905R88104
USEPA CONTRACT LABORATORY PROGRAM
xSTATEMENT OF WORK
V
FOR
ORGANICS ANALYSIS
Multi-Media
Multi-Concentration
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STATEMENT OF WORK
Table of Contents
EXHIBIT A: SUMMARY OF REQUIREMENTS
EXHIBIT B: REPORTING AND DELIVERABLES REQUIREMENTS
EXHIBIT C: TARGET COMPOUND LIST (TCL) AND CONTRACT REQUIRED QUANTITATION
LIMITS (CRQL)
EXHIBIT D: ANALYTICAL METHODS
EXHIBIT E: QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
EXHIBIT F: CHAIN-OF-CUSTODY, DOCUMENT CONTROL AND STANDARD OPERATING
PROCEDURES
EXHIBIT G: GLOSSARY OF TERMS
EXHIBIT H: DATA DICTIONARY AND FORMAT FOR DATA DELIVERABLES IN
COMPUTER-READABLE FORMAT
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EXHIBIT A
SUMMARY OF REQUIREMENTS
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SECTION I
GENERAL REQUIREMENTS
The Contractor shall use proven instruments and techniques to identify and
measure the concentrations of volatile, semivolatile and pesticide compounds
listed on the Target Compound List (TCL) in Exhibit C. The Contractor shall
employ state-of-the-art GC/MS and/or GC procedures to perform all analyses,
including all 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. 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.
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 achieved for each of the TCL compounds.
During preparation, the Contractor shall fortify all samples, blanks, matrix
spikes, and matrix spike duplicates with the surrogate spiking compounds
listed in Exhibit E. Additionally, all sample semivolatile extracts and
aliquots for volatile organics analysis shall be spiked with the internal
standard compounds listed in Exhibit E 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) nonsurrogate volatile components and up to twenty (20) nonsurrogate
semivolatile components that are not on the Target Compound List (Exhibit C).
Exhibit F contains chain-of-custody and sample documentation requirements
which the Contractor must follow in processing samples under this contract,
and specifies requirements for written laboratory standard operating
procedures.
Sample analysis data, sample documentation and other deliverables shall be
reported as specified in Exhibit B. Specifications for reporting data in
computer-readable form appear in Exhibit H.
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.
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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.
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SECTION II
SPECIFIC REQUIREMENTS
A. For each sample, the Contractor shall perform the following tasks:
Task I: Receive and Prepare Hazardous Waste Samples.
1. 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). If separately funnel or sonication
procedures are employed for extractions for semivolatile and
pesticide analyses, extraction of water samples shall be completed
within 5 days of VTSR, and extraction of soil samples shall be
completed within 10 days of VTSR. If continuous liquid-liquid
extraction procedures are employed, extraction of water samples
shall be started within 5 days of VTSR.
Extracts of either water or soil samples must be analyzed within 40
days of VTSR. This does not release the Contractor from the data
turnaround time specified in Exhibit B, Section I.
Task II: Extraction and Analysis for Identification of Specific
Organic Compounds.
1. Extracts and aliquots prepared in Task I shall be analyzed by GC
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.
Task III: Qualitative Verification of the Compounds Identified in
Task II.
1. The 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. 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, and
b. Correspondence of the sample component and standard component
mass spectra. This procedure requires the use of multiple
internal standards.
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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 tuning requirements of Tables 1.1 and 1.2 in Exhibit E. 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 in (1) must agree
within plus or minus 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/PCB 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 E) of the
standard component analyzed on the same GC column and
instrument, as part of the same 72-hour analytical sequence
specified in Exhibit D PEST.
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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.
Task IV: Quantification of Compounds Verified in Task III.
1. The Contractor shall quantify components analyzed by GC/MS
techniques and 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 E, Part 2, Tables 2.1 or 2.2.
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 E.
3. The Contractor shall quantify components analyzed by GC/EC
techniques and identified in Task II and verified in Task III by
the external standard method stipulated in Exhibit D PEST.
4. The Contractor shall perform an initial three-point calibration,
verify its linearity, determine the degradation of labile
components, and determine calibration factors for all standards
analyzed by GC/EC techniques as part of a 72-hour analytical
sequence, as described in Exhibit D PEST and Exhibit E.
Task V: Tentative Identification of Non-TCL 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 the ten (10) nonsurrogate organic compounds of greatest
concentration which are not listed in Exhibit C. For each
base/neutral/acid fraction, the Contractor shall conduct a search
to determine the possible identification of the (20) nonsurrogate
organic compounds of greatest concentration which are not listed in
Exhibit C. In performing searches, the 1985 (or most recent)
release of the National Bureau of Standards library (containing
42,261 spectra) must be used. NOTE: Substances with responses
less than 10 percent of the nearest internal standard are not
required to be searched in this fashion.
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,
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unknown chlorinated compound). If probable molecular weights can
be distinguished, include them.
The Contractor shall pot report as tentatively identified compounds
(TIC) any TCL compounds from another analytical fraction (i.e., do
not report late eluting volatile compounds as TICs in the
semivolatile analysis).
Task VI: Quality Assurance/Quality Control Procedures.
1. All specific quality assurance procedures prescribed in Exhibit E
shall be strictly adhered to by the Contractor. Records
documenting the use of the protocol shall be maintained in
accordance with the document control procedures prescribed in
Exhibit F, and shall be reported in accordance with Exhibit B,
Reporting Requirements and Deliverables.
2. 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 soil samples only),
once:
o each Case of field samples received, OR
o each 20 samples in a Case, OR
o each 14 calendar day period during which field samples in a
Case were received (said period beginning with the receipt of
the first sample in that Sample Delivery Group),
whichever is most frequent.
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).
3. 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 or continuous liquid-liquid extraction), and a
similar concentration level (for soil samples only), once:
o each Case of field samples received, OR
o each 20 samples in a Case, including matrix spikes and
reanalyses, OR
o each 14 calendar day period during which field samples in a
Case were received (said period beginning with the receipt of
the first sample in that Sample Delivery Group), OR
o whenever samples are extracted,
whichever is most frequent
Volatile analysis requires one method blank for each 12-hour time
period when volatile TCL compounds are analyzed.
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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).
4. The Contractor shall perform instrument calibration (by "hardware
tune") for each 12-hour time period, to include:
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 Performance Evaluation check samples submitted to the
laboratory by EPA. The results of comparison studies are due as
stipulated in the Delivery Schedule in Exhibit B, Section I. The
results of all such control or PE check samples may be used as
grounds for termination of noncompliant contractors. "Compliant
performance" is defined as that which yields correct compound
identification and concentration values as determined by EPA, as
well as meeting the contract requirements for analysis (Exhibits C
and 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).
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 floppy 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
he ade r info rmat ion.
3. The data reported by the Contractor on the hardcopy data forms and
the associated computer-readable data submitted by the Contractor
must contain identical information. If during government
inspection discrepancies are found, the Contractor shall be
required to resubmit either or both sets of data at no additional
cost to the government.
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C. The Contractor shall provide analytical equipment and technical
expertise for this contract as specified following:
1. The Contractor shall have sufficient gas chromatograph (GC) and gas
chromatograph/mass spectrometer/data system (GC/MS/DS) capability
to meet all the terms and conditions of the Contract. Instrument
requirements are defined in Section III, Detailed Technical &
Management Requirements. The Contractor shall maintain, at a
minimum, all analytical equipment allocated for this contract at
the time of contract award.
2. The Contractor's instrument systems shall have the following:
a. The GC/MS shall be equipped with a glass jet separator when
using packed columns.
b. The computer shall be interfaced by hardware to the mass
spectrometer and be capable of acquiring continuous mass scans
for the duration of the chromatographic program.
c. The computer shall be equipped with mass storage devices for
saving all data from the GC/MS runs.
d. Computer software shall be available to allow searching GC/MS
runs for specific ions and plotting the intensity of the ions
with respect to time or scan number.
e. 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.
f. The GC for pesticide analysis shall be equipped with packed
columns or wide bore capillary columns (see Exhibit D, Section
IV, for an optional FSCC confirmation column) and a suitable
detector as described in Exhibit D.
3. The Contractor shall use a magnetic tape storage device capable of
recording data and suitable for long-term, off-line storage. The
Contractor shall retain all raw GC/MS data acquired under this
contract on magnetic tape in appropriate instrument manufacturer's
format. The Contractor is required to retain the magnetic tapes
with associated hardcopy tape logbook identifying tape contents
(see Exhibit B) for 365 days after data submission. During that
time, the Contractor shall submit tapes and logbook within 7 days
of request, as specified in the Contract Performance/Delivery
Schedule.
4. The Contractor shall have a computerized MS library search system
capable of providing a forward comparison, utilizing the standard
spectra contained in the mass spectral library. The 1985 (or most
recent) release of the National Bureau of Standards library
(containing 42,261 spectra) must be used.
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a. The system shall provide a numerical ranking of the standard
spectra most closely corresponding to the sample spectra
examined.
b. The data system shall have software capable of removing
background signals from spectra.
5. The Contractor shall have, in-house and operable, a device capable
of analyzing purgeable organics as described in Exhibit D.
6. The Contractor shall have, in-house, the appropriate standards for
all target compounds listed in Exhibit C prior to accepting any
samples from SMO. Standards provided by EPA for use in the
Preaward Performance Evaluation may not contain all the target
compounds and thus must not be used for routine analyses unless or
until they have been supplemented with commercially-available
standard materials.
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 diskettes, in ASCII
text file format and in accordance with the file, record and field
specifications listed in Exhibit H.
E. The minimum functional requirements necessary to meet the terms and
conditions of this contract are listed below. The Contractor shall
designate and utilize key personnel to perform these functions. The EPA
reserves the right to review personnel qualifications and experience.
See Section III, Detailed Technical & Management Requirements.
o GC/MS/DS operation.
o Mass spectral interpretation.
o Sample extraction and concentration.
o Purge and trap volatile organic compounds analysis.
o Pesticide residue analysis of organochlorine pesticides and PCBs,
including clean-up procedures.
o Quality assurance/quality control
o Sample receipt, storage, and tracking, including chain-of-custody
procedures.
F. The Contractor shall respond in a timely manner to requests from data
recipients for additional information or explanations that result from
the Government's inspection activities.
G. The Contractor shall preserve all sample extracts after analysis in
bottles/ vials with Teflon-lined septa and shall maintain stored
extracts at 4*C (±2*C). The Contractor is required to retain the sample
extracts for 365 days after data submission. During that time, the
Contractor shall submit the extracts within 7 days after request, as
specified in the Contract Performance/Delivery Schedule.
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H. The Contractor shall adhere to chain-of-custody procedures described in
Exhibit F. Documentation, as described therein, shall be required to
show that all procedures are being strictly followed. This
documentation shall be reported as the complete Case file purge (see
Exhibit B).
1. 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 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.
J. Sample analyses will be scheduled by groups of samples, each defined as
a Case and identified by a unique EPA Case number assigned by SMO. A
Case signifies a group of samples collected at one site or geographical
area over a finite time period, and will include one or more field
samples with associated blanks. Samples may be shipped to the
Contractor in a single shipment or multiple shipments over a period of
time, depending on the size of the Case.
A Case consists of one or more Sample Delivery Group(s). A Sample
Delivery Group (SDG) is defined by the following, whichever is most
frequent:
o each Case of field samples received, OR
o each 20 field samples within a Case, OR
o each 14 calendar day period during which field samples in a Case are
received (said period beginning with the receipt of the first sample
in the Sample Delivery Group).
Samples may be assigned to Sample Delivery Groups by matrix (i.e., all
soils in one SDG, all waters in another), at the discretion of the
laboratory. Such assignment must be made at the time the samples are
received, and may not be made retroactively.
Data for all samples in a Sample Delivery Group are due concurrently 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
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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, Section I.
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 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 routinely be shipped 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.
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, Task VI, the Contractor shall have the following
technical and management capabilities:
A. TECHNICAL CAPABILITY
1. Technical Functions
a. GC/MS Laboratory Supervisor
(1) Responsible for all technical efforts of the GC/MS
laboratory to meet all terms and conditions of the EPA
contract.
(2) Qualifications:
(a) Education:
Minimum of Bachelor's degree in chemistry or any
physical science.
(b) Experience:
Minimum of three years of laboratory experience,
including at least one year of supervisory
experience.
b. GC/MS Operator Qualifications
(1) Education:
Minimum of Bachelor's degree in chemistry or any physical
science.
(2) Experience:
One year of experience in operating and maintaining
GC/MS/DS with degree in chemistry or a physical science,
or three years of experience in operating and maintaining
GC/MS/DS.
c. Mass Spectral Interpretation Specialist Qualifications
(1) Education:
o Minimum of Bachelor's degree in chemistry or any
physical science.
o Training course(s) in mass spectral interpretation.
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(2) Experience:
Minimum of two years of experience.
d. GC Laboratory Supervisor
(1) Responsible for all technical efforts of the GC
laboratory.
(2) Qualifications:
(a) Education:
Minimum of Bachelor's degree in chemistry or any
physical science.
(b) Experience:
Minimum of three years of laboratory experience,
including at least one year of supervisory
experience.
e. Pesticide Residue Analysis Expert Qualifications
(1) Education:
Minimum of Bachelor's degree in chemistry or any physical
science.
(2) Experience:
Minimum of two years of experience in operating and
maintaining GC and interpreting GC chromatograms.
f. Sample Preparation Laboratory Supervisor
(1) Responsible for all technical efforts of sample
preparations to meet all terms and conditions of the EPA
contract.
(2) Qualifications:
(a) Education:
Minimum of Bachelor's degree in chemistry or any
physical science.
(b) Experience:
Minimum of three years of laboratory experience,
including at least one year of supervisory
experience.
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g. Extraction/Concentration Expert Qualifications
(1) Education:
Minimum of High school diploma and knowledge of general
chemistry.
(2) Experience:
Minimum of one year of experience.
h. 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.
(1) Education:
Minimum of Bachelor's degree in chemistry or any physical
science.
(2) Experience: Minimum of one year in each of the following
areas -
o GC/MS operation and maintenance for volatiles and
semivolatiles analyses.
o Mass spectral interpretation.
o Extraction.
o Pesticide analysis.
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.
a. Sample Receipt Area
Adequate, contamination-free, well ventilated work space
provided with chemical resistant bench top for receipt and
safe handling of EPA samples.
b. 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. NOTE: Volatiles.
semivolatiles. extracts, and standards must each be stored
separately.
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c. Sample Preparation Area
Adequate, contamination-free, well-ventilated work space
provided with:
(1) Benches with chemical resistant tops, exhaust hoods.
Note: Standards must be prepared in a glove box or
isolated area.
(2) Source of distilled or demineralized organic-free water.
(3) Analytical balance(s) located away from draft and rapid
change in temperature.
3. 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.
NOTE: The following primary and secondary instrument requirements
(a. and b. below) have been provided for both 100 samples/month
capacity contracts (Open Market) and 50 samples/month capacity
contracts (Small Business). The Contractor is responsible for the
requirements for their contract(s) (i.e., if you have an open
market (100 samples/month capacity) contract, you need to refer to
the open market requirements, and if you have a small business (50
samples/month capacity) contract, you need to refer to the small
business requirements).
a. Primary Instrument Requirements
(1) 100 Samples/Month Capacity (Open Market Contracts Only)
Fraction
Volatiles
Semivolatiles
(BNA)
Pesticides/PCBs
No. of
Ins trument ( s )
1
2
2
Type of
Instrument
GC/MS/DS with
purge and
trap device
GC/MS/DS
GC/EC with
dual column
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(2) 50 Samples/Month Capacity (Small Business Contracts Only)
Fraction
Volatiles
Semivolatiles
(BNA)
Pesticides/PCBs
No. of
Instrument (s)
1
1
1
Type of
Instrument
GC/MS/DS with
purge and
trap device
GC/MS/DS
GC/EC with
dual column
For contracts with three (3) bid lots or more:
o Minimum of three (3) GC/MS/DS and two (2) GC syterns
are required at time of bidding.
o An additional one (1) GC/MS/DS and one (1) GC system
are required as a back-up system
b. Secondary Instrument Requirements
(1) 100 Samples/Month Capacity (Open Market Contracts Only)
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
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 turnaround times.
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(2) 50 Samples/Month Capacity (Small Business Contracts Only)
The Contractor shall have one GC/MS/DS as a back-up
system, to be in place within 6 months from the date of
contract award.
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 turnaround times.
c. 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 Exhibits A and D
o GC Exhibit D
4. Data Handling and Packaging
The Contractor shall 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:
a. Provide space, tables and copy machines to meet the contract
requirements.
b. Designate personnel.
B. 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 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:
1. Technical Staff
Responsible for all technical efforts for the EPA contract.
2. 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 Project Officer and Regional Deputy Project
Officers.
A-18 2/88
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Custodian
Responsible for receiving the EPA samples (logging, handling and
storage) .
Quality Assurance Officer
Responsible for overseeing the quality assurance aspects of the
data and reporting directly to upper management.
Data Reporting and Delivery Officer
Responsible for all aspects of data deliverables: organization,
packaging, copying, and delivery.
A-19 2/88
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EXHIBIT B
REPORTING AND DELIVERABLES REQUIREMENTS
B-l 2/88
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EXHIBIT B
REPORTING AND DELIVERABLES REQUIREMENTS
B-l 2/88
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Table of Contents
SECTION I:
SECTION II:
SECTION III:
SECTION IV:
Page
Contract Reports/Deliverables Distribution B-3
Report Descriptions and Order of Data
Deliverables
B-6
Forms Instruction Guide B-23
Data Reporting Forms B-43
B-2
2/88
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SECTION I
CONTRACT REPORTS/DELIVERABLES DISTRIBUTION
The following table reiterates the Contract reporting and deliverables
requirements specified in the Contract Schedule 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 Project Officer will notify the Contractor in writing of such changes
when they occur.
Item
No.
Copies
Delivery
Schedule
Distribution
m
*A. Contract Start-Up
Plan
B. Updated SOPs
7 days after contract
receipt.
120 days after contract
receipt.
Item
No.
Copies
Delivery
Schedule
Distribution
(U) (5) (6)
**C. Sample Traffic
Reports
***D. Sample Data Summary
Package
***E. Sample Data Package
***F. Data in Computer- 1
Readable Form
3 days after
receipt of last
sample in Sample
Delivery Group
(SDG).****
35 days after
receipt of last
sample in SDG.
35 days after
receipt of last
sample in SDG.
35 days after
receipt of last
sample in SDG.
XXX
Distribution:
(1) Project Officer (PO)
(2) Contract Officer (CO)
(3) Sample Management Office (SMO)
(4) EMSL-LV
(5) Region-Client
(6) NEIC
B-3
2/88
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G.
Item
GC/MS Tapes
No.
Cooies
Lot
Delivery
Schedule (
Retain for 365 days
Distribution
3) (4) (5-) (6}
As Directed
H.
Extracts
Complete Case
File Purge
after data submis-
sion, or submit with-
in 7 days after
receipt of written
request by PO 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 PO or SMO.
1 Pkg Submit no less than 180
and no more than 240
days after data submission
or 7 days after receipt of
written request by PO
or SMO.
As Directed
* Contractor must be prepared to receive samples within 30 days of
contract award. NOTE: EPA can't guarantee exact adherence to start-up
plan that is agreed upon by the PO & Contractor, but will attempt to
meet it as close as possible.
** Also required in the Sample Data Package.
*** Concurrent delivery required. Delivery shall be made such that all
designated recipients receive the item on the same calendar day.
**** Sample Delivery Group (SDG) is a group of samples within a Case,
received over a period of 14 days or less and not exceeding 20 samples.
Data for all samples in the SDG are due concurrently. (See SOW Exhibit
A, paragraph J., for further description).
NOTE: As specified in the Contract Schedule (G.6 Government Furnished
Supplies and Materials), unless otherwise instructed by the CLP Sample
Management Office, "the Contractor shall dispose of unused sample
volume and used sample bottles/ containers no earlier than sixty (60)
days following submission of analytical data.
B-4
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Distribution Addresses:
(1) USEPA Analytical Operations Branch (WH 548A)
401 M Street, SW
Washington, DC 20460
ATTN: (Project Officer's Name)
(2) USEPA Office of Administration
Procurements & Contracts Management Division (PM-214)
401 M Street, SW
Washington, DC 20460
ATTN: (Contract Officer's Name)
(3) USEPA Contract Lab Program
Sample Management Office (SMO)
P. 0. Box 818
Alexandria, VA 22313
For overnight delivery service, use street address:
209 Madison Street, Suite 200
Alexandria, VA 22314
(4) USEPA Environmental Monitoring
Systems Laboratory (EMSL-LV)
P. 0. Box 15027
Las Vegas, NV 89114
ATTN: Data Audit Staff
For overnight delivery service, use street address:
944 E. Harmon, Executive Center
Las Vegas, NV 89109
ATTN: Data Audit Staff
(5) USEPA REGIONS:
The CLP Sample Management Office, acting on behalf of the 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.
(6) NEIC, Contractor Evidence Audit Team
12600 West Colfax, Suite 310
Lakewood, Colorado 80215
B-5 2/88
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SECTION II
REPORT DESCRIPTIONS AND ORDER OF DATA DELIVERABLES
The Contractor laboratory shall provide reports and other deliverables as
specified in the Contract Schedule (Performance/Delivery Schedule, Section
F.I). The required content and form of each deliverable is described in this
Exhibit.
All reports and documentation MUST BE:
o Legible,
o Clearly labeled and completed in accordance with instructions in this
Exhibit,
o Arranged in the order specified in this Section, and
o Paginated.
If submitted documentation does not conform to the above criteria, the
Contractor will be required to resubmit such documentation with
deficiency(ies) corrected, at no additional cost to the Agency.
Whenever the Contractor is required to submit or resubmit data as a result of
an on-site laboratory evaluation or through a PO/DPO action, the data must be
clearly marked as ADDITIONAL DATA and must be sent to all three contractual
data recipients (SMO, EMSL-LV, and Region). A cover letter shall be included
which describes what data is being delivered, to which EPA Case(s) it
pertains, and who requested the data.
Whenever the Contractor is required to submit or resubmit data as a result of
Contract Compliance Screening (CCS) review by SMO, the data must be sent to
all three contractual data recipients (SMO, EMSL/LV and Region), and in all
three instances must be accompanied by a color-coded COVER SHEET (Laboratory
Response To Results of Contract Compliance Screening) provided by SMO.
Section III of this Exhibit contains copies of the required data reporting
forms in Agency-specified formats, along with instructions to assist the
Contractor in accurately providing the Agency all required data. Data
elements with field parameters for reporting data in computer readable form
are contained in Exhibit H.
Descriptions of the requirements for each deliverable item cited in the
Contract Performance/Delivery Schedule (Contract Schedule, Section F.I) are
specified in parts A-G of this Section. Items submitted concurrently MUST BE
arranged in the order listed. Additionally, the components of each item MUST
BE arranged in the order presented in this Section when the item is
submitted.
Examples of specific data deliverables not included herein may be obtained by
submitting a written request to the EPA Project Officer, stating the
information requested, and signed by the Laboratory Manager.
B-6 2/88
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A. Contract Start-Up Plan
The Contractor shall submit a contract start-up plan for EPA approval as
specified in the Contract Performance/Delivery Schedule. The plan shall
set forth the Contractor's proposed schedule for receiving samples
starting with the 30th calendar day after award and ending with the date
the Contractor is capable of receiving the full monthly sample allotment
stipulated in the Contract. The Project Officer will review the
contract start-up plan within 7 days of submission and will notify the
Contractor of the plan's status.
NOTE: The Contractor shall be required to receive samples within 30
days of contract award. EPA can't guarantee exact adherence to start-up
plan that is agreed upon by the PO and Contractor, but will attempt to
meet it as close as possible.
B. Updated SOPs
The Contractor shall submit updated copies of all required Standard
Operating Procedures (SOPs) that were submitted with the prebid
Performance Evaluation sample results. The updated SOPs must address
any and all issues of laboratory performance and operation identified
through the review of the Performanc Evaluation sample data and the
evaluation of Bidder-Supplied Documentation.
The Contractor must supply SOPs for:
1. Sample receipt and logging.
2. Sample and extract storage.
3. Preventing sample contamination.
4. Security for laboratory and samples.
5. Traceability/Equivalency of standards.
6. Maintaining instrument records and logbooks.
7. Sample analysis and data control systems.
8. Glassware cleaning.
9. Technical and managerial review of laboratory operation and data
package preparation.
10. Internal review of contractually-required quality assurance and
quality control data for each individual data package.
11. Sample analysis, data handling and reporting.
12. Chain-of-custody.
13. Document control, including case file preparation.
Note: Such documentation is not required to conform specifically
(i.e.. in every detail) to this contract's requirements, but shall be
representative of standard laboratory operations, and shall give clear
evidence of the Contractor's ability to successfully fulfill all
contract requirements.
B-7 2/88
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C. 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 (TRs), all the samples on one multi-sample TR may not
necessarily be in the same SDG. In this instance, the laboratory must
make the appropriate number of photocopies of the TR, and submit one
copy with each SDG cover sheet.
D. Cample Data gupngrv 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 described under part E, Sample Data Package.
B-8 2/88
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The Sample Data Summary Package shall be ordered as follows and shall be
submitted separately (i.e., separated by rubber bands, clips or other
means) directly preceding the Sample Data Package. Sample data forms
shall be arranged in increasing EPA sample number order, considering
both letters and numbers. 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. Case Narrative
2. By fraction (VOA, SV, PEST) and by sample within each fraction -
tabulated target compound results (Form I) and tentatively
identified compounds (Form I, TIC)(VOA 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).
E. 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/PCBs). 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.
1. Case Narrative
This document shall be clearly labeled "Case Narrative" and shall
contain: laboratory name; Case number; sample numbers in the Sample
Delivery Group (SDG), differentiating between initial analyses and
re-analyses; SDG number; Contract number; and detailed documentation
of any quality control, sample, shipment and/or analytical problems
encountered in processing the samples reported in the data package.
Whenever data from sample re-analyses are submitted, the Contractor
shall state in the Case Narrative for each re-analysis, whether it
considers the re-analysis to be billable, and if so, why.
B-9 2/88
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The Contractor oust also include any problems encountered; both
technical and administrative, the corrective actions taken, and
resolution.
The Case 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 floppy 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 Case 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.
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) Surrogate Percent Recovery Summary (Form II VOA)
(2) Matrix Spike/Matrix Spike Duplicate Summary (Form III VOA)
(3) Method Blank Summary (Form IV VOA)
(If more than a single form is necessary, forms must be
arranged^in chronological order by date of analysis of the
blank.)
(4) GC/MS Tuning and Mass Calibration (Form V VOA)
BFB in chronological order; by instrument.
(5) Internal Standard Area Summary (Form VIII VOA)
In chronological order; by instrument.
B-10 2/88
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b. Sample Data
Sample data shall be arranged in packets with the Organic
Analysis Data Sheet (Form I VOA, including Form I VOA-TIC),
followed by the raw data for volatile samples. These sample
packets should then be placed in increasing EPA sample number
order, considering both letters and numbers in ordering
samples.
(1) TCL Results - Organic Analysis Data Sheet (Form I VOA).
Tabulated results (identification and quantitation) of the
specified target compounds (Exhibit C). The validation
and release of these results is authorized by a specific,
signed statement in the Case Narrative (reference C.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 Case Narrative.
On Form I, the appropriate concentration units shall be
entered. For example, ug/L for water samples or ug/Kg for
soil/sediment samples. No other units are acceptable.
NOTE: Report analytical results to one significant figure
if the value is less than 10; to two significant figures
above 10.
(2) Tentatively Identified Compounds (Form I VOA-TIC).
This form must be included even if no compounds are found.
If so, indicate this on the form by entering "0" in the
field for "Number found."
Form I VOA-TIC is the tabulated list of the highest
probable match for up to 10 of the nonsurrogate organic
compounds not listed in Exhibit C (TCL), including the CAS
(Chemical Abstracts Registry) number, tentative
identification and estimated concentration. For
estimating concentration, assume a response factor of 1,
and estimate the concentration by comparison of the
compound peak height or total area count to the peak
height or total area count of the nearest internal
standard free of interferences on the reconstructed ion
chromatogram. NOTE: The laboratory must be consistent
(i.e., use peak height for all comparisons or use total
area count for all comparisons).
(3) Reconstructed total ion chromatograms (RIC) for each
sample or sample extract.
RICs must be normalized to the largest nonsolvent
component, and must contain the following header
information:
B-ll 2/88
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o EPA sample number
o Date and time of analysis
o GC/MS instrument ID
o Lab file ID
Internal standard and surrogate spiking 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
Compound List (TCL) 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 TCL 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
(4) For each sample, by each compound identified:
(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 TCL 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-12 2/88
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Standards Data
(1) Initial Calibration Data (Form VI 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 the
initial (five point) calibration, labeled as in b.(3)
above. Spectra are not required.
(b) All initial calibration data 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.
(3) Internal Standard Area Summary (Form VIII VOA) - in order
by instrument, if more than one instrument used.
When more than one continuing calibration is performed,
forms must be in chronological order, by instrument.
Raw QC Data
(1) BFB (for each 12-hour period, for each GC/MS system
utilized)
(a) Bar graph spectrum, labeled as in b.(3) above.
(b) Mass listing, labeled as in b.(3) above.
(2) Blank Data - in chronological order. NOTE: This order is
different from that used for samples.
(a) Tabulated results (Form I VOA)
(b) Tentatively Identified Compounds (Form I VOA-TIC)
even if none found.
(c) Reconstructed ion chromatogram(s) and quantitation
report(s) or legible facsimile (GC/MS), labeled as in
b.(3) above.
B-13 2/88
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(d) TCL spectra with lab generated standard, labeled as
in b.(4) above. Data systems which are incapable of
dual display shall provide spectra in order:
o Raw TCL compound spectra
o Enhanced or background subtracted spectra
o Laboratory generated TCL 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 nonspiked TCL
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 nonspiked TCL
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.
Semivolatiles Data
a. QC Summary
(1) Surrogate Percent Recovery Summary (Form II SV)
(2) Matrix Spike/Matrix Spike Duplicate Summary (Form III SV)
(3) Method Blank Summary (Form IV SV)
(If more than a single form is necessary, forms must
be arranged in chronological order by date of
analysis of the blank.)
(4) GC/MS Tuning and Mass Calibration (Form V SV)
DFTPP in chronological order; by instrument.
B-14 2/88
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(5) Internal Standard Area 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 should then be placed in increasing EPA sample
number order, considering both letters and numbers in ordering
samples.
(1) TCL 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 Case Narrative (reference E.I).
In the event that the Laboratory Manager cannot validate
all data reported for each sample, the Laboratory Manager
shall provide a detailed description of the problems
associated with the sample in the Case Narrative.
On Form I, the appropriate concentration units shall be
entered. For example, ug/L for water samples or ug/Kg for
soil/sediment samples. No other units are acceptable.
NOTE: Report analytical results to one significant figure
if the value is less than 10; to two significant figures
above 10.
(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 nonsurrogate organic
compounds not listed in Exhibit C (TCL), including the CAS
(Chemical Abstracts Registry) number, tentative
identification and estimated concentration. For estimating
concentration, assume a response factor of 1, and estimate
the concentration by comparison of the compound peak
height or total area count to the peak height or total
area count of the nearest internal standard free of
interferences on the reconstructed ion chromatogram.
NOTE: The laboratory must be consistent (i.e., use peak
height for all comparisons or use total area count for all
comparisons).
B-15 2/88
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(3) Reconstructed total ion chromatograms (RIC) for each
sample, sample extract, standard, blank, and spiked
sample.
RICs must be normalized to the largest nonsolvent
component, and must contain the following header
information:
o EPA sample number
o Date and time of analysis
o GC/MS instrument ID
o Lab file ID
Internal standard and surrogate spiking 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
Compound List (TCL) 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 TCL 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
(4) For each sample, by each compound identified:
(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 TCL 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-16 2/88
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(b) Copies of mass spectra of nonsurrogate organic
compounds not listed in Exhibit C (TCL) (Tentatively
Identified Compounds) witb associated best-match
spectra (three best matches), labeled as in (4)(a)
above.
(c) GPC chromatograms (if GPC performed).
Standards Data
(1) Initial Calibration Data (Form VI SV-1, SV-2) - in order
by instrument, if more than one instrument used.
(a) BNA 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 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) BNA 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) Internal Standard Area Summary (Form VIII SV-1, SV-2) - in
order by instrument, if more than one instrument used.
When more than one continuing calibration is performed,
forms must be in chronological order by instrument.
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.
(2) Blank Data - in chronological order. NOTE: This order is
different from that used for samples.
B-17 2/88
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(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) TCL spectra with lab generated standard, labeled as
in b.(4) above. Data systems which are incapable of
dual display shall provide spectra in order:
o Raw TCL compound spectra
o Enhanced or background subtracted spectra
o Laboratory generated TCL 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 nonspiked TCL
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 nonspiked
TCL 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/PCB Data
a. QC Summary
(1) Surrogate Percent Recovery Summary (Form II PEST)
(2) Matrix Spike/Matrix Spike Duplicate Summary (Form III
PEST)
B-18 2/88
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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) TCL 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 Case Narrative (reference E.I).
In the event that the Laboratory Manager cannot validate
all data reported for each sample, the Laboratory Manager
shall provide a detailed description of the problems
associated with the sample in the Case Narrative.
On Form I PEST, the appropriate concentration units shall
be entered. For example, ug/L for water samples or ug/Kg
for soil/sediment samples. No other units are acceptable.
NOTE: Report analytical results to two significant figures
for all pesticide/PCB samples.
(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)
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
confirmation. Chromatograms to be labeled as in (2)
above.
B-19 2/88
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(4) GC Integration report or data system printout and
calibration plots (area vs. concentration) for 4,4'-DDT,
4,4'-ODD, 4,4'-DDE or toxaphene (where appropriate).
(5) Manual work sheets.
(6) UV traces from GPC (if available).
(7) If pesticide/PCBs are confirmed by GC/MS, the Contractor
shall submit copies of raw spectra and copies of
background-subtracted mass spectra of target compounds
listed in Exhibit C (TCL) that are identified in the
sample and corresponding background-subtracted TCL
standard mass spectra. Compound names must be clearly
marked on all spectra. For multicomponent pesticides/PCBs
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) Form VIII PEST - Pesticide Evaluation Standards Summary
(all GC columns)
(2) Form IX PEST - Pesticide/PCB Standards Summary (all GC
columns)
(3) Form X PEST - Pesticide/PCB Identification (only required
for positive results)
(4) Pesticide standard chromatograms and data system printouts
for all standards to include:
o Evaluation Standard Mix A
o Evaluation Standard Mix B
o Evaluation Standard Mix C
o Individual Standard Mix A
o Individual Standard Mix B
o All multiresponse pesticides/PCBs
o All quantitation standards
o A copy of the computer reproduction or strip chart
recorder output covering the 100 fold range
(a) All chromatograms are required to have the following:
o Label all chromatograms with the "EPA Sample
Number" for standards, i.e. EVALA, EVALB, etc.
(See Forms Instructions for details).
B-20 2/88
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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.
List total ng injected for each standard.
A printout of retention times and corresponding
peak areas must accompany each chromatogram.
Date and time of injection.
GC column identification (by stationary phase).
GC instrument identification.
d. Raw QC Data
(1) Blank Data - in chronological order. 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 nonspike TCL
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 nonspike TCL
compounds.
(b) Chromatogram(s) and data system printout(s) (GC),
labeled as in b.(2) above.
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
or a high density 1.2 M-byte diskette.
When submitted, floppy 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.
B-21 2/88
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The data shall be recorded in ASCII, text file format, and shall adhere
to the file, record and field specifications listed in Exhibit H, Data
Dictionary and Format for Data Deliverables in Computer-Readable Format.
If the Contractor wishes to use a reporting format other than the one
specified, equivalence must be demonstrated and approved by the Project
Officer prior to the award of the contract.
G. GC/MS Tapes
The Contractor must store all raw and processed GC/MS data on magnetic
tape, in appropriate instrument manufacturer's format. This tape must
include data for samples, blanks, matrix spikes, matrix spike
duplicates, initial calibrations, continuing calibrations, BFB and
DFTPP, as well as all laboratory-generated spectral libraries and
quantitation reports required to generate the data package. The
Contractor shall maintain a written reference logbook of tape files to
EPA sample number, calibration data, standards, blanks, matrix spikes,
and matrix spike duplicates. The logbook should include EPA sample
numbers and standard and blank ID's, identified by Case and Sample
Delivery Group.
The Contractor is required to retain the GC/MS tapes for 365 days after
data submission. During that time, the Contractor shall submit tapes
and associated logbook pages within seven days after receipt of a
written request from the Project Officer.
H. Extracts
The Contractor shall preserve sample extracts at 4sC (±2"C) in
bottles/vials with Teflon-lined septa. Extract bottles/vials shall be
labeled with EPA sample number, Case number and Sample Delivery Group
(SDG) number. A logbook of stored extracts shall be maintained, listing
EPA sample numbers and associated Case and SDG numbers.
The Contractor is required to retain extracts for 365 days following
data submission. During that time, the Contractor shall submit extracts
and associated logbook pages within seven days following receipt of a
written request from the Project Officer or the Sample Management
Office.
I. Complete Case File Purge
(Formerly, Document Control and Chain-of-Custody Package).
The complete case file purge includes all laboratory records received or
generated for a specific Case that have not been previously submitted to
EPA as a deliverable. These items include but are not limited to:
sample tags, custody records, sample tracking records, analysts logbook
pages, bench sheets, chromatographic charts, computer printouts, raw
data summaries, instrument logbook pages, correspondence, and the
document inventory (see Exhibit F).
B-22 2/88
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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/PCB), and in some instances specific to a given
matrix (water or soil) within each fraction. The contractor shall submit
only those forms pertaining to the fractions analyzed for a given sample or
samples. For instance, if a sample is scheduled for volatile analysis only,
provide only VOA forms. There are two pages relating to the semivolatile
fraction for Forms I, VI, VII, and VIII. Whenever semivolatiles are analyzed
and one of the above-named forms is required, both pages (SV-1 and SV-2) must
be submitted. These instructions are arranged in the following order:
A. General Information and Header Information
B. Organic Analysis Data Sheets (Form I, All Fractions)
C. Surrogate Recovery (Form II, All Fractions)
D. Matrix Spike/Matrix Spike Duplicate Recovery (Form III, All
Fractions)
E. Method Blank Summary (Form IV, All Fractions)
F. GC/MS Tuning and Mass Calibration (Form V VOA, Form V SV)
G. Initial Calibration Data (Form VI VOA, Form VI SV)
H. Continuing Calibration Data (Form VII VOA, Form VII SV)
I. Internal Standard Area Summary (Form VIII VOA, Form VIII SV)
J. Pesticide Evaluation Standards Summary (Form VIII Pest)
K. Pesticide/PCB Standards Summary (Form IX Pest)
L. Pesticide/PCB Identification (Form X Pest)
B-23 2/88
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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 TCL 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 Project Officer. The names of the various fields
and compounds (i.e., "Lab Code," "Chloromethane") must appear as they do
on the forms in the contract, including the options specified in the
form (i.e., "Matrix: (soil/water)" must appear, not just "Matrix").
For items appearing on the uncompleted forms (Section IV), the use of
uppercase and lowercase letters is optional.
Alphabetic entries made onto the forms by the Contractor shall be in ALL
UPPERCASE letters (i.e., "LOW", not "Low" or "low"). If an entry does
not fill the entire blank space provided on the form, null characters
shall be used to remove the remaining underscores that comprise the
blank line. (See Exhibit H for more detailed instructions.) However,
do not remove the underscores or vertical bar characters that delineate
"boxes" on the forms. The only exception would be those underscores at
the bottom of a "box" that are intended as a data entry line (for
instance, see 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. This information must be entered on every form and
must match on every form.
The "Lab Name" shall be the name chosen by the Contractor to identify
the laboratory. It may not exceed 25 characters.
B-24 2/88
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The "Lab Code" is an alphabetical abbreviation of up to 6 letters,
assigned by EPA, to identify the laboratory and aid in data processing.
This lab code shall be assigned by EPA at the time a contract is
awarded, and shall not be modified by the Contractor, except at the
direction of EPA.
The "Case No." is the EPA-assigned Case number (up to 5 digits)
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 D'elivery
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 "EPA Sample No." is entered into the triple-spaced box in
the upper righthand corner of Form I 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 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.
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-analyzed sample
XXXXXDL - sample analyzed at a secondary dilution
Form VIII Pest requires that all samples analyzed in a given 72-hour
analytical sequence be specified, regardless of whether or not they are
part of the SDG being reported. Therefore, use "ZZZZZ" as the EPA
B-25 2/88
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Sample No. for any sample analyses 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/PCB blanks shall be identified as PBLK##.
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, VBLKAl, VBLKB2, VBLK10,
VBLKAB, etc.
4. 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., 20, 50, 100, 150, and 200) or the amount
injected in ng for semivolatile standards (i.e., 20,
50, 80, 120, and 160).
As for the blank identifiers, these designations will have to be
concatenated with other information to uniquely identify each
standard.
5. Pesticide/PCB standards shall be identified as specified in the
instructions for Form VIII.
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 "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.
B-26 2/88
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"Lab Sample ID" is an optional laboratory-generated internal
identifier. Up to 12 alpha-numeric characters may be reported here.
"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.
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 them
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." Only number pages within a fraction-specific
and matrix-specific form.
For rounding off numbers to the appropriate level of precision,
observe the following common rules. If the figure following those
to be retained is less than 5, drop it (round down). If the figure
is greater than 5, drop it and increase the last digit to be
retained by 1 (round up). If the figure following the last digit to
be retained equals 5, round up if the digit to be retained is odd,
and round down if that digit is even.
B. Organic Analysis Data Sheet (Form I)
1. Form I VOA, Form I SV-1, Form I SV-2, Form I Pest
This form is used for tabulating and reporting sample analysis
results for Target Compound List (TCL) compounds. If all fractions
are not requested to be analyzed, only the pages specifically
required must be submitted. If VOA analysis only is requested, Form
I VOA and Form I VOA TIC must be submitted. If the pesticide/PCB
analysis is the only analysis requested, only Form I Pest must be
submitted for that sample.
Complete the header information on each page of Form I required,
according to the instructions in part A. and as follows:
For volatiles, for "% moisture not dec.", enter the nondecanted
percent moisture. For semivolatiles and pesticides/PCB, enter
values for both nondecanted percent moisture and decanted percent
moisture, in the appropriate fields. Report percent moisture
(decanted or not decanted) to the nearest whole percentage point
(i.e., 5%, not 5.3%). If a decanted percent moisture is not
determined, because the sample has no standing water over it, leave
"% moisture dec." blank. Leave these fields blank for Form I for
method blanks.
B-27 2/88
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For volatiles, enter the type of GC column used in "Column:
(pack/cap)." Enter "PACK" for packed columns, and "CAP" for
capillary columns, whether megabore or narrow bore.
For semivolatiles and pesticides/PCBs, enter the method of
extraction as "SEPF" for separatory funnel, and "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.
For soil samples only, enter pH for semivolatile and
pesticides/PCBs, reported to 0.1 pH units.
"Date Received" is the date of sample receipt at the laboratory, as
noted on the Traffic Report (i.e., the VTSR). It should be entered
as MM/DD/YY.
"Date Extracted" and "Date Analyzed" should be entered in a similar
fashion. If continuous liquid-liquid extraction procedures are
used, enter the date on which the procedure was started for "Date
Extracted". If separatory funnel or sonication procedures are used,
enter the date on which the procedure was completed. For
pesticide/PCB 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.
If a sample has been diluted for analysis, enter the "Dilution
Factor" as a single number, such as 100 for a 1 to 100 dilution of
the sample. Enter 0.1 for a concentration of 10 to 1. If a sample
was not diluted, enter 1.
For positively identified TCL 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 above 10.
Report all pesticides/PCB 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 Case
Narrative.
B-28 2/88
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For reporting results to the USEPA, the following contract specific
qualifiers are to be used. The seven qualifiers defined below are
not subject to modification by the laboratory. Up to five
qualifiers may be reported on Form I for each compound.
The seven EPA-defined qualifiers to be used are as follows:
U - Indicates compound was analyzed for but not detected. The
sample quantitation limit must be corrected for dilution and
for percent moisture. For example, 10 U for phenol in water if
the sample final volume is the protocol-specified final volume.
If a 1 to 10 dilution of extract is necessary, the reported
limit is 100 U. For a soil sample, the value must also be
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
at 24% moisture, D - 100-24 - 0.76
100
(330 U> x 10 - 4300 U rounded to the appropriate number of
.76 significant figures
For soil samples subjected to GPC clean-up procedures, the CRQL
is also multiplied by 2, to account for the fact that only half
of the extract is recovered.
J - Indicates an estimated value. This flag is used either when
estimating a concentration for tentatively identified compounds
where a 1:1 response is assumed, or when the mass spectral data
indicate the presence of a compound that meets the
identification criteria but the result is less than the sample
quantitation limit but greater than zero. For example, if the
sample quantitation limit is 10 ug/L, but a concentration of 3
ug/L is calculated, report it as 3J. The sample quantitation
limit must be adjusted for both dilution and percent moisture
as discussed for the U flag, so that if a sample with 24%
moisture and a 1 to 10 dilution factor has a calculated
concentration of 300 ug/L and a sample quantitation limit of
430 ug/kg, report the concentration as 300J on Form I.
C - This flag applies to pesticide results where the identification
has been confirmed by GC/MS. Single component pesticides >10
ng/ul in the final extract shall be confirmed by GC/MS.
B-29 2/88
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B - This flag is used when the analyte is found in the associated
blank as well as in the sample. It indicates possible/probable
blank contamination and warns the data user to take appropriate
action. This flag must be used for a TIC as well as for a
positively identified TCL compound.
E - This flag identifies compounds whose concentrations exceed the
calibration range of the GC/MS instrument for that specific
analysis. This flag will not apply to pesticides/PCBs analyzed
by GC/EC methods. If one or more compounds have a response
greater than full scale, 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 Forms I.
The Form I for the diluted sample shall have the "DL" suffix
appended to the sample number. NOTE: For total xylenes, where
three isomers are quantified as two peaks, the calibration
range of each peak should be considered separately, e.g., a
diluted analysis is not required for total xylenes unless the
concentration of either peak separately exceeds 200 ug/L.
D - This flag identifies all compounds identified in an analysis at
a secondary dilution factor. If a sample or extract is
re-analyzed at a higher dilution factor, as in the "E" flag
above, the "DL" suffix is appended to the sample number on the
Form I for the diluted sample, and all concentration values
reported on that Form I are flagged with the "D" flag.
A - This flag indicates that a TIC is a suspected
aldol-condensation product.
X - Other specific flags may be required to properly define the
results. If used, they must be fully described and such
description attached to the Sample Data Summary Package and the
Case Narrative. Begin by using "X". If more than one flag is
required, use "Y" and "Z", as needed. If more than five
qualifiers are required for a sample result, use the "X" flag
to combine several flags, as needed. For instance, the "X"
flag might combine the "A", "B", and "D" flags for some sample.
The combination of flags "BU" or"UB" is expressly prohibited. Blank
contaminants are flagged "B" only when they are also detected in the
sample.
If analyses at two different dilution factors are required (see
Exhibit D), follow the data reporting instructions given in Exhibit
D and with the "D" and "E" flags above.
B-30 2/88
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2. Form I VOA-TIC and Form I SV-TIC
Fill in all header information as above.
Report Tentatively Identified Compounds (TIC) 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 unknown.
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-TCL semivolatile compounds to be searched.
C. Surrogate Recovery (Form II)
Form II is used to report the recoveries of the surrogate compounds
added to each sample, blank, matrix spike, and matrix spike duplicate.
Form II is matrix-specific as well as fraction-specific, so that
surrogate recoveries for volatile water samples are reported on a
different version of Form II than volatile soil sample surrogate
recoveries.
Complete the header information and enter EPA Sample Numbers as
described in part A. For soil samples only, specify the "level" as
"LOW" or "MED", as on Form I. go not mix low and medium level samples
on one form. Complete 'one for each level. For each surrogate, report
the percent recovery 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.
B-31 2/88
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If no surrogates were outside the limits, enter "0".
If the surrogates are diluted out in any analysis, enter the calculated
recovery or "0" (zero) if the surrogate is not detected, and flag the
surrogate recoveries with a "D" in the column under the "#" symbol. Do
not include results flagged "D" in the total number of recoveries for
each sample outside the QC limits.
The pesticide surrogate recovery limits are only advisory, but the
Contractor must flag those recoveries outside the advisory QC limits or
diluted out, nonetheless.
Number all pages as described in part A.
Matrix Spike/Matrix Spike Duplicate Recovery (Form III)
This form is used to report the results of the analyses of a matrix
spike and matrix spike duplicate. As with the surrogate recovery form
(II), the form is matrix-specific within each fraction.
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 soil samples, specify "level" as "LOW" or "MED", as on Form I.
Cases 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 100 ug of spike are added to 1 g of soil, the resulting
concentration is 100,000 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 E, and enter under "MS % REC". Flag all
percent recoveries outside the QC limits with an asterisk (*). The
asterisk must be placed in the last space of the percent recovery
column, under the "#" symbol.
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". 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.
B-32 2/88
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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.
E. Method Blank Summary (Form IV)
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.
For volatile and 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 semivolatile and pesticide/PCB blanks, enter the method of
extraction as "SEPF" for separately funnel, or "SONG" for sonication, or
"CONT" for continuous liquid-liquid extraction. For semivolatile and
pesticide/PCB method blanks, enter the date of extraction of the blank.
Pesticide/PCB 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 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
Form X. Otherwise (1) shall be the first analysis, and (2) the second.
Identify both GC columns by stationary phase under "GC Column ID". For
mixed phase columns, do not enter "mixed". If the stationary phase
identifier contains a manufacturer's identifier, such as "SP" or "DB",
these characters may be deleted in order to fit the identifier into the
10-character field.
For Pesticide/PCB blanks, enter "Matrix" and "Level" in a similar
fashion as for the other fractions. All water samples are "LOW". Enter
"Lab File ID" only if GC/MS confirmation was required. 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. For semivolatiles and pesticides/PCBs, enter the date
of analysis of each sample. For pesticide/PCBs, if only one analysis is
required (i.e., no pesticides/PCBs to be confirmed), leave blank the
fields for the second analysis.
Number all pages as described in part A.
F. GC/MS Tuning and Mass Calibration (Form V)
This form is used to report the results of GC/MS 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 GC/MS tune.
B-33 2/88
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Complete the header information as in part A. Enter the "Lab File ID"
for the injection containing the GC/MS tuning compound (BFB for
volatiles, DFTPP for semivolatiles). Enter the "Instrument ID". Enter
the date and time of injection of the tuning compound. Enter time as
military time. For volatiles, enter the matrix and level, as there are
separate calibrations for water samples, low soil samples, and medium
samples (see Exhibit D). For volatiles, also enter the type of GC
column used as "PACK" or "CAP", under "Column."
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.
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 tune 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 tune expires twelve hours from the time of injection of the
tuning compound (BFB or DFTPP) listed at the top of the form. In order
to meet the tuning requirements, a sample, standard, blank, matrix
spike, or matrix spike duplicate must be injected within twelve hours of
the injection of the tuning compound.
Number all pages as described in part A.
G. Initial Calibration Data (Form VI)
After a GC/MS system has undergone an initial five-point calibration at
the specific concentration levels described in Exhibit E, and after all
initial calibration criteria have been met, the laboratory must complete
and submit a Form VI for each volatile or semivolatile TCL 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.
For Semivolatiles, nine compounds: Benzoic Acid, 2,4-Dinitrophenol,
2,4,5-Trichlorophenol, 2-Nitroaniline, 3-Nitroaniline, 4-Nitroaniline,
4-Nitrophenol, 4,6-Dinito-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-34 2/88
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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. For volatiles, enter matrix, level, and column, 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 TCL and surrogate compounds. The laboratory must report the %RSD
for all compounds. All CCC compounds must have a %RSD of less than or
equal to 30.0 percent. All VOA SPCC compounds must have a minimum
average relative response factor (RRF) of 0.300 (0.250 for Bromoform).
All Semivolatile (BNA) SPCC compounds must have a. minimum average
relative response factor (RRF) of 0.050.
x 100
x
where:
%RSD - Relative Standard Deviation
SD - Standard Deviation of initial 5 response factors (per
compound)
where: SD -
V 1-1 —
N-l
x - mean of initial 5 response factors (per compound)
H. Continuing Calibration Data (Form VII)
The Continuing Calibration Data Form is used to verify the calibration
of the GC/MS system by the analysis of specific calibration standards.
A Continuing Calibration Data Form is required for each twelve (12) hour
time period for both volatile and semivolatile TCL compound analyses.
The Contractor laboratory must analyze calibration standards and meet
all criteria outlined in Exhibit E. After meeting specific criteria for
both SPCC and CCC compounds, a Continuing Calibration Data Form must be
completed and submitted.
Complete all header information as in part A. Enter instrument ID, date
and time of continuing calibration, the Lab File ID of the continuing
calibration standard, and date of initial calibration (give inclusive
dates if initial calibration is performed over more than one date). For
volatiles, enter matrix, level, and column, as on Forms V and VI. Using
the appropriate Initial Calibration (Volatile or Semivolatile) fill in
the average relative response factor (RRF) for each TCL compound.
B-35 2/88
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Report the relative response factor (RRF50) from the continuing
calibration standard analysis. Calculate the Percent Difference (%D)
for all compounds. For CCC compounds, ensure that the %D is less than
or equal to 25.0 percent. After this criterion has been met, report the
Percent Difference for all TCL and surrogate compounds.
RRFj - RRFC
% Difference - x 100
where,
RRFj
RRFj - average relative response factor from initial calibration.
RRFC - relative response factor from continuing calibration
standard.
All semivolatile standards are analyzed at 50 total ng.
I. Internal Standard Area Summary (Form VIII VOA and SV)
This form is used to summarize the peak areas 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 tune as an initial calibration.
Complete the header information as in part 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
GC/MS tune 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 matrix, level, and column, as on Forms 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 under the appropriate column in the row labeled "12 HOUR STD". For
each internal standard, calculate the upper limit 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 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.
B-36 2/88
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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.
Number all pages as described in part A.
J. Pesticide Evaluation Standards Summary (Form VIII Pest)
This form is used to report the seventy-two (72) hour analytical
sequence for pesticide analysis.
The laboratory shall complete all the header information as in Part A.
Enter dates of analyses, GC column ID and Instrument ID. Identify GC
Column by stationary phase. For mixed phase columns, do not enter
"mixed". If the stationary phase identifier contains a manufacturer's
identifier, such as "SP" or "DB", these characters may be deleted in
order to fit the identifier into the 10-character field.
Evaluation Standard Mix A, B, and C must be analyzed at the initiation
of every 72 hour sequence to check the linearity of the GC system.
Calculate and report the Calibration Factor (total peak area /amount
injected in nanograms) for each of the three pesticides and the
surrogate (Aldrin, Endrin, 4,4'-DDT and Dibutylchlorendate) at each
concentration level (see Exhibit D). Calculate and report the percent
relative standard deviation (%RSD) for each of the four compounds (Eq.
1.1). The RSD must be less than 10.0 percent for Aldrin, Endrin, and
Dibutylchlorendate. The 10% RSD criteria pertain only to the column
being used for quantitation, however, to determine that no
pesticides/PCBs are present is a form of quantitation.
If the %RSD for 4,4'-DDT exceeds 10.0 percent, plot a standard curve and
determine the ng for each sample from that curve.
en
%RSD - —— x 100 Eq. 1.1
where: SD
V1"1 -
N-l
x - mean of initial three Calibration factors (per compound)
Evaluation Standard Mix B must be analyzed near the beginning of the
analytical sequence, after the first five samples, and then every ten
samples thereafter during a 72-hour period (see Exhibits D and E).
The term peak height may be substituted for the term peak area.
B-37 2/88
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Calculate and report the percent breakdown for 4,4'-DDT and/or Endrin
for the mixed phase GC column using Equations 1.2 and 1.3. (See Exhibit
E). Enter the Date Analyzed and Time Analyzed for each analysis of the
Evaluation Standard Mix B.
Calculate the percent breakdown for Endrin and/or 4,4'-DDT on the OV-1
or equivalent GC column using Equations 1.2 and 1.3. The combined
percent breakdown must not exceed 20.0 percent for Endrin and 4,4'-DDT.
% breakdown Total DDT degradation peak area (DDE + DDD)
for 4,4'-DDT x 100 Eq. 1.2
Total DDT peak area3 (DDT + DDE + DDD)
Total Endrin degradation peak areas
% breakdown (Endrin Aldehyde + Endrin Ketone)
for Endrin - X 100 Eq. 1.3
Total Endrin Peak Area3(Endrin +
Endrin Aldehyde + Endrin Ketone)
Enter the values for the breakdown of Endrin and 4,4'-DDT in their
respective columns.
If Endrin cannot be separated from 4,4'-DDT on the OV-1 or equivalent GC
column, calculate a combined percent breakdown for Endrin/4,4'-DDT using
Equation 1.4. The combined degradation must not exceed 20.0 percent.
Leave the endrin and 4,4'-DDT columns blank if they cannot be separated,
and report only the combined breakdown.
Total Endrin/DDT degradation peak area3
Combined (DDD, DDE, Endrin Aldehyde, Endrin Ketone)
% breakdown - — X 100 Eq. 1.4
Total Endrin/DDT degradation peak area
(Endrin, Endrin Aldehyde, Endrin Ketone,
DDD, DDE, DDT)
Complete the header information on the second page of Form VIII Pest as
on the first page.
For each sample, standard, matrix spike, matrix spike duplicate, and
blank, enter the EPA sample number, lab sample ID, date and time of
analysis. Each sample analyzed as part of the 72-hour analytical
sequence must be reported on the second page of Form VIII PEST even if
it is not associated with the SDG, in order to determine if the proper
sequence of samples and standards was followed. However, the laboratory
may use the EPA Sample No. of "ZZZZZ" to distinguish all samples that
are not part of the SDG being reported.
The term peak height may be substituted for the term peak area.
B-38 2/88
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For pesticide/PCB standards, the following scheme shall be used to enter
"EPA Sample Number".
Name EPA Sample Number
Evaluation Mix A EVALA
Evaluation Mix B EVALB
Evaluation Mix C EVALC
Individual Mix A INDA
Individual Mix B INDB
Toxaphene TOXAPH
Aroclor 1016 AR1016
Aroclor 1221 AR1221
Aroclor 1232 AR1232
Aroclor 1242 AR1242
Aroclor 1248 AR1248
Aroclor 1254 AR1254
Aroclor 1260 AR1260
If Individual Mix A and Individual Mix B are combined into one mixture
(see Exhibit D), the EPA Sample Number shall be entered as INDAB.
Similarly, the permitted mixture of Aroclor 1016 and Aroclor 1260 shall
be entered as AR1660.
Every standard, sample, matrix spike, matrix spike duplicate, and blank
must contain the surrogate dibutylchlorendate (DBC) at the specified
level for both water or soil/sediment samples. The retention time shift
for Dibutylchlorendate on packed columns must not exceed 2.0 percent
(0.3 percent for capillary columns) difference (%D) between the
initial standard (Evaluation Standard Mix A) and any blank, standard,
sample, matrix spike, or matrix spike duplicate analyzed during the
72-hour time period. Calculate and report the percent difference (%D)
for all samples, matrix spike, matrix spike duplicate, standards, and
blanks, according to Eq. 1.5.
RTi - RTS
% Difference - x 100 Eq 1.5
RT^
where,
RTj - absolute retention time of dibutylchlorendate in the initial
standard (Evaluation Mixture A).
RTg - absolute retention time of dibutylchlorendate in the sample,
matrix spike, matrix spike duplicate, blank, or any standard
analyzed after Evaluation Mixture A.
Enter the retention time shift for DBC in the "%Dn column. Flag all
those values outside the QC limits by entering an asterisk (*) in the
last column, under the "*". If the retention time shift cannot be
calculated due to interfering peaks, leave the %D column blank, flag the
value with an asterisk, and document the problem in the Case Narrative.
Number this page as described in Part A.
B-39 2/88
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Form VIII PEST is required for each seventy-two (72) hour period, for
each GC system and for each GC column used to analyze TCL
Pesticide/PCBs.
K. Pesticide/PCB Standards Summary (Form IX)
This form is used to monitor variations in the Calibration Factor and
retention time for each pesticide/PCB standard during each seventy-two
(72) hour period.
The laboratory shall complete the header information as in Part A.
Enter dates of analyses, GC column ID and instrument 10. Identify GC
column identification must be by stationary phase. For mixed phase
columns, do not enter "mixed." If the stationary phase identifier
contains a manufacturer's identifier, such as "SP" or "DB", these
characters may be deleted in order to fit the identifier into the 10-
character field.
Individual Standard Mix A and B must be analyzed at or near the
beginning of a seventy-two (72) hour sequence (before the analysis of
any samples). Individual Standard Mix A and B must also be analyzed
periodically during sample analysis (at the intervals specified in
Exhibits D and E), and at the end of the seventy-two (72) hour sequence.
Form IX is designed to compare the first analysis of each of the
standards to each subsequent analysis. Therefore, a copy of Form IX
must be completed for each analysis of Individual Standard Mix A and B,
and each multiresponse standard after the analysis of samples has begun.
For each copy of Form IX for a given analytical sequence, the data
entered in the lefthand column will be identical. The header over the
lefthand column contains the inclusive dates and times of analysis of
the standards reported on the left side of Form IX. Considering the
first analysis of Individual Standard Mix A, Individual Mix B, and all
the multiresponse pesticides and PCBs, enter the first and last dates
and times of analysis of these standards. If Aroclors 1221 and 1232 are
not analyzed as part of the sequence being reported, do not include the
dates and times of their analyses, but do include the data on Form IX.
Report the retention time of each compound in the left hand column
labeled "RT". Retention times must be reported in minutes and decimal
minutes (i.e., 1.99 minutes), not in seconds, or minutes:seconds.
Calculate the retention time window for each compound, according to the
instructions in Exhibit E, Section III, Part 4. Report the retention
time window for each compound as a range of two values, i.e., from 1.48
to 1.54. Enter the lower value of the range in the column under "RT
WINDOW" labeled "FROM". Enter the upper value of the range in the
column under "TO". Do not separate the two values with a hyphen, and do
not enter the retention time window as a plus/minus value such as ±0.03.
NOTE: By definition, the center of the retention time window must be the
retention time listed immediately to the left of the retention time
window.
Calculate the calibration factor for each compound according to Equation
1.6, and the value report under the left hand column labeled
"CALIBRATION FACTOR".
B-40 2/88
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For each subsequent analysis of an Individual Standard Mix A or B, or a
multiresponse compound, complete the right hand spaces for date and time
of analysis and the EPA Sample No. for the standard (see Section J) , and
the columns labeled "RT" and "CALIBRATION FACTOR" with the results from
that analysis. NOTE: While the lefthand side of Form IX will contain
retention times, retention time windows, and calibration factors for all
the compounds, the righthand side will contain data from the analysis of
only some of the compounds .
Total peak area of a Standard
Calibration Factor - - Eq 1.6
Total mass injected (ng)
Calculate and report the percent difference in the Calibration Factor
for each pesticide/PCB using Equation 1.7.
- Ab2|
Percent Difference (%D) - - x 100 Eq. 1.7
Abl
where,
Abi - Calibration Factor from the initial standard for the 72-hour
period
Ab2 - Calibration Factor from each subsequent standard
The absolute percent difference between the individual Calibration
Factors for each compound in the pesticide standard may vary no more
than 15.0 percent for a quantitation run, or more than 20.0 percent for
a confirmation run. Primary runs must meet the criteria required for
quantitation if no other analyses are performed.
If the results of analyses of compounds in the Individual Standard Mix
are to be used for quantifying pesticide/PCB concentrations in the
samples preceding the analysis on the right hand side of the form, then
enter "Y" for yes, in the column labeled "QNT Y/N" for each compound
quantified. If the results are not used for quantitation of a
particular compound, enter "N", for no. Determining that no compounds
are present above the CRQL is a form of quantitation.
For each subsequent analysis of an Individual Standard Mix A or B, or
multiresponse compound, complete the right hand side of a copy of Form
IX, with the results of the initial analyses of all the compounds as the
data in the left hand side.
For multicomponent analytes, the single largest peak characteristic of
the compound must be used. A characteristic peak will not exist for
similar compounds such as Aroclor 1016 and Aroclor 1242. In these cases
utilization of a common peak is acceptable.
The term peak height may be substituted for the term peak area.
B-41 2/88
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Regardless of which standards are reported on subsequent pages of Form
IX, number all pages sequentially as described in Part A. As Individual
Mix A and Mix B must be analyzed at the end of an analytical sequence,
there will always be at least two pages of Form IX, 1 of 2, and 2 of 2,
except where Mixes A & B have been combined for capillary column
analysis.
L. Pesticide/PCB Identification (Form X)
This form summarizes the tentative and confirmed identity of all TCL
pesticides/PCBs 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. One copy of Form X is required for each sample or
blank in which TCL pesticides or PCBs 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 Part A. Enter the GC Column ID
(by stationary phase) for each of the two columns, one as GC Column (1),
the other as (2). For mixed phase columns, do not enter "mixed". If
the stationary phase identifier contains a manufacturer's identifier,
such as "SP" or "DB", these characters may be deleted in order to fit
the identifier into the 10-character field. Enter the Instrument ID
associated with each GC column directly below. Enter Lab File ID only
if the compounds were confirmed by GC/MS.
For each TCL pesticide or PCB detected, enter the name of the compound
as it appears abbreviated on Form IX (limited to 14 characters) under
"PESTICIDE/PCB". Use the abbreviations of compound names given on Form
IX. 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 of the appropriate
standard. These data must correspond with those on Form IX, and are
entered in a similar manner. The lower value is entered under the
"FROM" column, the upper value under the "TO" column. Do not use a
hyphen.
Under "Quant? (Y/N)" enter "Y" for the GC column (1 or 2) used for
quantitation, and "N" for the other column, for each compound. Do not
leave this field blank for either GC column.
Under "GC/MS? (Y/N)" enter "Y" for both GC columns if the compound was
confirmed by GC/MS. Enter "N" for both GC columns if the compound was
not confirmed by GC/MS.
If more Pesticide/PCB TCL 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 Part A.
B-42 2/88
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SECTION IV
DATA REPORTING FORMS
-------
1A
VOLATILE ORGANICS ANALYSIS DATA SHEET
EPA SAMPLE NO.
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Matrix: (soil/water)
Sample wt/vol:
Level: (low/med)
% Moisture: not dec.
Column: (pack/cap)
CAS NO.
.(g/mL).
Lab Sample ID:
Lab File ID:
Date Received:
Date Analyzed:
COMPOUND
Dilution Factor:
CONCENTRATION UNITS:
(ug/L or ug/Kg)
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
108-05-4 Vinyl Acetate
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
71-43-2 Benzene
10061-02-6 trans-1,3-Dichloropropene
75-25-2 Bromoform
108-10-1 4-Methyl-2-Pentanone
591-78-6 2-Hexanone
127-18-4 Tetrachloroethene
79-34-5 1,1,2,2-Tetrachloroethane
108-88-3 Toluene
108-90-7 Chlorobenzene
100-41-4 Ethylbenzene
100-42-5 Styrene
1330-20-7 Xylene (total)
FORM I VOA
1/87 Rev
-------
IB
SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET
EPA SAMPLE NO
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Matrix: (soil/water)
Sample wt/vol:
Level: (low/med)
% Moisture: not dec.
,(g/mL).
dec.
Extraction: (SepF/Cont/Sonc)
GPC Cleanup: (Y/N) pH:.
Lab Sample ID:
Lab File ID:
Date Received:
Date Extracted:
Date Analyzed:
CAS NO.
COMPOUND
Dilution Factor:
CONCENTRATION UNITS:
(ug/L or ug/Kg)
KA T _"7"5_1 ____
i no_Kn _£____
oc:_c;n_i _____
i no _c n_l ___
1 O£_/1 /t_R___
/;o i _£ /t _ "?____
QQ OR 1____
"7 Q t> O H
/ O D ^ X
O Q *7 ^ ^
O O / O ^
i r\R /;T_Q _
>- r o c f\
O O O D U
111 _O1 — .1 ____
1 "5 A Q"}_O____
1 "5 n — O O — 1 ____
Q 1 O A *)
y j. & u <3
i n^— 4"7— fl— — — —
Q1 —C;*? _<;_____
"7"7_^ *?_/—____
OQ_AC *)_____
^ *^ i i ^ *)
f' f\ f f\ r\ *\
O U O 4L \J £•
2_vr«+-Vn»i v\KAvt/<^i
4_MA^Viir1 »%Vi/!k«^v1
VT VT «^W»«««B^^ «44 .• ^ f
•• • ^ . «
«h j — .• 4^1»«*T»»l»«»«» T
M ,• •«. • ^-^ T *» *«• «^»*l» *^«« T
f_j ..» WT .««».WaA-«kjd« MA
1
FORM I SV-1
1/87 Re-
-------
1C
SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET
EPA SAMPLE NO.
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Matrix: (soil/water)
Sample wt/vol: (g/mL)
Level: (low/med)
% Moisture: not dec. dec.
Extraction: (SepF/Cont/Sonc)
GPC Cleanup: (Y/N) pH:
Lab Sample ID:
Lab File ID:
Date Received:
Date Extracted:
Date Analyzed:
CAS NO.
COMPOUND
Dilution Factor:
CONCENTRATION UNITS:
(ug/L or ug/Kg)
99-09-2 3-Nitroaniline
83-32 -9 Acenaphthene
51-28-5 2,4-Dinitrophenol
100-02-7 4-Nitrophenol
132-64-9 Dibenzofuran
121-14-2 2,4-Dinitrotoluene
84-66-2 Diethylphthalate
7005-72-3 4-Chlorophenyl-phenylether_
86-73-7 Fluorene "_
100-01-6 4-Nitroaniline
534-52-1 4,6-Dinitro-2-methylphenol
86-30-6 N-Nitrosodiphenylamine (1) ~
101-55-3 4-Bromophenyl-phenylether_J
118-74-1 Hexachlorobenzene
87-86-5 Pentachlorophenol
85-01-8 Phenanthrene
120-12-7 Anthracene
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
1/87 Rev
-------
ID
PESTICIDE ORGANICS ANALYSIS DATA SHEET
EPA SAMPLE NO,
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Matrix: (soil/water)
Sample wt/vol:
Level: (low/med)
% Moisture: not dec.
.(g/mL).
dec.
Extraction: (SepF/Cont/Sonc)
GPC Cleanup: (Y/N) pH:
Lab Sample ID:
Lab File ID:
Date Received:
Date Extracted:
Date Analyzed:
CAS NO.
COMPOUND
Dilution Factor:
CONCENTRATION UNITS:
(ug/L or ug/Kg)
Q
319-84-6 alpha-BHC
319-85-7 beta-BHC
319-86-8 delta-BHC
58-89-9 gamma-BHC (Lindane)
76-44-8 Heptachlor '
309-00-2 Aldrin
1024-57-3 Heptachlor epoxide_
959-98-8 Endosulfan I
60-57-1 Dieldrin
72-55-9 4 , 4 ' -DDE
72-20-8 Endrin
33213-65-9 Endosulfan II
72-54-8 4,4'-DDD
1031-07-8 Endosulfan sulfate_
50-29-3 4,4 • -DDT
72-43-5 Methoxychlor
53494-70-5 Endrin ketone
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
1/87 Rev
-------
Lab Name:
Lab Code:
IE
VOLATILE ORGANICS ANALYSIS DATA SHEET
TENTATIVELY IDENTIFIED COMPOUNDS
Contract:
SAS No.:
EPA SAMPLE NO.
"I
Case No.:
SDG No.:
Matrix: (soil/water)
Sample wt/vol:
Level: (low/med)
% Moisture: not dec.
Column: (pack/cap)
Number TICs found:
(g/mL)
Lab Sample ID:
Lab File ID:
Date .Received:
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 VOA-TIC
1/87 Re-
-------
IF
SEMIVOIATILE ORGANICS ANALYSIS DATA SHEET
TENTATIVELY IDENTIFIED COMPOUNDS
EPA SAMPLE NO.
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Matrix: (soil/water)
Sample wt/vol: (g/mL)
Level: (low/med)
% Moisture: not dec. dec.
Extraction: (SepF/Cont/Sonc)
GPC Cleanup: (Y/N) pH:
Number TICs found:
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
1
EST. CONC.
1
1
Q
1
1
1
1
FORM I SV-TIC
1/87 Rev
-------
2A
WATER VOLATILE SURROGATE RECOVERY
Lab Name:
Lab Code:
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.
SI
(TOL) #
S2
(BFB) |
S3
(DCE) |
OTHER
TOT
OUT
QC LIMITS
SI (TOL) = Toluene-d8 (88-110)
S2 (BFB) = Bromofluorobenzene (86-115)
S3 (DCE) = l,2-Dichloroethane-d4 (76-114)
# Column to be used to flag recovery values
* Values outside of contract required QC limits
D Surrogates diluted out
page
of
FORM II VOA-1
1/87 Re'
-------
2B
SOIL VOLATILE SURROGATE RECOVERY
Lab Name:
Lab Code:
Level:(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.
SI
(TOL) #
S2
(BFB) #
=====
S3
(DCE)#
=====
OTHER
TOT
OUT
QC LIMITS
SI (TOL) = Toluene-d8 (81-117)
S2 (BFB) = Bromofluorobenzene (74-121)
S3 (DCE) - l,2-Dichloroethane-d4 (70-121)
# Column to be used to flag recovery values
* Values outside of contract required QC limits
D Surrogates diluted out
page of
FORM II VOA-2
1/87 Re<
-------
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) *
OTHER |
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
I
I
SI (NBZ) = Nitrobenzene-d5
S2 (FBP) - 2-Fluorobiphenyl
S3 (TPH) - Terphenyl-dl4
S4 (PHL) - Phenol-d6
S5 (2FP) = 2-Fluorophenol
S6 (TBP) = 2,4,6-Tribromophenol
QC LIMITS
(35-114)
(43-116)
(33-141)
(10-94)
(21-100)
(10-123)
# Column to be used to flag recovery values
* Values outside of contract required QC limits
D Surrogates diluted out
page
of
FORM II SV-1
1/87 Rev
-------
2D
SOIL SEMIVOLATILE SURROGATE RECOVERY
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Level:(low/med)
| EPA
j SAMPLE NO.
I ===:=:=3=====:=r=
on
02|
03|
04|
05|
06|
07|
08|
09 |
10|
HI
12|
13|
14|
15|
16|
17|
18|
19|
20|
211
22|
23|
24|
25|
26|
27|
28|
29|
30|
SI
(NB2)#
S2
(FBP)#|
S3
(TPH) |
S4
(PHL) #
S5
(2FP)f
S6
(TBP) #
OTHER
TOT
OUT
SI (NBZ) - Nitrobenzene-d5
S2 (FBP) = 2-Fluorobiphenyl
S3 (TPH) = Terphenyl-dl4
S4 (PHL) « Phenol-d6
S5 (2FP) = 2-Fluorophenol
S6 (TBP) = 2,4,6-Tribromophenol
QC LIMITS
(23-120)
(30-115)
(18-137)
(24-113)
(25-121)
(19-122)
# Column to be used to flag recovery values
* Values outside of contract required QC limits
D Surrogates diluted out
page of
FORM II SV-2
1/87 Re\
-------
2E
WATER PESTICIDE SURROGATE RECOVERY
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
| EPA
| SAMPLE NO.
01|
02|
031
04|
05|
06|
07|
08 |
09 |
10|
HI
12|
13|
14|
15|
16|
17|
181
191
20|
211
22 |
23|
24|
25|
26|
27|
28|
29|
30|
SI
(DBC)#
OTHER
ADVISORY
QC LIMITS
SI (DEC) - Dobutylchlorendate (24-154)
# Column to be used to flag recovery values
* Values outside of QC limits
D Surrogates diluted out
page of
FORM II PEST-1
1/87 Rev
-------
2F
SOIL PESTICIDE SURROGATE RECOVERY
Lab Name:
Lab Code:
Case No. :
Contract :
SAS No . : s
Level:(low/med)
SDG No.
| EPA
j SAMPLE NO.
4 ^ ^— •— ,
on
02|
03|
04|
05|
06|
07|
08|
09|
10 |
HI
121
131
141
151
161
171
181
191
20|
211
22|
231
241
25|
261
271
28|
29|
30|
SI
(DEC) #
OTHER
ADVISORY
QC LIMITS
SI (DEC) = Dibutylchlorendate (24-150)
# Column to be used to flag recovery values
* Values outside of QC limits
D Surrogates diluted out
page of
FORM II PEST-2
1/87 Rev
-------
3A
WATER VOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Lab Name:
Lab Code:
Case No.:
Matrix Spike - EPA Sample No.:
Contract:
SAS No.:
SDG No.:
1
1
| COMPOUND
1 ~~ - -
I 1, 1-Dichloroethene
1 Trichloroethene
I Benzene
| Toluene
I Chlorobenzene
1
SPIKE
ADDED
(ug/L)
SAMPLE
CONCENTRATION
(ug/L)
MS
CONCENTRATION
(ug/L)
MS | QC
% | LIMI1]
REC # | REC.
I ~ "
161-1'
I7i-i:
l?6-i:
l?6-i:
l75-i:
1
COMPOUND
1 , 1 -Dichl oroethene
Trichloroethene
Benzene
Toluene
Chlorobenzene
SPIKE
ADDED
(ug/L)
MSD
CONCENTRATION
(ug/L)
MSD
%
REC #
=s=s==5=s=
1
% | QC LIMITS
RPD || RPD | REC
====== 1 ====== | =====
I 14 161-1-
| 14 |71-i:
| 11 |76-i;
| 13 176-1!
| 13 |75-i:
1 1
# Column to be used to flag recovery and RPD values with an asterisk
* Values outside of QC limits
RPD: out of outside limits
Spike Recovery: out of outside limits
COMMENTS:
FORM III VOA-1
1/87 Re\
-------
3B
SOIL VOLATILE MATRIX SPIKE/MATRIX SPIKE' DUPLICATE RECOVERY
Lab Name:
Lab Code:
Case No.:
Matrix Spike - EPA Sample No.:
Contract:
SAS No.:
SDG No.:
Level:(low/med)
1 1
1 1
| COMPOUND |
| 1,1-Dichloroethene |
I Trichloroethene |
| Benzene |
| Toluene |
I Chlorobenzene I
1 1
SPIKE
ADDED
(ug/Kg)
SAMPLE
CONCENTRATION
(ug/Kg)
MS
CONCENTRATION
(ug/Kg)
MS
%
REC #
QC
LIMIr
REC
59-1'
62-1.
66-1^
59-1:
60-1:
COMPOUND
==========.==============
1, 1-Dichloroethene
Trichloroethene
Benzene
Toluene
Chlorobenzene
SPIKE
ADDED
(ug/Kg)
=========
MSD | MSD
CONCENTRATION | %
(ug/Kg) | REC #
============= 1 ======
1
1
1
1
1
1
%
RPD #
======
QC LIMITS
RPD | REC
======= 1 ====:
22 |59-r
24 |62-i:
21 (66-1.
21 |59-i:
21 |60-i:
1
# Column to be used to flag recovery and RPD values with an asterisk
* Values outside of QC limits
RPD: out of outside limits
Spike Recovery: out of outside limits
COMMENTS:
FORM III VOA-2
1/87 Re\
-------
3C . -
WATER SEMIVOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Lab Name:
Lab Code:
Case No.:
Matrix Spike - EPA Sample No.:
Contract:
SAS No.:
SDG No.:
COMPOUND
Phenol
2-Chlorophenol
1 , 4-Dichlorobenzene
N-Nitroso-di-n-prop. (1)
1,2, 4-Trichlorobenzene
4-Chloro-3-methylphenol
Acenaphthene
4-Nitrophenol
2 , 4-Dinitrotoluene
Pentachlorophenol
Pyrene
SPIKE
ADDED
(ug/L)
SAMPLE
CONCENTRATION
(ug/L)
MS
CONCENTRATION
(ug/L)
MS | QC
% | LIMI:
REC #| REC.
______ i _____
1
|12- <
127-1.
|36- <
|4i-i:
|39- <
|23- <
l46-i:
(10- .
|24- .
| 9-K
t26-i;
1
COMPOUND
Phenol
2-Chlorophenol
1 , 4-Dichlorobenzene
N-Nitroso-di-n-prop. (l)
1,2, 4-Trichlorobenzene
4-Chloro-3-methylphenol
Acenaphthene
4-Nitrophenol
2 , 4-Dinitrotoluene
Pentachlorophenol
Pyrene
SPIKE
ADDED
(ug/L)
MSD
CONCENTRATION
(ug/L)
MSD
%
REC #
%
RPD #
QC L]
RPD
42
40
28
38
28
42
31
50
38
50
31
CMITS
REC
12- 1
27-i:
36- !
41-1:
39- !
23- <
46-i:
10- i
24- <
9-K
26-1.
(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
1/87 Re\
-------
3D
SOIL SEMIVOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Matrix Spike - EPA Sample 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
Pentachlorophenol
Pyrene
SPIKE
ADDED
(ug/Kg)
SAMPLE
CONCENTRATION
(ug/Kg)
MS
CONCENTRATION
(ug/Kg)
MS
%
REC #
QC
LIMITS
REC.
26- 9C
25-102
28-104
41-12€
38-101
26-102
31-13:
11-114
28- 8S
17-10S
35-142
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/Kg)
MSD
CONCENTRATION
(ug/Kg)
MSD
%
REC *
%
RPD #
======
QC L]
RPD
======
35
50
27
38
23
33
19
50
47
47
36
:MITS
REC.
======
26- 9C
25-102
28-104
41-126
38-107
26-103
31-137
11-114
28- 8S
17-109
35-142
(1) N-Nitroso-di-n-propylamine
3 Column to be used to flag recovery and RPD values with an asterisk
* Values outside of QC limits
RPD: out of outside limits
Spike Recovery: out of outside limits
COMMENTS:
FORM III SV-2
1/87 Rev.
-------
3E
WATER PESTICIDE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Matrix Spike - EPA Sample No.:
COMPOUND
gamma -BHC (Lindane)
Heptachlor
Aldrin
Dieldrin
Endrin
4,4' -DDT
SPIKE
ADDED
(ug/L)
| SAMPLE
j CONCENTRATION
1 (ug/L)
I
1
1
1
1
1
1
MS
CONCENTRATION
(ug/L)
MS | QC.
% | LIMITS
REC #| REC.
156-123
140-131
140-120
152-126
|56-121
138-127
1
COMPOUND
gamma -BHC (Lindane)
Heptachlor
Aldrin
Dieldrin
Endrin
4,4' -DDT
SPIKE
ADDED
(ug/L)
MSD
CONCENTRATION
(ug/L)
MSD
%
REC #
% QC
RPD # RPD
15
20
22
18
21
27
LIMITS
| REC.
(56-123
(40-131
140-120
152-126
156-121
138-127
1
# Column to be used to flag recovery and RPD values with an asterisk
* Values outside of QC limits
out of outside limits
Spike Recovery: out of outside limits
COMMENTS:
FORM III PEST-1
8/87 Rev.
-------
3F
SOIL PESTICIDE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Matrix Spike - EPA Sample No.:
Level:(low/med)
COMPOUND
gamxna-BHC (Lindane)
Heptachlor
Aldrin
Dieldrin
Endrin
4,4' -DDT
SPIKE
ADDED
(ug/Kg)
SAMPLE
CONCENTRATION
(ug/Kg)
MS
CONCENTRATION
(ug/Kg)
MS | QC.
% j LIMIT
REC #| REC.
146-12
135-12
134-1:
131-12
|42-i:
123-1:
1
COMPOUND
========================
gamma-BHC (Lindane)
Heptachlor
Aldrin
Dieldrin
Endrin
4,4' -DDT
SPIKE
ADDED
(ug/Kg)
=========
MSD
CONCENTRATION
(ug/Kg)
============
MSD
%
REC #
======
%
RPD f
=====
QC L]
RPD
======
50
31
43
38
45
50
[MITS
REC.
=====
46-12
35-12
34-12
31-12
42-12
23-12
# Column to be used to flag recovery and RPD values with an asterisk
* Values outside of QC limits
RPD: out of outside limits
Spike Recovery: out of outside limits
COMMENTS:
FORM III PEST-2
8/87 Rev
-------
Lab Name:
Lab Code:
4A
VOLATILE METHOD BLANK SUMMARY
Contract:
Case No.:
SAS No.: .
SDG No.:
Lab File ID:
Date Analyzed:
Matrix: (soil/water)
Instrument ID:
Lab Sample ID:
Tine Analyzed:
Level:(low/med)
THIS METHOD BLANK APPLIES TO THE FOLLOWING SAMPLES, MS AND MSD:
| EPA
| SAMPLE NO.
i
oil
02|
03|
04 |
05|
06|
07|
08 |
09|
10|
HI
12|
13|
14|
15|
16|
17|
18|
19|
20|
211
22|
23|
24|
25|
26|
27|
28|
29|
30|
LAB
SAMPLE ID
LAB
FILE ID
TIME
ANALYZED
COMMENTS:
page
of
FORM IV VOA
1/87 Rev
-------
4B
SEMIVOLATILE METHOD BLANK SUMMARY
Lab Name:
Lab Code:
Case No. :
Contract:
SAS No.:
SDG No.:
Lab File ID:
Date Extracted:
Date Analyzed:
Matrix: (soil/water)
Instrument ID:
Lab Sample ID:
Extraction:(SepF/Cont/Sonc)
Time Analyzed:
Level:(low/med)
THIS METHOD BLANK APPLIES TO THE FOLLOWING SAMPLES, MS AND MSD:
| EPA
| SAMPLE NO.
1 _____ ___
Oil
02|
03|
04|
05|
06 |
07|
08|
09|
10|
HI
121
131
141
151
16|
17|
18|
19|
20|
211
22|
23|
24|
251
26|
27|
28)
29|
30|
LAB
SAMPLE ID
LAB
FILE ID
DATE
ANALYZED
COMMENTS:
page of
FORM IV SV
1/87 Re'
-------
Lab Name:
Lab Code:
4C
PESTICIDE METHOD BLANK SUMMARY
Contract:_
SAS No.:
Case No.:
SDG No.:
Lab Sample ID:
Matrix:(soil/water)
Date Extracted:
Date Analyzed (1) :
Time Analyzed (1):
Instrument ID (2):
GC Column ID (1) :
Lab File ID:
Level:(low/med)
Extraction: (SepF/Cont/Sonc)
Date Analyzed (2):
Time Analyzed (2):
Instrument ID (2) :
GC Column ID (1):
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
1/87 Re'
-------
Lab Name:
Lab Code:
5A
VOLATILE ORGANIC GC/MS TUNING AND MASS
CALIBRATION - BROMOFLUOROBENZENE (BFB)
Contract:
SAS No.:
Lab File ID:
Instrument ID:
Case No. :
SDG No.:
BFB Injection Date:
BFB Injection Time:
Matrix:(soil/water)
Level:(low/med)
Column:(pack/cap)
m/e
50
75
95
96
173
174
175
176
177
ION ABUNDANCE CRITERIA
15.0 - 40.0% of mass 95
30.0 - 60.0% of mass 95
Base peak, 100% relative abundance_
5.0 - 9.0% of mass 95
Less than 2.0% of mass 174
Greater than 50.0% of mass 95
5.0 - 9.0% of mass 174
Greater than 95.0%, but less than 101.0% of mass 174
5.0 - 9.0% of mass 176
% RELATIVE
ABUNDANCE
1-Value is % mass 174 2-Value is % mass 176
THIS TUNE APPLIES TO THE FOLLOWING SAMPLES, MS, MSD, BLANKS, AND STANDARDS
| EPA
| SAMPLE NO.
j ===========
on
02 |
03|
04|
05|
06|
07|
08|
09|
10|
HI
121
131
14|
15|
16|
17|
18|
19|
20|
211
22|
LAB
SAMPLE ID
==============
LAB
FILE ID
DATE
ANALYZED
TIME
ANALYZED
==========
page of
FORM V VOA
1/87 Re
-------
5B
SEMIVOIATILE ORGANIC GC/MS TUNING AND MASS
CALIBRATION - DECAFLUOROTRIPHENYLPHOSPHINE (DFTPP)
Lab Name:
Lab Code:
Case No.
Contract:
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 - 60.0% of mass 198
Less than 2.0% of mass 69
Mass 69 relative abundance
Less than 2.0% of mass 69
40.0 - 60.0% 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 1.00% of mass 198
Present, but less than mass 443
Greater than 40.0% of mass 198
17.0 - 23.0% of mass 442
% RELATIVE
ABUNDANCE
)2
1-Value is % mass 69
2-Value is % mass 442
THIS TUNE APPLIES TO THE FOLLOWING SAMPLES, MS, MSD, BLANKS, AND STANDARDS
page of
| EPA
| SAMPLE NO.
02|
03|
04 |
05|
06|
07 |
08|
09 |
10 |
HI
12 |
13 |
14 |
15 |
16 |
17 |
18 |
19 |
20|
21 |
22|
LAB
SAMPLE ID
^
LAB
FILE ID
DATE
ANALYZED
TIME
ANALYZED
FORM V SV
1/87
-------
6A
VOLATILE ORGANICS INITIAL CALIBRATION DATA
Lab Name:
Lab Code:
Case No. :
Contract :
SAS No. : S
SDG No.:
Instrument ID:
Matrix:(soil/water)
Min RRF for SPCC(|)
Calibration Date(s):
Level:(low/med) Column:(pack/cap)
0.300 (0.250 for Bromoform) Max %RSD for CCC(*) - 30.0
ILAB FILE ID: RRF20
RRF50 =
|RRF100= RRF150= RRF200=
1
1
j COMPOUND
| Chloromethane •
| Bromomethane
| Vinyl Chloride *
I Chi or oe thane
IMethylene Chloride
I Acetone
I Carbon Disulfide
1 1 , 1-Dichloroethene <
1 1 , 1-Dichloroethane ^
jl,2-Dichloroethene ( total )_
| Chloroform <
j 1 , 2-Dichloroethane
|2-Butanone
11,1, 1-Trichloroethane
| Carbon Tetrachloride
1 Vinyl Acetate
j Bromodichloromethane
| 1 , 2-Dichloropropane *
|cis-l,3-Dichloropropene
I Trichloroethene
j Dibromochloromethane
| 1 , 1 , 2-Trichloroethane
| Benzene
| trans-1 , 3-Dichloropropene
j Bromoform
I 4-Methyl-2-Pentanone
| 2-Hexanone
| Tetrachloroethene
| 1 , 1 , 2 , 2-Tetrachloroethane
| Toluene
I Chlorobenzene
I Ethylbenzene
| Styrene
IXylene (total)
|Toluene-d8
| Broroof luorobenzene
| 1 , 2-Dichloroethane-d4
I
RRF20
k
1
!
fc
1
k
RRF50
RRF100
RRF150
RRF200
RRF
%
RSD
FORM VI VOA
1/87 Rev
-------
6B
SEMIVOLATILE ORGANICS INITIAL CALIBRATION DATA
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Instrument ID:
Calibration Date(s):
Min RRF for SPCC(f) - 0.050
Max %RSD for CCC(*) =30.0
ILAB FILE ID: RRF20
RRF50 =
IRRF80 - RRF120= RRF160=
1
1 1
| COMPOUND |RRF20
I Phenol *
1 bis (2-Chloroethyl) ether
I 2-Chlorophenol
1 1 , 3-Dichlorobenzene
j 1 , 4 -Dichlorobenzene '
I Benzyl alcohol
| 1,2-Dichlorobenzene
1 2-Methylphenol
|bis(2-Chloroisopropyl)ether
I 4-Methylphenol
JN-Nitroso-di-n-propylamine •
I Hexachloroe thane
j Nitrobenzene
| Isophorone
|2-Nitrophenol <
| 2 , 4-Dimethylphenol
JBenzoic acid
| bis (2-Chloroethoxy) methane_
|2,4-Dichlorophenol *
| 1 , 2 , 4-Trichlorobenzene
j Naphthalene
j 4-Chloroaniline
| Hexachlorobutadiene <
| 4-Chloro-3-methylphenol *
j 2-Methylnaphthalene
| Hexachlorocyclopentadiene
| 2,4,6-Trichlorophenol <
| 2 , 4 , 5-Trichlorophenol
j 2-Chloronaphthalene
|2-Nitroaniline
| Dimethylphthalate
| Acenaphthylene
| 2 , 6-Dinitrotoluene
|3-Nitroaniline
k
\
\t
k
k
k
\
k
j Acenaphthene *
I 2 , 4 -Dinitrophenol #
|4-Nitrophenol #
1 1
RRF50
RRF80
RRF120
RRF160
RRF
RSD
~^^2.
T
1
1
1
FORM VI SV-1
1/87 Rev.
-------
6C
SEMIVOLATILE ORGANICS INITIAL CALIBRATION DATA
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.
Instrument ID:
Calibration Date(s):
Min RRF for SPCC(f) - 0.050
Max %RSD for CCC(*) = 30.(
ILAB FILE ID: RRF20
RRF50 =
IRRF80 = RRF120= RRF160=
1
1
| COMPOUND
1 Dibenzof uran
| 2 , 4-Dinitrotoluene
1 Diethylphthalate
| 4-Chlorophenyl-phenylether
I Fluorene
| 4-Nitroaniline
| 4 , 6-Dinitro-2-methylphenol
| N-Nitrosodiphenylamine (1) *
| 4-Bromophenyl-phenylether
| Hexachlorobenzene
| Pentachlorophenol <
| Phenanthrene
| Anthracene
| Di-n-butylphthalate
| Fluoranthene <
| Pyrene
| Butylbenzylphthalate
| 3 , 3 ' -Dichlorobenzidine
| Benzo (a) anthracene
| Chrysene
| bis (2-Ethylhexyl) phthalate
| Di-n-octylphthalate *
\ Benzo (b) f luoranthene
| Benzo (k) f luoranthene
|Benzo(a)pyrene *
| Indeno (1,2, 3-cd) pyrene
| Dibenz (a , h) anthracene
I Benzo(g,h, i)perylene
*
I Nitrobenzene-d5
| 2-Fluorobiphenyl
I Terphenyl-dl4
I Phenol-d6
| 2-Fluorophenol
| 2 , 4 , 6-Tribromophenol
1
RRF20
k
k
RRF50
RRF80
RRF120
RRF160
mu
RRF
%
RSD
======
(1) Cannot be separated from Diphenylamine
FORM VI SV-2
1/87 Rev
-------
7A
VOLATILE CONTINUING CALIBRATION CHECK
Lab Name:
Lab Code:
Contract:
Case No.:
SAS No.:
Instrument ID:
Lab File ID:
Calibration Date:
SDG No.:
Time:
Matrix:(soil/water)
_ Init. Calib. Date(s)
Level:(low/med)
Column:(pack/cap)
Min RRF50 for SPCC(f) « 0.300 (0.250 for Bromoform) Max %D for CCC(*) = 25.0
1
| COMPOUND
| Chi orome thane
| Bromomethane
I Vinyl Chloride
| Chi oroe thane
(Methylene Chloride
| Acetone
| Carbon Disulfide
1 1, 1-Dichloroethene
1 1 , 1-Dichloroethane
| 1 , 2-Dichloroethene (total)
I Chloroform
j 1,2-Dichloroethane
| 2-Butanone
1 1, 1, 1-Trichloroethane
| Carbon Tetrachloride
| Vinyl Acetate
j Bromodichloromethane
| 1 , 2-Dichloropropane
j cis-1 , 3-Dichloropropene
j Trichloroethene
| Dibromochloromethane
| 1 , 1 , 2-Trichloroethane
| Benzene
| trans-1, 3-Dichloropropene
| Bromoform
| 4-Methyl-2-Pentanone
|2-Hexanone
| Tetrachloroethene
11,1,2, 2-Tetrachloroethane
| Toluene
j Chlorobenzene
| Ethylbenzene
| Styrene
IXylene (total)
1 Toluene-d8
j Bromofluorobenzene
I l,2-Dichloroethane-d4
1
1
| RRF
I
1
1
*
1
1
1
1
*
I
1
*
1
1
1
1
1
1
*
1
1
1
1
1
1
f
1
1
1
1
*
1
*
1
I
1
1
1
1
RRF50
========
%D
4
4
*
4
4
'•
=======
FORM VII VOA
1/87 Rev
-------
7B
SEMIVOLATILE CONTINUING CALIBRATION CHECK
Lab Name:
Contract:
Lab Code:
Case No.:
SAS No.:
Instrument ID:
Lab File ID:
Calibration Date:
Init. Calib. Date(s):
Min RRF50 for SPCC(f) = 0.050
SDG No.:
Time:
Max %D for CCC(*) = 25.0%
1
| COMPOUND
1 Phenol <
I bis (2-Chloroethyl) ether
I 2-Chlorophenol
1 1, 3 -Dichlorobenzene
(1,4 -Dichlorobenzene *
I Benzyl alcohol
1 1, 2 -Dichlorobenzene
|2-Methylphenol
j bis (2-Chloroisopropyl) ether
I 4-Methylphenol
j N-Nitroso-di-n-propylamine_
I Hexachloroethane
| Nitrobenzene
I Isophorone
I 2-Nitrophenol <
1 2 , 4-Dimethylphenol
j Benzoic acid
| bis (2 -Chloroethoxy) methane
I 2 , 4-Dichlorophenol <
j 1 , 2 , 4-Trichlorobenzene
I Naphthalene
1 4-Chloroaniline
j Hexachlorobutadiene '
| 4-Chloro-3-methylphenol '
| 2-Methylnaphthalene
I Hexachlorocyclopentadiene 1
j 2 , 4 , 6-Trichlorophenol i
I 2 , 4 , 5-Trichlorophenol
| 2-Chloronaphthalene
|2-Nitroaniline
| Dimethylphthalate
I Acenaphthylene
I 2 , 6-Dinitrotoluene
1 3-Nitroaniline
| Acenaphthene
| 2 , 4-Dinitrophenol
|4-Nitrophenol
1
RRF
•
k
1
*
k
k
k
f
k
*
I
\
RRF50
%D
•
*
••
*
i
*
1
1
FORM VII SV-1
1/87 Rev.
-------
Lab Name:
7C
SEMIVOLATILE CONTINUING CALIBRATION CHECK
Contract:
Lab Code:
Instrument ID:
Case No.: SAS No.:
Calibration Date:
SDG No.:
Time:
Lab File ID:
Init. Calib. Date(s):
Min RRF50 for SPCC(t) « 0.050
Max %D for CCC(*) = 25.C
1
| COMPOUND
1 Dibenzof uran
j 2 , 4-Dinitrotoluene
| Diethylphthalate
| 4-Chlorophenyl-phenylether
| Fluorene
|4-Nitroaniline
j 4 , 6-Dinitro-2-methylphenol
| N-Nitrosodiphenylamine (1) <
| 4-Bromophenyl-phenylether
| Hexachlorobenzene
| Pentachlorophenol 1
| Phenanthrene
| Anthracene
| Di-n-butylphthalate
| Flucranthene *
| Pyrene
| Butylbenzylphthalate
13,3' -Dichlorobenzidine
| Benzo (a) anthracene
I Chrysene
| bis (2-Ethylhexyl) phthalate
| Di-n-octylphthalate *
| Benzo (b) f luoranthene
| Benzo (k) f luoranthene
| Benzo(a)pyrene <
| Indeno (1,2, 3-cd) pyrene
j Dibenz (a , h) anthracene
| Benzo (g,h,i)perylene
1 Nitrobenzene-d5
I 2-Fluorobiphenyl
j Terphenyl-dl4
| Phenol -d6
| 2-Fluorophenol
| 2 , 4 , 6-Tribromophenol
1
RRF
k
k
k
k
k
RRF50
%D
i
4
4
4
4
=======
(1) Cannot be separated from Diphenylamine
FORM VII SV-2
1/87 Rev.
-------
8A
VOLATILE INTERNAL STANDARD AREA SUMMARY
Lab Name:
Lab Code:
Case No.
Contract:
SAS No.:
SDG No.:
Lab File ID (Standard):
Instrument ID:
Date Analyzed:
Time Analyzed:
Matrix:(soil/water)
Level:(low/ned)
Column:(pack/cap)
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
12 HOUR STD
UPPER LIMIT
LOWER LIMIT
EPA SAMPLE
NO.
ISl(BCM)
AREA #
========
RT
IS2(DFB)
AREA *
===««
RT
IS3(CBZ)
AREA #
•8T-T— — — — — — — —
RT
IS1 (BCM) » Bromochloromethane
IS2 (DFB) = 1,4-Difluorobenzene
IS3 (CBZ) = Chlorobenzene-d5
UPPER LIMIT - + 100%
of internal standard area,
LOWER LIMIT - - 50%
of internal standard area
I Column used to flag internal standard area values with an asterisk
page of
FORM VIII VOA 1/87 Rev
-------
85
SEMIVOLATILE INTERNAL STANDARD AREA SUMMARY
Lab Name:
•
Lab Code:
Case No.:
Lab File ID (Standard):
Instrument ID:
Contract:
SAS No.:
SDG No.
Date Analyzed:
Tine Analyzed:
1
==
| 12 HOUR STD
| UPPER LIMIT
| LOWER LIMIT
| EPA SAMPLE
| NO.
01|
02|
03|
04 |
05|
06|
07|
08 |
09|
10|
HI
12|
13|
14|
15|
16|
17|
181
191
20|
211
22|
ISl(DCB)
AREA |
IP - i • i i
RT
"™ — — — ^— ^—
IS2(NPT)
AREA *
===— tn— ~===
RT
""""" *»—
IS3(ANT)
AREA f
_ ,-r ,- „ CJC.SSS
~~
RT
=»srssw=
=====
IS1 (DCB) m l/4-Dichlorobenzene-d4
IS2 (NPT) - Naphthalene-dS
IS3 (ANT) = Acenaphthene-dlO
UPPER LIMIT « + 100%
of internal standard area.
LOWER LIMIT « - 50%
of internal standard area.
Column used to flag internal standard area values with an asterisk
page
of
FORM VIII SV-1
1/87 Rev.
-------
8C
SEMIVOLATILE INTERNAL STANDARD AREA SUMMARY
Lab Name:
Lab Code:
Case No.:
Lab File ID (Standard):
Instrument ID:
Contract:
SAS No.:
SDG No.
Date Analyzed:
Time Analyzed:
1
1
1 _.______..___ ..
| 12 HOUR STD
| UPPER LIMIT
•
| LOWER LIMIT
1 ^»«K^B^»^B^H^» <^B_V-«»^»
| EPA SAMPLE
| NO.
1 ==•— m=-r «r
1 *»-»•« =
on
021
03|
04|
05|
06|
071
08 |
09|
10|
HI
12 |
13 |
14 |
15 |
16|
17 |
18|
19|
20|
211
22|
IS4(PHN)
AREA |
._ ^ __
RT
,_ _ : _
IS5(CRY)
AREA I
__
RT
IS6(PRY)
AREA 1
*"~ •"-*•--—
._
III l ill • "
RT
======
IS4 (PHN)
IS5 (CRY)
IS6 (PRY)
Phenanthrene-dlO
Chrysene-dl2
Perylene-dl2
UPPER LIMIT «= + 100%
of internal standard area
LOWER LIMIT - - 50%
of internal standard area
# Column used to flag internal standard area values with an asterisk
page of
FORM VIII SV-2
1/87 Rev.
-------
80
PESTICIDE EVALUATION STANDARDS SUMMARY
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.
Instrument ID:
GC Column ID:
Dates of Analyses:
to
Evaluation Check for Linearity
PESTICIDE
Aldrin
Endrin
4,4' -DDT
DEC
CALIBRATION
FACTOR
EVAL MIX A
CALIBRATION |
FACTOR |
EVAL MIX B |
1
1
1
1
1
CALIBRATION
FACTOR
EVAL MIX C
%RSD
( 10.0% RSD, plot a standard curve and determine the ng
for each sample in that set from the curve.
Evaluation Check for 4,4'-DDT/Endrin Breakdown
(percent breakdown expressed as total degradation)
01
02
03
04 |
05|
06
07|
08
09
10 i
111
12
13
INITIAL
EVAL MIX B
EVAL MIX B
EVAL MIX B
EVAL MIX B
EVAL MIX B
EVAL MIX B
EVAL MIX B
EVAL MIX B
EVAL MIX B
EVAL MIX B
EVAL MIX B
EVAL MIX B
EVAL MIX B
EVAL MIX B
DATE
ANALYZED
TIME
ANALYZED
ENDRIN
4,4' -DDT
COMBINED
(2)
(2) See Form instructions.
FORM VIII PEST-1
8/87 Re\
-------
8E
PESTICIDE EVALUATION STANDARDS SUMMARY
Evaluation of Retention Time Shift for Dibutylchlorendate
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Instrument ID:
GC Column ID:
Dates of Analyses:
to
| EPA
| SAMPLE NO.
on
021
031
041
05|
06|
071
08 |
09|
101
111
121
131
141
15 |
161
17 |
18 |
19 |
20|
211
22|
23|
24|
25|
26)
27|
28|
29|
30|
311
32|
331
34|
351
36|
37|
38|
LAB SAMPLE
ID
DATE
ANALYZED
•
TIME
ANALYZED
%
D
*
* Values outside of QC limits (2.0% for packed columns,
0.3% for capillary columns)
page
of
FORM VIII PEST-2
1/87 Re
-------
PESTICIDE/PCB STANDARDS SUMMARY
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Instrument ID:
GC Column ID:
1
| COMPOUND
1
| alpha-BHC
Ibeta-BHC
I delta-BHC
| gamma -BHC
| Heptachlor
I Aldrin
JHept. epoxide
JEndosulfan I
IDieldrin
|4,4' -DDE
j Endrin
jEndosulfan II
| 4 , 4 ' -DDD
|Endo. sulfate
14,4' -DDT
| Methoxychlor
| Endrin ketone
|a. Chlordane
|g. Chlordane
| Toxaphene
|Aroclor-1016
|Aroclor-1221
|Aroclor-1232
(Aroclor-1242
|Aroclor-1248
jAroclor-1254
|Aroclor-1260
1
DATE(S) OF FROM:
ANALYSIS
TO:
TIME(S) OF FROM:
ANALYSIS
RT
]
WI1
FROM
TO:
*T
1DOW
TO
CALIBRATION
FACTOR
DATE OF ANALYSIS
TIME OF ANALYSIS
EPA SAMPLE NO.
(STANDARD)
RT
CALIBRATION
FACTOR
QNT
Y/N
%D
Under QNT Y/N: enter Y if quantitation was performed, N if not performed.
%D must be less than or equal to 15.0% for quantitation, and less than
or equal to 20.0% for confirmation.
Note: Determining that no compounds were found above the CRQL is a form of
quantitation, and therefore at least one column must meet the 15.0% criteric
For multicomponent analytes, the single largest peak that is characteristic
of the component should be used to establish retention time and %D.
Identification of such analytes is based primarily on pattern recognition.
page of
FORM IX PEST
8/87
-------
Lab Name:
Lab Code:
10
PESTICIDE/PCB IDENTIFICATION
Contract:
SAS No.:
EPA SAMPLE NO.
GC Column ID (1):
Instrument ID (1):
Lab Sample ID:
Lab File ID:
Case No.
SDG No.:
GC Column ID (2):
Instrument ID (2):
(only if confirmed by GC/MS)
PESTICIDE/PCB
01
02
03
04
05
06
07
08
09
10
11
12
Comments:
RETENTION TIME
Column 1
Column 2
Column 1
Column 2
Column 1
Column 2
Column 1
Column 2
Column 1
Column 2
Column 1
Column 2
RT WINDOW
OF STANDARD
From TO
QUANT? GC/MS?
(Y/N) (Y/N)
page of
FORM X PEST
1/87 Rev
-------
EXHIBIT C
TARGET COMPOUND LIST (TCL) AND
CONTRACT REQUIRED QUANTITATION LIMITS (CRQL)
C-l 2/88
-------
Target Compound List (TCP and
Contract Required Quantitation Limits (CROP*
Ouantitation Limits**
Volatiles
1. Chloromethane 74-87-3
2. Bromomethane 74-83-9
3. Vinyl Chloride 75-01-4
4. Chloroethane 75-00-3
5. Methylene Chloride 75-09-2
6. Acetone 67-64-1
7. Carbon Disulfide 75-15-0
8. 1,1-Dichloroethene 75-35-4
9. 1,1-Dichloroethane 75-34-3
10. 1,2-Dichloroethene (total) 540-59-0
11. Chloroform 67-66-3
12. 1,2-Dichloroethane 107-06-2
13. 2-Butanone 78-93-3
14. 1,1,1-Trichloroethane 71-55-6
15. Carbon Tetrachloride 56-23-5
16. Vinyl Acetate 108-05-4
17. Bromodichloromethane 75-27-4
18. 1,2-Dichloropropane 78-87-5
19. cis-l,3-Dichloropropene 10061-01-5
20. Trichloroethene 79-01-6
21. Dibromochloromethane 124-48-1
22. 1,1,2-Trichloroethane 79-00-5
23. Benzene 71-43-2
24. trans-l,3-Dichloropropene 10061-02-6
25. Bromoform 75-25-2
26. 4-Methyl-2-pentanone 108-10-1
27. 2-Hexanone 591-78-6
28. Tetrachloroethene 127-18-4
29. Toluene 108-88-3
30. 1,1,2,2-Tetrachloroethane 79-34-5
(continued)
ug/L
10
10
10
10
5
10
5
5
5
5
5
5
10
5
5
10
5
5
5
5
5
5
5
5
5
10
10
5
5
5
Low Soil/Sediment3
ug/Kg
10
10
10
10
5
10
5
5
5
5
5
5
10
5
5
10
5
5
5
5
5
5
5
5
5
10
10
5
5
5
C-2
2/88
-------
Quantisation Limits**
Water Low Soil/Sediment3
Volatiles CAS Number ug/L ug/Kg
31. Chlorobenzene 108-90-7 5 5
32. Ethyl Benzene 100-41-4 5 5
33. Styrene 100-42-5 5 5
34. Xylenes (Total) 1330-20-7 5 5
a Medium Soil/Sediment Contract Required Quantitation Limits (CRQL) for
Volatile TCL Compounds are 125 times the individual Low Soil/Sediment
CRQL.
* Specific quantitation limits are highly matrix dependent. The
quantitation limits listed herein are provided for guidance and may not
always be achievable.
** Quantitation limits listed for soil/sediment are based on wet weight. The
quantitation limits calculated by the laboratory for soil/sediment,
calculated on dry weight basis as required by the contract, will be
higher.
C-3 2/88
-------
Target Compound List (TCP and
Contract Reauired Quantisation Limits (CROD*
Ouantitation Limits**
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50,
51.
52.
53
54,
55.
56.
57.
58.
59,
60,
61,
62,
63,
64
65.
66.
67,
68
69
Semivolatiles
Phenol
, bis(2-Chloroethyl) ether
. 2-Chlorophenol
, 1 , 3-Dichlorobenzene
1 ,4-Dichlorobenzene
, Benzyl alcohol
1 , 2-Dichlorobenzene
, 2-Methylphenol
, bis (2-Chloroisopropyl)
ether
4 -Methylphenol
, N-Nitroso-di-n-
dipropylamine
Hexachloroe thane
Nitrobenzene
, Isophorone
2-Nitrophenol
. 2 ,4-Dimethylphenol
, Benzoic acid
, bis(2-Chloroethoxy)
methane
2 ,4-Dichlorophenol
. 1 , 2 ,4-Trichlorobenzene
Naphthalene
. 4-Chloroaniline
. Hexachlorobutadiene
. 4-Chloro-3-methylphenol
(para-chloro-meta-cresol)
. 2-Methylnaphthalene
, Hexachlorocyclopentadiene
. 2 ,4, 6-Trichlorophenol
. 2,4,5-Trichlorophenol
. 2-Chloronaphthalene
2-Nitroaniline =-
. Dimethylphthalate
. Acenaphthylene
. 2 , 6-Dinitrotoluene
. 3-Nitroaniline
. Acenaphthene
CAS Number
108-95-2
111-44-4
95-57-8
541-73-1
106-46-7
100-51-6
95-50-1
95-48-7
108-60-1
106-44-5
621-64-7
67-72-1
98-95-3
78-59-1
88-75-5
105-67-9
65-85-0
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
Water
ue/L
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
50
10
10
10
10
10
10
10
10
10
10
50
10
50
10
10
10
50
10
Low Soil/Sediment13
uz/Kz
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
330
1600
330
330
330
330
330
330
330
330
330
330
1600
330
1600
330
330
330
1600
330
(continued)
C-4
2/88
-------
Quantitation Limits**
Semivolatiles CAS Number
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.
98.
99.
2 ,4-Dinitrophenol
4-Nitrophenol
Dibenzofuran
2 ,4-Dinitrotoluene
Diethylphthalate
4-Chlorophenyl-phenyl ether
Fluorene
4-Nitroaniline
4, 6-Dinitro-2-methylphenol
N-nitrosodiphenylamine
4-Bromophenyl-phenylether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
3,3' -Dichlorobenzidine
Benzo (a) anthracene
Chrysene
bis(2-Ethylhexyl)phthalate
Di-n-octylphthalate
Benzo (b ) f luoranthene
Benzo (k) f luoranthene
Benzo(a)pyrene
Indeno(l , 2 , 3-cd)pyrene
Dibenz (a , h) anthracene
Benzo(g,h, i)perylene
51-28-5
100-02-7
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
84-74-2
206-44-0
129-00-0
85-68-7
91-94-1
56-55-3
218-01-9
117-81-7
117-84-0
205-99-2
207-08-9
50-32-8
193-39-5
53-70-3
191-24-2
Water
ue/L
50
50
10
. 10
10
10
10
50
50
10
10
10
50
10
10
10
10
10
10
20
10
10
10
10
10
10
10
10
10
10
Low Soil/Sediment0
ug/Ke
1600
1600
330
330
330
330
330
1600
1600
330
330
330
1600
330
330
330
330
330
330
660
330
330
330
330
330
330
330
330
330
330
Medium Soil/Sediment Contract Required Quantitation Limits (CRQL) for
SemiVolatile TCL Compounds are 60 times the individual Low Soil/Sediment
CRQL.
* Specific quantitation limits are highly matrix dependent. The
quantitation limits listed herein are provided for guidance and may not
always be achievable.
** 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.
The
C-5
2/88
-------
Target Compound List (TCP and
Contract Required Ouantitation Limits (CROP*
Pesticides/PCBs
CAS Number
Ouantitation Limits**
Water Low Soil/Sedimentc
ue/L ug/Kg
100. alpha-BHC
101. beta-BHC
102. delta-BHC
103. gamma-BHC (Lindane)
104. Heptachlor
105. Aldrin
106. Heptachlor epoxide
107. Endosulfan I
108. Dieldrin
109. 4,4'-DDE
110. Endrin
111. Endosulfan II
112. 4,4'-DDD
113. Endosulfan sulfate
114. 4,4'-DDT
115. Methoxychlor
116. Endrin ketone
117. alpha-Chlordane
118. gamma-Chlordane
119. Toxaphene
120. Aroclor-1016
121. Aroclor-1221
122. Aroclor-1232
123. Aroclor-1242
124. Aroclor-1248
319-84-6
319-85-7
319-86-8
58-89-9
76-44-8
309-00-2
1024-57-3
959-98-8
60-57-1
72-55-9
72-20-8
33213-65-9
72-54-8
1031-07-8
50-29-3
72-43-5
53494-70-5
5103-71-9
5103-74-2
8001-35-2
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.5
0.10
0.5
0.5
1.0
0.5
0.5
0.5
0.5
0.5
8.0
8.0
8.0
8.0
8.0
8.0
8.0
8.0
16.0
16.0
16.0
16.0
16.0
16,0
16.0
80.0
16.0
80.0
80.0
160.0
80.0
80.0
80.0
80.0
80.0
125. Aroclor-1254
126. Aroclor-1260
11097-69-1
11096-82-5
1.0
1.0
160.0
160.0
Medium Soil/Sediment Contract Required Quantitation Limits (CRQL) for
Pesticide/PCB TCL compounds are 15 times the individual Low Soil/Sediment
CRQL.
* Specific quantitation limits are highly matrix dependent. The
quantitation limits listed herein are provided for guidance and may not
always be achievable.
** 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.
The
C-6
2/88
-------
EXHIBIT D
ANALYTICAL METHODS
FOR VOLATILES
D-l/VOA 2/38
-------
Table of Contents
Page
SECTION I - Introduction D-3/VOA
SECTION II - Sample Preparation and Storage D-5/VOA
PART A - Sample Storage and Holding Times D-6/VOA
PART B - Protocols for Hexadecane
Extraction of Volatiles from
Water and Soil/Sediment for
Optional Screening D-7/VOA
SECTION III - Optional Screening of Hexadecane
Extracts for Volatiles D-10/VOA
SECTION IV - GC/MS Analysis of Volatiles D-14/VOA
D-2/VOA 2/88
-------
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 2/88
-------
1. Method for the Determination of Volatile (Purgeable) Organic Compounds
1.1 Scope and Application
This method covers the determination of the TCL 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.
D-A/VOA 2/85
-------
SECTION II
SAMPLE PREPARATION AND STORAGE
D-5/VOA 2/88
-------
PART A - SAMPLE STORAGE AND HOLDING TIMES
1. Procedures for Sample Storage
1.1 The samples must be protected from light and refrigerated at 4°C (±2eC)
from the time of receipt until analysis or extraction.
2. Contract Required Holding Times
2.1 VOA analysis of water or soil/sediment samples must be completed within
10 days of VTSR.
D-6/VOA 2/88
-------
PART B - PROTOCOLS FOR HEXADECANE EXTRACTION OF VOLATILES FROM WATER AND
SOIL/SEDIMENT FOR OPTIONAL SCREENING
1. Summary of Method
WATER - a 40 ml aliquot of sample is extracted with 2 ml of hexadecane.
This provides a minimum quantitation limit (MQL) of:
Compounds MQL ug/L
non-halogenated aromatics 40- 50
halogenated methanes 800-1000
halogenated ethanes ' 400- 500
SOIL/SEDIMENT - Forty 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.
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.
4. Apparatus and Materials
4.1 Vials and caps, 2 mL for GC auto sampler.
D-7/VOA 2/8S
-------
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 - Reagent water is 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)- Stock standard solutions
can be 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 dilute to volume yin a 10 mL
volumetric flask. Larger volumes can be used at the
convenience of the analyst. If compound purity is
certified at 96% or greater, the weight can be used
without correction to calculate the concentration of
the stock standard.
5.3.1.2 Transfer the stock 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 2/88
-------
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:
o pulling the emulsion through a small plug of Pyrex
glass wool packed in a pipet, or
o transferring the emulsion to a centrifuge tube and
centrifuging for several minutes.
6.1.3 Add 200 uL of working standard mixture #1 and #2 to separate 40
mL portions of reagent water. Follow steps 6.1.1 - 6.1.2
beginning 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 2/8!
-------
SECTION III
OPTIONAL SCREENING OF HEXADECANE
EXTRACTS FOR VOLATILES
D-10/VOA 2/88
-------
1. Summary of Method
1.1 The hexadecane extracts of water and soil/sediment are screened on a
gas chromatograph/flame ionization detector (GC/FID). The results of
the screen will determine if volatile organics are to be analyzed by
low or medium level GC/MS procedures if the sample is a soil/sediment,
or to determine the appropriate dilution factor if the sample is water.
2. Apparatus and Materials
2.1 Gas chromatograph - An analytical system complete with gas
chromatograph suitable for on-column injection and all required
accessories including syringes, analytical columns, gases, detector,
and strip-chart recorder. A data system is recommended for measuring
peak areas.
2.1.1 Above-described GC, equipped with flame ionization detector.
2.1.2 GC column - 3 m x 2 mm ID glass column packed with 10% OV-101
on 100-120 mesh Chromosorb W-HP (or equivalent). The column
temperature should be programmed from 80"C to 280°C at
16°C/min. and held at 280°C for 10 minutes.
3. Reagents
3.1 Hexadecane - pesticide residue analysis grade or equivalent.
4. Limitations
A.I The flame ionization detector varies considerably in sensitivity when
comparing aromatics and halogenated methanes and ethanes. Halomethanes
are approximately 20 X less sensitive than aromatics and haloethanes
approximately 10 X less sensitive. Low molecular weight, water soluble
solvents e.g. alcohols and ketones, will not extract from the water,
and therefore will not be detected by the GC/FID.
4.2 Following are two options for interpreting the GC/FID chromatogram.
4.2.1 Option A is to use standard mixture #1 containing the aromatics
to calculate an approximate concentration of the aromatics in
the sample. Use this information to determine the proper
dilution for purge and trap if the sample is a water or whether
to use the low or medium level GC/MS purge and trap methods if
the sample is a soil/sediment (see Table 1, paragraph 6.2.1.3
for guidance). This should be the best approach, however, the
aromatics may be absent or obscured by higher concentrations of
other purgeables. In these cases, Option B may be the best
approach.
4.2.2 Option B is to use standard mixture #2 containing nonane and
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
D-ll/VOA 2/88
-------
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 of the mix #1 and mix #2
compounds, prepared in paragraph 5.3.1 of Section II, Part B. Use the
GC conditions specified in 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 x 50 - Dilution
peak area of n-nonane factor
The water sample will be diluted using the
calculated factor just prior to purge and trap GC/MS
analysis.
6.2 Soil/Sediment
6.2.1 Compare the chromatograms of the hexadecane extract of the
sample with those of the reagent blank and extract of the
standard.
6.2.1.1 If no peaks are noted, other than those also in the
reagent blank, analyze a 5 g sample by low level
GC/MS.
D-12/VOA 2/88
-------
6.2.1.2 If peaks are present prior to the n-dodecane and the
aromatics are distinguishable, follow Option A
(paragraph 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, use
Option B as follows: Calculate a factor using the
following formula:
peak area of sample malor 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 10X higher.
6.3 Sample Analysis
Proceed to Section IV, GC/MS Analysis of Volatiles.
D-13/VOA 2/8:
-------
SECTION IV
GC/MS ANALYSIS
OF VOLATILES
D-14/VOA 2/88
-------
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 a 5 g
sample and reagent water contained in a suggested specially
designed purging chamber (illustrated in Figure 5) at elevated
temperatures. The purgeables are efficiently transferred from
the aqueous phase to the vapor phase. The vapor is swept
through a sorbent column where the purgeables are trapped.
After purging is completed, the sorbent column is heated and
backflushed with the inert gas to desorb the purgeables onto a
gas chromatographic column. The gas chromatograph is
temperature programmed to separate the purgeables which are
then detected with a mass spectrometer.
1.2.2 Medium Level. A measured amount of soil is extracted with
methanol. A portion of the methanol extract is diluted to 5 mL
with reagent water. An inert gas is bubbled through this
solution in a specifically designed purging chamber at ambient
temperature. The purgeables are effectively transferred from
the aqueous phase to the vapor phase. The vapor is swept
through a sorbent column where the purgeables are trapped.
After purging is completed, the sorbent column is heated and
backflushed with the inert gas to desorb the purgeables onto a
gas chromatographic column. The gas chromatograph is
temperature programmed to separate the purgeables which are
then detected with a mass spectrometer.
2. Interferences
2.1 Impurities in the purge gas, organic compounds out-gassing from the
plumbing ahead of the trap, and solvent vapors in the laboratory
account for the majority of contamination problems. The analytical
system must be demonstrated to be free from contamination under the
conditions of the analysis by running laboratory reagent blanks as
described in Exhibit E. The use of non-TFE tubing, non-TFE thread
sealants, or flow controllers with rubber components in the purging
device should be avoided.
D-15/VOA 2/88
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2.2 Samples can be contaminated by diffusion of volatile organics
(particularly fluorocarbons and methylene chloride) through the septum
seal into the sample during storage and handling. A holding blank
prepared from reagent water and carried through the holding period and
the analysis protocol serves as a check on such contamination. One
holding blank per case should be analyzed. Data must be retained by
laboratory and made available for inspection during on-site
evaluations.
2.3 Contamination by carry-over can occur whenever high level and low level
samples are sequentially analyzed. To reduce carryover, the purging
device and sampling syringe must be rinsed with reagent water between
sample analyses. Whenever an unusually concentrated sample is
encountered, it should be followed by an analysis of reagent water to
check for cross contamination. For samples containing large amounts of
water soluble materials, suspended solids, high boiling compounds or
high purgeable levels, it may be necessary to wash out the purging
device with a detergent solution, rinse it with distilled water, and
then dry it in a 105eC oven between analyses. The trap and other parts
of the system are also subject to contamination; therefore, frequent
bakeout and purging of the entire system may be required.
2.4 The laboratory where volatile analysis is performed should be
completely free of solvents.
3. Apparatus and Materials
3.1 Micro syringes - 25 uL and larger, 0.006 inch ID needle.
3.2 Syringe valve - two-way, with Luer ends (three each), if applicable to
the purging device.
3.3 Syringe - 5 mL, gas tight with shut-off valve.
3.4 Balance-Analytical, capable of accurately weighing + 0.0001 g. and a
top-loading balance capable of weighing + 0.1 g.
3.5 Glassware
3.5.1 o Bottle - 15 mL, screw cap, with Teflon cap liner.
o Volumetric flasks - class A with ground-glass stoppers.
o Vials - 2 mL for GC autosampler.
3.6 Purge and trap device - The purge and trap device consists of three
separate pieces of equipment; the sample purger, trap and the desorber
Several complete devices are now commercially available.
3.6.1 The sample purger must be designed to accept 5 mL samples with
a water column at least 3 cm deep. The gaseous head space
between the water column and the trap must have a total volume
of less than 15 mL. The purge gas must pass through the water
column as finely divided bubbles, each with a diameter of less
than 3 mm at the origin. The purge gas must be introduced no
D-16/VOA 2/88
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more than 5 mm from the base of the water column. The sample
purger, illustrated in Figure 1, meets these design criteria.
Alternate sample purge devices may be utilized provided
equivalent performance is demonstrated.
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). The minimum specifications for the trap are
illustrated in Figure 2.
3.6.3 The desorber should be capable of rapidly heating the trap to
180°C. The polymer section of the trap should not be heated
higher than 180°C and the remaining sections should not exceed
220°C during bakeout mode. The desorber design, illustrated in
Figure 2, meets these criteria.
3.6.4 The purge and trap device may be assembled as a separate unit
or be coupled to a gas chromatograph as illustrated in Figures
3 and 4.
3.6.5 A heater or heated bath capable of maintaining the purge device
at 40°C + 1°C.
3.7 GC/MS system
3,7.1 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, and gases.
3.7.2 Column - 6 ft long x 0.1 in ID glass, packed with 1% SP-1000 on
Carbopack B (60/80 mesh) or equivalent. NOTE: Capillary
columns may be used for analysis of volatiles, as long as the
Contractor uses the instrumental parameters in EPA Method 524.2
as guidelines, uses the internal standards and surrogates
specified in this contract, and demonstrates that the analysis
meets all of the performance and QA/QC criteria contained in
this contract.
3.7.3 Mass spectrometer - Capable of scanning from 35 to 260 amu •
every 3 seconds or less, utilizing 70 volts (nominal) electron
energy in the electron impact ionization mode and producing a
mass spectrum which meets all the criteria in Table 2 when 50
ng of 4-bromofluorobenzene (BFB) is injected through the gas
chromatograph inlet.
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 acceptable performance criteria (Exhibit E) may be
used. Gas chromatograph to mass spectrometer interfaces
D-17/VOA 2/88
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constructed of all-glass or glass-lined materials are
recommended. Glass can be deactivated by silanizing with
dichlorodimethylsilane.
3.7.5 Data system - A computer system must be interfaced to the mass
spectrometer that allows the continuous acquisition and storage
on machine readable media of all mass spectra obtained
throughout the duration of the chromatographic program. The
computer must have software that allows searching any GC/MS
data file for ions of a specified mass and plotting such ion
abundances versus time or scan number. This type of plot is
defined as an Extracted Ion Current Profile (EICP) . Software
must also be available that allows integrating the abundance in
any EICP between specified time or scan number limits.
4. Reagents
4.1 Reagent water - Reagent water is 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 &
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.
4.4 Stock standard solutions - Stock standard solutions may be prepared
from pure standard materials or purchased and must be traceable to
EMSL/LV supplied standards. Prepare stock standard solutions in
methanol using assayed liquids or gases as appropriate.
4.4.1 Place about 9.8 mL of methanol into a 10.0 mL tared 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.
4.4.2 Add the assayed reference material as described below.
4.4.2.1 Liquids - Using a 100 uL syringe, immediately add
two or more drops of assayed reference material to
the flask then reweigh. The liquid must fall
D-18/VOA 2/88
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directly into the alcohol without contacting the
neck of the flask.
4.4.2.2 Gases - To prepare standards for any of the four
halocarbons that boil below 30°C (bromomethane,
chloroethane, chloromethane, and vinyl chloride),
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 heavy gas rapidly dissolves 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 value and direct a gentle
stream of gas into the methanol meniscus.
4.4.3 Reweigh, dilute to volume, stopper, then mix by inverting the
flask several times. Calculate the concentration in micrograms
per microliter from the net gain in weight. When compound
purity is assayed to be 96% or greater, the weight may be used
without correction to calculate the concentration of the stock
standard. Commercially prepared standards may be used at any *
concentration if they are certified by the manufacturer.
Commercial standards must be traceable to EMSL/LV-supplied
standards.
4.4.4 Transfer the stock standard solution into multiple Teflon-
sealed screw-cap bottles. Store with no headspace at -10"C to
-20eC and protect from light. Once one of the bottles
containing the standard solution has been opened, it may be
used for at most one week.
4.4.5 Prepare fresh standards every two months--for gases or for
reactive compounds such as styrene. All other standards must
be replaced after six months, or sooner if comparison with
check standards indicates a problem.
4.5 Secondary dilution standards - Using stock standard solutions, prepare
secondary dilution standards in methanol that contain the compounds of
interest, either singly or mixed together. (See GC/MS Calibration in
Exhibit E). Secondary dilution standards should be stored with minimal
headspace and should be checked frequently for signs of degradation or
evaporation, especially just prior to preparing calibration standards
from them.
4.6 Surrogate standard spiking solution. Prepare stock standard solutions
for toluene-dg, p-bromofluorobenzene, and 1,2-dichloroethane-d^ in
methanol as described in paragraph 4.4. Prepare a surrogate standard
spiking solution from these stock standards at a concentration of 250
ug/10 mL in methanol.
D-19/VOA 2/88
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4.7 Purgeable Organic Matrix Standard Spiking Solution
4.7.1 Prepare a spiking solution in methanol that contains the
following compounds at a concentration of 250 ug/10.0 mL:
Purgeable Organics
1,1-dichloroethene
trichloroethene
chlorobenzene
toluene
benzene
4.7.2 Matrix spikes also serve as duplicates; therefore, add an
aliquot of this solution to each of two portions from one
sample chosen for spiking.
4.8 BFB Standard - Prepare a 25 ng/uL solution of BFB in methanol.
4.9 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.
5. Calibration •
5.1 Assemble a purge and trap device that meets the specification in
paragraph 3.6. Condition the trap overnight at 180°C in the purge mode
with an inert gas flow of at least 20 cm /min. Daily, prior to use,
condition the traps for 10 minutes while backflushing at 180°C with the
column at 220°C.
5.2 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 paragraph 7.1.2. Calibrate the purge
and trap-GC/MS system using the internal standard technique (paragraph
5.3).
5.3 Internal standard calibration procedure. The three internal standards
are bromochloromethane, 1,4-difluorobenzene, and chlorobenzene-d^, at
50 ug/L at time of purge. Separate initial and continuing calibrations
must be performed for water samples, and medium level soil samples.
5.3.1 Prepare calibration standards at a minimum of five
concentration levels for each TCL parameter and each surrogate
compound. The concentration levels are specified in Exhibit E.
Standards may be stored up to 24 hours, if held in sealed vials
with zero headspace at -10°C to -20"C and protected from light.
If not so stored, they must be discarded after an hour.
5.3.2 Prepare a spiking solution containing each of the internal
standards using the procedures described in paragraphs 4.4 and
4.5. It is recommended that the secondary dilution standard be
prepared at a concentration of 25 ug/mL of each internal
standard compound. The addition of 10 uL of this standard to
D-20/VOA
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5.0 mL of sample or calibration standard would be equivalent of
50 ug/L.
5.3.3 Tune the GC/MS system to meet the criteria in Exhibit E by
injecting BFB. Analyze each calibration standard, according to
paragraph 7, adding 10 uL of internal standard spiking solution
directly to the syringe. Tabulate the area response of the
characteristic ions against concentration for each compound and
internal standard and calculate relative response factors (RRF)
for each compound using equation 1.
EQ. 1 RRF - —
cis
Ais Cx
Where:
Ax - Area of the characteristic ion for the compound
to be measured.
A; - Area of the characteristic ion for the
specific internal standard from Exhibit E.
«
C; - Concentration of the internal standard.
C - Concentration of the compound to be measured.
5.3.4 The average relative response factor (RRF) must be calculated
for all compounds. A system performance check must be made
before this calibration curve is used. Five compounds (the
system performance check compounds) are checked for a minimum
average relative response factor. These compounds (the SPCC)
are chloromethane, 1,1-dichloroethane, bromoform,
1,1,2,2-tetrachloroethane, and chlorobeflSene. Six compounds
(the calibration check compounds, CCC) are used to evaluate the
curve. These compounds the (CCC) are 1,1-Dichloroethene,
Chloroform, 1,2,-Dichloropropane, Toluene, Ethylbenzene, and
Vinyl Chloride. Calculate the % Relative Standard Deviation
(%RSD) of RRF values over the working range of the curve. A
minimum %RSD for each CCC must be met before the curve is
valid.
%RSD - Standard deviation x 100
mean
See instructions for Form VI, Initial Calibration Data for more
details.
5.3.5 Check of the calibration curve must be performed once every 12
hours. These criteria are described in detail in the
instructions for Form VII, Continuing Calibration Check. (see
Exhibit B, Section III). The minimum relative response factor
for the system performance check compounds must be checked. If
this criteria is met, the relative response factor of all
D-21/VOA 2/88
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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. The maximum percent difference allowed for each
compound flagged as 'CCC' in Form VII is checked. Only after
both these criteria are met can sample analysis begin.
5.3.6 Internal standard responses and retention times in all •
standards must be evaluated during or immediately after data
acquisition. If the retention time for any internal standard
changes by more than 30 seconds from the latest daily (12 hour)
calibration standard, the chromatographic system must be
inspected for malfunctions, and corrections made as required.
The extracted ion current profile (EICP) of the internal
standards must be monitored and evaluated for each 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.
6. GC/MS Operating Conditions
%
6.1 These performance tests require the following instrumental parameters:
Electron Energy: 70 Volts (nominal)
Mass Range: 35 - 260
Scan Time: to give at least 5 scans per peak
and not to exceed 3 seconds per scan.
7. Sample Analysis
7.1 Water Samples *
7.1.1 All samples and standard solutions must be allowed to warm to
ambient temperature before analysis.
7.1.2 Recommended operating conditions for the gas chromatograph
Packed column conditions: Carbopak B (60/80 mesh) with 1%
SP-1000 packed in a 6 foot by 2 mm ID glass column with helium
carrier gas at a flow rate of 30 cm /min. Column temperature
is isothermal at 45°C for 3 minutes, then programmed at 8°C per
minute to 220°C and held for 15 minutes. Injector temperature
is 200-225'C. Source temperature is set according to the
manufacturer's specifications. Transfer line temperature is
250-300eC. The recommended carrier gas is helium at 30
cm /sec. (See EPA Method 5.2.4.2 for capillary column
condition.)
7.1.3 After achieving the key ion abundance criteria, calibrate the
system daily as described in Exhibit E.
D-22/VOA 2/88
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7.1.4 Adjust the purge gas (helium) flow rate to 25-40 cm /min.
Variations from this flow rate may be necessary to achieve
better purging and collection efficiencies for some compounds,
particularly chloromethane and bromoform.
7.1.5 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 careful'ly 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 a time when the analyst has determined that the
first sample has been analyzed properly. Filling one 20 mL
syringe would allow the use of only one syringe. If a second
analysis is needed from the 20 mL syringe, it must be analyzed
within 24 hours. Care must also be taken to prevent air from
leaking into the syringe.
»
7.1.6 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.
7.1.6.1 The following procedure will allow for dilutions
near the calculated dilution factor from the
screening procedure: "
7.1.6.1.1 All dilutions are made in volumetric
flasks (10 mL to 100 mL).
7.1.6.1.2 Select the volumetric flask that will
allow for the necessary dilution.
Intermediate dilutions may be necessary
for extremely large dilutions.
7.1.6.1.3 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.
7.1.6.1.4 Inject the proper aliquot from the
syringe prepared in paragraph 7.1.5
into the volumetric flask. Aliquots of
less than 1 mL increments are
prohibited. Dilute the flask to the
D-23/VOA 2/88
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mark with reagent water. Cap the
flask, invert, and shake three times.
7.1.6.1.5 Fill a 5 mL syringe with the diluted
sample as in paragraph 7.1.5.
7.1.6.1.6 If this is an intermediate dilution,
use it and repeat above procedure to
achieve larger dilutions.
7.1.7 Add 10.0 uL of the surrogate spiking solution (4.6) and 10.0 uL
of the internal standard spiking solution (5.3.2) through the
valve bore of the syringe, then close the valve. The surrogate
and internal standards may be mixed and added as a single
spiking solution. The addition of 10 uL of the surrogate
spiking solution to 5 mL of sample is equivalent to a
concentration of 50 ug/L of each surrogate standard.
7.1.8 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.
7.1.9 Close both valves and purge the sample for 11.0 + 0.1 minutes
at ambient temperature.
7.1.10 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 180°C while backflushing
the trap with an inert gas between 20 and 60 cm /rain for four
minutes. If this rapid heating requirement cannot be met, the
gas chromatographic column must be used as a secondary trap by
cooling it to 30°C (or subambient, if problems persist) instead
of the recommended initial temperature of 45°C.
7.1.11 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
pollutant compounds.
7.1.12 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.
7.1.13 If the initial analysis of a sample or a dilution of a sample
has concentration of TCL compounds that exceeds the initial
D-24/VOA 2/88
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calibration range, the sample must be reanalyzed at a higher
dilution. Note: For total xylenes, where three isomers are
quantified as two peaks, the calibration range of each peak
should be considered separately, e.g., a diluted analysis is
not required for total xylenes unless the concentration of
either peak separately exceeds 200 ug/L. Secondary ion
quantitation is only allowed when there are sample
interferences with the primary ion. If secondary ion
quantitation is used, document the reasons in the Case
Narrative. When a sample is analyzed that has saturated ions
from a compound, this analysis must be followed by a blank
reagent water analysis. If the blank analysis is not free of
interferences, the system must be decontaminated. Sample
analysis may not resume until a blank can be analyzed that is
free of interferences.
7.1.14 For water samples, add 10 uL of the matrix spike solution
(paragraph 4.7) to the 5 mL of sample purged. Disregarding any
dilutions, this is equivalent to a concentration of 50 ug/L of
each matrix spike standard.
7.1.15 All dilutions must keep the response of the major constituents
(previously saturated peaks) in the upper half of the linear "
range of the curve.
7.2 Soil/Sediment Samples
Two approaches may be taken to determine whether the low level or
medium level method may 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).
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.
7.2.1 Low Level Soil Method
The low level soil method is based on purging a heated
sediment/ soil sample mixed with reagent water containing the
surrogate and internal standards. Analyze all reagent 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.
D-25/VOA 2/88
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7.2.1.1 The GC/MS system should be set up as in 7.1.2-7.1.4.
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 (5.3)
except for the addition of a 40"C purge temperature.
7.2.1.2 To prepare the reagent water containing the
surrogates and 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 each of the surrogate spiking
solution (4.6) and the internal standard solution to
the syringe through the valve. (Surrogate spiking
solution and internal standard solution may be mixed
together). The addition of 10 uL of the surrogate
spiking solution to 5 g of soil/sediment is
equivalent to 50 ug/kg of each surrogate standard.
7.2.1.3 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 7.2.1 into a tared
purge device. Use a top loading balance. Note and
record the actual weight to the nearest 0.1 g.
7.2.1.4 Immediately after weighing the sample, weigh 5-10 g
of the sediment into a tared crucible. Determine
the percent moisture by drying overnight at 105°C.
Allow to cool in a desiccator before weighing.
Concentrations of individual analytes will be
reported relative to the dry weight of sediment.
Percent moisture
g of sample-g of drv sample
g of sampleX 100 - % moisture
7.2.1.5 Add the spiked reagent water to the purge device and
connect the device to the purge and trap system.
Note: Prior to the attachment of the purge device,
steps 7.2.1.2 and 7.2.1.3 must be performed rapidly
to avoid loss of volatile organics. These steps
must b« performed in a laboratory free of solvent
fumes.
7.2.1.6 Heat the sample to 40°C + 1'C and purge the sample
for 11.0 + 0.1 minutes.
D-26/VOA 2/88
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7.2.1.7 Proceed with the analysis as outlined in 7.1.10
7.1.13. Use 5 mL of the same reagent water as the
reagent blank.
7.2.1.8 For low level soils/sediment add 10 uL of the matrix
spike solution (4.7) to the 5 mL of water (7.2.1.2).
The concentration for a 5 g sample would be
equivalent to 50 ug/kg of each matrix spike '
standard.
7.2.2 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 surrogate and
internal standards. This is purged at ambient temperature. All
samples with an X Factor >1.0 should 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.
7.2.2.1 The GC/MS system should be set up as in 7.1.2 -
7.1.A. This should be done prior to the addition of*
the methanol extract to reagent water. Initial and
continuing calibrations (5.3) are performed by
adding standards in methanol to reagent water and
purging at ambient temperature.
7.2.2.2 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 7.2.1.4.
7.2.2.3 Quickly add 9.0 mL of methanol, then 1.0 mL of the
surrogate spiking solution to the vial. Cap and
shake for 2 minutes. NOTE: Steps 7.2.2.1 and
7.2.2.2 must be performed rapidly to avoid loss of
volatile organics. These steps must be performed in
a laboratory free of solvent fumes.
7.2.2.4 Using a disposable pipette, transfer approximately 1
mL of extract into a GC vial for storage. The
remainder may be disposed of. Transfer
approximately 1 mL of the reagent methanol to a GC
vial for use as the method blank for each case or
set of 20 samples, whichever is more frequent.
These extracts may be stored in the dark at 4°C
(+2°C) prior to analysis.
D-27/VOA 2/88
-------
The addition of a 100 uL aliquot of each of these
extracts in paragraph 7.2.2.6 will give a
concentration equivalent to 6,200 ug/kg of each
surrogate standard.
7.2.2.5 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 Take this Volume of
X Factor Concentration Ranee Methanol Extract
ugAg
0.25
0.5
2.5
12.5
5.0
- 10.0
- 50.0
- 250
500 -
1000 -
5000 -
25,000 -
10,000
20,000
100,000
500,000
uL
100
50
10
100 of 1/50 dilution3
Calculate appropriate dilution factor for concentrations exceeding the table.
Actual concentration ranges could be 10 to 20 times higher than this if
the compounds are halogenated and the estimates are*'from GC/FID.
r\
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.
7.2.2.6 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 7.2.2.5 and a volume of methanol
solvent to total 100 uL (excluding methanol in
standards).
D-28/VOA 2/88
-------
7.2.2.7 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.
7.2.2.8 Proceed with the analysis as outlined in 7.1.9 -
7.1.13. Analyze all reagent blanks on the same
instrument as the samples. The standards should
also contain 100 uL of methanol to simulate the
sample conditions.
7.2.2.9 For a matrix spike in the medium level sediment/soil
samples, add 8.0 mL of methanol, 1.0 mL of surrogate
spike solution (4.6), and 1.0 mL of matrix spike
solution (4.7) in paragraph 7.2.2.2. This results
in a 6,200 ug/kg concentration of each matrix spike
standard 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 7.2.2.6).
8. Qualitative Analysis
8.1 The compounds listed in the Target Compound List (TCL), Exhibit C,
shall be identified by an analyst competent in the interpretation of
mass spectra (see Bidder Responsibility description) by comparison of
the sample mass spectrum to the mass spectrum of a standard of the
suspected compound. Two criteria must be satisfied to verify the
identifications: (1) elution of the sample component at the same GC
relative retention time as the standard component, and (2)
correspondence of the sample component and standard component mass
spectra.
8.1.1 For establishing correspondence of the GC relative retention
time (RRT), the sample component RRT musfr compare within +0.06
RRT units of the RRT of the standard component. For reference,
the standard must be run on the same shift as the sample. If
coelution of interfering components prohibits accurate
assignment of the sample component RRT from the total ion
chromatogram, the RRT should be assigned by using extracted ion
current profiles for ions unique to the component of interest.
8.1.2 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 tuning requirements for BFB. These standard spectra
may be obtained from the run used to obtain reference RRTs.
8.1.3 The requirements for qualitative verification by comparison of
mass spectra are as follows:
8.1.3.1 All ions present in the standard mass spectra at a
relative intensity greater than 10% (most abundant
D-29/VOA 2/88
-------
ion in the spectrum equals 100%) must be present in
the sample spectrum.
8.1.3.2 The relative intensities of ions specified in
8.1.3.1 must agree within plus or minus 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).
8.1.3.3 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 negatives. 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."
8.1.4 If a compound cannot be verified by all of the criteria in
8.1.3.3, but in the technical judgement of the mass spectral
interpretation specialist, the identification is correct, ther.'
the Contractor shall report that identification and proceed
with quantification in 9.
8.2 A library search shall be executed for non-TCL sample components for
the purpose of tentative identification. For this purpose, the 1985
release of the National Bureau of Standards Mass Spectral Library (or
more recent release), containing 42,261 spectra, shall be used.
Computer generated library search routines must not use normalization
routines that would misrepresent the library or unknown spectra when
compared to each other.
f
8.2.1 Up to 10 nonsurrogate organic compounds of greatest apparent
concentration not listed in Exhibit C for the purgeable organic
fraction shall be tentatively identified via a forward search
of the NBS mass spectral 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.
8.2.2 Guidelines for making tentative identification:
8.2.2.1 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.
8.2.2.2 The relative intensities of the major ions should
agree within + 20%. (Example: For an ion with an
D-30/VOA 2/88
-------
abundance of 50 percent of the standard spectra, the
corresponding sample ion abundance must be between
30 and 70 percent.)
8.2.2.3 Molecular ions present in reference spectrum should
be present in sample spectrum.
8.2.2.4 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.
8.2.2.5 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.
8.2.3 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.
9. Quantitative Analysis
9.1 TCL components identified shall be quantified by the internal standard
method. The internal standard used shall be that which is listed in
Exhibit E, Table 2.1. The EICP area of the characteristic ions of
analytes listed in Tables 2 and 3 in this Section^are used.
9.2 Internal standard responses and retention times in all standards must
be evaluated during or immediately after data acquisition. If the
retention time for any internal standard changes by more than 30
seconds from the latest daily (12 hour) calibration standard, the
chromatographic system must be inspected for malfunctions, and
corrections made as required. The extracted ion current profile (EICP)
of the internal standards must be monitored and evaluated for each
sample, blank, matrix spike and matrix spike duplicate. If the EICP
area for any internal standard changes by more than a factor of two
(-50% to +100%), the mass spectrometric system must be inspected for
malfunction and corrections made as appropriate. When corrections are
made, reanalysis of samples analyzed while the system was
malfunctioning is necessary.
9.2.1 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, only submit
data from the analysis with EICPs within the contract limits.
D-31/VOA 2/88
-------
This is considered the initial analysis and must be reported as
such on all data deliverables.
9.2.2 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 Case Narrative all
inspection and corrective actions taken.
9.3 The relative response factor (RRF) from the daily standard analysis is
used to calculate the concentration in the sample. Use the relative
response factor as determined in paragraph 5.3.3 and the equations
below. When TCL 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.n
Water
Concentration
(Ais)(RRF)(V0)
Where:
AX - Area of the characteristic ion for the compound to be
measured
A^s - Area of the characteristic ion for the specific internal
standard from Exhibit E.
Is - Amount of internal standard added in nanograms (ng)
VQ - Volume of water purged in milliliters (mL) (take into
account any dilutions)
Sediment/Soil (medium level)
(Ax)(Is)(Vt)
Concentration ug/kg -
Sediment/Soil (low level)
Concentration ug/kg - (Ais)(RRF)(Wg)(D)
(Dry weight basis)
Where:
AJJ, Ig, A£S - same as for water, above
Vt - Volume of total extract (uL) (use 10,000 uL or a
factor of this when dilutions are made)
D-32/VOA 2/88
-------
V^ - Volume of extract added (uL) for purging
D - 100 - % moisture
100
Ws - Weight of sample extracted (g) or purged
9.4 An estimated concentration for non-TCL components tentatively
identified shall be quantified by the internal standard method. For
quantification, the nearest internal standard free of interferences
shall be used.
9.4.1 The formula for calculating concentrations is the same as in
paragraph 9.3. 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 value from this
quantitation shall be qualified as estimated. This estimated
concentration should be calculated for all tentatively
identified compounds as well as those identified as unknowns.
9.5 Xylenes (o-,m-, & p- isomers) are to be reported as Xylenes (total).
Since o- and p-Xylene overlap, the Xylenes must be quantitated as
m-Xylene. The concentration of all Xylene isomers must be added
together to give the total.
9.6 1,2-Dichloroethene (trans and cis stereoisomers) are to be reported as
1,2-Dichloroettiene (total). The concentrations of both isomers must be
added together to give the total.
9.7 Calculate surrogate standard recovery on all samples, blanks and
spikes. Determine if recovery is within limits and report on
appropriate form.
9.7.1 Calculation for surrogate recovery.
Percent Surrogate Recovery - Q^
_ X 100%
Qa
Where:
Q. - quantity determined by analysis
Q - quantity added to sample
9.7.2 If recovery is not within limits, the following is required:
o Check to be sure 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.
9.7.3 If the reanalysis of the sample solves the problem, then the
problem was within the laboratory's control. Therefore, only
D-33/VOA 2/88
-------
submit data from the analysis with surrogate spike recoveries
within the contract limits. This shall be considered the
initial analysis and shall be reported as such on all data
deliverables.
9.7.4 If the reanalysis of the sample does not solve the problem,
i.e., surrogate recoveries are outside the contract limits for
both analyses, then submit the surrogate spike recovery data
and the sample data from both analyses. Distinguish between
the initial analysis and the reanalysis on all data
deliverables, using the sample suffixes specified in Exhibit B.
9.7.5 If the sample with surrogate recoveries outside the limits is
the sample used for the matrix spike and matrix spike
duplicate, and the surrogate recoveries of the matrix spike and
matrix spike duplicate show the same pattern (i.e., outside the
limits), then the sample, matrix spike, and matrix spike
duplicate do not require reanalysis. Document in the narrative
the similarity in surrogate recoveries.
Table 2
Characteristic Ions for Surrogate and
Internal Standards for Volatile Organic Compounds
Compound Primary Ion Secondary lonCs)
SURROGATE STANDARDS
4-Bromofluorobenzene 95 174, 176
1,2-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-34/VOA 2/88
-------
Table 3
Characteristic Ions for Volatile TCL Compounds
Parameter
Chi or ome thane
Bromome thane
Vinyl chloride
Chloroethane
Methylene chloride
Acetone
Carbon disulfide
1 , 1-Dichloroethene
1 , 1-Dichloroethane
1 , 2-Dichloroethene
Chloroform
1 , 2 -Dichloroethane
2-Butanone
1,1, 1-Trichloroethane
Carbon tetrachloride
Vinyl acetate
Bromodichlorome thane
1,1,2, 2 -Tetrachloroethane
1 , 2 -Dichloropropane
trans-1 , 3-Dichloropropene
Trichloroethene
Dibromochlor ome thane
1,1,2 -Trichloroethane
Benzene
cis-1 , 3-Dichloropropene
Bromoform
2-Hexanone
4-Methyl-2-pentanone
Tetrachloroethene
Toluene
Chlorobenzene
Ethyl benzene
Styrene
Total xylenes
Primary Ion*
50
94
62
64
84
43
76
96
63
96
83
62
72
97
117
43
83
83
63
75
130
129
97
78
75
173
43
43
164
92
112
106
104
106
Secondary
lonCs")
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
86
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
91
114
91
78, 103
91
* The primary ion should be used unless interferences are present, in which
case, a secondary ion may be used.
D-35/VOA
2/88
-------
IV.
^ Simple Inlet
— 2'woy Syringe vetve
£*~ 17cm 20 geuge tyring* needle
6mm O.D. Rubber Septum
V,. in. O.O.
Steinless Steel
113X moleculer
A sieve purge
t/\ gos filter
Purge get
flow control
10mm gloss frit
medium porosity
1. Purging device
Feeling procedure
Construction
Clett
wool 9mm
Crode IS
Silice gel 8em
TonoM 16cm
Clest Snun
wool fr«p "****
Compression fitting
•nui end ferrules
14ft 7-V/oof resistance
wire wrepped solid
Thermocouple/contnHor
sensor
Tubing 25 cm.
0.105 in. I.D.
0.125 in. O.D.
Steinless steel
2. Trep pocking* end construction to include dosorb cepebility
D-36/VOA
2/88
-------
IV.
Corrtof got flow control
Protturo rogulotor
Pur go got
flow control ^
13X moloculor
tiltor
Liquid infection porti
Column ovon
__ ConfirmttofY column
To dotoctor
"-"Xna/yf/ۥ/ column
option*! 4-port column
control
Not*.
All lints
trip ind GC
thould bt hootod
lo*OeC
3. Schematic of pure* ond trop dmvic* — ourgo mod*
Corrtor got How control Liouid injection pom
Column ovon
Pur go got
ftow control ] ,
13X moloculor
^ firtor
n "I "I T—!• c— Confirmotorf column
n -n -v_L> To *«•<*<>'
ional 4-port column
toloction vohro
Hootor control
Not*
All linot,
trop ond GC
thould bo hootod
to S5°C
Hgur* 4. Schomottc of purgo ond trop dovico — dotorb mod*
D-37/VOA
2/88
-------
IV.
FURGE INLET FITTING
SAMPLE OUTLET FITTING
3" i 6mm O 0. GLASS TUBING
SEPTUM
CAP
40ml VIAL
Figure 5. Low Soils Implnger
D-38/VOA
2/88
-------
EXHIBIT D
ANALYTICAL METHODS
FOR SEMIVOLATILES
D-l/SV 2/88
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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 - PROTOCOLS FOR SOIL/SEDIMENT D-12/SV
1. Medium Level Preparation for
Screening and Analysis of
Semivolatiles (BNA) D-12/SV
2. Low Level Preparation for
Screening and Analysis of
Semivolatiles (BNA) D-16/SV
SECTION III - SCREENING OF SEMIVOLATILE ORGANIC EXTRACTS D-27/SV
SECTION IV - GC/MS ANALYSIS OF SEMIVOLATILES D-31/SV
D-2/SV 2/88
-------
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
(Base/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 2/88
-------
1. Method for the Determination of Extractable Semivolatiles fBase/Neutral
and Acid) 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 TCL compounds and the contract required
quantitation limits are listed in Exhibit C.
Problems have been associated with the following compounds covered by
this method. Dichlorobenzidine and 4-chloroaniline can be subject to
oxidative losses during solvent concentration. This is especially true
in the soil/sediment method when concentrating the methylene chloride/
acetone extraction solvent. Hexachlorocyclopentadiene is subject to
thermal decomposition in the inlet of the gas chromatograph, chemical
reaction in acetone solution and photochemical decomposition.
N-nitrosodiphenylamine decomposes in the gas chromatographic inlet
forming diphenylamine and, consequently, cannot be separated from
diphenylamine native to the sample.
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 (UNA) organic
compounds present in the sample.
D-4/SV 2/88
-------
SECTION II
SAMPLE PREPARATION AND STORAGE
D-5/SV 2/88
-------
PART A - SAMPLE STORAGE AND HOLDING TIMES
1. Procedures for Sample Storage
1.1 The samples must be protected from light and refrigerated at 4°C (±2°C)
from the time of receipt until extraction and analysis.
1.2 After analysis, extracts and unused sample volume must be protected
from light and refrigerated at 4eC (±2°C) for the periods specified in
the contract schedule.
2. Contract Required Holding Times
2.1 If separatory funnel or sonication procedures are employed for
extractions for semivolatile analyses, extraction of water samples
shall be completed within 5 days of VTSR (Validated Time of Sample
Receipt), and extraction of soil/sediment samples shall be completed
within 10 days of VTSR. If continuous liquid-liquid extraction
procedures are employed, extraction of water samples shall be started
within 5 days of VTSR.
Extracts of either water or soil/sediment samples must be analyzed
within 40 days following extraction.
D-6/SV 2/88
-------
PART B - SAMPLE PREPARATION FOR EXTRACTABLE SEMIVOIATILES (SNA') IN WATER
1. Summary of Method
A measured volume of sample, approximately one liter, is serially
extracted with methylene chloride at a pH greater than 11 and again at
pH less than 2, using a separatory funnel or a continuous extractor.
The methylene chloride extracts are dried and concentrated separately
to a volume of 1 mL.
2. Interferences
2.1 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 (TICPs). 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.
3. Apparatus and Materials
3.1 Glassware (Brand names and catalog numbers are included for
illustration purposes only).
3.1.1 Separatory funnel - 2,000 mL, with teflon stopcock.
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 stopper is 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).
3.1.7 Vials - Amber glass, 2 mL capacity with Teflon-lined screw cap.
3.1.8 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.)
D-7/SV 2/88
-------
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 - Reagent water is defined as a water in which an
interferent is not observed at or above the CRQL of each parameter of
interest.
4.2 Sodium hydroxide solution (ION) - Dissolve 40 g NaOH in reagent water
and dilute to 100 mL.
4.3 Sodium thiosulfate - (ACS) Granular.
4.4 Sulfuric acid solution (1+1) - Slowly add 50 mL of H2S04 (sp gr.1.84)
to 50 mL of reagent water.
4.5 Acetone, methanol, methylene chloride - Pesticide quality or
equivalent.
4.6 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.
4.7 Surrogate standard spiking solution.
4.7.1 Surrogate standards are added to all samples and calibration
solutions; the compounds specified for this purpose are
phenol-d/-; 2,4,6 tribromophenol; 2-fluorophenol;
nitrobenzene-d^; terphenyl-dj^ and 2-fluorobiphenyl. Two
additional surrogates, one base/neutral and one acid, may be
added.
4.7.2 Prepare a surrogate standard spiking solution that contains the
base/neutral compounds at a concentration of 100 ug/mL, and the
acid compounds at 200 ug/mL. Store the spiking solutions at
4'C (+2'C) in Teflon-sealed containers. The solutions should
checked frequently for stability. These solutions must be
replaced after twelve months, or sooner if comparison with
quality control check samples indicates a problem.
4.8 BNA Matrix standard spiking solution. The matrix spike solution
consists of:
D-8/SV 2/88
-------
Base/Neutrals Acids
1,2,4-trichlorobenzene pentachlorophenol
acenaphthene phenol
2,4-dinitrotoluene 2-chlorophenol
pyrene 4-chloro-3-methylphenol
N-nitroso-di-n-propylamine 4-nitrophenol
1,4-dichlorobenzene
Prepare a spiking solution that contains each of the base/neutral
compounds above at 100 ug/1.0 mL in methanol and the acid compounds at
200 ug/1.0 ml in methanol. Analyze duplicate aliquots of a sample
spiked with 8NA matrix spiking solution.
5. Sample Extraction - Separators Funnel
5.1 Samples may be extracted using separately funnel techniques. If
emulsions prevent acceptable solvent recovery with separatory funnel
extraction, continuous extraction (paragraph 6.) may be used. The
separatory funnel extraction scheme described below assumes a sample
volume of 1-liter.
5.2 Using a 1-liter graduated cylinder, measure out a 1-liter sample
aliquot and place it into a 2-liter separatory funnel. Pipet 1.0 mL
surrogate standard spiking solution into the separatory funnel and mix
well. Check the pH of the sample with wide range pH paper and adjust to
pH >11 with ION sodium hydroxide. Add 1.0 mL of BNA matrix spiking
solution to each of two 1-liter portions from the sample selected for
spiking.
5.3 Add 60 mL methylene chloride to the separatory funnel and extract the
sample by shaking the funnel for two minutes, with periodic venting to
release excess pressure. Allow the organic layer to separate from the
water phase for a minimum of 10 minutes. If the emulsion interface
between layers is more than one-third the volume of the solvent layer,
the analyst must employ mechanical techniques to complete the phase
separation. The optimum technique depends upon the sample, and may
include: stirring, filtration of the emulsion through glass wool,
centrifugation or other physical methods.
Collect the methylene chloride extract in a 250-mL Erlenmeyer flask. If
the emulsion cannot be broken (recovery of less than 80% of the
methylene chloride, corrected for the water solubility of methylene
chloride), transfer the sample, solvent and emulsion into the
extraction chamber of a continuous extractor. Proceed as described in
paragraph 6.3.
5.4 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. Label the combined extract as the base/neutral fraction.
5.5 Adjust the pH of the aqueous phase to less than 2 using sulfuric acid
(1 + 1). Serially extract three times with 60-mL aliquots of methylene
D-9/SV 2/88
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chloride, as per paragraph 5.3. Collect and combine the extracts in a
250-mL Erlenmeyer flask and label the combined extract as the acid
fraction.
5.6 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 extractable organics listed in Exhibit C.
5.7 Transfer the individual base/neutral and acid fractions by pouring
extracts through separate drying columns containing about 10 cm of
anhydrous granular sodium sulfate, and collect the extracts in the
separate K-D concentrators. Rinse the Erlenmeyer flasks and columns
with 20 to 30 mL of methylene chloride to complete the quantitative
transfer.
5.8 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 (80* to 90*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
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 1-2 mL of methylene chloride. A
5-mL syringe is recommended for this operation.
5.9 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 a hot
water bath (80° to 90°C) so that the concentrator tube is partially
immersed in the hot water. Adjust the vertical position of the
apparatus and the water temperature as required to complete the
concentration in 5 to 10 minutes. At the proper rate of distillation
the balls of the column will actively chatter but the chambers will not
flood with condensed solvent. When the apparent volume of liquid
reaches about 0.5 mL, remove the K-D apparatus from the water bath and
allow it to drain for at least 10 minutes while cooling. Remove the
Snyder column and rinse its flask and its lower joint into the
concentrator tube with 0.2 mL of methylene chloride. Adjust the final
volume to 1.0 mL with methylene chloride. If GC/MS analysis will not
be performed immediately, stopper the concentrator tube and store
refrigerated. If the extracts will be stored longer than two days,
they should be transferred to individual Teflon-sealed screw cap
bottles and labeled base/neutral or acid fraction, as appropriate.
D-10/SV 2/88
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5.10 Nitrogen blowdown technique (taken from ASTM Method D3086)
The following method may be used for final concentration, instead of
the procedure outlined in paragraph 5.9. Place the concentrator tube
in a warm water bath (35°C) and evaporate the solvent volume to just
below 1 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, as it may
introduce interferences. The internal wall of the tube must be rinsed
down several times with oethylene chloride during the operation and the
final volume brought to 1 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.
6. Sample Extraction - Continuous Liquid-Liquid Extractor
6.1 Check the pH of the sample with wide-range pH paper and adjust to pH 11
with 10 N sodium hydroxide. Transfer a 1-liter sample aliquot to the
continuous extractor; using a pipet, add 1 mL of surrogate standard
spiking solution and mix well.
6.2 Add 500 mL of methylene chloride to the distilling flask. Add
sufficient reagent water to ensure proper operation and extract for 18
hours. Allow to cool, then detach the boiling flask and dry.
Concentrate the extract as in paragraphs 5.6 through 5.8. Hold the
concentrated extract for combining with the acid extract (see paragraph
6.4).
6.3 Add 500 mL of methylene chloride to a clean distilling flask and attach
it to the continuous extractor. Carefully adjust the pH of the aqueous
phase to less than 2 using sulfuric acid (1 + 1). Extract for 18
hours. Dry and concentrate the extract as described in paragraphs 5.6
through 5.8. Hold the concentrated extract and label as the acid
extract.
6.3.1 If the base/neutral and/or acid extracts cannot be concentrated
to a final volume of 1 mL, dilute the more concentrated extract
to the final volume of the least concentrated extract.
7. The samples 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.
D-ll/SV 2/88
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PART C - PROTOCOLS FOR 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 - 20,000 ug/kg for the low level analysis and
>20,000 ug/kg for medium level analysis for BNA extractables. For soils
only, the extract for pesticide/PCB analysis may be prepared from an aliquot
of the extract for semivolatiles , or in a separate extraction procedure. If
it is prepared from the semivolatile extract, refer to Exhibit D PEST for the
procedures for extraction of pesticides/PCBs .
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 >20,000 ug/kg proceed with GC/MS
analysis of the organics. If the sample concentration is <20,000 ug/kg
discard the medium level extract and follow the low level method.
Screen from 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 concentration is >20,000 ug/kg
in the original sample, discard the 30 g extract and follow the medium level
methods for organics, using medium level surrogates. If the sample
concentration is <20,000 ug/kg, proceed with concentration and the remainder
of the low level method.
1 . Medium Level Preparation for Screening and Analysis of Sernivolatiles
1.1 Scope and Application
This procedure is designed for the preparation of sediment/soil samples
which may contain organic chemicals at a level greater than 20,000
ugAg-
1.1.1. The extracts and sample aliquots prepared using this method are
screened by GC/MS or FID, using capillary columns for
base/neutral and acid priority pollutants, and related organic
chemicals. The results of these screens will determine whether
D-12/SV 2/88
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sufficient quantities of pollutants are present to warrant
analysis by low or medium protocol.
1.1.2 If the screenings indicate no detectable pollutants at the
lower limits of quantitation, the sample should be prepared by
the low level protocol in Section II, Part C, paragraph 2.
1.2 Summary of Method
1.2.1. Approximately 1 g portions of sediment/soil are transferred to
vials and extracted with methylene chloride. The methylene
chloride extract is screened for extractable organics by GC/FID
or GC/MS.
1.2.2 If organic compounds are detected by the screen, the methylene
chloride extract is 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 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.
1.4 Limitations
1.4.1. The procedure is designed to allow quantitation limits for
screening purposes as low as 20,000 ug/kg for extractable
organics. For analysis purposes, the quantitation limits are
20,000 ug/kg for extractable organics. If peaks are present
based on the GC/FID screen, the sample is determined to require
a medium level analysis by GC/MS. Some samples may contain
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.
D-13/SV 2/88
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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 Methylene chloride. Pesticide residue analysis grade or
equivalent.
1.5.3 Methanol. Pesticide residue analysis grade or equivalent.
1.5.4 Acetone. Pesticide residue analysis grade or equivalent.
1.5.5 Base/Neutral and Acid Surrogate Standard Spiking Solution
The compounds specified are phenol-dg, 2,4,6-tribromophenol,
2-fluorophenol, nitrobenzene-dj, terphenyl-d^ and
2-fluorobiphenyl. Prepare a solution containing these
compounds for base/neutral surrogates at a concentration of 100
ug/1.0 mL, and for acid surrogate standards at a concentration
of 200 ug/1.0 mL in methanol. 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.
1.5.6 Base/Neutral and Acid Matrix Standard Spiking solution.
Prepare a spiking solution in methanol that contains the
following compounds at a concentration of 100 ug/1.0 mL for
base/neutrals and 200 ug/1.0 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.
Base 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.
D-14/SV 2/88
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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 15-mL concentrator tubes.
1.6.7 Ultrasonic cell disrupter, Heat Systems Ultrasonics, Inc.,
Model W-385 SONICATOR (475 Watt with pulsing capability, No.
200 1/2 inch tapped disrupter horn plus No. 207 3/4 inch tapped
disrupter 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.
1.7 Medium Level Sample Preparation.
1.7.1. Transfer the sample container into a fume hood. Open the
sample vial. Decant and discard any water layer and then mix
the sample. Transfer 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
proceeding with the next sample to avoid any
cross -contamination.
1.7.1.1 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 Deputy Project Officer
cited in the contract for instructions on how to
handle the sample. Document the instructions in the
Case Narrative. Discard this portion of sample.
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
D-15/SV 2/88
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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 .....
~ g of sample * ~ X 10° ' % molsture
1.7.3 Add 2.0 g of anhydrous powdered sodium sulfate to sample in the
20 mL vial from paragraph 1.7.1 and mix well.
1.7.4 Surrogate Standards are added to all samples, spikes, and
blanks. Add 1.0 mL of surrogate spiking solution to sample
mixture.
1.7.5 Add 1.0 mL of matrix standard spiking solution to each of two 1
g portions from the sample chosen for spiking.
1.7.6 Immediately add 9.0 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.
1.7.6.1. Add only 8.0 mL of methylene chloride to the matrix
spike samples to achieve a final volume of 10 mL.
1.7.7 Loosely pack disposable Pasteur pipets with 2-3 cm glass wool
plugs. Filter the extract through the glass wool and collect
5.0 mL in a concentrator tube.
1.7.8 Concentrate the extract to 1.0 mL by the nitrogen blowdown
technique described in paragraph 2.7.3.
1.7.9 Transfer the concentrate to an autosampler vial for GC/FID or
GC/MS capillary column screening. If the concentrate is
screened, the quantitation limits should be approximately
20,000 ugAg.
1.7.10 Proceed to Section III, paragraph 1.
2. Low Level Preparation" for Screening and Analysis of Semivolatiles (BNA.)
2.1 Summary of Method
A 30 gram portion of sediment is mixed with anhydrous powdered sodium
sulfate and extracted with 1:1 methylene chloride/acetone using an
ultrasonic probe. If the optional low level screen is used, a portion
of this dilute extract is concentrated fivefold and is screened by
GC/FID or GC/MS. If peaks are present at greater than 20,000 ugAg.
discard the extract and prepare the sample by the medium level method.
D-16/SV 2/88
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If no peaks are present at greater than 20,000 ug/kg, the extract is
concentrated. An optional gel permeation column cleanup may be used
before analysis.
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 mist 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 coexrracted from the sample. The extent of
matrix interferences will vary considerably from source to source.
2.3 Apparatus and Materials
2.3.1 Apparatus for determining percent moisture
2.3.1.1 Oven, drying
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 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.
2.3.3.1 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 FiltBT paper, Whatman No. 41 or equivalent.
2.3.6 Kudema-Danish (K-D) apparatus.
2.3.6.1 Concentrator tube - 10 mL, graduated (Kontes
K-570040-1025 or equivalent).
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2.3.6.2 Evaporative flask - 500 mL (Kontes K-570001-0500 or
equivalent).
2.3.6.3 Snyder column - three-ball macro (Kontes
K-503000-0121 or equivalent).
2.3.6.4 Snyder column - two-ball micro (Kontes
K-569001-0219) or equivalent).
2.3.7 Silicon carbide boiling chips - approximately 10/40 mesh. Heat
to 400*C for 30 minutes or Soxhlet extract with methylene
chloride.
2.3.8 Water bath - heated, with concentric ring cover, capable of
temperature control (±2"C). The bath should be used in a hood.
2.3.9 Balance, capable of accurately weighing + 0.01 g.
2.3.10 Vials and caps, 2 mL for GC auto sampler.
2.3.11 Balance - Analytical, capable of accurately weighing + O.OOOlg.
2.3.12 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.
2.3.13 Gel permeation chromatography (GPC) cleanup device. NOTE: GPC
cleanup is highly recommended for all extracts for low level
soils.
2.3.13.1 Automated system
2.3.13.1.1 Gel permeation chromatograph Analytical
Biochemical Labs, Inc. GPC Autoprep
1002 or equivalent including:
2.3.13.1.2 25 mm ID X 600 - 700 mm glass column
packed with 70 g of Bio-Beads SX-3.
2.3.13.1.3 Syringe, 10 mL with Luer-Lock fitting.
2.3.13.1.4 Syringe filter holder and filters -
stainless steel and TFE, Gelman 4310 or
equivalent.
2.3.13.2 Manual system assembled from parts. (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)
D-18/SV 2/88
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2.3.13.2.1 25 mm ID X 600 - 700 mm heavy wall
glass column packed with 70 g of
BIO-Beads SX-3.
2.3.13.2.2 Pump: Altex Scientific, Model No.
1001A, semipreparative, solvent
metering system. Pump capacity - 28
mL/min.
2.3.13.2.3 Detector: Altex Scientific, Model No.
153, with 254 nm UV source and 8-ul
semi-preparative flowcells (2-mm
pathlengths)
2.3.13.2.4 Microprocessor/controller: Altex
Scientific, Model No. 420,
Microprocessor System Controller, with
extended memory.
2.3.13.2.5 Injector: Altex Scientific, Catalog
No. 201-56, sample injection valve,
Tefzel, with 10 mL sample loop.
2.3.13.2.6 Recorder: Linear Instruments, Model
No. 385, 10-inch recorder.
2.3.13.2.7 Effluent Switching Valve: Teflon
slider valve, 3-way with 0.060" ports.
2.3.13.2.8 Supplemental Pressure Gauge with
connecting Tee: U.S.Gauge, 0-200 psi,
stainless steel. Installed as a
"downstream" monitoring device between
column and detector.
Flow rate was typically 5 mL/min. of
methylene chloride. Recorder chart
speed was 0.50 cm/min.
2.3.14 Pyrex glass wool.
2.3.15 Pasteur pipets, disposable.
2.4 Reagents
2.4.1 Sodium Sulfate - anhydrous powdered reagent grade, heated at
400eC for four hours, cooled in a desiccator, and stored in a
glass bottle. Baker anhydrous powder, catalog #73898 or
equivalent.
2.4.2 Methylene chloride, methanol, acetone, isooctane, 2-propanol
and benzene pesticide quality or equivalent.
D-19/SV 2/88
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2.4.3 Reagent water - Reagent water is defined as a water in which an
interferent is not observed at or above the CRQL of each
parameter of interest.
2.4.4 GPC calibration solutions:
2.4.4.1 Corn oil - 200 mg/mL in methylene chloride.
2.4.4.2 Bis(2-ethylhexylphthalate) and pentachlorophenol 4.0
mg/mL in methylene chloride.
2.4.5 Sodium Sulfite, reagent grade.
2.4.6 Surrogate standard spiking solution.
2.4.6.1 Base/neutral and acid surrogate solution.
2.4.6.1.1 Surrogate standards are added to all
samples, blanks, matrix spikes, matrix
spike duplicates, and calibration
solutions; the compounds specified for
this purpose are phenol-dg,
2,4,6-tribromophenol, 2 -fluorophenol,
nitrobenzene-dj, terphenyl-d^ and
2-fluorobiphenyl. Two additional
surrogates, one base/neutral and one
acid may be added.
2.4.6.1.2 Prepare a surrogate standard spiking
solution at a concentration of 100
ug/1.0 mL for base/ neutral and 200
ug/1.0 mL for acids in methanol. Store
the spiking solutions at 4"C (±2°C) in
Teflon-sealed containers. The
solutions must be replaced after twelve
months, or sooner if comparison with
quality control check samples indicate
a problem.
2.4.7 Matrix standard spiking solutions.
2.4.7.1 Base/neutral and acid matrix spiking solution
consists of:
Base/Neutrals (100 ug/1.0 mL) Acids (200 ug/1.0 mL)
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
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Prepare a spiking solution that contains each of the
above 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 indicate a problem.
Matrix spikes also serve as duplicates, therefore,
add volume specified in Sample Extraction section to
each of two 30-g portions from one sample chosen for
spiking.
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.
2.5.1.1 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 Deputy Project Officer
cited in the contract for instructions on how to
handle the sample. Document the instructions in the
Case Narrative. Discard this portion of sample.
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.
g of sample - g of dry sample
2 5 x 100 - % moisture
g of sample
2.5.2.2 Weigh out two 30 g (record weight to nearest 0.1 g)
portions for use as matrix and matrix spike
duplicates according to 2.5.2. When using GPC
cleanup, add 2.0 mL of the base/neutral and acid
matrix spike to each of two portions. When not
D-21/SV 2/88
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using GPC cleanup, add 1.0 mL of base/neutral and
acid matrix spike to each of the other two portions.
2.5.2.3 When using GPC, add 1.0 mL of base/neutral and acid
surrogate standard to the sample. When not using
GPC, add 0.5 mL of BNA surrogate standard to the
sample.
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%. Do NOT use MICROTIP probe.
(If using a sonicator other than Models W-375 or W-385, contact
the Project Officer for appropriate output settings).
2.5.5 Decant and filter extracts through Whatman #41 filter paper
using vacuum filtration or centrifuge and decant extraction
solvent.
2.5.6 Repeat the extraction two more times with 2 additional 100 mL
portions of 1:1 methylene chloride - acetone. Before each
extraction, make certain that the sodium sulfate is free
flowing and not a consolidated mass. As required, break up
large lumps with a clean spatula, or very carefully with the
tip of the probe. Decant off 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.
2.5.6.1 If the sample is to be screened from the low level
method, take 5.0 mL and concentrate to 1.0 mL
following paragraph 2.7.2 or 2.7.3. Note that the
sample volume in this case is 5.0 mL not 10.0 mL as
given in 2.7.2. Screen the extract as per Section
III, paragraph 1., "Screening of Extractable Organic
Extracts." Transfer the remainder of the 1 mL back
to the total extract from paragraph 2.5.6 after
GC/FID or GC/MS screening. (CAUTION: To minimize
sample loss, autosamplers which pre-flush samples
through the syringe should not be used.)
2.5.7 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.
2.5.8 Add one or two clean boiling chips to the evaporative flask and
attach a three-ball Snyder column. Pre-wet the Snyder column
D-22/SV 2/88
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by adding about 1 mL methylene chloride to the top. Place the
K-D apparatus on a hot water bath (80 to 90'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, and make up to 10 mL
volume with methylene chloride.
2.5.9 If GPC cleanup is not used proceed to paragraph 2.7.
2.6. Extract Cleanup
2.6.1 GPC Setup and Calibration
2.6.1.1 Packing the column - Place 70 g of Bio Beads SX-3 in
a 400 mL beaker. Cover the beads with methylene
chloride; allow the beads to swell overnight (before
packing the columns). Transfer the swelled beads to
the column and start pumping solvent through the
column, from bottom to top, at 5.0 mL/min. After
approximately 1 hour, adjust the pressure on the
column to 7 to 10 psi and pump an additional 4 hours
to remove air from the column. Adjust the column
pressure periodically as required to maintain 7 to
10 psi.
2.6.1.2 Calibration of the column - Load 5 mL of the corn
oil solution into sample loop No. 1 and 5 mL of the
phthalatephenol solution into loop No. 2. Inject
the corn oil and collect 10 mL fraction (i.e.,
change fraction at 2-minute intervals) for 36
minutes. Inject the phthalate-phenol solution and
collect 15 mL fractions for 60 minutes. Determine
the corn oil elution pattern by evaporation of each
fraction to dryness followed by a gravimetric
determination of the residue. Analyze the
phthalate-phenol fractions by GC/FID on the DB-5
capillary column, a UV spectrophotometer or a GC/MS
system. Plot the concentration of each component in
each fraction versus total eluent volume (or time)
from the injection points. Choose a "dump time"
which allows >85% removal of the corn oil and >85%
recovery of the bis(2-ethylhexyl)-phthalate. Choose
the "collect time" to extend at least 10 minutes
after the elution of pentachlorophenol. Wash the
column at least 15 minutes between samples. Typical
parameters selected are: Dump time, 30 minutes (150
mL), collect time, 36 minutes (180 mL) and wash
time, 15 minutes (75 mL). The column can also be
D-23/SV 2/88
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calibrated by the use of a 254 mm UV detector in
place of gravimetric and GC analyses of fractions.
Measure the peak areas at various elution times to
determine appropriate fractions.
The SX-3 Bio Beads column may be reused for several
months, even if discoloration occurs. System
calibration usually remains constant over this
period of time if column flovrate remains constant.
2.6.2 GPC Extract Cleanup
Prefilter or load all extracts via the filter holder to avoid
particulates that might stop the flow. Load one 5.0 mL aliquot
of the extract onto the GPC column. Do not apply excessive
pressure when loading the GPC. Purge the sample loading tubing
thoroughly with solvent between extracts. After especially
dirty extracts, run a GPC blank (methylene chloride) to check
for carry-over. Process the extracts using the dump, collect
and wash parameters determined from the calibration and collect
the cleaned extracts in 400 mL beakers tightly covered with
aluminum foil. The phthalate-phenol calibration solution shall
be taken through the cleanup cycle with each set of 23 extracts
loaded into the GPC. The recovery for each compound must be
>85%. This must be determined on a GC/FID, using a DB-5
capillary column, a UV recording spectrophotometer or a GC/MS
system. A copy of the printouts of standard and check solution
are required as deliverables with each case. Show % recovery
on the copy.
2.6.3 Concentrate the extract as per paragraphs 2.5.7 and 2.5.8.
2.7 Final Concentration of Extract with Optional Extract Splitting
Procedure
If the extract in 2.5.8 is to be used only for semivolatile analysis,
it must be concentrated to a volume of 1.0 mL, following the procedure
in 2.7.2.1.
If the extract in 2.5.8 is to be used for both semivolatile and
pesticide/PCB analyses, then it must be split into two portions. In
that case, follow the procedure in 2.7.1 to obtain the pesticide
portion, and follow that with the procedure in 2.7.2.2 to obtain the
semivolatile portion.
Refer to Exhibit D PEST for specific instructions regarding the
treatment of extracts for pesticide analysis.
2.7.1 If the same extract is used for both semivolatile and
pesticide/PCB analyses, to split out the pesticide extract,
transfer 0.5 mL of the 10 mL methylene chloride extract from
2.5.8 to a separate concentrator tube. Add 5 mL of hexane and
a silicon carbide boiling chip and mix using vortex mixer.
Attach a two-ball micro-Snyder column. Pre-wet the Snyder
D-24/SV 2/88
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column by adding 0.5 mL of hexane to the top of the column.
Place the K-D apparatus on a hot water bath (80 - 90eC) 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. Concentrate the extract to an apparent volume of
less than 1 mL. Use Nitrogen blowdown (see 2.7.3) to reduce
the volume to 0.5 mL. Add 0.5 mL of acetone. The pesticide
extract must now be passed through an alumina column to remove
the SNA surrogates and polar interferences. Proceed to
paragraph 2.8 of the pesticide/PCB method (Exhibit D PEST).
2.7.2 Concentration of the semivolatile extract.
2.7.2.1 If the extract in 2.5.8 was not split to obtain a
portion for pesticide analysis, reattach the
micro-Snyder column to the concentrator tube used in
2.5.8 which contains the 10 mL extract and add a
fresh silicon carbide boiling chip to the
concentrator tube. Pre-wet the Snyder column with
0.5 mL of methylene chloride. Place the K-D
apparatus on the hot water bath (80 - 90°C) so that
the concentrator tube is partially immersed in the
hot water. Adjust the vertical position of the
apparatus and the water temperature as required to
complete the concentration in 5 to 10 minutes. When
the apparent volume of the liquid reaches 0.5 mL,
remove the K-D apparatus from the water bath and
allow it to drain for at least 10 minutes while
cooling. Remove the Snyder column and rinse the
lower joint into the concentrator tube with 0.2 mL
of methylene chloride. Adjust the final volume to
1.0 mL with methylene chloride. If GPC cleanup was
used, this 1.0 mL represents a two-fold dilution to
account for only half of the extract going through
the GPC.
2.7.2.2 If the extract in 2.5.8 was split in 2.7.1 to obtain
a portion for pesticide analysis, reattach the
micro-Snyder column to the concentrator tube used in
2.5.8 which contains the 9.5 mL extract and add a
fresh 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 - 90eC) so that
thS concentrator tube in partially immersed in the
hot water. Adjust the vertical position of the
apparatus and the water temperature as required to
complete the concentration in 5 to 10 minutes. When
the apparent volume of the liquid reaches 0.5 mL,
remove the K-D apparatus from the water bath and
allow it to drain for at least 10 minutes while
cooling. Remove the Snyder column and rinse the
lower joint into the concentrator tube with 0.2 mL
D-25/SV 2/88
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of methylene chloride. Adjust the final volume to
0.95 mL with methylene chloride. If GPC cleanup was
used, this 0.95 mL represents a twofold dilution to
account for only half of the extract going through
the GPC, and therefore, the sample detection limit
for the sample would be 2x CRQL (see Exhibit B).
2.7.3 Nitrogen blowdown technique (taken from ASTM Method D 3086).
The following method may be used for final concentration of the
UNA extract instead of the procedures in paragraph 2.7.2.
Place the concentrator tube in a warm water bath (35°C) and
evaporate the solvent volume to below 1 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.
If the extract in 2.5.8 was not split for both semivolatile and
pesticide analyses, bring the final volume of the extract to
1.0 mL with methylene chloride. This represents a ten-fold
concentration. If the extract in 2.5.8 was split in 2.7.1,
then bring the final volume of the semivolatile portion to 0.95
mL with methylene chloride. This represents a similar ten-fold
concentration. In either case, if GPC cleanup techniques were
employed, the final volume (1.0 or 0.95 mL) represents a
two-fold dilution to account for the fact that only half the
extract went through the GPC.
2.7.4 Store all extracts at 4eC (±2'C) in the dark in Teflon-sealed
containers.
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SECTION III
SCREENING OF SEMIVOLATILE
ORGANIC EXTRACTS
D-27/SV 2/88
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1. Summary of Method
1.1 The solvent extracts of water and sediment/soil are screened on a gas
chromatograph/flame ionization detector (GC/FID) using a fused silica
capillary column (FSCC). The results of the screen will determine the
concentration of extract taken for GC/MS analysis.
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 96% or greater, the weight may be used
without correction to calculate the concentration
of the stock standard. Commercially prepared stock
standards may be used at any concentration if they
are certified by the manufacturer or by an
independent source and are traceable to
EMSL/LV-supplied standards.
3.2.1.2 Transfer the stock standard solutions into Teflon
sealed screw-cap bottles. Store at -10*C to -20°C
and protect from light. Stock standard solutions
should be checked frequently for signs of
degradation or evaporation, especially just prior
to preparing calibration standards from them.
Stock standard solutions must be replaced after six
months or sooner if comparison with quality control
D-28/SV 2/88
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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
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:
4.1.1 Standardized for half scale response from 50 ng of
phenanthrene.
4.1.2 Adequately separates phenol from the solvent front.
4.1.3 Minimum of quarter scale response for 50 ng of
di-n-octylphthalate.
5. GC/FID Screening
5.1 Suggested GC operating conditions:
Initial Column Temperature Hold - 50*C for 4 minutes
Column Temperature Program - 50 - 280°C at 8 degrees/min.
Final Column Temperature Hold - 280*C for 8 minutes
Injector - Grob-type, splitless
Sample Volume - 1 uL - 2 uL
Carrier Gas - Helium at 30 cm /sec
5.2 Inject the GC calibration standard and ensure the criteria specified in
4. are met before injecting samples. Estimate the response for 10 ng
of phenanthrene.
5.3 Inject the appropriate extracts from Section II, including blanks.
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.
D-29/SV 2/88
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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, paragraph 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 6. to perform the GC/MS analysis of extracta-
bles in Section IV, GC/MS Analysis of Semivolatiles, paragraph 1.
D-30/SV 2/88
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SECTION IV
GC/MS ANALYSIS OF SEMIVOLATILES
D-31/SV 2/88
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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/PCBs identified by GC/EC, if concentrations permit.
2. Apparatus and Materials
2.1 Gas chromatograph/mass spectrometer system.
2.1.1 Gas chromatograph - An analytical system complete with a
temperature programmable gas chromatograph suitable for
splitless injection and all required accessories including
syringes, analytical columns and gases.
2.1.2 Column - 30 m x 0.25 mm ID (or 0.32 mm) bonded-phase silicone
coated fused silica capillary column (J&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 required criteria when 50 ng of
decafluorotriphenylphosphine (DFTPP) is injected through the GC
inlet. 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 Government.
2.1.4 Data system - A computer system must be interfaced to the mass
spectrometer that allows the continuous acquisition and storage
on machine readable media of all mass spectra obtained
throughout the duration of the chromatographic program. The
computer must have software that allows searching any GC/MS
data file for ions of a specific mass and plotting such ion
abundances versus time or scan number. This type of plot is
defined as an Extracted Ion Current Profile (EICP). Software
must also be available that allows integrating the abundance in
any EICP between specified time or scan number limits.
3. Reagents
3.1 Internal standards - 1,4 dichlorobenzene-d^, naphthalene-dg,
acenaphthene-d^Q, phenanthrene-d^Q, chrysene-dj^, perylene-dj^.
An internal standard solution can be prepared by dissolving 200 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
4000 ng/uL. A 10 uL portion of this solution should be added to each 1
D-32/SV 2/88
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mL of sample extract. This will give a concentration of 40 ng/uL of
each constituent.
3.2 Prepare calibration standards at a minimum of five concentration
levels. Each calibration standard should contain each compound of
interest and each surrogate standard. (See GC/MS calibration in
Exhibit E for calibration standard concentration.)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 should be prepared
weekly and stored at 4°C (±2eC).
4. Calibration
4.1 Each GC/MS system must have the hardware tuned to meet the criteria
listed in Exhibit E for a 50 ng injection of decafluorotriphenyl
phosphine (DFTFP). No sample analyses can begin until all these
criteria are met. This criteria must be demonstrated each 12 hour
shift. DFTPP has to be injected to meet this criterion.
Post-acquisition manipulation of abundances is not acceptable.
4.2 The internal standards selected in paragraph 2.3.1 should permit most
components of interest in a chromatogram to have retention times of
0.80 to 1.20 relative to the internal standards (see instructions for
Form VI, Initial Calibration Data). Use the base peak ion from the
specific internal standard as the primary ion for quantification, found
in Exhibit E, Table 2.2. If interferences are noted, use the next most
intense ion as the secondary ion, i.e. For 1,4-dichlorobenzene-d- use
m/z 152 for quantification.
4.2.1 The internal standards are added to all calibration standards
and all sample extracts 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.
4.3 Analyze 1 uL of each calibration standard and tabulate the area of the
primary characteristic ion against concentration for each compound
including the surrogate compounds. Calculate relative response factors
(RRF) for each compound using Equation 1.
AX Cis
RRF - -T— X 75— Equation 1.
Ais cx
Where:
Ay - Area of the characteristic ion for the compound to be measured.
Aj_ - Area of the characteristic ion for the specific internal
standard from Exhibit E.
Cis " Concentration of the internal standard (ng/uL).
C-, - Concentration of the compound to be measured (ng/uL).
X
D-33/SV 2/88
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4.3.1 The average relative response factor (RRF) should be calculated
for all compounds. A system performance check must be made
before this calibration curve is used. Four compounds (the
system performance check compounds) are checked for a minimum
average relative response factor. These compounds (the SPCC)
are N-nitroso-di-n-propylamine, hexachlorocyclopentadiene,
2,4-dinitrophenol, 4-nitrophenol. See instructions in Exhibit
E for Form VI, Initial Calibration Data for more details.
4.3.2 A % Relative Standard Deviation (%RSD) is calculated for
thirteen compounds labeled the Calibration Check Compounds
(CCC) on Form VI SV and in Table 2.3, Exhibit E, III SV. A
maximum % RSD is also specified for these compounds. These
criteria must be met for the calibration curve to be valid.
4.4 A check of the calibration curve must be performed once every 12 hours
during analysis. These criteria are described in detail in the
instructions for Form VII, Calibration Check. The minimum relative
response factor for the system performance check compounds must be
checked. If this criteria is met, the relative response factors of all
compounds are calculated. A percent difference of the daily (12 hour)
relative response factor compared to the average relative response
factor from the initial curve is calculated. A maximum percent
difference is allowed for each compound flagged as 'CCC' on Form VII.
Only after both these criteria are met can sample analysis begin.
4.5 Internal standard responses and retention times in all standards must
be evaluated during or immediately after data acquisition. If the
retention time for any internal standard changes by more than 30
seconds from the latest daily (12 hour) calibration standard, the
chromatographic system must be inspected for malfunctions, and
corrections made as required. The extracted ion current profile (EICP)
of the internal standards must be monitored and evaluated for each
standard. If 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.
5. GC/MS Analysis
5.1 The following instrumental parameters are required for all performance
tests and for all sample analyses:
Electron Energy - 70 volts (nominal)
Mass Range - 35 to 500 amu
Scan Time - not to exceed 1 second per scan
5.2 Combine 0.5 ml of the base/neutral extract and 0.5 mL of acid from the
water extract prior to analysis.
5.3 Internal standard solution is added to each sample extract. For water
and/or medium soil extracts, add 10 uL of internal standard solution to
each accurately measured 1.0 mL of sample extract. If the low soil
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extracts required a pesticide split (see Section II, Part C, paragraph
2.7), add 9.5 uL of internal standard solution to each accurately
measured 0.95 mL of sample extract. Analyze the 1.0 mL extract by
GC/MS using a bonded-phase silicone-coated fused silica capillary
column. The recommended GC operating conditions to be used are as
follows:
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 — 1 - 2 uL
Carrier Gas - Helium at 30 cm3/sec
NOTE: 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/uL of each constituent in the extract
volume. If the concentration on the column of any compound
exceeds the initial calibration range, the extract must be
diluted and reanalyzed. See Exhibit E, Section III, SV, Part 6.
Secondary ion quantisation is only allowed when there are
sample interferences with the primary ion. If secondary ion
quantitation is performed, document the reasons in the Case
Narrative.
6. Qualitative Analysis
6.1 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 PreAward Bid Confirmation description) by comparison
of the sample mass spectrum to the mass spectrum of a standard of the
suspected compound. Two criteria must be satisfied to verify the
identifications: (1) elution of the sample component at the GC
relative retention time as the standard component, and (2)
correspondence of the sample component and standard component mass
spectra.
6.1.1 For establishing correspondence of the GC relative retention
time (RRT), the sample component RRT must compare within ±0.06
RRT units of the RRT of the standard component. For reference,
the standard must be run on the same shift as the sample. If
coelution of interfering components prohibits accurate
D-35/SV 2/88
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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.
6.1.2 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 tuning requirements. These standard spectra
may be obtained from the run used to obtain reference RRTs.
6.1.3 The requirements for qualitative verification by comparison of
mass spectra are as follows:
6.1.3.1 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.
6.1.3.2 The relative intensities of ions specified in (1)
must agree within plus or minus 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.)
6.1.3.3 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."
6.1.4 If a compound cannot be verified by all of the criteria in
6.1.3, 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 7.
6.2 A library search shall be executed for non-TCL sample components for
the purpose of tentative identification. For this purpose, the 1985
release of the National Bureau of Standards Mass Spectral Library (or
more recent release), containing 42,261 spectra, shall be used.
6.2.1 Up to 20 nonsurrogate organic compounds of greatest apparent
concentration not listed in Exhibit C for the combined base/
neutral/acid fraction shall be tentatively identified via a
forward search of the NBS 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
D-36/SV 2/88
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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.
6.2.2 Guidelines for making tentative identification:
6.2.2.1 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.
6.2.2.2 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.)
6.2.2.3 Molecular ions present in reference spectrum should
be present in sample spectrum.
6.2.2.4 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.
6.2.2.5 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 can
sometimes create these discrepancies.
6.2.3 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.
7. Quantitation
7.1 TCL 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 Exhibit E, Tables 2.1
and 2.2). The EICP area of characteristic ions of analytes listed in
Tables 4, 5 and 6 are used.
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 30
seconds from the latest daily (12 hour) calibration standard, the
chromatographic system must be inspected for malfunctions, and
D-37/SV 2/88
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corrections made as required. The extracted ion current profile (EICP)
of the internal standards must be monitored and evaluated for each
sample, blank, matrix spike and matrix spike duplicate. The criteria
are described in detail in the instructions for Form VIII, Internal
Standard Area Summary. If the EICP area for any internal standard
changes by more than a factor of two (-50% to +100%), the mass
spectrometric system must be inspected for malfunction and corrections
made as appropriate. If the analysis of a subsequent sample or
standard indicates that the system is functioning properly, then
corrections may not be required. The samples or standards with EICP
areas outside the limits must be re-analyzed, and treated according to
7.1.1 and 7.1.2 below. If collections 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.
7.1.1 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, only submit
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.
7.1.2 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 Case Narrative all
inspection and corrective actions taken.
7.2 The relative response factor (RRF) from the daily standard analysis is
used to calculate the concentration in the sample. Secondary ions may
be used if interferences are present. 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 TCL
Compounds are below contract required quantitation limits (CRQL) but
the spectra 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."
7.2.1 Calculate the concentration in the sample using the relative
response factor (RRF) as determined in paragraph 4.3 and the
following equation:
D-38/SV 2/88
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Concentration ug/L - (Ais)(RRF)(VQ)(V1)
A^ - Area of the characteristic ion for the compound to be
measured
A^g - Area of the characteristic ion for the internal standard
I — Amount of internal standard injected in nanograms (ng)
VQ - Volume of water extracted in milliliters (mL)
V, - Volume of extract injected (uL)
Vt - Volume of total extract
(Use 2000 uL or a factor of this when dilutions are made. The
2,000 uL is derived from combining half of the 1 mL UN extract
and half of the 1 mL A extract.)
Soil/Sediment
Concentration ug/kg - -
(Dry weight basis) (Ais) (RRF) (V^ (Wg) (D)
Where:
Aj^.Ig.A^g - Same as given for water, above
Vt - Volume of low level total extract (Use 1000
uL or a factor of this when dilutions are
made. If GPC cleanup is used, the volume is
2,000 uL. The 1000 uL is derived from
concentrating the 9.5 mL extract to 0.95
mL.)
- OR -
Vfc - Volume of medium level extract (Use 2,000 uL
or a factor of this when dilutions are made.
The 2,000 uL is derived from concentrating 5
mL of the 10 mL extract to 1 mL.)
V* - Volume of extract injected (uL)
D - 100 - % moisture
100
W - Weight of sample extracted (grams)
s
D-39/SV 2/88
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7.3 An estimated concentration for non-TCL components tentatively
identified shall be quantified by the internal standard method. For
quantification, the nearest internal standard free of interferences
shall be used.
7.3.1 The formula for calculating concentrations is the same as in
paragraph 7.2.1. 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 value from this
quantitation shall be qualified as estimated. This estimated
concentration should be calculated for all tentatively
identified compounds as well as those identified as unknowns.
7.4 Calculate surrogate standard recovery on all samples, blanks and
spikes. Determine if recovery is within limits and report on
appropriate form.
7.4.1 If recovery is not within limits (i.e., if two surrogates from
either base/neutral or acid fractions are out of limits or if
recovery of any one surrogate in either fraction is below 10%),
the following is required.
o Check to be sure 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.
7.4.2 If the reanalysis of the sample solves the problem, then the
problem was within the laboratory's control. Therefore, only
submit 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.
7.4.3 If none of the steps in 7.4.1 or 7.4.2 solve the problem, then
reextract and reanalyze the sample. If the reextraction and
reanalysis of the sample solves the problem, then the problem
was within the laboratory's control. Therefore, only submit
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.
7.4.4 If the reextraction 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
spike recovery data and the sample analysis data from analysis
of both sample extracts. Distinguish between the initial
analysis and the reanalysis on all data deliverables, using the
sample suffixes specified in Exhibit B.
D-40/SV 2/88
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7.4.5 If the sample with surrogate recoveries outside the limits is
the sample used for the matrix spike and matrix spike duplicate
and the surrogate recoveries of the matrix spike and matrix
spike duplicate show the same pattern (i.e., outside the
limits), then the sample, matrix spike and matrix spike
duplicate do not require re-analysis.
Document in the narrative the similarity in surrogate
recoveries.
D-41/SV 2/88
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Table 4.
Characteristic Ions for Semivolatile TCL Compounds
Parameter
Primary Ion
Secondary Ion(s)
Phenol
bis(-2-Chloroethyl)Ether
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Benzyl Alcohol
1,2-Dichlorobenzene
2-Methylphenol
b is(2 -chloro isopropyl)Ether
4-Methylphenol
N-Nitroso-Di-Propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2,4-Dimethylphenol
Benzoic Acid
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
(continued)
94
93
128
146
146
108
146
108
45
108
70
117
77
82
139
107
122
93
162
180
128
127
225
107
142
237
196
196
162
65, 66
63, 95
64, 130
148, 113
148, 113
79, 77
148, 113
107
77, 79
107
42, 101, 130
201, 199
123, 65
95, L38
65, 109
121. 122
105, 77
95, 123
164, 98
182, 145
129, 127
129
223, 227
144, 142
141
235, 272
198, 200
198, 200
164, 127
D-42/SV
2/88
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Table 4. (continued)
Characteristic Ions for Semivolatile TCL Compounds
Parameter Primary Ion Secondary lonfs")
2-Nitroaniline 65 92, 138
Dimethyl Phthalate 163 194, 164
Acenaphthylene 152 151, 153
3-Nitroaniline 138 108, 92
Acenaphthene 153 152, 154
2,4-Dinitrophenol 184 63, 154
4-Nitrophenol 109 139, 65
Dibenzofuran 168 139
2,4-Dinitrotoluene 165 63, 182
2,6-Dinitrotoluene 165 89, 121
Diethylphthalate 149 177, 150
4-Chlorophenyl-phenylether 204 206, 141
Fluorene 166 165, 167
4-Nitroaniline 138 92, 108
4,6-Dinitro-2-Methylphenol 198 182, 77
N-Nitrosodiphenylamine 169 168, 167
4-Bromophenyl-phenylether 248 250, 141
Hexachlorobenzene 284 142, 249
Pentachlorophenol 266 264, 268
Phenanthrene 178 179, 176
Anthracene 178 179, 176
Di-N-Butylphthalate 149 150, 104
Fluoranthene 202 101, 100
Pyrene 202 101, 100
Butylbenzylphthalate 149 91, 206
3,3'-Dichlorobenzidine 252 254, 126
Benzo(a)Anthracene 228 229, 226
bis(2-Ethylhexyl)Phthalate 149 167, 279
Chrysene 228 226, 229
Di-N-Octyl Phthalate 149
Benzo(b)Fluoranthene 252 253, 125
Benzo(k)Fluoranthene 252 253, 125
Benzo(a)Pyrene 252 253, 125
Indeno(1,2,3-cd)Pyrene 276 138, 227
Dibenz(a, h)Anthracene 278 139, 279
Benzo(g, h, i)Perylene 276 138, 277
D-43/SV 2/88
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Table 5.
Characteristic Ions for Pesticides/PCBs
Parameter Primary Ion Secondary lonCs)
Alpha-BHC 183 181, 109
Beta-BHC 181 183, 109
Delta-BHC 183 181, 109
Gannna-BHC (Lindane) 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
Endosulfan II 337 339, 341
4,4'-ODD 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
Endrin Ketone 317 67, 319
D-44/SV 2/88
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Table 6.
Characteristic Ions for Surrogates and
Internal Standards for Semivolatile Compounds
SURROGATES Primary Ion Secondary lon(s)
Phenol-d5 99 42, 71
2-Fluorophenol 112 64
2,4,6-Tribromophenol 330 332, 141
d-5 Nitrobenzene 82 128, 54
2-Fluorobiphenyl 172 171
Terphenyl 244 122, 212
INTERNAL STANDARDS
l,4-Dichlorobenzene-d4 152 115
Naphthalene-dg 136 68
Acenapthene-d1Q 164 162, 160
Phenanthrene-d1Q 188 94, 80
Chrysene-d12 24° 120> 236
Perylene-d12 264 ' 260, 265
D-45/SV 2/88
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EXHIBIT D
ANALYTICAL METHODS
FOR PESTICIDES/PCBs
D-l/PEST
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Table of Contents
Page
SECTION I INTRODUCTION D-3/PEST
SECTION II SAMPLE PREPARATION AND STORAGE D-5/PEST
PART A SAMPLE STORAGE AND HOLDING TIMES D-6/PEST
PART B SAMPLE PREPARATION FOR PESTICIDES/PCBs
IN WATER D-7/PEST
PART C PROTOCOLS FOR SOIL/SEDIMENT D-14/PEST
1. Medium Level Preparation for Analysis
of Pesticide/PCBs D-14/PEST
2. Low Level Preparation for Analysis
of Pesticide/PCBs D-19/PEST
SECTION III SCREENING OF PESTICIDE/PCB EXTRACTS D-31/PEST
SECTION IV GC/EC ANALYSIS OF PESTICIDES/PCBs D-33/PEST
D-2/PEST
2/88
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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 608
(Pesticides and PCBs).
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 detector to
determine the concentration level of pesticides/PCBs. The analysis section
contains the gas chromatograph/electron capture detector (GC/EC) method for
pesticides and PCBs.
D-3/PEST 2/88
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1. Method for the Determination of Pesticides
1.1 Scope and Application
This method covers the determination of certain TCL organochloride
pesticides and polychlorinated biphenyls as listed in Exhibit C. The
contract required quantitation limits are also listed in Exhibit C.
Because weathering and/or different formulations of chlordane usually
modify the chromatographic pattern exhibited by technical chlordane,
the use of this method is not appropriate for the determination of
technical chlordane.
The analysis of the isomers alpha chlordane and gamma chlordane by this
method is appropriate however.
1.2 The method involves solvent extraction of the matrix, analysis of the
extract on a gas chromatograph/electron capture detector (GC/EC) using
a packed column, and confirmation on a GC/EC using a second packed
column. (An optional fused silica capillary column may be used for
confirmation.) If concentration permits, confirmation is to be done on
GC/MS.
D-4/PEST 2/88
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SECTION II
SAMPLE PREPARATION AND STORAGE
D-5/PEST 2/88
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PART A - SAMPLE STORAGE AND HOLDING TIMES
1. Procedures for Sample Storage
1.1 The samples must be protected from light and refrigerated at 4°C (+
2eC) from the time of receipt until extraction and analysis.
1.2 After analysis, extracts and unused sample volume must be protected
from light and refrigerated at 4" C (+ 2° C) for the periods specified
in the contract schedule.
2. Contract Required Holding Times
2.1 If separatory funnel or sonication procedures are employed for
extractions for pesticide/ PCB analyses, extraction of water samples
shall be completed within 5 days of VTSR (Validated Time of Sample
Receipt), and extraction of soil/ sediment samples shall be completed
within 10 days of VTSR. If continuous liquid-liquid extraction
procedures are employed, extraction of water samples shall be started
within 5 days of VTSR.
2.2 Extracts of either water or soil/sediment samples must be analyzed
within 40 days following extraction.
D-6/PEST 2/88
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PART B - SAMPLE PREPARATION FOR PESTICIDES/PCBs IN WATER
1. Summary of Method
A measured volume of sample, approximately one-liter, is solvent
extracted with methylene chloride using a separatory funnel or a
continuous extractor. The methylene chloride extract is dried,
exchanged to hexane and adjusted to a final volume of 10 mL.
2. Interferences
2.1 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 gas chromatograms. All
of these materials must be routinely demonstrated to be free from
interferences under the conditions of the analysis by running
laboratory reagent blanks. Interferences by phthalate esters can pose
a major problem in pesticide analysis when using the electron capture
detector. These compounds generally appear in the chromatogram as broad
eluting peaks. Common flexible plastics contain varying amounts of
phthalates. These phthalates are easily extracted or leached from such
materials during laboratory operations. Cross-contamination of clean
glassware routinely occurs when plastics are handled. Interferences
from phthalates can best be minimized by avoiding the use of plastics
in the laboratory. Exhaustive cleanup of reagents and glassware may be
required to eliminate background phthalate contamination.
2.2 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. The cleanup procedures in
paragraphs 7.1 thru 7.5 must be used to overcome such interferences to
attempt to achieve the CRQLs. The cleanup procedures in paragraph 8.1
through 8.5 may be used to remove sulfur interferences.
3. Apparatus and Materials
3.1 Glassware (Brand names and catalog numbers included for illustration
purposes only).
3.1.1 Separatory funnel - 2000 mL with Teflon stopcock.
3.1.2 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.)
3.1.3 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 stopper is used
to prevent evaporation of extracts.
3.1.4 Evaporative flask - Kudema-Danish, 500 mL (Kontes K-570001-
0500 or equivalent). Attach to concentrator tube with springs.
D-7/PEST 2/88
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3.1.5 Snyder column - Kudema-Danish, Three-ball macro (Kontes
K-503000-0121 or equivalent).
3.1.6 Snyder column - Kuderna-Danish, Two-ball micro (Kontes
K-569001-0219 or equivalent).
3.1.7 Continuous liquid-liquid extractors - Equipped with Teflon or
glass connecting joints and stopcocks requiring no lubrication.
(Hershberg-Wolf Extractor-Ace Glass Company, Vineland, NJ P/N
6841-10, or equivalent.)
3.1.8 Vials - Amber glass, 10 to 15 mL capacity, with Teflon-lined
screw cap.
3.1.9 Bottle or test tube - 50 mL with Teflon-lined screw cap for
sulfur removal.
3.1.10 Chromatographic column for alumina - 8 mL (200 mm X 8 mm ID)
Polypropylene column (Kontes K-420160 or equivalent) or 6 mL
(150 mm x 8 mm ID) glass column (Kontes K-420155 or equivalent)
or 5 mL serological pipettes plugged with a small piece of
Pyrex glass wool in the tip. The Kontes columns may be plugged
with Pyrex glass wool or a polyethylene porous disk (Kontes
K-420162).
3.2 Pyrex glass wool - Pre-rinse glass wool with appropriate solvents to
ensure its cleanliness.
3.3 Silicon carbide boiling chips - Approximately 10/40 mesh. Heat to
400°C for 30 minutes or Soxhlet extract with methylene chloride.
3.4 Water bath - Heated, with concentric ring cover, capable of temperature
control (+ 2°C) . The bath should be used in a hood.
3.5 Balance - Analytical, capable of accurately weighing + 0.0001 g.
3.6 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 - Reagent water is defined as a water in which an
interferent is not observed at or above the CRQL of each parameter of
interest.
4.2 Acetone, hexane, isooctane (2,2,4-trimethylpentane), methylene chloride
Pesticide quality or equivalent.
4.3 Sodium sulfate - (ACS) granular, anhydrous. Purify by heating at 400°C
for 4 hours in a shallow tray.
4.4 Alumina - Neutral, Super I Woelm (Universal Scientific, Incorporated,
Atlanta, Georgia) or equivalent. Prepare activity III by adding 7%
D-8/PEST 2/88
-------
(v/w) reagent water to the Super I neutral alumina. Tumble or shake in
a wrist action shaker for a minimum of 2 hours or preferably overnight.
There should be no lumps present. Store in a tightly sealed glass
container. A 25 cycle soxhlet extraction of the alumina with methylene
chloride is required if a solvent blank analyzed by the pesticide
technique indicates any interferences for the compounds of interest.
4.4.1 Alumina Equivalency Check. Test the alumina by adding the BNA
surrogates (see Exhibit D SV) in 1:1 acetone/hexane to the
alumina and following paragraph 7.1. The tribromophenol should
not be detected by GC/EC if the alumina and its activation are
acceptable. Also check recovery of all single component
pesticides following the same procedure. The percent recovery
for all single component pesticides must be >80%, except for
endosulfan sulfate which must be >60% and endrin aldehyde which
is not recovered. The data must be retained by the laboratory
and made available for inspection during on-site evaluations.
If the alumina deactivated with 7% (v/w) reagent water does not
prove adequate to remove the BNA surrogates and other
interferences, the alumina may be deactivated with as much as
9% reagent water, so long as the criteria for tribromophenol
and the recovery of all single component pesticides can be met.
4.5 Sodium hydroxide solution (ION)-(ACS). Dissolve 40 g NaOH in reagent
water and dilute to 100 mL.
4.6 Tetrabutylammonium (TEA) - Sulfite reagent. Dissolve 3.39 g
tetrabutylammonium hydrogen sulfate in 100 mL distilled water. To
remove impurities, extract this solution three times with 20 mL
portions of hexane. Discard the hexane extracts, and add 25 g sodium
sulfite to the water solution. Store the resulting solution, which is
saturated with sodium sulfite, in an amber bottle with a Teflon-lined
screw cap. This solution can be stored at room temperature for at
least one month.
4.7 Pesticide surrogate standard spiking solution.
4.7.1 The surrogate standard is added to all samples and calibration
solutions; the compound specified for this purpose is
dibutylchlorendate.
4.7.2 Prepare a surrogate standard spiking solution at a
concentration of 1 ug/1.00 mL in acetone. 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.
4.8 Sulfuric acid solution (H-l)-(ACS). Slowly, add 50 mL H2S04 (sp. gr.
1.84) to 50 mL of reagent water.
D-9/PEST 2/88
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4.9 Pesticide matrix standard spiking solution. Prepare a spiking solution
of acetone or methanol that contains the following pesticides in the
concentrations specified.
Pesticide UE/I.O mL
Lindane 0.2
Heptachlor 0.2
Aldrin 0.2
Dieldrin 0.5
Endrin 0.5
4,4' DDT 0.5
Matrix spikes are also to serve as duplicates by spiking two 1-liter
portions from the one sample chosen for spiking.
4.10 See Exhibit A for a summary of the quality control requirements of this
contract. See Exhibit E for contract-required quality
assurance/quality control procedures.
5. Sample Extraction - Separatory Funnel
5.1 Samples may be extracted using separatory funnel techniques. If
emulsions prevent acceptable solvent recovery with separatory funnel
extractions, continuous liquid-liquid extraction (paragraph 6.1) may be
used. The separatory funnel extraction scheme described below assumes
a sample volume of one liter.
5.2 Using a 1-liter graduated cylinder, measure out a 1-liter sample
aliquot and place it into a 2-liter separatory funnel. Check the pH of
the sample with wide range pH paper and adjust to between 5 and 9 pH
with 10 N sodium hydroxide and/or 1:1 sulfuric acid solution. (NOTE:
Recovery of dibutylchlorendate will be low if pH is outside this range.
Alpha-BHC, gamma-BHC, Endosulfan I and II and Endrin are subject to
decomposition under alkaline conditions and therefore may not be
detected if the pH is above 9.) Pipet 1.0 mL surrogate standard
spiking solution into the separatory funnel and mix well. Add 1.0 mL
of pesticide matrix spiking solution to each of two 1-liter portions
from the sample selected for spiking.
5.3 Add 60 mL methylene chloride to the separatory funnel and extract the
sample by shaking the funnel for two minutes, with periodic venting to
release excess pressure. Allow the organic layer to separate from the
water phase for a minimum of 10 minutes. If the emulsion interface
between layers is more than one-third the volume of the solvent layer,
the analyst must employ mechanical techniques to complete the phase
separation. The optimum technique depends upon the sample, and may
include: stirring, filtration of the emulsion through glass wool,
centrifugation or other physical means. Drain methylene chloride into
a 250 mL Erlenmeyer flask.
5.4 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.
D-10/PEST 2/88
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5.5 Assemble a Kudema-Danish (K-D) concentrator by attaching a 10-mL
concentrator tube to a 500-mL evaporative flask. Other concentration
devices or techniques may be used in place of the K-D if equivalency is
demonstrated for all pesticides listed in Exhibit C.
5.6 Pour the combined 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 column with 20 to 30
mL of methylene chloride to complete the quantitative transfer.
5.7 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 (80 to 90°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. Allow it to drain and cool for
at least 10 minutes.
5.8 Momentarily remove the Snyder column, add 50 mL of hexane and a new
boiling chip and re-attach the Snyder column. Pre-wet the column by
adding about 1 mL of hexane to the top. Concentrate the solvent
extract as before. The elapsed time of concentration should be 5 to 10
minutes. When the apparent volume of liquid reaches 1 mL, remove the
K-D apparatus and allow it to drain and cool at least 10 minutes.
5.9 Remove the Snyder column, rinse the flask and its lower joint into the
concentrator tube with 1 to 2 mL of hexane. If sulfur crystals are a
problem, proceed to paragraph 8.1; otherwise continue to paragraph
5.10.
5.10 Nitrogen blowdown technique (taken from ASTM Method D 3086)
Place the concentrator tube in a warm water bath (35*C) and evaporate
the solvent volume to 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, as it may introduce interferences. The internal wall of the
tube must be rinsed down several times with hexane during the operation
and the final volume brought to 0.5 mL. 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.
5.11 Dilute the extract to 1 mL with acetone and proceed to 7.1 (Alumina
Column Cleanup).
6. Sample Extraction - Continuous Liquid-Liquid Extractor
6.1 When experience with a sample from a given source indicates that a
serious emulsion problem will result, or if an emulsion is encountered
D-11/PEST 2/88
-------
in paragraph 5.3 using a separatory funnel, a continuous extractor
should be used.
6.2 Using a 1-liter graduated cylinder, measure out a 1-liter sample
aliquot and place it into the continuous extractor. Pipet 1.0 mL
surrogate standard spiking solution into the continuous extractor and
mix well. Check the pH of the sample with wide range pH paper and
adjust to between 5 and 9 pH with ION sodium hydroxide and/or 1:1
sulfuric acid solution.
6.3 Add 500 mL of methylene chloride to the distilling flask. Add
sufficient reagent water to ensure proper operation and extract for 18
hours. Allow to cool, then detach the boiling flask and dry.
Concentrate the extract as in paragraphs 5.5 through 5.11.
7. Alumina Column Cleanup
7.1 Add 3 g of activity III neutral alumina to the 10-mL chromatographic
column. Tap the column to settle the alumina. Do not pre-wet the
alumina.
7.2 Transfer the 1 mL of hexane/acetone extract from paragraph 5.11 to the
top of the alumina using a disposable Pasteur pipet. Collect the
eluate in a clean 10-mL concentrator tube.
7.3 Add 1 mL of hexane to the original extract concentrator tube to rinse
it. Transfer these rinsings to the alumina column. Elute the column
with an additional 9 mL of hexane. Do not allow the column to go dry
during the addition and elution of the sample.
7.4 Adjust the extract to a final volume of 10 mL using hexane.
7.5 The pesticide/PCB fraction is ready for analysis. Proceed to Section
IV, paragraph 3. Store the extracts at 4°C (±2"C) in the dark in
Teflon-sealed containers until analyses are performed.
8. Optional Sulfur Cleanup
8.1 Concentrate the hexane extract from paragraph 5.9 to 1 mL.
8.2 Transfer the 1 mL to a 50 mL clear glass bottle or vial with a
Teflon-lined screw cap. Rinse the concentrator tube with 1 mL of
hexane, adding the rinsings to the 50 mL bottle.
8.3 Add 1 mL TBA-sulfite reagent and 2 mL 2-propanol, cap the bottle, and
shake for at least 1 min. If the sample is colorless or if the initial
color is unchanged, and if clear crystals (precipitated sodium sulfite)
are observed, sufficient sodium sulfite is present. If the
precipitated sodium sulfite disappears, add more crystalline sodium
D-12/PEST 2/88
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sulfite in approximately 100 mg portions until a solid residue remains
after repeated shaking.
8.4 Add 5 mL distilled water and shake for at least 1 minute. Allow the
sample to stand 5-10 minutes. Transfer the hexane layer (top) to a
concentrator ampule and go back to paragraph 5.10.
D-13/PEST 2/88
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PART C - PROTOCOLS FOR SOIL/SEDIMENT
It is mandatory that all soil/sediment samples be characterized as to
concentration level so that the appropriate analytical protocol may be chosen
to ensure proper quantitation limits for the sample.
The use of GC/EC methods is recommended for screening soil/sediment samples
for pesticides/PCBs, however, the Contractor is at liberty to determine the
specific method of characterization.
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 concentration range covered by the low level analysis may be considered
to be less than 1000 ug/kg of pesticides/PCBs. The concentration range
covered by the medium level analysis is greater than 1000 ug/kg.
1. Medium Level Preparation for Analysis of Pesticides/PCBs in
Soil/Sediment
1.1 Scope and Application
This procedure is designed for the preparation of sediment/soil samples
which may contain pesticides/PCBs at a level greater than 1,000 ug/kg.
1.1.1 Samples to be prepared and analyzed by this method should have
been screened by GC/EC techniques. The results of those
screens will determine whether sufficient quantities of
pesticides/PCBs are present to warrant analysis by the medium
level protocol.
1.1.2 If the screenings indicate no detectable pollutants at a level
of quantitation of 1000 ug/kg, the sample should be prepared by
the low level protocol in this Section.
1.1.3 If the extract for pesticide/PCB analysis is to be prepared
from an aliquot of the semivolatile extract, also refer to the
specific instructions in Exhibit D SV.
1.2 Summary of Method
1.2.1 Portions of soil/sediment are extracted and screened by methods
of the Contractor's choice.
1.2.2 If pesticides/PCBs are detected in the screen at levels above
approximately 1000 ug/kg. a 1 g sample is extracted with 10.0
mL of hexane for analysis by GC/EC.
1.2.3 If no pesticides/PCBs are detected above 1000 ug/kg, then the
sample shall be prepared by the low level protocol.
D-14/PEST 2/88
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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 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.
1.4 Limitations
1.4.1 The procedure is designed to allow quantitation limits as low
as 1000 ug/kg for pesticides/PCBs. If peaks are present based
on GC screen, the sample is determined to require a medium
level analysis by GC/EC. Some samples may contain 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.
1.5 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 Methylene chloride. Pesticide residue analysis grade or
equivalent.
1.5.3 Hexane. Pesticide residue analysis grade or equivalent.
1.5.4 Methanol. Pesticide residue analysis grade or equivalent.
1.5.5 Acetone. Pesticide residue analysis grade or equivalent.
1.5.6 Pesticide/PCB Surrogate Standard Spiking solution.
1.5.6.1 The compound specified is dibutylchlorendate.
Prepare a solution at a concentration of 20 ug/1.0
mL in methanol. Store the spiking solutions at 4°C
(±2eC) 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.
1.5.7 Pesticide/PCB Matrix Standard Spiking solution
1.5.7.1 Prepare a spiking solution in methanol that contains
the following pesticides in the concentrations
specified below. Store the spiking solutions at 4°C
D-15/PEST 2/88
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(+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.
Pesticide ug/1.OmL
lindane 2.0
heptachlor 2.0
aldrin 2.0
dieldrin 5.0
endrin 5.0
4,4' DDT 5.0
1.5.8 Alumina - neutral, super I Woelm (Universal Scientific,
Atlanta, GA) or equivalent. Prepare activity III by adding 7%
(v/w) reagent water to the Super I neutral alumina. Tumble or
shake on a wrist action shaker for a minimum of 2 hours or
preferably overnight. There should be no lumps present. Store
in a tightly sealed glass container. A 25 cycle soxhlet
extraction of the alumina with methylene chloride is required
if a solvent blank analyzed by the pesticide techniques
indicates any interferences for the compounds of interest.
1.5.8.1 Alumina Equivalency Check. Test the alumina by
adding the BNA surrogates (see Exhibit D SV) in 1:1
acetone/hexane to the alumina and following
paragraph 2.8.1. The tri-bromophenol should not be
detected by GC/EC if the alumina and its activation
are acceptable. Also check recovery of all single
component pesticides following the same procedure.
The percent recovery for all single component
pesticides must be >80%, except for endosulfan
sulfate which must be >60% and endrin aldehyde which
is not recovered. The data must be retained by the
laboratory and made available for inspection during
on-site evaluations. If the alumina deactivated
with 7% (v/w) reagent water does not prove adequate
to remove the BNA surrogates and other
interferences, the alumina may be deactivated with
as much as 9% reagent water, so long as the criteria
for tribromophenol and the recovery of all single
component pesticides can be met.
1.5.9 Reagent Water_ - Reagent water is defined as water in which an
interferent is not observed at or above the CRQL of each
parameter of interest.
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.
D-16/PEST 2/88
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1.6.3 Balance capable of weighing 100 g to the nearest 0.01 g.
1.6.4 Vials and caps, 2 mL for GC auto sampler.
1.6.5 Disposable pipettes, Pasteur; glass wool rinsed with methylene
chloride.
1.6.6 15-mL concentrator tubes.
1.6.7 Ultrasonic cell disrupter, Heat Systems-Ultrasonics, Inc.,
Model W-385 SONICATOR (475 Watt with pulsing capability, No.
200 1/2 inch tapped disrupter 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 Chromatography column for alumina. 8 mL (200 mm 6e 8 mm ID)
Polypropylene column (Kontes K-420160 or equivalent) or 6 mL
(150 mm X 8 mm ID) glass column (Kontes K-420155 or equivalent)
or 5 mL serological pipettes plugged with a small piece of
Pyrex glass wool in the tip. (Pyrex glass wool shall be
pre-rinsed with appropriate solvents to insure its
cleanliness). The Kontes columns may be plugged with Pyrex
glass wool or a polyethylene porous disk (Kontes K-420162).
1.7 Sample Preparation
1.7.1 Medium Level preparation for analysis of Pesticide/PCBs
(Determine results of GC/EC screen before proceeding.)
1.7.1.1 Transfer the sample container into a fume hood.
Open the sample vial and mix the sample. Transfer
approximately 1 g (record weight to 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 the sample taken. Cap
the vial before proceeding with the next sample to
avoid any cross contamination.
D-17/PEST 2/88
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1.7.1.1.1 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 Deputy Project
Officer cited in the contract for
instructions on how to handle the
sample. Document the instructions in
the Case Narrative. Discard this
portion of sample. NOTE: Recovery of
dibutylchlorendate will be low if pH is
outside this range.
1.7.1.2 Add at least 2 g of anhydrous powdered sodium
sulfate to the sample and mix well.
1.7.1.3 Surrogate standards are added to all samples, spikes
and blanks. Add 50 uL of surrogate spiking solution
to the sample mixture.
1.7.1.4 Add 1.0 mL of matrix standard spiking solution to
each of two 1 g portions from the sample chosen for
spiking.
1.7.1.5 Immediately add 10.0 mL (only 9.0 mL for the matrix
spike sample) of hexane to the sample and disrupt
the sample with the 1/8 inch tapered MICROTIP
ultrasonic probe for 1 minute with the W-385 (or 2
minutes with the W-375) with output control setting
at 5 and mode switch on "1 sec. pulse" and % duty
cycle set at 50%. (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 clear spatula,
or very carefully with the tip of the unenergized
probe.
1.7.1.6 Loosely pack disposable Pasteur pipettes with 2-3 cm
glass wool plugs. Filter the extract through the
glass wool and collect at approximately 5 mL in a
concentrator tube.
1.7.1.7 Transfer 1.0 mL of the hexane extract to a glass
concentrator tube and concentrate to 0.5 mL using
Nitrogen blowdown. Add 0.5 mL of acetone to 0.5 mL
of hexane extract. Swirl to mix. The pesticide
extract must now be passed through an alumina column
to remove polar interferences.
D-18/PEST 2/88
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1.7.1.8 Follow the procedures for low level soil sediment
preparation outlined in paragraphs 2.8.1.1 through
2.8.3.3 for alumina cleanup and sulfur removal.
2. Low Level Preparation for Analysis of Pesticides/PCBs in Soil/Sediment
2.1 Summary of Method
2.1.1 If based on the results of a GC/EC screen, no pesticides/PCBs
are present in the sample above 1000 ug/kg, a 30 gram portion
of soil/ sediment is mixed with anhydrous powdered sodium
sulfate and extracted with 1:1 methylene chloride/acetone using
an ultrasonic probe. The extract is concentrated and an
optional gel permeation column cleanup may be used. The
extract is cleaned up using a micro alumina column and analyzed
by GC/EC for pesticides.
2.2 Interferences
2.2.1 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.
2.3 Apparatus and Materials
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 pipettes, 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" disruptor horn or No. 208 3/4
inch standard solid disruptor 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 probe must be replaced if the tip begins
to erode. Erosion of the tip is evidenced by a rough surface.
2.3.3.1 Sonabox acoustic enclosure - recommended with above
disrupters for decreasing cavitation sound.
2.3.4 Beakers, 400 mL
D-19/PEST 2/88
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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).
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 ± 0.0001
g-
2.3.12 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.
2.3.13 Gel permeation chromatography (GPC) cleanup device. NOTE: GPC
cleanup is highly recommended for all extracts for low level
soils.
2.3.13.1 Automated system
2.3.13.1.1 Gel permeation chromatograph Analytical
Biochemical Labs, Inc. GPC Autoprep
1002 or equivalent including:
2.3.13.1.2 25 mm ID X 600 - 700 mm glass column
packed with 70 g of Bio-Beads SX-3.
2.3.13.1.3 Syringe, 10 mL with Luer-Lock fitting.
D-20/PEST 2/88
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2.3.13.1.4 Syringe filter holder and filters -
stainless steel and TFE, Gelman 4310 or
equivalent.
2.3.13.2 Manual system assembled from parts. (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.)
2.3.13.2.1 25 mm ID X 600 - 700 mm heavy wall
glass column packed with 70 g of
BIO-Beads SX-3.
2.3.13.2.2 Pump: Altex Scientific, Model No.
1001A, semipreparative, solvent
metering system.
Pump capacity - 28 mL/min.
2.3.13.2.3 Detector: Altex Scientific, Model No.
153, with 254 nm UV source and 8-ul
semi-preparative flowcells (2-mm
pathlengths)
2.3.13.2.4 Microprocessor/controller: Altex
Scientific, Model No. 420,
Microprocessor System Controller, with
extended memory.
2.3.13.2.5 Injector: Altex Scientific, catalog
No. 201-56, sample injection valve,
Tefzel, with 10 mL sample loop.
2.3.13.2.6 Recorder: Linear Instruments, Model
No. 385, 10-inch recorder.
2.3.13.2.7 Effluent Switching Valve: Teflon
slider valve, 3-way with 0.060" ports.
2.3.13.2.8 Supplemental Pressure Gauge with
connecting Tee: U.S.Gauge, 0-200 psi,
stainless steel. Installed as a
"downstream" monitoring device between
column and detector. Flow rate was
typically 5 mL/min. of methylene
chloride. Recorder chart speed was
0.50 cm/min.
2.3.14 Chromatography column for alumina. 8 mL (200 mm & 8 mm ID)
Polypropylene column (Kontes K-420160 or equivalent) or 6 mL
(150 mm X 8 mm ID) glass column (Kontes K-420155 or equivalent)
or 5 mL serological pipettes plugged with a small piece of
Pyrex glass wool in the tip. (Pyrex glass wool shall be
D-21/PEST 2/88
-------
pre-rinsed with appropriate solvents to ensure its
cleanliness).' The Kontes columns may be plugged with Pyrex
glass wool or a polyethylene porous disk (Kontes K-420162).
2.3.15 Pyrex glass wool.
2.3.16 Bottle or test tube, 50 mL with Teflon-lined screw cap for
sulfur removal.
2.3.17 Pasteur pipettes, disposable.
2.4 Reagents
2.4.1 Sodium Sulfate - anhydrous powdered reagent grade, heated at
400"C for four hours, cooled in a desiccator, and stored in a
glass bottle. Baker anhydrous powder, catalog #73898 or
equivalent.
2.4.2 Methylene chloride, hexane, acetone, isooctane, 2-propanol and
benzene - pesticide quality or equivalent.
2.4.3 Alumina - neutral, super I Woelm (Universal Scientific,
Atlanta, GA) or equivalent. Prepare activity III by adding 7%
(v/w) reagent water to the Super I neutral alumina. Tumble or
shake on a wrist action shaker for a minimum of 2 hours or
preferably overnight. There should be no lumps present. Store
in a tightly sealed glass container. A 25 cycle soxhlet
extraction of the alumina with methylene chloride is required
if a solvent blank analyzed by the pesticide techniques
indicate any interferences for the compounds of interest.
2.4.3.1 Alumina Equivalency Check. Test the alumina by
adding the BNA surrogates (see Exhibit D SV) in 1:1
acetone/hexane to the alumina and following
paragraph 2.8.1. The tribromophenol should not be
detected by GC/EC if the alumina and its activation
are acceptable. Also check recovery of all single
component pesticides following the same procedure.
The percent recovery for all single component
pesticides must be >80%, except for endosulfan
sulfate which must be >60% and endrin aldehyde which
is not recovered. The data must be retained by the
Contractor and made available for inspection during
on-site evaluations. If the alumina deactivated with
7%^(v/w) reagent water does not prove adequate to
remove the BNA surrogates and other interferences,
the alumina may be deactivated with as much as 9%
reagent water, so long as the criteria for
tribromophenol and the recovery of all single
component pesticides can be met.
2.4.4 Reagent water - Reagent water is defined as water in which an
interferent is not observed at or above the CRQL of each
parameter of interest.
D-22/PEST 2/88
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2.4.5 Tetrabutylammonium (TEA) - sulfite reagent. Dissolve 3.39 g
tetrabutylammonium hydrogen sulfate in 100 mL distilled water.
To remove impurities, extract this solution three times with 20
mL portions of hexane. Discard the hexane extracts and add 25
g sodium sulfite to the water solution. Store the resulting
solution, which is saturated with sodium sulfite, in an amber
bottle with a Teflon-lined screw cap. This solution can be
stored at room temperature for at least one month.
2.4.6 GPC calibration solutions:
2.4.6.1 Corn oil - 200 mg/mL in methylene chloride.
2.4.6.2 Bis(2-ethylhexylphthalate) and pentachlorophenol -
4.0 mg/mL in methylene chloride.
2.4.7 Sodium Sulfite, reagent grade.
2.4.8 Surrogate standard spiking solution.
2.4.8.1 Pesticide surrogate standard spiking solution.
2.4.8.1.1 The surrogate standard is added to all
samples, blanks, matrix spike, matrix
spike duplicates and calibrations
solutions; the compound specified for
this purpose is dibutylchlorendate.
2.4.8.1.2 Prepare a surrogate standard spiking
solution at a concentration of 20
ug/1.0 mL in methanol. Store the
spiking solutions at 4°C (±2"C)
Teflon-sealed containers. The
solutions should be checked frequently
for stability. These solutions must be
replaced after twelve months, or sooner
if comparison with quality control
check samples indicates a problem.
2.4.9 Matrix standard spiking solutions.
2.4.9.1 Pesticide matrix standard spiking solution. Prepare
a spiking solution in methanol that contains the
following pesticides in the concentrations specified
below. Store spiking solutions at 4°C (±2°) 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
indicate a problem.
D-23/PEST 2/88
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Pesticide ug/1.0 mL
lindane 2.0
heptachlor 2.0
aldrin 2.0
dieldrin 5.0
endrin 5.0
4,4' DDT 5.0
Matrix spikes are also to serve as duplicates,
therefore, add volume specified in Sample Extraction
section to each of two 30 g portions from one sample
chosen for spiking.
2.5 Sample Extraction
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.
2.5.1.1 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 Deputy Project Officer
cited in the contract for instructions on how to
handle the sample. Document the instructions in the
Case Narrative. Discard this portion of sample.
NOTE: Recovery of dibutylchlorendate will be low if
pH is outside this range.
2.5.2 The following step 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.
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.
g of sample - g of dry sample
j 3 x 100 - % moisture
g of sample
2.5.2.2 Weigh out two 30 g (record weight to nearest 0.1 g)
portions for use as matrix and matrix spike
duplicates. Follow 2.5.2. When using GPC cleanup,
add 800 uL of the pesticide matrix spike to each of
D-24/PEST 2/88
-------
the other two portions. When not using GPC cleanup,
add 400 uL of the pesticide matrix spike to each of
the two portions.
2.5.2.3 When using GPC, add 200 uL of pesticide surrogate to
the sample. When not using GPC, add 100 uL of
pesticide surrogate to the sample.
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%. Do NOT use MICROTIP probe.
(If using a sonicator other than Models W-375 or W-385, contact
the Project Officer for appropriate output settings).
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 off 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.
2.5.7 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
and pesticide compounds listed in Exhibit C.
2.5.8 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 (80 to 90°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, and make up to 10 mL
volume with methylene chloride.
D-25/PEST 2/88
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2.5.9 If GPC cleanup Is not used proceed to paragraph 2.7.
2.6. Extract Cleanup
2.6.1 GPC Setup and Calibration
2.6.1.1 Packing the column - Place 70 g of Bio Beads SX-3 in
a 400 mL beaker. Cover the beads with methylene
chloride; allow the beads to swell overnight (before
packing the columns). Transfer the swelled beads to
the column and start pumping solvent through the
column, from bottom to top, at 5.0 mL/min. After
approximately 1 hour, adjust the pressure on the
column to 7 to 10 psi and pump an additional 4 hours
to remove air from the column. Adjust the column
pressure periodically as required to maintain 7 to
10 psi.
2.6.1.2 Calibration of the column - Load 5 mL of the corn
oil solution into sample loop No. 1 and 5 mL of the
phthalate-phenol solution into loop No. 2. Inject
the corn oil and collect 10 mL fraction (i.e.,
change fraction at 2-minute intervals) for 36
minutes. Inject the phthalate-phenol solution and
collect 15 mL fractions for 60 minutes. Determine
the corn oil elution pattern by evaporation of each
fraction to dryness followed by a gravimetric
determination of the residue. Analyze the
phthalate-phenol fractions by GC/FID on the DB-5
capillary column, a UV spectrophotometer or a GC/MS
system. Plot the concentration of each component in
each fraction versus total eluent volume (or time)
from the injection points. Choose a "dump time"
which allows >85% removal of the corn oil and >85%
recovery of the bis(2-ethylhexyl)-phthalate. Choose
the "collect time" to extend at least 10 minutes
after the elution of pentachlorophenol. Wash the
column at least 15 minutes between samples. Typical
parameters selected are: Dump time, 30 minutes (150
mL), collect time, 36 minutes (180 mL), and wash
time, 15 minutes (75 mL). The column can also be
calibrated by the use of a 254 mm UV detector in
place of gravimetric and GC analyses of fractions.
Measure the peak areas at various elution times to
determine appropriate fractions.
i^-
The SX-3 Bio Beads column may be reused for several
months, even if discoloration occurs. System
calibration usually remains constant over this
period of time if column flow rate remains constant.
D-26/PEST 2/88
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2.6.2 GPC Extract Cleanup
Prefilter or load all extracts via the filter holder to avoid
particulates that might stop the flow. Load one 5.0 mL aliquot
of the extract onto the GPC column. Do not apply excessive
pressure when loading the GPC. Purge the sample loading tubing
thoroughly with solvent between extracts. After especially
dirty extracts, run a GPC blank (methylene chloride) to check
for carry-over. Process the extracts using the dump, collect
and wash parameters determined from the calibration and collect
the cleaned extracts in 400 mL beakers tightly covered with
aluminum foil. The phthalate-phenol calibration solution shall
be taken through the cleanup cycle with each set of 23 extracts
loaded into the GPC. The recovery for each compound must be
>85%. This must be determined on a GC/FID, using a DB-5
capillary column, a UV recording spectrophotometer or a GC/MS
system. A copy of the printouts of standard and check solution
are required as deliverables with each case. Show % recovery
on the copy.
2.6.2.1 If GPC cleanup of samples is required because of
poor GC/ EC chromatography in Section IV, dilute the
extract to 10 mL with methylene chloride and perform
GPC cleanup as per paragraph 2.6.2. The reagent
blank accompanying the samples should be included,
unless only one or a partial group of samples
requires cleanup. In this case, set up a new
reagent blank with 10 mL of methylene chloride and
appropriate surrogate standard added.
2.6.3 Concentrate the extract as per paragraphs 2.5.7 and 2.5.8.
2.7 Final Concentration of Extract with Optional Extract Splitting
Procedure
If the extract in 2.5.8 is to be used only for pesticide/PCB analysis,
it must be concentrated to a volume of 1.0 mL, following the procedure
in 2.7.1.
If the extract in 2.5.8 is to be used for both semivolatile and
pesticide/ PCB analyses, then it must be split into two portions. In
that case, follow the procedure in 2.7.1 to obtain the pesticide
portion, and follow that with the procedure in 2.7.2 to obtain the
semivolatile portion. Refer to Exhibit D SV for specific instructions
regarding the treatment of extracts for semivolatile analysis.
2.7.1 If the extract is to be used only for the pesticide/PCB
analysis, or if the same extract is used for both semivolatile
and pesticide/ PCB analyses, to split out the pesticide/PCB
extract, transfer 0.5 mL of the 10 mL methylene chloride
extract to a separate concentrator tube. Add 5 mL of hexane
and a silicon carbide boiling chip and mix using vortex mixer.
Attach a two-ball micro-Snyder column. Pre-wet the Snyder
column by adding 0.5 mL of hexane to the top of the column.
D-27/PEST 2/88
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Place the K-D apparatus on a hot water bath (80 - 90°C) so that
the concentrator tube is partially immersed in the hot water.
Adjust the vertical position of the apparatus and the water
temperature as required to complete the concentration in 5 to
10 minutes. Concentrate the extract to an apparent volume of
less than 1 mL. Use Nitrogen blowdown (see 2.7.3) to reduce
the volume to 0.5 mL. Add 0.5 mL of acetone. The pesticide
extract must now be passed through an alumina column to remove
the BNA surrogates.and polar interferences. Proceed to
paragraph 2.8.
2.7.2 If the extract in 2.5.8 was split in 2.7.1 to obtain a portion
for pesticides analysis, the portion for semivolatile analysis
must be treated according to the procedures in Exhibit D SV,
Section II, Part C, paragraph 2.7.2.2.
2.7.3 Nitrogen blowdown technique (taken from ASTM Method D 3086).
Place the concentrator tube in a warm water bath (35°C) and
evaporate the solvent volume to below 1 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 hexane 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. If GPC
cleanup techniques were employed, the 0.5 mL volume represents
a two-fold dilution to account for the fact that only half the
extract went through the GPC, and therefore, the sample
detection limit would be 2x CRQL (see Exhibit B).
2.7.4 Store all extracts at 4°C (±2°C) in the dark in Teflon-sealed
containers until all analyses are performed.
2.8 Pesticide/PCB
2.8.1 Alumina Column Cleanup
All samples prepared from the same extract as used for the
semivolatile analysis must be taken through this cleanup
technique to eliminate BNA surrogates that will interfere in
the GC/EC analysis.
2.8.1.1 Add 3 g of activity III neutral alumina to the 10 mL
chromatographic column. Tap the column to settle
the alumina. Do not pre-wet the alumina.
2.8.1.2 Transfer the 1.0 mL of hexane/acetone extract from
paragraph 2.7.1 to the top of the alumina using a
disposable Pasteur pipette. Collect the eluate in a
clean, 10 mL concentrator tube.
D-28/PEST 2/88
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2.8.1.3 Add 1 mL of hexane to the original extract
concentrator tube to rinse it. Transfer these
rinsings to the alumina column. Elute the column
with an additional 9 mL of hexane. Do not allow the
column to go dry during the addition and elution of
the sample.
2.8.1.4 Concentrate the extract to 1.0 mL following either
paragraph 2.7.1 or 2.7.3, using hexane where
methylene chloride is specified. When concentrating
medium level extracts, the Nitrogen blowdown
technique should be used to avoid contaminating the
micro Snyder column.
2.8.2 Observe the appearance of the extract.
2.8.2.1 If crystals of sulfur are evident or sulfur is
expected to be present, proceed to paragraph 2.8.3.
2.8.2.2 If the sulfur is not expected to be a problem,
transfer the 1.0 mL to a GC vial and label as
Pesticide/PCB fraction. The extract is ready for
GC/EC analysis. Proceed to Section IV. Store the
extracts at 4°C (±2°C) in the dark until analyses
are performed.
2.8.3 Optional Sulfur Cleanup
2.8.3.1 Transfer the 1.0 mL from paragraph 2.8.2 to a 50 mL
clear glass bottle or vial with a Teflon-lined screw
cap. Rinse the concentrator tube with 1.0 mL of
hexane, adding the rinsings to the 50 mL bottle. If
only a partial set of samples requires sulfur
cleanup, set up a new reagent blank with 1.0 mL of
hexane and take it through the sulfur cleanup.
Include the surrogate standards.
2.8.3.2 Add 1 mL TBA-sulfite reagent and 1 mL 2-propanol,
cap the bottle, and shake for at least 1 min. If
the sample is colorless or if the initial color is
unchanged, and if clear crystals (precipitated
sodium sulfite) are observed, sufficient sodium
sulfite is present. If the precipitated sodium
sulfite disappears, add more crystalline sodium
sulfite in approximately 100 mg portions until a
solid residue remains after repeated shaking.
2.8.3.3 Add 5 mL distilled water and shake for at least 1
min. Allow the sample to stand for 5-10 min. and
remove the hexane layer (top) for analysis.
Concentrate the hexane to 1.0 mL as per paragraphs
D-29/PEST 2/88
-------
2.7.1 and 2.7.3 using hexane where methylene
chloride is specified. The temperature for the
water bath should be about 80°C for the micro Snyder
column technique. Continue as outlined in paragraph
2.8.2.2.
D-30/PEST 2/88
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SECTION III
SCREENING OF PESTICIDE/PCB EXTRACTS
D-31/PEST 2/88
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1. It is mandatory that all soil/sediment samples be characterized as to
concentration level so that the appropriate analytical protocol may be
chosen to ensure proper quantitation limits for the sample.
The use of GC/EC methods is recommended for screening soil/sediment
samples for pesticides/PCBs. The contractor is at liberty to determine
the specific method of characterization. The protocols for sample
preparation (Section II) and sample analysis (Section IV) are broken
down by concentration level.
2. The terms "low level" and "medium level" are not used as a judgement of
the degree of contamination, but rather as a description of the
concentration ranges that are encompassed by the "low" and "medium"
protocols.
The concentration range encompassed by the low level protocols may be
considered to be appropriate for those samples with less than 1000
ug/kg of pesticides/ PCBs. The concentration range encompassed by the
medium level protocols may be considered to appropriate for those
samples with more than 1000 ug/kg of pesticides/PCBs.
D-32/PEST 2/88
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SECTION IV
GC/EC ANALYSIS OF PESTICIDES/PCBs
D-33/PEST 2/88
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1, Summary of Method
1.1 The hexane extracts of water and soil/sediment are analyzed on a gas
chromatograph/electron capture detector (GC/EC). If pesticides or PCBs
are tentatively identified, a second GC/EC analysis is required using
an alternate column. Quantitation must be on a packed column or a vide
bore capillary column (ID X3.32 mm), whereas, confirmation can be on
either a packed or a capillary column. NOTE: To determine that no
pesticides/FCBs are present at or above the contract required
quantitation limit jg a form of quantitation.
2. Interferences
2.1 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 gas chromatograms. All
of these materials must be routinely demonstrated to be free from
interferences under the conditions of the analysis by running
laboratory method blanks.
3. Apparatus and Materials
3.1 Gas chromatograph - An analytical system complete with gas
chromatograph and all required accessories including syringes,
analytical columns, gases, electron capture detector and strip-chart
recorder with recording integrator. A data system is required for
measuring peak areas or peak heights and recording retention times. An
electrolytic conductivity detector is also acceptable if the required
quantitation limits are met. Overlapping peaks on chromafrogfups are not
acceptable.
3.1.1 Quantitation and/or confirmation columns.
3.1.1.1 Column 1 - Gas Chrom Q (100/120 mesh) or equivalent
coated with 1.5% 0V-17/1.95% OV-210 or equivalent
packed in a 1.8m long x 4 mm ID (6 mm OD) glass
column.
NOTE: The 2mm ID column cited in Table 7 as Column
1 will not adequately separate dibutylchlorendate
and endrin ketone.
3.1.1.2 Column 2 - Gas Chrom Q (100/120 mesh) or equivalent
coated with 3% OV-1 or equivalent packed in a 1.8 m
long x 2 mm ID (6 mm OD) glass column.
3.1.1.3 Column 3 - Gas Chrom Q (80/100 mesh) or equivalent
coated with 5% OV-210 or equivalent packed in a 1.8
jt long x 2 mm ID (6 mm OD) glass column.
3.1.1.4 Vide bore capillary columns (ID >0.32 mm) may be
employed for these analyses in place of packed
columns. Strictly speaking, there are no
equivalent wide bore columns for the mixed phase
D-34/PEST Rev. 9/88
-------
Column 1 above. However, wide bore columns such as
DB-5 or DB-1701 may provide equivalent performance.
It is the responsibility of the Contractor to
demonstrate the equivalence of any wide bore
columns employed for these analyses. Equivalence is
demonstrated by meeting all of the performance
criteria for pesticide analyses given in Exhibit D
and E. Such data should be kept on file by the
laboratory, and be available during on-site
evaluations.
3 1.2 Confirmation column only. Column - 30 m X 0.25 mm ID, 0.25
micron film thickness, bonded-phase silicone coated, fused
silica capillary column (J&W Scientific DB-5 or DB-1701 or
equivalent). pOTE: DB-1701 provides better separation of TCL
D-34a/PEST
9/88
-------
pesticides. Column 10 m x 0.32 mm ID, 1 micron film thickness
has been used.
3.2 Balance - analytical, capable of accurately weighing ±0.0001 g.
4. Reagents
4.1 Isooctane (2,2,4-trimethylpentane), hexane and toluene - Pesticide
quality or equivalent.
4.2 Stock standard solutions (1.00 ug/uL) - Stock standard solution can be
prepared from pure standard materials or purchased as certified
solutions.
4.2.1 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 isooctane.
Larger volumes can be used at the convenience of the analyst.
If compound purity is certified at 96% or greater, the weight
can be used without correction to calculate the concentration
of the stock standard. Commercially prepared stock standards
can be used at any concentration if they are traceable to
EMSL/LV supplied standards.
4.2.2 Transfer the stock standard solutions into a bottle/vial with
Teflon-lined septa. Store at 4"C (±2°C) and protect from
light. Stock standard solutions must be replaced after twelve
months, or sooner if comparison with check standards indicate a
problem.
4.3 Working standards solutions - Prepare mixtures of standards diluted
with hexane that will provide approximately half scale response for all
the compounds of interest. This should be at the attenuation setting
capable of achieving the contract-required quantitation limits (Exhibit
C). (This would be approximately 0.01 ng/uL for aldrin.) Two mixtures
of the individual component standards are recommended to prevent
co-elution of components on packed columns. However, all individual
component standards may be included in one mixture on packed or
capillary columns if the laboratory demonstrates that the components
may be separated with no overlap of peaks. Include dibutylchlorendate
in all standard mixtures. All multicomponent standards, i.e., PCB
Aroclors and toxaphene must be in separate solutions with the exception
of Aroclors 1016/1260. Include dibutylchlorendate in all
multicomponent standard mixtures.
4.3.1 Evaluation Standard Mixtures - Prepare working standard
mixtures diluted with hexane containing aldrin, endrin, 4,4'
DDT and dibutylchlorendate to evaluate the GC column. Prepare
three concentration levels to provide the following criteria:
4.3.1.1 Low level will be approximately 20% above base line
(Evaluation Standard Mix A).
D-35/PEST 2/88
-------
4.3.1.2 Mid level will be approximately half scale
(Evaluation Standard Mix B).
4.3.1.3 High level will be approximately full scale
(Evaluation Standard Mix C). (Dibutylchlorendate
must be 0.1 ng/uL to correspond with 100% surrogate
recovery in 10 mL final volume. This may be
slightly greater than full scale but should still be
in linear range).
4.3.2 Individual Standard Mixtures - These include all single
component TCL pesticides plus alpha chlordane, gamma chlordane,
endrin ketone, endrin aldehyde and dibutylchlorendate (see
paragraph 6.1.4 for suggested mixtures). Alpha and gamma
chlordane should be in Mixture B to avoid overlap with other
pesticides.
5. Calibration
5.1 The gas chromatographic system must be calibrated using the external
standard technique for all packed columns used for quantitation.
5.2 External standard calibration procedure:
5.2.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding
volumes of one or more stock standards to a volumetric flask
and diluting to volume with hexane. One of the external
standards should be at a concentration near, but above, the
CRQL and the other concentrations should correspond to the
expected range of concentrations found in real samples or
should define the working range of the detector. This should be
done on each quantitation column and each instrument at the
beginning of the contract period and each time a new column is
installed. The data must be retained by the laboratory and
made available for inspection during on-site evaluations.
5.2.2 Using injections of 2 to 5 uL of each calibration standard,
tabulate peak height or area responses against the mass
injected. The results can be used to prepare a calibration
curve for each compound.
6. GC/EC Primary Analysis (Quantitation may be performed on primary or
confirmation analyses.)
Adjust oven temperature and carrier gas flow rates so that the
retention time for 4,4'-DDT is equal to or greater than 12 minutes.
Table 7 provides examples of operating conditions for the gas
chromatograph. Separation should be > 25% resolution between peaks.
Percent resolution is calculated by dividing the height of the valley
by the peak height of the smaller peak being resolved, multiplied by
100. This criterion must be considered when determining whether to
quantitate on the Primary Analysis or the Confirmation Analysis. When
D-36/PEST 2/88
-------
this criterion cannot be net, quantitation is adversely affected
because of the difficulty in determining where to establish the
baseline.
6.1 Inject 2 to 5 uL of the sample or standard extract using the
solvent-flush technique or auto sampler. Smaller (1.0 uL) volumes can
be injected only if automatic devices are employed. Record the volume
injected to the nearest 0.05 uL and the total extract volume. NOTE:
Dibutylchlorendate recovery nay be calculated from a capillary or
packed column GC/EC meeting all QC requirements for quantitation.
However, matrix spike duplicates must be quantitated on a packed column
or vide bore capillary column.
6.1.1 Inject Individual Standard Mix A and B and all vultiresponse
pesticides/FCBs at the beginning of each 72 hour sequence.
(See paragraph 6.1.3.5) To establish the RT window within each
72-hour sequence for the pesticide/PCB of interest, use the
absolute RT from the above chromatograms as the nid-point, and
+ three times the standard deviation calculated in Exhibit E
for each compound. Individual Standard Mix A and B are analyzed
alternately and intermittently throughout the analysis as shown
in 6.1.3.5. Any pesticide outside of its established retention
time window requires immediate investigation and correction
before continuing the analysis. The laboratory must reanalyze
all affected samples.
6.1.2 Sample analysis of extracts from Section II, Sample
Preparation, can begin when linearity and degradation QA/QC
requirements specified in Exhibit E have been net.
NOTE: The 10.0% RSD linearity criterion is onlv required on
the column(s) being used for pesticide/PCBs quantitation. If a
column is used for surrogate quantitation only, the 10.0% RSD
is required only for dibutylchlorendate.
Analyze samples in groups of no more than 5 camples. After the
analysis of the first group of up to 5 samples, analyze
Evaluation Mix B. Analyze another group of up to 5 samples,
followed by the analysis of Individual Mix A or B. Subsequent
groups of up to 5 samples may be analyzed by repeating this
sequence, alternately analyzing Evaluation Mix B and Individual
Mix A or B between the groups as shown in 6.1.3.5. The
Pesticide/PCB analytical sequence m&£ end with Individual Mix
A and B regardless of the number of camples--.analyzed (see
6.1.3.5).
If • nultiresponse pesticide/PCB is detected in either of the
preceding groups of 5 samples, the appropriate •ultiresponse
pesticide/PCB may be substituted for Individual Mix A or B. All
standards listed in 6.1.3.5 Bust be included for every Case and
«ust be analyzed within the came 72-hour period as the camples,
with the exception of Aroclors 1221 and 1232 which are analyzed
at a minimum of once per month (see footnote in 6.1.3.5). If
the camples are cplit between 2 or nore instruments, the
D-37/PEST Rev. 9/88
-------
complete set of standards must be analyzed on each instrument
with the same 72-hour requirement. All standards must be
analyzed prior to the samples to avoid the effects of poor
chromatography caused by the unsuspected injection of a highly
concentrated sample.
6.1.3 Paragraphs 6.1.3.1 - 6.1.3.5 contain GC performance criteria.
If it is determined during the course of a 72-hour sequence
that one or more of the criteria have been violated, stop the
run and take corrective action (see Exhibit E, Section III
PEST, 4.3.3.8). After the corrective action has been taken,
the 72-hour sequence may be restarted as follows. If a
standard violated the criterion, restart the sequence with that
standard, determine that the criteria have been met and
continue with sample analyses, according to 6.1.3.5. If a
sample violated the criterion, restart the sequence with the
standard that would have followed that group of samples
(thereby preserving the sequence of standards in 6.1.3.5),
determine that the criteria have been met and continue with
sample analyses, according to 6.1.3.5.
If it is determined after the completion of a 72-hour sequence
that one or more of the criteria have been violated, proceed as
follows. If a standard violated the criterion, all samples
analyzed after that standard must be re-analyzed as part of a
new 72-hour sequence. If a subsequent standard in the original
sequence met all the criteria, then only those samples analyzed
between the standard that did not meet the criterion and the
standard that did meet the criterion must be re-analyzed as
part of a new 72-hour sequence. If only samples violated the
criteria, then those samples must be re-analyzed as part of a
new 72-hour sequence.
6.1.3.1 Differences in the Calibration Factors for each
standard in Individual Standard Mix A and B must not
exceed 20.0% (15.0% for any standard compound used
for quantitation) during the 72-hour Primary
Analysis. Calculate the % difference using the
initial Individual Standard Mix versus all
subsequent Individual Standard Mixes analyzed during
the 72-hour sequence. (The equations for
calculation of Calibration Factor and % difference
are in Exhibit E, Section III PEST, paragraph
4.3.4.2.) NOTE: To determine that no
pesticides/PCBs are present at or above the contract
required quantitation limit is a form of
quantitation.
The retention time shift of dibutylchlorendate in
any standard or sample must be less than 2.0%
difference for packed columns, less than 1.5%
difference for wide bore capillary columns (ID
greater than 0.32 mm) and less than 0.3% difference
D-38/PEST 2/88
-------
for narrow bore capillary columns (ID less than 0.32
mm) .
6.1.3.2 Samples must also be repeated if the degradation of
DDT and/or endrin exceeds 20.0% respectively on the
intermittent analysis of Evaluation Standard Mix B.
6.1.3.3 All pesticide standards must fall within the
established 72-hour retention time windows.
6.1.3.4 Highly colored extracts may require a dilution.
6.1.3.5 The 72-hour sequence must be as follows.
72-Hour Sequence for Pesticide/PCB Analysis:
1. Evaluation Standard Mix A
2. Evaluation Standard Mix B
3. Evaluation Standard Mix C
4. Individual Standard Mix A*
5. Individual Standard Mix B*
6. Toxaphene
7. Aroclors 1016/1260
8. Aroclor 1221**
9. Aroclor 1232**
10. Aroclor 1242
11. Aroclor 1248
12. Aroclor 1254
13. 5 samples
14. Evaluation Standard Mix B
15. 5 samples
16. Individual Standard Mix A or B
17. 5 samples
18. Evaluation Standard Mix B
19. 5 samples
20. Individual Standard Mix A or B
(whichever not run in step 16)
21. 5 samples
22. Repeat the above sequence starting
with Evaluation Standard Mix B (step
14 above).
23. Pesticide/PCB analysis sequence must
end with the analyses of both
Individual Standard Mix A and B
regardless of number of samples
^ analyzed.
*These may be combined into one mixture (see
paragraph 4.3).
**Aroclors 1221 and 1232 must be analyzed on each
instrument and each column at a minimum of once per
month.
D-39/PEST 2/88
-------
6.1.4
Copies of these chromatograms must be submitted for
sample analyses performed during the applicable
month.
Suggested groups of compounds and concentrations for Individual
Standard Mix A and B follow, which are recommended to prevent
overlap of compounds on the two packed columns (3% OV-1 and
1.5% OV-17/1.95% OV-210). Some of the compounds overlap on the
5% OV-210 column (see Table 7). The concentration is based on
a 5 uL injection.
Individual
Standard Mix A ng/uL
gamma-BHC 0.005
heptachlor 0.010
aldrin* 0.010
heptachlor epoxide 0.010
endosulfan I 0.010
dieldrin 0.010
p,p'-DDT 0.020
endrin aldehyde 0.025
endosulfan II 0.020
methoxychlor 0.100
dibutylchlorendate 0.050
*For RRT determination.
Individual
Standard Mix B ng/uL
alpha-BHC 0.005
beta-BHC 0.010
delta-BHC 0.010
aldrin* 0.010
p,p'-DDE 0.010
endrin 0.010
p.p'-DDD 0.020
endosulfan sulfate 0.020
endrin ketone 0.020
alpha chlordane 0.010
gamma chlordane 0.010
dibutylchlorendate 0.050
6.1.5
Inject the method blank (extracted with each set of samples) on
every instrument and GC column on which the samples are
analyzed.
6.2 Evaluation of Chromatograms.
6.2.1 Consider the sample negative when its peaks, depending on the
pesticide's response factor, result in concentrations less than
the required quantitation level. The sample is complete at .
this point. Confirmation is not required.
6.2.2 Tentative identification is made when the unknown's retention
time matches the retention time of a corresponding standard
that was chromatographed on the same instrument within a
72-hour period.
6.2.3 Determine if any pesticides/PCBs listed in Exhibit C are
present. Pattern recognition techniques, based on chromatograms
of standards, are recommended for the identification of PCB
compounds.
6.2.3.1 If the response for any of these compounds is 100%
or less of full scale, the extract is ready for
confirmation and quantitation.
D-40/PEST
2/88
-------
6.2.3.2 If the response for any compound is greater than
full scale, dilute the extract so that the peak will
be between 50 and 100% full scale and reanalyze on
the packed column. Use this dilution also for
confirmation and quantitation.
6.2.3.3 For dilution >10 fold. Also inject an aliquot of a
dilution 10 fold more concentrated to determine if
other compounds of interest are present at lower
concentrations.
6.2.3.4 Computer reproductions of chromatograms manipulated
to ensure all peaks are on scale over a 100 fold
range are an accepted substitute. However, this can
be no greater than a 100 fold range. This is to
prevent retention time shifts by column or detector
overload. Linearity must be demonstrated over the
100 fold range using higher concentrations of the
evaluation mixture.
6.2.4 Quantitation may be performed on the primary analysis, with the
exception of toxaphene and possibly the DDT series. If DDT
exceeds the 10.0% RSD linearity criterion, then quantitations
for any DDE, ODD and DDT in a sample must be on the
confirmation analysis. Toxaphene must always be quantitated on
the confirmation analysis. See Exhibit E for special QC
requirements for quantitation.
6.2.5 If identification of compounds of interest are prevented by the
presence of interferences, further cleanup is required. If
sulfur is evident go to Sulfur Cleanup (Section II, Part B,
paragraph 8.). If unknown interferences or poor chromatography
are noted only in the sample chromatogram, it is recommended
that gel permeation chromatography cleanup (Section II, Part C,
paragraph 2.6) be applied.
6.2.6 When selecting a GC column for confirmation and/or
quantitation, be sure that none of the compounds to be
confirmed/quantitated overlap, i.e., do not select the 3% OV-1
column if DDE and dieldrin are to be confirmed and/or
quantitated. When samples are very complex, it may be
necessary to use all three packed columns to achieve adequate
separation (>25% resolution) of all compounds being
quantitated.
7. GC/EC Confirmation Analysis
7.1 Confirmation Analysis is to confirm the presence of all compounds
tentatively identified in the Primary Analysis. Therefore, the only
standards that are required are the Evaluation Standard Mixes (to
check linearity and degradation criteria) and standards of all
compounds to be confirmed. The linearity criterion on the confirmation
column for pesticides is not required unless the column is used for
quantitation. The 72-hour sequence in 6.1.3.5 is, therefore, modified
D-41/PEST 2/88
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to fit each case. Quantitation may be performed on the confirmation
analysis. If toxaphene or DDT is to be quantitated, additional
linearity requirements are specified in 7.3.1.
7.2 Table 7 provides examples of operating conditions for the gas
chromatograph. Separation should be >25% resolution between peaks.
Percent resolution is calculated by dividing the height of the valley
by the peak height of the smaller peak being resolved, multiplied by
100. This criterion must be considered when determining whether to
quantitate on the Primary Analysis or the Confirmation Analysis. When
this criterion cannot be met, quantitation is adversely affected
because of the difficulty in determining where to establish the
baseline.
For a fused silica capillary column (FSCC) confirmation, there must be
>25 percent resolution (valley) between the following pesticide pairs:
o beta-BHC and delta-BHC
o Dieldrin and 4,4'-DDT
o 4,4'-ODD and Endrin Aldehyde
o Endosulfan Sulfate and 4,4'-DDT
All QC requirements specified in Exhibit E must be adhered to, i.e.,
the >12 min. retention time for 4,4'-DDT, the criteria for 4,4'-DDT and
endrin degradation, linearity, calibration factor for standards and
retention time shift for dibutylchlorendate. The retention time
criterion for 4,4'-DDT does not have to be met if the confirmation
column is OV-1 or OV-101. Apply instructions from 6.1.3 to the
confirmation analysis.
7.3 Inject 2 to 5 uL (1-2 uL for capillary columns) of the sample extract
and standards using the solvent-flush technique or auto samplers. A
volume of 1 uL can be injected only if automatic devices are employed.
Record the volume injected to the nearest 0.05 uL and the total extract
volume. The detector attenuation must provide peak response equivalent
to the Primary Analysis response for each compound to be confirmed.
7.3.1 Begin the Confirmation Analysis GC sequence with the three
concentration levels of Evaluation Standard Mixes A, B and C.
The exception to this occurs when toxaphene and/or DDT series
are to be confirmed and quantitated. There are four
combinations of pesticides that could occur, therefore, the
following sequences must be followed depending on the
situation.
7.3.1.1 Toxaphene only - Begin the sequence with Evaluation
Mix B to check degradation, followed by three
concentration levels of toxaphene. Check linearity
by calculating %RSD.
If <10.0% RSD, use the appropriate equation in
paragraph 8 for calculation. If >10.0% RSD, plot a
standard curve and determine the ng for each sample
in that set from the curve.
D-42/PEST 2/88
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7.3.1.2 DDT, DDE, ODD only - Begin the sequence with
Evaluation Mix B. Then inject three concentration
levels of a standard containing DDE, DDD and DDT.
Calculate linearity and follow the requirements
specified in 7.3.1.1 for each compound to be
quantitated.
7.3.1.3 DDT series and toxaphene - Begin the sequence with
Evaluation Mix B. Then inject three concentration
levels of toxaphene and another three levels of the
DDT series. Calculate linearity and follow the
requirements specified in 7.3.1.1 for each compound
to be quantitated. NOTE: Capillary quantitation
would be allowed only in this situation.
7.3.1.4 Other pesticides/PCBs plus DDT series and/or
toxaphene — Begin the sequence with Evaluation
Standard Mixes A, B and C. Calculate linearity on
the four compounds in the Evaluation Standard mixes.
If DDT and/or one or more of the other compounds are
>10.0% RSD and/or degradation exceeds the criterion,
corrective maintenance as outlined in Exhibit E,
Section III PEST, paragraph 4.3.3.8, should be
performed before repeating the above chromatography
evaluations. If only DDT exceeds the linearity
criterion and one or more of the DDT series is to be
quantitated, follow 7.3.1.2 (do not repeat
Evaluation Mix B).
If none of the DDT series is to be quantitated and
DDT exceeds the 10.0% RSD, simply record the % RSD
on the proper form. Any time toxaphene is to be
quantitated, follow 7.3.1.1.
7.3.2 After the linearity standards required in 7.3.1 are injected,
continue the confirmation analysis sequence by injecting
standards for all compounds tentatively identified in the
primary analysis, to establish the 72-hour retention time
windows. (See paragraph 6.1.1.) Analyze all confirmation
standards for a case at the beginning, at intervals specified
in 7.3.3 and at the end. Any pesticide outside of its
established retention time window requires immediate
investigation and correction before continuing the analysis.
The laboratory must reanalyze all samples which follow the
standard that exceeds the criterion.
7.3.3 After injection of the appropriate standards (see 7.3.2), begin
injection of samples. Analyze groups of 5 samples. Analyze
Evaluation Mix B after the first group of 5 samples. After the
second group of 5 samples, analyze a standard pertaining to the
samples in the preceding groups (i.e., substitute standards
pertaining to the preceding samples for Individual Mix A or B
in 6.1.3.5). Continue analyzing groups of 5 samples,
alternately analyzing Evaluation Mix B and standards pertaining
D-43/PEST 2/88
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to the preceding samples between groups of 5 samples. The
alternating standard's calibration factors must be within 15.0%
of each other if quantitation is performed. Deviations larger
than 15.0% require the laboratory to repeat the analyses of
samples which were analyzed after the standard that exceeded
the criterion. The 15.0% criterion only pertains to compounds
being quantitated.
If more than one standard is required to confirm all compounds
tentatively identified in the Primary Analysis, alternate the
standards with Evaluation Mix B. Samples oust also be repeated
if the degradation of either DDT and/or andrin exceeds 20.0% on
the intermittent Evaluation Standard Mix B.
If the samples are split between 2 or more instruments, all
standards and blanks pertaining to those samples oust be
analyzed on each instrument.
7.3.4 Inject the method blank (extracted with each set of samples) on
every GC and GC column on which the samples are analyzed.
7.4 Evaluation of Chromatograms
7.4.1 A compound tentatively identified in the primary analysis is
confirmed if the retention time from the confirmation analysis
falls within the retention time window of a corresponding
standard that was chromatographed on the same instrument within
a 72-hour period.
7.4.2 Quantitation should be on the packed column or wide bore
capillary column chromatogram (primary or confirmation) that
provides the best separation from interfering peaks. NOTE: To
determine that no pesticides/PCBS are present at or above the
contract required quantitation limit jg * form of quantitation.
7.4.2.1 Quantitation of Chlordane - Because weathering
and/or different formulations of chlordane usually
modify the pattern exhibited by technical chlordane,
this method is not appropriate for determining
technical chlordane. Instead, standards for alpha
chlordane and gamma chlordane are used for
quantitation, and each isomer of chlordane is
reported separately.
•»_
7.4.3 Computer reproductions of Chromatograms that are attenuated to
ensure all peaks are on scale over a 100 fold range are
acceptable. However, this can be no greater than a 100 fold
range. This is to prevent retention time shifts by column or
detector overload. Also, peak response oust be >25% of full
scale deflection to allow visual pattern recognition of
Bulticomponent compounds, and individual compounds Bust be
visible.
D-44/PEST Rev. 9/88
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7.4.4 If identification of compounds of interest are prevented by the
presence of interferences, further cleanup is required. If
sulfur is evident, go to Sulfur Cleanup (Section II, Part B,
paragraph 8).
If unknown interferences or poor chromatography are noted only
in the sample chromatogram, it is recommended that gel
permeation chromatography cleanup (Section II, Part C,
paragraph 2.6) be applied.
7.4.5 Calculate surrogate standard recovery on all samples, blanks
and spikes unless the surrogate was diluted out. Determine if
recovery is within limits and repoTt on Form II. See formula
for calculation in 8.3.
7.4.6 If TCL pesticide/PCB compounds were identified in the unspiked
sample from which the matrix spike and matrix spike duplicate
were prepared, confirmation analysis is required for the matrix
spike and matrix spike duplicate. If TCL pesticide/PCB
compounds were not identified in the unspiked sample,
confirmation of the matrix spike and matrix spike duplicate is
not required. Calculate matrix spike duplicate recoveries and
report on Form III (see Exhibit B, Section III).
8. Calculations
8.1 Calculate the concentration in the sample using the following equation
for external standards. Response can be measured by the manual peak
height technique or by automated peak height or peak area measurements
from an integrator.
8.1.1 Water
(Av)(Ic)(Vt.)
Concentration ug/L - (As)(Vi)(Vg)
Where:
AX — Response for the parameter to be measured.
Ag — Response for the external standard.
Vt - Volume of total extract (uL) (take into account
any dilutions)
Ig - Amount of standard injected in nanograms (ng)
Y£ - Volume of extract injected (uL)
Vg - Volume of water extracted (mL)
-^~
8.1.2 Sediment/Soil
Concentration ugAg - (As) (Vj) (Wg) (D)
(Dry weight basis)
D-45/PEST 2/88
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Where:
AJJ, ISiAs.vi ~ same as given above in 8.1.1
Vc - Volume of low level total extract
(Use 20,000 uL or a factor of this when
dilutions are made other than those accounted
for below):
o 1/20 total extract taken for pesticide
analysis (derived from 0.5 mL of 10 mL
extract)
o final concentration to 1.0 mL for pesticide
analysis
- or -
Vc - Volume of medium level total extract
(Use 10,000 uL or a factor of this when
dilutions are made.)
D - 100 - % moisture (% moisture from Section II,
100 Part C)
Wg - Weight of sample extracted (g)
8.2 For multicomponent mixtures (chlordane, toxaphene and PCBs) match
retention times of peaks in the standards with peaks in the sample.
Quantitate every identifiable peak (>50% of the total area must be
used) unless interference with individual peaks persist after cleanup.
Add peak height or peak area of each identified peak in the
chromatogram. Calculate as total response in the sample versus total
response in the standard.
8.3 Calculation for surrogate and matrix spike recoveries.
Percent Recovery - Q^
.r- X 100%
^a
where,
QJ — quantity determined by analysis
Qa - quantity added to sample.
Be sure all dilutions are taken into account. Soil/Sediment has a
20-fold dilution factor built into the method when accounting for
one-twentieth of extract taken for pesticide analysis and final
dilution to 1 mL.
8.4 Report results in micrograms per liter or micrograms per kilogram
without correction for recovery data.
D-46/PEST 2/88
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9. GC/MS Confirmation of Pesticides
9.1 Any compounds confirmed by two columns must also be confirmed by GC/MS
if the concentration is sufficient for detection by GC/MS. The
following paragraphs should be used as guidance when determining if a
pesticide/PCB compound can be confirmed by GC/MS.
9.1.1 The GC/MS analysis normally requires a minimum concentration of
10 ng/uL in the final extract, for each single component
compound. For the BNA extract of a water sample, a
concentration of 10 ng/uL in extract is approximately 20 ug/L
(ppb) in the sample. For the BNA extract of a low level soil
sample, the equivalent sample concentration would be
approximatly 170 ug/Kg if no GPC was performed. For the BNA
extract of a medium soil, the equivalent sample concentration
is on the order of 10,000 ug/Kg.
9.1.2 The pesticide extract and associated blank should be analyzed
by GC/MS as per Exhibit D SV, Section IV, paragraph 5.
9.1.3 The confirmation may be from the GC/MS analysis of the
semivolatile extracts (sample and blank). However, if the
compounds are not detected in the semivolatile extract even
though the concentration is high enough, a GC/MS analysis of
the pesticide extract is required.
9.1.4 A reference standard for the compound must also be analyzed by
GC/MS. The concentration of the reference standard must be at
a level that would demonstrate the ability to confirm the
pesticides/PCBs identified by GC/EC. Use the sample
concentration calculated from the GC/EC results as guidance.
The concentration of the reference standards must be no greater
than the sample extract concentration predicted from the GC/EC
sample concentration. For instance, as in paragraph 9.1.1
above, a 20 ug/L sample result from GC/EC requires a 10 ng/uL
GC/MS reference standards in order to demonstrate adequate
sensitivity for a water sample.
9.1.5 In the event the GC/MS does not confirm the presence of the
pesticides/PCBs identified by GC/ECD, those compounds should be
reported as not detected. The minimum quantitation limits ("U"
values) should be adjusted to reflect the interferences. The
inability to confirm the compounds by GC/MS must be noted in
the Case Narrative.
9.1.6 For GC/MS confirmation of multicomponent pesticides and PCBs,
required deliverables are spectra of 3 major peaks of
multicomponent compounds from samples and standards.
9.1.7 Quantitation by GC/MS must use the characteristic quantitation
ions for pesticides/PCBs given in Table 5 of Exhibit D SV.
D-47/PEST 2/88
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Table 7
Examples of Orders of Elution of Pesticides/PCBs
Parameter
Column 1
Column 2
Column 3
alpha-BHC
gamma -BHC
beta-BHC
Heptachlor
delta -BHC
Aldrin
Heptachlor epoxide
Endosulfan I
4, 4 '-DDE
Dieldrin
Endrin
4 ,4' -ODD
Endosulfan II
4, 4 '-DDT
Endrin aldehyde
Endosulfan sulfate
Endrin ketone
gamma Chlordane
alpha Chlordane
Toxaphene
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
methoxychlor
dibutvlchlorendate
1.45
1.86
2.18
2.27
2.55
2.76
4.31
5.46
6.37
6.74
8.25
10.08
10.14
12.06
13.64
16.73
22.70
4.77
5.24
mr
mr
mr
or
mr
mr
mr
mr
24.07
21.80
1.64
1.94
1.76
3.21
2.01
4.01
4.98
6.26
7.51
7.38
8.35
9.53
8.35
12.75
9.53
11.09
-
5.74
6.39
mr
mr
mr
mr
mr
mr
mr
mr
19.60
27.21
1.86
2.37
2.75
2.55
2.80
2.93
5.53
7.08
6.03
8.59
10.14
10.57
12.88
11.55
21.11
31.27
33.16
5.25
5.70
mr
mr
mr
mr
mr
mr
mr
mr
18.12
22.26
mr - multiresponse compounds.
Column 1 conditions: Gas Chrom Q (80/100 mesh) or equivalent coated with
1.5% 0V-17/1.95% OV-210 or equivalent packed in a 1.8 m long x 2 mm ID (6 mm
OD) glass column with 5% methane/95% argon carrier gas at a flow rate of 30
mL/min. (HP 5880) Column temperature, isothermal at 192°C. 2 mm ID column
with 80/100 mesh does not adequately resolve dibutyl chlorendate and endrin
ketone.
Column 2 conditions: Gas Chrom Q (100/120 mesh) or equivalent coated with 3%
OV-1 or equivalent packed in a 1.8 m long x 2 mm ID (6 mm OD) glass column
with 5% methane/95% argon carrier gas at a flow rate of 30 mL/min. (30
mL/min makeup gas). (Tracer 222). Column temperature, isothermal at 194°C.
D-48/PEST
2/88
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Table 7 (continued)
Column 3 conditions: Gas Chrom Q (80/100 mesh) or equivalent coated with 5%
OV-210 packed in a 1.8 m x 2 mm ID (6 mm OD) glass column with 5% methane/
95% argon carrier gas at a flow rate of 30 mL/min. (30 mL/min. make-up gas).
HP5840. Column temperature, isothermal at 183"C.
Capillary column 1 conditions: 30 m x 0.25 mm ID, 0.25 micron film thickness,
fused silica DB-5 (or equivalent) splitless mode
Helium carrier gas: 4 mL/min at 280eC and 25 PSI
Septum purge: 15 mL/min
Split vent: none
Initial temperature: 160"C, initial hold - 2 min
Program at 5eC/min
Final temperature: 270°C, final hold - 4 min
Injection port temperature: 225°C
Capillary column 2 conditions: 10 m x 0.32 mm ID, 1 micron film thickness,
fused silica DB-1701, splitless mode
Helium carrier gas: 4 mL/min at 280°C and 25 PSI
Septum purge: 15 mL/min
Split vent: none
Initial temperature: 160°C, initial hold - 3 min
Program at 10°C/min to 240"C
Program from 240 to 270"C at 5°C/min
Final Hold: 4 min
Injection port temperature: 235°C
D-49/PEST 2/88
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EXHIBIT E
QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
E-l 2/88
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Table of Contents
Section Page
I INTRODUCTION E-3
II QA/QC STANDARD OPERATING PROCEDURES E-4
*
III QA/QC REQUIREMENTS
Volatiles (VOA) QA/QC Requirements E-10/VOA
Semivolatiles (SV) QA/QC Requirements E-28/SV
Pesticides/PCBs (PEST) QA/QC Requirements E-47/PEST
•«
IV ANALYTICAL STANDARDS E-65
V LABORATORY EVALUATION PROCEDURES E-67
E-2 2/88
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SECTION I
INTRODUCTION
The purpose of the Quality Assurance/Quality Control (QA/QC) program outlined
herein is the definition of procedures for the evaluation and documentation
of subsampling, analytical methodologies, and the reduction and reporting of
data. The objective is to provide a uniform basis for subsampling, sample
handling, instrument conditions, methods control, performance evaluation, and
analytical data generation and reporting.
The scope of the program is for all laboratory operations (from sample
receipt, through analysis, to data reduction/reporting) applied to trace
organics samples. The scope includes those audit procedures used to evaluate
the application of the procedures defined within this QA/QC program.
E-3 2/88
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SECTION II
QA/QC STANDARD OPERATING PROCEDURES
E-4 2/88
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1. The Contractor shall have a written QA/QC standard operating procedures
(SOP) which describes the in-house procedures that he employs to
guarantee, to the extent possible, the quality of all analysis
activities. It should describe the quality assurance and the quality
control procedures used during the analysis. Each Contractor should
prepare his own SOPs to suit the needs of his organization as he has
best determined. The QA/QC SOP should contain the essential elements
described in this section.
2. Elements of a QA/QC SOP
2.1 All routine laboratory tasks should have written QA/QC Standard
Operating Procedures. Standard Operating Procedures should be detailed
documents describing who does what, when, where, how, and why. They
shall be sufficiently complete and detailed to ensure that:
•*
2.1.1 Data of known quality and integrity are generated.
2.1.2 The loss of data due to out-of-control conditions is minimized.
2.2 Standard Operating Procedures shall be:
2.2.1 Adequate to establish the traceability of standards,
instrumentation, samples, and environmental data.
2.2.2 Simple, so a user with basic education, experience and/or
training can properly use them.
2.2.3 Complete enough so the user can follow the directions in a
stepwise manner.
2.2.4 Consistent with sound scientific principles.
2.2.5 Consistent with current EPA regulations.^guidelines, and
contract requirements.
2.2.6 Consistent with the instrument manufacturer's specific
instruction manuals.
2.3 Standard Operating Procedures shall also provide for documentation
sufficiently complete to:
2.3.1 Record the performance of all tasks and their results.
2.3.2 Explain the cause of missing data.
2.3.3 Demonstrate the validation of data each time they are recorded,
calculated, or transcribed.
2.4 To accomplish these objectives, Standard Operating Procedures should
address the major elements upon which the final quality of the
Contractor's work depends. In the following descriptions these six
major areas have been divided into sub-elements, where applicable.
These elements include but are not limited to:
E-5 2/88
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2.4.1 Organization and personnel,
2.4.2 Facilities and equipment,
2.4.3 Analytical methodology,
2.4.4 Sample custody procedures,
2.4.5 Quality control, and
2.4.6 Data handling.
3. Organization and Personnel
3.1 QA Policy and Objectives - Each organization should have a written
quality assurance policy that should be made known to all organization
personnel. Objectives should be established to produce data that meet
contract requirements in terms of completeness, precision, accuracy,
representativeness, documentation, and comparability. The SOP should
require the preparation of a specific QA plan for the analysis.
3.2 QA Organization - The organization and management of the QA function
should be described in the Contractor's SOP. Reporting relationships .
and responsibilities should be clearly defined. A QA Coordinator or
Supervisor should be appointed and his responsibilities established. A
description of the QC paperwork flow should be available. There should
be a clear designation of those who are authorized to approve data and
results. Responsibilities for taking corrective action should be
assigned to appropriate management personnel.
3.3 Personnel training - It is highly desirable that there be a training
program for employees. This system should include motivation toward
producing data of acceptable quality and should involve "practice work"
by the new employee. The quality of this work ca/i be immediately
verified and discussed by the supervisor, with appropriate corrective
action taken.
3.4 Document Control and Revisions. The SOP should include a system for
documenting:
3.4.1 Calibration procedures,
3.4.2 Analytical procedures,
3.4.3 Computational procedures,
3.4.4 Quality control procedures,
3.4.5 Bench data,
3.4.6 Operating procedures, or any changes to these procedures, and
3S4.7 Laboratory notebook policy.
E-6 2/88
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3.5 Procedures for making revisions to technical procedures or documents
must be clearly defined, with the lines of authority indicated.
Procedural revisions should be written and distributed to all affected
individuals, thus ensuring implementation of changes.
4. Facilities and Equipment
4.1 Procurement and Inventory Procedures - Purchasing guidelines fortall
equipment and reagents having an effect on data quality should be
well-defined and documented. Similarly, performance specifications
should be documented for all items of equipment having an effect on
data quality. Once any item which is critical to the analysis such as
an in situ instrument, or reagent is received and accepted by the
organization, documentation should be retained of the type, age, and
acceptance status of the item. Reagents should be dated upon receipt
in order to establish their order of use and to minimize the
possibility of exceeding their useful shelf life.
4.2 Preventive Maintenance - Preventive maintenance procedures should be
clearly defined and written for each measurement system and required
support equipment. When maintenance activity is necessary, it should
be documented on standard forms maintained in logbooks. A history of
the maintenance record of each system serves as an indication of the
adequacy of maintenance schedules and parts inventory.
5. Analytical Methodology
5.1 Calibration and Operating Procedures - Calibration is the process of
establishing the relationship of a measurement system output to a known
stimulus. In essence, calibration is a reproducible reference point to
which all sample measurements can be correlated. A sound calibration
SOP should include provisions for documentation of frequency,
conditions, standards, and records reflecting the calibration history
of a measurement system. ^
5.1.1 The accuracy of the calibration standards is an important point
to consider since all data will be in reference to the
standards used. An SOP for verifying the accuracy of all
working standards against primary grade standards should be
routinely followed.
5.2 Feedback and corrective action - The SOP should specify the corrective
action that is to be taken when an analytical or sampling error is
discovered or the analytical system is determined to be out of control.
The SOP should require documentation of the corrective action and
notification of the analyst of the error and correct procedures.
6. Sample Custody
6.1 Sample custody is a part of any good laboratory or field operation.
Where samples may be needed for legal purposes, "chain-of-custody"
procedures, as defined in Exhibit F must be used. However, at a
minimum, the following sample custody procedures should be addressed in
the QA/QC SOP.
E-7 2/88
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6.2 Chain-of-custody in laboratory operations
6.2.1 Identification of responsible party to act as sample custodian
at the laboratory facility authorized to sign for incoming
field samples, obtain documents of shipment (e.g., bill of
lading number or mail receipt), and verify the data entered
onto the sample custody records.
6.2.2 Provision for a laboratory sample custody log consisting of
serially numbered standard lab-tracking report sheets.
6.2.3 Specification of laboratory sample custody procedures for
sample handling, storage and dispersement for analysis.
7. Quality Control
••
7.1 Quality Control Procedures - The quality control procedures used during
analysis should be described and must conform to those described in
Exhibit E. The quality control checks routinely performed during
sample analysis include method blank analysis to establish analyte
levels, duplicate analysis to establish analytical precision, spiked
and blank sample analysis to determine analytical accuracy. The
frequency of these quality control checks are defined in the contract. •
Limits of acceptance or rejection are also defined for analysis and
control charts should be used. Confirmation procedures should be
described in the SOP.
7.2 Control Checks and Internal Audits - A good SOP will make provision for
and describe control checks and internal audits by the Contractor.
Several approaches are used for control checks. These include:
7.2.1 Reference material analysis. Analytical reference materials
are available from several commercial and government sources,
or they may be prepared in-house. The ckemical analysis of
these materials has been well established. Such materials can
be analyzed alongside routine samples and the results used to
check the accuracy of analytical procedures.
7.2.2 Blank analysis. The procedures and the frequency of blank
analyses are defined in the contract.
7.2.3 Matrix spike and matrix spike duplicate analysis. The
procedures and the frequency of matrix spike analyses are
defined in the contract.
7.2.4 Internal audits. Internal audits should be periodically
conducted to evaluate the functioning of the QA SOP. This
involves an independent check of the performance of the
laboratory analysts to determine if prescribed procedures are
closely followed.
E-8 2/88
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8. Data HandlinE
8.1 Data Handling, Reporting, and Recordkeeping - Data handling, reporting,
and recordkeeping procedures should be described. Data handling and
reporting includes all procedures used to record data on standard
forms, and in laboratory notebooks. The reporting format for different
types of bench data should be described and the forms provided. The
contents of notebooks should be specified.
8.1.1 Recordkeeping of this type serves at least two useful
functions: (1) it makes possible the reanalysis of a set of
data at a future time, and (2) it may be used in support of the
experimental conclusions if various aspects of the analysis are
called into question.
8.2 Data, Validation - Data validation procedures, defined ideally as a set
of computerized and manual checks applied at various appropriate levels
of the measurement process, should be in written form and clearly
defined for all measurement systems.
8.2.1 Criteria for data validation must be documented and include
limits on:
•
8.2.1.1 Operational parameters such as GC conditions;
8.2.1.2 Calibration data;
8.2.1,3 Special checks unique to each measurement, e.g.,
successive values/averages;
8.2.1.4 Statistical tests, e.g., outliers; and
8.2.1.5 Manual checks such as hand calculations.
«»
8.2.2 The limits defined in the contract ensure a high probability of
detecting invalid data for either all or the majority of the
measurement systems. The required data validation activities
(GC operating conditions, analytical precision, etc.) should be
recorded on standard forms in a logbook.
E-9 2/88
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SECTION III
VOLATILES QA/QC REQUIREMENTS
E-10/VOA 2/88
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This section outlines the minimum quality control (QC) operations necessary
to satisfy the analytical requirements associated with the determination of
volatile organic TCL compounds in water and soil/sediment samples. These QC
operations are as follows:
o Documentation of GC/MS Mass Calibration and Abundance Pattern
o Documentation of GC/MS Response Factor Stability
o Internal Standard Response and Retention Time Monitoring
o Method Blank Analysis
o Surrogate Spike Response Monitoring
o Matrix Spike and Matrix Spike Duplicate Analysis
PART 1 - TUNING AND GC/MS MASS CALIBRATION
1. Summary
It is necessary to establish that a given GC/MS meets the standard mass
spectral abundance criteria prior to initiating any on-going data
collection. This is .accomplished through the analysis of
p-Bromofluorobenzene (BFB).
*
Definition: The twelve (12) hour time period for GC/MS system tuning,
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
tune. The time period ends after twelve (12) hours has elapsed
according to the system clock.
1.1 p-Bromofluorobenzene (BFB)
1.1.1 Each GC/MS system used for the analysis of volatile TCL
compounds must be hardware tuned to meet'the abundance criteria
listed in Table 1.1 for a maximum of a 50 nanogram injection of
BFB. Alternately, add 50 ng of BFB solution to 5.0 ml of
reagent water and analyze according to Exhibit D VOA, Section
IV. BFB shall not be analyzed simultaneously with any
calibration standards or blanks. This criterion must be
demonstrated daily or for each twelve-hour time period,
whichever is more frequent. If required, background subtraction
must be straightforward and designed only to eliminate column
bleed or instrument background ions. Background subtraction
actions resulting in spectral distortions for the sole purpose
of meeting the contract specifications are unacceptable.
NOTE: All instrument conditions must be identical to those used
in sample analysis, except that a different temperature program
may be used.
1.1.2 BFB criteria MUST be met before any standards, samples, or
blanks are analyzed. Any samples analyzed when tuning criteria
E-ll/VOA 2/88
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have not been met may require reanalysis at no cost to the
Agency.
1.1.3 Whenever the Contractor takes corrective action which may
change or affect the tuning criteria for BFB (e.g., ion source
cleaning or repair, etc.), the tune must be verified
irrespective of the twelve-hour tuning requirements.
TABLE 1.1. BFB KEY IONS AND ABUNDANCE CRITERIA
Mass Ion Abundance Criteria
50 15.0-40.0 percent of the base peak
75 30.0-60.0 percent of the base peak
95 base peak, 100 percent relative abundance
96 5.0-9.0 percent of the base peak
173 less than 2.0 percent of mass 174
174 greater than 50.0 percent of the base peak
175 5.0 - 9.0 percent of mass 174
176 greater than 95.0 percent but less than 101.0
percent of mass 174
177 5.0 - 9.0 percent of mass 176
1.2 Documentation
The Contractor shall provide documentation of the calibration in the
form of a bar graph spectrum and as a mass listing.
1.2.1 The Contractor shall complete a Form V (GC/MS Tuning and Mass
Calibration) each time an analytical system is tuned. In
addition, all standards, samples, blanks, matrix spikes, and
matrix spike duplicates analyzed during a particular tune must
be summarized in chronological order on *he bottom of the
appropriate Form V. Detailed instructions for the completion
of Form V are in Exhibit B, Section III.
PART 2 - CALIBRATION OF THE GC/MS SYSTEM
2. Summary
Prior to the analysis of samples and required blanks and after tuning
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 TCL compound standards. Once the system has been
calibrated, the calibration must be verified each twelve (12) hour time
period for each GC/MS system.
2.1 Prepare calibration standards as described in Exhibit D VGA, Section
IV, to yield the following specific concentrations:
E-12/VOA 2/88
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2.1.1 Volatile TCL Compounds
Initial calibration of volatile TCL compounds is required at
20, 50, 100, 150 and 200 ug/L. Surrogate and internal'
standards shall be used with each of the calibration standards.
Utilizing the analytical protocol specified in Exhibit D this
will result in 100-1000 total ng analyzed. If an analyte
saturates at the 200 ug/L concentration level, and the G.C/MS
system is calibrated to achieve a detection sensitivity of no
less than 5 ug/L, the laboratory must document it in the Case
Narrative, and attach a quantitation report and RIC. In this
instance, the laboratory should calculate the results based on
a four-point initial calibration for the specific analyte that
saturates. The use of separate calibration methods which
reflect the two different low and medium soil/sediment methods
is required. Secondary ion quantitation is only allowed when
there are sample interferences with the primary ion. If
secondary ion quantitation is used, document the reasons in the
Case Narrative. Analyze all method blanks and standards under
the same conditions as the samples.
2.2 The USEPA plans to develop performance based criteria for response
factor data acquired during this program. To accomplish this goal, tha
Agency has specified both the concentration levels for initial
calibration and has also specified the specific internal standard to be
used on a compound-by-compound basis for quantitation (see Table 2.1).
Establishment of standard calibration procedures is necessary and
deviations by the Contractor will not be allowed.
2.3 Analyze each calibration standard and tabulate the area of the primary
characteristic ion (Exhibit D VOA, Table 3) against concentration for
each compound including all contract required surrogate compounds. The
relative retention times of each compound in each calibration run
should agree within 0.06 relative retention time«*inits. Late eluting
compounds usually will have much better agreement.
Using Table 2.1 and Equation 2.1, calculate the relative response
factors (RRF) for each compound at each concentration level.
*x Cis
RRF - x Eq. 2.1
Ais Cx
where,
AX - Area of the characteristic ion for the compound to be
measured.
Ais - Area of the characteristic ion for the specific internal
standards from Table 2.1 or 2.2.
^is " Concentration of the internal standard (ng/uL).
Cx - Concentration of the compound to be measured (ng/uL).
E-13/VOA 2/88
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TABLE 2.1. VOLATILE INTERNAL STANDARDS WITH CORRESPONDING
TCL ANALYTES ASSIGNED FOR QUANTITATION
Bromochloromethane
1,4-Difluorobenzene
Chlorobenzene-
Chloronethane
Bromomethane
Vinyl Chloride
Chloroethane
Methylene Chloride
Acetone
Carbon Bisulfide
1,1-Dichloroethene
1,1-Dichloroethane
l,2-Dichloroethene(tot.
Chloroform
1,2-Dichloroethane
2-Butanone
1,2-Dichloroethane-d^
(surr)
1,1,1-Trichloroethane
Carbon Tetrachloride
Vinyl Acetate
Bromodichloromethane
1,2-Dichloropropane
trans -1,3-Dichloropropene
Trichloroethene
D ibromochloromethane
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)
Bromo fluorobenz ene
(surr)
Toluene-dg (surr)
(surr) — surrogate compound
2.3.1 Using the relative response factors (RRF) from the initial
calibration, calculate the percent relative standard deviations
(%RSD) for compounds labeled on Form VI as Calibration Check
Compounds and shown in Table 2.2 (see 2.6.2), using Equation
2.2 below.
%RSD
SD
X 100
Eq. 2.2
where,
RSD
SD
- Relative Standard Deviation
Standard Deviation of initial relative
response factors (per compound)
where: SD
- x)
N-l
mean of initial relative response factors
(per compound)
E-14/VOA
2/88
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The %RSD for each individual Calibration Check Compound must be
less than or equal to 30.0 percent. This criteria must be met
for the initial calibration to be valid.
2.4 A system performance check must be performed to ensure that minimum
average relative response factors are met before the calibration curve
is used.
t
2.4.1 For volatiles, the five System Performance Check Compounds
(SPCCs) are: chloromethane, 1,1-dichloroethane, bromoform,
1,1,2,2-tetrachloroethane and chlorobenzene. The minimum
acceptable average relative response factor (RRF) for these
compounds is 0.300, 0.250 for Bromoform. These compounds
typically have RRFs of 0.4-0.6 and are used to check compound
instability and check for degradation caused by contaminated
lines or active sites in the system. For instance:
o Chloromethane - this compound is the most likely
compound to be lost if the purge flow is too fast.
o Bromoform - this compound is one of the compounds most
likely to be purged very poorly if the purge flow is too
slow. Cold spots and/or active sites in the transfer
lines may adversely affect response. Response of the
quantitation ion (m/z 173) is directly affected by the
tuning of BFB at ions m/z 174/176. Increasing the m/z
174/176 ratio may improve bromoform response.
o Tetrachloroethane, 1,1-Dichloroethane - These compounds
can be deteriorated by contaminated transfer lines in
purge and trap systems and/or active sites in trapping
materials.
2.4.2 The initial calibration is valid_emly after both the %RSD for
CCC compounds and the minimum RRF for SPCC have been met. Only
after both these criteria are met can sample analysis begin.
2. 5 Documentation
Once the initial calibration is validated, calculate and report the
average relative response factor (RRF) and percent relative standard
deviation (%RSD) for all TCL compounds. The Contractor shall complete
and submit Form V (the GC/MS tune for the initial calibration) and Form
VL (Initial Calibration Data) for each instrument used to analyze
samples under this protocol. Detailed instructions for completion of
Form VI are in Exhibit B, Section III.
2.6 Continuing Calibration
A calibration standard(s) containing all volatile TCL compounds,
including all required surrogates, must be performed each twelve hours
during analysis (see definition of twelve hour time period, paragraph
1. of this Section). Compare the relative response factor data from
the standards each twelve hours with the average relative response
E-15/VOA 2/88
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factor from the initial calibration for a specific instrument. A
system performance check must be made each twelve hours. If the SPCC
criteria are met, a comparison of relative response factors is made for
all compounds . This is the same check that is applied during the
initial calibration (Form VI) . If the minimum relative response
factors are not met, the system must be evaluated and corrective action
must be taken before sample analysis begins.
•
2.6.1 Some possible problems are standard mixture degradation,
injection port inlet contamination, contamination at the front
end of the analytical column, and active sites in the column or
chromatography system. This check must be met before analysis
begins . The minimum relative response factor (RRF) for
volatile System Performance Check Compounds (SPCC) is 0.300
(0.250 for Bromoform) .
2.6.2 Calibration Check Compounds (CCC)
After the system performance check is met, Calibration Check
Compounds listed in Table 2.2 are used to check the validity of
the initial calibration. Calculate the percent difference
using Equation 2.3.
- RRFC
% Difference - - - - x 100 Eq. 2.3
RRFj
where
RRFr - average relative response factor from initial
calibration
RRF - relative response factor from current
calibration check standard
2.6.2.1 If the percent difference for any compound is
greater than 20%, the laboratory should consider
this a warning limit. If the percent difference for
each CCC is less than or equal to 25.0%, the initial
calibration is assumed to be valid. If the criteria
are not met (>25.0% difference), for any one
calibration check compound, corrective action MUST
be taken. Problems similar to those listed under
SPCC could affect this criteria. If no source of
the problem can be determined after corrective
action has been taken, a new initial five point
calibration MUST be generated. These criteria MUST
be met before sample analysis begins.
E-16/VOA 2/88
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TABLE 2.2 VOLATILE CALIBRATION CHECKCOMPOUNDS
1,1-Dichloroethene
Chloroform
1,2-Dichloropropane
Toluene
Ethylbenzene
Vinyl Chloride
2.6.3 Concentration Levels for Continuing Calibration Check
The USEPA plans to evaluate the long tern stability of relative
response factors during this program. Standardization among
contract laboratories is necessary to reach these long tern
goals. Along with contract specified concentrations for initial
calibration, the USEFA is requiring specific concentrations for
each continuing calibration standard(s).
2.6.3.1 The concentration for each volatile TCL compound in
the continuing calibration standard(s) is 50 ug/L.
2.7 Documentation
The Contractor shall complete and submit a Form VII for each GC/MS system
utilized for each twelve hour time period. Calculate and report the
relative response factor and percent difference (%D) for all compounds.
Ensure that the minimum RRF for volatile SPCCs is 0.300 and 0.250 for
Bromoform. The percent difference (%D) for each CCC compound must be
less than or equal to 25.0 percent. Additional instructions for
completing Form VII are in Exhibit B, Section III.
PART 3 - METHOD BLANK ANALYSIS
3. Summary
A method blank is a volume of deionized, distilled laboratory water for
water samples, or a purified solid matrix for soil/sediment samples,
carried through the entire analytical scheme. The method blank volume or
weight must be approximately equal to the sample volumes or sample
weights being processed.
3.1 Method blank analysis Bust be performed at the following frequency:
3.1.1 For the analysis of volatile TCL compounds, a method blank
analysis must be performed once for each 12-hour tine period.
See Part 1, paragraph 1 for the definition of the 12-hour tine
period. The method blank must be analyzed after the calibration
standard(s).
3.2 It is the Contractor's responsibility to ensure that nethod interferences
caused by contaminants in solvents, reagents, glassware, and other saople
processing hardware that lead to discrete artifacts and/or elevated
baselines in gas chromatograms be minimized.
E-17/VOA Rev. 9/88
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3.2.1 For the purposes of this protocol, an acceptable laboratory
method blank should meet the criteria of paragraphs 3.2.1.1 and
3.2.1.2.
3.2.1.1 A method blank for volatile analysis must contain
less than or equal to five times (5X) the Contract
Required Quantitation Limit (CRQL from Exhibit C) of
methylene chloride, acetone, toluene, and
2-butanone.
3.2.1.2 For all other TCL compounds not listed above, the
method blank must contain less than or equal to the
Contract Required Quantitation Limit of any single
TCL analyte.
3.2.2 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 Case Narrative (Exhibit B).
3.3 Documentation
The Contractor shall report results of method blank analysis using the
Organic Analysis Data Sheet (Form I) and the form for tentatively
identified compounds (Form I, TIC). In addition, the samples
associated with each method blank must be summarized on Form IV (Method
Blank Summary). Detailed instructions for the completion of these
forms can be found in Exhibit B, Section III. "
3.3.1 The Contractor shall report ALL sample concentration data as
UNCORRECTED for blanks.
PART 4 - SURROGATE SPIKE CSS) ANALYSIS
4. Summary
Surrogate standard determinations are performed on all samples and
blanks. All samples and blanks are fortified with surrogate spiking
compounds before purging or extraction in order to monitor preparation
and analysis of samples.
4.1 Each sample, matrix spike, matrix spike duplicate, and blank are spiked
with surrogate compounds prior to purging or extraction. The surrogate
spiking compounds shown in Table 4.1 are used to fortify each sample,
matrix spike, matrix spike duplicate, and blank with the proper
concentrations. Performance based criteria are generated from
laboratory results. Therefore, deviations from the spiking protocol
will not be permitted.
E-18/VOA 2/88
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TABLE 4.1 SURROGATE SPIKING COMPOUNDS
Amount in Sample/Extract*
Compounds (before any optional dilutions)
Fraction Water Low/Medium Soil
Toluene -dg
4-Bromofluorobenzene
1 , 2 - Dichloroe thane - d^
VOA
VOA
VOA
50 ug
50 ug
50 ug
50 ug
50 ug
50 ug
* At the time of injection.
4.2 Surrogate spike recovery must be evaluated by determining whether the
concentration (measured as percent recovery) falls inside the contract
required recovery limits listed in Table 4.2.
TABLE 4.2 CONTRACT REQUIRED SURROGATE SPIKE RECOVERY LIMITS
Fraction Surrogate Compound Water Low/Medium Soil
VOA
VOA
VOA
Toluene -do
4 - Bromof luorobenzene
1 , 2 -Dichloroe thane - d/
88-110
86-115
76-114
81-117
74-121
70-121
4.3 Treatment of surrogate spike recovery information is according to
paragraphs 4.3.1 through 4.3.2.
*
4.3.1 Method Blank Surrogate Spike Recovery
The laboratory must take the actions listed below if recovery
of any one surrogate compound in the volatiles fraction of the
method blank is outside of the required surrogate spike
recovery limits.
4.3.1.1 Check calculations to ensure that there are no
errors; check internal standard and surrogate
spiking solutions for degradation, contamination,
etc; also check instrument performance.
4.3.1.2 Reanalyze the blank or extract if steps in 4.3.1.1
fail to reveal the cause of the noncompliant
surrogate recoveries.
4.3.1.3 If the blank is a methanol extract for medium level
soil samples, reextract and reanalyze the blank if
steps in 4.3.1.2 fail to reveal the cause of the
noncompliant surrogate recoveries.
E-19/VOA 2/88
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4.3.1.4 If the measures listed in 4.3.1.1 thru 4.3.1.3 fail
to correct the problem, the analytical system must
be considered out of control. The problem MUST be
corrected before continuing.
This may mean recalibrating the instrumentation but
it may also mean more extensive action. The
specific corrective action is left up to the GC/MS
operator. When surrogate recovery(ies) in the blank
is outside of the contract required windows, all
samples associated with that blank MUST be
reanalyzed at no additional cost to the Agency.
4.3.2 Sample Surrogate Spike Recovery
The laboratory must take the actions listed below if recovery
of any one surrogate compound in the volatiles fraction of the
sample is outside of the contract surrogate spike recovery
limits.
4.3.2.1 The Contractor laboratory shall document (in this
instance, document means to write down and discuss
problem and corrective action taken in the Case
Narrative (see Exhibit B) deviations outside of
acceptable quality control limits by taking the
following actions:
4.3.2.1.1 Check calculations to ensure that there
are no errors; check internal standard
and surrogate spiking solutions for
degradation, contamination, etc; also
check instrument performance.
4.3.2.1.2 If the steps in 4T.3.2.1.1 fail to
reveal a problem, then reanalyze the
sample or extract. If reanalysis of the
sample or extract solves the problem,
then the problem was within the
laboratory's control. Therefore, only
submit 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.
4.3.2.1.3 If the sample was a soil extracted with
methanol and the steps in 4.3.2.1.2
fail to solve the problem, then
reextract and reanalyze the sample. If
the reextraction and reanalysis solves
the problem, then the problem was in
the laboratory's control. Therefore,
only submit data from the extraction
E-20/VOA 2/88
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and 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.
4.3.2.1.4 If the reextraction and/or reanalysis
of the sample does not solve the
problem; i.e., surrogate recoveries are
outside the contract windows for both
analyses, then submit the surrogate
spike recovery data and the sample data
from both analyses according to
paragraph 4.4. Distinguish between the
initial analysis and the reanalysis on
all data deliverables, using the sample
suffixes specified in Exhibit B.
4.4 Documentation
The Contractor is required to report surrogate recovery data for the
following:
o Method Blank Analysis
o Sample Analysis
o Matrix Spike/Matrix Spike Duplicate Analyses
o All sample reanalyses that substantiate a matrix effect
The surrogate spike recovery data are summarized on the Surrogate Spike
Percent Recovery Summary (Form II). Detailed instructions for the
completion of Form II are in Exhibit B, Section III.
«»
PART 5 - MATRIX SPIKE/MATRIX SPIKE DUPLICATE ANALYSIS (MS/MSP)
5. Summary
In order to evaluate the matrix effect of the sample upon the
analytical methodology, the USEPA has developed the standard mixes
listed in Table 5.1 to be used for matrix spike and matrix spike
duplicate analyses. These compounds are subject to change depending
upon availability and suitability for use as matrix spikes.
5.1 MS/MSD Frequency of Analysis
A matrix spike and matrix spike duplicate must be performed for each
group of samples of a similar matrix, once:
o each Case of field samples received, OR
o each 20 field samples in a Case, OR
E-21/VOA 2/88
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o each group of field samples of a similar concentration level
(soils only). OR
o each 14 calendar day period during which field samples in a
Case were received (said period beginning with the receipt of
the first sample in that Sample Delivery Group),
whichever is most frequent.
5.2 Use the compounds listed in Table 5.1 to prepare matrix spiking
solutions according to protocols described in Exhibit D VOA. The
analytical protocols in Exhibit D VOA stipulate the amount of matrix
spiking solution to be added to the sample aliquots. Each method
allows for optional dilution steps which must be accounted for when
calculating percent recovery of the matrix spike and matrix spike
duplicate samples.
TABLE 5.1. MATRIX SPIKING SOLUTIONS
Volatiles
Chlorobenzene 1,1-Dichloroethene
Toluene Trichloroethene
Benzene
5.2.1 Samples requiring optional dilutions and chosen as the matrix
spike/ matrix spike duplicate samples, must be analyzed at the
same dilution as the original unspiked sample.
5.3 Individual component recoveries of the matrix spike are calculated
using Equation 5.1.
*
Matrix Spike SSR - SR
Percent Recovery - x 100 Eq. 5.1
SA
where,
SSR - Spike Sample Results
SR - Sample Result
SA - Spike Added From Spiking Mix
:^*
5.4 Relative Percent Difference (RPD)
The Contractor is required to calculate the relative percent difference
between the matrix spike and matrix spike duplicate. The relative
percent differences (RPD) for each component are calculated using
Equation 5.2.
E-22/VOA 2/88
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Dl - D2
RPD - - X 100 Eq. 5.2
D2)/2
where ,
RPD - Relative Percent Difference
D]_ - First Sample Value
Do ~ Second Sample Value (duplicate)
5 . 5 Documentation
The matrix spike (MS) results (concentrations) for nonspiked volatile
TCL compounds shall be reported on Form I (Organic Analysis Data Sheet)
and the matrix spike percent recoveries shall be summarized on Form III
(MS/MSD Recovery) . These values will be used by EPA to periodically
update existing performance based QC recovery limits (Table 5.2).
The results for nonspiked volatile TCL compounds in the matrix spike
duplicate (MSD) analysis shall be reported on Form I (Organic Analysis
Data Sheet) and the percent recovery and the relative percent
difference shall be summarized on Form III (MS/MSD Recovery) . The RPD
data will be used by EPA to evaluate the long term precision of the
analytical method. Detailed instructions for the completion of Form III
are in Exhibit B, Section III.
TABLE 5.2. MATRIX SPIKE RECOVERY LIMITS
Fraction Matrix Spike Compound Water Soil/Sediment
VOA
VOA
VOA
VOA
VOA
1, 1-Dichloroethene
Trichlorethene
Chlorobenzene
Toluene
Benzene
61-145
71-120
75-130
76-125
76-127
59-172
62-137
60-133
59-139
66-142
PART 6 - SAMPLE ANALYSIS
6. Summary
The intent of Part 6 is to provide the Contractor with a brief summary
of ongoing QC activities, involved with sample analysis. Specific
references are provided to help the Contractor meet specific reporting
and deliverables requirements of this contract.
6.1 Sample Analysis
Samples can be analyzed upon successful completion of the initial QC
activities. When twelve (12) hours have elapsed since the initial tune
E-23/VOA 2/B8
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was completed, it is necessary to conduct an instrument tune and
calibration check analysis (described in Part 2 of this Section). Any
major system maintenance, such as a source cleaning or installation of
a new column, may necessitate a retune and recalibration irrespective
of the twelve-hour requirement (see Initial Calibration, Part 2).
Minor maintenance should necessitate only the calibration verification
(Continuing Calibration, Part 2)
6.1.1 Internal Standards Evaluation - Internal standard responses and
retention times in all samples must be evaluated immediately
after or during data acquisition. If the retention time for
any internal standard changes by more than 30 seconds, the
chromatographic system must be inspected for malfunctions, and
corrections made as required. The extracted ion current
profile (EICP) of the internal standards must be monitored and
evaluated for each sample, blank, matrix spike, and matrix
spike duplicate. The criteria are described in detail in the
instructions for Form VIII, Internal Standard Area Summary (see
Exhibit B, Section III). If the extracted ion current profile
(EICP) area for any internal standard changes by more than a
factor of two (-50% to 100%), from the latest daily (12 hour
time period) calibration standard, the mass spectrometric
system must be inspected for malfunction, and corrections made
as appropriate. Breaking off 1 foot of the column (when using"
capillary column) or cleaning the injector sleeve (when using
either packed or capillary column) will often improve high end
sensitivity for the late eluting compounds; repositioning or
repacking the front end of the column will often improve front
end column performance. Poor injection technique can also lead
to variable IS ratios. When corrections are made, re-analysis
of samples analyzed while the system was malfunctioning is
necessary.
6.1.1.1 If after reanalysis, 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, only submit 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.
6.1.1.2 If the reanalysis 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
reanalysis on all data deliverables, using the
sample suffixes specified in Exhibit B. Document in
the Case Narrative all inspection and corrective
actions taken.
E-24/VOA 2/88
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6.1.2 Each analytical run must also be checked 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 method calibration (Part 2) requires
that the system should not be saturated for high response
compounds at 200 ug/L for VOA TCL compounds.
6.1.2.1 If the on-column concentration of any compound in
any sample exceeds the initial calibration range,
that sample must be diluted, the internal standard
concentration readjusted, and the sample reinjected,
as described in specific methodologies in Exhibit D
VOA. Note: 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. Secondary ion quantitation is
only allowed when there are sample matrix
interferences with the primary ion. If secondary
ion quantitation is performed, document the reasons
in the Case Narrative.
6.1.2.2 If the dilution of the sample causes any compound
detected in the first analysis to be undetectable in
the second analysis, then the results of both
analyses shall be reported on separate Forms I,
according to the instructions in Exhibit B.
6.1.3 Qualitative Analysis
The compounds listed in the Target Compound List (TCL), Exhibit
C, shall be identified by an analyst competent in the
interpretation of mass spectra, by comparison of the suspect
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 (Exhibit D, Section IV).
6.1.3.1 For establishing correspondence of the GC relative
retention time (RRT), the sample component RRT must
compare within ±0.06 RRT units of the RRT of the
standard component. For reference, the standard must
be run on the same shift as the sample.
6.1.3.2 For comparison of standard and sample component mass
spectra, mass spectra obtained on the Contractor's
GC/MS are required. The BFB tuning requirements
listed in Part 1 of this Section must be met on that
same GC/MS.
E-25/VOA 2/88
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6.1.3.2.1 The requirements for qualitative
verification by comparison of mass
spectra are as follows:
o 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.
o The relative intensities of ions
specified in the above paragraph
must agree within ±20% between the
standard and sample spectra.
o 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. 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 (Exhibit D, Section
IV).
6.1.3.2.2 If a compound cannot be verified by all
of the criteria in 6.1.3.2.1, but in
the technical judgement of the mass
spectral interpretation specialist the
identification is correct, the
Contractor shall report the
identification and proceed with the
quantitation.
6.1.3.3 A library search shall be executed for nonsurrogate
and non-TCL sample components for the purpose of
tentative identification. For this purpose, the
1985 or most recent available version of the
National Bureau of Standards Mass Spectral Library,
containing 42,261 spectra should be used.
6.1.4 Quantitation
6.1.4.1 TCL components identified shall be quantitated by
the internal standard method. The internal
standards used shall be the ones assigned in Table
2.1 of this Section. The EICP area of characteristic
ions of TCL analytes are used (Exhibit D VOA,
Section IV).
E-26/VOA 2/88
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6.1.4.2 An estimated concentration for non-TCL components
tentatively identified shall be quantitated by the
internal standard method. For quantification, the
nearest internal standard free of interferences must
be used.
6.1.4.3 Calculate surrogate standard recovery (see Part 4)
for all surrogate compounds in all samples, blanks,
matrix spikes, and matrix spike duplicates. If
recovery is within contractual limits, report on
Form II (see Exhibit B). If recovery is outside
contractual limits, take specific steps listed in
Surrogate Spike Recoveries (Part 4).
6.1.4.4 Calculate matrix spike and matrix spike duplicate
percent recovery (see Part 5 of this Section) for
all compounds and report results on Form III (see
Exhibit B). Calculate Relative Percent Differences
(RPDs) for all matrix spiking compounds and report
results on Form III. Ensure that the" proper
frequency of MS/MSD analysis is maintained.
6.1.5 Reporting and Deliverables
Refer to Exhibit B of this Statement of Work for specific
details on contract deliverables and reporting formats.
Exhibit B contains specific instructions for completing all
required Forms, as well as a detailed itemization of reporting
and deliverables requirements. Exhibit H contains the format
requirements for delivery of data in computer-readable format.
E-27/VOA 2/88
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SECTION III SV
SEMIVOLATILES QA/QC
REQUIREMENTS
E-28/SV 2/88
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This Section outlines the minimum quality control (QC) operations necessary
to satisfy the analytical requirements associated with the determination of
seraivolatile organic TCL compounds in water and soil/sediment samples. These
QC operations are as follows:
o Documentation of GC/MS Mass Calibration and Abundance Pattern
o Documentation of GC/MS Response Factor Stability
o Internal Standard Response and Retention Time Monitoring
o Method Blank Analysis
o Surrogate Spike Response Monitoring
o Matrix Spike and Matrix Spike Duplicate Analysis
PART 1 - TUNING AND GC/MS MASS CALIBRATION
1. Summary
It is necessary to establish that a given GC/MS meets the standard mass
spectral abundance criteria prior to initiating any on-going data
collection. This is accomplished through the analysis of
Decafluorotriphenylphosphine (DFTPP).
Definition: The twelve (12) hour time period for GC/MS system tuning
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 tune. The time
period ends after twelve (12) hours has elapsed according to the system
clock.
1.1 Decafluorotriphenylphosphine (DFTPP)
1.1.1 Each GC/MS system used for the analysis of semivolatile or
pesticide TCL compounds must be hardware tuned to meet the
abundance criteria listed in Table 1.2 for a 50 ng injection of
decafluorotriphenylphosphine (DFTPP). DFTPP may be analyzed
separately or as part of the calibration standard. The
criteria must be demonstrated daily or for each twelve (12)
hour period, whichever is more frequent, before samples can be
analyzed. DFTPP must be injected to meet this criterion. If
required, background subtraction must be straightforward and
designed only to eliminate column bleed or instrument
background ions. Background subtraction actions resulting in
spectral distortions for the sole purpose of meeting the
contract specifications are unacceptable. NOTE: All
instrument conditions must be identical to those used in sample
analysis, except that a different temperature program may be
used.
1.1.2 Whenever the Contractor takes corrective action which may
change or affect the tuning criteria for DFTPP (e.g., ion
source cleaning or repair, etc.), the tune must be verified
irrespective of the 12-hour tuning requirements.
E-29/SV 2/88
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TABLE 1.2. DFTPP KEY IONS AND ION ABUNDANCE CRITERIA
Mass Ion Abundance Criteria
51 30.0-60.0 percent of mass 198
68 less than 2.0 percent of mass 69
70 less than 2.0 percent of mass 69
127 40.0 - 60.0 percent of mass 198
197 less than 1.0 percent of mass 198
198 base peak, 100 percent relative abundance
199 5.0 - 9.0 percent of mass 198
275 10.0 - 30.0 percent of mass 198
365 greater than 1.00 percent of mass 198
441 present but less than mass 443
442 greater than 40.0 percent of mass 198
443 17.0 - 23.0 percent of mass 442
1.2 Documentation
The Contractor shall provide documentation of the calibration in the
form of a bar graph spectrum and as a mass listing.
1.2.1 The Contractor shall complete a Form V (GC/MS Tuning and Mass
Calibration) each time an analytical system is tuned. In
addition, all samples, standards, blanks, matrix spikes, and
matrix spike duplicates analyzed during a particular tune must
be summarized in chronological order on the bottom of the
appropriate Form V. Detailed instructions for the completion
of Form V are found in Exhibit B, Section III.
PART 2 - CALIBRATION OF THE GC/MS SYSTEM
2. Summary
Prior to the analysis of samples and required blanks and after tuning
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 TCL compound standards. Once the system has been
calibrated, the calibration must be verified each twelve (12) hour time
period for each GC/MS system.
2.1 Prepare calibration standards as described in Exhibit D SV, Section IV,
to yield the following specific concentrations:
2.1.1 Semivolatile TCL Compounds
Initial calibration of semivolatile TCL compounds is required
at 20, 50, 80, 120, and 160 total nanograms. If an analyte
saturates at the 160 total nanogram concentration level, and
the GC/MS system is calibrated to achieve a detection
sensitivity of no less than the CRQL, the laboratory must
document it on Form VI and in the Case Narrative, and attach a
quantitation report and RIC. In this instance, the laboratory
E-30/SV 2/88
-------
should calculate the results based on a four-point initial
calibration for the specific analvte. The use of a secondary
ion for quantitation is only allowed when there are sample
interferences with the primary ion. If secondary ion
quantitation is performed, document the reasons in the Case
Narrative. Nine compounds: Benzoic Acid, 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 since
detection at less than 50 nanograms per injection is difficult.
2.2 The USEPA plans to develop performance based criteria for response
factor data acquired during this program. To accomplish this goal, the
Agency has specified both the concentration levels for initial
calibration and has also specified the specific internal standard to be
used on a compound-by-compound basis for quantitation (Table 2.2).
Establishment of standard calibration procedures is necessary and
deviations by the Contractor will not be allowed.
2.3 Analyze each calibration standard and tabulate the area of the primary
characteristic ion (Exhibit D SV, Table 4) against concentration for
each compound including all contract required surrogate compounds. The *
relative retention times of each compound in each calibration run
should agree within 0.06 relative retention time units. Late eluting
compounds usually will have much better agreement.
Using Table 2.2, calculate the relative response factors (RRF) for each
compound at each concentration level using Equation 2.1.
AX is
RRF - x Eq. 2.1
where,
Ais Cx
A^ - Area of the characteristic ion for the compound to be
measured.
A^s - Area of the characteristic ion for the specific internal
standards from Table 2.1 or 2.2.
C^is - Concentration of the internal standard (ng/uL).
C - Concentration of the compound to be measured (ng/uL).
2.3.1 Using the relative response factors (RRF) from the initial
calibration, calculate the percent relative standard deviations
(%RSD) for compounds labeled on Form VI as Calibration Check
Compounds and shown in Table 2.3 (see 2.6.2) using Equation
2.2.
%RSD - SD X 100 Eq. 2.2
"x
where,
RSD - Relative Standard Deviation
E-31/SV 2/88
-------
SD - Standard Deviation of initial response factors
(per compound)
where: SD
N-l
x - mean of initial relative response factors (per
compound)
The %RSD for each individual Calibration Check Compound must be
less than or equal to 30.0 percent. This criteria must be met
for the initial calibration to be valid.
2.4 A system performance check must be performed to ensure that minimum
average relative response factors are met before the calibration curve
is used.
2.4.1 For semivolatiles, the System Performance Check Compounds
(SPCCs) are: N-Nitroso-Di-n-Propylamine,
Hexachlorocyclopentadiene , 2 ,4-Dinitrophenol and 4-Nitrophenol*.
The minimum acceptable average relative response factor (RRF)
for these compounds is 0.050. SPCCs typically have very low
RRFs (0.1-0.2) and tend to decrease in response as the
chromatographic system begins to deteriorate or the standard
material begins to deteriorate. These compounds are usually
the first to show poor performance. Therefore, they must meet
the minimum requirement when the system is calibrated.
2.4.2 The initial calibration is valid only after both the %RSD for
CCC compounds and the minimum RRF for SPCC have been met. Only
after both these criteria are met can sarfple analysis begin.
2.5 Documentation
Once the initial calibration is validated, calculate and report the
average relative response factor (RRF) and percent relative standard
deviation (%RSD) for all TCL compounds. The Contractor shall complete
and submit Form V (the GC/MS tune for the initial calibration) and Form
VI (Initial Calibration Data) for each instrument used to analyze
samples under this protocol. Detailed instructions for completion of
Form VI are in Exhibit B, Section III.
2.6 Continuing Calibration
A calibration standard(s) containing all semivolatile TCL compounds,
including all required surrogates, must be analyzed each twelve hours
during analysis (see definition of twelve hour time period, paragraph
1. of this Section). Compare the relative response factor data from
the standards each twelve hours with the average relative response
factor from the initial calibration for a specific instrument. A
system performance check must be made each twelve hours. If the SPCC
E-32/SV 2/88
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criteria are met, a comparison of relative response factors is made for
all compounds. This is the same check that is applied during the
initial calibration (Form VI). If the minimum relative response
factors are not met, the system must be evaluated and corrective action
must be taken before sample analysis begins.
2.6.1 Some possible problems are standard mixture degradation,
injection port inlet contamination, contamination at the* front
end of the analytical column, and active sites in the column or
chromatography system. This check must be met before analysis
begins. The minimum relative response factor (RRF) for
semivolatile System Performance Check Compounds (SPCC) is
0.050.
2.6.2 Calibration Check Compounds (CCC)
After the system performance check is met, Calibration Check
Compounds listed in Table 2.3 are used to check the validity of
the initial calibration. Calculate the percent difference
using Equation 2.3.
RRFj - RRFC
% Difference - x 100 Eq. 2.3
where,
RRFX
. RRFj - average response factor from initial
calibration.
RRF - response factor from current verification check
standard.
2.6.2.1 If the percent difference for any compound is
greater than 20%, the laboratory should consider
this a warning limit. If the percent difference for
each CCC is less than or equal to 25.0%, the initial
calibration is assumed to be valid. If the criteria
are not met (>25.0% difference), for any one
calibration check compound, corrective action MUST
be taken. Problems similar to those listed under
SPCC could affect this criteria. If no source of
the problem can be determined after corrective
action has been taken, a new initial five point
calibration MUST be generated. These criteria MUST
be met before sample analysis begins.
E-34/SV 2/88
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TABLE 2.3. CALIBRATION CHECK COMPOUNDS
Base/Neutral Fraction Acid Fraction
Acenaphthene 4-Chloro-3-Methylphenol
1,4-Dichlorobenzene 2,4-Dichlorophenol
Hexachlorobutadiene 2-Nitrophenol
N-Nitroso-di-n-phenylamine Phenol
Di-n-octylphthalate Pentachlorophenol
Fluoranthene 2,4,6-Trichlorophenol
Benzo(a)pyrene
2.6.3 Concentration Levels for Continuing Calibration Check
The USEPA plans to evaluate the long term stability of response
factors during this program. Standardization among contract
laboratories is necessary to reach these long term goals. Along
with contract specified concentrations for initial calibration,
the USEPA is requiring specific concentrations for each
continuing calibration standard(s).
»
2.6.3.1 The concentration for each semivolatile TCL compound
in the continuing calibration standard(s) is 50
total nanograms for all compounds.
2.7 Documentation
The Contractor shall complete and submit a Form VII for each GC/MS
system utilized for each twelve hour time period. Calculate and report
the relative response factor and percent difference (%D) for all
compounds. Ensure that the minimum RRF for semivolatile SPCCs is
0.050. The percent difference (%D) for each CCC oompound must be less
than or equal to 25.0 percent. Additional instructions for completing
Form VII are found in Exhibit B, Section III.
PART 3 - METHOD BLANK ANALYSIS
3. Summary
A method blank is a volume of deionized, distilled laboratory water for
water samples, or a purified solid matrix for soil/sediment samples,
carried through the entire analytical scheme (extraction,
concentration, and analysis). For soil/sediment samples, a solid
matrix suitable for semivolatile analyses is available from EMSL/LV.
The method blank volume or weight must be approximately equal to the
sample volumes or sample weights being processed.
3.1 Method blank analysis must be performed at the following frequency.
3.1.1 For the analysis of semivolatile TCL compounds, a method blank
analysis must be performed once:
E-35/SV 2/88
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o each Case, OR
o each 14 calendar day period during which samples in a Case
are received (said period beginning with the receipt of the
first sample in that Sample Delivery Group), OR
o each 20 samples in a Case, including matrix spikes and
reanalyses, that are of similar matrix (water or soil)- or
similar concentration (soil only), OR
o whenever samples are extracted by the same procedure
(separatory funnel, continuous liquid-liquid extraction, or
sonication),
whichever is most frequent, on each GC/MS or GC system used to
analyze samples.
3.2 It is the Contractor's responsibility to ensure that method
interferences caused by contaminants in solvents, reagents, glassware,
and other sample processing hardware that lead to discrete artifacts
and/or elevated baselines in gas chromatograms be minimized.
3.2.1 For the purposes of this protocol, an acceptable laboratory
method blank should meet the criteria of paragraphs 3.2.1.1 and
3.2.1.2.
3.2.1.1 A method blank for semivolatile analysis must
contain less than or equal to five times (5X) the
Contract Required Quantitation Limit (CRQL from
Exhibit C) of the phthalate esters in the TCL.
3.2.1.2 For all other TCL compounds not listed above, the
method blank must contain less than or equal to the
Contract Required Quantitation J,imit of any single
TCL analyte.
3.2.2 If a laboratory method blank exceeds these criteria, the
Contractor must consider the analytical system to be out of
control. The source of the contamination must be investigated
and appropriate corrective measures MUST be taken and
documented before further sample analysis proceeds. All
samples processed with a method blank that is out of control
(i.e., contaminated) MUST be reextracted and reanalyzed at no
additional cost to the Agency. The Laboratory Manager, or his
designee, must address problems and solutions in the Case
Narrative (Exhibit B).
3.3 Documentation
The Contractor shall report results of method blank analysis using the
Organic Analysis Data Sheet (Form I) and the form for tentatively
identified compounds (Form I, TIC). In addition, the samples
associated with each method blank must be summarized on Form IV (Method
E-36/SV 2/88
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Blank Summary). Detailed instructions for the completion of these
forms are in Exhibit B, Section III.
3.3.1 The Contractor shall report ALL sample concentration data as
UNCORRECTED for blanks.
PART 4 - SURROGATE SPIKE (SS) ANALYSIS
4. Summary
Surrogate standard determinations are performed on all samples and
blanks. All samples and blanks are fortified with surrogate spiking
compounds before purging or extraction in order to monitor preparation
and analysis of samples.
4.1 Each sample, matrix spike, matrix spike duplicate, and blank are spiked
with surrogate compounds prior to extraction. The surrogate spiking
compounds shown in Table 4.1 are used to fortify each sample, matrix
spike, matrix spike duplicate, and blank with the proper
concentrations. Performance based criteria are generated from
laboratory results. Therefore, deviations from the spiking protocol
will not be permitted.
TABLE 4.1. SURROGATE SPIKING COMPOUNDS
Amount in Sample Extract*
Compounds (before any optional dilutions)
Fraction Water Low/Medium Soil
Nitrobenzene -d^
2-Fluorobiphenyl
p-Terphenyl-d^^
Phenol -d^
2 - Fluorophenol
2,4, 6 -Tribromophenol
BNA
BNA
BNA
BNA
BNA
BNA
50 ug
50 ug
50 ug
100 ug "
100 ug
100 ug
50 ug
50 ug
50 ug
100 ug
100 ug
100 ug
* At the time of injection.
4.2 Surrogate spike recovery must be evaluated by determining whether the
concentration (measured as percent recovery) falls inside the contract
required recovery limits listed in Table 4.2.
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TABLE 4.2. CONTRACT REQUIRED SURROGATE SPIKE RECOVERY LIMITS
Fraction Surrogate Compound Water Low/Medium Soil
BNA
BNA
BNA
BNA
BNA
BNA
Nitrobenzene -dj
2-Fluorobiphenyl
p-Terphenyl-dj^
Phenol -d5
2 - Fluorophenol
2 ,4,6-Tribromophenol
35-114
43-116
33-141
10-94
21-100
10-123
23-120
30-115
18-137
24-113
25-121
19-122
4.3 Treatment of surrogate spike recovery information is according to
paragraphs 4.3.1 through 4.3.2.
4.3.1 Method Blank Surrogate Spike Recovery
The laboratory must take the actions listed below if recovery
of any one surrogate compound in either the base/neutral or
acid fraction is outside of contract surrogate spike recovery
limits.
4.3.1.1 Check calculations to ensure that there are no
errors; check internal standard and surrogate
spiking solutions for degradation, contamination,
etc; also check instrument performance.
4.3.1.2 Reanalyze the blank extract if steps in 4.3.1.1 fail
to reveal the cause of the noncompliant surrogate
recoveries.
*
4.3.1.3 Reextract and reanalyze the blank.
4.3.1.4 If the measures listed in 4.3.1.1 thru 4.3.1.3 fail
to correct the problem, the analytical system must
be considered to be out of control. The problem
MUST be corrected before continuing. This may mean
recalibrating the instrumentation but it may also
mean more extensive action. The specific corrective
action is left up to the GC/MS operator. When
surrogate recovery(ies) in the blank is outside of
the contract required windows, all samples
associated with that blank MUST be reanalyzed at no
additional cost to the Agency.
4.3.2 Sample Surrogate Spike Recovery
The laboratory must take the actions listed below if either of
the following conditions exists:
E-38/SV 2/88
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o Recovery of any one surrogate compound in either base
neutral or acid fraction is below 10%.
o Recoveries of two surrogate compounds in either base
neutral or acid fractions are outside surrogate spike
recovery limits.
4.3.2.1 The Contractor shall document (in this instance*,
document means to write down and discuss the problem
and corrective action taken in the Case Narrative,
see Exhibit B) deviations outside of acceptable
quality control limits and take the following
actions:
4.3.2.1.1 Check calculations to ensure that there
are no errors; check internal standard
and surrogate spiking solutions for
degradation, contamination, etc.; also
check instrument performance.
4.3.2.1.2 If the steps in 4.3.2.1.1 fail to
T«veal a problem, then reanalyze the
extract. If reanalysis of the extract
solves the problem, then the problem
was within the laboratory's control.
Therefore, only submit 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.
4.3.2.1.3 If the steps in 4.3.2.1.2 fail to solve
the problem, then ceextract and
reanalyze the sample. If the
reextraction and reanalysis solves the
problem, then the problem was in the
laboratory's control. Therefore, only
submit data from the extraction and
.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.
If the reextraction and reanalysis of
the sample does not solve the problem;
i.e., surrogate recoveries are outside
the contract windows for both analyses,
then submit the surrogate spike
recovery data and the sample data from
both analyses according to paragraph
•4.4. Distinguish between the initial
analysis and the reanalysis on all data
E-39/SV 2/88
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deliverables, using the sample suffixes
specified in Exhibit B.
4.4 Documentation
The Contractor shall report surrogate recovery data for the following:
o Method Blank Analysis
o Sample Analysis
o Matrix Spike/Matrix Spike Duplicate Analyses
o All sample reanalyses that substantiate a matrix effect
The surrogate spike recovery data is summarized on the Surrogate Spike
Percent Recovery Summary (Form II). Detailed instructions for the
completion of Form II are in Exhibit B, Section III.
PART 5 - MATRIX SPIKE/MATRIX SPIKE DUPLICATE ANALYSIS (MS/MSP)
5. Summary
In order to evaluate the matrix effect of the sample upon the
analytical methodology, the USEPA has developed the standard mixes
listed in Table 5.1 to be used for matrix spike and matrix spike
duplicate analyses. These compounds are subject to change depending
upon availability and suitability for use as matrix spikes.
5.1 MS/MSD Frequency of Analysis
A matrix spike and matrix spike duplicate must be performed for each
group of samples of a similar matrix, once:
o each Case of field samples received, OR
o each 20 field samples in a Case, OR
o each group of field samples of a similar concentration level
(soils only), OR
o each 14 calendar day period during which field samples in a
Case were received (said period beginning with the receipt of
the first sample in that Sample Delivery Group),
whichever is most frequent.
5.2 Use the compounds listed in Table 5.1 to prepare matrix spiking
solutions according to protocols described in Exhibit D SV. The
analytical protocols in Exhibit D SV stipulate the amount of matrix
spiking solution to be added to the sample aliquots prior to
extraction. Each method allows for optional dilution steps which must
be accounted for when calculating percent recovery of the matrix spike
and matrix spike duplicate samples.
E-40/SV 2/88
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TABLE 5.1. MATRIX SPIKING SOLUTIONS
Base/Neutrals
1,2,4-Trichlorobenzene
Acenaphthene
2,4-Dinitrotoluene
Pyrene
N-Nitroso-Di-n-Propylamine
1,4-Dichlorobenzene
Pentachlorophenol
Phenol
2-Chlorophenol
4-Chloro-3-Methylphenol
4-Nitrophenol
5.2.1 Samples requiring optional dilutions and chosen as the matrix
spike/ matrix spike duplicate samples, must be analyzed at the
same dilution as the original unspiked sample.
5.3 Individual component recoveries of the matrix spike are calculated
using Equation 5.1.
SSR - SR
Matrix Spike Percent Recovery - x 100
SA
Eq. 5.1
where
SSR - Spike Sample Results
SR - Sample Result
SA - Spike Added from spiking mix
5.4 Relative Percent Difference (RPD)
The Contractor is required to calculate the relative percent difference
between the matrix spike and matrix spike duplicate. The relative
percent differences (RPD) for each component are calculated using
Equation 5.2.
Dl - D2
RPD
x 100
(Dl + D2)/2
Eq. 5.2
where
RPD - Relative Percent Difference
Dl - First Sample Value
D2 - Second Sample Value (duplicate)
5.5 Documentation
The matrix spike (MS) results (concentrations) for nonspiked
semivolatile TCL compounds shall be reported on Form I (Organic
Analysis Data Sheet) and the matrix spike percent recoveries shall be
summarized on Form III (MS/MSD Recovery). These values will be used by
E-41/SV
2/88
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EPA to periodically update existing performance based QC recovery
limits (Table 5.2).
The results for nonspiked semivolatile TCL compounds in the matrix
spike duplicate (MSD) analysis shall be reported on Form I (Organic
Analysis Data Sheet) and the percent recovery and the relative percent
difference shall be summarized on Form III (MS/MSD Recovery). The RPD
data will be used by EPA to evaluate the long term precision of the
analytical method. Detailed instructions for the completion of Form
III are in Exhibit B, Section III.
TABLE 5.2. MATRIX SPIKE RECOVERY LIMITS*
Fraction Matrix Spike Compound Water Soil/Sediment
BN
BN
BN
BN
BN
BN
Acid
Acid
Acid
Acid
Acid
1 , 2 , 4-Trichlorobenzene
Acenaphthene
2 , 4-Dinitrotoluene
Pyrene
N-Nitroso-Di-n-Propylamine
1 ,4-Dichlorobenzene
Pentachlorophenol
Phenol
2-Chlorophenol
4-Chloro-3-Methylphenol
4-Nitrophenol
39-98
46-118
24-96
26-127
41-116
36-97
9-103
12-89
27-123
23-97
10-80
38-107
31-137
28-89
35-142
41-126
28-104
17-109
26-90
25-102
26-103
11-114
PART 6 - SAMPLE ANALYSIS
6. Summary
The intent of Part 6 is to provide the Contractor with a brief summary
of ongoing QC activities involved with sample analysis. Specific
references are provided to help the Contractor meet specific reporting
and deliverabies requirements of this contract.
6.1 Sample Analysis
Samples can be analyzed upon successful completion of the initial QC
activities. When twelve (12) hours have elapsed since the initial tune
was completed, it is necessary to conduct an instrument tune and
calibration check analysis (described in Part 2 of this Section). Any
major system maintenance, such as a source cleaning or installation of
a new column, may necessitate a retune and recalibration (see Initial
Calibration, Part 2). Minor maintenance should necessitate only the
calibration verification (Continuing Calibration, Part 2).
6.1.1 Internal Standards Evaluation - Internal standard responses and
retention times in all samples must be evaluated immediately
after or during data acquisition. If the retention time for
E-42/SV 2/88
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any Internal standard changes by more than 30 seconds, the
chromatographic system must be Inspected for malfunctions, and
corrections made as required. The extracted ion current.
profile (EICP) of the internal standards must be monitored and
evaluated for each sample, blank, matrix spike, and matrix
spike duplicate. The criteria are described in detail in the
instructions for Form VIII, Internal Standard Area Summary (see
Exhibit B, Section III). If the extracted ion current profile
(EICP) area for any internal standard changes by more than a
factor of two (-50% to 100%), from the latest daily (12 hour
time period) calibration standard, the mass spectrometric
system must be inspected for malfunction, and corrections made
as appropriate. Breaking off 1 foot of the column or cleaning
the injector sleeve will often improve high end sensitivity for
the late eluting compounds; repositioning or repacking the
front end of the column will often improve front end column
performance. Poor injection technique can also lead to
variable IS ratios. When corrections are made, reanalysis of
samples analyzed while the system was malfunctioning is
necessary.
6.1.1.1 If after reanalysis, 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, only submit 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.
6.1.1.2 If the reanalysis of the sample does not solve the
problem, i.e., the EICP areas are outside contract
limits for both analyses, then submit the EICP data
and sample data from both analyses. Distinguish
between the initial analysis and the reanalysis on
all data deliverables, using the sample suffixes
specified in Exhibit B. Document in the Case
Narrative all inspection and corrective actions
taken.
6.1.2 Each analytical run must also be checked 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 method calibration (Part 2) requires
that the system should not be saturated for high response
compounds at 160 nanograms for semivolatile TCL compounds.
6.1.2.1 If the on-column concentration of any compound in
any sample exceeds the initial calibration range,
that sample must be diluted, the internal standard
concentration readjusted, and the sample reinjected,
as described in specific methodologies in Exhibit D
SV. Secondary ion quantitation is only allowed when
E-43/SV 2/88
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there are sample matrix interferences with the
primary ion.
6.1.2.2 If the dilution of the sample causes any compound
detected in the first analysis to be undetectable in
the second analysis, then the results of both
analyses shall be reported on separate Forms I,'
according to the instructions in Exhibit B.
6.1.3 Qualitative Analysis
The semivolatile compounds listed in the Target Compound List
(TCL), Exhibit C, shall be identified by an analyst competent
in the interpretation of mass spectra, by comparison of the
suspect 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 (see Exhibit D SV, Section IV).
6.1.3.1 For establishing correspondence of the GC relative
retention time (RRT), the sample component RRT must
compare within ±0.06 RRT units of the RRT of the
standard component. For reference, the standard
must be run on the same shift as the sample.
6.1.3.2 For comparison of standard and sample component mass
spectra, mass spectra obtained on the Contractor's
GC/MS are required. The DFTPP tuning requirements
listed in Part 1 must be met on the same GC/MS.
6.1.3.2.1 The requirements for qualitative
verification by comparison of mass
spectra are as follows:
o 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.
o The relative intensities of ions
specified in the above paragraph
-- must agree within ±20% between the
standard and sample spectra.
o 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. When GC/MS
computer data processing programs
are used to obtain the sample
E-44/SV 2/88
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component spectrum, both the
processed and the raw spectra must
be evaluated. In Task III, the
verification process should favor
false negatives (Exhibit D SV,
Section IV).
6.1.3.2.2 If a compound cannot be verified by all
of the criteria in 6.1.3.2.1, but in
the technical judgement of the mass
spectral interpretation specialist the
identification is correct, the
Contractor shall report the
identification and proceed with the
quantitation.
6.1.3.3 A library search shall be executed for nonsurrogate
and non-TCL sample components for the purpose of
tentative identification. For this purpose, the 1985
or most recent available version of the National
Bureau of Standards Mass Spectral Library,
containing 42,261 spectra, should be used.
6.1.4 Quantitation
6.1.4.1 Semivolatile TCL components identified shall be
quantitated by the internal standard method. The
internal standards used shall be the ones assigned
in Table 2.2 of this Section. The EICP area of
characteristic ions of TCL analytes are used
(Exhibit D SV, Section IV).
6.1.4.2 An estimated concentration for non-TCL components
tentatively identified shall be quantitated by the
internal standard method. Fot*"quantification, the
nearest internal standard free of interferences must
be used.
6.1.4.3 Calculate surrogate standard recovery (see Part 4)
for all surrogate compounds on all samples, blanks,
matrix spikes, and matrix spike duplicates. If
recovery is within contractual limits, report on
Form II (see Exhibit B, Section III). If recovery
is outside contractual limits, take specific steps
listed in Surrogate Spike Recoveries (Part 4).
6.1.4.4 Calculate matrix spike and matrix spike duplicate
percent recovery (see Part 5) for all compounds and
report results on Form III (see Exhibit B, Section
III). Calculate Relative Percent Differences (RPDs)
for all matrix spiking compounds and report results
on Form III. Ensure that the proper frequency of
MS/MSD analysis is maintained.
E-45/SV 2/88
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6.1.5 Reporting and Deliverables
Refer to Exhibit B of this Statement of Work for specific
details on contract deliverables and reporting formats. Exhibit
B contains specific instructions for completing all required
Forms, as well as a detailed itemization of reporting and
deliverables requirements. Exhibit H contains the format
requirements for delivery of data in computer-readable format.
E-46/SV 2/88
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SECTION III PEST
PESTICIDES/PCBs QA/QC
REQUIREMENTS
E-47/PEST 2/88
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This Section outlines the minimum quality control (QC) operations necessary
to satisfy the analytical requirements associated with the determination of
pesticide/PCB organic TCL compounds in water and soil/sediment samples.
These QC operations are as follows:
o Method Blank Analysis
o Surrogate Spike Response Monitoring
o Matrix Spike and Matrix Spike Duplicate Analysis
o Specific QA/QC for Pesticide Analysis
PART 1 - METHOD BLANK ANALYSIS
1. Summary
A method blank is a volume of deionized, distilled laboratory water for
water samples, or a purified solid matrix for soil/sediment samples,
carried through the entire analytical scheme (extraction,
concentration, and analysis). For soil/sediment samples, a solid
matrix suitable for pesticide analyses is available from EMSL-LV. The
method blank volume or weight must be approximately equal to the sample
volumes or sample weights being processed.
1.1 Method blank analysis must be performed at the following frequency:
1.1.1 For the analysis of pesticide/PCB TCL compounds, a method blank
analysis must be performed once:
o each Case, OR
o each 14 calendar day period during which samples in a Case
are received (said period beginning with the receipt of the
first sample in that Sample Delivery Gztmp), OR
o each 20 samples in a Case, including matrix spike 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
(separatory funnel or continuous extraction),
whichever is most frequent, on each GC/MS or GC system used to
analyze samples.
1.2 It is the Contractor's responsibility to ensure that method
interferences caused by contaminants in solvents, reagents, glassware,
and other sample processing hardware that lead to discrete artifacts
and/or elevated baselines in gas chromatograms be minimized.
1.2.1 For the purposes of this protocol, an acceptable laboratory
method blank should meet the criteria of paragraph 1.2.1.1.
1.2.1.1 The method blank must contain less than or equal to
the Contract Required Quantitation Limit of any
single pesticide/PCB Target Compound (Exhibit C).
E-48/PEST 2/88
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1.2.2 If a laboratory method blank exceeds these criteria, the
Contractor must consider the analytical system to be out of
control. The source of the contamination must be investigated
and appropriate corrective measures MUST be taken and
documented before further sample analysis proceeds. All
samples processed with a method blank that is out of control
(i.e., contaminated) MUST be reextracted and reanalyzed at no
additional cost to the Agency. The Laboratory Manager, 'or his
designee, must address problems and solutions in the Case
Narrative (Exhibit B).
1.3 Documentation
The Contractor shall report results of method blank analysis using the
Organic Analysis Data Sheet (Form I). In addition, the samples
associated with each method blank must be summarized on Form IV (Method
Blank Summary). Detailed instructions for the completion of these
forms can be found in Exhibit B, Section III.
1.3.1 The Contractor shall report ALL sample concentration data as
UNCORRECTED for blanks.
PART 2 - SURROGATE SPIKE CSS) ANALYSIS
2. Summary
Surrogate standard determinations are performed on all samples and
blanks. All samples and blanks are fortified with surrogate spiking
compounds before purging or extraction in order to monitor preparation
and analysis of samples.
2.1 Each sample, matrix spike, matrix spike duplicate, and blank are spiked
with surrogate compounds prior to extraction. The surrogate spiking
compounds shown in Table 4.1 are used to fortify"each sample, matrix
spike, matrix spike duplicate, and blank with the proper
concentrations. Performance based criteria are generated from
laboratory results. Therefore, deviations from the spiking protocol
will not be permitted.
TABLE 4.1. SURROGATE SPIKING COMPOUND
Amount in Sample Extract*
Compound (before any optional dilutions)
FractiSh Water Low/Medium Soil
Dibutylchlorendate Pest. 0.1 ug 0.1 ug
* At the time of injection.
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2.2 Surrogate spike recovery must be evaluated by determining whether the
concentration (measured as percent recovery) falls inside the advisory
recovery limits listed in Table 4.2.
TABLE 4.2. ADVISORY SURROGATE SPIKE RECOVERY LIMITS
Low/Medium
Fraction Surrogate Compound Water Soil/Sediment
Pest. Dibutylchlorendate (24-154)* (20-150)*
•t
* These limits are for advisory purposes only. They are not used to
determine if a sample should be reanalyzed. When sufficient data becomes
available, the USEPA may set performance based contract required windows.
2.3 Documentation
The Contractor shall report surrogate recovery data for the following:
o Method Blank Analysis
o Sample Analysis
o Matrix Spike/Matrix Spike Duplicate Analyses
The surrogate spike recovery data is summarized on the Surrogate Spike
Percent Recovery Summary (Form II). Detailed instructions for the
completion of Form II are in Exhibit B, Section III.
PART 3 - MATRIX SPIKE/MATRIX SPIKE- DUPLICATE ANALYSIS (MS/MSP')
3. Summary
In order to evaluate the matrix effect of the sample upon the
analytical methodology, the USEPA has developed the standard mixes
listed in Table 5.1 to be used for matrix spike and matrix spike
duplicate analyses. These compounds are subject to change depending
upon availability and suitability for use as matrix spikes.
3.1 MS/MSD Frequency of Analysis
A matrix spike and matrix spike duplicate must be performed for each
group of samples of a similar matrix, once:
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
E-50/PEST 2/88
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o each 14 calendar day period during which field samples in a Case
were received (said period beginning with the receipt of the first
sample in that Sample Delivery Group),
whichever is most frequent.
3.2 Use the compounds listed in Table 5.1 to prepare matrix spiking
solutions according to protocols described in Exhibit D PEST. The
analytical protocols in Exhibit D PEST stipulate the amount of matrix
spiking solution to be added to the sample aliquots prior to
extraction. Each method allows for optional dilution steps which must
be accounted for when calculating percent recovery of the matrix spike
and matrix spike duplicate samples.
TABLE 5.1. MATRIX SPIKING SOLUTIONS
Pesticides
Heptachlor Lindane
Aldrin Endrin
Dieldrin 4,4'-DDT
3.2.1 Samples requiring optional dilutions and chosen as the matrix
spike/matrix spike duplicate samples, must be analyzed at the
same dilution as the original unspiked sample.
3.3 Individual component recoveries of the matrix spike* are calculated
using Equation 5.1.
SSR - SR
Matrix Spike Percent Recovery - x 100 Eq. 5.1
SA
where
SSR - Spike Sample Results
SR - Sample Result
SA - Spike Added from spiking mix
3.4 Relative Percent Difference (RPD)
The Contractor is required to calculate the relative percent difference
between the matrix spike and matrix spike duplicate. The relative
percent differences (RPD) for each component are calculated using
Equation 5.2.
E-51/PEST 2/88
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Dl - D2
RPD - i — x 100 Eq. 5.2
(D1 + D2)/2
where
RPD - Relative Percent Difference
Di - First Sample Value
Do - Second Sample Value (duplicate)
3.5 Documentation
The matrix spike (MS) results (concentrations) for nonspiked
pesticide/PCB TCL compounds shall be reported on Form I (Organic
Analysis Data Sheet) and the matrix spike percent recoveries shall be
summarized on Form III (MS/MSD Recovery). These values will be used by
EPA to periodically update existing performance based QC recovery
limits (Table 5.2).
The results for nonspiked pesticide/PCB TCL compounds in the matrix
spike duplicate (MSD) analysis shall be reported on Form I (Organic .
Analysis Data Sheet) and the percent recovery and the relative percent
difference shall be summarized on Form III (MS/MSD Recovery). The RPD *
data will be used by EPA to evaluate the long term precision of the
analytical method. Detailed instructions for the completion of Form
III are in Exhibit B, Section III.
TABLE 5.2. MATRIX SPIKE RECOVERY LIMITS*
Fraction Matrix Spike Compound Water Soil/Sediment
Pest.
Pest.
Pest.
Pest.
Pest.
Pest.
Lindane
Heptachlor
Aldrin
Dieldrin
Endrin
4,4' -DDT
56-123
40-131
40-120
52-126 .
56-121
38-127
* 46-127
35-130
34-132
31-134
42-139
23-134
* These limits are for advisory purposes onlv. They are not to be
used to determine if a sample should be reanalyzed. When sufficient
multi-lab data are available, standard limits will be calculated.
PART 4 - PESTICIDE QA/OC REQUIREMENTS
4. Summary
Part 4 summarizes ongoing QC activities involved with pesticide/PCB
analysis that were detailed in Parts 1, 2 and 3 of this Section, and
describes the additional QA/QC procedures required during the analysis
of pesticide/PCBs that are not covered in Parts 1, 2, and 3.
E-52/PEST 2/88
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4.1 The Contractor must perform the following:
4.1.1 Method Blank analysis as per Part 1 of this Section.
4.1.2 Spike all standards, samples, blanks, matrix spike and matrix
spike duplicate samples with the surrogate spike compound
(dibutylchlorendate) as per Part 2 of this Section.
4.1.3 Matrix Spike/Matrix Spike duplicate analysis as per Part 3 of
this Section.
4.2 The external standard quantitation method must be used to quantitate
all pesticides/PCBs. Before performing any sample analysis, the
laboratory is required to determine the retention time window for each
pesticide/PCB target compound listed in Exhibit C and the surrogate
spike compound, dibutylchlorendate. These retention time windows are
used to make tentative identification of pesticides/PCBs during sample
analysis.
4.2.1 Prior to establishing retention time windows, the GC operating
conditions (oven temperature and flow rate) must be adjusted
such that 4,4'-DDT has a retention time of > 12 minutes on
packed GC columns, except on OV-1 or OV-101 columns.
Conditions listed in Table 7, Exhibit D PEST, Section IV may be
used to achieve this criteria.
4.2.2 Establish retention time windows as follows:
4.2.2.1 At the beginning of the contract and each time a new
GC column is installed, make three injections of all
single component pesticides mixtures, multi-response
pesticides, and PCBs throughout the course of a 72-
hour period. The concentration of each
pesticide/PCB should be sufficient to provide a
response that is approximately half scale. The
three injections of each compound should be made at
approximately equal intervals during the 72-hour
period, (e.g., each compound should be injected near
the beginning, near the middle, and near the end of
the 72-hour period).
4.2.2.2 Verify the retention time shift for
dibutylchlorendate in each standard. The retention
time shift between the initial and subsequent
standards must be less than 2.0% difference for
packed columns, less than 1.5% difference for wide
bore capillary columns (ID greater than 0.32 mm),
and less than 0.3% difference for narrow bore
capillary columns (ID less than 0.32 mm). If this
criterion is not met, continue injecting replicate
standards to meet this criterion.
4.2.2.3 Calculate the standard deviation of the three
absolute retention times for each single component
E-53/PEST 2/88
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pesticide. For multiresponse pesticides or PCBs,
choose one major peak from the envelope and
calculate the standard deviation of the three
retention times for that peak.
4 2.2.U The standard deviations determined in 4.2-2,3 shall
ae asaif. "te detaBTsainfi the retention tia»e -windows for
a particular 72-hour sequence. Apply plus or*minus
three times the standard deviations in 4.2.2.3 to
the retention time of each pesticide/PCB determined
for the first analysis of the pesticide/PCB standard
in a given 72 hour analytical sequence. This range
of retention times defines the retention time window
for the compound of interest for that 72-hour
sequence. NOTE: By definition, the retention time
of a pesticide/PCB from the first analysis of that
compound in the 72 hour sequence is the center of
the retention time window. Do not use the retention
time measured in 4.2.2.1 as the center of the
retention time window. The experience of the
analyst should weigh heavily in the interpretation
of chromatograms. For miitiresponse pesticide/PCBs.
the analyst should utilize the retention time window
but should primarily rely on pattern recognition.
For example, the three injections of aldrin in
4.2.2.1 have a mean retention time of 1.40 minutes
and a standard deviation of 0.01 minutes. The
retention time of the aldrin standard at the
beginning of the 72-hour sequence begun today is
1.51 minutes. Three times the standard deviation
(D.01) is applied to the retention time of aldrin
from the sequence begun today, e.g., 1.51 + 3(0.01)
- 1.48-1.54. If aldrin has a"retention time of 1.60
minutes at the beginning of the next 12-hour
sequence, then the retention time window becomes:
1.60 + 3(0.01) - 1.57-1.63 for that 72-hour
sequence.
5 In those cases where the retention time window for a
particular pesticide/PCB is less than 0.01 minutes,
the laboratory may substitute whichever of the
following formulae apply.
o For packed columns, the retention time window of
the particular pesticide/PCB shall be calculated
as ± 1% of the initial retention time of the
compound in the 72-hour sequence.
o For wide bore capillary columns (IB greater than
0.32 mm), the retention time window of the
particular pesticide/PCB shall be calculated as
+ 0.75% of the initial retention time of the
compound in the 72-hour sequence.
E-54/PEST 2/88
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o For narrow bore capillary columns (ID less than
0.32 mm), the retention time window of the
particular pesticide/PCB shall be calculated as
+ 0.15% of the initial retention time of the
compound in the 72-hour sequence.
4.2.2.6 Regardless of whether the retention time windows are
calculated by the method in 4.2.2.4 or 4.2.2.5, the
retention time windows must be reported as a range
of values, not as, for example, 1.51 minutes + 1%.
4.2.2.7 The laboratory must calculate retention time windows
for each pesticide/PCB on each GC column used at the
beginning of the program and whenever a new GC
column is installed. The data must be retained by
the laboratory and made available during an on-site
laboratory evaluation.
4.3 Primary GC Column Analysis
4.3.1 Primary Analysis establishes whether or not pesticides/PCBs are
present in the sample, and establishes a tentative
identification of each compound. Quantitation may be performed,
on the primary analysis if the analysis meets all of the QC
criteria specified for quantitation. NOTE: To determine that
no pesticides/PCBs are present at or above the contract
required quantitation limit is a form of quantitation.
4.3.2 Separation should be > 25 percent resolution between peaks.
This criteria must be considered when determining whether to
quantitate on the Primary Analysis or the Confirmation
Analysis. When this criterion cannot be met, quantitation is
adversely affected because of the difficulty in determining
where to establish the baseline.
4.3.3 Evaluation Standard Mixtures
4.3.3.1 Prepare Evaluation Standard Mixes A, B, and C
(Aldrin, Endrin, 4,4'-DDT and Dibutylchlorendate) at
the 3 concentration levels described in Exhibit D
PEST. Analyze the three Evaluation Standard Mixes
sequentially at the beginning of each seventy-two
(72) hour period (See Figure 4.1).
4.3.3.2 Calculate the Calibration Factor (ratio of the total
area to the mass injected) for each compound in
Evaluation Standard Mix A, B and C using Equation
4.1.
Calibration Total Area of Peak
Factor - Eq.4.1
Mass Injected (in nanograms)
E-55/PEST 2/88
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4.3.3.3 Using the Calibration Factors from 4.3.3.2 above,
calculate the percent relative standard deviation
(%RSD) for each compound at the three concentration
levels using Equation 4.2. The percent relative
standard deviation for Aldrin, Endrin, and
Dibutylchlorendate must be less than or equal to
10.0 percent. If the %RSD exceeds 10.0% for
4,4'-DDT, see Section 4.5.4.4.
Note: The 10.0% RSD linearity criteria pertains
only to columns being used for Pesticide/PCB
quantitation. If a column is used only for surrogate
quantitation, the 10.0% RSD is only required for
Dibutylchlorendate.
% Relative
Standard Deviation -
SD
x 100
Eq. 4.2
where Standard Deviation (SD) -
N-l
x - mean of initial three Calibration Factors (per
compound).
4.3.3.4 Evaluate the chromatogram from the analysis of the
Evaluation Mix B. The appearance of peaks in
addition to the four main pesticide peaks indicates
a breakdown of Endrin and/or 4,4'-DDT.
4.3.3.5 Calculate the percent breakdoifn for Endrin and/or
4,4'-DDT on the mixed phase (1.5% 0V-16/1.95% OV-210
or equivalent) GC column using Equations 4.3 and
4.4. The percent breakdown for Endrin or 4,4'-DDT
must not exceed 20.0 percent. Corrective action
must be taken before analysis continues.
% breakdown Total DDT degradation peak area (DDE + ODD)
for :
4,4'-DDT
% breakdown
for Endrin
Total DDT peak area1 (DDT + DDE + ODD)
Total Endrin degradation peak areas
(Endrin Aldehyde + Endrin Ketone)
Total Endrin Peak Area^(Endrin +
Endrin Aldehyde + Endrin Ketone)
x 100 Eq. 4.3
X 100
Eq. 4.4
The term peak height may be substituted for the term peak area.
E-56/PEST 2/88
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4.3.3.6 Calculate the percent breakdown for Endrin and/or
4,4'-DDT on the OV-1 or equivalent GC column using
Equations 4.3 and 4.4 The percent breakdown for
Endrin or 4,4'-DDT must not exceed 20.0 percent.
Corrective action must be taken before analysis
continues.
4.3.3.7 If there is evidence of a peak at the retention time
for Endrin aldehyde/4,4'-ODD (which coelute on the
OV-1 or equivalent GC column), calculate a combined
percent breakdown for Endrin/4,4'-DDT using Equation
4.5. The combined Endrin/4,4'-DDT percent breakdown
must not exceed 20.0 percent, else corrective action
must be taken before analysis continues.
Total Endrin/DDT degradation peak areas2
Combined (ODD, DDE, Endrin Aldehyde, Endrin Ketone)
% breakdown X 100 Eq. 4.5
Total Endrin/DDT degradation peak area
(Endrin, Endrin Aldehyde, Endrin Ketone,
ODD, DDE, DDT)
4.3.3.8 Suggested Maintenance
Corrective measures may require any one or more of
the following remedial actions:
4.3.3.8.1 Packed columns - For instruments with
off-column injection; replace the
demister trap, clean and deactivate the
glass injection port insert or replace
with a cleaned and deactivated insert.
Inspect the injection end of the column
and remove any foreign material (broken
glass from the rim of the column or
pieces of septa). Replace the glass
wool with fresh deactivated glass wool.
Also, it may be necessary to remove the
first few millimeters of packing
material if any discoloration is noted,
also swab out the inside walls of the
column if any residue is noted. If
these procedures fail to eliminate the
degradation problem, it may be
necessary to deactivate the metal
injector body (described below) and/or
repack/replace the column.
4.3.3.8.2 Capillary columns - Clean and
deactivate the glass injection port
insert or replace with a cleaned and
The term peak height may be substituted for the term peak area.
E-57/PEST 2/88
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deactivated insert. Break off the
first few inches, up to one foot, of
the injection port side of the'column.
Remove the column and solvent backflush
according to the manufacturer's
instructions. If these procedures fail
to eliminate the degradation problem,
it may be necessary to deactivate the
metal injector body and/or replace the
column.
4.3.3.8.3 Metal Injector Body - Turn off the oven
and remove the analytical column when
the oven has cooled. Remove the glass
injection port insert (instruments with
off-column injection or Grob). Lower
the injection port temperature to room
temperature. Inspect the injection
port and remove any noticeable foreign
material.
Place a beaker beneath the injector
port inside the GC oven. Using a wash
bottle, serially rinse the entire
inside of the injector port with
acetone and then toluene, catching the
rinsate in the beaker.
Prepare a solution of deactivating
agent (Sylon-CT or equivalent)
following manufacturer's directions.
After all metal surfaces inside the
injector body have been thoroughly
coated with the deactivation solution,
serially rinse the injector body with
toluene, methanol, acetone and hexane.
Reassemble the injector and replace the
GC column.
4.3.4 Individual Standard Mixtures A and B
4.3.4.1 Prepare Individual Standard Mixtures A and B
containing the single component pesticides. These
may be divided into the groups suggested in Exhibit
D PEST, which are recommended to prevent overlap of
compounds on two of the packed columns. One mixture
of all of the single component pesticides is
acceptable when using capillary column. Prepare
separate solutions of all multi-response pesticides
and PCBs. (Aroclor 1016 and Aroclor 1260 may be
combined in a single mixture.)
4.3.4.2 Analyze Individual Standard Mixtures A and B and all
multi-response pesticide/PCBs at the beginning of
E-58/PEST 2/88
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each 72 hour period (see Figure 4.1) and analyze
Individual Standard Mixtures A and B at the
intervals specified in the analytical sequence in
Figure 4.1, and whenever sample analysis is
completed. The Calibration Factor for each standard
quantitated (Individual Standard Mix A or B)
(Equation 4.6), must not exceed & 15.0 percent
difference for a quantitation run nor exceed a 20.0
percent difference for a confirmation run during the
72 hour period. Calculate percent difference using
Equation 4.7. Deviations greater than 15.0 percent
require the laboratory to repeat the samples
analyzed following the quantitation standard that
exceeded the criterion.
NOTE: Aroclors 1221 and 1232 must be analyzed at a
minimum of once a month on each instrument and each
column. Copies of these chromatograms must be
submitted with each case for instruments and columns
used to quantitate samples in that case, when
identity of these two pesticides (Aroclor 1221 and
1232) has been confirmed.
*
Total Area of Peak*
Calibration Factor - —= -.—:—„ . ,. r— Eq. 4.6
Mass injected (in nanograms) ^
* For multiresponse pesticides/PCBs use the total
area of all peaks used for quantitation.
Rl " R2
Percent Difference - x 100 Eq. 4.7
Rl
*
where
Ri - Calibration Factor from first analysis
R2 - Calibration Factor from second or subsequent
analysis
4.4 Sample Analysis (Primary GC Column)
4.4.1 Samples are analyzed per the sequence described in Figure 4.1.
4.4.2 The retention time shift for Dibutylchlorendate must be
evaluated after the analysis of each sample. The retention
time shift must be less than 2.0% difference for packed GC
columns between the initial standard analysis and any sample or
standard analyzed during the 72 hour period. The percent
difference for wide bore capillary columns (ID greater than
0.32 mm) must be less than 1.5%. The percent difference for
narrow bore capillary columns (ID less than 0.32 mm) must be
less than 0.3% (Equation 4.8).
E-59/PEST 2/88
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RT - RT
Percent Difference (%D) - —^1 S x ioo Eq. 4.8
where
RTj - absolute retention time of Dibutylchlorendate in the
initial standard (Evaluation Standard Mix A).
RTg - absolute retention time of Dibutylchlorendate in the
sample or subsequent standard.
4.4.3 Evaluate the GC column throughout the analysis of samples by
injecting Evaluation Standard Mix B at the frequency outlined
in Figure 4.1.
4.4.4 Calculate the percent breakdown for 4,4'-DDT and Endrin
according to 4.3.3.5. Take corrective action when the
breakdown for 4,4'-DDT or Endrin exceeds 20.0 percent.
FIGURE 4.1 72 HOUR SEQUENCE FOR PESTICIDE/PCB ANALYSIS
1. Evaluation Standard Mix A
2. Evaluation Standard Mix B
3. Evaluation Standard Mix C
4. Individual Standard Mix A*
5. Individual Standard Mix B*
6. Toxaphene
7. Aroclors 1016/1260
8. Aroclor 1221**
9. Aroclor 1232**
10. Aroclor 1242
11. Aroclor 1248
12. Aroclor 1254
13. 5 Samples
14. Evaluation Standard Mix B
15. 5 Samples
16. Individual Standard Mix A or B "
17. 5 Samples
18. Evaluation Standard Mix B
19. 5 Samples
20. Individual Standard Mix A or B (whichever not run in step 16)
21. 5 Samples
22. Repeat the above sequence starting with Evaluation Standard Mix B (step
14 above).
23. Pesticide/PCB analysis sequence must end with the analysis of both
Individual Standard Mix A and B regardless of number of samples
analyzed.
* These may be one mixture.
** Aroclors 1221 and 1232 must be analyzed at a minimum of once per month on
each instrument and each column. Copies of these chromatograms must be
submitted with each Case for instruments and columns used to quantitate
samples in that Case.
E-60/PEST 2/88
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4.4.5 If one or more compounds have a response greater than full
scale, the extract requires dilution according to the
specifications in Exhibit D PEST. If the dilution of the
extract causes any compounds tentatively identified in the
first analysis to be undetectable in the second analysis, then
the results of both analyses shall be reported on separate
Forms I, according to the instructions in Exhibit B. For
dilutions greater than 10-fold, also see the instructions in
Exhibit D PEST.
4.5 Confirmation Analysis (GC/EC)
4.5.1 Confirmation Analysis is to confirm the presence of all
compounds tentatively identified in the Primary Analysis.
Therefore, the only standards that are required are the
Evaluation Standard Mixes (to check linearity and degradation
criteria) and standards of all compounds to be confirmed. The
72-hour sequence described in Figure 4.1 is, therefore,
modified to fit each case. Quantitation may be performed on
the confirmation analysis. If toxaphene or DDT is to be
quantitated, the linearity requirements are specified in
Section 4.5.4.
4.5.2 Separation should be > 25 percent resolution between peaks.
This criteria must be considered when determining whether to
quantitate on the Primary Analysis or the Confirmation
Analysis. "When this criterion cannot be met, quantitation is
adversely affected because of the difficulty in determining
where to establish the baseline.
4.5.2.1 For a fused silica capillary (FSCC) confirmation,
there must be > 25 percent resolution (valley)
between the following pesticide pairs:
o beta-BHC and delta-BHC
o Dieldrin and 4,4'-DDT
o 4,4'-DDD and Endrin Aldehyde
o Endosulfan Sulfate and 4,4'-DDT
4.5.3 All QC specified previously must be adhered to, i.e., the £ 12
minutes retention time for 4,4'-DDT, and the specified criteria
for 4,4'-DDT and endrin degradation, linearity, calibration
factor for standards, and retention time shift for
dibutylchlorendate. The retention time requirement 4,4'-DDT
does not have to be met if the confirmation column is OV-1 or
OV-101.
4.5.4 Begin the Confirmation Analysis GC sequence with the three
concentration levels of Evaluation Standard Mixes A, B and C.
The exception to this occurs when toxaphene and/or DDT series
are to be confirmed and quantitated. There are four
combinations of pesticides that could occur, therefore, the
E-61/PEST Rev. 9/88
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following sequences must be followed depending on the
situation.
A.5.4.1 Toxaphene only - Begin the sequence with Evaluation
Mix B to check degradation, followed by three
concentration levels to toxaphene. Check linearity
by calculating %RSD. If < 10.0% RSD, use the
appropriate equation in Exhibit D PEST for
calculation. If >10.0% RSD, plot a standard curve
and determine the ng for each sample in that set
from the curve.
4.5.4.2 DDT, DDE, ODD only - Begin the sequence with
Evaluation Mix B. Then inject three concentration
levels of a standard containing DDE, ODD and DDT.
Calculate linearity and follow the requirements
specified in 4.5.4.1 for each compound to be
quantitated.
4.5.4.3 DDT series and toxaphene - Begin the sequence with
Evaluation Mix B. Then inject three concentration
levels of toxaphene and another three levels of the
DDT series. Calculate linearity and follow the
requirements specified in 4.5.4.1 for each compound"
to be quantitated.
4.5.4.4 Other pesticides/PCBs plus DDT series and/or
toxaphene Begin the sequence with Evaluation
Standard Mixes A, B and C. Calculate linearity on
the four compounds in the Evaluation Standards
mixes. If DDT and/or one or more of the other
compounds are >10.0% RSD and/or degradation exceeds
the criterion, corrective maintenance as outlined in
paragraph 4.3.3.8 should be performed before
repeating the above chromatogifaphy evaluations. If
DDT only exceeds the linearity criteria and one or
more of the DDT series is to be quantitated, follow
4.5.4.2 (do not repeat Evaluation Mix B). If none of
the DDT series is to be quantitated and DDT exceeds
the 10.0% RSD, simply record the % RSD on the proper
form. Anytime toxaphene is to be quantitated,
follow 4.5.4.1.
4.5.5 After the linearity standards required in 4.5.4 are injected,
continue the confirmation analysis injection sequence with all
compounds tentatively identified during primary analysis to
establish the daily retention time windows during primary
analysis. Analyze all confirmation standards for a case at the
beginning, at intervals specified in 4.5.6, and at the end. Any
pesticide outside of its established retention time window
requires immediate investigation and correction before
continuing the analysis. The laboratory must reanalyze all
samples between the standard that exceeds the criterion and a
subsequent standard that meets the criterion.
E-62/PEST 2/88
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4.5.6 Begin injection of samples at this point of the Confirmation
Analysis sequence. Analyze groups of 5 samples with a standard
pertaining to the samples after each group (Evaluation Mix B is
required after the first 5 samples, and every 10 samples
thereafter, e.g., after 5, 15, 25, etc). The alternating
standard's calibration factors must be within 15.0 percent of
each other if quantitation is performed. Deviations larger
than 15.0 percent require the laboratory to repeat the samples
analyzed between the standard that exceeds the criterion'and a
subsequent standard that meets the criterion. The 15.0 percent
criterion only pertains to compounds being quantitated.
4.5.6.1 If more than one standard is required to confirm all
compounds tentatively identified in the Primary
Analysis, include an alternate standard after each
10 samples.
4.5.6.2 Samples must also be repeated if the degradation of
either DDT and/or Endrin exceed 20.0 percent on the
intermittent Evaluation Standard Mix B.
4.5.6.3 If the samples are split between 2 or more
instruments, all standards and blanks pertaining to
those samples must be analyzed on each instrument.
4.5.7 Inject the method blanks (extracted with each set of samples)
on every GC and GC column on which the samples are analyzed.
4.5.8 If quantitation is performed on the confirmation analysis,
follow the instructions in 4.4.5 regarding dilution of extracts
and reporting results.
4.6 GC/MS Pesticide/PCB Confirmation
4.6.1 Any pesticide/PCB confirmed by two dissimilar GC columns must
also be confirmed by GC/MS if the concentration in the final
sample extract is sufficient for GC/MS analysis (based on
laboratory GC/MS detection limits).
4.6.1.1 Pesticides/PCBs may be confirmed utilizing the
extract prepared for semivolatile GC/MS analysis;
however, the absence of pesticide/PCBs in the
semivolatile extract would require the analysis of
the pesticide/PCB (fraction) extract.
4.6.2 The tuning and mass calibration criteria for DFTPP (50 ng) MUST
be met prior to any confirmation of pesticides/PCBs is
undertaken. Refer to the tuning and mass calibration
instruction for semivolatiles. The characteristic ions for
GC/MC analysis of pesticides/PCBs are given in Exhibit D SV,
Table 5.
E-63/PEST 2/88
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4.6.3 The pesticide/PCB sample extract(s) and the associated
pesticide/PCB blank(s), and reference standard(s) must be
analyzed by GC/MS.
4.7 Documentation
See Exhibit B for complete instructions for the completion of all
required forms and the Deliverable Index for all reporting and
deliverables requirements.
E-64/PEST 2/88
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SECTION IV
ANALYTICAL STANDARDS
The Environmental Protection Agency's Quality Assurance Materials Bank will
supply primary standards (calibration standards, surrogate standards, matrix
spiking standards, and internal standards), contingent upon their
availability, only for traceability and quantitative verification of
Contractor standards. It is emphasized that these primary standards are for
traceability only. There are insufficient quantities to have these available
to serve as working standards. The Contractor is responsible for preparing
its own working standards from commercial sources.
Caution should be exercised when mixing these standards together,
particularly the multicomponent standards. Chemical reactions, such as
acid/base reactions, Schiff base formations (reactions of aldehydes and
ketones with primary amines), hydrolysis, isotopic exchange, and others may
occur.
EPA contract laboratories can call or write directly to the QAMB (address and
phone number on the following request form) to obtain reference standards.
Standards will be provided based on the reasonableness of the request and
their availability. Any request from a commercial laboratory that is not
currently under contract to EPA will be denied.
Upon award of a contract, a list of available standards will be provided by
the EMSL/LV upon request.
E-65 2/88
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QUALITY ASSURANCE MATERIALS BANK
REQUEST FOR REFERENCE STANDARDS
Quality Assurance Materials Bank (MD-8)
Research Triangle Park. NC 27711 USA
Telephone: RequestsONLY: (919)541-4019
(FTS) 629-40 19
Information: (702)545-2690
(FTS) 54S-269Q
Technical Assistance: (919) 541-3951
(FTS) 629-3951
The following reference standards are required for our program:
Number
Reauired
Standard
Coae
Numaer
.
Date Reaucst Received
Date of Shipment
Laboratory Code Number
Reaucst Number
Verified
THIS 8LOOC FOR AGENCY USE ONLY
Compound(s)
Solvent
^
r>urity
• Concentration
(jtg/ml)
»'««i« came*!* *»-i *O"« i> M. MMTMa O* TY»6 flam* *"• «acr«u. 'JM 9Uu «« ^ eou.o<« -'» »<<> at wt*«r to comp^-« rti .* n*c«v>ry Me
Name and Address of laboratory:
IMPOHTANT:
. 'o< nt«
Request for Reference Standards
E-66
2/88
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SECTION V
LABORATORY EVALUATION PROCEDURES
This section outlines the procedures which will be used by the Project
Officer or his authorized representative during the contract period of
performance to conduct laboratory audits to determine the Contractor's
continuing ability to meet the terms and conditions of this contract. The
evaluation process incorporates two major steps: 1) evaluation of laboratory
performance, and 2) on-site inspection of the laboratory to verify continuity
of personnel, instrumentation and quality control requirements of the
contract. The following is a description of these two steps.
PART 1 - EVALUATION OF LABORATORY PERFORMANCE
1. Performance Evaluation Sample Analysis
1.1 The Performance Evaluation (PE) sample set will be sent to a
participating laboratory on a quarterly basis to verify the
laboratory's continuing ability to produce acceptable analytical
results. These samples will be provided either single blind
(recognizable as a PE material and of unknown composition), or double
blind (not recognizable as a PE material and of unknown composition).
If received as a single blind, the Contractor is required to submit PE
sample data in a separate SDG package in accordance with Delivery
Schedule requirements for sample data. PE samples received as double
blind would be treated as routine samples and data would be submitted
in the SDG deliverables package per normal procedure.
1.2 When the PE data are received, results will be scored routinely for
identification and quantitation. Results of thes*e scorings will be
provided to the Contractor. The government may adjust the scores on
any given PE sample to compensate for unanticipated difficulties with a
particular sample.
1.3 If a laboratory performs unacceptably, the laboratory will be
immediately notified by the Project Officer. A laboratory so notified
may expect, but the government is not limited to, the following
actions: a. site visit, a full data audit, and/or laboratory analysis
of a second PE sample. Failure by the laboratory to take corrective
actions and/or failure of two successive PE sample analyses will
require that the laboratory discontinue analysis of samples until such
time as the Project Officer has determined that the laboratory may
resume analyses.
2. Organic Data Audit
2.1 Organic data audits are conducted on CLP Contractor's Reporting and
Deliverables packages by EMSL/LV. The organic data audit provides the
Agency with an in-depth inspection and evaluation of the Case data
packages with regard to achieving QA/QC acceptability.
E-67 2/88
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PART 2. ON-SITE LABORATORY EVALUATION
2. The on-site laboratory evaluation helps to ensure that all the
necessary quality control is being applied by the Contractor in order
to deliver a quality product.
2.1 Quality assurance evaluations allow the evaluators to determine that:
2.1.1 The organization and personnel are qualified to perform
assigned tasks,
2.1.2 Adequate facilities and equipment are available,
2.1.3 Complete documentation, including chain-of-custody of samples
is being implemented,
2.1.4 Proper analytical methodology is being used,
2.1.5 Adequate analytical Quality Control, including reference
samples, control charts, and documented corrective action
measures, is being provided, and
2.1.6 Acceptable data handling and documentation techniques are being
used.
2.2 The on-site visit also serves as a mechanism for discussing weaknesses
identified through the Performance Evaluation sample analysis or
through Contract Compliance Screening or other review of data
deliverables. Lastly, the on-site visit allows the evaluation team to
determine if the laboratory has implemented the recommended and/or
required corrective actions, with respect to quality assurance, made
during the previous on-site visit.
E-68 2/88
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EXHIBIT F
CHAIN-OF-CUSTODY, DOCUMENT CONTROL,
AND STANDARD OPERATING PROCEDURES
F-l 2/88
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1. Sample Chain-of-Custody
A sample is physical evidence collected from a facility or from the
environment. An essential part of hazardous waste investigations is
that samples and data may be used as evidence in EPA enforcement
proceedings. To satisfy enforcement uses of the data, the following
chain-of-custody procedures have been established.
1.1 Sample Identification
To assure traceability of samples while in possession of the
Contractor, a method for sample identification shall be developed and
documented in laboratory Standard Operating Procedures (SOPs) (see
Section 3). Each sample or sample preparation container shall be
labeled with a unique number identifier (or the SMO number). This
identifier shall be cross-referenced to the sample tag number and the
SMO number. There shall be a written description of the method of
assigning this identifier and attaching it to the sample container
included in the laboratory SOPs.
1.2.1 A sample is under custody if:
1.2.1.1 It is in your actual possession,
1.2.1.2 It is in your view after being in your physical
possession,
1.2.1.3 It was in your possession and then you locked or
sealed it up to prevent tampering, or
1.2.1.4 It is in a secure area.
1.2.2 Upon receipt of the samples in custody, the Contractor shall
inspect the shipping container and sampl€ bottles and shall
document receiving information as specified in Section 3.2.
The sample custodian or a designated representative shall
sign and date all appropriate receiving documents at the time
of receipt (i.e., EPA chain-of-custody forms, traffic
reports, airbills, etc.). The Contractor shall contact SMO
if documents are absent, information on receiving documents
does not agree, custody seals are not intact, or the sample
is not in good condition. The Contractor shall document
resolution of any discrepancies, and this documentation shall
become a part of the permanent case file.
1.2.3 Once samples have been accepted by the laboratory, checked,
and logged in, they must be maintained in accordance with
custody and security requirements specified in 3.3.
F-2 2/88
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2. Document Control Procedures
The goal of the laboratory document control program is to assure that
all documents for a specified case 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 Data Sheets and Logbooks
Preprinted data sheets shall contain the name of the laboratory and
be dated and signed by the analyst or individual performing the work.
All documents produced by the laboratory 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 case file. For that
reason, all observations and results recorded by the laboratory but
not on preprinted data sheets are entered into permanent laboratory
logbooks. The person responsible for the work shall sign and date
each entry and/or page in the logbook. When all data from a case is *
compiled, copies of all EPA case-related logbook entries shall be
included in the documentation package. Analysts' logbook entries
must be in chronological order and shall include only one case per
page. Instrument run logs shall be maintained so as to enable a
reconstruction of the run sequences 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 SMO sample identification numbers in the logs for
sample ID rather than government agency or commercial client names.
*
Using laboratory or SMO sample IDs only in the run sequences will
assist the laboratory in preserving the confidentiality of commercial
clients.
2.2 Error Correction Procedure
All documentation in logbooks and other documents shall be in ink.
If an error is made, corrections shall be made by crossing a line
through the error and entering the correct information. Changes
shall be dated and initialed. No information shall be obliterated or
rendered unreadable.
2.3 Consistency of Documentation
Before releasing analytical results, the laboratory shall assemble
and cross-check the information on sample tags, custody records, lab
bench sheets, personal and instrument logs, and other relevant data
to ensure that data pertaining to each particular sample or case is
consistent throughout the case file.
F-3 2/88
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2.4 Document Numbering and Inventory Procedure
In order to provide document accountability of the completed analysis
records, each item in a case shall be inventoried and assigned a
serialized number and identifier associating it to the case and
Region.
Case # - Region - Serialized number (For example: 75-2-0240)
The number of pages of each it«m must be accounted for if each page
is not individually numbered. All documents relevant to each case,
including logbook pages, bench sheets, mass spectra, chromatograms,
custody records, library search results, etc., shall be inventoried.
The laboratory shall be responsible for ensuring that all documents
generated are placed in the file for inventory and are delivered to
EPA.., Figure 1 is an example of a document inventory.
2.5 Shipping Data Packages and Case Files
The Contractor shall have written procedures to document shipment of
deliverables packages to the recipients. Case File Purge shipments
require custody seals on the container(s) placed such that it cannot
be opened without damaging or breaking the seal. The Contractor
shall also document what was sent, to whom, the date, and the method
(carrier) used.
3. Standard Operating Procedures
The Contractor must have written standard operating procedures (SOPs)
for (1) receipt of samples, (2) maintenance of custody, (3) sample
storage, (4) tracking the analysis of samples, and (5) assembly of
completed data.
An SOP is defined as a written narrative step-wise description of
laboratory operating procedures including examples of laboratory
documentation. The SOPs must 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 a designated sample custodian responsible
for receipt of samples and have written SOPs describing his/her
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:
F-4 2/88
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o Presence or absence of EPA chain-of-custody forms
o Presence or absence of airbills
o Presence or absence of EPA Traffic Reports or SAS packing
lists
o Presence or absence of custody seals on shipping and/or-
sample containers and their condition
o Presence or absence of sample tags
o Sample tag ID numbers if not recorded on the chain-of-
custody record(s) or packing list(s)
•• o Condition of the shipping container
o Condition of the sample bottles
o Verification of agreement or nonagreement of information on
receiving documents
o Resolution of problems or discrepancies with the Sample
Management Office
3.3 The Contractor shall have written SOPs for maintenance of the
security of samples after log-in and shall demonstrate security of
the sample storage and laboratory areas. The SOPs shall specifically
include descriptions of all storage areas for EPA samples in the
laboratory, and steps taken to prevent sample contamination. The
SOPs shall include a list of authorized personnel who have access or
keys to secure storage areas.
3.4 The Contractor shall have written SOPs for tracking the work
performed on any particular sample. The tracking SOP shall include
the following:
3.4.1 A description of the documentation used to record sample
receipt, sample storage, sample transfers, sample
preparations, and sample analyses.
3.4.2 A description of the documentation used to record instrument
calibration and other QA/QC activities.
3.4.3 Examples of the document formats and laboratory documentation
used in the sample receipt, sample storage, sample transfer,
and sample analyses.
3.5 The Contractor shall have written SOPs for organization and assembly
of all documents relating to each EPA case, including technical and
managerial review. Documents shall be filed on a Case-specific
basis. The procedures must ensure that all documents including
logbook pages, sample tracking records, chromatographic charts,
computer printouts, raw data summaries, correspondence, and any other
F-5 2/88
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written documents having reference to the Case are compiled in one
location for submission to EPA. The system must include a document
numbering and inventory procedure.
3.6 The Contractor shall have written SOPs for laboratory safety.
3.7 The Contractor shall have written SOPs for cleaning of glassware used
in preparing and analyzing samples under this contract.
3.8 The Contractor shall have SOPs for traceability of standards used in
sample analysis QA/QC.
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 logs these documents into a
Confidential Inventory Log. The information is then made available
to authorized personnel but only after it has beeti 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 Contracting
Officer. The DCO will enter all copies into the document control
system. In addition, this information may not be disposed of except
upon approval by the EPA Contracting Officer. The DCO shall remove
and retain the cover page of any confidential information disposed of
for one year and shall keep a record of the disposition in the
Confidential Inventory Log.
F-6 2/88
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Figure 1
Example
DOCUMENT INVENTORY
Document Control #*
Document Type
# Pages
232-2'
232-2-
232-2
232-2-
232-2^
232-2-
232-2-
232-2-
232-2-
232-2-
232-2-
232-2-
etc.
0001
0002
0003
0004"
0005
0006
0007
0008
0009
0010
0011
0012
Case File Document Inventory Sheet
Chain-of-Custody Records
Shipping Manifests
Sample Tags
SMO Inorganics Traffic Reports
GC/MS spectra for sample B0310
GC/MS spectra for sample B0311
GC/MS spectra for sample B0319
Analyst's logbook pages
GC/MS library search worksheets
GC instrument log pages
GC/MS QC data sheets
etc.
1
2
2
50
10
20
20
20
6
15
5
4
etc.
*This number is to be recorded on each set of documents.
F-7
2/88
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EXHIBIT G
GLOSSARY OF TERMS
G-l 2/88
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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
tuning performance for volatile analyses.
»»
CALIBRATION CHECK COMPOUNDS (CCC) - target compounds used to evaluate the
calibration stability (precision) of the GC/MS system. Maximum percent
deviations of the CCCs are defined in the protocol.
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.
CONFIRMATION ANALYSIS - see Primary Analysis. •"
CONTINUING CALIBRATION - analytical standard run every 12 hours to verify the
calibration of the GC/MS system.
CONTINUOUS LIQUID-LIQUID EXTRACTION - used herein synonymously with the terms
continuous extraction, continuous liquid extraction, and liquid extraction.
DAY - unless otherwise specified, day shall mean calendar day.
DECAFLUOROTRIPHENYLPHOSPHINE (DFTPP) - compound chosen to establish mass
spectral tuning 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 BNA and pesticide/PCB compounds.
IN-HOUSE - at the Contractor's facility.
G-2 2/88
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INITIAL CALIBRATION - analysis of analytical standards for a series of
different specified concentrations; used to define the linearity and dynamic
range of the response of the mass spectrometer to the target compounds.
INTERNAL STANDARDS - compounds added to every standard, blank, matrix spike,
matrix spike duplicate, sample (for VOAs), and sample extract (for
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.
MATRIX - the predominant material of which the sample to be analyzed is
composed. For the purpose of this SOW, a sample matrix is either water or
soil/sediment. Matrix is not synonymous with phase (liquid or solid).
MATRIX SPIKE - aliquot of a matrix (water or soil) fortified (spiked) with
known quantities of specific compounds and subjected to the entire analytical
procedure in order to indicate the appropriateness of the method for the
matrix by measuring recovery.
MATRIX SPIKE DUPLICATE - a second aliquot of the same matrix as the matrix
spike (above) that is spiked in order to determine the precision of the
method.
METHOD BLANK (previously termed reagent blank) - an analytical control
consisting of all reagents, internal standards and surrogate standards, that
is carried through the entire analytical procedure. The method blank is used
to define the level of laboratory background contamination.
NARRATIVE (Case 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 Case Narrative
specifications are included in Exhibit B.
PERCENT MOISTURE - an approximation of the amount of water in a soil/sediment
sample made by drying an aliquot of the sample at 105"C. The percent
moisture determined in this manner also includes contributions from all
compounds that may volatilize at 105°C, including water. Percent moisture is
determined from decanted samples and from samples that are not decanted.
PRIMARY ANALYSIS - one of two types of pesticide/PCB analysis by GC/EC
techniques, the other being the Confirmation Analysis. If the two analyses
are run at separate times, the Primary Analysis is the first analysis
chronologically, and is used to establish the tentative identification of any
pesticides/PCBs detected. The identification is then confirmed in the
confirmation analysis. If the two analyses are simultaneous, either may be
considered the Primary Analysis.
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 2/88
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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 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.
RECOVERY - a determination of the accuracy of the analytical procedure made
by comparing measured values for a fortified (spiked) sample against the
known spike values. Recovery is determined by the following equation:
measured value
%Rec - -= = x 100%
known value
RELATIVE RESPONSE FACTOR (RRF) - a measure of the relative mass spectral
response of an analyte compared to its internal standard. Relative Response
Factors are determined by analysis of standards and are used in the
calculation of concentrations of analytes in samples. RRF is determined by
the following equation:
Where
A - area of the characteristic ion measured "
C - concentration
is - internal standard
x - analyte of interest
RESOLUTION - also termed separation, the separation between peaks on a
chromatogram, calculated by dividing the height of the valley between the
peaks by the peak height of the smaller peak being resolved, multipled by
100.
SAMPLE - a portion of material to be analyzed that is contained in single or
multiple containers and identified by a unique sample number.
SAMPLE DELIVERY GROUP (SDG) - a unit within a single Case that is used to
identify a group of samples for delivery. An SDG is a group of 20 or fewer
field samples within a Case, received over a period of up to 14 calendar
days. Data from all samples in an SDG are due concurrently. A Sample
Delivery Group is defined by one of the following, whichever occurs first:
G-4 2/88
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o Case; or
o Each 20 field samples within a Case; or
o Each 14-day calendar period during which field samples in a Case are
received, beginning with receipt of the first sample in the Case or SDG.
Samples may be assigned to Sample Delivery Groups by matrix (i.e., all s*oils
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) - 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 PERFORMANCE CHECK COMPOUNDS (SPCC) - target compounds designated to
monitor chromatographic performance, sensitivity and compound instability or
degradation on active sites. Minimum response factor criteria for the SPCCs
are defined in the protocol.
*
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 or surrogate standards. Up to
30 peaks (those greater than 10% of peak areas or heights of nearest internal
standards) are subjected to mass spectral library searches for tentative
identification.
TIME - when required to record time on any deliverable item, time shall be
expressed as Military Time, i.e., a 24-hour clock.
TRAFFIC REPORT (TR) - an EPA sample identification form filled out by the
sampler, which accompanies the sample during shipment to the laboratory and
which documents sample condition and receipt by the laboratory.
TWELVE-HOUR TIME PERIOD - The twelve (12) hour time period for GC/MS system
tuning, 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 compliant tune. The time
period ends after 12 hours has elapsed according to the system clock.
G-5 2/88
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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
•re classified as narrow bore capillaries.
G-6 Rev. 9/88
-------
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-3
SECTION III: Format B Specifications H-63
H-l 2/88
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SECTION I
DESCRIPTION OF DELIVERABLE
1. Introduction
1.1 Two file formats are specified for delivery of computer-readable data.
Format A is oriented to the structure of the hardcopy reporting forms
required by the contract. Format B is oriented to the general data
required by the contract. Information sufficient to generate required
hardcopy forms is contained in either format.
1.2 The file or files for a Sample Delivery Group (SDG, see Exhibit A,
Section I, B) must be submitted on a diskette or diskettes (see
Deliverable, 2.1). Information on a diskette or diskettes for any
single SDG must be in one, and only one, of the two formats. The
format used is at the option of the laboratory. The option used must
be included in the File Name specification (paragraph 2.2).
1.3 Format A consists of variable length ASCII records, and Format B
consists of fixed-length 80-byte ASCII records.
1.4 All information for one SDG must be in one file if format A is used.
Use of Format B may require information for one SDG to be in a number
of files. Format B may require more than one 360 K diskette for a
valid SDG.
2. Deliverable
2.1 The file or files must be submitted on a 5-1/4 inch floppy diskette,
which may be either a double-sided, double density, 360 K-byte or a
high capacity 1.2 M-byte diskette. The diskette or diskettes must
contain all information relevant to one and only one SDG, and must
accompany the hardcopy package for the SDG submitted to the Sample
Management Office (see Exhibit B). Information on the diskette or
diskettes must correspond exactly with information submitted in the
hardcopy data package and on the hardcopy data package forms. Blank or
unused records in either format should not be included on the
diskettes.
2.2 Each diskette must be identified with an external label containing (in
this order) the following information:
Disk Density
File Name(s)
Laboratory Name (optional)
Laboratory Code
Case Number (where applicable)
SAS Number (where applicable)
H- 2 2/88
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SECTION II
FORMAT A SPECIFICATION
1. Format Characteristics
1.1 Format A is based upon the structure of the hardcopy reporting forms
required by the contract. With two exceptions, Form Suffix and Record
Type, all fields in the format correspond directly with entries or
items on the hardcopy forms. The record structure is obtained by
taking entries in sequence from the appropriate hardcopy form. For
example, the Header record (page H-7) from Form 1A is a concatenation
of all entries on the hardcopy form that precede the reported results
and qualifiers.
1.2 All Format A fields are character. Alphanumeric values should be left
justified and numeric values should be right justified in appropriate
fields. Field lengths are such that all possible valid values can be
written to the file. The maximum format is specified for each field.
For example, "Numeric 13.3" is specified for "Result" on Detail Record
Dl of Form 1A (see page H-7). Numeric values reported may take any
form (e.g., integer 13, integer 3, real 13.3, real 5.1, etc.) provided
they do not exceed the specifications. (Requirements for the number of
significant figures to be reported on the appropriate hardcopy form are
given in the Form Instruction Guide, Exhibit B, Section III.)
2. Record Types
2.1 Format A consists of variable length ASCII records. The last two bytes
of each record must contain "carriage return" and "line feed",
respectively. Unused bytes in partially filled fields must be blank-
filled.
2.2 Format A has three types of records: Header Records, Detail Records
and Comment Records.
Type Type ID Contents
Header H Nonrepeating fields which
together are unique to the
associated hardcopy form
Detail D A group of fields that are
repeated on a form, and are
uniquely positioned by (e.g.)
CAS Number or Sequence Number
Comment C Nonrepeating fields containing
text that comments on informa-
tion reported on the form
H-3 2/88
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3.
Record Length
Table 3.1 summarizes the length and {in parentheses) the number of
records in Format A. The maximum number of detail and comment records
is shown, corresponding to a submission of hardcopy forms on which
information is written on all possible lines. The Form Totals are the
maximum lengths (excluding carriage return/line feed) required for a
complete set of each type of form.
Table 3.1 Format A Summarv
Form
1A
IB
1C
ID
IE
IF
l(Total)
2A
2B
2C
2D
2E
2F
2(Total)
3A
3B
3C
3D
3E
3F
3(Total)
4A
4B
4C
4(Total)
5A
5B
5(Total)
Record
Header
fil
153a(1)b
168 (1)
168 (1)
168 (1)
155 (1)
170 (1)
982 (6)
67(1)
70(1)
67(1)
70(1)
67(1)
70(1)
411(6)
85(1)
84(1)
85(1)
88(1)
85(1)
988(1)
519(6)
123(1)
135(1)
177(1)
435(3)
115(1)
103(1)
Detail
El
35(34)
35(33)
35(32)
35(27)
71(30)
71(30)
8670(186)
37(30)
37(30)
49(30)
49(30)
28(30)
28(30)
6840(180)
70( 5)
70( 5)
70(11)
70(11)
70( 6)
70( 6)
3080(44)
51(30)
55(30)
49(26)
4454(86)
20(9)
21(13)
Comment
£2
61( 5)
61( 5)
61(11)
61(11)
61( 6)
€1( 6)
2684(44)
72(1)
72(1)
72(1)
216(3)
59(24)
59(22)
£1
72(1)
M<1)
72(1)
72(1)
72(1)
72(1)
432(6)
72(1)
72(1)
72(1)
216(3)
£2
72(1)
72(1)
72(1)
72(1)
72(1)
72(1)
432(6)
218(2)
453(22)
2714(46)
H-4
2/88
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Form
6A
6B
6C
6(Total)
7A
7B
7C
7(Total)
8A
8B
8C
8D
8E
8(Total)
9
9(Total)
10
lO(Total)
Table 3.1 Format A Summary
Record
Header
HI
173(1)
161(1)
161(1)
495(3)
129(1)
117(1)
117(1)
363(3)
115(1)
103(1)
103(1)
101(1)
103(1)
525(5)
135(1)
135(1)
145(1)
145(1)
Detail
£1
69(37)
69(37)
69(36)
7590(110)
49(37)
49(37)
49(36)
5390(110)
106(1)
106(1)
106(1)
58(4)
51(38)
2488(45)
72(27)
1944(27)
43(6)
258(6)
Comment
69(26)
69(22)
69(22)
36(14)
5334(84)
43(6)
258(6)
72(1)
72(1)
72(1)
72(1)
a - length of record in bytes (excluding carriage return/line feed)
b - maximum number of records required for a form. ^
4. Form Suffix
The fourth and fifth bytes of each record contain the form suffix (AA-
ZZ), which must be unique (within a type of form (e.g., Form IA, Form
IIC, etc.,) for each set of records that corresponds to one hardcopy
form. For example, the form suffix for records for the first
occurrence in the file of a Form 1C must be AA-. The second occurrence
must be AB, and the twenty-eighth must be BA.
5. Record Listing
The remainder of this section contains detailed specifications for
every record required for a full set of hardcopy forms.
H-5
2/88
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FORM I FILE DESCRIPTION
(FORM1J
H - 6 1/87 REV
-------
VOLATILE DRGANICS ANALYSIS DATA SHEET - (FORM 1AJ
HEADER RECORD 1 (HI)
COLUMN (S)
LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8- 19
20- 44
45- 55
56- 61
62- 66
67- 72
73- 77
78- 82
83- 94
95- 99
* 100-101
102-115
116-118
119-126
127-128
129-136
137-140
141-148
149-153
3
2
2
12
25
11
6
5
, 6
5
5
12
5
2
14
3
8
2
8
4
8
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
EPA SAMPLE NO.
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
MATRIX
LAB SAMPLE ID
SAMPLE HT/VOL
SAMPLE WT/VOL UNITS
LAB FILE ID
LEVEL
DATE RECEIVED
XMOISTURE NOT DEC
DATE ANALYZED
COLUMN
DILUTION FACTOR
CONCENTRATION UNITS
'1A'
'AA'-'ZZ'
•Hlf
•SOIL ' OR 'WATER'
NUMERIC 5.1
•G » OR 'ML'
•LOW* OR 'MED'
MM/DD/YY
NUMERIC 2
MM/DD/YY
•PACK' OR 'CAP '
NUMERIC 8
•UG/L ' OR 'UG/KG*
DETAIL RECORD 1 (Dl)
COLUMN (S) LENGTH CONTENTS
1-3
4-5
6-7
8-17
18-30
31-35
3
2
2
10
13
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
CAS NO.
RESULT
QUALIFIER
-------
SEMIVOLATILE ORGANICS ANALTSIS DATA SHEET - (FORM IB)
HEADER RECORD 1 (HI)
COLUMN (S) LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8- 19
20- «4
45- 55
56- 61
62- 66
67- 72
73- 77
78- 82
83- 94
95- 99
, 100-101
102-115
116-118
119-126
127-128
129-130
131-138
139-142
143-150
151
152-155
156-163
164-168
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8-17
18-30
31-35
3
2
2
12
25
11
6
5
6
- 5
5
12
5
2
14
3
8
2
2
8
4
8
1
4
8
5
1 (Dl)
LENGTH
3
2
2
10
13
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
EPA SAMPLE NO.
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
MATRIX
LAB SAMPLE ID
SAMPLE WT/VOL
SAMPLE WT/VOL UNITS
LAB FILE ID
LEVEL
DATE RECEIVED
% MOISTURE NOT DEC
% MOISTURE DEC
DATE EXTRACTED
EXTRACTION
DATE ANALYZED
GPC CLEANUP
PH
DILUTION FACTOR
CONCENTRATION UNITS
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
CAS NO.
RESULT
QUALIFIER (Q)
•IB'
'AA'-'ZZ'
•Hl»
•SOIL ' OR 'WATER'
NUMERIC 5.1
'G ' OR 'ML'
•LOW1 OR 'MED'
MM/DD/YY
NUMERIC 2
NUMERIC 2
MM/DD/YY
'SEPF', 'CONT' OR 'SONC'
MM/DD/YY
•Y' OR 'N'
NUMERIC 4.1
NUMERIC 8
•UG/L ' OR 'UG/KG'
^
FORMAT/CONTENTS
•IB'
•AA'-'ZZ'
•Dlf
NUMERIC 13.3
H - 8
1/87 REV.
-------
SEMIVOLATILE ORSANICS ANALYSIS DATA SHEET - CFORM
HEADER RECORD 1 (HI)
COLUMN (S) LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8- 19
20- 44
45- 55
56- 61
62- 66
67- 72
73- 77
78- 82
83- 94
95- 99
100-101
* 102-115
116-118
119-126
127-128
129-130
131-138
139-142
143-150
151
152-155
156-163
164-168
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8-17
18-30
31-35
3
2
2
12
25
11
«
5
6
-5
5
12
5
2
14
3
8
2
2
8
4
8
1
4
8
5
1 (Dl)
LENGTH
3
2
2
10
13
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
EPA SAMPLE NO.
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
MATRIX
LAB SAMPLE ID
SAMPLE MT/VOL
SAMPLE WT/VOL UNITS
LAB FILE ID
LEVEL
DATE RECEIVED
* MOISTURE NOT DEC
% MOISTURE DEC
DATE EXTRACTED
EXTRACTION
DATE ANALYZED
GPC CLEANUP
PH
DILUTION FACTOR
CONCENTRATION UNITS
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
CAS NO.
RESULT
QUALIFIER (Q)
'1C'
'AA'-'ZZ'
•HI*
'SOIL ' OR 'WATER'
NUMERIC 5.1
'G ' OR 'ML'
'LOW OR 'MED'
MM/DD/YY
NUMERIC 2
NUMERIC 2
MM/DD/YY
'SEPF', 'CONT' OR 'SONC'
MM/DD/YY
'Y' OR 'N'
NUMERIC 4.1
NUMERIC 8
'UG/L ' OR 'UG/KG'
*
FORMAT/CONTENTS
•1C'
'AA'-'ZZ*
'Dl'
NUMERIC 13.3
H - 9
1/87 REV.
-------
PESTICIDE ORGANICS ANALYSIS DATA SHEET - (FORM ID)
HEADER RECORD 1 (HI)
COLUMN (S)
LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8-19
20- 44
45- 55
56- 61
62- 66
67- 72
73- 77
78- 82
83- 94
95- 99
* 100-101
102-115
116-118
119-126
127-128
129-130
131-138
139-142
143-150
151
152-155
156-163
164-168
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8-17
18-30
31-35
3
2
2
12
25
11
6
5
.. 6
5
5
12
5
2
14
3
8
2
2
8
4
8
1
4
8
5
1 (Dl)
LENGTH
3
2
2
10
13
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
EPA SAMPLE NO.
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
MATRIX
LAB SAMPLE ID
SAMPLE WT/VOL
SAMPLE WT/VOL UNITS
LAB FILE ID
LEVEL
DATE RECEIVED
X MOISTURE NOT DEC
% MOISTURE DEC
DATE EXTRACTED
EXTRACTION
DATE ANALYZED
GPC CLEANUP
PH
DILUTION FACTOR
CONCENTRATION UNITS
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
CAS NO.
RESULT
QUALIFIER (Q)
•ID'
•AA'-'ZZ'
•HI'
•SOIL ' OR 'WATER'
NUMERIC 5.1
'G ' OR 'ML'
•LOW' OR 'MED'
MM/DD/YY
NUMERIC 2
NUMERIC 2
MM/DD/YY
'SEPF', 'CONT' OR 'SONC'
MM/DD/YY
•Y» OR 'N'
NUMERIC 4.1
NUMERIC 8
'UG/L ' OR 'UG/KG'
^
FORMAT/CONTENTS
•ID'
'AA'-'ZZ'
•Dl '
NUMERIC 13.3
H - 10
1/87 REV.
-------
VOLATILE ORGANICS ANALYSIS DATA SHEET - (FORM IE)
TENTATIVELY IDENTIFIED COMPOUNDS
HEADER RECORD 1 (HI)
COLUMN (S)
LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8- 19
20- 44
45- 55
56- 61
62- 66
67- 72
73- 77
78- 82
83- 94
' 95- 99
100-101
102-115
116-118
119-126
127-128
129-136
137-140
141-148
149-150
151-155
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8- 9
10-19
20-47
48-53
54-66
67-71
3
2
2
12
2*
11
6
5
-6
5
5
12
5
2
14
3
8
2
8
4
8
2
5
1 CD1)
LENGTH
3
2
2
2
10
28
6
13
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE'
EPA SAMPLE NO.
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
MATRIX
LAB SAMPLE ID
SAMPLE WT/VOL
SAMPLE WT/VOL UNITS
LAB FILE ID
LEVEL
DATE RECEIVED
* MOISTURE NOT DEC
DATE ANALYZED
COLUMN
DILUTION FACTOR
NUMBER TICS FOUND
CONCENTRATION UNITS
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
CAS NO.
COMPOUND
RT
ESTIMATED CONCENTRATION
QUALIFIER (Q)
•IE*
•AA'-'ZZ'
•HI*
•SOIL • OR 'WATER'
NUMERIC 5.1
•G ' OR 'ML'
•LOW' OR 'MED'
MM/DD/YY
NUMERIC 2
MM/DD/YY
•PACK' OR 'CAP '
NUMERIC 8
NUMERIC 2
•UG/L ' OR 'UG/KG'
FORMAT/CONTENTS
•IE*
'AA'-'ZZf
•Dl'
NUMERIC 2
NUMERIC 6.2
NUMERIC 13.3
H - 11
1/87 REV.
-------
SEMIVOLATILE ORtSANICS ANALYSIS DATA SHEET - (FORM IF)
TENTATIVELY IDENTIFIED COMPOUNDS
HEADER RECORD 1 (HI)
COLUMN (S)
LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8- 19
20- 44
45- 55
56- 61
62- 66
67- 72
73- 77
78- 82
83- 94
95- 99
100-101
102-115
116-118
119-126
127-128
129-130
131-138
139-142
143-150
151
152-155
156-163
164-165
166-170
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8- 9
10-19
20-47
48-53
54-66
67-71
3
2
2
12
25
11
6
, 5
6
5
5
12
5
2
14
3
8
2
2
8
4
8
1
4
8
2
5
1 (Dl)
LENGTH
3
2
2
2
10
28
6
13
5
FORM NUMBER
FORM SUFFIX
RECORD TYPE
EPA SAMPLE NO.
I.AB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
MATRIX
LAB SAMPLE ID
SAMPLE MT/VOL
SAMPLE WT/VOL UNITS
LAB FILE ID
LEVEL
DATE RECEIVED
X MOISTURE NOT DEC
X MOISTURE DEC
DATE EXTRACTED
EXTRACTION
DATE ANALYZED
GPC CLEANUP
PH
DILUTION FACTOR
NUMBER TICS FOUND
CONCENTRATION UNITS
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
CAS NO.
COMPOUND
RT
ESTIMATED CONCENTRATION
QUALIFIER (Q)
•IF'
f AAf-fZZf
•HI'
•SOIL ' OR 'WATER'
NUMERIC 5.1
•G ' OR 'ML'
•
'LOW* OR 'MED'
MM/DD/YY
NUMERIC 2
NUMERIC 2
MM/DD/YY
'SEPF', 'CONT' OR 'SONC'
MM/DD/YY
•Y' OR 'N'
NUMERIC 4.1
NUMERIC 8
NUJ1ERIC 2
'UG/L ' OR 'UG/KG'
FORMAT/CONTENTS
•IF'
•AA'-'ZZ'
•Dl'
NUMERIC 2
~
NUMERIC 6.2
NUMERIC 13.3
H - 12
1/87 REV
-------
FORM II FILE DESCRIPTION
(FORM2)
H - 13 1/87 REV
-------
WATER VOLATILE SURROGATE RECOVERY - (FORM 2A>
HEADER RECORD 1 CHI)
COLUMN (S)
LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8-32
33-43
44-49
50-54
55-60
61-65
66
67
DETAIL RECORD
*
COLUMN «S>
1- 3
4- 5
6- 7
8- 9
10-21
22-24
25
26-28
29
30-32
33
34-36
37
3
2
2
25
11
6
5
6
,5
1
1
1 (Dl)
LENGTH
3
2
2
2
12
3
1
3
1
3
1
3
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
PAGE
OF
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
EPA SAMPLE NO.
SI (TOD
SI OUT FLAG
52 (BFB)
S2 OUT FLAG
S3 (DCE)
S3 OUT FLAG
OTHER
TOTAL OUT
•2A'
'AA'-'ZZ'
'HI'
NUMERIC 1
NUMERIC 1
FORMAT/CONTENTS
'2A'
' AAf-'Z2f
'Dl'
NUMERIC 2
NUMERIC 3
BLANK OR *D' OR «*'
NUMERIC 3
BLANK OR 'D' OR '*'
NUMERIC 3
BLA/JK OR 'D* OR **'
NUMERIC 3
NUMERIC 1
H - 14
1/87 REV
-------
SOIL VOLATILE SURROGATE RECOVERY - (PORN 2B)
HEADER RECORD 1 (HI)
COLUMN (S) LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8-32
33-43
44-49
50-54
55-60
61-65
66-68
69
70
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8- 9
10-21
22-24
25
26-28
29
30-32
33
34-36
37
3
2
2
25
11
6
5
6
5
, 3
1
1
1 (Dl)
LENGTH
3
2
2
2
12
3
1
3
1 -
3
1
3
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
LEVEL
PAGE
OF
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
EPA SAMPLE NO.
SI (TOD
SI OUT FLAG
S2 (BFB)
S2 OUT FLAG
S3 (DCE)
S3 OUT FLAG
OTHER
TOTAL OUT
•2B'
•AA'-'ZZ'
•Hlf
'LOW OR 'MED'
NUMERIC 1
NUMERIC 1
FORMAT/CONTENTS
'2B'
'AA'-'ZZ'
'Dl'
NUMERIC 2
NUMERIC 3
BLANK OR 'D' OR '*'
NUMERIC 3
BLANK OR 'D' OR '«'
NUMERIC 3
BLANK OR 'D1 OR '*'
NUMERIC 3
NUMERIC 1
H - 15
1/87 REV
-------
HATER SEMIVOtATILE SURROGATE RECOVERY - (FORM 2C)
HEADER RECORD 1 CHI)
COLUMN (S)
LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8-32
33-43
44-49
50-54
55-60
61-65
66
67
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8- 9
10-21
22-24
25
26-28
29
30-32
33
34-36
37
38-40
41
42-44
45
46-48
49
3
2
2
25
11
6
5
6
,5
1
1
1 (Dl)
LENGTH
3
2
2
2
12
3
1
3
1
3
1
3
1
3
1
3
1
3
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
PAGE
OF
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
EPA SAMPLE NO.
SI (NBZ)
SI OUT FLAG
S2 (FBP)
S2 OUT FLAG
S3
-------
SOIL SEMIVOLATILE SURROGATE RECOVERY - (FORM 2D)
HEADER RECORD 1 (HI)
COLUMN (S)
LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8-32
33-43
44-49
50-54
55-60
61-65
66-68
69
70
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8- 9
10-21
22-24
25
26-28
29
30-32
33
34-36
37
38-40
41
42-44
45
46-48
49
3
2
2
25
11
6
5
6
,5
3
1
1
1 (Dl)
LENGTH
3
2
2
2
12
3
1
3
1
3
1
3
1
3
1
3
1
3
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
LEVEL
PAGE
OF
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
EPA SAMPLE NO.
SI (NBZ)
SI OUT FLAG
S2 (FBP)
S2 OUT FLAG
S3 (TPH)
S3 OUT FLAG
S4 (PHD
S4 OUT FLAG
S5 (2FP)
S5 OUT FLAG
S6 (TBP)
S6 OUT FLAG
OTHER
TOTAL OUT
•2Df
fAAf-fZZf
•HI'
'LOW OR *MEDf
NUMERIC 1
NUMERIC 1
FORMAT/CONTENTS
•2D'
'AA'-'ZZ'
•Dl'
NUMERIC 2
NUMERIC 3
BLANK OR 'D' OR '*'
NUMERIC 3
BLA^K OR 'D' OR '*'
NUMERIC 3
BLANK OR 'Df OR '»'
NUMERIC 3
BLANK OR 'D' OR '*'
NUMERIC 3
BLANK OR 'D' OR '*'
NUMERIC 3
BLANK OR 'D' OR '«'
NUMERIC 3
NUMERIC 1
H - 17
1/87 REV
-------
HATER PESTICIDE SURROGATE RECOVERY - (FORM 2E)
HEADER RECORD 1 (HI)
COLUMN LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8-32
33-43
44-49
50-54
55-60
61-65
66
67
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8- 9
1Q-21
22-24
25
26-28
3
2
2
25
11
6
5
6
5
- 1
1
1 tDl)
LENGTH
3
2
2
2
12
3
1
3
FORM NUMBER
FORM SUFFIX
RECORD TYPE
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
PAGE
OF
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
EPA SAMPLE NO.
SI (DBC)
SI OUT FLAG
OTHER
•2Ef
•AA'-'ZZ'
•HI*
NUMERIC 1
NUMERIC 1
FORMAT/CONTENTS
*2E<
•AA'-'ZZ'
*D1 *
NUMERIC 2
NUMERIC 3
BLANK OR 'D* OR
NUMERIC 3
H - 18
1/87 REV,
-------
SOIL PESTICIDE SURROGATE RECOVERY - (FORM 2F)
HEADER RECORD 1 (HI)
COLUMN (S)
LENGTH CONTENTS
.DETAIL RECORD 1 (Dl)
COLUMN (S) LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8-32
33-43
44-49
50-54
55-60
61-65
66-68
69
70
3
2
2
25
11
6
5
6
5
- 3
1
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
LEVEL
PAGE
OF
f2F'
•AA'-'ZZf
•HI'
'LOW OR 'MED1
NUMERIC 1
NUMERIC 1
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8- 9
10-21
23-24
25
26-28
3 FORM NUMBER
2 FORM SUFFIX
2 RECORD TYPE
2 SEQUENCE NUMBER
12 EPA SAMPLE NO.
3 51 (DBC)
1 SI OUT FLAG
3 OTHER
•2F'
'AA'-'ZZ'
'Dl'
NUMERIC 2
NUMERIC 3
BLANK OR '
NUMERIC 3
OR
H - 19
1/87 REV,
-------
FORM III FILE DESCRIPTION
(FORM3)
H - 20 1/87 REV.
-------
WATER VOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY - (FORM3A)
HEADER RECORD 1 (HI)
COLUMN (S)
LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8-32
33-43
44-45
50-54
55-60
61-65
66-77
78-79
80-81
82-83
84-85
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8-31
32-40
41-53
54-66
67-69
70
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8-31
32-40
41-53
54-56
57
58-60
61
3
2
2
25
11
6
5
6
,5
12
2
2
2
2
1 tDl)
LENGTH
3
2
2
24
9
13
13
3
1
2 (D2)
LENGTH
3
2
2
24
9
13
3
1
3
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
MATRIX SPIKE -
EPA SAMPLE NO.
RPD: * OUTSIDE PC LIMITS
RPD: TOTAL
SPIKE RECOVERY: * OUT
SPIKE RECOVERY: TOTAL
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
SPIKE ADDED (UG/L)
SAMPLE CONC. (UG/L)
MS CONC. (UG/L)
MS% REC.
MS* REC. FLAG
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
SPIKE ADDED (UG/L)
MSD CONC. (UG/L)
MSDX REC.
MSDX REC. OUT FLAG
% RPD
X RPD OUT FLAG
'3A'
•AA'-'ZZ'
•Hlf
NUMERIC 2
NUMERIC 2
NUMERIC 2
NUMERIC 2
FORMAT/CONTENTS
' 3A'
'AA'-'ZZ*
•Dlf
NUMERIC 9.3
NUMERIC 13.3
NUMERIC 13.3
NUMERIC 3
BLANK OR '*'
FORMAT/CONTENTS
'3Af
f AAf-'ZZf
•02'
NUMERIC 9.3
NUMERIC 13.3
NUMERIC 3
BLANK OR '*'
NUMERIC 3
BLANK OR •«•
H - 21
1/87 REV
-------
COMMENT RECORD 1 (CD
COLUMN (S) LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8-72
3
2
2
65
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMMENT LINE 1
«3A
•AA
•ci
f
'-'ZZ'
i
COMMENT RECORD 2 (C2)
COLUMN CS) LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8-72
3
2
,2
65
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMMENT LINE 2
•3A'
fAA'-'ZZ'
•C2«
H - 22
1/87 REV
-------
SOIL VOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY - CFORM3B)
HEADER RECORD 1 (HI)
COLUMN (S)
LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8-32
33-43
44-49
53-54
55-60
61-65
66-77
78-80
81-82
83-84
85-86
87-88
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8-31
32-40
41-53
54-66
67-69
70
3
2
2
25
11
6
5
6
5
,12
3
2
2
2
2
1 (Dl)
LENGTH
3
2
2
24
9
13
13
3
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
MATRIX SPIKE -
EPA SAMPLE NO.
LEVEL
RPD: f OUTSIDE QC LIMITS
RPD: TOTAL
SPIKE RECOVERY: t OUT
SPIKE RECOVERY: TOTAL
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
SPIKE ADDED (UG/L)
SAMPLE CONC. (UG/KG)
MS CONC. (UG/KG)
MS3S REC.
MSX REC. FLAG
'3Bf
'AA'-'ZZ'
•HI*
•LOW OR 'MED'
NUMERIC 2
NUMERIC 2
NUMERIC 2
NUMERIC 2
FORMAT/CONTENTS
•3B'
•AA'-'ZZ'
•Dl'
NUMERIC 9.3
NUMERIC 13.3
NUMERIC 13.3
NUMERIC 3
BLANK OR '*'
H - 23
1/87 REV.
-------
DETAIL RECORD 2 CD2)
COLUMN (S)
LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8-31
32-40
41-53
54-56
57
58-60
61
COMMENT
COLUMN (
1- 3
4- 5
6- 7
8-72
COMMENT
COLUMN (
1- 3
4- 5
6- 7
8-72
3
2
2
24
9
13
3
1
3
1
RECORD 1 (CD
S) LENGTH
3
2
2
65
RECORD 2 (C2)
S) LENGTH
3
2
2
65
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
SPIKE ADDED (UG/L)
NSD CONC. CUG/KG)
MSD% REC.
MSDX REC. OUT FLAG
X RPD
X RPD OUT FLAG
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMMENT LINE 1
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMMENT LINE 2
f3B'
' AA'-'ZZ'
•D2*
NUMERIC 9.3
NUMERIC 13.3
NUMERIC 3
BLANK OR '*'
NUMERIC 3
BLANK OR '*'
FORMAT/CONTENTS
•38'
' AA'-'ZZ'
•Cl'
FORMAT/CONTENTS
•3B*
' AA'-'ZZ'
«C2'
H -
1/87 REV
-------
WATER SEMIVOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY-(FORM3CJ
HEADER RECORD 1 (HI)
COLUMN (S)
LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5 ~
6- 7
8-32
33-43
44-49
50-54
55-60
61-65
66-77
78-79
80-81
* 82-83
84-85
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8-31
32-40
41-53
54-66
67-69
70
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8-31
32-40
41-53
54-56
57
58-60
61
3
2
2
25
11
6
5
6
5
12
2
2
2
2
1 (Dl)
LENGTH
3
2
2
24
9
13
13
3
1
2 (D2)
LENGTH
3
2
2
24
9
13
3
1
3
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
MATRIX SPIKE -
EPA SAMPLE NO.
RPD: * OUTSIDE QC LIMITS
RPD: TOTAL
SPIKE RECOVERY: t OUT
SPIKE RECOVERY: TOTAL
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
SPIKE ADDED (UG/L)
SAMPLE CONC. (UG/L)
MS CONC. (UG/L)
MS* REC.
MS* REC. OUT FLAG
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
SPIKE ADDED (UG/L)
MSD CONC. (UG/L)
MSD% REC.
MSDX REC. OUT FLAG
X RPD
X RPD OUT FLAG
•3Cf
•AA'-'ZZ'
•Hlf
NUMERIC 2
NUMERIC 2
NUMERIC 2
NUMERIC 2
FORMAT/CONTENTS
•3C'
'AA'-'ZZ*
«Dlf
NUMERIC 9.3
NUMERIC 13.3
NUMERIC 13.3
NUMERIC 3
BLANK OR •«'
FORMAT/CONTENTS
«3C'
*AA'-'ZZf
«D2'
NUMERIC 9.3
NUMERIC 13.3
NUMERIC 3
BLANK OR '«'
NUMERIC 3
BLANK OR '*«
H - 25
1/87 REV.
-------
COMMENT RECORD 1 (CD
COLUMN (S) LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8-72
3
2
2
65
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMMENT LINE 1
COMMENT RECORD 2 (C2>
COLUMN (S) LENGTH CONTENTS
•3C»
•AA'-'ZZ'
'Cl
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8-72
3
2
,2
65
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMMENT LINE 2
•3Cf
'AA'-'ZZ'
C2
H - 26
1/87 REV
-------
SOU SEWIVOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY - tFORHSD)
HEADER RECORD 1 (HI)
COLUMN (S) LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8-32
33-43
44-49
50-54
55-60
61-65
66-77
78-80
. 81-82
83-84
85-86
87-88
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8-31
32-40
41-53
54-66
67-69
70
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8-31
32-40
41-53
54-56
57
58-60
61
3
2
2
25
11
6
5
6
- 5
12
3
2
2
2
2
1 (Dl)
LENGTH
3
2
2
24
9
13
13
3
1
2 (D2)
LENGTH
3
2
2
24
9
13
3
1
3
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SD6 NO.
MATRIX SPIKE -
EPA SAMPLE NO.
LEVEL
RPD: t OUTSIDE QC LIMITS
RPD: TOTAL
SPIKE RECOVERY: * OUT
SPIKE RECOVERY: TOTAL
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
SPIKE ADDED (UG/KG)
SAMPLE CONC. (UG/KG)
MS CONC. (UG/KG)
MS% REC.
MS* REC. OUT FLAG
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
SPIKE ADDED (UG/KG)
MSD CONC. (UG/KG)
MSDX REC.
MSD* REC. OUT FLAG
X RPD
% RPD OUT FLAG
'3D'
•AA'-'ZZ'
•HI'
•LOW OR 'MED'
NUMERIC 2
NUMERIC 2
NUMERIC 2
NUMERIC 2
FORMAT/CONTENTS
«3Df
'AA'-'ZZ'
•Dlf
NUKERIC 9.3
NUMERIC 13.3
NUMERIC 13.3
NUMERIC 3
BLANK OR '*'
FORMAT/CONTENTS
•3D*
•AA'-'ZZ*
•D2*
NUMERIC 9.3
NUMERIC 13.3
NUMERIC 3
BLANK OR '«'
NUMERIC 3
BLANK OR '*•
H - 27
1/87 REV.
-------
COMMENT RECORD 1 (CD
COLUMN (S) LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
-------
HATER PESTICIDE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY-(FORM3E)
HEADER RECORD 1 (HI)
COLUMN (S) LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8-32
33-43
44-49
50-54
55-60
61-65
66-77
78-79
80-81
* 82-83
84-85
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8-31
32-40
41-53
54-66
67-69
70
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8-31
32-40
41-53
54-56
57
58-60
61
3
2
2
25
11
6
5
6
5
12
2
2
2
2
1 (Dl)
LENGTH
3
2
2
24
9
13
13
3
1
2 (D2)
LENGTH
3
2
2
24
9
13
3
1
3
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
MATRIX SPIKE -
EPA SAMPLE NO.
RPDJ t OUTSIDE QC LIMITS
RPD? TOTAL
SPIKE RECOVERY: * OUT
SPIKE RECOVERY: TOTAL
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
SPIKE ADDED (UG/L)
SAMPLE CONC. (UG/L)
MS CONC. (UG/L)
MS% REC.
MS* REC. OUT FLAG
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
SPIKE ADDED (UG/L)
MSD CONC. (UG/L)
MSDX REC.
WSDX REC. OUT FLAG
X RPD
* RPD CUT FLAG
«3E'
•AA'-'ZZ'
'HI'
NUMERIC 2
NUMERIC 2
NUMERIC 2
NUMERIC 2
FORMAT/CONTENTS
f3E*
•AA'-'ZZ'
'Dl'
NUMERIC 9.3
NUMERIC 13.3
NUMtRIC 13.3
NUMERIC 3
BLANK OR '*'
FORMAT/CONTENTS
'3E'
'AA'-'ZZ'
'02'
NUMERIC 9.3
NUMERIC 13.3
NUMERIC 3
BLANK OR '*«
NUMERIC 3
BLANK OR '«'
H - 29
1/87 REV
-------
COMMENT RECORD 1 (CD
COLUMN (S)
LENGTH CONTENTS
COMMENT RECORD 2 (C2>
COLUMN (S) LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8-72
3
2
2
65
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMMENT LINE 1
f3Ef
•AA*
•Cl*
-'ZZ'
FORMAT/CONTENTS
1- 3
<•- 5
6- 7
8-72
3
2
2
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMMENT LINE 2
•3E*
•AA'-'ZZ1
•C2«
H - 30
1/87 REV
-------
SOIL PESTICIDE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY - IFORM3P5
HEADER RECORD 1 (HI)
COLUMN (S) LENGTH CONTENTS FORMAT/CONTENTS
1- 3
4- 5
6- 7
8-32
33-43
44-49
50-54 _
55-60
61-65
66-77
78-80
81-82
83-84
* 85-86
87-88
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8-31
32-40
41-53
54-66
67-69
70
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8-31
32-40
41-53
54-56
57
58-60
61
3
2
2
25
11
6
5
6
5
12
3
2
2
2
2
1 (Dl)
LENGTH
3
2
2
24
9
13
13
3
1
2 (D2)
LENGTH
3
2
2
24
9
13
3
1
3
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
MATRIX SPIKE -
EPA SAMPLE NO.
LEVEL
RPD: * OUTSIDE QC LIMITS
RPD: TOTAL
SPIKE RECOVERY: t OUT
SPIKE RECOVERY: TOTAL
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
SPIKE ADDED (UG/KG)
SAMPLE CONC. (UG/KG)
MS CONC. (UG/KG)
MS% REC.
MS% REC. OUT FLAG
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMPOUND
SPIKE ADDED (UG/KG)
MSD CONC. (UG/KG)
MSDX REC.
MSDX REC. OUT FLAG
X RPD
% RPD OUT FLAG
-3F'
•AA'-*ZZf
fHlf
'LOW OR 'MED'
NUMERIC 2
NUMERIC 2
NUMERIC 2
NUMERIC 2
FORMAT/CONTENTS
'3F«
•AA'-'ZZ'
•Dl'
NUMERIC 9.3
NUMERIC 13.3
NUMERIC 13.3
NUM!RIC 3
BLANK OR '*'
FORMAT/CONTENTS
•3F*
•AA'-'ZZ'
'D2'
NUMERIC 9.3
NUMERIC 13.3
NUMERIC 3
BLANK OR '*'
NUMERIC 3
BLANK OR •«'
H - 31
1/87 REV
-------
COMMENT RECORD 1 (CD
COLUMN (S) LENGTH CONTENTS
COMMENT RECORD 2 (C2)
COLUMN (S) LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
-------
FORM IV FILE DESCRIPTION
(FORMA)
H - 33 1/87 REV.
-------
VOLATILE METHOD BLANK SUMMARY - (FORM 4A)
HEADER RECORD 1 CHI)
COLUMN (S)
LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8- 32
33- 43
44- 49
50- 54
55- 60
61- 65
66- 79
80- 91
92- 99
100-103
104-108
109-111
112-121
122
123
DETAIL RECORD
COLUMN (S)
1- 3
4- 5
6- 7
8- 9
10-21
22-33
34-47
48-51
3
2
2
25
11
6
5
6
5
,1*
12
8
4
5
3
10
1
1
1 (Dl)
LENGTH
3
2
2
2
12
12
14
4
FORM NUMBER
FORM SUFFIX
RECORD TYPE
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
LAB FILE ID
LAB SAMPLE ID
DATE ANALYZED
TIME ANALYZED
MATRIX
LEVEL
INSTRUMENT ID
PAGE
OF
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
EPA SAMPLE NO.
LAB SAMPLE ID
LAB FILE ID
TIME ANALYZED
•4A'
'AA'-'ZZ'
•HI'
MM/DD/YY
HHMM
•SOIL ' OR 'WATER'
•LOW OR fMED»
NUMERIC 1
NUMERIC 1
FORMAT/CONTENTS
'4A'
•AA'-'ZZ'
«D1*
NUMERIC 2
^P
HHMM
COMMENT RECORD 1 (CD
COLUMN CS)
1- 3
4-5
6- 7
8-72
LENGTH
3
2
2
65
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMMENT LINE 1
FORMAT/CONTENTS
'4A'
f AA'-'ZZ'
•Clf
COMMENT RECORD 2 CC2)
COLUMN (S)
1- 3
4- 5
6- 7
8-72
LENGTH
3
2
2
65
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMMENT LINE 2
FORMAT/CONTENTS
•4Af
'AA'-'ZZ'
'C2'
H - 34
1/87 REV.
-------
SEMIVOLATILE METHOD BLANK SUMMARY - (FORM 4B)
HEADER RECORD 1 (HI)
COLUMN (S) LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8- 32
33- 43
44- 49
50- 54
55- 60
61- 65
66- 79
80- 91
92- 99
100-103
104-111
' 112-115
116-120
121-123
124-133
134
135
DETAIL RECORD
COLUMN CS)
1- 3
4- 5
6- 7
8- 9
10-21
22-33
34-47
48-55
3
2
2
25
11
6
5
6
5
.14
12
8
4
8
4
5
3
10
1
1
1 (Dl)
LENGTH
3
2
2
2
12
12
14
8
FORM NUMBER
FORM SUFFIX
RECORD TYPE
LAB NAME
CONTRACT
LAB CODE
CASE NO.
SAS NO.
SDG NO.
LAB FILE ID
LAB SAMPLE ID
DATE EXTRACTED
EXTRACTION
DATE ANALYZED
TIME ANALYZED
MATRIX
LEVEL
INSTRUMENT ID
PAGE
OF
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
SEQUENCE NUMBER
EPA SAMPLE NO.
LAB SAMPLE ID
LAB FILE ID
DATE ANALYZED
•4B'
'AA'-'ZZ'
•HI'
MM/DD/YY
'SEPF', 'CONT' OR 'SONC'
MM/DD/YY
HHMM
•SOIL ' OR 'WATER'
'LOW OR 'MED'
NUMERIC 1
NUMERIC 1
FORMAT/CONTENTS
•4B'
•AA'-'ZZ'
•DJ,'
NUMERIC 2
MM/DD/YY
COMMENT RECORD 1 (CD
COLUMN (S)
1- 3
4- 5
6- 7
8-72
LENGTH
3
2
2
65
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMMENT LINE 1
FORMAT/CONTENTS
'4B'
•AA'-'ZZ'
•Cl'
COMMENT RECORD 2 (C2)
COLUMN (S)
1- 3
4- 5
6- 7
9-72
LENGTH
3
2
2
65
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
COMMENT LINE 2
FORMAT/CONTENTS
•4B'
•AA'-'ZZ'
'C2'
H - 35
1/87 REV
-------
PESTICIDE METHOD BLANK SUMMARY -
|