United States Office of
Environmental Protection Solid Waste and
Agency Emergency Response
December 1994
Superfund
&EPA USEPA CONTRACT
LABORATORY PROGRAM
STATEMENT OF WORK
FOR ORGANICS ANALYSIS
MULTI-MEDIA,
MULTI-CONCENTRATION
OLMO1.0
INCLUDING REVISIONS
OLMO1.1 (DECEMBER 1990)
OLMO 1.2 (JANUARY 1991)
OLMO 1.3 (FEBRUARY 1991)
OLMO 1.4 (MARCH 1991)
OLMO 1.5 (APRIL 1991)
OLMO 1.6 (JUNE 1991)
OLMO 1.7 (JULY 1991)
OLMO 1.8 (AUGUST 1991)
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9240.1-07
PB95-963508
EPA540/R-94/078
USEPA CONTRACT LABORATORY PROGRAM
STATEMENT OF WORK
FOR
ORGANICS ANALYSIS
Multi-Media, Multi-Concentration
Document Number OLM01.0
Including Revisions OLM01.1 (December 1990),
OLM01.2 (January 1991), OLM01.3 (February 1991),
OLM01.4 (March 1991), OLM01.5 (April 1991),
OLM01.6 (June 1991), OLM01.7 (July 1991),
and OLM01.8 (August 1991)
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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
OLM01.0
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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) volatile components and up to twenty (20) semivolatile
components that are neither system monitoring compounds, surrogates, internal
standards, or volatile or semivolatile target compounds (see 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 deliverables 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, potentially, 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 Time of Sample Receipt). Separately 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
10 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 extraction. 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 comparison of the suspect mass spectrum to the mass
spectrum of a standard of the suspected compound. This
procedure requires the use of multiple internal standards.
Two criteria must 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. The 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 most recent
release of the NIST/EPA/MSDC mass spectral library 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.
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2. Only after visual comparison of sample spectra with the
spectra from 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
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, and Exhibit H, Data Dictionary and Format for
Data Deliverables in Computer-Readable Format.
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 (7 calendar day period for 14-day
data turnaround contracts) (said period beginning with
the receipt of the first sample in that Sample Delivery
Group).
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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).
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 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, including matrix spikes and
reanalyses, OR
o Each 14 calendar day period (7 calendar day period for
14-day data turnaround contracts) 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 time, and mass spectra.
Additional quality control shall be conducted in the form of
the analysis of laboratory evaluation samples submitted to the
laboratory by the Agency. The results of all such control or
laboratory evaluation 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).
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B. 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.
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 submitted in the hardcopy data
package(s) provided that the forms are in EXACT EPA FORMAT. This
means that the order of data elements is the same as on each EPA
required form, including form numbers and titles, page numbers 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 the hardcopy forms, or the computer
readable data, 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/electron
capture/data systems (GC/EC/DS) 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 dura'tion 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.
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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-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 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 personnel.
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/EC/DS for pesticide analysis shall be equipped with
wide bore capillary columns and a suitable detector and data
system 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 E) for 365 days after data submission. During that
time, the Contractor shall submit tapes and logbook within 7 days
of request from EMSL/LV or the Administrative Project Officer
(APO), as specified in the Contract Performance/Delivery Schedule
and Exhibit E.
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 most recent
release of the NIST/EPA/MSDC mass spectral library, 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.
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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.
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
field 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 Project Manager
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
o Sample Custodian
o Data Reporting and Delivery Officer
F. The Contractor shall respond within seven days to written requests from
data recipients for additional information or explanations that result
from the Government's inspection activities unless otherwise specified
in the contract.
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The Contractor shall store all samples and unused sample volume at 4eC
(±2°C), protected from light, from time of receipt until 60 days after
data submission. Samples and unused sample volumes must be stored
separately from sample extracts and standards. 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 seven days of a written request by TPO/APO, as
specified in the Contract Performance/Delivery Schedule.
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).
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
ensure 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.
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
Ca'se 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 (7 calendar day period for 14-day data
turnaround contracts) during which field samples in a Case are
received (said period beginning with the receipt of the first sample
in the Sample Delivery Group).
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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 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 reported on all data
reporting forms.
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
Exhibit B) and communication with SMO personnel.
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 time the delivery service is operating, including
Saturdays.
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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. Note: For those technical functions which require
a minimum educational degree and experience, an advanced degree in chemistry
or any scientific/engineering discipline, (e.g., Master's or Doctorate) does
not substitute for the minimum experience requirements.
Any personnel changes affecting the key personnel as stated in Exhibit A,
Section III, Items I and II, the Contractor shall notify in writing the
Technical Project Officer and the Administrative Project Officer within 14
days of the personnel change. The Contractor shall provide a detailed resume
to the Technical Project Officer, Administrative Project Officer, and EMSL/LV
for the replacement personnel within 14 days of the Contractor's assignment
of the personnel. The resume shall include position description of titles,
education (pertinent to this contract), number of years of experience
(pertinent to this contract) month and year hired, previous experience and
publications.
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 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 in
operating a GC/MS, 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.
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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 in
operating a GC/EC, including at least one year of
supervisory experience.
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 in
organic sample preparation, 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.
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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.
(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 laboratory
reports.
6. Programmer Analyst
a. Responsible for the installation, operation and
maintenance of software and programs generating, updating
and 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 laboratory
reports.
A-17 OLM01.2 1/91
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7. GC/MS Operator Qualifications
One year of experience in operating and maintaining GC/MS/DS
and a minimum of a Bachelor's degree in chemistry or a
scientific/engineering discipline, or in lieu of the minimum
education requirement, 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.
9. GC/EC Operator Qualifications
One year of experience in operating and maintaining GC/EC and
a minimum of a Bachelor's degree in chemistry or a
scientific/engineering discipline, or in lieu of the minimum
education requirement, 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.
A-18 OLM01.2 1/91
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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.
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. Samples, sample extracts, and
standards must be stored separately to prevent cross contamination.
Semivolatile and pesticide/Aroclor standards and extracts must be
stored separately from volatile standards and extracts.
3. Sample Preparation Area
Adequate, contamination-free, well-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.
A-19 OLM01.2 1/91
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b. Source of distilled or demineralized organic-free water.
c. Analytical balance(s) located away from draft and rapid change
in temperature.
C. Instrumentation
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.
1. Primary Instrument Requirements for up to 200 Samples/Month
Capacity
Fraction
Volatiles
Semivolatiles
Pesticides/
Aroclors
No. of
Ins trument ( s )
1
2
2
Type of
Instrument
GC/MS/DS with
purge and
trap device
GC/MS/DS
GC/EC/DS with
dual column
This equates to three GC/MS/DS and 2 GC/EC/DS.
NOTE: For 300-400 Samples/Month Capacity, twice as much instrumentation
is needed as is listed in item 1. For 500-600 Samples/Month Capacity,
three times as much instrumentation is needed as is listed in item 1.
For 700-800 Samples/Month Capacity, four times as much instrumentation
is needed as is listed in item 1.
2. Secondary Instrument Requirements for up to 400 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
Instruments
GC/MS/DS
Purge and Trap Device
GC/EC/DS
Note: For over 400 samples/month capacity, twice as much
instrumentation is needed as listed in item 2.
A-20
OIH01.3 2/91
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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/DS Exhibit D
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 720 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 Asynchronous, Hayes-compatible modem capable of at least 2,400
baud transmission speed. In addition, MNP level 5
compatibility is recommended.
o Modem capable of at least 2,400 baud transmission speed which
is compatible with the EPA Telecommunications Network.
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.
A-21 OLM01.2 1/91
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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. The
Contractor shall have adequate number of technical personnel to
meet the requirements of this contract.
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. Document Control Officer
Responsible for all aspects of data deliverables: organization,
packaging, copying, and delivery. Responsible for ensuring that
all documents generated are placed in the Complete SDG File for
inventory and are delivered to the appropriate EPA Regional
personnel or other receiver.
A-22 OLM01.3 2/91
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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/Deliverables Distribution B-3
SECTION II: Report Descriptions and Order of Data
Deliverables B-6
SECTION III: Forms Instructions B-24
SECTION IV: Data Reporting Forms B-53
B-2 OLM01.0
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SECTION I
CONTRACT REPORTS/DELIVERABLES DISTRIBUTION
(For 35-Day Turnaround Contracts)
The following table reiterates the Contract reporting and deliverables requirements
specified in the Contract Schedule and specifies the distribution that is required
for each deliverable. NOTE: Specific recipient names and addresses are subject to
change during the term of the contract. The Administrative Project Officer (APO)
will notify the Contractor in writing of such changes when they occur.
Item
No. Delivery Distribution
Copies Schedule (1) (2) (3) (4)
*****A. Standard Operating
Procedures
60 days after
contract award,
and as required
in Exhibit E.
X X
*B. Sample Traffic
Reports
***C. Sample Data Summary
Package
***D. Sample Data Package
***E. Complete SDG File
****
*****F. Quality
Assurance
Plan
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 days after
receipt of last
sample in SDG.
60 days after
contract award,
and as required
in Exhibit E.
As directed
***G. Data in Computer-
Readable Form
35 days after
receipt of last
sample in SDG.
B-3A
OLM01.3 2/91
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SECTION I
CONTRACT REPORTS/DELIVERABLES DISTRIBUTION
(For 14-Day Turnaround Contracts)
The following table reiterates the Contract reporting and deliverables requirements
specified in the Contract Schedule and specifies the distribution that is required
for each deliverable. NOTE: Specific recipient names and addresses are subject to
change during the term of the contract. The Administrative Project Officer will
notify the Contractor in writing of such changes when they occur.
Item
No. Delivery Distribution
Copies Schedule (I) (2) (3) C4")
*****A. Standard Operating
Procedures
60 days after
contract award,
and as required
in Exhibit E.
*B. Sample Traffic
Reports
***C. Sample Data Summary
Package
***D. Sample Data Package
***E. Complete SDG File
****
*****p. Quality
Assurance
. Plan
1 . 3 days after
receipt of last
sample in Sample
Delivery Group
(SDG).**
1 14 days after
receipt of last
sample in SDG.
! 14 days after
receipt of last
sample in SDG.
14 days after
receipt of last
sample in SDG.
J 60 days after
contract award,
and as required
in Exhibit E.
As directed
***G. Data in Computer-
Readable Form
14 days after
receipt of last
sample in SDG.
B-3B
OLM01.3 2/91
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Item
No.
Copies
Delivery Distribution
Schedule (1) (2) (3) (U)
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
(4) NEIC
* 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 (7 days or less for 14-day data turnaound
contracts) 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 (Section G, 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 the
reconciled complete SDG file.
B-4
OLM01.3 2/91
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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 22314
(2) 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/name lists as necessary throughout the period of the contract and
identify other client recipients on a case-by-case basis.
(3) 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
(4) USEPA National Enforcement Investigations Center (NEIC)
Attn: CLP Audit Program
Denver Federal Center Bldg. 53
P.O. Box 25227
Denver, CO 80225
B-5 OLM01.4 3/91
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SECTION II
REPORT DESCRIPTIONS AND ORDER OF DATA DELIVERABLES
Th'e Contractor laboratory shall provide reports and other deliverables as
specified in the Contract Schedule (Performance/Delivery Schedule, Section
F). 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 consecutively in ascending order starting from the SDG
Narrative.
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 Administrative Project
Officer/Technical Project Officer action, or through a Regional data
reviewer's request, 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) 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.
A. Quality Assurance Plan and Standard Operating Procedures
See Exhibits E and F for requirements.
B-6 OLM01.3 2/91
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B. Sample 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.
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 must 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 (TRs1) , 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 Summary 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
B-7 OLM01.0
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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:
1. SDG 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. By 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)
Sample Data Package
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.
B-8 OLM01.0
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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.
The Contractor must also list the pH determined for each water
sample submitted for volatiles analysis. This information may
appear as a simple list or table in the SDG Narrative. The purpose
of this pH determination is to ensure that all volatiles samples
were acidified in the field. No pH adjustment is to be performed by
the Contractor on water samples for volatiles analysis.
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 designee, 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 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 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 VOA)
(2) Matrix Spike/Matrix Spike Duplicate Summary (Form III VOA)
B-9 OLM01.2 1/91
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(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, by instrument.)
(4) GC/MS Instrument Performance Check (Form V VGA)
In chronological order; by instrument.
(5) Internal Standard Area and RT Summary (Form VIII VGA)
In chronological order; by instrument.
b. Sample Data
Sample data shall be arranged in packets with the Organic
Analysis Data Sheet (Form I VGA, including Form I VGA-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 numbers in ordering
samples.
(1) Target Compound Results - Organic Analysis Data Sheet
(Form I VGA),
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 D.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 VGA-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 VGA-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 chromatograms (RIG) for each
sample or sample extract.
RICs must be normalized to the largest nonsolvent
component, and must contain the following header
information:
B-10 OLM01.2 1/91
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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.
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,"
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 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-ll OLM01.0
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(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
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.
d. 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
B-12 OLM01.0
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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.
(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 VGA) 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.)
B-13 OLM01.0
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(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 semivolatile samples. These
sample packets must 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 SV-1, SV-2).
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 D.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.
B-14 OLM01.2 1/91
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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,"
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 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.
B-15 OLM01.0
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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.
(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
showing 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 (RIC), labeled
as in b.(3) above.
B-16 OLM01.0
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(2) Blank Data - in chronological order by extraction date.
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.
(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.
5. Pesticide/Aroclor Data
a. QC Summary
(1) Surrogate Percent Recovery Summary (Form II PEST)
(2) Matrix Spike/Matrix Spike Duplicate Summary (Form III
PEST)
B-17 OLM01.2 1/91
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(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 (Form 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 D.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) 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.
B-18 OLM01.2 1/91
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(6) If pesticide/Aroclors are confirmed by GC/MS, the
Contractor shall submit copies of reconstructed ion
chromatograms, raw spectra and 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.
(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 Individual 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
increasing EPA sample number.
B-19 OLM01.2 1/91
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(10) Pesticide Identification Summary for Multicomponent
Analytes (Form X PEST-2) - for all samples with positively
identified multicomponent analytes, in order by increasing
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.
(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) 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.
B-20 OLM01.2 1/91
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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.
(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.
B-21 OLM01.0
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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.
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.
B-22 OLM01.0
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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.
G. GC/MS Tapes
See Exhibit E for requirements.
H. Extracts
The Contractor shall preserve sample extracts at 4°C (+2eC) 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.
B-23 OLM01.2 1/91
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SECTION III
FORMS INSTRUCTIONS
B-24 OLM01.0
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SECTION III
FORM INSTRUCTION GUIDE
This section includes specific instructions 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 VGA 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 (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 Calibration Verification Summary(Form VII PEST)
L. Internal Standard Area and RT 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)
B-25 OLM01.2 1/91
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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 (e.g., "Lab Code," "Chloromethane")
must appear as they do on the forms in the contract, including the
options specified in the form (e.g., "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 (e.g., "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.
B-26 OLM01.0
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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 by 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.
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.
B-27 OLM01.4 3/91
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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. Semivolatile blanks shall be identified as SBLK##.
3. Pesticide/Aroclor method blanks shall be identified as
PBLK##.
4. Pesticide/Aroclor instrument blanks shall be identified as
PIBLK##.
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, VBUKAB, 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.
B-28 OLM01.0
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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 AR1660##.
The laboratory must create a unique "EPA Sample No." within an SDG by
replacing the two-character "##" terminator of the identifier with one
or two characters or numbers, or a combination of both.
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 "SOIL" for soil/sediment samples, and enter "WATER"
for water samples. NOTE: The matrix must be spelled out.
Abbreviations such as "S" or "W" shall not be used.
For "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.
B-29
OLM01.2 1/91
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"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.
"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 a 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.
Organic Analysis Data Sheet (Form I. All Fractions)
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
VGA analysis only is requested, Form I VOA 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.
B-30 OLM01.0
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Complete the header information on each page of Form I required,
according to the instructions in Part A and as follows:
For soil samples analyzed 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 VGA vial are considered as the sample. For water samples, leave
this field blank.
For soil samples analyzed for semivolatiles and pesticides/Aroclors,
enter the values for the percent moisture determined during the
analysis. 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
water samples, 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
separatory 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. When continuous liquid-liquid extraction procedures are used
for water samples, enter the date on which the procedure was started
for "Date Extracted". If separatory funnel (pesticides only) 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.
B-31 OLM01.2 1/91
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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).
For semivolatiles, enter the actual volume of the most concentrated
sample extract, in microliters, under "Concentrated Extract Volume".
This volume typically will be 1000 uL (water), or 500 uL (water and
soil) when GPC was performed. For pesticides/Aroclors, the volume of
the most concentrated extract typically will be 10000 uL (water), or
5000 uL (water and soil) when GPC is performed. For
pesticides/Aroclors, the volume of the most concentrated extract is not
the volume taken through the Florisil and sulfur cleanup steps. 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
pesticide/Aroclors are analyzed using two GC columns connected to a
single injection port, the "Injection Volume" must be entered as half
the volume in the syringe, i.e., assume that the extract injected is
evenly divided between the two columns.
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 I. 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 footnotes. 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.
B-32 OLM01.3 2/91
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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
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 semivolatile soil samples, the extract must be concentrated
to 0.5 mL, and the sensitivity of the analysis is not
compromised by the cleanup procedures. Similarly, pesticide
samples subjected to GPC are concentrated to 5.0 mL.
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 under the
following circumstances: 1) when estimating a concentration for
tentatively identified compounds where a 1:1 response is
assumed, 2) when the mass spectral and rentention time data
indicate the presence of a compound that meets the volatile and
semivolatile GC/MS identification criteria, and the result is
less than the CRQL but greater than zero, 3) when the retention
time data indicate the presence of a compound that meets the
pesticide/Aroclor identification criteria and the result is
less than the CRQL but greater than zero. Note: the "J" code
is not used and the compound is not reported as being
identified for pesticide/Aroclor results less than the CRQL, if
the technical judgement of the pesticide residue analysis
expert determines that the peaks used for compound
identification resulted from instrument noise or other
interferences (column bleed, solvent contamination, etc.). 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 must be adjusted for dilution as
discussed for the U flag.
B-33 OLM01.8 8/91
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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. For generic characterization of
a TIC, such as chlorinated hydrocarbon, the N code is not used.
B-33a OLM01.8 8/91
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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
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.
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 the
peak representing the single isomer exceeds 200 ug/L or the
peak representing the two coeluting isomers on that GC column
exceeds 400 ug/L. Similarly, if the two 1,2-Dichloroethene
isomers coelute, a diluted analysis is not required unless the
concentration exceeds 400 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.
B-(page) OLM01.2 1/91
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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
samples. The laboratory-defined flags are limited 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.
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 in 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 unlgnown.
Include a Form 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 termed volatile surrogates, are used
to monitor the performance of the purge and trap-gas chromatograph-mass
B-35 OLM01.3 2/91
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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. D.Q not mix low and medium
level samples on one form. 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.
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".
B-36 OLM01.0
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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 columns 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
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. The total number outside the QC limits
includes all values, regardless of GC column.
Number all pages as described in part A.
E. 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
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 D, and enter under "MS % REG". Flag all
B-37 OLM01.3 2/91
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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 for 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 also 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.
Complete the lower 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 (RPD) 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
limits given on the form, and flag each RPD outside the QC limits with
an asterisk (*) in the last space of the "% RPD" column, under the "#"
symbol.
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 separatory funnel, "SONG" for sonication, or "CONT" for continuous
liquid-liquid extraction.
B-38 OLM01.1 12/90
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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
IV associating all the samples with the method blank, and a second
version of Form IV listing only those samples associated with the
separate sulfur cleanup blank. Note: Subjecting all samples
associated with a method blank to sulfur cleanup avoids the need for
two forms.
Pesticide/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 VOA 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
B-39 OLM01.0
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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.
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.
B-40 OLM01.0
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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 spike 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 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 - Standard Deviation x 100
Mean
Where,
n
E
Standard Deviation -
n-1 |
Where,
X£ - each individual value used to calculate the mean
x — the mean of n values
n — the total number of values
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 nanograms per injection is
difficult. If a four-point calibration is performed for these compounds,
leave RF20 blank.
B-41 OLM01.2 1/91
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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 form 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 time windows, and
calibration factors. For single component pesticide target compounds,
these data are calculated from the analyses of the Individual Standard
Mixtures A and B at three different concentration levels. For the
multicomponent target compounds, these data are calculated from a
single point calibration.
For the three analyses of Individual Standard Mixture A (low point, mid
point, and high point), and the three analyses of Individual Standard
Mixture B performed on each GC column during an initial calibration,
complete one copy of Form VI for each GC column used.
Complete the 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 six 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 specified in Exhibit D as
four times the low point, therefore, enter "4.0" for "mid". The high
point standard must be at least 16 times the low point, but may be
higher, if that value lies within the linear range of the instrument,
as specified in Exhibit D. Therefore, enter the appropriate multiplier
to the high point standard concentration to one decimal place.
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".
Calculate the retention time window for each analyte using the
specifications in Exhibit D, 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 from the analyses of
Individual Mixture A and the windows are only required to be calculated
for Individual Mixture A.
For the six analyses of the Individual Standard Mixtures, 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 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
B-42 OLM01.2 1/91
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standards, and calculate a mean calibration and a percent relative
standard deviation (%RSD), and enter on the form. As with surrogate
retention times, the calibration factors are only required from
Individual Mixture A analyses.
In order to be used for sample analyses, the %RSD of the calibration
factors for each single component target compound must be less than or
equal to 20.0 percent except as noted in the following. The %RSD of
the calibration factors for the two surrogates must be less than or
equal to 30.0 percent. Up to two single component target compounds
(but not surrogates) may exceed the 20.0 percent limit for %RSD, but
these compounds must have a %RSD of less than of equal to 30.0 percent.
These criteria apply to both GC columns.
For the multicomponent target compounds, the retention times, retention
time windows, and calibration factor must 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.
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 pf 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
definition in Exhibit D PEST. 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
B-43 OLM01.2 1/91
-------
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%.
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
over more than 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 relative
response factor (RRF50) from the continuing calibration standard
analysis. Calculate the Percent Difference (%D) for all compounds.
- RRFC
% Difference x 100
Where
Average relative response factor from initial calibration.
RRFC - Relative response factor from continuing calibration
standard.
All semivolatile standards are analyzed at 50 total ng.
B-44 OLM01.2 1/91
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K. GC/EC Calibration Verfication Summary (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 over 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.
When reporting data for the PEM at the beginning of the initial
calibration sequence, leave blank the "EPA Sample No.", "Lab Sample
ID", and "Date" and "Time Analyzed" fields for the instrument blank
(PIBLK), as no instrument blank is analyzed before this PEM. When
reporting all other PEM analyses, the instrument blank fields must be
completed.
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 decimal places. 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".
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 mid point concentrations of Individual
Standard 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.
B-45 OLM01.2 1/91
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L. Internal Standard Area and RT Summary (Form VIII VGA 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 times 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
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 the 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.
B-46 OLM01.0
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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 decachlorobipheny1 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 time (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 time 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
RT column blank for that 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
B-47 OLM01.0
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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 column used to determine the
recovery of the analytes in the Florisil cartridge check solution,
under "GC Column (1)". If more than one GC column is used, enter the
information for a second column under "GC Column (2)", etc., as
discussed previously.
In the upper table, enter the amount of spike added and spike recovered
in nanograms for each analyte.
Calculate to the nearest whole percent, and enter the percent recovery
in the "% REG" 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 must be used to process all
soil sample extracts for pesticide/Aroclor analyses.
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.
B-48 OLM01.2 1/91
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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
as 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 Aroclors 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
I, 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
the concentrations entered on this form, using the equation below, and
report it to a tenth of a percent under "%D".
%D » ConcH - Conct
x 100
Conct
B-49 OLM01.2 1/91
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Where,
ConcH — The higher of the two concentraiton for the target compound in
question
Conct — The lower of the two concentrations for the target compound in
question
Note that using this equation will result in percent difference values
that are always positive. The value will also be greater than a value
calculated using the higher concentration in the denominator, however,
given the likelihood of a positive interference raising the
concentration determined on one GC column, this is a conservative
approach to comparing the two concentrations.
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 any target compound. If the percent difference
between the calculated concentrations is greater than 25.0 percent,
flag the concentration on Form I, as described previously. This will
alert the data user to the potential problems in quantitating this
analyte.
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 time and concentration of each
peak chosen for quantitation in the target analyte, 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.
B-50 OLM01.2 1/91
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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 the container, remove the enclosed sample documentation, and
record the presence/absence of chain-of-custody record(s), SMO forms
(i.e., Traffic Reports, Packing Lists), and airbills or airbill
stickers in items 3-5 on Form DC-1. Specify if there is an airbill
present or an airbill sticker in item 5 on Form DC-1. Record the
airbill or sticker number in item 6.
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.
B-51 OLM01.0
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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.
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-52 OLM01.0
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SECTION IV
DATA REPORTING FORMS
B-53 OLM01.0
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jab Name:
..ab Code:
1A
VOLATILE ORGANICS ANALYSIS DATA SHEET
Contract:
SAS No.:
EPA SAMPLE NO.
Case No.:
SDG No.:
latrix: (soil/water)
sample wt/vol: (g/mL)
jevel: (low/med)
; Moisture: not dec.
;c 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
74-83-9 Bromomethane
75-01-4 Vinyl Chloride
75-00-3 Chloroethane
.75-09-2 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 Dibromochloromethane
79-00-5 1,1, 2-Trichloroethane
71-4 3-2 Benzene
10061-02-6 trans-l,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 VOA
3/90
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b Name:
b Code:
IB
SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET
Contract:
Case No.: SAS No.:
EPA SAMPLE NO.
SDG No.:
trix: (soil/water)
mple wt/vol: (g/mL)
vel: (low/med)
Moisture: decanted: (Y/N)
•ncentrated Extract Volume: (uL)
jection Volume: (uL)
C 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)
108-95-2 Phenol
111-44-4 bis (2-Chloroethyl) ether
9 5-57-8 2 -Chlorophenol
541-73-1 1,3-Dichlorobenzene
106-46-7 i, 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
77-4 7-4 Hexachlor ocyclopentadiene
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
-------
L.ab Name:
Code:
1C
SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET
Contract:
SAS No.:
EPA SAMPLE NO.
Case No.:
SDG No.:
latrix: (soil/water)
Sample wt/vol: (g/»L)
jevel: (low/med)
; Moisture: decanted: (Y/N)
:oncentrated Extract Volume: (uL)
Injection Volume: (uL)
5PC 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)
51-28-5 2,4-Dinitrophenol
100-02-7 4-Nitrophenol
132-64-9 pibenzofuran
121-14-2 2,4-Dinitrotoluene
84-66-2 Diethylphthalate
7005-72-3 4-Chloropheny 1-pheny lether
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-Bromopheny 1-pheny lether
118-74-1 Hexachlorobenzene
87-86-5 Pentachlorophenol
85-01-8 Phenanthrene
120-12-7 Anthracene
86-74-8 Carbazole
84-74-2 Di-n-butylphthalate
206-4 4-0 Fluoranthene
129-00-0 Pyrene
85-68-7 Butylbenzylphthalate
91-94-1 3,3'-Dichlorobenzidine
56-55-3 Benzo (a) anthracene
218-01-9 Chrysene
117-81-7 bis (2-Ethylhexyl) phthalate
117-84-0 Di-n-octylphthalate •
205-99-2 Benzo (b) f luoranthene
207-08-9 Benzo (k) f luoranthene
50-32-8 Benzo (a) pyrene
193-39-5 Indeno(1,2, 3-cd)pyrene
53-70-3 Dibenz (a,h)anthracene
191-24-2 Benzo (g, h, i) perylene
(1) - Cannot be separated from Diphenylamine
FORM I SV-2
3/90
-------
ID
PESTICIDE ORGANICS ANALYSIS DATA SHEET
EPA SAMPLE NO.
ib Name:
ib Code:
Case No.:
Contract:
SAS No.:
itrix: (soil/water)
imple wt/vol: (g/mL)
Moisture: decanted: (Y/N)
{traction: (SepF/Cont/Sonc)
jncentrated Extract Volume:
ijection Volume: (uL)
5C 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 deita-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
EPA SAMPLE NO.
TENTATIVELY
_,ab Name:
jab Code: Case No
fatrix: (soil/water)
sample wt/vol:
jevel: (low/med)
; Moisture: not dec.
;c Column: ID:
>oil Extract Volume:
IDENTIFIED COMPOUNDS
Contract:
SAS No.: SDG No. :
Lab Sample ID:
(g/mL) Lab File ID:
Date Received:
Date Analyzed:
(mm) Dilution Factor:
fuL) Soil Aliquot Volume: (uL)
Number TICs found:
CONCENTRATION UNITS:
(ug/L or ug/Kg)
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. CONG.
Q
FORM I VOA-TIC
3/90
-------
IF
SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET
EPA SAMPLE NO.
TENTATIVELY IDENTIFIED COMPOUNDS
ib Name: Contract:
ib Code: Case No.: SAS No.: SDG No.:
itrix: (soil/water)
imple wt/vol: (g/mL)
rvel: (low/med)
Moisture: decanted: (Y/N)
mcentrated Extract Volume:
ijection Volume: (uL)
>C Cleanup: (Y/N) pH:
lumber TICs found:
(uL)
Lab Sample ID:
Lab File ID:
Date Received:
Date Extracted:
Date Analyzed:
Dilution Factor:
CONCENTRATION UNITS:
(ug/L or ug/Kg)
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
FORM I SV-TIC
3/90
-------
2A
WATER VOLATILE SYSTEM MONITORING COMPOUND RECOVERY
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SOG No.
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
SAMPLE NO.
SMC1
(TOL) #
SMC2
(BFB) #
SMC3
(DCE)#
OTHER
TOT
OUT
QC LIMITS
SMC1 (TOL) = Toluene-d8 (88-110)
SMC2 (BFB) = Broroofluorobenzene (86-115)
SMC3 (DCE) = l,2-Dichloroethane-d4 (76-114)
# 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
b Name:
b Code:
vel: (low/med)
Case No.:
Contract:
SAS No.:
SDG No.
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
SAMPLE NO.
SMC1
(TOL)#
SMC2
(BFB) #
SMC3
(DCE)#
OTHER
TOT
OUT
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
ge 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) #
S7
(2CP)#
SB
(DCB)#
TOT
OUT
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
QC LIMITS
SI (NBZ) = Nitrobenzene-d5 (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-Tribroroophenol (10-123)
S7 (2CP) = 2-Chlorophenol-d4 (33-110)
S8 (DCB) = l,2-Dichlorobenzene-d4 (16-110)
(advisory)
(advisory)
# Column to be used to flag recovery values
* Values outside of contract required QC limits
D Surrogate diluted out
page of
FORM II SV-1
3/90
-------
2D
SOIL SEMIVOLATILE SURROGATE RECOVERY
ib Name:
ib Code:
Case No.:
Contract:
SAS No.:
SDG No.
ivel:(low/med)
01
02
03
04
Ob
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.
SI
(NBZ)#
S2
(FBP) #
S3
(TPH) f
S4
(PHL)#
S5
(2FP)#
S6
(TBP)#
S7
(2CP)#
S8
(DCB)#
TOT
OUT
QC LIMITS
SI (NBZ) = Nitrobenzene-d5 (23-120)
S2 (FBP) = 2-Fluorobiphenyl (30-115)
S3 (TPH) = Terphenyl-dl4 (18-137)
S4 (PHL) = Phenol-d5 (24-113)
S5 (2FP) = 2-Fluorophenol (25-121)
S6 (TBP) = 2,4,6-Tribromophenol (19-122)
S7 (2CP) = 2-Chlorophenol-d4 (20-130)
S8 (DCB) = l,2-Dichlorobenzene-d4 (20-130)
(advisory)
(advisory)
# Column to be used to flag recovery values
* Values outside of contract required QC limits
D Surrogate diluted out
ige
of
FORM II SV-2
3/90
-------
2E
WATER PESTICIDE SURROGATE RECOVERY
Lab Name:
Lab Code:
3C Column (1):
Contract:
SAS No.:
SDG No.:
(nan) GC Column(2):
ID:
(nan)
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
SAMPLE NO.
TCX 1
%REC #
TCX 2
%REC #
DCS 1
%REC #
DCB 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-1
3/90
-------
2F
SOIL PESTICIDE SURROGATE RECOVERY
ib Name:
ib Code:
: Column(1):
Contract:
SAS No.:
SDG No.:
(mm) GC Column(2) :
ID:
(mm)
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
SAMPLE NO.
TCX 1
%REC #
TCX 2
%REC #
DCB 1
%REC #
DCB 2
%REC #
OTHER
(1)
OTHER
(2)
TOT
OUT
TCX = Tetrachlorb-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
age 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
COMPOUND
1 , 1-Dichloroethene
Trichloroethene
Benzene
Toluene
Chlorobenzene
SPIKE
ADDED
(ug/L)
MSD
CONCENTRATION
(ug/L)
MSD
%
REC #
%
RPD #
QC L]
RPD
14
14
11
13
13
CMITS
REC.
61-145
71-120
76-127
76-125
75-130
# Column to be used to flag recovery and RPD values with an asterisk
* Values outside of QC limits
RPD: out of outside limits
Spike Recovery: out of outside limits
COMMENTS:
FORM III VOA-1
3/90
-------
3B
SOIL VOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
b Name:
b Code:
Case No.:
trix Spike - EPA Sample No.:
Contract:
SAS No.:
SDG No.:
Level:(low/med)
COMPOUND
1 , 1-Dichloroethene
Trichloroethene
Benzene
Toluene
Chlorobenzene
SPIKE
ADDED
(ug/Kg)
SAMPLE
CONCENTRATION
(ug/Kg)
MS
CONCENTRATION
(ug/Kg)
MS
%
REC #
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
%
REC #
%
RPD #
QC L]
RPD
22
24
21
21
21
[MITS
REC.
59-172
62-137
66-142
59-139
60-133
Column to be used to flag recovery and RPD values with an asterisk
Values outside of QC limits
•D: out of outside limits
like Recovery: out of outside limits
)MMENTS:
FORM III VOA-2
3/90
-------
3C
WATER SEMIVOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Matrix Spike - EPA Sample 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
Pyrene
SPIKE
ADDED
(ug/L)
SAMPLE
CONCENTRATION
(ug/L)
_
MS
CONCENTRATION
(ug/L)
MS
%
REC #
QC.
LIMITS
REC.
12-110
27-123
36- 97
41-116
39- 98
23- 97
46-118
10- 80
24- 96
9-103
26-127
COMPOUND
Phenol
2-Chlorophenol
1, 4-Dichlorobenzene
N-Nitroso-di-n-prop. (i")
1,2, 4-Trichlorobenzene
4 -Chloro- 3 -methy Iphenol
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
EMITS
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
# 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:
b Code:
Case No.:
trix Spike - EPA Sample No.:
Contract:
SAS No.:
SDG No.:
Level:(low/med)
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
Pent achl or opheno 1
Pyrene
SPIKE
ADDED
(ug/Kg)
SAMPLE
CONCENTRATION
(ug/Kg)
MS
CONCENTRATION
(ug/Kg)
MS
%
REC #
QC.
LIMITS
REC.
26- 90
25-102
28-104
41-126
38-107
26-103
31-137
11-114
28- 89
17-109
35-142
COMPOUND.
Phenol
2 -Ch lor opheno 1
1 , 4-Dichlorobenzene
N-Nitroso-di-n-prop. (1)
1,2, 4-Trichlorobenzene
4-Chloro-3-methylphenol
Acenaphthene
4-Nitrophenol
2 , 4-Dinitrotoluene
Pentachloropheno 1
Pyrene
SPIKE
ADDED
(ug/Kg)
MSD
CONCENTRATION
(ug/Kg)
MSD
%
REC #
%
RPD #
QC L3
RPD
35
50
27
38
23
33
19
50
47
47
36
[MITS
REC.
26- 90
25-102
28-104
41-126
38-107
26-103
31-137
11-114
28- 89
17-109
35-142
1) N-Nitroso-di-n-propylamine
Column to be used to flag recovery and RPD values with an asterisk
Values outside of QC limits
>D: out of outside limits
)ike Recovery: out of outside limits
)MMENTS:
FORM III SV-2
3/90
-------
3E
WATER PESTICIDE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Lab Name:
Lab Code:
Case No.:
Matrix Spike - EPA Sample No.:
Contract:
SAS No.:
SDG 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
CONCENTRATION
(ug/L)
MSD
REC #
RPD #
QC L]
RPD
15
20
22
18
21
27
CMITS
REC.
56-123
40-131
40->120
52-126
56-121
38-127
# Column to be used to flag recovery and RPD values with an asterisk
* Values outside of QC limits
RPD: out of outside limits
Spike Recovery: out of outside limits
COMMENTS:
FORM III PEST-1
3/90
-------
3F
SOIL PESTICIDE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
ib Name:
ib Code:
Case No.:
Contract:
SAS No.:
SDG No.:
itrix Spike - EPA Sample No.:
COMPOUND
gamma-BHC (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 L:
RPD
50
31
43
38
45
50
EMITS
REC.
46-127
35-130
34-132
31-134
42-139
23-134
Column to be used to flag recovery and RPD values with an asterisk
Values outside of QC limits
'D: out of outside limits
3ike Recovery: out of outside limits
3MMENTS:
FORM III PEST-2
3/90
-------
Lab Name:
Lab Code:
4A
VOLATILE METHOD BLANK SUMMARY
Contract:
SAS No.:
EPA SAMPLE NO.
Case No.:
SDG No.:
Lab File ID:
Date Analyzed:
3C Column:
Lab Sample ID:
Time Analyzed:
ID:
(mm)
Heated Purge: (Y/N)
Instrument ID:
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
TIME
ANALYZED
COMMENTS:
page of
FORM IV VOA
3/90
-------
ib Name:
ib Code:
4B
SEMIVOLATILE METHOD BLANK SUMMARY
Contract:
SAS No.:
EPA SAMPLE NO.
Case No.:
SDG No.:
ib File ID:
istrument ID:
itrix: (soil/water)
ivel:(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
DMMENTS:
age 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:(SepF/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:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
EPA
SAMPLE NO.
LAB
SAMPLE ID
DATE
ANALYZED 1
DATE
ANALYZED 2
COMMENTS:
page of
FORM IV PEST
3/90
-------
5A
VOLATILE ORGANIC INSTRUMENT PERFORMANCE CHECK
BROMOFLUOROBENZENE (BFB)
.b Name:
b Code:
Case No.:
Contract:
SAS No.:
SDG No.:
b File ID:
.strument ID:
: Column:
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
( )1
( )1
( )1
( )2
1-Value is % mass 174 2-Value is % mass 176
IIS CHECK APPLIES TO THE FOLLOWING SAMPLES, MS, MSD, BLANKS, AND STANDARDS:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
EPA
SAMPLE NO.
LAB
SAMPLE ID
-
LAB
FILE ID
DATE
ANALYZED
TIME
ANALYZED
ige of
FORM V VOA
3/90
-------
5B
SEMIVOLATILE ORGANIC INSTRUMENT PERFORMANCE CHECK
DECAFLUOROTRIPHENYLPHOSPHINE (DFTPP)
Lab Name:
Lab Code:
Contract:
Case No.:
SAS No.:
SDG No.:
Lab File ID:
Instrument ID:
DFTPP Injection Date:
DFTPP Injection Time:
m/e
51
68
69
70
127
197
198
199
275
365
441
442
443
ION ABUNDANCE CRITERIA
30.0 - 80.0% of mass 198
Less than 2.0% of mass 69
Mass 69 relative abundance
Less than 2.0% of mass 69
25.0 - 75.0% of mass 198
Less than 1.0% of mass 198
Base Peak, 100% relative abundance
5.0 to 9.0% of mass 198
10.0 - 30.0% of mass 198
Greater than 0.75% of mass 198
Present, but less than mass 443
40.0 - 110.0% of mass 198
15.0 - 24.0% of mass 442
% RELATIVE
ABUNDANCE
( )1
( )1
( )2
1-Value is % mass 69 . 2-Value is % mass 442
THIS CHECK APPLIES TO THE FOLLOWING SAMPLES, MS, MSD, BLANKS, AND STANDARDS:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
EPA
SAMPLE NO.
LAB
SAMPLE ID
LAB
FILE ID
DATE
ANALYZED
TIME
ANALYZED
page __ of
FORM V SV
3/90
-------
6A
VOLATILE ORGANICS INITIAL CALIBRATION DATA
ib Name:
ib Code:
Case No.:
Contract:
SAS No.:
SDG No.
istrument ID:
sated Purge: (Y/N)
: Column: ID:
Calibration Date(s):
Calibration Times:
(mm)
jAB FILE ID: RRF10 =
RRF20 =
*RF50 - RRF100- RRF200=
COMPOUND
:h lor ome thane
RRF10
Bromomethane *
/inyl Chloride *
:hloroethane
fethylene Chloride
Acetone
Zarbon Disulfide
L , l-Dichloroethene *
L , l-Dichloroethane *
L , 2-Dichloroethene (total)
Chloroform *
L , 2 -Dichloroethane *
2-Butanone
1,1, 1-Trichloroethane *
Carbon Tetrachloride *
Sromodichloromethane *
L , 2-Dichloropropane
=is-l, 3-Dichloropropene *
Trichloroethene *
D ibromochloromethane *
L.I, 2-Trichloroethane *
Benzene *
trans-1, 3-Dichloropropene *
Bromoform *
4 -Methyl-2-Pentanone
2-Hexanone
Tetrachloroethene *
1,1,2,2 -Tetrachloroethane *
Toluene *
Chlorobenzene *
Ethylbenzene *
Styrene *
Xylene (total) *
Toluene-dS
Bromof luorobenzene *
1 , 2-Dichloroethane-d4
RRF20
RRF50
-
RRF100
RRF200
RRF
%
RSD
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
4
i
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:
LAB FILE ID: RRF20 = RRF50 =
RRF80 = RRF120= RRF160=
COMPOUND RRF20
Phenol *
bis (2-Chloroethyl) ether *
2-Chlorophenol *
1,3-Dichlorobenzene *
1,4-Dichlorobcnzene *
1 , 2 -Dichlorobenzene *
2 -Methy Iphenol *
2,2' -oxybis ( 1-Chloropropane)
4-Methylphenol *
N-Nitroso-di-n-propylamine *
Hexachloroethane *
Nitrobenzene *
Isophorone *
2-Nitrophenol *
2 , 4 -Dimethy Iphenol *
bis ( 2 -Chloroethoxy) methane *
2,4-Dichlorophenol *
1,2,4 -Tr ichlor obenz ene *
Naphthalene *
4 -Chlor oani 1 ine
Hexachlorobutadiene
4 -Chlor o-3 -methy Iphenol *
2-Methylnaphthalene *
Hexachlorocyclopentadiene
2,4, 6-Trichlorophenol *
2,4, 5-Trichlorophenol *
2-Chloronaphthalene *
2-Nitroaniline
Dimethy Iphtha late
Acenaphthylene *
2,6-Dinitrotoluene *
3-Nitroaniline
Acenaphthene *
2 , 4-Dinitrophenol
4 -N i tr opheno 1
Dibenzofuran *
2 , 4 -Dinitrotoluene *
RRF50
RRF80
RRF120
* Compounds with required minimum RRF and maximum %RSD val
RRF160
RRF
RSD
^
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
ues.
All other compounds must meet a minimum RRF of 0.010.
FORM VI SV-l
3/90
-------
6C
SEMIVOLATILE ORGANICS INITIAL CALIBRATION DATA
ab Name:
ib Code:
Case No.:
Contract:
SAS No.:
SDG No.
istrument ID:
Calibration Date(s):
Calibration Times:
JVB FILE ID: RRF20 =
>T>T?Qn _ DD1P1 O f\-
<±cr ou — KKr i/u-
COMPOUND
Jiethylphthalate
l-Chlorophenyl-phenylether *
rluorene *
l-Nitroaniline
1 , 6-Dinitro-2-mettiyiphenol
J-Nitrosodiphenylamine (1)
1 -Bromopheny 1-pheny lether *
iexachlorobenzene *
3entachlorophenol *
5henanthrene ^
Vnthracene "
:arbazole
) i -n-buty Iphtha 1 at e
^luoranthene ^
fyrene J
Jutylbenzylphthalate
$ , 3 ' -Dichlorobenzidine
Senzo (a) anthracene •>
:hrysene *
sis (2-Ethylhexyl) phthalate
) i -n-octy Iphtha late
Jenz o ( b ) f luor anthene i
Jenz o ( k ) f luor anthene *
Jenzo(a)pyrene i
Cndeno(l,2,3-cd)pyrene *
)ibenz( a, h) anthracene '
Jenzo(g,h,i)perylene ^
Jitrobenzene-d5
'-Fluorobiphenyl '
:erphenyl-d!4 '
3henol-d5
J-Fluorophenol
l , 4 , 6-Tr ibromophenol
j-Chlorophenol-d4
L , 2-Dichlorobenzene-d4
RRF20
k
k
b
It
k
b
t
b
k
It
k
k
It
t
k
t
k
k
k
fc
k
*
k
RRF50
— — ™- ^-••••••i
RRF50
•OUT?! C
RRF80
— -^^^ .!•!•—-
=
*\ —
KRF120
RRF160
RRF
%
RSD
4
4
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
4
*
4
4
4
4
4
L) Cannot be separated from Diphenylamine
Compounds with required minimum RRF and maximum %RSD values.
All other compounds must meet a minimum RRF of 0.010.
FORM VI SV-2
3/90
-------
6D
PESTICIDE INITIAL CALIBRATION OF SINGLE COMPONENT ANALYTES
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
Instrument ID:
3C Column:
Level (x low): low
ID: (mm) Date(s) Analyzed:
SDG No.: _
mid high
COMPOUND
alpha-BHC
beta-BHC
delta-BHC
gamma -BHC (Lindane)
Heptachlor
Aldrin
Heptachlor epoxide
Endosulfan I
Dieldrin
4, 4 '-DDE
Endrin
Endosulfan II
4,4'-DDD
Endosulfan sulfate
4.4'-DDT
Methoxychlor
Endrin ketone
Endrin aldehyde
alpha-Chlordane
aamma-chlordane
Tetrachloro-m-xylene
Decachlorobiphenyl
RT O]
LOW
F STANDS
MID
URDS
HIGH
MEAN
RT
RT w:
FROM
ENDOW
TO
* Surrogate retention times are measured from Standard Mix A analyses.
Retention time windows are + 0.05 minutes for all compounds that elute
before Heptachlor epoxide, +0.07 minutes for all other compounds,
except ±0.10 minutes for Decachlorobiphenyl.
FORM VI PEST-1
3/90
-------
6E
PESTICIDE INITIAL CALIBRATION OF SINGLE COMPONENT ANALYTES
ab Name:
ab Code:
istrument ID:
- 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 -BHC (Lindane)
Heptachlor
Aldrin
Heptachlor epoxide
Endosulfan I
Dieldrin
4, 4 '-DDE
Endrin
Endosulfan 11
4,4'-DDD
Endosulfan sulfate
4, 4 '-DDT
Methoxychlor
Endrin ketone
Endrin aldehyde
alpha-Chlordane
gamma-Chlordane
Tetrachloro-m-xylene
Decachlorobiphenyl
LOW
CALIBRATK
MID
DN FACTORS
HIGH
MEAN
%RSD
Surrogate calibration factors are measured from Standard Mix A analyses.
ISD must be less than or equal 20.0 % for all compounds except the
irrogates, where %RSD must be less than or equal to 30.0%. Up to
to target compounds, but not surrogates, may have %RSD greater than
).0* but less than or equal to 30.0%.
FORM VI PEST-2
3/90
-------
6F
PESTICIDE INITIAL CALIBRATION OF MULTICOMPONENT ANALYTES
Lab Name:
Lab Code:
Instrument ID:
3C Column:
Contract :
Case No . : SAS No . : SDG No . :
Date(s) Analyzed:
ID: (nan)
COMPOUND
Toxaphene
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
AMOUNT
(ng)
PEAK
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
RT
_
RT W
FROM
INDOW
TO
CALIBRATION
FACTOR
* Denotes required peaks
FORM VI PEST-3
3/90
-------
6G
PESTICIDE ANALYTE RESOLUTION SUMMARY
ib Name:
ib Code:
Case No.:
Contract:
SAS No.:
SDG No.
: Column (1):
ID:
>A Sample No. (Standard 1):
ite Analyzed (1):
: Column (2):
ID:
>A Sample No. (Standard 2):
ite Analyzed (2):
(mm) Instrument ID (1) :
Lab Sample ID (1):
Time Analyzed (1) :
01
02
03
04
05
06
07
08
09
ANALYTE
RT
RESOLUTION
(%)
(mm) Instrument ID (2):
Lab Sample ID (2):
Time Analyzed (2):
01
02
03
04
05
06
07
08
09
ANALYTE
RT
RESOLUTION
(%)
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
-------
7A
VOLATILE CONTINUING CALIBRATION CHECK
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
Instrument ID:
Lab File ID:
Calibration Date:
Heated Purge: (Y/N)
3C Column: ID:
Init. Calib. Date(s):
Init. Calib. Times:
(mm)
SDG No.:
Time:
COMPOUND
Chloromethane
Bromomethane
Vinyl Chloride
Chloroethane
Methylene Chloride
Acetone
Carbon Disulfide
1 , 1-Dichloroethene
1 , 1-Dichloroethane
1 , 2 -Dichlor oethene ( total )
Chloroform
1 , 2 -Dichlor oethane
2-Butanone
1,1, l-Trichloroethane
Carbon Tetrachloride
Bromod i chlor omethane
1 , 2-Dichloropropane
cis-1, 3-Dichloropropene
Tr ichlor oethene
D ibromochlor omethane
1,1, 2-Trichloroethane
Benzene
trans- 1 , 3-Dichloropropene
Bromof orm
4 -Methy 1-2 -Pent anone
2-Hexanone
Tetrachloroethene
1,1,2, 2 -Tetrachlor oethane
Toluene
Chlorobenzene
Ethylbenzene
Styrene
Xylene (total)
Toluene-d8
Bromof luor obenz ene
1 , 2 -Dichlor oethane-d4
RRF
RRF50
MIN
RRF
0.100
0.100
0.100
0.200
0.200
0.100
0.100
0.100
0.200
0.200
0.300
0.100
0.100
0.500
0.100
0.100
0.200
0.500
0.400
0.500
0.100
0.300
0.300
0.200
%D
MAX
%D
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
All other compounds must meet a minimum RRF of 0.010.
FORM VII VOA
3/90
-------
ib Name:
ib Code:
7B
SEMIVOLATILE CONTINUING CALIBRATION CHECK
Contract:
SAS No. :
Case No.:
istrument ID:
ib File ID:
Calibration Date:
SDG No.
Time:
Init. Calib. Date(s):
Init. Calib. Times:
COMPOUND
Phenol
bis (2-Chloroethyl) ether
2 -Chloropheno 1
1 , 3-Dichlorobenzene
1 , 4-Dichlorobenzene
1 , 2-Dichlorobenzene
2 -Methy Ipheno 1
2,2' -oxybis ( 1-Chloropropane)
4 -Methy Ipheno 1
N-Ni t roso-d i -n-pr opy lamine
Hexachloroe thane
Nitrobenzene
Isophorone
2 -Nitrophenol
2 , 4-Dimethylphenol
bis (2-Chloroethoxy) methane
2 , 4-Dichlorophenol
1 , 2 , 4-Trichlorobenzene
Naphthalene
4-Chloroaniline
Hexachlorobutadiene
4-Chloro-3-methylphenol
2-Methylnaphthalene
Hexachlorocyclopentadiene
2,4, 6-Tr ichlorophenol
2,4, 5-Trichlorophenol
2 -Chlor ©naphthalene
2-Nitroaniline
Dimethy Iphtha late
Acenaphthy lene
2 , 6-Dinitrotoluene
3-Nitroaniline
Acenaphthene
2 , 4-Dinitrophenol
4 -N itr opheno 1
Dibenzofuran
2 , 4-Dinitrotoluene
RRF
RRF50
MIN
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
%D
MAX
%D
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
All other compounds must meet a minimum RRF of 0.010.
FORM VII SV-1
3/90
-------
7C
SEMIVOLATILE CONTINUING CALIBRATION CHECK
Lab Name:
Lab Code:
Instrument ID:
Case No . :
Contract :
SAS No . :
Calibration Date:
SDG No.:
Time:
Lab File ID:
Init. Calib. Date(s):
Init. Calib. Times:
COMPOUND
Diethylphthalate
4-Chlorophenyl-phenylether
Fluorene
4 -Ni tr oan i 1 ine
4 , 6-Dinitro-2-methylphenol
N-Nitrosodiphenylamine (1)
4-Bromophenyl-phenylether
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 , i) pery lene
Nitrobenzene-d5
2 -F luor ob ipheny 1
Terphenyl-dl4
Phenol-d5
2 -F luor opheno 1
2,4, 6-Tribromophenol
2 -Ch lor opheno 1 -d4
1, 2-Dichlorobenzene-d4
RRF
RRF50
MIN
RRF
0.400
0.900
0.100
0.100
0.050
0.700
0.700
0.600
0.600
0.800
0.700
0.700
0.700
0.700
O.5OO
0.400
0.500
0.200
0.700
0.500
0.800
0.600
0.800
0.400
%D
MAX
%D
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. O
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
(1) Cannot be separated from Diphenylamine
All other compounds must meet a minimum RRF -of 0.010.
FORM VII SV-2
3/90
-------
7D
PESTICIDE CALIBRATION VERIFICATION SUMMARY
.b Name:_
.b Code:
: Column:
Contract:
SAS No.:
Case No.: SAS No.: SDG No.:
ID: (ma) Init. Calib. Date(s):
•A Sample No. (PIBLK) :
.b Sample ID (PIBLK) :
'A Sample No. (PEM) : _
.b Sample ID (PEM) :
Date Analyzed
Time Analyzed
Date Analyzed
Time Analyzed
PEM
COMPOUND
alpha-BHC
beta-BHC
gamma-BHC (Lindane)
Endrin
4, 4 '-DDT
Methoxychlor
RT
RT w:
FROM
ENDOW
TO
CALC
AMOUNT
(ng)
NOM
AMOUNT
(ng)
RPD
4'-DDT % breakdown (1):
>mbined % breakdown (1):
Endrin % breakdown (1)
: 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%
FORM VII PEST-1
3/90
-------
7E
PESTICIDE CALIBRATION VERIFICATION SUMMARY
Lab Name:_
Lab Code:
GC Column:
EPA Sample No.(PIBLK):
Lab Sample ID (PIBLK):
EPA Sample No.(INDA):
Lab Sample ID (INDA):
Contract:
SAS No.:
SDG No.:
(mm) Init. Calib. Date(s):
Date Analyzed :
Time Analyzed :
Date Analyzed :
Time Analyzed :
INDIVIDUAL MIX A
COMPOUND
alpha-BHC
qamma-BHC (Lindane)
Heptachlor
Endosulfan I
Dieldrin
Endrin
-4, 4 '-ODD
4, 4 '-DDT
Methoxychlor
Tetrachloro-m-xylene
Decachloroblphenyl
RT
RT W]
FROM
•
ENDOW
TO
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
qarama-Chlordane
Tetrachloro-m-xylene
Decachlorobiphenyl
RT
RT W]
FROM
ENDOW
TO
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
ib Name:
ib Code:
Case No.:
Contract:
SAS No.:
SDG No.:
ib File ID (Standard):
istrument ID:
: Column: ID:
Date Analyzed:
Time Analyzed:
(mm)
Heated Purge: (Y/N)
12 HOUR STD
UPPER LIMIT
LOWER LIMIT
EPA SAMPLE
NO.
ISl(BCM)
AREA #
RT #
IS2 (DFB)
AREA #
RT #
IS3 (CBZ)
AREA #
RT #
)2
13
)4
15
16
17
18
)9
.0
.1
.2
.3
.4
.5
.6
.7
.8
.9
20
22
ISI (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.
»ge of
FORM VIII VOA
3/90
-------
SB
SEMIVOLATILE INTERNAL STANDARD AREA AND RT SUMMARY
Name:
jab Code:
Case No.:
Contract:
SAS No.:
SDG No.
jab File ID (Standard):
Instrument ID:
Date Analyzed:_
Time Analyzed:
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(DCB)
AREA #
RT #
IS2 (NPT)
AREA #
.
RT #
IS3(ANT)
AREA #
RT #
IS1 (DCB) = l,4-Dichlorobenzene-d4
IS2 (NPT) = Naphthalene-d8
IS3 (ANT) = Acenaphthene-dIO
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-1
3/90
-------
8C
SEMIVOLATILE INTERNAL STANDARD AREA AND RT SUMMARY
ab Name:
ab Code:
Case No.:
Contract:
SAS No.:
SDG No.
ab File ID (Standard):
istrument ID:
Date Analyzed:
Time Analyzed:
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.
IS4 (PHN)
AREA #
RT #
ISS(CRY)
AREA #
RT #
IS6(PRY)
AREA #
RT #
IS4 (PHN) = Phenanthrene-dlO
IS5 (CRY) = Chrysene-dl2
IS6 (PRY) = Perylene-dl2
AREA UPPER LIMIT = +100% of internal standard area
AREA LOWER LIMIT = - 50% of internal standard area
RT UPPER LIMIT = +0.50 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.
age of
FORM VIII SV-2
3/90
-------
Lab Name:_
Lab Code:
GC Column:
8D
PESTICIDE ANALYTICAL SEQUENCE
Contract:
SAS No.:
Case No.: SAS No.: SDG No.:
ID: (mm) Init. Calib. Date(s):
Instrument ID:
THE ANALYTICAL SEQUENCE OF PERFORMANCE EVALUATION MIXTURES, BLANKS,
SAMPLES, AND STANDARDS IS GIVEN BELOW:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
JO
31
32
MEAN SURROGATE RT FROM INITIAL CALIBRATION
TCX: DCB:
EPA
SAMPLE NO.
LAB
SAMPLE ID
DATE
ANALYZED
. TIME
ANALYZED
TCX
RT #
DCB
RT #
TCX = Tetrachloro-m-xylene
DCB = Decachlorobiphenyl
QC LIMITS
(+ 0.05 MINUTES)
(± 0.10 MINUTES)
# Column used to flag retention time values with an asterisk.
* Values outside of QC limits.
page of
FORM VIII PEST
3/90
-------
9A
PESTICIDE FLORISIL CARTRIDGE CHECK
ib Name:
Contract:
ib Code:
Case No.:
SAS No.:
SDG No.:
.orisil Cartridge Lot Number:
: Column(l) : ID: _
Date of Analysis:
(mm) GC Column(2):
ID:
(mm)
COMPOUND
alpha-BHC
gamma -BHC (Lindane)
Heptachlor
Endosulfan I
Dieldrin
Endrin
4,4'-DDD
4,4' -DDT
Methoxychlor
Tetrachloro-m-xy lene
Decach lor ob ipheny 1
SPIKE
ADDED
(ng)
SPIKE
RECOVERED
(ng)
%
REC #
QC
LIMITS
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
# 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
18
19
20
21
22
23
EPA
SAMPLE NO.
N
LAB
SAMPLE ID
DATE
ANALYZED 1
DATE
ANALYZED 2
ige of
FORM IX PEST-1
3/90
-------
9B
PESTICIDE GPC CALIBRATION
Lab Name:
Lab Code:
GPC Column:
GC Column(1):
Case No.:
Contract:
SAS No.:
SDG No.:
ID:
Calibration Date:
(mm) GC Column (2) :
ID:
(mm)
COMPOUND
gamma -BHC (Lindane)
Heptachlor
Aldrin
Dieldrin
Endrin
4, 4 '-DDT
SPIKE
ADDED
(ng)
SPIKE
RECOVERED
(ng)
%
REC #
QC.
LIMITS
REC.
80-110
80-110
80-110
80-110
80-110
80-110
# 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
EPA
SAMPLE NO.
LAB
SAMPLE ID
DATE
ANALYZED 1
DATE
ANALYZED 2
page of
FORM IX PEST-2
3/90
-------
ib Name:
ib Code:
10 A
PESTICIDE IDENTIFICATION SUMMARY
FOR SINGLE COMPONENT ANALYTES
Contract:
SAS No.:
EPA SAMPLE NO.
Case No.:
SDG No.:
ib Sample ID :
istrument ID (1) :
: Column(1):
ID:
Date(s) Analyzed:
Instrument ID (2):
(mm) GC Column(2):
ID:
(mm)
ANALYTE
COL
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
RT
RT W3
FROM
:NDOW
TO
CONCENTRATION
%D
.ge of
FORM X PEST-1
3/90
-------
Lab Name:
Lab Code:
10B
PESTICIDE IDENTIFICATION SUMMARY
FOR MULTICOMPONENT ANALYTES
Contract:
SAS No.:
EPA SAMPLE NO.
Case No.:
SDG No.:
Lab Sample ID :
Instrument ID
GC Column(1):
ID:
Date(s) Analyzed:
Instrument ID (2):
(mm) GC Column(2):
ID:
(mm)
ANALYTE .
COLUMN 1
COLUMN 2
COLUMN 1
COLUMN 2
COLUMN 1
COLUMN 2
PEAK
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
RT
RT w;
FROM
=====
[NDOW
TO
CONCENTRATION
MEAN
CONCENTRATION
%D
At least 3 peaks are required for identification of multicomponent analytes
page of
FORM X PEST-2 3/90
-------
SAMPLE L.OG-IN SHEET
Lab Name: Ptfc of
Received By ( Print Name): , , Log-in Dat—
Received By (Signature):
Cite Number:
Simple Delivery
Group No.:
SAS Number
REMARKS:
1. Custody Seal(i) Prcient/Abaeni*
biuct/Brakea
1 Cnaady Sal Not=
3 . Chaim-of-Cusody Present/Absent*
Packw( Us
5. Aubffl Aiibill/Slicker
Pirseal/Afaccac*
fi. AnMlINa.:
7. SuapIeTap Pieuas/Abieaf
SonpIeTic Uae*N* Liaed
Numben oa Cbaia-of-
Outody -
S Sunple Condicioa- Intfta/Brefcen*/
Lealciat
. 9. Does infonBitioa oa
ousto^f irffird^ tnuK
Tcpotu. tat unple
Uti acne? Ye>/No*
• 10, D»le Rcceivai u L
-------
ORGANICS COMPLETE SDG FILE (CSF) INVENTORY SHEET
LABORATORY NAME
CITY/STATE
CASE NO. SDG NO.
SDG NOS. 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. SDG Cover Sheet/Traffic Report
4. Volatlles Data
a. QC Summary
System Monitoring Compound Summary
(Form II VGA)
Matrix Spike/Matrix Spike Duplicate Summary
(Form III VOA)
Method Blank Summary (Form IV VOA)
GC/MS Instrument Performance Check
(Form V VOA)
Internal Standard Area and RT Summary
(Form VIII VOA)
b. Sample Data
TCL Results - (Form I VOA)
Tentatively Identified Compounds
(Form I VOA-TIC)
Reconstructed total ion chromatograms (RIC>
for each sample
For each sample:
Raw spectra and background-subtracted
mass spectra of target compounds
identified
Quantisation reports
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 Data (Form VII VOA)
RICs and Quantitation Reports for all Standards
d. Raw QC Data
BFB
Blank Data.
Matrix Spike/Matrix Spike Duplicate Daca
FORM DC-2-1
OLM01.7 7/91
-------
ORGANICS COMPLETE SDG FILE (CSF) INVENTORY SHEET (Cent.)
CASE NO.
SDG NO.
SDG NOS. TO FOLLOW
SAS NO.
PAGE NOs
FROM TO
CHECK
LAB EPA
Seaivolatiles Data
a. QC Summary
Surrogate Percent Recovery Summary (Form II SV)
MS/USD Summary (Form III SV)
Method Blank Summary (Fora IV SV)
GC/MS Instrument Performance Check
(Form V SV)
Internal Standard Area and RT Summary
(Form VIII SV)
b. Sample Data
TCL Results (Form I SV-1, SV-2)
Tentatively Identified Compounds (Form I SV-TIC)
Reconstructed total ion chromatograms (RIG)
for each sample
For each sample:
Raw spectra and background-subtracted
mass spectra of target compounds
Quantitation reports
Mass spectra of TICs with three best library matches
GPC chromatograms (if GPC performed)
c. Standards Data (All Instruments)
Initial Calibration Data (Form VI SV-1, SV-2)
RICs and Quan Reports for all Standards
Continuing Calibration Data (Form VII SV-1, SV-2)
RICs and Quantitation Reports for all Standards
Semivolatile GPC Calibration Data-UV
detector traces
d. Raw QC Data
DFTPP
Blank Data
Matrix Spike/Matrix Spike Duplicate Data
Pesticides
a. QC Summary
Surrogate Percent Recovery Summary (Form II PEST)
MS/MSD Duplicate Summary (Form III PEST)
Method Blank Summary (Form IV PEST)
FORM DC-2-2
OLM01.7 7/91
-------
ORGANTCS .COMPLETE SDG FILE (CSF) INVENTORY SHEET (Cone.)
CASE NO. SDG NO. SDG NOS. TO FOLLOW
SAS NO.
PAGE NOs CHECK
FROH TO LAB EPA
6. Pesticides (cont.)
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
• Manual work sheets
For pesticides/Aroclors confirmed by GC/MS, copies
of raw spectra and copies of background-subtracted mass
spectra of target compounds (samples & standards)
c. Standards Data
Initial Calibration of Single Component
Analytes (Form VI PEST-1 and PEST-2)
Initial Calibration of Multicomponent Analytes
(Form VI PEST-3)
Analyte Resolution Summary (Form VI PEST-4)
Calibration Verification Summary (Form VII PEST-1)
Calibration Verification Summary (Form VII PEST-2)
Analytical Sequence (Form VIII PEST)
Florisil Cartridge Cheek (Form IX PEST-1)
Pesticide GPC Calibration (Form IX PEST-2)
Pesticide Identification Summary for Single Component
Analytes (Form X PEST-1)
Pesticide Identification Summary for Multicomponent
Analytes (Form X PEST-2)
Chromatograms and data system printouts
A printout of retention times and corresponding peak
areas or peak heights
Pesticide GPC calibration data - UV detector traces
d. Raw QC Data
Blank Data
Matrix Spike/Matrix Spike Duplicate Data
FORM DC-2-3 OLM01.7 7/91
-------
ORGANICS COMPLETE SDG FILE (CSF) INVENTORY SHEET (Cent.)
CASE NO. SDG NO. SDG NOS. TO FOLLOW
SAS NO.
PAGE NOs CHECK
FROM TO LAB EPA
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 • ZZHZ
All instrument output, including strip charts
from screening activities (describe or list)
EPA Shipping/Receiving Documents
Airbills (No. of shipments )
Chain-of-Custody Records
Sample Tags
Sample Log-In Sheet (Lab & DC1)
Miscellaneous Shipping/Receiving Records
(describe or list)
Internal Lab Sample Transfer Records and Tracking Sheets
(describe or list)
Other .Records (describe or list)
Telephone Communication Log
Comments:
npleted by: _^___
(CLP Lab) (Signature) (Printed Name/Title) (Date)
iited by:
(EPA) (Signature) (Printed Name/Title) (Date)
FORM DC-2-4
OLM01.7 7/91
-------
EXHIBIT C
TARGET COMPOUND LIST (TCL) AND
CONTRACT REQUIRED QUANTITATION LIMITS (CRQL)
NOTE: The values in these tables are quantitation 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.
Chlor ome thane
Bromome thane
Vinyl Chloride
Chloroethane
Methylene Chloride
Acetone
Carbon Disulfide
1 , 1-Dichloroethene
1 , 1-Dichloroethane
1,2-Dichloroethene (total)
Chloroform
1 , 2-Dichloroethane
2 - Butanone
1,1, 1-Trichloroethane
Carbon Tetrachloride
Bromodichlorome thane
1 , 2-Dichloropropane
cis - 1 , 3 -Dichloropropene
Trichloroethene
Dibromochlorome thane
1 , 1 , 2-Trichloroethane
Benzene
trans - 1 , 3 -Dichloropropene
Bromoform
4 -Methyl - 2 -pentanone
2-Hexanone
Tetrachloroethene
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
Ouantitation
Low
Water Soil
ug/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
(ng)
(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.
Note that the CRQL values listed on the preceding page may not be those •
C-2
OLM01.0
-------
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 VGA. 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"3 Kg/g) - 50 x 10'3 ug - 50 ng on the GC column
Medium Level Soil/Sediment Samples
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)
Quantisation
Low
Water Soil
Semivolatiles
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
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-
propylamine
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
ug/L
10
10
10
10
10
10
10
10
10
10
ug/Kg
330
330
330
330
330
330
330
330
330
330
Limits*
Med.
Soil
ug/Kg
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
On
Column
(ng)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
67-72-1
98-95-3
78-59-1
88-75-5
105-67-9
10
10
10
10
10
330
330
330
330
330
10000
10000
10000
10000
10000
(20)
(20)
(20)
(20)
(20)
44. Hexachloroethane
45. Nitrobenzene
46. Isophorone
47. 2-Nitrophenol
48. 2,4-Dimethylphenol
49. bis(2-Chloroethoxy)
methane
50 2,4-Dichlorophenol
51. 1,2,4-Trichlorobenzene
52. Naphthalene
53. 4-Chloroaniline
54. Hexachlorobutadiene
55. 4-Chloro-3-methylphenol
56. 2 -Me thyInaphthalene
57. Hexachlorocyclopentadiene
58. 2,4,6-Trichlorophenol
59. 2,4,5-Trichlorophenol
60. 2 -Chloronaphthalene
61. 2-Nitroaniline
62. Dimethylphthalate
63. Acenaphthylene
64. 2,6-Dinitrotoluene
65. 3-Nitroaniline
66. Acenaphthene
67. 2,4-Dinitrophenol
68. 4-Nitrophenol
# Previously known by the name bis(2-Chloroisopropyl) ether
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
10
10
10
10
10
10
10
10
10
10
25
10
25
10
10
10
25
10
25
25
330
330
330
330
330
330
330
330
330
330
800
330
800
330
330
330
800
330
800
800
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
25000
10000
25000
10000
10000
10000
25000
10000
25000
25000
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(50)
(20)
(50)
(20)
(20)
(20)
(50)
(20)
(50)
(50)
C-4
OLM01.2 1/91
-------
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
Semivolatiles
Dibenzofuran
2,4-Dinitrotoluene
Diethylphthalate
4 - Chlorophenyl -phenyl
ether
Fluorene
4 - Ni troani 1 ine
4, 6-Dinitro-2-methylphenol
N-nitrosodiphenylamine
4 - Bromopheny 1 -phenyle ther
Hexachlo robenz ene
Pentachlorophenol
Phenanthrene
Anthracene
Carbazole
Di-n-butylphthalate
Fluo r anthene
Pyrene
Butylbenzylphthalate
3,3' -Dichlorobenzidine
Benzo (a) anthracene
Chrysene
b i s ( 2 - E thy Ihexy 1 ) phthalate
Di-n-octylphthalate
Benzo (b) f luoranthene
Benzo (k) f luoranthene
Benzo ( a ) pyrene
Indeno (1,2,3-cd) pyrene
Dibenz( a, h) anthracene
Benzo (g,h,i)perylene
CAS Number
132-64-9
121-14-2
84-66-2
7005-72-3
86-73-7
100-01-6
534-52-1
86-30-6
101-55-3
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
Quant i
Water
ue/L
10
10
10
10
10
25
25
10
10
10
25
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
tation
Low
Soil
ug/Kg
330
330
330
330
330
800
800
330
330
330
800
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
Limits*
Med.
Soil
ue/Ke
10000
10000
10000
10000
10000
25000
25000
10000
10000
10000
25000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
10000
On
Column
(nz)
(20)
(20)
(20)
(20)
(20)
(50)
(50)
(20)
(20)
(20)
(50)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
(20)
The
* Quantitation limits listed for soil/sediment are based on wet weight.
quantitation limits calculated by the laboratory for soil/sediment,
calculated on dry weight basis as required by the contract, will be higher.
C-5
OLM01.1 12/90
-------
SEMIVOLATILES
Water Samples
AIL volume of water is extracted in a continuous liquid-liquid extractor
with 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) (W3 mL/uL) - 20 x 10'3 ug - 20 ng on the GC column
Low Soil Samples
A 30 g soil sample is extracted three times with methylene chloride/acetone
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/acetone,
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
oRQL of 10,000 ug/Kg:
(10,000 ug/Kg) (lg) (10-3 Kg/g) = 10 ug
(continued)
C-6 OLM01.2 1/91
-------
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
Eight semivolatile compounds are calibrated using only a four point initial
calibration, with the lowest standard at 50 ng. Therefore, the CRQL values
for these eight compounds are 2.5 times higher for all matrices and levels.
C-7 OLM01.1 12/90
-------
TARGET COMPOUND LIST (TCL) AND CONTRACT REQUIRED QUANTITATION LIMITS (CRQL)
Pesticides/Aroclors
CAS Number
Quantitation Limits*
Water Soil On Column
ue/L ue/Ke (vs.)
98.
99.
100.
101.
102.
alpha -BHC
beta-BHC
delta -BHC
gamma -BHC (Lindane)
Heptachlor
319-84-6
319-85-7
319-86-8
58-89-9
76-44-8
0.05
0.05
0.05
0.05
0.05
1.7
1.7
1.7
1.7
1.7
5
5
5
5
5
103. Aldrin
104. Heptachlor epoxide
105. Endosulfan I
106. Dieldrin
107. 4,4'-DDE
108. Endrin
109. Endosulfan II
110. 4,4'-ODD
111. Endosulfan sulfate
112. 4,4'-DDT
113. Methoxychlor
114. Endrin ketone
115. Endrin aldehyde
116. alpha-Chlordane
117. gamma-Chlordane
118. Toxaphene
119. Aroclor-1016
120. Aroclor-1221
121. Aroclor-1232
122. Aroclor-1242
123. Aroclor-1248
124. Aroclor-1254
125. Aroclor-1260
309-00-2
1024-57-3
959-98-8
60-57-1
72-55-9
72-20-8
33213-65-9
72-54-8
1031-07-8
50-29-3
0.05
0.05
0.05
0.10
0.10
0.10
0.10
0.10
0.10
0.10
1.7
1.7
1.7
3.3
3.3
3.3
3.3
3.3
3.3
3.3
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
8001-35-2
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
5.0
1.0
2.0
1.0
1.0
1.0
1.0
1.0
170.0
33.0
67.0
33.0
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
200
100
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
OLM01.1 12/90
-------
PESTICIDES/AROCLORS
Water Samples
AIL volume of water is extracted three times with methylene chloride or by
a continuous liquid-liquid extractor. This extract is reduced in volume to
approximately 3-5 mL, and diluted up to 10.0 mL with clean solvent. When Gel
Permeation Chromatography is performed, only 5 of the 10 mL of extract are
collected after GPC.
Regardless of whether GPC is performed, either 1.0 or 2.0 mL of the 10.0 mL
of the original extracts are taken through the remaining clean up steps
(Florisil and sulfur removal). The volume taken through Florisil cleanup and
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 volume taken through Florisil and the final
volume. If the autosampler cannot reliably handle 1.0 mL volumes, the 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 and an autosampler
requiring a 1.0 mL volume:
(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/acetone 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, either 1.0 or 2.0 mL of
that extract are 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) (10'3 Kg/g) - 51 x 10'3 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 OLM01.2 1/91
-------
Pesticides/Aroclors, continued -
Of which, only 1.0 or 2.0 mL are carried through the remaining cleanup 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.
If a single injection is used for two GC columns attached to a single
injection port, it may be necessary to use an injection volume greater than 2
uL.
C-10 OLM01.5 4/91
-------
EXHIBIT D
ANALYTICAL METHODS
FOR VOLATILES
D-l/VOA OLM01.0
-------
Table of Contents
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
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 GC/MS operation and
the purge and trap technique are interrelated.
D-3/VOA OLM01.0
-------
SECTION I
1. Method for the Determination of Volatile (Purgeable) 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 Chioromethane, 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 is 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.
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, sample extracts, and standards must be stored separately.
Volatiles standards must be stored separately from semivolatile and
pesticide/Aroclor standards.
2. Contract Required Holding Times
Analysis of water and soil/sediment samples must be completed within 10
days of validated time of sample receipt (VTSR).
D-6/VOA OLM01.2 1/91
-------
PART B - PROTOCOLS FOR HEXADECANE EXTRACTION OF VOIATILES 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
-------
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 97% or greater, the weight
can be used without correction to calculate the
concentration of the stock standard.
5.3.1.2 Transfer the stock standard 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 OLM01.2 1/91
-------
6. Sample 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 Fulling 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 each of working standard #1 and #2 to separate 40 mL
portions of reagent water in 50 mL volumetric flasks. 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 OLM01.2 1/91
-------
SECTION III
OPTIONAL SCREENING OF HEXADECANE
EXTRACTS FOR VOLATILES
D-10/VOA OLM01.0
-------
SECTION III
Summary of Method
The hexadecane extracts of water and soil/sediment are screened on a
gas chromatograph/flame ionizatlon 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 a temperature
programmable 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 are
approximately lOx less sensitive than aromatics. 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.
D-ll/VOA OLM01.2 1/91
-------
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
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 », CQ —, 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.
D-12/VOA OLM01.0
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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.
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 fug/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 20x
higher, and that for haloethanes is lOx higher.
6.3 Sample Analysis
Proceed to Section IV, GC/MS Analysis of Volatiles.
D-13/VOA OLM01.0
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SECTION IV
GC/MS ANALYSIS
OF VOIATILES
D-14/VOA OLM01.0
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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
1.2.1 Low level - an inert gas is bubbled through a mixture of
reagent water and 5 g of sample contained in a specifically
designed purging chamber that is held at an elevated
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.
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.
D-15/VOA OLM01.2 1/91
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SECTION IV
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 must be analyzed. Data must be retained by the
laboratory and be made available for inspection during on-site
laboratory 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 must 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, it may be necessary to wash out the purging
device with a detergent solution between analyses, rinse it with
distilled water, and then dry it in 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
Brand names, suppliers, and part numbers are for illustrative purposes
only. No endorsement is implied. Equivalent performance may be
achieved using apparatus and materials other than those specified here,
but demonstration of equivalent performance meeting the requirements of
this SOW is the responsibility of the Contractor.
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
3.5.1 Bottle - 15 mL, screw cap, with Teflon cap liner.
3.5.2 Volumetric flasks - class A with ground-glass stoppers.
3.5.3 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.
D-16/VOA OLM01.2 1/91
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SECTION IV
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
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 1808C 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 for low level soil
analysis, but not for waters or medium level soil analyses.
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.
D-17/VOA OLM01.2 1/91
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SECTION IV
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.
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 urn 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 6.4.3.
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.
D-18/VOA OLM01.2 1/91
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SECTION IV
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 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 personnel.
3.7.6 Magnetic tape storage device - must be capable of recording
data and must be suitable for long-term, off-line storage.
3.7.8 pH paper - wide range.
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.
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. Standards
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 certified. Manufacturer's
certificates of analysis must be retained by the Contractor and
presented upon request.
D-19/VOA OLM01.3 2/91
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SECTION IV
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.
5.2.2 Add the assayed reference material as described below.
5.2.2.1 If the compound is a liquid, using a 100 uL
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. For non-gaseous and compounds, 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. For gaseous compounds,
calculate the concentration in micrograms per microliter,
using the Ideal Gas Law, taking into account the temperature
and pressure conditions within the laboratory.
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.
D-20/VOA OLM01.5 4/91
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SECTION IV
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.
5.4 Working Standards
5.4.1 Instrument Performance Check Solution - p-Bromofluorobenzene
(BFB)
Prepare a 25 ng/uL 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/uL concentration is
used with a 2 uL injection volume. The laboratory may prepare
a 50 ng/uL solution of BFB if a 1 uL injection volume is used.
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.
5.4.3 Internal Standard Spiking Solution
Prepare an internal standard spiking solution containing
Bromochloromethane, Chlorobenzene-d5, and 1,4-Difluorobenzene
in methanol at the concentration of 25.0 ug/mL for each
internal standard. Add 10 uL of this spiking solution into
5.0 mL of sample or calibration standard for a concentration
of 50 ug/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-d4 in methanol at a concentration of 25.0
ug/mL. Add 10.0 uL of this spiking solution into 5.0 mL of
sample, for a. concentration of 50 ug/L. Prepare fresh spiking
solution weekly, or sooner if the solution has degraded or
evaporated.
D-21/VOA OLM01.5 4/91
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SECTION IV
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 ug/mL: 1,1-Dichloroethene,
Trichloroethene, Chlorobenzene, Toluene, and
Benzene. Prepare fresh spiking solution weekly, or
sooner if the solution has degraded or evaporated.
5.4.5.2 Matrix spikes are analyzed in duplicate; therefore,
add an aliquot of this solution to each of two
portions from one sample chosen for spiking.
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 ug/L
levels. Note: These are not the same levels as have been
used in previous Statements of Work. It is required that all
three Xylene isomers (o-, p-, and m-Xylene) be present in the
calibration standards at concentrations of each isomer equal
to that of the other target compounds (i.e., 10, 20, 50, 100,
and 200 ug/L). Similarly, the cis and trans isomers of 1,2-
dichloroethene must both be present in the standards at
concentrations of each isomer equal to that of the other
target compounds.
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.
D-22/VOA OLM01.5 4/91
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SECTION IV
5.5.3 The 50 ug/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 -20eC. 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.
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 recommended purge and trap analytical conditions
except as stated below:
Purge Conditions:
Purge Gas:
Purge Time:
Purge Flow Rate:
Purge Temperature:
Desorb Conditions:
Desorb Temperature:
Desorb Flow Rate:
Desorb Time:
Helium or Nitrogen
11.0 + 0.1 min
25-40 mL/min
Ambient (water or medium
level soil), required
40°C (low level soil),
required
180 °C
15 mL/min
4.0 + 0.1 min
D-23/VOA
OLM01.5 4/91
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Trap Reconditioning Conditions:
Reconditioning Temperature: 180"C
Reconditioning Time: 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.
6.2 Gas Chromatograph
The following are the recommended GC 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: 8eC/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)
Ramp Rate: 6°C/min
Final Temperature: 160°C
Final Hold Time: Until all target
compounds elute
6.2.3 Optimize GC conditions for analyte separation and sensitivity.
Once optimized, the same GC conditions must be used for the
analysis of all standards, samples, blanks, matrix spikes, and
matrix spike duplicates.
D-24/VOA OLM01.1 12/90
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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 2 seconds per
scan for capillary column
To give at least 5 scans per
peak, not to exceed 3 seconds per
scan for packed column
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).
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 subsequent standards, samples, MS/MSD, and blanks
associated with a BFB analysis must use identical mass
spectrometer instrument conditions.
D-25/VOA OLM01.8 8/91
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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.
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 injection 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.
D-26/VOA OLM01.0
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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-d5, 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.
Tabulate the area response of the characteristic ions in the
extracted ion current profile (EICP) against concentration for
each compound and internal standard and calculate relative
response factors (RRF) for each compound as follows:
Ax cis
RRF - — x —
Ais Cx
Where,
Ax - Area of the characteristic ion (EICP) for the compound
to be measured (see Table 4)
A£S - Area of the characteristic ion (EICP) for the
specific internal standard (see Table 3)
cis = Concentration of the internal standard
Cx = Concentration of the compound to be measured
D-27/VOA OLM01.0
-------
Calculating the relative response factor of the Xylenes and the
cis and trans isomers of 1,2-Dichloroethene requires special
attention. On packed columns, o-and p-Xylene isomers coelute.
On capillary columns, the m- and p-Xylene isomers coelute.
Therefore, when calculating the relative response factor in the
equation above, use the area response (Ax) and concentration
(Cx) of the peak that represents the single isomer on the GC
column used for analysis.
For the cis and trans isomers of 1,2-Dichloroethene which may
coelute on packed columns but not on capillary columns, both
isomers must be present in the standards. If the two isomers
coelute, use the area of the coeluting peak and the total
concentration of the two isomers in the standard to determine
the relative response factor. If the two isomers do not
coelute, sum the areas of the two peaks and the concentrations
of the two isomers in the standard to determine the relative
response factor.
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
Where,
* -o I. V2
Standard Deviation
n-1
Where,
Xi — each individual value used to calculate the mean
x — the mean of n values
n - the total number of values
7.4.5 The response factors of the compounds listed below (Table 2)
must meet the minimum RRF criteria at each concentration level
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-28/VOA OLM01.2 1/91
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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-1,3-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-1,3-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 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
Ch1oromethane Toluene-dg
1,2-Dichloroethene (total) l,2-Dichloroethane-d4
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
average relative response factor from the initial curve is
D-29/VOA OLM01.2 1/91
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SECTION IV
calculated. Calculate the percent difference for each compound
and compare with the maximum percent difference criteria listed
above. For negative percent difference values, the value must
be greater than or equal to -25.0%, but less than 0%. 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 required.
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 dees 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-30/VOA OLM01.3 2/91
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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 Once the sample aliquots have been taken from the VOA vial, the
pH of the water sample must be determined. The purpose of the
pH determination is to ensure that all VOA samples were
acidified in the field. Test the pH by placing one or two
drops of sample on the pH paper (do not add pH paper to the
vial). Record the pH of each sample, and report these data in
the SDG Narrative, following the instructions in Exhibit B. No
pH adjustment is to be performed by the Contractor.
D-31/VOA OLM01.2 1/91
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SECTION IV
8.1.8 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.
8.1.8.1 The following procedure will allow for dilutions
near the calculated dilution factor from the
screening procedure:
.8.1.8.1.1 All dilutions are made in volumetric
flasks (10 mL to 100 mL).
8.1.8.1.2 Select the volumetric flask that will
allow for the necessary dilution.
Intermediate dilutions may be necessary
for extremely large dilutions.
8.1.8.1.3 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.
8.1.8.1.4 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.
8.1.8.1.5 Fill a 5 mL syringe with the diluted
sample as in paragraph 8.1.6.
8.1.8.1.6 If this is an intermediate dilution,
use it and repeat the above procedure
to achieve larger dilutions.
8.1.9 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.
8.1.10 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.
D-32/VOA OLM01.0
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SECTION IV
8.1.11 Close both valves and purge the sample for 11.0 + 0.1 minutes
at ambient temperature.
8.1.12 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
column by rapidly heating the trap to 180CC 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 458C.
8.1.13 While the trap is being desorbed into the gas chromatograph,
empty the purging chamber. Wash the chamber with a. minimum of
two 5 mL flushes of reagent water to avoid carryover of target
compounds.
8.1.14 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.
8.1.15 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. In addition, the system must not be
saturated by the two Xylene isomers that coelute on the GC
column used for analysis when the coeluting peak represents 400
ug/L, or, for the two 1,2-Dichloroethene isomers that may
coelute when the coeluting peak represents 400 ug/L. 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
demonstrates that the system is free of interferences. Once
the system is free of interferences, the sample that saturated
the detection must be diluted and reanalyzed.
8.1.16 To prepare a matrix spike and matrix spike duplicate for water
D-33/VOA OLM01.2 1/91
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SECTION IV
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.
8.1.17 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).
8.1.17.1 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
internal standards, and carried through the
analytical procedure.
8.1.17.2 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.
8.1.17.3 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.
8.1.17.4 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.
8.1.18 The Contractor must demonstrate that there is no carryover from
a contaminated sample before data from subsequent analyses may
be submitted. After a sample that contains a target compound
at a level exceeding the initial calibration range, the
Contractor must either:
8.1.18.1 Analyze a method blank immediately after the
contaminated sample. If an autosampler is used, a
method blank must also be analyzed using the same
purge inlet that was used for the contaminated
sample. The method blanks must meet the technical
acceptance criteria for blank analysis (see 8.1.17),
or
8.1.18.2 Monitor the sample analyzed immediately after the
contaminated sample for all compounds that were in
the contaminated sample and that exceeded the limits
above. The maximum contamination criteria are as
follows: the sample must not contain a
concentration above the CRQL for the target
D-34/VOA OLM01.2 1/91
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SECTION IV
compounds that exceeded the limits in the
contaminated sample. If an autosampler is used, the
next sample analyzed using the same purge inlet that
was used for the contaminated sample also must meet
the maximum contamination criteria.
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 a heated purge of a
soil/sediment 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.
o If the X Factor is >1, use the medium soil method.
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
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 40eC.
D-35/VOA OLM01.2 1/91
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SECTION IV
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 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.
8.2.1.5 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
8.2.1.6 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
8.1.11 - 8.1.14. Requirements for dilution of
samples are given in paragraphs 8.2 and 10.7.
D-36/VOA OLM01.2 1/91
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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 mL 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.
contaminated 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.
8.2.1.10 The Contractor must demonstrate that there is no
carryover from a contaminated sample before data
from subsequent analyses may be submitted. After a
sample that contains a target compound at a level
exceeding the initial calibration range, the
Contractor must either:
D-37/VOA OLM01.2 1/91
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SECTION IV
8.2.1.10.1 Analyze a method blank immediately
after the contaminated sample. If an
autosampler is used, a method blank
must also be analyzed using the same
purge inlet that was used for the
contaminated sample. The method blanks
must meet the technical acceptance
criteria for blank analysis (see
8.2.1.9), or
8.2.1.10.2 Monitor the sample analyzed immediately
after the contaminated sample for all
compounds that were in the contaminated
sample and that exceeded the limits
above. The maximum contamination
criteria are as follows: the sample
must not contain a concentration above
the CRQL for the target compounds that
exceeded the limits in the contaminated
sample. If an autosampler is used, the
next sample analyzed using the same
purge inlet that was used for the
contaminated sample also must meet the
maximum contamination criteria.
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
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 8.2.1.5.
D-38/VOA OLM01.2 1/91
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SECTION IV
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 (±2eC) 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.
Estimated n Take this Volume of
Methanol Extract
0.25
0.5
2.5
12.5
5.0
- 10.0
- 50.0
- 250
500 -
1000 -
5000 -
25,000 -
O f\f O
Of O
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.
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SECTION IV
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
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 4
g of a purified solid matrix spiked
with the system monitoring compounds,
extracted with methanol, and carried
through the analytical procedure.
D-40/VOA OLM01.3 2/91
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SECTION IV
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.
8.2.2.11 The Contractor must demonstrate that there is no
carryover from a contaminated sample before data
from subsequent analyses may be submitted. After a
sample that contains a target compound at a level
exceeding the initial calibration range, the
Contractor must either:
8.2.2.11.1 Analyze a method blank immediately
after the contaminated sample. If an
autosampler is used, a method blank
must also be analyzed using the same
purge inlet that was used for the
contaminated sample. The method blanks
must meet the technical acceptance
criteria for blank analysis (see
8.2.2.10), or
8.2.2.11.2 Monitor the sample analyzed immediately
after the contaminated sample for all
compounds that were in the contaminated
sample and that exceeded the limits
above. The maximum contamination
criteria are as follows: the sample
must not contain a concentration above
the CRQL for the target compounds that
exceeded the limits in the contaminated
sample. If an autosampler is used, the
next sample analyzed using the same
purge inlet that was used for the
contaminated sample also must meet the
maximum contamination criteria.
D-41/VOA OLM01.2 1/91
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SECTION IV
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 Exhibit A, Section III) 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,
the standard must be run in the same 12-hour time period as the
sample. If samples are analyzed during the same 12-hour time
period as the initial calibration standards, use the RRT values
from the 50 ug/L standard. 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).
D-42/VOA OLM01.3 2/91
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SECTION IV
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 identification criteria must be reported with
their spectra. For all compounds below the CRQL
report the actual value followed by a "J", e.g.,
"3J."
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 most
recent release of the NIST/EPA/MSDC mass spectral library, 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.
9.2.1 Up to 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.
D-43/VOA OLM01.3 2/91
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SECTION IV
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
characteristic ions of analytes listed in Tables 3 and 4 in this
Section are used.
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 initializing
and dating the changes made to the report.
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. For samples analyzed during the same 12-
hour time period as the initial calibration standards, compare the
internal standard responses and retention times against the 50 ug/L
calibration standard.' 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.
D-44/VOA OLK01.2 1/91
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SECTION IV
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.
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 "3J."
Concentration
(Ais)(RRF)(V0)
Where,
Ax - Area of the characteristic ion (EICP) for the compound
to be measured (see Table 4)
Area of the characteristic ion (EICP) for the specific
internal standard (see Table 3)
Is - Amount of internal standard added in nanograms (ng)
RRF - Relative response factor from the ambient temperature
purge of the calibration standard.
Vo = 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., V0 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.
D-45/VOA OLM01.0
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SECTION IV
Low Soil
Concentration (AX)(IS)
(Dry weight basis) ug/Kg -
(Ais)(RRF)(Ws)(D)
Where,
AJJ, Is , A£S are as given for water.
RRF - Relative response factor from the heated purge of the
calibration standard.
D - 100 - % moisture
100
Ws - Weight of sample added to the purge tube, in grams (g)
Medium Soil
Concentration (AX) ( Is ) (Vt) ( 1000) (Df )
(Dry weight basis) ug/Kg - (A.S) (RRF) (va) (Ws) (D)
Where,
Ax , A^s , Is are as given for water above .
RRF - Relative response factor from the ambient temperature
purge of the calibration standard.
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
Ws - 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 Va. 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 Vt from mL to uL.
D-46/VOA OLM01.2 1/91
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SECTION IV
10.4 An estimated concentration for non-target components tentatively
identified shall be determined 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
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-, and p- isomers) are to be reported as Xylenes (total).
Because the o- and p-Xylene isomers coelute on packed columns, and the
m- and p-Xylene isomers coelute on capillary columns, special attention
must be given to the quantitation of the Xylenes. The relative
response factor (RRF) determined in paragraph 7.4 is based on the peak
that represents the single isomer on the GC column used (m-Xylene on
packed columns, o-Xylene on capillary columns). In quantitating sample
concentrations, use the areas on both peaks and the RRF from paragraph
7.4. The areas of the two peaks may be summmed, and the concentration
determined, or the concentration represented by each of the two peaks
may be determined separately, and then summed. It is required that all
three Xylene isomers be present in the initial and continuing
calibration standards.
10.6 The cis and trans steriosomers of 1,2-Dichloroethene are to be reported
as 1,2-Dichloroethene (total). If the two isomers coelute on the GC
column used for analysis, use the area of the coeluting peaks and the
RRF determined in 7.4 to determine the concentration. If the isomers
do not coelute, use the single RRF values determined in 7.4 to
determine the concentration. The areas of the two peaks may be summed
and the concentration determined, or the concentration represented by
each of the two peaks may be determined separately, and then summed.
It is required that both the cis and trans isomers of the 1,2-
Dichloroethene be present in the initial and continuing calibration
standards.
10.7 If the on-column concentration of any compound in any sample exceeds
the initial calibration range, a new aliquot of that sample must be
diluted and purged. 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 the
largest analyte peak for a target compound in the upper half of
the initial calibration range of the instrument.
D-47/VOA OLM01.2 1/91
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SECTION IV
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/MSD samples to get either spiked or non-spiked
analytes within calibration range. If the sample from which the
MS/MSD aliquots were taken contains high levels of the spiked
analytes, calculate the concentration and recovery of the
analytes from the undiluted analysis, and note the problem in
the SDG Narrative.
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 the peak representing the
single isomer exceeds 200 ug/L or the peak representing the two
coeluting isomers on the GC column exceeds 400 ug/L.
Similarly, if the cis and trans isomers of 1,2-Dichloroethene
coelute, a diluted analysis is not required unless the
concentration of the coeluting peak exceeds 400 ug/L. If the
two isomers do not coelute, a diluted analysis is not required
unless the concentration of either peak 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:
%Recovery - Concentration (or amount) found x 100
Concentration (or amount) spiked
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 If an undiluted analysis with acceptable monitoring
compound recoveries is being submitted, do not reanalyze
diluted samples if the system monitoring compound
recoveries are outside the limits.
D-48/VOA OLM01.2 1/91
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SECTION IV
o Never reanalyze the matrix spike or matrix spike duplicate
(MS/USD), 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 semivolatile 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.
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
D-49/VOA OLM01.0
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SECTION IV
o Each 14 calendar day period (7 calendar day period for 14-day data
turnaround contracts) during which field samples in a Case were
received (said period beginning with the receipt of the first sample
in that 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:
SSR - SR
Matrix Spike Recovery - x 100
SA
Where,
SSR - Spiked sample result
SR - Sample result
SA - Spike added
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 - IMSR - MSDRj 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-50/VOA OLM01.2 1/91
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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).
D-51/VOA OLM01.0
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SECTION IV
TABLE 3
CHARACTERISTIC IONS FOR
SYSTEM MONITORING COMPOUNDS AND
INTERNAL STANDARDS FOR VOLATILE ORGANIC COMPOUNDS
Compound Primary Ion Secondary lon(s)
SYSTEM MONITORING COMPOUNDS
4-Bromofluorobenzene 95 174, 176
l,2-Dichloroethane-d-4 65 102
Toluene-d-8 98 70, 100
INTERNAL STANDARDS
Bromochloromethane 128 49, 130, 51
1,4-Difluorobenzene 114 63, 88
Chlorobenzene-d-5 117 82, 119
D-52/VOA OLM01.0
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SECTION IV
TABLE 4
CHARACTERISTIC IONS FOR VOLATILE TARGET COMPOUNDS
Analvte
Chlorome thane
Bromome thane
Vinyl chloride
Chloroe thane
Methylene chloride
Acetone
Carbon disulfide
1 , 1-Dichloroethene
1, 1-Dichloroe thane
1 , 2 - Dichloroethene
Chloroform
1,2-Dichloroethane
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 - Me thy 1 - 2 - pentanone
Tetrachloroethene
Toluene
Chlorobenzene
Ethyl benzene
Styrene
Total Xylenes
Primarv 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-53/VOA
OLM01.0
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SECTION IV
TABLE 5
VOLATILE INTERNAL STANDARDS WITH CORRESPONDING TARGET COMPOUNDS
AND SYSTEM MONITORING COMPOUNDS ASSIGNED FOR QUANTITATION
Bromochloromethane
1,4-Difluorobenzene
Chlorobenzene-
Chloromethane
Bromomethane
Vinyl Chloride
Chloroethane
Methylene Chloride
Acetone
Carbon Disulfide
1,1-Dichloroethene
1,1-Dichloroethane
l,2-Dichloroethene(tot.
Chloroform
1,2-Dichloroethane
2 -Butanone
l,2-Dichloroethane-d4
(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-Methyl-2-Pentanone
Tetrachloroethene
1,1,2,2-Tetrachloroethane
Toluene
Chlorobenzene
Ethylbenzene
Styrene
Xylene (total)
Bromofluorobenzene (smc)
Toluene-dg (smc)
(smc) - system monitoring compound
D-54/VOA
OLM01.0
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EXHIBIT D
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 (BNA) 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.
1.2 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.
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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
reconciled 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.
Sample extracts 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.
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PART B - SAMPLE PREPARATION FOR EXTRACTABLE SEMIVOLATILES (SNA) IN WATER
1. Summary of Sample Preparation Method
1.1 A one liter aliquot of sample 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 and/or elevated baselines in the total ion current profiles
(TICPs). All of these materials routinely must be demonstrated to be
free from interferences under the conditions of the analysis by running
laboratory method blanks. Matrix interferences may be caused by
contaminants that are coextracted from the sample. The extent of
matrix interferences will vary considerably from source to source.
3. Apparatus and Materials
Brand names, suppliers, and part numbers are for illustrative purposes
only. No endorsement is implied. Equivalent performance may be
achieved using apparatus and materials other than those specified here,
but demonstration of equivalent performance meeting the requirements of
this SOW is the responsibility of the Contractor.
3.1 Glassware (brand names and catalog numbers are included for
illustration purposes only).
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).
3.1.2 Drying column - 19 mm ID chromatographic column with coarse
frit (substitution of a small pad of Pyrex glass wool for the
frit will prevent cross contamination of sample extracts).
3.1.3 Concentrator tube - Kuderna-Danish, 10 mL, graduated (Kontes
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, 500 mL (Kontes K-570001-
0500 or equivalent). Attach to concentrator tube with springs.
3.1.5 Snyder column - Kuderna-Danish, three-ball macro (Kontes
K-503000-0121 or equivalent).
3.1.6 Snyder column - Kuderna-Danish, two-ball micro (Kontes K569001-
0219 or equivalent).
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3.1.7 Vials - amber glass, 2 mL capacity with Teflon-lined screw cap.
3.1.8 Syringes - 0.2 mL, 0.5 mL, and 5 mL volumes.
3.2 Silicon carbide boiling chips - approximately 10/40 mesh. Heat to
400°C for 30 minutes or Soxhlet extract with methylene chloride.
3.3 Water bath - 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 ^804 (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-ds, 2,4,6-Tribromophenol, 2-Fluorophenol,
Nitrobenzene-d5, Terphenyl-d]^, 2-Fluorobiphenyl, 2-
Chlorophenol-d4, and l,2-Dichlorobenzene-d4. Additional
surrogates may be added at the laboratory's discretion.
4.6.2 Prepare a surrogate standard spiking solution that contains
Nitrobenzene-d5, Terphenyl-d]^, 2-Fluorobiphenyl, and 1,2-
Dichlorobenzene-d4 at a concentration of 100 ug/mL; Phenol-d5,
2,4,6-Tribromophenol, 2-Fluorophenol, and 2-Chlorophenol-d4 at
a concentration of 150 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
150 ug/1.0 ml in methanol. 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.
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 well. 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
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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
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 15 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
evaporation 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
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SECTION II
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
a Teflon-sealed screw-cap bottle, label the bottle,
and store at 4CC (±2°C).
5.2.4.2 Nitrogen Evaporation Technique (taken from ASTM
Method D3086)
Place the concentrator tube with an open micro
Snyder attached in a warm water bath (30eC to 35°C)
and evaporate the solvent volume to just below 1 mL
by blowing a gentle stream of clean, dry nitrogen
(filtered through a column of activated carbon)
above the extract. CAUTION: Gas lines from the gas
source to the evaporation apparatus must be
stainless steel, copper, or 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
PART C - SAMPLE PREPARATION FOR EXTRACTABLE SEMIVOLATILES (SNA) 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 XLO.OOO 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 Semivolatiles
1.1 Scope and Application
This procedure is designed for the preparation of soil/sediment samples
which may contain organic chemicals at a level greater than 10,000
ugAg-
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 the 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, Part C, beginning at
paragraph 2.
1.2 Summary of Method
1.2.1. Approximately 1 g portions of soil/sediment 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 10,000 ug/kg for extractable
organics. For analysis purposes, the quantitation limits are
10,000 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, Methanol, 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-d5,
2,4,6-Tribromophenol, 2-Fluorophenol, Nitrobenzene-d$,
Terphenyl-di4, 2-Fluorobiphenyl, 2-Chlorophenol-d4, and 1,2-
Dichlorobenzene-d4. Prepare a surrogate standard spiking
solution that contains Nitrobenzene-d$, Terphenyl-d^,
2-Fluorobiphenyl, and 1,2-Dichlorobenzene-d4 at a concentration
of 100 ug/mL; Phenol-d5, 2,4,6-Tribromophenol, 2-Fluorophenol,
and 2-Chlorophenol-d4 at a concentration of 150 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 150 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-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 W-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 that sufficient energy is transferred to the sample
during extraction, the MICROTIP 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.
1.6.13 Syringes - 0.5 mL volume.
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
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SECTION II
approximately 1 g (record weight to the nearest 0.1 g) of
sample to a 20-mL vial. Wipe the mouth of the vial with a
tissue to remove any sample material. Record the exact weight
of sample taken. Cap the vial before of sample tal
sample to avoid any cross-contamination.
1.7.1.1 Transfer 50 g of soil/sediment to a 100 mL 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.
g of sample - g of dry sample i«/» „ . ^
s £— e__^ i E-— x 100 - % moisture
g of sample
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.
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.
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SECTION II
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
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 evaporation 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 10,000
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 evaporation 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 20,000 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 10,000 ug/kg,
discard the extract and prepare the sample by the medium level method.
If no peaks are present at greater than 10,000 ug/kg, the entire
extract is concentrated, subjected to GPC clean up, and analyzed by
GC/MS for extractable organics.
2.2 Interferences
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.
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2.3 Apparatus and Materials
Brand names, suppliers, and part numbers are for illustrative purposes
only. No endorsement is implied. Equivalent performance may be
achieved using apparatus and materials other than those specified here,
but demonstration of equivalent performance meeting the requirements of
.this SOW is the responsibility of the Contractor.
2.3.1 Apparatus for determining percent moisture
2.3.1.1 Oven - drying.
2.3.1.2 Desiccator.
2.3.1.3 Crucibles - porcelain.
2.3.2 Disposable Pasteur glass pipets - 1 mL.
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 (Kontes
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).
D-18/SV OLM01.2 1/91
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SECTION II
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.
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.
2.3.15 Syringes - 0.5 mL volume.
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-propane1,
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-dj,
2,4,6-Tribromophenol, 2-Fluorophenol, Nitrobenzene-65,
Terphenyl-di4, 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-d4 at a concentration
of 100 ug/mL; Phenol-d5, 2,4,6-Tribromophenol, 2-Fluorophenol,
and 2-Chlorophenol-d4 at a concentration of 150 ug/mL. Store
the spiking solutions at 4eC (±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
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 150 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.
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
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
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.
2.5.2 The following steps should be performed rapidly to avoid loss
of the more volatile extractables. Weigh approximately 30 g of
sample to 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 weighing. Concentrations of
individual analytes will be reported relative to the
dry weight of sediment.
D-20/SV OLM01.0
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g of sample - g of dry sample
g of sample x 100 - % moisture
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 UNA matrix spike solution to each of two
portions. The frequency of MS/MSD analysis is given
in Section IV, paragraph 8.6.
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 W-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 MIGROTIP 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 unenergized 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.
D-21/SV OLM01.2 1/91
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2.5.6.1 If the sample is to be screened from the low level
method prior to GPC, take 5.0 mL and concentrate to
1.0 mL following paragraph 3.6.1 or 3.6.2, but note
that the final volume for screening is 1.0 mL, not
0.5 mL. Screen the extract as per Section III,
paragraph 1., "Screening of Extractable Organic
Extracts."
2.5.6.2 After GC/FID or GC/MS screening, transfer the
remainder of the 1 mL back to the total extract from
paragraph 2.5.6. CAUTION: To minimize sample loss,
autosamplers which pre-flush samples through the
syringe should not be used.
2.6 Concentration and Solvent Exchange
2.6.1 Low level soil/sediment samples prepared by the procedures in
paragraph 2.5 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 2.6.2-2.6.4.
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. Do not allow the
evaporator to go dry.
2.6.4 Dilute the extract to 10.0 mL with methylene chloride, and
proceed with GPC clean up (see paragraph 3).
D-22/SV OLM01.2 1/91
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3. Extract Cleanup by Gel Permeation Chromatography
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.
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
Brand names, suppliers, and part numbers are for illustrative purposes
only. No endorsement is implied. Equivalent performance may be
achieved using apparatus and materials other than those specified here,
but demonstration of equivalent performance meeting the requirements of
this SOW is the responsibility of the Contractor.
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.
D-23/SV OLM01.2 1/91
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SECTION II
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.
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 the following analytes (in
elution order):
D-24/SV OLM01.0
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SECTION II
Compound
corn oil
bis(2 -ethylhexyl)phthalate
methoxychlor
perylene
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 gm of Bio Beads (SX-3). Transfer them to a quart
bottle with a Teflon-lined cap or a 500 mL separatcry 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.
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
D-25/SV OLM01.0
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SECTION II
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 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.
3.3.7 Push the plunger until it meets the gel, then compress the
column bed about four centimeters.
3.3.8 Pack the optional 5 cm column with approximately 5 gin 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 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 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
D-26/SV OLM01.0
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SECTION II
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 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.
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
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
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SECTION II
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 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.
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%,
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.
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SECTION II
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 22 "C.
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
extract through the filter and into the glass container. Draw
a minimum of 8 mL of extract into a 10 mL 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-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 waste.
3.5.4 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.
D-29/SV OLM01.2 1/91
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SECTION II
3.5.5 After loading each sample loop, wash the loading port with
methylene chloride in a PTFE 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
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
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SECTION II
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 methylene chloride. Concentrating the
extract to 0.5 mL will result in no loss of sensitivity despite
the volume of extract (5 mL) not recovered after GPC.
3.6.2 Nitrogen evaporation 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 result in
no loss of sensitivity despite 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.
3.8 If the extract was not screened prior to GPC, proceed to Section III
for the screening procedures. If the extract was screened prior to
GPC, proceed with the GC/MS analysis in Section IV.
D-31/SV OLM01.2 1/91
-------
SECTION III
SCREENING OF SEMIVOIATILE
ORGANIC EXTRACTS
D-32/SV OLM01.0
-------
SECTION III
1. Summary of Method
1.1 The solvent extracts of water and soil/sediment are screened on a gas
chromatograph/flame 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 & W 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 97% 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).
D-33/SV OLM01.2 1/91
-------
SECTION III
3.2.1.2 Transfer the stock standard solutions into Teflon-
sealed screw-cap bottles. Store at -10eC 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 as 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 - 280eC for 8 minutes.
o Injector - Grob-type, splitless.
o Sample Volume - 1-2 uL.
o Carrier Gas - Helium at 30 mL/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.
D-34/SV OLM01.2 1/91
-------
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 cleanup.
NOTE: The choice of screening sample extracts before or after GPC
cleanup is left to the laboratory.
D-35/SV OLM01.3 2/91
-------
SECTION IV
GC/MS ANALYSIS OF SEMIVOLATILES
D-36/SV OLM01.0
-------
SECTION IV
1. Summary of Method
This method is to be used for the 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
Brand names, suppliers, and part numbers are for illustrative purposes
only. No endorsement is implied. Equivalent performance may be
achieved using apparatus and materials other than those specified here,
but demonstration of equivalent performance meeting the requirements of
this SOW is the responsibility of the Contractor.
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&W 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 GC 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
dichlorodimethylsilane.
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
D-37/SV OLM01.2 1/91
-------
SECTION IV
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
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 personnel.
2.1.6 Syringes - 2 uL and 10 uL volumes.
3. Reagents
3.1 Internal standards - 1,4 Dichlorobenzene-d^, Naphthalene-dg,
Acenaphthene-diQ, Phenanthrene-d^Q, Chrysene-d^2> Perylene-d]^.
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, 50, 80, 120, and 160 total ng per 2 uL). Each calibration
standard should contain each compound of interest and each surrogate.
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 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 4CC (±2°C).
In order to facilitate the confirmation of pesticides and Aroclors from
the semivolatile library search data (see Exhibit D 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 may 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.
D-38/SV OLM01.3 2/91
-------
SECTION IV
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.
4. Instrument Operating Conditions
4.1 Gas Chromatograph
The following are the recommended GC 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 mL/sec
Optimize GC conditions for analyte separation and sensitivity.
Once optimized, the same GC conditions must be used for the
analysis of all standards, samples, blanks, matrix spikes, and
matrix spike duplicates.
4.2 Mass Spectrometer
The following are the required mass spectrometer analytical
conditions:
»Electron Energy - 70 volts (nominal)
Mass Range - 35 to 500 amu
Scan Time - not to exceed 1 second per scan
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).
D-39/SV OLM01.2 1/91
-------
SECTION IV
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).
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
Ion Abundance Criteria
51 30.0-80.0 percent of mass 198
68 Less than 2.0 percent of mass 69
69 Present
70 Less than 2.0 percent of mass 69
127 25.0 - 75.0 percent of mass 198
197 Less than 1.0 percent of mass 198
198 Base peak, 100 percent relative abundance (see note)
199 5.0 - 9.0 percent of mass 198
275 10.0 - 30.0 percent of mass 198
365 Greater than 0.75 percent of mass 198
441 Present but less than mass 443
442 40.0 - 110.0 percent of mass 198
443 15.0 - 24.0 percent of mass 442
NOTE: All ion abundances MUST be normalized to m/z 198, the nominal base
peak, even though the ion abundances of m/z 442 may be up to 110 percent that
of m/z 198.
D-40/SV OLM01.0
-------
SECTION IV
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. Note: All
subsequent standards, samples, MS/MSD, and blanks
associated with a DFTPP analysis must use identical
mass spectrometer instrument conditions.
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
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 (initial or continuing calibration
criteria) begins at the moment of injection of the
DFTPP analysis that the laboratory submits as
documentation of a compliant instrument performance
check. The time period ends after 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.
D-41/SV OLM01.3 2/91
-------
SECTION IV
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.
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 - -T- x
Ais cx
Where,
Ax - 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)
C^s - 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 using the following equation:
%RSD - Standard Deviation x 100
Mean
Where,
n | 1/2
£ (?C - T/Q |
Standard Deviation - i-1
n-1
Where
xi — each individual value used to calculate the mean
x = the mean of n values
n = the total number of values
D-42/SV OLM01.2 1/91
-------
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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-ds 136 68
Acenapthene-dio 164 162, 160
Phenanthrene-diQ 188 94, 80
Chrysene-d12 240 120, 236
Perylene-d12 264 260> 265
D-44/SV OLM01.0
-------
SECTION IV
TABLE 4
CHARACTERISTIC IONS FOR SEMIVOLATILE TARGET COMPOUNDS AND SURROGATES
Parameter
Primary Ion Secondary Ion(s)
Phenol
bis(2 -Chloroethyl)ether
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
2-Methylphenol
2,2'-oxybis(l-Chloropropane)
4-Me thyIpheno1
N-Nitroso-di-propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2,4-Dimethylphenol
bis(2-Chloroethoxy)methane
2,4-Dichlorophenol
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-Dinitrophenol
4-Nitrophenol
Dibenzofuran
2,4-Dinitrotoluene
2,6-Dinitrotoluene
(continued)
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
65, 66
63, 95
64, 130
148, 113
148, 113
148, 113
107
77, 79
107
42, 101, 130
201, 199
123, 65
95, 138
65, 109
121, 122
95, 123
164, 98
182, 145
129, 127
129
223, 227
144, 142
141
235, 272
198, 200
198, 200
164, 127
92, 138
194, 164
151, 153
108, 92
152, 154
63, 154
139, 65
139
63, 182
89, 121
D-45/SV
OLM01.0
-------
SECTION IV
TABLE 4 (continued)
CHARACTERISTIC IONS FOR SEMIVOLATILE TARGET COMPOUNDS AND SURROGATES
Parameter
Primary Ion Secondary Ion(s)
Piethylphthalate
4-Chlorophenyl-phenylether
Fluorene
4-Nitroaniline
4,6-Dinitro-2-methylphenol
N-Nitrosodiphenylamine
4-Bromophenyl-phenylether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Carbazole
Di-n-butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
3,3'-Dichlorobenzidine
Benz o(a)anthracene
bis(2-Ethylhexyl)phthalate
Chrysene
Di-n-Octyl phthalate
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(l,2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(g,h,i)perylene
SURROGATES
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
177, 150
206, 141
165, 167
92, 108
182, 77
168, 167
250, 141
142, 249
264, 268
179, 176
179, 176
166, 139
150, 104
101, 100
101, 100
91, 206
254, 126
229, 226
167, 279
226, 229
253, 125
253, 125
253, 125
138, 227
139, 279
138, 277
Phenol -d5
2 - Fluorophenol
2,4, 6 -Tribromophenol
Nitrobenzene - d5
2 - Fluorob ipheny 1
Terphenyl
2 - Chlorophenol - 64
l,2-Dichlorobenzene-d4
99
112
330
82
172
244
132
152
42,
64
332,
128,
171
122,
68,
115,
71
141
54
212
134
150
D-46/SV
OLM01.0
-------
SECTION IV
5.6 Response factor criteria have been established for the calibration of
the semivolatile target compounds and semivolatile surrogate compounds.
5.6.1 The response factors of the compounds listed in Table 5 must
meet the minimum RRF criteria at each concentration level and
maximum %RSD 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-Methylphenol
N-Nitroso-Di-propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2,4- Dime thy Iphenol
bis ( - 2 - Chloroethoxy )me thane
2,4-Dichlorophenol
1 , 2 , 4-Trichlorobenzene
Naphthalene
4-Chloro-3-methylphenol
2 -Methylnaphthalene
2,4,6 -Tr ichlorophenol
2,4, 5-Trichlorophenol
2-Chloronaphthalene
Acenaphthylene
2 ,6-Dinitrotoluene
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)
D-47/SV
OLM01.1 12/90
-------
SECTION IV
TABLE 5 (continued)
RELATIVE RESPONSE FACTOR CRITERIA FOR INITIAL AND CONTINUING
CALIBRATION OF SEMIVOLATILE TARGET COMPOUNDS
Semi volatile
Compounds
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo (a) anthracene
Chrysene
Benzo (b) f luoranthene
Benzo (k) f luoranthene
Benzo (a)pyrene
Indeno (1,2,3-cd) pyrene
Dibenzo (a , h) anthracene
Benzo (g,h, i)perylene
Nitrobenzene -d5
2 - Fluor obiphenyl
Terphenyl-d]^4
Phenol -d5
2 - Fluor opheno 1
2 - Chlorophenol - d^
1, 2-Dichlorobenzene-d4
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
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(l-Chloropropane)
4-Chloroaniline
Hexachlorobutadiene
Hexachlorocyclopentadiene
2-Nitroaniline
DimethyIphthalate
3-Nitroaniline
2,4-D ini tropheno1
4-Nitrophenol
DiethyIphthalate
4-Nitroaniline
4,6-Dinitro-2-methyIpheno1
N-Nitrosodiphenylamine
Di-n-butyIphthalate
ButylbenzyIphthalate
3,3'-Dichlorobenzidine
bis(2-Ethylhexyl)phthalate
Di-n-octyIphthalate
2,4,6-Tribromophenol
Carbazole
5.7
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)
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. For
negative percent difference values, the value must be greater than or
equal to -25.0%, but less than 0%.
D-48/SV
OLM01.2 1/91
-------
SECTION IV
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 than 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 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.
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 same concentration as the
continuing calibration standard meets the continuing calibration
acceptance criteria. Quantify all sample results against the initial
calibration standard that is the same 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 must 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.
D-49/SV OLM01.0
-------
SECTION IV
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
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
water sample extract. For soil samples and water samples subjected to
GPC, add 5 uL of internal standard solution to each accurately measured
0.5 mL of sample extract. This will result in a concentration of 20
ng/uL of each internal standard.
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 into the GC/MS. This 2 uL volume must
contain 40 ng of each internal standard.
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 Exhibit A, Section III) 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 samples
analyzed during the same 12-hour time period as the initial
calibration standards, compare the sample retention times to
those from the 50 ng calibration standard. 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:
D-50/SV OLM01.3 2/91
-------
SECTION IV
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.
7.1.3.2 The relative intensities of ions specified in
7.1.3.1 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 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 the 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 most
recent release of the NIST/EPA/MSDC mass spectral library, 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/MSDC mass spectral library. Substances with
responses less than 10% of the nearest 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.
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 searched and reported but not counted
as part of the 20 most intense non-target semivolatile
compounds.
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.
D-51/SV OLM01.3 2/91
-------
SECTION IV
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..
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 the 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.
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 initializing and dating the
changes made to the report.
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. For samples analyzed during
the same 12-hour time period as the initial calibration standards, compare the
internal standard responses and retention times to those of the 50 ng calibration
standard. The extracted ion current profile
D-52/SV OLM01.0
-------
SECTION IV
(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
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 MS/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. For samples
analyzed during the same 12-hour time period as the initial calibration
standards, use the RRF values from the 50 ng calibration standard.
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 5.4 and the following equation:
Water
(Ax)(Is)(Vt)(Df)
Concentration ug/L -
(Ais)(RRF)(V0)(Vi)
D-53/SV OLM01.2 1/91
-------
SECTION IV
Where,
Ax - Area of the characteristic ion for the compound to be
measured
Ais " Area of the characteristic ion for the internal standard
Is - Amount of internal standard injected in nanograms (ng)
V0 - Volume of water extracted in milliliters (mL)
V^ - Volume of extract injected in microliters (uL)
Vt - 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.
Soil/Sediment
(Ax)(Is)(Vt)(Df)(2.0)
Concentration ug/kg -
(Dry weight basis) (Ais) (RRF)(Vi)(WS)(D)
Where,
AX,!S,A£S are as given for water, above.
Vt - Volume of the concentrated extract in microliters (uL)
Vj^ - 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 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.
The factor of 2.0 in the numerator is used to account for the amount of
extract that is not recovered from the mandatory use of GPC cleanup.
Concentrating the extract collected
D-54/SV OLM01.3 2/91
-------
SECTION IV
after GPC to 0.5 mL, rather than 1.0 mL for water samples not
subjected to GPC, maintains the sensitivity of the soil method
comparable to that of the water method, but correction of the
numerical result is still required.
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 extract 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.
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 the most
concentrated dilution analyzed and one further dilution.
8.4.4 Do not dilute MS/MSD samples to get either spiked or non-spiked
analytes within the calibration range. If the sample from which
the MS/MSD aliquots were taken contains high levels of the
spiked analytes, calculate the concentration and recovery of
the analytes from the undiluted analysis, and note the problem
in the SDG Narrative.
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:
%Recovery = Concentration (or amount) found x 100
Concentration (or amount) spiked
D-55/SV OLM01.2 1/91
-------
SECTION IV
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-d5, 2-
Fluorobiphenyl, and Terphenyl-dj^); acid compounds (Phenol-
ds, 2-Fluorophenol, and 2,4,6-Tribromophenol); and
compounds with advisory QC limits (2-Chlorophenol-d4 and
1,2 -Dichlorobenzene-d4.
o If a single surrogate recovery from any group is not within
the contract windows, the sample does not require reanalysis
or re-extraction.
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 re-extraction.
o Do not reanalyze or re-extract 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 or 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.
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 a re-analysis 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.
D-56/SV OLM01.2 1/91
-------
SECTION IV
8.5.5 If none of the steps in paragraph 8.5.3 or 8.5.4 solves the
problem, then, except as noted below, re-extract and reanalyze
the sample. If the re-extraction 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 re-extracted along with
the blank. The blank is intended to detect contamination in
samples processed at the same time.
o Do not re-extract diluted samples if surrogate recoveries
are outside the limits.
o Never re-extract 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
a reanalysis must not be submitted.
Document in the narrative the similarity in surrogate
recoveries.
8.5.6 If the re-extraction 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 (e.g., the first
analysis of both extracts of the sample). Distinguish between
the initial analysis and the analysis of the re-extracted
sample on all data deliverables, using the sample suffixes
supplied in Exhibit B.
D-57/SV OLM01.2 1/91
-------
SECTION IV
TABLE 6
SURROGATE RECOVERY LIMITS
Compound
Nitrobenzene-d5
2 - Fluorobiphenyl
Terphenyl-d]^
Phenol -d5
2 - Fluorophenol
2,4, 6 -Tribromophenol
2 - Chlorophenol - £4
1 , 2-Dichlorobenzene-d4
%Recovery
Water
35-114
43-116
33-141
10-110
21-110
10-123
33-110
16-110
%Recovery
Soil
23-120
30-115
18-137
24-113
25-121
19-122
20-130
20-130
(advisory)
(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 (7 calendar day period for 14-day
data turnaround contracts) during which field samples in a
Case were received (said period beginning with the receipt of
the first sample in that Sample 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 same equations as used for target compounds.
Calculate the recovery of each matrix spike compound as
follows:
SSR - SR
Matrix Spike Recovery - x 100
^A
Where,
SSR — Spike sample result
SR - Sample result
SA - Spike added
8.6.2 Calculate the relative percent difference of the recoveries of
each compound in the matrix spike and matrix spike duplicate as
follows:
|MSR - MSDR|
RPD - x 100
(1/2)(MSR+MSDR)
D-58/SV OLM01.2 1/91
-------
SECTION IV
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
%Recovery RPD %Recovery RPD
Compound Water Water Soil Soil
Phenol 12-110 ' 42
2-Chlorophenol 27-123 40
1,4-Dichlorobenzene 36- 97 28
N-Nitroso-di-n-propylamine 41-116 38
1,2,4-Trichlorobenzene 39- 98 28
4-Chloro-3-methylphenol 23- 97 42
Acenaphthene 46-118 31
4-Nitrophenol 10- 80 50
2,4-Dinitrotoluene 24- 96 38
Pentachlorophenol 9-103 50
Pyrene 26-127 31
26- 90
25-102
28-104
41-126
38-107
26-103
31-137
11-114
28- 89
17-109
35-142
35
50
27
38
23
33
19
50
47
47
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 (7 calendar day period for 14-day data
turnaround contracts) 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 similar concentration
(soil only), OR
o Whenever samples are extracted by the same procedure (continuous
liquid-liquid extraction or sonication).
D-59/SV
OLM01.2 1/91
-------
SECTION IV
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 re-extracted and re-analyzed at no additional cost
to the Agency. The Laboratory Manager, or his designee, must address
problems and solutions in the SDG Narrative (Exhibit B).
9. 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.
D-60/SV OLM01.0
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TABLE 8
CHARACTERISTIC IONS FOR PESTICIDES/AROCLORS
Parameter Primary Ion Secondary Ion(s)
alpha-BHC 183 181, 109
beta-BHC 181 183, 109
delta-BHC 183 181, 109
ganuna-BHC (Ltndane) 183 181, 109
Heptachlor 100 272, 274
Aldrin 66 263, 220
Heptachlor epoxide 353 355, 351
Endosulfan I 195 339, 341
Dieldrin 79 263, 279
4,4'-DDE 246 248, 176
Endrin 263 82, 81
Endrin ketone 317 67, 319
Endrin aldehyde 67 250, 345
Endosulfan II 337 339, 341
4,4'-DDD 235 237, 165
Endosulfan sulfate 272 387, 422
4,4'-DDT 235 237, 165
Methoxychlor 227 228
Chlordane (alpha and/or gamma) 373 375, 377
Toxaphene 159 231, 233
Aroclor-1016 222 260, 292
Aroclor-1221 190 222, 260
Aroclor-1232 190 222, 260
Aroclor-1242 222 256, 292
Aroclor-1248 292 362, 326
Aroclor-1254 292 362, 326
Aroclor-1260 360 362, 394
D-61/SV OLM01.0
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EXHIBIT D
ANALYTICAL METHODS
FOR PESTICIDES/AROCLORS
D-l/PEST OLM01.0
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EXHIBIT D
Table of Contents
Page
SECTION I - Introduction D-3/PEST
SECTION II - 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
SECTION III - GC/EC Analysis of Pesticides
and Aroclors D-35/PEST
D-2/PEST OLM01.0
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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) to 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/EC technique.
1.3 Sample extracts, standards, and blanks must be analyzed within an
analytical sequence as defined in Section III. GC/EC 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 must 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.
D-3/PEST OLM01.0
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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 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 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 16 times greater than the CRQL.
Single-point calibrations for multicomponent analytes are sufficient
for quantitation by this method.
1.11 The BCD 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 ECD
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 from the mean RT of the standard, using the
retention time window specifications in Section III, paragraph 8.4.
1.13 The surrogates, 2,4,5,6-Tetrachloro-m-xylene and decachlorobiphenyl,
must be added to all samples, blanks, matrix spikes, and matrix spike
duplicates prior to extraction. The retention time of both surrogates
must fall within the retention time 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.
D-4/PEST OLM01.1 12/90
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1.14 The criteria in Section III, paragraph 14, are used to determine
whether an analysis is complete or whether additional cleanup,
dilution, or reextraction is required.
1.15 Resolution difficulties have been associated with the following pairs
of compounds using this method:
o On a DB-608 or equivalent column, DDE and Dieldrin; Methoxychlor
and Endrin ketone; and Endosulfan I and gamma-Chlordane.
o On a DB-1701 or equivalent column, Endosulfan I and gamma-
Chlordane; and Methoxychlor and Endosulfan sulfate.
D-5/PEST OLM01.0
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SECTION II
SAMPLE PREPARATION AND STORAGE
D-6/PEST 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 4'C (±2eC)
from the time of receipt until 60 days after delivery of a complete
reconciled 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.
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.
Sample extracts 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
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 sample extracts must be completed within 40 days following
the start of extraction.
D-7/PEST OLM01.3 2/91
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PART B - SAMPLE PREPARATION FOR EXTRACTABLE PESTICIDES AND AROCLORS
1. Summary of Sample Preparation Methods
1.1 Water Samples
A 1-L volume of sample is spiked with the 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 (GPC is
required when higher molecular weight compounds are present that
interfere with the analyses of target compounds; GPC is optional for
all other circumstances), exchanged to hexane, cleaned up by Florisil
cartridge, and adjusted to a final volume of 1.0 mL or 2.0 mL as
described beginning at paragraph 7.2.
1.2 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 adjusted to
a final volume of 1.0 or 2.0 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 the 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 site being sampled. The cleanup procedures must be used to remove
such interferences in order to achieve the Contract Required
Quantitation Limits.
D-8/PEST OLM01.2 1/91
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SECTION II
3. Apparatus and Materials
Brand names, suppliers, and part numbers are for illustrative purposes
only. No endorsement is implied. Equivalent performance may be
achieved using apparatus and materials other than those specified here,
but demonstration of equivalent performance meeting the requirements of
this SOW is the responsibility of the Contractor.
3.1 Continuous liquid-liquid extractors - with Teflon or glass connecting
lines for use with methylene chloride, (Hershberg-Wolf Extractor, Ace
Glass Company, Vineland, NH, P/N 6841-10 or equivalent).
3.2 Separatory funnel - 2000 mL with Teflon stopcock.
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 disrupter
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 disrupter 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).
D-9/PEST OLM01.2 1/91
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SECTION II
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.
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 and for water extracts
containing higher molecular weight contaminants that interfere with the
analyses of the target compounds (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).
D-10/PEST OLM01.2 1/91
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SECTION II
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 some lots. In addition to fines
having a detrimental effect on chromatography, they also can
pass through the column screens and damage the valve.
3.15.4 Ultraviolet detector - fixed wavelength (254 run) 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.
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.
3.15.9 Glass bottle - 1 liter volume, for use in preparation of Bio
beads for packing into column.
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 that
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.
D-11/PEST OLM01.2 1/91
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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 extracts.)
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.
3.27 Flask - Volumetric 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/EC 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.
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SECTION II
4.2 Methylene chloride, hexane, acetone, toluene, iso-octane, and methane1
(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.
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.
D-13/PEST OLM01.0
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SECTION II
4.9.2.2 Transfer the stock standard solutions into a
bottle/vial with Teflon-lined cap or septa. Store
at 4°C (±28C) 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:
Analvte 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.
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 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. The
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:
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Pesticide ug/mL
gamma-BHC (Lindane) 0.5
4,4'-DDT 1.0
Endrin 1.0
Heptachlor 0.5
Aldrin 0.5
Dieldrin 1.0
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.
4.9.7 Store all standard solutions in amber glass bottles or vials
with a teflon-lined screw cap at 4°C (±2*C) and protect from
light.
5. Extraction of Water Samples
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.
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
D-15/PEST OLM01.2 1/91
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SECTION II
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.
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. Allow to cool, then detach the
distillation flask and label.
D-16/PEST OLM01.2 1/91
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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 Kuderna-Danish (K-D) concentrator by attaching a 10
mL concentrator tube to a 500 mL evaporative flask. Other
concentration devices or techniques may be used in place of the
K-D if equivalency is demonstrated for all the
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.
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/Sediment Samples
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
D-17/PEST OLM01.0
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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 Wt of sample - Wt of Dry Sample
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).
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 1.0 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.
(Twice as much of the surrogate solution is added to soil
samples than to water samples because of the increased
likelihood that the soil sample extracts will require
dilution).
6.2.5 Immediately add 80 to 100 mL of 1:1 methylene chloride/acetone
to the sample.
D-18/PEST OLM01.1 12/90
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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/acetone 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.
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
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SECTION II
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 evaporation 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
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.
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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. Pentachloropheno1
especially is susceptible to this problem. GPC system
performance must be validated at least once every seven
calendar days by demonstrating 80-110 percent recovery of the
pesticide matrix spike mixture and examining the pattern of
peaks from 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 1 liter 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).
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
D-21/PEST OLM01.0
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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.
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.
7.1.2.9 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
D-22/PEST OLM01.0
-------
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.
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.
D-23/PEST OLM01.0
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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.
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.
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 mL/min).
If the flow rate is outside of this range,
corrective action must be taken to achieve this flow
rate. 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
D-24/PEST OLM01.2 1/91
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SECTION II
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.
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.
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. Exchange the solvent to hexane and
analyze the concentrate by GC/EC. If the blank
exceeds one half the CRQL of any analyte, assuming
that the blank represents the extract from a one
liter water sample, 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
No Florisil cleanup is used in the GPC calibration check.
D-25/PEST OLM01.2 1/91
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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.
7.1.4.4 The pattern of the Aroclor quantitation peaks and
the recovery of each single component analyte must
be determined for evaluation and reporting purposes.
If the recovery of each of the single component
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 must 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.
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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
22°C.
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
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
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filter and into the glass container. Draw a minimum
of 8 mL of extract into a 10 mL syringe.
INTRODUCTION OF PARTICIPATES OR GLASS WOOL INTO THE
GPC SWITCHING VALVES MAY 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.
7.1.6.6 After loading each sample loop, wash the loading
port with methylene chloride in a PTFE 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
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-------
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, the solvent must be
exchanged to hexane as described in 7.2.
7 .1.6 .10 Any samples that were loaded into two or more loops
must be recombined before proceeding to 7.2.
7.2 Solvent exchange into hexane
This procedure applies to both extracts of water samples and extracts
of soil samples.
7.2.1 With the extract in a k-D apparatus, 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
described previously. 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 10 mL vial by using
hexane.
7.2.3 For samples which have not been subjected to GPC cleanup,
adjust the volume of the hexane extract to 10.0 mL. For
samples which have been subjected to GPC cleanup, concentrate
the hexane extract to 5.0 mL using nitrogen evaporation, as
described in 7.3.2. 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.
D-29/PEST OLM01.3 2/91
-------
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 ug/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 phe cartridge.
Reduce the final volume to 1.0 mL using nitrogen (7.3.2) and
analyze the solution by GC/EC using at least one of the GC
columns specified for sample analyses. The recovery of each
analyte must be determined for evaluation and reporting
purposes. Calculate the percent recovery using the equation
below. The lot of Florisil cartridges is acceptable if all
pesticides are recovered at 80 to 120 percent, if the recovery
of trichlorophenol is less than 5%, and if no peaks interfering
with the target analytes are detected.
Qd EQ- !
Percent Recovery - x 100
Qa
Where,
Q(j - Quantity determined by analysis
Qa - Quantity added to sample/blank
7.3.2 Nitrogen evaporation 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.
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 times with hexane and then dried
prior to use.
7.3.3 Florisil cartridge cleanup
7.3.3.1 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.
D-30/PEST OLM01.2 1/91
-------
SECTION II
7.3.3.2 Place one Florisil cartridge into the vacuum
manifold for each sample extract.
7.3.3.3 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 requires 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.
7.3.3.4 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.
7.3.3.5 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
solvent line from each cartridge is placed inside of
the appropriate volumetric flask as the manifold top
is replaced.
7.3.3.6 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.
7.3.3.7 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.
7.3.3.8 The pesticides/Aroclors in the extract concentrates
are then eluted through the column with 8 mL of
hexane/acetone (90:10) and are collected into the
10-mL volumetric flasks held in the rack inside the
vacuum manifold.
D-31/PEST OLM01.2 1/91
-------
7.3.3.9 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.
7.3.3.10 Concentrate the extract to 1.0 or 2.0 mL as required
in paragraph 7.3.4.3 by using 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.
7.3.3.11 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.
7.3.3.12 If sulfur is not present, transfer the sample to a
GC vial and label the vial. The extract is ready
for GC/EC analysis. Proceed to Section III. Store
the extracts at 4°C (+2°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
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 evaporation 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.
D-32/PEST OLM01.0
-------
SECTION II
7.4.2 Mercury technique
Add one to three drops of mercury to each hexane extract in a
clean vial. Tighten the top on the vial and agitate the sample
for 30 seconds. Filter or centrifuge the extract. Pipet the
extract to another vial and leave all solid precipitate and
liquid mercury. If the mercury appears shiny, proceed to
Section 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-33/PEST OLM01.0
-------
SECTION III
GC/EC ANALYSIS OF PESTICIDES AND AROCLORS
D-34/PEST 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/EC 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.
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 be accomplished by
the external standard method. Three-point calibration curves for
single component analytes and the surrogates must be generated during
D-35/PEST OLM01.0
-------
the initial calibration. A linear response range must be demonstrated
from the CRQL to a high point at least 16 times greater than the CRQL.
Single-point calibrations for multicomponent analytes are sufficient
for quantitation by this method.
1.10 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 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 from the RT of the standard, using the
retention time window specifications in Paragraph 8.4.
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 chroraatographs that are available from some manufacturers
may have difficulty in meeting certain method QC requirements
because of Endrin and DDT breakdown in the injector. This
problem can be minimized by operating the injector at 200-
205°C, using a Pyrex (not quartz) methyl silicone deactivated
injector liner, and deactivating any metal parts in the
injector with dichlorodimethyl silane. In some cases, using a
0.25 inch packed column injector converted for use with 0.53 mm
capillary columns works better than a Grob-type injector. If a
Grob-type injector is used, a 4 mm liner may be required to
meet breakdown criteria.
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
columns may be employed if they meet the requirements for
resolution, initial calibration, and calibration verification
listed in this section.
D-36/PEST OLM01.1 12/90
-------
SECTION III
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.,
Bellefonte, PA, Catalog No. 2-3660, or equivalent). Use of
this adapter allows simultaneous injection onto both columns.
The laboratory should follow manufacturer's recommendations for
mounting 0.53 mm capillary columns in injector ports.
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 make-up gas must be P-5, P-10
(argon/methane) or nitrogen according to the instrument specification.
The linearity of the response of the ECD may be greatly dependent on
the flow rate of the make-up gas. Care must be taken to maintain
stable and appropriate flow of make-up gas to the detector. The GC/EC
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/EC. The data
system must allow the continuous acquisition of data throughout the
duration of the chromatographic program and must permit, at the
minimum, the output of time vs. intensity (peak height or peak area)
data. Also, the data system must be able to rescale chromatographic
data in order to report chromatograms meeting the requirements listed
within this method.
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/mL
Endosulfan sulfate 20.0 ng/mL
D-37/PEST OLM01.1 12/90
-------
3.2
3.3
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.
gamma-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
Tetrachloro-m-xylene
Decachlorobiphenyl
50.0 ng/mL
250.0 ng/mL
20.0 ng/mL
20.0 ng/mL
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 4 times the low point concentration. The high
point concentration must be at least 16 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
5.
5.
5,
.0 ng/mL
.0 ng/mL
.0 ng/mL
5.0 ng/mL
10.0 ng/mL
10.0 ng/mL
10.0 ng/mL
10.0 ng/mL
50.0 ng/mL
5.0 ng/mL
10.0 ng/mL
Individual Standard Mixture B- Low Point Concentration
beta-BHC 5.0 ng/mL
delta-BHC 5.0 ng/mL
Aldrin 5.0 ng/mL
Heptachlor expoxide 5.0 ng/mL
alpha-Chlordane 5.0 ng/mL
gamma-Chlordane 5.0 ng/mL
p,p'-DDE 10.0 ng/mL
Endosulfan sulfate 10.0 ng/mL
Endrin aldehyde 10.0 ng/mL
Endrin ketone 10.0 ng/mL
Endosulfan II 10.0 ng/mL
Tetrachloro-m-xylene 5.0 ng/mL
Decachlorobiphenyl 10.0 ng/mL
D-38/PEST
OLM01.1 12/90
-------
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)
Column Flow: 5 mL/min
Make-up Gas: P-5/P-10 or N2 (required)
Injector Temperature: > 200°C (see 4.2)
Injection: On-column
Injection Volume: 1 or 2 uL (see 4.1)
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. Once
optimized, the same GC conditions must be used for the analysis of all
standards, samples, blanks, and MS/MSDs.
The linearity of the ECD may be greatly dependent on the flow rate of
the make-up gas. Care must be taken to maintain stable and appropriate
flow of make-up gas to the detector.
4.1 Manual injections must be 2.0 uL. Auto injectors may use 1.0 uL
volumes. The same inj ection 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-39/PEST OLM01.2 1/91
-------
5.
5.1
Analysis Sequence for Standards and Samples
All acceptable samples must be analyzed within a valid analysis
sequence as given below.
Material Injected
0 hr.
1 - 15
16
17
18
First 15 steps of the
Initial Calibration
Instrument Blank at end of
Initial Calibration
PEM at end of
Initial Calibration
First Sample
12 hr.
Another 12 hr.
Another 12 hr.
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.
Subsequent Samples
Last sample
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-40/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.
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.
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).
D-41/PEST OLM01.0
-------
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 (apply to each GC column
independently)
6.2.1 The initial calibration sequence must be analyzed in the order
listed in paragraph 6.1 using the optimized GC/EC 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.
6.2.2 The resolution criterion is that the depth of the valley
between two adjacent peaks in the Resolution Check Mixture must
be greater than or equal to 60.0% 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.
D-42/PEST OLM01.3 2/91
-------
6.2.3 The breakdown of DDT and Endrin in both of the Performance
Evaluation Mixtures must be less than 20.0 percent, and the
combined breakdown of DDT and Endrin must be less than 30.0
percent where,
EQ.2
% Breakdown DDT - Amount found in ng (DDD+DDE) * 100
Amount in ng of DDT injected
EQ.3
% Breakdown Endrin —
Amount found in ng (Endrin aldehyde 4- Endrin ketone) * 100
Amount of Endrin injected in ng
EQ.4
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
the retention time windows determined from the three-point
initial calibration, in paragraph 8.4.
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 5.
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 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.
6.2.9 The % RSD of the calibration factors for each single component
target compound must be less than or equal to 20.0 percent,
except as noted below. The % RSD of the calibration factors
for the two surrogates must be less than or equal to 30.0
percent. Up to two single component target compounds (but not
surrogates) per column may exceed the 20.0 percent limit for
%RSD, but those compounds must have a % RSD of less than or
equal to 30.0 percent.
%RSD - Standard Deviation x 100
Mean
D-43/PEST OLM01.5 4/91
-------
Where,
n _, | 1/2
V fv • "Vi I
Standard Deviation - i-1 I
n-1 I
Where,
Xj - each individual value used to calculate the mean
x - the mean of n values
n - the total number of values
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 the 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 BCD
manufacturer. DO NOT OPEN THE DETECTOR. THE BCD CONTAINS
RADIOCHEMICAL SOURCES.
6.3.3 If a laboratory cleans out a detector using an elevated
temperature, the BCD 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
D-44/PEST OLM01.2 1/91
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calibration. Sample data are not acceptable unless bracketed by
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-45/PEST OLM01.0
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7.8 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.
7.9 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
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.
7.10 Technical Acceptance Criteria (apply to each GC column independently)
7.10.1 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.
7.10.2 The absolute retention time for each of the single component
pesticides and surrogates in the PEMs and mid point
concentration of the Individual Standard Mixtures used to
demonstrate continuing calibration must be within the retention
time window determined from the three-point initial calibration
in paragraph 8.4.
7 . 10 . 3 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 5 .
I cnom " ccalc I
RPD -- x 100 EQ. 5
Cnom = true concentration of each analyte
^calc = calculated concentration of each analyte from the
analyses of the standard
D-46/PEST OLM01.3 2/91
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Note: The vertical bars in the equation indicate the absolute
value, hence RPD is always a positive number.
7.10.4 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.
7.10.5 All instrument blanks must meet the acceptance criteria in
paragraph 15.3.
7.11 Corrective Action
7.11.1 If the technical acceptance criteria for the calibration
verification are not met, inspect the system for problems and
take corrective action to achieve the acceptance criteria.
7.11.2 Major corrective actions such as replacing the GO column or
baking out the detector will require that a new initial
calibration be performed and meets the technical acceptance
criteria in 6.2.
7.11.3 Minor corrective actions may not require performing a new
initial calibration, provided that a new analysis of the
standard (PEM or Individual Mixture) that originally failed the
criteria and an associated instrument blank immediately after
the corrective action do meet all the acceptance criteria.
7.11.4 If the analysis of the standard and instrument blank in 7.11.3
fail any of the technical acceptance criteria, a new initial
calibration must be performed.
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.
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-47/PEST OLM01.2 1/91
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8.4 Retention time windows for single and multicomponent analytes and
surrogates.
Retention Time Window
Compound in Minutes
alpha-BHC ±0.05
beta-BHC ± 0.05
gamma-BHC ±0.05
delta-BHC ±0.05
Heptachlor ±0.05
Aldrin ±0.05
alpha-Chlorodane ±0.07
gamma-Chlorodane ±0.07
Heptachlor epoxide ±0.07
Dieldrin ±0.07
Endrin ±0.07
Endrin aldehyde ±0.07
Endrin ketone ±0.07
ODD ±0.07
DDE ±0.07
DDT ±0.07
Endosulfan I ±0.07
Endosulfan II ±0.07
Endosulfan sulfate ±0.07
Methoxychlor ±0.07
Aroclors ±0.07
Toxaphene ±0.07
Tetrachloro-m-xylene ±0.05
Decachlorobiphenyl ±0.10
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 ±0.07 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
D-48/PEST OLM01.1 12/90
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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 6. The calibration factors for the surrogates
are calculated from the three analyses of Individual Standard
Mixture A only.
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 7 and 8.
GF — Peak Area (or Height) of the Standard EQ. 6
Mass Injected (ng)
_ n CFi
CF - £ EQ. 7
i-1 n
% RSD - Standard Deviation
— x 100
CF EQ. 8
CF - Calibration factor
Where,
Standard Deviation »
n _2 | 1/2
I (* - 4
n-1
Where,
xj — each individual value used to calculate the mean
x - the mean of n values
n - the total number of values
9.2.3 The linearity of the calibration is considered acceptable when
the % RSD of the three point calibration is less than 20.0
percent except as noted in the following.
The % RSD of the two surrogates must be less than or equal to
30.0 percent. Up to two single component target compounds (but
not surrogates) per column may exceed the 20.0 percent limit
for % RSD., but those compounds must have a % RSD of less than
or equal to 30.0 percent.
D-49/PEST OLM01.5 4/91
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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
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 Chromatograms 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 elution time of
decachlorobiphenyl.
D-50/PEST OLM01.0
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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-column injection is used (see paragraph
4.2), the injector must be heated to at least 200°C. The optimized 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
volumes. The same injection volume must be used for all standards,
samples, and blanks associated with the same initial calibration. If a
single injection is used for two GC columns attached to a single
injection port, it may be necessary to use an injection volume greater
than 2 uL. However, the same injection volume must be used for all
analyses.
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.
D-51/PEST OLM01.5 4/91
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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
during a valid analytical sequence 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.
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 analyte 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.
D- 5 2/PEST OLM01.2 1/91
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SECTION III
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 Analytes
13.1 Quantitation of target analytes and surrogates 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
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 the instrument.
13.4.4 Do not submit data for more than two analyses, i.e., the
original sample extract and one dilution, or, 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 to get either spiked or non-spiked
analytes within the calibration range. If the sample from
which the MS/MSD aliquots were taken contains high levels of
the spiked analytes, calculate the concentration and recovery
of the analytes from the undiluted analysis and note the
problem in the SDG Narrative.
D-53/PEST OLM01.2 1/91
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13.5 The concentrations of the single component pesticides are calculated
separately for both GC columns by using the following equations:
13.5.1 Water
(-Ax) (Vt) (Df) EQ. 9
Concentration ug/L -
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)
V0 - Volume of water extracted in milliliters (mL)
V^ - Volume of extract injected in microliters (uL)
(If a single injection is made onto two columns, use one
half the volume in the syringe as the volume injected
onto to each column.)
Vt = Volume of the concentrated extract in microliters (uL)
(this volume must be 10000 uL, see Section II, 7.2.3)
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, extrac't used to make dilution
If no dilution is performed, Df - 1.0.
If GPC is performed on a water sample extract, Vt becomes 5000
uL, and a factor of 2 must be added to the numerator, as
described below for soil/sediment samples.
13.5.2 Soil/Sediment
(Ax)(Vt)(Df)(2.0) EQ. 10
Concentration ug/Kg -
(Dry weight basis) (CF)(V£)(Ws)(D)
Where
Ax and CF are as given for water, above.
Vt - Volume of the concentrated extract in microliters (uL)
(this volume must be 5000 uL, see Section II, 7.2.3)
Vi - Volume of extract injected in microliters (uL)
(If a single injection is made onto two columns, use one
half the volume in the syringe as the volume injected
onto to each column.)
D = 100 - % moisture
100
Ws = Weight of sample extracted in grams (g)
D-54/PEST OLM01.3 2/91
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SECTION III
Df - Dilution Factor. The dilution factor for analysis of
soil 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.
The factor of 2.0 in the numerator is used to account for the
amount of extract that is not recovered from the mandatory use
of GPC cleanup. Concentrating the extract collected after GPC
to 5.0 mL rather than 10.0 mL for water samples not subjected
to GPC (see Section II, 7.2.3), maintains the sensitivity of
the soil method comparable to that of the water method, but
correction of the numerical result is still required.
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.
13.5.4 Because of the likelihood that compounds co-eluting with the
target compounds will cause positive interferences and increase
the concentration determined by the method, the lower of the
two concentrations calculated for each single component
pesticide is reported on Form I. In addition, the
concentrations calculated for both the GC columns are reported
on Form X, along with a percent difference comparing the two
concentrations. The percent difference is calculated according
to Equation 11.
EQ. 11
%D = ConcH - ConcL x 100
Conct
Where,
ConcH - The higher of the two concentrations for the target compound in
question
Conct "" The lower of the two concentrations for the target compound in
question
Note that using this equation will result in percent difference values
that are always positive. The value will also be greater than a value
calculated using the higher concentration in the denominator, however,
given the likelihood of a positive interference raising the
concentration determined on one GC column, this is a conservative
approach to comparing the two concentrations.
D-55/PEST OLM01.3 2/91
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SECTION III
3.6 The concentrations of the surrogates are calculated separately for both
GC columns in a similar manner as the other analytes, using Equations 9
and 10. Use the calibration factors from the midpoint concentration of
Individual Standard Mixture A. The recoveries of the surrogates are
calculated for both GC columns acccording to Equation 12.
Qd EQ. 12
Surrogate Percent Recovery - j?— x 100
xa
Where,
QQ- - Quantity determined by analysis
Qa - 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. Surrogate recovery data from both GC columns are reported (see
Exhibit B).
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 > 16 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. If the concentration is calculated to be 10 times the CRQL,
the Contractor shall contact the SMO immediately.
13.8 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 9 and 10, where Ax is the area for each of the major
peaks of the multicomponent analyte. The concentration of each peak is
determined and then a mean concentration for three to five major peaks
is determined on both columns. The following table lists the number of
potential quantitation peaks for each Aroclor and Toxaphene.
No. of Potential
Analyte Ouantitation Peaks
Aroclor 1016/1260 5/5
Aroclor 1221 3
Aroclor 1232 4
Aroclor 1242 5
Aroclor 1248 5
Aroclor 1254 5
Toxaphene 4
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SECTION III
13.9 The reporting requirements for Toxaphene and the Aroclors are similar
to those for the single component analytes, except that the lower mean
concentration (from three to five peaks) is reported on Form X, and the
two mean concentrations are compared using Equation 11.
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 below 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 for both GC
columns.
14.4 Reportable data for a sample must 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 always 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 blank 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.
D-57/PEST OLM01.3 2/91
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SECTION III
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 GC/EC system
used to analyze samples:
o Each Case, OR
o Each 14 calendar day period (7 calendar day period for 14-
day data turnaround contracts) 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.
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.
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SECTION III
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, assuming that the material in the sulfur blank
resulted from the extraction of a 1 L water sample. Calculate
the concentration of each analyte using the equation in
paragraph 13.5.1. Compare the results to the CRQL values for
water samples in Exhibit C. 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. For comparing the results of the instrument
blank analysis to the CRQLs, assume that the material in the
instrument resulted from the extraction of a 1 L water sample
and calculate the concentration of each analyte using the
equation in paragraph 13.5.1. Compare the results to one-half
the CRQL values for water samples in Exhibit C.
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
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
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SECTION III
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 per
SDG.
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. 12
Where ,
SSR - Spike sample result
SR - Sample result
SA - Spike added
|MSR - MSDR|
X
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.
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
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.
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SECTION III
MATRIX SPIKE RECOVERY AND
RELATIVE PERCENT DIFFERENCE LIMITS
%Recovery RPD %Reco
Compound Water Water Soil Soil
gamma-BBC (Lindane) 56-123 15 46-127 50
Heptachlor 40-131 20 35-130 31
Aldrin 40-120 22 34-132 43
Dieldrin 52-126 18 31-134 38
Endrin 56-121 21 42-139 45
4,4'-DDT 38-127 27 23-134 50
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.
o For soil samples prepared according to the
semivolatile low level soil method (i. e. 30 g
of soil), the corresponding sample concentration
is 330 ug/Kg.
o For soil samples prepared according to the
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SECTION III
semivolatile medium level soil method (i. e. 1 g
of soil), the corresponding sample concentration
is 10,000 ug/Kg.
Therefore, based on the values given above, any pesticide
sample in which the sample concentration is greater than or
equal to an extract concentration of 10 ng/uL should enable the
laboratory to confirm the pesticide/Aroclor by GC/MS analysis
of the semivolatile extract.
7.1.3 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 to identify the analyte in question, the
concentration of the standard should be no greater than 10
ng/uL.
17.1.3.1 To facilitate the confirmation of the
pesticide/Aroclor analytes from the semivolatile
library search data, the 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 the GC/MS
calibration data reporting forms. As only a single
concentration of each analyte would be analyzed, no
linearity (%RSD) or percent difference criteria
would be applied to the response factors for these
additional analytes.
17.1.3.2 The laboratory is advised that 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.,
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
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SECTION III
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 PLAN E-6
III STANDARD OPERATING PROCEDURES E-10
IV QA/QC REQUIREMENTS
Volatiles (VGA) QA/QC Requirements E-16/VOA
Semivolatiles (SV) QA/QC Requirements E-22/SV
Pesticides/Aroclors (PEST) QA/QC Requirements E-28/PEST
V ANALYTICAL STANDARDS REQUIREMENTS E-36
VI CONTRACT COMPLIANCE SCREENING E-41
VII REGIONAL DATA REVIEW E-42
VIII LABORATORY EVALUATION SAMPLES E-43
IX GC/MS TAPE AUDITS E-46
X DATA PACKAGE AUDITS E-49
XI ON-SITE LABORATORY EVALUATIONS E-51
XII QUALITY ASSURANCE AND DATA TREND ANALYSIS E-54
XIII DATA MANAGEMENT E-55
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OVERVIEW
Quality assurance and quality control are integral parts of the Environmental
Protection Agency's (EPA) Contract Laboratory Program (CLP). 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.
During the planning of an environmental data collection program, QA
activities focus on defining data quality criteria and designing a QC system
to measure the quality of data being generated. During the implementation of
the data collection effort, QA activities ensure that the QC system is
functioning effectively, and that the deficiencies uncovered by the QC system
are corrected. After environmental data are collected, QA activities focus
on assessing the quality of data obtained to determine its suitability to
support enforcement or remedial decisions.
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 large 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 parameters
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. Laboratory evaluation samples, magnetic tape
audits, and data package 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
Technical Project Officers and Administrative 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:
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A written Quality Assurance Plan, the elements of which are designated in
Section II.
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 to
corrective action procedures.
Submission of all original documentation generated during sample analyses
for Agency review.
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SECTION II
QUALITY ASSURANCE PLAN
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 Plan (QAP) 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 QAP. The QAP must be available during On-Site Laboratory evaluation.
Additional information relevant to the preparation of a QAP can be found in
EPA and ASTM publications.
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
3. Personnel
a. Resumes
b. Education and Experience Pertinent to This Contract
c. Training Progress
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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.
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
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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Updating and Submission of the OAP:
Within 60 Days of contract award:
During the contract solicitation process, the Contractor was required to
submit their QAP to EMSL/LV and NEIC. Within sixty (60) days after contract
award, the Contractor shall send a revised QAP, fully compliant with the
requirements of this contract, to the Technical Project Officer, EMSL/LV and
NEIC. The revised QAP will become the official QAP under the contract. The
revised QAP must include:
1) Changes resulting from A) The Contractor's internal review of their
organization, personnel, facility, equipment, policy and procedures and
B) The Contractor's implementation of the requirements of the contract;
and,
2) Changes resulting from the Agency's review of the laboratory evaluation
sample data, bidder supplied documentation, and recommendations made
during the pre-award On-Site laboratory evaluation
Subsequent submissions:
During the term of contract, the Contractor shall amend the QAP when the
following circumstances occur:
1) The Agency modifies the contract,
2) The Agency notifies the Contractor of deficiencies in the QAP document
3) The Agency notifies the Contractor of deficiencies resulting from the
Agency's review of the Contractor's performance,
4) The Contractor identifies deficiencies resulting from their internal
review of their QAP document,
5) The Contractor's organization, personnel, facility, equipment, policy or
procedures change,
6) The Contractor identifies deficiencies resulting from the internal
review of>their organization, personnel, facility, equipment, policy or
procedures changes.
The Contractor shall amend the QAP within 30 days of when the circumstances
listed above result in a discrepancy between what was previously described in
the QAP and what is presently occurring at the Contractor's facility.
When the QAP is amended, all changes in the QAP must be clearly marked (e.g.,
a bar in the margin indicating where the change is found in the document, or
highlighting the change by underlining the change, bold printing the change,
or using a different print font). The amended section pages must have the
date on which the changes were implemented. The Contractor shall incorporate
all amendments to the current QAP document. The Contractor shall archive all
amendments to the QAP document for future reference by the Agency.
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The Contractor shall send a copy of the current QAP document within 14 days
of a request by the Technical Project Officer or Administrative Project
Officers to the designated recipients.
Corrective Action:
If a Contractor fails to adhere to the requirements listed in Section II, a
Contractor may expect, but the Agency is not limited to the following
actions: reduction of numbers of samples sent under this contract,
suspension of sample shipment to the Contractor, GC/MS tape audit, data
package audit, an On-Site laboratory evaluation , remedial laboratory
evaluation sample, and/or contract sanctions, such as a Cure Notice.
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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, must
reflect activities as they are currently performed in the laboratory. In
addition, all SOPs must be:
o Consistent with current EPA regulations, guidelines, and the CLP
contract's requirements.
o Consistent with instruments manufacturers's specific instruction manuals.
o Available to the EPA during an On-Site Laboratory Evaluation. A complete
set of SOPs shall be bound together and available for inspection at such
evaluations. During On-Site Laboratory evaluations, laboratory personnel
may be asked to demonstrate the application of the SOPs.
o Capable of providing for the development of documentation that is
sufficiently complete to record the performance of all tasks required by
the protocol.
o Capable of demonstrating the validity of data reported by the Contractor
and explain the cause of missing or inconsistent results.
o Capable of describing the corrective measures and feedback mechanism
utilized when analytical results do not meet protocol requirements.
o Reviewed regularly and updated as necessary when contract, facility, or
Contractor procedural modifications are made.
o Archived for future reference in usability or evidentiary situations.
o Available at specific work stations as appropriate
o Subject to a document control procedure which precludes the use of
outdated or inappropriate SOPs.
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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:
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 for required chain-of-custody and document control are
discussed in Exhibit F, "Specification for Written Standard Operating
Procedures"
2. Sample Receipt and Storage
a. Sample receipt and identification logbooks
b. Refrigerator temperature logbooks
c. Extract storage logbooks
d. Security precautions
3. Sample preparation
a. Reagent purity check procedures and documentation
b. Extraction procedures
c. Extraction bench sheets
d. Extraction logbook maintenance
4. Glassware cleaning
5. Calibration (Balances, GPC)
a. Procedures
b. Frequency requirements
c. Preventative maintenance schedule and procedures
d. Acceptance criteria and corrective actions
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e. Logbook maintenance authorization
6. Analytical procedures (for each analytical system)
a. Instrument performance specifications
b. Instrument operating procedures
c. Data acquisition system operation
d. Procedures when automatic quantitation algorithms are overridden
e. QC required parameters
f. Analytical run/injection logbooks
g. Instrument error and editing flag descriptions and resulting
corrective actions
7. Maintenance activities (for each analytical system)
a. Preventative maintenance schedule and procedures
b. Corrective maintenance determinants and procedures
c. Maintenance authorization
8. Analytical standards
a. Standard coding/identification and inventory system
b. Standards preparation logbook(s)
c. Standard preparation procedures
d. Procedures for equivalency/traceability analyses and
documentation
e. Purity logbook (primary standards and solvents)
f. Storage, replacement, and labelling requirements
g. QC and corrective action measures
9. Data reduction procedures
a. Data processing systems operation
b. Outlier identification methods
c. Identification of data requiring corrective action
d. Procedures for format and/or forms for each operation
10. Documentation policy/procedures
a. Laboratory/analyst's notebook policy, including review policy
b. Complete SDG File contents
c. Complete SDG File organization and assembly procedures, including
review policy
d. Document inventory procedures, including review policy
11. Data validation/self inspection procedures
a. Data flow and chain-of-command for data review
b. Procedures for measuring precision and accuracy
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c. Evaluation parameters for identifying systematic errors
d. Procedures to assure that hardcopy and diskette deliverables are
complete and compliant with the requirements in SOW Exhibits B
and H.
e. Procedures to assure that hardcopy deliverables are in agreement
with their comparable diskette deliverables.
f. Demonstration of internal QA inspection procedure (demonstrated
by supervisory sign-off on personal notebooks, internal
laboratory evaluation samples, etc.).
g. Frequency and type of internal audits (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.
12. 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:
Updating and submission of SOPs:
Within 60 days of contract award:
During the contract solicitation process, the Contractor was required to
submit their SOPs to EMSL/LV and NEIC. Within sixty (60) days after contract
award, the Contractor shall send a complete revised set of SOPs, fully
compliant with the requirements of this contract, to the Technical Project
Officer, EMSL/LV and NEIC. The revised SOPs will become the official SOPs
under the contract. The revised SOPs must include:
1) Changes resulting from A) the Contractor's internal review of their
procedures and B) the Contractor's implementation of the requirements
of the contract;
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2) Changes resulting from the Agency's review of the laboratory evaluation
sample data, bidder supplied documentation, and recommendations made
during the pre-award On-Site laboratory evaluation.
Subsequent Submissions:
During the term of contract, the Contractor shall amend the SOPs when the
following circumstances occur:
1) The Agency modifies the contract,
2) The Agency notifies the Contractor of deficiencies in their SOPs
documentation
3) The Agency notifies the Contractor of deficiencies resulting from the
Agency's review of the Contractor's performance,
4) The Contractor's procedures change,
5) The Contractor identifies deficiencies resulting from the internal
review of their SOPs documentation, or
6) The Contractor identifies deficiencies resulting form the internal
review of their procedures.
The SOPs must be amended or new SOPs must be written within 30 days of when
the circumstances listed above result in a discrepancy between what was
previously described in the SOPs and what is presently occurring at the
Contractor's facility. All changes in the SOPs must be clearly marked (e.g.,
a bar in the margin indicating where the change is in the document, or
highlighting the change by underlining the change, bold printing the change,
or using a different print font) . The amended/new SOPs must have the date on
which the changes were implemented.
When the SOPs are amended or new SOPs are written, the Contractor shall
document in a letter the reasons for the changes, and submit the amended SOPs
or new SOPs to the Technical Project Officer, EMSL/LV (quality
assurance/technical SOPs) and NEIC (evidentiary SOPs). The Contractor shall
send the letter and the amended sections of the SOPs or new SOPs within 14
days of the change. An alternate delivery schedule for the submittal of the
letter and amended/new SOPs may be proposed by the Contractor, but it is the
sole decision of the Agency, represented either by the Technical Project
Officer or Administrative Project Officer, to approve or disapprove the
alternate delivery schedule. If an alternate delivery schedule is proposed,
the Contractor shall describe in a letter to the Technical Project Officer,
Administrative Project Officer, and the Contracting Officer why he/she is
unable to meet the delivery schedule listed in this section. The Technical
Project Officer/Administrative Project Officer will not grant an extension
for greater than 30 days for amending/writing new SOPs. The Technical
Project Officer/Administrative Project Officer will not grant an extension
for greater than 14 days for submission of the letter documenting the reasons
for the changes and for submitting amended/new SOPs. The Contractor shall
proceed and not assume that an extension will be granted until so notified by
the TPO and/or APO.
E-14 OLM01.2 1/91
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The Contractor shall send a complete set of current SOPs within 14 days of a
request by the Technical Project Officer or Administrative Project Officer to
the recipients he/she designates.
Corrective action:
If a Contractor fails to adhere to the requirements listed in Exhibit E,
Section III, a Contractor may expect, but the Agency is not limited to the
following action: reduction of number of samples sent under this contract,
suspension of sample shipment to the Contractor, GC/MS tape audit, data
package audit, On-Site laboratory evaluation, remedial laboratory evaluation
sample, and/or contract sanction, such as a Cure Notice.
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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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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 to 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 Table 5.
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 at each concentration level 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.
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.
E-17/VOA OLM01.4 3/91
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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, 7.4.6 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 GC/MS data system
printout for the analysis of the volatile calibration standard.
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.
E-18/VOA OLM01.4 3/91
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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 VOA, Section IV, paragraphs 8.1.17, 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, 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.
E-19/VOA OLM01.2 1/91
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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 6. If the recovery of any one
system monitoring compound is outside these limits, the
Contractor must follow the steps outlined in Ex. D 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 accordance with the appropriate method.
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, paragraph 10.9.2.
7.3 The quality control limits for recovery and relative percent
difference are given in Ex. D VOA, 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 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.
E-20/VOA OLM01.2 1/91
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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 to get either spiked or non-spiked
analytes within calibration range. If the sample from which the
MS/MSD aliquots were taken contains high levels of the spiked
analytes, calculate the concentration and recovery of the
analytes from the undiluted analysis, and note the problem in
the SDG Narrative.
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.
E-21/VOA OLM01.1 12/90
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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 D 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.
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.
E-22/SV OLM01.0
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1.3 The documentation includes Form V SV, and a mass listing 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,
120, 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 at each concentration level 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.
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.
3.2 The standard is to be analyzed according to the procedures
given in Ex. D SV, Section IV, paragraph 5, and at the
E-23/SV OLM01.4 3/91
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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 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 %D must be less than or equal to
40.0% for the continuing calibration to be acceptable.
3.4 The documentation includes Form VII SV, a GC/MS data system
printout for the analysis of the semivolatile calibration
standard.
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 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 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.
E-24/SV OLM01.4 3/91
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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.
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 semivolatile 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, 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 the 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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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.
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 accordance with the appropriate method.
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. D
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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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 semivolatile
screening procedure was employed, from the most concentrated
dilution analyzed and one further dilution.
8.4 Do not dilute MS/MSD samples to get either spiked or, non-spiked
analytes within the calibration range. If the sample from which
the MS/MSD aliquots were taken contains high levels of the
spiked analytes, calculate the concentration and recovery of
the analytes from the undiluted analysis, and note the problem
in the SDG Narrative.
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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 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 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.
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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1.2 Additional resolution 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 7.10.
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. Multicomponent 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
4 times the low point concentration. The concentration of the
high point initial calibration standard must be at least 16
times the low point concentration, and may be higher 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.
E-29/PEST OLM01.2 1/91
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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 7.10.
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.
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4.1 The identification of all target compounds analyzed by the
procedures described in Ex. D PEST is based on the use of
absolute retention time. 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 described in Ex. D, Section III, paragraph 8.4.
4.3 The retention time shifts of the surrogates are used to
evaluate the stability of the gas chromatographic 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,
paragraphs 7.10 and 8.4.
4.4 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 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.
6.1.1 The frequency of method blank extraction is
described in Ex. D PEST, Section III, paragraph
15.1.1.
E-31/PEST OLM01.2 1/91
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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 15.1.2.
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 to
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 not 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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6.4 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 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 chromatograms and
GC/EC data system printouts 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.
7.4 The documentation includes Form II PEST, a chromatogram and a
E-33/PEST OLM01.2 1/91
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GC/EC data system printout for the analysis of each sample,
blank, matrix spike, and matrix spike duplicate.
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 accordance with the appropriate
method.
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 matrix 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.
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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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/MSD samples to get either spiked or non-spiked
analytes within the calibration range. If the sample from
which the MS/MSD aliquots were taken contains high levels of
the spiked analytes, calculate the concentration and recovery
of the analytes from the undiluted analysis and note the
problem in the SDG Narrative.
E-35/PEST OLM01.1 12/90
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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 independant 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.
3. Mis-identification of compounds occasionally occurs and it is
E-36 OLM01.0
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possible that a mislabeled compound may be received from a chemical
supply house. It is the contract laboratory's responsibility to
have analytical documentation ascertaining that all compounds used
in the preparation of solution standards 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-37 OLM01.0
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The Contractor must 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 - (Y! + Y2 + Y3 + Y4 + Y5 + Y6 )/6
Equation 3 222222 2
VARIANCE -
-------
The test statistic must be calculated:
Equation 5
TEST STATISTIC = | (M3 /l.l) - (M! /0.9)|/(Vp /3)°'5
If the test statistic exceeds 2.13 then the supplier has failed
to demonstrate a twenty percent difference between the high and
low standards. In such a case, the standards are not
acceptable.
e. The test statistic must be calculated:
Equation 6
TEST STATISTIC - |M2 - (M! /I. 8) - (M3 /2.2)|/(Vp /4)°'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 - HI + (2.13)(Vp /6)°'5
Equation 8
Interval for Target Standard - M2 ± (2.13)(Vp /6)°'5
Equation 9
Interval for High Standard - M3 + (2.13) (Vp /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,
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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.
The Agency may generate a CCS trend report which summarizes CCS results over
a given period of time. The Agency may send the CCS trend report or discuss
the CCS trend report during an On-Site laboratory evaluation. In a detailed
letter to the Technical Project Officer and Administrative Project Officer,
the Contractor shall address the deficiencies and the subsequent corrective
action implemented by the Contractor to correct the deficiencies within 14
days of receipt of the report or the On-Site laboratory evaluation. An
alterante delivery schedule may be proposed by the Contractor, but it is the
sole decision of the Agency, represented by the Technical Project Officer or
Administrative Project Officer to approve or disprove the alternate delivery
schedule. If an alternate delivery schedule is proposed, the Contractor
shall describe in a letter to the Technical project Officer, Administrative
Project Officer, and Contracting Officer why he/she is unable to meet the
delivery schedule listed in this section. The Technical Project Officer will
not grant an extension for greater than 14 days for the Contractor's response
to the CCS trend report.
If new SOPs are required to be written or SOPs are required to be amended
because of the deficiencies and the subsequent corrective action implemented
by the Contractor, the Contractor shall write/amend and submit the SOPs per
the requirements listed in Exhibit E, Section III.
If the Contractor fails to adhere to the requirements listed in Section VI,
the Contractor may expect, but the Agency is not limited to the following
actions: reduction of number of samples sent under the contract, suspension
of sample shipment to the Contractor, GC/MS tape audit, data package audit,
an On-Site laboratory evaluation, a remedial laboratory evaluation sample,
and/or contract sanctions, such as a Cure Notice.
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SECTION 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
rcumstances.
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, also referred to as performance evaluation (PE) 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 minimum, 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.
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.
An alternate delivery schedule may be proposed by the Contractor, but it
is the sole decision of the Agency, represented either by the Technical
Project Officer or Administrative Project Officer, to approve of
disapprove the alternate delivery schedule. If an alternate delivery
schedule is proposed, the Contractor shall describe in a letter to the
Technical Project Officer, Administrative Project Officer, and the
Contracting Officer why he/she is unable to meet the delivery schedule
listed in this section. The Technical Project Officer /Administrative
Project Officer will not grant an extension for greater than 14 days for
the Contractor's response letter to the laboratory evaluation sample
report. The Contractor shall proceed and not assume that an extension
will be granted until so notified by the TPO and/or APO.
If new SOPs are required to be written or SOPs are required to be
amended because of the deficiencies and the subsequent corrective action
implemented by the Contractor, the Contractor shall write/amend and
submit the SOPs per the requirements listed in Exhibit E, Section III.
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.
An alternate delivery schedule may be proposed by the Contractor, but it
is the sole decision of the Agency, represented either by the Technical
Project Officer or Administrative Project Officer, to approve of
disapprove the alternate delivery schedule. If an alternate delivery
schedule is proposed, the Contractor shall describe in a letter to the
Technical Project Officer, Administrative Project Officer, and the
Contracting Officer why he/she is unable to meet the delivery schedule
listed in this section. The Technical Project Officer /Administrative
Project Officer will not grant an extension for greater than 14 days for
the Contractor's response letter to the laboratory evaluation sample
report.
If new SOPs are required to be written or SOPs are required to be
amended because of the deficiencies and the subsequent corrective action
implemented by the Contractor, the Contractor shall write/amend and
submit the SOPs per the requirements listed in Exhibit E, Section III.
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The Contractor shall be notified by the Technical Project Officer or
Administrative Project Officer concerning the remedy for their
unacceptable performance. A Contractor may expect, but the Agency is
not limited to, the following actions: reduction of the number of
samples sent under the contract, suspension of sample shipment to the
Contractor, an On-Site laboratory evaluation, GC/MS tape audit, data
package audit, remedial laboratory evaluation sample, and/or a contract
sanction, such as 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 may facilitate continuation of full sample
delivery.
If the Contractor fails to adhere to the requirements listed in Section
VIII, a Contractor may expect, but the Agency is not limited to the
following actions: reduction in the number of samples sent under the
contract, suspension of sample shipment to the Contractor, an On-Site
laboratory evaluation, GC/MS tape audit, data package audit, a remedial
laboratory evaluation sample and/or contract sanctions, such as a Cure
Notice.
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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 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 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.
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.
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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.)
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.
Submission of the GC/MS tape:
Upon request of the Administrative Project Officer or EMSL/LV, the Contractor
shall send the required GC/MS tapes and all necessary documentation to
EMSL/LV within seven days of notification. An alternate delivery schedule
may be proposed by the Contractor, but it is the sole decision of the Agency,
represented either by the Technical Project Officer or Administrative Project
Officer, to approve or disapprove the alternate delivery schedule. If an
alternate delivery schedule is proposed, the Contractor shall describe in a
letter to the Technical Project Officer, Administrative Project Officer, and
the Contracting Officer why he/she is unable to meet the delivery schedule
listed in this section. The Technical Project Officer/Administrative Project
Officer will not grant an extension for greater than seven days for
submission of the GC/MS tape. The Contractor shall proceed and not assume
that an extension will be granted until so notified by the TPO and/or APO.
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Responding to the GC/MS tape audit report:
After completion of the GC/MS tape audit, the Agency may send a copy of the
GC/MS tape audit report to the Contractor or may discuss the GC/MS tape audit
report on an On-Site laboratory evaluation. In a detailed letter to the
Technical Project Officer, Administrative Project Officer, and EMSL/LV, the
Contractor shall discuss the corrective actions implemented to resolve the
deficiencies listed in the GC/MS tape audit report within 14 days of receipt
of the report. An alternate delivery schedule may be proposed by the
Contractor, but it is the sole decision of the Agency, represented either by
the Technical Project Officer or Administrative Project Officer, to approve
or disapprove the alternate delivery schedule. If an alternate delivery
schedule is proposed, the Contractor shall describe in a letter to the
Technical Project Officer, Administrative Project Officer, and the
Contracting Officer why he/she is unable to meet the delivery schedule listed
in this section. The Technical Project Officer/Administrative Project
Officer will not grant an extension for greater than 14 days for the
Contractor's response letter to the GC/MS tape report. The Contractor shall
proceed and not assume that an extension will be granted until so notified by
the TPO and/or APO.
If new SOPs are required to be written or SOPs are required to be amended
because of the deficiencies and the subsequent corrective action implemented
by the Contractor, the Contractor shall write/amend and submit the SOPs per
•i requirements listed in Exhibit E, Section III.
Corrective actions
If the Contractor fails to adhere to the requirements listed in Section IX,
the Contractor may expect, but the Agency is not limited to the following
actions: reduction in the number of samples sent under the contract,
suspension of sample shipment to the Contractor, an On-Site laboratory
evaluation, GC/MS tape audit, data package audit, remedial laboratory
evaluation sample, and/or contract sanctions, such as a Cure Notice.
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SECTION X
DATA PACKAGE AUDITS
Data package audits are performed by the Agency for program overview and
specific Regional concerns. Standardized procedures have been established to
assure uniformity of the auditing process. Data packages are periodically
selected from recently received cases. They are evaluated for the technical
quality of hardcopy raw data, quality assurance, and the adherence to
contractual requirements. This function provides external monitoring of
program QC requirements.
Data package audits are used to assess the technical quality of the data and
evaluate overall laboratory performance. It provides the Agency with an in-
depth inspection and evaluation of the Case data package with regard to
achieving QA/QC acceptability. A thorough review of the raw data is
completed including: a check of instrument printouts, quantitations reports,
chromatograms, spectra, library searches and other documentation for
deviations from the contractual requirements, a check for transcription and
calculation errors, a review of the qualifications of the laboratory
personnel involved with the Case, and a review of all current SOPs on file.
Responding to the data package audit report:
After completion of the data package audit, the Agency may send a copy of the
data package audit report to the Contractor or may discuss the data package
audit report on an On-Site laboratory evaluation. In a detailed letter to
the Technical Project Officer, Administrative Project Officer, and EMSL/LV,
the Contractor shall discuss the corrective actions implemented to resolve
the deficiencies listed in the data package audit report within 14 days of
receipt of the report. An alternate delivery schedule may be proposed by the
Contractor, but it is the sole decision of the Agency, represented either by
the Technical Project Officer or Administrative Project Officer, to approve
or disapprove the alternate delivery schedule. If an alternate delivery
schedule is proposed, the Contractor shall describe in a letter to the
Technical Project Officer, Administrative Project Officer, and the
Contracting Officer, why he/she is unable to meet the delivery schedule
listed in this section. The Technical Project Officer/Administrative Project
Officer will not grant an extension for greater than 14 days for the
Contractor's response letter to the data package report. The Contractor
shall proceed and not assume that an extension will be granted until so
notified by the TPO and/or APO.
If new SOPs are required to be written or SOPs are required to be amended
because of the deficiencies and the subsequent corrective action implemented
by the Contractor, the Contractor shall write/amend and submit the SOPs per
the requirements listed in Exhibit E, Section III.
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Corrective Actions
If the Contractor fails to adhere to the requirements listed in Section X,
the Contractor may expect, but the Agency is not limited to the following
actions: reduction in the numbers of samples sent under the contract,
suspension of sample shipment to the Contractor, an On-Site laboratory
evaluation, GC/MS tape audit, data package audit, remedial laboratory
evaluation sample, and/or contract sanctions, such as a Cure Notice.
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SECTION XI
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 the QAP and 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/data management procedures
Prior to an On-Site evaluation, various documentation pertaining to
performance of the specific Contractor is integrated in a profile
package for discussion during the evaluation. Items that may be
included are previous On-Site reports, laboratory evaluation sample
scores, Regional review of data, Regional QA materials, GC/MS tape audit
reports, data 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
On-site laboratory evaluation:
Following an On-Site laboratory evaluation, quality assurance and/or
evidentiary audit reports which discuss deficiencies found during the
On-Site evaluation may be sent to the Contractor. In a detailed letter,
the Contractor shall discuss the corrective actions implemented to
resolve the deficiencies discussed during the On-Site evaluation and
discussed in the report(s) to the Technical Project Officer,
Administrative Project Officer, and EMSL/LV (response to quality
assurance/technical report) and NEIC (response to the evidentiary
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report), within 14 days of receipt of the report. An alternate delivery
schedule may be proposed by the Contractor, but it is the sole decision
of the Agency, represented either by the Technical Project Officer or
Administrative Project Officer, to approve or disapprove the alternate
delivery schedule. If an alternate delivery schedule is proposed, the
Contractor shall describe in a letter to the Technical Project Officer,
Administrative Project Officer, and the Contracting Officer why he/she
is unable to meet the delivery schedule listed in this section. The
Technical Project Officer/Administrative Project Officer will not grant
an extension for greater than 14 days for the Contractor's response
letter to the quality assurance and evidentiary audit report. The
Contractor shall proceed and not assume that an extension will be
granted until so notified by the TPO and/or APO.
If new SOPs are required to be written or SOPs are required to be
amended because of the deficiencies and the subsequent corrective action
implemented by the Contractor, the Contractor shall write/amend and
submit the SOPs per the requirements listed in Exhibit E, Section III.
Corrective actions
If the Contractor fails to adhere to the requirements listed in Section
XI, the Contractor may expect, but the Agency is not limited to the
following actions: reduction in the number of samples sent under the
contract, suspension of sample shipment to the Contractor, an On-Site
laboratory evaluation, GC/MS tape audit, data package audit, a remedial
laboratory evaluation sample, and/or contract sanctions, such as a Cure
Notice.
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SECTION XII
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 laboratory 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
^rogram-wide statistical results are used to rank laboratories in order to
oserve 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 XIII
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.
Lifecycle 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 the 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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EXHIBIT F
CHAIN-OF-CUSTODY, DOCUMENT CONTROL,
AND STANDARD OPERATING PROCEDURES
F-l OLM01.0
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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 traceability of the samples while in possession of the
Contractor, the Contractor shall have a specified method for
maintaining identification of samples throughout the laboratory.
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 stickers
o Custody seals
o EPA custody records
o EPA traffic reports or SAS packing lists
o Sample tags
1.3.6 The sample custodian or his/her representative shall sign and
date all forms (e.g., custody records, traffic reports or
packing lists, and airbills) accompanying the samples at the
time of sample receipt.
1.3.7 The Contractor shall contact the Sample Management Office
(SMO) to resolve discrepancies and problems such as absent
documents, conflicting information, broken custody seals, and
unsatisfactory sample condition (e.g., leaking sample bottle).
1.3.8 The Contractor shall record the resolution of discrepancies
and problems on Telephone Contact Logs.
1.3.9 The following information shall be recorded on Form DC-1 (See
Exhibit B) by the sample custodian or his/her representative
as samples are received and inspected:
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 tag identification numbers cross-referenced to the
EPA 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 to supporting documents and raw data shall be made
by drawing a single line through the error and entering the
correct information. Corrections and additions to supporting
documents and raw data shall be dated and initialed. No
information shall be obliterated or rendered unreadable.
All notations shall be recorded in ink.
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 the method (carrier) used. |
3. SPECIFICATIONS FOR WRITTEN STANDARD OPERATING PROCEDURES
The Contractor shall have written standard operating procedures (SOPs)
for receipt of samples, maintenance of custody, sample identification,
sample storage, sample tracking, and assembly of completed data.
An SOP is defined as a written narrative stepwise description of
laboratory operating procedures including examples of laboratory
documents. The SOPs shall accurately describe the actual procedures
used in the laboratory, and copies of the written SOPs shall be
available to the appropriate laboratory personnel. These procedures
are necessary to ensure that analytical data produced under this
contract are acceptable for use in EPA enforcement case preparation and
litigation. The Contractor's SOPs shall provide mechanisms and
documentation to meet each of the following specifications and shall be
used by EPA as the basis for laboratory evidence audits.
3.1 The Contractor shall have written SOPs describing the sample
custodian's duties and responsibilities.
3.2 The Contractor shall have written SOPs for receiving and logging in of
the samples. The procedures shall include but not be limited to
documenting the following information:
3.2.1 Presence or absence of EPA chain-of-custody forms
3.2.2 Presence or absence of airbills or airbill stickers
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3.2.3 Presence or absence of traffic reports or SAS packing lists
3.2.4 Presence or absence of custody seals on shipping and/or sample
containers and their condition
3.2.5 Custody seal numbers, when present
3.2.6 Airbill or airbill sticker numbers
3.2.7 Presence or absence of sample tags
3.2.8 Sample tag ID numbers
3.2.9 Condition of the shipping container
3.2.10 Condition of the sample bottles
3.2.11 Verification of agreement or non-agreement of information on
receiving documents and sample containers
3.2.12 Resolution of problems or discrepancies with the SMO
3.2.13 An explanation of any terms used by the laboratory to describe
sample condition upon receipt (e.g., good, fine, OK)
3.3 The Contractor shall have written SOPs for maintaining identification
of EPA samples throughout the laboratory.
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:
o A description of the documents used to record sample receipt,
sample storage, sample transfers, sample preparations, and
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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 charts, computer printouts, raw data summaries,
correspondence, and any other written documents having reference to the
SDG are compiled in one location for submission to EPA. The written
SOPs shall include:
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
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
F-8 OLM01.0
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information disposed of for one year and shall keep a record on the
disposition in the Confidential Inventory Log.
F-9 OLM01.0
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EXHIBIT G
GLOSSARY OF TERMS
G-l OLM01.0
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GLOSSARY OF TERMS
ALIQUOT - a measured portion of a sample taken for analysis.
ANALYSIS DATE/TIME - the date 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.
This extraction technique involves boiling the extraction solvent in a flask
and condensing the solvent above the aqueous sample. The condensed solvent
drips through the sample, extracting the compounds of interest from the
aqueous phase.
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 (SNA) 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 or electron capture detector
to the target compounds.
G-2 OLM01.2 1/91
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INTERNAL STANDARDS - compounds added to every standard, blank, matrix spike,
matrix spike duplicate, sample (for VOAs), and sample extract (for
semivolatiles) at a known concentration, prior to analysis. Internal
standards are used as the basis for quantitation of the target compounds.
LABORATORY - synonymous with Contractor as used herein.
m/z - Mass to charge ratio, synonymous with "m/e".
MATRIX - the predominant material of which the sample to be analyzed is
composed. For the purpose of this SOW, 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 and reagent contamination.
NARRATIVE (SDG Narrative) - portion of the data package which includes
laboratory, contract, Case and sample number identification, and descriptive
documentation of any problems encountered in processing the samples, along
with corrective action taken and problem resolution. Complete SDG Narrative
specifications are included in Exhibit B.
PERCENT DIFFERENCE (%D) - As used in this SOW and elsewhere to compare two
values, the percent difference indicates both the direction and the magnitude
of the comparison, i.e., the percent difference may be either negative,
positive, or zero. (In contrast, see relative percent difference below).
PERCENT MOISTURE - an approximation of the amount of water in a soil/sediment
sample made by drying an aliquot of the sample at 105°C. The percent
moisture determined in this manner also includes contributions from all
compounds that may volatilize at or below 105°C, including water. Percent
moisture may be 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).
G-3 OLM01.2 1/91
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PURGE AND TRAP (DEVICE) - analytical technique (device) used to isolate
volatile (purgeable) organics by stripping the compounds from water or soil
by a stream of inert gas, trapping the compounds on an adsorbent such as a
porous polymer trap, and thermally desorbing the trapped compounds onto the
gas chromatographic column.
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 (RIC) - a mass spectral graphical
representation of the separation achieved by a gas chromatograph ; a plot of
total ion current versus retention time.
RELATIVE PERCENT DIFFERENCE (RPD) - As used in this SOW and elsewhere to
compare two values, the relative percent difference is based on the mean of
the two values, and is reported as an absolute value, i.e., always expressed
as a positive number or zero. (In contrast, see percent difference above).
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:
RRF
Ais cx
Where
A - area of the characteristic ion measured
C — concentration
is — internal standard
x - analyte of interest
RESOLUTION - also termed separation or percent resolution, the separation
between peaks on a chromatogram, calculated by dividing the depth of the
valley between the peaks by the peak height of the smaller peak being
resolved, multipled by 100.
Resolution = A^ x ICO
B
G-4 OLM01.2 1/91
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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 within a Case, received over a period of up to 14 calendar days
(7 calendar days for 14-day data turnaround contracts). 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 (7-day calendar period for 14-day data
turnaround contracts) 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.
SEMIVOLATILE COMPOUNDS - compounds amenable to 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 to be detected in environmental media.
TARGET COMPOUND LIST (TCL) - a list of compounds designated by the Statement
of Work (Exhibit C) for analysis.
TENTATIVELY IDENTIFIED COMPOUNDS (TIC) - compounds detected in samples that
are not target compounds, internal standards, 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.
G-5 OLM01.2 1/91
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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 have elapsed
according to the system clock. For pesticide/Aroclor analyses performed by
GC/EC, the twelve hour time period in the analytical sequence begins at the
moment of injection of the instrument blank that precedes sample analyses,
and ends after twelve hours have elapsed according to the system clock.
VALIDATED TIME OF SAMPLE RECEIPT (VTSR) - the date on which a sample is
received at the Contractor's facility, as recorded on the shipper's delivery
receipt and Sample Traffic Report.
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-6 OLM01.2 1/91
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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
OLM01.0
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AGENCY STANDARD IMPLEMENTATION
FOR ORGANICS OLM01.0
(This document will replace existing formats as of October 1991)
1. Format Characteristics
1.1 This constitutes an implementation of the EPA Agency Standard for Electronic Data
Transmission based upon analytical results and ancillary information required by
the contract. All data generated by a single analysis are grouped together, and
the groups are aggregated to produce files that report data from an SDG. Because
this implementation is only a subset of the Agency Standard, some fields have
been replaced by delimiters as place holders for non-CLP data elements.
1.2 This implementation includes detailed specifications for the required format of
each record. The position in the record where each field is to be contained
relevant to other fields is specified, as well as the maximum length of the
field. Each field's required contents are specified as literal (contained in
quotes), which must appear exactly as shown (without quotes), or as a variable
for which format and/or descriptions are listed in the format/contents column.
Options and examples are listed for most fields. For fields where more than
three options are available, a list and description of options are supplied on a
separate page following the record descriptions. Fields are separated from each
other by the delimiter "|" (ASCII 124). Fields that do not contain data should
be zero length with the delimiter as place holder.
1.3 Numeric fields may contain numeric digits, a decimal place, and a leading minus
sign. A positive sign is assumed if no negative sign is entered in a numeric
field and must not be entered into any numeric field.
Requirements for significant figures and number of decimal places are specified
in Exhibit B. The numeric field lengths are specified such that all possible
numeric values can be written to the file. The size of the numeric field
indicates the maximum number of digits, decimal, and negative sign if appropriate
that can appear in the field at the same time. Therefore, the number reported
may .need to be rounded (using EPA Rounding Rules) to fit into the field. The
rounding must maintain the greatest significance possible providing the field
length limitation. In addition, the rounded number that appears on the form, and
therefore the field in the diskette file, must be used in any calculation that
may result in'other numbers reported on the same form or other forms in the SDG.
Field lengths should only be as long as necessary to contain the data; packing
with blanks is not allowed.
2. Record Types
2.1 The Agency Standard consists of variable length ASCII records. Maximum field
length specifications match the reporting requirements in Exhibit B. The last
two bytes of each record must contain "carriage return" and "line feed",
respectively.
H-l OLM01.8 8/91
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2.2 This implementation consists of eleven record types that can be summarized in
four groups, designated by the first record type in each group:
Type Type ID Contents
Run Header 10 Information pertinent to a group of samples processed
in a continuous sequence; usually several per SDG
Sample Header 20 Sample identifying, qualifying, and linking
information
Results Record 30 Analyte results and qualifications
Comments Record 90 Free form comments
2.3 A separate run header is used for volatiles, semivolatiles, and each column
analysis for pesticides (minimum of 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).
3. Production Runs
A production run represents a "group" or "batch" of samples that are processed in
a continuous sequence under relatively stable conditions. Specifically:
Calibration - All samples in a run use the same initial calibration data.
Method number - Constant.
Instrument conditions - Constant throughout a run. Results obtained on different
instruments cannot be combined in one run.
Analyses from each fraction consist of separate production runs, and are reported
in separate files. There will be a separate production run for each 72-hour
sequence for pesticides for each GC column utilized. Thus, a full three fraction
analysis will consist of a minimum of four production runs, and could consist of
more.
H-2 OLM01.8 8/91
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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.
32 Reports any auxiliary data necessary.
33 Reports compound names for TICs if necessary.
36 Reports any instrumental data necessary.
30 Values for the next analyte or parameter being measured.
Additional data may vary for each parameter, and records
32 may occur in any order. Multiple occurrences of the
33 same record type, however, must be consecutive.
36
30 Continues for as many as are necessary.
32
33
36
30
32
33
36
20 Next Sample Header record - The following applies to the next
21 sample or other group of data.
22
30
32
33
36
30
32
33
36
etc.
20
21
30
32
33
36
etc.
H-3 OLM01.8 8/91
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4.
Record Sequence
4.1 The sequence of records for Agency Standard 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 several
files.
4.2 Each environmental sample, calibration, or quality control sample is represented
by a group composed of type 20, 21, 22, 23, and 27 records, that hold sample
level identifying information, followed by type 30, 32, 33, and 36 records for
each method analyte 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, surrogates, internal standards plus each peak of the multi-component
pesticides (do not include TICs in this count). A separate field on the Type 23
record contains the number of TICs found. Type 20 records must occur in the
order of sample analysis. 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 in Section 10 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.
4.3 Type 90 comment records may be defined to occupy any position except before the
type 10 (header) record.
5. File/Record Integrity
All record types shall contain the following check fields to ensure file and
record integrity:
Record
Position
First Field
Field
Length
Field
Contents
Record type
Remarks
"10" or as appropriate
Last Field
4
2
Record sequence number
within file
Record checksum
Must contain CR and LF
00000-99999, numbered
sequentially
Four hexadecimal digits(*)
(*) The checksum is the sum of the ASCII representation of the data on the
record up to the Record Sequence Number plus the checksum of the previous record.
The sum is taken modulo 65536 (2 ) and represented as four hexadecimal digits.
6. Dates and Times
Date or time-of-day information consists of successive groups of two decimal
digits, each separated by delimiters. Dates are given in the order YY MM DD, and
times as HH MM. All hours must be given as 00 to 23 using a 24 hour-clock and
must be local time.
H-4
OLM01.8 8/91
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7. Multiple Volume Data
There is no requirement under this format that all the data from an entire sample
delivery group fit onto a single diskette. However, each single production run
must fit onto a single diskette if possible. If that is not possible, then it is
necessary that all files start with a type 10 record, and that the multiple type
10 records for each file of the same production run be identical. Information
for a single sample may not be split between files.
8. Deliverable
8.1 The file 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).
Agency Standard data from an entire SDG may not fit onto a single diskette. If a
single production run is being split onto multiple diskettes, then all files must
start with a type 10 record, and the multiple type 10 records for each file of
the same production run must be identical. Do not split the data from a single
sample onto multiple diskettes.
8.2 Information on the diskette must correspond to information submitted in the
hardcopy raw data package and on the hardcopy raw data package forms. For
example, type 30 results field specifies maximum length of 13. When reporting
CRQLs or results on Form 1 maximum length is 13 as is specified on Exhibit H;
when reporting 'calculated amounts' on Form 7D, hardcopy specified maximum length
of 8 and so, a maximum length of 8 should be used. Blank or unused records 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.
8.3 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.001 to XXXXX.099
where XXXXX is the SDG identifier, 0 designates organics, and 01
through 99 the file number.
Dimensions of the label must be in the range 4-3/4" to 5" long by 1-1/4" to 1-
1/2" wide for 5-1/4 inch floppy diskette; and 2" to 2-1/4" long by 2-1/8" to 2-
3/8" wide for 3.5 inch IBM-compatible diskette.
H-5 OLM01.8 8/91
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9. Record Listing
Following is a listing of every record type required to report data from a single
SDG.
PRODUCTION RUN HEADER RECORD (Type 10)
MAXIMUM FORMAT/
LENGTH CONTENTS CONTENTS
2 RECORD TYPE "10"
6 Delimiters I I I I I I
5 MEASUREMENT TYPE Character1
1 Delimiter |
8 METHOD NUMBER Character2
2 Delimiters | |
6 LAB CODE Character
4 Delimiters ||||
11 CONTRACT NUMBER Character
1 Delimiter |
10 INSTRUMENT ID Character
2 Delimiters ||
25 - LABORATORY NAME Character
2 Delimiters | |
5 RECORD SEQUENCE NUMBER Numeric
4 CHECKSUM Character
1 General descriptor GC/MS or GC.
2 OLM01.0V For Volatiles; OLM01.0B For Semivolatiles; OLM01.0P For Pesticides.
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CHROMATOGRAPHY RECORD (TYPE 11)
Use: To describe chromatograph condition. Must be present for volatiles and
pesticides. Is optional for semivolatiles.
MAXIMUM FORMAT/
LENGTH CONTENTS CONTENTS
2 RECORD TYPE "11"
1 Delimiter |
10 GC COLUMN Character
2 Delimiters ||
4 GC COLUMN ID Numeric (mm)
11 Delimiters I I I I I I I I I I I
5 RECORD SEQUENCE NO. Numeric
4 CHECKSUM Character
H-7 OLM01.8 8/91
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SAMPLE HEADER DATA RECORD (TYPE 20)
MAXIMUM
LENGTH CONTENTS
2 RECORD TYPE
2 Delimiters
12 EPA SAMPLE NUMBER
1 Delimiter
1 MATRIX
1 Delimiter
3 QC CODE
1 Delimiter
3 SAMPLE QUALIFIER
1 Delimiter
5 CASE NUMBER
1 Delimiter
6 SDG NO.
1 Delimiter
2 YEAR ANALYZED
1 Delimiter
2 MONTH ANALYZED
1 Delimiter
2 DAY ANALYZED
1 Delimiter
2 HOUR ANALYZED
1 Delimiter
2 MINUTE ANALYZED
2 Delimiters
2 SAMPLE WT/VOL UNITS
1 Delimiter
5 SAMPLE WT/VOL
1 Delimiter
3 ANALYTE COUNT
3 Delimiters
5 RECORD SEQUENCE NO.
4 CHECKSUM
FORMAT/
CONTENTS
"20"
II
As is exactly on
the hardcopy form
CHARACTER1
I
Character (See Section 10)
1 2
RIN/REX/REJ/SRN'1
I
Numeric
I
Character
I
YY
MM
I
DD
I
HH
I
MM
II 3
"GV"ML
I
Numeric
Numeric
III
Numeric
Character
1 "0" if not applicable (calibration, tune, etc.),"I" for water, "H" for soil.
2 "RIN" for reinjection, "REX" for re-extractions, "REJ" for rejected samples, and "SRN"
for dilutions.
3 Sample WT/VOL is the volume in mililiters for liquid and the wet weight in grams for
solids. The sample units code indicates which units are in use for the current
sample. Leave zero or blank if not applicable. Sample WT/VOL includes purge volume.
4 1-3 decimal digits; Counts all analytes including surrogates, internal standards, anc
all peaks for multi-component pesticides. For calibrations, count also DFTPP/BFB if
mixed in injection.
H-8
OLM01.8 8/91
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SAMPLE HEADER DATA RECORD (TYPE 21)
Use: Continuation of Type 20
Position: Follows the Type 20 to which it applies.
MAXIMUM
LENGTH CONTENTS
2 RECORD TYPE
1 Delimiter
1 PURGE
1 Delimiter
1 LEVEL
2 Delimiters
1 EXTRACTION
2 Delimeters
6 SAS NUMBER
1 Delimiter
14 LAB FILE/SAMPLE ID
1 Delimiter
2 YEAR EXTRACTED
1 Delimiter
2 MONTH EXTRACTED
1 Delimiter
2 DAY EXTRACTED
2 Delimiters
2 YEAR RECEIVED
1 Delimiter
2 MONTH RECEIVED
1 Delimiter
2 DAY RECEIVED
2 Delimiters
8 INJECTION/ALIQUOT VOLUME
2 Delimiters
5 RECORD SEQUENCE NO.
4 CHECKSUM
FORMAT/
CONTENTS
"21"
I
"N" for not heated; "Y" for heated
I
II
Character
I
Character-
I
YY
I
MM
I
DD
II
YY
I
MM
I
DD
11 4
Numeric
II
Numeric
Character
1 "L" for low level samples and "M" for medium level samples for volatile and
semivolatile analyses. Leave blank for calibrations and tunes.
2 "S" for separatory funnel, "C" for continuous liq-liq and "N" for sonication.
3 Lab file ID for Volatile, Semivolatile; Lab sample ID for Pesticides in same format as
on forms.
4 Injection volume for BNAs and PESTs; Soil Aliquot Volume for VOA.
H-9
OLM01.8 8/91
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SAMPLE CONDITION RECORD (TYPE 22)
Use: Continuation of Type 20. Used to describe additional Sample Conditions
Position: Follows the Type 20 and 21 to which it applies.
FORMAT/
CONTENTS
"22"
YY1
I
MM
I
DD
I
HH
I
MM
1 2
Character
I
Numeric
I
Numeric
I
"Y" or "N"
1 3
Numeric
I .
Numeric
III
Numeric
I
Numeric
Character
MAXIMUM
LENGTH
2
1
2
1
2
1
2
1
2
1
2
1
14
1
4
1
5
1
1
1
8
1
8
3
5
1
5
4
1 For average
2 If "AVERAGE
CONTENTS
RECORD TYPE
Delimiter
CALIBRATION YEAR
Delimiter
CALIBRATION MONTH
Delimiter
CALIBRATION DAY
Delimiter
CALIBRATION HOUR
Delimiter
CALIBRATION MINUTE
Delimiter
CALIBRATION FILE ID
Delimiter
PH
Delimiter
PERCENT MOISTURE
Delimeter
DECANTED
Delimeter
EXTRACT VOLUME
Delimiter
DILUTION FACTOR
Delimiters
LEVEL
Delimiter
RECORD SEQUENCE NO.
CHECKSUM
, use the date and t
" is entered, then I
with a QC code of "CLD". This field must match Lab Field/Sample ID on Type 21 for the
associated calibration.
3 Use the initial extract volume adjusted (multiplied) by all contract-mandated
dilutions that are to be excluded from the dilution factor. Soil extract volume for
VOA; Cone. Extract volume for BNA and Pest. (In microliters)
4 Dilution factor of sample analyzed (omit contract-mandated dilutions).
5 Concentration level of Pesticide Individual Mix A and B standards. Concentration of
low point, mid point and high point calibration standards as a multiplier of low
point. Low point - 1.0, Mid point = up to 10.0, High point - 30.0 to 100.0.
H-10 OLM01.8 8/91
-------
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 the 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.
MAXIMUM
LENGTH CONTENTS
2 RECORD TYPE
1 Delimiter
1 TUNE LABEL
1 Delimiter
2 INJECTION YEAR
1 Delimiter
2 INJECTION MONTH
1 Delimiter
2 INJECTION DAY
1 Delimiter
2 INJECTION HOUR
1 Delimiter
2 INJECTION MINUTE
1 Delimiter
14 DFTPP/BFB LAB FILE ID
1 Delimiter
2 INSTRUMENT BLANK LABEL
1 Delimiter
2 BLANK INJECTION YEAR
1 Delimiter
2 BLANK INJECTION MONTH
1 Delimiter
2 BLANK INJECTION DAY
1 Delimiter
2 BLANK INJECTION HOUR
1 Delimiter
2 BLANK INJECTION MINUTE
1 Delimiter
14 INSTRUMENT BLANK LAB FILE/SAMPLE ID
4 Delimiters
2 METHOD BLANK LABEL
1 Delimiter
2 BLANK INJECTION YEAR
1 Delimiter
2 BLANK INJECTION MONTH
1 Delimiter
2 BLANK INJECTION DAY
1 Delimiter
2 BLANK INJECTION HOUR
1 Delimiter
2 BLANK INJECTION MINUTES
1 Delimiter
14 METHOD BLANK LAB FILE/SAMPLE ID
1 Delimiter
FORMAT/
CONTENTS
"23"
I
"P" or blank
I
YY
I
MM
I
DD
I
HH
I
MM
I
Character
I
"IB" or blank
I
YY
I
MM
I
DD
I
HH
I
MM
I
Character
MM
"MB"
I
YY
I
MM
I
DD
I
HH
I
MM
I
CHARACTER
H-ll
OLM01.8 8/91
-------
ASSOCIATED INJECTION AND COUNTER RECORD (TYPE 23) CONT:
MAXIMUM
LENGTH
1
1
2
1
1
1
2
1
1
1
2
1
1
1
2
1
5
4
CONTENTS
SURROGATE RECOVERY LABEL
Delimiter
SURROGATE RECOVERIES OUT
Delimiter
TIC LABEL
Delimiter
NO. OF TICS
Delimiter
SPIKE RECOVERY LABEL
Delimiter
SPIKE RECOVERIES OUT
Delimiter
RPD LABEL
Delimiter
RPD OUT
Delimiter
RECORD SEQUENCE NO.
CHECKSUM
FORMAT/
CONTENTS
"P" for % recoveries
I
Numeric
I
T" for TICS
I
Numeric
I
"S" for Spikes
I
Numeric
"R" for RPD1
I
Numeric
I
Numeric
Character
•R" for Matrix Spike/Duplicate Recovery Relative Percent Differences.
H-12
OLM01.8 8/91
-------
SAMPLE CLEANUP RECORD (TYPE 27)
Use: Continuation of Type 20. Used to identify sample/blank cleanup procedures
and QC results. Used for Form 9.
Position: Follows type 20, 21, 22, and 23 to which it applies
MAXIMUM
LENGTH CONTENTS
2 RECORD TYPE
1 Delimiter
1 FIRST CLEAN-UP TYPE
1 Delimiter
2 GPC CALIBRATION CHECK YEAR
1 Delimiter
2 GPC CALIBRATION CHECK MONTH
1 Delimiter
2 GPC CALIBRATION CHECK DAY
1 Delimiter
2 GPC CALIBRATION CHECK HOUR
1 Delimiter
2 GPC CALIBRATION CHECK MINUTE
1 Delimiter
14 GPC Data Descriptor
1 Delimiter
1 SECOND CLEAN-UP TYPE
1 Delimiter
2 FLORISIL LOT CHECK YEAR
1 Delimiter
2 FLORISIL LOT CHECK MONTH
1 Delimiter
2 FLORISIL LOT CHECK DAY
1 Delimiter
2 FLORISIL LOT CHECK HOUR
1 Delimiter
2 FLORISIL LOT CHECK MINUTE
1 Delimiter
14 FLORISIL DATA DESCRIPTOR
1 Delimiter
i SULFUR "CLEAN-UP
1 Delimiter
2 SULFUR BLANK LABEL
1 Delimiter
2 BLANK INJECTION YEAR
1 Delimiter
2 BLANK INJECTION MONTH
1 Delimiter
FORMAT/
CONTENTS
"27"
I
"G" for GPC
I
YY
I
MM
I
DD
I
HH
I
MM
I i
Character
I
"F" or blank
I
YY
I
MM
I
DD
I
HH
I
MM
1 2
Character'1
I
Y/N
I
"SB"
I
YY
I
MM
1 Lab Sample ID for GPC (GPC Column). Format is "GPC" followed by unique identifier.
2 Lab Sample ID for Florisil lot check. Format is "FLO" followed by florisil cartridge
lot number.
H-13
OLM01.8 8/91
-------
SAMPLE CLEANUP RECORD (TYPE 27) Cont.
MAXIMUM FORMAT/
LENGTH CONTENTS CONTENTS
1 Delimiter |
2 BLANK INJECTION DAY DD
1 Delimiter |
2 BLANK INJECTION HOUR HH
1 Delimiter |
2 BLANK INJECTION MINUTE MM
1 Delimiter |
14 SULFUR BLANK LABORATORY FILE/SAMPLE ID Character
1 Delimiter |
5 RECORD SEQUENCE NO. Numeric
4 CHECKSUM Character
H-14 OLM01.8 8/91
-------
RESULTS DATA RECORD (TYPE 30)
MAXIMUM
LENGTH
CONTENTS
FORMAT/
CONTENTS
2
1
1
1
9
1
9
1
5
1
3
1
13
1
5
1
1
1
13
1
1
1
13
1
1
1
5
1
1
1
5
1
5
1
1
1
5
1
1
1
5
1
1
1
13
1
1
1
RECORD TYPE
Delimiter
ANALYTE LABEL
Delimiter
CAS NUMBER
Delimiter
INTERNAL STD. CAS NUMBER
Delimiter
CONCENTRATION UNITS
Delimiter
RESULT QUALIFIER
Delimiter
RESULTS
Delimiter
FLAGS
Delimiter
AMOUNT ADDED LABEL
Delimiter
AMOUNT ADDED
Delimiter
CRQL LABEL
Delimiter
CRQL
Delimiter
RSD LABEL
Delimiter
RSD VALUE
Delimiter
MS/MSD REC LABEL
Delimiter
MS % RECOVERY
Delimiter
MSD % RECOVERY
Delimiter
RPD LABEL
Delimiter
RPD VALUE
Delimiter
SURR/SPIKE RECOVERY LABEL
Delimiter
SURR/SPIKE RECOVERY
Delimiter
MEAN CONCENTRATION LABEL
Delimiter
MEAN CONCENTRATION
Delimiter
PERCENT DIFFERENCE LABEL
Delimiter
"30"
I
"C" for Cas Number
I
Numeric
I
Numeric
I
Character
I ,
Character
I
Numeric
1 2
Character
1 3
"A" for Amt. added"3
I
Numeric
I
"U" for "undetected"
or blank
I
Numeric
I
"R" for RSD
Numeric
I
"P" for % recovery
I
Numeric
I
Numeric
I
"D"
I 5
Numeric
I
"S" for % recovery
I 6
% Recovery
"M" for Mean cone.
I 7
Numeric
"F" or "P
npnO
H-15
OLM01.8 8/91
-------
RESULTS DATA RECORD (TYPE 30) CONT:
5 PERCENT DIFFERENCE Numeric
1 Delimiter |
1 INTERNAL STANDARD AREA LABEL "I" for IS Area
1 Delimiter |
13 INTERNAL STANDARD AREA Numeric
1 Delimiter |
5 RECORD SEQUENCE NO. Numeric
4 CHECKSUM Character
1 For Type 20 for calibration summary (MNC), use "AVG" for average RRFs and Mean
Calibration Factors.
2 A maximum of five flags (D,E,J,B,A,P or N) with no space between the flags can be
reported, each representing a qualification of the result as described in Exhibit B.
3 Also Nominal Amount for Pest Form (7D-7E).
4 "R" for % Resolution (Form 6G) or for RSD of Response factors under Calibration
summary (MNC) Type 20.
5 RPD for MS/MSD recoveries, or for Pest. Calibration Verification (Form 7D/7E).
6 Surrogate or Spike (Forms 2, Form 9A/9B) recovery.
7 Mean Concentration for Multicomponent analytes detected in Pesticide analyses.
8 "P" for Percent Difference between concentrations from two columns in Pesticide
analyses, or "F" for Percent Difference between average RRF (initial calibration) and
RRF50 (continuing calibration) in VOA/BNA analyses.
H-16 OLM01.8 8/91
-------
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.)
MAXIMUM
LENGTH CONTENTS
2 RECORD TYPE
3 Delimiters
2 RETENTION TIME LABEL
1 Delimiter
5 RETENTION TIME
1 Delimiter
3 FIRST LIMIT LABEL
1 Delimiter
5 RT WINDOW LOWER LIMIT
1 Delimiter
3 SECOND LIMIT LABEL
1 Delimiter
1 RT WINDOW UPPER LIMIT
2 Delimiters
2 THIRD LIMIT LABEL
1 Delimiter
5 % BREAKDOWN
1 Delimiter
5 COMBINED % BREAKDOWN
2 Delimiters
1 PEAK
1 Delimiter
5 RECORD SEQUENCE NO.
4 CHECKSUM
FORMAT/
CONTENTS
"32"
III
"RT"
I
Numeric
I
"RTF"
I
Numeric
I
"RTT"
I
Numeric
II
"PB" for % breakdown
I
Numeric (DDT/ENDRIN)
I
Numeric
11 1
1 THROUGH 51
I
Numeric
Character
Peaks 1, 2, and 3 are mandatory, peaks 4 and 5 are optional. Types 30 and 31 will be
repeated for each peak that is reported (a minimum of three, a maximum of five times).
This is for multicomponent analytes in PESTICIDE analyses.
H-17
OLM01.8 8/91
-------
NAME RECORD (Type 33)
Use: To carry an analyte name for TIC compounds
Position: Follows Type 30 for TIC compounds.
MAXIMUM FORMAT/
LENGTH CONTENTS CONTENTS
2 RECORD TYPE "33"
1 Delimiter |
67 NAME OF COMPOUND Character
1 Delimiter |
5 RECORD SEQUENCE NO. Numeric
4 CHECKSUM Character
H-18 OLM01.8 8/91
-------
INSTRUMENTAL DATA READOUT RECORD (TYPE 36)
Use: To describe DFTPP/BFB percent abundances for Form 5.
Position: Follows Type 30 for internal standards and DFTPP/BFB data.
MAXIMUM FORMAT/
LENGTH CONTENTS
2 RECORD TYPE
1 Delimiter
1 MASS LABEL
3 Delimiters
3 FIRST MASS (DFTPP/BFB)
2 Delimiters
5 FIRST PERCENT ABUNDANCE
1 Delimiter
3 SECOND MASS
1 Delimiter
5 SECOND PERCENT ABUNDANCE
1 Delimiter
5 PERCENT MASS
1 Delimiter
3 THIRD MASS
1 Delimiter
5 THIRD PERCENT ABUNDANCE
2 Delimiters
3 FOURTH MASS
1 Delimiter
5 FOURTH PERCENT ABUNDANCE
1 Delimiter
5 PERCENT MASS
1 Delimiter
3 FIFTH MASS
1 Delimiter
5 FIFTH PERCENT ABUNDANCE
1 Delimiter
5 PERCENT MASS
1 Delimiter
3 SIXTH MASS
1 Delimiter
5 SIXTH PERCENT ABUNDANCE
2 Delimiters
3 SEVENTH MASS
1 Delimiter
5 SEVENTH PERCENT ABUNDANCE
1 Delimiter
5 PERCENT MASS
1 Delimiter
3 EIGHTH MASS
1 Delimiter
5 EIGHTH PERCENT ABUNDANCE
1 Delimiter
5 PERCENT MASS
CONTENTS
"36"
I
"M"
III
Numeric
II
Numeric
I
Numeric
I
Numeric
I
% mass of 69, SNA only
I
Numeric
I
Numeric
II
Numeric
I
Numeric
I
% mass of 69, BNA only
I
Numeric
I
Numeric
I
% mass of 174, VGA only
I
Numeric
I
Numeric
II
Numeric
I
Numeric
I
% mass of 174, VOA only
I
Numeric
I
Numeric
I
% mass of 174, VOA only
H-19
OLM01.8 8/91
-------
INSTRUMENTAL DATA READOUT RECORD (TYPE 36) CONT:
MAXIMUM
LENGTH CONTENTS
1 Delimiter
3 NINTH MASS
1 Delimiter
5 NINTH PERCENT ABUNDANCE
1 Delimiter
5 PERCENT MASS
1 Delimiter
3 TENTH MASS
1 Delimiter
5 TENTH PERCENT ABUNDANCE
2 Delimiters
3 ELEVENTH MASS
1 Delimiter
5 ELEVENTH PERCENT ABUNDANCE
2 Delimiters
3 TWELFTH MASS
1 Delimiter
5 TWELFTH PERCENT ABUNDANCE
2 Delimiters
3 THIRTEENTH MASS
2 Delimiters
5 THIRTEENTH PERCENT ABUNDANCE
1 Delimiter
5 PERCENT MASS
1 Delimiter
5 RECORD SEQUENCE NO.
4 CHECKSUM
FORMAT/
CONTENTS
Numeric
I
Numeric
I
% mass of 176, VGA only
I
Numeric
I
Numeric
II
Numeric
I
Numeric
II
Numeric
I
Numeric
II
Numeric
II
Numeric
I
% mass of 442, BNA only
t
Numeric
Character
H-20
OLM01.8 8/91
-------
COMMENT RECORD (Type 90)
Use: To provide for Operator-Entered Comments.
Position: May occur anywhere
MAXIMUM FORMAT/
LENGTH CONTENTS CONTENTS
2 RECORD TYPE "90"
1 Delimiter |
67 ANY COMMENT Character
1 Delimiter |
5 RECORD SEQUENCE NO. Numeric
4 CHECKSUM Character
H-21 OLM01.8 8/91
-------
10. Definitions of Various Codes Used in Agency Standard Records
10.1 Quality Control and Related Codes (QCC) in Type 20 Records
Note: These codes appear in the QC code fields of type 20 records. They are used
to indicate the type of data that is being reported.
QCC
Name
LRB LABORATORY (REAGENT)
BLANK
LIB LABORATORY INSTRUMENT
BLANK
LSB LABORATORY SULFUR
BLANK
Definition
The "Method Blank" (See Exhibit G).
The "Instrument Blank"
If different from "Method Blank" (Pesticides)
LSD LABORATORY SPIKE
DUPLICATE BACKGROUND
(ORIGINAL) VALUES
LF1 LABORATORY SPIKED
SAMPLE - FINAL -
FIRST MEMBER
LF2 LABORATORY SPIKED
SAMPLE - FINAL -
SECOND MEMBER
An environmental sample which is analyzed according
to the analytical method, and subsequently used for
the matrix spike and the matrix spike duplicate
(See Exhibit G).
The "Matrix Spike*
LF2
(See Exhibit G) - must preceed
The "Matrix Spike Duplicate" (See Exhibit G)
LPC LABORATORY PERFORMANCE
CHECK SOLUTION
A solution of DFTPP (BNA) or BFB (VOA) or
method analytes (PEST/PCB) used to evaluate the
performance of an instrument with respect to a
defined set of criteria (Tune or Resolution Check
Sample) (See Exhibit G).
FLO FLORISIL CHECK
SOLUTION
GPC GPC CHECK
SOLUTION
A solution of pesticides used to check recovery
from each lot of Florisil cartridges.
A solution of pesticides used to check recovery
from each new GPC calibration.
CLM INITIAL CALIBRATION -
MULTI POINT
The Initial Calibration for GC/MS (See Exhibit G) ,
or the Initial Individual Standard Mixes (A,
B) for Pesticides (See Exhibit D PEST).
Response factors (GC/MS) or Calibration Factors
(Pesticides) rather than concentrations will be
reported on the following type 30 records.
H-22
OLM01.8 8/91
-------
CLS INITIAL CALIBRATION
SINGLE POINT
CLC CONTINUING CHECK
CALIBRATION
CLE CONTINUING PERFORMANCE
CHECK
CLD DUAL PURPOSE
CALIBRATION
The Initial Toxaphene/Aroclor Mixes used to determine
all calibration factors. (See Exhibit D PEST).
The continuing calibration for GC/MS (See Exhibit G).
The subsequent Individual Standard Mixes
(A,B) and Performance Evaluation Mixture for
Pesticides (See Exhibit D PEST).
A calibration solution as above used both as an
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
CALIBRATIONS
The data following represent mean values and
percent RSD's from the initial calibration
(GC/MS) or the mean calibration factors, mean
retention times amd retention time windows
(pesticides).
10.2 Codes For Sample Medium (Matrix, Source)
Medium
All Media, Specific Medium not Applicable.
Calibrations, Tunes, etc
Water
Code
Use for
H-23
OLM01.8 8/91
-------
10.3 List of Sample and Result Qualifiers
Definition: A sample 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 for an entire sample but it is qualified in
some respect relating to the type or validity of the result.
10.3.1 Sample Qualifiers
Qualifier Full Name
RIN
REX
REJ
RE-ANALYZED
RE-PREPARED
REJECTED
SRN
SRS
DILUTED
SECONDARY
DILUTION
Definition
The indicated analysis results were
generated from a re-injection of
the same sample extract or aliquot
The indicated analysis results were
generated from a re-extraction of
the same sample
The results for the entire sample analysis have
been rejected for an unspecified reason by the
laboratory. For initial calibration
data, these data were not utilized in the
calculation of the mean.
The indicated analysis results were
generated from a dilution of the
same sample (DL SUFFIX)
The indicated analysis results were
generated from a secondary dilution of
the same sample (DL2 SUFFIX - Pesticides)
10.3.2 Result Qualifiers in Type 30 Records
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 for a single analyte 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
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 o
values; e.g., relative response factors.
of
H-24
OLM01.8 8/91
-------
CBC
CANNOT BE CALCULATED
LTL
GTL
LLS
TIE
REJ
STD
STB
FBK
MSP
TFB
ALC
NRP
LESS THAN LOWER
CALIBRATION LIMIT
GREATER THAN UPPER
CALIBRATION LIMIT
LESS THAN LOWER STANDARD
TENTATIVELY IDENTIFIED
-ESTIMATED VALUE
REJECTED
INTERNAL STANDARD
INTERNAL STANDARD
BELOW DETECTION LIMITS
FOUND IN BLANK
PERCENT RECOVERY
TENTATIVELY IDENTIFIED
AND FOUND IN BLANK
ALDOL CONDENSATION
NON-REPRODUCIBLE
PRE
PRESUMPTIVE PRESENCE
The analysis result cannot be calculated
because an operand value is qualified.
Identifies analytes whose Internal
Standard is not found.
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 "MSD"
percent recovery and the Percent RPD.
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).
Results of two or more injections are
not comparable (Form ID "p" flag), e.g.,
Aroclor target analyte with greater than 25%
difference between column analyses.
Presumptive evidence of presence of material
for TIC (Form 1-E or 1-F "N" flag).
H-25
OLM01.8 8/91
-------
11.
Format of Records for Specific Uses
11.1 Format of the SAMPLE HEADER DATA RECORD (Type 20) for Mean Response Factors
MAXIMUM
LENGTH CONTENTS
2
3
1
1
3
2
5
1
6
9
3
3
5
4
"20"
Delimiters
"0"
Delimiter
"MNC"
Delimiters
Case Number
Delimiter
SDG No.
Delimiters
Analyte Count
Delimiters
Record Sequence No.
Checksum
FORMAT/
CONTENTS
Record Type
III
All matrices
I
Identifies Mean Response Factors
II
Numeric
I
Character
MINIMI
Numeric
III
Numeric
Character
11.2 Format of the RESULTS DATA RECORD (Type 30) for Mean Relative Response Factors
MAXIMUM
LENGTH CONTENTS
2
1
1
1
9
1
9
3
3
1
6
6
1
1
5
14
5
4
"30"
Delimiter
"C"
Delimiter
CAS NUMBER
Delimiter
INTERNAL STANDARD
CAS NUMBER
Delimiters
"AVG"
Delimiter
MEAN RESPONSE FACTOR
Delimiters
"R"
Delimiter
PERCENT RSD
Delimiters
RECORD SEQUENCE NO.
CHECKSUM
FORMAT/
CONTENTS
Record Type
I
"C" for CAS Number
I
Numeric
I
Numeric
Indicates Average Value
Right Justified
MINI
Indicates Percent
I
Numeric
Illlllllllllll
Numeric
Character
RSD
H-26
OLM01.8 8/91
-------
11.3 Format of the SAMPLE HEADER DATA RECORD (Type 20) for Matrix Spike Duplicates
CONTENTS FORMAT/CONTENTS
MAXIMUM
LENGTH
2
2
12
1
1
1
3
2
5
1
6
1
2
1
2
1
2
1
2
1
2
2
1
1
5
1
3
3
5
4
Record Type
Delimiters
EPA Sample Number
Delimiter
Matrix
Delimiter
QC Code
Delimiters
Case Number
Delimiter
SDG No.
Delimiter
Year Analyzed
Delimiter
Month Analyzed
Delimiter
Day Analyzed
Delimiter
Hour Analyzed
Delimiter
Minute Analyzed
Delimiters
Sample wt/vol unit
Delimiter
Sample wt/vol
Delimiter
Analyte Count
Delimiters
Record Sequence Number
Checksum
"20"
II
As is exactly on the Form
I
"H"
I
LF2
II
Numeric
I
Character
I
YY
I
MM
I
DD
I
HH
I
MM
II
"G"
I
Numeric
I
Numeric
III
Numeric
Character
11.4 Format of the COUNTER RECORD (Type 23) for Matrix Spike Duplicates (for VOA and
BNA)
Position: Follows the type 20 to which it applies.
MAXIMUM
LENGTH
2
2
2
1
2
1
2
1
2
1
CONTENTS
Record Type
Delimiters
Injection Year
Delimiter
Injection Month
Delimiter
Injection Day
Delimiter
Injection Hours
Delimiter
FORMAT/CONTENTS
"23"
II
YY
I
MM
I
DD
I
HH
H-27
OLM01.8 8/91
-------
2
1
14
11
2
1
2
1
2
1
2
1
2
1
2
1
14
1
1
1
2
3
1
1
2
1
1
1
2
1
5
4
Injection Minutes
Delimiter
DFTPP Lab File ID
Delimiters
Method Blank Label
Delimiter
Blank Injection Year
Delimiter
Blank Injection Month
Delimiter
Blank Injection Day
Delimiter
Blank Injection Hour
Delimiter
Blank Injection Minute
Delimiter
Method Blank Lab File ID
Delimiter
Surrogate Recovery Label
Delimiter
Surrogate Recovery Out
Delimiters
Spike Recovery Label
Delimiter
Spike Recovery Out
Delimiter
RPD Label
Delimiter
RPD Out
Delimiter
Record Sequence Number
Checksum
MM
I
Character
Illllllllll
"MB"
I
YY
I
MM
I
DD
I
HH
I
MM
I
Character
I
Numeric
III
"S"
I
Numeric
I
Numeric
I
Numeric
Character
H-28
OLM01.8 8/91
-------
(Type 23) for Matrix Spike Duplicates (for Pesticide)
Position: Follows the type 20 to which it applies.
MAXIMUM
LENGTH
2
8
2
1
2
1
2
1
2
1
2
1
2
1
14
4
2
1
2
1
2
1
2
1
2
1
2
1
14
1
1
1
2
3
1
1
2
1
1
1
1
1
5
4
CONTENTS
Record Type
Delimiters
Instrument Blank Label
Delimiter
Blank Injection Year
Delimiter
Blank Injection Month
Delimiter
Blank Injection Day
Delimiter
Blank Injection Hour
Delimiter
Blank Injection Minute
Delimiter
Instrument Blank Lab File ID
Delimiters
Method Blank Label
Delimiter
Blank Injection Year
Delimiter
Blank Injection Month
Delimiter
Blank Injection Day
Delimiter
Blank Injection Hour
Delimiter
Blank Injection Minute
Delimiter
Method Blank Lab File ID
Delimiter
Surrogate Recovery Label
Delimiter
Surrogate Recovery Out
Delimiters
Spike Recovery Label
Delimiter
Spike Recovery Out
Delimiter
RPD Label
Delimiter
RPD Out
Delimiter
Record Sequence Number
Checksum
FORMAT/CONTENTS
"23"
MINIM
"IB"
I
YY
I
MM
I
DD
I
HH
I
MM
I
Character
Illl
"MB"
I
YY
I
MM
I
DD
I
HH
I
MM
I
Character
I
Numeric
IN
"S"
I
Numeric
I
"R"
I
Numeric
I
Numeric
Character
H-29
OLM01.8 8/91
-------
11.5 Format of the RESULTS DATA RECORD (Type 30) for Matrix Spike Duplicates
MAXIMUM
LENGTH
2
1
1
1
9
1
9
1
2
1
3
1
13
2
1
1
13
1
1
3
1
1
5
2
1
1
1
1
5
1
1
1
1
1
5
1
1
1
13
1
5
4
CONTENTS
Record Type
Delimiter
Analyte Label
Delimiter
CAS Number
Delimiter
Internal Standard CAS Number
Delimiter
Concentration Unit
Delimiter
Result Qualifier
Delimiter
Results
Delimiters
Amount Added Label
Delimiter
Amount Added
Delimiter
CRQL Label
Delimiter
MS/MSD Recovery Label
Delimiter
MS/MSD % Recovery
Delimiters
RPD Label
Delimiter
Surrogate Recovery Label
Delimiter
Surrogate Recovery
Delimiter
Mean Concentration Label
Delimiter
Percent Difference Label
Delimiter
Percent Difference
Delimiter
Internal Standard Area Label
Delimiter
Internal Standard Area
Delimiter
Record Sequence Number
Checksum
FORMAT/CONTENTS
"30"
I
"C" for CAS No.
I
Numeric
I
Numeric
I
"NG"
I
STD
I
Numeric
II
A
I
Numeric
I
"U"
I
Numeric
II
itjjn
% Recovery
I
"M"
I
Numeric
I
Numeric
I
Numeric
Character
H-30
OLM01.8 8/91
-------
MAXIMUM
LENGTH
2
2
5
1
1
1
3
CONTENTS
"20"
Delimiters
PEM ##
Delimiter
"0"
Delimiter
"CLE"
11.6 Format of the Sample Header Data Record (Type 20) for Performance Evaluation
Mixture
FORMAT/
CONTENTS
Record Type
II
Sample I.D.
I
All matrices
I
Indicates Continuing Performance
Check (Pesticide Standard)
II
Numeric
I
Character
I
YY
I
MM
I
DD
I
HH
I
MM
III
Numeric
III
Numeric
Character
2
5
I
5
I
2
I
2
1
2
I
2
I
2
3
3
3
5
4
Delimiters
CASE NUMBER
Delimiter
SDG NO.
Delimiter
YEAR OF INSTRUMENTAL ANALYSIS
Delimiter
MONTH OF ANALYSIS
Delimiter
DAY OF ANALYSIS
Delimiter
HOUR OF INSTRUMENTAL ANALYSIS
Delimiter
MINUTES OF ANALYSIS
Delimiters
ANALYTE COUNT
Delimiters
RECORD SEQUENCE NO.
CHECKSUM
H-31
OLM01.8 8/91
-------
11.7 Format of the Auxiliary Data Record (Type 32) for Pesticide Calibration
Verification Summary (Percent Breakdown Data for 4,4'-DDT from Form 7D).
MAXIMUM
LENGTH
2
3
2
1
5
1
3
1
5
1
3
1
5
3
2
1
5
4
5
4
CONTENTS
"32"
Delimiters
«RT»
Delimiter
RT Value
Delimiter
"RTF"
Delimiter
RT Window Lower Limit
Delimiter
"RTT"
Delimiter
RT Window Upper Limit
Delimiters
»PBn
Delimiter
% Breakdown
Delimiters
Record Sequence No.
Checksum
FORMAT/
CONTENTS
Record Type
III
Retention time label.
I
Numeric
I
First limit value
I
Numeric
I
Second limit label
Numeric
III
% Breakdown Label
I
Numeric (for 4,4'-DDT)
INI
Numeric
Character
H-32
OLM01.8 8/91
-------
11.8 Format of the Sample Header Data Records (Type 20-30) for Continuing Checks (GC/MS
Methods) Format
FORMAT/
CONTENTS
Record Type
II
e.g., VSTD050
From Exhibit B
I
All matrices
I
Indicates
Continuing Check
I
See Section 7.3
I
Optional
I
Character
I
YY
I
MM
I
DD
I
HH
I
MM
III
Numeric
III
Numeric
Character
FORMAT/
CONTENTS
MAXIMUM
LENGTH
2
2
12
1
1
1
3
1
3
1
5
1
5
1
2
1
2
1
2
1
2
1
2
3
3
3
5
4
MAXIMUM
LENGTH
2
1
1
5
6
1
14
11
5
4
CONTENTS
"20"
Delimiters
EPA Sample I.D.
Delimiter
"0"
Delimiter
"CLC"
Delimiter
Sample Qualifier
Delimiter
Case Number
Delimiter
SDG No.
Delimiter
Year of Instrumental Analysis
Delimiter
Month of Analysis
Delimiter
Day of Analysis
Delimiter
Hour of Instrumental Analysis
Delimiter
Minute of Analysis
Delimiters
Analyte Count
Delimiters
Record Sequence No .
Checksum
CONTENTS
"21"
Delimiter
"Y" or "N"
Delimiters
SAS NUMBER
Delimiter
LAB FILE I.D.
Delimiters
RECORD SEQUENCE NO.
CHECKSUM
Record Type
I
"Y" for heated;
Mill
Leave Delimiter
if none
I
Character
Illllllllll
Numeric
Character
"N" for non-heated
H-33
OLM01.8 8/91
-------
MAXIMUM
LENGTH CONTENTS
2 "23"
1 Delimiter
1 "P"
1 Delimiter
2 INJECTION YEAR
1 Delimiter
2 INJECTION MONTH
1 Delimiter
2 INJECTION DAY
1 Delimiter
2 INJECTION HOUR
1 Delimiter
2 INJECTION MINUTES
1 Delimiter
14 DFTPP/BFB LAB FILE ID
26 Delimiters
5 RECORD SEQUENCE NO.
4 CHECKSUM
FORMAT/
CONTENTS
Record Type
1
Labels data as
"tune" data
I
Date of associated DFTPP/BFB
Injection
I
MM
I
DD
I
HH
I
MM
I
From Instrument data system
iiiimiiiiiiiiiiiiiiiiiii
Numeric
Character
MAXIMUM
LENGTH CONTENTS
2 "30"
1 Delimiter
1 "C"
1 Delimiter
9 CAS- NUMBER
1 Delimiter
9 CAS NUMBER INTERNAL STD. UTILIZED
1 Delimiter
5 UNITS OF MEASURE
1 Delimiter
3 RESULT QUALIFIER
1 Delimiter
13 ANALYTICAL RESULT
11 Delimiters
1 "D"
7 Delimiters
13 RF PERCENT DIFFERENCE
4 Delimiters
5 RECORD SEQUENCE NO.
4 CHECKSUM
FORMAT/
CONTENTS
Record Type
I
Numeric
I
Numeric
I
Character
Numeric
iiiimmi
Identifies Percent Difference
MINN
Numeric
INI
Numeric
Character
H-34
OLM01.8 8/91
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