/SV OLC03.2
-------
Exhibit D Semivolatiles -- Section 10
Procedure
10.0 PROCEDURE
10.1 Sample Preparation
10.1.1 This method is designed for analysis of water samples that contain
low concentrations of the semivolatile compounds listed in Exhibit C.
The majority of the samples are expected to come from drinking water
and well/ground water type sources around Superfund sites. If, upon
inspection of a sample, the Contractor suspects that the sample is
not amenable to this method, contact Sample Management Office (SMO).
SMO will contact the Region for instructions.
10.1.2 If insufficient sample volume (less than 90 percent of the required
amount) is received to perform the analyses, the Contractor shall
contact SMO to apprise 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.
10.1.3 Extraction of Sample
10.1.3.1 Allow the sample to come to ambient temperature (approximately 1
hour) .
10.1.3.2 Continuous liquid-liquid extraction is used to extract the
samples. Separatory funnel extraction cannot be used.
10.1.3.3 Continuous Liquid-Liquid Extraction Without Hydrophobic Membrane
10.1.3.3.1 Follow manufacturer's instructions for set-up.
10.1.3.3.2 Add methylene chloride to the bottom of the extractor and fill
it to a depth of at least one inch above the bottom sidearm.
10.1.3.3.3 Measure out a 1 L sample aliquot in a separate, clean graduated
cylinder; transfer the aliquot to the continuous extractor.
Measure and record the initial pH of the sample with a pH meter
or narrow range pH paper. Adjust the pH to 2.0 with 1:1 H2SO4
and record the final pH.
NOTE: With some samples, it may be necessary to place a layer
of glass wool between the methylene chloride and the water
layer in the extractor to prevent precipitation of suspended
solids into the methylene chloride during extraction.
10.1.3.3.4 Using a syringe or volumetric pipet, add 1.0 mL of the
Deuterated Monitoring Compound (DMC) standard spiking solution
(Section 7.2.3.1) into the sample and mix well.
10.1.3.3.5 Rinse the graduated cylinder with 50 mL of methylene chloride
and transfer the rinsate to the continuous extractor. If the
sample container is empty, rinse the container with 50 mL of
methylene chloride and add rinsate to the continuous extractor.
10.1.3.3.6 Add sufficient methylene chloride to the continuous extractor
to ensure proper solvent cycling during operation. Adjust the
drip rate to 5 to 15 mL/minute (recommended); optimize the
extraction drip rate. Extract for a minimum of 18 hours.
OLC03.2 D-24/SV
-------
Exhibit D Semivolatiles -- Section 10
Procedure (Con't)
NOTE 1: When a minimum drip rate of 10-15 mLs/min. is
maintained throughout the extraction, the extraction time may
be reduced to a minimum of twelve hours. Allow to cool, then
detach the distillation flask. Proceed to Section 10.1.4.
NOTE 2: Some continuous liquid-liquid extractors are also
capable of concentrating the extract within the extraction set-
up. Follow the manufacturer's instructions for concentration
when using this type of extractor.
10.1.3.4 Continuous Liquid-Liquid Extraction With Hydrophobic Membrane
10.1.3.4.1 Follow the manufacturer's instructions for set-up.-
10.1.3.4.2 Measure out each 1 L sample aliquot in a separate, clean
graduated cylinder. If the sample container is empty, rinse
the container with 50 mL of methylene chloride and add the
rinsate to the continuous extractor. If the sample container
is not empty, add 50 mL of methylene chloride to the continuous
extractor. Slowly transfer the aliquot to the continuous
extractor. Measure and record the initial pH of the sample
with a pH meter or a narrow range pH paper. Adjust the pH to
2.0 with 1:1 H2SO4 and record the final pH.
10.1.3.4.3 Using a syringe or volumetric pipet, add 1.0 mL of the DMC
standard spiking solution (Section 7.2.3.1) into the sample and
mix well.
10.1.3.4.4 Rinse the graduated cylinder with 50 mL of methylene chloride
"£•• and transfer the rinsate to the continuous extractor.
10.1.3-.:'4 .5 Add sufficient methylene chloride to the continuous extractor
to ensure proper solvent cycling during operation. Adjust the
"•• drip rate to 15 mL/minute (recommended) ; optimize the
—-' extraction drip rate. Extract for a minimum of 6 hours.
-4" NOTE 1: Due to the smaller volume of solvent used during the
extraction process, some sample matrices (e.g., oily samples,
samples containing a high concentration of surfactants) may
create an emulsion which will consume the solvent volume,
preventing the efficient extraction of the sample. When this
occurs, add additional solvent to assure efficient extraction
of the sample, and extend the extraction time for a minimum of
6 hours. If the sample matrix prevents the free flow of
solvent through the membrane, then the non-hydrophobic membrane
continuous liquid-liquid type extractor must be used.
Allow to cool, then detach the distillation flask. Proceed to
Section 10.1.4.
NOTE 2: Some continuous liquid-liquid extractors are also
capable of concentrating the extract within the extraction set-
up. Follow the manufacturer's instructions for concentration
when using this type of extractor. Using the hydrophobic
membrane type extractor, it may not be necessary to dry the
extract with sodium sulfate.
NOTE 3: If low DMC recoveries occur, assure 1) the apparatus
was properly assembled to prevent leaks,- 2) the drip
rate/solvent cycling was optimized; and 3) there was proper
cooling for condensation of solvent.
D-25/SV - OLC03.2
-------
Exhibit D Semivolatiles -- Section 10
Procedure (Con't)
NOTE 4: Alternate continuous liquid-liquid extractor types that
meet the requirements of the SOW may also be used. If using
alternate extractors or design types, follow the manufacturer's
instructions for set-up.
10.1.4 Concentrating the Sample Extract
10.1.4.1 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10 mL
concentrator tube to a 500 mL evaporative flask. Other
concentration devices or techniques may be used in place of the
K-D, if equivalency is demonstrated for all the semivolatile
target compounds listed in Exhibit C.
10.1.4.2 Transfer the extract by pouring the extract through a drying
column containing about 10 cm of anhydrous granular sodium
sulfate, and collect the extract in a K-D concentrator. Rinse the
distilling flask and column with 20 to 30 mL of methylene chloride
to complete the quantitative transfer.
10.1.4.3 Add one or two clean boiling chips and attach a three-ball Snyder
column to the evaporative flask. Pre-wet the Snyder column by
adding about 1 mL methylene chloride to the top of the column.
Place the K-D apparatus on a hot water bath (60°C to 80°C
recommended) so that the concentrator tube is partially immersed
in the hot water, and the entire lower rounded surface of the
flask is bathed with hot vapor. Adjust the vertical position of
the apparatus and the water temperature as required to complete
the concentration in 10 to 15 minutes. At the proper rate of
distillation, the balls of the column will actively chatter but
the chambers will not flood with condensed solvent. When the
apparent volume of liquid reaches 1 mL, remove the K-D apparatus
from the water bath and allow it to drain and cool for at least 10
minutes. DO NOT ALLOW THE EVAPORATIVE FLASK TO GO DRY. Remove
the Snyder column and rinse the flask and its lower joint into the
concentrator tube with 1 to 2 mL of methylene chloride. A 5 mL
syringe is recommended for this operation.
10.1.4.4 Two different types of concentration techniques are permitted to
obtain the final 1.0 mL volume: micro Snyder column and nitrogen
evaporation techniques.
10.1.4.4.1 Micro Snyder Column Technique
Add another one or two clean boiling chips to the concentrator
tube and attach a two-ball micro Snyder column. Pre-wet the
Snyder column by adding about 0.5 mL of methylene chloride to
the top of the column. Place the K-D apparatus in a hot water
bath (60°C to 80°C recommended) sp that the concentrator tube
is partially immersed in the hot water. Adjust the vertical
position of the apparatus and the water temperature as required
to complete the concentration in 5 to 10 minutes. At the
proper rate of distillation the balls of the column will
actively chatter but the chambers will not flood with condensed
solvent. When the apparent volume of liquid reaches about 0.5
mL, remove the K-D apparatus from the water bath and allow it
to drain for at least 10 minutes while cooling. DO NOT LET THE
EXTRACT GO DRY. Remove the Snyder column and rinse the
evaporative flask and its lower joint into the concentrator
tube with 0.2 mL of methylene chloride. Adjust the final
volume to 1.0 mL with methylene chloride. Transfer the extract
to a PTFE-sealed screw-cap bottle, label the bottle and store
at 4°C (±2°C).
OLC03.2 D-26/SV
-------
Bxhibit D Semivoiatlies -- Section 10
Procedure (Con't)
10.1.4.4.2 Nitrogen Evaporation Technique (taken from ASTM Method D3086) •
Place the concentrator tube in a warm water bath (30°C to 35°C)
and evaporate the solvent volume to just below 1 mL by blowing
a gentle stream of clean, dry nitrogen (filtered through a
column of activated carbon) above the extract. Caution: Gas
lines from the gas source to the evaporation apparatus must be
stainless steel, copper, or PTFE tubing. New plastic tubing
must not be used between the carbon trap and the sample since
it may introduce interferences. The internal wall of the
concentrator tube must be rinsed down several-times with
methylene chloride during the operation and the final volume
brought to 1.0 mL with methylene chloride. During evaporation,
the tube solvent level must be kept below the water level of
the bath. The extract must never be allowed to become dry.
Transfer the extract to a PTFE-sealed screw-cap bottle, label
the bottle and store at 4°C (±2°C).
10.2 Instrument Analysis of Sample
10.2.1 Set up the Gas Chromatograph/ Mass Spectrometer (GC/MS) system per
the requirements of Section 9.1. Before samples or required blanks
can be analyzed, the instrument must meet the decafluoro-
triphenylphosphine (DFTPP), initial calibration, and continuing
calibration technical acceptance criteria. All sample, blank
extracts, and standard/spiking solutions must be allowed to warm to
ambient temperature (approximately 1 hour) before analysis. All
sample extracts [including requested Matrix Spike/Matrix Spike
••"•. Duplicate (MS/MSD)] and required blanks must be analyzed under the
: same instrumental conditions as the calibration standards. ,
10.2.21/x Add 10.0 uL of the internal standard spiking solution (Section
?:?• 7.2.3.5) to the 1.0 mL extract. For sample dilutions, add an
-%•" appropriate amount of the internal standard spiking solution to
• '•§}- maintain a 20 nanograms per microliter (ng/uL) concentration of the
internal standards in the diluted extract.
NOTE: An alternate amount of internal standard solution may be added,
however the internal standards must be added to maintain the required
20 ng/uL of each internal standard in the sample extract.
10.2.3 Inject 1.0 uL of sample extract into the GC/MS, and start data
acquisition.
10.2.4 Three minutes after all semivolatile target compounds have eluted
from the GC, terminate the MS data acquisition and store data files
on the data system storage device. Use appropriate data output
software to display full range mass spectra and Extracted Ion Current
Profiles (EICPs).
10.2.5 Sample Dilutions
An original undiluted analysis must be made and results reported for
all samples.
10.2.5.1 When a sample extract is analyzed that has a semivolatile target
compound concentration greater than the upper limit of the initial
calibration range or in which ions from a target compound saturate
the detector (excluding the compound peaks in the solvent front),
the extract must be diluted, the internal standard concentration
must be readjusted, and the sample extract must be re-analyzed.
Secondary ion quantitation is only allowed when there are sample
D-27/SV OLC03.2
-------
Exhibit D Semivolatiles -- Section 10
Procedure (Con't)
interferences with the primary quantitation ion, not when
saturation occurs. If secondary ion quantitation is used,
calculate a relative response factor using the area response
(EICP) from the most intense secondary ion which is free of sample
interferences, and document the reasons for the use of the
secondary ion in the SDG Narrative.
NOTE: If the laboratory has evidence or highly suspects, because
of sample color or other physical property, that a sample may
contain extremely high concentrations of either target or non-
target compounds, then SMO shall be immediately contacted. SMO
will seek regional recommendations for diluted analysis.
10.2.5.2 Dilute the sample using the following procedure:
10.2.5.2.1 Calculate the sample dilution necessary to keep the
semivolatile target compounds that required dilution above the
mid-point standard in the initial calibration range and so that
no target compound has ions which saturate the detector
(excluding the compound peaks in the solvent front).
10.2.5.2.2 Dilute the sample extract quantitatively with methylene
chloride.
10.2.5.2.3 Analyze the sample dilution per Section 10.2, including the
addition of internal standards to maintain a 20 ng/uL
concentration of the internal standards (Section 10.2.2).
OLC03.2 D-28/SV
-------
Exhibit D Semivolatiles -- Section 11
Data Analysis and Calculations
11.0 DATA ANALYSIS AND CALCULATIONS
11.1 Qualitative Identification of Target Compounds
11.1.1 The compounds listed in the Target Compound List (TCL), Exhibit C,
shall be identified by an analyst competent in the interpretation of
mass spectra by comparison of the sample mass spectrum to the mass
spectrum of a standard of the suspected compound. Two criteria must
be satisfied to verify the identifications.
• Elution of the sample analyte within Gas Chromatograph (GC)
Relative Retention Time (RRT) unit window established from the
12-hour calibration standard.
• Correspondence of the sample analyte and calibration standard
component mass spectra.
11.1.2 For establishing'correspondence of the GC RRT, the sample component
RRT must be within ±0.06 RRT units of the RRT of the standard
component. For reference, the standard must be run on the same shift
as the sample. For samples analyzed during the same 12-hour time
period as the initial calibration standards, compare the analyte
retention times to those from the 20 nanograms per microliter (ng/uL)
(80 ng/uL for the seven compounds listed in Section 7.2.3.4.1)
calibration standard. If coelution of interfering compounds
prohibits accurate assignment of the sample component RRT from the
Extracted Ion Current Profile (EICP) for the primary ion, the RRT
must be assigned by using the total ion chromatogram.
11.1.3 For comparison of standard arid sample component mass spectra, mass
spectra obtained on the Contractor's GC/MS are required. These
standard spectra may be used for identification purposes only if the
Contractor's GC/MS meets the decafluorotriphenylphosphine (DFTPP)
technical acceptance criteria. These standard spectra may be
obtained from the analysis used to obtain reference RRTs.
11.1.4 The requirements for qualitative verification by comparison of mass
spectra are as follows:
11.1.4.1 All ions present in the standard mass spectra at a relative'
intensity greater than 10 percent (most abundant ion in the
spectrum equals 100 percent) must be present in the sample
spectrum.
11.1.4.2 The relative intensities of the major ions specified in Section
11.1.4.1 must agree within ±20 percent-between the standard and
sample spectra. (Example: For an ion with an abundance of 50
percent in the standard spectra, the corresponding sample ion
abundance must be between 30 and 70 percent.)
11.1.4.3 Ions greater than 10 percent in the sample spectrum but not
present in the standard spectrum must be considered and accounted
for by the analyst making the comparison. The verification
process should FAVOR FALSE POSITIVES. All compounds meeting the
identification criteria must be reported with their spectra. When
target compounds are below Contract Required Quantitation Limits
(CRQLs) but the spectrum meets the identification criteria, report
the concentration with a "J". For example, if the CRQL is 5.0
micrograms per liter (ug/L) and a concentration of 3.0 ug/L is
calculated, report the data as "3.0J".
D-29/SV OLC03.2
-------
Exhibit D Semivolatiles -- Section 11
Data Analysis and Calculations (Con't)
11.1.5 If a compound cannot be verified by all of the criteria in Sections
11.1.1 through 11.1.4, but in the technical judgment of the mass
spectral interpretation specialist, the identification is correct,
then the Contractor shall report that identification and proceed with
quantitation.
11.2 Qualitative Identification of Non-Target Compounds
11.2.1 A library search shall be executed for non-target compounds for the
purpose of tentative identification. The NIST/EPA/NIH (May 1992
release or later) and/or Wiley (1991 release or later), or equivalent
mass spectral library shall be used as the reference library (Section
6.10.5).
11.2.2 Up to 30 non-DMC/non-internal standard organic compounds of greatest
apparent concentration not listed in Exhibit C for the volatiles and
semivolatiles shall be tentatively identified via a forward search of
the NIST/EPA/NIH and/or Wiley mass spectral library, or equivalent
mass spectral library. The following are not to be reported:
• Compounds with responses less than 10 percent of the internal
standard (as determined by inspection of peak areas or heights);
• Compounds which elute earlier than 30 seconds before the first
semivolatile compound listed in Exhibit C (Semivolatiles) or
three minutes after the last semivolatile compound listed in
Exhibit C (Semivolatile) has eluted; and
• Volatile compounds listed in Exhibit C. Only after visual
comparison of sample spectra to spectra resulting from the
library search(es) will the mass spectral interpretation
specialist assign a tentative identification.
NOTE: Computer generated library search routines must not use
normalization routines that would misrepresent the library or unknown
spectra when compared to each other.
11.2.3 UP to 20 peaks of greatest apparent concentration (as determined by
inspection of peak areas or heights) that are suspected to be
straight-chain, branched, or cyclic alkanes, alone or part of an
alkane series shall be library searched. When the above alkanes are
tentatively identified, the concentration(s) are to be estimated as
described in Section 11.4 and reported in the SDG Narrative as
alkanes, by class (i.e., straight chain, branched, or cyclic; as a
series; as applicable). Alkanes are not counted as part of the 30
organic compounds described in Section 11.2.2.
11.2.4 Peaks that are suspected to be aldol-condensation reaction products
(e.g., 4-methyl-4-hydroxy-2-pentanone and 4-methyl-3-pentene-2-one)
shall be searched, reported, and counted as part of the 30 most
intense non-target semivolatile compounds, and qualified with an "A"
. flag on Form I LCSV-TIC.
11.2.5 Guidelines for making Tentative Identification
11.2.5.1 Major ions in the reference spectrum (ions greater than 10 percent
of the most abundant ion) should be present in the sample
spectrum.
11.2.5.2 The relative intensities of the major ions should agree within ±20
percent. (Example: For an ion with an abundance of 50 percent in
OLC03.2 D-30/SV
-------
Exhibit D Semivoiatiles -- Section 11
Data Analysis and Calculations (Con't)
the standard spectra, the corresponding sample ion abundance
should be between 30 and 70 percent.)
11.2.5.3 Molecular ions present in reference spectrum should be present in
sample spectrum.
11.2.5.4 Ions present in the sample spectrum but not in the reference
spectrum should be reviewed for possible background contamination
or presence of coeluting compounds.
11.2.5.5 Ions present in the reference spectrum but not in the sample
spectrum should be reviewed for possible subtraction from the
sample spectrum because of background contamination or coeluting
compounds.
NOTE: Data system library reduction programs can sometimes create
these discrepancies.
11.2.5.6 Non-target compounds receiving a library search match of 85% or
higher should be considered a "probable match". The compound
should be reported unless the mass spectral interpretation
specialist feels there is just evidence not to report the compound
as identified by the library search program. The lab should
include in the SDG Narrative the justification for not reporting a
compound as listed by the search program.
11.2.5.7 If the library search produces more than one compound at or above
85%, report the compound with the highest percent match (report
first compound if percent match is the same for two or more
compounds), unless the mass spectral interpretation specialist
feels that the highest match compound should not be reported, or
another compound with a lower match should be reported. The lab
should include in the Sample Delivery Group (SDG) Narrative the
justification for not reporting the compound with the highest
spectral match.
11.2.5.8 If the library search produces a series of obvious isomer -
compounds with library search matches greater than 85% (e.g.,
tetramethyl naphthalenes), the compound with the highest library
search percent match should be reported (or first compound if
library search matches are the same). A note should be placed in
the SDG Narrative indicating the exact isomer configuration as
reported may not be accurate.
11.2.5.9 If library search matches of less than 85% are produced and in the
technical judgement of the mass spectral interpretation
specialist, no valid tentative identification can be made, the
compound should be reported as unknown. The mass spectral
specialist should give additional classification of the unknown
compound, if possible (e.g., unknown phthalate, unknown
hydrocarbon, unknown acid type, unknown chlorinated compound). If
a probable molecular weight can be distinguished, include it.
11.2.5.10 The Contractor shall report pesticide target compounds listed in
Exhibit C (Pesticides) that appear as semivolatile tentatively
identified compounds.
11.3 Calculations for Target Compounds
11.3.1 Target compounds identified shall be quantitated by the internal
standard method. The internal standard used shall be the one
assigned to that analyte for quantitation (Table D-2). The Relative
D-31/SV . OLC03.2
-------
Exhibit D Semivolatiles -- Section 11
Data Analysis and Calculations (Con't)
Response Factor (RRF) from the continuing calibration analysis is
used to calculate the concentration in the sample. For samples
analyzed during the same 12-hour time period as the initial
calibration standards, use the RRF values from the mid-point initial
calibration standard.
11.3.2 Secondary ion quantitation is allowed only when there are sample
interferences with the primary ion. If secondary ion quantitation is
performed, document the reason in the SDG Narrative. The area of a
secondary ion cannot be used for the area of the primary ion unless a
relative response factor is calculated using the secondary ion.
NOTE: Unless otherwise stated, the area response is from the EICP of
the primary quantitation ion. The primary quantitation ions for the
target compounds, internal standards, and DMCs are listed in Table D-
3.
11.3.3 Calculate target compound concentrations using Equation 6.
EQ. 6
Where:
AX = Area response (EICP) of the characteristic ion for the
compound to be measured.
Ais = Area response (EICP) of the characteristic ion for the
internal standard. The target compounds are listed with
their associated internal standard in Table D-2.
Is '= Amount of internal standard injected in nanograms (ng).
RRF = Relative-response factor-from the most recent continuing
calibration as determined in Section 9.4.
V0 = Volume of water extracted in milliliters (mL).
Vi = Volume of extract injected in microliters (uL).
Vt = Volume of concentrated extract in microliters (uL).
(Vt = 1000 uL)
Df = Dilution Factor. The dilution factor for analysis of
water samples for semivolatiles by this method is defined
as follows:
uL most cone, extract used to make dilution + uL clean solvent
uL most cone, extract used to make dilution
If no dilution is performed, Df = 1.0.
11.3.4 When a target compound concentration is below the CRQL, but the
spectra meet the identification criteria, report the concentration
with a "J". For example, if the CRQL is 5.0 ug/L and a
concentration of 3.0 ug/L is calculated, report as "3.0 J". Report
ALL sample concentration data as UNCORRECTED for blanks.
OLC03.2 . D-32/SV
-------
Exhibit D Semivolatiles -- Section 11
Data Analysis and Calculations (Con't)
11.3.5 Calculate the adjusted CRQL for semivolatile compounds using Equation
7.
NOTE: If the adjusted CRQL is less than the CRQL listed in Exhibit C
(Semivolatiles), report the CRQL listed in Exhibit C (Semivolatiles).
EQ. 7
Contract Contract
Sample Vol Injection
Adjusted _ Contract, (1000 taL> --, Vt> , Vol (1 ufl.)
CRQL " CRQL v Contract V.
Ext. Vol
(1000 uL>
Where:
Contract CRQL = CRQL values reported in Exhibit C of the SOW.
V0 = Same as EQ. 6.
Vi = Same as EQ. 6.
Vt = Same .as EQ. 6.
Df = Same as EQ. 6.
11.3.6 It is expected that situations will arise where the automated
quantitation procedures in the GC/MS software provide inappropriate
quantitations. This normally occurs when there is compound co-
elution, baseline noise, or matrix interferences. In these
circumstances, the Contractor must perform a manual quantitation.
Manual quantitations are performed by integrating the area of the
quantitation ion of the compound. This integration shall only
include the area attributable to the specific TCL, DMC, or internal
standard compound. The area integrated shall not include baseline
background noise. The area integrated shall not extend past the
point where the sides of the peak intersect with the baseline noise.
Manual integration is not to be used solely to meet QC criteria, nor
is it to be used as a substitute for corrective action on the
chromatographic system. Any instance of manual integration must be
documented in the SDG Narrative.
11.3.7 In all instances where the data system report has been edited, or
where manual integration or quantitation has been performed, the
GC/MS operator must identify such edits or manual procedures by
initialing and dating the changes made to the report and shall
include the integration scan range. In addition, a hardcopy printout
of the EICP of the quantitation ion displaying the manual integration
shall be included in the raw data. This applies to all compounds
listed in Exhibit C (Semivolatiles), internal standards, and DMCs.
11.3.8 The requirements listed in 11.3.4 and 11.3.5 apply to all standards,
samples [including requested Matrix Spike/Matrix Spike Duplicate
(MS/MSD)], and blanks.
11.3.9 Internal Standard Responses and Retention Times
Internal standard responses and retention times in all samples and
blanks must be evaluated during or immediately after data
acquisition. Compare the sample/blank internal standard responses
D-33/SV OLC03.2
-------
Exhibit D Semivolatiles -- Section 11
Data Analysis and Calculations (Con't)
and retention times to the continuing calibration internal standard
responses and retention times. For samples and blanks analyzed
during the same 12-hour time period as the initial calibration
standards, compare the internal standard responses and retention
times against the 20 ng/uL (80 ng/uL for the seven compounds listed
in Section 7.2.3.4.1) calibration standard. The EICP of the internal
standards 'must be monitored and evaluated for each sample and blank.
11 . 4 Calculations for Non-Target Compounds
Equation 6 is used for calculating the concentrations of the non-target
compounds. Total area. counts (or peak heights) from the Reconstructed
Ion Chromatograms (RICs) are to be used for both the non-target compound
to be 'measured (A*) and the internal standard (Ais) . Associate the
nearest internal standard free of interferences with the non-target
compound to be measured. A RRF of one (1) is to be assumed. The value
from this quantitation shall be qualified as "J" (estimated due to lack
of a compound-specific relative response factor) , and "N" (presumptive
evidence of presence) , indicating the qualitative and quantitative
uncertainties associated with this non-target compound. This estimated
concentration must be calculated for all tentatively identified
compounds as well as those identified as unknowns.
11.5 Calculations for Deuterated Monitoring Compounds (DMCs)
11.5.1 Calculate the concentration of the DMCs using the same equation as
used for the target compounds.
11.5.2 Calculate the DMC percent recovery in all samples and blanks using
Equation 8. Determine if recovery is within limits (Table D-5) and
report on appropriate form.
EQ. 8
Percent fttccvtry - — « 100
Where:
Qd = Concentration or amount determined by analysis.
Qa = Concentration or amount added to sample/blank.
11 . 6 Technical Acceptance Criteria for Sample Analysis
11.6.1 The sample must be analyzed on a GC/MS system meeting the GC/MS
performance check, initial calibration, and continuing calibration
technical acceptance criteria.
11.6.2 The sample must be extracted and analyzed within the contract holding
times.
11.6.3 The sample must have an associated method blank meeting the blank
technical acceptance criteria.
11.6.4 The percent recovery for the DMCs in the sample must be within the
acceptance windows listed in Table D-5. Up to four DMCs per sample
may fail to meet the recovery limits listed in Table D-5.
OLC03.2 D-34/SV
-------
Exhibit D Semivolatiles -- Section 11
Data Analysis and Calculations (Con't)
NOTE: The DMC recovery requirements do not apply to a sample that has
been diluted.
11.6.5 The instrumental area response (EICP area) for each of the internal
standards in the sample must be within the inclusive range of -50
percent and +100 percent of its response in the most recent
continuing calibration standard analysis.
11.6.6 The retention time shift for each of the internal standards in the
sample must be within ±0.33 minutes (20.0 seconds) of its retention
time in the most recent continuing calibration standard analysis.
11.6.7 The RRT of each DMC in the sample must be within ±0.06 RRT units of
its relative retention time in the most recent continuing calibration
standard analysis.
11.6.8 Excluding those ions in the solvent front, no ion may saturate the
detector. No target compound concentration may exceed the upper
limit of the initial calibration range unless a more dilute aliquot
of the sample extract is also analyzed according to the procedures in
Section 10.2.5.
11.7 Corrective Action for Sample Analysis
11.7.1 If the sample technical acceptance criteria for the DMCs and internal
-..'•v~f'.. standards are not met, check calculations, DMC and internal standard
solutions, and instrument performance. It may be necessary to
recalibrate the instrument or take other corrective action procedures
••-.. • ::'.•• to meet the DMC and internal standard technical acceptance criteria.
11.7.2' • If the Contractor needs to analyze more than one (1) sample dilution
other than the original analysis to have all the target compounds
within the initial calibration range and to have no ions saturating
the detector (excluding.the peaks in the solvent front), contact
, Sample Management Office (SMO). SMO will contact the Region for
instructions.
11.7.3 Corrective actions for failure to meet instrument performance checks,
initial calibration, continuing calibration and method blanks must be
completed before the analysis of samples.
11.7.4 Sample analysis technical acceptance criteria MUST be met before data
is reported. Samples contaminated from laboratory sources or
associated with a contaminated method blank --or any samples
analyzed not meeting the technical acceptance criteria -- will
require re-extraction and/or re-analysis at no additional cost to
USEPA.
11.7.5 Sample reruns performed as a result of suspected matrix interferences
beyond the scope of the method will be reviewed on a case-by-case
basis for payment purposes by the USEPA Contract Laboratory Program
Project Officer (CLP PO). Send a copy of the SDG Narrative
(including your contract number), a description of the situation, and
the requested action to the CLP PO.
D-35/SV OLC03.2
-------
Exhibit D Semivolatiles -- Section 12
Quality Control
12.0 QUALITY CONTROL
12.1 Method Blank
12.1.1 Summary of Method Blank
A method blank is 1.0 liter (L) of reagent water carried through the
entire analytical scheme. The purpose of a method blank is to
determine the levels of contamination associated with the processing
and analysis of samples.
12.1.2 Frequency of Method Blank
12.1.2.1 A method blank must be extracted each time samples are extracted.
The number of samples extracted with each method blank shall not
exceed 20 field samples (excluding Matrix Spike/Matrix Spike
Duplicate(s) MS/MSD, if required, and Performance Evaluation (PE)
samples).
12.1.2.2 Each method blank must be analyzed on each Gas Chromatograph/Mass
Spectrometer (GC/MS) system used to analyze the samples prepared
with the method blank.
12.1.3 Procedure for Method Blank
-Measure out 1.0 L,of•reagent-water for. each, method blank aliquot.
Extract, concentrate and analyze the method blank at the same time as
the samples associated with the blank according to Section 10.
12.1.4 Calculations for Method Blank
Perform data analysis and calculations according to Section 11.
12.1.5 Technical Acceptance Criteria For Method Blank
12.1.5.1 All blanks must be analyzed at the/frequency described in Section
•12.1.2 on a GC/MS system meeting, the GC/MS-performance check,
initial calibration, and continuing calibration technical
acceptance criteria.
12.1.5.2 The percent recovery for each of the Deuterated Monitoring
Compounds (DMCs) in the blank must be within the acceptance
windows listed in Table D-5.
12.1.5.3 The area response for each of the internal standards in the blank
must be within the inclusive range of -50 percent and +100 percent
of its response in the most recent continuing calibration standard
analysis.
12.1.5.4 The retention time shift for each of the internal standards in the
blank must be within ±0.33 minutes (20.0 seconds) of its retention
time in the most recent continuing calibration standard analysis.
12.1.5.5 The Relative Retention Time (RRT) of each DMC in the blank must be
within ±0.06 RRT units of its relative retention time in the most
recent continuing calibration standard analysis.
12.1.5.6 The concentration of all target compounds (except the phthalate
esters listed in Exhibit C) in the blanks must be less than the
Contract Required Quantitation Limit (CRQL) for each target
compound. A method blank for semivolatile analysis must contain
less than five times (5X) the CRQL of the phthalate esters listed
OLG03.2 D-36/SV
-------
Exhibit D Semivolatiles -- Section 12
Quality Control (Con't)
in Exhibit C. The concentration of non-target compounds in the
blanks must not exceed 10 micrograms per liter (ug/L).
12.1.6 Corrective Action for Method.Blank
12.1.6.1 If a Contractor's blank does not meet the technical acceptance
criteria for method blanks the Contractor shall consider the
analytical system to be out of control.
12.1.6.2 It is the Contractor's responsibility to ensure that method
interferences caused by contaminants in solvents, reagents,
glassware, and sample storage and processing hardware that lead to
discrete artifacts and/or elevated baselines in gas chromatograms
be eliminated.
12.1.6.3 If contamination is a problem, the source of the contamination
must be investigated and appropriate corrective measures MUST be
taken and documented before further sample analysis proceeds.
Further, all samples (including requested MS/MSD and PE samples)
processed with a method blank that does not meet the blank
technical acceptance criteria (i.e., contaminated) will require
re-extraction and re-analysis at no additional cost to USEPA.
12.1.6.4 If DMC recoveries in the method blank do not meet the technical
acceptance criteria (Section 12.1.5.2), first re-analyze the
... :^i; method blank. If the DMC recoveries do not meet the technical
~ acceptance criteria after re-analysis, then all samples
4' (including requested MS/MSD and PE samples) associated with that
method blank must be re-extracted and re-analyzed at.no additional
cost to USEPA.
12.1.6.5 If the method blank fails to meet a technical acceptance criteria
other than Sections 12.1.5.6 and 12.1.5.2, then the problem is an
-•£» instrument problem. Correct the instrument problem, recalibrate
the instrument (if necessary), and re-analyze the method blank.
~'~ Sample analysis cannot proceed until the method blank meets these
•*~ ;:n- technical acceptance requirements.
12.2 Matrix Spike/Matrix Spike Duplicate (MS/MSD)
12.2.1 Summary of MS/MSD
In order to evaluate the effects of the sample matrix on the methods
used for semivolatile analyses, USEPA has prescribed a mixture of
semivolatile target compounds to be spiked into two aliquots of a
sample and analyzed in accordance with the appropriate method upon
request.
12.2.2 Frequency of MS/MSD Analyses
12.2.2.1 A matrix spike and matrix spike duplicate shall only be analyzed
if requested by the Region [(through the Sample Management Office
(SMO)] or specified on the Traffic Report (TR). If requested, a
matrix spike and matrix spike duplicate must be extracted and
analyzed for every 20 field samples in a Sample Delivery Group
(SDG), or each SDG, whichever is most frequent.
12.2.2.2 As part of USEPA's QA/QC program, water rinsate samples and/or
field/trip blanks (field QC) may be delivered to the laboratory
for analysis. The Contractor shall not perform MS/MSD analysis on
any of the field QC samples.
D-37/SV OLC03.2
-------
Exhibit D Semivolatiles -.- Section 12
Quality Control (Con't)
12.2.2.3 If the USEPA Region requesting MS/MSD designates a sample to be
used as an MS/MSD, then that sample must be used. If there is
insufficient sample remaining to perform an MS/MSD, then the
Contractor shall choose another sample on which to perform an
MS/MSD analysis. At the time the selection is made, the
Contractor shall notify the Region (through SMO) that insufficient
sample was received and identify the USEPA sample selected for the
MS/MSD analysis. The rationale for the choice of another sample
other than the one designated by USEPA shall be documented in the
SDG Narrative.
12.2.2.4 If there is insufficient sample remaining in any of the samples in
an SDG to perform the requested MS/MSD, then the Contractor shall
immediately contact SMO to inform them of the problem. SMO will
contact the Region for instructions. The Region will either
approve that no MS/MSD is required, or require that a reduced
sample aliquot be used for the MS/MSD analysis. SMO will notify
the Contractor of the Region's decision. The Contractor shall
document the decision in the SDG Narrative.
12.2.2.5 If it appears that the Region has requested MS/MSD analysis at a
greater frequency than specified in Section 12.2.2.1, then the
Contractor shall contact SMO. SMO will contact the Region to
determine which samples should have MS/MSD performed on them. SMO
will notify the Contractor of the Region's decision. The
Contractor shall document-the decision,in the SDG Narrative. If
this procedure is not followed, the Contractor will not be paid
for MS/MSD analysis performed at a greater frequency than required
by the contract.
12.2.2.6 When a Contractor receives only PE samples, no MS/MSD shall be
performed within that SDG.
12.2.2.7 When a Contractor receives a performance evaluation (PE) sample as
part of a larger SDG, a sample other than the PE sample must be
chosen for the requested MS/MSD analysis when the Region did not
designate a sample to be used for this purpose.
12.2.3 Procedure for Preparing MS/MSD
12.2.3.1 Measure out two additional 1 L aliquots of the sample chosen for
spiking in two continuous extractors. Add 1.0 mL of DMC spiking
solution (Section 7.2.3) and 1.0 mL of the matrix spiking solution
(Section 7.2.3.2) to each aliquot. Extract, concentrate, and
analyze the MS/MSD according to the procedures described in
Section 10.
12.2.4 Dilution of MS/MSD
MS/MSD samples must be analyzed at the same concentration as the most
concentrated extract for which the original sample results will be
reported. For example, if the original sample is to be reported at a
1:1 dilution and a 1:10 dilution, then analyze and report the MS/MSD
at a 1:1 dilution only. However, if the original sample is to be
reported at a 1:10 dilution and a 1:100 dilution, then the MS/MSD
must be analyzed and reported at a 1:10 dilution only. Do not
further dilute the MS/MSD samples to get either spiked or non-spiked
analytes within calibration range. Dilution of the sample must be
performed in accordance to the conditions in Section 10.2.5.
OLC03.2 . D-38/SV
-------
Exhibit D Semivolatiles -- Section 12
Quality Control (Con't)
12.2.5 Calculations for MS/MSD
12.2.5.1 Calculate the recovery of each matrix spike .compound in the matrix
spike and matrix spike duplicate samples and report on the
appropriate form. Calculate the concentrations of the matrix
spike compounds using the same equation as used for target
compounds (Equation 6). Calculate the recovery of each matrix
spike compound as follows:
EQ. 9
- SR
Spike Recovery • ±± _ * 100
Where:
SSR = Spike sample result.
SR = Sample result.
SA = Spike added.
12.2.5.2 Calculate the Relative Percent Difference (RPD) of the recoveries
of each compound in the matrix spike and matrix spike duplicate as
follows:
EQ. 10
RPD - I*8*" "*' » 100
= (HSR + KSDR>
Where:
MSR = Matrix spike recovery.
MSDR = Matrix spike duplicate recovery.
12.2.6 Technical Acceptance Criteria for MS/MSD
12.2.6.1 If requested, all MS/MSD must be prepared and analyzed at the
frequency described in Section 12.2.2. All MS/MSD must be
analyzed on a GC/MS system meeting decafluorotriphenylphosphine
(DFTPP), initial and continuing calibration technical acceptance
criteria, and the method blank technical acceptance criteria.
12.2.6.2 The MS/MSD must have an associated method blank meeting the blank
technical acceptance criteria.
12.2 .6.3 The MS/MSD must be extracted and analyzed within the contract
holding time.
12.2.6.4 The retention time shift for each of the internal standards must
be within ±0.33 minutes (20 seconds) between the MS/MSD sample and
the most recent continuing calibration standard.
12.2.6.5 The relative retention time for the DMCs must be within ±0.06 RRT
units of its standard retention time in the continuing calibration
standard.
D-39/SV 'OLC03.2
-------
Exhibit D Semivolatiles -- Section 12
Quality Control (Con't)
12.2.6.6 The limits for matrix spike compound recovery and RPD are given in
Table D-6. As these limits are only advisory, no further action
by the laboratory is required; however, frequent failures to meet
the limits for recovery or RPD warrant investigation by the
laboratory, and may result in questions from USEPA.
12 .2.6.7 Corrective Action for Matrix Spike/Matrix Spike Duplicate (MS/MSD)
Any MS/MSD which fails to meet the technical acceptance criteria
in Sections 12.2.6.1 through 12.2.6.5 must be re-analyzed at no
additional cost to USEPA.
12 .3 Method Detection Limit (MDL) Determination
12.3.1 Before any field samples are analyzed under this contract, the MDL
for each semivolatile target compound shall be determined for each
sample extraction procedure and on one of the instruments to be used
for sample analysis. The MDLs must be verified annually thereafter
(see Section 12.3.2 for MDL verification procedures), until the
contract expires or is terminated or after major instrument
maintenance. Major instrument maintenance includes, but is not
limited to cleaning or replacement of the mass spectrometer source,
mass filters (e.g., quadrupole, ion trap, etc.), or electron
multiplier (or similar device) , or replacement of gas chromatographic
column.
12.3.2 To determine the MDLs, the Contractor shall run an MDL study
following the procedures specified in 40.CFR Part 136. The
Contractor is only -required to analyze the MDL samples on one
instrument used for field sample analyses. MDL verification only is
then required on all other instruments used for field sample analysis
and at the frequency specified in Section 12.3.1. MDL verification
is achieved by analyzing a single reagent water blank spiked with .
each target compound at a concentration equal to two times the
analytical determined MDL. The resulting mass spectra of each target
compound must meet the qualitative identification criteria outlined
in Sections 11.1.1 through 11.1.4.3.
12.3.3 The determined concentration of the MDL must be less than the CRQL.
12.3.4 All documentation for the MDL studies shall be maintained at the
laboratory and provided to USEPA upon written request.
OLC03.2 D-40/SV
-------
Exhibit D Semivolatiles -- Sections 13-16
Method Performance
13.0 METHOD PERFORMANCE
Not Applicable.
14 . 0 POLLUTION PREVENTION
14.1 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.
.14.2 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.
15.0 WASTE MANAGEMENT
USEPA requires that laboratory waste management practices be conducted
^consistently 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 14.2.
16 . 0 ..'REFERENCES
Not Applicable.
D-41/SV OLC03.2
-------
Exhibit D Semivolatiles -- Section 17
Tables/Diagrams/Flowcharts
17.0 TABLES/DIAGRAMS/FLOWCHARTS
Table D-l
DFTPP KEY IONS AND ION ABUNDANCE CRITERIA
Mass Ion Abundance Criteria
51 30.0-80.0 percent of mass 198
68 Less than 2.0 percent of mass 69
69 Present
70 Less than 2.0 percent of mass 69
127 25.0 - 75.0 percent of mass 198
197 Less than 1.0 percent of mass 198
198 Base peak, 100 percent relative abundance (see note)
199 5.0 - 9.0 percent of mass 198
275 10.0 - 30.0 percent of mass 198
365 Greater than 0.75 percent of mass 198
441 Present but less than mass 443
442 40.0 - 110.0 percent of mass 198
443 15.0 - 24.0 percent of mass 442
NOTE: All ion abundances MUST be normalized to m/z 198, the nominal base
peak, even though the ion abundances of m/z 442 may be up to 110 percent
that of m/z 198.
OLC03.2 D-42/SV
-------
Exhibit D Semivolatiles -- Section 17
Tables/Diagrams/Flowcharts (Con't)
Table D-2
Send/volatile Internal Standards With Corresponding
Target and Deuterated Monitoring Compounds Assigned, for Quantitation
l,4-Dichlorobenzene-d4
Naphthalene-da
Acenaphthene - d10
Ben z a 1 dehyde
Phenol
bis(2-Chloroethyl)ether
2-Chlorophenol
2-Methylphenol
2,2'-oxybis-(1-Chloro-propane)
Ace tophenone
4-Methylphenol
N-Nitroso-Di-n-propylamine
Hexachloroethane
Phenol-ds (DMC)
Bis(2-chloroethyl)ether-d8 (DMC)
2-Chlorophenol-d4 (DMC)
4-Methylphenol-ds (DMC)
Nitrobenzene
Isophorone
2-Nitrophenol
2,4-Dimethylphenol
bis(2-Chloroethoxy)methane
2,4-Dichlorophenol
4 -Chioroani1ine
Hexachlorobutadiene
Caprolactam
4-Chloro-3-methylphenol
2-Methylnaphthalene
Naphthalene
Nitrobenzene-ds (DMC)
2 -Nitrophenol -d4 (DMC)
2,4-Dichlorophenol-d3 (DMC)
4-Chloroaniline-d, (DMC)
Hexachlorocyclopentadiene
2,4,6-Trichlorophenol
2,4,5-Trichlorophenol
1,1'-Biphenyl
2 - Chi or onapht ha 1 ene
2-Nitroaniline
Dimethylphthalate
Acenaphthylene
3-Nitroaniline
Acenaphthene
2,4-Dinitrophenol
4-Nitrophenol
Dibenzofuran
2,4-Dinitrotoluene
2,6-Dinitrotoluene
1,2,4,5-Tetrachlorobenzene
Diethylphthalate
4-Chlorophenyl-phenylether
Fluorene
4-Nitroaniline
Acenaphthylene-d8 (DMC)
4-Nitrophenol-d« (DMC)
Dimethylphthalate-d6 (DMC)
Fluorene-d10 (DMC)
D-43/SV
OLC03.2
-------
Exhibit D Semivolatiles -- Section 17
Tables/Diagrams/Flowcharts (Con't)
Table D-2 {Con't)
Semivolatile Internal Standards With Corresponding
Target and Deuterated Monitoring Compounds Assigned for Quantitation
Phenanthrene-d.
Chrysene-d12
Perylene-d12
4,6-Dinitro-2-methylphenol
N-nitrosodiphenylamine
4-Bromophenyl-phenylether
Hexachlorobenzene
Atrazine
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-butylphthalate
Fluoranthene
4,6-Dinitro-2-methylphenol-d2 (DMC)
Anthracene-dio (DMC)
Pyrene
Butylbenzylphthalate
3,3'-Dichlorobenzidine
Benzo(a)anthracene
bis(2-Ethylhexyl)phthalate
Chrysene
Pyrene-d10 (DMC)
Di-n-octylphthalate
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(1,2,3-cd)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
Benzo(a)pyrene-d12 (DMC)
OLC03.2
D-44/SV
-------
Exhibit D Semivolatiles -- Section 17
Tables/Diagrams/Flowcharts (Con't)
Table D-3
Characteristic Ions for Semivolatile Organic Compounds
Target Compounds
Ben z a 1 dehyde
Phenol
bis (2-Chloroethyl) ether
2 -Chlorophenol
2 -Methylphenol
2,2' -oxybis (1-Chloropropane)
Acetophenone
4 -Methylphenol
N-nitroso-di-n-propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2 , 4 -Dimethylphenol
bis ( -2 -Chloroethoxy) methane
2 , 4 -Dichlorophenol
Naphthalene
4 -Chloroaniline
Hexachlorobutadiene
Caprolactam
4 -Chloro- 3 -methylphenol
2 -Methylnaphthalene
Hexachlorocyclopentadiene
2 , 4 , 6-Trichlorophenol
2 , 4 , 5-Trichlorophenol
1,1' -Biphenyl
2 - Chloronaphthalene
2-Nitroaniline
Dimethyl phthalate
Acenaphthylene
3 -Nitroaniline
Acenaphthene
2 , 4 -Dinitrophenol
4-Nitrophenol
Dibenzofuran
2 , 4 -Dinitrotoluene
2 , 6 -Dinitrotoluene
Diethylphthalate
1,2,4,5 -Tetrachlorobenzene
4 -Chlorophenyl -phenylether
Fluorene
Primary Ion
77
94
93
128
108
45
105
108
70
117
77
82
139
107
93
162
128
127
225
113
107
142
237
196
196
154
162
65
163
152
138
153
184
109
168
165
165
149
216
204
166
Secondary Ion(s)
105, 106
65, 66
63, 95
64, 130
107
77, 79
77, 51
107
42, 101, 130
201, 199
123, 65
95, 138
65, 109
121, 122
95, 123
164, 98
129, 127
129
223, 227
55, 56
144, 142
141
235, 272
198, 200
198, 200
153, 76
164, 127
92, 138
194, 164
151, 153
108, 92
152, 154
63, 154
139, 65
139
63, 182
89, 121
177, 150
214, 179, 108, 143, 218
206, 141
165, 167
D-45/SV
OLC03.2
-------
Exhibit D Semivolatiles -- Section 17
Tables/Diagrams/Flowcharts (Con't)
Table D-3 (Con't)
Characteristic Ions for Semivolatile Organic Compounds
Target Compounds
4-Nitroaniline
4 , 6 -Dinitro-2 -methylphenol
N-Nitrosodiphenylamine
4 -Bromophenyl -phenylether
Hexachlorobenzene
Atrazine
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
3,3' -Dichlorobenzidine
Benzo (a) anthracene
bis (2-Ethylhexyl)phthalate
Chrysene
Di-n-octyl phthalate
Benzo (b) f luoranthene
Benzo (k) f luoranthene
Benzo (a) pyrene
Indeno ( 1 , 2 , 3 - cd ) pyrene
Dibenz (a, h) anthracene
Benzo (g , h , i ) perylene
Primary Ion
138
198
169
248
284
200
266
178
178
149
202
202
149
252
228
149
228
149
252
252
252
276
278
276
Secondary Ion(s)
92,
182
168,
250,
142,
173,
264,
179,
179,
150,
101,
101,
91,
254,
229,
167,
226,
253,
253,
253,
138,
139,
138,
108
, 77
167
141
249
215
268
176
176
104
100
100
206
126
226
279
229
-
125
125
125
227
279
277
Deuterated Monitoring Compounds
Phenol-ds 99 71, 42
bis-(2-Chloroethyl)ether-d8 67 99, 69
2-Chlorophenol-cU 132 134, 68, 66
4-Methylphenol-ds 113 115, 54
Nitrobenzene-d5 128 82, 54
2-Nitrophenol-d4 143 69, 41, 42
2,4-Dichlorophenol-d3 165 167, 101
4-Chloroaniline-d4 131 . 133, 69
Dimethylphthalate-d6. 166 78
Acenaphthylene-d8 160 80, 158
4-Nitrophenol-d, 143 113, 41, 42
Fluorene-d10 176 174, 87, 86
4,6-Dinitro-2-methylphenol-d2 200 170, 52
Anthracene-d10 188 94, 80
Pyrene-d10 212 106, 104
Benzo(a)pyrene-d12 264 132, 118
OLC03.2 D-46/SV
-------
Exhibit D Semivolatiles -- Section 17
Tables/Diagrams/Flowcharts (Con't)
Table D-3 (Con't)
Characteristic Ions for Semivolatile Organic Compounds
Internal Standard Compounds Primary Ion Secondary Ion(s)
l,4-Dichlorobenzene-d4 152 . 115
Naphthalene-d8 136 . 68
Acenapthene-d10 164 162, 160
Phenanthrene-d10 188 94, 80
Chrysene-d12 240 120, 236
Perylene-d12 264 260, 265
D-47/SV OLC03.2
-------
Exhibit D Semivolatiles - Section 17
Tables/Diagrams/Flowcharts (Con't)
Table D-4
Acceptance Criteria for Initial and Continuing Calibration of
Semivolatile Target Compounds and Deuterated Monitoring Compounds
Semivolatile Compounds
Benzaldehyde
Phenol
bis- (2-Chloroethyl) ether
2 -Chlorophenol
2 -Methylphenol
2,2' -oxybis- (1-Chloropropane)
Acetophenone
4 -Methylphenol
N-Nitroso-di-n-propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2 -Nitrophenol
2 , 4 -Dimethylphenol
bis- (2-Chloroethoxy) methane
2 , 4 -Dichlorophenol
Naphthalene
4 -Chloroaniline
Hexachlorobutadiene
Caprolactam
4 -Chloro- 3 -Methylphenol
2 -Methylnaphthalene
Hexachlorocyclopentadiene
2,4,6 -Trichlorophenol
2,4,5 -Trichlorophenol
1,1' -Biphenyl
2 -Chloronaphthalene
2 -Nitroaniline
Dimethylphthalate
2 , 6-Dinitrotoluene
Acenaphthylene
3 -Nitroaniline
Acenaphthene
2 , 4 -Dinitrophenol
4 -Nitrophenol
Dibenzofuran
2 , 4 -Dinitrotoluene
Diethylphthalate
1,2,4, 5-Tetrachlorobenzene
4 -Chlorophenyl -phenylether
Fluorene
4 -Nitroaniline
4 , 6 -Dinitro-2 -Methylphenol
4 -Bromophenyl -phenylether
N-Nitrosodiphenylamine
Hexachlorobenzene
Atrazine
Pentachlorophenol
Phenanthrene
Minimum RRF
0.010
0.800
0.700
0.800
0.700
0.010
0.010
0.600
0.500
0.300
0.200
0.400
0.100
0.200
0.300
0.200
0.700
0.010
0.010
0.010
0.200
0.400
0.010
0.200
0.200
0.010
0.800
0.010
0.010
0.200
0.900
0.010
0.900
0.010
0.010
0.800
0.200 .
0.010
0.010
0.400
0.900
0.010
0.010
0.100
0.010
0.100
0.010
0.050
0.700
Maximum %RSD
none
20.5
20.5
20.5
20.5
none
none
20.5
20.5
20.5
20.5
20.5
30.0
30.0
20.5
20.5
20.5
none
none
none
20.5
20.5
none
20.5
20.5
none
20.5
none
none
20.5
20.5
none
20.5
none
none
20.5
30.0
none
none
20.5
20.5
none
none
20.5
none
20.5
none
20.5
20.5
Maximum %Diff
none
±25.0
±25.0
±25.0
±25.0
none
none
±25.0
±25.0
±25.0
±25.0
±25.0
' ±30.0
±30.0
±25.0
±25.0
±25.0
none
none
none
±25.0
±25.0
none
±25.0
±25.0
none
±25.0
none
none
±25.0
±25.0
none
±25.0
none
none
±25.0
±30.0
none
none
±25.0
±25.0
none
none
±25.0
none
±25.0
none
±25.0
±25.0
OLC03.2
D-48/SV
-------
Exhibit D Semivolatiles -- Section 17
Tables/Diagrams/Flowcharts (Con't)
Table D-4 (Con't)
Acceptance Criteria for Initial and Continuing Calibration of
Semivolatile Target Compounds and Deuterated Monitoring Compounds
Semivolatile Compounds
Anthracene
Di-n-butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
3,3' -Dichlorobenzidine
Benzo (a) anthracene
Chrysene
bis- (2-Ethylhexyl)phthalate
Di -n-Octylphthalate
Benzo (b) f luoranthene
Benzo (k) f luoranthene
Benzo (a) pyrene
Indeno ( 1 , 2 , 3 - cd ) pyrene
Dibenzo (a, h) anthracene
Benzo (g,h, i)perylene
Deuterated Monitoring Compounds
Phenol -d5
bis- ( 2 -Chloroethyl) ether-da
2-Chlorophenol-d4
4-Methylphenol-d8
Nitrobenzene-ds
2 -Nitrophenol -d4
2,4 -Dichlorophenol -d3
4-Chloroaniline-cl,
Dimethylphthalate-d6
Acenaphthylene - dB
4 -Nitrophenol -d4
Fluorene-d10
4, 6-Dinitro-2-methylphenol-d2
Anthracene-d10
Pyrene -d10
Benzo ( a ) pyrene - d12
Minimum RRF
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.700
.010
.600
.600
.010
.010
.800
.700
.010
.010
.700
.700
.700
.500
.400
.500
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
Maximum %RSD
20.5
none
20.5
20.5
none
none
20.5
20.5
none
none
20.5
20.5
20.5
20.5
20.5
20.5
none
npne
none
none
none
none
none
none
none
none
none
none
none
none
none
none
Maximum %Diff
±25.0
none
±25.0
±25.0
none
none
±25.0
±25.0
none
none
±25.0
±25.0
±25.0
±25.0
±25.0
±25.0
none
none
none
none
none
none
none
none
none
none
none
none
none
none
none
none
D-49/SV
OLC03.2
-------
Exhibit D Semivolatiles - Section 17
Tables/Diagrams/Flowcharts (Con't)
Table D-5
Deuterated Monitoring Compound Recovery Limits
Compound
Phenol-ds
bis-(2-Chloroethyl)ether-da
2-Chlorophenol-dj
4-Methylphenol-dB
Nitrobenzene-ds
2-Nitrophenol-d,
2,4-Dichlorophenol-d3
4-Chloroani1ine-d<
Dimethylphthalate-d6
Acenaphthylene-da
4-Nitrophenol-d4
Fluorene-d10
4,6-Dinitro-2-methylphenol-d2
Anthracene -d10
Pyrene-d10
Benzo (a) pyrene-d12
% Recovery
10-110
41-94
33-liO
38-95
35-114
40-106
42-98
8-70
62-102
49-98
9-181
50-97
53-153
55-116
47-114
54-120
OLC03.2
D-50/SV
-------
Exhibit D Semivolatiles -- Section 17
Tables/Diagrams/Flowcharts (Con't)
Compound
Table D-6
Matrix Spike Recovery and Relative Percent Difference Limits
% Recovery
RPD
Phenol
2-Chlorophenol
N-Nitroso-di-n-propylamine
4-Chloro-3-methylphenol
Acenaphthene
4-Nitrophenol
2,4-Dinitrotoluene
Pentachlorophenol
Pyrene
12-110
27-123
41-116
23-97
46-118
10-80
24-96
9-103
26-127
42
40
38
42
31
50
38
50
31
D-51/SV
OLC03.2
-------
EXHIBIT D
METHOD FOR THE ANALYSIS OF LOW CONCENTRATION WATER FOR
PESTICIDES AND AROCLORS
D-l/PEST OLC03.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
OLC03.2 D-2/PEST
-------
Exhibit D -- Analytical Methods for Pesticides/Aroclors
Table of Contents
Page
1.0 SCOPE AND APPLICATION. 5
2.0 SUMMARY OF METHOD . . . . : 6
3.0 DEFINITIONS 6
4.0 INTERFERENCES 7
4.1 Method Interferences 7
4.2 Matrix Interferences 7
5.0 SAFETY 7
6.0 EQUIPMENT AND SUPPLIES 8
6.1 Glassware 8
6.2 Florisil Cleanup Equipment 9
6.3 pH Paper 9
6.4 pH Meter 9
6.5 Boiling Chips 9
6.6 Water Bath 9
6.7 Balances 9
6.8 Nitrogen Evaporation Device 9
6.9 Mechanical Shaker or Mixer 9
6.10 Gas Chromatograph/Electron Capture Detector (GC/ECD) System 10
7.0 REAGENTS AND STANDARDS 13
7.1 Reagents 13
7.2 Standards 14
8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE 18
8.1 Sample Collection and Preservation 18
8.2 Procedure for Sample Storage 18
8.3 Procedure for Sample Extract Storage 18
8.4 Records for Sample and Sample Extract Storage 18
8.5 Contract Required Holding Times 18
9.0 CALIBRATION AND STANDARDIZATION 19
9.1 Gas Chromatograph (GC) Operating Conditions 19
9.2 Initial Calibration 19
9.3 Calibration Verification 26
10.0 PROCEDURE 31
10.1 Sample Preparation 31
10.2 GC Analysis 39
11.0 DATA ANALYSIS AND CALCULATIONS 43
11.1 Qualitative Identification of Target Compounds 43
11.2 Calculations 43
11.3 Technical Acceptance Criteria for Sample Analyses 46
11.4 Corrective Action for Sample Analysis ....'. ' 47
12.0 QUALITY CONTROL 49
12.1 Blank Analyses 49
12.2 Laboratory Control Sample (LCS) 53
12.3 Matrix Spike/Matrix Spike Duplicate (MS/MSD) .' 54
12.4 Method Detection Limit (MDL) Determination 57
D-3/PEST OLC03.2
-------
Exhibit D -- Analytical Methods for Pesticides/Aroclors
Table of Contents (Continued)
Page
13 . 0 METHOD PERFORMANCE 58
14 . 0 POLLUTION PREVENTION ' 58
15.0 WASTE MANAGEMENT . . 58
16.0 REFERENCES 58
17.0 TABLES/DIAGRAMS/FLOWCHARTS 59
OLC03.2 • D-4/PEST
-------
Exhibit D Pesticides/Aroclors -- Section 1
Scope and Application
1. 0 SCOPE AND 'APPLICATION
1.1 The analytical method that follows is designed to analyze water in order
to determine the presence and concentrations of the chlorinated
pesticides and Aroclors found in the Target Compound List (Exhibit C -
Pesticides). The majority of the samples are expected to be from
drinking water and well/ground water type sources around Superfund
sites. The method can be used for determining analyte concentrations as
low as ten parts per trillion. The method is based on EPA Method 608.
The method includes sample extraction, extract cleanup techniques, and
the Gas Chromatograph/Electron Capture Detector (GC/ECD) analytical
method for chlorinated pesticides and aroclors.
1.2 Resolution difficulties have been associated with the following pairs of
compounds using this method:
• On a DB-608 or equivalent column, DDE and Dieldrin,- Methoxychlor arid
Endrin ketone; and Endosulfan I and gamma-Chiordane.
• On a DB-1701 or equivalent column, Endosulfan I and gamma-Chlordane;
and Methoxychlor and Endosulfan sulfate.
1.3 There are two isomers of heptachlor epoxide, the endo epoxy isomer
(isomer A) and the exo epoxy isomer (isomer B). The two isomers are
separable using current GC capillary columns. Only the exo epoxy isomer
(isomer B) is of environmental significance. This is the isomer that
must be used as an analytical standard, identified and quantitated in
.sample analysis, and reported on appropriate forms as heptachlor
epoxide.
D-5/PEST OLC03.2
-------
Exhibit D Pesticides/Arociors -- Sections 2 & 3
Summary of Method
2.0 SUMMARY OF METHOD
2.1 A one liter aliquot of sample is spiked with the surrogate solution and
extracted with methylene chloride by using a continuous liquid-liquid
extractor or separatory funnel. The methylene chloride extract is dried
and concentrated, exchanged to hexane, cleaned up to remove
interferences, and adjusted to a final volume of 2.0 milliliters (mL).
2.2 The hexane extract is injected onto two wide-bore capillary columns in a
Gas Chromatograph (GO. The GC is temperature programmed to separate
the pesticides and Aroclors which are then detected with an Electron
Capture Detector (BCD). Calibration and run sequence specifications of
the GC/ECD method apply independently to each GC column.
2.3 A single component pesticide is identified if a peak is detected within
its appropriate Retention Time (RT) window on each of two GC columns.
Quantitative analysis of pesticides/Aroclors must be accomplished by the
external standard method. Single component analytes and the surrogates
must be analyzed at three concentration levels during the initial
calibration.
2.4 Toxaphene and Aroclors are identified primarily by pattern recognition,
but RTs of three to five major peaks must also be taken into
consideration. Single-point calibrations for multicomponent analytes
are sufficient for quantitation by this method. Standards for
identified Aroclors and Toxaphene must be run within 72 hours of the
sample analysis in which they were observed. These standards are used
to verify identification only; quantitation is based on the standards
analyzed during initial calibration.
3.0 DEFINITIONS
See Exhibit G for a complete list of definitions.
OLC03.2 D-6/PEST
-------
Exhibit D Pesticides/Aroclors -- Sections 4 & 5
Interferences
4.0 INTERFERENCES
4 .1 Method Interferences
Method interferences may be caused by contaminants in solvents,
reagents, glassware, and sample processing hardware. These contaminants
lead to discrete artifacts or to elevated baselines in gas
chromatograms. These materials must be routinely demonstrated to be
free from interferences under the sample preparation and analysis
conditions by analyzing instrument blanks and method blanks.
Interferences caused by phthalate esters can pose a major problem in
pesticide analysis. Because common flexible plastics contain varying
amounts of phthalates which are easily extracted during laboratory
operations, cross-contamination of glassware frequently occurs when
plastics are handled. Interferences from phthalates can best be
minimized by avoiding the use of such plastics in the laboratory.
4.2 Matrix Interferences
Matrix interferences may be caused by contaminants that are co-extracted
from the sample. The extent of matrix interferences will vary
considerably from source to source, depending upon the nature of the
site being sampled. The cleanup procedures in this method must be used
to remove such interferences in order to achieve the Contract Required
Quantitation Limits (CRQL).
5.0 SAFETY
5.1 The toxicity or carcinogenicity of each reagent used in this method has
not been precisely determined; however, each chemical should be treated
as a potential health hazard. Exposure to these reagents should be
reduced to the lowest possible level. The laboratory is responsible for
maintaining a current awareness file of OSHA regulations regarding the
safe handling of the chemicals specified in this method. A reference
file of data handling sheets should be made available to all personnel
involved in these analyses. -Specifically, concentrated sulfuric acid
and the 10 N sodium hydroxide solution are moderately toxic and
extremely irritating to skin and mucous membranes. Use these reagents
in a fume hood whenever possible and if eye or skin contact occurs,
flush with large volumes of water. Always wear safety glasses or a
shield for eye protection, protective clothing, and observe proper
mixing when working with these reagents.
5.2 The following analytes covered by this method have been tentatively
classified as known or suspected human or mammalian carcinogens: 4,4'-
DDT, 4,4'-DDD, the BHCs, and the Aroclors. Primary standards of these
toxic compounds should be prepared in a hood. A NIOSH/MESA approved
toxic gas respirator should be worn when the analyst handles high
concentrations of these toxic compounds.
D-7/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- 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,
but demonstration of equivalent performance meeting the requirements of
the Statement of Work (SOW) is the responsibility of the Contractor.
The Contractor must document in its Sample Delivery Group (SDG)
Narrative when it uses equipment and supplies other than those specified
here.
6.1 Glassware
6.1.1 Continuous Liquid-Liquid Extractors
Continuous Liquid-Liquid Extractors equipped with PTFE or glass
connecting joints and stopcocks requiring no lubrication (Hershberg-
Wolf extractor, Ace Glass Company, Vineland, NJ P/N 6841-10 or
equivalent) or Hydrophobic Membrane-based Extractor (Accelerated One
Step™ Extractor, Corning series 3195 or equivalent).
6.1.2 Separatory Funnels - 2 liter with PTFE stopcock. '
6.1.3 Graduated Cylinder - 1 liter capacity.
6.1.4 Drying column, chromatographic column approximately. 400 millimeters
(mm) long x 19 mm ID, with coarse frit. (Substitution of a small pad
of disposable Pyrex glass wool for the frit will help prevent cross-
contamination of sample extracts.)
6.1.5 Kuderna-Danish Apparatus
6.1.5.1 Concentrator Tubes - 10 milliliters (mL), graduated (Kontes,
K-570050-1025, or equivalent).
6.1.5.2 Evaporative Flasks - 500 mL (Kontes K-570001-0500, or equivalent).
Attach to concentrator tube with springs.
6.1.5.3 Snyder Columns - three-ball macro (Kontes K-50300-0121, or
equivalent).
6.1.5.4 • Snyder Columns, micro two or three ball with a 19 mm ground glass
joint.
6.1.6 Pipet, Volumetric 1.00 mL or 2.00 mL.
6.1.7 Microsyringe, 1.0 microliter (uL) and larger, 0.006 (0.15 mm) inch ID
needle.
6.1.8 Syringe, 1.00 mL or 2.00 mL (optional).
6.1.9 Volumetric flask, 10.00 mL, and 1 or 2 mL.
6.1.10 Vials and caps, 20 and 10 mL, with screw cap and PTFE or aluminum
foil liner, 2 or 1 mL for Gas Chromatograph (GC) auto sampler.
6.1.11 Bottle or test tube, 20 mL with PTFE-lined screw cap for sulfur
removal.
6.1.12 Centrifuge tubes, calibrated, 12 mL, for sulfur removal.
6.1.13 Micropipet, 200 uL, with disposable tips.
OLC03.2 D-8/PEST
-------
Exhibit D Pesticides/Aroclors — Section 6
Equipment and Supplies (Con't)
6.2 Florisil Cleanup Equipment
6.2.1 Florisil bonded silica. 1 g cartridges with stainless steel or PTFE
frits. Catalog No. 694-313 (Analytichem, 24201 Frampton Ave., Harbor
City, CA, or equivalent).
6.2.2 Vacuum system for eluting multiple cleanup cartridges. Vac Elute
Manifold, Analytichem International, J.T. Baker, or Supelco (or
equivalent).
6.2.3 Vacuum trap made from a 500 mL sidearm flask fitted with a one-hole
stopper and glass tubing. -
6.2.4 Vacuum pressure gauge.
6.2.5 Rack for holding 10 mL volumetric flasks in the manifold.
NOTE: Other types of equivalent systems, such as an automated system
using syringe pressure are considered acceptable for elution of
Florisil cartridges, as long as all quality control (QC) and sample
technical acceptance criteria are met.
6.3 pH Paper, Wide Range
6.4 pH Meter — - With a combination glass electrode. Calibrate according to
manufacturer's instructions. pH meter must be calibrated prior to each
use.
6.5 Boiling Chips
6.5.1 Silicon carbide boiling chips, approximately 10 to 40 mesh. Heat the
chips to 400°C for 30 minutes or solvent rinse before use.
6.5.2 PTFE boiling chips (optional). Solvent rinse the chips before use.
6.6 Water Bath, heated, with concentric ring cover, capable of temperature
control.
NOTE: To prevent the release of solvent fumes into the laboratory, the
water bath must be used in a hood.
6.7 Balances
Analytical balances, capable of weighing accurately to ±0.0001 g. The
balances must be calibrated with class S weights or known reference
weights once per each 12-hour work shift. The balances must be
calibrated with class S weights at a minimum of once per month. The
balances must also be -annually checked by a certified technician.
6.8 Nitrogen Evaporation Device
Nitrogen evaporation device equipped with a heated bath that can be
maintained at 35 to 40°C (N-Evap by Organomation Associates, Inc., South
Berlin, MA, or equivalent). To prevent the release of solvent fumes
into the laboratory, the nitrogen evaporation device must be used in a
hood.
6.9 Mechanical Shaker or Mixer, for Sulfur Removal
D-9/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section S
Equipment and Supplies (Con't)
6.10 Gas Chromatograph/Electron Capture Detector (GC/ECD) System
6.10.1 Gas Chromatograph (GC)
6.10.1.1 The GC must adequately regulate temperature in order to give a
reproducible temperature program and have a flow controller that
maintains a constant column flow rate throughout temperature
program operations. The system must have all required accessories
including syringes, analytical columns, and gases.
6.10.1.2 GCs that are available from some manufacturers may have difficulty
in meeting certain method QC requirements because of endrin and
DDT breakdown in the injector. This problem can be minimized by
operating the injector at 200-205°C, using a Pvrex (not quartz)
methyl silicone deactivated injector liner, and deactivating the
metal parts in the injector with dichlorodimethyl silane. In some
cases, using a 0.25 inch packed column injector converted for use
with 0.53 mm capillary columns works better than a Grob-type
injector. If a Grob-type injector is used, a 4 mm liner may be
required to meet breakdown criteria.
6.10.1.3 Gas Chromatograph Columns .-- Two wide-bore (0.53 mm ID) fused
silica GC columns are required. A separate detector is required
for each column. The specified analytical columns are a 30 m x
0.53 mm ID, 1.0 urn film thickness DB-1701 (J&W Scientific); SPB
1701 (Supelco); AT 1701 (Alltech); RTX-1701 (Restek); CP-Sil 19CB
(Chrompack); 007-1701 (Quadrex); BP-10 (SGE); or'equivalent, and a
30 m x 0.53 mm ID, 0.5 to 1.0 micrometer (• m) film thickness DB-
608 (J&W Scientific); HP-608 (Hewlett Packard); SPB-608 (Supelco);
007-608 (Quadrex); BP-608 (SGE); CP-Sil 8CB (Chrompack); or
equivalent.
NOTE: The column length stated above is the minimum requirement.
Longer columns that meet resolution and calibration requirements
may be used. A description of the GC columns used for analysis
shall be provided in the SDG Narrative.
6.10.1.3.1 A capillary column is considered equivalent if:
• The column does not introduce contaminants which, interfere
with identification and quantitation of the compounds
listed in Exhibit C (Pesticides).
• The analytical results generated using the column meet the
initial calibration and calibration verification technical
acceptance criteria listed in the SOW and the Contract
Required Quantitation Limits (CRQLs) listed in Exhibit C
(Pesticides).
•' The column can accept at least 16 times the low point
standard for individual standard mixtures A and B for each
compound listed in Exhibit C (Pesticides) without becoming
overloaded.
• The column pair chosen must have dissimilar phases/chemical
properties in order to separate the compounds of interest
in different Retention Time (RT) order.
6.10.1.3.2 Although the instructions included in the SOW are for wide bore
capillary columns, narrower bore capillary columns may be
evaluated for use. Follow manufacturer's instructions for use
OLC03.2 D-10/PEST
-------
Exhibit D Pesticides/Aroclors — Section 6
Equipment and Supplies (Con't)
of its product. Document in SDG Narrative if other columns are
used'by specifying the column used (Exhibit B Section 2.5.1) .
6.10.1.3.3 As applicable, follow the manufacturer's instructions for use
of its product.
6.10.1.3.4 The Contractor must maintain documentation that the alternate
column met the criteria in Sections 9.2.5 and 9.3.5. The
minimum documentation is as follows:
6.10.1.3.4.1 Manufacturer provided information concerning the performance
characteristics of the column;
6.10.1.3.4.2 GC chromatograms and data system reports generated on the
GC/ECD and used for CLP analyses:
• From instrument blanks which demonstrate that there are
no contaminants which interfere with the pesticide
analysis when using the alternate column;
• For initial calibration standards analyzed using the
alternate column; and
• For calibration verification standards analyzed using
the alternate column.
6.10.1.3.5 Based on the Contractor generated data described in Section
6.10.1.3.4.2, the Contractor must complete a written comparison
and review, signed by the Laboratory Manager certifying that:
• The alternate column performance is comparable to the
required column performance in its ability to produce
initial calibrations and calibration verifications which
meet the technical acceptance criteria in Sections 9.2.5
and 9.3.5;
• The low point initial calibration standard analyses have
adequate sensitivity to meet the pesticide CRQLs;
• The high point initial calibration standard analyses were
not overloaded; and
• The alternate column does not introduce contaminants which
interfere with identification and quantitation of compounds
listed in Exhibit C (Pesticides).
6.10.1.3.6 The documentation must be made available to USEPA during on-
site laboratory evaluations or sent to USEPA upon request of
the Contract Laboratory Program Project Officer (CLP PO).
6.10.1.3.7 PACKED COLUMNS CANNOT BE USED.
6.10.1.4 Columns are mounted in a 0.25-inch injector ports by using glass
adapters available from a variety of commercial sources (J&W
Scientific, Supelco, Inc., Hewlett-Packard, Varian, Inc., Perkin
Elmer, or equivalent). The two columns may be mounted into a
single injection port with a tee adapter (Supelco, Inc.,
Bellefonte, PA, Catalog No. 2-3660, or equivalent). Use of this
adapter allows simultaneous injection onto both columns. The
laboratory should follow manufacturer's recommendations for
mounting 0.53 mm capillary columns in injector ports.
D-11/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors — Section 6
Equipment and Supplies (Con't)
6.10.1.5 The carrier gas for routine applications is helium. Laboratories
may choose to use hydrogen as a carrier gas, but they must clearly
identify its use in the SDG Narrative and on all divider pages
preceding raw chromatographic data in submissions to USEPA.
Laboratories that choose to use hydrogen are advised to exercise
caution in its use. Use of a hydrogen leak detector is highly
recommended when hydrogen is used as the carrier gas. All GC
carrier gas lines must be constructed from stainless steel or
copper tubing. Non-polytetrafluoroethylene (PTFE) thread sealants
or flow controllers with rubber components are not to be used.
6.10.2 Electron Capture Detector (BCD)
The linearity of the response of the BCD may be greatly dependent on
the flow rate of the make-up gas. The make-up gas must be P-5, P-10
(argon/methane) or nitrogen according to the instrument
specification. Care must be taken to maintain stable and appropriate
flow of make-up gas to the detector. The GC/ECD system must be in a
room in which the atmosphere has been demonstrated to be free of all
contaminants which may interfere with the analysis. The instrument
must be vented to outside the facility or to a trapping system which
prevents the release of contaminants into the instrument room.
6.10.3 Data System
A data system must be interfaced to the GC/ECD. The data system must
allow the continuous acquisition of data throughout the duration of
the chromatographic program and must permit, at the minimum, the
output of time vs. intensity (peak height or peak area) data. Also,
the data system must be able to rescale chromatographic data in order
to report chromatograms meeting the requirements listed within this
method.
6.10.4 Magnetic Tape Storage Device
Magnetic tape storage devices must be capable of recording data and
suitable for long-term, off-line storage of GC/ECD data.
OLC03.2 D-12/PEST
-------
Exhibit D Pesticides/Aroclors -- Section 7
Reagents and Standards
7.0 REAGENTS AND STANDARDS
7.1 Reagents
Reagents shall be dated with the receipt date and used on a first-in,
first-out basis. The purity of the reagents shall be verified before
use.
7.1.1 Reagent water -- Defined as water in which no target analyte is
observed at the Contract Required Quantitation Limits (CRQL) for that
compound.
7.1.1.1 Reagent water may be generated by passing tap water through a
carbon filter bed containing about 453 grams (g) (1 pound) of
activated carbon (Calgon Corp., Filtrasorb-300, or equivalent).
7.1.1.2 Reagent water may be generated using a water purification system
(Millipore Super-Q or equivalent).
7.1.2 Sodium sulfate, granular-anhydrous reagent grade, heated at 400°C for
4 hours, or at 120°C for 16 hours, cooled in a desiccator, and stored
in a glass bottle. Each lot must be extracted with hexane and
analyzed by Gas Chromatograph/Electrdn Capture Detector (GC/ECD) to
demonstrate that it is free of interference before use. J. T. Baker
anhydrous granular, Catalog No. 3375, or equivalent.
CAUTION: An open container of sodium sulfate may become contaminated
during storage in the laboratory.
7.1.3 Methylene chloride, hexane, acetone, toluene, iso-octane, and
methanol (optional), pesticide quality, or equivalent. It is
recommended that each lot of solvent be analyzed to demonstrate that
it is free of interference before use. Methylene chloride must be
certified as acid free or must be tested to demonstrate that it is
free of hydrochloric acid. Acidic methylene chloride must be passed
through basic alumina and then demonstrated to be free of
hydrochloric acid.
7.1.4 Mercury, triple distilled, for sulfur clean-up.
7.1.5 Copper powder (optional), fine, granular (Mallinckrodt 4649 or
equivalent). Copper may be used instead of mercury for sulfur clean-
up. Remove oxides by treating with dilute nitric acid, rinse with
distilled water to remove all traces of acid, rinse with acetone, and
dry under a stream of nitrogen.
7.1.6 Sodium hydroxide solution (10 N). Carefully dissolve 40 g of NaOH in
reagent water and dilute the solution to 100 milliliters (mL).
7.1.7 Concentrated sulfuric acid, (Sp. Gr. 1.84)-36N.
7.1.8 Nitric acid, dilute, for sulfur removal with copper.
7.1.9 Ten percent acetone in hexane (v/v). Prepare by adding 10.0 mL of
acetone to 90.0 mL of hexane.
NOTE: Prepare this mixture accurately or the results from the
Florisil cartridge cleanup will be adversely affected. Water in the
acetone will also adversely affect Florisil performance.
D-13/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 7
Reagents and Standards (Con't)
7.2 Standards
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. 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 Stock Standard Solutions
7.2.1.1 Stock standard solutions may be purchased as certified solutions
or prepared from pure standard materials.
7.2.1.2 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure material. Dissolve the material in toluene,
dilute to volume in a 10 mL volumetric flask with toluene or
acetone. Larger volumes may be used at the convenience of the
analyst.
7.2.1.3 When compound purity is assayed to be 97 percent or greater, the
weight may be used without correction to calculate the
concentration of the stock solution. If the compound purity is
assayed to be less than -97 percent, the weight must be corrected
when calculating the concentration of the stock solution.
7.2.1.4 Fresh stock standards must be prepared once every six months, or
sooner, if standards have degraded or concentrated. Stock
standards must be checked for signs of degradation or
concentration just prior to preparing working standards from them.
7.2.2 Secondary Dilution Standards
7.2.2.1 Using stock standards, prepare secondary dilution standards in
acetone that contain the compounds of interest either singly or
mixed together.
7.2.2.2 Fresh secondary dilution standards must be prepared once every six
months, or sooner, if standards have degraded or concentrated.
Secondary dilution standards must be checked for signs of
degradation or concentration just prior to preparing working
standards from them.
7.2.3 Working Standards
.7.2.3.1 Surrogate Standard Spiking Solution
The surrogates, tetrachloro-m-xylene and decachlorobiphenyl, are
added to all standards, samples (including Laboratory Control
Samples), matrix spike, matrix spike duplicates and if required,
Performance Evaluation (PE) samples, and required blanks
(method/sulfur clean-up/instrument). Prepare a surrogate spiking
.solution of 0.20 micrograms per milliliter (ug/mL) of each of the
two compounds in acetone. The solution should be checked
frequently for stability. The solution must be replaced every 6
months, or sooner if the solution has degraded or concentrated.
7.2.3.2 Matrix Spiking Solution
Prepare a matrix spiking solution in acetone or methanol that
contains the following pesticides at the concentrations specified.
The solution must be replaced every six months, or sooner if the
solution has degraded or concentrated.
OLC03.2 ' D-14/PEST
-------
7.2.3.3
Exhibit D Pesticides/Aroclors -- Section 7
Reagents and Standards (Con't)
Pesticide
gamma- BHC (Lindane)
4,4'-DDT
Endrin
Heptachlor
Aldrin
Dieldrin
Resolution Check Mixture
• Concentration (uq/mL)
0.1
0.2
0.2
0.1
0.1
0.2
The Resolution Check Mixture is composed of the pesticides and
surrogates at the concentrations listed below in hexane or iso-
octane. The mixture must be prepared every six months, or sooner,
if the solution has degraded or concentrated.
Compounds
gamma- Chlordane
Endosulfan I
4,4'-DDE
Dieldrin
Endosulfan sulfate
Endrin ketone
Methoxychlor
Tetrachloro-m-xylene
Decachlorobiphenyl
Concentration (na/mL)
10.0
10.0
20.0
20.0
20.0
20.0
100.0
20.0
20.0
7.2.3.4 Performance Evaluation Mixture (PEM)
The PEM is prepared in hexane or iso-octane, as listed below.
PEM must be prepared weekly, or sooner if the solution has
degraded or concentrated.
The
Compounds
gamma-BHC
alpha-BHC
4,4'-DDT
beta-BHC
Endrin
Methoxychlor
Tetrachloro-m-xylene
Decachlorobiphenyl
Concentration (nq/mL)
10.0
10.0
100.0
10.0
50.0
250.0
20.0
20.0
D-15/PEST
OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 7
Reagents and Standards (Con't)
7.2.3.5 Individual Standard Mixtures A and B
The Individual Standard Mixture solutions must be prepared in
either hexane or iso-octane. The concentrations of the pesticides
in the low point standard mixtures are given below. The midpoint
concentration must be 4 times the low point concentration for each
analyte, including the surrogates. The high concentration must be
at least 16 times the low point concentration for each analyte,
including the surrogates, but a higher concentration may be chosen
by the Contractor. The high point concentration defines the upper
end of the concentration range for which the calibration is valid.
The solution must be prepared every six months, or sooner, if the
solution has degraded or concentrated.
Individual Standard
Mix A
Low Point
Concentration
(ng/mL)
Individual Standard
Mix B
Low Point
Concentration
(ng/mL)
alpha-BHC
Heptachlor
gamma-BHC
Endosulfan I
Dieldrin
Endrin
4,4'-DDD
4,4'-DDT
. Methoxychlor
Tetrachloro-m-xylene
Decachlorobiphenyl
5.0 beta-BHC
5.0 delta-BHC
5.0 Aldrin
5.0 Heptachlor-epoxide
(exo-epoxy isomer)
10.0 alpha-Chiordane
10.0 gamma-Chiordane
10.0 4,4'-DDE
10.0 Endosulfan sulfate
50.0 Endrin aldehyde
5 .0 Endrin ketone
10.0 Endosulfan II
Tetrachloro-m-xylene
Decachloro-biphenyl
5.0
5.0
5.0
5.0
5.0
5.0
10.0
10.0
10:0
10.0
10.0
5.0
10.0
NOTE: Only the exo-epoxy isomer (isomer B) of heptachlor expoxide is used as
an analytical standard.
7.2.3.6 Multicomponent Standards
Toxaphene and Aroclor standards must be prepared individually
except for Aroclor 1260 and Aroclor 1016 which may be combined in
one standard mixture. The calibration standards for the Aroclors
must be prepared at concentrations of 100 nanograms (ng)/mL,
except for Aroclor 1221 which must be prepared at 200 ng/mL.
Toxaphene must be prepared at 500 ng/mL. All multicomponent
standards must contain the surrogates at 20.0 ng/mL. The Aroclor
and toxaphene solutions must be prepared in hexane or iso-octane.
Each solution must be prepared every 6 months, or sooner, if the
solution has degraded or concentrated.
7.2.3.7 Florisil Cartridge Check Solution
Prepare a 0.10 ug/mL solution of 2,4,5-trichlorophenol in acetone.
The solution must be prepared every six months, or sooner, if the
solution has degraded or concentrated.
OLC03.2
D-16/PEST
-------
Exhibit D Pesticides/Aroclors -- Section 7
Reagents and Standards (Con't)
7.2.3.8 Laboratory Control Sample (LCS) Spiking Solution
Prepare a LCS spiking solution that contains each of the analytes
at the concentrations- listed below in methanol or acetone. The
LCS solution must be prepared every six months, or sooner, if the
solution has degraded or concentrated.
Compounds Concentration (uq/mL)
gamma-BHC 0.10
Heptachlor epoxide . 0.10
Dieldrin 0.20
4,4'-DDE 0.20
Endrin 0.20
Endosulfan sulfate 0.20
gamma-Chlordane 0.10
7.2.4 Ampulated Standard Extracts
Standard solutions purchased from a chemical supply house as
ampulated extracts in glass vials may be retained and used until the
expiration date provided by the manufacturer. If no manufacturer's
expiration date is provided, the standard solutions as ampulated
extracts may be retained and used for 2 years from the preparation
date. Standard solutions prepared by the Contractor which are
immediately ampulated in glass vials may be retained for 2 years from
preparation date. Upon breaking the glass seal, the expiration times
listed in Sections 7.2.1 to 7.2.3 will apply. The Contractor is
responsible for assuring that the integrity of the standards has not
degraded (Section 7.2.5.5).
7.2.5 Storage of Standards
7.2.5.1 Store the stock and secondary.standard solutions at 4°C (±2°C) in
PTFE-lined, screw-cap, amber bottles/vials.
7.2.5.2 Store the working standard solutions at 4°C (±2°C) in PTFE-lined
screw-cap, amber bottles/vials. The working standards must be
checked frequently for signs of degradation or evaporation.
7.2.5.3 Protect all standards from light.
7.2.5.4. Samples, sample extracts, and standards must be stored separately.
7.2.5.5 The Contractor is responsible for maintaining the integrity of
standard solutions and verifying prior to use. Storage of
standard solutions in the freezer may cause some compounds to
precipitate. This means at the minimum, the standards must be .
brought to room temperature prior to use, checked for losses, and
checked that all components have remained in solution. Additional
steps may be necessary to ensure all components are in solution.
7.2.6 Temperature Records for Storage of Standards
7.2.6.1 The temperature of all standard storage refrigerators/freezers
shall be recorded daily.
7.2.6.2 Temperature excursions shall be noted and appropriate corrective
actions shall be taken to correct problems, when required.
D-17/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Sections 7 6 S
Sample Collection, Preservation, and Storage
7.2.6.3 Corrective action SOPs shall be posted on the refrigerators.
8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE
8.1 Sample Collection and Preservation
8.1.1 Water samples may be collected in 1 L (or 1 quart) amber glass
containers, fitted with screw-caps lined with PTFE. If amber
containers are not available, the samples should be protected from
light. The specific requirements for site sample collection are
outlined by the Region.
8.1.2 All samples must be iced or refrigerated at 4°C (±2°C) from the time
of collection until extraction.
8.2 Procedure for Sample Storage
8.2.1 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 sample data package to 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". 3 Procedure for Sample Extract Storage
8:3.1 Sample extracts must be protected from light and stored at 4°C (±2°C)
until 365 days after delivery of a complete reconciled data package
5 to USEPA.
8.3.2 Sample extracts must be stored in an atmosphere demonstrated to be
free of all potential contaminants.
8"3.3 Samples, sample extracts, and standards must be stored separately.
8.4 Records for Sample and Sample Extract Storage
8.4.1 The temperature of all sample and sample extract storage
refrigerators shall be recorded daily.
8.4.2 Temperature excursions shall be noted and appropriate corrective
actions shall be taken to correct problems, when required.
8.4.3 Corrective action SOPs shall be posted on the refrigerators.
8.5 Contract Required Holding Times
8.5.1 Extraction of water samples by separatory funnel procedures must be
completed within 5 days of the Validated Time of Sample Receipt
(VTSR). Extraction of water samples by continuous liquid-liquid
extraction must be started within 5 days of VTSR.
8.5.2 As part of USEPA's QA program, USEPA may provide Performance
Evaluation (PE) Samples as standard extracts which the Contractor is
required to prepare per instructions provided by USEPA. PE samples
must be prepared and analyzed concurrently with the samples in the
SDG. The extraction holding time (5 days after VTSR) does not apply
for PE Samples received as standard extracts.
OLC03.2 D-18/PEST
-------
Exhibit D Pesticides/Aroclors -- Sections 8 & 9
Calibration and Standardization
8.5.3 Analysis of sample extracts must be completed within 40 days
following the start of extraction.
9.0 CALIBRATION AND STANDARDIZATION
9.1 Gas Chromatograph (GC) Operating Conditions
9.'1.1 The following are the gas chromatographic analytical conditions. The
conditions are recommended unless otherwise noted.
Carrier Gas: Helium (Hydrogen may be used, Section
6.10.1.5)
Column Flow: 5 mL/min
Make-up Gas: Argon/Methane (P-5 or P-10) or N2
(required)
Injector Temperature: > 200°C (Section 9.1.5)
Injection Technique: On-column
Injection Volume: 1 or 2 pi (Section 9.1.3)
Injector: Grob-type, splitless
Initial Temperature: 150°C
Initial Hold Time: 0.5 min
Temperature Ramp: 5°C to 6°C/min
Final Temperature: 275°C
Final Hold Time: After Decachlorobiphenyl has eluted
(approximately 10 minutes)
9.1.2 Optimize GC conditions for analyte separation and sensitivity. Once
optimized, the same GC conditions must be used for the analysis of
all standards, samples (including Laboratory Control Samples,
requested matrix spike, and matrix spike duplicate), and required
blanks (method/sulfur clean-up/instrument).
9.1.3 Manual injections must be 2.0 microliter (uL). Auto injectors may
use 1.0 uL volumes. The same injection volume must be used for all
standards, samples (including Laboratory Control Samples, requested
matrix spike, and matrix spike duplicate) and required blanks
(method/sulfur clean-up/instrument).
9.1.4 The linearity of the Electron Capture Detector (BCD) may be greatly
dependent on the flow rate of the make-up gas. Care must be taken to
maintain stable and appropriate flow of make-up gas to the detector.
9.1.5 Cold (ambient temperature) on-column injectors that allow injection
directly onto a 0.53 mm ID column may be used as long as the initial
calibration and calibration verification technical acceptance
criteria are met.
9.2 Initial Calibration
9.2.1 Summary of Initial Calibration
Prior to sample (including Laboratory Control Samples, requested
matrix spike and matrix spike duplicate) and required blanks
D-19/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 9
Calibration and Standardization (Con't)
(method/sulfur clean-up) analysis, each GC/ECD system must be
initially calibrated at a minimum of three concentrations for single
component analytes and surrogates in order to determine instrument
sensitivity and the linearity of GC response. Multicomponent target
analytes are calibrated at a single point.
9.2.2 Frequency of Initial Calibration
Each GC/ECD system must be initially calibrated upon award of the
contract, whenever major instrument maintenance or modification is
performed (e.g., column replacement or repair, cleaning or
replacement of BCD, etc.), or if the calibration verification
technical acceptance criteria have not been met.
9.2.3 Procedure for Initial Calibration
9.2.3.1 Set up the GC/ECD system as described in Section 9.1.
9.2.3.2 Prepare the initial calibration standards using the procedures,
the analytes, and the concentrations according to Section 7.2.
9.2.3.3 All standards, samples (including Laboratory Control Samples,
requested matrix spike, and matrix spike duplicate) and required
blanks (method/sulfur clean-up) extracts must be allowed to warm
to ambient temperature before analysis.
9.2.3.4 Analyze the initial calibration sequence as given below.
NOTE: Steps 16 and 17 are used as part of the calibration
verification as well (Section 9.3).
INITIAL CALIBRATION SEQUENCE
J 1 • Resolution Check
2. Performance Evaluation Mixture
:.••'"'• . 3. Aroclor 1016/1260
4. Aroclor .1221
5. Aroclor 1232
6. Aroclor 1242
7. Aroclor 1248
8. Aroclor 1254
9. Toxaphene
10. 'Low Point Standard A
11. Low Point Standard B
12. Midpoint Standard A
13. Midpoint Standard B
14. High Point Standard A
15. High Point Standard B
16. Instrument Blank
17. Performance Evaluation Mixture
9.2.4 Calculations for Initial Calibration
9.2.4.1 During the initial calibration sequence, absolute Retention Times
(RTs) are determined for all single component pesticides, the
surrogates, and at least three major peaks of each multicomponent
analyte.
OLC03.2 D-20/PEST
-------
Exhibit D Pesticides/Aroclors -- Section 9
Calibration and Standardization (Con't)
9.2.4.2 For each single component pesticides, a RT is measured in each of
the three calibration standards (low point, midpoint, high point)
for Individual Standard Mixture A and Individual Standard Mixture
B. The RT for the surrogates is measured from each of the three
analyses of Individual Standard Mixture A during the initial
calibration. The mean RT is calculated for each single component
pesticide and surrogate as the average of the three values.
Calculate a mean absolute RT for each single component pesticide
and surrogate using Equation 1.
EQ. 1
RT.
Where:
RT = Mean absolute retention time of analyte.
RTj = Absolute retention time of analyte.
n = Number of measurements (3).
9.2.4.3 A RT window is calculated for each single component analyte and
surrogate and for the major peaks (3 to 5) of each multicomponent
analyte by using Table D-l. Windows are centered around the
average absolute RT for the analyte established during the initial
calibration. Analytes are: identified when peaks are observed in
the RT window for the compound on both GC columns.
9.2.4.4 The linearity of the instrument is determined by calculating a
percent relative standard deviation (%RSD) of the calibration
. factors from a three-point calibration curve for each of the
single component pesticide and surrogates. Either peak area or
peak height may be used to calculate calibration factors used in
the %RSD equation. For example, it is permitted to calculate
linearity for endrin based on peak area and to calculate linearity
for aldrin based on peak height. It is not permitted within a
%RSD calculation for an analyte to use calibration factors
calculated from both peak area and peak height. For example, it
is not permitted to calculate the calibration factor for the low
point standard for endrin using peak height and calculate the
midpoint and high point standard calibration factors for endrin
using peak area.
9.-2.4.5 Calculate the calibration factor for each single component
pesticide and surrogate over the initial calibration range using
Equation 2. The calibration factors for surrogates are calculated
from the three analyses of Individual Standard A mixture only.
9.2.4.6 Calculate the mean and the %RSD of the calibration factors for
each single component pesticide and surrogate over the initial
calibration range using Equation 3 and Equation 4.
D-21/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 3
Calibration and Standardization (Con't)
EQ. 2
__ m Peafc area tog Height} ot the «t«ndmrd
Ibsat Injected
EQ. 3
er - ^
£ ert
EQ. 4
*R5D - —2- * 100
EF
Where:
%RSD = Percent relative standard deviation.
-- ,-s. SDCP = Standard deviation of calibration factors.
-.: *•• CFi = Calibration factor.
CF = Mean calibration factor.
n = Total number of values (3).
9.2.4.7 A calibration factor is calculated for each peak in a selected set
of three to five major peaks for each multicomponent analyte using
Equation 2.
9.2.4.8 Calculate the percent breakdown of DDT, the percent breakdown of
Endrin, and the combined breakdown of DDT and Endrin in the
Performance Evaluation Mixture (PEM) using Equations 5, 6, 7, and
8.
EQ. 5
tftimrt riuti - P***: *re* (or Peak height) of compound in PEH
OLC03.2 D-22/PEST
-------
Exhibit D Pesticides/Aroclors -- Section 9
Calibration and Standardization (Con't)
Where:
CFmp = The calibration factor for the compound determined from
the midpoint standard in the most recent initial
calibration.
NOTE: If during the initial calibration, linearity was determined
based on peak area for the compound, then the midpoint CF must be
based on peak area. .If during the initial calibration, the
linearity for the compound was determined based on peak height for
the compound, then the midpoint CF must be based on peak height.
EQ. 6
^Breakdown DDT - Amount found (ng> (DDD+DDE> .
iaaunc (&a} el DDT injected
EQ. 7
^Breakdown Endrln - ***""* *<"""> (*>fl) (endrin aldehyde + endrin fcetone) „
Attoune (&0> at endrin inflected)
EQ; 8
Coubined % Breakdown - * Breakdown DDT + % Breakdown Endrin
9.2.4.9 Calculate the percent difference for each pesticide and surrogate
in trie PEM using Equations 5 and 9.
EQ. 9
Where:
%D = Percent Difference.
Cnom = Nominal concentration of each analyte.
Ccaic = Calculated concentration of each analyte from the
analysis of the standard.
9.2.4.10 Calculate the resolution between the analytes in the Resolution
Check Mixture, PEM and the midpoint concentrations of Individual
Standard Mixtures A and B using Equation 10.
D-23/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 9
Calibration and Standardization (Con't)
EQ. 10
^Resolution - _ * 100
H
Where:
V = Depth of the valley between the two peaks. The depth of
the.valley is measured along a vertical line from the
level of the apex of the shorter peak to the floor of the
valley between the two peaks.
H = Height of the shorter of the adjacent peaks.
9.2.5 Technical Acceptance Criteria for Initial Calibration
All initial calibration technical acceptance criteria apply
independently to each GC column.
9.2.5.1. The initial calibration sequence must be analyzed according to the
procedure and in the order listed in Section 9.2.3, at the
concentrations listed in Section 7.2.3, and at the frequency
listed in Section 9.2.2. The GC/ECD operating conditions
optimized in Section 9.1 must be followed.
9.2.5.2 The resolution between two adjacent peaks in the Resolution Check
Mixture must be greater than or equal to 60.0 percent.
9.2.5.3 All single component pesticides and surrogates in both runs of the
PEM must be greater than or equal to 90.0 percent resolved on each
column.
9.2.5.4 The absolute RTs of each of the single component pesticides and
surrogates in both runs of the PEM must be within the RT window
determined from the three-point initial calibration in Section
9.2.4.3.
9.2.5.5 The percent difference of the calculated amount (amount found) and
the nominal amount (amount added) for each of the single component
pesticides and surrogates in both of the PEM runs of each GC
column must be greater than or equal to -25 percent and less than
or equal to 25 percent using Equation 9.
OLC03.2
D-24/PEST
-------
Exhibit D Pesticides/Aroclors -- Section 9
Calibration and Standardization (Con't)
9.2.5.6 The percent breakdown of DDT and endrin in each of the PEM runs
must be less than or equal to 20.0 percent. The combined
breakdown of DDT and endrin must be less than or equal to 30.0
percent.
9.2.5.7 The %RSD of the calibration factors for each single component
target compound must be less than or equal to 20.0 percent, except
alpha-BHC and delta-BHC. The %RSD of the calibration factors for
alpha-BHC and delta-BHC must be less than or equal to 25.0
percent. The %RSD of the calibration factors for the two
surrogates must be less than or equal to 30.0 percent. Up to two
single component target compounds (not surrogates) per column may
exceed the 20.0 percent limit for %RSD (25.0 percent for alpha-BHC
and delta-BHC), but those compounds must have a %RSD of less than
or equal to 30.0 percent.
9.2.5.8 The resolution between any two adjacent peaks in the midpoint
concentrations of Individual Standard Mixtures A and B in the
initial calibration must be greater than or equal to 90.0 percent.
9.2.5.9 All instrument blanks must meet the technical acceptance criteria
in Section 12.1.4.5.
9.2.5.10 The identification of single component pesticides by gas
chromatographic methods is based primarily on RT data. The RT of
the apex of a peak can only be verified from an on-scale
chromatogram. The identification of multicomponent analytes by
gas chromatographic methods is based primarily on recognition of
patterns of RTs displayed on a chromatogram. Therefore, the
following requirements apply to all data presented for single
component and multicomponent analytes.
• The chromatograms that result from the analyses of the
Resolution Check Mixture, the PEM, and Individual Standard
Mixtures A and B during the initial calibration sequence must
display the single component analytes present in each standard
at greater than 10 percent'of full scale but less than 100
percent of full scale.
• The chromatograms for at least one of the three analyses each
of Individual Standard Mixtures A and B from the initial
calibration sequence must display the single component
analytes at greater than 50 percent and less than 100 percent
of full scale.
• The chromatograms of the standards for the multicomponent
analytes analyzed during the initial calibration sequence must
display the peaks chosen for identification of each analyte at
greater than 25 percent and less than 100 percent of full
scale.
• For all Resolution Check Mixtures, PEMs, Individual Standard
Mixtures, and blanks, the baseline of the chromatogram must
return to below 50 percent of full scale before the elution
time of alpha-BHC, and return to below 25 percent of full
scale after the elution time of alpha-BHC and before the
elution time of decachlorobiphenyl.
• If a chromatogram is replotted electronically to meet
requirements, the scaling factor used must be displayed on the
chromatogram.
D-25/PEST . OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 9
Calibration and Standardization (Con't)
• If the chromatogram of any standard needs to be replotted
electronically to meet these requirements, both the initial
chromatogram and the replotted chromatogram must be submitted
in the data package.
9.2.6 Corrective Action for Initial Calibration
9.2.6.1 If the technical acceptance criteria for the initial calibration
are not met, inspect the system for problems. It may be necessary
to change the column, bake out the detector, clean the injection
port, or take other corrective actions to achieve the technical
acceptance criteria.
9.2.6.2 Contamination should be suspected as a cause if the detector
cannot achieve acceptable linearity using this method. In the
case of low level contamination, baking out the detector at
elevated temperature (350°C) should be sufficient to achieve
acceptable performance. In the case of heavy contamination,
passing hydrogen through the detector for 1-2 hours at elevated
temperature may correct the problem. In the case of severe
contamination, the detector may require servicing by the BCD
manufacturer. DO NOT OPEN THE DETECTOR. THE BCD CONTAINS
RADIOCHEMICAL SOURCES.
9.2.6.3 If a laboratory cleans out a detector using elevated temperature,
'- ' the BCD electronics must be turned off during the bake out
procedure.
' 9.2.6\4 After bake out or hydrogen reduction, the detector must be
-'. ••'.'-• ''" recalibrated using the initial calibration sequence.
. ,, . ->•
9.2.6.5 Initial calibration technical acceptance criteria MUST be met
•v; -*:"?' ".. before any samples (including Laboratory Control Samples, matrix
••''•'•"''•* "'; spike, and matrix spike duplicate, if required) or required blanks
'¥'"'•"-" "' (method/sulfur clean-up) are analyzed. Any samples or required
•: •'!;' ' blanks analyzed when the initial calibration technical acceptance
-';*•' ••?-,- "" criteria have not been met will require re-analysis at no
additional cost to USEPA.
.9.3 Calibration Verification
9.3.1 Summary of Calibration Verification
Three types of analyses are used to verify the calibration and
evaluate instrument performance. The analyses of instrument blanks,
• PEMs, and the mid point concentration of Individual Standard Mixtures
A and B constitute the calibration verification. Sample (including
Laboratory Control Sample and matrix spike and matrix spike
duplicate, if required) and required blank (method/sulfur clean-up)
data are not acceptable unless bracketed by acceptable analyses of
instrument blanks, PEM, and both Individual Standard Mixtures A and
B.
9.3.2 Frequency of Calibration Verification
9.3.2.1 An instrument blank and the PEM must bracket one end of a 12-hour
period during which sample and required blank data are collected,
and a second instrument blank and the mid point concentration of
Individual Standard Mixtures A and B must bracket the other end of
the 12-hour period.
OLC03.2 D-26/PEST
-------
Exhibit D Pesticides/Aroclors -- Section 9
Calibration and Standardization (Con't)
9.3.2.2 For the 12-hour period immediately following the initial
calibration sequence, the instrument blank and the PEM that are
the last two steps in the initial calibration sequence bracket the
front end of that 12-hour period. The injection of the instrument
blank starts the beginning of the 12-hour period (Section
10.2.2.1). Samples [including Laboratory Control Samples (LCSs)
and matrix spike and matrix spike duplicate (MS/MSD), if required]
and required blanks (method/sulfur clean-up) may be injected for
12 hours from the injection of the instrument blank. The first
three injections immediately after that 12-hour period must be an
instrument blank. Individual Standard Mixture A, and Individual
Standard Mixture B. The instrument blank must be analyzed first,
before either standard. The Individual Standard Mixtures may be
analyzed in either order (A,B or B,A).
9.3.2.3 The analyses of the instrument blank and Individual Standard
Mixtures A and B immediately following one 12-hour period may be
used to begin the subsequent 12-hour period, provided that they
meet the technical acceptance criteria in Section 9.3.5. In that
instance, the subsequent 12-hour period must be bracketed by the
acceptable analyses of an instrument blank and a PEM, in that
order. Those two analyses may in turn be used to bracket the
front end of yet another 12-hour period. This progression may
continue every 12 hours until such time as any of the instrument
blanks, PEMs, or Individual Standard Mixtures fails to meet the
technical acceptance criteria in Section 9.3.5. The 12-hour time
period begins with the injection of the instrument blank.
9.3.2.4 Standards (PEM or Individual Standard Mixtures), samples and
required blanks may be injected for 12 hours from the time of
injection of the instrument blank.
9.3.2:5 If more than 12 hours have elapsed since the injection of the
instrument blank that bracketed.a previous 12-hour period, an
- acceptable instrument blank and PEM,must be. analyzed in order to
. start a new sequence. . This requirement applies even if no
analyses were performed since that standard was injected.
9.3.2.6 The requirements for running the instrument blanks, PEM, and
Individual Standard Mixtures A and B are waived when no samples
(including Laboratory Control Samples, requested matrix spike and
matrix spike duplicate) dilutions, re-analyses, required blanks
(method/sulfur clean-up), and multicomponent analytes for the 72-
hour confirmation requirement are analyzed during that 12-hour
period. To resume analysis, using the existing initial
calibration, the Contractor must first analyze an instrument blank
and PEM which meet the technical acceptance criteria.
9.3.2.7 If the entire 12-hour period is not required for the analyses of
all samples and blanks to be reported and all data collection is
to be stopped, the sequence must be ended with either the
instrument blank/PEM combination or the instrument
blank/Individual Standard Mixtures A and B combination, whichever
was due to be performed at the end of the 12-hour period.
9.3.3 Procedure for Calibration Verification
9.3.3.1 All Standards and blanks must warm to ambient temperature prior to
analysis.
D-27/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 9
Calibration and Standardization (Con't)
9.3.3.2 Analyze the instrument blank, PEM, and the mid point concentration
of Individual Standard Mixtures A and B at the required
frequencies (Section 9.3.2).
9.3.4 Calculations for Calibration Verification
9.3.4.1 For each analysis of the PEM used to demonstrate calibration
verification, calculate the percent difference between the amount
of each analyte (including the surrogates) found in the PEM and
the nominal amount, using Equations 5 and 9.
9.3.4.2 For each analysis of the PEM used to demonstrate calibration
verification, calculate the percent breakdown of Endrin and DDT,
and the combined breakdown, using Equations 5, 6, 7, and 8.
9.3.4.3 For each analysis of the mid point concentration of Individual
Standard Mixtures A and B used to demonstrate calibration
verification, calculate the percent difference between the amount
of each analyte (including the surrogates) found in the standard
mixture and the nominal amount, using Equations 5 and 9. Do not
attempt to calculate the breakdown of Endrin and DDT in the
Individual Standard Mixtures, as these standards contain the
breakdown products as well as the parent compounds.
9.3.5 Technical Acceptance Criteria For Calibration Verification
..- .. All calibration verification technical acceptance criteria apply
independently to each GC column.
9.3:5.'l The PEMs, Individual Standard Mixtures, and instrument blanks must
~ : be analyzed at the' required frequency (Section 9.3.2), on a GC/ECD
system that has met the initial calibration technical acceptance
^U criteria.
9.3V5V2 All single component pesticides and surrogates in the PEMs used to
•"'• -. demonstrate calibration verification must be greater than or equal
~?K::: to 90.0 percent resolved. The resolution between any two adjacent
peaks in the midpoint concentrations of Individual Standard
Mixtures A and B used to demonstrate calibration verification must
be greater than or equal to 90.0 percent.
9.3.5.3 The absolute RT for each of the single component pesticides and
surrogates in the PEMs and mid point concentration of the
Individual Standard Mixtures used to demonstrate calibration
verification must be within the RT windows determined from the
three-point initial calibration in Section 9.2.4:3.
9.3.5.4 The percent difference of the calculated amount (amount found) and
the nominal amount (amount added) for each of the single component
pesticides and surrogates in the PEM and midpoint concentration of
the Individual Standard Mixtures used to demonstrate calibration
verification must be greater than or equal to -25.0 percent and
less than or equal to 25.0 percent.
9.3.5.5 The percent breakdown of 4,4"-DDT in the PEM must be less than or
equal to 20.0 percent on each column. The percent breakdown of
Endrin in the PEM must be less than or equal to 20.0 percent on
each column. The combined breakdown of DDT and endrin must be
less than or equal to 30.0 percent on each column.
9.3.5.6 All instrument blanks must meet the technical acceptance criteria
• in Section 12.1.4.5.
OLC03.2 D-28/PEST
-------
Exhibit D Pesticides/Aroclors >•- Section 9
Calibration and Standardization (Con't)
9.3.5.7 The identification of single component pesticides by gas
chromatographic methods is based primarily on RT data. Since the
RT of the apex of a peak can only be verified from an on-scale
chromatogram, the following requirements must be met for
calibration verification to be acceptable:
• The chromatograms that result from the analyses of the PEM and
the Individual Standard Mixtures must display the single
component analytes present in each standard at greater than 10
percent of full scale but less, than 100 percent of full scale;
• For any PEM, Individual Standard Mixture, or blank, the
baseline of the chromatogram must return to below 50 percent
of full scale before the elution time of alpha-BHC, and return
to below 25 percent of full scale after the elution time of
alpha-BHC and before the elution time of decachlorobiphenyl;
• If a chromatogram is replotted electronically to meet these
requirements, the scaling factor used must be displayed on the
chromatogram; and
• If the chromatogram of any standard or blank needs to be
replotted electronically to meet these requirements, both the
initial chromatogram and the replotted chromatogram(s) must be
submitted in the data package.
9.3.6 Corrective Action for Calibration Verification
9.3.6.1 If the technical acceptance criteria for the calibration
verification are not met, inspect the system for problems and take
corrective action to achieve the technical acceptance criteria.
9.3.6.2 Major corrective actions such as replacing the GC column or baking
out the detector will require that a new initial calibration be
performed that meets the technical acceptance criteria in Section
9.2.5.
9.3.6.3 Minor corrective actions may not require performing a new initial
calibration, provided that a new analysis of the standard (PEM or
Individual Mixtures) that originally failed the criteria and an
associated instrument blank immediately after the corrective
action do meet all the technical acceptance criteria.
9.3.6.4 If a PEM or Individual Standard Mixture does not meet the
technical acceptance criteria listed above, it must be reinjected
immediately. If the second injection of the PEM or Individual
Standard Mixture meets the criteria, sample analysis may continue.
If the second injection does not meet the criteria, all data
collection must be stopped. Appropriate corrective action must be
taken, and a new initial calibration sequence must be run before
more sample data are collected.
9.3.6.5 If an instrument blank does not meet the technical acceptance
criteria listed in Section 12.1.4.5, all data collection must be
stopped. Appropriate corrective action must be taken to clean out
the system, and an acceptable instrument blank must be analyzed
before more sample data are collected.
9.3.6.6 Analysts are reminded that running an instrument blank and a PEM
or Individual Standard Mixtures once every 12 hours are the
minimum contract requirements. Late eluting peaks may carry over
from one injection to the next if highly complex samples are
D-29/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 9
Calibration and Standardization (Con't)
analyzed or if the GC conditions are unstable. Such carryover is
unacceptable. Therefore, it may be necessary to run instrument
blanks and standards more often to avoid discarding data.
9.3.6.7 If a successful instrument blank and PEM cannot be run after an
interruption in analysis (Section 9.3.2.6), an acceptable initial
calibration must be run before sample data may be collected. All
acceptable sample (including Laboratory Control Samples, requested
matrix spike and matrix spike duplicate) and required blank
(method/sulfur clean-up) analyses must be preceded and followed by
acceptable standards and instrument blanks, as described in
Section 9.3.2.
9.3.6.8 Calibration verification technical acceptance criteria must be met
before, any samples (including the Laboratory Control Sample,
requested matrix spike and matrix spike duplicate) and required
blanks (method/sulfur clean-up) are reported. Any samples and
required blanks associated with a calibration verification which
did not meet the technical acceptance criteria will require re-
analysis at no additional cost to USEPA.
OLC03.2 D-30/PEST
-------
Exhibit D Pesticides/Aroclors -- Section 10
Procedure
10.0 PROCEDURE
10.1 Sample Preparation
10.1.1 This method is designed for analysis of water samples that contain
low concentrations of the pesticides and Aroclors listed in Exhibit
C. The majority of the samples are expected to come from drinking
water and well/ground water type sources around Superfund sites. If,
upon inspection of a sample, the Contractor suspects that the sample
is not amenable to this method, contact Sample Management Office
.(SMO). SMO will contact the Region for instructions.
10.1.2 If insufficient sample volume (less than 90 percent of the required
amount) is received to perform the analyses, the Contractor shall
contact SMO to apprise 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.
10.1.3 Extraction of Samples
Water samples may be extracted by either separatory funnel procedure
or a continuous liquid-liquid extraction procedure. If an emulsion
prevents acceptable solvent recovery with the separatory funnel
procedure, continuous liquid-liquid extraction must be employed.
Allow the samples to come to ambient temperature (approximately one
hour).
10.1.3.1 Separatory Funnel Extraction
10.1.3.1.1 Measure out each 1 L sample aliquot in a separate graduated
cylinder. Measure and.record the pH of the sample with wide
range pH paper and adjust the pH to between 5 and 9 with 10 N
sodium hydroxide or concentrated sulfuric acid, if required.
Samples requiring pH adjustment must be noted in the SDG
narrative. Place the sample aliquot into a 2 L separatory
funnel.
10.1.3.1.2 Using a syringe or a volumetric pipet add 200 microliter (uL)
of the surrogate solution (Section 7.2.3.1) to all water
samples.
10.1.3.1.3 Rinse the graduated cylinder with 30 milliliters (mL) of
methylene chloride and transfer the rinsate to the separatory
funnel. If the sample container is empty, rinse the container
with 30 mL of methylene chloride and add the rinsate to the
separatory funnel. If the sample container is not rinsed, then
add another 30 mL of methylene chloride to the separatory
funnel and extract the sample by shaking the funnel for two
minutes, with periodic venting to release excess pressure.
NOTE: The total volume of solvent used for extraction is 60 mL.
Allow the organic layer to separate from the water phase for a
minimum of 10 minutes. If the emulsion interface between
layers is more than one-third the volume of the solvent layer,
the analyst must employ mechanical techniques to complete the
phase separation. The optimum technique depends upon the
sample, and may include stirring, filtration through glass
wool, centrifugation or other physical means. Drain the
methylene chloride into a 250 mL Erlenmeyer flask.
D-31/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 10
Procedure (Con't}
10.1.3.1.4 Add a second 60 mL volume of methylene chloride to the
separatory funnel and repeat the extraction procedure a second
time, combining the extracts in the Erlenmeyer flask. Perform
a third extraction in the same manner.
10.1.3.2 Continuous Liquid-Liquid Extraction
10.1.3.2.1 Continuous Liquid-Liquid Extraction Without Hydrophobic
Membrane
10.1.3.2.1.1 Follow manufacturer's instructions for set-up.
10.1.3.2.1.2 Add methylene chloride to the bottom of the extractor and
fill it to a depth of at least one inch above the bottom
sidearm.
10.1.3.2.1.3 Measure out each 1 L sample aliquot in a separate, clean
graduated cylinder; transfer the aliquot to the continuous
extractor. Measure the pH of the sample with wide range pH
paper or pH meter and record pH. Adjust the pH to between 5
and 9 with 10 N sodium hydroxide or concentrated sulfuric
acid, as required. Samples requiring the pH adjustment must
be noted in the SDG Narrative.
NOTE: With some samples, it may be necessary to place a
s'. layer of glass wool between the methylene chloride and the
•••..•• water layer in the extractor to prevent precipitation of
-« suspended solids into the methylene chloride during
extraction.
10 .1.3;;,2 .1.4 Using a syringe or volumetric pipet, add 200 uL of the
surrogate standard spiking solution (Section 7.2.3.1) into
•/?'•> the sample and mix well.
i'3'~-'
10.1.3V2.1.5 Rinse the graduated cylinder with 50 mL of methylene
„'- chloride and transfer the rinsate to the continuous
--• extractor. If the sample container is empty, rinse the
container with 50 mL of methylene chloride and add the
rinsate to the continuous extractor.
10.1.3.2.1.6 Add sufficient methylene chloride to the continuous
extractor to ensure proper solvent cycling during operation.
Adjust the drip rate to 5 to 15 mL/minute (recommended);
optimize the extraction drip rate. Extract for a minimum of
18 hours.
NOTE 1: When a minimum drip rate of 10-15 tnLs/minute is
maintained throughout the extraction, the extraction time
may be reduced to a minimum of 12 hours. Allow to cool,
then detach the distillation flask. Proceed to Section
10.1.4.
NOTE 2: Some continuous liquid-liquid extractors are also
capable of concentrating the extract within the extraction
set-up. Follow the manufacturer's instructions for
concentration when using this type of extractor.
OLC03.2 D-32/PEST
-------
Exhibit D Pesticides/Aroclors -- Section 10
Procedure (Con't)
10.1.3.2.2 Continuous Liquid-Liquid Extraction With Hydrophobic Membrane
10.1.3.2.2.1 Follow the manufacturer's instructions for set-up.
10.1.3.2.2.2 Measure out each 1 L sample aliquot in a separate, clean
graduated cylinder. If the sample container is empty, rinse
the container with 50 mL of methylene chloride and add the
rinsate to the continuous extractor. If the sample was not
received in a 1 L container, add 50 mL of methylene chloride
to the continuous extractor. Slowly transfer the aliquot to
the continuous extractor. Measure the pH of the sample with
wide range pH paper or pH meter and record pH. Adjust the
pH to between 5 and 9 with 10 N sodium hydroxide or
concentrated sulfuric acid, as required. Samples requiring
the pH adjustment must be noted in the SDG Narrative.
10.1.3.2.2.3 Using a syringe or volumetric pipet, add 200 uL of the
surrogate standard spiking solution (Section 7.2.3.1) into
the sample and mix well.
10.1.3.2.2.4 .Rinse the graduated cylinder with 50 mL of methylene
chloride and transfer the rinsate to the continuous
extractor.
10.1.3.2.2.5 Add sufficient methylene chloride to the continuous
extractor to ensure proper solvent cycling during operation.
Adjust the drip rate to 15 mL/minute (recommended); optimize
the extraction drip rate. Extract for a minimum of 6 hours.
NOTE 1: Due to the smaller volume of solvent used during the
extraction process, some .sample matrices (e.g., oily
samples, samples containing a high concentration of
surfactants) may create, an .emulsion which will consume the
solvent volume, preventing the efficient extraction of the
sample.' When this-occurs, add additional solvent to ensure
efficient extraction of the sample, and extend the
extraction time for a minimum of 6 hours. If the sample
matrix prevents the free flow of solvent through the
membrane, then the non-hydrophobic membrane continuous
liquid-liquid type extractor must be used.
Allow to cool, then detach the distillation flask. Proceed
to Section 10.1.4.
NOTE 2: Some continuous liquid-liquid extractors are also
capable of concentrating the extract within the extraction
set-up. Follow the manufacturer's instructions for
concentration when using this type of extractor. Using the
hydrophobic membrane, it may not be necessary to dry the
extract with sodium sulfate.
NOTE 3: If low surrogate recoveries occur, assure 1) the
apparatus was properly assembled to prevent leaks,- 2) the
drip rate/solvent cycling was optimized; and 3) there was
proper cooling for condensation of solvent. Document the
problem and the corrective action.
NOTE 4: Alternate continuous liquid-liquid extractor types
that meet the requirements of the SOW may also be used. If
using alternate extractors or design types, follow the
manufacturer's instructions for set-up. Optimize the
extraction procedure.
D-33/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 10
Procedure (Con't)
10.1.4 Extract Drying and Concentration
10.1.4.1 Assemble a kuderna-Danish (K-D) concentrator by attaching a 10 mL
concentrator tube to a 500 mL evaporative flask. Other
concentration devices or techniques may be used in place of the
K-D, if equivalency is demonstrated for all the target pesticides
and Aroclors listed in Exhibit C.
10.1.4.1 Pour the extract through a drying column containing about 10
centimeters (cm) of anhydrous granular sodium sulfate and collect
the extract in the K-D concentrator. Rinse the Erlenmeyer flask
and the sodium sulfate with at least two additional 20 to 30 mL
portions of methylene chloride to complete the quantitative
transfer.
10.1.4.3 Add one or two clean boiling chips to the evaporative flask and
attach a three-ball Snyder column. Pre-wet the Snyder column by
adding about 1 mL of methylene chloride to the top of the column.
Place the K-D apparatus on a hot water bath (60-90°C recommended)
so that the concentrator tube is partially immersed in the hot
water and the entire lower rounded surface of the flask is bathed
with hot vapor. Adjust the vertical position of the apparatus and
the water temperature as required to complete the concentration in
15 to 30 minutes. At the proper rate of distillation, the balls
of the column will actively chatter, but the chambers will not
*.' flood with condensed solvent. When the apparent volume of liquid
? reaches 3 to 5 mL, remove the K-D apparatus. Allow it to drain
and cool for at least 10 minutes. DO NOT ALLOW THE EVAPORATOR TO
GO DRY. Proceed with the solvent exchange to hexane.
"^:
10.1.4>4 Solvent Exchange to Hexane
X*
10.1.47-4.1 Momentarily remove the three-ball Snyder column, add 50 mL of
-Kit hexane and a new boiling chip, and reattach the Snyder column.
"S- Pre-wet the column by adding about 1 mL of hexane to the top.
'•••;, Concentrate the solvent extract as before. When the apparent
:** volume of liquid reaches 1 mL, remove the K-D apparatus and
allow it to drain and cool for at least 10 minutes. DO NOT
ALLOW THE EVAPORATOR TO GO DRY.
10.1.4.4.2 Remove the Snyder column; using 1 to 2 mL of hexane, rinse the
flask and its lower joint into the concentrator tube.
10.1.4.4.3 Use the micro Snyder column or the nitrogen blowdown technique
to concentrate the hexane extract to 2.0 mL.
10.1.4.5 Final Concentration of Extract
Two different techniques are permitted to concentrate the extract
to 2.0 mL. They are the micro Snyder column and nitrogen
evaporation techniques.
10.1.4.5.1 Micro Snyder Column Technique
Add another one or two clean boiling chips to the concentrator
tube and attach a two-ball micro Snyder column. Pre-wet the
Snyder column by adding about 0.5 mL of hexane to the top of
the column. Place the K-D apparatus in a hot water bath (80°C
to 90°C recommended) so that the concentrator tube is partially
immersed in the hot water. Adjust the vertical position of the
apparatus and the water temperature as required to complete the
concentration in 5 to 10 minutes. At the proper rate of
OLC03.2 D-34/PEST
-------
Exhibit D Pesticides/Aroclors -- Section 10
Procedure (Con't)
distillation the balls of the column will actively chatter but
the chambers will not flood with condensed solvent. When the
apparent volume of liquid reaches about 0.5 inL, remove the K-D
apparatus from the water bath and allow it to drain for at
least 10 minutes while cooling. Remove the Snyder column and
rinse its flask and lower joint into the concentrator tube with
0.2 mL of hexane. Adjust the final volume with hexane to 2.0
mL.
10.1.4.5.2 Nitrogen Evaporation Technique (taken from ASTM Method D 3086).
10.1.4.5.2.1 Place the concentrator tube with an open micro Snyder column
attached in a warm water bath (30°C to 35°C recommended) and
evaporate the solvent volume to just below 1 or 2 mL by
blowing a gentle stream of clean, dry nitrogen filtered
through a column of activated carbon above the solvent.
Adjust the final volume with hexane to 1.0 mL (Florisil
cartridge check) or 2.0 mL (sample extract).
10.1.4.5.2.2 CAUTION: Gas lines from the gas source to the evaporation
apparatus must be stainless steel, copper, or PTFE tubing.
Plastic tubing must not be used between the carbon trap and
the sample as it may introduce interferences. The internal
wall of new tubing must be rinsed several times with hexane
and then dried prior to use.
10.1.4.5.2.3 During evaporation, the tube solvent level must be kept
below the water level of the bath. DO NOT ALLOW THE EXTRACT
TO GO TO DRYNESS.
10.1.4.6 Proceed to Section 10.1.5 for extract cleanup. Otherwise,
transfer the extract to a PTFE-lined screw-cap bottle and label
the bottle. Store at 4°C (±2°C) but not greater than 6°C.
10.1.5 Extract Cleanup
10.1.5.1 The two cleanup procedures specified in this method are Florisil
cartridge and sulfur cleanup. Florisil cartridge cleanup is
required for all extracts. Sulfur cleanup must be performed on
all extracts containing sulfur at levels that interfere with Gas
Chromatograph/Electron Capture Detector (GC/ECD) analysis. Sulfur
contamination in a sample analysis is unacceptable. Method blanks
must be subjected to the same cleanup procedures as the samples.
10.1.5.2 Florisil Cleanup
10.1.5.2.1 Introduction
Florisil cartridge cleanup significantly reduces matrix
interference caused by polar compounds and is required for all
extracts. The same volume of the concentrated extract taken
for Florisil cleanup must be maintained after Florisil cleanup
(2 mL) .
10.1.5.2.2 Florisil Cartridge Performance Check
10.1.5.2.2.1 Summary of Florisil Cartridge Performance Check
Every lot number of Florisil cartridges must be tested
before they'are used for sample cleanup.
D-35/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 10
Procedure ( Con ' t )
10.1.5.2.2.2 Frequency of Florisil Cartridge Performance Check
Cartridge performance check must be conducted at least once
on each lot of cartridges used for sample cleanup or every 6
months whichever is most frequent.
10.1.5.2.2.3 Procedure for Florisil Cartridge Performance Check
Add 0.5 tnL of 2,4,5-trichlorophenol solution (0.1 ug/mL in
acetone, Section 7.2.3.7) and 0.5 mL of Standard Mixture A,
midpoint concentration. Section 7.2.3.5) to 4 mL of hexane.
Reduce the volume to 0.5 mL using nitrogen (Section
10.1.4.5.2). Place the mixture onto the top of a washed
Florisil cartridge, and elute it with 9 mL of hexane/acetone
[(90:10) (V/V) ] . Use two additional 1 mL hexane rinses to
ensure quantitative transfer of standard from the cartridge .
Concentrate to a final volume of 1 mL and analyze the
solution by GC/ECD using at least one of the GC columns
specified for sample analysis . Determine the recovery of
each arialyte for evaluation and reporting purposes.
Calculate the percent recovery using Equation 11.
EQ. 11
Percent Rtcovfcry - — » 100
Where :
.-!_.. Qd = Quantity determined by analysis.
,^T Qa = Quantity added.
10.1 .5. ,2 .2 .4 Technical Acceptance Criteria for Florisil Cartridge
Performance Check
~i>:- '
10.1.5.2.2.4.1 The cartridge performance check solution must be analyzed
on a GC/ECD meeting the initial calibration and
calibration verification technical acceptance criteria.
10.1.5.2.2.4.2 The lot of Florisil cartridges is acceptable if all
pesticides are recovered at 80 to 120 percent, if the
recovery of trichlorophenol is less than 5 percent, and
if no peaks interfering with the target analytes are
detected .
10.1.5.2.2.5 Corrective Action for Florisil Cartridge Performance Check
Any lot of Florisil cartridges that does not meet the
criteria above must be discarded and a new lot, meeting
criteria, used for sample cleanup.
10.1.5.2.3 Sample Cleanup by Florisil Cartridge
The required Florisil cartridge size is a 1 g cartridge and the
final volume of the extract after Florisil cleanup is 2 mL.
OLC03.2 D-36/PEST
-------
Exhibit D Pesticides/Aroclors -- Section 10
Procedure (Con't)
10.1.5.2.3.1 Frequency of Sample Cleanup by Florisil Cartridge
All sample extracts (including Laboratory Control Samples
and requested matrix spike and matrix spike duplicate) and
method blank extracts are required to be cleaned up by the
Florisil cartridge technique.
10.1.5.2.3.2 Procedure for Sample Cleanup by Florisil Cartridge
10.1.5.2.3.2.1 Attach the vacuum manifold to a water aspirator or to a-
vacuum pump with a trap installed between the manifold
and the vacuum source. Adjust the vacuum pressure in the
manifold to between 5 and 10 pounds of vacuum.
10.1.5.2.3.2.2 Place one Florisil cartridge into the vacuum manifold for
each sample extract.
10.1.5.2.3.2.3 Prior to cleanup of samples, the cartridges must be
washed with hexane/acetone (90:10). This is accomplished
by placing the cartridge on the vacuum manifold, by
pulling a vacuum, and by passing at least 5 mL of the
. hexane/acetone solution through the cartridge. While the
cartridges are being washed, adjust the vacuum applied to
each cartridge so that the flow rate through each
cartridge is approximately equal. DO NOT ALLOW THE
CARTRIDGES TO GO DRY AFTER THEY HAVE BEEN WASHED.
10.1.5.2.3.2.4 After the cartridges on the manifold are washed, the
vacuum is released, and a rack containing labeled 10 mL
volumetric flasks is placed inside the manifold. Care
must be taken to ensure that the solvent line from each
cartridge is placed inside-of the appropriate volumetric
flask as the manifold top is replaced.
10.1.5.2.3.2.5 After the volumetric flasks are in place, the vacuum to
the manifold is restored, and a volume of extract equal
to the required final volume from each sample and method
blank extract is transferred to the top frit of the
appropriate Florisil cartridge. This must equal the
final volume after Florisil cleanup.
10.1.5.2.3.2.6 Because the volumes marked on concentrator tubes are not
necessarily accurate at the 1 mL level, the use of a
syringe or a volumetric pipet is required to transfer the
extract to the cleanup cartridge.
10.1.5.2.3.2.7 The pesticides/Aroclors in the extract concentrates are
then eluted through the column with 8 mL of
• hexane/acetone (90:10) and are collected into the 10 mL
volumetric flasks held in the rack inside the vacuum
manifold.
10.1.5.2.3.2.8 Transfer the eluate in each volumetric flask to a clean
centrifuge tube or 10 mL vial. Use two additional 1 mL
hexane rinses to ensure quantitative transfer of the
cartridge eluate.
10.1.5.2.3.2.9 Adjust the extract to 2 mL aliquot volume as was taken
for cleanup using either nitrogen blowdown or a micro
Snyder column (Section 10.1.4.5). Measure the final
volume with a syringe or by transferring the extract to a
volumetric flask.
D-37/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 10
Procedure (Con't)
10.1.5.2.3.2.10 If sulfur cleanup is to be performed, proceed to Section
10.1.5.3.3. Otherwise, transfer the sample to a GC vial
and label the vial. The extract is ready for GC/ECD
analysis.
10.1.5.3 Sulfur Cleanup
10.1.5.3.1 Introduction
10.1.5.3.1.1 Sulfur contamination will cause a rise in the baseline of a
chromatogram and may interfere with the analyses of the
later eluting pesticides. If crystals of sulfur are evident
or if the presence of sulfur is suspected, sulfur removal
must be performed. Interference which is due to sulfur is
not acceptable. Sulfur can be removed by one of two
methods, according to laboratory preference. If the sulfur
concentration is such that crystallization occurs in the
concentrated extract, centrifuge the extract to settle the
crystals, and remove the sample extract with a disposable
pipette, leaving the excess sulfur in the centrifuge tube.
Transfer the extract to a clean centrifuge tube or clean
concentrator tube before proceeding with further sulfur
cleanup.
10.1.5.3.1.2 If only part of a set of samples require sulfur cleanup,
then, a sulfur cleanup blank is required for that part of
the set (Section 12.1.3.2).
•10.1.5.3'.2 Frequency of Sulfur Cleanup
-' Sulfur removal is required for all sample extracts that contain
•'•'57 '<•" sulfur.
10.1.5.3.3 Procedure for Sulfur Cleanup
•1-0-. 1.5.3-.3.1 Mercury Technique
Add one to three drops of mercury to each hexane extract in
a clean vial. Tighten the top on the vial and agitate the
sample for 30 seconds. Filter or centrifuge the extract.
Pipet the extract to another vial and leave all solid
precipitate and liquid mercury. If the mercury appears
shiny, proceed to Section 10.2 and analyze the extract. If
the mercury turns black, repeat sulfur removal as necessary.
The extract transferred to the vial still represents the 2.0
mli final volume. CAUTION: Waste containing mercury should
be segregated and disposed of properly.
NOTE: Mercury is a highly toxic metal and therefore must be
used with great care. Prior to using mercury, it is
recommended that the analyst become acquainted with proper
handling and cleanup techniques associated with this metal.
10.1.5.3.3.2 Copper Technique
Add approximately 2 grams (g) of cleaned copper powder to
the extract in the centrifuge or concentrator tube (2 g will
fill the tube to about the 0.5 mL mark). Mix the copper and
extract for at least 1 minute on a mechanical shaker.
Separate the extract from the copper powder by drawing off
the extract with a disposable pipet, and transfer the
extract to a clean vial. The extract transferred to the
OLC03.2 D-38/PEST
-------
Exhibit D Pesticides/Aroclors -- Section 10
Procedure (Con't)
vial still represents the 2.0 mL final volume. The
separation of the extract from the copper powder is
necessary to prevent degradation of the pesticides. If the
copper appears bright, proceed to Section 10.2 and analyze
the extracts. If the copper changes color, repeat the
sulfur removal procedure as necessary.
10.2 GC Analysis
10.2.1 Introduction
10.2.1.1 Before samples (including Laboratory Control Samples and requested
matrix spike and matrix spike duplicate) and required blanks
(method/sulfur clean-up) can be analyzed, the instrument must meet
the initial calibration and calibration verification technical
acceptance criteria. All sample extracts, required blanks, and
calibration standards must be analyzed under the same instrumental
conditions. All sample extracts, required blank extracts, and
standard/spiking solutions must be allowed to warm to ambient
temperature (approximately 1 hour) before preparation/analysis.
Sample analysis on both GC columns is required for all samples and
blanks.
10.2.1.2 Set up the GC/ECD system per the requirements in Section 9.1.
Unless ambient temperature on-column injection is used (Section
9.1), the injector must.be heated to at least 200°C. The
optimized gas chromatographic conditions from Section 9.1 must be
used.
10.2.2 Procedure for Sample Analysis by GC/ECD
The injection must be made on-column by using either automatic or
manual injection. If autoinjectors are used, 1.0 uL injection
volumes may be used. Manual injections must use at least 2.0 uL
injection volumes. The same injection volume must be used for all
standards, samples, and'blanks associated:with the same initial
calibration. If a single injection is used for two GC columns
attached to a single injection port, it may be necessary to use an
injection volume greater than 2 uL. However, the same injection
volume must be used for all analyses.
10.2.2.1 Analytical Sequence
*
All samples and required blanks must be analyzed within a valid
analysis sequence as given below.
Iniection
Material Injected
0 hr.
12 hr.
1-15
16
17
18
0
0
0
0
First 15 steps of the initial
calibration
Instrument blank at end of
initial calibration
PEM at end of initial
calibration
First sample
Subsequent samples
Last sample
D-39/PEST
OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 10
Procedure (Con't)
Time
Another 12 hr.
Another 12 hr.
In-jection #
1st injection past
12:00 hr.
2nd and 3rd
injections past
12:00 hr.
0
0
0
0
0
0
1st injection past
12 hr.
2nd injection
0
0
0
0
0
0
1st injection past
12:00 hr.
2nd and 3rd
injections past
12:00 hr.
0
0
0
0
0
etc.
Material Injected
Instrument blank
Individual Standard Mixtures
A and B
Sample
Subsequent samples
Last sample
Instrument blank
PEM
Sample
Subsequent samples
Last sample
Instrument blank
Individual Standard Mixtures
A and B
Sample
Subsequent samples
10.2.2.1.1 The first 12 hours are counted from injection #16 (the
Instrument Blank at the end of the initial calibration
sequence), not from injection #1. Samples and required blanks
may be injected until 12:00 hours have elapsed. All subsequent
12-hour periods are timed from the injection of the instrument
blank that brackets the front end of the samples. Because the
12-hour time period is timed from injection of the instrument
blank until the injection of the last sample, each 12-hour
period may be separated by the length of one chromatographic
run, that of the analysis of the last sample. While the 12-
hour period may not be exceeded, the laboratory may run
instrument blanks and standards more frequently, for instance,
to accommodate staff working on 8-hour shifts.
10.2.2.1.2 After the initial calibration, the analysis sequence may
continue as long as acceptable instrument blanks, PEMs and
Individual Standard Mixtures A and B are analyzed at the
required frequency. This analysis sequence shows only the
minimum required blanks and standards. More blanks and
standards may be run at the discretion of the Contractor;
however, the blanks and standards must also satisfy the
OLC03.2
D-40/PEST
-------
Exhibit D Pesticides/Aroclors -- Section 10
Procedure (Con't)
criteria presented in Section 9 in order to continue the run
sequence.
10.2.2.1.3 An analysis sequence must also include all samples and
required blank analyses, but the Contractor may decide at
what point in the sequence they are to be analyzed.
10.2.2.1.4 The requirements for the analysis sequence apply to each GC
column and for all instruments used for these analyses.
10.2.3 Sample Dilutions
10.2.3.1 The sample must first be analyzed at the most concentrated level
(injection taken from the 2.0 mL final extract after the clean-up
steps).
10.2.3.2 If the concentration of any single component pesticide is greater
than the upper limit of the initial calibration range on both GC
columns, then the extract must be diluted. If the concentration
of any single component pesticide is greater than the upper limit
of the initial calibration range on one GC column, but not the
other, then the extract must be diluted only if the percent
difference between the two concentrations is less than or equal to
25%. The on-column concentration of the pesticide compound(s) in
the diluted extract must be between the initial calibration low
point and high point standards.
10.2.3.3 If the calculated concentration of any multicomponent peak, used
for quantitation is greater than the concentration of the most
intense single component analyte in the initial calibration high
point standard, then the sample must be diluted to have the
concentration of the largest peak in the multicomponent analyte
between the initial calibration midpoint and high point standards
of that single component pesticide.
10.2.3.4 If dilution is employed solely to bring a peak within the
calibration range or to get a multicomponent pattern on scale, the
results for both the more and the less concentrated extracts must.
be reported. The resulting changes in quantitation limits and
surrogate recovery must be reported also for the diluted samples.
10.2.3.5 If the dilution factor is greater than 10, an additional extract
10 times more concentrated than the diluted sample extract must be
analyzed and reported with the sample data. If the dilution
factor is less than 10, but greater than 1, the results of the
original undiluted analysis must also be reported.
10.2.3.6 If the analysis of the most concentrated extract does not meet the
requirement for dilution in Section 10.2.3.2 and 10.2.3.3, then
the analysis is at no additional cost to USEPA.
10.2.3.7 When diluted, the chromatographic data for the single component
pesticide must be able to be reported at greater than 10 percent
of full scale but less than 100 percent of full scale.
10.2.3.8 When diluted, multicomponent analytes must be able to be reported
at greater than 25 percent of full scale but less than 100 percent
of full scale.
10.2.3.9 If a chromatogram is replotted electronically to meet these
requirements, the scaling factor used must be displayed on the
chromatogram. If the chromatogram of any sample needs to be
replotted electronically to meet these requirements, both the
D-41/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 10
Procedure (Con't)
initial chromatogram and the replotted chromatogram(s) must be
submitted in the data package.
10.2.3.10 Dilute the sample using the following procedure:
10.2.3.10.1 Calculate the extract dilution in order for the single
component pesticides to meet the requirement listed in Section
10.2.3.7.
10.2.3.10.2 Calculate the extract dilution in order for the multicomponent
analytes to meet the requirement listed in Section 10.2.3.8.
10.2.3.10.3 Dilute the sample extract quantitatively with hexane.
OLC03.2 D-42/PEST
-------
Exhibit D Pesticides -- Section 11
Data Analysis and Calculations
11.0 DATA ANALYSIS AND CALCULATIONS
11.1 Qualitative Identification of Target Compounds
11.1.1 The laboratory will identify single component analyte peaks based on
the Retention Time (RT) windows established during the initial
calibration sequence. Single component analytes are identified when
peaks are observed in the RT window for the analyte on both Gas
Chromatograph (GC) columns.
11.1.2 A set of three to five major peaks is selected for each
multicomponent analyte. RT windows for each peak are determined from
the initial calibration analysis. Identification of a multicomponent
analyte in the sample is based on pattern recognition in conjunction
with the elution of three to five sample peaks within the RT window
of the corresponding peaks of the standard on both GC columns. The
number.of potential quantitation peaks is listed in Table D-2.
11.1.3 A standard of any identified multicomponent analyte must be run
within 72 hours of its detection in a sample chromatogram within a
valid 12-hour sequence.
11.1.4 The choice of the peaks used for multicomponent analyte
identification and the recognition of those peaks may be complicated
by the environmental alteration of the toxaphene or Aroclors, and by
the presence of coeluting analytes, or matrix interferences, or both.
Because of the alteration of these materials in the environment,
multicomponent analytes in samples may give patterns similar to, but
not identical with, those of the standards.
11.1.5 Toxaphene and Aroclors require only a single-point calibration.
Identification requires visual inspection of an on-scale pattern.
11.2 Calculations
11.2.1 Target Compounds
11.2.1.1 Quantitation for all analytes and surrogates must be performed and
reported for each GC column.
11.2.1.2 Manual integration of peaks (e.g., measuring peak height with a
ruler) is only permitted when accurate electronic integration of
peaks cannot be done. If manual integration of peaks is required,
it must be documented in the Sample Delivery Group (SDG)
Narrative.
11.2.1.3 The Contractor must quantitate each single component analyte and
surrogate based on the calibration factor from the most recent
initial calibration midpoint standard mixture analyses. Do not
use the analyses of the Individual Standard Mixtures used to
demonstrate calibration verification for quantitation of samples.
11.2.1.4 The Contractor must quantitate each multicomponent analyte based
on the calibration factor from the most recent initial calibration
standard.
11.2.1.5 If more than one multicomponent analyte is present, the Contractor
must choose separate peaks to quantitate the different
multicomponent analytes. A peak common to both analytes present
in the sample must not be used to quantitate either analyte.
D-43/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 11
Data Analysis and Calculations (Con't)
11.2.1.6 Before reporting data to USEPA, it is required that the Contractor
check for flags generated by the data system that indicate
improper quantitation of analytes.
11.2.1.7 The chromatograms of all samples (including Laboratory Control
Samples, requested matrix spike/matrix spike duplicate) standards,
and required blanks must be reviewed by a qualified pesticide
analyst before they are reported.
11.2.1.8 Calculate the concentration of the single component pesticides and
surrogates by using the following equation:
EQ. 12
|1J (Vfc) (Bt)
Concentration
CFtap
Where:
AX = Response (peak area or height) of the compound to be
measured.
CFmp= Calibration factor for the mid-point from initial
calibration standard (area per ng).
•••"' Vt = Volume of concentrated extract (uL) . (This volume is
2000 uL).
•'.'•• Vi = Volume of extract injected (uL) . (If a single injection
is made onto two columns, use one-half the volume in the
>:F>- syringe as the volume injected onto each column) .
»?.?.
Vx = Volume of water extracted (mL). (NOTE: for instrument
blanks and sulfur cleanup blanks, assume a 1,000 mL
volume).
Df = Dilution factor. The dilution factor for analysis of
water samples by this method is defined as follows:
uL most concentrated extract used to make dilution + uL clean solvent
uL most concentrated extract used to make dilution
If no dilution is performed, Df = 1.0.
The calibration factors used in Equation 12 are those from the
most recent mid-point standard from the initial calibration. If
the calibration factors used to determine the linearity of the
initial calibration were based on peak area, then the
concentration of the analyte in the sample must be based on peak
area. Similarly, if peak height was used to determine linearity,
use peak height to determine the concentration in the sample.
11.2.1.9 Contract Required Quantitation Limit (CRQL) Calculation
If the adjusted CRQL is less than the CRQL listed in Exhibit C
(Pesticides), report the CRQL in Exhibit C (Pesticides).
Calculate the adjusted CRQL for pesticides by using the following
equation:
OLC03.2 ' D-44/PEST
-------
Exhibit D Pesticides -- Section 11
Data Analysis and Calculations (Con't)
EQ. 13
Contract Stomp le
Adjusted Contract Vol (1000 nL> M Vt
CRfiL " CROL * v Contract Ext.
Vol (2000uL)
Where :
Contract CRQL = Take exact CRQL values reported in Exhibit C
of the SOW.
Vx = Same as EQ. 12.
Vc = Same as EQ. 12.
Df = Same as EQ . 12 .
11.2.1.10 During initial calibration, a set of three to five quantitation
peaks was chosen for each multicomponent analyte. Calculate the
concentration of each of the selected Aroclor or toxaphene peaks
individually using Equation 12. Determine the mean concentration
for all of the selected peaks. The mean value is reported on Form
X (Exhibit B) for both GC columns.
11.2.1.11 For the single component pesticides, report the lower of the two
values quantitated from the two GC columns of Form I . For the
multicomponent analytes, report the lower of the two mean values
from the two GC columns on Form I .
11.2.1.12 The percent difference is calculated according to Equation 14.
EQ. 14
Cone. - Cone.
• - — - — * 100
Where :
ConcH = The higher of the two concentrations for the target
compound in question.
ConcL = The lower of the two concentrations for the target
compound in question.
NOTE: Using this equation will result in percent difference values
that are always positive. The value will also be greater than a
value calculated using the higher concentration in the
denominator, however, given the likelihood of a positive
interference raising the concentration determined on one GC
column, this is a conservative approach to comparing the two
concentrations .
11.2.2 Surrogate Recoveries
11.2.2.1 The concentrations of the surrogates are calculated separately for
each GC column in a similar manner as the other analytes using
Equation 12 . Use the calibration factors from the midpoint
concentration of Individual Standard Mixture A from the initial
calibration.
D-45/PEST OLC03.2
-------
Exhibit D Pesticides /Aroclors -- Section 11
Data Analysis and Calculations (Con't)
11.2.2.2 The recoveries of the surrogates are calculated according to
Equation 15.
EQ. 15
Percent Recovery • — - * 100
Where:
Qd = Quantity determined by analysis.
Qa = Quantity added to sample/blank.
11 . 3 Technical Acceptance Criteria for Sample Analyses
The requirements below apply independently to each GC column and to all
instruments used for these analyses. (See exception in Section 11.3.7)
Quantitation must be performed on each GC column.
11.3.1 Samples must be analyzed under the Gas Chromatograph/Electron Capture
Detector (GC/ECD) operating conditions in Section 9.1. The
instrument must have met all initial calibration and calibration
verification technical acceptance criteria. Samples must be cleaned-
up using Florisil that meets the technical acceptance criteria for
Florisil. Sample data must be bracketed at 12-hour intervals (or
less) by acceptable analyses of instrument blanks. Performance
Evaluation Mixtures (PEMs) , and Individual Standard Mixtures A and B,
' as described in Section 10.2.2.1.
11.3.2'r The sample must be extracted and analyzed within the contract holding
times .
11.3.3 The Laboratory Control Sample (LCS) associated with the samples must
.;:•. meet the LCS technical acceptance criteria.
11.3.4 The samples must have an associated method blank meeting the method
blank technical acceptance criteria. If a sulfur cleanup blank is
associated with the samples, that blank must meet the sulfur cleanup
blank technical acceptance criteria.
11.3.5 The RT for each of the surrogates must be within the RT window as
calculated in Section 9.2.4.3, for both GC columns.
11.3.6 The percent recovery for the surrogates must be between 30.0 and 150
percent, inclusive. These limits are not advisory.
NOTE: The surrogate recovery requirements do not apply to a sample
that has been diluted.
11.3.7 No target analyte concentrations may exceed the upper limit of the
initial calibration or else extracts must be diluted and re-analyzed.
If a target analyte concentration exceeds the upper limit of the
initial calibration on one GC column, but not the other, the extract
must be diluted and re-analyzed only if the percent difference
between the two concentrations is less than or equal to 25%.
11.3.8 A standard for any identified multicomponent analyte must be analyzed
on the same instrument within 72 hours of its detection in a sample
within a valid 12 hour sequence.
OLC03.2 D-46/PEST
-------
Exhibit D Pesticides -- Section 11
Data Analysis and Calculations (Con't)
11.3.9 The identification of single component pesticides by gas
chromatographic methods is based primarily on RT data. The RT of the
apex of a peak can only be verified from an on-scale chromatogram.
The identification of multicomponent analytes by gas chromatographic
methods is based primarily on recognition of patterns of RTs
displayed on a chromatogram. Therefore, the following requirements
apply to all data presented for single component and multicomponent
analytes.
11.3.9.1 When no analytes are identified in a sample, the chromatograms
from the analyses of the sample extract must use the same scaling
factor as was used for the low point standard of the initial
calibration associated with those analyses.
11.3.9.2 Chromatograms must display single component pesticides detected in
the sample at less than full scale.
11.3.9.3 Chromatograms must display the largest peak of any multicomponent
analyte detected in the sample at less than full scale.
11.3.9.4 If an extract must be diluted, chromatograms must display single
component pesticides between 10 and 100 percent of full scale.
11.3.9.5 If an extract must be diluted, chromatograms must display
multicomponent analytes between 25 and 100 percent of full scale.
11.3.9.6 For any sample or blank, the baseline of the chromatogram must
return to below 50 percent of full scale before the elution time
of alpha-BHC, and return to below 25 percent of full scale after
the elution time of alpha-BHC and before the elution time of
decachlorobiphenyl.
11.3.9.7 If a chromatogram is replotted electronically to meet these
requirements, the scaling factor-used must be displayed on the
chromatogram.
11.3.9.8 If the chromatogram of any sample needs to be replotted
electronically to meet these requirements, both the initial
chromatogram and the replotted chromatogram(s) must be submitted
in the data package.
11.4 Corrective Action for Sample Analysis
11.4.1 Sample analysis technical acceptance criteria MUST be met before data
are reported. Samples contaminated from laboratory sources or
associated with a contaminated method blank or sulfur cleanup blank
will require re-extraction and re-analysis at no additional cost to
USEPA. Any samples analyzed that do not meet the technical
acceptance criteria will require re-extraction and/or re-analysis at
no additional cost to USEPA.
11.4.2 If the sample analysis technical acceptance criteria are not met,
check calculations, surrogate solutions, and instrument performance.
It may be necessary to recalibrate the instrument or take other
corrective action procedures to meet the technical acceptance
criteria, in which case, the affected samples must be re-analyzed .at
no additional cost to USEPA after the corrective action.
11.4.3. If the Contractor needs to analyze more than the most concentrated
extract and two (2) sample dilutions to have all the
pesticide/Aroclor compounds within the calibration range of the
instrument, contact Sample Management Office (SMO). SMO will contact
the Region for instructions.
D-47/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 11
Data Analysis and Calculations (Con't)
11.4.4 Sample re-extraction/re-analyses performed as a result of suspected
matrix interferences beyond the scope of the method will be reviewed
on a case-by-case basis for payment purposes by the USEPA Contract
Laboratory Program Project Officer (CLP PO). Send a copy of the SDG
Narrative (including your contract number), a description of the
situation, and the requested action to the CLP PO.
OLC03.2 D-48/PEST
-------
Exhibit D Pesticides/Aroclors -- Section 12
Quality Control
12.0 QUALITY CONTROL
12.1 Blank Analyses
12.1.1 Introduction
There are two types of blanks required by this method: the method
blank and the instrument blank. A'separate sulfur cleanup blank may
also be required if some, but not all of the samples are subjected to
sulfur cleanup. Samples that are associated with a sulfur cleanup
blank are also associated with the method blank with which they were
extracted. Both the method and sulfur cleanup blanks must meet the
respective technical acceptance criteria for the sample analysis
technical acceptance criteria to be met.
12.1.2 Method Blank
12.1.2.1 Summary of Method Blank
A method blank is 1.0 liter of reagent water carried through the
entire analytical scheme. The purpose of a method blank is to
determine the levels of contamination associated with the
processing and analysis of samples.
12.1.2.2 Frequency of Method Blank
A method blank must be extracted each time samples are extracted.
The number of samples extracted with each method blank shall not
exceed 20 field samples (excluding matrix spike/matrix spike
duplicate, PE samples, and Laboratory Control Samples). In
addition, a method blank shall:
• Be extracted by the same procedure used to extract samples;
and
• Be analyzed on each Gas Chromatograph/Electron Capture
(GC/ECD) system used to analyze associated samples.
12.1.2.3 Procedure for Method Blank
Measure 1.0 liter of reagent water for each method blank aliquot.
Add 200 uL of the surrogate solution (Section 7.2.3.1). Extract,
concentrate and analyze the method blank according to Section 10.
12.1.2.4 Calculations for Method Blank
Calculate method blank results according to Section 11.
12.1.2.5 Technical Acceptance Criteria for Method Blank
12.1.2.5.1 The requirements below apply independently to each GC column
and to all instruments used for these analyses. Quantitation
must be performed on each GC column.
12.1.2.5.2 All method blanks must be prepared and analyzed at the
frequency described in Section 12.1.2.2, using the procedure in
Section 12.1.2.3 on a GC/ECD system meeting the initial
calibration and calibration verification technical acceptance
criteria. Method blanks must be cleaned-up using Florisil
meeting the technical acceptance criteria for florisil.
12.1.2.5.3 Method blanks must be bracketed at 12-hour intervals (or less)
by acceptable analyses of instrument blanks, PEMs, and
D-49/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 12
Quality Control (Con't)
individual Standard Mixtures A and B as described in Section
10.2.2.1.
12.1.2.5.4 The concentration of the target compounds (Exhibit C -
Pesticides)in the method blank must be less than the Contract
Required Quantitation Limit (CRQL) for each target compound.
12.1.2.5.5 The method blank must meet all sample technical acceptance
criteria in Sections 11.3.5 to 11.3.9.
12.1.2.5.6 Surrogate recoveries must fall within the acceptance window of
30-150 percent. These limits are not advisory.
12.1.2.6 Corrective Action for Method Blank
12.1.2.6.1 If a method blank does not meet the technical acceptance
criteria the Contractor must consider the analytical system to
be out of control.
12.1.2.6.2 If contamination is a problem, the source of the contamination
must be investigated and appropriate corrective measures MUST
be taken and documented before further sample analysis
proceeds. Further, all samples (including Laboratory Control
Samples, requested matrix spike/matrix spike duplicate, and PE
samples) processed with a method blank that does not meet the
method blank technical acceptance criteria (i.e., contaminated)
- will require re-extraction and re-analysis at no additional
,f cost to USEPA. It is the Contractor's responsibility to ensure
.»V- that method interferences caused by contaminants in solvents,
•-•£ reagents, glassware, and sample storage and processing hardware
that lead to discrete artifacts and/or elevated baselines in
gas chromatograms be eliminated.
12.1.2.6.3 If surrogate recoveries in the method blank do not meet the
technical acceptance criteria, listed in 12.1.2.5.6, first re-
"& analyze the method blank. If the surrogate recoveries do not
'•* meet the technical acceptance criteria after re-analysis, then
the method blank and all samples (including Laboratory Control
Samples, requested matrix spike/matrix spike duplicate, and PE
samples) associated with that method blank must be re-extracted
and re-analyzed at no additional cost to USEPA.
12.1.2.6.4 If the method blank fails to meet a technical acceptance
criteria other than Sections 12.1.2.5.4 and 12.1.2.5.6, then
the problem is an instrument problem. Correct the instrument
problem, recalibrate the instrument (if necessary) and re-
analyze the method blank.
12.1.3 Sulfur Cleanup Blank
12.1.3.1 Summary of Sulfur Cleanup Blank
The sulfur cleanup blank is a modified form of the method blank.
The sulfur cleanup blank is hexane spiked with the surrogates and
passed through the sulfur cleanup and analysis procedures. The
purpose of the sulfur cleanup is to determine the levels of
contamination associated with the separate sulfur cleanup-steps.
12.1.3.2 Frequency of Sulfur Cleanup Blank
The sulfur cleanup blank is prepared when only part of a set of
samples extracted together requires sulfur removal. A method
blank is associated with the entire set of samples. The sulfur
OLC03.2 D-50/PEST
-------
Exhibit D Pesticides/Aroclors -- Section 12
Quality Control (Con't)
cleanup blank is associated with the part of the set which
required sulfur cleanup. If all the samples associated with a
given method blank are subjected to sulfur cleanup, then no
separate sulfur cleanup blank is required.
12.1.3.3 Procedure for Sulfur Cleanup Blank
The concentrated volume of the blank must be the same as the final
volume of the samples associated with the blank. The sulfur blank
must also contain the surrogates at the same concentrations as the
sample extracts (assuming 100.0 percent recovery). Therefore, add
0.2 milliliters (mL) of the surrogate spiking solution (Section
7.2.3.1) to 1.8 mL of h'exane in a clean vial.
12.1.3.3.2 Proceed with the sulfur removal (Section 10.1.5.3). using the
same technique (mercury or copper) as the samples associated
with the blank.
12.1.3.3.3 Analyze the sulfur blank according to Section 10.2.
12.1.3.4 Calculations for Sulfur Cleanup Blank
12.1.3.4.1 Assuming that the material in the sulfur blank resulted from
the extraction of a 1 L water sample, calculate the
concentration of each analyte using Equation 12 in Section
11.2.1.8. Compare the results to the CRQL values in Exhibit C
(Pesticides).
12.1.3.4.2 See Section 11.2 for the equations for the other calculations.
12.1.3.5 - Technical Acceptance•Criteria for Sulfur Cleanup.Blanks
12.1.3.5.1 ' The-requirements below apply independently to each GC column
and to all instruments used for.these analyses. Quantitation
must be performed on each column. -
12.1.3.5.2 All sulfur cleanup blanks'must be prepared and analyzed at the
frequency described in Section 12.1.3.2 using the procedure in
Section 12.1.3.3 on a GC/ECD system meeting the initial
calibration and calibration verification technical acceptance
criteria.
12.1.3.5.3 Sulfur cleanup blanks must be bracketed at 12-hour intervals
(or less) by acceptable analyses of instrument blanks, PEMs and
Individual Standard Mixtures A and B, as described in Section
10.2.2.1.
12.1.3.5.4 The concentration of the target compounds (Exhibit C -
Pesticides) in the sulfur cleanup blank must be less than the
CRQL for each target compound.
12.1.3.5.5 The sulfur cleanup blank must meet all sample technical
acceptance criteria in Sections 11.3.5 to 11.3.9.
12.1.3.5.6 Surrogate recoveries must fall within the acceptance windows of
30-150 percent.
12.1.3.6 Corrective Action for Sulfur Cleanup Blank
12.1.3.6.1 If a sulfur cleanup blank does not meet the technical
acceptance criteria, the Contractor must consider the
analytical system to be out of control.
D-51/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 12
Quality Control (Con't)
12.1.3.6.2 If contamination is a problem, the source of the contamination
must be investigated and appropriate corrective measures MUST
be taken and documented before further sample analysis
proceeds. Further, all samples processed with a sulfur cleanup
blank that does not meet the sulfur cleanup blank technical
acceptance criteria (i.e., contaminated) will require re-
extraction and re-analysis at no additional cost to USEPA. It
is the Contractor's responsibility to ensure that method
interferences caused by contaminants in solvents, reagents,
glassware, and sample storage and processing hardware that lead
to discrete artifacts and/or elevated baselines in gas
chromatograms be eliminated.
12.1.3.6.3 If surrogate recoveries in the sulfur cleanup blank do not meet
the technical acceptance criteria, in Section 12.1.3.5.6, first
re-analyze the sulfur cleanup blank. If the surrogate
recoveries do not meet the technical acceptance criteria after
re-analysis, then the sulfur cleanup blank and all samples
associated with that sulfur cleanup blank must be re-
prepared/re-extracted and re-analyzed at no additional cost to
USEPA.
12.1.3.6.4 If the sulfur cleanup blank fails to meet a technical
acceptance criteria other than Sections 12.1.3.5.4, and
12.1.3.5.6, then the problem is an instrument problem. Correct
the instrument problem, recalibrate the instrument (if
necessary) and re-analyze the sulfur cleanup blank.
12.1.4' Instrument Blank
12.1..4-1 Summary of Instrument Blank
• '•&, An instrument blank is a volume of clean solvent spiked with the
-iX- surrogates and analyzed on each GC column and instrument used for
•-• sample analysis. The purpose of the instrument blank is to
determine the levels of contamination associated with the
•% instrumental analysis particularly with regard to carryover of
analytes from standards or highly contaminated samples into other
analysis.
12.1.4.2 Frequency of Instrument Blank
The first analysis in a 12-hour analysis sequence (Section 9.3.2)
must be an instrument blank. All groups of acceptable sample
analyses are to be preceded and followed by acceptable instrument
blanks (Section 10.2.2.1). If more than 12 hours have elapsed
since the injection of the instrument blank that bracketed a
previous 12-hour period, an instrument blank must be analyzed to
initiate a new 12-hour sequence (Section 9.3.2).
12.1.4.3 Procedure for Instrument Blank
12.1.4.3.1 Prepare the instrument blank by spiking the surrogates into
hexane or iso-octane for a concentration of 20.0 nanograms per
milliliter (ng/mL) of Tetrachloro-m-xylene and
Decachlorobiphenyl.
12.1.4.3.2 Analyze the instrument blank according to Section 10.2 at the
frequency listed in Section 12.1.4.2.
OLC03.2 D-52/PEST
-------
Exhibit D Pesticides/Aroclors -- Section 12
Quality Control (Con't).
12.1.4.4 Calculations for Instrument Blank
12.1.4.4.1 Assuming that the material in the instrument blank resulted
from the extraction of a 1 L water sample, calculate the
concentration of each analyte using Equation 12 in Section
11.2.1.8. Compare the results to the CRQL values for water
samples in Exhibit C (Pesticides).
12.1.4.4.2 See Section 11.2 for the equations for the other calculations.
12.1.4.5 Technical Acceptance Criteria for Instrument Blanks
12.1.4.5.1 The requirements'below apply independently to each GC column
and to all instruments used for these analyses. Quantitation
must be performed on each GC column.
12.1.4.5.2 All instrument blanks must be prepared and analyzed at the
frequency described in Section 12.1.4.2 using the procedure in
Section 10.2 on a GC/ECD system meeting the initial calibration
and calibration verification technical acceptance criteria.
12.1.4.5.3 The concentration of each target analyte (Exhibit C -
Pesticides) in the instrument blank must be less than the CRQL
for that analyte.
12.1.4.5.4 The instrument blank must meet all sample technical acceptance
criteria in Sections 11.3.5 to 11.3.9.
12.1.4.6 Corrective Action for Instrument Blank
12.1.4.6.1 If analytes are detected at concentrations greater than the
CRQL or the surrogate Retention Times (RTs) are outside the RT
• windows, all data collection must-be stopped, and corrective
action must be taken. Data for. samples.which were run between
the last-acceptable instrument blank and the unacceptable blank
are considered suspect. An acceptable instrument blank must be
run before additional data are collected. All samples
(including Laboratory Control Samples, requested matrix
spike/matrix spike duplicate, and PE samples) and required
blanks which were run after the last acceptable instrument
blank must be reinjected during a valid run sequence and must
be reported at no additional cost to USEPA.
12.2 Laboratory Control Sample (LCS)
12.2.1 Summary of LCS
The LCS is an internal laboratory quality control sample designed to
assess [on a Sample Delivery Group (SDG)-by-SDG basis] the capability
of the contractor to perform the analytical method listed in this
Exhibit.
12.2.2 Frequency of LCS
The LCS must be prepared, extracted, analyzed, and reported once per
Sample Delivery Group. The LCS must be extracted and analyzed
concurrently with the samples in the SDG using the same extraction
protocol and instrumentation as the samples in the SDG.
D-53/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 12
Quality Control (Con't)
12.2.3 Procedure for LCS >
Measure a 1 liter aliquot of reagent water in a 1 liter graduated
cylinder and transfer the water to a continuous extractor or 2 L
separatory funnel. Pipet 1.0 mL of the LCS spiking solution (Section
7.2.3.8} and 200 uL of the surrogate standard spiking solution into
the water and mix well. Extract, concentrate, and analyze the sample
according to Section 10.
12.2.4 Calculations for LCS
12.2.4.1 Calculate the results according to Section 11.
12.2.4.2 Calculate individual compound recoveries of the LCS using Equation
15.
12.2.5 Technical Acceptance Criteria For LCS
12.2.5.1 The requirements below apply independently to each GC column and
to all instruments used for these analyses. Quantitation must be
performed on each GC column.
12.2.5.2 The LCS must be analyzed at the frequency described in Section
12.2.2 on a GC/ECD system meeting the initial calibration and
calibration verification technical acceptance criteria.
12.2.5.3 The LCS must be prepared as described in Section 12.2.3.
12.2.5V4 The LCS must meet all sample technical acceptance criteria in
Sections 11.3.5 to 11.3.9.
Sfc."
12.2.5"S5 The percent recovery for each of the compounds in the LCS must be
"Si-- within the recovery limits listed in Table D-3.
*xri*.
~>t~
12.2.6iT.> Corrective Action for LCS
-.**-•
12.2.6V1 If the LCS technical acceptance criteria for the surrogates.or the
LCS compound recovery are not met, check calculations, the
surrogate and LCS solutions, and instrument performance. It may
be necessary to recalibrate the instrument or take other
corrective action procedures to meet the surrogate and LCS
recovery criteria.
12.2.6.2 LCS technical acceptance criteria MUST be met before data are
reported. LCS contamination from laboratory sources or any LCS
analyzed not meeting the technical acceptance criteria will
require re-extraction and re-analysis of the LCS at no additional
cost to USEPA.
12.2.6.3 All samples (including matrix spike/matrix spike duplicate and PE
samples) and required blanks, prepared and analyzed in an SDG with
an LCS that does not meet the technical acceptance criteria, will
also require re-extraction and re-analysis at no additional cost
to USEPA.
12.3 Matrix Spike/Matrix Spike Duplicate (MS/MSD)
12.3.1 Summary of MS/MSD
In order to evaluate the effects of the sample matrix on the methods
used for pesticide/Aroclor analyses, USEPA has prescribed a mixture
of pesticide/Aroclor target compounds to be spiked into two aliquots
of a sample, and analyzed in accordance with the appropriate method.
OLC03.2 D-54/PEST
-------
Exhibit D Pesticides/Aroclors -- Section 12
Quality Control (Con't)
12.3.2 Frequency of MS/MSD Analysis
12.3.2.1 MS/MSD samples shall only be analyzed if requested by the Region
[through Sample Management Office (SMO)3 or specified on the
Traffic Report (TR). If requested, a matrix spike and matrix
spike duplicate must be extracted and analyzed for every 20 field
samples in an SDG.
12.3.2.2 As part of USEPA's QA/QC program, water rinsate samples and/or
field blanks may be delivered to a laboratory for analysis. Do
not perform MS/MSD analysis on a water rinsate sample or field
blank.
12.3.2.3 If the USEPA Region requesting MS/MSD designates a sample to be
used as an MS/MSD, then that sample must be used. If there is
insufficient sample volume remaining to perform an MS/MSD, then
the Contractor shall choose.another sample to perform an MS/MSD"
analysis. At the time the selection is made, the Contractor shall
notify the Region (through SMO) that insufficient sample was
received and identify the USEPA sample selected for the MS/MSD
analysis. The rationale for the choice of another sample other
than the one designated by USEPA shall be documented in the SDG
Narrative.
12.3.2.4 If there is insufficient sample volume remaining in any of the
samples in an SDG to perform the requested MS/MSD, the Contractor
shall immediately contact SMO to inform them of the problem. SMO
will contact the Region for instructions. The Region will either
approve that no MS/MSD be performed, or require that a reduced
sample aliquot be used for the MS/MSD analysis. SMO will notify
the Contractor of the Region's decision. The Contractor shall
document the decision in the SDG Narrative.
12.3.2.5 If it appears that the Region has requested MS/MSD analysis at a
greater frequency than specified in Section 12.3.2.1, the
Contractor shall contact SMO. SMO will contact the Region to
determine which samples should have MS/MSD performed on them. SMO
will notify the Contractor of the Region's decision. The
Contractor shall document the decision in the SDG Narrative. If
this procedure is not followed, the Contractor will not be paid
for MS/MSD analysis performed at a greater frequency than required
by the contract.
12.3.2.6 When a Contractor receives only Performance Evaluation (PE)
samples, no MS/MSD shall be performed within that SDG.
12.3.2.7 When a Contractor receives a PE sample as part of a larger SDG, a
sample other than the PE sample must be chosen for the requested
MS/MSD analysis when the Region did not designate a sample to be
used for this purpose.
12.3.3 Procedure for Preparing MS/MSD
12.3.3.1 Measure out two additional 1 L aliquots of the sample chosen for
spiking. Adjust the pH of the samples (if required) and fortify
each with 1 mL of the matrix spiking solution (Section 7.2.3.2) .
Using a syringe or volumetric pipet, add 200 uL of the surrogate
spiking solution (Section 7.2.3.1) to each sample. Extract,
concentrate, cleanup, and analyze the matrix spike and matrix
spike duplicate according to Section 10.0.
12.3.3.2 Matrix spike and matrix spike duplicate samples must be analyzed
at the same concentration as the most concentrated extract for
D-55/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 12
Quality Control (Con't)
which the original sample results will be reported. Do not
further dilute the MS/MSD samples to get either spiked or
nonspiked analytes within calibration range.
12.3.4 Calculations for MS/MSD"
The percent recoveries and the relative percent difference between
the recoveries of each of the compounds in the matrix spike and
matrix spike duplicate samples will be 'calculated and reported by
using the following equations:
EQ. 16
AtACB — *tl>
B*trix Spike Recovery • SL * 100
Where:
SSR =
SR =
SA =
Spike sample result.
Sample result.
Spike added.
EQ. 17
•••v
IHSR -
£ (HSR «• KSDR)
* 100
Where:
RPD =
MSR =
MSDR :
Relative percent difference.
Matrix spike recovery.
Matrix spike duplicate recovery.
12.3.5 Technical Acceptance Criteria for MS/MSD
12.3.5.1 The requirements below apply independently to each GC column and
to all instruments used for these analyses. Quantitation must be
performed on each GC column.
12.3.5.2 If requested, all MS/MSD must be prepared and analyzed at the
frequency described in Section 12.3.2, using the procedure above
and in Section 10 on a GC/ECD system meeting the initial
calibration, calibration verification, and blank technical
acceptance criteria. MS/MSD must be cleaned-up using florisil
meeting the technical acceptance criteria for florisil. MS/MSD
must be bracketed at 12-hour intervals (or less) by acceptable
analyses of instrument blanks, PEMs, and individual standard
mixtures A and B as described in Section 10.2.2.1.
12.3.5.3 The samples must be extracted and analyzed within the contract
required holding times.
12.3.5.4 The RT for each of the surrogates must be within the RT window as
calculated in Section 9 for both GC columns.
OLC03.2
D-56/PEST
-------
Exhibit D Pesticide's/Aroclors -- Section 12
Quality Control (Con't)
12.3.5.5 The limits for matrix spike compound recovery and RPD are given in
Table D-4. As these limits are only advisory, no further action
. by the laboratory is required. However, frequent failures to meet
the limits for recovery or RPD warrant investigation by the
laboratory, and may result in questions from USEPA.
12.3.6 Corrective Action for MS/MSD
Any MS/MSD which fails to meet the technical acceptance criteria in
Sections 12.3.5.1 through 12.3.5.4 must be re-analyzed at no
additional cost to USEPA.
12.4 Method Detection Limit (MDL) Determination
12.4.1 Before any field samples are analyzed under this contract, the MDL
for each pesticide target compound shall be determined for each
sample extraction procedure and on one of 'the instruments to be used
for sample analysis. The MDLs must be verified annually thereafter
(see Section 12.4.2 for MDL verification procedures), until the
contract expires or is terminated or after major instrument
maintenance. Major instrument maintenance includes, but is not
limited to replacement of gas chromatographic column or replacement
of the electron capture detector.
12.4.2 To determine the MDLs, the Contractor shall run an MDL study
following the procedures specified in 40 CFR Part 136. The
Contractor is only required to analyze the'MDL samples on one
instrument used for field sample analyses. MDL verification only is
then required on all other instruments used for field sample analysis
and at the frequency^specified in Section 12.4.1. MDL verification
is achieved by analyzing a;'single reagent,water blank spiked with
each target compound at-a concentration equal to two times .the
analytical determined MDL. The resulting chromatogram.must meet the
qualitative identification criteria outlined in Sections 11.1.1
through 11.1.5.
12.4.3 The determined concentration of the MDL must be less than the CRQL.
12.4.4 All documentation for the MDL studies shall be maintained at the
laboratory and provided to USEPA upon written request.
D-57/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors - Sections 13-16
Method Performance
13.0 METHOD PERFORMANCE
Not Applicable.
14.0 POLLUTION PREVENTION
14.1 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. The 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 feasiblely reduced at the
source, USEPA recommends recycling as the next best option.
14.2 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, B.C. 20036, (202)872-
4477.
15.0 WASTE MANAGEMENT
The Environmental Protection Agency requires that laboratory waste
management practices be conducted consistent with all applicable rules
and regulations. USEPA urges laboratories to protect the air, water,
Sv.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
.ijwaste regulations, particularly the hazardous waste identification rules
' 'Sand 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 14.2.
•="rv
16.0 REFERENCES
Not Applicable.
OLC03.2 D-58/PEST
-------
Exhibit D Pesticides/Aroclors -- Section 17
Tables/Diagrams/Flowcharts
17.0 TABLES/DIAGRAMS/FLOWCHARTS
TABLE D-l
RETENTION TIME WINDOWS FOR SINGLE AND MULTICOMPONENT
ANALYTES AND SURROGATES.
Compound Identification
Compound Window (minutes)
alpha-BHC ±0.05
beta-BHC ±0.05
gamma-BHC ±0.05
delta-BHC ±0.05
Heptachlor ±0.05
Aldrin ±0.05
alpha-Chiordane ±0.07
gamma-Chiordane ±0.07
Heptachlor epoxide ±0.07
Dieldrin ±0.07
Endrin ±0.07
Endrin aldehyde ±0.07
Endrin ketone . ±0.07
4,4'-ODD ±0.07
4,4'-DDE ±0.07
4,4'-DDT ±0.07
Endosulfan I ±0.07
Endosulfan II ±0.07
Endosulfan sulfate ±0.07
Methoxychlor ±0.07
Aroclors ±0.07
Toxaphene ±0.07
Tetrachloro-m-xylene ±0.05
Decachlorobiphenyl ±0.10
D-59/PEST OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 17
Tables/Diagrams/Flcwcnarts {Con't)
TABLE D-2
NUMBER OF POTENTIAL QUANTITATION PEAKS
Multicomponent Analyte
No. of Potential Quantitation Peaks
Aroclor 1016/1260
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Toxaphene
5/5
3
4
5
5
5
4
OLC03.2
D-60/PEST
-------
Exhibit D Pesticides/Aroclors — Section 17
Tables/Diagrams/Flowcharts (Con't)
TABLE D-3
LABORATORY CONTROL SAMPLE RECOVERY LIMITS
Compound % Recovery
gamma-BHC 50-120
Heptachlor epoxide 50-150
Dieldrin 30-130
4,4'-DDE 50-150
Endrin 50-120
Endosulfan sulfate 50-120
gamma - Chi or dane 30-130
NOTE: The recovery limits for any of the compounds in the LCS may be
expanded at any time during the period of performance if USEPA
determines that the limits are too restrictive.
D-61/PEST . OLC03.2
-------
Exhibit D Pesticides/Aroclors -- Section 17
Tables/Diagrams/Flowcharts (Con't)
TABLE D-4
MATRIX SPIKE RECOVERY AND RELATIVE PERCENT DIFFERENCE LIMITS
Compound % Recovery RPD
gamma-BHC (Lindane) 56-123 15
Heptachlor 40-131 20
Aldrin 40-120 22
Dieldrin 52-126 . 18
Endrin 56-121 21
4,4'-DDT 38-127 27
OLC03.2 D-62/PEST
-------
EXHIBIT E
QUALITY ASSURANCE/QUALITY CONTROL PROCEDURES AND REQUIREMENTS
E-l OLC03.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
OLC03.2 E-2
-------
Exhibit E -- Quality Assurance/Quality Control Procedures and Requirements
Table of Contents
Page
1.0 OVERVIEW 5
1.1 Quality Assurance/Quality Control (QA/QC) Activities 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) 'PRACTICES -7
4.0 SPECIFIC QUALITY ASSURANCE/QUALITY CONTROL (QA/QC) 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 Quality Assurance/Quality Control Measurements 8
5.0 QUALITY ASSURANCE PLAN (QAP) 9
5.1 Introduction 9
5.2 Required Elements of a Quality Assurance Plan 10
5.3 Updating and Submitting the Quality Assurance Plan 11
5.4 Corrective Actions 12
6.0 STANDARD OPERATING PROCEDURES (SOPs) 13
' 6.1' Introduction 13
6.2 . Format 14
6.3 Requirements 14
6:4, Updating and Submitting SOPs 16
6.5 Corrective Action 18
7..0 .CONTRACT COMPLIANCE SCREENING (CCS) 19
7.1 Overview 19
7.2 CCS Results 19
7.3 CCS Trend Report 19
7.4 Corrective Actions 19
8.0 ANALYTICAL STANDARDS REQUIREMENTS . . . .' 20
8.1 Overview 20
8.2 Preparation of Chemical Standards from the Neat High
Purity Bulk Material 20
8.3 Purchase of Chemical Standards Already in Solution 21
8.4 Requesting Standards from the USEPA Standards Repository 23
8.5 Documentation of the Verification and Preparation of
Chemical Standards 23
8.6 Corrective Actions 24
9.0 DATA PACKAGE AUDITS 25
9.1 Overview 25
9.2 Responding to the Data Package Audit Report 25
9.3 Corrective Actions 25
10.0 REGIONAL DATA REVIEW 26
10.1 Overview 26
11.0 PROFICIENCY TESTING 26
11.1 Performance Evaluation (PE) Samples .- 26
11.2 Quarterly Blind (QB) Audits 27
11.3 Corrective Actions 29
E-3 OLC03.2
-------
Exhibit E — Quality Assurance/Quality Control Procedures and Requirements
Table of Contents (Continued)
Section Page
12.0 ON-SITE LABORATORY EVALUATIONS 30
12.1 Overview 30
12.2 Quality Assurance On-Site Evaluation 30
12.3 Evidentiary Audit ' 30
12.4 Discussion of the On-Site Team's Findings . . . 31
12.5 Corrective Action Reports for Follow-Through to Quality
Assurance and Evidentiary Audit Reports 31
12.6 Corrective Actions 32
13.0 ELECTRONIC DATA 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 Corrective Actions 35
13.5 Maintenance of the Magnetic Tape Storage Device 36
14.0 DATA MANAGEMENT 37
14.1 Overview 37
14.2 Documenting Data Changes 37
14.3 Lifecycle Management Procedures 37
14.4 Personnel Responsibilities 38
OLC03.2 E-4
-------
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.
E-5 OLC03.2
-------
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
methods. The methods in this contract have been validated on samples
typical of those received by the laboratories in the Contract Laboratory
Program (CLP). However, the validation of these methods does not
guarantee that they perform equally well for all sample matrices
encountered. Inaccuracies can also result from causes other than
unanticipated matrix effects, such as sampling artifacts, equipment
malfunctions, and operator error. Therefore, the QC component of each
method is indispensable.
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, 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 necessary components of a complete QA/QC program include internal
QC criteria that demonstrate acceptable levels of performance, as
determined by QA review. External review of-data and procedures is
accomplished by the monitoring activities of the National Program
Office, 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 CLP Project
Officer (CLP PO).
2.1.2 This exhibit does not provide specific instructions for constructing
QA Plans, QC systems, or a QA organization. It is, however, an
explanation of the QA/QC requirements of the program. It outlines
some minimum standards for QA/QC programs. It also includes specific
items that are required in a Quality Assurance 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, USEPA requires the following from the Contractor:
• Preparation of, and adherence to, a written QAP, the elements of
which are designated in Section 5;
, • Preparation of, and adherence to, Standard Operating Procedures
(SOPs) as described in Section 6;
OLC03.2 E-6
-------
Exhibit E -- Sections 2 & 3
General QA/QC Practices
• Adherence to the analytical methods and associated QC
requirements specified in the contract;
• Verification of analytical standards and documentation of the
purity of neat materials and the purity and accuracy of solutions
obtained from private chemical supply houses;
• Submission of all raw data and pertinent documentation for
Regional review;
• Participation in the analysis of laboratory evaluation samples,
including. adherence to corrective action procedures;
• Submission, upon request, of instrument data tapes and applicable
documentation for tape audits, including a copy of the Sample
Data Package ;
• Participation in on- site laboratory evaluations, including
adherence to corrective action procedures; and
• Submission of all original documentation generated during sample
analyses for USEPA review.
3.0 GENERAL QUALITY ASSURANCE/QUALITY CONTROL (QA/QC) PRACTICES
Contractor shall adhere to 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 OLC03.2
-------
Exhibit E -- Section 4
Specific QA/QC Procedures
4.0 SPECIFIC QUALITY ASSURANCE/QUALITY CONTROL (QA/QC) PROCEDURES •
The QA/QC procedures defined herein shall be used by the Contractor when
performing the methods specified in Exhibit D. When additional QA/QC
procedures are specified in the methods in Exhibit D, the Contractor
shall also follow these procedures.
NOTE: The cost of performing all QA/QC procedures specified in this
Statement of Work (SOW) is included in the price of performing the bid
lot.
4.1 Purpose
4.1.1 The purpose of this document is to provide a uniform set of
procedures for the analysis of organic samples, documentation of
methods and their performance, and verification of the sample data
generated. The program will also assist laboratory personnel in
recalling and defending their actions under cross examination if
required to present court testimony in enforcement case litigation.
Although it is impossible to address all analytical situations in one
document, the approach taken here is to define the minimum
requirements for all major steps relevant to any organic low
concentration analysis.
4.1.2 The primary function of the QA/QC program is the definition of
procedures for the evaluation and documentation of analytical
methodologies and the reduction and reporting of data. 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 (Exhibit D).
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 can expect
to analyze at least two Performance Evaluation (PE) samples per calendar
quarter during the contract period for organic low concentration
analyses.
4.3 Annual Verification of Method Detection Limits (MDLs)
The Contractor shall perform annual verification of MDLs in accordance
with the specifications in Exhibit D. All the MDLs shall meet the
Contract Required Quantitation Limits (CRQLs) specified in Exhibit C.
4.4 Quality Assurance/Quality Control Measurements
4.4.1 In this Exhibit, as well as other places within this SOW, the term
"analytical sample" is used in discussing the required frequency or
placement of certain QA/QC measurements. As the term is used,
analytical sample includes all field samples, including PE samples,
received from an external source. It also includes all required
QA/QC samples [requested Matrix Spike/Matrix Spike Duplicate(s)
(MS/MSD), and Laboratory Control Sample (LCS)] except those directly
related to instrument calibration or calibration verification
(calibration standards, Initial Calibration, Continuing Calibration,
and tunes).
OLC03.2 E-8
-------
Exhibit E -- Sections 4 & 5
Quality Assurance Plan
4.4.2 In order for the QA/QC information to reflect the status of the
samples analyzed, all samples and their QA/QC analysis shall be
analyzed under the same operating and procedural conditions.
4.4.3 If any QC measurement fails to meet contract criteria,-the analytical
measurement must not be repeated prior to taking the appropriate
corrective action as specified in Exhibit D.
4.4.4 The Contractor shall report all QC data in the exact format specified
in Exhibits B and H.
4.4.5 In addition, the Contractor shall establish a QA program 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.
5.0 QUALITY ASSURANCE 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.
5.1.1 As evidence of such a program, the Contractor shall prepare'a written
QAP which describes the procedures that are implemented to achieve
the following:
• Maintain data integrity, validity, and usability;
• Ensure that analytical measurement systems are maintained in an
acceptable state of stability and reproducibility,-
• Detect problems through data assessment and establish corrective
action procedures which keep the analytical process reliable,- and
• Document all aspects of the measurement process in order €o
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.
Where applicable, 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 within 7 days of written request by the USEPA Regional
Contract Laboratory Program Project Officer (CLP PO). Additional
information relevant to the preparation of a QAP can be found in
USEPA and American Society for Testing and Materials (ASTM)
publications.
E-9 OLC03.2
-------
Exhibit E -- Section 5
Quality Assurance Plan (Con't)
5.2 Required Elements of a Quality Assurance Plan
The required elements of a laboratory's QAP are outlined in this
section. This outline should be used as a framework for developing the
QAP.
A. Organization and Personnel
1. QA Policy and Objectives
2. QA Management
a. Organization
b. Assignment of QA/QC Responsibilities
c. Reporting Relationships
d. QA Document Control Procedures
e. QA Program Assessment Procedures
3. Personnel
a. Resumes
b. Education and Experience Pertinent to this Contract
c. Training Progress
B. Facilities and Equipment
1. Instrumentation and Backup Alternatives
2. Maintenance Activities and Schedules
C. Document Control
1. Laboratory Notebook Policy
2 . Sample Tracking/Custody Procedures
3. Logbook Maintenance and Archiving Procedures
4. Sample Delivery Group (SDG) File Organization, Preparation, and
Review Procedures
5. Procedures for Preparation, Approval, Review, Revision, and
Distribution of Standard Operating Procedures (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
OLC03.2 E-10
-------
Exhibit E -- Section 5
Quality Assurance Plan (Con't)
5. Decision Processes, Procedures, and.Responsibility for Initiation
of Corrective Action
E. Data Generation
1. Data Collection Procedures
2 . Data Reduction Procedures
3. Data Validation Procedures ;
4. Data Reporting and Authorization Procedures
F. Quality Assurance
1. Data Quality Assurance
2. Systems/Internal Audits
3. Performance/External Audits
4 . Corrective Action Procedures
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 Plan
5.3.1 Initial Submission. During the contract solicitation process, the
Contractor is required to submit its QAP to the CLP Contracting
Officer. Within sixty days after contract award, the Contractor
shall maintain on file a revised OAP. fully compliant with the
recruirements of this contract. The revised QAP will become the
official QAP under the contract and may be used during legal
proceedings. The Contractor shall maintain the QAP on file at the
Contractor's facility for the term of the contract. Both the initial
submission and the revised QAP shall be paginated consecutively in
ascending order. The revised QAP shall include:
• 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. ^
E-ll OLC03.2
-------
Exhibit E -- Section 5
Quality Assurance Plan (Con't)
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. The USEPA
requestor will designate the recipients.
5.3.2 Subsequent Updates and Submissions. During the term of contract, the
Contractor shall amend the QAP when the following circumstances
occur:
• USEPA modifies the contract;f
• USEPA notifies the Contractor of deficiencies in the QAP
document;
• USEPA notifies the Contractor of deficiencies resulting from
USEPA's review of the Contractor's performance;
• The Contractor identifies deficiencies resulting from their
internal review of their QAP document;
• 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 30 days of when the
circumstances listed above result in a discrepancy between what
was previously described in the QAP and what is presently
occurring at the Contractor's facility. When the QAP is amended,
all changes in the QAP shall be clearly marked (e.g., a bar in the
margin indicating where the change is found in the document, or
highlighting the change by underlining the change, bold printing
the change, or using a different print font). The amended section
pages shall have the date on which the changes were implemented.
The Contractor shall incorporate all amendments to the latest
version of the QAP document. The Contractor shall archive all
amendments to the QAP document for future reference by USEPA.
5.3.2.2 The Contractor shall send a copy of the latest version of the QAP
document within 7 days of a written request by the Regional CLP PO
as directed. The USEPA requestor will designate the recipients.
5.4 Corrective Actions
If the Contractor fails to adhere to the requirements listed in this
section, the Contractor may expect, but USEPA is not limited to the
following actions: reduction in the numbers of samples sent under this
contract, suspension of sample shipment to the Contractor, data, package
audit, electronic data audit (i.e., Gas Chromatograph/Mass Spectrometer
(GC/MS) tape audit), an on-site laboratory evaluation, remedial
performance evaluation sample, and/or contract sanctions.
OLC03.2 E-12
-------
Exhibit E -- Section 6
Standard Operating Procedures
6.0
6.1
STANDARD OPERATING PROCEDURES (SOPs)
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, a SOP is
a written document which provides directions for the step-by-step
execution of an operation, analysis, or action which is commonly
accepted as the method for performing certain routine or repetitive
tasks.
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 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) contract's 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
•i.. inspection at such evaluations. During on-site laboratory
f' evaluations, laboratory personnel may be asked to demonstrate the
application of the SOPs.
'*."
• Available to the designated recipients within 7 days, upon
'i' request by the USEPA Regional CLP Project Officer (CLP PO) .
v • Capable of-providing for the development of documentation that is
sufficiently complete to record the performance of all tasks
required by the protocol.
• Capable of demonstrating the validity of data reported by the
Contractor and explain the cause of missing or inconsistent
results.
• Capable of describing the corrective measures and feedback
mechanism utilized when analytical results do not meet protocol
requirements.
• Reviewed regularly and updated as necessary when contract,
facility, or Contractor procedural modifications are made.
• Archived for future reference in usability or evidentiary
situations.
• Available at specific work stations as appropriate.
• Subject to a document control procedure which precludes the use
of outdated or inappropriate SOPs.
E-13
OLC03.2
-------
Exhibit E -- Section 6
Standard Operating Procedures (Con't)
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;
• Scope and application;
• Definitions;
• Procedures;
• Quality Control (QC) limits;
• Corrective action procedures, including procedures for secondary
review of information being generated;
• Documentation description and example forms;
• Miscellaneous notes and precautions; and
• References.
6.3 Requirements
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.
6.3.2 Sample Receipt and Storage
• Sample receipt and identification logbooks;
• Refrigerator temperature logbooks; and
• Security precautions.
6.3.3 Sample Preparation
• Reagent purity check procedures and documentation;
• Extraction procedures;
• Extraction bench sheets,- and
• Extraction logbook maintenance.
6.3.4 Glassware Cleaning
6.3.5 Calibration (Balances, etc.)
• Procedures;
• Frequency requirements;
• Preventive maintenance schedule and procedures; and
• Acceptance criteria and corrective actions.
OLC03.2 E-14
-------
Exhibit E -- Section 6
Standard Operating Procedures (Con't)
6.3.6 Analytical Procedures (for each analytical system)
• Instrument performance specifications;
• Instrument operating procedures;
• Data acquisition system operation;
• Procedures when automatic quantitation algorithms are overridden;
• QC required parameters;
• Analytical run/injection logbooks; and
• 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;
• 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 SDG File contents;
• Complete SDG File organization and assembly procedures, including
review policy; and
• Document inventory procedures, including review policy.
E-15 OLC03.2
-------
Exhibit E -- Section 6
Standard Operating Procedures (Con't)
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 QA inspection procedure (demonstrated
by supervisory sign-off on personal notebooks, internal
laboratory evaluation samples, etc.);
• Frequency and type of internal audits (e.g., random, quarterly,
spot checks, perceived trouble areas) ,-
• Demonstration of problem identification, corrective actions, and
resumption of analytical processing. Sequence resulting from
internal audit (i.e., QA feedback); and
• Documentation of audit reports (internal and external), response,
corrective action, etc.
6.3.12 Data Management and Handling
• Procedures for controlling and estimating data entry errors,-
• Procedures for reviewing changes to data and deliverables and
ensuring traceability of updates;
• Lifecycle management procedures for testing, modifying, and
implementing changes to existing computing systems including
hardware, software, and documentation or installing new systems;
• 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,-
• Specifications for staff training procedures; and
• Virus protection procedures for software and electronic
deliverables.
6.4 Updating and Submitting SOPs
6.4.1 Initial Submission. During the contract solicitation process, the
Contractor is required to submit their SOPs to the CLP Contracting
Officer. Within 60 days after contract award, the Contractor shall
maintain on file a complete revised set of SOPs. fully compliant with
the requirements of this contract. The revised SOPs will become the
official SOPs under the contract and may be used during legal
OLC03.2 E-16
-------
Exhibit E -- Section 6
Standard Operating Procedures (Con't)
proceedings. The Contractor shall maintain the complete set of SOPs
on file at the Contractor's facility for the term of the contract.
Both the initial submission of SOPs and the revised SOPs shall be
paginated consecutively in ascending order. The revised SOPs shall
include:
• 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
• Changes resulting from USEPA's review of the laboratory
evaluation sample data, bidder supplied documentation, and
recommendations made during the preaward 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. The USEPA requestor 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:
• USEPA modifies the contract;
• USEPA notifies the Contractor of deficiencies in their SOP's
documentation;
• 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 their SOPs documentation; or
• 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
30 days of when the circumstances listed above result in a
discrepancy between what was previously described in the SOPs and
what is presently occurring at the Contractor's facility. All
changes in the SOPs shall be clearly marked (e.g., a bar in the
margin indicating where the change is in the document, or
highlighting the change by underlining the change, bold printing
the change, or using a different print font). The amended/new
SOPs shall have the date on which the changes were implemented.
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. An alternate delivery schedule
for submitting the letter and amended/new SOPs may be proposed by
the Contractor, but it is the sole decision of the USEPA
Contracting Officer to approve or disapprove the alternate
delivery schedule. If an alternate delivery schedule is proposed,
E-17 OLC03.2
-------
Exhibit E -- Section 6
Standard Operating Procedures (Con't)
the Contractor shall describe in a letter to the USEPA Regional
CLP PO and the Contracting Officer why it is unable to meet the
delivery schedule listed in this section. The USEPA Regional CLP
PO may grant an extension of up to 30 days for amending/writing
new SOPs. An extension for amending/writing new SOPs beyond 30
days must be approved by the USEPA Contracting Officer.
Similarly, an extension of up to 14 days for submission of the
letter documenting the reasons for the changes and for submitting
amended/new SOPs may be approved by the USEPA Regional CLP PO. An
extension beyond the 14 days must be approved by the USEPA
- Contracting Officer. The Contractor shall proceed and not assume
that an extension will be granted until so notified by the USEPA
Regional CLP PO and/or Contracting Officer.
6.5 Corrective Action
If the Contractor fails to adhere to the requirements listed in this
section, the Contractor may expect, but USEPA is not limited to the
following actions: reduction in the number of samples sent under this
contract, suspension of sample shipment to the Contractor, data package
audit, electronic data audit, an on-site laboratory evaluation, remedial
performance evaluation sample, and/or contract sanctions.
OLC03.2 E-18
-------
Exhibit E -- Section 7
Contract Compliance Screening
7.0 CONTRACT COMPLIANCE SCREENING (CCS)
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 mailed to the Contractor and all other data recipients.
The Contractor has a period of time to correct deficiencies. The
Contractor shall send all corrections to the Regional client and SMO
within 6 business days. 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 may generate a CCS trend report which summarizes CCS results over
a given period of time. USEPA may 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 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 of the on-site laboratory evaluation. An
alternate delivery schedule may be proposed by the Contractor, but it is
the sole decision of USEPA to approve or disapprove the alternate
delivery schedule. If an alternate delivery schedule is proposed, the
Contractor shall describe in a letter to the USEPA Regional CLP PO and
Contracting Officer why it is unable to meet the delivery schedule
listed in this section. The USEPA Regional CLP PO may grant an
extension of up to 14 days for the Contractor's response to the CCS
trend report. An extension beyond 14 days must be approved by the USEPA
Contracting Officer. The Contractor shall proceed and not assume that
an extension will be granted until so notified by the appropriate USEPA
official.
7.4 Corrective Actions
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 Section 6.
7.4.2 If the Contractor fails to adhere to the requirements listed in this
section, the Contractor may expect, but USEPA is not limited to the
following actions: reduction in the number of samples sent under the
contract, suspension of sample shipment to the Contractor, data
package audit, electronic data audit, an on-site laboratory
evaluation, a remedial performance evaluation sample, and/or contract
sanctions.
E-19
OLC03.2
-------
Exhibit E -- Section 8
Analytical Standards Requirements
8.0 ANALYTICAL STANDARDS REQUIREMENTS
8.1 Overview
USEPA may 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 its 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 If required by the manufacturer, the chemical standards shall be kept
refrigerated when not being used in the preparation of standard
solutions. Proper storage of chemicals is essential in order to
safeguard them from decomposition.
8.2.3 The purity of a compound can sometimes be misrepresented by a
chemical supply house. Since knowledge of purity is needed to
calculate the concentration of solute in a solution standard, it is
the Contractor's responsibility to have analytical documentation
ascertaining that the purity of each compound is correctly stated.
Purity confirmation, when performed, should use appropriate
techniques. Use of two or more independent methods is recommended.
The correction factor for impurity when weighing neat materials in
the preparation of solution standards is:
EQ. 1
weight ot impure expound - reiobt ot pure
(percent pur icy/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 When compound purity is assayed to be 97 percent or greater, the
weight may be used without correction to calculate the concentration
of the stock standard. If the compound purity is assayed to be less
than 97 percent, the weight shall be corrected when calculating the
concentration of the stock solution.
8.2.5 Mis-identification of compounds occasionally occurs and it is
possible that a mislabeled comp'ound may be received from a chemical
supply house. It is the Contractor's responsibility to have
analytical documentation ascertaining that all compounds used in the
preparation of solution standards are correctly identified.
Identification confirmation, when performed, shall use Gas
Chromatography/Mass Spectrometry (GC/MS) analysis on at least two
different analytical columns, or other appropriate techniques.
8.2.6 Calculate the weight of material to be weighed out for a specified
volume, taking into account the purity of the compound and the
OLC03.2 E-20
-------
Exhibit E -- Section 8
Analytical Standards Requirements (Con't)
desired concentration. A second person shall verify the accuracy of
the calculations. Check balances for accuracy with a set of standard
weights every 12 hours. All weighing shall be performed on an
analytical balance to the nearest 0.1 milligram (mg) and verified by
a second person. The solvent used to dissolve the solute shall be
compatible with the protocol in which the standard is to be used; the
solute shall be soluble, stable, and non-reactive with the solvent.
In the case of a multicomponent solution, the components must not
react with each other.
8.2.7 Transfer the solute to a volumetric, flask and dilute to the specified
solution volume with solvent after ensuring dissolution of the solute
in the solvent. Sonication or warming may be performed to promote
dissolution of the solute. This solution shall be called the primary
standard and all subsequent dilutions shall be traceable back to the
primary standard.
8.2.8 Log notebooks are to be kept for all weighing and dilutions. All
subsequent dilutions from the primary standard and the calculations
for determining their concentrations are to be recorded and verified
by a second person. All solution standards are to be refrigerated,
if required, when not in use. All solution standards are to be
clearly labeled as to the identity of the analyte or analytes,
concentration, date prepared, solvent, and initials of the preparer.
'•'8.3 Purchase of Chemical Standards Already in Solution
Solutions of analytical reference standards can be purchased by
Contractors provided they meet the following criteria.
8.3.1 ... Contractors shall maintain documentation of the purity confirmation
.>:', of the material to verify the integrity of the standard solutions
=•*! they purchase.
8.3.2 The Contractor shall purchase standards for which the quality is
demonstrated statistically and analytically by a method of the
supplier's choice. One way this can be demonstrated is to prepare
and analyze three solutions: a high standard, a low standard, and a
standard at the target concentration (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 percent of the target concentration
using the equations in Section 8.3.2.6. If the procedure described
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 percent greater than the target
standard. This is called the "high standard". One further
aliquot is taken from the second solution and diluted to a
concentration 10 percent less than the target standard. This is
called the "low standard".
E-21 OLC03.2
-------
Exhibit E -- Section 8
Analytical Standards Requirements (Con't)
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
Y. + Y. + Y, + Y. + YK + Y.
BEAM - * * * • * *
EQ. 3
Y* + Y* + Y* + Y* + Y* + Y* - 6(HE1N>*
VARIANCE • = = * 4 * *
The values YK Y2, Y3, ..., represent the results of the six
analyses of each standard. The means of the low, target, and high
standards are designated Mlr M2, and M3, respectively. The
variances of the low, target, and high.standards are designated
Vlf V2, and V3, respectively. Additionally, a pooled variance, Vp,
is calculated.
EQ. 4
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
_!».- A
1.1 0.9
„,...
TEST STATISTIC •
If the test statistic exceeds 2.13, then the supplier has failed
to demonstrate a 20 percent difference between the high and low
standards. In such a case, the standards are not acceptable.
OLC03.2 E-22
-------
Exhibit E -- Section 8
Analytical Standards Requirements (Con't)
3_
2.2
8.3.2.5 The test statistic shall be calculated:
EQ. 6
TEST STATISTIC -
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 percent confidence intervals for the mean result of each
standard shall be calculated:
EQ. 7
Interval tor Low Standard - H, ±2.13
EQ. B
Interval tor Target Standard - Hj ± 2.13
EQ. 9
Interval tor High Standard - H, ± 2.13
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 percent 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.
E-23 OLC03.2
-------
Exhibit E -- Section 8
Analytical Standards Requirements (Con't)
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 may generate a report discussing deficiencies in the
Contractor's documentation for the verification and preparation of
chemical standards or may discuss the deficiencies during an on-site
laboratory evaluation. In a detailed letter to the USEPA Regional
CLP PO and Quality Assurance Technical Support (QATS), the Contractor
shall address the deficiencies and the subsequent corrective action
implemented by the Contractor to correct the deficiencies within 14
days of receipt of the report or the on-site laboratory evaluation.
An alternate delivery schedule may be proposed by the Contractor, but
it is the sole decision of USEPA to approve or disapprove the
alternate delivery schedule. If an alternate delivery schedule is
proposed, the Contractor shall describe in a letter to the USEPA
Regional CLP PO and the Contracting Officer why it is unable to meet
the delivery schedule listed in this section. The USEPA Regional CLP
PO may grant an extension of up to 14 days for the Contractor's
response letter to the standards documentation report. An extension
beyond 14 days must be approved by the USEPA Contracting Officer.
The Contractor shall proceed and not assume that an extension will be
granted until so notified by the appropriate USEPA official.
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 Section 6.
8.6 Corrective Actions
If the Contractor fails to adhere to the requirements listed in this
section, a Contractor may expect, but USEPA is not limited to the
following actions: reduction in the number of samples sent under the
contract, suspension of sample shipment to the Contractor, data package
audit, electronic data audit, an on-site laboratory evaluation, a
remedial laboratory evaluation sample, and/or contract sanctions.
OLC03.2- E-24
-------
Exhibit E -- Section 9
Data Package Audits
9.0
DATA PACKAGE 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 the 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 may send a copy of
:— ;,. the data package audit report to the Contractor or may discuss the
data package audit report on an on-site laboratory evaluation. In a
detailed letter to the USEPA Regional Contract Laboratory Program
Project Officer (CLP PO) and the USEPA designated recipient, the
•'•• : •.'•; Contractor shall discuss the corrective actions implemented to
-r resolve the deficiencies listed in the data package audit report
• - ••";• within 14 days of receipt of the report.
- - - f\
9.2.2 An alternate delivery schedule may be proposed by the Contractor, but
-'•:'': ."•, it is the sole decision of USEPA to approve or disapprove the
"'-"• ;• alternate delivery schedule. If an alternate delivery schedule is
~^::. -j~ proposed, the Contractor shall describe in a letter to the USEPA
Regional CLP PO and the Contracting Officer why it is unable to meet
the delivery schedule listed in this section. The USEPA Regional CLP
PO may grant an extension of up to 14 days for the Contractor's
response letter to the data package report. An extension beyond 14
days must be approved by the USEPA Contracting Officer. The
Contractor shall proceed and not assume that an extension will be
granted until so notified by the appropriate USEPA official.
9.2.3 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
Section 6.
9.3 Corrective Actions
If the Contractor fails to adhere to the requirements listed in this
section, the Contractor may expect, but USEPA is not limited to the
following actions: reduction in the number of samples sent under the
contract, suspension of sample shipment to the Contractor, an.on-site
laboratory evaluation, data package audit, electronic data audit,
remedial -performance evaluation sample, and/or contract sanctions.
E-25
OLC03.2
-------
Exhibit E -- Sections 10 & 11
Regional Data Review
10.0 REGIONAL DATA REVIEW
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 National Program Office. Each Region
uses these guidelines as the basis for data evaluation. Individual
Regions may augment the basic guideline review process with additional
1 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 performed at the Sample Management Office (SMO), which is
designed to identify contractual discrepancies, and the review
performed by the National Program Office, which is designed to
evaluate Contractor and method performance. These individual
evaluations are integrated into a collective review that is necessary
for Program and Contractor administration and management, and may be
used to take appropriate action to correct deficiencies in the
Contractor's performance.
11.0 PROFICIENCY TESTING
As a means of measuring and evaluating both the Contractor's and the
method's analytical performance, the Contractor must participate in
USEPA's Proficiency Testing Program. USEPA's Proficiency Testing
Program involves the analysis of Case specific Performance Evaluation
(PE) samples and the participation in interlaboratory 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.
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 National Program Office.
PE samples will 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 prepared 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 also be met. The PE
OLC03.2 E-26
-------
Exhibit E -- Section 11
Proficiency Testing (Con't)
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/parameters 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/parameter. USEPA will notify the
Contractor of unacceptable performance. USEPA reserves the right to
adjust the PE sample acceptance windows in order to compensate for
any unanticipated difficulties with a particular PE sample.
11.1.5 The Contractor shall demonstrate acceptable analytical performance
for both identification and quantitation of PE sample analytes/
parameters. For unacceptable PE sample performance, USEPA may take,
but is not limited to,-the following actions: reduce value or
rejection of data for the samples, SDG, or Case impacted, contract
sanctions, reduction in the number of samples shipped to the
laboratory, suspension of sample shipment, an on-site laboratory
inspection, a full data package audit, electronic data audit, and/or
require the laboratory to analyze a Remedial QB.
NOTE: A Contractor's prompt response demonstrating that corrective
actions have been taken to ensure the Contractor's capability to meet
contract requirements may facilitate continuation of full sample
delivery.
11.2 .'Quarterly Blind (QB) Audits
ill.2.1-'£ QB Audits may be scheduled concurrently with all contract
:-". -:.=; .:~: office (SMO) . QB samples will assist USEPA in monitoring Contractor
:n:-. \: 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.
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 preparati.on and
method analysis sections of Exhibit D. All contract required QC
shall also be met. 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/parameters 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/parameter. USEPA wil-1 notify the
E-27 OLC03.2
-------
Exhibit E -- Section 11
Proficiency Testing (Con't)
Contractor of .unacceptable performance. USEPA reserves the right to
adjust the PE sample acceptance windows in order to compensate for
any unanticipated difficulties with a particular PE sample. The
Contractor's QB sample performance will be assessed into one of the
following three categories:
11.2.4.1 Acceptable, No Response Required: Score greater than or equal to
90 percent. 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 percent, but less than 90 percent.
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 percent. Deficiencies exist in the
Contractor's performance to the extent that the National Program
Office has determined that the Contractor has not demonstrated the
capability to meet the contract requirements. 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 Regional Contract Laboratory Program
Project Officer (CLP PO) and CLP Quality Assurance (QA) Coordinator
within 14 days of receipt of notification from USEPA.
11.2.5.1 An alternate delivery schedule for the corrective action letter
may .be proposed by the Contractor, but it is the sole decision of
USEPA to approve or disapprove the alternate delivery schedule.
If an alternate delivery schedule is proposed, the Contractor
shall describe in a letter to the USEPA Regional CLP PO and
Contracting Officer why the laboratory is unable to meet the
original delivery schedule listed in Section 11.2.5. The USEPA
Regional CLP PO may grant an extension of up to 14 days for the
Contractor's corrective action .letter. An extension beyond 14
days must be approved by the USEPA Contracting Officer. The
Contractor shall proceed and not assume that an extension will be
granted until so notified by the appropriate USEPA official.
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 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. For unacceptable QB sample performance
(Section 11.2.4.3), USEPA may take, but is not limited to, the
following actions: reduction in the number of samples shipped to the
laboratory, suspension of sample shipment, an on-site laboratory
inspection, electronic data audit, a full data package audit, and/or
require the laboratory to analyze a Remedial QB sample, and/or
contract sanctions.
NOTE: A Contractor's prompt response demonstrating that corrective
actions have been taken to ensure the Contractor's capability to meet
contract requirements may facilitate continuation of full sample
delivery.
OLC03.2 . E-28
-------
Exhibit E -- Section 11
Proficiency Testing (Con't)
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 National
Program Office with the Contractor(s) for any of the following
reasons: unacceptable PE sample performance, unacceptable QB sample
performance, arid/or major change in the laboratory (e.g., relocation,
new owner, or high turnover of key personnel). Sections 11.2.2
through 11.2.7 apply to the Remedial QB Audit process.
11.3 Corrective Actions
If the Contractor fails to adhere to the requirements lasted in this
section, the Contractor may expect, but USEPA is not limited to, the
following actions: reduction in the number of samples sent under the
contract, suspension of sample shipment to the Contractor,»a full data
package audit, electronic data audit, an on-site laboratory inspection,
a Remedial QB sample, and/or contract sanctions.
E-29 OLC03.2
-------
Exhibit E -- Section 12
On-Site Laboratory Evaluations
12.0 ON-SITE LABORATORY EVALUATIONS
12.1 Overview
As dictated by a contract laboratory's performance, the USEPA Regional
Contract Laboratory Program Project Officer (CLP PO) or their authorized
representative will conduct an on-site laboratory evaluation. On-site
laboratory evaluations are carried out to monitor the Contractor's
ability to meet selected terms and conditions specified in the contract.
The evaluation process incorporates two separate categories: Quality
Assurance (QA) Evaluation and an 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.
12.2.1 The Contractor should expect that items to be monitored will include,
but not be limited to, the following:
• Size and appearance of the facility;
• Quantity, age, availability, scheduled maintenance, and
performance of instrumentation;
• Availability, appropriateness, and utilization of the Quality
Assurance Plan (QAP) and Standard Operating Procedures (SOPs);
• Staff qualifications, experience, and personnel training
programs;
• Reagents, standards, and sample storage facilities;
• Standard preparation logbooks and raw data;
• Bench sheets and analytical logbook maintenance and review; and
• 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 in a profile
package for discussion during the evaluation. Items that may be
included are previous on-site reports, performance evaluation sample
scores, Regional review of data, Regional QA materials, data audit
reports, results of 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 Standard Operating
Procedures (SOPs), and an audit of analytical project file
documentation.
12.3.1 Procedural Audit. The procedural audit consists of review and
examination of actual SOPs and accompanying documentation for the
following laboratory operations: sample receiving, sample storage,
OLC03.2 E-30
-------
Exhibit E -- Section 12
On-Site Laboratory Evaluations (Con't)
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;
• 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
"•5.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.
12.5 '-'-Corrective Action Reports for Follow-Through to Quality Assurance and
Evidentiary Audit Reports
Following an on-site laboratory evaluation, QA and/or evidentiary audit
reports which discuss deficiencies found during the on-site evaluation
may be sent to the Contractor. In a detailed letter, the Contractor
shall discuss the corrective actions implemented to resolve the
deficiencies discussed during the on-site evaluation and discussed in
the report(s) to the USEPA Regional CLP PO within 14 days of receipt of
the report.
12.5.1 An alternate delivery schedule may be proposed by the Contractor, but
it is the sole decision of USEPA to approve or disapprove the
alternate delivery schedule. If an alternate delivery schedule is
proposed, the Contractor shall describe in a letter to the USEPA
Regional CLP PO and the Contracting Officer why it is unable to meet
the delivery schedule listed in this section. The USEPA Regional CLP
PO may grant an extension of up to 14 days for the Contractor's
response letter to the QA and evidentiary audit report. An extension
beyond 14 days must be approved by the USEPA Contracting Officer.
The Contractor shall proceed and not assume that an extension will be
granted until so notified by the appropriate USEPA official.
12.5.2 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
E-31 OLC03.2
-------
Exhibit E -- Section 12
On-Site Laboratory Evaluations (Con't)
Contractor shall write/amend the SOPs per the requirements listed in
Section 6.
12.6 Corrective Actions
If the Contractor fails to adhere to the requirements listed in this
section, the Contractor may expect, but USEPA is not limited to, the
following actions: reduction in the number of samples sent under the
contract, suspension of sample shipment to the Contractor, an on-site
laboratory evaluation, data package audit, electronic data audit, a
remedial performance evaluation sample, and/or contract sanctions.
OLC03.2 E-32
-------
Exhibit E -- Section 13
Electronic Data Audits
13 . 0 ELECTRONIC DATA 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;
• 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 Spike/Matrix
Spike Duplicate(s) (MS/MSD), Laboratory Control Sample (LCS),
instrument performance checks [4-Bromofluorobenzene (BFB) and
decafluorotriphenylphosphine (DFTPP)], initial calibrations,
Continuing Calibration, as well as all Contractor-generated spectral
libraries and quantitation reports required to generate the data
package. In addition, the Contractor shall supply raw data for the
Method Detection Limit (MDL) studies and values for the year in which
the Sample Delivery Group (SDG) was analyzed. The Contractor shall
maintain a written 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 Trie Contractor is required to retain the instrument electronic data
for three years after submission of the reconciled Complete SDG File.
Electronic media shipped to 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 by
the Contractor upon prior written approval by USEPA. When submitting
electronic instrument data to a USEPA, the following materials shall
be delivered in response to the request.
E-33
OLC03.2
-------
Exhibit E -- Section 13
Electronic Data Audits (Con't)
13.1.3.1 All associated raw data files for all analytical samples and all
QC samples. For example, files for LCS, blanks, initial and
continuing calibration standards and instrument performance check
solutions (BFB and DFTPP). ^
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 Mass Spectral library files (NIST/EPA/NIH
and/or Wiley, or equivalent, library not required).
13.1.3.5 A copy of the Contractor's written reference logbook relating data
files to EPA sample number, LCS, BFB and DFTPP, calibration data,
standards, blanks, and spikes. 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:
• Contractor name;
• Date of submission;
• Case number;
• SDG number;
• Instrument make and model number for each instrument;
• Instrument operating software name and version number;
• Data software name and version used for acquisition,
requantitation, and hardcopy/report generation;
• Data system computer;
• System operating software;
• Data system network;
• Data backup software;
• Data backup hardware;
OLC03.2 E-34
-------
Exhibit E -- Section 13
Electronic Data Audits (Con't)
• 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 (CLP)
Project Officer (CLP PO), the Contractor shall send the required
instrument electronic data and all necessary documentation to USEPA
designated recipient [e.g., Quality Assurance Technical Support (QATS)]
within 7 days of notification. An alternate delivery schedule may be
proposed by the Contractor, but it is the sole decision of USEPA to
approve or disapprove the alternate delivery schedule. If an alternate
delivery schedule is proposed, the Contractor shall describe in a letter
to the USEPA Regional CLP PO and the Contracting Officer why it is
unable to meet the delivery schedule listed in this section. The USEPA
Regional CLP PO may grant an extension of up to 7 days for submission of
the instrument electronic data. An extension beyond 7 days must be
approved by the USEPA Contracting Officer (CO). The Contractor shall
proceed and not assume that an extension will be granted until so
notified by the appropriate USEPA official.
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 may 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
•3- ?discuss the corrective actions implemented to resolve the deficiencies
- 'listed in the electronic data audit report within 14 days of receipt of
the report.
13.3.1 An alternate delivery schedule may be proposed by the Contractor, but
it is the sole decision of USEPA to approve or disapprove the
alternate delivery schedule. If an alternate delivery schedule is
proposed, the Contractor shall describe in a letter to the USEPA
Regional CLP PO and the Contracting Officer why it is unable to meet
the delivery schedule listed in Section 13.3. The USEPA Regional CLP
PO may grant an extension of up to 14 days for the Contractor's
response letter to the electronic data report. An extension beyond
14 days must be approved by. the USEPA Contracting Officer. The
Contractor shall proceed and not assume that an extension will be
granted until so notified by the appropriate USEPA official.
13.3.2 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 Section 6.
i3.4 Corrective Actions
If the Contractor fails to adhere to the requirements listed in Section
13, the Contractor may expect, but USEPA is not limited to, the
following actions: reduction in the number of samples sent under the
contract, suspension of sample shipment to the Contractor, an on-site
laboratory evaluation, an electronic data audit, a data package audit, a
remedial laboratory evaluation sample, and/or contract sanctions.
E-35 OLC03.2
-------
Exhibit E -- Section 13
Electronic Data Audits (Con't)
13.5 Maintenance of the Magnetic Tape Storage Device
13.5.1 The Contractor shall certify that the tape head alignment on the
magnetic tape storage device is in compliance with the ANSI standards
for nine track magnetic tapes. If the Contractor does not have
documentation of alignment within the last 12 months, the Contractor
must perform or have performed the manufacturer's documented head
alignment procedure within 60 days of contract award. This is
generally performed with a "skew" tape, certified to be in
conformance with ANSI standards. The alignment must be performed by
qualified personnel. The tape head alignment must be performed at a
minimum once every 12 months, or whenever there is evidence that the
tape head may be out of alignment.
13.5.2 The tape system, including recording head, must be in conformance with
the manufacturer's physical and electrical standards. Alignment of
the remaining components of the tape system such as the retracting
arms, must be performed at intervals not to exceed 24 months. If the
Contractor cannot demonstrate that the remaining components of the
tape system are in alignment, then the Contractor must perform or have
performed the manufacturer's recommended alignment procedure.
OLC03.2 ' E-36
-------
Exhibit E -- Section 14
Data Management
14.0 DATA MANAGEMENT
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.
• Justification or rationale for the change.
• Date and 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.
E-37
OLC03.2
-------
Exhibit E -- Section 14
Data Management (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 .
(CLP) Project Officer (CLP PO).
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.
OLC03.2 E-38
-------
EXHIBIT F
CHAIN-OF-CUSTODY, DOCUMENT CONTROL
AND WRITTEN STANDARD OPERATING PROCEDURES
F-l OLC03.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
OLC03.2 F-2
-------
Exhibit F - Chain-of-iCustody, Document Control and
Written Standard Operating Procedures
Table of Contents
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 7
2.6 Computer-Resident Sample Data Control 8
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 Control 14
3.7 CSF Organization and Assembly 15
F-3 OLC03.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
OLC03.2 p-4
-------
Exhibit F -- Section 1
Introduction
1.0 INTRODUCTION
A sample is physical evidence collected from a facility or 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;
• Ensuring the integrity of sample identity while in possession of the
Contractor;
• Ensuring sample-related activities are recorded on documents or in
other formats for USEPA sample receipt, storage, preparation,
analysis, and disposal;
• Ensuring all laboratory records for each specified Sample Delivery
Group (SDG) will be accounted for when the project is completed; and
• 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 OLC03.2
-------
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;
• Custody seal numbers when present;
• Condition of the sample bottles;
• Presence or absence of airbills or airbill stickers;
• Airbill or airbill sticker numbers;
• Presence or absence of Chain-of-Custody records;
• Sample tags listed/not listed on Chain-of-Custody records;
• Presence or absence of Traffic Reports (TRs) or Packing Lists;
• Presence or absence of cooler temperature indicator bottle;
• Cooler temperature;
• Date of receipt;
• Time of receipt;
• EPA sample numbers;
OLC03.2 F-6
-------
Exhibit F -- Section 2
Standard Operating Procedures (Con't)
• Presence or absence of sample tags;
• Sample tag numbers;
• Assigned laboratory numbers;
• Samples delivered by hand; and
• 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., Chain-of-Custody records, TRs 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; and unsatisfactory sample condition (e.g., leaking sample
container).
2.-1.9 The Contractor shall record resolution of problems and discrepancies
by SMO.
2.2'' Sample Identification
2.2'-. 1 ;; The Contractor shall maintain the identity of USEPA samples and
~ prepared samples (including extracted samples, digested samples, and
distilled samples) throughout the laboratory.
•;;•• •'•»•••
2.2'-"2 ~:v 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:
• It is in your possession; or
• It is in your view after being in your possession; or
• It is locked in a secure area after being in your possession; or
• It is in a designated secure area, 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.
2.5 Sample Tracking and Document Control
2.5.1 The Contractor shall record all activities performed on USEPA
samples.
F-7 OLC03.2
-------
Exhibit F -- Section 2
Standard Operating Procedures (Con't)
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 (i.e., GC/MS-VOA) 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.
2.5.5 The laboratory name shall be identified on pre-printed laboratory
documents.
2.5.6 Each laboratory document entry shall be dated with the month/day/year
(e.g., 01/01/2000) and signed (or initialed) by the individual(s)
responsible for performing the recorded activity at the time the
activity is recorded.
2.5.7 Notations on laboratory documents shall be recorded in ink.
2.5.8 Corrections to laboratory 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
event where^SDGs "share" Quality Control (QC) samples (e.g.,
instrument run logs and extraction logs).
2.5.14 Information inserted into laboratory documents shall be affixed
permanently in-place. The individual responsible for inserting
information shall sign and date across the insert and logbook page at
the time information is inserted.
2.5.15 The Contractor shall document disposal or retention of 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.
OLC03.2 F-8
-------
Exhibit F -- Section 2
Standard Operating Procedures (Con't)
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 that 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
-• "fi 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.
2.7.6 Documents relevant to each SDG including, but not limited to, the
following shall be included in the CSF:
• logbook pages; • records of failed or
• bench sheets; attempted analysis;
• mass spectra; • custody records,-
• chromatograms; • sample tracking records;
• screening records; • raw data summaries;
• preparation records; • computer printouts;
• repreparation records; • correspondence;
• analytical records; • FAX originals;
• re-analysis records; • library search results; and
• other.
F-9 OLC03.2
-------
Exhibit F -- Section 2
Standard Operating Procedures (Con't)
2.7.7 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.
2.7.8 CSF documents shall be organized and assembled on an SDG-specific
basis.
2.7.9 Original documents which include information relating to more than
one SDG (e.g., Chain-of-Custody records, TRs, 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 packages were sent, the date, and the. carrier used.
2.7.14 Shipments of deliverable packages, including re-submittals, shall be
sealed with custody seals by the document control officer or a
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.
OLC03.2 F-10
-------
Exhibit F -- Section 3
Written Standard Operating Procedures
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:
?'•'• • Custody seals;
:iv
-•"• ?:' • Chain-of-Custody records;
••"-'• sA • Traffic Reports (TRs) or Packing Lists,-
~v- - • Airbills or airbill stickers;
• Sample tags; and
• 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:
• Presence or absence and condition of custody seals on shipping
and/or sample containers;
• Custody seal numbers when present;
• Condition of the sample bottles;
• Presence or absence of airbills or airbill stickers;
• Airbill or airbill sticker numbers;
F-ll OLC03.2
-------
Exhibit F -- Section 3
Written Standard Operating Procedures (Con't)
• Presence or absence of Chain-of-Custody records;
• Sample tags listed/not listed on Chain-of-Custody records;
• Presence or absence of TRs or Packing Lists;
• Presence or absence of cooler temperature indicator bottle;
• Cooler temperature;
• Date of receipt;
• Time of receipt;
• EPA sample numbers;
• Presence or absence of sample tags;
• Sample tag numbers;
• Assigned laboratory numbers; :
• Samples delivered by hand; and
• Problems and discrepancies.
3.1.2.6 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., Chain-of-Custody
records, TRs or packing lists, and airbills).
NOTE: Initials are not acceptable.
3.1.2.7 The Contractor shall contact the Sample Management Office (SMO) to
resolve problems and discrepancies, including, but not limited to:
absent documents; conflicting information; absent or broken
custody seals; and unsatisfactory sample condition (e.g., leaking
sample container).
3.1.2.8 The Contractor shall record resolution of problems and
discrepancies by SMO.
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, thus 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, thus the written SOPs
shall include their definitions; and
OLC03.2 F-12
-------
Exhibit F -- Section 3
Written Standard Operating Procedures (Con't)
• The Contractor uses methods to uniquely identify
fractions/parameter groups and matrix type, thus the written
SOPs shall include a description of these methods.
3.2.2.2 Each sample and sample preparation container is labeled with the
EPA sample number or a unique laboratory sample identification
number.
3.3 Sample Security
3.3.1 The Contractor shall have written SOPs for sample security which
accurately reflect the procedures used by the laboratory._
3.3.2 The written SOPs for sample security shall include the items listed
below.
3.3.2.1 Procedures which ensure the following:
• 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.K-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;
• Titles which identify the activities recorded are printed on
each page of all laboratory documents;
• Information recorded in columns is identified with column
headings;
• Reviewers' signatures are identified on laboratory documents;
• The laboratory name is included on pre-printed laboratory
documents;
F-13 OLC03.2
-------
Exhibit F -- Section 3
Written Standard Operating Procedures (Con't)
• Laboratory document entries are signed arid dated with the
month/day/year (e.g., 01/01/2000);
• Entries on all laboratory documents are recorded in ink;
• Corrections and additions to laboratory documents are made by
drawing single lines through the errors, entering the correct
information, and initialing and dating the new information;
• Unused portions of laboratory documents are lined-out;
• Pages in bound and unbound logbooks are sequentially numbered;
• Instrument-specific run logs are maintained to enable the
reconstruction of run sequences;
• Logbook entries are recorded in chronological order;
• Entries are recorded for only one SDG per page, except in the
event where SDGs "share" Quality Control (QC) samples (e.g.,
instrument run logs and extraction logs);
• Information inserted in laboratory documents is affixed
permanently, signed or initialed, 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.
3.6.2.1 Procedures which ensure the following:
• Contractor personnel responsible for original data entry are
identified;
• Changes to electronic data are made such that the original data
entry is preserved, the editor is identified, and the revision
date is recorded;
• The accuracy of manually entered data, electronically entered
data, and data acquired from instruments is verified;
• Report documents produced by the electronic data collection
system are routinely verified to ensure the accuracy of the
information reported;
• Electronic data collection system security is maintained;
• Archives of electronic data and accompanying software are
maintained in a secure location; and
• Off-site backup and storage of electronic data is maintained.
OLC03.2 F-14
-------
Exhibit F -- Section 3
Written Standard Operating Procedures (Con'ti
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".
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;
• All documents relevant to each SDG are included in the CSF;
• Sample tags are encased in clear plastic bags by the document
control officer or a designated representative before being placed
in the CSF;
• The CSF is organized and assembled on an SDG-specific basis;
-.«/ • Original documents which contain information relating to more than
vtf: one SDG are filed in the CSF of the lowest SDG and copies are
referenced to originals in the event that an original document
contains information relating to more than one SDG;
'-. • Each CSF is submitted with a completed Form DC-2, and re-submitted
CSFs are submitted with a new or revised Form DC-2;
• Each page of the CSF is stamped with a sequential number and the
page number ranges are recorded in the columns provided on Form
DC-2. Intentional gaps in the page numbering sequence are
recorded in the "Comments" section of Form DC-2. Inserted
documents are recorded in the "Other Records" section of Form
DC-2;
• Consistency and completeness of the CSF are verified by the
document control officer or 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; and
• Custody seals are signed and dated by the document control officer
or a designated representative before placing them on deliverable
packages.
F-15 OLC03.2
-------
EXHIBIT G
GLOSSARY OF TERMS
G-l OLC03.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
OLC03.2 G-2
-------
Exhibit G -- Glossary of Terms
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
injection of the sample, standard, or blank into the GC/MS or GC system.
BAR GRAPH SPECTRUM - A plot of the mass-to-charge ratio (m/e) versus relative
intensity of the ion current.
BLANK - An analytical sample designed to assess specific sources of
contamination. See individual definitions for types of blanks.
BREAKDOWN - A measure of the decomposition of certain analytes (DDT and
Endrin) into by-products.
4-BROMOFLUOROBENZENE (BFB) - The compound chosen to establish mass spectral
instrument performance for volatile (VOA) analyses.
CALIBRATION FACTOR (CF) - A measure of the gas chromatographic response of a
target analyte to the mass injected.
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).
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 - Analytical standard run every 12 hours to verify the
initial calibration of the system.
CONTINUOUS LIQUID-LIQUID EXTRACTION - Used herein synonymously with the terms
continuous extraction, continuous liquid extraction, and liquid extraction.
This extraction technique involves boiling the extraction solvent in a flask
and condensing the solvent above the aqueous sample. The condensed solvent
drips through the sample, extracting the compounds of interest from the
aqueous phase.
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.
DECAFLUOROTRIPHENYLPHOSPHINE (DFTPP) - Compound chosen to establish mass
spectral instrument performance for semivolatile analysis.
DEUTERATED MONITORING COMPOUNDS (DMCs) - Compounds added to every calibration
standard, blank, and sample used to evaluate the efficiency of the
extraction/purge and trap procedures, and the performance of the gas
chromatograph/mass spectrometer (GC/MS) systems. DMCs are isotopically
labeled (deuterated) analogs of native target compounds. DMCs are not
expected to be naturally detected in the environmental media.
G-3 OLC03.2
-------
Exhibit G -- Glossary of Terms
EXTRACTABLE - A compound that can be partitioned into an organic solvent from
the sample matrix and is amenable to gas. chromatography. Extractables include
semivolatile (SVGA) and pesticide/Aroclor compounds.
EXTRACTED ION CURRENT PROFILE (EICP) - A plot of ion abundance versus time (or
scan number) for ion(s) of specified mass(es).
FIELD SAMPLE - A portion of material to be analyzed that is contained in
single or multiple containers and identified by a unique sample number.
GAS CHROMATOGRAPH (GC) - The instrument used to separate analytes on a
stationary phase within a chromatographic column. The analytes are volatized
directly from the sample (VOA), or injected as extracts (SVA and PEST). In
VOA and SVA analysis, the compounds are detected by a Mass Spectrometer. In
PEST analysis, the compounds are detected by an Electron Capture Detector.
IN-HOUSE - At the Contractor's facility.
INITIAL CALIBRATION - Analysis of analytical standards for a series of
different specified concentrations; used to define the linearity and dynamic
range of the response of the mass spectrometer or electron capture detector to
the target compounds.
INTEGRATION SCAN RANGE - The scan number of the scan at the beginning of the
area of integration to the scan number at the end of the area of integration.
Performed in accordance with Exhibit D VOA and SVOA.
INTEGRATION TIME RANGE - The retention time at the beginning of the area of
integration to the retention time at the end of the area of integration.
INTERNAL STANDARDS - Compounds added to every standard, blank, sample (for
volatiles), sample extract (for semivolatiles), including Laboratory Control
Sample, at a known concentration, prior to analysis. Internal standards are
used as the basis for quantitation of the target compounds.
INSTRUMENT BLANK - A blank designed to determine the level of contamination
associated with the analytical instruments.
LABORATORY - Synonymous with Contractor as used herein.
LABORATORY CONTROL SAMPLE (LCS) - The LCS is an internal laboratory quality
control sample designed to assess (on an SDG-by-SDG basis) the capability of
the contractor to perform the analytical method.
m/z - Mass to charge ratio, synonymous with "m/e".
MATRIX - The predominant material of which the sample to be analyzed is
composed. For the purpose of this SOW, the sample matrix is water.
MATRIX EFFECT - In general, the effect of a particular matrix (water), on the
constituents with which it contacts. Matrix effects may prevent efficient
purging/extraction of target analytes, and may affect DMC and surrogate
recoveries. In addition, nontarget analytes may be extracted from the matrix
causing interferences.
OLC03.2 G-4
-------
Exhibit G -- Glossary of Terms
MATRIX SPIKE - Aliquot of the water sample 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.
MATRIX SPIKE DUPLICATE - A second aliquot of the same sample as the matrix
spike (above) that is spiked in order to determine the precision of the
method.
METHOD BLANK - An analytical control consisting of all reagents, internal
standards, and surrogate standards (or DMCs for VGA and SV), that is carried
throughout the entire analytical procedure. The method blank is used to
define the level of laboratory, background, and reagent contamination.
NARRATIVE (SDG Narrative) - Portion of the data package which includes
laboratory, contract, Case and sample number identification, and descriptive
documentation of any problems encountered in processing the samples, along
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 percent difference indicates both the direction and the magnitude
of the comparison, i.e., the percent difference may be either negative,
positive, or zero.
PERFORMANCE EVALUATION MIXTURE - A calibration solution of specific analytes
used to evaluate both recovery and percent breakdown as measures of
performance.
PERFORMANCE EVALUATION SAMPLE - An external quality control sample prepared by
USEPA and is designed to assess the capability of the Contractor to perform
the analytical method.
PRIMARY QUANTITATION ION - A contract specified ion used to quantitate a
target analyte.
PROTOCOL - Describes the exact procedures to be followed with respect to
sample receipt and handling, analytical methods, data reporting and
deliverables, and document control. Used synonymously with Statement of Work
(SOW) .
PURGE AND TRAP (DEVICE) - Analytical technique (device) used to isolate
volatile (purgeable) organics by stripping the compounds from water by a
stream of inert gas, trapping the compounds on an adsorbent such as a porous
polymer trap, and thermally desorbing the trapped compounds onto the gas
chromatographic column.
PURGEABLES - Volatile compounds.
RECONSTRUCTED ION CHROMATOGRAM (RIC) - A mass spectral graphical
representation of the separation achieved by a gas chromatograph; a plot of
total ion current versus retention time.
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.
G-5 OLC03.2
-------
Exhibit G -- Glossary of Terms
RELATIVE RESPONSE FACTOR (RRF) - A measure of the relative mass spectral
response of an analyte compared to its internal standard. RRFs are determined
by analysis of standards and are used in the calculation of concentrations of
analytes in samples.
RELATIVE RETENTION TIME (RRT) - The ratio of the retention time of a compound
to that of a standard (such as an internal standard).
RESOLUTION - Also termed separation or percent resolution, the separation
between peaks on a chromatogram, calculated by dividing the depth of the
valley between the peaks by the peak height of the smaller peak being
resolved, multiplied by 100.
RESOLUTION CHECK MIXTURE - A solution of specific analytes used to determine
resolution of adjacent peaks; used to assess instrumental performance.
RESPONSE - or Instrumental Response - A measurement of the output of the GC
detector (MS, or EC) in which the intensity of the signal is proportionate to
the amount (or concentration) detected. Measured by peak area or peak height.
RETENTION TIME (RT) - The time a target analyte is retained on a GC column
before elution. The identification of a target analyte is dependent on a .
target compound's retention time falling within the specified retention time
window established for that compound. Retention time is dependent on the
nature of the column's stationary phase, column diameter, temperature, flow
rate, and other parameters.
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 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.
SAMPLE MANAGEMENT OFFICE (SMO) - A contractor operated facility operated under
the Contract Laboratory Analytical Services Support (CLASS) contract, awarded
and administered by USEPA.
SAMPLE NUMBER (EPA Sample Number) - A unique identification number designated
by USEPA to each sample. The EPA sample number appears on the sample Traffic
Report (TR) which documents information on that sample.
SECONDARY QUANTITATION ION - Contract specified ion(s) to be used in
quantitation of target analytes when interferences prevent the use of the
primary quantitation ion.
OLC03.2 G-6
-------
Exhibit G -- Glossary of Terms
SEMIVOLATILE (SV) COMPOUNDS - Compounds amenable to analysis by extraction of
the sample with an organic solvent. Used synonymously with Base/Neutral/Acid
(BNA) compounds.
STANDARD ANALYSIS - An analytical determination made with known quantities of
target compounds; used to determine response factors.
STORAGE BLANK - Reagent water (two 40.0 mL aliquots) stored with volatile
samples in an SDG. It is analyzed after all samples in that SDG have been
analyzed; and it is used to determine the level of contamination acquired
during storage.
SULFUR CLEANUP BLANK -. A modified method blank that is prepared only when some .
of the samples in a batch are subjected to sulfur cleanup. It is used to
determine the level of contamination associated with the sulfur cleanup
procedure. When all of the samples are subjected to sulfur cleanup, then the
method blank serves this purpose. When none of the samples are subjected to
sulfur cleanup, no sulfur cleanup blank is required.
SURROGATES (Surrogate Standard) - For pesticides/Aroclors, compounds added to
every blank, sample, including Laboratory Control Sample, requested MS/MSD,
and standard; used to evaluate analytical efficiency by measuring recovery.
Surrogates are not expected to be detected in environmental media.
TARGET COMPOUND LIST (TCL) - A list of compounds designated by the Statement
of Work (Exhibit C) for analysis.
TENTATIVELY IDENTIFIED COMPOUNDS (TIC) - Compounds detected in samples that
are not target compounds, internal standards, deuterated monitoring compounds,
or surrogates. Up to 30 peaks, not including those identified as alkanes
(those greater than 10% of the peak area or height of the nearest internal
standard), are subjected to mass spectral library searches for tentative
identification.
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 (TR) - A USEPA sample identification form filled out by the
sampler, which accompanies the sample during shipment to the laboratory and
which documents sample condition and receipt by the laboratory.
TWELVE-HOUR TIME PERIOD - The twelve (12)-hour time period for GC/MS system
instrument performance check, standards calibration (initial or continuing
calibration), and method blank analysis begins at the moment of injection of
the DFTPP or BFB analysis that the laboratory submits as documentation of
instrument performance. The time period ends after 12 hours have elapsed
according to the system clock. For pesticide/Aroclor analyses performed by
GC/EC, the 12-hour time period in the analytical sequence begins at the moment
of injection of the instrument blank that precedes sample analyses, and ends
after twelve hours have elapsed according to the system clock.
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.
G-7 OLC03.2
-------
Exhibit G -- Glossary of Terms
VOLATILE COMPOUNDS - Compounds amenable to analysis by the purge and trap
technique. Used synonymously with purgeable compounds.
WIDE BORE CAPILLARY COLUMN - A gas chromatographic column with an internal
diameter (ID) that is greater than or equal to 0.53 mm. Columns with lesser
diameters are classified as narrow bore capillary columns.
OLC03.2 G-8
-------
EXHIBIT H
AGENCY STANDARD IMPLEMENTATION
H-l OLC03.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
OLC03.2 H-2
-------
Exhibit H - Agency Standard Implementation
Table of Contents
Section . Page
1.0 FORMAT CHARACTERISTICS . . 5
2.0 RECORD TYPES 7
3.0 PRODUCTION RUNS . . 8
4.0 RECORD SEQUENCE 9
5.0 FILE/RECORD INTEGRITY 10
6.0 DATES AND TIMES 10
7.0 MULTIPLE VOLUME DATA 10
8.0 DELIVERABLE 11
9.0 RECORD LISTING . . 12
9.1 Production Run Header Record (Type 10) 12
9.2 Chromatography Record (Type 11) 13
9.3 Sample Header Data Record (Type 20) 14
9.4 Sample Header Data Record (Type 21) 16
9.5 Sample Condition Record (Type 22) 18
9.6 Associated Injection and Counter Record (Type 23) 19
9.7 Sample Cleanup Record (Type 27) 22
9.8 Results Data Record (Type 30) 23
9.9 Auxiliary Data Record (Type 32) 26
9.10 Name Record (Type' 33) '. . 27
9.11 Instrumental Data Readout Record (Type 36) : . . . . 28
9.12 Comment Record (Type 90) 30
10.0 DEFINITIONS OF VARIOUS CODES USED IN AGENCY STANDARD RECORDS 31
10.1 Quality Control and Related Codes (QCC) in Type 20 Records 31
10.2 Codes For Sample Medium (Matrix, Sources) 33
10.3 List of Sample and Result Qualifiers 33
H-3 OLC03.2
-------
THIS PAGE INTENTIONALLY LEFT BLANK
OLC03.2 H-4
-------
Exhibit H -- Section 1
Format Characteristics
1.0 FORMAT CHARACTERISTICS
1.1 This 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 Agency Standard, some fields have
been replaced by delimiters as place holders for non-Contract Laboratory
Program (non-CLP) data elements.
1.2 This implementation includes detailed specifications for the required
format of each record. The position in the record where each field is
to be contained relevant to other fields is specified, as well as the
maximum length of the field. Each field's required contents are
specified as literal (contained in quotes), which must appear exactly as
shown (without quotes), or as a variable for which format and/or
descriptions are listed in the format/contents column. Options and
examples are listed for most fields. For fields where more than three
options are available, a list and description of options are supplied on
a separate page 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.
1.3 Numeric fields may contain numeric digits, a decimal place, and a
leading minus sign. A positive sign is assumed if no negative sign is
entered in a numeric field and shall 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.
1.4 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 shall maintain the greatest significance possible
providing the field length limitation. In addition, the rounded number
that appears on the form, and therefore in the field on 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. The numbers/values
reported by the Contractor are .used by CCS to calculate a result [e.g.,
Contract Required Quantitation Limit (CRQL)]. The final value
calculated .by CCS is then rounded according to rounding rules described
in Exhibit B and is used for comparison to the final value (e.g., CRQL)
reported by the Contractor. Field lengths should only be as long as
necessary to contain the data; packing with blanks is not allowed.
1.5 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
H-5 OLC03.2
-------
Exhibit H -- Section 1
Format Characteristics (Con't)
this alternate electronic data delivery strategy by the CLP and prior to
submission of data in alternate format(s), the Contractor must first
demonstrate its ability to provide electronic data as stated in this
Exhibit H, and obtain written permission from the CLP 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 CLP, all electronic data deliverables must be provided as specified
in this Exhibit H.
OLC03.2 H-6
-------
Exhibit H -- Section 2
Record Types
2.0 RECORD TYPES
2.1 The Agency Standard consists of variable length ASCII records. Maximum
field length specifications match the reporting requirements in Exhibit
B. The last two bytes of each record shall contain "carriage return"
and "line feed", respectively.
2.2 This implementation consists of twelve record types that can be
summarized in four groups, designated by the first record type in each
group:
Type Type ID Contents
Run Header 10 Information pertinent to a group of
samples processed in a continuous
sequence; usually several per SDG
Sample Header 20 Sample identifying, qualifying, and
linking information
Results Record . 30 Analyte results and qualifications
Comments Record 90 Free form comments
2.3 A separate run header is used for volatiles (VOA) , semivolatiles (SV),
and for each column analysis for pesticides (PEST) [minimum of four type
10 series for VOA/SV/PEST Sample Delivery Group (SDG)]. The 20 series
records contain sample characteristics and link samples within an SDG to
the corresponding calibrations, blanks, and other Quality Controls
(QCs). The 30 series records contain the actual analytical results by
analyte within each sample. The 10, 20, and 30 records are associated
with each other by their position in the file (i.e., 30 series records
follow the corresponding 20 series, which in turn follow the 10 series
run header records).
H-7 OLC03.2
-------
Exhibit H -- Section 3
Production Runs
3 . 0 PRODUCTION RUNS
3.1 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.
3.1.2 Method number - Constant throughout a run.
3.1.3 Instrument conditions - Constant throughout a run.
3.2 Each instrumental analysis consists of a separate production run and is
reported in a separate file. There will be a separate production run
for each of the two pesticide Gas Chromatograph (GC) columns utilized.
Thus, a full three fraction analysis will consist of a minimum of four
production runs.
3.3 Example of the Sequence of Record Types in a File
10 Contains Run Header information.
11 Contains additional run-wide information.
20 Occurs once for each sample, calibration, mean response
factor, matrix spike duplicate result, etc. Acts as a
• header.
21
, 22 Contains additional information for samples.
23
it •
$'• 27
30 Occurs once for each final analytical result. Reports
the value being determined as defined by the type 20.
32 Reports any auxiliary data necessary.
33 Reports compound names for tentatively identified.
compounds (TICs) if necessary.
36 Reports any instrumental data necessary.
30 Values for the next analyte or parameter being measured.
32 Additional data may vary for each parameter, and may
33 occur in any order. Multiple occurrences of the same
36 record type, however, must be consecutive.
30 Continues for as many as are necessary.
32
33
36
30
32
33
36
20 Next Sample Header record. The following applies to the
21 next sample or other group of data.
22
30
32
33
36
30
32
33
36
OLC03.2 H-8
-------
Exhibit H -- Sections 3 & 4
Record Sequence
etc.
20
21
30
32
33
• 36
etc.
4.0 RECORD. SEQUENCE
4.1 The sequence of records for Agency Standard files is as follows: A Run
Header (type 10) record shall be present once and once only (per file)
. as the first record in a file. Therefore, a complete VOA/SV/PEST SDG
will consist of several files.
4.2 • Each environmental sample, calibration standard, or Quality Control (QC)
sample is represented by a group composed of type 20, 21, 22, 23, and 27
records, that hold sample level identifying information, followed by
type 30, 32, 33, and 36 records for each method analyte including
surrogates, deuterated monitoring compounds, and internal standards in
the sample. The type 20 record holds a count for the number of method
analytes being determined and includes all target compounds, surrogates,
deuterated monitoring compounds, and internal standards plus each peak
of the multi-component pesticides [do not include Tentatively Identified
Compounds (TICs) in this count]. A separate field on the type 23 record
contains the number of TICs found. Type 20 records shall occur in the
order of sample analysis. In addition, a type 20 record with a QC code
"MNC", followed by a type 30 record for each method analyte (reporting
values such as mean response factors) will appear after the type 10 or
type 11 record and before the type 20 record that initiates the
analytical sequence. Similarly, for pesticide runs, a type 20 record
with a Quality Control (QC) code "FLO" for Florisil recovery, followed
by type 30 records for each of the method analytes (and the two
surrogates) included in the Florisil check will appear before the type
20 record that initiates the analytical sequence.
4.3 Type 90 comment records may be defined to occupy any position after the
type 10 (header) record.
H-9 OLC03.2
-------
Exhibit H -- Sections 5-7
File/Record Integrity
5.0 FILE/RECORD INTEGRITY
All record types shall contain the following check fields to ensure file
and record integrity:
Record Field Field
Position Length Contents
First Field 2 Record type "10" or as appropriate
Last Field 5 Record sequence number 00001-99999, numbered
within file sequentially
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 two
decimal digits (except year, which is four decimal digits), each
separated by delimiters. Dates are given in the order YYYY MM DD, and
times as HH MM. All hours shall be given as 00 to 23 using a 24-hour
clock and shall be local time. All days shall be given as 01 to 31.
All months shall be given as 01 to 12 (e.g., Ql is January, 02 is
February).
7.0 _ MULTIPLE VOLUME DATA
2"'. .
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
shall not be split between files.
1The 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).
OLC03.2 H-10
-------
Exhibit H -- Section 8
Deliverable
8. 0 DELIVERABLE
8.1 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
MS-DOS Operating System. 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 the USEPA.
8.2 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.
8.3 Information on the diskette must correspond to information submitted in
the hardcopy raw data package and on the hardcopy raw data package
forms. For example, type 30 results field specifies maximum length of
13. When reporting Contract Required Quantitation Limits (CRQLs) or
results on Form 1, maximum length is 13 as is specified in this exhibit;
when reporting 'calculated amounts' on Form 7D, hardcopy specified
maximum length is 8. 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 the USEPA.
8.4 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;
• Client Number (where applicable); and
• Initial Submission or Resubmission (as applicable) and Date.
8.5 The format for File Name shall be XXXXX.001 to XXXXX.O99. Where XXXXX
is the SDG identifier, 0 designates Organics, and 01 through 99 is the
file number.
8.6 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 inch IBM-compatible diskette.
8.7 Section 9.0 (Record Listing) 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.
8.7.1 A record type 30 for each Target Compound List (TCL) compound,
surrogate, deuterated monitoring compound, and internal standard
shall be reported. If the TCL is not detected, the 'U' qualifier in
the appropriate field shall be indicative of that.
8.7.2 For multicomponent analytes (Aroclors/toxaphene), if the
multicomponent analyte is detected, a record type 30 and 32 shall be
reported for each peak identified.
H-ll OLC03.2
-------
Exhibit H -- Section 9
Record Listing
9.0 RECORD LISTING
The following lists every record type required to report data from a
single Sample Delivery Group (SDG).
9.1 Production Run Header Record (Type 10)
Use: Each production run will start with a record type 10.
CONTENTS FORMAT/CONTENTS
RECORD TYPE . "10"
Delimiters . ||||||
INSTRUMENT/DETECTOR Character2
Delimiter |
METHOD NUMBER . Character3
Delimiters ||
LAB CODE • Character
Delimiters | | | |
CONTRACT NUMBER Character
Delimiter |
INSTRUMENT ID Character
Delimiters ||
LABORATORY NAME Character
Delimiters ||
RECORD SEQUENCE NUMBER Numeric
CHECKSUM Character
2General descriptor (GC/MS for VOA/SV analysis or GC for pesticide
analysis on GC/ECD).
3OLC03.1V for volatiles; OLC03.1B for semivolatiles; OLC03.1P for
pesticides. (0 for Organic, L for Low, C for Concentration, zero three point
zero for document number, V for volatiles, B for semivolatiles, P for
pesticides.)
OLC03.2 H-12
-------
Exhibit H -- Section 9
Record Listing (Con't)
9.2 Chromatography Record (Type 11)
Use: To describe chromatograph condition. Must be present once for
each production run immediately following the record type 10.
CONTENTS FORMAT/CONTENTS
RECORD TYPE "11"
Delimiter |
GC COLUMN IDENTIFICATION Character
Delimiters | |
GC COLUMN ID4 Numeric (mm)
Delimiters . I I I I I I I II II
RECORD SEQUENCE NO. Numeric
CHECKSUM Character
* Internal Diameter of the GC column used.
H-13 OLC03.2
-------
Exhibit H -- Section 9
Record Listing (don't)
9.3 Sample Header Data Record (Type 20)
MAXIMUM
LENGTH
2
2
12
1
1
1
3
1
3
1
5
1
6
1
4
1
2
1
2
1
2
1
2
2
2
1
5
CONTENTS
RECORD TYPE
Delimiters
EPA SAMPLE NUMBER
Delimiter
MATRIX
Delimiter
QC CODE
Delimiter
SAMPLE QUALIFIER
Delimiter
CASE NUMBER
Delimiter
SDG NO.
Delimiter
SAMPLE/BLANK/STANDARDS YEAR
ANALYZED
Delimiter
SAMPLE/BLANK/STANDARDS MONTH
ANALYZED
Delimiter
SAMPLE/BLANK/STANDARDS DAY ANALYZED
Delimiter
SAMPLE/BLANK/STANDARDS HOUR
ANALYZED
Delimiter
SAMPLE/BLANK/STANDARDS MINUTE
ANALYZED
Delimiters
SAMPLE VOL UNITS
Delimiter
SAMPLE VOL
FORMAT/CONTENTS
"20"
II
As is exactly on the
hardcopy form
I
CHARACTER5
I
Character (See Section 10)
I
RIN/REX/REJ/SRN/blank6
I
Numeric
I
Character
I
YYYY
MM
I
DD
I
HH
I
MM
II
"ML"/blank7
I
Numeric8
5"0" if not applicable (calibration, tune, etc.); "1" for water.
6"RIN" for reinjection,- "REX" for re-extractions; "REJ" for rejected
samples,- "SRN" for dilutions; and leave blank (empty field with zero length)
when none of the previous conditions apply. In case of multiple operations on
a sample, the final operation will be indicated (e.g., reinjection of a
dilution; AAA12DLRE would have a QC Code of "RIN").
7Sample VOL unit is ML (milliliters) for liquids. Leave blank (zero
length) if not applicable.
8Sample VOL is the volume in milliliters for liquid. Sample VOL
includes the purge volume.
OLC03.2
H-14
-------
Sample Header Data Record (Type 20) (Con't)
MAXIMUM
LENGTH-
1
3
3
5
4
CONTENTS
Delimiter
ANALYTE COUNT
Delimiters
RECORD SEQUENCE NO.
CHECKSUM
Exhibit H -- Section 9
Record Listing (Con't)
FORMAT/CONTENTS
I
Numeric9
III
Numeric
Character
9Counts TCL analytes, surrogates, deuterated monitoring compounds (DMC),
internal standards, and all peaks reported for multi-component PCBs. Do not
include the count for TICs in this field. For calibrations, also count DFTPP,
if included in calibration solution.
H-15
OLC03.2
-------
Exhibit H -- Section 9
Record Listing (Con't)
9.4 Sample Header Data Record (Type 21)
Use: Continuation of Type 20.
Position: Follows the Type 20 to which it applies.
MAXIMUM
LENGTH CONTENTS
2 RECORD TYPE
1 Delimiter
1 PURGE
3 Delimiters
1 EXTRACTION
2 Delimiters
6 CLIENT NUMBER
1 Delimiter
14 LAB FILE/SAMPLE ID
1 Delimiter
4 YEAR EXTRACTED
1 Delimiter
2 MONTH EXTRACTED
1 Delimiter
2 DAY EXTRACTED
2 Delimiters
4 YEAR RECEIVED
1 Delimiter
2 MONTH RECEIVED
1 Delimiter
2 DAY RECEIVED
1 Delimiter
7 IDENTIFICATION/LOT
NUMBER OF LCS
1 Delimiter
FORMAT/CONTENTS
"21"
I
"N" (for VOA); blank (for SV or PEST10
III
S/C/H/blank (for all volatile samples)11
II
Character
I
Character12
I
YYYY/blank (for volatiles)
I
MM/blank (for volatiles)
I
DD/blank (for volatiles)
II
YYYY/blank (for standards, tunes, and
blanks)
I
MM/blank (for standards, tunes, and
blanks)
I
DD/blank (for standards, tunes, and
blanks)
I
Character13
10"N" for not heated purge. All low concentration volatile samples are
required to be purged at ambient temperature.
11"S" for separatory funnel; "C" for continuous liq-liq without
hydrophobic membrane; "H" for continuous liq-liq with hydrophobic membrane,-
blank (zero length field) for all volatile samples.
12Lab File ID for volatile and semivolatile analyses. Lab Sample ID for
pesticides in same format as on forms.
13lf the LCS solution was purchased by the Contractor from a third
party, report the identification number used by the third party to identify
the LCS lot, if available (Form 3). If the LCS solution was prepared in-
house, leave this entry blank.
OLC03.2
H-16
-------
Exhibit H -- Section 9
Record Listing (Con't)
Sample Header Data Record (Type 21) (Con't)
MAXIMUM
LENGTH CONTENTS FORMAT/CONTENTS
8 INJECTION VOLUME Numeric/blank (for VGA)"
2 Delimiters ||
5 RECORD SEQUENCE NO. Numeric
4 CHECKSUM Character
14Injection volume, in uL/ for SVs and PESTs.
H-17 OLC03.2
-------
Exhibit H -- Section 9
Record Listing (Con't)
9.5 Sample Condition Record (Type 22}
Use: Continuation of type 20. Used to describe additional Sample
Conditions.
Position: Follows the type 20 and 21 to .which it applies.
CONTENTS
RECORD TYPE
Delimiter
CALIBRATION YEAR
Delimiter
CALIBRATION MONTH
Delimiter
CALIBRATION DAY
Delimiter
CALIBRATION HOUR
Delimiter
CALIBRATION MINUTE
Delimiter
CALIBRATION FILE ID
Delimiters
EXTRACT VOLUME
Delimiter
DILUTION FACTOR
Delimiters
LEVEL
Delimiter
RECORD SEQUENCE NO.
CHECKSUM
FORMAT/CONTENTS
"22"
I
YYYY/blank (for PEST)15
I
MM/blank (for PEST)
I
DD/blank (for PEST)
I
HH/blank (for PEST)
I
MM/blank (for PEST)
I
Character/blank (for PEST)16
INI
Numeric/blank (for VOA)17
I
Numeric18
III
Numeric/blank (for VOA/SV)19
I
Numeric
Character
15For volatiles and semivolatiles, enter the date and time of analysis
of the most recent 5 ug/L (VOAs) or the 20 ng/uL (SVs) standard run prior to
the sample reported in the associated type 20 record. Leave blank for
pesticides.
16Lab File ID of standard specified in 15 above (volatiles/semivolatiles
only). This field must match the Lab File ID on Type 21 for the associated
calibration (VSTD005/SSTD020). Leave blank for pesticides.
17Enter the Concentrated Extract Volume for all SV and PEST. The value
should be reported in microliters.
"Dilution factor of sample analyzed.
"Concentration level of Pesticide Individual Mix A and B standards.
Concentration of low point, mid point and high point calibration standards as
a multiplier of low point. Low point = 1.0; Mid point = 4.0; High point •
16.0.
OLC03.2
H-18
-------
Exhibit H -- Section 9
Record Listing (Con't)
9.6 Associated Injection and Counter Record (Type 23)
Use: Continuation of type 20. Used to identify associated blanks
and tunes, and the number of surrogates/DMCs and spikes
outside of the Quality Control (QC) limits and the number of
tentatively identified compounds (TICs).
Position: Follows the type 20, 21, and 22 to which, it applies.
MAXIMUM
LENGTH CONTENTS
2 RECORD TYPE
1 Delimiter
1 INSTRUMENT PERFORMANCE
CHECK (IPC/TUNE) LABEL
1 Delimiter
4 IPC/TUNE INJECTION YEAR
1 Delimiter
2 IPC/TUNE INJECTION
MONTH
1 Delimiter
2 IPC/TUNE INJECTION DAY
1 Delimiter
2 IPC/TUNE INJECTION HOUR
1 Delimiter
2 IPC/TUNE INJECTION
MINUTE
1 Delimiter
14 DFTPP/BFB LAB FILE ID
1 Delimiter
2 VOLATILE STORAGE BLANK
LABEL
1 Delimiter
4 STORAGE BLANK INJECTION
YEAR
1 Delimiter
2 STORAGE BLANK INJECTION
MONTH
1 Delimiter
2 STORAGE BLANK INJECTION
DAY
1 Delimiter
2 STORAGE BLANK INJECTION
HOUR
1 Delimiter
2 STORAGE BLANK INJECTION
MINUTE
1 Delimiter
14 STORAGE BLANK LAB
FILE ID (VOA ONLY)
4 Delimiters
FORMAT/CONTENTS
"23"
I
"P" (for BFB and DFTPP IPC) or blank
(for pesticides)
I
YYYY/blank (for PEST)
I
MM/blank (for PEST)
I
DD/blank (for PEST)
I
HH/blank (for PEST) .
I
MM/blank (for PEST)
I
Character/blank (for PEST)
I
"HB" (fpr VOA) or blank (for SV and
PEST)
I
YYYY/blank (for SV and PEST)
I
MM/blank (for SV and PEST)
I
DD/blank (for SV and PEST)
I
HH/blank (for SV and PEST)
I
MM/blank (for SV and PEST)
I
Character
H-19
OLC03.2
-------
Exhibit H -- Section 9
Record Listing (Con't)
Associated Injection and Counter Record (Type 23) (Con't)
MAXIMUM
LENGTH CONTENTS
2 METHOD BLANK LABEL
1 Delimiter
4 METHOD BLANK INJECTION
YEAR
1 Delimiter
2 METHOD BLANK INJECTION
MONTH
1 Delimiter
2 METHOD BLANK INJECTION
DAY
1 Delimiter
2 METHOD BLANK INJECTION
HOUR
1 Delimiter
2 METHOD BLANK INJECTION
MINUTES
1 Delimiter
14 METHOD BLANK LAB
FILE (for VOA and
SV)/SAMPLE ID (for
PEST)
1 • Delimiter
1 SURROGATE (for PEST)/
DMC (for VOA and SV)
RECOVERY LABEL
1 Delimiter
2 SURROGATE (for PEST)/
DMC (for VOA and SV)
RECOVERIES OUT
1 Delimiter
1 TIC LABEL
1 Delimiter
2 NO. OF TICS
1 Delimiter
1 SPIKE RECOVERY LABEL
1 Delimiter
FORMAT/CONTENTS
"MBn/blank (for standard, tune, and
method blanks)
I
YYYY/blank (for standard, tune, and
method blanks)
I
MM/blank (for standard, tune, and method
blanks)
I
DD/blank (for standard, tune, and method
blanks)
I
HH/blank (for standard, tune, and method
blanks)
I
MM/blank (for standard,.tune, and method
blanks)
I
CHARACTER
"P" for % recoveries/blank (for STD/IPC)
Numeric20
"T" (for VOA and SV TICs)/blank (for
PEST)
I
Numeric
I
"S" for LCS (Pest)/MS/MSD (all
fractions)/blank for anything else
20This will be the number of surrogate (for PEST) or DMC (for VOA and
SV) recoveries outside QC limits for a specific column. It should not be
cumulative of the two columns for pesticides.
OLC03.2
H-20
-------
Exhibit H -- Section 9
Record Listing (Con't)
Associated Injection and Counter Record (Type 23) (Con't)
MAXIMUM
LENGTH CONTENTS FORMAT/CONTENTS
2 SPIKE RECOVERIES OUT Numeric/blank21
1 Delimiter |
1 RPD LABEL "R" for RPD/blank22
1 Delimiter |
2 RPD OUT Numeric
1 Delimiter |
5 RECORD SEQUENCE NO. Numeric
4 CHECKSUM Character
21Enter the number of spike recoveries out. Enter "0"(zero) if none of
the spike recoveries are outside of the QC limit.
22"R" for Matrix Spike/Matrix Spike Duplicate Recovery Relative Percent
Difference. Leave blank for all other samples.
H-21 OLC03.2
-------
Exhibit H -- Section 9
Record Listing (Con't)
9.7 Sample Cleanup Record (Type 27)
Use: Continuation of type 20. Used to identify sample/blank cleanup
procedures and QC results.
Position: Follows type 20, 21, 22, and 23 to which it applies.
MAXIMUM
LENGTH CONTENTS
2 RECORD TYPE.
8 Delimiters
1 . FLORISIL CLEANUP TYPE
1 Delimiter
4 FLORISIL LOT CHECK YEAR
1 Delimiter
2 FLORISIL LOT CHECK MONTH
1 Delimiter
2 FLORISIL LOT CHECK DAY
1 Delimiter
2 FLORISIL LOT CHECK HOUR
1 Delimiter
2 FLORISIL LOT CHECK MINUTE
1 Delimiter
14 FLORISIL DATA DESCRIPTOR
1 Delimiter
1 SULFUR CLEANUP
1 Delimiter
2 SULFUR BLANK LABEL
1 Delimiter
4 SULFUR BLANK INJECTION YEAR
1 Delimiter
2 SULFUR BLANK INJECTION MONTH
2 Delimiters
2 SULFUR BLANK INJECTION DAY
1 Delimiter
2 SULFUR BLANK INJECTION HOUR
1 Delimiter
2 SULFUR BLANK INJECTION MINUTE
1 Delimiter
14 SULFUR BLANK LABORATORY/
SAMPLE ID
1 Delimiter
5 RECORD SEQUENCE NO.
4 CHECKSUM
FORMAT/CONTENTS
"27"
mini
"F"/blank (for VOA and SV)
I
YYYY/blank (for VOA and SV)
I
MM/blank (for VOA and SV)
I
DD/blank (for VOA and SV)
I
HH/blank (for VOA and SV)
I
MM/blank (for VOA and SV)
I
Character23
I
Y/N (for PEST)/blank (for VOA
and SV)
I
"SB"/blank (if no separate
sulfur blank was prepared for
pesticides; also blank for VOA
and SV)
I
YYYY/blank (for VOA and SV)
I
MM/blank (for VOA and SV)
II
DD/blarik (for VOA and SV)
I
HH/blank (for VOA and SV)
I
MM/blank (for VOA and SV)
I
Character
Numeric
Character
"Lab Sample ID of associate Florisil lot check. This is a unique
identifier assigned to a lot of Florisil cartridges.
OLC03.2
H-22
-------
Results Data Record (Type 30) (Con't)
Exhibit H -- Section 9
Record Listing (Con't)
MAXIMUM
LENGTH
1
CONTENTS
Delimiter
FORMAT/CONTENTS
MEAN CONCENTRATION LABEL
1 Delimiter
13 MEAN CONCENTRATION
1 Delimiter
1 PERCENT DIFFERENCE LABEL
1 Delimiter
5 PERCENT DIFFERENCE
1 Delimiter
1 INTERNAL STANDARD AREA LABEL
1 Delimiter
13 INTERNAL STANDARD AREA
1 Delimiter
5 RECORD.SEQUENCE NO.
4 CHECKSUM
"M" for Mean cone, (for
multicomponent PEST only)/blank
(for VOA and SV)
I
Numeric (for PEST)/blank (for VOA
and SV)32
I
"F" or "P" (PEST)/blank (for VOA
and SV field sample analysis)33
I '• .
Numeric
I
"I" for IS Area (for VOA and
SV)/blank (for PEST)
I
Numeric (for VOA and SV)/blank
(for PEST)
I
Numeric
Character
32Mean Concentration for Multicomponent analytes detected in pesticide
analyses.
33npn for percent Difference between concentrations from two columns in
pesticide analyses, or "F" for Percent Difference between average RRF (initial
calibration) and RRF5/RRF20 (continuing calibration) in VOA/SV analyses.
Leave blank for volatile and semivolatile sample, blank, and tune analysis.
H-25
OLC03.2
-------
Exhibit H -- Section 9
Record Listing (Con't)
9.9 Auxiliary Data Record {Type 32)
Use: Used to report retention time (in minutes) for Internal
Standards and for TICs (for Volatiles and Semivolatiles). Used
to. report retention- time data and percent breakdown (for
pesticides).
Position: Follows type 30. (Record will only be required as specified
above.)
MAXIMUM
LENGTH CONTENTS
2 RECORD TYPE
3 Delimiters
2 RETENTION TIME LABEL
1 Delimiter
5 RETENTION TIME
1 Delimiter
3 FIRST LIMIT LABEL
1 Delimiter
5 RT WINDOW LOWER LIMIT
1 Delimiter
3 SECOND LIMIT LABEL
1 Delimiter
5 RT WINDOW UPPER LIMIT
2 Delimiters
2 % BREAKDOWN LABEL
1 Delimiter
5 % BREAKDOWN
1 Delimiter
5 COMBINED % BREAKDOWN
2 Delimiters
1 PEAK
1 Delimiter
5 RECORD SEQUENCE NO.
4 CHECKSUM
FORMAT/CONTENTS
"32"
III
"RT"
I
Numeric
I
"RTF"
I
Numeric
I
"RTT"
I
Numeric
II
"PB" for % breakdown/blank (for
VOA and SV)
I
Numeric (DDT/ENDRIN)/blank (for
VOA and SV)
I
Numeric/blank (for VOA and SV)34
II
1 THROUGH 5 (for pesticide
multicomponent compounds)/blank
(for VOA and SV) 3S
I
Numeric
Character
34The combined %breakdown will be reported on both the record type 32s
for DDT and Endrin.
35For positively identified compounds, a minimum of 3 peaks and a
maximum of 5 peaks are allowed. Types 30 and 32 will be repeated for each
peak that is reported (a minimum of three, a maximum of five times).
for multicomponent analytes in pesticide analyses.
This is
OLC03.2
H-26
-------
Exhibit H -- Section 9
Record Listing (Con't)
9.10 Name Record (Type 33)
Use: This record type is used for volatile and semivolatile
analyses only to carry an analyte name for TICs. This record
is not used for pesticide analysis.
Position: Follows types 30 and 32 for TICs.
MAXIMUM
LENGTH CONTENTS FORMAT/CONTENTS
2 RECORD TYPE "33"
1 .Delimiter |
67 NAME OF COMPOUND Character
1 Delimiter |
5 RECORD SEQUENCE NO. Numeric
4 CHECKSUM Character
H-27 OLC03.2
-------
Exhibit H -- Section 9
Record Listing (Con't)
9.11 Instrumental Data Readout Record (Type 36)
Use:
Position:
MAXIMUM
LENGTH
2
1
1 •
3
3
2
5
1
3
1
5
1
5
1
3
1
5
2
3
1
5
1
5
1
3
1
5
1
5
1
3
1
This record type is only used for volatile and semivolatile
analyses to describe decafluorotriphenylphosphine/4-
bromofluorobenzene (DFTPP/BFB) percent abundances. This
record is not used for pesticide analysis.
Follows type 30 for DFTPP/BFB data.
CONTENTS
RECORD TYPE
Delimiter
MASS LABEL
Delimiters
FIRST MASS (DFTPP/BFB)
Delimiters
FIRST PERCENT RELATIVE
ABUNDANCE
Delimiter
SECOND MASS
Delimiter
SECOND PERCENT RELATIVE
ABUNDANCE
Delimiter
PERCENT MASS OF 69
Delimiter
THIRD MASS
Delimiter
THIRD PERCENT RELATIVE
ABUNDANCE
Delimiters
FOURTH MASS
Delimiter
FOURTH PERCENT RELATIVE
ABUNDANCE
Delimiter
PERCENT MASS OF 69
Delimiter
FIFTH MASS
Delimiter
FIFTH PERCENT RELATIVE
ABUNDANCE
Delimiter
PERCENT MASS OF 174
Delimiter
SIXTH MASS
Delimiter
FORMAT/CONTENTS
"36"
III
Numeric (DFTPP for SV or BFB for VOA)
II
Numeric
I -
Numeric
I
Numeric
I
Numeric, DFTPP only/blank (for VOA)
I
Numeric
I
Numeric
II '
Numeric
I
Numeric
I
Numeric, DFTPP only/blank (for VOA)
I
Numeric
I
Numeric
I
Numeric, BFB only/blank (for SV)
I
Numeric
OLC03.2
H-28
-------
Exhibit H -- Section 9
Record Listing (Con't)
Instrumental Data Readout Record (Type 36} (Con't)
MAXIMUM
LENGTH CONTENTS
5 SIXTH PERCENT RELATIVE
ABUNDANCE
2 Delimiters
3 SEVENTH MASS
1 Delimiter
5 SEVENTH PERCENT RELATIVE
ABUNDANCE
1 Delimiter
5 PERCENT MASS OF 174
1 Delimiter
3 EIGHTH MASS
1 Delimiter
5 EIGHTH PERCENT RELATIVE
ABUNDANCE
1 Delimiter
5 PERCENT MASS OF 174
1 Delimiter
3 NINTH MASS
1 Delimiter
5 NINTH PERCENT RELATIVE
ABUNDANCE
1 Delimiter
5 PERCENT MASS OF 176
1 Delimiter
3 TENTH MASS
'1 Delimiter
5 TENTH PERCENT RELATIVE
ABUNDANCE
2 Delimiters
3 ELEVENTH MASS
1 Delimiter
5 ELEVENTH PERCENT
RELATIVE ABUNDANCE
2 • Delimiters
3 TWELFTH MASS
1 Delimiter
5 TWELFTH PERCENT RELATIVE
ABUNDANCE
2 Delimiters
3 THIRTEENTH MASS
2 Delimiters
5 THIRTEENTH PERCENT
RELATIVE ABUNDANCE
1 Delimiter
5 PERCENT MASS OF 442
1 Delimiter
5 RECORD SEQUENCE NO.
4 CHECKSUM
FORMAT/CONTENTS
Numeric
II
Numeric
I
Numeric
I
Numeric, BFB only/blank (for SV)
I
Numeric
I
Numeric
Numeric, BFB only/blank (for SV)
I
Numeric
I
Numeric
Numeric, BFB only/blank (for SV)
I
Numeric/blank (for VGA)
I
Numeric/blank (for VOA)
II
Numeric/blank (for VOA)
I
Numeric/blank (for VOA)
II
Numeric/blank (for VOA)
I
Numeric/blank (for VOA)
II
Numeric/blank (for VOA)
II
Numeric/blank (for VOA)
I
Numeric, DFTPP only (blank for VOA)
I
Numeric
Character
H-29
OLC03.2
-------
Exhibit H -- Section 9
Record Listing (Con't)
3.12 Comment Record (Type 90)
Use: To provide for operator-entered comments.
Position: May occur anywhere in the file after the type 10 record.
MAXIMUM
LENGTH CONTENTS FORMAT/CONTENTS
2 RECORD TYPE "90"
1 Delimiter |
67 ANY COMMENT Character
1 Delimiter |
5 RECORD SEQUENCE NO. Numeric
4 CHECKSUM Character
OLC03.2 H-30
-------
• Exhibit H -- Section 10
Definitions of Various Codes
10.0 DEFINITIONS OF VARIOUS CODES USED IN AGENCY STANDARD RECORDS
10.1 Quality Control and Related Codes (QCC) in Type 20 Records
10.1.1 NOTE: These codes appear in the quality control (QC) code fields of
type 20 records. They are used to indicate the type of data that is
being reported.
OCC Name
LRB LABORATORY (REAGENT)
BLANK
LIB LABORATORY INSTRUMENT
BLANK
LSB LABORATORY SULFUR BLANK
LHB LABORATORY STORAGE BLANK
FRB FIELD BLANK
FRM FIELD REFERENCE SAMPLE
Definition
The "Method Blank" (Exhibit G).
The "Instrument Blank".
If different from "Method Blank"
(pesticides).
The storage blank (volatiles).
This is any sample that is submitted
from the field and is identified as
a blank. This includes trip blanks,
rinsates, equipment blanks, etc.
This is any sample that is submitted
for a Case and is identified as a
Performance Evaluation (PE) sample.
LSD LABORATORY SPIKE
DUPLICATE BACKGROUND
(ORIGINAL) VALUES
LF1
LABORATORY SPIKE SAMPLE
FINAL FIRST MEMBER
LF2 LABORATORY SPIKE SAMPLE
FINAL SECOND MEMBER
An environmental sample which is
analyzed according to the analytical
method, and subsequently used for
the matrix spike, and the matrix
spike duplicate (Exhibit G).
The "Matrix spike" (Exhibit G); must
precede LF2.
The "Matrix spike Duplicate"
(Exhibit G).
LCM LABORATORY CONTROL SAMPLE
The Laboratory Control Sample
(Exhibit G).
(LCS)
LPC LABORATORY PERFORMANCE
CHECK SOLUTION
A solution of DFTPP (SV) or BFB
(VOA) or method analytes (PEST/PCB)
used to evaluate the performance of
an instrument with respect to a
defined set of criteria (Tune or
Resolution Check Sample) (Exhibit
G) .
FLO FLORISIL CHECK SOLUTION
A solution of pesticides used to
check recovery from each lot of
Florisil cartridges. These recovery
results will be provided in every
production run where associated
samples are analyzed.
H-31
OLC03.2
-------
Exhibit H -- Section 10
Definitions of Various Codes (Con't)
OCC Name
CLM INITIAL CALIBRATION -
MULTI-POINT
CLS INITIAL CALIBRATION
SINGLE POINT
CLC CONTINUING CALIBRATION
CHECK
CLE CONTINUING PERFORMANCE
CHECK
CLD DUAL PURPOSE CALIBRATION
Definition
The Initial Calibration for GC/MS
(Exhibit G), or the Initial
Individual Standard Mixes (A, B) for
pesticides (Exhibit D PEST).
Response factors (GC/MS) or
Calibration Factors (pesticides)
will be reported on the following
type 30 records.
The Initial Toxaphene/Aroclor Mixes
used to determine all calibration
factors (Exhibit D PEST).
The continuing calibration (VSTD005/
SSTD020) for GC/MS.
The subsequent Individual Standard
Mixes (A,B), Performance Evaluation
Mixture, and for subsequent
injections of Toxaphene/Aroclor
mixes for pesticides (Exhibit D
PEST).
A calibration solution as above used
both as an initial calibration (CLM)
and a continuing check (CLC).
10.1.2 The following QCC values are used on type 20 records which act as a
header, and indicate that additional (usually calculated) analyte
* specific data will be present on type 30 (and following type)
•'-' records. Usually, these data will apply to an entire production run,
•:-' in which case they will appear immediately following the type 10
record or type 11 record if present. If the data apply to only a
portion of the samples in the run, they shall be placed immediately
preceding the samples to which they apply. Much of the rest of the .
information in the type 20 record may be blank, indicating that these
data do not apply to these results.
MNC
MEAN VALUES FROM
CALIBRATIONS
The data following represent mean
values and percent RSDs from the
initial calibration (GC/MS) or the
mean calibration factors, mean
retention times, and retention
time windows (pesticides).
OLC03.2
H-32
-------
Exhibit H -- Section 10
Definitions of Various Codes (Con't)
10.2 Codes For Sample Medium (Matrix, Sources)
Medium Code
All Media, Specific Medium not Applicable. 0 (zero)
Use for Calibrations, Tunes, etc.
Water 1
10.3 List of Sample and Result Qualifiers
Definition: A sample qualifier consists of three characters which act
as an indicator of the fact and the reason that the subject analysis (a)
did not produce a numeric result, or (b) produced a numeric result for
an entire sample but it is qualified in some respect relating to the
type or validity of the result.
10.3.1 Sample Qualifiers
Qualifier Full Name Definition
RIN RE-ANALYZED The indicated analysis results were
generated from a re-injection of the same
sample extract or aliquot (RE SUFFIX).
REX RE-PREPARED The indicated analysis results were
generated from a re-extraction of the same
sample (RE SUFFIX).
REJ REJECTED The results for the entire sample analysis
have been rejected for an unspecified
reason by the laboratory. For initial
calibration data, these data were not
utilized in the calculation of the mean.
SRN DILUTED The indicated analysis results were
generated from a dilution of the same
sample (DL SUFFIX).
10.3.2 Result Qualifiers in Type 30 Records
A result qualifier consists of three characters which act as an
indicator of the fact and the reason that the subject analysis (a)
did not produce a numeric result, or (b) produced a numeric result
for a single analyte but it is qualified in some respect relating to
the type or validity of the result. This qualifier is complementary
to the flags field on a type 30 record. A tentatively identified
compound (TIC) must have either a TIE, TFB, or PRE result qualifier.
BDL BELOW DETECTABLE Indicates compound was analyzed for but
LIMITS not detected (Form 1 "U" Flag).
NAR NO ANALYSIS RESULT There is no analysis result required
for this subject parameter.
AVG AVERAGE VALUE Average value -- used to report a range
of values (e.g., relative response
factors).
CBC CANNOT BE CALCULATED The analysis result cannot be
calculated because an operand value is
qualified (e.g., identifies analytes
whose internal standard is not found)
(Form 1 "X" Flag).
H-33 OLC03.2
-------
Exhibit H -- Section 10
Definitions of Various Codes (Con't)
LTL LESS THAN LOWER
CALIBRATION LIMIT
GTL GREATER THAN UPPER
CALIBRATION LIMIT
LLS LESS THAN LOWER
STANDARD
TIE TENTATIVELY IDENTIFIED
ESTIMATED VALUE
REJ REJECTED
STD INTERNAL STANDARD
STB INTERNAL STANDARD
BELOW DETECTION LIMITS
FBK FOUND IN BLANK
TFB TENTATIVELY IDENTIFIED
AND FOUND IN BLANK
NRP NON-REPRODUCIBLE
PRE PRESUMPTIVE PRESENCE
ALC ALDOL CONDENSATION
Analysis result is from a diluted
sample (DL suffix) and may be less
accurate than the result from an
undiluted sample (Form 1 "D" Flag).
Actual value is known to be greater
than the upper calibration range (Form
1 "E" Flag).
The analysis result is less than the
sample quantitation limit (Form 1 "J"
Flag).
The indicated analyte is a tentatively
identified analyte; its concentration
has been estimated (Form 1LCF or 1LCG
"J" Flag).
Results for the analyte are rejected by
the laboratory.
The indicated compound is an internal
standard.
A combination of "STD" and "BDL".
The indicated compound was found in the
associated method blank (LRB) as well
as the sample (Form 1 "B" Flag).
A Combination of "TIE" and
'1LCF or 1LCG "B" Flag).
'FBK" (Form
Results of two or more injections are
not comparable (Form 1LCE "P" flag),
e.g., Aroclor target analyte with
greater than 25% difference between
mean concentrations of the two column
analyses.
Presumptive evidence of presence of
material for TIC (Form 1LCF or 1LCG
"N" Flag).
Labels a suspected Aldol Condensation
product for TICs (Form 1LCG)
OLC03.2
H-34
-------
PURCHASE CARD LOG FOR BILLING PERIOD: May 1 - 31, 2001
PAGE 1 OF 2
PRINTED NAME OF
PURCHASE CARDHOLDER: Mary S. Price
ACCOUNT NUMBER: 4486 8600 0014 0972
ITEMS
PURCHASED
Plastic inserts for ID'S (500)
Toner for Fax (E126/A224)
Floor Tread/Sealer/Floor Prep
Safety Signs/labels
Battery for 2-way radio (John J.)
Overhead bulbs (FXL)/labels
Repair signaling module on fire pump
Cartridges for Label Maker used for
name plates
Safety Glasses (Luisa S.)
V
Battery for 2-way Radio (Skip)
Whiteboard (A235)
VENDOR/
MERCHANT
Identicard
Dove Data
Lab Safety
Lab Safety
Townex Communications
Mali
Honeywell
Mali
Unicor
Townex Communications
Herman Miller
APPROVALS
(IF APPROPRIATE)
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
DATE
ORDERED
05/02/01
05/02/01
05/03/01
5//7/01
05/07/01
05/10/01
05/14/01
05/14/01
05/15/01
05/22/01
05/22/01
TOTAL
COST
$148.43
$116.70
$606.39
$438.54
$69.00
$109.95
$305.00
$78.32
$53.00
$116.00
$92.54
OBJECT
CLASS
26.15
26.15
25.82
25.82
31.48
26.15
25.82
26.15
26.29
31.48
31.43
DATE RECONCILED
IN EAGLS
05/09/01
05/11/01
05/11/01
05/11/01
05/17/01
05/17/01
06/04/01
05/21/01
06/04/01
SIGNATURE OF SIGNATURE OF
PURCHASE CARDHOLDER: APPROVING OFFICIAL:
DEFAULT
DCN*
0103JM0013
0103JM0010
0103JM0010
0103JM0010
0103JM0013
0103JM0010
0103JM0013
0103JM0013
0103JM0012
0103JM0013
0103JM0010
-------
PURCHASE CARD LOG FOR BILLING PERIOD: May 1-31, 2001 PAGE 2 OF 2
ACCOUNT NUMBER: 4486860000140972
FINANCIAL DATA FOR PURCHASES NOT CHARGEABLE TO CARDHOLDER'S "DEFAULT DCN"
I DON I BUDGET I FUND I ORG I PRO I SITE7PROJ I COST/ORG I OBJ CLASS I AMOUNT
I FISCAL YEAR I | | I I I \
-------
PURCHASE CARD LOG FOR BILLING PERIOD: May 1-31, 2001
PAGE 1 OF 2
PRINTED NAME OF
PURCHASE CARDHOLDER: Mary S. Price
ACCOUNT NUMBER: 4486 8600 0014 0972
ITEMS
PURCHASED
Sign for B202
Toner for Xerox copier (A1 01 )
E-Z Seal for Postage Meter
VENDOR/
MERCHANT
Environmental Siq
XEROX
Pitney Bowes
APPROVALS
(IF APPROPRIATE)
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE OF
PURCHASE CARDHOLDER:
TELEPHONE NUMBER: 410-305-2646
DATE:
DATE
ORDERED
05/25/01
05/25/01
05/31/01
TOTAL
COST
$60.00
$103.00
$93.09
OBJECT
CLASS
25.82
26.15
26.15
••
E RECONC
IN EAGLS
SIGNATURE OF
APPROVING OFFICIAL:
TELEPHONE NUMBER: 215-814-5 DATE:
DEFAULT
DCN*
0103JM0012
0103JM0013
0103JM0013
0103JMOO
0103JMOO
0103JMOO
0103JMOO
0103JMOO
0103JMOO
0103JMOO
0103JMOO
0003JM0009
0003JM0009
0003JM0009
0003JM0009
*PAGE 2 MUST BE COMPLETED IF ITEM PURCHASED WAS NOT CHARGED TO DEFAULT DCN/ACCOUNT NUMBER(S).
-------
PAGE 1 OF 2
PRINTED NAME OF
PURCHASE CARDHOLDER: Mary S. Price
ACCOUNT NUMBER: 4486 8600 0000 9714
ITEMS
PURCHASED
VENDOR/
MERCHANT
APPROVALS
(IF APPROPRIATE)
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
SIGNATURE/TITLE
DATE
ORDERED
TOTAL
COST
OBJECT
CLASS
TE RECONCIL
IN EAGLS
SIGNATURE OF SIGNATURE OF
PURCHASE CARDHOLDER: APPROVING OFFICIAL:
DEFAULT
DCN*
0003JM0009
0003JM0009
0003JM0009
0003JM0009
0003JM0009
0003JM0009
0003JM0009
0003JM0009
0003JM0009
TELEPHONE NUMBER: 410-305-26 DATE:
TELEPHONE NUMBER: 215-814- DATE:
•PAGE 2 MUST BE COMPLETED IF ITEM PURCHASED WAS NOT CHARGED TO DEFAULT DCN/ACCOUNT NUMBER(S).
------- |