United States Office of Publication 9240.1 -10
Environmental Protection Solid Waste and Dp^54^^^075
Agency Emergency Response SowriSr"994
Superfund
£EPA SUPERFUND ANALYTICAL
METHODS rOR LOW
CONCENTRATION WATER FOR
ORGANICS ANALYSIS
-------
9240.1-10
PB95-963505
EPA540/R-94/075
SUPERFOND ANALYTICAL METHODS
FOR
LOW CONCENTRATION WATER FOR ORGANICS ANALYSIS
6/91
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
6/91
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EXHIBIT B
REPORTING AND DELIVERABLES REQUIREMENTS
B-l 6/91
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Table of Contents
Page
SECTION I: Contract Reports/Deliverables Distribution B-3
SECTION II: Report Descriptions and Order of Data
Deliverables B-6
SECTION III: Foras Instruction Guide B-24
SECTION IV: Data Reporting Foras B-45
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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 ten of the contract.
SMO will notify the Contractor in writing of such changes when they occur.
I ten
No.
Copies
Delivery
Schedule
Distribution
(1) (2) (3) (4)
1. Updated SOPs
60 days after
contract award
and as required in
Exhibit E.
XXX
*2. Sample Traffic
Reports
***3. Sample Data Summary
Package
***4. Sample Data Package
*** 5. Complete SDG File
***6. Data in Computer-
Readable Form
3 days after
receipt of last
sample in Sample
Delivery Group
(SDG).**
14 days after
receipt of last
sample in SDG.
14 days after
receipt of last
sample in SDG.
14 days after
receipt of last
sample in SDG.
14 days after
receipt of last
sample in SDG.
X
X
X
X
X
X
Distribution:
(1) Sample Management Office (SMO)
(2) EMSL-LV
(3) Region-Client (Technical Project Officer)
(4) NEIC
B-3
6/91
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Item
No.
Copies
Delivery
Schedule
Distribution
(1) (2) (3) (4)
7.
GC/MS Tapes
8.
Extracts
9.***** QA Plan
Lot Retain for 365 days As Directed
after data submis-
sion, or submit with-
in 7 days after
receipt of written
request.
Lot Retain for 365 days As Directed
after data submis-
sion, or submit with-
in 7 days after
receipt of written
request.
3 Copy Submit within 60 days As Directed
after contract award,
and as required in
Exhibit E.
NOTE:
*
**
Contractor must be prepared to receive the full contract sample
requirement at the time of contract award.
Also required in the Sample Data Summary Package.
Sample Delivery Group (SDG) is a group of samples within a Case,
received over a period of 7 days or less and not exceeding 20
samples. Data for all samples in the SDG are due concurrently. The
date of delivery of the SDG or any samples within the SDG is the
date that all samples have been delivered.
Concurrent delivery required. Delivery shall be made such that all
designated recipients receive the item on the same calendar day.
Complete SDG file will contain the original sample data package plus
all of the original documents described under Complete SDG File
paragraph 5.
***** See Exhibit E for a more detailed description.
NOTE: As specified in the Contract Schedule (Section G, Government
Furnished Supplies and Materials), unless otherwise instructed by
the CLP Sample Management Office, the Contractor shall dispose of
unused sample volume and used sample bottles/containers no earlier
than sixty (60) days following submission of the reconciled complete
SDG file. Sample disposal and disposal of unused sample
bottles/containers is the responsibility of the Contractor and
B-4
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should be done in accordance with all applicable laws and
regulations governing disposal of such materials.
Distribution Addresses :
(1) USEPA Contract Lab Program
Sample Management Office (SMO)
P. 0. Box 818
Alexandria, VA 22313
For overnight delivery, service, use street address:
300 North Lee Street, Suite 200
Alexandria, VA 22314
(2) 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
(3) USEPA REGIONS:
The CLP Sample Management Office will provide the Contractor with the
list of addressees for the ten EPA Regions. SMO will provide the
Contractor with updated Regional address/name lists as necessary
throughout the period of the contract and identify other client
recipients on a case-by-case basis.
(4) USEPA National Enforcement Investigations Center (NEIC)
ATTN: CLP Audit Program
Denver Federal Center Bldg. S3
P.O. Box 25227
Denver, CO 80225
B-5 6/91
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SECTION II
REPORT DESCRIPTIONS AHD ORDER OF DATA PELI7ERABLBS
The Contractor laboratory shall provide reports and other deliverables as
specified in the Contract Schedule (Performance/Delivery Schedule, Section
F). The required content and form of each deliverable is described in this
Exhibit.
All reports and documentation MOST BE:
o Legible
o Clearly labeled and completed in accordance with instructions in this
Exhibit
o Arranged in the order specified in this Section
o Paginated consecutively in ascending order starting from the SDG Narrative
If submitted documentation does not conform to the above criteria, the
Contractor will be required to resubmit such documentation with the
deficiencies corrected, at no additional.''^"-J^ •
«
Whenever the Contractor is required to submit or resubmit data as a result of
an on-site laboratory evaluation, through a SMO action, or through a Regional
Data Reviewer's request, the data must be clearly marked as ADDITIONAL DATA
and must be sent to all three contractual data recipients (SMO, EMSL/LV, and
Region). A cover letter shall be included which describes what data are
being delivered, to which EPA Case(s)/SDGs it pertains, and who requested the
data.
Whenever the Contractor is required to submit or resubmit data as a. result of
Contract Compliance Screening (CCS) review by SMO, the data must be sent to
all three contractual data recipients (SMO, EMSL/LV, and Region), and in all
three instances must be accompanied by a color-coded COVER SHEET (Laboratory
Response To Results of Contract Compliance Screening) provided by SMO.
Descriptions of the requirements for each deliverable item cited in the
Contract Performance/Delivery Schedule (Contract Schedule, Section F) are
specified in this Section. Items submitted concurrently MOST BE arranged in
the order listed. The components of each item MOST BE arranged in the order
presented in this Section when the item is submitted.
Section III contains the form instructions to assist the Contractor in
providing all the required data. Section IV of this Exhibit contains copies
of the required data reporting forms in specified formats.
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1 QUALITY ASSURANCE PLAH AND STANDARD OPERATING PROCEDURES
See contract for specifications.
2. SAt!?LE TFAg?Tc REPORTS
2.1 Original Sample Traffic Report page narked "Lab Copy for Return to SMO"
with lab receipt information and signed in original Contractor
signature, for each sample in the Sample Delivery Group.
2.2 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.
2.3 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).
2.4 When more ttvm one sample is received in the first or last SDG
shipment, the "first" sample received would be the lowest sample number
(considering both alpha and numeric designations); the "last" sample
received would be the highest sample number (considering both alpha and
numeric designations).
2.5 The EPA Sample Number of the first sample received in the SDG is the
SDG number. Each Traffic Report must be clearly marked with the SDG
Number. This information should be entered below the Lab Receipt Date
on the TR. The TR for the last sample received in the last SDG
shipment must be clearly marked "SDG - FINAL SAMPLE."
2.6 If samples are received at the laboratory with multi-sample Traffic
Reports (TRs), all the samples on one multi-sample TR may not
necessarily be in the same SDG. In this instance, the laboratory must
make the appropriate number of photocopies of the TR, and submit one
copy with each SDG cover sheet.
3. SAMPLE DATA SUMMARY PACKAGE
3.1 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 shall be submitted
separately (i.e., separated by rubber bands, clips or other means)
directly preceding the Sample Data Package.
3.2 The Sample Data Summary Package consists of specified items from the
Sample Data Package in the following order:
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o SDG Narrative
o Organics Analysis Data Sheet for target contpound results (Form
I) and for tentatively identified compounds (Form I, TIC) by
fraction (VOA, SV, PEST) and by sample within each fraction.
(No Fora I, TIC for PEST fraction.)
o Surrogate Recovery (Font II) by fraction (VOA, SV, PEST)
o Laboratory Control Sample Recovery (Fora III) by fraction (VOA,
SV, PEST)
o Method Blank Suaaary (Fora IV), Organics Analysis Data Sheet for
target coapound results (Fora I) and for tentatively identified
coapounds (Fora I, TIC) by fraction (VOA, SV).
o Peak Area and Retention Time Summary of Internal Standards for
initial calibration standards (Fora VIII) and saaples (Form
VIII) by fraction (VOA, SV only).
3.3 Saaple data forms shall be arranged in increasing EPA Saaple Number
order.
4. gAifpr.ii; DATA PACKAGE
4.1 The Saaple Data Package shall include data for analyses of all saaples
in each Saaple Delivery Group, specifically including field saaples,
reanalyses, dilutions, blanks, Laboratory Control Saaples, and
Performance Evaluation Saaples. The Saaple Data Package is divided
into the five major units as follows:
o SDG Narrative
o Sample Traffic Reports
o Volatiles Data
o Seaivolatiles Data
o Pestieides/Aroclors Data
4.2 The Volatiles, Semivolatiles, and Pestieides/Aroclors data are each
specific to an analytical fraction. If the analysis of that fraction
is not required, then that fraction-specific unit is not a required
deliverable.
The Contractor shall retain a copy of the saaple data package for 365
days after final acceptance of data. After *h*« time, the Contractor
may dispose of the package.
4.3. SDG Narrative
4.3.1 This document shall be clearly labeled "SDG Narrative". The
SDG Narrative shall contain: laboratory name; Case number; EPA
Sample Numbers in the Sample Delivery Group (SDG),
differentiating between initial analyses, dilutions and
reanalysis; SDG number; Contract number; and detailed
documentation of any quality control sample, shipment and/or
B-8 6/91
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analytical problems encountered in processing the samples
reported in the data package.
4.3.2 Whenever data from sample reanalyses are submitted, the
Contractor shall state in the SDG Narrative for each
reanalysis, whether it considers the reanalysis to be billable,
and if so, why. A copy of the narrative should be sent to SMO
for their review. The Contractor must also include any
problems encountered; both technical and administrative, the
corrective actions taken, and resolution.
4.3.3 The Contractor must also list the pH determined for each water
sample submitted for volatiles analysis. This information may
appear as a simple list or table in the SDG Narrative. The
purpose of this pH determination is to ensure that all
volatiles samples were acidified in the field. No pH
adjustment is to be performed by the Contractor on water
samples for volatiles analysis.
4.3.4 The SDG Narrative shall contain the following statement
varfrafr1"- "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 data package and
in the computer-readable data submitted on diskette has been
authorized by the Laboratory Manager or his designee, as
verified by the following signature.* This statement shall be
directly followed by signature of the Laboratory Manager or his
designee with a typed line below it containing the signer's
name and title, and the date of signature.
4.3.5 In the event that the Laboratory Manager cannot verify all data
reported for each saople, the Laboratory Manager shall provide
a detailed description of the problems associated with the
samples in the SDG Narrative.
4.3.6 The SDG Narrative itself must be signed with original signature
by the Laboratory Manager or his designee and dated.
4.4 Sample Traffic Reports
Copies of the Sample Traffic Reports for all of the samples in the SDG
are also included in the Sample Data Summary Package. The Traffic
Reports shall be arranged in increasing EPA Sample Number order,
considering both letters and numbers 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), not all samples on one multi-sample TR are necessarily
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
B-9 6/91
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sane data package, the laboratory oust submit a copy of the SDG cover
sheet with copies of the TRs.
4.5 Volatiles Data
4.5.1 Volatiles QC Summary
If more than a single fora is necessary, each type of fora oust
be arranged in chronological order by instrument.
o Surrogate Recovery (Fora II LC7)
o Laboratory Control Saaple Recovery (Fora III LCV)
o Method Blank Suaaary (Fora 17 LCV)
o GC/MS Tuning and Mass Calibration - BFB (Fora V LCV)
o Internal Standard Area and Retention Tine Suaaary (Fora
VIII LCV)
4.5.2 Volatiles Saaple Data
Saaple data, including FES, shall be arranged in packets with
both of the Organic Analysis Data Sheets (Fora I LCV and Fora I
LCV-TIC), followed by the raw data for volatile saaples. These
saaple packets should then be placed in increasing EPA Saaple
Number order.
4.5.2.1 Organics Analysis Data Sheet for target compound
results (Fora I LCV).
4.5.2.2 Organics Analysis Data Sheet for tentatively
identified coapounds (Fora I LCV-TIC). This fora
aust be included even if no TIC's are found.
4.5.2.3 Reconstructed total ion chroaatograas (RIG)
The RIG for each saaple, extract, standard, and
blank Bust be normalized to the largest nonsolvent
component, and must contain the following header
information:
o EPA Saaple 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 the compounds,
either directly out from the peak, or on a print-out
of retention times if retention times are printed
over the peak.
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4.5.2.4 Quantisation Report
If automated data systems are used for quantisation
of the target compounds, the complete data system
quantitation report must be included in all sample
data packages, in addition to the reconstructed ion
chromatogram. The complete data system quantitation
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* quantitation report containing the
following information must be included in the sample
data package in addition to the chromatogram.
o EPA Sample Number
o Date and time of analysis
o RT or scan number of identified target
compounds
o Ion used for quantitation with measured
o Copy of area table from data system
o GC/MS instrument ID
o Lab file ID
In all instances where the data system report has
been edited, or where manual integration or
quantitation has been performed, the GC/MS operator
must identify such edits or manual procedures by
initialing and dating the changes made to the report
and include the scan range integration.
4.5.2.5 Target Compound Mass Spectra
For each sample, by each compound identified, copies
of raw spectra and copies of background-subtracted
mass spectra of target compounds that are identified
in the sample and corresponding background-
subtracted target compound standard mass spectra are
required. The raw spectra and die background-
subtracted 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.
4.5.2.6 Tentatively Identified Compound Mass Spectra and
Library Matches
B-ll 6/91
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For each sample, by each compound identified, copies
of mass spectra of non-target and non-surrogate
organic compounds (Tentatively Identified Compounds)
with the associated spectra of the three best
library matches are labeled with EPA Sample Number,
lab file ID, date and time of analysis, and GC/MS
instrument ID.
4.5.3 Volatiles Standards Data
4.5.3.1 Initial Calibration
All initial calibration data must be included for
all analyses associated with the SDG. When more
than one initial calibration is performed, the
reconstructed ion chromatograms and quantitation
reports and each type of form must be put in
chronological order, by instrument.
Initial Calibration Summary (Form VI LCV).
Internal Standard Area and Retention Time Summary
(Form VIII LCV)
Volatile standard(s) reconstructed ion chromatograms
and quantitation reports for the initial (five
point) calibration are labeled as in Paragraphs
4.5.2.3 and 4.5.2.4. Spectra are not required.
4.5.3.2 Continuing Calibration
When more than one continuing calibration is
performed, the reconstructed ion chromatogram and
quantitation reports and each type of form must be
in chronological order, and by instrument if more
than one instrument is used.
Continuing Calibration Summary (Form VII LCV)
Internal Standard Area and Retention Time Summary
(Form VIII LCV)
VGA standard(s) reconstructed ion chromatograms and
quantitation reports for all continuing (12 hour)
calibrations are labeled as in Paragraph 4.5.2.3 and
4.5.2.4. Spectra are not required.
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4.5.4 Volatiles QC Data
4.5.4.1 GC/MS Tuning Data
GC/MS Turning - BFB data, for each 12-hour period,
shall be arranged in chronological order by
instrument for each GC/MS system utilized.
GC/MS Tuning and Mass Calibration - BFB (Fora V LCV)
Bar graph spectrum, labeled as in Paragraph 4.5.2.3.
Mass listing, labeled as in Paragraph 4.5.2.3.
4.5.4.2 Blank Data
Blank data shall be arranged in chronological order
by instrument. NOTE: This order is different from
that used for samples.
Blank data shall be arranged in packets with both of
the Organic Analysis Data Sheets (Form I LCV and
Form I LCV-TIC), followed by the raw data for
volatile samples (see paragraphs 4.5.2.1 to
4.5.2.6).
4.5.4.3 Laboratory Control Sample Data
Organics Analysis Data Sheet for target compound
results (Form I LCV). Form I LCV-TIC is not
required.
Reconstructed icn chromatogram(s) and qusntitation
report(s), labeled as in Paragraph 4.5.2.3 and
4.5.2.4. Spectra are not required.
4.6 Semivolatiles Data
4.6.1 Semivolatiles QC Summary
If more than a single form is necessary, each type of form must
be arranged in chronological order, by instrument.
o Surrogate Recovery (Form II LCSV)
o Laboratory Control Sample Recovery (Form III
LCSV)
o Method Blank Summary (Form IV LCSV)
o GC/MS Tuning and Mass Calibration - DFTPP (Form
V LCSV)
o Internal Standard Area and Retention Time
Summary (Form VIII LCSV-1, LCSV-2)
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4.6.2 Semivolatiles Sample Data
Sample data, including FES, shall the arranged in packets with
both of the Organic Analysis Data* S&eets (Fora I LCSV and Form
I LCSV-TIC) , followed by the saw dtaea for seaivolatile samples.
These sample packets should them Bmt gliaced in increasing EPA
Sample Number order.
4.6.2.1 Organic Analysis Wmtm il&aet for target compound
results (Fora I LOSP-U, M57-2).
4.6.2.2 Tentatively Idmiftfffrnfl fPimji !• (Font I LCSV-TIC).
This fora must be inulhiiftrf even if no TICs are
found.
4.6.2.3 Reconstructed total ion cnromatograas (RICs)
The RIC for each mmyBii „ extract, standard, and
blank must be nonm££zBdi to the largest nonsolvent
component, and move ffiimmiUfi the following header
information:
o EPA Sample BmmBor
o Date and time oS. aomfflysis
o GO/MS inst
o Lab file ID
Internal standard andt smntDgace spiking compounds
are to be labeled w£Q& en« names of the compounds,
either directly ostx fennt ttne peak, or on a print-out
of retention fimrj isE raatetction times are printed
over the peak.
4.6.2.4 Quantitation
If automated data sy»cam» procedures are used for
preliminary < adl of the information listed
below. For laboracmcdtes vhich do not use the
automated data sjacumi procedures, a laboratory "raw
data sheet" quantfcat&cnc report containing the
following infdrmmiLiui nose be included in the sample
data package in a*£Lt=ixinx to the chromatogram.
EPA Sample
Date and time aS analysis
B-14 6/91
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o RT or scan number of identified target
compounds
o Ion used for quantisation with measured
area
o Copy of peak area table from data system
o GC/MS instrument ID
o Lab file ID
In all instances where the data system report has
been edited, or where manual integration or
quantitation has been performed, the GC/HS operator
oast Identity such edits or manual procedures by
*q^«?'t«T,
-------
Initial Calibration Data (Form VI LCSV-1, LCSV-2).
Internal Standard Area and RT Summary (Form VIII
LCSV-1, LCSV-2)
Semivolatile standard(s) reconstructed Ion
ehroaatograas and quantitation reports for the
initial (five point) calibration are labeled as in
Paragraphs 4.6.2.3 and 4.6.2.4. Spectra are not
required.
4.6.3.2 Continuing Calibration
When acre than one continuing calibration is
performed, the reconstructed ion chroaatogram and
quantitation reports and each type of fora must be
in chronological order, by instrument.
Continuing Calibration Summary(Form VII LCSV-1,
LCSV-2).
Internal Standard Area and Retention Time Summary
(Form VIII LCSV-1, LCSV-2).
Semivolatile standard(s) reconstructed ion
ehromatograas and quantitation reports for all
continuing (12 hour) calibrations are labeled as in
Paragraphs 4.6.2.3 and 4.6.2.4. Spectra are not
required.
4.6.4. Seaivolatiles QC Data
4.6.4.1 GC/HS Tuning Data
GC/MS Tuning-DFTPP data, for each 12-hour period
shall be arranged in chronological order by
instrument, for each GC/MS system utilized.
GC/MS Tuning and Mass Calibration-BFB (Form V LCSV)
Bar graph spectrum, labeled as in Paragraph 4.6.2.3.
Mass listing, labeled as in Paragraph 4.6.2.3.
4.6.4.2 Blank Data
Blank data shall be arranged in chronological order
by instrument. NOTE: This order is different from
that used for samples.
Blank data shall be arranged in packets with both of
the Organic Analysis Data Sheets (Form I LCSV and
Form I LCSV-TIC), followed by the raw data for
B-16 6/91
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semi-volatile samples (see paragraphs 4.6.2.1 to
4.6.2.6)
4.6.4.3 Laboratory Control Sample Data
Organic Analysis Data Sheet for target compounds
(Fora I LCSV-1, LCSV-2). Form I LCSV-TIC is saj
required.
Reconstructed ion chromatogram(s) and quantitation
report(s), are labeled as in Paragraphs 4.6.2.3 and
4.6.2.4. Spectra are not required.
4.7 Pesticide/Aroclor Data
4.7.1 Pesticide/Aroclor QC Summary
If more than a single form is necessary, forms must be arranged
in chronological order by instrument.
o Surrogate Percent Recovery Summary (Form II LCP)
o Laboratory Control Sample Recovery (Form III LCP)
o Method Blank Summary (Form IV LCP)
If more than a single method blank summary form is
necessary, forms must be arranged in chronological order
by type (method or sulfur blank) by instrument, and by
date of analyses.
4.7.2 Pesticide/Aroclor Sample Data
Sample data, including PES, shall be arranged in packets with
the Organic Analysis Data Sheet (Form I LCP), followed by the
raw data for pesticide samples. These sample packets should
then be placed in increasing EPA Sample Number order.
4.7.2.1 Organic Analysis Data Sheet for target compounds
(Form I LCP).
4.7.2.2 Pesticide Identification Summary for Single
Component Analytes (Form X LCP-1), only required for
positively identified analytes.
4.7.2.3 Pesticide Identification Summary for Multicomponent
Analytes (Form X LCP-2) , only required for
positively identified analytes.
4.7.2.4 Pesticide chromatograms
All chromatograms must be labeled with the following
information:
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o EPA Sample Number
o Volume injected (ul)
o Date and time of analyses
o GC column identification (by stationary
phase and internal diameter)
o GC instrument identification
o Scaling Factor
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.
4.7.2.5 Copies of pesticide chromatograms from second GC
column, labeled as in Paragraph 4.7.2.4.
4.7.2.6 Data System Printouts
Data system printouts of retention time and
corresponding peak areas or height must accompany
each chromatogram are labeled with the following
information:
o EPA Sample Number
o Volume injected (ul)
o Date and time of analyses
o GC column identification (by stationary
phase and internal diameter)
o GC instrument identification
o Scaling Factor
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.
In all instances where the data system report has
been edited, or where manual integration or
quantitation has been performed, the GC/EC operator
must identify such edits or manual procedures by
B-18 6/91
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initialing and dating the change* made to the report
and include the integration lime range.
4.7.2.7 Manual work sheets.
4.7.3 Pesticide/Aroclor Standards Data
4.7.3.1 Initial Calibration
Data oust be included for all calibration analyses
pertaining to the SDG. Uhen more than one initial
calibration is performed, the data and each type of
form must be put in chronological order, by
instrument and GC column.
Initial Calibration for Single Component Analytes
(Form VI LCP-1, LCP-2).
Initial Calibration for Multicomponent Analytes
(Form VI LCP-3).
Resolution Check Summary (Form VI LCP-4).
Analytical Sequence (Form VIII LCP), containing
initial calibration standards.
4.7.3.2 Calibration Verification
Calibration Verification Summary (Form VII LCP) for
all GC columns.
Uhen more than one calibration verification is
performed, forms must be in chronological order, by
instrument and GC column.
4.7.3.3 Chromatograms and data system printouts are required
for all standards and arranged in chronological
order by instrument and each GC column:
o Resolution Check Mixture.
o Performance Evaluation Mixtures, each initial
calibration and all those that bracket samples
in the SDG.
o Individual Standard Mixture A, at three
concentrations, each initial calibration,
plus all those that bracket samples in
the SDG.
o Individual Standard Mixture B, at three
concentrations, each initial calibration,
plus all those that bracket samples in
the SDG.
B-19 6/91
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o All nultieomponent analytes (Toxaphene
and Aroclors), each initial
calibration.
o All multieomponent analyte standards
analyzed for confiraaeion.
4.7.3.4 Data system printouts of retention tines and
corresponding peak areas or peak heights oust
acconpany each chromatogram. In addition, all
chromatograms and data system printouts are required
to be labeled with the following:
o EPA Sample Number for the standard,
i.e., INDAl, DJDA2, etc. (See Forms
Instructions for details).
o Label all standard peaks for all
individual compounds either directly
out from the peak or on the printout of
retention times if retention times are
printed over the peak.
o Total nanograms injected for each
standard.
o Date and time of injection.
o GC column identification (by stationary
phase and internal diameter).
o GC instrument identification.
o Scaling factor
In all instances where the data system report has
been edited, or where manual integration or
quantitation has been performed, the GC/EC operator
must identity such edits or manual procedures by
initialing and dating the changes made to the report
and include the integration time range.
4.7.4 Festicide/Aroclor QC Data
4.7.4.1 Blank Data
Blank data instrument - grouped by type of blank
(i.e., method and sulfur) and arranged in
chronological order. NOTE: This order is different
from that used for samples.
Organics Analysis Data Sheet for target compounds
(Form I LCP).
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Blank data shall be arranged in packets with the
Organics Analysis Data Sheet (Form I LCP) followed
by the raw data (paragraph 4.7.2.2, to 4.7.2.7).
4.7.4.2 Laboratory Control Sample
Organics Analysis Data Sheet for target compounds
(Form I LCF).
Chromatograms and data system printouts are labeled
as in Paragraph 4.7.2.4 and 4.7.2.6.
4.7.4.3 Florisil Cartridge Check
Florisil Cartridge Check (Form IX LCP), for all lots
of cartridges used to process samples in the SDG.
Each Form IX LCP shall be followed by the
Chromatograms and data system printouts, labeled as
in 4.7.2.4 and 4.7.2.6.
5. COMPLETE SDG PILE
As specified in the Delivery Schedule, one Complete SDG File (CSF)
including the original sample data package shall be delivered to the
Region concurrently with delivery of copies of the Sample Data Package
to SMO and EMSL/LV. The contents of the CSF will be numbered according
to the method described in Section III of Exhibit B. The Document
Inventory Sheet, Form DC-2, is contained in Section IV. The CSF will
contain all original documents where possible. No copies will be
placed in the CSF unless the originals are bound in a logbook which is
maintained by the laboratory. The CSF will contain all original
documents specified in Section III, and Form DC-2 of Exhibit B.
The CSF will consist of the following original documents in the order
listed in paragraph 5.1 through 5.6 below:
5.1 The original sample data package (see Exhibit B, Section 4).
5.2 A completed and signed Document Inventory Sheet (Form DC-2).
5.3 All original shipping documents, including, but not limited to, the
following documents:
o EPA Chain of Custody Record
o Airbills.
o EPA Traffic Reports.
o Sample Tags (if present) sealed in plastic bags.
5.4 All original receiving documents, including, but not limited to, the
following documents:
o Form DC-1
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o Other receiving forms or copies of receiving logbooks
o SDG Cover Sheet
5.5 All original laboratory records, not already submitted in the Sample
Data Package, of sample transfer, preparation and analysis, including,
but not limited to, the following documents:
o Original preparation and analysis forms or copies of preparation
and analysis logbook pages.
o Internal sample and sample extract transfer chain-of-custody
records.
o Screening records.
o All instrument output, including strip charts from screening
activities.
5.6 All other original SDG-related documents in the possession of the
laboratory, including, but not limited to, the following documents:
o Telephone contact logs
o Copies of personal logbook pages
o All hand written SDG-specific notes
o Any other SDG specific documents not covered by the above.
NOTE: All SDG-related documentation may be used or admitted as
evidence in subsequent legal proceedings. Any other SDG-specific
documents generated after the CSF is sent to EPA, as well as copies
that are altered in any fashion, are also deliverables to EPA.
(Original to the Region and copies to SMO and EMSL/LV).
If the laboratory does submit SDG-specific documents to EPA after
submission of the CSF, the documents shall be numbered as an addendum
to the CSF and a revised DC-2 form shall be submitted, or the documents
should be numbered as a new CSF and a new DC-2 form should be
submitted. The revised DC-2 fora is sent to the Region only.
6. DATA IN COMfUTmt-BKAP*Rirfi TQPKf
The Contractor shall provide a computer-readable copy of the data on
data reporting Forms I-X for all samples in the Sample Delivery Group,
as specified in the Contract Performance/Delivery Schedule.
Computer-readable data deliverables shall be submitted on IBM or
IBM-compatible, 5.25 inch double-sided, double density 360 K-byte or a
high density 1.2 M-byte diskette or 3.5 inch double-sided double
density 720 K-byte or 1.44 M-byte diskette.
When submitted, diskettes shall be packaged and shipped in such a
manner that the diskette(s) cannot be bent or folded, and will not be
exposed to extreme heat or cold or any type of electromagnetic
radiation. The diskette(s) must be included in the same shipment as
the hardcopy data and shall, at a minimum, be enclosed in a diskette
mailer. The data shall be recorded in ASCII text file format, and
shall adhere to the file, record and field specifications listed in
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Exhibit H, Data Dictionary and Format for Data Deliverables in
Computer-Readable Format.
7. GC/MS TAPES
See Exhibit E for requirements.
8. EXTRACTS
The Contractor shall store sample extracts at 4*C (±2*C) in
bottles/vials with Teflon-lined septa. Extract bottles/vials shall be
labeled with EPA Sample Number, Case number and Sample Delivery Group
(SDG) number. A logbook of stored extracts shall be maintained,
listing EPA Sample Numbers and associated Case and SDG numbers.
The Contractor is required to retain extracts for 365 days following
data submission. During that time, the Contractor shall submit
extracts and associated logbook pages within seven days following
receipt of a written request from the Sample Management Office.
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SECTION III
FORK INSTRUCTION GUIDE
This section includes specific instructions for the completion of all
required forms. Each of the forms is specific to a given fraction (volatile,
semivolatile, pesticide/Aroclor). The Contractor shall submit only those
forms pertaining to the fractions analyzed for a given sample or samples.
For instance, if a sample is scheduled for volatile analysis only, submit
only VGA forms. There are two pages relating to the semivolatile fraction
for Forms I, VI, VII, and VIII and four pages relating to the
pesticide/Azoclor fraction for Form VI. Whenever semivolatiles or
pesticides/Aroclors are analyzed and one of the above named forms is
required, all pages (LCSV-1, LCSV-2, etc.) must be submitted. These
instructions are arranged in the following order:
1. General Information and Header Information
2. Organic Analysis Data Sheet (Form I, All Fractions)
3. Surrogate Recovery (Fora II, All Fractions)
4. Laboratory Control Sample Recovery (Form III, All Fractions)
5. Method Blank Summary (Form IV, All Fractions)
6. GC/MS Tuning and Mass Calibration (Form V LCV, LCSV)
7. Initial Calibration Summary (Form VI, All Fractions)
8. Pesticide Resolution Check Summary (Form VI LCP-4)
9. Continuing Calibration Summary (Form VII LCV, LCSV)
10. Calibration Verification Summary (Form VII LCP)
11. Internal Standard Area and Retention Time Summary (Form VIII LCV,
LCSV)
12. Pesticide/Aroclor Analytical Sequence (Form VIII LCP)
13. Pesticide/Aroclor Florisil Cartridge Check (Form IX LCP)
14. Pesticide/Aroclor Identification (Form X LCP)
15. Sample Log-In Sheet (Form DC-1)
16. Document Inventory Sheet (Form DC-2)
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1. GENERAL INFORMATION AND HEADER INFORMATION
1.1 The data reporting forms presented in Section IV have been designed in
conjunction with the computer-readable data format specified in Exhibit
H, Data Dictionary and Format for Data Deliverables in
Computer-Readable Format. The specific length of each variable for
computer-readable data transmission purposes is given in the data
dictionary (Exhibit H). Information entered on these forms oust not
exceed the size of the field given on the form, including such
laboratory-generated items as Lab Name and Lab Sample ID.
1.2 Note that on the hardeopy forms (Section IV), the space provided for
entries is greater in some instances than the length prescribed for the
variable as written to diskette (see Exhibit H). Greater space is
provided on the hardeopy forms for visual clarity.
1.3 Values must be reported on the hardeopy forms according to the
individual form instructions in this Section. For example, results for
concentrations of VOA target compounds must be reported to two
significant figures if the value is greater than or equal to 10.
Values can be written to the diskette file in any format that does not
exceed the field specification as given in the record specifications
and discussed in "Record Structure", in Exhibit H.
1.4 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 exactly 5, round up if the digit to be retained is odd, and
round down if that digit is even.
1.5 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 this Superfund Analytical Method.
No information may be added, deleted, or moved from its specified
position without prior written approval by SMO. The names of the
various fields and compounds (i.e., "Lab Code", "Coloromethane") on the
uncompleted forms must appear as they do in the this Superfund
Analytical Method (Section IV of this exhibit) , except that the use of
uppercase and lowercase letters is optional.
1.6 Alphabetic entries made onto the forms by the Contractor shall be in
AL1 UPPERCASE letters. If an entry does not fill the entire blank
space provided on the form, null characters shall be used to remove the
remaining underscores that comprise the blank line. (See Exhibit H for
more detailed instructions.) However, do not remove the underscores or
vertical bar characters that delineate "boxes" on the forms. The only
exception would be those underscores at the bottom of a "box" that are
intended as a data entry line (for instance, see Form II LCV, line 30.
If data must be entered on line 30, it will replace the underscores).
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1.7 Forms II, IV, V, VIII, IX, and X 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 sane fraction-specific form, duplicating all header
information. If a second page is required, number them consecutively,
as "page 1 of 2" and "page 2 of 2". If a second page is not required,
number the page "page 1 of 1." NOTE: These forms are
fraction-specific. For example, Form II LCV, Form II LCSV, and'Form II
LCF are for different data. Therefore, dp not number the pages of all
three versions of Form II as "1 of 3, 2 of 3, etc.* Only number pages
within a fraction-specific form.
1.8 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, if it applies, must be entered
on every form and must match on every form.
1.8.1 The "Lab Name* shall be the name chosen by the Contractor to
identify the laboratory. It may not exceed 25 characters.
1.8.2 The "Lab Code" is an alphabetical abbreviation of up to 6
letters, assigned by SMO, to identify the laboratory and aid in
data processing. This lab code shall be assigned at the time a
contract is awarded, and shall not; be modified by the
Contractor, except at the direction of SMO. If a change of
name or ownership occurs at the laboratory, the lab code will
remain the same until the Contractor is directed by SMO to use
another lab code assigned by SMO.
1.8.3 The "Case No." is the assigned Case Number (up to 5 digits)
associated with the sample, and reported on the Traffic Report.
1.8.4 The "Contract" is the number of the SMO contract under which
the analyses were performed.
1.8.5 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).
1.8.6 The "SAS No." is the EPA-assigned number for analyses performed
under Special Analytical Services. If samples are to be
analyzed under SAS only, and reported on these forms, then
enter SAS No., and leave Case No. blank. If samples are
analyzed according to the "Routine Analytical Services* (IFB)
protocols and have additional "SAS" requirements, list both
Case No. and SAS No. on all forms. If the analyses have no SAS
requirements, leave "SAS No." blank. NOTE: Some samples in an
SDG may have a SAS No. while others do not.
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1.9 EPA Sample Number
1.9.1 EPA Sample Number must be entered on several of the forms.
This field 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 the form,
it should be entered on the middle line of the three lines that
comprise the box.
1.9.2 All samples, including Laboratory Control Samples and
Performance Evaluation Samples, blanks, and standards shall be
identified with an EPA Sample Number.
1.9.3 For samples, the EPA Sample Number is the unique identifying
number given in the Traffic Report that accompanied that
sample. In order to facilitate data assessment, the following
identification scheme must be used for samples:
XXXXX - EPA Sample Number assigned
XJOuumE - re-analyzed sample
XXXXXDL - sample analyzed at a dilution
XXXXXDL2 - sample analyzed at a secondary dilution (for PEST
only)
1.9.4 The EPA Sample Number must be unique for each Laboratory
Control Sample within an SDG. The EPA Sample Number for a
Laboratory Control Sample must be FLCS##, where:
F - fraction (V for volatiles; S for semivolatiles; P for
pesticides/Aroclors).
LCS - indicates a Laboratory Control Sanple.
## - suffix consisting of characters or numbers or both that
makes the EPA Sample Number for the LCS unique in the SDG.
1.9.5 The EPA Sample Number must be unique for each blank within an
SDG. Within a fraction, a laboratory must replace the "##"
terminator of the identifier with one or two characters or
numbers, or a combination of both. For example, possible .
identifiers for volatile blanks would be VBLK1, VBLK2, VBLKAl,
VBLKB2, VBLK10, VBLKAB, etc.
Volatile method blanks shall be identified as VBLK##.
Volatile storage blank shall be identified in VSBLK##.
Volatile instrument blank shall be identified as VTBLK##.
Semivolatile method blanks shall be identified as SBLK##.
Pesticide/Axoclor method blanks shall be identified as PBLK##.
B-27 6/91
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Pesticide/Aroclor instrument blanks shall be identified as
PIBLK**.
If a separate sulfur cleanup blank is required (e.g., when not
all Pesticide/Aroclor samples associated with a given method
blank are subjected to sulfur cleanup) the PesCicide/Aroclor
sulfur cleanup blanks shall be identified as PCBLK##.
1.9.6 The EPA Sample Number must be unique for each standard within
an SDG.
The EPA Sample Numbers for volatile and semivolatile standards
must be FSTD#**, where:
F - fraction (V for volatiles; S for semivolatiles).
STD - indicates a standard.
### - the concentration in ug/L of volatile standards (i.e.,
001, 002, 005, 010) or the amount injected in ng for
semivolatile standards (i.e., 005, 010, 020, 050, and 080).
These designations will have to be concatenated with other
information to uniquely identify each standard in the SDG.
For pesticide/Aroclor standards, the following scheme shall be
used to enter EPA Sample Number.
Name
EPA Sanmle Number
Individual Mix A (low point) INDAL*#
Individual Mix A (mid point) INDAMtf*
Individual Mix A (high point) INDAH##
Individual Mix B (low point) INDBLa*
Individual Mix B (mid point) INDBM##
Individual Mix B (high point) INDBH##
Resolution Check RESC##
Performance Evaluation Mixture PEM##
Toxaphene TOXAPH##
Aroclor 1016 AR1016**
Aroclor 1221 AR1221##
Aroclor 1232 AR1232##
Aroclor 1242 AR1242##
Aroclor 1248 AR1248##
Aroclor 1254 AR1254#*
Aroclor 1260 AR1260##
Aroclor 1016/1260 AR1660##
The laboratory must create a unique "EPA Sample No." within an
SDG by replacing the two-character "##" terminator of the
identifier with one or two characters or numbers, or a
combination of both.
If the standards are injected onto both GC columns on the same
instrument simultaneously, the same EPA Sample Number may be
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6/91
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used for reporting data for the standards for both columns. If
simultaneous Injections are not made, then the same number may
not be used.
1.10 Several other pieces of information are common to the header
information on some of the data reporting forms. These include: Lab
Sample ID, Lab File ID, Purge or Sample Volume, GC Column - ID,
Instrument ID, Time Analyzed, Date Received, Extracted, and Date
Analyzed.
1.10.1 "Lab Sample ID" is an optional laboratory-generated internal
identifier. Up to 12 alpha-numeric characters may be reported
here.
1.10.2 "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.
1.10.3 "Purge Volume" or "Sample Volume* is the total volume of water
that was purged or extracted, in milliliters.
1.10.4 There are two fields to be entered under "GO Column - ID".
Enter the stationary phase of the GC column after "GC Column"
and enter the internal diameter in millimeters after "ID*.
1.10.5 "Instrument ID" is the identifier that distinguishes each
instrument used for analysis in the SDG.
1.10.6 The "Time Analyzed" shall be in military time.
1.10.7 "Date Received" is the date of sample receipt at the
laboratory, as noted on the Sample Traffic Report (i.e., the
Validated Time of Sample Receipt). "Date Received" is entered
as MM/DD/YY.
1.10.8 Enter the date on which the extraction procedure was started
for "Date Extracted". "Date Extracted" is entered as MM/DD/YY.
1.10.9 For each fraction, the "Date Analyzed* is the date of the
sample analysis. The date of sample receipt will be compared
with the extraction and analysis dates of each fraction to
ensure that contract holding times were not exceeded. "Date
Analyzed" is entered as MM/DD/YY.
1.11 For pesticide/Aroclors, analyses on two GC columns are required. The
information on the two analyses is differentiated on some of the forms
as "Date Analyzed (1)", "Date Analyzed (2)", etc. The order of
reporting is not important, but must be consistent with the information
reported on Form X. When simultaneous injection is made on both GC
columns, the dates (and times) will be the same. If simultaneous
injections are not made, the (1) shall refer to the first analysis, and
(2) the second. If only one analysis is required, leave blank the
fields for the second analysis.
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2. ORGANIC ANALYSIS DATA SHEET fFOBK T\
2.1 Target Compounds. Fora I LCV, LCSV-1, LCSV-2, and LCP
This form is used for reporting the detected concentrations of the
target compounds in the samples, Laboratory Control Samples,
Performance Evaluation Samples, and all blanks analyzed, including
method blanks, instrument blanks, sulfur cleanup blanks, and storage
blanks.
Complete the header information on each Form I required, according to
the instructions in paragraph 1.
Enter 1 for the "Dilution Factor", if a sample was not diluted or
concentrated for analysis. If a sample has been diluted for analysis,
enter the "Dilution Factor* as a single number, such as 100 when a
sample is diluted by a factor of 100. Enter 0.1 when a sample is
concentrated by a factor of 10.
For volatiles, the "Purge Volume" is the total volume (in mL) purged
for the analysis.
For semivolatiles and pesticides, enter the "Concentrated Extract
Volume" and the "Injection Volume* in microliters. The "Concentrated
Extract Volume* is the actual volume of the most concentrated sample
extract. If a dilution of the sample extract is made in a subsequent
analysis, this volume will remain the same, but the dilution factor
will change. Enter the *pH" of the sample before extraction, reported
to 0.1 pH units. Enter "Y" or "N" for "Yes* or "No" under the "Sulfur
Cleanup* for the pesticides.
In the concentration column, for positively identified target
compounds, the Contractor shall report the concentrations as
uncorrected for blank contaminants.
For volatile and senu.volati.le results, report analytical results to one
significant figure if the value is less than 10, and to two significant
figures if greater than or equal to 10.
Report all pesticide/Aroclor results to two significant figures.
If the analytical result is greater than or equal to the quantitation
limit, report the result.
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 (however, see "X" below). The
definition of such flags must be explicit and must be included in the
SDG Narrative.
For reporting results to the USEPA, the following contract specific
qualifiers are to be used. The nine qualifiers defined below are not
subject to modification by the laboratory. Up to five qualifiers may
be reported on Form I for each compound.
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The nine defined qualifiers to be used are as follows:
U - Indicates compound was analyzed for but not detected. The
numerical value is the sample quantitation limit and must be
corrected for dilution. For example, 5 U for phenol in water
if the sample final volume is the protocol-specified final
volume. If a 1 to 10 dilution of the extract is necessary, the
reported limit is SO 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 data
indicate the presence of a compound that meets the
identification criteria but the result is less than the sample
quantitation limit but greater than zero. For example, if the
sample quantitation limit is 10 ug/L, but a concentration of 3
ug/L is calculated, report it as 3J. The sample quantitation
limit must be adjusted for dilution as discussed for the U
flag.
N - Indicates presumptive evidence of a compound. This flag is
only used for tentatively identified compounds, where the
identification is based on a mass spectral library search. It
is applied to all TIC results. For generic characterization of
a TIC, such as chlorinated hydrocarbon, the M code is not used.
B - This flag is used on the sample Form I when the analyte is
found in the associated blank as well as in the sample. It
indicates possible/probable blank contamination and warns the
data user to take appropriate action. This flag must be used
for a, TIC as well as for a positively identified target
compound.
The combination of flags "BU" or "TIB" is expressly prohibited.
Blank contaminants are flagged "B" only when they are detected
in the sample.
E - This flag identifies compounds whose concentrations exceed the
initial calibration range of the instrument for that specific
analysis. If one or more compounds have a response that exceed
the initial calibration range, the sample or extract must be
diluted and reanalyzed according to the specifications in
Exhibit D. All such compounds should have the concentration
flagged with an "E" on the Form I for the original analysis.
The dilution of the extract may cause some compounds identified
in the first analysis to be below the calibration range in the
second analysis. The results of both analyses shall be
reported on separate Forms I. The Form I for the diluted
sample shall have the "DL" (or "DL2") (for pesticide samples
only) suffix appended to the EPA Sample Number. NOTE: For
total xylenes, where three isouers are quantified as two peaics,
the calibration range of each peak should be considered
separately, e.g., a diluted analysis is not required for total
xylenes unless the concentration of the peak representing the
B-31 6/91
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single isomer exceeds 25 ftg/L or the peak representing the two
coeluting isomers on that GC column exceeds 50 /*g/L.
D - If a sample or extract is diluted and re-analyzed, as in the
"E" flag above, all concentration values reported on that Form
I are flagged with the "D" flag. The "DL" or "DL2" (for
pesticide samples only) suffix is appended to the EPA Sample
Number on the Form I for the diluted sample.
A - This flag is not used under this contract, but; is reserved.
P - This flag is used for a pesticide/Aroclor target analyte when
there is greater than 25.0% difference between the
concentration calculated from the two GC columns (see Form X)
The lower of the two values is reported on Form I and flagged
with a "P".
X - Other specific flags may be required to properly define the
results. If used, they must be fully described and such
description attached to the Sample Data Summary Package and the
SDG Narrative. Begin by using "X". If more than one flag is
required, use "Y" and "Z", as needed. If more than five
qualifiers are required for a sample result, use the "X* flag
to combine several flags, as needed. For instance, the "X"
flag might combine the "A", "B", and "D" flags for some sample.
2.2 Non-target Compounds. Form I LCV-TIC and LCSV-TIC
Fora I LCV-TIC and LCSV-TIC are used for reporting the tentative
identification and estimated concentration for up to 10 of the non-
surrogate and non-target organic compounds in the volatile fraction and
up to 20 of the non-surrogate and non-target organic compounds in the
semivolatile fraction.
Include a Form I LCV-TIC or LCSV-TIC for every volatile and
semivolatile fraction of every sample, Performance Evaluation Sample,
and blank analyzed. Form I LCV-TIC or LCSV-TIC must be provided for
every analysis (except for the Laboratory Control Samples) that
requires a Form I for target compounds, including required dilutions
and reanalyses, even if no TICs are found.
Fill in all header information as section 2.1.
Report tentatively identified compounds (TICs) including CAS number,
compound name, retention time, and the estimated concentration
(criteria for reporting TICs are given in Exhibit D). Retention time
must be reported in minutes and decimal minutes, not seconds or minutes
and 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.
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Total the number of TICs found and enter this number in the "Number
TICs found." If no TICs 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.).
All TIC results, except "generics" (See N flag) are flagged "JN" in the
"Q" column to emphasize the quantitative and qualitative uncertainties
associated with these data. This includes "unknowns*.
3. SURROGATE RECOVERY. POBM II LCV. LCSV. AND LCP
Form II is used to report the recovery of the surrogate compounds added
to each sample, blank, Laboratory Control Sample, and Performance
Evaluation Sample.
Complete the header information on each Form II required, according to
the instructions in paragraph 1.
In the table, enter EPA Sample Numbers for each analysis as described
in paragraph 1. For each sample, report the percent recovery for each
surrogate to the nearest whole number.
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 a sample or extract is diluted and the surrogate recovery is below
the recovery limits in any analysis, enter the calculated recovery or
"0* (zero) if the surrogate is not detected. Flag the surrogate
recovery 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.
Pesticide/Aroclor samples are analyzed on two GC columns, and
surrogates recoveries must be reported for both analyses. Enter the
information on the stationary phases and internal diameters of the two
GC columns, as described in paragraph 1.10.4, differentiating the GC
columns as "(1)" and "(2)". Enter the recoveries of the two surrogates
for each column in a similar fashion.
Number the Form II pages as described in paragraph 1.7.
4. LABORATORY CONTROL SAKPTJt BECOVERY. FORM III LCV. LCSV. AND LCP
Form III is used to report the recovery of the spiked analytes in the
Laboratory Control Sample (LCS).
Complete the header information on each Form III required, according to
the instructions in Sections 1 and 2.
B-33 6/91
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The "LCS Lot No. * is an identification number assigned by the Agency to
the LCS spiking solution, if the solution is provided by the Agency.
If the LCS solution is purchased by the Contractor from a third party,
report the identification number used by the laboratory under "LCS Lot
No.".
The "LCS Aliquot" is the volume in microliters of LCS spiking solution
that was added to reagent water before purging or extraction.
For pesticides, the LCS is reported for both GC columns. Enter the
Instrument ID and GC Column - ID for analyses on both GC columns. The
order of reporting is not important, but must be consistent with the
information reported on Form X, If simultaneous injections are not
made, the "Date Analyzed" is the earlier date of the two LCS analyses.
In the upper box in Form III, under "AMOUNT ADDED", enter the amount in
nanograms of each analyte added to the sample. Under "AMOUNT
RECOVERED", enter the amount in nanograms of each analyte in the sample
calculated from analysis. Calculate the percent recovery of each
compound in the sample to the nearest whole percent, according to
Exhibit D, and enter under "% REG". Enter the limits for each analyte
in the column for "QC LIMITS*. The limits should be entered as two
whole numbers (lower and upper limits) separated by a hyphen. Flag all
percent recoveries which do not meet the contract requirements with an
asterisk (*). The asterisk must be placed in the last space of the
percent recovery column, under the •#• symbol.
Summarize the values outside the QC limits at the bottom of the page.
5. METHOD BLANK SUMMARY. FORM IV LCV. LCSV. AND LCP
Form IV lists the samples including LCS and FES associated with each
method blank. A copy of the appropriate Form IV is required for each
method blank.
Complete the header information on each Form IV required, according to
the instructions in Sections 1.
For semi-volatile and pesticide/Aroclor method blanks, enter the date of
extraction of the blank.
For pesticide/Aroclors, enter the "Date Analyzed", "Time Analyzed",
"Instrument ID", and "GC Column - ID* for analyses on both GC columns.
For all three fractions, as appropriate, summarize the samples,
including LCS and PES 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 Analyzed for each sample.
For seaivolatiles, enter the Lab File ID and Date Analyzed. For
pesticides/Aroclors, enter the Date Analyzed on each GC column for each
sample.
For pesticides/Aroclors, enter "Y" or "N" (for yes or no) under "Sulfur
Cleanup". If a separate sulfur cleanup blank is prepared, when not all
B-34 6/91
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samples associated with a method blank are subjected to sulfur cleanup,
then complete & separate Form IV for the sulfur cleanup blank, listed
the EPA Sample No. of the blank, as described in paragraph 1.9.6, in
the box in the upper right hand corner of the form. These samples
associated with the sulfur cleanup blank will be listed in the lower
portion of the form, as well as on a copy of Fora IV for their
associated method blank. Whenever all the .samples and their associated
method blank are subjected to sulfur cleanup, no separate sulfur blank
is required, and only one Form TV needs to be completed.
Number the Form TV pages as described in paragraph 1.7.
6. GC/MS TUNING ASP MAS? Cf LT??f TTQK • FORM V LCV AMD LCSV
This form is used to report the results of GC/MS tuning for volatiles
and semivolatiles, and to summarize the date and time of analysis of
samples, standards, and blanks associated with each GC/MS tune
(including Laboratory Control and Performance Evaluation Samples).
Complete the header information on each Form V required, according to
the instructions in paragraph 1.
Enter the "Lab File ID" for the injection containing the GC/MS tuning
compound (BFB for volatiles, DFTPP for semivolatiles). Enter the date
and time of injection of the tuning compound. Enter injection time as
military time.
In the upper table, for each ion listed on the form, enter the %
Relative Abundance in the right-hand column. Report relative
abundances to the number of significant figures given for each ion in
the ion abundance criteria column.
Note that for both BFB and DFTPP, one or more of the high mass ions may
exceed the abundance of the ion listed on the form as the base peak
(m/z 95 for BFB, and m/z 198 for DFTPP). Despite this possibility, all
ion abundances are to be normalized to the nominal base peaks listed on
Form V (see Exhibit D).
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, and blanks
analyzed under that tune in chronological order. by time of analysis
(in military time). Refer to paragraph 1 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 including LCS and PES, and blanks.
Number che Form V pages as described in paragraph 1.7.
B-35 6/91
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7. INITIAL CALIBRATION SUMMARY. FORM VI LCV. LCSV-1. LCSV-2. LCP-1. LCP-2
AND LCP-3
For each fraction, after a GO/MS or GC system has undergone an initial
calibration, and after all initial calibration technical criteria have
been met, the laboratory must complete and submit all Fora Vis for
initial calibrations performed relevant to the samples including LCS
and FES and blanks in the SDG, regardless of when that calibration was
performed.
Complete the header information on each Form VI required, according to
the instructions in paragraph 1.
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 10" and "Calibration Date(s)". If the
calendar date changes during the calibration procedure, the inclusive
dates should be given on Form VI.
For the volatile and semivolatile fractions, enter the "Lab File ID"
for each of the five calibration standards injected. Complete the
response factor data for the five calibration points. The relative
response factor (RRF) is reported for each target compound and
surrogate. The laboratory must report the average RSLF and the percent
relative standard deviation (%RSD) for the RRFs for each target
compound and surrogate.
The initial calibration of pesticides and Aroclors involves the
determination of retention times, retention time windows, and
calibration factors. For single component pesticide target compounds,
these data are calculated from the analyses of the Individual Standard
Mixtures A and B at three different concentration levels. For the
multicomponent target compounds, these data are calculated from a
single point calibration.
Complete header information on Form VI, LCP-1 and LCP-2 according to
the instructions in paragraph 1. For the three analyses of Individual
Standard {fixture A (low point, mid point, and high point), and the
three analyses of Individual Standard Mixture B performed on each GC
column during an initial calibration, complete one copy of Form VI for
each GC column used. Enter the Instrument ID, GC Column, and ID as
described previously. Enter the dates of analysis of the first and
last of the six standards on each form under "Date(s) Analyzed". Under
•Level (x low)", enter the concentration of the low point, mid point,
and high point calibration standards as a multiplier of the low point.
Therefore, for the low point, enter "1.0". The concentration of the
mid point standard is specified in Exhibit D as four times the low
point, therefore, enter "4.0" for "mid". If the concentration is not
exactly 4.0 times the low point, enter the appropriate multiplier in a.
similar format. The high point standard must be at least 16 times the
low point, but may be higher if that value lies within the linear range
of the instrument, as specified in Exhibit D. Therefore, enter the
appropriate multiplier to the high point standard concentration to one
decimal place.
B-36 6/91
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For the pesticides/Aroclors fraction, one Fora VI (LCP-1 and LCF-2) is
required for each initial calibration performed on each GC column. In
the table, on Form VI LCP-1, enter the retention time of each analyte
in the low, mid, and high point Standard Mixtures A and B in the
columns labeled "RT of Standards". Use the values from Standard
Mixture A for the surrogates. Calculate and report in the appropriate
column the mean retention time and the retention time windows for each
analyte. Report the retention time window for each analyte as a range
of two values, i.e., from 1.44 to 1.54. Enter the lower value of the
range in the column under "RT WINDOW" labeled "FROM". Enter the upper
value of the range in the column under "TO". Do not separate the two
values with a hyphen, and do not enter the retention time window as a
plus/minus value such as ±0.05. NOTE: By definition, the center of the
retention time window must be the mean retention time listed to the
left of the retention time window.
On Form VI LCF-2, calculate the calibration factor for each analyte in
the low, mid, and high point Standard Mixtures A and B. Use the values
from Standard Mixture A for the surrogates. Report the values under
the columns labeled "CALIBRATION FACTORS". Calculate the mean of the
three calibration factors and the percent relative standard deviation
(%RSD) for the calibration factor values for each analyte. Report the
calculated values under the "MEAN" column the "%RSD" columns,
respectively.
On Form VI LCP-3, for the initial calibration of multicomponent
analytes, enter the amount of standard injected in nanograms of each
analyte, under the "AMOUNT" column. The number of peaks with an
asterisk under the "Peak" column indicates the minimum number of peaks
calibrated for each analyte. Enter the retention time of each peak
used to quantitate under the "RT" column. Data for two additional
peaks may be reported for each multicomponent analyte. Calculate and
report the calibration factor for each peak used under "CALIBRATION
FACTOR".
8. PESTICIDE RESOLUTION CHECK SUMMARY. FORM VI LCP-4
Pesticide Resolution Check Summary Form VI is used to report the
resolution of each analyte in the Resolution Check Mixture analyzed at
the beginning of each initial calibration on each GC column.
Complete the header information on each Form VI required according to
the instructions in paragraph 1.
For each GC column, enter the "EPA Sample Number" of the Resolution
Check Mixture, as described in paragraph 1.9.7, for the mixture
injected on the first GC column. Enter the Lab Sample ID, Date
Analyzed (1), and Time Analyzed (1).
In the table, under "ANALYTE", enter the name of each analyte as it
appears on Form I, in elution order, starting with the first target
analyte or surrogate to elute. Enter the retention time of each of the
analytes listed under "RT".
B-37 . 6/91
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Calculate the percent resolution between each pair of consecutive peaks
according to Exhibit D. Enter the percent resolution of each pair in
the "RESOLUTION" field of the analyte that elutes earlier (the analyte
listed first). The resolution must be calculated for each adjacent
peaks so that the resolution of peak 1 and peak 2 is calculated, as
well as peak 2 vs. peak 3, peak 3 vs. peak 4, etc. The "RESOLUTION"
field will be left blank for the last analyte in the in the table. The
percent resolution must meet the QC limits listed at the bottom 'of the
page.
Complete the information for the second GC column in the same fashion.
9. coNTiNUJj^e CALIBRATION SUMMARY. FORM vn LCV. LCSV-I AND Lcsv-2
The Continuing Calibration Summary Form VII is used to verify the
calibration of the GC/MS system by the analysis of specific calibration
standards. Form VII is required for each 12 hour time period for both
volatile and semivolatile analysis.
Complete the header information on each Form VII required, according to
the instructions in paragraph 1.
Enter date and time of continuing calibration standard analysis, the
Lab File ID of the continuing calibration standard, and date(s) of
initial calibration. Give inclusive dates if initial calibration is
performed over more than one date. Enter the average relative response
factor (RRF) for each target compound that was calculated from the
initial calibration data (referred to in the initial calibration
date(s) analyzed field). Report the relative response factor for each
target compound and surrogate from the continuing calibration standard
analysis.
10. PSSTICIDE/AROCLQH, CALIBRATION VERIFICATION
Calibration Verification Summary. Form VII LCP-1 and LCP-2
The Calibration Verification Summary Form VII is used to report the
results of the Performance Evaluation Mixtures (PEM), instrument
blanks, and Individual Standard Mixtures A and B analyzed at the
beginning and end of a twelve hour sequence. The laboratory must
submit this form for each twelve hour sequence analyzed.
Complete the header information on each Form VII required according to
the instructions in paragraph 1.
Enter the initial calibration date(s) analyzed. Give inclusive dates
if initial calibration is performed over more than one date.
On Form VII, LCP-1, enter the EPA Sample No., Lab Sample ID, Date
Analyzed, and Time Analyzed for the instrument blank that preceded the
twelve hour sequence (PIBLK). For the PEM that initiated or terminated
the twelve hour sequence (PEM), enter the EPA Sample No., Lab Sample
ID, Date Analyzed, and Time Analyzed.
B-38 6/91
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When reporting data for Che PEM at the beginning of the initial
calibration sequence, leave blank the "EPA Sample No.", "Lab Sample
ID", and "Date" and "Time Analyzed" fields for the instrument blank
(PIBLK), as no instrument blank is analyzed before this PEM. When
reporting all other PEM analyses, the instrument blank fields must be
completed.
In the table, report the retention time for each analyte in the PEM as
veil as the retention time windows. For each analyte in the PEM, enter
the amount of the analyte in nanograms, to three decimal places,
calculated to be in the PEM, under "CALC AMOUNT". Enter the nominal
amount of each analyte in the PEM under "NOM AMOUNT". Calculate the
relative percent difference between the calculated amount and nominal
amount for each analyte according to Exhibit D. Report the values
under "%D".
Calculate the percent breakdown for endrin and 4,4'-DDT, and the
combined percent breakdown in the PEM according to Exhibit D. Enter
the values for the breakdown of endrin and 4,4'-DDT in their respective
fields immediately under the table.
Form VII LCP-2 is used to report the dates and times of analysis of the
instrument blanks and the results of the analyses of the midpoint
concentrations of Individual Standard Mixtures A and B that, along with
the PEM, bracket each 12-hour period of sample analyses. One copy of
Form VII LCP-2 must be completed each time the Individual Standard
Mixtures are analyzed, for each GC column used. The form is completed
in a.- similar fashion to Form VII LCP-1, entering the EPA Sample No.,
Lab Sample ID, Date Analyzed, and Time Analyzed for the instrument
blank immediately preceding the Individual Standard Mixtures A and B,
and for the standards themselves. The upper table on the form contains
the retention time and amount data for Individual Standard Mixture A
compounds. The lower table contains the data for Mixture B. Enter the
data in these tables in a. fashion similar to that for the PEM.
Complete copies of Form VII LCP-1 and 2 for each standard reported in
Form VIII LCP.
ASP LCSV-2
Fora VIII is used to summarize the peak areas and retention times of
the internal standards added to all volatile and semivolatile samples
and blanks. Form VIII is also used to check the internal standards in
the initial calibration sequences. The data are used to determine when
changes in internal standard responses will adversely affect
quantisation of target compounds. This form must be completed each
time an initial calibration or a continuing calibration is performed,
or when samples are analyzed under the same GC/MS tune as an initial
calibration.
Complete the header information on each Form VIII required, according
to the instructions in paragraph 1.
B-39 6/91
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Enter the Lab File ID, Date Analyzed, and Tine Analyzed for the
continuing calibration standard. If samples are analyzed immediately
following an initial calibration, before another GC/MS tune and a
continuing calibration, Fora VIII shall be completed for the initial
calibration standard that is the same concentration as the continuing
calibration standard. Enter the Lab File ID, the date and time of
analysis, the areas and retention tines of this initial calibration
standard in place of those of a continuing calibration standard.-
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 rov labeled "12 HOUR
STD". For each volatile internal standard, calculate the area upper
limit as the area of the particular internal standard plus 40 percent
of its area, and the area lower limit as the area of the internal
standard minus 40 percent of its area. For each semivolatile internal
standard, calculate the area 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 area 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 "LOVER
LIMIT* respectively.
For each volatile and semivolatile internal standard, calculate the
retention time (RT) upper limit as the RT of the particular internal
standard plus 0.33 minutes. The lower limit is the RT of the internal
standard minus 0.33 minutes. Report these values in the boxes labeled
"UPPER LIMIT* and "LOVER LIMIT* respectively.
For each sample including LCS and PES and blank 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 or retention time is outside the upper or lower
limits calculated above, flag that value with an asterisk (*). The
asterisk must be placed in the far right hand space of the box for each
internal standard area or retention time, directly under the "#"
symbol.
If samples are analyzed immediately following an initial calibration as
described above, enter the EPA Sample Number, internal standard areas,
and retention times for all five of the initial calibration standards.
Number the Form VIII pages as described in paragraph 1.7.
12. PESTICIDE/AROCLOR ANALYTICAL SEQUENCE. FORM VIII LCP
Form VIII LCP is required for each analytical sequence for each GC
system and for each GC column used to analyze pesticide/Aroclors in an
SDG.
Complete the header information on each Form VIII required, according
to the instructions in paragraph 1.
B-40 6/91
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Enter the initial calibration date(s). Give inclusive dates if initial
calibration is performed over more than one date.
At the top of the table, report the mean retention time for surrogates
tetrachloro-m-xylene and decachlorobiphenyl calculated from the initial
calibration sequence under "TCX" and "DCS", respectively. For every
analysis associated with a particular analytical sequence starting with
the initial calibration, enter the EPA Sample Number, Lab Sample ID,
Date Analyzed, and Time Analyzed. Each sample analyzed as part of the
sequence must be reported on Form VIII LCF even if it is not associated
with the SDG. The laboratory may use the EPA Sample No. of "Z2ZZZ" to
distinguish all samples that are not part of the SDG being reported.
Report the retention time of the surrogates for each analysis under
•TCX RT* and "DCS RT". All sample analyses must be bracketed by
acceptable analyses of instrument blanks, a FEM, and Individual
Standard Mixtures A and B. Given the fact that the initial calibration
may remain valid for some time (see Exhibit D), it is not necessary to
report the data from 12-hour periods when no samples in an SDG were
run. The laboratory must deliver the Form VIII for the initial
calibration sequence, and Forms that include the PEMs and Individual
Standard Mixtures that bracket any and all samples in the SDG. While
the data for time periods between the initial calibration and samples
in the SDG is not a routine deliverable, it must be made available on
request during on-site evaluations, etc. Here again, non-EPA samples
may be indicated with "ZZZZZ".
Flag all those values which do not meet the contract requirements by
entering an asterisk (#) in the last column, under the "*". If the
retention time cannot be calculated due to interfering peaks, leave the
RT column blank for that surrogate, enter an asterisk in the last
(i.e., under "DCS") column, and document the problem In the SDG
Narrative.
Number the Form VIII pages as described in paragraph 1.7.
13. PESTICIDE/AROCLOR FLORISIL CARTRIDGE CHECK. FORM IX LCP
Form IX is required for each lot of Florisil cartridges that is used
with samples associated with the SDG.
Complete the header information on each Form IX required, according to
the instructions in paragraph 1.
Enter the "Case No." and "SDG No." for the current data package,
regardless of the original Case for which the cartridge check was
performed. Enter the "Florisil Cartridge Lot Number". Enter under the
"Date Analyzed", the date the Florisil cartridge check solution was
analyzed.
In the upper table, enter the amount of spike added and spike recovered
in nancgrams for each analytt.
Calculate to the nearest whole percent, and enter the percent recovery
in the "% REG" field. Flag each spike recovery outside the QC limits
B-41 6/91
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with an asterisk (*). The asterisk must be placed in Che last space in
the "% Rec* column, under the "#" symbol.
In the lower table, enter the "EPA Sample No.", the "Lab Sample ID",
and "Date Analyzed" for each sample and blank that was cleaned up using
this lot of Florisil cartridges.
Number the Form IX pages as described in paragraph 1.7.
14. PESTICIPg/AROCLOR IDENTIFICATION. FORM X LCP-1. LCP-2
Form X summarizes the data used to identify and quantify all
pesticide/Aroclor target analytes detected in a given sample. Form X
LCP-1 is required for each sample (including PES and LCS) or blank in
which any single component analytes is detected. Form X LCP-2 is
required for each sample (including PES and LCS) or blank in which any
multicomponent analyte is detected. If no single component analyte or
multicomponent analyte is detected in a sample, no copy of the
applicable Form X is required for that sample.
Complete the header information on each Form X required, according to
the instructions in paragraph 1.
For each target pesticide or Aroclor detected, enter the name of the
analyte on Form X in the column labeled "Analyte", spelling the name as
is appears on Form I. For the multicomponent analytes, there are
spaces (fields) for up to 5 peaks for each analyte. The asterisks
indicate the number of peaks that are required, and data for additional
peaks may be reported. The retention time, retention time window, and
concentration are calculated separately for each peak used for a
multicomponent analyte. For each GC column, enter the retention times
of the analytes detected in the sample next to the appropriate column
designation (1 or 2). Enter the retention time windows on each column
of the appropriate standard. The lower value is entered under the
"FROM" column, the upper value under the "TO* column. Do not use a
hyphen. These data must correspond with those on Form VI, and are
entered in a similar manner. Calculate the concentration of the analyte
using the calibration factors derived from the initial calibration
sequence. For the multicomponent analytes, calculate and report the
mean concentration by averaging the concentration values from the peaks
used for quantitation. Calculate and report the percent difference to
a tenth of a percent between the concentration values (or mean
concentration values for multicomponent analytes) on the two GC columns
under "%D* as described in Exhibit D.
Number the Form X pages as described in paragraph 1.7.
THE FOLLOWING ARE DOCUMENT CONTROL FORMS
(To be submitted as hardcopy only)
15. SAMPT.g LOG-IH SHEET (FORM DC-1^
This form is used to document the receipt and inspection of samples and
containers. One original of Form DC-1 is required for each sample
B-42 6/91
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shipping container. If the samples in a single sample shipping
container (e.g., coolers) must be assigned to more than one Sample
Delivery Group, the original Form DC-1 shall be placed with the
deliverables for the Sample Delivery Group with the lowest sample
number and a copy of Form DC-1 must be placed with the deliverables for
the other Sample Delivery Group(s). The copies should be identified as
"copy(ies), • and the location of the original should be noted on the
copies.
Sign and date the airbill (if present). Examine the shipping container
and record the presence/absence of custody seals and their condition
(i.e., intact, broken) in item 1 on Form DC-1. Record the custody seal
numbers in item 2.
Open the container, remove the enclosed sample documentation, and
record the presence/absence of chain-of-custody record(s), SMO forms
(i.e., Traffic Reports, Packing Lists), and airbills or airbill
stickers in items 3-5 on Form DC-1. Specify if there is an airbill
present or an airbill sticker in item 5 on Form DC-1. Record the
airbill or sticker number in item 6.
Remove the samples from the shipping container(s), examine the samples
and the sample tags (if present), and record the condition of the
sample bottles (i.e., intact, broken, leaking) and presence of absence
of sample tags in items 7 and 8 on Form DC-1.
Review the sample shipping documents and complete the header
information described in Part A. Compare the information recorded on
all the documents and samples and mark the appropriate answer in item 9
on Form DC-1.
If there are no problems observed during receipt, sign and date
(include time) Form DC-1, the chain-of-custody record, and Traffic
Report, and write the sample numbers on Form DC-1. Record the
appropriate sample tags and assigned laboratory numbers if applicable.
The log-in date should be recorded at the top of Form DC-1 and the date
and time of cooler receipt at the laboratory should be recorded in
items 10 and 11. Cross out unused columns and spaces.
If there are problems observed during receipt or an answer marked with
an asterisk (i.e., "absent*") was marked, contact SMO and document the
contact as well as resolution of the problem on a CLP Communication
Log. Following resolution, sign and date the forms as specified in the
preceding paragraph and note, where appropriate, the resolution of the
problem.
Record the fraction designation (if appropriate) and the specific area
designation (e.g., refrigerator number) in the. Sample Transfer block
located in the bottom left corner of Form I. Sign and date the Sample
Transfer block.
B-43 6/91
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16. DOCUMENT IKVKNTORY SHEET (FORM DC-2^
This form is used to record the inventory of the Complete SDG File
documents and count of documents in the original Sample Data Package
which is sent to the Region.
Organize all complete SDG file documents as described in Exhibit B,
Section II, paragraph 5. Assemble the documents in the order specified
on Form DC-2, and stamp each page with a consecutive number. (Do not
number the DC-2 form). Inventory the CSF by reviewing the document
numbers and recording page number ranges in the columns provided in the
Form DC-2. If there are no documents for a specific document type,
enter an "NA" in the empty space.
Certain laboratory specific documents related to the CSF may not fit
into a clearly defined category. The laboratory should review DC-2 to
determine if it is most appropriate to place them under No. 7, 8, 9, or
10. Category 10 should be used only if there is no appropriate
previous category. These types of documents should be described or
listed in the blanks under each appropriate category.
B-44 6/91
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SECTION IV
DATA REPORTING FORMS
B-45 6/91
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1LCA
LOW CONG. WATER VOLATILE ORGANICS ANALYSIS DATA SHEET
EPA SAMPLE NO.
' b Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Lab Sample ID:
Lab File ID:
Purge Volume:
CAS NO.
Date Received:
Date Analyzed:
(mL)
COMPOUND
Dilution Factor:
CONCENTRATION
(ug/L)
7 4-87-3 Chloromethane
75-01-4 Vinvl chloride
75-00-3 Chloroethane
75-09-2 Methylene chloride
67-64-1 Acetone
75-15-0 Carbon disulfide
75-35-4 1. 1-Dichloroethene
•7 K _ t A _.^ _________ 1 1 _n i r^i ^ m*»n A+-1* ana
/ 3— j*— j— — — x , x— uxcii.Loroci.rm nc
156-59-4 cis-1 . 2-Dichloroethene
156-60-5 trans-1, 2-Dichloroethene
67-66-3 Chloroform
107-06-2 1 , 2-Dichloroethane
78-93-3 2 -Butanone
74-97 -5 Br omochlor omethane
71-55-6 1 , 1 , 1-Trichloroethane
56-23-5 Carbon tetrachloride
75-27-4 Bromodichloromethane
78-87-5 1, 2-Dichloropropane
10061-01-5 cis-1 , 3-Dichloropropene
/ j»— ux— o— — — AiiciiAoroeiineiie
124-4 8-1 D ibr omochlor omethane
79-00-5 1 , 1 , 2-Trichloroethane
71-43-2 Benzene
10061-02-6 trans-l, 3-Dichloropropene
108-10-1 4-Methyl-2-pentanone
591-78-6 — 2-Hexanone
127-18-4 Tetrachlor oethene
*7Q_1 A _RM__.______1 1 *} *>_fPn^»— a«-tH 1 n-*-rtn^H a«rt
/y — j* —3— — — x, x, *• i *• — i e ti acn j.or oe unane
106-93-4 -1,2-Dibromoethane
108-88-3 Toluene
108-90-7 — — — Chlor obenz ene
100-41-4 Ethylbenzene
100-42-5 Styrene
541-73-1 1,3-Dichlorobenzene
95-50-1 1 , 2-Dichlorobenzene
FORM I LCV
6/91
-------
1LCB
LOW CONG. WATER SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET
EPA SAMPLE NO.
i Name:
Lab Code:
Lab Sample ID:
Lab File ID:
Sample Volume:
Case No.:
Contract:
SAS No.:
SDG No.:
Concentrated Extract Volume:
Injection Volume: (uL)
.(uL)
Date Received:
Date Extracted:
Date Analyzed:
Dilution Factor:
pH:
CAS NO.
COMPOUND
CONCENTRATION
(ug/L)
-Phenol
111-44-4 bis (2-Chloroethyl) ether_
95-57-8- 2-Chlorophenol_
2 -Methy Iphenol'
2,:
106-44-5 4-Methy Iphenol
95-48-7
621-64-7 N-Nitroso-di-n-propylamine
67-72-1—
98-95-3—
——Nitrobenzene,
Isophorone "
2-i
•2,4-DimethyIphenol
111-91-1
120-83-2 2,4-Dichlorophenol
120-82-1 1,2,4-Trichlorobenzene
106-47-8-
87-68-3—
59-50-7—
91-57-6—
77-47-4—
88-06-2—
95-95-4—
91-58-7—
131-11-3-
208-96-8-
606-20-2-
99-09-2—
83-32-9—
4 -Chloroaniline
— Hexachlorobutadiene
4-Chloro-3-methylphenol_
-2-Methylnaphthalene_
——Hexachlorocyclopentadiene_
2,4,6-Trichlorophenol ~_
2,4,5-Trichlorophenol
2 -Ch 1 or onaphthalene
2-Nitroaniline
•—Dimethylphthalate_
-Acenaphthylene
2,6-Dinitrotoluene
3-Nitroaniline [
——Acenaphthene
FORM I LCSV-1
6/91
-------
1LCC
LOW CONG. WATER SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET
EPA SAMPLE NO.
" b Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Lab Sample ID:
Lab File ID:
Sample Volume:
Date Received:
Date Extracted:
Date Analyzed:
Concentrated Extract Volume:
Injection Volume: (uL)
CAS NO.
COMPOUND
Dilution Factor:
PH:
CONCENTRATION
(ug/L)
100-02-7—
132-64-9 —
4-Nitrophenol
Dibenzofuran
121-14-2 2 , 4-Dinitrotoluene
84-66-2
7005-72-3-
86-73-7
100-01-6 —
534-52-1 —
86-30-6—
101-55-3 —
118-74-1 —
87-86-5
85-01-8
120-12-7—
84-74-2
206-44-0 —
129-00-0 —
85-68-7
91-94-1
56-55-3
218-01-9 —
117-81-7 —
117-84-0 —
2Q5-99-2 —
207-08-9 —
50-32-8
193-39-5 —
53-70-3 — -
191-24-2 —
Diethylphthalate
-— 4 -Chlorophenyl-phenyiether
Fluorene
4-Nitroaniline
4 , 6-Dinitro-2-methylphenol
— N-Nitrosodipheny lamine ( 1 )
4-Bromophenyl-phenylether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
--Anthracene
Di-n-butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
3 , 3 ' -Dichlorobenzidine
— Benzo (a) anthracene
cnrysene
bis (2-Ethylhexyl) phthalate
D±-n-octylphthalate
——Benzo (b) f luoranthene
Benzo (Jc) f luoranthene
Benzo (a) pyrene
indeno (1,2,3 -cd) pyrene
Dibenz (a , h) anthracene
Benzo (g,h, i) perylene
(1) - Cannot be separated from Diphenylamine
FORM I LCSV-2
6/91
-------
1LCD
LOW CONC. WATER PESTICIDE ORGANICS ANALYSIS DATA SHEET
EPA SAMPLE NO,
T '•> Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Lab Sample ID:
Sample Volume:
Concentrated Extract Volume:
Injection Volume: (uL)
Sulfur Cleanup: (Y/N)
.(uL)
Date Received:
Date Extracted:
Date Analyzed:
Dilution Factor:
pH:
CAS NO.
COMPOUND
CONCENTRATION
(ug/L)
319-85-7
58-89-9—
76-44-8-
309-00-2—
1024-57-3-
959-98-8—
60-57-1-
72-55-9-
33213-65-9
1031-07-8
53494-70-5-
7421-36-3-
5103-71-9
5103-74-2
8001-35-2
12674-11-2—
11104-28-2—
11141-16-5—
53469-21-9—
12672-29-6—
11097-69-1—
11096-82-5—
beta-BHC
—gamma-BHC (Lindane)
—Heptachlor 'm
-Aldrin
-Heptachlor epoxo.de_
-Endosulf an I ~_
-Dieldrin
•4,4' -DDE
-Endrin
Endosulf an II
:'-
— Endosulfan sulf ate
—Endrin ketone
-Endrin aldehyde_
—alpha-Chlordane"
—gamma-Chlordane~
—Toxaphene
-Aroclor-1016
—Aroclor-1221"
—Aroclor-12 3 2"
—Aroclor-1242"
—Aroclor-1248^
—Aroclor-1254~
—Aroclor-12 6 o"
FORM I LCP
6/91
-------
1LCE
LOW CONG. WATER VOLATILE ORGANICS ANALYSIS DATA SHEET
TENTATIVELY IDENTIFIED COMPOUNDS
EPA SAMPLE NO.
" b Name:
Lab Code:
Lab Sample ID:
Lab File ID:
Purge Volume:
Case No.:
Contract:.
SAS No.:
SDG No.:
Date Received:
Date Analyzed:
(mL)
Dilution Factor:
Number TICs found:
CAS NUMBER
1.
2.
3.
4.
5.
6.
7.
8.
9.
.0.
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.
(ug/L)
Q
FORM I LCV-TIC
6/91
-------
1LCF
LOW CONG. WATER SEMIVOLATILE ORGAHICS ANALYSIS DATA SHEET
TENTATIVELY IDENTIFIED COMPOUNDS
EPA SAMPLE NO.
b Name:
Lab Code:
Case No.:
Lab Sample ID:
Lab File ID:
Sample Volume:
Concentrated Extract Volume:
Injection Volume: (uL)
Contract:.
SAS No.:
SDG No.:
Date Received:
Date Extracted:
Date Analyzed:
Dilution Factor:
pH:
Number TICs found:
CAS NUMBER
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
IS.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
COMPOUND NAME
RT
EST. CONC.
(ug/L)
-
Q
FORM I LCSV-TIC
6/91
-------
2LCA
LOW CONC. WATER VOLATILE SURROGATE RECOVERY
* b Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
SAMPLE NO.
BFB
%REC t
OTHER
TOT
OUT
BFB = Bromofluorobenzene
QC LIMITS
%REC
(80-120)
# Column to be used to flag recovery values.
* Values outside of contract required QC limits.
D Surrogate diluted out.
page of
FORM II LCV
6/91
-------
2LCB
LOW CONG. WATER SEMIVOLATILE SURROGATE RECOVERY
b Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG NO.
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
SAMPLE NO.
NBZ
%REC #
FBP
%REC #
TPH
%REC t
PEL
%REC #
2FP
%REC f
TBP
%REC #
OTHER
TOT
OUT
NBZ » Nitrobenzene-dS
FBP = 2-Fluorobiphenyl
TPH » Terphenyl-dl4
PHL = Phenol-d5
2FP = 2-Fluorophenol
TBP = 2,4,6-Tribromophenol
QC LIMITS
%REC
(40-112)
(42-110)
(24-140)
(17-113)
(16-108)
(18-126)
# Column to be used to flag recovery values.
* Values outside of contract required.QC limits.
D Surrogate diluted out.
page of
FORM II LCSV
6/91
-------
2LCC
LOW CONG. WATER PESTICIDE SURROGATE RECOVERY
* b Name:
Lab Code:
GC Column(1):
Contract:_
SAS No.:
SDG No.:
(mm) GC Column(2):
ID:
(mm
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
SAMPLE NO.
TCX(l)
%REC t
TCX(2)
%REC f
DCB(l)
%REC #
DCS (2)
%REC #
OTHER
(1)
OTHER
(2)
TOT
OUT
TCX «• Tetrachloro-m-xylene
DCS - Decachlorobiphenyl
QC LIMITS
%REC
(60-150)
(60-150)
# Column to be used to flag recovery values.
* Values outside of contract required QC limits,
D Surrogate diluted out.
page of
FORM II LCP
6/91
-------
3LCA
LOW CONG. WATER VOLATILE LAB CONTROL SAMPLE RECOVERY
EPA SAMPLE NO.
T 'i Name:_
Lab Code:
Lab Sample ID:
Lab File ID:
Purge Volume:
LCS Aliquot:
Case No.:
(uL)
Contract:
SAS No.:
SDG No.:
LCS Lot No.:
Date Analyzed:
Dilution Factor:
COMPOUND
Vinyl chloride
1 , 2-Dichloroethane
Carbon tetrachloride
1 , 2-Dichloropropane
Trichloroethene
1,1, 2-Trichloroethane
Benzene
cis-1, 3-Dichloropropene
Bromoform
Tetrachloroethene
1, 2-Dibromoethane
1 , 4-Dichlorobenzene
AMOUNT
ADDED
(ng)
AMOUNT
RECOVERED
(ng)
%REC t
QC
LIMITS
# Column to be used to flag LCS recovery with an asterisk.
* Values outside of QC limits.
LCS Recovery:
outside limits out of
total.
COMMENTS:
FORM III LCV
6/91
-------
3LCB
LOW CONG. WATER SEMTVOLATILE LAB CONTROL SAMPLE RECOVERY
EPA SAMPLE NO.
T~b Name:
Lab Code:
Lab Sample ID:
Lab File ID:
LCS Aliquot:
Case No.:
(UL)
Contract:_
SAS No.:
SDG No.:
Concentrated Extract Volume:
Injection Volume: (uL)
.(uL)
LCS Lot No.:
Date Extracted:
Date Analyzed:
Dilution Factor:
PH:
COMPOUND
Phenol
bis (2-Chloroethyl) ether
2 -Chlorophenol
N-Nitroso-di-n-propylamine
Hexachloroethane
Isophorone
1,2, 4-Trichlorbbenzene
Naphthalene
4 -Chlor oaniline
2,4, 6-Trichlorophenol
2 , 4-Dinitrotoluene
Diethvlphthalate
N-Nitrosodiphenylamine
Hexachlorobenzene
Benzo (a) pyrene
AMOUNT
ADDED
(ng)
AMOUNT
RECOVERED
(ng)
%REC #
QC
LIMITS
# Column to be used to flag LCS recovery with an asterisk.
* Values outside of QC limits.
LCS Recovery:
outside limits out of
total.
COMMENTS:
FORM III LCSV
6/91
-------
3LCC
LOW CONG. WATER PESTICIDE LAB CONTROL SAMPLE RECOVERY
EPA SAMPLE NO.
T b Name:
Lab Code:
Case No.:
Lab Sample ID:
LCS Aliquot:
(uL)
Concentrated Extract Volume:
Injection Volume: (uL)
Sulfur Cleanup: (Y/N)
Instrument ID(1)
Instrument ID(2) :
Contract:
SAS No.:
SDG No
LCS Lot No.:
Date Extracted:
Date Analyzed:
Dilution Factor:
pH:
GC Column(1):
ID:
(mm)
COMPOUND
gamma -BHC (Lindane)
Heptachlor epoxide
Dieldrin
4, 4 '-DDE
Endrin
Endosulf an sulf ate
gamma-Chlordane
AMOUNT
ADDED
(ng)
AMOUNT
RECOVERED
(ng)
%REC f
QC
LIMITS
GC Column(2):
ID:
(mm)
COMPOUND
gamma-BHC (Lindane)
Heptachlor epoxide
Dieldrin
4. 4 '-DDE
Endrin
Endosulf an sulf ate
gamma-Chlordane
AMOUNT
ADDED
(ng)
AMOUNT
RECOVERED
(ng)
%REC f
QC
LIMITS
# Column to be used to flag recovery values with an asterisk.
* Values outside of QC limits.
~.CS Recovery: outside limits out of total.
COMMENTS:
FORM III LCP
6/91
-------
4LCA
LOW CONG. WATER VOLATILE METHOD BLANK SUMMARY
EPA SAMPLE NO.
T > Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Lab Sample ID:
Lab File ID:
Instrument ID:
Date Analyzed:
Time Analyzed:
THIS METHOD BLANK APPLIES TO THE FOLLOWING SAMPLES AND LCS:
COMMENTS:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
SAMPLE NO.
LAB
SAMPLE ID
LAB
FILE ID
TIME
ANALYZED
page of
FORM IV LCV
6/91
-------
4LCB
LOW CONG. WATER SEMIVOLATILE METHOD BLANK SUMMARY
EPA SAMPLE NO.
7 '•> Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SOG No.:
Lab Sample ID:
Lab File ID:
Instrument ID:
Date Extracted:
Date Analyzed:
Time Analyzed:
THIS METHOD BLANK APPLIES TO THE FOLLOWING SAMPLES AND LCS:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
SAMPLE NO.
LAB
SAMPLE ID
LAB
FILE ID
DATE
ANALYZED
COMMENTS:
page of
FORM IV LCSV
6/91
-------
4LCC
LOW CONG. WATER PESTICIDE METHOD BLANK SUMMARY
EPA SAMPLE NO.
7 *•> Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No. :
Date Extracted:
Lab Sample ID:
Date Analyzed (1):
Time Analyzed (1):
Instrument ID (1):
GC Column (l):
ID:
(mm)
Date Analyzed (2):
Time Analyzed (2):
Instrument ID (2):
GC Column (2): ID:
(mm)
Sulfur Cleanup: (Y/N)
THIS METHOD BLANK APPLIES TO THE FOLLOWING SAMPLES AND LCS:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
EPA
SAMPLE NO.
LAB
SAMPLE ID
DATE
ANALYZED 1
DATE
ANALYZED 2
COMMENTS:
page of
FORM IV LCP
6/91
-------
5LCA
LOW CONC. WATER VOLATILE ORGANIC GC/MS TONING AND MASS
CALIBRATION - BROMOFLUOROBENZENE (BFB)
T *i Name:
Lab Code:
Lab File ID:
Instrument ID:
GC Column:
Case No.
ID:
(am)
Contract:.
SAS No.:
SDG No.:
BFB Injection Date:
BFB Injection Tine:
m/e
50
75
95
96
173
174
175
176
177
ION ABUNDANCE CRITERIA
8.0 - 40.0% of mass 95
30.0 - 66.0% of mass 95
Base peak, 100% relative abundance
5.0 - 9.0% of mass 95
Less than 2.0% of mass i?4
50.0 - 120.0% of mass 95
4.0 - 9.0 % of mass 174
93.0 - 101.0% of mass 174
5.0 - 9.0% of mass 176
% RELATIVE
ABUNDANCE
( )1
( >1
( )1
( )2
1-Value is % mass 174
2-Value is % mass 176
THIS TUNE APPLIES TO THE FOLLOWING SAMPLES, LCS, BLANKS, AND STANDARDS:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
EPA
SAMPLE NO.
LAB
SAMPLE ID
LAB
FILE ID
DATE
ANALYZED
TIME
ANALYZED
page
of
FORM V LCV
6/91
-------
5LCB
LOW CONC. WATER SEMIVOLATILE ORGANIC GC/MS TUNING AND MASS
CALIBRATION - DECAFLUOROTRIPHENYLPHOSPHINE (DFTPP)
T h Name:_
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Lab File ID:
Instrument ID:
DFTPP Injection Date:
DFTPP Injection Time:
m/e
51
68
69
70
127
197
198
199
275
365
441
442
443
ION ABUNDANCE CRITERIA
30.0 - 80.0% of mass 198
Less than 2.0% of mass 69
Mass 69 relative abundance
Less than 2.0% of mass 69
25.0 - 75.0% of mass 198
Less than 1.0% of mass 198
Base Peak, 100% relative abundance
5.0 to 9.0% of mass 198
10.0 - 30.0% of mass 198
Greater than 0.75% of mass 198
Present, but less than mass 443
40.0 - 110.0% of mass 198
15.0 - 24.0% of mass 442
% RELATIVE
ABUNDANCE
( )1
( )1
( )2
1-Value is % mass 69
2-Value is % mass 442
THIS TUNE APPLIES TO THE FOLLOWING SAMPLES, LCS, BLANKS, AND STANDARDS:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
EPA
SAMPLE NO.
LAB
SAMPLE ID
LAB
FILE ID
DATE
ANALYZED
TIME
ANALYZED
page of
FORM V LCSV
6/91
-------
6LCA
LOW CONG. WATER VOLATILE ORGANICS INITIAL CALIBRATION SUMMARY
Lab Name: Contract:
^ .o Code: ' Case No.: SAS No.: SDG No.:
Instrument ID: Calibration Date(s) :
LAB FILE ID: RRF1 -
RRF5 » RRF10-
COMPOUND
Chloromethane
Bromomethane '
Vinyl chloride <
Chloroethane
Methylene chloride
Acetone
Carbon disulfide
1,1-Dichloroethene i
1 , 1-Dichloroethane *
cis-1, 2-Dichloroethene
trans-1 , 2-Dichloroethene
Chloroform *
1 , 2-Dichloroethane i
2-Butanone
nromochloromethane i
1 , 1-Trichloroethane i
carbon tetrachloride 3
Bromodichloromethane '
1 , 2-Dichloropropane
cis-1 , 3 -Dichloropropene *
Trichloroethene <
Dibromochloromethane '
1,1, 2-Trichloroethane '
Benzene i
trans- l , 3 -D ichlor opropene <
Bromoform i
4 -Methy 1-2 -pentanone
2-Hexanone
Tetrachloroethene ^
1,1,2,2 -Tetr achlor oethane '
1 , 2 -Dibr omoethane ^
Toluene '
Chlorobenzene '
Ethylbenzene :
Styrene '
Xylenes (total) '
1 , 3-Dichlorobenzene '
1 , 4-Dichlorobenzene '
1,2-Dichlorobenzene '
1, 2-Dibromo-3-chloropropane__
RRF1
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
RRF2
RRF:
RRF:
RRF5
i -
25-
RRF10
RRF25
RRF
RSD
-romofluorobenzene *
1
* Compounds with required minimum RRF and maximum %RSD values.
All other compounds must meet a minimum RRF of 0.010,
FORM VI LCV
6/91
-------
6LCB
LOW CONG. WATER SEMIVOLATILE ORGANICS INITIAL CALIBRATION SUMMARY
•> Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Instrument ID:
Calibration Date(s):
Calibration Times:
LAB FILE ID: RRF5 -
RRF20- RRF50-
COMPODND
Phenol
bis ( 2-Chloroethyl) ether
2 -Chlorophenol
2 -Methy Iphenol
2,2' -oxybis ( 1 -Chlor opropane)
4 -Methy Iphenol
N-Nitroso-di-n-propylamine
Hexachloroethane
Nitrobenzene
Isophorone
"• -Nitrophenol
, 4-Dimethy Iphenol
bis (2-Chloroethoxy) methane
2 , 4-Dichlorophenol
1,2, 4-Trichlorobenzene
Naphthalene
4 -Chlor oaniline
Hexachlorobutadiene
4 -Chloro-3 -methy Iphenol '
2-Methylnaphthalene '
Hexachlorocyclopentadiene
2,4, 6-Trichlorophenol '
2,4, 5-Trichlorophenol '
2 -Chloronaphthalene
2 -Nitr oaniline
Dimethylphthalate
Acenaphthylene <
2 , 6-Dinitrotoluene '
3 -Nitroaniline
Acenaphthene *
2 , 4-Dinitrophenol
4 -Nitrophenol
Dibenzofuran *
2 , 4 -D ini tr ot o luene i
RRF5
k
k
k
k
k
k
t
k
k
RRF10
RRF:
RRFl
RRF20
L0=
30=
RRF50
RRF80
RRF
RSD
'ompounds with required minimum RRF and maximum %RSD values.
All other compounds must meet a minimum RRF of 0.010.
FORM VI LCSV-1
6/91
-------
6LCC
LOW CONG. WATER SEMIVOLATILE ORGANICS INITIAL CALIBRATION SUMMARY
T "•» Name:
Lab Code:
Instrument ID:
Contract:_
Case No.: SAS No.:
Calibration Date(s):
Calibration Times:
SD6 No.:
LAB FILE ID: RRF5 *
RRF20* RRF50*
COMPOUND
Diethylphthalate
4-Chlorophenyl-phenylether <
Fluorene *
4-Nitroaniline
4 , 6-Dinitro-2-methylphenol
N-Nitrosodiphenylamine (1)
4-Bromophenyl-phenylether *
Hexachlorobenzene '
Pentachlorophenol *
Phenanthrene 5
Anthracene <
-n-butylphthalate
Fluoranthene '
Pyrene *
Butylbenzylphthalate
3,3' -Dichlorobenzidiiie
Benzo ( a) anthracene •>
Chrysene 1
bis (2-Ethylhexyl) phthalate
Di-n-octvlphthalate
Benzo (b) f luoranthene
Benzo (k) f luoranthene
Benzo (a) pyrene
Indeno (1,2,3 -cd) pyrene
Dibenz ( a , h) anthracene
Benzo ( g , h , i ) pery lene
Nitrobenzene-d5
2 -Fluor obiphenyl
Terpheny 1-dl 4
Phenol-dS '
2-Fluorophenol '
2,4, 6-Tribromopheribi
RRF5
*
k
»
k
k
k
k
k
k
k
k
k
k
RRF10
RRF]
RRFi
RRF20
LO-
JO*
RRF50
RRF80
RRF
%
RSD
:
T
T
:
•:
-
-
r
7
f
•Sc
4
4
•i
i
•i
•i
y
4
r
T
(1) Cannot be separated from Diphenylamine
* Compounds with required minimum RRF and maximum %RSD values.
11 other compounds must meet a minimum RRF of 0.010.
FORM VI LCSV-2
6/91
-------
6LCD
LOW CONG. WATER PESTICIDE INITIAL CALIBRATION OF SINGLE COMPONENT ANALYTES
7 "> Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Instrument ID:
GC Column:
Level (x low): low mid
ID: (mm) Date(s) Analyzed:
high
COMPOUND
alpha-BHC
beta-BHC
delta-BHC
gamma-BHC (Lindane)
Heptachlor
Aldrin
Heptachlor epoxide
Endosulfan I
Dieldrin
4, 4 '-DDE
Endrin
Endosulfan II
4,4'-DDD
Endosulfan sulfate
4,4'-DDT
Hethoxychlor
Endrin ketone
Endrin aldehyde
alpha-Chlordane
gamma -Chlordane
Tetrachloro-m-xylene
Decachlorobiphenyl
RT 0]
LOW
— :
**
? STANDS
MID
aossa-s
*RDS
HIGH
=3=
MEAN
RT
=====
RT W]
FROM
CNDOW
TO
:
* Surrogate retention times are measured from Ind. Mix A analyses.
Retention time windows are ±0.05 minutes for all compounds that
elute before Heptachlor epoxide, ±0.07 minutes for all other
compounds, except ±0.10 minutes for Decachlorobiphenyl.
FORM VI LCP-1
6/91
-------
6LCE
LOW CONC. WATER PESTICIDE INITIAL CALIBRATION OF SINGLE COMPONENT ANALYTES
T •> Name:
Lab Code:
Instrument ID:
GC Column:
Case No.:
Contract:
SAS No.:
SDG No.:
Level (x low): low mid
ID: (mm) Date(s) Analyzed:
high
COMPOUND
alpha-BHC
beta-BHC
delta-BHC
gamma-BHC (Lindane)
Heptachlor
Aldrin
Heptachlor epoxide
Endosulf an I
Dieldrin
4. 4 '-DDE
Endrin
Endosulf an II
.4/-DDD
Endosulf an sulf ate
4. 4 '-DDT
Methoxychlor
Endrin ketone
Endrin aldehyde
alpha-Chlordane
gamma-Chlordane
Tetrachloro-m-xylene
Decachlorobiphenyl
LOW
CALIBRATIC
MID
>N FACTORS
HIGH
MEAN
%RSD
* Surrogate calibration factors are measured from Ind. Mix A analyses.
%RSD must be less than or equal to 20.0% for all compounds, except the
surrogates, where %RSD must be less than or equal to 30.0%. Up to two
target compounds, but not surrogates, may have %RSD greater than 20.0%,
but less than or equal to 30.0%.
FORM VI LCP-2
6/91
-------
6LCF
LOW CONG. WATER PESTICIDE INITIAL CALIBRATION OF MULTICOMPONENT ANALYTES
T > Name:
Lab Code:
Instrument ID:
GC Column:
Contract:
Case No.: SAS No.: SDG No.:
Date(s) Analyzed:
ID: (mm)
COMPOUND
Toxaphene
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
AMOUNT
(ng)
PEAK
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
RT
RT w:
FROM
CNDOW
TO
CALIBRATION
FACTOR
* Denotes required peaks
FORM VI LCP-3
6/91
-------
6LC6
LOW CONG. WATER PESTICIDE RESOLUTION CHECK SUMMARY
" •> Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.
GC Column (1):
ID:
EPA Sample No. (Standard 1):
Date Analyzed (1):
GC Column (2):
ID:
EPA Sample No. (Standard 2):
Date Analyzed (2):
(mm) Instrument ID (1):
Lab Sample ID (1):
Time Analyzed (1):
01
02
03
04
05
06
07
08
09
ANALYTE
RT
RESOLUTION
(%)
(mm) Instrument ID (2):
Lab Sample ID (2):
Time Analyzed (2):
01
02
03
04
05
06
07
08
09
ANALYTE
RT
RESOLUTION
(%)
Resolution of two adjacent peaks must be calculated as a percentage of the
height of the smaller peak, and must be greater than or equal to 60.0%.
FORM VI LCP-4
6/91
-------
7LCA
LOW CONG. WATER VOLATILE ORGANICS CONTINUING CALIBRATION SUMMARY
Lab Name:
..—o Code:
Case No.:
Contract:
SAS No.:
Instrument ID:
Lab File ID:
Calibration Date:
Init. Calib. Date(s) :.
SDG No.:
Time:
All other compounds must meet a minimum RRF of 0.010.
FORM VII LCV
COMPOUND
Chloromethane
Bromomethane
Vinyl chloride
Chloroethane
Methylene chloride
Acetone
Carbon disulfide
1 , 1-Dichloroethene
1 , l-Dichloroethane
cis-1 , 2-Dichloroethene
trans -1 , 2-Dichloroethene
Chloroform
1 , 2-Dichloroethane
2-Butanone
Bromochloromethane
1, 1, 1-Trichloroethane
Carbon tetrachloride
Bromodi Chloromethane
1 , 2-Dichloropropane
cis-1 , 3-Dichloropropene
Tr ichlor oethene
Dibromochloromethane
1,1, 2 -Tr ichlor oethane
Benzene
trans-l , 3-Dichloropropene
Bromoform
4 -Methy 1-2 -pentanone
2-Hexanone
Tetrachloroethene
1,1,2, 2-Tetrachloroethane
1 , 2-Dibromoethane
Toluene
Chlorobenzene
Ethy Ibenz ene
Styrene
Xylenes (total)
1 , 3-Dichlorobenzene
1, 4-Dichlorobenzene
1 , 2-Dichlorobenzene
1 , 2-Dibromo-3-chloroprdpane
Bromofluorobenzene
RRF
RRF5
— =
MIN
RRF
0.100
0.100
0.100
0.200
0.100
0.200
0.100
0.050
0.100
0.100
0.200
0.200
0.300
0.100
0.100
0.500
0.100
0.050
0.200
0.100
0.100
0.400
0.500
0.100
0.300
0.300
0.600
0.500
0.400
0.200
%D
— — "
MAX
%D
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
30.0
6/91
-------
7LCB
LOW CONC. WATER SEMIVOLATILE ORGANICS CONTINUING CALIBRATION SUMMARY
" '•> Name:
Lab Code:
Case No.:
Contract:
SAS No.:
Instrument ID:
Lab File ID:
Calibration Date:
Init. Calib. Date(s).\
Init. Calib. Times:
SDG No.:
Time:
COMPOUND
Phenol
bis (2-Chloroethyl) ether
2 -Chlor ophenol
2 -Methy Iphenol
2,2' -oxybis ( l-Chloropropane)
4 -Methy Iphenol
N-Nitroso-di-n-propy'Ia^aine
Hexachloroethane
Nitrobenzene
Isophorone
2 -Nitrophenol
2 , 4 -Dimethy Iphenol
bis ( 2 -Chlor oethoxy ) methane
2 , 4 -Dichlor ophenol
1,2, 4-Trichlorobenzene
Naphthalene
4-Chloroaniline
Hexachlorobutadiene
4 -Chlor o-3 -methy Iphenol
2 -Methy Inaphthalene
Hexachlorocyclopentadlene
2,4, 6-Trichlorophenol
2,4, 5-Trichlorophenol
2 -Chloronaphthalene
2-Nitroaniline
Dimethy Iphthalate
Acenaphthylene
2 , 6-Dinitrotoluene
3 -Nitr oaniline
Acenaphthene
2 , 4-Dinitrophenol
4 -Nitrophenol
Dibenzofuran
2 , 4-Dinitrotoluene
RRF
RRF20
MIN
RRF
0.800
0.700
0.700
0.700
0.600
0.500
0.300
0.200
0.400
0.100
0.200
0.300
0.200
0.200
0.700
0.200
0.400
0.200
0.200
0.800
1.300
0.200
0.800
0.800
0.200
%D
MAX
%D
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
All other compounds must meet a minumum RRF of 0.010.
FORM VII LCSV-1
6/91
-------
7LCC
LOW CONG. WATER SEMIVOLATILE ORGANICS CONTINUING CALIBRATION SUMMARY
T ^ Name:.
Lab Code:
Case No.:
Contract:
SAS No.:
Instrument ID:
Lab File 10:
Calibration Date:
Init. Calib. Date(s) :
Init. Calib. Tines:
SDG No.:
Time:
COMPOUND
Diethylphthalate
4-Chlorophenyl-phenylether
Fluorene
4-Nitroaniline
4 , 6-Dinitro-2-methylphenol
N-Nitrosodipheny lamine ( 1 }
4 -Bromopheny 1-pheny lether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-butylphthalate
F luor anthene
Pyrene
Butylbenzylphthalate
3,3' -Dichlorobenzidine
Benzo (a) anthracene
Chrysene
bis (2-Ethylhexyl) phthalate
Di-n-octylphthalate
Benzo (b) f luor anthene
Benzo (k) f luor anthene
Benzo ( a) pyrene
Indeno (1,2,3 -cd) pyrene
Dibenz ( a , h) anthracene
Benzo (g , h , i ) perylene
Nitrobenzene~d5
2 -Fluor obipheny 1
Terphenyl-dl4
Phenol-d5
Fluorophenol
2,4, 6-Tribromophenol
RRF
RRF20
MIN
RRF
0.400
0.900
0.100
0.100
0.050
0.700
0.700
0.600
0.600
0.800
0.700
0.700
0.700
0.700
0.500
0.400
0.500
0.010
0.700
0.500
0.800
0.600
%D
MAX
%D
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
25.0
(1) Cannot be separated from Diphenylamine
All other compounds must meet a minimum RRF of 0.010.
FORM VII LCSV-2
6/91
-------
7LCD
LOW CONC. WATER PESTICIDE CALIBRATION VERIFICATION SUMMARY
' b Name:_
Lab Code:
GC Column:
Contract:
SAS No.:
Case No.: SAS No.: SDG No.:
ID: (mm) Init. Calib. Date(s):
EPA Sample No.(PIBLK):
Lab Sample ID (PIBLK) :.
EPA Sample No.(PEM): _
Lab Sample ID (PEM):
Date Analyzed
Time Analyzed
Date Analyzed
Time Analyzed
PEM
COMPOUND
alpha-BHC
beta-BHC
gamma-BHC (Lindane)
Endrin
4, 4 '-DDT
Methoxychlor
RT
RT W]
FROM
ENDOW
TO
CALC
AMOUNT
(ng)
NOM
AMOUNT
(ng)
%D
4,4'-DDT % breakdown (1):
Combined % breakdown (1):
Endrin % breakdown (1):
QC LIMITS:
Absolute values of %D of amounts in PEM must be less than or equal to
25.0%
4,4'-DDT breakdown must be less than or equal to 20.0%
Endrin breakdown must be less than or equal to 20.0%
Combined breakdown must be less than or equal to 30.0%
FORM VII LCP-1
6/91
-------
7LCE
LOW CONC. WATER PESTICIDE CALIBRATION VERIFICATION SUMMARY
^ Name:_
Lab Code:
GC Column:
Contract:
SAS No.:
Case No.: SAS No.: SDG No.:
ID: (mm) Init. Calib. Date(s):
EPA Sample No.(PIBLK):
Lab Sample ID (PIBLK):
EPA Sample No.(INDA):
Lab Sample ID (INDA):
Date Analyzed :_
Time Analyzed :
Date Analyzed :.
Time Analyzed :
INDIVIDUAL MIX A
COMPOUND
alpha-BHC
gamma-BHC (Lindane)
Heptachlor
Endosulf an I
Dieldrin
Endrin
4. 4 '-ODD
4. 4 '-DDT
iethoxychlor
Tetrachloro-m-xylene
Decachlorobiphenyl
RT
RT W]
FROM
ENDOW
TO
CALC
AMOUNT
(ng)
NOM
AMOUNT
(ng)
%D
EPA Sample No.(INDB):
Lab Sample ID (INDB):
Date Analyzed
Time Analyzed
INDIVIDUAL MIX B
COMPOUND
beta-BHC
delta-BHC
Aldrin
Heptachlor epoxide
4. 4 '-DDE
Endosulfan II
Endosulf an sulfate
Endrin ketone
Enrin aldehyde -
alpha-Chlordane
gamma-Chlorodane
Tetrachloro-m-xylene
Decachlorobiphenyl
RT
RT W]
FROM
ENDOW
TO
CALC
AMOUNT
(ng)
NOM
AMOUNT
(ng)
%D
QC LIMITS:
Absolute value of %D of amounts in the Individual Mixes must b
less than or equal to 25.0%.
FORM VTI LCP-2
6/91
-------
8LCA
LOW CONG. WATER VOLATILE INTERNAL STANDARD AREA AND RT SUMMARY
* '•) Name:
Lab Code:
Case No.:
Contract:
SA5 No.:
SDG No.
Lab File ID (Standard):
Instrument ID:
GC Column: ID:
Date Analyzed:
Time Analyzed:
(mm)
01
02
03
04
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
12 HOUR STD
UPPER LIMIT
LOWER LIMIT
EPA SAMPLE
NO.
ISl(CBZ)
AREA t
RT #
IS2 (DFB)
AREA #
RT #
IS3 (DCB)
AREA #
RT #
IS1 (CBZ) — Chlor obenz ene-d5
IS2 (DFB) = 1,4-Difluorobenzene
IS3 (DCB) = l,4-Dichlorobenzene-d4
AREA UPPER LIMIT - +40% of internal standard area.
AREA LOWER LIMIT = -40% of internal standard area.
RT UPPER LIMIT - +0.33 minutes of internal standard RT.
RT LOWER LIMIT = -0.33 minutes of internal standard RT.
# Column used to flag internal standard area and RT values with an asteris
* Values outside of QC limits.
page of
FORM VIII LCV
6/91
-------
8LCB
LOW CONC. WATER SEMIVOIATILE INTERNAL STANDARD AREA AND RT SUMMARY
b Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.
Lab File ID (Standard):
Instrument ID:
Date Analyzed:
Time Analyzed:
01
02
03
04
05
^6
7
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
12 HOUR STD
UPPER LIMIT
LOWER LIMIT
EPA SAMPLE
NO.
ISl(DCB)
AREA t
RT #
IS2 (NPT)
AREA f
RT #
IS3 (ANT)
AREA f
RT #
IS1 (DCS) » l,4-Dichlorobenzene-d4
IS2 (NPT) = Naphthalene-d8
IS3 (ANT) » Acenaphthene-dlO
AREA UPPER LIMIT = +100% of internal standard area.
AREA LOWER LIMIT - -50% of internal standard area.
RT UPPER LIMIT = +0.33 minutes of internal standard RT.
RT LOWER LIMIT = -0.33 minutes of internal standard RT.
# Column used to flag internal standard area and RT values with an asteris]
* Values outside of QC limits.
page of
FORM VIII LCSV-1
6/91
-------
8LCC
LOW CONG. WATER SEMIVOLATILE INTERNAL STANDARD AREA AND RT SUMMARY
' "3 Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.
Lab File ID (Standard):
Instrument ID:
Date Analyzed:
Time Analyzed:
12 HOUR STD
UPPER LIMIT
LOWER LIMIT
EPA SAMPLE
NO.
IS4 (PHN)
AREA f
.
RT #
ISS(CRY)
AREA #
RT #
IS6(PRY)
AREA #
RT #
01
02
03
04
05
"6
7
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
IS4 (PHN)
IS5 (CRY)
IS6 (PRY)
Phenanthrene-dl0
Chrysene-dl2
Perylene-dl2
AREA UPPER LIMIT = +100% of internal standard area.
AREA LOWER LIMIT = -50% of internal standard area.
RT UPPER LIMIT = +0.33 minutes of internal standard RT.
RT LOWER LIMIT = -0.33 minutes of internal standard RT.
# Column used to flag internal standard area and RT values with an aster is
* Values outisde of QC limits.
page of
FORM VIII LCSV-2
6/91
-------
Lab Name:_
- .o Code:
GC Column:
8LCD
LOW CONG. WATER PESTICIDE ANALYTICAL SEQUENCE
Contract:
SAS No.: SDG No.:
Case No.:
__ ID: (mm) Init. Calib. Date(s):
Instrument ID:
THE ANALYTICAL SEQUENCE OF PERFORMANCE EVALUATION MIXTURES, BLANKS,
SAMPLES, AND STANDARDS IS GIVEN BELOW:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
MEAN SURRO<
TCX:
EPA
SAMPLE NO.
3ATE RT FROM :
DCS:
LAB
SAMPLE ID
CNITIAL CAL:
DATE
ANALYZED
[BRATION
TIME
ANALYZED
TCX
RT #
DCB
RT #
TCX = Tetrachloro-m-xylene
DCB = Decachlorobiphenyl
QC LIMITS
(± 0.05 MINUTES)
(± 0.10 MINUTES)
# Column used to flag retention time values with an asterisk.
* Values outside of QC limits.
page of
FORM VIII LCP
6/91
-------
9LCA
LOW CONC. WATER PESTICIDE FLORISIL CARTRIDGE CHECK
Lab Name:
o Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Florisil Cartridge Lot Number:
GC Column(l) : ID:
Date Analyzed:
(mm) GC Column(2):
ID:
(mm
COMPOUND
alpha-BHC
gamma-BHC
Heptachlor
Endosulfan I
Dieldrin
Endrin
4,4' -ODD
4,4'-DDT
Methoxychlor
Tetrachloro-m-xylene
Decachlorobiphenyl
SPIKE
ADDED
(ng)
SPIKE
RECOVERED
(ng)
%
REC t
QC
LIMITS
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
80-120
f Column to be used to flag recovery with an asterisk
* Values outside of QC limits
THIS CARTRIDGE LOT APPLIES TO THE FOLLOWING SAMPLES, BLANKS, AND LCS:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
EPA
SAMPLE NO.
LAB
SAMPLE ID
"
DATE
ANALYZED 1
DATE
ANALYZED 2
page of
FORM IX LCP
6/91
-------
10LCA
LOW CONG. WATER PESTICIDE IDENTIFICATION SUMMARY
FOR SINGLE COMPONENT ANALYTES
EPA SAMPLE NO.
Y Name:
Lab Code:
Case No.:
Contract:^
SAS No.:
SDG No.:
Lab Sample ID :
Instrument ID (1):
GC Column (1):
ID:
Date(s) Analyzed:
Instrument ID (2):
(mm) GC Column(2):
ID:
ANALYTE
COL
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
RT
RT W]
FROM
ENDOW
TO
CONCENTRATION
%D
page of
FORM X LCP-1
6/91
-------
10LCB
LOW CONC. WATER PESTICIDE IDENTIFICATION SUMMARY
FOR MULTICOMPONENT ANALYTES
EPA SAMPLE NO.
b Name:_
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Lab Sample ID :
Instrument ID (1)
GC column(1):
ID:
Date(s) Analyzed:
Instrument ID (2):
(mm) GC Column(2):
ID:
(mm
ANALYTE
COLUMN 1
COLUMN 2
COLUMN 1
COLUMN 2
COLUMN 1
COLUMN 2
PEAK
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
4
5
*1
*2
*3
• 4
5
RT
"™
RT W]
FROM
"
=
ENDOW
TO
=====
=
CONCENTRATION
MEAN
CONCENTRATION
%D
: least 3 peaks are required for identification of multicomponent analyses
page of
FORM X LCP-2
6/91
-------
SAMPLE LOG-EN SHEET
Lab Name:
Received Bv ( Print Name* Log in Dale:
Received By fSipumre^:
Cue Number:
Sample Delivery
Group No^ ,
SAS Number:
REMARKS:
1. Custody Se*l(s) Pnsent/Abseat*
Intact/Broken
2. Cuaodv Sal Not_-
3. Quim-of-Cuaody Present/Absent*
Recoris
4. Tnffic Repoiu or Present/Absent"
Picking List
S. Aiifafll Aiibfll/Sticker
Present/Absent*
. Annul No.:
7. Sample T««J PreseBt/Absenl*
SampfeTag Liaed/Nbt Liaed
Nmnben on Cham-of-
Gttody
8. Sample Coodition: Inuct/Broken*/
Leaking
9. Does infonnation on
icportit JOQ SMDJMC
tags une? Yes/No*
10. Due Received at L«tr
11. TuneReeoved;
Sample Transfer
nn. r. _.
EPA
SAMPLE
#
CORRESPONDING
SAMPLE
TAG
*
ASSIGNED
LAB
*
REMARKS:
CONDITION
OF SAMPLE
SHIPMENT, ETC.
• Conua SMO and attach recort of resolution
Reviewed By: ________________
Date:
Logbook No,;
Logbook Page No:
FORM DC-1
-------
LOW CONCENTRATION WATER FOR ORGANICS COMPLETE SDO FILE (CSF) INVENTORY SHEET
LABORATORY NAME CITY/STATE
CASE NO. _ SOC NO. _ SDG NOS. TO FOLLOW
NO. _
CONTRACT NO. _ SOU NO.
All documents delivered in the complete SDG file must be original documents
where possible. (REFERENCE EXHIBIT B, SECTION II, PARAGRAPH 5, and SECTION III,
PARAGRAPH 16.)
PAGE NOs CHECK
FROM TO LAB EPA
1. Inrentcrr Sheet (Form DC*2) (Do not number)
2. SPG case Narrative
3. Traffic Report
4. Volatile* Data
a.. QC Summary
Surrogate Percent Recovery Summary (Form II LCV)
Lab Control Sample Recovery (From III LCV)
Method Blank Summary (Form IV LCV)
Tuning and Mass Calibration (Form V LCV)
b. Sample Data
TCL Results • (Form I LCV)
Tentatively Identified Compounds (Form I LCV-TIC)
Reconstructed total ion chromatograms (RIC)
and Quantitation Reports for each sample
For each sample:
Raw spectra and background-subtracted
mass spectra of target compounds identified
Mass spectra of all reported TICs with three
best library matches
c. Standards Data (All Instruments)
Initial Calibration Summary (Form VI LCV)
RICs and Quan Reports for all Standards
Continuing Calibration (Form VII LCV)
RICs and Quant Reports for all Standards
Internal Standard Area and RT Summary
(Form VIII LCV)
d. QC Data
BFB
Blank Data
LCS Data
PES Data
5. semivola'ti.laa Data
a. QC Summary
Surrogate Percent Recovery Summary (Form II LCSV)
Lab Control Sample Recovery (Form III LCSV)
Method Blank Summary (Form IV LCSV)
Tuning and Mass Calibration (Form V LCSV)
FORM DC-2-1
6/
-------
LOW COHCEHTRAXIOX WATER FOR ORGAHICS COMPLETE SDO FILE (CSF) INVENTORY SHEET (Coat.)
CASE NO. SDG MO. SOG NOS. TO FOLLOW SAS MO.
PAGE NOs CHECK
FROM TO LAB EPA
5. 8»iH^ol»-tHe» Pa'fca (cont.)
b. Sample Data
TCL Results (Form I LCSV)
Tentatively Identified Compounds (Form I LCSV-TIC)
Reconstructed total ion chromatograms (RIC)
and Quantitation Reports for each sample
For each sample:
Raw spectra and background-subtracted
mass spectra of TCL compounds
Mass spectra of TICs with three best library matches
GFC chromatograms (if GPC performed)
c. Standards Data (All Instruments)
Initial Calibration Summary (Form VI LCSV)
RICs and Quan Reports for all Standards
Continuing Calibration (Form VII LCSV)
RICs and Quan Reports for all Standards
Internal Standard Area and RT Summary
(Form VIII LCSV)
d. QC Data
DFTPP
Blank Data
LCS Data
FES Data
6. Pesticide*
a. QC Summary
Surrogate Percent Recovery Summary (Form II LCP)
Lab Control Sample Recovery (Form III LCP)
Method Blank Summary (Form IV LCP)
b. Sample Data
TCL Results - Organic Analysis Data Sheet
(Form I LCP)
Chromatograms (Primary Column)
Chromatograms from second GC column confirmation
GC Integration report or data system printout and
calibration plots
Manual work sheets
For pesticides/Aroclors confirmed by GC/MS, copies
of raw spectra and copies of background-subtracted mass
spectra of target compounds (samples & standards)
FORM DC-2-2
-------
LOW CONCENTRATION WATER FOR ORGANZCS COMPLETE SCO FILE (CSF) INVENTORY SHEET (Cont.)
CASE NO.
SOG NO.
soc MOS. TO rau.au
SAS HO.
PAGE NOs
FROM TO
CHECK
IAB EPA
5. Pertieidea (cont.)
c. Standards Data
Initial Calibration Data (Form VI LCP)
Calibration Verification (Form VII LCP)
Pesticides Analytical Sequence (Form VIII,
LCP-1 and -2)
PesticideFlorisil Cartridge Check (Form IX, LCP)
Pesticide Identification (Form X LCP)
Standard chromatograms and data system printout
for all Standards
For pesticides/Aroclors confirmed by GC/MS, copies
of spectra for standards used
d. QC Data
Blank Data
LCS Data
PES Data
Original preparation and analysis forms or copies of
preparation and analysis logbook pages
Internal sample and sample extract transfer
chain-of-custody records
Screening records
All instrument output, including strip charts
from screening activities (describe or list)
3.
EPA Shli
lino/
Airbills (No. of shipments )
Chain-of-Custody Records
Sample Tags
Sample Log-In Sheet (Lab & DC1)
SDG Cover Sheet
Miscellaneous Shipping/Receiving Records
(describe or list)
9. IntemaJ. I»ab Saaple Transfer1 Records and Tracking Sheet*
(describe or list)
FORM DC-2-3
-------
LOW CONCENTRATION WATER FOR ORGANICS COMPLETE SDG FILE (CSF) INVENTORY SHEET (Cont.)
CASE NO.
SOG NO.
SOG MOS. TO FOLLOW
.0. Other Record* (describe or list)
Telephone Commmication Log
1.1.
SAS NO.
PAGE NOs CHECK
FROM TO LAB EPA
Zompleted by:
(CLP Lab)
(Signature)
(Printed Name/Title)
(Date)
Audited by:
(EPA)
(Signature)
(Printed Name/Title)
(Date)
FORM DC-2-4
-------
EXHIBIT C
TARGET COMPOUND LIST (TCL) AND
CONTRACT REQUIRED QUANTITATION LIMITS (C&QLs)
NOTE: The values in these tables are quantitation limits, not absolute
detection limits. The amount of material necessary to produce a
detector response that can be identified and. reliably quantified is
greater than that needed to simply be detected above the background
noise. Except as noted, the quantitation limits in these tables are
set at the concentrations in the sample equivalent to the
concentration of the lowest calibration standard analyzed for each
analyte.
C-l 6/91
-------
TARGET COMPOUND LIST (TCL) AND
CONTRACT REQUIRED QUANTITATION LIMITS (CRQL)
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.
Volatiles
Chlorone thane
Bromome thane
Vinyl chloride
Chloroethane
Methylene chloride
Acetone
Carbon disulfide
1,1- Dichloroe thene
1 , 1-Dichloroe thane
cis -1,2 -Dichloroe thene
trans -1,2 -Dichloroe thene
Chloroform
1 , 2 - Dichloroe thane
2-Butanone
Bromochlorome thane
1 , 1 , 1-Trichloroethane
Carbon Tetrachloride
Bromodichlorome thane
1 , 2 -Dichloropropane
cis - 1 , 3 - Dichloropropene
Trichloroe thene
Oibroaochlorome thane
1,1, 2 -Trichloroe thane
Benzene
trans - 1 , 3 -Dichloropropene
Brontoform
4-Methyl-2-pentanone
2-Hexanone
Tetrachloroe thene
CAS Number
74-87-3
74-83-9
75-01-4
75-00-3
75-09-2
67-64-1
75-15-0
75-35-4
75-34-3
156-59-4
156-60-5
67-66-3
107-06-2
78-93-3
74-97-5
71-55-6
56-23-5
75-27-4
78-87-5
10061-01-5
79-01-6
124-48-1
79-00-5
71-43-2
10061-02-6
75-25-2
108-10-1
591-78-6
127-18-4
Quantisation Limits
Water
"g/L
1
1
1
1
2
5
1
1
1
1
1
1
1
5
1
1
1
1
1
1
1
1
1
1
1
1
5
5
1
C-2
6/91
-------
TARGET COMPOUND LIST (TCL) AND
CONTRACT REQUIRED QUANTITATION LIMITS (CRQL)
(CONT'D.)
Quantitation Limits
Volatiles
CAS Number
Water
ug/L
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
1,1,2, 2-Tetrachloroethane
1 , 2-Dibromoethane
Toluene
Chlorobenzene
Ethylbenzene
Styrene
Xylenes (total)
1, 3-Dichlorobenzene
1,4- Dichlorobenzene
1 , 2 -Dichlorobenzene
79-34-5
106-93-4
108-88-3
108-90-7
100-41-4
100-42-5
1330-20-7
541-73-1
106-46-7
95-50-1
1
1
1
1
1
1
1
1
1
1
40. l,2-Dibromo-3-chloropropane
96-12-8
NOTE: Except for Methylene chloride, the quantitation limits in this table
are set at the concentrations in the sample equivalent to the
concentration of the lowest calibration standard analyzed for each
analy te.
In the case of Methylene chloride, the CRQL value in this table is
based on the lowest level of detection in samples contaminated with
this common laboratory solvent that can be achieved by reasonable
means in a production laboratory.
C-3
6/91
-------
TARGET COMPOUND LIST (TCI.) AND
CONTRACT REQUIRED OPAMTITATTOM T,TMITS (CROP
(CONT'D.)
Quantisation Limits
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
Sentivo latiles
Phenol
bis- (2-Chloroethyl)ether
2 -Chlorophenol
2-Methylphenol
2,2'- oxyb is ( 1 - caxloropropane )
4-Methylphenol
N- Nitroso - di - n- pr opy lamine
Hexachloroe thane
Nitrobenzene
Isophorone
2-Nitrophenol
2 , 4-Dimechylphenol
bis- (2-Chloroethoxy)me thane
2 , 4-Oichlorophenol
1,2,4-Trichlorobenzene
Naphthalene
4-Chloroaniline
Hexachlorobutadiene
4-Chloro- 3 -methylphenol
2 -Me thy Inaphthalene
Hexachlorocyclopentadiene
2,4,6- Trichloropheno 1
2,4,5- Trichloropheno 1
2 - Chloronaphthalene
2-Nitroaniline
Dime thy Iphthalate
Acenaphthylene
2 , 6 -Dinitro toluene
3-Nitroaniline
Acenaphthene
2 , 4-Dinitrophenol
4 - Ni tropheno 1
Dibenzofuran
CAS Number
108-95-2
111-44-4
95-57-8
95-48-7
108-60-1
106-44-5
621-64-7
67-72-1
98-95-3
78-59-1
88-75-5
105-67-9
11-91-1
120-83-2
120-82-1
91-20-3
106-47-8
87-68-3
59-50-7
91-57-6
77-47-4
88-06-2
95-95-4
91-58-7
88-74-4
131-11-3
208-96-8
606-20-2
99-09-2
83-32-9
51-28-5
100-02-7
132-64-9
Water
US/L
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
20
5
20
5
5
5
20
5
20
20
5
C-4
6/91
-------
TARGET COMPOUND LIST (TCL) AND
CONTRACT REQUIRED QUANTITATION LIMITS (CRQL)
(CONT'D.)
Quancitacion Limits
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
Semivolaciles
2 , 4-Dinitrotoluene
Oiethylphthalate
4- Chloropheny 1 - pheny le ther
Fluorene
4-Nitroaniline
4, 6-Dinitro-2-methylphenol
N-Nitrosodiphenylamine
4-Bronophenyl-phenylether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Di -n-butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
3,3' -Dichlorobenzidine
Benzo(a) anthracene
Chrysene
b is - ( 2 - Ethy Ihexyl ) phthalate
Di -n-octylphthalate
Benzo (b ) fluoranthene
Benzo (k) fluoranthene
Benzo ( a ) pyr ene
Indeno ( 1 , 2 , 3 - cd) pyrene
Dibenz ( a , h) anthracene
Benzo (g,h,i)perylene
CAS Number
121-14-2
84-66-2
7005-72-3
86-73-7
100-01-6
534-52-1
86-30-6
101-55-3
118-74-1
87-86-5
85-01-8
120-12-7
84-74-2
206-44-0
129-00-0
85-68-7
91-94-1
56-55-3
218-01-9
117-81-7
117-84-0
205-99-2 -
207-08-9
50-32-8
193-39-5
53-70-3
191-24-2
Water
ug/L
5
5
5
5
20
20
5
5
5
20
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
C-5
6/91
-------
TARGET COMPOUND LIST (TCL) AND
CONTRACT REQUIRED QUANTITATION LIMITS (CRQL)
(CONT'D.)
Quaneitation Limits
Pcsticides/PCBs
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.
alpha-BHC
beta-BHC
delta-BHC
gamma-BBC (Lindane)
Heptachlor
Aldrin
Heptachlor epoxide
Endosulfan I
Dieldrin
4, 4' -DDE
Endrin
Endosulfan II
4,4' -ODD
Endosulfan sulfate
4, 4' -DDT
Methoxychlor
Endrin ketone
Endrin aldehyde
alpha- Chlordane
gamna- Chlordane
Toxaphene
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
CAS Number
319-84-6
319-85-7
319-36-8
58-89-9
76-44-8
309-00-2
1024-57-3
959-98-8
60-57-1
72-55-9
72-20-8
33213-65-9
72-54-8
1031-07-8
50-29-3
72-43-5
53494-70-5
7421-36-3
5103-71-9
5103-74-2
8001-35-2
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
Water
ug/L
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.10
0.02
0.02
0.01
0.01
1.0
0.20
0.40
0.20
0.20
0.20
0.20
0.20
C-6
6/91
-------
EXHIBIT D
METHOD FOR THE ANALYSIS OF LOW CONCEIITBATIOH BATES. FOR
VOLATILE (FURGEABLE) ORGANIC COMPOUNDS
VOA D-l 6/91
-------
Table of Contents
Page
SECTION I: Introduction VOA D- 3
SECTION II:
Part A - Sample Storage and Holding Tines VOA D-4
Part B - VOA D-5
SECTION III: Instrument Quality Control Procedures
and Requirements
Part A - Instrument Operating Conditions VOA D-15
Part B - Tuning the Mass Spectrometer VOA D-17
Part C - Calibration of the GC/MS System VOA D-19
SECTION IV: Sample Analysis and Compound Identification
and Quantitation VOA D-26
SECTION V: Sample Quality Control Procedures and
Requirements VOA D-36
VOA D-2
6/91
-------
SECTION I
INTRODUCTION
The analytical method that follows is designed to analyze samples containing
low concentrations of the volatile compounds listed in the Target Compound
List (TCL) in Exhibit C. The majority of the samples are expected to be from
drinking water and well/ground water sources around Superfund sites. The
method is based on EPA Method 524.2 and the volatile method contained in the
CLP Statement of Work, "Organic Analysis, Hulti Media, Multi Concentrations
by GO/MS and GC/EC Techniques". Specific quality control requirements are
incorporated in the method in order to minimize contamination of the samples
from laboratory sources.
Problems have been associated with the following compounds analyzed by this
method.
o Chloromethane, vinyl chloride, bromomethane, and chloroethane may display
peak broadening if the compounds are not delivered to the GC column in a
tight band.
o Acetone, hexanone, 2-butanone. and 4-methyl-2-pentanone have poor purge
efficiencies.
o 1,1,1-Trichloroethane and all of the dichloroethanes may dehydrohalogenate
during storage or analysis.
o Tetrachloroethane and 1,1-dichloroethane may be degraded by contaminated
transfer lines in purge and trap systems and/or active sites in trapping
materials.
o Chloromethane may be lost if the purge flow is too fast.
o Bromoform is one of the compounds most likely to be adversely affected by
cold spots and/or active sites in the transfer lines. Response of its
quantitation ion (m/z 173) is directly affected by the tuning of BFB at
ions m/z 174/176. Increasing the m/z 174/176 ratio within the specified
QC limits may improve bromoform response.
o Due to the lower quantitation limits required by this method, extra
caution must be exercised when identifying compounds.
VOA D-3 6/91
-------
SECTION II
PART A - SAMPLE STORAGE AND HOLDING TIMES
1. PROCEDURES FOR SAMPTg STORAGE
The samples oust be protected from light and refrigerated at 4*0 (±2*C)
froa the time of receipt until 60 days after delivery of a complete
reconciled sample data package. After 60 days, the samples may be
disposed of in a manner that complies with all applicable regulations.
The samples must be stored in an atmosphere demonstrated to be free of
all potential contaminants and in a refrigerator used only for storage
of purgeable samples received under this contract.
Samples, sample extracts, and standards must be stored separately.
Volatiles standards must be stored separately from semivolatile and
pesticide/Aroclor standards.
2. CONTRACT REQUIRED HOLDING TIMES
Analysis of samples must be completed within 10 days of the validated
time of sample receipt (VTSR).
VGA D-4 6/91
-------
FART B
3. SUMMARY OF METHOD
3.1 An inert gas is bubbled through a 25 mL sample contained in a specially
designed purging chamber at ambient temperature causing the purgeables
to be 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
chromatograph (GO) wide-bore capillary column. The gas chromatograph
is temperature programmed to separate the purgeables, which are then
detected with a mass spectrometer (MS) .
3.2 Target and surrogate compounds are identified in the samples by
analyzing standards under the same conditions used for samples and
comparing resultant mass spectra and GC retention times. Internal
standards are added to all samples and standards. A response factor is
established for each target and surrogate compound during the initial
and continuing calibrations by comparing the MS response from the
extracted ion current profile (EICP) for the primary ion produced by
the target and surrogate compound to the MS response for the primary
ion produced by an internal standard compound. Each identified target
and surrogate compound in a sample is quantified by comparing the
responses for the target compound and the internal standard, while
taking into account the response factor from the most recent
calibration, the sample volume, and any sample dilutions.
3.3 Non- target compounds are identified by comparing the resultant mass
spectra from the non- target compounds to mass spectra contained in the
National Institute of Standards and Technology Mass Spectral Library.
Non- target compounds are quantified by comparing the MS response from
the reconstructed ion chromatogram (RIG) for the non- target compound
peaks to the MS response for a peak produced by the nearest internal
standard compound. A response factor of 1 is assumed.
4.
4.1 Impurities in the purge gas or methanol, organic compounds out-gassing
from the plumbing ahead of the trap, and solvent vapors in the
laboratory account for the majority of contamination problems. Gas
lines from the gas tanks to the instrument must be either stainless
steel or copper tubing. Non-polytetrafluoroethylene (PTFE) thread
sealants, or flow controllers with rubber components are not to be
used. When potential interfering peaks are noted in laboratory method
blanks, it may be necessary to reduce solvent contamination in the
laboratory, purge the methanol used to prepare standard solutions,
purge the reagent water with helium or nitrogen, change the purge gas
source, or regenerate the molecular sieve purge gas filter.
4.2 Samples can be contaminated by diffusion of purgeable organics
(particularly methylene chloride, fluorocarbons , and other common
laboratory solvents) through the septum seal into the sample during
storage and handling. Therefore, these samples must be stored
VGA D-5 6/91
-------
separately from other laboratory samples and standards and must be
analyzed in a room whose atmosphere is demonstrated to be free of all
potential contaminants which will interfere with the analysis. Since
methylene chloride will permeate through PTFE tubing, all gas
chromatography carrier gas lines and purge gas plumbing lines are to be
constructed from stainless steel or copper tubing.
Non-polytetrafluoroethylene (PTFE) thread sealants, or flow controllers
with rubber components are not to be used. Laboratory clothing worn by
the analyst must be clean of solvents since clothing previously exposed
to methylene chloride and other laboratory solvent fumes during common
liquid/liquid extraction procedures can contribute to sample
contamination.
4.3 Contamination by carryover can occur whenever a sample is analyzed
after a. high level sample which contain high levels of organic
compounds. To reduce carryover, the sample purger and sampling syringe
must be rinsed with reagent water between sample analyses. Whenever an
unusually concentrated sample is encountered, it must either be
followed by analysis of an instrument blank or the next sample must be
closely monitored to check for cross contamination. For samples
containing large amounts of water soluble materials, suspended solids,
high boiling compounds, or high purgeable levels, it is necessary to
wash out the sample purger with a detergent solution between analyses,
rinse it with distilled water, and then dry it in a 105*C oven. The
trap and other parts of the system are also subject to contamination;
therefore, frequent bakeout and purging of the entire system may be
required.
5. APPARATUS AMD MATERIALS
Brand names, suppliers and part numbers are for illustrative purposes
only. No endorsement is implied. Equivalent performance may be
achieved using apparatus and materials other than those specified here,
but demonstration of equivalent performance meeting the requirements of
the method is the responsibility of the Contractor.
5.1 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. Purge gas plumbing lines are to be constructed from stainless
steel or copper tubing. Non-polytetrafluoroethylene (PTFE) thread
sealants, or flow controllers with rubber components are not to be
used.
5.1.1 Sample Purger - The sample purger must be designed to accept 25
mL samples with a water column at least 10 cm deep. The
gaseous head space between the water column and the trap must
have a total volume of less than 15 mL. The purge gas must
pass through the water column as finely divided bubbles, each
with a diameter of less than 3 mm at the origin. The purge gas
must be introduced no more than 5 mm from the base of the water
column. Alternate sample purge devices may be utilized
provided equivalent performance is demonstrated. A set of
sample purgers sufficient to meet contract requirements must be
reserved for exclusive use in this contract.
VGA D-6 6/91
-------
5.1.2 Trap Packing
5.1.2.1 2,6-Diphenylene oxide polymer, 60/80 mesh,
chromatographic grade (Tenax GC or equivalent).
5.1.2.2 Methyl silicone packing, 3 percent OV-1 on
Chromosorb V, 60/80 mesh (or equivalent).
5.1.2.3. Silica gel (35/60 mesh, Davison, grade 15 or
equivalent).
5.1.3 Trap - The trap must be at least 25 cm long and have an inside
diameter of at least 0.105 inch (0.2667 cm). Starting from the
inlet, pack the column in the following order: 0.5 cm silanized
glass wool, 1 cm methyl silicone coated packing, 15 cm
2,6-diphenylene oxide polymer, 8 cm silica gel, and 0.5 cm
silanized glass wool.
5.1.4 Trap Heater
5.1.4.1 The trap heater must be capable of rapidly heating
the trap to 180*0. The polymer section of the trap
should not be heated to greater than 180*C and the
temperature of the remaining sections should not
exceed 220*C during bakeout mode.
5.1.4.2 The purge and trap device may be assembled as a
separate unit or be coupled to a gas chromatograph.
5.2 Gas Chromatograph/Mass Spectrometer
5.2.1 Gas Chromatograph - The gas chromatograph (GC) system must be
capable of temperature programming and have a flow controller
that maintains a constant column flow rate throughout
desorption and temperature program operations. The system must
include or be interfaced to a purge and trap system as
specified in Section 5.1 and have all required accessories
including syringes, analytical columns, and gases. All GC
carrier gas lines must be constructed from stainless steel or
copper tubing. Non-polytetrafluoroethylene (PTFE) thread
sealants, or flow controllers with rubber components are not to
be used. The column oven must be cooled to 10*C; therefore, a
subambient oven controller is required.
5.2.1.1 Gas Chromatography Columns
Column 1-30 m long x 0.53 mm ID VOCOL (Supelco,
Inc.) or equivalent fused silica wide-bore capillary
column with 3 um film thickness.
Column 2-30 m long x 0.53 mm ID DB-624 fused silica
wide-bore (J&W Scientific, Inc.) or equivalent
column with 3 um film thickness.
VOA D-7 6/91
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5.2.2 Mass Spectrometer - The mass spectrometer must be capable of
scanning from 35 to 300 amu every 1 second or less, utilizing
70 volts (nominal) electron energy in the electron impact
ionization mode and producing a mass spectrum which meets all
the tuning acceptance criteria when 50 ng of
p-bromofluorobenzene (BFB) are injected through the gas
chromatograph inlet. To ensure sufficient precision of mass
spectral data, the MS scan rate must allow acquisition of at
least five spectra while a sample compound elutes from the GC.
The purge and trap GO/MS system must be in a room whose
atmosphere is demonstrated to be free of all potential
contaminants which will interfere with the analysis. The
instrument must be vented to outside the facility or to a
trapping system which prevents the release of contaminants into
the instrument room.
5.2.3 GO/MS Interface - Any gas chromatograph to mass spectrometer
interface may be used that gives acceptable calibration points
at 25 ng or less per injection for each of the purgeable target
and surrogate compounds and achieves all acceptable performance
criteria. Gas chromatograph to mass spectrometer interfaces
constructed of all-glass or glass-lined materials are
recommended. Glass can be deactivated by silanizing with
dichlorodimethylsilane.
5.2.4 Data System - A computer system must be interfaced to the mass
spectrometer that allows the continuous acquisition and storage
on inrhln* readable media of all mass spectra obtained
throughout the duration of the chromatographic program. The
computer must have software that allows searching any GC/HS
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 (EICF). Software
must also be available that allows integrating the abundance in
any EICF between specified time or scan number limits. Also,
for the non-target compounds, software must be available that
allows comparing sample spectra against reference library
spectra. The most recent release of the National Institute of
Standards and Technology Mass Spectral Library shall be used as
the reference library.
5.3 Magnetic Tape Storage Device - The magnetic tape storage device must be
capable of recording data and must be suitable for long-term, off-line
storage.
5.4 pH paper - wide range.
5.5 Glassware - A set of glassware sufficient to meet the contract
requirements must be reserved for exclusive use in this contract.
5.5.1 Bottles - 15 mL, screw-cap, with Teflon cap liner.
5.5.2 Volumetric flasks - class A with ground-glass stoppers.
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5.6 Micro syringes - 10 uL and larger, 0.006 inch ID needle.
5.7 Syringe valve - two-way, with Luer ends (three each), if applicable to
the purging device.
5.8 Syringe - 25 mLt gas tight with shut-off valve.
5.9 Analytical Balance - capable of accurately weighing ±0.0001 g. The
balance must be calibrated with class S weights once per each 12-hour
workshift. The balance must also be annually checked by a certified
technician.
5.10 Gases - Heliun, Nitrogen. Ultra-pure grade.
5.11 Gas line tubing - polytetrafluoroethylene, stainless steel, or copper
tubing.
6. REAGENTS
6.1 Reagent water - Reagent water is defined as water in which no purgeable
target compound is observed at or above the CRQL listed in Exhibit C
for that compound and in which no non-target compound is observed at or
above 2.0 ug/L.
6.1.1 Reagent water may be generated by passing tap water through a.
carbon filter bed containing about 453 g (1 Ib.) of activated
carbon (Calgon Corp., Filtrasorb-300, or equivalent).
6.1.2 Reagent water may be generated using a water purification
system (Millipore Super-Q, or equivalent).
6.1.3 Reagent water may be prepared by boiling water for 15 minutes.
Subsequently, while maintaining the temperature at 90*C, bubble
a contaminant-free inert gas through the water for one hour.
While still hot, transfer the water to a narrow-mouth screw-cap
bottle, seal with a Teflon-lined septum, and cap.
6.2 Methanol - HFLC quality or equivalent--Each lot of methanol used for
analysis under this contract must be purged with nitrogen and must be
demonstrated to be free of contaminants that interfere with the
measurement of purgeable compounds listed in the Exhibit C.
7. STANDARDS
7.1 The Contractor must provide all standards to be used with this
contract. These standards may be used only after they have been
certified according to the procedure in Exhibit E. The Contractor oust
be able to verify that the standards are certified. Manufacturer's
certificates of analysis must be retained by the Contractor and
presented upon request.
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7.2 Stock Standard Solutions
Stock standard solutions may be purchased or may be prepared in
methanol from pure standard materials.
7.2.1 Prepare stock standard solutions by placing about 9.8 mL of
methanol into a 10.0 mL ground- glass stoppered volumetric
flask. Allow the flask to stand, unstoppered, for about 10
minutes or until all alcohol wetted surfaces have dried. Weigh
the flask to the nearest 0.1 mg.
7.2.2 Add the assayed reference material as described below.
7.2.2.1 If the compound is a liquid, using a 100. uL syringe,
immediately add two or more drops of assayed
reference material to the flask, then reweigh. The
liquid must fall directly into the alcohol without
contacting the neck of the flask.
7.2.2.2 If the compound is a gas at room temperature, fill a
5 mL valved gas-tight syringe with the reference
standard to the 5.0 mL mark. Lower the needle to 5
mm above the methanol meniscus. Slowly introduce
the reference standard above the surface of the
liquid. The gas will rapidly dissolve in the
methanol. This may also be accomplished by using a
lecture bottle equipped with a Hamilton Lecture
Bottle Septum (#86600). Attach Teflon tubing to the
side-arm relief valve and direct a gentle stream of
the reference standard into the methanol meniscus.
7.2.3 Reweigh, dilute to volume, stopper, then M* by inverting the
flask several times. For non- gaseous compounds, calculate the
concentration in micrograms per microliter from the net gain in
weight. When compound purity is assayed to be 97 percent or
greater, the weight may be used without correction to calculate
the concentration of the stock standard. If the compound
purity is assayed to be less than 97 percent, the weight must
be corrected when calculating the concentration of the stock
solution. For gaseous compounds, calculate the concentration
in micrograms per microliter, using the Ideal Gas Law, taking
into account the temperature and pressure conditions within the
laboratory .
7.2.4 Prepare fresh stock standards every two months for gases or for
reactive compounds such as styrene. All other stock standards
for non- gases/non- reactive purgeable compounds must be replaced
after six months, or sooner, if standard has degraded or
evaporated.
7.3 Secondary Dilution Standards
7.3.1 Using stock standard solutions, prepare secondary dilution
standards in methanol that contain the compounds of interest,
VGA D-10 6/91
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either singly or mixed together. Secondary dilution standard
solutions should be prepared at concentrations that can be
easily diluted to prepare working standard solutions.
7.3.2 Prepare fresh secondary dilution standards for gases and for
reactive compounds, such as styrene, every month or sooner, if
standard has degraded or evaporated. Secondary dilution
standards for the other purgeable compounds must be rep-laced
after six months, or sooner, if standard has degraded or
evaporated.
7.4 Working Standards
7.4.1 Tuning Solution - p-Bromofluorobenzene (BFB)
Prepare a 25 ng/uL solution of BFB in methanol. Prepare fresh
BFB solution every six months, or sooner, if the solution has
degraded or evaporated. Note: The 25 ng/uL concentration is
used with a 2 uL injection volume. The laboratory may prepare
a 50 ng/uL solution of BFB if a 1 uL injection volume is used.
7.4.2 Calibration Standard Solution
Prepare the working calibration standard solution containing
all of the purgeable target compounds in methanol. The
concentration of the non-ketone target compounds and the
surrogate must be 5.0 ug/mL in the standard (i.e., final
concentration). The concentration of the ketones (acetone,
butanone, 2-hexanone, 4-methyl-2-pentanone) must be 25.0 ug/mL
in the standard (i.e., final concentration). Prepare fresh
working calibration standard solutions weekly, or sooner, if
solutions have degraded or evaporated.
7.4.3 Internal Standard Spiking Solution
Prepare an internal standard spiking solution containing 1,4-
dichlorobenzene-d4, chlorobenzene-d5, and 1,4-difluorobenzene
in methanol at the concentration of 12.5 ug/mL for each
internal standard. Add 10 uL of this spiking solution into
25.0 mL of sample or calibration standard for a concentration
of 5.0 ug/L. Prepare fresh spiking solution every three
months. or sooner, if the solution has degraded or evaporated.
7.4.4 Surrogate Compound Spiking Solution
Prepare 12.5 ng/uL solution of p-bromofluorobenzene in
methanol. For samples and blanks, add 10 uL of the surrogate
compound solution to 25 mL of sample or reagent water for a
final concentration of 5 ug/L. The surrogate compound is added
to the working calibration standards so it is not to be added
again when aqueous calibration standards are prepared. Prepare
fresh surrogate compound solution every six months. or sooner,
if the solution has degraded or evaporated.
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7.4.5 Laboratory Control Sample (LCS) Spiking.Solution
Prepare the laboratory control sample spiking solution
containing all of the analytes listed below at 12.5 ng/uL in
methanol. The laboratory control sample is prepared by adding
10 uL of this solution into 25.0 mL of reagent water for a
concentration of 5.0 ug/L. Prepare fresh LCS spiking solution
every six months, or sooner, if the solution has degraded or
evaporated. The LCS must contain the following compounds:
1,2-Dibromoethane
Benzene
1,2-Dichloroethane
1,2-Dichloropropane
Tetrachoroethene
Carbon tetrachloride
1,4-Dichlorobenzene
cis-1,3-Dichloropropene
1,1,2-Trichloroethane
Vinyl chloride
Bromoform
Trichloroethene
7.5 Aqueous Calibration Standard Solutions
7.5.1 Prepare five aqueous initial calibration standard solutions
containing all of the purgeable target compounds and the
surrogate compound at the 1.0, 2.0, 5.0, 10, and 25 ug/L
levels, except the ketones which are at the 5.0, 10, 25, 50,
and 125 ug/L levels. It is required that all three xylene
isomers (o-,p- and m-xylene) be present in the calibration
standards at concentrations of each isomer equal to that of the
other target compounds (i.e., 1.0, 2.0, 5.0, 10.0 and 25 ug/L).
The preparation procedure for the aqueous calibration standard
solutions is listed in Table 0-1. The internal standards are
added to each calibration standard according to the procedures
in Section 14.3.5.
TABLE D-l
VOL OF
WORKING
STANDARD
(uL added
to 25 mL)
5
10
25
50
125
FINAL
CONG. OF
AQUEOUS
STANDARD FOR
NON-KETONES
(ug/L)
1
2
5
10
25
FINAL
CONG. OF
AQUEOUS
STANDARD FOR
KETONES
(ug/L)
5
10
25
50
125
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6/91
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7.5.2 Aqueous calibration standards may be prepared in a volumetric
flask or in the syringe used to inject the standard into the
purging device.
7.5.2.1 Volumetric flask - Add an appropriate volume of
working calibration standard solution to an aliquot
of reagent water in a volumetric flask. Use a
microsyringe and rapidly inject the alcohol standard
into the expanded area of the filled volumetric
flask. Remove the needle as quickly as possible
after injection. Bring to volume. Mix by inverting
the flask three times only. Discard the contents
contained in the head of the flask.
7.5.2.2 Syringe - Remove the plunger from a 25 mL syringe
and close the syringe valve. Pour reagent water
into the syringe barrel to just short of
overflowing. Replace the syringe plunger and
compress the water. Invert the syringe, open the
syringe valve and vent any residual air. Adjust the
water volume to 25.0 mL minus the amount of
calibration standard to be added. Withdraw the
plunger slightly and add an appropriate volume of
working calibration standard through the valve bore
of the syringe. Close the valve and invert three
times.
7.5.3 The 5 ug/L (25 ug/L for ketones) aqueous calibration standard
solution is the continuing calibration standard.
7.5.4 A smaller sample or standard volume (5 to 25 mL) may be purged
but the CRQL and all QC criteria must be met. The same purge
volume must be used for all samples, standards, and blanks in a.
single SDG.
7.5.5 The methanol contained in each of the aqueous calibration
standards must not exceed 1% by volume.
7.6 Storage of Standards
7.6.1 Store the stock standards in Teflon sealed screw-cap bottles
with zero headspace at -10'C to -20'C. Protect the standards
from light. Once one of the bottles containing the stock
standard solution has been opened, it may be used for no longer
than one week.
7.6.2 Store secondary dilution standards in Teflon sealed screw-cap
bottles with minimal headspace at -10*C to -20*C. Protect the
standards from light. The secondary dilution standards must be
checked frequently for signs of degradation or evaporation,
especially just prior to preparing the working calibration
standards from them.
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7.6.3 Aqueous standards may be stored up to 24 hours if held in
Teflon sealed screw-cap vials with zero headspace at 4*C
(±2*C). Protect the standards from light. If not so stored,
they must be discarded after one hour unless they are set up to
be purged by an autosaopler. When using an autosampler, the
standards may be kept up to 12 hours in purge tubes connected
via the autosampler to the purge and trap device.
7.6.4 Purgeable standards must be stored separately from other
standards.
VOA D-14 6/91
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SECTION III
INSTRUMENT QUALITY CONTROL PROCEDURES AND REQUIREMENTS
VOA D-15 6/91
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FART A - INSTRUMENT OPERATING CONDITIONS
Purge and Trap
The following are the recommended purge and trap analytical conditions
except as stated below:
Purge Conditions:
Purge Gas:
Purge Tine:
Purge Flow Rate:
Purge Temperature:
Desorb Conditions:
Desorb Temperature:
Desorb Flow Rate:
Desorb Time:
Trap Reconditioning Conditions:
Reconditioning Temperature:
Reconditioning Time:
Helium or Nitrogen
11.0 ±0.1 min
25-40 mL/min
Ambient
180 *C
15 mL/min
4.0 ±0.1 min
180'C
7.0 min ±0.1 min (minimum). A
longer time may be required to
bake contamination or water from
the system.
Before initial use, condition the trap overnight at 180*C by backflushing
with at least 20 mL/min flow of inert gas. Vent the trap effluent to the
hood and not to the analytical column. Prior to daily use, condition the
trap by heating at 180'C for 10 minutes while backflushing. The trap may be
vented to the analytical column during daily conditioning; however, the
column must be run through the temperature program prior to analysis of
samples.
Optimize purge and trap conditions for sensitivity and to minimize cross
contamination between samples. Once optimized, the same purge and trap
conditions must be used for the analysis of all standard, samples, blanks,
Performance Evaluation Samples and Laboratory Control Samples
Gas Chromatograph
The following are the recommended gas chromatographic analytical
conditions:
Carrier Gas:
Flow Rate:
Initial Temperature:
Initial Hold Time:
Ramp Rate:
Final Temperature:
Final Hold Time:
Helium
15 mL/min
10" C
1.0 - 5.0 min (±0.1 min
precision)
6'C/min
160* C
Until all target compounds elute
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6/91
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Optimize GC conditions for compound separation and sensitivity. Once
optimized, the same GC conditions must be used for the analysis of all
standards, samples, blanks, performance evaluation samples, and laboratory
control samples.
Mass Spectrometer
The following are the required mass spectrometer conditions:
Electron Energy: 70 Volts (nominal)
lonization Mode: El
Mass Range: 35-300 amu
Scan Time: To give at least 5 scans per
peak, not to exceed 1 second per
scan.
VGA D-17 6/91
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PART B - TUNING THE MASS SPECTROMETER
8. 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).
9.
Each GC/MS used for volatile analysis must be hardware tuned once per
twelve (12) hour time period of operation. Also, whenever the
Contractor takes corrective action which could change or affect the
tuning for BFB (e.g., ion source cleaning or repair, column
replacement, etc.), the tune must be verified before continuing
analysis irrespective of the twelve-hour daily tuning requirement. 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 Contractor submits as
documentation of a compliant tune. The time period ends after twelve
(12) hours have elapsed. In order to meet the tuning requirements, a
sample, LCS, PES, standard, or blank must be injected within twelve
hours of the BFB injection.
10. PROCEDURE
10.1 Inject 50 ng BFB into the GC/MS system. Alternatively, add 50 ng of
BFB solution to 25.0 mL of reagent water and analyze according to
Section 17. All instrument conditions must be identical to those
listed in Section III, Part A, except that a different temperature
program may be used.
10.2 For the tune, BFB may not be analyzed simultaneously with any
calibration standards or blanks.
11. TECHNICAL ACCEPTANCE CRITERIA FOR BFB ANALYSIS
11.1 The GC/MS system must be tuned at the frequency described in Section 9.
11.2 The abundance criteria listed in Table D-2 must be met for a 50 ng
injection of BFB. The mass spectrum of BFB must be acquired in the
following manner. Three scans (the peak apex scan and the scans
immediately preceding and following the apex) are acquired and
averaged. Background subtraction is required, and must be accomplished
using a single scan prior to the elution of BFB. Note: All
subsequent standards and samples, including LCS, PES and blanks
associated with a BFB analyses must use identical mass spectrometer
instrument conditions.
11.3 The criteria listed in Table D-2 are based on adherence to the
acquisition specifications identified in Section 11.2 and were
developed for the specific target compound list associated with this
method. The criteria are based on performance characteristics of
VOA D-18 6/91
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instruments currently utilized in routine support of Program
activities. These specifications, in conjunction with relative
response factor criteria for 28 target compounds (see Table 0-5), are
designed to control and monitor instrument performance associated with
the requirements of this method. As they are performance based
criteria for these specific analytical requirements, they may not be
optimal for additional target compounds.
TABLE D-2 BFB KEY IONS AND ABUNDANCE CRITERIA
Mass Ion Abundance Criteria
SO 8.0-40.0 percent of mass 95
75 30.0 - 66,0 percent of mass 95
95 base peak, 100 percent relative abundance
96 5.0-9.0 percent of mass 95 (see note)
173 less than 2.0 percent of mass 174
174 50.0 - 120.0 percent of mass 95
175 4.0 - 9.0 percent of mass 174
176 93.0 - 101.0 percent of mass 174
177 5.0 - 9.0 percent of mass 176
Note: All ion abundances must be normalized to m/z 95, the nominal
base peak, even though the ion abundance of m/z 174 may be up to 120
percent that of m/z 95.
12. CORRECTIVE ACTION
12.1 If the BFB technical acceptance criteria are not met, retune the GC/MS
system. It may also be necessary to clean the ion source, clean the
quadrupole rods, or take other corrective actions to achieve the
technical acceptance criteria.
12.2 BFB technical acceptance criteria MUST be met before any standards,
samples or required blanks are analyzed. Any samples (including LCS
and FES), or required blanks analyzed when tuning technical acceptance
criteria have not been met will require reanalysis at no additional
cost.
VOA D-19 6/91
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FART C • CALIBRATION OF THE GO/MS SYSTEM
14. IHTTIAL CALIBRATION
14.1 Summary - Prior to the analysis of samples and required blanks and
after BFB technical acceptance criteria have been net, each GC/MS
system must be calibrated at a minimum of five concentrations to
determine instrument sensitivity and the linearity of GC/MS response
for the purgeable target and surrogate compounds.
14.2 Frequency
14.2.1 Each GC/MS system must be calibrated upon award of the
contract, whenever the Contractor takes corrective action which
may change or affect the initial calibration criteria (i.e.,
ion source cleaning or repair, column replacement, etc.), or if
the continuing calibration acceptance criteria have not been
met.
14.2.2 If time remains in the 12 hour time period after meeting the
technical acceptance criteria for the initial calibration,
samples may be analyzed. It is not necessary to analyze a
continuing calibration standard, if the initial calibration
standard that is the same concentration as the continuing
calibration standard meets the continuing calibration technical
acceptance criteria. A method blank is required. Quantify all
sample and quality control sample results and quality control
criteria results, such as internal standard area response
change and retention time shift, against the initial
calibration standard that is the same concentration as the
continuing calibration standard.
14.3 Procedure
14.3.1 Set-up the purge and trap GC/MS system per the requirements of
Section III, Part A.
14.3.2 All samples, required blanks, and standard/spiking solutions
must be allowed to warm to ambient temperature (approximately 1
hour) before analysis.
14.3.3 Tune the GC/MS system to meet the BFB technical acceptance
criteria in Section 11.
14.3.4 Prepare a spiking solution containing the internal standards
using the procedure described in Section 7.4.3.
14.3.5 Prepare five aqueous calibration standards containing all the
purgeable target compounds and the surrogate using the
procedure described in Section 7.5. Add 10 uL of the internal
standard solution to each aqueous standard. Analyze each
calibration standard, according to Section 17. If a compound
saturates at the highest standard concentration (Section
7.5.1), and the GC/MS system is calibrated to achieve a
VOA D-20 6/91
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detection sensitivity of no less than 1.0 ug/L. the Contractor
must document it in the SDG Narrative and attach a quantitation
report and RIC. In this instance, the Contractor must
calculate the results based on a four-point initial calibration
for the specific compound that saturates. Secondary ion
quantitation is only allowed when there are sample
interferences with the primary quantitation ion. If secondary
ion quantitation is used, calculate a relative response'factor
using the area response from the most intense secondary ion
which is free of sample interferences and document the reasons
for the use of the secondary ion in the SDG Narrative.
14.4 Calculations
NOTE: Unless otherwise stated the area response is that of the primary
quantitation ion.
Calculating the relative response factor of the xylenes requires
special attention. On capillary columns, the m- and p-xylene isomers
coelute. Therefore, when calculating the relative response factor in
the equation below, use the area response (A^) and concentration (C^)
of the peak from o-xylene.
14.4.1 Calculate relative response factors (RRF) for each purgeable
target compound and the surrogate using Equation D.I. See
Table D-3 to associate purgeable target compounds with the
proper internal standard. See Table D-4 for primary
quantitation ions to be used for each purgeable target,
surrogate, and internal standard compounds.
EQ. D.I AX Cis
RRF - x
Ais Cx
Where:
AX - Area response (EIC?) for the compound to be measured.
Ais - Area response (EICF) for the internal standard.
cis ~ Concentration of the internal standard.
GX — Concentration of the compound to be measured.
14.4.2 Equation D.2 is the general formula for standard deviation (SD)
for a statistically small set of values.
EQ. D.2.
n-1
VOA D-21 6/91
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SO - Standard deviation for a set of values.
K£ - Value.
x - Mean value.
n - Number of values.
14.4.3 Calculate the percent relative standard deviation (% RSD) of
BKF values for each purgeable target and surrogate compound
over the initial calibration range using Equation D.3 in
conjunction with Equation D.2.
EQ- D.3 %RSD . SDm* x loo
x
Where:
%RSD - Percent relative standard deviation.
SDssr - Standard deviation of initial calibration response
factors (per compound).
From EQ. 0.2:
X£ - RRF^ - Relative response factors from initial calibration
standard (per compound).
x - RRF - Mean of initial calibration response
factors (per compound).
14.4.4 Equation D.4 is the general formula for the mean of a set of
values.
EQ. D.4
n
x -
Xi - Value.
x - Mean value.
n — Number of values.
14.4.5 Calculate the mean of the relative retention times (RRT) for
each purgeable target and surrogate compound over the initial
calibration range using Equation 0.4 and Equation 0.5.
EQ. 0.5 RTC
RRT -
RTis
RTC - Retention time for the purgeable target and surrogate
compound.
VOA D-22 6/91
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RT^g- Retention time for the internal standard.
From EQ D.4:
X£ - RRl£ - Relative retention times for the purgeable target
or surrogate compound for each initial calibration
standard.
x - RRT - Mean relative retention time (per compound) .
n - Number of values.
14.4.6 Calculate the area response (Y) mean for each internal standard
over the initial calibration range using Equation D.4.
Where:
— Area responses for the internal standard in each
of the calibration standards.
x - Y - Area response mean.
n - Number of values.
14.4.7 Calculate the mean of the absolute retention times (RT) for
each internal standard over the initial calibration range using
Equation D.4.
Where:
xi ~ RTi - Retention times for the internal standard in each
of the calibration standards.
x - RT - Mean absolute retention time.
n — Number of values.
14.5 Technical Acceptance Criteria For Initial Calibration
14 . 5 . 1 All initial calibration standards must be analyzed at the
concentration levels described in Section 14.3, and at the
frequency described in Section 14.2 on a GC/MS system meeting
the BFB technical acceptance criteria.
14.5.2 The relative response factor (RRF) at each calibration
concentration for each purgeable target and surrogate compound
that has a required minimum response factor value must be
greater than or equal to the compound's minimum acceptable
response factor listed in Table D-5.
VOA D-23 6/91
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14.S.3 The %RSD for each target or surrogate compound listed in Table
D-5 must be less than or equal to that value listed.
14.5.4 Up to two compounds may fail the criteria listed in paragraphs
14.5.2 and 14.5.3 and still meet the minimum response factor
and %RSD requirements. However, these compounds must have a
M-tpfntiim RRF greater than or equal to 0.010, and the %RSD must
be less than or equal to 40.0%.
14.5.5 The relative retention tine (RUT) at each calibration level
must be within +0.06 RRT units of mean relative retention time
(RRT) over all the calibration levels for each purgeable target
compound and the surrogate.
14.5.6 The area response (Y) for each internal standard compound in
each calibration standard must be within the inclusive range of
+40.0 percent of the mean area response (7) of the internal
standard in all of the calibration standards.
14.5.7 The retention time (RT) shift for each internal standard at
each calibration level must be less than or equal to +0.33
minutes (20.0 seconds) from the mean retention time (RT) over
all calibration levels for each internal standard.
14.6 Corrective Action
14.6.1 If the initial calibration technical acceptance criteria are
not met, inspect the system for problems. It may be necessary
to clean the ion source, change the column, service the purge
and trap device or take other corrective actions to achieve the
technical acceptance criteria.
14.6.2 Initial calibration technical acceptance criteria MUST be met
before any samples or required blanks are analyzed. Any
samples (including LCS and FES) or required blanks analyzed
when initial calibration technical acceptance criteria have not
been met will require reanalysis at no additional cost.
15. CONTINUING CALIBRATION
15.1 Summary - Prior to the analysis of samples and required blanks and
after BFB and initial calibration acceptance criteria have been met,
each GC/MS system must be routinely checked by analyzing a continuing
calibration standard containing all the purgeable target and surrogate
compounds to ensure that the instrument continues to meet the
instrument sensitivity and linearity requirements of the method.
15.2 Frequency
15.2.1 Each GC/MS used for analysis must be calibrated once per each
twelve (12) hour time period of operation. The twelve hour
time period begins with the injection of BFB.
VOA D-24 6/91
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15.2.2 If time remains in the 12 hour time period after meeting the
technical acceptance criteria for the initial calibration,
samples may be analyzed. It is not necessary to analyze a
continuing calibration standard, if the initial calibration
standard that is the same concentration as the continuing
calibration standard meets the continuing calibration technical
acceptance criteria. A method blank is required. Quantify all
sample results against the initial calibration standard -that is
the same concentration as the continuing calibration standard
(5 ug/L for non-ketones, 25 ug/L for ketones).
15.3 Procedure
15.3.1 Set up the purge and trap GC/MS system per the requirements of
Section III, Part A.
15.3.2 All samples, required blanks, and standard/spiking solutions
must be allowed to warm to ambient temperature (approximately 1
hour) before analysis.
15.3.3 Tune the GC/MS system to meet the BFB technical acceptance
criteria in Section 11.
15.3.4 Prepare a working continuing calibration standard solution
containing all the purgeable target and surrogate compounds
using the procedure listed in Section 7.4.2. The concentration
for the non-ketones and the surrogate compound will be 5 ug/L.
The concentration of the ketones will be 25 ug/L.
15.3.5 Prepare the aqueous continuing calibration solution by adding
25 uL of the working calibration standard to reagent water as
described in Paragraph 7.5.
15.3.6 Add 10 uL of internal standard spiking solution (prepared as
described in Paragraph 7.4.3) to the 25 mL syringe or
volumetric flask containing the continuing calibration
standard. Analyze the continuing calibration standard,
according to Section 17.
15.4 Calculations
15.4.1 Calculate a relative response factor (RRF) for each target and
surrogate compound according to Section 14.4.1.
15.4.2 Calculate the percent difference between the continuing
calibration relative response factor and the most recent
initial calibration mean relative response factor for each
purgeable target and surrogate compound using Equation D.6.
RRFj - RRF
EQ D. 6 % D RHF - x 100
VGA D-25 6/91
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Where:
% DBBF ~ Percent difference between relative
response factors.
RRF - Relative response factor from current continuing
calibration standard.
- Mean relative response factor froa the most recent
initial calibration.
15.5 Technical Acceptance Criteria For Continuing Calibration
15.5.1 The concentration of the volatile organic target and surrogate
compounds in the continuing calibration standard must be 5.0
ug/L for non-ketones and 25.0 ug/L for ketones. The continuing
calibration standard must be analyzed at the frequency
described in Section 15.2 on a GC/MS system meeting the BFB and
the initial calibration technical acceptance criteria.
15.5.2 The relative response factor for each purgeable target and
surrogate compound that has a required Tinlmii response factor
value must be greater than or equal to the compound's «ifTri"M"»
acceptable response factor listed in Table D-5.
15.5.3 The relative response factor percent difference for each
purgeable target and surrogate compound listed in Table D-5
must be less than or equal to that value listed.
15.5.4 Up to two compounds may fail the requirements-listed in
paragraph 15.5.2 and 15.5.3 and still meet the minimum response
factor criteria and percent difference criteria. However,
these compounds must have a mf.Mai'^ response factor greater
than or equal to 0.010 and the percent difference must be
within the inclusive range of ±40.0%.
15.6 Corrective Action
15.6.1 If the continuing calibration technical acceptance criteria are
not met, recalibrate the GC/MS instrument according to Section
14. It may be necessary to clean the ion source, change the
column or take other corrective actions to achieve the
continuing calibration technical acceptance criteria.
15.6.2 Continuing calibration technical acceptance criteria MUST be
met before any samples (including LCS and FES) or required
blanks are analyzed. Any samples, or required blanks analyzed
when continuing calibration technical acceptance criteria have
not been met will require reanalysis at no additional cost.
VOA D-26 6/91
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SECTION 17
SAMPLE ANALYSIS AND COMPOUND IDENTIFICATION AND QUANTITATION
VOA D-27 6/91
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16. SUMMARY
16.1 This method is designed for analysis of samples that contain low
concentrations of the target compounds listed in Exhibit C. It is
expected that the samples will come from drinking water and
well/ground water type sources around Superfund sites. If, upon
inspection of a sample, the Contractor suspects that the sample is
not amenable to this method, contact SMO for instructions.
16.2 Before samples or required blanks may be analyzed, the purge and
trap, and the GC/MS instrument must meet the BFB (Section 11),
initial calibration (Section 14) and continuing calibration (Section
15) technical acceptance criteria listed. Also, before samples may
be analyzed, a method blank must be analyzed which meets blank
technical acceptance criteria listed in Section 26. All samples,
required blanks, and calibration standards must be analyzed under the
same instrument conditions. All samples, required blanks, and
standard/spiking solutions must be allowed to warm to ambient
temperature (approximately 1 hour) before analysis.
17. PROCEDURE
17.1 Set up the purge and trap GC/MS system per the requirements of
Section III, Part A.
17.2 Remove the plunger from a 25 mL syringe that has a closed syringe
valve attached. Open the sample or standard container which has been
allowed to come to ambient temperature (approximately 1 hour), and
carefully decant the sample into the syringe barrel to just short of
overflowing. Replace the syringe plunger and compress the sample.
Invert the syringe, open the syringe valve, and vent any residual air
while adjusting the sample volume to 25.0 mL. This process of taking
an aliquot destroys the validity of the sample for future analysis,
unless the excess sample is immediately transferred to a smaller vial
with zero headspace and stored at 4*C (±2*C).
NOTE: A smaller sample volume (5 to 25 mL) may be analyzed but the
CROL and all technical acceptance criteria must oe met. The same
sample volume must be used for all standards, samples, and blanks
that apply to a single SDG.
17.3 Once the sample allquots have been taken from the VOA vial, the pH of
the water sample must be determined. The purpose of the pH
determination is to ensure that all VOA samples were acidified in the
field. Test the pH by placing one or two drops of sample on the pH
paper (do not add pH paper to the vial). Record the pH of each
sample and report these data in the SDG Narrative, following the
instructions in Exhibit B. No pH adjustment is to be performed by
the Contractor.
17.4 Add 10.0 uL of the internal standard spiking solution and 10.0 uL of
the surrogate standard solution through the valve bore of the
syringe, then close the valve. Invert the syringe three times.
VOA D-28 6/91
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17.5 Attach the valve assembly on the syringe to the valve on the sample
purger. Open the valves and inject the sample into the purging
chamber.
17.6 Close both valves and purge the sample for 11.0 (±0.1) minutes at
ambient temperature.
17.7 Sample Desorption
After the 11 minute purge, attach the trap to the gas chromatograph,
adjust the purge and trap system to the desorb mode, initiate the
temperature program sequence of the gas chromatograph and start data
acquisition. Introduce the trapped material to the GC column by
rapidly heating the trap to 180*C while backflushing the trap with
inert gas at 15 mL/oin for 4.0 +0.1 min. While the trapped material
is being introduced into the gas chromatograph, empty the sample
purger and rinse it with reagent water. For samples containing large
amounts of water soluble materials, suspended solids, high boiling
compounds or high purgeable levels, it may be necessary to wash out
the sample purger with a detergent solution, rinse it with reagent
water, and then dry it in a 105*C oven between analyses.
17.8 Trap Reconditioning — After desorbing the sample, recondition the
trap for a minimum of 7.0 ±0.1 min at 180*C by returning the purge
and trap system to purge mode.
17.9 Gas Chromatography - Hold the column temperature at 10*C for 1.0 to
5.0 min, then program at 6C*/min to 160*C and hold until all target
compounds have eluted. Note: Once an initial hold time has been
chosen and the GC operating conditions optimized, the same GC
condition must be used for the analysis.
18. TERMINATION OP DATA ACQUISITION
When all purgeable target compounds have eluted from the GC,
terminate the MS data acquisition and store data files on the data
system storage device. Use appropriate data output software to
display full range mass spectra and appropriate extracted ion current
profiles (EICPs).
19. DILUTIONS
19.1 If the initial analysis of a sample indicates the sample must be
reanalyzed at a dilution, the dilution must be made just prior to
GC/MS analysis of the sample. Until the diluted sample is in a gas
tight syringe, all steps in the dilution procedure must be performed
without delay. Secondary ion quantitation is only allowed when there
are sample interferences with the primary quantitation ion, not when
saturation occurs. If secondary ion quantitation is used, calculate
a relative response factor using the area response (EICP) from the
most intense secondary ion which is free of sample interferences, and
document the reasons in the SOG Narrative.
VOA D-29 6/91
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19.2 All dilutions must keep the response of the target compounds that
required dilution in the upper half of the initial calibration range.
19.3 Dilutions are made in volumetric flasks or in a 25 mL "Luerlock"
syringe.
19.3.1 To dilute the sample in a volumetric flask, use the following
procedure:
19.3.1.1 Select the volumetric flask that will allow for
the necessary dilution (25 mL to 100 mL).
19.3.1.2 Calculate the approximate volume of reagent water
which will be added to the volumetric flask
selected and add slightly less than this quantity
of reagent water to the flask.
19.3.1.3 Inject the proper sample aliquot from a syringe
into the volumetric flask. Aliquots of less than
1 mL are prohibited. Dilute the flask to the mark
with reagent water. Cap the flask, invert, and
shake three times.
19.3.1.4 Fill a 25.0 mL syringe with the diluted sample and
analyze according to Section 17.
19.3.2 To dilute the sample in a 25 mL syringe, use the following
procedure:
19.3.2.1 Calculate the volume of the reagent water
necessary for the dilution. The final volume of
the diluted sample should be 25 mL.
19.3.2.2 Close the syringe valve, remove the plunger from
the syringe barrel, and pour reagent water into
the syringe barrel to just short of overflowing.
19.3.2.3 Replace the syringe plunger and compress the
water.
19.3.2.4 Invert the syringe, open the syringe valve, and
vent any residual air. Adjust the water volume to
the desired amount.
19.3.2.5 Adjust the plunger to the 25 mL mark to
accommodate the sample aliquot. Inject the proper
aliquot of sample from another syringe through the
valve bore of the 25 mL syringe. Close the valve
and invert three times.
19.3.2.6 Analyze according to Sections 17.4 to 18.
VOA D-30 6/91
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20. IDENTIFICATION OP TARGET COMPOUNDS
20.1 The compounds listed in the Target Compound List (TCL), Exhibit C,
shall be identified by an analyst competent in the interpretation of
mass spectra by comparison of the sample mass spectrum to the mass
spectrum of a standard of the suspected compound. Two criteria must
be satisfied to verify the identifications: (1) elution of the
sample compound at the same GC relative retention time as the
standard compound, and (2) correspondence of the sample compound and
standard compound mass spectra.
20.2 For establishing correspondence of the GC relative retention time
(RRT), the sample compound RRT must be within ±0.06 RRT units of the
RRT of the standard compound in the continuing calibration analysis.
If co-elution of interfering compounds prohibits accurate assignment
of the sample compound RRT from the extracted ion current profile for
the primary ion, the RRT must be assigned by using the total ion
chromatogram.
20.3 For comparison of standard and sample compound 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 BFB technical
acceptance criteria. These standard spectra may be obtained from the
continuing calibration analysis that was also used to obtain the
reference relative retention times.
20.4 The guidelines for qualitative verification by comparison of mass
spectra are as follows:
20.4.1 All ions present in the standard mass spectra at a relative
intensity greater than 25 percent (most abundant ion in the
spectrum equals 100 percent) should be present in the sample
spectrum.
20.4.2 The relative intensities of ions specified in Section 20.4.1
must agree within ±20 percent between the standard and sample
spectra. (Example: For an ion with an abundance of 50
percent in the standard spectra, the corresponding sample
abundance must be between 30 and 70 percent).
20.4.3 Ions greater than 25 percent in the sample spectrum but not
present in the standard spectrum must be considered and
accounted for by the analyst making the comparison. The
verification process should FAVOR FALSE POSITIVES. All
compounds meeting the identification criteria must be
reported with their spectra.
20.4.4 If a compound cannot be verified by all of the spectral
identification criteria listed in Sections 20.4.1 - 20.4.3,
but in the technical judgment of the mass spectral
interpretation specialist, the identification is correct,
then the Contractor shall report that identification and
proceed with quantitation.
VGA D-31 6/91
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21. IDEKTIPICATION OP NON-TARGET COMPOUNDS
21.1 A library search shall be executed for non-target sample compounds
for the purpose of tentative identification. For this purpose, the
most recent release of the National Institute of Standards and
Technology Mass Spectral Library shall be used.
21.2 Up to ten (10) non-internal standard and non-surrogate organic '
compounds of greatest apparent concentration not listed in Exhibit C
for the purgeable organic fraction shall be tentatively identified
via a forward search of the NIST Mass Spectral Library. (Compounds
with a peak area response less than 40 percent of the peak area
response of the best matched 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 must not use normalization routines
if those routines would misrepresent the library or unknown spectra
when compared to each other.
21.3 Guidelines for making tentative identification:
21.3.1 All ions present in the standard mass spectra at a relative
intensity greater than 25 percent (most abundant ion in the
spectrum equals 100 percent) must be present in the sample
spectrum.
21.3.2 The relative intensities of the major ions specified in
Section 20.4.1 must agree within ±20 percent between the
standard and sample spectra. (Example: For an ion with an
abundance of SO percent in the standard spectra, the
corresponding sample ion abundance must be between 30 and 70
percent.)
21.3.3 Molecular ions present in reference spectrum should be
present in sample spectrum.
21.3.4 Ions present in the sample spectrum but not in the reference
spectrum should be reviewed for possible background
contamination or presence of co-eluting compounds.
21.3.5 Ions present in the reference spectrum but not in the sample
spectrum should be reviewed for possible subtraction from the
sample spectrum because of background contamination or
co-eluting compounds. Data system library reduction programs
can sometimes create these discrepancies.
21.3.6 Ions greater than 25 percent in the sample spectrum but not
present in the standard spectrum must be considered and
accounted for by the analyst making the comparison. The
verification process should FAVOR FALSE POSITIVES. All
compounds meeting the identification criteria must be
reported with their spectra.
VOA
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21.3.6 If in the technical Judgment of the mass spectral
interpretation specialist, no valid tentative identification
can be made, the compound should be reported as unknown. The
mass spectral specialist should give additional
classification of the unknown compound, if possible (e.g.,
unknown aromatic, unknown hydrocarbon, unknown chlorinated
compound). If a probable molecular weight can be
distinguished, include it.
22. CALCULATIONS
NOTE: Unless otherwise stated the area response is that of the
extracted ion current profile (EICF) of the primary quantitation ion.
22.1 Target Compounds
22.1.1 Calculate target compound and surrogate concentrations using
Equation D.7.
EQ. D.7 Concentration in ug/L - (Ax)(Is)(Df)
(Aia)(RRF)(V0)
Where:
AX - Area response (EICF) for the compound to be measured.
The primary quantitation ions for the target, internal
standards, and the surrogate compounds are listed in
Table D-4.
A£S - Area response (EICF) for the internal standard.
The target compounds are listed with their associated
internal standards in Table D-3.
Is - Amount of internal standard added in nanograms (ng).
RRF - The relative response factor from the continuing
calibration standard.
V0 - Total volume of water purged, in milliliters (mL).
Df - Dilution factor. The dilution factor for analysis of
water samples for volatiles by this method is defined
as the ratio of the number of milliliters (mL) of water
purged (i.e., V0 above) to the number of mL of the
original water sample used for purging. For example,
if 12.5 mL of sample is diluted to 25.0 mL with reagent
water and purged, Df-25.0 mL/12.5 mL-2.0. If no
dilution is performed, Df-1.0.
22.1.2 When target compounds are below contract required
quantitation limits (CRQL) but the spectra meet the
identification criteria, report the concentration wirh a "J".
For example, if the CRQL is 1.0 ug/L and a concentration of
VQA D-33 6/91
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0.5 ug/L is calculated, report as "0.5 J". Report ALL sample
concentration data as UNCORRECTED for blanks.
22.1.3 Xylenes (o-, a-, and p- isomers) are to be reported as
xylenes (total). Because m- and p-xylene isomers coelute on
capillary columns, special attention must be given to the
quantitation of the xylenes. The relative response factor
(RRF) is based on the peak that represents the single isomer
on the GC column using o-xylene on capillary columns. In
quantitating sample concentrations, use the areas on both
peaks and the RRF. The areas of the two peaks may be summed
and the concentration determined, or the concentration
represented by each of the two peaks may be determined
separately, and then summed.
22.1.4 The stereoisomers, trans-l,2-dichloroethene and cis-
1,2-dichloroethene, are to be reported separately.
22.2 Non-Target Compounds
Equation D.7 is also used for calculating non-target compound
concentrations. Total area counts (or peak heights) from the total
ion chroma to grams (RIG) are to be used for both the non-target
compound to be measured (Ax) and the internal standard (A^s).
Associate the nearest internal standard free of interferences with
the non-target compound to be measured. A relative response factor
(RRF) of 1.0 is to be assumed. The value from this quantitation
shall be qualified as estimated ("J"). This estimated concentration
must be calculated for all tentatively identified compounds as well
as those identified as unknowns. Do not report any non-target
compound whose concentration is less than 2.0 ug/L (peak area
response is less than 40% of the peak area response of the nearest
internal standard).
22.3 Surrogates
Calculate the surrogate percent recovery using Equation D.8.
Qd
EQ. D.8 Surrogate Percent Recovery - x 100
Qa
Where:
Q(l - Quantity determined by analysis.
Qa - Quantity added to sample/blank.
22.4 Internal Standards
22.4.1 Calculate the percent area response change (%ARC) between the
sample/blank analysis and the most recent continuing
calibration standard analysis for each of the internal
standards using Equation D.9.
VOA D-34 6/91
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EQ. D.9 % ARC - AS ' ^ x 100
AC
Where:
% ARC - Percent area response change.
As - Area response of the internal standard (EICF) in the
sample/blank analysis.
AC - Area response of the internal standard (EICP) in the
most recent continuing calibration standard.
22.4.2 Calculate the retention time shift (RTS) between the
sample/blank analysis and the most recent continuing
calibration standard analysis for each of the internal
standards using Equation D.IO.
EQ. D.IO RTS - RTS - RTC
Where:
RTS - Retention time shift.
RTS - Retention time of the internal standard in a
sample/blank.
RTe - Retention time of the internal standard in
the most recent continuing calibration standard.
23. TECHNICAL ACCEPTANCE CRITERIA FOR SAMPLE ANALYSIS
23.1 The sample must be analyzed on a GC/MS system meeting the BFB,
initial calibration, continuing calibration, and blank technical
acceptance criteria.
23.2 The sample must be analyzed within the contract holding times. The
sample must have an LCS associated with it meeting the LCS technical
acceptance criteria. The sample must have a FES associated with ic
meeting the FES technical acceptance criteria.
23.3 The surrogate compound percent recovery must be between 80 and 120
percent inclusive.
23.4 The difference of the area response between the sample and the most
recent continuing calibration standard analysis for each of the
internal standards must be within the inclusive range of +40.0
percent of the continuing calibration standard.
23.5 The retention time shift between the sample and the most recent
continuing calibration standard analysis for each of the internal
standards must be within ±0.33 minutes (20.0 seconds).
VOA D-35 6/91
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23.6 Excluding those ions in the solvent front, no ion may saturate the
detector. No target compound concentration may exceed the upper
limit of the initial calibration range unless a more dilute aliquot
of the sample is also analyzed according to the procedures in Section
19.
23.7 The Contractor must demonstrate that there is no carryover from a
contaminated sample before data from subsequent analyses may be
submitted. After a sample that contains a target compound at a level
exceeding the initial calibration range, or a non-target compound at
a concentration greater than 100 ug/L, or saturated ions from a
compound (excluding the compound peaks in the solvent front), the
Contractor must either:
23.7.1 Analyze an instrument blank immediately after the
contaminated sample. If an autosampler is used, an
instrument blank must also be analyzed using the same purge
inlet that was used for the contaminated sample. The
instrument blanks must meet the technical acceptance criteria
for blank analysis (Section 26.4), or
23.7.2 Monitor the sample analyzed immediately after the
contaminated sample for all compounds that were in the
contaminated sample and that exceeded the limits above. The
maximum contamination criteria are as follows: the sample
must not contain a concentration above the CRQL for the
target compounds or above 2 ug/L for the non- target compounds
that exceeded the limits in the contaminated sample. If an
autosampler is used, the next sample analyzed using the same
purge inlet that was used for the contaminated sample also
must meet the maximum contamination criteria.
24. COMtgUTlVH ACTION
24.1 If the technical acceptance criteria for the internal standards and
surrogate compound are not met, check calculations, internal standard
solutions and instrument performance. It may be necessary to bake-
out the system to remove the water from the purge and trap transfer
lines of the trap, to recalibrate the instrument, or take other
corrective action procedures to meet the technical acceptance
criteria.
24.2 If the Contractor needs to analyze more than one (1) sample dilution
other than the original analysis to have all the target compounds
within the initial calibration range (excluding the compound peaks in
the solvent front), contact SMO. SMO will contact the Region for
instructions.
24.3 All samples to be reported must meet the maximum contamination
criteria in Section 23.7. If any sample fails to meet these
criteria, each subsequent analysis must be checked for cross
contamination. The analytical system is considered contaminated
until a sample has been analyzed that meets the maximum contamination
W)A n.Tfi A/01
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criteria or an instrument blank has been analyzed that meets the
technical acceptance criteria for blanks.
24.4 Sample technical acceptance criteria MUST be met before data are
reported. Samples contaminated from laboratory sources or any
samples not meeting the sample technical acceptance criteria will
require reanalysis at no additional cost.
24.5 Sample reruns performed as a result of suspected matrix interference
beyond the scope of the method will be evaluated on a case-by-case
basis for payment purposes by SMO.
25. [This paragraph has been intentionally left blank and has been
reserved.]
VOA D-37 6/91
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SECTION V
SAMPLE QUALITY CONTROL PROCEDURES AND REQUIREMENTS
VOA D-38 6/91
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26. BLANK ANALYSIS
26.1 Summary
There are three different types of blanks required by this method.
26.1.1 Method Blank - 25 mL of reagent water spiked with 10.0 ul
internal standard and 10.0 ul surrogate solution, and carried
through the entire analytical scheme. The method blank is
analyzed Immediately following the continuing calibration
standard and before any samples are analyzed. The method
blank must be analyzed immediately after the initial
calibration sequence if samples are analyzed before the 12
hour time period expires. The method blank measures reagent
and system contamination.
26.1.2 Storage Blank - Upon receipt of the first samples from a
Sample Delivery Group, two-40 mL screw cap VOA vials with a
FIFE-faced silicon septum are filled with reagent water (80
mL total). The vials are stored under the same conditions as
the samples in the Sample Delivery Group. A 25.0 mL aliquot
of this reagent water is spiked with a 10.0 uL internal
standard and 10.0 uL of surrogate solution and analyzed after
all samples in the Sample Delivery Group have been analyzed.
The storage blank indicates whether contamination may have
occurred during storage of samples.
26.1.3 Instrument Blank - 25 mL of reagent water spiked with 10.0 uL
of internal and 10.0 uL of surrogate solution carried through
the entire analytical scheme. Instrument blanks are analyzed
after a sample/dilution which contains a target compound at a
concentration greater than 25 ug/L (ketones 125 ug/L) or a
non-target compound at a concentration greater than 100 ug/L
or saturated ions from a compound (excluding the compound
peaks in the solvent front). The results from instrument
blank analysis indicate whether there is contamination from a
previous sample.
26.2 Frequency
26.2.1 The method blank must be analyzed after the continuing
calibration standard and before any samples or storage blanks
are analyzed. The method blank must be analyzed after the
initial calibration sequence if samples are analyzed before
the 12 hour time period expires. A method blank must be
analyzed in each 12-hour time period in which samples,
including LCS, FES and storage blanks from an SDG are
analyzed.
26.2.2 Storage blanks must be analyzed once per Sample Delivery
Group, after all of the samples have been analyzed.
26.2.3 The Contractor must demonstrate that there is no carryover
from contaminated samples before data from subsequent
VOA D-39 6/91
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analyses may be used. Samples may contain target compounds
at levels exceeding the initial calibration range (25 ug/L
for non-ketones, 125 ug/L for ketones) or non-target
compounds at concentrations greater than 100 ug/L. or ions
from a compound that saturate the detector (excluding the
compound peaks in the solvent front). An instrument blank
must be analyzed immediately after the contaminated sample
(also in the same injection port if an autosampler is used)
or a sample that meets the m^»^i««» contamination criteria in
Section 23.7 must be analyzed. For these purposes, if the
instrument blank meets the technical acceptance criteria for
blank analysis or the sample meets the MX*™"!! contamination
criteria, the system is considered to be uncontaminated. If
the instrument blank or sample does not meet the criteria
(i.e., is contaminated), the system must be decontaminated.
Until an instrument blank meets the blank technical
acceptance criteria or a sample meets the matimm
contamination criteria (Section 23.7), any samples analyzed
since the original contaminated sample will require
reanalysis at no additional expense.
26.3 Procedure
Prepare and analyze the blanks and calculate results according to
Sections 17 through 22.
26.4 Technical Acceptance Criteria For Blank Analysis
26.4.1 All blanks must be analyzed on a GC/MS system meeting the
BFB, initial calibration, and continuing calibration
technical acceptance criteria and at the frequency described
in Section 26.2.
26.4.2 The storage blank must be analyzed on a GC/MS system chat
also meets the technical acceptance criteria for the method
blank.
26.4.3 Surrogate compound recovery in the blank must be between 80
and 120 percent inclusive.
26.4.4 The difference of the area response between the blank and the
most recent continuing calibration standard analysis for each
of the internal standards must be within the inclusive range
of ±40.0 percent of the response in the continuing
calibration standard.
26.4.5 The retention time shift between the blank and the most
recent continuing calibration standard analysis for each of
the internal standards must be less than or equal to ±0.33
minutes (20.0 seconds).
26.4.6 The concentration of the target compounds in the blank must
be less than the CRQL for each target compound. The
n./.n
-------
concentration of non- target compounds in the blank must be
less than 2.0 ug/L.
26.5 Corrective Action
26.5.1 It is the Contractor's responsibility to ensure that method
interferences caused by contaminants in solvents, reagents,
glassware, laboratory air and other sample storage and '
processing hardware that lead to discrete artifacts and/or
elevated baselines in gas chromatograns be eliminated. If a
Contractor's blanks exceed the criteria in Paragraph 26.4.6,
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.
26.5.2 Any method blank or instrument blank that fails to meet the
technical acceptance criteria must be reanalyzed at no
additional cost. Further, all samples processed within the
same 12-hour time period with a method blank or instrument
blank that does not meet the blank technical acceptance
criteria will require reanalysis at no additional cost.
Mote: Storage blank data must be retained by the Contractor
and be made available for inspection during the on- site
laboratory evaluation.
27. LABORATORY CONTROL
27 . 1 Summary
The LCS is an internal laboratory quality control sample designed to
assess (on an SDG-by-SDG basis) the capability of the contractor to
perform the analytical method listed in this Exhibit.
27 . 2 Frequency
The LCS must be prepared, analyzed, and reported once per Sample
Delivery Group. The LCS must be prepared and analyzed concurrently
with the samples in the SDG using the same instrumentation as the
samples in the SDG.
27 . 3 Procedure
27.3.1 Prepare the LCS using the procedure described in Section 17 .
Spike 25 mL of reagent water with 10.0 uL of LCS spiking
solution (see Paragraph 7.4.5), 10.0 uL of internal standard,
and 10.0 uL of surrogate solution.
27.3.2 Analyze the LCS as described in Sections 17 to 22.
VOA D-41 6/91
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27.4 Calculations
27.4.1 Calculate individual compound recoveries of the LCS using
Equation D.8, substicuting LCS percent recovery for surrogate
percent recovery.
27.4.2 See Section 22 for equations necessary for other
calculations.
27.5 Technical Acceptance Criteria For Laboratory Control Sample Analysis
27.5.1 The LCS oust be analyzed on a GC/MS system meeting the BFB,
initial calibration, continuing calibration, and blank
technical acceptance criteria at the frequency described in
Section 27.2.
27.5.2 The LCS oust be prepared as described in Paragraph 27.3.
27.5.3 The LCS must be prepared and analyzed with a method blank
that meets the blank technical acceptance criteria.
27.5.4 Surrogate compound recovery in the LCS must be between 80 and
120 percent inclusive.
27.5.5 The area response change between the LCS and .the most recent
continuing calibration standard analysis for each of the
internal standards must be within the inclusive range of
±40.0 percent.
27.5.6 The retention time shift between the LCS and the most recent
continuing calibration standard analysis for each of the
internal standards must be within ±0.33 minutes (20.0
seconds).
27.5.7 The percent recovery for each of the compounds in the LCS
must be within the recovery limits listed in Table D-6.
TABLE 0-6
Percent
Compound Recovery Limits
Vinyl chloride60-140
1,2-Dichloroethane 60-140
Carbon tetrachloride 60-140
1,2-Dichloropropane ' 60-140
Trichloroethene 60-140
1,1,2-Trichloroethane 60-140
Benzene 60-140
cis-l,3-Dichloropropene 60-140
Bromoform 60-140
Tetrachloroethene 60-140
1,2-Dibromoethane 60-140
1,4-Dichlorobenzene 60-140
wu
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NOTE: The recovery limits for any of the compounds listed above may
be expanded ac any time during the period of performance if SMO
determines that the limits are too restrictive.
27.6 Corrective Action
27.6.1 If the LCS technical acceptance criteria for the internal
standards and surrogate are not met, check calculations,
internal standard and surrogate solutions, and instrument
performance. It may be necessary to recalibrate the
instrument or take other corrective action procedures to meet
the internal standard and surrogate criteria.
27.6.2 The laboratory may not submit data from an SDG until the LCS
technical acceptance criteria are met. LCS contamination
from laboratory sources or any LCS not meeting the criteria
will require reanalysis of the LCS at no additional cost.
27.6.3 Further, all samples in the SDG prepared and analyzed with an
LCS that does not meet the LCS technical acceptance criteria
will also require reanalysis at no additional cost. Any LCS
failing to meet these technical acceptance criteria must be
reanalyzed at no additional cost.
28. PERFORMANCE EVALUATION SAMPT.g (PES^
28.1 Summary
The PES is an external laboratory quality control sample prepared and
designed to assess (on an SDG-by-SDG basis) the capability of the
Contractor to perform the analytical method listed in this Exhibit.
28.2 Frequency
The Contractor must analyze and report the PES once per SDG, if
available. The PES must be prepared and analyzed concurrently with
the samples in the SDG using the same instrumentation as the samples
in the SDG.
28.3 Procedure
28.3.1 The PES will be received either as an ampulated extract or as
a full volume sample. If received as an ampulated extract,
the Contractor will receive instructions concerning the
dilution procedure to bring the extract to full volume prior
to preparation and analysis of the PES.
28.3.2 Prepare the PES for analysis using the procedure described in
Section 17. Add 10.0 uL of internal standard and 10.0 uL of
surrogate solution to the aqueous PES. Analyze the PES as
described in Sections 17 to 22.
28.4 Calculations
VOA D-43 6/91
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See Section 22 for equations necessary for calculations.
28.5 Technical Acceptance Criteria for the FES
28.5.1 The FES must be analyzed on a GC/MS system meeting the BFB,
initial calibration, continuing calibration, and blanks
technical acceptance criteria at a frequency described in
Section 28.2.
28.5.2 The FES must be prepared according to the procedure in
Section 28.3.
28.5.3 The surrogate compound percent recovery in the FES must be
between 80 and 120 percent inclusive.
28.5.4 The difference of the area response between the FES and the
most recent continuing calibration standard analysis for each
of the internal standards must be within the inclusive range
of ±40.0 percent.
28.5.5 The retention time shift between the FES and the most recent
continuing calibration standard analysis for each of the
internal standards must be within ±0.33 minutes (20.0
seconds).
28.6 Corrective Action
28.6.1 If the FES technical acceptance criteria for the internal
standards and the surrogate are not met, check calculations,
standard solutions and instrument performance. It may be
necessary to recalibrate the instrument or take other
corrective action procedures to meet the internal standard
criteria. Any FES failing to meet these technical acceptance
criteria must be reanalyzed at no additional cost. If
insufficient FES spiking extract remains or if insufficient
full volume PES remains, document this in the SDG Narrative
by stating that the FES could not be reanalyzed because
insufficient volume remains.
28.6.2 In addition to complying with the PES technical acceptance
criteria, the Contractor will be responsible for correctly
identifying and quantifying the compounds included in the
PES. SMO will notify the Contractor of unacceptable
performance.
Note: Unacceptable performance for identification and
quantitation of compounds is defined as a score less than 75
percent.
28.6.3 The PES technical acceptance criteria MUST be met before
sample data are reported. Also, the Contractor must
demonstrate acceptable performance for compound
identification and quantitation.
VOA n-4£ fi/QI
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TABLE D-3
VOLATILE TARGET COMPOUNDS AND SURROGATE WITH CORRESPONDING
INTERNAL STANDARDS FOR QUANTITATION
1.4-DIFLUOROBENZENE
CHLOROBENZENE-d5
Acetone
Bromochloromethane
Brooome thane
2-Butanone
Carbon dlsulfide
Chloroe thane
Chloroform
Chloromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-1,2-Dichloroethene
trans-1,2-Dichloroethene
Methylene chloride
Vinyl chloride
4-Bromo£luorobenzene
Benzene
Bromodichloromethane
Carbon tetrachloride
Chlorobenzene
Dibromochloromethane
1,2-Dibromoethane
1,2-Dichloropropane
cis-1,3-Dichloropropene
trans-1,3-Dichloropropene
Ethylbenzene
2-Hexanone
4-Methy1-2-pentanone
Styrene
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Xylenes (total)
1.4-DICHLOROBENZENE-d4
Br onto form
1,2-Dibromo-3-chloropropane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
VOA D-45
6/91
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TABLE 0-4
PRIHARY QUANTITATION IONS (M/Z) AND SECONDARY
IONS FOR VOLATILE ORGANIC COMPOUNDS
Volatile
Target
Conroounds
Acetone
Benzene
Bromochlorome thane
Broaodiehlorome thane
Bromoform
Bromome thane
2-Butanone
Carbon dlsulfide
Carbon tetrachloride
Chlorobenzcne
Chloroethane
Chloroform
Chlorome thane
Dlbromochlorome thane
1 , 2 -Dibromo- 3 - chloropropane
1 , 2 -Dibromoe thane
1 , 2 -Dichlorobenzene
1 , 3 -Dichlorobenzene
1 , 4-Dichlorobenzexie
1 , 1-Dichloroe thane
1 , 2-Dichloroethane
1,1- Dichloroethene
cis - 1 , 2 -Dichloroethene
trans -1,2- Dichloroethene
1 , 2-Dichloropropane
cis-1 , 3-Dichloropropene
trans -1,3- Dichloropropene
Ethylbenzene
2-Hexanone
Methylene chloride
4 - Methyl - 2 - pentanone
Styrene
1,1,2, 2 -Tetrachloroechane
Tetrachloroethene
Toluene
1,1, 1-Trichloroe thane
1,1, 2 -Trichloroe thane
Trichloroe thene
Vinyl chloride
Xylenes (total)
SURROGATE COMPOUND AND INTERNAL
4 - Bromo fluorobenzene
Chlorobenzene - d$
l,4-Dichlorobenzene-d4
1 , 4-Difluorobenzene
Primary
Quant i tat ion
Ion
43
78
128
83
173
94
43
76
117
112
64
83
50
129
75
107
146
146
146
63
62
96
96
96
63
75
75
91
43
84
43
104
83
166
91
97
97
95
62
106
STANDARDS :
174
117
152
114
Secondary
Ions
58
_
49,130
85 , 127
175,254
96
72*
78
119
77 , 114
66
85
52
127
155,157
109,188
111,148
111,148
111,148
65,83
98
61,63
61,98
61,98
112
77
77
106
58,57,100
86,49
58 , 100
78
131,85
168,129
92
99,61
83,85,99,132,134
130,132
64
91
95,176
82,119
115,150
63,88
Quantitation of this analyte is based on m/z 43 but m/z 72
must be present in the spectrum.
VOA D-46
6/91
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TABLE D-5
TECHNICAL ACCEPTANCE CRITERIA FOR INITIAL AND CONTINUING
CALIBRATION FOR VOLATILE ORGANIC COMPOUNDS
Volatile Minimum Maximum Maximum
Compound RRF %RSD %Dlf E
Benzene 0.500 30.0 +30.0
Bromochloromethane 0.05 30.0 +30.0
Bromodichloromethane 0.200 30.0 +30.0
Bromoform 0.05 30.0 +30.0
Bromomethane 0.100 30.0 +30.0
Carbon cecrachloride 0.100 30.0 +30.0
Chlorobenzene 0.500 30.0 +30.0
Chloroform 0.200 30.0 +30.0
Dibromochloromechane 0.100 30.0 +30.0
1,2-Dibromoechane 0.100 30.0 +30.0
1,2-Dichlorobenzene 0.400 30.0 +30.0
1,3-Dichlorobenzene 0.600 30.0 +30.0
1,4-Dichlorobenzene 0.500 30.0 +30.0
1,1-Dichloroechane 0.200 30.0 +30.0
1,2-Dichloroechane 0.100 30.0 _ +30.0
1,1-Dichloroechene 0.100 30.0 +30.0
cis-1,3-Dichloropropene 0.200 30.0 +30.0
crans-1,3-Dichloropropene 0.100 30.0 +30.0
Ethylbenzene 0.100 30.0 +30.0
Scyrene 0.300 30.0 +30.0
1,1,2,2-Tetrachloroethane 0.100 30.0 ±30.0
Tetrachloroechene 0.200 30.0 +30.0
Toluene 0.400 30.0 +30.0
1,1,1-Trichloroethane 0.100 30.0 +30.0
1,1,2-Trichloroethane 0.100 30.0 +30.0
Trichloroethene 0.300 30.0 +30.0
Vinyl chloride 0.100 30.0 +30.0
Xylenes (total) 0.300 30.0 +30.0
4-Bromofluorobenzene 0.200 30.0 +30.0
The following compounds have no maximum %RSD or maximum % Difference
criteria, but must meet a minimum RRF criterion of 0.010:
Carbon disulfide trans-1,2-Dichloroethene
Choroethane 1,2-Dichloropropane
Chloromethane Methylene Chloride
cis-1,2 -Dichloroethene
Note: At the present time, the Agency has not set minimum RRF or %RSD
criteria for Acetone, 2-Butanone, 1,2-Dibromo-3-chloropropane, 2-Hexanone and
4-Methyl- 2-pentanone.
VOA D-47 6/91
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EXHIBIT D
METHOD FOR THE ANALYSIS OF LOW CONCENTRATION WATER FOR SEHT70LATILE ORGANIC
COMPOUNDS
SV D-l 6/91
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Table of Contents
Page
SECTION I: Introduction SV D-3
SECTION II:
Part A - Sample/Sample Extract Storage and
Holding Times SV D-4
Part B - Equipment and Standards SV D-5
SECTION III: Instrument Quality Control Procedures
and Requirements
Part A - Instrument Operating Conditions SV D-13
Part B - Tuning the Mass Spectrometer SV D-14
Part C - Calibration of the GC/MS System SV D-16
SECTION IV: Sample Preparation, Analysis, and Compound
Identification and Quantitation SV D-23
SECTION V: Sample Quality Control Procedures and
Requirements SV D-33
SV D-2
6/91
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SECTION I
INTRODUCTION
The analytical method that follows is designed to analyze samples containing
low concentrations of the semivolatile compounds listed on the Target
Compound List (TCL) in Exhibit C. The majority of the samples are expected
to be from drinking water and well/ground water sources around Superfund
sites. The method is based upon the semivolatile method contained in the CLP
Statement Of Work, "Organic Analysis, Multi-Media, Multi-Concentration by
GO/MS and GC/EC Techniques*, except that a single extraction at a pH 2.0 is
used. Incorporated in the method are specific requirements to minimize
contamination of the samples from laboratory sources.
Problems have been associated with the following compounds covered by this
method:
o Oichlorobenzidine and 4-chloroaniline may be subject to oxidative losses
during solvent concentration.
o Hexachlorocyclopentadiene is subject to thermal decomposition in the inlet
of the gas chromatograph, chemical reactions in acetone solution, and
photochemical decomposition.
o N-nitrosodiphenylamine decomposes in the gas chroma to graphic inlet forming
diphenylamine and, consequently, may be detected as diphenylamine.
o Due to the lower quantitation limits required by this method, extra
caution must be exercised when identifying compounds.
SV D-3 6/91
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SECTION II
PART A - SAMPLE/SAMPLE EXTRACT STORAGE AND HOLDING TIMES
1. PROCEDURES FOR SAMPT-3 STORAGE
The samples must be protected from light and refrigerated at 4*C (±2*C)
from the tine of receipt until 60 days after delivery of a complete
reconciled data package. After 60 days the samples may be disposed of
in a. manner that complies with all applicable regulations.
Samples must be stored in an atmosphere demonstrated to be free of all
potential contaminants.
Samples, sample extracts, and standards must be stored separately.
2. PROCEDURE FOR SAMPLE EXTRACT STORAGE
Sample extracts must be protected from light and stored at 4'C (±2*0)
until 365 days after delivery of a complete data package.
Sample extracts must be stored in an atmosphere demonstrated to be free
of all potential contaminants.
Samples, sample extracts, and standards must be stored separately.
3. CONTRACT REQUIRED HOLDING TIMES
The extraction shall be started within 5 days of the Validated Time of
Sample Receipt (VTSR).
Extracts must be analyzed within 40 days following the start of the
extraction.
SV D-4 6/91
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PART B - EQUIPMENT AND STANDARDS
4. SUMMARY OP METHOD
4.1 A one liter aliquot of sample is acidified to pH 2.0 and extracted with
methylene chloride using a continuous liquid-liquid extractor. The
methylene chloride extract is dried and concentrated to a volume of 1.0
mL. The extract is injected onto a gas chromatograph (GC) capillary
column. The gas chromatograph is temperature programmed to separate
the seaivolatile compounds, which are then detected with a mass
spectrometer (MS).
4.2 Target and surrogate compounds are identified in the samples by
analyzing standards under the same conditions used for samples and
comparing resultant mass spectra and GC retention times. Internal
standards are added to all samples and standards. A response factor is
established for each target and surrogate compound during the initial
and continuing calibrations by comparing the MS response for the
primary ion produced by the compound extracted ion current profile
(EICP) to the MS response for the primary ion produced by an internal
standard. Each identified target and surrogate compound in a sample is
quantified by comparing the responses for the target compound and the
internal standard, while taking into account the response factor from
the most recent calibration, the sample volume, and any sample
dilutions.
4.3 Non-target compounds are identified by comparing the resultant mass
spectra from the non-target compounds to mass spectra contained in the
National Institute of Standards and Technology Mass Spectral Library.
Non-target compounds are quantified by comparing the MS response from
the reconstructed ion chromatogram (RIG) for the non-target compound
peaks to the MS response produced by the nearest internal standard. A
response factor of 1 is assumed.
5. INTERFERENCES
Contaminants in solvents, reagents, glassware and other sample
processing hardware, may cause method interferences such as discrete
artifacts and/or elevated baselines in the reconstructed ion current
(RIC) profiles (TICPs). 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.
6. APPARATUS AND MATERIALS
Brand names, suppliers and part numbers are for illustrative purposes
only. No endorsement is implied. Equivalent performance may be
achieved using apparatus and materials other than those specified here,
but demonstration of equivalent performance meeting the requirements of
the method is the responsibility of the Contractor.
SV D-5 6/91
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6.1 Gas Chromatograph/Mass Spectrometer
6.1.1 Gas Chromatograph - The gas chromatograph (GC) system must be
capable of temperature programming and have a flow controller
that maintains a constant column flow rate throughout the
temperature program . The system must be suitable for
splitless injection and have all required accessories including
syringes, analytical columns, and gases. All GC carrier gas
lines must be constructed from stainless steel or copper
tubing. Non-polytetrafluoroethylene (PTFE) thread sealants, or
flow controllers with rubber components are not to be used.
Gas Chromatography Column - A 30 m x 0.25 mm ID (or 0.32 am)
bonded-phase silicone coated fused silica capillary column (J&W
Scientific OB-5 or equivalent). A film thickness of 0.25 to
1.0 urn may be used.
6.1.2 Mass Spectrometer - The mass spectrometer must be capable of
scanning from 35 to 500 amu every 1 second or less, utilizing
70 volts (nominal) electron energy in the electron impact
ionization mode and producing a mass spectrum which meets all
die tuning acceptance criteria when 50 ng of
decafluorotriphenylphosphine (DFTPP) is injected through the
gas chromatograph inlet. To ensure sufficient precision of
mass spectral data, the MS scan rate must allow acquisition of
at least five spectra while a sample compound elutes from the
GC. The GC/MS system must be in a room whose atmosphere is
demonstrated to be free of all potential contaminants which
will interfere with the analysis. The instrument must be
vented outside the facility or to a trapping system which
prevents the release of contaminants into the instrument room.
6.1.3 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 (EIC?). Software
must also be available that allows integrating the abundance in
any EICP between specified time or scan number limits. Also,
for the non-target compounds, software must be available that
allows comparing sample spectra against reference library
spectra. The most recent release of the National Institute of
Standards and Technology Mass Spectral Library shall be used as
the reference library.
6.2 Magnetic Tape Storage Device - The magnetic tape storage device must be
capable of recording data and suitable for long-term, off-line storage.
SV D-6 6/91
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6.3 Glassware: A set of glassware sufficient to meet contract requirements
must be reserved for exclusive use in this contract.
6.3.1 Continuous liquid-liquid extractors - Equipped with Teflon or
glass connecting joints and stopcocks requiring no lubrication
(Hershberg-Wolf Extractor-Ace Glass Company, Vineland, NJ, P/N
6841-10 or equivalent.)
6.3.2 Drying column - 19 mm ID chromatographic column with coarse
frit. (Substitution of a small pad of Pyrex pre-extracted glass
wool for the frit will prevent cross contamination of sample
extracts.)
6.3.3 Concentrator tube - Kuderna-Danish, 10 mL, graduated (Kontes,
Vineland, NJ, K-570050-1025 or equivalent).
6.3.4 Evaporation flask - Kuderna-Danish, 500 mL (Kontes K-570001 -
0500 or equivalent). Attach to concentrator tube with springs.
6.3.5 Snyder column - Kuderna-Danish, Three-ball macro (Kontes
K-50300-0121 or equivalent).
6.3.6 Snyder column - Kuderna-Danish, Two-ball micro (Kontes K-
569001-0219 or equivalent).
6.3.7 Vials - Amber glass, 2 mL capacity with Teflon-lined screw-cap.
6.3.8 Syringes - 0.2 mL, 0.5 mL, and 5 mL volumes.
6.4 Gases - Helium, Nitrogen, ultra pure grade.
6.5 Gas-line tubing - stainless steel, or copper tubing.
6.6 Silicon carbide boiling chips - approximately 10/40 mesh. Heat to
400*C for 30 minutes or Soxhlet extract with methylene chloride.
6.7 Water bath - Heated, with concentric ring cover, capable of temperature
control. To prevent the release of solvent fumes into the laboratory,
the bath must be used in a hood.
6.8 Balance - Analytical, capable of accurately weighing +0.0001 g. The
balances must be calibrated with class S weights once per each 12-hour
workshift. The balances must also be annually checked by a certified
technician.
6.9 Nitrogen evaporation device equipped with a water bath that can be
maintained at 30*C to 35*C. To prevent the release of solvent fumes
into the laboratory, the nitrogen evaporation device must be used in a
hood. The N-Evap by Organomation Associates, Inc. South Berlin, MA (or
equivalent) is suitable.
SV D-7 6/91
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6.10 Micro-syringes - 10 uL and larger, 0.006 inch ID needle.
6.11 pH meter - Calibrate according to manufacturer's instructions. pH
meter must be calibrated before each use.
7. REAGZNTg
7.1 Reagent water - Reagent water is defined as water in which no
semivolatile target compound is observed at or above the CRQL listed in
Exhibit C for that compound and in which no non-target compound is
observed at or above 10 ug/L.
7.1.1 Reagent water may be generated by passing tap water through a
carbon filter bed containing about 453 g (1 Ib) of activated
carbon (Calgon Corp., Filtrasorb-300 or equivalent).
7.1.2 Reagent water may be generated using a water purification
system (Millipore Super-Q or equivalent).
7.2 Solvents - Acetone, methanol, methylene chloride. Pesticide quality or
equivalent.
7.3 Sodium sulfate - (ACS) Granular, anhydrous (J.T. Baker anhydrous
powder, catalog #73898, or equivalent). Purify by heating at 400*C for
four hours in a shallow tray, cool in a desiccator, and store in a
glass bottle.
7.4 Sulfuric acid solution (1:1) - slowly add 50 mL of concentrated 0*2804
(Sp. Gr. 1.84) to 50 mL of reagent water.
8.
8.1 The Contractor must provide all standard solutions to be used with this
contract. These standards may be used only after they have been
certified according to the procedure in Exhibit E. The Contractor must
be able to verify that the standards are certified. Manufacturer's
certificates of analysis must be retained by the Contractor and
presented upon request.
8.2 Stock Standard Solutions
Stock standard solutions may be purchased or prepared using the
following procedure.
8.2.1 Accurately weigh about 0.0100 g of pure material. Dissolve the
material in methylene chloride or another suitable solvent and
dilute to volume in a 10 mL volumetric flask. Larger volumes
may be used at the convenience of the analyst.
SV D-8 6/91
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8.2.2 When compound purity is assayed to be 97 percent or greater,
the weight may be used without correction to calculate the
concentration of the stock solution. If the compound purity is
assayed to be less than 97 percent, the weight must be
corrected when calculating the concentration of the stock
solution.
8.2.3 Fresh stock standards must be prepared once every twelve'
months, or sooner, if standards have degraded or concentrated.
Stock standards must be checked for signs of degradation or
concentration just prior to preparing secondary dilution and
working standards from them.
8.3 Secondary Dilution Standards
8.3.1 Using stock standards, prepare secondary dilution standards in
methylene chloride that contain the compounds of interest
either singly or mixed together.
8.3.2 Fresh secondary dilution standards must be prepared once every
twelve months, or sooner, if standards have degraded or
concentrated. Secondary dilution standards must be checked for
signs of degradation or concentration just prior to preparing
working standards from them.
8.4 Working Standards
8.4.1 Tuning Solution - Decafluorotriphenylphosphine (DFTPP)
Prepare a 50 ng/uL solution of DFTPP in methylene chloride.
The DFTPP solution must be prepared fresh once every twelve
months, or sooner, if the solution has degraded or
concentrated.
8.4.2 Initial and Continuing Calibration Solutions
8.4.2.1 Five initial calibration standard solutions are
required- for all target and surrogate compounds.
Standard concentrations of 5, 10, 20, 50, and 80
ng/uL are required for five of the surrogates and
all but eight of the target compounds. Nine
compounds: 2,4-dinitrophenol, 2,4,5-
trichlorophenol, 2-nitroaniline, 3-nitroaniline, 4-
nitroaniline, 4-nitrophenol, 4,6-dinitro-2-
methylphenol and pentachlorophenol, 2,4,6
tribromophenol (surrogate), require calibration at
20, 50, 80, 100, and 120 ng/uL.
8.4.2.2 To prepare a calibration standard solution, add an
appropriate volume of secondary dilution standard to
methylene chloride in a volumetric flask. Dilute to
volume with methylene chloride.
SV D-9 6/91
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8.4.2.3 Add 10.0 uL of internal standard spiking solution
(Paragraph 8.6.1) to 1.0 mL of each calibration
standard for a concentration of 20 ng/uL for each
internal standard.
8.4.2.4 The 20 ng/uL initial calibration solution (80 ng/uL
for the nine compounds listed in 8.4.2.1) is the
continuing calibration solution.
8.4.2.5 The five initial calibration solutions must be
prepared fresh before use. The continuing
calibration standard solution must be prepared
weekly, or sooner, if the solution has degraded or
concentrated.
8.5 Surrogate Standard Spiking Solution
8.5.1 Prepare a surrogate standard spiking solution in methanol that
contains, 2,4,6-tribromophenol (an acid surrogate compound), at
a concentration of 120 ug/aL. The other acid surrogate
compounds: phenol-dg and 2-fluorophenol, and the base/neutral
compounds: nitrobenzene-ds, terphenyl-d^, and 2-
fluorobiphenyl are at a concentration of 40 ug/mL.
8.5.2 The surrogate standard spiking solution must be prepared every
twelve months, or sooner, if the solution has degraded or
concentrated.
8.6 Internal Standard Spiking Solution
8.6.1 Prepare an internal standard spiking solution in methylene
chloride or another suitable solvent that contains 1,4
dichlorobenzene-d^, naphthalene•dg, acenaphthene-d^g,
phenanthrene-diQ, chrysene-dj^, and perylene-di2 at 2000 ng/uL.
It may be necessary to use 5 to 10 percent benzene or toluene
in this solution and a few minutes of ultrasonic mixing in
order to dissolve all the constituents.
8.6.2 The internal standard spiking solution must be prepared every
six months, or sooner, if the solution has degraded or
concentrated.
8.7 Laboratory Control Sample (LCS) Spiking Solution
8.7.1 Prepare a laboratory control sample spiking solution that
contains each of the compounds at the concentrations listed
below in methanol.
SV D-10 6/91
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Concentration
Compounds (ug/nL)
Phenol 40.0
2-Chlorophenol 40.0
4-Chloroaniline 40.0
2,4,6-Trichlorophenol 40.0
bis(2-Chloroethyl)ether 20.0
N-Nitroso-di-n-propylamine 20.0
Hexachloroe thane 20.0
Isophorone 20.0
1,2,4-Trichlorobenzene 20.0
Naphthalene 20.0
2,4-Dinitrotoluene 20.0
Diethylphthalate 20.0
N-Nitrosodiphenylamine 20.0
Hexachlorobenzene 20.0
Benzo(a)pyrene 20.0
8.7.2 The laboratory control sample solution must be prepared every
twelve months, or sooner, if the solution has degraded or
concentrated.
8.8 Storage of Standard Solutions
8.8.1 Store the stock and secondary standard solutions at -10*C to
-20*0 in Teflon-lined screw-cap amber bottles.
8.8.2 Store the working standard solutions at 4*C (+2*C) in Teflon-
lined screw-cap amber bottles.
8.8.3 Protect all standards from light.
8.8.4 Samples, sample extracts, and standards must be stored
separately.
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SECTION III
INSTRUMENT QUALITY CONTROL PROCEDURES AND REQUIREMENTS
SV D-12 6/91
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PART A - INSTRUMENT OPERATING CONDITIONS
Gas Chromacograph
The following are the recommended gas chromatographic analytical
conditions.
Carrier Gas:
Linear Velocity:
Injector Temperature:
Injector:
Initial Temperature:
Initial Hold Time:
Ramp Rate:
Final Temperature:
Final Hold Time:
Helium
25-30 cm/sec
250-300*C
Grob-type, splitless
40* C
4.0 ±0.1 min
10*C/min
290-C
10 min or until all compounds of interest
have eluted.
Optimize GC conditions for compound separation and sensitivity. Once
optimized, the same GC conditions must be used for the analysis of all
standards, samples, blanks, performance evaluation samples, and laboratory
control samples.
Mass Spectrometer
The following are the required mass spectrometer conditions:
Transfer Line Temperature:
Source Temperature:
Electron Energy:
lonization Mode:
Mass Range:
Scan Time:
250-300*C
According to manufacturer's
specifications.
70 volts (nominal)
El
35 to 500 amu
At least 5 scans per peak, not to exceed
1 second per scan.
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PART B - TUNING THE MASS SPECTROMETER
9. SUMMARY
It is necessary to establish that a given GC/MS meets the standard mass
spectral abundance criteria prior to initiating any on-going data
collection. This is accomplished through the analysis of
decafluorotriphenylphosphine (DFTPP).
10. FREQUENCY
Each GC/MS system used must be hardware tuned once per twelve (12) hour
time period of operation. Also, whenever the Contractor takes
corrective action which may change or affect the tuning criteria for
DFTPP (e.g., ion source cleaning or repair, column replacement, etc.).
the tune must be verified irrespective of the twelve-hour tuning
requirement. The twelve (12) hour time period for GC/MS system tuning
and standards calibration (initial or continuing calibration criteria)
begins at the moment of injection of the DFTPP analysis that the
Contractor submits as documentation of a compliant tune. The time
period ends after twelve (12) hours have elapsed. In order to meet
tuning requirements, samples, PES, LCS, blanks, and standards must be
injected within twelve hours of the DFTPP injection.
11. PROCEDURE
11.1 Inject 50 ng of DFTPP into the GC/MS system. All instrument conditions
must be identical to those listed in Section III, Part A, except that a
different temperature program may be used.
11.2 DFTPP may be analyzed separately or as part of the calibration
standard.
12. TECHNICAL ACCEPTANCE CRITERIA FOR DFTPP ANALYSIS
12.1 The GC/MS system must be tuned at the frequency described in Section
10.
12.2 The abundance criteria listed in Table D-7 must be met for a 50 ng
injection of DFTPP. The mass spectrum of DFTPP must be acquired in the
following manner. Three scans (the peak apex scan and the scans
immediately preceding and following the apex) are acquired and
averaged. Background subtraction is required, and must be accomplished
using a single scan prior to the elution of DFTPP. Note: All
subsequent standards samples, including LCS, PES, and blanks, must use
identical mass spectrometer instrument conditions.
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Table D-7
DFTPP KEY IONS AND ION ABUNDANCE CRITERIA
Mass Ion Abundance Criteria
51 30.0-80.0 percent of mass 198
68 Less than 2.0 percent of mass 69
69 Present
70 Lass than 2.0 percent of mass 69
127 25.0 - 75.0 percent of mass 198
197 Less than 1.0 percent of mass 198
198 . Base peak, 100 percent relative abundance (see note)
199 5.0 - 9.0 percent of mass 198
275 10.0 - 30.0 percent of mass 198
365 Greater than 0.75 percent of mass 198
441 Present but less than mass 443
442 40.0 - 110.0 percent of mass 198
443 15.0 - 24.0 percent of mass 442
Note: All ion abundance MUST be normalized to m/z 198, the nominal base
peak, even though the ion abundances of m/z 442 may be up to 110
percent that of m/z 198.
12.3 The criteria above are based on adherence to the acquisition
specifications identified in paragraph 12.2. The criteria are based on
performance characteristics of instruments currently utilized in
routine support of Program activities. These specifications, in
conjunction with relative response factor criteria for 51 target
compounds (see Table D-10), are designed to control and monitor
instrument performance associated with the requirements of this method.
13. CORRECTIVE ACTION
13.1 If the DFTPP acceptance criteria are not met, retime the GC/MS system.
It may be necessary to clean the ion source, clean quadrupoles, or take
other actions to achieve the acceptance criteria.
13.2 DFTPP acceptance criteria MUST be met before any standards, samples
(including LCS and PES), or required blanks are analyzed. Any samples
or required blanks analyzed when tuning criteria have not been met will
require reanalysis at no additional cost.
14. [This paragraph has been intentionally left blank and has been
reserved.]
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PART C - CALIBRATION OF THE GC/MS SYSTEM
15. INITIAL CALIBRATION
15.1 Summary - Prior co Che analysis of samples and required blanks and
after tuning criteria have been met, each GC/MS system must be
initially calibrated at a minimum of five concentrations to determine
instrument sensitivity and the linearity of GC/MS response for the
semivolatile target and surrogate compounds.
15.2 Frequency
15.2.1 Each GC/MS system must be initially calibrated upon award of
the contract, whenever the Contractor takes corrective action
which may change or affect the initial calibration criteria
(e.g., ion source cleaning or repair, column replacement,
etc.), or if the continuing calibration technical acceptance
criteria have not been met.
15.2.2 If time still remains in the 12 hour time period after meeting
the technical acceptance criteria for the initial calibration,
samples may be analyzed. It is not necessary to analyze a
continuing calibration standard within this 12 hour time
period, if the initial calibration standard that is the same
concentration as the continuing calibration standard meets the
continuing calibration technical acceptance criteria. Quantify
all sample and quality control sample results and quality
control criteria results, such as internal standard area
response change and retention time shift, against the initial
calibration standard that is the same concentration as the
continuing calibration standard.
15.3 Procedure
15.3.1 Set-up the GC/MS system per the requirements of Section III,
Part A.
15.3.2 All standard/spiking solutions and blanks must be allowed to
warm to ambient temperature (approximately 1 hour) before
preparation or analysis.
15.3.3 Prepare five calibration standards containing all the
semivolatile target and surrogate compounds at the
concentrations described in Paragraph 8.4.2.
15.3.4 Prepare an internal standard spiking solution using the
procedure described in Section 8.6.
15.3.5 Tune the GC/MS system to meet the technical acceptance criteria
in Section 12 for DFTPP.
15.3.6 Analyze each calibration standard by injecting 1.0 uL of
standard. If a compound saturates when the 80 ng/uL standard
is injected (120 ng/uL for the nine compounds listed in
SV D-16 6/91
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Paragraph 8.4.2), and the GC/MS system is calibrated to achieve
a detection sensitivity of no less than the CRQL for each
compound,' the Contractor must document it in the SOG Narrative,
and attach a quantitation report and RIG. In this instance,
the Contractor must calculate the results based on a four-point
initial calibration for the specific compound that saturates.
Secondary ion quantitation is only allowed when there are
sample interferences with the primary quantitation ion. If
secondary ion quantitation is used, calculate a relative
response factor using the area response from the most intense
secondary ion which is free of interferences, and document the
reasons for the use of the secondary ion in the SDG Narrative.
15.4 Calculations
NOTE: Unless otherwise stated the area response is that of the primary
quantitation ion.
15.4.1 Calculate relative response factors (RRF) for each semivolatile
target and surrogate compounds using Equation D.ll. See Table
D-8 to associate semivolatile target and surrogates compounds
with the proper internal standard. See Table D-9 for primary
quantitation ions to be used for each semivolatile target
compound, surrogate, and internal standard.
EQ. D.ll AX Cls
RRF - X -p
Ais °x
Where:
AX - Area of the primary quantitation ion response (EICP) for
the compound to be measured.
A£S - Area of the primary quantitation ion response (EICP) for
the internal standard.
cis ~ Concentration of the internal standard.
GX - Concentration of the compound to be measured.
15.4.2 Equation D.12 is the general formula for standard deviation
(SD) for a statistically small set of values.
EQ. D.12
»-
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Where:
SD - Standard deviation for set of values.
x^ - Value.
x - Mean value.
n - Number of values.
15.4.3 Calculate the percent relative standard deviation (%RSD) of RRP
values for each semivolatile target and surrogate compound over
the initial calibration range using Equation D.13 in
conjunction with Equation D.12.
EQ. D.13 SDBBF
%RSD - —7- x 100
x
Where:
%RSD - Percent relative standard deviation.
SDRRT - Standard deviation of initial calibration response
factors (per compound).
From EQ. D.12
*i - RRF - Relative response factors from initial calibration
standard (per compound).
x - RRF - Mean value of initial calibration response factors
(per compound).
15.4.4 Equation D.14 is the general formula for the mean of a set of
values.
EQ. D.14 x -
n
X£ - Value.
x - Mean value.
n — Number of values.
15.4.5 Calculate the mean of the relative retention times (RRT) for
each semivolatile target and surrogate compound over the
initial calibration range using Equation D.14 and Equation
D.15.
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EQ. D.15 RTC
RRT -
RTC - Retention time for the scmivolatile target and surrogate
compound.
- Retention time for the internal standard.
From EQ. D.14:
- Relative retention times for the semivolatile
target or surrogate compound for each initial
calibration standard.
x - RRT - Mean relative retention time.
15.4.6 Calculate the area response (Y) mean for each internal standard
compound over the initial calibration range using Equation
D.14.
Where:
Xi - Y - Area responses of the primary quantitation ion (EICF)
for the internal standard for each initial calibration
standard.
x - Y - Area response mean.
15.4.7 Calculate the mean of the absolute retention times (RT) for
each internal standard over the initial calibration range using
Equation D.14.
Where:
X£ — RT - Retention time for the internal standard for each
initial calibration standard.
x - RT - Mean retention time.
n - Number of values.
15.5 Technical Acceptance Criteria For Initial Calibration
15.5.1 All initial calibration standards must be analyzed at the
concentration levels described in paragraph 8.4.2 and at the
frequency described in Section 15.2 on a GC/MS system meeting
the DFTPP technical acceptance criteria.
15.5.2 The relative response factor (RRF) at each calibration
concentration for each semivolatile target and surrogate
SV D-19 6/91
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compound must be greater than or equal to the compound's
minimum acceptable relative response factor listed in Table D-
10.
15.5.3 The %RSD over the initial calibration range for relative
response factor for each semivolatile and surrogate compound
that has a required %RSD must be less than or equal to the %RSD
listed in Table D-10.
15.5.4 Up to four compounds may fail the criteria listed in paragraph
15.5.2 and 15.5.3 and still meet the minimum RRF and %RSD
requirements. However, these four compounds must have a
minimum RRF greater than 0.010 and %RSD less than or equal to
40.0%.
15.5.5 The relative retention time (RRT) for each of the semivolatile
target and surrogates compounds at each calibration level must
be within ±0.06 relative retention time units of the mean
relative retention time (RRT) for each compound.
15.5.6 The area response (Y) for each internal standard compound in
each calibration standard must be within the inclusive r_ange of
-50 percent to +100 percent of the mean area response (Y) of
the internal standard in all of the calibration standards.
15.5.7 The retention time (RT) shift for each of the internal
standards at each calibration level must be within ±0.33
minutes (20.0 seconds) compared to the mean retention time (RT)
over the initial calibration range for each internal standard.
15.6 Corrective Action
15.6.1 If the technical acceptance criteria for initial calibration
are not met, inspect the system for problems. It may be
necessary to clean the ion source, change the column, or take
other corrective actions to achieve the acceptance criteria.
15.6.2 Initial calibration technical acceptance criteria MUST be met
before any samples (including the LCS and FES) or required
blanks are analyzed. Any samples or required blanks analyzed
when initial calibration criteria have not been met will
require reanalysis at no additional cost.
16. CONTINUING CALIBRATION
16.1 Summary
Prior to the analysis of samples and required blanks and after tuning
criteria and initial calibration criteria have been met, each GC/MS
system must be routinely checked by analyzing a continuing calibration
standard to ensure that the instrument continues to meet the instrument
sensitivity and linearity requirements of the method. The continuing
calibration standard contains all the semivolatile target compounds,
surrogates, and internal standards.
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16.2 Frequency
16.2.1 Each GC/HS used for analysis must be calibrated once every
twelve (12) hour time period of operation. The 12 -hour time
period begins with the injection of DFTPP.
16.2.2 If time still remains in the 12 hour time period after meeting
the technical acceptance criteria for the initial calibration,
samples may be analyzed. It is not necessary to analyze a
continuing calibration standard within this 12 hour time
period, if the initial calibration standard that is the same
concentration as the continuing calibration standard meets the
continuing calibration technical acceptance criteria. Quantify
all sample results against the 20 ng/uL (80 ng/uL for the nine
compounds listed in Section 8.4.2.1) calibration standard.
16 . 3 Procedure
16.3.1 Set up GC/MS system per the requirements of Section III, Part
A.
16.3.2 Prepare a continuing calibration standard solution containing
all the semivolatile target and surrogate compounds using the
procedure listed in Section 8.4.2.
16.3.3 All standard/ spiking solutions and blanks must be allowed to
warm to ambient temperature (approximately 1 hour) before
preparation or analysis.
16.3.4 Tune the GC/MS system to meet the DFTPP technical acceptance
criteria in Section 12.
16.3.5 Start the analysis of the continuing calibration standard by
injecting 1.0 uL of standard.
16 . 4 Calculations
16.4.1 Calculate a relative response factor (RRF) for each
semivolatile target and surrogate compound using Equation D.ll.
16.4.2 Calculate the percent difference between the mean relative
response factor from the most recent initial calibration and
the continuing calibration relative response factor for each
semivolatile target and surrogate compound using Equation D.17.
- RRFC
EQ D.17 % Difference R» - - — — - x 100
RRFj.
SV D-21 6/91
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Where:
RRFj[ - Average relative response factor from the most
recent initial calibration.
RRFC - Relative response factor from continuing calibration
standard.
16.5 Technical Acceptance Criteria For Continuing Calibration
16.5.1 The continuing calibration standard oust be analyzed at the 20
ng/uL (80 ng/uL for the nine compounds listed in 8.4.2.1)
concentration level at the frequency described in Section 16.2
on a GC/MS system meeting the DFTPP tuning and the initial
calibration technical acceptance criteria.
16.5.2 The relative response factor for each semivolatile target and
surrogate compound must be greater than or equal to the
compound's «
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SECTION IV
SAMPLE PREPARATION, ANALYSIS, AND COMPOUND IDENTIFICATION AND QUANTITATION
SV D-23 6/91
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17. SUMMARY
This method is designed for analysis of samples that contain low
concentrations of the semivolatile compounds listed in Exhibit C. The
majority of the samples are expected to come from drinking water
sources and well/ground water around Superfund sices. If, upon
inspection of a sample, the Contractor suspects that the sample is not
amenable to this method, contact SMO for instructions.
18. PROCZPT3S2
18.1 Extraction
Continuous liquid-liquid extraction is required for the extraction of
the samples.
18.1.1 Add methylene chloride to the bottom of the extractor and fill
it to a depth of at least 1 inch above the bottom side arm.
18.1.2 Using a 1 liter graduated cylinder, measure out a 1.0 liter
sample aliquot. Transfer the 1 liter sample aliquot to the
continuous extractor. Pipet 1.0 mL of surrogate standard
spiking solution into the sample and mix well. Check the pH of
the sample with a pH meter and adjust the pH to 2.0 with 1:1
H2S04.
18.1.3 Add sufficient methylene chloride to the distilling flask to
ensure proper solvent cycling during operation. Extract for 18
hours. Allow to cool, then detach the distilling flask and
label.
18.1.4 If the sample was received in a 1 liter container, rinse the
empty container with 60 mL of methylene chloride after taking
the sample aliquot. Add the rinsate to the continuous
extractor.
18.2 Concentrating the Extracts
18.2.1 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10
mL concentrator tube to a SOO mL evaporative flask. Other
concentration devices or techniques may be used in place of the
K-D, if equivalency is demonstrated for all the semivolatile
target compounds listed in Exhibit C.
18.2.2 Transfer the extract by pouring the extract through a drying
column containing about 10 cm of anhydrous granular sodium
sulfate, and collect the extract in a K-D concentrator. Rinse
the distilling flask and column with 20 to 30 mL of methylene
chloride to complete the quantitative transfer.
18.2.3 Add one or two clean boiling chips and attach a three-ball
Snyder column to the evaporative flask. Pre-wet the Snyder
column by adding about 1 mL methylene chloride to the top of
the column. Place the K-D apparatus on a hot water bath (60*C
SV D-24 6/91
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co 80*C) so thac Che concentrator Cube is partially immersed in
Che hot water, and the entire lover rounded surface of the
flask is bathed with hot vapor-: Adjust the vertical posicion
of the apparatus and the water temperature as required to
complete Che concentration in 10 to 15 minutes. At the proper
rate of distillation, the balls of Che column will accively
chatter but the chambers will not flood with condensed solvent.
When Che apparent volume of liquid reaches 1 mL, remove the K-D
apparatus from Che waCer bath and allow ic Co drain and cool
for ac least 10 minutes. Remove the Snyder column and rinse
the flask and its lower joint into the concentrator tube with 1
to 2 mL of mechylene chloride. A 5 mL syringe is recommended
for this operation.
18.2.4 Two different types of concentration techniques are permitted
to obtain Che final 1.0 mL volume: micro Snyder column and
nitrogen evaporation techniques.
18.2.4.1 Micro Snyder Column Technique
Add another one or two clean boiling chips to the
concentrator cube and attach a two-ball micro Snyder
column. Pre-wec Che Snyder column by adding abouc
0.5 mL of mechylene chloride Co Che cop of Che
column. Place Che K-D apparatus in a hoc water bath
(60*C to 80*C) so that che concentrator Cube is
partially immersed in che hoc water. Adjust the
vertical posicion of Che apparatus and che water
temperature as required to complete che
concentration in 5 to 10 minutes. At che proper
race of distillation che balls of che column will
accively chatter but Che chambers will noC flood
with condensed solvent. When Che apparent volume of
liquid reaches about 0.5 mL, remove che K-D
apparatus from Che water bath and allow it to drain
for at least 10 minutes while cooling. Do not let
che extract go to dryness. Remove che Snyder column
and rinse its flask and its lower joint into che
concencrator tube with 0.2 mL of methylene chloride.
Adjust Che final volume Co 1.0 mL with mechylene
chloride. Transfer Che excracc Co a Teflon-sealed
screw-cap bottle, label che bottle and store at 4*C
(±2'C).
18.2.4.2 Nitrogen Evaporation Technique (taken from ASTM
Method D3086)
Place the concentrator tube with an open micro
Snyder column attached in a warm water bach (30*C to
35*C) and evaporate che solvenc volume co just below
1 mL by blowing a gentle stream of clean, dry
nitrogen (filtered chrough a column of activated
carbon) above the extract. Caution: Gas lines from
the gas source to the evaporation apparatus must be
SV D-25 6/91
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stainless steel, copper, -or Teflon tubing. The
internal vail of the concentrator tube must be
rinsed down several times with methylene chloride
during the operation and the final volume brought to
1.0 mL with methylene chloride. During evaporation,
the tube solvent level must be kept below the water
level of the bath. The extract must never be
allowed to become dry. Transfer the extract to a
Teflon-sealed screw-cap bottle, label the bottle and
store at 4*C (±2*C).
18.3 Instrumental Analysis
18.3.1 Set up the GC/MS system per the requirements of Section III,
Part A. Before samples or required blanks can be analyzed, the
instrument must meet the DFTPP, initial calibration, and
continuing calibration technical acceptance criteria. All
samples, required blanks, extracts, and standard/spiking
solutions must be allowed to warm to ambient temperature
. (approximately 1 hour) before preparation/analysis. All sample
extracts and required blanks must be analyzed under the same
instrumental conditions as the calibration standards.
18.3.2 Add 10.0 uL of the internal standard spiking solution (2000
ng/uL) to the 1.0 mL extract. For sample dilutions, add an
appropriate amount of the internal standard spiking solution to
maintain a 20 ng/uL concentration of the internal standards in
the diluted extract.
18.3.3 Inject 1.0 uL of sample extract into the GC/MS, and start data
acquisition.
18.3.4 When all semivolatile target compounds have eluted from the GC,
terminate the MS data acquisition and store data files on the
data system storage device. Use appropriate data output
software to display full range mass spectra and EICPs.
19. DILUTIONS
19.1 When a sample extract is analyzed that has a semivolatile target
compound concentration greater than the upper limit of the initial
calibration range or in which ions from a compound saturate the
detector (excluding the compound peaks in the solvent front), the
extract must be diluted and reanalyzed. Secondary ion quantitation is
only allowed when there are sample interferences with the primary
quantitation ion, not when saturation occurs. If secondary ion
quantitation is used, calculate a relative response factor using the
area response (EICP) from the most intense secondary ion which is free
of sample interferences, and document the reasons for the use of the
secondary ion in the SDG Narrative.
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19.2 Dilute the sample using the following procedure:
19.2.1 Calculate the sample dilution necessary to keep the
semi-volatile target compounds that required dilution within the
upper half of the initial calibration range and so that no
compound has ions which saturate the detector (excluding the
compound peaks in the solvent front). Note: Do not dilute
sample solely to get 2,4,6 tribromophenol value within the
initial calibration range.
19.2.2 Dilute the sample extract with methylene chloride in a
volumetric flask.
19.2.3 Analyze the sample dilution per Section 18.3, including the
addition of internal standards to maintain a 20 ng/uL
concentration of the internal standards (see 18.3.2).
20. IDENTIFICATION OF TARGET COMPOUNDS
20.1 The compounds listed in the Target Compound List (TCL), Exhibit C,
shall be identified by an analyst competent in the interpretation of
mass spectra by comparison of the sample mass spectrum to the mass
spectrum of a standard of the suspected compound. Two criteria must be
satisfied to verify the identifications: (1) elution of the sample
compound at the same GO relative retention time as the standard
compound, and (2) correspondence of the sample compound and standard
compound mass spectra.
20.2 For establishing correspondence of the GC relative retention time
(RRT), the sample compound RRT must be within ±0.06 BRT units of the
RRT of the standard compound. For reference, the standard must be run
on the same shift as the sample. If co-elution of interfering
compounds prohibits accurate assignment of the sample compound RRT from
the extracted ion current profile for the primary ion, the RRT must be
assigned by using the total ion chromatogram.
20.3 For comparison of standard and sample compound mass spectra, mass
spectra obtained on the Contractor's GC/MS are required. These standard
spectra may be used for identification purposes, only if the
Contractor's GC/MS meets the DFTPP daily tuning technical acceptance
criteria. These standard spectra may be obtained from the analysis
used to obtain reference relative retention times.
20.4 The guidelines for qualitative verification by comparison of mass
spectra are as follows:
20.4.1 All ions present in the standard mass spectra at a relative
intensity greater than 25 percent (most abundant ion in the
spectrum equals 100 percent) must be present in the sample
spectrum.
20.4.2 The relative intensities of the major ions specified in Section
20.4.1 must agree within +20 percent between the standard and
sample spectra. (Example: For an ion with an abundance of 50
SV D-27 6/91
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percent: in the standard spectra, the corresponding sample ion
abundance must be between 30 and 70 percent.)
20.4.3 Ions greater than 25 percent in the sample spectrum but not
present in the standard spectrum must be considered and
accounted for by the analyst making the comparison. The
verification process should FAVOR FALSE POSITIVES. All
compounds meeting the identification criteria must be reported
with their spectra.
20.4.4 If a compound cannot be verified by all of Che criteria in
Sections 20.4.1 • 20.4.3, but in the technical Judgment of the
mass spectral interpretation specialist, the identification is
correct, then the Contractor shall report that identification
and proceed with quantitation.
21. IDENTIFICATION OF SON-TARGET COMPOUNDS
21.1 A library search shall be executed for non-target compounds for the
purpose of tentative identification. The most recent release of the
National Institute of Standards and Technology Mass Spectral Library
shall be used as the reference library.
21.2 Up to 20 non-surrogate/non-internal standard organic compounds of
greatest apparent concentration not listed in Exhibit C for the
semivolatiles shall be tentatively identified via a forward search of
the National Institute of Standards and Technology Mass Spectral
Library. (Compounds with a peak area response less than 50 percent of
the area response for the nearest internal standard and compounds which
elute before the first semivolatile target compound elutes 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 must not use normalization routines
if those routines would misrepresent the library or unknown spectra
when compared to each other.
21.3 Guidelines for making tentative identification
21.3.1 Relative intensities of major ions in the reference spectrum
(ions greater than 25 percent of the most abundant ion) should
be present in the sample spectrum.
21.3.2 The relative intensities of the major ions should agree within
±20 percent. (Example: For an ion with an abundance of 50
percent in the standard spectra, the corresponding sample ion
abundance should be between 30 and 70 percent.
21.3.3 Molecular ions present in reference spectrum should be present
in sample spectrum.
21.3.4 Ions present in the sample spectrum but not in the reference
spectrum should be reviewed for possible background
contamination or presence of co-eluting compounds.
SV D-28 6/91
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21.3.5 Ions present in the reference spectrum but not in the sample
spectrum should be reviewed for possible subtraction from the
sample spectrum because of background contamination or
coeluting compounds. Data system library reduction programs
can sometimes create these discrepancies.
21.3.6 If in the technical judgment of the mass interpretation
spectral specialist, no valid tentative identification can be
made, the compound should be reported as unknown. The mass
spectral specialist should give additional classification of
the unknown compound, if possible (e.g., unknown phthalate,
unknown hydrocarbon, unknown acid type, unknown chlorinated
compound). If a probable molecular weight can be distinguished,
include it.
22. CALCULATIONS
NOTE: Unless otherwise stated, the area response is from the extracted
ion current profile (EICP) of the primary quantitation ion.
22.1 Target Compounds
22.1.1 Calculate target compound concentrations using Equation D.18.
EQ. D.18 (A,)(Is)(Vc)(Df)
Concentration in ug/L -
(Ais)(RRF)(V0)(Vi)
Where:
AX - Area response (EICF) for the compound to be measured.
The primary quantitation ions for the target compounds,
internal standards, and surrogates are listed in
Table D-9.
Ais ~ Area response (EICF) for the internal standard. The
target compounds are listed with their associated
internal standard in Table D-8.
Is - Amount of internal standard inj ected in nanograins (ng).
RRF - The RRF from the most recent continuing calibration as
determined in Section 15.4.1.
V0 - Volume of water extracted in milliliters (mL).
V^ - Volume of extract injected in microliters (uL).
Vt - Volume of final extract in microliters (uL).
Df - Dilution Factor. The dilution factor for analysis of
water samples for semivolatiles by this method is defined
as follows:
SV D-29 6/91
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u^ mo^t: cone . extract used to make dilution •+• ul^ clean solvent
uL most cone, extract used to make dilution
If no dilution is performed, Df - 1.0.
22.1.2 When target compounds are below contract required quantisation
limits (CRQL), but the spectra meet the identification
criteria., report the concentration with a "J". For example, if
the CRQL is 5 ug/L and a concentration of 3.0 ug/L is
calculated, report as "3.0 J*. Report ALL saf|*ple concentration
PNCORRECTED for
22.2 Hen-Target Compounds
Equation D.18 is used for calculating the concentrations of the non-
target compounds. Total area counts (or peak heights) from the
reconstructed ion chromatograms (RIG) are to be used for both the non-
target compound to be measured (A^) and the internal standard (A^s) .
Associate the nearest internal standard free of interferences with the
non- target compound to be measured. A relative response factor (KEIF)
of one (1) is to be assumed. The value from this quantitation shall be
qualified as estimated ("J"). This estimated concentration must be
calculated for all tentatively identified compounds as well as those
identified as unknowns.
22 . 3 Surrogates
Calculate the surrogate percent recovery using Equation D.19.
Qd
EQ. D.19 Surrogate Percent Recovery - = — x 100
Where:
Qd - Quantity determined by analysis.
Qa - Quantity added to sample/blank.
22.4 Internal Standards
22.4.1 Calculate the percent area response change (% ARC) for the
sample/blank analysis compared to the most recent continuing
calibration standard analysis for each of the internal standard
compounds using Equation D.20.
A« - A-
EQ. D.20 % ARC - » x 100
SV D-30 6/91
-------
Where:
% ARC - Percent area response change.
As - Area response of the internal standard in
the sample/blank analysis.
AC - Area response of the internal standard in the most
recent continuing calibration standard.
22.4.2 Calculate the retention time shift (RTS) between the
sample/blank analysis and the most recent continuing
calibration standard analysis for each of the internal
standards using Equation D.21.
EQ. D.21 RTS - RTS - RTC
Where:
RTS - Retention time shift.
RTS - Retention time of the internal standard in a
sample/blank.
RTC - Retention time of the internal standard in the
most recent continuing calibration standard.
23. TECHNICAL ACCEPTARCE CRITERIA FOR SAMPLE ANALYSIS
23.1 The sample must be analyzed on a GC/HS system meeting the DFTPP,
initial calibration, and continuing calibration technical acceptance
criteria.
23.2 The sample must be extracted and analyzed within the contract holding
times.
23.3 The sample must have an associated method blank meeting the blank
technical acceptance criteria. The sample must have a Laboratory
Control Sample associated with it meeting the LCS technical acceptance
criteria. The sample must also have a PES associated with it meeting
the PES techncial acceptance criteria.
23.4 The percent recovery for each of the surrogates in the sample must be
within the acceptance windows listed in Table D-ll.
23.5 The difference of the area response change for each of the internal
standards for the sample must be within the inclusive range of -50
percent and +100 percent of the response of the internal standards in
the most recent continuing calibration analysis.
23.6 The retention time shift for each of the internal standards must be
within ±0.33 minutes (20.0 seconds) between the sample and the most
recent continuing calibration standard analysis.
SV D-31 6/91
-------
23.7 Excluding those ions in the solvent front, no ion may saturate the
detector. No target compound concentration may exceed the upper limit
of the initial calibration range unless a more dilute aliquot of the
sample extract is also analyzed according to the procedures in Section
19.
Table 0-11
CONTRACT REQUIRED SURROGATE SPIKE RECOVERY LIMITS
Surrogate Compound % Recovery
Nitrobenzene-d$ 40-112
2-Fluorobiphenyl 42-110
Terphenyl-d14 24-140
Phenol-d5 17-113
2-Fluorophenol 16-110
2,4,6-Tribromophenol 18-126
24. CORggCTTvE ACTION
24.1 If the sample technical acceptance criteria for the surrogates and
internal standards are not net, check calculations, surrogate and
internal standard solutions, and instrument performance. It may be
necessary to recalibrate the instrument or take other corrective action
procedures to meet the surrogate and internal standard technical
acceptance criteria.
24.2 If the Contractor needs to analyze more than one (1) sample dilution
other than the original analysis to have all the target compounds
within the initial calibration range and to have no ions saturating the
detector (excluding the peaks in the solvent front), contact SMO. SMO
will contact the Region for instructions.
24.3 Sample analysis technical acceptance criteria MUST be met before data
are reported. Samples contaminated from laboratory sources, or
associated with a contaminated method blank or any samples analyzed not
meeting the technical acceptance criteria will require reextraction
and/or reanalysis at no additional cost.
24.4 Sample reruns performed as a result of suspected matrix interferences
beyond the scope of the method will be reviewed on a case-by-case basis
for payment purposes by SMO.
25. [This paragraph has been intentionally left blank and has been
reserved.]
SV D-32 6/91
-------
SECTION V
SAMPLE QUALITY CONTROL PROCEDURES AND REQUIREMENTS
SV D-33 6/91
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26. BLANK ANALYSIS
26.1 Summary - A method blank is 1.0 liter of reagent water carried through
the entire analytical scheme.
26.2 Frequency
26.2.1 A method blank must be extracted at least once:
o every 20 samples, AND
o whenever samples are extracted.
26.2.2 Each method blank must be analyzed on each GC/MS used to
analyze the samples prepared with the method blank.
26.3 Procedure for Method Blank Preparation
26.3.1 Prepare the method blank at the frequency listed in Section
26.2. Measure out 1.0 liter of reagent water for each method
blank aliquot. Extract and concentrate the method blank at the
sane time as the samples associated with the blank according to
Sections 18.1.1 and 18.2.
26.3.2 Analyze the method blank and calculate the results according to
Sections 18-22.
26.4 Technical Acceptance Criteria For Blank Analysis
26.4.1 All blanks must be analyzed at the frequency described in
Section 26.2 on a GC/MS system meeting the DFTPP, initial
calibration, and continuing calibration technical acceptance
criteria.
26.4.2 The percent recovery for each of the surrogates in the blank
must be within the acceptance windows listed in Table D-ll.
26.4.3 The area response change for each of the internal standards for
the blank must be within the inclusive range of -50 percent and
+100 percent compared to the internal standards in the most
recent continuing calibration analysis.
26.4.4 The retention time shift for each of the internal standards
must be within ±0.33 minutes (20.0 seconds) between the blank
and the most recent continuing calibration analysis.
26.4.5 The concentration of the target compounds in the blanks must be
less than or equal to the CRQL for each target compound. The
concentration of non-target compounds in the blanks must not
exceed 10 ug/L.
26.5 Corrective Action
26.5.1 If a Contractor's blanks do not meet the technical acceptance
criteria, the Contractor must consider the analytical system to
SV D-34 6/91
-------
be out of control. It is the Contractor's responsibility to
ensure that method interferences caused by contaminants in
solvents, reagents, glassware, and sample storage and
processing hardware that lead to discrete artifacts and/or
elevated baselines in gas chromatograms be eliminated. If
contamination is a problem, the source of the contamination
must be investigated and appropriate corrective measures MUST
be taken and documented before further sample analysis
proceeds .
26.5.2 Any method blank that fails to meet the technical acceptance
criteria must be reextracted and reanalyzed at no additional
cost. Further, all samples processed with a method blank that
is out of control (i.e., contaminated) will require
reextraction and reanalysis at no additional cost.
27. LABORATORY CONTROL
27.1 Summary
The LCS is an internal laboratory quality control sample designed to
assess (on an SDG-by-SDG basis) the capability of the contractor to
perform the analytical method listed in this Exhibit.
27 . 2 Frequency
The LCS must be prepared, extracted, analyzed, and reported once per
Sample Delivery Group. The LCS must be extracted and analyzed
concurrently with the samples in the SDG using the same instrumentation
as the samples in the SDG.
27 . 3 Procedure
27.3.1 Measure a 1.0 liter aliquot of reagent water in a 1 liter
graduated cylinder and transfer the water to a continuous
extractor. Pipet 1.0 mL of the LCS spiking solution (Paragraph
8.7.1) and 1.0 mL of the surrogate standard spiking solution
into the water and mix well. Extract and concentrate the
sample according to Sections 18.1 and 18.2.
27.3.2 Analyze the LCS per Sections 18-21.
27 . 4 Calculations
27.4.1 Calculate individual compound recoveries of the LCS using
Equation D.19, substituting LCS percent recovery for surrogate
percent recovery.
27.4.2 See Section 22 for equations necessary for other calculations.
SV D-35 6/91
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27.5 Technical Acceptance Criteria For Laboratory Control Sample Analysis
27.5.1 The LCS must be analyzed at the frequency described in Section
27.2 on a GC/MS system meeting the DFTPP, initial calibration,
and continuing calibration technical acceptance criteria.
27.5.2 The LCS must be prepared as described in Paragraph 27.3.
27.5.3 The LCS must be prepared and analyzed with a method blank that
met the blank technical acceptance criteria.
27.5.4 The percent recovery for each of the surrogates in the LCS must
be within the acceptance windows listed in Table D-ll.
27.5.6 The area response change for each internal standard for the LCS
must be within the inclusive range of -50 percent and +100
percent compared to the internal standard in the most recent
continuing calibration analysis.
27.5.7 The retention time shift for each of the internal standards
within ±0.33 minutes (20.0 seconds) between the LCS and the
continuing calibration standard analysis.
27.5.8 The percent recovery for each of the compounds in the LCS must
be within the recovery limits listed in Table D-12.
Table D-12
LABORATORY CONTROL SAMPLE PERCENT RECOVERY LIMITS
COMPOUND % RECOVERY
Phenol 44 - 120
2-Chlorophenol 58 - 110
4-Chloroaniline 35 - 98
2,4,6-Trichlorophenol 65 - 110
bis(2-Chloroethyl)ether 64 - 110
N-Nitroso-di-n-propylamine 34 - 102
Hexachloroethane 32 - 77
Isophorone 49 - 110
1,2,4-Trichlorobenzene 44-96
Naphthalene 56 - 160
2,4-Dinitrotoluene 61 - 140
Diethylphthalate 76 - 104
N-Nitrosodiphenylamine 35 - 120
Hexachlorobenzene 30 - 95
Benzo(a)pyrene 55 - 92
NOTE: The recovery limits for any of the compounds in the LCS may be
expanded at any time during the period of performance if SMO determines
that the limits are too restrictive.
SV D-36 6/91
-------
27.6 Corrective Action
27.6.1 If the LCS technical acceptance criteria for the surrogates and
internal standards are not met, check calculations, surrogate
and internal standard solutions, and instrument performance.
It may be necessary to recalibrate the instrument or take other
corrective action procedures to meet the surrogate and internal
standard criteria.
27.6.2 The laboratory may not submit data from an SDG until the LCS
technical acceptance criteria are met. LCS contamination from
laboratory sources or any LCS not meeting the criteria will
require reanalysis and reextraction of the LCS at no additional
cost.
27.6.3 Further, all samples in the SDG prepared and analyzed with an
LCS that does not meet the LCS technical acceptance criteria
will also require reanalysis at no additional cost. Any LCS
failing to meet these technical acceptance criteria must be
reanalyzed and reextracted at no additional cost.
28. PERFORMANCE EVALUATION SAMPLE fPES^
28.1 Summary
The FES is an external laboratory quality control sample prepared and
designed to assess (on an SDG-by-SDG basis) the capability of the
Contractor to perform the analytical method listed in this Exhibit.
28.2 Frequency
The Contractor must extract, analyze, and report the results of the PE
sample once per SDG, if available. The FES must be extracted and
analyzed concurrently with the samples in the SDG using the same
instrumentation as the samples in the SDG.
28.3 Procedure
28.3.1 The PES will be received either as an ampulated extract or as a
full volume sample. If received as an ampulated extract, the
Contractor will receive instructions concerning the dilution
procedure to bring the extract to full volume prior to
preparation and analysis of the PES.
28.3.2 Extract and concentrate the PES using the procedure described
in Section 18. Add 1.0 mL of surrogate solution to 1 liter of
reagent water spiked with the PES solution. Analyze the PES as
described in Sections 18 to 21.
28.4 Calculations
See Section 22 for equations necessary for calculations.
28.5 Technical Acceptance Criteria for the PES
SV D-37 6/91
-------
28.5.1 The PES must be analyzed on a GC/MS system meeting the DFTPP
tuning, initial calibration, and continuing calibration
technical acceptance criteria at the frequency described in
Section 28.2.
28.5.2 The PES must be extracted and concentrated according to Section
28.3.
28.5.3 The PES must be prepared and analyzed with a method blank that
met the blank technical acceptance criteria.
28.5.4 The percent recovery for each of the surrogates in the PES must
be within the acceptance windows listed in Table D-ll.
28.5.5 The area response change between the PES and. the most recent
continuing calibration standard analysis for each of the
internal standards must be within the inclusive range of -50
percent and +100 percent.
28.5.6 The retention tine shift between the PES and the most recent
continuing calibration standard analysis for each of the
internal standards must be within ±0.33 minutes (20.0 seconds).
28.6 Corrective Action
28.6.1 If the PES technical acceptance criteria for the internal
standards and the surrogate are not met, check calculations,
standard solutions and instrument performance. It may be
necessary to recalibrate the instrument or take other
corrective action procedures to meet the internal standard
criteria. Any PES failing to meet these technical acceptance
criteria must be reextracted and reanalyzed at no additional
cost. If insufficient PES spiking extract remains or if
insufficient full volume PES remains, document this in the SDG
Narrative by stating that the PSS could not be reextracted and
reanalyzed because insufficient volume remained.
28.6.2 In addition to complying with the PES technical acceptance
criteria, the Contractor will be responsible for correctly
identifying and quantitating the compounds included in the PES.
SMO will notify the Contractor of unacceptable performance.
Note: Unacceptable performance for identification and
quantitation of compounds is defined as a score less than 75
percent.
28.6.3 The PES technical acceptance criteria MUST be met before sample
data are reported. Also, the Contractor must demonstrate
acceptable performance for compound identification and
quantitation.
SV D-38 6/91
-------
TABLE D-B
SEHIVOLATILE INTERNAL STANDARDS UITH
CORRESPONDING TARGET ANALVTES ASSIGNED FOR QUANTITATION
1,4-Dfchlorobenzene-d4
Naphthaitne-da
Actnaphthcna-djO
Phenanthrene-dio
Chrysene-d)2
Perylene-di2
Phenol
bis(2-Chloroethyl)ether
2-Chlorophenol
2-Hethylphenol
bls(2-Chloroisopropyl)ether
4-Hethylphenol
N-Nitroso-dl-n-propytamlne
2-fluorophenol (surr)
Phenol-d6 (surr)
C/l
o
UJ
Nitrobenzene
Isophorona
2-Mltrophenol
2,4-Dimethylphenol
bi*(2-Chloroethoxy)methane
2,4-Oichlorophenol
4-ChloroanHlne
Hexachlorobutadlene
4-Chloro-3-methylphenol
2-Hethylnaphthalene
N1trobenien«-dS (turr)
Hexachlorocyclopent adIene
2,4,6-Trichlorophenol
2,4,5-Trlchlorophenol
2-Chloronaphthalene
2-Nltroaniline
Dimethyl phthalate
Acenaphthylene
3-Mltroanlline
Acenaphthene
2,4-Dinltrophenol
4-Nltrophenol
Dlbcntofuran
2,4-Dlnltrotoluene
2,6-D < nl t rotoluene
DUthylphthalate
A-Chlorophenyl phenyl ether
Fluorine
4-Nltroanlline
2-Fluorobiphenyl (surr)
2,4,6-Trlbromophenol (surr)
4,6-Dlnltro-2-methylphenol
M-Mitrosodlphenylamlne
4-Bromophenyl phenyl ether
Hexachlorobenzene
PentachIorophenoI
Phenanthrene
Anthracene
DI-n-Butyl phthalate
Fluoranthene
Pyrene
ButylbenzylphthaUte
3,3-Dichlorobenzldlne
Benzo(a)Anthracene
bis(2-Ethylhexyl)phthalate
Chrysene
Terphenyl-dU (surr)
Dl-n-octylphthalate
Benzo(b)fIuoranthene
Benzo(k)fIuoranthene
Benio(a)pyrene
lndeno(1,2,3-cd)Pyrene
Dibeni(a,h)anthracene
Benzo(g,h,I)perylene
Surr =• surrogate compound
-------
Table D-9
Primary Quantitation Ions (m/z) and Secondary Ions
for Semivolatile Organic Compounds
PaTame tei*
Ion
Phenol
bis(2-Chloroethyl)ether
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dtchlorobenzene
1,2-Dichlorobenzene
2-Methylpheno1
2,2'-oxybis(l-Chloropropane)
4-Methylphenol
N-nitroso-di-n-propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2,4-Dimethylphenol
bis(-2-Chloroethoxy)methane
2,4-Oichlorophenol
1,2,4-Trichlorobenzene
Naphthalene
4-Chloroaniline
Hexachlorobutadiene
4-Chloro-3-methylphenol
2-Me thylnaphthalene
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-Oinitrotoluene
2,6-Dinitrotoluene
94
93
128
146
146
146
108
45
108
70
117
77
82
139
107
93
162
180
128
127
225
107
142
237
196
196
162
65
163
152
138
153
184
109
168
165
165
65, 66
63, 95
64, 130
148, 113
148, 113
148, 113
107
77, 79
107
42, 101, 130
201, 199
123, 65
95, 138
65, 109
121, 122
95, 123
164, 98
182, 145
129, 127
129
223, 227
144, 142
141
235, 272
198. 200
198, 200
164, 127
92, 138
194, 164
151, 153
108, 92
152, 154
63, 154
139, 65
139
63, 182
89, 121
SV D-40
6/91
-------
Table D-9 (continued)
Parameter Primary Ton Secondary lonf
Oiethylphthalate
4 • Chlorophenyl • phenyle ther
Fluorene
4-Nitroaniline
4, 6-Dinitro-2-methylphenol
N-Nitrosodiphenylamine
4 - Bromophenyl - phenyle ther
Hexachlorobenzene
Pentachloropheno 1
Phenanthrene
Anthracene
Di - n- butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
3,3' -Dichlorobenzidine
Benzo (a) anthracene
b is ( 2 - Ethylhexyl ) phthalate
Chrysene
Di-n-octyl phthalate
Benzo (b ) fluoranthene
Benzo (k) fluoranthene
Benzo (a) pyr one
Zndeno ( 1 , 2 , 3 - cd) pyrene
Oibenz ( a , h) anthracene
Benzo ( g , h , i ) perylene
Surrogates
Phenol -d5
2 - Fluor ophenol
2,4, 6 -Tribromophenol
Nitrobenzene £5
2 - Fluor ob ipheny 1
Terphenyl
Internal Standards
1 , 4-Dichlorobenzene - 04.
Naphthalene - dg
Acenapthene -d^Q
Phenanthrene - d^Q
Chrysene -dj^2
Perylene -d^2
149
204
166
138
198
169
248
284
266
178
178
149
202
202
149
252
228
149
228
149
252
252
252
276
278
276
99
112
330
82
172
244
152
136
164
188
240
264
177, 150
206, 141
165, 167
92, 108
182. 77
168, 167
250, 141
142, 249
264, 268
179, 176
179, 176
150, 104
101, 100
101, 100
91, 206
254, 126
229, 226
167, 279
226, 229
-
253, 125
253, 125
253, 125
138, 227
139, 279
138, 277
42, 71
64
332, 141
128, 54
171
122, 212
115
68
162, 160
94,80
120,236
260, 265
SV D-41 6/91
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TABLE D-10
ACCEPTANCE CRITERIA FOR INITIAL AND CONTINUING
CALIBRATION FOR SEMIVOLATILE ORGANIC COMPOUNDS
Semlvolatile
Compounds
Phenol
bis (2 -Chloroethyl) ether
2 - Chlorophenol
2-Methylphenol
4-Methylphenol
N-Nitroso-dl-n-propylamine
Hexachloroe thane
Nitrobenzene
Isophorone
2-Nitrophenol
2 , 4-Dinethylphenol
bis (2-Chloroethoxy)me thane
2 , 4-Dichlorophenol
1,2, 4-Trichlorobenzene
Naphthalene
4 -Chloro - 3 -me thylphenol
2 -Methylnaphthalene
2,4, 6-Trichlorophenol
2,4, 5-Trichlorophenol
2 - Chloronaphthalene
Acenaphthylene
Acenaphthene
Dibenzofuran
2 , 4 -Dinitro toluene
2 , 6-Dinitrotoluene
4 - Chloropheny 1 - pheny le Cher
Fluorene
4 - Bromopheny 1 - pheny lether
Hexachlorobenzene
Pentachloropheno 1
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo (a) anthracene
Chrysene
Benzo (b ) fluoranthene
Benzo (k) fluoranthene
Benzo(a)pyrene
Indeno (1,2,3-cd) pyr ene
Dibenzo (a, h) anthracene
Benzo ( g , h , i ) perylene
Minimum
RRF
0.800
0.700
0.700
0.700
0.600
0.500
0.300
0.200
0.400
0.100
0.200
0.300
0.200
0.200
0.700
0.200
0.400
0.200
0.200
0.800
1.300
0.800
0.800
0.200
0.200
0.400
0.900
0.100
0.100
0.050
0.700
0.700
0.600
0.600
0.800
0.700
0.700
0.700
0.700
0.500
0.400
0.500
Ma-vtimmi
%RSD
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
30.0
30.0
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
30.0
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
20.5
Maximum
%Diff
±25.0
+25.0
±25.0
±25.0
+25.0
±25.0
±25.0
±25.0
±25.0
±30.0
±30.0
±25.0
+25.0
±25.0
±25.0
±25.0
±25.0
±25.0
+25.0
±25.0
±25.0
+25.0
±25.0
±30.0
±25.0
±25.0
+25.0
+25.0
±25.0
+25.0
+25.0
±25.0
±25.0
+25.0
+25.0
±25.0
+25.0
±25.0
±25.0
+25.0
±25.0
±25.0
(continued)
SV D-42 6/91
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TABLE D-10
ACCEPTANCE CRITERIA FOR INITIAL AND CONTINUING
CALIBRATION FOR SEMIVOLATILE ORGANIC COMPOUNDS
Semivolatile
Compounds
RRF
Maximum
%RSD
Maximum
%Dlff
Phenol -d5
2 - Fluorophenol
2 - Fluorobipheny 1
0.800
0.600
0.500
0.700
20.5
20.5
20.5
20.5
±25.0
±25.0
+25.0
+25.0
The following compounds have no maximum %RSD or maximum %D criteria, but must
meet a minimum RRF criterion of 0.010:
2,2'-oxybis(1-Chloropropane)
4-Chloroaniline
Hexachlorobutadiene
Hexachlorocyclopentadiene
2-Nitroaniline
DimethyIphthalate
3-Nitroaniline
2,4-Dinitrophenol
4-Nitrophenol
Diethylphthalate
4-Nitroaniline
4,6-Dinitro-2-methyIpheno 1
N-Nitrosodiphenylamine
01-n-butyIphthalate
ButylbenzyIphthalate
3,3'-Dichlorobenzidine
bis(2-Ethylhexyl)phthalate
Di-n-octyIphthalate
2,4,6-Tribromopheno1
Nitrobenzene-d
SV D-43
6/91
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EXHIBIT D
METHOD FOR THE ANALYSIS OF LOW CONCENTRATION WATER FOR
PESTICIDES AND AROCLORS
PEST D-l 6/91
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Table of Contents
Page
SECTION I: Introduction PEST D-3
SECTION II:
Part A - Sample Storage and Holding
Tines PEST D-4
Part B - Equipment and Standards PEST D-5
SECTION III: Instrument Quality Control Procedures
and Requirements
Part A - Instrument Operating Conditions PEST 0-15
Part B - Calibration of the GC/ECD System PEST D-15
SECTION IV: Sample Preparation, Extraction and
Cleanup PEST D-27
SECTION V: Sample Analysis and Compound
Identification and Quantitation PEST D-35
SECTION VI: Sample Quality Control Procedures
and Requirements PEST D-44
PEST D-2
6/91
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SECTION I
INTRODUCTION
The analytical method that follows is designed to analyze water in order to
determine the presence and concentration of the chlorinated pesticides and
Aroclors found in the Target Compound List (Exhibit C). The majority of the
samples are expected to be from drinking water and well/ground water sources
around Superfund sites. The method can be used for determining analyte
concentrations as low as ten parts per trillion. The method is based on EPA
Method 608. Quality control requirements are incorporated in the method in
order to maximize GC/ECD sensitivity and column resolution and to minimize
contamination of the samples from laboratory sources.
Resolution difficulties have been associated with the following pairs of
compounds using this method:
o On a DB-608 or equivalent column, ODE and dieldrin; Methoxychlor and
Endrin ketone; and Endosulfan I and gamma-Chlordane.
o On a DB-1701 or equivalent column, Endosulfan I and gamma - Chlor dane; and
Methoxychlor and Endosulfan sulfate.
PEST D-3 6/91
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SECTION II
FART A - SAMPLE STORAGE AND HOLDING TIMES.
1. PROCEDURES FOR SAMyrfl STORAGE
The samples mist be protected from light and refrigerated at 4'C (±2*C)
from the tine of receipt until 60 days after delivery of a complete
reconciled sample data package. After 60 days the samples may be
disposed of in a manner that complies with all applicable regulations.
The samples must be stored in an atmosphere demonstrated to be free of
all potential contaminants and in a refrigerator used only for storage
of samples received under this contract.
Samples, sample extracts, and standards must be stored separately.
2. PROCEDURE TOR gAU^TJ; ETfBACf STORAGE
Sample extracts must be protected from light and stored at 4*0 (±2'C)
until 365 days after delivery of a complete data package.
Sample extracts must be stored in an atmosphere demonstrated to be free
of all potential contaminants.
Samples, sample extracts, and standards must be stored separately.
CONTRACT REOUTBifl* HOLDING TIMES
The extraction of all samples must be started within 5 days of the
Validated Time of Sample Receipt (VTSR) .
Analysis of samples must be completed within 40 days following the
stare of extraction.
PEST D-4 6/91
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PART B - ffinil'PMENT AND STANDARDS
3. SUMMARY OF METHOD
3.1 A one liter aliquot of sample is spiked with the surrogate solution and
extracted with methylene chloride by using a continuous liquid- liquid
extractor. The methylene chloride extract is dried and concentrated,
exchanged to hexane, cleaned up to remove interferences, and adjusted
to a final volume of 2.0 mL.
3.2 The hexane extract is injected onto two wide-bore capillary columns in
a gas chromatograph (GC) . The gas chromatograph is temperature
programmed to separate the pesticides and Aroclors which are then
detected with an electron capture detector (ECD) . Calibration and run
sequence specifications of the GC/ECD method apply independently to
both GC columns.
3.3 A single component pesticide is identified if a peak is detected within
its appropriate retention time window on each of two GC columns.
Quantitative analysis of pesticides/Aroclors must be accomplished by
the external standard method. Single component analytes and the
surrogates must be analyzed at three concentrations during the initial
calibration.
3.4 Toxaphene and Aroclors are identified primarily by pattern recognition,
but retention times of three to five major peaks must also be taken
into consideration. Single-point calibrations for multicomponent
analytes are sufficient for quantitation by this method. Standards for
identified Aroclors and Toxaphene must be run within 72 hours of the
sample analysis in which they were observed. These standards are used
to verify identification only; quantitation is based on the standards
analyzed during initial calibration.
4.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and sample processing hardware. These
contaminants lead to discrete artifacts or to elevated baselines in gas
chroma to grams. These materials must be routinely demonstrated to be
free from interferences under the sample preparation and analysis
conditions by analyzing instrument blanks and method blanks.
Interferences caused by phthalate esters can pose a major problem in
pesticide analysis. Because common flexible plastics contain varying
amounts of phthalates which are easily extracted during laboratory
operations, cross -contamination of glassware frequently occurs when
plastics are handled. Interferences from phthalates can best be
minimized by avoiding the use of such plastics in the laboratory.
4.2 Matrix interferences may be caused by contaminants that are co-
extracted from the sample. The extent of matrix interferences will
vary considerably from source to source, depending upon the nature of
the site being sampled. The cleanup procedures in Section 12 must be
used to remove such interferences in order to achieve the Contract
Required Quantitation Limits (CRQL).
PEST D-5 6/91
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5. APPARATUS AND
Brand names, suppliers, and part numbers are for illustrative purposes
only. No endorsement is implied. Equivalent performance may be
achieved using apparatus and materials other than those specified here,
but demonstration of equivalent performance meeting the requirements of
method is the responsibility of the Contractor.
5.1 Gas Chromatograph/Electron Capture Detector (GC/ECD)
5.1.1 Gas Chromatograph
5.1.1.1 The gas chromatograph (GO) system must regulate
temperature in order to give a reproducible
temperature program and have a flow controller that
maintains a constant column flow rate throughout the
temperature program. The system must be suitable
for splitless injection and have all required
accessories including syringes, analytical columns,
and gases.
5.1.1.2 Gas chromatographs that are available from some
manufacturers may have difficulty in meeting certain
method QC requirements because of Endrin and DDT
breakdown in the injector. This problem can be
minimized by operating the injector at 200-205'C,
using a Pvrex (not quartz) methyl silicone
deactivated injector liner, and deactivating any
metal parts in the injector with dichlorodimethyl
silane. In some cases, using a 0.25-inch packed
column injector converted for use with 0.53 mm
capillary columns works better than a Grob-type
injector. If a Grob-type injector is used, a 4 mm
liner may be required to meet breakdown criteria.
5.1.2 Gas Chromatograph Columns
5.1.2.1 Two wide-bore (0.53 mm ID) fused silica GC columns
are required. A separate detector is required for
each column. The specified analytical columns are a
DB-1701, 30 m x 0.53 mm ID, 1.0 urn film thickness,
Jfiff Scientific, Folsom, CA, and a DB-608, 30 m x
0.53 mm ID, 0.5 to 1.0 urn film thickness from J&tf
Scientific. Equivalent columns may be employed if
they meet the requirements in Section III.
5.1.2.2 Columns are mounted in 0.25-inch injector ports by
using glass adapters available from a variety of
commercial sources (J&W Scientific, Supelco, Inc.,
Hewlett-Packard, Varian, Inc., Perkin Elmer, or
equivalent). The two columns may be mounted into a
single injection port with a tee adapter, (Supelco,
Inc., Beliefonte, PA, Catalog No. 2-3660, or
equivalent). Use of this adapter allows
PEST D-6 6/91
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simultaneous injection onto both columns.
Laboratories should follow the manufacturer's
recommendation on mounting 0.53 mm capillaries into
injection ports.
S.I.3 The carrier gas for routine applications is helium.
Laboratories may choose to use hydrogen as a carrier gas, but
they must clearly identify its use in the SDG Narrative and on
all divider pages preceding raw chromatographic data in
submissions to SMO. Laboratories that choose to use hydrogen
are advised to exercise caution in its use. Use of a hydrogen
leak detector is highly recommended if hydrogen is used as a
carrier gas. All GO carrier gas lines must be constructed from
stainless steel or copper tubing. Non-polytetrafluoroethylene
(PTFE) thread sealants, or flow controllers with rubber
components are not to be used.
5.1.4 Electron Capture Detector - The makeup gas must be P-5, P-10
(argon/methane) or nitrogen according to the instrument
specification. The GC/ECD system must be in a room in which
the atmosphere has been demonstrated to be free of all
contaminants which may interfere with the analysis. The
instrument must be vented to outside the facility or to a
trapping system which prevents the release of contaminants into
the instrument room.
5.1.5 Data System - A data system must be interfaced to the GC/ECD.
The data system must allow the continuous acquisition of data
throughout the duration of the chromatographic program and must
permit, at the minimum, the output of time vs. intensity (peak
height or peak area) data. Also, the data system must be able
to rescale chromatographic data in order to report
chromatograms meeting the requirements listed within this
method.
5.2 Glassware - A set of glassware sufficient to meet contract requirements
must be reserved for exclusive use in this contract.
5:2.1 Continuous liquid-liquid extractors equipped with Teflon or
glass connecting lines for use with methylene chloride
(Hershberg-Wolf Extractor, Ace Glass Company, Vineland, NJ, P/N
6841-10, or equivalent).
5.2.2 Concentrator tube - Kude ma-Danish, 10 mL, graduated (Kontes,
Vineland, NJ K-570050-1025, or equivalent).
5.2.3 Evaporative flask - Kuderna-Danish, 500 mL (Kontes K-570001 -
0500, or equivalent). Attach to concentrator tube with
springs.
5.2.4 Snyder column - Kuderna-Danish, three-ball macro (Kontes
K-50300-0121, or equivalent).
PEST D-7 6/91
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5.2.5 Drying column, chromatographic column approximately 400 mm long
x 19 mm ID. with coarse frit. (Substitution of a small pad of
disposable Pyrex glass wool for the frit will help prevent
cross-contamination of sample extracts.)
5.2.6 Pipet, Volumetric 1.00 mL or 2.00 mL (optional).
5.2.7 Microsyringe, 1.0 uL and larger, 0.006 inch ID needle.
5.2.8 Syringe, 1.00 mL or 2.00 mL (optional).
5.2.9 Flask, Volumetric 10.00 mL.
5.2.10 Flask, Volumetric 1.00 mL or 2.00 mL (optional).
5.2.11 Snyder column, micro two or three ball with a 19 mm ground
glass joint.
5.2.12 Glass vials, minimum of 20 mL, with screw cap and Teflon or
aluminum foil liner.
5.2.13 Vials, 10 mL, with screw cap and Teflon liner (optional).
5.2.14 Vials and caps, 1 or 2 mL for GC auto sampler.
5.2.15 Bottle or test tube, 50 mL with Teflon-lined screw cap for
sulfur removal.
5.2.16 Centrifuge tubes, calibrated, 12 mL, for sulfur removal.
5.2.17 Micropipet, 250 uL, with disposable tips.
5.3 pH Paper, wide range.
5.4 Boiling chips.
5.4.1 Silicon carbide boiling chips, approximately 10 to 40 mesh.
Heat the chips to 400*0 for 30 minutes or solvent rinse before
use.
5.4.2 Teflon boiling chips (optional). Solvent rinse the chips
before use.
5.5 Water bath, heated, with concentric ring cover, capable of temperature
control. NOTE: To prevent the release of solvent fumes into the
laboratory, the water bath must be used in a hood.
5.6 Balance. Analytical, capable of accurately weighing ±0.0001 g. The
balances must be calibrated with class S weights once per each 12-hour
workshift. The balances must also be annually checked by a certified
technician.
PEST D-8 6/91
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5.7 Nitrogen evaporation device equipped with a heated bath that can be
maintained at 30 to 35*C (N-Evap by Organomation Associates, Inc.,
South Berlin, HA, or equivalent). To prevent the release of solvent
fumes into the laboratory, the nitrogen evaporation device must be used
in a hood.
5.8 Florisil Cleanup Equipment
5.8.1 Florisil bonded silica. 1-g cartridges with stainless steel or
Teflon frits, Catalog No. 694-313 (Analytichem, 24201 Frampton
Ave., Harbor City, CA, or equivalent).
5.8.2 Vacuum system for eluting multiple cleanup cartridges. Vac
Elute Manifold, Analytichem International (J.T. Baker, or
Supelco) or equivalent.
5.8.3 Vacuum trap made from a 500 mL sidearm flask fitted with a one-
hole stopper and glass tubing.
5.8.4 Vacuum pressure gauge.
5.8.5 Rack for holding 10 mL volumetric flasks in the manifold.
5.9 Mechanical shaker or mixer, for sulfur removal.
6.
6.1 Sodium sulfate, granular-anhydrous reagent grade, heated at 400"C for 4
hours, or at 120*C for 16 hours, cooled in a desiccator, and stored in
a glass bottle. Each lot must be extracted with hexane and analyzed by
GC/ECD to demonstrate that it is free of interference before use (J.T.
Baker anhydrous granular, Catalog No. 3375, or equivalent).
6.2 Methylene chloride, hexane, acetone, toluene, iso-octane, and methanol
(optional), pesticide quality, or equivalent. It is recommended that
each lot of solvent be analyzed to demonstrate that it is free of
interference before it is used. Methylene chloride must be certified
as acid free or must be tested to demonstrate that it is free of
hydrochloric acid. Acidic methylene chloride must be passed through
basic alumina and then demonstrated to be free of hydrochloric acid.
6.3 Mercury, triple distilled, for sulfur clean-up.
6.4 Copper powder (optional), fine, granular (Mallinckrodt 4649 or
equivalent). Copper may be used instead of mercury for sulfur clean-
up. Remove oxides by treating with dilute nitric acid, rinse with
distilled water to remove all traces of acid, rinse with acetone, and
dry under a stream of nitrogen.
6.5 Sodium hydroxide solution (10 N) . Carefully dissolve 40 g of NaOH in
reagent water and dilute the solution to 100 mL.
6.6 Concentrated sulfuric acid, (Sp. Gr. 1.84).
PEST D-9 6/91
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6.7 Nitric acid, dilute, for sulfur removal with copper.
6.8 Reagent water. Reagent water is defined as a water in which no target
analyte is observed at the CRQL for that compound.
6.8.1 Reagent water nay be generated by passing tap water through a
carbon filter bed containing about 453 g (1 Ib.) of activated
carbon (Calgon Corp., Filtrasorb-300, or equivalent).
6.8.2 Reagent water may be generated using a water purification
system (Millipore Super -Q or equivalent) .
6 . 9 Ten percent acetone in hexane (v/v) . Prepare by f*«M»ig 10 . 0 mL of
acetone to 90.0 mL of hexane. NOTE: Prepare this mixture accurately
or the results from the Florisil cartridge cleanup will be adversely
affected. Vater in the acetone will also adversely affect Florisil
performance.
7. STANDARDS
7.1 The Contractor must provide all standards to be used with this
contract. These standards may be used only after they have been
certified according to the procedure in Exhibit E. The Contractor must
be able to verify that the standards are certified. Manufacturer's
certificates of analysis must be retained by the Contractor and
presented upon request.
7.2 Stock standard solutions (1.00 ug/uL) - Stock standard solutions may be
purchased as certified solutions or prepared from pure standard
materials.
7.2.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure material. Dissolve the material in toluene,
dilute to volume in a 10 mL volumetric flask with toluene or
acetone. Larger volumes may be used at the convenience of the
analyst.
7.2.2 When compound purity is assayed to be 97 percent or greater,
the weight may be used without correction to calculate the
concentration of the stock solution. If the compound purity is
assayed to be less than 97 percent, the weight must be
corrected when calculating the concentration of the stock
solution.
7.2.3 Fresh stock standards must be prepared once every twelve
months, or sooner, if standards have degraded or concentrated.
Stock standards must be checked for signs of degradation or
concentration just prior to preparing working standards from
them.
PEST D-10 6/91
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7.3 Working Standards
7.3.1 Surrogate Standard Spiking Solution
The surrogates, tetrachloro-m-xylene and decachlorobiphenyl,
are added to all standards, samples, and blanks. Prepare a
surrogate spiking solution of 0.20 ug/mL of each of the two
compounds in acetone. The solution should be checked
frequently for stability. The solution oust be replaced after
six months or at an earlier time, if the solution has degraded
or concentrated.
7.3.2 Resolution Check Mixture
The Resolution Check Mixture is composed of the pesticides and
surrogates at the concentrations listed below in hexane or iso-
octane. The mixture must be prepared every six months or
sooner, if the solution has degraded or concentrated.
Compounds Concentration fng/mL)
gamma-Chlordane 10.0
Endosulfan I 10.0
p,p'-DDE 20.0
Dieldrin 20.0
Endosulfan sulfate 20.0
Endrin ketone 20.0
Methoxychlor 100.0
Tetrachloro-m-xylene 20.0
Decachlorobiphenyl 20.0
7.3.3 Performance Evaluation Mixture
The Performance Evaluation Mixture is prepared in hexane or
iso-octane as listed below. The PEM must be prepared weekly or
more often, if the solution has degraded or concentrated.
ComDounds Concentration (tip /m1L)
gamma-BHC 10.0
alpha-BHC 10.0
4,4'-DDT 100.0
beta-BHC 10.0
Endrin 50.0
Methoxychlor 250.0
Tetrachloro-m-xylene 20.0
Decachlorob iphenyl 20.0
7.3.4 Single Component Pesticides
The Individual Standard Mixture solutions must be prepared in
either hexane or iso-octane. The concentrations of the
pesticides in the low point standard mixtures are given below.
The midpoint concentration must be 4 times the low point
PEST D-ll 6/91
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concentration for each analyte, including the surrogates. The
high concentration must be at least 16 times the low point
concentration for each analyte, including the surrogates, but a
higher concentration may be chosen by the Contractor. The high
point concentration defines the upper end of the concentration
range for which the calibration is valid. The solution oust be
prepared every 6 months or sooner, if the solution has degraded
or concentrated.
Low Point
Concentration
(ng/aLl
Individual
Standard Mix A
alpha-BHC 5.0
Heptachlor 5.0
gamma-BBC 5.0
Endosulfan I 5.0
Dieldrin 10.0
Endrin 10.0
p.p'-DDD 10.0
p.p'-DDT 10.0
Methoxychlor 50.0
Tetrachloro-m-xylene 5.0
Decachlorob ipheny1 10.0
Individual
Standard Mix B
beta-BHC
delta- BHC
Aldrin
Heptachlor epoxide
alpha-Chlordane
gamna-Chlordane
p.p'-DDE
Endosulfan sulfate
Endrin aldehyde
Endrin ketone
Endosulfan II
Tetrachloro-m-xylene
Decachlorobiphenyl
Low Point
Concentration
(ng/mL)
.0
.0
.0
.0
.0
.0
5.
5.
5.
5.
5.
5.
10.0
10.0
10.0
10.0
10.0
5.0
10.0
7.3.5 Multicomponent Standards
Toxaphene and Aroclor standards must be prepared individually
except for Aroclor 1260 and Aroclor 1016 which nay be combined
in one standard mixture. The calibration standards for the
Aroclors must be prepared at concentrations of 100 ng/mL,
except for Aroclor 1221 which must be prepared at 200 ng/mL.
Toxaphene must be prepared at 500 ng/mL. All multicomponent
standards must contain the surrogates at 20.0 ng/mL. The
Aroclor and Toxaphene solutions must be prepared in hexane or
iso-octane. Each solution must be prepared every 6 months, or
sooner, if the solution has degraded or concentrated.
7.3.6 Florisil Cartridge Check Solution
Prepare a 0.10 ug/mL solution of 2,4,5-trichlorophenol in
acetone. The solution must be prepared every 6 months, or
sooner, if the solution has degraded or concentrated.
7.3.7 Laboratory Control Sample (LCS) Spiking Solution
Prepare a laboratory control sample (LCS) spiking solution that
contains each of the analytes at the concentrations listed
below in methanol or acetone. The LCS solution must be
prepared every six months or sooner, if the solution has
degraded or concentrated.
PEST D-12
6/91
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Compounds Concentration f*'g/"'Tr)
gamma-BHC 0.10
Heptachlor epoxide 0.10
Dieldrin 0.20
4,4'-DDE 0.20
Endrin 0.20
Endosulfan sulfate 0.20
gamna-Chlordane 0.10
7.4 Storage of Standards
7.4.1 Store the stock and secondary standard solutions at -10*C to -
20*C in Teflon-lined screw-cap amber bottles.
7.4.2 Store the working standard solutions at 4*C (±2'C) in Teflon-
lined screw-cap amber bottles. The working standards must be
checked frequently for signs of degradation or evaporation.
7.4.3 Protect all standards from light.
7.4.4 Samples, sample extracts, and standards must be stored
separately.
PEST D-13 6/91
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SECTION in
mSTBIJMEHT QUALITY COHTROL PROCEDURES AHD REQUIREMEHTS
PEST D-14 6/91
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PART A - INSTRUMENT OPERATING CONDITIONS
8. GAS CHROMATOGRAPH / ELECTRON CAPTURE DETECTOR
The following are the gas chromatographic analytical conditions. The
conditions are recommended unless otherwise noted.
Carrier Gas: Helium
Column Flow: 5 aL/min
Make-up Gas: Argon/Methane (P-5 or P-10) or N2
(required)
Injector Temperature: > 200*C (required)
Injection Technique: On-column
Injection Volume: 1 or 2 ul (see note below)
Injector: Grob-type, splitless
Initial Temperature: 150*C
Initial Hold Time: 1/2 min
Temperature Ramp: S"C to 6'C/ain
Final Temperature: 275*C
Final Hold Time: After Decachlorobiphenyl has eluted
(approximately 10 minutes)
Optimize GC conditions for analyte separation and sensitivity. Once
optimized, the same GC conditions must be used for the analysis of all
standards, samples, blanks, performance evaluation samples and
laboratory control samples. NOTE: Manual injections must be 2.0 uL.
Auto injectors may use 1.0 uL volumes. The same injection volume must
be used for all standards, blanks, and samples.
The linearity of the ECD may be greatly dependent on the flow rate of
the make-up gas. Care must be taken to maintain stable and appropriate
flow of make-up gas to the detector.
Cold (ambient temperature) on-column injectors that allow injection
directly onto a 0.53 mm ID column may be used as long as the acceptance
criteria for resolution, calibration, and analyte breakdown are met.
PEST D-15 6/91
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PART B - CALIBRATION OF THE GC/ECD SYSTEM
9. INITIAL CALIBRATION
9.1 Summary
Prior to sample analysis, each GC/ECD system oust be initially
calibrated at a minimum of three concentrations for single component
analytes in order to determine instrument sensitivity and the linearity
of GC response. Each multicomponent analyte is analyzed at one
concentration.
9.2 Frequency
Each GC/ECD system must be initially calibrated upon award of the
contract, whenever major instrument maintenance or modification is
performed (e.g., column replacement or repair, cleaning or replacement
of ECD, etc.) , or if the calibration verification technical acceptance
criteria have not been met.
9.3 Procedure
9.3.1 Set up the GC/ECD system as described in Section 8.
9.3.2 Prepare the initial calibration standards using the procedures,
the analytes, and the concentrations according to Section 7.
9.3.3 All standards, samples, and blanks must be allowed to warm to
ambient temperature before preparation or analysis.
9.3.4 Analyze the initial calibration sequence as given below. NOTE:
Steps 16 and 17 are used as part of the calibration
verification as well (see Section 10).
INITIAL CALIBRATION SEQUENCE
1. Resolution Check
2. Performance Evaluation Mixture
3. Aroclor 1016/1260
4. Aroclor 1221
5. Aroclor 1232
6. Aroclor 1242
7. Aroclor 1248
8. Aroclor 1254
9. Toxaphene
10. Low Point Standard A
11. Low Point Standard B
12. Midpoint Standard A
13. Midpoint Standard B
14. High Point Standard A
15. High Point Standard B
16. Instrument Blank
17. Performance Evaluation Mixture
PEST D-16 6/91
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9.4 Calculations
9.4.1 For each single component pesticide and surrogate, a retention
time (RT) is measured in each of three of the calibration
standards analyses (low point, midpoint, high point) during the
initial calibration for Individual Standard Mixture A and
Individual Standard Mixture B. The RT for the surrogates is
measured from the Individual Standard Mixture A analyses. The
mean RT is calculated as the average of the three values.
Calculate a mean absolute retention time (RT) for each single
component pesticide and surrogate using Equation D.22.
n
EQ. D.22. RT - Z
1-1
RT - Mean absolute retention time of analyte.
RTi - Absolute retention time of analyte.
n - Number of measurements (3).
9.4.2 A retention time window is calculated for each single component
analyte and surrogate and for the major peaks (3 to 5) of each
multicomponent analyte by using Table D.13. Windows are
centered around the average absolute retention time for the
analyte established during the initial calibration.
TABLE D.13
RETENTION TIME WINDOWS FOR SINGLE AND MULTICOMPONENT
ANALYTES AND SURROGATES.
Compound Identification
Compound Window (minutes)
alpha-BHC ±0.05
beta-BHC ±0.05
gamma-BBC ±0.05
delta-BHC ±0.05
Heptachlor ±0.05
Aldrin ±0.05
alpha-Chlordane ±0.07
gamma-Chlordane ±0.07
Heptachlor epoxide ±0.07
Dieldrin ±0.07
Endrin ±0.07
Endrin aldehyde ±0.07
Endrin ketone ±0.07
DDD ±0.07
DDE ±0.07
DDT ±0.07
PEST D-17 6/91
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TABLE D.13 (continued)
RETENTION TIME WINDOWS FOR SINGLE AND MULTICOMPONENT
ANAIYTES AND SURROGATES.
Compound Identification
Compound Window (minutes)
Endosulfan I ±0.07
Endosulfan II ±0.07
Endosulfan sulfate ±0.07
Hethoxychlor ±0.07
Aroclors ±0.07
Toxaphene ±0.07
Tetrachloro-m-xylene ±0.OS
Decachlorobiphenyl ±0.10
9.4.3 The linearity of the instrument is determined by calculating a.
percent relative standard deviation (%RSD) of the calibration
factors from a three-point calibration curve for each of the
single component pesticide and surrogates. Either peak area or
peak height may be used to calculate calibration factors used
in the %RSD equation. For example, it is permitted to
calculate linearity for endrin based on peak area and to
calculate linearity for aldrin based on peak height. It is not
permitted within a %RSD calculation for an analyte to use
calibration factors calculated from both peak area and peak
height. For example, it is not permitted to calculate the
calibration factor for the low point standard for endrin using
peak height and calculate the midpoint and high point standard
calibration factors for endrin using peak area.
9.4.3.1 Calculate the calibration factor for each single
component pesticide and surrogate over the initial
calibration range using Equation D.23.
9.4.3.2 Calculate the mean and the %RSD of the calibration
factors for each single component pesticide and
surrogate over the initial calibration range using
Equation D.24 and Equation D.25.
EQ. D.23 CF — Peak Area (or Height) of the Standard
Mass Injected (ng)
n
— 2 CF*
EQ. D.24 CF - i-1
EQ. D.25 % RSD - SDcF
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-------
%D - Percent Difference
~ nominal concentration of each analyte
ccalc ~ Calculated concentration of each analyte from the
analyses of the standard
9.4.7 Calculate the resolution between the analytea in the Resolution
Check Mixture and the midpoint concentrations of individual
standard mixtures A and B using Equation D.31.
EQ. D.31 % Resolution - jj * 100%
V - Depth of the valley between the two peaks. The depth of
the valley is measured along a vertical line from the level
of the apex of the shorter peak to the floor of the valley
between the two peaks.
H - Height of the shorter of the adjacent peaks
9.5 Technical Acceptance Criteria For Initial Calibration
All initial calibration technical acceptance criteria apply
independently to both GC columns.
9.5.1 The initial calibration sequence must be analyzed according to
the procedure and in the order listed in Section 9.3, at the
concentrations listed in Section 7, and at the frequency listed
in Section 9.2. The GC/ECD operating conditions optimized in
Section 8 must be followed.
9.5.2 The resolution between two adjacent peaks in the Resolution
Check Mixture must be greater than or equal to 60.0%. On the
DB-1701 GC column, resolution difficulties are most likely
between Endosulfan I and gamma- Chlordane and between
Methoxychlor and endosulfan sulfate. On the DB-608 GC column,
the poorest resolution will probably be between p.p'-DDE and
Dieldrin; Methoxychlor and Endrin ketone; and Endosulfan I and
gamna- Chlordane .
9.5.3 All single component pesticides and surrogates in both runs of
the Performance Evaluation Mixture (PEM) must be 100 percent
resolved.
9.5.4 The absolute retention times of each of the single component
pesticides and surrogates in both runs of the PEM must be
within the retention time window determined from the three -
point initial calibration in paragraph 9.4.2.
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9.S.5 The absolute value of the percent difference of the calculated
amount and the true amount for each of the single component
pesticides and surrogates in both of the PEM runs must be less
than or equal to 25.0 percent, using Equation D.30.
9.5.6 The percent breakdown of DOT and endrin in each of the PEM runs
must be less than or equal to 20.0 percent. The combined
breakdown of DDT and endrin must be less than or equal to 30.0
percent.
9.5.7 The %RSD of the calibration factors for each single component
target compound must be less than or equal to 20.0 percent,
except as noted. The %RSD of the calibration factors for the
two surrogates must be less than or equal to 30.0 percent. Up
to two single component target compounds (but not surrogates)
may exceed the 20.0 percent limit for %RSD, but those compounds
must have a %RSD of less than or equal to 30.0 percent.
9.5.8 The resolution between any two adjacent peaks in the midpoint
concentrations of Individual Standard Mixtures A and B in the
initial calibration must be greater than or equal to 90.0
percent.
9.5.9 All instrument blanks must meet the technical acceptance
criteria in Paragraph 20.3.4.
9.5.10 The identification of single component pesticides by gas
chromatographic methods is based primarily on retention time
data. The retention time of the apex of a peak can only be
verified from an on-scale chromatogram. The identification of
multicomponent analytes by gas chromatographic methods is based
primarily on recognition of patterns of retention times
displayed on a chromatogram. Therefore, the following
requirements apply to all data presented for single component
and multicomponent analytes.
9.5.10.1 The chromatograms that result from the analyses of
the Resolution Check Mixture, the Performance
Evaluation Mixture, and Individual Standard Mixtures
A and B during the initial calibration sequence must
display the single component analytes present in
each standard at greater than 10 percent of full
scale but less than 100 percent of full scale.
9.5.10.2 The chromatograms for at least one of the three
analyses each of Individual Standard Mixtures A and
B from the initial calibration sequence must display
the single component analytes at greater than 50
percent and less than 100 percent of full scale.
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9.5.10.3 The ehromatograms of the standards for the
multieomponent analytes analyzed during the initial
calibration sequence must display the peaks chosen
for identification of each analyte at greater than
25 percent and less than 100 percent of full scale.
9.5.10.4 For all Resolution Check Mixtures, Performance
Evaluation Mixtures, Individual Standard Mixtures,
and blanks, the baseline of the chromatogram must
return to below 50 percent of full scale before the
elution time of alpha-BHC, and return to below 25
percent of full scale after the elution time of
alpha-BHC and before Che elution time of
decachlorobiphenyl.
9.5.10.5 If a chromatogram is replotted electronically to
meet requirements, the scaling factor used must be
displayed on the chromatogram.
9.5.10.6 If the chromatogram of any standard needs to be
replotted electronically to meet these requirements,
both the initial chromatogram and the replotted
chromatogram must be submitted in the data package.
9.6 Corrective Action
9.6.1 If the technical acceptance criteria for the initial
calibration are not met, inspect the system for problems. It
may be necessary to change the column, bake out the detector,
clean the injection port, or take other corrective actions to
achieve the acceptance criteria.
9.6.2 Contamination should be suspected as a cause if the detector
cannot achieve acceptable linearity using this method. In the
case of low level contamination, baking out the detector at
elevated temperature (350*C) should be sufficient to achieve
acceptable performance. In the case of heavy contamination,
passing hydrogen through the detector for 1-2 hours at elevated
temperature may correct the problem. In the case of severe
contamination, the detector may require servicing by the ECO
manufacturer. DO NOT OPEN THE DETECTOR. THE ECD CONTAINS
RADIOCHEMICAL SOURCES.
9.6.3 If a laboratory decontaminates a detector using elevated
temperature, the ECD electronics must be turned off during the
bake out procedure.
9.6.4 After bake out or hydrogen reduction, the detector must be
recalibrated using the initial calibration sequence.
PEST D-22 6/91
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9.6.5 Initial calibration technical acceptance criteria MOST be met
before any samples (including the LCS and PES) or required
blanks are analyzed. Any samples (including the LCS and PES)
or required blanks analyzed after the initial calibration
criteria have not been met will require reanalysis at no
additional cost.
10. CAVpfltftTIOH VERIFICATION
10 . 1 Summary
Three types of analyses are used to verify the calibration and evaluate
instrument performance. The analyses of instrument blanks, Performance
Evaluation Mixtures (PEM) , and the mid point concentration of
Individual Standard Mixtures A and B constitute the continuing
calibration. Sample data are not acceptable unless bracketed by
acceptable analyses of instrument blanks, PEM, and both Individual
Standard Mixtures A and B.
10.2 Frequency
10.2.1 An instrument blank and the Performance Evaluation Mixture must
bracket one end of a 12 -hour period during which sample data
are collected, and a second instrument blank and the mid point
concentration of Individual Standard Mixtures A and B must
bracket the other end of the 12 -hour period.
10.2.2 For the 12 -hour period immediately following the initial
calibration sequence, the instrument blank and the PEM that are
the last two steps in the initial calibration sequence bracket
the front end of that 12 -hour period. The injection of the
instrument blank starts the beginning of that 12 -hour period
(see Section 13.3). Samples may be injected for 12 hours from
the injection of the instrument blank. The first three
injections ^imnad^fltelY after that 12 -hour period must be an
instrument blank, Individual Standard Mixture A, and Individual
Standard Mixture B. The instrument blank must be analyzed
first, before either standard. The Individual Standard
Mixtures may be analyzed in either order (A,B or B,A).
10.2.3 The analyses of the instrument blank and Individual Standard
Mixtures A and B immediately following one 12 -hour period may
be used to begin the subsequent 12 -hour period, provided that
they meet the acceptance criteria in Section 10.5. In that
instance , the subsequent 12 -hour period must be bracketed by
the acceptable analyses of an instrument blank and a PEM, in
that order. Those two analyses may in turn be used to bracket
the front end of yet another 12 -hour period. This progression
may continue every 12 hours until such time as any of the
instrument blanks, PEMs, or Individual Standard Mixtures fails
to meet the acceptance criteria in Section 10.5. The 12 -hour
time period begins with the injection of the instrument blank.
Standards (PEM or Individual Standard Mixtures) , samples and
PEST D-23 6/91
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required blanks may be injected for 12:00 hours from the time
of injection of the instrument blank.
10.2.4 If more than 12 hours have elapsed since the injection of the
instrument blank that bracketed a previous 12-hour period, an
acceptable instrument blank and PEM must be analyzed in order
to start a new sequence. This requirement applies even if no
analyses were performed since that standard(s) was injected.
10.2.5 After a break in sample analyses, the laboratory may only
resume the analysis of samples using the current initial
calibration for quantitation by analyzing an acceptable
instrument blank and a PEM.
10.2.6 If the entire 12-hour period is not required for the analyses
of all samples to be reported and all data collection is to be
stopped, the incomplete sequence must be ended with either the
instrument blank/PEM combination or the instrument
blank/Individual Standard Mixtures A and B combination,
whichever was due to be performed at the end of 12-hour period.
10.3 Procedure
10.3.1 Set up the GC/ECD system as described in Section 8.
10.3.2 Prepare the PEM standard and the mid point concentration of
Individual Standard Mixtures A and B as in Section 7, and the
instrument blank as in Section 20.3.
10.3.3 The PEM, the Individual Standard Mixtures, and the instrument
blank must be at ambient temperature at the time of preparation
and analysis.
10.3.4 Analyze the PEM, instrument blank, and the mid point
concentration of Individual Standard Mixtures A and B at the
required frequencies (Sections 10.2 and 13.3).
10.4 Calculations
10.4.1 For each analysis of the Performance Evaluation Mixture used to
demonstrate continuing calibration, calculate the percent
difference between the amount of each analyte (including the
surrogates) found in the PEM and the nominal amount, using
Equations D.26 and D.30.
10.4.2 For each analysis of the Performance Evaluation Mixture used to
demonstrate continuing calibration, calculate the percent
breakdown of Endrin and DDT, and the combined breakdown, using
Equations D.26, D.27, D.28, and D.29.
10.4.3 For each analysis of the mid point concentration of Individual
Standard Mixtures A and B used to demonstrate continuing
calibration, calculate the percent difference between the
amount of each analyte (including the surrogates) found in the
PEST D-24 6/91
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standard mixture and the nominal amount, using Equations D.26
and D.30. Do not attempt to calculate the breakdown of Endrin
and DDT in the Individual Standard Mixtures, as these standards
contain the breakdown products as well as the parent compounds.
10.5 Technical Accepcance Criteria For Calibration Verification
All calibration verification technical acceptance criteria apply
independently to both columns.
10.5.1 The PEMs, Individual Standard Mixtures, and instrument blanks
must be analyzed at the required frequency (paragraph 10.2),
using the procedure in paragraph 10.3, on a GC/ECD system that
has met the initial calibration technical acceptance criteria.
10.5.2 All single component pesticides and surrogates in the
Performance Evaluation Mixtures used to demonstrate continuing
calibration must be 100 percent resolved. The resolution
between any two adjacent peaks in the midpoint concentrations
of Individual Standard Mixtures A and B in the initial
calibration must be greater than or equal to 90.0 percent.
10.5.3 The absolute retention time for each of the single component
pesticides and surrogates in the PEMs and mid point
concentration of the Individual Standard Mixtures used to
demonstrate continuing calibration must be within the retention
time windows determined from the three-point initial
calibration in paragraph 9.4.2.
10.5.4 The absolute value of the percent difference of the calculated
amount and the true amount for each of the single component
pesticides and surrogates in the PEM and mid point
concentration of the Individual Standard Mixtures used to
demonstrate continuing calibration must be less than or equal
to 25.0 percent, using Equation D.30.
10.5.5 The percent breakdown of DDT and endrin in the PEM must be less
than or equal to 20.0 percent each on both columns. The
combined breakdown of DDT and endrin must be less than or equal
to 30.0 percent on both columns.
10.5.6 All instrument blanks must meet the technical acceptance
criteria in Paragraph 20.3.4.
10.5.7 The identification of single component pesticides by gas
chromatographic methods is based primarily on retention time
data. The retention time of the apex of a peak can only be
verified from an on-scale chromatogram. The identification of
multicomponent analyses by gas chromatographic methods is based
primarily on recognition of patterns of retention times
displayed on a chromatogram. Therefore, the following
requirements apply to all data presented for single component
and multicomponent analytes.
PEST D-25 6/91
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10.5.7.1 The chromatograas that result from the analyses of
the Performance Evaluation Mixture and the
Individual Standard Mixtures must display the single
component analytes present in each standard at
greater than 10 percent of full scale but less than
100 percent of full scale.
10.5.7.2 For any PEM, Individual Standard Mixture, or blank,
the baseline of the chrooatogram must return to
below 50 percent of full scale before the elution
time of alpha-BHC, and return to below 25 percent of
full scale after the elution time of alpha-BHC and
before the elution time of decachlorobiphenyl.
10.5.7.3 If a chromatogram is replotted electronically to
meet these requirements, the scaling factor used
must be displayed on the chromatogram.
10.5.7.4 If the chromatogram of any standard or blank needs
to be replotted electronically to meet these
requirements, both the initial chromatogram and the
replotted chronatogram(s) must be submitted in the
data package.
10.6 Corrective Action.
10.6.1 If the technical acceptance criteria for the calibration
verification are not met, inspect the system for problems and
take corrective action to achieve the acceptance criteria.
10.6.2 Major corrective actions such as replacing the GC column or
baking out the detector will require that a new initial
calibration be performed and meets the technical acceptance
criteria.
10.6.3 Minor corrective actions may not require performing a new
initial calibration, provided that a new analysis of the
standard (PEM or Individual Mixtures) that originally failed
the criteria and an associated instrument blank immediately
after the corrective action do meet all the acceptance
criteria.
10.6.4 If a Performance Evaluation Mixture or Individual Standard
Mixture does not meet the technical acceptance criteria listed
above, it must be reinjected immediately. If the second
injection of the FEM or Individual Standard Mixture meets the
criteria, sample analysis may continue. If the second
injection does not meet the criteria, all data collection must
be stopped. Appropriate corrective action must be taken, and a
new initial calibration sequence must be run before more sample
data are collected.
PEST D-26 6/91
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10.6.5 If an instrument blank does not meet the technical acceptance
criteria listed in Paragraph 20.3.4, all data collection must
be stopped. Appropriate corrective action must be taken to
clean out the system, and an acceptable instrument blank must
be analyzed before more sample data are collected.
10.6.6 Analysts are cautioned that running an instrument blank and a
Performance Evaluation Mixture or Individual Standard Mixtures
once every 12 hours are the minimum contract requirements.
Late eluting peaks may carry over from one injection to the
next if highly complex samples are analyzed or if the GC
conditions are unstable. Such carryover is unacceptable.
Therefore, it may be necessary to run instrument blanks and
standards more often to avoid discarding data.
10.6.7 If a successful instrument blank and FEM cannot be run after an
interruption in analysis (Paragraph 10.2.5), an acceptable
initial calibration must be run before sample data may be
collected. All acceptable sample analyses must be preceded and
followed by acceptable standards and instrument blanks, as
described in Section 10.2.
10.6.8 Calibration verification technical acceptance criteria must be
met before any samples (including LCS, PES) and required blanks
are reported. Any samples, including LCS and PES required with
a calibration verification which did not meet the technical
acceptance criteria will require reanalysis at no additional
cost.
PEST D-27 6/91
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SECTION IV
SAMPLE FHEPABATION, EXTRACTION, AHD CLEAHDF
PEST D-28 6/91
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11. SUMMARY
11.1 This method is designed for analysis of samples that contain low
concentrations of the pesticides and Aroclors listed in Exhibit C. The
majority of the samples are expected to come from drinking water
sources and well/ground water around Superfund sites. If, upon
inspection of a sample, the Contractor suspects that the sample is not
amenable to this method, contact SMO for instructions.
12. PROCEDURE
12.1 Extraction
Continuous Liquid-Liquid Extraction is required for the extraction of
the samples.
12.1.1 Add methylene chloride (100 to 250 mL) to the bottom of the
extractor and fill it to a depth of at least one inch above the
bottom sidearm.
12.1.2 Measure out each 1.0 liter sample aliquot in a separate 1 liter
graduated cylinder. Measure and record the pH of the sample
with wide range pH paper and adjust the pH to between 5 and 9
with 10 N sodium hydroxide or concentrated sulfuric acid, if
required. Samples requiring pH adjustment must be noted in the
SDG Narrative. Transfer the sample aliquot into the continuous
extractor.
12.1.3 Using-a micropipet with disposable tip, add 200 uL of the
surrogate solution to all samples and method blanks.
12.1.4 Adjust the level of methylene chloride in the extractor so that
the bottom sidearm is half filled with solvent.
12.1.5 If the sample was received in a 1 liter container, rinse the
empty container with 60 mL of methylene chloride after taking
the sample aliquot. Add the rinsate to the continuous
extractor.
12.1.6 Add sufficient methylene chloride to the distilling flask to
ensure proper solvent cycling during operation. Extract the
solution for 18 hours. Allow to cool, then detach the
distillation flask and label.
12.2 Extract Drying and Concentration
12.2.1 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10
mL concentrator tube to a 500 mL evaporative flask. Other
concentration devices or techniques may be used in place of the
K-D, if equivalency is demonstrated for all the target
pesticides and Aroclors listed in Exhibit C.
PEST D-29 6/91
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12.2.2 Pour the extract through a drying column containing about 10 cm
of anhydrous granular sodium sulfate and collect the extract in
the K-D concentrator. Rinse the Erlenneyer flask and the
sodium sulfate with at least two additional 20 to 30 mL
portions of methylene chloride to complete the quantitative
transfer.
12.2.3 Add one or two clean boiling chips to the evaporative flask and
attach a three-ball Snyder column. Pre-wet the Snyder column by
adding about 1 mL of methylene chloride to the top of the
column. Place the K-D apparatus on a hot water bath (60-80*0)
so that the concentrator tube is partially immersed in the hot
water and the entire lower rounded surface of the flask is
bathed with hot vapor. Adjust the vertical position of the
apparatus and the water temperature as required to complete the
concentration in 15 to 30 minutes. At the proper rate of
distillation, the balls of the column will actively chatter,
but the chambers will not flood with condensed solvent. When
the apparent volume of liquid reaches 3 to 5 mL, remove the K-D
apparatus. Allow it to drain and cool for at least 10 minutes.
DO NOT ALLOW THE EVAPORATOR TO GO DRY.
12.2.4 Proceed with the solvent exchange to hexane.
12.3 Solvent Exchange To Hexane
12.3.1 Momentarily remove the three-ball Snyder column, add 50 mL of
hexane and a new boiling chip, and reattach the Snyder column.
Pre-wet the column by adding about 1 mL of hexane to the top.
Concentrate the solvent extract as before. When the apparent
volume of liquid reaches 1 mL, remove the K-D apparatus and
allow it to drain and cool for at least 10 minutes. DO NOT
ALLOW THE EVAPORATOR TO GO DRY.
12.3.2 Remove the Snyder column; using 1 to 2 mL of hexane, rinse the
flask and its lower joint into the concentrator tube.
12.3.3 Use the micro Snyder column or the nitrogen blowdown technique
(Section 12.5) to concentrate the hexane extract to 1.0 mL.
12.4 Extract Cleanup
12.4.1 The two cleanup procedures specified in this method are
Florisil cartridge and sulfur cleanup. Florisil cartridge
cleanup is required for all extracts. Sulfur cleanup must be
performed on all extracts containing sulfur at levels that
interfere with GC/ECD analysis. Sulfur contamination in a
sample analysis is unacceptable. Method blanks must be
subjected to the same cleanup procedures as the samples.
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12.4.2 Florisil Cartridge Procedure
Florisil cartridge cleanup significantly reduces matrix
interferences caused by polar compounds and is required for all
extracts.
12.4.2.1 Cartridge Performance Check. Every lot number of
Florisil cartridges must be tested by the following
procedure before they are used for sample cleanup.
Add 0.50 mL of 2,4,5•triehlorophenol solution (0.1
ug/mL in acetone) and 0.50 mL of Standard Mixture A,
midpoint concentration (Section 7.3.4) to 4 mL of
hexane. Reduce the final volume to 1.0 mL using the
extract concentration techniques in paragraph 12.5.
Place the mixture onto the top of a washed Florisil
cartridge, and elute it with 9 mL of hexane/acetone
[(90:10)(V/V)]. Use two additional 1 mL hexane
rinses to ensure quantitative transfer of standard
from the cartridge. Reduce the final volume to 1.0
mL using micro Snyder column or nitrogen evaporation
techniques (Section 12.5). Analyze the solution by
GC/ECD. This solution must be analyzed on a GC/ECD
meeting the initial and calibration verification
technical acceptance criteria. The recovery of each
analyte must be determined for evaluation and
reporting purposes. The lot of Florisil cartridges
is acceptable if all pesticides and surrogates are
recovered at 80 to 120 percent, if the recovery of
triehlorophenol is less than 5%, and no peaks
interfering with the target analytes are detected.
12.4.2.2 Florisil cartridge cleanup procedure
12.4.2.2.1 Attach the vacuum manifold to a water
aspirator or to a vacuum pump with a
trap installed between the manifold and
the vacuum source. Adjust the vacuum
pressure in the manifold to between 5
and 10 pounds of vacuum.
12.4.2.2.2 Place a 1 g Florisil cartridge into the
vacuum manifold for each sample
extract.
12.4.2.2.3 Prior to cleanup of samples, the
cartridges must be washed with
hexane/acetone (90:10). This is
accomplished by placing the cartridge
in the vacuum manifold, by pulling a
vacuum, and by passing at least 5 mL of
the hexane/acetone solution through the
cartridge. While the cartridges are
being washed, adjust the vacuum applied
to each cartridge so that the flow rate
PEST D-31 6/91
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through each cartridge is approximately
equal. DO NOT ALLOW THE CARTRIDGES TO
GO DRY AFTER THEY HAVE BEEN WASHED.
12.4.2.2.4 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.
12.4.2.2.5 Transfer the 1 mL extract to the top
frit of the appropriate Florisil
cartridge. Rinse the concentrator tube
twice with 0.5 mL of hexane/acetone
(90:10) and transfer each rinse to the
top frit of the cartridge.
12.4.2.2.6 The pescieides/Aroclors in the extract
concentrates are then eluted through
the column with 8.0 mL of
hexane/acetone (90:10) and are
collected into die 10 mL volumetric
flasks held in the rack inside the
vacuum manifold.
12.4.2.2.7 Transfer the eluate in each volumetric
flask to a clean centrifuge tube or 10
mL vial. Use two additional 1 mL
hexane rinses to ensure quantitative
transfer of the cartridge eluate.
12.4.2.2.8 Concentrate the extract to 2.0 mL using
either a micro Snyder column or
nitrogen evaporation (Section 12.5).
Measure the final volume with a syringe
or by transferring the extract to a
volumetric flask.
12.4.2.2.9 If crystals of sulfur are evident or if
the presence of sulfur is suspected,
proceed to Section 12.4.3. Sample
analyses with interference caused by
sulfur are not acceptable and the
extracts must be cleaned up and
reanalyzed.
12.4.2.2.10 If the extract is not contaminated with
sulfur, transfer the sample to a. GC
vial and label the vial. The extract
is ready for GC/ECD analysis. Proceed
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to Section 13. Store the extracts at
4*C in the dark until analyses are
completed.
12.4.3 Sulfur Removal
Sulfur can be removed by one of two methods, according to
laboratory preference. Interference which is due to sulfur is
not acceptable. If the sulfur concentration ia such that
crystallization occurs in the concentrated extract, centrifuge
the extract to settle the crystals, and remove the sample
extract with a disposable pipette, leaving the excess sulfur in
the centrifuge tube. Transfer the extract to a clean
centrifuge tube or clean concentrator tube before proceeding
with further sulfur cleanup.
12.4.3.1 If only part of a set of samples requires sulfur
cleanup, then two blanks are required for that set:
one that is shaken with mercury or copper, and one
that is not. If only part of a set of samples
requires sulfur cleanup, do not subject the
associated method blank to sulfur cleanup, but
prepare a separate sulfur cleanup blank as described
below. If all the samples are subjected to sulfur
cleanup, process the method blank along with the
samples. In this ease, no additional sulfur cleanup
blank is required.
Sulfur cleanup blank. Add 200 uL of surrogate to 10
mL of hexane in a clean centrifuge tube or 10 mL
vial. Concentrate the solution to 2.0 mL by using
either nitrogen blowdown or a micro Snyder column.
The concentrated volume of the blank must be the
same as the final volume of the samples associated
with the blank. Measure the volume with a syringe
or by transferring the solution to a volumetric
flask. Proceed with the sulfur removal using the
same technique (mercury or copper) as the samples
associated with the blank.
12.4.3.2 Mercury technique
Add one to three drops of mercury to each hexane
extract in a clean vial. Tighten the top on the
vial and agitate the sample for 30 seconds. Filter
or centrifuge the extract. Fipet the extract to
another vial and leave all solid precipitate and
liquid mercury. If the mercury appears shiny,
proceed to Section 13 and analyze the extract. If
the mercury turns black, repeat sulfur removal as
necessary. CAUTION: Waste containing mercury
should be segregated and disposed of properly.
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6/91
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NOTE: Mercury is a highly toxic metal and
therefore, mist be used with great care. Prior to
using mercury, it is recommended that the analyst
become acquainted with proper hand!ing and cleanup
techniques associated with this metal.
12.4.3.3 Copper technique
Add approximately 2 g of cleaned copper powder to
the extract in the centrifuge or concentrator tube.
(2 g will fill the tube to about the 0.5 mL mark).
Mix the copper and extract for at least 1 minute on
a mechanical shaker. Separate the extract from the
copper powder by drawing off the extract with a
disposable pipet, and transfer the extract to a
clean vial. The extract transferred to the vial
still represents the 2.0 mL final volume. The
separation of the extract from the copper powder is
necessary to prevent degradation of the pesticides.
If the copper appears bright, proceed to Section 13
and analyze the extract. If the copper changes
color, repeat the sulfur removal procedure as
necessary.
12.5. Extract Concentration
Two different techniques are permitted to concentrate the extract to
1.0 nL (volume before Florisil cleanup) or 2.0 mL (extract volume
before instrumental analysis). They are the micro Snyder column and
nitrogen evaporation techniques.
12.5.1 Micro Snyder Column Technique
Add another one or two clean boiling chips to the concentrator
tube and attach a two-ball micro Snyder column. Pre-wet the
Snyder column by adding about 0.5 mL of hexane to the top of
the column. Place the K-D apparatus in a hot water bath (60*C
to 65 *C) so that the concentrator tube is partially immersed in
the hot water. Adjust the vertical position of the apparatus
and the water temperature as required to complete the
concentration in 5 to 10 minutes. At the proper rate of
distillation the balls of the column will actively chatter but
the chambers will not flood with condensed solvent. When the
apparent volume of liquid reaches about 0.5 mL, remove the K-D
apparatus from the water bath and allow it to drain for at
least 10 minutes while cooling. Remove the Snyder column and
rinse its flask and lower joint into the concentrator tube with
0.2 mL of hexane. Adjust the final volume with hexane to 1.0
mL (Florisil) or 2.0 mL (analysis).
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12.5.2 Nitrogen Evaporation Technique (taken from ASTM Method D 3086).
12.5.2.1 Place the concentrator tube with an open micro
Snyder column attached in a warm water bath (30*C to
35*C) and evaporate the solvent volume to Just below
1 or 2 mL by blowing a gentle stream of clean, dry
nitrogen filtered through a column of activated
carbon above the solvent. Adjust the final volume
with hexane to 1.0 mL (Florisil) or 2.0 mL
(analysis).
12.5.2.2 CAUTION: Gas lines from the gas source to the
evaporation apparatus must be stainless steel,
copper, or Teflon tubing. The internal wall of new
tubing must be rinsed several times with hexane and
then dried prior to use. During evaporation, the
tube solvent level must be kept below the water
level of the bath. DO NOT ALLOW THE EXTRACT TO GO
TO DRYNESS.
12.5.3 If the extract has not been put through Florisil yet, proceed
to Section 12.4 for extract cleanup. Otherwise, transfer the
extract to a Teflon-lined screw-cap bottle and label the
bottle. Store at 4*C (±2»C).
PEST D-35 6/91
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SECTIOH V
SAMPLE AHALYSIS AHD COMPOUND IDENTIFICATION AND QUANTITAXION
PEST D-36 6/91
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13. INSTRUMENTAL ANALYSIS
Before samples or required blanks can be analyzed, the instrument must
meet the initial calibration and calibration verification technical
acceptance criteria. All sample extracts, including LCS and FES,
required blanks, and calibration standards must be analyzed under the
same instrumental conditions. All samples (Including the LCS and FES),
required blanks, extracts, and standard/spiking solutions must be
allowed to warm to ambient temperature (approximately 1 hour) before
preparation/analysis.
13.1 Set up the GC/ECD system per the requirements in Section III. Unless
ambient temperature on-column injection is used (see Section 8), the
injector must be heated to at least 200*C. The optimized gas
chromatographic conditions from Section 8 must be used.
13.2 The injection must be made on-column by using either automatic or
manual injection. If autoinjectors are used, 1.0 uL injection volumes
may be used. Mnmial injections must use at least 2.0 uL injection
volumes. The same injection volume must be used for all standards,
samples, and blanks associated with the same initial calibration. If a
single injection is used for two GO columns attached to a single
injection port, it may be necessary to use an injection volume greater
than 2 uL. However, the same injection volume must be used for all
analyses.
PEST D-37 6/91
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13.3
All acceptable samples must be analyzed within a valid analysis
sequence as given below.
Tii
0 hr.
12 hr.
Another 12 hr.
Another 12 hr.
Infection #
1 - 15
16
17
18
o
o
o
o
1st injection
past 12:00 hr.
2nd and 3rd
injections
past 12:00 hr.
o
o
o
o
o
o
1st injection
past 12:00 hr.
2nd injection
o
o
o
o
o
o
1st injection
past 12:00 hr.
2nd and 3rd
inj actions
past 12 hr.
o
o
o
o
o
etc.
Material Iniected
First 15 steps of the
Initial Calibration
Instrument Blank at end of
PEM at end of
Initial Calibration
First Sample
Subsequent Samples
Last sample
Instrument Blank
Individual Standard Mixtures A and B
Sample
Subsequent Samples
Last Sample
Instrument Blank
Performance Evaluation Mixture
Sample
Subsequent Samples
Last Sample
Instrument Blank
Individual Standard Mixtures A and B
Sample
Subsequent Samples
NOTE: The first 12 hours are counted from the injection #16 (the
Instrument Blank at the end of the initial calibration sequence), not
from injection #1. Samples may be injected until 12:00 hours have
elapsed. All subsequent 12-hour periods are timed from the injection
of the instrument blank that brackets the front end of the samples.
Because the 12-hour time period is timed from injection of the
PEST D-38
6/91
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instrument blank until the in1action of the last sample, each 12-hour
period nay be separated by the length of one chronatographic run, that
of the analysis of the last sample. While the 12-hour period may not
be exceeded, the laboratory may run instrument blanks and standards
more frequently, for instance, to accomodate staff working on 8-hour
shifts.
13.4 Included with the subsequent samples in the analysis sequence are all
of the required method blanks and sulfur cleanup blanks. The
Contractor may decide at what point in the sequence the method blanks
and sulfur cleanup blanks are to be analyzed.
13.5 Termination of Data Acquisition
After decachlorooiphenyl has eluted from the GO column, the data
acquisition may be terminated for that analysis.
14. DILUTIONS
14.1 The sample or blank must first be analyzed at the most concentrated
level (injection taken from the 2.0 mL final extract after the clean-up
steps).
14.1.1 If the response of any single component pesticide is greater
than the response of that analyte in the initial calibration
high point standard, then the extract must be diluted to have
the response of that analyte between the initial calibration
low point and high point standard.
14.1.2 If the response of the largest peak in a multicomponent analyte
is greater than the most intense single component analyte
response in the initial calibration high point standard, then
the response of the largest peak in a multicomponent analyte
must be diluted to have its response between the responses of
the initial calibration midpoint and high point standard of
that single component pesticide.
14.1.3 If a greater than 10 times dilution is needed (for example, 50
to 1 dilution), then a 10 times more concentrated dilution (5
to 1 dilution) also must be analyzed.
14.2 When diluted, the chromatographic data for the single component
pesticide must be able to be reported at greater than 10 percent of
full scale but less than 100 percent of full scale.
14.3 When diluted, multicomponent analytes must be able to be reported at
greater than 25 percent of full scale but less than 100 percent of full
scale.
14.4 If a chromatogram is replotted electronically to meet these
requirements, the scaling factor used must be displayed on the
chromatogram. If the chromatogram of any sample needs to be replotted
electronically to meet these requirements, both the initial
PEST D-39 6/91
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chromatogram and the replotted cfarooatogram(s) must be submitted in the
data package.
14.5 Dilute the sample using the following procedure:
14.5.1 Calculate the extract dilution in order for the single
component pesticides to meet the requirement listed in
paragraph 14.2.
14.5.2 Calculate the extract dilution in order for the multicomponent
analytes to meet the requirement listed in 14.3.
14.5.3 Dilute the sample extract with hexane in a volumetric flask.
15. IDENTIFICATION OF TARGET AHALTTSS
15.1 The laboratory will identify single component analyte peaks based on
the retention time windows established during the initial calibration
sequence. Single component analytes are identified when peaks are
observed in the RT window for the analyte on both GC columns.
15.2 A set of three to five major peaks is selected for each multicomponent
analyte. Retention time windows for each peak are determined from the
initial calibration analysis. Identification of a multicomponent
analyte in the sample is based on pattern recognition in conjunction
with the elution of three to five sample peaks within the retention
time window of the corresponding peaks of the standard on both GC
columns. The number of potential quantitation peaks is listed in Table
D.14.
TABLE D-14
MulticonrDonenC Analvte No of Potential Ouantitatiem Peaks
Aroclor 1016/1260 5/5
Aroclor 1221 3
Aroclor 1232 4
Aroclor 1242 5
Aroclor 1243 5
Aroclor 1254 5
Toxaphene 4
15.3 A standard of any identified multicomponent analyte must be run within
72 hours of its detection in a sample chromatogram within a valid 12
hour sequence.
15.4 The choice of the peaks used for multicomponent analyte identification
and the recognition of those peaks may be complicated by the
environmental alteration of the Toxaphene or Aroclors, and by the
presence of coeluting analytes, or matrix interferences, or both.
Because of the alteration of these materials in the environment,
multicomponent analytes in samples may give patterns similar to, but
not identical with, those of the standards.
PEST D-40 6/91
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15.5 Toxaphene and Aroclors require only a single-point calibration.
Identification requires visual inspection of an on-scale pattern.
16. OTJAMTITATION OF AHALYTES
16.1 Quantitation for all analytes and surrogates oust be performed and
reported on both columns.
16.2 Manual integration of peaks (e.g., measuring peak height with a ruler)
is only permitted when accurate electronic integration of peaks cannot
be done. If manual integration of peaks is required, it must be
documented in the SDG Narrative.
16.3 The Contractor must quantitate each single component analyte and
surrogate based on the calibration factor from the most recent initial
calibration midpoint standard mixture analyses. Do not use the
analyses of the Individual Standard Mixtures used to demonstrate
continuing calibration for quantitation of samples.
16.4 The Contractor must quantitate each multicomponent analyte based on the
calibration factor from the most recent initial calibration standard.
16.5 If more than one multicomponent analyte Is present, the Contractor must
choose separate peaks to quantitate the different multicomponent
analytes. A peak common to both analytes present in the sample must
not be used to quantitate either analyte.
16.6 Before reporting data, it is required that the Contractor check for
flags generated by the data system that indicate improper quantitation
of analytes.
16.7 The chromatograms of all samples, standards, and blanks must be
reviewed by a qualified pesticide analyst before they are reported.
16.8 Calculations.
16.8.1 Calculate the concentration of the single component pesticides
and surrogates by using the following equation:
EQ D 32 Concentration ug/L - (^
(CF) (Vj.) (Vx)
Where:
AX - Response (peak area or height).
CF - Calibration factor for the external standard (Paragraph 9.4.3)
(per ng).
Vt - Volume of total extract (uL). (This volume is 2000 uL.)
PEST D-41 6/91
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V^ - Volume of extract injected (uL) . (If a single injection is
made onto two columns, use one -half the volume of the syringe
as the volume injected onto each column.)
Vx - Volume of water extracted (mL) . (NOTE: for instrument blanks
and sulfur cleanup blanks, assume a 1,000 mL volume).
Df - Dilution factor. The dilution factor for analysis of water
samples by this method is defined as follows:
"L Tost cone, extract "ged to make dilution + **i- clean solvent
uL most cone, extract used to make dilution
If no dilution is performed, Of - 1.0.
The calibration factors used in Equation D.32 are those from
the most recent Initial calibration. If the calibration
factors used to determine the linearity of the initial
calibration were based on peak area, then the response of the
analyte in the sample must be based on peak area. Similarly,
if peak height was used to determine linearity, use peak height
to determine the concentration in the sample.
16.8.2 During initial calibration, a set of three to five quantitation
peaks was chosen for each multicomponent analyte. Calculate
the concentration of each of the selected Aroclor or Toxaphene
peaks individually using Equation D.32. Determine the mean
concentration for all of the selected peaks. The mean value is
reported on Form X (Exhibit B) for both GC columns.
16.8.3 For the single component pesticides, report the lover of the
two values quantitated from the two columns of Form I. For the
multicomponent analytes, report the lower of the two mean
values from the two columns on Form I.
16.8.4 The recoveries of the surrogates are calculated according to
Equation D.33.
EQ. D.33 qd
Surrogate Percent Recovery - jr— x 100
Where:
Qd - Quantity determined by analysis.
Qa - Quantity added to sample/blank.
16.8.5 The percent difference is calculated according to Equation
D.34.
EQ. D.34 Concfl - Conc^
%D - x 100
PEST D-42 6/91
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Where,
Concg - The higher of the two concentrations for the target
compound in question.
ConcL - The lower of the two concentrations for the target
compound in question.
Note that using this equation will result in percent difference
values that are always positive. The value will also be
greater than a value calculated using the higher concentration
in the denominator, however, given the likelihood of a positive
interference raising the concentration determined on one GC
column, this is a conservative approach to comparing the two
concentrations.
17. TECHNICAL ACCEPTANCE CRITERIA FOR SA*?TtB ANALYSIS
All requirements listed below apply independently to both GC columns
and to all instruments used for these analyses.
17.1 Samples must be analyzed under the GC/ECD operating conditions in
Section 8. The instrument must have met all initial calibration and
calibration verification technical acceptance criteria. Sample data
must be bracketed at 12-hour intervals (or less) by acceptable analyses
of instrument blanks, Performance Evaluation Mixtures, and Individual
Standard Mixtures A and B, as described in Section 10.2.
17.2 The sample must be extracted and analyzed within the contract holding
times.
17.3 The LCS associated with the samples must meet the LCS technical
acceptance criteria. The FES associated with the samples must meet the
FES technical acceptance criteria. The method blank extracted with the
samples must meet the method blank technical acceptance criteria. If a
sulfur cleanup blank is associated with the samples, that blank must
meet the sulfur cleanup blank technical acceptance criteria.
17.4 The retention time for each of the surrogates must be within the
retention time window as calculated in Section 9.
17.5 The percent recovery for the surrogates must be between 60.0 and 150
percent, inclusive.
17.6 No target analyte concentrations may exceed the upper limit of the
initial calibration (See paragraph 14.1.1 and 14.1.2) or else extracts
must be diluted and reanalyzed.
17.7 A standard for any identified multicomponent analyte must be analyzed
on the same instrument within 72 hours of its detection in a sample
within a valid 12 hour sequence.
PEST D-43 6/91
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17.8 The identification of single component pesticides by gas
chronatographic methods is based primarily on retention time data. The
retention time of the apex of a peak can only be verified from an on-
scale chromatogram. The identification of multicomponant analytes by
gas chromatographic methods is based primarily on recognition of
patterns of retention times displayed on a chromatogram. Therefore,
the following requirements apply to all data presented for single
component and multicomponent analytes.
17.8.1 When no analytes are identified in a sample, the chromatograms
from the analyses of the sample extract must use the same
scaling factor as was used for the low point standard of the
initial calibration associated with those analyses.
17.8.2 Chromatograms must display single component pesticides detected
in the sample at less than full scale.
17.8.3 Chromatograms must display the largest peak of any
multicomponent analyte detected in the sample at less than full
scale.
17.8.4 If an extract must be diluted, chromatograms must display
single component pesticides between 10 and 100 percent of full
scale.
17.8.5 If an extract must be diluted, ehromatograms must display
multicomponent analytes between 25 and 100 percent of full
scale.
17.8.6 For any sample or blank, the baseline of the chromatogram must
return to below 50 percent of full scale before the elution
time of alpha-BHC, and return to below 25 percent of full scale
after the elution time of alpha-BHC and before the elution time
of decachlorobiphenyl.
17.8.7 If a chromatogram is replotted electronically to meet these
requirements, the scaling factor used must be displayed on the
chromatogram.
17.8.8 If the chromatogram of any sample needs to be replotted
electronically to meet these requirements, both the initial
chromatogram and the replotted chromatogram(s) must be
submitted in the data package.
18. COPBgCTIVg ACTION
18.1 If the sample technical acceptance criteria are not met, check
calculations, surrogate solutions, and instrument performance. It may
be necessary to recalibrate the instrument or take other corrective
action procedures to meet the technical acceptance criteria, in which
case, the affected samples must be reanalyzed at no additional cost
after the corrective action.
PEST D-44 6/91
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18.2 If the Contractor needs to analyze more than the most concentrated
extract and two (2) sample dilutions to have all the pesticide/Aroclor
compounds within the calibration range of the instrument, contact SMO.
SMO will contact the Region for instructions.
18.3 Sample analysis technical acceptance criteria MUST be met before data
are reported. Samples contaminated from laboratory sources or
associated with a contaminated method blank or sulfur cleanup blank
will require reextraction and reanalysis at no additional cost. Any
samples analyzed that do not meet the technical acceptance criteria
will require reextraction and\or reanalysis at no additional cost.
18.4 Sample reextraction/reanalyses performed as a result of suspected
matrix interferences beyond the scope of the method will be reviewed on
a case-by-case basis for payment purposes by SMO.
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SECTIOH 71
SAMPLE QUALITY CONTROL PROCEDURES AND REQUIREMENTS
PEST D-46 6/91
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20.
Summary
There are two types of blanks required by this method: the method blank
and the Instrument blank. A separate sulfur cleanup blank may also be
required If some, but not all of the samples are subjected to sulfur
cleanup. Samples that are associated with a sulfur cleanup blank are
also associated with the method blank with which they were extracted.
Both the method and sulfur cleanup blanks must meet the respective
technical acceptance criteria for the sample analysis technical
acceptance criteria to be met.
20.1 Method Blanks
20.1.1 Summary
A method blank is 1.0 liter of reagent water carried through
the entire analytical scheme.
20.1.2 Frequency
A method blank must be extracted and analyzed:
o once every 20 samples, AND
o every time samples are extracted.
20.1.3 Procedure
20.1.3.1 Measure 1.0 liter of reagent water for each method
blank aliquot. Add 200 uL of the surrogate
solution. Extract and concentrate the method blank
according to Section 12.
20.1.3.2 Analyze the method blank according to Section 13.
Calculate the results according to Section 16.
20.1.4 Technical Acceptance Criteria for Method Blanks
20.1.4.1 All method blanks must be prepared and analyzed at
the frequency described in Paragraph 20.1.2 using
the procedure in Paragraph 20.1.3 on a GC/ECD system
meeting the initial calibration and calibration
verification technical acceptance criteria.
20.1.4.2 The concentration in the method blank of the target
compounds in Exhibit C must be less than or equal to
the CRQL for each target compound.
20.1.4.3 The method blank must meet all sample technical
acceptance criteria in Section 17.
PEST D-47 6/91
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20.1.5 Corrective Action
20.1.5.1 If a method blank does not meet the technical
acceptance criteria, the Contractor must consider
the analytical system to be out of control. It is
the Contractor's responsibility to ensure that
method interferences caused by contaminants in
solvents, reagents, glassware, and sample storage
and processing hardware that lead to discrete
artifacts and/or elevated baselines in gas
chromatograms be eliminated. If contamination is a
problem, the source of the contamination must be
investigated and appropriate corrective measures
MUST be taken and documented before further sample
analysis proceeds.
20.1.5.2 Any method blank that fails to meet the technical
acceptance criteria must be reextraeted and
reanalyzed at no additional cost. Further, all
samples (including LCS and PES) processed with a
method blank that does not meet the blank technical
acceptance criteria (i.e., contaminated) will
require reextraetion and reanalysis at no additional
cost.
20.2 Sulfur Cleanup Blank
20.2.1 Summary
The sulfur cleanup blank is a modified form of the method
blank. The sulfur cleanup blank is hexane spiked with the
surrogates and passed through the sulfur cleanup procedure
(Section 12.4.3).
20.2.2 Frequency
The sulfur cleanup blank is prepared when only part of a set of
samples extracted together requires sulfur removal. A method
blank is associated with the entire set of samples. The sulfur
cleanup blank is associated with the part of the set which
required sulfur cleanup. If all the samples associated with a
given method blank are subjected to sulfur cleanup, then no
separate sulfur cleanup blank is required.
20.2.3 Procedure
20.2.3.1 Prepare the sulfur cleanup blank per Paragraph
12.4.3.1 at the frequency listed in Paragraph
20.2.2.
20.2.3.2 Analyze the sulfur cleanup blank according to
Section 13. Calculate the results according to
Section 16.
PEST D-48 6/91
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20.2.4 Technical Acceptance Criteria for Sulfur Cleanup Blanks
20.2.4.1 All sulfur cleanup blanks must be prepared and
analyzed at the frequency described in Paragraph
20.2.2 using the procedure in Paragraph 20.2.3 on a
GC/ECD system meeting the initial calibration and
calibration verification technical acceptance
criteria.
20.2.4.2 The concentration in the sulfur cleanup blank of the
target compounds in Exhibit C must be less than or
equal to the CBQL for each target compound.
20.2.4.3 The sulfur cleanup blank must meet all sample
technical acceptance criteria in Section 17.
20.2.5 Corrective Action
20.2.5.1 If a sulfur blank does not meet the technical
acceptance criteria, the Contractor must consider
the analytical system to be out of control. It is
the Contractor's responsibility to ensure that
interferences caused by contaminants in solvents,
reagents, glassware, and sample storage and
processing hardware that lead to discrete artifacts
and/or elevated baselines in gas chromatograms be
eliminated. If contamination is a problem, the
source of the contamination must be investigated and
appropriate corrective measures MUST be taken and
documented before further sample analysis proceeds.
20.2.5.2 Any sulfur blank that fails to meet the technical
acceptance criteria must be reextracted and
reanalyzed at no additional cost. Further, all
samples (including LCS and PES) processed with a
sulfur blank that does not meet the blank technical
acceptance criteria (i.e., contaminated) will
require reextraction and reanalysis at no additional
cost.
20.3 Instrument Blanks
20.3.1 Summary
An instrument blank is a volume of clean solvent containing the
surrogates that is analyzed to determine the extent of
contamination in the GC/ECD system.
20.3.2 Frequency
The first analysis after a 12-hour analysis sequence (see
Section 10.2) must be an instrument blank.. All groups of
acceptable sample analyses are to be preceded and followed by
acceptable instrument blanks. If more than 12 hours have
PEST D-49 6/91
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elapsed since the injection of the instrument blank that
bracketed a previous 12-hour period, an instrument blank must
be analyzed to initiate a new 12-hour sequence (see Section
10.2).
20.3.3 Procedure
20.3.3.1 Prepare the instrument blank by spiking the
surrogates into hexane or iso-octane for a
concentration of 20.0 ng/mL of Tetrachloro-m-xylene
and Decachlorobiphenyl.
20.3.3.2 Analyze the instrument blank according to Section 13
at the frequency listed in paragraph 20.3.2.
Calculate the results according to Section 16.
20.3.4 Technical Acceptance Criteria for Instrument Blanks
20.3.4.1 All instrument blanks must be prepared and analyzed
at the frequency described in Paragraph 20.3.2 using
the procedure in Paragraph 20.3.3 on a GC/ECD system
meeting the initial calibration and calibration
verification technical acceptance criteria.
20.3.4.2 The concentration in the instrument blank of each
target analyte in Exhibit C must be less than or
equal to the CRQL for that analyte.
20.3.4.3 The instrument blank must meet all sample technical
acceptance criteria in Section 17.
20.3.5 Corrective Action
20.3.5.1 If analytes are detected at greater than the CRQL or
the surrogate RTs are outside the RT windows, all
data collection must be stopped, and corrective
action must be taken. Data for samples which were
run between the last acceptable instrument blank and
the unacceptable blank are considered suspect. An
acceptable instrument blank must be run before
additional data are collected. All samples which
were run after the last acceptable instrument blank
must be reinjected during a valid run sequence and
must be reported at no additional cost.
20.3.S.2 Analysts are cautioned that running an instrument
blank once every 12 hours (see Section 10) is the
minimum contract requirement. Late eluting peaks
may carry over from one injection to the next if
highly complex samples are analyzed or if the GC
PEST D-50 6/91
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conditions are unstable. Such carryover is
unacceptable. Therefore, it may be necessary to run
instrument blanks more often to avoid discarding
data.
21. LABORATORY COOTROL SAMPLES (LCS)
21.1 Summary
The laboratory control sample (LCS) is an internal laboratory quality
control sample designed to assess (on an SDG-by-SDG basis) the
capability of the contractor to perform the analytical method listed in
this Exhibit.
21.2 Frequency
The LCS must be prepared, extracted, analyzed, and reported once per
Sample Delivery Group. The LCS must be extracted and analyzed
concurrently with the samples in the SDG using the same instrumentation
as the samples in the SDG.
21.3 Procedure
21.3.1 Measure a 1 liter aliquot of reagent water in a 1 liter
graduated cylinder and transfer the water to a continuous
extractor. Pipet 1.0 mL of the LCS spiking solution (Paragraph
7.3.7) and 200 uL of the surrogate standard spiking solution
into the water and mix well. Extract and concentrate the
sample according to Section 12.
21.3.2 Analyze the LCS per Section 13.
21.4 Calculations
21.4.1 Calculate the results according to Section 16.
21.4.2 Calculate individual compound recoveries of the LCS using
Equation D.33, substituting LCS percent recovery for surrogate
percent recovery.
21.5 Technical Acceptance Criteria For Laboratory Control Sample Analysis
21.5.1 The LCS must be analyzed at the frequency described in Section
21.2 on a GC/ECD system meeting the initial calibration and
calibration verification technical acceptance criteria.
21.5.2 The LCS must be prepared as described in Paragraph 21.3.
21.5.3 The LCS must meet all sample technical acceptance criteria in
Section 17.
21.5.4 The percent recovery for each of the compounds in the LCS mist
be within the recovery limits listed in Table D-15.
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Table D-15
LABORATORY CONTROL SAMPLE RECOVERY LIMITS
COMPOUND % RECOVERY
•BHC 56-123
Heptaehlor epoxide 74-150
Dieldrin 33-130
4, 4 '-ODE 50-150
Endrln 56-121
Endosulfan sulfate 50-100
gamma- Chlordane 33-130
NOTE: The recovery limits for any of the compounds in the LCS
may be expanded at any time during the period of performance if
SMO determines that the limits are too restrictive.
21.6 Corrective Action
21.6.1 If the LCS technical acceptance criteria for the surrogates or
the LCS compound recovery are not met, check calculations, the
surrogate and LCS solutions, and instrument performance. It
may be necessary to recalibrate the instrument or take other
corrective action procedures to meet the surrogate and LCS
recovery criteria.
21.6.2 LCS technical acceptance criteria MUST be met before data are
reported. LCS contamination from laboratory sources or any LCS
analyzed not meeting the technical acceptance criteria will
require reextraction and reanalysis of the LCS at no additional
cost.
21.6.3 All samples prepared and analyzed in an SDG with an LCS that
does not meet the technical acceptance criteria will also
require reextraction and reanalysis at no additional cost.
22.
22 . 1 Summary
The PES is an external laboratory quality control sample prepared and
designed to assess (on an SDG-by-SDG basis) the capability of the
contractor to perform the analytical method listed in this Exhibit.
PEST D-52 6/91
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22.2 Frequency
The Contractor must extract, analyze, and report the PES once per SDG,
if available. The PES must be extracted and analyzed concurrently with
the samples in the SDG using the same instrumentation as the samples in
the SDG.
22.3 Procedure
22.3.1 The PES will be received either as an aapulated extract or as a
full volume sample. If received as an ampulated extract, the
Contractor will receive instructions concerning the dilution
procedure to bring the extract to full volume prior to
preparation and analysis of the PES.
22.3.2 Add 200 uL of surrogate solution to 1 liter of reagent water
spiked with the PES solution. Extract and concentrate the FES
using the procedure described in Section 12. Analyze the PES
as described in Section 13.
22.4 Calculations
See paragraph 16 for all equations necessary for calculations.
22.5 Technical Acceptance Criteria for Performance Evaluation Sample
22.5.1 The PES must be analyzed on a GC/ECD system meeting the initial
calibration and calibration verification technical acceptance
criteria at the frequency described in Section 22.2.
22.5.2 The PES must be extracted and concentrated according to Section
22.3.
22.5.3 The PES must meet all sample technical acceptance criteria in
Section 17.
22.6 Corrective Action
22.6.1 If the PES technical acceptance criteria for the surrogates are
not met, check calculations, standard solutions and instrument
performance. It may be necessary to recalibrate the instrument
or take other corrective action procedures to meet the
technical acceptance criteria. Any PES failing to meet these
technical acceptance criteria must be reextracted and
reanalyzed at no additional cost. If insufficient PES extract
remains or if an insufficient volume of the PES remains,
document this in the SDG Narrative by stating that the PES
could not be reextracted and reanalyzed because insufficient
volume remained.
22.6.2 In addition to complying with the PES technical acceptance
criteria, the Contractor will be responsible for correctly
identifying and quantifying the compounds included in the
PEST D-53 6/91
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Performance Evaluation Sample. SMO will notify the Contractor
of unacceptable performance.
Note: Unacceptable performance for identification and
quantitation of compounds is defined as a score less than 75
percent.
22.6.3 The FES technical acceptance criteria HOST be met before sample
data are reported. Also, the Contractor must demonstrate
acceptable performance for compound identification and
quantitation.
U S. Environmental Protection Agency
Region 5.Library (PL-12J)
77 West Jackson Boulevard, 12th Moor
Chicago, IL 60604-3590
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