R
EPA-540/R
94-097
United States Office of Publication 9240.1 -1 6
Environmental Protection Solid Waste and S^SSST097
Agency Emergency Response PB95-963511
a r December 1994
Superfund
xvEPA USEPA CONTRACT
LABORATORY PROGRAM
STATEMENT OF WORK
FOR ORGANICS ANALYSIS
MULTI-MEDIA,
MULTI-CONCENTRATION
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IfB No. DuO'./4fc3R|i
ATlACruMtNl A
9240.1-16
PB95-963511
EPA540/R-94/097
CONTRACT LABORATORY PROGRAM
STATEMENT OF WORK
: FOR
ORGANICS'ANALYSIS
Multi-Media, Multi-Concentration
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STATEMENT OF WORK
TABLE OF CONTENTS
EXHIBIT A: SUMMARY OF REQUIREMENTS
EXHIBIT B: REPORTING AND DELIVERABLES REQUIREMENTS
EXHIBIT C: TARGET COMPOUND LIST (TCL) AND CONTRACT REQUIRED QUANTITATION
LIMITS (CRQL)
EXHIBIT D: ANALYTICAL METHODS
EXHIBIT E: QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
EXHIBIT F: CHAIN-OF-CUSTODY, DOCUMENT CONTROL AND STANDARD OPERATING
PROCEDURES
EXHIBIT G: GLOSSARY OF TERMS
EXHIBIT H: DATA DICTIONARY AND FORMAT FOR DATA DELIVERABLES IN
COMPUTER-READABLE FORMAT
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EXHIBIT A
SUMMARY OF REQUIREMENTS
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SECTION I
GENERAL REQUIREMENTS
The Contractor shall use proven instruments and techniques to identify
and measure the concentrations of volatile, semivolatile, and pesticide
compounds listed on the Target Compound List (TCL) in Exhibit C. The
Contractor shall employ state-of-the-art GC/MS and/or GC/EC procedures to
perform all analyses; including the necessary preparations for analysis.
In Exhibit D, the EPA provides the Contractor with the specific
analytical procedures to be used and defines the specific application of
these procedures to this contract. For volatiles and semivolatiles, this
includes instructions for sample preparation, gas chromatographic screening,
mass spectrometric identification, and data evaluation. Specific ions used
for searching the mass spectral data for each compound are included. For
pesticides, this includes instructions for sample preparation, gas
chromatography, confirmation of identification by gas chromatography and/or
mass spectrometry, and data evaluation.
The Contractor shall prepare extracts and dilutions of samples. The
Contractor shall screen extracts by methods of his choice (soil
characterization mandatory; water characterization optional) at an initial
extract concentration. Then, based on the screening response, the Contractor
shall use the specific analytical methods described in Exhibit D to extract
and concentrate samples to achieve the Contract Required Quantitation Limits
(CRQL) listed in Exhibit C. Exhibit D lists the analytical methods and
starting points to be utilized for each of the target compounds.
During preparation, the Contractor shall fortify all semivolatile and
pesticide samples, blanks, matrix spikes, and matrix spike duplicates with
the surrogate spiking compounds listed in Exhibit D. The Contractor shall
fortify all volatile samples, blanks, matrix spikes, and matrix spike
duplicates with the system monitoring compounds listed in Exhibit D.
Additionally, all sample semivolatile extracts and aliquots for volatile
organics analysis shall be spiked with the internal standard compounds listed
in Exhibit D before injection or purging.
Additionally, for each sample analyzed by GC/MS, the Contractor shall
conduct mass spectral library searches to determine the possible identity of
up to ten (10) non-system nonitoring compounds volatile components and up to
twenty (20) non-surrogate semivolatile components that are not on the Target
Compound List (Exhibit C).
Exhibit F contains chain-of-custody and sample documentation
requirements which the Contractor must follow in processing samples under
this contract, and specifies requirements for written laboratory standard
operating procedures.
Sample analysis data, sample documentation and other deliverabl.es shall
be reported as specified in Exhibit B. Specifications for reporting data in
computer-readable form appear in Exhibit H.
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To ensure proper understanding of language utilized in this contract,
Exhibit G contains a glossary of terms. When a term is used in the text
without explanation, the glossary meaning shall be applicable.
The samples to be analyzed by the Contractor are from known or
suspected hazardous waste sites and, potenti lly, may contain hazardous
organic and/or inorganic materials at high concentration levels. The
Contractor should be aware of the potential hazards associated with the
handling and analyses of these samples. It is the Contractor's
responsibility to take all necessary measures to ensure the health and safety
of its employees.
In addition, the Contractor must be aware of the importance of
maintaining the integrity of the data generated under the contracts as it is
used to make major decisions regarding public health and environmental
welfare. In addition, it may be used in litigation against potentially
responsible parties in the enforcement of Superfund legislation.
Prior to accepting any samples from the Agency, the Contractor shall
have, in-house, the appropriate standards for all target compounds listed in
Exhibit C.
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SECTION II
SUMMARY OF REQUIREMENTS
I. For each sample, the Contractor shall perform the following tasks:
A. Task I Receive and Prepare Hazardous Waste Samples.
1. Receive and handle samples under the chain-of-custody
procedures described in Exhibit F.
2. Prepare samples as described in Exhibit D. VOA analysis of
water or soil samples must be completed within 10 days of VTSR
(Validated Tine of Sample Receipt). Separatory funnel
extractions for pesticides in water samples must be completed
within 5 days of VTSR. Sonication extractions for pesticides
and/or semivolatiles in soil samples must be completed within
5 days of VTSR. Continuous liquid-liquid extraction for
semivolatile samples must be started within 5 days of VTSR.
Extracts of either water or soil samples must be analyzed
within 40 days of VTSR. This does not release the Contractor
from the data turnaround time specified in Exhibit B, Section
I.
B. Task II Analysis for Identification of Specific Organic Compounds.
1. Extracts and aliquots prepared in Task I shall be analyzed by
GC/EC and GC/MS techniques given in Exhibit D for the target
compounds listed in Exhibit C.
2. 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.
C. Task III Qualitative Verification of the Compounds Identified in
Task II.
1. The volatile and semivolatile compounds analyzed by GC/MS
techniques and initially identified in Task II shall be
verified by an analyst competent in the interpretation of mass
spectra by conparison 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.
Two criteria oust be satisfied to verify the identifications:
a. Elution of the sample component at the same GC relative
retention time as the standard component.
b. Correspondence of the sample component and standard
component mass spectra.
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2. For establishing correspondence of the GC relative retention
time (RRT), the sample component RRT must compare within ±
0.06 RRT units of the RRT of the standard component. For
reference, the calibration standard must be run on the same
12-hour time period as the sample.
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 DFTPP or BFB daily instrument performance check
requirements specified in Exhibit D. Toe standard spectra
used may be from a laboratory generated library on the same
instrument or obtained from the calibration standard run used
to obtain reference RRTs. The requirements for qualitative
verification by comparison of mass spectra are as follows:
a. All ions present in the standard 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.
b. The relative intensities of ions specified above must
agree within ± 20 percent between the standard and sample
spectra.
c. 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.
When GC/MS computer data processing programs are used to
obtain the sample component spectrum, both the processed
and the raw spectra must be evaluated. In Task III, the
verification process should favor false positives.
3. If a compound analyzed by GC/MS techniques and initially
identified in Task II cannot be verified by all of the
criteria in items 1 and 2 above, but in the technical
judgement of the mass spectral interpretation specialist the
identification is correct, then the Contractor shall report
that identification, and proceed with quantification in Task
IV.
4. The Pesticide/Aroclor compounds listed in Exhibit C and
analyzed by GC/EC techniques shall have their identifications
verified by an analyst competent in the interpretation of gas
chromatograms. Two criteria must be satisfied to verify the
identifications:
a. Elution of the sample component within the retention time
window (established by the procedures in Exhibit D) of the
standard component analyzed on the same GC column and
instrument, as specified in Exhibit D.
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b. Analysis of the sample and standard on a second GC column with
a stationary phase with retention characteristics dissimilar
to that used in a. above, and meeting the same criteria for
elution of the sample component and the standard as in a.
above.
D. Task IV Quantification of Compounds Verified in Task III.
1. The Contractor shall quantify components analyzed by GC/MS
techniques, identified in Task II and verified in Task III by
the internal standard method stipulated in Exhibit D. Where
multiple internal standards are required by EPA, the
Contractor shall perform quantitation utilizing the internal
standards specified in Exhibit D.
2. The Contractor shall determine response factors for each
12-hour time period of GC/MS analysis and shall include a
calibration check of the initial five point calibration as
described in Exhibit D.
3. The Contractor shall quantify components analyzed by GC/EC
techniques, identified in Task II and verified in Task III by
the external standard method stipulated in Exhibit D.
4. The Contractor shall perform an initial three-point
calibration, verify its linearity, determine the breakdown of
labile components, and determine calibration factors for all
standards analyzed by GC/EC techniques as described in Exhibit
D.
E. Task V Tentative Identification of Non-target Sample Components.
1. For each analysis of a sample, the Contractor shall conduct
mass spectral library searches to determine tentative compound
identifications as follows. For each volatile fraction, the
Contractor shall conduct a search to determine the possible
identity of up to ten (10) organic compounds of greatest
concentration which are not system monitoring compounds and
are not listed in Exhibit C. For each semivolatile fraction,
the Contractor shall conduct a search to determine the
possible identification of up to twenty (20) non-surrogate
organic compounds of greatest concentration which are not
listed in Exhibit C. In performing searches, the 1989 (or
most recent) release of the NIST/EPA/MSDC mass spectral
library (containing 50,000 spectra) must be used. NOTE:
Substances with responses less than 10 percent of the nearest
internal standard are not required to be searched in this
fashion.
2. Only after visual comparison of sample spectra with the
spectra froa the library searches will the mass spectral
interpretation specialist assign a tentative identification.
If the compound does not meet the identification criteria of
Task III, it shall be reported as unknown. The mass spectral
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specialist should give additional classification of the
unknown compound, if possible (i.e., unknown aromatic, unknown
hydrocarbon, unknown acid type, unknown chlorinated compound).
If probable molecular weights can be distinguished, include
them.
3. The Contractor shall not report as semivolatile tentatively
identified compounds (TIC) any target compounds from the
volatile fraction (i.e., do not report late eluting volatile
compounds as TICs in the semivolatile analysis). However, the
Contractor may report pesticide target compounds that appear
as semivolatile tentatively identified compounds.
F. Task VI Quality Assurance/Quality Control Procedures.
1. All specific quality assurance procedures prescribed in
Exhibits D and E shall be strictly adhered to by the
Contractor. Records documenting the use of the protocol shall
be maintained in accordance with the document control
procedures prescribed in Exhibit F, and shall be reported in
accordance with Exhibit B, Reporting Requirements and
Deliverables.
2. The Contractor shall establish a Quality Assurance Plan (QAP)
with the objective of providing sound analytical chemical
measurements. This program shall incorporate the quality
control procedures, any necessary corrective action, and all
documentation required during data collection as well as the
quality assessment measures performed by management to ensure
acceptable data production.
3. The Contractor shall perform one spiked sample analysis
(matrix spike) and one duplicate spiked sample analysis
(matrix spike duplicate) for each group of samples of a
similar matrix (for water or soil samples) and concentration
level (for volatile and semivolatile soil samples only) for
the following, whichever is most frequent:
o Each Case of field samples received, OR
o Each 20 samples in a Case, OR
o Each 14 calendar day period during which field samples in
a Case were received (said period beginning with the
receipt of the first sample in that Sample Delivery
Group).
Matrix spikes and matrix spike duplicates shall be carried
through the entire analytical process from extraction to final
GC/MS or GC/EC analysis, including all Contract
Performance/Delivery Requirements (see Contract Schedule).
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4. The Contractor shall prepare and analyze one laboratory
reagent blank (method blank) for each group of samples of a
similar matrix (for water or soil samples), extracted by a
similar method (separatory funnel, continuous liquid-liquid
extraction, or sonication, as specified in Exhibit D), and a
similar concentration level (for •••olatile and semivolatile
soil samples only) for the following, whichever is most
frequent:
o Each Case of field samples received, OR
o Each 20 samples in a Case, including matrix spikes and
reanalyses, OR
o Each 14 calendar day period during which field samples in
a Case were received (said period beginning with the
receipt of the first sample in that Sample Delivery
Group), OR
o whenever samples are extracted.
Volatile analysis requires one method blank for each 12-hour
time period when volatile target compounds are analyzed.
Semivolatile and pesticide method blanks shall be carried
through the entire analytical process from extraction to final
GC/MS or GC/EC analysis, including all Contract
Performance/Delivery Requirements (see Contract Schedule).
5. The Contractor shall verify instrument performance for each
12-hour time period, to include the following:
Decafluorotriphenylphosphine (DFTPP) and/or Bromofluorobenzene
(BFB) as applicable, and a specific calibration using
standards of defined concentration to monitor response,
retention tine, and mass spectra.
Additional quality control shall be conducted in the form of
the analysis of Performance Evaluation check samples submitted
to the laboratory by the Agency. The results of all such
control or PE check samples may be used as grounds for
termination of noncompliant Contractors. "Compliant
performance" is defined as that which yields correct compound
identification and concentration values as determined by the
Agency, as well as meeting the contract requirements for
analysis (Exhibit D), quality assurance/quality control
(Exhibit E), data reporting and other deliverables (Exhibits B
and H), and sample custody, sample documentation and SOP
documentation (Exhibit F).
The EPA has provided to the Contractor formats for the reporting of data
(Exhibits B and H). The Contractor shall be responsible for completing
and returning analysis data sheets and submitting computer-readable data
on diskette in the format specified in this SOW and within the time
specified in the Contract Performance/Delivery Schedule.
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1. Use of formats other than those designated by EPA will be deemed as
noncompliance. Such data are unacceptable. Resubmission in the
specified format at no additional cost to the government will be
required.
2 Computer generated forms may be subritted in the hardcopy data
package(s) provided that the forms are in EXACT EPA FORMAT. This
means that the order of data elements is the same as on each EPA
required form, including form numbers and titles, page numbers and
header information.
3. The data reported by the Contractor on the hardcopy data forms and
the associated computer-readable data submitted by the Contractor
must contain identical information. If during government
inspection discrepancies are found, the Contractor shall be
required to resubmit either or both sets of data at no additional
cost to the government.
C. The Contractor shall provide analytical equipment and technical
expertise for this contract as specified by the following:
1. The Contractor shall have sufficient gas chromatograph (GC) and gas
chromatograph/mass spectrometer/data system (GC/MS/DS) capability
to meet all the terms and conditions of the Contract. The
Contractor shall maintain, at a minimum, all analytical equipment
allocated for this contract at the time of contract award.
2. The Contractor's instrument systems shall have the following:
a. The GC/MS shall be equipped with a glass jet separator when
using packed columns.
b. The computer shall be interfaced by hardware to the mass
spectrometer and be capable of acquiring continuous mass scans
for the duration of the chromatographic program.
c. The computer shall be equipped with mass storage devices for
saving all data from the GC/MS runs.
d. Computer software shall be available to allow searching GC/MS
runs for specific ions and plotting the intensity of the ions
with respect to time or scan number.
e. A computer data 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 abundances versus tine 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,
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software must be available that allows for the comparison of
sample spectra against reference library spectra. The 1989
(or most recent) release of the NIST/EPA/MSDC 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 oersonnel.
f. The GC/MS shall be equipped with a GC to MS interface capable
of extending a fused silica capillary column into the ion
source. The column is to be 30 meters long by 0.25 or 0.32 mm
inside -diameter, bonded DB-5, fused silica, or equivalent.
g. The GC for pesticide analysis shall be equipped with wide bore
capillary columns and a suitable detector as described in
Exhibit D.
3. The Contractor shall use a magnetic tape storage device capable of
recording data and suitable for long-term, off-line storage,. The
Contractor shall retain all raw GC/MS data acquired under this
contract on magnetic tape in appropriate instrument manufacturer's
format. The Contractor is required to retain the magnetic tapes
with associated hardcopy tape logbook identifying tape contents
(see Exhibit B) for 365 days after data submission. During that
time, the Contractor shall submit tapes and logbook within 7 days
of request, as specified in the Contract Performance/Delivery
Schedule.
4. The Contractor shall have a computerized MS library search system
capable of providing a forward comparison, utilizing the standard
spectra contained in the mass spectral library. The 1989 (or most
recent) release of the NIST/EPA/MSDC mass spectral library,
containing 50,000 spectra, must be used.
a. The system shall provide a numerical ranking of the standard
spectra most closely corresponding to the sample spectra
examined.
b. The data system shall have software capable of removing
background signals from spectra.
5. The Contractor shall have, in-house and operable, a device capable
of analyzing purgeable organics as described in Exhibit D.
6. The Contractor shall have, in-house, the appropriate standards for
all target compounds listed in Exhibit C prior to accepting any
samples from the Agency. Standards provided by the EPA for use in
the Preaward Performance Evaluation may not contain all the target
compounds and thus must not be used for routine analyses unless or
until they have been supplemented with commercially-available
standard materials.
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D. The Contractor shall have an IBM or IBM-compatible mini-computer or PC
capable of recording required sample data on 5.25 inch floppy
double-sided double-density 360 K-byte or 1.2 M-byte or a 3.5 inch
double-sided, double density 720 K-byte or 1.44 M-byte diskette, in
ASCII text file format, and in accordance with the file, record and
fie]i specifications listed in Exhibit H.
E. The Contractor shall designate and utilize key personnel to perform the
minimum functional requirements necessary to meet the terms and
conditions of this contract. The EPA reserves the right to review
personnel qualifications and experience. The minimum functional
requirements are listed below:
o GC/MS Laboratory Supervisor
o GC/EC Laboratory Supervisor
o Sample Preparation Laboratory Supervisor
o Quality Assurance Officer
o Systems Manager
o Programmer Analyst
o GC/MS Operator
o Mass Spectral Interpretation Specialist
o GC/EC Operator
o Pesticide Residue Analysis Expert
o Extraction/Concentration Expert
F. The Contractor shall respond within seven days to requests from data
recipients for additional information or explanations that result from
the Government's inspection activities.
G. The Contractor shall preserve all sample extracts after analysis in
bottles/ vials with Teflon-lined septa and shall maintain stored
extracts at 4*C (±2°C). The Contractor is required to retain the sample
extracts for 365 days after data submission. During that time, the
Contractor shall submit the extracts within 7 days after request, as
specified in the Contract Performance/Delivery Schedule.
H. The Contractor shall adhere to chain-of-custody procedures described in
Exhibit F. Documentation, as described therein, shall be required to
show that all procedures are being strictly followed. This
documentation shall be reported as the complete SDG file purge (see
Exhibit B).
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I. Sample shipments to the Contractor's facility will be scheduled and
coordinated by the EPA CLP Sample Management Office (SMO) acting on
behalf of the Administrative Project Officer. The Contractor shall
communicate with SMO personnel by telephone, as necessary throughout the
process of sample scheduling, shipment, analysis and data reporting, to
ensuro that samples are properly processed.
If there are problems with the samples (e.g., mixed media, containers
broken or leaking) or sample documentation/paperwork (e.g., Traffic
Reports not with shipment, sample and Traffic Report numbers 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 notify SMO personnel in
advance regarding sample data that will be delivered late and shall
specify the estimated delivery date.
J. Sample analyses will be scheduled by groups of samples, each defined as
a Case and identified by a unique EPA Case number assigned by SMO. A
Case signifies a group of samples collected at one site or geographical
area over a finite time period, and will include one or more field
samples with associated blanks. Samples may be shipped to the
Contractor in a single shipment or multiple shipments over a period of
time, depending on the size of the Case.
A Case consists of one or more Sample Delivery Group(s). A Sample
Delivery Group (SDG) is defined by the following, whichever is most
frequent:
o Each Case of field samples received, OR
o Each 20 field samples within a Case, OR
o Each 14 calendar day period during which field samples in a Case are
received (said period beginning with the receipt of the first sample
in the Sample Delivery Group).
Samples may be assigned to Sample Delivery Groups by matrix (i.e., all
soils in one SDG, all waters in another), at the discretion of the
laboratory. Such assignment must be made at the time the samples are
received, and may not be made retroactively.
All data (hardcopy and computer-readable format) for all samples in a
Sample Delivery Group are due concurrently to all data recipients as
stipulated in the Delivery Schedule in Exhibit B, Section I. Data for
all samples in a Sample Delivery Group must be submitted together (in
one package) in the order specified in Exhibit B. The Sample Delivery
Group 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 nuaber shall be the lowest sample number (considering
both alpha and numeric designations) in the first group of samples
received under the SDG. The SDG number is reported on all data
reporting forms.
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The SDG Receipt Date is the day the last sample in the SDG is received.
Data for all samples in the SDG are due as stipulated in the Delivery
Schedule in Exhibit B.
The Contractor is responsible for identifying each Sample Delivery Group
as samples are received, through proper sample documentation (see
Exhi>it B) and communication with SMO persoinel.
K. Each sample received by the Contractor will be labeled with an EPA
sample number, and accompanied by a Traffic Report form bearing the
sample number and descriptive information regarding the sample. The
Contractor shall' complete and sign the Traffic Report, recording the
date of sample receipt and sample condition on the receipt for each
sample container.
The Contractor shall submit signed copies of Traffic Reports for all
samples in a Sample Delivery Group to SMO within 3 calendar days
following receipt of the last sample in the Sample Delivery Group.
Traffic Reports shall be submitted in Sample Delivery Group sets (i.e.,
all Traffic Reports for a Sample Delivery Group shall be clipped
together) with an SDG Cover Sheet containing information regarding the
Sample Delivery Group, as specified in Exhibit B.
L. EPA Case numbers (including SDG numbers) and EPA sample numbers shall be
used by the Contractor in identifying samples received under this
contract both verbally and in reports/correspondence.
M. 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 required for the receipt of
sample shipments, including pick-up of samples at the nearest servicing
airport, bus station or other carrier service within the Contractor's
geographical area. The Contractor shall be available to receive sample
shipments at any tine the delivery service is operating, including
Saturdays.
N. 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.
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SECTION III
DETAILED TECHNICAL & MANAGEMENT REQUIREMENTS
As cited in Section II the Contractor shall have the following technical and
management capabilities:
I. TECHNICAL CAPABILITY
A. Technical Functions
1. GC/MS Laboratory Supervisor
a.. Responsible for all technical efforts of the GC/MS
laboratory to meet all terms and conditions of the EP*
contract.
b. Qualifications:
(1) Education:
Minimum of Bachelor's degree in chemistry or any
scientific/engineering discipline.
(2) Experience:
Minimum of three years of laboratory experience,
including at least one year of supervisory
experience.
2. GC/EC Laboratory Supervisor
a. Responsible for all technical efforts of the GC/EC
laboratory to meet all terms and conditions of the EPA
contract.
b. Qualifications:
(1) Education:
Minimum of Bachelor's degree in chemistry or any
scientific/engineering discipline.
(2) Experience:
Minimum of three years of laboratory experience,
including at least one year of supervisory
experience.
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3. Sample Preparation Laboratory Supervisor
a. Responsible for all technical efforts of sample
preparations to meet all terms and conditions of the EPA
contract.
b. Qualifications:
(1) Education:
Minimum of Bachelor's degree in chemistry or any
scientific/engineering discipline.
(2) Experience:
Minimum of three years of laboratory experience,
including at least one year of supervisory
experience.
4. Quality Assurance Officer
a. Responsible for overseeing the quality assurance aspects
of the data and reporting directly to upper management to
meet all terms and conditions of the EPA contract.
b. Qualifications:
(1) Education:
Minimum of Bachelor's degree in chemistry or any
scientific/engineering discipline.
(2) Experience:
Minimum of three years of laboratory experience,
including at least one year of applied experience
with QA principles and practices in an analytical
laboratory.
5. Systems Manager
a. Responsible for the management and quality control of all
computing systems (hardware, software, documentation and
procedures), generating, updating, and quality
controlling automated deliverables to meet all terms and
conditions of the EPA contract.
b. Qualifications:
(1) Education:
Minimum of Bachelor's degree with four or more
intermediate courses in programming, information
management, database management systems, or systems
requirements analysis.
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(2) Experience:
Minimum of three years experience in data or
systems management or programming including one
year of experience with the software being utilized
for data management and generation of deliverables.
6. Programmer Analyst
a. Responsible for the installation, operation and
maintenance of software and programs generating, updating
an'd quality controlling analytical databases and
automated deliverables to meet all terms and conditions
of the EPA contract.
b. Qualifications:
(1) Education:
Minimum of Bachelor's degree with four or more
intermediate courses in programming, information
management, information systems, database
management systems, or systems requirements
analysis.
(2) Experience:
Minimum of two years experience in systems or
applications programming including one year of
experience with the software being utilized for
data management and generation of deliverables.
7. GC/MS Operator Qualifications
One year of experience in operating and maintaining GC/MS/DS
with a Bachelor's degree in chemistry or a
scientific/engineering discipline, or in lieu of the
Bachelor's degree, three years of experience in operating and
maintaining the GC/MS and interpreting GC/MS data.
8. Mass Spectral Interpretation Specialist Qualifications
a. Education:
o Minimum of Bachelor's degree in chemistry or any
scientific/engineering discipline.
o Training course(s) in mass spectral interpretation.
b. Experience:
Minimum of two years of experience in mass spectral
interpretation.
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9. GC/EC Operator Qualifications
One year of experience in operating and maintaining GC/EC with
a Bachelor's degree in chemistry or a scientific/engineering
discipline, or in lieu of the Bachelor's degree, three years
of experience in operating and maintaining the GC/EC and
interpreting GC/EC data.
10. Pesticide Residue Analysis Expert Qualifications
a. Education:
Minimum of Bachelor's.degree in chemistry or any
scientific/engineering discipline.
b. Experience:
Minimum of two years of experience in operating and
maintaining GC and interpreting GC chromatograms.
11. Extraction/Concentration Expert Qualifications
a. Education:
Minimum of High school diploma and a college level
course in general chemistry.
b. Experience:
Minimum of one year of experience in
extraction/concentration.
12. Technical Staff Redundancy
The bidder shall have a minimum of one (1) chemist available
at any one time as a back-up technical person with the
following qualifications, to ensure continuous operations to
accomplish the required work as specified by EPA contract.
a. Education:
Minimum of Bachelor's degree in chemistry or any
scientific/engineering discipline.
b. Experience: Minimum of one year in each of the following
areas
o GC operation and maintenance for volatiles and
semivolatiles analyses.
o Mass spectral interpretation.
o Extraction.
o Pesticide/ Aroclors analysis.
A-17 OLM01.0
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B. Facilities
The adequacy of the facilities and equipment is of equal importance as
the technical staff to accomplish the required work as specified by the
EPA contract.
1. Sample Receipt Area
Adequate, contamination-free, well ventilated work space provided
with chemical resistant bench top for receipt and safe handling of
EPA samples..
2. Storage Area
Sufficient refrigerator space to maintain unused EPA sample volume
for 60 days after data submission and sample extracts for 365 days
after data submission. Samples must be stored in an atmosphere
demonstrated to be free from all potential contaminants. Volatile
samples must be stored in a refrigerator used only for storage of
volatile samples from this contract.
3. Sample Preparation Area
Adequate, contamination-free, we11-ventilated work space provided
with the following:
a. Benches with chemical resistant tops, exhaust hoods. NOTE:
Standards must be prepared in a glove box or isolated area.
b. Source of distilled or demineralized organic-free water.
c. Analytical balance(s) located away from draft and rapid change
in temperature.
C. Ins truroentation
At a minimum, the Contractor shall have the following instruments
operative at the time of the Preaward Site Evaluation and committed for
the full duration of the contract.
A-18 OLM01.0
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1. Primary Instrument Requirements for up to 200 Samples/Month
Capacity
Fraction
Volatiles
Semivolatiles
Pesticides/
Aroclors
No. of
Instrument (s)
1
2
2
Type of
Instrument
GC/MS/DS with
purge and
trap device
GC/MS/DS
GC/EC with
dual column
NOTE: For 300-400 Samples/Month Capacity, twice as much instrumentation
is needed as is listed in item 1.
2. Secondary Instrument Requirements for up to 200 Samples/Month
Capacity
The Contractor shall have the following instruments in place and
operational at any one time as a back-up system;
Quantity
One
One
One
Ins tr*T^ent s
GC/MS/DS
Purge and Trap Device
GC
These instruments must be included in the bidder's inventory of
equipment along with those in 1, above.
In addition, the Contractor shall have an in-house stock of
instrument parts and circuit boards to ensure continuous operation
to meet contract-specified holding and turn-around times.
3. Instrument Specifications
Instrument specifications are described in detail in the Statement
of Work (SOW) in the following Exhibits:
o Purge and trap device Exhibit D
o GC/MS/DS Exhibit D
o GC/EC Exhibit D
A-19
OLM01.0
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D. Data Management and Handling
1. Hardware - Contractor shall have an IBM or IBM-compatible mini-
computer or PC capable of recording required sample data on 5.25
inch double-sided, double-density 360 K-byte or high density 1.2 M-
byte diskettes; or 3 5 inch double-sided, double-density 72? K-byte
or 1.44 M-byte diskettes in ASCII text file format and in
accordance with the file, record and field specifications listed in
SOW, Exhibit H.
Other minimum requirements include:
o Hard disk of at least 20 M-bytes.
o Synchronous modem capable of at least 4,800 baud transmission
speed.
o PC hardware and software enabling IBM SNA 3270 emulation.
2. Software - Software, utilized in generating, updating and quality
controlling analytical databases and automated deliverables shall
have the following additional capabilities:
o Editing and updating databases.
o QC of automated deliverables.
o Controlled access using user ID and file password protection.
3. The Contractor shall also be able to submit reports and data
packages as specified in the Statement of Work Exhibit B. To
complete this task, the Contractor shall be required to provide
space, tables and adequate copy machines to meet the contract
requirements.
II. LABORATORY MANAGEMENT CAPABILITY
The Contractor must have an organization with well-defined
responsibilities for each individual in the management system to
ensure sufficient resources for the EPA contract(s)and to maintain
a successful operation. To establish this capability, the
Contractor shall designate personnel to carry out the following
responsibilities for the EPA contract. Functions include, but are
not limited to, the following:
A. Technical Staff
Responsible for all technical efforts for the EPA contract.
A-20 OLM01.0
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B. Project Manager
Responsible for overall aspects of EPA contract(s) (from sample
receipt through data delivery) and shall be the primary contact for
EPA Headquarters Administrative Project Officer and Regional
Technical Project Officers.
C. Sample Custodian
Responsible for receiving the EPA samples (logging, handling and
storage).
D. Quality Assurance Officer
Responsible for overseeing the quality assurance aspects of the
data and reporting directly to upper management.
E. Data Reporting and Delivery Officer
Responsible for all aspects of data deliverables: organization,
packaging, copying, and delivery.
A'21 OLM01.0
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EXHIBIT B
REPORTING AND DELIVERABLES REQUIREMENTS
B-l OLM01.0
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Table of Contents
Page
SECTION I: Contract Reports/De.iverables Distribution B-3
SECTION II: Report Descriptions and Order of Data
Deliverables B-6
SECTION III: Forms Instructions B-26
SECTION IV: Data Reporting Forms B-54
B-2 OLM01.0
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SECTION I
CONTRACT REPORTS/DELIVERABLES DISTRIBUTION
The following table reiterates the Contract reporting and deliverables requirements
specified in the Contract Schedule ari specifies the distribution that is required
for each deliverable. NOTE: Specific recipient names and addresses are subject to
change during the term of the contract. The Administrative Project Officer will
notify the Contractor in writing of such changes when they occur.
Item
No.
Copies
Delivery
Schedule
Distribution
(I) (2) (3)
A. Updated SOPs
45 days after
contract receipt.
*B. Sample Traffic
Reports
***C. Sample Data Summary
Package
***D. Sample Data Package
***E. Complete SDG File
****
*****F. Quality
Assurance
Plan
G. Data in Computer-
Readable Form
3 days after
receipt of last
sample in Sample
Delivery Group
(SDG).**
35 days after
receipt of last
sample in SDG.
35 days after
receipt of last
sample in SDG.
35 day- after
receipt of last
sample in SDG.
Submit copy
within 7 days
of written
request by APO
35 days after
receipt of last
sample in SDG.
As directed
B-3
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Item
No.
Copies
Delivery
Schedule
Distribution
H. GC/MS Tapes
I. Extracts
Lot Retain for 365 days
after data submis-
sion, or submit with-
in 7 days after
receipt of written
request by APO and/or
EMSL/LV.
Lot Retain for 365 days
after data submis-
sion, or submit with-
in 7 days after
receipt of written
request by APO or SMO.
As Directed
As Directed
Distribution:
(1) Sample Management Office (SMO)
(2) Region-Client (Technical Project Officer)
(3) EMSL-LV
*
**
***
****
*****
Also required in the Sample Data Summary Package.
Sample Delivery Group (SDG) is a group of samples within a Case,
received over a period of 14 days or less and not exceeding 20
samples. Data for all samples in the SDG are due concurrently. The
date of delivery of the SDG or any samples within the SDG is the
date that all samples have been delivered. (See Exhibit A for
further description).
Concurrent delivery required. Delivery shall be made such that all
designated recipients receive the item on the same calendar day.
Complete SDG File will contain the original sample data package plus
all of the original documents described under Complete SDG File
paragraph E.
See Exhibit E for a more detailed description.
NOTE: As specified in the Contract Schedule (G.6 Government Furnished
Supplies and Materials), unless otherwise instructed by the CLP Sample
Management Office, the Contractor shall dispose of unused sample volume and
used sample bottles/containers no earlier than sixty (60) days following
submission of analytical data.
B-4
OLM01.0
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Distribution Addresses:
(1) USEPA Contract Lab Program
Sample Management Office (SMO)
P. 0. Box 818
Alexandria, VA 22313
For overnight delivery service, use street address:
300 North Lee Street
Alexandria, VA 22313
(2) USEPA Environmental Monitoring
Systems Laboratory (EMSL-LV)
P. 0. Box 93478
Las Vegas, NV 89193-3478
ATTN: Data Audit Staff
For overnight delivery service, use street address:
944 E. Harmon, Executive Center
Las Vegas, NV 89109
ATTN: Data Audit Staff
3) USEPA REGIONS:
The CLP Sample Management Office, acting on behalf of the Administrative
Project Officer, will provide the Contractor with the list of addressees
for the ten EPA Regions. SMO will provide the Contractor with updated
Regional address/Mae lists as necessary throughout the period of the
contract and identify other client recipients on a case-by-case basis.
B-5 OLM01.0
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SECTION II
REPORT DESCRIPTIONS AND ORDER OF DATA DELIVERABLES
Tl a Contractor laboratory shall provide reports and other deliverables as
specified in the Contract Schedule (Performance/Delivery Schedule, Section
F.I). The required content and form of each deliverable is described in this
Exhibit.
All reports and documentation MUST BE as follows:
o Legible,
o Clearly labeled and completed in accordance with instructions in this
Exhibit,
o Arranged in the order specified in this Section, and
o Paginated.
If submitted documentation does not conform to the above criteria, the
Contractor will be required to resubmit such documentation with
Deficiency(ies) corrected, at no additional cost to the Agency.
Whenever the Contractor is required to submit or resubmit data as a result of
an on-site laboratory evaluation or through a APO/TPO action, the data must
be clearly marked as ADDITIONAL DATA and must be sent to all three
contractual data recipients (SMO, EMSL/LV, and Region). A cover letter shall
be included which describes what data is being delivered, to which EPA
Case(s) it pertains, and who requested the data.
Whenever the Contractor is required to submit or resubmit data as a result of
Contract Compliance Screening (CCS) review by SMO, the data must be sent to
all three contractual data recipients (SMO, EMSL/LV and Region), and in all
three instances must be accompanied by a color-coded COVER SHEET (Laboratory
Response To Results of Contract Compliance Screening) provided by SMO.
Section III of this Exhibit contains forms instructions to assist the
Contractor in accurately providing the Agency with all required data.
Section IV contains copies of the required data reporting forms in
Agency-specified formats. Data elements with field parameters for reporting
data in computer readable form are contained in Exhibit H.
Descriptions of the requirements for each deliverable item cited in the
Contract Performance/Delivery Schedule (Contract Schedule, Section F.I) are
specified in A-H of this Section. Items submitted concurrently MUST BE
arranged in the order listed. Additionally, the components of each item MUST
BE arranged in the order presented in this Section when the item is
submitted.
Examples of specific data deliverables not included herein nay be obtained by
submitting a written request to the EPA Administrative Project Officer,
stating the information requested, and signed by the Laboratory Manager.
B-6 OLM01.0
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A. Updated SOPs
The Contractor shall submit updated copies of all required Standard
Operating Procedures (SOPs) that were submitted with the prebid
Performance Evaluation sample results. The updated SOPs must address
any and all issues of laboratory performance and operation identified
chrough the review of the Performance E/aluation sample data and the
evaluation of Bidder-Supplied Documentation.
The Contractor must supply SOPs for the following:
1. Sample'receipt and logging.
2. Sample storage.
3. Preventing sample contamination.
4. Security for laboratory and samples.
5. Standards purity/preparation.
6. Maintaining instrument records and logbooks.
7. Sample analysis and data control systems.
8. Glassware cleaning.
9. Technical and managerial review of laboratory
operation and data package preparation.
10. Internal review of contractually-required quality
assurance and quality control data for each
individual data package.
11. Sample analysis, data handlir _, and reporting.
12. Chain-of-Custody procedures and document control
including SDG file preparation.
13. Laboratory data validation/laboratory self -
inspection system.
14. Data Management and Handling
B. S*"role Traffic Reports
Original Sample Traffic Report page marked "Lab Copy for Return to SMO"
with lab receipt information and signed in original Contractor
signature, for each sample in the Sample Delivery Group.
Traffic Reports (TRs) shall be submitted in Sample Delivery Group (SDG)
sets (i.e., TRs for all samples in an SDG shall be clipped together),
with an SDG Cover Sheet attached.
B-7 OLM01.0
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The SDG Cover Sheet shall contain the following items:
o Lab name.
o Contract number.
o Sample Analysis Price - full sample price from contract.
o Case Number.
o 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) .
In addition, each Traffic Report must be clearly marked with the SDG
Number, the sample number of the first sample in the SDG (as described
in the following paragraph) . This information should be entered below
the Lab Receipt Date on the TR. In addition, the TR for the last sample
received in the SDG Bust be clearly marked "SDG - FINAL SAMPLE."
The EPA sample number of the first sample received in the SDG is the SDG
number. When several samples are received together in the first SDG
shipment, the SDG number shall be the lowest sample number (considering
both alpha and numeric designations) in the first group of samples
received under the SDG. The SDG number is also reported on all data
reporting forms (see Section III, Forms Instruction Guide).
If samples are received at the laboratory with multi- sample Traffic
Reports (TRs) , all the samples on one multi-sample TR may not
necessarily be in the same SDG. In this instance, the laboratory must
make the appropriate number of photocopies of the TR, and submit one
copy with each SDG cover sheet.
C . Sample Data Siy^^arv Package
As specified in the Delivery Schedule, one Sample Data Summary Package
shall be delivered to SMO concurrently with delivery of other required
sample data. The Sample Data Summary Package consists of copies of
specified items from the Sample Data Package. These items are listed
below and are described under part D, Sample Data Package.
The Sample Data Summary Package shall be ordered as follows and shall be
submitted separately (i.e., separated by rubber bands, clips or other
means) directly preceding the Sample Data Package. Sample data forms
shall be arranged in increasing EPA sample number order, considering
both letters and numbers. For example, BE400 is a lower sample number
than BF100, as E precedes F in the alphabet.
The Sample Data Summary Package shall contain data for samples in one
Sample Delivery Group of the Case, as follows:
B-8 OLM01.0
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1. Case Narrative
2. By fraction (VGA, SV, PEST) and by sample within each fraction -
tabulated target compound results (Form I) and tentatively
identified compounds (Form I, TIC) (VGA and SV only)
3. ty fraction (VOA, SV, PEST) - surrogate spike analysis results (Form
II) by matrix (water and/or soil) and for soil, by concentration
(low or medium)
4. By fraction (VOA, SV, PEST) - matrix spike/matrix spike duplicate
results (Form III)
5. By fraction (VOA, SV, PEST) - blank data (Form IV) and tabulated
results (Form I) including tentatively identified compounds (Form I,
TIC) (VOA and SV only)
6. By fraction (VOA, SV only) - internal standard area data (Form VIII)
Data Packae
The Sample Data Package is divided into the five major units described
below. The last three units are each specific to an analytical fraction
(volatiles, semivolatiles , 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 analyses of all samples
in one Sample Delivery Group, including field samples, reanalyses,
blanks, matrix spikes, and matrix spike duplicates.
The Contractor shall retain a copy of the sample Data Package for 365
days after final acceptance of data. After this time, the Contractor
may dispose of the package.
1. SDG Narrative
This document shall be clearly labeled "SDG Narrative" and shall
contain: laboratory name; Case number; sample numbers in the Sample
Delivery Group (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.
Whenever data from sample re -analyses are submitted, the Contractor
shall state in the SDG Narrative for each re-analysis, whether it
considers the re-analysis to be billable, and if so, why.
The Contractor must also include any problems encountered: both
technical and administrative, the corrective actions taken, and
resolution and an explanation for all flagged edits (i.e., manual
edits) on quantitation lists.
B-9 OLM01.0
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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 designet, as verified by the following
signature." This statement shall be directly followed by signature
of the Laboratory Manager or his designee with a typed line below it
containing the signer's name and title, and the date of signature.
Additionally, the SDG Narrative itself must be signed in original
signature by the Laboratory Manager or his designee and dated.
2. Traffic Reports
A copy of the Sample Traffic Reports submitted in Item A for all of
the samples in the SDG. The Traffic Reports shall be arranged in
increasing EPA sample number order, considering both letters and
numbering in ordering samples. Copies of the SDG cover sheet is to
be included with the copies of the Traffic Reports.
If samples are received at the laboratory vith multi-sample Traffic
Reports (TRs), all the samples on one multi-sample TR may not
necessarily be in the same SDG. In this instance, the laboratory
must make the appropriate number of photocopies of the TR so that a
copy is submitted with each data package to which it applies. In
addition, in any instance where samples from more than one multi-
sample TR are in the same data package, the laboratory must submit a
copy of the SDG cover sheet with copies of the TRs.
3. Volatiles Data
a. QC Summary
(1) System Monitoring Compound Summary (Form II VGA)
(2) Matrix Spike/Matrix Spike Duplicate Summary (Form III VGA)
(3) Method Blank Summary (Form IV VGA)
(If more than a single form is necessary, forms must be
arranged in chronological order by date of analysis of the
blank.)
(4) GC/MS Instrument Performance Check (Form V VGA)
In chronological order; by instrument.
(5) Internal Standard Area and RT Saury (Form VIII VGA)
In chronological order; by instrument.
B-10 OLM01.0
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b. Sample Data
Sample data shall be arranged in packets with the Organic
Analysis Data Sheet (Form I VOA, including Form I VOA-TIC),
followed by the raw data for volatile samples. These sample
packets should then be placed in increasing EPA sample number
order, considering both letters and Lumbers in ordering
samples.
(1) Target Compound Results - Organic Analysis Data Sheet
(Fora I VOA).
Tabulated results (identification and quantitation) of the
specified target compounds (Exhibit C). The validation
and release of these results is authorized by a specific,
signed statement in the SDG Narrative (reference E.I). In
the event that the Laboratory Manager cannot validate 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) Tentatively Identified Compounds (Form I VOA-TIC).
This form must be included even if no compounds are found.
If so, indicate this on the form by entering "0" in the
field for "Number found."
Form I VOA-TIC is the tabulated list of the highest
probable match for up to 10 organic compounds that are not
system monitoring compounds and are not listed in Exhibit
C (TCL). It includes the CAS (Chemical Abstracts Service)
Registry Number, tentative identification, and estimated
concentration.
(3) Reconstructed total ion chr^matograms (RIC) for each
sample or sample extract.
RICs must be normalized to the largest nonsolvent
component, and must contain the following header
information:
o EPA sample number.
o Date and time of analysis.
o GC/MS instrument ID.
o Lab file ID.
Internal standards and system monitoring compounds are to
be labeled with the names of compounds, either directly
out from the peak, or on a print-out of retention times if
retention times are printed over the peak.
B-ll OLM01.0
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If automated data system procedures are used for
preliminary identification and/or quantification of the
target compounds, the complete data system report must 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 no; use the automated data
system procedures, a laboratory "raw data sheet,"
containing the following information, must be included in
the sample data package in addition to the chromatogram.
o ' EPA sample number.
o Date and time of analysis.
o RT or scan number of identified target compounds.
o Ion used for quant i tat ion with measured area.
o Copy of area table from data system.
o GC/MS instrument ID.
o Lab file ID.
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.
(4) For each sample, by each compound identified, the
following shall be included in the data package:
(a) Copies of raw spectra and copies of
background-subtracted mass spectra of target
compounds listed in Exhibit C (TCL) that are
identified in the sample and corresponding
background-subtracted target compound standard mass
spectra. Spectra must be labeled with EPA sample
number, lab file ID, date and time of analysis, and
GC/MS instrument ID; compound names must be clearly
marked on all spectra.
(b) Copies of mass spectra of organic compounds not
listed in Exhibit C (TCL), Tentatively Identified
Compounds, with associated best-match spectra (three
best matches), labeled as in (4)(a) above.
c. Standards Data
(1) Initial Calibration Data (Form VI VGA) - in order by
instrument, if more than one instrument used.
(a) VOA standard(s) reconstructed ion chromatograms and
quantitation reports (or legible facsimile) for the
B-12 OLM01.0
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initial (five point) calibration, labeled as in b.(3)
above. Spectra are not required.
(b) All initial calibration data that pertain to samples
in the data package must be included, regardless of
when it was performed and for which Case. When more
than one initial calibration is performed, the data
must be put in chronological order, by instrument.
(2) Continuing Calibration (Form VII VOA) - in order by
instrument, if more than one instrument used.
(a) VOA standard(s) reconstructed ion chromatograms and
quantitation reports (or legible facsimile) for all
continuing (12 hour) calibrations, labeled as in
b.(3) above. Spectra are not required.
(b) When more than one continuing calibration is
performed, forms must be in chronological order,
within fraction and instrument.
Raw QC Data
(1) BFB (for each 12-hour period, for each GC/MS system
utilized)
(a) Bar graph spectrum, labeled as in b.(3) above.
(b) Mass listing, labeled as in b.(3) above.
(c) Reconstructed total ion chromatogram (RIC), labeled
as in b.(3) above.
(2) Blank Data - in chronological order. NOTE: This order is
different from that used for samples.
(a) Tabulated results (Form I VOA).
(b) Tentatively Identified Compounds (Form I VOA-TIC)
even if none found.
(c) Reconstructed ion chromatogram(s) and quantitation
report(s) or legible facsimile (GC/MS), labeled as in
b.(3) above.
(d) Target compound spectra with lab generated standard,
labeled as in b.(4) above. Data systems which are
incapable of dual display shall provide spectra in
the following order:
o Raw target compound spectra.
o Enhanced or background subtracted spectra.
o Laboratory generated standard spectra.
B-13 OLM01.0
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(e) GC/MS library search spectra for Tentatively
Identified Compounds (TIC), labeled as in b.(4)
above.
(f) Quantitation/Calculation of Tentatively Identified
Compound(s) (TIC) concentrations.
(3) Matrix Spike Data
(a) Tabulated results (Form I VOA) of target compounds.
Form I VOA-TIC not required.
(b) Reconstructed ion chromatogram(s) and quantitation
report(s) or legible facsimile (GC/MS), labeled as in
b.(4) above. Spectra not required.
(4) Matrix Spike Duplicate Data
(a) Tabulated results (Form I VOA) of target compounds.
Form I VOA-TIC not required.
(b) Reconstructed ion chromatogram(s) and quantitation
report(s) or legible facsimile (GC/MS), labeled as in
b.(4) above. Spectra not required.
4. Semivolatiles Data
a. QC Summary
(1) Surrogate Percent Recovery Summary (Form II SV)
(2) Matrix Spike/Matrix Spike Duplicate Summary (Form III SV)
(3) Method Blank Summary (Form IV SV)
(If more than a single form is necessary, forms must be
arranged in chronological order by date of analysis of the
blank.)
(4) GC/MS Instrument Performance Check (Form V SV)
In chronological order; by instrument.
(5) Internal Standard Area and RT Summary (Form VIII SV)
In chronological order; by instrument.
b. Sample Data
Sample data shall be arranged in packets with the Organic
Analysis Data Sheet (Form I SV. including Form I SV-TIC) ,
followed by the raw data for semi volatile samples. These
sample packets should then be placed in increasing EPA sample
B-14 OLM01.0
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number order, considering both letters and numbers in ordering
samples.
(1) Target Compound Results - Organic Analysis Data Sheet
(Form I SV-1. SV-2).
Tabulated results (identification anc quantitation) of the
specified target compounds (Exhibit C). The validation
and release of these results is authorized by a specific,
signed statement in the SDG Narrative (reference E.I). In
the event that the Laboratory Manager cannot validate 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) Tentatively Identified Compounds (Form I SV-TIC).
This form must be included even if no compounds are found.
If so, indicate this on the form by entering "0" in the
field for "Number found".
Form I SV-TIC is the tabulated list of the highest
probable match for up to 20 of the non-surrogate organic
compounds not listed in Exhibit C (TCL). It includes the
CAS (Chemical Abstracts Service) Registry Number,
tentative identification, and estimated concentration.
(3) Reconstructed total ion chromatograms (RIC) for each
sample, sample extract, standard, blank, and spiked
sample.
RICs must be normalized to the largest nonsolvent
component, and must contain the following header
information:
o EPA sample number.
o Date and time of analysis.
o GC/MS instrument ID.
o Lab file ID.
Internal standards and surrogates compounds are to be
labeled with the names of compounds, either directly out
from the peak, or on a print-out of retention times if
retention times are printed over the peak.
If automated data system procedures are used for
preliminary identification and/or quantification of the
target compounds, the complete data system report must 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,"
B-15 OLM01.0
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containing the following information, oust be included in
the sample data package in addition to the chromatogram.
o EPA sample number.
o Date and time of analysis.
o RT or scan number of identified .arget compounds.
o Ion used for quantitation with measured area.
o Copy of area table from data system.
o . GC/MS instrument ID.
o Lab file ID.
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.
(4) For each sample, by each compound identified, the
following shall be included in the data package:
(a) Copies of raw spectra and copies of
background-subtracted mass spectra of target
compounds listed in Exhibit C (TCL) that are
identified in the sample and corresponding
background-subtracted target compound standard mass
spectra. Spectra must be labeled with EPA sample
number, lab file ID, date and time of analysis, and
GC/MS instrument ID; compound names must be clearly
marked on all spectra.
(b) Copies of mass spectra of nonsurrogate organic
compounds not listed in Exhibit C (TCL), Tentatively
Identified Compounds with associated best-match
spectra (three best matches), labeled as in (4)(a)
above.
c. Standards Data
(1) Initial Calibration Data (Form VI SV-1, SV-2) - in order
by instrument, if more than one instrument used.
(a) Semivolatile standard(s) reconstructed ion
chromatograms and quantitation reports (or legible
facsimile) for the initial (five point) calibration,
labeled as in b.(3) above. Spectra are not required.
(b) All initial calibration data that pertain to samples
in the data package must be included, regardless of
when it was performed and for which Case. When more
than one initial calibration is performed, the data
must be put in chronological order, by instrument.
B-16 OLM01.0
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(2) Continuing Calibration (Form VII SV-1, SV-2) - in order by
instrument, if more than one instrument used.
(a) Semivolatile standard(s) reconstructed ion
chromatograms and quantitation reports (or legible
facsimile) for all continuing (12 hour) calibrations,
labeled as in b.(3) above. Spectra are not required.
(b) When more than one continuing calibration is
performed, forms must be in chronological order, by
instrument.
(3) Semivolatile GPC Calibration Data - UV detector traces
shoving peaks that correspond to the compounds in the
semivolatile GPC calibration mixture. Traces must be
labeled with GPC column identifier, date of calibration,
and with compound names labeled either directly out from
the peak, or on a printout of retention times, if
retention times are printed over the peak. Do not include
Form IX Pest-2, as the compounds used on that form are not
appropriate for semivolatile sample extracts.
d. Raw QC Data
(1) DFTPP (for each 12-hour period, for each GC/MS system
utilized)
(a) Bar graph spectrum, labeled as in b(3) above.
(b) Mass listing, labeled as in b.(3) above.
(c) Reconstructed total ion chromatogram (RIG), labeled
as in b.(3) above.
(2) Blank Data - in chronological order. NOTE: This order is
different from that used for samples.
(a) Tabulated results (Form I SV-1, SV-2)
(b) Tentatively Identified Compounds (Form I SV-TIC) -
even if none found.
(c) Reconstructed ion chromatogram(s) and quantitation
report(s) or legible facsimile (GC/MS), labeled as in
b(3) above.
(d) Target compound spectra with lab generated standard,
labeled as in b(4) above. Data systems which are
incapable of dual display shall provide spectra in
the following order:
o Raw target compound spectra.
o Enhanced or background subtracted spectra.
o Laboratory generated standard spectra.
B-17 OLM01.0
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(e) GC/MS library search spectra for Tentatively
Identified Compounds (TIC), labeled as in b(4) above.
(f) Quantitation/Calculation of Tentatively Identified
Compound(s) (TIC) concentrations
(3) Matrix Spike Data
(a) Tabulated results (Form I) of target compounds. Form
1 SV-TIC not required.
(b) Reconstructed ion chromatogram(s) and quantitation
report(s) or legible facsimile (GC/MS), labeled as in
b(3) above. Spectra not required.
(4) Matrix Spike Duplicate Data
(a) Tabulated results (Form I SV-1, SV-2) of target
compounds. Form 1 SV-TIC not required.
(b) Reconstructed ion chromatogram(s) and quantitation
report(s) or legible facsimile (GC/MS), labeled as in
b(3) above. Spectra not required.
Pesticide/Aroclor Data
a. QC Summary
(1) Surrogate Percent Recovery Summary (Form II PEST)
(2) Matrix Spike/Matrix Spike Duplicate Summary (Form III
PEST)
(3) Method Blank Summary (Form IV PEST)
(If more than a single form is necessary, forms must be
arranged in chronological order by date of analysis of the
blank.)
b. Sample Data
Sample data shall be arranged in packets with the Organic
Analysis Data Sheet (Fore I PEST), followed by the raw data for
pesticide samples. These sample packets should then be placed
in increasing EPA sample number order, considering both letters
and numbers in ordering samples.
(1) Target Compound Results - Organic Analysis Data Sheet
(Form I PEST).
Tabulated results (identification and quantitation) of the
specified target compounds (Exhibit C). The validation
and release of these results is authorized by a specific,
signed statement in the SDG Narrative (reference E.I). In
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the event that the Laboratory Manager cannot validate 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) Copies of pesticide chromatograms.
All chromatograms must be labeled with the following
information:
o EPA Sample Number.
o Volume injected (uL).
o Date and time of injection.
o GC column identification (by stationary phase and
internal diameter).
o GC instrument identification.
o Positively identified compounds must be labeled with
the names of compounds, either directly out from the
peak, or on a print-out of retention times if
retention times are printed over the peak.
(3) Copies of pesticide chromatograms from second GC column,
labeled as in (2) above.
(4) GC Integration report or data system printout.
(5) Manual work sheets.
(6) If pesticide/Aroclors are confirmed by GC/MS, the
Contractor shall submit copies of raw spectra and copies
of background-subtracted mass spectra of target compounds
listed in Exhibit C (TCL) that are identified in the
sample and corresponding background-subtracted TCL
standard mass spectra. Compound names must be clearly
marked on all spectra. For multicomponent
pesticides/Aroclors confirmed by GC/MS, the Contractor
shall submit mass spectra of 3 major peaks of
multicomponent compounds from samples and standards.
c. Standards Data
(1) Initial Calibration of Single Component Analytes (Form VI
PEST-1 and PEST-2) - all GC columns, all instruments, in
chronological order by GC column and instrument.
(2) Initial Calibration of Multicomponent Analytes (Form VI
PEST-3) - all GC columns, all instruments, in
chronological order by GC column and instrument.
(3) Analyte Resolution Summary (Form VI PEST-4) - all GC
columns and instruments, in chronological order by GC
column and instrument.
B-19 OLM01.0
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(4) Calibration Verification Summary (Form VII PEST-1) - for
all Performance Evaluation Mixtures and Instrument: blanks,
on all GC columns and instruments, in chronological order
by GC column and instrument.
(5) Calibration Verification Summary (Form VII PEST-2) - for
all mid point concentrations of Iniividual Standard
Mixtures A and B and Instrument blanks used for
calibration verification, on all GC columns and
instruments, in chronological order by GC column and
instrument.
(6) Analytical Sequence (Form VIII PEST) - all GC columns and
instruments, in chronological order by GC column and
instrument.
(7) Florisil Cartridge Check (Form IX PEST-1) - for all lots
of cartridges used to process samples in the SDG.
(8) Pesticide GPC Calibration (Form IX PEST-2) - all GPC
columns, in chronological order by calibration date.
(9) Pesticide Identification Summary for Single Component
Analytes (Form X PEST-1) - for all samples with positively
identified single component analytes, in order by EPA
sample number.
(10) Pesticide Identification Summary for Mulcicomponent
Analytes (Form X PEST-2) - for all samples with positively
identified multicomponent analytes, in order by EPA sample
number.
(11) Chromatograms and data system printouts are required for
all standards including the following:
o Resolution Check Mixture.
o Performance Evaluation Mixtures, all.
o Individual Standard Mixture A, at three
concentrations, each initial calibration.
o Individual Standard Mixture B, at three
concentrations, each initial calibration.
o All multicomponent analytes (Toxaphene and Aroclors),
each initial calibration.
o All mid point concentrations of Individual Standard
Mixtures A and B used for calibration verification.
o Florisil cartridge check solution, all lots.
o Pesticide GPC Calibration Check Solution, all
calibrations relating to samples in the SDG.
o All multicomponent analyte standards analyzed for
confirmation.
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(12) A printout of retention times and corresponding peak areas
or peak heights must accompany each chromatogram. In
addition, all chromatograms are required to be labeled
with the following:
o EPA Sample Number for the standard, i.e., INDAl,
INDA2, etc. (See Forms Instructions for details.)
o Label all standard peaks for all individual compounds
either directly out from the peak or on the printout
of retention times if retention times are printed over
- the peak.
o Total nanograms injected for each standard.
o Date and time of injection.
o GC column identification (by stationary phase and
internal diameter).
o GC instrument identification.
(13) A copy of the computer reproduction output covering the
entire calibration range is required for each initial
calibration.
(14) Pesticide GPC Calibration Data - UV detector traces
showing peaks that correspond to the compounds in the
pesticide GPC calibration mixture. Traces must be labeled
with GPC column identifier, date of calibration, and with
compound names labeled either directly out from the peak,
or on a printout of retention times, if retention times
are printed over the peak.
d. Raw QC Data
(1) Blank Data - in chronological order, by type of blank
(method, instrument, sulfur clean up). NOTE: This order
is different from that used for samples.
(a) Tabulated results (Form I PEST).
(b) Chromatogram(s) and data system printout(s) (GC) for
each GC column and instrument used for analysis,
labeled as in b.(2) above.
(2) Matrix Spike Data
(a) Tabulated results (Form. I PEST) of target compounds.
(b) Chromatogram(s) and data system printout(s) (GC),
labeled as in b.(2) above.
B-21 OLM01.0
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(3) Matrix Spike Duplicate Data
(a) Tabulated results (Form I PEST) of target compounds.
(b) Chromatogram(s) and data system printout(s) (GC),
labeled as in b.(2) above.
E. Complete SPG File
As specified in the Delivery Schedule, one Complete SDG File (CSF)
including the original Sample Data Package shall be delivered to the
Region concurrently with delivery of the Sample Data Package to SMO and
EMSL-LV. The contents of the CSF will be numbered according to the
specifications described in Section III and IV of Exhibit B. The
Document Inventory Sheet, Form DC-2, is contained in Section IV. The
CSF will contain all original documents where possible. No copies will
be placed in the CSF unless the originals are bound in a logbook which
is maintained by the laboratory. The CSF will contain all original
documents specified in Section III and IV, and Form DC-2 of Exhibit B of
the SOW.
The CSF will consist of the following original documents in addition to
the documents in the Sample Data Package:
1. Original Sample Data Package
2. A completed and signed Document Inventory Sheet (Form DC-2).
3. All original shipping documents, including, but not limited to, the
following documents:
a. EPA Chain of Custody Record.
b. Airbills.
c. EPA Traffic Reports.
d. Sample Tags (if present) sealed in plastic bags.
4. All original receiving documents, including, but not limited to, the
following documents:
a. Form DC-1.
b. Other receiving forms or copies of receiving logbooks.
c. SDG Cover Sheet.
5. All original laboratory records, not already submitted in the Sample
Data Package, of sample transfer, preparation and analysis,
including, but not limited to, the following documents:
a. Original preparation and analysis forms or copies of preparation
and analysis logbook pages.
b. Internal sample and sample extract transfer chain-of-custody
records.
B-22 OLM01.0
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c. Screening records.
d. All instrument output, including strip charts from screening
activities.
6. All other original SDG-specific documents in the possession of the
laboratory, including, but not limited to, the following documents:
a. Telephone contact logs.
b. Copies of personal logbook pages.
c. All hand written case-specific notes.
d. Any other case-specific documents not covered by the above.
NOTE: All Case-related documentation may be used or admitted as
evidence in subsequent legal proceedings. Any other Case-specific
documents generated after the CSF is sent to EPA, as well as copies that
are altered in any fashion, are also deliverables to EPA. (Original to
the Region, and copies to SMO and EMSL-LV).
If the laboratory does submit SDG-specific documents to EPA after
submission of the CSF, the documents should be numbered as an addendum
to the CSF and a revised DC-2 form should be submitted, or the documents
should be numbered as a new CSF and a new DC-2 form should be submitted
to the Regions only.
F. Data in Computer-Readable Form
The Contractor shall provide a computer-readable copy of the data on
data reporting Forms I-X for all samples in the Sample Delivery Group,
as specified in the Contract Performance/Delivery Schedule.
Computer-readable data deliverables shall be submitted on IBM or
IBM-compatible, 5.25 inch floppy double-sided, double density 360
K-byte, a high density 1.2 M-byte or a 3.5 inch double-sided double
density 720 K-byte or 1.44 M-byte diskette.
When submitted, diskettes shall be packaged and shipped in such a manner
that the diskette(s) cannot be bent or folded, and will not be exposed
to extreme heat or cold or any type of electromagnetic radiation. The
diskette(s) must be included in the same shipment as the hardcopy data
and shall, at a minimum, be enclosed in a diskette mailer. The data
shall be recorded in ASCII, text file format, and shall adhere to the
file, record and field specifications listed in Exhibit H, Data
Dictionary and Format for Data Deliverables in Computer-Readable Format.
If the Contractor wishes to use a reporting format other than the one
specified, equivalence must be demonstrated and approved by the
Administrative Project Officer prior to the award of the contract.
G. GC/MS Tapes
The Contractor must store all raw and processed GC/MS data on magnetic
tape, in appropriate instrument manufacturer's format. This tape must
include data for samples, blanks, matrix spikes, matrix spike
duplicates, initial calibrations, continuing calibrations, BFB and
B-23 OLM01.0
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DFTPP, as well as all laboratory-generated spectral libraries and
quantitation reports required to generate the data package. The
Contractor shall maintain a written reference logbook of tape files to
EPA sample number, calibration data, standards, blanks, matrix spikes,
and matrix spike duplicates. The logbook should include EPA sample
numbers and standard and blank ID's, identified by Case and Sample
Delivery Group.
The Contractor is required to retain the GC/MS tapes for 365 days after
data submission. During that time, the Contractor shall submit tapes
and associated logbook pages within seven days after receipt of a
written request from the Administrative Project Officer.
When submitting GC/MS tapes to the Agency, the following materials must
be delivered in response to the request:
1. All associated raw data files for samples, blanks, matrix spikes,
matrix spike duplicates, initial and continuing calibration
standards, and instrument performance check solutions (BFB and
DFTPP).
2. All processed data files and quantitation output files associated
with the raw data files described above.
3. All associated identifications and calculation files used to
generate the data submitted in the data package.
4. All laboratory-generated mass spectral library files (NIST/EPA/MSDC
library not required).
5. A copy of the Contractor's written reference logbook relating tape
files to EPA Sample Number, calibration data, standards, blanks,
matrix spikes, and matrix spike duplicates. The logbook must:
include EPA Sample Numbers and Lab File identifiers for all samples,
blanks, and standards, identified by Case and SDG.
The laboratory must also provide a statement attesting to the
completeness of the GC/MS data tape submission, signed and dated by the
Laboratory Manager. This statement must be part of a cover sheet that
includes the following information relevant to the data tape submission:
1. Laboratory name
2. Date of submission
3. Case Number
4. SDG Number
5. GC/MS make and model number
6. Software version
7. Disk drive type (e.g. CDC, PRIAM, etc.)
B-24 OLM01.0
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8. File transfer method (e.g. DSD, DTD, FTP. Aquarius, etc.)
9. Names and telephone numbers of two laboratory contacts for further
information regarding the submission.
H. Extracts
The Contractor shall preserve sample extracts at 4°C (±2°C) in
bottles/vials with Teflon-lined septa. Extract bottles/vials shall be
labeled with EPA sample number, Case number and Sample Delivery Group
(SDG) number. A logbook of stored extracts shall be maintained, listing
EPA sample numbers and associated Case and SDG numbers.
The Contractor is required to retain extracts for 365 days following
data submission. During that time, the Contractor shall submit extracts
and associated logbook pages within seven days following receipt of a
written request from the Administrative Project Officer or the Sample
Management Office.
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SECTION III
FORMS INSTRUCTIONS
B-26 OLM01.0
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SECTION III
FORM INSTRUCTION GUIDE
This section includes specific instrueLions for the completion of all
required forms. Each of the forms is specific to a given fraction
(volatile, semivolatile, pesticide/Aroclor), and in some instances
specific to a given matrix (water or soil) within each fraction. The
contractor shall submit only those forms pertaining to the fractions
analyzed for a given sample or samples. For instance, if a sample is
scheduled for volatile analysis only, provide only VOA forms. There
are two pages relating to the semivolatile fraction for Forms I, VI,
VII, and VIII. Whenever semivolatiles are analyzed and one of the
above-named forms is required, both pages (SV-1 and SV-2) must be
submitted. These instructions are arranged in the following order:
A. General Information and Header Information
B. Organic Analysis Data Sheets (Form I, All Fractions)
C. System Monitoring Compound Recovery (Form II VOA)
D. Surrogate Recovery (Form II, SV and PEST)
E. Matrix Spike/Matrix Spike Duplicate Recovery (Form III, All
Fractions)
F. Method Blank Summary (Form IV, All Fractions)
G. GC/MS Instrument Performance Check and Mass Calibration (Form V VOA
and SV)
H. GC/MS Initial Calibration Data (Form VI VOA, SV-1, SV-2)
I. GC Initial Calibration Data (Form VI PEST-1, PEST-2, PEST-3, PEST-4)
J. GC/MS Continuing Calibration Data (Form VII VOA, SV-1, SV-2)
K. GC/EC Continuing Calibration (Form VII PEST)
L. Internal Standard Area Summary (Form VIII VOA and SV)
M. Pesticide Analytical Sequence (Form VIII PEST)
N. Pesticide Cleanup Procedures (Form IX PEST-1, PEST-2)
0. Pesticide/Aroclor Identification (Form X PEST-1, PEST-2)
P. Sample Log-In Sheet (Form DC-1)
Q. Document Inventory Sheet (Form DC-2)
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A. General Information and Header Information
The data reporting forms presented in Section IV have been designed in
conjunction with the computer-readable data format specified in Exhibit
H, Data Dictionary and Format for Data Deliverables in
Computer-Readable Format. The specific length of each variable for
computer-readable data transmission purposes is given in the Data
Dictionary (Exhibit H). Information entered on these forms must not
exceed the size of the field given on the form, including such
laboratory-generated items as Lab Name and Lab Sample ID.
Note that on the hardcopy forms (Section IV), the space provided for
entries is greater in some instances than the length prescribed for the
variable as written to diskette (see Exhibit H). Greater space is
provided on the hardcopy forms for the sake of visual clarity.
Values must be reported on the hardcopy forms according to the
individual form instructions in this Section. For example, results for
concentrations of VOA target compounds must be reported to two
significant figures if the value is greater than or equal to 10.
Values can be written to the diskette file in any format that does not
exceed the field specification as given in the record specifications
and discussed in "Record Structure", paragraph 5 of Exhibit H.
All characters which appear on the data reporting forms presented in
the contract (Exhibit B, Section IV) must be reproduced by the
Contractor when submitting data, and the format of the forms submitted
must be identical to that shown in the contract. No information may be
added, deleted, or moved from its specified position without prior
written approval of the EPA Administrative Project Officer. The names
of the various fields and compounds (i.e., "Lab Code," "Chloromethane")
must appear as they do on the forms in the contract, including the
options specified in the form (i.e., "Matrix: (soil/water)" must
appear, not just "Matrix"). For items appearing on the uncompleted
forms (Section IV), the use of uppercase and lowercase letters is
optional.
Alphabetic entries made onto the forms by the Contractor shall be in
ALL UPPERCASE letters (i.e., "LOW", not "Low" or "low"). If an entry
does not fill the entire blank space provided on the form, null
characters shall be used to remove the remaining underscores that
comprise the blank line. See Exhibit H for more detailed instructions.
However, do not remove the underscores or vertical bar characters 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 2A, line 30, if data must be entered on
line 30, it will replace the underscores).
Six pieces of information are common to the header sections of each
data reporting form. They are Lab Name, Contract, Lab Code, Case No.,
SAS No., and SDG No. Except as noted below for SAS No., this
information must be entered on every form and must match on every form.
n oo
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The "Lab Name" shall be the name chosen by the Contractor to identify
the laboratory. It may not exceed 25 characters.
The "Lab Code" is an alphabetical abbreviation of up to 6 letters,
assigned bv the EPA, to identify the laboratory and aid in data
processing. This lab code shall be assigned by the EPA at the time a
contract is awarded, and shall not be modified by the Contractor,
except at the direction of the EPA. If a change of name or ownership
occurs at the laboratory, the lab code will remain the same until the
contractor is directed by the EPA to use another lab code assigned by
the EPA.
The "Case No." is the EPA-assigned Case number associated with the
sample, and reported on the Traffic Report.
The "Contract" is the number of the EPA contract under which the
analyses were performed. In the case of multiple laboratories
operating under a corporate-wide contract, the contract number entered
shall be that of the corporate contract, regardless of the facility
performing the analyses (see Lab Code, above).
The "SDG No." is the Sample Delivery Group number. The Sample Delivery
Group (SDG) number is the EPA Sample Number of the first sample
received in the SDG. When several samples are received together in the
first SDG shipment, the SDG number shall be the lowest sample number
(considering both alpha and numeric designations) in the first group of
samples received under the SDG.
The "SAS No." is the EPA-assigned number for analyses performed under
Special Analytical Services. If samples are to be analyzed under SAS
only and reported on these forms, then enter SAS No. and leave Case No.
blank. If samples are analyzed according to the "Routine Analytical
Services" (IFB) protocols and have additional "SAS" requirements, list
both Case No. and SAS No. on all forms. If the analyses have no SAS
requirements, leave "SAS No." blank. NOTE: Some samples in an. SDG may
have a SAS No. while others do not.
The other information common to most of the forms is the "EPA Sample
No.". This number appears either in the upper righthand corner of the
form, or as the left column of a table summarizing data from a number
of samples. When the "EPA Sample No." is entered into the
triple-spaced box in the upper righthand 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.
All samples, matrix spikes, matrix spike duplicates, blanks, and
standards shall be identified with an EPA Sample Number. For field
samples, matrix spikes and matrix spike duplicates, the EPA Sample
Number is the unique identifying number given in the Traffic Report
that accompanied that sample.
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In order to facilitate data assessment, the following sample suffixes
must be used:
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 secondary dilution
Form VIII Pest requires that all samples analyzed in a given analytical
sequence be listed, regardless of whether or not they are part of the
SDG being reported. Therefore, use "ZZZZZ" as the EPA 'Sample No. for
any sample analysis not associated with the SDG being reported.
For blanks and standards, the following identification scheme must be
used as the "EPA Sample No."
1. Volatile blanks shall be identified as VBLK##.
2. Semivolacile blanks shall be identified as SBLK##.
3. Pesticide/Aroclor method blanks shall be identified as
4. Pesticide/Aroclor instrument blanks shall be identified as
PI3LK=-.
The "EPA Sample No." must be unique for each blank within an SDG.
Within a fraction, a laboratory must 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.
Volatile and semivolatile standards shall be identified as FSTD###,
where
F - Fraction (V for volatiles; S for semivolatiles) .
STD = Indicates a standard.
### - The concentration in ug/L of volatile standards
(i.e., 010, 020, 050, 100, and 200) or the amount
injected in ng for semivolatile standards
(i.e., 020, 050, 080, 120, and 160) .
As for the blank identifiers, these designations will have to be
concatenated with other information to uniquely identify each standard.
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For pesticide/Aroclor standards, the following scheme shall be used to
enter "EPA Sample Number".
Name
EPA Sanrole 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) INDBM##
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##
Aroclor 1254 AR1254##
Aroclor 1260 AR1260##
The permitted mixture of Aroclor 1016 and Aroclor 1260 shall be entered
as AR16603*.
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 may not be used.
Several other pieces of information are common to many of the Data
Reporting Forms. These include Matrix, Sample wt/vol, Level, Lab
Sample ID, and Lab File ID.
For "Matrix", enter "SOIL1
for water samples. NOTE:
Abbreviations such as "S"
for soil/sediment samples, and enter "WATER"
The matrix must be spelled out.
or "W" shall not be used.
For "Sample wt/vol" enter the number of grams (for soil) or milliliters
(for water) of sample used in the first blank line, and the units,
either "G" or "ML", in the second blank.
For volatiles and semivolatiles, for "Level", enter the determination
of concentration level made from the mandatory screening of soils.
Enter as "LOW" or "MED", not "L" or "M". All water samples are "LOW"
level and shall be entered as such. Note: There is no differentiation
between low and medium soil samples for the Pesticide/Aroclor forms,
and no level is entered on any of the these forms.
"Lab Sample ID* is an optional laboratory-generated internal
identifier. Up to 12 alpha-numeric characters may be reported here.
If the contractor does not have a Lab Sample ID, this field may be left
blank.
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"Lab File ID" is the laboratory-generated name of the GC/MS data system
file containing information pertaining to a particular analysis. Up to
14 alpha-numeric characters may be used here.
"Instrument ID" is common to many of the forms, particularly those
containing calibration data. The identifier used by the laboratory
must include some indication of the manufacturer and/or model of the
instrument, and contain additional characters that differentiate
between all instrument of the same type in the laboratory.
"GC Column" and "ID (mm)" are common to various other forms. These two
fields are to be used to identify the stationary phase of the GC column
(previously called GC Column ID), and the internal diameter of the GC
column in millimeters (mm). For packed columns, convert the ID from
inches to millimeters as necessary, and enter in the "ID" field.
Forms II, 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 & second page is required, number the pages
consecutively, as "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, and often matrix-specific within fraction. For
example, Form II VOA-1 and Form II VOA-2 are for different data.
Therefore, do not number the pages of all six versions of Form II as "1
of 6, 2 of 6, etc." Number only pages within a fraction-specific and
matrix-specific form.
For rounding off numbers to the appropriate level of precision, observe
the following common rules. If the figure following those to be
retained is less than 5, drop it (round down). If the figure is
greater than 5, drop it and increase the last digit to be retained by 1
(round up) . If the figure following the last digit to be retained
equals 5, round up if the digit to be retained is odd, and round down
if that digit is even.
B. Organic Analysis Data Sheet (Form I. All Fractions')
1. Form I VGA, Form I SV-1, Form I SV-2, Form I PEST
This form is used for tabulating and reporting sample analysis results
for target compounds. If all fractions are not requested to be
analyzed, only the pages specifically required must be submitted. If
VOA analysis only is requested, Form I VGA and Form I VOA TIC must be
submitted. If the pesticide/Aroclor analysis is the only analysis
requested, only Form I Pest must be submitted for that sample.
Complete the header information on each page of Form I required,
according to the instructions in Part A and as follows:
rtr un-i rt
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For volatiles, for "% moisture not dec.", enter the nondecanted percent
moisture. This is the only percent moisture determination made for
volatiles, as the entire contents of the VOA vial are considered as the
sample.
For semivolatiles and pesticides/Aroclors, enter the values for the
percent moisture determined during the ana.ysis. In the field
"decanted (Y/N)", enter "Y" if the sample had standing water above the
soil/sediment that was decanted, or "N" if no water was decanted off
the surface of the sample. Report percent moisture (decanted or not
decanted) to the nearest whole percentage point (i.e., 5%, not 5.3%).
Leave these fields blank for Form I for method blanks and instrument
blanks.
For volatiles, enter the GC column identifier under "GC Column", and
the internal diameters in millimeters (mm), to two decimal places,
under "ID". For packed columns, convert the ID from inches to
millimeters as necessary, and enter in this field.
For pesticides/Aroclors, enter the method of extraction as "SEPF" for
separately funnel, "CONT" for continuous liquid-liquid extraction, or
"SONG" for sonication (soils only).
If gel permeation chromatography, "GPC Cleanup", was performed, enter
"Y" for yes. Otherwise, enter "N" for no, if GPC was not performed.
NOTE: GPC is required for all soil samples analyzed for semivolatiles
and pesticides/Aroclors, therefore all soil sample forms will contain
"Y" in this field.
For soil samples only, enter pH for semivolatiles and
pesticides/Aroclors, reported to 0.1 pH units.
"Date Received" is the date of sample receipt at the laboratory, as
noted on the Traffic Report (i.e., the VTSR). It should be entered as
MM/DD/YY.
"Date Extracted" and "Date Analyzed* should be entered in a similar
fashion. If continuous liquid-liquid extraction procedures are used,
enter the date on which the procedure was started for "Date Extracted".
If separatory funnel or sonication procedures are used, enter the date
on which the procedure was completed. For pesticide/Aroclor samples,
the date of analysis should be the date of the first GC analysis
performed. 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.
For volatiles, if a medium soil sample is analyzed, under the "Soil
Extract Volume" enter total volume of the methanol extract in
microliters. This volume includes any methanol not collected from the
filtration of the extract through glass wool, and is typically 10000
uL, i.e., the 10 mL of methanol use for the extraction. If a medium
soil sample is analyzed, enter also the volume of the methanol extract
added to the reagent water in the purge tube and analyzed, under "Soil
Aliquot Volume". Enter this volume in microliters (uL).
B-33 muni
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For semlvolattles and pesticides/Aroclors, enter the actual volume of
the most concentrated sample extract, in aicroliters, under
"Concentrated Extract Volume". This volume typically will be 1000 uL,
or 500 uL when GPC was performed. 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.
For semivolatiles and pesticides/Aroclors, enter the volume of the
sample extract injected into the GC under "Injection Volume". Report
this volume in microliters to one decimal place, i.e., 1.0 uL. Note: A
2.0 microliter injection is required for semivolatile analyses.
If a sample or sample extract has been diluted for analysis, enter the
"Dilution Factor" as a single number, not a fraction, such as "100.0,"
for a 1 to 100 dilution of the sample. Enter 0.1 for a concentration
of 10 to 1. If a sample was not diluted, enter "1.0." Report dilution
factors to one decimal place.
For positively identified target compounds, the Contractor shall report
the concentrations detected as uncorrected for blank contaminants.
For volatile and semivolatile results, report analytical results to one
significant figure if the value is less than 10, and two significant
figures if the value is above 10.
Report all pesticide/Aroclor results to two significant figures.
The appropriate concentration units, ug/L or ug/kg, must be entered.
If the result is a value greater than or equal to the quantitation
limit, report the value.
Under the column labeled "Q" for qualifier, flag each result with the
specific Data Reporting Qualifiers listed below. The Contractor is
encouraged to use additional flags or foot-otes. The definition of
such flags must be explicit and must be included in the SDG Narrative.
For reporting results to the USEPA, the following contract specific
qualifiers are to be used. The seven qualifiers defined below are not
subject to modification by the laboratory. Up to five qualifiers may
be reported on Form I for each compound.
The seven EPA-defined qualifiers to be used are as follows:
U - Indicates compound was analyzed for but not detected. The
sample quantitation limit must be corrected for dilution and
for percent moisture. For example. 10 U for phenol in water if
the sample final volume is the protocol-specified final volume.
If a 1 to 10 dilution of extract is necessary, the reported
limit is 100 U. For a soil sample, the value must also be
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adjusted for percent moisture. For example, if the sample had
24% moisture and a 1 to 10 dilution factor, the sample
quantitation limit for phenol (330 U) would be corrected to
(330 U) x df where D - 100 - % moisture
D 100
and df - dilution factor
For example, at 24% moisture, D - 100-24 - 0.76
100
(330 U) x 10 - 4300 U rounded to the appropriate
number of significant figures
.76
For soil samples subjected to GPC clean-up procedures, the
extract must be concentrated to 0.5 mL, and the sensitivity of
the analysis is not compromised by the cleanup procedures.
Therefore, the CRQL values in Exhibit C will apply to all
samples, regardless of cleanup. However, if a sample extract
cannot be concentrated to the protocol-specified volume (see
Exhibit C), this fact must be accounted for in reporting the
sample quantitation limit.
J - Indicates an estimated value. This flag is used either when
estimating a concentration for tentatively identified compounds
where a 1:1 response is assumed, or when the mass spectral data
indicate the presence of a compound that meets the
identification criteria but the result is less than the sample
quantitation limit but greater than zero. For example, if the
sample quantitation limit is 10 ug/L, but a concentration of 3
ug/L is calculated, report it as 3J. The sample quantitation
limit arust be adjusted for dilution as discussed for the U
flag.
N - Indicates presumptive evidence of a compound. This flag is
only used for tentatively identified compounds, where the
identification is based on a mass spectral library search. It
is applied to all TIC results.
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
an -P".
C - This flag applies to pesticide results where the identification
has been confirmed by GC/MS. If GC/MS confirmation was
attempted but was unsuccessful, do not apply this flag, instead
use a laboratory-defined flag, discussed below.
R-35 mum
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B - This flag is used when the analyte is found in the associated
blank as well as in the sample. It indicates possible/probable
blank contamination and warns the data user to take appropriate
action. This flag must be used for a TIC as well as for a
positively identified target compound.
E - This flag identifies compounds whose concentrations exceed the
calibration range of the GC/MS instrument for that specific
analysis. If one or more compounds have a response greater
than full scale, except as noted in Exhibit D, the sample or
extract must be diluted and re-analyzed according to the
specifications in Exhibit D. All such compounds with a
response greater than full scale should have the concentration
flagged with an "E" on the Form I for the original analysis.
If the dilution of the extract causes any compounds identified
in the first analysis to be below the calibration range in the
second analysis, then the results of both analyses shall be
reported on separate copies of Form I. The Form I for the
diluted sample shall have the "DL" suffix appended to the
sample number. NOTE: For total xylenes, where three isomers
are quantified as two peaks, the calibration range of each peak
should be considered separately, e.g., a diluted analysis is
not required for total xylenes unless the concentration of
either peak separately exceeds 200 ug/L.
D - This flag identifies all compounds identified in an analysis at
a secondary dilution factor. If a sample or extract is
re-analyzed at a higher dilution factor, as in the "E" flag
above, the "DL" suffix is appended to the sample number on the
Form I for the diluted sample, and all concentration values
reported on that Form I are flagged with the "D" flag. This
flag alerts data users that any discrepancies between the
concentrations reported may be due to dilution of the sample or
extract.
A - This flag indicates that a TIC is a suspected
aldol-condensation product.
X - Other specific flags may be required to properly define the
results. If used, they must be fully described, and such
description attached to the Sample Data Summary Package and 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 combine several flags, as needed. For instance, the "X"
flag might combine the "A", "B", and "D" flags for some sample.
The laboratory-defined flags are linited to the letters "X",
"Y", and "Z".
The combination of flags "BU" or "UB" is expressly prohibited. Blank
contaminants are flagged "B" only when they are detected in the sample.
B-36 OLM01.0
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2. Form I VOA-TIC and Form I SV-TIC
Fill in all header information as above.
Report Tentatively Identified Compounds (TICs) including CAS number,
compound name, retention time, and the estimated concentration
(criteria for reporting TICs are given i.i Exhibit D, Section IV).
Retention time must be reported in minutes and decimal minutes, not
seconds or minutes:seconds.
If, in the opinion of the mass spectral interpretation specialist, no
valid tentative" identification can be made, the compound shall be
reported as unknown.
Include a Fora I VOA-TIC or SV-TIC for every volatile and semivolatile
fraction of every sample and method blank analyzed, even if no TICs are
found. Total the number of TICs found, including aldol-condensation
products (but see below), and enter this number in the "Number TICs
found." If none were found, enter "0" (zero). Form I VOA-TIC or SV-TIC
must be provided for every analysis, including required dilutions and
reanalyses, even if no TICs are found.
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: description to no more than 28 characters (i.e., unknown
hydrocarbon, etc.).
Peaks that are suspected as aldol-condensation reaction products (i.e.,
4-methyl-4-hydroxy-2-pentanone and 4-methyl-3-pentene-2-one) shall be
summarized on this form, flagged "A", and included in the total "Number
TICs found," but not counted as part of the 20 most intense non-target
semivolatile compounds to be searched.
C. System Monitoring Compound Recovery (Form II VGA)
For volatiles, Form II is used to report the recoveries of the system
monitoring compounds added to each volatile sample, blank, matrix
spike, and matrix spike duplicate prior to analysis. The system
monitoring compounds, previously less than accurately termed volatile
surrogates, are used to monitor the performance of the purge and trap-
gas chromatograph-mass spectrometer system as a whole. Form II VGA is
matrix-specific, so that system monitoring compound recoveries for
water samples are reported on a different version of Form II than the
recoveries in soil samples. Soil sample recoveries are further
differentiated by concentration level.
Complete the header information and enter EPA Sample Numbers as
described in part A. For volatile soil samples only, specify the
"level" as "LOW" or "MED", as on Form I. Do not mix low and medium
level samples on one font. Complete one for each level. For each
system monitoring compound, 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.
tt-1-7
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Flag each system monitoring compound recovery outside the QC limits
with an asterisk (*). The asterisk must be placed in the last space in
each appropriate column, under the "#" symbol. In the far righthand
column, total the number of system monitoring compound(s) recoveries
outside the QC limits for each sample. If no system monitoring
compound(s) were outside the limits, enter "0".
If the system monitoring compound(s) are diluted out in any analysis,
enter the calculated recovery, or "0" (zero) if the system monitoring
compound(s) is not detected, and flag the system monitoring compound(s)
recoveries with a "D" in the column under the "#" symbol. Do not
include results"flagged "D" in the total number of recoveries for each
sample outside the QC limits.
Number all pages as described in part A.
D. Surrogate Recovery (Form II, SV and PEST)
Form II is used to report the recoveries of the surrogate compounds
added to each semivolatile and pesticide/Aroclor sample, blank, matrix
spike, and matrix spike duplicate. For semivolatiles, Form II is
matrix-specific as well as fraction-specific, so surrogate recoveries
for semivolatile water samples are reported on a different version of
Form II than semivolatile soil sample surrogate recoveries.
Complete the header information and enter EPA Sample Numbers as
described in part A. For semivolatile soil samples only, specify the
"level" as "LOW" or "MED", as on Form I. Do not mix low and medium
level samples on one form. Complete one for each level. For each
surrogate, 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.
Flag each surrogate recovery outside the QC limits with an asterisk
(*). The asterisk must be placed in the last space in each appropriate
column, under the "#" symbol. In the far righthand column, total the
number of surrogate recoveries outside the QC limits for each sample.
If no surrogates were outside the limits, enter "0".
If the surrogates are diluted out in any analysis, enter the calculated
recovery, or "0" (zero) if the surrogate is not detected, and flag the
surrogate recoveries with a "D" in the column under the "#" symbol. Do
not include results flagged "D" in the total number of recoveries for
each sample outside the QC limits.
The pesticide surrogate recoveries must be reported from both GC
columns used for the analyses. Therefore, identify each GC column in
the header, entering the stationary phase under "GC Column" (previously
called GC Column ID), and the internal diameter (ID) of the column in
millimeters under "ID". The assignment of colons as "1" and "2" is
left to the discretion of the laboratory if 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" must be
consistent across all the reporting forms. If the analysis is not
B-38 OLM01.0
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performed by simultaneous injection, then the assignment of GC Column
number should be based on the chronological order of the two analyses.
The pesticide surrogate recovery limits are only advisory, but the
Contractor must flag those recoveries outside the advisory QC limits or
diluted out, nonetheless.
Number all pages as described in part A.
Matrix Spike/Matrix Spike Duplicate Recovery (Form III, All Fractions)
This form is used to report the results of the analyses of a matrix
spike and matrix spike duplicate. The form is matrix-specific for
volatiles and semivolatiles.
Complete the header information as instructed in Part A, including the
EPA Sample Number for the matrix spike, without the suffixes MS or MSD.
For volatile and semivolatile soil samples, specify "level" as "LOW" or
"MED", as on Form I. SDGs containing soil samples at both levels
require MS/MSD at each level, therefore, for soils, prepare one form
for each level.
All water samples are "LOW". Therefore, there is no MS/MSD for "medium
level waters", and none shall be reported.
In the upper box in Form III, under "SPIKE ADDED", enter the calculated
concentration in ug/L or ug/Kg (according to the matrix) that results
from adding each spiked compound to the aliquot chosen for the matrix
spike (MS). For instance, for base/neutral compounds in medium level
soils, if 50 ug of spike are added to 1 g of soil, the resulting
concentration is 50,000 ug/Kg. Enter the "SAMPLE CONCENTRATION",, in
50,000 similar units, 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). Under "MS
CONCENTRATION", enter the actual concentration of each spike compound
detected in the matrix spike aliquot. Calculate the percent recovery
of each spike compound in the matrix spike aliquot to the nearest whole
percent, according to Exhibit E, and enter under "MS % REC". Flag all
percent recoveries outside the QC limits with an asterisk (*). The
asterisk must be placed in the last space of the percent recovery
column, under the "#" symbol.
For pesticide/Aroclor matrix spikes and matrix spike duplicates, the
concentration used for "MS CONCENTRATION" AND "MSD CONCENTRATION" must
be the concentration of the spiked analyte reported on Form I that
those analyses. Of the two concentrations calculated for each
pesticide/Aroclor target compound, one on each GC column, the lower
concentration is reported on Form I, and both concentrations are
reported on Form X. The lower concentration is reported on Form III
and used in the calculation of spike recovery, even if that
concentration yields a recovery value that is outside the advisory QC
limits.
nrwm
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Complete the lover box on Form III in a similar fashion, using the
results of the analysis of the matrix spike duplicate (MSD) aliquot.
Calculate the relative percent difference (RFD) between the matrix
spike recovery and the matrix spike duplicate recovery, and enter this
value in the lower box under "% RPD". Report the relative percent
difference to the nearest whole percent. Compare the RPDs to the QC
limit s 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.
Summarize the values outside the QC limits at the bottom of the page.
No further action is required by the laboratory. Performance-based QC
limits will be generated and updated from recovery and RPD data.
F. Method Blank Summary (Form IV, All Fractions)
This form summarizes the samples associated with each method blank
analysis. A copy of the appropriate Form IV is required for each
blank.
Complete the header information on Form IV as described in Part A. The
"EPA Sample No.' entered in the box at the top of Form IV shall be the
same number entered on the Form I for the blank itself.
For volatile blanks, enter the "Instrument ID", "Date Analyzed" "Time
Analyzed", "GC Column", "ID", and "Heated Purge (Y/N)". Volatile
samples analyzed by the same purging technique, i.e., ambient purge, or
heated purge, may be reported together on the same Form IV, if the same
method blank applies to those samples. Thus, water samples and medium
soil sample may be combined on a single form, if run with a single
blank.
For semivolatile blanks, enter the "Instrument ID", "Date Analyzed",
"Matrix" and "Level". All water blanks are "LOW". The "Time Analyzed"
shall be in military time.
For pesticide/Aroclor blanks, enter the method of extraction as "SEPF"
for separatoxy funnel, "SONG" for sonication, or "CONT" for continuous
liquid-liquid extraction.
For pesticide/Aroclor blanks, there is no differentiation between
medium and low level soil samples, so no "Level" is entered on this
form.
For semivolatile and pesticide/Aroclor method blanks, enter the date of
extraction of the blank.
If the samples associated with pesticide/Aroclor blank are subjected to
sulfur cleanup, then the blank must also be subjected to sulfur
cleanup. If sulfur cleanup is employed, enter "Y" in the "Sulfur
Cleanup" field, else, enter "N". 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
B-40 OLM01.0
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IV associating all the samples with the method blank, and a. second
version of Fora 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.
Pestit ide/Aroclor contaminants must meet the identification criteria in
Exhibit D PEST, which requires analysis of the blank on two different
GC Columns. Therefore, enter the date, time and instrument ID of both
analyses of the blank on the pesticide method blank summary. 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 must be consistent with the
information reported on all other pesticide forms. Otherwise, (1)
shall be the first analysis, and (2) the second. Identify the GC
Column and internal diameter as described previously.
Enter "Lab File ID" only if GC/MS confirmation was attempted.
Otherwise, leave blank.
For all three fractions, as appropriate, summarize the samples
associated with a given method blank in the table below the header,
entering EPA Sample Number and Lab Sample ID. For volatiles, enter the
Lab File ID and time of analysis of each sample. For semivolatiles,
enter Lab File ID and Date Analyzed. For pesticides/Aroclors, enter
the dates of both analyses as Date Analyzed (1) and Date Analyzed (2) ,
as discussed above.
Number all pages as described in part A.
G. GC/MS Instrument Performance Check and Mass Calibration (Form V VGA and
SV)
This form is used to report the results of GC/MS instrument performance
check (previously.known as "Tuning") for volatiles and semivolatiles,
and to summarize the date and time of analysis of samples, standards,
blanks, matrix spikes, and matrix spike duplicates associated with each
analysis of the instrument performance check solution.
Complete the header information as in Instruction A. Enter the "Lab
File ID" for the injection containing the instrument performance check
solution (BFB for volatiles, DFTPP for semivolatiles). Enter the
"Instrument ID". Enter the date and time of injection of the
instrument performance check solution. Enter time as military time.
For volatiles, indicate the purging method by entering "Y" for heated
purge, and "N" for ambient temperature purge, as described previously.
Water samples and medium soil sample extracts may be reported on the
same Form V if analyzed together, as a single calibration may be
applied to both sample types.
For each ion listed on the form, enter the percent relative abundance
in the righthand column. Report relative abundances to the number of
significant figures given for each ion in the ion abundance criteria
column.
B-41 OLM01.0
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Note that 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 are to be normalized to the nominal base peaks
listed on Form V (see Exhibits D and E).
All relative abundances must be reported as a number. If zero, enter
"0", 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.
In the lower half of the form, list all samples, standards, blanks,
matrix spikes, and matrix spike duplicates analyzed under that
instrument performance check in chronological order, by time of
analysis (in military time). Refer to Part A for specific instructions
for identifying standards and blanks. Enter "EPA Sample No.", "Lab
Sample ID", "Lab File ID", "Date Analyzed", and "Time Analyzed" for all
standards, samples, blanks, matrix spikes, and matrix spike duplicates.
The GC/MS instrument performance check solution must be analyzed again
twelve hours from the time of injection of the instrument performance
check solution (BFB or DFTPP) listed at the top of the form. In order
to meet these requirements, a sample, standard, blank, matrix spike, or
matrix spike duplicate must be injected within twelve hours of the
injection of the instrument performance check solution.
Number all pages as described in Instruction A.
H. GC/MS Initial Calibration Data (Form VI VOA, SV-1, SV-2)
After a GC/MS system has undergone an initial five-point calibration
at the specific concentration levels described in Exhibits D and E, and
after all initial calibration criteria have been met, the laboratory
must complete and submit a Form VI for each volatile or semivolatile
target compound initial calibration performed .which is relevant to the
samples, blanks, matrix spikes, matrix ^pike duplicates in the SDG,
regardless of when that calibration was performed.
Complete all header information as in Part A. Enter the "Case No." and
"SDG No." for the current data package, regardless of the original Case
for which the initial calibration was performed. Enter "Instrument ID"
and the date(s) of the calibration. If the calendar date changes
during the calibration procedure, the inclusive dates should be given
on Form VI. Enter the injection times of the first and last of the
standards analyzed under "Calibration Times".
For Semivolatiles, eight compounds: 2,4-Dinitrophenol,
2,4,5-Trichlorophenol, 2-Nitroaniline, 3-Nitroaniline, 4-Nitroaniline,
4-Nitrophenol, 4,6-Dinitro-2-Methylphenol, and Pentachlorophenol will only
require a four-point initial calibration at 50, 80, 120, and 160 total
nanograms because detection at less than 50 nanograas per injection is
difficult. If a four-point calibration is performed for these compounds,
leave RF20 blank.
B-42 OLM01.0
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For volatiles, enter Heated Purge, and GC Column, ID, as on Form V.
Enter the "Lab File ID" 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. For volatiles, report the
response factors for the system monitoring compounds in the calibration
standards. For semivolatiles, report the response factors for all
surrogate compounds in the calibration standards. The laboratory must
report the relative standard deviation (%RSD) for all compounds.
%RSD - (SD/x) x 100
Where
SD - Standard Deviation of initial 5 response factors
(per compound), is calculated as:
n-1
and x -
Mean of initial 5 response factors (per compound)
In order to be used for the analysis of samples or sample extracts, the
volatile and semivolatile initial calibration must meet the acceptance
criteria for relative response factors outlined in Exhibits D and E.
The compounds for which criteria have been developed for minimum RRF
and maximum %RSD are indicated on the fora by an "*". All other
compounds must meet a minimum RRF of 0.010.
I. GC/EC Initial Calibration Data (Form VI PEST-1, PEST-2, PEST-3, PEST-4)
The initial calibration of pesticides and Aroclors involves the
determination of retention times, retention tine 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 levels. For the
multicomponent target compounds, these data are calculated from a
single point calibration.
For each set of three analyses of Individual Standard Mixture A (low
point, mid point, and high point), and set of three analyses of
Individual Standard Mixture B, during an initial calibration, complete
one copy of Form VI for each GC column used. Thus, each initial
calibration will require at least two foxas for the Individual Mixture
A analyses, and two for Individual Mixture B analyses. However, for
each of the forms, half of the compounds will have no entries, as they
are not in that mixture.
B-43 muni
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Complete Che header information as above. Enter the Instrument ID, GC
Column, and ID as described previously. Enter the dates of analysis of
the first and last of the three standards on each form under "Date(s)
Analyzed". Under "Level (x low)", 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 s{ ecified in Exhibit D as
ten times the low point, therefore, enter "10.0" for "mid". The high
point standard must be at least 30 times the low point, but may be up
to 100 times the low point, 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.
For each standard analyzed, enter the retention time of each applicable
analyte in minutes and decimal minutes, under the appropriate
concentration level. Calculate the mean retention time of each analyte
from the three individual mixtures, and report it under "Mean RT". The
retention time window of each analyte is defined as ± 0.04 minutes from
the mean retention time, except for Methoxychlor, where the width of
the window is ± 0.05 minutes. Calculate the retention time window for
each analyte, using these specifications, and enter the lower limit of
the window under RT Window "From", and the upper limit of the window
under "To". The retention times of the surrogates are reported for
both Individual mixtures, but the windows are only required to be
calculated for Individual Mixture A.
For each three analyses of the same Individual Standard Mixture (A or
B) , the laboratory must also complete the calibration factor data on
Form VI PEST-2. In a similar fashion as for the retention time data on
Form VI PEST-1, prepare one form for each group of three standards, for
each instrument and GC column used. Enter the concentration level of
the standards in the same fashion as on Form VI PEST-1.
Enter the calibration factor for each compound in each of the
standards, and calculate a mean calibration and a percent relative
standard deviation (%RSD), and enter on the form. As with surrogate
retention tines, the calibration factors are only required from
Individual Mixture A analyses.
In order to be used for sample analyses, the %RSD of the initial
calibration factors must be less than or equal to 10.0 percent for all
compounds except alpha-BHC, beta-BHC, gamma-BHC, DDT, Endrin, and
Methoxyclor, where the %RSD must be less than or equal to 15.0 percent.
These criteria apply to both GC columns.
For the multicomponent target compounds, the retention times, retention
time windows, and calibration factor Bust be reported in a similar
fashion for each single point calibration standard. For each
multicomponent compound, the laboratory must select at least three
peaks from each analyte, according to the specifications in Exhibit D.
The retention and calibration factor data apply to each peak. Complete
one version of Form VI PEST-3 for each GC column, for each initial
calibration that applies to samples in the data package.
B-44 OLM01.0
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Form VI is used also to report the results of analysis of the
Resolution Check Solution that must begin each pesticide/Aroclor
initial calibration sequence. The purpose of the Resolution Check
Solution is to demonstrate for each initial calibration that the GC
columns employed are capable of satisfactorily resolving the most
difficult of the target analytes. One copy of Form VI PEST-4 is
completed that covers both GC columns.
Complete the header information as described in Instruction A. Using
the same assignment of first and second GC columns made for Form IV,
enter the GC Column, ID, Instrument ID, and Date and Time Analyzed.
Enter the "EPA Sample No." for the Resolution Check Standard. If
simultaneous injections on a single GC are used, the EPA Sample No. may
be the same for both Resolution Check Standards. If simultaneous
injections were not used, use different' suffixes to identify the
standards.
In the boxes on the form, list each analyte, in retention time order.
including both surrogate compounds. Thus, the order of analytes in the
two boxes on a copy of 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 PEST. Spell out the names of the surrogates as
they appear on Form VII PEST-2.
Enter the retention time of each analyte from the analysis under "RT".
Calculate the resolution between each pair of analytes according to the
formulae in Exhibit D. The resolution is calculated as percentage of
the height of the smaller of each pair of adjacent peaks. 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. In order for these GC columns to be used for pesticide/Aroclor
analyses, the resolution of all pairs of peaks listed on this form must
be greater than or equal to 60.0%.
J. GC/MS Continuing Calibration Data (Form VII VOA, SV-1, SV-2)
For volatiles and semivolatiles, the Continuing Calibration Check form
is used to report the calibration of the GC/MS system by the analysis
of specific calibration standards. A Continuing Calibration Check form
is required for each twelve (12) hour time period for both volatile and
semivolatile target compound analyses.
The Contract laboratory must analyze calibration standards and meet all
criteria outlined in Exhibits D and E for the minimum RRF and maximum
percent difference between initial and continuing calibrations.
Complete all header information as in Instruction A. Enter instrument
ID, date and time of continuing calibration, the Lab File ID of the
continuing calibration standard, and dates and times of initial
calibration (give inclusive dates if initial calibration is performed
B_45 riTvcm n
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over more Chan one date). For volatiles, enter purge method and column
as on Forms IV, V and VI. Using the appropriate Initial Calibration
(volatile or semivolatile) fill in the average relative response factor
(RRF) for each target compound, each system monitoring compound for
volatiles, and each surrogate for semivolatiles. Report the alative
response factor (RRF50) from the continuing calibration standard
analysis. Calculate the Percent Difference (%D) for all compounds.
- RRFC
% Difference - — x 100
Where
RRF* - Average relative response factor from initial calibration.
RRF_ — Relative response factor from continuing calibration
standard.
All senivolatile standards are analyzed at 50 total ng.
GC/EC Continuing Calibration (Form VII PEST)
The Calibration Verification Summary Form VII is used to report the
results of the Performance Evaluation Mixtures (PEM), instrument
blanks, and Individual Standard Mixtures A and B analyzed at the
beginning and end of a twelve hour sequence. The laboratory must
submit this form for each twelve hour sequence analyzed.
Complete the header information on each Form VII required according to
the instructions in part A.
Enter the initial calibration date(s) analyzed. Give inclusive dates
if initial calibration is performed ove more than one date.
On Form VII PEST-1, enter the EPA Sample No., Lab Sample ID, Date
Analyzed, and Time Analyzed for the instrument blank that preceded the
twelve hour sequence (PIBLK). For the PEM that initiated or terminated
the twelve hour sequence (PEM), enter the EPA Sample No., Lab Sample
ID, Date Analyzed, and Time Analyzed.
In the table, report the retention time for each analyte in the PEM as
well as the retention time windows. For each analyte in the PEM, enter
the amount of the analyte calculated to be in the PEM, in nanograms to
three dee|na^ plages under "CALC AMOUNT". Enter the nominal amount of
each analyte in the PEM under "NOM AMOUNT". Calculate the relative
percent difference between the calculated amount and nominal amount for
each analyte according to Exhibit D. Report the values under "RPD".
B-46 OLM01.0
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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 PEST-2 is used to report the results of the analyses of the
instrument blank and the midpoint concentrations of Individual Stan lard
Mixtures A and B that, along with the PEM, bracket each 12-hour period
of sample analyses. One copy of Form VII PEST-2 must be completed each
time the Individual Standard Mixtures are analyzed, for each GC column
used. The form is completed in a fashion similar to Form VII, entering
the EPA Sample No., Lab Sample ID, Date Analyzed, and Time Analyzed for
the instrument blank immediately preceding the Individual Standard
Mixtures A and B, and for the standards themselves. The upper table on
the form contains the retention time and amount data for Individual
Standard Mixture A compounds. The lower table contains the data for
Mixture B. Enter the data in these tables in a fashion similar to that
for the PEM. Complete copies of Form VII PEST-1 and PEST-2 for each
standard reported on Form VIII PEST.
L. Internal Standard Area Summary (Form VIII VOA and SV)
This form is used to summarize the peak areas and retention times of
the internal standards added to all volatile and semivolatile samples,
blanks, matrix spikes, and matrix spike duplicates. The data are used
to determine when changes in internal standard responses will adversely
affect quantification of target compounds. This form must be completed
each time a continuing calibration is performed, or when samples are
analyzed under the same GC/MS instrument performance check as an
initial calibration.
Complete the header information as in Instruction A. Enter the Lab
File ID of the continuing calibration standard, as well as-the date and
time of analysis of the continuing calibration standard. 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 50 ug/L initial calibration standard for volatiles, and the 50 ng
initial calibration standard for semivolatiles. Use the date and time
of analysis of this standard, and its Lab File ID and areas in place of
those of a continuing calibration standard.
For volatiles, enter purge method and column, as on Forms IV, V, VI,
and VII.
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
row labeled "12 HOUR STD". For each internal standard, calculate the
upper limit of the area as the area of the particular standard plus
100% of its area (i.e., two tines the area in the 12 HOUR STD box), and
the lower limit of the area as the area of the internal standard minus
50% of its area (i.e., one half the area in the 12 HOUR STD box).
Report these values in the boxes labeled "UPPER LIMIT" and "LOWER
B-47 OLM01.0
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LIMIT" respectively. Calculate the upper limit of the retention time
as the retention of the internal standard plus 0.50 minutes (30
seconds), and the lower limit of the retention time as the retention
time in the standard minus 0.50 minutes (30 seconds).
For each sample, blank, matrix spike, and matrix spike duplicate
analyzed under a given continuing calibration, enter the EPA Sample
Number and che area measured for each internal standard and its
retention time. If the internal standard area is outside the upper or
lower limits calculated above, flag that area with an asterisk (*).
The asterisk must be placed in the far right hand space of the box 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.
Number all pages as described in Instruction A.
M. Pesticide Analytical Sequence (Form VIII Pest)
This form is used to report the analytical sequence for pesticide
analysis. At least one Form VIII PEST is required for each GC column
used for pesticide/Aroclor analyses.
The laboratory shall complete all the header information as in Part A.
Enter dates of analyses for the initial calibration, GC column, ID, and
Instrument ID, as on Forms IV, VI. and VII.
At the top of the table, report the mean retention time for
tetrachloro-m-xylene and decachlorobiphenyl calculated from the initial
calibration sequence under "TCX" and "DCB", respectively. For every
analysis associated with a particular analytical sequence starting with
the initial calibration, enter the EPA Sample Number, Lab Sample ID,
Date Analyzed, and Time Analyzed. Each sample analyzed as part of the
sequence must be reported on Form VIII PEST even if it is not
associated with the SDG. The laboratory may use the EPA Sample No. of
"ZZZZZ" to distinguish all samples that are not part of the SDG being
reported. Report the retention time of the surrogates for each
analysis under "TCX RT" and "DCB RT*. All sample analyses must 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 tine (see Exhibit D), it is not
necessary to report the data from 12-hour periods when no samples in an
SDG were run. The laboratory must deliver the 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 tine periods between the initial calibration
and samples in the SDG is not a routine deliverable, it must be made
available on request during on-site evaluations, etc. Here again, non-
EPA samples may be indicated with "ZZZZZ*.
Flag all those values which do not meet: the contract requirements by
entering an asterisk (*) in the last column, under the •*". If the
retention time cannot be calculated due to interfering peaks, leave the
B-48 OLM01.0
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RT column blank for chat surrogate, enter an asterisk In the last
column, and document the problem in the SDG Narrative.
If more than a single copy of Form VIII PEST is required, enter the
same header information on all subsequent pages for that GC Column and
Instrument, and number each page as described in Part A.
Form VIII PEST is required for each for each GC system and for each GC
column used to analyze target pesticides/Aroclors.
N. Pesticide Cleanup Summary (Form IX PEST-1, PEST-2)
This form summarizes the results of the checks performed for both
cleanup procedures employed during the preparation of pesticide
extracts for analysis. Form IX PEST-1 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. In this fashion, problems with a lot of cartridges may be
tracked across many samples.
Complete the header information on each Form IX required, according to
the instructions in Part A.
Enter the "Case No." and "SDG No." for the current data package,
regardless of the original Case for which the cartridge check was
performed. Enter the "Florisil Cartridge Lot Number". Enter under the
"Date Analyzed" the date the Florisil cartridge check solution was
analyzed.
Enter "GC Column" and "ID" for the GC columns used to determine the
recovery of the analytes in the Florisil cartridge check solution,
under "GC Column (1)", and "GC Column (2)", etc., as discussed
previously.
In the upper table, enter the amount of spike added and spike recovered
in nanograos for each analyte.
Calculate to the nearest whole percent, and enter the percent recovery
in the "% EEC" field. Flag each spike recovery outside the QC limits
with an asterisk (*). The asterisk must be placed in the last space in
the "% REC* column, under the "#" symbol.
In the lower table, enter the "EPA Sample No.*, the "Lab Sample ID",
and "Date Analyzed" for each sample and blank that was cleaned up using
this lot of Florisil cartridges.
Number the Form IX pages as described in Part A.
Form IX PEST-2 summarizes the results of the calibration of the Gel
Permeation Chromatography device (GPC) that oust be used to process all
soil sample extracts for pesticide/Aroclor analyses. Calibration of
the GPC is required at least once every 7 days, and each time the GPC
column is repacked.
R-/.0
-------
Complete all header information as in Part A. Enter an identifier for
the GPC Column, and the date of calibration in the appropriate fields.
Enter the two "GC Column" and "ID" fields, as discussed above.
For each of the pesticide matrix spike compounds listed in the box in
the upper portion of the form, enter the amount of the spike added to
the GPC column in ng, and the amount recovered, also in ng. Calculate
the percent recovery of each analyte, and enter these values on the
form, to the nearest percent. Compare the recoveries to the QC limits
shown on the form, and flag all those values outside the limits with an
asterisk (*) in the column under the "#" symbol.
For each sample in the data package that was subjected to GPC under
this calibration, enter the EPA Sample No. , Lab Sample ID, and the date
of both analyses in the lower portion of the form.
If more than one copy of Form IX PEST-2 is required, number all pages
?s described in Instruction A.
0. Pesticide/Aroclor Identification (Form X PEST-1, PEST-2)
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
copies of Form X are used for single component analytes and
multicomponent analytes.
Copies of Form X are required for each sample, blank, matrix spike, and
matrix spike duplicate in which target pesticides or Arodors are
detected. If none are detected in a given sample, no copy of Form X is
required for that sample.
Complete the header information as in Instruction A. Enter the GC
Column, and ID for each of the two columns, one as GC Column (1), the
other as (2), as described previously. Enter the Instrument ID
associated with each GC column directly below.
For each single component pesticide detected, enter the name of the
compound under "ANALYTE" as it appears on Form I. Enter the retention
times on each column of the compounds detected in the sample next to
the appropriate column designation (1 or 2). Enter the retention time
windows on each column from the initial calibration standard. These
data must correspond with those on Form VI, and are entered in a
similar manner. The lower value is entered under the "FROM" column,
the upper value under the "TO" column.
Enter the concentration calculated from each GC column under the column
labeled "CONCENTRATION". The units are the same as those used on Form
It ug/L for water samples, and ug/Kg for soil samples. However, do not
enter any units on Form X. Calculate the percent difference between
B-50 OLM01.0
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the concentrations entered, and report it to a tenth of a percent under
"%D".
The lower of the two concentrations is reported on Form I for each
pesticide compound. The lower concentration is used because, if
present, co-eluting interferences are likely to increase the calculated
concentration of a.\y target compound. If the percent dif. erence
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 quant-itating this
analyte.
If more pesticide compounds are identified in an individual sample than
can be reported on one copy of Form X, then complete as many additional
copies of Form X as necessary, duplicating all header information, and
numbering the pages as described in Instruction A.
Multicomponent analytes detected in samples are reported on a separate
version of Form X. Complete the header information and Instrument and
GC Column fields as described above. For multicomponent analytes, it
is necessary to report the retention tine and concentration of each
peak chosen for quantitation in the target analy te, in 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 as described
previously, if the mean concentrations from the two GC columns differ
by more than 25.0 percent.
If more multicomponent compounds are identified in an individual sample
than can be reported on one copy of Form X, then complete as many
additional copies of Form X as necessary, duplicating all header
information, and numbering the pages as described in Instruction A.
THE FOLLOWING ARE DOCUMENT CONTROL FORMS
(To be submitted as hardcopy only)
P. Sample Log-In Sheet (Form DC-1)
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. If the samples in a single sample shipping
container must be assigned to more than one Sample Delivery Group, the
original Form DC-1 shall be placed with the deliverables for the Sample
Delivery Group of the lowest Arabic number and a copy of Form DC-1
must be placed with the deliverables for the other Sample Delivery
Group(s). The copies should be identified as "copy(ies)," and the
location of the original should be noted on the copies.
Sign and date the airbill (if present). Examine the shipping container
and record the presence/absence of custody seals and their condition
(i.e., intact, broken) in item 1 on Form DC-1. Record the custody seal
numbers in item 2.
-------
Open Che container, remove the enclosed sample documentation, and
record the presence/absence of chain-of-custody record(s), SMO forms
(i.e., Traffic Reports, Packing Lists), and airbills or airbill
stickers in items 3-5 on Form DC-1. Specify if there is an airbill
present or an airbill sticker in item 5 on Form DC-1. Record the
airbill or sticker number in item 6.
Remove the samples from the shipping container(s), examine the samples
and the sample tags (if present), and record the condition of the
sample bottles (i.e., intact, broken, leaking) and presence of absence
of sample tags in items 7 and 8 on Form DC-1.
Review the sample shipping documents and complete the header
information described in Instruction A. Compare the information
recorded on all the documents and samples and circle the appropriate
answer in item 9 on Form DC-1.
If there are no problems observed during receipt, sign and date
(include time) Form DC-1, the chain-of-custody record, and Traffic
Report, and write the sample numbers on Form DC-1. Record the
appropriate sample tags and assigned laboratory numbers if applicable.
The log-in date should be recorded at the top of Form DC-1 and the date
and time of cooler receipt at the laboratory should be recorded in
items 10 and 11. Record the fraction designation (if appropriate) and
the specific area designation (e.g., refrigerator number) in the Sample
Transfer block located in the bottom left corner of Form DC-1. Sign
and date the Sample Transfer block. Cross out unused columns and
spaces.
If there are problems observed during receipt or an answer marked with
an asterisk (i.e., "absent*") was circled, contact SMO and document the
contact as well as resolution of the problem on a. CLP Communication
Log. Following resolution, sign and date the forms as specified in the
preceding paragraph and note, where appropriate, the resolution of the
problem.
Q. Document Inventory Sheet (Form DC-2)
This form is used to record the inventory of the SDG File Purge
documents and count of documents in the original Sample Data Package
which is sent to the Region.
Organize all EPA-CSF documents as described in Exhibit B, Section II
and Section III. Assemble the documents in the order specified on Form
DC-2 and Section II and III, and stamp each page with a consecutive
number. (Do not number the DC-2 form). Inventory the CSF by reviewing
the document numbers and recording page numbers ranges in the columns
provided in the Form DC-2. If there are no documents for a specific
document type, enter an "NA" in the empty space.
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Certain laboratory specific documents related to the CSF may not fit
into a clearly defined category. The laboratory should review DC-2 to
determine if it is most appropriate to place them under No. 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.
B-53 OLM01.0
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SECTION IV
DATA REPORTING FORMS
B-54
OLM01.0
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1A
VOLATILE ORGANICS ANALYSIS DATA SHEET
EPA SAMPLE NO.
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Matrix: (soil/water)
Sample wt/vol: (g/mL)
Level: (low/ned)
% Moisture: not dec.
GC Column: ID:
Soil Extract Volume: (uL)
Lab Sample ID:
Lab File ID:
Date Received:
Date Analyzed:
(mm)
Dilution Factor:
CAS NO.
COMPOUND
Soil Aliquot Volume:
CONCENTRATION UNITS:
(ug/L or ug/Kg)
.(uL)
74-87-3 Chloromethane
"4-83-9 Bromomethane
5-01-4 Vinyl Chloride
'•5-00-3 Chloroethane
'/ 5-09-2 Methylene Chloride
67-64-1 Acetone
75-15-0 Carbon Disulfide
75-35-4 1,1-Dichloroethene
75-34-3 1, 1-Dichloroethane
540-59-0 1, 2-Dichloroethene (total)
67-66-3 Chloroform
107-06-2 1, 2-Dichloroethane
78-93-3 2-Butanone
71-55-6 1,1,1-Trichloroethane
56-23-5 Carbon Tetrachloride
75-27-4 Bromodichloromethane
78-87-5 1, 2-Dichloropropane
10061-01-5 cis-1,3-Dichloropropene
79-01-6 Trichloroethene
124-48-1 Dibromochlorome thane
79-00-5 1,1, 2-Trichloroethane
71-43-2 Benzene
10061-02-6 trans-1,3-Dichloropropene_
75-25-2 Bromoform
108-10-1 4-Methyl-2-Pentanone
591-78-6 2-Hexanone
127-18-4 Tetrachloroethene
79-34-5 1,1,2, 2-Tetrachloroethane_
108-88-3 Toluene
108-90-7 Chlorobenzene
100-41-4 Ethylbenzene
100-42-5 Styrene
1330-20-7 Xylene (total)
FORM I VGA
3/90
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IB
SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET
EPA SAMPLE NO.
Name:
.Lab Code:
Case No.:
Contract:
SAS No.:
SDG NO.
Matrix: (soil/water)
Sample wt/vol:
Level: (low/med)
% Moisture: decanted: (Y/N)
Concentrated Extract Volume: (uL)
Injection Volume: (uL)
GPC Cleanup: (Y/N) pH:
Lab Sample ID:
Lab File ID:
Date Received:
Date Extracted:
Date Analyzed:
Dilution Factor:
CAS NO.
COMPOUND
CONCENTRATION UNITS:
(ug/L or ug/Kg)
1-.08-95-2 Phenol
111-44-4 bis (2-Chloroethyl) ether
95-57-8 2-Chlorophenol
541-73-1 1,3-Dichlorobenzene
106-46-7 1, 4-Dichlorobenzene
95-50-1 1, 2-Dichlorobenzene
95-48-7 2-Methylphenol
108-60-1 2,2 ' -oxybis (1-Chloropropane)
106-44-5 4-Methylphenol
621-64-7 N-Nitroso-di-n-propylamine
67-72-1 Hexachloroethane
98-95-3 Nitrobenzene
78-59-1 Isophorone
88-75-5 2-Nitrophenol
105-67-9 2 ,4-Dimethylphenol
111-91-1 bis (2-Chloroethoxy) methane
120-83-2 2 , 4-Dichlorophenol
120-82-1 1,2,4-Trichlorobenzene
91-20-3 Naphthalene
106-47-8 4-Chloroaniline
87-68-3 Hexachlorobutadiene
59-50-7 4-Chloro-3-methylphenol
91-57-6 2-Methylnaphthalene
77-47-4 Hexachlorocyclopentadiene
88-06-2 2 , 4 , 6-Trichlorophenol
95-95-4 2 ,4 , 5-Trichlorophenol
91-58-7 2-Chloronaphthalene
88-74-4 2-Nitroaniline
131-11-3 Dimethylphthalate
208-96-8 Acenaphthylene
606-20-2 2, 6-Dinitrotoluene
99-09-2 3-Nitroaniline
83-32-9 Acenaphthene
FORM I SV-1
3/90
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1C
SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET
EPA SAMPLE NO.
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Matrix: (soil/water)
Sample wt/vol:
Level: (low/med)
% Moisture:
_(g/mL)_
decanted: (Y/N)
Concentrated Extract Volume:
Injection Volume: (uL)
GPC Cleanup: (Y/N) pH:
(uL)
Lab Sample ID:
Lab File ID:
Date Received:
Date Extracted:
Date Analyzed:
Dilution Factor:
CAS NO.
COMPOUND
CONCENTRATION UNITS:
(ug/L or ug/Kg)
-2,4-Dinitrotoluene_
•Diethylphthalate_
f 1-28-5 2,4-Dinitrophenol
:.00-02-7 4-Nitrophenol
132-64-9 Dibenzofuran
121-14-2
84-66-2
7005-72-3 4-Chlorophenyl-phenylether
86-73-7 Fluorene
100-01-6 4-Nitroaniline
534-52-1 4,6-Dinitro-2-methylphenol
86-30-6 N-Nitrosodiphenylamine (1)
101-55-3 4-Bromophenyl-phenylether
118-74-1
87-86-5
85-01-8
120-12-7
86-74-8
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
-Hexachlorobenzene_
-Pentachlorophenol"
-Phenanthrene ~
-Anthracene
-Carbazole
-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_
•Dibenz(a,h)anthracene_^
-Benzo(g,h,ijperylene
(1) - Cannot be separated from Diphenylamine
FORM I SV-2
3/90
-------
ID
PESTICIDE ORGANICS ANALYSIS DATA SHEET
EPA SAMPLE NO.
Name:
Code:
Case No.:
Contract:
SAS No.:
Matrix: (soil/water)
Sample wt/vol: (g/ml.)
% Moisture: decanted: (Y/N)
Extraction: (SepF/Cont/Sonc)
Concentrated Extract Volume:
Injection Volume: (uL)
GPC Cleanup: (Y/N) pH:
(uL)
SDG No.:
Lab Sample ID:
Lab File ID:
Date Received:
Date Extracted:
Date Analyzed:
Dilution Factor:
Sulfur Cleanup: (Y/N)
CAS NO.
COMPOUND
CONCENTRATION UNITS:
(ug/L or ug/Kg)
319-84-6 alpha-BHC
319-85-7 beta-BHC
319-86-8 delta-BHC
58-89-9 gamma-BHC (Lindane)
76-44-8 Heptachlor "
309-00-2 Aldrin
1024-57-3 Heptachlor epoxide_
959-98-8 Endosulfan I
60-57-1 Dieldrin
72-55-9 4 ,4 ' -DDE
72-20-8 Endrin
33213-65-9 Endosulfan II
72-54-8 4 ,4 • -ODD
1031-07-8 Endosulfan sulfate_
50-29-3 4 , 4 ' -DDT
72-43-5 Methoxychlor
53494-70-5 Endrin ketone
7421-36-3 Endrin aldehyde
5103-71-9 alpha-Chlordane
5103-74-2 gamma-Chlordane
8001-35-2 Toxaphene
12674-11-2 Aroclor-1016
11104-28-2 Aroclor-1221
11141-16-5 Aroclor-1232
53469-21-9 Aroclor-1242
12672-29-6 Aroclor-1248
11097-69-1 Aroclor-1254
11096-82-5 Aroclor-1260
FORM I PEST
3/90
-------
IE
VOLATILE ORGANICS ANALYSIS DATA SHEET
TENTATIVELY IDENTIFIED COMPOUNDS
EPA SAMPLE NO.
Lab Name:
Lab Code:
Case No.:
Contract:_
SAS No.:
SDG No.:
Matrix: (soil/water)
sample wt/vol:
Level: (low/med)
% Moisture: not dec.
GC Column: ID:
Soil Extract Volume:
Number TICs found:
_(g/mL).
Lab Sample ID:
Lab File ID:
Date Received:
Date Analyzed:
(mm)
Dilution Factor:
(uL)
Soil Aliquot Volume:
CONCENTRATION UNITS:
(ug/L or ug/Kg)
(uL)
CAS NUMBER
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.
COMPOUND NAME
RT
EST. CONC.
Q
t
FORM I VOA-TIC
3/90
-------
Name:
Lab Code:
IF
SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET
TENTATIVELY IDENTIFIED COMPOUNDS
Contract:
SAS No.:
EPA SAMPLE NO.
Case No.:
SDG No.:
Matrix: (soil/water)
Jample wt/vol: (g/mL)
Level: (low/med)
% Moisture: decanted: (Y/N)
Concentrated -Extract Volume: (uL)
Injection Volume: (uL)
GPC Cleanup: (Y/N) pH:
Lab Sample ID:
Lab File ID:
Date Received:
Date Extracted:
Date Analyzed:
Dilution Factor:
Number TICs found:
CONCENTRATION UNITS:
(ug/L or ug/Kg)
CAS LUMBER
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.
9.
r— JO.
1
COMPOUND NAME
RT
EST. CONC.
Q
FORM I SV-TIC
3/90
-------
2A
WATER VOLATILE SYSTEM MONITORING COMPOUND RECOVERY
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.
| EPA
| SAMPLE NO.
1 -
on
021
031
04|
051
06|
071
08|
09|
101
111
121
131
141
151
16|
171
18|
19|
201
211
221
231
241
25|
26|
27|
281
291
301
SMC1
(TOL) #
SMC2
(BFB) £
SMC3
(DCE)#
OTHER
TOT
OUT
QC LIMITS
SMC1 (TOL) = Toluene-d8 (88-110)
SMC2 (BFB) = Bromofluorobenzene (86-115)
SMC3 (DCE) = l,2-Dichloroethane-d4 (76-114)
rf Column to be used to flag recovery values
* Values outside of contract required QC limits
D System Monitoring Compound diluted out
page of
FORM II VOA-1
3/90
-------
2B
SOIL VOLATILE SYSTEM MONITORING COMPOUND RECOVERY
_Lab Name:
Code:
Case No.:
Contract:
SAS No.:
SDG No.
Level:(low/med)
1 EPA
I SAMPLE NO.
1
01|
02|
03|
04 |
05 |
06 |
07|
08 |
09 |
10|
HI
12|
13|
14]
15|
16 |
17 |
18 |
19|
20|
21|
22|
23|
24)
25|
26|
27|
28|
29|
30|
I SMC1
1 (TOL) #
SMC2
(BFB) =
| SMC3
1 (DCE)#
OTHER
ITOT
[OUT
1
QC LIMITS
SMC1 (TOL) = Toluene-d8 (84-138)
SMC2 (BFB) = Bromofluorobenzene (59-113)
SMC3 (DCE) = l,2-Dichloroethane-d4 (70-121)
# Column to be used to flag recovery values
* Values outside of contract required QC limits
D System Monitoring Compound diluted out
page of
FORM II VOA-2
3/90
-------
2C
WATER SEMIVOLATILE SURROGATE RECOVERY
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.
EPA
SAMPLE NO.
SI
(NBZ)#
S2
(FBP)#
======
S3
(TPH) #
S4
(PHL)*
======
S5
(2FP)#
S6
(TBP) #
=S=====
S7
(2CP)#
S8
(DCB) |
TOT
OUT
01|
02|
03|.
04 |
05|'
061
o?i;
08 |
09|'
10i:
"I.
"I.
13|.
14!
151.
17|
18|
19|
20|.
21|
22|
23
24 j
25|'
26|
27|
28|
29|'
301
QC LIMITS
SI (NBZ) = Nitrobenzene-dS (35-114)
S2 (FBP) = 2-Fluorobiphenyl (43-116)
S3 (TPH) = Terphenyl-dl4 (33-141)
S4 (PHL) = Phenol-d5 (10-110)
S5 (2FP) = 2-Fluorophenol (21-110)
S6 (TBP) = 2,4,6-Tribromophenol (10-123)
S7 (2CP) = 2-Chlorophenol-d4 (33-110)
S8 (DCB) = l,2-Dichlorobenzene-d4 (16-110)
(advisory)
(advisory)
page
of
# Column to be used to flag recovery values
* Values outside of contract required QC limits
D Surrogate diluted out
FORM II SV-1
3/90
-------
2D
SOIL SEMIVOLATILE SURROGATE RECOVERY
J^ab Name:
Code:
Case No.:
Level:(low/med)
Contract:
SAS No.:
SDG No.:
EPA
SAMPLE NO.
SI
(NBZ)#
52
(FBP) |
-
S3
(TPH) f
S4
(PHL) #
S5
(2FP)#
_.
S6
(TBP) #
S7
(2CP)#
S8
(DCB) #
TOT
OUT
oil
02|
03|
04 |
05|
06)
07 |
08 |
09 ['
HI."
14|.
15|
19|
20|
21|
22 |
23|
24|
25|
26|
27|
28|
29|
301
SI (NBZ)
S2 (FBP)
S3 (TPH)
S4 (PHL)
S5 (2FP)
S6 (TBP)
S7 (2CP)
S8 (DCB)
QC LIMITS
Nitrobenzene-d5 (23-120)
2-Fluorobiphenyl (30-115)
Terphenyl-dl4 (18-137)
Phenol-d5 (24-113)
2-Fluorophenol (25-121)
2,4,6-Tribromophenol (19-122)
2-Chlorophenol-d4 (20-130)
(advisory)
l,2-Dichlorobenzene-d4 (20-130) (advisory)
I Column to be used to flag recovery values
* Values outside of contract required QC limits
D Surrogate diluted out
page of
FORM II SV-2
3/90
-------
2E
WATER PESTICIDE SURROGATE RECOVERY
Lab Name:
Lab Code:
GC Column(1):
Contract:
SAS No.:
SDG No.:
(mm) GC Column(2):
ID:
(mm)
EPA
SAMPLE NO.
TCX 1
%REC #
TCX 2
%REC #
DCB 1
%REC £
DCB 2
%REC #
OTHER
(1)
OTHER
(2)
TOT|
OUT
02|
03|.
04 |
05|
06 |
07
08 |
09 |
10 |
HI.
L2|
.
161.
17|
18 |
19 |
20|.
22
23
24
25
26
27
28
29
30
TCX = Tetrachloro-m-xylene
DCB = Decachlorobiphenyl
ADVISORY
QC LIMITS
(60-150)
(60-150)
# Column to be used to flag recovery values
* Values outside of QC limits
D Surrogate diluted out
page of
FORM II PEST-1
3/90
-------
2F
SOIL PESTICIDE SURROGATE RECOVERY
Name:
Code:
GC Column(1):
Case No.:
ID:
Contract:
SAS No.:
SDG No.:
(mm) GC Column(2):
ID:
(nun)
| EPA
| SAMPLE NO.
| ==========
oil
02|
03|
04 |
05|
06|
07 |
08)
09 |
10|
:i|
-'21
13|
14|
15|
16|
17|
18|
19|
20|
211
22|
23|
24|
25|
261
27|
28|
29|
30|
TCX 1
%REC #
TCX 2
%REC #
DCS 1
%REC £
DC3 2
*REC =
OTHER
(1)
OTHER
(2)
======
TOT
OUT!
TCX = Tetrachloro-m-xylene
DCB = Decachlorobiphenyl
ADVISORY
QC LIMITS
(60-150)
(60-150)
# Column to be used to flag recovery values
* Values outside of QC limits
D Surrogate diluted out
page of
FORM II PEST-2
3/90
-------
3A
WATER VOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Matrix Spike - EPA Sample No.:
COMPOUND
1, 1-Dichloroethene
Trichloroethene
Benzene
Toluene
Chlorobenzene
SPIKE
ADDED
(ug/L)
SAMPLE
CONCENTRATION
(ug/L)
MS
| CONCENTRATION
(ug/L)
.
MS
%
REC #
QC.
LIMITS
REC.
61-145
71-120
76-127
76-125
75-130
| SPIKE
j ADDED
COMPOUND | (ug/L)
1
1 , 1-Dichloroethene |
Trichloroethene |
Benzene |
Toluene I
Chlorobenzene |
1
MSD
CONCENTRATION
(ug/L)
MSD
%
REC #
%
RPD *
QC L]
RPD
14
14
11
13
13
EMITS j
REC. |
61-145|
71-1201
76-127J
76-125|
75-1301
1
# 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 VOA-1
3/90
-------
3B
SOIL VOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Matrix Spike - EPA Sample No.:
Level:(low/med)
1
1
| COMPOUND
| 1,1-Dichloroethene
| Trichloroethene
| Benzene
| Toluene
| Chlorobenzene
1
| SPIKE
| ADDED
1 (ug/Kg)
I
1
1
1
1
1
1
| SAMPLE
| CONCENTRATION
| (ug/Kg)
1
1
1
1
1
1
| MS
| CONCENTRATION
(ug/Kg)
MS
%
REC 1
QC. !
LIMITS !
REC. !
59-172
62-137
66-142
59-139
60-133
COMPOUND
1, 1-Dichloroethene
Trichloroethene
Benzene
Toluene
Chlorobenzene
SPIKE
ADDED
(ug/Kg)
MSD
CONCENTRATION
(ug/Kg)
MSD
%
REG |
%
RPD f
QC LIMITS
RPD | REC.
22 |59-172
24 (62-137
21 |66-142
21 |59-139
21 |60-133
1
# 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 VOA-2
3/90
-------
3C
WATER SEMIVOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Lab Name:
Lab Code:
Case No.:
Matrix Spike - EPA Sample No.:
Contract:
SAS No.:
SDG No. ;:
COMPOUND
Phenol
2-Chlorophenol
1 , 4-Dichlorobenzene
N-Nitroso-di-n-prop. (1)
1,2, 4-Trichlorobenzene
4-Chloro-3-methylphenol
Acenaphthene
4-Nitrophenol
2 , 4-Dinitrotoluene
Pentachlorophenol
Pyrer a
SPIKE
ADDED
(ug/L)
SAMPLE
CONCENTRATION
(ug/L)
MS
CONCENTRATION
(ug/L)
MS | QC.
% | LIMITS
REC || REC.
| 12-110
127-123
136- 97
141-116
139- 98
123- 97
146-118
110- 80
124- 96
| 9-103
126-127
1
COMPOUND
Phenol
2 -Chlorophenol
1 , 4-Dichlorobenzene
N-Nitroso-di-n-prop . ( 1 )
1,2, 4-Trichlorobenzene
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
28
38
28
42
31
50
38
50
31
CMITS
REC.
12-110
27-123
36- 97
41-116
39- 98
23- 97
46-118
10- 80
24- 96
9-103
26-127
(1) N-Nitroso-di-n-propylamine
f 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 SV-1
3/90
-------
3D
SOIL SEMIVOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
~~>b Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Matrix Spike - EPA Sample No.:
Level:(low/med)
COMPOUND
Phenol
2 -Chlorophenol
1 t 4-Dichlorobenzene
N-Nitroso-di-n-prop . (1)
1,2, 4-Trichlorobenzene_
4 -Chloro- 3 -methy Ipheno 1
Acenaphthene
4-Nitrophenol
2 , 4-Dinitrotoluene
Pentachlorophenol
Pyren;i
| SPIKE
ADDED
(ug/Kg)
SAMPLE
CONCENTRATION
(ug/Kg)
MS
CONCENTRATION
(ug/Kg)
MS | QC.
% [LIMITS
REC #| REC.
|26- 90
125-102
128-104
|41-126
|38-107
126-103
131-137
111-114
|28- 89
117-109
135-142
1
COMPOUND
Phenol
2 -Chlorophenol
1 , 4-Dichlorobenzene
N-Nitroso-di-n-prop. (l)
1, ** , 4-Trichlorobenzene
4-Chloro-3 -methy Iphenol
Acenaphthene
4-Nitrophenol
2 , 4-Dinitrotoluene
Pent achl or ophenol
Pyrene
SPIKE
ADDED
(ug/Kg)
MSD
CONCENTRATION
(ug/Kg)
MSD
%
REC #
%
RPD I
1
QC LIMITS |
RPD | REC. I
35 |26- 90|
50 |25-102|
27 | 28-104)
38 |41-126|
23 |38-107|
33 |26-103|
19 |31-137|
50 |11-114|
47 |28- 89|
47 |17-109|
36 |35-142|
1 1
(1) N-Nitroso-di-n-propylaraine
# 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 SV-2
3/90
-------
3E
WATER PESTICIDE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Matrix Spike - EPA Sample No.:
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 | MSD | |
CONCENTRATION! % j % |
(ug/L) | REC #| RPD #|
1 1 1
1 II
1 1 1
1 1 1
I 1 1
1 1 1
1 I I
1
QC LIMITS |
RPD | REC. |
15 |56-123|
20 |40-13'1|
22 1 40-120)
18 | 52-126|
21 |56-121|
27 | 38-127|
1 1
I 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 PEST-1
3/90
-------
3F
SOIL PESTICIDE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
-J^ab Name:
Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Matrix Spike - EPA Sample No.:
COMPOUND
gamma-BBC (Lindane)
Heptachlor
Aldrin
Dieldrin
Endrin
4,4' -DDT
SPIKE
ADDED
(ug/Kg)
SAMPLE
CONCENTRATION
(ug/Kg)
MS
CONCENTRATION
(ug/Kg)
MS
%
REC #
— _
QC.
LIMITS
REC.
46-127
35-130
34-132
31-134
42-139
23-134
COMPOUND
gamma-BHC (Lindane)
Heptachlor
Aldrin
Dieldrin
Endrin
4,4' -DDT
SPIKE
ADDED
(ug/Kg)
MSD
CONCENTRATION
(ug/Kg)
MSD
%
REC #
%
RPD #
QC LIMITS ;
RPD REC. |
50 46-127|
31 35-1301
43 34-132|
38 31-134]
45 42-139]
50 23-134]
1
# 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 PEST-2
3/90
-------
4A
VOLATILE METHOD BLANK SUMMARY
EPA SAMPLE NO.
Lab Name:
Lab Code:
Lab File ID:
Date Analyzed:
GC Column:
Instrument ID:
Case No.:
Contract:_
SAS No.:
SDG No.:
Lab Sample ID:
Time Analyzed:
ID:
(mm)
Heated Purge: (Y/N)
THIS METHOD BLANK APPLIES TO THE FOLLOWING SAMPLES, MS AND MSD:
| EPA
j SAKPLE NO.
Oil
02|
03|
04 |
05|
06 |
07|
081
09|
10|
111
121
131
141
151
16|
17|
18|
191
20|
211
221
231
24|
25|
26|
27|
28|
29|
30|
LAB
SAMPLE ID
LAB
FILE ID
TIME
ANALYZED
COMMENTS:
page of
FORM IV VOA
3/90
-------
4B
SEMIVOLATILE METHOD BLANK SUMMARY
EPA SAMPLE NO.
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Lab File ID:
Instrument ID:
Matrix: (soil/water)
Level:(low/med)
Lab Sample ID:
Date Extracted:
Date Analyzed:
Time Analyzed:
THIS METHOD BLANK APPLIES TO THE FOLLOWING SAMPLES, MS AND MSD:
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 SV
3/90
-------
Lab Name:
Lab Code:
4C
PESTICIDE METHOD BLANK SUMMARY
Contract:
SAS No.:
EPA SAMPLE NO.
Case No.:
SDG No.:
Lab Sample ID:
Lab File ID:
Matrix:(soil/water)
Sulfur Cleanup: (Y/N)
Date Analyzed (1):
Time Analyzed (1):
Instrument ID (1) :
GC Column (1):
ID:
Extraction:(Se^F/Cont/Sonc)
Date Extracted:
Date Analyzed (2):
Time Analyzed (2) :
Instrument ID (2):
(mm) GC Column (2):
ID:
(mm)
THIS METHOD BLANK APPLIES TO THE FOLLOWING SAMPLES, MS AND MSD:
COMMENTS:
page of
| EPA
| SAMPLE NO.
oil
02[
031
04 |
05|
06|
07|
08|
09|
10 |
HI
12 |
13 |
14 |
15 |
16 |
17|
18 |
19 |
20|
211
22|
23|
24|
25|
26|
LAB
SAMPLE ID
DATE |
ANALYZED 1|
DATE
ANALYZED 2
FORM IV PEST
3/90
-------
5A
VOLATILE ORGANIC INSTRUMENT PERFORMANCE CHECK
BROMOFLUOROBENZENE (BFB)
Lab Name:
Lab Code:
Lab File ID:
Instrument ID:
GC Column:
Case No.:
Contract:
SAS No.:
SDG No.:
ID:
(mm)
BFB Injection Date:
BFB Injection Time:
Heated Purge: (Y/N)
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
)2
1-Value is % mass 174
2-Value is % mass 176
THIS CHECK APPLIES TO THE FOLLOWING SAMPLES, MS, MSD, BLANKS, AND STANDARDS:
| EPA
| SAMPLE NO.
on
02|
03 |
04|
051
06|
07 |
08 |
09|
101
111
121
131
14|
15|
16|
17|
18 |
191
201
211
221
LAB
SAMPLE ID
LAB
FILE ID
DATE
ANALYZED
TIME
ANALYZED
page of
FORM V VOA
3/90
-------
SB
SEMIVOLATILE ORGANIC INSTRUMENT PERFORMANCE CHECK
DECAFLUOROTRIPHENYLPHOSPHINE (DFTPP)
Lab Name:
Contract:
Lab Code:
Case No.:
SAS No.:
SDG No.:
Lab File ID:
Instrument ID:
DFTPP Injection Date:
DFTPP Injection Time:
xn/e
K=3£=S =
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
1-Value is % mass 69
% RELATIVE
ABUNDANCE
1
)2
2-Value is % mass 442
THIS CHECK APPLIES TO THE FOLLOWING SAMPLES, MS, MSD, BLANKS, AND STANDARDS"
I EPA
| SAMPLE NO.
oil
02|
03|
04 |
05|
06|
07)
08|
09|
10|
HI
12|
13|
14|
15|
16|
17|
18|
19|
20|
21|
22|
LAB
SAMPLE ID
LAB
FILE ID
.
DATE
ANALYZED
TIME
ANALYZED
page of
FORM V SV
3/90
-------
6A
VOLATILE ORGANICS INITIAL CALIBRATION DATA
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Instrument ID:
Heated Purge: (Y/N)
GC Column: ID:
Calibration Date(s):_
Calibration Times:
(mm)
ILAB FILE ID: RRFIO = RRF20 =
IRRF50 = RRF100= RRF200=
1
1
| COMPOUND RRFIO RRF20
1 ~"
I Chi or ome thane
| Bromomethane *
I Vinyl Chloride *
| Chloroethane I
IMethylene Chloride
I Acetone I
(Carbon Disulfide |
| 1 , 1-Dichloroethene *
| l, 1-Dichloroethane *
(1,2-Dichloroethene (total)
| Chloroform *
1 1,2-Dichloroethane *
| 2-Butanone
[1,1, l-Trichloroethane *
(Carbon Tetrachloride *
| Bromodichloromethane * I
| 1 , 2-Dichloropropane
( cis-1, 3-Dichloropropene *
( Trichloroethene *
( Dibromochloromethane *
11,1,2-Trichloroethane *
| Benzene *
I trans-1 , 3-Dichloropropene *
| Bromof orm *
I 4-Methyl-2-Pentanone
I 2-Hexanone
ITetrachloroethene *
I 1,1,2,2-Tetrachloroethane *
( Toluene *
I Chlorobenzene *
I Ethylbenzene *
(Styrene *
(Xylene (total) *
1 =ss===rs==r==s==5=:======:=: = :==:== ===: ======
|Toluene-d8
RRF50
1
1
|
1
| Bromofluorobenzene *
| l,2-Dichloroethane-d4 I
1 1
RRF100
H
RRF200
RRF
I==SS=S==±=
% 1
RSD I
===== 1
i
*
*
1
1
1
1
*
*
|
*
*
1
*
*
*
I
*
*
*
*
*
*
*
1
1
*
*
*
*
*
*
*
I
*
1
1
* Compounds with required minimum RRF and maximum %RSD values.
All other compounds must meet a minimum RRF of 0.010.
FORM VI VOA
3/90
-------
6B
SEMIVOLATILE ORGANICS INITIAL CALIBRATION DATA
Lab Name:
Lab Code:
Case No.:
Contract:_
SAS No.:
SDG No.
Instrument ID:
Calibration Date(s):
Calibration Times:
I LAB FILE ID: RRF20 =
(RRF80 = RRF120=
1
1 1
| COMPOUND (RRF20
I Phenol *
|bis(2-Chloroethyl) ether *
| 2-Chlorophenol *
| 1 , 3-Dichlorobenzene *
| 1,4-Dichlorobenzene *
| 1,2-Dichlorobenzene *
|2-Methylphenol *
|2,2 '-oxybis(l-Chloropropane) |
|4-Methylphenol *
IN-Nitroso-di-n-propylamine *
(Hexachloroe thane *
| Nitrobenzene *
| Isophorone *
| 2-Nitrophenol *
| 2, 4-Dimethyl phenol *
| bis ( 2 -Chloroethoxy) methane *
| 2 , 4 -Dichlorophenol *
| 1,2,4-Trichlorobenzene *
(Naphthalene *
|4-Chloroaniline |
I Hexachlorobutadiene |
|4-chloro-3-raethylphenol *
| 2-Methylnaphthalene *
IHexachlorocyclopentadiene |
| 2,4, 6-Trichlorophenol *
| 2,4, 5-Trichlorophenol *
| 2-Chloronaphthalene *
| 2-Nitroaniline I
| Dimethylphthalate |
| Acenaphthylene *
| 2, 6-Dinitrotoluene *
| 3-Nitroaniline |
| Acenaphthene *
|2,4-Dinitrophenol |
|4-Nitrophenol j
| Dibenzofuran *
| 2,4-Dinitrotoluene *
1 1
RRF50
= =££====£
RRF50
RRF16
RRF80
sss=sgs=as^
=
D=
RRF120
RRF160
RRF
% 1
RSZ
*
*
*
*
*
*
*
1
*
*
*
•*
*
*
*
*
*
*
I
1
*
*
1
*
*
*
1
1
*
*
/
*
1
i
X
*
1
* Compounds with required minimum RRF and maximum %RSD values.
All other compounds must meet a minimum RRF of 0.010.
FORM VI SV-1
3/90
-------
6C
SEMIVOLATILE ORGANICS INITIAL CALIBRATION DATA
Lab Name:
Lab Code:
Case No.:
Contract:_
SAS No.:
SDG No.
Instrument ID:
Calibration Date(s):
Calibration Times:
|LAB FILE ID: RRF20 = RRF50 =
IRRF80 = RRF120= RRF160=
1
1 1
| COMPOUND (RRF20
| Diethylphthalate |
| 4-Chlorophenyl-phenylether *
| Fluorene *
|4-Nitroaniline |
| 4, 6-Dinitro-2-methylphenol |
| N-Nitrosodiphenylamine (1) |
| 4-Bromophenyl-phenylether *
| Hexachlorobenzene *
| Pentachlorophenol *
| Phenanthrene *
| Anthracene *
| Carbazole |
1 Di-n-butylphthalate [
| Fluoranthene *
| Pyrene *
(Butylbenzylphthalate |
j 3, 3 '-Dichlorobenzidine |
|Benzo (a) anthracene *
| Chrysene *
|bis(2-Ethylhexyl)phthalate |
j Di-n-octylphthalate |
| Benzo (b) f luoranthene *
| Benzo (Jc) f luoranthene *
| Benzo(a)pyrene *
| Indeno(l,2, 3-cd)pyrene *
I Dibenz (a, h) anthracene *
| Benzo (g,h, i)perylene *
RRF50 RRF80
I
|Nitrobenzene-d5 |
I 2-Fluorobiphenyl *
I Terphenyl-dl4 *
| Phenol-d5 * |
j 2-Fluorophenol * |
| 2, 4, 6-Tribromophenol J j
| 2-Chlorophenol-d4 *
| l,2-Dichlorobenzene-d4 *
1 1
RRF120|RRF160| RRF
*•
% 1
RSD |
1
*
*
i
1
1
*
*
*
*
*
1
1
*
*
1
1
*
*
1
i
*
*
*
*
*
*
1
*
*
*
*
1
*
*
1
(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.
FORI1 VI SV-2
3/90
-------
6D
PESTICIDE INITIAL CALIBRATION OF SINGLE COMPONENT ANALYTES
Lab Name:
Lab Code:
Instrument ID:
GC Column:
Case No.:
Contract:
SAS No.:
Level (x low): low
ID: (mm) Date(s) Analyzed:
SDG No.: _
mid high
COMPOUND
alpha-BHC
beta-BHC
delta-BHC
gamma-BBC (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-Chlordane
gamma-Chlordane
Tetrachloro-m-xylene
Decachlorobiphenyl
RT OI
LOW
• STANDARDS
MID | HIGH
1
MEAN
RT
RT W
FROM
v
ENDOW
TO
* Surrogate retention times are measured from Standard Mix A analyses.
Retention time windows are ± 0.04 minutes for all compounds except
Methoxychlor, at + 0.05 minutes.
FORM VI PEST-1
3/90
-------
6E
PESTICIDE INITIAL CALIBRATION OF SINGLE COMPONENT ANALYTES
Lab Name:
Lab Code:
Case No.:
Contract:_
SAS No.:
Instrument ID:
GC Column:
Level (x low): low
ID: (mm) Date(s) Analyzed:
SDG No.: _
mid high
COMPOUND
alpha-BHC
beta-BHC
delta-BHC
gaauna-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-Chlordane
gamma-Chlordane
Tetrachloro-m-xylene
Decachlorobiphenyl
LOW
CALIBRATIC
MID
DN FACTORS
HIGH
MEAN
1-
1
%RSD
* Surrogate calibration factors are measured from Standard Mix A analyses.
%RSD must be less than or equal 10.0 % for all compounds except alpha-BHC
beta-BHC, gamma-BHC, DDT, Endrin, and Methoxyclor, where %RSD must be less
than or equal to 15.0%
FORM VI PEST-2
3/90
-------
6F
PESTICIDE INITIAL CALIBRATION OF MULTICOMPONENT ANALYTES
Lab Name:
Lab Code:
Instrument ID:
GC Column:
Contract:
Case No.: SAS No.: SDG No.:
Date(s) Analyzed:
ID: (mm)
COMPOUND
Toxaphene
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
AMOUNT
(ng)
PEAK | RT
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
£-
*1
*2
*3
4
5
*1
*2
*3
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
RT W]
FROM
.
ENDOW
TO
1 1
CALIBRATION |
FACTOR
* Denotes required peaks
FORM VI PEST-3
3/90
-------
GG
PESTICIDE ANALYTE RESOLUTION SUMMARY
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.
GC Column (1):
ID:
EPA Sample No. (Standard 1) :
Date Analyzed (1) :
(mm) Instrument ID (1):
Lab Sample ID (1):
Time Analyzed (1):
01
02
03
04
05
06
07
08
09
1
ANALYTE | RT
I
1
I
1
I
1
!
!
1
RESOLUTION]
(%)
s.
GC Column (2) :
ID:
EPA Sample No. (Standard 2) :
Date Analyzed (2) :
(mm) Instrument ID (2):
Lab Sample ID (2):
Time Analyzed (2):
01
02
03
04
05
06
07
08
09
ANALYTE
| RESOLUTION
RT | (%)
1
1
|
1
i
|
|
|
|
1
Resolution of two adjacent peaks must be calculated as a percentage of the
height of the smaller peak, and must be greater than or equal to 60.0%.
FORM VI PEST-4
3/90
-------
Lab Name:
Lab Code:
7A
VOLATILE CONTINUING CALIBRATION CHECK
Contract:
SAS No.:
Case No.:
Instrument ID:
Lab File ID:
Calibration Date:
SDG No.:
Time:
Heated Purge: (Y/N)
GC Column: ID:
Init. Calib. Date(s) :_
Init. Calib. Times:
(mm)
1
| COMPOUND
| ===========================
| Chloromethane
| Bromomethane
I Vinyl Chloride
| Chloroethane
(Methylene Chloride
| Acetone
| Carbon Disulfide
| 1 , 1-Dichloroethene
1 1, 1-Dichloroethane
| 1,2-Dichloroethene (total)
| Chloroform
| 1 , 2-Dichloroethane
| 2-Butanone
| 1 , 1 , 1-Trichloroethane
(Carbon Tetrachloride
j Bromodichloromethane
1 1, 2-Dichloropropane
I cis-1, 3-Dichloropropene
| Trichloroethene
| Dibromochloromethane
1 1,1, 2-Trichloroethane
| Benzene
| trans-1, 3-Dichloropropene
j Bromof orm
| 4-Methyl-2-Pentanone
| 2-Hexanone
| Tetrachloroethene
| 1, 1, 2 , 2-Tetrachloroethane
(Toluene
| Chlorobenzene
(Ethylbenzene
| Styrene
IXylene (total)
|Toluene-d3
| Bromof luorobenzene
| 1, 2-Dichloroethane-d4
|
1
| RRF
1 ======
1
1
1
1
[
1
1
1
1
I
1
| MIN
RRF50 | RRF
====== | =====
1
10.100
10.100
1
1
I
1
10.100
I 0.200
1
10.200
| 0.100
1
10.100
| 0.100
| 0.200
1
(0.200
| 0.300
| 0.100
| 0. 100
| 0.500
| 0.100
[ 0.100
1
1
| 0. 200
| 0.500
| 0.400
|0.500
| 0. 100
| 0.300
10.300
I
1
1
| 0. 200
1
1
| MAX|
%D | W |
1 1
125.0)
|25.0|
1 1
1 1
1 1
1 1
125.01
125.01
1 1
125.01
125.01
1 1
(25.0!
125.01
125.01
i 1
I25..0I
125.. 0|
125.. 0|
125.01
125.01
125.01
125.01
1 1
1 1
|25.0|
125.01
125.01
125.01
125.01
|25.0|
125.01
===== — I — ==— I
1 I
! 1
|25.0|
1 1
1 1
All other compounds must meet a minimum RRF of 0.010.
FORM VII VOA
3/90
-------
7B
SEMIVOLATILE CONTINUING CALIBRATION CHECK
Lab Name:
Lab Code:
Instrument ID:
Contract:
Case No. : SAS No. :
Calibration Date:
SDG No. :
Time:
Lab File ID:
Init. Calib. Date(s):
Init. Calib. Times:
1
| COMPOUND
| Phenol
| bis (2-Chloroethyl ) ether
| 2-Chlorophenol
| 1, 3-Dichlorobenzene
| 1, 4-Dichlorobenzene
1 1, 2-Dichlorobenzene
| 2-Methylphenol
| 2 , 2 ' -oxybis (1-chloropropane)
[ 4-Methylphenol
| N-Nitroso-di-n-propylamine
[ Hexachloroethane
[Nitrobenzene
| Isophorone
| 2-Nitrophenol
j 2 , 4-Dimethylphenol
| bis (2-Chloroethoxy) methane
I 2 , 4-Dichlorophenol
j 1 , 2 , 4-Trichlorobenzene
| Naphthalene
| 4-Chloroaniline
| Hexachlorobutadiene
| 4-Chloro-3-methylphenol
| 2-Methylnaphthalene
| Hexachlorocyclopentadiene
(2,4, 6-Trichlorophenol
| 2 , 4 , 5-Trichlorophenol
| 2-Chloronaphthalene
| 2-Nitroaniline
| Dimethylphthalate
| Acenaphthylene
| 2 , 6-Dinitrotoluene
| 3-Nitroaniline
| Acenaphthene
1 2 , 4-Dinitrophenol
| 4-Nitrophenol
| Dibenzofuran
| 2, 4-Dinitrotoluene
1
RRF
1
1
RRF50
MIN |
RRF |
i _
1 _
0.800)
0.700|
0.800J
0.600|
0.500J
0.400|
0.700|
L
0.600|
0.500|
0.300|
0.200J
0.400)
0.100J
0.200|
0.300)
0.200)
0.200)
0.700|
1
1
0.200)
0.400)
1
0.200)
0.300|
0.900 |
!
1.400|
0.200)
1
0.900)
!
1
0.300|
0.200)
1
| MAX|
%D | %D |
— i — — i
1 1
(25.01
|25.0|
|25.0|
|25.0|
|25.0|
|25.0|
|25.0|
1 1
|25.0|
|25.0|
|25.0|
|25.0|
|25.0|
125.0)
|25.0|
|25.0(
|25.0(
.|25.0|
|25.0|
1 1
I (
|25.0|
|25.0|
1 1
|25.0|
[25.0)
125.0)
1 1
1 1
|25.0|
|25.0|
1 1
|25.0|
1 1
1 1
|25.0|
|25.0|
( 1
All other compounds must meet a minimum RRF of 0.010.
FORM VII SV-1
3/90
-------
7C
SEMIVOLATTLE CONTINUING CALIBRATION CHECK
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
Instrument ID:
Lab File ID:
Calibration Date:
SDG No.
Time:
Init. Calib. Date(s):_
Init. Calib. Times:
1
| COMPOUND
| Diethylphthalate
I 4-Chlorophenyl-phenylether
| Fluorene
I 4-Nitroaniline
| 4 , 6-Dinitro-2-methylphenol
IN-Nitrosodiphenylamine (l)
I 4-Bromophenyl-phenylether
I Hexachlorobenzene
I Pentachlorophenol
| Phenanthrene
| Anthracene
| Carbazole
1 Di-n-butylphthalate
| Fluoranthene
I Pyrene
| Butylbenzylphthalate
13,3' -Dichlorobenz idine
I Benzo (a) anthracene
| Chrysene
|bis(2-Ethylhexyl)phthalate
| Di-n-octylphthalate
I Benzo (b) f luoranthene
| Benzo (k) f luoranthene
| Benzo (a) pyrene
| Indeno(l, 2, 3 -cd) pyrene
| Dibenz (a,h) anthracene
| Benzo (g,h, i)perylene
1 Nitrobenzene-d5
| 2-Fluorobiphenyl
|Terphenyl-dl4
|Phenol-d5
| 2-Fluorophenol
| 2 , 4 , 6-Tribromophenol
| 2-Chlorophenol-d4
| 1 , 2-Dichlorobenzene-d4
1
RRF
RRF50
MIN | |
RRF | %D |
1 1
0.500| |
1.1001 |
! 1
1 . 1
1 1
0.1001 |
0.100| |
0.100) |
0.700| |
0.700| |
1 1
1 1
0.600) |
0.700| |
1 1
) 1
0.900) |
0.900) |
1 1
1 1
0.700) |
0.700) |
0.600) |
0.400) |
0.300) |
0.200) |
1 1
0.700) |
0.500) |
0.800) |
0.600) |
1 1
0.8001 |
0.400| |
1 1
MAX)
%D |
I
25.0|
25.0|
1
1
1
25.0|
25.0|
25.0|
25.0|
25.0|
1
1
25.0|
25.0|
1
1
25.0|
25.0|
1
1
25.0|
25.0|
25.. 0|
25.. 0|
25.. 0|
25.0)
~ 1
1
25.0|
25.0)
25.0)
25.0|
1
25.0|
25.0)
1
(1) Cannot be separated from Diphenylaniine
All other compounds must meet a miniinum RRF of 0.010.
FORM VII sv-2
3/90
-------
7D
PESTICIDE CALIBRATION VERIFICATION SUMMARY
Lab Name:_
Lab Code:
GC Column:
Contract:
Case No.: SAS No.: SDG No.:
_ ID: (mm) Init. Calib. Date(s):
EPA Sample No.(PIBLK):
Lab Sample ID (PIBLK):
EPA Sample No.(PEM): _
Lab Sample ID (PEM):
Date Analyzed
Time Analyzed
Date Analyzed
Time Analyzed
PEM |
COMPOUND 1 RT
1
alpha-BHC |
beta-BHC |
gamma-BBC (Lindane) |
Endrin I
4,4' -DDT |
Methoxychlor |
1
RT WINDOW
FROM | TO
1
1 —
1
1
1
I
1
1
1
CALC
AMOUNT
(ng).
NOM
AMOUNT
(ng)
RPD
4,4'-DDT % breakdown (1) :
Combined % breakdown (1):
Endrin % breakdown (1)
QC LIMITS:
RPD of amounts in PEM must be less than or equal to 25.0%
4,4'-DDT breakdown must be less than or equal to 20.0%
Endrin breakdown must be less than or equal to 20.0%
Combined breakdown must be less than or equal to 30.0%
FOR:I vii PEST-I
3/90
-------
Lab Name:_
Lab Code:
GC Column:
7E
PESTICIDE CALIBRATION VERIFICATION SUMMARY
Contract:
SAS i:o.:
Case No.: SAS Ho.: SDG No.:
ID: (mm) Init. Calib. Date(s):
EPA Sample No.(PIBLK):
Lab Sample ID (PIBLK):
EPA Sample No.(INDA):
Lab Sample ID (INDA):
Date Analyzed :
Time Analyzed :
Date Analyzed :
Time Analyzed :
INDIVIDUAL MIX A
COMPOUND
alpha-BF^
gamma-BBC (Lindane)
Heptachlor
Endosulfan I
Dieldrin
Endrin
4,4* -ODD
4,4' -DDT
Methoxychlor
Tetrachloro-m-xylene
Decachlorob ipheny 1
| RT WINDOW
RT | FROM | TO
1 1
— 1 1 —
! 1
1 !
1 1
1 1
1 1
1 1
1 1
1 1
1 1
i 1
1 . . 1
1 1
CALC
AMOUNT
(ng)
NOM
AMOUNT
(ng)
RPD
EPA Sample No.(INDB):
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-Chlordane
gamma-Chlorodane
Tetrachloro-m-xylene
Decachlorobiphenyl
RT
RT WINDOW
FROM | TO
1
1
1
1
1
1
I
1
!
I
1
1
1
1
1
1
CALC
AMOUNT
(ng)
NOM
AMOUNT
(ng)
RPD
QC LIMITS: RPD of amounts in the Individual Mixes must be less than
or equal to 25.0%.
FORM VII PEST-2
3/90
-------
8A
VOLATILE INTERNAL STANDARD AREA AND RT SUMMARY
Lab Name:_
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Lab File ID (Standard):
Instrument ID:
GC Column: ID:
Date Analyzed:
Time Analyzed:
(mm)
Heated Purge: (Y/N)
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.
ISl(BCM)
AREA £
RT *
IS2(DFB)
AREA #
RT f
IS3(CBZ)
AREA #
"
RT #
IS1 (BCM) = Bromochloromethane
IS2 (DFB) = 1,4-Difluorobenzene
IS3 (CBZ) = Chlorobenzene-d5
AREA UPPER LIMIT = +100% of internal standard area
AREA LOWER LIMIT = - 50% of internal standard area
RT UPPER LIMIT = +0.50 minutes of internal standard RT
RT LOWER LIMIT = -0.50 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 VOA
3/90
-------
SB
SEMIVOLATILE INTERNAL STANDARD AREA AND RT SUMMARY
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.
Lab File ID (Standard):
Instrument ID:
Date Analyzed:
Time Analyzed:_
12 HOUR STD
UPPER LIMIT
LOWER LIMIT
EPA SAMPLE
NO.
ISl(DCB)
AREA #
RT #
IS2(NPT)
AREA *
RT #
IS3 (ANT)
AREA #
RT #
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
IS1 (DCS) = 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 = -f-0.50 minutes of internal standard RT
RT LOWER LIMIT = -0.50 minutes of internal standard RT
# Column used to flag internal standard area values with an asterisk.
* Values outside of QC limits.
page of
FORM VIII SV-1
3/90
-------
8C
SEMIVOLATILE INTERNAL STANDARD AREA AND RT SUMMARY
Lab Name:
Lab Code:
Case No.:
Lab File ID (Standard) :
Instrument ID:
Contract:
SAS No.:
SDG No.
Date Analyzed:
Tine Analyzed:
12 HOUR STD
UPPER LIMIT
LOWER LIMIT
EPA SAMPLE
NO.
IS4(PHN)
AREA #
RT #
ISS(CRY) |
AREA #| RT #
1
!
1
1
!
1
1
1
1
1
1
1
1
1
1
1
j
1
1
1
1
1
1
1
1
1
IS6(PRY)
AREA #
RT #
oil
02|'
03|"
04 |
05|
06 |
07|
08 |
09 |
10 |
HI
12 |
161
20)
221
IS4 (PHN)
IS5 (CRY)
IS6 (PRY)
Phenanthrene-dlO
Chrysene-dl2
Perylene-dl2
AREA UPPER LIMIT = +100% of internal standard area
AREA LOWER LIMIT = - 50% of internal standard area
RT UPPER LIMIT = +0.50 minutes of internal standard RT
RT LOWER LIMIT = -0.50 minutes of internal standard RT
# Column used to flag internal standard area values with an asterisk.
* Values outside of QC limits.
page _ of _
FORM VIII SV-2
3/90
-------
Lab Name:_
Lab Code:
GC Column:
3D
PESTICIDE ANALYTICAL SEQUENCE
Contract:
SAS No.:
Case No.:
ID:
SDG No.
(mm) Init. Calib. Date(s):
Instrument ID:
THE ANALYTICAL SEQUENCE OF PERFORMANCE EVALUATION MIXTURES, BLANKS,
SAMPLES, AND STANDARDS IS GIVEN EELOW:
| MEAN SURROGATE RT FROM INITIAL CALIBRATION
| TCX: DCB:
1
| EPA I LAB
| SAMPLE NO. | SAMPLE ID
Oil 1
021
03| |
04 |
05|
06|
07| |
08| |
09 |
10 |
HI
12|
131
14 |
15 1
16 |
17 |
18 |
19 |
20|
211
22)
231
241
25|
26|
27|
28|
29|
30|
311
32|
DATE TIME
ANALYZED ANALYZED
^
1
I
TCX
RT #
DCB
RT #
TCX = Tetrachloro-m-xylene
DCB = Decachlorobiphenyl
QC LIMITS
(+ 0.04 MINUTES)
(± 0.04 MINUTES)
# Column used to flag retenetion time values with an asterisk.
* Values outside of QC limits.
page of
FORM VIII PEST
3/90
-------
9B
PESTICIDE GPC CALIBRATION
Lab Name:
Lab Code:
GPC Column:
GC Column(1):
Case No.:
ID:
Contract:_
SAS No.:
Calibration Date:
(mm) GC Column(2):
SDG No.:
ID:
_(mm)
COMPOUND
gamma-BHC (Lindane)
Heptachlor
Aldrin
Dieldrin
Endrin
4,4' -DDT
SPIKE ! SPIKE |
ADDED | RECOVERED j %
(ng) .| (ng) | REC *
____ I — — _«_ — f _ _*__
1 1
1 1
1 1
1 1
1 1
1 1
1 1
1 1 s
QC. |
LIMITS |
REC. |
1
80-1101
80-1101
80-1101
80-1101
80-1101
80-110)
1
# Column to be used to flag recovery values with an asterisk
* Values outside of QC limits
THIS GPC CALIBRATION APPLIES TO THE FOLLOWING SAMPLES, BLANKS, MS AND MSD:
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
page of
EPA
SAMPLE NO.
LAB
SAMPLE ID
DATE
ANALYZED 1
DATE
ANALYZED 2
FORM IX PEST-2
3/90
-------
9A
PESTICIDE FLORISIL CARTRIDGE CHECK
Lab Name:
Contract:
Lab Code:
Case Mo.:
SAS Mo.:
SDG No.:
Florisil Cartridge Lot Number:
GC Column(1) : ID: _
Date of Analysis:
(mm) GC Column(2):
ID:
(mm)
SPIKE
ADDED
COMPOUND (ng)
alpha-BHC
gamma-BHC (Lindane)
Heptachlor
Endosulfan I
Dieldrin
Endrin
4, 4 '-ODD
4,4' -DDT
Methoxychlor
Tetrachloro-m-xylene
Decachlorobiphenyl
SPIKE
RECOVERED
(ng)
%
REC #
.
QC
LIMITS
80-110
80-110
80-110
80-110
80-110
80-110
80-110
80-110
80-110
80-110
80-110
# Column to be used to flag recovery with an asterisk.
* Values outside of QC limits.
THIS CARTRIDGE LOT APPLIES TO THE FOLLOWING SAMPLES, BLANKS, MS, AND MSD:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
13
19
20
21
22
23
EPA
SAMPLE NO.
LAB
SAMPLE ID
DATE
ANALYZED 1
DATE
ANALYZED 2
page of
FORM IX PEST-1
3/90
-------
10A
PESTICIDE IDENTIFICATION SUMMARY
FOR SINGLE COMPONENT ANALYTES
EPA SAMPLE NO.
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Lab Sample ID :
Instrument ID (1):
GC Column(1):
ID:
Date(s) Analyzed:
Instrument ID (2):
(mm) GC Coluinn(2):
ID:
(mm)
ANALYTE
I
1
COL| RT
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
RT WINDOW
FROM | TO
1
I
:
1
CONCENTRATION | %D
s
i i
page of
FORM X PEST-1
3/90
-------
10B
PESTICIDE IDENTIFICATION SUMMARY
FOR MULTICOMPONENT ANALYTES
EPA SAMPLE NO.
Lab Name:
Lab Code:
Case No.:
Contract:
SAS 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
1
PEAK | RT
1
2
4
5
1
2
3
4
5
1
2
4
5
1
2
3
4
5
2
3
4
c
1
2
3
4
5
RT W]
FROM
1
1
======
ENDOW
TO
1
1
CONCENTRATION
1 1
! 1
1
i
! |
1 1
1
1 I
1
1
MEAN
CONCENTRATION
s
%D
At least 3 peaks are required for identification of multicomponent analytes
page of
FORM X PEST-2 3/90
-------
SAMPLE LOG-IN SHEET
Lab Name: Page of
Received By (Print Name): Log ;„ n.t,-
Received Bv (Siznature):
Case Number:
Sample Delivery
Group No.:
SAS Number:
REMARKS:
1 . Custody Seal(s) Present/Absent*
Intact/Broken
2. Custody Seal Noi.:
3. Chaim-of -Custody Present/Absent*
Records
Packing List
5. Airbill Airbill/Sucker
Present/Abfcal*
6. AirbQl No.:
7. Sample Tags Present/Abfcnt*
Sample Tag Luted/Not Lifted
Numbers on Chain-of-
Cusuxiy
. g. Sample Condition: Intact/Broken*/
Leaking
9. Doe* information on
custody record*, traffic
report*, and sonple
tagi agree? Yea/No*
10. Date Received H Labt
11. Time Received: _..
Sample Transfer
Area*:
By:
rw
EPA
SAMPLE
#
CORRESPONDING
SAMPLE
TAG
#
ASSIGNED
LAB
#
S
REMARKS:
CONDITION
OF SAMPLE
SHIPMENT, ETC.
* Contact SMO and attach record of laolaBon
Reviewed By:
Dale:
No,;
Logbook Page No:
PORMDC-1
-------
ORGANICS COMPLETE SDG FILE (CSF) INVENTORY SHEET
LABORATORY MAKE CITY/STATE
CASE NO. SDG NO. SDG MOS. TO FOLLOW SAS NO.
CONTRACT NO. SOW NO.
All documents delivered in the complete SDG file must be original documents
where possible. (REFERENCE EXHIBIT B, SECTION II and SECTION III.)
PAGE NOs CHECK
FROM TO LAB EPA
1. Inventory Sheet (Form DC-2) (Do not number)
2. SDG Case Narrative
3. Traffic Report
4. Volatiles Data
a. QC Summary
Surrogate Percent Recovery Summary (Form II VOA)
Lab Control Sample Recovery (From III VOA)
Method Blank Summary (Form IV VOA)
Tuning and Mass Calibration (Form V VOA)
b. Sample Data
TCL Results - (Form I VOA)
Tentatively Identified Compounds (Form I VOA-TIC)
Reconstructed total ion chromatograms (RIG)
for each sample
For each sample:
Raw spectra and background-subtracted
mass spectra of target compounds identified
Mass spectra of all reported TICs with three
best library matches
c. Standards Data (All Instruments)
Initial Calibration Data (Form VI VOA)
RICs and Quan Reports for all Standards
Continuing Calibration (Form VII VOA)
RICs and Quan Reports for all Standards
Internal Standard Area and RT Summary
(Form VIII VOA)
d. QC Data
BFB
Blank Data
Matrix Spike Data
Matrix Spike Duplicate Data
5. Semivolatiles Data
a. QC Summary
Surrogate Percent Recovery Summary (Form II SV)
MS/MSD Summary (Form III SV)
Method Blank Summary (Form IV SV)
Tuning and Mass Calibration (Form V SV)
FORM DC-2-1
OLM01.0
-------
ORGANICS COMPLETE SDG FILE (CSF) INVENTORY SHEET (Cont.)
CASE NO. SOG NO. SOG NOS. TO FOLLOW SAS NO.
PAGE NOs CHECK
FROM TO LAB EPA
5. Semivolatlles Data (cont.)
b. Sample Data
TCL Results (Form I SV)
Tentatively Identified Compounds (Form I SV-TIC)
Reconstructed total ion chromatograms (RIC)
for each sample
For each sample:
Raw spectra and background-subtracted
mass spectra of target compounds
Mass spectra of TICs with three best library matches
GPC chromatograms (if GPC performed)
c. Standards Data (All Instruments)
Initial Calibration Data (Form VI SV)
RICs and Quan Reports for all Standards
Continuing Calibration (Form VII SV)
RICs and Quan Reports for all Standards
Internal Standard Area and RT Summary
(Form VIIIB and Form VIIIC SV)
d. QC Data
DFTPP
Blank Data
Matrix Spike Data
Matrix Spike Duplicate Data
6. Pesticides
a. QC Summary
Surrogate Percent Recovery Summary (Form II PEST)
MS/MSD Duplicate Summary (Form III PEST)
Method Blank Summary (Form IV PEST)
b. Sample Data
TCL Results - Organic Analysis Data Sheet
(Form I PEST)
Chromatograms (Primary Column)
Chromatograms from second GC column confirmation
GC Integration report or data system printout and
calibration plots
Manual work sheets
UV traces from GPC (if available)
For pesticides/Aroclors confirmed by GC/MS, copies
of raw spectra and copies of background-subtracted mass
spectra of target compounds (samples & standards)
FORM DC-2-2
OLMOL.O
-------
ORGANICS COMPLETE SDG FILE (CSF) INVENTORY SHEET (Cont.)
CASE NO.
SDG NO.
SOG NOS. TO FOLLOW
SAS NO.
PAGE NOs
FROM TO
CHECK
LAB EPA
6. Pesticides (cont.)
c. Standards Data
Pesticides Evaluation Standards Summary
(Form VIII PEST-1)
Pesticides Evaluation Standards Summary
(Form VIII, PEST-2)
Pesticide/Aroclor Standards Summary (Form IX, PEST)
Pesticide/Aroclor Identification (Form X PEST)
Standard chromatograms and data system printout
for all Standards
For pesticides/Aroclors confirmed by GC/MS, copies
of spectra for standards used
d. QC Data
Blank Data
Matrix Spike Data
Matrix Spike Duplicate 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)
8. EPA Shipping/Receiving Documents
Airbills (No. of shipments )
Chain-of-Custody Records
Sample Tags
Sample Log-In Sheet (Lab & DC1)
SDG Cover Sheet
Miscellaneous Shipping/Receiving Records
(describe or list)
9 . Internal Lab Sample Transfer Records and Tracking Sheets
(describe or list)
FORM DC-2-3
OLM01.0
-------
ORGANICS COMPLETE SDG FILE (CSF) INVENTORY SHEET (Cont.)
CASE NO.
SOG MO.
SOG MOS. TO FOLLOW
SAS MO.
10. Other Records (describe or list)
Telephone Communication Log
11 Comments:
PAGE NOs
FROM TO
CHECK
LAB EPA
Completed by:
(CLP Lab)
(Signature)
(Printed Name/Title)
(Date)
Audited by:
(EPA)
(Signature)
(Printed Name/Title)
(Date)
FORM DC-2-4
OLM01.0
-------
EXHIBIT C
TARGET COMPOUND LIST (TCL) AND
CONTRACT REQUIRED QUANTITATION LIMITS (CRQL)
NOTE: The values in these tables are quantisation limits, not absolute
detection limits. The amount of material necessary to produce a detector
response that can be identified and reliably quantified is greater than that
needed to simply be detected above the background noise. The quantitation
limits in these tables are set at the concentrations in the sample equivalent
to the concentration of the lowest calibration standard analyzed for each
analyte.
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 the specifications given in Exhibit D. For each fraction
and matrix, a brief synopsis of the sampling handling and analysis steps is
given, along with an example calculation for the CRQL value. All CRQL values
are rounded to two significant figures. For soil samples, the moisture
content of the samples is not considered in these example calculations.
C-l OLM01.0
-------
TARGET COMPOUND LIST (TCL) AND CONTRACT REQUIRED QUANTITATION LIMITS (CRQL)
Volatiles
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.
Ch lo r ome thane
B r omome thane
Vinyl Chloride
Chloroe thane
Methylene Chloride
Acetone
Carbon Disulfide
1 , 1-Dichloroethene
1, 1-Dichloroethane
1,2-Dichloroethene (total)
Chloroform
1 , 2-Dichloroethane
2 - Butanone
1,1, 1 -Trichloroe thane
Carbon Tetrachloride
Bromodichlorome thane
1 , 2 -Dichloropropane
cis-1 , 3-Dichloropropene
Trichloroethene
Dibromochlorome thane
1, 1,2 -Trichloroe thane
Benzene
trans -1,3 - Dichloropropene
Bromoform
4 -Me thyl - 2 -pentanone
2-Hexanone
Te tr achloroe thene
Toluene
1,1,2, 2 -Tetrachloroethane
Chlorobenzene
Ethyl Benzene
Styrene
Xylenes (Total)
CAS Number
74-87-3
74-83-9
75-01-4
75-00-3
75-09-2
67-64-1
75-15-0
75-35-4
75-34-3
540-59-0
67-66-3
107-06-2
78-93-3
71-55-6
56-23-5
75-27-4
78-87-5
10061-01-5
79-01-6
124-48-1
79-00-5
71-43-2
10061-02-6
75-25-2
108-10-1
591-78-6
127-18-4
108-88-3
79-34-5
108-90-7
100-41-4
100-42-5
1330-20-7
Quant i tat ion
Low
Water Soil
u£/L ue/Ke
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
Limits*
Med.
Soil
ue/Ke
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
1200
On
Column
(nz.)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
(50)
* Quantitation limits listed for soil/sediment are based on wet weight. The
quantitation limits calculated by the laboratory for soil/sediment,
calculated on dry weight basis as required by the contract, will be higher.
C-2
OLM01.0
-------
Note that the CRQL values listed on the preceding page may not be those
specified in previous CLP Statements of Work. These values are set at
concentrations in the sample equivalent to the concentration of the lowest
calibration standard specified in Exhibit D VOA. Lower quantitation limits
may be achievable for water samples by employing the Statement of Work for
Low Concentration Water for Organic Analyses.
VOLATILES
Water Samples
A 5 mL volume of water is purged with an inert gas at ambient temperature.
The volatiles are trapped on solid sorbents, and desorbed directly onto the
GC/MS. For a sample with compound X at the CRQL of 10 ug/L:
(10 ug/L) (5 mL) (10"3 L/mL) - 50 x 10'3 ug - 50 ng on the GC column
Low Level Soil/Sediment Samples
A 5 g aliquot of the soil/sediment sample is added to a volume of water in a
purge tube, heated, and purged with an inert gas. The volatiles are trapped,
and later desorbed directly onto the GC/MS. For a sample with compound X at
the CRQL of 10 ug/Kg:
(10 ug/Kg) (5 g) (10"-* Kg/g) - 50 x 10° ug - 50 ng on the GC column
Medium Level Soil/Sediment S
A 4 g aliquot of soil/sediment is extracted with 10 mL of methanol, and
filtered through glass wool. Only 1 mL of the methanol extract is taken for
screening and analysis. Based on the results of a GC/FID screen, an aliquot
of the methanol extract is added to 5 mL of reagent water and purged at
ambient temperature. The largest aliquot of extract considered in Exhibit D
is 100 uL. For a sample with compound X at the CRQL of 1200 ug/Kg:
(1200 ug/Kg) (4 g) (10'3 Kg/g) - 4800 x 10'3 ug - 4800 ng
This material is contained in the 10 mL methanol extract:
(4800 ng)/ 10 mL - 480 ng/mL
Of which, 100 uL are purged from the reagent water.
(480 ng/mL) (100 uL) (10~3 mL/uL) - 480 x 10"1 ng = 50 ng on the GC column
Note that for both low and medium soil/sediment samples, while it may affect
the purging efficiency, the volume of reagent water used in the purging
process does not affect the calculations.
C-3 OLM01.0
-------
TARGET COMPOUND LIST (TCL) AND CONTRACT REQUIRED QUANTITATION LIMITS (CRQL)
Quant1Cation Limits*
Semivolatiles
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
Phenol
bis(2-Chloroethyl) ether
2-Chlorophenol
1 , 3 -Dichlorobenzene
1,4- Dichlorobenzene
1 , 2 -Dichlorobenzene
2-Methylphenol
2,2' -oxybis
( 1 - Chloropropane ) *
4-Methylphenol
N-Nitroso-di-n-
dipropylamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2 , 4 - Dime thy Iphenol
b is ( 2 - Chloroethoxy )
methane
2,4-Dichlorophenol
1,2,4-Trichlorobenzene
Naphthalene
4 - Chloroaniline
Hexachlorobutadiene
4 - Chloro - 3 -me thy Iphenol
2 -Methylnaphthalene
Hexachlorocyclopentadiene
2 ,4,6-Trichlorophenol
2,4,5 -Trichlorophenol
2 - Chloronaphthalene
2-Nitroaniline
Dime thy Iphthalate
Acenaphthylene
2, 6 -Dinitro toluene
3-Nitroaniline
Acenaphthene
2 , 4-Dinitrophenol
4-Nitrophenol
CAS Number
108-95-2
111-44-4
95-57-8
541-73-1
106-46-7
95-50-1
95-48-7
108-60-1
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
120-82-1
91-20-3
106-47-8
87-68-3
59-50-7
91-57-6
77-47-4
88-06-2
95-95-4
91-58-7
88-74-4
131-11-3
208-96-8
606-20-2
99-09-2
83-32-9
51-28-5
100-02-7
Water
ue/L
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
50
10
50
10
10
10
50
10
50
50
Low
Soil
ue/Kg
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
1700
330
1700
330
330
330
1700
330
1700
1700
Med.
Soil
ue/Ke
10000
10000
10000
10000
10000
10000
10000
10000
10000
s
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
50000
10000
50000
10000
10000
10000
50000
10000
50000
50000
On
Column
(ng)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(100)
(20)
(100)
(20)
(20)
(20)
(100)
(20)
(100)
(100)
# Previously known by the name bis(2-Chloroisopropyl) ether
C-4
OLM01.0
-------
(continued)
Semivolatiles
CAS Number
Ouantitation Limits*
Low Med.
Water Soil Soil
UE/L UE/KE UE/KE
69. Dibenzofuran 132-64-9
70. 2,4-Dinitrotoluene 121-14-2
71. Diethylphthalate 84-66-2
72. 4-Chlorophenyl-phenyl
ether 7005-72-3
73. Fluorene 86-73-7
74. 4-Nitroaniline 100-01-6
75. 4,6-Dinitro-2-methylphenol 534-52-1
76. N-nitrosodiphenylamine 86-30-6
77. 4-Bromophenyl-phenylether 101-55-3
78. Hexachlorobenzene 118-74-1
79. Pentachlorophenol 87-86-5
8 0. Phenanthrene 85-01-8
81. Anthracene 120-12-7
82. Carbazole 86-74-8
83. Di-n-butylphthalate 84-74-2
84. Fluoranthene 206-44-0
85. Pyrene 129-00-0
86. Butylbenzylphthalate 85-68-7
87. 3,3'-Dichlorobenzidine 91-94-1
88. Benzo(a)anthracene 56-55-3
89. Chrysene 218-01-9
90. bis(2-Ethylhexyl)phthalate 117-81-7
91. Di-n-octylphthalate 117-84-0
92. Benzo(b)fluoranthene 205-99-2
93. Benzo(k)fluoranthene 207-08-9
94. Benzo(a)pyrene 50-32-8
95. Indeno(l,2,3-cd)pyrene 193-39-5
96. Dibenr(a,h)anthracene 53-70-3
97. Benzo(g,h,i)perylene 191-24-2
10
10
10
10
10
50
50
10
10
10
50
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
330
330
330
330
330
1700
1700
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
10000
10000
10000
10000
10000
50000
50000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
(20)
(20)
(20)
(20)
(20)
(100)
(100)
(20)
(20)
(20)
1700
330
330
330
330
50000
10000
10000
10000
10000
(100)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
* Quantitation limits listed for soil/sediment are based on wet weight. The
quantitation limits calculated by the laboratory for soil/sediment,
calculated on dry weight basis as required by the contract, will be higher.
C-5
OLM01.0
-------
SEMIVOLATILES
Water Samples
AIL volume of water is extracted three times with 100 mL of methylene
chloride at a pH of approximately 2. This extract is reduced in volume to
1.0 mL, and a 2 uL volume is injected onto the GC/MS for analysis. For a
sample with compound X at the CRQL of 10 ug/L:
(10 ug/L) (1 L) - 10 ug in the original extract
When the extract is concentrated, this material is contained in the 1 mL
concentrated extract, of which 2 uL are injected into the instrument:
(10 ug/mL) (2 uL) (10'3 mL/uL) - 20 x 10"3 ug - 20 ng on the GC column
Low Soil Samples
A 3^ g soil sample is extracted three times with methylene chloride at
ambient pH, by sonication. The extract is reduced in volume to 1.0 mL, and a
2 uL volume is injected onto the GC/MS for analysis. For a sample with
compound X at the CRQL of 330 ug/Kg:
(330 ug/Kg) (30 g) (10'3 Kg/g) - 9900 x 10'3 ug - 9.9 ug
When the sample extract is to be subjected to Gel Permeation Chromatography
(required) to remove high molecular weight interferences, the volume of the
extract is initially reduced to 10 mL. This 10 mL is put through the GPC
column, and only 5 mL are collected off the GPC. That 5 mL volume is reduced
to 0.5 mL prior to analysis. Therefore:
(9.9 ug/10 mL) (5 mL) - 4.95 ug
This material is contained in the 0.5 mL extract, of which 2 uL are injected
into the instrument:
(4.95 ug/0.5 mL) (2 uL) (10~3 mL/uL) - 1.98 x 10"2 ug ~ 20 ng on the GC column
Medium Soil Samples
A 1 g soil sample is extracted once with 10 mL of methylene chloride, which
is filtered through glass wool to remove particles of soil. The filtered
extract is then subjected to GPC clean up, and only 5 mL of extract are
collected after GPC. This extract is reduced in volume to 0.5 mL, of which 2
uL are injected onto the GC/MS. For a sample with compound X at the CRQL of
10,000 ug/Kg:
(10,000 ug/Kg) (Ig) (10'3 Kg/g) - 10 ug
(continued)
C-6 OLM01.0
-------
Semivolatiles, Medium Soil, continued -
This material is contained in the 10 mL extract, of which only 5 mL are
collected after GPC:
(10 ug) (5 mL/10mL) - 5 ug
The volume of this extract is reduced to 0.5 mL, of which 2 uL are injected
into the instrument:
(5 ug/0.5 mL) (2 uL) (10"3 mL/uL) - 20 x 10"3 ug - 20 ng on the GC column
c'7 OLM01.0
-------
TARGET COMPOUND LIST (TCL) AND CONTRACT REQUIRED QUANTITATION LIMITS (CRQL)
_Pestic ides/Aroclors
_CAS Number
Ouantitation Limits*
Water Soil On Column
ug/L ug/Kg (pg)
98.
99.
100.
101.
102.
alpha- BHC
beta-BHC
delta -BHC
gamma -BHC (Lindane)
Heptachlor
319
319
319
58
-84-
-85-
-86-
-89-
76-44-
6
7
8
9
8
0
0
0
0
0
.05
.05
.05
.05
.05
1
1
1
1
1
.7
.7
.7
.7
.7
5
5
5
5
5
103. Aldrin 309-00-2 0.05 1.7
104. Heptachlor epoxide 1024-57-3 0.05 1.7
105. Endosulfan I 959-98-8 0.05 1.7
106. Dieldrin 60-57-1 0.10 3.3
107. 4,4'-DDE 72-55-9 0.10 3.3
108. Endrin 72-20-8 0.10 3.3
109. Endosulfan II 33213-65-9 0.10 3.3
110. 4,4'-ODD 72-54-8 0.10 3.3
111. Endosulfan sulfate 1031-07-8 0.10 3.3
112. 4,4'-DDT 50-29-3 0.10 3.3
113. Methoxychlor
114. Endrin ketone
115. Endrin aldehyde
116. alpha-Chlordane
117. gamma-Chlordane
118. Toxaphene 8001-35-2 5.0
119. Aroclor-1016 12674-11-2 1.0
120. Aroclor-1221 11104-28-2 1.0
121. Aroclor-1232 11141-16-5 2.0
122. Aroclor-1242 53469-21-9 1.0
123. Aroclor-1248 12672-29-6 1.0
124. Aroclor-1254 11097-69-1 1.0
125. Aroclor-1260 11096-82-5 1.0
72-43-5
53494-70-5
7421-36-3
5103-71-9
5103-74-2
0.50
0.10
0.10
0.05
0.05
17.0
3.3
3.3
1.7
1.7
170.0
33.0
33.0
67.0
33.0
33.0
33.0
33.0
5
5
5
10
10
10
10
10
10
10
50
10
10
5
5
500
100
100
200
100
100
100
100
* Quantitation limits listed for soil/sediment are based on wet weight. The
quantitation limits calculated by the laboratory for soil/sediment,
calculated on dry weight basis as required by the contract, will be higher.
There is no differentiation between the preparation of low and medium soil
samples in this method for the analysis of Pesticides/Aroclors.
C-8
OLM01.0
-------
PESTICIDES/AROCLORS
Water Samples
A 1 L volume of water is extracted three times with 100 mL of raethylene
chloride. This extract is reduced in volume to approximately 3-5 mL, and
diluted up to 10.0 mL with clean solvent. Although not required, if Gel
Permeation Chromatography is performed, only 5 of the 10 mL of extract are
collected after GPC.
Regardless of whether GPC is performed, only 1.0 mL of the 10.0 mL of the
original extract is taken through the remaining clean up steps (Florisil and
sulfur removal). The final volume of the extract after the clean up steps
depends on the requirements of the autosampler. If the autosampler can
handle 1.0 mL final extract volumes, this is the final volume. If the
autosampler cannot reliably handle 1.0 mL volumes, the final volume is 2.0
mL. When using an autosampler, the injection volume may be 1.0 or 2.0 uL.
Manual injections must use a 2.0 uL injection volume.
For a sample with compound X at the CRQL of 0.05 ug/L:
(0.05 ug/L) (1 L) - 0.05 ug in the original extract
This material is contained in the 10.0 mL of extract:
(0.05 ug)/ (10.0 mL) - 0.005 ug/mL
Of which, only 1.0 mL is carried through the remaining clean up steps. For a
final extract volume of 1.0 mL and a 1 uL injection volume:
(0.005 ug/mL) (1 uL)(10"3 mL/uL) - 5 x 10"6 ug - 5 pg on the GC column
Soil Samples
There is no differentiation between the preparation of low and medium soil
samples in this method for the analysis of pesticides/Aroclors. A 30 g soil
sample is extracted three times with methylene chloride by sonication. The
extract is reduced in volume to 10.0 mL and subjected to Gel Permeation
Chromatography. After GPC, only 5.0 mL of extract are collected. However,
as with the water sample described above, only 1,0 mL of that extract is
subjected to the other clean up steps, so no loss of sensitivity results from
the use of GPC. From this point on, the soil sample extract is handled in
the same fashion as the extract of a water sample. For a sample with
compound X at the CRQL of 1.7 ug/Kg:
(1.7 ug/Kg) (30 g) (10° Kg/g) - 51 x 10-i ug - 51 ng in the original extract
This material is contained in the 10.0 mL of extract:
(51 ng)/ 10 mL - 5.1 ng/mL
(continued)
C-9 OLM01.0
-------
Pesticides/Aroclors, continued -
Of which, only 1.0 mL is carried chrough the remaining clean up steps. For a
final extract volume of 1.0 mL and a 1 uL injection volume:
(5.1 ng/mL)(l uL)(10"3 mL/uL) - 5.1 x 10'3 ng « 5 pg on the GC column.
For either water or soil samples, if the autosampler used requires a 2.0 mL
final volume, the concentration in the 10.0 mL of extract above remains the
same.
Using a 2 uL injection volume, twice the total number of picograms are
injected onto the GC column. However, because the injection volume must be
the same for samples and standards, twice as much material is injected onto
the column during calibration, and thus the amount of compound X injected
from the sample extract is equivalent to the amount of compound X injected
from the calibration standard, regardless of injection volume.
C-10 OLM01.0
-------
EXHIBIT D
ANALYTICAL METHODS
FOR VOLATILES
D-l/VOA OML01.0
-------
Table of Contents
Page
SECTION I - Introduction D-3/VOA
SECTION II - Sample Preparation and Storage D-5/VOA
PART A - Sample Storage and Holding Times D-6/VOA
PART B - Protocols for Hexadecane
Extraction of Volatiles from
Water and Soil/Sediment for
Optional Screening D-7/VOA
SECTION III - Optional Screening of Hexadecane
Extracts for Volatiles D-10/VOA.
s
SECTION IV - GC/MS Analysis of Volatiles D-14/VOA
D-2/VOA OLM01.0
-------
SECTION I
INTRODUCTION
The analytical methods that follow are designed to analyze water, sediment
and soil from hazardous waste sites for the organic compounds on the Target
Compounds List (TCL, see Exhibit C). The methods are based on EPA Method 624
(Purgeables).
The methods are divided into the following sections: sample preparation,
screening, and analysis. Sample preparation covers sample storage, sample
holding times, and medium level sample extraction. As described in the
screening section, a portion of a hexadecane extract may be screened on a gas
chromatograph with appropriate detectors to determine the concentration level
of organics. The analysis section contains the GC/MS analytical methods for
organics. The purge and trap technique, including related sample
preparation, is included in the analysis section because GO/MS operation and
the purge and trap technique are interrelated.
D-3/VOA OLM01.0
-------
SECTION I
1. Method for the Determination of Volatile (Purgeablel Organic Compounds
1.1 Scope and Application
This method covers the determination of the target volatile (purgeable)
organics as listed in Exhibit C. The contract required quantitation
limits are also listed in Exhibit C. The method includes an optional
hexadecane screening procedure. The extract is screened on a gas
chromatograph/flame ionization detector (GC/FID) to determine the
approximate concentration of organic constituents in the sample. The
actual analysis is based on a purge and trap gas chromatographic/mass
spectrometer (GC/MS) method. For soil/sediment samples, the purge
device is heated.
1.2 Problems have been associated with the following compounds analyzed by
this method:
o Chloromethane, vinyl chloride, bromomethane, and chloroethane
can display peak broadening if the compounds are not delivered
to the GC column in a tight band. "
o Acetone, hexanone, 2-butanone, and 4-methyl-2-pentanone have
poor purge efficiencies.
o 1,1,1-Trichloroethane and all the dichloroethanes can
dehydrogenate during storage or analysis.
o Tetrachloroethane and 1,1-dichloroethane can be degraded by
contaminated transfer lines in purge and trap systems and/or
active sites in trapping materials.
o Chloromethane can be lost if the purge flow Ls too fast.
o 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 the GC/MS to meet the instrument
performance criteria for BFB at ions m/z 174/176. Increasing
the m/z 174/176 ratio may improve bromoform response.
1.3 Because performance data indicate erratic and poor linearity, Che
following compounds have no Maximum %RSD, or Maximum %0ifference
criteria; however, these compounds must meet a minimum RRF criterion of
0.010:
Acetone 1,2-Dichloropropane
2 -Butanone 2 -Hexanone
Carbon disulfide Methylene chloride
Chloroethane 4-Methyl-2-pentanone
Chloromethane Toluene-dg
1,2-Dichloroethene (total) 1,2-Dichloroethane-d^
D-4/VOA OLM01.0
-------
SECTION II
SAMPLE PREPARATION AND STORAGE
D-5/VOA OLM01.0
-------
SECTION II
PART A - SAMPLE STORAGE AND HOLDING TIMES
1. Procedures for Sample Storage
The samples must be protected from light and refrigerated at 4°C (±2°C)
from the time of receipt until 60 days after delivery of a complete
sample data package to the Agency. After 60 days, the samples may be
disposed of in a manner that complies with all applicable regulations.
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 purgeable samples received under this contract.
Samples and standards must be stored separately.
2. Contract Required Holding Times
Analysis of water samples must be completed within 10 days of validated
time of sample receipt (VTSR), and analysis of soil/sediment samples
must be completed within 10 days of VTSR.
D-6/VOA OLM01.0
-------
SECTION rr
• PROTOCOLS FOR HEXADECANE EXTRACTION OF VOLATILES FROM WATER AND
SOIL/SEDIMENT FOR OPTIONAL SCREENING
1. Summary of Method
1.1 Matrices
1.1.1 Water - a 40 mL aliquot of sample is extracted with 2 mL of
hexadecane. This provides a minimum quantitation limit (MQL)
as follows:
Compounds MOL ug/L
non-halogenated aromatics 40- 50
halogenated methanes 800-1000
halogenated ethanes 400- 500
1.1.2 Soil/sediment - 40 mL of reagent water are added to 10 g (wet
weight) of soil and shaken. The water phase is in turn
extracted with 2 mL of hexadecane. This provides a minimum
quantitation limit of approximately four times higher than
those listed for water.
1.2 The hexadecane extraction and screening protocols for purgeables are
optional. These protocols are included to aid the analyst in deciding
whether a sample is low or medium level. The use of these or other
screening protocols could prevent saturation of the purge and trap
system and/or the GC/MS system. It is recommended that these or other
screening protocols be used, particularly if there is some doubt about
the level of organics in a sample. This is especially true in
soil/sediment analysis.
2. Limitations
These extraction and preparation procedures were developed for rapid
screening of water samples from hazardous waste sites. The design of
the methods thus does not stress efficient recoveries or low limits of
quantitation. Rather, the procedures were designed to screen at
moderate recovery and sufficient sensitivity for a broad spectrum of
organic chemicals. The results of the analyses thus may reflect only a
minimum of the amount actually present in some samples. This is
especially true if water soluble solvents are present.
3. Interferences
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that lead to
discrete artifacts and/or elevated baselines in the total ion current
profiles. All of these materials must be routinely demonstrated to be
free from interferences under the conditions of the analysis by running
laboratory reagent 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,
depending upon the nature and diversity of the site being sampled.
D-7/VOA OLM01.0
-------
SECTION II
4. Apparatus and Materials
4.1 Vials and caps - 2 mL for GC auto sampler.
4.2 Volumetric flask - 50 mL with ground glass stopper.
4.3 Pasteur pipets - disposable.
4.4 Centrifuge tube - 50 mL with ground glass stopper or Teflon-lined screw
cap.
4.5 Balance - analytical, capable of accurately weighing + 0.0001 g.
5. Reagents
5.1 Hexadecane and methanol - pesticide residue analysis grade or
equivalent.
5.2 Reagent water - defined as water in which an interferent is not
observed at the CRQL of each parameter of interest.
5.3 Standard mixture #1 containing benzene, toluene, ethyl benzene and
xylene. Standard mixture #2 containing n-nonane and n-dodecane.
5.3.1 Stock standard solutions (1.00 ug/uL) - prepared from pure
standard materials or purchased as certified solutions.
5.3.1.1 Prepare stock standard solutions by accurately
weighing about 0.0100 g of pure material. Dissolve
the material in methanol and dilute to volume in a
10 mL volumetric flask. Larger volumes can be used
at the convenience of the analyst. If compound
purity is certified at 96% or greater, the weight
can be used without correction to calculate the
concentration of the stock standard.
5.3.1.2 Transfer the stock scandard solutions into multiple
Teflon-sealed screw-cap vials. Store, with no
head-space, at -10*C to -20°C, and protect: from
light. Stock standard solutions should be checked
frequently for signs of degradation or evaporation,
especially just prior to preparing calibration
standards from them. These solutions must: be
replaced after six months, or sooner, if comparison
with quality control check samples indicates a
problem. Standards prepared from gases or reactive
compounds such as styrene must be replaced after two
months, or sooner, if comparison with quality
control check samples indicates a problem.
5.3.2 Prepare working standards of mixtures #1 and #2 at 100 ng/uL of
each compound in methanol. Store these solutions as in 5.3.1.2
above.
D-8/VOA OLM01.0
-------
SECTION II
6. S_ample Extraction
6.1 Water
6.1.1 Allow the contents of the 40 mL sample vial to come to room
temperature. Quickly transfer the contents of the 40 mL sample
vial to a 50 mL volumetric flask. Immediately add 2.0 mL of
hexadecane, cap the flask, and shake vigorously for 1 minute.
Let phases separate. Open the flask and add sufficient reagent
water to bring the hexadecane layer into the neck of the flask.
6.1.2 Transfer approximately 1 mL of the hexadecane layer to a 2.0 mL
GC vial. If an emulsion is present after shaking the sample,
break it by doing the following:
o Pulling the emulsion through a small plug of Pyrex glass
wool packed in a pipet, or
o Transferring the emulsion to a centrifuge tube and
centrifuging for several minutes.
6.1.3 Add 200 uL of working standard mixture #1 and #2 to separate 40
mL portions of reagent water. Follow steps 6.1.1 - 6.1.2,
starting with the immediate addition of 2.0 mL of hexadecane.
6.2 Soil/Sediment
6.2.1 Add approximately 10 g of soil (wet weight) to 40 mL of reagent
water in a 50 mL centrifuge tube with a ground glass stopper or
teflon-lined cap. Cap and shake vigorously for one minute.
Centrifuge the capped flask briefly. Quickly transfer
supernatant water to a 50 mL volumetric flask equipped with a
ground-glass stopper.
6.2.2 Follow 6.1, starting with the addition of 2.0 mL of hexadecane.
7. Sample Analysis
The sample is ready for GC/FID screening. Proceed to Section III,
Optional Screening of Hexadecane Extracts for Volatiles.
D-9/VOA OLM01.0
-------
SECTION III
OPTIONAL SCREENING OF HEXADECANE
EXTRACTS FOR VOLATILES
D-10/VOA OLM01.0
-------
SECTION III
1. Summary of Method
The hexadecane extracts of water and soil/sediment are screened on a
gas chromatograph/flame ionization detector (GC/FID). The results of
the screen will determine if volatile organics are to be analyzed by
low or medium level GC/MS procedures if the sample is a soil/sediment,
or to determine the appropriate dilution factor if the sample is water.
2. Apparatus and Materials
2.1 Gas chromatograph - an analytical system complete with gas
chromatograph suitable for on-column injection and all required
accessories including syringes, analytical columns, gases, detector,
and strip-chart recorder. A data system is recommended for measuring
peak areas.
2.1.1 Above-described GC, equipped with flame ionization detector.
2.1.2 GC column - 3 m x 2 mm ID glass column packed with 10% OV-101
on 100-120 mesh Chromosorb W-HP (or equivalent). The column
temperature should be programmed from 80°C to 280°C at
16°C/min. and held at 280'C for 10 minutes.
3. Reagents
Hexadecane - pesticide residue analysis grade or equivalent.
4. Limitations
4.1 The flame ionization detector varies considerably in sensitivity when
comparing aromatics and halogenated methanes and ethanes. Halomethanes
are approximately 20x less sensitive than aromatics and haloethanes
approximately lOx less sensitive. Low molecular weight, water soluble
solvents, e.g., alcohols and ketones, will not extract from the water,
and therefore will not be detected by the GC/FID.
4.2 Following are two options for interpreting the GC/FID chromatogram.
4.2.1 Option A is to use standard mixture #1 containing the aromatics
to calculate an approximate concentration of the aromatics in
the sample. Use this information to determine the proper
dilution for purge and trap if the sample is a water, or
whether to use the low or medium level GC/MS purge and trap
methods if the sample is a soil/sediment (see Table 1,
paragraph 6.2.1.3 for guidance). This should be the best
approach; however, the aromatics may be absent or obscured by
higher concentrations of other purgeables. In these cases,
Option B may be the best approach.
4.2.2 Option B is to use standard mixture #2 containing n-nonane and
n-dodecane to calculate a factor. Use the factor to calculate
a dilution for purge and trap of a water sample or to determine
whether to use the low or medium level GC/MS purge and trap
methods for soil/sediment samples (see Table 1, paragraph
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SECTION III
6.2.1.3 for guidance). All purgeables of interest have
retention times less than the n-dodecane.
5. Extract Screening
5.1 External standard calibration - Standardize the GC/FID each 12 hr.
shift for half scale response. This is done by injecting 1-5 uL of the
extracts that contain approximately 10 ng/uL each of mix #1 and mix #2
compounds, as prepared in 5.3, Section II, Part B. Use the GC
conditions specified in paragraph 2.1.2.
5.2 Inject the same volume of hexadecane extract as the extracted standard
mixture in 5.1. Use the GC conditions specified in 2.1.2.
6. Analytical Decision Point
6.1 Water
6.1.1 Compare the chromatograms of the hexadecane extract of the
sample with those of the reagent blank and extract of the
standard.
6.1.1.1 If no peaks are noted, other than those also in the
reagent blank, analyze a 5 mL water sample by purge
and trap GC/MS.
6.1.1.2 If peaks are present prior to the n-dodecane and the
aromatics are distinguishable, follow Option A
(4.2.1).
6.1.1.3 If peaks are present prior to the n-dodecane but the
aromatics are absent or indistinguishable, use
Option B as follows: if all peaks are <3% of the
n-nonane, analyze a 5 mL water sample by purge and
trap GC/MS. If any peaks are >3% of the n-nonane,
measure the peak height or area of the major peak
and calculate the dilution factor as follows:
peak area of sample major peak en dilution
peak area of n-nonane factor
The water sample will be diluted using the
calculated factor just prior to purge and trap GC/MS
analysis.
6.2 Soil/Sediment
6.2.1 Compare the chromatograms of the hexadecane extract of the
sample with those of the reagent blank and extract of the
standard.
6.2.1.1 If no peaks are noted, other than those also in the
reagent blank, analyze a 5 g sample by low level
GC/MS.
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SECTION III
6.2.1.2 If peaks are present prior to the n-dodecane and the
aromatics are distinguishable, follow Option A
(4.2.1) and the concentration information in Table
1, paragraph 6.2.1.3, to determine whether to
analyze by low or medium level method.
6.2.1.3 If peaks are present prior to the n-dodecane but the
aromatics are absent or indistinguishable, and using
Option B as follows, calculate a factor using the
following formula:
peak area of sample major peak — X Factor
peak area of n-nonane
Table 1 - Determination of GC/MS Purge & Trap Method
Approximate
Concentration Range*
X Factor Analyze by (ug/kg)
0-1.0 low level method 0-1,000
>1.0 medium level method >1,000
* This concentration range is based on the response of aromatics to GC/FID.
When comparing GC/FID responses, the concentration for halomethanes is 2Ox
higher, and that for haloethanes is lOx higher.
6.3 Sample Analysis
Proceed to Section IV, GC/MS Analysis of Volatiles.
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SECTION IV
GC/MS ANALYSIS
OF VOLATILES
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SECTION IV
1. Summary of Methods
1.1 Water Samples
An inert gas is bubbled through a 5 mL sample contained in a
specifically designed purging chamber at ambient temperature. The
purgeables are efficiently transferred from the 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 chromatographic column. The gas chromatograph is
temperature programmed to separate the purgeables which are then
detected with a mass spectrometer.
An aliquot of the sample is diluted with reagent water when dilution is
necessary. A 5 mL aliquot of the dilution is taken for purging.
1.2 Soil/Sediment Samples
s
1.2.1 Low level - an inert gas is bubbled through a mixture of a 5 g
sample and reagent water contained in a suggested specially
designed purging chamber at elevated temperatures. The
purgeables are efficiently transferred from the 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
chromatographic column. The gas chromatograph is temperature
programmed to separate the purgeables, which are then detected
with a mass spectrometer.
1.2.2 Medium level - a measured amount of soil is extracted with
methanol. A portion of the methanol extract is diluted to 5 mL
with reagent water. An inert gas is bubbled through this
solution in a specifically designed purging chamber at: ambient
temperature. The purgeables are effectively transferred from
the 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 chromatographic column. The gas chromatograph is
temperature programmed to separate the purgeables, which are
then detected with a mass spectrometer.
2. Interferences
2.1 Impurities in the purge gas, organic compounds out-gassing from the
plumbing ahead of the trap, and solvent vapors in the laboratory
account for the majority of contamination problems. The analytical
system must be demonstrated to be free from contamination under the
conditions of the analysis by running laboratory reagent blanks as
described in Exhibit E. The use of non-TFE tubing, non-TFE thread
sealants, or flow controllers with rubber components in the purging
device should be avoided.
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2.2 Samples can be contaminated by diffusion of volatile organics
(particularly fluorocarbons and methylene chloride) through the septum
seal into the sample during storage and handling. A holding blank
prepared from reagent water and carried through the holding period and
the analysis protocol serves as a check on such contamination. One
holding blank per case should be analyzed. Data must be retained by
the laboratory and be made available for inspection during on-site
evaluations.
2.3 Contamination by carry-over 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 should be followed by an•analysis of reagent water to
check for cross contamination. For samples containing large amounts of
water soluble materials, suspended solids, high boiling compounds or
high purgeable levels, between analyses, it may be necessary to wash
out the purging device with a detergent solution, rinse it with
distilled water, and then dry it in a 105'C oven. 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.
2.4 The laboratory where volatile analysis is performed should be
completely free of solvents.
3. Apparatus and Materials
3.1 Micro syringes - 25 uL and larger, 0.006 inch ID needle.
3.2 Syringe valve - two-way, with Luer ends (three each), if applicable to
the purging device.
3.3 Syringe - 5 mL, gas-tight with shut-off valve.
3.4 Balance - analytical, capable of accurately weighing + 0.0001 g, and a
top-loading balance capable of weighing +0.1 g.
3.5 Glassware
o Bottle - 15 mL, screw cap, with Teflon cap liner.
o Volumetric flasks - class A with ground-glass stoppers.
o Vials - 2 mL for GC autosampler.
3.6 Purge and trap device - consists of three separate pieces of equipment:
the sample purger, trap, and the desorber. Several complete devices
are now commercially available.
3.6.1 The sample purger must be designed to accept 5 mL samples with
a water column at least 3 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
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SECTION IV
than 3 mm at the origin. The purge gas must be introduced no
more than 5 mm from the base of the water column.
3.6.2 The trap must be at least 25 cm long and have an inside
diameter of at least 0.105 inch. The trap must be packed to
contain the following minimum lengths of absorbents: 15 cm of
2,6-diphenylene oxide polymer (Tenax-GC, 60/80 mesh) and 8 cm
of silica gel (Davison Chemical, 35/60 mesh, grade 15, or
equivalent).
3.6.3 The desorber should 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.
3.6.4 The purge and trap device may be assembled as a. separate unit
or be coupled to a gas chromatograph.
3.6.5 A heater or heated bath capable of maintaining the purge device
at 40°C ± 1°C is to be used.
3.7 GC/MS system
3.7.1 Gas Chromatograph - the gas chromatograph (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 paragraph 3.6 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. If capillary columns are to be used (see below) , the
column oven must be cooled to 10*C; therefore, a subambient
oven controller is required.
3.7.2 Gas Chromatography Columns
3.7.2.1 Packed Columns - 6 ft long x 0.1 in ID glass, packed
with 1% SP-1000 on Carbopack B (60/80 mesh) or
equivalent.
NOTE: Capillary columns may be used for analysis of
volatiles, as long as the Contractor uses the
instrumental parameters in EPA Method 524.2 as
guidelines, uses the internal standards and
surrogates specified in this contract, and
demonstrates that the analysis meets all of the
performance and QA/QC criteria contained in this
contract.
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SECTION IV
3.7.2.2 Capillary Columns
o 30 m long x 0.53 mm ID VOCOL (Supelco, Inc., or
equivalent) fused silica wide-bore capillary
column with 3 urn film thickness.
OR
o 30 m long x 0.53 mm ID DB-624 fused silica wide-
bore (J&W Scientific, Inc., or equivalent) column
with 3 um film thickness.
3.7.3 Mass Spectrometer - must be capable of scanning from 35 to 300
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 instrument
performance acceptance criteria when 50 ng of
p-bromofluorobenzene (BFB) is injected through the gas
chromatograph inlet. The instrument conditions required for
the acquisition of the BFB mass spectrum are ^given in paragraph
6.4.4. NOTE: BFB criteria must be met before any sample
extracts are analyzed. Any samples analyzed when BFB criteria
have not been met will require reanalysis at no cost to the
Agency. To ensure sufficient precision of mass spectral data,
the MS scan rate should 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 the outside of the facility or to a trapping system
which prevents the release of contaminants into the instrument
room.
3.7.4 GC/MS interface - any gas chromatograph to mass spectrometer
interface that gives acceptable calibration points, at 50 ng or
less per injection, for each of the parameters of interest and
achieves all acceptance criteria may be used. Gas
chromatograph to mass spectrometer interfaces constructed of
all-glass or glass-lined materials are recommended. Glass can
be deactivated by silanizing with .dichlorodimethylsilane.
3.7.5 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 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 for the comparison of sample spectra
against reference library spectra. The 1989 (or most recent)
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SECTION IV
release of the NIST/EPA/MSDC 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.
3.7.6 Magnetic tape storage device - must be capable of recording
data and must be suitable for long-term, off-line storage.
4. Reagents
4.1 Reagent water - defined as water in which an interferent is not
observed at or above the CRQL of the parameters of interest.
4.1.1 Reagent water may be generated by passing tap water through a
carbon filter bed containing about 453 g of activated carbon
(Calgon Corp., Filtrasorb-300 or equivalent).
4.1.2 A water purification system (Millipore Super-Q or equivalent)
may be used to generate reagent water. s
4.1.3 Reagent water may also 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 and seal with a Teflon-lined
septum and cap.
4.2 Sodium thiosulfate - (ACS) granular.
4.3 Methanol - pesticide quality or equivalent.
5. S tandards
5.1 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 ertified. Manufacturer's
certificates of analysis must be retained by the Contractor and
presented upon request.
5.2 Stock Standard Solutions
Stock standard solutions may be purchased or may be prepared in
methanol from pure standard materials.
5.2.1 Prepare stock standard solutions by placing about 9.8 mL of
methanol into a 10.0 mL 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.
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SECTION IV
5.2.2 Add the assayed reference material as described below.
5.2.2.1 If the compound is a liquid, using a 100 /jL syringe,
immediately add two or more drops of assayed
reference material to the flask, then reweigh. The
liquid must fall directly into the alcohol without
contacting the neck of the flask.
5.2.2.2 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 5
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 Teflon tubing to the
side-arm relief valve and direct a gentle stream of
the reference standard into the methanol meniscus.
5.2.3 Reweigh, dilute to volume, stopper, then mix by inverting the
flask several times. Calculate the concentration in micrograms
per microliter 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.
5.2.4 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.
5.3 Secondary Dilution Standards
5.3.1 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.
5.3.2 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.
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SECTION IV
5.4 Working Standards
5.4.1 Instrument Performance Check Solution - p-Broraofluorobenzene
(BFB)
Prepare a 25 ng/VL solution of BFB in methanol. Prepare fresh
BFB solution every six months, or sooner, if the solution has
degraded or evaporated. NOTE: The 25 ng/^L concentration is
used with a 2 i±L injection volume. The laboratory may prepare
a 50 ng//*L solution of BFB if a 1 piL injection volume is used.
5.4.2 Calibration Standard Solution
Prepare the working calibration standard solution containing
all of the purgeable target compounds in methanol. The
recommended concentration of the target compounds is 100 ug/mL.
Prepare fresh working calibration standard solutions weekly, or
sooner, if solutions have degraded or evaporated.
s
5.4.3 Internal Standard Spiking Solution
Prepare an internal standard spiking solution containing
Bromochloromethane, Chlorobenzene-dg, and 1,4-Difluorobenzene
in methanol at the concentration of 25.0 ug/mL for each
internal standard. Add 10 nL of this spiking solution into 5.0
mL of sample or calibration standard for a concentration of 50
Pg/L. Prepare fresh spiking solution weekly or sooner if the
solution has degraded or evaporated.
5.4.4 System Monitoring Compound (SMC) Spiking Solution
Prepare a system monitoring compound spiking solution
containing Toluene-dg, p-Bromofluorobenzene, and 1-2-
Dichloroethane-d^ in methanol at a concentration of 25.0 /ig/mL.
Add 10.0 n~L of this spiking solution into 5.0 mL of sample, for
a concentration of 50 /*g/L. Prepare fresh spiking solution
every three months, or sooner if the solution has degraded or
evaporated.
5.4.5 Volatile Matrix Standard Spiking Solution
5.4.5.1 Prepare a spiking solution in methanol that contains
the following compounds at a concentration of 25.0
Mg/mL: 1,1-Dichloroethene, Trichloroethene,
Chlorobenzene, Toluene, and Benzene.
5.4.5.2 Matrix spikes also serve as duplicates; therefore,
add an aliquot of this solution to each of two
portions from one sample chosen for spiking.
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SECTION IV
5.5 Aqueous Calibration Standard Solutions
5.5.1 Prepare five aqueous initial calibration standard solutions
containing all of the purgeable target compounds and system
monitoring compounds at the 10, 20, 50, 100, and 200 ^g/L
levels. Note: These are not the same levels as have been used
in previous Statements of Work.
5.5.2 Aqueous calibration standards may be prepared in a volumetric
flask or in the syringe used to inject the standard into the
purging device.
5.5.2.1 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.
5.5.2.2 Syringe - remove the plunger from a 5 mL "Luerlock"
syringe. 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 5.0 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.
5.5.3 The 50 fig/L aqueous calibration standard solution is the
continuing calibration standard.
5.5.4 The methanol purged in each of the aqueous calibration
standards must not exceed 1% by volume.
5.6 Storage of Standards
5.6.1 Store the stock standards in Teflon-sealed screw-cap bottles
with zero headspace at -10°C to -20°C. 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.
5.6.2 Store secondary dilution standards in Teflon-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.
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SECTION IV
5.6.3 Aqueous standards may be stored for up to 24 hours if held in
Teflon-sealed screw-cap vials with zero headspace at 4°C.
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 for up to 12 hours in purge tubes connected via the
autosampler to the purge and trap device.
5.6.4 Purgeable standards must be stored separately from other
standards.
6. Instrument Operating Conditions
6.1 Purge and Trap Device
The following are the purge and trap analytical conditions:
Purge Conditions:
Purge Gas:
Purge Time:
Purge Flow Rate:
Purge Temperature:
Desorb Conditions:
Oesorb Temperature:
Desorb Flow Rate:
Desorb Time:
Trap Reconditioning Conditions:
Reconditioning Temperature:
Reconditioning Time:
Helium or Nitrogen
11.0 ±0.1 min
25-40 mL/min
Ambient
180°C
15 mL/min
4.0 ±0.1 min
180'C
7.0 min ±0.1 min
Before initial use, condition the trap overnight at 180°C by
backflushing with at least 20 mL/min flow of inert gas. Vent the trap
effluent to the room and not to 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 analysis of samples.
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SECTION IV
6.2 Gas Chromatograph
The following are the recommended gas chromatographic analytical
conditions:
6.2.1 Packed Columns
Carrier Gas: Helium
Flow Rate: 30 mL/min
Initial Temperature: 45°C
Initial Hold Time: 3 min
Ramp Rate: 8°C/min
Final Temperature: 220°C
Final Hold Time: 15 min
Transfer Line Temperature: 250-300°C
6.2.2 Capillary Columns
Carrier Gas: Helium
Flow Rate: 15 mL/min
Initial Temperature: 10"C
Initial Hold Time: 1.0 - 5.0 min (±0.1
min precision)
Ramp Rate: 6°C/min
Final Temperature: 160"C
Final Hold Time: Until all target
compounds elute
6.2.3 Optimize GC conditions for compound separation and sensitivity.
6.3 Mass Spectrometer
The following are the required mass spectrometer conditions:
Electron Energy: 70 Volts (nominal)
Mass Range: 35-300 amu
Scan Time: To give at least 5 scans per
peak, not to exceed 1 second per
scan
6.4 The GC/MS system must be tuned to meet the manufacturer's
specifications, using a suitable calibrant such as 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 (paragraph 5.4.1).
6.4.1 Prior to the analyses 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 p-
bromofluorobenzene (BFB).
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SECTION IV
6.4.2 The analysis of the instrument performance check .solution may
be performed as follows:
o As an injection of up to 50 ng of BFB into the GC/MS.
o By adding 50 ng of BFB to 5.0 ml of reagent water and
analyzing the resulting solution as if it were an
environmental sample (see section 8 below).
BFB may not be analyzed simultaneously with a calibration
standard.
6.4.3 The mass spectrum of BFB 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 prior to the elution of BFB.
NOTE: All instrument conditions must be identical to those
used in the sample analysis.
6.4.4 The analysis of the instrument performance check solution must
meet the ion abundance criteria given below.
TABLE 1
BFB KEY IONS AND ION 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.
6.4.5 The criteria listed above are based on adherence to the
acquisition specifications identified in paragraph 6.4.3, and
were developed for the specific target compound list associated
with this Statement of Work. The criteria are based on
performance characteristics of instruments currently utilized
in routine support of Program activities. These
specifications, in conjunction with relative response factor
criteria for 23 target compounds (see Table 2), are designed to
control and monitor instrument performance associated with the
requirements of this Statement of Work.
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SECTION IV
6.4.6 The instrument performance check solution must be injected once
at the beginning of each 12-hour period, during which samples
or standards are to be analyzed. The twelve (12) hour time
period for GC/MS Instrument Performance Check (BFB), standards
calibration (initial or continuing calibration criteria) and
method blank analysis begins at the moment of injeccion of the
BFB analysis that the laboratory submits as documentation of a
compliant instrument performance check. The time period ends
after twelve (12) hours has elapsed according to the system
clock.
7. Calibration
7.1 Prior to the analysis of samples and required blanks, and after the
instrument performance check solution 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 compounds.
7.2 Assemble a purge and trap device that meets the specification in 3.6.
Condition the trap overnight at 180'C in the purge mode with an inert
gas flow of at least 20 mL/min. Daily, prior to use, condition the
traps for 10 minutes while backflushing at 180"C with the column at
220°C.
7.3 Connect the purge and trap device to a gas chromatograph. The gas
chromatograph must be operated using temperature and flow rate
parameters equivalent to those in 6.2. Calibrate the purge and
trap-GC/MS system using the internal standard technique (7.4).
7.4 Internal standard calibration procedure. The three internal standards
are Bromochloromethane, 1,4-Difluorobenzene, and Chlorobenzene-dc, at
50 ug/L at time of purge. Separate initial and continuing calibrations
must be performed for water samples, and low level soil samples
(unheated purge vs. heated purge). Extracts of medium level soil
samples may be analyzed using the calibrations for water samples.
7.4.1 Prepare calibration standards at a minimum of five
concentration levels for each target compound and system
monitoring compound, as specified in 5.5. Standards may be
stored up to 24 hours, following the procedures in paragraph
5.6.3.
7.4.2 Prepare a spiking solution containing each of the internal
standards using the procedures described in paragraph 5.4.3.
7.4.3 Verify that the GC/MS system meets the instrument performance
criteria in paragraph 6.4 by injecting BFB. Analyze each
calibration standard, according to paragraph 7.1, adding 10 uL
of internal standard spiking solution directly to the syringe.
D-26/VOA OLM01.0
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SECTION IV
Tabulate Che area response of the characteristic ions in che
extracted ion current profile (EICP) against concentration for
each compound and internal standard and calculate relative
response factors (RRF) for each compound using Equation 1.
AX Cis EQ-1
RRF — x —
Ais Cx
Where
Ax - Area of the characteristic ion (EICP) for the compound
to be measured (see Table 4)
Ais ~ Area of the characteristic ion (EICP) for the
specific internal standard (see Table 3)
G£S - Concentration of the internal standard
C - Concentration of the compound to be*measured
7.4.4 The average relative response factor (RRF) must be calculated
for all compounds. Calculate the % Relative Standard Deviation
(%RSD) of RRF values over the working range of the curve.
%RSD - Standard deviation x 100
mean
7.4.5 Response factor criteria have been established for the
calibration of 23 of the volatile target compounds and one
volatile system monitoring compound. The compounds listed
below (Table 2) must meet the minimum RRF and maximum %RSD
criteria for the initial calibration, with allowance made for
up to two volatile compounds. However, the RRFs for those two
compounds must be greater than or equal to 0.010, and the %RSD
of those two compounds must be less than or equal to 40.0% for
the initial calibration to be acceptable.
D-27/VOA OLM01.0
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SECTION IV
TABLE 2
RELATIVE RESPONSE FACTOR CRITERIA FOR INITIAL AND CONTINUING
CALIBRATION OF VOLATILE ORGANIC COMPOUNDS
Volatile Minimum Maximum Maximum
Compound RRF %RSD %Diff
Bromomethane 0.100 20.5 25.0
Vinyl chloride 0.100 20.5 25.0
1,1-Dichloroethene 0.100 20.5 25.0
1,1-Dichloroethane 0.200 20.5 25.0
Chloroform 0.200 20.5 25.0
1,2-Dichloroethane 0.100 20.5 25.0
1,1,1-Trichloroethane 0.100 20.5 25.0
Carbon tetrachloride 0.100 20.5 25.0
Bromodichloromethane 0.200 20.5 25.0
cis-l,3-Dichloropropene 0.200 20.5 25.0
Trichloroethene 0.300 20.5 25.0
Dibromochloromethane 0.100 20.5 „ 25.0
1.1,2-Trichloroethane 0.100 20.5 25.0
Benzene 0.500 20.5 25.0
trans-l,3-Dichloropropene 0.100 20.5 25.0
Bromoform 0.100 20.5 25.0
Tetrachloroethene 0.200 20.5 25.0
1,1,2,2-Tetrachloroethane 0.500 20.5 25.0
Toluene 0.400 20.5 25.0
Chlorobenzene 0.500 20.5 25.0
Ethylbenzene 0.100 20.5 25.0
Styrene 0.300 20.5 25.0
Xylenes (total) 0.300 20.5 25.0
Bromofluorobenzene 0.200 20.5 25.0
7.4.6 Because performance data indicate erratic and poor linearity,
the following compounds have no Maximum %RSD, or Maximum
%Difference criteria; however, these compounds must meet a
minimum RRF criterion of 0.010:
Acetone 1,2-Dichloropropane
2 -Butanone 2-Hexanone
Carbon disulfide Methylene chloride
Chloroethane 4-Methyl-2-pentanone
Chloromethane Toluene-dg
1,2-Dichloroethene (total) 1,2-Dichloroethane-d^
7.4.7 A check of the calibration curve must be performed once every
12 hours (see paragraph 6.4.6 for the definition of the twelve
hour time period). Check the relative response factors of
those compounds for which RRF values have been established. If
these criteria are met, the relative response factors for all
compounds are calculated and reported. A percent difference of
the daily relative response factor (12 hour) compared to the
D-28/VOA OLM01.0
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SECTION IV
average relative response factor from che initial curve is
calculated. Calculate the percent difference for each compound
and compare with the maximum percent difference criteria listed
above. As with the initial calibration, up to two volatile
compounds in Table 2 may fail to meet the minimum RRF or
maximum %D criteria, but the RRFs of those two compounds must
be greater than or equal to 0.010, and the percent differences
must be less than or equal to 40.0% for the continuing
calibration to be acceptable.
7.4.8 Internal standard responses and retention times in all
standards must be evaluated during or immediately after data
acquisition. If the retention time for any internal standard
changes by more than 0.50 minutes (30 seconds) from the latest
daily (12 hour) calibration standard, the chromatographic
system must be inspected for malfunctions, and corrections made
as required. The extracted ion current profile (EICP) of the
internal standards must be monitored and evaluated for each
standard. If the EICP area for any internal standard changes
by more than a factor of two (-50% to +100%"), the mass
spectrometric system must be inspected for malfunction, and
corrections made as appropriate. When corrections are made,
re-analysis of samples analyzed while the system was
malfunctioning is necessary.
7.5 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 removal or replacement, etc.), or if the continuing
calibration acceptance criteria have not been met.
7.6 If time remains in the 12 hour time period after meeting the acceptance
criteria for the initial calibration, samples may be analyzed. It is
not necessary to analyze a continuing calibration standard, if the
initial calibration meets the calibration acceptance criteria above. A
method blank is necessary. Quantify all sample results against the
initial calibration standard that is the same concentration as the
continuing calibration standard (50 ug/L).
7.7 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.
7.8 The concentrations of volatile target compounds in the continuing
calibration standard are given in paragraph 5.5.3.
7.9 The response factors for the continuing calibration standard must meet
the criteria given in paragraph 7.4.5 prior to the analysis of any
blanks or samples.
D-29/VOA OLM01.0
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SECTION IV
8. Sample Analysis
8.1 Water Samples
8.1.1 All water samples must be allowed to warm to ambient
temperature before analysis.
8.1.2 Prior to the analysis of samples, establish the appropriate
GC/MS operating conditions, as outlined in paragraphs 6-6.4.6,
analyze the instrument performance check solution (6.4), and
calibrate the GC/MS system according to paragraphs 7-7.7.3.
8.1.3 If time remains in the 12-hour period (as described in
paragraph 7.6), samples may be analyzed without analysis of a
continuing calibration standard.
8.1.4 If time does not remain in the 12-hour period since the
injection of the instrument performance check solution, both
the instrument performance check solution and the continuing
calibration standard must be analyzed before" sample analysis
may begin (see paragraphs 7.7-7.9).
8.1.5 Adjust the purge gas (helium) flow rate to 25-40 mL/min.
Variations from this flow rate may be necessary to achieve
better purging and collection efficiencies for some compounds,
particularly Chloromethane and Bromoform.
8.1.6 Remove the plunger from a 5 mL syringe and attach a closed
syringe valve. Open the sample or standard bottle 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. Open the syringe valve and vent any residual air while
adjusting the sample volume to 5.0 mL. This process of taking
an aliquot destroys the validity of the sample for future
analysis so, if there is only one VOA vial, the analyst should
fill a second syringe at this time to protect against possible
loss of sample integrity. This second sample is maintained
only until such time as the analyst has determined that the
first sample has been analyzed properly. Filling one 5 mL
syringe would allow the use of only one syringe. If an
analysis is needed from the second 5 mL syringe, it must be
performed within 24 hours. Care must also be taken to prevent
air from leaking into the syringe.
8.1.7 The purgeable organics screening procedure (Section III), if
used, will have shown the approximate concentrations of major
sample components. If a dilution of the sample was indicated,
this dilution shall be made just prior to GC/MS analysis of the
sample. All steps in the dilution procedure must be performed
without delays until the point at which the diluted sample is
in a gas tight syringe.
D-30/VOA OLM01.0
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SECTION IV
8.1.7.1 The following procedure will allow for dilutions
near the calculated dilution factor from the
screening procedure:
8.1.7.1.1 All dilutions are made in volumetric
flasks (10 mL to 100 mL) .
8.1.7.1.2 Select the volumetric flask that will
allow for the necessary dilution.
Intermediate dilutions may be necessary
for extremely large dilutions.
8.1.7.1.3 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.
8.1.7.1.4 Inject the proper aLiquot from the
syringe prepared in paragraph 8.1.6
into the volumetric flask. Aliquots of
less than 1 mL increments are
prohibited. Dilute the flask to the
mark with reagent water. Cap the
flask, invert, and shake three times.
8.1.7.1.5 Fill a 5 mL syringe with the diluted
sample as in paragraph 8.1.6.
8.1.7.1.6 If this is an intermediate dilution,
use it and repeat the above procedure
to achieve larger dilutions.
8.1.8 Add 10.0 uL of the system monitoring compound spiking solution
(paragraph 5.4.4) and 10.0 uL of the internal standard spiking
solution (paragraph 5.4.3) through the valve bore of the
syringe, then close the valve. The system monitoring compounds
and internal standards may be mixed and added as a single
spiking solution. The addition of 10 uL of the system
monitoring compound spiking solution to 5 mL of sample is
equivalent to a concentration of 50 ug/L of each system
monitoring compound.
8.1.9 Attach the syringe-syringe valve assembly to the syringe valve
on the purging device. Open the syringe valves and inject the
sample into the purging chamber.
8.1.10 Close both valves and purge the sample for 11.0 + 0.1 minutes
at ambient temperature.
8.1.11 At the conclusion of the purge time, attach the trap to the
chromatograph, adjust the device to the desorb mode, and begin
the gas chromatographic temperature program. Concurrently,
introduce the trapped materials to the gas chromatographic
D-31/VOA OLM01.0
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SECTION IV
column by rapidly heating the trap to 180°C while backflushing
the trap with an inert gas between 20 and 60 mL/min for four
minutes. If this rapid heating requirement cannot be met, the
gas chromatographic column must be used as a secondary trap by
cooling it to 30"C (or subambient, if problems persist) instead
of the recommended initial temperature of 45°C.
8.1.12 While the trap is being desorbed into the gas chromatograph,
empty the purging chamber. Hash the chamber with a minimum of
two 5 mL flushes of reagent water to avoid carryover of target
compounds.
8.1.13 After desorbing the sample for four minutes, recondition the
trap by returning the purge and trap device to the purge mode.
Wait 15 seconds, then close the syringe valve on the purging
device to begin gas flow through the trap. The trap
temperature should be maintained at 180'C. Trap temperatures
up to 220*C may be employed, however the higher temperature
will shorten the useful life of the trap. After approximately
seven minutes, turn off the trap heater and *open the syringe
valve to stop the gas flow through the trap. When cool, the
trap is ready for the next sample.
8.1.14 Each analytical run must be checked also for saturation. The
level at which an individual compound will saturate the
detection system is a function of the overall system
sensitivity and the mass spectral characteristics of that
compound. The initial calibration requires that the system
should not be saturated for high response compounds at 200 ug/L
for VOA target compounds. Secondary ion quantitation is
allowed only when there are sample matrix interferences with
the primary ion. If secondary ion quantitation is performed,
document the reasons in the SDG Narrative. When a sample is
analyzed that has saturated ions from a compound, this analysis
must be followed by the analysis of a reagent water blank. If
the blank is not free of interferences, the system must be
decontaminated. Sample analysis may not resume until a blank
has been analyzed that is free of interferences.
8.1.15 To prepare a matrix spike and matrix spike duplicate for water
samples, add 10 uL of the matrix spike solution (paragraph
5.4.5) to each of the 5 mL aliquots of the sample chosen for
spiking. Disregarding any dilutions, this is equivalent to a
concentration of 50 ug/L of each matrix spike compound. The
frequency of MS/MSD analysis is given in paragraph 10.8.
8.1.16 A volatile method blank must be analyzed at least once during
every twelve hour time period, on each GC/MS system used for
volatile analysis (see paragraph 6.4.6 for the definition of
the twelve hour time period).
8.1.16.1 For water samples, a volatile method blank, consists
of a 5 mL volume of reagent water (paragraph 4.1)
spiked with the system monitoring compounds and
D-32/VOA OLM01.0
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SECTION IV
internal standards, and carried through the
analytical procedure.
8.1.16.2 An acceptable volatile method blank for water
samples must contain less than or equal to five
times (5x) the Contract Required Quantitation Limit
(CRQL, see Exhibit C) of Methylene chloride,
Acetone, and 2-Butanone, and less than or equal to
the CRQL of any other volatile target compound.
8.1.16.3 All volatile analyses associated with a blank that
does not meet the requirements above, (i.e., a
contaminated blank) must be repurged, reanalyzed,and
reported at no additional cost to the Agency.
8.1.16.4 The volatile method blank must be analyzed after the
calibration standards, to ensure that there is no
carryover of material from the standards into
samples. -
8.2 Soil/Sediment Samples
Two approaches may be taken to determine whether the low level or
medium level method must be followed.
o Assume the sample is low level and analyze a 5 g sample.
o Use the X factor calculated from the optional hexadecane screen
(Section III, paragraph 6.2.1.3) to determine the appropriate method
for analysis.
If peaks are saturated from the analysis of a 5 g sample, a smaller
sample size must be analyzed to prevent saturation. However, the
smallest sample size permitted is 1 g. If smaller than 1 g sample size
is needed to prevent saturation, the medium level method must be used.
8.2.1 Low Level Soil Method
The low level soil method is based on purging a heated
sediment/soil sample mixed with reagent water containing the
system monitoring compounds and the internal standards..
Analyze all method blanks and standards under the same
conditions as the samples.
Use 5 grams of sample, or use the X Factor to determine the
sample size for purging.
o If the X Factor is 0 (no peaks noted on the hexadecane
screen), analyze a 5 g sample.
o If the X Factor is between 0 and 1.0, analyze a minimum of a
1 g sample.
8.2.1.1 The GC/MS system should be set up as in paragraphs
7-7.7.3. This should be done prior to the
preparation of the sample to avoid loss of volatiles
D-33/VOA OLM01.0
-------
SECTION IV
from standards and sample. A heated purge
calibration curve must be prepared and used for the
quantitation of all samples analyzed with the
low-level method. Follow the initial and daily
calibration instructions (7.4 and 7.7), but increase
the purge temperature to 40°C.
8.2.1.2 To prepare the reagent water containing the system
monitoring compounds and the internal standards,
remove the plunger from a 5 mL "Luerlock" type
syringe equipped with a syringe valve and fill until
overflowing with reagent water. Replace the plunger
and compress the water to vent trapped air. Adjust
the volume to 5.0 mL. Add 10 uL of the system
monitoring compound spiking solution and 10 uL of
the internal standard solution to the syringe
through the valve.
8.2.1.3 The sample (for volatile organics-) consists of the
entire contents of the sample container. Do not
discard any supernatant liquids. Mix the contents
of the sample container with a narrow metal spatula.
Weigh the amount determined in paragraph 8.2.1 into
a tared purge device. Use a top loading balance.
Note and record the actual weight to the nearest 0.1
g-
8.2.1.4 Immediately after weighing the sample, weigh 5-10 g
of the sediment into a tared crucible. Determine
the percent moisture by drying overnight at 105°C.
Allow to cool in a desiccator before weighing.
Concentrations of individual analytes will be
reported relative to the dry weight of sediment.
g of wet sample-g of dry sample
g of wet sample x 100 - % moisture
8.2.1.5 Add the spiked reagent water to the purge device and
connect the device to the purge and trap system.
NOTE: Prior to the attachment of the purge device,
the steps in paragraphs 8.2.1.2 and 8.2.1.3 must be
performed rapidly to avoid loss of volatile
organics. These steps must be performed in a
laboratory free of solvent fumes.
8.2.1.6 Heat the sample to 40°C + 1°C and purge the sample
for 11.0 + 0.1 minutes.
8.2.1.7 Proceed with the analysis as outlined in paragraphs
8.1.10 - 8.1.13. Requirements for dilution of
samples are given in paragraphs 8.2 and 10.7.
D-3A/VOA OLM01.0
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SECTION IV
8.2.1.8 To prepare a matrix spike and matrix spike duplicate
for low level soils/sediment, add 10 uL of the
matrix spike solution (5.4.4) to the 5 raL of water
added to each of the two aliquots of the soil from
the sample chosen for spiking (paragraph 8.2.1.2).
The concentration for a 5 g sample would be
equivalent to 50 ug/kg of each matrix spike
compound. The frequency of MS/MSD analysis is given
in paragraph 10.8.
8.2.1.9 A volatile method blank must be analyzed at least
once during every twelve hour time period, on each
GC/MS system used for volatile analysis (see
paragraph 6.4.6 for the definition of the twelve
hour time period).
8.2.1.9.1 For low level soil/sediment samples, a
volatile method blank consists of a 5 g
of a purified solid matrix added to
reagent water, spiked!" with the system
monitoring compounds and internal
standards, and carried through the
analytical procedure.
8.2.1.9.2 An acceptable volatile method blank for
low level soil samples must contain
less than or equal to five times (5x)
the Contract Required Quantitation
Limit (CRQL, see Exhibit C) of
Methylene chloride, Acetone, and 2-
Butanone, and less than or equal to the
CRQL of any other volatile target
compound.
8.2.1.9.3 All volatile analyses associated with a
blank that does not meet the
requirements above, (i.e., a
cont-ainated blank) must be repurged,
reanalyzed,and reported at no
additional .cost to the Agency.
8.2.1.9.4 The volatile method blank must: be
analyzed after the calibration
standards, to ensure that there is no
carryover of material from the
standards into samples.
8.2.2 Medium Level Soil Method
The medium level soil method is based on extracting the soil/
sediment sample with methanol. An aliquot of the methanol
extract is added to reagent water containing the system
monitoring compounds and the internal standards. The reagent
water containing the methanol extract is purged at ambient
D-35/VOA OLM01.0
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SECTION IV
temperature. All samples with an X Factor >1.0 must be
analyzed by the medium level method. If saturated peaks
occurred, or would occur, when a 1 g sample was analyzed, the
medium level method must be used.
8.2.2.1 The GC/MS system should be set up as in paragraphs
7-7.7.3. This should be done prior to the addition
of the methanol extract to reagent water. Because
the methanol extract and reagent water mixture is
purged at ambient temperature, the instrument
performance check, initial calibration, and
continuing calibration for water samples may be used
for analyses of medium soil sample extracts.
8.2.2.2 The sample (for volatile organics) consists of the
entire contents of the sample container. Do not
discard any supernatant liquids. Mix the contents
of the sample container with a narrow metal spatula.
Weigh 4 g (wet weight) into a tared 15 mL vial. Use
a top loading balance. Note and record the actual
weight to the nearest 0.1 g. Determine the percent
moisture as in paragraph 8.2.1.4.
8.2.2.3 Quickly add 9.0 mL of methanol to the vial. Then
add 1.0 mL of the system monitoring compound spiking
solution to the vial. Cap and shake for 2 minutes.
NOTE: The steps in paragraphs 8.2.2.2 and 8.2.2.3
must be performed rapidly to avoid loss of volatile
organics. These steps must be performed in a
laboratory free of solvent fumes.
8.2.2.4 Using a disposable pipette, transfer approximately 1
mL of extract into a GC vial for storage. The
remainder may be discarded. Transfer approximately
1 mL of the reagent methanol to a GC vial for use as
the method blank for each Case, SDG, or day on which
medium soil sample extractions are performed,
whichever is most frequent. These extracts may be
stored in the dark at 4°C (±2°C) prior to analysis.
8.2.2.5 The following table can be used to determine the
volume of methanol extract to add to the 5 mL of
reagent water for analysis. If the Hexadecane
screen procedure was followed, use the X factor
(Option B) or the estimated concentration (Option A)
to determine the appropriate volume. Otherwise,
estimate the concentration range of the sample from
the low level analysis to determine the appropriate
volume. If the sample was submitted as a medium
level sample, start with 100 uL.
All dilutions must keep the response of the major
constituents (previously saturated peaks) in the
upper half of linear range of the curve.
D-36/VOA OLM01.0
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SECTION IV
Estimated Take this Volume of
I
X Factor Concentration Range Methanol Extract^
ug/kg
0.25
0.5
2.5
12.5
5.0
- 10.0
- 50.0
- 250
500 -
1000 -
5000 -
25,000 -
10,000
20.000
100,000
500,000
uL
100
50
10
100 of 1/50 dilution3
Calculate appropriate dilution factor for concentrations exceeding the table.
Actual concentration ranges could be 10 to 20 times higher than this if
the compounds are halogenated and the estimates are from GC/FID.
o
The volume of methanol added to the 5 mL of water being purged should be
kept constant. Therefore, add to the 5 mL syringe whatever volume of
methanol is necessary to maintain a volume of 100 uL added to the syringe.
Dilute an aliquot of the methanol extract and then take 100 uL for
analysis. *
8.2.2.6 Remove the plunger from a 5 mL "Luerlock" type
syringe equipped with a syringe valve and fill until
overflowing with reagent water. Replace the plunger
and compress the water to vent trapped air. Adjust
the volume to 4.9 mL. Pull the plunger back to 5 mL
to allow volume for the addition of sample and
standards. Add 10 uL of the internal standard
solution. Also add the volume of methanol extract
determined in paragraph 8.2.2.5 and a volume of
clean methanol to total 100 uL (excluding methanol
in standards).
8.2.2.7 Attach the syringe-syringe valve assembly to the
syringe valve on the purging device. Open the
syringe valve and inject the water/methanol sample
into the purging chamber.
8.2.2.8 Proceed with the analysis as outlined in paragraph
8. Analyze all method blanks on the same instrument
as the samples. Requirements for dilution of
samples are given in paragraphs 8.2 and 10.7.
8.2.2.9 To prepare a matrix spike and matrix spike duplicate
for the medium level soil/sediment samples, add 8.0
mL of methanol, 1.0 mL of the system monitoring
compound spiking solution, and 1.0 mL of matrix
spike solution (paragraph 5.4.4) as in paragraph
8.2.2.3, to each of the two aliquots of the soil
sample chosen for spiking. This results in a 6,200
ug/kg concentration of each matrix spike compound
when added to a 4 g sample. Add a 100 uL aliquot of
this extract to 5 mL of water for purging (as per
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SECTION IV
paragraph 8.2.2.6). The frequency of MS/MSD
analysis is given in paragraph 10.8.
8.2.2.10. A volatile method blank must be analyzed at least
once during every twelve hour time period, on each
GC/MS system used for volatile analysis (see
paragraph 6.4.6 for the definition of the twelve
hour time period).
8.2.2.10.1 For medium level soil/sediment samples,
a volatile method blank consists of a 1
g of a purified solid matrix spiked
with the system monitoring compounds,
extracted with methanol, and carried
through the analytical procedure.
8.2.2.10.2 An acceptable volatile method blank for
medium level soil/sediment samples must
contain less than or equal five times
(5x) the Contract Required Quantitation
Limit (CRQL, see Exhibit C) of
Methylene chloride, Acetone, and 2-
Butanone, and less than or equal ot the
CRQL of any other volatile target
compound.
8.2.2.10.3 All volatile analyses associated with a
blank that does not meet the
requirements above, (i.e. a
contaminated blank) must be repurged,
reanalyzed,and reported at no
additional cost to the Agency.
8.2.2.10.4 The volatile method blank must be
analyzed after the calibration
standards, to ensure that there is no
carryover of material from the
standards into samples.
9. Qualitative Analysis
9.1 The compounds listed in the Target Compound List (TCL), Exhibit C,
shall be identified by an analyst competent in the interpretation of
mass spectra (see Bidder Responsibility description) 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: (1) elution of the sample component at the same GC
relative retention time as the standard component, and (2)
correspondence of the sample component and standard component mass
spectra.
9.1.1 For establishing correspondence of the GC relative retention
time (RRT), the sample component RRT must compare within +0.06
RRT units of the RRT of the standard component. For reference,
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SECTION IV
the standard must be run in the same 12-hour time period as the
sample. If coelution of interfering components prohibits
accurate assignment of the sample component RRT from the total
ion chromatogram, the RRT should be assigned by using extracted
ion current profiles for ions unique to the component of
interest.
9.1.2 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 BFB. These
standard spectra may be obtained from the run used to obtain
reference RRTs.
9.1.3 The requirements for qualitative verification by comparison of
mass spectra are as follows:
9.1.3.1 All ions present in the standard mass spectra at a
relative intensity greater than 10% (most abundant
ion in the spectrum equals 100%) must be present in
the sample spectrum.
9.1.3.2 The relative intensities of ions specified, in
paragraph 9.1.3.1 must agree within ± 20% between
the standard and sample spectra. (Example: For an
ion with an abundance of 50% in the standard
spectra, the corresponding sample abundance must be
between 30 and 70 percent).
9.1.3.3 Ions greater than 10% in the sample spectrum but not
present in the standard spectrum must be considered
and accounted for by the analyst making the
comparison. In Task III, the verification process
should favor false positives. All compounds meeting
the identif icati'. a criteria must be reported with
their spectra. For all compounds below the CRQL
report the actual value followed by a "J", e.g.,
"3J.n
9.1.4 If a compound cannot be verified by all of the criteria in
paragraph 9.1.3.3, but in the technical judgement of the mass
spectral interpretation specialist, the identification is
correct, then the Contractor shall report that identification
and proceed with quantification in paragraph 10.
9.2 A library search shall be executed for non-target sample components for
the purpose of tentative identification. For this purpose, the 1989
(or more recent) release of the NIST/EPA/MSDC mass spectral library,
containing 50,000 spectra, shall be used. Computer generated library
search routines must not use normalization routines that would
misrepresent the library or unknown spectra when compared to each
other.
D-39/VOA OLM01.0
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SECTION IV
9.2.1 Up co 10 organic compounds of greatest apparent concentration
not listed in Exhibit C for the purgeable organic fraction,
excluding the system monitoring compounds, shall be tentatively
identified via a forward search of the NIST/EPA/MSDC Library
(substances with responses less than 10% of the internal
standard are not required to be searched in this fashion).
Only after visual comparison of sample spectra with the nearest
library searches will the mass spectral interpretation
specialist assign a tentative identification. Computer
generated library search routines must not use normalization
routines that would misrepresent the library or unknown spectra
when compared to each other.
9.2.2 Guidelines for making tentative identification:
9.2.2.1 Relative intensities of major ions in the reference
spectrum (ions greater than 10% of the most abundant
ion) should be present in the sample spectrum.
9.2.2.2 The relative intensities of the major ions should
agree within ± 20%. (Example: For an ion with an
abundance of 50 percent of the standard spectra, the
corresponding sample ion abundance must be between
30 and 70 percent.)
9.2.2.3 Molecular ions present in reference spectrum should
be present in sample spectrum.
9.2.2.4 Ions present in the sample spectrum but not in the
reference spectrum should be reviewed for possible
background contamination or presence of co-eluting
compounds.
9.2.2.5 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 co-eluting compounds.
Data system library reduction programs can sometimes
create these discrepancies.
9.2.3 If, 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 (i.e., unknown aromatic,
unknown hydrocarbon, unknown acid type, unknown chlorinated
compound). If probable molecular weights can be distinguished,
include them.
10. Quantitative Analysis
10.1 Target components identified shall be quantified by the internal
standard method. The internal standard used shall be that which is
assigned in Table 5 of this Section. The EICP area of the
D-40/VOA OLM01.0
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SECTION IV
characteristic ions of analytes listed in Tables 3 and 4 in this
Section are used.
10.2 Internal standard responses and retention times in all standards must
be evaluated during or immediately after data acquisition. If the
retention time for any internal standard changes by more than 30
seconds from the latest daily (12 hour) calibration standard, the
chromatographic system must be inspected for malfunctions, and
corrections made as required. The extracted ion current profile (EICP)
of the internal standards must be monitored and evaluated for each
sample, blank, matrix spike, and matrix spike duplicate. If the EICP
area for any internal standard changes by more than a factor of two
(-50% to +100%), the mass spectrometric system must be inspected for
malfunction and corrections made as appropriate. When corrections are
made, reanalysis of samples analyzed while the system was
malfunctioning is necessary.
10.2.1 If after re-analysis, the EICP areas for all internal standards
are inside the contract limits (-50% to +100%), then the
problem with the first analysis is considered to have been
within the control of the laboratory. Therefore, submit only
data from the analysis with EICPs within the contract: limits.
This is considered the initial analysis and must be reported as
such on all data deliverables.
10.2.2 If the re-analysis of the sample does not solve the problem,
i.e., the EICP areas are outside the contract limits for both
analyses, then submit the EICP data and sample data from both
analyses. Distinguish between the initial analysis and the
re-analysis on all data deliverables, using the sample suffixes
specified in Exhibit B. Document in the SDG Narrative all
inspection and corrective actions taken.
D-41/VOA OLM01.0
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SECTION IV
10.3 The relative response factor (RRF) from the continuing calibration
standard is used to calculate the concentration in the sample. Use the
relative response factor as determined in paragraph 7.4.3 and the
equations below. When target compounds are below contract required
quantitation limits (CRQL) , but the spectra meet the identification
criteria, report the concentration with a "J." For example, if CRQL is
10 ug/L and concentration of 3 ug/L is calculated, report as n3J."
Water
(Ax)(Is)(Df)
Concentration ug/L - (A.s> (RRF) (VQ)
Where
AX - Area of the characteristic ion (EICP) for the compound
to be measured (see Table 4)
Ais - Area of the characteristic ion (EI-CP) for the specific
internal standard (see Table 3)
Ig - Amount of internal standard added in nanograms (ng)
RRF - Relative response factor from the ambient temperature
purge of the calibration standard.
VQ - Volume of water purged in milliliters (mL)
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., VQ above) to the number of mL of the
original water sample used for purging. For example, if
2.5 mL of sample is diluted to 5.0 mL with reagent water
and purged, Df - 5.0 mL/2.5 mL - 2.0. If no dilution is
performed, Df - 1.0.
Low Soil
Concentration (AX)(IS)
(Dry weight basis) ug/Kg -
(RRF)(WS)(D)
Where
AX, Is , A£S RRFs are as given for water.
D - 100 - % moisture
100
W - Weight of sample added to the purge tube, in grams (g)
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SECTION IV
Medium Soil
Concentration (A%)Us)(Vt)(1000)(Df)
(Dry weight basis) ug/Kg - (A.s)(RRF)(va)(Ws)(57
Where
AX, Ais, Is, RRFs are as given for water above.
Vt - Total volume of the methanol extract in milliliters
(mL). NOTE: This volume is typically 10.0 mL, even
though only 1.0 mL is transferred to the vial in
paragraph 8.2.2.4.
Va - Volume of the aliquot of the methanol extract in
microliters (uL) added to reagent water for purging
W - Weight of soil extracted, in grams (g)
D - 100 - % moisture
100
Df - Dilution factor. The dilution factor for analysis of
soil/sediment samples for volatiles by the medium level
method is defined as the ratio of the number of
microliters (uL) of methanol added to the reagent water
for purging i.e., Va above, to the number of microliters
of the methanol extract of the sample contained in that
volume V&. The dilution factor is equal to 1.0 in all
cases other than those requiring dilution of the
methanol extract. Dilution of the extract is required
when the "X" factor (paragraph 8.2.2.5) is > 12.5.
The factor of 1,000 in the numerator converts the value
of V£ from mL to uL.
10.4 An estimated concentration for non-target components tentatively
identified shall be determined by fv.e internal standard method. For
quantification, the nearest internal standard free of interferences
shall be used.
The formula for calculating concentrations is the same as in paragraph
10.3. Total area counts (or peak heights) from the total ion
chromatograms are to be used for both the compound to be measured and
the internal standard. A relative response factor (RRF) of one (1) is
to be assumed. The resulting concentration shall be qualified as "J"
(estimated, due to lack of a compound-specific response factor), and
"N" (presumptive evidence of presence), indicating the quantitative and
qualitative uncertainties associated with this non-target component.
An estimated concentration should be calculated for all tentatively
identified compounds as well as those identified as unknowns.
10.5 Xylenes (o-,m-, & p- isomers) are to be reported as Xylenes (total).
Since o- and p-Xylene overlap, the Xylenes must be quantitated as
D-43/VOA • OLM01.0
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SECTION IV
m-Xylene. The concentration of all Xylene isoraers must be added
together to give the total.
10.6 Both trans and cis stereoisoraers of 1,2-Dichloroethene are to be
reported as 1,2-Dichloroethene (total). The concentrations of both
isomers must be added together to give the total.
10.7 If the on-column concentration of any compound in any sample exceeds
the initial calibration range, that sample must be diluted, the
internal standard concentration re-adjusted, and the sample repurged.
Guidance in performing dilutions, and exceptions to this requirement
are given below.
10.7,1 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.
10.7.2 The dilution factor chosen should keep the response of th°
largest analyte peak for a target compound in" the upper half of
the initial calibration range of the instrument.
10.7.3 Do not submit data for more than two analyses, i.e. , the
original sample and one dilution, or, if the volatile screening
procedure was employed, from the most concentrated dilution
analyzed and one further dilution.
10.7.4 Do not dilute MS/USD samples solely to get non-spiked analytes
within calibration range. The spiking level of each compound
in the volatile matrix spiking solution should not require the
dilution of the MS/MSD unless the sample from which these
aliquots were taken contains high levels of the spiked
analytes.
10.7.5 For total Xylenes, where three isomers are quantified as two
peaks, the calibration of each peak, should be considered
separately, i.e., a diluted analysis is not required for total
Xylenes unless the concentration of either peak separately
exceeds 200 ug/L.
10.8 Calculate the recovery of each system monitoring compound in all
samples, blanks, matrix spikes, and matrix spike duplicates. Determine
if the recovery is within limits (see Table 6), and report on
appropriate form.
10.8.1 Calculate the concentrations of the system monitoring compounds
using the same equations as used for target compounds.
Calculate the recovery of each system monitoring compound as
follows:
%R - Concentration (or amount) found x 100
Concentration (or amount) spiked
D-44/VOA OLM01.0
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SECTION IV
10.8.2 If the recovery of any one system monitoring compound is not
within limits, the following are required:
o Check to be sure that there are no errors in calculations,
formulation of the system monitoring compound spiking
solutions, and internal standards. Also check instrument
performance.
o Reanalyze the sample if none of the above steps reveal a.
problem.
o Do not reanalyze diluted samples if the system monitoring
compound recoveries are outside the limits.
o Never reanalyze the matrix spike or matrix spike duplicate
(MS/MSD), even if the system monitoring compound recoveries
are outside the limits.
o If the sample associated with the matrix spike and matrix
spike duplicate does not meet specifications, it should be
reanalyzed only if the MS/MSD system monitoring compound
recoveries are within the limits. If the^sample and
associated MS/MSD show the same pattern (i.e., outside the
limits), then the sample does not require reanalysis and a
reanalysis must not be submitted. Document in the
narrative the similarity in recoveries of the system
monitoring compounds in the sample and associated MS/MSD.
10.8.3 If the reanalysis of the sample solves the problem, then the
problem was within the laboratory's control. Therefore, submit
only data from the analysis with system monitoring compound
recoveries within the limits. This shall be considered the
initial analysis and shall be reported as such on all data
deliverables.
10.8.4 If the reanalysis of the sample does not solve the problem
(i.e., the system monitoring compound recoveries are outside
the limits for both analyses), then submit the data from both
analyses. Distinguish between the initial analysis and the
reanalysis on all data deliverables, using the sample suffixes
supplied in Exhibit B.
10.8.5 For medium level soil analyses, involving methanol extraction,
the treatment of system monitoring compound recoveries is
similar to that for send/volatile surrogate recoveries. If any
system monitoring compound recovery is outside the limits,
reanalyze the methanol extract first, to determine if the
problem was with the analysis. If reanalysis of the extract
does not solve the problem, then reextract the medium soil
sample and analyze the second extract. Follow paragraphs
10.8.3 and 10.8.4 when determining which analyses to submit.
10.8.6 If the recovery of any one system monitoring compound in a
method blank is outside the limits, then the method and all
associated samples must be reanalyzed at no additional cost to
the Agency.
D-45/VOA OLM01.0
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SECTION IV
10.9 A matrix spike and matrix spike duplicate must be performed for each
group of samples of a similar matrix, for the following, whichever is
most frequent:
o Each Case of field samples received, OR
o Each 20 field samples in a Case, OR
o Each group of field samples of a similar concentration level (soils
only), OR
o Each 14 calendar day period during which field samples in a Case
were received (said period beginning with the receipt of the first
sample in chat Sample Delivery Group).
10.9.1 Calculate the concentrations of the matrix spike compounds
using the same equations as used for target compounds.
Calculate the recovery of each matrix spike compound as
follows:
%R - Concentration (or amount) found x 100 -
Concentration (or amount) spiked
10.9.2 Calculate the relative percent difference (RPD) of the
recoveries of each compound in the matrix spike and matrix
spike duplicate as follows:
RPD - | MSR - MSDRI x 100
(1/2)(MSR+MSDR)
Where
MSR - Matrix Spike Recovery
MSDR - Matrix Spike Duplicate Recovery
The vertical bars in the formula above indicate the absolute
value of the difference, hence RPD is always expressed as a
positive value.
10.9.3 The limits for matrix spike compound recovery and RPD are given
in Table 7. 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 the Agency.
10.10 Determine the concentrations of any target compounds detected in the
volatile method blank, using the equations in paragraph 10.3. The
method blank must contain less than or equal to the Contract Required
Quantitation Limit (CRQL) of the volatile target compounds in Exhibit
C, except Methylene chloride, Acetone, and 2-Butanone, which must be
less than or equal to five times (5x) the CRQL. For soil/sediment
method blanks, CRQL value must be adjusted for percent moisture (see
Exhibit B).
D-46/VOA OLMOL.O
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SECTION IV
If a laboratory method blank exceeds these criteria, 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. All samples processed with a method blank that is out of
control (i.e., contaminated) MUST be reextracted/repurged and
reanalyzed at no additional cost to the Agency. The Laboratory
Manager, or his designee, must address problems and solutions in the
SDG Narrative (Exhibit B).
TABLE 3
CHARACTERISTIC IONS FOR
SYSTEM MONITORING COMPOUNDS AND
INTERNAL STANDARDS FOR VOLATILE ORGANIC COMPOUNDS
Compound Primary Ion Secondary lon(s)
oYSTEM MONITORING COMPOUNDS
4-Bromofluorobenzene 95 174, 176
l,2-Dichloroethane-d-4 65 102
Toluene-d-g 98 70, 100
INTERNAL STANDARDS
Bromochloromethane 128 49, 130, 51
1,4-Difluorobenzene 114 63, 88
Chlorobenzene-d-5 117 82, 119
D-47/VOA OLM01.0
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SECTION IV
TABLE 4
CHARACTERISTIC IONS FOR VOLATILE TARGET COMPOUNDS
Analvte
Chlorome thane
Broraome thane
Vinyl chloride
Chloroe thane
Methylene chloride
Acetone
Carbon disulfide
1, 1-Dichloroethene
1 , 1-Dichloroethane
1 , 2-Dichloroethene
Chloroform
1 , 2 -Dichloroe thane
2-Butanone
1,1, 1 -Trichloroethane
Carbon tetrachloride
Bromodichlorome thane
1, 1,2,2-Tetrachloroethane
1 , 2 -Dichloropropane
trans- 1, 3-Dichloropropene
Trichloroethene
Dibromochlorome thane
1,1, 2 -Trichloroethane
Benzene
cis-1, 3-Dichloropropene
Bromoform
2-Hexanone
4-Methyl-2-pentanone
Te trachloroe thene
Toluene
Chlorobenzene
Ethyl benzene
S ty rene
Total Xylenes
Primary Ion*
50
94
62
64
84
43
76
96
63
96
83
62
43**
97
117
83
83
63
75
130
129
97
78
75
173
43
43
164
91
112
106
104
106
Secondary
lon^s)
52
96
64
66
49, 51, 86
58
78
61, 98
65, 83. 85, 98, 100
61, 98
85
64. 100, 98
57
99, ,.117, 119
119, 121
85
85, 131, 133, 166
65, 114
77
95, 97, 132
208, 206
83, 85, 99, 132, 134
-
77
171, 175, 250, 252, 254, 256
58, 57, 100
58, 100
129, 131, 166
92
114
91
78, 103
91
**
The primary ion should be used unless interferences are present, in which
case, a secondary ion may be used.
m/z 43 is used for quantitation of 2-Butanone, but m/z 72 must be present
for positive identification.
D-48/VOA
OLM01.0
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SECTION IV
TABLE 5
VOLATILE INTERNAL STANDARDS WITH CORRESPONDING TARGET COMPOUNDS
AND SYSTEM MONITORING COMPOUNDS ASSIGNED FOR QUANTISATION
Bromochloromechane
1,4-Difluorobenzene
Chlorobenzene-dc
Chloromethane
Bromoraethane
Vinyl Chloride
Chloroethane
Methylene Chloride
Acetone
Carbon Disulfide
1,1-Dichloroethene
1,1-Dichloroethane
l,2-Dichloroethene(tot.
Chloroform
1, 2-Dichloroethane
2-Butanone
1,2-Dichloroethane-d,
(smc)
1,1,1-Trichloroethane
Carbon Tetrachloride
Bromodichloromethane
1,2-Dichloropropane
trans -1,3-Dichloropropene
Trichloroethene
Dibromochloromethane
1,1,2-Trichloroethane
Benzene
cis-1,3 -Dichloropropene
Bromoform
2-Hexanone
4-Me thy1-2 -Pentanone
Tetrachloroethene
1,1,2,2-Tecrachloroethane
Toluene
Chlorobenzene
Ethylbenzene
Styrene
Xylene (total)
Bromofluorobenzene (smc)
Toluene-dg (smc)
(smc) - system monitoring compound
D-49/VOA
OLM01.0
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SECTION IV
TABLE 6
SYSTEM MONITORING COMPOUND RECOVERY LIMITS
%R %R
Compound Water S_oll
Toluene-dg 88-110 84-138
Bromofluorobenzene 86-115 59-113
l,2-Dichloroethane-d4 76-114 70-121
TABLE 7
MATRIX SPIKE RECOVERY AND
RELATIVE PERCENT DIFFERENCE LIMITS
Compound
%R
Water
RPD
Water
%R
Soil
RPD
Soil
1,1-Dichloroethane 61-145 14 59-172 22
Trichloroethene 71-120 14 62-137 24
Benzene 76-127 11 66-142 21
Toluene 76-125 13 59-139 21
Chlorobenzene 75-130 13 60-133 21
D-50/VOA OLM01.0
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EXHIBIT n
ANALYTICAL METHODS
FOR SEMIVOLATILES
D-l/SV
OLM01.0
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Table of Contents
Page
SECTION I - INTRODUCTION D-3/SV
SECTION II - SAMPLE PREPARATION AND STORAGE D-5/SV
PART A - SAMPLE STORAGE AND HOLDING TIMES D-6/SV
PART B - SAMPLE PREPARATION FOR EXTRACTABLE
SEMIVOLATILES (SNA) IN WATER D-7/SV
PART C - SAMPLE PREPARATION FOR EXTRACTABLE
SEMIVOLATILES (BNA) IN
SOIL/SEDIMENT D-12/SV
1. Medium Level Preparation for
Screening and Analysis of
Semivolatiles (BNA) D-13/SV
2. Low Level Preparation for
Screening and Analysis of
Semivolatiles (BNA) D-17/SV
SECTION III - SCREENING OF SEMIVOLATILE ORGANIC EXTRACTS D-32/SV
SECTION IV - GC/MS ANALYSIS OF SEMIVOLATILES D-36/SV
D-2/SV OLM01.0
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SECTION I
INTRODUCTION
The analytical methods that follow are designed to analyze water, soil and
sediment from hazardous waste sites for the organic compounds on the Target
Compound List (TCL, see Exhibit C). The methods are based on EPA Method 625
(Bases/Neutrals and Acids).
The methods are divided into the following sections: sample preparation,
screening, and analysis. Sample preparation covers sample extraction and
cleanup techniques. As described in the screening section, a portion of the
extracts may be screened on a gas chromatograph with appropriate detectors to
determine the concentration level of organics. The analysis section contains
the GC/MS analytical methods for organics.
D-3/SV OLM01.0
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SECTION I
1. Method for the Determination of Extractable Semivolatile Organic
Compounds.
1.1 Scope and Application
This method covers the determination of a number of organic compounds
that are partitioned into an organic solvent and are amenable to gas
chromatography. These target compounds and the contract required
quantitation limits are listed in Exhibit C.
Problems have been associated with the following compounds analyzed by
this method:
o Dichlorobenzidine and 4-Chloroaniline can be subject to
oxidative losses during solvent concentration.
o Hexachlorocyclopentadiene is subject to thermal decomposition in
the inlet of the gas chromatograph, chemical reactions in
acetone solution, and photochemical decomposition.
o N-Nitrosodiphenylamine decomposes in the gas chromatograph inlet
forming diphenylamine and, consequently, may be detected as
diphenylamine.
o Benzoic acid exhibits poor extraction recoveries.
Because performance data indicate erratic and poor linearity and
sensitivity, the following compounds have Maximum %RSD, or Maximum
%Difference criteria; however, these compounds must meet a minimum RRF
criterion of 0.010:
1.2
1.3
2,2'-oxybis(l-Chloropropane)
4-Chloroaniline
Hexachlorobutadiene
Hexachlorocyclopentadiene
2-Nitroaniline
DimethyIphthalate
3-Nitroaniline
2,4-Dinitrophenol
4-Nitrophenol
DiethyIphthalate
4-Nitroaniline
4,6-Dinitro-2-methylphenol
N-Nitrosodiphenylamine
Di-n-butylphthalate
ButylbenzyIphthalate
3,3'-Dichlorobenzidine
bis(2-Ethylhexyl)phthalate
Di-n-octyIphthalate
2,4,6-Tribromophenol
In addition, Carbazole, a new target compound for which there is
insufficient performance data, must only meet a minimum RRF criterion
of 0.010.
The method involves solvent extraction of the matrix sample,
characterization to determine the appropriate analytical protocol to be
used, and GC/MS analysis to determine semivolatile organic compounds
present in the sample.
D-4/SV
OLM01.0
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SECTION II
SAMPLE PREPARATION AND STORAGE
D-5/SV OLM01.0
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SECTION II
PART A - SAMPLE STORAGE AND HOLDING TIMES
1. Procedures for Sample Storage
The samples must be protected from light and refrigerated at A°C (±2°C)
from the time of receipt until 60 days after delivery of a complete
data package to the Agency. After 60 days the samples may be disposed
of in a manner that complies with all applicable regulations.
Samples must be stored in an atmosphere demonstrated to be free of all
potential contaminants.
Samples, sample extracts, and standards must be stored separately.
2. Procedure for Sample Extract Storage
Sample extracts must be protected from light and stored at 4°C (±2°C)
until 365 days after delivery of a complete data package to the Agency.
Samples must be stored in an atmosphere demonstrated^to be free of all
potential contaminants.
Samples, sample extracts, and standards must be stored separately.
3. Contract Required Holding Times
Extraction of water samples by continuous liquid-liquid procedures
shall be started within 5 days of VTSR (Validated Time of Sample
Receipt). Extraction of soil/sediment samples by sonication procedures
shall be completed within 10 days of VTSR. NOTE: Separatory funnel
extraction procedures are not permitted.
Extracts of either water or soil/sediment samples must be analyzed
within 40 days following extraction.
D-6/SV OLM01.0
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SECTION II
- ' - 5 • •,--... . . f. v ••••'••,»-•. -5 " !. '•
PART_._B .- CAMPLE PREPARATION FOR EXTRACTABLE' SEMIVQLATILES' (SNA) IN WATER
I• Summary of Sample Preparation Method
1.1 A one ^liter aliquot of samp'le is acidified to pH 2 and extracted with
methyLene chloride using a continuous liquid"-liquid extractor .
Separatory funnel extraction is NOT permitted. The methylene chloride
extract is dried and concentrated to a volume of 1.0 mL.
2. Interferences
Contaminants in solvents, reagents, glassware, and other sample
processing hardware may cause method interferences such as discrete
artifacts arid/or elevated baselines in the total ion current profiles
JTICPs). All of these materials routinely must be demonstrated to be
free from interferences under ther condition's "of" £he .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.
'••«.' ^ ' ~ ,• U C' ' « * --' ' * "* «"'/'i'j(*'»- •*•,*" '' v"- **•>'•"
3. Apparatus and' Materials • ...
3.1 Glassware (brand names and catalog numbers are included for
illustration purposes 'only) 7 c v " ' *_,
3.1.1 Continuous liquid-liquid extractors - equipped with Teflon or
glass connnecting joints and stopcocks requiring no lubrication
(Hershberg-Wolf Extractor, Ace Glass Company, Vineland, NJ, P/N
6841-10 or equivalent).
. .,, ,. ^ t. 3._1.2 -^ •Drying* cojrumn--^ 3.9 mm LD,chrqmato§r.aphic cplumn^with coarse
frit "(substitution of *a small pad of Pyr'ex glass wool for the
,.f ^ ^ •', , • -. v, »^?^t-w^^ P??veH? cr-?s«s* contamination of sample extracts).
3.1.3 Concentrator tube - Kuderna-Danish, 10 mL, graduated (Kontes
' ' ' ~ r* ' K-570050:'1025 or equivalent)'."' Calibration'must "be checked at
the volumes employed in the test. Ground-glass stoppers are
used to 'prevent evaporation of extracts."
'3.1.4 Evaporative^flask -'Kuderna-Danish,* 5t)0'mL (Ko'ntes K-570001-
0500 or equivalent). Attach to concentrator tube with springs.
3~.1.5 Snyder-column - Kuderna-Danish, -three-ball macro (Kontes
" " "" " " "" "K-50"3000-0121 6r equivalent)." '" " '
' " " v ' 3.1.6"" Snyder'c&Iumn - Kuderna-Oanfsli,1 tvo'-'bStl 'micr'o ("Kdntes K569001-
0219 or equivalent).
. - - - . r . - • .
1 • 3.1.7 'Vials -Camber glass, 2 mL-capacity witrh Teflon-Lined screw cap.
- l- • '• - • f f -- -.-- r v i -t ' r '- • f * • r • j- . P *1 • v ••»*--•
3.2 Silican car-bide* boiling chips - approximately 10/40 mesh. Heat to
'• '' " 400°C" for ^d" miritit§sf oSr''Sbxhlet'extract with methylene chloride.
4 r
OLM01.0
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SECTION II
3.3 Water bach - heated, with concentric ring cover, capable of temperature
control (+ 2°C). The bath should be used in a hood.
3.4 Balance - analytical, capable of accurately weighing + 0.0001 g.
3.5 Nitrogen evaporation device equipped with a water bath that can be
maintained at 35-40°C. The N-Evap by Organomation Associates, Inc.,
South Berlin, MA (or equivalent), is suitable.
4. Reagents
4.1 Reagent water - defined as water in which an interferent is not
observed at or above the CRQL of each parameter of interest.
4.2 Sodium thiosulfate - (ACS) granular.
4.3 Sulfuric acid solution (1+1) - slowly add 50 mL of i^SO^ (sp gr 1.84)
to 50 mL of reagent water.
4.4 Acetone, methanol, methylene chloride - pesticide residue analysis
grade or equivalent.
4.5 Sodium sulfate - (ACS) powdered, anhydrous. Purify by heating at 400°C
for four hours in a shallow tray, cool in a desiccator and store in a
glass bottle (Baker anhydrous powder, catalog #73898, or equivalent).
4.6 Surrogate standard spiking solution.
4.6.1 Surrogate standards are added to all samples and calibration
solutions; the compounds specified for this purpose are
Phenol-dij, 2,4,6-Tribromophenol, 2-Fluorophenol,
Nitrobenzene-d5, Terphenyl-d^, 2-Fluorobiphenyl, 2-
Chlorophenol-d^, and 1,2-Dichlorobenzene-d^. Additional
surrogates may be added at the laboratory's discretion.
4.6.2 Prepare a surrogate standard spiking solution that contains
Nitrobenzene-dg, Terphenyl-d^, 2-Fluorobiphenyl, and 1,2-
Dichlorobenzene-d^ at a concentration of 100 ug/mL; Phenol-d^,
2,4,6-Tribromophenol, 2-Fluorophenol, and 2-Chlorophenol-d^ at
a concentration of 200 ug/mL. Store the spiking solutions at
4°C (+2°C) in Teflon-sealed containers. The solutions should
be checked frequently for stability. These solutions must be
replaced after twelve months, or sooner if comparison with
quality control check samples indicates a problem.
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SECTION II
4.7 BNA Matrix standard spiking solution - the matrix spike solution
consists of the following:
Bases/Neutrals Acids
1,2,4-Trichlorobenzene Pentachlorophenol
Acenaphthene Phenol
2,4-Dinitrotoluene 2-Chlorophenol
Pyrene 4-Chloro-3-methylphenol
N-Nitroso-di-n-propylamine 4-Nitrophenol
1,4-Dichlorobenzene
Prepare a spiking solution that contains each of the base/neutral
compounds above at 100 ug/1.0 mL in methanol and the acid compounds at
200 ug/1.0 ml in methanol. Analyze duplicate aliquots of a sample
spiked with BNA matrix spiking solution.
5. Water Sample Extraction
5.1 Continuous liquid-liquid extraction is used to extract the samples.
5.1.1 Add methylene chloride to the bottom of the extractor and fill
it to a depth of at least 1 inch above the bottom side arm.
5.1.2 Using a 1 liter graduated cylinder, measure out a 1.0 liter
sample aliquot. Transfer the 1 liter sample aliquot to the
continuous extractor. Pipet 0.5 mL of surrogate standard
spiking solution into the sample and mix veil. Check the pH of
the sample with wide range pH paper and adjust the pH to 2.0
with 1:1 H2S04.
5.1.3 Following the procedures in 5.1.1 and 5.1.2 above, prepare two
additional 1.0 Liter aliquots of the sample chosen for spiking.
Add 0.5 mL of the BNA Matrix Spiking Solution to each of the
additional aliquots. The frequency of MS/MSD analysis is given
in Section IV, paragraph 8.6.
5.1.4 Add 500 mL of methylene chloride to the distilling flask. Add
sufficient reagent water to ensure proper operation. Extract
for 18 hours. Allow to cool, then.detach the distilling flask,
and label the flask.
5.1.5 Prepare a method blank with each group of water samples
extracted. For semivolatile analyses, a method blank for water
samples consists of a 1 L volume of reagent water (see
paragraph 4.1), spiked with the surrogates and carried through
the entire analytical procedure. The frequency of method blank
analysis is given in Section IV, paragraph 8.7
5.2 Concentrating the Extracts
5.2.1 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
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SECTION II
K-D, if equivalency is demonstrated for all the semivolatile
target compounds listed in Exhibit C.
5.2.2 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 Erlenmeyer flask and column with 20 to 30 mL of methylene
chloride to complete the quantitative transfer.
5.2.3 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) 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 IS minutes. At 'the proper
rate of distillation, the balls of the column will chatter
actively, 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. 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.
5.2.4 Two different concentration techniques are permitted to obtain
the final 1.0 mL volume: micro Snyder column and nitrogen
blowdown techniques.
5.2.4.1 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 on a hot water bath
(60*C to 80*C) 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 distillation, the balls of the column will
chatter actively, 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. Remove the
Snyder column and rinse its 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
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SECTION rr
a Teflon-sealed screw-cap bottle, label the bottle,
and store at 4'C (±2'C).
5.2.4.2 Nitrogen Slowdown Technique (taken from ASTM Method
D3086)
Place the concentrator tube with an open micro
Snyder attached 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 blowdown apparatus must be stainless
steel, copper, or Teflon tubing. 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 Teflon-sealed
screw-cap bottle, label the bottle and store at 4*C
(±2'C).
6. The sample extracts are ready for GC/MS analysis. Proceed to Section
IV, GC/MS Analysis of Semivolatiles. If high concentrations are
suspected (e.g., highly colored extracts), the optional GC/FID screen
in Section III is recommended.
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SECTION II
PAST C - SAMPLE PREPARATION FOR EXTRACTABLE SEMIVOLATILES (BNA) IN
SOIL/SEDIMENT
It is mandatory that all soil/sediment samples be characterized as to
concentration level so that the appropriate analytical protocol is chosen to
ensure proper quantitation limits for the sample. Note that the terms "low
level" and "medium level" are not used here AS a judgement of degree of
contamination but rather as a description of the concentration ranges that
are encompassed by the "low" and "medium" level procedures.
The laboratory is at liberty to determine the method of characterization.
The following two screening methods may be used for soil/sediment sample
characterization:
o Screen an aliquot from the "low level" 30 g extract or an aliquot
from the "medium level" 1 g extract.
o Screen using either GC/FID or GC/MS as the screening instrument.
The concentration ranges covered by these two procedures may be considered to
be approximately 330 ug/kg - 10,000 ug/kg for the low level analysis and
>10,000 ug/kg for medium level analysis for semivolatile extractables.
Screen from the Medium Level Method
Take 5.0 mL from the 10.0 mL total extract and concentrate to 1.0 ml, and
screen. If the sample concentration is >10,000 ug/kg. proceed with GC/MS
analysis of the organics. If the sample concentration is <10,000 ug/kg,
discard the medium level extract and follow the low level method.
Screen from the Low Level Method
Take 5.0 mL from the 300 mL (approximate) total extract from the 30 g sample
and concentrate to 1.0 mL and screen. If the original sample concentration
is >10,000 ug/kg, discard the 30 g extract and follow the medium level
methods for organics, using medium level surrogates. If the sample
concentration is <10,000 ug/kg, proceed with concentration and the remainder
of the low level method.
Mandatory GPC Clean Up
Regardless of the concentration level, all soil/sediment sample extracts must
be subjected_to clean up by Gel Permeation Chromatography (GPC). Because the
effectiveness of GPC can be adversely affected by the amount of material
loaded onto the GPC column, it may be advisable to screen the sample extracts
described here prior to employing GPC.
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SECTION II
1. Medium Level Preparation for Screening and Analysis of Semivolaciles
1.1 Scope and Application
This procedure is designed for Che preparation of sediment/soil samples
which may contain organic chemicals at a level greater than 20,000
ug/kg.
1.1.1. The extracts and sample aliquots prepared using this method are
screened by GC/MS or FID, using capillary columns for
semivolatile priority pollutants, and related organic
chemicals. The results of these screens will determine whether
sufficient quantities of pollutants are present to warrant
analysis by low or medium protocol.
1.1.2 If the screenings indicate no detectable pollutants at the
lower limits of quantitation, the sample should be prepared by
the low level protocol in Section II, Fart C, beginning at
paragraph 2.
1.2 Summary of Method
1.2.1. Approximately 1 g portions of sediment/soil are transferred to
vials and extracted with methylene chloride. The methylene
chloride extract is screened for extractable organics by GC/FID
or GC/MS.
1.2.2 If organic compounds are detected by the screen, the methylene
chloride extract is subjected to GPC clean up and analyzed by
GC/MS for extractable organics.
1.2.3 If no organic compounds are detected by the medium level
screen, then a low level sample preparation is required.
1.3 Interferences
1.3.1. Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that
lead to discrete artifacts and/or elevated baselines in the
total ion current profiles. All of these materials routinely
must be demonstrated to be free from interferences under the
_ conditions of the analysis by running laboratory reagent
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.
1.4 Limitations
1.4.1. The procedure is designed to allow quantitation limits for
screening purposes as low as 20,000 ug/kg for extractable
organics. For analysis purposes, the quantitation limits are
20,000 ug/kg for extractable organics. If peaks are present
based on the GC/FID screen, the sample is determined to require
a medium level analysis by GC/MS. Some samples may contain
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SECTION II
high concentrations of chemicals that interfere with the
analysis of other components at lower levels; the quantitation
limits in those cases may be significantly higher.
1.4.2 These extraction and preparation procedures were developed for
rapid and safe handling of high concentration hazardous waste
samples. The design of the methods thus does not stress
efficient recoveries or low limits of quantitation of all
components. Rather, the procedures were designed to screen, at
moderate recovery and sufficient sensitivity, a broad spectrum
of organic chemicals. The results of the analyses thus may
reflect only a minimum of the amount actually present in some
samples.
1.5 Reagents
1.5.1. Sodium Sulfate - anhydrous powdered reagent grade, heated at
400*C for four hours, cooled in a desiccator, and stored in a
glass bottle (Baker anhydrous powder, catalog # 73898 or
equivalent). -
1.5.2 Acetone, ttethanol, Methylene chloride - pesticide residue
analysis grade or equivalent.
1.5.3 Base/Neutral and Acid Surrogate Spiking Solution
Surrogate standards are added to all samples and calibration
solutions. The compounds specified are Phenol-de,
2,4,6-Tribromophenol, 2-Fluorophenol, Nitrobenzene-dj,
Terphenyl-dj^, 2-Fluorobiphenyl, 2-Chlorophenol-d^, and 1,2-
Dichlorobenzene-d^. Prepare a surrogate standard spiking
solution that contains Nitrobenzene-dj, Terphenyl-d^,
2-Fluorobiphenyl, and 1,2-Dichlorobenzene-d^ at a concentration
of 100 ug/mL; Phenol-dg, 2,4,6-Tribromophenol, 2-Fluorophenol,
and 2-Chlorophenol-d^ at a concentration of 200 ug/mL. Store
the spiking solutions at 4*C (±2"C) in Teflon-sealed
containers. The solutions should be checked frequently for
stability. These solutions must be replaced after twelve
months, or sooner if comparison with quality control check
samples indicates a problem.
1.5.4— Base/Neutral and Acid Matrix Spiking solution
Prepare a spiking solution in methanol that contains the
following compounds at a concentration of 100 ug/mL for
base/neutrals and 200 ug/mL for acids. Store the spiking
solutions at 4*C (±2*C) in Teflon-sealed containers. The
solutions should be checked frequently for stability. These
solutions must be replaced after twelve months, or sooner if
comparison with quality control check samples indicates a
problem.
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SECTION II
Bases/ Neucrals
1,2,4-Trichlorobenzene Pentachlorophenol
Acenaphthene Phenol
2,4-Dinitrotoluene 2-Chlorophenol
Pyrene 4-Chloro-3-methylphenol
N-Nitroso-di-n-propylamine 4-Nitrophenol
1,4-Dichlorobenzene
1.6 Equipment
1.6.1. Glass scintillation vials - at least 20 mL, with screw cap and
teflon or aluminum foil liner.
1.6.2 Spatula - stainless steel or Teflon.
1.6.3 Balance - capable of weighing 100 g to ± 0.01 g.
1.6.4 Vials and caps - 2 mL for GC auto sampler.
1.6.5 Disposable pipets - Pasteur; glass wool rinsed with methylene
chloride.
1.6.6 Concentrator tubes - 15 mL.
1.6.7 Ultrasonic cell disruptor - Heat Systems, Ultrasonics, Inc.,
Model tf-385 SONICATOR (475 Watt with pulsing capability, No.
200, 1/2 inch tapped disruptor horn and No. 419, 1/8 inch
standard tapered MICROTIP probe), or equivalent device with a
minimum of 375 Watt output capability. NOTE: In order to
ensure Chat sufficient energy is transferred to the sample
during extraction, the MICROTZP probe must be replaced if the
tip begins to erode. Erosion of the tip is evidenced by a
rough surface.
1.6.8 Sonabox acoustic enclosure - recommended with above disrupters
for decreasing cavitation sound.
1.6.9 Test tube rack.
1.6.10 Oven - drying.
1.6.11_ Desiccator.
1.6.12 Crucibles - porcelain.
1.7 Medium Level Sample Preparation.
1.7.1. Transfer the sample container into a fume hood. Decant and
discard any water layer on a sediment sample. Mix samples
thoroughly, especially composited samples. Discard any foreign
objects such as sticks, leaves, and rocks. Transfer
approximately 1 g (record weight to the nearest 0.1 g) of
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SECTION II
sample to a 20-mL vial. Wipe che mouch of the vial with a
tissue to remove any sample material. Record the exact weight
of sample taken. Cap the vial before proceeding with the next
sample to avoid any cross -contamination.
1.7.1.1 Transfer 50 g of soil/sediment to a 100 m.L beaker.
Add 50 mL of water and stir for 1 hour. Determine
pH of sample with glass electrode and pH meter while
stirring. Report pH value on appropriate data
sheets. If the pH of the soil is greater than 11 or
less than 5, contact the Technical Project: Officer
cited in the contract for instructions on how to
handle the sample. Document the instructions in the
SDG Narrative. Discard this portion of sample.
NOTE: If limited sample volume is received, use 5 g
of soil and 5 mL of water for the pH determination.
Note this in the SDG Narrative.
1.7.2 Immediately after weighing the sample for extraction, weigh
5-10 g of the sediment into a tared crucible. Determine the
percent moisture by drying overnight at 105*C. Allow to cool
in a desiccator before weighing. Concentrations of individual
analytes will be reported relative to the dry weight of
sediment .
°f
1.7.3 Add 2.0 g of anhydrous powdered sodium sulfate to the sample in
the 20 mL vial from paragraph 1.7.1 and mix well .
1.7.4 Surrogates are added to all samples, spikes, and blanks. Add
0.5 mL of surrogate spiking solution to sample mixture.
1.7.5 Add 0.5 mL of matrix standard spiking solution to each of two 1
g portions from the sample chosen for spiking. The frequency
of MS/MSD analysis is given in Section IV, paragraph 8.6.
•n
1.7.6 Immediately add 9.5 mL of methylene chloride to the sample and
disrupt the sample with the 1/8 inch tapered MICROTIP
ultrasonic probe for 2 minutes at output control setting 5, in
continuous mode (if using a sonicator other than Models W-375
or W-385, contact the Project Officer for appropriate output
"settings). Before extraction, make certain that the sodium
sulfate is free flowing and not a consolidated mass. As
required, break up large lumps with a clean spatula or, very
carefully, with the tip of the unenergized probe.
Add only 9.0 mL of methylene chloride to the matrix spike
samples to achieve a final volume of 10 mL.
1.7.7 Prepare a method blank with each group of medium soil/sediment
samples extracted. For semivolatile analyses, a method blank
for medium soil/sediment samples consists of 1 g of sodium
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SECTION II
sulfate (see paragraph 1.5.1), spiked with the surrogates and
carried through the entire analytical procedure. The frequency
of method blank analysis is given in Section IV, paragraph 8.7
1.7.8 Loosely pack disposable Pasteur pipets with 2-3 cm glass wool
plugs. Filter the extract through the glass wool and collect
at least 8.0 mL in a concentrator tube.
1.7.9 If the extract is to be screened prior to GPC, concentrate 5.0
mL of the extract collected in paragraph 1.7.7 to 1.0 mL using
the nitrogen blowdown technique described in paragraph 3.6.2.
Transfer the concentrate to an autosampler vial for GC/FID or
GC/MS for screening. The quantitation limits for the screening
procedure in Section III are approximately 20,000 ug/Kg.
1.7.10 If the extract is to be cleaned up using GPC without screening,
take at least 8.0 mL of the extract in paragraph 1.7.7 and
proceed to paragraph 3 of this section. Following GPC, the 5.0
mL of extract collected must be concentrated to 0.5 mL by the
nitrogen blowdown technique described in paragraph 3.6.2, and
screened according to the procedures in Section III. In this
case, the quantitation limits for the screening procedures in
Section III are approximately 10,000 ug/Kg.
2. Low Level Preparation for Screening and Analysis of Semivolatiles
2.1 Summary of Method
A 30 gram portion of sediment is mixed with anhydrous powdered sodium
sulfate and extracted with 1:1 methylene chloride/acetone using an
ultrasonic probe. If the optional low level screen is used, a portion
of this dilute extract is concentrated fivefold and is screened by
GC/FID or GC/MS. If peaks are present at greater than 20,000 ug/kg,
discard the extract and prepare the sample by the medium level method.
If no peaks are present at greater than 20,000 ug/kg, the entire
extract is concentrated, subjected to GPC clean up, and analyzed by
GC/MS for extractable organics.
2.2 Interference's
Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample-processing hardware that lead to
discrete artifacts and/or elevated baselines in the total ion current
profiles. All of these materials routinely must be demonstrated to be
free from interferences under the conditions of the analysis by running
laboratory reagent blanks. Matrix interferences may be caused by
contaminants that are c©extracted from the sample. The extent of
matrix interferences will vary considerably from source to source.
2.3 Apparatus and Materials
2.3.1 Apparatus for determining percent moisture
2.3.1.1 Oven - drying.
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SECTION II
2.3.1.2 Desiccator.
2.3.1.3 Crucibles - porcelain.
2.3.2 Disposable Pasteur glass pipets - 1 raL.
2.3.3 Ultrasonic cell disrupter, Heat Systems, Ultrasonics, Inc.,
Model W-385 SONICATOR (475 Watt with pulsing capability, No.
305, 3/4 inch tapped high gain "Q" disrupter horn, or No. 208,
3/4 inch standard solid disrupter horn), or equivalent device
with a minimum of 375 Watt output capability. NOTE: In order
to ensure that sufficient energy is transferred to the sample
during extraction, the horn must be replaced if the tip begins
to erode. Erosion of the tip is evidenced by a rough surface.
Sonabox acoustic enclosure - recommended with above disrupters
for decreasing cavitation sound.
2.3.4 Beakers - 400 mL.
2.3.5 Vacuum filtration apparatus.
2.3.5.1 Buchner funnel.
2.3.5.2 Filter paper - Whatman No. 41 or equivalent.
2.3.6 Kuderna-Danish (K-D) apparatus.
2.3.6.1 Concentrator tube - 10 mL, graduated (Rentes
K-570040-1025 or equivalent).
2.3.6.2 Evaporative flask - 500 mL (Kontes K-570001-0500 or
equivalent).
2.3.6.3 Snyder column - three-ball macro (Kontes
K-503000-0121 or equivalent).
2.3*6.4 Snyder column - two-ball micro (Kontes K-569001-0219
or equivalent).
2.3.7 Silicon carbide boiling chips - approximately 10/40 mesh. Heat
to 400*C for 30 minutes or Soxhlet extract with methylene
_ chloride.
2.3.8 Water bath - heated, with concentric ring cover, capable of
temperature control (+2*C). The bath should be used in a hood.
2.3.9 Balance - capable of accurately weighing + 0.01 g.
2.3.10 Vials and caps - 2 mL for GC auto sampler.
2.3.11 Balance - analytical, capable of accurately weighing ± O.OOOlg.
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SECTION' II
2.3.12 Nitrogen evaporation device equipped with a water bath that can
be maintained at 35-40°C. (N-Evap by Organomation Associates,
Inc., South Berlin, MA, or equivalent).
2.3.13 Pyrex glass wool.
2.3.14 Pasteur pipets - disposable.
2.4 Reagents
2.4.1 Sodium Sulfate - anhydrous powdered reagent grade, heated at
400*C for four hours, cooled in a desiccator, and stored in a
glass bottle (Baker anhydrous powder, catalog #73898 or
equivalent).
2.4.2 Methylene chloride, methanol, acetone, isooctane, 2-propanol,
and benzene - pesticide residue analysis grade or equivalent.
2.4.3 Reagent water - defined as water in which an interferent is not
observed at or above the CRQL of each parameter of interest.
2.4.4 Sodium Sulfite - reagent grade.
2.4.5 Base/Neutral and Acid Surrogate Spiking Solution
Surrogate standards are added to all samples and calibration
solutions. The compounds specified are Phenol-de,
2,4,6-Tribromophenol, 2-Fluorophenol, Nitrobenzene-d^,
Terphenyl-dj^, 2-Fluorobiphenyl, 2-Chlorophenol-d4, and 1,2-
Dichlorobenzene-d^. Prepare a surrogate standard spiking
solution that contains Nitrobenzene-d5, Terphenyl-d^,
2-Fluorobiphenyl, and 1,2-Dichlorobenzene-d^ at a concentration
of 100 ug/mL; Phenol-dg, 2,4,6-Tribromophenol, 2-Fluorophenol,
and 2-Chlorophenol-d^ at a concentration of 200 ug/mL. Store
the spiking solutions at 4'C (±2*C) in Teflon-sealed
containers. The solutions should be checked frequently for
stability. These solutions must be replaced after twelve
months, or sooner if comparison with quality control check
samples indicates a problem.
2.4.6 Base/Neutral and Acid Matrix Spiking solution
Prepare a spiking solution in methanol that contains the
following compounds at a concentration of 100 ug/mL for
base/neutrals and 200 ug/mL for acids. Store the spiking
solutions at 4'C (+2*C) in Teflon-sealed containers. The
solutions should be checked frequently for stability. These
solutions must be replaced after twelve months, or sooner if
comparison with quality control check samples indicates a
problem.
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SECTION II
Bases/ Neutrals Acids
1,2,4-Trichlorobenzene Pentachlorophenol
Acenaphthene Phenol
2,4-Dinitrocoluene 2-Chlorophenol
Pyrene 4-Chloro-3-raechylphenol
N-Nitroso-di-n-propylamine 4-Nitropheno.L
1,4-Dichlorobenzene
2.5 Low Level Sample Preparation
2.5.1 Decant and discard any water layer on a sediment sample. Mix
samples thoroughly, especially composited samples. Discard any
foreign objects such as sticks, leaves, and rocks.
Transfer 50 g of soil/sediment to 100 mL beaker. Add 50 mL of
wacer and stir for 1 hour. Determine pH of sample with glass
electrode and pH meter while stirring. Report pH value on
appropriate data sheets. If the pH of the soil is greater than
11 or less than 5, contact the Technical Project Officer cited
in the contract for instructions on how to handle the sample.
Document the instructions in the SDG Narrative. Discard this
portion of sample. NOTE; If limited sample volume is
received, use 5 g of soil and 5 mL of water for the pH
determination. Note this in the SDG Narrative.
2.5.2 The following steps should be performed rapidly to avoid loss
of the more volatile extractables. Weigh approximately 30 g of
sample co the nearest 0.1 g into a 400-mL beaker and add 60 g
of anhydrous powdered sodium sulfate. Mix well. The sample
should have a sandy texture at this point. Immediately, add
100 mL of 1:1 methylene chloride-acetone to the sample, then
add the surrogates according to paragraph 2.5.2.3.
2.5.2.1 Immediately after weighing the sample for
extraction, weigh 5-10 g of the sediment into a
tared crucible. Determine the percent moisture by
drying overnight at 105*C. Allow to cool in a
- desiccator before weigh .ng. Concentrations of
individual analytes will be reported relative to the
dry weight of sediment.
g of sample - g of dry sample
f , x 100 - % moisture
- g of sample
2.5.2.2 Weigh out two 30 g (record weight to nearest 0.1 g)
portions for use as matrix and matrix spike
duplicates according to paragraph 2.5.2. Add 0.5 mL
of the SNA matrix spike solution to each of two
portions. The frequency of MS/MSD analysis is given
in Section IV, paragraph 8.6.
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SECTION II
2.5.2.3 Add 0.5 mL of base/neutral and acid surrogate
standard to the sample and each of the aliquots in
2.5.2.2.
2.5.2.4 Prepare a method blank with each group of low
soil/sediment samples extracted. For semivolatile
analyses, a method blank for low soil/sediment
samples consists of 30 g of sodium sulfate (see
paragraph 2.4.1), spiked with the surrogates and
carried through the entire analytical procedure.
The frequency of method blank analysis is given in
Section IV, paragraph 8.7
2.5.3 Place the bottom surface of the tip of the 3/4 inch disrupter
horn about 1/2 inch below the surface of the solvent but above
the sediment layer.
2.5.4 Sonicate for 1 1/2 minutes with the tf-385 (or 3 minutes with
the W-375), using No. 208, 3/4 inch standard disrupter horn
with output control knob set at 10 (or No. 305, 3/4 inch tapped
high gain "Q" disrupter horn at 5) and mode switch on "1 sec.
pulse" and % duty cycle knob set at 50% (if using a sonicator
other than Models W-375 or W-385, contact the Project Officer
for appropriate output settings). Do NOT use MICROTIP probe.
2.5.5 Decant and filter extracts through Whatman #41 filter paper
using vacuum filtration or centrifuge and decant extraction
solvent.
2.5.6 Repeat the extraction two more times with 2 additional 100 mL
portions of 1:1 methylene chloride-acetone. Before each
extraction, make certain that the sodium sulfate is free
flowing and not a consolidated mass. As required, break up
large lumps with a clean spatula or, very carefully, with the
tip of the probe. Decant the extraction solvent after each
sonication. On the final sonication, pour the entire sample
into the Buchner funnel and rinse with 1:1 methylene
chloride-acetone.
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SECTION II
2.6 Concentration and Solvent Exchange
2.6.1 Low level soil/sediment samples prepared by the procedures in
paragraph 2 will result in extracts containing a mixture of
acetone and methylene chloride. Because all soil/sediment
sample extracts must be subjected to GPC clean up prior to
analysis, the majority of the acetone must be removed from the
extract, otherwise it will have adverse effects on the GPC
column. To remove the acetone from the sample extract, follow
the steps in 2.6.2.
2.6.2 Transfer the extract to a Kuderna-Danish (K-D) concentrator
consisting of a 10 mL concentrator tube and a 500 mL
evaporative flask. Other concentration devices or techniques
may be used if equivalency is demonstrated for all extractable
compounds listed in Exhibit C.
2.6.3 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 methylene chloride to the top. Place the
K-D apparatus on a hot water bath (60 to 80°C) 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 and allow it to
drain and cool for at least 10 minutes.
2.6.4 Dilute the extract to 10.0 mL with methylene chloride, and
proceed with GPC clean up (see paragraph 3).
3. Extract Cleanup bv Gel Permeation Chromatoyraphv
Gel permeation chromatography (GPC) is a size exclusion cleanup
procedure using organic solvents and hydrophobic gels in the separation
of synthetic macromolecules. The packing gel is porous and is
characterized by the range or uniformity (exclusion range) of that pore
size. In the choice of gels, the exclusion range must be larger than
the molecular size of the molecules to be separated. A cross-linked
divinyl benzenestyrene copolymer (SX-3 Bio Beads or equivalent) is
specified for this method.
GPC is required for all soil/sediment samples, regardless of
concentration level, for the elimination of lipids, polymers,
copolymers, proteins, natural resins and polymers, cellular components,
viruses, steroids, and dispersed high-molecular-weight compounds from
the sample extract. GPC is appropriate for both polar and non-polar
analytes, therefore, it can be used effectively to clean up extracts
containing a broad range of analytes.
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SECTION II
Normally, this method is most efficient for removing high boiling
materials that condense in the injection port area of a. gas
chromatograph (GC) or in the front of the GC column. This residue
ultimately will reduce the chromatographic separation efficiency or
column capacity because of adsorption of the target analytes on the
active sites. Pentachlorophenol especially is susceptible to this
problem.
In the event that the Laboratory fails to appropriately employ GPC
clean-up procedures, the Agency will require the clean up and
reanalysis of all affected samples or sample extracts at no additional
cost to the Agency.
3.1 Apparatus and Materials
3.1.1 Gel permeation chromatography (GPC) cleanup device. NOTE: GPC
cleanup is required for all soil/sediment extracts.
Gel permeation chromatography system - GPC Autoprep Model 1002
A or B (Analytical Biochemical Laboratories, Inc., or
equivalent) Systems that perform very satisfactorily also have
been assembled from the following components - an HPLC pump, an
auto sampler or a valving system with sample loops, and a
fraction collector. All systems, whether automated or manual,
must meet the calibration requirements of paragraph 3.4.
3.1.1.1 Chromatographic column - 700 mm x 25 mm i.d. glass
column. Flow is upward. To simplify switching from
the UV detector during calibration to the GPC
collection device during extract cleanup, an
optional double 3-way valve (Rheodyne Type 50 Teflon
Rotary Valve #10-262 or equivalent) may be attached
so that the column exit flow can be shunted either
to the UV flow-through cell or to the GPC collection
device.
3.1.1.2 Guard column - (Optional) 5 cm, with appropriate
» fittings to connect to the inlet side of the
analytical column (Supelco 5-8319 or equivalent).
3.1.1.3 Bio Beads (S-X3) - 200-400 mesh, 70 gm (Bio-Rad
Laboratories, Richmond, CA, Catalog 152-2750 or
equivalent). An additional 5 gm of Bio Beads is
required if the optional guard column is employed.
The quality of Bio Beads may vary from lot to lot
because of excessive fines in some lots. In
addition to fines having a detrimental effect on
chromatography, they also can pass through the
column screens and damage the valve.
3.1.1.4 Ultraviolet detector - fixed wavelength (254 nm)
with a semi-prep flow*through cell.
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SECTION II
3.1.1.5 Strip chart recorder, recording integrator or
laboratory data system.
3.1.1.6 Syringe - 10-mL with Luerlok fitting.
3.1.1.7 Syringe filter assembly, disposable - Bio-Rad "Prep
Disc" sample filter assembly #343-0005, 25 mm, and 5
micron filter discs or equivalent. Check each batch
for contaminants. Rinse each filter assembly (prior
to use) with methylene chloride if necessary.
3.1.1.8 A description of a manual system assembled from
parts can be found in Wise, R.H., Bishop, D.F. ,
Williams, R.T. & Austern, B.M. "Gel Permeation
Chromatography in the GC/MS Analysis of Organics in
Sludges" U.S. EPA, Municipal Environmental Research
Laboratory, Cincinnati, Ohio, 45268.
3.2 Reagents
3.2.1 GPC Calibration Solution - prepare a calibration solution in
methylene chloride containing Che following analytes (in
elution order):
Compound mg/mL
corn oil 25.0
bis(2-ethylhexyl)phthalate 1.0
me choxychlor 0.2
perylene 0.02
sulfur (optional) 0.08
NOTE: If used, sulfur is not very soluble in methylene
chloride, however, it is soluble in warm corn oil. Therefore,
one approach is to weigh out the corn oil, warm it and transfer
the weighed amount of sulfur into the warm corn oil. Mix it
and then transfer into a volumetric flask with methylene
chloride, along with the other calibration compounds.
%
Store the calibration solution in an amber glass bottle with a.
Teflon-lined screw-cap at 4*C, and protect from light
(refrigeration may cause the corn oil to precipitate. Before
use, allow the calibration solution to stand at room
- temperature until the corn oil dissolves). Replace the
calibration standard solution every 6 months, or more
frequently if necessary.
3.3 Column Preparation
3.3.1 Weigh out 70 gn of Bio Beads (SX-3). Transfer them to a quart
bottle with a Teflon-lined cap or a 500 mL separatory funnel
with a large bore stopcock, and add approximately 300 mL of
methylene chloride. Swirl the container to ensure the wetting
of all beads. Allow the beads to swell for a minimum of 2
hours. Maintain enough solvent to cover the beads sufficiently
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SECTION II
at all times. If a guard column is to be used, repeat the
above with 5 gm of Bio Beads in a 125 mL bottle or a beaker,
using 25 mL of methylene chloride.
3.3.2 Turn the column upside down from its normal position, and
remove the inlet bed support plunger (the inlet plunger is
longer than the outlet plunger). Position and tighten the
outlet bed support plunger as near the end as possible, but no
closer than 5 cm (measured from the gel packing to the collar).
3.3.3 Raise the end of the outlet tube to keep the solvent in the GPC
column, or close the column outlet stopcock. Place a small
amount of solvent in the column to minimize the formation of
air bubbles at the base of poured column packing.
3.3.4 Swirl the bead/solvent slurry to get a homogeneous mixture and,
if the wetting was done in a quart bottle, quickly transfer it
to a 500 mL separatory funnel with a large bore stopcock.
Drain the excess methylene chloride directly into the waste
beaker, and then start draining the slurry into the column by
placing the separatory funnel tip against the column wall.
This will help to minimize bubble formation. Swirl
occasionally to keep the slurry homogeneous. Drain enough to
fill the column. Place the tubing from the column outlet into
a waste beaker below the column, open the stopcock (if
attached), and allow the excess solvent to drain. Raise the
tube to stop the flow, and close the stopcock when the top of
the gel begins to look dry. Add additional methylene chloride
to just rewet the gel.
3.3.5 Wipe any remaining beads and solvent from the inner walls of
the top of the column with a laboratory tissue. Loosen the
seal slightly on the other plunger assembly (long plunger) and
insert it into the column. Make the seal just tight enough so
that any beads on the glass surface will be pushed forward, but
loose enough so that the plunger can be pushed forward.
CAUTION: Do not tighten the seal if beads are between the seal
and the glass surface because this can damage the seal and
cause leakage.
3.3.6 Compress the column as much as possible without applying
excessive force. Loosen the seal and gradually pull out the
plunger. Rinse and wipe off the plunger. Slurry any remaining
beads and transfer them into the column. Repeat the step in
paragraph 3.3.5 and reinsert the plunger. If the plunger
cannot be inserted and pushed in without allowing beads to
escape around the seal, continue coapression of the beads
without tightening the seal, and loosen and remove the plunger
as described. Repeat this procedure until the plunger is
inserted successfully.
3.3.7 Push the plunger until it meets the gel, then compress the
column bed about four centimeters.
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SECTION II
3.3.8 Pack Che optional 5 cm column with approximately 5 got of
preswelled beads (different guard columns may require different
amounts). Connect the guard column to the inlet of the
analytical column.
3.3.9 Connect the column inlet to the solvent reservoir (reservoir
should be placed higher than the top of the column) and place
the column outlet tube in a waste container. Placing a
restrictor in the outlet tube will force air out of the column
more quickly. A restrictor can be made from a piece of
capillary stainless steel tubing of 1/16" OD x 10/1000" ID x
2". Pump methylene chloride through the column at a. rate of 5
mL/min for one hour.
3.3.10 After washing the column for at least one hour, connect the
column outlet tube, without the restricCor, to the inlet side
of the UV detector. Connect the system outlet to the outlet
side of the UV detector. A restrictor (same size as the one in
paragraph 3.3.9) in the outlet tube from the UV detector will
prevent bubble formation which causes a noisy UV baseline. The
restrictor will not effect flow rate. After pumping methylene
chloride through the column for an additional 1-2 hours, adjust
the inlet bed support plunger until approximately 6-10 psi
backpressure is achieved. Push the plunger in to increase
pressure or slowly pull outward to reduce pressure.
3.3.11 When the CPC column is not to be used for several days, connect
the column outlet line to the column inlet to prevent column
drying and/or channeling. If channeling occurs, the gel must
be removed from the column, reswelled, and repoured as
described above. If drying occurs, methylene chloride should
be pumped through the column until the observed column pressure
is constant and the column appears wet. Always recalibrate
after column drying has occurred to verify retention volumes
have not changed.
3.4 Calibration of the GPC Column
3.4.1 Using a 10 mL syringe, load sample .loop #1 with calibration
solution (paragraph 3.2). With the ABC automated system, the 5
mL sample loop requires a minimum of 8 mL of the calibration
- solution. Use a firm, continuous pressure to push the sample
onto the loop. Switch the valve so that GPC flow is through
the UV flow-through cell.
3.4.2 Inject the calibration solution and obtain a UV trace showing a
discrete peak for each component. Adjust the detector and/or
recorder sensitivity to produce a UV trace that meets the
following requirements. Differences between manufacturer's
cell volumes and detector sensitivities may require a dilution
of the calibration solution to achieve similar results. An
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SECTION II
analytical flow-through detector cell will require a much less
concentrated solution than the semi-prep cell and, therefore,
the analytical cell is not acceptable for use.
o Peaks must be observed and should be symmetrical for all
compounds in the calibration solution.
o Corn oil and phthalate peaks must exhibit >85% resolution.
o Phthalate and methoxychlor peaks must exhibit >85%
resolution.
o Methoxychlor and perylene peaks must exhibit >85%
resolution.
o Perylene and sulfur peaks must not be saturated and must
exhibit >90% baseline resolution.
3.4.3 Using the information from the UV trace, establish appropriate
collect and dump time periods to ensure collection of all
target analytes. Initiate column eluate collection just before
elution of bis(2-ethylhexyl)phthalate and after the elution of
the corn oil. Stop eluate collection shortly after the elution
of perylene. Collection should be stopped before sulfur
elutes. Use a "wash" time of 10 minutes after the elution of
sulfur. Each laboratory is required to establish its specific
time sequences.
3.4.4 Verify the flow rate by collecting column eluate for 10 minutes
in a graduated cylinder and measure the volume, which should be
45-55 mL (4.5-5.5 mL/min). If the flow rate is outside of this
range, corrective action must be taken, as described above.
Once the flow rate is within the range of 4.5-5.5 mL/min,
record the column pressure (should be 6-10 psi) and room
temperature. Changes in pressure, solvent flow rate, and
temperature conditions can affect analyte retention times and
must be monitored. If the flow rate and/or column pressure do
not fall within the above ranges, a new column should be
prepared. A UV trace that does not meet the criteria in
paragraph 3,4.2 would also indicate that a new column should be
prepared. It may be necessary to obtain a new lot of Bio Beads
if the column fails all the criteria.
3.4.5 Reinject the calibration solution after appropriate collect and
dump cycles have been set, and the solvent flow and column
pressure have been established.
3.4.5.1 Measure and record the volume of collected CPC
eluate in a graduated cylinder. The volume of GPC
eluate collected for each sample extract processed
may be used to indicate problems with the system
during sample processing.
3.4.5.2 The retention times for bis(2-ethylhexyl)phthalate
and perylene must not vary more than ±5% between
calibrations. If the retention time shift is >5%,
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SECTION II
take corrective action. Excessive retention time
shifts are caused by the following:
o Poor laboratory temperature control or system
leaks.
o An unstabilized column that requires pumping
methylene chloride through it for several more
hours or overnight.
o Excessive laboratory temperatures causing
outgassing of the methylene chloride.
3.4.6 Analyze a GPC blank by loading 5 mL of methylene
chloride into the GPC. Concentrate the methylene
chloride that passes through the system during the
collect cycle using a Kuderna-Danish (KD)
evaporator. Analyze the concentrate by GC/MS. If
the blank exceeds one half the CRQL of any analyte,
pump additional methylene chloride through the
system for 1-2 hours. Analyze another GPC blank to
ensure the system is sufficiently clean. Repeat the
methylene chloride pumping if necessary.
3.5 Sample Extract Cleanup
It is very important to have consistent laboratory temperatures during
an entire GPC run, which could be 24 hours or more. If temperatures
are not consistent, retention times will shift, and the dump and
collect times determined by the calibration standard no longer will be
appropriate. The ideal laboratory temperature to prevent outgassing of
the methylene chloride is 72'F.
3.5.1 In order to prevent overloading of the GPC column, highly
viscous sample extracts must be diluted prior to cleanup. Any
sample extract with a viscosity greater than that of a 1:1
glycerol:water solution Must be diluted and loaded into several
loops. Similarly, extracts containing more than 500 mg of
nonvolatile residue per 5 mL of extract must be diluted and
loaded into several loops. The nonvolatile residue may be
determined by evaporating a 100 uL aliquot of the extract to
dryness in a tared aluminum weighing pan, or other suitable
container.
3.5.2 Particles greater than 5 microns may scratch the valve, which
may result in a system leak and cross contamination of sample
extracts in the sample loops. To avoid such problems, filter
the extract through a 5 micron filter disc by attaching a
syringe filter assembly containing the filter disc to a 10 mL
syringe. Draw the sample extract through the filter assembly
and into the 10 mL syringe. Disconnect the filter assembly
before transferring the sample extract into a small glass
container, e.g., a 15 mL culture tube with a Teflon lined screw
cap. Alternatively, draw the extract into the syringe without
the filter assembly. Attach the filter assembly and force the
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SECTION II
extract through the filter and into the glass container. Draw
a minimum of 8 mL of extract into a 10 raL syringe.
3.5.3 Attach the syringe to the turn lock on the injection port. Use
firm, continuous pressure to push the sample onto the 5-raL
sample loop. If the sample is difficult to load, some part of
the system may be blocked. Take appropriate corrective action.
If the back pressure is normal (6-10 psi) the blockage is
probably in the valve. Blockage may be flushed out of the
valve by reversing the inlet and outlet tubes and pumping
solvent through the tubes (this should be done before sample
loading).
NOTE: Approximately 2 mL of the extract remains in the lines
between the injection port and the sample loop; excess sample
also passes through the sample loop to waste.
3.5.4 After loading a loop, and before removing the syringe from tl.e
injection port, index the GPC to the next loop. This will
prevent loss of sample caused by unequal pressure in the loops.
3.5.5 After loading each sample loop, wash the loading port with
methylene chloride in a FIFE wash bottle to minimize cross
contamination. Inject approximately 10 mL of methylene
chloride to rinse the common tubes.
3.5.6 After loading all the sample loops, index the GPC to the 00
position, switch to the "RUN" mode and start the automated
sequence. Process each sample using the collect and dump cycle
times established in 3.4.
3.5.7 Collect each sample in a 250-mL Erlenmeyer flask, covered with
aluminum foil to reduce solvent evaporation, or directly into a
Kuderna-Danish evaporator. Monitor sample volumes collected.
Changes in sample volumes collected may indicate one or more of
the following problems:
o Change in solvent flow rate, caused by channeling in the
column or changes in column pressure.
o Increase in column operating pressure due to the absorption
of particles or gel fines onto either the guard column or
the analytical column gel, if a guard column is not used.
o Leaks in the system or significant variances in room
temperature.
3.5.8 Concentrate the extract as per paragraphs 3.6.1 or 3.6.2.
3.5.9 Calibrate the GPC at least once per week, following the
procedure outlined in 3.4. The UV trace must meet the
requirements in paragraph 3.4.2. In addition, the retention
times of the calibration compounds must be within ±5% of their
retention times in the previous calibration. A copy of the UV
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SECTION II
trace of the calibration solution must be submitted with the
data for the associated samples.
3.5.10 If the requirements in paragraphs 3.4.2 and 3.5.9 cannot be
met, the column may be cleaned by processing several 5 mL
volumes of butyl chloride throught the system. Butyl chloride
removes the discoloration and particles that may have
precipitated out of the methylene chloride extracts. If a
guard column is being used, replace it with a new one. This
may correct the problem. If column maintenance does not
restore the performance of the column, the column must be
repacked with new packing and recalibrated.
3.6 Final Concentration of Extract
3.6.1 Transfer the sample extract to a. K-D evaporator, attach the
micro-Snyder column to the concentrator tube and add a silicon
carbide boiling chip to the concentrator tube. Pre-wet the
Snyder column with 0.5 mL of methylene chloride. Place the K-D
apparatus on the hot water bath (80-90'C) 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. When the apparent volume of the liquid reaches 0.4
mL, 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 the lower joint into the concentrator
tube with 0.1 mL of methylene chloride. Adjust the final
volume to 0.5 mL with nethylene chloride. Concentrating the
extract to 0.5 mL will account for the volume of extract (5 mL)
not recovered after GPC.
3.6.2 Nitrogen blowdown technique (taken from ASTM Method D 3086)
The following method may be used for final concentration of the
semivolatile extract instead of the procedures in paragraph
3.6.1. Place the concentrator tube in a warm water bath (35*C)
and evaporate the solvent volume to below 0.5 mL using a gentle
stream of clean, dry nitrogen (filtered through a column of
activated carbon). CAUTION: New plastic tubing must not be
used between the carbon trap and the sample, since it may
introduce interferences.
The internal wall of the tube must be rinsed down several times
with methylene chloride during the operation. 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. Concentrating the extract to 0.5 mL will account
for the volume of extract (5 mL) not recovered after GPC.
3.7 Store all extracts at 4'C (±2*C) in the dark in Teflon-sealed
containers.
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SECTION II
- -
proceed .lth th. OC/HS m.-"""- P«or to
D-31/SV
OLM01.0
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SECTION III
SCREENING OF SEMIVOLATILE
ORGANIC EXTRACTS
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SECTION HI
1. Summary of Method
L.L The solvent extracts of water and soil/sediment are screened on a gas
chromatograph/flarae ionization detector (GC/FID) using a fused silica
capillary column (FSCC). For water samples, the results of the screen
may be used to determine an appropriate dilution factor for the GC/MS
analysis of the sample extract. For soil/sedimant samples, the results
of the screen are used to determine which of the two sample preparation
procedures (low or medium) is required, and to determine an appropriate
dilution factor for GC/MS analysis. The results of the screen may be
used also to assist the analyst in performing Gel Permeation
Chromatography (GPC) clean up procedures on extracts of either water or
soil/sediment samples.
2. Apparatus and Materials
2.1 Gas chromatograph - an analytical system complete with a temperature
programmable gas chromatograph and all required accessories including
syringes, analytical columns, and gases. The injection port must be
designed for on-column injection when using packed columns and for
splitless injection when using capillary columns.
2.1.1 Above GC equipped with flame ionization detector.
2.1.2 GC column - 30 m x 0.32 mm, 1 micron film thickness, silicone
coated, fused silica capillary column (J & V Scientific DB-5
or equivalent).
3. Reagents
3.1 Methylene chloride - pesticide residue analysis grade or equivalent.
3.2 GC calibration standard - prepare a standard solution containing
phenol, phenanthrene and di-n-octylphthalate.
3.2.1 Stock standard solutions (1.00 ug/uL) - Stock standard
solutions can be prepared from pure standard materials or
purchased solutions.
3.2.1.1 Prepare stock standard solutions by accurately
weighing about 0.0100 g of pure material. Dissolve
the material in pesticide quality methylene
chloride and dilute to volume in a 10 mL volumetric
flask. Larger volumes may be used at the
convenience of the analyst. If compound purity is
assayed at 96% or greater, the weight may be used
without correction to calculate the concentration
of the stock standard. Commercially prepared stock
standards may be used at any concentration if they
are certified by the manufacturer or by an
independent source (see Exhibit E).
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SECTION III
3.2.1.2 Transfer the stock standard solutions into Teflon-
sealed screw-cap bottles. Store at -10°C to -20"C
and protect from light. Stock standard solutions
should be checked frequently for signs of
degradation or evaporation, especially just prior
to preparing calibration standards from them.
Stock standard solutions must be replaced after six
months, or sooner, if comparison with quality
control check samples indicates a problem.
Standards prepared from gases or reactive compounds
such as styrene must be replaced after two months,
or sooner, if comparison with quality control check
samples indicates a problem.
3.2.2 Prepare a working standard mixture of the three compounds in
methylene chloride. The concentration must be such that the
volume injected equals 50 ng of each compound. The storage
and stability requirements are the same as specified in •
paragraph 3.2.1.2.
4. GC Calibration
4.1 At the beginning of each 12 hour shift, inject the GC calibration
standard. The following criteria must be met:
4.1.1 The GC must be standardized for half scale response from 50 ng
of phenanthrene.
4.1.2 The GC must adequately separate phenol from the solvent front.
4.1.3 A minimum of quarter scale response for 50 ng of
di-n-octylphthalate must be exhibited.
5. GC/FID Screening
5.1 Suggested GC operating conditions are »s follows:
o Initial Column Temperature Hold - 50'C for 4 minutes.
o Column Temperature Program - 50-280*C at 8 degrees/min.
o Final Column Temperature Hold - 280*C for 8 minutes.
o Injector - Grob-type, splitless.
o Sample Volume - 1-2 uL.
o
o Carrier Gas - Helium at 30 cm /sec.
5.2 Inject the GC calibration standard and ensure the criteria specified in
4 are met before injecting samples. Estimate the response for 10 ng of
phenanthrene.
5.3 Inject the appropriate extracts from Section II, including blanks.
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SECTION III
6. Interpretation of Chromatograms
6.1 Water
6.1.1 If no sample peaks are detected, or all are less than full
scale deflection, the undiluted extract is analyzed on GC/MS.
6.1.2 If any sample peaks are greater than full scale deflection,
calculate the dilution necessary to reduce the major peaks to
between half and full scale deflection. Use this dilution
factor to dilute the extract for GC/MS analysis.
6.2 Soil/Sediment
6.2.1 If no sample peaks from the extract (from low or medium level
preparation) are detected, or all are less than 10% full scale
deflection, the sample must be prepared by the low level
protocol, Section II, Part C, beginning at 2.
6.2.2 Peaks are detected at greater than 10% full scale deflection
and less than or equal to full scale deflection.
6.2.2.1 If the screen is from the medium level extract,
proceed with GC/MS analysis of this extract with
appropriate dilution if necessary.
6.2.2.2 If screen is from the low level extract, discard
extract and prepare sample by medium level method
for GC/MS analysis.
6.2.3 Peaks are detected at greater than full scale deflection.
6.2.3.1 If the screen is from the medium level preparation,
calculate the dilution necessary to reduce the
major peaks to between half and full scale
deflection. Use this dilution factor to dilute the
extract. This dilution is analyzed by GC/MS for
extractable organics.
6.2.3.2 If the screen is from the low level preparation,
discard the extract and prepare a sample by the
medium level method for GC/MS analysis.
7. GC/MS Analysis
7.1 Use the information from paragraph 6 (Interpretation of Chromatograms)
to perform the GC/MS analysis, beginning Section IV, GC/MS Analysis of
Semivolatiles.
7.2 The information from paragraph 6 may be usefull also in processing
sample extracts through GPC clean up.
NOTE: The choice of screening sample extracts before or after GCP
clean up is left to the laboratory.
D-35/SV OLM01.0
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SECTION IV
GC/MS ANALYSIS OF SEMIVOLATILES
D-36/SV
OLM01.0
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SECTION IV
Summary of Method
This method is to be used for Che GC/MS analysis of semivolatiles
screened by Section III protocols and for confirmation of
pesticides/Aroclors identified by GC/EC, if concentrations permit.
2. Apparatus and Materials
2.1 Gas chromatograph/mass spectrometer system.
2.1.1 Gas chromatograph - an analytical system complete with a
temperature programmable gas chromatograph suitable for
splitless injection and all required accessories including
syringes, analytical columns and gases.
2.1.2 Column - 30 m x 0.25 mm ID (or 0.32 mm) bonded-phase silicone
coated fused silica capillary column (J&V Scientific DB-5 or
equivalent). A film thickness of 1.0 micron is recommended
because of its larger capacity. A film thickness of 0.25
micron may be used.
2.1.3 Mass Spectrometer - capable of scanning from 35 to 500 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 instrument performance
criteria in Table 1 when 50 ng of decafluorotriphenylphosphine
(DFTPP) is injected through the GO inlet. The instrument
conditions required for the acquisition of the DFTPP mass
spectrum are given in paragraph 4.3.4. NOTE: DFTPP criteria
must be met before any sample extracts are analyzed. Any
samples analyzed when DFTPP criteria have not been met will
require reanalysis at no cost to the Agency.
2.1.4 GC/MS interface - any gas chromatograph to mass spectrometer
interface that gives acceptable calibration points, at 50 ng or
less per injection, for each of the parameters of interest, and
achieves all acceptable performance criteria (Exhibit E), may
be used. Gas chromatograph to mass spectrometer interfaces
constructed of all-glass or glass-lined materials are
recommended. Glass can be deactivated by silanizing with
dichlorodiaethylsilane.
2.1.5 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 specific 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 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 spectra. The
D-37/SV OLM01.0
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SECTION IV
1989 (or most recent) release of the NIST/EPA/MSDC mass
spectral library shall be used as the reference library. The
data system must be capable of flagging all data files that
have been editted manually by laboratory personnel.
3. Reagents
3.1 Internal standards - 1,4 Dichlorobenzene-d^, Naphthalene-dg,
Acenaphthene-d^Q, Phenanthrene-d^g, Chrysene-di7, Perylene-dio-
An internal standard solution can be prepared by dissolving 100 mg of
each compound in 50 mL of methylene chloride. It may be necessary to
use 5 to 10 percent benzene or toluene in this solution and a few
minutes of ultrasonic mixing In order to dissolve all the constituents.
The resulting solution will contain each standard at a concentration of
2000 ng/uL. A 10 uL portion of this solution should be added to each 1
mL of sample extract. This will result in 40 ng of each internal
standard in the 2 uL volume of extract injected into the GC/MS.
"•»
3.2 Prepare calibration standards at a minimum of five concentration levels
(20, SO, 80, 120, and 160 total ng per 2 uL). Each calibration
standard should contain each compound of interest and each surrogate.
Nine compounds, Benzoic acid, 2,4-Dinitrophenol, 2,4,5-Trichlorophenol,
2-Nitroaniline, 3-Nitroaniline, 4-Nitroaniline, 4-Hitrophenol, 4,6-
Dinitro-2-methylphenol, and Pentachlorophenol will require only a four-
point initial calibration at 50, 80, 120, and 160 total ng, since
detection at less that 50 ng per injection is difficult. Great care
must be taken to maintain the integrity of all standard solutions.
Store all standard solutions at -10*C to -20*C in screw-cap amber
bottles with teflon liners. Fresh standards should be prepared every
twelve months at a minimum. The continuing calibration standard (50
ng) should be prepared weekly and stored at 4*C (±2*C).
In order to facilitate the confirmation of pesticides and Aroclors from
the semivolatile library search data (see Exhibit 0 PEST, paragraph
17), the laboratory may wish to include the pesticide/Aroclor target
compounds listed in Exhibit C in the semivolatile continuing
calibration standard. The laboratory nay add any or all of these
compounds to the semivolatile continuing calibration standard, but at a.
concentation of 10 ng/uL or less. If added to this GC/MS standard,
these additional analytes are not reported on the semivolatile
calibration form (Form VII), but must be included in the quantitation
report for the continuing calibration standard. As only a single point
calibration would be performed, no %RSD or percent difference criteria
would apply to these additional analytes.
3.3 Instrument performance check solution - prepare a solution of
decafluorotriphenylphosphine (DFTPP), such that a 2 uL injection will
contain 50 ng of DFTPP. The DFTPP also be included in the calibration
standards at this level.
D-38/SV OLM01.0
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SECTION IV
4. Instrument Operating Conditions
4.1 Gas Chromatograph
The following are Che recommended gas chromacographic
analytical conditions:
Initial Column Temperature Hold — 40"C for 4 minutes
Column Temperature Program - 40-270'C at 10
degrees/min.
Final Column Temperature Hold - 270*C for 10 minutes
Injector Temperature - 250-300'C
Transfer Line Temperature - 250-300'C
Source Temperature - according to
manufacturer's
specifications
Injector — Grob-type, splitless
Sample Volume - 2 uL
Carrier Gas - Helium at 30 cm3/sec
4.2 Mass Spectrometer
The following are the recommended mass spectrometer analytical
conditions:
Electron Energy - 70 volts (nominal)
Mass Range - 35 to 500 amu
Scan Time - not to exceed 1 second per scan
4.3 The GC/MS system must be tuned to meet the manufacturer's
specifications, using a suitable calibrant such as 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 (paragraph 3.3).
4.3.1 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
decafluorotriphenylphosphine (DFTPP).
D-39/SV OLM01.0
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SECTION IV
4.3.2 The analysis of the instrument performance check
solution may be performed as follows:
o As an injection of up to 50 ng of DFTPP into the
GC/MS
o By adding 50 ng of DFTPP to the calibration
standards (paragraph 3.2) and analyzing the
calibration standard.
4.3.3 The analysis of the instrument performance check
solution must meet the ion abundance criteria given
below.
TABLE 1
DFTPP KEY IONS AND ION ABUNDANCE CRITERIA FOR QUADRAPOLE MASS SPECTROMETERS
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/. 442 may be up to 110 percent that
of m/z 198.
4.3.4 The abundance criteria listed above 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 prior to the elution of DFTPP.
4.3.5 The criteria above are based on adherence to the
acquisition specifications identified in paragraph
4.3.4. The criteria are based on performance
characteristics of instruments currently utilized in
routine support of Program activities. These
D-40/SV OLM01.0
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SECTION IV
specifications, in conjunction with relative
response factor criteria for 54 target compounds
(see Table 2), are designed to control and monitor
instrument performance associated with the
requirements of this Statement of Work.
4.3.6 The instrument performance check solution must be
analyzed once at the beginning of each 12-hour
period during which samples or standards are
analyzed.
The twelve (12) hour time period for a GC/MS system
instrument performance check and standards
calibration (inicial 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 twelve (12) hours
has elapsed according to the system clock.
5. Calibration
5.1 Prior to the analysis of samples and required blanks, and after the
instrument performance check solution 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 semivolatile target compounds.
5.2 The internal standards are added to all calibration standards and all
sample extracts (including blanks, matrix spikes, and matrix spike
duplicates) just prior to analysis by GC/MS. A 10 uL aliquot of the
internal standard solution should be added to a 1 mL aliquot of
calibration standards. The internal standards specified in paragraph
3.1 should permit most of the semivolatile target compounds to have
relative retention times of 0.80 to 1.20, using the assignments of
internal standards to target compounds given in Table 2.
5.3 The quantitation ions for each internal standard are given in Table 3.
Use the primary ion listed in Table 3 for quantitation, 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 3.
D-41/SV OLM01.0
-------
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D-42/SV
OLM01.0
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SECTION IV
TABLE 3
CHARACTERISTIC IONS FOR INTERNAL STANDARDS FOR SEMIVOLATILE COMPOUNDS
INTERNAL STANDARDS Primary Ion Secondary Ions
l,4-Dichlorobenzene-d4 152 115
Naphthalene-dg 136 68
Acenapthene-d1Q 164 162. 160
Phenanthrene-d10 188 94, 80
Chrysene-d12 240 120, 236
Perylene-d12 264 260, 265
5.4 Prepare calibration standards at a minimum of five concentration levels
for each target compound and surrogate, as specified in paragraph 3.2.
Analyze 2 uL of each calibration standard and tabulate the area of the
primary characteristic ion against concentration for each compound
including the surrogate compounds. A 2 uL injection is required.
Calculate relative response factors (RRF) for each compound using
Equation 1.
AX Cis
RRF - -— x -,— EQ 1
Ais cx
Where
A^ - Area of the characteristic ion for the compound to be measured
(see Table 4)
A^s - Area of the characteristic ion for the specific internal
standard (see Table 3)
Cis ~ Concentration of the internal standard (ng/uL)
Cx — Concentration of the compound to be measured (ng/uL)
5.5 The average relative response factor (RRF) must be calculated for all
compounds. Calculate the % Relative Standard Deviation (%RSD) of the
RRF values for the initial calibration.
D-43/SV OLM01.0
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SECTION IV
TABLE 4
CHARACTERISTIC IONS FOR SEMIVOLATILE TARGET COMPOUNDS AND SURROGATES
Parameter
Phenol
bis(2-Chloroethyl)ether
2-Chlorophenol
1, 3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
2 -Methylphenol
2,2' -oxybis(l-Chloropropane)
4 -Methylphenol
N-Nitroso-di-propylamine
Hexachloroe thane
Nitrobenzene
Isophorone
2-Nitrophenol
2 , 4-Dimethylphenol
bis (2 -Chlo roe thoxy) methane
2 , 4 - D ichloropheno 1
1 , 2 , 4-Trichlorobenzene
Naphthalene
4-Chloroaniline
Hexachlorobutadiene
4-Chloro-3-methylphenol
2 -Methylnaphthalene
Hexachlorocyclopentadiene
2,4, 6 -Trichlorophenol
2,4, 5 -Trichlorophenol
2 -Chloronaphthalene
2-Nitroaniline
Dimethyl phthalate
Acenaphthylene
3-Nitroaniline
Acenaphthene
2 , 4 - D ini tropheno 1
4-Nitrophenol
Dibenzofuran
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Primary Ion
94
93
128
146
146
146
108
45
108
70
117
77
82
139
107
93
162
180
128
127
225
107
142
237
196
196
162
65
163
152
138
153
184
109
168
165
165
Secondary Ion(s)
65
63
64
148
148
148
107
77
* 107
42
201
123
95
65
121
95.
164
182
129
129
223
144
141
235
198
198
164
92
194
151
108
152
63
139
139
63
89
, 66
, 95
, 130
, 113
, 113
, 113
, 79
, 101. 130
, 199
, 65
, 138
, 109
. 122
123
, 98
, 145
, 127
, 227
, 142
, 272
, 200
, 200
. 127
, 138
, 164
. 153
, 92
, 154
, 154
, 65
, 182
, 121
(continued)
D-44/SV
OLM01.0
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SECTION IV
rHARArTroT<.~ TABLE 4 (continued)
CHARACTERISTIC IONS FOR SEMIVOLATILE TARGET COMPOUNDS AND SURROGATES
DIechylphthalate
4-Chlorophenyl-phenyle ther
Fluorene
4-Nitroaniline
4,6-Dinitro-2-methylphenol
N-Nitrosodiphenylaoine
4-Bromophenyl-phenylether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Carbazole
Di-n-butyIphthalate
Fluoranthene
Pyrene
ButylbenzyIphthalate
3,3'-Dichlorobenzidine
Benzo(a)anthracene
bis(2-Ethylhexyl)phthalate
Chrysene
Di-n-Octyl phthalate
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(1,2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(g,h,i)perylene
SURROGATES
Phenol-d5
2 -Fluorophenol
2,4,6-Tribromophenol
Nitrobenzene-dj
2 -Fluorobiphenyl
Terphenyl
2-Chlorophenol-d^
1, 2-Dichlorobenzene-d/.
149
204
166
138
198
169
248
284
266
178
178
167
149
202
202
149
252
228
149
228
149
252
252
252
276
278
276
99
112
330
82
172
244
132
152
177
206,
165,
92,
182,
168.
250,
142,
264,
179,
179,
166,
150,
101,
101,
91,
254,
229,
167,
226,
, 150
, 141
, 167
108
77
167
141
249
268
176
176
139
104
100
100
206
126
226
279
229
253, 125
253, 125
253, 125
138, 227
139, 279
138, 277
42, 71
64
332, 141
128, 54
171
122, 212
68, 134
115, 150
D-45/SV
OLM01.0
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SECTION IV
5.6 Response factor criteria have been established for the calibration of 45
of the semivolatile target compounds and 6 semivolatile surrogate
compounds.
5.6.1 The compounds listed in Table 5 must meet the minimum RRF and
maximum %RSO criteria for the initial calibration, with
allowance made for up to four semivolatile target and surrogate
compounds. However, the RRFs for those four compounds must be
greater than 0.010, and the %RSD of those four compounds must
be less than or equal to 40.0% for the initial calibration to
be acceptable.
TABLE 5
RELATIVE RESPONSE FACTOR CRITERIA FOR INITIAL AND CONTINUING
CALIBRATION OF SEMIVOLATILE TARGET COMPOUNDS
Semivolatile
Compounds
Phenol
bis(-2-Chloroethyl)ether
2-Chlorophenol
1, 3 -Dichlorobenzene
1,4- Dichlorobenzene
1,2- Dichlorobenzene
2-Methylphenol
4 - Me thy Ipheno 1
N-Nitroso-Di-propylamine
Hexach lo r oe thane
Nitrobenzene
Isophorone
2-Nitrophenol
2 , 4-Dimethylphenol
bis (-2-Chloroethoxy)me thane
2,4- Dichlorophenol
1 , 2 , 4-Trichlorobenzene
Naphthalene
4 - Chloro - 3 -me thy Ipheno 1
2 -Methylnaphthalene
2,4, 6 - TricRlorophenol
2,4, 5 -Trichlorophenol
2 - Chloronaphthalene
Acenaphthylene
2 , 6 - D ini tro to luene
Acenaphthene
Dibenzofuran
2,4-Dinitrotoluene
4-Chlorophenyl-phenylether
Fluorene
4-Bromophenyl-phenylether
Hexachlorobenzene
Pentachlorophenol
Minimum
RRF
0.800
0.700
0.800
0.600
0.500
0.400
0.700
0.600
0.500
0.300
0.200
0.400
0.100
0.200
0.300
0.200
0.200
0 . 700 .
0.200
0.400
0.200
0.200
0.800
1.300
0.200
0.800
0.800
0.200
0.400
0.900
0.100
0.100
0.050
Maximum
%RSD
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
Maximum
%Diff
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
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
(continued)
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SECTION IV
TABLE 5 (continued)
RELATIVE RESPONSE FACTOR CRITERIA FOR INITIAL AND CONTINUING
CALIBRATION OF SEMIVOLATILE TARGET COMPOUNDS
Semivolatile
Compounds
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo (a) anthracene
Chrysene
Benzo (b) f luoranthene
Benzo (k)fluoranthene
Benz o ( a ) pyrene
Indeno (1,2,3- cd) pyrene
Dibenzo (a , h) anthracene
Benzo (g , h , i)perylene
Nitrobenzene -d^
2 - Fluorobiphenyl
Terpheny 1 - d^^
Phenol -dj
2 - Fluorophenol
2-Chlorophenol-d^
1,2-Dichlorobenzene-d^
Minimum
RRF
0.700
0.700
0.600
0.600
0.800
0.700
0.700
0.700
0.700
0.500
0.400
0.500
0.200
0.700
0.500
0.800
0.600
0.800
0.400
Maximum
%RSD
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5"
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
Maximum
%Diff
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
25.0
25.0
5.6.2
Because performance data indicate erratic and poor linearity
and sensitivity, the following compounds have no Maximum %RSD,
or Maximum %Difference criteria; however, these compounds must
meet a minimum RRF criterion of 0.010:
2,2'-oxybis(1-Chloropropane)
4-Chloroaniline
Hexachlorobutadiene
Hexachlorocyclopentadiene
2-Nitroanlline
DimethyIphthalate
3-Nitroaniline
2,4-Dinitrophenol
4-Nitrophenol
DiethyIphthalate
4-Nitroaniline
4,6-Dinitro-2-methylphenol
N-Ni trosodiphenylamine
Di-n-butylphthalate
ButylbenzyIphthalate
3,3'-Dichlorobenzidine
bis(2-Ethylhexyl)phthalate
Di-n-octylphthalate
2,4,6-Tribromophenol
5.7
In addition, Carbazole, a new target compound for which there
is insufficient performance data, must only meet a minimum RRF
criterion of 0.010.
A check of the calibration curve must be performed once every 12 hours
(see paragraph 4.3.6 for the definition of the twelve-hour time period).
Check the relative response factors of those compounds for which RRF
values have been established. If these criteria are met, the relative
response factors for all compounds are calculated and reported. A
percent difference of the daily relative response factor (12 hour)
D-47/SV
OLM01.0
-------
SECTION IV
compared to the average relative response factor from the initial curve
is calculated. Calculate the percent difference for each compound and
compare with the maximum percent difference criteria listed above.
As with the initial calibration, up to four semivolatile target
compounds in Table 5 may fail to meet the minimum RRF or maximum %D
criteria, but the RRFs of those four compounds must be greater than or
equal to 0.010, and the percent differences must be less Chan or equal
to 40.0% for the continuing calibration to be acceptable.
5.8 Internal standard responses and retention times in all standards must be
evaluated during or immediately after data acquisition. If the retention
time for any internal standard changes by more than 0.50 minutes (30
seconds) from the latest daily (12 hour) calibration standard, the
chromatographic system must be inspected for malfunctions, and
corrections made as required. The extracted ion current profile (EICP)
of the internal standards must be monitored and evaluated for each
standard. If the EICP area for any internal standard changes by more
than a factor of two (-50% to +100%), the mass spectrometrie system must
be inspected for malfunction, and corrections made as appropriate. When
corrections are made, re-analysis of samples analyzed while the system
was malfunctioning is necessary.
5.9 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 removal or replacement, etc.), or if the continuing
calibration acceptance criteria have not been met.
5.10 If time remains in the 12 hour time period after meeting the acceptance
criteria for the initial calibration, samples may be analyzed. It is
not necessary to analyze a continuing calibration standard, if the
initial calibration standard that is the sane concentration as the
continuing calibration standard meets the continuing calibration
acceptance criteria. Quantify all sample results against the initial
calibration standard that is the saue concentration as the continuing
calibration standard (50ng/2uL).
5.11 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 oust be made. The DFTPP
may be included in the continuing calibration standard.
5.12 If the injection of the instrument performance check solution meets the
criteria in Table 1, calculate the response factors for the continuing
calibration standard and the percent difference of the response factors
from the mean response factors in the initial calibration.
5.13 The response factors from the continuing calibration standard must meet
the criteria in Table 5 prior to the analysis of any blanks or samples.
6. Sample Analysis
6.1 Sample extracts may be analyzed only after the GC/MS system has met the
instrument performance check, initial calibration, and continuing
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SECTION IV
calibration requirements above. The same instrument conditions must be
employed for the analysis of samples as were used for calibration.
6.2 Internal standard solution is added to each sample extract. Add 10 uL
of internal standard solution to each accurately measured 1.0 mL of
sample extract.
6.3 Make any extract dilution indicated by characterization prior to the
addition of internal standards. If any further dilutions of water or
soil/sediment extracts are made, additional internal standards must be
added to maintain the required 40 ng (20 ng/uL) of each internal
standard in the extract volume.
6.4 Inject 2 uL of the sample extract, containing 40 ng of each internal
standard, into the GC/MS.
7. Qualitative Analysis
7.1 The compounds listed in the Target Compound List (TCL), Exhibit C, shall
be identified by an analyst competent in the interpretation of mass
spectra (see Bidder Qualification description) 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:
o Elution of the sample component at the GC relative retention time as
the standard component.
o Correspondence of the sample component and standard component mass
spectra.
7.1.1 For establishing correspondence of the GC relative retention
time (RRT), the sample component RRT must compare 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. If
coelution of interfering components prohibits accurate
assignment of the sample component RRT from the total ion
chromatogram, the RRT should be assigned by using extracted ion
current profiles for ions unique .to the component of interest.
7.1.2 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 DFTPP daily instrument performance requirements. These
standard spectra may be obtained from the run used to obtain
reference RRTs.
7.1.3 The requirements for qualitative verification by comparison of
mass spectra are as follows:
7.1.3.1 All ions present in the standard mass spectra at a
relative intensity greater than 10% (most abundant
ion in the spectrum equals 100%) must be present in
the sample spectrum.
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SECTION IV
7.1.3.2 The relative intensities of ions specified in
7.1.3.1 must agree within ±20% between Che standard
and sample spectra. (Example: For an ion with an
abundance of 50% in the standard spectra, the
corresponding sample ion abundance must be between
30 and 70 percent.)
7.1.3.3 Ions greater than 10% in the sample spectrum but not
present in the standard spectrum must be considered
and accounted for by the analyst making the
comparison. In Task III, the verification process
should favor false positives. All compounds meeting
the identification criteria must be reported with
their spectra. For all compounds below the CRQL
report the actual value followed by "J", e.g., "3J."
7.1.4 If a compound cannot be verified by all of the criteria in
7.1.3, but in the technical judgement of trie mass spectral
interpretation specialist, the identification is correct, then
the Contractor shall report that identification and proceed
with quantification in paragraph 8.
7.2 A library search shall be executed for non-target sample components for
the purpose of tentative identification. For this purpose, the 1989 (or
most recent) release of the NIST/EPA/MSDC mass spectral library,
containing 50,000 spectra, shall be used.
7.2.1 Up to 20 nonsurrogate organic compounds of greatest apparent
concentration not listed in Exhibit C for the semivolatile
fraction shall be identified tentatively via a forward search
of the NIST/EPA/HSDC mass spectral library. Substances with
responses less than 10% of the nearesc internal standard are
not required to be searched in this fashion. 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 normalization routines that would
misrepresent the library or unknown spectra when compared to
each other.
7.2.2 Guidelines for making tentative identification.
7.2.2.1 Relative intensities of major ions in the reference
spectrum (ions greater than 10% of the most abundant
ion) should be present in the sample spectrum.
7.2.2.2 The relative intensities of the major ions should
agree within ± 20%. (Example: For an ion with an
abundance of 50% in the standard spectra, the
corresponding sample ion abundance must be between
30 and 70 percent.)
7.2.2.3 Molecular ions present in reference spectrum should
be present in sample spectrum.
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SECTION IV
7.2.2.4 Ions present in the sample spectrum but not in the
reference spectrum should be reviewed for possible
background contamination or presence of co-eluting
compounds.
7.2.2.5 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
sometimes can create these discrepancies.
7.2.3 If, in the technical judgement of Che mass interpretation
spectral 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 (i.e., unknown phthalate,
unknown hydrocarbon, unknown acid type, unknown chlorinated
compound). If probable molecular weights can be distinguished,
include them.
8. Quantitation
8.1 Target components identified shall be quantified by the internal
standard method. The internal standard used shall be the one nearest
the retention time to that of a given analyte (see Table 2). The EICP
area of characteristic ions of analytes listed in Table 4 are used for
quantitation.
Internal standard responses and retention times in all samples must be
evaluated during or immediately after data acquisition. If the
retention time for any internal standard changes by more than 0.50
minutes (30 seconds) from the latest daily (12 hour) calibration
standard, the chromatographic system must be inspected for malfunctions,
and corrections made as required. The extracted ion current profile
(EICP) of the internal standards must be monitored and evaluated for
each sample, blank, matrix spike, and matrix spike duplicate. The
criteria are described in detail in the instructions for Form VIII,
Internal Standard Area Summary. If the EICP area for any internal
standard changes by more than a factor of two (-50% to +100%), the mass
spectrometric system must be inspected for malfunction and corrections
made as appropriate. If the analysis of a subsequent sample or standard
indicates that the system is functioning properly, then corrections may
not be required. The samples or standards with EICP areas outside the
limits must be re-analyzed, and treated according to paragraphs 8.1.1
and 8.1.2 below. If corrections are made, then the laboratory must
demonstrate that the mass spectrometric system is functioning properly.
This must be accomplished by the analysis of a standard or sample that
does meet the EICP criteria. After corrections are made, the
re-analysis of samples analyzed while the system was malfunctioning is
required.
8.1.1 If after re-analysis, the EICP areas for all internal standards
are inside the contract limits (-50% to +100%), then the
problem with the first analysis is considered to have been
within the control of the laboratory. Therefore, submit only
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SECTION IV
data from the analysis with EICPs within the contract limits.
This is considered the initial analysis and must be reported as
such on all data deliverables.
8.1.2 If the re-analysis of the sample does not solve the problem,
i.e., the EICP areas are outside the contract limits for both
analyses, then submit the EICP data and sample data from both
analyses. Distinguish between the initial analysis and the
re-analysis on all data deliverables, using the sample suffixes
specified in Exhibit B. Document in the SDG Narrative all
inspection and corrective actions taken.
8.1.3 Do not re-analyze HS/MSD samples that do not meet the EICP area
limits.
8.2 The relative response factor (RRF) from the daily standard analysis is
used to calculate the concentration in the sample. Secondary ion
quantitation is allowed ONLY when there are sample Interferences with
the primary ion. If secondary ion quantitation is performed, document
the reasons in the SDG Narrative. The area of a secondary ion cannot be
substituted for the area of a primary ion unless a relative response
factor is calculated using the secondary ion.
When target compounds are below contract required quantitation limits
(CRQL) but the spectrum meets the identification criteria, report the
concentration with a "J." For example, if CRQL is 10 ug/L and
concentration of 3 ug/L is calculated, report as "3J."
Calculate the concentration in the sample using the relative response
factor (RRF) as determined in 4.3 and the following equation:
Water
(Ax)(Is)(Vt)(Df)
Concentration ug/L —
A^ - Area of the characteristic ion for the compound to be
measured
A£S - Area of the characteristic ion for the internal standard
Is - Amount of internal standard injected in nanograms (ng)
VQ - Volume of water extracted in milliliters (mL)
Vi - Volume of extract injected in microliters (uL)
Vc - Volume of the concentrated extract in microliters (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.
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SECTION IV
Soil/Sediment
(Ax)(Is)(Vc)(Df)
Concentration ug/kg -
(Dry weight basis) (Aig)(RRF)(V£)(Wg)(D)
Where
AX,IS,A£S are as given for water, above.
Vt - Volume of the concentrated extract in microliters (uL)
Df - Dilution Factor. The dilution factor for analysis of
soil samples for semivolatiles by this method is defined
as follows:
uL most cone, extract used to make dilution + mL clean solvent
uL most cone, extract used to make_ dilution
If no dilution is performed, Df - 1.0.
Vj - Volume of extract injected in microliters (uL)
D - 100 - % moisture
100
Ws - Weight of sample extracted in grams (g)
8.3 An estimated concentration for non-target components tentatively
identified shall be quantified by the internal standard method. For
quantification, the nearest internal standard free of interferences
shall be used. The formula for calculating concentrations is the same
as in paragraph 8.2. Total area counts (or peak heights) from the total
ion chromatograms are to be used for both the compound to be measured
and the internal standard. A relative response factor (RRF) of one (1)
is to be assumed. The resulting concentration shall be qualified as "J"
(estimated, due to lack of a compound-specific response factor), and "N"
(presumptive evidence of presence), indicating the quantitative and
qualitative uncertainties associated with this non-target component. An
estimated concentration should be calculated for all tentatively
identified compounds as well as those identified as unknowns.
8.4 If the on-column concentration of any compound in any sample exceeds the
initial calibration range, that sample must be diluted, the internal
standard concentration readjusted, and the sample extract reanalyzed.
Guidance in performing dilutions and exceptions to this requirement are
given below.
8.4.1 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.
8.4.2 The dilution factor chosen should keep the response of the
largest peak for a target compound in the upper half of the
initial calibration range of the instrument.
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SECTION IV
8.4.3 Do not submit data for more than two analyses, i.e., the
original sample extract and one dilution, or, if the
semivolatile screening procedure was employed, from che most
concentrated dilution analyzed and one further dilution.
8. A. 4 Do not dilute MS/MSD samples solely to get non- spiked analytes
within the calibration range. The spiking level of each
compound in the semivolatile matrix spiking solution should not
require the dilution of the MS/MSD unless the sample from which
these aliquots were taken contains high levels of the spiked
analytes .
8.5 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if recovery is within limits (see Table 6) and report
on appropriate form.
8.5.1 Calculate the concentrations of the surrogate compounds using
the same equations as used for the target compounds. Calculate
the recovery of each surrogate as follows :
%R • Concentration (or ^BOVT^y) found x 100
Concentration (or amount) spiked
8.5.2 Determine if the sample surrogate recovery meets specifications
as follows:
o The eight semivolatile surrogates can be divided into three
groups: base/neutral compounds (Nitrobenzene -d$, 2-
Fluorobiphenyl, and Terphenyl-dj^) ; acid compounds (Phenol -
dj, 2-Fluorophenol, and 2 ,4,6-Tribromophenol) ; and
compounds with advisory QC limits (2-Chlorophenol-d^ and
1 , 2 -Dichlorobenzene -d^ .
o If a single surrogate recovery from any group is not within
the contract windows, the sample does not require reanalysis
or reextraction.
o If a single surrogate recovery from the base/neutral group
and a single surrogate recovery from the acid group are not
within the contract windows, the sample does not require
reanalysis or reextraction.
o Do not reanalyze or reextract if only surrogates with
advisory QC limits are not within the contract windows.
8.5.3 If the sample surrogate recovery does not meet specifications
(i.e., if two base/neutral or two acid surrogates are out of
limits ££ if recovery of any one base/neutral or acid surrogate
is below 10%), the following are required:
o Check to be sure that there are no errors in calculations ,
surrogate solutions, and internal standards. Also check
instrument performance.
o Reanalyze the sample if none of the above reveal a problem.
o If surrogate recoveries in a blank do not meet
specifications, the blank may be reanalyzed alone.
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SECTION IV
o Do not reanalyze dilutions if surrogate recoveries are
outside the limits.
o Never reanalyze the matrix spike or matrix spike duplicate
(MS/MSD), even if surrogate recoveries are outside the
limits.
o If the sample associated with the matrix spike and matrix
spike duplicate does not meet specifications, it should be
reanalyzed only if the MS/MSD surrogate recoveries are
within the limits. If the sample and associated MS/MSD show
the same pattern (i.e., outside the limits), then the sample
does not require reanalysis and must not be submitted.
Document in the narrative the similarity in surrogate
recoveries.
8.5.4 If the reanalysis of the sample solves the problem, then the
problem was within the laboratory's control. Therefore, submit
only data from the analysis with surrogate Spike recoveries
within the contract windows. This shall be considered the
initial analysis and shall be reported as such on all data
deliverables.
8.5.5 If none of the steps in paragraph 8.4.1 or 8.4.2 solves the
problem, then, except as noted below, reextraet and reanalyze
the sample. If the reextraction and reanalysis of the sample
solves the problem, then the problem was within the
laboratory's control. Therefore, submit only data from the
analysis with surrogate recoveries within the contract windows.
This shall be considered the initial analysis and shall be
reported as such on all data deliverables.
o If surrogate recoveries in a blank do not meet
specifications even after reanalysis, all of the samples
associated with that blank must be reextracted along with
the blank. The blank is intended to detect contamination in
samples processed at the same time.
o Do not reextraet diluted samples if surrogate recoveries are
outside the limits.
o Never reextraet the matrix, spike or matrix spike duplicate
(MS/MSD), even if surrogate recoveries are outside the
limits.
o If the sample associated with the matrix spike and matrix
spike duplicate does not meet specifications after
reanalysis, it should be reextracted only if the reanalysis
surrogate recoveries are not within the limits and MS/MSD
surrogate recoveries are within the limits. If the sample
and associated MS/MSD show the same pattern (i.e., outside
the limits), then the sample does not require reanalysis and
must not be submitted.
Document in the narrative the similarity in surrogate
recoveries.
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SECTION IV
8.5.6 If the reexcraction and reanalysis of the sample does not solve
the problem (i.e., the surrogate recoveries are outside the
contract limits for both analyses), then submit the surrogate
recovery data and sample analysis data from the initial
analysis of both sample extracts. Distinguish between the
initial analysis and the reanalysis on all data deliverables,
using the sample suffixes supplied in Exhibit B.
TABLE 6
SURROGATE RECOVERY LIMITS
%R %R
Compound Water Soil
Nitrobenzene-d5 35-114 23-120
2-Fluorobiphenyl 43-116 30-115
Terphenyl-d14 . 33-141 18-137
Phenol-d5 10-110 24-113
2-Fluorophenol 21-110 25-121
2,4,6-Tribromophenol 10-123 19-122
2-Chlorophenol-d4 33-110 20-130 (advisory)
l,2-Dichlorobenzene-d4 16-110 20-130 (advisory)
8.6. A matrix spike and matrix spike duplicate must be performed for each
group of samples of a similar matrix, for the following, whichever is
most frequent:
o Each Case of field samples received, OR
o Each 20 field samples in a Case, OR
o Each group of field samples of a similar concentration level
(soils only) , OR
o Each 14 calendar day period during which field samples in a
Case were received (said period beginning with the receipt of
the first sample in that Samf'e Delivery Group).
Calculate the recovery of each matrix spike compound in the matrix spike
and matrix spike duplicate and report on appropriate form.
8.6.1. Calculate the concentrations of the matrix spike compounds
using the sane equations as used for target compounds.
Calculate the recovery of each matrix spike compound as
follows:
%R -. Concentration foy fllflffynt) found x 100
Concentration (or amount) spiked
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SECTION IV
8.6.2 Calculate the relative percent difference of the recoveries of
each compound in the matrix spike and matrix spike duplicate as
follows:
RPD - IMSR • MSDRI x 100
(1/2)(MSR+MSDR)
Where
RPD - Relative Percent Difference
MSR - Matrix Spike Recovery
MSDR - Matrix Spike Duplicate Recovery
The vertical bars in the formula above indicate the absolute
value of the difference, hence RPD is always expressed as a
positive value.
8.6.3 The limits for matrix spike compound recovery and RPD are given
in Table 7. 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 the Agency.
TABLE 7
MATRIX SPIKE RECOVERY AND
RELATIVE PERCENT DIFFERENCE LIMITS
%R RPD %R RPD
Compound Water Water Soil Soil
Phenol 12-110 42 26- 90 35
2-Chlorophenol 27-123 40 25-102 50
1,4-Dichlorobenzene 36- 97 28 28-104 27
N-Nitroso-di-n-propylamine 41-116 38 41-126 38
1,2,4-Trichlorobenzene 39- 98 28 38-107 23
4-Chloro-3-methylphenol 23- 97 42 26-103 33
Acenaphthene 46-118 31 31-137 19
4-Nitrophenol 10- 80 50 11-114 50
2,4-Dinicrotoluene 24- 96 38 28- 89 47
Pentachlorophenol 9-103 50 17-109 47
Pyrene - 26-127 31 35-142 36
8.7 Method blank analysis must be performed once for the following, on each
GC/MS system used to analyze samples, whichever is most frequent:
o Each Case, OR
o Each 14 calendar day period during which samples in a Case are
received (said period beginning with the receipt of the first sample
in that Sample Delivery Group), OR
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SECTION IV
o Each 20 samples in a. Case, including matrix spikes and reanalyzes,
chat are of similar matrix (water or soil) or similar concentration
(soil only), OR
o Whenever samples are extracted by the same procedure (continuous
liquid-liquid extraction or sonication).
Determine the concentrations of any target compounds detected in the
semivolatile method blank, using the equations in paragraph 8.2. The
method blank must contain less than or equal to the Contract: Required
Quantitation Limit (CRQL) of the semivolatile target compounds in
Exhibit C, except the phthalate esters, which must be less than or equal
to five times (5x) the CRQL. For soil/sediment method blanks, CRQL
value must be adjusted for percent moisture (see Exhibit B).
If a laboratory method blank exceeds these criteria, 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.
All samples processed with a method blank that is out of control (i.e.,
contaminated) MUST be reextracted and reanalyzed at no additional cost
to the Agency. The Laboratory Manager, or his designee, must address
problems and solutions in the SDG Narrative (Exhibit B).
GC/MS Confirmation of Pesticides and Aroclors
The requirements for GC/MS confirmation of pesticides and Aroclors are
given in paragraph 17 of Exhibit D PEST. When performed, the
characteristic ions to be used for these analytes are given in Table 8.
Also see paragraph 3.2 of this section regarding the inclusion of these
analytes in the semivolatile continuing calibration standard.
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SECTION IV
TABLE 8
CHARACTERISTIC IONS FOR PESTICIDES/AROCLORS
Paramet-
alpha-BHC
beta-BHC
delta-BHC
gamma-BHC (Lindane)
Hepcachlor
Aldrin
Heptachlor epoxide
Endosulfan I
Dieldrin
A,4'-DDE
Endrin
Endrin ketone
Endrin aldehyde
Endosulfan II
4,4'-ODD
Endosulfan sulfate
4,4'-DDT
Methoxychlor
Chlordane (alpha and/or gamma)
Toxaphene
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
183
181
183
183
100
66
353
195
79
246
263
317
67
337
235
272
235
227
373
159
222
190
190
222
292
292
360
181, 109
183, 109
181, 109
181, 109
272, 274
263, 220
355, 351
339, 341
263, 279
248. 176
82, 81
67, 319
250, 345
339, 341
237, 165
387, 422
237, 165
228
375, 377
231, 233
260, 292
222, 260
222, 260
256, 292
362, 326
362. 326
362, 394
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EXHIBIT D
ANALYTICAL METHODS
FOR PESTICIDES/AROCLORS
D-l/PEST
OLM01.0
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EXHIBIT D
SECTION I -
SECTION II •
SECTION III -
Table of Contents
Page
Introduction D-3/PEST
Sample Preparation and Storage D-6/PEST
PART A - Sample Storage and Holding Times D-7/PEST
PART B - Sample Preparation for
Extractable Pesticides
and Aroclors D-8/PEST
GC/EC Analysis of Pesticides
and Aroclors D-33/PEST
D-2/PEST
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SECTION I
INTRODUCTION
The analytical method that follows is designed to analyze water, sediment and
soil from hazardous waste sites to determine the presence and concentration
of the chlorinated pesticides and Aroclors found in the Target Compound List
(Exhibit C). The method can be used for determining analyte concentrations
in the range from the contract required quantitation limits (CRQL) Co one
million times the CRQL in these matrices. The method is based on EPA Method
608.
The method is divided into three sections: Introduction, Sample Preparation,
and Analysis. Sample preparation covers sample extraction and cleanup
techniques. The analysis section contains the specific GC/EC analytical
methods for pesticides and Aroclors.
1. Summary of the Method
1.1 Continuous liquid-liquid or separatory funnel extraction procedures are
employed for aqueous samples. Sonication extraction is required for
soil/sediment samples (Section II, beginning at 6.2). The method
specifies GPC, adsorption column cleanup, and sulfur cleanup techniques
(Section II, beginning at 7).
1.2 The chlorinated pesticides and Aroclors listed in Exhibit C are
determined by a two-column GC/ECD technique.
1.3 Sample extracts, standards, and blanks must be analyzed within an
analytical sequence as defined in Section III. GC/ECD analysis begins
with an initial demonstration of instrument performance and the
calibration of all pesticides and Aroclors. Acceptable initial
calibration is defined in Section III, beginning at 6. Initial
calibration must be repeated whenever the calibration verification
stipulated in Section III, 7, fails or when major instrument
maintenance or modification is performed.
^
1.4 An instrument blank and a Performance Evaluation Mixture are analyzed
no less than once in every 12 hour analytical sequence in order to
monitor retention times, calibration factors, and column performance.
Data can be collected only as long as the results for the Performance
Evaluation Mixtures and instrument blanks fall within the limits
defined in Section III, 7. If two consecutive unacceptable Performance
Evaluation Mixtures are run, all extracts run since the previous
acceptable Performance Evaluation Mixture mist be reanalyzed.
Additional Performance Evaluation Mixtures and blanks are recommended
when highly contaminated samples are suspected.
1.5 Calibration and analysis sequence specifications of the GC/EC method
apply independently to both GC columns.
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SECTION I
1.6 Matrix spike and a matrix spike duplicate analyses must be prepared and
analyzed at least once for each matrix type or once per Sample Delivery
Group (SDG), whichever is most frequent.
1.7 Analysis of a sample on both GC columns is required for all samples,
blanks, matrix spikes, and matrix spike duplicates.
1.8 A single component pesticide is identified if a peak is detected within
its appropriate retention tine window on each of two columns.
Toxaphene and Aroclors are identified primarily by pattern recognition,
but RTs of three to five major peaks must also be taken into
consideration. Guidance on quantitation of Aroclors is given in
Section III, paragraph 13.
1.9 Standards for all tentatively identified Aroclors 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 standard analyzed during initial calibration.
1.10 Quantitative analysis of pesticides/Aroclors must be accomplished by
the external standard method. Three-point calibration curves for
single component analytes and the surrogates must be generated during
the initial calibration. A linear response range must be demonstrated
from the CRQL to a high point at least 30 times greater than the CRQL.
Single-point calibrations for multicomponent analytes are sufficient
for quantitation by this method.
1.11 The ECD response for single component analytes must be within the
three-point calibration range in order for quantitative measurements to
be made. The ECD response for the Aroclors/toxaphene must not be
larger than the response for the high point calibration analysis of the
single component analytes. The extracts must be diluted if the ECO
response exceeds 'the calibration range. Quantitation must be performed
and reported for both GC columns.
1.12 Absolute retention times (RTs) are used for the identification of
pesticides/Aroclors. The absolute retention time window is calculated
during initial calibration as ±0.04 minutes of the mean RT of the
standard for all analytes except Methoxychlor, where the RT window is
±0.05 minutes of the mean RT of the standard. For the multicomponent
analytes, the absolute retention time window is calculated for each
peak (3 to 5) as ±0.04 minutes of the RT of the same peak in the
initial calibration standard analysis.
1.13 The surrogates, 2,4,5,6-Tetrachloro-m-xylene and decachlorobiphenyl,
must b« added to all samples, blanks, matrix spikes, and matrix spike
duplicates prior to extraction. The retention time of both surrogates
oust fall within the retention cine windows for an analysis to be
acceptable. The surrogate recoveries will be determined in all of
these samples and will be reported to the Agency as a measure of method
performance.
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1.14 - SECTION I
~-.^u aimculties have h..« , .- . .
the
D-5/PEST
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SECTION II
SAMPLE PREPARATION AND STORAGE
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SECTION II
PART A - SAMPLE STORAGE AND HOLDING TIMES.
1. Procedures for Sample Storage
The samples must be protected from light and refrigerated at 4°C (±2°C)
from the time of receipt until 60 days after delivery of a complete
sample data package to the Agency. After 60 days the samples may be
disposed of in a manner that complies with all applicable regulations.
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 samples received under this contract.
Samples and standards must be stored separately.
2. Contract Required Holding Times
The extraction of water samples by separatory funnel procedures must be
completed within five days of the Validated Time of Sample Receipt
(VTSR). Extraction of water samples by continuous liquid-liquid
extraction procedures must be started within five days of VTSR.
Extraction of soil/sediment samples by sonication must be completed
within 10 days of VTSR.
Analysis of samples must be completed within 35 days following the
start of extraction.
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SECTION II
PART B - SAMPLE PREPARATION FOR EXTRACTABLE PESTICIDES AND AROCLORS
1. Summary of Sample Preparation Methods
1.2 Water Samples
A 1-L volume of sample is spiked with che surrogate solution and is
extracted with methylene chloride by using a separatory funnel or a
continuous extractor. The methylene chloride extract is dried and
concentrated (5.3). The extract is then cleaned up by GPC (optional),
exchanged to hexane, cleaned up by Florisil cartridge, and adjusted to
a final volume of 10.0 mL (5.0 mL if GPC cleanup is performed) as
described beginning at paragraph 7.2.
1.3 Soil/sediment Samples
A 30 g aliquot of sample is spiked with the surrogate solution and then
mixed with sodium sulfate and extracted with a 1:1 acetone/methylene
chloride solvent mixture by sonication. The extract is then filtered,
dried, concentrated by K-D, and the solvent exchanged into methylene
chloride (6.3). The extract is then cleaned up by GPC (mandatory)..
exchanged to hexane, cleaned up by Florisil cartridge, and adj'Listed to
a final volume of 5.0 mL (7.2).
2. Interferences
2.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware. These
contaminants lead to discrete artifacts or to elevated baselines in gas
chromatograms. Routinely, all of these materials must be demonstrated
to be free from interferences under the conditions of the analysis by
running reagent blanks. Interferences caused by phthalate esters can
pose a major problem in pesticide analysis. Common flexible plastics
contain varying amounts of phthalates which are easily extracted during
laboratory operations, so cross-contamination of glassware frequently
occurs when plastics are handled. Interferences from phthalates can
best be minimized by avoiding che use of such plastics in the
laboratory.
2.2 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 sice being sampled. The cleanup procedures must be used to remove
such interferences In order to achieve the Contract Required
Quantisation Limits.
3. Apparatus and Materials (Brand names, suppliers, and pare numbers are
for illustrative purposes only)
3.1 Continuous liquid-liquid extractors - with Teflon or glass connecting
lines for use with methylene chloride, (Hershberg-tfolf Extractor,, Ace
Glass Company, Vineland, NH, P/N 6841-10 or equivalent).
3.2 Separatory funnel - 2000 mL with Teflon stopcock.
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SECTION II
3.3 Apparatus for determining percent moisture
3.3.1 Oven - drying.
3.3.2 Desiccator.
3.3.3 Crucibles - porcelain (optional).
3.3.4 Aluminum weighing pans (optional).
3.4 Sonic cell disrupter - Heat Systems, Ultrasonics, Inc., Model W-385
(475 watt with pulsing capability, No. 207 3/4-inch tapped disruptor
horn), or equivalent device with a minimum 375 Watt output capability.
NOTE: In order to ensure that sufficient energy is transferred to the
sample during extraction, the horn must be replaced if the tip begins
to erode. Erosion of the tip is evidenced by a rough surface.
3.5 Sonabox (or equivalent) for use with disruptor to decrease noise level.
3.6 Beakers - 400-mL.
3.7 Kuderna-Danish (K-D) apparatus.
3.7.1 Concentrator tube - 10-mL, graduated (Kontes K-570040-1029, or
equivalent).
3.7.2 Evaporative flask - 500-mL (Kontes K-470001-0500, or
equivalent).
3.7.3 Snyder column - three-ball macro (Kontes K-503000-0121, or
equivalent).
3.8 Funnels and Filter Paper.
3.8.1 Powder funnels - 10-cm diameter (optional), for
filtration/drying.
3.8.2 Buchner funnels - 9-cm diameter, for filtration (optional).
3.8.3 Filter paper - No. 41 Whatman (or equivalent), 9-cm circles
(optional).
3.9 Boiling chips.
3.9.1 Silicon carbide boiling chips - approximately 10 to 40 mesh.
Heat the chips to 400'C for 30 minutes or solvent rinse before
use.
3.9.2 Teflon boiling chips (optional) - solvent rinse the chips
before use.
3.10 Water bath - heated, with concentric ring cover, capable of temperature
control. NOTE: The water bath should be used in a hood.
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SECTION II
3.11 Top loading balance - capable of weighing accurately to ± 0.01 g.
3.12 Balance - analytical, capable of weighing accurately to + 0.0001 g.
The balance must be calibrated with class S weights once per each 12-
hour workshift. The balances must also be checked annually by a
certified technician.
3.13 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).
3.14 Vials and caps - 2-mL for GC auto sampler.
3.15 Gel permeation chromatography (GPC) cleanup device. NOTE: GPC cleanup
is required for all extracts for all soils (see paragraph 7.1.1).
Gel permeation chromatography system - GPC Autoprep Model 1002 A or B,
Analytical Biochemical Laboratories, Inc., or equivalent. Systems that
perform very satisfactorily also have been assembled from the following
components - an HPLC pump, an auto sampler or a valving system with
sample loops, and a fraction collector. All systems, whether automated
or manual, must meet the calibration requirements of 7.1.3.
3.15.1 Chromatographic column - 700 mm x 25 mm i.d. glass column.
Flow is upward. To simplify switching from the UV detector
during calibration to the GPC collection device during extract
cleanup, an optional double 3-way valve (Rheodyne Type 50
Teflon Rotary Valve #10-262 or equivalent) may be attached so
that the column exit flow can be shunted either to the UV flow-
through cell or to the GPC collection device.
3.15.2 Guard column - (Optional) 5 cm, with appropriate fittings to
connect to the inlet side of the analytical column (Supelco 5-
8319 or equivalent).
3.15.3 Bio Beads (S-X3) - 200-400 mesh, 70 gm (Bio-Rad Laboratories,
Richmond, CA, Catalog 152-2750 or equivalent). An additional 5
gm of Bio Beads is required if the optional guard column is
employed. The quality of Bio Beads may vary from lot to lot
because of excessive fines in s. me lots. In addition to fines
having a detrimental effect on chromatography, they also can
pass through the column screens and damage the valve.
3.15.4 Ultraviolet detector - fixed wavelength (254 nm) with a semi-
- prep flow-through cell.
3.15.5 Strip chart recorder, recording integrator or laboratory data
system.
3.15.6 Syringe - 10-mL with Luerlok fitting.
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SECTION II
3.15.7 Syringe filter assembly, disposable - Bio-Rad "Prep Disc"
sample filter assembly #343-0005, 25 mm, and 5 micron filter
discs or equivalent. Check each batch for contaminants. Rinse
each filter assembly (prior to use) with methylene chloride if
necessary.
3.15.8 A description of a manual system assembled from parts can be
found in Wise, R.H., Bishop, D.F., Williams, R.T. & Austern,
B.M. "Gel Permeation Chromatography in the GC/MS Analysis of
Organics in Sludges" U.S. EPA, Municipal Environmental Research
Laboratory, Cincinnati, Ohio, 45268.
3.16 Florisil - 500-mg or 1-g cartridges with stainless steel or Teflon
frits, (Catalog No. 694-313, Analytichem, 24201 Frampton Ave., Harbor
City, CA, or equivalent).
3.17 Vacuum system for eluting multiple cleanup cartridges.
3.17.1 Vac Elute Manifold - Analytichem International, J.T. Baker, or
Supelco (or equivalent). The manifold design must ensure chat
there is no contact between plastics containing phthalates and
sample extracts.
3.17.2 Vacuum trap made from a 500-mL sidearm flask fitted with a one-
hole stopper and glass tubing.
3.17.3 Vacuum pressure gauge.
3.17.4 Rack for holding 10-mL volumetric flasks in the manifold.
3.18 Pyrex glass wool - rinsed with methylene chloride and dried before use.
3.19 Bottle or test tube - 20-mL with Teflon-lined screw cap for sulfur
removal.
3.20 Drying column - chromatographic column approximately 400 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 extf acts.)
3.21 Glass vials - minimum of 20-mL, with screw cap and Teflon or aluminum
foil liner.
3.22 Spatula - stainless steel or Teflon.
3.23 pH Paper - wide range, (Hydrion Papers, Microessential Laboratory,
Brooklyn, NY, or equivalent).
3.24 Pipet - Volumetric 1.00-mL or 2.00-mL (optional).
3.25 Syringe - 1.00-mL or 2.00-mL (optional).
3.26 Flask - Volumetric 10.00-mL.
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SECTION II
3.27 Flask - Volumecric 1.00-mL or 2.00-mL (optional).
3.28 Vials - 10-mL, with screw cap and Teflon liner (optional).
3.29 Tube - centrifuge, 12- to 15-mL with 19-mm ground glass joint
(optional).
3.30 Snyder Column - micro two or three ball with a 19-mm ground glass
joint.
3.31 Centrifuge - table top (optional).
3.32 Vortex mixer - Genie, Model 550-6, Scientific Industrial, Inc.,
Bohemia, NY, or equivalent.
3.33 pH Meter with a combination glass electrode.
3.34 Magnetic stirrer motor - Model PC353, Corning Co., Corning, NY, or
equivalent.
3.35 Magnetic stir bar - Teflon coated, at least 4 cm long,
3.36 Graduated cylinder - 1 L capacity.
4. Reagents
4.1 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 GC/ECD to demonstrate that it is free of interference before use.
Baker anhydrous granular, Catalog No, 3375, or equivalent. CAUTION:
An open container of sodium sulfate may become contaminated during
storage in the laboratory.
4.2 Methylene chloride, hexane, acetone, toluene, iso-octane, and methanol
(optional) - pesticide quality or equivalent. It is recommended that
each lot of solvent used 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.
4.3 Mercury - triple distilled, for sulfur clean-up.
4.4 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.
4.5 Sodium hydroxide solution (10 N) - Carefully dissolve 40 g of NaOH in
reagent water and dilute the solution to 100 mL.
4.6 Concentrated sulfuric acid - 18 N.
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SECTION II
4.7 Reagent water - defined as a water in which no interferent is observed
at one-half the CRQL of any pesticide/Aroclor when one liter of the
reagent water is extracted and prepared by using the same workup
procedure as for a water sample.
4.8 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 also will adversely affect Florisil
performance.
4.9 Standards
4.9.1 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.
4.9.2 Stock standard solutions (1.00 ug/uL) - can be prepared from
pure standard materials or purchased as certified solutions.
4.9.2.1 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.
4.9.2.2 Transfer the stock standard solutions into a
bottle/vial with Teflon-lined cap or septa. Store
at 4°C (±2°C) and protect from light. Stock
standard solutions must be replaced after six months
or sooner, if comparison with check standards
indicates a problem.
4.9.3 GPC calibration solution - prepare a solution in methylene
chloride that contains the following analytes in the
concentrations listed below:
Analyte mg/mL
corn oil 25
bis-2-ethylhexyl phthalate 1.0
methoxychlor 0.2
perylene 0.02
sulfur 0.08
NOTE: Sulfur is not very soluble in methylene chloride,
however, it is soluble in warm corn oil. Therefore, one
approach is to weigh out the corn oil, warm it and transfer the
weighed amount of sulfur into the warm corn oil. Mix it and
then transfer into a volumetric flask with methylene chloride,
along with the other calibration compounds.
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SECTION II
Store Che calibration solution in an amber glass bottle with a
Teflon lined screw-cap at 4'C, and protect from light.
(Refrigeration may cause the corn oil to precipitate. Before
use, allow the calibration solution to stand at room
temperature until the corn oil dissolves.) Replace the
calibration standard solution every six months, or more
frequently if necessary.
4.9.4 Surrogate solution - the surrogates, Tetrachloro-m-xylene and
Decachlorobiphenyl, are added to all standards, samples, matrix
spikes, and blanks. Prepare a surrogate spiking solution of
0.2 ug/mL of each of the two compounds in acetone. Hie
solution should be checked frequently for stability. The
solution must be replaced after six months, or sooner,, if
comparison with quality control check samples indicates a
problem. CAUTION: Analysts must allow all spiking solutions
to equilibrate to room temperature before use.
4.9.5 Pesticide matrix spiking solution - prepare a spiking; solution
in acetone or methanol that contains the following pesticides
in the concentrations specified:
Pesticide ug/roL
gamma-BHC (Lindane) 1.0
4,4'-DDT 4.0
Endrin 4.0
Heptachlor 1.0
Aldrin 1.0
Dieldrin 4.0
The solution must be prepared every six months, or sooner if
the solution has degraded or concentrated.
4.9.6 Florisil cartridge check solution.
Prepare a solution of 2,4,5-trichlorophenol in acetone, at a
concentration of 0.1 ug/mL.
5. Extraction of Water S-afples
Water samples may be extracted by either a 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.
5.1 Separatory Funnel Extraction
5.1.1 Measure out each 1.0 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 cone, sulfuric acid, if required. Samples
requiring pH adjustment must be noted in the SDG Narrative.
Place the sample into a 2-L separatory funnel.
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SECTION II
5.1.2 For each sample selected for matrix spike and matrix spike
duplicate analyses, measure out two additional 1-L portions and
transfer those portions into separate funnels. Adjust the pH
of each, if required, and fortify each with 1.0 mL of matrix
spike solution before continuing the extraction. The frequency
of MS/MSD analysis is given in Section III, paragraph 16.
5.1.3 Using a syringe or a volumetric pipet, add 1.0 mL of the
surrogate solution to all water samples, matrix spikes, and
blanks.
5.1.4 Add 60 mL methylene chloride to the separatory funnel and
extract the sample by shaking the funnel for two minutes, with
periodic venting to release excess pressure. 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 of the emulsion through glass wool,
centrifugation or other physical means. Drain the methylene
chloride into a 250 mL Erlenmeyer flask.
5.1.5 Add a second 60 mL volume of methylene chloride to the sample
bottle and repeat the extraction procedure a second time,
combining the extracts in the Erlenmeyer flask. Perform a
third extraction in the same manner.
5.1.6 Prepare a method blank with each group of water samples
extracted. For pesticide/Aroclor analyses, a method blank for
water samples consists of a 1 L volume of reagent water (see
paragraph 4.7), spiked with the surrogates and carried through
the entire analytical procedure. The frequency of method blank
analysis is given in Section III, paragraph 15.
5.2 Continuous Liquid-Liquid Extraction
5.2.1 Add methylene chloride (100 to 250 mL) to the bottom of the
extractor and fill it to a depth of at least one inch above the
bottom sidearm.
5.2.2 Measure out each 1.0 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 into the continuous extractor.
5.2.3 With some samples it may be necessary to place a layer of glass
wool between the methylene chloride and the water layers in the
extractor to prevent precipitation of suspended solids into the
methylene chloride during extraction.
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SECTION II
5.2.4 For each sample selected for matrix spike and matrix spike
duplicate analyses, measure out two additional 1-L portions and
transfer those portions into separate funnels. Adjust the pH
of each, if required, and fortify each with 1.0 mL of matrix
spike solution before continuing the extraction. The frequency
of MS/MSD analysis is given in Section III, paragraph 16.
5.2.5 Using a syringe or a volumetric pipet, add 1.0 mL of the
surrogate solution to all water samples, matrix spikes, and
blanks.
5.2.6 Adjust the level of methylene chloride in the extractor so that
the bottom sidearm is half filled with solvent.
5.2.7 Add sufficient methylene chloride to the distilling flask to
ensure proper solvent cycling during operation and extract the
solution for 18 hours.
5.2.8 Prepare a method blank with each group of water samples
extracted. For pesticide/Aroclor analyses, a method blank for
water samples consists of a 1 L volume of reagent water (see
paragraph 4.7), spiked with the surrogates and carried through
the entire analytical procedure. The frequency of method blank
analysis is given in Section III, paragraph 15.
5.3 Extract Drying and Concentration
5.3.1 Assemble a Kudema-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
pesticide/Aroclor target compounds listed in Exhibit C.
5.3.2 Pour the extract through a drying column containing about 10 cm
of anhydrous granular sodium sulfate and collect the extract in
the K-D concentrator. Rinse the Erlenmeyer flask and the
column with at least two additional 20 to 30 mL portions of
methylene chloride to complete the quantitative transfer.
5.3.3 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* -
80*C) 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.
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SECTION II
5.3.4 If no GPC cleanup is required, proceed with the hexane exchange
described in paragraph 7.2. If GPC cleanup is to be used,
remove the Snyder column, rinse the flask and its lower joint
and collect the rinsate in the concentrator tube, adjust the
volume to 10.0 mL with methylene chloride. Proceed to 7.1.
6. Extraction of Soil/S
6.1 Sample Preparation
6.1.1 Mix samples thoroughly, especially composited samples. Discard
any foreign objects such as sticks, leaves and rocks. Also,
decant and discard any standing aqueous phase.
6.1.2 pH Determination - transfer 50 g of soil/sediment to a 100-mL
beaker. Add 50 mL of water and stir the solution with a
magnetic stirrer for 1 hour. Determine the pH of the sample by
using a glass electrode and the pH meter while the sample is
stirred. Report pH value on the appropriate data sheet. If
the pH of the soil is > 9 or < 5, document any subsequent
problems in the analysis related to pH in the SDG Narrative,
but do not attempt to adjust the pH of the sample. Discard the
portion of the sample used for pH determination.
NOTE: If insufficient volume of soil is received, use 5 g of
soil and 5 mL of water for the pH determination and note in the
SDG Narrative.
6.1.3 Percent Moisture - Weigh 5 to 10 g of the sediment to the
nearest 0.01 g into a tared crucible or aluminum weighing pan.
Determine the weight percent volatilized by drying overnight at
105°C (hereafter referred to as percent moisture). After the
sample is dry, remove the sample and pan and allow them to cool
in a desiccator before weighing. Calculate the percent
moisture according to Equation 1 below. Concentrations of
individual analytes will be reported relative to the dry weight
of sediment. CAUTION: Gases volatilized from some
soil/sediment samples may require that this drying procedure be
carried out in a hood.
Percent tft of Sample . Wt of Dry San,pie
Moisture - „ . - — x 100 EQ. 1
Wt of sample
6.2 Extraction with Sonication
6.2.1 Tune the sonicator according to the manufacturer's directions
prior to extracting samples by this procedure.
6.2.2 Weigh approximately 30 g of sample (to the nearest 0.1 g) into
a 250 or 400-mL beaker and add 60 g of anhydrous sodium sulfate
(granular).
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SECTION II
6.2.3 For a sample to be used for matrix spike and matrix spike
duplicate analysis, weigh out two additional 30 g (record
weight to nearest 0.1 g) portions of sample and add 2.0 mL of
the pesticide matrix spike solution to each soil aliquot. The
frequency of MS/MSD analysis is given in Section III, paragraph
16.
6.2.4 Add 2.0 mL of surrogate solution to all soil samples, matrix
spikes, and blanks by using a volumetric pipet or a syringe.
Mix the solution well. The sample and the added sodium sulfate
should be a homogeneous, granular mixture at this point.
6.2.5 Immediately add 80 to 100 mL of 1:1 methylene chloride/acetone
to the sample.
6.2.6 Place the bottom surface of the sonicator probe about 1/2 inch
below the surface of the solvent but above the sediment layer.
6.2.7 Sonicate for 3 minutes using a 3/4-inch horn at full power
(output control knob at 10) with pulse on and percent duty
cycle knob set at 50 percent. Do not use a microtip.
NOTE: These settings refer to the Model W-385. When using a
sonicator other than Model W-385, refer to the instructions
provided by the manufacturer for appropriate output settings.
6.2.8 The extracted sample can be filtered by using gravity or vacuum
filtration.
6.2.8.1 For gravity filtration, prepare a filtration/drying
bed by placing a plug of glass wool in the neck of a
10-cm powder funnel and filling the funnel to
approximately half its depth (4 or 5 cm) with
anhydrous sodium sulfate (80-100 g). Decant the
extract through the packed funnel and collect it in
a 500-mL evaporation (K-D) flask.
6.2.8.2 For vacuum filtration, use Whatman No. 41 paper in
the Buchner funnel. Pre-wet the paper with methy-
lene chloride/acet ne before decanting the solvent.
6.2.9 Repeat the extraction two more times with additional 80 to 100
mL portions of the 1:1 methylene chloride/acetone. Before each
extraction, thoroughly mix the solid residue, and make certain
that the sodium sulfate is free flowing and not a consolidated
mass. As required, break up large lumps with a clean spatula.
Decant and filter the extraction solvent after each sonication
by using the same funnel described in paragraph 6.2.8. After
the final sonication, pour the entire sample into the funnel
and rinse the beaker and funnel with 60 mL of 1:1 methylene
chloride/acetone.
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SECTION II
6.2.10 Prepare a method blank with each group of soil/sediment samples
extracted. For pesticide/Aroclor analyses, a method blank for
soil/sediment samples consists of 30 g of sodium sulfate (see
paragraph 4.1), spiked with the surrogates and carried through
the entire analytical procedure. The frequency of method blank
analysis is given in Section III, paragraph 15.
6.3 Soil Extract Concentration
6.3.1 Add one or two clean boiling chips to the evaporative flask and
attach a three-ball macro Snyder column. Pre-wet the Snyder
column by adding about 1 mL of methylene chloride to the top.
Place the K-D apparatus on a hot water bath (60 to 80°C) 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. Reduce
the volume of liquid to less than 10 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.
6.3.2 In order to remove most of the acetone, it is absolutely
necessary to further reduce the volume of all soil/sediment
extracts to 1.0 mL. This is best accomplished using the
nitrogen blowdown technique (7.3.2). The presence of acetone
will cause a dead volume to develop in the GPC column and thus
will cause loss of surrogates and analytes during GPC cleanups.
6.3.3 Adjust the extract volume to 10.0 mL with methylene chloride.
Proceed to 7, below, for mandatory GPC and Florisil cartridge
cleanup of soil extracts.
7. Extract Cleanup
There are three cleanup procedures specified in this method: GPC,
Florisil cartridge, and sulfur cleanup. GPC must be performed for all
soil extracts. GPC must be performed for water extracts that contain
higher molecular weight contaminants that interfere with the analysis
of the target analytes. Florisil cartridge cleanup is mandatory for
all extracts. Sulfur cleanup must be performed for all sample extracts
contaminated with sulfur. Blanks and matrix spike and matrix spike
duplicate samples must be subjected to the same cleanup as the unspiked
samples.
7.1 Extract Cleanup by Gel Permeation Chromatography (GPC)
7.1.1. GPC cleanup is mandatory for all soil/sediment extracts. GPC
must be performed for water extracts that contain higher
molecular weight contaminants that interfere with the analysis
of the target analytes. Gel permeation chromatography (GPC) is
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SECTION II
a size exclusion cleanup procedure using organic solvents and
hydrophobic gels in the separation of synthetic macromolecules.
The packing gel is porous and is characterized by the range or
uniformity (exclusion range) of that pore size. In the choice
of gels, the exclusion range must be larger than the molecular
size of the molecules to be separated. A cross-linked divinyl
benzenestyrene copolymer (SX-3 Bio Beads or equivalent) is
specified for this method.
GPC is recommended for the elimination from the sample of
lipids, polymers, copolymers, proteins, natural resins and
polymers, cellular components, viruses, steroids, and dispersed
high-molecular-weight compounds. GPC is appropriate for both
polar and non-polar analytes, therefore, it can be used
effectively to clean up extracts containing a broad range of
analytes.
Normally, this method is most efficient for removing high
boiling materials that condense in the injection port area of a
gas chromatograph (GC) or in the front of the GC column. This
residue ultimately will reduce the chromatographic separation
efficiency or column capacity because of adsorption of the
target analytes on the active sites. Pentachlorophenol
especially is susceptible to this problem. GPC system
performance must be validated at least once every seven days by
demonstrating 80-100 percent recovery of the pesticide matrix
spike mixture and an Aroclor 1016/1260 mixture.
7.1.2 GPC Column Preparation
7.1.2.1 Weigh out 70 gm of Bio Beads (SX-3). Transfer them
to a quart bottle with a Teflon-lined cap or a 500
mL separatory funnel with a large bore stopcock, and
add approximately 300 mL of methylene chloride.
Swirl the container to ensure the wetting of all
beads. Allow the beads to swell for a minimum of 2
hours. Maintain enough solvent to cover the beads
% sufficiently at all times. If a guard column is to
be used, repeat the above with 5 gm of Bio Beads in
a 125 mL bottle or a beaker, using 25 mL of
methylene chloride.
7.1.2.2 Turn the column upside down from its normal
position, and remove the inlet bed support plunger
(the inlet plunger is longer than the outlet
plunger). Position and tighten the outlet bed
support plunger as near the end as possible, but no
closer than 5 cm (measured from the gel packing to
the collar).
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SECTION II
7.1.2.3 Raise the end of the outlet tube to keep the solvent
in the GPC column, or close the column outlet
stopcock. Place a. small amount of solvent in the
column to minimize the formation of air bubbles at
the base of poured column packing.
7.1.2.4 Swirl the bead/solvent slurry to get a homogeneous
mixture and, if the wetting was done in a quart
bottle, quickly transfer it to a 500 mL separatory
funnel with a large bore stopcock. Drain the excess
methylene chloride directly into the waste beaker,
and then start draining the slurry into the column
by placing the separatory funnel tip against the
column wall. This will help to minimize bubble
formation. Swirl occasionally to keep the slurry
homogeneous. Drain enough to fill the column.
Place the tubing from the column outlet into a waste
beaker below the column, open the stopcock (if
attached), and allow the excess solvent to drain.
Raise the tube to stop the flow, and close the
stopcock when the top of the gel begins to look dry.
Add additional methylene chloride to just rewet the
gel.
7.1.2.5 Wipe any remaining beads and solvent from the inner
walls of the top of the column with a laboratory
tissue. Loosen the seal slightly on the other
plunger assembly (long plunger) and insert it into
the column. Make the seal just tight enough so that
any beads on the glass surface will be pushed
forward, but loose enough so that the plunger can be
pushed forward.
CAUTION: Do not tighten the seal if beads are
between the seal and the glass surface because this
can damage the seal and cause leakage.
7.1.2.6 Compress the column as much as possible without
applying excessive force. Loosen the seal and
gradually pull out the plunger. Rinse and wipe off
the plunger. Slurry any remaining beads and
transfer them into the column. Repeat the step in
paragraph 7.1.2.5 and reinsert the plunger. If the
plunger cannot be inserted and pushed in without
allowing beads to escape around the seal, continue
compression of the beads without tightening the
seal, and loosen and remove the plunger as
described. Repeat this procedure until the plunger
is inserted successfully.
7.1.2.7 Push the plunger until it meets the gel, then
compress the column bed about four centimeters.
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SECTION II
7.1.2.8 Pack the optional 5 cm column with approximately 5
gm of preswelled beads (different guard columns may
require different amounts). Connect the guard
column to the inlet of the analytical column.
7.1.Z/9 Connect the column inlet to the solvent reservoir
(reservoir should be placed higher than the top of
the column) and place the column outlet tube in a
waste container. Placing a restrictor in the outlet
tube will force air out of the column more quickly.
A restrictor can be made from a piece of capillary
stainless steel tubing of 1/16" OD x 10/1000" ID x
2". Pump methylene chloride through the column at a
rate of 5 mL/min for one hour.
7.1.2.10 After washing the column for at least one hour,
connect the column outlet tube, without the
restrictor, to the inlet side of the UV detector.
Connect the system outlet to the outlet side of the
UV detector. A restrictor (same size as the one in
paragraph 7.1.2.9) in the outlet tube from the UV
detector will prevent bubble formation which causes
a noisy UV baseline. The restrictor will not effect
flow rate. After pumping methylene chloride through
the column for an additional 1-2 hours, adjust the
inlet bed support plunger until approximately 6-10
psi backpressure is achieved. Push the plunger in
to increase pressure or slowly pull outward to
reduce pressure.
7.1.2.11 When the GPC column is not to be used for several
days, connect the column outlet line to the column
inlet to prevent column drying and/or channeling.
If channeling occurs, the gel must be removed from
the column, reswelled, and repoured as described
above. If drying occurs, methylene chloride should
be pumped through the column until the observed
column pressure is constant and the column appears
wet. Always recalibrate after column drying has
occurred to verify retention volumes have not
changed.
NOTE: The description of solvent flow rate and
column pressure applies only to the ABC GPC
apparatus. Laboratories using equivalent equipment
must develop the parameters for their apparatus
which give acceptable performance as described in
7.1.4.
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SECTION II
7.1.2.12 The GPC calibration procedure is based on monitoring
the elution of standards with a UV detector
connected to the GPC column. Care must be taken to
account for any difference in volume (elution time)
between the GC column and the detector and between
the GPC column and the collection vial.
NOTE: The UV detector calibration procedure
described in 7.1.3 is to be used for the analyses of
organochlorine pesticides and Aroclors listed in
Exhibit C. IT MUST NOT BE USED FOR THE ANALYSIS OF
GC/MS EXTRACTABLES OR OTHER ANALYTES WITHOUT A
RECOVERY STUDY.
7.1.3 Calibration of the GPC Column
7.1.3.1 Using a 10 mL syringe, load sample loop #1 with
calibration solution (paragraph 4.9.3). With the
ABC automated system, the 5 mL sample loop requires
a minimum of 8 mL of the calibration solution. Use
a firm, continuous pressure to push the sample onto
the loop. Switch the valve so that GPC flow is
through the UV flow-through cell.
7.1.3.2 Inject the calibration solution and obtain a UV
trace showing a discrete peak for each component.
Adjust the detector and/or recorder sensitivity to
produce a UV trace that meets the following
requirements. Differences between manufacturer's
cell volumes and detector sensitivities may require
a dilution of the calibration solution to achieve
similar results. An analytical flow-through
detector cell will require a much less concentrated
.solution than the semi-prep cell and, therefore, the
analytical cell is not acceptable for use.
o Peaks must be observed and should be symmetrical
for all compounds in the calibration solution.
s
o Corn oil and phthalate peaks must exhibit >85%
resolution.
o Phthalate and methoxychlor peaks must exhibit >85%
resolution.
o Methoxychlor and perylene peaks must exhibit >85%
resolution.
o Perylene and sulfur peaks must not be saturated
and must exhibit >90% baseline resolution,
7.1.3.3 Determine the elution times for the phthalate,
methoxychlor, and perylene. Phthalate will elute
first, perylene, last.
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SECTION II
7.1.3.4 Choose a "DUMP" time which removes > 85 percent of
the phthalate. Choose a. "COLLECT" time so that > 95
percent of the methoxychlor is collected, and
continue to collect until just prior to the elution
time of sulfur. Use a "WASH" time of 10 minutes.
7.1.3.5 NOTE: The DUMP and COLLECT times must be adjusted
to compensate for the difference in volume of the
lines between the detector and the collection flask.
7.1.3.6 Verify the flow rate by collecting column eluate for
10 minutes in a graduated cylinder and measure the
volume, which should be 45-55 mL (4.5-5.5 niL/min).
If the flow rate is outside of this range,
corrective action must be taken, as described above.
Once the flow rate is within the range of 4.5-5.5
mL/min, record the column pressure (should be 6-10
psi) and room temperature. Changes in pressure,
solvent flow rate, and temperature conditions can
affect analyte retention times and must be
monitored. If the flow rate and/or column pressure
do not fall within the above ranges, a new column
should be prepared. A UV trace that does not meet
the criteria in paragraph 7.1.3.2 would also
indicate that a new column should be prepared. It
may be necessary to obtain a new lot of Bio Beads if
the column fails all the criteria.
7.1.3.7 Reinject the calibration solution after appropriate
collect and dump cycles have been set, and the
solvent flow and column pressure have been
established.
7.1.3.7.1 Measure and record the volume of
collected GPC eluate in a graduated
cylinder. The volume of GPC eluate
collected for each sample extract
- processed may be used to indicate
problems with the system during sample
processing.
7.1.3.7.2 The retention times for bis(2-
ethylhexyl)phthalate and perylene must
not vary more than ±5% between
calibrations. If the retention time
shift is >5%, take corrective action.
Excessive retention time shifts are
caused by the following:
o Poor laboratory temperature control or
system leaks.
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SECTION II
o An unstabilized column that requires
pumping mechylene chloride through it
for several more hours or overnight.
o Excessive laboratory temperatures
causing outgassing of the methylene
chloride.
7.1.3.8 Analyze a GPC blank by loading 5 mL of methylene
chloride into the GPC. Concentrate the methylene
chloride that passes through the system during the
collect cycle using a Kuderna-Danish (KD)
evaporator. Analyze the concentrate by GC/MS. If
the blank exceeds one half the CRQL of any analyte,
pump additional methylene chloride through the
system for 1-2 hours. Analyze another GPC blank to
ensure the system is sufficiently, clean. Repeat the
methylene chloride pumping if necessary.
7.1.4 GPC Calibration Check
Mo Florisil cleanup is used in the GPC calibration check.
7.1.4.1 At least once every 7 days, the calibration of the
GPC must be verified with two check mixtures. The
first mixture is prepared by concentrating 2.0 mL of
the matrix spiking solution (paragraph 4.9.5) to
less than 1 mL under a stream of nitrogen (7.3.2),
and adjusting the final volume to 10.0 mL with
methylene chloride. The second mixture is prepared
with 2 ug of Aroclor 1016 and 2 ug of Aroclor 1260
in a. final volume of 10.0 mL methylene chloride.
7.1.4.2 Load the first 5.0 mL sample loop by using a 10 mL
syringe containing 8 mL of the diluted pesticide
matrix spike solution (paragraph 7.1.4.1). The
Aroclor mixture is loaded into Loop 2 in the same
manner. Fractions are collected in an auto sequence
by using the GPC program established by the UV
detector calibration procedure (Paragraph 7.1.3).
7.1.4.3 The collected GPC calibration fraction is
transferred to a K-D apparatus, and the collection
vessel is rinsed with two additional 10-mL portions
of methylene chloride to complete the transfer. The
volume of methylene chloride is reduced (described
in 7.3.2). After cooling, the solvent is exchanged
to hexane according to the instruction in 7.2. The
final volume is adjusted to 10.0 mL, and the sample
is analyzed by GC according to the procedures in
Section III. The analysis must be performed on at
least one of the GC columns used for samples
analysis.
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SECTION II
7.1.4.4 The pattern of the Aroclor quantisation peaks and
the recovery of each single component analyte must
" ~ be determined for evaluation and reporting purposes.
If the recovery of each of the analytes is 80 to 110
percent and if the Aroclor pattern is the same as
with previously run standards, then the analyst may
continue to use the column. If recoveries are out
of the acceptance window or if changes in the
relative peak heights of the patterns of the Aroclor
are observed, the column must be replaced and
recalibrated according to the instructions in 7.1.3.
7.1.4.5 Some samples may contaminate the SX-3 Bio Beads and
change the retention volume of the GPC column.
Therefore system calibration and analyte recovery
must be checked whenever a sample causes significant
discoloration of the GPC column. „ Even if no
darkening is visible, GPC calibration muse be
checked not less than once every seven days. In
many cases, the SX-3 Bio Beads may be used for
several months as long as the column calibration and
flow rate remain constant.
7.1.5 Daily UV calibration check (optional)
The calibration of the GPC may be monitored daily by use of the
UV-GPC calibration solution (paragraph 4.9.3) and the UV
Detector Calibration Procedure (7.1.3). The UV detector should
be used to monitor the elution times for the phthalate,
methoxychlor, and perylene, in that order. The precalibrated
GPC program should "DUMP" > 85 percent of the phthalate and
should "COLLECT" > 95 percent of the methoxychlor and perylene.
Significant changes in elution times of the analytes (e.g., >
0.5 minutes) indicate that the column is out of calibration and
must be recalibrated or replaced.
7.1.6 Sample Extract Cleanup
It is very important to have consistent laboratory temperatures
during an entire GPC run, which could be 24 hours or more. If
temperatures are not consistent, retention times will shift,
and the dump and collect times determined by the calibration
standard no longer will be appropriate. The ideal laboratory
temperature to prevent outgassing of the methylene chloride is
72'?.
7.1.6.1 In order to prevent overloading of the GPC column,
highly viscous sample extracts must be diluted prior
to cleanup. Any sample extract with a viscosity
greater than that of a 1:1 glycerol:water solution
must be diluted and loaded into several loops.
Similarly, extracts containing more than 500 mg of
nonvolatile residue per 5 mL of extract must be
diluted and loaded into several loops. The
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SECTION II
nonvolatile residue may be determined by evaporating
a 100 uL aliquot of the extract to dryness in a
tared aluminum weighing pan, or other suitable
container.
7.1.6.2 Particles greater than 5 micron may scratch the
valve, which may result in a system leak and cross
contamination of sample extracts in the sample
loops. To avoid such problems, filter the extract
through a 5 micron filter disc by attaching a
syringe filter assembly containing the filter disc
to a 10 mL syringe. Draw the sample extract through
the filter assembly and into the 10 mL syringe.
Disconnect the filter assembly before transferring
the sample extract into a small glass container,
e.g., a 15 mL culture tube with a Teflon lined screw
cap. Alternatively, draw the extract into the
syringe without the filter assembly. Attach the
filter assembly and force the extract through the
filter and into the glass container. Draw a minimum
of 8 mL of extract into a 10 mL syringe.
INTRODUCTION OF PARTICULATES OR GLASS WOOL INTO THE
GPC SWITCHING VALVES HAY REQUIRE FACTORY REPAIR OF
THE APPARATUS.
7.1.6.3 Prior to loading samples, put the GPC into the
"LOAD" mode, set the instrument terminal for the
number of loops to be loaded, and set the "DUMP",
"COLLECT", and "WASH" times for the values
determined by the calibration procedure described in
7.1.3.
7.1.6.4 Attach the syringe to the turn lock on the injection
port. Use firm, continuous pressure to push the
sample onto the 5-mL sample loop. If the sample is
difficult to load, some part of the system may be
blocked. Take appropriate corrective action. If
the back pressure is normal (6-10 psi) the blockage
is probably in the valve. Blockage may be flushed
out of the valve by reversing the inlet and outlet
tubes and pumping solvent through the tubes (this
should be done before sample loading).
NOTE: Approximately 2 mL of the extract remains in
the lines between the injection port and the sample
loop; excess sample also passes through the sample
loop to was te.
7.1.6.5 After loading a loop, and before removing the
syringe from the injection port, index the GPC to
the next loop. This will prevent loss of sample
caused by unequal pressure in the loops.
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SECTION II
7.1.6.6 After loading each sample loop, wash the loading
port with methylene chloride in a FIFE wash bottle
to minimize cross contamination. Inject
approximately 10 mL of methylene chloride to rinse
the common tubes.
7.1.6.7 After loading all the sample loops, index the GPC to
the 00 position, switch to the "RUN" mode and start
the automated sequence. Process each sample using
the collect and dump cycle times established in
7.1.3.
7.1.6.8 Collect each sample in a 250-mL Erlenmeyer flask,
covered with aluminum foil to reduce solvent
evaporation, or directly into a Kuderna-Danish
evaporator. Monitor sample volumes collected.
Changes in sample volumes collected may indicate one
or more of the following problems:
o Change in solvent flow rate, caused by channeling
in the column or changes in column pressure.
o Increase in column operating pressure due to the
absorption of particles or -gel fines onto either
the guard column or the analytical column gel, if
a guard column is not used.
o Leaks in the system or significant variances in
room temperature.
7.1.6.9 After the appropriate GPC fraction has been
collected for each sample, exchange the sample
extract solvent to hexane, as described beginning at
7.2. DO NOT ALLOW THE EXTRACT TO GO TO DRYNESS.
Adjust the final volume of the hexane extract to 5.0
mL.
7.1.6.10 Any samples that were loaded into two or more loops
should be recombined and adjusted to a final volume
of 5.0 mL in hexane before proceeding to 7.3,
Florisil Cartridge Procedure.
7.1.6.11 NOTE: A final volume of 5.0 mL is required for
extract concentrates after GPC cleanup because only
half of the sample is used in the GPC sample loop (5
mL of the 10 mL described in paragraph 5.3.4 or
6.3.3).
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SECTION II
7.2 Solvent exchange into hexane
This procedure applies to both extracts of water samples and extracts
of soil samples.
7.2.1 Momentarily remove the Snyder column, add 50 mL of hexane and a
new boiling chip, and reattach the Snyder column. 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 3 to 5 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.
7.2.2 Remove the Snyder column; using 1 to 2 mL of hexane, rinse the
flask and its lower joint into the concentrator tube. Complete
quantitative transfer of the extract to a vial by using hexane.
7.2.3 Adjust the volume of the hexane extract to 10.0 mL. Proceed to
7.3 for Florisil cartridge cleanup.
7.3 Florisil Cartridge Procedure
Florisil cartridge cleanup is required for all extracts. Cleanup
significantly reduces matrix interferences caused by polar compounds.
7.3.1 Cartridge Performance Check - every lot number of Florisil
cartridges must be tested by the following procedure before
they are used for sample cleanup. Add 0.5 mL of 2,4,5-
trichlorophenol solution (0.1 mg/mL in acetone) and 0.5 mL of
Standard Mixture A, midpoint concentration (Section III,
paragraph 3.3) to 4 mL of hexane. Reduce the final volume to
0.5 mL using nitrogen (paragraph 7.3.2). Place the mixture
onto the top of a washed Florisil cartridge (paragraph
7.3.4.4), 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.
Reduce the final volume to 1.0 mL using nitrogen (7.3.2) and
analyze the solution by GC/ECD. The recovery of each analyte
must be determined for evaluation and reporting purposes. The
lot of Florisil cartridges is acceptable if all pesticides are
recovered at 80 to 110 percent, if the recovery of
trichlorophenol is less than 5%, and if no peaks interfering
with the target analytes are detected.
7.3.2 Nitrogen blowdown technique (taken from ASTM Method D 3086)
7.3.2.1 Place the concentrator tube with an open mini-Snyder
column attached in a heating bath (30 to 35°C) and
evaporate the solvent to the final volume by blowing
a gentle stream of clean, dry nitrogen (filtered
through a column of activated carbon) onto the
solvent. DO NOT ALLOW THE EXTRACT TO GO TO DRYNESS.
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SECTION II
7.3.2.2 New 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 tines with hexane and then dried
prior to use.
7.3.3 Extract preparation before Florisil cartridge cleanup
For samples which have been run through the GPC cleanup,
exchange the solvent to hexane (7.2) and adjust the hexane
extract volume to 5.0 mL by using the nitrogen blowdown
technique described in 7.3.2. For those aqueous samples not
passed through the GPC step, adjust the hexane extract volume
to 10.0 mL. The different extract volumes are required because
only half of the methylene chloride concentrates are used in
the GPC cleanup.
7.3.4 Florisil cartridge cleanup
7.3.4.1 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.
7.3.4.2 Place one Florisil cartridge into the vacuum
manifold for each sample extract.
7.3.4.3 The required Florisil cartridge size and the final
volume of the extract after Florisil cleanup are a
function of the GC autosampler that a laboratory
uses. If the autosampler operates reliably with 1.0
mL of sample extract, then a 500-mg cartridge is
used and the required final volume is 1.0 mL. If
the autosampler requ* res more sample, prepare 2.0 mL
of sample extract using a 1-g cartridge. Manual
injection requires only a 1.0 mL final extract
volume and a 500-mg cartridge.
7.3.4.4 Prior to cleanup of samples, the cartridges must be
washed with hexane/acetone (90:10). This is
accomplished by placing the cartridge in 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.
7.3.4.5 After the cartridges in 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
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SECTION II
solvent line from each cartridge is placed inside of
the appropriate volumetric flask as the manifold top
is replaced.
7.3.4.6 After the volumetric flasks are in place, vacuum to
the manifold is restored, and a volume of extract
equal to the required final volume (1.0 or 2.0 mL)
from each sample, blank or matrix spike extract is
transferred to the top frit of the appropriate
Florisil cartridge.
7.3.4.7 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:
7.3.4.8 The pesticides/Aroclors in the extract concentrates
are then eluted through the column with 9 mL of
hexane/acetone (90:10) and are collected into the
10-mL volumetric flasks held in the rack inside the
vacuum manifold.
7.3.4.9 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.
7.3.4.10 Concentrate the extract to 1.0 or 2.0 mL as required
in paragraph 7.3.4.3 by vising either nitrogen
blowdown (7.3.2) or a micro-Snyder column. Measure
the final volume with a syringe or by transferring
the extract to a volumetric flask.
7.3.4.11 Sulfur contamination will cause a rise in the
baseline of the chromatogram that may interfere with
the analyses of the later eluting pesticides. If
crystals of sulfur are evident or if the presence of
sulfur is suspected, proceed to 7.4. Sample
analyses showing the presence of sulfur are not
acceptable and must be cleaned up and reanalyzed.
7.3.4.12 If sulfur is not present, transfer the sample to a
GC vial and label the vial. The extract is ready
for GC/ECD analysis. Proceed to Section III. Store
Che extracts at 4*C in the dark.
7.4 Sulfur Removal
Sulfur can be removed by one of two methods, according to laboratory
preference. Interference which is due to sulfur is not acceptable. If
the sulfur concentration is such that crystallization occurs in the
concentrated extract, centrifuge the extract to settle the sample
extract with a disposable pipette, leaving the excess sulfur in the
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SECTION II
centrifuge tube. Transfer the extract to a clean centrifuge tube or
clean concentrator tube before proceeding with further sulfur cleanup.
7.4.1 If only part of a set of samples requires sulfur cleanup, then
two method blanks are required for that set: one that is
shaken with mercury or copper, and one that is not.
Sulfur cleanup blank - add 1.0 mL of surrogate to 10 mL of
hexane in a clean centrifuge tube or 10-mL vial. Concentrate
the solution to 2.0 mL by using either nitrogen blowdown or a
micro Snyder column. The concentrated volume of the blank must
be the same as the final volume of the samples associated with
the blank. Measure the volume with a syringe or by
transferring the solution to a volumetric flask. Proceed with
the sulfur removal using the same technique (mercury or copper)
as the samples associated with the blank.
7.4.2 Mercury technique s
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 precipitate1, and
liquid mercury. If the mercury appears shiny, proceed to
Section III and analyze the extract. If the mercury turns
black, repeat sulfur removal as necessary. 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.
7.4.3 Copper technique
Add approximately 2 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 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 III and
analyze the extract. If the copper changes color, repeat the
sulfur removal procedure as necessary.
D-32/PEST OLM01.0
-------
SECTION III
GC/EC ANALYSIS OF PESTICIDES AND AROCLORS
PEST D-33 OLM01.0
-------
-------
SECTION III
GC/EC ANALYSIS OF PESTICIDES AND AROCLORS
1. Summary of GC/EC Analysis
1.1 The analysis of samples is accomplished by using a wide-bore (0.53 mm
ID) fused silica capillary column.
1.2 Sample extracts, standards, and blanks must be analyzed within an
analytical sequence as defined in 5. GC/ECD analysis begins with an
initial demonstration of instrument performance and the calibration of
all pesticides and Aroclors. Acceptable initial calibration is defined
in paragraph 6. Initial calibration must be repeated whenever the
calibration verification stipulated in paragraph 7 fails, or when major
instrument maintenance or modification is performed.
s
1.3 An instrument blank, a Performance Evaluation Mixture, and a second
instrument blank and the midpoint concentration of Individual Standard
Mixtures A and B are analyzed no less than once in every 12 hour
analytical sequence in order to monitor retention times, calibration
factors, and column performance. Data can be collected only as long as
the results for these standards and instrument blanks fall within the
limits defined in paragraph 7. If two consecutive unacceptable
standards are run, all extracts run since the previous acceptable
standard must be reanalyzed. Additional standards and blanks are
recommended when highly contaminated samples are suspected.
1.4 Calibration and run sequence specifications of the GC/EC method apply
independently to both GC columns.
1.5 Matrix spike and a matrix spike duplicate analyses must be prepared and
analyzed at least once for each matrix type or once per Sample Delivery
Group (SDG), whichever is most frequent.
1.6 Analysis of a sample on both GC columns is required for all samples,
blanks, matrix spikes, and matrix spike duplicates.
1.7 A single component pesticide is identified if a peak is detected within
its appropriate retention time window on each of two columns.
Toxaphene and Aroclors are identified primarily by pattern recognition,
but RTs of three to five major peaks must also be taken into
consideration. Guidance on quantitation of Aroclors is given beginning
at 13.9.
1.8 Standards for all tentatively identified Aroclors 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 standard analyzed during initial calibration.
1.9 Quantitative analysis of pesticides/Aroclors must b^e accomplished by
the external standard method. Three-point calibration curves for
single component analytes and the surrogates must be generated during
D-34/PEST OLM01.0
-------
SECTION III
Che initial calibration. A linear response range muse be demonstrated
from the CRQL to a high point at least 30 times greater than the CRQL.
Single-point calibrations for multicomponent analytes are sufficient
for quantitation by this method.
1.10 The ECO response for single component analytes must be within the
three-point calibration range in order for quantitative measurements to
be made. The ECO response for the Aroclors/toxaphene must not: be
larger than the response for the high point calibration analysis of the
single component analytes. The extracts must be diluted if the ECD
response exceeds the calibration range. Quantitation must be performed
and reported for both GC columns.
1.11 Absolute retention times (RTs) are used for the identification of
pesticides/Aroclors. ' The absolute retention time window is calculated
during initial calibration as ±0.04 minutes of the mean RT of the
standard for all analytes except Methoxychlor, where the RT window is
±0.05 minutes of the mean RT of the standard. For the multicomponent
analytes, the absolute retention time window is calculated for each
peak (3 to 5) as ±0.04 minutes of the RT of the same peak in the
initial calibration standard analysis.
2. Gas Chromatograph/Election Capture Detector (GC/EC)
2.1 Gas Chromatograph
2.1.1 The gas Chromatograph (GC) system 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 be suitable for splitless injection and have all
required accessories including syringes, analytical columns,
and gases.
2.1.2 Gas chromatographs that are available from some manufacturers
may have difficulty in meeting certain method QC requirements
because of Endrin and DOT breakdown in the injector. This
problem can be minimized by operating the injector at 200-
205'C, using a Pyrex^ (not quartz) methyl silicone deactivated
injector liner, and deactivating any metal parts in the
injector with dichlorodimethyl si lane. In some cases, using a.
~ 1/4 inch packed column injector converted for use with 0.53 urn
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.
2.2 Gas Chromatograph Columns
2.2.1 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 DB-1701, 30 m x 0.53 mm
ID, 1.0 urn film thickness, (J&W Scientific, Folsom, CA, or
equivalent), and a DB-608, 30 m x 0.53 mm ID, 0.5 to 1.0 urn
film thickness (J&W Scientific, or equivalent). Equivalent
D-35/PEST OLM01.0
-------
SECTION III
columns may be employed if they meet the requirements for
resolution, initial calibration, and calibration verification
listed in this section.
2.2.2 Columns are mounted in 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.,
Beliefonte, 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.
2.3 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 the Agency, 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.
2.4 Electron Capture Detector - the makeup gas must be P-5, P-10
(argon/methane) or nitrogen according to the instrument specification.
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.
2.5 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 Co rescale chromatographic
data in order to report chromatograms meeting the requirements listed
within this method.
3. Calibration Standards
3.1 Resolution Check Mixture - prepare the mixture of pesticides in hexane
or iso-octane at the concentrations listed below. The mixture must be
prepared every six months, or sooner if the solution has degraded or
concentrated.
gamma-Chlordane 10.0 ng/mL Endrin ketone 20.0 ng/mL
Endosulfan I 10.0 ng/mL Methoxychlor 100.0 ng/mL
p,p'-DDE 20.0 ng/mL Tetrachloro-m-xylene 20.0 ng/mL
Dieldrin 20.0 ng/mL Decachlorobiphenyl 20.0 ng/m
Endosulfan sulfate 20.0 ng/mL
D-36/PEST OLM01.0
-------
SECTION III
3.2
Performance Evaluation Mixture (PEM) - prepare the PEM In hexane or
iso-octane at the concentration levels listed below. The PEM must be
prepared weekly, or more often if the solution has degraded or
concentrated.
i-BHC
alpha-BHC
4,4'-DDT
beta-BHC
10.0 ng/mL
10.0 ng/mL
100.0 ng/mL
10.0 ng/mL
Endrin
Methoxychlor
Te trachloro-m-xylene
Decachlorobiphenyl
50.0 ng/mL
250.0 ng/mL
20.0 ng/mL
20.0 ng/mL
3.3
Individual Standard Mixtures A and B - the single component pesticide
standards must be prepared in hexane or iso-octane at three
concentrations for each analyte, including the surrogates. Two
separate calibration mixtures, A and B, (listed below) are used to
ensure that each peak is adequately resolved. The low point
concentration corresponds to the CRQL for each analyte. The midpoint
concentration must be 10 times the low point concentration. The high
point concentration must be at least 30 times that of the low point,
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 concentration is valid. The solution must be prepared
every six months, or sooner if the solution has degraded or
concentrated.
Individual Standard Mixture A - Low Point Concentration
alpha-BHC
Heptachlor
gamma-BHC
Endosulfan I
Dieldrin
Endrin
p.p'-DDD
p.p'-DDT
Methoxychlor
Tetrachloro-m-xylene
Decachlorobiphenyl
ng/mL
ng/mL
.0 ng/mL
.0 ng/mL
10.0 ng/mL
10.0 ng/mL
10.0 ng/mL
10.0 ng/mL
50.0 ng/mL
20.0 ng/mL
20.0 ng/mL
Individual Standard Mixture B- Low Point Concentration
beta-BHC 5.0
-delta-BHC 5.0
Aldrin 5.0
Heptachlor expoxide 5.0
alpha-Chlordane 5.0
gamma-Chlordane 5.0
p.p'-DDE 10.0
Endosulfan sulfate 10.0
Endrin aldehyde 10.0
Endrin ketone 10.0
Endosulfan II 10.0
Tetrachloro-m-xylene 20.0
Decachlorobiphenyl 20.0
ng/mL
ng/mL
ng/mL
ng/mL
ng/mL
ng/mL
ng/mL
ng/mL
ng/mL
ng/mL
ng/mL
ng/mL
ng/mL
D-37/PEST
OLM01.0
-------
SECTION III
3.4 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 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 six months, or sooner if the solution has degraded or evaporated.
4. Gas Chromatograph Operating Conditions
The following are the gas chromatographic analytical conditions. The
conditions are recommended unless otherwise noted.
Carrier Gas: Helium
(Hydrogen may be used, see 2.3)
t*
Column Flow: 5 mL/min
Make-up Gas: P-5/P-10 or N2 (required)
Injector Temperature: > 200*C (see 4.1)
Injection: On-column
Injection Volume: 1 or 2 uL (see 4.2)
Injector: Grob-type, splitless
Initial Temperature: 150*C
Initial Hold Time: 1/2 min
Temperature Ramp: 5*C to 6*C/min
Final Temperature: 275'C
Final Hold Time: Until after Decachlorobiphenyl has
eluted (approximately 10 minutes)
Optimize GC conditions for analyte separation and sensitivity.
4.1 Manual injections must be 2.0 uL. Auto injectors may use 1.0 uL
volumes. The same injection volume must be used for all standards,
blanks, and samples.
4.2 Cold (ambient temperature) on-column injectors that allow injection
directly onto a 0.53 mm ID column may be used as long as the acceptance
criteria for resolution, calibration, and analyte breakdown are met.
D-38/PEST OLM01.0
-------
SECTION III
5.
Analysis Seauence for Standards and Samples
5.1 All acceptable samples must be analyzed within a valid analysis
sequence as given below.
Time
0 hr.
12 hr.
Another 12 hr.
Another 12 hr.
Iniection #
1 - 15
16
17
18
o
o
o
o
1st injection
past 12:00 hr.
2nd and 3rd
injections
past 12:00 hr.
o
o
o
o
o
o
1st injection
past 12:00 hr.
2nd injection
o
o
o
o
o
o
1st injection
past 12:00 hr.
2nd and 3rd
injections
past 12 hr.
o
o
o
o
o
etc.
MaterialJniected
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 s
Instrument Blank
Individual Standard Mixtures A and B
Sample
Subsequent Samples
Last Sample
Instrument Blank
Performance Evaluation Mixture
Sample
Subsequent Samples
Last Sample
Instrument Blank
Individual Standard Mixtures A and B
Sample
Subsequent Samples
NOTE: The first 12 hours are counted from the injection #16 (the
Instrument Blank at the end of the initial calibration sequence) , not
from injection #1. Samples may be injected until 12:00 hours have
elapsed. All subsequent 12-hour periods are timed from the injection
D-39/PEST
OLM01.0
-------
SECTION III
of the instrument blank that bracketts 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 accomodate staff working on 8-hour
shifts. I
!
5.2 Before any samples are analyzed, it is necessary for the Contractor to
complete an acceptable initial calibration sequence (see paragraph 6).
5.3 After the initial calibration, the analysis sequence may continue as
long as acceptable instrument blanks, Performance Evaluation Mixtures,
and Individual Standard Mixtures A and B are analyzed at the required
frequency (see paragraph 7). This analysis sequence shows only the
minimum required blanks and standards. More blanks and standards may
be run at the discretion of the Contractor; these must also satisfy the
criteria presented in paragraph 7 in order to continue the run
sequence.
5.4 An analysis sequence must also include all required matrix spike/matrix
spike duplicate analyses and method blanks, but the Contractor may
decide at what point in the sequence they are to be analyzed.
5.5 A standard of any identified Aroclor must be run within 72 hours of its
detection in a sample chromatogram.
D-40/PEST OLM01.0
-------
SECTION III
6. Initial Calibration
6.1 Initial Calibration Sequence
6.1.1 Before any samples are analyzed, it is necessary for the
Contractor to complete the initial calibration sequence given
below.
NOTE: Steps 16 and 17 are used as part of the calibration
verification as well (see paragraph 7).
INITIAL CALIBRATION SEQUENCE
1. Resolution Check
2. Performance Evaluation Mixture
3. Aroclor 1016/1260
4. Aroclor 1221
5. Aroclor 1232
6. Aroclor 1242
7. Aroclor 1248
6. 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
6.1.2 Samples may be analyzed only after the initial calibration
acceptance criteria (6.2) are met. Otherwise, the analytical
system is not functioning adequately for use with this
protocol.
6.1.3 The initial calibration may continue to be used as long as the
analytical system remains under control. The proof that the
analytical system is under control is provided by the analyses
of the Performance Evaluation Mixtures. If those analyses do
not meet the criteria described in paragraph 7, appropriate
corrective action must be taken, and the initial calibration
sequence must be repeated. The calibration sequence must also
be repeated if any major change in instrument hardware or
instrument parameters is made (e.g., if a new column is
installed or if the detector temperature is changed).
6.2 Initial Calibration Acceptance Criteria
6.2.1 The initial calibration sequence must be analyzed in the order
listed in paragraph 6.1 using the GC/ECD operating conditions
described in paragraph 4. The standards must be prepared
according to paragraph 3. Calculate the calibration factors
and retention times according to paragraphs 8-10.
D-41/PEST OLM01.0
-------
SECTION III
6.2.2 The resolution criterion is that the height of the valley
between two adjacent peaks in the Resolution Check Mixture must
not be greater than 60% of the height of the shorter peak. The
poorest resolution on the DB-608 column probably will be
between DDE and Dieldrin, between Methoxychlor and Endrin
ketone and between Endosulfan I and gamma-Chlordane. On the
DB-1701 column, resolution difficulties most frequently occur
between Endosulfan I and gamma-Chlordane, and between
Methoxychlor and Endosulfan sulfate.
6.2.3 The breakdown of DDT and Endrin in both of the Performance
Evaluation Mixtures must be less Chan 20.0 percent, and the
combined breakdown of DDT and Endrin must be less than 30.0
percent where
EQ.l
% Breakdown DDT - Amount found in ne (DDD+DDE) * 100
Amount in ng of DDT injected
EQ.2
% Breakdown Endrin -
Amount found in ng (Endrin aldehyde + Endrin ketone) * 100
Amount of Endrin injected in ng
EQ.3
Combined % Breakdown - %Breakdown DDT + %Breakdown Endrin
6.2.4 All peaks in both of the Performance Evaluation Mixtures must
be 100 percent resolved on both columns.
6.2.5 The absolute retention times of each of the single component
pesticides and surrogates in both of the PEMs must be within
±0.02 minutes of their mean absolute retention time determined
from the three-point initial calibration, except Methoxychlor.
The absolute retention time for Methoxychlor in both of the
PEMs must be within ±0.025 minutes of its mean absolute
retention time determined from the three-point initial
calibration.
6.2.6" The relative percent difference of the calculated amount and
the true amount for each of the single component pesticides and
surrogates in both of the PEMs must be less than or equivalent
to 25.0 percent, using equation 4.
6.2.7 At least one chromatogram from each of the two Individual
Standard Mixtures A and B, run during the initial calibration,
must yield peaks that give recorder deflections of 50 to 100
percent of full scale.
6.2.8 The retention time of each single component pesticide in each
of the Individual Standard Mixtures must be within ±0.02
minutes of the mean RT calculated for that compound.
D-42/PEST OLM01.0
-------
SECTION III
6.2.9 The RT of each single component pesticide in each of the three
calibration standards must be within 0.02 minutes of the mean
RT calculated for that compound.
6.2.10 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.
6.2.11 The % RSO of the calibration factors for each single component
analyte and surrogate must be less than 10.0 percent, except
for alpha-BHC, beta-BHC, gamma-BHC, DDT, Endrin, and
Methoxychlor, where the % RSD must be less Chan 15.0 percent.
6.3 Corrective Action.
6.3.1 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 acceptance criteria.
6.3.2 Contamination should be suspected as a cause if the detector
cannot achieve acceptable linearity using this method. In the
case of light contamination, baking out the detector at: an
elevated temperature (350*C) should be sufficient to achieve
acceptable performance. In the case of heavy contamination,
passing hydrogen through Che detector 1-2 hours at an elevated
temperature may correct the problem. In the case of severe
contamination, the detector may require servicing by the ECD
manufacturer. DO NOT OPEN THE DETECTOR. THE ECD CONTAINS
RADIOCHEMICAL SOURCES.
6.3.3 If a laboratory cleans out a detector using an elevated
temperature, the ECD electronics must be turned off during the
bake out procedure.
6.3.4 After bake out or hydrogen reduction, the detector must be
recalibrated using the initial calibration sequence.
6.3.5" Initial calibration technical acceptance criteria MUST be met
before any samples or required blanks are analyzed. Any
samples or required blanks analyzed after the initial
calibration criteria have not been met will require reanalysis
at no additional cost to the Agency.
7. Calibration Verification
7.1 Three types of analyses are used to verify the calibration and evaluate
instrument performance. The analyses of instrument blanks, Performance
Evaluation Mixtures (PEM), and the mid point concentration of
Individual Standard Mixtures A and B constitute the continuing
calibration. Sample data are not acceptable unless bracketed by
D-43/PEST OLM01.0
-------
SECTION III
acceptable analyses of instrument blanks, PEM, and both Individual
Standard Mixtures A and B.
7.2 An instrument blank and the Performance Evaluation Mixture must bracket
one end of a 12-hour period during which sample data are collected, and
a second instrument blank and the the mid point concentration of
Individual Standard Mixtures A and B must bracket the other end of the
12-hour period.
7.3 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 that 12-hour period (see paragraph 5.1). Samples may be
injected for 12 hours from the injection of the instrument blank. The
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).
7.4 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 acceptance
criteria in paragraphs 7.8-7.14. 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 acceptance criteria in paragraphs 7.8-7.14. The 12-hour time
period begins with the injection of the instrument blank. Standards
(PEM or Individual Standard Mixtures), samples and required blanks may
be injected for 12:00 hours from the time of injection of the
instrument blank.
7.5 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(s) was injected.
7.6 After a break in sample analyses, the laboratory may only resume the
analysis of samples using the current initial calibration for
quantitation by analyzing an acceptable instrument blank and a PEM.
7.7 If the entire 12-hour period is not required for the analyses of all
samples to be reported and all data collection is to be stopped, the
incomplete 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 12-hour
period.
D-44/PEST OLM01.0
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SECTION III
7.8 All single component pesticides and surrogates in the Performance
Evaluation Mixtures used to demonstrate continuing calibration must be
100 percent resolved. 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.
7.9 The absolute retention time for each of the single component pesticides
(except methoxychlor) and surrogates in the PEMs and mid point
concentration of the Individual Standard Mixtures used to demonstrate
continuing calibration must be within ±0.02 minutes of their mean
absolute retention times determined from the three-point initial
calibration. The absolute retention time for Methoxychlor in the PEM
and Individual Standard Mixture must be within ± 0.025 minutes of its
mean absolute retention time determined from the three-point initial
calibration. NOTE: This is half the retention time window described
in paragraph 8.4.
7.10 The relative percent difference of the calculated amount and the true
amount for each of the single component pesticides and surrogates in
the PEM and mid point concentration of the Individual Standard Mixtures
used to demonstrate continuing calibration must be less than or equal
to 25.0 percent, using Equation 4.
Cnom ' Ccalc
RPD x 100 EQ. 4
nom
Cnom - nominal concentration of each analyte
Ccalc " calculated concentration of each analyte from the analyses of
the standard
7.11 The percent breakdown of DDT and Endrin in the PEM must be less than or
equal to 20.0 percent on both columns. The combined breakdown of DDT
and Endrin must be less than or equal to 30.0 percent on both columns.
7.12 All instrument blanks must meet the acceptance criteria in paragraph
15.3.
7.13 Analysts are cautioned that running an instrument blank and a
performance evaluation mixture once every 12 hours is the minimum
contract requirement. Late eluting peaks may carry over from one
injection to the next if highly complex samples are analyzed or if the
GC conditions are unstable. Such carryover is unacceptable.
Therefore, it may be necessary to run instrument blanks and performance
evaluation mixtures more often to avoid discarding data.
7.14 The requirements for running the instrument blanks, Performance
Evaluation Mixture, and Individual Standard Mixtures A and B are waived
when no samples, method blanks, or matrix spikes are run during that
12-hour period. After a break in sample analysis, a laboratory may
resume the analysis of samples, method blanks, and matrix spikes and
may use the current initial calibration for quantitation only after an
D-45/PEST OLM01.0
-------
SECTION III
acceptable PEM is run (paragraphs 7,2 - 7.6). If a successful PEM
cannot be run after an interruption, an acceptable initial calibration
must be run before sample data may be collected. All acceptable sample
analyses must be bracketed by acceptable performance evaluation
mixtures and instrument blanks.
8. Determination of Absolute Retention Times.
8.1 During the initial calibration sequence, absolute retention times (RT)
are determined for all single response pesticides, the surrogates, and
at least three major peaks of each multicomponent analyte.
8.2 For single component pesticides, an RT is measured in each of three
calibration standards and the mean RT is calculated as the average of
the three values. An RT is measured for the surrogates in each of the
three analyses of Individual Mixture A during the initial calibration
and the mean RT is calculated as the average of the three values. The
RT of each single component pesticide in each of the" three calibration
standards must be within 0.02 minutes of the mean RT calculated for
that compound.
8.3 A retention time window is calculated for each single component analyte
and surrogate by using the list in paragraph 8.4. Windows are centered
around the mean absolute retention time for the analyte established
during the initial calibrations.
D-46/PEST OLM01.0
-------
SECTION III
8.4 Retention time windows for single and multicomponent analytes and
surrogates.
Retention Time Window
Compound in Minutes
alpha-BHC ±0.04
beta-BHC ±0.04
gamma-BHC ±0.04
delta-BHC ±0.04
Heptachlor ±0.04
alpha-Chlorodane ±0.04
gamma-Chlorodane ±0.04
Aldrin ±0.04
Heptachlor epoxide ±0.04
Dieldrin ±0.04
Endrin ±0.04
Endrin aldehyde ± 0.04 „
Endrin ketone ±0.04
ODD ±0.04
DDE ±0.04
DDT ±0.04
Endosulfan I ±0.04
Endosulfan II ±0.04
Endosulfan sulfate ±0.04
Methoxychlor ±0.05
Aroclors ±0.04
Toxaphene ±0.04
Tetrachloro-m-xylene ±0.04
Decachlorobiphenyl ±0.04
8.5 For each multicomponent analyte, the RTs for three to five peaks are
calculated from the initial calibration standard analysis. An RT
window of ±0.04 minutes is used for all multicomponent analyte peaks.
8.6 Analytes are identified when peaks are observed in the RT window for
the compound on both GC columns.
9. Calibration Factors for Single Component Pesticides.
9.1 During the initial calibration sequence, the Contractor must establish
the magnitude of the linear ECD response range for each single
component pesticide and surrogate on each column and for each GC
system. This is accomplished by analyzing the Individual Standard
Mixtures A and B at three concentrations during the initial calibration
sequence in paragraph 6.
9.2 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 single component pesticide and
surrogate. 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
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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.
9.2.1 Calculate the calibration factor for each single component
pesticide and surrogate over the initial calibration range
using Equation 5.
9.2.2 Calculate the mean and the %RSD of the calibration factors for
each single component pesticide and surrogate over the initial
calibration range using Equations 6 and 7.
CF - Peak Area for Height) of the Standard EQ. 5
Mass Injected (ng)
_ n CFi
CF - £ EQ. 6
i-1 n
% RSD - SD
CF X 10°
CF EQ. 7
Where SD - Vi=l and n-3
n-1
9.2.3 The linearity of the calibration is considered acceptable when
the % RSD of the three point calibration is less than 10.0
percent for all-single component pesticides except alpha-BHC,
beta-BHC, gamma-BHC, DDT. Endrin, and Methoxychlor, where the %
RSD must be less than 15.0 percent.
9.2.4 If the linearity requirements listed above are met, the
calibration factor from the mid point concentration standard is
used for quantitation of each single component pesticide.
9.3 Sample analysis may not proceed until a satisfactory calibration has
been demonstrated.
10. Calibration Factors for Toxaphene and Aroclors
10.1 Toxaphene and Aroclors require only a single-point calibration and they
present special analytical difficulties. Because of the alteration of
these materials in the environment, it is probable that samples which
contain multicomponent analytes will give patterns similar to, but not
identical with, those of the standards.
10.2 A set of three to five major peaks is selected for each multicomponent
analyte. Retention times (see 8.4) and calibration factors are
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determined from the initial calibration analysis for each peak.
Guidance for the choice of which peaks to use is given in paragraph
13.9
11. Acceptance Criteria for Chromatoqrams of Calibration Standards
The identification of single component pesticides by gas
chromatographic methods is based primarily on rentention time data.
The retention time of the apex of a peak can be verified only from an
on-scale chromatogram. The identification of multicomponent analytes
is based primarily on recognition of patterns of retention times
displayed on a chromatogram. Therefore, the following requirements
apply to all data presented for single component and multicomponent
analytes.
11.1 The chromatograms that result from the analyses of the Resolution Check
Mixture, the Performance Evaluation Mixture, 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.
11.2 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.
11.3 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.
11.4 For any standard containing alpha-BHC, 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 e.ution time of
decachlorobiphenyl.
11.5 If a chromatogram is replotted electronically to meet requirements, the
scaling factor used must be displayed on the chromatogram.
11.6 If the chromatogram of any standard needs to be replotted
electronically to meet these requirements, both the initial
chromatogram and the replotted chromatogram must to submitted in the
data package.
12. Sample Analysis
12.1 Unless ambient temperature on-coluam injection is used (see paragraph
4.2), the injector must be heated to at least 200°C. The gas
chromatographic conditions from paragraph 4 must be used.
12.2 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 shall use at least 2.0 uL injection
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volumes. The same injection volume must be used for all standards,
samples, and blanks associated with the same initial calibration.
12.3 Analysis of a sample on both GC columns is required for all samples,
blanks, matrix spikes, and matrix spike duplicates.
12.4 The requirements for the analysis sequence apply to both GC columns and
for all instruments used for these analyses.
12.5 The laboratory will identify and quantitate analyte peaks based on RT
and calibration factor established during the initial calibration
sequence, as long as an acceptable calibration verification (see
paragraph 7) is performed every 12 hours.
12.6 The protocol is intended to achieve the quantitation limits shown in
Exhibit C whenever possible. If sample chromatograms have interfering
peaks, a high baseline, or off-scale peaks, then those samples must be
reanalyzed following dilution, further cleanup, or reextraction.
Samples which cannot be made to meet the given specifications after one
reextraction and three-step cleanup (GPC, Florisil, and sulfur removal)
are reported in the SDG Narrative and do not require further analysis.
No limit is placed on the number of reextractions of samples that may
be required because of contaminated method blanks.
12.7 The sample must be analyzed at the most concentrated level that is
consistent with achieving satisfactory chromatography (defined below).
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 extract must be reported. The
resulting changes in quantitation limits and surrogate recovery must be
reported also for the diluted samples.
12.8 If the Contractor has reason to believe that diluting the final
extracts will be necessary, an undiluted run may not be required. If
an acceptable chromatogram (as defined below) is achieved with the
diluted extract, an additional extract 10 times the concentration of
the dilute sample must be injected and reported with the sample data.
12.9 No target analyte concentrations may exceed the upper limit of the
initial calibration.
12.10 A standard for any identified multicomponent analyte must be analyzed
on the same instrument within 72 hours of its detection in a sample.
12.11 The identification of single component pesticides by gas
chromatographic methods is based primarily on retention time data. The
retention time of the apex of a peak can be verified only from an on-
scale chromatogram. The identification of multicomponent analytes is
based primarily on recognition of patterns of retention times displayed
on a chromatogram. Therefore, the following requirements apply to all
data presented for single component and multicomponent analytes.
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12.11.1 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.
12.11.2 Chromatograms must display single component pesticides detected
in the sample at less than full scale.
12.11.3 Chromatograms must display the largest peak of any
multicomponent axtalyte detected in the sample at less than full
scale.
12.11.4 If an extract must be diluted, Chromatograms must display
single component pesticides between 10 and 100 percent of full
scale.
12.11.5 If an extract must be diluted, Chromatograms must display the
peaks chosen for quantitation of multicomponent analytes
between 25 and 100 percent of full scale.
12.11.6 For any sample, 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.
12.11.7 If a chromatogram is replotted electronically to meet these
requirements, the scaling factor used must be displayed on the
chromatogram.
12.11.8 If the chromatogram of any sample needs to be replotted
electronically to meet these requirements, both the initial
chromatogram and the replotted chromatogram must be submitted
in the data package.
13. Quantitation of Analvtes
13.1 Quantitation must be performed and reported on both columns.
13.2 Analytes must be quantitated with an electronic integrator or with a
laboratory data system. The analyst can use either peak height or peak
area as the basis for quantitation. The use of an electronic
integrator or a laboratory data system is required.
13.3 The Chromatograms of all samples must be reviewed by a qualified
pesticide analyst before they are reported.
13.4 In order to be quantitated, the detector response (peak area or peak
height) of all of the single component analytes must lie between the
response of the low and high concentrations in the initial calibration.
If the analytes are detected below the CRQL, they are reported as
present below the CRQL, and flagged according to the instructions in
Exhibit B. If they are detected at a level greater than the high
calibration point, the sample must be diluted either to a maximum of
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1:100,000 or until the response is within the linear range established
during calibration. Guidance in performing dilutions and exceptions to
this requirement are given below.
13.4.1 If the response is still above the high calibration point after
the dilution of 1:100,000, the Contractor shall contact the SMO
immediately.
13.4.2 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.
13.4.3 The dilution factor chosen should keep the response of the
largest peak for a. target compound in the upper half of the
initial calibration range of Che instrument.
13.4.4 Do not submit data for more than two analyses, i.e., the
original sample extract and one dilution, of*, if a screening
procedure was employed, from the most concentrated dilution
analyzed and one further dilution.
13.4.5 Do not dilute MS/MSD samples solely to get non-spiked analytes
within the calibration range. The spiking level of each
compound in the pesticide/Aroclor matrix spiking solution
should not require the dilution of the MS/MSD unless the sample
from which these aliquots were taken contains high levels of
the spiked analytes.
13.5 The concentrations of the single component pesticides are calculated by
using the following equations:
13.5.1 Water
(V(Vt)(Df) EQ- 8
Concentration ug/L -
(CFXVCVi)
Where
AX - Area of the peak for the compound to be measured
CF - Calibration factor for the mid point concentration
external standard (area per ng)
VQ - Volume of water extracted in milliliters (mL)
V^ - Volume of extract injected in microliters (uL)
V£ - Volume of the concentrated extract in microliters (uL)
Df - Dilution Factor. The dilution factor for analysis of
water samples 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.
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13.5.2 Soil/Sediment
(Ax)(Vt)(Df) EQ. 9
Concentration ug/Kg -
(Dry weight basis) (CF)(Vi)(Ws)(D)
Where
A., and CF are as given for water, above.
Vc - Volume of the concentrated extract in microliters (uL)
V. — Volume of extract injected in microliters (uL)
D - 100 - % moisture
100
Ws - Weight of sample extracted in grams (g)
Df - Dilution Factor. The dilution factor for analysis of
soil samples by this method is defined as follows:
ML IB9ft 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.
13.5.3 Note that the calibration factors used for the quantitation of
the single component pesticides are the calibration factors
from the mid point concentration standard for each analyte.
13.6 The concentrations of the surrogates are calculated in a similar manner
as the other analytes, using Equations 8. and 9. The recoveries of the
surrogates are calculated acccording to Equation 10.
Qd EQ. 10
Surrogate Percent Recovery - g— x 100
Where
Q . - Quantity determined by analy is
Q — Quantity added to sample/blank
The limits for the recovery of the surrogates are 60-150 percent for
both surrogate compounds. As these limits are only advisory, no
further action is required by the laboratory is required, however,
frequent failures to meet the limits for surrogate recovery warrant
investigation by the laboratory, and may result in questions from the
Agency.
13.7 The quantitative determination of Toxaphene or Aroclors is somewhat
different from that of single component pesticides. Quantitation of
peaks within the detector linear range CRQL to > 30 times CRQL is based
on a single calibration point assuming linear detector response.
Alternatively, a linear calibration range may be established during a
run sequence by a three-point calibration curve for any multicomponent
analyte.
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13.8 The reporting requirements for multicomponent analytes are similar to
those for single component analytes. If the concentration is
calculated to be 10 times the CRQL, the Contractor shall contact the
SMO immediately.
13.9 The quantitation of toxaphene or Aroclors must be accomplished by
comparing the heights or the areas of each of the three to five major
peaks of the multicomponent analyte in the sample with the calibration
factor for the same peaks established during the initial calibration
sequence. The concentration of multicomponent analytes is calculated
by using Equations 8 and 9, where AX is the area for each of the major
peaks of the multicomponent analyte. The concentration of each peak is
determined and then an average concentration for three to five major
peaks is determined and reported on Form I (Exhibit B). The following
table lists the number of potential quantitation peaks for each Aroclor
and Toxaphene.
No. of Potential
Analvte Quantitation Peaks
Aroclor 1016/1260 5/5
Aroclor 1221 3
Aroclor 1232 4
Aroclor 1242 5
Aroclor 1248 5
Aroclor 1254 5
Toxaphene 4
13.10 The choice of the peaks used for multicomponent quantitation 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.
13.11 If more than one multicomponent analyte is observed in a sample, 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 compound.
14. Sample Data Acceptance Criteria
14.1 The requirements above apply to both columns, and quantitation must be
performed on both GC columns and reported.
14.2 All samples must be be analyzed as part of a valid analysis sequence
(paragraph 5). They must be bracketed by acceptable instrument blanks
(paragraph 15.3), acceptable Performance Evaluation Mixtures, and
acceptable Individual Standard Mixtures A and B (paragraph 7) that were
analyzed at the required frequency.
14.3 The retention times for both of the surrogates must be within the
retention time windows as calculated in paragraph 8.
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14.4 Reporcable data for a sample muse include a chromatogram in which a
baseline returns to below 50 percent of full scale before the elution
time of alpha-BHC, and to below 25 percent of full scale after alpha-
BHC and before decachlorobiphenyl.
14.5 If dilution has been applied and if no peaks are detected above 25
percent of full scale, analysis of a more concentrated sample is
required.
14.6 Reportable sample data must include chromatogram(s) which meet the
criteria in paragraph 12.11.
15. Blanks
There are two types of blanks required by this method: the method
blank and the instrument blank. A separate sulfur cleanup blank may be
required if all samples associated with a given method blank are not
subjected to sulfur cleanup. Samples that are associated with a sulfur
cleanup blank are also associated with the method bldnk with which they
were extracted. Both the method and sulfur cleanup blanks must meet
the respective acceptance criteria for the sample analysis acceptance
criteria to be met.
15.1 Method blank
15.1.1 Method blanks are spiked with the surrogate solution,
extracted, cleaned up, and analyzed by following the same
procedure that is used with the samples. A water method blank
is one liter of reagent water treated as the water sample
aliquot. A soil method blank is 30 g of sodium sulfate treated
as the soil sample aliquot.
Method blank analysis must be performed once for the following,
whichever is most frequent, and analyzed on each GO/EC system
used to analyze samples:
o Each Case, OR
o Each 14 calendar day period during which samples in a Case
are received (said period beginning with the receipt of the
first sample in that Sample Delivery Group), OR
o Each 20 samples in a Case, including matrix spikes and
reanalyses, that are of similar matrix (water or soil), OR
o Whenever samples are extracted by the same procedure
(separatory funnel, continuous liquid-liquid extraction, or
sonication).
15.1.2 In order to be acceptable, a method blank analysis cannot
contain any of the analytes listed in Exhibit C at greater than
the CRQL. The surrogate retention times must be within the
retention time windows calculated from the initial calibration
sequence mean retention time for both tetrachloro-m-xylene and
decachlorobiphenyl.
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15.1.3 All samples associated with an unacceptable method blank (see
Form IV) must be reextracted and reanalyzed at no additional
cost to the Agency.
15.2 Sulfur Cleanup Blank.
15.2.1 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 procedure (see
Section II, paragraph 7.4).
15.2.2 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
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 the
method blank must be subjected to sulfur cleanup, and no
separate sulfur cleanup blank is required.
15.2.3 In order to be acceptable, a sulfur blank analysis cannot
contain any of the analytes listed in Exhibit C at greater than
the CRQL. The surrogate retention times must be within the
retention time windows calculated from the initial calibration
sequence mean retention time for both tetrachloro-m-xylene and
decachlorobiphenyl.
15.2.4 All samples associated with an unacceptable sulfur blank (see
Form IV) must be reextracted and reanalyzed at no additional
cost to the Agency.
15.3 Instrument blank
15.3.1 An instrument blank is a hexane or iso-octane solution
containing 20.0 ng/mL of tetrachloro-m-xylene and
decachlorobiphenyl.
15.3.2. The first analysis in a 12-hour analysis sequence must be an
instrument blank. All acceptable samples analyses are to be
bracketed by acceptable instrument blanks, as described in
paragraph 5.1.
15.3.3 An acceptable instrument blank must be analyzed within a 12-
hour analysis sequence and must demonstrate that no analyte in
Exhibit C is detected at greater than 0.5 times the CRQL and
that the surrogate retention times are within the retention
time windows.
15.3.4 If analytes are detected at greater than half the CRQL or the
surrogate 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
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SECTION III
are collected. After an acceptable instrument blank is run,
all samples which were run after the last acceptable instrument
blank must be reinjected during a valid run sequence at no
additional cost to the Agency and must be reported.
15.3.5 Analysts are cautioned that running an instrument blank once
every 12 hours is the minimum contract requirement. Late
eluting peaks may carry over from one injection to the next if
highly complex samples are analyzed or if the GC conditions are
unstable. Such carryover is unacceptable. Therefore, it may
be necessary to run instrument blanks more often to avoid
discarding data.
16. Matrix Spike/Matrix Spike Duplicate
16 . 1 A matrix spike and matrix spike duplicate must be extracted and
analyzed at least once with every 20 samples of each matrix. NOTE:
There is no differentiation between "low" and "medium" soil samples in
this method. Therefore only one soil MS/MSD is to be submitted.
16.2 The surrogate retention times must be within the retention time windows
specified.
16.3 The percent recoveries and the relative percent difference between the
' recoveries of each of the 6 compounds in the matrix spike samples will
be calculated and reported by using the following equations:
SSR - SR
Matrix Spike Recovery - - x 100
SA Eq. 11
Where
SSR - Spike sample result
SR - Sample result
SA - Spike added
Where
RPD - Relative percent difference
MSR - Matrix spike recovery
MSDR - Matrix spike duplicate recovery
The vertical bars in the formula above indicate the absolute value of
the difference, hence RPD is always expressed as a positive value.
16.4 The Contractor shall report matrix spike and matrix spike duplicate
recoveries and percent difference values with the analytical results
(see Exhibit B) . The limits for matrix spike compound recovery and RPD
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are given below. 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 the Agency.
MATRIX SPIKE RECOVERY AND
RELATIVE PERCENT DIFFERENCE LIMITS
%R RPD %R RPD
Compound Water Water Soil Soil
gamma-BHC (Lindane) 56-123 50 46-127 15
Heptachlor 40-131 31 35-130 20
Aldrin 40-120 43 34-132 22
Dieldrin 52-126 38 31-134 18
Endrin 56-121 45 42-139 21
4,4'-DDT 38-127 50 23-134 27
s
17. GC/MS Confirmation of Pesticides and Aroclors
17.1 Any pesticide or Aroclor analyte listed in Ex. C for which a
concentration is reported from a GC/EC analysis must have the
identification confirmed by GC/MS if the concentration is sufficient
for that purpose. The following paragraphs are to be used as guidance
in performing GC/MS confirmation. If the the Contractor fails to
perform GC/MS confirmation as appropriate, the Agency may require
reanalysis of any affected samples at no additional cost to the Agency.
17.1.1 The GC/MS confirmation may be accomplished by one of three
general means.
o Examination of the semivolatile GC/MS library
search results (i.e. TIC data)
o A second analysis of the the semivolatile
extract
o Analysis of the pesticide/Aroclor extract,
following any solvent exchange and concentration
steps that may be necessary.
17.1.-2 The semivolatile GC/MS analysis procedures outlined in Ex. D SV
are based on the injection into the instrument of approximately
20 ng of a target compound in a 2 uL volume. The semivolatile
CRQL values in Ex. C are based on the sample concentration that
corresponds to an extract concentration of 10 ng/uL of target
analyte. However, these are quantitation limits, and the
detection of analytes and generation of reproducible mass
spectra will routinely be possible at levels 3-10 times lower.
The sample concentration corresponding to 10 ng/uL in extract
will depend on the sample matrix.
o For water samples, 20 ng/ 2 uL corresponds to a
sample concentration of 10 ug/L.
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o For soil samples prepared according Co Che
semivolatile low level soil method (i. e. 30 g
of soil), the corresponding sample concencraCion
is 330 ug/Kg.
o For soil samples prepared according Co Che
semivolatile medium level soil mechod (i. e. 1 g
of soil), Che corresponding sample concencraCion
is 10,000 ug/Kg.
Therefore, based on Che values given above, any pesCicide
sample in which Che sample concencraCion is greaCer Chan or
equal Co an excract concencraCion of 10 ng/uL should enable Che
laboratory to confirm the pesticide/Aroclor by GC/MS analysis
of Che semivolatile extract.
17.1.3 In order to confirm the identification of the target
pesticide/Aroclor, the laboratory must also analyze a reference
standard for the analyte. In order to demonstrate the ability
of the GC/MS system Co idenCify Che analyCe in question, Che
concencraCion of Che standard should be no greaCer Chan 10
ng/uL.
17.1.3.1 To facilicace Che confirmaCion of the
pesticide/Aroclor analytes from the semivolatile
library search data, Che laboratory may wish to
include these analytes in the semivolatile
continuing calibration standard at a concentration
of 10 ng/uL or less. If added to this GC/MS
standard, the response factors, retention times,
etc. for these analytes would be reported on the
GC/MS quantitation report, but not on Che GC/dS
calibration data reporting forms. As only a single
concencraCion of each analyCe would be analyzed, no
linearity (%RSD) or percent difference criteria
would be applied to Che response facCors for chese
addicional analyCes.
17.1.3.2 The laboraCory is advised chac library search
results from the NIST/EPA/MSDC mass spectral library
will not likely list the name of the
pesticide/Aroclor analyte as it appears in this SOW,
hence, the mass spectral interpretation specialist
is advised to compare the CAS Registry numbers for
the pesticides/Aroclors to those from the library
search routine.
17.1.4 If the analyte cannot be confirmed from the semivolatile
library search data for the original semivolatile GC/MS
analysis, the laboratory may analyze another aliquot of the
semivolatile sample extract after further concentration of the
aliquot. This second aliquot must either be analyzed as part
of a routine semivolatile GC/MS analysis, including instrument
performance checks (DFTPP), calibration standards containing
the pesticides/Aroclors as described in paragraph 17.1.3, etc.,
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or it must be analyzed along with separate reference standards
for the analytes to be confirmed.
17.1.5 If the analyte cannot be confirmed by either the procedures in
paragraphs 17.1.3 or 17.1.4, then an aliquot of the extract
prepared for the GC/EC analysis must be analyzed by GC/MS,
following any necessary solvent exchange and concentration
steps. As in paragraph 17.1.4, analysis of a reference
standard is required if the GC/MS continuing calibration
standard does not contain the analyte to be confirmed.
17.1.6 Regardless of which of the three approaches above is used for
GC/MS confirmation, the appropriate blank must also be analyzed
by GC/MS to demonstrate that the presence of the analyte was
not the result of laboratory contamination. If the
confirmation is based on the analysis of the semivolatile
extract, then the semivolatile method blank extracted with the
sample must also be analyzed. If the confirmation is based on
the analysis of the extract prepared for the GC/EC analysis,
then the pesticide method blank extracted with the sample must
be analyzed.
17.2 If the identification of the analyte can not be confirmed by any of the
GC/MS procedures above and the concentration calculated from the GC/EC
analysis is greater than or equal to the concentration of the reference
standard analyzed by GC/MS, then report the analyte as undetected,
adjust the sample quantitation limit (the value associated with the "U"
qualifier) to a sample concentration equivalent to the concentration of
the GC/MS reference standard, and qualify the result on Form I with one
of the laboratory-defined qualifiers ("X", "Y", or "Z"). In this
instance, define the qualifier explicitly in the SDG Narrative, and
describe the steps taken to confirm the analyte in the Narrative.
17.3 For GC/MS confirmation of single component analytes, the required
deliverables are copies of the library search results (three best TIC
matches) or analyte spectrum and the spectrum of the reference
standard. For multicomponent analytes, spectra of three characteristic
peaks are required for both the sample component and the reference
standard.
17.4 The purpose of GC/MS analysis is for confirmation of identification,
not quantitation. Therefore, the concentrations of all
pesticides/Aroclors shall be based on the GC/EC results. The exception
noted in paragraph 17.2 applies only to analytes that cannot be
confirmed at a concentration above that of the reference standard.
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EXHIBIT E
QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
E-l OLM01.0
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TABLE OF CONTENTS
SECTION
PAGE
OVERVIEW E-3
I INTRODUCTION E-4
II QUALITY ASSURANCE PLANS E-6
III STANDARD OPERATING PROCEDURES E-9
IV QA/QC REQUIREMENTS
Volatiles (VOA) QA/QC Requirements E-12/VOA
Semivolatiles (SV) QA/QC Requirements „ E-18/SV
Pesticides/Aroclors (PEST) QA/QC Requirements E-24/PEST
V ANALYTICAL STANDARDS REQUIREMENTS E-32
VI CONTRACT COMPLIANCE SCREENING E-37
VII REGIONAL DATA REVIEW 1 ... E-38
VIII LABORATORY EVALUATION SAMPLES E-39
IX GC/MS TAPE AUDITS E-41
X ON-SITE LABORATORY EVALUATIONS E-42
XI QUALITY ASSURANCE AND DATA TREND ANALYSIS E-45
XII DATA MANAGEMENT E-46
REFERENCES E-4.8
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OVERVIEW
Quality assurance and quality control are integral parts of the Environmental
Protection Agency's (EPA) Contract Laboratory Program (CLP)^lf 2> >5> ' . The
quality assurance (QA) process consists of management review and oversight at
the planning, implementation, and completion stages of the environmental data
collection activity, to ensure that data provided are of the quality
required. The quality control (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' .
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, arid 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^ '•'.
The purpose of this Exhibit is to describe the overall quality
assurance/quality control operations and the processes by which the Program
meets the QA/QC objective 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 the EPA 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.
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SECTION I
INTRODUCTION
Appropriate use of data generated under the great range of analytical
conditions encountered in environmental analyses requires reliance on the
quality control 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
quality control component of each method is indispensable.
The data acquired from quality control 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 means used
to estimate information content include precision, accuracy, detection limit,
and other quantitative and qualitative indicators. In addition, it gives an
overview of the activities required in an integrated program to generate data
of known and documented quality required to meet defined objectives.
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, NEIC, and EMSL/LV. Each external review
accomplishes a different purpose. These reviews are described in specific
sections of this Exhibit. Performance evaluation samples and magnetic tape
audits provide an external QA reference for the program. A laboratory 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
contract laboratories through direct communications with the Administrative
Project Officers and Technical Project Officers.
This Exhibit is not a guide to constructing quality assurance project plans,
quality control systems, or a quality assurance organization. It is,
however, an explanation of the quality control and quality assurance
requirements of the program. It outlines some minimum standards for QA/QC
programs. It also includes specific items that are required in a QA Plan and
by the QA/QC documentation detailed in this contract. Delivery of this
documentation provides the Agency 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.
In order to assure that the product delivered by the Contractor meets the
requirements of the contract, and to improve interlaboratory data comparison,
the Agency requires the following from the Contractor:
o A written Quality Assurance Plan, the elements of which are designated in
Section II.
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Written preparation of and adherence to" QA/QC Standard Operating
Procedures (SOPs) as described in Section III.
Adherence to the analytical methods and associated QC requirements
specified in the contract.
Verification of analytical standard 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 GC/MS tapes and applicable documentation for
tape audits.
Participation in On-Site Laboratory Evaluations, including adherence t~
corrective action procedures. s
Submission of all original documentation generated during sample analyses
for Agency review.
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SECTION II
QUALITY ASSURANCE FLAN
The Contractor shall establish a quality assurance program with the objective
of providing sound analytical chemical measurements. This program shall
incorporate the quality control procedures, any necessary corrective action,
and all documentation required during data collection as well as the quality
assessment measures performed by management to ensure acceptable data
production.
As evidence of such a program, the Contractor shall prepare a written Quality
Assurance Flan (QAF) which describes the procedures that are implemented to
achieve the following:
o Maintain data integrity, validity, and useability. „
o Ensure that analytical measurement systems are maintained in an
acceptable state of stability and reproducibility .
o Detect problems through data assessment and establishes corrective action
procedures which keep the analytical process reliable.
o Document all aspects of the measurement process in order to provide data
which are technically sound and legally defensible.
The QAP must present, in specific terms, the policies, organization,
objectives, functional guidelines, and specific QA and QC activities designed
to achieve the data quality requirements in this contract. Where applicable,
SOPs pertaining to each element shall be included or referenced as part of
the QAF. The QAF must be available during On-Site Laboratory evaluation and
upon written request by the Administrative Project Officer. Additional
information relevant to the preparation of a QAF can be found in EPA and ASTM
publication^2' '.
Elements of a Quality Assurance Plan
A. Organization and Personnel
1. QA Policy and Objectives
2. QA Management
a. Organization
b. Assignment of QC and QA Responsibilities
c. Reporting Relationships
d. QA Document Control Procedures
e. QA Program Assessment Procedures
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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. Samples Tracking/Custody Procedures
3. Logbook Maintenance and Archiving Procedures
4. Case File Organization, Preparation and Review Procedures.
t*
5. Procedures for Preparation, Approval, Review, Revision, and
Distribution of SOPs.
6. Process for Revision of Technical or Documentation Procedures
D. Analytical Methodology
1. Calibration Procedures and Frequency
2. Sample Preparation/Extraction Procedures
3. Sample Analysis Procedures
4. Standards Preparation Procedures
5. Decision Processes, Procedures, and Responsibility for Initiation
of Corrective Action
E. Data Generation
1. Data Collection Procedures
2. Data Reduction Procedures
3. Data Validation Procedures
4. Data Reporting and Authorization Procedures
F. Quality Control
1. Solvent, Reagent and Adsorbent Check Analysis
2. Reference Material Analysis
3. Internal Quality Control Checks
4. Corrective Action and Determination of QC Limit Procedures
5. Responsibility Designation
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G. Quality Assurance
1. Data Quality Assurance
2. Systems/Internal Audits
3. Performance/External Audits
4. Corrective Action Procedures
5. Quality Assurance Reporting Procedures
6. Responsibility Designation
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SECTION III
STANDARD OPERATING PROCEDURES
In order to obtain reliable results, adherence to prescribed analytical
methodology is imperative. In any operation that is performed on a repetitive
basis, reproducibility is best accomplished through the use of Standard
Operating Procedures (SOPs). As defined by the EPA, an SOP is a written
document which provides directions for the step-by-step execution of an
operation, analysis, or action which is commonly accepted as the method for
performing certain routine or repetitive tasks^ '.
SOPs prepared by the Contractor must be functional: i.e., clear,
comprehensive, up-to-date, and sufficiently detailed to permit duplication of
results by qualified analysts. All SOPs, as presented to the Agency, muat
reflect activities as they are currently performed in the laboratory. In
addition, all SOPs must:
o Be consistent with current EPA regulations, guidelines, and the CLP
contract's requirements(3 •4 •5 >6 •' / .
o Be consistent with instruments manufacturers's specific instruction
manuals.
o Be available to the EPA during an On-Site Laboratory Evaluation. A
complete.set of SOP's shall be bound together and available for inspection
at such evaluations. During On-Site evaluations, laboratory personnel may
be asked to demonstrate the application of the SOPs.
o Provide for the development of documentation that is sufficiently complete
to record the performance of all tasks required by the protocol.
o Demonstrate the validity of data reported by the Contractor and explain
the cause of missing or inconsistent results.
o Describe the corrective measures and feedback mechanism utilized when
analytical results do not meet protocol requirements.
o Be reviewed regularly and updated as necessary when contract, facility, or
Contractor procedural modifications are made:
o Be archived for future reference in usability or evidentiary situations.
o Be available at specific work stations as appropriate
o Be subject to a document control procedure which precludes the use of
outdated or inappropriate SOPs.
SOP FORMAT:
The format for SOPs may vary depending upon the kind of activity for which
they are prepared, however, at a minimum, the following sections must be
included:
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o Title Page
o Scope and Application
o Definitions
o Procedures
o QC Limits
o Corrective Action Procedures, Including Procedures for Secondary Review of
Information Being Generated
o Documentation Description and Example Forms
o Miscellaneous Notes and Precautions
o References
SOPs Required:
The following SOPs are required by the Agency: "
1. Evidentiary SOP
Evidentiary SOPs required are discussed in Exhibit F, "Specification
for Written Standard Operating Procedures"
2. Sample Receipt and logging
3. Sample storage
4.- Preventing sample contamination
5. Security for laboratory and samples
6. Standards purity/preparation
7. Maintaining instrument records and logbooks
8. Sample analysis and data control systems
9. Glassware cleaning
10. Technical and managerial review of laboratory operation and data
package preparation
11. Internal review of contractually-required quality assurance and quality
control data for each individual data package
12. Sample analysis, data handling and reporting
13. Chain-of-custody procedures and document control including SDG file
preparation
14. Laboratory data validation/laboratory self inspection system
a. Data flow and chain-of-command for data review
b. Procedures for measuring precision and accuracy
(O)
c. Evaluation parameters for identifying systematic errorsv
d. Procedures to assure that hardcopy and diskette deliverables are
complete and compliant with the requirements in SOW Exhibits B
and H.
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e. Procedures Co assure that hardcopy deliverables are in agreement
with their comparable diskette deliverables.
f. Demonstration of internal QA inspection procedure (demonstrated
by supervisory sign-off on personal notebooks, internal PE
samples, etc.).
g. Frequency and type of internal audits (eg., random, quarterly,
spot checks, perceived trouble areas).
h. Demonstration of problem identification-corrective actions and
resumption of analytical processing. Sequence resulting from
internal audit (i.e., QA feedback).
i. Documentation of audit reports, (internal and external),
response, corrective action, etc.
15. Data Management and Handling
a. Procedures for controlling and estimating data entry errors.
b. Procedures for reviewing changes to data and deliverables and
ensuring traceability of updates.
c. Lifecycle management procedures for testing, modifying and
implementing changes to existing computing systems including
hardware, software, and documentation or installing new systems.
d. Database security, backup and archival procedures including
recovery from system failures.
e. System maintenance procedures and response time.
f. Individuals(s) responsible for system operation, maintenance,
data integrity and security.
g. Specifications for staff training procedures.
SOPs Delivery Requirements:
Within forty-five (45) days of contract receipt, a complete set of SOPs,
relevant to this contract shall be sent to the Technical Project Officer, SMO
and EMSL/LV. Also, during the term of performance of the contract, copies of
SOPs which have been amended or new SOPs which have been written shall be
sent to the Technical Project Officer, EMSL/LV (quality assurance SOPs) and
NEIC (evidentiary SOPs).
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SECTION IV VOA
VOLATILE QA/QC REQUIREMENTS
INTRODUCTION
Sections II and III of this exhibit outline the requirements for the
quality assurance program that each laboratory must establish under
this contract. The purpose of Section III is to outline the minimum
quality control (QC) operations necessary to satisfy the analytical
requirements associated with the determination of the volatile organic
target compounds listed in Exhibit C using the procedures in Exhibit D
VOA for water and soil/sediment samples. This section is not intended
as a comprehensive quality control document, but rather as a guide to
the specific QC operations that must be considered for volatile
analyses. At a minimum, the laboratory is expected to address these
operations in preparing the quality assurance plan and QA/QC Standard
Operating Procedures discussed in Section II. „
These operations include the following:
o GC/MS Mass Calibration and Ion Abundance Patterns
o GC/MS Initial and Continuing Calibration
o Stability of Internal Standard Responses and Retention Times
o Method Blank Analysis
o System Monitoring Compound Recoveries
o Matrix Spike and Matrix Spike Duplicate Analyses
o Dilution of Samples, Matrix Spikes, and Matrix Spike Duplicates
Not discussed in this section are the requirements for quality
assurance of the data reporting aspects of volatile analyses which are
described in general terms in Section II and III of this exhibit.
1. GC/MS Mass Calibration and Ion Abundance Patterns
Prior to initiating any data collection activities involving samples,
blanks, or standards, it is necessary to establish that a given GC/MS
system meets the instrument performance criteria specified in Exhibit D
VOA, Section IV, paragraph 6. The purpose of this instrument
performance check is to assure correct mass calibration, mass
resolution, and mass transmission. This is accomplished through the
analysis of Bromofluorobenzene (BFB).
1.1 The required frequency of BFB analysis (once every 12 hours on
each GC/MS system) is described in detail in Ex. D VOA, Section
IV, paragraph 6.4.
1.2 The key ions produced during the analysis of BFB and their
respective ion abundance criteria are given in Table 1, Ex. D
VOA, Section IV, paragraph 6.4.4.
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SECTION IV
1.3 The documentation includes Form V VOA, and a mass listing and
bar graph spectrum of each BFB analysis.
2. GC/MS Initial Calibration for Target Compounds and System Monitoring
Compounds
Prior to the analysis of samples and required blanks and after
instrument performance criteria have been met, the GC/MS system must be
initially calibrated at a minimum of five concentrations to determine
the linearity of response utilizing target compound and system
monitoring compound standards.
2.1 The concentrations of the initial calibration standards for
volatile target compounds and system monitoring compounds are
10, 20, 50, 100, and 200 ug/L, as described in Ex. D VOA,
Section IV, paragraph 5.5.
2.2 The standards are to be analyzed according t$ the procedures
given in Ex. D VOA, Section IV, paragraph 7, and at the
frequency given in that paragraph.
2.3 The relative response factors (RRFs) are determined according
to the procedures in Ex. D VOA, Section IV, paragraph 7.4,
using the assignment of internal standard to target compounds
and system monitoring compounds given in Ex. D VOA, Section IV,
paragraph 7.4, and Tables 3 and 4.
2.4 The calibration of the GC/MS is evaluated on the basis of the
magnitude and stability of the relative response factors of
each target compound and system monitoring compound. The
minimum RRF of each compound in the initial calibration and the
percent relative standard deviation (%RSD) across all five
points must meet the criteria given Ex. D VOA, Section IV,
paragraphs 7.4.5 and 7.4.6, and Table 2. Allowance is made for
any two volatile compounds that fail to meet these criteria.
The minimum RRFs of those two compounds must be greater than or
equal to 0.010, and the %RSD must be less than or equal to
40.0% for the initial calibration to be acceptable.
2.5 The documentation includes Form VI VOA, a GC/MS data system
printout for the analysis of each volatile calibration
standard, and the mass spectrum of each target compound and
system monitoring compound.
3. GC/MS Continuing Calibration for Target Compounds and System Monitoring
Compounds.
Once the GC/MS system has been calibrated, the calibration must be
verified each twelve (12) hour time period for each GC/MS system.
3.1 The concentration of the continuing calibration standard for
volatile target compounds and system monitoring compounds is 50
ug/L, as described in Ex. D VOA, Section IV, paragraph 5.5.3.
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SECTION IV
3.2 The standard is to be analyzed according to the procedures
given in Ex. D VOA, Section IV, paragraph 7, and at the
frequency given in that paragraph.
3.3 The continuing calibration of the GC/MS system is evaluated on
the basis of the magnitude of the relative response factors and
the percent difference between the average RRF of each compound
from the initial calibration and the RRF of that compound in
the continuing calibration standard. The minimum RRF of each
compound in the continuing calibration and the percent
difference must meet the criteria given Ex. D VOA, Section IV,
paragraphs 7.4.5 and 7.4.7, and Table 2.. Allowance is made for
any two volatile compounds that fail to meet these criteria.
The minimum RRFs of those two compounds must be greater than or
equal to 0.010, and the percent difference must be less than or
equal to 40.0% for the continuing calibration to be acceptable.
3.4 The documentation includes Form VII VOA, a GQ/MS data system
printout for the analysis of the volatile calibration standard,
and the mass spectrum of each target compound and system
monitoring compound.
4. Internal Standard Responses and Retention Times
The response of each of the internal standards in all calibration
standards, samples, and blanks is crucial to the provision of reliable
analytical results, because the quantitative determination of volatile
compounds by these procedures is based on the use of internal standards
added immediately prior to analysis.
4.1 The specific compounds used as internal standards are given in
Ex. D VOA, Section IV, paragraph 5.4.3. The concentration of
each internal standard in the aliquot of the sample analyzed by
GC/MS must be 50 ug/L at the time of purging.
4.2 The retention time and the extracted ion current profile (EICP)
of each internal standard must be monitored for all analyses.
4.3 The area response of each internal- standard from the EICP and
the retention time of the internal standard are evaluated for
stability, according to the procedures in Ex. D VOA, Section
IV, paragraph 10.2. The area of the internal standard in a
sample must not vary by more than a factor of 2 (i.e. -50% to
+100%) from the area of the same internal standard in the
associated continuing calibration standard. Likewise, the
retention time of an internal standard must be within +0.50
minutes (30 seconds) of its retention time in the continuing
calibration standard (see Ex.D VOA, Section IV, paragraph
10.2).
4.4 Requirements for reanalysis of samples when internal standards
do not meet specifications are given in Ex. D VOA, Section IV,
paragraph 10.2.
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SECTION IV
4.5 The documentation Includes Form VIII VGA, and the GC/MS data
system printout for the analysis of each sample, blank, matrix
spike, matrix spike duplicate, and standard.
5. Method Blank Analysis
A method blank is a volume of a clean reference matrix (deionized
distilled water for water samples, or a purified solid matrix for
soil/sediment samples) that is carried through the entire analytical
procedure. The volume or weight of the reference matrix must be
approximately equal to the volume or weight of samples associated with
the blank. The purpose of a method blank is to determine the levels of
contamination associated with the processing and analysis of samples.
5.1 For volatile analysis, a method blank must be analyzed once
every 12 hours on each GC/MS system, as described in detail in
Ex. D VGA, Section IV, paragraphs 8.1.16, 8.2.1.9, and
8.2.2.10.
5.2 For the purposes of this protocol, an acceptable method blank
must meet the criteria in paragraphs 5.2.1. and 5.2.2 below.
5.2.1 A method blank for volatile analysis must contain
less than or equal to five times (5x) the Contract
Required Quantitation Limit (CRQL, see Exhibit C) of
Methylene chloride, Acetone, and 2-Butanone.
5.2.2 For all other target compounds not listed above, the
method blank must contain less than or equal to the
Contract Required Quantitation Limit (CRQL, see
Exhibit C) of any single target compound.
5.3 If a method blank exceeds the limits for contamination above,
the Contractor must consider the analytical system out of
control. The source of the contamination must be investigated
and appropriate corrective actions taken and documented before
further sample analysis proceeds. The requirements for
reanalysis of associated samples are given in Ex. D VOA,
Section IV, paragraph 10.10.
5.4 The documentation includes Form I VOA for the blank analysis,
Form IV VOA, associating the samples and the blank, and a GC/MS
data system printout for the analysis of the method blank.
6. System Monitoring Compound Recoveries
The recoveries of the three system monitoring compounds are calculated
from the analysis of each sample, blank, matrix spike and matrix spike
duplicate. The purpose of the system monitoring compounds is to
evaluate the performance of the entire purge and trap-gas
chromatograph-mass spectrometer system. Poor purging efficiency,
leaks, and cold spots in transfer lines are only a few of the potential
causes of poor recovery of these compounds.
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SECTION IV
6.1 The system monitoring compounds are added to each sample,
blank, matrix spike, and matrix spike duplicate prior to
purging or extraction (medium soils only), at the concentration
described in Ex. D VOA, Section IV, paragraph 5.4.4.
6.2 The recoveries of the system monitoring compounds are
calculated according to the procedures in Ex. D VOA, Section
IV, paragraph 10.8.1.
6.3 The recoveries must be within the quality control limits given
in Ex. D VOA,. Section IV, Table 5. If the recovery of any one
system monitoring compound is outside these limits, the
Contractor must follow the steps outlined in Ex. 0 VOA, Section
IV, paragraphs 10.8.2 to 10.8.6.
6.4 The documentation includes Form II VOA, and a GC/MS data system
printout for the analysis of each sample, blank, matrix spike,
and matrix spike duplicate. „
7. Matrix Spike and Matrix Spike Duplicate Analysis
In order to evaluate the effects of the sample matrix on the methods
used for volatile analyses, the Agency has prescribed a mixture of
volatile target compounds to be spiked into two aliquots of a sample,
and analyzed in duplicate.
7.1 The frequency of matrix spike and matrix spike duplicate
(MS/MSD) analysis is described in Ex. D VOA, Section IV,
paragraph 10.9.
7.2 The recoveries of the matrix spike compounds are calculated
according to the procedures in Ex. D VOA, Section IV, paragraph
10.9.1. The relative percent difference between the results
for each spiked analyte of the matrix spike and the matrix
spike duplicate are calculated according to the procedures in
Ex. D VOA, Section IV, paragrs .h 10.9.2.
7.3 The quality control limits for recovery and relative percent
difference are given in Ex. D VOA,' Section IV, Table 6. These
limits are only advisory at this time, and no further action is
required when the limits are exceeded.
7.4 The documentation includes Form I VOA for both the MS and MSD
analyses, Form III VOA, and a GC/MS printout for each analysis.
8. Dilution of Samples, Matrix Spikes, and Matrix Spike Duplicates
If the on-column concentration of any sample exceeds the initial
calibration range, that sample must be diluted and reanalyzed, AS
described in Ex. D VOA, Section IV, paragraph .10.7. Guidance in
performing dilutions and exceptions are given in that paragraph, and
reiterated here.
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SECTION IV
8.1 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.
8.2 The dilution factor chosen should keep the response of the
largest analyte peak for a target compound in the upper half of
the initial calibration range of the instrument.
8.3 Do not submit data for more than two analyses, i.e., the
original sample and one dilution, or, if the volatile screening
procedure was employed, from the most concentrated dilution
analyzed and one further dilution.
8.4 Do not dilute MS/MSD samples solely to get non-spiked analytes
within calibration range. The spiking level of each compound
in the volatile matrix spiking solution should not require the
dilution of the MS/MSD unless the sample from which these
aliquots were taken contains high levels of phe spiked
analytes.
8.5. For total Xylenes, where three isomers are quantified as two
peaks, the calibration of each peak, should be considered
separately, i.e., a diluted analysis is not required for total
Xylenes unless the concentration of either peak separately
exceeds 200 ug/L.
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SECTION IV SV
SEMIVOLATILE QA/QC REQUIREMENTS
INTRODUCTION
Sections II and III of this exhibit outline the requirements for the
quality assurance program that each laboratory must establish under
this contract. The purpose of Section III is to outline the minimum
quality control (QC) operations necessary to satisfy the analytical
requirements associated with the determination of the semivolatile
organic target compounds listed in Exhibit C using the procedures in
Exhibit 0 SV for water and soil/sediment samples. This section is not
intended as a comprehensive quality control document, but rather as a
guide to the specific QC operations that must be considered for
semivolatile analyses. At a minimum, the laboratory is expected to
address these operations in preparing the quality assurance plan and
QA/QC Standard Operating Procedures discussed in Section II.
These operations include the following:
o GC/MS Mass Calibration and Ion Abundance Patterns
o GC/MS Initial and Continuing Calibration
o Stability of Internal Standard Responses and Retention Times
o Method Blank Analysis
o Surrogate Recoveries
o Matrix Spike and Matrix Spike Duplicate Analyses
o Dilution of Samples, Matrix Spikes, and Matrix Spike Duplicates
Not discussed in this section are the requirements for quality
assurance of the data reporting aspects of semivolatile analyses which
are described in general terms in Section II and III of this exhibit.
1. GC/MS Mass Calibration and Ion Abundance Patterns
Prior to initiating any data collection activities involving samples,
blanks, or standards, it is necessary to establish that a given GC/MS
system meets the instrument performance criteria specified in Exhibit D
SV, Section IV, paragraph 4. The purpose of this instrument
performance check is to assure correct mass calibration, mass
resolution, and mass transmission. This is accomplished through the
analysis of Decafluorotriphenyl phosphine (DFTPP).
1.1 The required frequency of DFTPP analysis (once every 12 hours
on each GC/MS system) is described in detail in Ex. D SV,
Section IV, paragraph 4.3.6.
1.2 The key ions produced during the analysis of DFTPP and their
respective ion abundance criteria are given in Table 1, Ex. D
SV, Section IV, paragraph 4.3.3.
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SECTION IV
1.3 The documentation includes Form V SV, and a mass liscing and
bar graph spectrum of each DFTPP analysis.
2. GC/MS Initial Calibration for Target Compounds and Surrogates.
Prior to the analysis of samples and required blanks, and after
instrument performance criteria have been met, the GC/MS system must be
initially calibrated at a minimum of five concentrations to determine
the linearity of response utilizing target compound and surrogate
standards.
2.1 The levels of the initial calibration standards for
semivolatile target compounds and surrogates are 20, 50, 80,
100, and 160 ng, in a 2 uL injection volume, as described in
Ex. D SV, Section IV, paragraph 3.2.
2.2 The standards are to be analyzed according to the procedures
given in Ex. D SV, Section IV, paragraph 5, and at the
frequency given in that paragraph. -
2.3 The relative response factors (RRFs) are determined according
to the procedures in Ex. D SV, Section IV, paragraph 5.4, using
the assignment of internal standard to target compounds and
surrogates given in Ex. D SV, Section IV, paragraph 5.4, and
Tables 3 and 4.
2.4 The calibration of the GC/MS is evaluated on the basis of the
magnitude and stability of the relative response factors of
each target compound and surrogate. The minimum RRF of each
compound in the initial calibration and the percent relative
standard deviation (%RSD) across all five points must meet the
criteria given Ex. D SV, Section IV, paragraph 5.6, and Table
5. Allowance is made for any four semivolatile compounds that
fail to meet these criteria. The minimum RRFs of those four
compounds must be greater than or equal to 0.010, and the %RSD
must be less than or equal to 40.0% for the initial calibration
to be acceptable.
2.5 The documentation includes Form VI SV, a GC/MS data system
printout for the analysis of each semivolatile calibration
standard, and the mass spectrum of each target compound and
surrogate.
3. GC/MS Continuing Calibration for Target Compounds and Surrogates.
Once the GC/MS system has been calibrated, the calibration must be
verified each twelve (12) hour time period for each GC/MS system.
3.1 The level of the continuing calibration standard for
semivolatile target compounds and surrogates is 50 ng, in a 2
uL injection volume, as described in Ex. D SV, Section IV,
paragraph 3.2.
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SECTION IV
3.2 The standard is to be analyzed according to the procedures
given in Ex. 0 SV, Section IV, paragraph 5, and at the
frequency given in that paragraph.
3.3 The continuing calibration of the GC/MS system is evaluated on
the basis of the magnitude of the relative response factors and
the percent difference between the averaee RRF of each compound
from the initial calibration and the RRF of that compound in
the continuing calibration standard. The minimum RRF of each
compound in the continuing calibration and the percent
difference must meet the criteria given Ex. D SV, Section IV,
paragraphs 5.6, 5.7, and Table 5. Allowance is made for any
four semivolatile compounds that fail to meet these criteria.
The minimum RRFs of those four compounds must be greater than
or equal to 0.010, and the %RSD must be less than or equal to
40.0% for the continuing calibration to be acceptable.
^.4 The documentation includes Form VII SV, a GC/MS data system.
printout for the analysis of the semivolatile calibration
standard, and the mass spectrum of each target compound and
surrogate.
4. Internal Standard Responses and Retention Times
The response of each of the internal standards in all calibration
standards, samples, and blanks is crucial to the provision of reliable
analytical results because the quantitative determination of
semivolatile compounds by these procedures is based on the use of
internal standards added immediately prior to analysis.
4.1 The specific compounds used as internal standards are given in
Ex. D SV, Section IV, paragraph 3.1. The amount of each
internal standard in the injection volume (2 uL) of the sample
extract analyzed by GC/MS must be 40 ng (20 ng/uL).
4.2 The retention time and the extr sted ion current profile (EICP)
of each internal standard must be monitored for all analyses.
4.3 The area response of each internal standard from the EICF and
the retention time of the internal standard are evaluated for
stability, according to the procedures in Ex. D SV, Section IV,
paragraph 8.1. The area of the internal standard in a sample
must not vary by more than a factor of 2 (i.e. -50% to +100%)
from the area of the same internal standard in the associated
continuing calibration standard. Likewise, the retention time
of .an internal standard must be within ±0.50 minutes (30
seconds) of its retention time in the continuing calibration
standard (see Ex.D SV, Section IV, paragraph 8.1).
4.4 Requirements for reanalysis of samples when internal standards
do not meet specifications are given in Ex. D SV, Section IV,
paragraph 8.1.
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SECTION IV
4.5 The documentation includes Form VIII SV, and the GC/MS data
system printout for the analysis of each sample, blank, matrix
spike, matrix spike duplicate, and standard.
5. Method Blank Analysis
A method blank is a volume of a clean reference matrix (deionized
distilled water for water samples, or a purified sodium sulfate for
soil/sediment samples) that is carried through the entire analytical
procedure. The volume or weight of the reference matrix must be
approximately equal to the volume or weight of samples associated with
the blank. The purpose of a method blank is to determine the levels of
contamination associated with the processing and analysis of samples.
5.1 For semivolatile analysis, one method blank must be extracted
with each group of samples of a similar matrix and
concentration level (soils only), as described in Ex. D SV,
Section IV, paragraph 8.7.
H
5.2 For the purposes of this protocol, an acceptable method blank
must meet the criteria in paragraphs 5.2.1. and 5.2.2 below.
5.2.1 A method blank for semi volatile analysis must
contain less than or equal to five times (5x) the
Contract Required Quantitation Limit (CRQL, see Ex.
C) of the phthalate esters listed in Ex. C.
5.2.2 For all other target compounds not listed above, the
method blank must contain less than or equal to the
Contract Required Quantitation Limit (CRQL, see
Exhibit C) of any single target compound.
5.3 If a method blank exceeds the limits for contamination above,
the Contractor must consider the analytical system out of
control. The source of the contamination must be investigated
and appropriate corrective actions taken and documented before
further sample analysis proceeds. The requirements for
reextraction and reanalysis of associated samples are given in
Ex. D SV, Section IV, paragraph 8..7.
5.4 The documentation includes Form I SV for the blank analysis,
Form IV SV, associating the samples and the blank, and a GC/MS
data system printout for the analysis of Che method blank.
6. Surrogate Recoveries
The recoveries of the eight surrogates are calculated from the analysis
of each sample, blank, matrix spike and matrix spike duplicate. The
purpose of the surrogates is to evaluate the preparation and analysis
•of samples.
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SECTION IV
6.1 The surrogates are added to each sample, blank, matrix spike,
and matrix spike duplicate prior to extraction, at the
concentrations described in Ex. D SV, Section II, Part B
paragraph 4.6 and Part C paragraph 1.5.3 and 2.4.5.
6.2 . The recoveries of the surrogates are calculated according to
the procedures in Ex. D SV, Section IV, paragraph 8.5.1.
6.3 The recoveries must be within the quality control limits given
in Ex. D SV, Section IV, Table 6. If the recovery of any
surrogate is outside these limits, the Contractor must follow
the steps outlined in E. D SV, Section IV, paragraphs 8.5.2 to
8.5.6 to determine whether or not reextraction and/or
reanalysis is required.
6.4 The documentation includes Form II SV, and a GC/MS data system
printout for the analysis of each sample, blank, matrix spike,
and matrix spike duplicate.
H
7. Matrix Spike and Matrix Spike Duplicate Analysis
In order to evaluate the effects of the sample matrix on the methods
used for semivolatile analyses, the Agency has prescribed a mixture of
semivolatile target compounds to be spiked into two aliquots of a
sample, and analyzed in duplicate.
7.1 The frequency of matrix spike and matrix spike duplicate
(MS/MSD) analysis is described in Ex. D SV, Section IV,
paragraph 8.6.
7.2 The recoveries of the matrix spike compounds are calculated
according to the procedures in Ex. D SV, Section IV, paragraph
8.6.1. The relative percent difference between the results for
each spiked analyte of the matrix spike and the matrix spike
duplicate is calculated according to the procedures in Ex. 0
SV, Section IV, paragraph 8.6.2.
7.3 The quality control limits for recovery and relative percent
difference are given in Ex. D SV, Section IV, Table 7. These
limits are only advisory at this time, and no further action is
required when the limits are exceeded.
7.4 The documentation includes Form I SV for both the MS and MSD
analyses, Form III SV, and a GC/MS printout for each analysis.
8. Dilution of Samples, Matrix Spikes, and Matrix Spike Duplicates
If the on-column concentration of any sample exceeds the initial.
calibration range, that sample must be diluted and reanalyzed, as
described in Ex. D SV, Section IV, paragraph 8.4. Guidance in
performing dilutions and exceptions are given in that paragraph, and
reiterated here.
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SECTION IV
8.1 Use che results of the original analysis to determine the
approximate dilution factor required to get the largest analyte
peak within the initial calibration range.
8.2 The dilution factor chosen should keep the response of the
largest analyte peak for a target compound in the upper half of
the initial calibration range of the instrument.
8.3 Do not submit data for more than two analyses, i.e., the
original sample and one dilution, or, if the semivolatile
screening procedure was employed, from the most concentrated
dilution analyzed and one further dilution.
8.4 Do not dilute MS/MSD samples solely to get non-spiked analytes
within calibration range. The spiking level of each compound
in the semivolatile matrix spiking solution should not require
the dilution of the MS/MSD unless the sample from which these
aliquots were taken contains high levels of the spiked
analytes. -
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SECTION IV PEST
PESTICIDE/AROCLOR QA/QC REQUIREMENTS
INTRODUCTION
Sections II and III of this exhibit outline the requirements for the
quality assurance prograa that each laboratory must establish under
this contract. The purpose of Section III is to outline the minimum
quality control (QC) operations necessary to satisfy the analytical
requirements associated with the determination of the pesticide/Aroclor
target compounds listed in Exhibit C using the procedures in Exhibit D
PEST for water and soil/sediment samples. This section is not intended
as a comprehensive quality control document, but rather as a guide to
the specific QC operations that must be considered for
pesticide/Aroclor analyses. At a minimum, the laboratory is expected
to address these operations in preparing the quality assurance plan and
QA/QC Standard Operating Procedures discussed in Section II.
H
These operations include the following:
o GC Column Resolution
o GC/EC Initial and Continuing Calibration
o Determination of Retention Times and Retention Time Windows
o Analytical Sequence
o Blank Analyses
o Surrogate Recoveries
o Matrix Spike and Matrix Spike Duplicate Analyses
o Dilution of Samples, Matrix Spikes, and Matrix Spike Duplicates
Not discussed in this section are the requirements for quality
assurance of the data reporting aspects of pesticide/Aroclor analyses
which are described in general terms in section II and III of this
exhibit.
1. GC Column Resolution
Prior to initiating any data collection activities involving samples,
blanks, or standards, it is necessary to establish that a given GC
column meets the analyte resolution criteria specified in Exhibit D
PEST, Section III, paragraph 6.2.2. The purpose of this resolution
check is to demonstrate that at the time of the initial calibration,
the GC column is capable of chromatographically resolving the target
compounds. This is accomplished through the analysis of the Resolution
Check Mixture (see Ex. D, Section III, paragraph 3.1), which contains
the nine target compounds that are most difficult to resolve.
1.1 The Resolution Check Mixture must be analyzed at the beginning
of every initial calibration sequence, on each GC column and
instrument used for analysis.
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SECTION IV
1.2 Additional resoluCion criteria apply to the target compounds in
the standards used for initial calibration and calibration
verification, as described in Ex. D Section III, paragraphs
6.2.4, 6.2.10, and 7.8.
1.3 The documentation includes Form VI PEST-4, chromatograms and
data system printouts for the analysis of the Resolution Check
Mixture on each GC column and instrument used for analysis.
2. GC/EC Initial Calibration for Target Compounds and Surrogates.
Prior to the analysis of samples and required blanks, the GC/EC system
must be initially calibrated at a minimum of three concentrations to
determine the linearity of response utilizing single component target
compound and surrogate standards. Hulticomponent target compounds are
calibrated at a single point.
2.1 The concentrations of the low point initial calibration
standards for single component pesticide target compounds and
surrogates are described in Ex. D PEST, Section III, paragraph
3.3. The concentration of the mid point initial calibration
standards is specified in Ex. D, Section III, paragraph 3.3 as
10 times the low point concentration. The concentration of the
high point initial calibration standard must be at least 30
times the low point concentration, and may be as high as 100
times the low point concentration, as described in Ex. D PEST,
Section III, paragraph 3.3.
2.2 The standards are to be analyzed according to the procedures
given in Ex. D PEST, Section III, using the GC operating
conditions in paragraphs 4 and 6, and at the frequency given in
paragraph 6.1.
2.3 The calibration factors are determined according to the
procedures in Ex. D PEST, Section III, paragraphs 9 and 10.
2.4 The initial calibration of the GC/EC is evaluated on the basis
of the stability of the calibrations factors and retention
times of each target compound and surrogate, described in Ex. D
PEST, Section III, paragraphs 6.2.5 to 6.2.9.
2.5 The calibration is also evaluated on the basis of the extent of
breakdown of two target compounds, Endrin and 4,4'-DDT, as
described in Ex. D PEST, Section III, paragraph 6.2.3.
2.6 The documentation includes Form VI PEST, chromatograms and data
system printouts of all standards for the pesticide/Aroclor
calibration standards.
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SECTION IV
3. GC/EC Continuing Calibration for Target compounds and Surrogates.
Once the GC/EC system has been calibrated, the calibration must be
verified each twelve (12) hour time period for each GC column and
instrument used for analysis. The calibration is verified through the
analysis of instrument blanks, Performance Evaluation Mixtures (PEM),
and the mid point concentrations of Individual Standard Mixtures A and
B.
3.1 The concentrations of the PEM and Individual Standard Mixtures
used for continuing calibration are given in Ex. D PEST,
Section III, paragraphs 3.2 and 3.3.
3.2 The instrument blank is described in Ex. D PEST, Section III,
paragraph 15.3.
3.3 The instrument blank and the standards must be analyzed once
every twelve hours according to the procedures in Ex. D PEST,
Section III, paragraph 5, bracketing the sample analyses, as
described in Ex. D PEST, Section III, paragraph 7.
3.4 The continuing calibration is evaluated on the basis of the
stability of the retention times of the target compounds in the
standards.
3.5 The continuing calibration is evaluated on the basis of the
stability of the instrument response to the target compounds in
the PEM, as Judged by the reproducibility of the determinations
of the concentrations of these compounds in the standard, as
described in Ex. D PEST, Section III, paragraph 7.10.
3.6 The continuing calibration is evaluated on the basis of the
extent of breakdown of two target compounds in the PEM, Endrin
and 4,4'-DDT,-as described in Ex. D PEST, Section III,
paragraph 7.11.
3.7 The continuing calibration is evaluated on the basis of the
levels of contamination that are found in the instrument blank,
as described in Ex. D PEST, Section III paragraph 15.3.
3.8 The documentation includes Form VII PEST, Form VIII PEST,
chromatograms and data system printouts for all standards and
instrument blanks analyzed.
4. Determination of Retention Times and Retention Time Windows
The identification of single component pesticides by gas
chromatographic methods is based primarily on retention time data. The
identification of multicomponent analytes is based primarily on
recognition of patterns of retention times displayed on a chromatogram.
Therefore, the determination of retention times and retention time
windows is crucial to the provision of valid data for these target
compounds.
E-26/PEST OLM01.0
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SECTION IV
4.1 The identification of all target compounds analyzed by he
procedures described in Ex. D PEST is based on the use of
absolute retention tine. The mean retention time of each
target compound, or each peak in a multicomponent target
compound, is determined from the initial calibration standards,
according to the procedures outlined in Ex. D PEST. Section
III, paragraph 8.
4.2 The retention time window of each target compound peak is
determined as ± 0.04 minute of the mean retention time for all
analytes except tfethoxychlor, where the retention time window
is ± 0.05 minutes, as described in Ex. D, Section III,
paragraph 8.4.
4.3 The retention time of each analyte in each standard in the
initial and continuing calibrations must be within a retention
time window half as large as those described above, as detailed
in Ex D PEST, Section III, paragraphs 6.2.9 and 8.2.
4.4 The retention time shifts of the surrogates are used to
evaluate the stability of the gas chromatgraphic system during
analysis of samples and standards. The retention time of the
surrogates must be within the retention time windows determined
during the initial calibration (Ex. D PEST, Section III,
paragraph 8.4.
4.5 The documentation includes Form VI PEST, Form VII PEST, Form
VIII PEST, chromatograms and data system printouts for all
standards for the Pesticide/Aroclor initial and continuing
calibrations, on each instrument and GC column used for
analysis.
5. Analytical Sequence
The standards and samples analyzed according to the procedures in Ex. D
PEST Section III must be analyzed in a sequence described in paragraphs
5 and 6. This sequence includes requirements that apply to the initial
and continuing calibrations, as well as to the analysis of samples.
The documentation includes Form VIII PEST.
6. Blank Analysis
Two types of blanks are required for analyses using the procedures in
Ex. D PEST. They are method blanks and instrument blanks. A third
type of blank, a sulfur clean up blank, may be required.
6.1 A method blank is a volume of a clean reference matrix
(deionized distilled water for water samples, or a purified
sodium sulfate for soil/sediment samples) that is carried
through the entire analytical procedure. The volume or weight
of the reference matrix must be approximately equal to the
volume or weight of samples associated with the blank. The
purpose of a method blank is to determine the levels of
E-27/PEST OLM01.0
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SECTION IV
contamination associated with the processing and analysis of
samples.
6.1.1 The frequency of method blank extraction is
described in Ex. D PEST, Section III, paragraph
15.1.1.
6.1.2 The method blank must be analyzed on each GC column
and instrument used for the analysis of associated
samples.
6.1.3 For the purposes of this protocol, an acceptable
method blank must meet the criteria in Ex. D PEST,
Section, III, paragraph IS.1.2.
6.2 The instrument blank is a volume of clean solvent spiked with
the 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 itself, particularly with regard to the
carry-over of analytes from standards or highly contaminated
samples into other analyses.
6.2.1 The frequency of instrument blank analysis is part
of the initial and continuing calibration
requirements described in Ex. D, Section III,
paragraphs 5,6, and 7.
6.2.2 For the purposes of this protocol, an acceptable
instrument blank must meet the criteria in Ex. D
PEST, Section, III, paragraph 15.3.3.
6.3 The sulfur clean up blank is a volume of clean solvent spiked
with the surrogates and carried through the sulfur clean up and
analysis steps. The purpose of the sulfur clean up blank is Co
determine the levels of contamination associated with the
separate sulfur clean up steps.
6.3.1 The sulfur clean up blank is only required when all
the samples associated with a particular method
blank are no^; subjected to sulfur clean up, as
described in Ex. D PEST, Section III, paragraph
15.2.2.
6.3.2 The sulfur clean up blank must be analyzed on all GC
column and instruments used for analysis of samples
that received sulfur clean up.
6.3.3 For the purposes of this protocol, an acceptable
sulfur clean up blank must meet the criteria in Ex.
D PEST, Section, III, paragraph 15.2.3.
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SECTION IV
6.4 If a method blank exceeds Che limits for contamination above,
the Contractor must consider the analytical system out of
control. The source of the contamination must be investigated
and appropriate corrective actions taken and documented before
further sample analysis proceeds. The requirements for
reextraction and reanalysis of associated samples are given in
Ex. D PEST, Section III, paragraph 15.1.3.
6.5 If an instrument blank exceeds the limits for contamination
above, the Contractor must consider the analytical system out
of control. The source of the contamination must be
investigated and appropriate corrective actions taken and
documented before further sample analysis proceeds. The
requirements for reanalysis of associated samples are given in
Ex. D PEST, Section III, paragraph 15.3.4.
6.6 If a sulfur clean up blank exceeds the limits for contamination
above, the Contractor must consider the analytical system out
of control. The source of the contamination must be
investigated and appropriate corrective actions taken and
documented before further sample analysis proceeds. The
requirements for reextraction and reanalysis of associated
samples are given in Ex. D PEST, Section III, paragraph 15.2.4.
6.7 The documentation includes Form I PEST for the analysis of each
type of blank; Form IV PEST, associating the samples and the
method and sulfur clean up blank; Form VIII PEST, associating
the samples and the instrument blanks; and a GC/EC data system
printout for the analysis of each blank.
7. Surrogate Recoveries
The recoveries of the two surrogates are calculated from the analysis
on each GC column of each sample, blank, matrix spike and matrix spike
duplicate. The purpose of the surrogates is to evaluate the
preparation and analysis of samples.
7.1 The surrogates are added to each sample, blank, matrix spike,
and matrix spike duplicate prior to extraction, at the
concentrations described in Ex. D PEST, Section II, paragraph
4.9.4.
7.2 The recoveries of the surrogates are calculated according to
the procedures in Ex. D PEST, Section III, paragraph 13.6.
7.3 The quality control limits for surrogate recovery, given in Ex.
D PEST,. Section III, paragraph 13.6, are 60-150 percent.
These limits are only advisory, and no further action by the
laboratory is required if the limits are exceeded, however,
frequent failures to meet the limits for surrogate recovery
warrant investigation by the laboratory, and any result in
questions from the Agency.
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SECTION IV
7.4 The documentation includes Form II PEST, a chromatogram and a
GC/EC data system printout for the analysis of each sample,
blank, matrix spike, and matrix spike duplicate.
8. Matrix Spike and Matrix Spike Duplicate Analysis
In order to evaluate the effects of the sample matrix on the methods
used for pesticide/Aroclor analyses, the Agency has prescribed a
mixture of pesticide/Aroclor target compounds to be spiked into two
aliquots of a sample, and analyzed in duplicate.
8.1 The frequency of matrix spike and matrix spike duplicate
(MS/MSD) analysis is described in Ex. D PEST, Section III,
paragraph 16.1.
8.2 The recoveries of the matrix spike compounds are calculated
according to the procedures in Ex. D PEST, Section III,
paragraph 16.3. The relative percent difference for each
spiked analyte between the results of the maferix spike and the
matrix spike duplicate are calculated according to the
procedures in Ex. D PEST, Section III, paragraph 16.3.
8.3 The quality control limits for recovery and relative percent
difference are given in Ex. D PEST, Section III, paragraph
16.4. These limits are only advisory at this time, and no
further action is required when the limits are exceeded.
8.4 The documentation includes Form I PEST for both the MS and MSD
analyses, Form III PEST, and chromatograms and a GC/EC data
system printout for each analysis.
'9. Dilution of Samples, Matrix Spikes, and Matrix Spike Duplicates
If the on-column concentration of any sample exceeds the initial
calibration range, that sample must be diluted and reanalyzed, as
described in Ex. D PEST, Section III, paragraph 13.4. Guidance in
performing dilutions and exceptions are given in that paragraph, and
reiterated here.
9.1 If the response is still above the high calibration point after
the dilution of 1:100,000, the Contractor shall contact the SMO
immediately.
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.
9.3 The dilution factor chosen should keep the response of the
largest analyte peak for a target compound in the upper half of
the initial calibration range of the instrument.
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SECTION IV
9.4 Do not submit data for more than two analyses, i.e., the
original sample and one dilution, or, if the pesticide/Aroclor
screening procedure was employed, from the most concentrated
dilution analyzed and one further dilution.
9.5 . Do not dilute MS/USD samples solely to get non- spiked analytes
within calibration range. The spiking level of each compound
in the pesticide/Aroclor matrix spiking solution should not
require the dilution of the MS/USD unless the sample from which
these aliquots were taken contains high levels of the spiked
analytes.
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SECTION V
ANALYTICAL STANDARDS REQUIREMENTS
Overview
The U.S. Environmental Protection Agency will not supply analytical reference
standards either for direct analytical measurements or for the purpose of
traceability. All contract laboratories will be required to prepare from
neat materials or purchase from private chemical supply houses those
standards necessary to successfully and accurately perform the analyses
required in this protocol.
A. Preparation of Chemical Standards from the Neat High Purity Bulk
Material
A laboratory may prepare their chemical standards from^neat materials. .
Commercial sources for neat chemical standards pertaining to compounds
listed on the Compound Target List are given in the Appendix C of the
"Quality Assurance Materials Bank: Analytical Reference Standards"
Seventh Edition, January 1988. Laboratories should obtain the highest
purity possible when purchasing neat chemical standards; standards
purchased at less than 97% purity must be documented as to why a higher
purity could not be obtained.
1. Neat chemical standards must be kept refrigerated when not being
used in the preparation of standard solutions. Proper storage of
neat chemicals is essential in order to safeguard them from
decomposition.
2. The purity of a compound can sometimes be misrepresented by a
chemical supply house. Since knowledge of purity is needed to
calculate the concentration of solute in a solution standard, it is
the contract laboratory's responsibility to have analytical
documentation ascertaining that the purity of each compound is
correctly stated. Purity confirmation, when performed, should use
either differential scanning calorimetry, gas chromatography with
flame ionization detection, high performance liquid chromatography,
infrared spectrometry, or other appropriate techniques. Use of two
or more independent methods is recommended. The correction factor
for impurity when weighing neat materials in the preparation of
solution standards is:
Equation 1
weight of pure compound
weight of impure compound - (percent purity/100)
where "weight of pure compound" is that required to prepare a
specific volume of a solution standard of a specified concentration.
E-32 OLM01.0
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3. Mis-identification of compounds occasionally occurs and it is
possible that a mis labeled compound may be received from a chemical
supply house. It is che contract laboratory's responsibility to
have analytical documentation ascertaining that all compounds used
in the preparation of solution standards be correctly identified.
Identification confirmation, when performed, should use , gas
chromatographic/mass spectrometry analysis on at least two different
analytical columns, or other appropriate techniques.
4. Calculate the weight of material to be weighed out for a specified
volume taking into account the purity of the compound and the
desired concentration. A second person must verify the accuracy of
the calculations. Check balances for accuracy with a set of
standard weights. All weighing should be performed on an analytical
balance to the nearest 0.1 mg and verified by a second person. The
solvent used to dissolve the solute should be compatible with the
protocol in which the standard is to be used; the solute should be
soluble, stable, and nonreactive with the solvent. In the case of a
multicomponent solution, the components must not react with each
other.
5. 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 is to be called
the primary standard and all subsequent dilutions must be traceable
back to the primary standard.
6. 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
when not in use. All solution standards are to be clearly labeled
as to the identity of the compound or compounds, concentration, date
prepared, solvent, and initials of the preparer.
B. Purchase of chemical standards already in solution
Solutions of analytical reference standards can be purchased by
Contractors provided they meet the following criteria:
1. Laboratories must maintain the following documentation to verify the
integrity of the standard solutions they purchase:
a. mass spectral identification confirmation of the neat material
b. purity confirmation of the neat material
c. chromatographic and quantitative documentation that the
solution standard was QC checked according to the following
section
E-33 OLM01.0
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The Contractor muse purchase standards for which the quality is
demonstrated statistically and analytically by a method of the
supplier's choice. One way this can be demonstrated is to prepare
and analyze three solutions; a. high standard, a low standard, and a
standard at the target concentration (see parts a and b below) . The
supplier must then demonstrate that the analytical results for the
high standard and low standard are consistent with the difference in
theoretical concentrations. This is done by the Student's t-test in
part "d*. If this is achieved, the supplier must then demonstrate
that the concentration of the target standard lies midway between
the concentrations of the low and high standards. This is done by
the Student's t-test in part e. Thus the standard is certified to
be within 10 percent of the target concentration.
If the procedure above is used, the supplier must document that the
following have been achieved:
a. Two solutions of identical concentration must be prepared
independently from neat materials. An aliquot of the first
solution must be diluted to the intended concentration (the
"target standard"). One aliquot is taken from the second
solution and diluted to a concentration ten percent greater
than the target standard. This is called the "high standard".
One further aliquot is taken from the second solution and
diluted to a concentration 10 percent less that the target
standard. This is called the "low standard*.
b. Six replicate analyses of each standard (a total of 18
analyses) must be performed in the following sequence: low
standard, target, high standard, low standard, target standard,
high standard, . . .
c. The mean and variance of the six results for each solution must
be calculated.
Equation 2
MEAN - (YL + Y2 + Y3 + Y4 + Y5 + Yg )/6
Equation 3 222222 2
VARIANCE - (YI + Y2
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d. The test statistic must be calculated:
Equation 5
TEST STATISTIC - |(M3 /l.l) - (Mx /0.9)|/(Vp
If che test statistic exceeds 2.13 then the supplier has failed
to demonstrate a twenty percent difference between the high and
low standards. In such a case, the standards are not
acceptable.
e. The test statistic must be calculated:
Equation 6
TEST STATISTIC - [Hj - (Mx /I.8) - (M3 /2.2)|/(Vp /4)0'5
If the test statistic exceeds 2.13, the supplier has failed to
demonstrate that the target standard concentration is midway
between the high and low standards. In such a case, the
standards are not acceptable.
^
f. The 95 percent confidence intervals for the mean result of each
standard must be calculated:
Equation 7 _
Interval for Low Standard - Mt ± (2.13)(Vp /6)°'5
Equation 8
Interval for Target Standard - M2 ± (2.13)(Vp /6)0'3
Equation 9
Interval for High Standard - M3 ± (2.13)(V /6)°'5
These intervals must not overlap. If overlap is observed, then
the supplier has failed to demonstrate the ability to
discriminate the 10 percent difference in concentrations. In
such a case, the standards are not acceptable.
In any event, the laboratory is responsible for the quality of the
standards employed for analyses under this contract.
C. Requesting Standards From the EPA Standards Repository
Solutions of analytical reference materials can be ordered from the U.S.
EPA Chemical Standards Repository, depending on availability. The
Contractor can place an order for standards only after demonstrating
that these standards are not available from commercial vendors either in
solution or as a neat material.
D. Documentation of the Verification and Preparation of Chemical Standards
It is the responsibility of each laboratory to maintain the necessary
documentation to show that the chemical standards they have used in the
performance of CLP analysis conform to the requirements previously
listed. Weighing logbooks, calculations, chromatograms, mass spectra,
E-35 OLM01.0
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etc, whether produced by the laboratory or purchased from chemical
supply houses, oust be maintained by the laboratory and may be subject
to review during on-site inspection visits. Documentation of standards
preparation may be required to be sent to EPA for verification of
contract compliance. In those cases where the documentation is
supportive of the analytical results of data packages sent to EPA, such
documentation is to be kept on file by the laboratories for a period of
one year.
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SECTION VI
CONTRACT COMPLIANCE SCREENING
Contract Compliance Screening (CCS) is one aspect of the Government's
contractual right of inspection of analytical data. CCS examines the
Contractor's adherence to the contract requirements based on the sample data
package delivered to the Agency.
CCS is performed by the Sample Management Office (SMO) under the direction of
the EPA. To assure a uniform review, a set of. standardized procedures have
been developed to evaluate the sample data package submitted by a Contractor
against the technical and completeness requirements of the contract.
CCS results are mailed to the Contractor and all other data recipients. The
Contractor has a period of time to correct deficiencies. The Contractor must
send all corrections to the Regional Client, EMSL/LV, and SMO.
CCS results are used in conjunction with other information to measure overall
Contractor performance and to take appropriate actions to correct
deficiencies in performance.
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SECTION VII
REGIONAL DATA REVIEW
Contract laboratory data are generated to meet the specific needs of the
Regions. In order to verify the useability of data for the intended purpose,
each Region reviews data from the perspective of end-user, based upon
functional aspects of data quality. General guidelines for data review have
been developed jointly by the Region and the National Program Office. Each
Region uses these guidelines as the basis for data evaluation. Individual
Regions may augment the basic guideline review process with additional review
based on Region-specific or site-specific concerns. Regional reviews, like
the sites under investigation, vary based on the nature of the problems under
investigation and the Regional response appropriate to the specific
circumstances.
Regional data reviews, relating useability of the data to a specific site,
are part of the collective assessment process. They complement the review
done at the Sample Management Office, which is designed to identify
contractual discrepancies and the review done at EMSL/LV which is designed to
evaluate Contractor and method performance. These individual evaluations are
integrated into a collective review that is necessary for program and
laboratory administration and management and may be used to take appropriate
action to correct deficiencies in the Contractor's performance.
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SECTION VIII
LABORATORY EVALUATION SAMPLES
Although intralaboratory QC may demonstrate Contractor and method performance
that can be tracked over time, an external performance evaluation program is
an essential feature of a QA program. As a means of measuring Contractor and
method performance, Contractors participate in interlaboratory comparison
studies conducted by the EPA. Results from the analysis of these laboratory
evaluation samples will be used by the EPA to verify the Contractor's
continuing ability to produce acceptable analytical data. The results are
also used to assess the precision and accuracy of the analytical methods for
specific analytes.
Sample sets may be provided to participating Contractors as frequently as on
an SDG-by-SDG basis as a recognizable QC sample of known composition; as a
recognizable QC sample of unknown composition; or not recognizable as a QC
material. The laboratory evaluation samples may be sent either by the
Regional client or the National Program Office, and may be used for contract
action.
Contractors are required to analyze the samples and return the data package
and all raw data within the contract required turnaround time.
At a mini mini, the results are evaluated for compound identification,
quantification, and sample contamination. Confidence intervals for the
quantification of target compounds are based on reported values using
population statistics. EPA may adjust the scores on any given laboraotry
evaluation sample to compensate for unanticipated difficulties with a
particular sample. Normally, a fraction of the compounds spiked into the
sample are not specifically listed in the contract. Contractors are required
to use the NIST/EPA/MSDC mass spectral library to tentatively identify a
maximum number of non-target compounds in each fraction that are present
above a minimal response. Tentative identification of these compounds, based
on contractually described spectral interpretation procedures, is evaluated
and integrated into the evaluation process.
*s
A Contractor's results on the laboratory evaluation samples will determine
the Contractor's performance as follows:
1. Acceptable, No Response Required (Score greater than or equal to 90
percent):
Data meets most or all of the scoring criteria. No response is
required.
2. Acceptable, Response Explaining Deficiency(ies) Required (Score greater
than or equal to 75 percent but less than 90 percent):
Deficiencies exist in the Contractor's performance.
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Within 14 days of receipt of notification from EPA, the Contractor shall
describe the deficiency(ies) and the action(s) taken to correct the
deficiency(ies) in a letter to the Administrative Project Officer, the
Technical Project Officer and EMSL/LV.
3. Unacceptable Performance, Response Explaining Deficiency(ies) Required
(Score less than 75 percent):
Deficiencies exist in the Contractor's performance to the extent that
the National Program Office has determined that the Contractor has not
demonstrated the capability to meet the contract requirements.
Within 14 days of receipt of notification from EPA, the Contractor shall
describe the deficiency(ies) and the action(s) taken to correct the
deficiency (ies) in a letter to the Administrative Project Officer, the
Technical Project Officer and EMSL/LV.
The Contractor shall be notified by the Administrative Project Officer
or Technical Project Officer concerning the remedy for their
unacceptable performance. A Contractor may expect, but EPA is not
limited to, the following actions: Reduction of the number of samples
sent vnder the contract, suspension of sample shipment to the
Contractor, a site visit, a full data audit, analysis of remedial PE
samples, and/or a contract sanction, such aa a Cure Notice.
Note: A Contractor's prompt response demonstrating that corrective
actions have been taken to ensure the Contractor's capability to meet
contract requirements will facilitate continuation of full sample
delivery.
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SECTION IX
GC/MS TAPE AUDITS
Periodically, EPA requests from Contractors the GC/MS magnetic tapes
corresponding to a specific case in order to accomplish tape audits.
Generally, tape submissions and audits are requested for the following
reasons:
o Program overview
o Indication of data quality problems from EMSL/LV, SMO, or Regional data
reviews
o Support for on-site audits
o Specific Regional requests
Depending upon the reason for an audit, the tapes from a recent case, a
specific case, or a laboratory evaluation sample may be requested. Tape
audits provide a mechanism to assess adherence to contractual requirements
and to ensure the consistency of data reported on the hardcopy/floppy
diskettes with that generated on the GC/MS tapes. This function provides
external monitoring of Program QC requirements and checks adherence of the
Contractor to internal QA procedures. In addition, tape audits enable EPA to
evaluate the utility, precision, and accuracy of the analytical methods.
The GC/MS tape shall include raw data and quantitation reports for samples,
blanks, laboraotry evaluation samples, initial calibrations, continuing
calibration, BFB and DFTPP associated with the case requested. The specific
requirements for submissions of GC/MS tapes are discussed in Exhibit B.
Upon request of the Administrative Project Officer or EMSL/LV, the required
tapes and all necessary documentation shall be submitted to EPA within seven
(7) days of notification.
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SECTION X
ON-SITE LABORATORY EVALUATIONS
At a frequency dictated by a contract laboratory's performance, the
Administrative Project Officer, Technical Project Officer or their authorized
representative will conduct an on-site laboratory evaluation. On-site
laboratory evaluations are carried out to monitor the Contractor's ability to
meet selected terms and conditions specified in the contract. The evaluation
process incorporates two separate categories: Quality Assurance Evaluation,
and an Evidentiary Audit.
A. Quality Assurance On-Site Evaluation
o Quality assurance evaluators inspect the Contractor's facilities to
verify the adequacy and maintenance of instrumentation, the
continuity of personnel meeting experience or education requirements,
and the acceptable performance of analytical and QC procedures. The
Contractor should expect that items to be monitored will include, but
not be limited to the following items.
o Size and appearance of the facility
o Quantity, age, availability, scheduled maintenance and performance of
instrumentation
o Availability, appropriateness, and utilization of.SOPs
o Staff qualifications, experience, and personnel training programs
o Reagents, standards, and sample storage facilities
o Standard preparation logbooks and raw data
o Bench sheets and analytical logbook maintenance and review
o Review of the Contractor's sample analysis/data package inspection
procedures
Prior to an on-site evaluation, various documentation pertaining to
performance of the specific Contractor is integrated in a profile
package for"discussion during the evaluation. Items that may be
included are previous on-site reports, laboratory evaluation sample
scores, Regional review of data, Regional QA materials, GC/MS tape audit
reports, results of CCS, and date trend reports.
B. Evidentiary Audit
Evidence auditors conduct an on-site laboratory evaluation to determine
if laboratory policies and procedures are in place to satisfy evidence
handling requirements as stated in Exhibit F. The evidence audit is
comprised of the following three activities
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1. Procedural Audit
The procedural audit consists of review and examination of actual
standard operating procedures and accompanying documentation for the
following laboratory operations: sample receiving, sample storage,
sample identification, sample security, sample tracking (from
receipt to completion of analysis) and analytical project file
organization and assembly.
2. Written SOPs Audit
The written SOPs audit consists of review and examination of the
written SOPs to determine if they are accurate and complete for the
following laboratory operations: sample receiving, sample storage,
sample identification, sample security, sample tracking (from
receipt to completion of analysis) and analytical project file
organization and assembly.
3. Analytical Project File Evidence Audit
The analytical project file evidence audit consists of review and
examination of the analytical project file documentation. The
auditors review the files to determine:
o The accuracy of the document inventory
o The completeness of the file
o The adequacy and accuracy of the document numbering system
o Traceability of sample activity
o Identification of activity recorded on the documents
o Error correction methods
C. Discussion of the On-Site Team's Findings
The quality assurance and evidentiary auditors discuss their findings
with the Administrative Project Officer/Technical Project Officer prior
to debriefing the Contractor. During the debriefing, the auditors
present their findings and recommendations for corrective actions
necessary to the Contractor personnel.
D. Corrective Action Reports For Follow-Through to Quality Assurance and
Evidentiary Audit Reports
o Following an on-site evaluation, quality assurance and evidentiary
audit reports which discuss deficiencies found during the on-site
will be forwarded to the Contractor. The Contractor must discuss the
corrective actions taken to resolve the deficiencies discussed during
the on-site visit and discussed in the on-site reports in a letter to
the Administrative Project Officer, Technical Project Officer,
EMSL/LV (response to the quality assurance report) and NEIC (response
to the evidentiary report) within 14 days of receipt of the finding
or within the time agreed upon between the Administrative Project
Officer/Technical Project Officer and the Contractor. If SOPs are
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required Co be written or SOPs are required co be amended, the
Contractor must provide the SOPs to the Technical Project Officer,
EMSL/LV (quality assurance/technical SOPs) and NEIC (evidentiary
SOPs) within 30 days of receipt of the finding or within the time
agreed upon between the Administrative Project Officer/Technical
Project Officer and the Contractor.
If the Contractor fails to take appropriate corrective action to
resolve the deficiencies discussed in the on-site reports, a
Contractor may expect, but the Agency is not limited to, the
following actions: reduction of the number of samples sent under the
contract, suspension of sample shipment to the Contractor, a follow-
up site visit, a full data audit, analysis of remedial PE samples
and/or contract sanction, such as a Cure Notice.
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SECTION XI
QUALITY ASSURANCE AND DATA TREND ANALYSIS
Data submitted by laboratories are subject to review from several aspects:
compliance with contract-required QC, useability, and full data package
evaluation. Problems resulting from any of these reviews may determine the
need for a GC/MS tape audit, an on-site laboratory evaluation and/or a
remedial laboraotry evaluation sample. In addition, QC prescribed in the
methods provides information that is continually used by the Agency to assess
sample data quality, Contractor data quality and Program data quality via
data trend analysis. Trend analysis is accomplished by entering data into a
computerized data base. Statistical reports that evaluate specific anomalies
or disclose trends in many areas, including the following, are generated from
this data base:
o Surrogate Spike Recovery
o Laboratory Evaluation Sample
o Blanks
o GC/MS Instrument Performance Checks (BFB and DFTPP)
o Initial and Continuing Calibration Data
o Other QC and Method Parameters
Program-wide statistical results are used to rank laboratories in order to
observe the relative performance of each Contractor using a given protocol
against its peers. The reports are also used to identify trends within
laboratories. The results of many of these trends analyses are included in
overall evaluation of a Contractor's performance, and are reviewed to
determine if corrective action or an on-site laboratory evaluation is
indicated in order to meet the QA/QC requirements of the contract.
Contractor performance over time is monitored using these trend analysis
techniques to detect departures of Contractor output from required or desired
levels of quality control, and to provide an early warning of Contractor
QA/QC problems which may not be apparent from the results of an individual
case.
As a further benefit to the Program, the data base provides the information
needed to establish performance-based criteria in updated analytical
protocols, where advisory criteria has been previously used. The vast
empirical data set produced by contract laboratories is carefully analyzed,
with the results augmenting theoretical and research-based performance
criteria. The result is a continuously monitored set of quality control and
performance criteria specifications of what is routinely achievable and
expected of environmental chemistry laboratories in mass production analysis
of environmental samples. This, in turn, assists the Agency in meeting its
objectives of obtaining data of known and documented quality.
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SECTION XII
DATA MANAGEMENT
Data management procedures are defined as procedures specifying the
acquisition or entry, update, correction, deletion, storage and security of
computer readable data and files. These procedures should be in written form
and contain a clear definition for all databases and files used to generate
or resubmit deliverables. Key areas of concern include: system organization
(including personnel and security), documentation operations, traceability
and quality control.
Data manually entered from hard-copy must be quality controlled and the error
rates estimated. Systems should prevent entry of incorrect or out-of-range
data and alert data entry personnel of errors. In addition, data entry error
rates must be estimated and recorded on a monthly basis by reentering a
statistical sample of the data entered and calculating discrepancy rates by
data element.
The record of changes in the form of corrections and updates to data
originally generated, submitted, and/or resubmitted must be documented to
allow traceablilty of updates. Documentation must include the following for
each change:
o Justification or rationale for the change.
o Initials of the person making the change or changes. Data changes must be
implemented and reviewed by a person or group independant of the source
generating the deliverable.
o Change documentation must be retained according to the schedule of the
original deliverable.
o Resubmitted diskettes or other deliverables must be reinspected as a part
of the laboratories' internal inspection process prior to resubmission.
The entire deliverable, not just the changes, must be inspected.
o The Laboratory Manager must approve changes to originally submitted
deliverables *
o Documentation of data changes may be requested by laboratory auditors.
Lifecyele management procedures must be applied to computer software systems
developed by the laboratory to be used to generate and edit contract
deliverables. Such systems must be thoroughly tested and documented prior to
utilization.
o A software test and acceptance plan including test requirements, test
results and acceptance criteria must be developed, followed, and available
in written form.
o System changes must not be made directly to production systems generating
deliverables. Changes must be made first to a development system and
tested prior to implementation.
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o Each version of Che production system will be given an identification
number, date of installation, date of last operation and archived.
o System and operations documentation must be developed and maintained for
each system. Documentation must include a users manual and an operations
and maintenance manual.
Individual(s) responsible for the following functions must be identified:
o System operation and maintenance including documentation and training.
o Database integrity, including data entry, data updating and quality
control.
o Data and system security, backup and archiving.
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REFERENCES
1. Fisk, J.F. and Hanzo, S.M. "Quality Assurance/Quality Control in
Organics Analysis", Proceedings from the Water Pollution Control
Federation Meeting, May 1986.
2. Office of Monitoring Systems and Quality Assurance, U.S. Environmental
Protection Agency, "Interim Guidelines and Specifications for Preparing
Quality Assurance Project Plans", QAMS-005/80, December 1980.
3. Office of Solid Waste and Emergency Response, U.S. Environmental
Protection Agency, Test Methods for Evaluating Solid Waste, Third
Edition, SW-846, November 1986.
4. Laidlaw, R.H., "Document Control and Chain of Custody Considerations for
the National Contract Laboratory Program," Quality Control in Remedial
Site Investigations: Hazardous and Industrial Solid Waste Testing,
Fifth Volume, ASTM STP 925, C.L. Perket, ed. , American Society for
Testing and Materials, Philadelphia, 1986.
5. Health Effects Research Laboratory, U.S. Environmental Protection
Agency, Manual of Analytical Methods for the Analysis of Pesticides in
Humans and Environmental Samples, EPA-600/8-80-036, June, 1980.
6. Environmental Protection Agency, "Guidelines Establishing Test
Procedures for the Analysis of Pollutants Under the Clean Water Act;
Final Rule and Interim Final Rule and Proposed Rule", 40 CFR Part 136,
Federal Register, Vol..49, No. 209., pp 4^234-43442, October 26, 1984.
7. Health Effects Research Laboratory, U.S. Environmental Protection
Agency, Manual of Analytical Quality Control for Pesticides and Related
Compounds In Human and Environmental Samples-Second Revision, EPA-600/2-
81-059, April 1981.
8. Environmental Monitoring Systems Laboratory, U.S. Environmental
Protection Agency, Analytical Reference Standards and Supplemental Data:
The Pesticides and Industrial Chemicals Repository, EPA-600/4-84-082,
October 1984.
9. American Chemical Society Committee on Environmental Improvement„ and
Subcommittee on Environmental Analytical Chemistry, "Guidelines for Data
Acquisition and Data Quality Evaluation in Environmental Chemistry",
Analytical Chemistry, Volume 52. Number 14, December 1980.
10. Moore, J.M. and Pearson, J.G. "Quality Assurance Support for the
Superfund Contract Laboratory Program", Quality Control in Remedial Site
Investigation: Hazardous and Industrial Solid Waste Testing, Fifth
Volume, ASTM STP 925, C.L. Perket, ed., American Society for Testing and
Materials, Philadelphia, 1986.
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EXHIBIT F
CHAIN-OF-CUSTODY, DOCUMENT CONTROL,
AND STANDARD OPERATING PROCEDURES
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1. SAMPLE CHAIN-OF-CUSTODY
A sample is physical evidence collected from a facility or from the
environment. Controlling evidence is an essential part of the
hazardous waste investigation effort. To accomplish this, Contractors
are required to develop and implement the following sample
identification, chain-of-custody, sample receiving, and sample tracking
procedures.
1.1 Sample Identification
To assure traceabilicy of the samples while in possession of the
Contractor, the Contractor shall have a specified method for
maintaining identification of samples throughout the laboratorjr.
Each sample and sample preparation container shall be labeled with the
EPA number or a unique laboratory identifier. If a unique laboratory
identifier is used, it shall be cross-referenced to the EPA number.
1.2 Chain-of-Custody Procedures
Because of the nature of the data being collected, the custody of EPA
samples must be traceable from the time the samples are collected until
they are introduced as evidence in legal proceedings. The Contractor
shall have procedures ensuring that EPA sample custody is maintained
and documented. A sample is under custody if:
o It is in your possession, or
o It is in your view after being in your possession, or
o It was in your possession and you locked it up, or
o It is in a designated secure area. (Secure areas shall be
accessible only to authorized personnel.)
1.3 Sample Receiving Procedures
1.3.1 The Contractor shall designate a sample custodian responsible
for receiving all samples.
<*
1.3.2 The Contractor shall designate a representative to receive
samples in the event that the sample custodian is not
available.
1.3.3 The condition of the shipping containers and sample bottles
shall be inspected upon receipt by the sample custodian or
his/her representative.
1.3.4 The condition of the custody seals (intact/not intact) shall be
inspected upon receipt by the sample custodian or his/her
representative.
1.3.5 The sample custodian or his/her representative shall check for
the presence or absence of the following documents accompanying
the sample shipment:
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o Airbills or airbill scickers
o Custody seals
o EPA cuscody records
o EPA traffic reports or SAS packing lists
o Sample cngs
1.3.6 The sample custodian or his/her representative shall sign and
date all forms (e.g., custody records, traffic reports or
packing liscs, and airbills) accompanying the samples at the
time of sample receipt.
1.3.7 The'Contractor shall contact the Sample Management Office (SMO)
to resolve discrepancies and problems such as absent documents,
conflicting information, broken custody seals, and
unsatisfactory sample condition (e.g., leaking sample bottle).
1.3.8 The Contractor shall record the resolution of discrepancies and
problems on Telephone Contact Logs.
1.3.9 The following information shall be recorded on Form DC-1 (See
Exhibit B) by the sample custodian or his/her representative as
samples are received and inspected:
o Condition of the shipping container
o Presence or absence and condition of custody seals on
shipping and/or sample containers
o Custody seal numbers, when present
o Condition of the sample bottles
o Presence or absence of airbills or airbill stickers
o Airbill or airbill sticker numbers
o Presence or absence of EPA custody records
o Presence or absence of EPA traffic reports or SAS packing
lists
^
o Presence or absence of sample tags
o Sample cag identification numbers cross-referenced to the
EFA sample numbers
o Verification of agreement or non-agreement of information
recorded on shipping documents and sample containers
o Problems or discrepancies
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1.4 Sample Tracking Procedures
The Contractor shall maintain records documenting all phases of sample
handling from receipt to final analysis.
2. DOCUMENT CONTROL PROCEDURES
The goal of the laboratory document control program is to assure that
all documents for a specified Sample Delivery Group (SDG) will be
accounted for when the project is completed. Accountable documents
used by contract laboratories shall include, but not be limited to,
logbooks, chain-of-custody records, sample work sheets, bench sheets,
and other documents relating to the sample or sample analyses. The
following document control procedures have been established to assure
that all laboratory records are assembled and stored for delivery to
EPA or are available upon request from EPA prior, to the delivery
schedule.
2.1 Preprinted Laboratory Forms and Logbooks
2.1.1 All documents produced by the Contractor which are directly
related to the preparation and analysis of EPA samples shall
become the property of the EPA and shall be placed in the
complete sample delivery group file (CSF). All observations
and results recorded by the laboratory but not on preprinted
laboratory forms shall be entered into permanent laboratory
logbooks. When all data from a SDG is compiled, all original
laboratory forms and copies of all SDG-related logbook entries
shall be included in the documentation package.
2.1.2 The Contractor shall identify the activity recorded on all
laboratory documents which are directly related to the
preparation and analysis of EPA samples.
2.1.3 Pre-printed laboratory forms shall contain the name of the
laboratory and be dated (month/day/year) and signed by the
person responsible for performing the activity at the time an
activity is performed.
•»
2.1.4 Logbook entries shall be dated (month/day/year) and signed by
the person responsible for performing the activity at the time
an activity is performed.
2.1.5 Logbook entries shall be in chronological order. Entries in
logbooks, with the exception of instrument run logs and
extraction logs, shall include only one SDG per page.
2.1.6 Pages in both bound and unbound logbooks shall be sequentially
numbered.
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2.1.7 Instrument run logs shall be maintained so as to enable a
reconstruction of the run sequence of individual instruments.
Because the laboratory must provide copies of the instrument
run logs to EPA, the laboratory may exercise the option of
using only Laboratory or EPA sample identification numbers in
the logs for sample ID rather than government agency or
commercial client names to preserve the confidentiality of
commercial clients.
2.1.8 Corrections Co supporting documents and raw data shall be made
by drawing a single line through the error and entering the
correct information. Corrections and additions to supporting
documents and raw data shall be dated and initialed. No
information shall be obliterated or rendered unreadable.
All notations shall be recorded in ink.
Unused portions of documents shall be "z'd" out.
2.2 Consistency of Documentation
The Contractor shall assign a document control officer responsible for
the organization and assembly of the CSF.
All copies of laboratory documents shall be complete and legible.
Original documents which include information relating to more than one
SDG shall be filed in the CSF of the lowest SDG number. The copy(s)
shall be placed in the other CSF(s) and the Contractor shall record the
following information on the copy(s) in red ink:
"COPY
ORIGINAL IS FILED IN CSF "
The Contractor shall sign and date this addition to the copy(s).
Before releasing analytical results, the document control officer shall
assemble and cross-check the information on samples tags, custody
records, lab bench sheets, personal and instrument logs, and other
relevant deliverables to ensure that data pertaining to each particular
sample or sample delivery group is consistent throughout the CSF.
2.3 Document Numbering and Inventory Procedure
In order to provide document accountability of the completed analysis
records, each item in the CSF shall be inventoried and assigned a
serialized number as described in Exhibit B).
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All documents relevant to each sample delivery group, including logbook
pages, bench sheets, mass spectra, chromatograms, screening records,
re-preparation records, re-analysis records, records of failed or
attempted analysis, custody records, library research results, etc.
shall be inventoried.
The Document Control Officer (DCO) shall be responsible for ensuring
that all documents generated are placed in the CSF for inventory and
are delivered to the appropriate EPA region or other receiver as
designated by EPA. The DCO shall place the sample tags in plastic bags
in the file.
2.4 Storage of EPA Files
The Contractor shall maintain EPA laboratory documents in a secure
location.
2.5 Shipment of Deliverables
The Contractor shall document shipment of deliverables packages to the
recipients. These shipments require custody seals on the containers
placed such that they cannot be opened without damaging or breaking the
seal. The Contractor shall document what was sent, to whom, the date,
and che method (carrier) used.
A copy of the transmittal letter for the CSF shall be sent to the
NEIC/CEAT and the SMO.
3. SPECIFICATIONS FOR WRITTEN STANDARD OPERATING PROCEDURES
The Contractor shall have written standard operating- procedures (SOPs)
for receipt of samples, maintenance of custody, sample identification,
sample storage, sample tracking, and assembly of completed data.
An SOP is defined as a. written narrative stepwise description of
laboratory operating procedures including examples of. laboratory
documents. The SOPs shall accurately describe the actual procedures
used in the laboratory, and copies of the written SOPs shall be
available to the appropriate laboratory personnel. These procedures
are necessary to ensure that analytical data produced under this
contract are acceptable for use in EPA enforcement case preparation and
litigation. The Contractor's SOPs shall provide mechanisms and
documentation to meec each of the following specifications and shall be
used by EPA as the basis for laboratory evidence audits.
3.1 The Contractor shall have written SOPs describing the sample
custodian's duties and responsibilities.
3.2 The Contractor shall have written SOPs for receiving and logging in of
the samples. The procedures shall include but not be limited to
documenting the following information:
3.2.1 Presence or absence of EPA chain-of-custody forms
3.2.2 Presence or absence of airbills or airbill stickers
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3.2.3 Presence or absence of traffic reporcs or SAS packing lists
3.2.4 Presence or absence of custody seals on shipping and/or sample
containers and their condition
3.2.5 Custody seal numbers, when present
3.2.6 Airbill or airbill sticker numbers
3.2.7 Presence or absence of sample tags
3.2.8 Sample tag ID numbers
3.2.9 Condition of the shipping container
3.2.10 Condition of the sample bottles
3.2.11 Verification of agreement or non-agreement of information on
receiving documents and sample containers
3.2.12 Resolution of problems or discrepancies with the SMO ,
3.2.13 An explanation of any terms used by the laboratory to describe
sample condition upon receipt (e.g., good, fine, OK)
3.3 The Contractor shall have written SOPs for maintaining identification
of EPA samples throughout the laboratory.
If the Contractor assigns unique laboratory identifiers, written SOPs
shall include a description of the method used to assign the unique
laboratory identifier and shall include a description of the document
used to cross-reference the unique laboratory identifier to the EPA
sample number.
If the Contractor uses prefixes or suffixes in addition to sample
identification numbers, the written SOPs shall include their
definitions.
3.4 The Contractor shall have written SOPs describing all storage areas for
samples in the laboratory. The SOPs shall include a list of authorized
personnel who have access or keys to secure storage areas.
3.5 The Contractor shall have written SOPs describing the method by which
the laboratory maintains samples under custody.
3.6 The Contractor shall have written SOPs describing the method by which
the laboratory maintains the security of any areas identified as
secure.
3.7 The Contractor shall have written SOPs for tracking the work performed
on any particular samples. The tracking SOP shall include:
F-7 OLM01.0
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o A description of the documents used to record sample receipt,
sample storage, sample transfers, sample preparations, and
sample analyses.
o A description of the documents used to record calibration and
QA/QC laboratory work.
o Examples of document formats and laboratory documents used in
the sample receipt, sample storage, sample transfer, and sample
analyses.
o A narrative step-wise description of how documents are used to
track samples.
3.8 The Contractor shall have written SOPs for organization and assembly of
all documents relating to each SDG. Documents shall be filed on a
sample delivery group-specific basis. The procedures shall ensure that
all documents including logbook pages, sample tracking records,
chromatographic chares, computer printouts, raw data summaries,
correspondence, and any other written documents having reference to the
SDG are compiled in one location for submission to EPA. The written
SOPs shall include:
o A description of the numbering and inventory method.
o A description of the method used by the laboratory to verify
consistency and completeness of the CSF.
o Procedures for the shipment of deliverables packages using
custody seals.
4. HANDLING OF CONFIDENTIAL INFORMATION
A Contractor conducting work under this contract may receive EPA-
designated confidential information from the agency. Confidential
information must be handled separately from other documentation
developed under this contract. To accomplish this, the following
procedures for the handling of confidential information have been
established.
4.1 All confidential documents shall be under the supervision of a
designated ^document control officer (DCO).
4.2 Confidential Information
Any samples or information received with a request of confidentiality
shall be handled as "confidential." A separate locked file shall be
maintained to store this information and shall be segregated from other
nonconfidential information. Data generated from confidential samples
shall be treated as confidential. Upon receipt of confidential
information, the DCO will log these documents into a Confidential
Inventory Log. The information will then be available to authorized
personnel but only after it has been signed out to that person by the
DCO. The documents shall be returned to the locked file at the
conclusion of each working day. Confidential information may not be
reproduced except upon approval by the EPA Technical and Administrative
Project Officer. The DCO will enter all copies into the document
F-8 OLM01.0
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control system described above. In addition, this information may not
be disposed of except upon approval by the EPA project officer. The
DCO shall remove and retain the cover page of any confidential
information disposed of for one year and shall keep a record on the
disposition in the Confidential Inventory Log.
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EXHIBIT G
GLOSSARY OF TERMS
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GLOSSARY OF TERMS
ALIQUOT - a measured portion of a sample taken for analysis.
ANALYSIS DATE/TIME - the ciace and military time 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 - see Method Blank
4-BROMOFLUOROBENZENE (BFB) - compound chosen to establish mass spectral
instrument performance for volatile analyses.
CASE - a finite, usually predetermined number of samples collected over a
given time period from a particular site. Case numbers are assigned by the
Sample Management Office. A Case consists of one or more Sample Delivery
Groups.
CHARACTERIZATION - a determination of the approximate concentration range of
compounds of interest used to choose the appropriate analytical protocol.
CONCENTRATION LEVEL (low or medium) - characterization of soil samples or
sample fractions as low concentration or medium concentration is made on the
basis of the laboratory's preliminary screen, not on the basis of information
entered on the Traffic Report by the sampler.
'CONTINUING CALIBRATION - analytical standard run every 12 hours to verify the
calibration of the GC/MS system.
CONTINUOUS LIQUID-LIQUID EXTRACTION - used herein synonymously with the terms
continuous extraction, continuous liquid extraction, and liquid extraction.
DAY - unless otherwise specified, day shall mean calendar day.
DECAFLUOROTRIPHENYLPHOSPHINE (DFTPP) - compound chosen to establish mass
spectral instrument performance for semivolatile analysis.
EXTRACTABLE - a compound that can be partitioned into an organic solvent from
the sample matrix and is amenable to gas chromatography. Extractables
include semivolatile (BNA) and pesticide/Aroclor compounds.
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 to the target compounds.
INTERNAL STANDARDS - compounds added to every standard, blank, matrix spike,
matrix spike duplicate, sample (for VOAs), and sample extract (for
seraivolatiles) at a known concentration, prior to analysis. Internal
standards are used as the basis for quantitation of the target compounds.
G-2 OLM01.0
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LABORATORY - synonymous wich Contractor as used herein.
MATRIX - the predominant material of which the sample to be analyzed is
composed. For the purpose of this SOW, a sample matrix is either water or
soil/sediment. Matrix is not synonymous with phase (liquid or solid).
MATRIX SPIKE - aliquot of a matrix (water or soil) fortified (spiked) with
known quantities of specific compounds and subjected to the entire analytical
procedure in order to indicate the appropriateness of the method for the
matrix by measuring recovery.
MATRIX SPIKE DUPLICATE - a second aliquot of the same matrix as the matrix
spike (above) that is spiked in order to determine the precision of the
method.
METHOD BLANK (previously termed reagent blank) - an analytical control
consisting of all reagents, internal standards and surrogate standards, that
is carried through the entire analytical procedure. The method blank is used
to define the level of laboratory background 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 MOISTURE - an approximation of the amount of water in a soil/sediment
sample made by drying an aliquot of Che sample at 105"C. The percent
moisture determined in this manner also includes contributions from all
compounds that may volatilize at 105'C, including water. Percent moisture is
determined from decanted samples and from samples that are not decanted.
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 (purgeafile) organics by stripping the compounds from water or soil
by a stream of inert gas, crapping the compounds on a porous polymer trap,
and thermally desorbing the trapped compounds onto the gas chromatographic
column.
REAGENT WATER - water in which an interferent is not observed at or above the
minimum quantitation limit of the parameters of interest.
RECONSTRUCTED ION CHROMATOGRAM (RIG) - a mass spectral graphical
representation of the separation achieved by a gas chromatograph; a plot of
total ion current versus retention time.
G'3 OLM01.0
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RECOVERY - a determination of the accuracy of the analytical procedure made
by comparing measured values for a fortified (spiked) sample againsc the
known spike values. Recovery is determined by the following equation:
measured value
%Rec - n— , x 100%
spiked value
RELATIVE RESPONSE FACTOR (RRF) - a measure of the relative mass spectral
response of an analyte compared to its internal standard. Relative Response
Factors are determined by analysis of standards and are used in the
calculation of concentrations of analytes in samples. RRF is determined by
the following equation:
AX Cis
RRF - JL * J±
Ais cx
Where
A - area of the characteristic ion measured
C - concentration
is - internal standard
x - analyte of interest
RESOLUTION - also termed separation, 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, multipled by
100.
SAMPLE - a portion of material to be analyzed that is contained in single or
multiple containers and identified by a unique sample number.
SAMPLE DELIVERY GROUP (SDG) - a unit within a single Case that is used to
identify a group of samples for delivery. An SDG is a group of 20 or fewer
field samples wiphin a Case, received over a period of up to 14 calendar
days. Data from all samples in an SDG are due concurrently. A Sample
Delivery Group is defined by one of the following, whichever occurs first:
o Case; or
o Each 20 field samples within a Case; or
o Each 14-day calendar period during which field samples in a Case are
received, beginning with receipt of the first sample in the Case or SDG.
Samples may be assigned to Sample Delivery Groups by matrix (i.e., all soils
in one SDG, all waters in another), at the discretion of the laboratory.
SAMPLE NUMBER (EPA Sample Number) - a unique identification number designated
by EPA for each sample. The EPA sample number appears on the sample Traffic
Report which documents information on that sample.
G-4 , OLM01.0
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SEMIVOLATILE COMPOUNDS - compounds amenable co analysis by extraction of the
sample with an organic solvent. Used synonymously with Base/Neutral/Acid
(BNA) compounds.
SOIL - used herein synonymously with soil/sediment and sediment.
STANDARD ANALYSIS - an analytical determination made with known quantities of
target compounds; used to determine response factors.
SURROGATES (Surrogate Standard) - for semivolatiles and pesticides/Aroclors,
compounds added to every blank, sample, matrix spike, matrix spike duplicate,
and standard; used to evaluate analytical efficiency by measuring recovery.
Surrogates are brominated, fluorinated, or isotopically labelled compounds
not expected to be detected in environmental media.
SYSTEM MONITORING COMPOUNDS - compounds added to every blank, sample, matrix
spike, matrix spike duplicate, and standard for volatile analysis, and used
to evaluate the performance.of the entire purge and trap-gas chromatograph-
mass spectrometer system. These compounds are brominated or deuterated
compounds not expected tc 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, system monitoring compounds, or
surrogates. Up to 30 peaks (those greater than 10% of peak areas or heights
of nearest internal standards) 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.
TRAFFIC REPORT (TR) - an EPA 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 has 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.
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 0.32 mm. Columns with lesser diameters
are classified as narrow bore capillaries.
G-5 OLM01.0
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EXHIBIT H
DATA DICTIONARY AND FORMAT FOR DATA
DELIVERABLES IN COMPUTER-READABLE FORMAT
Page
SECTION I: Description of Deliverables H-2
SECTION II: Format A Specifications H-4
SECTION III: Format B Specifications H-67
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SECTION I
DESCRIPTION OF DELIVERABLE
1. Introduction
1.1 Format A and Format B are the file formats specified for delivery of
computer-readable data. Format A is oriented to the structure of the
hardcopy reporting forms required by the contract. Format B is
organized by analysis, with groups of analyses aggregated to produce
files corresponding to an SDG. Information sufficient to generate
required hardcopy forms is contained in each format.
1.2 The file(s) for a Sample Delivery Group (SDG, see Exhibit A, Section I,
B) must be submitted on diskette(s) (see Deliverable, 2.1).
1.3 Format A consists of variable length ASCII records.
Format B consists of fixed length ASCII records.
1.4 All information for one SDG must be in one and only one file for Format
A.
Format B data may be contained in more than one file as necessary.
2. Deliverable
2.1 The file must be submitted on 5-1/4 inch floppy diskette(s), which may
be either double-sided, double density, 360 K-byte or high capacity
1.2 M-byte diskette(s). IBM-compatible, 3.5 inch double-sided,double
density 720 K-byte or high density 1.44 M-byte diskettes may also be
submitted. The diskettes must be formatted and recorded using MS-DOS
Operating System. The diskettes must contain all information relevant
to one and only one SDG, and must accompany the hardcopy package for
the SDG submitted to the Sample Management Office (see Exhibit B).
Format B 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 must start with a type 10 record, and the multiple type 10
records for each file of the same production run must be identical. If
it is necessary to split the data from a single sample onto multiple
diskettes, then the type 20 (and following) type records for that
sample mist be repeated. In this situation, columns 7-30, which
collectively identify the sample, must be identical on each diskette.
H-2 OLM01.0
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2.2 Information on Che diskett must correspond exactly with information
submitted in the hardcopy data package and.on the hardcopy data package
forms. Blank or unused records in either format must not be included
on the diskettes. If the information submitted in the hardcopy data
package forms is changed, the information in the diskette file must be
changed accordingly, and a complete diskette containing all the
information for the SDG must be resubmitted along with the hard copy at
no additional cost to the EPA.
2.2 Each diskette must be identified with an external label containing (in
this order) the following information:
Disk Density
File Name(s)
Laboratory Name (optional)
Laboratory Code
Case Number
SAS Number (where applicable)
The format for the File Name must be XXXXX.OlA
where XXXXX is the SDG identifier
Dimensions of the label must be in the range 4-3/4" to 5" long by 1-1/4
to 1-1/2" wide.
H-3 OLM01.0
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SECTION II
FORMAT A SPECIFICATION
1. Format Characteristics
1.1 Format A is based upon the structure of the hardcopy reporting forms
required by the contract. Except for Record Type and the Variable Type,
all fields in the format must correspond directly with entries or items
on the hardcopy forms.
1.2 Format A includes detailed specifications for the required format of
each reporting Form's HEADER and DETAIL records. The exact column in
which each field is to be contained is specified, as well as the length
of the field. Each field 's required contents are specified either as a
literal (contained in single quotes) which must appear exactly as shown
(without the quotes), or as a variable for which a format is listed in
the format column. Each field's required format is specified either as
an option of two or more choices (separated by slashes), as MM/DD/YY for
a date, as HHMM for time, as a CHARACTER field, or as NUMERIC field.
1.3 All Format A fields listed as CHARACTER may contain standard ASCII
characters, and must be left-justified and padded to the right with
blanks. Formats listed as NUMERIC may contain numeric digits, a decimal
place, and a leading minus sign. Numeric entries muse be right-
justified and padded to the left with blanks. A positive sign is
assumed if no negative sign is entered in a numeric field. A positive
sign must: not be entered in a numeric field.
Requirements for significant figures and number of decimal places are
specified in Exhibit B. The numeric field length are specified such
that all possible numeric values can be written to the file. The size
of the numeric field indicates the maximum number of digits, decimal,
and negative sign if appropriate that can appear in the field at the
same time. Therefore, the number reported may need to be rounded (using
EPA Rounding Rules) to fit into the field. The rounding must maintain
the greatest significance possible providing the field length
limitation. In addition, the rounded number that appears on the form,
and therefore the feild in the diskette file, must be used in any
calculation that may result in other numbers reported on the same form
or other forms in the SDG.
The following examples describe the format NUMERIC with a field size of
6:
(Quotation marks indicate the limits of the field described and are not
included in the format.)
H-4 OLM01.0
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RAW DATA VALUE REPORTED NUMBER
1000000 "999999"
1000 " 1000"
100.1 " 100.1"
100.11 "100.11"
10.1 " 10.1"
0.29 " 0.29"
0.125559 ".12556"
-10.1 " -10.1"
-1000.1 " -1000"
-10000.1 "-10000"
-1000000 "-99999"
2. Record Types
2.1 Format A consists of variable length ASCII records. The last two bytes
of each record must contain "carriage return" and "line feed",
respectively. Unused bytes in partially filled fields must be blank-
filled.
2.2 Format A has three types of records: Header Records, Detail Records and
Comment Records.
Type Type ID Contents
Header H Nonrepeating fields which
together are unique to the
associated hardcopy form
Detail D A group of fields that are
repeated on a form, and are
uniquely positioned by (e.g.)
CAS Number or Sequence Number
Comment C Nonrepeating fields containing
text that comments on
information reported on the
form
Although there are forms with HEADER records which are not unique per
page, the Header record must be included as a place holder, indicating
that the DETAIL records follow.
The format for COMMENT records is the same for all forms, and is
described after all other formats.
2.3 The first 3 columns in each record contain the FORM ID, identifying the
hard copy Low Concentration Organics Reporting Form for which the
record contains data. The ID must be left-justified in the feild.
H-5 OLM01.0
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FORM ID FORM DESCRIBTION
1A VOLATILE ORGANIC ANALYSIS DATA SHEET
1BC SEMIVOLATILE ORGANIC ANALYSIS DATA SHEET
ID PESTICIDE ORGANIC ANALYSIS DATA SHEET
IE VOLATILE ORGANIC ANALYSIS DATA SHEET (TIC)
IF SEMIVOLATILE ORGANIC ANALYSIS DATA SHEET (TIC)
2A WATER VOLATILE SYSTEM MONITORING COMPOUND RECOVERY
2B SOIL VOLATILE SYSTEM MONITORING COMPOUND RECOVERY
2C WATER SEMIVOLATILE SURROGATE RECOVERY
2D SOIL SEMIVOLATILE SURROGATE RECOVERY
2E WATER PESTICIDE SURROGATE RECOVERY
2F SOIL PESTICIDE SURROGATE RECOVERY
3A WATER VOLATILE MATRIX SPIKE/DUPLICATE RECOVERY
3B SOIL VOLATILE MATRIX SPIKE/DUPLICATE RECOVERY
3C WATER SEMIVOLATILE MATRIX SPIKE/DUPLICATE RECOVERY
3D SOIL SEMIVOLATILE MATRIX SPIKE/DUPLICATE RECOVERY
3E WATER -PESTICIDE MATRIX SPIKE/DUPLICATE RECOVERY
3F SOIL PESTICIDE MATRIX SPIKE/DUPLICATE RECOVERY
4A VOLATILES METHOD BLANK SUMMARY
4B SEMIVOLATILES METHOD BLANK SUMMARY
4C PESTICIDES METHOD BLANK SUMMARY
5A VOLATILE ORGANIC INSTRUMENT PERFORMANCE CHECK
SB SEMIVOLATILE ORGANIC INSTRUMENT PERFORMANCE CHECK
6A VOLATILE ORGANIC INITIAL CALIBRATION DATA
6B SEMIVOLATILE ORGANIC INITIAL CALIBRATION DATA
6C SEMIVOLATILE ORGANIC INITIAL CALIBRATION DATA
6D PESTICIDES INITIAL CALIBRATION OF SINGLE
COMPONENT ANALYTES
6E PESTICIDES INITIAL CALIBRATION OF SINGLE
COMPONENT ANALYTES
6F PESTICIDES INITIAL CALIBRATION OF MULTICOMPONENT
ANALYTES
6G PESTICIDES RESOLUTION CHECK SUMMARY
7A VOLATILES CONTINUING CALIBRATION SUMMARY
7B SEMIVOLATILES CONTINUING CALIBRATION SUMMARY
1C SEMIVOLATILES CONTINUING CALIBRATION SUMMARY
7D , PESTICIDES CALIBRATION VERIFICATION SUMMARY
7E PESTICIDES CALIBRATION VERIFICATION SUMMARY
8A VOLATILES INTERNAL STANDARD AREA AND RT SUMMARY
8B SEMIVOLATILES INTERNAL STANDARD AREA AND RT
SUMMARY
8C SEMIVOLATILES INTERNAL STANDARD AREA AND RT
SUMMARY
8D PESTICIDES ANALYTICAL SEQUENCE
9A PESTICIDES FLORISIL CARTRIDGE CHECK
9B PESTICIDES GPC CALIBRATION
10A PESTICIDES IDENTIFICATION SUMMARY FOR SINGLE
COMPONENT ANALYTES
10B PESTICIDES IDENTIFICATION SUMMARY FOR
MULTICOMPONENT ANALYTES
H-6 OLM01.0
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FORM I FILE DESCRIPTION
(FORM 1)
H-9 OLM01.0
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VOLATILE ORGANICS ANALYSIS DATA SHEET - (FORM 1A)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
20
45
56
62
67
73
78
83
95
100
102
116
119
127
129
137
147
151
159
167
175
-
-
-
-
-
-
-
-
-
-
-
-
—
-
-
-
-
-
-
-
-
-
-
-
-
3
5
7
19
44
55
61
66
72
77
82
94
99
101
115
118
126
128
136
146
150
158
166
174
179
3
2
2
12
25
11
6
5
6
5
5
12
5
2
14
3
8
2
8
10
4
8
8
8
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
EPA SAMPLE NO.
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
MATRIX
LAB SAMPLE ID
SAMPLE WT/VOL
SAMPLE WT/VOL UNITS
LAB FILE ID
LEVEL
DATE RECEIVED
% MOISTURE: NOT DEC.
DATE ANALYZED
GC COLUMN
GC COLUMN ID
DILUTION FACTOR
SOIL EXTRACT VOLUME
SOIL ALIQUOT VOLUME
CONCENTRATION UNITS
FORMAT/CONTENTS
'1A'
'AA'-'ZZ1
•HI1
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
NUMERIC
'G' OR 'ML1
CHARACTER
'LOW'/'MED'
MM/DD/YY
NUMERIC
MM/DD/YY
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
•UG/L1 OR 'UG/KG1
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-17 10 CAS NO.
18-30 13 RESULT
31-35 5 QUALIFIER (Q)
FORMAT/CONTENTS
'AA'-'ZZ1
•Dl1
CHARACTER
NUMER'IC
CHARACTER
H-10
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3.
Form
1A
IB
1C
ID
IE
IF
2A
2B
2C
2D
2E
2F
3A
3B
3C
3D
3E
3F
4A
4B
4C
5A
5B
6A
6B
6C
6D
6E
6F
6G
Record Length
Table 3.1 summarizes the length and (in parencheses) the number of
records in Format A. The maximum number of detail and comment records
is shown, corresponding to a submission of hardcopy forms on which
information is written on all possible lines. The Form Totals are the
maximum lengths (excluding carriage return/line feed) required for a
complete set of each type of form.
Table 3.1 Format A Summary
Record
Header
HI
179a(l)b
179(1)
179(1)
181(1)
21(1)
21(1)
11(1)
14(1)
11(1)
11(1)
39(1)
39(1)
27(1)
30(1)
27(1)
30(1)
27(1)
27(1)
86(1)
87(1)
139(1)
62(1)
47(1)
126(1)
111(1)
111(1)
62(1)
62(1)
47(1)
127(1)
Detail
DJL PJ£
35(33)
35(33)
35(31)
35(28)
71(30)
71(30)
46(30)
46(30)
70(30)
70(30)
52(30)
52(30)
70(5) 61(5)
70(5) 61(5)
70(11) 61(11)
70(11) 61(11)
70(6) 61(6)
70(6) 61(6)
51(30)
55(30)
49(26)
20(9) 59(22)
21(13) 59(22)
69(36)
69(35)
69(35)
64(22)
79(22)
68(40)
45(9) 45(9)
Conn
£1
77(1)
77(1)
77(1)
77(1)
77(1)
77(1)
77(1)
77(1)
77(1)
lent
C2
77(1)
77(1)
77(1)
77(1)
77(1)
77(1)
77(1)
77(1)
77(1)
H-7
OLM01.0
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7A 82(1) 58(36)
7B 67(1) 58(35)
7C 67(1) 58(35)
7D 124(1) 70(6)
7E 145(1) 70(11) 70(13)
8A 62(1) 57(3) 66(22)
8B 47(1) 57(3) 66(22)
8C 47(1) 57(3) 66(22)
8D 57(1) 57(32)
9A 57(1) 62(11) 49(23) 77(1) 77(1)
9B 57(1) 62(6) 49(26) 77(1) 77(1)
10A 99(1) 97(8)
10B 99(1) 91(15) 65(3)
a • length of record in bytes (excluding carriage return/line feed)
b • maximum number of records required for a form.
4. Form Suffix
The fourth and fifth bytes of each record contain the form suffix (AA-
ZZ), which must be unique (within a type of form (e.g., Form 1A, Form
2C, etc.,) for each set of records that corresponds to one hardcopy
form. For example, the form suffix for records for the first occurrence
in the file of a Form 1C must be AA. The second occurrence must: be AB,
and the twenty-eighth must be BA.
5. Record Listing
The remainder of this section contains detailed specifications for every
record required for a full set of hardcopy forms.
H-8 OLM01.0
-------
SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET -
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
20
45
56
62
67
73
78
83
95
100
102
116
119
127
129
130
138
146
154
162
170
171
175
-
-
-
-
—
-
—
-
-
-
-
-
-
-
-
-
—
-
—
-
-
-
-
-
-
—
—
3
5
7
19
44
55
61
66
72
77
82
94
99
101
115
118
126
128
129
137
145
153
161
169
170
174
179
3
2
2
12
25
11
6
5
6
5
5
12
5
2
14
3
8
2
1
8
8
8
8
8
1
4
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
EPA SAMPLE NO.
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
MATRIX
LAB SAMPLE ID
SAMPLE WT/VOL
SAMPLE WT/VOL UNITS
LAB FILE ID
LEVEL
DATE RECEIVED
% MOISTURE
% MOISTURE (DECANTED)
DATE •EXTRACTED
CONG. EXTRACT VOLUME
DATE ANALYSED
INJECTION VOLUME
DILUTION FACTOR
GPC CLEANUP
PH
CONCENTRATION UNITS
(FORM IB)
*
FORMAT/CONTENTS
'IB'
'AA'-'ZZ'
'HI1
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
NUMERIC
'G' OR 'ML1
CHARACTER
'LOW'/'MED'
MM/DD/YY
NUMERIC
'Y'/'N1
MM/DD/YY
NUMERIC
MM/DD/YY
NUMERIC
NUMERIC
'Y'/'N'
NUMERIC
•UG/L' OR 'UG/KG1
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-17 10 CAS NO.
18-30 13 RESULT
31-35 5 QUALIFIER (Q)
FORMAT/CONTENTS
'IB1
'AA'-'ZZ1
'Dl'
CHARACTER
NUMERIC
CHARACTER
H-ll
OLM01.0
-------
SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET - (FORM 1C)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1 -
4 -
6 -
8 -
20 -
45 -
56 -
62 -
67 -
73 -
78 -
83 -
95 -
100 -
102 -
116 -
119 -
127 -
129 -
130 -
138 -
146 -
154 -
162 -
170 -
171 -
175 -
3
5
7
19
44
55
61
66
72
77
82
94
99
101
115
118
126
128
129
137
145
153
161
169
170
174
179
3
2
2
12
25
11
6
5
6
5
5
12
5
2
14
3
8
2
1
8
8
8
8
8
1
4
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
EPA SAMPLE NO.
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
MATRIX
LAB SAMPLE ID
SAMPLE WT/VOL
SAMPLE WT/VOL UNITS
LAB FILE ID
LEVEL
DATE RECEIVED
% MOISTURE
% MOISTURE (DECANTED)
DATE EXTRACTED
CONC. EXTRACT VOLUME
DATE ANALYSED
INJECTION VOLUME
DILUTION FACTOR
GPC CLEANUP
PH
CONCENTRATION UNITS
FORMAT/CONTENTS
11C'
'AA'-'ZZ'
•HI1
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
NUMERIC
•G' OR 'ML'
CHARACTER
'LOW'/'MED'
MM/DD/YY
NUMERIC
•Y'/'N'
MM/DD/YY
NUMERIC
MM/DD/YY
NUMERIC
NUMERIC
•Y«/'N'
NUMERIC
'UG/L1 OR 'UG/KG1
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-17 10 CAS NO.
18-30 13 RESULT
31-35 5 QUALIFIER (Q)
FORMAT/CONTENTS
•1C'
'AA'-'ZZ'
•Dl'
CHARACTER
NUMERIC
CHARACTER
H-12
OIHOl.O
-------
PESTICIDE ORGANICS ANALYSIS DATA SHEET - (FORM ID)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
20
45
56
62
67
73
78
83
95
100
102
116
118
119
127
131
139
147
155
163
171
172
176
177
-
-
-
—
—
—
-
-
-
-
-
—
—
-
-
—
-
-
—
-
-
-
-
-
-
-
-
-
3
5
7
19
44
55
61
66
72
77
82
94
99
101
115
117
118
126
130
138
146
154
162
170
171
175
176
181
3
2
2
12
25
11
6
5
6
5
5
12
5
2
14
2
1
8
4
8
8
8
8
8
1
4
1
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
EPA SAMPLE NO.
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
MATRIX
LAB SAMPLE ID
SAMPLE WT/VOL
SAMPLE WT/VOL UNITS
LAB FILE ID
% MOISTURE
% MOISTURE (DECANTED)
DATE RECEIVED
EXTRACTION
DATE EXTRACTED
CONC. EXTRACT VOLUME
DATE ANALYZED
INJECTION VOLUME
DILUTION FACTOR
GPC CLEANUP
PH
SULFUR CLEANUP
CONCENTRATION UNITS
FORMAT/CONTENTS
•ID'
'AA'-'ZZ'
•HI1
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
NUMERIC
•G1 OR 'ML1
CHARACTER
NUMERIC
'Y'/'N'
MM/DD/YY
CHARACTER
MM/DD/YY
NUMERIC
MM/DD/YY
NUMERIC
NUMERIC
'Y'/'N1
NUMERIC
'Y'/'N'
•UG/L1 OR 'UG/KG'
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-17 10 CAS NO.
18-30 13 RESULT
31-35 5 QUALIFIER (Q)
FORMAT/CONTENTS
•ID1
•AA'-'ZZ1
'Dl'
CHARACTER
NUMERIC
CHARACTER
H-13
OLM01.0
-------
VOLATILE ORGANICS ANALYSIS DATA SHEET - (FORM IE)
TENTATIVELY IDENTIFIED COMPOUNDS
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS FORMAT/CONTENTS
1-3 3 FORM NUMBER 'IE1
4-5 2 FORM SUFFIX 'AA'-'ZZ'
6-7 2 RECORD TYPE 'HI'
8-19 12 EPA SAMPLE NO. CHARACTER
20-21 2 NUMBER OF TICS FOUND NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS s fORMAT/CONTENTS
1-3 3 FORM NUMBER 'IE1
4-5 2 FORM SUFFIX 'AA'-'ZZ'
6-7 2 RECORD TYPE 'Dl1
8-9 2 SEQUENCE NUMBER NUMERIC
10 - 19 10 CAS NO. CHARACTER
20 - 47 28 COMPOUND NAME CHARACTER
48-53 6 RT NUMERIC
54-66 13 ESTIMATED CONCENTRATION NUMERIC
67-71 5 QUALIFIER (Q) CHARACTER
H-14 OLM01.0
-------
SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET - (FORM IF)
TENTATIVELY IDENTIFIED COMPOUNDS
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS FORMAT/CONTENTS
1-3 3 FORM NUMBER 'IF1
4-5 2 FORM SUFFIX 'AA'-'ZZ'
6 - * 7 2 RECORD TYPE 'HI1
8-19 12 EPA SAMPLE NO. CHARACTER
20-21 2 NUMBER OF TICS FOUND NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS «. FORMAT/CONTENTS
1-3 3 FORM NUMBER 'IF'
4-5 2 FORM SUFFIX 'AA'-'ZZ'
6-7 2 RECORD TYPE 'Dl'
8-9 2 SEQUENCE NUMBER NUMERIC
10 - 19 10 CAS NO. CHARACTER
20 - 47 28 COMPOUND NAME CHARACTER
48-53 6 RT NUMERIC
54 - 66 13 ESTIMATED CONCENTRATION NUMERIC
67-71 5 QUALIFIER (Q) CHARACTER
H-15 OLM01.0
-------
FORM II FILE DESCRIPTION
(FORM 2)
H-16 OLM01.0
-------
WATER VOLATILE SYSTEM MONITORING COMPOUND RECOVERY - (FORM 2A)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1 -
4 -
6 -
8 -
11 -
13 -
3
5
7
10
12
14
3
2
2
3
2
2
FORM NUMBER
FORM SUFFIX
RECORD TYPE
LEVEL
PAGE
OF
FORMAT/CONTENTS
'2A'
'AA'-'ZZ'
'HI*
CHARACTER
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
10
22
27
28
33
34
39
40
46
-
-
-
-
-
-
-
-
-
—
-
-
-
3
5
7
9
21
26
27
32
33
38
39
45
46
3
2
2
2
12
5
1
5
1
5
1
6
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
EPA SAMPLE NO.
TOL % RECOVERY
TOL % RECOVERY
BFB % RECOVERY
BFB % RECOVERY
DCE % RECOVERY
DCE % RECOVERY
OTHER
TOTAL OUT
FLAG
FLAG
FLAG
FORMAT/CONTENTS
'2A'
'AA'-'ZZ'
'Dl'
NUMERIC
CHARACTER
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
NUMERIC
H-17
OLM01.0
-------
SOIL VOLATILE SYSTEM MONITORING COMPOUND RECOVERY - (FORM 2B)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1 -
4 -
6 -
8 -
10 -
3
5
7
9
11
3
2
2
2
2
FORM NUMBER
FORM SUFFIX
RECORD TYPE
PAGE
OF
FORMAT/CONTENTS
•2B1
•AA'-'ZZ'
'HI1
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
10
22
27
28
33
34
39
40
46
-
-
-
-
—
-
-
-
-
-
-
-
-
3
5
7
9
21
26
27
32
33
38
39
45
46
3
2
2
2
12
5
1
5
1
5
1
6
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
EPA SAMPLE NO.
TOL % RECOVERY
TOL % RECOVERY FLAG
BFB % RECOVERY
BFB % RECOVERY FLAG
DCE % RECOVERY
DCE % RECOVERY FLAG
OTHER
TOTAL OUT
FORMAT/CONTENTS
•2B1
•AA'-'ZZ'
•Dl'
NUMERIC
CHARACTER
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
NUMERIC
H-18
OLM01.0
-------
WATER SEMIVOLATILE SURROGATE RECOVERY - (FORM 2C)
HEADER RECORD 1 (HI)
1 -
4 -
6 -
8 -
10 -
3
5
7
9
11
3
2
2
2
2
FORM NUMBER
FORM SUFFIX
RECORD TYPE
PAGE
OF
•2C1
'AA'-'ZZ'
•HI1
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1 -
4 -
6 -
8 -
10 -
22 -
27 -
28 -
33 -
34 -
39 -
40 -
45 _
46 -
51 -
52 -
57 -
58 -
63 -
64 -
69 -
70 -
3
5
7
9
21
26
27
32
33
38
39
44
45
50
51
56
57
62
63
68
69
70
3
2
2
2
12
5
1
5
1
5
1
5
1
5
1
5
1
5
1
5
1
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
EPA SAMPLE NO.
NBZ % RECOVERY
NBZ % RECOVERY
FBP
FBP
TPH
TPH
PHL
PHL
2FP
2FP
TBP
TBP
2CP
2CP
DCB
DCB
RECOVERY
RECOVERY
RECOVERY
RECOVERY
RECOVERY
RECOVERY
RECOVERY
RECOVERY
RECOVERY
RECOVERY
RECOVERY
RECOVERY
RECOVERY
RECOVERY
TOTAL OUT
FLAG
FLAG
FLAG
FLAG
FLAG
FLAG
FLAG
FLAG
FORMAT/CONTENTS
•2C1
'AA'-'ZZ1
•Dl1
NUMERIC
CHARACTER
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
«*'/BLANK
NUMERIC
H-19
OLM01.0
-------
SOIL SEMIVOLATILE SURROGATE RECOVERY - (FORM 2D)
HEADER RECORD 1 (HI)
1 -
4 -
6 -
8 -
10 -
3
5
7
9
11
3
2
2
2
2
FORM NUMBER
FORM SUFFIX
RECORD TYPE
PAGE
OF
•2D1
'AA'-'ZZ1
'HI'
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
10
22
27
28
33
34
39
40
45
46
51
52
57
58
63
64
69
70
-
-
-
-
-
-
-
-
—
-
-
-
-
-
-
-
-
—
-
-
-
-
3
5
7
9
21
26
27
32
33
38
39
44
45
50
51
56
57
62
63
68
69
70
3
2
2
2
12
5
1
5
1
5
1
5
1
5
1
5
1
5
1
5
1
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
EPA SAMPLE NO.
NBZ % RECOVERY
NBZ % RECOVERY FLAG
FBP % RECOVERY
FBP % RECOVERY FLAG
TPH % RECOVERY
TPH % RECOVERY FLAG
PHL * RECOVERY
PHL % RECOVERY FLAG
2FP % RECOVERY
2FP % RECOVERY FLAG
TBP % RECOVERY
TBP % RECOVERY FLAG
2CP % RECOVERY
2CP % RECOVERY FLAG
DCB % RECOVERY
DCB % RECOVERY FLAG
TOTAL OUT
FORMAT/ CONTENTS
'2D'
'AA'-'ZZ'
'Dl'
NUMERIC
CHARACTER
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
H-20
OLM01.0
-------
WATER PESTICIDE SURROGATE RECOVERY - (FORM 2E)
HEADER RECORD 1 (HI)
1
4
6
8
18
22
32
36
38
—
-
-
-
-
-
-
-
-
3
5
7
17
21
31
35
37
39
3
2
2
10
4
10
4
2
2
FORM NUMBER
FORM SUFFIX
RECORD TYPE
GC COLUMN 1
GC COLUMN ID
GC COLUMN 2
GC COLUMN ID
PAGE
OF
•2E'
'AA'-'ZZ1
•HI1
CHARACTER
NUMERIC
CHARACTER
NUMERIC
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
10
22
27
28
33
34
39
40
45
46
51
52
-
-
-
-
—
—
-
-
-
—
-
-
-
-
-
—
3
5
7
9
21
26
27
32
33
38
39
44
45
50
51
52
3
2
2
2
12
5
1
5
1
5
1
5
1
5
1
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
EPA SAMPLE NO.
(1)
(1)
TCX
TCX
TCX (2)
TCX (2)
DCB
DCB
DCB
DCB
(1)
(1)
(2)
(2)
% RECOVERY
% RECOVERY FLAG
% RECOVERY
% RECOVERY FLAG
% RECOVERY
% RECOVERY FLAG
% RECOVERY
% RECOVERY FLAG
OTHER (1)
OTHER (2)
TOTAL OUT
FORMAT/CONTENTS
•2E'
•AA'-'ZZ1
•Dl1
NUMERIC
CHARACTER
NUMERIC
•*'/BLANK
NUMERIC
•*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
NUMERIC
NUMERIC
H-21
OLM01.0
-------
SOIL PESTICIDE SURROGATE RECOVERY - (FORM 2F)
HEADER RECORD 1 (HI)
FORM NUMBER
FORM SUFFIX
RECORD TYPE
GC COLUMN 1
GC COLUMN ID 1
GC COLUMN 2
GC COLUMN ID 2
PAGE
OF
1
4
6
8
18
22
32
36
38
-
-
-
-
-
-
-
—
-
3
5
7
17
21
31
35
37
39
3
2
2
10
4
10
4
2
2
•2F«
'AA'-'ZZ'
'HI1
CHARACTER
NUMERIC
CHARACTER
NUMERIC
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1 -
4 -
6 -
8 -
10 -
22 -
27 -
28 -
33 -
34 -
39 -
40 -
45 .
46 -
51 -
52 -
3
5
7
9
21
26
27
32
33
38
39
44
45
50
51
52
3
2
2
2
12
5
1
5
1
5
1
5
1
5
1
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
EPA SAMPLE NO.
TCX (1) % RECOVERY
TCX (1) % RECOVERY FLAG
TCX (2) % RECOVERY
TCX (2) % RECOVERY FLAG
DCS (1) % RECOVERY
DCB (1) % RECOVERY FLAG
DCB (2) % RECOVERY
DCB (2) % RECOVERY FLAG
OTHER (1)
OTHER (2)
TOTAL OUT
fc ORMAT/CONTENTS
'2F'
'AA'-'ZZ1
'Dl'
NUMERIC
CHARACTER
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
NUMERIC
'*•/BLANK
NUMERIC
NUMERIC
NUMERIC
H-22
OLM01.0
-------
FORM III FILE DESCRIPTION
(FORM 3)
H-23 OLM01.0
-------
WATER VOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
(FORM 3A)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
FORMAT/CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-19 12 EPA SAMPLE NO.
20-21 2 RPD: # OUTSIDE LIMITS
22-23 2 RPD: TOTAL
24-25 2 SPIKE RECOVERY: OUTSIDE
26-27 2 SPIKE RECOVERY: TOTAL
•3A'
'AA'-'ZZ1
'HI'
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
32
41
54
67
70
3
5
7
31
40
53
66
69
70
3
2
2
24
9
13
13
3
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
SPIKE ADDED
SAMPLE CONG.
(UG/L)
(UG/L)
MS CONG. (UG/L)
MS % RECOVERY
MS % RECOVERY FLAG
FORMAT/CONTENTS
'3A'
'AA'-'ZZ1
•Dl1
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
'*'/BLANK
DETAIL RECORD 1 (D2)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-31 24 COMPOUND
32-40 9 SPIKE ADDED (UG/L)
41-53 13 MSD CONC. (UG/L)
54-56 3 MSD % RECOVERY
57-57 1 MSD % RECOVERY FLAG
58-60 3 % RPD
61-61 1 % RPD OUT FLAG
FORMAT/CONTENTS
•3A'
'AA'-'ZZ'
•D2'
CHARACTER
NUMERIC
NUMERIC
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
H-24
OLM01.0
-------
SOIL VOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
(FORM 3B)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-19 12 EPA SAMPLE NO.
20-22 3 LEVEL
23-24 2 RPD: I OUTSIDE LIMITS
25-26 2 RPD: TOTAL
27-28 2 SPIKE RECOVERY: OUTSIDE
29-30 2 SPIKE RECOVERY: TOTAL
FORMAT/CONTENTS
«3B'
'AA'-'ZZ'
'HI'
CHARACTER
1 LOW»/'MED1
NUMERIC
NUMERIC
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
FORMAT/CONTENTS
1
4
6
8
32
41
54
67
70
-
-
—
-
-
—
-
—
-
3
5
7
31
40
53
66
69
70
3
2
2
24
9
13
13
3
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
SPIKE ADDED
SAMPLE CONG.
(UG/L)
(UG/KG)
MS CONG. (UG/KG)
MS % RECOVERY
MS % RECOVERY FLAG
•3B1
'AA'-'ZZ1
'Dl'
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
'*'/BLANK
DETAIL RECORD 1 (D2)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-31 24 COMPOUND
32-40 9 SPIKE ADDED (UG/L)
41-53 13 MSD CONC. (UG/KG)
54-56 3 MSD % RECOVERY
57-57 1 MSD % RECOVERY FLAG
58-60 3 % RPD
61-61 1 % RPD OUT FLAG
FORMAT/CONTENTS
•3B'
'AA'-'ZZ1
•D2'
CHARACTER
NUMERIC
NUMERIC
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
H-25
OLM01.0
-------
WATER SEMIVOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
(FORM 3C)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-19 12 EPA SAMPLE NO.
20-21 2 RPD: I OUTSIDE LIMITS
22-23 2 RPD: TOTAL
24-25 2 SPIKE RECOVERY: OUTSIDE
26-27 2 SPIKE RECOVERY: TOTAL
FORMAT/CONTENTS
«3C'
'AA'-'ZZ1
'HI1
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-31 24 COMPOUND
32-40 9 SPIKE ADDED (UG/L)
41 - 53 13 SAMPLE CONG. (UG/L)
54 - 66 13 MS CONC. (UG/L)
67-69 3 MS % RECOVERY
70-70 1 MS % RECOVERY FLAG
FORMAT/CONTENTS
•3C'
•AA'-'ZZ1
•Dl1
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
•*'/BLANK
DETAIL RECORD 1 (D2)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-31 24 COMPOUND
32-40 9 SPIKE ADDED (UG/L)
41-53 13 MSD CONC. (UG/L)
54-56 3 MSD % RECOVERY
57-57 1 MSD % RECOVERY FLAG
58-60 3 % RPD
61-61 1 % RPD OUT FLAG
FORMAT/CONTENTS
•3C'
•AA'-'ZZ1
•D2«
CHARACTER
NUMERIC
NUMERIC
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
H-26
OLM01.0
-------
SOIL SEMIVOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
(FORM 3D)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8 - 19 12 EPA SAMPLE NO.
20-22 3 LEVEL
23-24 2 RPD: # OUTSIDE LIMITS
25-26 2 RPD: TOTAL
27-28 2 SPIKE RECOVERY: OUTSIDE
29-30 2 SPIKE RECOVERY: TOTAL
FORMAT/CONTENTS
•3D1
'AA'-'ZZ1
•HI1
CHARACTER
•LOW'/'MED1
NUMERIC
NUMERIC
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
32
41
54
67
70
-
-
—
-
—
—
-
-
-
3
5
7
31
40
53
66
69
70
3
2
2
24
9
13
13
3
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
SPIKE ADDED (UG/L)
SAMPLE CONC. (UG/KG)
MS CONC. (UG/KG)
MS % RECOVERY
MS % RECOVERY FLAG
FORMAT/CONTENTS
•3D'
•AA'-'ZZ1
• Dl'
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
'*'/BLANK
DETAIL RECORD 1 (D2)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-31 24 COMPOUND
32-40 9 SPIKE ADDED (UG/L)
41-53 13 MSD CONC. (UG/KG)
54-56 3 MSD % RECOVERY
57-57 1 MSD % RECOVERY FLAG
58-60 3 % RPD
61-61 1 % RPD OUT FLAG
FORMAT/CONTENTS
•3D1
'AA'-'ZZ1
•D2'
CHARACTER
NUMERIC
NUMERIC
NUMERIC
'*'/BLANK
NUMERIC
' *'/BLANK
H-27
OLM01.0
-------
WATER PESTICIDE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
(FORM 3E)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-19 12 EPA SAMPLE NO.
20-21 2 RPD: # OUTSIDE LIMITS
22-23 2 RPD: TOTAL
24-25 2 SPIKE RECOVERY: OUTSIDE
26-27 2 SPIKE RECOVERY: TOTAL
FORMAT/CONTENTS
•3E1
'AA'-"ZZ'
•HI1
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
32
41
54
67
70
3
5
7
31
40
53
66
69
70
3
2
2
24
9
13
13
3
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
SPIKE ADDED
SAMPLE CONC.
(UG/L)
(UG/L)
MS CONC. (UG/L)
MS % RECOVERY
MS % RECOVERY FLAG
FORMAT/CONTENTS
'3E'
'AA'-'ZZ'
•Dl'
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
'*'/BLANK
DETAIL RECORD 1 (D2)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-31 24 COMPOUND
32-40 9 SPIKE ADDED (UG/L)
41-53 13 MSD CONC. (UG/L)
54-56 3 MSD % RECOVERY
57-57 1 MSD % RECOVERY FLAG
58-60 3 % RPD
61-61 1 % RPD OUT FLAG
FORMAT/CONTENTS
«3E'
'AA'-'ZZ1
•D2«
CHARACTER
NUMERIC
NUMERIC
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
H-28
OLM01.0
-------
SOIL PESTICIDE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
(FORM 3F)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-19 12 EPA SAMPLE NO.
20-21 2 RPD: # OUTSIDE LIMITS
22-23 2 RPD: TOTAL
24-25 2 SPIKE RECOVERY: OUTSIDE
26-27 2 SPIKE RECOVERY: TOTAL
FORMAT/CONTENTS
'3F'
'AA'-'ZZ1
•HI1
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
32
41
54
67
70
3
5
7
31
40
53
66
69
70
3
2
2
24
9
13
13
3
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
SPIKE ADDED
SAMPLE CONC.
(UG/L)
(UG/KG)
MS CONC. (UG/KG)
MS % RECOVERY
MS % RECOVERY FLAG
FORMAT/CONTENTS
•3F1
•AA'-'ZZ1
•Dl1
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
'*'/BLANK
DETAIL RECORD 1 (D2)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-31 24 COMPOUND
32-40 9 SPIKE ADDED (UG/L)
41 - 53 13 MSD CONC. (UG/KG)
54-56 3 MSD % RECOVERY
57-57 1 MSD % RECOVERY FLAG
58-60 3 % RPD
61-61 1 % RPD OUT FLAG
FORMAT/CONTENTS
'3F'
'AA'-'ZZ'
•D21
CHARACTER
NUMERIC
NUMERIC
NUMERIC
'*'/BLANK
NUMERIC
'*'/BLANK
H-29
OLM01.0
-------
FORM IV FILE DESCRIPTION
(FORM 4)
H-30 OLM01.0
-------
VOLATILE METHOD BLANK SUMMARY - (FORM 4A)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
EPA SAMPLE NUMBER
LAB FILE ID
LAB SAMPLE ID
DATE ANALYZED
TIME ANALYZED
GC COLUMN
GC COLUMN ID
HEATED PURGE
INSTRUMENT ID
PAGE
OF
1
4
6
8
20
34
46
54
58
68
72
73
83
85
-
—
—
-
-
-
-
-
—
—
-
-
-
-
3
5
7
19
33
45
53
57
67
71
72
82
84
86
3
2
2
12
14
12
8
4
10
4
1
10
2
2
FORMAT/CONTENTS
'4A'
•AA'-'ZZ1
'HI1
CHARACTER
CHARACTER
CHARACTER
MM/DD/YY
HHMM
CHARACTER
NUMERIC
•Y'/'N'
CHARACTER
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
10
22
34
48
—
-
—
—
-
-
-
—
3
5
7
9
21
33
47
51
3
2
2
2
12
12
14
4
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
EPA SAMPLE NO.
LAB SAMPLE ID
LAB FILE ID
TIME ANALYZED
FORMAT/CONTENTS
•4A'
'AA'-'ZZ1
•Dl'
NUMERIC 2
CHARACTER
CHARACTER
CHARACTER
HHMM
H-31
OLM01.0
-------
SEMIVOLATILE METHOD BLANK SUMMARY - (FORM 4B)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
EPA SAMPLE NUMBER
LAB FILE ID
LAB SAMPLE ID
INSTRUMENT ID
DATE EXTRACTED
MATRIX
DATE ANALYZED
LEVEL
TIME ANALYZED
PAGE
OF
1
4
6
8
20
34
46
56
64
69
77
80
84
86
-
-
-
—
-
—
—
-
-
-
-
-
-
-
3
5
7
19
33
45
55
63
68
76
79
83
85
87
3
2
2
12
14
12
10
8
5
8
3
4
2
2
FORMAT/CONTENTS
»4B'
'AA'-'ZZ'
•HI1
CHARACTER
CHARACTER
CHARACTER
CHARACTER
MM/DD/YY
'SOIL' /'WATER'
MM/DD/YY
'LOW'/'MED'
HHMM
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
10
22
34
48
-
-
-
-
-
-
-
-
3
5
7
9
21
33
47
55
3
2
2
2
12
12
14
8
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
EPA SAMPLE NO.
LAB SAMPLE ID
LAB FILE ID
DATE ANALYZED
FORMAT/CONTENTS
«4B'
•AA'-'ZZ1
•Dl1
NUMERIC 2
CHARACTER
CHARACTER
CHARACTER
MM/DD/YY
H-32
OLM01.0
-------
PESTICIDE METHOD BLANK SUMMARY - (FORM 4C)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
20
32
46
51
55
56
64
72
80
84
88
98
108
118
122
132
136
138
-
-
—
—
-
-
-
-
—
-
-
-
-
-
-
-
-
-
-
-
-
-
3
5
7
19
31
45
50
54
55
63
71
79
83
87
97
107
117
121
131
135
137
139
3
2
2
12
12
14
5
4
1
8
8
8
4
4
10
10
10
4
10
4
2
2
FORM NUMBER
FORM SUFFIX
RECORD TYPE
EPA SAMPLE NUMBER
LAB SAMPLE ID
LAB FILE ID
MATRIX
EXTRACTION
SULFUR CLEANUP
DATE EXTRACTED
DATE ANALYZED (1)
DATE ANALYZED (2)
TIME ANALYZED (1)
TIME ANALYZED (2)
INSTRUMENT ID (1)
INSTRUMENT ID (2)
GC COLUMN (1)
GC COLUMN ID (1)
GC COLUMN (2)
GC COLUMN ID (2)
PAGE
OF
FORMAT/CONTENTS
i4Ci
'AA'-'ZZ1
•HI'
CHARACTER
CHARACTER
CHARACTER
•SOIL'/'WATER1
CHARACTER
'Y'/'N1
MM/DD/YY
MM/DD/YY
MM/DD/YY
HHMM
HHMM
CHARACTER
CHARACTER
CHARACTER
NUMERIC
CHARACTER
NUMERIC
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-92 SEQUENCE NUMBER
10 - 21 12 EPA SAMPLE NO.
22 - 33 12 LAB SAMPLE ID
34-41 8 DATE ANALYZED 1
42-49 8 DATE ANALYZED 2
FORMAT/CONTENTS
•4C'
'AA'-'ZZ1
• Dl'
NUMERIC
CHARACTER
CHARACTER
MM/DD/YY
MM/DD/YY
H-33
OLM01.0
-------
FORM V FILE DESCRIPTION
(FORM 5)
H_34 OLM01.0
-------
VOLATILE ORGANIC INSTRUMENT PERFORMANCE CHECK - (FORM5A)
BROMOFLUOROBENZENE (BFB)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
22
30
40
44
54
58
59
61
-
-
—
-
-
-
—
-
-
—
-
-
3
5
7
21
29
39
43
53
57
58
60
62
3
2
2
14
8
10
4
10
4
1
2
2
FORM NUMBER
FORM SUFFIX
RECORD TYPE
LAB FILE ID
BFB INJECTION DATE
INSTRUMENT ID
BFB INJECTION TIME
GC COLUMN
GC COLUMN ID
HEATED PURGE
PAGE
OF
FORMAT/CONTENTS
•5A1
•AA'-'ZZ1
•HI1
CHARACTER
MM/DD/YY
CHARACTER
HHMM
CHARACTER
NUMERIC
•Y'/'N'
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
FORMAT/CONTENTS
1 -
4 -
6 -
8 -
11 -
16 -
3
5
7
10
15
20
3
2
2
3
5
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
M/E
% RELATIVE ABUNDANCE
% MASS (WHERE APPLICABLE)
•5A'
•AA'-'ZZ1
NUMERIC
NUMERIC
NUMERIC
DETAIL RECORD 2 (D2)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
10
22
34
48
56
-
-
-
-
-
-
-
-
-
3
5
7
9
21
33
47
55
59
3
2
2
2
12
12
14
8
4
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
EPA SAMPLE NO.
LAB SAMPLE ID
LAB FILE ID
DATE ANALYZED
TIME ANALYZED
FORMAT/CONTENTS
'5A'
•AA'-'ZZ1
• D2'
NUMERIC
CHARACTER
CHARACTER
CHARACTER
MM/DD/YY
HHMM
H-35
OLM01.0
-------
SEMIVOLATILE ORGANIC INSTRUMENT PERFORMANCE CHECK - (FORM5B)
DECAFLUOROTRIPHENYLPHOSPHINE (DFTPP)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
22
30
40
44
46
-
-
-
-
-
-
-
-
-
3
5
7
21
29
39
43
45
47
3
2
2
14
8
10
4
2
2
FORM NUMBER
FORM SUFFIX
RECORD TYPE
LAB FILE ID
DFTPP INJECTION DATE
INSTRUMENT ID
DFTPP INJECTION TIME
PAGE
OF
FORMAT/CONTENTS
•5B'
'AA'-'ZZ'
'HI'
CHARACTER
MM/DD/YY
CHARACTER
HHMM
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
FORMAT/CONTENTS
1 -
4 -
6 -
8 -
11 -
17 -
3
5
7
10
16
21
3
2
2
3
6
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
M/E
% RELATIVE ABUNDANCE
'5B'
'AA'-
'ZZ'
• Dl'
NUMERIC
NUMERIC
% MASS (WHERE APPLICABLE) NUMERIC
DETAIL RECORD 2 (D2)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-9 2 SEQUENCE NUMBER
10 - 21 12 EPA SAMPLE NO.
22-33 12 LAB SAMPLE ID
34 - 47 14 LAB FILE ID
48-55 8 DATE ANALYZED
56-59 4 TIME ANALYZED
FORMAT/CONTENTS
«5B'
'AA'-'ZZ1
•D21
NUMERIC
CHARACTER
CHARACTER
CHARACTER
MM/DD/YY
HHMM
H-36
OLM01.0
-------
FORM VI FILE DESCRIPTION
(FORM 6)
H-37 OLM01.0
-------
VOLATILE ORGANICS INITIAL CALIBRATION DATA - (FORM 6A)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
18
26
34
35
39
43
53
57
71
85
99
113
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
3
5
7
17
25
33
34
38
42
52
56
70
84
98
112
126
3
2
2
10
8
8
1
4
4
10
4
14
14
14
14
14
FORM NUMBER
FORM SUFFIX
RECORD TYPE
INSTRUMENT ID
CALIBRATION DATE 1
CALIBRATION DATE 2
HEATED PURGE
CALIBRATION TIME 1
CALIBRATION TIME 2
GC COLUMN
GC COLUMN ID
RRF10 LAB FILE ID
RRF20 LAB FILE ID
RRF50 LAB FILE ID
RRF100 LAB FILE ID
RRF200 LAB FILE ID
FORMAT/CONTENTS
«6A'
'AA'-'ZZ1
•HI1
CHARACTER
MM/DD/YY
MM/DD/YY
'Y'/'N1
HHMM
HHMM
CHARACTER
NUMERIC
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1 -
4 -
6 -
8 -
35 -
40 -
45 -
50 -
55 -
60 -
65 -
3
5
7
34
39
44
49
54
59
64
69
3
2
2
27
5
5
5
5
5
5
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
RRF10
RRF20
RRF50
RRF100
RRF200
AVERAGE RRF
% RSD
FORMAT/CONTENTS
'6A1
'AA'-'ZZ'
•Dl1
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
H-38
OLM01.0
-------
SEMIVOLATILE ORGANICS INITIAL CALIBRATION DATA - (FORM 6B)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
18
26
34
38
42
56
70
84
98
3
5
7
- 17
- 25
- 33
- 37
- 41
- 55
- 69
- 83
- 97
- Ill
3
2
2
10
8
8
4
4
14
14
14
14
14
FORM NUMBER
FORM SUFFIX
RECORD TYPE
INSTRUMENT ID
CALIBRATION DATE 1
CALIBRATION DATE 2
CALIBRATION TIME 1
CALIBRATION TIME 2
RRF20 LAB FILE ID
RRF50 LAB FILE ID
RRF80 LAB FILE ID
RRF120 LAB FILE ID
RRF160 LAB FILE ID
FORMAT/CONTENTS
•6B1
•AA'-'ZZ'
•HI1
CHARACTER
MM/DD/YY
MM/DD/YY
HHMM
HHMM
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
DETAIL RECORD 1 (Dl)
COLUMN (S) LENGTH CONTENTS
1 -
4 -
6 -
8 -
35 -
40 -
45 -
50 -
55 -
60 -
65 -
3
5
7
34
39
44
49
54
59
64
69
3
2
2
27
5
5
5
5
5
5
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
RRF20
RRF50
RRF80
RRF120
RRF160
AVERAGE RRF
% RSD
FORMAT/CONTENTS
«6B«
'AA'-'ZZ'
•Dl'
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
H-39
OLM01.0
-------
SEMIVOLATILE ORGANIC INITIAL CALIBRATION DATA - (FORM 6C)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
18
26
34
38
42
56
70
84
98
-
-
-
-
-
-
-
-
-
-
-
-
-
3
5
7
17
25
33
37
41
55
69
83
97
111
3
2
2
10
8
8
4
4
14
14
14
14
14
FORM NUMBER
FORM SUFFIX
RECORD TYPE
INSTRUMENT ID
CALIBRATION DATE 1
CALIBRATION DATE 2
CALIBRATION TIME 1
CALIBRATION TIME 2
RRF20 LAB FILE ID
RRF50 LAB FILE ID
RRF80 LAB FILE ID
RRF120 LAB FILE ID
RRF160 LAB FILE ID
FORMAT/CONTENTS
'6C»
'AA'-'ZZ1
•HI1
CHARACTER
MM/DD/YY
MM/DD/YY
HHMM
HHMM
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
35
40
45
50
55
60
65
-
-
-
-
-
-
—
—
-
—
—
3
5
7
34
39
44
49
54
59
64
69
3
2
2
27
5
5
5
5
5
5
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
RRF20
RRF50
RRF80
RRF120
RRF160
AVERAGE RRF
% RSD
FORMAT/CONTENTS
• 6C'
•AA'-'ZZ'
•Dl1
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
H-40
OLM01.0
-------
PESTICIDES INITIAL CALIBRATION OF SINGLE COMPONENT ANALYTES -
(FORM 6D)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
18
23
28
33
43
47
55
—
-
-
-
-
-
-
-
-
-
-
3
5
7
17
22
27
32
42
46
54
62
3
2
2
10
5
5
5
10
4
8
8
FORM NUMBER
FORM SUFFIX
RECORD TYPE
INSTRUMENT ID
LOW LEVEL
MID LEVEL
HIGH LEVEL
GC COLUMN
GC COLUMN ID
DATE ANALYZED
DATE ANALYZED
FORMAT/CONTENTS
•6D'
•AA'-'ZZ1
'HI1
CHARACTER
NUMERIC
NUMERIC
NUMERIC
CHARACTER
NUMERIC
MM/DD/YY
MM/DD/YY
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
35
40
45
50
55
60
-
—
—
-
-
-
-
-
—
-
3
5
7
34
39
44
49
54
59
64
3
2
2
27
5
5
5
5
5
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
RT OF LOW STANDARD
RT OF MID STANDARD
RT OF HIGH STANDARD
MEAN RT
RT WINDOW LOWER LIMIT
RT WINDOW UPPER LIMIT
FORMAT/CONTENTS
•6D1
'AA'-'ZZ'
•Dl1
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
H-41
OLM01.0
-------
PESTICIDES INITIAL CALIBRATION OF SINGLE COMPONENT ANALYTES -
(FORM 6E)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
18
23
28
33
43
47
55
-
-
-
-
-
-
-
-
-
-
-
3
5
7
17
22
27
32
42
46
54
62
3
2
2
10
5
5
5
10
4
8
8
FORM NUMBER
FORM SUFFIX
RECORD TYPE
INSTRUMENT ID
LOW LEVEL
MID LEVEL
HIGH LEVEL
GC COLUMN
GC COLUMN ID
DATE ANALYZED
DATE ANALYZED
FORMAT/CONTENTS
'6E'
'AA'-'ZZ'
'HI'
CHARACTER
NUMERIC
NUMERIC
NUMERIC
CHARACTER
NUMERIC
MM/DD/YY
MM/DD/YY
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
35
45
55
65
75
-
-
-
-
-
—
-
-
-
3
5
7
34
44
54
64
74
79
3
2
2
27
10
10
10
10
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
LOW CAL. FACTOR
MID CAL. FACTOR
HIGH CAL. FACTOR
MEAN CAL. FACTORS
% RSD
FORMAT/CONTENTS
'6E(
'AA'-'ZZ'
'Dl'
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
H-42
OLM01.0
-------
PESTICIDES INITIAL CALIBRATION OF MULTICOMPONENT ANALYTES -
(FORM 6F)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
18
26
34
44
-
-
-
-
-
-
-
-
3
5
7
17
25
33
43
47
3
2
2
10
8
8
10
4
FORM NUMBER
FORM SUFFIX
RECORD TYPE
INSTRUMENT ID
DATE ANALYZED
DATE ANALYZED
GC COLUMN
GC COLUMN ID
FORMAT/CONTENTS
• 6F'
'AA'-'ZZ'
'HI'
CHARACTER
MM/DD/YY
MM/DD/YY
CHARACTER
NUMERIC
DETAIL RECORD 1 fDl)
COLUMN(S) LENGTH CONTENTS
1
4 -
6 -
8 -
35 -
43 -
44 -
49 -
54 -
59 -
3
5
7
34
42
43
48
53
58
68
3
2
2
27
8
1
5
5
5
10
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
AMOUNT
PEAK
RT
RT WINDOW LOWER LIMIT
RT WINDOW UPPER LIMIT
CALIBRATION FACTOR
FORMAT/CONTENTS
•6F'
•AA'-'ZZ'
•Dl'
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
H-43
OLM01.0
-------
PESTICIDES RESOLUTION CHECK SUMMARY (FORM 6G)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
GC COLUMN 1
GC COLUMN 1 ID
INSTRUMENT ID 1
EPA SAMPLE NO. (STD 1)
LAB SAMPLE ID 1
DATE ANALYZED 1
TIME ANALYZED 1
GC COLUMN 2
GC COLUMN 2 ID
INSTRUMENT ID 2
EPA SAMPLE NO. (STD 2)
LAB SAMPLE ID 2
DATE ANALYZED 2
TIME ANALYZED 2
1
4
6
8
18
22
32
44
56
64
68
78
82
92
104
116
124
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
•
3
5
7
17
21
31
43
55
63
67
77
81
91
103
115
123
127
3
2
2
10
4
10
12
12
8
4
10
4
lu
12
12
8
4
FORMAT/CONTENTS
•6G«
•AA'-'ZZ'
•HI1
CHARACTER
NUMERIC
CHARACTER
CHARACTER
CHARACTER
MM/DD/YY
HHMM
CHARACTER
NUMERIC
CHARACTER
CHARACTER
CHARACTER
MM/DD/YY
HHMM
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
9
36
41
-
-
-
-
-
-
-
3
5
7
8
35
40
45
3
2
2
1
27
5
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
ANALYTE
RT
RESOLUTION (%)
DETAIL RECORD 2 (D2)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
9
36
41
-
-
-
-
-
-
-
3
5
7
8
35
40
45
3
2
2
1
27
5
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
ANALYTE
RT
RESOLUTION (%)
FORMAT/CONTENTS
'6G'
'AA'-'ZZ'
•Dl1
CHARACTER
CHARACTER
NUMERIC
NUMERIC
FORMAT/CONTENTS
'6G'
'AA'-'ZZ1
•D2«
CHARACTER
CHARACTER
NUMERIC
NUMERIC
H-44
OLM01.0
-------
FORM VII FILE DESCRIPTION
(FORM 7)
H-45 OLM01.0
-------
VOLATILE CONTINUING CALIBRATION SUMMARY - (FORM 7A)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
18
26
30
44
52
60
61
65
69
79
-
-
-
-
-
-
-
-
-
-
-
-
-
-
3
5
7
17
25
29
43
51
59
60
64
68
78
82
3
2
2
10
8
4
14
8
8
1
4
4
10
4
FORM NUMBER
FORM SUFFIX
RECORD TYPE
INSTRUMENT ID
CALIBRATION DATE
CALIBRATION TIME
LAB FILE ID
INIT. CALIB. DATE 1
INIT. CALIB. DATE 2
HEATED PURGE
INIT. CALIB. TIME 1
INIT. CALIB. TIME 2
GC COLUMN
GC COLUMN ID
FORMAT/CONTENTS
•7A1
'AA'-'ZZ1
•HI1
CHARACTER
MM/DD/YY
HHMM
CHARACTER
MM/DD/YY
MM/DD/YY
' Y ' / ' N"
HHMM
HHMM
CHARACTER
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
35
40
45
50
55
-
-
-
-
-
-
-
-
-
3
5
7
34
39
44
49
54
58
3
2
2
27
5
5
5
5
4
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
AVERAGE RRF
RRF50
MIN RRF
% D
MAX % D
FORMAT/CONTENTS
«7A'
•AA'-'ZZ1
•Dl'
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
H-46
OLM01.0
-------
SEMIVOLATILE CONTINUING CALIBRATION SUMMARY - (FORM 7B)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
18
26
30
44
52
60
64
-
-
-
-
-
-
—
-
-
-
-
3
5
7
17
25
29
43
51
59
63
67
3
2
2
10
8
4
14
8
8
4
4
FORM NUMBER
FORM SUFFIX
RECORD TYPE
INSTRUMENT ID
CALIBRATION DATE
CALIBRATION TIME
LAB FILE ID
INIT. CALIB. DATE 1
INIT. CALIB. DATE 2
INIT. CALIB. TIME 1
INIT. CALIB. TIME 2
FORMAT/CONTENTS
•7B1
'AA'-'ZZ1
'HI'
CHARACTER
MM/DD/YY
HHMM
CHARACTER
MM/DD/YY
MM/DD/YY
HHMM
HHMM
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-34 27 COMPOUND
35-39 5 AVERAGE RRF
40-44 5 RRF50
45-49 5 MIN RRF
50-54 5 % D
55-58 4 MAX % D
FORMAT/CONTENTS
•7B1
•AA'-'ZZ1
'Dl'
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
H-47
OLM01.0
-------
SEMIVOLATILE CONTINUING CALIBRATION SUMMARY - (FORM 7C)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1 -
4 -
6 -
8 -
18 -
26 -
30 -
44 -
52 -
60 -
64 -
3
5
7
17
25
29
43
51
59
63
67
3
2
2
10
8
4
14
8
8
4
4
FORM NUMBER
FORM SUFFIX
RECORD TYPE
INSTRUMENT ID
CALIBRATION DATE
CALIBRATION TIME
LAB FILE ID
INIT. CALIB. DATE
INIT. CALIB. DATE
INIT. CALIB. TIME
INIT. CALIB. TIME 2
FORMAT/CONTENTS
•7C1
'AA'-'ZZ'
'HI1
CHARACTER
MM/DD/YY
HHMM
CHARACTER
MM/DD/YY
MM/DD/YY
HHMM
HHMM
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-34 27 COMPOUND
35-39 5 AVERAGE RRF
40-44 5 RRF50
45-49 5 MIN RRF
50-54 5 % D
55-58 4 MAX % D
FORMAT/CONTENTS
'7C1
'AA'-'ZZ'
•Dl«
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
H-48
OLM01.0
-------
PESTICIDES CALIBRATION VERIFICATION SUMMARY -
(FORM 7D)
HEADER RECORD V (HI)
COLUMN(S) LENGTH CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
GC COLUMN
GC COLUMN ID
INIT. CALIB. DATE 1
INIT. CALIB. DATE 2
EPA SAMPLE NO. (PIBLK)
LAB SAMPLE ID. (PIBLK)
EPA SAMPLE NO. (PEM)
LAB SAMPLE ID. (PEM)
DATE ANALYZED (PIBLK)
DATE ANALYZED (PEM)
TIME ANALYZED (PIBLK)
TIME ANALYZED (PEM)
4,4'-DDT % BREAKDOWN (1)
ENDRIN % BREAKDOWN (1)
COMBINED % BREAKDOWN (1)
1
4
6
8
18
22
30
38
50
62
74
86
94
102
106
110
115
120
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
3
5
7
17
21
29
37
49
61
73
85
93
101
105
109
114
119
124
3
2
2
10
4
8
8
12
12
12
12
8
8
4
4
5
5
5
FORMAT/CONTENTS
• 7D1
'AA'-'ZZ'
•HI1
CHARACTER
NUMERIC
MM/DD/YY
MM/DD/YY
CHARACTER
CHARACTER
CHARACTER
CHARACTER
MM/DD/YY
MM/DD/YY
HHMM
HHMM
NUMERIC
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
35
40
45
50
58
66
-
-
-
-
-
-
-
-
-
-
3
5
7
34
39
44
49
57
65
70
3
2
2
27
5
5
5
8
8
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
RT
RT LOWER LIMIT
RT UPPER LIMIT
CALCULATED AMOUNT
NOMINAL AMOUNT"
RPD
FORMAT/CONTENTS
•7D«
'AA'-'ZZ1
'Dl1
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
H-49
OLM01.0
-------
PESTICIDES CALIBRATION VERIFICATION SUMMARY
FORM 7E)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
GC COLUMN
GC COLUMN ID
INIT. CALIB.
INIT. CALIB.
EPA SAMPLE
LAB SAMPLE
EPA SAMPLE
LAB SAMPLE
EPA SAMPLE
LAB SAMPLE
DATE ANALYZED
DATE ANALYZED
DATE ANALYZED
TIME ANALYZED
TIME ANALYZED
TIME ANALYZED
1
4
6
8
18
22
30
38
50
62
74
86
98
110
118
126
134
138
142
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
3
5
7
17
21
29
37
49
61
73
85
97
109
117
125
133
137
141
145
3
2
2
10
4
8
8
12
12
12
12
12
12
8
8
8
4
4
4
FORMAT/CONTENTS
•7E1
'AA'-'ZZ1
1
:D
I. DATE 1
I. DATE 2
NO. (PIBLK)
ID. (PIBLK)
NO. (INDA)
ID. (INDA)
NO. (INDB,
ID. (INDB) *
ED (PIBLK)
ED (INDA)
ED (INDB)
ED (PIBLK)
ED (INDA)
ED (INDB)
'HI1
CHARACTER
NUMERIC
MM/DD/YY
MM/DD/YY
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
MM/DD/YY
MM/DD/YY
MM/DD/YY
HHMM
HHMM
HHMM
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-34 27 COMPOUND
35-39 5 RT
40-44 5 RT LOWER LIMIT
45-49 5 RT UPPER LIMIT
50-57 8 CALCULATED AMOUNT
58-65 8 NOMINAL AMOUNT
66-70 5 RPD
FORMAT/CONTENTS
•7E'
'AA'-'ZZ1
•Dl'
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
H-50
OLM01.0
-------
DETAIL RECORD 2 (D2)
COLUMN(S) LENGTH CONTENTS FORMAT/CONTENTS
1-3 3 FORM NUMBER ' 7E'
4-5 2 FORM SUFFIX 'AA'-'ZZ1
6-7 2 RECORD TYPE 'D21
8 - 34 27 COMPOUND CHARACTER
35-39 5 RT NUMERIC
40-44 5 RT LOWER LIMIT NUMERIC
45-49 5 RT UPPER LIMIT NUMERIC
50-57 8 CALCULATED AMOUNT NUMERIC
58-65 8 NOMINAL AMOUNT NUMERIC
66-70 5 RPD NUMERIC
H-51 OLM01.0
-------
FORM VIII FILE DESCRIPTIOH
(FORM 8)
H-52 OLM01.0
-------
VOLATILE INTERNAL STANDARD AREA AND RT SUMMARY - (FORM 8A)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
22
30
40
44
54
58
59
61
-
-
-
—
-
—
—
-
—
—
-
—
3
5
7
21
29
39
43
53
57
58
60
62
3
2
2
14
8
10
4
10
4
1
2
2
FORM NUMBER
FORM SUFFIX
RECORD TYPE
LAB FILE ID (STANDARD)
DATE ANALYZED
INSTRUMENT ID
TIME ANALYZED
GC COLUMN
GC COLUMN ID
HEATED PURGE
PAGE
OF
FORMAT/CONTENTS
•8A1
•AA'-'ZZ'
•HI'
CHARACTER
MM/DD/YY
CHARACTER
HHMM
CHARACTER
NUMERIC
•Y'/'N'
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
3 FORM NUMBER
2 FORM SUFFIX
2 RECORD TYPE
11 ENTRY TYPE
8 IS1 (BCM) AREA
5 IS1 (BCM) RT
8 IS2 (DFB) AREA
5 IS2 (DFB) RT
8 IS3 (CBZ) AREA
5 IS3 (CBZ) RT
1 -
4 -
6 -
8 -
19 -
27 -
32 -
40 -
45 -
53 -
3
5
7
18
26
31
39
44
52
57
FORMAT/CONTENTS
•8A1
•AA'-'ZZ1
•Dl1
'12 HOUR STD1/
•UPPER LIMIT1/
•LOWER LIMIT1
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
H-53
OLM01.0
-------
DETAIL RECORD 2 (D2)
COLUMN(S) LENGTH CONTENTS FORMAT/CONTENTS
1-3 3 FORM NUMBER '8A'
4-5 2 FORM SUFFIX 'AA'-'ZZ1
6-7 2 RECORD TYPE »D2'
8-9 2 SEQUENCE NUMBER NUMERIC
10 - 21 12 EPA SAMPLE NO. CHARACTER
22 - 29 8 IS1 (BCM) AREA NUMERIC
30-30 1 IS1 (BCM) AREA FLAG BLANK / '*'
31-35 5 IS1 (BCM) RT NUMERIC
36-36 1 IS1 (BCM) RT FLAG BLANK / •*•
37-44 8 IS2 (DFB) AREA NUMERIC
45-45 1 IS2 (DFB) AREA FLAG BLANK / '*'
46-50 5 IS2 (DFB) RT NUMERIC
51-51 1 . IS2 (DFB) RT FLAG BLANK / '*'
52-59 8 IS3 (CBZ) AREA NUMERIC
60-60 1 IS3 (CBZ) AREA FLAG BLANK / •*•
61-65 5 IS3 (CBZ) RT NUMERIC
66-66 1 IS3 (CBZ) RT FLAG BLANK / '*'
H-54 OLM01.0
-------
SEMIVOLATILE INTERNAL STANDARD AREA AND RT SUMMARY - (FORM SB)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS FORMAT/CONTENTS
1-3 3 FORM NUMBER '8B1
4-5 2 FORM SUFFIX 'AA'-'ZZ'
6-7 2 RECORD TYPE 'HI1
8-21 14 LAB FILE ID (STANDARD) CHARACTER
22-29 8 DATE ANALYZED MM/DD/YY
30 - 39 10 INSTRUMENT ID CHARACTER
40-43 4 TIME ANALYZED HHMM
44-45 2 PAGE NUMERIC
46-47 2 OF NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS FORMAT/CONTENTS
1-3 3 FORM NUMBER »8B»
4-5 2 FORM SUFFIX 'AA'-'ZZ1
6-7 2 RECORD TYPE 'Dl1
8-18 11 ENTRY TYPE '12 HOUR STD1/
•UPPER LIMIT'/
•LOWER LIMIT1
19-26 8 IS1 (DCB) AREA NUMERIC
27-31 5 IS1 (DCB) RT NUMERIC
32-39 8 IS2 (NPT) AREA NUMERIC
40-44 5 IS2 (NPT) RT NUMERIC
45-52 8 IS3 (ANT) AREA NUMERIC
53-57 5 IS3 (ANT) RT NUMERIC
H-55 OLM01.0
-------
DETAIL RECORD 2 (D2)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-9 2 SEQUENCE NUMBER
10 - 21 12 EPA SAMPLE NO.
22-29 8 IS1 (DCS) AREA
30-30 1 IS1 (DCB) AREA FLAG
31-35 5 IS1 (DCB) RT
36-36 1 IS1 (DCB) RT FLAG
37-44 8 IS2 (NPT) AREA
45-45 1 IS2 (NPT) AREA FLAG
46-50 5 IS2 (NPT) RT
51-51 1 IS2 (NPT) RT FLAG
52-59 3 IS3 (ANT) AREA
60-60 1 IS3 (ANT) AREA FLAG
61-65 5 IS3 (ANT) RT
66-66 1 IS3 (ANT) RT FLAG
FORMAT/CONTENTS
•8B'
'AA'-'ZZ1
•D21
NUMERIC
CHARACTER
NUMERIC
BLANK: / •*•
NUMERIC
BLANK / '*•
NUMERIC
BLANK / '*'
NUMERIC
BLANK / •*•
NUMERIC
BLANK / '*•
NUMERIC
BLANK / '*•
H-56
OLM01.0
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SEMIVOLATILE INTERNAL STANDARD AREA AND RT SUMMARY - (FORM 8C)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
22
30
40
44
46
-
-
-
-
—
-
-
-
-
3
5
7
21
29
39
43
45
47
3
2
2
14
8
10
4
2
2
FORM NUMBER
FORM SUFFIX
RECORD TYPE
LAB FILE ID (STANDARD)
DATE ANALYZED
INSTRUMENT ID
TIME ANALYZED
PAGE
OF
FORMAT/CONTENTS
•8C1
'AA'-'ZZ'
'HI1
CHARACTER
MM/DD/YY
CHARACTER
HHMM
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-18 11 ENTRY TYPE
19-26 8 IS4 (PHN) AREA
27-31 5 IS4 (PHN) RT
32-39 8 IS5 (CRY) AREA
40-44 5 IS5 (CRY) RT
45-52 8 IS6 (PRY) AREA
53-57 5 IS6 (PRY) RT
FORMAT/CONTENTS
•8C'
'AA'-'ZZ1
•Dl'
•12 HOUR STD1/
•UPPER LIMIT'/
•LOWER LIMIT'
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
H-57
OLM01.0
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DETAIL RECORD 2 (D2)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-9 2 SEQUENCE NUMBER
10 - 21 12 EPA SAMPLE NO.
22-29 8 IS4 (PHN) AREA
30-30 1 IS4 (PHN) AREA FLAG
31-35 5 IS4 (PHN) RT
36-36 1 IS4 (PHN) RT FLAG
37-44 8 IS5 (CRY) AREA
45-45 1 IS5 (CRY) AREA FLAG
46-50 5 IS5 (CRY) RT
51-51 1 IS5 (CRY) RT FLAG
52-59 8 IS6 (PRY) AREA
60-60 1 IS6 (PRY) AREA FLAG
61-65 5 IS6 (PRY) RT
66-66 1 IS6 (PRY) RT FLAG
FORMAT/CONTENTS
•8C«
•AA'-'ZZ1
«D2«
NUMERIC
CHARACTER
NUMERIC
BLANK / '*'
NUMERIC
BLANK / '*'
NUMERIC
BLANK / '*'
NUMERIC
BLANK / '*'
NUMERIC
BLANK / '*•
NUMERIC
BLANK / •*•
H-58
OLM01.0
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PESTICIDE ANALYTICAL SEQUENCE - (FORM 8D)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
GC COLUMN
GC COLUMN ID
INIT. CALIB. DATE 1
INIT. CALIB. DATE 2
INSTRUMENT ID
MEAN RT (TCX)
MEAN RT (DCB)
1 -
4 -
6 -
8 -
18 -
22 -
30 -
38 -
48 -
53 -
3
5
7
17
21
29
37
47
52
57
3
2
2
10
4
8
8
10
5
5
FORMAT/CONTENTS
•8D1
'AA'-'ZZ1
•HI'
CHARACTER
NUMERIC
MM/DD/YY
MM/DD/YY
CHARACTER
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
10
22
34
42
46
51
52
57
-
—
-
—
—
-
—
-
-
-
-
-
3
5
7
9
21
33
41
45
50
51
56
57
3
2
2
2
12
12
8
4
5
1
5
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
EPA SAMPLE NUMBER
LAB SAMPLE ID
DATE ANALYZED
TIME ANALYZED
TCX RT
TCX RT FLAG
DCB RT
DCB RT FLAG
FORMAT/CONTENTS
'8D»
'AA'-'ZZ'
•Dl1
NUMERIC
CHARACTER
CHARACTER
MM/DD/YY
HHMM
NUMERIC
CHARACTER
NUMERIC
CHARACTER
H-59
OLM01.0
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FORM IX FILE DESCRIPTION
(FORM 9)
H-60 OIM01
-------
PESTICIDE FLORISIL CARTRIDGE CHECK - (FORM 9A)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-17 10 FLOR. CART. LOT NO.
18-25 8 DATE OF ANALYSIS
26 - 35 10 GC COLUMN 1
36-39 4 GC COLUMN 1 ID
40 - 49 10 GC COLUMN 2
50-53 4 GC COLUMN 2 ID
54-55 2 PAGE
56-57 2 OF
FORMAT/CONTENTS
'9A1
'AA'-'ZZ'
'HI1
CHARACTER
MM/DD/YY
CHARACTER
NUMERIC
CHARACTER
NUMERIC
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
35
43
51
56
57
—
-
-
—
—
—
—
-
-
3
5
7
34
42
50
55
56
62
3
2
2
27
8
8
5
1
6
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
SPIKE ADDED
SPIKE RECOVERED
% REC
% REC FLAG
QC LIMIT
FORMAT/CONTENTS
'9A»
•AA'-'ZZ1
•Dl1
CHARACTER
NUMERIC
NUMERIC
NUMERIC
CHARACTER
•80-110'
DETAIL RECORD 2 (D2)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-9 2 SEQUENCE NUMBER
10-21 12 EPA SAMPLE NUMBER
22 - 33 12 LAB SAMPLE ID
34-41 8 DATE ANALYZED 1
42-49 8 DATE ANALYZED 2
FORMAT/CONTENTS
•9A»
•AA'-'ZZ'
•D2»
NUMERIC
CHARACTER
CHARACTER
MM/DD/YY
MM/DD/YY
H-61
OLM01.0
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PESTICIDE GPC CALIBRATION - (FORM 9B)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-17 10 GPC COLUMN
18-25 8 CALIBRATION DATE
26 - 35 10 GC COLUMN 1
36-39 4 GC COLUMN 1 ID
40 - 49 10 GC COLUMN 2
50-53 4 GC COLUMN 2 ID
54-55 2 PAGE
56-57 2 OF
FORMAT/CONTENTS
•9B'
'AA'-'ZZ'
•HI1
CHARACTER
MM/DD/YY
CHARACTER
NUMERIC
CHARACTER
NUMERIC
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1
4
6
8
35
43
51
56
57
-
-
-
-
—
-
-
-
-
3
5
7
34
42
50
55
56
62
3
2
2
27
8
8
5
1
6
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
SPIKE ADDED
SPIKE RECOVERED
% REC
% REC FLAG
QC LIMIT
FORMAT/CONTENTS
'9B'
'AA'-'ZZ1
'Dl1
CHARACTER
NUMERIC
NUMERIC
NUMERIC
CHARACTER
'80-110'
DETAIL RECORD 2 (D2)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-9 2 SEQUENCE NUMBER
10-21 12 EPA SAMPLE NUMBER
22 - 33 12 LAB SAMPLE ID
34-41 8 DATE ANALYZED 1
42-49 8 DATE ANALYZED 2
FORMAT/CONTENTS
«9B»
'AA'-'ZZ1
•D2'
NUMERIC
CHARACTER
CHARACTER
MM/DD/YY
MM/DD/YY
H-62
OLM01.0
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FORM X FILE DESCRIPTION
(FORM 10)
H-63 OLM01.0
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PESTICIDE IDENTIFICATION SUMMARY FOR SINGLE COMPONENT ANALYTES
(FORM 10A)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-19 12 EPA SAMPLE NO.
20 - 31 12 LAB SAMPLE ID
32-39 8 DATE ANALYZED
40-47 8 DATE ANALYZED
48 - 57 10 INSTRUMENT ID
58-67 10 INSTRUMENT ID
68 - 77 10 GC COLUMN 1
78-81 4 GC COLUMN 1
82 - 91 10 GC COLUMN 2
92-95 4 GC COLUMN 2
96-97 2 PAGE
98-99 2 OF
1
2
1
2
ID
ID
FORMAT/CONTENTS
'IDA'
'AA'-'ZZ'
•HI'
CHARACTER
CHARACTER
MM/DD/YY
MM/DD/YY
CHARACTER
CHARACTER
CHARACTER
NUMERIC
CHARACTER
NUMERIC
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
FORMAT/CONTENTS
1
4
6
8
10
37
42
47
52
65
70
75
80
93
-
-
-
-
-
-
-
-
-
-
-
-
-
-
3
5
7
9
36
41
46
51
64
69*
74
79
92
97
3
2
2
2
27
5
5
5
13
5
5
5
13
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
ANALYTE
COLUMN 1 RT
COLUMN 1 RT LOWER LIMIT
COLUMN 1 RT UPPER LIMIT
COLUMN 1 CONCENTRATION
COLUMN 2 RT
COLUMN 2 RT LOWER LIMIT
COLUMN 2 RT UPPER LIMIT
COLUMN 2 CONCENTRATION
% D
•IDA1
'AA'-'ZZ1
• Dl'
NUMERIC
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
H-64
OLM01.0
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PESTICIDE IDENTIFICATION SUMMARY FOR MULTICOMPONENT ANALYTES -
(FORM 10B)
HEADER RECORD 1 (HI)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-19 12 EPA SAMPLE NO
20-31 12 LAB SAMPLE ID
32-39 8 DATE ANALYZED
40-47 8 DATE ANALYZED
48 - 57 10 INSTRUMENT ID
58-67 10 INSTRUMENT ID
68 - 77 10 GC COLUMN 1
78-81 4 GC COLUMN
82 - 91 10 GC COLUMN 2
92-95 4 GC COLUMN 2
96-97 2 PAGE
98-99 2 OF
1
2
1
2
1 ID
ID
FORMAT/CONTENTS
'10B1
'AA'-'ZZ1
'HI1
CHARACTER
CHARACTER
MM/DD/YY
MM/DD/YY
CHARACTER
CHARACTER
CHARACTER
NUMERIC
CHARACTER
NUMERIC
NUMERIC
NUMERIC
DETAIL RECORD 1 (Dl)
COLUMN(S) LENGTH CONTENTS
1 -
4 -
6 -
8 -
35 -
36 -
41 -
46 -
51 -
64 -
69 -
74 -
79 -
3
5
7
34
35
40
45
50
63
68-
73
78
91
3
2
2
27
1
5
5
5
13
5
5
5
13
FORM NUMBER
FORM SUFFIX
RECORD TYPE
ANALYTE
PEAK
COLUMN 1
COLUMN 1
COLUMN 1 RT UPPER LIMIT
COLUMN 1
COLUMN 2
COLUMN 2
COLUMN 2
COLUMN 2
RT
RT LOWER LIMIT
CONCENTRATION
RT
RT LOWER LIMIT
RT UPPER LIMIT
CONCENTRATION
FORMAT/CONTENTS
•10Bf
'AA'-'ZZ1
•Dl1
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
DETAIL RECORD 2 (D2)
COLUMN(S) LENGTH CONTENTS
1-3 3 FORM NUMBER
4-5 2 FORM SUFFIX
6-7 2 RECORD TYPE
8-34 27 ANALYTE
35 - 47 13 COLUMN 1 MEAN CONC.
48 - 60 13 COLUMN 2 MEAN CONC.
61-65 5 % D
FORMAT/CONTENTS
•10B1
'AA'-'ZZ'
'D2'
CHARACTER
NUMERIC
NUMERIC
NUMERIC
H-65
OLM01.0
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COMMENT RECORDS
COMMENT records are optional for some Forms as specified in
Table 3.1 in Section I of this Exhibit, and as appears on the
hard copy of the Reporting Forms in Section IV of Exhibit B.
They must come after the DETAIL records and be formatted as
follows:
COLUMN (S) LENGTH CONTENTS FORMAT/ CONTENTS
1-3 3 FORM NUMBER ' 3A1/ ' 3B1/ ' 3C '
•9A«
4-5 2 FORM SUFFIX 'AA'-'ZZ1
6-7 2 RECORD TYPE IC1'/'C2'
8-77 70 COMMENT CHARACTER
H-66 OLM01.0
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SECTION III
FORMAT B SPECIFICATION
1. Format Characteristics
1.1 Format B is an implementation of the EPA Agency Standard for Electronic Data
Transmission based upon analytical results and ancillary information required by
the contract. All data generated by a single analysis are grouped together, and
the groups are aggregated to produce files that report data from an SDG. Because
Format B is based on the Agency Standard, some non-CLP fields have been replaced
by blanks.
1.2 Format B includes detailed specifications for the required format of each record.
The exact position in the fixed-length record where each field is to be contained
is specified, as well as the 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 blanks.
1.3 All Format B character fields must be left-justified and padded to the right with
blanks. Numeric fields may contain numeric digits, a decimal place, and a
leading minus sign. A positive sign is assumed if no negative sign is entered in
a numeric field and must not be entered into any numeric field. Numeric entries
must be right justified and padded to the left with blanks. Allowance is made
within the Agency Standard for exponential notation.
Requirements for significant figures and number of decimal places are specified
in Exhibit B. The numeric field length are specified such that all possible
numeric values can be written to the file. The size of the numeric field
indicates the maximum number of digits, decimal, and negative sign if appropriate
that can appear in the field at the same time. Therefore, the number reported
may need to be rounded (using EPA Rounding Rules) to fit into the field. The
rounding must maintain the greatest significance possible providing the field
length limitation. In addition, the rounded number that appears on the form, and
therefore the field in the diskette file, must be used in any calculation that
may result in other numbers reported on the same form or other forms in the SDG.
2. Record Types
2.1 Format B consists of fixed-length 80-byte ASCII records. The last two bytes of
each record must contain "carriage return" and "line feed", respectively. Unused
bytes in partially filled fields must be blank-filled.
H-67 OLM01.0
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2.2 Format B consists of eleven record types than 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 and flags
A separate run header is used for volatiles, semivolatiles, and each column
analysis for pesticides (four Type 10 series for VOA/SV/PEST SDG). The 20 series
records are used to link samples within an SDG to the corresponding calibrations,
blanks, and so on for screening purposes. 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).
2.3 The sequence of records for Format B files is as follows: A Run Header (type 10}
record must 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 sevral files.
Each environmental sample, calibration, or quality control sample is represented
by a group composed of type 20, 21, 22, 23, and 27 records, which hold sample
level identifying information, followed by type 30, 31, and 32 records for each
method analyte or standard in the sample. The type 20 record holds a count for
the number of method analytes being determined, and includes all target compounds
plus any tentatively identified compounds. Type 20 records must occur in the
order of sample analysis. The type 20 records for quality control items have the
additional rule that the LF1 record must occur before the LF2 record, but the
records need not be adjacent (matrix spike data). In addition, a type 20 record
is used as a header for any additional run-wide data that must be reported for
each method analyte (such as mean response factors). Unique identifiers given on
page H-85 are used in place of "QC codes" to indicate the type of data that
follows. Type 30 records for each analyte must occur in the order specified on
hardcopy deliverable Form 6.
Type 90 comment records may be defined to occupy any position except before the
type 10 (header) record.
H-68 OLM01.0
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EXAMPLE OF THE SEQUENCE OF RECORD TYPES IN A FILE
10 Contains Run Header information
11 Contains additional run-wide information if required.
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
27
30 Occurs once for each final analytical result. Reports
the value being determined as defined by the type 20.
31 Reports any instrumental data necessary.
32 Reports any auxiliary data necessary.
33 Reports component names if necessary.
30 Values for the next analyte or parameter being measured.
31 Additional data may vary for each parameter, and records
32 may occur in any order. Multiple occurrences of the
32 same record type, however, must be consecutive.
33
30 Continues for as many as are necessary.
31
32
33
30
31
32
33
20 Next Sample Header record - The following applies to the next
21 sample or other group of data.
22
30
31
32
33
30
31
32
31
etc.
20
21
30
31
32
33
etc.
H-69 OLM01.0
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File/Record Integrity
All record types shall contain the following check fields to ensure file and
record integrity:
Record Field Field
Position Length Contents
1-2 2 Record type
72-74 3 Record sequence number
within file
75-78 . 4 Record checksum
79-80 2 Must contain CR and LF
Remarks
"10" or a.s appropriate
000-999, repeated as
necessary
Four hexadecimal digits(*)
4.
(*) The checksum is the sum of the thirty-five Integers that make up the data in
columns 1 to 70, when data are represented in the format 35A2 on processors which
store data bytes in left to right order. The sum is taken modulo 65536 (2 ) and
represented as four hexadecimal digits. For processors which use an A70
character representation of data, the checksum is the sum of all the even
character position values -plus 256 times the sum of all the odd character
position values.
Dates and Times
Date or time-of-day information consists of successive groups of one or two
decimal digits, each separated by blanks. Dates are given in the order YY MM DD,
and times as HH MM. All hours must be given as 0 to 23 using a 24 hour clock and
must be local time.
5. Record Listing
Following is a listing of every record type required to report data from a
SDG.
single
H-70
OLM01.0
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PRODUCTION RUN HEADER RECORD (TYPE 10)
POSITION LENGTH CONTENTS FORMAT/CONTENTS
1-2 2 RECORD TYPE "10"
3-18 16 blank
19-23 5 MEASUREMENT TYPE "GC/MS" for VGA and SV
"GC/EC" for Pesticides.
24-26 3 blank
27-30 4 METHOD NUMBER "6241" for Volatiles;
"625C" for Semivolatiles;
"6081"for Pesticides
31-35 5 blank
Character
MBER Character
63-68 6 INSTRUMENT ID e.g. 59951G; provided by
contract lab; left justi-
fied; must be unique and
permanent within lab. First
four characters are vendors
designator; fifth and sixth
are lab assigned so each
instrument is unique.
36-41
42-51
52-61
62
6
10
10
1
LAB CODE
blank
CONTRACT
blank
H-71 OLM01.0
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CHROMATOGRAPHY RECORD (TYPE 11)
Use: To describe chromatograph conditions.
pesticides. Is optional for seraivolatiles.
Position: Follows type 10.
POSITION LENGTH CONTENTS
Must be present for volatiles and
1-2
3
4-11
12-17
18-21
2
1
8
6
4
RECORD TYPE
blank
GC COLUMN
blank
GC COLUMN ID
FORMAT/CONTENTS
"11'
Left justified.
e.g., SP2330
mm e.g., 2 or .3
Right justified
H-72
OLM01.0
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SAMPLE HEADER DATA RECORD (TYPE 20)
POSITION LENGTH CONTENTS
NOTE:
FORMAT/CONTENTS
"20"
Left justified. Raw Sample
No. only; no suffixes.
"0" if not applicable
(calibrations, tunes, etc.)
"1" for water
"H" for soil
Codes type of data to be
reported (see page H-85)
"RIN" - reanalyzed
"REX" - reprepared
"REJ" - rejected
"SRN" - diluted
Required for blanks,
EPA samples, optional
otherwise
Left justified
YY MM DD
HH MM
"L" - liters for water
"K" - kilograms for soil
right justified;
see Note
Numeric; 1-3 decimal digits;
right justified. Counts all
analytes including TIC's.
For calibrations, count all
analytes, surrogates, and
DFTPP/BFB if mixed in
injection.
SAMPLE WT/VOL is the volume in liters for liquids and the wet weight in
kilograms for solids. The Sample Units Code indicates which units are in vise
for the current sample. Leave zero or blank if not applicable. SAMPLE
WT/VOL includes purge volume
1-2
3-6
7-13
14-15
16
17
18-20
21
22-24
25
26-30
31-33
34-38
39
40-47
48
49-53
54-56
57
58
59-66
67
68-70
2
4
7
2
1
1
3
1
3
1
5
3
5
8
1
5
3
1
1
8
1
3
RECORD TYPE
blank
EPA SAMPLE NO.
blank
MATRIX
blank
QC CODE
blank
SAMPLE QUALIFIER
blank
CASE NUMBER
blank
SDG NO.
blank
DATE ANALYZED
blank
TIME ANALYZED
blank
SAMPLE WT/VOL UNITS
blank
SAMPLE WT/VOL
blank
ANALYTE COUNT
H-73
OLM01.0
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SAMPLE HEADER DATA RECORD (TYPE 21)
Use: Continuation of type 20.
Position: Follows the type 20 to which it applies.
POSITION LENGTH CONTENTS
1-2
3
4
5
6
7
8
9-11
12
13-17
18-23
24
2
1
1
1
1
1
1
3
1
5
6
1
RECORD TYPE
blank
PURGE
blank
LEVEL
blank
CLEAN-UP
blank
EXTRACTION
blank
SAS NO.
blank
25-35
36
37-44
45-47
48-55
56-64
65-70
11 LAB FILE/SAMPLE ID
1 blank
8 DATE OF EXTRACTION
3 blank
8 DATE RECEIVED
9 „ blank
6 INJECTION/ALIQUOT VOLUME
FORMAT/CONTENTS
'21"
"H" for heated
"L" - low
"M" - medium
(See note).
"G" for GPC or blank
"S" - Separately Funnel
"C" - Continuous Liq-Liq
"N" - Sonicacion
Leave blank if none.
Optional for calibrations
From instrument data
system. Lab File ID for VGA
or Semivolatiles; Lab Sample
ID for Pesticides.
YY MM DD
YY MM DO
ul, Injection Volume for
BNA's and PEST's Volume of
aliquot for VGA's.
Note: The LEVEL is an estimate of overall level for all analytes. It is
blank for calibrations and tunes.
H-74
OLM01.0
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SAMPLE CONDITIONS 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.
POSITION
LENGTH
CONTENTS
1-2
3
4-11
12
13-17
18
19-29
2
1
8
1
5
1
11
RECORD TYPE
blank
CALIBRATION DATE
blank
CALIBRATION TIME
blank
CALIBRATION FILE ID
FORMAT/CONTENTS
"22"
YY MM DD; see Note 1
(Date of Source of the
response factor used)
HH MM
Lab File ID of associated
continuing calibration, or
"AVERAGE", position 21-27
and padded with blanks
(Note 2)
XX or XX.X or zero, right
justified
decanted or nondecanted value
used to correct to dry weight;
use zero if not applicable
report nondecanted % water if
water was decanted; use
zero if not applicable
ul, e.g., 1,000 or 500
(See Note 3)
Right justified; from Form 1
e.g., 2000
Note 1: For average, use the date and time average was calculated.
Note 2: If "AVERAGE" is entered, then Form 8 will be constructed using the initial
calibration with a QC code of "CLD". This field must match columns 25-35 of
record type 21 for the associated calibration.
Note 3: Use the initial extract volume adjusted (multiplied) by all contract-mandated
dilutions that are to be excluded from the dilution factor.
30
31-34
35
36-37
38
39-40
41
42-46
47
48-54
1
4
1
2
1
2
1
5
•t
1
7
blank
PH
blank
% MOISTURE
blank
AUXILLIARY
MOISTURE
blank
PERCENT
CONG. EXTRACT VOLUME
blank
DILUTION FACTOR
H-75
OLM01.0
-------
ASSOCIATED INJECTION AND COUNTER RECORD (TYPE 23)
Use: Continuation of type 20. Used to identify associated blanks and tunes,
and to count the number of surrogates and spikes outside of QC limits and
the number of TIC compounds. Used for Forms 3, 4, and 5.
Position: Follows the type 20, 21, and 22 to which it applies.
POSITION
LENGTH
CONTENTS
1-2
3
4
5
6-13
14
15-19
20
21-31
32
33
34
35-42
43
44-48
49
50-60
61
62
63
64-65
66
67
68
69-70
2
1
1
1
8
1
5
1
11
1
1
1
8
1
5
1
11
1-
1
1
2
1
1
1
2
RECORD TYPE
blank
TUNE LABEL
blank
INJECTION DATE
blank
INJECTION TIME
blank
DFTPP/BFB LAB FILE ID
blank
BLANK LABEL
blank
BLANK INJECTION DATE
blank
BLANK INJECTION TIME
blank
BLANK LAB FILE/SAMPLE ID
blank
RECOVERY NO. LABEL
blank
NO. OF RECOVERIES OUT
blank
TIC/RPD LABEL
blank
NO. TIC/RPD
FORMAT/CONTENTS
"23"
"P" or blank
Labels data as "tune" data.
YY MM DD. Acquisition date
of tune to be linked with
sample (if applicable).
HH MM (if applicable)
From instrument data system
"B" or blank
Labels data as "blank" data.
(use blank if none)
YY MM DO. Acquisition date
of method blank to be linked
with sample (if applicable).
HH MM (if applicable)
From instrument data system
Lab File ID - VOA/BNA
Lab Sample ID - Pest
Identifies following counter
"P" - # of % Recoveries
Outside of QC limits
Use the Counter from Form
2 or 3 for each sample.
"T" - # of TIC compounds.
blank - TIC's not searched
"R" - # of % RPD's outside
limits
From Form 1-E or 1-F
or Form 3
H-76
OLM01.0
-------
SAMPLE CLEANUP RECORD (TYPE 27)
Use: Continuation of Type 20. Used to identify sample clean-up procedures and
QC results. Used for Form 9.
Position: Follows Type 20, 21, 22 and 23 to which it applies
POSITION
1-2
3
4
5
6-13
14
15-19
20
21-31
32
33
34
35-42
LENGTH
2
1
1
1
4
1
10
1
1
1
8
43
44-48
49
50-60
61
62
1
4
1
10
1
1
CONTENTS
RECORD TYPE
blank
FIRST CLEANUP TYPE
blank
GPC CALIBRATION CHECK DATE
blank
GPC CALIBRATION CHECK TIME
blank
LAB DATA DESCRIPTOR
blank
SECOND CLEANUP TYPE
blank
FLORISIL LOT CHECK DATE
blank
FLORISIL LOT CHECK TIME
blank
LAB DATA DESCRIPTOR
blank
SULFUR CLEANUP
FORMAT/CONTENTS
"27"
"G" for GPC
YY MM DD. Check of GPC
calibration to be linked
with this sample
HHMM
Lab Sample ID for GPC
check
"F" for Florisil
YY MM DD. Check of
Florisil lot check
cartridge lots to be
linked with this sample
HHMM
Lab Sample ID for
Florisil lot check
*S" or blank
H-77
OLM01.0
-------
RESULTS DATA RECORD (TYPE 30)
POSITION LENGTH CONTENTS
1-2
3
4
5
6-14
15
16-24
25
26-30
31
32-34
35
36-41
42
43-45
46
47
48
49-54
55
56-58
59
60
61
62-66
67
68-70
2
1
1
1
9
1
9
1
5
1
3
1
6
1
3
1
1
1
6
1
3
1
1
1
5
1
3
RECORD TYPE
blank
ANALYTE LABEL
blank
CAS NUMBER
blank
INTERNAL STANDARD
CAS NUMBER
blank
CONCENTRATION UNITS
blank
RESULT QUALIFIER
blank
RESULT
blank or 'E'
EXPONENT
blank
FIRST VALUE LABEL
blank
FIRST RELATED VALUE
blank or "E"
EXPONENT
blank
SECOND VALUE LABEL
BLANK
SECOND RELATED VALU
blank or 'E'
EXPONENT
Note: Units apply to the results field for samples
for calibrations.
FORMAT/CONTENTS
•30'
"C" - CAS Number
"I" - Combined DDT and
Endrin breakdown.
"M" - mean cone for Form 10B
Right justified.
"COMBINED" - combined DDT
and Endrin breakdown.
"MEANCONC" - mean
concentration (Form 10B)
Right justified - blank for
pesticides
"UG/KG" for Soil;
"UG/L " for Water;
"PERCT" for percent
(See Note).
See page H-87. First flag.
Right justified; fixed
point or scientific
notation
Blanks in field will be
interpreted as "zeros"
Describes following value
(See page H-89)
Value of item described
above. Formal:
same as 36-45 .
Describes following value
(See page H-89)
Value of item described
above.
and the related calculated value
H-78
OLM01.0
-------
CALCULATION OF RESULTS ON TYPE 30 RECORDS
The following equations are used Co calculate all results reported on type 30 records.
RELATIVE RESPONSE FACTORS OR CALIBRATION FACTORS
RRF - (ANALYTE AREA) (I.S. AMOUNT) (BNA's AND VOA's)
(I.S. AREA) (ANALYTE AMOUNT)
CF - (ANALYTE AREA) (PEST's)
(ANALYTE AMOUNT [ng injected])
UNKNOWN CONCENTRATIONS
SAMPLE SIZE - Sample Volume (in L) for water
Sample Weight (in Kg) X C10Q - aWater^ for soil
100
CONG - (ANALYTE AREA1 (I.S. injected) (Extract Vol) (b.F.XBNA, VGA)
(I.S. AREA) (R.F.) (Injected Vol) (SAMPLE SIZE)
CONG - fANALYTE AREA) (Extract Vol) (D.F.) (PEST's)
(R.F.) (Injected Vol) (SAMPLE SIZE)
CRQL CORRECTION
CRQL - CCROL [ng injected]1) (Extract Vol) fP.F.)
(Injected Vol) SAMPLE SIZE)
The Sample Volume or Weight is in Type 20 Col. 59-66. The % Water is in Type 22
Col. 36-37. The Extract Vol is in Type 22 Col. The Dilution Factor is in Type 22
Col. 48-54. The Injection Volume is in Type 21 Col. 65-70.
H-79 OLM01.0
-------
INSTRUMENTAL DATA READOUT RECORD (TYPE 31)
Use: To describe peak areas for internal standards to be used in Form 8 and
DFTPP/BFB percent abundances for Form 5.
Position: Follows type 30 for internal standards and DFTPP/BFB data.
POSITION LENGTH CONTENTS
1-2
3
RECORD TYPE
blank
FORMAT/CONTENTS
"31"
4
5
7-9
MASS LABEL
blank
VALUE LABEL
blank
10-17
18
19-28
29
30-37
38
39-48
49
50-57
58
8
1
10
1
8
1
10
1
8
1
FIRST MASS
blank
FIRST VALUE
blank
SECOND MASS
blank
(DFTPP/BFB)
SECOND PERCENT ABUNDANCE
blank
THIRD MASS
blank
"M" - mass for DFTPP/BFB data
"I" - internal standard
A - Area (Internal Standards).
P - % Abundance of base peak
(DFTPP/BFB);
S - % Abundance of secondary ion.
Gives the DFTPP/BFB masses
(right justified), e.g., 442.
up to 10 decimal digits,
right justified
(% abundance or area)
59-68
10
THIRD PERCENT ABUNDANCE
Note 1: Columns 30-68 will be blank on records reporting internal standard data.
Note 2: Up to three masses and percent abundances may be reported on each record for
DFTPP/BFB data. Those ions that require two percent abundance values must be
listed twice.
H-80
OLM01.0
-------
AUXILIARY DATA RECORD (TYPE 32)
Use: Used to report scan number and retention time (in minutes) for Internal
Standards and for TIC compounds. Used to report retention time data and
percent breakdown for Pesticides.
Position: Follows type 30. (Record will only be required as specified above.)
POSITION LENGTH CONTENTS
1-2 2 RECORD TYPE
3-8 6 blank
9-10 2 RETENTION TIME LABEL
11 1 blank
12-21 10 RETENTION TIME
22 1 blank
23-24 2 FIRST LIMIT LABEL
25 1 blank
26-35 10 RT WINDOW LOWER LIMIT
36 1 blank
37-38 2 SECOND LIMIT LABEL
39 1 blank
40-49 10 RT WINDOW UPPER LIMIT
50 1 blank
51-52 2 THIRD LIMIT LABEL
53 1 blank
54-63 10 % BREAKDOWN or % DIFFERENCE
64 1 blank
65 1 PEAK
FORMAT/CONTENTS
"32"
"RT"
In decimal minutes
"SC" - scan number for
GC/MS
"RF" - RT "From" Value
for" Pesticides (Form 7D).
In decimal minutes.
"RO" - RT "To" Value
for Pesticides (Form 7D)
In decimal minutes.
"PB" indicates
% breakdown for Pesticides
"PD" indicates % difference
in quantitation from two
columns (Form 10)
Peak identification
(1 through 5)
H-81
OLM01.0
-------
NAME RECORD (TYPE 33)
Use: To carry an analyte name for TIC compounds.
Position: Follows type 30 for TIC compounds.
POSITION LENGTH CONTENTS FORMAT/CONTENTS
1-2 2 RECORD TYPE "33"
3 1 blank
4-70 67 NAME OF COMPOUND
H-82 OLM01.0
-------
COMMENT RECORD (TYPE 90)
Use: To provide for Operator-Entered Comments.
Position: May occur anywhere.
POSITION LENGTH CONTENTS FORMAT/CONTENTS
1-2 2 RECORD TYPE "90"
3 1 blank
4-70 67 ANY COMMENT
H-83 OLM01.0
-------
FLAGS RECORD (TYPE 91)
Use: To provide for multiple Form 1 Results Qualifier Flags.
Position: Immediately follows the type 30 record to which it applies.
POSITION
1-2
3
4-6
8-10
11
12-14
15
16-18
19
20-22
LENGTH
2
1
3
1
3
1
3
1
3
CONTENTS
RECORD TYPE
blank
SECOND FLAG
FLAG
blank
THIRD FLAG
blank
FOURTH FLAG
bl»nk
FIFTH FLAG
blank
SIXTH FLAG
FORMAT/CONTENTS
"91"
Result Qualifiers
(See page H-87)
H-84
OLM01.0
-------
6. Definitions of Codes Used in Format: 8 Records • • < . . .
.1 Quality Control and Related Codes (QCC) in'Type 20 Records. - - f
Note: These codes appear in the QC code fields of type 20-records. They are
used to indicate the type of data that are being reported.
QCC
Name
LRB LABORATORY'(REAGENT)
BLANK
r ' * ' * - r • .
LIB LABORATORY INSTRUMENT
BLANK '
LSB LABORATORY SULFUR
. , . BLANK
Definition
, The. "Method Blank" (See Exhibit G) .
• ^
The "Instrument Blank" (Pesticides)
•If different from "Method Blank" (Pesticides)
LSD LABORATORY SPIKE '
- r .. DUPLICATE' BACKGROUND
(ORIGINAL)'VALUES' '~
LF1 LABORATORY SPIKED
SAMPLE-->INAL -
FIRST MEMBER
LF2 LABORATORY SPIKED
SAMPLE - FINAL -.
SECOND"MEMBER -
"An environmental sample which is -analyzed according
to the analytical method, and subsequently used for
Che* matrix -spike and the matrix spike duplicate
(See Exhibit G). - .
The "Matrix Spike" (See Exhibit G) - must preceed
LF2-- - • .
The "Matrix Spike Duplicate" (See Exhibit G)
LPC - LABORATORY PERFORMANCE
' ' CHECK SOLUTION- - ... ..
A solution 'of DFFPP tBNA) or -BFB, CVOA) 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) (See Exhibit G).- * -
FLO FLORISIL CHECK'
SOLUTION
GPC . GPC CHECK
SOLUTION'
A .solution of pesticides used to check recovery
from each lot of Flori'sll cartridges.
A solution of pesticides used to check recovery
from each new GPC calibration.
CLM INITIAL. CALIBRATION
MULTI POINT*
CLS
INITIAL CALIBRATION *
SINGLE-POINT ^ - ._ .
The .Initial Calibration for GC/MS (See Exhibit G),
x>r the' Initial Evaluation Standard Mixes (A,
B) for Pesticides (See Exhibit D^PEST).
Response factors.(GC/MS)v or, Calibration Factors
(Pesticides) rather than concentrations will be
reported'on the following .type, ,3.0 records.
The Initial1 Individual ^tandar,d/Toxaphene/Aroclor
.Mixes used to determine all calibration factors.
(See Exhibit D" PEST)'. - - . -» tv,_ ~
--
-H-85'-
OLM01.0
-------
QCC Name Definition
CLE CONTINUING PERFORMANCE The subsequent Individual/Evaluation Standard
CHECK Mixes (A,B) and Performance Evaluation Mixture for
Pesticides (See Exhibit D PEST).
CLC CONTINUING CHECK The Continuing Calibration for GC/MS
CALIBRATION (See Exhibit G.)
CLD DUAL PURPOSE A calibration solution as above used both as an
CALIBRATION initial calibration (CLM) and a continuing check
(CLC). [50 level initial calibration if needed
for Form 8]
blank Sample, not associated with any quality
control item.
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. If the data apply to only a portion of the samples in the
run, they should 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 The data following represent mean values and
CALIBRATIONS percent RSD's from the initial calibribration
(GC/MS) or the evaluation mixes (Pesticides).
SDR MATRIX SPIKE DUPLICATE The data following represent calculated QC
CALCULATED RESULTS results for the triplicate of samples LSD,
LF1, and LF2. Data will consist of the LF1
percent recovery, the LF2 percent recovery,
and the percent RSD for each method analyte
that was spiked according to the analytical
method as is present on hardcopy deliverable
Form 3.
H-86 OLM01.0
-------
6.2 Result Qualifiers in Type 30 Records
A sample qualifier or a result qualifier (also called a non-numeric result)
consists of 3 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 but it is qualified in some respect relating to the type or
validity of the result.
BDL BELOW DETECTABLE LIMITS
NAR NO ANALYSIS RESULT
AVG AVERAGE VALUE
CBC CANNOT BE CALCULATED
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
MSP PERCENT RECOVERY
Indicates compound was analyzed for but
not detected; (Form 1 "U" Flag).
There is no analysis result required for
this subject parameter.
Average value - used to report a range of
values; e.g., relative response factors.
The analysis result cannot be calculated
because an operand value is qualified.
Identifies analytes whose Internal
Standard is not found.
s
Actual value is known to be less than the
lower calibration range due to dilution.
(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 1-E or 1-F "J"
Flag)
Results rejected by the laboratory.
The indicated compound is an internal
standard. There is no analysis result to
report.
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)
The following value represents the percent
recovery for the "MS" sample. The
remaining two values give the "USD"
percent recovery and the Percent RPD.
H-87
OLM01.0
-------
CON CONFIRMED
TFB TENTATIVELY IDENTIFIED
AND FOUND IN BLANK
ALC ALDOL CONDENSATION
EST ESTIMATED VALUE
PRE PRESUMPTIVE PRESENCE
Pesticide identification has been
confirmed by GC/MS (Form 1 "C" Flag).
A Combination of "TIE" and "FBK" (Form 1-
E or 1-F "B" flag).
Labels a suspected Aldol Condensation-
product for TIC's (Form 1-E or 1-F "A"
Flag).
Present above detection limit but not
quantified within expected limits of
precision (Form 1-D "P" flag).
Presumptive evidence of presence of
material; tentative identification
(Form 1-E or 1-F "N" flag).
H-88
OLM01.0
-------
6.3 Value Labels in Type 30 Records
These codes appear in column 47 (FIRST VALUE LABEL) of Type 30 records to
identify the value in columns 49-58.
Qualifier
A
AMOUNT ADDED
PERCENT RECOVERY
Definition
Identifies the amount of matrix spike analyte
added (for QC codes "LF1" and "LF2") or
nominal amount for pesticide standards.
Identifies the Percent Recovery of the "USD"
Sample in the Matrix Spike Results Record
(for QC Code "SDR")
These codes appear in column 60 (SECOND VALUE LABEL) of Type 30 records to
identify the value in columns 62-70.
Qualifier
U
Full N*"»e
UNDETECTED
PERCENT RSD
SURROGATE RECOVERY
PERCENT DIFFERENCE
PESTICIDE LEVEL
Definition
Value is the corrected sample quantitation
limit (Form 1 "U" ValueX.
Value is the Percent RPD for the Matrix Spike
and Matrix Spike Duplicate (QC Code "SDR") or
RSD for the Mean Response Factors (QC Code
"MNC").
Value is the Percent Recovery for the indicated
Surrogate or Spike (Form 2, Form 9A, Form 9B).
Value is the Percent Difference of the Result
of the Continuing Check from that of the
Initial Calibration (as on Form 7).
Value is the concentration of pesticide standard
(LOW, MED, HIGH) as a factor of the LOW
(e.g., LOW-1, MED-10)
H-89
OLM01.0
-------
7.
Format of Records for Specific Uses
7.1 Format of the SAMPLE HEADER DATA RECORD (Type 20) for Mean Relative Response
Factors
7.2
POSITION
LENGTH
CONTENTS
FORMAT/CONTENTS
1-2
3-15
16
17
18-20
21-66
67-69
Format of the
POSITION
1-2
3
4
5
6-14
15
16-24
25-31
32-34
35
36-41
42
43-45
46-59
60
61
62-66
67
2
13
1
1
3
46
3
RESULTS DATA
LENGTH
2
1
1
1
9
1
9
7
3
1
6
1
3
14
1
1
5
1
"20"
blank
"0-
blank
"MNC"
blank
ANALYTE COUNT
Record Type
All matrices
Identifies Mean Response
Factors
Numeric; 1-3 decimal
digits; right
justified.
RECORD (Type 30) for Mean Relative Response Factors
<*
CONTENTS
"30"
blank
-C"
blank
CAS NUMBER
blank
INTERNAL
STANDARD CAS NUMBER
blank
"AVG"
blank
RESULT
blank or '£'
EXPONENT
blank
"R"
blank
SECOND RELATED VALUE
blank or '£'
FORMAT/CONTENTS
Record Type
Right justified.
Right justified
Indicates Average Value
Mean Relative Response Factor
Right justified; fixed
or scientific notation
Blank field will be
interpreted as "+00"
Indicates Percent RSD
Percent RSD
68-70
EXPONENT
H-90
OLM01.0
-------
7.3 Format of the SAMPLE HEADER DATA RECORD (Type 20) for Matrix Spike Duplicates
POSITION LENGTH CONTENTS FORMAT/CONTENTS
Record Type
Left justified. Raw
Sample I.D. only;
no suffixes.
"1" for water
"H" for soil
Identifies Matrix Spike
Duplicate Results
1-2
3-6
7-11
12-15
16
17
18-20
21-25
26-30
31-33
34-38
39-66
2
4
5
4
1
1
3
5
5
3
5
2
"20"
blank
EPA SAMPLE NO.
blank
MATRIX
blank
"SDR"
blank
CASE NUMBER
blank
SDG NO.
blank
67-69 3 ANALYTE COUNT Numeric; 1-3 decimal
digits; right
justified. Counts
number of spiked
analytes.
7.4 Format of the COUNTER RECORD (Type 23) for Matrix Spike Duplicates
Position: Follows the type 20 to which it applies.
POSITION LENGTH CONTENTS FORMAT/CONTENTS
1-2 2 "23" Record Type
3-61 59 blank
62 1 "P" Identifies Number of %
63 1 blank Recoveries outside of
limits.
64-65 2 NO. RECOVERIES OUT • Use the counter from
Form 3 for each sample.
66 1 blank
67 1 "R" # of % RPD's outside
68 1 blank limits.
69-70 2 NO. RPD LIMITS From Form 3.
H-91 OLM01.0
-------
7. 5 Format of Che
POSITION
RESULTS DATA RECORD (Type 30) for Matrix Spike Duplicates
LENGTH
CONTENTS
1-2
3
4
5
6-14
15
16-24
25
26-30
31
32-34
35
36-41
42
43-45
46
47
48
49-54
55
56-58
59
60
61
62-66
67
2
1
1
1
9
1
9
1
5
1
3
1
6
1
3
1
I
1
6
1
3
1
1
1
5
1
"30"
blank
"C"
blank
CAS NUMBER
blank
INTERNAL
STANDARD CAS NUMBER
blank
"PERCT"
blank
-MSP"
blank
RESULT
blank or 'E'
EXPONENT
blank
npn
blank
FIRST RELATED VALUE
blank or 'E'
EXPONENT
blank
"R"
blank
SECOND RELATED VALUi
blank or 'E'
FORMAT/CONTENTS
Record type
Right justified.
Right justified
Units are "Percent"
Indicates Hatrix Spike
Percent recovery
MS Percent Recovery
Right justified; fixed
or scientific notation
Blank field is
interpreted as "+00"
Indicates Matrix Spike
Duplicate Percent Recovery
MSD Percent Recovery
Format same as 36-46.
Indicates Percent RSD
Percent RPD
68-70
EXPONENT
H-92
OLM01.0
-------
7.6 Format of the SAMPLE HEADER DATA RECORD (Type 20) for Pesticide Evaluation Mix B
POSITION
1-2
3-6
7-11
12-15
16
17
18-20
21-25
26-30
31-38
39-46
47
48-52
53-66
67-69
LENGTH
2
4
5
4
1
1
5
8
8
1
5
14
CONTENTS
"20"
blank
"EVALB"
blank
•0"
blank
"CLC"
blank
CASE NUMBER
blank
DATE ANALYZED
blank
TIME ANALYZED
blank
ANALYTE COUNT
FORMAT/CONTENTS
Record Type
Sample I.D.
All matrices
Indicates Continuing
Check (Pesticide
Standard)
YY MM DD
HH MM
Numeric; 1-3 decimal
digits; right
justified.
H-93
OLM01.0
-------
7.7 Format of the RESULTS DATA RECORD (Type 30) for Pesticide'Evaluation Mix B
(Percent Breakdown Data From Form 8D)
The following type 30 record occurs once if reporting "Combined" breakdown only,
or three times if reporting separate breakdowns for Endrin and DDT along with the
Combined value.
POSITION
1-2
3
5
6-14
15-25
26-30
31-46
47
48
49-54
55
56-58
LENGTH
2
1
1
9
11
5
16
1
1
1
3
CONTENTS
"30"
blank
"C" or "I"
blank
CAS NUMBER
blank
"PERCT"
blank
"B"
blank
FIRST RELATED VALUE
blank or 'E'
EXPONENT
FORMAT/CONTENTS
Record Type
Use "C" - CAS Number
unless identifying
combined DDT and
Endrin, in which case
use "I"
Right justified. Use
"COMPINED" for combined
DDT and Endrin.
H
Units
Identifies Percent
Breakdown
Percent Breakdown of
Indicated Conrpound(s) Right
justified; fixed scientific
notation
Blank field will be
interpreted as "+00"
H-94
OLM01.0
-------
Format of the
(Type 30) for
POSITION
SAMPLE HEADER DATA RECORDS (Type 20-23)
Continuing Checks (GC/MS Methods)
67-69
POSITION
LENGTH
CONTENTS
1-2
3-6
7-13
14
15
16
17
18-20
21
22-24
25
26-30
31-38
39-46
47
48-52
53-66
2r_
4
7
1
1
1
1
3
1
3
1
5
8
8
1
5
14
"20"
blank
Identifier
Daily Sequence Number
blank
"0"
blank
"CLC"
blank
SAMPLE QUALIFIER
blank
CASE NUMBER
blank
DATE ANALYZED
blank
TIME ANALYZED
blank
ANALYTE COUNT
LENGTH CONTENTS
and RESULTS DATA RECORD
FORMAT/CONTENTS
e.g., VTD050
From Exhibit B
All matrices
Indicates
Continuing Check
See page H-85
YY MM DD
HH MM
Numeric; 1-3
decimal digits;
right justified.
FORMAT/CONTENTS
1-2
3-13
14-16
17
L8-23
24
2
11
3
1
6
1
"21"
blank
"H"
blank
SAS NUMBER
blank
Record Type
Indicates heated purge
Leave blank
if none.
25-35
11
LAB FILE I.D.
H-95
OLM01.0
-------
POSITION
LENGTH CONTENTS
1-2
3
4
5
6-13
14
15-19
20
2
1
1.
i
8
1
5
1
"23"
blank
n pit
blank
INJECTION DATE
blank
INJECTION TIME
blank
21-31
POSITION
11
DFTPP/BFB LAB FILE ID
LEI;GTH CONTENTS
1-2
3
4
5
6-14
15
16-24
25-31
32-34
35
36-41
42
43-45
46-59
60
61
62-66
67
68-70
2
1
1
1
9
1
9
7
3
1
6
1
3
14
1
1
5
1
3
"30"
blank
"C"
blank
CAS NUMBER
blank
INTERNAL
STANDARD CAS
blank
NUMBER
RESULT QUALIFIER
blank
RESULT
blank or '£'
EXPONENT
blank
"D"
blank
SECOND RELATED VALUE
blank or 'E'
EXPONENT
FORMAT/CONTENTS
Record Type
Labels data as
"tune" data.
YY MM DD.
Aquisition date
of tune to be
linked with this
calibration.
HH MM
From instrument
data system.
FORMAT/CONTENTS
Right justified.
Right justified.
See page H-87;
Response Factor
Right justified;
fixed or scientific
notation
Blank field will be
interpreted as "+00".
Identifies Percent
Difference.
RRF Percent Difference
From Initial
Calibration
(from Form 7).
H-96
OLM01.0
-------
------- |