United States
Environmental Protection
Agency
Office of
Solid Waste and
Emergency Response
Publication 9240.1-08
E P A/540/R/94/077
PB95-963507
December 1994
Superfund
oEPA USEPA CONTRACT
LABORATORY PROGRAM
STATEMENT OF WORK
FOR ORGANICS ANALYSIS
MULTI-MEDIA, HIGH
CONCENTRATION
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9240 .1-08
PB95-963 507
EPA54 0/R-94/077
USEPA CONTRACT LABORATORY PROGRAM
STATEMENT OF WORK
FOR
ORGANICS ANALYSIS
Multi-Media, High-Concentration
SOW No. Rev. 9/88
including Rev. 4/89
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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
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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 and extractable compounds listed
on the Target Compound List (TCL) in Exhibit C. The Contractor shall employ
state-of-the-art GC/MS and 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 separate multiphase samples into single phase
units and prepare extracts and dilutions of samples. The Contractor shall
screen extracts 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 single phase
units, blanks, and control matrix spikes with the surrogate spiking compounds
listed in Exhibit E. Aliquots for volatile organics analysis shall be spiked
with the internal standard compounds listed in Exhibit E before purging.
Additionally, for each single phase unit 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 extractable 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.
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 perforin 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. Documentation, as described therein, shall
be required to show that all procedures are being strictly followed.
2. Prepare samples as described in Exhibit D. Samples are separated
into single phase units (if required) and screened to determine the
proper dilution for GC/MS analysis.
Extracts must be analyzed within 40 days of VTSR.
Task II: Analysis for Identity 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.
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.
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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 DFTFP 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 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.
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.
The Toxaphene and the Aroclor compounds listed in Exhibit C and
analyzed by GC/EC techniques shall have their identifications
verified by an analyst competent in the interpretation of gas
chromatograms. Two criteria must be satisfied to verify the
identifications:
a, Elution of the sample component within the retention time
window (established by the procedures in Exhibit E) of the
standard component analyzed on the same GC column and
instrument, as part of the same analytical sequence specified
in Exhibit D ARO.
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.
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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 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 ARQ.
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 an analytical sequence, as
described in Exhibit D ARQ and Exhibit E.
Task V: Tentative Identification of Non-TCL Sample Components.
1. For each 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 extractable 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,
unknown chlorinated compound). If probable molecular weights can be
distinguished, include them.
The Contractor shall not 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).
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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, Single phase units, method blanks and control matrix
spikes shall be carried through the entire analytical process from
extraction, GC screen, to final GC/MS analysis, including all data
reporting requirements and magnetic tape data storage.
2. The Contractor shall perform one control matrix spike sample
analysis for each case received, or for each 20 single phase units,
or each 14 calendar day period during which single phase units in a
Case were received (said period beginning with the receipt of the
first sample in that Sample Delivery Group) whichever is most
frequent.
Samples, blanks and control matrix spikes shall be carried through
the entire analytical process from extraction to final GC/MS
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 once for:
o each Case of single phase units received, OR
o each 20 single phase units in a Case, OR
o each 14 calendar day period during which single phase units 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.
Extractable 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 within
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40 calendar days of receipt of the samples. The results of all such
control or PE check samples may be used as grounds for termination
of noncompliant contractors.
B. EPA has provided to the Contractor formats for the reporting of data
(Exhibit B). The Contractor shall be responsible for completing and
returning analysis data sheets in the format specified in this SOW and
within the time specified in the Contract Performance/Delivery Schedule.
1. Use of formats other than those designated by EPA will be deemed as
noncompliance. Such data are unacceptable. Resubmission in the
specified format at no additional cost to the government will be
required.
2. Computer generated forms may be submitted in the hardcopy data
package(s) provided that the forms are in EXACT EPA FORMAT. This
means that the order of data elements is the same as on each EPA
required form, including form numbers and titles, page numbers and
header information
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 split/splitless injector and
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.
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f. The GC for Aroclor analysis shall be equipped, with dual wide
bore (>0,53 mm) capillary columns and a suitable detector as
described in Exhibit D. The instrument must be capable of
operating with a temperature program.
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.
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.
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.
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.
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•
F. 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 single phase unit extracts within 7 days
after request, as specified in the Contract Performance/Delivery
Schedule.
G. 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).
H. 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.
I. 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 single phase units received, OR
o each 20 single phase units within a Case, OR
o each 14 calendar day period during which single phase units in a Case
are received (said period beginning with the receipt of the first
sample in the Sample Delivery Group).
Data for all samples in a Sample Delivery Group are due concurrently 40
days after receipt of the last sample received in the Sample Delivery
Group. Data for all samples in a Sample Delivery Group must be
submitted together (in one package) in the order specified in Exhibit B.
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The Sample Delivery Group number is the EPA sample number of the first
sample received in the SDG. When several samples are received together
in the first SDG shipment, the SDG number shall be the lowest sample
number (considering both alpha and numeric designations) in the first
group of samples received under the SDG. The SDG number is reported on
all data reporting forms.
The SDG Receipt Date is the day the last sample in the SDG is received.
Data for all samples in the SDG are due 40 days following this date.
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.
J. 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 davs
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.
K. 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.
L. 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.
M, 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,
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.
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.
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
seraivolatiles analyses.
o Mass spectral interpretation.
o Extraction.
o Pesticide analysis.
2. 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.
a. Primary Instrument Requirements
(1) 60 Phase Units/Month Capacity
| Purpose
i 1
| Fraction |
1 I
No. of
Instrument(s)
j Type of
| Instrument
i
(Analysis
1 I
|Volatiles |
1 1
1 i
I 1
1
1
|GC/MS/DS with
|purge and trap
|device
i
|Extractables|
1 1
1
IGC/MS/DS
1
I
1
|Aroclors/ |
|Toxaphene |
1 1
1
|GC/EC with
|dual column
I
|GPC Cleanup
1
1
|Extractables |
1 1
1 1
1
|GPC with UV
j detector
1
|Screening
I
1 1
1 1
1
| GC/FID
1
Note: For contracts of two (2) bid lots or more:
o Minimum of three (3) GC/MS/DS and three (3) GC systems are
required at the time of on-site laboratory evaluation.
o An additional one (1) GC/MS/DS and one (1) GC system with
dual detectors are required as a back-up system at the time
of on-site laboratory evaluation.
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b. Secondary Instrument Requirements
(1) 60 Phase Units/Month Capacity
The Contractor shall have the following instruments in
place and operational at any one time as a back-up system;
Quantity Instruments
One GC/MS/DS
One Purge and Trap Device
One GC with dual detectors (FID and EC)
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.
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:
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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.
3. Sample Custodian
Responsible for receiving the EPA samples (logging, handling and
storage).
4. Quality Assurance Officer
Responsible for overseeing the quality assurance aspects of the data
and reporting directly to upper management.
5. Data Reporting and Delivery Officer
Responsible for all aspects of data deliverables: organization,
packaging, copying, and delivery.
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EXHIBIT B
REPORTING AND DELIVERABLES REQUIREMENTS
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EXHIBIT B
REPORTING AND DELIVERABLES REQUIREMENTS
Page No.
SECTION I: Contract Reports/Deliverables Distribution B-2
SECTION II: Report Descriptions and Order of Data
Deliverables B-5
SECTION III: Forms Instruction Guide B-21
SECTION IV: Data Reporting Forms B-40
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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
_OJ £21
Contract Start-Up
Plan
7 Days after
contract award
B. Updated SOPs
120 days after
contract award
Item
No.
Copies
Delivery
Schedule
Distribution
(3)
(U)
111
(61
**C. Sample Traffic
Reports
3 days after
receipt of
last sample
in Sample
Delivery Group
(SDG)****
***D. Sample Data 1
Summary Package
last sample
in SDG
35 days after
receipt of
X
***E. Sample Data
Package
35 days after
receipt of
last sample
in SDG
X
F. GC/MS Tapes
Lot Retain for 365
days after data
submission, or
submit within 7
days after
receipt of
written request
by PO and/or EMSL/LV.
As Directed
B-2
Rev. 1/89
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No. Delivery
Copies Schedule
Distribution
Item
(3^ (4) CD L61
G. Extracts
Lot Retain for 365
As Directed
days after data
submission, or
submit within 7
days after
receipt of
written request
by PO or SHO
H. Complete Case 1 Submit 180 days
File Purge Pkg after data
X
submission or 7
days after receipt
of written request
by PO or SMO.
* Contractor must be prepared to receive samples within 30 days of contract
award. NOTE: EPA cannot 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.
** 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.
Distribution Addresses:
(1) USEPA Analytical Operations Branch (WH 548A)
401 M Street, SW
Washington, DC 20460
ATTN: (Project Officer's Name)
(2) USEPA
Contracts Management Division (MD-33)
Administration Building Lobby, Alexander Drive
Research Triangle Park, NC 27711
ATTN; (Contract Officer's Name)
B-3
Rev. 9/88
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(3) USEPA Contract Lab Program
Sample Management Office (SMQ)
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. SM0 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-4
Rev. 9/88
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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.1). 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 . 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. ¦
Descriptions of the requirements for each deliverable item cited in the
Contract Performance/Delivery Schedule (Contract Schedule, Section F.l) 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-5
Rev. 9/88
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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. Undated 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 Performance 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.
B-6
Rev. 9/88
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C. Sample Traffic Reports
Original Sample Traffic Report page marked "Lab Copy for Return to SKO"
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, all the samples on one multi-sample TR may not be necessarily
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. Sample Data Summary Package
As specified in the Delivery Schedule, one Sample Data Summary Package
shall be delivered to SMO concurrently with delivery of other required
sample data. The Sample Data Summary Package consists of copies of
specified items from the Sample Data Package. These items are listed
below and described under part C, Sample Data Package.
B-7
Rev. 9/88
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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 (HCV, HCE, and HCA,) and by phase unit within each
fraction - tabulated target compound results (Form I) and
tentatively identified compounds (Form I, TIC) (HCV, HCE only).
3. By fraction (HCV, HCE, HCA) - surrogate spike analysis results (Form
II).
4. By fraction (HCV, HCE, HCA) - control matrix spike results (Form
III)
5. By fraction (HCV, HCE, HCA) - blank data (Form IV) and tabulated
results (Form I) including tentatively identified compounds (Form I,
TIC)(HCV, HCE only).
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, extractables, Aroclors). If the analysis of a fraction is
not required, then that fraction-specific unit is not required as a
deliverable.
The Sample Data Package shall include data for analyses of all samples
in one Sample Delivery Group, including field samples, reanalyzes,
blanks, and control matrix spikes.
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) and the phase units analyzed from'each sample,
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-8
Rev. 9/88
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The Contractor must 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 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. Copies of the SDG cover sheet are to
be included with the copies of the Traffic Reports.
If samples are received at the laboratory with multi-sample Traffic
Reports (TRs) all the samples on one multi-sample TR may not
necessarily be in the same SDG. In this instance, the laboratory
must make the appropriate number of photocopies of the TR so that a
copy is submitted with each data package to which it applies. In
addition, in any instance where samples from more than one multi-
sample TR are in the same data package, the laboratory must submit a
copy of the SDG cover sheet with copies of the TRs.
3. High Concentration Volatiles Data
a. QC Summary
(1) Surrogate Percent Recovery Summary (Form II HCV)
(2) Control Matrix Spike Summary (Form III HCV)
(3) Method Blank Summary (Form IV HCV)
(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 HCV)
BFB in chronological order; by instrument.
B-9
Rev. 9/88
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Sample Data
Sample data shall be arranged in packets with the High
Concentration Volatile Analysis Data Sheet (Form 1 HCV,
including Form I HCV-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. Phase units within a sample
should be placed in order by phase unit suffix (i.e. AB123-11,
AB123-12, etc.)
(1) TCL Results - High Concentration Volatile Analysis Data
Sheet (Form I HCV).
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.l).
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
mg/kg. 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 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 HCV-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-10
Rev. 9/88
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o EPA sample number
o Date and tine 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 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
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-11
Rev. 9/88
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Standards Data
(1) Initial Calibration Data (Form VI HCV) - in order by-
instrument, if more than one instrument used.
(a) HCV 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 HCV) - in order by-
instrument , if more than one instrument used.
(a) HCV 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 HCV) - 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 HCV).
(b) Tentatively Identified Compounds (Form I HCV-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-12
Rev. 9/88
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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-otder:
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) Control Matrix Spike Data
(a) Tabulated results (Form I HCV) of nonspiked TCL
compounds. Form I HCV-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. Extractables Data
a. QC Summary
(1) Surrogate Percent Recovery Summary (Form II HCE)
(2) Control Matrix Spike Summary (Form III HCE)
(3) Method Blank Summary (Form IV HCE)
(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 HCE)
DFTPP in chronological order; by instrument.
b. Sample Data
Sample data shall be arranged in packets with the High
Concentration Extractable Analysis Data Sheet (Form I HCE,
including Form I HCE-TIC), followed by the raw data for
extractable samples. These sample packets should then be
placed in increasing EPA sample number order, considering both
letters and numbers in ordering samples. Phase units within a
sample should be placed in order by phase unit suffix (i.e.,
AB123-11, AB123-12, etc.).
B-13
Rev. 9/88
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(1) TCL Results - High Concentration Extractable Analysis Data
Sheet (Form I HCE-1, HCE-2, HCE-3),
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.l).
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
me/kg. 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 HCE-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 HCE-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).
(3) Reconstructed total ion chromatograms (RIG) 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
B-14
Rev. 9/88
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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 ehromatogram. 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 ehromatogram.
o EPA sample number
o Date and time of analysis
o RT 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.
c. Standards Data
(1) Initial Calibration Data (Form VI HCE-1, HCE-2, HCE-3) -
in order by instrument, if more than one instrument used.
(a) Extractables standard(s) reconstructed ion
chromatograms and quantitation reports (or legible
facsimile) for the initial (three 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
B-15
Rev. 9/88
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case. When more than one initial calibration is
performed, the data must be put in chronological
order, by instrument.
(2) Continuing Calibration (Form VII HCE-1, HCE-2, HCE-3) - in
order by instrument, if more than one instrument used.
(a) Extractable 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 KCE-1, HCE-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.
(4) GPC Calibration (Form IX HCE) - in order by calibration
date.
(a) Copies of UV traces for each GPC calibration
performed labeled with date and time of the
calibration, and labeling each peak in the
calibration standard with the name of the compound
and its retention time. -~-
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.
(a) Tabulated results (Form I HCE-1, HCE-2, HCE-3)
(b) Tentatively Identified Compounds (Form I HCE-TIC) -
even if none found.
(c) Reconstructed ion ehromatogram(s) and quantitation
report(s) or legible facsimile (GC/MS), labeled as in
b.(3) above.
B-16
Rev. 9/88
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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) Control Matrix Spike Data
(a) Tabulated results (Form I) of nonspiked TCL
compounds. Form 1 HCE-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. Aroclor/Toxaphene Data ,
a. QC Summary
(1) High Concentration Aroclor Surrogate Recovery Summary
(Form II HCA)
(2) High Concentration Aroclor Control Matrix Spike Recovery
Summary (Form III HCA)
(3) High Concentration Aroclor Method Blank Summary (Form IV
HCA-1)
(If more than a single form is necessary, forms must be
arranged in chronological order by date of analysis of the
blank.)
(4) High Concentration Aroclor Instrument Blank Summary (Form
IV HCA-2)
(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 High
Concentration Aroclor Analysis Data Sheet (Form I HCA),
followed by the raw data for samples. These sample packets
B-17
Rev. 9/88
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should then be placed in increasing EPA sample number order,
considering both letters and numbers in ordering samples.
(1) TCL Results - High Concentration Aroclor Analysis Data
Sheet (Form I HCA).
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.l).
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
mg/kg. No other units are acceptable.
NOTE: Report analytical results to two significant figures
for all Aroclor/Toxaphene samples.
(2) Copies of Aroclor/Toxaphene analysis 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 Aroclor/Toxaphene analysis chromatograms from
second GC column confirmation. Chromatograms to be
labeled as in (2) above.
(4) Manual work sheets,
c. Standards Data
(1) Form VI HCA-1 and HCA-2 - High Concentration Initial
Calibration of Multicomponent Analytes (all GC columns)
(2) Form VII HCA - High Concentration Continuing Calibration
of Multicomponent Analytes (all GC columns)
(3) Form VIII HCA - High Concentration Analytical Sequence
(all GC columns)
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(4) Form IX HCA - High Concentration Single Component
Pesticide Retention Times (all GC columns)
(5) Form X HCA - High Concentration Aroclor Identification
Summary (only required for positive results)
(6) Form XI HCA - High Concentration Aroclor Diol Cartridge
Check (all lot numbers used)
(7) Aroclor/Toxaphene standard chromatograms and data system
printouts for all standards to include:
o All Aroclors and Toxaphene
o All quantitation standards
o Diol cartridge check standard for each lot of
cartridges used
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 standard peaks for all individual
compounds either directly out from the peak or on
the printout of retention times if retention times
are printed over the peak,
o Label the chromatogram for multicomponent
standards, (i.e., Aroclor 1242, Toxaphene)
o List total ng injected for each standard.
o A printout of retention times and corresponding
peak areas must accompany each chromatogram.
o Date and time of injection.
o GC column identification (by stationary phase).
o GC instrument identification.
Raw QC Data
(1) Method Blank Data - in chronological order. NOTE: This
order is different from that used for samples.
(a) Tabulated results (Form I HCA).
(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) Instrument Blank Data - in chronological order. NOTE:
This order is different from that used for samples.
(a) Tabulated results (Form I HCA).
(b) Chromatogram(s) and data system printout(s) (GC) for
each GC column and instrument used for analysis,
labeled as in b.(2) above.
B-19 Rev. 4/89
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(3) Control Matrix Spike Data
(a) Tabulated results (Form I HCA) of tionspike TCL
compounds.
(b) Chromatograni(s) and data system printout(s) (GC) ,
labeled as in b. (2) above-.
F. C,C/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, control matrix spikes, 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 EFA sample number,
calibration data, standards, blanks, and control matrix spikes. 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 or the Sample Management
Office.
G. Extracts
The Contractor shall preserve sample extracts at 4°C (+2°C) in
bottles/vials with teflon-lined septa. Extract bottles/vials shall be
labeled with EFA 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.
H. 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).
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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,
or extractable). 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 high concentration volatile analysis only, provide
only HCV forms. There are three pages relating to the extractable fraction
for Forms I, VI, VII, and VIII. Whenever extraetables are analyzed and one
of the above named fdrms is required, all three pages (HCE-1, HCE-2, and HCE-
3) must be submitted. In addition to the forms for high concentration
volatiles and high concentration extractable, forms are provided for the
Aroclor-specific GC/EC analysis of high concentration samples (HCA). 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. Control Matrix Spike Recovery (Form III, All Fractions)
E. Method Blank Summary (Form IV, All Fractions)
F. GC/MS Tuning and Mass Calibration (Form V HCV, Form V HCE)
G. Initial Calibration Data (Form VI HCV, Form VI HCE, Form VI HCA)
H. Continuing Calibration Data (Form VII HCV, Form VII HCE, Form VII
HCA)
I. Internal Standard Area Summary (Form VIII HCV, Form VIII HCE) and
Analytical Sequence (Form VIII HCA)
J. GPC Calibration (Form IX HCE) and Pesticide Retention Times (Form IX
HCA)
K. Aroclor Identification Summary (Form X HCA)
L. Diol Cartridge Check (Form XI HCA)
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A, General Information and Header Information
Values must be reported on the forms according to the individual form
instructions in this Section. For example, results for concentrations of HCV
TCL compounds must be reported to two significant figures if the value is
greater.than or equal to 10.
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. For
items appearing on the uncompleted forms (Section IV), the use of uppercase
and lowercase letters is optional.
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 2HA, 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.
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 l:SDG No." is the Sample Delivery Group number. The Sample Delivery Group
(SDG) number is the EPA Sample Number of the first sample received in the
SDG. When several samples are received together in the first SDG shipment,
the SDG number shall be the lowest sample number (considering both alpha and
numeric designations) in the first group of samples received under the SDG.
The "SAS No." is the EPA-assigned number for analyses performed under Special
Analytical Services. If samples are to be analyzed under SAS only, and
reported on these forms, then enter SAS No., and leave Case No. blank. If
samples are analyzed according to the "Routine Analytical Services" (IFB)
protocols and have additional "SAS" requirements, list both Case No. and SAS
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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 right-hand 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 right-
hand corner of Form I, it should be entered on the middle line of the three
lines that comprise the box.
All samples, control matrix spikes, blanks and standards shall be identified
with an EPA Sample Number. Because a sample may comprise a number of single -
phase units, the use of sample number suffixes is necessary to differentiate
between phase units. The following system of suffixes must be used:
XXXXX - EPA sample number
XXXXX-11 - first phase unit
XXXXX-12 - second phase unit
through
XXXXX-19 - ninth phase unit
XXXXX-YYRE - reanalysis of phase unit YY
XXXXX-YYDL - phase unit YY analyzed at a secondary dilution.
CMS - Control Matrix Spike
Note: If more than nine phases are separated from a single sample,
contact SMO for instructions on numbering the phases.
Use of the suffixes "RE" and/or "DL" assumes that data are also being
submitted for an analysis of a phase unit that represents the "original"
analysis of the phase unit. If only one set of data are being submitted, do
not use the suffix "RE" or "DL".
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. Extractable blanks shall be identified as EBLK##.
3. Aroclor method blanks shall be identified as ABLK##.
4. Aroclor instrument blanks shall be identified as IBLK##.
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
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characters or numbers, or a combination of both. For example,
possible identifiers for volatile blanks would be VBLK1, VBLK2,
VBLK1Q, VBLKAB, etc.
5. Volatile and extractable standards shall be identified as:
FSTD###, where:
F - fraction (V for volatiles; E for extractable).
### - the concentration in ug/L of volatile standards (i.e., 20,
50, 100, 150, 200)
the amount injected in ng for extractable standards (i.e. 50, 80,
160). For PCB standards, the amounts injected would be 10, 30,
50 or 20, 60, 100 ng. If PCB standards are coinjected in
different amounts, use the lower amount (i.e., ESTD10 for
coinjection of 10 and 20 ng of PCBs)
6. Aroclor 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: Phase type, Phase weight, and Lab Sample ID.
For the purposes of this contract, there are only three possible phase types.
They are:
Solids
Water Immiscible Liquids
Water Miscible Liquids
For "Phase Type", enter "SOLID" for solid phase units. Enter "WIL" for water
immiscible liquids, and enter "WML" for water miscible liquids. Water
samples are considered as water miscible liquids, and would be entered as
"WML", not "WATER".
For "Phase weight" enter the number of grams of phase unit used.
"Lab Sample ID" is an optional laboratory-generated internal identifier.
"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, and VIII contain a field labeled "page _ of in the bottom
left-hand 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."
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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 HCV, Form I HCE-1, Form I HCE-2, Form I HCE-3, Form I HCA
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 HCV analysis only is
requested, Form I HCV and Form I HCV TIC must be submitted. If
the Aroclor-specific analysis is the only analysis requested,
only Form I HCA 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:
Enter pH for Extractables and Aroclors, reported to 0.1 pH units.
"Date Received" is the date of sample receipt at the laboratory,
as noted on the Traffic.Report (i.e., the VTSR). It should be
entered as MM/DD/YY,
"Date Separated", "Date Extracted" and "Date Analyzed" should be
entered in a similar fashion. For Aroclor-specific samples, the
date of analysis should be the date of the first GC analysis
performed.
For all fractions,, enter the final volume in milliliters of the
sample extract under "Final Extract Volume". Report volume to
one tenth of a milliliter (i.e. 10.0, not 10).
For volatiles, enter the number of microliters of the extract
that was added to the reagent water under "Aliquot Volume".
For extractable, enter the number of microliters of the extract
that is injected under "Injection Volume".
For all three fractions, enter under "Conversion Factor" the
value used to convert your raw data into the concentration values
in rag/Kg reported on Form I for all detected compounds. Note:
this conversion factor must incorporate the phase weight, the
final extract volume, the injection or aliquot volume, the use of
GPC clean-up procedures, and any dilution of the extract or
sample that is required. The units associated with this factor
will vary, depending on the units given in the raw data.
Therefore, no units for the conversion factor are to be reported
on Form I.
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If samples for Aroclor/Toxaphene analysis were subjected to
sulfur clean-up procedures, enter "Y" under "Sulfur Clean-up
(Y/N)." If no sulfur clean-up was performed enter "N".
For positively identified TCL compounds, the contractor shall
report the concentrations detected as uncorrected for blank
contaminants.
For volatile and extractable results, report analytical results
to one significant figure if the value is less than 10, and two
significant figures above 10.
Report all Aroclor-specific results to two significant figures.
The concentration units are mg/Kg for all phase types and
fractions.
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.
For reporting results to the USEPA,' the following contract
specific qualifiers are to be used. The eight 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 eight 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. For example,
20 U for phenol 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 200 U.
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 or
GC/EC 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 mg/Kg, but a concentration of 3
mg/Kg is calculated, report it as 3J. The sample quantitation
limit must be adjusted for dilution as discussed for the U flag.
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.
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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 Aroclors analyzed by GC/EC
methods. If one or more compounds have a response greater than
full scale, the 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.
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.
N - This flag identifies Aroclor or Toxaphene compounds where one or
more of the peaks used for quantitation are more than two times
the width of the corresponding peaks in the highest concentration
calibration standard. It indicates an uncertainty in the
quantitation for the compound other than those discussed under
the "J" flag.
X - Other specific flags and footnotes may be required to properly
define the results. In order to limit the number of laboratory-
defined flags and not use such flags as may be part of the
Agency's data review processes, the laboratory-defined flags are
restricted to the three letters "X", "Y", and "Z". If used, they
must be fully described and such description attached to the
Sample Data Summary Package and the Case Narrative. If more than
one is required, use "Y" and "Z", as needed. If more than five
qualifiers are required for a sample result, use the "X" flag to
combine several flags, as needed. For instance, the "X" flag
might combine the "A", "B", and "D" flags for some samples.
The 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.
Form I HCV-TIC and Form I HCE-TIC
Fill in all header information as above.
Rev. 9/88
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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 HCV-TIC or HCE-TIC for every volatile and extractable
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).
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-me thy1- 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
extractable compounds to be searched. NOTE: The name of the first of
these aldol-condensation reaction products will have to be truncated to
28 characters (i.e., "4-methyl-4.-hydroxy-2-pentano").
Surrogate Recovery (Form II)
Form II is used to report the recoveries of the surrogate compounds
added to each sample, blank, and control matrix spike. Form II is
fraction-specific.
Complete the header information and enter EPA Sample Numbers as
described in part A. 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 right-hand column, total the
number of surrogate recoveries outside the QC limits for each sample.
If no surrogates were outside the limits, enter "0".
If the surrogates are diluted out in any analysis, enter the calculated
recovery or "0" (zero) if the surrogate is not detected, and flag the
surrogate recoveries with a "D" in the column under the symbol. Do
not include results flagged "D" in the total number of recoveries for
each sample outside the QC limits.
On Form II HCA, for Aroclcr-specific analyses by GC/EC, report the
surrogate recoveries from both GC columns, identifying each column by
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stationary phase in the fields labelled "GC Column ID (1)" and "GC
Column ID (2)".
If an interference prevents the quantitation of one of the two Aroclor
surrogates, enter that value as "0", flag it in column under the
symbol, and describe the problem in the Case Narrative.
Number all pages as described in part A.
D, Control Matrix Spike Recovery (Form III)
This form is used to report the results of the analyses of the control
matrix spike.
Complete the header information as instructed in Part A.
In the box on Form III, under "SPIKE ADDED", enter the calculated
concentration in mg/Kg that results from adding each spiked compound to
the aliquot chosen for the control matrix spike (CMS), For instance,
for extractable compounds, if 100 ug of spike are added to 1 g of
sample, the resulting concentration is 100 mg/Kg. Under "CMS
CONCENTRATION", enter the actual concentration of each spike compound
detected in the control matrix spike aliquot. Calculate the percent
recovery of each spike compound in the control matrix spike to the
nearest whole percent, according to Exhibit E, and enter under "CMS %
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.
On Form III HCA, there are no QC limits on recovery at this time.
For volatiles and extractables, 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 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 extractable blanks, enter the "Instrument ID", "Date
Analyzed", and "Time Analyzed". The "Time Analyzed" shall be in
military time.
For extractable blanks and Aroclor method blanks, enter the date of
extraction of the blank.
If some of the samples associated with a given method blank are
subjected to sulfur clean-up procedures and some samples are not, then
two method blanks are required, one subjected to sulfur clean-up and one
not. (See Exhibit D for suggestions regarding the aliquotting of method
B- 29
Rev. 9/88
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blank extracts). If the method blank has been subjected to sulfur
clean-up, then enter "Y" under "Sulfur Clean-up (Y/N)," and list in the
table only those samples associated with that blank that have also
undergone sulfur clean-up. Complete a separate Form IV HCA-1 for the
aliquot of the method that did not undergo sulfur clean-up, listing the
associated samples that also did not undergo sulfur clean-up. NOTE:
The aliquotting of the method blank will require that different blank
identifiers be used in place of the EPA Sample Number for each blank on
all deliverables. (See Section A above),
Aroclor/Toxaphene contaminants must meet the identification criteria in
Exhibit D ARO, which requires analysis of the blank on two different GC
Columns. Therefore, enter the aate, 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 bj stationary phase under "GC Column ID".
Aroclor/Toxaphene analyses also require the analysis of an instrument
blank at specified points in the analytical sequence. For each
instrument blank that is associated with phase units in a data package,
complete a copy of Form IV HCA-2, and summarize the samples associated
with that instrument blank, as described below. NOTE: The samples
associated with an instrument blank may not be the same as those
associated with a method blank. Samples associated with an instrument
blank are those that were analyzed in the 12-hour period prior to the
instrument blank in question, and after the previous acceptable
instrument 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 extractables,
enter Lab File ID and the date and time of analysis of each sample.
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 extractable, and to summarize the date and time of analysis of
samples, standards, blanks, and control matrix spikes associated with
each GC/MS tune.
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 extractable). Enter the "Instrument ID". Enter
the date and time of injection of the tuning compound. Enter time as
military time.
For each ion listed on the form, enter the percent relative abundance in
the right-hand column. Report relative abundances to the number of
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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, and
control matrix spikes 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, and contro.l matrix spikes.
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, or control
matrix spike must be injected within twelve hours of the injection of
the tuning compound.
Number all pages as described in part A.
Initial Calibration Data (Form VI)
After a GC/MS system has undergone an initial 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 extractable TCL initial
calibration performed which is relevant to the samples, blanks, or
control matrix spikes in the SDG, regardless of when that calibration
was performed. A five-point initial calibration is required for
volatiles. A three-point calibration is required for extractables.
Complete all header information as in part A. Enter the "Case No." and
"SDG No." for the current data package, regardless of the original Case
for which the initial calibration was performed. Enter "Instrument ID"
and the date(s) of the calibration. If the calendar date changes during
the calibration procedure, the inclusive dates should be given on Form
VI. Enter the "Lab File ID" for each of the calibration standards
injected. Complete the response factor data for the 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 HCV SPCC compounds must have a minimum
average relative response factor (RRF) of 0.300 (0.250 for Bromoform).
All extractable SPCC compounds must have a minimum average relative
response factor (RRF) of 0.050.
%RSD x 100
x
B- 31
Rev. 9/88
-------
where: %RSD
Relative Standard Deviation
SD — Standard Deviation of initial response factors (per
compound)
2 - 9
SI I (Xi—x)
i-l
n-1
"x — mean of initial response factors (per compound)
The PCBs listed on Form VI HCE-3 are injected in different amounts than
the other extractable standards, and the octa-decachlorinated biphenyls
are injected at twice the amount as the lower levels of chlorination.
Enter the two sets of Lab File IDs for the injections of the PCBs in the
appropriate spaces on the lower half of this form. If the PCBs are
injected along with the other standards, enter the same Lab File IDs as
at the top of the form. If the PCBs are all injected in one standard
regardless of level of chlorination, but separate from the other
extractable standards, enter one set of Lab File IDs for the extractable
standards, and enter a second set of Lab File IDs for the PCBs, using
the same Lab File ID for RRF10 as for RRF2C, etc.
The initial calibration of the Aroclors and Toxaphene is reported on
Form VI HCA-1 and HCA-2. Complete all header information as in part A.
For each GC column used for Aroclor/Toxaphene analyses, complete a copy
of Form VI HCA-1 and HCA-2, identifying the stationary phase of the GC
Column under "GC Column ID". Each analyte requires a three-point
calibration, therefore, for each GC Column, there will be three pages of
Form VI HCA-1. The "Date(s) Analyzed" at the top of the form must be
the inclusive dates of analysis for all 24 of the standards in the
initial calibration.
For each injection of each standard, enter the date and time of
injection, and the amount injected in nanograms.
The calibration of these multicomponent analytes requires the use of at
least three chromatographic peaks. Two additional peaks may be reported
as well to allow for coeluting interference's. For each peak used, enter
the retention time in minutes and decimal minutes (not minutes and
seconds) , and the calibration factor for each peak.
Calculate a mean' of the three retention times for each peak of each
analyte, and enter under "MEAN RT". Calculate a mean deviation at the
three retentions for each peak, according to the formula in Ex. D. ARO,
and report this value under "MD RT".
Calculate a mean and relative standard deviation of the three
calibration factors for each peak in each analyte according to Ex. D
ARO, and enter them on Form VI HCA-2 under "Mean Cal. Factor" and
"%RSD".
B- 32
Rev. 4/89
-------
If the mean and %RSD do not meet the specifications in Ex. D. ARO, the
laboratory may use a regression line through all three calibration
points, or a two segment regression line (see Ex. D. ARO). If the mean
and %RSD meet the specifications in Ex. D. ARO, leave blank the
regression coefficients and intercept fields.
If a single correlation line is used, enter the mean, %RSD, and the
regression coefficient "r (1)" and the intercept "INTCPT (1)".
If a two segment regression line is used, enter both correlation
coefficients and intercepts "r (l)"and "r (2)", etc. Also enter the
mean RT and %RSD.
H. Continuing Calibration Data (Form VII)
1. Form VII HCV, HCE-1, HCE-2, and HCE-3
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
extractable 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). Using the appropriate Initial Calibration (Volatile
or extractable) fill in the average relative response factor (RRF)
for each TCL compound. Report the relative response factor 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
RRF
I
where,
RRFj = average relative response factor from initial
calibration.
RRF^ = relative response factor from continuing calibration
standard.
B- 33
Rev. 4/89
-------
All continuing calibration standards for extractables (except PCBs) are
analyzed at 80 total ng. The PCB standards are analyzed at 30 total ng
for mono-heptachlorinated biphenyls, and 60 total ng for octa-
decachlorinated biphenyls. As on Form VI, if these standards are co-
injected, enter the same Lab File ID in both locations on the form.
2. Form VII HCA
The calibration of multicomponent analytes is verified by a
comparison of the initial calibration factors to those obtained by
the periodic analysis of Performance Evaluation Mixtures (PEM),
Complete the header information as in Part A. The GC Column ID must
match that on the corresponding Form VI HCA. For each PEM injected,
record the date and time of analysis on Form VII, along with amount
injected in nanograms. For each of the three required peaks, and
any additional peaks, enter the retention time of the peak, in
minutes and decimal minutes. For each peak, calculate the percent
difference between the retention time of each peak in the PEM and
the mean retention time of that peak on Form VI HCA-2, according to
the formula above. Report this value under "%D" on Form VII HCA.
Enter initial calibration factor for each peak from Form VI HCA
under "Initial Gal. Factor". Enter the calibration factor from the
injection listed on Form VII HCA under "Continuing Cal. Factor."
Calculate the relative percent difference according to Ex. D. ARO,
and enter "RPD".
Number all pages as part A.
I. Form VIII
1. Internal Standard Area Summary (Form VIII HCV and HCE)
This form is used to summarize the peak areas of the internal
standards added to all volatile and extractable samples, blanks, and
control matrix spikes. 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 80 ng initial
calibration standard for extractables. 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.
B-34
Rev. 9/88
-------
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.
For each sample, blank, and control matrix spike 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.
2. Analytical Sequence (Form VIII HCA)
This form is used to record the sequence of analysis of samples and
standards for all Aroclor/Toxaphene analyses. Data must be provided
for the initial calibration standards as well as the samples in the
SDG. If samples in the SDG being reported were analyzed immediately
after the initial calibration, list them immediately following the
calibration standards. If an older calibration is being used, list
the initial calibration standards on one Form VIII HCA, and the
samples on separate forms, (as with Form V for volatiles or
extractables).
For each Form VIII HCA, complete all header information as in part
A. Enter the stationary phase of the GC column under "GC Column
ID". Begin each Form VIII HCA with calibration standards or
performance evaluation mixtures associated with the samples.
For Aroclor/Toxaphene standards, the following scheme must be used
to enter "EPA Sample Number".
Name
EPA Sample Number
Toxaphene
TOXAPH
AR1016
AR1221
AR1232
AR1242
AR1248
AR1254
AR1260
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
B-35
Rev. 9/88
-------
If Aroclor 1016 and Aroclor 1260 are combined into one standard
mixture, use AR1660 as the "EPA Sample Number",
Instrument Blanks must be identified as "IBLK##", where "##" may be
any combination of numbers or letters needed to distinguish between
various instrument blanks in one SDG.
For each sample, standard, control matrix spike, and blank, enter
the EPA sample number, lab sample ID, date and time of analysis.
Every sample, standard, control matrix spike, method blank, and
instrument blank must contain the surrogates Tetrachloro-meta-Xylene
(TMX) and Decachlorobiphenyl (DEC) at the level specified in Ex, D.
ARO. Calculate the retention time shift for each of the surrogates
on both GC columns according to the following formula, and report
under the appropriate column for %D on Form VIII HCA.
RT - RTS
% Difference - —
RT
where:
RT = Mean retention time from initial calibration of the
surrogate
RTS - Retention time of the sample of interest
The %D for the surrogates in every sample, standard, control matrix
spike, and blank must be less than or equal to 0.5%, as calculated
above. Flag each retention time shift outside the QC limits with an
asterisk in the last column, under the . If the surrogates have
been diluted out, and no %D can be calculated, enter "dil" under
"%D", and describe in the Case Narrative.
Number all pages according to part A,
Form IX
1. Extractable GPC Calibration (Form IX HCE)
This form reports the results of the calibration of the gel
permeation chromatographic apparatus (GPC) used to clean-up
sample extracts. It reports the retention times of the four
GPC calibration compounds, and lists the phase units associated
with that calibration.
Complete the header information as in Part A. Enter the
laboratory's GPC column identifier under "GPC Column ID", and
the date of the GPC calibration.
For each of the four GPC calibration compounds, enter the
retention time of that compound during the initial calibration
under "INITIAL CALIB. RT". Enter the retention time of each
calibration compound from the calibration verification standard
B-36
Rev. 4/89
-------
under "CALIB. VERIF. RT". Calculate the percent difference in
the two retention times according to the formula for the
surrogates above, and enter under "%D". There are no QC limits
on percent difference for Polystrene or Pentachlorophenol. The
QC limit on the other two GPC calibration compounds is 5%.
In the lower portion of the form, list the phase units which
are associated with this GPC calibration. Enter the EPA Sample
No., including the phase unit suffix, and the Lab Sample ID,
Lab File ID, and the date and time analyzed by GC/MS.
Include a copy of Form IX HCE for each GPC calibration
performed that is associated with samples in a data package.
Number all pages as in Part A.
2. Pesticide Retention Times (Form IX HCA)
This form reports the retention times and retention time
windows of the single component pesticide compounds. While
these pesticides are not target compounds by the GC/EC methods
used for Aroclors and Toxaphene, their retention times are
reported with the Aroclor/Toxaphene data to ensure that peaks
for pesticide compounds are not misidentified as Aroclor or
Toxaphene peaks.
The retention times of the single compound pesticides must be
determined at least once per initial calibration on each
instrument and each GC column used for sample analysis. These
data must be submitted with each group of samples analyzed
under that initial calibration.
Retention time windows are determined as a plus/minus
percentage of the retention time. For the four BHC compounds
and Heptachlor, the retention time window is ±1.5% of the
retention time. The retention time windows of the remaining 15
compounds are ±1.0% of the retention time.
Complete the header information as in Part A. Enter the GC
Column ID by stationary phase. This GC Column ID must match
that on Forms II, VII, and VIII HCA. Enter the inclusive dates
of analysis under "Date(s) of Analysis".
Enter the retention time of each pesticide under "RT" in
minutes and decimal minutes, not minutes and seconds.
Calculate the retention time windows according to the
percentages above, and report as a part of from/to values, not
as a plus/minus percentage.
No Form X HCA is required for the analyses of these single
component pesticides.
Number all pages as in Part A.
Aroclor/Toxaphene Identification Summary (Form X)
B- 37
Rev. 4/89
-------
This form summarizes the tentative and confirmed identity of all TCL
Aroclors/Toxaphene detected in a given sample. It reports the
retention times of each quantitation peak in the compound on both
columns on which it was analyzed, as well as the retention time
windows of the same peaks in the standard for that compound on both
of these columns. One copy of Form X is required for each sample,
control matrix spike, or blank in which Aroclors/Toxaphene 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). Enter the Instrument ID associated
with each GC column directly below.
For each Aroclor/Toxaphene detected, enter the name of the target
compound on the line under "COMPOUND". For each of the
quantification peaks selected for that compound (at least 3 peaks
are required), enter the retention time of that peak on each GC
column in the appropriate box under "RT" in decimal minutes. Enter
the retention time windows of the same peaks in the standard for
that compound. The retention time window of the standard is defined
as ±1.0% of the mean retention time of the peak determined in the
initial calibration. The lower value is entered under the "FROM"
column, the upper value under the "TO" column.
Calculate the concentration of each Aroclor or Toxaphene peak
reported on Form X from the calibration factors on each of the two
columns used. Enter the concentration under the "CONCENTRATION"
column. Calculate a mean of the 3-5 concentrations for each analyte
on each column that result, and enter this value under the "MEAN
CONCENTRATION" column. Note: There will be one mean concentration
per compound in each column. Report the lower of the two mean
concentrations on Form I KCA.
Calculate the percent difference between the two mean
concentrations, according to the formula below, and enter this value
under the "%D" column. If the percent difference is greater than
25% of the lower value, flag the result on Form I with one of the
optional flags "X,Y,or Z". Define your use of the flag in the Case
Narrative.
where:
CL = lower mean concentration (based on 3-5 peaks)
= higher mean concentration (based on 3-5 peaks)
If more 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,
B- 38
Rev. 4/89
-------
and numbering the pages as described in Part A.
Diol Cartridge Check (Form XI)
This form is used to report the results of the Diol cartridge check.
The amount of the spike compound passed through the cartridge and
removed from the eluent must meet the QC limits listed on the form
before that lot of Diol cartridges may be used for extract clean-up.
The form also lists all the phase units in the data package which
were cleaned using Diol cartridges from this lot.
Complete all header information as in Part A. Enter the lot number
of the Diol cartridges, and the date of the analysis of the
cartridge check solution.
Enter the amount of Aroclor 1254 spiked in the solution in nanograms
and the amount recovered under "SPIKE ADDED" and "SPIKE RECOVERY"
respectively.
Calculate a percent recovery according to the formula in Ex. D ARO,
and enter under "% REC". This value must be within the QC limits of
80-110%.
In the lower portion of the form, enter the EPA Sample No.,
including phase unit suffix, of each phase unit which was cleaned
using a cartridge from this lot. If there is a Lab Sample ID, enter
it here as well. If more than 25 phase units used cartridges from
the same lot, duplicate the header information, and continue on
another copy of Form XI, numbering the pages as in Part A.
B- 39
Rev. 4/89
-------
SECTION IV
DATA REPORTING FORMS
B-40
-------
1HA
HIGH CONCENTRATION VOLATILE ANALYSIS DATA SHEET
EPA SAMPLE NO.
Lab Name;
Contract:
Lab Code;
Case No,
SAS No.:
SDG No.
Phase Type:
Phase weight:
Final Extract Volume:
Aliquot Volume:
(g)
(mL)
-------
1HB
'HIGH CONCENTRATION EXTRACTABLE ANALYSIS DATA SHEET
EPA SAMPLE NO,
Lab Name:
Lab Code:
Case No,
Contract:
SAS No.:
SDG No,
Phase Type:
Phase weight:
(g)
Final Extract Volume:
Injection Volume:
Conversion Factor:
pH:
CAS NO.
(mL)
(UL)
Lab Sample ID:
Lab File ID:
Date Received:
Date Separated:
Date Extracted:
Date Analyzed:
COMPOUND
CONCENTRATION
(mg/Kg)
108-95-2 Phenol
111-44-4 bis (2-Chloroethyl) ether
95-57-8 2-Chlorophenol
541-73-1 1,3-Dichlorobenzene
"106-46-7 1,4-Dichlorobenzene
•100-51-6 -Benzyl alcohol
95-50-1- 1,2-Dichlorobenzene
95-48-7 2 -Methy lpheno 1
108-60-1 bis (2-Chloroisopropyl)ether_
106-44-5 4-Methylphenol ~
621-64-7 N-Nitroso-di-n-propylamine
67-72-1 Hexachloroethane
98-95-3 Nitrobenzene
78-59-1 Isophorone
88-75-5 2-Nitrophenol
105-67- 9 2,4-Diroethylphenol
•65-85-0 Benzoic acid
111-91-1 bis (2 -Chi oroethoxy) methane
120-83-2 2, 4-Dichlorophenol
120-82-1 1, 2 , 4-Trichlorobenzene
91-20-3 Naphthalene_
106-47- 8 4-Chloroaniline_
87-68- 3 Hexachlorobutadiene
59-50-7 4-Chloro-3-methylphenol
91-57-6 2-Methylnaphthalene
77-47-4 Hexa chlorocy c 1 opentadiene
88-06- 2 2, 4 , 6-Trichlorophenol
95-95-4 2,4, 5-Trichlorophenol
91-58-7 2-Chloronaphthalene
88-74-4 2-Nitroaniline
131-11-3 Dimethylphthalate
208-96-8 Acenaphthylene
606-20-2 2 , 6-Dinitrotoluene
I
FORM I HCE-1
Rev. 9/8"
-------
1HC
HIGH CONCENTRATION EXTRACTABLE ANALYSIS DATA SHEET
EPA SAMPLE NO.
Lab Name:_
Lab Code:
Case No.:
Phase Type:
Phase weight:
(g)
Final Extract Volume:
Injection Volume:
Conversion Factor:
pH:
CAS NO.
(mL)
(uL)
Contract:
SAS No.:
SDG No.:
Lab Sample ID:
Lab File ID:
Date Received:
Date Separated:
Date Extracted:_
Date Analyzed:
COMPOUND
CONCENTRATION
(rog/Kg) Q
99-09-2 3-Nitroaniline_
8 3-32-9 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-phenyl ether
319-84-6 alpha-BHC
118-74-1 Hexachlorobenzene
319-85-7 beta-BHC
87-86-5 Pentachlorophenol
58-89-9 gamma-BHC (Lindane)
85-01-8 Phenanthrene
12 0-12-7 Anthracene
319-86-8 delta-BHC
76-44-8 Heptachlor
309-00-2 Aldrin
84-74-2 Di-n-butylphthalate_
206-44-0 Fluoranthene
1024-57-3 Heptachlor epoxide
27323-18-8 Monochlorobipheny1_
2051-60-7 Dichlorobiphenyl
2 051-61-8 Trichlorobiphenyl
2051-62-9 Tetrachlorobiphenyl_
129-00-0 Pyrene
5103-74-2 gamma-Chlordane
(1) - Cannot be separated from Diphenylamine
FORM I HCE-2
Rev. 9/8£
-------
1HD
HIGH CONCENTRATION EXTRACTABLE ANALYSIS DATA SHEET
EPA SAMPLE NO.
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Phase Type:
Phase weight:
(g)
Final Extract Volume:
Injection Volume:
Conversion Factor:
pH:
CAS NO.
(mL)
(UL)
Lab Sample ID:
Lab File ID:
Date Received:
Date Separated:
Date Extracted:
Date Analyzed:
COMPOUND
CONCENTRATION
(mg/Kg) Q
959-98-8
5103-71-9
25429-29-2
72-55-9
60-57-1
26601-64-9
72-20-8
33213-65-9
72-54-8
28655-71-2
85-68-7
1031-07-8
50-29-3
53494-70-5
56-55-3
72-43-5
218-01-9
55722-26-4
91-94-1
117-81-7
53742-07-7
2051-24-3
117-84-0
205-99-2
207-08-9
50-32-8
193-39-5
53-70-3
191-24-2
Endosulfan I
alpha-Chlordane
Pentachlorobiphenyl
4 , 4 ' -DDE "
Dieldrin
Hexachlorobiphenyl_
Endrin
Endosulfan II
4,41-DDD
-—Heptachlorobiphenyl
Butylbenzylphthalate_
Endosulfan sulfate
4,4•-DDT
Endrin ketone
Benzo(a)anthracene_
Methoxychlor
Chrysene_
Octachlorobiphenyl
3,3'-Dichlorobenzidine
bis(2-Ethylhexyl)phthalate_
Nonachlorobiphenyl
Decachlorobiphenyl
Di-n-octylphthalate
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(1,2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(g,h,i)perylene
FORM I HCE-3
Rev. 9/8
-------
1HE
HIGH CONCENTRATION VOLATILE ANALYSIS DATA SHEET
TENTATIVELY IDENTIFIED COMPOUNDS
EPA SAMPLE NO.
Lab Name:
Lab Code:
Case No.:
Contract:_
SAS No.:
SDG NO.
Phase Type:
Phase weight:
Final Extract Volume:
Aliquot Volume:
(g)
(mL)
(uL)
Conversion Factor:
Number TICs found:
Lab Sample ID:
Lab File ID:
Date Received:
Date Separated:
Date Analyzed:
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.
(mg/Kg)
FORM I HCV-TIC
Rev. 9/88
-------
1HF
HIGH CONCENTRATION EXTRACTABLE ANALYSIS DATA SHEET
TENTATIVELY IDENTIFIED COMPOUNDS
EPA SAMPLE NO.
Lab Name:
Lab Code:
Case No.:
Contract
SAS No.:
SDG No.
Phase Type:
Phase weight:
(g)
Final Extract Volume:
Injection Volume:
Conversion Factor:
pH:
Number TICs found:
(mL)
(uL)
Lab Sample ID:
Lab File ID:
Date Received:
Date Separated:
Date Extracted:
Date Analyzed:
CAS NUMBER
1.
2.
3 .
4 .
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
•2 3 .
24 .
25.
26.
27.
28.
29.
30.
COMPOUND NAME
RT
EST. CONC.
(mg/Kg)
Q
FORM I HCE-TIC
Rev. 9/
-------
1HG
HIGH CONCENTRATION AROCLOR ANALYSIS DATA SHEET
EPA SAMPLE NO.
Lab Name:_
Lab Code:
Case No.:
Phase Type:
Phase weight:
(g)
Final Extract Volume:
Injection Volume:
Conversion Factor:
pH:
CAS NO.
(mL)
(UL)
COMPOUND
Contract:
SAS No.:
SDG No.
8001-35-2 Toxaphene
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
Aroclor-1016_
Aroclor-1221_
Aroclor-1232~
Aroclor-1242_
Aroclor-1248_
Aroclor-1254_
Aroclor-1260
Lab Sample ID:
Date Received:
Date Separated:
Date Extracted:
Date Analyzed:
Sulfur Clean-up:
CONCENTRATION
(mg/Kg)
(Y/N)
Q
FORM I HCA
Rev. 9/88
-------
2 HA
HIGH CONCENTRATION VOLATILE SURROGATE RECOVERY
Lab Name: Contract:
Lab Code: Case No.: 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
51 (TOL) = Toluene-d8 (50-160)
52 (BFB) = Bromofluorobenzene (50-160)
53 (DCE) = 1,2-Dichloroethane-d4 (50-160)
# Column to be used to flag recovery values
D Surrogates diluted out
Method blanks are required to meet the QC limits. For samples
and control matrix spikes, the QC limits are advisory.
page of
FORM II HCV
Rev. 9/88
-------
2HB
HIGH CONCENTRATION- EXTRACTABLE SURROGATE RECOVERY
Lab Name: Contract:
Lab Code: Case No.: 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
(NBZ)#
(FBP)#
S3
(TPH)#
S4
(PHL)#
S5
(2FP)#
S6
(TBP)#
OTHER
TOT
OUT
51 (NBZ) = Nitrobenzene-d5
52 (FBP) = 2-Fluorobiphenyl
53 (TPH) = Terphenyl-dl4
54 (PHL) = Phenol-d5
55 (2FP) = 2-Fluorophenol
56 (TBP) = 2,4,6-Tribromophenol
QC LIMITS
(20-140)
(20-140)
(20-150)
(20-140)
(20-140)
(10-140)
# Column to be used to flag recovery values
D Surrogates diluted out
Method blanks are required to meet the QC limits. For samples
and control matrix spikes, the QC limits are advisory
page of
FORM II HCE
Rev. 9/88
-------
2HC
HIGH CONCENTRATION AROCLOR SURROGATE RECOVERY
Lab Name:
Lab Code:
GC Column ID (1) :
Case No.:
Contract:
SAS No.:
GC Column ID (2):
SDG No.
EPA
SAMPLE NO.
2|
|COL.1 jCOL. 2|COL.1 |COL.
j SI j SI j S2 j S2 |
|(TMX)#|(TMX)#1(DEC)#|(DEC)#|
01|.
02 |
03 j"
04 |"
05 |"
06 |"
07 j"
08 j"
09 |"
l°l!
HI.
12|.
"I.
14 [.
151.
16|.
17!.
18|.
19 |
20 j
211;
22 |
23 |"
24 |
25|;
26 |
27 |
28 f
29 j'
30 |
X
51 (TMX) = Tetrachloro-meta-Xylene
52 (DEC) = Decachlorobiphenyl
QC LIMITS
(40-120)
(40-120)
# Column to be used to flag recovery values
D Surrogate diluted out
page of
FORM II HCA
-------
3HA
HIGH CONCENTRATION VOLATILE CONTROL MATRIX SPIKE RECOVERY
Lab Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.
| | SPIKE | CMS | CMS | QC. |
| | ADDED |CONCENTRATION[ % |LIMITS|
I COMPOUND I (mg/Kg) I (mg/Kg) [ REC #! REC. |
| 1,1-Dichloroethene | j | | 60-150 |
| Trichloroethene j | 1 I 60-150 1
j Benzene | j j j 60-150 j
j Toluene j j j j 60-150 j
j Chlorobenzene j j j | 60-150 |
# Column to be used to flag recovery values with an asterisk
* Values outside of QC limits
Spike Recovery: out of outside limits
COMMENTS:
FORM III HCV
Rev. 9/88
-------
3HB
HIGH CONCENTRATION EXTRACTABLE CONTROL MATRIX SPIKE RECOVERY
Lab Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
1 1
SPIKE
| CMS |
CMS
1 QC. |
1 1
ADDED
|CONCENTRATION|
%
|LIMITS|
| COMPOUND |
(mg/Kg)
| (mg/Kg) |
REC
#| REC. |
I Phenol |
1 1
1 1
- 1 1
|10-120|
I 2-Chlorophenol |
1 1
|10-120|
I 1,4-Dichlorobenzene |
1 1
| 30-140|
| N-Nitroso-di-n-prop.(1)|
| 1,2,4-Trichlorobenzene j
j 4-Chloro-3-methylphenolj
I Acenaphthene |
1 1
1 1
1 1
1 1
| 30-140|
|30-140|
|10-120|
| 30-140|
I 4-Nitrophenol |
1 1
|10-120|
I 2,4-Dinitrotoluene |
1 1
| 30-140|
I Pentachlorophenol |
1 1
|10-120|
I Heptachlor |
1 1
| 30-140|
| Pyrene |
1 1
| 30-140|
I Dieldrin |
1 1
| 30-140|
1 II III
(1) N-Nitroso-di-n-propylamine
# Column to be used to flag recovery values with an asterisk
* Values outside of QC limits
Spike Recovery: out of outside limits
COMMENTS:
FORM III HCE
Rev. 9/88
-------
3HC
HIGH CONCENTRATION AROCLOR CONTROL MATRIX SPIKE RECOVERY
Lab Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
| COMPOUND
| SPIKE
| ADDED
|(mg/Kg)
| CMS |
|CONCENTRATION|
| (mg/Kg) |
CMS
%
REC
1 QC. |
|LIMITS|
| REC. |
I Aroclor 1254
1
1
1 1
1 1
-1 1
| none |
1 II III
COMMENTS:
FORM III HCA
Rev. 9/88
-------
4 HA
HIGH CONCENTRATION VOLATILE METHOD BLANK SUMMARY
Lab Name:
Lab Code: Case No. :
Lab Sample ID:
Lab File ID:
Instrument ID:
Contract:
SAS No. : SDG No. :
Date Analyzed:
Time Analyzed:
THIS METHOD BLANK APPLIES TO THE FOLLOWING SAMPLES AND CMS:
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
COMMENTS:
EPA
SAMPLE NO.
LAB
SAMPLE ID
LAB
FILE ID
TIME
ANALYZED
page
of
FORM IV HCV
Rev. 9/8P
-------
4HB
HIGH CONCENTRATION EXTRACTA3LE METHOD BLANK SUMMARY
Lab Name:_
Lab Code:
Lab Sample ID:
Lab File ID:
Instrument ID:
Case No.:
Contract:
SAS No.:
SDG No.
Date Extracted:
Date Analyzed:
Time Analyzed:
THIS METHOD BLANK APPLIES TO THE FOLLOWING SAMPLES AND CMS:
EPA
SAMPLE NO.
LAB
SAMPLE ID
LAB
FILE ID
DATE
ANALYZED
TIME
ANALYZED
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
COMMENTS:
page of
FORM IV HCE
Rev. 9/88
-------
4HC
HIGH CONCENTRATION AROCLOR METHOD BLANK SUMMARY
Lab Name:_
Lab Code:
Case No.:
Contract:
SAS No. :
SDG No.
Lab Sample ID:
Date Analyzed (1)
Time Analyzed (1)
Instrument ID (1)
GC Column ID (1)
Sulfur Clean-up:
Date Extracted:
Date Analyzed (2)
Time Analyzed (2)
Instrument ID (2)
GC Column ID (2)
(Y/N)
THIS METHOD BLANK APPLIES TO THE FOLLOWING SAMPLES AND CMS:
EPA
SAMPLE NO.
LAB
SAMPLE ID
DATE
ANALYZED 1
TIME
ANALYZED 1
DATE
ANALYZED 2
TIME
ANALYZED 2
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
181
191
20
21
22
23
241
2 5
26"
27
28
29
30
COMMENTS:
page
of
FORM IV HCA-1
Rev. 9/b
-------
4HD
HIGH CONCENTRATION AROCLOR INSTRUMENT BLANK SUMMARY
Lab Name:
Lab Code:
Lab Sample ID:
Date Analyzed (1):
Time Analyzed (1):
Instrument ID (1):
GC Column ID (1):
Case No,
Contract:
SAS No.:
SDG NO,
Date Prepared:
Date Analyzed (2)
Time Analyzed (2)
Instrument ID (2)
GC Column ID (2)
THIS INSTRUMENT BLANK APPLIES TO THE FOLLOWING SAMPLES AND CMS:
EPA
SAMPLE NO.
LAB
SAMPLE ID
| DATE | TIME | DATE | TIME
I ANALYZED II ANALYZED II ANALYZED 2 1 ANALYZED 2
01 1
02 [
03 |
04 |
05 |
06 j
07 |
08 j
09 |
10 |
HI
12 |
13 |
14 |
15 |
16 |
17 |
18 |
19 |
20 |
21|
22 |
23 [
241
25 |
26|
27 |
28 |
29 |
30 |
COMMENTS:
page
of
FORM IV HCA-2
Rev. 9/88
-------
5 HA
HIGH CONCENTRATION VOLATILE GC/MS TUNING AND MASS
CALIBRATION - BROMOFLUOROBENZENE (BFB)
Lab Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
Lab File ID: BFB Injection Date:
Instrument ID: BFB Injection Time:
1
% RELATIVE |
1 n/e
ION ABUNDANCE CRITERIA |
ABUNDANCE |
| 50
1"
15.0 - 40.0% of mass 95 |
1 75
30.0 - 60.0% of mass 95 |
1 95
Base peak, 100% relative abundance I
1 96
5.0 - 9.0% of mass 95 I
| 173
Less than 2.0% of mass 174 I
( ) 11
| 174
Greater than 50.0% of mass 95 I
| 175
5.0 - 9.0% of mass 174 |
( ) 11
| 176
Greater than 95.0%, but less than 101.0% of mass 174|
( ) 11
| 177
5.0 - 9.0% of mass 176 I
1
( )2\
1-Value is % mass 174 2-Value is % mass 176
THIS TUNE APPLIES TO THE FOLLOWING SAMPLES, CMS, BLANKS, AND STANDARDS:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
EPA
SAMPLE NO.
LAB
SAMPLE ID
LAB
FILE ID
DATE
ANALYZED
TIME
ANALYZED
page of
FORM V HCV
Rev. 9/88
-------
5HB
HIGH CONCENTRATION EXTRACTABLE GC/MS TUNING AND MASS
CALIBRATION - DECAFLUOROTRIPHENYLPHOSPHINE (DFTPP)
Lab Name: Contract:
Lab Code: Case No. : SAS No. : SDG No. :
Lab File ID: DFTPP Injection Date:
Instrument ID: DFTPP Injection Time:
1 m/e
ION ABUNDANCE CRITERIA
| % RELATIVE |
j ABUNDANCE |
1 51
30.0 - 60.0% of mass 198
1 1
| 68
Less than 2.0% of mass 69
1 ( )H
| 69
Mass 69 relative abundance
1 1
1 70
Less than 2.0% of mass 69
1 ( ) 11
| 127
40.0 - 60.0% of mass 198
1 1
| 197
Less than 1.0% of mass 198
1 1
| 198
Base Peak, 100% relative abundance
1 1
| 199
5.0 to 9.0% of mass 198
1 1
| 275
10.0 - 30.0% of mass 198
1 1
| 365
Greater than 1.00% of mass 198
1 1
| 441
Present, but less than mass 443
1 1
| 442
Greater than 40.0% of mass 198
1 1
| 443
17.0 - 23.0% of mass 442
1 ( ) 2 I
1 1
1-Value is % mass 69 2-Value is % mass 442
THIS TUNE APPLIES TO THE FOLLOWING SAMPLES, CMS, BLANKS, AND STANDARDS:
EPA
SAMPLE NO.
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
LAB
SAMPLE ID
LAB
FILE ID
DATE
ANALYZED
TIME
ANALYZED
page of
FORM V HCE
Rev. 9/88
-------
6 HA
HIGH CONCENTRATION VOLATILE INITIAL CALIBRATION DATA
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Instrument ID:
Calibration Date(s):
Min RRF for SPCC(#) = 0.300 (0.250 for Bromoform) Max %RSD for CCC(*) = 30.0%
LAB FILE ID:
RRF100=
RRF20 =
RRF150=~
RRF50 =
RRF200=~
COMPOUND
RRF2 0
RRF50
RRF100
RRF150
RRF2 00
RRF
RSD
Chloromethane
Bromomethane
Vinyl Chloride_
Chloroethane
Methylene Chloride_
Acetone
Carbon Disulfide
1,1-Dichloroethene
1.1-Dichloroethan e
1.2-Dichloroethene (total)
Chloroform
1,2-Dichloroethane_
2-Butanone
1,1,l-Trichloroethane_
Carbon Tetrachloride
Vinyl Acetate
Bromodichloromethane
1,2-Dichloropropane
cis-1,3-Dichloropropene_
Trichloroethene
Dibromochloromethane
1,1,2-Trichloroethane
Benzene
trans-1,3-Dichloropropene
Bromoform
4-Methyl-2-Pentanone_
2-Hexanone
Tetrachloroethene
1-r-l, 2 , 2-Tetrachloroethane #_
Toluene *"
Chlorobenzene #~
Ethylbenzene *'
Styrene |"
Xylene (total) |
Toluene-d8
Bromofluorobenzene
1,2-Dichloroethane-d4
FORM VI HCV
Rev. 9/'
-------
6HB
HIGH CONCENTRATION EXTRACTABLE INITIAL CALIBRATION DATA
Lab Name:_
Lab Code:
Case No.:
Contract:_
SAS No.:
SDG No.:
Instrument ID:
Calibration Date(s):
Min RRF for SPCC(#) = 0.050
Max %RSD for CCC(*) = 3 0.0^
LAB FILE ID:
RRF50 =
RRF160=
RRF80 =
COMPOUND
IRRF50
Phenol
bis(2-Chloroethy1)ether_
2-Chlorophenol
1.3-Dichlorobenzene_
1.4-Dichlorobenzene_
Benzyl alcohol_
1, 2-Dichlorobenzene_
2-Methylpheno1_
bis(2-Chloroisopropyl)ether|
4-Methylphenol j
N-Nitroso-di-n-propylamine_#
Hexachloroethane |
Nitrobenzene j
Isophorone j
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 j _
2-Nitroaniline .
Dimethylphthalate_
Acenaphthylene_
.1.
2,6-Dinitrotoluene_
3-Nitroaniline
Acenaphthene
2,4-Dinitrophenol_
4-Nitrophenol
RRF80
RRF160
RRF
%
RSD
J
*
J
*
_#
*
J
~
"#
"#
FORM VI HCE-1
Rev. 9/88
-------
6HC
HIGH CONCENTRATION EXTRACTABLE INITIAL CALIBRATION DATA
Lab Name:
Contract;
Lab Code;
Case No.:
SAS No.;
SDG NO.
Instrument ID:
Calibration Date(s)
Min RRF for SPCC(#) - 0.050
Max %RSD for CCC(*) = 30.0%
[LAB FILE ID:
RRF50 =
RRF160=
RRF80
| COMPOUND
j Dibenzofuran
|2,4-Dinitrotoluene
j Diethylphthalate
j 4-Chlorophenyl-phenylether_
j Fluorene ~
4-Nitroaniline
|RRF50
IRRF80 IRRF160I
RRF
RSD
|4,6-Dinitro-2-methylphenol_|_
|N-Nitrosodiphenylamine (1)
14-Bromophenyl-phenylether |"
j alpha-BHC j ~
j Hexachlorobenzene j"
beta-BHC
|Pentaehlorophenol
j gamma-BHC {Lindane)
j Phenanthrene j
|Anthracene
|delta-BHC
j Heptachlor
j Aldrin_
Di-n-butylphthalate_
Fluoranthene
|Heptachlor epoxide_
j Pyrene ~
j gamma-Chlordane
Endosulfan I
|alpha-Chlordane
| 4,4 ' -DDE ^
j Dieldrin
Endrin
|Endosulfan
I 4,41-DDD
II
[Butylbenzylphthalate
IEndosulfan sulfate
4,4'-DDT
|Endrin ketone
j Benzo(a)anthracene_
j Methoxychlor ~
(1) Cannot be separated from Diphenylamine
FORM VI HCE-2
Rev.9/^ ^
-------
6HD
HIGH CONCENTRATION EXTRACTABLE INITIAL CALIBRATION DATA
Lab Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
Instrument ID: Calibration Date(s) :
Min RRF for SPCC(#) = 0.050 Max %RSD for CCC(*) = 30.C
LAB FILE ID:
RRF50 =
RRF 160="
RRF80 =
COMPOUND
Chrysene
3,3*-Dichlorobenz idine
bis(2-Ethylhexyl)phthalate_
Di-n-octylphthalate
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(1,2,3-cd)pyrene_
Dibenz(a,h)anthracene_^
Benzo(g,h,i)perylene
RRF50
RRF80
RRF160
RRF
%
RSD
N itrobenzene-d5
2-Fluorob ipheny1_
Terphenyl-dl4
Phenol-d5
2-Fluorophenol
2,4,6-Tribromophenol_
LAB FILE ID:
RRF10 =
RRF50 ="
Monochlorobiphenyl
Dichlorobiphenyl
Trichlorobiphenyl
Tetrachlorobiphenyl_
Pentachlorobiphenyl_
Hexachlorobipheny1
Heptachlorob ipheny1_
RRF30 =
RRF10 IRRF30 IRRF50
RRF
%
RSD
LAB FILE ID: RRF20 =
RRF100="
Octachlorobipheny1_
Nonachlorobipheny1_
Decachlorob ipheny1_
RRF60 =
RRF20
RRF60
RRF100
RRF
%
RSD
FORM VI HCE-3
Rev.9/88
-------
6HE
HIGH CONCENTRATION INITIAL CALIBRATION OF MULTICOMFONENT AHALYTES
Lab Name:_
Lab Code:
Instrument ID:
Case No.
Contract:
SAS No.:
SDG No.
GC Column ID:
COMPOUND
Toxaphene
Date:
Time:
Aroclor 1016
Date:
Time:
Aroclor 1221
Date:
Time:
Aroclor 1232
Date:
Time:
Aroclor 1242
Date:
Time:
Aroclor 1248
Date:
Time:
Aroclor 1254
Date:
Time:
Aroclor 1260
Date:
Time:
AMOUNT | |
(ng) |PEAK|
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
RT
|CALIBRATION|
I FACTOR I
* Denotes required peaks
page of
FORM VI HCA-1
Rev. 9/.
-------
6HF
HIGH CONCENTRATION INITIAL CALIBRATION OF MULTICOMPONENT ANALYTES
Lab Name:.
Lab Code:
Case No.:
Contract:.
SAS No.:
SDG No.:
Instrument ID:
GC Column ID:
Date(s) Analyzed:
PEAK
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
MEAN
RT
MEAN CAL.
FACTOR
%
RSD
r
CD
INTCP
(1)
r
(2)
INTCP
(2)
COMPOUND
Toxaphene
Arolcor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
* Denotes required peaks
page of
FORM VI HCA-2
Rev.
-------
7 HA
HIGH CONCENTRATION VOLATILE CONTINUING CALIBRATION CHECK
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
Instrument ID:
Lab File ID:
Calibration Date:
SDG No.:
Time:
Init. Calib. Date(s):
Min RRF50 for SPCC(#) = 0.300 (0.250 for Bromoform) Max %D for CCC(*) = 25.0%
COMPOUND
Chloromethane
Bromomethane
Vinyl Chloride_
Chloroethane
Methylene Chloride_
Acetone
Carbon Disulfide
1,1-Dichloroethene
1.1-Dichloroethan e
1.2-Dichloroethene (total)
Chloroform
1,2-Dichloroethane_
2-Butanone
1,1,l-Trichloroethane_
Carbon Tetrachloride
Vinyl Acetate_
Bromodichloromethane_
1,2-Dichloropropane
cis-1,3-Dichloropropene_
Trichloroethene
Dibromochloromethane
1,1,2-Trichloroethane_
Benzene
trans-1,3-Dichloropropene
Bromoform
4-Methyl-2-Pentanone_
2-Hexanone
Tetrachloroethene
1,1,2,2-Tetrachloroethane_
Toluene
Chlorobenzene
Ethylbenzene
Styrene
RRF
Xylene (total)
Toluene-d8
Bromofluorobenzene
1,2-Dichloroethane-d4
RRF50
j
*
*
"#
.#
*
\
J
FORM VII HCV
Rev. 9/8?
-------
7HB
HIGH CONCENTRATION EXTRACTABLE CONTINUING CALIBRATION CHECK
Lab Name
Lab Code:
Case No.:
Contract:
SAS No.:
Instrument ID:
Lab File ID:
Calibration Date:
SDG No.:
Time:
Init. Calib. Date(s):
Min RRF80 for SPCC(#) = 0.050
Max %D for CCC(*) = 25.0%
COMPOUND
RRF
IKRF80
%D
V
]Phenol
|bis(2-Chloroethyl)ether_
|2-Chlorophenol_
1.3-Dichlorobenzene_
1.4-Dichlorobenzene~
Benzyl alcohol_
1,2-Dichlorobenzene_
2-Methylphenol_
|bis(2-Chloroisopropyl)ether|_
I 4-Methylphenol j _
j N-Nitroso-di-n-propylamine_#~
j Hexachloroethane | ~
| Nitrobenzene j ~
j Isophorone j ~
j 2-Nitrophenol *_
| 2, 4-Dimethylphenol | ~
j Benzoic acid |_
j bis(2-Chloroethoxy)methane_j_
| 2,4-Dichlorophenol *"
11,2,4-Trichlorobenzene |_
j Naphthalene^
4-Chloroaniline
|Hexachlorobutadiene
j 4-Chloro-3-methylphenol_
j 2-Methylnaphthalene_
Hexachlorocyclopentadiene #_
| 2,4, 6~Trichlorophenol
j 2 , 4 , 5-Trichlorophenol | ~
j 2-Chloronaphthalene |_
j 2-Nitroaniline |_
| Dimethylphthalate | _
j Acenaphthy1ene_
2,6-Dinitrotoluene_
3-Nitroaniline
Acenaphthene_
I.
2,4-Dinitrophenol_
4-N itrophenol
*
T
*
j
J
*
*
"*
J
*
"#
"#
j
FORM VII HCE-1
Rev. 1/89
-------
7HC
HIGH CONCENTRATION EXTRACTABLE CONTINUING CALIBRATION CHICK
Lab Name:
Lab Code:
Case No.
Contract:
SAS No.:
Instrument ID:
Lab File ID:
Calibration Date:
SDG No.:
Time:
Init. Calib. Date(s):
Min RRF80 for SPCC(#) - 0.050
Max %D for CCC(*) = 25.0%
| COMPOUND
'.i
IPentachlorophenol
j ganaaa-BHC ( Lindane)
j Phenanthrene [
j Anthracene
jdelta-BHC
j Heptachlor
Aldrin
|Di-n-butylphthalate_
j Fluoranthene_
|Heptachlor epoxide_
| Pyrene_
| gaxnma-Chlordane_
Endosulfan I
|alpha-Chlordane
I 4, 4 • -DDE ~
|Dieldrin
Endrin
IEndosulfan II
j 4 , 4 * -DDD_
Butylbenzylphthalate_
|Endosulfan sulfate ~
|4,41-DDT
j Endrin ketone
|Benzo(a)anthracene_
IMethoxychlor
I
'I'
| Dibenzofuran | _
12,4-Dinitrotoluene | ~
j Diethylphthalate |~
j 4-Chioropheny1-phenylether_j"
| Fluorene j ~
14-Nitroaniline j~
j 4,6-Dinitro-2-iaethylphenol_ j"
j N-Nitrosodiphenylamine (l)
j 4-Bromopheny1-phenylether
j alpha-BHC
jHexachlorobenzene_
j beta-BHC_
| RRF |RRF80 | %D |
= 1
I.
X.
J
*
(1) Cannot be separated from Diphenylamine
FORM VII HCE-2
Rev.9/t
-------
7HD
HIGH CONCENTRATION EXTRACTABLE CONTINUING CALIBRATION CHECK
Lab Name:_
Lab Code:
Case No.
Contract:
SAS No.:
Instrument ID:
Lab File ID:
Calibration Date:
SDG No.:
Time:
Init. Calib. Date(s):
Min RRF80 for SPCC(#) = 0.050
Max %D for CCC(*) = 25.03
COMPOUND
RRF
Chrysene | _
3,31-Dichlorobenzidine j~
bis(2-Ethylhexyl)phthalate_|~
Di-n-octylphthalate *_
Benzo(b) fluoranthene |_
Benzo(k) fluoranthene |_
Benzo(a)pyrene_
Indeno(1,2,3-cd)pyrene_
Dibenz(a,h)anthracene
Benzo(g,h,i)perylene
N itrobenzene-d5
2-Fluorobiphenyl_
Terphenyl-dl4
Phenol-d5
2-Fluorophenol
2,4,6-Tribromophenol
LAB FILE ID:
RRF10 =
Monochlorob ipheny1_
Dichlorobiphenyl
Trichlorobiphenyl
Tetrachlorobiphenyl_
Pentachlorobiphenyl"
Hexachlorob ipheny1
Heptachlorobipheny1_
| RRF
.1
.1
LAB FILE ID:
RRF20 =
I
| RRF
Octachlorobiphenyl_
Nonachlorobipheny1_
Decachlorobipheny1_
RRF80
RRF30
RRF60
%D
%D
%D
FORM VII HCE-3
Rev.1/89
-------
7 HE
HIGH CONCENTRATION CONTINUING CALIBRATION OF MULTICOMPONENT ANALYTES
Lab Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
Instrument ID: GC Column ID:
| COMPOUND
| AMOUNT
1 (ng)
1 1
|PEAK|
RT
| | INITIAL |CONTINUING | |
| %D |CAL. FACTOR|CAL. FACTOR| RPD |
| Toxaphene
1
1
1 1"
1 *1 1
II 1 II
II 1 II
| Date:
1
1 *2 |
II 1 II
1
1 *3 |
II 1 II
| Time:
1
1 4 |
II 1 II
1
1 5 |
II 1 II
| Aroclor
1016
1
1 *1 1
II 1 II
| Date:
1
1 *2 |
II 1 II
1
1 *3 |
II 1 II
| Time:
1
1 4 |
II 1 II
1
1 5 |
II 1 II
| Aroclor
1248
1
1 *1 1
II 1 II
| Date:
1
1 *2 |
II 1 II
1
1 *3 |
II 1 II
| Time:
1
1 4 |
1
1 5 |
II 1 II
| Aroclor
1254
1
1 *1 1
II 1 II
| Date:
1
1 *2 |
II 1 II
1
1 *3 |
II 1 1 i
| Time:
1
1 4 |
II 1 1
1
1 5 |
II 1 V
| Aroclor
1260
1
1 *1 1
II 1 II
| Date:
1
1 *2 |
II 1 II
1
1 *3 |
II 1 II
| Time:
1
1 4 |
II 1 II
1
1 5 |
II 1 II
1
1 1
II 1 II
* Denotes required peaks
page of
FORM VII HCA
Rev. 9.
-------
8HA
HIGH CONCENTRATION VOLATILE INTERNAL STANDARD AREA SUMMARY
Lab Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
Lab File ID (Standard) : Date Analyzed:
Instrument ID: Time Analyzed:
ISl(BCM)
AREA #
RT
IS2(DFB)
AREA #
RT
IS3(CBZ)
AREA
RT
12 HOUR STD
UPPER LIMIT
LOWER LIMIT
EPA SAMPLE
NO.
151 (BCM) = Bromochloromethane
152 (DFB) = 1,4-Difluorobenzene
153 (CBZ) = Chlorobenzene
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 HCV
Rev.
-------
8HB
HIGH CONCENTRATION EXTRACTABLE 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:
ISl(DCB)
AREA
RT
IS2(NPT)
AREA #
RT
IS3(ANT)
AREA
RT
12 HOUR STD|
UPPER LIMIT|
LOWER LIMIT!
EPA SAMPLE |
NO. |
01|
02 |
03 |
04 |
05 |
06 |
07 |
08 |
09 j
10|
HI
12|
13|
14 |
15 |
16 |
1?|
18|
19 |
2 0 |
2-11
-22 I
\
J
151 (DCB) = 1,4-Dichlorobenzene-d4
152 (NPT) — Naphthalene-d8
153 (ANT) = Acenaphthene-d8
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 HCE-1
Rev. 9/8P
-------
8HC
HIGH CONCENTRATION EXTRACTABLE INTERNAL STANDARD AREA SUMMARY
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
Lab File ID (Standard):
Instrument ID:
SDG No,
Date Analyzed:
Time Analyzed:
IS4(PHN)
AREA
RT
IS5(CRY)
AREA
RT
IS6(PRY)
AREA
RT
12 HOUR STD
UPPER LIMIT
LOWER LIMIT
EPA SAMPLE
NO.
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
154 (PHN) = Phenanthrene-dlO
155 (CRY) = Chrysene-dl2
156 (PRY) = 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 oi
FORM VIII HCE-2
Rev.
-------
8HD
HIGH CONCENTRATION ANALYTICAL SEQUENCE
Lab Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
Instrument ID: GC Column ID:
Date(s) Analyzed:
THE ANALYTICAL SEQUENCE OF INITIAL CALIBRATION STANDARDS, PERFORMANCE
EVALUATION MIXES, INSTRUMENT BLANKS, METHOD BLANKS, SAMPLES, AND CONTROL
MATRIX SPIKES IS GIVEN BELOW.
| EPA j LAB j DATE j TIME | %D | %D j
|SAMPLE NO.| SAMPLE ID | ANALYZED |ANALYZED| TMZ #| DEC #|
01! ! i i i i i
02 | [ I j | ] |
03 | | | | | I I
04 | | | | | | |
05 | |___ | | | | |
06 | | |_ I | | 1
0?j I I i I I I
08! I I I I I I
09 | | | i | |
10 | | | | |_ | |
HI I 1 1 I I I
12| | I | | | I
13 | I I I I I I
14 | I I I I 1 I
15 i I | | | | |
16 | | | | | | |
171 I I J I I I
18 1 I 1 I i I I
191 1 I I I ! I
20 | | | | | | |
'21| | | | | | |
22 | | | | | | |
23 1 I ! I I I I
24 | I | I 1 I I
25| i | | | I |
26 | | | | | |.
27 | | 1 I I I.
28 | | | | | |.
29 1 I i I I 1.
30! I I I I i.
311 I I I I I
32 | | |
33 | | I.
34| | |
35 | I I
36 | | |
# Column used to flag values outside of QC limits (+ 0.5%).
page of
FORM VIII HCA Rev,
-------
9 HA
HIGH CONCENTRATION EXTRACTABLE GPC CALIBRATION
Lab Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
GPC Column ID: Calibration Date:
| COMPOUND
| Polystyrene
j Bis(2-ethylhexy1)phthalate
j Pentachlorophenol
| Perylene
INITIAL|CALIB.| % | QC |
CALIB.|VERIF.| D |LIMITS 1
RT | RT | | |
I 1 I I
I I I 5% |
I I I I
I I I 5% |
I I I I
THIS GPC CALIBRATION APPLIES TO THE FOLLOWING SAMPLES, AND CMS:
I gpj j lA§ j jjyjj j DATE | TIME |
| SAMPLE NO. | SAMPLE ID | FILE ID | ANALYZED | ANALYZED |
01 1 I I | I I
02 | | | | | |
03 | _| | i I 1
04 | | | | | |
051 I I I I 1
06 | | | | |_ |
07 | | | | | |
08 | | | i | |
09 I I I I I I
101 I I I 1 I
Hi I I I I i
12 I | | |. |_ |
13 I I | | I !
14! 1 i I I i
¦151 I | | | |
161 I I 1 I i
171 I I I I I
18 I I 1 1 1 |
19 I I I I I I
201 I I I I I
211 I 1 I I 1
221 | ) 1 I |
COMMENTS:
page of
FORM IX HC1 Rev.9/88
-------
9HB
HIGH CONCENTRATION SINGLE COMPONENT PESTICIDE RETENTION TIMES
Lab Name: Contract:
Lab Code: ' Case No.: SAS No.: SDG No.:
Instrument ID: GC Column ID:
Date(s) Analyzed:
| | 1 RT WINDOW J
j COMPOUND | RT | FROM | TO |
| alpha-BHC | | | )
| beta-BHC 1 ] | I
| delta-BHC 1 | | |
| gamma-BHC | j j |
j Heptachlor j j | j
| Aldrin | _| | |
Heptachlor
epoxide 1 | ]
Endosulfan
I III
Dieldrin
1 1 1
4,4'-DDE | [ I
Endrin 1 1 1
Endosulfan
II 1 1 1
4,4'-DDD
1 1 1
Endosulfan
sulfate | | |
4,4'-DDT
1 f I
| Methoxychlor
I Endrin ketone
| Endrin aldehyde
j alpha-Chlordane_
j gamma-Chiordane
Retention times of single component pesticides must be determined
at least once per initial calibration on each instrument and column
used for the analysis of Aroclors and Toxaphene. See the Forms
instructions for the calculation of retention time windows. These
data must be submitted with the data package for each group of
samples analyzed under that initial calibration.
COMMENTS:
page of
FORM IX HCA
Rev. 9/88
-------
10H
HIGH CONCENTRATION AROCLOR IDENTIFICATION SUMMARY
EPA SAMPLE NO.
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.
Instrument ID (1):
GC Column ID (1):
Lab Sample ID (1):
Instrument ID (2):
GC Column ID (2):
Lab Sample ID (2):
COMPOUND
COLUMN 1
COLUMN 2
|PEAK| RT |
I
*1
*2
*3
4
5
*1
*2
*3
4
5
I.
.1.
RT WINDOW
OF STANDARD
FROM | TO
.1.
I | MEAN |
|CONCENTRATION j CONCENTRATION|
%D
.1.
.1
I
COLUMN 1
COLUMN 2
*1
*2
*3
4
5
*1
*2
*3
4
5
COLUMN 1
COLUMN 2
I *1
I *2
I *3
I 4
i 5
t
i *1
I *2
I *3
I 4
I 5
.1
I
* Denotes required peaks. Report the lower mean concentration on Form I.
If %D >25%, flag the value on Form I according to the instructions in Ex.
page of
FORM X HCA
Rev. 9/88
-------
11H
HIGH CONCENTRATION AROCLOR DIOL CARTRIDGE CHECK
Lab Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
Diol Cartridge Lot Number: Date of Analysis:
| SPIKE
| SPIKE 1
%
1 QC.
| ADDED
|RECOVERY|
REC
|LIMITS
COMPOUND
1 (ng)
1 (ng) |
Aroclor 1254
1
1
1 1
1 1
|80-110
THIS LOT OF DIOL CARTRIDGES WAS USED FOR THE FOLLOWING SAMPLES AND CMS:
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
COMMENTS:
EPA
SAMPLE NO.
LAB
SAMPLE ID
page of
FORM XI HCA
Rev. 9/88
-------
EXHIBIT C
TARGET COMPOUND LIST (TCL) AND
CONTRACT REQUIRED QUANTITATION LIMITS (CRQL)
-------
Target Compound List (TCL'S arid
Contract Required Quantitation Limits (CROP*
Quantitation Limits
Volatiles
CAS Number
(me/Ke)
1
Chloromethane
74-87-3
5.0
2
Bromomethane
74-83-9
5.0
3
Vinyl Chloride
75-01-4
5.0
4
Chloroethane
75-00-3
5.0
5
Methylene Chloride
75-09-2
2.5
6
Acetone
67-64-1
5.0
7
Carbon Disulfide
75-15-0
2.5
8
1,1-Dichloroethene
75-35-4
2.5
9
1,1-Dichloroethane
75-34-3
2.5
10
1, 2-Dichloroethene (total)
540-59-0
2.5
11
Chloroform
67-66-3
2.5
12
1,2-Dichloroethane
107-06-2
2.5
13
2 -Butanone
78-93-3
5.0
14
1,1,1-Trichloroethane
71-55-6
2.5
15
Carbon Tetrachloride
56-23-5
2.5
16
Vinyl Acetate
108-05-4
5.0
17
Bromodichloromethane
75-27-4
2.5
18
1,2-Dichloropropane
78-87-5
2.5
19
cis-1,3-Dichloropropene
10061-01-5
2.5
20
Trichloroethene
79-01-6
2.5
21
Dibromochloromethane
124-48-1
2.5
22
1,1,2-Trichloroethane
79-00-5
2.5
23
Benzene
71-43-2
2.5
24
trans-1,3-Dichloropropene
10061-02-6
2.5
25
Bromoform
75-25-2
2.5
26
4-Methyl-2-pentanone
108-10-1
5.0
27
2-Hexanone
591-78-6
5.0
28
Tetrachloroethene
127-18-4
2.5
29
1,1,2,2-Tetrachloroethane
79-34-5
2.5
30
Toluene
108-88-3
2.5
31.
Chlorobenzene
108-90-7
2.5
32.
Ethylbenzene
100-41-4
2.5
33.
Styrene
100-42-5
2.5
34.
Xylene (Total)
1330-20-7
2.5
"Specific quantitation limits are highly matrix dependent. The quantitation
limits listed herein are provided for guidance and may not always be
achievable.
C-2
Rev. 9/88
-------
Target Compound List (TCL) and
Contract Required Quantitation Limits "(CROP*
Quantitation Limits
Extractables
CAS Number
fme/Ke)
35.
Phenol
108-95-2
20
36.
bis(2-Chloroethyl) ether
111-44-4
20
37.
2-Chlorophenol
95-57-8
20
38.
1,3-Dichlorobenzene
541-73-1
20
39.
1,4-Dichlorobenzene
106-46-7
20
40.
Benzyl alcohol
100-51-6
20
41.
1,2-Dichlorobenzene
95-50-1
20
42.
2-MethyIpheno1
95-48-7
20
43.
bis(2-Chloroisopropyl)
ether
108-60-1
20
44.
4-Me thyIpheno1
106-44-5
20
45.
N-Nitroso-di-n-
dipropylamine
621-64-7
20
46.
Hexachloroethane
67-72-1
20
47.
Nitrobenzene
98-95-3
20
48.
Isophorone
78-59-1
20
49.
2-Nitrophenol
88-75-5
20
50.
2,4-DimethyIpheno1
105-67-9
20
51.
Benzoic acid
65-85-0
100
52.
bis(2 -Chloroethoxy)
methane
111-91-1
20
53
2,4-Dichlorophenol
120-83-2
20
54.
1,2,4-Trichlorobenzene
120-82-1
20
55.
Naphthalene
91-20-3
20
56.
4-Chloroaniline
106-47-8
20
57.
Hexachlorobutadiene
87-68-3
20
58.
4-Chloro- 3-methyIpheno1
(para-chloro-meta-cresol)
59-50-7
20
59.
2-Methylnaphthalene
91-57-6
20
60.
Hexachlorocyclopentadiene
77-47-4
20
61.
2,4,6-Trichlorophenol
88-06-2
20
62.
2,4,5-Trichlorophenol
95-95-4
100
63.
2 -Chloronaphthalene
91-58-7
20
64.
2-Nitroaniline
88-74-4
100
65.
Dime thylphthalate
131-11-3
20
66.
Acenaphthylene
208-96-8
20
67.
2,6-Dinitrotoluene
606-20-2
20
68.
3-Nitroaniline
99-09-2
100
(continued)
C-3
Rev. 9/88
-------
Extractables
CAS Number
Quantitation Limits
(mg/Kg)
69.
Acenaphthene
83-32-9
20
70.
2,4-Dinitrophenol
51-28-5
100
71.
4-Ni trophenol
100-02-7
100
72.
Dibenzofuran
132-64-9
20
73.
2,4-Dinitrotoluene
121-14-2
20
74.
Diethylphthalate
84-66-2
20
75.
4-Chlorophenyl-phenylether
7005-72-3
20
76.
Fluorene
86-73-7
20
77.
4-Nitroaniline
100-01-6
100
78.
4,6-D ini tro- 2 -me thylpheno1
534-52-1
100
79.
N-nitrosodiphenylamine (1)
86-30-6
20
80.
4-Bromophenyl-phenylether
101-55-3
20
81.
alpha-BHC
319-84-6
20
82.
Hexachlorobenzene
118-74-1
20
83.
beta-BHC
319-85-7
20
84.
Pentachlorophenol
87-86-5
100
85.
gamma-BHC (Lindane)
58-89-9
20
86.
Phenanthrene
'85-01-8
20
87.
Anthracene
120-12-7
20
88.
delta-BHC
' 319-86-8
20
89.
Heptachlor
76-44-8
20
90.
Aldrin
309-00-2
20
91.
Di-n-butylphthalate
84-74-2
20
92.
Fluoranthene
206-44-0
20
93.
Heptachlor epoxide
1024-57-3
20
94.
Monochlorobiphenyl
27323-18-8
100
95.
Dichlorobiphenyl
2051-60-7
100
96.
Trichlorobiphenyl
2051-61-8
100
97.
Tetrachlorobiphenyl
2051-62-9
100
98.
Pyrene
129-00-0
20
99.
gamma-Chlordane
5103-74-2
20
100.
Endosulfan I
959-98-8
20
101.
alpha-Chlordane
5103-71-9
20
102.
4,4'-DDE
72-55-9
20
103,
Dieldrin
60-57-1
20
104.
Hexachlorob ipheny1
26601-64-9
100
105.
Pentachlorobiphenyl
25429-29-2
100
(continued)
C-4
Rev. 9/88
-------
Extractables
CAS Number
Quantitation Limits
(mg/Kg)
106. Endrin
72-20-8
20
107. Endosulfan II
33213-65-9
20
108. 4,4'-DDD
72-54-8
20
109. Heptachlorobiphenyl
28655-71-2
100
110. Butylbenzylphthalate
85-68-7
20
111. Endosulfan sulfate
1031-07-8
20
112. 4,4'-DDT
50-29-3
20
113. Endrin ketone
53494-70-5
20
114. Benzo(a)anthracene
56-55-3
20
115. Methoxychlor
72-43-5
20
116. Chrysene
218-01-9
20
117. Octachlorobiphenyl
55722-26-4
200
118. 3,3'-Dichlorobenzidine
91-94-1
40
119. bis(2-Ethylhexyl)phthalate
S 117-81-7
20
120. Nonachlorobiphenyl
53742-07-7
200
121. Decachlorobiphenyl
2051-24-3
200
122. Di-n-octylphthalate
117-84-0
20
123, Benzo(b)fluoranthene
205-99-2
20
124. Benzo(k)fluoranthene
207-08-9
20
125. Benzo(a)pyrene
50-32-8
20
126. Indeno(1,2,3-cd)pyrene
193-39-5
20
127. Dibenz(a,h)anthracene
53-70-3
20
128. Benzo(g,h,i)perylene
191-24-2
20
*Specific quantitation limits are highly matrix dependent. The quantitation
limits listed herein are provided for guidance and may not always be
achievable.
C-5
Rev, 9/88
-------
Target Compound List CTCL-) and
Contract Required Quantitation Limits CCRQL>*
Aroclor-Specific/Toxaphene Quantitation Limits
bv GC/EC Method CAS Number (mg/Kg-)
129. Toxaphene 8001-35-2 50
130. Aroclor 1016 12674-11-2 10
131. Aroclor 1221 11104-28-2 10
132. Aroclor 1232 11141-16-5 10
133. Aroclor 1242 53469-21-9 10
134. Aroclor 1248 12672-29-6 10
135. Aroclor 1254 11097-69-1 10
136. Aroclor 1260 11096-82-5 10
*Specific quantitation limits are highly matrix dependent. The quantitation
limits listed herein are provided for guidance and may not always be
achievable.
C-6
Rev. 9/88
-------
EXHIBIT D
ANALYTICAL PROCEDURES FOR
HIGH CONCENTRATION VOLATILE ORGANIC WASTE SAMPLES
-------
TABLE OF CONTENTS
Page No
SECTION I - INTRODUCTION . VOA D-I
SECTION II - SAMPLE PREPARATION AND STORAGE . . ! VOA D-4
PART A - SAMPLE STORAGE VOA D-5
PART B - HIGH LEVEL METHODS FOR SCREENING
AND ANALYSIS OF VOLATILE ORGANICS VOA D-6
SECTION III - SCREENING OF METHANOL EXTRACTS
FOR VOLATILES VOA D-12
SECTION IV - GC/MS ANALYSIS OF VOLATILE ORGANICS . VOA D-17
Rev. 9/88
-------
SECTION I
INTRODUCTION
The samples received for high concentration analysis will consist of three
types of phases: solids, water immiscible liquids, and water miscible
liquids. It is also possible to receive samples that have multiple phases
such as soil, water and oil, in the same sample jar. Because of this
possibility the samples are to be "phase separated" into their individual
phases. The weight of each phase and the phase type are to be recorded on
appropriate data sheets and reported with the sample.
The phase separation techniques employed will vary according to the types
of sample received. Since it is impossible to know the number and types of
phases that will be present in a sample, the choice of phase separation
techniques is left to the discretion of the analyst. Various techniques
can be employed to separate the phases. These include pipetting off liquid
phases (decanting should not be done), centrifuging to remove suspended
solids, use of spatulas to remove solids (wooden tongue depressors work
well). Whenever possible, phase separation operations should be done with
disposable glassware. This eliminates the problem of cleaning contaminated
glassware. The phases should be separated into glass containers with
teflon-lined screw caps. This allows for storage and handling of the waste
in a safe manner. Under no circumstances are samples to be homogenized to
eliminate separate phases.
Each individual phase is then taken through the procedures as a sub-sample.
The results of the analyses are to be reported for each phase of the
sample.
The analyical methods that follow are designed to analyze the organic
compounds on the Target Compound List (TCL) (See Exhibit C). The methods
are divided into the following sections: sample preparation, screening and
analysis. Sample preparation covers sample storage. The analysis section
contains the GC/MS analytical methods for volatile 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.
VOA D-l
Rev. 9/88
-------
1• Method for the Determination of Volatile (Purgeable1 High
Concentration Organic Compounds
1.1 Scope and Application
These procedures are designed for the preparation of waste samples
which may contain organic chemicals at a level greater than 20 mg/kg.
The extracts and sample aliquots prepared using these methods are
screened by gas chromatograph/flame ionization detector (GC/FID) for
volatile organic chemicals. The results of these screens will determine
the dilution required for gas chromatograph/mass spectrometer (GC/MS)
analysis. The analytical scheme is summarized in flowchart form (Figure
Dl).
VOA D-2
Rev. 9/88
-------
Sample
Phase
ao
Weigh lg sample phase
into 20 b! vial
Procede with Che analysis
of each phase as an
Individual sample
Estimate relative volume
of multiple phases and
perform phase separation
1. Add 10 ml methanol
2. Add 100 ul surrogates
3. Shake to disperse/
dissolve sample
4. Allow to settle
Remove two 1 ml aliquots
Add 2 |il (10 Ug) of nonane/
dodecane to one of the aliquots
(optional)
yes
GC screen
Store one aliquot at
4"C for CC/MS analysts
Add 100 ul of methanol
extract to 5 ml organic-
free water
Add 5 ui
Internal
(250 ng)
Standards
\
f
Analyze
and trap
by purge
CC/MS
Estimate concentration
of major component(s)
i
I
4,
Determine amount of
extract required for
500-1000 ng of major
components(s); (Hake
secondary dilution
If necessary)
•i,
I
(Finish)
Add appropriate
amount of methanol
extract to 5 ml of
organic-free ua er
Add additional
methanol so total
volume of methanol
is 100 ul
Add 5 ul <250 ng)
Internal Standards
Estimate the
concentration
of aromatlcs
1 1
±
Compare concentra-
tion of aromatlcs
to that of other
major peaks
satu
Finish
Analyze by purge
and trap CC/MS
FIGURE D1 - FLOWCHART FOR ANALYSIS OF HIGH CONCENTRATION
VOLATILE ORGANICS
V0A D-3
Rev. 9/88
-------
SECTION II
SAMPLE STORAGE AND PREPARATION
VOA D-4
Rev. 9/88
-------
PART A - SAMPLE STORAGE
Procedures for Sample Storage
The samples must be protected from light and refrigerated at 4°C (±2°C)
from the time of receipt until analysis or extraction.
VOA D-5
Rev. 9/88
-------
PART B - HIGH LEVEL METHODS FOR SCREENING AND ANALYSTS OF VOLATILE ORGANICS
1. Summary of Methods
1.1 Samples received for high concentration analysis will consist of
three types of phases: solids, water immiscible liquids, and water
miscible liquids. It is possible to receive samples that will be
multiple phase, such as soil, water and oil in the same sample
container. Multi-phase samples are to be "phase-separated" into
single phase units.
1.2 One gram aliquots of the samples are transferred to vials and
extracted with methanol. The methanol extracts are screened for
volatile organics by GC/FID.
1.3 If organic compounds are not detected by the screen, then a 100 uL
aliquot of the methanol extract is analyzed by purge and trap GC/MS
for volatile organics. If compounds are detected by the screen, the
screening data are used to determine the amount of methanol extract
appropriate for GC/MS analysis.
2. Limitations
2.1 The procedure is designed to allow detection limits for screening
purposes as low as 0.5 - 1 mg/kg for volatile organics. If peaks are
present based on the GC/FID screens, a dilution of the methanol
extract prior to GC/MS analysis is required. Some samples may
contain high concentrations of chemicals that interfere with the
analysis of other components at lower levels; the detection limits in
those cases may be significantly higher.
2.2 These extraction and preparation procedures were developed for rapid
and safe handling of high concentration hazardous waste samples. The
design of the methods does not stress efficient recoveries or low
limits of detection for all components. Rather, the procedures were
designed for moderate recovery and sufficient sensitivity of a broad
spectrum of volatile organic chemicals. The results of the analyses
thus may reflect only a minimum of the amount of pollutants actually
present in some samples.
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 the.se materials must be routinely
demonstrated to be free from interferences under the conditions of
the analysis by running laboratory method blanks. Matrix
interferences may be caused by contaminants that are coextracted from
the sample. The extent of matrix interferences will vary
considerably from source to source, depending upon the nature and
diversity of the samples.
VOA D-6
Rev. 9/88
-------
3.2
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.
4. Apparatus and Equipment
4.1 Analytical balance capable of accurately weighing 0.0001 g and a top-
loading balance capable of weighing 0.1 g.
4.2 Glassware
Bottles - 15 mL, screw cap, with teflon cap liner.
Volumetric flasks - Class A with ground glass stoppers.
Vials - 2 mL for GC autosampler.
5. Reagent Specifications
5.1 Reagent water is defined as water in which an interferent is not
observed at the minimum detection limit of the parameters of
interest.
5.1.1 Reagent water may be generated by passing tap water through
a carbon filter bed containing activated carbon (Calgon
Corp., Filtrasorb-300, or equivalent).
5.1.2 A water purification system (Millipore Super-Q or equivalent)
may be used to generate reagent water.
5.1.3 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 1 hour. While still hot, transfer the water to a narrow-
mouth, screw-cap bottle and seal with a teflon-lined septum
and cap or maintain the water under a continuous purge of
inert gas.
5.2 Methanol - Pesticide residue analysis grade, or equivalent. Methanol
must be demonstrated to be free from purgeable interferences.
5.3 Preparation of Spiking Standards and Analytical Standards
5.3.1 Stock standard solutions may be prepared from pure standard
materials or purchased as certified (compound purity of 96%
or greater) solutions. Commercially prepared stock standards
may be used at any concentration if they are certified by the
manufacturer or by an independent source. Prepare stock
standard solutions in methanol using assayed liquids or gases
as appropriate.
5.3.2 Great care must be taken to maintain the integrity of all
standard solutions. All standard solutions should be stored
at -10°C to -20°C in amber bottles with teflon liners in the
VOA D-7
Rev. 9/88
-------
screw caps. For storage of calibration standards, bottle
caps with syringe valves are recommended.
5.3.3 Place about 9.8 raL 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
0.0001 g.
5.3.4 Add the assayed reference material as described below.
5.3.4.1 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
directly into the alcohol without contacting the
neck of the flask.
5.3.4.2 Gases - To prepare standards for any of the four
halocarbons that boil below 30°C (i.e.,
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.
5.3.5 Reweigh, dilute to volume, stopper, then mix by inverting the
flask several times. Calculate the concentration from the
net gain in weight.
5.3.6 Transfer the stock standard solution into a teflon-sealed,
screw-cap bottle. Store with minimal headspace at -10°C to
-20°C and protect from light.
5.3.7 Prepare fresh stock standards every two months for the four
gases. All other standards must be replaced after six
months, or sooner if comparison with check standards indicate
a problem.
5.3.8 Using stock standard solutions, prepare secondary dilution
standards in methanol that contain the compounds of interest,
either singularly 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.
5.4 Surrogate Standard Spiking Solution - Prepare stock standard
solutions for toluene-dg, p-bromofluorobenzene (BFB), and 1,2-
dichloroe thane -d^ in methanol. Prepare a surrogate standard spiking
solution from these stock standards at a concentration of 250 ug/mL
in methanol.
VOA D-8
Rev. 9/88
-------
5.5 Purgeable Organic Control Matrix Spiking Solution - Prepare in
methanol a spiking solution that contains the following compounds at
a concentration of 250 ug/mL: 1,1-dichloroethene, trichloroethene,
chlorobenzene, toluene, and benzene.
5.6 Screening Standards - Prepare standard mixture #1 containing benzene,
toluene, ethylbenzene, and xylene in methanol. Prepare standard
mixture #2 containing n-nonane and n-dodecane in methanol.
5.6.1 Stock standard solutions (1.00 mg/mL) can be prepared from
pure standard materials or purchased as certified solutions.
5.6.1.1 Prepare stock standard solutions by accurately
weighing approximately 0.0100 grams of pure
material. Dissolve the material in methanol;
dilute to volume in a 10 mL volumetric flask.
Larger volumes can be used at the convenience of
the analyst. Compound purity should be certified
at 96% or greater.
5.6.1.2 Transfer the stock standard solutions into teflon-
sealed, screw-cap bottles. Store with minimal
headspace 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.
:v . 5.6.2 Prepare working standards of mixtures #1 and #2 at 10 ng/uL
" of each compound in methanol. Prepare spiking mixture of #2
at 5000 /ig/mL in methanol. The spiking mixture is added to
each screening extract.
5.7 Internal Standard Spiking Solution - Prepare stock standard solutions
for bromochloromethane, 1,4-difluorobenzene, and chlorobenzene-d^ in
methanol. Prepare an internal standard spiking solution from these
stock standards at a concentration of 50 ug/mL in methanol. This 50
ug/mL solution is the working standard solution.
5.8 p-bromofluorobenzene (BFB) Standard - Prepare a 25 ug/mL solution of
BFB in methanol.
5.9 Calibration Standards - Prepare a stock standard solution(s) for the
34 volatile target compounds listed in Exhibit C. Prepare working
standard solutions from these stock standards at a concentration of
50 ug/mL in methanol. The working standard(s) will be used to
prepare calibration standards at five specified concentrations as
described in Section IV, 6.3.1. Prepare fresh working standards
weekly for the four gases. All other working standards must be
replaced after one month.
VOA D-9
Rev. 9/88
-------
6, Phase Separation
6.1 The samples received for high concentration analysis will
consist of three phase types:
Water miscible liquid
Water immiscible liquid
Solid
It is possible to receive samples that contain multiple phases such
as water, oil, and soil in the same sample jar. Because of this
possibility, the samples are to be "phase separated" into individual
phases.
6.2 Each individual phase is taken through the procedures as a subsample.
Report analytical results for each sample phase.
6.3 Do not analyze any phase that represents less than 10% of the total
sample volume.
6.4 In the following procedures, where applicable, references to
"samples" explicitly mean "single phase units".
7. Sample Preparation for Volatile Oreanics
The high concentration method is based on extracting the sample with
methanol. A portion of the extract is used for a screen on the
GC/FID. From the results of the screen, an aliquot of the methanol
extract is added to reagent water containing the internal standards.
This is purged at ambient temperature.
7.1 Weigh 1 g of each sample phase into separate tared 15 mL vials using
a top loading balance. Record the actual weight to the nearest
0.1 g.
7.2 Weigh 1.0 g of corn oil into a tared 15 mL vial for use as the
control matrix spike.
7.3 Quickly add 10 mL of methanol to all vials, then add 100 uL of
surrogate spiking solution (5.4). For the control matrix spike, add
10 mL of methanol, 100 uL of surrogate spiking solution, and 100 uL
of matrix spiking solution (5.5).
7.4 Prepare a method blank by adding 100 uL of surrogate spiking
solution to 10 mL of methanol in a 15 mL vial.
7.5 Cap all vials and shake for 2 minutes. (Note: Steps 7.1 through 7.4
must be performed rapidly to avoid loss of volatile organics. These
steps must be performed in a laboratory free of solvent fumes.)
7.6 In order to enhance sample extraction tfith methanol, the sample may
be agitated in cold water in an ultrasonic bath for 2-3 minutes.
V0A D-10
Rev. 9/88
-------
7.7 Transfer for storage 1 mL of extract to a GC vial using a disposable
pipet. Transfer an additional 1 mL of extract to a GC vial for use
as a screening extract. These extracts may be stored in the dark at
4°C prior to analysis. Mark the level of liquid in the vial to check
for evaporation of the extract. Add 2 uL of 5000 ug/mL #2 spiking
mixture (n-nonane and n-dodecane) (5.6.2) to each screening extract.
The sample is now ready for screening.
VOA D-11
Rev. 9/88
-------
SECTION III
SCREENING OF METHANOL EXTRACTS
FOR VOLATILES
"\
VOA D-12
Rev. 9/88
-------
1.
Summary of Method
The methanol extracts of the samples are screened on a gas
chromatograph/flame ionization detector (GC/FID). The results of the
screen will determine at what dilution level the volatile organics
extracts are to be analyzed by GC/MS.
2. Apparatus and Materials
2.1 Gas Chromatograph - A gas chromatograph suitable for on-column
injection, and all required accessories including syringes,
analytical columns, gases, flame ionization detector, and strip-chart
recorder. A data system is recommended for measuring peak areas,
2.2 GC Column - 3 m x 2 mm ID glass column packed with 10% SP-2100 on
100-120 mesh Supelcoport (or equivalent). The column temperature
should be programmed from 55° C to 280°C at 16°C/minute and held at
280°C for 10 minutes. (Other chromatographic conditions may also
provide acceptable results.)
3. Reagents
3.1 Methanol - Pesticide residue analysis grade, or equivalent. Methanol
must be demonstrated to be free from purgeable interferences.
3 .-2 Screening Standards - Prepare standard mixture #1 containing benzene;
toluene, ethylbenzene, and xylene in methanol. Prepare standard
mixture #2 containing n-nonane and n-dodecane in methanol.
3.2.1 Stock standard solutions (1.00 mg/mL) can be prepared from
pure standard materials or purchased as certified solutions.
3.2.1.1 Prepare stock standard solutions by accurately
weighing approximately 0.0100 grams of pure
material. Dissolve the material in methanol;
dilute to volume in a 10 mL volumetric flask.
Larger volumes can be used at the convenience of
the analyst. Compound purity should be certified
at 96% or greater.
3.2.1.2 Transfer the stock standard solutions into Teflon-
sealed, screw-cap bottles. Store with minimal
headspace at -ICC 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.
V0A D-13
Rev. 9/88
-------
3.2.2 Prepare working standards of mixtures #1 and #2 at 10 ng/uL
of each compound in methanol.
Screening Standard #1
Screening Standard #2
Benzene
Toluene
n-nonane
n-dodecane
Ethylbenzene
Xylene
4.
5.
5.1
5.2
6.
6.1
Limitations
The flame ionization detector varies considerably in sensitivity when
comparing aromatics and halogenated methanes and ethanes.
Halomethanes are approximately 20 times less sensitive than aromatics
and haloethanes are approximately 10 times less sensitive.
Extract Screening
External Standard Calibration - Standardize the GC/FID each 12 hour
shift for half scale response when injecting 1-5 uL of the screening
standards, mix #1 (aromatics) and the mix #2 (n-nonane, n-dodecane),
at the 10ng/^L concentration.
Inject the same volume of methanol sample extract as the standard
mixture.
Interpretation of Screening Results
Compare the methanol sample extract chromatogram with the method
blank and standard chromatograms.
6.1.1 If no peaks are noted, other than those also in the method
blank, analyze 100 uL of the sample by GC/MS. (See Table 1)
6.1.2 If peaks are present prior to the n-dodecane, and the
aromatics are distinguishable, follow Option A below to
determine the dilution needed to analyze by GC/MS.
6.1.3 If peaks are present prior to the n-dodecane, but the
aromatics are absent or indistinguishable, use Options B or C
below. Calculate a factor using Equation Dl:
Equation Dl
X Factor, - peak area of sample malor peak
peak area of n-nonane
See Table 1 to determine the dilution needed to analyze by
GC/MS.
VOA D-14
Rev. 9/88
-------
6.2 Following are three options for interpreting the GC/FID chromatogram.
6.2.1 Option A - Use standard mixture #1 as an external standard to
calculate an approximate concentration of the aromatics in
the sample. If aromatics appear to be the most concentrated
materials in the sample, use the screening information to
determine the proper dilution for purge and trap. Use a
volume of methanol to give 500 - 1000 ng of the most
concentrated aromatics. This should be the best approach;
however, the aromatics may be absent or obscured by higher
concentrations of other purgeables. If this is the case,
Options B or C may be more suitable.
6.2.2 Option B - Use standard mixture #2 as an internal standard
to calculate the factor in Equation Dl. Use this factor and
Table 1 to determine a dilution for purge and trap. All
purgeables of interest have retention times less than n-
dodecane.
6.2.3 Option C - Use standard mixture #2 as an internal standard to
estimate the concentration of the major peaks. Calculate a
volume of methanol that gives 500 - 1000 ng of the most
concentrated constituents. Use that volume of methanol for
purge and trap analysis.
6.2.4 If the screening results indicate that less than 5 uL of
extract should be used for GC/MS analysis, prepare a
secondary dilution in methanol and use the secondary dilution
for GC/MS analysis.
6.2.5 NOTE: The screening procedure can also provide information
regarding certain late-eluting compounds (e.g., naphthalene)
which may complicate subsequent GC/MS analyses. Calculate
the appropriate dilution factor for the concentrations
exceeding the table.
TABLE 1 - DETERMINATION OF GC/MS PURGE AND TRAP DILUTION LEVEL
Estimated
Volume of
Concentration
Methanol
X Factor
Range (mg/kg)*
Extract (uL)**
0
5
0 -
• 10
100
0.5 -
10
1 -
• 20
50
2.5 -
50
5 •
¦ 100
10
12.5 -
250
25 -
• 500
100
of 1/50
dilution***
VOA D-15
Rev. 9/88
-------
Actual concentration ranges could be 10 to 20 times higher
than this if the compounds are halogenated and the estimates
are from a GC/FID.
** The volume of methanol extract added to the 5 mL of water
being purged. Add additional PURE methanol to bring the
total volume of methanol to 100 uL.
*** Concentrations at this and higher levels require an initial
dilution of the extract in methanol before removing an
aliquot for analysis by GC/MS.
VOA D-16
Rev. 9/88
-------
SECTION IV
GC/MS ANALYSIS OF VOLATILE ORGANICS
VOA D-17
-------
1.
Summary of Method
A portion of the methanol extract, prepared as described in the
preceeding sections, 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 method blanks.
Teflon tubing, thread sealants, and flow controllers should be used
in the purging device.
2.2 Samples can be contaminated by diffusion of volatile organics
(particularly fluorocarbons, acetone, and methylene chloride)
through the septum seal into the sample during storage and handling.
Blanks prepared from methanol and carried through the holding period
and the analysis protocol may serve as a check on such contamination.
2.3 Contamination by carry-over can occur whenever highly concentrated
and minimally concentrated samples are sequentially analyzed. To
reduce carry-over, the purging device and sampling syringe must be
rinsed with reagent water between sample analyses. Whenever a highly
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 levels of
purgeables , it may be necessary to wash out the purging device with
a detergent solution, rinse it with distilled water, and then dry it
in a 105°C oven 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 Contamination can also occur when samples contain certain late-
eluting compounds (e.g., naphthalene). The screening results should
provide an indication of the presence of such contamination. When
contamination due to late-eluting compounds is suspected, a prolonged
bakeout of the GC column and the trap is recommended.
3. Apparatus. Materials. and Equipment
3.1 Micro syringes - 10 uL and larger, 0.006 inch ID needle.
VOA D-18
Rev. 9/88
-------
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 Analytical balance, capable of accurately weighing 0.0001 g. and a
top-loading balance capable of weighing 0.1 g.
3.5 Glassware
3.5.1 Bottles - 15 mL, screw cap, with Teflon cap liner.
3.5.2 Volumetric flasks - class A with ground-glass stoppers.
3.5.3 Vials - 2 mL for GC autosampler.
3.6 Purge and Trap Device. The purge and trap device consists of three
separate pieces of equipment; the sample purger, the trap, and the
trap heater. 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 with a diameter of
less than 3 mm at the origin. The purge gas must be
introduced no more than 5 mm from the base of the water
column. The sample purger, illustrated in Figure D2, 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 D3.
3.6.3 The trap heater 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. The heater design, illustrated in Figure
D3, 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 D4 and D5.
3.7 GC/MS System
3.7.1 Gas Chromatograph - A temperature programmable gas
chromatograph suitable for on-column injection, and all
VOA D-19
Rev. 9/88
-------
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 seven 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.
GC/MS Interface - Any gas chromatograph to mass spectrometer
interface that gives acceptable calibration points at 50 ng
or less per injection for each of the parameters of interest
and achieves all acceptable performance criteria (Exhibit E)
may be used. Gas chromatograph to mass spectrometer
interfaces constructed of all-glass or glass-lined materials
are recommended. Glass can be deactivated by silanizing with
dichlorodimethylsilane.
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.
3.7.4
3.7.5
VOA D-20
Rev. 9/88
-------
14 mm
Inlet '/, m.
Opttona!
foam
Trap
V, in.
O.O exit
Sample Inlet
2-war Syringe valve
17 cm 20 gauge syringe needle
\*6mm 0.0. Rubber Septum
10mm 0.0. •/„ in. 0.0.
— Inlet =%/Stainless Steel
V, in 0 0
13X molecular
j sieve purge
gas Utter
10mm glass frit
medium porositf
Purge ges
(low control
FIGURE D2
PURGING DEVICE
Packing procedure
Carmruet—n
Class
wool
Grade IS
Si/tea gel
Smm
8cm
Tana* 16cm
3% OV-1
Glass
wool
1cm'
\
Smm
¦/.
Trap inlet
Compression Irtting
and lerrules
14ft T'Sfoot resistance
mire wrapped solid
Thermocouple/coraroHm
sensor
Electronic
temperature
control
and
pyrometer
Tubing 25 cm
0. f OS in I D.
0 125 in 0.0
stainless steel
FIGURE D3 - TRAP PACKINGS AND CONSTRUCTION TO INCLUDE
DESORB CAPABILITY
VOA D-21
Rev. 9/88
-------
Carrtar gas /tew control
Frassura ragulator
\
Purgm gas
Ho** control
13X motacular
sta*a filtar
Uqim4 mfcfron port*
' ^fnhtmn crr*n
-eruriiW4v-T Confirmatorr column
H1 I ? ?9 dataCtOt
Analytica! column
optional 4 -port column
S'port **/*ctl0n *al*a
*•/*• / Tf*p inl*t
a/ Raststanca wira
sHaatat control
Nota:
AH Unas batmvan
trap ana GC
^ should ba haatad
*"c* to 80°C
FIGURE D4
SCHEMATIC OF PURGE AND TRAP DEVICE - PURGE MODE
Csrrmr g*s fh*r control Uau«t in^actton porta c0jum„ 0Yf„
Prassura ragulator
Purga gas
fk><* control
f 3X molacular ——y^
Mn filtar
— Confirmatory column
_ To d*t actor
!""! rl p * w
] U U [ —Analytic*1 column
optional 4'port column
salacuon *ahra
6-port jrtp in/0(
***** I ffaststanca wira
Purging
da*
-------
4. Reagents
4.1 Reagent water is defined as water in which an interferent is not
observed at the minimum detection- limit of the parameters of
interest.
4.1.1 Reagent water may be generated by passing tap water through a
carbon filter bed containing 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 1 hour. While still hot, transfer the water to a narrow-
mouth, screw-cap bottle and seal with a Teflon-lined septum
and cap or maintain the water under a continuous purge of
inert gas.
4.2 Methanol - Pesticide residue analysis grade, or equivalent. Methanol
must be demonstrated to be free from purgeable interferences.
4.3 Preparation of Spiking Standards and Analytical Standard's.
4.3.1 Stock standard solutions may be prepared from pure standard
materials or purchased as certified (compound purity of 96%
or greater) solutions. Prepare stock standard solutions in
methanol using assayed liquids or gases as appropriate.
Commercially prepared stock standards may be used at any
concentration if they are certified by the manufacturer or by
an independent source.
4.3.2 Great care must be taken to maintain the integrity of all
standard solutions. All standard solutions should be stored
at -10°C to -20°C in amber bottles with teflon liners in the
screw caps. For storage of calibration standards, bottle
caps with syringe valves are recommended.
4.3.3 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
0.0001 g.
4.3.4 Add the assayed reference material as described below.
4.3.4.1 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
directly into the alcohol without contacting the
neck of the flask.
VOA D-23
Rev. 9/88
-------
4.3.4.2 Gases - To prepare standards for any of the four
halocarbons that boil below 30°C (i.e.,
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.
4.3.5 Reweigh, dilute to volume, stopper, then mix by inverting the
flask several times. Calculate the concentration from the
net gain in weight.
4.3.6 Transfer the stock standard solution into a Teflon-sealed,
screw-cap bottle. Store with minimal headspace at -10°C to -
20°C and protect from light.
4.3.7 Prepare fresh stock standards every two months for the four
gases. All other standards must be replaced after six
months, or sooner if comparison with check standards indicate
a problem.
4.3.8 Using stock standard solutions, prepare secondary dilution
standards in methanol that contain the compounds of interest,
either singularly 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 j
signs of degradation or evaporation, especially just prior to
preparing calibration standards from them.
4.4 Surrogate Standard Spiking Solution - Prepare stock standard
solutions for toluene-dg, p-bromofluorobenzene (BFB), and 1,2-
dichloroethane-d^ in methanol. Prepare a surrogate standard spiking
solution from these stock standards at a concentration of 250 ug/mL
in methanol.
4.5 Purgeable Organic Control Matrix Spiking Solution - Prepare in
methanol a spiking solution that contains the following compounds at
a concentration of 250 ug/mL: 1,1-dichloroethene, trichloroethene,
chlorobenzene, toluene, and benzene.
4.6 Internal Standard Spiking Solution - Prepare stock standard solutions
for bromochloromethane, 1,4-difluorobenzene, and chlorobenzene-d^ in"
methanol. Prepare an internal standard spiking solution from these
stock standards at a concentration of 50 ug/mL in methanol. This 50
ug/mL solution is the working standard solution.
4.7 P-bromofluorobenzene (BFB) Standard - Prepare a 25 ug/mL solution of
BFB in methanol.
4.8 Calibration Standards - Prepare a stock standard solution(s) for the
34 target compounds listed in Exhibit C. Prepare working standard
solutions from these stock standards at a concentration of 50 ug/mL
VOA D-24
Rev. 9/88
-------
5.
5.1
5.2
5.3
in methanol. The working standard(s) will be used to prepare
calibration standards at five specified concentrations as described
in 6.3.1. Prepare fresh working standards weekly for the four gases.
All other working standards must be replaced after one month.
Instrument Operating Conditions
The following are recommended purge and trap conditions:
Purge Flow:
Desorb Flow:
Purge:
Desorb:
Bake:
25-40 mL per minute.
20-60 mL per minute.
11 minutes with trap temperature of
26°C or less.
4 minutes at 180°C.
12 - 15 minutes at 180°C.
The following are recommended operating conditions for the gas
chromatograph:
Column:
Carrier:
Temperature Program:
Carbopack B (60/80 mesh) with 1%
SP-1000 packed in a 6 foot by
2 mm ID glass column.
Helium - 30 mL per minute.
45°C for 3 minutes,
program at 8°C per minute to
220"C and hold for 15 minutes.
Establish the following operating conditions for the mass
spectrometer:
Electron Energy:
Mass Range:
Scan Time:
70 Volts (nominal)
35 - 260
To give at least 5 scans per peak,
but not to exceed 3 seconds per
scan.
6. Calibration
6.1 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 mL/min. Prior to use,
daily condition traps 10 minutes while backflushing at 180°C with the
column at 220°C.
6.2 Connect the purge and trap device to a gas chromatograph. The gas
chromatograph must be operated using temperature and flow rate
VOA D-25
Rev. 9/88
-------
parameters equivalent to those in paragraph 5.2. Calibrate the purge
and trap-GC/MS system using the internal standard technique described
below.
6.3 Internal Standard Calibration Procedure. The three internal
standards are: bromochloromethane, 1,4-difluorobenzene, and
chlorobenzene-dj.
6.3.1 From working standards in methanol, prepare calibration
standards at the following five concentration levels for each
target parameter: 20, 50, 100, 150, and 200 ug/L in reagent
water (corresponding to 10, 25, 50, 75, and 100 rag/kg in a 1
g sample). Add additional methanol so that the total amount
of methanol is 100 uL per 5 mL of aqueous standards. Aqueous
standards may be stored up to 24 hours, if held in sealed
vials with zero headspace. If not so stored, they must be •
discarded after an hour unless they are set up to be purged
by an autosampler. When using an autosampler, the standards
may be kept up to 12 hours in purge tubes connected via the
autosampler to the purge and trap device.
6.3.2 Add 5 uL of the 50 ug/mL internal standard spiking solution
(4.6) to each 5 mL standard, blank, and sample.
6.3.3 • After the ion abundance criteria for- BFB (Table 2) are met,
analyze each calibration standard (6.1.3). Tabulate the area
response of the characteristic ions against the concentration
for each compound and internal standard. Calculate relative
response factors (RRF) for each compound using Equation D2.
The characteristic ions and internal standards for the
volatile compounds are shown in Table 3.
TABLE 2 ¦
• BFB KEY IONS AND ABUNDANCE CRITERIA
Mass
Ion Abundance Criteria
50
15.0 - 40.0 percent of mass 95
75
30.0 - 60.0 percent of mass 95
95
Base peak, 100 percent relative abundance
96
5.0 - 9.0 percent of mass 95
173
Less than 2.00 percent of mass 95
174
Greater than 50.0 percent of mass 95
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
VOA D-26
Rev. 9/88
-------
NOTE 1: BFB criteria MUST be met before any samples, blanks, or
standards are analyzed. Any samples analyzed when tuning
criteria have not been met will require reanalysis at no
additional cost to the Agency,
NOTE 2: Whenever the laboratory 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 12-hour tuning requirements.
NOTE 3: 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 BFB
analysis that the laboratory submits as documentation of
compliant tune. The time period ends after twelve (12) hours
has elapsed according to the system clock.
Equation D2 RRF - fx_ X
Ais Cx
Area of the characteristic ion for
the compound to be measured.
Area of the characteristic ion for
the specific internal standard from
Table 3.
Concentration of the internal
standard.
Concentration of the compound to be
measured.
Where:
Ax -
Ais "
VOA D-27
Rev. 9/88
-------
TABLE 3 - CHARACTERISTIC IONS FOR VOLATILE COMPOUNDS
Primary Secondary Internal
Compound Ion Ion(s) Standard
SURROGATE STANDARDS
4-Bromofluorobenzene
95
174,
176
3
1,2-Dichloroethane-d^
65
102
1
Toluene-dg
98
70,
100
3
INTERNAL STANDARDS
Bromochlororaethane (1)
128
49,
130, 51
1
1,4-Difluorobenzene (2)
114
63,
88
2
Chlorobenzene-d^ (3)
117
82,
119
3
TARGET COMPOUNDS
Chloromethane
50
52
1
Bromomethane
94
96
1
Vinyl Chloride
62
64
1
Chloroethane
64
66
1
Methylene Chloride
84
49,
51, 86
1
Acetone
43
58
1
Carbon Disulfide
76
78
1
1,1-Dichloroethene
96
61,
98
. 1
1,1-Dichloroethane
63
65,
83, 85, 98, 100
1
1,2-Dichloroethene
96
61,
98
1
Chloroform
83
85
1
1,2 -Dichloroethane
62
64,
100, 98
1
2 -Butanone
72
57
1
1,1,1-Trichloroethane
97
99,
117, 119
2
Carbon Tetrachloride
117
119,
121
2
Vinyl Acetate
43
86
2
Broraodichlororaethane
83
85,
129
2
1,2-Dichloropropane
63
65,
114
2
trans-1,3-Dichloropropene
75
77
2
Trichloroethene
130
95,
97, 132
2
Dibromochloromethane
129
208,
206
2
1,1,2-Trichloroethane
97
83,
85, 99, 132, 134
2
Benzene
78
2
cis-1,3-Dichloropropene
75
77
2
Bromoform
173
171,
175, 250, 252, 254, 256
2
2-Hexanone
43
58,
57, 100
3
4 -Me thy1- 2 -Pentanone
43
58,
100
3
Tetrachloroethene
164
129,
131, 166
3
1,1,2,2-Tetrachloroethane
83
85,
131, 133, 166
3
Toluene
92
91
3
Chlorobenzene
112
114
3
Ethylbenzene
106
91
3
Styrene
104
78,
103
3
Total Xylenes
106
91
3
VOA D-28
Rev. 9/88
-------
6.3.4 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. The following five
System Performance Check Compounds (SPCC) are checked for a
minimum average response factor: chloromethane, 1,1-
dichloroethane, bromoform, 1,1,2,2-tetrachloroethane, and
chlorobenzene. The minimum average response factor for
bromoform is 0.250; the minimum average response factor for
all other SPCCs is 0.300.
The following five Calibration Check Compounds (CCC) are used
to evaluate the curve: vinyl chloride, 1,1-dichloroethene,
chloroform, 1,2-dichloropropane, toluene, and ethylbenzene.
Calculate the Percent Relative Standard Deviation (%RSD)
(Exhibit E, Section III, Equation 2.2) of RRF values over the
working range of the curve. A maximum %RSD of 30.0% for each
CCC must be met before the curve is valid.
6.3.5 Once each 12 hours (beginning with the injection of the
tuning compound), after demonstrating the key ion abundance
criteria for BFB (Table 2), a continuing calibration check
must be performed. Analyze the 50 ug/L standard, using the
same conditions as those used for the initial calibration.
6.3.5.1 Calculate the response factors as in 6.3.3. Check
the minimum response factors for the system
performance check compounds (SPCC). . The minimum
response factor for bromoform is 0.250; the
minimum response factor for all other SPCCs is
0.300.
6.3.5.2 Calculate the response factors for the calibration
check compounds (CCC) and compare against those
determined in the initial calibration. Calculate
the percent difference (%D) (Exhibit E, Section
III, Equation 2.3). The maximum %D for CCCs is
25.0%.
6.3.5.3 After verifying that the continuing calibration
meets the criteria for SPCCs and CCCs, calculate
the relative response factors for the remaining
compounds.
7. Sample Analysis
An aliquot of the methanol extract is added to reagent water
containing the internal standards. This is purged at ambient
temperature and analyzed by GC/MS.
7.1 All samples and standard solutions must be allowed to warm to ambient
temperature before analysis.
7.2 Adjust the purge gas (helium) flow rate to 25-40 (±3) mL per minute.
Variations from this flow rate may be necessary to achieve better
VOA D-29
Rev. 9/88
-------
purging and collection efficiencies for some compounds, particularly
chloromethane and bromoform.
7.3 After achieving the key ion abundance criteria for BFB (Table 2),
perform the daily system calibration, as described in 6,3.5.
7.4 The purgeable organics screening procedure will show the approximate
concentrations of major sample components. If a dilution of the
sample is indicated, this dilution shall be made just prior to GC/MS
analysis of the sample.
7.5 Remove the plunger from a 5 iL "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 5 uL of the
internal standard solution. Add the volume of methanol extract
determined from the screening procedure and a volume of pure methanol
to total 100 uL (excluding methanol in the standards).
7.6 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.
7.7 Proceed with the analysis as outlined. Analyze all method blanks on
the same instrument as the samples.
7.8 Close both valves and purge the sample for 11.0 (±0.1) minutes at
ambient temperature.
7.9 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 mL/min for 4 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.
7.10 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 carry-over of pollutant compounds.
Baking out the purging chamber to remove traces of possible
contamination is highly recommended.
7.11 After desorbing the sample for 4 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 7 minutes, turn off the trap heater and open the
VOA D-30
Rev. 9/88
-------
syringe valve to stop the gas flow through the trap. When cool, the
trap is ready for the next sample.
7.12 If the initial analysis of a sample or a dilution of a sample has
concentration of target compounds that exceeds the initial
calibration range, the sample must be reanalyzed at a higher
dilution. 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
an acceptable blank can be analyzed that is free of interferences.
(Exhibit E, Part III)
7.13 All dilutions must be made such that major constituents are not
saturated but give a response greater than that of the nearest
internal standard.
7.14 Internal standard responses and retention times in all samples and
standards must be evaluated immediately after or during 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. If the extracted ion
current profile (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. Internal
Standard Areas and Retention Times are reported on Form VIII HCV, as
described in Exhibit B.
8. Qualitative Analysis
8.1 Criteria for Verification of Target Compound Identifications
8.1.1 The target compounds listed in Exhibit C shall be identified
by an analyst competent in the interpretation of mass spectra
by comparison of the sample mass spectrum to the mass
spectrum of a standard of the suspected compound.
8.1.2 Two criteria must be satisfied to verify the identifications:
8.1.2.1 Elution of the sample component at the same GC
relative retention time as the standard component.
8.1.2.2 Correspondence of the sample component and
standard component mass spectra.
8.1.3 For establishing correspondence of the GC relative retention
time (RRT), the sample component RRT must compare within
±0.06 RRT units (or ±5 seconds) of the RRT of the standard
component. For reference, the calibration standard must be
rur. on the same shift as the sample. If coelution of
interfering components prohibits accurate assignment of the
VOA D-31
Rev. 9/88
-------
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.
8.1.4 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 (Table 2). These
standard spectra may be obtained from the daily calibration
standard or from the user-created mass spectral library. The
requirements for qualitative verification by comparison of
mass spectra are as follows:
8.1.4.1 . All ions present in the standard mass spectrum at
a relative intensity greater than 10% (most
abundant ion in the spectrum equals 100%) must be
present in the sample spectrum.
8.1.4.2 The relative intensities of ions specified in the
above paragraph must agree within ±20% between the
standard and sample spectra. (Example: For an
ion with an abundance of 50% in the standard
spectrum, the corresponding sample abundance must
be between 30 and 70 percent).
8.1.4.3 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. Both raw and background
subtracted spectra must be evaluated. The
verification process should favor false positives.
All compounds meeting the identification criteria
must be reported with their spectra. For all
compounds below the CRQL report the actual value
followed by a "J", e.g., "3J."
8.1,5 If a compound cannot be verified by all of the criteria in
8.1.4.3, 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 9.
8.2 A library search shall be executed for non-target sample components
for the purpose of tentative identification. For this purpose, the
most recent available version of the NBS Mass Spectral Library shall
be used. Computer generated library search routines should not use
normalization routines that would misrepresent the library or unknown
spectra when compared to each other.
8.2.1 Up to 10 nonsurrogate organic compounds of greatest apparent
concentration not listed in Exhibit C shall be tentatively
identified via a forward search of the NBS Mass Spectral
Library. (Substances with responses less than 10% of the
VOA D-32
Rev. 9/88
-------
<
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.
8.2.2 Guidelines for making tentative identification are as
follows:
Major ions in the reference spectrum (ions greater
than 10% of the most abundant ion) should be
present in the sample spectrum.
The relative intensities of the major ions should
agree within ±20%. (Example: For an ion with an
abundance of 50 percent in the standard spectrum,
the corresponding sample abundance must be between
30 and 70 percent.)
The molecular ion of the reference spectrum must
be present in sample spectrum.
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.
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 opinion of the mass 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 aromatic, unknown hydrocarbon,. unknown
acid type, unknown chlorinated compound). If probable
molecular weights can be distinguished, include them.
9. Quantitative Analysis
9.1 Target compounds identified shall be quantified by the internal
standard method. The internal standard used shall be the one
assigned in Table 2.1, Volatile Internal Standards with Corresponding
Target Analytes Assigned for Quantitation (Exhibit E). The EICP area
of the characteristic ions of analytes listed in Table 3 is used.
The relative response factor (RRF) from the daily calibration
standard analysis is used to calculate the concentration in the
sample. Use the relative response factor as determined in paragraph
6.3.3 and calculate the analyte concentration in the sample using
Equation D3.
8.2.2.1
8.2.2.2
8.2.2.3
8.2.2.4
8.2.2.5
VOA D-33
Rev. 9/88
-------
Xylenes (o, m, and p isomers) are to be reported as total xylenes.
Since o- and p-xylene overlap, the two xylene peaks (o/p and m) must
be added together to give the total concentration of all xylene
isomers.
Equation D3
(Ax>^»)(vt)
Sample Concentration (rag/kg) -
(Ais)(RF)(VL)(Ws)
Where:
^ - Area of the characteristic ion for the
compound to be measured.
A|s - Area of the characteristic ion for the
specific internal standard from Table 3.
I. - Amount of internal standard added in
s
nanograms (ng),
Vt - Volume of total extract (uL).
V£ - Volume of extract added (uL) for purging.
Ws - Weight of sample extracted (mg).
9.2 An estimated concentration for non-target compounds tentatively
identified shall be quantified by the internal standard method. For
quantification, the nearest internal standard free of interferences
must be used.
Equation D3 is used to calculate concentrations. 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.
9.3 Use Equation D4 to calculate surrogate standard recoveries on all
samples, blanks and spikes. Determine if recovery is within
specified limits.
Equation D4
Qd
Percent Surrogate Recovery - -— X 100%
^a
VOA D-34
Rev. 9/88
-------
Where:
- Quantity determined by analysis
Qa - Quantity added to sample
9.4 If recovery is not within specified limits, the following is
required:
9.4.1 Check to be sure there are no errors in calculations,
surrogate solutions, and internal standards. Also, check
instrument performance.
9.4.2 Recalculate the sample data if any of the above checks reveal
a problem.
9.4.3 If surrogates cannot be detected due to dilution factors,
this requirement need not be met. (Report the value as DL.)
NOTE: Surrogate recovery limits are MANDATORY for method
blanks. However, surrogate recoveries for high concentration
samples and control matrix spikes are ADVISORY at this time.
Reanalysis of samples and control matrix spikes is not
required if surrogate recoveries are outside of contractually
specified limits. However, the analyst must, verify that the
deviation is not a result of laboratory error.
VOA D-35
Rev. 9/88
-------
EXHIBIT D
ANALYTICAL PROCEDURES FOR HIGH CONCENTRATION EXTRACTABLE ORGANIC WASTE
SAMPLES
Rev. 9/
-------
TABLE OF CONTENTS
Page
SECTION I - INTRODUCTION EXT D-l
SECTION II - SAMPLE STORAGE AND PREPARATION EXT D-3
SECTION III - SCREENING FOR EXTRACTABLE TARGET COMPOUNDS EXT D-17
SECTION IV - GC/MS ANALYSIS OF EXTRACTABLE TARGET COMPOUNDS EXT D-21
Rev. 9/88
-------
SECTION I
INTRODUCTION
The samples received for high concentration analysis will consist of three
types of phases: solids, water immiscible liquids, and water miscible
liquids. It is also possible to receive samples that will be multiple phase
such as soil, water and oil in the same sample jar. Because of this
possibility, the samples are to be "phase separated" into their individual
phases. The weight of the aliquot of each phase analyzed, and the phase type
are recorded on appropriate data sheets and reported with the sample data.
The phase separation techniques employed will vary according to the types of
samples received. Since it is impossible to know the number and types of
phases that will be present in a sample, the choice of phase separation
techniques is left to the discretion of the analyst. "Various techniques can
be employed to separate the phases. These include pipetting off liquid
phases (decanting should not be done), centrifuging to remove suspended
solids, use of spatulas to remove solids (wooden tongue depressors work
well). All operations should be done with disposable phthalate-free labware.
This eliminates the problem of cleaning contaminated glassware. The separate
phases should be stored into glass containers with teflon-lined screw caps.
This allows for storage and handling of the waste in a safe manner. Under no
circumstances are samples to be homogenized to eliminate separate phases:
Each individual phase is treated as a subsample, and is taken through the
separate GC/MS and GC/ECD procedures as a sub-sample. The results of each of
the analyses are to be reported for each phase of the sample.
The analytical methods that follow are designed to analyze the organic
compounds on the Target Compound List (TCL) (See Exhibit C). The methods are
divided into the following sections: sample preparation, screening, and
analysis. Sample preparation covers sample storage.
EXT D-l
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1• Method For The Determination of Extractable Organic Compounds
1.1 Scope and Application
These procedures are designed for the preparation of waste samples
which may contain organic chemicals at a level greater than 20 mg/kg.
1,1.1 The extracts prepared using these methods are screened by
GC/FXD for Base/Neutrals, Acids and Pesticides/PCBs target
compounds. The results of these screens will determine whether
sufficient quantities of pollutants are present to warrant
analysis by the high or low/medium protocol.
EXT D-2
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SECTION II
SAMPLE STORAGE AND PREPARATION
EXT D-3
Rev. 9/88
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PART A - SAMPLE STORAGE
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 4°C (+2°C) for the periods specified in
the contract schedule.
PART B - SAMPLE PREPARATION FOR EXTRACTABLES
1. Summary of Method
Approximately 1.0 g portions of the single phase unit are transferred
to vials and extracted with methylene chloride and are cleaned-up using
GPC. The methylene chloride extract, prepared using Gel Permeation
Chromatography may be prepared in methylene chloride or a 1:1 mixture
of methylene chloride/butyl chloride, at the option of the laboratory,
prior to GPC cleanup. Following GPC cleanup, a 1 il aliquot of the
collected fraction is screened for target compounds by GC/F1D (See
Section 9). If organic compounds are detected by the high level
screen, the methylene chloride extract is analyzed by GC/MS for the
extractable target compounds listed in Exhibit C. If organic compounds
are not detected by the high level screen, contact SMO immediately.
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 must be routinely demonstrated to be
free from interferences under the conditions of the analysis by running
laboratory method blanks. Matrix interferences may be caused by
contaminants that are coextracted from the sample. The extent of
matrix interferences will vary considerably from source to source,
depending upon the nature and diversity of the samples.
3. Limitations
3.1 The extraction procedure is designed to allow detection limits for
screening purposes as low as 20 mg/kg for Base/Neutrals, Acids,
chlorinated pesticides and individual PCB congeners. For analysis
purposes, the detection limits for Base/Neutrals, Acids, chlorinated
pesticides and individual PCB congeners range from 20-200 mg/Kg (see
Ex. C). The pesticides and PCBs tend to have low responses when using
a GC/FID detector. Peaks that are present where pesticides and PCBs
may elute must be viewed with extra caution; the concentration may be
higher than the response would indicate. If peaks are present in the
GC/FID screens, high level analysis by GC/MS is required. Some samples
may contain high concentrations of chemicals that interfere with the
analysis of other components at lower levels.
EXT D-4
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3.2 These extraction and preparation procedures were developed for rapid
and safe handling of high concentration hazardous waste samples. The
design of the methods does not stress efficient recoveries or low
limits of detection 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 the
sample.
4. Reagents
4.1 Sodium Sulfate - Powdered anhydrous and reagent grade, heated at 400°C
for four hours, cooled in a desiccator, and stored in a glass bottle.
Baker anhydrous powder, catalog number 73898 or equivalent.
4.2 Methylene chloride - Pesticide residue analysis grade, or equivalent.
4.3 Methanol - Pesticide residue analysis grade, or equivalent.
4.4 Toluene - Pesticide residue analysis grade, or equivalent.
4.5 Benzene - Pesticide residue analysis grade, or equivalent.
4.6 Butyl chloride (1-chlorobutanol) - Analytical reagent grade, or
equivalent (optional).
4.7 Base/Neutral and Acid Surrogate Standard Spiking Solution
Prepare a solution in methanol containing the following compounds at a
concentration of 1000 ug/mL for base/neutral surrogates, and 2000 ug/mL
for the acid surrogate standards:
4.8 Base/Neutral and Acid Control Matrix Spiking Solution.
Prepare a spiking solution in methanol that contains the following
compounds at a concentration of 1000 ug/mL for base/neutrals and 2000
ug/mL for acids;
Base/Neutrals
Acids
nitrobenzene-d^
p - terpheny 1 - d^
2-fluorobiphenyl
phenol-d
2,4,6-tr
2-fluorophenol
phenol
Base/Neutrals
Acids
1,2,4-trichlorobenzene
acenaphthene
2,4-dinitrotoluene
pyrene
N-nitroso-di-n-propylamine
1,4-dichlorobenzene
pentachlorophenol
phenol
2-chlorophenol
4-chloro- 3-me thylpheno1
4-nitrophenol
EXT D-5
Rev. 9/88
-------
4.9
Pesticide/PCB Control Matrix'Spiking Solution,
Prepare a spiking solution in methanol that contains the following
pesticides in the concentrations specified:
Pesticide
ug/roL
heptachlor
dieldrin
1,000
1,000
4.10 Corn oil.
4.11 Purified solid matrix, supplied by EMSL/LV upon availability.
5. Apparatus and Materials
5.1 Glass vials, at least 20 mL, with screw cap and teflon or aluminum foil
liner.
5.2 Spatula - Stainleiss steel or teflon.
5.3 Balance capable of weighing 100 g to the nearest 0.01 g.
5.4 Vials and caps, 2 mL for GC auto sampler.
5.5 Disposable Pasteur pipets, packed with glass wool rinsed with methylene
chloride.
5.6 15-mL.concentrator tubes.
5.7 Ultrasonic cell disruptor, Heat Systems Ultrasonics, Inc., Model W-385
SONICATOR (475 Watt with pulsing capability, No. 200 1/2 inch tapped
disruption horn, No. 419 1/8 inch standard tapered MICROTI? 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.
5.8 Sonabox acoustic enclosure - recommended with above disruptors for
decreasing cavitation sound.
5.9 Test tube rack.
5.10 Pyrex glass wool.
5.11 pH paper range 1-14. (Fischer Part No. A979 wide range test ribbons or
equivalent).
6. Sample Preparation.
6.1 Transfer approximately 1 g of each phase (record weight to the nearest
0.1 g) of the sample to separate 20 mL vials. Wipe the mouth of the
EXT D-6
Rev. 9/88
-------
vial with a tissue before weighing to remove any sample material. Cap
the vial before proceeding with the next sample to avoid any cross
contamination.
6.1.1 Prepare a 1.0 g control matrix consisting of corn oil.
6.1.2 Prepare a 1.0 g method blank consisting of purified solid
matrix. (May be available through EMSL/LV).
6.1.3 Determine pH of sample with pH paper. (Add 1 mL of water to 1
g of soil or water immiscible liquid and shake. Decant water
portion and measure pH of water with pH paper.)
6.2 Add 100 uL surrogate spiking solution to each sample, blank and the
control matrix.
6.3 Add 100 uL of each control matrix standard spiking solution to the
control matrix.
6.4 Add 2.0 g of powdered anhydrous sodium sulfate to sample.
6.5 Immediately add 10 mL of methylene chloride to the sample.
6.6 Disrupt the sample by ultrasonic probe for 2 minutes at 100 watts
power.
6.7 Loosely pack disposable Pasteur pipets with 2-3 cm glass wool plugs.
Filter the extract through the glass wool and collect a minimum of 8.0
mL of the extract in a concentrator tube.
6.8 Proceed to extract clean-up by GPC, Section 7.
7. Apparatus and Materials for Gel Permeation Chromatography fGPC) Clean
UlL.
7.1 Beakers, 400 mL.
7.2 Kuderna-Danish (K-D) apparatus.
7.2.1 Concentrator tube - 10 mL, graduated (Kontes K-570040-1029 or
equivalent).
7.2.2 Evaporative flask - 500 mL (Kontes K-570001-0500 or
equivalent).
7.2.3 Snyder column - three-ball macro (Kontes K-503000-0121 or
equivalent).
7.2.4 Snyder column - two ball micro (Kontes K-569001-0219 or
equivalent).
7.3 Silicon carbide boiling chips - approximately 10/40 mesh. Heat to
400°C for 30 minutes or Soxhlet extract with methylene chloride.
EXT D-7
Rev. 9/88
-------
7.4 Water bath - heated, with concentric ring cover, capable of temperature
control (±2"C). The bath should be used in a hood.
7.5 Top loading balance, capable of accurately weighing 0.01 g.
7.6 Balance - Analytical, capable of accurately weighing 0.0001 g.
7.7 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.
7.8 0.45 micron teflon membrane filter, stainless steel and/or teflon
filter holder with a 13 to 25 diameter (Millipore, Schleicher and
Schuell or equivalent).
7.9 Syringes, 10 mL glass with luer lock tip.
7.10 Gel permeation chromatography cleanup device. (Automated system.)
7.10.1 Gel permeation chromatograph (GPC) Analytical Biochemical Labs,
Inc., Columbia, MO, GPC Autoprep 1002 or equivalent.
7.10.2 25 mm ID X 700 mm glass column.
7.10.3 Optional 5 cm guard column (Supelco 5-8319 or equivalent) with
appropriate fittings to connect to the inlet side of the
analytical column.
7.10.4 70 g 200-400 mesh Bio Beads (S-X3), Bio Rad Laboratories,
Richmond, CA Catalog 152-2750 or equivalent (an additional 5 g
of Bio Beads is required if the optional guard column is
employed).
7.10.5 Fixed wavelength ultraviolet detector (254 nm) with a semi-prep
flow-through cell.
7.10.6 Strip chart recorder.
8. Reagents
8.1 Methylene chloride, pesticide residue analysis grade, or equivalent.
8.1.1 Some brands of methylene chloride may contain unacceptably high
levels of acid (HC1). Check the pH by shaking equal portions
of methylene chloride and water, then check the pH of the water
layer.
If the pH of the methylene chloride is less than or equal to 5,
filter the solvent through a 2 in. X 15 in. glass column
containing activated basic alumina. This column should be
sufficient for processing approximately 20-30 liters of
solvent. Alternatively a different source of methylene
chloride should be found.
EXT D-8
Rev. 9/88
-------
8.2 Cyclohexane, pesticide residue analysis grade, or equivalent.
8.3 GPC solution
8.3.1 Calibration solution prepared in methylene chloride containing
the following analytes (in order of elution):
8.3.2 Store the calibration solution in an amber glass bottle with a
teflon lined scrtew cap at 4°C, and protect from light.
(Refrigeration may cause the corn oil to precipitate. Allow
the calibration solution to stand at room temperature until the
corn oil dissolves.) Replace the calibration standard solution
as necessary or a minimum of every 3 months.
9. Extract Cleanup
The GC screen may be performed before the GPC column cleanup. The
results from the screen will indicate" how much sample should be loaded
onto the GPC column so as not to contaminate the column and, at the
same time, have enough extract for GC/MS analysis. This will preserve
the life of the GPC column since these columns are easily contaminated
by high concentration samples.
9.1 GPC Setup and Calibration
9.1.1 Column Preparation
9.1.1.1 Weight 70.0 g (75.0 g if using optional guard
column) of Bio Beads (S-X3) into a 400 mL beaker.
9.1.1.2 Add an excess quantity of a 1:3 (v/v mixture) of
methylene chloride/cyclohexane to ensure that the
beads will be completely submerged during the
swelling process. Cover the beaker to prevent
solvent evaporation and allow the beads to swell for
a minimum of 16 hours.
9.1.1.3 Prepare a slurry of approximately 50% swelled beads
and 50% solvent. Turn the column upside down from
its normal position, and remove the inlet bed
support plunger (the inlet plunger is longer than
the outlet plunger). Position and tighten the
outlet bed support plunger as near to the column end
as possible (approximately 2.5 cm from the end).
polystyrene (MW 300,000)
mg/mL
2.8 (Optional)
corn oil
b is(2 -ethylhexyl)phthalate
pentachlorophenol
perylene
60.0
3.0
0.3
0.02
EXT D-9
Rev. 9/88
-------
9.1.1.4 Ensure that the outlet stopcock is closed. Place a
small amount of solvent in the column to minimize
the formation of air bubbles at the base of poured
column packing. Swirl the bead/solvent slurry to
get a homogeneous mixture, and quickly and
consistently pour the swelled slurry into the glass
column. Never allow the beads to settle completely
while pouring the column. A glass rod can be used
to facilitate pouring the mixture down the side of
the column and to help minimize bubble formation.
Use additional solvent to rinse the beaker and
transfer all of the beads to the column.
9.1.1.5 When the transfer solvent has drained into the
column bed, the inlet bed support plunger can be
used to temporarily compress the gel bed. Do not
tighten the column/plunger seal if beads are caught
between it and the glass column. Remove the plunger
and rinse it and the sides of the glass column with
minimal solvent. A clean paper towel can be used to
remove any remaining beads.
9.1.1.6 Insert the inlet bed support bed plunger, compress
the gel bed approximately 1 cm and tighten.
9.1.1.7 Pack the optional 5 cm guard column with
approximately 2-3 g of the remaining pre-swelled
beads (different guard columns may require different
amounts.) . Connect the guard column to the inlet of
the analytical column.
9.1.1.8 Connect the column inlet to the solvent reservoir
(reservoir should be placed higher than the top of
the column) and place the column outlet tube in a
waste container. Pump methylene chloride through
the column at a rate of 5 mL/min for 1 hour. While
the solvent in the column is being changed from
methylene chloride/cyclohexane to methylene chloride
only, the gel may pack down or undergo additional
swelling, which will change the pressure.
9.1.1.9 After washing the column for at least one hour.,
connect the column outlet tube to the inlet side of
the UV detector. Connect the system outlet to the
outlet side of the UV detector. While still pumping
methylene chloride through the column, adjust the
inlet bed support plunger until approximately 6-10
psi backpressure is achieved.
9.1.1.10 When the GPC column is not used for several days,
evaporation of methylene chloride may cause column
drying, which can cause stratification or channeling
in the gel. To prevent this drying, connect the
column outlet line to the column inlet. This will
EXT D-10
Rev. 9/88
-------
allow a continuous recycling of Che solvent when the
system is not in use. If channeling occurs, the gel
must be removed from the column, reswelled, and
repoured as described above. If drying occurs,
methylene chloride should be pumped through the
column until the observed column pressure is
constant and the same as when the column was new.
9.1.2 Calibration of the GPC column
9.1.2.1 Using a 10 mL syringe, load sample loop #1 with
calibration solution (8.3.1). With the ABC automated
system, the 5 mL sample loop requires a minimum of 8
mL of the calibration solution. Use a firm,
continuous pressure to push the sample onto the
loop.
9.1.2.2 Inject the calibration solution and obtain a UV
trace showing a discrete peak for each component.
Adjust the detector and/or recorder sensitivity to
produce a UV .trace similar to Figure 1 that meets
the following requirements. Differences between
manufacturer's cell volumes detector sensitivities
may require a dilution of the calibration solution
to achieve similar results. An analytical flow-
through detector cell will require a much less
concentrated solution than the semi-prep cell, and
therefore the analytical cell is not acceptable for
use.
UV Trace Requirements:
o Peaks must be observed for all compounds
in the calibration solution.
o Perylene peaks must not be saturated and
must exhibit baseline resolution.
o Corn oil and phthalate peaks must exhibit
baseline resolution.
9.1.2.3 Using the information from the UV trace, establish
appropriate collect and dump time periods to ensure
collection of all target analytes. Initiate column
eluate collection just before elution of bis(2-
ethylhexyl)phthalate (approximately 30 minutes) and
after the elution of the corn oil (approximately 20
minutes). Stop eluate collection shortly after the
elution of perylene (approximately 50 minutes).
Collection should be stopped before sulfur would
elute, if it were present (approximately 55
minutes). Each laboratory is required to establish
its specific time sequences. The times provided are
for general guidance only.
EXT D-11
Rev. 9/88
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NOTE: The collect and dump times must be adjusted to
compensate for the difference in volume of the lines
between the UV detector cell and the collection
flask.
9.1.2.6 Verify the flow rate by collecting column eluate for
10 minutes in a graduated cylinder and measure the
volume, which should be 45-55 mL <4.5-5.5 mL/min).
If the flow rate is outside of this range,
corrective action must be taken, as described above.
Once the flow rate is within the range of 4.5-5.5
mL/min, record the column pressure and room
temperature. Changes in pressure, solvent flow
rate, and temperature conditions can affect analyte
retention times and must be monitored.
9.1.2.7 Reinject the calibration solution after appropriate
collect and dump cycles have been set and the
solvent flow and column pressure have been
established.
9.1.2.7.1 Measure and record the volume of
collected GPC eluate in a graduated
cylinder. The volume of GPC eluate
collected for each sample extract
processed may be used to indicate
problems with the system during sample
processing.
9.1.2.7.2 The retention times for bis(2-
ethylhexyl)phthalate and perylene must
not vary more than plus or minus 5%
between calibrations. If the retention
time shift is greater than 5%, take
corrective action.
9. 2 GPC Extract Cleanup
9.2.1 Studies have demonstrated that the recovery of certain aromatic
compounds is improved when samples are introduced into the GPC
in a 1:1 solvent mixture of methylene chloride/butyl chloride.
If it is used, reduce the 8.0 mL sample volume to 3.5-4.0 mL
under a stream of dry nitrogen (Paragraph 8.4.3). Reconstitute
to the 8.0 mL volume with butyl chloride. Thoroughly mix the
sample before proceeding.
9.2.2 Pre-filter each sample extract through a 0.45 micron PTFE
filter (Millipore, Schleicher and Schuell or equivalent).
Samples that contain suspended particles must be centrifuged
prior to filtration. Clean the filter holder assembly between
s amp1e s.
EXT D-12
Rev. 9/88
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9.2.3 Using a 10 mL syringe, load the nominal 5 mL sample loop.
CAUTION: Approximately 2 mL of the extract remains in the
lines between the injection port and the sample loop; excess
sample also passes through the sample loop to waste.
Attach the syringe to the turn lock on the injection port. Use
firm, continuous pressure to push the sample onto the loop. If
the sample is difficult to load, some part of the system may be
blocked. Take appropriate corrective action.
9.2.4 After loading a loop, and before removing the syringe from the
injection port index the GPC to the next loop. This will
prevent loss of sample caused by unequal pressure in the loops.
9.2.5 After loading each sample loop, wash the loading port with
methylene chloride in a PTFE wash bottle to minimize cross
contamination. Inject approximately 10 mL of methylene
chloride to rinse the common tubes.
9.2.6 Column overloading.
9.2.6.1 Column overloading can occur when too much material
is loaded in a sample loop.
9.2.6.1.1 For highly contaminated samples, dilute
the extract and process in more than
one sample loop. An example dilution
procedure is to mix 10 mL of sample
extract with 10 mL of methylene
chloride or 1:1 butyl
chloride/methylene chloride, shake well
to thoroughly mix, and load into two
sample loops.
9.2.6.1.2 After GPC cleanup, combine the
collected fractions and treat as a
single sample. Therefore, no
additional dilution factor will be
required when a sample extract is
diluted and divided for GPC cleanup.
9.2.7 After loading all the sample loops, index the GPC to the 00
position, switch to the "run" mode and start the automated
sequence.
9.2.8 Process each sample using the collect and dump cycle times
established in 9.1.2. Process calibration standards, control
matrix (GPC blank), samples and method blanks in the following
order:
EXT D-13
Rev. 9/88
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Loop 1 Calibration Standard.
Loop 2 Control Matrix (corn oil)
Loop 3-22 Samples
Loop 23 Calibration Standard (Verification)
NOTE: GPC cleanup sequence must end with a calibration
standard verification regardless of the number of samples
processed.
9.2.9 Collect each sample in a 250 mL Erlenmeyer flask, covered with
aluminum foil to reduce solvent evaporation. Monitor sample
volumes collected. Do not concentrate the processed GPC
extract at this point. Changes in sample volumes collected may
indicate one or more of the following problems:
9.2.9.1 Change in solvent flow rate, caused by channeling in
the column or changes in column pressure.
9.2.9.2 Increase in column operating pressure due to the
absorbtion of particles or gel fines onto either the
guard column or the analytical column gel, if a
guard column is not used.
9.2.9.3 Leaks in the system or significant variances in room
temperature.
9.2.10 Evaluation of calibration standards.
9.2.10.1 Evaluate the retention times for bis(2- •
ethylhexyl)phthalate and perylene in each daily
calibration standard UV trace. The retention time
for either compound cannot exceed a 5% retention
time shift when compared to the retention time
established in the initial calibration (loop 1).
9.2.10.2 Corrective action must be taken before sample
cleanup can proceed. All samples processed prior to
an unacceptable calibration verification must be
identified in the case narrative.
9.2.10.3 Acceptable GPC performance is demonstrated by the
successful analysis of the calibration standard
solution. Corrective actions may include those
listed in 9.1.1 and 9.1.2 above or may require
repacking and recalibration of the column.
9.3 Transfer a 1.0 mL aliquot of the processed extract to a GC vial. Do
not discard the remaining extract until the GC/FID screen has been
performed. Proceed to GC/FID screen, Section III.
9.3.1 For the control matrix sample and method blank, concentrate the
extract (9.4).
EXT D-14
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9.3.2 Store all extracts at 4*C In the dark in teflon-sealed
containers until all analyses are performed.
9.4 If no sample peaks are detected or all are less than 10% full scale
deflection during the GC/FID screen, the sample must be concentrated.
The control matrix samples and the method blanks are also concentrated.
9.4.1 Transfer the extract (9.2.9) 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.
9.4.2 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.
9.4.3 Nitrogen blowdown technique (taken from ASTM Method D 3086).
The following method must be used for final concentration of
the extracts. 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, since it may introduce
interferences. The internal wall of the tube must be rinsed
down several times with methylene chloride during the
operation, and the final volume brought to 1.0 mL with
methylene chloride. During evaporation, the tube solvent level
must be just above the water level of the bath. The extract
must never be allowed to become dry.
9.5 Store all extracts at 4°C in the dark in teflon-sealed containers until
all analyses are performed.
EXT D-15
Rev. 9/88
-------
88/6 'ASH 91-Q XX3
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UV Detector Response, millivolts
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Polystyrene MW 300,000 14 mg
Corn Oil 300 mg
Bis[2-ethylhexyllphthalate 15 mg
Pentachlorophenol 1.4 mg
Perylene 0.1 mg
-------
SECTION III
GC/FID SCREENING FOR EXTRACTABLE TARGET COMPOUNDS
EXT D-17
Rev. 9/88
-------
1.
Summary of Method
The solvent extracts of the single phase units 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
volume 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 splitless injection using capillary columns.
2.1.1 Above GC equipped with a flame ionization detector.
2.1.2 GC column - 30 i 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 stock-standard solution containing
phenol, phenanthrene, and di-n-octylphthalate in methylene chloride.
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.
3.2.1.2 Transfer the stock standard solutions into teflon-
sealed screw-cap bottles. Stored standard solutions
should be checked frequently for signs of
degradation or evaporation, especially just prior to
preparing calibration standards from them. Stock
standard solutions must be replaced after six months
or sooner if comparison with quality control check
samples indicates a problem.
EXT D-18
Rev. 9/88
-------
3.2.1.3 Prepare a working standard of the GC calibration
standard 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 met:
4.1.1 Standardized for 50% full scale response for 50 ng of
phenanthrene.
4.1.2 Adequately separates phenol from the solvent front.
4.1.3 Minimum of 25% full scale response for 50 ng of di-n-
oc tylphthalate.
5. GC/FID Screening
5.1 Suggested GC operating conditions:
Initial Column Temperature Hold - 50°C for 4 minutes.
Column Temperature Program - 50" to 280°C at 8 degrees per minute.
Final Column Temperature Hold -280*C for 8 minutes.
Injector - Grob-type; splitless.
Sample Volume - 1 uL to 2 uL.
Carrier Gas - Helium at 30 cm per sec.
5.2 Inject the GC calibration standard and ensure the criteria specified in
4.1 are met before Injecting samples. Estimate the response for 10 ng
of phenanthrene.
5.3 Inject the extracts of all single phase units to be screened, including
blanks (Section II, paragraphs 9.3 and 9.4).
6. Interpretation of Chromatoerams
6.1 If no sample peaks from the extract are detected or all are less than
10% full scale deflection, the sample must be concentrated as per
Section II (9.4), rescreened, and analyzed by GC/MS. If no peaks are
detected or all are less than 10% full scale deflection after
concentration, contact the Sample Management Office for instructions.
6.2 If peaks are detected at greater than 10% deflection and less than or
equal to 100% full scale deflection, proceed with GC/MS analysis of
this extract with appropriate dilution if necessary.
EXT D-19
Rev. 9/88
-------
If peaks are detected at greater than 100% full scale deflection,
calculate the dilution necessary to reduce the major peaks to between
50% and 100% full scale deflection. Use this dilution factor to dilute
the extract for GC/MS analysis.
EXT D-20
Rev. 9/88
-------
SECTION.IV
GC/MS ANALYSIS OF EXTRACTABLE TARGET COMPOUNDS
EXT D-21
Rev. 9/88
-------
1, Summary of Method
This method is to be used for the GC/MS analysis of extractable
extracts screened by Section III protocols.
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 510 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 (DFTPF) is injected through the GC
inlet (Exhibit E, Table E-l).
NOTE: DFTFP 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 additional 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^, napthalene-dg,
acenaphthene-d^Q, phenanthrene-d-^Q, chrysene-d-^ , perylene-d-^. 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% 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
EXT D-22
Rev. 9/88
-------
4000 ng/uL. A 10 uL portion of this solution should be added to each 1
mL of sample extract. This will give a concentration of 40 ng/uL of
each constituent.
3.2 Target Compound Calibration Standards
3.2.1 Prepare calibration standards at a minimum of three
concentration levels. Each calibration standard shall contain
each compound of interest and each surrogate standard. See
GC/MS calibration in Exhibit E (Section 2.1.1) for calibration
standard concentration.
^¦ Calibration
4.1 Great care must be taken to maintain the integrity of all standard
.solutions. It is recommended that all standard solutions be stored at
4°C or less in screw cap amber bottles with teflon liners. Fresh
standards should be prepared every six months at a minimum.
4.2 Each GC/MS system must be hardware tuned to meet the criteria listed in
Table E-1 in Exhibit E for a 50 ng injection of
decafluorotriphenylphosphine (DFTPP). 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.
4.3 The internal standards selected in paragraph 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 Table D-5. If interferences are noted, use the next most intense
ion as the secondary ion, i.e. For 1,4-dichlorobenzene-d^ use m/z 115
for quantification.
4.3.1 The internal standards are added to all sample extracts just
prior to analysis by GC/MS and to all calibration standards. A
10 uL aliquot of the internal standard solution should be added
to a 1 mL aliquot of calibration standards.
4.4 Target Compound Relative Response Factors
4.4.1 Analyze 1 to 2 uL of each calibration standard and tabulate the
area of the primary characteristic ion (Table D-l) against
concentration for each compound including¦the surrogate
compounds. Calculate relative response factors (RRF) for each
compound using Equation 1.
EXT D-23
Rev. 9/88
-------
Equation 1, j^p _ ^ X ^is
Ais Cx
Where:
A^. - Area of the characteristic ion for the compound to
be measured.
Ais ~ Area of the characteristic ion for the specific
internal standard from Exhibit E.
C£s — Concentration of the internal standard (ng/uL),
Cx - Concentration of the compound to be measured
(ng/uL).
4.4.2 The average relative response factor (R£F) should be calculated
for all compounds. A system performance check must be made
before this calibration curve is used. Four system performance
check compounds (SPCCs) are checked for a minimum average
response factor. These compounds are N-nitroso-di-n
propylamine, hexachlorocyclopentadiene, 2,4-dinitrophenol, 4-
nitrophenol. The minimum acceptable average relative response
factor for extractable System Performance Check Compounds is
0.050.
4.4.3 A maximum % Relative Standard Deviation (% RSD) of 30.0% for
the thirteen Calibration Check Compounds (CCC) must be met for
the calibration curve to be valid (see Exhibit E, Section III,
2.3.2) .
4.4.4 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 HCE. The minimum
response factor for the system performance check compounds - is
0.050. If this criteria is met, the response factor of all
compounds is calculated. A percent difference of the daily
response factor (12 hour) compared to the average response
factor from the initial curve is calculated. A maximum percent
difference of 25.0% 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 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 malfunction
and corrections made as required. 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) calibration
standard, 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.
EXT D-24
Rev. 9/88
-------
Retention times and EICP areas are reported on Form VIII.
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 510 amu
Scan Time - 1 second per scan
5.2 Internal standard solution is added to each sample extract. Add 10 uL
of internal standard solution to 1.0 mL (accurately measured) of sample
extract.
NOTE: Make appropriate extract dilutions as indicated by the screening
procedure prior to the addition of internal standards. If any further
dilutions of the extracts are made, additional internal standards must
be added to maintain the required 40 ng/uL of each constituent in the
extract volume. If any compound saturates the detector, the extract
must be diluted and reanalyzed.
Analyze an aliquot of 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 - 30°C for 4 minutes
Column Temperature Program
Final Column Temperature Hold
Injector Temperature
Transfer Line Temperature
Source Temperature
Injector
Injection Volume
Carrier Gas
6• Qualitative Analysis
6.1 Single Component Extractable Target Compounds
6.1.1 The single component target compounds, listed in Exhibit C,
shall be identified 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.
- 30° to 300°C at 8 degrees per
minute
- 300°C for 10 minutes
- 250° to 300°C
- 250° to 300°C
- According to manufacturer's
specifications
- Grob Type, Splitless
- 1 to 2 uL
3
- Helium at 30 cm /min
EXT D-25
Rev. 9/88
-------
6.1.2 For establishing correspondence of the GC relative retention
time (RK.T), the sample component RRT must compare within +0.05
of the RRT of the standard component. For reference, the
standard must be run on the same shift as the sample. The RRT
should be assigned by using extracted ion current profiles for
ions unique to the component of interest.
6.1.3 For comparison of standard and sample component mass spectra,
mass spectra obtained on the Contractor's GC/MS are required.
Once obtained, these standard spectra may be used for
identification purposes, only if the Contractor's GC/MS meets
the DFTPP daily tuning requirements. These standard spectra
may be obtained from the run used to obtain reference RRTs.
6.1.3.1. The requirements for qualitative verification by
comparison of mass spectra are as follows:
(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.
(2) The relative intensities of ions
specified in (1) must agree within +20%
between the standard and sample spectra.
(Example: For an ion with an abundance
of 50% in the standard spectra, the
corresponding sample ion abundance must
be between 30 and 70%.)
(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.
The verification process should favor
false positives.
6.2 PCB Congener Analysis
6.2.1 PCB's are identified and measured by level of chlorination.
Concentration is measured for each PCB isomer group.
The ten individual PCB congeners listed in Table D-2 are used
as concentration calibration compounds for PCB determinations.
One isomer at each level of chlorination is used as the
concentration calibration standard for all isomers at that
level of chlorination.
EXT D-26
Rev. 9/88
-------
6.2.2 Identification and measurement
Special software can be used for automated identification and
measurement of PCBs. Unprocessed GC/MS data are handled
without human interaction with the software operationg on the
dedicated computer. A concentration for each PCB isomer group
is calculated automatically.
Examine each PCB candidate spectrum after background correction
routines have been applied. Verify the absence of any ions
with mass greater than the highest mass possible for the
compound of concern. (Ions in PCB M+ ion clusters are shown in
Table D-3).
6.2.2.1 For all PCB candidates, confirm the presence of an
(M+70)+ ion cluster by examining ICPs or spectra for
at least one of the most intense ions in the
appropriate ion cluster.
6.2.2.2 For CI3-CI7 isomer groups, examine the extracted ion
current profiles (EICPs) or spectra for intense
(M+70)+ ions that would indicate a coeluting PCB
containing two additional chlorines.
6.2.2.3 For C^-Clg-PCB candidates, examine ICPs or spectra
for intense (M+35)+ ions that would indicate a
coeluting PCB containing one additional chlorine.
This coelution causes interferences because of the
natural abundance of C. (This interference will
be small and can be neglected except when measuring
the area of a small amount of a PCB coeluting with a
large amount of another PCB containing one more
chlorine).
6.2.2.4 Use ICP data to calculate the ratio of the measured
peak areas of the quantitation ion and confirmation
ion(s), and compare to the acceptable ratio (Table
D-3). If acceptable ratios are not obtained, a
coeluting or partially coeluting compound may be
interfering.
6.2.2.5 Quantitation and confirmation ions for each PCB
isomer group must maximize within +1 scan of each
other.
6.2.2.6 The integrated ion current for each quantitation and
confirmation ion must be at least three times
background noise and must not have saturated the
detector.
6.2.2.7 For each PCB isomer group candidate, the ratio of
the quantitation ion area to the confirmation ion
EXT D-27
Rev. 9/88
-------
area must be within limits shown in Table D-3; at
least one ion in the (M-70)+ ion cluster must be
present.
6.3 A library search shall be executed for non-target compound sample
components for the purpose of tentative identification. For this
purpose, the most recent available version of the EPA/NBS Mass Spectral
Library should be used.
6.3.1 Up to 20 nonsurrogate organic compounds of greatest apparent
concentration not listed in Exhibit C for the extractable
fraction shall be tentatively identified via a forward search
of the EPA/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
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.
6.3.2 Guidelines for making tentative identification:
(1) Relative intensities of major ions in the reference
spectrum (ions greater than 10% of the most
abundant) should be present in the sample spectrum.
(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%.
(3) Molecular ions present in reference spectrum should
be present in sample spectrum.
(A) Ions present in the sample spectrum but not in the
reference spectrum should be reviewed for possible
background contamination or presence of coeluting
compounds.
(5) Ions present in the reference spectrum bur. not in
the sample spectrum should be reviewed for possible
subtraction from the sample spectrum because of
background contamination or coeluting compounds.
Data system library reduction programs can
sometimes create these discrepancies.
6.3.3 If in the opinion of the mass 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
EXT D-28
Rev. 9/88
-------
type, unknown chlorinated compound). If probable molecular
weights can be distinguished, include them.
7. Quantitation
7.1 Target Compound Quantitation
7.1.1 The target compounds components identified shall be quantified
by the internal standard method. The internal standard used
shall be the one assigned in Table E-3, in Exhibit E. The EICP
area of characteristic ions of analytes listed in Tables D-l,
D-3, and D-5 are used. The relative response factor (RRF) from
the daily standard analysis is use;d 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 response
factor is calculated using the secondary ion.
7.1.1.1 Calculate the concentration in the sample using the
relative response factor (RRF) as determined in
paragraph 4.4 and the following equation:
- f- /v (Av)
-------
7,2.1 The formula for calculating concentrations is the same as in
paragraph 7.1.1.1. Total area counts 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.
7.3 Calculate surrogate standard recovery on all samples, control matrix
spikes, and method blanks. Determine if recovery is within the
suggested limits and report on appropriate form.
7.3.1 If recovery is not within the suggested limits for a sample,
the following is required:
7.3.1.1 Check to be sure there are no errors in
calculations, surrogate solutions and internal
standards. Also, check instrument performance.
7.3.1.2 Recalculate the data and/or reanalyze the extract if
any of the above checks reveal a problem.
7.3.1.3 If surrogates cannot be detected due to dilution
factors, the requirement in 7.3.1.2 need not be met.
7.3.2 Method Blank Surrogate Recoveries
If one or more surrogates are outside the contract required
limits (listed in Table E-5), the laboratory must take the
following actions:
7.3.2.1 Check to be sure there are no errors in
calculations, surrogate solutions and internal
standards. Also, check instrument performance.
7.3.2.2 Recalculate the data and/or reanalyze the extract if
any of the above checks reveal a problem.
7.3.2.3 If the above measures fail to correct the problem,
the analytical system must be considered out of
control. The method blank and all associated single
phase units, including control matrix spikes must be
re-extracted and reanalyzed at no additional cost to
the agency.
EXT D-30
Rev. 9/88
-------
TABLE D-l. Characteristic
Parameter
Phenol
bis(-2-Chloroethyl)ether
2-Chlorophenol
1.3-Dichlorobenzene
1.4-Dichlorobenzene
Benzyl Alcohol
1,2-Dichlorobenzene
2-MethyIpheno1
bis(2-chloroisopropyl)ether
4-MethyIpheno1
N-Nitroso-di-propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2,4-DimethyIpheno1
Benzoic Acid
b is(-2-Chloroethoxy)methane
2 ,4-Dichlorophenol
1.2.4-Trichlorobenzene
Naphthalene
4-Chloroaniline
Hexachlorobutadiene
4-Chloro-3-methylphenol
2-Methylnaphthalene
Hexachlorocyclopentadiene
2 ,4,6-Trichlorophenol
2.4.5-Trichlorophenol
2 -Chloronaphthalene
2-Nitroaniline
Dimethyl phthalate
Acenaphthylene
3-Nitroaniline
Acenaphthene
2,4-Dinitrophenol
4-Nitrophenol
Dibenzofuran
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diethylphthalate
4-Chlorophenyl-phenylether
Fluorene
4-Nitroaniline
4,6-Dinitro-2-methylphenol
N-Nitrosodiphenylamine
4-Bromophenyl-phenylether
Hexachlorobenzene
Ions for Extractable Target Compounds
Primary Ion Secondary Ion(s)
94 65, 66
93 63, 95
128 64, 130
146 148, 113
146 148, 113
108 79, 77
146 148, 113
108 107
45 77, 79
108 107
70 42, 101, 130
117 201, 199
77 123, 65
82 95, 138
139 65, 109
107 121, 122
122 105, 77
93 95, 123
162 164, 98
180 182, 145
128 129, 127
127 129
225 223, 227
107 144, 142
142 141
237 235, 272
196 198, 200
196 198, 200
162 164, 127
65 92, 138
163 194, 164
152 151, 153
138 108, 92
153 152, 154
184 63, 154
109 139, 65
168 139
165 63, 182
165 89, 121
149 177, 150
204 206, 141
166 165, 167
138 92, 108
198 182, 77
169 168, 167
248 250, 141
284 142, 249
EXT D-31
Rev. 1/89
-------
TABLE D-l, (Continued)
Parameter Primary Ion Secondary Ion(st
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(l,2,3-cd)pyrene
276
138,
227
Dibenz(a, h)anthracene
278
139,
279
Benzo(g, h, i)perylene
276
138,
277
Alpha-BHC
183
181,
109
Beta-BHC
181
183,
109
Delta-BHC
183
181,
109
Gamma-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'-DDD
235
237,
165
Endosulfan Sulfate
272
387,
422
4,4'-DDT
235
237,
165
Methoxyehlor
227
228
Ch1ordane-alpha
373
375,
377
Chlordane-gamma
373
375,
377
Endrin Ketone
317
67,
319
EXT D-32
Rev. 9/88
-------
TABLE D-2.
PCB Congeners Used as Calibration Standards
PCB Isomer Group
Concentration Calibration Standard
Monochlorobiphenyl
Dichlorobiphenyl
Trichlorob ipheny1
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyl
Octachlorobiphenyl
Nonachlorobiphenyl
Decachlorobiphenyl
IUPAC
Congener
Number
1
5
29
50
87
154
188
200
207
209
Chlorine Substitution of
Congener in
Calibration Standard
2
2,3
2,4,5
2,2',4,6
2,2',3,4,5'
2,2',4,4',5,6'
2,2',3,4',5,6,6'
2,2',3,3',4,5',6,6'
2,2',3,3',4,4',5,6,6'
2,2',3,3',4,4',5,5',6,6'
EXT D-33
Rev. 9/88
-------
TABLE D-3. Quantitation, Confirmation, and Interference Check
Ions and PCBs and Internal Standards
Analyte/ Nom. Quant, Confirm, Expected
IS MW Ion Ion Ratio3
M-70
Accept. Confirm.
Ratio3, Ion
Interference
Check Ions
M+70 M+35
PCB Isomer Group
Cli
188
188
190
3.0
2.5-3.5
15 2b
256
222
Cl2
222
222
224
1.5
1.3-1.7
152
292
256
Cl3
256
256
258
1.0
0.8-1.2
186
326
290
Cl4
290
292
290
1.3
1.1-1.5
220
360
326
els
324
326
324
1.6
1.4-1.8
254
394
360
C16
358
360
362
1.2
1.0-1.4
288
430
394
C17
392
394
396
1.0
0.8-1.2
322
464
430
Clg
426
430
428
1.1
0.9-1.3
356
498
464
Cl9
460
464
466
1.3
1.1-1.5
390
-
498
C110
494
498
500
1.1
0.9-1.3
424
-
-
Internal Standard
Chrysene-d^2
240 240
241
5,1
4,3-5.9
a Ratio of quantitation ion to confirmation ion.
Monodichlorobiphenyls lost HC1 to produce an ion at m/z 152.
EXT D-34
Rev. 9/88
-------
TABLE D-4.
Known Relative Abundances of Ions in PCB Molecular Ion Clusters
Relative
Relative
Relative
m/z
Intensity
m/z
Intensity
m/z
Intensity
Monochlorobiphenyls
Hexachlorobiphenyls
Nonachlorobiphenyls
188
100
358
50.9
460
26.0
189
13.5
359
6.89
461
3.51
190
33.4
360
100
462
76.4
192
4.41
361
13.5
463
10.3
362
82.0
464
100
Dichlorobiphenyls
363
11.0
465
13.4
222
100
364
36.0
466
76.4
223
13.5
365
4.77
467
10.2
224
66.0
366
8.92
468
37.6
225
8.82
367
1.17
469
5.00
226
11.2
368
1.20
470
12.4
227
1.44
369
0.15
471
1.63
472
2.72
Trichlorobiphenyls
Heptachlorobiphenyls
473
0.35
256
100
392
43.7
474
0.39
257
13.5
393
5.91
258
98.6
394
100
Decachlorobiphenyls
259
13.2
395
13.5
494
20.8
260, ¦
32.7
3.96
98.3
495
2.81
261
4.31
397
13.2
496
68.0
262
3.73
398
53.8
497
9.17
263
0.47
399.
7.16
498
100
400
17.7
499
13.4
Tetrachlorobiphenyls
401
2.34
500
87.3
290
76.2
402
3.52
501
11.7
291
10.3
403
0.46
502
50.0
292
100
404
0.40
503
6.67
293
13.4
504
19.7
294
49.4
Octaehlorobiphenyls
505
2.61
295
6.57
426
33.4
506
5.40
296
11.0
427
4.51
507
0.71
297
1.43
428
87.3
508
1.02
298
0.95
429
11.8
509
0.13
430
100
Pentachlorobiphenyls
431
13.4
324
61.0
432
65.6
325
8.26
433
8.76
326
100
434
26.9
327
13.5
435
3.57
328
65.7
436
7.10
329
8.78
437
0.93
330
21.7
438
1.18
331
2.86
439
0.15
332
3.62
440
0.11
333
0.47
334
0.25
Source:
J.W. Rote and W.J.
Morris, J.
Assoc. Anal.
Chera. 56, 188,
1973.
EXT D-
-35
Rev. 9/88
-------
TABLE D-5. Characteristic Ions for Surrogates and Internal
Standards for Extractable Target Compounds
Surrogates
Phenol-dj
2-Fluorophenol
2,4,6-Tribromophenol
Nitrobenzene-d^
2 -Fluorobiphenyl
Terphenyl-d^
Internal Standards
1,4-D ichlorobenzene-d^
Naphthalene-dg
Acenapthene-dg
Phenanthrene - d-^g
Chrysene-d^2
Perylene-d-^2
Primary Ion Secondary IonCs*)
99 42, 71
112 64
330 332, 141
82 128, 54
172 171
244 122, 212
152 115
136 68
164 162, 160
188 94, 80
240 120, 236
264 260, 265
EXT D-36
Rev. 9/88
-------
EXHIBIT D
GC/ECD ANALYSES OF AROCLORS AND TOXAPHENE
-------
1.
Summary of Method
1.1 The analytical method that follows is designed to determine the
concentration of Aroclors and Toxaphene (Target Compound List [Exhibit
C]) in high concentration samples. The method can be used for analyte
concentrations from the contract required quantitation limits (CRQL) to
one million times the CRQL in medium and high level waste matrices.
1.2 The Aroclors and Toxaphene listed in Exhibit C are determined by a two-
column GC/ECD technique.
1.3 This method specifies treatment of extracts with sulfuric acid and
potassium permanganate.
1.4 GC/ECD analysis begins with initial demonstration of instrument
performance and calibration of all Aroclors and Toxaphene. Acceptable
initial calibration is defined in Section 6.3. This must be repeated
whenever the required 12-hour performance evaluation test of Section
6.4.4 fails or when major instrument maintenance or modification is
performed.
1.5 Sample extracts must be analyzed within a run sequence as defined in
Section 6.4. At a minimum, the sequence consists of an initial
calibration check using Aroclor standards, method blank analysis,
sample extract analysis and periodic evaluation mixtures and instrument
blanks. (NOTE; Data can only be collected as long as the results for
the evaluation mixture and instrument blank fall within the limits
defined in Sections 6.4.3 and 6.4.4. If two consecutive unacceptable
evaluation standards are analyzed, all extracts with analytes present
at >CRQL which have been run since the previous acceptable evaluation
standard must be reanalyzed.) Additional evaluation mixtures and blanks
are recommended when highly contaminated samples are suspected.
1.6 Calibration and run sequence specifications for the GC method apply
separately to both columns.
1.7 One control matrix spike analysis must be run for every 20 single phase
units in a Case, or once per Case, whichever is more frequent.
1.8 Absolute retention times (RT's) are used for identification of Aroclors
and Toxaphene.
1.9 The absolute retention time window is calculated from the most recent
standard as ±1.0 percent of the RT of the standard.
1.10 Aroclors and Toxaphene are identified primarily by pattern recognition,
but RT's of three to five major peaks must also be taken into
consideration. Guidance on analysis of Aroclors and Toxaphene is given
in Section 6.7.
1.11 Quantitative analysis of Aroclors and Toxaphene must be accomplished by
the external standard method as described in Section 6.8. Three point
calibration curves for Aroclors and Toxaphene must be generated during
the initial calibration phase. A linear response range must be
ARO D-l
Rev. 9/88
-------
demonstrated from the CRQL Co a high point at least 30 times greater
than the CRQL.
1.12 Quantitative measurements are made from extracts which have been
diluted such that ECD response is within the established linear range
determined by the three-point calibration curve. Quantitation must be
performed and reported for both GC columns.
1.13 The surrogates, Tetrachloro-meta-xylene and Decachlorobiphenyl, must be
added to all samples, blanks, and control matrix spikes analyzed by
GC/ECD prior to extraction. The recovery the surrogates will be
determined in all of these samples and reported to the EPA as a measure
of method performance. The retention time shift of the surrogates in
any standard, sample, control matrix spike, or blank may not excede
0.5%.
1.14 Section 6.6 gives criteria which determine whether an analysis is
complete or whether additional cleanup or dilution is required.
1.15 All samples must be protected from light and refrigerated at 4°C from
the time of receipt until extraction.
2. Apparatus and Materials
2.1 Kuderna-Danish (K-D) apparatus.
2.1.1 Concentrator tube, 10 mL, graduated (Kontes K- 570040-1029, or
equivalent).
2.1.2 Evaporative flask, 500 mL (Kontes K-470001-0500, or
equivalent).
2.1.3 Snyder column, three-ball macro (Kontes K-503000-0121, or
equivalent).
2.2 Boiling chips.
2.2.1 Silicon carbide boiling chips (optional), approximately 10-40
mesh. Heat to 400°C for 30 minutes or solvent rinse before
use.
2.2.2 Teflon boiling chips (optional).. Solvent rinse before use.
2.3 Water bath, heated, with concentric ring cover, capable of temperature
control. NOTE: The bath water should be used in a hood.
2.4 Top loading balance, capable of accurately weighing to +0.01 g.
2.5 Balance-analytical, capable of accurately weighing to +0.0001 g.
2.6 Nitrogen evaporation device equipped with a heated bath that can be
maintained at 35-40°C, N-Evap by Organomation Associates, Inc., South
Berlin, MA (or equivalent).
ARO D-2
Rev. 9/88
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2.7 Vials and caps, 1 or 2 iL for GC auto sampler,
2.8 Vacuum system for eluting multiple cleanup cartridges.
2.8.1 Vac Elute Manifold (Analytichem International, Harbor City,
J.T. Baker or Supelco) or equivalent.
2.8.2 Vacuum trap made from a 500 mL sidearm flask fitted with a one-
hole stopper and glass tubing.
2.8.3 Vacuum pressure gauge.
2.8.4 Rack for holding 10 mL volumetric flasks in the manifold.
2.9 Glass vials, at least 20 mL, with screw cap and teflon or inert plastic
liner for sample extraction and for sulfuric acid and permanganate
treatment.
2.10 Spatula, stainless steel or teflon.
2.11 Pipet, Volumetric 1.00 mL or 2.00 mL (optional),
2.12 Syringe, 1.00 mL or 2.00 mL (optional).
2.13' Flask, Volumetric 10.00 mL.
2.14 Flask, Volumetric 1.00 mL or 2.00 mL (optional).
2.15 Vials, 10 mL, with screw cap and teflon liner (optional).
2.16 Tube, centrifuge, 12 to 15 mL with 19 mm ground glass joint,
(optional).
2.17 Snyder Column, micro two or three ball with a 19 mm ground glass joint.
2.18 Centrifuge, table top (optional)
2.19 Gas chromatographic system, including a 0.25 inch injector and an
electron capture detector. The GC must be equipped with an integrator
or data system rather than a strip chart recorder. Detector makeup gas
is required for capillary analysis.
2.19.1 Two wide bore (0.53 mm ID) fused silica GC columns are
required. A separate detector is required for each column.
The specified analytical columns are DB-1701, 30 m x 0.53 mm
ID, 1.0 to 1.5 urn film thickness, J&W Scientific, Folsom, CA
and a DB-608 or SPB-608, 30 m x 0,53 mm ID, 0.8 to 1.5 um film
thickness (or equivalent) from J&W Scientific or Supelco, Inc.,
Bellefonte, PA. Equivalent columns may be employed if they
meet the requirements in 2.19.3.
AR0 D-3
Rev. 9/88
-------
Columns are mounted in 1/4 inch injector ports using glass
adapters available from a variety of commercial sources (J&W
Scientific, Supelco, Inc., Hewlett-Packard, Varian, Inc.,
Perkin Elmer).
Column equivalence is demonstrated by running the calibration
standards mixtures described in Section 6.3.1. Each equivalent
column must be calibrated according to the procedures described
in Section 6.3 and satisfy all of the acceptance criteria
described therein (if an equivalent column is used, it must be
described in the Case Narrative).
The carrier gas must be helium.
Because the column flow for wide bore capillary systems is 5
mL/minute which is slower than for packed column systems, it is
necessary to have precise control of the carrier gas flow and
to supply makeup gas to the detector. The makeup gas must be
P-5, P-10 (argon/methane) or nitrogen according to the
instrument specification.
2.20 Vortex mixer, Genie, Model 550-6, Scientific Industrial, Inc., Bohemia,
NY (or equivalent).
2.21 Disposable Pasteur pipets, packed with glass wool rinsed with hexane.
2.22 Ultrasonic cell disruptor, Heat Systems Ultrasonics, Inc.,- Model W-385
SONICATOR (475 Watt with pulsing capability, No. 419 1/8 inch standard
tapered MICROTIP probe), of 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.
2.23 Sonabox acoustic enclosure - recommended with above disruptors for
decreasing cavitation sound.
3. Reagents
3.1 Hexane, acetone, iso-octane (optional), and methanol (optional)
solvents of pesticide residue analysis grade or equivalent. It is
recommended that each lot of solvent be analyzed to demonstrate that it
is free of interference before use.
3.2 Primary Aroclor standards will be obtained from the EPA Quality
Assurance Materials Bank, Pesticides and Industrial Chemicals
Repository, Research Triangle Park, NC, if available. Commercial
standards must be used for all working solutions after they have been
shown to be the proper material and at least 95 percent pure by
comparison to primary standards.
3.3 Mercury (optional).
3.4 Copper powder (optional), bright and non-oxidized.
2.19.2
2.19.3
2.19.4
2.19.5
ARO D-4
Rev. 9/88
-------
3.5 Concentrated sulfuric acid (Sp. gr. 1.84),
3.6 Potassium permanganate solution (5 percent w/v). Slowly add 100 mL
water to 5 g of potassium permanganate in a Pyrex vessel.
3.7 Diol bonded silica 500-mg, cartridges with stainless steel frits
Catalog No. 614313, Analytichem, 24201 Frampton Ave., Harbor City, CA
(or equivalent).
3.8 Ten percent acetone in hexane (v/v). Prepare the mixture by adding 10
mL of acetone to 90.0 mL of hexane. NOTE: Prepare this mixture
accurately or the results from the Diol cartridge cleanup will be
adversely affected.
3.9 Surrogate Standard Solution.
The surrogates, tetrachloro-meta-xylene and decachlorobiphenyl, are
added to all samples, the control matrix spike, and blanks, Prepare a
surrogate standard spiking solution of 1.0 ug/mL of each of the
surrogates in acetone. The solution must be replaced after six months,
or sooner, if comparison with quality control check samples indicates a
problem.
CAUTION: Analysts must allow all spiking solutions to equilibrate to
room temperature before use.
3.10 Aroclor control matrix spike solution. Prepare a spiking solution in
acetone or methanol that contains 25 ug/mL of Aroclor 1254.
3.11 Performance evaluation standards are a series of 12 mixtures each
containing the surrogates and one other analyte, at three concentration
levels (low, medium, and high). The other analytes are specified in
6.4.4.1 (note that the mixture of Aroclors 1016 and 1260 is considered
as a single analyte). The concentration level of the low level
standard is given in 6.3.3. The medium level standards are 10 times
the low level concentrations in 6,3.3, and the high level standards are
30 times the low level concentrations.
4. Sample Preparation For GC/ECD Analyses
4.1 High concentration samples are initially separated into individual
phases. An aliquot of 500 mg of each phase is transferred to a
separate 20 mL vial. Wipe the mouth of the vial with a tissue to
remove any sample material. To avoid cross contamination, cap the vial
before proceding to the next phase unit.
4.1.1 Add 1.0 mL of the surrogate spiking solution to each vial.
4.1.2 Add 1.0 g of anhydrous sodium sulfate to each vial, and mix
with a clean spatula.
4.1.3 Add 9.0 mL of hexane to each vial, and sonicate each vial for 2
minutes at 100 watts power. For control matrix spike, add only
8.0 mL of hexane (see 4.3 below).
ARQ D-5
Rev. 9/88
-------
4.1.4 Filter the extract through a disposable pipet loosely packed
with glass wool. Collect at least 7 mL of extract in a clean
vial.
4.1.5 Proceed to paragraph 5.1 for extract cleanup procedures.
4.2 Control matrix spikes, blanks and all single phase units are spiked
with the surrogate solution. The control matrix spike and the blanks
are subjected to the same extraction, cleanup, and dilution procedures
as the samples.
4.3 Once per Case, or for every group of 20 single phase units (whichever
is more frequent), a control matrix spike sample is prepared with 1.0
mL of the Aroclor 1254 spiking solution and 500 mg of corn oil. The
control matrix spike must be extracted, cleaned up, and analyzed in the
same fashion as all other single phase units (see 4.1 above). Note:
Add only 8.0 mL of hexane to the vial during the extraction of the
control matrix spike.
4.4 Interferences
4.4.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware;
these contaminants lead to discrete artifacts, and/or elevated
baselines, in gas chromatograms. All of these materials should
be routinely demonstrated to be free from interferences under
the conditions of the analysis by running reagent blanks.
Interferences by phthalate esters can pose a major problem in
Aroclor analysis when using the electron capture detector.
Common flexible plastics contain varying amounts of phthalate
esters which are easily extracted 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 such plastics in the
laboratory.
4.4.2 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 of the site being sampled. The
cleanup procedures in Section 5 must be used to remove such
interferences in order to achieve the contract required
quantitation limits.
5. Extract Cleanup For GC/ECD Analyses
5.1 Requirements
5.1.1 This procedure is only suitable for Aroclors and Toxaphene.
Because the cleanup involves the use of sulfuric acid and
potassium permanganate, the final solutions are not suitable
for pesticide analysis.
ARO D-6
Rev. 9/88
-------
5.1.2 Diol cartridge cleanup is required for all samples, control
matrix spikes and blanks. This -procedure removes polar organic
molecules such as phenols. Each lot number of Diol cartridges
must pass a cartridge performance check.
5.1.3 Sulfur can be removed by one of two methods according to
laboratory preference (Section 5.6),
5.1.4 Blanks and control matrix spikes must be subjected to the same
cleanup as the field samples.
5.1.5 It is required that all the waste aliquots be diluted with
hexane before initiating the following treatments.
5.1.6 No GPC cleanup is used in the preparation of samples for GC/ECD
analysis under this protocol.
5.2 Sulfuric Acid Cleanup
5.2.1 Using a syringe or a volumetric pipet, transfer 2.0 mL of the
hexane solution to a 10 mL vial and carefully add 5 mL of conc.
sulfuric acid. This procedure must always be done in a fume
hood. NOTE; If the remaining extract from the method blank is
saved at this point, it may be used in paragraph 5.6.3.2 to
prepare a sulfur blank.
5.2.2 CAUTION: Make sure that there is no exothermic reaction nor
evolution of gas prior to proceeding.
5.2.3 Cap the vial tightly and vortex for one minute. A vortex must
be visible in the vial.
5.2.4 CAUTION: Stop the vortexing immediately if the vial leaks,
AVOID CONTACTING THE SOLUTION WITH BARE SKIN, SULFURIC ACID
WILL BURN.
5.2.5 Allow the phases to separate for at least one minute. Examine
the top (hexane) layer, it should not be highly colored nor
should it have a visible emulsion or cloudiness.
5.2.6 If a clean phase separation is achieved proceed to Step 5.2.10.
5.2.7 If the hexane layer is colored or the emulsion persists for
several minutes, remove the sulfuric acid layer from the vial
via a glass pipette and dispose of it properly. Add another 5
mL of clean sulfuric acid.
5.2.8 Note: Do not remove any hexane at this stage of the procedure.
5.2.9 Vortex the sample and allow the phases to separate as described
previously.
5.2.10 Transfer the hexane layer to a clean 10 mL vial.
ARO D-7
Rev. 9/88
-------
5.2.11 Add an additional 1 mL of hexane to the sulfuric acid layer,
cap the vial securely and shake. This second extraction is
done to ensure quantitative transfer of all analytes.
5.2.12 Remove the second hexane layer and combine with the hexane from
Step 5.2.10.
5.3 Permanganate Cleanup
5.3.1 Add 5 mL of the five percent aqueous potassium permanganate
solution to the combined hexane fractions from 5.2.12.
5.3.2 CAUTION: Make sure that there is no exothermic reaction nor
evolution of gas prior to proceeding.
5.3.3 Cap the vial tightly and vortex for one minute. A vortex must
be visible in the vial.
5.3.4 CAUTION: Stop the vortexing immediately if the vial leaks,
AVOID CONTACTING THE SOLUTION WITH BARE SKIN, POTASSIUM
PERMANGANATE WILL BURN.
5.3.5 Allow the phases to separate for at least one minute. Examine
the top (hexane) layer, it should not be highly colored nor
should it have a visible emulsion or cloudiness.
5.3.6 If a clean phase separation is achieved, proceed to Step
5.3.10.
5.3.7 If the hexane layer is colored or the emulsion persists for
several minutes, remove the permanganate solution from the vial
via a glass pipette and dispose of it properly. Add another 5
mL of the clean aqueous permanganate solution.
5.3.8 NOTE: Do not remove any hexane at this stage of the procedure.
5.3.9 Vortex the sample and allow the phases to separate.
5.3.10 Transfer the hexane layer to a clean 10-mL vial.
5.3.11 Add an additional 1 mL of hexane to the permanganate layer, cap
the vial securely and shake. This second extraction is done to
ensure quantitative transfer of all Aroclors and Toxaphene.
5.3.12 Remove the second hexane layer and combine with the hexane from
Step 5.3.10.
5.4 Final Preparation
5.4.1 Reduce the volume of the combined hexane layers to 1.0 mL under
a stream of dry nitrogen.
5.4.1.1 Nitrogen Blowdown Technique (Taken from ASTM Method
D 3086).
ARO D-8
Rev. 9/88
-------
5.4.1.1.1 Place the concentrator tube in a
heating bath (30-35°C) and evaporate
the solvent to the final volume using a
gentle stream of clean, dry nitrogen
(filtered through a column of activated
carbon). The extract must never be
allowed to become dry.
5.4.1.1.2 CAUTION: New plastic tubing must not be
used between the carbon trap and the
sample, as it may introduce
interferences. The internal wall of
new tubing must be rinsed several times
with hexane then dried prior to use.
5.4.2 Prepare the extracts using the Diol cartridge cleanup as
described below.
5.5 Diol Cartridge Procedure
5,5.1 Cartridge Performance Check
Each lot number of Diol cartridges must be tested by the
following procedure before it is used for sample cleanup. Add
1,0 mL of the control matrix spike solution to 4 mL of hexane.
Place a 1.0 mL aliquot of the diluted solution onto the top of
a prewashed Diol cartridge, and elute it with 9 mL of
hexane/acetone [90:10(V/V)]. Adjust the final volume to 10.0
mL and analyze by GC/ECD. The recovery of Aroclor 1254 must be
determined for evaluation and reporting purposes.. The lot of'
Diol cartridges is acceptable if the Aroclor is recovered at 80
to 110 percent.
5,5.2 Diol Cartridge Cleanup
5.5.2.1 Attach the Vac Elute vacuum manifold to a water
aspirator or a vacuum pump with a trap installed
between the manifold and the vacuum source. Adjust
the vacuum pressure in the manifold to between 5 and
10 pounds of vacuum.
5.5.2.2 A 500 mg Diol cartridge is selected for each hexane
solution of waste and placed into the vacuum
manifold.
5.5.2.3 Prior to cleanup of the hexane solutions of waste,
the cartridges must be washed with hexane/acetone
(90:10). This is accomplished by placing the
cartridge in the vacuum manifold, pulling a vacuum
and passing 5 mL of the hexane/acetone solution
through the cartridge.
ARO D-9
Rev. 9/88
-------
5.5.2.4 After the cartridges in the manifold are washed, the
vacuum is released and a rack containing labeled 10
mL volumetric flasks is placed inside the manifold.
Care must be taken to ensure that the solvent line
from each cartridge is placed inside of the
appropriate volumetric flask as the manifold top is
replaced.
5.5.2.5 After the volumetric flasks are in place, vacuum to
the manifold is restored and 1 mL (the entire
volume) from each sample, blank, or control matrix
spike solution is transferred to the top frit of the
appropriate Diol cartridge.
5.5.2.6 The Aroclors and Toxaphene in the solution
concentrates are then eluted through the column with
9 mL of hexane/acetone (90:10) and collected into
the 10 mL volumetric flasks held in the rack inside
of the vacuum manifold.
5.5.2.7 Transfer the eluate in each volumetric flask to a
clean centrifuge tube or 10 mL vial. Use two
additional 1 mL hexane rinses of the flask to ensure
quantitative transfer of the cartridge eluate.
5.5.2.8 Adjust the extract volume to 10.0 mL with hexane
5.5.2.9 If crystals of sulfur are evident or the presence of
sulfur is suspected, proceed to Section 5.6.
5.5.2.10 If sulfur is not expected to be a problem, transfer
the 1 mL of solution to a GC vial and label the
vial. (Some autosamplers require 1 mL solvent
volumes, others require 2 mL.) The solution is ready
for the GC/ECD analysis detailed in Section 6.
Store the extracts at 4°C in the dark until analyses
are performed.
5.6 Sulfur Removal
5.6.1 Two options are available for the removal of sulfur from
samples. The mercury technique appears to be the most
reliable, but requires the use of small volumes of mercury in
the laboratory.
5.6.2 CAUTION: Mercury containing waste should be segregated and
disposed of properly.
5.6.3 Mercury Technique
5.6.3.1 Add 1 to 3 drops of mercury to 1.0 mL of each hexane
solution in a clean vial. Tighten the top on the
vial and agitate it for 30 seconds. Filter or
centrifuge and decant the solution to remove all
ARO D-10
Rev. 9/88
-------
solid precipitates and liquid mercury. Proceed to
Section 6 for GC/ECD analysis if the mercury appears
shiny. If the mercury turns black, repeat the
process as necessary until it remains shiny.
Dispose of the mercury waste properly.
5.6.3.2 If only a partial set of the hexane concentrates
require sulfur cleanup, an additional reagent blank
of hexane and mercury (or copper) is required. This
additional blank may be prepared from the remaining
blank extract in paragraph 4.14.
5.6.4 Copper Technique
5.6.4.1 Bright (non-oxidized) granular copper (one to three
granules) can be used in place of mercury in the
procedure described in Section 5.6.3. If the copper
appears shiny, proceed to Section 6 for GC/ECD
analysis. If the copper changes color, repeat
sulfur removal as necessary.
6. GC/ECD Analysis For Aroclors
6.1 Summary.
6.1.1 This GC/ECD method is used for the analysis of the Aroclors and
Toxaphene only from Exhibit C. Although this method is similar
to GC/ECD methods for pesticides, this method is only
appropriate for Aroclors and Toxaphene.
6.1.2 1.0 mL of the surrogate spiking solution is added to all single
phase units, control matrix spikes and blanks prior to
extraction and surrogate recoveries will be reported with
sample data. The retention time shift of the surrogates in any
standard, sample, control matrix spike, or blank may not excede
0.5%.
6.1.3 Control matrix spikes are required for this method and are
prepared from the Aroclor 1254 control matrix spike solution.
6.1.4 Quantitation of Aroclors and Toxaphene is done by external
standard techniques using three-point curves generated during
an initial calibration sequence. Quantitation is based on
comparison of three to five sample peaks with the corresponding
peaks in the standard.
6.1.5 The absolute retention times of single component organochlorine
pesticides are determined as part of this method and reported
with the sample data in order to prevent misidentification of
these compounds as constituent peaks of Aroclors or Toxaphene.
6.1.6 Sample data are collected after an initial calibration sequence
is run. The RT's, calibration factors, and column performance
are monitored no less than once every 12 hours with an
ARO D-ll
Rev. 9/88
-------
instrument blank and with a standard. Data can be collected
only as long as all evaluation criteria given in Section 6,4.4
• are met. In all GC runs, the injector must be heated to at
least 205°C, The injection must be made on column, using
either automatic or manual injection. If autoinjectors are
used, 1.0 uL injection volumes may be used. Manual injections
must use at least 2.0 uL injection volumes.
6.1.7 The carrier gas must be helium.
6.1.8 The analysis of samples is accomplished by using two wide bore
(0.53 mm ID) fused silica GC columns. A separate detector is
required for each column. The specified analytical columns are
DB-1701, 30 m x 0.53 mm ID, 1.0 to 1.5 um film thickness, J&W
Scientific, Folsom, CA and a DB-608 or SFB-608, 30 m x 0.53 mm
ID, 0.8 to 1.5 um film thickness (or equivalent) from J&W
Scientific or Supelco, Inc., Bellefonte, PA. Equivalent
columns may be employed if they meet the requirements in
2.19.3.
6.1.9 Analysis of a sample on both columns is only required when one
column gives at least one positive result. Peak identification
and quantitation must be reported separately for both columns
if any Aroclors or Toxaphene are detected in a sample.
6.1.10 Wide bore capillary columns are installed in standard 0.25 inch
packed column injector and detector ports by use of suitable
glass adapters and ferrules. Because the column flow used is 5
mL/minute of helium, it is necessary to have precise carrier
gas flow and to supply makeup gas to the detector.
6.1.11 Electron capture detectors must be plumbed with F-5, F-10
(argon/methane) or nitrogen as a detector makeup gas according
to the instrument specification.
6.1.12 The temperature program for GC analysis is:
Tt 150*C
Initial time _ 1/2 minute
Temperature ramp 5"/minute to 275"C
Final hold 10 minutes
NOTE; It may be necessary to adjust this temperature program
for individual gas chromatographs. It is a requirement for
this method that the oven(s) regulate temperature.
6.1.13 All calibration and run sequence requirements of the following
sections apply independently to both the specified columns.
6.2 Calibration Standards
6.2.1 The resolution check standard must be run after the first blank
in the calibration sequence in order to demonstrate the ability
of the GC column to resolve certain pesticide compounds. The
ARO D-12
Rev. 9/88
-------
resolution check standard must contain the following seven
compounds each with a concentration of 50 ng/mL:
Methoxychlor
Endrin ketone
p,p'-DDE
Dieldrin
Endosulfan sulfate
Endosulfan I
gamma-Chlordane
6.2.2 The resolution criterion is that the height of the valley
between two adjacent peaks in the mixture must not be greater
than 60% of the height of the shorter peak. Experience to date
suggests that the poorest resolution on the DB-608 column will
be between DDE and Dieldrin and between Methoxychlor and Endrin
ketone. On the DB-1701 column, resolution difficulties should
be expected between Endosulfan I and gamma-Chlordane and
between Methoxychlor and Endosulfan sulfate.
6.2.3 Each Aroclor must be analyzed at the three concentrations given
in 6.3.1 and 6.3-6.5 in order to establish the response factors
for the quantitation peaks for each Aroclor and to demonstrate
detector linearity.
The high point concentration defines the upper end of the
concentration range for which the calibration is valid.
6.2.4 Aroclor and Toxaphene standards must be prepared individually,
except for Aroclor 1260 and Aroclor 1016, which can be combined
in one standard mixture.
6.2.5 The performance of the GC system is monitored by the use of a
standard and an instrument blank, both of which must be run no
less than once every 12 hours (see Section 6.4.4 for the one
exception to this requirement). The instrument blank is a
hexane solution containing 20 ng/mL of each of the surrogates.
6.3 Initial Calibration
6.3.1 All columns in all GC systems used to collect data using this
method must be calibrated with the following sequence of
standards (1) during the initial set up and (2) whenever
corrective action is required because a 12-hour check has shown
the instrument to be out of control (Section 6.4.4).
ARO D-13
Rev. 1/89
-------
No. of Potential
Injection No. Concentration Aroclor Quantitation Peaks
1
Blank
—
—
2
Resolution Check -
—
3
Low
1221
4
4
Medium
1221
4
5
High
1221
4
6
Low
1232
4
7
Medium
1232
4
8
High
1232
4
9
Low
1242
5
10
Medium
1242
5
11
High
1242
5
12
Low
1248
5
13
Medium
1248
5
14
High
1248
5
15
Low
1254
5
16
Medium
1254
5
17
High
1254
5
18
Low
1016/1260
5/5
19
Medium
1016/1260
5/5
20
High
1016/1260
¦ 5/5
21
Low
Toxaphene
4
22
Medium
Toxaphene
4
23
High
Toxaphene
4
24
Low
Pesticide A
—
25
Low
Pesticide B
—
26
Blank
_
—
6.3.2 Select four or five major peaks from each Aroclor and four
major peaks from Toxaphene as potential quantitation peaks.
The same peaks must be used throughout the run sequence,
including: initial calibration, 12-hour performance checks,
sample quantitation, and control matrix spike analyses.
6.3.3 The low-point concentration calibration standards for the
method analytes are:
LOW POINT AROCLOR CALIBRATION SOLUTIONS
ComDound
CAS Number
Low Concentration
1.
Aroclor 1016
12674-11-2
50
ng/mL
Aroclor 1260
11096-82-5
50
ng/mL
2.
Aroclor 1221
11104-28-2
50
ng/mL
3.
Aroclor 1232
11141-16-5
50
ng/mL
4.
Aroclor 1242
53469-21-9
50
ng/mL
5.
Aroclor 1248
12672-29-6
50
ng/mL
6.
Aroclor 1254
11097-69-1
50
ng/mL
7.
Toxaphene
8001-35-2
500
ng/mL
8.
Tetrachloro-meta-xylene
877-09-8
20
ng/mL
9.
Decaclorobiphenyl
2051-24-3
20
ng/mL
ARO D-14
Rev. 9/88
-------
6.3.4 The mid-point concentration of each standard is prepared at 10
times the concentrations given in 6.3.3. The surrogates must
be added at 200 ng/mL to all mid-point calibration solutions.
6.3.5 The high point concentration is prepared at 30-100 times the
concentrations given in Section 6.3.3. The surrogates must be
added at at least 600 ng/mL to all high point calibration
solutions.
6.3.6 Determine the absolute retention times (RT) for the selected
major peaks for each Aroclor and Toxaphene as well as the
relative mean deviation (RMD) for each peak,
100% 3
5110 " 3 X |RTi - RT | / RT
i-1
where RT is the mean RT for a specific peak in a particular
Aroclor and Toxaphene. The RMD for each Aroclor and Toxaphene
must be less than 0.5 percent before analytical results can be
reported.
6.3.7 Only three peaks are required for sample quantitation, however,
the peaks chosen must not co-elute with matrix interference.
Therefore, linearity of response is required for each of the
four or five potential quantitation peaks selected during the
initial calibration in order to establish system performance.
6.3.8 Three-point instrument calibration is required for each
potential quantitation peak of each Aroclor and Toxaphene. The
laboratory has three choices on how to establish a three point
calibration. Only one of the three calibration methods can be
used to quantitate samples in any single run sequence.
Laboratories may not mix calibration techniques for samples
quantitated using a single initial calibration.
6.3.8.1 The laboratory can use a mean calibration factor
(CF) determined from the three concentrations, but
only if the % RSD for the three points is < 15.0
percent.
Response of
CF - J i
3
Selected Peaks in Standard
3 Mass Injected (ng)
SD
%RSD - = x 100
CF
ARO D-15
Rev. 9/88
-------
——
Where SD - J (CFi - CF)
Y _
and ti—3
6.3.8.2 The laboratory can use a calibration line drawn
through all three calibration points if the value
for r (correlation coefficient from the linear
regression calculation) is >0.975 and if the zero
concentration intercept is <0.20.
(1/n) £ (X£ - x)(y-_ - y)
Where r -
[(1/n) 2 (Xi - x)2]H[(l/n) S (7i - y)2]H
6.3.8.3 Laboratories with electronic integrators or data
systems that automatically calculate calibration
curves as line segments between calibration points
may use two line segment calibration curves for each
quantitation peak of the Aroclor or Toxaphene. This
technique may be used only if r (the correlation
coefficient from the linear regression calculation)
is >0.975 for all three points for each peak and if
the zero concentration intercept is <0.20 times the
low point response for each Aroclor or Toxaphene
peak quantitated.
6.3.9 Mixtures of single component pesticides are injected as part of
the calibration sequence to establish the RT of individual
pesticides because they are potential method interferences.
Calibration factors are not calculated for the individual
pesticide standards.
6.3.10 Single Component Pesticide Mixtures
Individual
Standard
Mix A
Concentration
(ng/mL)
Individual
Standard Concentration
Mix B (ng/mL)
alpha-BHC
25.0
beta-BHC
25.0
Heptachlor
25.0
delta-BHC
25.0
gamma-BHC
25.0
Aldrin
25.0
Endosulfan I
25.0
Heptachlor epoxide
25.0
Dieldrin
50.0
alpha-Chlordane
25.0
Endrin
50.0
gamma-Chlordane
25.0
p,p'-DDD
50.0
p,p'-DDE
50.0
p,p'-DDT
50.0
Endosulfan sulfate
50.0
Methoxychlor
50.0
Endrin aldehyde
50.0
Tetrachloro-meta-xyl
ene 20.0
Endrin Ketone
50.0
Decachlorobiphenyl
20.0
Endosulfan II
50.0
Tetrachloro-meta-xylene
20.0
Decachlorobiphenyl
20.0
ARO D-16
Rev. 4/89
-------
6.3.11 The average retention times of the surrogates must be
calculated using all 26 injections listed in 6.3,1. This value
is used to establish the acceptance criteria for all subsequent
injections.
26
RT (surrogate) - I (|urr,gate)
6.3.12 The mean response for each surrogate in the low-point
calibration analysis is used as the surrogate calibration
factor (CF),
6.3.13 Sample analysis may not proceed until a satisfactory
calibration has been demonstrated.
6.3.14 The equivalence of GC columns other than those specified in
2.19.1 may be demonstrated by:
o Successful initial calibration of the gas chromatographic
system including meeting the requirements in 6,3.6 and
6.3.8.
o Meeting the resolution criterion in 6.2.2.
o Achieving baseline resolution of each of the components in
Individual Mix A from one another and baseline resolution of
each of the components in Individual Mix B from one another.
6.4 Sample Analysis Run Sequence
6.4.1 Summary
6.4.1.1 Extracts of single phase units are analyzed as part
of a run sequence that includes both instrument
blanks and performance evaluation standards, which
provide both calibration verification and instrument
performance evaluation. Both an instrument blank
and a standard must be analyzed successfully on each
column no less than once in every 12 hours that
sample data are collected. In addition, the
laboratory must analyze at least one method blank
for each Case, or once per 20 single phase units,
whichever is more frequent. Acceptance criteria for
the instrument blanks (Section 6.4.3), method blanks
(Section 6.4.2), and for the performance evaluation
standards (Section 6.4,4) are given below.
6.4.1.2 The laboratory may identify and quantitate analyte
peaks based on data collected during the initial
calibration as long as an acceptable instrument
blank and an acceptable evaluation mixture are
analyzed every 12 hours. The requirements for the
run sequence apply to both columns in all
instruments used in these analyses.
ARO D-17
Rev. 9/88
-------
6.4.1.3
Example Run Sequence
Note: The 12 hours are counted from the injection
of the sample in step 27, not from step 1.
Time Injection # Material Injected
1
2
3 - 26
0 hr, 27
o
o
o
o
12 hr, o
1st injection
past 12 hr.
2nd injection
o
o
o
o
o
24 hr. o
1st injection
past 24 hr.
2nd injection
o
o
Instrument Blank
Resolution Check
Initial Calibration
Standards and Blanks
First Sample
Subsequent
Samples
Instrument Blank
Evaluation Mixture
Sample
Subsequent
Samples
Instrument Blank
Evaluation Mixture
Sample
6.4.1.4 The run continues until an unacceptable instrument
blank or standard is analyzed. This example run
sequence shows only the minimum number of instrument
blanks and evaluation mixtures necessary to meet the
requirements. More instrument blanks and
evaluations may be run at the discretion of the
laboratory, but these must satisfy the criteria
presented in Section 6.4.3 and 6.4.4.
6.4.1.5 A run sequence must include all required control
matrix spike analyses and method blanks, but each
laboratory may decide at what point in the run
sequence they are analyzed.
6.4.2 Method Blanks
The method blank consists of 500 mg of corn oil spiked with the
surrogates at 20 ng/raL that is subjected to the same cleanup as
a sample, in order to check for system contamination. None of
the Aroclors or Toxaphene listed in Exhibit C may be present at
greater than the CRQL in the analysis of a method blank. If
any of the Aroclors or Toxaphene are present at >CRQL, data
ARO D-18
Rev. 9/88
-------
collection must be stopped, and the data for all single phase
units analyzed since the last acceptable blank are considered
suspect. Therefore all single phase units with Aroclors and
Toxaphene detected at levels >CRQL that were prepared during
the same 12-hour shift as a contaminated method blank must be
reextracted and reanalyzed at no additional expense to the
Agency. At least one method blank must be included for every
20 single phase units.
6.4.3 Instrument Blank
An instrument blank is a hexane solution containing 20 ng/mL of
the surrogates. An acceptable instrument blank analysis must
demonstrate that no Aroclor or Toxaphene can be detected at
greater than 0.5 times the CRQL. If Aroclors or Toxaphene are
detected at greater than half the CRQL, all data collection
must be stopped and corrective action taken. Data for samples
with analytes detected at >CRQL analyzed between the last
acceptable instrument blank and the unacceptable blank are
considered suspect. An acceptable instrument blank must be
analyzed before additional data are collected. After an
acceptable instrument blank is analyzed, all single phase units
with Aroclors or Toxaphene detected at levels >CRQL that were
analyzed after the previous acceptable instrument blank must be
reinjected during a valid run sequence and reported at no
additional expense to the Agency.
6.4.4 Performance Evaluation Standards
6.4.4.1 The performance evaluation standards injected at 12
hour intervals will be rotated so as to include the
common Aroclors and Toxaphene at low, medium, and
high concentrations according to the following
schedule:
NOTE: The time clock starts after the completion of
the initial calibration as in 6.14.3. The
performance evaluation mixture is injected following
an instrument blank, as in 6.4.13 .
Concentration
Compound
Hour
low
Toxaphene
12
low
1248
24
low
1254
36
low
1016/1260
48
medium
Toxaphene
60
medium
1248
72
medium
1254
84
medium
1016/1260
96
high
Toxaphene
108
high
1248
120
high
1254
132
high
1016/1260
144
Repeat
ARO D-19
Rev. 9/88
-------
6.4.4.2 For each of the four or five potential quantitation
peaks (Section 6.3.1), the RT in the standard must
be within the retention time window of ±1.0 percent
of the mean RT calculated during the initial
calibration.
6.4.4.3 For each of the four or five potential quantitation
peaks (Section 6.3.1), the response (area or height)
must be within 20.0 percent (±20.0 RPD) of the mean
response obtained during the initial calibration.
CF - CFp
RPD - ^ x 100
CF
Where:
CF - Average calibration factor from initial
calibration (Equation 6.2).
CFp - Calibration factor from current
E evaluation mixture.
6.4.4.4 The retention time shift of the surrogates must be
within 0.5 percent of the average retention time
established during the initial calibration.
6.4.4.5 If a performance evaluation standard does not meet
the criteria listed above, it must be reinjected
immediately. If the second injection also does not
meet the criteria, all data collection must be
stopped. Appropriate corrective action must be
taken and a new initial calibration sequence must be
analyzed before more sample data are collected.
Data collected after the last acceptable evaluation
mixture are considered suspect and all extracts with
analytes present at > CRQL must be reinjected and
reported at no additional expense to the Agency.
6.4.4.6 Analysts are cautioned that running an instrument
blank and an evaluation mixture once every 12 hours
is the minimum contract requirement. Highly complex
samples or unstable GC equipment may cause peaks
from one injection to be carried over into the next.
It may be necessary to analyze instrument blanks and
evaluation mixtures more often in order to avoid
discarding data.
6.4.4.7 The requirement for running the 12 hour instrument
blanks and evaluation standards is waived when no
sample or control matrix spikes are analyzed during
the 12-hour period. After a break in sample data
analysis, a laboratory may resume the analysis of
ARO D-20
Rev. 9/88
-------
samples and control matrix spikes using the current
initial calibration after an acceptable performance
evaluation standard is analyzed. If a successful
continuing calibration cannot be demonstrated after
an interruption, an acceptable initial calibration
must be run before sample data can be collected,
NOTE: This section does not affect the requirement
that all acceptable sample analyses must be
bracketed by acceptable evaluation mixtures.
6.4.5 Control Matrix Spike
6.4.5.1 A control matrix spike must be analyzed once per
Case, or once for every 20 single phase units,
whichever is more frequent.
The percent recovery of each of the five Aroclor
1254 peaks is calculated using the following
equation:
Matrix
Spike - SSR-SR x 100
Recovery SA
Where:
SSR - Spike Sample Recovery
SR - Sample Result
SA — Spike Added
These results are reported per Aroclor 1254 peak (5
total).
6.4.5.2 Control matrix spike recoveries will be reported by
the Contractor. (See Exhibit B.)
6.5 Sample Analyses
6.5.1 The protocol is intended to achieve the quantitation limits
shown in Exhibit C whenever possible. If sample chromatograms
have interfering peaks, a high baseline, or off-scale peaks,
then samples must be reanalyzed following dilution, or another
aliquot of the original dilution should be cleaned up and
analyzed. Samples which cannot be made to meet specifications
given in this section after the second full cleanup (sulfuric
acid, permanganate, Diol and mercury sulfur removal) are
reported as intractable in the Case Narrative and do not
require further analysis. No limit is placed on the number of
repeat full cleanups of samples that may be required because of
contaminated method blanks.
6.5.2 The sample must be analyzed at the most concentrated level
consistent with achieving satisfactory chromatography. If
dilution is employed solely to bring a peak within the
ARO D-21
Rev. 9/88
-------
calibration range or to produce an on-scale Aroclor or
Toxaphene pattern, the results for both a more and a less
concentrated extract must be reported. The resulting changes
in quantitation limits and surrogate recovery must also be
reported for the dilute samples.
6.5.3 If the laboratory has reason to believe that diluting the final
extracts will be necessary, an undiluted run may not be
required. If an acceptable chromatogram (as defined in 6.6) is
achieved with the diluted cleaned sample extract, an additional
analysis at 10 times the concentration of the dilution must be
injected and reported with the sample data.
6.5.4 The peak response of sample peaks in diluted cleaned samples
must be >25 percent of full scale to allow visual pattern
recognition of the Aroclors and Toxaphene.
6.5.5 An on-scale chromatogram(s) of all selected Aroclor
quantitation peaks must be presented with the sample data.
6.5.6 Chromatographic data may be replotted electronically in order
to produce an on-scale chromatogram, except when the off-scale
sample peaks are larger than the high point calibration peaks.
In that case, the samples must be diluted and reinjected.
6.5.7 The peak response of sample peaks on the replotted chromatogram
must be >25 percent of full scale to allow visual pattern
recognition of the Aroclors or Toxaphene.
6.6 Data Acceptance Criteria
6.6.1 Reportable data for a sample must include a chromatogram with a
baseline which returns to below 50 percent of full scale before
the elution time of Aroclor 1221 and to below 25 percent of
full scale after Aroclor 1221 and before the elution time of
Decachlorobiphenyl.
6.6.2 If dilution has been applied and no peaks are detected above 25
percent of full scale, analysis of a more concentrated sample
is required.
6.6.3 Reportable sample data must include chromatogram(s) with all
detected Aroclor or Toxaphene peaks in the linear range of the
quantitation determined by the initial calibration.
6.6.4 NOTE: If more than one chromatogram is required to satisfy the
criteria for a sample, the results of all chromatograms must be
reported. These requirements apply to both columns.
6.6.5 Peaks used for quantitation that are more than two times the
width of the high concentration calibration peaks for that
analyte must be reported with an appropriate data flag. (See
Exhibit B.)
ARO D-22
Rev. 9/88
-------
6.6.6 The retention time shift of the surrogates in any standard,
sample, control matrix spike, performance evaluation standard,
or blank may not excede 0.5%,
6.7 Identification Of Aroclors And Toxaphene
6.7.1 Aroclors and Toxaphene present special analytical difficulties.
Because of the alteration of these materials in the
environment, it is probable that samples which contain Aroclors
or Toxaphene will give similar but not identical patterns as
Aroclor or Toxaphene standards. Thus, identification requires
visual inspection of an on-scale pattern. The pattern may be
brought on-scale either by diluting the sample and reinjecting,
or by replotting the chromatograph stored in a laboratory data
system.
6.7.2 The choice of the peaks used for quantitation and recognition
of those peaks may be complicated by the environmental
alteration of the Aroclors and Toxaphene and by the presence of
coeluting analytes and/or matrix interferences.
6.7.3 The numbers of potential quantitation peaks are listed in
6.3.1.
6.7.4 The more highly chlorinated components of the Aroclors and
Toxaphene are more stable in the environment. Therefore, the
analyst should emphasize the later eluting peaks of a pattern
in identifying analytes when weathered Aroclors or Toxaphene
are detected.
6.8 Quantitation Of Analytes
6.8.1 Analytes may be quantitated using either a modern electronic
integrator or a laboratory data system. The analyst may use
either peak height or peak area as the basis for quantitation,
however the use of area versus height must be consistent
between samples. The use of an electronic integrator or a
laboratory data system is required.
6.8.2 The chromatograms of all samples must be reviewed by a
qualified Pesticide/PCB analyst before they are reported.
6.8.3 Using an electronic integrator, one of three calibration
techniques may be employed (6.3.5). It is the responsibility
of the analyst to set the integration parameters such that off-
scale chromatograms are within the dynamic range of the
instrument. The analyst should also check for data flags
generated by the instrument that indicate improper quantitation
of peaks prior to reporting data to the EPA.
6.8.4 In order to be quantitated, the detector response (peak area or
peak height) of all analytes must lie between the responses of
the low and high concentrations in the initial calibration. If
the analytes are detected below the CROL, they are reported
ARO D-23
Rev. 9/88
-------
with the appropriate flags (See Exhibit B). If they are
detected at a level greater than the high calibration point,
the sample must be diluted either to a maximum of 1:100,000, or
until the response is within the linear range established
during calibration.
6.8.6 The analyst must select 3-5 quantitation peaks for each
detected Aroclor or Toxaphene that do not co-chromatograph with
matrix interferences and determine the concentration using each
peak separately. Concentrations are calculated using the
following equations:
6.8.7 Samples:
Concentration mg/Kg - _ (V (V
(CF)(Vi)(Wx)(1000)
Where:
— Response for the parameter to be measured (height or
area).
CF - Calibration factor for the external standard
(Section 6.3.5).
Vt - Volume of total extract (uL) (take into account any
extra dilution).
- Volume of extract injected (uL).
Wx — Weight of waste diluted (mL).
6.8.8 The laboratory will quantitate each of the selected Aroclor or
Toxaphene peaks individually, and determine an average
concentration from all of the selected peaks. Quantitation is
performed on both columns; the lower value is reported on Form
I. See Exhibit B for instructions on completing Form I and
Form X.
6.8.9 Detected Aroclors and Toxaphene must be reported as: (1) a
concentration between the CRQL and 10 x CRQL, or (2) as an
estimated value below the CRQL. (See Exhibit B.)
6.8.10 If more than one Aroclor is observed in a sample or if an
Aroclor and Toxaphene are observed in the same sample, the
laboratory must choose separate congener peaks to quantitate
the different analytes. A peak common to both analytes present
in the sample must not be used to quantitate both analytes.
6.8.11 The concentrations of the surrogates are calculated using the
equation in 6.8.7, where the mean response of the surrogate
established during the initial calibration serves as the
surrogate calibration factor (CF).
6.8.12 The retention time shift of the surrogates in any standard,
sample, control matrix spike, or blank may not excede 0.5%.
ARO D-24
Rev. 4/89
-------
EXHIBIT E
Quality Assurance/Quality Control Requirements
-------
TABLE OF CONTENTS
Section Page Number
I. Introduction E-l
II. QA/QC Standard Operating Procedures E-2
III. QA/QC Requirements
Volatile QA/QC Requirements VOA E-8
Extractables QA/QC Requirements EXT E-25
Aroclors/Toxaphene QA/QC Requirements ARO E-45
IV. Analytical Standards E-63
V. Laboratory Evaluation Procedures... E-65
Rev, 9/88
-------
QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
SECTION I
INTRODUCTION AND SCOPE
The Quality Assurance/Quality Control (QA/QC) procedures defined herein
must be used by the Contractor when performing analyses according to the
methods specified in Exhibit D. This exhibit summarizes the QA/QC procedures
and criteria that are mandatory for the performance of the Contract.
The purpose of this document is to provide a uniform set of procedures
for the analysis of high-concentration organic samples, documentation of
methods and their performance, and verification of the sample data generated.
The program will also assist laboratory personnel in recalling and defending
their actions under cross examination if required to present court testimony
in enforcement case litigation.
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SECTION II
QA/QC STANDARD OPERATING PROCEDURES
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1.
General OA/OC Consideration
The Contractor shall have a written QA/QC SOP (Standard Operating
Procedure) which describes the inhouse 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 OA/OC 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:
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 follows 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 will 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.
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2.4 To accomplish these objectives, Standard Operating Procedures should
address the major elements upon which the final quality of the
contractors work depends. In the following descriptions these six
major areas have been divided into subelements, where applicable.
These
elements include but are not
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. Ihe 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 can 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,
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3.4.5 Bench data,
3.4.6 Operating procedures, or any changes to these procedures, and
3.4.7 Laboratory notebook policy.
3.5 Procedures making revisions to technical procedure 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 for all
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.
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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.
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 of 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 reagent blank analysis to establish analyte
levels, control matrix spike and blank sample analysis to determine
analytical accuracy. The frequency of these quality7 assurance 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 inhouse. The chemical 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 Control Matrix Spike Analysis - The procedures and the
frequency of matrix spike analyses are defined in the contract.
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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.
Data Handling
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.
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:
Operational parameters such as GC conditions;
Calibration data;
Special checks unique to each measurement, e.g.,
successive values/averages;
Statistical tests, e.g. outliers; and
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
activities. (GC operating conditions, analytical precision,
etc. should be recorded on standard forms in a logbook.)
8.2.1.1
8.2.1.2
8.2.1.3
8.2.1.4
8.2.1.5
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SECTION III
VOLATILES QA/QC REQUIREMENTS
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TABLE OF CONTENTS
Page Number
PART 1 - Tuning and GC/MS Mass Calibration VOA E-10
Part 2 - Calibration of the GC/MS System VOA E-11
Part 3 - Method Blank Analysis VOA E-16
Part 4 - Surrogate Spike (SS) Analysis VOA E-17
Part 5 - Control Matrix Spike Analysis VOA E-19
Part 6 - Sample Analysis VOA E-20
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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 target compounds in waste 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 Control Matrix Spike 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
and standards calibration (initial or continuing calibration criteria)
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 (12.0) 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 target
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. This criterion must be demonstrated daily or for each
twelve (12) hour time period, whichever is more frequent. If
required, background subtraction should be straightforward and
designed only to eliminate column bleed or instrument
background ions. Background subtraction actions that result in
spectral distortions for the 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 will be used.
1.1.2 BFB criteria MUST be met before any standards, samples or
blanks are analyzed. Any samples analyzed when tuning criteria
have not been met may require reanalysis at no additional cost
to the Agency.
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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 12-hour tuning requirements.
TABLE 1.1 BFB KEY IONS AND ABUNDANCE CRITERIA
Mass Ion Abundance Criteria
50
15.0 - 40.0 percent of mass 95
75
30.0 - 60.0 percent of mass 95
95
Base peak, 100 percent relative abundance
96
5.0 - 9.0 percent of mass 95
173
Less than 2.00 percent of mass 95
174
Greater than 50.0 percent of mass 95
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, control matrix spikes and
blanks 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 in
Exhibit B, Section III.
PART 2 - CALIBRATION OF THE GC/MS SYSTEM
2. Summary
Prior to the analysis of samples, method blanks or control matrix
spikes, 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 target compound
standards. Once the system has been calibrated, the calibration must
be verified each twelve (12) hour time period for each GC/MS system.
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2.1. Prepare calibration standards as described in Exhibit D VOA, Section
IV, to yield the following specific concentrations;
2.1.1 Initial calibration of volatile target compounds is required
at 20, 50, 100, 150 and 200 ug/L in water. (This corresponds
to 10, 25, 50, 75, and 100 mg/kg in a 1 g sample.) Add
working standards of the target compounds (in methanol) to
reagent water. Add additional methanol so that the total
volume of methanol is 100 uL per 5 mL of aqueous standard.
Utilizing the analytical protocol specified in Exhibit D,
this will result in 100-1000 total ng analyzed. If a
standard analyte saturates at the 200 ug/L concentration
level, and the GC/MS system is calibrated to achieve a
detection sensitivity of equal to or greater than 5 ug/L (in
water), the Contractor must document it in the Case
Narrative, and proceed with a four-point initial calibration
for that specific analyte.
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 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 Contractors 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 units. 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.
A|s - Area of the characteristic ion for the
specific internal standards from Table 3 in
Exhibit D.
Cis - Concentration of the internal standard
(ng/uL).
Cx - Concentration of the compound to be measured
(ng/uL).
RRF - x
A,- „
Equation 2.1
where,
A^ - Area of the characteristic ion for the
compound to be measured.
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TABLE 2.1 VOLATILE INTERNAL STANDARDS WITH CORRESPONDING
TARGET ANALYTES ASSIGNED FOR QUANTITATION
Bromochloromethane
I,4-Difluorobenzene
Chlorobenzene-
Chio rome thane
Bromomethane
Vinyl Chloride
Chloroethane
Methylene Chloride
Acetone
Carbon Disulfide
1,1-Dichloroethene
1.1-Dichloroethane
1.2-Dichloroethene
1.1.1-Trichloroethane
Carbon Tetrachloride
Vinyl Acetate
Bromodichlororaethane
1,2-Dichloropropane
trans-1,3-Dichloropropene
Trichloroethene
Dibromochloromethane
1.1.2-Trichloroethane
Benzene
2-Hexanone
4-Me thy1- 2 -Pentanone
Tetrachloroethene
1,1,2,2-Tetrachloroethane
Toluene
Chlorobenzene
Ethylbenzene
Styrene
Total Xylenes
Bromofluorobenz ene
(total)
Chloroform
1,2-Dichloroethane
cis-1,3-Dichloropropene
Bromoform
Toluene-dg (surr)
(surr)
2-Butanone
1,2-Dichloroethane-d^
(surr)
(surr) - surrogate compound
2.3.1 Using the average 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 (CCC) and shown in Table 2.2 (see
2.6.2) using Equation 2.2 below. The calibration check
compounds for volatiles are: vinyl chloride, 1,1-
dichloroethene, chloroform, 1,2-dichloropropane, toluene, and
ethylbenzene.
%RSD - x 100 Equation 2.2
X
where,
RSD - Relative Standard Deviation
SD - Standard Deviation of 5 initial
response factors (per compound)
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x - mean of 5 initial response factors (per
compound)
The %RSD for each individual Calibration Check
Compound must be less than or equal to 30.0 percent.
This criterion 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 volatiles, the five System Performance Check
Compounds (SPCC) 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 Coo 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 and 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 only after the criteria for
the %RSD for the CCC and the minimum average RRF for the SPCC
have both been met. Only after both of 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 target compounds. The Contractor shall
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complete and submit Form V (the CC/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 Forms V and VI are found in Exhibit B,
Section III.
2.6 Continuing Calibration
A calibration standard(s) containing all volatile target compounds,
including all required surrogates, must be performed each twelve (12)
hours during analysis (see definition of twelve-hour time period,
paragraph 1 of this Section). Compare the relative response factor
data from the standards run 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 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 (CCC) listed in Table 2.2 are used to
check the validity of the initial calibration.
Calculate the percent difference using Equation 2.3.
% Difference - x ^qq Equation 2.3
RRF x
where,
RRFj - average relative response factor from initial
calibration.
RRFC - relative response factor from current
verification check standard.
2.6.2.1 If the percent difference for any compound is
greater than 20%, the Contractor 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
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the criteria are riot met (>25.0% difference), for
any one calibration check compound, corrective
action MUST be taken. Problems similar to those
listed under SPCC could affect these 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,
TABLE 2.2 VOLATILE CALIBRATION CHECK
COMPOUNDS (CCC)
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 term stability of
relative 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 volatile target
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. The percent difference (%D)
for each CCC compound must be less than or equal to 25.0
percent. Ensure that the minimum RRF for volatile SPCCs is
0.300 (0.250 for bromoforra). Additional instructions for
completing Form VII are found in Exhibit B, Section III.
PART 3 - METHOD BLANK ANALYSIS
3 • Summary
The method blank is prepared by adding 100 pL of surrogate to 10 mL
of methanol. A volume of the methanol is added to 5 mL of reagent
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water and carried through the entire analytical scheme. The method
blank volume must be approximately equal to the sample volumes being
processed.
3.1 Method blank analysis must be performed at the following frequency:
3.1.1 For the analysis of volatile target compounds, a method blank
analysis must be performed once for each twelve hour time
period. The twelve hour period begins with the injection of
BFB. The method blank must be analyzed after the calibration
standard(s).
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 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, 2-butanone, and
toluene.
3.2.1.2 For all other target compounds not listed above,
the method blank must contain less than or equal
to the Contract Required Quantitation Limit of any
single target analyte.
3.2.2 If a laboratory method blank exceeds this criterion, 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.
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3.3.1 The Contractor shall report ALL sample concentration
data as UNCORRECTED for blanks.
PART 4 - SURROGATE'SPIKE fSS) ANALYSIS
4. Summary
Surrogate standard determinations are performed on all samples and
blanks. All blanks are fortified with surrogate spiking compounds
before extraction in order to monitor preparation and analysis of
samples.
4.1 Each sample, blank, and control matrix spike must be fortified
with the surrogate compounds (shown in Table 4.1) prior to
extraction and purging. Performance based criteria are generated
from laboratory results. Therefore, deviations from the spiking
protocol will not be permitted.
TABLE 4.1 SURROGATE SPIKING LEVELS AND RECOVERY LIMITS
Recovery
Compound Concentration* Limit(%)**
Toluene-dg 50 ug 50 - 160
' 4-Broraofluorobenzene 50 ug 50 - 160
1,2-Dichloroethane-d^ " 50 ug 50 - 160
*In sample extract at the time of injection (before any optional
dilutions).
**These limits are mandatory for method blanks and advisory for
samples and control matrix spikes. They are not used to
determine if a sample or a control matrix spike should be
reanalyzed.
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 4.1.
4.3 Treatment of surrogate spike recovery information shall be according
to paragraphs 4.3.1 and 4.3.2.
4.3.1 Method Blank Surrogate Spike Recovery
The laboratory must take actions listed below if recovery of
any one surrogate compound in the volatiles fraction of the
method blank is outside of the contract required surrogate
spike recovery limits (Table 4.1).
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4.3.1.1 Check calculations to ensure there are no errors;
check internal standard and surrogate spiking
solutions for degradation, contamination, etc;
also, check instrument performance.
4.3.1.2 Recalculate or re- inj ec t/repurge the blank if
steps in 4.3.1.1 indicate this may produce
compliant surrogate recoveries.
4.3.1.3 Re-extract and re-analyze the blank and any
associated samples.
t
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 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.
When the recovery of any one surrogate compound in the
volatiles fraction of the sample or control matrix spike is
outside of the contract surrogate spike recovery limits-" -
(Table 4.1), it is the responsibility of the Contractor to
establish that the deviation is not due to laboratory
problems. The surrogate spike recovery windows for high
concentration samples and control matrix spikes are advisory
at this time.
4.4 Documentation
The Contractor is required to report surrogate recovery data
for the following:
o Method Blank Analyses
o Sample Analyses
o Control Matrix Spike Analyses
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.
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PART 5 - CONTROL MATRIX SPIKE ANALYSIS
5. Summary
in order to evaluate the efficiency of the analytical methodology,
the USEFA has developed standards to be used for control matrix spike
analysis. These compounds are subject to change depending upon
availability and suitability for use as control matrix spikes.
5.1 The Contractor shall perform one control matrix spike sample analysis
for each Case received, or for each 20 single phase units, or each 14
calendar day period during which single phase units 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 following compounds to prepare control matrix spiking
solutions (Exhibit D, Section II, 5.5.1), which require that a
uniform amount of control matrix spiking solution be added to a
control matrix aliquot prior to extraction. The spiking solution
contains the following compounds: 1,1-dichloroethene,
trichloroethene, chlorobenzene, toluene, and benzene.
Analyze the control matrix spike and calculate the individual
component recoveries using Equation 5.1.
Control Matrix Spike CR
Percent Recovery ~ — x 100 Equation 5.1-
where,
CR - Control matrix spike concentration
SA - Concentration of spike added from spiking mix
5.3 Documentation
Matrix spike recovery limits are 60% - 150% for all of the volatile
control matrix spike compounds. These limits are for advisory
purposes only. (They should not be used to determine reanalysis of
a control matrix spike.) When sufficient multi-laboratory data
become available, standard recovery limits will be calculated.
The control matrix spike percent recoveries shall be summarized on
Form III. These values will be used by EPA to establish performance
based QC recovery limits. Complete instructions for the completion
of Form III can be found in Exhibit B, Section III.
PART 6 - SAMPLE ANALYSIS
6. Summary
6.1 Samples can be analyzed upon successful completion of the initial
calibration analysis. When twelve (12) hours have elapsed since the
initial calibration was completed, it is necessary to conduct an
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Rev. 9/88
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instrument tune and continuing calibration analysis. Any major
system maintenance, such as a source cleaning or installation of a
new column, will necessitate a retune and recalibration (See Initial
Calibration, Part 3).
6.1.1 Internal Standards Evaluation
Internal standard response 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. 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 cJaily (12 hour time
period) calibration standard, the mass spectrometric 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
single phase unit, method blank and control matrix. The
criteria are described in detail in the instructions for Form
VIII, High Concentration Internal Area Summary (See Exhibit
B). Breaking off 1 foot of the column or cleaning the
injector sleeve will often improve high end sensitivity for
the late eluting compounds.
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 EICP's with 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
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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 target compounds.
If any compound in any sample exceeds the initial
calibration range, that sample must be diluted,
the internal standard concentration readjusted,
and the sample re-injected, as described in
specific methodologies in Exhibit D VOA.
Secondary ion quantitation is only allowed when
there are sample matrix interferences with the
primary ion.
If the dilution of the sample extract 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 instructions in
Exhibit B.
6.1.3 Qualitative Analysis
The target compounds listed in 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).
6.1.3.1 For establishing correspondence of the GC relative
retention time (RRT), the sample component RJRT
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.
6.1.3.3 The requirements for qualitative verification by
comparison of mass spectra are as follows:
6.1.3.3.1 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.
6.1.2.1
6.1.2.2
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6.1.3.3.2 The relative intensities of ions
specified in the above paragraph must
agree within ±20% between the
standard and sample spectra.
6.1.3.3.3 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. 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. The
verification process should favor
false positives.
6.1.3.4 If a compound cannot be verified by all of the
criteria in 6.1.3.3, 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.
6.1.3.5 A library search shall be executed for
nonsurrogate and non-target 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 Target compounds 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 target analytes are used
(Exhibit D).
6.1.4.2 An estimated concentration for non-target
compounds 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 for all
surrogate compounds, on all single phase units,
method blanks, and control matrix spikes. If
recovery is within contractual or advisory limits,
report on Form II. If recovery is outside
contractual limits for the method blank, take
specific steps listed in Section 4.3, Surrogate
Spike Recoveries.
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6.1.4.4 Calculate control matrix spike present recovery
for all spiked compounds. Report results on Form
III.
6.1.5 Reporting and Deliverables
Refer to Exhibit B of this document 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.
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SECTION III
EXTRACTABLES QA/QC REQUIREMENTS
EXT E-25
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TABLE OF CONTENTS
Part 1 - Tuning and GC/MS Mass Calibration
PAGE NUMBER
EXT E-27
Part 2 - Calibration of the GC/ MS System
EXT E-28
Part 3 - Method Blank Analysis
EXT E-35
Part 4 - Surrogate Spike (SS) Analysis
EXT E-36
Part 5 - Control Matrix Spike Analysis
EXT E-38
Part 6 - Sample Analysis
EXT E-40
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This Section outlines the minimum Quality Control (QC) operations necessary
to satisfy the analytical requirements associated with the determination of
high concentration extractable target compounds in waste 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 Control Matrix Spike Analysis
Part 1 - Tuning and GC/MS Mass Calibration
1. Summary
Prior to initiating any on going data collection, it is necessary to
establish that a given GC/MS meets the standard mass spectral abundance
criteria. This is accomplished through the analysis of
Decafluorotriphenylphosphine (DFTPP), The ion abundance criteria for
each calibration compound MUST be met before any single phase units,
method blanks, or control matrix spikes can be analyzed.
1.1 Decafluorotriphenylphosphine (DFTPP)
1.1.1 Each GC/MS system used for the analysis of semi-volatile or
pesticide target compounds must be hardware tuned to meet the
abundance criteria listed in Table E-l 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. DFTPP must be
injected to meet this criterion. Background subtraction should
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 contrary to the
objectives of Quality Assurance and are unacceptable.
NOTE: All instrument conditions must be identical to those in sample
analyses, except that a different (faster) temperature program
may be used.
1.1.2 Whenever the Contractor takes corrective action which may
change or affect the tuning criteria of DFTPP (e.g., ion source
cleaning or repair, etc.), the tune must be verified
irrespective of the twelve (12) hour tuning requirements.
1.1.3 Any samples analyzed when tuning criteria have not been met
will require reanalysis at no additional "cost to the Agency.
The twelve (12.0) hour time period for GC/MS system tuning and
standards calibration (initial or continuing calibration
EXT E-27
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criteria) begins at the moment of injection of the DFTPP
analysis that the laboratory submits as documentation of
compliant tune. The time period ends after twelve (12) hours
has elapsed according to the GC/MS system clock.
1.2 Documentation
Documentation of the calibration must be provided in the form of a bar
graph plot and as a mass listing.
1.2.1 The Contractor shall complete a Form V (High Concentration
Extractable GC/MS Tuning and Mass Calibration) each time an
analytical system is tuned. In addition, all single phase
units, standards, method blanks, and control matrix spikes
analyzed during a particular tune must be summarized on the
bottom of the appropriate Form V. Detailed instructions for
the completion of Form V are found in Exhibit B, Section III.
TABLE E-l. DFTPP Key Ions and Ion Abundance Criteria
Mass Ion Abundance Criteria
51 30.0 to 60.0 percent of mass 198
68 Less than 2.0 percent of mass 69
69 Mass 69 relative abundance
70 Less than 2.0 percent of mass 69
127 40.0 to 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 to 9.0 percent of mass 198
275 10.0 to 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 to 23.0 percent of mass 442
Part 2 - Calibration of the GC/MS System
2. Summary
Prior to the analysis of samples, method blanks, or control matrix
spikes, and after tuning criteria have been met, the GC/MS system must
be initially calibrated at a minimum of three concentrations to
EXT E-28
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determine the linearity of response utilizing target 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, Section 4, to
yield the following specific concentrations:
2.1.1 Extractable Target Compounds
Initial calibration of all extractable target compounds except
PCBs are required at 50, 80 and 160 total nanograms. Initial
calibration of PGB homolog: one solution containing mono-
through heptachlorobiphenyl are required at 10, 30 and 50 total
nanograms. Octa-, nona- and decachlorobiphenyl are required at
20, 60 and 100 total nanograms (due to their low responses).
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 internal standard to be used on
a compound by compound basis for quantitation. Establishment of
standard calibration procedures is necessary and deviations by
contractor laboratories will not be allowed.
2.3 Analysis of Calibration Standard
2.3.1 Analyze each calibration standard and tabulate the area of the
primary characteristic ion (Exhibit D, Table 1) 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 ±0.05 RRT.
Late eluting compounds usually will have much better agreement.
Using Table E-3, calculate the relative response factors (RRF)
for each target compound at each concentration level using
Equation 3.1.
Equation 3.1
Dpr _ a n
KKt x is
Ais Cx
Where:
Ax - Area of the characteristic ion for the compound to be
measured.
A^s - Area of the characteristic ion for the specified internal
standards from Table E-3,
Cis - Concentration of the internal standard (ng/uL).
Cx — Concentration of the compound to be measured (ng/uL).
EXT E-29
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2.3.2 Using the relative response factors (RRF) from the initial
calibration, calculate the percent relative standard deviations
(% RSD) for compounds labeled as Calibration Check Compounds
using Equation 3.2.
Equation 3.2
% RSD - SD x 100
x
Where:
RSD - Relative Standard Deviation.
SD - Standard Deviation of 3 Initial Relative
Response Factors (Per Compound).
Where:
/n (X£ - X)2
sdWI —i
yi-l n-l
x - Mean of 3 Initial Relative Response Factors (Per Compound).
The % RSD for each individual Calibration Check Compound must
be less than 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 minimum average
relative response factors are met before the calibration curve is used.
2.4.1 For extractables, the System Performance Check Compounds
(SPCC's) 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. These compounds (SPCC's) typically have very low RRF's
(0.1-0.2) and tend to decrease in response as the
chromatographic system or the standard material begin 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 RF for SPCC have been met. Only
after both these criteria are met can sample analysis begin.
EXT E-30
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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 target compounds. The laboratory is required
to submit a Form VI (Initial Calibration Data) for each instrument used
to analyze samples under this protocol. Detailed instructions for
completion of Form VI are found in Exhibit B, Section III.
2.6 Continuing Calibration
The analysis of a calibration standard(s) containing all required
target compounds, including all required surrogates, must be performed
each twelve (12) hours during analysis. Compare the 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 (12) hours. If the
SPCC criteria are met, a comparison of response factors is made for all
compounds. This is the same check that is applied during the initial
calibration (Form VI). If the minimum 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
extractable 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 E-2 are used to check the validity of
the initial calibration. Calculate the percent difference
using Equation 3.3.
Equation 3.3
% Difference - RRFj - RRFC
x 100
RRF j
Where:
RRFj - Average Relative Response Factor from Initial
Calibration.
RRFC - Relative Response Factor from Current Verification Check
Standard.
EXT E-31
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2.6.2.1 If the percent difference for any compound is
greater than 20.0%, the laboratory should consider
this a warning limit. If the percent difference for
each CCC is less than 25.0%, the initial calibration
is assumed to be valid. If the criteria are not met
(greater than 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. This criteria MUST
be net before sample analysis begins.
TABLE E-2. Extractable Calibration Check Compounds
Acenaphthene
1,4-Dichlorobenzene
Hexachlorobutadiene
N-Nitroso-di-n-phenylamine
Di-n-octylphthalate
Fluoranthene
Benzo(a)pyrene
4-Chloro-3-Methylphenol
2,4-Dichlorophenol
2-Nitrophenol
Phenol
Pentachlorophenol
2,4,6-Trichlorophenol
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 calibration standard(s).
2.6.3.1 The concentration for each extractable target
compound except PCBs in the continuing calibration
standard(s) is 80 total nanograms. For the
continuing calibration of the PCBs, one solution
containing mono-through heptachlorobiphenyl is
required at 30 total nanograms, octa-, nano-, and
decachlorobiphenyl are required at 60 total
nanograms for the continuing calibration solution.
2.7 Documentation
The laboratory is required to complete and submit a Form VII
for each GC/MS system utilized for each twelve (12) hour time
period. Calculate and report the response factor and percent
difference (% D) for all compounds. Ensure the minimum RF for
SPCC's is 0.050. The percent difference (% D) for each CCC
EXT E-32
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compound must be less than 25,0 percent. Additional
instructions for completing Form VII are found in Exhibit B,
Deliverables, Section III.
EXT E-33
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TABLE E-3. Standards With Corresponding Extractable Target Compounds
Analytes Assigned For Quantitation
1,4-Dichlorobenzene-d,
Naphthalene-ds
Acenaphthene-d
1Q_
Phenol
bis(2-Chloroethyl)ether
2 -Chlorophenol
1,3-Dichlorobenzene
1, 4-Dichlorobenzene
Benzyl alcohol
1,2 -Dichlorobenzene
2-Methylphenol
b is(2 -Chloro isopropy1)ether
4-Methylphenol
N-Nitroso-di-n-propylamine
Hexachloroethane
2-Fluorophenol (surr)
Phenol-d5 (surr)
Nitrobenzene
Isophorone
2-Nitrophenol
2,4-Dimethylpheno1
Benzoic acid
bis(2-Chloroethoxy)methane
2,4-Dichlorophenol
1,2,4-Trichlorobenzene
Naphthalene
4-Chloroaniline
Hexachlorobutadiene
4-Chloro-3-methylphenol
2-Methylnaphthalene
Nitrobenzene-d5 (surr)
surr — surrogate compound
Hexachlorocyclopenta-
diene
2,4,6-Trichlorophenol
2.4.5-Trichlorophenol
2-Chloronaphthalene
2-Nitroaniline
Dimethyl phthalate
Acenaphthylene
3-Nitroaniline
Acenaphthene
2,4-Dinitrophenol
4-Nitropheno1
Dibenzofuran
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diethyl phthalate
4-Chlorophenyl-phenyl
ether
Fluorene
4-Nitroaniline
2 -Fluorobiphenyl
(surr)
2.4.6-Tribromophenol
(surr)
EXT E- 34
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TABLE E-3. (Continued)
Phenanthrene-d
10
Chrysene-d^2
Perylene-d^2
4,6-Dinitro-2-methylphenol
N-nitrosodiphenylamine
1,2-Diphenylhydrazine
4-Bromophenyl phenyl ether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-butyl phthalate
Fluoranthene
alpha-BHC
beta-BHC
gamma-BHC
delta-BHC
Heptachlor
Aldrin
Heptaclor epoxide
Endrin ketone
Pyrene
Butylbenzyl phthalate
3,3'-Dichlorobenzidine
Benzo(a)anthracene
b is(2 -ethylhexy1)phthalate
Chrysene
Terphenyl-dl4 (surr)
gamma-Chlordane
Endosulfan I
Alpha-Chlordane
Dieldrin
4,4'-DDE
Endrin
Endosulfan II
4,4'-DDD
Endosulfan sulfate
4,4'-DDT
Methoxychlor
Monochlorobiphenyl
Dichlorobiphenyl
Trichlorobiphenyl
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyl
Octachlorobiphenyl
Nonachlorobiphenyl
Decachlorobiphenyl
Di-n-octyl phthalate
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(1,2,3 -cd)
Pyrene
Dibenz(a,h)anthracene
Benzo(g,h,i)perylene
surr — surrogate compound
EXT E-35
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Part 3 - Method Blank Analysis Summary
3, Summary
A method blank is an aliquot of the reagent(s) that is carried through the
entire analytical scheme (extraction, concentration, and analysis). The
method blank weight must be approximately equal to the sample weights being
processed.
3,1 Method blank analysis must be performed at the following frequency:
3.1.1 For the analysis of extractable target compounds, a method blank
analysis must be performed for each case received, or for each 20
single phase units, or whenever single phase units are extracted,
whichever is most frequent. The method blank associated with a
specific set or group of single phase units must be analyzed on each
GC/MS or GC system used to analyze that specific group or set.
3.1.2 It is the laboratory'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.
3.1.2.1 For the purposes of this protocol, an acceptable
laboratory method blank must meet the criteria of
paragraphs 3.1.2.1.1 and 3,1.2.1.2.
3.1.2.1.1- A method blank for extractable analysis must
contain less than two times (2X) the
Contract Required Quantitation Limit (CRQL
from Exhibit C) of phthalate esters in the
TCL,
3.1.2.1.2 For all other extractable target compounds
not listed above, the method blank must
contain less than or equal to the Contract
Required Quantitation Limit (CRQL) of any
target analyte.
3.2.2 If a laboratory method blank exceeds criteria, the Contractor must
consider the analytical system out of control. The source of the
contamination must be investigated and appropriate corrective
measures must be taken before further sample analysis proceeds. All
single phase units 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
designate, must address problems and solutions in the Case Narrative
(Exhibit B).
EXT E-36
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3,3 Documentation
Results of extractable method blank analysis shall be reported using the
High Concentration Extractable Analysis Data Sheet (Form I), and the
tentatively identified compounds (Form I, TIC). In addition, the single
phase units associated with each method blank must be summarized on Form IV
(High Concentration Extractable Method Blank Summary). Specific
instructions for the completion of these forms can be found in Exhibit B
(Reporting and Deliverables), Section III.
3.3.1 The Contractor will report ALL sample concentration data as
UNCORRECTED for blanks. It shall be the responsibility of the EPA
evaluator, and/or data auditor, to correct analyte concentrations
for concentrations detected in the method blank(s). It is the
Contractor's responsibility to ensure the proper number of method
blanks are analyzed and the data properly reported.
Part 4 - Surrogate CSS) Analysis
4. Summary
Surrogate standard determinations are performed on all single phase units,
method blanks, and control matrix spikes. ALL single phase units, method
blanks, and control matrix spikes are fortified with surrogate spiking
compounds before extraction in order to monitor preparation and analysis of
samples.
4.1 Each single phase unit (including control matrix spike and method blank) is
spiked with surrogate compounds prior to extraction. The surrogate spiking
compounds shown in Table E-4 are used to fortify each single phase unit with
the proper concentrations. Performance based criteria are generated from
laboratory results. Therefore deviations from spiking protocol will not be
permitted.
TABLE E-4,Extractable Surrogate Spiking Compounds
Amount in Sample Extract
Compound (before any optional dilutions')
Nitrobenzene-d^ 50 ug
2-Fluorobiphenyl 50 ug
p-Terphenyl-d^ 50 ug
Phenol-d5 100 ug
2-Fluorophenol 100 ug
2 ,4,6-Tribromophenol 100 ug
4.2 Surrogate recovery must be evaluated for acceptance by determining whether
the concentration (measured as percent recovery) falls inside the advisory
recovery limits listed in Table E-5.
EXT E-37
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4.3 Surrogate'spike recovery information is treated according to paragraphs
4,3.1 through 4,3.1.2.
4.3.1 Method Blank Surrogate Recovery
When the surrogate recovery of any one extractable surrogate
compound is outside of the contract required surrogate recovery
limits (listed in Table E-5) for a method blank, the laboratory must
take the following actions:
4.3.1.1 Check calculations to assure there are no errors. Check
internal standard and surrogate spiking solutions for
degradation, contamination, etc. Also, check instrument
performance,
4.3.1.2 Recalculate and/or reinject the extract if steps in
4.3.1.1 reveal the cause of the non-compliant surrogate
recoveries.
4.3.1.3 If the measures listed above fail to correct the problem,
the analytical system must be considered out of control.
The problem MUST be corrected before continuing. This
may mean recalibration of the instrumentation but it may
also mean more extensive action. The specific corrective
action is left up to the GC/MS operator. The method
blank and all associated single phase units, including
any control matrix spikes must be re-extracted and re-
analyzed at no additional cost to the Agency.
TABLE E-5.Surrogate Recovery Limits*
Surrogate Compound % Recovery
Nitrobenzene-dj 20-140
2 -Fluorobiphenyl 20-140
p-Terphenyl-d^ 20-150
Phenol-d^ 20-140
2-Fluorophenol 20-140
2,4,6-Tribromophenol 10-140
* Mandatory for method blanks. Advisory for single phase units and
control matrix spikes.
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4.3.2 Sample Surrogate Recovery
When the surrogate recovery of any one extractable surrogate
compound is outside of the advisory recovery limits (listed in
Table E-5) for any single phase unit (including the control matrix
spike(s)), the laboratory must take the following actions:
4.3.2.1 Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
4.3.2.2 Recalculate the data and/or reanalyze the extract if any
of the above checks reveal a problem.
"4.3.2.3 If surrogates cannot be detected due to dilution factors,
this requirement (4.3.2.1) need not be met, report the
value(s) as
-------
5.2 Use the compounds listed in Table E-6 to prepare control matrix spiking
solutions according to protocols described in Exhibit D, Section II, 4.8.
The analytical protocols in Exhibit D, require that a uniform amount of
control matrix spiking solution be added to the control matrix prior to
extraction.
5.3 Individual component recoveries of the control matrix spike are calculated
using Equation 5.1.
Matrix Spike Percent Recovery - SSR - SR x ^qq Equation 5.1
SA
Where:
SSR - Spike Sample Results
SR - Sample Result
SA - Spike Added from Spiking Mix
TABLE E-6.Control Matrix Spiking Solutions*
Base/Neutrals Acids
1,4-Dichlorobenzene
N-Nitroso-di-n-propylamine
1,2,4-Trichlorobenzene
Acenaphthene
2,4-Dinitrotoluene
Pyrene
Phenol
2 -Chloropheno1
4-Chloro-3-me thyIpheno1
4-Nitrophenol
Penpachlorophenol
Pesticides
Heptachlor
Dieldr-in
*Base/Neutrals and Acids are combined in one solution,
are prepared in a separate solution.
The pesticides
5.4 Documentation
The control matrix spike percent recoveries shall be summarized on Form
III. These values will be used by EPA to periodically update existing
performance based QC recovery limits.
See Exhibit B, Deliverables, Section III, for complete instructions on the
completion of Form III,
EXT E-40
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TABLE E-7.Control Matrix Spike Recovery Limits*
Compound Class Matrix Spike Compound
% Recovery*
BN
BN
BN
BN
BN
BN
N-Nitroso-di-n-propylamine
1,4-Dichlorobenzene
1,2,4-Trichlorobenzene
Acenaphthene
2,4-Dinitrotoluene
Pyrene
30-140
30-140
30-140
30-140
30-140
30-140
Acid
Acid
Acid
Acid
Acid
Phenol
2-Chlorophenol
4-Chloro-3-methylphenol
4-Nitrophenol
Pentachlorophenol
10-120
10-120
10-120
10-120
10-120
Pesticide
Pesticide
Heptachlor
Dieldrin
30-140
30-140
* These limits are for advisory purposes only. They are not to be used to
determine if a sample should be reanalyzed. When sufficient data are
available, standard-limits will be calculated.
Part 6 - Quality Control
6. Summary
6.1 Samples can be analyzed upon successful completion of the initial QC
activities. When twelve (12) hours have elapsed since the initial QC was
completed, it is necessary to conduct an instrument tune and calibration
check analysis (described in Part 1 of this Exhibit). Any major system
maintenance, such as a source cleaning or installation of a new column, will
necessitate a retune and recalibration (See Initial Calibration, Section
III, Part 2).
6.1.1 Internal Standards Evaluation
Internal standard response 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. 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. The extracted ion current profile (EICP) of the
internal standards must be monitored and evaluated for each single
phase unit, method blank, and control matrix. The criteria are
described in detail in the instructions for Form VIII, High
Concentration Internal Area Summary (See Exhibit B). Breaking off 1
foot of the column or cleaning the injector sleeve will often
improve high end sensitivity for the late eluting compounds.
EXT E-41
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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 EICP's
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 satura-te 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.
If any compound in any sample exceeds the initial
calibration range, that sample must be diluted, the
internal standard concentration re-adjusted, and the
sample re-injected, as described in Exhibit D, Section
III, 5.2. Secondary ion quantitation is only allowed
when there are sample matrix interferences with the
primary ion.
If the dilution of the sample extract 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
instructions in Exhibit B.
6.1.3 Qualitative Analysis
The target compounds listed in 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).
6.1.2.1
6.1.2.2
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6.1,3.1 For establishing correspondence of the GC relative
retention time (RRT), the sample component KRT must
compare within +0.05 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
Exhibit E, Part 1 must be met on the Contractor's same
GC/MS.
6.1.3.3 The requirements for qualitative verification by
comparison of mass spectra are as follows:
6.1.3.3.1 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 same
spectrum.
6.1.3.3.2 The relative intensities of ions specified
in the above paragraph must agree within
±20% between the standard and sample
spectra.
6.1.3.3.3 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. 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. The verification process
should favor false positives (Exhibit D).
6.1.3.4 A library search shall be executed for non-target sample
components for the purpose of tentative identification.
For this purpose, the most recent available version of
the EPA/NBS Mass Spectral Library should be used.
6.1.4 Quantitation
6.1.4.1 Target components identified shall be quantitated by the
internal standard method. The internal standard used
shall be the ones assigned in Table E-3, Exhibit E. The
EICP area of characteristic ions of target analytes are
used (Exhibit D tables D-l, D-5).
6.1.4.2 An estimated concentration for non-target components
tentatively identified shall be quantitated by the
internal standard method. For quantification, the
nearest internal standard free of interferences must be
used.
EXT E-43
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6.1.4.3 Calculate surrogate standard recovery for all surrogate '
compounds, on all single phase units, method blanks, and
control matrix spikes. If recovery is within contractual
or advisory limits, report on Form II (See Exhibit B).
If recovery is outside contractual limits for the method
blank, take specific steps listed in Exhibit E, Surrogate
Spike Recoveries.
6.1.4.4 Calculate control matrix spike percent recovery for all
spiked compounds. Report results on Form III.
6.1.5 Reporting and Deliverables
Refer to Exhibit B of this document 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.
EXT E-44
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EXHIBIT E
AROCLORS/TOXAPHENE QA/QC REQUIREMENTS
ARO E-45
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1. Summary
This section outlines the minimum quality control (QC) operations
necessary to satisfy the analytical requirements associated with the
determination of Aroclors and Toxaphene in high concentration samples
using the analytical method described in Exhibit D. The QC operations
described below apply to analyses performed on both GC columns of all
instruments.
Initial PC requirements:
o Determination of potential quantitation peaks for each analyte and
determination of their Absolute Retention Times (RT) and
calibration factors.
Periodic QC requirements:
o Continued monitoring of RTs and calibration factors.
o Instrument blank analysis,
o Method blank analysis,
o Control matrix spike analysis.
Additional PC requirements:
o Surrogate recoveries are reported for all samples, blanks, and
control matrix spike analyses.
o Retention time shifts of the surrogates are reported for the
analyses of all standards, samples, control matrix spikes and
blanks.
These QC operations are designed to facilitate comparison of analytical
data from different laboratories. These requirements do not release
the analytical laboratory from maintaining their own checks on the
performance of their instruments. These checks may include, but are
not limited to, determining detector standing current, monitoring the
number of theoretical plates per column and establishing the limits of
quantitation for each of the analytes.
2. DEFINITICNS
2.1 Instrument Blank
The instrument blank is a solution containing the surrogates
Tetrachloro-meta-xylene and Decachlorobiphenyl (20 ng/mL) in hexane.
This solution must be injected no less than once every 12 hours on each
GC column used in order to demonstrate that none of the Aroclors or
Toxaphene listed in the Exhibit C are detected at > 0.5 the contract
required quantitation limit (CRQL).
2.2 Method Blank
A method blank is 500 mg of corn oil spiked with the surrogates (20
ng/mL) that is carried through the entire analytical scheme given in
Exhibit D. An acceptable method blank is required for each full or
ARO E-46
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partial sec of 20 samples analyzed in a sample delivery group (SDG).
An acceptable method blank, has none of the Aroclors or Toxaphene listed
in Exhibit C at > CRQL.
2,3 Control Matrix Spike
A control matrix spike is prepared by spiking an aliquot of corn oil
with the Aroclor 1254 spiking solution (25 ug/mL). The Contractor
shall perform one control matrix spike sample analysis for each Case
received, or for each 20 single phase units, or each 14 calendar day
period during which single phase units 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. INITIAL CALIBRATION
3.1 Prior to analysis of samples, it is necessary to run a successful
calibration sequence using this sequence of injections:
TABLE E.l. INITIAL CALIBRATION
No. of Potential
Injection No. Concentration Aroclor Quantitation Peaks
1
Blank
—
—
2
Resolution Check -
—
3
Low
1221
4
4
Medium
1221
4
5
High
1221
4
6
Low
1232
4
7
Medium
1232
4
8
High
1232
4
9
Low
1242
5
10
Medium
1242
5
11
High
1242
5
12
Low
1248
5
13
Medium
1248
5
14
High
1248
5
15
Low
1254
5
16
Medium
1254
5
17
High
1254
5
18
Low
1016/1260
5/5
19
Medium
1016/1260
5/5
20
High
1016/1260
5/5
21
Low
Toxaphene
4
22
Medium
Toxaphene
4
23
High
Toxaphene
4
24
Low
Pesticide A
_
25
Low
Pesticide B
—
26
Blank
_
_
This sequence will establish potential quantitation peaks and their
retention times. It will also establish a linear response calibration
for each analyte peak.
ARO E-47
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3.2 Each Aroclor and Toxaphene calibration standard must be run at three
concentrations. The analytes and the concentrations required for the
low point are given in Table E.2. The midpoint concentrations are 10
times the low point concentration, and the high point concentration is
selected by the laboratory in the concentration range between 30 to 100
times the low point concentration. It is recommended that a
concentration 100 times the CRQL be used for the high point
calibration, provided that it lies within the linear range of the
detector. The high point calibration point defines the upper end of
the concentration range for which the calibration is valid.
TABLE E.2. LOW POINT AROCLOR CALIBRATION SOLUTIONS
Compound
CAS Number Low Concentration
1. Aroclor 1016 12674-11-2 50 ng/mL
Aroclor 1260 11096-82-5 50 ng/mL
2. Aroclor 1221 11104-28-2 50 ng/mL
3. Aroclor 1232 11141-16-5 50 ng/mL
4. Aroclor 1242 53469-21-9 50 ng/mL
5. Aroclor 1248 12672-29-6 50 ng/mL
6. Aroclor 1254 11097-69-1 50 ng/mL
7. Toxaphene 8001-35-2 500 ng/mL
8. Tetrachloro-meta-xylene 877-09-8 20 ng/mL
9. Decaclorobiphenyl 2051-24-3 20 ng/mL
3.3 An on-scale chromatogram must be presented for each calibration run.
3.4 During the initial calibration sequence absolute retention times (RT)
are determined for four or five major peaks of each Aroclor and
Toxaphene.
3.5 If the mean deviation (M.D.) of the absolute retention time for the
three calibration measurements for any peak exceeds 0.5 percent of the
mean absolute retention time (RT) for that peak, the analytical system
is out of control and corrective action must be taken before collecting
any data.
M.D.
13 _
3 I |RTt - RT|
i-1
(3.1)
RTt
- Absolute retention time of quantitation peak.
RT - Mean absolute retention time of the quantitation
peak.
3.6 A retention time window of +1.0 percent of the RT established during
the initial calibration is calculated for each quantitation peak.
3.7 Three-point instrument calibration is required for each potential
quantitation peak. The laboratory has three choices on how to
establish three-point calibration (sections 3.7.1 - 3.7.3). Only one
ARO E-48
Rev. 9/88
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of the three calibration methods may be used to quantitate samples in
any single run sequence. Therefore, once a system is calibrated,
laboratories may not change calibration techniques for samples until a
new initial calibration is run,
3.7.1 The laboratory may use a mean calibration factor (CF)
determined from the three concentrations but only if the % RSD
for the three points is <15 percent.
Response of
— 1 V Peak Area (or Height1) of the Standard
^ ~ T ^ Mass Injected (ng)
i i-1 6 (3.2)
S£
%RSD - == x 100
CF (3.3)
in z
Where SD - / T (CF, - CF)
^-1 L and n-3 (3.4)
n-1
3.7.2 The laboratory may use a calibration line drawn through all
three calibration points if the value for r (the correlation
coefficient from the linear regression calculation) is >0.975
and if the zero concentration intercept is <0.20 times the low
point response for each analyte quantitated.
3.7.3 Laboratories with electronic integrators or data systems that
automatically calculate calibration curves as line segments
between calibration points may use two line segment calibration
curves for each quantitation peak of the Aroclor or Toxaphene.
This technique may be used only if r (the correlation
coefficient from the linear regression calculation) is >0.975
for all three points for each peak and if the zero
concentration intercept is <0.20 times the low point response
for each Aroclor or Toxaphene peak quantitated.
3.8 Because they are potential method interferences, mixtures of single
component pesticides are injected as part of the calibration sequence
to establish the RT of individual pesticides. Calibration factors are
not calculated for the individual pesticide standards.
ARO E-49
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3.9
TABLE E.3. PESTICIDE MIXTURES
Individual
Standard
Mix A
Concentration
(ng/mL)
Individual
Standard
Mix B
Concentration
(ng/mL)
alpha-BHC
Heptachlor
gamma-BHC
Endosulfan I
Dieldrin
Endrin
p,p'-DDD
p,p'-DDT
Me thoxychlo r
Tetrachloro-meta-xylene
Decachlorobiphenyl
25.0 beta-BHC
25.0 delta-BHC
25.0 Aldrin
25.0 Heptachlor epoxide
50.0 alpha-Chlordane
50.0 gamma-Chlordane
50.0 p,p'-DDE
50.0 Endosulfan sulfate
50.0 Endrin aldehyde
20.0 Tetrachloro-meta-xylene
20.0 Decachlorobiphenyl
25.0
25.0
25.0
25.0
25.0
25.0
50.0
50.0
50.0
20.0
20.0
50.0
50.0
Endrin Ketone
Endosulfan II
3.10 Sample analysis may not proceed until a satisfactory calibration has
been demonstrated.
3.11 The more highly chlorinated Aroclor and Toxaphene components are more
stable in the environment. Therefore, the analyst should emphasize the
later eluting peaks of a pattern in identifying and quantitating
weathered Aroclors and Toxaphene
3.12 If more than one Aroclor is observed in a sample, or if an Aroclor and
Toxaphene occur in the same sample, the laboratory must choose separate
peaks to quantitate the different analytes. A peak common to both
analytes present in the sample must not be used to quantitate both
Aroclors.
3.13 The surrogates must be added to all calibration standards. The
retention time shifts of the surrogates may not excede 0.5% for the
analysis of any calibration standard.
3.14 Documentation for Initial Calibration
3.14.1 Documentation of the RT and calibration factors for potential
quantitation peaks on both columns must be provided in tabular
form. Form VI will be used to report the RT of each potential
quantitation peak at each of the three concentrations. The
average RT and the relative mean deviation of the three
measurements shall also be reported. Form VI will be used to
report the CF for each peak at each concentration injected, the
concentrations injected, the average CF and the relative
standard deviation of the calibration factors at each of the
three concentrations.
ARO E-50
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3.14.2 Documentation of sequence of calibration standards and their
retention time shifts must be provided in tabular form on Form
VIII.
3.14.3 Documentation of the RT for pesticides on both columns must be
provided in tabular form using Form IX.
3.15 Copies of Forms VI, VIII, and IX, as well as instructions for
completion of those forms, are presented in Exhibit B of this document.
All chromatograms, as well as integration reports or data system
printouts for calibration analyses must be submitted in hard copy with
the data package.
4. CONTINUED GC PERFORMANCE EVALUATION
4.1 Summary
4.1.1 The performance of the GC must be monitored every 12 hours by
running an instrument blank (Section 2.1) and an evaluation
standard. The evaluation standard is used to verify that the
RT's and CF's of the analyte quantitation peaks have not
changed since the initial calibration.
4.1.2 Analysts are cautioned that analyzing an instrument blank and
an evaluation mixture once every 12 hours is the minimum
contract requirement. Highly complex samples or unstable GC
equipment may cause peaks from one injection to be carried over
to the next. It may be necessary to analyze these more often
to avoid discarding data.
4.1.3 The requirement for running the 12 hour instrument blanks and
evaluation mixture is waived when no samples or spike control
matrix analyses are run during that 12-hour period. After a
break in sample data analysis, a laboratory can resume the
analysis of samples and control matrix spikes using the current
initial calibration only after an acceptable evaluation mixture
is analyzed (3.2). If a successful evaluation mixture cannot
be analyzed after an interruption, an acceptable initial
calibration must be run before sample data can be collected.
NOTE: This section does not affect the requirement that all
acceptable sample analyses must be bracketed by acceptable
evaluation mixtures.
4.2 Performance Evaluation Standard
4.2.1 A performance evaluation standard must be run at least once in
every 12 hours. If that analysis does not meet the criteria
below, a second injection of the same standard at the same
concentration must be made immediately.
4.2.2 The performance evaluation standards injected at 12 hour (or
less) intervals will be rotated so as to include the Toxaphene
and common Aroclors at low, medium, and high concentrations
according to the following schedule:
ARO E-51
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TABLE E.4.
12 HOUR EVALUATIONS
Concentration
Comoound
Hour
low
Toxaphene
12
low
1248
24
low
1254
36
low
1016/1260
48
medium
Toxaphene
60
medium
1248
72
medium
1254
84
medium
1016/1260
96
high
Toxaphene
108
high
1248
120
high
1254
132
high
1016/1260
144
Repeat
4.2.3 For each of the four or five potential quantitation peaks, the
RT in the standard must be within the retention time window of
±1.0 percent of the mean RT calculated during the initial
calibration.
4.2.4 For each of the four or five potential quantitation peaks, the
response (area or height) must be within 20.0 percent (+20.0
RPD) of the mean response obtained during the initial
calibration.
RPD
CF - CFr
x 100
CF
(4.1)
CF - Average calibration factor from initial
calibration (Equation 3.2).
CFp - Calibration factor from current
E evaluation mixture.
4.2.5 The retention time shifts of the surrogates in the evaluation
standard must not excede 0.5%.
4.2.6 If the performance evaluation mixture does not meet all of the
criteria listed above, the GC system is out of control and
appropriate corrective action must then be taken before
additional data are collected. After corrections have been
made, the initial calibration must be run successfully. All
samples analyzed since the previous acceptable evaluation must
be reinjected at no additional cost to the Agency. The
laboratory manager, or his designate, must address problems and
solutions in the narrative.
ARO E-52
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4.3 Documentation
4.3.1 Documentation of an acceptable performance evaluation mixture
analysis on each column shall be submitted on Form Vll for each
12 hours of analysis. In addition, each analysis of a
performance evaluation mixture must be listed on the analytical
sequence given on Form VIII regardless of whether or not it was
acceptable.
4.3.2 A hard copy of all chromatograms of performance evaluation
analyses, as well as integration reports or data system
printouts, must be submitted with the data package.
4.4 Instructions for completing the data reporting forms are contained in
Exhibit B.
5. BLANK ANALYSIS
5.1 Two types of blanks are required as part of this protocol. Method
blanks, which provide a measure of total laboratory contamination, and
instrument blanks, which provide a measure of instrument contamination
and sample carry over between injections.
5.2 Method Blank
5.2.1 A method blank of corn oil (500 mg) must be extracted and
cleaned up using the protocols given in Exhibit D.
5.2.2 A method blank analysis must be performed for each twenty
single phase units in each sample delivery group. It is
suggested that blanks be run more often whenever particularly
dirty samples are analyzed.
5.2.3 If only a partial set of samples require sulfur cleanup, then
two method blanks are required, [one that is shaken with
mercury (or copper) and one that is not] .
5.2.4 The method blanks must be injected directly after a sample in
the run sequence. They may not be run immediately after an
instrument blank.
5.2.5 The method blank may not contain more than the contract
required quantitation limit of any Aroclor or Toxaphene
quantitation peak. If a method blank exceeds the criterion,
the analytical system is out of control. The source of the
contamination must be investigated and appropriate corrective
measures must be taken. All samples processed with a method
blank that is out of control (i.e., contaminated) must be re-
extracted, cleaned up again, and reanalyzed at no additional
cost to the Agency. The laboratory manager, or his designate,
must address problems and solutions in the narrative (Exhibit
B).
5.2.6 The retention time shifts of the surrogates in the method blank
must not excede 0.5%.
ARO E-53
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5.3 Instrument Blank
5.3.1 An instrument blank is a hexane solution containing 20 ng/mL of
both of the surrogates. An acceptable instrument blank must be
run at least once every 12 hours. An instrument blank must be
run immediately prior to the performance evaluation mixture in
the run sequence (see Exhibit D). To avoid the necessity of
reanalysis, it is recommended that additional blanks be
analyzed whenever particularly dirty samples are analyzed.
5.3.2 An acceptable instrument blank analysis must demonstrate that
no potential quantitation peak of an Aroclor or Toxaphene is
detected at greater than 0.5 times the CRQL. If quantitation
peaks identified during the initial calibration are detected at
greater than half the CRQL, all data collection must be stopped
and corrective action taken. Data for samples with analytes
detected at >CRQL which were analyzed between the last
acceptable instrument blank and the unacceptable blank must be
considered suspect. An acceptable instrument blank must be run
before additional data is collected. After an acceptable
instrument blank is run, all samples with Aroclors or Toxaphene
detected at levels >CRQL analyzed after the last acceptable
instrument blank must be reinjected during a valid run sequence
and reported at no expense to the Agency.
5.3.3 If an instrument blank exceeds the 0.5 x CRQL criteria, the
Contractor must consider the analytical system out of control.
The source of the contamination must be investigated and
appropriate corrective measures must be taken. The laboratory
manager, or his designate, must address problems and solutions
in the narrative (Exhibit B).
5.3.4 The retention time shifts of the surrogates in the instrument
blank must not excede 0.5%.
5.4 Documentation
5.4.1 Results of method blank analysis must be reported using Form I
(Aroclor/Toxaphene Analysis Data Sheet). In addition, the
samples associated with each method blank must be summarized on
Form IV. Specific instructions for the completion of these
forms can be found in Exhibit B.
5.4.2 Results of instrument blank analyses must be reported using
Form I. In addition, the samples associated with each
instrument blank must be summarized on Form IV. Specific
instructions for the completion of these forms can be found in
Exhibit B.
5.4.3 In addition, each analysis of a method blank or instrument
blank must be reported on Form VIII for each analytical
sequence.
ARO E-54
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5.4.4 Chromatograms, as well as integration reports or data system
printouts for calibration analyses must be submitted in hard
copy with the data package.
5.4.5 The Contractor will report ALL sample concentration data
UNCORRECTED for blanks. It shall be the responsibility of the
EPA evaluator, or data auditor, to correct analyte
concentrations for concentrations detected in the blank(s). It
is the Contractor's responsibility to ensure that the proper
number of blanks are analyzed and that the data are properly
reported.
6. CONTROL MATRIX SPIKE ANALYSIS
6.1 Control Matrix Spike Requirements
6.1.1 In order to evaluate the effect of the sample matrix upon the
analytical methodology, the EPA has specified that a solution
containing Aroclor 1254 at 25 ug/mL) be used to spike a control
matrix of corn oil (500 mg).
6.1.2 A control matrix spike must be analyzed once for each Case, or
for every 20 single phase units.
6.2 Calculations
6.2.1 The recovery of each Aroclor 1254 in the control matrix spike
is calculated using Equation 6.1.
Control
Matrix
Spike - SSR x 100 (fil)
Percent SA
Recovery
Where:
SSR - Spike Sample Results
SA - Spike Added from Spiking Mix
6.3 Documentation
6.3.1 The concentration of nonspike target compounds in the control
matrix spike must be reported on Form I. The quantitation of
each Aroclor 1254 peak on both columns must be reported on Form
X. The recovery of Aroclor 1254 must be reported on Form III.
Specific instructions on the completion of these forms may be
found in Exhibit B.
6.3.2 Chromatograms as well as integration reports or data system
printouts of control matrix spike analyses, will be submitted
in hard copy with the data package.
ARO E-55
Rev. 4/89
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7. SAMPLE CLEANUP
7.1. Summary
The cleanup of sample requires Diol cartridges for all samples.
Every lot number of Diol cartridges must be tested by the
following procedure before they are used for sample cleanup.
Add 0.5 mL of Aroclor, midpoint concentration (described in
Exhibit D, Section 5.5.1) to 4 mL of hexane, then reduce the
final volume to 0.5 mL using nitrogen (Exhibit D, Section 5.4).
Place the mixture onto the top of a prewashed Diol cartridge,
and elute it with 9 mL of hexane/acetone [(90:10)(V/V)].
Adjust the final volume to 10.0 mL and analyze by GC/ECD.
The recovery of Aroclor 1254 must be determined for evaluation
and reporting purposes. The lot of Diol cartridges is
acceptable if the Aroclor is recovered at 80 to 110 percent.
7.4 Documentation
7.4.1 Documentation of the Diol cartridge performance will be
provided on Form XI by reporting the recovery of Aroclor 1254.
8. SAMPLE ANALYSIS SUMMARY
8.1 General
8.1.1 This section DOES NOT replace or supersede the specific
analytical methods or QA/QC activities described in previous
sections. The intent of this subsection is to provide the
contractor laboratory with a BRIEF summary of QC activities
involved with sample analysis to help the contractor laboratory
meet specific reporting and deliverables required by this
contract.
8.1.2 Samples may only be analyzed upon successful completion of the
initial QC activities. The laboratory must run an evaluation
mixture and an instrument blank (described in Section 2.1) at
least every 12 hours. The laboratory may continue to
quantitate data using the initial calibration until an
instrument blank shows greater than half the contract minimum
level of any Aroclor or Toxaphene, an unacceptable evaluation
mixture is analyzed, or the calibration factor of a
multicomponent analyte changes by more than 20 percent. Any
major system maintenance, such as installation of a new column
or, changing or cleaning the detector will also necessitate
reanalysis of the initial calibration sequence.
8.1.3 All acceptable data must be bracketed with an acceptable
instrument blank and an acceptable evaluation mixture. Any
samples analyzed which do not meet this criteria must be
reinjected and reported at no expense to the Agency.
7.1.1
7.1.2
ARO E-56
Rev, 9/88
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8.1.4 At least one acceptable evaluation mixture must be run every 12
hours. If an unacceptable evaluation run is made, the
laboratory must run a second evaluation mixture immediately.
If the results of two successive evaluation runs do not meet
the specifications of Section 4.2, then all analyses since the .
last acceptable evaluation mixture are not valid. They must be
reinjected after the GC is inspected for malfunction and
corrections made as appropriate. Loss of sensitivity or
resolution could result from a damaged septum or column. High
detector standing current (background) could result from
contaminated carrier gas or from a dirty detector.
8.1.5 An acceptable instrument blank analysis must demonstrate that
no potential quantitation peak of an Aroclor or Toxaphene is
detected at greater than 0.5 times the CRQL. If quantitation
peaks identified during the initial calibration are detected at
greater than half the CRQL, all data collection must be stopped
and corrective action taken. Data for samples with analytes
detected at >CRQL which were analyzed between the last
acceptable instrument blank and the unacceptable blank must be
considered suspect. An acceptable instrument blank must be run
before additional data is collected. After an acceptable
instrument blank is run, all samples with Aroclors or Toxaphene
detected at levels >CRQL analyzed after the last acceptable .
instrument blank must be reinjected during a valid run sequence
and reported at no expense to the Agency.
8.1.6 At least one method blank must be analyzed for each 20 single
phase units analyzed. If any Aroclor or Toxaphene is detected,
in a method blank, at more than the CRQL, all sample data
collection must stop. The laboratory must then immediately run
an instrument blank to demonstrate that the instrument is not
contaminated. When an acceptable instrument blank has been
analyzed, the same method blank must be reinjected. If the
method blank is unacceptable after the second injection, all
single phase units that were analyzed since the last acceptable
method blank must be re-extracted, cleaned up again and
analyzed at no expense to the Agency.
8.2 Sample Dilution
8.2.1 The protocol is intended to achieve the quantitation limits
shown in Exhibit C whenever possible. Whenever sample
chromatograms have interfering peaks, a high baseline, or off-
scale peaks, the samples must be reanalyzed following further
dilution. Samples which cannot be made to meet the
specifications given in this section after dilution and cleanup
(sulfuric acid, permanganate, Diol cartridge and mercury
removal) are discussed in detail in the Case Narrative and do
not require further analysis. No limit is placed on the number
of re-extractions and cleanups of samples that may be required
because of contaminated method blanks.
ARO E-57
Rev. 9/88
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The sample must be analyzed at the most concentrated level
consistent with achieving satisfactory chromatography (defined
below). If dilution is employed solely to bring a peak within
the calibration range or produce an on-scale chromatogram for
the multicomponent analyte, the results for both a more and a
less concentrated dilution must be reported. The resulting
changes in quantitation limits and surrogate recoveries must
also be reported for the dilute samples.
If the laboratory has reason to believe that diluting the final
volume will be necessary, an undiluted run may not be required.
If an acceptable chromatogram (as defined in Section 5.) is
achieved with the diluted final volume, an additional analysis
at 10 times the concentration of the diluted material must be
injected and reported with the sample data.
The response of peaks in the sample must be >25 percent of full
scale to allow visual pattern recognition of multicomponent
analytes.
An on-scale chromatogram(s) of all identified peaks must be
presented with the sample data.
Chromatographic data may be replotted electronically in order
to get an on-scale chromatogram, except when the off-scale
sample peaks are larger than the high point calibration peaks.
In that case, the samples must be diluted and reinjected.
The peak response of sample peaks on the replotted chromatogram
must be >25 percent of full scale to allow visual pattern
recognition of multicomponent analytes.
8.3 Data Acceptance Criteria
8.3.1 Reportable data for a sample must include a chromatogram with a
baseline which returns to below 50 percent of full scale before
the elution time of Aroclor 1221 and to below 25 percent of
full scale after Aroclor 1221 and before the elution time of
Decachlorobiphenyl.
8.3.2 If dilution has been applied and no peaks are detected above 25
percent of full scale, analysis of a more concentrated extract
is required.
8.3.3 Reportable sample data must include chromatogram(s) with all
Aroclor and Toxaphene quantitation peaks in the linear range of
the quantitation curve determined by the initial calibration.
8.3.4 Reportable sample data must include chromatogram(s) with all
Aroclor and Toxaphene peaks on-scale.
NOTE: If more than one chromatogram is required to satisfy the
criteria for a sample, the results of all chromatograms must be
reported. These requirements apply to both columns.
8.2.3
8.2.4
8.2.5
8.2.6
8.2.7
ARO E-58
Rev. 9/88
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8.3.5 The retention time shifts for the surrogates in any sample must
not excede 0.5%. If the surrogates have been diluted out, so
that no retention time shift can be calculated, report the
percent difference as "dil" (see Forms Instructions), and
explain in the Case Narrative.
8.4 Quantitation of Analyses
8.4.1 Analytes can be quantitated using either a modern electronic
integrator or with a laboratory data system. The analyst can
use either peak height or peak area as the basis for
quantitation. The use of an electronic integrator or a
laboratory data system is required.
8.4.2 The chromatograms of all samples must be reviewed by a
qualified pesticide/PCB analyst before they are reported.
8.4.3 Using an electronic integrator, one of three calibration
techniques may be employed (Section 3.7). It is the
responsibility of the analyst to set the integration parameters
such that off-scale chromatograms are within the dynamic range
of the instrument. The analyst should also check for data
flags generated by the instrument that indicate improper
quantitation of peaks prior to reporting data to the EPA.
8.4.4 In order to be quantitated, the detector response (peak area or
peak height) of all analytes must lie between the responses of
the low and high concentrations in the initial calibration. If
the analytes are detected below the CRQL, they are reported
with the appropriate flags (See Exhibit B). If they are
detected at a level greater than the high calibration point,
the sample must be diluted either to a maximum of 1:100,000, or
until the response is within the linear range established
during calibration.
8.4.5 The concentration of the Aroclor and Toxaphene quantitation
peaks are calculated using the following equations:
Concentration ug/L -
(AaXV,.)
(CF)(vi)(Wx) (8.1)
Where:
Ax — Response for the peak to be measured.
CF - Calibration factor from the initial calibration.
Vc - Volume of total waste dilution (uL) (take into
account any dilution).
?£ - Volume of waste dilution injected (uL).
Wx - Weight of waste diluted (gm).
AR0 E-59
Rev. 9/88
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8.4.6
The the recoveries of the surrogates are calculated using the
following equations:
SA - SR
Percent Recovery — x 100%
SA (8.2)
SA — Concentration of surrogate added
SR — Concentration of surrogate recovered
8.4.7 The laboratory will quantitate each of the selected Aroclor or
Toxaphene peaks individually, and determine an average
concentration from all of the selected peaks. Quantitation is
performed on both columns, and the lower value is reported on
Form I. See Exhibit B for instructions on completing Form I
and Form X.
8.4.8 Detected Aroclors and Toxaphene must be reported as: (1) a
concentration between the CRQL and 10 x CRQL, or (2) as an
estimated value below the CRQL. (See Exhibit B.)
8.4.9 The choice of the peaks used for Aroclor or Toxaphene
quantitation and recognition of those peaks may be complicated
by the environmental alteration of the Aroclor or Toxaphene,
and by the presence of coeluting analytes or matrix
interferences.
8.4.10 The more highly chlorinated components of the Aroclors and
Toxaphene are more stable in the environment. Therefore, the
analyst should emphasize the later eluting peaks of a pattern
when identifying and quantitating weathered Aroclors or
Toxaphene.
8.4.11 If more than one Aroclor is observed in a sample or if an
Aroclor and Toxaphene are both observed in a sample the
laboratory must choose separate quantitation peaks for the
different Aroclors and Toxaphene. A peak common to both
analytes in the sample must not be used to quantitate both
compounds.
8.5 Documentation
8.5.1 Refer to Exhibit B of this document for specific details on
contract deliverable and reporting formats. Exhibit B contains
specific instructions for completing all required forms, as
well as detailed itemization of deliverables and reporting
requirements.
9. Surrogates
9.1 Requirements
9.1.1 Tetrachloro-meta-xylene and Decachlorobiphenyl must be added to
each sample, control matrix spike, and blank analyzed as part
of this protocol.
ARO E-60 Rev. 4/89
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9,1,2 The recoveries of the surrogates are calculated using equation
8.2,
9.2 Documentation
9.2.1 The recoveries of the surrogates are reported for each sample,
diluted sample, and control matrix spike on Form II.
9.2.2 Complete instructions for the completion of Form II are given
in Exhibit B.
10, GC Maintenance
10.1 Laboratory Responsibility
10.1.1 It is critical that the gas chromatographs used for these
analyses be maintained properly and that all manufacturers'
recommendation be followed. Although not addressed in this
document, it is expected that each analytical laboratory will
maintain performance checks on their instruments, including
monitoring detector standing current and monitoring the number
of theoretical plates per column.
10.2 Suggested Maintenance
10.2.1 GC Columns - When degradation in column performance is
observed, it is usually the result of a build up of
nonvolatiles on the head of the column. These can best be
removed by cutting off 1-2 feet of the injector end of the
column. The analyst must cool the column(s) to room
temperature before exposing them to air or the column(s) will
oxidize and lose some ability to resolve analytes,
10.2.2 Septa - must be replaced regularly to prevent degradation of
chromatographic performance and destruction of the columns.
They must be replaced at least once per day whenever data are
collected.
10.2.3 Carrier Gas - should be high purity, oxygen, and water free.
The use of in-line water and oxygen traps is recommended even
if ultra-high purity gas is used.
10.3.4 Electron Capture Detector - The condition of the detector can
be monitored by its standing current. A high standing current
usually indicates contaminated carrier gas, a high column bleed
rate, or a dirty detector. Changing the gas filters, oxygen
traps, or the column may correct the problem. If it does not,
raise the detector temperature overnight to bake out the
detector.
10.2.5 NOTE: Do not collect data while cleaning the detector.
ARO E-61
Rev, 9/88
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10,2,6 More serious contamination will require steam cleaning the
detector or detector repair by the manufacturer. Steam
cleaning or detector repair will necessitate recalibration of
the instrument.
10.3 Documentation
10.3.1 All major instrument maintenance or repair will be recorded,
dated, and initialed in an instrument log that will be made
available to auditors during on-site inspections.
11. Solvents and Reagents
11.1 Aliquots of 100 mL of all lots of solvents used for the analysis of
samples by this method will be concentrated, exchanged to a final
volume of 1.0 mL of hexane and analyzed by GC/ECD, The solvent lot is
acceptable only if no analyte is detected at >0.5 CRQL.
11.2 Commercial standards must be diluted and analyzed by GC/ECD to
demonstrate that they give acceptable retention times and that they
give a response between 95 to 105 percent of EPA repository standards.
11.3 Documentation
11.3.1 Chromatograas for all lots of solvents, and commercial
standards must be on file at the laboratory. They are not a
contract deliverable.
ARO E-62
Rev. 9/88
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SECTION IV
ANALYTICAL STANDARDS
A. The Environmental Protection Agency's Quality Assurance Materials Bank will
supply primary standards (calibration standards, surrogate standards, control
matrix spiking standards, and internal standards), contingent upon their
availability, 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 laboratory is responsible for preparing its
own working standards from commercial sources.
B. Caution should be exercised in the mixing of these standards, 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.
C. 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.
D. Upon award of a contract, a list of available standards will be provided by
EMSL-LV upon request.
E-63
Rev. 9/88
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QUAUTY ASSURANCE MATERIALS BANK
REQUEST for reference standards
MAIL TO: VS. Environmental Protection Agency
Quality Assurance Materials Bank (MD-8)
Research Triangle Park. NC 27711 USA
Telephone: Requests ONLY: (91915*1-4019
(FTS) 629-4019
Information: (702)545-2690
(FTS) 545-2690
Technical Assistance: <919)541-3951
(FT9629-39S1
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Request for Reference Standards
E-64
Rev. 9/88
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SECTION V
LABORATORY EVALUATION PROCEDURES
This section outlines the procedures which will be used by the Project Officer or
his/her 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. Hie following is a description
of these two steps.
Part 1 - Evaluation of Laboratory Performance
1. Performance Evaluation Sample Analysis
1.1 A Performance Evaluation (PE) sample set may 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 as 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 these 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-65
Rev. 9/88
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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 Contractor
has implemented the recommended and/or required corrective actions, with
respect to quality assurance, made during the previous on-site visit.
E-66
Rev,
9/88
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EXHIBIT F
CHAIN-OF-CUSTODY, DOCUMENT CONTROL,
AND STANDARD OPERATING PROCEDURES
-------
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 sample 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.
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
F-2
Rev. 9/88
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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.
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Rev. 9/88
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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 item 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
Rev, 9/88
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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, arid1" 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
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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.
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 been signed out to that
person by the DCO. The documents shall be returned to the locked
file at the conclusion of each working day. Confidential information
may not be reproduced except upon approval by the EPA 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.
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Figure 1
Example
DOCUMENT INVENTORY
Document Control #* Document Type # Pages
232-2-0001
Case File Document Inventory Sheet
1
232-2-0002
Chain-of-Custody Records
2
232-2-0003
Shipping Manifests
2
232-2-0004
Sample Tags
50
232-2-0005
SMO Organics Traffic Reports
10
232-2-0006
GC/MS spectra for sample B0310
20
232-2-0007
GC/MS spectra for sample B0311
20
232-2-0008
GC/MS spectra for sample B0319
20
232-2-0009
Analyst's logbook pages
6
232-2-0010
GC/MS library search worksheets
15
232-2-0011
GC instrument log pages
5
232-2-0012
GC/MS QC data sheets
4
etc.
etc.
etc.
*This number is to be recorded on each set of documents.
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EXHIBIT G
GLOSSARY OF TERMS
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GLOSSARY OF TERMS
ALIQUOT - a measured portion of a sample taken for analysis.
ANALYSIS DATE/TIME - the date and military time of the injection of the
sample, standard, or blank into the GC/MS or GC system.
AROCLOR - trade name (Monsanto) for a series of commercial polychlorinated
biphenyls and polychlorinated terphenyl mixtures marketed in the United
States.
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. BFB tuning criteria must be met
before GC/MS analysis can begin. (BFB is also used as a surrogate.)
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.
CONFIRMATION ANALYSIS - see Primary Analysis.
CONTINUING CALIBRATION - analytical standard run every 12 hours to verify the
calibration of the purge and trap-GC/MS system,
CONTINUOUS LIQUID-LIQUID EXTRACTION - used herein synonymously with the terms
continuous extraction, continuous liquid extraction, and liquid extraction.
CONTROL MATRIX SPIKE - corn oil fortified with known quantities of specified
compounds analyzed to measure the recovery (accuracy) of the entire
analytical method.
DAY - unless otherwise specified, day shall mean calendar day.
DECAFLUOROTRIPHENYLPHOSPHINE (DFTPP) - compound chosen to establish mass
spectral tuning performance for extractable analysis, DFTPP tuning criteria
must be met before GC/MS analysis can begin.
EXTRACTABLE - a compound that can be partitioned into an organic solvent from
the sample matrix and is amenable to gas chromatography. Extractables
include Base/Neutrals, Acids and Festiciue/PCB compounds.
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HOMOLQG - one of the 10 levels of chlorination of PCBs (C]_2H9C^ through
C12C^10^ or ot;her group of compounds, varying by systematic addition of
substituent.
IN-HOUSE - at the Contractor's facility.
INITIAL CALIBRATION - analysis of analytical standards for a series of
different specified concentrations; used to define the linearity and dynamic
range of the response of the mass spectrometer to the target compounds.
INTERNAL STANDARDS - compounds added to every standard, blank, control matrix
spike and sample extract 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.
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) - first portion of the data package which includes
laboratory name, contract number, 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 solid phase
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.
PHASE - describes the physical state(s) of the sample. Three "phase
designatores" are used: Solid; Water miscible liquid; Water immiscible
liquid, A sample may contain multiple phases.
PCB CONGENER - one of 209 PCBs at any level of chlorination.
PCB ISOMER - any PCB or other compound which has the same molecular formula,
but different positional substitutions. (2,2' dichlorobiphenyl and 2,3
dichlorobiphenyl are isomeric.)
POLYCHLORINATED BIPHENYLS (PCBS) - a class of 209 discrete chemical compounds
in which one to ten chlorine atoms are attached to biphenyl; i.e.,
monochlorobiphenyl through decachlorobiphenyl with the formula C12H10.nCLn
where n - 1-10.
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
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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).
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;
%Rec - measured value x 10o%
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:
RRF - K X cts
A P
is Sc
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
chromatograms, calculated by dividing the height of the valley between the
peaks by the peak height of the smaller peak being resolved, multipled by
100.
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SAMPLE - a portion of material to be analyzed that is contained in single or
multiple containers and identified by a unique sample number. A sample may
contain more than one phase.
SAMPLE DELIVERY GROUP (SDG) - a unit within a sample Case that is used to
identify a group of samples for delivery. An SDG is a group of 20 or fewer
single phase units within a Case, received over a period of up to 14 calendar
days. Data from all single phase units in an SDG are due concurrently. A
Sample Delivery Group is defined by one of the following, whichever occurs
first:
o Case; or
o Each 20 single phase units within a Case; or
o Each 14-day calendar period during which samples in a Case are
received, beginning with receipt of the first sample in the Case or
SDG.
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.
SINGLE PHASE UNIT - a subsample consisting of a single phase. Multiple phase
samples are phase separated into single phase units. According to the
protocol, single phase units are analyzed and reported as discrete samples.
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 and thereby calibrate
the mass spectrometer.
SURROGATES (Surrogate Standard) - compounds added to every blank, sample,
control matrix spike, and standard; used to evaluate analytical efficiency by
measuring recovery. Surrogates are brominated or isotopically labeled
compounds not expected to be detected in environmental media.
SYSTEM PERFORMANCE CHECK COMPOUNDS (SPCC) - target compounds designated to
monitor purge and trap/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.
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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 and standards calibration (initial or continuing calibration) 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.
VALIDATED TIME OF SAMPLE RECEIPT (VTSR) - the date on which a sample is
received at the Contractor's facility, as recorded on the shipper's delivery
receipt and Sample Traffic Report.
VOLATILE COMPOUNDS - compounds amenable to analysis by the purge and trap
technique. Used synonymously with purgeable compounds.
WIDE BORE CAPILLARY COLUMN - a gas chromatographic column with an internal
diameter (ID) that is greater than 0.32 mm. Columns with lesser diameters
are classified as narrow bore capillaries.
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