WA-87J001
WA-87J002
WA-87J003
ATTACHMENT A
USEPA Contract Laboratory Program
STATEMENT OF WORK
FOR
ORGANICS ANALYSIS
Multi-Media
*
Multi-Concentration
10/86
-------
STATEMENT OF WORK
TABLE OF CONTENTS
EXHIBIT A: SUMMARY OP REQUIREMENTS
EXHIBIT B: REPORTING AND DELIVERABLES REQUIREMENTS
EXHIBIT C: TARGET COMPOUND LIST (TCL) AND CONTRACT REQUIRED
QUANTITATION LIMITS (CRQL)
EXHIBIT D: ANALYTICAL METHODS
EXHIBIT E: QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
EXHIBIT F: CHAIN-OF-CUSTODY, DOCUMENT CONTROL AND STANDARD
OPERATING PROCEDURES
EXHIBIT G: GLOSSARY OF TERMS
EXHIBIT H: DATA DICTIONARY AND FORMAT FOR DATA DELIVERABLES
IN COMPUTER-READABLE FORMAT
10/86
-------
EXHIBIT A
SUMMARY OF REQUIREMENTS
10/86
-------
SECTION I
GENERAL REQUIREMENTS
The Contractor shall use proven instruments and techniques to identify
and measure the concentrations of volatile, semivolatile and pesticide com-
pounds listed on the Target Compound List (TCL) in Exhibit C. The Contractor
shall employ state-of-the-art GC/MS and/or GC procedures to perform all analyses,
including all necessary preparations for analysis.
In Exhibit D, the EPA provides the Contractor with the specific analyti-
cal procedures to be used and defines the specific application of these proce-
dures to this contract. This includes instructions for sample preparation,
gas chromatographic screening, mass spectromecric identification and data
evaluation. Specific ions used for searching the mass spectral data for each
compound are included.
The Contractor shall prepare extracts and dilutions of samples. The
Contractor shall screen extracts by methods of his choice (soil character-
ization mandatory; water characterization optional) at an initial extract
concentration. Then, based on the screening response, the Contractor shall use
the specific analytical methods described in Exhibit D to extract and concen-
trate samples to achieve the Contract Required Quantitation Limits (CRQL)
listed in Exhibit C. Exhibit D lists the analytical methods and starting
points to be achieved for each of the TCL compounds.
During preparation, the Contractor shall fortify all samples, blanks,
matrix spikes, and matrix spike duplicates with the surrogate spiking compounds
listed in Exhibit E. Additionally, all sample semivolatile extracts and
aliquots for volatile organics analysis shall be spiked with the internal standard
compounds listed in Exhibit E before injection or purging.
Additionally, for each sample analyzed by GC/MS, the Contractor shall
conduct mass spectral library searches to determine the possible identity- of up
to ten (10) nonsurrogate volatile components and up to twenty (20) nonsurrogate
semivolatile components that are not on the Target Compound List (Exhibit C).
Exhibit F contains chain-of-custody and sample documentation requirements
which the contractor must follow in processing samples under this contract, and
specifies requirements for written laboratory standard operating procedures.
Sample analysis data, sample documentation and other deliverables shall be
reported as specified in Exhibit B. Specifications for reporting data in
computer-readable form appear in Exhibit H.
To ensure proper understanding of language utilized in this contract,
Exhibit G contains a glossary of terms. When a term is used in the text with-
out explanation, the glossary meaning shall be applicable.
The samples to be analyzed by the Contractor are from known or suspected
hazardous waste sites and, potentially, may contain hazardous organic and/or
inorganic materials at high concentration levels. The Contractor should be
aware of the potential hazards associated with the handling and analyses of
these samples. It is the Contractor's responsibility to take all necessary
measures to ensure the health and safety of its employees.
A-l
10/86
-------
SECTION II
SPECIFIC REQUIREMENTS
A. For each sample, Che Contractor shall perform the following tasks:
Task I; Receive and Prepare Hazardous Waste Samples.
1. Receive and handle samples under the chain-of-custody procedures
described in Exhibit F.
2. Prepare samples as described in Exhibit D. VOA analysis of water
or soil samples must be completed within 10 days of VTSR (Validated
Time of Sample Receipt). If separatory funnel or sonication pro"
cedures are employed for extractions for semivolatile and pesticide
analyses, extraction of water samples shall be completed within 5
days of VTSR, and extraction of soil samples shall be completed within
10 days of VTSR. If continuous liquid-liquid extraction procedures
are employed, extraction of water samples shall be started within
5 days of VTSR, and extraction of soil samples shall be completed
within 10 days of VTSR.
Extracts of either water or soil samples must be analyzed within 40
days of VTSR.
Task II: Extraction and Analysis for Identity of Specific Organic Compounds.
1. Extracts and aliquots prepared in Task I shall be analyzed by GC and
6C/MS techniques given in Exhibit 0 for the target compounds listed
in Exhibit C.
2. The target compounds listed in Exhibit C shall be Identified as
described in the methodologies given in Exhibit 0. Automated computer
programs may be used to facilitate the identification.
Task III: Qualitative Verification of the Compounds Identified in Task II.
1. The compounds analyzed by GC/MS techniques and initially identified
in Task II shall be verified by an analyst competent in the interpre-
tation of mass spectra by comparison of the suspect mass spectrum to
the mass spectrum of a standard of the suspected compound. Two cri-
teria must be satisfied to verify the identifications:
a. Elution of the sample component at the same GC relative retention
time as the standard component, and
b. Correspondence of the sample component and standard component
mass spectra. This procedure requires the use of multiple internal
standards.
2. For establishing correspondence of the GC relative retention time
(RRT), the sample component RRT must compare within +0.06 RRT units
of the RRT of the standard"component. For referenceT the calibration
standard must be run on the same 12-hour time period as the sample.
A-2
10/86
-------
For comparison of standard and sample component mass spectra, mass
spectra obtained on the contractor's GC/MS are required. Once
obtained, these standard spectra may be used for identification
purposes only if the contractor's GC/MS meets the DFTPP or BFB daily
tuning requirements of Tables 1.1 and 1.2 in Exhibit E. The standard
spectra used may be from a laboratory generated library or obtained
from the calibration standard run used to obtain reference RRTs. The
requirements for qualitative verification by comparison of mass
spectra are as follows:
a. All ions present in the standard mass spectrum at a relative in-
tensity greater than 10 percent (most abundant ion in the spectrum
equals 100 percent) must be present in the sample spectrum.
b. The relative intensities of ions specified in (1) must agree
within plus or minus 20 percent between the standard and sample
spectra.
c. Ions greater than 10 percent in the sample spectrum but not
present in the standard spectrum must be considered and accounted
for by the analyst making the comparison. When GC/MS computer
data processing programs are used to obtain che sample component
spectrum, both the processed and the raw spectra must be evaluated.
In Task. Ill, the verification process should favor false positives.
3. If a compound analyzed by GC/MS techniques and initially identified
in Task II cannot be verified by all of the criteria in items 1 and 2
above, but in the technical judgement of the mass spectral interpre-
tation specialist the identification is correct, then the Contractor
shall report that identification, and proceed with quantification in
Task IV.
4. The pesticide/PCB compounds listed in Exhibit C and analyzed by GC/EC
techniques shall have their identifications verified by an analyst
competent in the interpretation of gas chroraatograms. Two criteria
must be satisfied to verify the identifications:
a. Elution of the sample component within the retention time window
(established by the procedures in Exhibit E) of the standard com-
ponent analyzed on the same GC column and instrument, as part of
the same 72-hour analytical sequence specified in Exhibit D PEST.
b. Analysis of the sample and standard on a second GC column with a
stationary phase with retention characteristics dissimilar to
that used in a. above, and meeting the same criteria for elution
of the sample component and the standard as in a. above.
Task IV; Quantification of Compounds Verified in Task III.
1. The Contractor shall quantify components analyzed by GC/MS techniques
and identified in Task II and verified in Task III by the internal
standard method stipulated in Exhibit D. Where multiple internal
standards are required by EPA, the Contractor shall perform quanti-
utilizing the internal standards specified in Exhibit E, Part 2,
Tables 2.1 or 2.2.
A-3
10/86
-------
2. The Contractor shall determine response factors for each 12-hour time
period of GC/MS analysis and shall include a calibration check of the
initial five point calibration as described in Exhibit E.
3. The Contractor shall quantify components analyzed by GC/EC techniques
and identified in Task II and verified in Task III by the external
standard method stipulated in Exhibit 0 PEST.
4. The Contractor shall perform an initial three-point calibration, verify
its linearity, determine the degradation of labile components, and deter-
mine calibration factors for all standards analyzed by GC/EC techniques
as part of a 72-hour analytical sequence, as described in Exhibit D PEST
and Exhibit E.
Task V: Tentative Identification of Non-TCL Sample Components.
1. For each sample, the Contractor shall conduct mass spectral library
searches to determine tentative compound identifications as follows.
For each volatile fraction, the Contractor shall conduct a search
to determine the possible identity of the ten (10) nonsurrogate or-
ganic compounds of greatest concentration which are not listed in
Exhibit C. For each base/neutral/acid fraction, the Contractor shall
conduct a search to determine the possible identification of the (20)
nonsurrogate organic compounds of greatest concentration which
are not listed in Exhibit C. In performing searches, the 1985 (or
most recent) release of the National Bureau of Standards library
(containing 42,261 spectra) must be used. NOTE: Substances with
responses less than 10 percent of the nearest internal standard are
not required to be searched in this fashion.
Only after visual comparison of sample spectra with the spectra from
the library searches will the mass spectral interpretation specialist
assign a tentative identification. If the compound does not meet the
identification criteria of Task III, it shall be reported as unknown.
The mass spectral specialist should give additional classification of
the unknown compound, if possible (i.e., unknown aromatic, unknown
hydrocarbon, unknown acid type, unknown chlorinated compound). If
probable molecular weights can be distinguished, include them.
The Contractor shall not report as tentatively Identified compounds
(TIC) any TCL compounds from another analytical fraction (i.e., do
not report late-eluting volatile compounds as TICa in the semivolatile
analysis.).
Task VI: Quality Assurance/Quality Control Procedures.
1. All specific quality assurance procedures prescribed in Exhibit E
shall be strictly adhered to by the Contractor. Records documenting
the use of the protocol shall be maintained In accordance with the
document control procedures prescribed in Exhibit F, and shall be
reported in accordance with Exhibit B, Reporting Requirements and
Deliverables.
A-4
10/86
-------
The Contractor shall perform one spiked sample analysis (matrix spike)
and one duplicate spiked sample analysis (matrix spike duplicate) for
each group of samples of a similar matrix (for water or soil samples)
and concentration level (for soil samples only), once:
o each Case of field samples received, OR
o each 20 field samples in a Case, OR
o each 14 calendar day period during which field samples In a Case
were received (said period beginning with the receipt of the first
sample in that Sample Delivery Group),
whichever is most frequent.
Matrix spikes and matrix spike duplicates shall be carried through
the entire analytical process from extraction to final GC/MS or
GC/EC analysis, including all Contract Performance/Delivery Require-
ments (see Contract Schedule).
Thie Contractor shall prepare and analyze one laboratory reagent blank
(method blank) for each group of samples of a similar matrix (for water
or soil samples), extracted by a similar method (separatory funnel or
continuous liquid-liquid extraction), and a similar concentration
level (for soil samples only), once:
o each Case of field samples received, OR
o each 20 field samples in a Case, OR
o each 14 calendar day period during which field samples in a Case
were received (said period beginning with the receipt of the fir$t
sample in that Sample Delivery Group), OR
o whenever samples are extracted,
whichever Is most frequent.
Volatile analysis requires one method blank for each 12-hour time
period when volatile TCL compounds are analyzed.
Semlvolatile and pesticide method blanks shall be carried through the
entire analytical process from extraction to final GC/MS or GC/EC
analysis, including all Contract Performance/Delivery Requirements
(see Contract Schedule).
The contractor shall perform instrument calibration (by "hardware
tune") for each 12-hour time period, to include: decafluorotriphenyl-
phosphine (DFTPP) and/or broraofluorobenzene (BFB) as applicable, and
a specific calibration using standards of defined concentration to
monitor response, retention time and mass spectra.
Additional quality control shall be conducted in the form of the
analysis of Performance Evaluation check samples submitted to the
laboratory by EPA. The results of comparison studies are due within
40 calendar days of receipt of the samples. The results of all such
A-5
10/86
-------
control or PE check samples may be used as grounds for termination of
noncompliant contractors. "Compliant performance" is defined as that
which yields correct compound identification and concentration values
as determined by EPA, as well as meeting the contract requirements for
analysis (Exhibits C and 0), quality assurance/quality control (Exhibit
E), data reporting and other deliverables (Exhibits B and H), and sample
custody, sample documentation and SOP documentation (Exhibit F).
EPA has provided to the Contractor formats for the reporting of data
(Exhibits B and H). The Contractor shall be responsible for completing
and returning analysis data sheets and submitting computer-readable data
on floppy diskette in the format specified in this SOW and within the time
specified in the Contract Performance/Delivery Schedule.
1. Use of formats other than those designated by EPA will be deemed as
noncompliance. Such data are unacceptable. Resubmission in the speci-
fied format at no additional cost to the government will be required.
2. Computer generated forms may be submitted in the hardcopy data package(s)
provided that the forms are in EXACT EPA FORMAT. This means that Che
order of data elements is the same as on each EPA required form, including
form numbers and titles, page numbers and header information.
3. The data reported by the Contractor on the hardcopy data forms and the
associated computer-readable data submitted by the Contractor must
contain identical information. If during government inspection
discrepancies are found, the Contractor shall be required to resubmit
either or both seta of data at no additional cost to the government.
The Contractor shall provide analytical equipment and technical expertise
for this contract as specified following:
1. The Contractor shall have sufficient gas chromatograph (GC) and gas
chromatograph/mass spectrometer/data system (GC/MS/DS) capability to
meet all the terms and conditions of the Contract. Instrument re-
quirements are defined In IFB Attachment B, Preaward Bid Confirmations.
The Contractor shall maintain, at a minimum, all analytical equip-
ment allocated for this contract at the time of contract award.
2. The Contractor's instrument systems shall have the following:
a. The GC/MS. shall be equipped with a glass jet separator when
using packed columns.
b. The computer shall be interfaced by hardware to the mass spectro-
meter and be capable of acquiring continuous mass scans for the
d r on o c romatographic program.
c. The computer shall be equipped with a-n ; lmja for
saving all data from the GC/MS runs.
A-6
10/86
-------
d. Computer software shall be available to allow searching GC/MS
runs for specific Ions and plotting the intensity of the ions
with respect to time or scan number*
e. The GC/MS shall be equipped with a split/splitless injector and
GC Co MS interface capable of extending a fused silica capillary
column into the ion source. The column is to be 30 meters long
by 0.25 or 0.32 mm inside diameter, bonded DB-5, fused silica or
equivalent.
f. The GC for pesticide analysis shall be equipped with packed
columns (see Exhibit 0, Section IV, for an optional FSCC confirma-
tion column) and a suitable detector as described in Exhibit 0.
3. The Contractor shall use a magnetic tape storage device capable of
recording data and suitable for long-term, off-line storage. The
Contractor shall retain all raw GC/MS data acquired under this
contract on magnetic tape in appropriate instrument manufacturer's
format. The Contractor is required to retain the magnetic tapes with
associated hardcopy tape logbook identifying tape contents (see
Exhibit B) for 365 days after data submission. During that time,
the contractor shall submit tapes and logbook within 7 days of request,
as specified in the Contract Performance/Delivery Schedule.
4. The Contractor shall have a computerized MS library search system
capable of providing a forward comparison, utilizing the standard
spectra contained in the mass spectral library. The 1985 (or most
recent) release of the National Bureau of Standards library (contain-
ing 42,261 spectra) must be used.
a. The system shall provide a numerical ranking of the standard
spectra most closely corresponding to the sample spectra examined.
b. The data system 3hall have software capable of removing background
signals from spectra.
5. The Contractor shall have, in-house and operable, a device capable of
analyzing purgeable organics as described in Exhibit 0.
The Contractor shall have an IBM or IBM-compatible mini-computer or PC
capable of recording required sample data on 5.25 inch floppy double-sided
double-density 360 K-byte or 1.2 M-byte diskettes, in ASCII text file
format and in accordance with the file, record and field specifications
listed in Exhibit H.
The minimum functional requirements necessary to meet the terms and condi-
tions of this contract are listed below. The Contractor shall designate
and utilize key personnel to perform these functions. The EPA reserves
the right to review personnel qualifications and experience.
A-7
10/86
-------
o GC/MS/DS operation.
o Mass spectral interpretation.
o Sample extraction and concentration.
o Purge and trap volatile organic compounds analysis.
o Pesticide residue analysis of organochlorine pesticides and PCBs,
including clean->up procedures,
o Quality assurance/quality control
o Sample receipt, storage, and tracking, including chain-of-custody
procedures.
F. The Contractor shall respond in a timely manner to requests from data
recipients for additional information or explanations that result from
the Government's inspection activities.
G. The Contractor shall preserve all sample extracts after analysis in bottles/
vials with Teflon-lined septa and shall maintain stored extracts at 49C
(+29C). The Contractor is required to retain the sample extracts for 365
days after data submission. During that time, the contractor shall submit
the extracts within 7 days after request, as specified in the Contract
Performance/Delivery Schedule.
H. The Contractor shall adhere to chain-of-custody procedures described in
Exhibit F. Documentation, as described therein, shall be required to show
that all procedures are being strictly followed. This documentation shall
be reported as the complete Case file purge (see Exhibit B).
I. Sample shipments to the Contractor's facility will be scheduled and
coordinated by the EPA CLP Sample Management Office (SMO) acting on
behalf of the Project Officer. The Contractor shall communicate with SMO
personnel by telephone as necessary throughout the process of sample
scheduling, shipment, analysis and data reporting, to ensure that samples
are properly processed.
If there are problems with the samples (e.g., mixed media, containers
broken or leaking) or sample documentation/paperwork (e.g., Traffic Reports
not with shipment, sample and Traffic Report numbers do not correspond)
the Contractor shall immediately contact SMO for resolution. The Contractor
shall immediately notify SMO regarding any problems and laboratory conditions
that affect the timeliness of analyses and data reporting. In particular,
the Contractor shall notify SMO personnel in advance regarding sample data
that will be delivered late and shall specify the estimated delivery date.
J. Sample analyses will be scheduled by groups of samples, each defined
as a Case and identified by a unique EPA Case number assigned by SMO.
A Case signifies a group of samples collected at one site or geographical
area over a finite time period, and will include one or more field samples
with associated blanks. Samples may be shipped to the Contractor in a
single shipment or multiple shipments over a period of time, depending
on the size of the Case.
A-8
10/86
-------
A Case consists of one or more Sample Delivery Group(s). A Sample Delivery
Group (SDG) is defined by the following, whichever is most frequent:
o each Case of field samples received, OR
o each 20 field samples within a Case, OR
o each 14-day calendar period during which field samples in a Case
are received (said period beginning with the receipt of the first
sample in the Sample Delivery Group).
Data for all samples in a Sample Delivery Group are due concurrently
40 days after receipt of the last sample received in the Sample Delivery
Group. Data for all samples in a Sample Delivery Group must be submitted
together (in one package) in the order specified in Exhibit 3. The
Sample Delivery Group number is the EPA sample number of the first sample
received in the SDG. When several samples are received together In the
first SDG shipment, the SDG number shall be the lowest sample number
(considering both alpha and numeric designations) in the first group of
samples received under Che SDG. The SDG number is reported on all data
reporting forms.
The SDG Receipt Date is the day the last sample in the SDG is received.
Data for all samples in the SDG are due 40 days following this date.
The Contractor is responsible for identifying each Sample Delivery Group
as samples are received, through proper sample documentation (see Exhibit
B) and communication with SMO personnel.
Each sample received by the Contractor will be labeled with an EPA
sample number, and accompanied by a Traffic Report form bearing the sample
number and descriptive information regarding the sample. The Contractor
shall complete and sign the Traffic Report, recording the date of sample
receipt and sample condition on receipt for each sample container.
The Contractor shall submit signed copies of Traffic Reports for all
samples in a Sample Delivery Group to SMO within 3 calendar days following
receipt of the last sample in the Sample Delivery Group. Traffic Reports
shall be submitted in Sample Delivery Group sets (i.e., all Traffic Reports
for a Sample Delivery Group shall be clipped together) with an SDG Cover
Sheet containing information regarding the Sample Delivery Group, as
specified in Exhibit 3.
EPA Case numbers (including SDG numbers) and EPA sample numbers shall be used
by the Contractor in identifying samples received under this contract both
verbally and in reports/correspondence.
Samples will routinely be shipped to the Contractor through an over-
night delivery service. However, as necessary, the Contractor shall
be responsible for any handling or processing required for the receipt
of sample shipments, including pick-up of samples at Che nearest
servicing airport, bus station or ocher carrier service within the
Contractor's geographical area. The Contractor shall be available to
receive sample shipments at any time the delivery service is operating,
including Saturdays.
A-9
10/86
-------
N. The Contractor shall accept all samples scheduled by SMO, provided
Chat the total number of samples received in any calendar month does
not exceed the monthly limitation expressed in the contract. Should
the Contractor elect to accept additional samples, the Contractor
shall remain bound by all contract requirements for analysis of those
samples accepted.
A-10
10/86
-------
EXHIBIT B
REPORTING AND DELIVERABLES REQUIREMENTS
Page No.
SECTION I: Contract Reports/Deliverables Distribution B-l
SECTION II: Report Descriptions and Order of Data
Deliverables • . B-3
SECTION III: Forra Instruction Guide B-18
10/86
-------
SECTION I
CONTRACT REPORTS/DELIVERABLES DISTRIBUTION
The following cable reiterates the Contract reporting and deliverables require-
ments specified in the Contract Schedule and specifies the distribution that is
required for each deliverable. NOTE: Specific recipient names and addresses
are subject to change during the term of the contract. The Project Officer
will notify the contractor in writing of such changes when they occur.
Distribution
Item
Delivery
No. Copies Schedule
SMO EMSL-LV Region-
(1) (2) Client(3) NEIC (41
*A. Sample Traffic
Reports
1
**B. Sample Data Summary 1
Package
3 days after
receipt of
last sample
in Sample
Delivery
Group (SDG)***
40 days after
receipt of
last sample
in SDG
**C. Sample Data Package
40 days after
receipt of
last sample
in SDG
X
**D. Data in Computer-
Readable Form
40 days after X
receipt of
last sample
in SDG
E. GC/MS Tapes
F. Extracts
G. Complete Case File
Purge
Lot Retain for 365 days
after data submission,
or submit within 7 days
after receipt of written
request by P0 or SMO
Lot Retain for 365 days
after data submission,
or submit within 7 days
after receipt of written
request by P0 or SMO
1 P5cg Submit 180 days after
data submission or 7 days
after receipt of written
request by P0 or SMO.
As Directed
As Directed
B-l
10/86
-------
* Also required In Che Sample Data Package.
** Concurrent delivery required. Delivery shall be made such that all designated
recipients receive the item on the same calendar day.
*** Sample Delivery Group (SDG) is a group of samples (of similar matrix and
concentration) within a Case, received over a period of 14 days or less and
not exceeding 20 samples. Data for all samples in the SDG are due con-
currently. (See SOW Exhibit A, paragraph J., for further description).
NOTE: As specified in the Contract Schedule (G.6 Government Furnished Supplies
and Materials), unless otherwise instructed by the CLP Sample Management Office,
the Contractor shall dispose of unused sample volume and used sample bottles/
containers no earlier than sixty (60) days following submission of analytical
data.
Distribution Addresses:
(1) USEPA Contract Lab Program
Sample Management Office (SMO)
P. 0. Box 818
Alexandria, VA 22313
For overnight delivery service, use street address:
300 N. 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 acting on behalf of the Project Officer,
will provide the Contractor with the list of addressees for the ten
EPA Regions. SMO will provide the Contractor with updated Regional
address/name lists as necessary throughout the period of the contract
and identify other client recipients on a case-by-case basis.
(4) NEIC, Contractor Evidence Audit Team
12600 West Colfax, Suite 310
Lakewood, Colorado 80215
8-2
10/86
-------
SECTION II
REPORT DESCRIPTIONS AND ORDER OF DATA DELIVERABLES
The Contractor laboratory shall provide reports and other deliverables as
specified in the Contract Schedule (Performance/Delivery Schedule, Section F.l).
The required content and form of each deliverable is described in this Exhibit.
All reports and documentation MUST BE:
o Legible,
o Clearly labeled and completed in accordance with instructions in this
Exhibit,
o Arranged in the order specified in this Section, and
o Paginated.
If submitted documentation does not conform to the above criteria, the
Contractor will be required to resubmit such documentation with deficiency(ies)
corrected, at no additional cost to the Agency.
Whenever the Contractor is required to submit or resubmit data as a result
of an on-site laboratory evaluation or through a PO/DPO action, the data must
be clearly marked as ADDITIONAL DATA and must be sent to all three contractual
data recipients (SMO, EMSL-LV, and Region). A cover letter shall be included
which describes what data is being delivered, to which EPA Case(s) it pertains,
and who requested the data.
Whenever the Contractor is required to submit or resubmit data as a result
of Contract Compliance Screening (CCS) review by SMO, the data must be sent to
all three contractual data recipients (SMO, EMSL/LV and Region), and in all
three instances must be accompanied by a color-coded COVER SHEET (Laboratory
Response To Results of Contract Compliance Screening) provided by SMO.
Section III of this Exhibit contains copies of the required data report-
ing forms in Agency-specified formats, along with instructions to assist the
Contractor in accurately providing the Agency all required data. Data
elements with field parameters for reporting data in computer readable form
are contained in Exhibit H.
Descriptions of the requirements for each deliverable Item cited in the
Contract Performance/Delivery Schedule (Contract Schedule, Section F.l) are
specified in parts A-G of this Section. Items submitted concurrently MUST BE
arranged in the order listed. Additionally, the components of each item MUST
BE arranged in the order presented in this Section when the item is submitted.
Examples of specific data deliverables not Included herein may be obtained by
submitting a written request to the EPA Project Officer, stating the information
requested, and signed by the Laboratory Manager.
B-3
10/86
-------
A. Sample Traffic Reports
Original Sample Traffic Report page marked "Lab Copy for Return to SMO"
with lab receipt Information and signed in original Contractor signature,
for each sample in the Sample Delivery Group.
Traffic Reports (TRs) shall be submitted in Sample Delivery Group (SDG)
sets (i.e., TRs for all samples in an SDG shall be clipped together),
with an SDG Cover Sheet attached.
The SDG Cover Sheet shall contain the following items:
o Lab name
o Contract number
o Sample Analysis Price - full sample price from contract,
o Case Number
o List of EPA sample numbers of all samples in the SDG, identifying the
• first and last samples received, and their dates of receipt (LRDs).
NOTE: When more Chan one sample is received in the first or last SDG
shipment, the "first" sample received would be the lowest sample number
(considering both alpha and numeric designations); the "last" sample
received would be the highest sample number (considering both alpha and
numeric designations).
In addition, each Traffic Report muse be clearly marked with the SDG
Number, the sample number of Che first sample in the SDG (as described in
the following paragraph). This information should be entered below the
Lab Receipt Date on the TR. In addition, the TR for the last sample,
received in the SDG must be clearly marked "SDG - FINAL SAMPLE."
The EPA sample number of the first sample received in the SDG is the SDG
number. When several samples are received together in the first SDG
shipment, the SDG number shall be the lowest sample number (considering
both alpha and numeric designations) in the first group of samples received
under the SDG. (The SDG number is also reported on all data reporting
forms. See Section III, Forms Instruction Guide.)
B. Sample Data Summary Package
As specified in the Delivery Schedule, one Sample Data Summary Package
shall be delivered to SMO concurrently with delivery of other required
sample data. The Sample Data Summary Package consists of copies of
specified items from the Sample Data Package. These icems are listed
below and described under part C, Sample Data Package.
The Sample Data Summary Package shall be ordered as follows and shall be
submitted separately (i.e., separated by rubber bands, clips or other
means) directly preceding the Sample Data Package. Sample data forms shall
B-4
10/86
-------
be arranged in Increasing EPA sample number order, considering both letters
and numbers. BE400 is a lower sample number Chan BF100, as C precedes F in
the alphabet.
The Sample Data Summary Package shall contain data for samples in one Sample
Delivery Group of the Case, as follows:
1. Case Narrative
2. By fraction (VOA, SV, PEST) and by sample within each fraction - tabulated
target compound results (Form I) and tentatively identified compounds
(Form I, TIC)(VOA and SV only)
3. By fraction (VOA, SV, PEST) - surrogate spike analysis results (Form
II) by matrix (water and/or soil) and for soil, by concentration (low
or medium)
4. By fraction (VOA, SV, PEST) - matrix spike/matrix spike duplicate
results (Form III)
5. By fraction (VOA, SV, PEST) - blank data (Form IV) and tabulated results
(Form I) including tentatively identified compounds (Form I, TIC)(VOA
and SV only).
C. Sample Data Package
The Sample Data Package is divided into the five major units described below.
The last three units are each specific to an analytical fraction (tfolatiles,
semlvolatiles, pesticides/PCBs). If the analysis of a fraction is not
required, then that fraction-specific unit is not required as a deliverable.
The Sample Data Package shall include data for analyses of all samples in one
Sample Delivery Group, including field samples, reanalyses, blanks, matrix
spikes, and matrix spike duplicates.
1. Case Narrative
This document shall be clearly labeled "Case Narrative" and shall
contain: laboratory name; Case number; sample numbers in the
Sample Delivery Group (SDG), differentiating between initial analyses
and re-analyses; SDG number; Contract number; and detailed documentation
of any quality control, sample, shipment and/or analytical problems
encountered in processing the samples reported in the data package.
Whenever data from sample re-analyses are submitted, the Contractor
shall state in the Case Narrative for each re-analysis, whether it
considers the re-analysis to be billable, and if so, why.
The Contractor must also include documentation of any internal quality
control processes used, a summary of corrective actions taken, and
the resolution.
B-5
10/S6
-------
The Case Narrative shall contain the following statement, verbatim:
"Release of the data contained in this hardcopy data package and in
the computer-readable data submitted on floppy diskette has been
authorized by the Laboratory Manager or his designee, as
verified by the following signature." This statement shall be
directly followed by signature of the Laboratory Manager or his
designee with a typed line below it containing the signer's name and
title, and the date of signature.
Additionally, the Case Narrative Itself oust be signed in original
signature by the Laboratory Manager or his designee and dated.
Traffic Reports
A copy of the Sample Traffic Reports submitted in Item A for all of
the samples in the SOG . The Traffic Reports shall be arranged in
increasing EPA sample number order, considering both letters and
numbering in ordering samples.
Volatiles Data
a. QC Summary
(1) Surrogate Percent Recovery Summary (Form II VOA)
(2) Matrix Spike/Matrix Spike Duplicate Summary (Form III VOA)
(3) Method Blank Summary (Form IV VOA)
(If more than a single form is necessary, forms must be
arranged in chronological order by date of analysis of the
blank.)
(4) GC/MS Tuning and Mass Calibration (Form V VOA)
BFB in chronological order; by instrument.
b. Sample Data
Sample data shall be arranged in packets with the Organic Analysis
Data Sheet (Form I VOA, including Form I VOA-TIC), followed by
the raw data for volatile samples. These sample packets should
then be placed in increasing EPA sample number order, considering
both letters and numbers in ordering samples.
(L) TCL Results - Organic Analysis Data Sheet (Form I VOA).
Tabulated results (identification and quantitation) of the
specified target compounds (Exhibit C). The validation and
release of these results is authorized by a specific, signed
statement in the Case Narrative (reference C.l). In the
event that the Laboratory Manager cannot validate all data
B-6
10/86
-------
reported for each sample, the Laboratory Manager shall
provide a detailed description of the problems associated
with the sample In the Case Narrative.
On Form I, the appropriate concentration units shall be
entered. For example, ug/L for water samples or ug/Kg for
soil/sediment samples. No other units are acceptable. NOTE:
Report analytical results to one significant figure if the
value is less than 10; to two significant figures above 10.
(2) Tentatively Identified Compounds (Form I VOA-TIC).
This form must be included even if no compounds are found.
If so, indicate this on the form by entering "0" in the
field for "Number found."
Form I VOA-TIC is the tabulated list of the highest probable
match for up to 10 of the nonsurrogate organic compounds
not listed in Exhibit C (TCL), including the CAS (Chemical
Abstracts Registry) number, tentative identification and
estimated concentration. For estimating concentration,
assume a response factor of 1, and estimate the concentration
by comparison of the compound peak height or total area
count to the peak height or total area count of the nearest
internal standard free of interferences on the reconstructed
Ion chromatogram. NOTE: The laboratory must be consistent
(i.e., use peak height for all comparisons or_ use total area
count for all comparisons).
(3) Reconstructed total ion chroraatograms (RIC) for. each sample^
sample extract, standard, blank, and spiked sample.
RICs must be normalized to the largest nonsolvent component,
and must contain the following header information:
o EPA sample number
o Date and time of analysis
o GC/MS instrument 10
Internal standard and surrogate spiking compounds are to be
labeled with the names of compounds, either directly out
from the peak, or on a print-out of retention times if
retention times are printed over the peak. If automated
data system procedures are used for preliminary identifica-
tion and/or quantification of the Target Compound List (TCL)
compounds, the complete data system report must be Included
in all sample data packages, in addition to the reconstructed
ion chromatogram. The complete data system report shall
Include all of the information listed below. For laboratories
which do not use the automated data system procedures, a
laboratory "raw data sheet," containing the following
information, must be included in the sample data package in
addition to the chromatogram.
B-7
10/86
-------
o EPA sample number
o Data and elme of analysis
o RT or scan number of identified TCL compounds
o Ion used for quancication with measured area
o Copy of area table from data system
o GC/KS instrument 10
(4) For each sample, by each compound identified:
(a) Copies of raw spectra and copies of background-subtracted
mass spectra of target compounds listed in Exhibit C (TCL)
that are identified in the sample and corresponding
background-subtracted TCL standard mass spectra.
Compound names must be clearly marked on all spectra.
(b) Copies of mass spectra of nonsurrogate organic compounds
not listed In Exhibit C (TCL) (Tentatively Identified
Compounds) with associated best-match spectra (three
best matches).
c. Standards Data
(1) Initial Calibration Data (Form VI VOA) - in order by instrument,
if more than one instrument used.
(a) VOA standard(s) reconstructed ion chromatograms and quanti-
tation reports (or legible facsimile) for the initial (five
point) calibration. Spectra are not required.
(b) All initial calibration data must be included, regardless of
when it was performed and for which case. When more than
one initial calibration is performed, the data must be put
In chronological order, by instrument.
(2) Continuing Calibration (Form VII VOA) - in order by instrument,
if more than one instrument used.
(a) VOA standard(s) reconstructed ion chromatograms and quanti-
tation reports (or legible facsimile) for all continuing (12
hour) calibrations. Spectra are not required.
(b) Whan more Chan one continuing calibration is performed,
forms must be in chronological order, within fraction and
instrument.
(3) Internal Standard Area Summary (Form VIII VOA) - in order
by instrument, if more than one instrument used.
When more than one continuing calibration is performed,
forms must be in chronological order, by instrument.
B-8
10/86
-------
d. Raw QC Data
(1) BFB (for each 12-hour period, for each GC/MS system utilized)
(a) Bar graph spectrum
(b) Mass listing
(2) Blank Data - in chronological order. NOTE: This order is
different from that used for samples.
(a) Tabulated results (Form I VOA)
(b) Tentatively Identified Compounds (Form I VOA-TIC)
even if none found.
(c) Reconstructed ion chromatogram(s) and quantitation
report(s) or legible facsimile (GC/MS)
(d) TCL spectra with lab generated standard. Data systems
which are incapable of dual display shall provide
spectra in order:
o Raw TCL compound spectra
o Enhanced or background subtracted spectra
o Laboratory generated TCL standard spectra
(e) GC/MS library search 3pectra for Tentatively Identified
Compounds (TIC)
(f) Quantitation/Calculation of Tentatively Identified
Compound(s) (TIC) concentrations
(3) Matrix Spike Data
(a) Tabulated results (Form I VOA) of nonspiked TCL compounds
Form I VOA-TIC not required.
(b) Reconstructed ion chromatogram(s) and quantitation
report(s) or legible facsimile (GC/MS). Spectra not
required.
(4) Matrix Spike Duplicate Data
(a) Tabulated results (Form I VOA) of nonspiked TCL compounds.
Form I VOA-TIC not required.
(b) Reconstructed ion chroraatograra(s) and quantitation
report(s) or legible facsimile (GC/MS). Spectra
not required.
B-9
10/86
-------
4. Semivolatiles Data
a. QC Summary
(1) Surrogate Percent Recovery Summary (Form II SV)
(2) Matrix Spike/Matrix Spike Duplicate Summary (Form III SV)
(3) Method Blank Summary (Form IV SV)
(If more Chan a single form is necessary, forms must be
arranged In chronological order by dace of analysis of the
blank*)
(4) GC/MS Tuning and Mass Calibration (Form V SV)
DFTPP in chronological order; by instrument.
b. Sample Data
Sample data shall be arranged in packets with the Organic Analysis
Data Sheet (Form I SV, including Form I SV-TIC), followed by the
raw data for semivolatile samples. These sample packets should
then be placed in increasing EPA sample number order, considering
both letters and numbers in ordering samples.
(1) TCL Results - Organic Analysis Data Sheet (Form I SV-1, SV-2).
Tabulated results (identification and quantitation) of Che
specified earget compounds (Exhibit C). The validation and
release of these results is authorized by a specific, signed
statement in the Case Narrative (reference C.l). In the event
that the Laboratory Manager cannot validate all data reported
for each sample, the Laboratory Manager shall provide a detailed
description of the problems associated wich Che sample in the
Case Narrative.
On Form I, the appropriate concentration units shall be entered.
For example, ug/L for water samples or ug/Kg for soil/sediment
samples. No other units are acceptable. NOTE: Report analytical
results to one significant figure if the value is less Chan 10;
to two significant figures above 10.
(2) Tentatively Identified Compounds (Form I SV-TIC).
This form oust be Included even if no compounds are found. If
so, Indicate this on the form by entering "0" in the field for
"Number found".
B-10
10/86
-------
Form I SV-TIC is che tabulated list of the highest probable
match for up to 20 of the nonsurrogate organic compounds
not listed in Exhibit C (TCL), including the CAS (Chemical
Abstracts Registry) number, tentative identification and
estimated concentration. For estimating concentration,
assume a response factor of 1, and estimate the concentration
by comparison of the compound peak height or total area count
to the peak height or total area count of the nearest internal
standard free of interferences on the reconstructed ion
chromatogram. NOTE: The laboratory must be consistent
(i.e., use peak height for all comparisons or use total area
count for all comparisons).
(3) Reconstructed total ion chromatograms (RIC) for each sample,
sample extract, standard, blank, and spiked sample.
RICs must be normalized to the largest nonsolvent component,
and must contain the following header information:
o EPA sample number
o Date and time of analysis
o GC/MS instrument ID
Internal standard and surrogate spiking compounds are to be
labeled with the names of compounds, either directly out from
the peak, or on a print-out of retention times if retention
times are printed over che peak. If automated data system
procedures are used for preliminary identification and/or
quantification of- the Target Compound List (TCL) compounds,*
the complete data system report must be included in all sample
data packages, in addition to the reconstructed ion chromato-
gram. The complete data system report shall include all of
the information listed below. For laboratories which do
not use the automated data system procedures, a laboratory
"raw data sheet," containing the following information, must
be included in the sample data package in addition to the
chromatogram.
o EPA sample number
o Date and time of analysis
o RT or scan number of identified TCL compounds
o Ion used for quantitation with measured area
o Copy of area table from data system
o GC/MS instrument ID
(4) For each sample, by each compound identified:
(a) Copies of raw spectra and copies of background-subtracted
mass spectra of targec compounds listed in Exhibit C
(TCL) that are identified in the sample and corresponding
background-subtracted TCL standard mass spectra. Compound
names must be clearly marked on all spectra.
B-ll
10/86
-------
(b) Copies of mass spectra of nonsurrogate organic compounds
not listed in Exhibit C (TCL) (Tentatively Identified
Compounds) with associated best-natch spectra (three
best matches).
(c) GPC chromatograms (if GPC performed).
Standards Data
(1) Initial Calibration Data (Form VI SV-1, SV-2) - in order
by instrument, if more than one Instrument used.
(a) BNA standard(s) reconstructed ion chromatograms and quanti-
tation reports (or legible facsimile) for the initial (five
point) calibration. Spectra are not required.
(b) All initial calibration data must be included, regardless of
when it was performed and for which case. When more than
one initial calibration is performed, the data must be put
in chronological order, by instrument.
(2) Continuing Calibration (Form VII SV-1, SV-2) - in order by
instrument, if more than one instrument used.
(a) BNA standard(s) reconstructed ion chromatograms and quanti-
tation reports (or legible facsimile) for all continuing (12
hour) calibrations. Spectra are not required.
(b) When more than one continuing calibration is performed,
forms must be in chronological order, by instrument.
(3) Internal Standard Area Summary (Form VIII SV-1, SV-2) -in order
by instrument, if more than one Instrument used.
When more than one continuing calibration is performed, forms
must be in chronological order by Instrument.
Raw QC Data
(1) DFTPP (for each 12-hour period, for each GC/MS system utilized)
(a) Bar graph spectrum
(b) Mass listing
(2) Blank Data - in chronological order. NOTE: This order is
different from that used for samples.
(a) Tabulated results (Form I SV-1, SV-2)
(b) Tentatively Identified Compounds (Form I SV-TIC) - even
if none found.
B-12
10/86
-------
(c) Reconstructed ion chromatogram(s) and quantitation
report(s) or legible facsimile (GC/MS)
(d) TCL spectra with lab generated standard. Data systems
which are incapable of dual display shall provide
spectra in order:
o Raw TCL compound spectra
o Enhanced or background subtracted spectra
o Laboratory generated TCL standard spectra
(e) GC/MS library search spectra for Tentatively Identified
Compounds (TIC)
(f) Quantitation/Calculation of Tentatively Identified
Compound(s) (TIC) concentrations
(3) Matrix Spike Data
(a) Tabulated results (Form I) of nonspiked TCL compounds.
Form 1 SV-TIC not required.
(b) Reconstructed ion chroraatogram(s) and quantitation
report(s) or legible facsimile (GC/MS). Spectra not
required.
(4) Matrix Spike Duplicate Data
(a) Tabulated results (Form I SV-l, SV-2) of nonspiked TGL
compounds. Form 1 SV-TIC not required.
(b) Reconstructed ion chromatogram(s) and quantitation
report(s) or legible facsimile (GC/MS). Spectra
not required.
5. Pesticide/PCB Data
a. QC Summary
(1) Surrogate Percent Recovery Summary (Form II PEST)
(2) Matrix Spike/Matrix Spike Duplicate Summary (Form III PEST)
(3) Method Blank Summary (Form IV PEST)
(If more than a single form is necessary, forms oust be
arranged in chronological order by date of analysis of the
blank.)
b. Sample Data
Sample data shall be arranged in packets with the Traffic Report
copy, the Organic Analysis Data Sheet (Form I PEST), followed
B-13
10/86
-------
by che raw data for pescicide samples. These sample packets should
then be placed In Increasing EPA sample number order, considering
both letters and numbers in ordering samples*
(1) TCL Results - Organic Analysis Data Sheet (Form I PEST).
Tabulated results (identification and quantitation) of the
specified target compounds (Exhibit C). The validation and
release of these results is authorized by a specific,
signed statement in the Case Narrative (reference C.l). In
the event that the Laboratory Manager cannot validate all
data reported for each sample, the Laboratory Manager shall
provide a detailed description of the problems associated
with the sample in the Case Narrative.
On Form I PEST, the appropriate concentration units shall be
entered. For example, ug/L for water samples or ug/Kg for
soil/sediment samples. No other units are acceptable.
NOTE: Report analytical results to two significant figures
for all pesticlde/PCB samples.
(2) Copies of pesticide chromatograms.
All chromatograms must be labeled with the following
information:
o Sample I.D. (EPA sample number from Traffic Report)
or blank I.D.
o Volume injected (ul)
o Date and time of injection
o GC column identification (by stationary phase)
o GC instrument identification
o Positively identified compounds muse be labeled with the
names of compounds, either directly out from the peak,
or on a print-out of retention times if retention times
are printed over the peak.
(3) Copies of pesticide chromatograms from second GC column
confirmation. Chromatograms to be labeled as in (2) above.
(4) GC Integration report or data system printout and calibra-
tion plots (area vs." concentration) for 4,4'-DDT, 4,4'-DDD,
4,4'-DDE or toxaphene (where appropriate).
(5) Manual work sheets.
(6) GPC chromatograms (if GPC performed).
(7) If pesticide/PCBs are confirmed by GC/MS, the contractor
shall submit copies of raw spectra and copies of background-
subtracted mass spectra of target compounds listed in
Exhibit C (TCL) that are identified in the sample and
B-14
10/86
-------
corresponding background-subtracted TCL standard mass
spectra* Compound names must be clearly marked on all
spectra. For multicomponent pesticides/PCBs confirmed by
GC/MS, the contractor shall submit mass spectra of 3 major
peaks of multicomponent compounds from samples and standards.
c. Standards Data
(1) Form VIII PEST - Pesticide Evaluation Standards Summary
(all GC columns)
(2) Form IX PEST - Pesticide/PCB Standards Summary (all
GC columns)
(3) Form X PEST - Pesticide/PCB Identification (only required
for positive results)
(4) Pesticide standard chromatograms and data system printouts
for all standards to include:
o Evaluation Standard Mix A
o Evaluation Standard Mix B
o Evaluation Standard Mix C
o Individual Standard Mix A
o Individual Standard Mix B
o All mul'tiresponse pesticides/PCBs
o All quantitation standards
o A copy of the computer reproduction or strip chart record*
output covering.the 100 fold range
(a) All chromatograms are required to have the following:
o Label all standard peaks for all individual compounds
either directly out from the peak or on the printout
of retention times if retention times are printed
over the peak.
o Label the chroraatogram for multicomponent standards,
(i.e., Aroclor 1242, Toxaphene)
o List total ng Injected for each standard.
o A printout of retention times and corresponding peak
areas muse accompany each chromatogram.
o Date and time of injection.
o GC column identification (by stationary phase),
o GC instrument identification.
B-15
10/86
-------
d. Raw QC Data
(1) Blank Data - in chronological order. NOTE: This order is
different from that used for samples.
(a) Tabulated results (Form I PEST)
(b) Chromatogram(s) and data system printout(s) (GC) for
each SC column and instrument used for analysis*
(2) Matrix Spike Data
(a) Tabulated results (Form I PEST) of nonspike TCL
compounds.
(b) Chromatogram(s) and data system printout(s) (GC).
(3) Matrix Spike Duplicate Data
(a) Tabulated results (Form I PEST) of nonspike TCL
compounds *
(b) Chromatogram(s) and data system printout(s) (GC)
D. Data in Computer-Readable Form
The Contractor shall provide a computer-readable copy of the data on data
reporting Forms I-X for all samples in the Sample Delivery Group, as speci-
fied in the Contract Performance/Delivery Schedule. Computer-readable data
deliverables shall be submitted on IBM or IBM-compatible, 5.25 inch floppy
double-sided, double density 360 K-byte or a high density 1.2 M-byte diskette.
The data shall be recorded in ASCII, text file format, and shall adhere to
the file, record and field specifications listed in Exhibit H, Data Dictionary
and Format for Data Deliverables in Computer-Readable Format.
If the Contractor wishes to use a reporting format other than the one
specified, equivalence must be demonstrated and approved by the Project
Officer prior to the award of the contract.
E. GC/MS Tapes
The Contractor must store all raw GC/MS data (including data for samples,
blanks, matrix spikes, matrix spike duplicates, standards, BFB and DFTPP)
on magnetic tape, In appropriate instrument manufacturer's format. The
Contractor shall maintain a written reference logbook of tape files to EPA
sample number, calibration data, standards, blanks, matrix spikes, and
matrix spike duplicates. The logbook should include EPA sample numbers
and standard and blank ID's, identified by Case and Sample Delivery Group.
B-16
10/86
-------
The Contractor is required co retain the GC/MS tapes for 365 days after
data submission. During that time, the Contractor shall submit tapes
and associated logbook pages within seven days after receipt of a written
request from the Project Officer or the Sample Management Office.
Extracts
The Contractor shall preserve sample extracts at 4°C (+2°C) in bottles/vials
with Teflon-lined septa. Extract bottles/vials shall be labeled with EPA
sample number, Case number and Sample Delivery Group (SDG) number. A
logbook of stored extracts shall be maintained, listing EPA sample numbers
and associated Case and SDG numbers.
The Contractor is required co retain extracts for 365 days following data
submission. During that time, the Contractor shall submit extracts and
associated logbook pages within seven days following receipt of a written
request from the Project Officer or the Sample Management Office.
Complete Case File Purge
(Formerly, Document Control and Chain-of-Custody Package).
The complete case file purge includes all laboratory records received or
generated for a specific Case that have not been previously submitted to
EPA as a deliverable. These items include buc are not limited to: sample
tags, custody records, sample tracking records,, analysts logbook pages, bench
sheets, chromatographic charts, computer printouts, raw data summaries,
instrument logbook pages, correspondence, and the document inventory (see
Exhibit F).
B-17
10/86
-------
SECTION III
FORM INSTRUCTION GUIDE
This section includes specific instructions for the completion of all
required forms. Each of the forms is specific to a given fraction (volatile,
semivolatile, pesticide/PCB), and in some instances specific to a given matrix
(water or soil) within each fraction. The contractor shall submit only those
forms pertaining to the fractions analyzed for a given sample or samples. For
Instance, if a sample is scheduled for volatile analysis only, provide only VOA
forms. There are two pages relating to the semivolatile fraction for Forms I,
VI, VII, and VIII. Whenever semlvolatlles are analyzed and one of the above
named forms is required, both pages (SV-1 and SV-2) must be submitted. These
instructions are arranged in the following order:
A. General Information and Header Information
B. Organic Analysis Data Sheets (Form I, All Fractions)
C. Surrogate Recovery (Form II, All Fractions)
D. Matrix Spike/Matrix Spike Duplicate Recovery (Form III, All Fractions)
E. Method Blank Summary (Form IV, All Fractions)
F. GC/MS Tuning and Mass Calibration (Form V VOA, Form V SV)
G. Initial Calibration Data (Form VI VOA, Form VI SV)
H. Continuing Calibration Data (Form VII VOA, Form VII SV)
I. Internal Standard Area Summary (Form VIII VOA, Form VIII SV)
J. Pesticide Evaluation Standards Summary (Form VIII Pest)
K. Pesticide/PCB Standards Summary (Form IX Pest)
L. Pesticide/PCB Identification (Form X Pest)
B—18
10/86
-------
A. General Information and Header Information
The data reporting forms presented in Section IV have been designed in
conjunction with the computer-readable data format specified in Exhibit
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). Informa-
tion entered on these forms must not exceed the size of the field given on
the form, including such laboratory-generated items as Lab Name and Lab
Sample ID.
Note that on the hardcopy forms (Section IV), the space provided for
entries is greater in some instances than the length prescribed for the
variable as written to diskette (see Exhibit H). Greater space is
provided on the hardcopy forms for the sake of visual clarity.
Values must be reported on the hardcopy forms according to the individual
form instructions in this Section. For example, results for concentrations
of VOA TCL compounds must be reported to two significant figures if the
value is greater than or equal to 10. Values can be written to the diskette
file in any format that does not exceed the field specification as given
in the record specifications and discussed in "Record Structure", paragraph
5 of Exhibit H.
All characters which apppear on the data reporting forms presented in the
contract (Exhibit B, Section IV) must be reproduced by the contractor when
submitting data, and the format of the forms submitted must be Identical
to that shown in the contract. No information may be added, deleted, or
moved from its specified position without prior written approval of the
EPA Project Officer. The names of the various fields and compounds (i.e.,
"Lab Code," "Chloromethane") must appear as they do on the forms in the
contract, including the options specified in the form (i.e., "Matrix:
(soil/water)" must appear, not just "Matrix"). For items appearing on the
uncompleted forms (Section IV), the use of uppercase and lowercase letters
is optional.
Alphabetic entries made onto the forms by the contractor shall be in ALL
UPPERCASE letters (i.e., "LOW", not "Low" or "low"). If an entry does
not fill the entire blank space provided on the form, null characters
shall be used to remove the remaining underscores that comprise the blank
line. (See Exhibit H for more detailed instructions.) However, do not
remove the underscores or vertical bar characters that delineate "boxes"
on the forms. The only exception would be those underscores at the bottom
of a "box" that are intended as a data entry line (for instance, see
Form 2A, line 30). If data must be entered on line 30, it will replace
the underscores. Whenever an entry is made in a double spaced "box" on a
form (e.g., compound names on Form III V0A—1), the entry should be on the
line shown in the box.
Six pieces of information are common to the header sections of each data
reporting form. They are: Lab Name, Contract, Lab Code, Case No., SAS
No., and SDG No. This information must be entered on every form and must
match on every form.
B-19
10/86
-------
The "Lab Name" shall be che name chosen by Che concraccor Co idendfy Che
laboracory. It may noc exceed 25 characters.
The "Lab Code" is an alphabetical abbreviation of up to 6 letters, assigned
by EPA, co idencify the laboracory and aid in daca processing. This lab
code shall be assigned by EPA ac Che time a contract is awarded, and shall
not be modified by che concraccor, except at che direction of EPA.
The "Case No*" is the EPA-assigned Case number (up to S digits) associated
with the sample, and reported on the Traffic Report.
The "Contract" is the number of Che EPA concracC under which che analyses
were performed.
The "SOG No." is che Sample Delivery Group number. The Sample Delivery Group
(SDG) number is Che EPA Sample Number of che firsc sample received in the
SOG. When several samples are received Cogecher in the firsc SDG shipmenc,
Che SDG number shall be Che lowesc sample number (considering both alpha
and numeric designations) in che firsc group of samples received under
che SDG.
The "SAS No." is che EPA-assigned number for analyses performed under
Special Analytical Services. If samples are to be analyzed under SAS
only, and reported on chese forms, Chen encer SAS No., and leave Case No.
blank. If samples are analyzed according co Che "Routine Analytical
Services" (IFB) protocols and have additional "SAS" requiremencs, Use
both Case No. and SAS No. on all forms. If the analyses have no SAS
requiremencs, leave "SAS No." blank.
The ocher information common to most of the forms is the "EPA Sample No."
This number appears either in the upper righthand corner of the form, or
as che lefc column of a cable summarizing daca from a number of samples.
When "EPA Sample No." Is encered into the triple-spaced box in the upper
righthand corner of Form I or Form X, ic should be encered on Che middle
line of che three lines that comprise the box.
All samples, matrix splices, macrlx spike dupllcaCes, blanks and scandards
shall be identified with an EPA Sample Number. For samples, matrix spikes
and macrlx spike dupllcaCes, Che EPA Sample Number is the unique identifying
number given in che Traffic Reporc that accompanied thac sample.
In order Co facilicaee daca assessmenc, the following sample suffixes muse
be used:
xxxxx
"
EPA sample number
XXXXXMS
-
macrlx spike sample
XXXXXMSD
-
macrlx spike duplicace sample
XXXXXRE
m
re-analyzed sample
XXXXXDL
m
sample analyzed ac a secondary dilucion
B-20
10/86
-------
Form VIII Pest requires that all samples analyzed in a given 72-hour
analytical sequence be specified, regardless of whether or not they are
part of the SDG being reported. Therefore, use "ZZZZZ" as the CPA Sample
No. for any sample analyses not associated with the SOG being reported.
For blanks, standards and tuning compounds, the following identification
scheme must be used as the "EPA Sample No."
1. Volatile blanks shall be identified as:
MMDDVXBI# where:
MMDD ¦ the month and day of analysis of the volatile
blank
V - volatile fraction.
X ¦ matrix used for the volatile blank (S for soil/
sediment, and W for water). If a water blank
is run for soil samples, enter "W".
B - the designator for a blank.
I * an alphabetic instrument identifier. The
contractor shall assign a letter (A-Z) to each
GC/MS and GC system used for analysis under
this contract. These identifiers must remain
consistent throughout the term of this contract,
and any instruments acquired during the term of
the contract must be identified with a new
letter designation. The contractor must maintain
a list of instruments and identifiers, and proving
the list to the agency upon the written request
of the Project Offier or SMO.
# ¦ a daily sequential number for volatile blanks
on each instrument, reset to 1 each day.
For example, the second volatile water blank analyzed on GC/MS
system A on March IS, 1986 would be 0315VWBA2.
2. Semivolatile and pesticide/PCB blanks shall be Identified as:
MMDDFXBI# where:
MMDD ¦ the month and day of extraction of the blank
F ¦ fraction (S for semivolatiles, and P for pesticides/p^^
X ¦ matrix (S for soil/sediment, and W for water)
B » the designator for a blank
B-21
10/86
-------
I ¦ an alphabetic instrument identifier (as described in
paragraph 1. above.
# » a daily sequential number within each fraction,
reset to 1 each day.
For example, the first pesticide/PCB water blank extracted on March 15,
1986 would be 0315PWB1. The designation for the instrument could
not be added until the analysis took place. If the analysis of
samples extracted with this blank was run on April 7, 1986 on GC
system F, the complete blank identifier would be 0315PWBF1. Note
that the analysis date does not appear In a blank Identifier for
semivolatlies or pestlcides/PCBs.
3. Volatile and semivolatile standards shall be identified as:
MMDDFSI# where:
MMDD - the date of analysis of the standard
F * fraction (V for volatlles, and S for semi volatlles)
S ¦ a number one through five (1-5) designating the
standard. Because the amounts or concentrations of
the standards are specified in the contract, each
standard within a fraction can be specified by a
single number.
Volatlles
Semivolatlles ¦
S-
(utt/L)
(nuc)
1
20
20
2
50
50
3
100
80
4
150
120
5
200
160
I ¦ an alphabetic instrument identifier, (as described
in paragraph 1. above)
0 ¦ a dally sequential number on each instrument, to
account for multiple injections of standards,
particularly the continuing calibration standards.
4. Pesticide/PCB standards shall be identified as specified in the
instructions for Form XIII.
5. The tuning compounds brooofluorobenzene and decaflurotriphenyl-
phosphlne shall be identified as follows:
MMDDBF3I# and MMDDDFTI#, respectively,
B-22
10/86
-------
where:
MMDD ¦ the month and day of injection of the tuning
compound
I - the instrument identifier (as described in para-
graph 1. above).
# « a daily sequential number for the tuning compound
injection on that instrument.
If DFTPP is injected as part of a calibration standard, this
method of identifying the injection will not be used. Because
BFB may not be injected as part of a calibration standard this
method of identification must be used for BFB.
Several other pieces of information are common to many of the Data Reporting
Forms. These include: Matrix, Sample wt/vol, Level, and Lab Sample ID.
For "Matrix" enter "SOIL" for soil/sediment samples, and enter "WATER" for
water samples. NOTE: The matrix must be spelled out. Abbreviations such
as "S" or "W" shall not be used.
For "Sample wt/vol" enter the number of grams (for soil) or milliliters
(for water) of sample used in the first blank line, and the units, either
"G" or "ML" in the second blank.
For "Level" enter the determination of concentration level made from the
mandatory screening of soils. Enter as "LOW" or "MED", not "L" or "M".
All water samples are "LOW" level and shall be entered as such.
"Lab Sample ID" is an optional laboratory-generated internal identifier.
Up to 12 alpha-numeric characters may be reported here.
"Lab File ID" is the laboratory-generated name of the GC/MS data system
file containing information pertaining to a particular analysis. Up
to 14 alpha-numeric characters may be used here.
Forms II, IV, V, VIII, IX, and X contain a field labeled "page __ of "
in the bottom lefthand corner. If the number of entries required on~any
of these forms exceeds the available space, continue entries on another
copy of the same fraction-specific form, duplicating all header information
If a second page is required, number them consecutively, as "page 1 of 2"
and "page 2 of 2". If a second page is not required, number the page
"page 1 of 1." NOTE: These forms are fraction-specific, and often matrix-
specific within fraction. For example, Form II VOA-1 and Form II VOA-2
are for different data. Therefore, do not number the pages of all six
versions of Form II as "1 of 6, 2 of 6, etc." Only number pages within a
fraction-specific and matrix-specific form.
For rounding off numbers to the appropriate level of precision, observe eh«
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
B-23
10/86
-------
It and Increase the last digit to be retained by 1 (round up). If the
figure following the last digit to be retained equals 5, round up If the
digit to be retained Is odd, and round down If that digit Is even.
B. Organic Analysis Data Sheet (Form I)
1. Form I VOA, Form I SV-1, Form I SV-2, Form I Pest
This form 1s used for tabulating and reporting sample analysis results
for Target Compound List (TCL) compounds. If all fractions are not
requested to be analyzed, only the pages specifically required oust be
submitted. If VOA analysis only is requested, Form I VOA and Form I
VOA TIC must be submitted. If the pestlcide/PCB analysis is the only
analysis requested, only Form I Pest must be submitted for that sample.
Complete the header information on each page of Form I required,
according to the Instructions in part A. and as follows:
For volatlles, for "Z moisture not dec.", enter the nondecanted percent
moisture. For semivolatlles and pesticides/PCB, enter values for both
nondecanted percent moisture and decanted percent moisture, in the
appropriate fields. Report percent moisture (decanted or not decanted)
to the nearest whole percentage point (i.e., 5%, not 5.32). If a
decanted percent moisture Is not determined, because the sample has no
standing water over it, leave "Z moisture dec." blank.
For semivolatlles and pestlcldes/PCBs, enter the method of extraction
as "SEPF" for separatory funnel, and "CONT" for continuous liquid -
liquid extraction, or "SONC" for sonicatlon (soils only).
If gel permation chromatography, "GPC Cleanup" was performed, enter "Y"
for yes. Otherwise, enter "N" for no, if GPC was not performed.
Enter pH for semivolatile and pestlcldes/PCBs, reported to 0.1 pH units.
"Date Received" is the date of sample receipt at the laboratory, as
noted on the Traffic Report (i.e., the VTSR). It should be entered
as MM/DD/YY.
"Date Extracted" and "Date Analyzed" should be entered in a similar
fashion. For peaticlde/PCB samples, the date of analysis should be the
date of the first GC analysis performed. The date of sample receipt
will be compared with the extraction and analysis dates of each
fraction to ensure that contract holding times were not exceeded.
If a sample has been diluted for analysis, enter the "Dilution Factor"
as a decimal number, such as 0.001 for a 1 to 1000 dilution of the
sample. If a sample was not diluted, enter 1.
For positively identified TCL compounds, the contractor shall report the
concentrations detected as uncorrected for blank contaminants.
B-24
10/86
-------
For volatile and semivolatile results, reporc analytical results to
one significant figure if the value is less than 10, and two significant
figures above 10*
Report all pesticides/PCB results to two significant figures.
The appropriate concentration units, ug/L or ug/kg, must be entered.
If the result is a value greater than or equal to the quantitation
limit, report the value.
Under the column labeled MQ" for qualifier, flag each result with the
specific Data Reporting Qualifiers listed below. The Contractor is
encouraged to use additional flags or footnotes. The definition of
such flags must be explicit and must be included in the Case Narrative.
For reporting results to the USEPA, the following contract specific quali-
fiers are to be used. The seven qualifiers defined below are not subject
to modification by the laboratory. Up to five qualifiers may be reported
on Form I for each compound.
The seven EPA-defined qualifiers to be used are as follows:
U - Indicates compound was analyzed for but not detected. The
sample quantitation limit must be corrected for dilution and for
percent moisture. For example, 330 U for phenol in water if the
sample final volume is the protocol-specified final volume. If
a 1 to 10 dilution of extract is necessary, the reported limit
is 3300 U. For a soil sample, the value must also be adjusted
for percent moisture. For example, if the sample had 24% moisture
and a 1 to 10 dilution factor, the sample quantitation limit for
phenol (330 U) would be corrected to:
(330 U) x df where D • 100 - % moisture
D 100
and df « dilution factor
at 242 moisture, D « 100-24 ¦ 0.76
100
(330 U? x 10 ¦ 430 U rounded to the appropriate number of
.76 significant figures
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 daca
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 quanti-
tation limit is 10 ug/L, but a concentration of 3 ug/L is calcu-
lated, report it as 3J. The sample quantitation limit must be
adjusted for both dilution and percent moisture as discussed for •
B-25
10/86
-------
the U flag, so that if a sample with 24% moisture and a 1 to 10
dilution factor has a calculated concentration of 300 ug/L and a
sample quantitation limit of 430 ug/kg, report the concentration
as 300J on Form I.
C - This flag applies to pesticide results where the identification
has been confirmed by GC/MS. Single component pesticides
M0 ng/ul in the final extract shall be confirmed by GC/MS.
B - This flag is used vhen the analyte is found in the associated
blank as well as in the sample. . It indicates possible/probable
blank contamination and warns the data user to take appropriate
action. This flag must be used for a TIC as well as for a
positively identified TCL compound.
0 - This flag identifies compounds whose concentrations are outside
the calibration range of the analysis. If one or more compounds
have a response greater than full scale, the extract must be
diluted and reanalyzed, according to the specifications in
Exhibit 0. If the dilution of the extract causes any compounds
Identified in the first analysis to be below the calibration
range in the second analysis, then the results of both analyses
shall be reported on separate Forms I. The Form I for the
diluted sample shall have the "DL" suffix appended to the sample
number. Compounds whose concentrations are above the calibration
range of the first analysis shall be flagged with "0" on the
Form I from that first analysis. Compounds Identified in that
first analysis but below the calibration range of the second
analysis shall be flagged "0" on the Form I for the second
analysis. The contractor shall report the results of at most two
analyses, one with the "DL" suffix, and one without the suffix.
A - This flag indicates that a TIC is a suspected aldol-condensation
product.
X - Other specific flags and footnotes may be required Co properly
define the results. If used, they must be fully described and
such description attached to the Sample Data Summary Package
and the Case Narrative. If more than one is required, use "Y"
and "Z", as needed.
The combination of flags "BU" or"UB" is expressly prohibited. Blank
contaminants are flagged "B" only when they are also detected in the
sample.
If analyses at two different dilution factors are required (see Exhibit
0), follow the data reporting instructions given in Exhibit 0 and with
the "0" flag above.
2. Form I V0A-TIC and Form I SV-TIC
Fill in all header information as above.
B-26
10/86
-------
Report Tentatively Identified Compounds (TIC) including CAS number,
compound name, retention time, and the estimated concentration (criteria
for reporting TICs are given in Exhibit D, Section IV). Retention time
must be reported in minutes arid decimal minutes, not seconds or
minutes:seconds.
If in the opinion of the mass spectral interpretation specialist, no
valid tentative identification can be made, the compound shall be reported
as unknown.
Include a Form I VOA-TIC or SV-TIC for every volatile and semivolatile
fraction of every sample and method blank analyzed, even if no TICs are
found. Total the number of TICs found, including aldol-condensation
products (but see below), and enter this number in the "Number TICs found
If none were found, enter "0" (zero).
If the name of a compound exceeds the 28 spaces in the TIC column, trun-
cate the name to 28 characters. If the compound is an unknown, restrict
description to no more than 28 characters (i.e., unknown hydrocarbon,
etc.).
Peaks that are suspected as aldol-condensation reaction products (i.e.
4-methyl-4-hydroxy-2-pentanone and 4-methyl-3-pentene-2-one) shall be *
summarized on this form, flagged "A", and included in the total "Number
TICs found," but not counted as part of the 20 most intense non-TCL semi—
volatile compounds to be searched*
C. Surrogate Recovery (Form II)
Form II is used to report the recoveries of Che surrogate compounds added t0
each sample, blank, matrix spike, and matrix spike duplicate. Form II is
matrix-specific as well as fraction-specific, so that surrogate recoveries
for volatile water samples are reported on a different version of Form II
than volatile soil sample surrogate recoveries.
Complete the header information and enter EPA Sample Numbers as described
in part A. For soil samples only, specify the "level" as "LOW" or "MED",
as on Form I. Oo not mix low and medium level samples on one form. Complete
one for each level. For each surrogate, report the percent recovery to the
number of significant figures given by the QC limits at the bottom of the
form*
Flag each surrogate recovery outside che QC limits with an asterisk (*).
The asterisk must be placed in the last space in each appropriate column,
under the symbol. In the far righthand column, total the number of
surrogate recoveries outside the QC limits for each sample. If no surro-
gates were outside the limits, enter "0".
The pesticide surrogate recovery limits are only advisory, but che contractor
must flag chose recoveries outside che advisory QC limits nonetheless.
Number all pages as described in part A.
B-27
10/86
-------
Matrix Spike/Matrix Spike Duplicate Recovery (Form III)
This form is used to report the results of the analyses of a matrix spike
and matrix spike duplicate. As with the surrogate recovery form (II), the
form is matrix-specific within each fraction.
Complete the header information as Instructed in Part A, Including the EPA
Sample Number for the matrix spike without the suffixes MS or MSO.
For soil samples, specify "level" as "LOU" or "MED", as on Form I. Cases
containing soil samples at both levels require MS/MSD at each level,
therefore, for soils, prepare one form for each level.
Report the amount in nanograms of matrix spike analyte added to each
aliquot. For each matrix spike compound, enter the concentration in
the sample extract. For low level volatile analyses, enter the concen-
tration in the sample. For medium level volatile analyses, enter the
concentration in the methanol extract. If a matrix spike compound was
not detected during the analysis of the original unspiked sample, enter
the sample results as "0" (zero). For semivolatile, pesticide/PCB, and
medium level methanol extracted volatile analyses, calculate and report
the concentration found in the extract of the matrix spike and the extract
of the matrix spike duplicate. For low level volatile analyses, calculate
and report the concentration found in the matrix spike and matrix spike
duplicate analyses.
Calculate the percent recovery of spiked compounds for the matrix spike
and matrix spike duplicate according to Exhibit E. Calculate the relative
percent difference (RPD) between the matrix spike recovery and the matrix
spike duplicate recoveries. Enter the percent recovery of the matrix
spike in both the upper and lower sections of the form. Compare the
recoveries and the RPDs to the QC limits given on the form. Flag each
recovery or RPD outside the QC limits with an asterisk (*). The asterisk
must be placed in the last space of the recovery and RPD columns, under
the symbol.
Summarize the values outside the QC limits at the bottom of the page. No
further action is required by the laboratory. Performance-based QC limits
will be generated and updated from recovery and RPD data.
Method Blank Summary (Form IV)
This form summarlzles the samples associated with each method blank analysis.
A copy of the appropriate Form IV Is required for each blank.
Complete the header Information on Form IV as described in Part A, being sure
to enter the appropriate "EPA Sample Number for Method Blank".
For volatile and semivolatile blanks, enter the "Instrument ID", "Date
Analyzed", "Matrix" and "Level". All water blanks are "LOW". The "Time
Analyzed" shall be in military time.
B-28
10/86
-------
For semivolatile and pescicide/PCB blanks, enter the method of extraction
as "SEPF" for separator? funnel, or "SONC" for sonication, or "CONT" for
continuous liquid-liquid extraction.
For semivolatile and pesticide/PCB method blanks, enter the date of extrac-
tion of the blank. Pesticide/PCB contaminants must meet the identification
criteria in Exhibit 0 PEST, which requires analysis of the blank on two
different GC Columns. Therefore, enter the date, time and Instrument ID
of both analyses on the pesticide method blank summary. The information
on the two analyses is differentiated as Date Analyzed (1), Date Analyzed
(2), etc. If the analyses were run simultaneously, the order of reporting
is not Important. Otherwise (1) shall be the first analysis, and (2) the
second. Identify both GC columns by stationary phase under "GC Column ID".
For Pesticide/PCB blanks, enter "Matrix" and "Level" in a similar fashion
as for the other fractions. All water samples are "LOW". Enter "Lab File
ID" only if GC/MS confirmation was required. Otherwise, leave blank.
For all three fractions, as appropriate, summarize the samples associated
with a given method blank in the table below the header, entering EPA
Sample Number, and Lab Sample ID. For volatiles, enter the Lab File ID and
time of analysis of each sample. For semivolatiles, enter Lab File ID.
For semivolatiles and pesticides/PCBs, enter the date of analysis of each
sample. For pesticide/PCBs, if only one analysis is required (i.e., no
pesticides/PCBs to be confirmed), leave blank the fields for the second
analysis.
Number all pages as described in part A.
F. GC/MS Tuning and Mass Calibration (Form V)
This form is used to report the results of GC/MS tuning for volatiles and
semivolatiles, and to summarize the date and time of analysis of samples,
standards, blanks, matrix spikes, and matrix spike duplicates associated
with each GC/MS tune.
Complete the header information as in part A. Enter the "Lab File ID"
for the injection containing the GC/MS tuning compound (BFB for volatiles,
DFTPP for semivolatiles). Enter the "Instrument ID". Enter the date and
time of injection of the tuning compound. Enter time as military time.
For each ion listed on the form, enter the percent relative abundance in
the righthand column. Report relative abundances to the number of signi-
ficant figures given for each ion in the ion abundance criteria column.
All relative abundances must be reported as a number. If zero, enter "0",
not a dash or other non-numeric character. Where parentheses appear,
compute the percentage of the ion abundance of the mass given in the
appropriate footnote, and enter that value in the parentheses.
In the lower half of the form, list all samples, standards, blanks, matrix
spikes, and matrix spike duplicates analyzed under that tune in chronological
order, by time of analysis (in military time). Refer to part A. for specific
instructions for identifying standards and blanks.
B-29
10/86
-------
The GC/MS tune expires twelve hours from the doe of injection of the
tuning compound (BFB or DFTFP) listed at the top of the form. In order to
meet the tuning requirements, a sample, standard, blank, matrix spike, or
matrix spike duplicate must be injected within twelve hours of the injection
of the tuning compound*
Number all pages as described in part A.
G. Initial Calibration Data (Form VI)
After a GC/MS system has undergone an Initial five-point* calibration at the
specific concentration levels described in Exhibit E, and after all initial
calibration criteria have been met, the laboratory must complete and submit a
Form VI for each volatile or semlvolatile TCL initial calibration performed
which is relevant to the samples, blanks, matrix spikes, matrix spike dupli-
cates in the SDG.
Complete all header information as in part A. Enter the "Case No." and
"SDG No." for the current data package, regardless of the original Case
for which the initial calibration was performed. Enter "Instrument ID"
and the date(s) of the calibration. If the calendar date changes during the
calibration procedure, the inclusive dates should be given on Form VI.
Enter the "Lab File ID" for each of the five calibration standards injected.
Complete the response factor data for the five calibration points, and
then calculate and report the average relative response factor (RRF) for
all TCL and surrogate compounds. The laboratory must report the ZRSD for
all' compounds. All CCC compounds must have a 2RSD of less than or equal
to 30.0 percent. All SPCC compounds must have a minimum average relative
response factor (RRF) of 0.300 (0.2S0 for Bromoform).
SD
%RSD - x 100
x
where: ZRSD * Relative Standard Deviation
SD - Standard Deviation of initial 5 response factors (per
compound)
where: SD 1 _
Yi-1 —-
N-l
x - mean of initial 5 response factors (per compound)
*For- Semivolatiles, nine compounds: Benzoic Acid, 2,4-Dinitrophenol,
2,4,5-Trichlorophenol, 2-Nitroaniline, 3-Nitroaniline, 4-Nitroaniline,
4-Nitrophenol, 4,6-Dinitro-2-Methylphenol, and Pentachlorophenol will only
require a four-point initial calibration at SO, 80, 120, and 160 total nanograms
because detection at less than 50 nanograms per injection is difficult. If a
four-point calibration is performed for these compounds, leave RF20 blank.
B-30
10/86
-------
H. Continuing Calibration Data (Form VII)
The Continuing Calibration Data Form is used to verify the calibration
of the GC/MS system by Che analysis of specific calibration standards. A
Continuing Calibration Data Form Is required for each twelve (12) hour time
period for both volatile and semivolatile TCL compound analyses.
The Contractor laboratory must analyze calibration standards and meet
all criteria outlined in Exhibit E. After meeting specific criteria for both
SPCC and CCC compounds, a Continuing Calibration Data Form must be completed
and submitted.
Complete all header information as in part A. Enter instrument ID, date
and time of continuing calibration, the Lab File 10 of the continuing
calibration standard, and date of initial calibration (give inclusive dates
if initial calibration is performed over more than one date). Using the
appropriate Initial Calibration (Volatile or Semivolatile) fill In the
average relative response factor (RRF) for each TCL compound. Report the
relative response factor (RRF50) from the continuing calibration standard
analysis. Calculate the Percent Difference (%D) for all compounds. For CCC
compounds, ensure that the %D is less than or equal to 25.0 percent.
After this criterion has been met, report the Percent Difference for all
TCL and surrogate compounds.
RRFj - RRFC
Z Difference ¦ x 100
RRF I
where,
RRFj ¦ average relative response factor from initial calibration.
RRFC ¦ relative response factor from continuing calibration standard.
All semivolatile standards are analyzed at SO total ng.
I. Internal Standard Area Summary (Form VIII VOA and SV)
This form Is used Co summarize the peak areas of the internal standards
added to all volatile and semivolatile samples, blanks, matrix spikes, and
matrix spike duplicates. The data are used to determine when changes in
internal standard responses will adversely affect quantification of target
compounds. This form must be completed each time a continuing calibration
is performed, or when samples are analyzed under the same GC/MS tune as
an Initial calibration.
Complete the header information as in part A. Enter the EPA Sample Number
and Lab File ID of the continuing calibration standard, as well as the
date and time of analysis of the continuing calibration standard. If
samples are analysed immediately following an initial calibration, before
another GC/MS time and a continuing calibration, Form VIII shall be
B-31 10/86
-------
completed on che basis of Che Internal standard areas of the 50 ug/L
initial calibration standard for volaclles, and the 50 ng initial cali-
bration standard for semi volatiles. Use the dace and time of analysis of
this standard, and its Lab File 10 and areas in place of those of a contin-
uing calibration scandard.
From che results of che analysis of Che concinuing calibration scandard,
enter Che area measured for each incernal standard and ics retention time
under the appropriate column in che row labeled "12 HOUR STD". For each
internal standard, calculate Che upper limic as che area of che parcicular
scandard plus 100% of ics area (i.e., cwo Cimes che area in Che 12 HOUR
STD box), and the lower limit as Che area of Che internal standard minus
50% of its area (i.e., one half the area in the 12 HOUR STD box). Report
these values in the boxes labeled "UPPER LIMIT" and "LOWER LIMIT" respeccively.
For each sample, blank, matrix spike, and matrix spike duplicate analyzed
under a given continuing calibration, encer che EPA Sample Number and the
area measured for each internal scandard and ics retention time. If che
internal standard area is outside the upper or lower limits calculated
above, flag thac area wich an ascerlsk (*). The ascerisk must be placed
in the far rlghc hand space of the box for each incernal scandard area,
directly under the symbol.
Number all pages as described in part A.
J. Pesticide Evaluation Standards Summary (Form VIII Pest)
This form is used to report che seventy-two (72) hour analytical sequence
for pesticide analysis.
The laboratory shall complete all the header information as in Part A.
Encer dates of analyses, GC column and instrument ID. Idencify GC Column
by scationary phase. Enter the Lab Sample ID for each scandard, If it
applies.
Evaluation Standard Mix A, B, and C must be analyzed at the initiation of
every 72-hour sequence Co check the linearity of the GC system. Calculate
and reporc the Calibration Factor (total peak area*/amounc injected in
nanograms) for each of Che three pesticides and che surrogate (Aldrln,
Endrln, 4,4'-DDT and Dlbucylchlorendate) at each concencradon level (see
Exhibic D). Calculace and reporc Che percenc relacive scandard deviaeion
(%RSD) for each of che four compounds (Eq. l.l). The RSD must be less
than 10.0 percent for Aldrin, Endrln, and Dibutylchlorendate. The 10% RSD
criteria pertain only to the column being used for quantitation, however,
Co decermine chac no pescicides/PCBs are presenc Is a form of quandtaclon.
*Noce: The cerm peak height may be subsclcuced for Che Cerm peak area.
B-32
10/86
-------
If the 2RSD for 4,4'-DDT exceeds 10.0 percent, plot a standard curve and
determine the ng for each sample from that curve
SO
ZRSD x 100 Eq. 1.1
x
where: SD ¦
N-l
x - mean of Initial three Calibration factors (per compound)
Evaluation Standard Mix B must be analyzed near the beginning of the
analytical sequence, after the first five samples, and then every ten
samples thereafter during a 72-hour period (see Exhibits 0 and E). Calcu-
late and report the percent breakdown for 4,4'-DDT and/or Endrin for the
mixed phase GC column (see Exhibit E). Enter the lab sample ID and time of
analysis for each analysis of the Evaluation Standard Mix 3.
Calculate the percent breakdown for Endrin and/or 4,4'-DDT on the 0V-1 or
equivalent GC column using Equations 1.2 and 1.3. The combined percent
breakdown must not exceed 20.0 percent for Endrin and 4,4'-DDT.
Total DDT degradation peak area*(DDE + DDD)
Z breakdown ¦ • ———— x 100 Eq. 1.2
for 4,4'-DDT Total DDT peak area* (DDT + DDE + DDD)
Z breakdown for Endrin » Eq. 1.3
Total Endrin degradation peak areas*(Endrin Aldehyde + Endrin Ketone)
Total Endrin Peak Area*(Endrin + Endrin Aldehyde + Endrin Ketone)
Enter the values for the breakdown of Endrin and 4,4*-DDT in their respective
columns. Calculate the combined breakdown according to Equation 1.4 and enter
in the "COMBINED" column.
If Endrin cannot be separated from 4,4'-DDT on a given GC column, calculate a
combined percent breakdown for Endrin/4,4'-DDT using Equation 1.4. The combined
degradation must not exceed 20.0 percent. Leave the endrin and 4,4'-DDT
columns blank if they cannot be separated, and report only the combined
breakdown.
*Note: The term peak height may be substituted for Che term peak area.
B-33 '10/86
-------
Combined % Breakdown - Eq. 1.4
Total Endrin/DDT degradation peak area*(DDD, DDE, Endrln Aldehyde, Endrln Ketone)
Total Endrin/DDT peak area*(Endrin, Endrin Aldehyde, Endrin Ketone, DDD, DDE, DDT)
Complete the header Information on the second page of Form VIII Pest as on the
first page.
For each sample, standard, matrix spike, matrix spike duplicate, and blank,
enter the EPA sample number, lab sample ID, date and time of analysis. Each
sample analyzed as part of the 72-hour analytical sequence must be reported
on the second page of Form VIII PEST even if it is not associated with the
SDG, "inorder to determine if the proper sequence of samples and standards
was followed. However, the laboratory may use the EPA Sample No. of "ZZZZZ"
to distinguish all samples that are not part of the SDG being reported.
For pesticlde/PCB standards, the following scheme shall be used to enter
Sample Number".
*EPA
Name
Evaluation Mix A
Evaluation Mix B
Evaluation Mix C
Individual Mix A
Individual Mix B
Toxaphene
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
EPA Sample Number
EVALA
EVALB
EVALC
INDA
INDB
TOXAPH
AR1016
AR1221
AR1232
AR1242
AR1243
AR1254
A&1260
If Individual Mix A and Individual Mix B are combined into one mixture on
a capillary column (see Exhibit D), the EPA Sample Number shall be entered
as INDAB. Similarly, the permitted mixture of Aroclor 1016 and Aroclor 1260
shall be entered as AR1660.
Every standard, sample, matrix spike, matrix spike duplicate, and blank must
contain the surrogate dibutylchlorendate (DBC) at the specified level for
both water or soil/sediment samples. The retention time shift for Dlbutyl-
chlorendate on packed columns must not exceed 2.0 percent (0.3 percent for
capillary columns) difference (ZD) between the initial standard (Evaluation
Standard Mix A) and any blank, standard, sample, matrix spike, or
matrix spike duplicate analyzed during the 72-hour time period. Calculate
and report the percent difference (ZD) for all samples, matrix spike,
matrix spike duplicate, standards, and blanks, according to Eq. 1.5.
*Note: The term peak height may be substituted for the term peak area.
B-34
10/86
-------
RTi - RTg
Z Difference » x 100 Eq 1.5
RTi
where,
RT^ - absolute retention time of dibutylchorendate in Che initial
standard (Evaluation Mixture A).
RTS - absolute retention time of dibutylchlorendate in the sample,
matrix spike, matrix spike duplicate, blank, or any standard
analyzed after Evaluation Mixture A*
Enter the retention time shift for OBC in the "ZD" column. Flag all those
values outside the QC limits by entering an asterisk (*) in the last column,
under the If the retention time shift cannot be calculated due to
interfering peaks, leave the ZD column blank, flag the value vith an asterisk,
and document the problem in the Case Narrative.
Number this page as described in Part A.
Form VIII PEST is required for each seventy-two (72) hour period, for each
GC system and for each GC column used to analyze TCL Pesticide/PCBs.
K. Pesticide/PCB Standards Summary (Form IX)
This form is used to monitor variations in the Calibration Factor and
retention time for each pesticide/PCB standard during each seventy-two
(72) hour period.
The laboratory shall complete Che header information as in Part A. Enter
instrument ID, and GC column ID. GC column identification must be by
stationary phase. This form is required for each GC system and for e-ach
GC column used to analyze TCL Pesticides/PCBs.
Individual Standard Mix A and B must be analyzed at or near the beginning
of a seventy-two (72) hour sequence (before the analysis of any samples).
Individual Standard Mix A and B must also be analyzed periodically during
sample analysis (at the intervals specified in Exhibits D and E), and at
the end of the seventy-two (72) hour sequence. Form IX is designed to
compare the first analysis of each of the standards to each subsequent
analysis. Therefore, a copy of Form IX must be completed for each analysis
of Individual Standard Mix A and B, and each multlresponse standard after
the analysis of samples has begun. For each copy of Form IX for a given
analytical sequence, the data entered in the lefthand column will be identical.
The header over the lefthand column contains the inclusive dates and times of
analysis of the standards reported on the left side of Form IX. Considering
the first analysis of Individual Standard Mix A, Individual Mix B, and all
the multlresponse pesticides and PCBs, enter the first and last dates and
times of analysis of these standards.
B-35
10/86
-------
Report Che retention time of each compound in the left hand column
labelled "RT". Retention times must be reported in minutes and decimal
minutes (i.e., 1.99 minutes), not in seconds, or minutes:seconds.
Calculate the retention time window for each compound , according to the
Instructions in Exhibit E, Section III, Part 4. Report the retention
time window for each compound as a range of two values, i.e., from 1.48
to 1.54. Enter the lower value of the range in the column under "RT
WINDOW" labeled "FROM". Enter the upper value of the range in the
column under "TO". Do not separate the two values with a hyphen, and do
hot enter the retention time window as a plus/minus value such as ±0.03.
NOTE: By definition, the center of the retention time window must be the
retention time listed immediately to the left of the retention time
window.
Calculate the calibration factor for each compound according to Equation
1.6, and the value report under the left hand column labeled "CALIBRATION
FACTOR".
For each subsequent analysis of an Individual Standard Mix A or B, or a
multlresponse compound, complete the right hand spaces for date and time
of analysis and lab sample ID, and the columns labeled* "RT" and "CALIBRATION
FACTOR" with the results from that analysis. NOTE: While the lefthand
side of Form IX will contain retention times, retention time windows, and
calibration facctors for all the compounds, the righthand side will contain
data from the analysis of only some of the compounds.
Total peak area* of a Standard
Calibration Factor ¦ —— —— Eq 1.6
Total mass injected (ng)
Calculate and report the percent difference in the Calibration Factor for
each pesticlde/PCB using Equation 1.7.
|AbL - Ab2|
Percent Difference (ZD) " x 100 Eq. 1.7
Abj
where,
Abi • Calibration Factor from the Initial standard for the 72-hour
period
Ab2 • Calibration Factor from each subsequent standard
The absolute percent difference between the individual Calibration Factors
for each compound in the pesticide standard may vary no more than 15.0
percent for a quantitation run, or more than 20.0 percent for a confirm-
ation run. Primary runs must meet the criteria required for quantitation
if no other analyses are performed.
*Note: The term "peak height" may be substituted for the term "peak area".
B-36
10/86
-------
If Che results of analyses of compounds In the Individual Standard
Mix are to be used for quantifying pesticide/PCB concentrations in the
samples preceding the analysis on the right hand side of the form, then
enter "Y" for yes, in the column labeled "QNT Y/N" for each compound
quantified. If the results are not used for quantitation of a particular
compound, enter "N", for no. Determining that no compounds are present
above the CRQL is a form of quantitation.
For each subsequent analysis of an Individual Standard Mix A or B, or
multiresponse compound, complete the right hand side of a copy of Form
IX, with the results of the initial analyses of all the compounds as the
data in the left hand side.
For mult1component analytes, the single largest peak characteristic of the
compound must be used. A characteristic peak will not exist for similar
compounds such as Aroclor 1016 and Aroclor 1242. In these cases
utilization of a common peak is acceptable.
Regardless of which standards are reported on subsequent pages of Form IX,
number all pages sequentially as described in Part A. A3 Individual Mix A
and Mix B must be analyzed at the end of an analytical sequence, there will
always be at least two pages of Form IX, 1 of 2, and 2 of 2, except
where Mixes A & B have been combined for capillary column analysis.
L. Pesticide/PCB Identification (Form X)
This form summarizes the tentative and confirmed identity of all TCL
pesticldes/PCBs detected in a given sample. It reports the retention
times of the compound on both columns on which it was analyzed, as well
as the retention time windows of the standard for that compound on both
of these columns. One copy of Form X is required for each sample in which
TCL pesticides or PCBs are detected. If none are detected in a given
sample, no copy of Form X is required for that sample.
Complete the header information as in Part A. Enter the GC Column ID
(by stationary phase) for each of the two columns, one as GC Column (1),
the other as (2). Enter the Instrument ID and Lab Sample ID associated
with each GC column directly below. Enter Lab File ID only if the
compounds were confirmed by GC/MS.
For each TCL pesticide or PCB detected, enter the name of the compound
under "PESTICIDE/PCB**. Enter the retention times on each column of the
compounds detected in the sample next to the appropriate column designation
(1 or 2). Enter the retention time windows on each column of the appro-
priate standard. These data must correspond with those on Form IX, and
are entered in a similar manner. The lower value is entered under the
"FROM" column, the upper value under the "TO" column. Do not use a
hyphen.
Under "Quant? (Y/N)" enter "Y" for the GC column (1 or 2) used for quanti-
tation, and "N" for the other column, for each compound. Do not leave
this field blank for either GC column.
B-37
10/86
-------
Under "GC/MS? (Y/N)" enter "Y" for both GC columns if the compound was
"confirmed by GC/MS. Enter "N" for both GC columns if the compound was
not confirmed by GC/MS.
If more Pesticide/PCB TCL compounds are identified in an Individual sample
than can be reported on one copy of Form X, then complete as many addi-
tional copies of Form X as necessary, duplicating all header information,
and numbering the pages as described in Part A.
B-38
10/86
-------
SECTION IV
DATA REPORTING FORMS
B-39
10/86
-------
1A
VOLATILE ORGANICS ANALYSIS DATA SHEET
EPA SAMPLE NO.
Lab Name:,
Lab Code:
Case No.:
Contract:
SAS No.:
SOG No.:
Matrix: (soil/water)
Sample wt/vol:
Level: (low/med)
% Moisture: not dec.
(g/mL)
Lab Sample ID:
Lab File ID:
Date Received:
Date Analyzed:
CAS NO.
COMPOUND
Dilution Factor:
CONCENTRATION UNITS:
(ug/L or uq/Kg)
74-87-3
74-83- 9
75-01- 4
75-00-3
75-09-2
67-64-1
75-15-0
75-35-4
75-34-3
540-59-0
67-66-3
107-06- 2
78-93-3
71-55-6
56-23-5
108-05- 4
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
79-34-5
108-88-3
108-90-7
100-41-4
100-42-5
133-02-7
—Chloromethane__
—Bromomethane
Vinyl Chloride.
Chloroethane
Methylene Chloride.
Acetone _
—Carbon Disulfide
—1,l-Dichloroethene.
—1,l-Dichloroethane"
1,2-Dichloroethene (total)
Chloroform
-—1,2-Dichloroethane.
2-Butanone
—-1,l,l-Trichloroethane.
Carbon Tetrachloride^
Vinyl Acetate.
—Broraodichloromethane.
1,2-Dichloropropane."
—-cis-1,3-Dichloropropene_
Trichloroethene
Dibromochloromethane.
1,1,2-Trichlorethane"
Benzene
—-trans-1,3-Dichloropropene
Bromoform
4-Methyl-2-Pentanone.
2-Hexanone
Tetrachloroethene
1,1,2,2-Tetrachloroethane_
—-Toluene
Chlorobenzene.
Ethylbenz ene_]
-—Styrene_
-—Xylene (total)
FORM I VOA
10/86
-------
IB
SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET
EPA SAMPLE NO.
Lab Name:.
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Matrix: (soil/water)
Sample wt/vol: (g/mL)
Level: (low/med)
% Moisture: not dec. dec.
Extraction: (SepF/Cont/Sonc)
GPC Cleanup: (Y/N) pH:.
Lab Sample ID:
Lab File ID:
Date Received:
Date Extracted:
Date Analyzed:
CAS NO.
COMPOUND
Dilution Factor:
CONCENTRATION UNITS:
(ug/L or ug/Kg)
108-95-2
111-44-4
95-57-8
541-73-1
106-46-7
100-51-6
95-50-1
95-48-7
108-60-1
106-44-5
621-64-7
67-72-1
98-95-3
78-59-1
88-75-5
105-67-9-
65-85-0
111-91-1
120-83-2
120-82-1
91-20-31
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
Phenol
bis(2-Chloroethyl)ether_
2-Chlorophenol_
1,3-Dichlorobenzene_
1,4-Dichlorobenzene]
Benzyl alcohol_
1,2-Dichlorobenzene
2-Methylphenol
bis-(2-Chloroisopropyl)ether
4 -Methylphenol
N-Nitroso-di-n-propvlamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol_
2,4-Dimethylphenol_
Benzoic acid
bis(2-Chloroethoxy)methane
-2,4-Dichlorophenol
-—-1,2,4-Trichlorobenzene_
Naphthalene_
4-Chloroaniline
Hexachlorobutadiene
-—-4-Chloro-3-methylphenol_
2-Methylnaphthalene_
——Hexachlorocyclopentadiene_
2,4,6-Trichlorophenol ~
2,4,5-Trichlorophenol
2-Chloronaphthalene
—-2-Nitroaniline_
Dimethylphthalate_
Acenaphthylene_
2/6-Dinitrotoluene_
FORM I sv-i
10/86
-------
Lab Name:
Lab Code:
1C
SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET
Contract:
SAS No.:
EPA SAMPLE NO,
Case No.:
Matrix: (soil/water)
Sample wt/vol: (g/mL)
Level: (low/med)
* Moisture: not dec. dec.
Extraction: (SepF/Cont/Sonc)
GPC Cleanup: (Y/N) pH:
CAS NO.
COMPOUND
SDG No.:
Lab Sample ID:
Lab File ID:
Date Received:
Date Extracted:
Date Analyzed:
Dilution Factor:
CONCENTRATION UNITS:
(ug/L or ug/Kg)
99-09- 2 3 -Ni tr oani 1 ine
83-3 2 -9——Acenaphthene
51-28-5————2,4-Dinitrophenol
100-02- 7 4-Nitrophenol
132-64-9 Dibenzofuran
121-14-2 2,4-Dinitrotoluene
84-66-2————Diethvlphthalate
7005-7 2-3 ——4-Chlorophenyl-phenylether
86-73-7 —Fluorene ]
100-01-6 ———4-Nitroaniline
534-52-1——4,6-Dinitro-2-raethylphenol
86-30-6 N-Nitrosodiphenylamine (1)"
101-55- 3 —4-Bromophenyl-phenylether_
118-74-1——Hexachlorobenz ene
8 7 -8 6-5— —Pentachl or opheno 1
8 5 -01-8 ————Phenanthrene
120-12-7 —Anthracene
84-74-2— — Di-n-butylphthalate
206-44-0-———Fluoranthen e
129-00-0 ——Pyrene
85-68-7———-Butylbenzylphthalat e
91-94-1——3,3 ' -Dichlorobenzidine
56-55-3 ———Benzo(a) anthracene
218-01-9—-——Chrysene
117-81-7——bis (2-Ethylhexyl) phthalate
117-84-0—-—Di-n-octylphthalate |
205-99-2———Benzo(b) fluoranthene
207-08- 9 -Benzo(k)fluoranthene
50-32-8 Benzo (a) pyrene
193-39-5 1ndeno (1,2,3 -cd) pyrene
53-70-3 Dibenz (a,h) anthracene
191-24-2——-Benzo(g,h, i) perylene
(1) - Cannot be separated from diphenylamine
FORM I SV-2
10/86
-------
Lab Name:
Lab Code:
ID
PESTICIDE ORGANICS ANALYSIS DATA SHEET
Contract:
SAS No.:
EPA SAMPLE NO.
Case No.:
Matrix: (soil/water)
Sample wt/vol: (g/mL).
Level: (low/med)
% Moisture: not dec. dec.
Extraction: (SepF/Cont/Sonc)
GPC Cleanup: (Y/N) pH:_
CAS NO.
COMPOUND
SDG No.:
Lab Sample ID:
Lab File ID:
Date Received:
Date Extracted:
Date Analyzed:
Dilution Factor:
CONCENTRATION UNITS:
(ug/L or ug/Kg)
319-84-6 alpha-BHC
319-85-7 beta-BHC
319-86-8 delta-BHC
58-89-9 gamma-BHC (Lindane)
76-4 4 -8—— Heptachlor
3 09-00-2 —-—-—Aldrin
1024-57-3— —Heptachlor epoxide
959-98-8 Endosulfan I ^
60-57-1 Dieldrin
72-55-9 4 , 4 ' -DDE
72-20-8— -Endrin
33213-65-9- Endosulfan II
72-54-8 4,4'-ODD
1031-07-8 Endosulfan sulfate
50-29-3 4,4 '-DDT j
72-43-5————Methoxychlor
53494-70-5 —Endrin ketone
5103-71-9 alpha-Chlordane
5103-7 4 -2 — ganuna-Chlordane
8001-35-2 —Toxaphene
12674-11-2— Aroclor-1016
11104-28-2 Aroclor-1221
11141-16-5 Aroclor-1232
53469-22-9 Aroclor-1242
12672-29-6 —Aroclor-1248__
11097-69-1 Aroclor-1254
11096-82-5 Aroclor-1260
FORM I PEST
10/86
-------
IE EPA SAMPLE NO.
VOLATILE ORGANICS ANALYSIS DATA SHEET
TENTATIVELY IDENTIFIED COMPOUNDS |
Lab Name: Contract: J
Lab Code: Case No.: SAS No.: SDG No.:
Katrix: (soil/water) Lab Sample ID:
Sample wt/vol: (g/nL) Lab File ID:
Level: (low/med) Date Received:
\ Moisture: not dec. Date Analyzed:
Dilution Factor:
CONCENTRATION UNITS:
Number TICs found: (ug/L or ug/Kg)
CAS NUMBER
1.
2.
3.
4.
5."
6."
7.'
8.'
9."
10."
11.
12.
13 .
14.'
15."
16.
17."
18.
19.
20.
21.
22."
23 ."
24.
25."
26."
27.
28.
29."
30.
COMPOUND NAME
RT
EST. CONC.
FORM I VOA-TIG
10/86
-------
Lab Name:
Lab Code:
IF
SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET
TENTATIVELY IDENTIFIED COMPOUNDS
Contract:
SAS No.:
EPA SAMPLE NO.
Case No.:
SDG No.:
Matrix: (soil/water)
Sample wt/vol: (g/mL)
Level: (low/med)
% Moisture: not dec. dec.
Extraction: (SepF/Cont/Sonc)
GPC Cleanup: (Y/N) pH:.
Number TICs found:
Lab Sample ID:
Lab File ID:
Date Received:
Date Extracted:
Date Analyzed:
Dilution Factor:
CONCENTRATION UNITS:
(ug/L or ug/Kg)
CAS NUMBER
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16."
17."
18."
19."
20."
21."
22."
23."
24."
25."
26."
27."
28."
29."
30."
COMPOUND NAME
RT
EST. CONC.
FORM I SV-TIC
10/86
-------
2A
WATER VOLATILE SURROGATE RECOVERY
Lab Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
EPA
SI | S2
S3 |OTHER
| TOT |
SAMPLE NO.
(TOL)#|(BFB)#
(DCE)#|
|OUT|
01
1
1
02
1
1
03
1
1
04
1
1
05
1
1
06
1
1
07
1
I
08
1
1
09
1
10
1
11
1
12
1
1
13
1
1
14
1
1
15
1
1
16
1
1
17
1
1
18
1
19
1
1
20
1
1
21
1
1
22
1
23
1
1
24
1
1
25
1
1
26
1
1
27
1
28
1
29
1
1
30
1
1
QC LIMITS
51 (TOL) « Toluene-d8 (88-110)
52 (BFB) - Bromofluorobenzene (86-115)
53 (DCE) ¦ 1,2-Dichloroethane-d4 (76-114)
# Column to be used to flag recovery values with an asterisk
* Values outside of contract required QC limits
page of
FORM II VOA-1
10/86
-------
2B
SOIL VOLATILE SURROGATE RECOVERY
Lab Name; Contract:
Lab Code: Case No.: SAS No.: SDG No.:
Level: (1ow/med)
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
SAMPLE NO.
SI
(TOL) #
S2
(BFB) #
S3
(DCE) #
OTHER
TOT
OUT
51 (TOL) ¦ Toluene-d8
52 (BFB) » Bromafluorobenzene
53 (DCE) » 1,2-Dichloroethane-d4
QC LIMITS
(81-117)
(74-121)
(70-121)
# Column to be used to flag recovery values with an asterisk
* Values outside of contract required QC limits
page of
FORM II VOA-2
10/86
-------
2C
WATER SEMIVOLATILE SURROGATE RECOVERY
Lab Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
r EPA 1 SI
S2
S3
S4 | S5
S6 |OTHER
| TOT |
|SAMPLE NO. 1 (NBZ)#
(FBP)#
(TPH)#
(PHL)#|(2FP)#
(TBP)#|
| OUT |
011 1
1
1
021 1
1
1
03"l 1
1
041 I
1
1
051 1
1
1
06 1 I
1
1
07 1 1
1
1
081 1
1
1
09! 1
1
1
101 1
1
1
111 1
1
121 1
1
1
13 1 1
1
1
14 1 1
1
1
151 1
1
1
161 1
1
1
17 1 1
1
1
181 1
1
1
191 1
1
1
201 1
1
1
211 1
1
1
221 1
1
1
231 1
1
1
24| |
1
1
251 1
1
1
261 1
1
1
271 1
1
1
281 1
1
291 1
1
1
301 1
1
1
51 (NBZ) * Nitrobenzene-d5
52 (FBP) » 2-Fluorobiphenyl
53 (TPH) - Terphenyl-dl4
54 (PHL) - Phenol-d5
55 (2FP) ¦ 2-Fluorophenol
56 (TBP) * 2,4,6-Tribromophenol
QC LIMITS
(35-114)
(43-116)
(33-141)
(10-94)
(21-100)
(10-123)
# Column to be used to flag recovery values with an asterisk
* Values outside of contract required QC limits
page
of
FORM II SV-1
10/86
-------
2D
SOIL SEMIVOLATILE SURROGATE RECOVERY
Lab Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
Level:(low/med)
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
23
29
30
EPA
SAMPLE NO.
SI
(NBZ)#
S2
(FBP)#
S3
(TPH)#
S4
(PHL)#
S5
(2FP) #
S6
(TBP)#
OTHER
TOT
OUT
51 (NBZ) «¦ Nitrobenzene-d5
52 (FBP) = 2-Fluorobiphenyl
53 (TPH) - Terphenyl-dl4
54 (PHL) - Phenol-d5
55 (2FP) » 2-Fluorophenol
56 (TBP) » 2,4,6-Tribroraophenol
QC LIMITS
(23-120)
(30-115)
(18-137)
(24-113)
(25-121)
(19-122)
# Column to be used to flag recovery values with an asterisk
* Values outside of contract required QC limits
page
of
FORM II SV-2
10/86
-------
2E
WATER PESTICIDE SURROGATE RECOVERY
Lab Name:.
Lab Code:
Case No.:
Contract:_
SAS No.:
SDG No.:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
SAMPLE NO.
OTHER
ADVISORY
QC LIMITS
SI (DBC) » Dibutylchlorendate (20-150)
# Column used to flag recovery values with an asterisk
* Values outside of QC limits
page of
FORM II PEST-1
10/86
-------
2F
SOIL PESTICIDE SURROGATE RECOVERY
Lab Name Contract;
Lab Code; Case No.: SAS No.: SDG No.:
Level:(low/med)
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
IS
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
SAMPLE
NO.
SI
(DBC) #
OTHER
ADVISORY
QC LIMITS
SI (DBC) » Dibutylchlorendate (24-154)
# Column to be used to flag recovery values with an asterisk
* Values outside of QC limits
page of
FORM II PEST-2 10/86
-------
3A
WATER VOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Lab Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
Matrix Spike - EPA Sample No.:
COMPOUND
1,1-Dichloroethene
Tnchloroethene
Benzene
Toluene
Chiorobenz ene
AMOUNT
ADDED
(ng)
SAMPLE CONC.
(ug/L)
MS CONC.
(ug/L)
MS%
REC #
QC
LIMITS
REC.
61-145
71-120
76-127
76-125
75-130
COMPOUND
1,1-Dichloroethene
Trichloroethene
Benzene
Toluene
Chlorobenzene
MSD CONC.
(ug/L)
MSD%
REC #
MS%
REC #
%
RPD #
QC LIMITS
RPD
| REC.
sasa
¦as j
14
|61-145
I
14
171-120
|
11
176-127
j
13
176-125
|
13
175-130
r Column to be used to flag recovery and RPD values with an asterisk
* Values outside of QC limits
*PD: out of outside limits
Spike Recovery: out of outside limits
:OMMENTS:
FORM III VOA-1
10/86
-------
3B
SOIL VOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
.Lab .Name: Contract:
Lab Code: .... . Case No.: SAS No.: SDG No.:
Matrix Spike - EPA Sample No.: Level: (low/med)
J
AMOUNT
|SAMPLE CONC. |
MS CONC.
1
QC |
X
ADDED
1 1
| MS%
LIMITS |
1 -
COMPOUND
(ng)
1 (ug/L) |
(ug/L)
I REC #
REC. |
I
1
1,1-Dichloroethene
1 1
1
59-172|
62-137)
66-142|
59-139|
60-133|
I 1
1
1
1
Trichloroethene
1 1
1
1 1
1
1
1
Benzene
1 1
1
1 1
1
1
1
Toluene
1 1
1
1 1
1
1
Chlorobenzene
1 1
1
1 1
1
COMPOUND
1,1-Dichloroethene
Trichloroethene
Benzene
Toluene
Chlorobenzene
MSD CONC.
(ug/L)
MSD%
REC #
MS%
REC #
%
RPD #
QC LIMITS •
RPD | REC.
22 |59-172
I
24 |62-137
I
21 |66-142
I
21 |59-139
I
21 160-133
# Column to be used to flag recovery and RPD values with an asterisk
* Values outside of QC limits
RPD: out of outside limits
Spike Recovery: out of outside limits
COMMENTS:
FORM III VOA-1
10/86
-------
3C
WATER SEMIVOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Lab Name:
Lab Code:
Case No.:
Matrix Spike - EPA Sample No.:
Contract:
SAS No.:
SOG No.:
COMPOUND
Phenol
2-Chlorophenol_
1,4-Dichloro-
benzene
N-Nitroso-di-n-
Propylamine_
1,2,4-Trichloro-
benzene
4-Chloro-3-Methyl-
phenol
Acenaphthene_
4-N itropheno 1
2,4-Dinitrotoluene_
Pentachlor ophenol_J
Pyrene
AMOUNT
ADDED
(ng)
SAMPLE CONC.
IN EXTRACT
(ug/L)
MS CONC.
IN EXTRACT
(ug/L)
MS%
REC #
QC
LIMITS
REC.
12-89
27-123
36-97
41-116
39-98
23-97
46-118
10-80
24-96
9-103
26-127
COMPOUND
Phenol
MSD CONC. IN
EXTRACT(ug/L)
2-Chlorophenol_
1,4-Dichloro-
benzene
N-Nitroso-di-n-
Propylamine_
1,2,4-Trichloro-
benzene
4-Chioro-3-Methyl-
phenol_
Acenaphthene
4-Nitropheno 1
2,4-Dinitrotoluene_
Pentachlorophenol_]
Pyrene
MSD%
REC #
MS%
REC
%
RPD #
QC LIMITS
RPD
I REC.
ssaa
um | saaaaa
42
1-12-89
40
|27-123
!
28
1
|36-97
38
141-116
28
|39-98
i
42
1
|23-97
31
146-118
50
|10-80
38
124-96
50
| 9-103
31
126-127
it Column to be used to flag recovery and RPD values with an asterisk
* Values outside of QC limits
RPD: out of outside limits
Spike Recovery: out of outside limits
-OMMENTS:
FORM III SV-1
10/86
-------
3D
SOIL SEMIVOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Lab Name:.
Lab Code:
Case No.:
Matrix Spike - EPA Sample No.:
Contract:
SAS No.:
SDG No.:
Level:(low/med)
COMPOUND
Phenol
2 -Chlorophenol_
1,4--Dichloro- "
benzene
N-Nitroso-di-n-
Propylamine__
1,2,4-Trichloro-
benzene
4-Chloro-3-Methyl-
phenol
Acenaphthene
4-Nitrophenol
2,4-Dinitrotoluene_
Pentachl orophenol_J]
Pyrene
AMOUNT
ADDED
(ng)
SAMPLE CONC.
IN EXTRACT
(ug/L)
MS CONC.
IN EXTRACT
(ug/L)
MS%
REC #
QC
LIMITS
REC.
26-90
25-102
28-104
41-126
38-107
26-103
31-137
11-114
28-89
17-109
35-142
COMPOUND
Phenol
MSD CONC. IN
EXTRACT(ug/L)
2-Chlorophenol_
1,4-Dichloro-
benzene
N-Nitroso-di-n-
Propylamine___
1,2,4-Trichloro-
benzene
4-Chioro-3-Methyl-
pheno1
Acenaphthene
4-Nitrophenol
2,4-Dinitrotoluene_
Pentachlorophenol_^
Pyrene
MSD%
REC #
MS%
REC #
%
RPD #
QC LIMITS
RPD
| REC.
¦ j aaaaaa
35
|26-90
50
|25-102
1
27
|28-104
38
I 41-126
[
23
|38-107
33
|26-103
19
|31-137
50
111-114
47
|28-89
47
|17-109
36
135-142
# Column to be used to flag recovery and RPD values with an asterisk
* Values outside of QC limits
RPD: out of outside limits
Spike Recovery: out of outside limits
COMMENTS:
FORM III SV-1
10/86
-------
3E
WATER PESTICIDE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Lab Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
Matrix Spike - EPA Sample No.:
COMPOUND
Lindane
Heptachlor
Aldrin
Dieldrin
Endrin
4,4'-DDT
AMOUNT
ADDED
(ng)
SAMPLE CONC.
IN EXTRACT
(ug/L)
MS CONC.
IN EXTRACT
(ug/L)
MS%
REC #
QC
LIMITS
REC.
56-123
40-131
40-120
52-126
56-121
33-127
COMPOUND
:siaauaa«
Lindane
Heptachlor
Aldrin
Dieldrin
Endrin
4,4'-DDT
MSD CONC.
IN EXTRACT
(ug/L)
MSD%
REC #
MS%
REC #
%
RPD #
QC LIMITS
RPD
| REC.
aaas
¦ j amanmai
15
| 56-.123
20
1
|40-131
1
22
|40-120
1
18
|52-126
21
|56-121
1
27
133-127
# Column to be used to flag recovery and RPD values with an asterisk
* Values outside of QC limits
RPD: out of outside limits
Spike Recovery: out of outside limits
COMMENTS:
FORM III PEST-1
10/36
-------
3F
SOIL PESTICIDE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Lab Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
Matrix Spike - EPA Sample No.: Level:(low/med)
COMPOUND
Lindane
Heptachlor
Aldrin
Dieldrm
Endrin
4,4'-DDT
AMOUNT
ADDED
(ng)
SAMPLE CONC.
IN EXTRACT
(ug/L)
MS CONC.
IN EXTRACT
(ug/L)
MS%
REC #
QC
LIMITS
REC.
46-127
35-130
34-132
31-134
42-139
23-134
COMPOUND
Lindane
Heptachlor
Aldrin
Dieldrin
Endrin
4,4'-DDT
MSD CONC.
IN EXTRACT
(ug/L)
MSD%
REC #
MS%
REC #
%
RPD #
QC LIMITS
RPD
REC.
50
46-127
31
35-130
43
34-132
38
31-134
45
42-139
50
23-134
# Column to be used to flag recovery and RPD values with an asterisk
* Values outside of QC limits
RPD: out of outside limits
Spike Recovery: out of outside limits
COMMENTS:
FORM III PEST-1
10/86
-------
4A
VOLATILE METHOD BLANK SUMMARY
Lab Name:,
Lab Code:
Case No.:
EPA Sample No. for Method Blank:,
Instrument ID.:
Date Analyzed:
Matrix: (soil/water)
Contract:
SAS No.:
SDG No.
Lab Sample ID:
Lab File ID:
Time Analyzed:
Leve1: (1ow/med)
THIS METHOD BLANK APPLIES TO THE FOLLOWING SAMPLES, MS AND MSD:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
COMMENTS:
EPA
SAMPLE NO.
LAB
SAMPLE ID
LAB
FILE ID
TIME OF
ANALYSIS
page
of
FORM IV VOA
10/86
-------
4B
SEMIVOLATILE METHOD BLANK SUMMARY
Lab Name:,
Lab Code:
Case No.
Contract:a
SAS No.:
SDG No.:
EPA Sample No. for Method Blank:.
Instrument ID:
Date Extracted:
Date Analyzed:
Matrix: (soil/water)
Lab Sample ID:
Lab File ID:
Extraction:(SepF/Cont/Sonc)
Time Analyzed:
Level: (low/med)
THIS METHOD BLANK APPLIES TO THE FOLLOWING SAMPLES, MS AND MSD:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
EPA
SAMPLE NO.
LAB
SAMPLE ID
LAB
FILE ID
DATE OF
ANALYSIS
COMMENTS:
page of
FORM IV SV 10/3 6
-------
4C
PESTICIDE METHOD BLANK SUMMARY
Lab Name:.
Lab Code:
Case No.:
Contract:.
SAS No.:
SD6 No.:
EPA Sample No. for Method Blank:
Matrix:(soil/water) Level:(low/med)
Date Extracted:
Lab Sample ID:
Lab File ID:
Date Analyzed (1)
Time Analyzed (1)
Instrument ID (1)
GC Column ID (1)
Extraction: (SepF/cont/Sonc)
Date Analyzed (2):
Time Analyzed (2):
Instrument ID (2):
GC Column ID (2):
THIS METHOD BLANK APPLIES TO THE FOLLOWING SAMPLES, MS AND MSD:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
COMMENTS:
EPA
SAMPLE NO.
LAB SAMPLE
ID (1)
DATE
ANALYZED 1
LAB SAMPLE
ID (2)
DATE
ANALYZED 2
page of
FORM IV PEST
10/86
-------
jr
5A
VOLATILE ORGANIC GC/MS TUNING AND MASS
CALIBRATION - BROMO FLUORO BEN ZENE (BFB)
Lab Name: Contract:
lab Code: Case No.: SAS No.: SDG No,
Lab File ID: BFB Injection Date:_
Instrument ID.: BFB Injection Time:
1
m/e |
ION ABUNDANCE CRITERIA |
—¦ — ¦—. ¦¦ — — ¦¦ — -¦ — — — 1
% RELATIVE
ABUNDANCE
5
-------
5B
SEMIVOLATILE ORGANIC GC/MS TUNING AND MASS
CALIBRATION - DECAFLUOROTRIPHENYLPHOSPHINE (DFTPP)
jab Nana: Contract:
^ab Code: Case No.: SAS No.: SDG No.:
'^ab File ID: DFTPP Injection Date:
Instrument ID.: DFTPP Injection Time:
| % RELATIVE
a/e
ION ABUNDANCE CRITERIA
| ABUNDANCE
51
30.0 - 60.0% of mass 198
1
68
less than 2.0% of mass 69
1 ( )1
69
mass 69 relative abundance
1
70
less than 2.0% of mass 69
1 ( )1
127
40.0 - 60.0% of mass 198
1
197
less that 1.0% of mass 198
1
198
Base Peak, 100% relative abundance
1
199
5.0 to 9.0% of mass 198
1
275
10.0 - 30.0% of mass 198
1
365
greater than 1.00% of mass 198
441
present, but less than mass 443
442
greater than 40.0% of mass 198
I
443
17.0 - 23.0% of mass 442
1 ( )2
1
l-Value is % mass 69 2-Value is % mass 442
THIS TUNE APPLIES TO THE FOLLOWING SAMPLES, MS, MSD, BLANKS; AND STANDARDS
page
EPA
SAMPLE NO.
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
LAB
SAMPLE ID
of
LAB
FILE ID
DATE OF
ANALYSIS
TIME OF
ANALYSIS
FORM V SV
10/86
-------
6A
VOLATILE ORGANICS INITIAL CALIBRATION DATA
Lab- Name:
Contract:
Lab Code:
Case No.:
SAS No.:
SDG No.:
Instrument- ID.:
Calibration Date(s):
Minimum RRF for SPCC(#) is 0.300
(0.2S0 for Bromoform)
Maximum % RSD for CCC(*) is 30.0%
[LAB FILE ID:
RRF100-
I
I
| COMPOUND
\Chloromethane_
Bromomethane
RRF20 >
RRF1503
RRF50 »
RRF200'
I Vinyl Chloride_
Chloroethane
[Methylene chloride_
Acetone ~
i Carbon Disulfide
1,l-Dichloroethene_
1,l-Dichloroethane"
1,2-Dichloroethene (total)_
Chloroform
1,2-Dichloroethane_
2-Butanone
1,1,l-Trichloroethane_
I Carbon Tetrachloride^
I Vinyl Acetate_
Bromodichloromethane_
1,2-Dichloropropane
j cis-l,3-Dichloropropene
ITrichloroethene
Dibromochloromethane___
1,1,2-Trichloroethane_
Benzene
i trans-1,3-Dichloropropene
Bromoform
4-Methyl-2-Pentanone
2-Hexanone
RRF20
| Tetrachloroethene
11,1,2,2-Tetrachloroethane f
: Toluene *"
*
Chlorobenzene_
Ethylbenzene_J
Styrene_
Xylene (total)
.1.
RRF50
Toluene-d8
Bromofluorobenzene
1,2-Dichloroethane-d4
RRF100
RRF150
RRF200
RRF
FORM VI VOA
10/86
-------
6B
SEMIVOLATILE ORGANICS INITIAL CALIBRATION DATA
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
Instrument ID.:
Calibration Date(s):
Minimum RRF for SPCC(#) is 0.050
Maximum % RSD for CCC(*) is 30.0%
LAB FILE ID;
RRF80 -
RRF20 -
RRF 120-"
RRF50 *
RRF1601
COMPOUND
Phenol
RRF20
bis(-2-Chloroethyl)Ether
2-Chlorophenol
1/3-Dichlorobenzene_
l,4-Dichlorobenzene~
Benzyl Alcohol
1,2-Dichlorobenzene
2-Methylphenol
bis(2-chloroisopropyl)Etherj
4 -Methy lphenol j
N-Nitroso-Di-n-Propylamine #
Hexachloroethane ~|
N itrobenz ene |
Isophorone j
2 -N i t r opheno 1 *
2 , 4-Dimethyl phenol |
Benzoic Acid
bis(2-Chloroethoxy)Methane_j~
2,4-Dichlorophenol
1,2,4-Trichlorobenzene |"
Naphthalene j"
4-Chloroaniline
Hexachlorobutadiene
4-Chloro-3-Methylphenol
2-Methylnaphthalena
*
Hexachlorocyclopentadiene #
2,4,6-Trichlorophenol *[
2,4,5-Trichlorophenol | "
2-Chloronaphthalene j "
2 -Ni troanil ine j ~
Dimethyl Phthalate j"
Acenaphthylene j"
2,6-Dinitrotoluene_
3-Mitroaniline ~
Acenaphthene_
2,4-Dinitrophenol_
4-Nitrophenol "
RRF50
RRF80
RRF120
RRF160
RRF
% I
RSD |
*
*
j
*
it
j
.#
*
4
T
FORM VI SV-1
10/86
-------
6C
SEMIVOLATILE ORGANICS INITIAL CALIBRATION DATA
Lab Name:,
lab Code:
Case No.:
Contract:,
SAS No.:
SOG No.:
Instrument ID.:
Calibration Date(s):
Minimum RRF for SPCC(#) is 0.050
Maximum % RSD for CCC(*) is 30.0%
LAB FILE ID:
RRF80 -
RRF20 =
RRF120-
RRF50 =
RRF160a
COMPOUND
Dibenzofuran
2,4-Dinitrotoluene_
Diethylphthalate_
4 -Chi o r opheny 1 -pheny 1 ether__
Fluorene ~~
4-Nitroaniline
4,6-Dinitro-2-methylphenol_
N-Nitrosodiphenylamine(1) ~
4-Bromophenyl-phenylether
Hexachlorobenzene
Pentachlorophenol
Phena'nthrene
Anthracene
Di-n-butylphthalate_
Fluor anthene ~
Pyrene_
Butylbenzylphthalate
3,3'-Dichlorobenzidine
Benzo(a)anthracene ^
Chrysene
bis(2-Ethylhexyl)phthalate_
Di-n-octylphthalate ~
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(1,2,3-cd)pyrene_
Dibenz(a, h)anthracene_J
Benzo(g,h,i)perylene
RRF20
RRF50
RRF80
RRF120
RRF160
RRF
R:
Nitrobenzene-d5_
2-Fluorobiphenyl_
Terphenyl-dl4 ]
Phenol-d5
2-Fluorophenol
2,4,6-Tribromophenol_
FORM VI SV-2
10/8
-------
7A
VOLATILE CONTINUING CALIBRATION CHECK
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
Instrument ID:
Lab File ID:
Calibration Date:
SDG No.:
Time:
Init. Calib. Date(s):
Minimum RRF50 for SPCC(#) is 0.300
(0.250 for Bromoform)
Maximum % D for CCC(*) is 25.0%
COMPOUND
Chioromethane_
Bromomethane
vinyl Chloride_
Chloroethane
Methylene Chloride_
Acetone
Carbon Disulfide
1,1-Dichloroethene
1.1-Dichloroethan e
1.2-Dichloroethene (total)_
Chloroform
1,2-Dichloroethane_
2-Butanone
1,1,l-Trichloroethane_
Carbon Tetrachloride^
Vinyl Acetate
Bromodichloromethane
1,2-Dichloropropane_
cis-1,3-Dichloropropene_
Trichloroethene
Dibromochloromethane
1,1,2-Trichloroethane_
Benzene
trans-1,3-Dichloropropene^
Bromoform
4-Methyl-2-Pentanone_
2-Hexanone
Tetrachloroethene
1,1,2,2-Tetrachloroethane_
Toluene ~
Chlorobenzene
Ethylbenzene
Styrene
RRF
A
*
;#•
*
Xylene (total)
Toluene-d8
Bromofluorobenzene
1,2-Dichloroethane-d4
RRF 50
%D
.#
•k
;#
*
FORM VII VOA
10/86
-------
Jf
7B
SEMIVOLATILE CONTINUING CALIBRATION CHECK
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
Instrument ID:
Lab File ID:
Calibration Date:
SDG No.:
Time:
Init. Calib. Date(s):
Minimum RRF50 for SPCC(#) is 0.050
Maximum % D for CCC(*) is 25.0%
bis(-2-Chloroethyl)Ether_
_2-Chlorophenol_
COMPOUND
Phenol
RRF
1.3-Dichlorobenzene_
1.4-Dichlorobenzene"
Benzyl Alcohol_
1,2-Dichlorobenzene_
2-Methylphenol_
,1.
bis(2-chloroisopropyl)Ether|
4-Methylphenol | _
N-Nitroso-Di-n-Propylamine_#~
Hexachloroethane |"
Nitrobenzene j ~
Isophorone j"
2 -Nitrophenol *"
2,4-Dimethylphenol_
Benzoic Acid
I
bis(2-Chloroethoxy)Methane_|_
2,4-Dichlorophenol
1,2,4-Trichlorobenzene |"
Naphthalene
4-Chloroaniline
Hexachlorobutadiene
4-Chloro-3-Methylphenol^
2-Methylnaphthalene_
*
Hexachlorocyclopentadiene #_
2,4, 6-Trichlorophenol
2,4,5-Trichlorophenol | ~
2-Chloronaphthalene j ~
2-Nitroaniline j"
Dimethyl Phthalate |"
Acenaphthylene_
2,6-Dinitrotoluene_
3-Nitroaniline
Acenaphthene
2,4-Dinitrophenol_
4-Nitrophenol
#"
Y
RRF 50
%D |
*
"*
j
.#
*
ff
FORM VII SV-1 10/86
-------
7C
SEMIVOLATILE CONTINUING CALIBRATION CHECK
Lab Name:.
Lab Code:
Case No.:
Contract:.
SAS No.:
Instrument ID:
Lab File ID:
Calibration Date:
SDG No.:
Time:
Init. Calib. Date(s):
Minimum RRF50 for SPCC(#) is 0.050
Maximum % D for CCC(*) is 25.0%
COMPOUND
Dibenzofuran
2,4-Dinitrotoluene_
Diethylphthalate
4-Chlorophenyl-phenylether_
Fluorene ~~
4-Nitroaniline
4,6-Dinitro-2-methylphenol_
N-Nitrosodiphenylamine (1)_
4-Bromopheny1-pheny1ether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-butylphthalate
Fluoranthene ~
Pyrene
Butylbenzylphthalate
3,3'-Dichlorobenzidine_
Benz o(a)anthracene "
Chrysene
bis (2-Ethylhexyl) phthalate__
Di-n-octylphthalate ~
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benz o (a) pyr ene_
Indeno(1,2,3-cd)pyrene
Dibenz(a, h)anthracene^
Benzo(g,h,i)perylene_
Nitrobenzene-d5
2-Fluorobiphenyl_
Terphenyl-dl4 "
Phenol-d5
2-Fluorophenol
2,4,6-Tribromophenol
RRF
RRF50
%D
FORM VII SV-2
10/86
-------
8A
VOLATILE INTERNAL STANDARD AREA SUMMARY
Lab Name:
Lab Code: Case No.:
EPA Sample No.(Standard):
Lab File ID (Standard):
Instrument ID:
Contract:
SAS No.: SDG No.:
Date Analyzed:
Time Analyzed:
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
151 (BCM)
152 (DFB)
153 (CBZ)
12 HOUR
STD_
UPPER
LIMIT_
LOWER
LIMIT_
EPA SAMPLE
NO.
ISl(BCM)
AREA #
RT
IS2(DFB)
AREA #
RT
IS3(CBZ)
AREA #
RT
Bromochloromethane
1,4-Difluorobenzene
Chlorobenzene
UPPER LIMIT - + 100%
of internal standard area.
LOWER LIMIT - - 50%
of internal standard area.
# Column used to flag internal standard area values with an asterisk
page of
10/36
FORM VIII VOA
-------
8B
SEMIVOLATILE INTERNAL STANDARD AREA SUMMARY
Lab Name:
Lab Code: Case No.:
EPA Sample No.(Standard):
Lab File ID (Standard):
Instrument ID:
Contract:
SAS No.: SDG No.:
Date Analyzed:
'Time Analyzed:
12 HOUR
STD_
UPPER
LIMIT,
LOWER
LIMIT_
EPA SAMPLE
NO.
ISl(DCB)
AREA
RT
IS2(NPT)
AREA #
1,4-Dichlorobenzene-d4
Naphthalene-d8
Acenaphthene-d8
RT
IS3(ANT)
AREA #
RT
UPPER LIMIT « + 100% Of
internal standard area.
LOWER LIMIT - - 50% of
internal standard area.
# Column used to flag internal standard area values with an asterisk
?age of
FORM VIII SV-1
10/86
-------
8C
SEMIVOLATILE INTERNAL STANDARD AREA SUMMARY
Lab Name:,
Lab Code:
Case No.:
Contract
SAS No.:
SDG No.:
EPA Sample No.(Standard):a
Lab File ID (Standard):
Instrument ID:
Date Analyzed:
Time Analyzed:
12 HOUR
STD_
UPPER
LIMIT,
laaaasa
LOWER
LIMIT
EPA SAMPLE
NO.
IS4(PHN)
AREA #
RT
Phenanthrene-dlO
Chrysene-dl2
Perylene-dl2
IS5(CRY)
AREA #
RT
IS4(PRY)
AREA #
RT
UPPER LIMIT - + 100%
of internal standard area.
LOWER LIMIT - - 50%
of internal standard area.
# Column used to flag internal standard area values with an asterisk
page of
FORM VIII SV-2
10/8
6
-------
8D
PESTICIDE EVALUATION STANDARDS SUMMARY
Lais Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
Instrument ID: GC Column ID:
Dates of Analyses: to
Evaluation Check for Linearity
LAB SAMPLE
ID (STANDARD)
PESTICIDE
ALDRIN
ENDRIN
4,4'-DDT
DIBUTYL
CHLORENDATE
CALIBRATION
FACTOR
EVAL MIX A
CALIBRATION
FACTOR
EVAL MIX B
CALIBRATION
FACTOR
EVAL MIX C
%RSD
( 10.0% RSD, plot a standard curve and determine the ng
for each sample in that set from the curve.
Evaluation Check for 4,4*-DDT/Endrin Breakdown
(percent breakdown expressed as total degradation)
1
| LAB SAMPLE |
TIME OF | ENDRIN |4,4•-DDT|COMBINED|
1
1
|ID(STANDARD)|
- 1 1
ANALYSIS | | | (2) |
1
1
INITIAL
. | |
1 1
oil
EVAL
MIX
B
1 1
1 1 1 1
02 |
EVAL
MIX
B
1 1
1 1 1 1
03 |
EVAL
MIX
B
1 1
1 1 1 1
04 |
EVAL
MIX
B
1 1
1 1 1 1
05 |
EVAL
MIX
B
1 1
1 1 1 1
06 |
EVAL
MIX
B
1 1
1 1 1 1
07 |
EVAL
MIX
B
1 1
1 1 1 1
08 |
EVAL
MIX
B
1 1
1 1 1 1
09 |
EVAL
MIX
B
1 1
1 ! 1 1
10 |
EVAL
MIX
B
1 1
III!
HI
EVAL
MIX
B
1 1
1 1 1 1
12|
EVAL
MIX
B
1 1
1 1 1 1
13 |
EVAL
MIX
B
1 1
1 ! 1 1
14 |
EVAL
MIX
B
1 1
1
1 1
1 1 1 1
(2) See Form instructions.
FORM VIII PEST-1 10/86
-------
8E
PESTICIDE EVALUATION STANDARDS SUMMARY
Evaluation of Retention Time Shift for Dibutylchlorendate
Lab Name
Lab Code:
Case No.:
Instrument ID:
"Dates of Analyses:
to
Contract:
SAS No.:
SDG No.:
GC Column ID:
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
33
34
35
36
37
38
EPA
SAMPLE NO.
LAB SAMPLE
ID
DATE OF
ANALYSIS
TIME OF
ANALYSIS
%
D
* Values outside of QC limits (2.0% for packed columns,
0.3% for capillary columns)
of
FORM VIII PEST-2
10/8
6
-------
9
PESTICIDE/PCB STANDARDS SUMMARY
Lab Name:,
Lab Code:
Instrument ID:
COMPOUND
alpha-BHC
beta-BHC "
delta-BHC_
gamma-BHC~
Heptaclor]
Aldrin
Hept. Epoxide
Endosulfan I_
Dieldrin ""
4,4'-DDE
Endrin
Endosulfan II
4,4'-DDD
Endo.Sulfate
4,4'-DDT
Methoxychlor_
Endrin Ketone
a. Chlordane_
g. Chlordane"
Toxaphene
Aroclor-1016
Aroclor-1221~
Aroclor-1232~
Aroclor-1242~
Aroclor-1248"
Aroclor-1254"
Aroclor-1260~
Case No.:
Contract:
SAS No.:
SDG No.:
GC Column ID:
DATE(S) OF FROM:
ANALYSIS TO:'
TIME (S) OF FROM:'
ANALYSIS TO:'
RT
RT
WINDOW
FROM I TO
CALIBRATION
FACTOR
DATE OF ANALYSIS
TIME OF ANALYSIS
LAB SAMPLE ID
(STANDARD)
RT
CALIBRATION
FACTOR
QNT
Y/N
%D |
Under QNT Y/N: enter Y if quantitation was performed, N if not performed.
%D must be less than or equal to 15.0% for quantitation, and less than
or equal to 20.0% for confirmation.
Note: Determining that no compounds were found above the CRQL is a form of
quantitation, and therefore at least one column must meet the 15.0% criteria.
For multicomponent analytes, the single largest peak that is characteristic
of the component should be used to establish retention time and %D.
Identification of such analytes is based primarily on pattern recognition
page of
FORM IX PEST
10/86
-------
Lab Name:
Lab Code:
10
PESTICIDE/PCB IDENTIFICATION
Contract:
SAS No.:
EPA SAMPLE NO,
Case No.:
GC Column ID (1):
Instrument ID (1):
Lab Sample ID (1):
Lab File ID:
SDG No.:
GC Column ID (2):
Instrument ID (2):
Lab Sample ID (2):
(only if confirmed by GC/MS)
PESTICIDE/PCB
01_
02
RETENTION TIME
Column 1
Column 2
RT WINDOW
OF STANDARD
FROM TO
QUANT? GC/MS?
(Y/N) (Y/N)
03,
04
Column 1
Column 2
05.
06
Column 1
Column 2
07.
08
Column 1
Column 2
09.
10
Column 1
Column 2
ll.
12
Column 1
Column 2
lomments:
page of
FORM X PEST
10/86
-------
EXHIBIT C
TARGET' COMPOUND LIST (TCL) AND
CONTRACT REQUIRED QUANTITATION LIMITS (CRQL)
10/86
-------
Target Compound List (TCL) and
Contract Required Quantitation Limits (CRQL)*
Quantitation Limits**
Water Low Soil/Sedlmenta
Volatile sr CAS Number ug/L ug/Kg
1.
Chloromethane
74-87-3
10
10
2.
Bromomethane
74-83-9
10
10
3.
Vinyl Chloride
75-01-4
10
10
4.
Chloroethane
75-00-3
10
10
5.
Methylene Chloride
75-09-2
5
5
6.
Acetone
67-64-1
10
10
7.
Carbon Disulfide
75-15-0
5
5
8.
1,1-Dichloroethene
75-35-4
5
5
9.
1,1-Dichloroethane
75-35-3
5
5
10.
1,2-Dichloroethene (total)
540-59-0
5
5
11.
Chloroform
67-66-3
5
5
12.
1,2-Dichloroethane
107-06-2
5
5
13.
2-Butanone
78-93-3
10
10
14.
1,1,1-Trichloroethane
71-55-6
5
5
15.
Carbon Tetrachloride
56-23-5
5
5
16.
Vinyl Acetate
108-05-4
10
10
17.
Bromodichlororaethane
75-27-4
5
5
18.
1,1,2,2-Tetrachloroethane
79-34-5
5
5
19.
1,2-Dichloropropane
78-87-5
5
5
20.
cis-1,3-Dichloropropene
10061-01-5
5
5
21.
Trichloroethene
79-01-6
5
5
22.
Dibromochloromethane
124-48-1
5
5
23.
1,1,2-Trichloroethane
79-00-5
5
5
24.
Benz ene
71-43-2
5
5
25.
trans-1,3-Dichloropropene
10061-02-6
5
5
26.
Bromoform
75-25-2
5
5
27.
2-Hexanone
591-78-6
10
10
28.
4-Methyl-2-pentanone
108-10-1
10
10
29.
Tetrachloroethene
127-13-4
5
5
30.
Toluene
108-88-3
5
5
(continued)
C-l
10/86
-------
Quantitation Limits**
Volatiles
CAS Number
Water
ug/L
Low Soil/Sedlmenta
ug/Kg
31. Chlorobenzene
32. Ethyl Benzene
33. Styrene
34. Xylenes (Total)
108-90-7
100-41-4
100-42-5
133-02-7
5
5
5
5
5
5
S
5
Medium Soil/Sediment Contract Required Quantitation Limits (CRQL) for Volatile
TCL Compounds are 100 times the individual Low Soil/Sediment CRQL.
*Speci£ic quantitation limits are highly matrix dependent. The quantitation
limits listed herein are provided for guidance and may not always be achievable.
^Quantitation limits listed for soil/sediment are based on wet weight. The
quantitation limits calculated by the laboratory for soil/sediment, calculated
on dry weight basis as required by the contract, will be higher.
C-2
10/86
-------
Target Compound List (TCL) and
Contract Required Quantitation Limits (CRQL)*
Quantitation Limits**
witer Low Soil/Sedimentb
Semivolatiles CAS Number ug/L ug/Kg
35• Phenol
108-95-2
10
330
36. bis(2-Chloroethyl) ether
111-44-4
10
330
37. 2-Chlorophenol
95-57-8
10
330
38. 1,3-Dichlorobenzene
541-73-1
10
330
39. 1,4-Dichlorobenzene
106-46-7
10
330
AO. Benzyl Alcohol
100-51-6
10
330
41." 1,2-Dichlorobenzene
95-50-1
10
330
42. 2-Methylphenol
95-48-7
10
330
43. bls(2-Chloroisopropyl)
ether
39638-32-9
10
330
44. 4-Methylphenol
106-44-5
10
330
45. N-Nltroso-Dipropylamine
621-64-7
10
330
46. Hexachloroethane
67-72-1
10
330
47. Nitrobenzene
98-95-3
10
330
48. Isophorone
78-59-1
10
330
49. 2-Nitrophenol
88-75-5
10
330
50. 2,4-Diraethylphenol
105-67-9
10
330
51. Benzoic Acid
65-85-0
50
1600
52. bis(2-Chloroethoxy)
methane
111-91-1
10
330
53 2,4-Dichlorophenol
120-83-2
10
330
54. 1,2,4-Trichlorobenzene
120-82-1
10
330
55. Naphthalene
91-20-3
10
330
56. 4-Chloroaniline
106-47-8
10
330
57. Hexachlorobutadlene
87-68-3
10
330
58. 4-Chloro-3-methylphenol
(para-chloro-meta-cresol)
59-50-7
10
330
59. 2-Methylnaphthalene
91-57-6
10
330
60. Hexachlorocyclopentadiene
77-47-4
10
330
61. 2,4,6-Trichlorophenol
88-06-2
10
330
62. 2,4,5-Trichlorophenol
95-95-4
50
1600
63. 2-Chloronaphthalene
91-58-7
10
330
64. 2-Nitroaniline
88-74-4
50
1600
(continued)
C-3
10/86
-------
Semlvolatiles
CAS Number
Quantitation Limits**
Water Low Soil/Sediment*^*
"g/Rg
ug/L
65. Dimethyl Phthalate 131-11*3
66. Acenaphthylene 208-96-8
67. 2,6-Dinitrotoluene 606-20-2
68. 3-Nitroaniline 99-09-2
69. Acenaphthene 83-32-9
70. 2,4-Dinltrophenol 51-28-5
71. 4-Nitrophenol 100-02-7
72. Dibenzofuran 132-64-9
73. 2,4-Dinitrotoluene 121-14-2
74. Diethylphthalate 84-66-2
75. 4-Chlorophenyl Phenyl
ether 7005-72-3
76. Fluorene 86-73-7
77. 4-Nitroaniline 100-01-6
78. 4,6-Dinitro-2-methylphenol 534-52-1
79. N-nitrosodiphenylamine 86-30-6
80. 4-Bromophenyl Phenyl ether 101-55-3
81. Hexachlorobenzene 118-74-1
82. Pentachlorophenol 87-86-5
83. Phenanchrene 85-01-8
84. Anthracene 120-12-7
85. Di-n-butylphthalate 84-74-2
86. Fluoranthene 206-44-0
87. Pyrene 129-00-0
88. Butyl Benzyl Phthalate 85-68-7
89. 3,3'-Dichlorobenzidine 91-94-1
90. Benzo(a)anthracene 56-55-3
91. Chryaene 218-01-9
92. bis(2-ethylhexyl)phthalate 117-81-7
93. Di-n-octyl Phthalate 117-84-0
94. Benzo(b)fluoranthena 205-99-2
10
10
10
50
10
50
50
10
10
10
10
10
50
50
10
10
10
50
10
10
10
10
10
10
20
10
10
10
10
10
330
330
330
1600
330
1600
1600
330
330
330
330
330
1600
1600
330
330
330
1600
. 330
330
330
330
330
330
660
330
330
330
330
330
(continued)
C-4
10/86
-------
Quantitation Limits**
Low Soil/Sediment0
"g/Rg
Semlvolacilea
CAS Number
Water
_us/L
98. DibenzCa,h)anthracene
99. Benzo(g,h,i)perylene
95. Benzo(k)fluoranthene
96.*BenroCaJpyrene
97. Indeno(l,2,3-cd)pyrene
207-08-9
50-32-8
193-39-5
53-70-3
191-24-2
10
10
10
10
10
330
330
330
330
330
^Medium Soil/Sediment Contract Required Quantitation Limits (CRQL) for Semi-
Volatile TCL Compounds are 60 times the individual Low Soil/Sediment CRQL.
*Specific quantitation limits are highly matrix dependent. The quantitation
limits listed herein are provided for guidance and may not always be achievable.
^Quantitation limits listed for soil/sediment are based on wet weight. The
quantitation limits calculated by the laboratory for soil/sediment, calculated
on dry weight basis as required by the contract, will be higher.
C-5
10/86
-------
Target Compound List (TCL) and
Contract Required Quantitation Limits (CRQL)*
Quantitation Limits**
Water Low Soil/Sediment0
Pesticides/PCBs
CAS Number
ur/L
ug/Kg
100. alpha-BHC
319-84-6
0.05
8.0
101. beta-BHC
319-85-7
0.05
8.0
102. delta-BHC
319-86-8
0.05
8.0
103. gamma-BHC (Lindane)
58-89-9
0.05
8.0
104. Heptachlor
76-44-8
0.05
8.0
105. Aldrin
309-00-2
0.05
8.0
106. Heptachlor Epoxide
1024-57-3
0.05
8.0
107. Endosulfan I
959-98-8
0.05
8.0
108. Dleldrln
60-57-1
0.10
16.0
109. 4,4'-DDE
72-55-9
0.10
16.0
110. Endrln
72-20-8
0.10
16.0
111. Endosulfan II
33213-65-9
0.10
16.0
112. 4,4'-ODD
72-54-8
0.10
16.0
113. Endosulfan Sulfate
1031-07-8
0.10
16.0
114. 4,4'-DDT
50-29-3
0.10
16.0
115. Endrln Ketone
53494-70-5
O.'IO
16.0
116. Methoxychlor
72-43-5
0.5
80.0
117. alpha-chlordane
5103-71-9
0.5
80.0
118. gamma-chlordane
5103-74-2
0.5
80.0
119. Toxaphene
8001-35-2
1.0
160.0
120. Aroclor-1016
12674-11-2
0.5
80.0
121. Aroclor-1221
11104-28-2
0.5
80.0
122. Aroclor-1232
11141-16-5
0.5
80.0
123. Aroclor-1242
53469-21-9
0.5
80.0
124. Aroclor-1248
12672-29-6
0.5
80.0
125. Aroclor-1254
11097-69-1
1.0
160.0
126. Aroclor-1260
11096-82-5
1.0
160.0
cMedium Soil/Sediment Contract Required Quantitation Limits (CRQL) for Pesticide/PCB
TCL compounds are 15 times the individual Low Soil/Sediment CRQL.
*Speciflc quantitation limits are highly matrix dependent. The quantitation
limits listed herein are provided for guidance and may not always be
achievable.
**Quantitation limits listed for soil/sediment are based on wet weight. The quan-
titation Limits calculated by the laboratory for soil/sediment, calculated on dry
weight basis as required by the contract, will be higher.
C-6
10/86
-------
EXHIBIT D
ANALYTICAL METHODS
FOR VOLATILES
10/86
-------
TABLE OF CONTENTS
Page
SECTION I - INTRODUCTION VOA D-l
SECTION II - SAMPLE PREPARATION AND STORAGE VOA D-3
PART A - SAMPLE STORAGE AND HOLDING TIMES VOA D-4
PART B - PROTOCOLS FOR HEXADECANE EXTRACTION OF VOLATILES
FROM WATER AND SOIL/SEDIMENT FOR OPTIONAL SCREENING . VOA D-5
SECTION III - OPTIONAL SCREENING OF HEXADECANE EXTRACTS FOR
VOLATILES VOA D-8
SECTION IV - GC/MS ANALYSIS OF VOLATILES VOA D-12
10/86
-------
I
SECTION I
INTRODUCTION
The analytical methods that follow are designed Co analyze water, sediment
and soil from hazardous waste sites for the organic compounds on the Target
Compounds List (TCL) (See Exhibit C). The methods are based on EPA Method
624 (Purgeables).
The methods are divided Into the following sections: sample preparation,
screening, and analysis. Sample preparation covers sample storage, sample
holding times, and medium level sample extraction. As described in the
screening section, a portion of a hexadecane extract may be screened on a gas
chrooatograph with appropriate detectors to determine the concentration level
of organics. The analysis section contains the GC/MS analytical methods for
organlcs. The purge and trap technique, including related sample preparation,
Is included in the analysis section because GC/MS operation and the purge
and trap technique are interrelated.
VOA D-l
10/86
-------
1. Method for Che Determination of Volatile (Purgeable) Organic Compounds.
1.1 Scope and Application
This method covers the determination of a number of the TCL volatile
(purgeable) organics as listed in Exhibit C. The contract required
quantitation limits are also listed in Exhibit C. The method Includes
an optional hexadecane screening procedure. The extract is screened on a
gas chromatograph/ flame ionization detector (GC/FID) to determine the
approximate concentration of organic constituents in the sample. The
actual analysis is based on a purge and trap gas chromatograph!c/mass
spectrometer (GC/MS) method. For soil/sediment samples, the purge
device is heated.
VOA D-2
10/86
-------
SECTION II
SAMPLE PREPARATION AND. STORAGE
VOA 0-3
10/86
-------
II. A
PART A - SAMPLE STORAGE AND HOLDING TIMES
1. Procedures for Sample Storage
1*1 The samples muse be protected from light and refrigerated at 4'c
(+2'C) from the time of receipt until analysis or extraction.
2. Contract Required Holding Times
2.1 VOA analysis of water or soil/sediment samples must be completed
within 10 days of VTSR.
VOA D-4
10/86
-------
II. B
PART B - PROTOCOLS FOR HEXADECANE EXTRACTION OF VOLATILES FROM WATER AND
SOIL/SEDIMENT FOR OPTIONAL SCREENING
1. Summary of Method
WATER - a 40 ml aliquot of sample is extracted with 2 ml of hexadecane. This
provides a minimum quantitation limit (MQL) of:
Compounds MQL ug/L
non-halogenated aromatics 40- 50
halogenated methanes 800-1000
halogenated ethanes 400- 500
SOIL/SEDIMENT - Forty mL of reagent water are added to 10 g (vet veight)
of soil and shaken. The water phase is in turn extracted with 2 mL of
hexadecane. This provides a minimum quantitation limit of approximately four
times higher than those listed for water.
The hexadecane extraction and screening protocols for purgeables are optional.
These protocols are included to aid the analyst in deciding whether a sample
is low or medium level. The use of these or other screening protocols could
prevent saturation of the purge and trap system and/or the GC/MS system. It
is recommended that these or other screening protocols be used, particularly
if there is some doubt about the level of organics in a sample. This is
especially true in soil/sediment analysis *
2. Limitations
These extraction and preparation procedures were developed for rapid screening
of water samples from hazardous waste sites. The design of the methods thus
does not stress efficent recoveries or low limits of quantitation. Rather,
the procedures were designed to screen at moderate recovery and sufficient
sensitivity for a broad spectrum of organic chemicals. The results of the
analyses thus may reflect only a minimum of the amount actually present in
some samples. This is expeclally true if water soluble solvents are present.
3. Interferences
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that lead to
discrete artifacts and/or elevated baselines in the total ion current
profiles. All of these materials must be routinely demonstrated to be
free from interferences under the conditions of the analysis by running
laboratory reagent blanks. Matrix interferences may be caused by
contaminants that are coextraceed from the sample. The extent of
matrix interferences will vary considerably from source to source,
depending upon the nature and diversity of the site being sampled.
V0A 0-5
10/86
-------
3F
II. B
Apparatus and Materials
4.1 Vials and caps, 2 mL for GC auto sampler.
4.2 Volumetric flask, 50 mL with ground glass stopper.
4.3 Pasteur plpets, disposable.
4.4 Centrifuge tube, 50 mL with ground glass stopper or Teflon-lined
screw cap.
4.5 Balance - Analytical, capable of accurately weighing +_ 0.0001 g.
Reagents
5.1 Hexadecane and methanol - pesticide residue analysis grade or equivalent.
5.2 Reagent water - Reagent water is defined as water in which an interfer-
ent is not observed at the CRQL of each parameter of interest.
5.3 Standard mixture #1 containing benzene, toluene, ethyl benzene and
xylene. Standard mixture //2 containing n-nonane and n-dodecane.
5.3.1 Stock standard solutions (1.00 ug/uL)- Stock standard solutions
can be prepared from pure standard materials or purchased as
certified solutions.
5.3.1.1 Prepare stock standard solutions by accurately weigh-
ing about 0.0100 g of pure material. Dissolve
the material in methanol dilute to volume in a 10 mL
volumetric flask. Larger volumes can be used at the
convenience of the analyst. If compound purity.is
certified at 96Z or greater, the weight can be used
without correction to calculate the concentration
of the stock standard.
5.3.1.2 Transfer the stock standard solutions into multiple
Teflon-sealed screw-cap vials. Store, with no head-
space, at -10°C to -20°C, and protect from light.
Stock standard solutions should be checked frequently
for signs of degradation or evaporation, especially
just prior to preparing calibration standards from
then. These solutions must be replaced after six
months, or sooner if comparison with quality control
check samples indicates a problem. Standards prepared
from gases or reactive compounds such as styrene must
be replaced after two months, or sooner if comparison
with quality control check samples indicates a problem.
5.3.2 Prepare working standards of mixtures #1 and #2 at 100 ng/uL of
each compound in methanol. Store these solutions as in 5.3.1.2
above.
VOA D-6
10/86
-------
II.
Sample Extraction
6.1 Water
6.1.1 Allow the contents of the 40 mL sample vial to come to room
temperature. Quickly transfer the contents of the 40 mL sample
vial to a 50 mL volumetric flask. Immediately add 2.0 mL of
hexadecane, cap the flask, and shake vigorously for 1 minute.
Let phases separate. Open the flask and add sufficient reagent
water to bring the hexadecane layer into the neck of the flask.
6.1.2 Transfer approximately 1 mL of the hexadecane layer to a 2.0 mL
GC vial. If an emulsion is present after shaking the sample,
break it by:
o pulling the emulsion through a small plug of Pyrex glass
wool packed in a pipet, or
o transferring the emulsion to a centrifuge tube and cen-
trifuging for several minutes.
6.1.3 Add 200 uL of working standard mixture #1 and #2 to separate
40 mL portions of reagent water. Follow steps 6.1.1 - 6.1.2
beginning with the immediate addition of 2.0 mL of hexadecane.
6.2 Soil/Sediment
6.2.1 Add approximately 10 g of soil (wet weight) to 40 mL of
reagent water in a 50 mL centrifuge tube with a ground glass
stopper or teflon-lined cap. Cap and shake vigorously for
one minute. Centrifuge the capped flask briefly. Quickly
transfer supernatant water to a 50 mL volumetric flask
equipped with a ground glass stopper.
6.2.2 Follow 6.1, starting with the addition of 2.0 mL of hexade-
cane.
Sample Analysis
The sample is ready for GC/FI0 screening. Proceed to Section III, Optional
Screening of Hexadecane Extracts for Volatiles.
V0A D-7
10/86
-------
SECTION III
OPTIONAL SCREENING OF HEXADECANE
EXTRACTS FOR VOLATILES
VOA D-8
10/86
-------
III.
1. Summary of Method
1*1 The hexadecane extracts'of water and soil/sediment are screened on a
gas chromatograph/flame Ionization detector (GC/FID). The results of
the screen will determine if volatile organlcs are to be analyzed by
low or medium level GC/MS procedures if the sample is a soil/sediment,
or to determine the appropriate dilution factor if the sample Is water*
2. Apparatus and Materials
2.1 Gas chromatograph - An analytical system complete with gas chromatograph
suitable for on-column injection and all required accessories including
syringes, analytical columns, gases, detector, and' strip-chart recorder.
A data system is recommended for measuring peak areas.
2.1.1 Above-described GC, equipped with flame ionization detector.
2.1.2 GC column - 3 m x 2 mm ID glass column packed with 10% 0V-101
on 100-120 mesh Chroraosorb W-HP (or equivalent). The column
temperature should be programmed from 80°C to 2809C at 16'C/min.
and held at 280"C for 10 minutes.
3. Reagents
3.1 Hexadecane - pesticide residue analysis grade or equivalent.
4. Limitations
4.1 The flame ionization detector varies considerably in sensitivity when
comparing aromatlcs and halogenated methanes and ethanes. Haloraethanes
are approximately 20 X less sensitive than aromatlcs and haloethanes
approximately 10 X less sensitive. Low molecular weight, water soluble
solvents e.g. alcohols and ketones, will not extract from the water, and
therefore will not be detected by the GC/FID.
4.2 Following are two options for interpreting the GC/FID chromatogram.
4.2.1 Option A is to use standard mixture #1 containing the the
aromatlcs to calculate an approximate concentration of the
aromatlcs in the sample. Use this information to determine the
proper dilution for purge and trap if the sample is a water or
whether to use the low or medium level GC/MS purge and trap
methods if the sample is a soil/sediment (see Table 1, paragraph
6.2.1.3 for guidance). This should be the best approach,
however, the aromatlcs may be absent or obscured by higher
concentrations of other purgeables. In these cases, Option 5
may be the best approach.
VOA D-9
10/86
-------
III.
4.2.2 Option B is Co use standard mixture #2 containing nonane and
dodecane to calculate a factor. Use che factor Co calculaCe a
dilution for purge and trap of a water sample or to determine
whether to use the low or medium level GC/MS purge and trap
methods for soil/sediment samples (see Table 1, paragraph
6.2.1.3 for guidance). All purgeables of interest have reten-
tion times less than the n-dodecane.
5. Extract Screening
5.1 External standard calibration - Standardize the GC/FIO each 12 hr.
shift for half scale response. This is done by injecting 1-5 uL of the
extracts that contain approximately 10 ng/uL of the mix //I and mix #2
compounds, prepared in paragraph 5.3.1 of Section II, Part B. Use the
GC conditions specified in 2.1.2.
5.2 Inject the same volume of hexadecane extract as the extracted standard
mixture in 5.1. Use the GC conditions specified in 2.1.2.
6. Analytical Decision Point
6.1 Water
6.1.1 Compare the chromatograms of the hexadecane extract of the
sample with those of the reagent blank and extract of the
standard.
6.1.1.1 If no peaks are noted, other than those .also in the
reagent blank, analyze a 5 mL water sample by purge
and trap GC/MS.
6.1.1.2 If peaks are present prior to the n-dodecane and the
aromatics are distinguishable, follow Option A (4.2.1).
6.1.1.3 If peaks are present prior to the n-dodecane but the
aromatics are absent or indistinguishable, use Option B
as follows: If all peaks are <3Z of the n-nonane,
analyze a 5 mL water sample by purge and trap GC/MS.
If any peaks are X3Z of the n-nonane, measure the
peak height or area of the major peak and calculate
the dilution factor as follows:
peak area of sample major peak X 50-dilution
peak area of n-nonane factor
The water sample will be diluted using the calculated
factor just prior to purge and trap GC/MS analysis.
VOA D-10
10/86
-------
6.2 Soli/Sediment
6.2.1 Compare Che chroraatograms of Che hexadecane extract of the
sample with chose of Che reagenc blank and excracc of che
standard.
6.2.1.1 If no peaks are noced, other than those also in the
reagent blank, analyze a 5 g sample by low level
GC/MS.
6.2.1.2 If peaks are present prior to the n-dodecane and
the arooatics are distinguishable, follow Opcion A
(paragraph 4.2.1) and che concencracion information
in Table 1, paragraph 6.2.1.3, to determine whether to
analyze by low or medium level method.
6.2.1.3 If peaks are present prior to che n-dodecane but
Che aromacics are absenc or indiscinguishable, use
Opcion B as follows: Calculace a factor using che
following formula:
peak area of sample major peak ¦ X Faccor
peak area of n-nonane
Table 1 - Determination of GC/MS Purge & Trap Mechod
Approximate
X Factor Analyze by Concentration Range*
ug/kg
0-1.0 low level method 0-1,000
>1.0 medium level mechod >1,000
* This concentration range is based on the response of aromatics Co GC/FIO.
When comparing GC/FID responses, the concentration for halomethanes is
20X higher, and that for haloethanes 10X higher.
6.3 Sample Analysis
Proceed to Section IV, GC/MS Analysis of Volatiles.
VOA D—11 10/86
-------
SECTION IV
GC/MS ANALYSIS
OF VOLATILES
VOA D-12
-------
IV
1. Summary of Methods
1*1 Water samples
An inert gas is bubbled through a 5 mL sample contained In a specifically
designed purging chamber at ambient temperature. The purgeables are
efficiently transferred from the aqueous phase to the vapor phase. The
vapor Is swept through a sorbent column where the purgeables are trapped.
After purging is completed, the sorbent column is heated and backflushed
with the inert gas to desorb the purgeables onto a gas chromatographic
column. The gas chromatograph is temperature programmed Co separate
the purgeables which are then detected with a mass spectrometer.
An aliquot of the sample is diluted with reagent water when dilution is
necessary* A 5 mL aliquot of the dilution is taken for purging.
1*2 Soil/Sediment Samples
1.2.1 Low Level. An inert gas is bubbled through a mixture of a 5 g
sample and reagent water contained in a suggested specially
designed purging chamber (illustrated in Figure 5) at elevated
temperatures* The purgeables are efficiently transferred from
the aqueous phase to the vapor phase. The vapor is swept through
a sorbent column where the purgeables are trapped. After
purging is completed, the sorbent column is heated and back*
flushed with the inert gas to desorb the purgeables onto a gas
chromatographic column. The gas chromatograph is temperature
programmed to separate the purgeables which'are then detected'
with a mass spectrometer.
1.2.2 Medium Level. A measured amount of soil is extracted with
methanol* A portion of the methanol extract is diluted to 5 mL
with reagent water. An inert gas is bubbled through this
solution in a specifically designed purging chamber at ambient
temperature. The purgeables are effectively transferred from
the aqueous phase to the vapor phase. The vapor is swept
through a sorbent column where the purbeables are trapped.
After purging is completed, the sorbent column is heated and
backflushed with the inert gas to desorb the purgeables onto a
gas chromatographic column. The gas chromatograph is temperature
programmed to separate the purgeables which are then detected
with a mass spectrometer.
VOA 0-13
10/86
-------
IV.
2. Interferences
2.1 Impurities in the purge gas, organic compounds out-gassing from the
plumbing ahead of the trap, and solvent vapors in the laboratory account
for the majority of contamination problems. The analytical system must
be demonstrated to be free from contamination under the conditions of
the analysis by running laboratory reagent blanks as described in
Exhibit E. The use of non-TFE tubing, non-TFE thread sealants, or flow
controllers with rubber components in the purging device should be
avoided.
2*2 Samples can be contaminated by diffusion of volatile organics (parti-
cularly fluorocarbons and methylene chloride) through the septum seal
into the sample during storage and handling. A holding blank prepared
from reagent water and carried through the holding period and the
analysis protocol serves as a check on such contamination. One holding
blank per case should be analyzed. Data must be retained by laboratory
and made available for inspection during on-site evaluations.
2.3 Contamination by carry-over can occur whenever high level and low level
samples are sequentially analyzed. To reduce carryover, the purging
device and sampling syringe must be rinsed with reagent water between
sample analyses. Whenever an unusually concentrated sample is encountered,
it should be followed by an analysis of reagent water to check for
cross contamination. For samples containing large amounts of water-
soluble materials, suspended solids, high boiling compounds or high
purgeable levels, it may be necessary to wash out the purging device .
with a detergent solution, rinse it with distilled water, and then dry
it in a 105"C oven between analyses. The trap and other parts of the
system are also subject to contamination; therefore, frequent bakeout
and purging of the entire system may be required.
2.4 The laboratory where volatile analysis is performed should be completely
free of solvents.
3. Apparatus and Materials
3.1 Micro syringes - 25 uL and larger, 0.006 inch ID needle.
3.2 Syringe valve - two-way, with Luer ends (three each), if applicable to
the purging device.
3.3 Syringe - 5 mL, gas tight with shut-off valve.
3.4 Balance-Analytical, capable of accurately weighing ± 0.0001 g. and a
top-loading balance capable of weighing £ 0.1 g.
VOA D-14
10/86
-------
IV.
3.5 Glassware
3.5.1 o Bottle - 15 mL, screw cap, with Teflon cap liner.
o Volumetric flasks - class A with ground-glass stoppers,
o Vials - 2 mL for GC autosampler.
3.6 Purge and trap device - The purge and trap device consists of three
separate pieces of equipment; the sample purger, trap and the desorber.
Several complete devices are now commercially available.
3.6.1
3.6.2
3.6.3
3.6.4
3.6.5
3.7 GC/MS system
3.7.1 Gas chromatograph - An analytical system complete with a tempera-
ture programmable gas chromatograph suitable for on-column
Injection and all required accessories including syringes,
analytical columns, and gases.
The sample purger must be designed to accept 5 mL samples with
a water column at least 3 cm deep. The gaseous head space
between the water column and the trap must have a total volume
of less than 15 mL. The purge gas must pass through the water
column as finely divided bubbles, each with a diameter of less
than 3 mm at the origin. The purge gas must be Introduced no
more than 5 mm from the base of the water column. The sample
purger, illustrated in Figure 1, meets these design criteria.
Alternate sample purge devices may be utilized provided equiva-
lent performance is demonstrated.
The trap must be at least 25 cm long and have an inside diameter
of at least 0.105 inch. The trap must be packed to contain the
following minimum lengths of absorbents: 15 cm of 2,6-diphenylene
oxide polymer (Tenax-GC 60/80 mesh) and 8 cm of silica gel (Davison
Chemical, 35/60 mesh, grade 15, or equivalent). The minimum
specifications for the trap are illustrated in Figure 2.
The desorber should be capable of rapidly heating the trap to
180*C. The polymer section of the trap should not be heated
higher than 180°C and the remaining sections should not exceed
220°C during bakeout mode. The desorber design, illustrated
in Figure 2, meets these criteria.
The purge and trap device may be assembled as. a separate unit
or be coupled to a gas chromatograph as illustrated in Figures
3 and 4.
A heater or heated bath capable of maintaining the purge device
at 40 #C + l'C.
VOA D-15
10/86
-------
IV.
3.7.2 Column - 6 ft long x 0.1 In 10 glass, packed with 1Z SP-1000 on
Carbopack B (60/80 mesh) or equivalent. NOTE: Capillary
columns may be used for analysis of volatiles, as long as the
Contractor follows the analytical procedures in EPA Method
524.2, uses the internal standards and surrogates specified
in this contract, and demonstrates that the analysis meets all
of the performance and QA/QC criteria contained in this contract.
3.7.3 Mass spectrometer - Capable of scanning from 35 to 260 amu
every 3 seconds or less, utilizing 70 volts (nominal) electron
energy in the electron impact ionization mode and producing a
mass spectrum which meets all the criteria in Table 2 when 50
ng of 4-bromofluorobenzene (BFB) is injected through
the gas chromatograph inlet*
3.7.4 GC/MS interface - Any gas chromatograph to mass spectrometer
interface that gives acceptable calibration points at 50 ng or
less per injection for each of the parameters of interest and
achieves all acceptable performance criteria (Exhibit E) may be
used. Gas chromatograph to mass spectrometer interfaces con-
structed of all-glass or glass-lined materials are recommended.
Glass can be deactivated by silanizing with dichlorodimethylsilane,
3.7.5 Data system - A computer system must be interfaced to the mass
spectrometer that allows the continuous acquisition and storage
on machine readable media of all mass spectra obtained through-
out the duration of the chromatographic program. The computer
must have software that allows searching any GC/MS data file
for ions of a specified mass and plotting such ion abundances
versus time or scan number. This type of plot is defined as an
Extracted Ion Current Profile (EICP). Software must also be
available that allows integrating the abundance in any EICP
between specified time or scan number limits.
4. Reagents
4.1 Reagent water - Reagent water is defined as water in which an interferent
is not observed at or above the CRQL of the parameters of interest.
4.1.1 Reagent water may be generated by passing tap water through a
carbon filter bed containing about 453 g of activated carbon
(Calgon Corp., Filtrasorb-300 or equivalent).
4.1.2 A water purification system (Millipore Super-Q or equivalent)
may be used to generate reagent water.
4.1.3 Reagent water may also be prepared by boiling water for 15
minutes. Subsequently, while maintaining the temperature at
90°C, bubble a contaminant-free inert gas through the water for
one hour. While still hot, transfer the water to a narrow-mouth
screw—cap bottle and seal with a Teflon—lined septum and cap.
VOA D-16 10/86
-------
IV.
4.2 Sodium thiosulfate - (ACS) Granular.
4.3 Methanol - Pesticide quality or equivalent.
4.4 Stock standard solutions - Stock standard solutions may be prepared
from pure standard materials or purchased and must be traceable to
EMSL/LV supplied standards. Prepare stock standard solutions in methanol
using assayed liquids or gases as appropriate.
4.4.1 Place about 9.8 mL of methanol Into a 10.0 mL tared ground
glass stoppered volumetric flask. Allow the flask to stand,
unstoppered, for about 10 minutes or until all alcohol vetted
surfaces have dried. Weigh the flask to the nearest 0.1 mg.
4.4.2 Add the assayed reference material as described below.
4.4.2.1 Liquids - Using a 100 uL syringe, immediately add two
or more drops of assayed reference material to the
flask then reweigh. The liquid must fall directly
into the alcohol without contacting the neck of the
flask.
4.4.2.2 Gases - To prepare standards for any of the four
halocarbons that boil below 30°C (bromomethane,
chloroethane, chloromethane, and vinyl chloride),
fill a 5 mL valved gas-tight syringe with the reference
standard to she 3.0 oL mark. Lower the needle to 3 am
above the methanol meniscus. Slowly introduce the
reference standard above the surface of the liquid.
The heavy gas rapidly dissolves in the methanol. This
may also be accomplished by using a lecture bottle
equipped with a Hamilton Lecture Bottle Septum (//86600).
Attach Teflon tubing to the side-arm relief value and
direct a gentle stream of gas into the methanol
meniscus.
4.4.3 Reweigh, dilute to volume, stopper, then mix by inverting the
flask several times. Calculate the concentration in micrograms
per microliter from the net gain in weight. When compound
purity is assayed to be 96Z or greater, the weight may be used
without correction to calculate the concentration of the stock
standard. Commercially prepared standards may be used at any
concentration if they are certified by the manufacturer.
Commercial standards must be traceable to EMSL/LV-supplied
standards.
4.4.4 Transfer the stock standard solution into multiple Teflon-
sealed screw-cap bottles. Store with no headspace at -10 °C to
-20°C and protect from light. Once one of the bottles containing
the standard solution has been opened, it may be used for at
most one week.
V0A 0-17
10/86
-------
IV.
4.4.5 Prepare fresh standards every cwo months for gases or for
reactive compounds such as styrene. All other standards must
be replaced after six months, or sooner if comparison with
check standards indicates a problem.
4.5 Secondary dilution standards - Using stock standard solutions, prepare
secondary dilution standards in methanol that contain the compounds of
Interest, either singly or mixed together. (See GC/MS Calibration in
Exhibit E). Secondary dilution standards should be stored with minimal
headspace and should be checked frequently for signs of degradation or
evaporation, especially just prior to preparing calibration standards
from them.
4.6 Surrogate standard spiking solution. Prepare stock standard solutions
for toluene-da, p-bromofluorobenzene, and 1,2-dichloroethane-d4 in
methanol as described in paragraph 4.4. Prepare a surrogate standard
spiking solution from these stock standards at a concentration of 250
ug/10 mL in methanol.
4.7 Purgeable Organic Matrix Standard Spiking Solution
4.7.1 Prepare a spiking solution in methanol that contains the following
compounds at a concentration of 250 ug/10.0 mL:
Purgeable Organics
1,1-dichloroethene
trichloroethene
chlorobenzene
toluene
benzene
4.7.2 Matrix spikes also serve as duplicates; therefore, add an
aliquot of this solution Co each of cwo portions from one
sample chosen for spiking.
4.8 BFB Standard - Prepare a 25 ng/uL solution of BFB in methanol.
4.9 Great care must be taken to maintain the integrity of all standard
solutions. Store all standard solutions at -10 °C to -20®C in screw-cap
amber bottles with teflon liners.
5. Calibration
5.1 Assemble a purge and trap device chat meets the specification in paragraph
3.6. Condition Che trap overnight at 180 °C in the purge mode wich an
inert gas flow of at least 20 cm^/min. Daily, prior to use, condition
the traps for 10 minutes while backflushing at 180°C with the column at
220"C.
VOA D-18
10/86
-------
IV.
Connecc Che purge and .crap device Co a gas chromacograph. The gas
chroraacograph muse be operated using temperature and flow race parameters
equivalent to those in paragraph 7.1.2 Calibrate the purge and trap-GC/MS
system using the internal standard technique (paragraph 5.3).
Internal standard calibration procedure. The three internal standards
are bromochloromethane, 1,4-difluorobenzene, and chlorobenzene-ds, at
50 ug/L at time of purge.
5.3.1 Prepare calibration standards at a minimum of five concentration
levels for each TCL parameter. The concentration levels are
specified in Exhibit E. Aqueous standards may be stored up to
24 hours, if held in sealed vials with zero headspace at -10°C
to -20°C and protected from light. If not so stored, they oust
be discarded after an hour.
5.3.2 Prepare a spiking solution containing each of the internal
standards using the procedures described in paragraphs 4.4 and
4*5. It is recommended that the secondary dilution standard be
prepared at a concentration of 25 ug/mL of each internal standard
compound. The addition of 10 uL of Chis standard to 5.0 mL of
sample or calibration standard would be equivalent of 50 ug/L.
5.3.3 Tune the GC/MS system to meet the criteria in Exhibit E by
injecting BFB. Analyze each calibration standard, according to
paragraph 7, adding 10 uL of internal standard spiking solution
directly to the syringe. Tabulate the area response of the
characteristic Ions against concentration for each compound and
internal standard and calculate relative response'factors- (RRF)
for each compound using equation 1.
EQ. 1 RRF - -3- X ,.la
*13
Where:
Ax ¦ Area of the characteristic ion for the compound
to be measured.
Aj>3 ¦ Area of the characteristic ion for the
specific internal standard from Exhibit E.
cis " Concentration of the internal standard.
Cg - Concentration of the compound to be measured.
5.3.4 The average relative response factor (RRF) must be calculated
for all compounds. A system performance check must be made
before Chis calibration curve is used. Five compounds (the
system performance check compounds) are checked for a minimum
average relative response factor. These compounds (the SPCC)
are chloromethane, 1,1-dichloroethane, bromoform, 1,1,2,2-
V0A D-19
10/86
-------
IV.
tetrachloroethane, and chlorobenzene. Six compounds (che
calibration check compounds, CCC) are used Co evaluate the
curve. These compounds the (CCC) are 1,1-Dichloroethene,
Chloroform, 1,2 -Dichloropropane, Toluene, Ethylbenzene, and
Vinyl Chloride. Calculate the Z Relative Standard Deviation
(ZRSD) of RRF values over the working range of the curve. A
minimum ZRSD for each CCC must be met before the curve is
valid.
ZRSD ¦ Standard deviation x 100
mean
See instructions for Form VI, Initial Calibration Data for more
details.
5.3.5 Check of the calibration curve must be performed once every 12
hours. These criteria are described in detail in the instruc-
tions for Form VII, Continuing Calibration Check, (see Exhibit
B, Section III). The minimum relative response factor for the
system performance check compounds must be checked. If this
criteria is met, the relative response factor of all compounds
are calculated and reported. A percent difference of the dally
relative response factor (12 hour) compared to the average
relative response factor from the initial curve is calculated*
The maximum percent difference allowed for each compound flagged
as 'CCC' in Form VII is checked. Only after both these criteria
are met can sample analysis begin.
5.3.6 Internal standard responses and retention times in all standards
must be evaluated during or immediately after data acquisition.
If the retention time for any internal standard changes by more
than 30 seconds from the latest daily (12 hour) calibration
standard, the chromatographic system must be inspected for
malfunctions, and corrections made as required. The extracted
ion current profile (EICP) of the internal standards must be
monitored and evaluated for each standard. If the EICP area
for any internal standard changes by more than a factor of two
(-50Z to +100Z), the mass spectrometric system must be inspected
for malfunction and corrections made as appropriate. When
corrections are made, re-analysis of samples analyzed while che
system was malfunctioning is necessary.
6. GC/MS Operating Conditions
6.1 These performance tests require the following instrumental
parameters:
Electron Energy: 70 Volts (nominal)
Mass Range: 35 - 260
Scan Time: to give at least 5 scans per peak
and not to exceed 3 seconds per scan.
V0A D-20
10/86
-------
IV.
7. Sample Analysis
7.1 Water Samples
7.1.1 All samples and standard solutions oust be allowed Co warm Co
ambient temperature before analysis.
7.1.2 Recommended operating conditions for the gas chrooatograph -
Packed column conditions: Carbopak B (60/80 mesh) with 1% SP-1000
packed in a 6 foot by 2 mm ID glass column with helium carrier
gas at a flow rate of 30 cm^/min. Column temperature is isother-
mal at 45®C for 3 minutes, then programmed at 8°C per minute to
220"C and held for 15 minutes. Injector temperature is 200-225aC.
Source temperature is set according to the manufacturer's speci-
fications. Transfer line temperature is 250-300®C. The recom-
mended carrier gas is helium at 30 cm^/sec. (See EPA Method
5.2.4.2 for capillary column condition.)
7.1.3 After achieving the key ion abundance criteria, calibrate the
system daily as described in Exhibit E.
7.1.4 Adjust the purge gas (helium) flow rate to 25-40 cm^/min.
Variations from this flow rate may be necessary to achieve
better purging and collection efficiencies for some compounds,
particularly chloromethane and bromoform.
7.1.5 Remove the plunger from a 5 mL syringe and attach a closed
syringe valve. Open the sample or standard bottle which has
been allowed to come to ambient temperature, and carefully pour
the sample into the syringe barrel to just short of overflowing.
Replace che syringe plunger and compress the sample. Open the
syringe valve and vent any residual air while adjusting the
sample volume to 5.0 mL. This process of taking an aliquot
destroys the validity of the sample for future analysis so if
there is only one VOA vial, the analyst should fill a second
syringe at this time to protect against possible loss of sample
integrity. This second sample is maintained only until such a
time when the analyst has determined that the first sample has
been analyzed properly. Filling one 20 mL syringe would allow
the use of only one syringe. If a second analysis is needed
from the 20 mL syringe, it must be analyzed within 24 hours.
Care must also be caken to prevent air from leaking into the
syringe.
7.1.6 The purgeable organlcs screening procedure (Section III),
if used, will have shown the approximate concentra-
tions of major sample components. If a dilution of the
sample was indicated, this dilution shall be made just
prior to GC/MS analysis of the sample. All steps in che
dlluclon procedure must be performed without delays until
the point at which the diluted sample is in a gas tight
syringe.
VOA D-21
10/86
-------
IV.
7,1.6.1 The following procedure will allow for dilutions
near che calculated dilution factor from Che screening
procedure:
7.1.6.1.1 All dilutions are made in volumetric
flasks (10 mL to 100 mL).
7.1.6.1.2 Select the volumetric flask that will
allow for the necessary dilution. Inter-
mediate dilutions may be necessary for
extremely large dilutions.
7.1.6.1.3 Calculate the approximate volume of
reagent water which will be added to Che
volumetric flask selected and add slightly
less than this quantity of reagent water
to the flask.
7.1.6.1.4 Inject the proper aliquot from the syringe
prepared in paragraph 7.1.5 into the
volumetric flask. Aliquots of less Chan
1 mL increments are prohibited. Dilute
the flask to the mark with reagent
water. Cap che flask, invert, and shake
three times.
7.1.6.1.5 Fill a 5 mL syringe with the diluted
sample as in paragraph 7.1.5..
7.1.6.1.6 If this Is an intermediate dilution, use
it and repeat above procedure to achieve
larger dilutions.
7.1.7 Add 10.0 uL of the surrogate spiking solution (4.6) and 10.0
uL of the internal standard spiking solution (5.3.2) through
the valve bore of the syringe, then close Che valve. The
surrogate and internal standards may be mixed and added as a
single spiking solution. The addicion of 10 uL of che surrogate
spiking solution to 5 mL of sample is equivalent to a concen-
tration of 50 ug/L of each surrogate standard.
7.1.8 Attach the syringe-syringe valve assembly Co che syringe valve
on the purging device. Open the syringe valves and inject the
sample into the purging chamber.
7.1.9 Close both valves and purge che sample for 11.0 + 0.1 minutes
at ambient temperature.
7.1.10 Ac the conclusion of the purge time, attach the trap to the
chromatograph, adjust the device to the desorb mode, and begin
the gas chromatographic temperature program. Concurrently,
introduce the trapped materials Co che gas chromacographic
column by rapidly heacing the crap Co 180°C while backflushing
VOA D-22
10/86
-------
IV
the Crap with an inert gas between 20 and 60 cm^/min for four
minutes. If this rapid heating requirement cannot be met, Che
gas chromatographic column must be used as a secondary trap by
cooling it to 30*C (or subambient, if problems persist) instead
of the recommended initial temperature of 45°C.
7.1.11 While Che trap is being desorbed into the gas chromatograph,
empty the purging chamber. Wash the chamber with a minimum of
two 5 mL flushes of reagenc water to avoid carryover of pollutant
compounds.
7.1.12 After desorbing the sample for four minutes, recondition the
trap by returning the purge and trap device to the purge mode.
Wait 15 seconds, then close the syringe valve on the purging
device to begin gas flow through Che crap. The trap temperature
should be maincained at 180°C. Trap temperatures up to 220®C
may be employed, however the higher temperature will shorten the
useful life of the crap. After approximately seven minuces,
turn off the trap heater and open the syringe valve to 3top the
gas flow through the trap. When cool, the trap is ready for the
next sample.
7.1.13 If the initial analysis of a sample or a dilution of a sample
has concentration of TCL compounds that exceeds the initial
calibration range, the sample must be reanalyzed at a higher
dilution. Secondary ion quantitation is only allowed when
there are sample interferences with the primary ion. If secon-
dary ion quantitation is used, document the reasons in the Case
Narrative. When a sample is analyzed that has saturated ions
from a compound, this analysis must be followed by a blank
reagenc wacer analysis. If Che blank analysis is noc free of
lncerferences, Che system must be decontaminated. Sample
analysis may noc resume uncll a blank can be analyzed Chat is
free of interferences.
7.1.14 For water samples, add 10 uL of the matrix spike solution
(paragraph 4.7) to the 5 mL of sample purged. Disregarding any
dilutions, this is equivalent to a concentration of 50 ug/l of
each matrix spike standard.
7.1.15 All dilutions must keep the response of Che major conscicuencs
(previously sacuraced peaks) in che upper half of the linear
range of Che curve.
Soil/SedlmenC Samples
Two approaches may be caken to detannine whether che low level or
medium level method may be followed.
o Assume the sample is low level and analyze a 5 g sample.
o Use the X factor calculated from the optional hexadecane screen
(Section III, paragraph 6.2.1.3).
V0A D-23
10/86
-------
IV.
If peaks are saturated from the analysis of a 5 g sample, a smaller
sample size muse be analyzed to prevent saturation. However, the
smallest sample size permitted is 1 g. If smaller than 1 g sample size
is needed to prevent saturation, the medium level method must be used.
7.2.1 Low Level Soil Method
The low level soil method is based on purging a heated sediment/
soil sample mixed with reagent water containing the surrogate
and internal standards* Analyze all reagent blanks and standards
under the same conditions as the samples.
Use 5 grams of sample or use the X Factor to determine the
sample size for purging.
o If the X Factor is 0 (no peaks noted on the hexadecane
screen), analyze a 5 g sample.
o If the X Factor is between 0 and 1.0, analyze a minimum
of a 1 g sample.
7.2.1.1 The GC/MS system should be set up as in 7.1.2 -
7.1.4. This should be done prior to the preparation
of the sample to avoid loss of volatiles from standards
and sample. A heated purge calibration curve must be
prepared and used for the quantitation of all samples
analyzed with the low-level method. Follow the
initial and daily calibration instructions except for
the addition of a 40°C purge temperature.
7.2.1.2 To prepare the reagent water containing the surrogates
and internal standards, remove the plunger from a 3
mL "Luerlock" type syringe equipped wich a syringe
valve and fill until overflowing with reagent water.
Replace the plunger and compress the water to vent
trapped air. Adjust the volume to 5.0 mL. Add 10 uL
each of the surrogate spiking solution (4.6) and the
internal standard solution to the syringe through the
valve. (Surrogate spiking solution and internal
standard solution may be mixed together). The addition
of 10 uL of the surrogate spiking solution to 5 g of
soil/sediment is equivalent to 50 ug/kg of each
surrogate standard*
7.2.1.3 The sample (for volatile organics) consists of the
entire concents of the sample container. Do not discard
any supernatant liquids. Mix the contents of the
sample container with a narrow metal spatula. Weigh
the amount determined in 7.2.1 into a tared purge
device. Use a top loading balance. Note and record
the actual weight to the nearest 0.1 g.
7.2.1.4 Immediately after weighing the sample, weigh 5-10 g
of the sediment into a tared crucible. Determine the
percent moisture by drying overnight at 105aC. Allow
VOA D-24
10/86
-------
IV.
Co cool in a desiccator before weighing. Concentra-
tions of individual analytes will be reported relative
to the dry weight of sediment.
Percent moisture
g of aample-g of dry sample
g of saaple X 100 - Z moisture
7.2.1.5 Add the spiked reagent water to the purge device and
connect the device to the purge and trap system.
MOTE: Prior to the attachment of the purge device,
steps 7.2.1.2 and 7.2.1.3 must be performed rapidly to
avoid loss of volatile organics. These steps muse be
performed in a laboratory free of solvent fumes.
7.2.1.6 Heat the sample to 40#C + 18C and purge the sample
for 11*0 + 0*1 minutes*
7*2*1*7 Proceed with the analysis as outlined in 7*1*10 -
7*1*13* Use 5 mL of the same reagent water as the
reagent blank.
7.2.1*8 For low level soils/sediment add 10 uL of the matrix
spike solution (4.7) to the 5 mL of water (7*2*1.2).
The concentration for a 5 g sample would be equivalent
to SO ug/kg of each matrix spike standard.
7*2*2 Medium Level Soil Method
The medium level soil method is based on extracting the soil/
sediment sample with methanol* An aliquot of the methanol
extract is added to reagent water containing the surrogate and
internal standards. This is purged at ambient temperature*
All samples with an X Factor >1*0 should be anal/zed by the
medium level method. If saturated peaks occurred or would
occur when a 1 g sample was analyzed, the medium level method
must be used.
7*2*2*1 The GC/MS system should be set up as in 7*1*2 - 7.1*4.
This should be done prior to the addition of the
methanol extract to reagent water.
7*2*2*2 The sample (for volatile organics) consists of the
entire contents of the sample container* Oo not
discard any supernatant liquids* Mix the contents of
the sample container with a narrow metal spatula.
Weigh 4 g (wet weight) into a tared 15 mL vial. Use
a top loading balance. Note and record the actual
weight to the nearest 0*1 g. Determine Che percent
moisture as in 7*2*1*4*
VOA 0-25
10/86
-------
IV.
7.2.2.3 Quickly add 9.0 mL of methanol, Chen 1.0 mL of the
surrogate spiking solution to the vial. Cap and
shake for 2 minutes. NOTE: Steps 7.2.2.1 and 7.2.2.2
must be performed rapidly to avoid loss of volatile
organics. These steps must be performed in a labora-
tory free of solvent fumes.
7.2.2.4 Using a disposable pipette, transfer approximately 1
mL of extract into a GC vial for storage. The remainder
may be disposed of. Transfer approximately 1 mL of
the reagent methanol to a GC vial for use as the
method blank for each case or set of 20 samples,
whichever is more frequent. These extracts may be
stored in the dark at 4°C (+2"C) prior to analysis.
The addition of a 100 uL aliquot of each of these
extracts in paragraph 7.2.2.6 will give a concentration
equivalent to 6,200 ug/kg of each surrogate standard.
7.2.2.5 The following table can be used to determine the
volume of methanol extract to add to the 5 mL. of
reagent water for analysis. If the Hexadecane screen
procedure was followed, use the X factor (Option B) or
the estimated concentration (Option A) to determine the
appropriate volume. Otherwise, estimate the concen-
tration range of the sample from the low level analysis
to determine Che appropriate volume. If the sample
was submicced as a medium level sample, start with
100 uL.
All dilutions muse keep Che response of the major
constituents (previously saturated peaks) in the-
upper half of linear range of the curve.
Estimated Take this Volume of
X Factor Concentration Ranged Methanol Extract^/
ug/kg uL
0.25 - 5.0 500 - 10,000 100
0.5 - 10.0 1000 - 20,000 50
2.5 - 50.0 5000 - 100,000 10
12.5 - 250 25,000 - 500,000 100 of 1/50 dilution3/
VOA D-26
10/86
-------
IV.
Calculate appropriate dilation, factor for concentrations exceeding the table.
1/ Actual concentration ranges could be 10 to 20 times higher than this If
the compounds are halogenated and the estimates are from GC/FID.
2/ The volume of methanol added to the 5 mL of water being purged should be
kept constant. Therefore, add to the 5 mL syringe whatever volume of
methanol is necessary to maintain a volume of 100 uL added to the syringe.
3/ Dilute an aliquot of the methanol extract and then take 100 uL for
analysis.
7.2.2.6 Remove the plunger from a 5 mL "Luerlock" type syringe
equipped with a syringe valve and fill until overflow-
ing with reagent water. Replace ehe plunger and
compress the water to vent trapped air. Adjust the
volume to 4.9 mL. Pull the plunger back to 5 mL to
allow volume for the addition of sample and standards.
Add 10 uL of the internal standard solution. Also
add the volume of methanol extract determined in 7.2.2.5
and a volume of methanol solvent to total 100 uL
(excluding methanol in standards).
7.2.2.7 Attach the syringe-syringe valve assembly to the
syringe valve on the purging device. Open the syringe
valve and Inject the water/methanol sample into the
purging chamber.
7.2.2.8 Proceed with the analysis as outlined in 7.1.9 -
7.1.13. Analyze all reagent blanks on the same
instrument as Che samples. The standards should also
contain 100 uL of methanol to simulate the sample
conditions•
7.2.2.9 For a matrix spike in the medium level sediment/soil
samples, add 8.0 mL of methanol, 1.0 mL of surrogate
spike solution (4.6), and 1.0 mL of matrix spike
solution (4.7) in paragraph 7.2.2.2. This results in
a 6,200 ug/kg concentration of each matrix spike
standard when added to a 4 g sample. Add a 100 uL
aliquot of this extract to 5 mL of water for purging
(as per paragraph 7.2.2.6).
8. Qualitative Analysis
8.1 The compounds listed in the Target Compound List (TCL), Exhibit C,
shall be identified by an analyst competent in the interpretation of
mass spectra (see PreAward Bid Confirmation description) by comparison
of the sample mass spectrum to the mass spectrum of a standard of the
suspected compound. Two criteria must be satisfied to verify the iden-
tifications: (1) elution of the sample component at the same GC relative
retention time as the standard component, and (2) correspondence of the
sample component and standard component mass spectra.
VOA D-27
10/86
-------
IV.
8>1.1 For establishing correspondence of Che GC relative retention
time (RRT), the sample component RRT must compare within + 0.06
RRT units of the RRT of the standard component. For reference,
the standard must be run on the same shift as the sample. If
coelution of interfering components prohibits accurate assignment
of the sample component RRT from the total ion chromatogram, the
RRT should be assigned by using extracted ion current profiles
for ions unique to the component of interest.
8.1.2 For comparison of standard and sample component mass spectra,
mass spectra obtained on the contractor's GC/MS are required.
Once obtained, these standard spectra may be used for identifi-
cation purposes, only if the contractor's GC/MS meet3 the daily
tuning requirements for BFB. These standard spectra may be
obtained from the run used to obtain reference RRTs.
8.1.3 The requirements for qualitative verification by comparison of
mass spectra are as follows:
8.1.3.1 All ions present in the standard mass spectra at
a relative intensity greater than 10 X (most abundant
ion in the spectrum equals 100%) must be present in
the sample spectrum.
8.1.3.2 The relative intensities of ions specified in 8.1.3.1
must agree within plus or minus 20? between the stan-
dard and sample spectra* (Example: For an ion with an
abundance of 502 in the standard spectra) the correspond—
ing sample abundance must be between 30 and 70 percent).
8.1.3.3 Ions greater than 10% in the sample spectrum but not
present in the standard spectrum must be considered and
accounted for by the analyst making the comparison. In
Task III, the verification process should favor false
positives. All compounds meeting the identification
criteria must be reported with their spectra. For all
compounds below the CRQL report the actual value fol-
lowed by a "J", e.g., M3J."
8.1.4 If a compound cannot be verified by all of the criteria in
8.1.3.3, but in the technical judgement of the mass spectral
interpretation specialist, the identification is correct, then
the Contractor shall report that identification and proceed
with quantification in 9.
A library search shall be executed for non-TCL sample components for
the purpose of tentative identification. For this purpose, the 1985
release of the National Bureau of Standards Mass Spectral Library (or
more recent release), containing 42,261 spectra, shall be used. Computer
generated library search routines must not use normalization routines
that would misrepresent the library or unknown spectra when compared to
each other.
VOA D-28
10/86
-------
IV.
8.2.1 Up Co 10 nonsurrogate organic compounds of greatest apparent
concentration not listed in Exhibit C for the purgeable organic
fraction shall be tentatively identified via a forward search of
the NBS mass spectral library. (Substances vith responses less than
10Z of the Internal standard are not required to be searched in
this fashion). Only after visual comparison of sample spectra
with the nearest library searches will the mass spectral inter-*
pretation specialist assign a tentative identification. Computer
generated library search routines must not use normalization
routines that would misrepresent the library or unknown spectra
when compared to each other.
8.2.2 Guidelines for making tentative identification:
8.2.2.1 Relative intensities of major ions in the reference
spectrum (ions greater than 10% of the most abundant
ion) should be present in the sample spectrum.
8.2.2.2 The relative intensities of the major ions should
agree within + 20%. (Example: For an ion with an
abundance of SO percent of the standard spectra, the
corresponding sample ion abundance must be between 30
and 70 percent.)
8.2*2.3 Molecular ions present in reference spectrum
should be present in sample spectrum.
8.2.2.4 Ions present in the sample spectrum but not in
the reference spectrum should be reviewed for possible
background contamination or presence of co-elutlng
compounds.
8.2.2.5 Ions present in the reference spectrum but not in
the sample spectrum should be reviewed for possible
subtraction from the sample spectrum because of back-
ground contamination or co-eluting compounds. Data
system library reduction programs can sometimes
create these discrepancies.
8.2.3 If in the technical judgement of the mass spectral interpretation
specialist, no valid tentative identification can be made, the
compound should be reported as unknown. The mass spectral specia-
list should give additional classification of the unknown compound,
if possible (i.e. unknown aromatic, unknown hydrocarbon, unknown
acid type, unknown chlorinated compound). If probable molecular
weights can be distinguished, include them.
9. Quantitative Analysis
9.1 TCL components identified shall be quantified by the internal standard
method. The internal standard used shall be that which is listed in
Exhibit E, Table 2.1. The EICP area of the characteristic ions of analytes
listed in Tables 2 and 3 in this Section are used.
VOA D-29 10/86
-------
IV
9.2 Internal standard responses and retention times In all standards must
be evaluated during or immediately afcer data acquisition. If the
retention time for any internal standard changes by more than 30
seconds from the latest dally (12 hour) calibration standard, the
chromatographic system oust be inspected for malfunctions, and
corrections made as required. The extracted ion current profile (EICP)
of the internal standards must be monitored and evaluated for each
sample, blank, matrix spike and matrix spike, duplicate. If the EICP
area for any internal standard changes by more than a factor of two
(-50% to -*-1002), the mass spectrometrlc system must be inspected for
malfunction and corrections made as appropriate. When corrections
are made, reanalysis of samples analyzed while the system was malfunc-
tioning is necessary.
If after re-analysis, the EICP areas for all internal standards
are inside the contract limits (-50% to +100%), then the
problem with the first analysis Is considered to have been
within the control of the laboratory. Therefore, only submit
data from the analysis with EICP's within the contract limits.
This is considered the initial analysis and must be reported
as such on all data deliverables.
If the re-analysis of the sample does not solve the problem,
i.e., the EICP areas are outside the contract limits for
both analyses, then submit the EICP data and sample data from
both analyses. Distinguish between the initial analysis and
the re-analysis on all data deliverables, using the sample
suffixes specified in Exhibit B. Document in the Case Narrative
all inspection and corrective actions taken.
9.3 The relative response factor (RRF) from the daily standard analysis is
used to calculate the concentration in the sample. Use the relative
response factor as determined in paragraph 5.3.3 and the equations'
below. When TCL compounds are below contract required quantitation
limits (CRQL) but the spectra meet the identification criteria,
report the concentration with a "J." For example, if CRQL is 10 ug/L
and concentration of 3 ug/L is calculated, report as "3J."
9.2.1
9.2.2
Water
(AgXlg)
Concentration ug/L ¦ (A£3)(RRF)(V0)
Where:
Ax ¦ Area of the characteristic ion for the compound to be
measured
Aj3 * Area of the characteristic ion for the specific Internal
standard from Exhibit E.
Ig ¦ Amount of internal standard added in nanograms (ng)
V0 ¦ Volume of water purged in milliliters (mL) (take into
account any dilutions)
1°/86
V0A D-30
-------
IV.
Sediment/Soil (medium level)
Concentration
(AxXIsKVc)
ug/kg - (Ala)(RRF)(Vi)(Wa)(D)
Sediment/Soil (low level)
Concentration
(Dry weight basis)
(Ax)(I8)
ug/kg - (Ais)(RRF)(Ws)(D)
Where:
• same as for water, above
¦ Volume of total extract (uL) (use 10,000 uL
0
Vi
or a factor of this when dilutions are made)
¦ Volume of extract added (uL) for purging
¦ 100 - % moisture
100
¦ Weight of sample extracted (g) or purged
An estimated concentration for non-TCL components tentatively identified
shall be quantified by the internal standard method. For quantification,
the nearest internal standard free of interferences shall be used.
9.4.1 The formula for calculating concentrations is the same as in
paragraph 9.3. Total area counts (or peak heights) from the total
ion chromatograms are to be used for both the compound to be
measured and the internal standard. A relative response factor.
(R&F) of one (1) Is to be assumed. The value from this quantita-
tion shall be qualified as estimated. This estimated concentration
should be calculated for all tentatively identified compounds as
well as those identified as unknowns.
9.4.2 Xylenes (o,m, & p - isomers) are to be reported as Xylenes (total).
Since o- and p-Xylene overlap, the Xylenes must be quantitated as
m-Xylene. The concentration of all Xylene isomers must be added
together to give the total.
9.4.3 1,2-Dichloroethene (trans and cis stereoisomers) are to be reported
as 1,2-Dichloroethene (total). The concentrations of both isomers
must be added together to give the total.
Calculate surrogate standard recovery on all samples, blanks
and spikes. Determine if recovery is within limits and report
on appropriate form.
V0A D-31
10/86
-------
9.5.1 Calculation for surrogate recovery.
IV.
Percent Surrogate Recovery ¦ Qd X 100%
Qa
where: Q4 * quantity determined by analysis
Qa - quantity added to sample
9.5.2 If recovery is not within limits, the following is required:
o Check to be sure there are no errors in calculations, surrogate
solutions and internal standards. Also, check instrument
performance.
o Reanalyze the sample if none of the above reveal a problem.
9.5.3 If Che reanalysis of the sample solves the problem, then the
problem was within the laboratory's control. Therefore, only
submit data from the analysis with surrogate spike recoveries
within the contract limits. This shall be considered the initial
analysis and shall be reported as such on all data deliverables.
9.5.4 If the reanalysis of the sample does not solve the problem, i.e.,
surrogate recoveries are outside the contract limits for both
analyses, then submit the the surrogate spike recovery data and
the sample data from both analyses. Distinguish between the
initial analysis and the reanalysis on all data deliverables,
using the sample suffixes specified in Exhibit B.
9.5.5 If the sample with surrogate recoveries out3lde the limits is the
sample used for the matrix spike and matrix spike duplicate, and
the surrogate recoveries of the matrix spike and matrix spike
duplicate show the same pattern (i.e., outside the limits), then
the sample, matrix spike, and matrix spike duplicate do not
require reanalysis. Document in the narrative the similarity in
surrogate recoveries.
Table 2
Characteristic Ions for Surrogate and
Internal Standards for Volatile Organic Compounds
Compound
Primary Ion
Secondary Ionfa^
SURROGATE STANDARDS
4-Bromofluorobenz ene
1,2-Dichloroethane d-4
Toluene d-8
INTERNAL STANDARDS
Broraochloromethane
1,4-Difluorobenz ene
Chlorobenzene d-5
95
65
98
128
114
117
174, 176
102
70, 100
49, 130, 51
63, 88
82, 119
VOA D-32
10/86
-------
IV.
Table 3
Characteristic Ions for Volaclle TCL Compounds
Parameter
Primary Ion*
Secondary Ion(s)
Chloronethane
50
52
Bromoraethane
94
96
Vinyl chloride
62
64
Chloroethane
64
66
Methylene chloride
84
49, 51, 86
Acetone
43
58
Carbon disulfide
76
78
1,l-Dlchloroethene
96
61, 98
1,1-Dichloroechane
63
65, 83, 85, 98,
1,2-Dlchloroethene
96
61, 98
Chloroform
83
85
1,2-Dlchloroechane
62
64, 100, 98
2-Butanone
72
57
1,1,1-Trlchloroethane
97
99, 117, 119
Carbon tetrachloride
117
119, 121
Vinyl acetate
43
86
Broraodlchlorooethane
83
85
1,1,2,2-Tetrachloroethane
83
85, 131, 133,
1,2-Dichloropropane
63
65, .114
trans-1,3-Dichloropropene
75
77
Trlchloroethene
130
95, 97, 132
~lbromochloromethane
129
208, 206
1,1,2-Tri chloroe thane
97
83, 85, 99, 132
Benzene
78
-
cis-l,3-Dichloropropene
75
77
Bromoform
173
171, 175, 250, 252,
2-Hexanone
43
58, 57, 100
4-Methyl-2-pentanone
43
58, 100
Te t rachloroe t hene
164
129, 131, 166
Toluene
92
91
Chlorobenzene
112
114
Ethyl benzene
106
91
Styrene
104
78, 103
Total xylenes
106
91
* The primary ion should be used unless interferences are present, in which
case, a secondary ion may be used*
VOA D-33 10/86
-------
IV
Optional
foam >\
Trap ' ^
^.Cmh V4 in.
OO.
L 14mm
v*j 0.0.
^J~ Inlet '/* in.
'/4 »».
O.O «*<(
_ Sample Inlet
2-way Syringe vaiva
/ 7cm 20 gauge syringe needle
^Sm/n 0.0. Rubber Saptum
_ TO mm 0.0. in. 0.0.
;jjr molecular
i siava purge
^ A gas filter
Purge gas
flow eontroi
10mm glass frit
medium porosity
f^uK 1. Purging dav*em
Fading procedure
Construction
Glass _
woo/ m
Grada 15
Silica gat 8em
Tanas 16cm
FT:
Glass
woof
Smm
Trap iff tat
Compression fining
•nut and farruias
14ft 7-Vfoot resistance
wit a wrapped solid
^ -TL | Thermocouple/controMar
s — T i^-sansof
e-V\ f
Electronic
temperature
control
and
pyrometer
f Tubing 25 cm.
0.105 in. ID.
0.125 in. O.D.
stainless staal
Ptgur* 2. Trap packings and construction to incfuda desorb capability
VOA u-34
10/86
-------
IV.
Carrier ges flow control
Pressure regulator ^iQii
Purgo got
flow control
13X mo/ocular
IMv» filtor
Liquid in/action ports
^Column own
VTWf
riI\I\J^ U dat9Ctor
jLTU U | m-~-Anolyticsl column
\ options/ 4-port column
S'port *»!*etion voho
voi*e
Trop Mot
ftosistonco wiro
w' control
Trao (Off)
22*C
Purging
device
Noto:
AII linos between
trap and GC
should bo heeled
to 40* C
Figure 3. Schematic of purgo and trop device — purge- modo
Carrier got flow control Liquid infection ports ^umn ortn
Pressure reguietor
Purgo got
flew control I , f
1
13X molecular——^
filler
ft "1"! 1—i- Confirmatory column
vST~\ J.L^u^_l> To detector
—
J
»Analytical column
optional 4-port column
selection valve
6'port frap infat
valve J Resistance wiro
, Heater control
Tr*P I On
i7
-------
IV.
PURGE INLET FITTING
SAMPLE OUTLET FITTING
3" * 6mm O D. GLASS TUBING
SEPTUM
CAP
40mi VIAL
Figure 5. Low Soils Impinger
VOA D-36
10/86
-------
EXHIBIT D
ANALYTICAL METHODS
FOR SEMIVOLATILES
-------
TABLE OF CONTENTS
Zass.
SECTION I - INTRODUCTION SV D-l
SECTION II - SAMPLE PREPARATION AND STORAGE SV D-3
PART A - SAMPLE STORAGE AND HOLDING TIMES SV D-4
PART B - SAMPLE PREPARATION FOR EXTRACTABLE
SEMIVOLATILES (BNA) IN WATER SV D-5
PART C - PROTOCOLS FOR SOIL/SEDIMENT SV D-10
1. Medium Level Preparation for Screening and Analysis of
Semivolatiles (BNA) SV D-10
2. Low Level Preparation for Screening and Analysis of
Semivolatiles (BNA) SV D-14
SECTION III - SCREENING OF SEMIVOLATILE ORGANIC EXTRACTS SV D-25
SECTION IV - GC/MS ANALYSIS OF SEMIVOLATILES SV D-29
10/86
-------
SECTION I
INTRODUCTION
The analytical methods that follow are designed to analyze water, soil and
sediment from hazardous waste sites for the organic compounds on the Target
Compound List (TCL) (See Exhibit C). The methods are based on EPA Method
625 (Base/Neutrals and Acids).
The methods are divided into the following sections: sample preparation,
screening, and analysis. Sample preparation covers sample extraction and
cleanup techniques. As described in the screening section, a portion of
the extracts may be screened on a gas chromatograph with appropriate
detectors to determine the concentration level of organics. The analysis
section contains the GC/MS analytical methods for organics.
St D-l
10/86
-------
Method for the Determination of Extractable Semivolatlles (Base/Neutral
and Acid) Organic Compounds.
1.1 Scope and Application
This method covers the determination of a number of organic compounds
that are partitioned into an organic solvent and are amenable to gas
chromatography. These TCL compounds and the contract required
quantitation limits are listed in Exhibit C.
Problems have been associated with the following compounds covered by
this method. Olchlorobenzidine and 4-chloroaniline can be subject to
oxidative losses during solvent concentration. This is especially true
in the soil/sediment method when concentrating the methylene chloride/
acetone extraction solvent. Hexachlorocyclopentadiene is subject to
thermal decomposition in the inlet of the gas chromatograph, chemical
reaction in acetone solution, and photochemical decomposition.
N-nitrosodiphenylamine decomposes in the gas chromatographic inlet forming
diphenylamlne and, consequently, cannot be separated from diphenylamine
native to the sample.
1.2 The method involves solvent extraction of the matrix sample characteri-
zation to determine the appropriate analytical protocol to be used, and
GC/MS analysis to determine semivolatile (BNA) organic compounds present
In the sample.
SV D-2
10/86
-------
SECTION II
SAMPLE PREPARATION AND STORAGE
SV D-3
10/86
-------
II. A
PART A - SAMPLE STORAGE AND HOLDING TIMES
1. Procedures for Sample Storage
1.1 The samples muse be protected from light and refrigerated at 4°C
(+2°C) from the time of receipt until extraction and analysis.
2. Contract Required Holding Times
2.1 If separator/ funnel procedures are employed for extractions for
semivolatile analyses, extraction of water samples shall be
completed within 5 days of VTSR. (Validated Time of Sample Receipt),
and extraction of soil/sediment samples shall be completed within 10
days of VTSR. If continuous liquid-liquid extraction procedures are
employed, extraction of water samples shall be started within 5 days
of VTSR, and extraction of soil/sediment samples shall be started
within 10 days of VTSR.
Extracts of either water or soil/sediment samples must be analyzed
within 40 days of VTSR.
SV 0-4
10/86
-------
II. B
PART B - SAMPLE PREPARATION FOR EXTRACTABLE SEMIVOLATILES (BWA) IN WATER
1. Summary of Method
A measured volume of sample, approximately one liter, Is serially extracted
with methylene chloride at a pK greater than 11 and again at pH less than 2,
using a separatory funnel or a continuous extractor. The methylene chloride
extracts are dried and concentrated separately to a volume of 1 mL. The ex-
tract for pesticlde/PCB analysis may be prepared from an aliquot of the
extract for semivolatiles, or in a separate extraction procedure* If it is
prepared from the semivolatile extract, refer to Exhibit 0 PEST for the pro-
cedures for extraction of pesticides/PCBs.
2. Interferences
2.1 Method interferences may be caused by contaminants in solvents, reagents,
glassware and other sample processing hardware, that lead to discrete
artifacts and/or elevated baselines in the total ion current profiles
(TICPs). All of these materials must be routinely demonstrated to be
free from interferences under the conditions of the analysis by running
laboratory reagent blanks. Matrix interferences may be caused by
contaminants that are coextracted from the sample. The extent of
matrix interferences will vary considerably from source to source.
3. Apparatus and Materials
3*1 Glassware (Brand names and catalog numbers are Included for illustration
purposes only).
3.1.1 Separatory funnel - 2,000 mL, with teflon stopcock.
3.1.2 Drying column - 19 mm ID chromatographic column with coarse
frit. (Substitution of a small pad of Pyrex glass wool for the
frit will prevent cross contamination of sample extracts.)
3.1.3 Concentrator tube - Kudema-Danish, 10 mL, graduated (Kontes
K-570050-1025 or equivalent). Calibration must be checked at
the volumes employed in the test. Ground glass stopper is used
to prevent evaporation of extracts*
3.1.4 Evaporative flask - Kudema-Danish, 500 mL (Kontes K-570001 0500
or equivalent). Attach to concentrator tube with springs.
3.1.5 Snyder column - Kuderna-Danish, Three-ball macro (Kontes K-503000
0121 or equivalent).
3.1.6 Snyder column - Kuderna-Danish, Two-ball micro (Kontes K569001
0219 or equivalent).
3.1.7 Vials - Amber glass, 2 mL capacity with Teflon-lined screw cap.
SV 0-5
10/86
-------
3.1.8 Continuous liquid-liquid extractors - Equipped with Teflon or
glass connnecting joints and stopcocks requiring no lubrication
(Hershberg-Wolf Extractor-Ace Glass Company, Vineland, NJ P/N
6841-10 or equivalent.)
3.2 Silicon carbide boiling chips - approximately 10/40 mesh. Heat to 400
°C for 30 minutes or Soxhlet extract with methylene chloride.
3.3 Water bath - Heated, with concentric ring cover, capable of temperature
control (+ 2°C). The bath should be used in a hood.
3.4 Balance - Analytical, capable of accurately weighing 0.0001 g.
3.5 Nitrogen evaporation device equipped with a water bath that can be
maintained at 35-40"C. The N-Evap by Organomation Associates, Inc.
South Berlin, MA (or equivalent) is suitable.
Reagents
4.1 Reagent water - Reagent water is defined as a water in which an inter-
ferent is not observed at or above the CRQL of each parameter of interest
4.2 Sodium hydroxide solution (10N) - Dissolve 40 g NaOH in reagent water
and dilute to 100 mL.
4.3 Sodium thiosulfate - (ACS) Granular.
4.4 Sulfuric acid solution (1+1) - Slowly add 50 aL of H2SO4 (sp gr.1.84) to
50 mL of reagent water.
4.5 Acetone, methanol, methylene chloride - Pesticide quality or equivalent.
4.6 Sodium sulfate - (ACS) Powdered, anhydrous. Purify by heating at 400°C
for four hours in a shallow tray, cool in a desiccator, and score in a
glass bottle. Baker anhydrous powder, catalog #73898 or equivalent.
4.7 Surrogate standard spiking solution.
4.7.1 Surrogate standards are added to all samples and calibration
solutions; the compounds specified for this purpose are phenol-d$
2,4,6 tribromophenol; 2 fluorophenol; nltrobenzene-d5;
terphenyl-d^4 and 2-fluorobiphenyl. Two additional surrogates,
one base/neutral and one acid, may be added.
4.7.2 Prepare a surrogate standard spiking solution that contains the
base/neutral compounds at a concentration of 100 ug/mL, and the
acid compounds at 200 ug/mL. Store the spiking solutions at
4°C (+2°C) in Teflon-sealed containers. The solutions should
checked frequently for stability. These solutions must be
replaced after twelve months, or sooner if comparison with
quality control check samples indicates a problem.
4.8 BNA Matrix standard spiking solution. The matrix spike solution
consists of:
SV D-6
10/86
-------
II. B
Base/Neutral3 Acids
1,2 f4-trlchlorobenzene pencachlorophenol
acenaphthene phenol
2,4-dinitrotoluene 2-chlorophenol
pyrene 4-chloro-3-methylphenol
N-nitroso-di-n-propylamine 4-nltrophenol
1,4-dlchlorobenzene
Prepare a spiking solution that contains each of the base/neutral
compounds above at 100 ug/1.0 mL in methanol and the add compounds at
200 ug/1.0 ml in methanol. Analyze duplicate aliquots of a sample
spiked with BNA matrix spiking solution.
5. Sample Extraction - Separatory Funnel
5.1 Samples may be extracted using separatory funnel techniques. If emulsions
prevent acceptable solvent recovery with separatory funnel extraction,
continuous extraction (paragraph 6.) may be used. The separatory
funnel extraction scheme described below assumes a sample volume of
1-liter.
5.2 Using a 1-liter graduated cylinder, measure out a 1-liter sample aliquot
and place it into a 2-liter separatory funnel. Pipet 1.0 mL surrogate
standard spiking solution into the separatory funnel and mix well.
Check the pH of the sample with wide range pH paper and adjust to pH >
11 with 10N sodium hydroxide. Add 1.0 mL of BNA matrix spiking solution
to each of two 1-llter portions from the sample selected for spiking.
5.3 Add 60 mL methylene chloride to the separatory funnel and extract the
sample by shaking the funnel for two minutes, with periodic venting to
release excess pressure. Allow the organic layer to separate from the
water phase for a minimum of 10 minutes. If the emulsion interface
between layers is more than one-third the volume of the solvent layer,
the analyst must employ mechanical techniques to complete the phase
separation. The optimum technique depends upon the sample, and may
Include: stirring, filtration of the emulsion through glass wool,
centrlfugation, or other physical methods.
Collect the methylene chloride extract in a 250-mL Erlenmeyer flask.
If the emulsion cannot be broken (recovery of less than 80Z of the
methylene chloride, corrected for the water solubility of methylene
chloride), transfer the sample, solvent and emulsion into the
extraction chamber of a continuous extractor. Proceed as described
in paragraph 6.3.
5.4 Add a second 60-mL volume of methylene chloride to the sample bottle
and repeat the extraction procedure a second time, combining the
extracts in the Erlenmeyer flask. Perform a third extraction in the
same manner. Label the combined extract as the base/neutral fraction.
SV D-7 -10/86
-------
II. B
5.5 Adjusc Che pH of che aqueous phase co less chan 2 using sulfuric acid
(1 + 1). Serially extract three times with 60-mL aliquots of methylene
chloride, as per paragraph 5.3. Collect and combine the extracts in a
250-mL Erlenmeyer flask and label the combined extract as the acid fraction4
5.6 Assemble a Kudema-Danish (K-D) concentrator by attaching a 10-mL
concentrator tube to a 500-mL evaporative flask. Other concentration
devices or techniques may be used in place of the K-D, If equivalency is
demonstrated for all extractable organics listed in Exhibit C.
5.7 Transfer the individual base/neutral and acid fractions by pouring
extracts through separate drying columns containing about 10 cm of
anhydrous sodium sulfate, and collect the extracts in the separate K-D
concentrators. Rinse the Erlenmeyer flasks and columns with 20 to 30
oL of methylene chloride to complete the quantitative transfer.
5.8 Add one or two clean boiling chips and attach a three-ball Snyder
column to the evaporative flask. Pre-vet the Snyder column by adding
about I mL methylene chloride to the top of the column. Place Che K-D
apparatus on a hot water bath (80° to 90°C) 'so that the concentrator
tube is partially immersed in the hot water, and thie entire lower
rounded surface of the flask is bathed with hot vapor. Adjust che
vertical position of Che apparatus and the water temperature as required
to complete the concentration in 10 to 15 minutes. At the proper rate
of distillation, che balls of the column will actively chatter but the
chambers will not flood with condensed solvent. When the apparent
volume of liquid reaches 1 mL, remove the K-D apparatus from the water
bath and allow it to drain and cool for at least 10 minutes. Remove
the Snyder column and rinse che flask and its lower jolnc into che
concentrator tube with 1-2 mL of methylene chloride. A 5-mL syringe is
recommended for this operation.
5.9 Micro Snyder column technique - Add another one or two clean boiling
chips to the concentrator cube and attach a cwo-ball micro Snyder column.
Pre-wet the Snyder column by adding about 0.5 mL of methylene chloride
to the top of the column. Place the K-D apparatus on a a hot water
bath (80° to 90°C) so that the concentrator tube Is partially Immersed
In the hot water. Adjust Che vertical position of the apparatus and the
water temperature as required to complete the concentration in 5 to 10
minutes. Ac Che proper race of distillation the balls of the column will
actively chatter but the chambers will not flood with condensed solvent.
When Che apparent volume of liquid reaches about 0.5 mL, remove che K-D
apparacus from Che wacer bach and allow it to drain for ac lease 10
mlnuCes while cooling. Remove che Snyder column and rinse ics flask
and ics lower joinc lnco Che concentracor Cube wlch 0.2 mL of mechylene
chloride. Adjusc Che final volume co 1.0 mL with methylene chloride, if
GC/MS analysis will not be performed immediately, stopper the concentrator
tube and store refrigerated. If the extracts will be stored longer
than Cwo days, they should be transferred to Individual Teflon-sealed
screw cap bottles and labeled base/neutral or acid fraction, as
appropriate.
SV D-8
10/86
-------
II. B
5.10 Nitrogen blowdown technique (taken from ASTM Method 03086)
The following method may be used for final concentration, instead of
the procedure outlined in paragraph 5.9. Place the concentrator tube
in a warm water bath (35"C) and evaporate the solvent volume to just
below 1 mL using a gentle stream of clean, dry nitrogen filtered through
a column of activated carbon). Caution: New plastic tubing must not be
used between the carbon trap and the sample, as it may Introduce intef-
ferences. The internal wall of the tube must be rinsed down several
times with methylene chloride during the operation and the final volume
brought to I 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.
Sample Extraction - Continuous Liquid-Liquid Extractor
6.1 Check the pH of the sample with wide-range pH paper and adjust to pH 11
with 10 N sodium hydroxide. Transfer a 1-liter sample aliquot to the
continuous extractor; using a plpet, add 1 mL of surrogate standard
spiking solution and mix well.
6.2 Add 500 mL of methylene chloride to Che distilling flask. Add sufficient
reagent water to ensure proper operation and extract for 18 hours.
Allow to cool, then detach the boiling flask and dry. Concentrate the
extract as In paragraphs 5.6 through 5.8. Hold the concentrated extract
for combining with the acid extract (see paragraph 6.4).
6.3 Add 500 mL of methylene chloride to a clean distilling flask and attach
it to the contlnous extractor. Carefully adjust the pH of the aqueous
phase to less than 2 using sulfuric aicd (1 + 1). Extract for 18
hours. Dry and concentrate the extract as described in paragraphs 5.6
through 5.8. Hold the concentrated extract and label as the acid
extract.
6.3.1 If the base/neutral and/or add extracts cannot be concentrated
to a final volume of 1 mL, dilute the more concentrated extract
to the final volume of the least concentrated extract.
The samples extracts are ready for GC/MS analysis. Proceed to Section IV,
GC/MS Analysis of Semlvolatlles. If high concentrations are suspected (e.g.,
highly colored extracts) the optional GC/FIO screen in Section III is
recommended.
SV D-9
10/86
-------
II. c
PART C - PROTOCOLS FOR SOIL/SEDIMENT
Ic is mandatory thac all soil/sediment samples be characterized as co concen-
tration level so that the appropriate analytical protocol is chosen to
ensure proper quantitation limits for the sample.
Note that the terms "low level" and "medium level" are not used here as a judge-
ment of degree of contamination but rather as a description of the concentration
ranges that are encompassed by the "low" and "medium" level procedures.
The laboratory is at liberty to determine the method of characterization. The
following two screening methods may be used for soil/sediment sample character-
ization:
o Screen an aliquot from the "low level" 30 g extract or an aliquot from the
"medium level" 1 g extract
o Screen using either GC/FID or GC/MS as the screening instrument.
The concentration ranges covered by these two procedures may be considered to
be approximately 330 ug/kg - 20,000 ug/kg for the low level analysis and >20,000
ug/kg for medium level analysis for BNA extractables. The extract for pesticide/
PCB analysis may be prepared from an aliquot of the extract for semivolaciles, or
in a separate extraction procedure. If it is prepared from the semivolatile ex-
tract, refer to Exhibit D PEST for the procedures for extraction of pesticides/PCBs%
Screen from the Medium Level Method
Take 5.0 mL from the 10.0 mL total extract and concentrate to 1.0 mL and screen.
If the sample concentration is >20,000 ug/kg proceed with GC/MS analysis of the
"organics. If the sample concentration is <20,000 ug/kg discard the medium
level extract and follow the low level method.
Screen from Low Level Method
Take 5.0 mL from the 300 mL (approximate) total extract from the 30 g sample and
concentrate to 1.0 mL and screen. If the concentration is >20,000 ug/kg in the
original sample, discard the 30 g extract and follow the medium level methods
for organics, using medium level surrogates. If the sample concentration is
<20,000 ug/kg, proceed with concentration and the remainder of the low level
method.
1. Medium Level Preparation for Screening and Analysis of Semivolatiles (BNA)
1.1 Scope and Application
This procedure is designed for the preparation of sediment/soil samples
which may contain organic chemicals at a level greater than 20,000 ug/kg.
1.1.1 The extracts and sample aliquots prepared using this method are
screened by GC/MS or FID, using capillary columns for base/neutral
and acid priority pollutants, and related organic chemicals.
The results of these screens will determine whether sufficient
quantities of pollutants are present to warrant analysis by low
or medium protocol.
ct?
-------
II. c
1.1.2 If Che screenings indicate no detectable pollutants at the lower
limits of quantitation, the sample should be prepared by the low
level protocol in Section II, Part C, paragraph 2.
1.2 Summary of Method
1.2.1 Approximately 1 g portions of sediment/soil are transferred
to vials and extracted with methylene chloride. The methylene
chloride extract is screened for extractable organics by GC/FID
or GC/MS.
1.2.2 If organic compounds are detected by the screen, the methylene
chloride extract is analyzed by GC/MS for extractable organics.
1.2.3 If no organic compounds are detected by the medium level screen,
then a low level sample preparation is required.
1.3 Interferences
1.3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that
lead to discrete artifacts and/or elevated baselines in the
total ion current profiles. All of these materials must be
routinely demonstrated to be free from interferences under the
conditions of Che analysis by running laboratory reagent blanks.
Matrix interferences may be caused by contaminants that are
coextracted from the sample. The extent of matrix interferences
will vary considerably from source to source.
1.4 Limitations
1.4.1 The procedure is designed to allow quantitation limits for screen-
ing purposes as low as 20,000 ug/kg for extractable organics.
For analysis purposes, the quantitation limits are 20,000 ug/kg
for extractable organics* If peaks are present based on the
GC/FIO screen, the sample Is determined to require a medium
level analysis by GC/MS. Some samples may contain high concen-
tratlons of chemicals that interfere with the analysis of other
components at lower levels; the quantitation limits In those cases
may be significantly higher.
1.4.2 These extraction and preparation procedures were developed for
rapid and safe handling of high concentration hazardous waste
samples. The design of the methods thus does not stress effi-
cient recoveries or low limits of quantitation of all components.
Rather, the procedures were designed to screen at moderate
recovery and sufficient sensitivity, a broad spectrum of organic
chemicals. The results of the analyses thus may reflect only a
minimum of the amount actually present in some samples.
SV D-ll
10/86
-------
II. c
1.5 Reagents
1.5.1 Sodium Sulfate - anhydrous powdered reagent grade, heated at
400®C for four hours, cooled in a desiccator, and stored in a
glass bottle Baker anhydrous powder, catalog if 73898 or
equivalent.
1.5.2 Methylene chloride. Pesticide residue analysis grade or
equivalent.
1.5.3 Methanol. Pesticide residue analysis grade or equivalent.
1.5.4 Acetone. Pesticide residue analysis grade or equivalent.
1.5.5 Base/Neutral and Acid Surrogate Standard Spiking Solution
The compounds specified are phenol-d6, 2,4,6-tribromophenol,
2-fluorophenol, nitrobenzene-d5, terphenyl-di4 and 2-fluoro-
biphenyl. Prepare a solution containing chese compounds for
base/neutral surrogates at a concentration of 100 ug/1.0 mL,
and for acid surrogate standards at a concentration of 200 ug/l.o
mL in methanol. Store the spiking solutions at 4*C (+28C) in
Teflon-sealed containers. The solutions should be checked
frequently for stability. These solutions must be replaced
after twelve months, or sooner, if comparison with quality
control check samples indicates a problem.
1.5.6 Base/Neutral and Acid Matrix Standard Spiking solution.
Prepare a spiking solution in methanol that contains the following
compounds at a concentration of 100 ug/1.0 mL for base/neutrals
and 200 ug/1.0 mL for acids. Store the spiking solutions at
49C (+2°C) in Teflon-sealed containers. The solutions should
be checked frequently for stability. These solutions must be
replaced after twelve months, or sooner, If comparison with
quality control check samples indicates a problem.
Base Neutrals
1,2,4-tri chlorobenz ene
acenaphthene
2,4-dini t rot oluene
pyrene
N-nitroso-di-n-propylamine
1,4-di chlorobenz ene
1.6 Equipment
1.6.1 Glass scintillation vials, at least 20 mL, with screw cap and
teflon or aluminum foil liner.
Acids
pentachlorophenol
phenol
2-chlorophenol
4-chloro-3-raethylphenol
4-nitrophenol
SV D-12
10/86
-------
II. c
1.6.2 Spatula. Stainless steel or Teflon.
1.6.3 Balance capable of weighing 100 g to the nearest 0.01 g.
1.6.4 Vials and caps, 2 mL for GC auto sampler.
1.6.5 Disposable pipets, Pasteur; glass wool rinsed with methylene
chloride.
1.6.6 15-mL concentrator tubes.
1.6.7 Ultrasonic cell disruptor, Heat Systems Ultrasonics, Inc., Model
W-375 S0NICAT0R or equivalent (375 Watt with pulsing capability,
No. 200 1/2 inch tapped disruptor horn, and No. 419 1/8 inch
standard tapered MICROTI? probe). NOTE: In order to ensure
that sufficient energy is transferred to the sample during
extraction, the MICROTIP probe must be replaced if the tip
begins to erode. Erosion of the tip is evidenced by a rough
surface.
1.6.8 Sonabox - recommended with above disruptors for decreasing
cavitation sound.
1.6.9 Test tube rack.
1.6.10 Oven, drying.
1.6.11 Oesiccator.
1.6.12 Crucibles, porcelain.
Medlmum Level Sample Preparation.
1.7.1 Transfer the sample container into a fume hood. Open the
sample vial. Decant and discard any water layer and then mix
the sample. Transfer approximately 1 g (record weight to the
nearest 0.1 g) of sample to a 20-mL vial. Wipe the mouth of
the vial with a tissue to remove any sample material. Record
the exact weight of sample taken. Cap the vial before proceeding
with the next sample to avoid any cross-contamination.
1.7.2 Immediately after weighing the sample for extraction, weigh
5-10 g of the sediment into a tared crucible. Determine the
percent moisture by drying overnight at 105aC. Allow to cool
in a desiccator before weighing. Concentrations of individual
analytes will be reported relative to the dry weight of sediment.
2 of sample - g of dry sample
g of sample X 100 - Z moisture
1.7.3 Add 2.0 g of anhydrous powdered sodium sulfate to sample in the
20 mL vial from paragraph 1.7.1 and mix well.
SV D-13
10/86
-------
II
1.7.4 Surrogate Standards are added to all samples, spikes, and
blanks. Add 1.0 mL of surrogate spiking solution to sample
mixture.
1.7.5 Add 1.0 mL of matrix standard spiking solution to each of two 1
g portions from the sample chosen for spiking.
1.7.6 Immediately add 9.0 mL of methylene chloride to the sample and
disrupt the sample with the 1/8 inch tapered MICROTIP ultrasonic
probe for 2 minutes ac output control setting S. (If using a
sonicator other than Model W-375, refer to the manufacturer's
instructions for appropriate output settings). Before extrac-
tion, make certain that the sodium sulfate is free flowing and
not a consolidated mass. As required, break up large lumps
with a clear spatula, or very carefully with the tip of the
probe.
1.7.6.1 Add only S.O mL of methylene chloride to the matrix
spike samples to achieve a final volume of 10 mL.
1.7.7 Loosely pack disposable Pastuer pipets with 2-3 cm glass wool
plugs. Filter the extract through the glass wool and collect
5.0 mL in a concentrator tube.
1.7.8 Concentrate the extract to 1.0 mL by the nitrogen blowdown
technique described in paragraph 2.7.3.
1.7.9 Transfer the concentrate to an autosampler vial for GC/FID or
GC/MS capillary column screening. If the concentrate is scre'enag
the quantitation limits should be approximately 20,000 ug/kg.
1.7.10 Proceed to Section III, paragraph 1.
Low Level Preparation for Screening and Analysis of Semlvolatlles (BNA)
2.1 Summary of Method
A 30 gram portion of sediment is mixed with anhydrous powdered sodium
sulfate and extracted with 1:1 methylene chloride/acetone using an
ultrasonic probe. If the optional low level screen is used, a portion
of this dilute extract is concentrated fivefold and is screened by
GC/FID or GC/MS. If peaks are present at greater than 20,000 ug/kg,
discard the extract and prepare the sample by the medium level method.
If no peaks are present at greater than 20,000 ug/kg, the extract is
concentrated. An optional gel permeation column cleanup may be used
before analysis.
2.2 Interferences
Method interferences may be caused by contaminants in solvents, reagents
glassware, and other sample processing hardware chat lead co discrete '
artifacts and/or elevated baselines in the total ion current profiles.
SV 0-14
10/86
-------
II. c.
All of these materials must be routinely demonstrated to be free from
interferences under the conditions of the analysis by running laboratory
reagent blanks. Matrix interferences may be caused by contaminants
that are coextracted from the sample. The extent of matrix interferences
will vary considerably from source to source.
2.3 Apparatus and Materials
2.3.1 Apparatus for determining percent moisture
2.3.1.1 Oven, drying
2.3.1.2 Desiccator
2.3.1.3 Crucibles, porcelain
2.3.2 Disposable Pasteur glass pipets, 1 mL
2.3.3 Ultrasonic cell disruptor, Heat Systems - Ultrasonics, Inc.
Model 375 SONICATOR or equivalent (375 watt with pulsing capa-
bility, No. 305 1/4 inch tapped high gain "Q" disruptor horn or
Model 208 3/4 inch standard tip solid horn). NOTE: In order
to ensure that sufficient energy is transferred to the sample
during extraction, the horn must be replaced if the tip begins
to erode. Erosion of the tip is evidenced by a rough surface.
2.3.4 Beakers, 400 mL
2.3.5 Vacuum filtration apparatus
2.3.5.1 Buchner funnel.
2.3.5.2 Filter paper, Whatman No. 41 or equivalent.
2.3.6 Kuderaa-Danish (K-D) apparatus.
2.3.6.1 Concentrator tube - 10 mL, graduated (Kontes K-570040-
1025 or equivalent).
2.3.6.2 Evaporative flask - 500 mL (Kontes K-570001-0500 or
equivalent).
2.3.6.3 Snyder column - three-ball macro (Kontes K-503000-0121
or equivalent).
2.3.6.4 Snyder column - two ball micro (Kontes K-569001-0219)
or equivalent).
2.3.7 Silicon carbide boiling chips - approximately 10/40 mesh.
Heat to 400°C for 30 minutes or Soxhlet extract with methylene
chloride.
SV D-15
10/86
-------
II. c
2.3.8 Water bath - heated, with concentric ring cover, capable of tem-
perature control (+2°C). The bath should be used in a hood.
2.3.9 Balance, capable of accurately weighing +0.01 g.
2.3.10 Vials and caps, 2 mL for GC auto sampler.
2.3.11 Balance - Analytical, capable of accurately weighing + 0.0001 g.
2.3.12 Nitrogen evaporation device equipped with a water bath that can
be maintained at 35-40°C. The N-Evap by Organomation Associates,
Inc. South Berlin, MA (or equivalent) is suitable.
2.3.13 Gel permeation chromatography (GPC) cleanup device. NOTE: GPC
cleanup is highly recommended for all extracts for low level
soils.
2.3.13.1 Automated system
2.3.13.1.1 Gel permeation chromatograph Analytical
Biochemical Labs, Inc* GPC Autoprep 1002
or equivalent including:
2.3.13.1.2 25 mm 10 X 600 - 700 mm glass column
packed with 70 g of Bio-Beads SX-3.
2.3.13.1.3 Syringe, 10 mL with Luer-Lok. fitting.
2.3.13.1.4 Syringe filter holder and filters -
stainless steel and TFE, Gelman 4310 or
equivalent.
2.3.13.2 Manual system assembled from parts.*
2.3.13.2.1 25 mm ID X 600 - 700 mm heavy wall glass
column packed with 70 g of BIO-Beads SX-3.
2.3.13.2.2 Pump: Altex Scientific, Model No. 1001A,
semipreparative, solvent metering system.
Pump capacity « 28 mL/min.
2.3.13.2.3 Detector: Altex Scientific, Model No.
153, with 254 nm UV source and 8-ul
semi-preparative flowcells (2-mm
pathlengths)
2.3.13.2.4 Microprocessor/controller: Altex Scienti-
fic, Model No. 420, Microprocessor System
Controller, with extended memory.
*Wise, R.H., Bishop, D.F., Williams, R.T. & Austem, B.M. "Gel Permeation
Chromatography in the GC/MS Analysis of Organics in Sludges" U.S. EPA,
Municipal Environmental Research Laboratory - Cincinnati, Ohio 45268
SV 0-16
10/86
-------
II. c
2.3.13.2.5 Injector: Altex Scientific, catalog No.
201-56, sample injection valve, Tefzel,
with 10 mL sample loop.
2.3*13.2.6 Recorder: Linear Instruments, Model No.
385, 10-inch recorder.
2.3.13.2.7 Effluent Switching Valve: Teflon slider
valve, 3-way with 0.060" ports.
2.3*13.2.8 Supplemental Pressure Gauge with connecting
Tee: U.S.Gauge, 0-200 psi, stainless steel.
Installed as a "downstream" monitoring
device between column and detector.
Flow rate was typically 5 mL/min. of methy-
lene chloride. Recorder chart speed was
0.50 cm/min.
2.3.14 Pyrex glass wool.
2.3.15 Pasteur plpets, disposable.
2.4 Reagents
2.4.1 Sodium Sulfate - anhydrous powdered reagent grade, heated at
400"C for four hours, cooled in a desiccator, and stored in a
glass bottle. Baker anhydrous powder, catalog #73898 or equi-
valent .
2.4.2 Methylene chloride, methanol, acetone, isoooctane, 2-propanol
and benzene pesticide quality or equivalent.
2.4.3 Reagent water - Reagent water is defined as a water in which
an Interferent Is not observed at or above the CRQL of each
parameter of interest.
2.4.4 GPC calibration solutions:
2.4.4.1 Corn oil - 200 mg/mL in methylene chloride.
2.4.4.2 Bis(2-ethylhexylphthalate) and pentachlorophenol -
4.0 mg/mL in methylene chloride.
2.4.5 Sodium Sulfite, reagent grade.
2.4.6 Surrogate standard spiking solution.
2.4.6.1 Base/neutral and acid surrogate solution.
SV D-17
10/86
-------
II. c
2.4.6.1.1 Surrogate standards are added to all
samples, blanks, matrix spikes, matrix
spike duplicates, and calibration solu-
tions; the compounds specified for this
purpose are phenol-dg, 2,4,6-tribromo-
phenol, 2-fluorophenol, nitrobenzene-^,
terphenyl-dj4, and 2-fluorobiphenyl. Two
additional surrogates, one base/neutral
and one acid may be added.
2.4.6.1.2 Prepare a surrogate standard spiking solu-
tion at a concentration of 100 ug/1.0 mL
for base/ neutral and 200 ug/1.0 mL for
adds In methanol. Store the spiking
solutions at 4°C (+2°C) in Teflon-sealed
containers. The solutions must be replaced
after twelve months, or sooner if comparison
with quality control check samples indicate
a problem.
2.4.7 Matrix standard spiking solutions.
2.4.7.1 Base/neutral and acid matrix spiking solution con-
sists of:
Base/Neutrals (100 ug/1.0 mL)
1,2,4-trichlorobenzene
acenaphthene
2,4-dinitrotoluene
pyrene
N-nitroso-di-n-propylamine
1,4-dichlorobenzene
Acids (200 ug/1.0 mL)
pentachlorophenol.
phenol
2-chlorophenol
4-chloro-3-methylphenol
4-nitrophenol
Prepare a spiking solution that contains each of the
above in methanol. Store Che spiking solutions at
48C (+2°C) in Teflon-sealed containers. The solutions
should be checked frequently for stability. These
solutions must be replaced after twelve months, or
sooner If comparison with quality control check
samples indicate a problem.
Matrix spikes also serve as duplicates, therefore,
add volume specified in Sample Extraction section to
each of two 30-g portions from one sample chosen for
spiking.
2.5 Low Level Sample Preparation
2.5.1 Decant and discard any water layer on a sediment sample. Mix
samples thoroughly, especially composited samples. Discard any
foreign objects such as sticks, leaves, and rocks.
SV 0-18
10/86
-------
II. c
2.5.1.1 Transfer 50 g of soil/sediment Co 100 ml beaker.
Add 50 ml of water and stir for 1 hour. Determine pH
of sample with glass electrode and pH meter while
stirring. Report pH value on appropriate data sheets.
If the pH of the soil Is greater than 11 or less than
5, contact the Deputy Project Officer cited in the
contract for instructions on how to handle the sample.
Document the instructions in the Case Narrative.
Discard this portion of sample.
2.5.2 The following step should be performed rapidly to avoid loss
of the more volatile extractables. Weigh approximately 30 g
of sample to the nearest 0.1 g into a 400-mL beaker and add 60
g of anhydrous powdered sodium sulfate. Mix well. The sample
should have a sandy texture at this point. Immediately, add
100 mL of 1:1 methylene chloride - acetone to the sample.
2.5.2.1 Immediately after weighing the sample for extraction,
weigh 5-10 g of the sediment into a tared crucible.
Determine the percent moisture by drying overnight
at 105*C. Allow to cool in a desiccator before
weighing. Concentrations of individual analytes will
be reported relative to the dry weight of sediment.
Percent moisture
g of sample - g of dry sample
g of sample X 100 - 2 moisture
2.5.2.2 Weigh out two 30 g (record weight to nearest 0.1 g).
portions for use as matrix and matrix spike dupli-
cates according to 2.5.2. When using 6PC cleanup,
add 2.0 mL of the base/neutral and acid matrix spike
to each of two portions. When not using GPC cleanup,
add 1.0 mL of base/neutral and acid matrix spike to
each of the other two portions.
2.5.2.3 When using GPC, add 1.0 mL of base/neutral and acid
surrogate standard to the sample. When not using GPC,
add 0.5 mL of BNA surrogate standard to the sample.
2.5.3 Place the bottom surface of the tip of the 3/4 inch disruptor
horn about 1/2 inch below the surface of the solvent but above
the sediment layer.
2.5.4 Sonicate for 3 minutes using 3/4 inch disruptor horn with
output control knob set at 10 and mode switch on "pulse" and
X duty cycle knob set at 50%. Do MOT use the MICROTIP probe.
(If using a sonicator other than Model W-375, refer to the
manufacturer's instructions for appropriate output settings).
2.5.5 Decant and filter extracts through Whatman /Ml filter paper
using vacuum filtration or centrifuge and decant extraction
solvent.
SV D-19
10/86
-------
2.5.6- Repeat Che extraction two more times with 2 additional 100 mL
portions of 1:1 methylene chloride - acetone. Before each
extraction, make certain that the sodium sulfate is free
flowing and not a consolidated mass. As required, break up
large lumps with a clean spatula, or very carefully with the
tip of the probe. Decant off the extraction solvent after
each sonication. On the final sonlcation, pour the entire
sample into the Buchner funnel and rinse with 1:1 methylene
chloride - acetone.
2.5.6.1 If the sample is to be screened from the low level
method, take 5.0 mL and concentrate to 1.0 mL
following paragraph 2.7.2 or 2.7.3. Note that the
sample volume in this case is 5.0 mL not 10.0 mL as
given in 2.7.2. Screen the extract as per Section
III, paragraph I., "Screening of Extractable Organic
Extracts". Transfer the remainder of the 1 mL back
to the total extract from paragraph 2.5.6 after
GC/FID or GC/MS screening. (CAUTION: To minimize
sample loss, autosamplers which pre-flush samples
through the syringe should not be- used.)
2.5.7 Transfer the extract to a Kudema-Danish (K-D) concentrator
consisting of a 10 mL concentrator tube and a 500 mL evapora-
tive flask. Other concentration devices or techniques may be
used if equivalency is demonstrated for all extractable
compounds listed in Exhibit C.
2.5.8 Add one or two clean boiling chips to the evaporative flask
and attach a three-ball Snyder column. Pre-wet the Snyder
column by adding about 1 mL methylene chloride to the top.
Place the K-D apparatus on a hot water bath (80 to 90 aC) so
that the concentrator Cube is partially immersed in the hot
water and the entire lower rounded surface of the flask is
bathed with hot vapor. Adjust the vertical position of the
apparatus and the water temperature as required to complete
the concentration in 10 to 15 minutes. At the proper rate of
distillation the balls of the column will actively chatter but
the chambers will not flood with condensed solvent. When the
apparent volume of liquid reaches 1 mL, remove phe K-D appara-
tus and allow It to drain and cool for at least 10 minutes,
and make up to 10 mL volume with methylene chloride.
2.5.9 If GPC cleanup Is not used proceed to paragraph 2.7.
Extract Cleanup
2.6.1 GPC Setup and Calibration
2.6.1.1 Packing the column - Place 70 g of Bio Beads SX-3
in a 400 mL beaker. Cover the beads with methylene
chloride; allow the beads to swell overnight (before
packing the columns). Transfer the swelled beads to
SV D-20
10/86 -
-------
II. c
Che column and scare pumping solvenc through the
column, from boCCom Co Cop, at 5.0 mL/min. After
approximately 1 hour, adjust the pressure on the
column Co 7 to 10 psl and pump an additional.4 hours
Co remove air from the column. Adjust the column
pressure periodically as required Co maintain 7 to
10 psl.
2.6.1.2 Calibration of Che column - Load 5 mL of the com
011 solution into sample loop No. 1 and 5 mL of che
phthalatephenol solution into loop No. 2. Inject the
corn oil and collect 10 oL fraction (i.e., change
fraction ac 2-minute intervals) for 36 minuCes. Inject
Che phthalate-phenol solution and collecC 15 mL frac-
tions for 60 mlnuces. Decermine the corn oil elutlon
paccern by evaporadon of each fraccion to dryness
followed by a gravimetric determination of the residue.
Analyze the phthalate-phenol fractions by GC/FID on
the DB-5 capillary column, a UV spectrophotometer,
or a GC/MS system. Plot che concencraclon of each
component in each fraction versus tocal eluenc volume
(or Clma) from che injection points. Choose a "dump
clme" which allows >_ 852 removal of che corn oil and
£ 85Z recovery of che bls(2-ethylhexyl)-phchalace.
Choose Che "collect time" to extend at least 10 minutes
after Che eluCion of pencachlorophenol. Wash the
column at lease 15 mlnuces between samples* Typical
paramecers selected are: Dump time, 30 minuCes (150
mL), collecC clme, 36 minuCes (180 mL), and wash eitne,
15 minuCes (75 mL). The column can also be calibraCed
by the use of a 254 mm UV decector in place of gravi-
metric and GC analyses of fractions. Measure the
peak areas ac various elutlon times to determine
appropriate fracclons.
The SX-3 Bio Beads column may be reused for several
months, even if discoloration occurs. Syscem calibra-
tion usually remains constane over chis period of Clme
if column flowrace remains conscane.
2.6.2 GPC Extract Cleanup
Prefilter or load all extracts via the filter holder to avoid
particulates that might stop the flow. Load one 5.0 mL aliquot
of the excracc onco che GPC column. Oo noc apply excessive
pressure when loading Che GPC. Purge che sample loading tubing
thoroughly with solvent between extracts. After especially
dirty excraccs, run a GPC blank (methylene chloride) Co check
for carry-over. Process che extraccs using che dump, collece,
and wash paramecers determined from the calibration and collect
the cleaned extracts in 400 mL beakers tightly covered with
aluminum foil. The phthalate-phenol calibration solution shall
SV D-21
10/86
-------
II.
be taken through the cleanup cycle with each set of 23 extracts
loaded into the GPC. The recovery for each compound must be
£ 85%. This must be determined on a GC/FID, using a DB-5
capillary column, a UV recording spectrophotometer, or a GC/MS
system. A copy of the printouts of standard and check solution
are required as deliverables with each case. Show X recovery
on the copy.
2.6.3 Concentrate the extract as per paragraphs 2.5.7 and 2.5.8.
Final Concentration of Extract with Optional Extract Splitting
Procedure
If the extract in 2.5.8 is to be used only for seal volatile analysis,
it must be concentrated to a volume of 1.0 ml, following the proce-
dure in 2.7.2*1.
If the extract in 2.5.8 is to be used for both semivolatile and pesti-
cide/PCB analyses, then it must be split into two portions. In that
case, follow the procedure in 2.7.1 to obtain the pesticide portion,
and follow that with the procedure in 2.7.2.2 to obtain the semi-
volatile portion.
Refer to Exhibit 0 PEST for specific instructions regarding the
treatment of extracts for pesticide analysis.
2.7.1 If the same extract 13 used for both semivolatile and pesti-
cide/PCB analyses, to split out the pesticide extract, trans-'
fer 0*5 mL of the 10 mL methylene chloride extract from 2.5.3
to a separate concentrator tube. Add 5 mL of hexane and a
silicon carbide boiling chip and mix using vortex mixer.
Attach a two-ball micro-Snyder column. Pre-vet the Snyder
column by adding 0.5 mL of hexane to the top of the column.
Place the K-D apparatus on a hot water bath (80°-90°C).so that
the concentrator tube Is partially immersed in the hot water.
Adjust the vertical position of the apparatus and the water
temperature as required to complete the concentration in 5
to 10 minutes. Concentrate the extract to an apparent volume
of less than 1 mL. Use Nitrogen blowdown (see 2.7.3) to
reduce the volume to 0.5 mL. Add 0.5 mL of acetone. The
pesticide extract must now be passed through an alumina
column to remove the BNA surrogates and polar interferences.
Proceed to paragraph 2.8 of the pesticide/PCB method
(Exhibit D PEST).
2.7.2 Concentration of the semivolatile extract.
2.7.2.1 If the extract in 2.5.8 was not split to obtain a
portion for pesticide analysis, reattach the micro-
Snyder column to the concentrator tube used in 2.5.8
which contains the 10 mL'extract and add a fresh
silicon carbide boiling chip to the concentrator
tube. Pre-wet the Snyder column with 0.5 mL of
SV D-22
10/86
-------
II. c
methylene chloride. Place Che K-D apparatus on che
hot water bath (80°-90°C) so that the concentrator
tube Is partially Immersed In the hot water. Adjust
the vertical position of the apparatus and the water
temperature as required to complete Che concentration
in 5 to 10 minutes. When the apparent volume of the
liquid reaches 0.5 mL, remove the K-D apparatus from
the water bath and allow it to drain for at least 10
minutes while cooling. Remove the Snyder column and
rinse the lower joint into the concentrator tube with
0.2 mL of methylene chloride. Adjust the final
volume to 1.0 mL with methylene chloride. If GPC
cleanup was used, this 1.0 mL represents a twofold
dilution to account for only half of the extract going
through the GPC.
2.7.2.2 If the extract in 2.5.8 was split in 2.7.1 to
obtain a portion for pesticide analysis, reattach
the mlcro-Snyder column to the concentrator tube used
In 2.5.8 which contains the 9.5 mL extract and add a
fresh silicon carbide boiling chip to the concentrator
tube. Pre-wet the Snyder column with 0.5 mL of methylene
chloride. Place the K-D apparatus on the hot water
bath (80#-90"C) so that the concentrator tube in
partially immersed In the hot water. Adjust the
vertical position of the apparatus and the water
temperatjire as required to complete the concentration
in 5 to 10 minutes. When the apparent volume of the
liquid reaches 0.5 mL, remove the K-D apparatus from
the water bath and allow it to drain drain for at
least 10 minutes while cooling. Remove the Snyder
column and rinse the lower joint into the concentrator
tube with 0.2 mL of methylene chloride. Adjust the
final volume to 0.95 mL with methylene chloride. If
GPC cleanup was used, this 0.95 mL represents a
twofold dilution to account for only half of the
extract going through the GPC.
2.7.3 Nitrogen blowdown technique (taken from ASTM Method 0 3086).
The following method may be used for final concentration of
the BNA extract instead of the procedures in paragraph
2.7.2. Place the concentrator tube in a warm water bath
(35SC) and evaporate the solvent volume to below 1 mL using
a gentle stream of clean, dry nitrogen (filtered through a
column of activated carbon). Caution: New plastic tubing
must not be used between the carbon trap and the sample,
since it may Introduce interferences.
The internal wall of the tube must be rinsed down several
times with methylene chloride during the operation. During
evaporation, the tube solvent level must be kept below the
water level of the bath. The extract must never be allowed
to become dry.
SV D-23
10/86
-------
II. c
If Che excracc in 2.5.8 was not split for boCh semivolatile
and pesticide analyses, bring Che final volume of Che extracc
Co 1.0 nL wich methylene chloride. This represencs a ten-fold
concentration. If che excracc in 2.5.8 was split in 2.7.1,
then bring che final volume of che semivolacile porcion to
0.95 mL wich methylene chloride. This represencs a similar
ten-fold concentration. In either case, if GPC cleanup
Cechniques were employed, che final volume (1.0 or 0.95 mL)
represencs a Cwo-fold dilution to account for the fact that
only half Che extracc wenc through the GPC.
2.7.4 Store all extracts at 4®C (+2®C) in che dark in Teflon-sealed
containers uncil all analyses are performed.
SV D-24
10/86
-------
SECTION III
SCREENING OF SEMIVOLATILE
ORGANIC EXTRACTS
SV D-25
10/86
-------
III.
1. Summary of MeChod
1.1 The solvent extracts of water and sediment/soil are screened on a
gas chromatograph/flame ionization detector (GC/FID) using a fused
silica capillary column (FSCC). The results of the screen will deter-
mine the concentration of extract taken for GC/MS analysis.
2. Apparatus and Materials
2.1 Gas chromatograph - An analytical system complete with a temperature
programmable gas chromatograph and all required accessories including
syringes, analytical columns, and gases. The injection port must be
designed for on-column injection when using packed columns and for
splitless injection when using capillary columns.
2.1.1 Above GC equipped with flame ionization detector.
2.1.2 GC column - 30 it x 0.32 mm, 1 micron film thickness, silicone
coated, fused silica capillary column (J & W Scientific DB-5
or equivalent).
3. Reagents
3.1 Methylene chloride - pesticide residue analysis grade or equivalent.
3.2 GC calibration standard. Prepare a standard solution containing
phenol, phenanthrene, and dl-n-octylphthalate.
3.2.1 Stock standard solutions (1.00 ug/uL)-Stock standard solutions
can be prepared from pure standard materials or purchased
solutions.
3.2.1.1 Prepare stock standard solutions by accurately
weighing about 0.0100 g of pure material. Dissolve
the material in pesticide quality methylene chloride
and dilute to volume in a 10 mL volumetric flask.
Larger volumes may be used at the convenience of the
analyst. If compound purity is assayed at 96% or
greater, the weight may be used without correction
to calculate the concentration of the stock standard.
Commercially prepared stock standards may be used at
any concentration if they are certified by the
manufacturer or by an independent source and are
traceable to EMSL/LV-supplied standards.
3.2.1.2 Transfer the stock standard solutions into Teflon-
sealed screw-cap bottles. Store at -10°C to -208C
and protect from light. Stock standard solutions
should be checked frequently for signs of degradation
or evaporation, especially just prior to preparing
calibration standards from them. Stock standard
SV 0-26
10/86
-------
III.
solutions muse be replaced after six months or sooner
If comparison with quality control check samples
Indicates a problem* Standards prepared from gases
or reactive compounds such as styrene must be replaced
after two months, or sooner if comparison with quality
control check samples indicates a problem.
3.2.2 Prepare a working standard mixture of the three compounds in
methylene chloride. The concentration must be such that the
volume injected equals 50 ng of each compound. The storage and
stability requirements are the same as specified in 3.2.1.2.
GC Calibration
4.1 At the beginning of each 12 hour shift, inject the GC calibration
standard. The following criteria must be:
4.1.1 Standardized for half scale response from SO ng of phenan-
threne.
4.1.2 Adequately separates phenol from the solvent front.
4.1.3 Minimum of quarter scale response for 50 ng of di-n-octylph-
thalate.
GC/FID Screening
5.1 Suggested GC operating conditions:
Initial Column Temperature Hold - 50°C for 4 minutes
Column Temperature Program - 50 - 280*C at 8 degrees/min.
Final Column Temperature Hold - 280°C for 8 minutes
Injector - Grob-type, splitless
Sample Volume - 1 uL - 2 uL
Carrier Gas - Helium at 30 cm^/sec
5.2 Inject the GC calibration standard and ensure the criteria specified in
4. are met before injecting samples. Estimate the response for 10 ng
of phenanthrene.
5.3 Inject the appropriate extracts from Section II, including blanks.
Interpretation of Chromatograms
6.1 Water
6.1.1 If no sample peaks are detected, or all are less than
full scale deflection, the undiluted extract is
analyzed on GC/MS.
SV 0-27
10/86
-------
6.1.2 If any sample peaks are greater chan full scale deflec-
tion, calculate the dilution necessary to reduce the major
peaks to between half and full scale deflection. Use this
dilution factor to dilute the extract for GC/MS analysis.
6.2 Soil/Sediment
6.2.1 If no sample peaks from the extract (from low or medium level
preparation) are detected, or all are less than 10% full scale
deflection, the sample must be prepared by the low level proto-
col, Section II, Part C, paragraph 2.
6.2.2 Peak3 are detected at greater than 10% full scale deflection
and less than or equal to full scale deflection.
6.2.2.1 If the screen is from the medium level extract,
proceed with GC/MS analysis of this extract with
appropriate dilution if necessary.
6.2.2.2 If screen Is from the low level extract, discard
extract and prepare sample by medium level method
for GC/MS analysis.
6.2.3 Peaks are detected at greater than full scale deflection:
6.2.3.1 If the screen is from the medium level preparation-,
calculate the dilution necessary to reduce the major
peaks to between half and full scale deflection.
Use this dilution factor to dilute Che extract.
This dilution is analyzed by GC/MS for extractable
organlcs.
6.2.3.2 If the screen is from the low level preparation,
discard the extract and prepare a sample by the
medium level method for GC/MS analysis.
GC/MS Analysis
7.1 Use the information from 6. to perform the GC/MS analysis of extract-*
ables in Section IV, GC/MS Analysis of Semivolatiles, paragraph 1.
SV D-28
10/86
-------
IV.
SECTION IV
GC/MS ANALYSIS OF SEMIVOLATILES
SV D-29
10/86
-------
IV.
1. Summary of Method
This method is Co be used for Che GC/MS analysis of semivolatiles screened
by Section III protocols and for confirmation of pesticides/PCBs identified
by GC/EC, if concentrations permit.
2. Apparatus and Materials
2.1 Gas chromatograph/mass spectrometer system.
2.1.1 Gas chromatograph - An analytical system complete with
a temperature programmable gas chromatograph suitable
for splitless injection and all required accessories
including syringes, analytical columns, and gases.
2.1.2 Column - 30 m x 0.25 mm 10 (or 0.32 mm) bonded-phase
silicone coated fused silica capillary column (J&W
Scientific DB-5 or equivalent). A film thickness
of 1.0 micron is recommended because of its larger
capacity. A film thickness of 0.25 micron may be used.
2.1.3 Mass Spectrometer - Capable of scanning from 35 to 500
amu every 1 second or less, utilizing 70 volts (nominal)
electron energy in the electron impact ionization mode
and producing a mass spectrum which meets all required
criteria when 50 ng of decafluorotriphenylphosphine
(DFTPP) is injected through the GC inlet.
NOTE: DFTPP criteria must be met before any sample
extracts are analyzed. Any samples analyzed when
DFTPP criteria have not been met will require
reanalysis at no cost to the Government.
2.1.4 Data system - A computer system must be interfaced
to the mass spectrometer that allows the continuous
acquisition and storage on machine readable media
of all mass spectra obtained throughout the duration
of the chromatographic program. The computer must
have software that allows searching any GC/MS data
file for ions of a specific mass and plotting such
ion abundances versus time or scan number. This
type of plot is defined as an Extracted Ion Current
Profile (EICP). Software must also be available that
allows integrating the abundance in any EICP between
specified time or scan number limits.
3. Reagents
3.1 Internal standards - 1,4 dichlorobenzene-d4, naphthalene-dg,
acenaphthene-dio> phenanthrene-djo> chrysene-di2» perylene-di2«
An internal standard solution can be prepared by dissolving
SV D-30
10/86
-------
IV.
200 mg of each compound in SO raL of methylene chloride. It may be
necessary to use 5 to 10 percent benzene or toluene In this solution
and a few minutes of ultrasonic mixing in order to dissolve all the
constituents. The resulting solution will contain each standard at
a concentration of 4000 ng/uL. A 10 uL portion of this solution
should be added to each 1 oL of sample extract. This will give a
concentration of 40 ng/uL of each constituent.
3.2 Prepare calibration standards at a minimum of five concentration
levels. Each calibration standard should contain each compound of
Interest and each surrogate standard. See GC/MS calibration in Exhibit
E for calibration standard concentration.
Great care must be taken to maintain the integrity of all standard
solutions. Store all standard solutions at -10"C to -20®C in screw-cap
amber bottles with teflon liners. Fresh standards should be prepared
every twelve months at a minimum. The continuing calibration standard
should be prepared weekly and stored at 4aC (+2°C).
4. Calibration
4.1 Each GC/MS system must have the hardware tuned to meet the criteria
listed in Exhibit E for a 50 ng injection of decafluorotriphenyl
phosphine (DFTPP). No sample analyses can begin until all these
criteria are met. This criteria must be demonstrated each 12 hour
shift. DFTPP has to be injected to meet this criterion. Post-acquisi-
tion manipulation of abundances is not acceptable.
4.2 The internal standards selected in paragraph 2.3.1 should permit most
components of Interest in a chromatogram to have retention times of
0.80 to 1.20 relative to the internal standards (see instructions, for
Form VI, Initial Calibration Data). Use the base peak ion from the
specific internal standard as the primary ion for quantification, found
in Exhibit E, Table 2.2. If interferences are noted, use the next most
intense ion as the secondary ion, i.e. For l,4-dichlorobenzene-d4 use
m/z 152 for quantification.
4.2.1 The internal standards are added to all calibration standards
and all sample extracts just prior to analysis by GC/MS. A 10
uL aliquot of the Internal standard solution should be added to
a 1 oL aliquot of calibration standards.
4.3 Analyse 1 uL of each calibration standard and tabulate the area of the
primary characteristic ion against concentration for each compound in-
cluding the surrogate compounds. Calculate relative response factors
(RRF) for each compound using Equation 1.
RRF ¦ ^ x Cl9 Equation 1.
Sis ^T
SV D-31
10/86
-------
IV
tfhere:
Ax » Area of Che characteristic ion for Che compound to be measured.
Ais « Area of the characteristic ion for the specific internal standard
from Exhibit E.
C^g ¦ Concentration of the internal standard (ng/uL).
Cg ¦ Concentration of the compound to be measured (ng/uL).
4.3.1 The average relative response factor (RRF) should be calculated
for all compounds. A system performance check oust be made
before this calibration curve is used. Four compounds (the
system performance check compounds) are checked for a minimum
average relative response factor. These compounds (the SPCC)
are N-nitroso-di-n-propylamine, hexachlorocyclopentadiene,
2,4-dinitrophenol, 4-nitrophenol. See instructions in Exhibit E
for Form VI, Initial Calibration Data for more details.
4.3.2 A % Relative Standard Deviation (%RSD) is calculated for eleven
compounds labeled the Calibration Check Compounds (CCC) on Form
VI SV and in Table 2.3, Exhibit E, III SV. A maximum Z RSD is
also specified for these compounds. These criteria must be met
for the calibration curve to be valid.
4.4 A check of the calibration curve must be performed once every 12 hours,
during analysis. These criteria are described in detail in the instruc-
tions for Form VII, Calibration Check. The minimum relative response
factor for the system performance check compounds must be checked. If
this criteria is met, the relative response factors of all compounds are
calculated. A percent difference of Che dally (12 hour) relative
response factor compared to the average relative response factor from
the initial curve is calculated. A maximum percent difference is
allowed for each compound flagged as 'CCC* on Form VII. Only after
both these criteria are met can sample analysis begin.
4.5 Internal standard responses and retention times in all standards oust
be evaluated during or immediately after data acquisition. If the re-
tention time for any Internal standard changes by more than 30 seconds
from the latest daily (12 hour) calibration standard, the chromatographic
system must be inspected for malfunctions, and corrections made as
required. The extracted ion current profile (EICP) of the internal
standards must be monitored and evaluated for each standard. If ECIP
area for any internal standard changes by more than a factor of two
(-50% to +100%), the mass spectroraetric system must be inspected for
malfunction and corrections made as appropriate. When corrections
are made, reanalysis of samples analyzed while the system was mal-
functioning is necessary.
SV D-32
10/86
-------
IV.
GC/MS Analysis
5.1 The following instrumental parameters are required for all performance
tests and for all sample analyses:
Electron Energy - 70 volts (nominal)
Mass Range - 35 to 500' amu
Scan Time - not to exceed 1 second per scan
5.2 Combine 0.5 mL of the base/neutral extract and 0.5 mL of acid from the
water extract prior to analysis.
5.3 Internal standard solution is added to each sample extract. For water
and/or medium soil extracts, add 10 uL of internal standard solution to
each accurately measured 1.0 mL of sample extract* If the low soil
extracts required a pesticide split (see Section II, Part C, paragraph
2.7), add 8 uL of internal standard solution to each accurately measured
0.8 mL of sample extract.
Analyze the 1.0 mL extract by GC/MS using a bonded-phase si11cone-coated
fused silica capillary column. The recommended GC operating conditions
to be used are aa follows:
Initial Column Temperature Hold
Column Temperature Program
Final Column Temperature Hold
Injector Temperature
Transfer Line Temperature
Source Temperature
Injector-Grob-type, splitless
Sample Volume
Carrier Gas
- 40aC for 4 minutes
- 40-270°C at 10 degrees/min.
- 270°C for 10 minutes
- 250-300°C
- 250-300°C
- according to manufacturer's
specifications
- 1 - 2 uL
- Helium at 30 cm^/sec
NOTE: Make any extract dilution indicated by characterization prior to
the addition of internal standards. If any further dilutions of water
or soil/sediment extracts are made, additional internal standards must
be added to maintain the required 40 ng/uL of each constituent in the
extract volume. If the concentration of any compound exceeds the
initial calibration range, the extract must be diluted and reanalyzed.
See Exhibit E, Section III, SV, Part 6. Secondary ion quantitation is
only allowed when there are sample Interferences with the primary ion.
If secondary ion quantitation is performed, document the reasons in the
Case Narrative.
Qualitative Analysis
6.1 The compounds listed in the Target Compound List (TCL), Exhibit C,
shall be identified by an analyst competent In the interpretation
SV 0-33
10/86
-------
IV.
of mass spectra (see PreAward Bid Confirmation description) by
comparison of the sample mass spectrum to the mass spectrum of a
standard of the suspected compound* Two criteria must be satisfied
to verify the identifications: (1) elution of the sample component
at the GC relative retention time as the standard component, and
(2) correspondence of the sample component and standard component
mass spectra.
6.1.1 For establishing correspondence of the GC relative retention
time (RRT), the sample component RRT must compare within
+ 0.06 RRT units of the RRT of the standard component. For
reference, the standard must be run on the same shift as the
sample. If coelution of interfering components prohibits
accurate assignment of the sample component RRT from the
total ion chromatogram, the RRT should be assigned by using
extracted ion current profiles for ions unique to the component
of Interest.
6.1.2 For comparison of standard and sample component mass spectra,
mass spectra obtained on the contractor's GC/MS are required.
Once obtained, these standard spectra may be used for identifi-
cation purposes, only if the contractor's GC/MS meets the DFTPP
daily tuning requirements. These standard spectra may be
obtained from the run used to obtain reference RRTs.
6.1.3 The requirements for qualitative verification by comparison of
mass spectra are as follows:
6.1.3.1 All ions present in the standard mass spectra at a
relative Intensity greater than 10% (most abundant
ion In the spectrum equals 100%) must be present
in the sample spectrum.
6.1.3.2 The relative intensities of ions specified in (1) must
agree within plus or minus 207. between the standard
and sample spectra. (Example: For an ion with an
abundance of 50% in the standard spectra, the corre-
sponding sample ion abundance must be between 30 and
70 percent.)
6.1.3.3 Ions greater than 10% in the sample spectrum but not
present in the standard spectrum must be considered
and accounted for by the analyst making the comparison.
In Task III, the verification process should favor
false positives. All compounds meeting the identi-
fication criteria must be reported with their spectra.
For all compounds below the CRQL report the actual
value followed by "J", e.g. "3J."
SV D-34
10/86
-------
IV.
6.1.4 if a compound cannoc be verified by all of the criteria in
6.1.3, but in the technical judgement of the mass spectral
interpretation specialist, the identification is correct, then
the Contractor shall report that identification and proceed
with quantification in 7.
6.2 A library search shall be executed for non-TCL sample components for
the purpose of tentative identification. For this purpose, the 1985
release of the National Bureau of Standards Mass Spectral Library (or
more recent release), containing 42,261 spectra, shall be used.
6.2.1 Up to 20 nonsurrogate organic compounds of greatest apparent
concentration not listed in Exhibit C for the combined base/
neutral/acid fraction shall be tentatively identified via a
forward search of the NBS mass spectral library. (Substances
with responses less than 10% of the nearest internal standard
are not required to be searched in this fashion). Only after
visual comparison of sample spectra with the nearest library
searches will the mass spectral interpretation specialist
assign a tentative identification. NOTE: Computer generated
library search routines must not use normalization routines
that would misrepresent the library or unknown spectra when
compared to each other.
6.2.2 Guidelines for making tentative identification:
6.2.2.1 Relative intensities of major ions in the reference
spectrum (ions greater than 10% of the most abundant
ion) should be present in the sample spectrum.
6.2.2.2 The relative intensities of the major ions should
agree within + 20%. (Example: For an ion with an
abundance of 50% in the standard spectra, the corre-
sponding sample ion abundance must be between 30 and
70 percent.
6.2.2.3 Molecular ions present in reference spectrum should
be present in sample spectrum.
6.2.2.4 Ions present in the sample spectrum but not in the re-
ference spectrum should be reviewed for possible back-
ground contamination or presence of co-eluting compounds.
6.2.2.5 Ions present in the reference spectrum but not in the
sample spectrum should be reviewed for possible sub-
traction from the sample spectrum because of back-
ground contamination or coeluting compounds. NOTE:
Data system library reduction programs can sometimes
create these discrepancies.
SV D-35
10/86
-------
IV
6.2.3 If In Che technical judgement of Che mass interpretation spec-
tral specialist, no valid tentative identification can be made,
Che compound should be reporced as unknown. The mass spectral
specialise should give addicional classification of the unknown
compound, If possible (i.e., unknown phchalace, unknown hydro-
carbon, unknown acid cype, unknown chlorlnaced compound). If
probable molecular welghcs can be distinguished, include them.
7. Quantitation
7.1 TCL components identified shall be quantified by the Internal standard
method. The internal standard used shall be Che one nearest the reten-
tion time to chat of a given analyte (see Exhlblc E, Tables 2.1 and 2.2).
The EIC? area of characteristic Ions of analytes lisced in Tables 4,
5 and 6 are used.
Incernal standard responses and recencion cimes in all samples muse be
evaluaeed during or immediacely after data acquisition. If ehe recencion
time for any internal standard changes by more than 30 seconds from the
latest daily (12 hour) calibration standard, the chromatographic system
must be inspected for malfunctions, and corrections made as required.
The extracted ion current profile (EIC?) of the internal standards muse
be monitored and evaluated for each sample, blank, matrix spike, and
matrix spike duplicate. The criteria are described An detail in the
instructions for Form VIII, Internal Standard Area Summary. If the EICP
area for any internal standard changes by more than a factor of two
(-50Z co +100Z), che mass spectrometric system muse be inspected for
malfunction and corrections made as appropriate. When corrections are
made, re-analysis of samples analyzed while the system was malfunctioning
is necessary.
7.1.1 If after re-analysis, the EICP areas for all internal standards
are inside che concract limits (-50Z co +100%), then the problem
with the first analysis is considered to have been within the
control of the laboratory. Therefore, only submit data from the
analysis with EICP's within the contract limits. This is con-
sidered the initial analysis and must be reported as such on all
data deliverables.
7.1.2 If che re-analysis of che sample does noc solve ehe problem,
I.e., Che EIC? areas are oueside che contract limits for both
analyses, then submit the EICP data and sample data from both
analyses. Distinguish between the initial analysis and the
re-analysis on all data deliverables, using the sample suffixes
specified in Exhibit B. Document in the Case Narrative all
inspection and corrective actions taken.
SV D-36
10/86
-------
The relative response factor (RRF) from the dally standard analysis
is used to calculate the concentration in the sample. Secondary ions
may be used if interferences are present. The area of a secondary
ion cannot be substituted for the area of a primary ion unless a
relative response factor is calculated using the secondary ion. When
TCL Compounds are below contract required quantitation limits (CRQL)
but the spectra meets the identification criteria, report the concen-
tration with a "J." For example, if CRQL is 10 ug/L and concentration
of 3 ug/L is calculated, report as "3J."
7.2.1 Calculate the concentration in the sample using the relative
reponse factor (RRF) as determined in paragraph 4.3 and the
following equation:
Water
(Ax)(I3)(Vt)
Concentration ug/L « (A^g)(RRF)(V0)(V^)
0% » Area of the characteristic ion for the compound
to be measured
A^s - Area of the characteristic ion for the internal
standard
I3 - Amount of internal standard injected in nanograms
(ng)
V0 - Volume of water extracted in milliliters (mL)
- Volume of extract injected (uL)
Vc ¦ Volume of total extract
(Use 2000 uL or a factor of this when dilutions
are made. The 2,000 uL is derived from com-
bining half of the 1 mL BN extract and half
of the 1 mL A extract.)
SV D-37
10/86
-------
IV.
Soil/Sediment
Concentration ug/kg
(Dry weight basis)
Where:
" (A^XIoKVf)
(Ais)(RRF)(Vi)(Ws)(D)
Ax,IslAis ¦ Same as given for water, above
Vg » Volume of low level total extract
(Use 1000 uL or a factor of this
when dilutions are made. If G?C
cleanup is used, the volume is
2,000 uL. The 1000 uL is derived
from concentrating the 8 mL extract
to 0.8 mL.)
-or - Vc ¦ Volume of medium level extract
(Use 2,000 uL or a factor of this
when dilutions are made. The 2,000
uL is derived from concentrating 5
mL of the 10 mL extract to 1 mL.)
» Volume of extract injected (uL)
D - 100 - % moisture
100
V4 - Weight of sample extracted (grams)
7.3 An estimated concentration for Non-TCL components tentatively identi-
fied shall be quantified by the internal standard method. For quanti-
fication, the nearest internal standard free of interferences shall
be used.
7.3.1 The formula for calculating concentrations is the same as in
paragraph 7.2.1. Total area counts (or peak heights) from
the total ion chromatograms are to be used for both the
compound to be measured and the internal standard. A relative
response factor (RRF) of one (1) is to be assumed. The value
from this quantitation shall be qualified as estimated. This
estimated concentration should be calculated for all tentatively
Identified compounds as well as those identified as unknowns.
7.4 Calculate surrogate standard recovery on all samples, blanks and spikes.
Determine if recovery is within limits and report on appropriate form.
7.4.1 If recovery is not within limits (i.e., if two surrogates
from either base/neutral or acid fractions are out of limits
or if recovery of any one surrogate in either fraction is
below 102), the following is required.
SV D-38
10/86
-------
IV.
o Check Co be sure Chere are no errors In calculations,
surrogate solutions and Internal standards. Also, check
Instrument performance.
o Reanalyze the sample If none of the above reveal a problem.
7.4.2 If the reanalysis of the sample solves the problem, then
the problem was within Che laboratory's control. Therefore,
only submit data from the analysis vith surrogate spike
recoveries within the contract windows. This shall be
considered the initial analysis and shall be reported as
such on all data deliverables.
7.4.3 If none of the steps in 7.4.1 or 7.4.2 solve the problem,
then reextract and reanalyze Che sample. If Che reexcraction
and reanalysis of the sample solves the problem, then the
problem was within the laboratory's control. Therefore,
only submit data from the analysis with surrogate spike
recoveries within the contract windows. This shall be
considered the Initial analysis and shall be reported as
such on all data deliverables.
7.4.4 If the reextraction and reanalysis of of the sample does
not solve the problem, i.e., the surrogate recoveries are
outside the contract limits for both analyses, then submit
the surrogate spike recovery data and Che sample analysis .
data from analysis of both sample extracts. Distinguish
between the initial analysis and the reanalysis on.all data
deliverables, using the sample suffixes specified in Exhibit
3.
7.4.5 If the sample with surrogate recoveries outside the limits-
is the sample used for the matrix spike and matrix spike
duplicate and the surrogate recoveries of the matrix spike
and matrix spike duplicate show the same pattern (i.e.,
outside the limits),.then the sample, matrix spike, and
matrix spike duplicate do not require re-analysis.
Document in the narrative the slmiliarity in surrogate
recoveries.
SV D-39
10/86
-------
Table 4.
Characteristic Ions for Semivolatile TCL Compounds
Parameter
Primary Ion
Secondary Ion(s)
Phenol
94
65, 66
bis(-2-Chloroethyl)Echer
93
63, 95
2-Chlorophenol
128
64, 130
1,3-Dichlorobenz ene
146
148, 113
1,4-Di chlorobenz ene
146
148, 113
Benzyl Alcohol
108
79, 77
1,2-Dichlorobenz ene
146
148, 113
2-Methylphenol
108
107
bis(2-chloroisopropyl)Ether
45
o\
N
*
K
4-Methylphenol
108
107
N-Ni troso-Di-Propylamine
70
42, 101, 130
Hexachloroethane
117
201, 199
Nitrobenzene
77
123, 65
Isophorone
82
95, 138
2-Nitrophenol
139
65, 109
2,4-Dimethylphenol
107
121, 122
Benzoic Acid
122
105, 77
bis(-2-Chloroethoxy)Methane
93
95, 123
2,4-Dichlorophenol
162
164, 98
1,2,4-Tri chlorobenz ene
180
182, 145
Naphthalene
128
129, 127
4-Chloroaniline
127
129
Hexachlorobutadiene
225
223, 227
4-Chloro-3-Methylphenol
107
144, 142
2-Methylnaphthalene
142
141
Hexachlorocyclopentadiene
237
235, 272
2,4,6-Trichlorophenol
196
198, 200
2,4,5-Trichlorophenol
196
198, 200
2-Chloronaphthalene
162
164, 127
2-Nitroaniline
65
92, 138
Dimethyl Phthalate
163
194, 164
Acenaphthylene
152
151, 153
3-Nitroaniline
138
108, 92
Acenaphthene
153
152, 154
2,4-Dinitrophenol
184
63, 154
4-Nitrophenol
109
139, 65
Dibenzofuran
168
139
2,4-Dini trotoluene
165
63, 182
2,6-Dinitrotoluene
165
89, 121
Diethylphthalate
149
177, 150
4-Chlorophenyl-phenylather
204
206, 141
(continued)
SV D-40
10/86
-------
Table 4. (continued)
Characteristic Ions for Semivolatile TCL Compounds
Parameter Primary Ion Secondary Ion(s)
Fluorene
166
165,
167
4-Nitroaniline
138
92,
108
4,6-Dinitro-2-Methylphenol
198
182,
77
N-Nitrosodiphenylamine
169
168,
167
4-Bromophenyl-phenylether
248
250,
141
Hexachlorobenz ene
284
142,
249
Pentachlorophenol
266
264,
268
Phenanthrene
178
179,
176
Anthracene
178
179,
176
Di-N-Butylphthalate
149
150,
104
Fluoranthene
202
101,
100
Pyrene
202
101,
100
Butylbenz ylphthalate
149
91,
206
3,3'-Dichlorobenz idine
252
254,
126
Benzo(a)Anthracene
228
229,
226
bis(2-Ethylhexyl)Phthalate
149
167,
279
Chrysene
228
226,
229
Di-N-Octyl Phthalate
149
-
Benz o(b)Fluoranthene
252
253,
125
Benzo(k)Fluoranthene
252
253,
125
Benao(a)Pyrene
252
253,
125
Indeno(1,2,3—cd)Pyrene
276
138,
227
Dibenz(a, h)Anthracene
278
139-,
279
Benzo(g, h, i)Perylene
276
138,
277
SV 0-41
10/86
-------
Table 5.
Characteristic Ions for Pescicldes/PCBs
Parameter
Primary Ion
Secondary Ion(s)
Alpha-BHC
183
181, 109
Beta-BHC
181
183, 109
Delta-BHC
183
181, 109
Gamma-BHC (Lindane)
183
181, 109
Heptachlor
100
272, 274
Aldrin
66
263, 220
Heptachlor Epoxide
353
355, 351
Endosulfan I
195
339, 341
Dieldrin
79
263, 279
4,4'-DDE
246
248, 176
Endrln
263
82, 81
Endosulfan II
337
339, 341
4,4'-DDD
235
237, 165
Endosulfan Sulfate
272
387, 422
4,4'-DDT
235
237, 165
Methoxychlor
227
228
Chlordane (alpha and/or gamma)
373
375, 377
Toxaphene
159
231, 233
Arochlor-1016
222
260, 292
Arochlor-1221
190
222, 260
Arochlor-1232
190
222, 260
Arochlor-1242
222
256, 292
Arochlor-1248
292
362, 326
Arochlor-1254
292
362, 326
Arochlor-1260
360
362, 394
Endrin Ketone
317
67, 319
Table 6.
Characteristic Ions for Surrogates and
Internal Standards for Semivolatile Compounds
SURROGATES Primary Ion Secondary Ion(s)
Phenol-d5 99 42, 71
2-Fluorophenol 112 64
2,4,6-Tribroraophenol 330 332, 141
d-5 Nitrobenzene 82 128, 54
2-Fluorobiphenyl 172 171
Terphenyl 244 122, 212
INTERNAL STANDARDS
1,4-Dichlorobenzene-d4 152 115
Naphthalene-ds 136 68
Acenapthene-d^o 162, 160
Phenanthrene-d^o
Chrysene-di2
Perylene-di2
240 120, 236
264 260, 265
-------
EXHIBIT D
ANALYTICAL METHODS
FOR PESTICIDES/PCBs
-------
TABLE OF CONTENTS
SECTION I - INTRODUCTION D-2
SECTION II - SAMPLE PREPARATION AND STORAGE D-4
PART A - SAMPLE STORAGE AND HOLDING TIMES D-5
PART B - SAMPLE PREPARATION FOR PESTICIDES/PCBs IN WATER D-6
PART C - PROTOCOLS FOR SOIL/SEDIMENT D-12
1* Medium Level Preparation for Analysis of
Pesticide/PCBs D-12
2. Low Level Preparation for Analysis of
Pescidde/PCBs D-16
SECTION III - SCREENING OF PESTICIDE/PCB EXTRACTS D-28
SECTION IV - GC/EC ANALYSIS OF PESTICIDES/PCBs D-30
PEST D-l
10/86
-------
SECTION I
INTRODUCTION
The analytical methods that follow are designed to analyze water, soil and
sediment from hazardous waste sites for the organic compounds on the Target
Compound List (TCL) (See Exhibit C). The methods are based on EPA Method
608 (Pesticides and PCBs).
The methods are divided into the following sections: sample preparation,
screening and analysis. Sample preparation covers sample extraction and
cleanup techniques. As described in the screening section, a portion of
the extracts may be screened on a gas chromatograph with appropriate detector
to determine the concentration level of pesticldes/PCBs. The analysis section
contains the gas chromatograph/electron capture detector (6C/EC) method for
pesticides and PCBs.
PEST D-2
10/86
-------
Method for the Determination of Pesticides
1*1 Scope and Application
This method covers the determination of certain TCL organochlorlde
pesticides and polychlorinated biphenyls as listed in Exhibit C. The
contract required quantitation limits are also listed in Exhibit C.
Problems have been associated with the following compounds covered by
this method. Alpha-BHC, gamma-BHC, Endosulfan I and II, and Endrln
are subject to decomposition under alkaline conditions.
Because weathering and/or different formulations of chlordane usually
modify the chromatographic pattern exhibited by technical chlordane,
the use of this method is not appropriate for the determination of
technical chlordanne.
The analysis of the isomers alpha chlordane and gamma chlordane by this
method is. appropriate however.
1.2 The method involves solvent extraction of the matrix, analysis of the
extract on a gas chromatograph/electron capture detector (GC/EC) using
a packed column, and quantitation and confirmation on a GC/EC using a
second packed column. (An optional fused silica capillary column may be
used for confirmation.) If concentration permits, confirmation is to be
done on GC/MS.
PEST 0-3
10/86
-------
SECTION II
SAMPLE PREPARATION AND STORAGE
PEST D-4
-------
II. A
PART A - SAMPLE STORAGE AND HOLDING TIMES
1. Procedures for Sample Storage
1.1 The samples must be protected from light and refrigerated at 4°C (+2°C)
from the time of receipt until extraction and analysis.
2. Contract Required Holding Times
2.1 If separatory funnel procedures are employed for extractions for pesticide/
PCB analyses, extraction of water samples shall be completed within 5
days of VTSR (Validated Time of Sample Receipt), and extraction of soil/
sediment samples shall be completed within 10 days of VTSR. If continuous
liquid-liquid extraction procedures are employed, extraction of water
samples shall be started within 5 days of VTSR, and extraction of soil/
sediment samples shall be started within 10 days of VTSR.
2.2 Extracts of either water or soil/sediment samples must be analyzed
within 40 days of VTSR (Validated Time of Sample Receipt).
PEST D-5
10/86
-------
II. B
PART B - SflfUrUi. fUSfAKAX1UM FUR PESTICIDES/PCBS IN WATER
Summary of Method
A measured volume of sample, approximately one-licer, is solvent extracted
with methylene chloride using a separatory funnel or a continuous extractor.
The methylene chloride extract is dried, exchanged to hexane, and adjusted to
a final volume of 10 oL. The extract for pesticide/PCB analysis may be
prepared from an aliquot of the extract for semivolatiles, or in a separate
extraction procedure. If it is prepared from the semivolatile extract,
refer to Exhibit 0 SV for the procedures for extraction of semivolatiles.
Interferences
2.1 Method interferences may be caused by contaminants in solvents, reagents,
glassware, and other sample processing hardware that lead to discrete
artifacts and/or elevated baselines in gas chroraatograms. All of
these materials must be routinely demonstrated to be free from inter-
ferences under the conditions of the analysis by running laboratory
reagent blanks. Interferences by phthalate esters can pose a major
problem in pesticide analysis when using the electron capture detector.
These compounds generally appear in the chromatogram as broad eluting
peaks. Common flexible plastics contain varying amounts of phthalates.
These phthalates are easily extracted or leached from such materials
during laboratory operations. Crosscontamination of clean glassware
routinely occurs when plastics are handled. Interferences from phthalates
can best be minimized by avoiding the use of plastics in the laboratory.
Exhaustive cleanup of reagents and glassware may be required to eliminate
background phthalate contamination.
2.2 Matrix Interferences may be caused by contaminants that are coextracted
from the sample. The extent of matrix interferences will vary considerably
from source to source, depending upon the nature and diversity of the
site being sampled. The cleanup procedures in paragraphs 7.1 thru 7.5
must be used to overcome such interferences to attempt to achieve the
CRQLs. The cleanup procedures in paragraph 8.1 through 8.5 may be
used to remove sulfur Interferences.
Apparatus and Materials
3.1 Glassware (Brand names and catalog numbers included for illustration
purposes only).
3.1.1 Separatory funnel - 2000 mL with Teflon stopcock.
3.1.2 Drying column - Chromatographic column approximately 400 mm
long x 19 mm ID, with coarse frit. (Substitution of a small
pad of disposable Pyrex glass wool for the frit will help
prevent cross-contamination of sample extracts.)
PEST D-6
10/86
-------
II.B
3.1.3 Coacencraeor Cube - Kuderna-Danish, 10 mL, graduated (Konces
K-570050-1025 or equivalent). Calibration oust be checked at the
volumes employed in the test. Ground glass stopper is used to
prevent evaporation of extracts.
3.1.4 Evaporative flask - Kudema-Danish, 500 mL (Kontes K-5700010500
or equivalent). Attach to concentrator tube with springs.
3.1.5 Snyder column - Kudema-Danish, Three-ball macro (Kontes K-503000-
0121 or equivalent).
3.1.6 Snyder column - Kuderna-Danish, Two-ball micro (Kontes K-569001-
0219 or equivalent).
3.1.7 Continuous liquid-liquid extractors - Equipped with Teflon or
glass connecting joints and stopcocks requiring no lubrication.
(Hershberg-Wolf Extractor-Ace Glass Company, Vineland, NJ P/N
6841-10, or equivalent.)
3.1.8 Vials - Amber glass, 10 to 15 mL capacity, with Teflon-lined
screw cap.
3.1.9 Bottle or test tube - 50 mL with Teflon lined 3crew cap for
sulfur removal.
3.1.10 Chromatographic column for alumina - 8 mL (200 aim X 8 mm ID)
Polypropylene column (Kontes K-420160 or equivalent) or 6 mL
(150 mm x 8 mm ID) glass column (Kontes K-420155 or equivalent-),
or 5 mL serological pipettes plugged with a small piece of Pyrex
glass wool in the tip. The Kontes columns may be plugged with
Pyrex glass wool or a polyethylene porous disk (Kontes K-420162).
3.2 Pyrex glass wool - pre-rinse glass wool with appropriate solvents to
ensure its cleanliness.
3.3 Silicon carbide boiling chips - Approximately 10/40 mesh. Heat to
400°C for 30 minutes or Soxhlet extract with methylene chloride.
3.4 Water bath - Heated, with concentric ring cover, capable of temperature
control (+ 2#C). The bath should be used in a hood.
3.5 Balance - Analytical, capable of accurately weighing 0.0001 g.
3.6 Nitrogen evaporation device equipped with a water bath that can be
maintained at 35-40°C. The N-Evap by Organomation Associates,
Inc. South Berlin, MA (or equivalent) is suitable.
4. Reagents
4.1 Reagent water - Reagent water is defined as a water in which an in-
terferent is not observed at or above the CRQL of each parameter of
interest.
PEST D-7
10/86
-------
II. B
4.2 Acecone, hexane, isooctane (2,2,4-triraethylpentane), methylene chloride -
Pesticide quality or equivalent.
4.3 Sodium sulfate - (ACS) granular, anhydrous. Purify by heating at
400°C for 4 hours in a shallow tray.
4.4 Alumina - Neutral, Super I Woelm or equivalent. (Universal Scientific,
Incorporated, Atlanta, Georgia or equivalent.) Prepare activity III by
adding 7% (v/w) reagent water to the Super I neutral alumina. Tumble or
shake in a wrist action shaker for a minimum of 2 hours or preferably
overnight. There should be no lumps present. Store in a tightly sealed
glass container. A 25 cycle soxhlet extraction of the alumina with
methylene chloride is required if a solvent blank analyzed by the pesticide
technique Indicates any interferences for the compounds of interest.
4.4.1 Alumina Equivalency Check. Test the alumina by adding the BNA
surrogates (see Exhibit D SV) in 1:1 acetone/hexane to the alumina
and following paragraph 7.1. The trlbromophenol should not be
detected by GC/EC if the alumina and its activation are acceptable.
Also check recovery of all single component pesticides following
the same procedure. The percent recovery for all single component
pesticides must be >80%, except for endosulfan sulfate which
must be >60% and endrin aldehyde which is not recovered. The
data must be retained by the laboratory and made available for
inspection during on-site evaluations.
4.5 Sodium hydroxide solution (lON)-(ACS). Dissolve 40 g NaOH in reagent
water and dilute to 100 mL.
4.6 Tetrabutylammonium (TBA) - Sulfite reagent. Dissolve 3.39 g tetrabutyl-
ammonlum hydrogen sulfate in 100 mL distilled water. To remove impurities,
extract this solution three times with 20 mL portions of hexane. Discard
the hexane extracts, and add 25 g sodium sulfite to the water solution.
Store the resulting solution, which is saturated with sodium sulfite, in
an amber bottle with a Teflon-lined screw cap. This solution can be
stored at room temperature for at least one month.
4.7 Pesticide surrogate standard spiking solution.
4.7.1 The surrogate standard is added to all samples and calibration
solutions; the compound specified for this purpose is dibutyl-
chlorendate.
4.7.2 Prepare a surrogate standard spiking solution at a concentration
of 1 ug/1.00 mL in acetone* Store the spiking solutions at 49C
(+ 2°C) in Teflon-sealed containers. The solutions should be
checked frequently for stability. These solutions must be replaced
after twelve months, or sooner, If comparison with quality control
check samples indicates a problem.
4.8 Sulfuric acid solution (1+1)-(ACS). Slowly, add 50 aL H2SO4 (sp. gr.
1.84) to 50 mL of reagent water.
PEST D-8
10/86
-------
II. B
4.9 Pesticide matrix standard spiking solution. Prepare a spiking solution
of acetone or methanol that contains the following pesticides in the
concentrations specified.
Pesticide ug/1.0 aL
Lindane 0.2
Heptachlor 0.2
Aldrln 0.2
Dieldrln 0.5
Endrln 0.5
4,4' DDT 0.5
Matrix spikes are also to serve as duplicates by spiking two 1-liter
portions from the one sample chosen for spiking.
4.10 See Exhibit A for a summary of the quality control requirements of this
contract. See Exhibit E for contract-required quality assurance/quality
control procedures.
5. Sample Extraction - Separatory Funnel
5.1 Samples may be extracted using separatory funnel techniques. If emulsions
prevent acceptable solvent recovery with separatory funnel extractions,
continuous liquid-liquid extraction (paragraph 6.1) may be used. The
separatory funnel extraction scheme described below assumes a sample
volume of one liter. NOTE: If the pesticide/PCB extract is prepared
from an aliquot of the semivolatile extract, refer to Exhibit D SV, as
well as these procedures.
5.2 Using a 1-liter graduated cylinder, measure out a 1-liter sample aliquot
and place it into a 2-liter separatory funnel. Pipet 1.0 oL surrogate
standard spiking solution into the separatory funnel and mix well. '
Check the pH of the sample with wide range pH paper and adjust to between
5 and 9 pH with 10N sodium hydroxide and/or 1:1 sulfuric acid solution.
(NOTE: Recovery of dibutylchlorendate will be low if pH is outside this
range.) Add 1.0 mL of pesticide matrix spiking solution to each of two
1-llter portions from the sample selected for spiking.
5.3 Add 60 mL methylene chloride to the separatory funnel and extract the
sample by shaking the funnel for two minutes, with periodic venting to
release excess pressure. Allow the organic layer to separate from the
water phase for a minimum of 10 minutes. If the emulsion interface
between layers is more than one-third the volume of the solvent layer,
the analyst must employ mechanical techniques to complete the phase
separation. The optimum technique depends upon the sample, and may
include: stirring, filtration of the emulsion through glass wool,
centrifugation, or other physical means. Drain methylene chloride into
a 250 mL Erlenmeyer flask.
5.4 Add a second 60 mL volume of methylene chloride to the sample bottle and
repeat the extraction procedure a second time, combining the extracts in
the Erlenmeyer flask. Perform a third extraction in the same manner.
PEST D-9
10/86
-------
II. B
5.5 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-mL concen-
trator tube to a 500-mL evaporative flask. Other concentration devices or
techniques may be used in place of the K-D if equivalency is demonstrated
for all pesticides listed in Exhibit C.
5.6 Pour the combined extract through a drying column containing< about 10 cm
of anhydrous sodium sulfate, and collect the extract in the K-D concen-
trator. Rinse the Erlenmeyer flask and column with 20 to 30 mL of
methylene chloride to complete the quantitative transfer.
5.7 Add one or two clean boiling chips to the evaporative flask and attach a
three-ball Snyder column. Pre-wet the Snyder column by adding about
1 mL methylene chloride to the top. Place the K-D apparatus on a hot
water bath (80 to 90°C) so that the concentrator tube is partially
immersed in the hot water and the entire lower rounded surface of the
flask is bathed with hot vapor. Adjust the vertical position of the
apparatus and the water temperature as required to complete the concen-
tration in 10 to 15 minutes. At the proper rate of distillation, the
balls of the column will actively chatter but the chambers will not
flood with condensed solvent. When the apparent volume of liquid reaches
1 mL, remove the K-D apparatus. Allow it to drain and cool for at least
10 minutes.
5.8 Momentarily remove the Snyder column, add 50 mL of hexane and a new
boiling chip and re-attach the Snyder column. Pre-wet the column by
adding about 1 mL of hexane to the top. Concentrate the solvent extract
as before. The elapsed time of concentration should be 5 to 10 minutes.
When the apparent volume of liquid reaches 1 mL, remove the K-D apparatus
and allow it to drain and cool at least 10 minutes.
5.9 Remove the Snyder column, rinse the flask and its lower joint into the
concentrator tube with 1 to 2 mL of hexane. If sulfur crystals- are a
problem, proceed to paragraph 8.1; otherwise continue to paragraph'
5.10.
5.10 Nitrogen blowdown technique (taken from ASTM Method D 3086)
Place the concentrator tube in a warm water bath (35°C) and evaporate
the solvent volume to 0.5 mL using a gentle stream of clean, dry nitrogen
(filtered through a column of activated carbon). Caution: New plastic
tubing must not be used between the carbon trap and the sample, as it
may introduce interferences. The internal wall of the tube must be
rinsed down several times with hexane during the operation and the final
volume brought to 0.5 mL. During evaporation, the tube solvent level
must be kept below the water level of the bath. The extract must never
be allowed to become dry.
5.11 Dilute the extract to 1 mL with acetone and proceed to 7.1 Alumina
Column Cleanup.
PEST D-10
10/86
-------
II. B
6. Sample Extraction - Continuous Liquid-Liquid Extractor
6.1 When experience with a sample from a given source indicates chat a serious
emulsion problem will result, or if an emulsion is encountered in paragraph
5.3 using a separatory funnel, a continuous extractor should be used.
6.2 Using a 1-liter graduated cylinder, measure out a 1-liter sample aliquot
and place it into Che continuous extractor. Pipet 1.0 mL surrogate stand-
ard spiking solution into the continuous extractor and mix well. Check
Che pH of the sample with wide range pH paper and adjust to between S and
9 pH with ION sodium hydroxide and/or 1:1 sulfuric acid solution.
6.3 Add 500 mL of methylene chloride to the distilling flask. Add sufficient
reagent water to ensure proper operation and extract for 18 hours. Allow
to cool, then detach the boiling flask and dry. Concentrate the extract
as in paragraphs 5.5 through 5.11.
7. Alumina Column Cleanup
7.1 Add 3 g of activity III neutral alumina to the 10-mL chromatographic
column. Tap the column to'settle the alumina. Do not pre-wet the
alumina.
7.2 Transfer the 1 mL of hexane/acetone extract from paragraph 5.11 to Che
top of the alumina using a disposable Pasteur pipet. Collect the eluate
in a clean 10-mL concentrator tube.
7.3 Add 1 mL of hexane to the original extract concentrator tube to rinse it.
Transfer these rinsings to the alumina column. Elute the column with ah
additional 9 mL of hexane. Do not allow the column to go dry during the
addition and elutlon of the sample.
7.4 Adjust the extract to a final volume of 10 mL using hexane.
7.5 The pesticide/?C2 fraction is ready for analysis. Proceed to Section IV,
paragraph 3. Store the extracts at 4°C (+2"C) in the dark in Teflon-
sealed containers until analyses are performed.
8. Optional Sulfur Cleanup
8.1 Concentrate the hexane extract from paragraph 5.9 to 1 mL.
8.2 Transfer the 1 mL to a 50 mL clear glass bottle or vial with a Teflon-lined
screw cap. Rinse the concentrator Cube wlch 1 mL of hexane, adding Che
rinsings Co Che 50 mL bottle.
8.3 Add 1 mL TBA-sulfite reagent and 2 mL 2-propanol, cap the bottle, and
shake for at least 1 min. If the sample is colorless or if the initial
color is unchanged, and If clear crystals (precipated sodium sulfite) are
observed, sufficient sodium sulfite is present. If Che precipicaced sodium
sulfite disappears, add more crystalline sodium sulfice in approximately
100 mg portions uncil a solid residue remains afcer repeated shaking.
PEST 0-11
10/86
-------
II. B
8.4 Add 5 mL distilled water and shake for ae least 1 minute. Allow the
sample to stand 5—10 minutes. Transfer the hexane layer (top) to a
concentrator ampul and go back to paragraph 5.10.
PEST D-12
10/86
-------
II. c
PART C - PROTOCOLS FOR SOIL/SEDIMENT
Ic Is mandatory chac all soil/sediment samples be characterized as co concen-
tration level so that the appropriate analytical protocol may b« chosen to
ensure proper quantitation limits for the sample.
The use of GC/EC methods is recommended for screening soil/sediment samples for
pesticides/PCBs, however, the contractor is at liberty to determine the specific
method of characterization.
Note that the terms "low level" and "medium level" are not used here as a judge-
ment of degree of contamination but rather as a description of the concentration
ranges that are encompassed by the "low" and "medium" level procedures.
The concentration range covered by the low level analysis may be considered to
be less than 1000 ug/kg of pesticides/PCBs. The concentration range covered by
the medium level analysis is greater than 1000 ug/kg.
1. Medium Level Preparation for Analysis of Pesticides/PCBs in Soil/Sediment
1.1 Scope and Application
This procedure is designed for the preparation of sediment/soil samples
which may contain pesticides/PCBs at a level greater than 1,000 ug/kg.
1.1.1 Samples to be prepared and analyzed by this method should have
been screened by GC/EC techniques. The results of those screens
will determine whethher sufficient quantities of pesticides/PCBs
are present to warrant analysis by the medium level protocol.
1.1.2 If the screenings indicate no detectable pollutants at a level of
quantitation of 1000 ug/kg, the sample should be prepared by the
low level protocol in this Section.
1.1.3 If the extract for pesticide/PCB analysis is to be prepared from
an aliquot of the semivolatile extract, also refer to the specific
instructions in Exhibit D SV.
1.2 Summary of Method
1.2.1 Portions of soil/sediment are extracted and screened by methods
of the contractor's choice.
1.2.2 If pesticides/PCBs are detected in the screen at levels above
approximately 1000 ug/kg, a 1 g sample is extracted with 10.0 niL
of hexane for analysis by GC/EC.
1.2.3 If no pesticides/PCBs are detected above 1000 ug/kg, then the
sample shall be prepared by the low level protocol.
1.3 Interferences
1.3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that
lead to discrete artifacts and/or elevated baselines in the
owe* rw i,
>0/86
-------
II. c
total ion current profiles. All of these materials oust be
routinely demonstrated to be free from interferences under the
conditions of the analysis by running laboratory reagent blanks.
Matrix interferences may be caused by contaminants that are
coextracted from the sample. The extent of matrix interferences
will vary considerably from source to source.
1.4 Limitations
1.4.1 The procedure is designed to allow quantitation limits as low as
1000 ug/kg for pesticldes/PCBs. If peaks are present based on GC
screen, the sample is determined to require a medium level analysis
by GC/EC. Some samples may contain high concentrations of chemicals
that interfere with the analysis of other components at lower levels;
the quantitation limits in those cases may be significantly higher.
1.5 Reagents
1.5.1 Sodium Sulfate - anhydrous powdered reagent grade, heated at 400 °C
for four hours, cooled in a desiccator, and stored in a glass bottle
Baker anhydrous powder, catalog # 73898 or equivalent.
1.5.2 Methylene chloride. Pesticide residue analysis grade or equivalent.
1.5.3 Hexane. Pesticide residue analysis grade or equivalent.
1.5.4 Methanol. Pesticide residue analysis grade or equivalent.
1.5.5 Acetone. Pesticide residue analysis grade or equivalent.
1.5.6 Pesticlde/PCB Surrogate Standard Spiking solution.
1.5.6.1 The compound specified is dlbutylchlorendate* Prepare a
solution at a concentration of 20 ug/1.0 mL in methanol.
Store the spiking solutions at 4®C (+2°C) in Teflon-sealed
containers. The solutions should be checked frequently
for stability. These solutions must be replaced after
twelve months, or sooner, if comparison with quality
control check samples indicates a problem.
1.5.7 Pesticlde/PCB Matrix Standard Spiking solution
1.5.7.1 Prepare a spiking solution in methanol that contains the
following pesticides In the concentrations specified
below. Store the spiking solutions at 4°C (+29C) in
Teflon-sealed containers. The solutions should be checked
frequently for stability. These solutions must be replaced
after twelve months, or sooner, if comparison with quality
control check samples indicates a problem.
PEST D-14
10/86
-------
II. c
Pesticide
ug/l.OmL
lindane
heptachlor
aldrin
dleldrln
endrin
4,4' DOT
2.0
2.0
2.0
S.O
5.0
5.0
1.5.8 Alumina - neutral, super I Woelm (Universal Scientific, Atlanta,
GA) or equivalent. Prepare activity III by adding 73! (v/w)
reagent water to the Super I neutral alumina. Tumble or shake
on a vrist action shaker for a minimum of 2 hours or preferably
overnight. There should be no lumps present. Store in a tightly
sealed glass container. A 25 cycle soxhlet extraction of the
alumina with methylene chloride is required if a solvent blank
analyzed by the pesticide techniques indicates any Interferences
for the compounds of interest.
1.5.8.1 Alumina Equivalency Check. Test the alumina by adding the
BNA surrogates (see Exhibit 0 SV) in 1:1 acetone/hexane
to the alumina and following paragraph 2.8.1. The tri-
bromophenol should not be detected by GC/EC if the alumina
and Its activation are acceptable. Also check recovery of
all single component pesticides following the same procedure.
The percent recovery for all single component pesticides
oust be >80%, except for endosulfan sulfate which must be
>602 and endrin aldehyde which is not recovered. The d'ata
must be retained by the laboratory and made available for
inspection during on-site evaluations.
1.5.9 Reagent Water - Reagent water is defined as water in which an
lncerferent is not observed at or above the CRQL of each parameter
of interest.
Equipment
1.6.1 Glass scintillation vials, at least 20 mL, with screw cap and
teflon or aluminum foil liner.
1.6.2 Spatula. Stainless steel or Teflon.
1.6.3 Balance capable of weighing 100 g to the nearest 0.01 g.
1.6.4 Vials and caps, 2 mL for GC auto sampler.
1.6.5 Disposable pipettes, Pasteur; glass wool rinsed with methylene
chloride.
1.6.6 15-mL concentrator tubes.
1.6.7 Ultrasonic cell disruptor, Heat Systems Ultrasonics, Inc., Model
W-375 SONICATOR or equivalent (375 Watt with pulsing capability,
No. 200 1/2 inch tapped disruptor horn, and No. 419 1/8 inch
PEST D-15
10/86
-------
II. c
standard tapered MICROTIP probe). NOTE: In order to ensure that
sufficient energy is transferred to the sample during extraction,
the MICROTIP probe oust be replaced if the dp begins to erode.
Erosion of the tip is evidenced by a rough surface.
1.6.8 Sonabox - recommended with above disruptors for decreasing cavita-
tion sound.
1.6.9 Test tube rack.
1.6.10 Oven, drying
1.6.11 Desiccator
1.6.12 Crucibles, porcelain
1.6.13 Chromatography column for alumina. 8 oL (200 mm & 8 am ID) Poly-
propylene column (Kontes K-420160 or equivalent) or 6 mL (150 mm X
8 mm ID) glass column (Kontes K-420155 or equivalent) or 5 mL
serological pipettes plugged with a small piece of Pyrex glass
wool in the tip. (Pyrex glass wool shall be pre-rinsed with
appropriate solvents to insure its cleanliness). The Kontes
columns may be plugged with Pyrex glass wool or a polyethylene
porous disk (Kontes K-420162).
Sample Preparation
1.7.1 Medium Level prep for analysis of Pesticide/PCBs (Determine results
of GC/EC screen before proceeding.)
1.7.1.1 Transfer the sample container into a fume hood. Open
the sample vial and mix the sample. Transfer approx-
imately 1 g (record weight to nearest 0.1 g) of sample
to a 20 mL vial. Wipe the mouth of the vial with a tissue
to remove any sample material. Record the exact weight
of the sample taken. Cap the vial before proceeding
with the next sample to avoid any cross contamination.
1.7.1.1.1 Transfer 50 g of soil/sediment to 100 ml
beaker. Add 50 ml of water and stir for 1
hour. Determine pH of sample with glass
electrode and pH meter while stirring.
Report pH value on appropriate data sheets.
If the pH of the soil is greater than 11 or
less than 5, contact the Deputy Project
Officer cited in Che contract for instructions
on how to handle the sample. Document the
instructions in the Case Narrative. Discard
this portion of sample. NOTE: Recovery of
dibutylchlorendate will be low if pH is out-
side this range.
PEST D—16
10/86
-------
IX.
1.7.1.2 Add 2 g of anhydrous powdered sodium sulfate Co the
sample and mix veil.
1.7.1.3 Surrogate standards are added to all samples, spikes,
and blanks. Add 50 uL of surrogate spiking solution
to Che sample mixture.
1.7.1.4 Add 1.0 mL of macrix standard spiking solution to each
of two 1 g portions from the sample chosen for spiking.
1.7.1.5 Immediately add lO.OmL (only 9.0 mL for the matrix spike
sample) of hexane to the sample and disrupt the sample
with the 1/8 inch tapered MICR0T1P ultrasonic probe for 2
minutes with output control setting at 5 and mode switch
on "pulse" and % duty cycle set at 502. (If using a sonl-
cator other than Model W-375, refer to the manufacturer's
instructions for appropriate output settings.) Before
extraction, make certain that the sodium sulface is free
flowing and not a consolidated mass. As required, break
up large lumps with a clear spatula, or very carefully
with the tip of the probe.
1.7.1.6 Loosely pack disposable Pasteur pipettes with 2-3 cm
glass wool plugs. Filter the extract through the glass
wool and collect at approximately 5 mL in a concentrator
tube.
1.7.1.7 Transfer 1.0 mL of the hexane extract to a glass con-
centrator tube and concentrate to 0.5 mL using Nitrogen
blowdown. Add 0.5 mL of acetone to 0.5 mL of hexane
extract. Swirl to mix. The pesticide extract must now
be passed through an alumina column to remove polar
Interferences.
1.7.1.8 Follow the procedures for low level soil sediment prepare
ation outlined in paragraphs 2.8.1.1 through 2.8.3.3 for
alumina cleanup and sulfur removal.
Low Level Preparation for Analysis of Pescicides/PCBs in Soil/Sediment
2.1 Summary of Method
2.1.1 If based on the results of a GC/EC screen, no pesticldes/PCSs are
present in the sample above 1000 ug/kg, a 30 gram portion of soil/
sediment is mixed with anhydrous powdered sodium sulfate and
extracted with 1:1 methylene chloride/acetone using an ultrasonic
probe. The extract is concentrated and an optional gel permeation
column cleanup may be used. The extract is cleaned up using a
micro alumina column and analyzed by GC/EC for pesticides.
PEST D-17
10/86
-------
II. c
2.2 Interferences
2.2.1 Method Interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that
lead to discrete artifacts and/or elevated baselines in the total
ion current profiles. All of these materials must be routinely
demonstrated to be free from interferences under the conditions
of the analysis by running laboratory reagent blanks. Matrix
Interferences may be caused by contaminants that are coextracted
from the sample. The extent of matrix interferences will vary
considerably from source to source.
2.3 Apparatus and Materials
2.3.1 Apparatus for determining percent moisture
2.3.1.1 Oven, drying
2.3.1.2 Desiccator
2.3.1.3 Crucibles, porcelain
2.3.2 Disposable Pasteur glass pipettes, 1 mL
2.3t3 Ultrasonic cell disruptor, Heat Systems - Ultrasonics, Inc. Model
W-375 SONICATOR or equivalent (375 watt with pulsing capability,
No. 303 1/4 inch tapped high gain "Q" dlsruptor horn or Model 208
3/4 inch standard tip solid horn). NOTE: In order to ensure
that sufficient energy is transferred to the sample during extraction,
the probe must be replaced if the tip begins to erode. Erosion
of the tip is evidenced by a rough surface.
2.3.4 Beakers, 400 mL
2.3.5 Vacuum filtration apparatus
2.3.5.1 Buchner funnel.
2.3.5.2 Filter paper, Whatman No. 41 or equivalent.
2.3.6 Kuderna-Danish (K-D) apparatus.
2.3.6.1 Concentrator tube - 10 mL, graduated (Kontes K-570040-
1025 or equivalent).
2.3.6.2 Evaporative flask - 500 mL (Kontes K-570001-0500 or
equivalent).
2.3.6.3 Snyder column - three-ball macro (Kontes K-503000-0121
or equivalent).
2.3.6.4 Snyder column - two ball micro (Kontes K-569001-0219)
or equivalent).
PEST D-18
10/86
-------
II. c
2.3.7 Silicon carbide boiling chips - approximately 10/40 mesh. Heac
to 400°C for 30 minutes or Soxhlet extract with methylene chloride.
2.3.8 Water bath - heated, with concentric ring cover, capable of tem-
perature control (+2°C). The bath should be used in a hood.
2.3.9 Balance, capable of accurately weighing + 0.01 g.
2.3.10 Vials and caps, 2 mL for GC auto sampler.
2.3.11 Balance - Analytical, capable of accurately weighing +_ 0.0001 g.
2.3.12 Nitrogen evaporation device equipped with a water bath that can be
maintained at 35-40°C. The N-Evap by Organoraation Associates, Inc.
South Berlin, MA (or equivalent) is suitable.
2.3.13 Gel permeation chromatography (GPC) cleanup device. NOTE: GPC
cleanup is highly recommended for all extracts for low level soils.
2.3.13.1 Automated system
2.3.13.1.1 Gel permeation chromatograph Analytical Bio-
chemical Labs, Inc. GPC Autoprep 1002 or
equivalent including:
2.3.13.1.2 25 mm 10 X 600 - 700 mm glass column packed
with 70 g of Bio^Beads SX-3.
2.3.13.1.3 Syringe, 10 mL with Luer-Lok fitting.
2.3.13.1.4 Syringe filter holder and filters - stainless
steel and TFE, Gelman 4310 or equivalent.
2.3.13.2 Manual system assembled from parts.*
2.3.13.2.1 25 mm ID X 600 - 700 mm heavy wall glass
column packed with 70 g of BIO-Beads SX-3.
2.3.13.2.2 Pump: Altex Scientific, Model No. 1001A,
semipreparative, solvent metering system.
Pump capacity * 28 mL/min.
2.3.13.2.3 Detector: Altex Scientific, Model No. 153,
with 254 nm UV source and 8-ul semi-prepar-
ative flowcells (2-mm pathlengths)
2.3.13.2.4 Microprocessor/controller: Altex Scientific,
Model No. 420, Microprocessor System Con-
troller, with extended memory.
*tfise, R.H., Bishop, D.F., Williams, R.T. & Austern, B.M. "Gel Permeation
Chromatography in the GC/MS Analysis of Organics in Sludges" U.S. EPA,
Municipal Environmental Research Laboratory - Cincinnati, Ohio 45268
PEST D-19 10/86
-------
II. c
2.3.13.2.5 Injector: Altex Scientific, catalog No.
201-56, sample injection valve, Tefzel, with
10 mL sample loop.
2.3.13.2.6 Recorder: Linear Instruments, Model No. 385,
10-inch recorder.
2.3.13.2.7 Effluent Switching Valve: Teflon slider
valve* 3-way with 0.060"* ports.
2.3.13.2.8 Supplemental Pressure Gauge with connecting
Tee: U.S.Gauge, 0-200 psi, stainless steel.
Installed as a "downstream" monitoring device
between column and detector. Flow rate was
typically 5 mL/mln. of methylene chloride.
Recorder chart speed was 0.50 cm/mln.
2.3.14 Chromatography column for alumina. 8 mL (200 mm & 8 mm ID) Poly-
propylene column (Kontes K-420160 or equivalent) or 6 mL (150 mm
X 8 mm ID) glass column (Kontes K-420155 or equivalent) or 5 mL
serological pipettes plugged with a small piece of Pyrex glass wool
in the tip. (Pyrex glass wool shall be pre-rinsed with approp-
riate solvents to insure its cleanliness). The Kontes columns
may be plugged with Pyrex glass wool or a polyethylene porous
disk (Kontes K-420162).
2.3.15 Pyrex glass wool.
2.3.16 Bottle or test tube, 50 mL with Teflon-lined screw cap for sulfur
removal.
2.3.17 Pasteur pipettes, disposable.
2.4 Reagents
2.4.1 Sodium Sulfate - anhydrous powdered reagent grade, heated at 400aC
for four hours, cooled in a desiccator, and stored in a glass
bottle. Baker anhydrous powder, catalog #7.3898 or equivalent.
2.4.2 Methylene chloride, hexane, acetone, isoooctane, 2-propanol and
benzene pesticide quality or equivalent.
2.4.3 Alumina - neutral, super I Woelm (Universal Scientific, Atlanta,
GA) or equivalent. Prepare activity III by adding 7X (v/w) reagent
water to the Super I neutral alumina. Tumble or shake on a wrist
action shaker for a minimum of 2 hours or preferably overnight.
There should be no lumps present. Store in a tightly sealed glass
container. A 25 cycle soxhlet extraction of the alumina with
methylene chloride ta required if a solvent blank analyzed by the
pesticide techniques indicate any interferences for the compounds
of interest.
PEST D-20
10/86
-------
II. c
2.4.3.1 Alumina Equivalency Check. Test Che alumina by adding
the BNA surrogates (see Exhibit 0 SV) in 1:1 acetone/hexane
to the slumina and following paragraph 2.8.1. The tri-
bromophenol should not be detected by GC/EC if the alumina
and its activation are acceptalbe. Also check recovery of
all single component pesticides following the same proce-
dure. The percent recovery for all single component pesti-
cides following the same procedure. The percent recovery
for all single component pesticides following the same
procedure. The percent recovery for all single component
pesticides must be >802, except for endosulfan sulfate
which must be >60% and endrin aldehyde which is not recov-
ered. The data must be retained by the contractor and
made available for Inspection during on-site evaluations.
2.4.4 Reagent water - Reagent water is defined as water in which an
interferent is not observed at or above the CRQL of each parameter
of interest.
2.4.5 Tetrabutylatnmonium (TBA) - sulfite reagent. Dissolve 3.39 g tetra-
butylammonium hydrogen sulfate in 100 mL distilled water. To
remove impurities, extract this solution three times with 20 mL
portions of hexane. Discard the hexane extracts, and add 25g
sodium sulfite to the water solution. Store the resulting solution,
which is saturated with sodium sulfite, in an amber bottle with a
Teflon-lined screw cap. This solution can be stored at room temp-
erature for at least one month.
2.4.6 GPC calibration solutions:
2.4.6.1 Com oil - 200 mg/mL in methylene chloride.
2.4.6.2 Bis(2-ethylhexylphthalate) and pentachlorophenol - 4.0
mg/mL in methylene chloride.
2.4.7 Sodium Sulfite, reagent grade.
2.4.8 Surrogate standard spiking solution.
2.4.8.1 Pesticide surrogate standard spiking solution.
2.4.8.1.1
2.4.8.1.2
PEST D-21 10/86
The surrogate standard Is added to all samples,
blanks, matrix spike, matrix spike duplicates,
and calibrations solutions; the compound spec-
ified for this purpose is dibutylchlorendate.
Prepare a surrogate standard spiking solution
at a concentration of 20 ug/1.0 mL in methanol.
Store the spiking solutions at 4°C (+2aC) Tef-
lon-sealed containers. The solutions should be
checked frequently for stability. These solutions
must be replaced after twelve months, or sooner
if comparison with quality control check samples
indicates a problem.
-------
II. c
2.4.9 Matrix standard spiking solutions.
2.4.9.1 Pesticide matrix standard spiking solution. Prepare a
spiking solution in methanol that contains the following
pesticides in the concentrations specified belov. Store
spiking solutions ac 4aC (+2a) in Teflon-sealed containers.
The solutions should be checked frequently for stability.
These solutions oust be replaced after twelve months, or
sooner if comparison with quality control check samples
indicate a problem.
Pesticide ug/1.0 mL
lindane 2.0
heptachlor 2.0
aldrln 2.0
dleldrln 5.0
endrln 5.0
4,4' DDT 5.0
Matrix spikes are also to serve as duplicates, therefore,
add volume specified in Sample Extraction section to each
of two 30 g portions from one sample chosen for spiking.
2.5 Sample Extraction
2.5.1 Decant and discard any water layer on a sediment sample. Mix
samples thoroughly, especially composited samples. Discard any
foreign objects such as sticks, leaves, and rocks.
2.5.1.1 Transfer 50 g of soil/sediment to 100 ml beaker. Add 50
ml of water and stir for 1 hour. Determine pH of sample
with glass electrode and pH meter while stirring. Report
pH value on appropriate data sheets. If the pH of the soil
is greater than 11 or less than 5, contact the Deputy
Project Officer cited in the contract for instructions
on how to handle the sample. Document the instructions
in the Case Narrative. Discard this portion of sample.
NOTE: Recovery of dibutylchlorendate will be low if pH
is outside this range.
2.5.2 The following step should be performed rapidly to avoid loss of
the more volatile excractables. Weigh approximately 30 g of sample
to the nearest 0.1 g Into a 400-mL beaker and add 60 g of anhydrous
powdered sodium sulfate. Mix well. The sample should have a sandy
texture at this point. Immediately, add 100 mL of 1:1 methylene
chloride - acetone to the sample.
2.5.2.1 Immediately after weighing the sample for extraction,
weigh 5-10 g of the sediment into a tared crucible.
Determine the percent moisture by drying overnight at
105°C. Allow to cool in a desiccator before weighing.
Concentrations of individual analytes will be reported
relative to the dry weight of sediment.
PEST D-22
10/86
-------
II. c
g of 3ample - g of dry sample
g of sample ^ ^ moisture
2.5.2.2 Weigh out two 30 g (record weight to nearest 0.1 g) portions
for use as matrix and matrix spike duplicates. Follow
2.5.2. When using GPC cleanup, add 800 uL of the pesticide
matrix spike to each of the other two portions. When not
using GPC cleanup, add 400 uL of the pesticide matrix spike
to each of the two portions.
2.5.2.3 When using GPC, add 200 uL of pesticide surrogate to the
sample. When not using GPC, add 100 uL of pesticide
surrogate to the sample.
2.5.3 Place the bottom surface of the tip of the 3/4 inch disruptor horn
about 1/2 inch below the surface of the solvent but above the
sediment layer.
2.5.4 Sonicate for 3 minutes using 3/4 inch disruptor horn with output
control knob set at 10 and mode switch on "pulse" and 7, duty cycle
knob set at 50X. When using a sonicator other than Model W-375,
refer to the manufacturer's Instructions for appropriate output
settings. Do NOT use the MICR0TIP probe.
2.5.5 Decant and filter extracts through Whatman #41 filter paper using
vacuum filtration or centrifuge and decant extraction solvent.
2.5.6 Repeat the extraction two more times with 2 additional 100 mL
portions of 1:1 methylene chloride - acetone. Before each
extraction, make certain that the sodium sulfate is free flowing
and not a consolidated mass. As required, break up large lumps
with a clean spatula, or very carefully with the tip of the.
probe. Decant off the extraction solvent after each sonication.
On the final sonication, pour the entire sample into the Buchner
funnel and rinse with 1:1 methylene chloride - acetone.
2.5.7 Transfer the extract to a Kuderna-Danish (K-D) concentrator con-
sisting of a 10 mL concentrator tube and a 500 mL evaporative
flask. Other concentration devices or techniques may be used if
equivalency is demonstrated for all extractable and pesticide
compounds listed in Exhibit C.
2.5.8 Add one or two clean boiling chips to the evaporative flask and
attach a three-ball Snyder column. Pre-wet the Snyder column by
adding about 1 mL methylene chloride to the top. Place the K-D
apparatus on a hot water bath (80 to 90°C) so that the concentrator
tube is partially immersed in the hot water and the entire lower
rounded surface of the flask is bathed with hot vapor. Adjust
the vertical position of the apparatus and Che water temperature
as required to complete the concentration in 10 to 15 minutes.
At the proper rate of distillation the balls of the column will
actively chatter but the chambers will not flood with condensed
PEST D-23
10/86
-------
II. c
solvent. When che apparent volume of liquid reaches 1 mL, remove
the K-D apparatus and allow it Co drain and cool for at lease 10
mlnuces, and make up to 10 mL volume with methylene chloride.
2.5.9 If GPC cleanup is not used proceed to paragraph 2.7.
2.6. Extract Cleanup
2.6.1 GPC Setup and Calibration
2.6.1.1 Packing che column - Place 70 g of Bio Beads SX-3 in a
400 mL beaker. Cover the beads with methylene chloride;
allow the beads to swell overnight (before packing the
columns). Transfer che swelled beads Co Che column and
scart pumping solvent Chrough Che column, from boccom Co
top, at 5.0 mL/min. After approximately 1 hour, adjust
the pressure on the column to 7 to 10 psi and pump an
additional 4 hours to remove air from the column. Adjust
Che column pressure periodically as required to maintain
7 to 10 psi.
2.6.1.2 Calibration of the column - Load 5 mL of the'com oil
solution into sample loop No. 1 and 5 mL of the phthalate-
phenol solution into loop Ho. 2. Inject the corn (oil and
collect 10 mL fraction (i.e., change fraction at 2-tninute
intervals) for 36 minutes. Inject the phthalate-phenol
solution and collect 15 mL fractions for 60 minutes.
Determine the corn oil elution pattern by evaporation of
each fraction co dryness followed by a gravimetric deter-
mination of the residue. Analyze the phthalate-phenol
fractions by GC/FID on the DB-5 capillary column, a UV
spectrophotometer, or a GC/MS system. Plot che concentra-
tion of each component In each fraction versus total
eluent volume (or time) from the injection points. Choose
a "dump time" which allows >. 85% removal of che corn oil
and >_ 85Z recovery of Che bis(2-ethylhexyl)-phthalate.
Choose che "collect time" to extend at least 10 minutes
after the elution of pentachlorophenol. "Wash the column
at least 15 minutes between samples. Typical parameters
selected are: Dump time, 30 minutes (150 mL), collect
time, 36 minutes (ISO mL), and wash time, 15 minutes (75
mL). The column can also be calibrated by the use of a
254 mm UV detector in place of gravimetric and GC analyses
of fractions. Measure the peak areas at various elution
times to determine appropriate fractions.
The SX-3 Bio Beads column may be reused for several months,
even if discoloration occurs. System calibration usually
remains constant over this period of time if column flow
rata remains constant.
PEST D-24
10/86
-------
II. c
2.6.2 GPC Extract Cleanup
Prefilter or load all extracts via the filter holder to avoid
particulates Chat might stop the flow. Load one S.O tnL aliquot
of the extract onto the GPC column. Oo not apply excessive
pressure when loading the GPC. Purge the sample loading tubing
thoroughly with solvent between extracts. After especially dirty
extracts, run a GPC blank (methylene chloride) to check for
carry-over. Process the extracts using the dump, collect, and
wash parameters determined from the calibration and collect the
cleaned extracts in 400 mL beakers tightly covered with aluminum
foil. The phthalate-phenol calibration solution shall be taken
through the cleanup cycle with each set of 23 extracts loaded into
Che GPC. The recovery for each compound must be >. 85%. This
must be determined on a GC/FID, using a DB-5 capillary column, a
UV recording spectrophotometer, or a GC/MS system. A copy of the
printouts of standard and check solution are required as deliver-
ables with each case. Show X recovery on the copy.
2.6.2.1 If GPC cleanup of samples Is required because of poor GC/
EC chromatography in Section IV, dilute the extract to 10
mL with methylene chloride and perform GPC cleanup as per
paragraph 2.6.2. The reagent blank accompanying the
samples should be included, unless only one or a partial
group of samples requires cleanup. In this case, set up
a new reagent blank with 10 mL of methylene chloride and
appropriate surrogace scandard added.
2.6.3 Concentrate the extract as per paragraphs 2.5.7 and 2.5.8.
Final Concentration of Extract with Optional Extract Splitting Procedure
If the extract in 2.5.8 is to be used only for pesticide/PCB analysis,
it must be concentrated to a volume of 1.0 mL, following the procedure
in 2.7.1.
If the extract in 2.5.8 is to be used for both semivolatile and pesticide/
PCB analyses, then it must be split into two portions. In that case,
follow the procedure in 2.7.1 co obtain the pesticide portion, and follow
that with the procedure In 2.7.2 to obtain the semlvolatlle portion.
Refer to Exhibit D SV for specific instructions regarding the treatment
of extracts for semivolatile analysis.
2.7.1 If the extract is to be used only for the pesticide/PCB analysis,
or if the same extract is used for both semlvolatlle and pesticide/
PCB analyses, to split out the pesticide/PCB extract, transfer
0.5 mL of the 10 mL methylene chloride extract to a separate con-
centrator tube. Add 5 mL of hexane and a silicon carbide boiling
chip and mix using vortex mixer. Attach a two-ball micro-Snyder
column. Pre-wet the Snyder column by adding 0.5 mL of hexane to the
top of the column. Place the K-D apparatus on a hot water bath
(80°-908C) so that the concentrator tube is partially immersed in
the hot water. Adjust the vertical position of the apparatus and
PEST D-25
10/86
-------
II. c
Che water temperature as required to complete the concentration in
5 to 10 minutes. Concentrate the extract to an apparent volume of
less than 1 mL. Use Nitrogen blowdown (see 2.7.3) to reduce the
volume to 0.5 mL. Add 0.S mL of acetone. The pesticide extract
must now be passed through an alumina column to remove the BNA
surrogates and polar interferences. Proceed to paragraph 2.8.
2.7.2 If the extract in 2.5.8 was split in 2.7.1 to obtain a portion for
pesticides analysis, the portion for semivolatile analysis must
be treated according to the procedures in Exhibit 0 SV, Section II,
Pare G, paragraph 2.7.2.2.
2.7.3 Nitrogen blowdown technique (taken from ASTM Method 0 3086). Place
the concentrator tube in a warm water bach (35° C) and evaporate
the solvent volume to below 1 mL using a gentle stream of clean,
dry nitrogen (filtered through a column of activated carbon).
Caution: New plastic tubing must not be used between the carbon
crap and the sample, since it may introduce interferences.
The internal wall of the tube must be rinsed down several times
with hexane during the operation. During evaporation, the tube
solvent level must be kept below the water level of the bath. The
extract must never be allowed to become dry* If GPC cleanup tech-
niques were employed, the 0.5 mL volume represents a two-fold
dilution to account for the fact that only half the extract went
through the GPC.
2.7.4 Store all extracts at 48C (+2°C) in the dark in Teflon-sealed
containers until all analyses are performed.
2.8 Pesticlde/PCB
2.8.1 Alumina Column Cleanup
All samples prepared from the same extract as used for the semlvol-
atlle analysis must be taken through this cleanup technique to
eliminate BNA surrogates that will interfere in the GC/EC analysis.
2.8.1.1 Add 3 g of activity III neutral alumina to Che 10 mL
chromatographic column. Tap the column to settle the
alumina. Do not pre-vet the alumina.
2.8.1.2 Transfer the 1.0 mL of hexane/acetone extract from paragraph
2.7.1 to the top of the alumina using a disposable Pasteur
pipette. Collect the eluate in a clean, 10 mL concentrator
tube.
2.8.1.3 Add 1 mL of hexane to the original extract concentrator
tube to rinse it. Transfer these rinsings eo the alumina
column. Elute the column with an additional 9 mL of hexane.
Do not allow the column to go dry during Che addicion and
eluclon of the sample.
PEST D-26 10/86
-------
II. c
2.8.1.4 Coneencrace Che excract Co 1.0 mL following elCher paragraph
2.7*1 or 2.7.3, using hexane where methylene chloride is
specified. When concentrating medium level extracts, the
Nitrogen blowdovn technique should be used to avoid contam-
inating the micro Snyder column.
2.8.2 Observe the appearance of Che excract.
2.8.2.1 If crystals of sulfur are evident or sulfur is expected to
be present, proceed to paragraph 2.8.3.
2.8.2.2 If the sulfur is not expected to be a problem, transfer
the 1.0 mL to a GC vial and label as Pesticide/PCB fraction.
The extract is ready for GC/EC analysis. Proceed to
Section IV. Store the extracts at 4°C (+2°C) in the dark
until analyses are performed.
2.8.3 Optional Sulfur Cleanup
2.8.3.1 Transfer the 1.0 mL from paragraph 2.8.2 to a SO mL clear
glass bottle or vial with a Teflon-lined screw cap. Rinse
the concentrator tube with 1.0 mL of hexane, adding the
rinsings to the 50 mL bottle. If only a partial set of
samples requires sulfur cleanup, sec up a new reagent
blank with 1.0 mL of hexane and take it through the sulfur
cleanup. Include Che surrogace standards.
2.8.3.2 Add 1 mL TBA-sulfice reagent and 1 mL 2-prppanol, cap che
bottle, and shake for at least 1 min. If the sample is'
colorless or if the initial color is unchanged, and if
clear crystals (precipitated sodium sulfite) are observed,
sufficient sodium sulfite is present. If the precipitated
sodium sulfite disappears, add more crystalline sodium
sulfite in approximately 100 mg portions until a solid
residue remains after repeated shaking.
2.8.3.3 Add 5 mL distilled water and shake for at least 1 min.
Allow the sample to stand for 5-10 min. and remove the
hexane layer (top) for analysis. Concentrate the hexane
to 1.0 mL as per paragraphs 2.7.1 and 2.7.3 using hexane
where methylene chloride is specified. The temperature
for the water bach should be about 80®C for the micro Snydep
column column technique. Continue as outlined in paragraph
2.8.2.2.
PEST D-27
10/86
-------
SECTION III
SCREENING OF PESTICIDE/PCB EXTRACTS
PEST D-28
10/86
-------
III.
Ic is mandatory that all soil/sediment samples be characterized as Co concen-
tration level so that the appropriate analytical protocol may be chosen to
ensure proper quantitation limits for the sample.
The use of GC/EC methods Is recommended for screening soil/sediment samples
for pesticides/PCBs. The contractor is at liberty to determine the specific
method of characterization. The protocols for sample preparation (Section II)
and sample analysis (Section IV) are broken down by concentration level.
The terms "low level" and "medium level" are not used as a judgement of the
degree of contamination, but rather as a description of the concentration
ranges that are encompassed by the "low" and "medium" protocols.
The concentration range encompassed by the low level protocols may be considered
to be appropriate for chose samples with less Chan 1000 ug/kg of pesclcldes/
PCBs. The concencracion range encompassed by the medium level prococols may
be considered co appropriate for those samples with more than 1000 ug/kg of
pesticides/PCBs.
PEST 0-29
10/86
-------
SECTION IV
GC/EC ANALYSIS OF PESTICIDES/PCBs
PEST 0-30
10/86
-------
IV.
Summary of Method
1.1 The hexane extracts of water and soil/sediment are analyzed on a gas
chromatograph/electron capture detector (GC/EC). If pesticides or PC3s
are tentatively identified, a second GC/EC analysis is required using an
alternate column. Quantitation must be on a packed column, whereas,
confirmation can be on either a packed or a capillary column.
Interferences
2.1 Method interferences may be caused by contaminants in solvents, reagents,
glassware, and other sample processing hardware that lead to discrete
artifacts and/or elevated baselines in gas chromatograms. All of these
materials must be routinely demonstrated to be free from interferences
under the conditions of the analysis by running laboratory method blanks.
Apparatus and Materials
3.1 Gas chromatograph - An analytical system complete with gas chromatograph
and all required accessories Including syringes, analytical columns,
gases, electron capture detector, and strip-chart recorder with recording
integrator. A data system is required for measuring peak areas or peak
heights and recording retention times. An electrolytic conductivity
detector is also acceptable if the required quantitation limits are met.
Overlapping peaks on chromatograms are not acceptable.
3.3.1.1 Quantitation and/or confirmation columns.
3.3.1.1.1 Column 1 - Gas Chrom Q (100/120 mesh) or equivalent
coated with 1.5Z OV-17/1.95% OV-210 or equivalent
packed in a 1.8 m long x 4 mm ID (6 mm 0D) glass
column.
NOTE: The 2mm 10 column cited in Table 7 as Column
1 will not adequately separate dibutylchlorendate
and endrin ketone.
3.3.1.1.2 Column 2 - Gas Chrom Q (100/120 mesh) or equivalent
coated with 3Z 0V-1 or equivalent packed in a 1.8 m
long x 2 mm ID (6 mm 00) glass column.
3.3.1.1.3 Column 3 - Gas Chrom Q (80/100 mesh) or equivalent
coated with 5% OV-210 or equivalent packed in a
1.8 m long x 2 mm ID (6 mm 0D) glass column.
3.1.2 Confirmation column only. Column - 30 m X 0.25 mm ID, 0.25 micron
film thickness, bonded-phase silicone coated, fused silica capillary
column (J&W Scientific DB-5 or DB-1701 or equivalent). NOTE:
DB-1701 provides better separation of TCL pesticides. Column -
10 m x 0.32 mm ID, I micron film thickness has been used.
3.2 Balance - analytical, capable of accurately weighing +0.0001 g.
PEST D-31 10/86
-------
IV.
4. Reagents
4.1 Isooctane (2,2,4-trimethylpentane), hexane, and toluene - Pesticide
quality or equivalent.
4.2 Stock standard solutions (1.00 ug/uL) - Stock standard solution can be.
prepared from pure standard materials or purchased as certified solutions.
4.2.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure material. Dissolve the material in toluene,
dilute to volume in a 10 ml volumetric flask with isooctane.
Larger volumes can be used at the convenience of the analyst.
If compound purity is certified at 96% or greater, the weight can
be used without correction to calculate the concentration of the
stock standard. Commercially prepared stock standards can be
used at any concentration if they are traceable to EMSL/LV supplied
standards.
4.2.2 Transfer the stock standard solutions into a bottle/vial with
Teflon-lined septa. Store at 4°C (+2°C) and. protect from light.
Stock standard solutions must be replaced after twelve months, or
sooner if comparison with check standards indicate a problem.
4.3 Working standards solutions - Prepare mixtures of standards diluted with
hexane that will provide approximately half scale response for all the
compounds of interest. This should be at the attenuation setting capable
of achieving the contractrequired quantitation limits (Exhibit C). (This
would be approximately 0.01 ng/uL for aldrln.) All individual component
standards must be in two mixtures for packed column. One mixture is
acceptable when using capillary. Include dibutylchlorendate in the all
standard mixtures. All multlcomponent standards, i.e., PC3 Aroclors and
toxaphene must be in separate solutions with the exception of Aroclors
1016/1260. Include dibutylchlorendate in all multicomponent standard
mixtures.
4.3.1 Evaluation Standard Mixtures - Prepare working standard mixtures
diluted with hexane containing aldrln, endrin, 4,4' 00T and
dibutylchlorendate to evaluate the GC column. Prepare three
concentration levels to provide the following criteria:
4.3.1.1 Low level will be approximately 20% above base line
(Evaluation Standard Mix A).
4.3.1.2 Mid level will be approximately half scale (Evaluation
Standard Mix B).
4.3.1.3 High level will be approximately full scale (Evaluation
Standard Mix C). (Dibutylchlorendate must be 0.1 ng/uL
to correspond with 100% surrogate recovery in 10 mL
final volume. This may be slightly greater than full
scale but should still be in linear range).
PEST D-32
10/86
-------
IV.
4.3*2 Individual Standard Mixtures - These Include all single component
TCL pesticides plus alpha chlordane, gamma chlordane, endrln
ketone, endrln aldehyde and dlbutylchlorendate (see paragraph
6.1.4 for suggested mixtures). Alpha and gamma chlordane
should be In Mixture B to avoid overlap with other pesticides.
Calibration
5.1 The gas chromatographic system must be calibrated using the external
stanard technique for all packed columns used for quantitation.
5.2 External standard calibration procedure:
5.2.1 Prepare calibration standards at a minimum of three concentration
levels for each parameter of Interest by adding volumes of one or
more stock standards to a volumetric flask and diluting to volume
with hexane. One of the external standards should be at a concen-
tration near, but above, the CRQL and the other concentrations
3hculd correspond Co the expected range of concentrations found
In real samples or should define the working range of the detector.
This should be done on each quantitation column and each Instrument
at the beginning of the contract period and each time a new
column is installed. The data must be retained by the laboratory
and made available for inspection during on-site evaluations.
5.2.2 Using injections of 2 to 5 uL of each calibration standard,
tabulate peak height or area responses against the mass injected.
The results can be used to prepare a calibration curve for each
compound.
GC/EC Primary Analysis (Quantitation may be performed on primary or confirmation
analyses.)
Adjust oven temperature and carrier gas flow rates so that the retention time
for 4,4'-DDT is equal to or greater than 12 minutes.
Table 7 provides examples of operating conditions for the gas chromatograph.
Separation should be >_ 252 resolution between peaks. Percent resolution is
calculated by dividing the height of the valley by the peak height of the
smaller peak being resolved, multiplied by 100. This criterion must be considered
when determining whether to quantitate on the Primary Analysis or the Confirmation
Analysis. When this criterion cannot be met, quantitation is adversely affected
because of the difficulty in determining where to establish the baseline.
6.1 Inject 2 to 5 uL of the sample or standard extract using the solvent-flush
technique or auto sampler. Smaller (1.0 uL) volumes can be injected only
if automatic devices are employed. Record the volume injected to the
nearest 0.05 uL and the total extract volume. NOTE: Dibutylchlorendate
recovery may be calculated from a capillary or packed column GC/EC meeting
all QC requirements for quantitation. However, matrix spike duplicates
must be quanticated on a packed column.
PEST D-33
10/86
-------
IV.
6.1.1 Inject Individual Standard Mix A and B and all multi-response
pesticides/PCBs at the beginning of each 72 hour sequence. (See
paragraph 6.1.3.5) To establish the RT window within each 72-hour
sequence for the pesticide/PCB of interest, use the absolute RT
from the above chromatograms as the mid-point, and + three times
the standard deviation calculated in Exhibit E for each compound.
Individual Standard Mix A and B are analyzed alternately and
intermittently throughout the analysis as shown in 6.1.3.5. Any
pesticide outside of its established retention time window requires
immediate investigation and correction before continuing the
analysis. The laboratory must reanalyze all affected samples.
6.1.2 Sample analysis of extracts from Section II, Sample Preparation,
can begin when linearity and degradation QA/QC requirements
specified in Exhibit E have been met.
NOTE: The 10.0Z RSD linearity criterion is only required on the
column(s) being used for pesticlde/PCBs quantitation. If a
column is used for surrogate quantltitation only, the 10.0% RSD
is required only for dibutylchlorendate.
Analyze samples in groups of no more than 5 samples. After the
analysis of the first group of up to 5 samples, analyze Evalua-
tion Mix B. Analyze another group of up to 5 samples, followed
by the analysis of Individual Mix A or B. Subsequent groups of
up to 5 samples may be analyzed by repeating this sequence,
alternately analyzing Evaluation Mix B and Individual Mix A or B
between the groups as shown in 6.1.3.5. The Pesticide/PCB
analytical sequence must end with Individual Mix A and B regard-
less of the number of samples analyzed (see 6.1.3.5).
If a multlresponse pesticide/PCB is detected in either of the
preceding groups of 5 samples, the appropriate multlresponse
pesticide/PCB may be substituted for Individual Mix A or B.
All standards listed in 6.1.3.5 must be included for every Case
and must be analyzed within the same 72-hour period as the
samples, with the exception of Aroclors 1221 and 1232 which are
analyzed at a minimum of once per month (see footnote in 6.1.3.5).
If the samples are split between 2 or more instruments, the
complete set of standards must be analyzed on each instrument
with the same 72-hour requirement. All standards must be analyzed
prior to the samples to avoid the effects of poor chromatography
caused by the unsuspected injection of a highly concentrated
sample.
6.1.3 Paragraphs 6.1.3.1 - 6.1.3.5 contain GC performance criteria.
If it is determined during the course of a 72-hour sequence
that one or more of the criteria have been violated, stop the
run and take corrective action (see Exhibit E, Section III PEST,
4.3.3.8). After the corrective action has been taken, the 72-hour
sequence may be restarted as follows. If a standard violated the
criterion, restart the sequence with that standard, determine
that the criteria have been met, and continue with sample analyses,
PEST D-34
10/86
-------
IV.
according Co 6.1.3.5. If a sample violated Che criterion,
restart the sequence with the standard that would have followed
that group of samples (thereby preserving the sequence of
standards in 6.1.3.5), determine that the criteria have been
met, and continue with sample analyses, according to 6.1.3.5.
If it is determined after the completion of a 72-hour sequence
Chat one or more of Che crlceria have been violaced, proceed as
follows. If a standard violaced the criterion, all samples
analyzed after that standard muse be re-analyzed as part of a
new 72-hour sequence. If a subsequent standard in the original
sequence met all the criteria, then only those samples analyzed
between the standard that did not meet the criterion and the
standard that did meet the criterion must be re-analyzed as
part of a new 72-hour sequence. If only samples violated the
criteria, then those samples must be re-analyzed as part of a
new 72-hour sequence.
6.1.3.1 Differences in the Calibration Factors for each standard
in Individual Standard Mix A and B must not exceed
20.0% (15.0% for any standard compound used for quanti—
tation) during the 72-hour Primary Analysis. Calculate
the % difference using the initial Individual Standard
Mix versus all subsequent Individual Standard Mixes
analyzed during the 72-hour sequence. (The equations
for calculation of Calibration Factor and Z difference
are in Exhibit E, Section III PEST, paragraph 4.3.4.2.)
The retention time shift of dibutylchlorendate in
any standard or sample must be less than 2.0% for
packed columns (<0.3% for capillary columns).
6.1.3.2 Samples must also be repeated if the degradation of
DDT and/or endrin exceeds 20.0% respectively on the
intermittent analysis of Evaluation Standard Mix B.
6.1.3.3 All pesclcide standards muse fall within Che
established 72-hour retention time windows.
6.1.3.4 Highly colored extracts may require a dilution.
PEST D-35
10/86
-------
IV.
6.1.3.5 The 72-hour sequence must be as follows.
72-Hour Sequence for Pesticide/PCB Analysis
1. Evaluation Standard Mix A
2. Evaluation Standard Mix B
3. Evaluation Standard Mix C
4. Individual Standard Mix A*
5. Individual Standard Mix B*
6. Toxaphene
7. Aroclors 1016/1260
8. Aroclor 1221**
9. Aroclor 1232**
10. Aroclor 1242
11. Aroclor 1248
12. Aroclor 1254
13. 5 samples
14. Evaluation Standard Mix B
15. 5 samples
16. Individual Standard Mix A or B
17. 5 samples
18. Evaluation Standard Mix B
19. 5 samples
20. Individual Standard Mix A or B
(whichever not run in step 16)
21. 5 samples
22. Repeat the above sequence starting
with Evaluation Standard Mix B (step
14 above).
23. Pestlclde/PCB analysis sequence must
end with Individual Standard Mix A and
B regardless of number of samples
analyzed.
*These may be combined into one mixture for capillary
column analyses, (see paragraph 4.3).
**Arodors 1221 and 1232 must be analyzed on each instru-
ment and each column at a minimum of once per month.
Copies of these chromatograms must be submitted for
sample analyses performed during the applicable
month.
6.1.4 Suggested groups of compounds and concentrations for Individual
Standard Mix A and B follow, which are recommended to prevent
overlap of compounds on the two packed columns (3% 0V-1 and
1.5% 0V-17/1.95% 0V-210). Some of the compounds overlap on the
5Z 0V-210 column (see Table 7). The concentration is based on
a 5 uL injection.
PEST 0-36
10/86
-------
IV.
Individual
Individual
Standard Mix A
njf/uL
Standard Mix B
ng/uL
gamma-BHC
0.005
alpha-BHC
0.005
hepcachlor
0.010
beta-BHC
0.010
aldrin*
0.010
delta-BHC
0.010
hepcachlor epoxide
0.010
aldrin*
0.010
endosulfan I
0.010
p,p'-DDE
0.010
dieldrin
0.010
endrin
0.010
p.p'-DDT
0.020
p,p'-DDD
0.020
endrin aldehyde
0.025
endosulfan sulfate
0.020
endosulfan II
0.020
endrin ketone
0.020
mechoxychlor
0.100
alpha chlordane
0.010
dibutyl chlorendate
0.050
gamma chlordane
0.010
dlbutylchlorendate
0.050
*For RRT determination.
6.1.5 Inject Che method blank (excracced with each set of samples) on
every Instrument and GC column on which the samples are analyzed
Evaluation of Chromatograms.
6.2.1 Consider the sample negative when its peaks, depending on the
pesticide's response factor, result in concentrations less than
the required quantitation level. The sample is complete at this
point. Confirmation is not required.
6.2.2 Tentative identification is made when the unknown's retention
time matches the retention time of a corresponding standard that
was chromatographed on the same instrument within a 72-hour
period.
6.2.3 Determine if any pesticides/PCBs listed in Exhibit C are present
Pattern recognition techniques, based on chromatograms of stan-
dards, are recommended for Che identification of PCB compounds.
6.2.3.1 If the response for any of these compounds is 100Z or
less of full scale, the extract.is ready for confirma-
tion and quantitation.
6.2.3.2 If the response for any compound is greater than full
scale, dilute the extract so that the peak will be
between 50 and 100% full scale and reanalyze on the
packed column. Use this dilution also for confirma-
tion and quantitation.
6.2.3.3 For dilution > 10 fold. Also inject an aliquot of
a dilution 10 fold more concentrated to determn if
other compounds of interest are present at lower
concentrations.
6.2.3.4 Computer reproductions of chromatograms manipulated
to ensure all peaks are on seals over a 100 fold range
are an accepted substitute. However, this can be no
PEST D-37 10/86
-------
IV.
greater Chan a 100 fold range. This Is Co prevent
retention time shifts by column or detector overload.
Linearity must be demonstrated over the 100 fold range
using higher concentrations of the evaluation mixture.
6.2.4 Quantitation may be performed on the primary analysis, with the
exception of toxaphene and possibly the DOT series. If DDT
exceeds the 10.07, RSD linearity criterion, then quantitations for
any DDE, DDD and DDT in a sample must be on the confirmation
analysis. Toxaphene must always be quantltated on the confirma-
tion analysis. See Exhibit E for special QC requirements for
quantitation.
6.2.5 If identification of compounds of interest are prevented by the
presence of interferences, further cleanup is required. If
sulfur is evident go to Sulfur Cleanup (Section II, Part B,
paragraph 8.). If unknown interferences or poor chromatography
are noted only In the sample chromatogram, it is recommended that
gel permeation chromatography cleanup (Section II, Part C,
paragraph 2.6) be applied.
6.2.6 When selecting a GC column for confirmation and/or quantitation,
be sure that none of the compounds to be confirmed/quantitated
overlap, i.e., do not select the 3% OV-1 column if DDE and dieldrin
are to be confirmed and/or quantltated. When samples are very
complex, it may be necessary to use all three packed columns to
achieve adequate separation (>25% resolution) of all compounds
being quantltated.
7. GC/EC Confirmation Analysis
7.1 Confirmation Analysis is co confirm Che presence of all compounds tenta-
tively identified in the Primary Analysis. Therefore, Che only standards
chac are required are Che Evaluation Standard Mixes (to check linearity and
degradation criteria) and standards of all compounds to be confirmed.
The linearity criterion on the confirmation column for pesticides is not
required unless the column is used for quantitation. The 72-hour sequence
in 6.1.3.5 is, therefore, modified to fit each case. Quantitation may be
performed on the confirmation analysis. If coxaphene or DDT is Co be
quanticaced, additional linearity requirements are specified in 7.3.1.
7.2 Table 7 provides examples of operating conditions for the gas chromatograph.
Separation should be .> 25% resolution between peaks. Percent resolution
is calculated by dividing the height of the valley by the peak height of
the smaller peak being resolved, multiplied by 100. This criterion must
be considered when determining whether to quantitate on the Primary
Analysis or the Confirmation Analysis. When this criterion cannot be
met, quantitation is adversely affected because of the difficulty in
determining where to establish the baseline.
For a fused silica capillary column (FSCC) confirmation, there must be
>. 25 percent resolution (valley) between the following pesticide pairs:
PEST D-38
10/86
-------
IV.
o beta-BHC and delta-BHC
o Deildrin and 4,4'-DDT
o 4,4'-ODD and Endrin Aldehyde
o Endosulfan Sulfate and 4,4'-DDT
All QC requirements specified in Exhibit E oust be adhered to, i.e., the
>_12 min. retention time for 4,4'-DDT, the criteria for 4,4'-DDT and
endrin degradation, linearity, calibration factor for standards, and
retention time shift for dlbutylchlorendate. The retention time criterion
for 4,4'-DDT does not have to be met if the confirmation column is OV-1
or OV-101. Apply instructions from 6.1.3 to the confirmation analysis.
Inject 2 to 5 uL (1-2 uL for capillary columns) of the sample extract and
standards using the solvent-flush technique or auto samplers* One uL
volumes can be injected only if automatic devices are employed. Record
the volume injected to the nearest 0.05 uL and the total extract volume.
The detector attenuation must provide peak response equivalent to the
Primary Analysis response for each compound to be confirmed.
7.3.1 Begin the Confirmation Analysis GC sequence with the three con-
centration levels of Evaluation Standard Mixes A, 8 and C. The
exception to this occurs when toxaphene and/or DDT series are to
be confirmed and quantitated. There are four combinations of
pesticides that could occur, therefore, the following sequences
must be followed depending on the situation.
7.3.1.1 Toxaphene only - Begin the sequence with Evaluation Mix
B to check degradation, followed by thr?e concentration
levels of toxaphene. Check linearity by calculating
ZRSD.
If £10.02 RSD, use the appropriate equation in paragraph
8 for calculation. If >10.02 RSD, plot a standard
curve and determine the ng for each sample In that set
from the curve.
7.3.1.2 DDT, DDE, DDD only - Begin the sequence with Evaluation
Mix B. Then inject three concentration levels of a
standard containing DDE, DDD and DDT. Calculate line-
arity and follow the requirements specified in 7.3.1.1
for each compound to be quantitated.
7.3.1.3 DDT series and toxaphene - Begin the sequence with
Evaluation Mix B. Then inject three concentration levels
of toxaphene and another three levels of the DDT series.
Calculate linearity and follow the requirements specified
in 7.3.1.1 for each compound to be quantitated. NOTE:
Capillary quantitation would be allowed only in this
situation.
7.3.1.4 Other pesticides/PCBs plus DDT series and/or toxaphene -
Begin the sequence with Evaluation Standard Mixes
A, B and C. Calculate linearity on the four compounds
PEST D-39 10/86
-------
IV.
In che Evaluation Standard mixes. If DOT and/or one
or more of the other compounds are >10.0% RSO and/or
degradation exceeds the criterion, corrective main-
tenance as outlined in Exhibit E, Section III PEST,
paragraph 4.3.3.8, should be performed before repeating
che above chromatography evaluations. If only DOT
exceeds Che linearity criterion and one or more of
Che DOT series is Co be quantltated, follow 7.3.1.2 (do
not repeat Evaluation Mix B).
If none of the DDT series is to be quantltated and
DDT exceeds Che 10.0% RSD, simply record che Z RSD
on che proper form. Any time Coxaphene is Co be
quantltated, follow 7.3.1.1.
7.3.2 Afcer Che linearity standards required in 7.3.1 are Injected,
continue the confirmation analysis sequence by injecting standards
for all compounds tentatively identified in the primary analysis,
to establish the 72-hour retention time windows. (See paragraph
6.1.1.) Analyze all confirmation standards for a case at the
beginning, at intervals specified In 7.3.3, and at the end.
Any pesticide outside of its established retention time window
requires immediate investigation and correction before continuing
the analysis. The laboratory must reanalyze all samples which
follow the standard that exceeds the criterion.
7.3.3 After injection of Che appropriate standards (see 7.3.2), begin
injection of samples. Analyze groups of 5 samples. Analyze
Evaluation Mix B after the first group of 5 samples. After the
second group of S samples, analyze a standard pertaining to the
samples in the preceeding groups (i.e., substitute standards
pertaining to the proceeding samples for Individual Mix A or B
in 6.1.3.5). Continue analyzing groups of 5 samples, alternately
analyzing Evaluation Mix B and standards pertaining to the
preceding samples between groups of 5 samples. The alternating
standard's calibration factors must be within 15.0% of each
other if quantitation is performed. Deviations larger than 15.0%
require the laboratory to repeat the analyses of samples which were
analyzed after the standard that exceeded the criterion. The
15.0% criterion only pertains to compounds being quantltated.
If more than one standard is required to confirm all compounds
tentatively identified in the Primary Analysis, alternate the
standards with Evaluation Mix B. Samples must also be repeated
if the degradation of either DDT and/or endrin exceeds 20.0% on
the intermittent Evaluation Standard Mix B.
If the samples are split between 2 or more instruments, all
standards and blanks pertaining to those samples muse be analyzed
on each instrument.
7.3.4 Inject the method blank (extracted with each set of samples) on
every GC and GC column on which the samples are analyzed.
PEST D-40
10/86
-------
IV.
Evaluation of Chromatograms
7.4.1 A compound tentatively identified in the primary analysis is
confirmed if Che retention time from the confirmation analysis
falls within the retention time window of a corresponding
standard that was chromatographed on the same instrument within
a 72-hour period.
7.4.2 Quantitation should be on the packed column chromatogram (primary
or confirmation) that provides the best separation from interfering
peaks.
7.4.2.1 Quantitation of Chlordane - Because weathering and/or
different formulations of chlordane usually modify the
pattern exhibited by technical chlordane, this method
is not appropriate for determining technical chlordane.
Instead, standards for alpha chlordane and gamma chlordane
are used for quantitation, and each isomer of chlordane
is reported separately.
7.4.3 Computer reproductions of chromatograms that are attenuated to
ensure all peaks are on scale over a 100 fold range are acceptable.
However, this can be no greater than a 100 fold range. This is
to prevent retention time shifts by column or detector overload.
Also, peak response must be >25Z of full scale deflection to
allow visual pattern recognition of nrulticomponent compounds, and
Individual compounds must be visible.
7.4.4 If identification of compounds of interest are prevented by the
presence of interferences, further cleanup is required. If sulfur
is evident go to Sulfur Cleanup (Section II, Part B, paragraph 8).
If unknown interferences or poor chromatography are noted only in
the sample chromatogram, it is recommended that gel permeation
chromatography cleanup (Section II, Fart C, paragraph 2.6) be
applied.
7.4.5 Calculate surrogate standard recovery on all samples, blanks, and
spikes unless the surrogate was diluted out. Determine if recovery
is within limits and report on Form II. See formula for calcu-
lation in 8.3.
7.4.6 If TCL pesticide/PCB compounds were identified in the unspiked
sample from which the matrix spike and matrix spike duplicate
were prepared, confirmation analysis is required for the matrix
spike and matrix spike duplicate. If TCL pestlclde/PCB compounds
were not identified in the unspiked sample, confirmation of the
matrix spike and matrix spike duplicate is not required. Calculate
matrix spike duplicate recoveries and report on Form III (see
Exhibit B, Section III).
PEST D-41
10/86
-------
IV.
8. Calculations
8.1 Calculate the concentration In che sample using the following equation
for external standards* Response can be measured by the manual peak
height technique or by automated peak height or peak area measurements
from an integrator.
8.1.1 Water
(A^XI.XV,.)
Concentration ug/L - (*&)(vi)vs)
Where:
Ag ¦ Response for the parameter to be measured.
Ag ¦ Response for the external standard.
Vc - Volume of total extract (uL) (take into account
any dilutions)
Is ¦ Amount of standard injected in nanograms (ng)
V^ ¦ Volume of extract injected (uL)
Va ¦ Volume of water extracted (mL)
8.1.2 Sediment/Soil
(*x)(Is)(vt)
Concentration ug/kg - (AS)(V£)(WS)(D)
(Dry weight basis)
Where:
A^ IS»AS,V£ ¦ same as given above In 8.1.1
Vt « Volume of low level total extract
(Use 20,000 uL or a factor of this when dilutions
are made other than those accounted for below):
o 1/20 total extract taken for pesticide analysis
(derived from 0.5 mL of 10 mL extract)
o final concentration to 1.0 mL for pesticide
analysis
- or - Vc • Volume of medium level total extract
(Use 10,000 uL or a factor of this when dilutions
are made.)
D » 100 - Z moisture (Z moisture from Section II, Part C)
100
Ws - Weight of sample extracted (g)
8.2 For rnulttlcomponent mixtures (chlordane, toxaphene and PCBs) match retention
times of peaks In the standards with peaks in the sample. Quantltate
every Identifiable peak (>50% of the total area must be used) unless
interference with individual peaks persist after cleanup. Add peak
height or peak area of each identified peak In the chromatogram. Calculate
as total response in the sample versus total response in the standard.
PEST D-42
10/86
-------
IV.
8.3 Calculation for surrogate and matrix spike recoveries.
Percent Recovery » Qd X 100%
vhere,
Q
-------
IV.
Table 7
Examples of Orders of Elutlon of Pesticides/PCBs
Parameter
Column 1
Column 2
Column 3
alpha-BHC
1.45
1.64
1.86
gamma-BHC
1.86
1.94
2.37
beta-BHC
2.18
1.76
2.75
Heptachlor
2.27
3.21
2.55
delta-BHC
2.55
2.01
2.80
Aldrin
2.76
4.01
2.93
Heptachlor epoxide
4.31
4.98
5.53
Endosulfan I
5.46
6.26
7.08
4,4'-DDE
6.37
7.51
6.03
Dieldrin
6.74
7.38
8.59
Endrin
8.25
8.35
10.14
4,4'-DDD
10.08
9.53
10.57
Endosulfan II
10.14
8.35
12.88
4,4'-DDT
12.06
12.75
11.55
Endrin aldehyde
13.64
9.53
21.11
Endosulfan sulfate
16.73
11.09
31.27
Endrin ketone
22.70
33.16
gamma Chlordane
4.77
5.74
5.25
alpha Chlordane
5.24
6.39
5.70
Toxaphene
mr
mr
mr
Aroclor-1016
mr
mr
mr
Aroclor-1221
mr
mr
mr
Aroclor-1232
mr
mr
mr
Aroclor-1242.
mr
mr
mr
Aroclor-1248
mr
mr
mr
Aroclor-1254
mr
mr
mr
Aroclor-1260
mr
mr
mr
methoxyclor
24.07
19.60
18.12
dibutyl chlorendate
21.80
27.21
22.26
mr » multiresponse compounds.
Column 1 conditions: Gas Chrom Q (80/lOOmesh) or equivalent coated with 1.52
OV-17/1.95Z OV-210 or equivalent packed in a 1.8 m long x 2 mm ID (6 mm
00) glass column with 52 methane/952 argon carrier gas at a flow rate of
30 mL/min. (HP 5880) Column temperature, isothermal at 192°C. 2 mm ID
column with 80/100 mesh does not adequately resolve dibutyl chlorendate
and endrin ketone.
Column 2 conditions: Gas Chrom Q (100/120 mesh) or equivalent coated with 32
0V-1 or equivalent packed in a 1.8 m long x 2 mm ID (6 mm 0D) glass column
with 52 methane/952 argon carrier gas at a flov rate of 30 mL/mln. (30
mL/mln makeup gas). (Tracor 222). Column temperature, isothermal at 194°C.
Column 3 conditions: Gas Chrom Q (80/100 mesh) or equivalent coated with 52
OV-210 packed in a 1.8 m x 2 mm ID (6 mm 0D) glass column with 52 methane/
952 argon carrier gas at a flow rate of 30 mL/min. (30 mL/min. make-nip
gas). HP5840. Column temperature, isothermal at 183°C.
PEST D-44
10/86
-------
Table 7 (continued)
Capillary column 1 conditions: 30 m x 0.25 am 10, 0.25 micron
film thickness, fused silica DB-5 (or equivalent) splitless mode
Helium carrier gas: 4 mL/min at 280°C and 25 PSI
Septum purge: 15 mL/mln
Split vent: none
Initial temperature: 160°C, initial hold - 2 mln
Program at 5°C/min
Final temperature: 270*C, final hold - 4 mln
Injection port temperature: 225°C
Capillary column 2 conditions: 10 m x 0.32 mm ID, 1 micron
film thickness, fused silica DB-1701, splitless mode
Helium carrier gas: 4 mL/min at 280°C and 25 PSI
Septum purge: 15 mL/mln
Split vent: none
Initial temperature: 160®C, initial hold - 3 mln
Program at 10°C/mln to 240 ®C
Program from 240 to 270°C at 5°C/min
Final Hold: 4 mln
Injection port temperature: 235®C
PEST D-45
10/86
-------
EXHIBIT E
QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
10/86
-------
EXHIBIT E
TABLE OF CONTENTS
Section Page
I INTRODUCTION E-2
II QA/QC STANDARD OPERATING PROCEDURES E-3
III QA/QC REQUIREMENTS E-9
Volatiles (VOA) QA/QC Requirements E-9
Semivolatiles (SV) QA/QC Requirements E-27
Pesticides/PCBs (PEST) QA/QC Requirements E-46
IV ANALYTICAL STANDARDS E-64
V LABORATORY EVALUATION PROCEDURES E-66
E-l 10/86
-------
SECTION I
INTRODUCTION
The purpose of Che Quality Assurance/Quality Control (QA/QC) program out-
lined herein Is the definition of procedures for the evaluation and documentation
of subsampllng, analytical methodologies, and the reduction and reporting of
data. The objective is to provide a uniform basis for subsampllng, sample
handling, Instrument conditions, methods control, performance evaluation, and
analytical data generation and reporting.
The scope of the program is for all laboratory operations (from sample
receipt, through analysis, to data reduction/reporting) applied to trace
organlcs samples. The scope includes those audit procedures used to evaluate
the application of the procedures defined within this QA/QC program.*
E-2
10/86
-------
SECTION II
QA/QC STANDARD OPERATING PROCEDURES
E-3
10/86
-------
II
1. The contractor shall have a written QA/QC standard operating procedure
(SOP) which describes the in-house procedures that he employs to guarantee,
to the extent possible, the quality of all analysis activities. It should
"describe the quality assurance and the quality control procedures used during
the analysis* Each contractor should prepare his own SOPs to suit the needs
of his organization as he has best determined* The QA/QC SOP should contain
the essential elements described in this section.
2. Elements of a QA/QC SOP
2.1 All routine laboratory tasks should have written QA/QC Standard Operat-
ing Procedures. Standard Operating Procedures should be detailed
documents describing who does what, when, where, how, and why. They
shall be sufficiently complete and detailed to ensure that:
2.1.1 Data of known quality and integrity are generated.
2.1.2 The loss of data due to out-of-control conditions is minimized.
2.2 Standard Operating Procedures shall be:
2.2.1 Adequate to establish the traceabillty of standards, instru-
mentation, samples, and environmental data.
2.2.2 Simple, so a user with basic education, experience and/or
training can properly use them.
2.2.3 Complete enough so the user can follow the directions in a
stepwise manner.
2.2.4 Consistent with sound scientific principles.
2.2.5 Consistent with current EPA regulations, guidelines, and
contract requirements.
2.2.6 Consistent with the instrument manufacturer's specific instruc-
tion manuals.
2.3 Standard Operating Procedures shall also provide for documentation suffi-
ciently complete to:
2.3.1 Record the performance of all tasks and their results.
2.3.2 Explain the cause of missing data.
2.3.3 Demonstrate the validation of data each time they are recorded,
calculated, or transcribed.
E-4
10/86
-------
II.
2.4 To accomplish these objectives, Standard Operating Procedures should
address the major elements upon which the final quality of the contractors wor
depends. In the following descriptions these six major areas have been
divided into subelements, where applicable. These elements include but
are not limited to:
2.4.1 Organization and personnel,
2.4.2 Facilities and equipment,
2.4.3 Analytical methodology,
2.4.4 Sample custody procedures,
2.4.5 Quality control, and
2.4.6 Data handling.
3. Organization and Personnel
3.1 QA Policy and Objectives - Each organization should have a written
quality assurance policy that should be made known to all organization
personnel. Objectives should be established to produce data that meet
contract requirements in terms of completeness, precision, accuracy,
representativeness, documentation, and comparability. The SOP should
require the preparation of a specific QA plan for-the analysis.
3.2 QA Organization - The organization and management of the QA function
should be described in the contractor's SOP. Reporting relationships
and responsibilities should be clearly defined. A QA Coordinator or
Supervisor should be appointed and his responsibilities established.
A description of the QC paperwork flow should be available. There
should be a clear designation of those who are authorized to approve
data and results. Responsibilities for taking corrective action should
be assigned to appropriate management personnel.
3.3 Personnel training - It is highly desirable that there be a training
program for employees. This system should include motivation toward
producing data of acceptable quality and should involve "practice work"
by the new employee. The quality of this work can be immediately
verified and discussed by the supervisor, with appropriate corrective
action taken.
3.4 Document Control and Revisions The SOP should Include a system for
documenting:
3.4.1 Calibration procedures,
3.4.2 Analytical procedures,
10/86-
-------
II.
3.4.3 Computational procedures,
J.4.4 Quality control procedures,
3.4.5 Bench data,
3.4.6 Operating procedures, or any changes to these procedures, and
3.4.7 Laboratory notebook policy.
3.5 Procedures for making revisions to technical procedures or documents
must be clearly defined, with the lines of authority indicated. Proce-
dural revisions should be written and distributed to all affected
Individuals, thus ensuring implementation of changes.
Facilities and Equipment
4.1 Procurement and Inventory Procedures - Purchasing guidelines for all
equipment and reagents having an effect on data quality should be
well-defined and documented. Similarly, performance specifications
should be documented for all items of equipment having an effect on
data quality. Once any item which is critical to the analysis such as
an in situ instrument, or reagent is received and accepted by the
organisation, documentation should be retained o£ the type, age, and
acceptance status of the Item. Reagents should be dated upon receipt
in order to establish their order of use and to minimize the possi-
bility of exceeding their useful shelf life.
4.2 Preventive Maintenance - Preventive maintenance procedures should be
clearly, defined and written for each measurement system and required
support equipment. When maintenance activity is necessary, it should
be documented on standard forms maintained in logbooks. A history of
the maintenance record of each system serves as an indication of the
adequacy of maintenance schedules and parts inventory.
Analytical Methodology
5.1 Calibration and Operating Procedures - Calibration is the process of
establishing the relationship of a measurement system output to a
known stimulus. In essence, calibration is a reproducible reference
point to which all sample measurements can be correlated* A sound
calibration SOP should include provisions for documentation of frequency,
conditions, standards, and records reflecting the calibration history
of a measurement system.
5.1.1 The accuracy of Che calibration standards is .an important point
to consider since all data will be in reference to the standards
used. An SOP for verifying the accuracy of all working standards
against primary grade standards should be routinely followed.
E-6
10/86
-------
II.
5.2 Feedback and corrective action - The SOP should specify the corrective
action that is to be taken when an analytical or sampling error Is
discovered or the analytical system is determined to be out of control.
The SOP should require documentation of the correclve action and noti-
fication of the analyst of the error and correct procedures.
6. Sample Custody
6.1 Sample custody is a part of any good laboratory or field operation.
Where samples may be needed for legal purposes, "chain-of-custody"
procedures, as defined in Exhibit F must be used. However, at a
minimum, the following sample custody procedures should be addressed
in the QA/QC SOP.
6.2 Chain-of-custody in laboratory operations
6.2.1 Identification of responsible party to act as sample custodian
at the laboratory facility authorized to sign for incoming
field samples, obtain documents of shipment (e.g., bill of
lading number or mall receipt), and verify the data entered
onto the sample custody records.
6.2.2 Provision for a laboratory sample custody log consisting of
serially numbered standard lab-tracking report sheets.
6.2.3 Specification of laboratory sample custody procedures for sample
handling, storage and dlspersement for analysis.
7. Quality Control
7.1 Quality Control Procedures - The quality control procedures used during
analysis should be described and must conform to those described in
Exhibit E. The quality control checks routinely performed during
sample analysis include method blank analysis to establish analyte
levels, duplicate analysis to establish analytical precision, spiked
and blank sample analysis to determine analytical accuracy. The frequency
of these quality control checks are defined in the concract. Limits of
acceptance or rejection are also defined for analysis and control
charts should be used. Confirmation procedures should be described in
the SOP.
7.2 Control Checks and Internal Audits - A good SOP will make provision for
and describe control checks and internal audits by the contractor.
Several approaches are used for control checks. These Include:
7.2.1 Reference material analysis. Analytical reference materials
are available from several commercial and government sources,
or they may be prepared ln-house. The chemical analysis of
these materials has been well established. Such materials can
be analyzed alongside routine samples and Che results used to
check the accuracy of analytical procedures.
E-7
10/86
-------
II.
7*2*2 Blank analysis* The procedures and Che frequency of blank
analyses are defined in the contract.
7*2*3 Matrix spike and matrix spike duplicate analysis. The proce-
dures and the frequency of matrix spike analyses are defined in
the contract.
7.2*4 Internal audits* Internal audits should be periodically con-
ducted to evaluate the functioning of the QA SOP. This involves
an independent check of the performance of the laboratory
analysts to determine if prescribed procedures are closely
followed.
8. Data Handling
8.1 Data Handling, Reporting, and Recordkeeping - Data handling, reporting,
and recordkeeping procedures should be described. Data handling and
reporting includes all procedures used to record data on standard
forms, and in laboratory notebooks. The reporting format for different
types of bench data should be described and the forms provided- The
contents of notebooks should be specified.
8.1.1 Recordkeeping of this type serves at least two useful functions:
(1) it makes possible the reanalysls of a set of data at a future
time, and (2) it may be used in support of the experimental con-
clusions if various aspects of the analysis are called into
question.
8.2 Data Validation - Data validation procedures, defined ideally as a set
of computerized and manual checks applied at various appropriate levels of
the measurement process, should be in written form and clearly defined for
all measurement systems.
8.2.1 Criteria for data validation must be documented
and include limits on:
8*2.1.1 Operational parameters such as GC conditions;
8.2.1.2 Calibration data;
8*2*1.3 Special checks unique to each measurement, e.g.,
successive values/averages;
8.2.1*4 Statistical tests, e.g., outliers; and
8.2.1.5 Manual checks such as hand calculations.
8.2.2 The limits defined in the contract ensure a high probability of
detecting invalid data for either all or the majority of the
measurement systems. The required data validation activities
(GC operating conditions, analytical precision, etc.) should be
recorded on standard forms in a logbook.
10/86
-------
SECTION III VOA
VOLATILES QA/QC REQUIREMENTS
E-9
10/86
-------
Ill VOA
This section outlines the minimum quality control (QC) operations necessary to
satisfy the analytical requirements associated with the determination of volatile
organic TCI'compounds in Vater and soil/sediment samples. These QC operations
are as follows:
o Documentation of GC/MS Mass Calibration and Abundance Pattern
o Documentation of GC/MS Response Factor Stability
o Internal Standard Response and Retention Time Monitoring
o Method Blank Analysis
o Surrogate Spike Response Monitoring
o Matrix Spike and Matrix Spike Duplicate Analysis
PART 1 - TUNING AW) GC/MS MASS CALIBRATION
1. Summary
It Is necessary to establish that a given GC/MS meets the standard
mass spectral abundance criteria prior to initiating any on-going data
collection. This is accomplished through the analysis of p-Bromoflaoro—
benzene (BFB).
Definition: The tvelve (12) hour time period for GC/MS system tuning and
standards calibration (initial or continuing calibration criteria) begins
at the moment of Injection of the BFB analysis that the laboratory submits
as documentation of a compliant tune. The time period ends after twelve
(12) hours has elapsed according to the system clock.
1.1 p-Bromofluorobenzene (BFB)
1.1.1 Each GC/MS system used for the analysis of volatile TCL compounds
must be hardware tuned to meet the abundance criteria listed in
Table 1.1 for a maximum of a 50 nanogram injection of BFB.
Alternately, add SO ng of BFB solution to 5.0 ml of reagent
water and analyze according to Exhibit D VOA, Section IV. BFB
shall not he analyzed simultaneously with any calibration
standards or blanks. This criterion must l>e demonstrated daily
or for each twelve-hour time period, whichever Is more frequent.
If required, background subtraction must be straightforward and
designed only to eliminate column bleed or instrument background
ions. Background subtraction actions resulting In spectral
distortions for the sole purpose of meeting the contract speci-
fications are unacceptable.
NOTE: All Instrument conditions must be identical to those used
in sample analysis, except that a different temperature program
may be used.
1.1.2 BFB criteria MUST be met before any standards, samples, or blanks
are analyzed. Any samples analyzed when tuning criteria have
not been met may require reanalysls at no cost to the Agency.
E-10
10/86
-------
Ill VOA
1.1.3 Whenever Che contractor takes corrective action which may
change or affect the tuning criteria for OFTPP or BF3 (e.g.,
Ion source cleaning or repair, etc.), the tune must be
verified irrespective of the twelve-hour tuning requirements.
TABLE 1.1. BFB KEY IONS AND ABUNDANCE CRITERIA
Mass
Ion Abundance Criteria
50
15.0 - 40.0 percent of the base peak
75
30.0 - 60.0 percent of the base peak
95
base peak, 100 percent relative abundance
96
5.0 - 9.0 percent of the base peak
173
less than 2.0 percent of mass 174
174
greater than 50.0 percent of the base peak
175
5.0 - 9.0 percent of mass 174
176
greater than 95.0 percent but less than 101.0
percent of mass 174
177
5.0 - 9.0 percent of mass 176
1.2 Documentation
The contractor shall provide documentation of the calibration in the
form of a bar graph spectrum and as. a mass listing.
1.2.1 The contractor shall to complete a Form V (GC/MS Tuning and
Mass Calibration) each time an analytical system is tuned.
In addition, all standards, samples, blanks, matrix spikes,
and matrix spike duplicates analyzed during a particular tune
must be summarized in chronological order on the bottom of the
appropriate Form V. Detailed instructions for the completion
of Form V are in Exhibit B, Section III.
PART 2 - CALIBRATION OF THE GC/MS SYSTEM
2. Summary
Prior to the analysis of samples and required blanks and after tuning criteria
have been met, the GC/MS system must be initially calibrated at a minimum of
five concentrations to determine the linearity of response utilizing TCL com-
pound standards. Once Che system has been calibrated, the calibration must
be verified each twelve (12) hour time period for each GC/MS system.
2.1 Prepare calibration standards as described In Exhibit D VOA, Section IV,
to yield the following specific concentrations:
E-U
10/86
-------
Ill VOA
2.1.1 Volatile TCL Compounds
Initial calibration of volatile TCL compounds is required at 20,
50, 100, 150 and 200 ug/L. Surrogate and Internal standards
shall be used with each of the calibration standards. Utilizing
the analytical protocol specified in Exhibit 0 this will result
in 100-1000 total ng analyzed. If an analyte saturates at the
200 ug/L concentration level, and the GC/MS system is calibrated
to achieve a detection sensitivity of no less than 5 ug/L, the
laboratory must document it on Form VI and In the Case narrative,
and attach a quantitation report and RIC. In this instance,
the laboratory should calculate the results based on a four-point
initial calibration for the specific analyte that saturates.
The use of separate calibration methods which reflect the two
different low and medium soil/sediment methods is required.
Secondary Ion quantitation is only allowed when there are
sample interferences with the primary ion. If secondary ion
quantitation is used, document the reasons in the Case Narrative.
Analyze all method blanks and standards under the same conditions
as the samples.
The USEPA plans to develop performance based criteria for response
factor data acquired during this program. To accomplish this goal, the
Agency has specified both the concentration levels for initial calibra-
tion and has also specified the specific internal standard to be used
on a compound-by-compound basis for quantitation (see Table 2.1).
Establishment of standard calibration procedures is necessary and
deviation? by the contractor will not be allowed.
Analyse each calibration standard and tabulate the area of the primary
characteristic ion (Exhibit 0 VOA, Table 3) against concentration for
each compound including all contract required surrogate compounds. The
relative retention times of each compound in each calibration run
should agree within 0.06 relative retention time units. Late eluting
compounds usually will have much better agreement.
Using Table 2.1 and Equation 2.1, calculate the relative response
factors (RRF) for each compound at each concentration level.
^s
RRF - x Eq. 2.1
*is
where,
Ax « Area of the characteristic ion for the compound to be measured.
A^s ¦ Area of the characteristic ion for the specific internal standards
from Table 2.1 or 2.2.
C^s * Concentration of the internal standard (ng/uL).
Cx ¦ Concentration of the compound to be measured (ng/uL).
E-12
10/86
-------
Ill VOA
TABLE 2.1. VOLATILE INTERNAL STANDARDS WITH CORRESPONDING
TCL ANALYTES ASSIGNED FOR QUANTITATION
Bromochloromethane 1,4-Difluorobenzene Chlorobenzene-d5
Chloromethane
Bromoraethane
Vinyl Chloride
Chloroethane
Methylene Chloride
Acetone
Carbon Disulfide
L,1-Dichloroethene
1.1-Dichloroethane
1.2-Dichloroethene(total)
Chloroform
1,2-Dichloroethane
I,2-Dichloroethane-d4
(surr)
2-Butanone
1.1.1-Trichloroethane
Carbon Tetrachloride
Vinyl Acetate
Bromodichloromethane
1,2-Dichloropropane
trans-1,3-Dichloropropene
Trichloroethene
Dibromochloromethane
1.1.2-Trichloroethane
Benz ene
cis-l,3-Dichloropropene
Bromoform
2-Hexanone
4-Methyl-2-Pentanone
Tetrachloroethene
1,1, 2,2-Tetrachloroetl
Toluene
Chlorobenzene
Ethylbenzene
Styrene
Xylene(total)
Bromofluorobenz ene
(surr)
Toluene—d0 (surr)
(surr) ¦ surrogate compound
2.3.1 Using the relative response factors (RRF) from the initial calibra-
tion, calculate the percent relative standard deviations (ZRSD)
for compounds labeled on Form IV as Calibration Check Compounds and
shown in Table 2.2 (see 2.6.2), using Equation 2.2 below.
SD
ZRSD - X 100 Eq. 2.2
x
where,
RSD ¦ Relative Standard Deviation
SD ¦ Standard Deviation of Initial relative response factors (per
compound)
where: SD • \ 2 (*i - x)^
N-l
x ¦ mean of initial relative response factors (per compound)
The %RSD for each individual Calibration Check Compound must
be less than or equal to 30.0 percent. This criteria must be
met for the initial calibration to be valid.
E-13
10/86
-------
Ill VOA
2.4 A ayscam performance check must be performed eo ensure Chat minimum
average relative response factors are met before the calibration curve
is used*
2.4.1 For volatiles, the five System Performance Check Compounds
(SPCCs) are: chloromethane, 1,1-dichloroethane, bromoform,
1,1,2,2-tetrachloroethane and chlorobenzene. The minimum
acceptable average relative response factor (RRF) for these com-
pounds is 0.300, 0.250 for Bromoform. These compounds typically
have RRF's of 0.4-0.6 and are used to check compound Instability
and check for degradation caused by contaminated lines or
active sites in the system. For instance:
o Chloromethane - this compound is the most likely compound
to be lost if the purge flow is too fast.
o Bromoform - this compound is one of the compounds most
likely to be purged very poorly if the purge flov is too
slow. Cold spots and/or active sites in the transfer lines
may adversely affect response. Response of the quantitation
ion (m/z 173) is directly effected by the tuning o£ BFB at
ions m/z 174/176. Increasing the m/z 174/176 ratio may
Improve bromoform response.
0 Tetrachloroethane, 1,1-Dichloroethane - These compounds
can be deteriorated by contaminated transfer lines in purge
and trap systems and/or active sites in trapping materials.
2.4.2 The initial calibration is valid only after both the ZRSD for
CCC compounds and the minimum RRF for SPCC have been mee. Only
after both these criteria are met can sample analysis begin.
2.5 Documentation
Once the Initial calibration is validated, calculate and report the
average relative response factor (RRF) and percent relative standard
deviation (ZRSD) for all TCL compounds. The contractor shall complete
and submit Form V (the GC/MS tune for the initial calibration) and Form .
VI (Initial Calibration Data) for each Instrument used to analyze
samples under this protocol. Detailed instructions for completion of
Form VI are in Exhibit B, Section III.
2.6 Continuing Calibration
A calibration standard(s) containing all volatile TCL compounds, in-
cluding all required surrogates, must be performed each twelve hours
during analysis (see definition of twelve hour time period, paragraph
1. of this Section). Compare the relative response factor data from
the standards each twelve hours with the average relative response
factor from the initial calibration for a specific Instrument. A
system performance check must be made each twelve hours. If the SPCC
criteria are met, a comparison of relative response factors is made for
E-14
10/86
-------
Ill VOA
all compounds. This Is Che same check chat is applied during che
inicial calibration (Form VI). If the minimum relative response factors
are not met, Che system must be evaluated and corrective action oust be
taken before sample analysis begins*
2.6.1 Some possible problems are scandard mixture degradation,
Injection port inlet contamination, contamination at the front
end of ehe analytical column, and active sites in the column or
chromatography system. This check must be met before analysis
begins. The minimum relative response factor (RRF) for volatile
System Performance Check Compounds (SPCC) is 0.300 (0.250 for
Bromoform).
2.6.2 Calibration Check Compounds (CCC)
After the system performance check is met, Calibration Check
Compounds listed in Table 2.2 are used to check the validity of
the initial calibration. Calculate the percent difference
using Equation 2.3.
RRTX - RSJC
Z Difference » — x 100 Eq. 2.3
RRFj
where
rSFj * average relative response factor from initial calibration
RRFC « relative response factor from current calibration check
standard
2*6.2.1 If Che percent difference for any compound is greater than
202, che laboratory should consider this a warning limlc.
If che percenc difference for each CCC is less than or
equal to 25.0Z, the initial calibration is assumed Co be
¦ valid. If the criteria are not met (>25.0% difference),
for any one calibration check compound, corrective action
MUST be taken. Problems similar to those listed under SPCC
could affect this criteria. If no source of the problem
can be determined after corrective action has been taken,
a new initial five point calibration MUST be generated.
These criteria MUST be met before sample analysis begins.
TABLE 2.2. VOLATILE CALIBRATION CHECK COMPOUNDS
1.1-Dichloroethene
Chloroform
1.2-Dichloropropane
Toluene
Ethylbenzene
Vinyl Chloride
E-15
10/86
-------
Ill VOA
2.6.3 Concentration Levels for Continuing Calibration Check
The USEPA plans to evaluate the long term stability of relative
resporwe factors during this'program. Standardization among
contract laboratories is necessary to reach these long term
goals. Along with contract specified concentrations for initial
calibration, the USEPA is requiring specific concentrations for
each continuing calibration standard(s).
2.6.3.1 The concentration for each volatile TCL compound in
the continuing calibration standard(s) is 50 ug/L.
2.7 Documentation
The contractor shall complete and submit a Form VII for each GC/MS
system utilised for each twelve hour time period. Calculate and report
the relative response factor and percent difference (ZD) for all compounds.
Ensure that the minimum RRF for volatile SPCC's is 0.300 and 0.250 for
Bromoform. The percent difference (ZD) for each CCC compound must be
less than or equal to 25.0 percent. Additional instructions for
completing Form VII are in Exhibit B, Section III.
PART 3 - METHOD BLANK ANALYSIS
3. Summary
A method blank is a volume of deionized, distilled laboratory water for
water samples, or a purified solid matrix for soil/sediment samples, carried
through the entire analytical scheme. The method blank volume or weight
must be approximately equal to the sample volumes or sample weights being
processed.
3.1 Method blank analysis must be performed at the following frequency:
3.1.1 For the analysis of volatile TCL compounds, a method blank analysis
must be performed once for each 12-hour time period during the
analysis of samples from:
o each Case, OR
o each 14 calendar day period during which samples in a Case are
received (said period beginning with the receipt of the first
sample in that Sample Delivery Group), OR
o each 20 samples in a Case that are of similar matrix (water or
soil) or similar concentration (soil only),
whichever is most frequent, on each GC/MS system used to analyse
samples.
3.2 It is the contractor's responsibility to ensure that method interferences
caused by contaminants in solvents, reagents, glassware, and other sample
processing hardware that lead to discrete artifacts and/or elevated base-
lines in gas chromatograms be minimized.
E-16
10/86
-------
Ill VOA
3.2.1 For Che purposes of this protocol, an acceptable laboratory method
blank should meet the criteria of paragraphs 3.2.1.1 and 3.2.1.2.
3.2.1.1 A method blank for volatile analysis must contain no
greater than five times (5X) the Contract Required
Quantitation Limit (CRQL from Exhibit C) of methylene
chloride, acetone, toluene, and 2-butanone.
3.2.1.2 For all other TCL compounds not listed above, the method
blank must contain less than the Contract Required
Quantitation Limit of any single TCL analyte.
3.2.2 If a laboratory method blank exceeds these criteria, the contractor
must consider the analytical system to be out of control. The source
of the contamination must be investigated and appropriate corrective
measures MUST be taken and documented before further sample analysis
proceeds. All samples processed with a method blank that is out of
control (i.e., contaminated) MUST be reextracted/repurged and
reanalyzed at no additional cost to the Agency. The Laboratory
Manager, or his designee, must address problems and solutions in
the Case Narrative (Exhibit B).
3.3 Documentation
The contractor shall report results of method blank analysis using the
Organic Analysis Data Sheet (Form I) and the form for tentatively Identified
compounds (Form I, TIC). In addition, the samples associated with each
method blank must be summarized on Form IV (Method Blank Summary). Detailed
instructions for the completion of these forms can be found i.n Exhibit 8,
Section III.
3.3.1 The Contractor shall report ALL sample concentration data as
UNCORRECTED for blanks.
PART 4 - SURROGATE SPIKE (SS) ANALYSIS
4. Summary
Surrogate standard determinations are performed on all samples and blanks.
All samples and blanks are fortified with surrogate spiking compounds
before purging or extraction in order to monitor preparation and analysis
of samples.
4.1 Each sample, matrix spike, matrix spike duplicate, and blank are spiked
with surrogate compounds prior to purging or extraction. The surrogate
spiking compounds shown in Table 4.1 are used to fortify each sample,
matrix spike, matrix spike duplicate, and blank with the proper concen-
trations. Performance based criteria are generated from laboratory results.
Therefore, deviations from the spiking protocol will not be permitted.
E-17
10/86
-------
Ill VOA
TABLE 4.1. SURROGATE SPIKING COMPOUNDS
Compounds
Amount in Sample/Extract*
(before any optional dilutions)
Fraction
Water
Low/Medium Soil
Toluene-dg VOA
4-Bromofluorobeozene VOA
1,2-D1chloroethane-d4 VOA
50 ug
50 ug
50 ug
50 ug
50 ug
50 ug
* At the time of injection.
4.2 Surrogate spike recovery must be evaluated by determining whether the
concentration (measured as percent recovery) falls inside the contract
required recovery limits listed in Table 4.2.
TABLE 4.2. CONTRACT REQUIRED SURROGATE SPIKE RECOVERY LIMITS
Fraction
Surrogate Compound
Water
Low/Medium Soil
VOA
VOA
VOA
Toluene-dg
4-Bromofluorobenz ene
1,2-Dichloroethane-d4
88-110
86-115
76-114
81-117
74-121
70-121
4.3 Treatment of surrogate spike recovery information is according to
paragraphs 4.3.1 through 4.3.2.
4.3.1 Method Blank Surrogate Spike Recovery
The laboratory must take the actions listed below if recovery of
any one surrogate compound in the volatiles fraction of the method
blank is outside of the required surrogate spike recovery limits.
4.3.1.1 Check calculations to ensure that there are no errors; check
internal standard and surrogate spiking solutions for
degradation, contamination, etc; also check instrument
performance.
4.3.1.2 Reanalyze the blank or extract if steps in 4.3.1.1 fail
to reveal the cause of the noncompliant surrogate recoveries«
E-18
10/86
-------
Ill VOA
4.3.1.3 If che blank is a methanol extract for medium level soil
samples, reextract and reanalyze Che blank If seeps In
4.3.1.2 fall Co reveal che cause of che noncompllanc
surrogate recoveries.
4.3.1.4 If che measures lisced In 4.3.1.1 Chru 4.3.1.3 fail co
correct che problem, che analyclcal system must be con-
sidered out of control. The problem MUST be corrected
before conclnuing.
This may mean recallbracing Che inscrumencacion but ic may
also mean more extensive acCion. The specific correcclve
accion is left up Co che GC/MS operacor. When surrogate
recovery(ies) in Che blank is outside of Che concracc
required windows, all samples associaCed with that blank
MUST be reanalyzed at no addiclonal cost to che Agency.
4.3.2 Sample Surrogace Spike Recovery
The laboracory muse Cake Che accions lisced below if recovery- of
any one surrogace compound in che volaciles fraction of the sample
is outside of the concracc surrogace spike recovery limits.
4.3.2.1 The concraccor laboracory shall documenc (in this
insGance, documenc means Co wrice down and discuss
problem and correcclve accion taken in che Case Narracive
(see Exhibic B) deviations outside of acceptable qualiey.
control limics by Caking che following acelons:
4.3.2.1.1 Check calculaclons Co ensure chac there are no
errors; check inceraal standard and surrogace
spiking solucions for degradaeion, contami-
nation, etc; also check inscrumenc performance.
4.3.2.1.2 If Che seeps in 4.3.2.1.1 fail Co reveal a
problem, then reanalyze ehe sample or excrace.
If reanalysis of Che sample or excrace solves
Che problem, Chen che problem was within che
laboracory's concrol. Therefore, only submit
daca from Che analysis wich surrogace spike
recoveries wlchin the concracc windows. This
shall be reporced as such on all daca
deliverables.
4.3.2.1.3 If Che sample was a soil excracced wich meehanol
and Che seeps in 4.3.2.1.2 fall Co solve che
problem, Chen reextracc and reanalyze che sample.
If Che reexcraccion and reanalysis solves che
problem, Chen che problem was in che laboratory's
control. Therefore, only submit data from
che extraction and analysis with surrogate
E-19 10/86
-------
Ill VOA
spike recoveries within Che contract windows.
This shall be considered the initial analysis
and shall be reported as such on all data
deliverables.
4.3.2.1.4 If the reextraction and/or reanalysis of the
sample does not solve the problem; i.e.,
surrogate recoveries are outside the contract
windows for both analyses, then submit the
surrogate spike recovery data and the sample
data from both analyses according to paragraph
4.4. Distinguish between the initial analysis
and the reanalysis on all data deliverables,
using the sample suffixes specified in Exhibit B.
4.4 Documentation
The contractor is required to report surrogate recovery data for the
following:
o Method Blank Analysis
o Sample Analysis
o Matrix Spike/Matrix Spike Duplicate Analyses
o All sample reanalyses that substantiate a matrix effect
The surrogate spike recovery data is summarized on the Surrogate Spike
Percent Recovery Summary (Form II). Detailed instructions for the completion
of Form II are in Exhibit B, Section III.
PART 5 - MATRIX SPIKE/MATRIX SPIKE DUPLICATE ANALYSIS (MS/MSD)
5. Summary
In order to evaluate the matrix effect of the sample upon the analytical method-
olgy, the USEPA has developed the standard mixes listed in Table 5.1 to be used
for matrix spike and matrix spike duplicate analyses. Th
-------
Ill VOA
5.2 Use Che compounds listed in Table 5.1 eo prepare matrix spiking solutions
according to protocols described in Exhibit D VOA. The analytical protocols
in Exhibit 0 VOA stipulate the amount of matrix spiking solution to be added
to the sample aliquots. Each method allows for optional dilution steps
which must be accounted for when calculating percent recovery of the matrix
spike and matrix spike duplicate samples.
TABLE 5.1. MATRIX SPIKING SOLUTIONS
Volatiles
Chlorobenz ene 1,1-Dichloroethene
Toluene Trlchloroethene
Benz ene
5.2.1 Samples requiring optional dilutions and chosen as the matrix spike/
matrix spike duplicate samples, must be analyzed at Che same dilution
as the original unsplked sample.
5.3 Individual component recoveries of Che oacrlx spike are calculated using
Equation 5.1.
Matrix Spike Percent Recovery « — x 100 Eq. 5.1
where,
SSR * Spike Sample Results
SR ¦ Sample Result
SA * Spike Added from spiking mix
5.4 Relative Percent Difference (RPO)
The contractor is required to calculate the relative percent difference
between the matrix spike and matrix spike duplicate.- The relative percent
differences (RPO) for each component are calculated using Equation 5.2.
Di — D2 Eq. 5.2
RPO — x 100
(D! + D2)/2
where,
RPD • Relative Percent Difference
Di » First Sample Value
O2 ¦ Second Sample Value (duplicate)
E-21 10/86
-------
Ill VOA
5.5 Documentation
The matrix spike (MS) results (concentrations) for nonspiked volatile TCL
compounds shall be reported on Form I (Organic Analysis Data Sheet) and
the"matrix spike percent recoveries shall be summarized on Form III (MS/MSD
Recovery). These values will be used by EPA to periodically update existing
performance based QC recovery limits (Table 5.2).
The results for nonspiked volatile TCL compounds in the matrix spike
duplicate (MSD) analysis shall be reported on Form I (Organic Analysis
Data Sheet) and the percent recovery and the relative percent difference
shall be summarized on Form III (MS/MSD Recovery). The RPD data will be
used by EPA to evaluate the long term precision of the analytical method.
Detailed instructions for the completion of Form III are in Exhibit B,
Section III.
TABLE 5.2. MATRIX SPIKE RECOVERY LIMITS
Fraction
Matrix Spike Compound
Water
Soil/Sediment
VOA
1,1-Dichloroethene
61-145
59-172
VOA
Trichlorethene
71-120
62-137
VOA
Chlorobenzene
75-130
60-133
VOA
Toluene
76-125
59-139
VOA
Benz ene
76-127
66-142
PART 6 - SAMPLE ANALYSIS
6. Summary
The intent of Part 6 is to provide the Contractor with a brief summary of
ongoing QC activities involved with sample analysis. Specific references
are provided to help the Contractor meet specific reporting and deliverables
requirements of this contract.
6.1 Sample Analysis
Samples can be analyzed upon successful completion of the initial QC
activities. Vhen twelve (12) hours have elapsed since the initial tune
was completed, it is necessary to conduct an instrument tune and calibra-
tion check analysis (described in Part 2 of this Section). Any major system
maintenance, such as a source cleaning or installation of a new column,
may necessitate a retune and recalibratlon irrespective of the twelve-hour
requirement (see Initial Calibration, Part 2). Minor maintenance should
necessitate only the calibration verification (Continuing Calibration,
Part 2)
6.1.1 Internal Standards Evaluation - Internal standard responses and re-
tention times In all samples must be evaluated immediately after or
during data acquisition. If the retention time for any internal
E-22
10/86
-------
Ill VOA
standard changes by more Chan 30 seconds, the chromatographic
system must be inspected for malfunctions, and corrections made as
required. The extracted Ion current profile (EICP) of the Internal
standards must be monitored and evaluated for each sample, blank,
matrix spike, and matrix spike duplicate. The criteria are described
in detail in the instructions for Form VIII, Internal Standard Area
Summary (see Exhibit B, Section III). If the extracted ion current
profile (EICP) area for any internal standard changes by more than
a factor of two (-502 to 1002), from the latest daily (12 hour time
period) calibration standard, the mass spectrometric system must b«
inspected for malfunction, and corrections made as appropriate.
Breaking off 1 foot of the column or cleaning the injector sleeve
will often Improve high end sensitivity for the late elutlng compounds;
repositioning or repacking the front end of the column will often
improve front end column performance. Poor injection technique can
also lead to variable IS ratios. When corrections are made, re-
analysis of samples analyzed while the system was malfunctioning is
necessary.
6.1.1.1 If after reanalysls, the EICP areas for all internal
standards are Inside the contract limits (-502 to +1002),
then the problem with the first analysis is considered to
have been within the control of the laboratory. Therefore,
only submit data from the analysis with EICP's within the
contract limits. This is considered the initial analysis
and must be reported as such on all data deliverables.
6.1.1.2 If the reanalysls of the 3ample does not solve the problem,
i.e., the EICP areas are outside the contract limits for.
both analyses, then submit the EICP data and sample data
from both analyses. Distinguish between the initial analysis
and Che reanalysls on all data deliverables, using the
sample suffixes specified in Exhibic B. Document in the
Case Narrative all inspection and correcclve actions taken.
6.1.2 Each analytical run must also be checked for saturation. The level
at which an individual compound will saturate the detection system
is a function of the overall system sensitivity and the mass spectral
characterlsclcs of chac compound. The lnicial method calibration
(Pare 2) requires chat the system should not be saturated for high
response compounds at 200 ug/L for VOA TCL compounds.
6.1.2.1 If any compound in any sample exceeds the initial calibra-
tion range, that sample must be diluted, the internal
standard concentration readjusted, and the sample re-
injected, as described in specific methodologies in
Exhibit D VOA. Secondary ion quantitation is only allowed
when there are sample matrix interferences with the
primary ion. If secondary ion quantitation is performed,
document thhe reasons in the Case Narrative.
E-23
10/86
-------
Ill VOA
6.1*2.2 If the dilution of che sample causes any compound detected
In the first analysis to be undetectable In the second
analysis, then the results of both analyses shall be
•reported on separate Forms I, according to the instructions
in Exhibit B.
6.1.3 Qualitative Analysis
The compounds listed in the Target Compound List (TCL), Exhibit C,
shall be identified by an analyst competent in the interpretation
of mass spectra, by comparison of the suspect mass spectrum to the
mass spectrum of a standard of the suspected compound. Two criteria
must be satisfied to verify the identifications: (1) elution of the
sample component at the same GC relative retention time as the stan-
dard component, and (2) correspondence of the sample component and
standard component mass spectra (Exhibit 0, Section IV).
6.1.3.1 For establishing correspondence of Che GC relative reten-
tion time (RRT), the sample component RRT must compare
vlthln +0.06 RRT units of the RRT of the standard component.
For reference, the standard must be ran on the »ame shift
as the sample.
6.1.3.2 For comparison of standard and sample component mass spectra,
mass spectra obtained on the Contractor's GC/MS are required.
The BFB tuning requirements listed in Part 1 of this Section
must be met on that same GC/MS.
6.1.3.2.1 The requirements for qualitative verification
by comparison of mass spectra are as follows:
o All ions present in the standard mass spectra
at a relative intensity greater than 10Z
(most abundant ion in the spectrum
equals 100Z) must be present In the
sample spectrum.
o The relative intensities of ions specified'
in the above paragraph must agree vlthln
+20Z between che standard and sample
spectra.
o Ions greater than 10Z in the sample
spectrum but not present In the
standard spectrum must be considered and
accounted for by the analyst making the
comparison. When GC/MS computer data
processing programs are used to obtain
the sample component spectrum, both the
processed and che raw spectra must be
evaluated. In Task III, Che verifica-
tion process should favor false positives
(Exhibit D, Section IV).
E-24
10/86
-------
Ill VOA
6.1.3.2.2 If a compound cannot be verified by all of
Che criteria in 6.1.3.2.1, but in the technical
judgement of the mass spectral interpretation
specialist the identification is correct, the
contractor shall report the identification and
proceed with the quantitation.
6.1.3.3 A library search shall be executed for nonsurrogate and
non-TCL sample components for the purpose of tentative
Identification. For this purpose, the 1985 or most recent
available version of the National Bureau of Standards Mass
Spectral Library, containing 42,261 spectra should be used.
6.1.4 Quantitation
6.1.4.1 TCL components Identified shall be quantitated by the
internal standard method. The internal standards used
shall be the ones assigned in Table 2.1 of this Section.
The EICF area of characteristic ions of TCL analytes are
used (Exhibit 0 VOA, Section IV).
6.1.4.2 An estimated concentration for non-TCL components tentatively
identified shall be quantitated by the internal standard
method. For quantification, the nearest internal standard
free of interferences must be used.
6.1.4.3 Calculate surrogate standard recovery (see Part 4) for all
surrogate compounds la all samples, blanks, matrix spikes,
and matrix spike duplicates. If recovery is within contractual
limits, report on Form II (see Exhibit B). If recovery is
outside contractual limits, take specific steps listed in
Surrogate Spike Recoveries (Fart 4).
6.1.4.4 Calculate matrix spike and matrix spike duplicate percent
recovery (see Part S of this Section) for all compounds
and report results on Form III (see Exhibit B). Calculate
Relative Percent Differences (RPD's) for all matrix spiking
compounds and report results on Form III. Ensure that the
proper frequency of MS/MSD analysis is maintained.
6.1.5 Reporting and Deliverables
Refer to Exhibit B of this Statement of Work for specific details
on contract deliverables and reporting formats. Exhibit B contains
specific instructions for completing all required Forms, as well
as a detailed itemization of reporting and deliverables requirements.
Exhibit H contains che format requirements for delivery of data in
computer-readable format.
E-25 10/86
-------
SECTION III SV
SEMIVOLATILES QA/QC
REQUIREMENTS
E-26
10/86
-------
Ill sv
This Section outlines Che minimum quality control (QC) operations necessary
to satisfy the analytical requirements associated vlth the determination of semi-
volatile organic TCL compounds in water and soil/sediment samples. These QC
operations are as follows:
o Documentation of GC/MS Mass Calibration and Abundance Pattern
o Documentation of GC/MS Response Factor Stability
o Internal Standard Response and Retention Time Monitoring
o Method Blank Analysis
o Surrogate Spike Response Monitoring
o Matrix Spike and Matrix Spike Duplicate Analysis
PART 1 - TUNING AND GC/MS MASS CALIBRATION
1. Summary
It is necessary to establish that a given GC/MS meets the standard mass
spectral abundance criteria prior to initiating any on-going data collection.
This is accomplished through Che analysis of Decafluorotriphenylphosphine
(DFTPP).
Definition: The twelve (12) hour time period for GC/MS system tuning and
standards calibration (initial or continuing calibration criteria) begins
at the moment of injection of Che DFTPP analysis that Che laboracory submits
as documencacion of a coraplianc tune. The cime period ends afcer twelve (12)
hours has elapsed according Co Che syscem clock.
1.1 Decafluorocriphenylphosphine (DFTPP)
1.1.1 Each GC/MS system used for che analysis of semivolatile or
pesclclde TCL compounds anise be hardware Cuned Co meec Che
abundance cricerla lisced in Table 1.2 for a SO ng injection
of decafluorocriphenylphosphine (DFTPP). DFTPP may be analyzed
separately or as part of the calibration standard. The criteria
must be demonstrated dally or for each twelve (12) hour period,
whichever is more frequent, before samples can be analysed.
DFTPP must be injected to meet this criterion. If required,
background subtraction must be straightforward and designed only
to eliminate column bleed or instrument background ions.
Background subtraction actions resulting in speccral distortions
for Che sole purpose of meecing che contract specifications are
unacceptable. NOTE: All inscrument condicions muse be identical
to those used in sample analysis, except that a different
temperature program may be used.
E-27
10/86
-------
Ill sv
1.1.2 Whenever che contractor cakes corrective accion which may
change or affect che tuning criteria for DFTPP (e.g., ion
source cleaning or repair, etc.), Che cune muse be verified
irrespective of the 12-hour tuning requirements.
TABLE 1.2. DFTPP KEY IONS AND ION ABUNDANCE CRITERIA
Mass Ion Abundance Criteria
51
30.0 - 60.0 percent of mass 198
68
less than 2.0 percent of mass 69
70
less than 2.0 percent of mass 69
127
40.0 - 60.0 percent of mass 198
197
less than 1.0 percent of mass 198
198
base peak, 100 percent relative abundance
199
5.0 -9.0 percent of mass 198
275
10.0 - 30.0 percent of mass 198
365
greater than 1.00 percent of mass
198
441
present but less than mass 443
442
greater than 40.0 percent of mass
198
443
17.0 - 23.0 percent of mass 442
1.2 Documentatlon
The concractor shall provide documentation of che calibration in che
form of a bar graph spectrum and as a mass lisclng.
1.2.1 The contractor shall complete a Form V (GC/MS Tuning and Mass
Calibration) each time an analytical system Is tuned. In
addition, all samples, standards, blanks, matrix spikes, and
macrlx spike duplicates analyzed during a particular tune must
be summarized in chronological order on the bottom of the appro-*
priate Form V. Detailed instructions for the completion of Form
V are found in Exhibit B, Section III.
PART 2 - CALIBRATION OF THE GC/MS SYSTEM
2* Summary
Prior to the analysis of samples and required blanks and after tuning cri-
teria have been met, the GC/MS system must be initially calibrated at a
minimum of five concentrations to decermlne Che llnearlcy of response
ucilizlng TCL compound scandards. Once che sysCem has been calibrated,
the calibration must be verified each twelve (12) hour Cime period for
each GC/MS system.
2.1 Prepare calibracion standards as described in Exhibit D SV, Section IV,
to yield the following specific concentrations:
E-28
10/86
-------
Ill sv
2.1.1 Semivolatile TCL Compounds
Inlelal calibration of semivolatile TCL compounds is required
at 20, 50, 80, 120, and 160 total nanograms. If an analyte
saturates at the 160 total nanogram concentration level, and
the GC/MS system is calibrated to achieve a detection sensi-
tivity of no less than the CRQL, the laboratory must document
it on Form VI and in the Case narrative, and attach a quantita-
tion report and RIC. In this instance, the laboratory should
calculate the results based on a four-point initial calibration
for the specific analyte. The use of a secondary ion for quanti-
tation is only allowed when there are sample interferences wleh
the primary ion. If secondary ion quantitation is performed,
document the reasons in the Case Narrative. Nine compounds:
Benzoic Acid, 2,4-Dinitrophenol, 2,4,5-Trichlorophenol,
2-Nitroaniline, 3-Nitroaniline, 4-Nitroaniline, 4-Nitrophenol,
4,6-Dinitro-2-Methylphenol, and Pentachlorophenol will only
require a four-point initial calibration at 50, 80, 120, and 160
total nanograms since detection at less than 50 nanograms per
injection is difficult.
2.2 The USEPA plans to develop performance based criteria for response factor
data acquired during this program. To accomplish this goal, the Agency
has specified both the concentration levels for initial calibration and
has also specified the specific Internal standard to be used on a
compound-by-compound basis for quantitation (Table 2.2). Establishment
of standard calibration procedures is necessary and deviations by
the contractor will not be allowed.
2.3 Analyze each calibration standard and tabulate the area of the primary
characteristic ion (Exhibit 0 SV, Table 4) against concentration for
each compound including all contract required surrogate compounds*
The relative retention times of each compound in each calibration run
should agree within 0.06 relative retention time units. Late elutlng
compounds usually will have much better agreement.
Using Table 2.2, calculate the relative response factors (RRF) for each
compound at each concentration level using Equation 2.1*
^ cis
RRF ¦ x Eq. 2.1
*13
where,
Ax m Area of the characteristic Ion for the compound to be measured.
A^s ¦ Area of the characteristic ion for the specific internal
standards from Table 2.1 or 2.2.
Cis - Concentration of the internal standard (ng/uL).
C^ ¦ Concentration of the compound to be measured (ng/uL).
E-29
10/86
-------
Ill sv
2.3.1 Using the relative response factors (RRF) from the initial
calibration, calculate the percent relative standard deviations
(ZRSD) for compounds labeled on Form VI as Calibration Check
Compounds and shown in Table 2.3 (see 2.6.2) using Equation 2.2.
SD
ZRSD - —— X 100 Eq. 2.2
x
where,
RSD " Relative Standard Deviation
SD ¦ Standard Deviation of initial response factors (per
compound)
where: SD ¦ _
V 1-1 ¦
N-l
x ¦ mean of initial relative response factors (per compound)
The ZRSD for each Individual Calibration Check Compound must be
less than or equal to 30.0 percent. This criteria must be met
for the initial calibration to be valid.
2.4 A system performance check must be performed to ensure Chat minimum aver-
age relative response factors are met before the calibration curve is 'used.
2.4.1 For semivolatiles, the System Performance Check Compounds
(SPCC's) are: N-Nitroso-Di-n-Propylamine, Hexachlorocyclo-
pentadiene, 2,4-Dini trophenol and 4-Nitrophenol. The minimum
acceptable average relative response factor (RRF) for these com-
pounds is 0.050. SPCC's typically have very low RRFs (0.1-0.2)
and tend to decrease in response as the chromatographic system
begins to deteriorate or the standard material begins to deter-
iorate. These compounds are usually the first to show poor
performance. Therefore, they muse meet Che minimum requirement
when the system Is calibrated.
2.4.2 The Initial calibration is valid only after both the ZRSD for
CCC compounds and Che minimum RRF for SPCC have been met. Only
after both these criteria are met can sample analysis begin.
2.5 Documentation
Once the initial calibration is validated, calculate and report the
average relative response factor (RRF) and percent relative standard
deviation (ZRSD) for all TCL compounds. The contractor shall complete
and submit Form V (the GC/MS tune for the initial calibration) and Form
VI (Initial Calibration Data) for each instrument used to analyze
samples under this protocol. Detailed Instructions for completion of
Form VI are in Exhibit B, Section III.
E-30 10/86
-------
TABLE 2.2. SEMIVOLATILE INTERNAL STANDARDS WITH CORRESPONDING TCL ANALYTES ASSIGNED FOR QUANTITATION
1,4-Dichlorobenzene-d
Naphthalene-d
Acenaphthene-d
Phenanthrene-d
Chrysene-d
Perylene-d
Phenol
Nitrobenzene
Hexachlorocyclo-
4,6-Dinitro-2-
Pyrene
Di-n-octyl
bis(2-Chloroethyl)
Isophorone
pentadiene
methylphenol
Butylbenz yl
Phthalate
ether
2-Nltrophenol
2,4,6-Trichloro-
N-nitrosodi-
Phthalate
Benzo(b)fluor-
2-Chlorophenol
2,4-Di«ethyl-
phenol
phenylanine
3,3'-Dichloro-
anthene
1,3-Dichlorobenzene
phenol
2,4,5-Trichloro-
1,2-Diphenylhy-
benzidine
Benzo(k)fluor-
1,4-Dichlorobenzene
Benzoic acid
phenol
draz ine
Benzo(a)-
anthene
Benzyl Alcohol
bls(2~Chloro-
2-Chloronaphthalene
4-Bromophenyl
anthracene
Benzo( a) pyrene
1,2-Dichlorobenzene
ethoxy)oethane
2-Nitroaniline
Phenyl Ether
bifl(2-ethylhexyl)
Indeno(1,2,3-c
2-Methylphenol
2,4-Dichloro-
Dimethyl Phthalate
Hexachloro-
Phthalate
pyrene
bis(2-Chlorolso-
phenol
Acenaphthylene
benzene
Chrysene
Dibenz(a,h)
propyl)ether
I,2,4-Trichloro-
3-Nitroaniline
Pentachloro-
Terphenyl-dj4
anthracene
4-Methylphenol
benzene
Acenaphthene
phenol
(surr)
Benzo(g,h,i)
N-nitroao-Di-n-
Naphthalene
2,4-Dinitrophenol
Phenanthrene
perylene
propylamlne
4-Chloroanillne
4-Nitrophenol
Anthracene
liexachloroe thane
llexachloro-
Dlbenzofuran
Di-n-butyl
2-Fluorophenol
butadiene
2,4-Dlnltrotoluene
Phthalate
(surr)
4-Chloro-3-
2,6-Dini trotoluene
Fluoranthene
Phenol-dg (surr)
muthylphenol
Diethyl Phthalate
2-Methylnaphth-
alene
Nitrobenzene-d5
(surr)
4-Chlorophenyl-
phenyl ether
Fluorene
4-Nitroanlllne
2-Fluoroblphenyl
(surr)
2,4,6-Tribromo
Phenol (surr)
Surr ¦ surrogate compound
-------
hi sv
Continuing Calibration
A calibration standard(s) containing all semivolatile TCL compounds,
including all required surrogates-, must be analyzed each twelve hours
during analysis (see definition of twelve hour time period, paragraph
1. of this Section). Compare the relative response factor data from
the standards each twelve hours with the average relative response
factor from the initial calibration for a specific instrument* A
system performance check oust be made each twelve hours. If the SPCC
criteria are met, a comparison of relative response factors is made for
all compounds. This is the same check that is applied during the
initial calibration (Form VI). If the minimum relative response factors
are not met, the system must be evaluated and corrective action must be
taken before sample analysis begins.
2.6.1 Some possible problems are standard mixture degradation, injec--
tion port inlet contamination, contamination at the front end
of the analytical column, and active sites in the column or
chromatography system. This check must be met before analysis
begins. The minimum relative response factor (RRF) for semi-
volatile System Performance Check Compounds-(SPCC) i» 0.050.
2.6.2 Calibration Check Compounds (CCC)
After the system performance check is met, Calibration Check
Compounds listed in Table 2.3 are used to check the validity of
the initial calibration. Calculate the percent difference
using Equation 2.3.
Bfj - RRFC
X Difference * --------- x 100 Eq. 2.3
RRFj
where,
RRFj - average response factor from initial calibration.
RRFe * response factor from current verification check
standard.
2.6.2.1 If the percent difference for any compound is greater
than 202, the laboratory should consider this a warn-
ing limit. If the percent difference for each CCC
is less than or equal to 25.02, the initial calibration
is assumed to be valid. If Che criteria are not met
(>25.02 difference), for any one calibration check com-
pound, corrective action MUST be taken. Problems
similar to those listed under SPCC could affect this
criteria. If no source of the problem can be determined
after corrective action has been taken, a new initial
five point calibration MUST be generated. These criteria
MOST be met before sample analysis begins.
E-32
10/86
-------
Ill sv
TABLE 2.3. CALIBRATION CHECK COMPOUNDS
Base/Neutral Fraction
Add Fraction
Acenaphthene
1,4-Dichlorobenz ene
Hexachlorobutadlene
4-Chloro-3-Methylphenol
2,4-Dichlorophenol
2-Nltrophenol
N-Nitroso-di-n-phenylamine Phenol
Di-n-octylphthalate
Fluoranthene
Benzo(a)pyrene
Pentachlorophenol
2,4,6-Tri chlorophenol
2.6.3 Concentration Levels for Continuing Calibration Check
The USEPA plans to evaluate the long term stability of response
factors during this program. Standardization among contract
laboratories Is necessary to reach these long term goals.
Along with contract specified concentrations for Initial cali-
bration, the USEPA is requiring specific concentrations for
each continuing calibration standard(s).
2.6.3.1 The concentration for each semivolatile TCL compound
in the continuing calibration standard(s) is SO
.total nanograms for all compounds.
2*7 Documentation
The contractor shall complete and submit a Form VII for each GC/MS
system utilized for each twelve hour time period. Calculate and report
the relative response factor and percent difference (ZD) for all com-
pounds. Ensure that the minimum RRF for semivolatile SPCC's is 0.050.
The percent difference (%D) for each CCC compound must be less than or
equal to 25.0 percent. Additional instructions for completing Form VII
are found in Exhibit B, Section III.
PART 3 - METHOD BLANK ANALYSIS
3. Summary
A method blank is a volume of deionized, distilled laboratory water for
water samples, or a purified solid matrix for soil/sediment samples,
carried through the entire analytical scheme (extraction, concentration,
and analysis). For soil/sediment samples, a solid matrix suitable for
semivolatile analyses is available from EMSL/LV. The method blank volume
or weight must be approximately equal to the sample volumes or sample
weights being processed.
3.1 Method blank analysis must be performed at the following frequency.
E-33
10/86
-------
Ill sv
3*1.1 For the analysis of semivolatile TCL compounds, a mathod blank
analysis oust be performed once:
o each Case, OR
o each 14 calendar day period during which samples In a Case
are received (said period beginning with che receipt of the
first sample In that Sample Delivery Group), OR
o each 20 samples In a Case that are of similar matrix (water
or soil) or similar concentration (soil only), OR
o whenever samples are extracted by the same procedure (separa-
tor y funnel, continuous liquid-liquid extraction, or sonlcatlon),
whichever Is most frequent, on each GC/MS or GC system used to
analyze samples.
3.2 It is the contractor's responsibility to ensure that method interfer-
ences caused by contaminants in solvents, reagents, glassware, and
other sample processing hardware that lead to discrete artifacts
and/or elevated baselines in gas chromatograms be minimized.
3.2.1 For the purposes of this protocol, an acceptable laboratory
method blank should meet the criteria of paragraphs 3.2.1.1
and 3.2.1.2.
3.2.1.1 A method blank for semivolatile analysis must contain
no greater than five times (5X) the Contract Required
Quantitation Limit (CRQL from Exhibit C) of the
phthalate esters in the TCL.
3.2.1.2 For all other TCL compounds not listed above, the
method blank must contain less than the Contract
Required Quantitation Limit of any single TCL analyte.
3.2.2 If a laboratory method blank exceeds these criteria, the con-
tractor must consider the analytical system to be out of control.
The source of the contamination must be investigated and appro-
priate corrective measures MUST be taken and documented before
further sample analysis proceeds. All samples processed with a
method blank that is out of control (i.e., contaminated) MUST
be reextracted and reanalyzed at no additional cost to the
Agency. The Laboratory Manager, or his designee, must address
problems and solutions in the Case Narrative (Exhibit B).
3.3 Documentation
The contractor shall report results of method blank analysis using the
Organic Analysis Data Sheet (Form I) and the form for tentatively
identified compounds (Form I, TIC). In addition, the samples associated
with each method blank must be summarized on Form IV (Method Blank
Summary). Detailed instructions for the completion of these forms
are In Exhibit Bt Section III.
3.3.1 The Contractor shall report ALL sample concentration data as
UNCORRECTED for blanks.
E-34
10/86
-------
Ill sv
PART 4 - SURROGATE SPIKE (SS) ANALYSIS
4. Summary
Surrogate standard determinations are performed on all samples and blanks.
All samples and blanks are fortified with surrogate spiking compounds
before purging or extraction in order to monitor preparation and analysis
of samples*
4.1 Each sample, matrix spike, matrix spike duplicate, and blank are spiked
with surrogate compounds prior to extraction. The surrogate spiking
compounds shown in Table 4,1 are used to fortify each sample, matrix
spike, matrix spike duplicate, and blank with the proper concentrations.
Performance based criteria are generated from laboratory results.
Therefore, deviations from the spiking protocol will not be permitted.
TABLE 4.1. SURROGATE SPIKING COMPOUNDS
Compounds
Amount in Sample Extract*
(before any optional dilutions)
Fraction
Water
Low/Medium Soil
Nitrobenzene-d5
BNA
50 ug
50 ug
2-Fluorobi phenyl
BNA
50 ug
50 ug
p-Terphenyl-di4
BNA
50 ug
50 ug
Phenol-ds
BNA
100 ug
100 ug
2-Fluorophenol
BNA
100 ug
100 ug
2,4,6-Tri bromophenol
BNA
100 ug
100 ug
* At the time of injection.
4.2 Surrogate spike recovery must be evaluated by determining whether the
concentration (measured as percent recovery) falls Inside the contract
required recovery limits listed in Table 4.2.
TABLE 4.2. CONTRACT REQUIRED SURROGATE SPIKE RECOVERY LIMITS
Fraction Surrogate Compound Water Low/Medium Soil
BNA Nitrobenz ene-dj 35-114 23-120
BNA 2-Fluorobiphenyl 43-116 30-115
BNA p-Terphenyl-dj[4 33-141 18-137
BNA Phenol-d5 10-94 24-113
BNA 2-Fluorophenol 21-100 25-121
BNA 2,4,6-Tri bromophenol 10-123 19-122
i— mm mm ¦ w— ¦ ¦ ¦ ¦ ¦ m «"¦»
E-35
10/86
-------
Ill sv
4.3 Treatment of surrogate spike recovery information is according to
paragraphs 4.3.1 through 4.3.2.
4.3-. 1 Method Blank Surrogate Spike Recovery
The laboratory must take the actions listed below if recovery
of any one surrogate compound in either the base/neutral or
acid fraction is outside of contract surrogate spike recovery
limits.
4.3.1.1 Check calculations to ensure that there are no errors;
check internal standard and surrogate spiking solutions
for degradation, contamination, etc; also check instru-
ment performance.
4.3.1.2 Reanalyze the blank extract if steps in 4.3.1.1 fall
to reveal the cause of the noncompliant surrogate
recoveries.
4.3.1.3 Reextract and reanalyze the blank.
4.3.1.4 If the measures listed in 4.3.1.1 thru 4.3.1.3 fail
to correct the problem, the analytical system must be
considered to be out of control. The problem MUST be
corrected before continuing. This may mean recali-
brating the instrumentation but it may also mean more
extensive action. The specific corrective action is
left up to the GC/MS operator. When surrogate
recoveryCies) in the blank is outside of the contract
required windows, all samples associated with that
blank MOST be reanalyzed at no additional cost to the
Agency.
4.3.2 Sample Surrogate Spike Recovery
The laboratory must take the actions listed below if either of
the following conditions exists:
o Recovery of any one surrogate compound in either base
neutral or add fraction is below 10Z.
o Recoveries of two surrogate compounds in either base
neutral or acid fractions are outside surrogate spike
recovery limits.
4.3.2.1 The contractor shall document (in this instance,
document means to write down and discuss the problem
and corrective action taken in the Case Narrative,
see Exhibit B) deviations outside of acceptable
quality control limits and take the following actions:
E-36
10/86
-------
Ill sv
4.3.2.1.1 Check calculations Co ensure chat chere
are no errors; check internal standard and
surrogate spiking solutions for degradation,
contamination, etc.; also check instrument
performance.
4.3.2.1.2 If the steps in 4.3.2.1.1 fall to reveal
a problem, then reanalyze the extract. If
reanalysis of the extract solves the
problem, then the problem was within the
laboratory's control. Therefore, only
submit data from the analysis with surrogate
spike recoveries within the contract
windows. This shall be reported as such
on all data deliverables.
4.3.2.1.3 If the steps in 4.3.2.1.2 fail to solve
the problem, then reextract and reanalyze
the sample. If the reextractlon and
reanalysis solves the problem, then the
problem was in the laboratory's control.
Therefore, only submit data from the
extraction and analysis with surrogate
spike recoveries within the contract
windows. This shall be considered the
initial analysis and shall be reported as
such on all data deliverables..
If the reextractlon and reanalysis of the *
sample does not solve the problem; i.e.,
surrogate recoveries are outside the
contract windows for both analyses, then
submit the surrogate spike recovery data
and the sample data from both analyses
according to paragraph 4.4. Distinguish
between the initial analysis and the
reanalysis on all data deliverables, using
the sample suffixes specified in Exhibit 3.
4.4 Documentation
The contractor shall report surrogate recovery data for the following:
o Method Blank Analysis
o Sample Analysis
o Matrix Spike/Matrix Spike Duplicate Analyses
o All sample reanalyses that substantiate a matrix effect
The surrogate spike recovery data is summarized on the Surrogate Spike
Percent Recovery Summary (Form II). Detailed Instructions for the
completion of Form II are in Exhibit B, Section III.
E-37
10/86
-------
Ill sv
PART 5 - MATRIX SPIKE/MATRIX SPIKE DUPLICATE ANALYSIS CMS /MSP)
5. -Summary
In order Co evaluate Che matrix effect of the sample upon the analytical
methodology, the USEPA has developed the standard mixes listed in Table
5*1 to be used for matrix spike and matrix spike duplicate analyses.
These compounds are subject to change depending upon availability and
suitability for use as matrix spikes.
5.1 MS/MSD Frequency of Analysis
A matrix spike and matrix spike duplicate must be performed for each
group of samples of a similar matrix, once:
o each Case of field samples received, OR
o each 20 field samples in a Case, OR
o each group of samples of a similar concentration level (soils only), OR
o each 14 calendar day period during which samples In a Case were
received (said period beginning with the receipt- of the. first
sample in Chat Sample Delivery Group),
whichever is most frequent*
5.2 Use the compounds listed in Table 5.1 to prepare matrix spiking solu-
tions according to protocols described in Exhibit D SV. The analytical
protocols in Exhibit D SV stipulate the amount of matrix spiking solution
to be added to the sample aliquots prior to extraction. Each method
allows for optional dilution steps which must be accounted for when
calculating percent recovery of the matrix spike and matrix spike
duplicate samples.
TABLE 5.1. MATRIX SPIKING SOLUTIONS
Base/Neutrals
1,2,4-Tri chlorobenz ene
Acenaphthene
2,4-Dinitrotoluene
Pyrene
N-Nitroso-Di-n-Propylamine
1,4-Dichlorobenzene
Acids
Pent a chlorophenol
Phenol
2-Chlorophenol
4-Chloro-3-Methylphenol
4-Nitrophenol
5.2.1 Samples requiring optional dilutions and chosen as the matrix
spike/ matrix spike duplicate samples, must be analyzed at Che
same dilution as the original unspiked sample.
E-38
10/86
-------
Ill sv
5.3 Individual component recoveries of the matrix spike are calculated using
Equation 5.1.
SSR - SR
Matrix Spike Percent Recovery » —-——— x 100 Eq. 5.1
SA
vhere
SSR ¦ Spike Sample Results
SR ™ Sample Result
SA ¦ Spike Added from spiking mix
5.4 Relative Percent Difference (RPD)
The contractor is required to calculate the relative percent difference
between the matrix spike and matrix spike duplicate. The relative percent
differences (RPD) for each component are calculated using Equation 5.2.
Dj - D2 Eq. 5.2
RPD x 100
(Di + D2)/2
where
RPD ¦ Relative Percent Difference
Dj • First Sample Value
D2 ¦ Second Sample Value (duplicate)
5.5 Document ati on
The matrix spike (MS) results (concentrations) for nonsplked semi-
volatile TCL compounds shall be reported on Form I (Organic Analysis
Data Sheet) and the matrix spike percent recoveries shall be summarized
on Form III (MS/MSD Recovery). These values will be used by EPA to
periodically update existing performance based QC recovery limits
(Table 5.2).
The results for nonsplked semivolatile TCL compounds In the matrix
spike duplicate (MSD) analysis shall be reported on Form I (Organic
Analysis Data Sheet) and the percent recovery and the relative percent
difference shall be summarized on Form III (MS/MSD Recovery). The RPD
data will be used by EPA to evaluate the long term precision of the
analytical method. Detailed instructions for the completion of Form III
are in Exhibit 3, Section III.
E-39
10/86
-------
TABLE 5.2. MATRIX SPIKE RECOVERY LIMITS
Fraction
"Matrix'Spffca Compound
Water
Soil/Sediment
BN
1,2,4-Trlchlorobenz ene
39-98
38-107
BN
Acenaphthene
46-118
31-137
BN
2,4-0initrot oluene
24-96
28-89
BN
Pyrene
26-127
35-142
BN
N-Nltroso-Di-n-Propylamine
41-116
41-126
BN
1,4-01chlorobenz ene
36-97
28-104
Add
Pentachlorophenol
9-103
17-109
Acid
Phenol
12-89
26-90
Acid
2-Chlorophenol
27-123
25-102
Acid
4-Chloro-3-Methylphenol
23-97
26-103
Acid
4-Nitrophenol
10-80
11-114
PART 6 - SAMPLE ANALYSIS
6. Summary
The intent of Part 6 is co provide Che Contractor with a brief summary of
ongoing QC activities involved with sample analysis. Specific references are
provided Co help Che Concraccor meet specific reporting and deliverables
requirements of this contract.
6.1 Sample Analysis
Samples can be analyzed upon successful completion of the initial QC
activities. When twelve <12) hours have elapsed since the initial tune
was completed, it is necessary to conduct an instrument tune and call'
bratlon check analysis (described in Part 2 of this Section). Any major
system maintenance, such as a source cleaning or installation of a new
column, may necessitate a retune and recalibratiori (see Initial Calibra-
tion, Part 2). Minor maintenance should necessitate only the calibra-
tion verification (Continuing Calibration, Part 2).
6*1.1 Internal Standards Evaluation - Internal standard responses and
retention times in all samples must be evaluated immediately
after or during data acquisition. If the retention time for any
internal standard changes by more than 30 seconds, the chromato-
graphic system must be Inspected for malfunctions, and correc-
tions made as required. The extracted ion current profile
(EICP) of the Internal standards must be monitored and evaluated
for each sample, blank, matrix spike, and matrix spike duplicate.
The criteria are described in detail in the instructions for
Form VIII, Internal Standard Area Summary (see Exhbit B, Section
III). If the extracted ion current profile (EICP) area for any
internal standard changes by more than a factor of two (-502 to
E-40
10/86
-------
Ill sv
100%), from the latest dally (12 hour time period) calibra-
tion standard, the mass spectrometric system must be inspected
for malfunction, and corrections made as appropriate. Breaking
off 1 foot of the column or cleaning the Injector sleeve will
often Improve high end sensitivity for the late elutlng com-
pounds; repositioning or repacking the front end of the column
will often Improve front end column performance. Poor Injection
technique can also lead to variable IS ratios. When corrections
are made, reanalysls of samples analyzed while the system was
malfunctioning Is necessary.
6.1.1.1 If after reanalysls, the EICP areas for all Internal
standards are Inside the contract limits (-50Z to
+100Z), then the problem with the first analysis is
considered to have been within the control of the
laboratory. Therefore, only submit data from the
analysis with EICF's within the contract limits.
This Is considered the Initial analysis and must be
reported as such on all data deliverables.
6.1.1.2 If the reanalysls of the sample does not solve the
problem, I.e., the EICP areas are outside contract
limits for both analyses, then submit the EICP data
and sample data from both analyses. Distinguish
between the initial analysis and the reanalysls on
all data deliverables, using the sample suffixes
specified in Exhibit B. Document in the Case Narratlv*
all inspection and corrective actions taken.
6.1.2 Each analytical run must also be checked for saturation. The
level at which an individual compound will saturate the detection
system is a function of the overall system sensitivity and the
mass spectral characteristics of that compound. The Initial
method calibration (Part 2) requires that the system should not
be saturated for high response compounds at 160 nanograms for
semivolatile TCL compounds. -
6.1.2.1 If any compound in any sample exceeds the Initial c
allbration range, that sample must be diluted, the
Internal standard concentration readjusted, and the
sample reinjected, as described In specific methodolo-
gies In Exhibit D SV. Secondary ion quantitation is
only allowed when there are sample matrix interferences
with the primary Ion.
6.1.2.2 If the dilution of the sample causes any compound de-
tected in the first analysis to be undetectable In
the second analysis, then the results of both analyses
shall be reported on separate Forms I, according to
the instructions in Exhibit B.
E-41
10/86
-------
Ill sv
6.1.3 Qualitative Analysis
The semivolatile compounds listed in the Target Compound List
(TCL), Exhibit C, shall be Identified by an analyst competent
in che interpretation of mass spectra, by comparison of the
suspect mass spectrum to the mass spectrum of a standard of the
suspected compound. Two criteria must be satisfied to verify
the identifications: (1) elution of the sample component at the
seme GC relative retention time as the standard component, and
(2) correspondence of the sample component and standard component
mass spectra (see Exhibit D SV, Section IV).
6.1.3.1 For establishing correspondence of the GC relative
retention time (RRT), the sample component RRT must
compare within +0.06 RRT units of the RRT of the stan-
dard component. For reference, the standard must be
run on the same shift as the sample.
6.1.3.2 For comparison of standard and sample component mass
spectra, mass spectra obtained on the Contractor's
GC/MS are required. The DFTFP tuning requirements
listed in Part 1 must be met on the same GC/MS.
6.1.3.2.1 The requirements for qualitative verifica-
tion by comparison of mass spectra are as
follows:
o All ions present in the standard mass
spectra at a relative intensity greater
than 10Z (most abundant ion in the
spectrum equals 100Z) must be present
in the sample spectrum.
o The relative Intensities of ions speci-
fied in the above paragraph must agree
within +20% between the standard and
sample spectra.
o Ions greater than 10Z in the sample
spectrum but not present in the
standard spectrum must be considered and
accounted for by the analyst oaicing the
comparison. When GC/MS computer data
processing programs are used to obtain
the sample component spectrum, both the
processed and the raw spectra must be
evaluated. In Task III, the verifica-
tion process should favor false positives
(Exhibit D SV, Section IV).
E-42
10/86
-------
Ill sv
6.1.3.2.2 If a compound cannot be verified by all of
Che criteria in 6.1.3.2.1, but in the tech-
nical judgement of the mass spectral inter-
pretation specialist the identification
is correct, the contractor shall report
the identification and proceed with the
quantitation.
6.1.3.3 A library search shall be executed for non-
surrogate and non-TCL sample components
for the purpose of tentative identification.
For this purpose, the 1985 or most recent
available version of the National Bureau
of Standards Mass Spectral Library, containing
42,261 spectra, should be used.
6.1.4 Quantitation
6.1.4.1 Semlvolatlle TCL components identified shall be quanti-
tated by the Internal standard method. The internal
standards used shall be the ones assigned in- Table
2.2 of this Section. The EICP area of characteristic
ions of TCL analytes are used (Exhibit D SV, Section IV).
6.1.4.2 An estimated concentration for non-TCL components tenta-
tively identified shall be quantitated by the internal
standard method. For quantification, the nearest
internal standard free of interferences must be used.
6.1.4.3 Calculate surrogate standard recovery (see Part 4) for
all surrogate compounds on all samples, blanks, matrix
spikes, and matrix spike duplicates. If recovery is
within contractual limits, report on Form II (see
Exhibit B, Section III). If recovery is outside con-
tractual limits, take specific steps listed in Surrogate
Spike Recoveries (Part 4).
6.1.4.4 Calculate matrix spike and matrix spike duplicate
percent recovery (see Part 5) for all compounds and
report results on Form III (see Exhibit B, Section III),
Calculate Relative Percent Differences (RPD's) for all
matrix spiking compounds and report results on Form
III. Ensure that the proper frequency of MS/MSD analyst
is maintained.
6.1.5 Reporting and Deliverables
Refer to Exhibit B of this Statement of Work for specific
details on contract deliverables and reporting formats.
Exhibit B contains specific instructions for completing all
required Forms, as well as a detailed itemization of reporting
and deliverables requirements. Exhibit H contains the format
requirements for delivery of data in computer—readable format.
E-43
10/86
-------
SECTION III PEST
PESTICIDES/PCBs QA/QC
REQUIREMENTS
E-44
10/86
-------
Ill PEST
This Section outlines Che minimum quality control (QC) operations necessary
Co satisfy Che analytical requirements associated with the determination of
pesticide/?CB organic TCL compounds in water and soil/sediment samples. These
QC operations are as follows:
o Method Blank Analysis
o Surrogate Spike Response Monitoring
o Matrix Spike and Matrix Spike Duplicate Analysis
o Specific QA/QC for Pesticide Analysis
PART 1 - METHOD BLANK ANALYSIS
1. Summary
A method blank is a volume of deionized, distilled laboratory water for
water samples, or a purified solid matrix for soil/sediment samples,
carried through the entire analytical scheme (extraction, concentration,
and analysis). For soil/sedimenc samples, a solid matrix suitable for
pesticide analyses is available from EMSL-LV. The method blank volume or
weight must be approximately equal to the sample volumes or sample weights
being processed.
1.1 Method blank analysis must be performed at Che following frequency:
1.1.1 For Che analysis of pesCicide/PCB TCL compounds, a method
blank analysis must be performed once:
o each Case, OR
o each 14 calendar day period during which samples In a Case
are received (said period beginning wich Che receipc of Che
first sample in that Sample Delivery Group), OR
o each 20 samples in a Case that are of similar matrix (water
or soil) or similar concentration (soil only), OR
o whenever samples are extracted by the same procedure (separa-
tory funnel or continuous extraccion), -
whichever is most frequent, on each GC/MS or GC system used to
analyze samples.
1.2 It is the contractor's responsibility to ensure that method interferences
caused by concaminancs in solvencs, reagencs, glassware, and ocher sample
processing hardware Chat lead to discrete artifacts and/or elevated base-
lines in gas chromatograms be minimized.
1.2.1 For the purposes of this protocol, an accepcable laboracory
method blank should meec Che cricerla of paragraph 1.2.1.1.
1.2.1.1 The mechod blank must concain less Chan Che Concract
Required Quantitation Limit of any single pesticide/PCB
Target Compound (Exhibit C).
E-45
10/86
-------
Ill PEST
1.2.2 If a laboratory method blank exceeds these criteria, the con-
tractor oust consider the analytical system to be out of control.
The source of the contamination must be investigated and appro-
priate corrective measures MUST be taken and documented before
further sample analysis proceeds. All samples processed with a
method blank that is out of control (i.e., contaminated) MUST
be reextracted and reanalyzed at no additional cost to the
Agency. The Laboratory Manager, or his designee, must address
problems and solutions in the Case Narrative (Exhibit B).
1.3 Documentation
The contractor shall report results of method blank analysis using
the Organic Analysis Data Sheet (Form I). In addition, the samples
associated with each method blank must be summarized on Form IV (Method
Blank Summary). Detailed instructions for the completion of these
forms can be found in Exhibit B, Section III.
1.3.1 The Contractor shall report ALL sample concentration data as
UNCORRECTED for blanks.
PART 2 - SURROGATE SPIKE (SS) ANALYSIS
2. Summary
Surrogate standard determinations are performed on all samples and blanks.
All samples and blanks are fortified with surrogate spiking compounds
before purging or extraction in order to monitor preparation and analysis
of samples.
2.1 Each sample, matrix spike, matrix spike duplicate, and blank are spiked
with surrogate compounds prior to extraction. The surrogate spiking
compounds shown in Table 4.1 are used to fortify each sample, matrix
spike, matrix spike duplicate, and blank with the proper concentrations.
Performance based criteria are generated from laboratory results.
Therefore, deviations from the spiking protocol will not be permitted.
TABLE 4.1. SURROGATE SPIKING COMPOUND
Amount in Sample Extract*
Compound (before any optional dilutions)
Fraction Water Low/Medium Soil
Dlbutylchlorendate Pest. 0.1 ug 0.1. ug
* At the time of injection.
E-46
10/86
-------
Ill PEST
2.2 Surrogate spike recovery must be evaluated by determining whether the
concentration (measured as percent recovery) falls inside the advisory
recovery limits listed in Table 4.2.
TABLE 4.2. ADVISORY SURROGATE SPIKE RECOVERY LIMITS
Low/Medium
Fraction
Surrogate Compound
Water
Soil/Sediment
Pest.
Dlbutylchlorendate
(24-154)*
(20-150)*
* These limits are for advisory purposes only. They are not used to determine
if a sample should be reanalyzed. When sufficient data becomes available
the USEFA may set performance based contract required windows. *
2.3 Documentation
The contractor shall report surrogate recovery data for the following:
o Method Blank Analysis
o Sample Analysis
o Matrix Spike/Matrix Spike Duplicate Analyses
The surrogate spike recovery data is summarized on the Surrogate Spike
Percent Recovery Summary (Form II). Detailed instructions for the
completion of Form II are in Exhibit 8, Section III.
PART 3 - MATRIX SPIKE/MATRIX SPIKE DUPLICATE ANALYSIS (MS/MSP)
3. Summary
In order to evaluate the matrix effect of the sample upon the analytical
methodology, the USEPA has developed the standard mixes listed in Table
5.1 to be used for matrix spike and matrix spike duplicate analyses.
These compounds are subject to change depending upon availability and
suitability for use as matrix spikes.
3.1 MS/MSD Frequency of Analysis
A matrix spike and matrix spike duplicate must be performed for each
group of samples of a similar matrix, once:
o each Case of field samples received, OR
o each 20 field samples in a Case, OR
o each group of samples of a similar concentration level (soils
only), OR
o each 14 calendar day period during which samples in a Case were
received (said period beginning with the receipt of the first
sample in that Sample Delivery Group),
whichever is most frequent.
E-47
10/86
-------
Ill PEST
3.2 Use Che compounds listed in Table 5.1 Co prepare macrix spiking solu-
tions according to protocols described in Exhibit D PEST. The analyti-
cal protocols in Exhibit 0 PEST stipulate the amount of matrix spiking
solution to be added to the sample aliquots prior to extraction. Each
method allows for optional dilution steps which must be accounted for
when calculating percent recovery of the matrix spike and matrix spike
duplicate samples.
TABLE 5.1. MATRIX SPIKING SOLUTIONS
Pesticides
Heptachlor Lindane
Aldrin Endrin
Dieldrin 4,4'-DDT
3.2.1 Samples requiring optional dilutions and chosen as the matrix
spike/matrix spike duplicate samples, must be analyzed at the
same dilution as the original unspiked sample.
3.3 Individual component recoveries of the matrix spike are calculated
using Equation 5.1.
SSR - SR
Matrix Spike Percent Recovery ¦ x iqo Eq. 5.1
SA
where
SSR » Spike Sample Results
SR ¦ Sample Result
SA ¦ Spike Added from spiking mix
3.4 Relative Percent Difference (RFD)
The contractor is required to calculate the relative percent differ-
ence between the matrix spike and matrix spike duplicate. The relative
percent differences (RPD) for each component are calculated using
Equation 5.2.
D} - D2 Eq. 5.2
RPD x 100
(DX + D2)/2
where
RPD * Relative Percent Difference
D} ¦ First Sample Value
D2 ¦ Second Sample Value (duplicate)
E-48
10/86
-------
Ill PEST
3.5 Documentation
The matrix spike (MS) results (concentrations) for nonspiked pestl-
cide/PCB TCL compounds shall be reported on Form I (Organic Analysis
Data Sheet) and the matrix spike percent recoveries shall be summarized
on Form III (MS/MSD Recovery). These values will be used by EPA to
periodically update existing performance based QC recovery limits
(Table 5.2).
The results for nonspiked pestlcide/PCB TCL compounds in the matrix
spike duplicate (MSD) analysis shall be reported on Form I (Organic
Analysis Data Sheet) and the percent recovery and the relative percent
difference shall be summarized on Form III (MS/MSD Recovery). The RPD
data will be used by EPA to evaluate the long term precision of the
analytical method. Detailed instructions for the completion of Form
III are in Exhibit B, Section III.
TABLE 5.2. MATRIX SPIKE RECOVERY LIMITS*
Fraction Matrix Spike Compound Water Soil/Sediment
Pest. Lindane
Pest. Heptachlor
Pest. Aldrin
Pest. Dleldrln
Pest. Endrln
Pest. 4,4'-DDT
56-123 46-127
40-131 35-130
40-120 34-132
52-126 31-134
56-121 42-139
38-127 23-134
* These limits are for advisory purposes only. They are not to be used to
determine if a sample should be reanalyzed. When sufficient multi-lab data
are available, standard limits will be calculated.
PART 4 - PESTICIDE QA/QC REQUIREMENTS
4. Summary
Part 4 summarizes ongong QC activities involved with pestlcide/PCB
analysis that were detailed in Parts 1, 2 and 3 of this Section, and
describes the additional QA/QC procedures required during the analysis of
pesticide/?CB8 that are not covered in Parts 1, 2, and 3.
4.1 The Contractor must perform the following:
4.1.1 Method Blank analysis as per Part 1 of this Section.
E-49
10/86
-------
Ill PEST
4.1.2 Spike all standards, samples, blanks, matrix spike and matrix
spike duplicate samples with the surrogate spike compound
(dlbutylchlorendate) as par Part 2 of this Section.
4.1.3 Matrix Spike/Matrix Spike duplicate analysis as per Part 3 of
this Section.
4.2 The external standard quantitation method must be used to quantitate
all pestlcides/PCBs. Before performing any sample analysis, the
laboratory is required to determine the retention time window for each
pesticide/PCB target compound listed in Exhibit C and the surrogate
spike compound, dlbutylchlorendate. These retention time windows are
used to nudce tentative identification of pestlcides/PCBs during sample
analysis.
4.2.1 Prior to establishing retention time windows, the GC operat-
ing conditions (oven temperature and flow rate) must be ad-
justed such that 4,4'-DDT has a retention time of >_ 12 minutes
on packed GC columns. Conditions listed in Table 7, Exhibit D
PEST, Section IV .may be used to achieve this criteria..
4.2.2 Establish retention time windows as follows:
4.2.2.1 At the beginning of the contract and each time a
new GC column is installed, make three injections
of all single component pesticides mixtures, multi-
response pesticides, and PCBs throughout the course
of a 72-hour period. The concentration.of each
pesticide/PCB should be sufficient to provide a
response that Is approximately half scale. The three
injections of each compound should be made at approxi-
mately equal intervals during the 72-hour period,
(e.g., e&ch compound should be injected near the
beginning, near the middle, and near the end of the
72-hour period).
4.2.2.2 Verify the retention time shift,for dlbutylchlorendate
in each standard. The retention time shift between
the initial and subsequent standards must be less
than a 2.0 percent difference for packed columns
(<0.3 percent for capillary column). If this criterion
is not oat, continue injecting replicate standards to
meet this criterion.
4.2.2.3 Calculate the standard deviation of the three absolute
retention times for each single component pesticide.
For multlresponse pesticides or PCBs, choose one
major peak from the envelope and calculate the standard
deviation of the three retention times for that peak.
4.2.2.4 The standard deviations determined in 4.2.2.3 shall be
used to determine the retention time windows for a parti-
cular 72-hour sequence. Apply plus or minus three times
the standard deviations in 4.2.2.3 to the retention
E-50 10/86
-------
Ill PEST
time of each pesticide/PCB determined for the first
analysis of the pesticide/PCB standard In a given 72
hour analytical sequence. This range of retention
times defines the retention time window for the compound
of Interest for that 72-hour sequence. Note that, by
definition, the retention time of a pestlclde/PCB
from the first analysis of that compound in the 72 hour
sequence is the center of the retention time window.
Do not use the retention time measured in 4.2.2.1 as
the center of the retention time window. The experience
of the analyst should weigh heavily In the interpretation
of chromatograms. For multlresponse pesticide/PCBs,
the analyst should utilize the retention time window
but should primarily rely on pattern recognition.
For example, the three injections of aldrin in 4.2.2.1
have a mean retention time of 1.40 minutes and a stand-
ard deviation of 0.01 minutes. The retention time of
the aldrin standard at the beginning the 72-hour
sequence begun today is 1.51 minutes. Three, times
the standard deviation (0.01) is applied to the
retention time of aldrin from the sequence begun
today, e.g., 1.51 +3(0.01) - 1.48-1.54. If aldrin
has a retention time of 1.60 minutes at the beginning
of the next 72-hour sequence, then the retention time
window becomes: 1.60 + 3(0.01) • 1.57-1.63 for that
72-hour sequence.
4.2.2.5 In those cases where the retention time window for a
particular pesticide/PCB is less than 0.01 minutes,
the laboratory may substitute whichever of the follow-
ing formulae apply.
o For packed columns, the retention time window of
the particular pesticide/PCB shall be calculated
as + 1% of the initial retention time of the
compound In the 72-hour sequence.
o For capillary columns, the retention time window
of the particular pesticide/PCB shall be calculated
as + 0.15% of the initial retention time of the
compound in the 72-hour sequence.
4.2.2.6 Regardless of whether the retention time windows are
calculated by the method in 4.2.2.4 or 4.2.2.5, the
retention time windows must be reported as a range of
values, not as, for example, 1.51 minutes £ 1%.
4.2.2.7 The laboratory must calculate retention time windows
for each pesticide/PCB on each GC column used at the
beginning of the program and whenever a new GC column
is installed. The data must be retained by the
laboratory and made available during an on-site
laboratory evaluation.
E-51
10/86
-------
Ill PEST
4.3 Primary GC Column Analysis
4.3.1 Primary Analysis establishes whether or not pestlddes/PCBs
are present in the sample, and establishes a tentative identi-
fication of each compound. Quantitation may be performed on
the primary analysis if the analysis meets all of the QC criteria
specified for quantitation.
4.3.2 Separation should be >_ 25 percent resolution between peaks.
This criteria must be considered when determining whether to
quantltate on the Primary Analysis or the Confirmation Analysis.
When this criterion cannot be met, quantitation is adversely
affected because of the difficulty in determining where to
establish the baseline.
4.3.3 Evaluation Standard Mixtures
4.3.3.1 Prepare Evaluation Standard Mixes A, B, and C
(Aldrin, Endrln, 4,4'-DDT and Oibutylchlorendate) at
the 3 concentration levels described in Exhibit.0
PEST. Analyze the three Evaluation Standard Mixes
sequentially at the beginning of each seventy-two
(72) hour period (See Figure 4.1).
4.3.3.2 Calculate the Calibration Factor (ratio of the total
area to the mass injected) for each compound in
Evaluation Standard Mix A, B and C using Equation
4.1.
Total Area of Peak Eq.4.1
Calibration Factor ¦ — — ¦
Mass Injected (in nanograms)
4.3.3.3 Using the Calibration Factors from 4.3.3.2 above,
calculate the percent relative standard deviation
(ZRSD) for each compound at the three concentration
levels using Equation 4.2. The-percent relative
standard deviation for Aldrin, Endrln, and Oibutyl-
chlorendate must be < 10*0 percent. If the ZRSD ex-
ceeds 10.0% for 4,4'-DDT, see Section 4.5.4.4.
Note: The 10.0Z RSD linearity criteria pertains only
to columns being used for Pesticlde/PCB quantitation.
If a column is used only for surrogate quantitation,
the 10.OZ RSD is only required for Oibutylchlorendate.
E-52
10/86
-------
Ill PEST
SD
X Relative Standard Deviation ¦ ---- x 100 Eq. 4.2
x
where Standard Deviation (SD)
N-l
x ¦ mean of initial three Calibration Factors
(per compound).
4.3.3.4 Evaluate the chromatogram from the analysis of the
Evaluation Mix B. The appearance of peaks in addition
to the four main pesticide peaks indicates a breakdown
of Endrin and/or 4,4'-DDT.
4.3.3.5 Calculate the percent breakdown for Endrin and/or
4,4'-DDT on the mixed phase (1.5Z 0V-16/1.95Z 0V-210
or equivalent) GC column using Equations 4.3" and 4.4.
The percent breakdown for Endrin or 4,4'-DDT must not
exceed 20.0 percent. Corrrective action must be taken
before analysis continues.
Total DOT degradation peak area (DDE + DDD) Eq. 4.3
Z breakdown ¦ —• ——— — x 100
for 4,4'-DDT Total DDT peak area (DDT + DDE + DDD)
Z breakdown for Endrin « Eq. 4.4
Total Endrin degradation peak areas (Endrin Aldehyde + Endrin Ketone)
Total Endrin Peak Area (Endrin * Endrin Aldehyde + Endrin Ketone)
4.3.3.6 Calculate the percent breakdown for Endrin and/or
4,4'-DDT on the 07-1 or equivalent GC column using
Equations 4.3 and 4.4 The percent breakdown for
Endrin or 4,4'-DDT must not exceed 20.0 percent.
Corrective action must be taken before analysis
continues.
x 100
4.3.3.7 If there is evidence of a peak at the retention time
for Endrin aldehyde-/4,4'-DDD (which coelute on the
OV-1 or equivalent GC column), calculate a combined
percent breakdown for Endrin/4,4'-DDT using Equation
4.5. The combined Endrin/4,4'-DDT percent breakdown
must not exceed 20.0 percent, else corrective action must
be taken before analysis continues.
NOTE: The term "peak height" may be substituted for the term "peak area."
-------
Ill PEST
Combined Z breakdown • Eq. 4.5
Total Endrln/DDT degradation peak areas (000, DDE, Endrin Aldehyde + Endrin Ketone)
Total Endrin/DDT peak area (Endrin, Endrin Aldehyde, Endrin Ketone, DOT, ODD, ODE)
4.3.3*8 Suggested Maintenance
Corrective measures may require any one or more of
the following remedial actions:
4.3.3.8.1 Packed columns - For instruments with
off-column injection; replace the demister
trap, clean and deactivate the glass
injection port Insert or replace with a
cleaned and deactivated insert. Inspect
the injection end of the column and remove
any foreign material (broken glass from the
rim of the column or pieces of septa).
Replace the glass wool- with fresh, deacti-
vated glass wool. Also, it may be necesary
to remove the first few millimeters of
pecking material if any discoloration is
noted, also swab out the inside walls of
the column if any residue is noted. If these
procedures fail to eliminate the degradation
problem, it may be necessary to deactivate
the metal injector body (described below)
and/or repack/replace the column.
4.3.3.8.2 Capillary columns - Clean and deactivate the
glass injection port insert or replace with
a cleaned and deactivated insert. Break off
the first few Inches, up to one foot, of the
Injection port side of the column. Remove
the column and solvent backflush according
to the manufacturer's Instructions. If
these procedures fail to eliminate the de-
gradation problem, it may be necessary to
deactivate the metal injector body and/or
replace the column.
4.3.3.8.3 Metal Injector Body - Turn off the oven and
remove the analytical column when the oven
has cooled. Remove the glass injection port
insert (instruments with off-column injec-
tion or Grob). Lower the injection port
temperature to room temperature. Inspect
the injection port and remove any noticeable
foreign material.
NOTE: The term "peak height" may be substituted for the term "peak area."
E-54 9/86
-------
Ill PEST
Place a beaker beneach the injector port
inside the GC oven. Using a wash bottle,
serially rinse the entire inside of the
injector port with acetone and then toluene,
catching the rlnsate in the beaker.
Prepare a solution of deactivating agent
(Sylon-CT or equivalent) following manufac-
turer's directions. After all metal surfaces
inside the injector body have been thoroughly
coated with the deactivation solution, serially
rinse the injector body with toluene, methanol,
acetone and hexane. Reassemble the injector
and replace the GC column.
4.3.4 Individual Standard Mixtures A and B
4.3.4.1 Prepare Individual Standard Mixtures A and B contain-
ing the single component pesticides. These may be
divided into the groups suggested in Exhibit D PEST,
which are recommended to prevent overlap of compounds
on two of the packed columns. One mixture of all of
the single component pesiticldes is acceptable when
using capillary column. Prepare separate solutions
of all multi-response pesticides and PCBs. (Aroclor
1016 and Aroclor 1260 may be combined in a single
mixture.) •
4.3.4.2 Analyze Individual Standard Mixtures A and B and
all multi-response pesticlde/PCB's at the beginning
of each 72 hour period (see Figure 4.1) and analyze
Individual Standard Mixtures A and B at the intervals
specified in the analytical sequence in Figure 4.1,
and whenever sample analysis is completed. The
Calibration Factor for each standard quantitated
(Individual Standard Mix A or B) (Equation 4.6), must
not exceed a 15.0 percent difference for a quantitation
run nor exceed a 20.0 percent difference for a con-
firmation run during the 72 hour period. Calculate
percent difference using Equation 4.7. Deviations
greater than 15.0 percent require the laboratory to
repeat the samples analyzed following the quantitation
standard that exceeded the criterion.
NOTE: Aroclors 1221 and 1232 must be analyzed at a
minimum of once a month on each instrument and each
column. Copies of these chromatograms must be sub-
mitted with each case for instruments and columns
used to quantitate samples in that case, when identity
of these two pesticides (Aroclor 1221 and 1232) has
been confirmed.
NOTE: The terra "peak height" may be substituted for the term "peak area."
E-55 10/86
-------
Ill PEST
Total Area of Peak*
Calibration Factor • Eq. 4.6
"Miss injected (in nanograms)
* For multiresponse pesticides/PCBs use the total area of
all peaks used for quantitation*
- R2
Percent Difference * x iqq Eq. 4.7
*1
where R^ ¦ Calibration Factor from first analysis
&2 " Calibration Factor from second or
subsequent analysis
4.4 Sample Analysis (Primary GC Column)
4.4.1 Samples are analyzed per the sequence described in Figure 4.1.
4.4.2 The retention time shift for Dibutylchlorendate oust be eval-
uated after the analysis of each sample. The retention time
shift may not exceed a 2.0 percent difference for packed GC
columns between the initial standard analysis and any sample
or standard analyzed during the 72 hour period. The percent
difference for capillary columns muse not exceed 0.3 percent
(Equation 4.8).
RTj - RTg
Percent Difference (%D) " x jqO Eq. 4.8
RTj
where RTj • absolute retention time of Dibutylchlorendate
in the initial standard (Evaluation Standard Mix
A).
RTs * absolute retention time of Dibutylchlorendate
in the sample or subsequent standard.
4.4.3 Evaluate the GC column throughout the analysis of samples
by injecting Evaluation Standard Mix B at the frequency
outlined in Figure 4.1.
4.4.4 Calculate the percent breakdown for 4,4'-DDT and Endrin
according to 4.3.3.5 Take corrective action when the
breakdown for 4,4'-DDT or Endrin exceeds 20.0 percent.
NOTE: The term "peak height" may be substituted for the term "peak area."
E-56 10/86
-------
Ill PEST
FIGURE 4.1 72 HOUR SEQUENCE FOR PESTICIDE/PCB ANALYSIS
1.
Evaluation Standard
Mix A
2.
Evaluation Standard
Mix B
3.
Evaluation Standard
Mix C
4.
Individual Standard
Mix A*
5.
Individual Standard
Mix B*
6.
Toxaphene
7.
Aroclors 1016/1260
8.
Aroclor 1221**
9.
Aroclor 1232**
10.
Aroclor 1242
11.
Aroclor 1248
12.
Aroclor 1254
13.
5 Samples
14.
Evaluation Standard
Mix B
15.
5 Samples
16.
Individual Standard
Mix A or B
17.
5 Samples
18.
Evaluation Standard
Mix B
19.
5 Samples
Mix A or B (whichever not run
20.
Individual Standard
in step 16)
21.
5 Samples
22.
Repeat Che above sequence starting with Evaluation
Standard Mix B (step 14 above).
23.
Pesticide/PCB analysis sequence must end with Individual
Standard Mix A and B regardless of number of samples analyzed.
* These may be one mixture.
** Aroclors 1221 and 1232 must be analyzed at a'minimum of once per
month on each Instrument and each column. Copies of these
chromatograms must be submitted with each Case for instruments
and columns used to quantitate samples in that Case.
E-57
10/86
-------
Ill PEST
4.4.5 If ou or mora compounds have a response greater Chan full
scale, the extract requires dilution according to the specifi-
cations in Exhibit 0 PEST. If the dilution of the extract
causes any compounds tentatively identified in the first analysis
to be undetectable in the second analysis, then the results of
both analyses shall be reported on separate Forms I, according
to the instructions In Exhibit B. For dilutions greater than
10-fold, also see the instructions in Exhibit 0 PEST.
Confirmation Analysis (GC/EC)
4.5.1 Confirmation Analysis is to confirm the presence of all com-
pounds tentatively identified in the Primary Analysis.
Therefore, the only standards that are required are the Eval-
uation Standard Mixes (to check linearity and degradation
criteria) and standards of all compounds to be confirmed. The
72-hour sequence described in Figure 4.1 is, therefore, modified
to fit each case. Quantitation may be performed on the con-
firmation analysis. If toxaphene or DOT is. to be quantltated,
additional linearity requirements are specified in in Section
4.5.4.
4.5.2 Separation should be >. 25 percent resolution between peaks.
This criteria oust be considered when determining whether to
quantitate on the Primary Analysis or the Confirmation Analysis.
When this criterion cannot be met, quantitation is adversely
affected because of the difficulty In determining where to
establish the baseline.
4.5.2.1 For a fused silica capillary (FSCC) confirmation,
there must be >, 25 percent resolution (valley) be-
tween the following pesticide pairs:
o beta-BHC and delta-BHC
o Dieldrin and 4,4*-DDT
o 4,4'-ODD and Endrin Aldehyde,
o Endosulfan Sulfate and 4,4'-DDT
4.5.3 All QC specified previously must be adhered to, i.e., the .> 12
minutes retention time for 4,4'-DDT, and the specified criteria
for 4,4'-DDT and endrin degradation, linearity, calibration
factor Cor standards, and retention time shift for dibutyl-
chlorendate. The retention time requirement 4,4'-DDT does not
have to be met if the confirmation column is OV-1 or OV-101.
E-58
10/86
-------
Ill PEST
4.5.4 Begin ehe Confirmation Analysis GC sequence with Che chree con-
centration levels of Evaluation Standard Mixes A, B and C. The
exception to this occurs when toxahpene and/or DOT series are
to confirmed and quantltated. There are four combinations of
pesticides Chat could occur, therefore, the following sequences
must be followed depending on the situation.
4.5.4.1 Toxaphene only - Begin the sequence wich Evaluacion
Mix B to check degradation, followed by three concen-
tration levels to toxaphene. Check linearity by
calculating ZRSD. If £ 10.0% RSD, use the appropriate
equation in Exhibit 0 PEST for calculation. If >10.02
RSD, plot a standard curve and determine the ng for
each sample in that sec from Che curve*
4.5.4.2 DOT, DOE, 000 only - Begin Che sequence with Evalua-
tion Mix B. Then inject chree concencraclon levels
of a standard concaining DDE, ODD and DDT. Calculate
llnearlcy and follow che requirements specified in
4.5.4.1 for each compound to be quanclcated.
4.5.4.3 DOT series and toxaphene - Begin the sequence with
Evaluation Mix 3. Then inject chree concentration
levels of toxaphene and another three levels of the
DDT series. Calculate llnearlcy and follow che
requiremencs specified in 4.5.4.1 for each compound
co be quancicaced.
4.5.4.4 Ocher pescicldes/PCBs plus DDT series and/or toxaphene -
Begin che sequence wich Evaluacion Standard Mixes A,
B and C. Calculate linearity on the four compounds
in the Evaluation Standards mixes. If DDT and/or one
or more of Che ocher compounds are >10.OX RSD and/or
degradation exceeds che cricerlon, corrective-maintenance
as ouclined in paragraph 4.3.3.8 should be performed
before repeacing che above chromaCography evaluations.
If DOT only exceeds che linearity criteria and one or
more of Che DDT series is Co be quancicaced, follow
4.5.4.2 (do not repeat Evaluacion Mix 3).
If none of the DDT series is to be quantltaced and
DOT exceeds the 10.QZ RSD, simply record the Z RSD on
the proper form. Anytime toxaphene is to be quantitated
follow 4.5.4.1.
4.5.5 After the llnearlcy scandards required in 4.5.4 are lnjecced,
concinue che confirmaclon analysis injecclon sequence wich all
compounds cencacively idencified during primary analysis to
escablish the daily retention time windows during primary
analysis. Analyze all confirmation standards for a case at
E-59
10/86
-------
Ill PEST
the beginning, ac intervals specified In 4.5.6, and at Che end.
Any pesticide outside of its established retention time window
requires immediate investigation and correction before continuing
the analysis. The laboratory must reanalyze all samples between
the standard that exceeds the criterion and a subsequent standard
that meets the criterion.
4.5.6 Begin injection of samples at this point of the Confirmation
Analysis sequence. Analyze groups of 5 samples with a standard
pertaining to the samples after each group (Evaluation Mix B
is required after the first 5 samples, and every 10 samples
thereafter, e.g., after 5, 15, 25, etc). The alternating
standard's calibration factors must be within 15.0 percent of
each other if quantitation is performed. Deviations larger
than 15.0 percent require the laboratory to repeat the samples
analyzed between the standard that exceeds the criterion and
a subsequent standard that meets the criterion. The 15.0
percent criterion only pertains to compounds being quantitated.
4.5.6.1 If more than one standard is required to confirm all
compounds tentatively identified In the Primary *
Analysis, include an alternate standard after each 10
samples.
4.5.6.2 Samples must also be repeated if the degradation of
either DDT and/or Endrin exceed 20.0 percent on the
intermittent Evaluation Standard Mix B.
4.5.6.3 If the samples are split between 2 or more Instruments,
all standards and blanks pertaining to those samples
must be analyzed on each instrument.
4.5.7 Inject the method blanks (extracted with each set of samples)
on every GC and GC column on which the samples are analyzed.
4.5.8 If quantitation is performed on the confirmation analysis,
follow the instructions in 4.4.5 regarding dilution of ex-
tracts and reporting results.
4.6 GC/MS Pestlclde/PCB Confirmation
4.6.1 Any pesticlde/PCB confirmed by two dissimilar GC columns must
also be confirmed by GC/MS if the concentration in the final
sample extract is sufficient for GC/MS analysis (based on
laboratory GC/MS detection limits).
I
E-60
10/86
-------
Ill PEST
4.6.1.1 Pescicides/PCB8 may be confirmed utilizing the
extract prepared for semivolatile GC/MS analysis;
however, the absence of pesticlde/PCBs In the semi-
volatlle extract would require the analysis of the
pestlclde/PCB (fraction) extract.
4.6.2 The tuning and mass calibration criteria for DFTPP (50 ng)
MUST be met prior to any confirmation of pestlcldes/PCBs Is
undertaken. Refer to the tuning and mass calibration instruc-
tion for semlvolatiles. The characteristic Ions for 6C/MC
analysis of pestlcldes/PCBs are given in Exhibit D SV, Table 5.
4.6.3 The pestlclde/PCB sample extract(s) and the associated pestl-
clde/PCB blank(s), and reference standard(s) must be analyzed
by GC/MS.
Documentation
See Exhibit B for complete instructions for the completion of all re-
quired forms and the Deliverable Index for all reporting and deliver-
ables requirements.
E-61
10/86
-------
SECTION IV
ANALYTICAL STANDARDS
The Environmental Protection Agency's Quality Assurance Materials Bank
will supply primary standards (calibration standards, surrogate standards,
matrix spiking standards, and internal standards), contingent upon cheir
availability, only for traceability and quantitative verification of Contractor
9tandards. It is emphasized that these primary standards are for traceability
only. There are insufficient quantities to have these available to serve as
working standards* The contractor is responsible for preparing its own working
standards from commercial sources.
Caution should be exercised when mixing these standards together, particu-
larly the multlcomponent standards. Chemical reactions, such as acid/base
reactions, Schlff base formations (reactions of aldehydes and ketones with
primary amines), hydrolysis, isotopic exchange, and others may occur.
EPA contract laboratories can call or write directly to the QAMB (address
and phone number on the following request form) to obtain reference standards.
Standards will be provided based on the reasonableness of the request and their
availability. Any request from a commercial laboratory that is not currently
under contract to EPA will be denied.
Upon award of a contract, a list of available standards will be provided
by the EMSL/LV upon request.
E-62
10/86
-------
QUALITY ASSURANCE MATERIALS BANK
REQUEST FOR REFERENCE STANDARDS
MAJLTO':
Telephone:
U.S. Environmental Protection Agency
Quality Assurance Materials Sank (MD-8)
Research Triangle Park, NC 27711 USA
"555"
Requests ONLY:
Information:
Technical Assistance:
The feitevwinq reference itwidards in required tor our program:
(919)541-4019
(FTS) 629-4019
(702) 5*5-2690
(FTS) 545-2690
(919)541-3951
(FTS) 629-3951
Oat* Request M<»»v«d_
Oat* of Shipment,
Laboratory Cade Number.
Request Number
Verified
THIS ILOOC POM AGtkCY US« ONtY
Number
Required
Standard
Cm*
Campownd(s)
Solvent | Purity |' Can^f9n
i
r 1
1
1
1
1 1
! 1
I
1 1
1 I
1 !
k«i« *n>i « tat. MUMTma OH TYfnta ttm mv«u. JM JHo i
u>*«r .«n»» .t im«w
Nam* and A4dr*ss of laboratory:
IMPORTANT:
I * —« —» grfiTM 'a a* vM 3<"» •» »n jeonrofy Or au*«h*a '<» »• su/oott a# eeweewi» enact.
»*4iyt.cii or«Mur*i
-------
SECTION V
LABORATORY EVALUATION PROCEDURES
This document outlines the procedures which will be used by the Project
Officer or his authorized representative to conduct laboratory audits to
determine the contractor's ability to meet the terms and conditions of this
contract. The evaluation process incorporates two major steps: 1) evalua-
tion of laboratory performance, and 2) on-site Inspection of the laboratory
to verify continuity of personnel, instrumentation and quality control
requirements of the contract. The following Is a description of these
two steps.
PART 1 - EVALUATION OF LABORATORY PERFORMANCE
1. Performance Evaluation Sample Analysis
1*1 The Performance Evaluation (PE) sample set will be sent to a participating
laboratory on a quarterly basis to verify the laboratory's continuing
ability to produce acceptable analytical results. These samples will be
provided either single blind (recognizable as a PE material and of unknown
composition), or double blind (not recognizable as a PE material and of
unknown composition). Contractors are required to return PE analytical
data within thirty (30) calendar days of receipt.
1.2 When the PE data are received, results will be scored routinely for
identification and quantitation, according to the elements and weighting
factors shown in Figure 1. Results of these scorings will be-provided for
the contractor via coded evaluation spread sheets by compound classes. The
government may adjust the scores on any given PE sample to compensate for
unanticipated difficulties with a particular sample.
Timeliness in delivering PE sample data to the government is essential and
is reflected In the deduction of points from the gross score (Figure 1) for
late data submissions. Late is defined as 31 days or more from the
documented date of PE sample receipt.
1.3 If a laboratory performs unacceptably, the laboratory will be Immediately
notified by the Project Officer* A laboratory so notified may expect,
but the government is not limited to, the following actions: a site visit,
a full data audit, and/or laboratory analysis of a second PE sample.
Failure by the laboratory to take corrective actions and/or failure of two
successive PE sample analyses will require that the laboratory discontinue
analysis of samples until such time as the Project Officer has determined
that the laboratory may resume analyses.
2. Organic Data Audit
2.1 Organic data audits are conducted on CLP Contractor's Reporting and Deliver-
ables packages by EMSL/LV. The organic data audit provides the Agency
with an in-depth inspection and evaluation of the Case data packages with
regard to achieving QA/QC acceptability.
E-64
10/86
-------
PART 2 - ON-SITE LABORATORY EVALUATION
2. The on-site laboratory evaluation helps to ensure that all the necessary
quality control is being applied by the contractor in order to deliver a quality
product.
2.1 Quality assurance evaluations allow the evaluacors to determine that:
2.1.1 The organization and personnel are qualified to perform assigned
tasks,
2.1.2 Adequate facilities and equipment are available,
2.1.3 Complete documentation, including chain-of-custody of samples is
being implemented,
2.1.4 Proper analytical methodology is being used,
2.1.5 Adequate analytical Quality Control, including reference samples,
control charts, and documented corrective action measures, is being
provided, and
2.1.6 Acceptable data handLing and documentation techniques are being used*
2.2 The on-site visit also serves as a mechanism for discussing weaknesses
Identified through the Performance Evaluation sample analysis or
through Contract Compliance Screening or other review of data deliver-
ables. Lastly, the on-site visit allows the evaluation team to deter-
mine if the laboratory has implemented the recommended and/or required
corrective actions, with respect to quality assurance, made during the
previous on-site visit.
E-65
10/86
-------
EXHIBIT F
CHAIN-OF-CUSTODY, DOCUMENT CONTROL,
AND STANDARD OPERATING PROCEDURES
10/86
-------
i. Sample Oiain-Qf-Custodv
A sample is physical evidence collected from a facility or from the environ-
ment. An essential part of hazardous waste investigations is that samples and
data may be used as evidence in EPA enforcement proceedings. To satisfy
enforcement uses of the data, the following chain-of-custody procedures have
been established.
1.1 Sample Identification
To assure traceability of samples while in possession of the laboratory,
a method for sample identification shall be developed and documented
in laboratory Standard Operating Procedures (SOPs) (see Section 3).
Each sample or sample preparation container shall be labeled with a
unique number identifier (or the SMO number). This identifier shall
be cross-referenced to the sample tag number and the SMO number.
There shall be a written description of the method of assigning this
identifier and attaching it to the sample container included in the
laboratory SOPs.
1.2.1 A sample is under custody if:
1.2.1.1 It is in your actual possession,
1.2.1.2 It is in your view after being in your physical posses-
sion,
1.2.1.3 It was in your possession and then you locked or
sealed it up to prevent tampering, or
1.2.1.4 It is in a secure area.
1.2.2 Upon receipt of the samples in custody, the contractor shall
inspect the shipping container and sample bottles and shall
document receiving information as specified in Section 3.2.
The sample custodian or a designated representative shall sign
and date all appropriate receiving documents at the time of
receipt (i.e., EPA chain-of-custody forms, traffic reports, air-
bills, etc.). The contractor shall contact SMO if documents are
absent, information on receiving documents does not agree,
custody seals are not intact, or the sample is not in good
condition. The contractor shall document resolution of any
discrepancies, and this documentation shall become a part of
the permanent case file.
1.2.3 Once samples have been accepted by the laboratory, checked,
and logged in, they must be maintained in accordance with
custody and security requirements specified in 3.3.
F-l
10/86
-------
2. Document Control Procedures
The goal of the laboratory document control program is to assure that all
documents for a specified case will be accounted for when the project is
completed. Accountable documents used by contract laboratories shall
include, but not be limited to, logbooks, chain-of-custody records, sample
work sheets, bench sheets, and other documents relating to the sample or
sample analyses. The following document control procedures have been
established to assure that all laboratory records are assembled and stored for
delivery to EPA or are available upon request form EPA prior to the delivery
schedule.
2.1 Preprinted Data Sheets and Logbooks
Preprinted data sheets shall contain the name of the laboratory and be
dated and signed by the analyst or individual performing the work.
All documents produced by the laboratory which are directly related
to the preparation and analysis of EPA samples shall become the
property of the EPA and shall be placed in the case file. For that
reason, all observations and results recorded by the laboratory.but not
on preprinted data sheets are entered into permanent laboratory log-
books. The person responsible for the work shall sign and date each
entry and/or page in the logbook. When all data from a case is com-
piled, copies of all EPA case-related logbook entries shall be included
in the documentation package. Analysts' logbook entries must be in
chronological order and shall include only one case per page. Instru-
ment run logs shall be maintained so as to enable a reconstruction of
the run sequences of individual instruments.
Because the laboratory must provide copies of the instrument run logs
to EPA, the laboratory may exercise the option of using only labora-
tory or SMO sample identification numbers in the logs for sample ID
rather than government agency or commercial client names.
Using laboratory or SMO sample IDs only in the run sequences will
assist the laboratory in preserving the confidentiality of commercial
clients.
2.2 Error Correction Procedure
All documentation in logbooks and other documents shall be in ink. If
an error is made, corrections shall be made by crossing a line through
the error and entering the correct information. Changes shall be dated
and initialed. Mo information shall be obliterated or rendered
unreadable.
2.3 Consistency of Documentation
Before releasing analytical results, the laboratory shall assemble and
cross-check the information on sample tags, custody records, lab bench
sheets, personal and instrument logs, and other relevant data to ensure
that data pertaining to each particular sample or case is consistent
throughout the case file.
F-2
10/86
-------
2.4 Document Numbering and Inventory Procedure
In order to provide document accountability of the completed analysis
records, each item in a case shall be inventoried and assigned a serial-
ized number and identifier associating it to the case and Region.
Case * - Region • Serialized number (For example: 75-2-0240)
The number of pages of each item must be accounted for if each page
is not individually numbered. All documents relevant to each case,
including logbook pages, bench sheets, mass spectra, chromatograms,
custody records, library search results, etc., shall be inventoried. The
laboratory shall be responsible for ensuring that all documents gener-
ated are placed in the file for inventory and are delivered to EPA.
Figure 1 is an example of a document inventory.
2.5 Shipping Data Packages and Case Files
The contractor shall have written procedures to document shipment of
deliverables packages to the recipients. These shipments require
custody seals on the containers placed such that it cannot be opened
without damaging or breaking the seal. The contractor shall also
document what was sent, to whom, the date, and the method (carrier)
used.
3. Standard Operating Procedures
The contractor must have written standard operating procedures (SOPs) for
(1) receipt of samples, (2) maintenance of custody, (3) sample storage, (4)
tracking the analysis of samples, and (5) assembly of completed data.
An SOP is defined as a written narrative step-wise description of laboratory
operating procedures including examples of laboratory documentation. The
SOPs must accurately describe the actual procedures used in the laboratory,
and copies of the written SOPs shall be available to the. appropriate labora-
tory personnel. These procedures are necessary to ensure that analytical data
produced under this contract are acceptable for use in EPA enforcement case
preparation and litigation. The contractor's SOPs shall provide mechanisms
and documentation to meet each of the following specifications and shall be
used by EPA as the basis for laboratory evidence audits.
3.1 The contractor shall have a designated sample custodian responsible
for receipt of samples and have written SOPs describing his/her duties
and responsibilities.
3.2 The contractor shall have written SOPs for receiving and logging in of
the samples. The procedures shall include but not be limited to docu-
menting the following information:
o Presence or absence of EPA chain-of-custody forms
o Presence or absence of airbills
F-3
10/36
-------
o Presence or absence of EPA Traffic Reports or SAS packing lists
o Presence or absence of custody seals on shipping and/or sample
containers and their condition
o Presence or absence of sample tags
o Sample tag ID numbers if not recorded on the chain-of-custody
record(s) or packing list(s)
o Condition of the shipping container
o Condition of the sample bottles
o Verification of agreement or nonagreement of information on
receiving documents
o Resolution of problems or discrepancies with the Sample Manage*
ment Office
3.3 The contractor shall have written SOPs for maintenance of the
security of samples after log-in and shall demonstrate security of the
sample storage and laboratory areas. The SOPs shall specifically
include descriptions of all storage areas for EPA samples in the
laboratory, and steps taken to prevent sample contamination. The
SOPs shall include a list of authorized personnel who have access or
keys to secure storage areas.
3.4 The contractor shall have written SOPs for tracking the work per-
formed on any particular sample. The tracking SOP shall include the
following:
3.4.1 A description of the documentation used to record sample
receipt, sample storage, sample transfers, sample preparations,
and sample analyses.
3.4.2 A description of the documentation used to record instrument
calibration and other QA/QC activities.
3.4.3 Examples of the document formats and laboratory documenta-
tion used in the sample receipt, sample storage, sample
transfer, and sample analyses.
3.5 The contractor shall have written SOPs for organization and assembly
of all documents relating to each EPA case, including technical and
managerial review. Documents shall be filed on a Case-specific basis.
The procedures must ensure that all documents including logbook
pages, sample tracking records, chromatographic charts, computer
printouts, raw data summaries, correspondence, and any other written
documents having reference to the Case are compiled in one location
for submission to EPA. The system must include a document
numbering and inventory procedure.
3.6 The contractor shall have written SOPs for laboratory safety.
F-4
10/86
-------
3.7 The contractor shall have written SOPs for cleaning of glassware used
in preparing and analyzing samples under this contract.
3.S The contractor shall have SOPs for traceability of standards used in
sample analysis QA/QC.
4. Handling of Confidential Information
A contractor conducting work under this contract may receive EPA-desig-
nated confidential information from the agency. Confidential information
must be handled separately from other documentation developed under this
contract. To accomplish this, the following procedures for the handling of
confidential information have been established.
4.1 All confidential documents shall be under the supervision of a desig-
nated document control officer (DCO).
4.2 Confidential Information
Any samples or information received with a request of confidentiality
shall be handled as "confidential." A separate locked file shall be
maintained to store this information and shall be segregated from
other nonconfidential information. Data generated from confidential
samples shall be treated as confidential. Upon receipt of confidential
information, the OCO logs these documents into a Confidential Inven-
tory Log. The information is then made available to authorized per-
sonnel but only after it has been signed out to that person by the
DCO. The documents shall be returned to the locked file at the con-
clusion of each working day. Confidential information may not be
reproduced except upon approval by the EPA Contracting Officer.
The DCO will enter all copies into the document control system. In
addition, this information may not be disposed of except upon
approval by the EPA Contracting Officer. The DCO shall remove and
retain the cover page of any confidential information disposed of for
one year and shall keep a record of the disposition in the Confidential
Inventory Log.
F-5
10/86
-------
Figure 1
Example
DOCUMENT INVENTORY
Document Control »» POWmtttt TVPS *IlS£S.
232-2-0001 Case File Document Inventory Sheet 1
232-2-0002 Chain-of-Custody Records 2
232-2-0003 Shipping Manifests 2
232-2-0004 Sample Tags 50
232-2-000S SMO Inorganics Traffic Reports 10
232-2-0006 GC/MS spectra for sample B0310 20
232-2-0007 GC/MS spectra for sample B0311 20
232-2-0008 GC/MS spectra for sample B0319 20
232-2-0009 Analyst's logbook pages 6
232-2-0010 GC/MS library search worksheets 15
232-2-0011 GC instrument log pages 5
232-2-0012 GC/MS QC data sheets 4
etc. etc. etc.
•This number is to be recorded on each set of documents.
F-6
10/86
-------
EXHIBIT G
GLOSSARY OF TERMS
-------
GLOSSARY OF TERMS
ALIQUOT - a measured portion of a sample taken for analysis.
ANALYSIS DATE/TIME - the date and military time of the injection of the
sample, standard, or blaiik into the GC/MS or GC system.
BAR GRAPH SPECTRUM - a plot of the mass-to-charge ratio (m/e) versus relative
Intensity of the ion current.
BLANK - see Method Blank
4-BROMOFLUOROBENZENE (BFB) * compound chosen to establish mass spectral tuning
performance for volatile analyses.
CALIBRATION CHECK COMPOUNDS (CCC) - target compounds used to evaluate the
calibration stability (precision) of the GC/MS system. Maximum percent
deviations of the CCCa are defined in the protocol.
CASE - a finite, usually predetermined number of samples collected over a
given time period from a particular site. Case numbers are assigned by
the Sample Management Office. A case consists of one or more Sample
Delivery Groups.
CHARACTERIZATION - a determination of the approximate concentration range of
compounds of interest used to choose the appropriate analytical protocol.
CONCENTRATION LEVEL (low or medium) - characterization of soil samples or sample
fractions as low concentration or medium concentration is made on the basis of
the laboratory's preliminary screen, not on the basis of information entered on
the Traffic Report by the sampler.
CONFIRMATION ANALYSIS - see Primary Analysis.
CONTINUING CALIBRATION - analytical standard run every 12 hours to verify the
calibration of the GC/MS system.
CONTINUOUS LIQUID-LIQUID EXTRACTION - used herein synonymously with the terms
continuous extraction, continuous liquid extraction, and liquid extraction.
DAY - unless otherwise specified, day shall mean calendar day.
DECAFLUOROTRIPHENYLPHOSPHINE (DFTPP) - compound chosen to establish mass spectral
tuning performance for semivolatile analysis.
EXTRACTABLE - a compound that can be partitioned into an organic solvent from
the sample matrix and is amenable to gas chromatography. Extractables include
BNA and pestlcide/PCB compounds.
IN-HOUSE - at the Contractor's facility.
INITIAL CALIBRATION - analysis of analytical standards for a series of
different specified concentrations; used to define the linearity and dynamic
range of the response of the mass spectrometer to the target compounds.
G-l
10/86
-------
INTERNAL STANDARDS - compounds added to every standard, blank, matrix spike,
matrix spike duplicate, sample (for VOAs), and sample extract (for semivolatlles)
at a known concentration, prior to analysis. Internal standards are used as the
basis for quantitation of the target compounds.
LABORATORY - synonymous with Contractor as used herein.
MATRIX - the predominant material of which the sample to be analyzed Is composed.
For the purpose of this SOU, a sample matrix is either water or soil/sediment.
Matrix Is not synonymous with phase (liquid or solid).
MATRIX SPIKE - aliquot of a matrix (water or soil) fortified (spiked) with
known quantities of specific compounds and subjected to the entire analytical
procedure in order to indicate the appropriateness of the method for the matrix
by measuring recovery.
MATRIX SPIKE DUPLICATE - a second aliquot of the same matrix as the matrix
spike (above) that is spiked in order to determine the precision of the method.
METHOD BLANK (previously termed reagent blank) - an analytical control con-
sisting of all reagents, internal standards and surrogate standards,. that Is
carried through the entire analytical procedure. The method blank Is used to
define the level of laboratory background contamination.
NARRATIVE (Case Narrative) - portion of the data package which includes
laboratory, contract, Case and sample number identification, and descriptive
documentation of any problems encountered in processing the samples, along with
corrective action taken and problem resolution. Complete Case Narrative
specifications are included in Exhibit B.
PERCENT MOISTURE - an approximation of the amount of water in a soil/sediment
sample made by drying an aliquot of the sample at 105°C. The percent moisture
determined in this manner also includes contributions from all compounds chat
may volatilize at 105°C, including water. Percent moisture is determined from
decanted samples and from samples that are not decanted.
PRIMARY ANALYSIS - one of two types of pesticide/PCB analysis by GC/EC techniques>
the other being the Confirmation Analysis. If the two analyses are run at
separate times, the Primary Analysis is the first analysis chronologically, and
is used to establish the tentative identification of any pesticides/PCBs detected.
The Identification is then confirmed in the confirmation analysis. If the two
analyses are simultaneously, either may be considered Che Primary Analysis.
PROTOCOL - describes the exact procedures to be followed with respect to sample
receipt and handling, analytical methods, data reporting and deliverables, and
document control. Used synonymously with Statement of Work (SOW).
PURGE AND TRAP (DEVICE) - analytical technique (device) used to Isolate volatile
(purgeable) organics by stripping the compounds from water or soil by a stream
of inert gas, trapping the compounds on a porous polymer crap, and thermally
desorbing the trapped compounds onto the gas chromatographic column.
REAGENT WATER - water in which an interferent is not observed at or above
the minimum quantitation limit of the parameters of interest.
G-2
10/86
-------
RECONSTRUCTED ION CHROMATOGRAM (RIC) - a mass spectral graphical representation
of Che separation achieved by a gas chromatograph; a plot of total ion current
versus retention tine*
RECOVERY - a determination of the accuracy of the analytical procedure made by
comparing measured values for a fortified (spiked) sample against the known
spike values. Recovery is determined by the following equation:
measured value
ZRac " •" ¦ x 100%
known value
RELATIVE RESPONSE FACTOR (RRF) - a measure of the relative mass spectral response
of an analyte compared to its internal standard. Relative Response Factors are
determined by analysis of standards and are used in the calculation of
concentrations of analytes in samples. RRF is determined by the following
equation:
" ^x_ x £la.
Ais
Where -A * area of the characteristic Ion measured
C - concentration
is ¦ Internal standard
x ¦ analyte of Interest
RESOLUTION - also termed separation, the separation between peaks on a
chromatogram, calculated by dividing the height of the valley between the
peaks by the peak height of the smaller peak being resolved, multlpled by 100.
SAMPLE - a portion of material to be analyzed that is contained in single or
multiple containers and identified by a unique sample number.
SAMPLE DELIVERY GROUP (SDG) - a unit within a sample Case that is used to
identify a group of samples for delivery. An SDG is a group of 20 or fewer
samples within a Case, received over a period of up to 14 calendar days. Data
from all samples In an SDG are due concurrently. A Sample Delivery Group is
defined by one of the following, whichever occurs first:
o Case; or
o Each 20 samples within a Case; or
o Each 14-day calendar period during which samples in a Case
are received, beginning with receipt of the first sample in
the Case or SDG.
SAMPLE NUMBER (EPA Sample Number) - a unique Identification number designated
by EPA for each sample. The EPA sample number appears on the sample Traffic
Report which documents information on that sample.
SEMIV0LATILE COMPOUNDS - compounds amenable to analysis by extraction of the
sample with an organic solvent. Used synonymously wlch Base/Neutral/Acid (BNA)
compounds•
SOIL - used herein synonymously with soil/sediment and sediment.
G-3
10/86
-------
STANDARD ANALYSIS - an analytical determination made with known quantities of
target compounds; used to determine response factors.
SURROGATES (Surrogate Standard) - compounds added to every blank, sample,
matrix spike, matrix spike duplicate, and standard; used to evaluate analytical
efficiency by measuring recovery. Surrogates are brominated, fluorinated, or
isotopically labelled compounds not expected to be detected in environmental
media.
SYSTEM PERFORMANCE CHECK COMPOUNDS (SPCC) - target compounds designated to
monitor chromatographic performance, sensitivity and compound instability or
degradation on active sites. Minimum response factor criteria for the SPCCs
are defined in the protocol.
TARGET COMPOUND LIST (TCL) - a list of compounds designated by the Statement of
Work (Exhibit C) for analysis.
TENTATIVELY IDENTIFIED COMPOUNDS (TIC) - compounds detected in samples that
are not target compounds, internal standards or surrogate standards. Up to
30 peaks (those greater than 10% of peak areas or heights of nearest internal
standards) are subjected to mass spectral library searches.for tentative
identification.
TIME - when required to record time on any deliverable item, time shall be
expressed as Military Time, i.e., a 24-hour clock.
TRAFFIC REPORT (TR) - an EPA sample identification form filled out by the
sampler, which accompanies the sample during shipment to the laboratory and
which documents sample condition and receipt by the laboratory.
TWELVE-HOUR TIME PERIOD - The twelve (12) hour time period for GC/MS system
tuning and standards calibration (initial or continuing calibration) begins at
the moment of Injection of the DFTPP or BFB analysis that the laboratory submits
as documentation of compliant tune. The time period ends after 12 hours has
elapsed according to the system clock.
VALIDATED TIME OF SAMPLE RECEIPT (VTSR) - the date on which a sample is
received at the Contractor's facility, as recorded on the shipper's delivery
receipt and Sample Traffic Report.
VOLATILE COMPOUNDS - compounds amenable to analysis by the purge and trap
technique. Used synonymously with purgeable compounds.
G-4
10/86
-------
EXHIBIT H
DATA DICTIONARY AND FORMAT FOR DATA DELIVERABLES
IN COMPUTER-READABLE FORMAT
-------
1. Introduction
1.1 The format for delivery of computer-readable data Is based upon the
structure of the hardcopy reporting forms required by the contract.
With two exceptions, Form Suffix and Record Type, all fields in the
format directly correspond with entries or items on the hardcopy forms.
1.2 The format is such that one 360K diskette (see 2. below) should be able
to contain all required Information (including blanks, MS/MSO, etc.)
for full (three fraction: volatiles, semivolatiles and pesticides/PCB)
analyses of fifteen water or soil samples.
2. Deliverable
2.1 The file must be submitted on an IBM or IBM-compatible 5-1/4 inch
floppy diskette, which may be either a double-sided, double density,
360 K-byte or a high capacity 1.2 M-byte diskette. The diskette must
accompany the hardcopy data packages submitted to the Sample Management
Office (see Exhibit B). Information on the diskette must correspond
exactly with information submitted on the hardcopy data package forms.
3. File Structure
3.1 The file is composed of 80-byte ASCII records. Unused bytes on
partially filled fields must be blank-filled. Unspecified bytes
at the end of each record should be blank-filled. Each record
must end with a carriage return/line feed. The file must be named
"LLLLLL.CCCCC.ORG" where LLLLLL is the six-character Lab Code and
CCCCC is the Case Number. The file name must be clearly shown on the,
diskette sleeve.
3.2 A data element delimiter, a comma, must follow all fields, with the
exception of the form and suffix number.
4. Record Types
4.1 There are three types of record in the proposed format: Header
Records, Detail Records, and Comment Records.
1221
Izes_J£
H
Contents
Header
Nonrepeating fields which
together are unique to the
associated hardcopy form.
Detail
D
A group of fields that are
repeated on a form, and are
uniquely positioned by (e.g.)
CAS Number or Sequence Number
Comment
C
Nonrepeating fields contain-
ing text that qualifies a
form.
H-l
10/86
-------
5. Record Structure
5.1 All fields are character unless otherwise specified. Field lengths are
such that all possible valid values can be written to the file. The
format of each field Is specified. For example "Numeric 13.2" for
"Result" on Detail Record 01 of Form 1A. The format specification
indicates the maximum length of numeric variables and the maximum number
of decimal places that may be reported. Actual numeric values reported
may take any integer or real form, provided they do not exceed the
specifications. For example a "Result" on 01 of Form 1A could be
reported as integer 13, Integer 3, real 13.2, real 5.1, or any other
permutation which does not exceed the specification.
5.2 The first three bytes of each record will contain the Form Number
(e.g., 1A) as it appears on the hardcopy form. The fourth and fifth
bytes of each record will contain the form suffix (AA - ZZ) which must
be unique for each set of records that corresponds to one type of
hardcopy form.
For example, the first occurrence of a form must contain the suffix
AA, the second occurrence must contain A3, and the twenty-eighth
occurrence must contain BA.
5.3 The sixth and seventh bytes of each record contain the Record Type
identifier.
5.4 Detailed specifications for every record required for a full set
of hardcopy forms comprise the remainder of this Exhibit.
H-2
10/86
-------
PORN I FILE DESCRIPTION
(FORM!)
H - 3
10/86
-------
VOLATILE ORGANICS ANALYSIS DATA SHEET - (FORM IA)
HEADER RECORD 1 (HI)
COLUMN (S)
1- 3
4- 5
6- 7
8
9-18
19
20-44
45
46-56
57
58-63
64
65-69
70
71-76
77
LENGTH CONTENTS
FORMAT/CONTENTS
10
25
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
EPA SAMPLE NO.
DELIMITER
LAB NAME
DELIMITER
CONTRACT
DELIMITER
LAB CODE
DELIMITER
CASE NO.
DELIMITER
SAS NO.
DELIMITER
1A
A-ZZ
HI
HEADER RECORD 2 CH2)
COLUMN
-------
HEADER RECORD 3 (H3)
COLUMN CS) LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
A- 5
6- 7
8
9-16
17
18-25
26
27-31
32
3
2
2
1
8
1
8
1
5
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
DATE ANALYZED
DELIMITER
DILUTION FACTOR
DELIMITER
CONCENTRATION UNITS
DELIMITER
1A
A-ZZ
H3
MM/DD/YY
U6/L OR UG/KG
DETAIL RECORD 1 (Dl)
COLUMN CS) LENGTH CONTENTS
1- 3
4- 5
6- 7
8
9-18
19
20-^7
*8
49-61
62
63-67
68
3
2
2
1
10
1
28
1
13
1
5
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
CAS NO.
DELIMITER
COMPOUND
DELIMITER
RESULT
DELIMITER
QUALIFIER CQ)
DELIMITER
FORMAT/CONTENTS
1A
A-ZZ
Dl
NUMERIC 13.2
H - 5
10/86
-------
SEMIVOLATILE
0R6ANICS
ANALYSIS DATA SHEET -
(FORM IB)
HEADER RECORD
1 (HI)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
I- 3
3
FORM NUMBER
IB
4- 5
2
FORM SUFFIX
A-Z2
6- 7
2
RECORD TYPE
HI
1
DELIMITER
»
9-18
10
EPA SAMPLE NO.
19
1
DELIMITER
i
20-44
25
LAB NAME
45
1
DELIMITER
t
46-56
11
CONTRACT
57
1
DELIMITER
t
58-63
6
LAB CODE
64
1
DELIMITER
t
65-69
5
CASE NO.
70
1
DELIMITER
t
71-76
6
SAS NO.
77
1
DELIMITER
i
HEADER RECORD
2 (H2)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
IB
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
H2
8
1
DELIMITER
»
9-13
5
SDG NO.
14
1
DELIMITER
i
15-19
5
MATRIX
SOIL OR MATER
20
1
DELIMITER
*
21-32
12
LAB SAMPLE ID
33
1
DELIMITER
34-38
5
SAMPLE WT/VOL
NUMERIC 5.1
39
1
DELIMITER
t
40-41
2
SAMPLE WT/VOL UNITS
G OR ML
42
1
DELIMITER
i
43-56
14
LAB FILE ID
57
1
DELIMITER
*
58-60
3
LEVEL
LOW OR MED
61
1
DELIMITER
i
62-69
8
DATE RECEIVED
MM/DD/YY
70
1
DELIMITER
»
71-72
2
X MOISTURE NOT DEC
NUMERIC 2
73
1
DELIMITER
i
H - 6 10/36
-------
CONTENTS
FORMAT/CONTENTS
1-3 3
4-5 2
6-7 2
8 1
9-10 2
11 1
12-19 8
20 1
21-28 8
29 1
30-33 4
34 1
35 1
36 1
37-40 4
41 1
42-49 8
50 1
51-55 5
56 1
DETAIL RECORD 1 CD1)
COLUMN (5) LENGTH
1-3 3
4-5 2
6-7 2
8 1
9-18 10
19 1
20-47 28
48 1
49-61 13
62 1
63-67 5
68 1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
X MOISTURE DEC
DELIMITER
DATE ANALYZED
DELIMITER
DATE EXTRACTED
DELIMITER
EXTRACTION
DELIMITER
GPC CLEANUP
DELIMITER
PH
DELIMITER
DILUTION FACTOR
DELIMITER
CONCENTRATION UNITS
DELIMITER
CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
CAS NO.
DELIMITER
COMPOUND
DELIMITER
RESULT
DELIMITER
QUALIFIER (Q)
DELIMITER
IB
A-ZZ
H3
NUMERIC 2
MM/DD/YY
*
MM/DD/YY
SEPF, CQNT, OR SONC
Y OR N
»
NUMERIC 4.1
U6/L0R UG/KS
FORMAT/CONTENTS
IB
A-ZZ
D1
NUMERIC 13.2
H - 7
10/86
-------
SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET - (FORM 1C)
HEADER RECORD 1 (HI)
COLUMN (S) LENGTH 'CONTENTS
FORMAT/CONTENTS
I- 3
3
FORM NUMBER
4- 3
2
FORM SUFFIX
6- 7
RECORD TYPE
8
1
DELIMITER
9-18
10
EPA SAMPLE NO.
19
1
DELIMITER
20-44
25
LAB NAME
45
1
DELIMITER
46-56
11
CONTRACT
57
1
DELIMITER
58-63
6
LAB CODE
64
1
DELIMITER
65-69
CASE NO.
70
1
DELIMITER
71-76
6
SAS NO.
77
1
DELIMITER
1C
A-2Z
HI
HEADER RECORD 2 (H2)
LUMN (S)
LENGTH
CONTENTS
I- 3
3
FORM NUMBER
4- 5
2
FORM SUFFIX
6- 7
2
RECORD TYPE
8
1
DELIMITER
9-13
5
SD6 NO.
14
1
DELIMITER
15-19
5
MATRIX
20
1
DELIMITER
21-32
12
LAB SAMPLE ID
33
1
DELIMITER
34-38
5
SAMPLE WT/VOL
39
1
DELIMITER
40-41
2
SAMPLE WT/VOL UNITS
42
1
DELIMITER
43-56
14
LAB FILE ID
57
1
DELIMITER
58-60
3
LEVEL
61
1
DELIMITER
62-69
8
DATE RECEIVED
70
1
DELIMITER
71-72
2
X MOISTURE NOT DEC
75
1
DELIMITER
FORMAT/CONTENTS
1C
A-ZZ
H2
SOIL OR MATER
NUMERIC 5.1
6 OR ML
LOU OR MED
MM/DD/YY
NUMERIC 2
H - 8
10/36
-------
HEADER RECORD 3 CH3)
COLUMN (S)
1- 3
4- 5
6- 7
8
9-10
11
12-19
20
21-28
29
30-33
34
35
36
37-40
41
42-49
50
51-55
56
LENGTH CONTENTS
FORMAT/CONTENTS
3
2
2
1
2
1
8
1
8
1
4
1
1
1
4
1
8
1
5
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
X MOISTURE DEC
DELIMITER
DATE ANALYZED
DELIMITER
DATE EXTRACTED
DELIMITER
EXTRACTION
DELIMITER
GPC CLEANUP
DELIMITER
PH
DELIMITER
DILUTION FACTOR
DELIMITER
CONCENTRATION UNITS
DELIMITER
1C
A-ZZ
H3
NUMERIC 2
MM/DD/YY
9
MM/DD/YY
SEPF, CONT, OR SONC
Y OR N
NUMERIC 4.1
UG/L OR UG/MG-
DETAIL RECORD 1 (Dl)
COLUMN (S) LENGTH CONTENTS
FORMAT/CONTENTS'
I- 3
3
FORM NUMBER
1C
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
Dl
8
1
DELIMITER
9
9-18
10
CAS NO.
19
1
DELIMITER
9
20-47
28
COMPOUND
48
1
DELIMITER
9
49-61
13
RESULT
NUMERIC
62
1
DELIMITER
9
63-67
5
QUALIFIER CQ)
68
1
DELIMITER
9
H - 9
10/86
-------
PESTICIDE ORGANICS ANALYSIS DATA SHEET - (FORM ID)
HEADER RECORD 1 (HI)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
PORN NUMBER
ID
4- 5
2
PORM SUPFIX
A-Z2
6- 7
2
RECORD TYPE
HI
8
1
DELIMITER
9
9-18
10
EPA SAMPLE NO.
19
1
DELIMITER
9
20-44
25
LAB NAME
45
1
DELIMITER
9
46-56
11
CONTRACT
57
1
DELIMITER
9
58-63
6
LAB CODE
64
1
DELIMITER
9
65-69
5
CASE NO.
70
1
DELIMITER
9
71-76
6
SAS NO.
77
1
DELIMITER
9
HEADER RECORD 2 (H2)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
——————
————————— ____—______
1- 3
3
FORM NUMBER
ID
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
H2
8
1
DELIMITER
9
9-13
5
SDG NO.
14
1
DELIMITER
9
15-19
5
MATRIX
SOIL OR MATER
20
1
DELIMITER
9
21-32
12
LAB SAMPLE ID
33
1
DELIMITER
9
34-38
5
SAMPLE WT/VOL
NUMERIC 5.1
39
1
DELIMITER
9
40-41
2
SAMPLE HT/VOL UNITS
6 OR ML
42
1
DELIMITER
9
43-56
14
LAB FILE ID
57
1
DELIMITER
9
58-60
3
LEVEL
LOU OR MED
61
1
DELIMITER
9
62-69
8
DATE RECEIVED
MM/DD/YY
70
1
DELIMITER
9
71-72
2
% MOISTURE NOT DEC
NUMERIC 2
73
1
DELIMITER
9
H - 10
10/86
-------
HEADER RECORD 3
-------
VOLATILE 0R6ANZCS ANALYSIS DATA SHEET - (FORM IE)
TENTATIVELY IDENTIFIED COMPOUNDS
HEADER RECORD 1 CHI)
COLUMN CS)
1- 3
4- 5
6- 7
3
9-18
19
20-44
45
46-56
57
58-63
64
65-69
70
71-76
77
LENGTH CONTENTS
FORMAT/CONTENTS
10
25
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
EPA SAMPLE NO,
DELIMITER
LAB NAME
DELIMITER
CONTRACT
DELIMITER
LAB CODE
DELIMITER
CASE NO.
DELIMITER
SAS NO.
DELIMITER
IE
A-ZZ
HI
HEADER RECORD 2 CH2)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3 .
3
FORM NUMBER
IE
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
H2
8
1
DELIMITER
9
9-13
SDG NO.
14
1
DELIMITER
9
15-19
MATRIX
SOIL OR UATER
20
1
DELIMITER
9
21-32
12
LAB SAMPLE ID
33
1
DELIMITER
9
34-38
5
SAMPLE WT/VOL
NUMERIC 5.1
39
DELIMITER
9
40-41
2
SAMPLE WT/VOL UNITS
6 OR ML
42
1
DELIMITER
9
43-56
14
LAB FILE ID
57
1
DELIMITER
9
58-60
3
LEVEL
LOW OR MED
61
1
DELIMITER
9
62-69
DATE RECEIVED
MM/OO/YY
70
1
DELIMITER
9
71-72
2
X MOISTURE NOT DEC
NUMERIC 2
75
1
DELIMITER
9
H - 12
10/86
-------
HEADER RECORD 3 (H3)
COLUMN (S)
LEN6TH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
IE
4- 5
2
FORM SUFFIX
»-
I
N
N
6- 7
2
RECORD TYPE
H3
S
1
DELIMITER
9
9-16
8
DATE ANALYZED
MM/DD/YY
17
1
DELIMITER
9
18-25
8
DILUTION FACTOR
26
1
DELIMITER
9
27-28
2
NUMBER TICS FOUND
NUMERIC 2
39
1
DELIMITER
I
*0-44
5
CONCENTRATION UNITS
UG/L OR UG/KS
45
1
DELIMITER
f
DETAIL RECORD
1 (Dl)
COLUMN CS)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
IE
4- 5
2
FORM SUFFIX
>¦
1
IM
N
6- 7
2
RECORD TYPE
Dl
8
1
DELIMITER
9
9-10
2
SEQUENCE NUMBER
NUMERIC 2
11
1
DELIMITER
9
12-21
10
CAS NO.
22
1
DELIMITER
9
23-50
28
COMPOUND
51
1
DELIMITER
9
52-57
6
RT
NUMERIC 6.2
58
1
DELIMITER
9
59-71
13
ESTIMATED CONCENTRATION
NUMERIC 13.2
72
1
DELIMITER
9
73-77
5
QUALIFIER CQ)
78
1
DELIMITER
9
H - 13
10/86
-------
SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET
TENTATIVELY IDENTIFIED COMPOUNDS
- (FORM IF)
HEADER RECORD 1 (HI)
COLUMN (S)
1- 3
4- 5
6- 7
8
9-18
19
2 0-44
45
46-56
57
58-63
64
65-69
70
71-76
77
LENGTH CONTENTS
FORMAT/CONTENTS
3
2
10
25
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
EPA SAMPLE NO.
DELIMITER
LAB NAME
DELIMITER
CONTRACT
DELIMITER
LAB CODE
DELIMITER
CASE NO.
DELIMITER
SAS NO.
DELIMITER
IF
A-ZZ
HI
HEADER RECORD 2 (H2)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
IF
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
H2
8
1
DELIMITER
»
9-13
5
SDG NO.
14
1
DELIMITER
*
15-19
5
MATRIX
SOIL OR WATER
20
1
DELIMITER
»
21-32
12
LAB SAMPLE ID
33
1
DELIMITER
»
34-38
5
SAMPLE WT/VOL
NUMERIC 5.1
39
1
DELIMITER
t
40-41
2
SAMPLE WT/VOL UNITS
G OR ML
42
1
DELIMITER
t
43-56
14
LAB FILE ID
57
1
DELIMITER
i
58-60
3
LEVEL
LOW OR MED
61
1
DELIMITER
t
62-69
8
DATE RECEIVED
MM/DD/YY
70
1
DELIMITER
»
71-72
2
X MOISTURE NOT DEC
NUMERIC 2
73
1
DELIMITER
»
H - 14 10/86
-------
CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8
9-10
11
12-19
20
21-28
29
30-33
34
35
36
37-40
41
42-49
50
51-52
53
54-58
59
3
2
2
1
2
1
8
1
8
1
4
1
1
1
4
1
8
1
2
1
5
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
X MOISTURE DEC
DELIMITER
DATE ANALYZED
DELIMITER
DATE EXTRACTED
DELIMITER
EXTRACTION
DELIMITER
6PC CLEANUP
DELIMITER
PH
DELIMITER
DILUTION FACTOR
DELIMITER
NUMBER TICS FOUND
DELIMITER
CONCENTRATION UNITS
DELIMITER
IF
A-ZZ
H3
NUMERIC 2
*
MM/DD/YY
MM/DD/YY
9
SEPF, CONT» OR SONC
#
Y OR N
NUMERIC 4.1
NUMERIC 2
U6/L OR UG/KG
DETAIL RECORD 1 CD1)
COLUMN CS) LENSTH CONTENTS
1- 3
4- 5
6- 7
S
9-10
11
12-21
22
23-50
51
52-57
58
59-71
72
73-77
78
3
2
2
1
2
1
10
1
28
1
6
1
13
1
5
1
FORMAT/CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
SEQUENCE NUMBER
DELIMITER
CAS NO.
DELIMITER
COMPOUND
DELIMITER
RT
DELIMITER
ESTIMATED CONCENTRATION
DELIMITER
QUALIFIER (Q)
DELIMITER
IF
A-ZZ
D1
NUMERIC 2
NUMERIC 6.2
NUMERIC 13.2
H - 15
10/86
-------
FORM II FILE DESCRIPTION
C FORM2)
H
- 16
10/86
-------
HATER VOLATILE SURROGATE RECOVERY - (FORM ZA)
HEADER RECORD 1 (HI)
COLUMN CS) LENGTH CONTENTS
1- 3
4- 5
6- 7
8
9-33
34
35-45
46
47-52
53
54-58
59
60-65
66
67-71
72
25
1
5
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
LAB NAME
DELIMITER
CONTRACT
DELIMITER
LAB CODE
DELIMITER
CASE NO.
DELIMITER
SAS NO.
DELIMITER
SDG NO.
DELIMITER
FORMAT/CONTENTS
2A
A-ZZ
HI
DETAIL RECORD 1 (Dl)
COLUMN (S)
LENGTH CONTENTS
1-
4-
6—
3
5
7
8
9-10
11
12-21
22
23-25
26
27
28
29-31
32
33
34
35-37
38
39
40
41-43
44
45-46
47
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
SEQUENCE NUMBER
DELIMITER
EPA SAMPLE NO.
DELIMITER
SI (TOL)
DELIMITER
51 OUT FLAG
DELIMITER
52 (BFB)
DELIMITER
52 OUT FLAG
DELIMITER
53 (DCE)
DELIMITER
S3 OUT FLAG
DELIMITER
OTHER
DELIMITER
TOTAL OUT
DELIMITER
FORMAT/CONTENTS
2'A
A-ZZ
Dl
NUMERIC 2
NUMERIC 3
BLANK OR *
NUMERIC 3
BLANK OR *
NUMERIC 3
BLANK OR *
NUMERIC 3
NUMERIC 2
H - 17
10/86
-------
SOIL VOLATILE SURROGATE RECOVERY - (FORM 2B)
HEADER RECORD 1 CHI)
COLUMN (S)
1- 3
4- 5
6- 7
8
9-33
34
35-45
46
47-52
53
54-58
59
60-65
66
67-71
72
73-75
76
LENGTH
CONTENTS
FORMAT/CONTENTS
25
I
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
LAB NAME
DELIMITER
CONTRACT
DELIMITER
LAB CODE
DELIMITER
CASE NO.
DELIMITER
SAS NO.
DELIMITER
SOG NO.
DELIMITER
LEVEL
DELIMITER
2B
A-ZZ
HI
LOW OR MED
DETAIL RECORD 1 (Dl)
COLUMN (S) LENGTH CONTENTS FORMAT/CONTENTS
1- 3
3 FORM NUMBER
2B
4- 5
2 FORM SUFFIX
A-ZZ
6- 7
2 RECORD TYPE
Dl
8
1 DELIMITER
9
9-10
2 SEQUENCE NUMBER
NUMERIC 2
11
1 DELIMITER
9
12-21
10 EPA SAMPLE NO.
22
1 DELIMITER
9
23-25
3 SI CTOL)
NUMERIC 3
26
1 DELIMITER
9
27
1 SI OUT FLAG
BLANK OR *
28
1 DELIMITER
9
29-31
3 S2 (BFB)
NUMERIC 3
32
1 DELIMITER
9
33
1 S2 OUT FLAG
BLANK OR *
34
1 DELIMITER
9
35-37
3 S3 (DCE)
NUMERIC 3
38
1 DELIMITER
9
39
1 S3 OUT FLAG
BLANK OR *
40
1 DELIMITER
9
41-43
3 OTHER
NUMERIC 3
44
1 DELIMITER
9
45-46
2 TOTAL OUT
NUMERIC 2
47
1 DELIMITER
9
H - 48
10/86
-------
HATER SEMIVOLATILE SURROGATE RECOVERY - (FORM 2C)
HEADER RECORD 1 (HI)
LUMN (S)
LENGTH
CONTENTS
1- 3
3
FORM NUMBER
4- 5
2
FORM SUFFIX
6- 7
2
RECORD TYPE
8
1
DELIMITER
9-33
25
LAB NAME
34
1
DELIMITER
35-45
11
CONTRACT
46
1
DELIMITER
47-52
6
LAB CODE
53
1
DELIMITER
54-58
CASE NO.
59
1
DELIMITER
60-65
6
SAS NO.
66
1
DELIMITER
67-71
5
SDG NO.
72
1
DELIMITER
FORMAT/CONTENTS
2C
A-ZZ
HI
H - 19
10/86
-------
DETAIL RECORD I (Dl)
COLUMN (S) LENGTH CONTENTS FORMAT/CONTENTS
1-3 3 FORM NUMBER 2C
4-5 2 FORM SUFFIX A-2Z
6-7 2 RECORD TYPE D1
8 1 DELIMITER
9-10 2 SEQUENCE NUMBER NUMERIC 2
11 1 DELIMITER ,
12-21 10 EPA SAMPLE NO.
22 1 DELIMITER ,
23-25 3 SI (NBZ) NUMERIC 3
26 1 DELIMITER ,
27 1 SI OUT FLAG BLANK OR *
28 1 DELIMITER
29-31 3 S2 (FBP) NUMERIC 3
32 1 DELIMITER ,
33 1 S2 OUT FLAG BLANK OR *
34 I DELIMITER ,
35-37 3 S3 CTPH) NUMERIC 3
38 1 DELIMITER ,
39 1 S3 OUT FLAG BLANK OR *
40 1 DELIMITER
41-43 3 S4 CPHL) NUMERIC 3
44 1 DELIMITER ,
45 1 S4 OUT FLAG BLANK OR *
46 1 DELIMITER »
47-49 3 S5 (2FP) NUMERIC 3
50 1 DELIMITER »
51 1 S5 OUT FLAG BLANK OR *
52 1 DELIMITER
53-55 3 S6 CTBP) NUMERIC 3
56 1 DELIMITER ,
57 1 S6 OUT FLAG BLANK OR *
58 1 DELIMITER *
59-61 3 OTHER NUMERIC 3
62 1 DELIMITER
63-64 2 TOTAL OUT NUMERIC 2
65 1 DELIMITER ,
H - 20
10/86
-------
SOIL SEMIVOLATILE SURROGATE RECOVERY - (FORM 2D)
HEADER RECORD 1 CHI)
OLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
2D
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
HI
8
1
DELIMITER
9
9-33
25
LAB NAME
34
1
DELIMITER
35-45
11
CONTRACT
46
1
DELIMITER
9
47-52
6
LAB CODE
53
1
DELIMITER
to
in
1
-------
DETAIL RECORD 1 (Dl)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
2D
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
Dl
8
1
DELIMITER
9
9-10
2
SEQUENCE NUMBER
NUMERIC 2
11
1
DELIMITER
9
12-21
10
EPA SAMPLE NO.
22
1
DELIMITER
9
23-25
3
SI (NBZ)
NUMERIC 3
26
1
DELIMITER
9
27
I
SI OUT FLAG
BLANK OR *
28
1
DELIMITER
*
29-31
S2 (FBP)
NUMERIC 3
32
1
DELIMITER
»
33
1
S2 OUT FLAG
BLANK OR *
34
1
DELIMITER
t
35-37
S3 (TPH)
NUMERIC 3
38
1
DELIMITER
t
39
S3 OUT FLAG
BLANK OR *
40
1
DELIMITER
t
41-43
3
S4 (PHL)
NUMERIC 3
. 44
1
DELIMITER
>
45
1
S4 OUT FLAG
.BLANK OR *
46
1
DELIMITER
47-49
S5 (2FP)
NUMERIC 3
50
1
DELIMITER
»
51
1
S5 OUT FLAG
BLANK OR *
52
1
DELIMITER
t
53-55
3
S6 (TBP)
NUMERIC 3
56
1
DELIMITER
»
57
1
S6 OUT FLAG
BLANK OR *
58
1
DELIMITER
t .
Ul
1
H
3
OTHER
NUMERIC 3
62
1
DELIMITER
>
63-64
2
TOTAL OUT
NUMERIC 2
65
1
DELIMITER
>
H - 22
10/86
-------
FORMAT/CONTENTS
1- 3
4- 5
6- 7
S
9-33
34
35-45
46
47-52
53
54-53
59
60-65
66
67-71
72
FORM NUMBER 2E
FORM SUFFIX A-ZZ
RECORD TYPE HI
DELIMITER
LAB NAME
DELIMITER
CONTRACT
DELIMITER
LAB CODE
DELIMITER
CASE NO.
DELIMITER
SAS NO.
DELIMITER
5 SDG NO.
1 DELIMITER
DETAIL RECORD I (Dl)
COLUMN
-------
SOIL PESTICIDE SURROGATE RECOVERY
(FORM 2F)
HEADER RECORD 1 (HI)
COLUMN (S)
1- 3
A- 5
6- 7
8
9-33
34
35-45
46
47-52
53
54-58
59
60-65
66
67-71
72
73-75
76
LENGTH CONTENTS
FORMAT/CONTENTS
25
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
LAB NAME
DELIMITER
CONTRACT
DELIMITER
LAB CODE
DELIMITER
CASE NO.
DELIMITER
SAS NO.
DELIMITER
SDG NO.
DELIMITER
LEVEL
DELIMITER
2F
A-ZZ
HI
LOW OR MEDIUM
DETAIL RECORD 1 (Dl)
:OLUMN (S)
I- 3
4- 5
6- 7
8
9-10
11
12-21
22
23-25
26
27
28
29-31
32
LENGTH
3
2
CONTENTS
FORMAT/CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
SEQUENCE NUMBER
DELIMITER
EPA SAMPLE NO.
DELIMITER
SI (DBC) .
DELIMITER
SI OUT FLAG
DELIMITER
OTHER
DELIMITER
2F
A-ZZ
Dl
NUMERIC 2
NUMERIC 3
BLANK OR *
NUMERIC 3
H - 24
10/86
-------
FORM 111 FILE DESCRIPTION
CFORM3)
H
25
10/86
-------
!ATER VOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY - (F0RM3A)
IEADER RECORD 1 (HI)
:OLUMN (S)
LENGTH CONTENTS
FORMAT/CONTENTS
I- 3
3
FORM NUMBER
3A
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
HI
a
I
DELIMITER
9
9-43
25
LAB NAME
44
1
DELIMITER
9
45-55
11
CONTRACT
56
1
DELIMITER
9
57-62
6
LAB CODE
63
1
DELIMITER
9
64-68
5
CASE NO.
69
1
DELIMITER
9
70-75
6
SAS NO.
76
1
DELIMITER
9
DEADER RECORD
2 (H 2 )
COLUMN CS)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3A
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
H2
8
1
DELIMITER
9
9-13
5
SDG NO.
14
1
DELIMITER
9
15-24
10
MATRIX SPIKE -
EPA SAMPLE NO
25
1
DELIMITER
9
"ETAIL RECORD
1 CD1)
OLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3A
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
D1
8
1
DELIMITER
P
9-36
28
COMPOUND
37
1
DELIMITER
t
38-43
6
AMT. ADD CNG)
NUMERIC 6
44
1
DELIMITER
»
45-57
13
SAMPLE CONC. CUG/L)
NUMERIC 13.2
58
1
DELIMITER
9
59-71
13
MS CONC.
NUMERIC 13.2
72
1
DELIMITER
9
73-75
3
MS% REC.
NUMERIC 3
76
1
DELIMITER
9
77
1
MS% REC. FLAG
BLANK OR *
78
1
DELIMITER
9
H - 26
10/
-------
DETAIL RECORD 2 (D2)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3A
4- 5
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
D2
8
1
DELIMITER
9
9-36
28
COMPOUND
37
1
DELIMITER
9
38-50
13
MSD CONC.
NUMERIC 13.2
51
1
DELIMITER
t
52-54
3
MSDX REC.
NUMERIC 3
55
1
DELIMITER
»
56
1
MSDX REC. OUT FLAG
BLANK OR *
57
1
DELIMITER
t
58-60
3
MS* REC.
NUMERIC 3
61
1
DELIMITER
t
62
1
MSX REC. OUT FLAG
BLANK OR »
63
1
DELIMITER
t
64-66
3
X RPD
NUMERIC 3
67
1
DELIMITER
»
68
1
X RPD OUT FLAG
BLANK OR *
69
1
DELIMITER
»
H - 27
10/86
-------
DETAIL RECORD
i 3 (D3)
COLUMN CS)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3A
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
D3
8
1
DELIMITER
I
9-10
2
RPD: * OUTSIDE QC
LIMITS
NUMERIC 2
11
1
DELIMITER
1
12-13
2
RPD: TOTAL
NUMERIC 2
14
1
DELIMITER
9
15-16
2
SPIKE RECOVERY: *
OUT
NUMERIC 2
17
1
DELIMITER
9
18-19
2
SPIKE RECOVERY: TOTAL
NUMERIC 2
20
1
DELIMITER
$
21-22
2
SPIKE RECOVERY: *
OUT
NUMERIC 2
23
1
DELIMITER
i
COMMENT RECORD 1 (CI)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3A
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
CI
8
1
DELIMITER
t
9-79
71
COMMENT LINE 1
80
1
DELIMITER
t
COMMENT RECORD 2 CC2)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3A
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
C2
8
1
DELIMITER
9
9-79
71
COMMENT LINE 2
80
1
DELIMITER
9
COMMENT RECORD 3 CC3)
COLUMN
-------
SOIL VOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY - (FORM3B)
HEADER RECORD 1 (HI)
QLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3B
4- 5
2
FORM SUFFIX
A-22
6- 7
2
RECORD TYPE
HI
8
1
DELIMITER
t
9-43
25
LAB NAME
44
1
DELIMITER
9
45-55
11
CONTRACT
56
¦ 1
DELIMITER
9
57-62
6
LAB CODE
63
1
DELIMITER
9
64-68
5
CASE NO.
69
1
DELIMITER
$
70-75
6
SAS NO.
76
1
DELIMITER
9
EADER RECORD
2 (H2)
OLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
I- 3
3
FORM NUMBER
3B
4- 5
2
FORM SUFFIX
N
N
1
<
6- 7
2
RECORD TYPE
H2
8
1
DELIMITER
9
9-13
5
SDG NO.
14
1
DELIMITER
9
15-24
10
MATRIX SPIKE -
EPA SAMPLE NO
25
1
DELIMITER
9
26-28
3
LEVEL
LOU OR MED
29
1
DELIMITER
9
ETAIL RECORD
1 (Dl)
OLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3B
4- 5
2
FORM SUFFIX
A-Z2
5- 7
2
RECORD TYPE
Dl
8
1
DELIMITER
9
9-36
28
COMPOUND
37
1
DELIMITER
9
38-43
6
AMT. ADD (NG)
NUMERIC 6
44
1
DELIMITER
9
45-57
13
SAMPLE CONC. (UG/L)
NUMERIC 13.2
58
1
DELIMITER
9
59-71
13
MS CONC.
NUMERIC 13.2
72
1
DELIMITER
9
73-75
3
MSX REC-.
NUMERIC 3
76
1
DELIMITER
9
77
1
MSX REC. FLAG
BLANK OR *
78
1
DELIMITER
9
H - 29
10/86
-------
DETAIL RECORD 2 (D2)
:OLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3B
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
D2
a
1
DELIMITER
9
9-36
28
COMPOUND
37
1
DELIMITER
9
38-50
13
MSD CONC.
NUMERIC 13.2
51
1
DELIMITER
*
52-54
3
MSD* REC.
NUMERIC 3
55
1
DELIMITER
t
56
1
MSD* REC. OUT FLAG
BLANK OR »
57
1
DELIMITER
»
58-60
3
MS* REC.
NUMERIC 3
61
1
DELIMITER
»
62
1
MS* REC. OUT FLAG
BLANK OR *
63
1
DELIMITER
»
64-66
3
* RPD
NUMERIC 3
67
1
DELIMITER
•
68
1
* RPD OUT FLAG.
BLANK OR *
6*
1
DELIMITER
«
DETAIL RECORD
3 (03)
:pLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3B
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
D3
8
1
DELIMITER
i
9-10
2
RPD: * OUTSIDE
15-16
2
SPIKE RECOVERY: ~ OUT
NUMERIC 2
17
1
DELIMITER
»
18-19
2
SPIKE RECOVERY: TOTAL
NUMERIC 2
20
1
DELIMITER
»
21-22
2
SPIKE RECOVERY: 4 OUT
NUMERIC 2
23
1
DELIMITER
t
H - 30
10/86
-------
COMMENT RECORD 1 CCD
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3B
<~- 5
2
FORM SUFFJX
A-ZZ
S- 7
2
RECORD TYPE
CI
8
1
DELIMITER
1
9-79
71
COMMENT LINE 1
80
1
DELIMITER
9
COMMENT RECORD 2 CC2)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
5- 7
8
9-79
80
3
2
2
1
71
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
COMMENT LINE
DELIMITER
3B
A-ZZ
C2
COMMENT RECORD 3 CC3)
COLUMN (S) LENGTH CONTENTS
1- 3
4- 5
5- 7
8
9-79
80
3
2
2
I
71
1
FORMAT/CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
COMMENT LINE
DELIMITER
3B
A-ZZ
C3
H - 31
10/86
-------
1ATER SEMIVOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY-
-------
ETAIL RECORD 1 (Dl)
OLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3C
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
Dl
8
1
DELIMITER
.»
9-36
28
COMPOUND
37
1
DELIMITER
9
38-43
6
AMT. ADD (NG)
NUMERIC 6
44
1
DELIMITER
»
45-57
13
SAMPLE CONC.
IN EXTRACT CUG/L)
NUMERIC 13.2
58
1
DELIMITER
»
59-71
13
MS CONC.
IN EXTRACT (UG/L)
NUMERIC 13.2
72
1
DELIMITER
»
73-75
3
MSX REC.
NUMERIC 3
76
1
DELIMITER
»
77
1
MSX REC. FLAG
BLANK OR »
78
1
DELIMITER
$
ETAIL RECORD
2 CD2)
OIUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3C
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
D2
8
1
DELIMITER
»
9-36
28
COMPOUND
37
1
DELIMITER
»
38-50
13
MSO CONC.
IN EXTRACT (UG/L)
NUMERIC 13.2
51
1
DELIMITER
»
52-54
3
MSDX REC.
NUMERIC 3
55
1
DELIMITER
»
56
1
MSDX REC. OUT FLAG
BLANK OR »
57
1
DELIMITER
»
0
1
CO
in
3
MSX REC.
NUMERIC 3
61
1
DELIMITER
»
62
1
MSX REC. OUT FLAG
BLANK OR *
63
1
DELIMITER
t
64-66
3
X RPD
NUMERIC 3
67
1
DELIMITER
#
68
1
X RPD OUT FLAG
BLANK OR «
69
1
DELIMITER
*
H - 33
10/36
-------
ETAIL RECORD 3
21-22
2
SPIKE RECOVERY: * OUT
NUMERIC
2
23
1
DELIMITER
f
OMMENT RECORD 1 (CD
OLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3C
4- 5
2
FORM SUFFIX
A-ZZ
S- 7
2
RECORD TYPE
CI
8
1
DELIMITER
t
9-79
71
COMMENT LINE
1
80
¦ 1
DELIMITER
f
OMMENT RECORD 2 (C2)
OLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3C
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
C2
8
1
DELIMITER
»
9-79
71
COMMENT LINE
2
80
1
DELIMITER
*
OMMENT RECORD 3 (C3J
OLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3C
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
C3
8
1
DELIMITER
»
9-79
71
COMMENT LINE 3
80
1
DELIMITER
9
H - 34
10/86
-------
SOIL SEMIVOLATILE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY - CFORM3D)
-iEAOER RECORD
1 CHI)
:QLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3D
4- 5
2
FORM SUFFIX
A-Z2
6- 7
RECORD TYPE
HI
8
1
DELIMITER
9
9-43
25
LAB NAME
44
1
DELIMITER
9
45-55
11
CONTRACT
56
DELIMITER
9
57-62
6
LAB CODE
63
DELIMITER
9
64-68
CASE NO.
69
1
DELIMITER
9
70-75
6
SAS NO.
76
1
DELIMITER
9
HEADER RECORD
2 (H2)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3D
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
H2
8
I
DELIMITER
t
9-13
5
SD6 NO.
14
1
DELIMITER
9
15-24
10
MATRIX SPIKE -
EPA SAMPLE NO
25
1
DELIMITER
9
26-28
3
LEVEL
LOU OR MED
29
1
DELIMITER
f
H - 35
10/86
-------
DETAIL RECORD 1 (01)
:OLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3D
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
D1
8
1
DELIMITER
9
9-36
28
COMPOUND
37
1
DELIMITER
9
38-43
6
AMT. ADD (NG)
NUMERIC 6
44
1
DELIMITER
9
45-57
13
SAMPLE CONC.
• IN EXTRACT (UG/L)
NUMERIC 13.2
58
1
DELIMITER
9
59-71
13
MS CONC.
IN EXTRACT (UG/L)
NUMERIC 13.2
72
1
DELIMITER
t
73-75
3
MS* REC.
NUMERIC 3
76
1
DELIMITER
9
77
1
MS* REC. FLAG
BLANK OR *
78
1
DELIMITER
>
DETAIL RECORD
2 (D2 )
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3D
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
D2
8
1
DELIMITER
»
9-36
28
COMPOUND
37
1
DELIMITER
i
38-50
13
MSD CONC.
IN EXTRACT (UG/L)
NUMERIC 13.2
51
1
DELIMITER
i
52-54
3
MSDX REC.
NUMERIC 3
55
1
DELIMITER
r
56
1
MSD* REC. OUT FLAG
BLANK OR »
57
1
DELIMITER
»
58-60
3
MS* REC.
NUMERIC 3 '
61
1
DELIMITER
»
62
1
MS* REC. OUT FLAG
BLANK OR »
63
1
DELIMITER
t
64-66
3
X RPD
NUMERIC 3
67
1
DELIMITER
»
68
1
% RPD OUT FLAG
BLANK OR »
69
1
DELIMITER
*
H - 36
10/36
-------
ETAIL RECORD
3
(03)
OLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3D
4- 5
2
FORM SUFFIX
A-Z2
5- 7
2
RECORD TYPE
D3
8
1.
DELIMITER
9
9—10
2
RPD s • OUTSIDE
QC
LIMITS
NUMERIC 2
11
1
DELIMITER
9
12-13
2
RPD: TOTAL
NUMERIC 2
14
1
DELIMITER
9
15-16
2
SPIKE RECOVERY:
~
OUT
NUMERIC 2
17
1
DELIMITER
9
18-19
2
SPIKE RECOVERY:
TOTAL
NUMERIC 2
20
1
DELIMITER
»
21-22
2
SPIKE RECOVERY:
*
OUT
NUMERIC 2
23
1
DELIMITER
#
:OMMENT RECORD 1
(CI)
:OLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3D
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
CI
8
1
DELIMITER
i
9-79
71
COMMENT LINE 1
80
1
DELIMITER
»
iOMMENT RECORD 2
(C2)
;olumn (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3D
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
C2
8
1
DELIMITER
i
9-79
71
COMMENT LINE 2
80
1
DELIMITER
i
COMMENT RECORD 3
CC3)
:olumn CS)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3D
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
C3
8
1
DELIMITER
t
9-79
71
COMMENT LINE 3
80
1
DELIMITER
*
H - 37
10/86
-------
I ATE R PESTICIDE MATRIX SPIKE/MATRIX SPIKE DUPLICATE REC0VERY-CF0RM3E)
IEADER RECORD 1 (HI)
:QLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3E
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
HI
8
1
DELIMITER
»
9-43
25
LAB NAME
44
1
DELIMITER
*
45-55
11
CONTRACT
56
1
DELIMITER
»
57-62
6
LAB CODE
63
1
DELIMITER
»
64-68
5
CASE NO.
69
1
DELIMITER
70-75
6
SAS NO.
76
1
DELIMITER
t
IEADER RECORD 2 (H2)
:OLUMN (S)
1- 3
4- 5
6- 7
8
9-13
14
15-24
25
CONTENTS
LENGTH
3 FORM NUMBER.
2 FORM SUFFIX
2 RECORD TYPE
1 DELIMITER
5 SDG NO.
1 DELIMITER
10 MATRIX SPIKE -
EPA SAMPLE NO
1 DELIMITER
FORMAT/CONTENTS
3E
A-ZZ
H2
H - 38
10/86
-------
DETAIL RECORD 1 (01)
:OLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
FORM NUMBER
3E
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
D1
8
1
DELIMITER
»
9-36
28
COMPOUND
37
1
DELIMITER
r
38-43
6
AMT. ADD (NG)
NUMERIC 6
44
1
DELIMITER
>
45-57
13
SAMPLE CONC.
IN EXTRACT (UG/L)
NUMERIC 13.2
58
1
DELIMITER
»
59-71
13
MS CONC.
IN EXTRACT (UG/L)
NUMERIC 13.2
72
1
DELIMITER
»
73-75
3
MS* REC.
NUMERIC 3
76
1
DELIMITER
»
77
1
MSX REC. FLAG
BLANK OR *
7
1
DELIMITER
»
DETAIL RECORD
2 (D2)
:olumn (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3E
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
D2
8
1
DELIMITER
t
9-36
28
COMPOUND
37
1
DELIMITER
t
38-50
13
MSD CONC.
IN EXTRACT (UG/L)
NUMERIC 13.2
51
1
DELIMITER
»
52-54
3
MSDX REC.
NUMERIC 3
55
1
DELIMITER
»
56
MSDX REC. OUT FLAG
BLANK OR »
57
1
DELIMITER
i
58-60
3
MSX REC.
NUMERIC 3
61
1
DELIMITER
t
62
1
MSX REC. OUT FLAG
BLANK OR *
63
1
DELIMITER
t
64-66
3
X RPD
NUMERIC 3
67
1
DELIMITER
*
68
1
X RPD OUT FLAG
BLANK OR »
69
1
DELIMITER
$
H - 39
10/86
-------
ETAIL
OLUMN
RECORD 3 (03)
(S) LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3E
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
D3
8
1
DELIMITER
9
9-10
2
RPD: * OUTSIDE QC
LIMITS
NUMERIC 2
11
1
DELIMITER
9
12-13
2
RPD: TOTAL
NUMERIC 2
14
1
DELIMITER
9
15-16
2
SPIKE RECOVERY: 4
OUT
NUMERIC 2
17
1
DELIMITER
9
18-19
2
SPIKE RECOVERY: TOTAL
NUMERIC 2
20
1
DELIMITER
9
21-22
2
SPIKE RECOVERY: *
OUT
NUMERIC 2
23
1
DELIMITER
f
COMMENT RECORD 1
(CI)
:OLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3E
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
CI
8
1
DELIMITER
9
9-79
71
COMMENT LINE 1
80
1
DELIMITER
9
COMMENT RECORD 2
CC2)
:OLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3E
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
C2
8
1
DELIMITER
9
9-79
71
COMMENT LINE 2
80
1
DELIMITER
9
;OMMENT RECORD 3
(C3)
:olumn (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3E
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
C3
8
1
DELIMITER
9
9-79
71
COMMENT LINE 3
80
1
DELIMITER
9
H - 40
10/86
-------
SOIL PESTICIDE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY - CFORM3F)
HEADER RECORD 1' (HI)
COLUMN (S) LENGTH CONTENTS FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3F
4- 5
2
FORM SUFFIX
A-Z2
6- 7
2
RECORD TYPE
HI
8
1
DELIMITER
1
9-43
25
LAB NAME
44
1
DELIMITER
1
45-55
11
CONTRACT
56
DELIMITER
9
57-62
6
LAB CODE
63
1
DELIMITER
9
64-68
CASE NO.
69
1
DELIMITER
9
70-75
6
SAS NO.
76
1
DELIMITER
9
HEADER RECORD
2 CH2)
COLUMN CS)
LENGTH
CONTENTS
FORMAT/CONTENTS
1-3
3
FORM NUMBER
3F
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
H2
8
1
DELIMITER
f
9-13
5
SDG NO.
14
1
DELIMITER
9
15-24
10
MATRIX SPIKE -
EPA SAMPLE NO
25
1
DELIMITER
9
26-28
3
LEVEL
LOU OR MED
29
1
DELIMITER
9
H - 41
10/86
-------
DETAIL RECORD
1 (Dl)
COLUMN' (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3F
4- 5
2
FORM SUFFIX
A-Z2
5- 7
2
RECORD TYPE
Dl
8
1
DELIMITER
9
9-36
28
COMPOUND
37
1
DELIMITER
9
38-43
6
AMT. ADD (NG}
NUMERIC 6
44
1
DELIMITER
9
45-57
13
SAMPLE CONC.
IN EXTRACT CUG/L)
NUMERIC 13.2
58
1
DELIMITER
9
59-71
13
MS CONC.
IN EXTRACT (UG/L)
NUMERIC 13.2
72
1
DELIMITER
9
73-75
3
MSX REC.
NUMERIC 3
76
1
DELIMITER
»
77
1
MSX REC. FLAG
BLANK OR *
78
1
DELIMITER
i
DETAIL RECORD
2 (D2)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3F
4- 5
2
FORM SUFFIX
M
N
»
<
5- 7
2
RECORD TYPE
D2
8
1
DELIMITER
9-36
28
COMPOUND
37
1
DELIMITER
t
38-50
13
MSD CONC.
IN EXTRACT (UG/L)
NUMERIC 13.2
51
1
DELIMITER
*
52-54
3
MSD% REC.
NUMERIC 3
55
1
DELIMITER
»
56
1
MSDX REC. OUT FLAG
BLANK OR *
57
1
DELIMITER
*
58-60
3
MS% REC.
NUMERIC 3
61
1
DELIMITER
»
62
1
MS* REC. OUT FLAG
BLANK OR *
63
1
DELIMITER
t
64-66
3
X RPD
NUMERIC 3
67
1
DELIMITER
>
68
1
% RPD OUT FLAG
BLANK OR *
69
1
DELIMITER
*
H - 42 10/86
-------
FORMAT/CONTENTS
I- 3
3
FORM NUMBER
3F
<~- S
2
FORM SUFFIX
A-Z2
5- 7
2
RECORD TYPE
D3
8
1
DELIMITER
9
9-10
2
RPD: • OUTSIDE QC
LIMITS
NUMERIC 2
11
1
DELIMITER
t
12-13
2
RPD: TOTAL
NUMERIC 2
14
1
DELIMITER
t
15-16
2
SPIKE RECOVERY: *
OUT
NUMERIC 2
17
1
DELIMITER
»
18-19
2
SPIKE RECOVERY: TOTAL
NUMERIC 2
20
1
DELIMITER
t
21-22
2
SPIKE RECOVERY: *
OUT
NUMERIC 2
23
1
DELIMITER
»
COMMENT RECORD 1 (CI)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3F
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
CI
8
1
DELIMITER
t
9-79
71
COMMENT LINE
1
80
1
DELIMITER
»
COMMENT RECORD 2 CC2)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3F
*- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
C2
8
1
DELIMITER
i
9-79
71
COMMENT LINE
2
80
1
DELIMITER
t
COMMENT RECORD 3 CC3)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
3F
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
C3
8
1
DELIMITER
t
9-79
71
COMMENT LINE
3
80 i DELIMITER
H - *3
10/86
-------
FORM IV FILE DESCRIPTION
(FORM*)
H - 44
10/36
-------
VOLATILE METHOD BLANK SUMMARY - (FORM 4A)
HEADER RECORD 1 (HI)
COLUMN (S)
LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
4A
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
HI
8
1
DELIMITER
1
9-33
25
LAB NAME
34
1
DELIMITER
9
35-45
11
CONTRACT
46
1
DELIMITER
9
47-52
6
LAB CODE
53
1
DELIMITER
9
54-58
CASE NO.
59
1
DELIMITER
9
59-65
6
SAS NO.
66
1
DELIMITER
9
67-71
5
SDG NO.
72
1
DELIMITER
9
ADER RECORD
2 (H2)
LUMN (S>
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
4A
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
H2
8
1
DELIMITER
9
9-18
10
EPA SAMPLE NO. FOR
METHOD BLANK
19
1
DELIMITER
9
20-31
12
LAB SAMPLE ID
32
1
DELIMITER
9
33-42
10
INSTRUMENT ID
43
1
DELIMITER
9
44-57
14
LAB FILE ID
58
1
DELIMITER
9
59-66
8
DATE ANALYZED
MM/DD/YY
67
1
DELIMITER
9
68-71
4
TIME ANALYZED
HHMM
72
1
DELIMITER
9
73-77
5
MATRIX
SOIL OR WATER
78
1
DELIMITER
I
H - AS
10/86
-------
HEADER RECORD 3 CH3)
COLUMN (5) LENGTH CONTENTS
1- 3
4- 5
6- 7
8
9-11
12
3
2
2
1
3
1
FORMAT/CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
LEVEL
DELIMITER
4A
A-ZZ
H3
LOU OR MED
DETAIL RECORD 1 (Dl)
COLUMN (S)
1-
4-
5-
3
5
7
8
9-10
11
12-21
22
23-34
35
36-49
50
51-54
55
LENGTH
3
2
2
1
2
1
10
1
12
1
14
1
4
1
CONTENTS
FORMAT/CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
SEQUENCE NUMBER
DELIMITER
EPA SAMPLE NO.
DELIMITER
LAB SAMPLE ID
DELIMITER
LAB FILE ID
DELIMITER
TIME OF ANALYSIS
DELIMITER
4A
A-ZZ
Dl
NUMERIC 2
HHMM
COMMENT RECORD 1 CC1)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
4A
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
CI
8
1
DELIMITER
»
9-79
71
COMMENT LINE 1
80
1
DELIMITER
9
COMMENT RECORD 2 (C2)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
4A
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
C2
8
1
DELIMITER
I
9-79
71
COMMENT LINE 2
80
1
DELIMITER
9
H - 46
10-/86
-------
SEMIVOLATILE METHOD BLANK SUMMARY - (FORM 4B)
HEADER RECORD 1 (HI)
COLUMN (S)
1- 3
4- 5
6- 7
3
9-33
34
35-45
46
47-52
53
54-58
59
59-65
66
67-71
72
LENGTH
CONTENTS
FORMAT/CONTENTS
25
1
5
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
LAB NAME
DELIMITER
CONTRACT
DELIMITER
LAB CODE
DELIMITER
CASE NO.
DELIMITER
SAS NO.
DELIMITER
SD6 NO.
DELIMITER
4B
A-Z2
HI
HEADER RECORD 2 CH2)
COLUMN (S) LENGTH CONTENTS FORMAT/CONTENTS
1- 3 3 FORM NUMBER 4B
4-5 2 FORM SUFFIX A-ZZ
6-7 2 RECORD TYPE H2
8 1 DELIMITER ,
9-18 10 EPA SAMPLE NO. FOR
METHOD BLANK
19 1 DELIMITER ,
20-31 12 LAB SAMPLE ID
32 1 DELIMITER ,
33-42 10 INSTRUMENT ID
43 1 DELIMITER #
44-57 14 LAB FILE ID
58 1 DELIMITER ,
59-66 8 DATE EXTRACTED MM/DD/YY
67 1 DELIMITER ,
68-71 4 EXTRACTION (SEPF/CONT) SEPF OR CONT
72 1 DELIMITER ,
H - 47
10/86
-------
HEADER RECORD 3 CH3)
COLUMN (S) LENGTH CONTENTS FORMAT/CONTENTS
1- 3
3
FORM NUMBER
4B
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
H3
8
1
DELIMITER
P
9-16
8
DATE ANALYZED
MM/DD/YY
17
1
DELIMITER
18-21
4
TIME ANALYZED
HHMM
22
1
DELIMITER
23-27
5
MATRIX
SOIL OR MATER
28
1
DELIMITER
9
29-31
3
LEVEL
LOW OR MED
32
1
DELIMITER
#
DETAIL RECORD
1 CD1)
COLUMN CS)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
4B
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
D1
8
1
DELIMITER
t
9-10
2
SEQUENCE NUMBER
NUMERIC 2
11
1
DELIMITER
t
12-21
10
EPA SAMPLE NO.
22
. 1
DELIMITER
t
23-34
12
LAB SAMPLE ID
35
1
DELIMITER
>
36-49
14
LAB FILE ID
50
1
DELIMITER
»
51-58
8
DATE OF ANALYSIS
MM/DD/YY
59
1
DELIMITER
»
COMMENT RECORD 1 (CI)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
4B
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
CI
8
1
DELIMITER
*
9-79
71
COMMENT LINE 1
80
1
DELIMITER
i
COMMENT RECORD 2 CC2)
COLUMN CS)
LENGTH
CONTENTS
FORMAT/CONTENTS
1-3 3
4- 5 2
5-7 2
8 1
9-79 71
80 1
H - 48 10/86
FORM NUMBER 4B
FORM SUFFIX A-ZZ
RECORD TYPE C2
DELIMITER ,
COMMENT LINE 2
DELIMITER
-------
PESTICIDE METHOD BLANK SUMMARY - (FORM 4C)
HEADER RECORD 1 (HI)
COLUMN (S) LENGTH CONTENTS
1- 3
4- 5
6- 7
3
9-33
34
35-45
46
47-52
53
54-58
59
59-65
66
67-71
72
3
2
25
1
5
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
LAB NAME
DELIMITER
CONTRACT
DELIMITER
LAB CODE
DELIMITER
CASE NO.
DELIMITER
SAS NO.
DELIMITER
SD6 NO.
DELIMITER
FORMAT/CONTENTS
4C
A-2Z
HI
HEADER RECORD 2 CH2)
COLUMN (S) LENGTH : CONTENTS
1- 3
4- 5
6- 7
8
9-18
19
20-31
32
33-42
43
44-57
58
59-66
67
68-71
72
3
2
2
1
10
1
12
1
10
1
14
1
8
1
4
1
FORMAT/CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
EPA SAMPLE NO. FOR
METHOD BLANK
DELIMITER
LAB SAMPLE ID
DELIMITER
INSTRUMENT ID
DELIMITER
LAB FILE ID
DELIMITER
DATE EXTRACTED
DELIMITER
EXTRACTION
DELIMITER
4C
A-ZZ
H2
MM/DD/YY
SEPF OR CONT
H - 49
10/86
-------
HEADER RECORD 3 (H3)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
4C
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
H3
8
1
DELIMITER
9
9-16
8
DATE ANALYZED
(1)
MM/DD/YY
17
1
DELIMITER
9
18-25
8
DATE ANALYZED
(2)
MM/DD/YY
26
1
DELIMITER
9
27-30
4
TIME ANALYZED
(1)
HHMM
31
1
DELIMITER
9
32-35
4
TIME ANALYZED
(2)
HHMM
36
1
DELIMITER
9
37-46
10
INSTRUMENT ID
(1)
47
1
DELIMITER
9
48-57
10
INSTRUMENT ID
(2)
53
1
DELIMITER
59-69
11
GC COLUMN ID
(1)
70
1
DELIMITER
9
HEADER RECORD
4 (H4)
COLUMN (S) i
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
4C
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
H4
8
1
DELIMITER
t
9-19
11
GC COLUMN ID
(1)
20
1
DELIMITER
*
DETAIL RECORD
1 (Dl)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
I- 3
3
FORM NUMBER
4C
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
Dl
8
1
DELIMITER
9
9-10
2
SEQUENCE NUMBER
NUMERIC 2
11
1
DELIMITER
9
12-21
10
EPA SAMPLE NO
•
22
1
DELIMITER
9
23-34
12
LAB SAMPLE ID
<1>
35
1
DELIMITER
9
36-43
8
DATE ANALYZED
(1)
MM/DD/YY
44
1
DELIMITER
9
45-56
12
LAB SAMPLE ID
(2)
57
1
DELIMITER
9
58-65
8
DATE ANALYZED
(2)
MM/DD/YY
66
1
DELIMITER
9
H - 50
10/86
-------
COMMENT RECORD 1 (CI)
COLUMN (S) LENGTH CONTENTS FORMAT/CONTENTS
1-3 3 FORM NUMBER 4C
«- 5 2 FORM SUFFIX A-ZZ
S- 7 2 RECORD TYPE CI
8 1 OELZMITER ,
9-79 71 COMMENT LINE 1
80 1 DELIMITER ,
COMMENT RECORD 2 (C2)
COLUMN
-------
FORM V FILE DESCRIPTION
(FORM5)
H
52
10/86
-------
VOLATILE ORGANIC GC/MS TUNING AND MASS CALIBRATION - (F0RM5A)
BR0M0FLU0R08ENZENE (BFB)
HEADER RECORD I (HI)
COLUMN (S) LENGTH CONTENTS FORMAT/CONTENTS
1-3 3 FORM NUMBER 5A
4-5 2 FORM SUFFIX . A-ZZ
6- 7 2 RECORD TYPE HI
B 1 DELIMITER »
9-33 25 LAB NAME
34 1 DELIMITER ,
35-45 11 CONTRACT
46 1 DELIMITER ,
47-52 6 LAB CODE
53 1 DELIMITER ,
54-58 5 CASE NO.
59 1 DELIMITER »
60-65 6 SAS NO.
. 66 1 DELIMITER ,
67-71 5 SDS NO.
72 1 DELIMITER ,
HEADER RECORD 2 (H2)
COLUMN
-------
DETAIL
COLUMN
RECORD 1 CDi)
(S) LENGTH
CONTENTS
FORMAT/CONTENTS
1-3 3 FORM NUMBER 5A
4-5 2 FORM SUFFIX A-ZZ
5-7 2 RECORD TYPE D1
8 I DELIMITER ,
9-11 3 M/E NUMERIC 3
12 1 DELIMITER
13-52 40 ION ABUNDANCE CRITERION
53 1 DELIMITER ,
54-58 5 . X RELATIVE ABUNDANCE NUMERIC 5.1
59 1 DELIMITER
60-64 5 X MASS NUMERIC 5.1
65 1 DELIMITER ,
DETAIL RECORD 2 (D2)
COLUMN
-------
SEMIVOLATILE ORGANIC GC/MS TUNING AND MASS CALIBRATION - CF0RM5B)
DECAFLUOROTRIPHENYLPHOSPHINE (DFTPP)
HEADER RECORD 1 (HI)
COLUMN (S) LENGTH CONTENTS
I- 3
4- 5
6- 7
8
9-33
34
35-45
46
47-52
53
54-58
59
60-65
66
67-71
72
2
1
5
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
LAB NAME
DELIMITER
CONTRACT
DELIMITER
LAB CODE
DELIMITER
CASE NO.
DELIMITER
SAS NO.
DELIMITER
SDG NO.
DELIMITER
FORMAT/CONTENTS
5B
A-ZZ
HI
HEADER RECORD 2 (H2)
LUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
5B
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
H2
8
1
DELIMITER
1
9-22
14
LAB FILE ID
23
1
DELIMITER
9
24-31
8
DFTPP INJECTION
DATE
MM/DD/YY
32
1
DELIMITER
i
33-42
10
INSTRUMENT ID
43
1
DELIMITER
9
44-47
4
DFTPP INJECTION
TIME
HHMM
48
1
DELIMITER
9
H - 55
10/86
-------
3ETAIL RECORD 1 (01)
:OLUMN
-------
PORN VZ FILE DESCRIPTION
CFORM6)
H - 57 10/86
-------
VOLATILE ORSANICS INITIAL CALIBRATION DATA - (FORM 6A)
HEADER RECORD 1 (HI)
IOLUMN (S)
1- "3
4- 5
6- 7
8
9-33
34
35-45
46
47-52
53
54-58
59
60-65
66
67-71
72
LENGTH CONTENTS
FORMAT/CONTENTS
3
2
2
I
25
1
II
1
6
1
5
I
6
1
5
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
LAB NAME
DELIMITER
CONTRACT
DELIMITER
LAB CODE
DELIMITER
CASE NO.
DELIMITER
SAS NO.
DELIMITER
SDG NO.
DELIMITER
6 A
A-ZZ
HI
HEADER RECORD 2 (H2)
ILUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
6A
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
H2
8
1
DELIMITER
9
9-18
10
INSTRUMENT ID
19
1
DELIMITER
9
20-27
8
CALIBRATION DATE
1
MM/DD/YY
28
1
DELIMITER
*
29-36
8
CALIBRATION DATE
2
MM/DD/YY
37
1
DELIMITER
9
H - 58
10/86
-------
HEADER RECORD 3 (H3)
COLUMN (S)
LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
4- 5
2
FORM SUFFIX
6- 7
2
RECORD TYPE
a
1
DELIMITER
9-ia
10
RRF20 LAB
FILE
ID
19
1
DELIMITER
20-29
10
RRF50 LAB
FILE
ID
30
1
DELIMITER
31-40
10
RRF100 LAB
FILE
ID
41
1
DELIMITER
42-51
10
RRF150 LAB
FILE
ID
52
1
DELIMITER
53-62
10
RRF200 LAB
FILE
ID
63
1
DELIMITER
6A
A-ZZ
H3
DETAIL RECORD 1 (Dl)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
6A
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
Dl
8
1
DELIMITER
9
9-36
28
COMPOUND
37
1
DELIMITER
9
38-42
5
RRF20
NUMERIC
5.3
43
1
DELIMITER
»
44-48
5
RRF50
NUMERIC
5.3
49
1
DELIMITER
t
50-54
5
RRF100
NUMERIC
5.3
55
1
DELIMITER
#
56-60
5
RRF150
NUMERIC
5.3
61
1
DELIMITER
#
62-66
5
RRF200
NUMERIC
5.3
67
1
DELIMITER
t
68-72
5
AVERAGE RRF
NUMERIC
5.3
73
1
DELIMITER
»
74-78
5
X RSD
NUMERIC
5.1
79
1
DELIMITER
»
H - 39 10/86
-------
SEMIVOLATILE ORSANICS INITIAL CALIBRATION DATA - (FORM SB)
HEADER RECORD 1 (HI)
COLUMN (S) LENGTH CONTENTS
1- 3
4- 5
6- 7
8
9-33
34
35-45
46
47-52
53
54-58
59
60—65
66
67-71
72
3
2
25
1
5
1
FORM NUMBER
FO-RM SUFFIX
RECORD TYPE
DELIMITER
LAB NAME
DELIMITER
CONTRACT
DELIMITER
LAB CODE
DELIMITER
CASE NO.
DELIMITER
SAS NO.
DELIMITER
SD6 NO.
DELIMITER
FORMAT/CONTENTS
6B
A-ZZ
HI
HEADER RECORD 2 (H2)
COLUMN (S)
1-
4-
6-
3
5
7
8
9-18
19
20-27
28
29-36
37
LENGTH CONTENTS
3
2
2
1
10
1
8
1
8
1
FORMAT/CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
INSTRUMENT ID
DELIMITER
CALIBRATION DATE 1
DELIMITER
CALIBRATION DATE 2
DELIMITER
6B
A-ZZ
H2
MM/DD/YY
MM/DD/YY
H - 60
10/86
-------
HEADER RECORD 3 (H3)
COLUMN (S)
1- 3
4- 5
6- 7
8
9-ia
19
20-29
30
31-40
41
42-51
52
53-62
63
LENGTH CONTENTS
FORMAT/CONTENTS
3
Z
2
1
10
1
10
1
10
1
10
1
10
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
RRF20 LAB FILE ID
DELIMITER
RRF50 LAB FILE ID
DELIMITER
RRF80 LAB FILE ID
DELIMITER
RRF120 LAB FILE ID
DELIMITER
RRF160 LAB FILE ID
DELIMITER
68-
A-ZZ
H3
DETAIL RECORD 1 CD1)
COLUMN (S)
1- 3
4- 5
6- 7
8
9-36
37
38-42
43
44-48
49
50-54
55
56-60
61
62-66
67
68-72
73
74-78
79
LENGTH CONTENTS
FORMAT/CONTENTS
5
1
FORM NUMBER
6B
FORM SUFFIX
A-ZZ
RECORD TYPE
Dl
DELIMITER
$
COMPOUND
DELIMITER
9
RRF20
NUMERIC
5.3
DELIMITER
»
RRF50
NUMERIC
5.3
DELIMITER
»
RRF80
NUMERIC
5.3
DELIMITER
»
RRF120
NUMERIC
5.3
DELIMITER
i
RRF160
NUMERIC
5.3
DELIMITER
»
AVERAGE RRF
NUMERIC
5.3
DELIMITER
*
X RSD
NUMERIC
5.1
DELIMITER
t
H - 61
10/86
-------
SEMIVOLATILE ORGANICS INITIAL CALIBRATION DATA
- (FORM 6C)
HEADER RECORD 1 (HI)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
6C
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
RECORD TYPE
HI
8
1
DELIMITER
r
9-33
25
LAB NAME
34
1
DELIMITER
i
35-45
11
CONTRACT
46
1
DELIMITER
9
47-52
6
LAB CODE
53
1
DELIMITER
9
54-58
CASE NO.
59
1
DELIMITER
9
60-65
6
SAS NO.
66
1
DELIMITER
9
67-71
5
SDG NO.
72
1
DELIMITER
9
HEADER RECORD
2 (H2 )
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
I- 3
3
FORM NUMBER
6C
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
H2
8
1
DELIMITER
9
9-18
10
INSTRUMENT ID
19
1
DELIMITER
9
20-27
8
CALIBRATION DATE 1
MM/DO/YY
28
1
DELIMITER
9
29-36
8
CALIBRATION DATE 2
MM/DD/YY
37
1
DELIMITER
9
H - 62
10/86
-------
HEADER RECORD 3 (H3)
COLUMN CS)
LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8
9-18
19
20-29
30
31-40
41
42-31
32
53-62
63
3
2
2
1
10
1
10
1
10
1
10
1
10
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
RRF20 LAB FILE ID
DELIMITER
RRF50 LAB FILE ID
DELIMITER
RRF80 LAB FILE ID
DELIMITER
RRF120 LAB FILE ID
DELIMITER
RRF160 LAB FILE ID
DELIMITER
6C
A-ZZ
H3
DETAIL RECORD 1 (Dl)
COLUMN (S) LENGTH CONTENTS
FORMAT/CONTENTS
l-
4-
6-
9-3
3
38-4
4
44-48
4
50-3
5
36-6
6
62-6
6
68-7
7
74-78
79
28
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
COMPOUND
DELIMITER
RRF20
DELIMITER
RRF50
DELIMITER
RRF80
DELIMITER
RRF120
DELIMITER
RRF160
DELIMITER
AVERAGE RRF
DELIMITER
X RSD
DELIMITER
6C
A-ZZ
Dl
NUMERIC 5.3
NUMERIC 5.3
9
NUMERIC 5.3
NUMERIC 5.3
NUMERIC 5.3
NUMERIC 5.3
NUMERIC 5.1
H - 63
10/86
-------
FORM VII FILE DESCRIPTION
< F0RM7)
H
64
10/86
-------
/QUTXI.S CONTINUING CALIBRATION CHECK - (FORM 7A)
iEADEK RECORD I (HI)
:0LUMN (S) LENGTH CONTENTS
1-
*-
6-
f-J
3
33-4
4
*7-3
3
34-3
5
60-6
6
67-7
72
25
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
LAB NAME
DELIMITER
CONTRACT
DELIMITER
LAB CODE
DELIMITER
CASE NO.
DELIMITER
SAS NO.
DELIMITER
SD6 NO.
DELIMITER
FORMAT/CONTENTS
7A
A-ZZ
HI
DEADER RECORD 2 (H2)
:OLUMN (S) LENGTH CONTENTS
I- 3
4- 3
6- 7
a
9-18
19
20-27
28
29-32
33
34-47
48
49-36
37
38-63
66
1
14
8
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER.
INSTRUMENT ID
DELIMITER
CALIBRATION DATE
DELIMITER
CALIBRATION TIME
DELIMITER
LAB FILE ID
DELIMITER
INIT. CALIB. DATE 1
DELIMITER
INIT. CALIB. DATE 2
DELIMITER
FORMAT/CONTENTS
7A
A-ZZ
H2
MM/DD/YY
t
HHMM
*
MM/DD/YY
MM/DD/YY
H - 65
10/86
-------
DETAIL RECORD 1 (Dl)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
7A
4- 5
2
FORM SUFFIX
A-ZZ
5- 7
2
RECORD TYPE
01
8
1
DELIMITER
»
9-36
28
COMPOUND
37
1
DELIMITER
9
38-42
5
AVERAGE RRF
NUMERIC
5.3
43
1
DELIMITER
9
44-48
5
RRF50
NUMERIC
5.3
49
1
DELIMITER
9
50-54
5
% D
NUMERIC
5.1
55
1
DELIMITER
t
H - 66 10/86
-------
SEHIVOIATILE CONTINUING CALIBRATION CHECK - (FORM 7B)
HEADER RECORD 1 (HI)
COLUMN (S) LENGTH CONTENTS
1- 3
4- 5
4- 7
8
34
35-45
46
47-52
53
54-58
59
40-65
66
47-71
72
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
LAB NAME
DELIMITER
CONTRACT
DELIMITER
LAB CODE
DELIMITER
CASE NO.
DELIMITER
SAS NO.
DELIMITER
SDG NO.
DELIMITER
FORMAT/CONTENTS
7B
A-Z2
HI
HEADER RECORD 2 (H2)
COLUMN (S) LENGTH CONTENTS
FORMAT/CONTENTS
1-
4-
6-
9-1
1
20-2
2
29-32
3
34-4
4
49-5
5
58-6
6
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
INSTRUMENT ID
DELIMITER
CALIBRATION DATE
DELIMITER
CALIBRATION TIME
DELIMITER
LAB FILE ID
DELIMITER
INIT. CALIB. DATE 1
DELIMITER
INIT. CALIB. DATE 2
DELIMITER
7B
A-2Z
H2
MM/DD/YY
HHMM
i
MM/DD/YY
»
MM/DD/YY
H - 47
10/84
-------
DETAIL RECORD 1 CD1)
LUMN (S)
LENGTH
CONTENTS
I- 3
3
FORM NUMBER
4- 5
2
FORM SUFFIX
5- 7
2
RECORD TYPE
a
1
DELIMITER
9-36
23
COMPOUND
37
1
DELIMITER
38-42
5
AVERAGE RRF
43
1
DELIMITER
44-48
5
RRF50
49
1
DELIMITER
50-54
5
X D
55
1
DELIMITER
FORMAT/CONTENTS
7B
A-ZZ
D1
9
NUMERIC 5.3
NUMERIC 5.3
NUMERIC 5.1
H - 68
10/86
-------
SENIVOIpATXLE CONTINUING CALIBRATION CHECK -
(FORM 7C)
HEADER RECORD 1 (HI)
COLUMN (S) LENGTH CONTENTS
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
LAB NAME
DELIMITER
CONTRACT
DELIMITER
LAB CODE
DELIMITER
CASE NO.
DELIMITER
SAS NO.
DELIMITER
SDG NO.
DELIMITER
FORMAT/CONTENTS
7C
A-ZZ
HI
HEADER RECORD 2 (H2)
COLUMN (S) ' LENGTH CONTENTS
1-
4-
6-
9-1
1
20-2
2
29-3
3
34-4
4
49-3
5
58-6
6
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
INSTRUMENT ID
DELIMITER
CALIBRATION DATE
DELIMITER
CALIBRATION TIME
DELIMITER
LAB FILE ID
DELIMITER
INIT. CALIB. DATE 1
DELIMITER
INIT. CALIB. DATE 2
DELIMITER
FORMAT/CONTENTS
7C
A-ZZ
H2
MM/DD/YY
HHMM
MM/DD/YY
MM/DD/YY
H - 69
10/86
-------
3ETAIL RECORD 1 CD1)
:olumn CS)
1- 3
4- 5
5- 7
8
9-36
37
33-42
43
44-48
49
50-54
55
H - 70 10/86
LENGTH CONTENTS
3 FORM NUMBER
2 FORM SUFFIX
2 RECORD TYPE
1 DELIMITER
28 COMPOUND
1 DELIMITER
5 AVERAGE RRF
1 DELIMITER
5 RRF50
1 DELIMITER
5 X D
I DELIMITER
FORMAT/CONTENTS
7C
A-ZZ
01
NUMERIC 5.3
t
NUMERIC 5.3
NUMERIC 5.1
-------
FORM VIII FILE DESCRIPTION
(FORMS)
H - 71
10/86
-------
VOLATILE INTERNAL STANDARD AREA SUMMARY - (FORM 8A)
HEADER RECORD 1 (HI)
COLUMN (S)
1- 3
4- 5
6- 7
8
9-33
34
35-45
46
47-52
53
54-58
59
60-65
66
67-71
72
LENGTH
3
2
25
1
CONTENTS
FORMAT/CONTENTS
5
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
LAB NAME
DELIMITER
CONTRACT
DELIMITER
LAB CODE
DELIMITER
CASE NO.
DELIMITER
SAS NO.
DELIMITER
SD6 NO.
DELIMITER
8A
A-ZZ
HI
HEADER RECORD 2 (H2)
COLUMN (S) LENGTH CONTENTS FORMAT/CONTENTS
1- 3
3
FORM NUMBER
8A
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
HZ
8
1
DELIMITER
»
9-18
10
EPA SAMPLE NO. (STANDARD)
19
1
DELIMITER
t
20-27
8
DATE ANALYZED
MM/DD/YY
28
1
DELIMITER
i
29-42
14
LAB FILE ID (STANDARD)
43
1
DELIMITER
*
44-47
4
TIME ANALYZED
HHMM
48
1
DELIMITER
p
49-58
10
INSTRUMENT ID
59
1
DELIMITER
»
H - 72
10/86
-------
DETAIL RECORD 1 (01)
COLUMN (S)
1- 3
4- 5
6- 7
3
9-17
13
19-24
25
26-34
35
36-41
42
43-51
52
53-58
59
LENGTH CONTENTS
FORMAT/CONTENTS
3
2
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
12 HOUR STANDARD •
151 (BCM) AREA
DELIMITER
RT
DELIMITER
152 (DFB) AREA
DELIMITER
RT
DELIMITER
153 (CBZ) AREA
DELIMITER
RT
DELIMITER
8A
A-Z2
D1
NUMERIC 9
NUMERIC 6.2
NUMERIC 9
NUMERIC 6.2
NUMERIC 9
NUMERIC 6.2
DETAIL RECORD 2 CD2)
COLUMN (S)
1- 3
4- 5
6- 7
8
9-17
18
19-27
28
29-37
38
LENGTH CONTENTS
FORMAT/CONTENTS
3
2
2
1
9
1
9
1
9
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
UPPER LIMIT -
151 (BCM) AREA
DELIMITER
152 (DFB) AREA
DELIMITER
153 (CBZ) AREA
DELIMITER
8A
A-ZZ
D2
NUMERIC 9
NUMERIC 9
NUMERIC 9
DETAIL RECORD 3 (D3)
COLUMN (S) LENGTH CONTENTS
1- 3
4- 5
6- 7
8
9-17
18
19-27
28
29-37
38
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
LOWER LIMIT -
151 (BCM) AREA
DELIMITER
152 (DFB) AREA
DELIMITER
153 (CBZ) AREA
DELIMITER
FORMAT/CONTENTS
8A
A-ZZ
D3
f
NUMERIC 9
NUMERIC 9
NUMERIC 9
H - 73
10/86
-------
DETAIL RECORD 4 (D4)
COLUMN (S) LENGTH CONTENTS FORMAT/CONTENTS
1-3 3 FORM NUMBER • 8A
4- 5 2 FORM SUFFIX A-ZZ
6-7 2 RECORD TYPE D4
8 I DELIMITER ,
9-10 2 SEQUENCE NUMBER NUMERIC 2
II 1 DELIMITER ,
12-21 10 EPA SAMPLE NO.
22 1 DELIMITER ,
23-31 9 IS1 (BCM) AREA NUMERIC 9
32 I DELIMITER ,
33 1 ISl (BCM) AREA FLAS
34 1 DELIMITER ,
35-40 6 RT NUMERIC 6.2
' 41 1 DELIMITER ,
42-50 9 IS2 (DFB) AREA NUMERIC 9
51 1 DELIMITER ,
52 1 IS2 (DFB) AREA FLAG
53 1 DELIMITER ,
54-59 6 RT NUMERIC 6.2
60 1 DELIMITER
61-69 9 IS3 (CBZ) AREA NUMERIC 9
70 1 DELIMITER ,
71 1 IS3 (CBZ) AREA FLAG
72 1 DELIMITER ,
73-78 6 RT NUMERIC 6.2
79 1 DELIMITER ,
H - 74
10/86
-------
aEMIVOLATXLE INTERNAL STANDARD AREA SUMMARY - (FORM 83)
DEADER RECORD 1 (HI)
:0LUMN (S) LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
4- 5
6- 7
8
9-33
34
35-45
46
47-52
53
54-58
59
60-65
66
67-71
72
25
1
5
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
LAB NAME
DELIMITER
CONTRACT
DELIMITER
LAB CODE
DELIMITER
CASE NO.
DELIMITER
SAS NO.
DELIMITER
SD6 NO.
DELIMITER
8B
A-Z2
HI
HEADER RECORD 2 (H2)
COLUMN (S) LENGTH CONTENTS' FORMAT/CONTENTS
1-3 3 FORM NUMBER 8B
4-5 2 FORM SUFFIX A-ZZ
6-7 2 RECORD TYPE H2
8 1 DELIMITER *
9-18 10 EPA SAMPLE NO. (STANDARD)
19 1 DELIMITER #
20-27 8 DATE ANALYZED MM/DD/YY
28 1 DELIMITER
29-42 14 LAB FILE ID (STANDARD)
43 1 DELIMITER ,
44-47 4 TIME ANALYZED HHMM
48 1 DELIMITER
49-58 10 INSTRUMENT ID
59 1 DELIMITER
H - 75
10/86
-------
DETAIL RECORD 1 (01)
COLUMN (S) LENGTH CONTENTS FORMAT/CONTENTS
1-3 3 FORM NUMBER SB
4-5 2 FORM SUFFIX A-ZZ
6-7 2 RECORD TYPE D1
8 1 DELIMITER ,
12 HOUR STANDARD -
9-17 9 IS1 CDCB) AREA NUMERIC 9
18 1 DELIMITER ,
19-24 6 RT NUMERIC 6.2
25 1 DELIMITER ,
26-34 9 IS2 (NPT) AREA NUMERIC 9
35 1 DELIMITER ,
36-41 6 RT NUMERIC 6.2
42 1 DELIMITER ,
43-51 9 IS3 (ANT) AREA NUMERIC 9
52 1 DELIMITER
53-58 6 RT NUMERIC 6.2
59 1 DELIMITER ,
DETAIL RECORD 2 (D2)
COLUMN (S) LENGTH CONTENTS FORMAT/CONTENTS
1-3 3 FORM NUMBER 8B
4-5 2 FORM SUFFIX A-ZZ
6-7 2 RECORD TYPE D2
8 1 DELIMITER ,
UPPER LIMIT -
9-17 9 IS1 (DCB) AREA NUMERIC 9
18 1 DELIMITER #
19-27 9 IS2 (NPT) AREA NUMERIC 9
28 1 DELIMITER >
29-37 9 IS3 (ANT) AREA NUMERIC 9
38 1 DELIMITER
DETAIL RECORD 3 (D3)
COLUMN (S) LENGTH CONTENTS FORMAT/CONTENTS
1-3 3 FORM NUMBER SB
4-5 2 FORM SUFFIX A-ZZ
6-7 2 RECORD TYPE D3
8 1 DELIMITER ,
LOWER LIMIT -
9-17 9 IS1 (DCB) AREA NUMERIC 9
18 1 DELIMITER ,
19-27 9 IS2 (NPT) AREA NUMERIC 9
28 1 DELIMITER ,
29-37 9 IS3 (ANT) AREA NUMERIC 9
38 1 DELIMITER ,
H - 76 10/86
-------
DETAIL RECORD 4 (D4)
COLUMN CS) LENGTH CONTENTS FORMAT/CONTENTS
1-3 3 PORN NUMBER 8B
4-5 2 FORM SUFFIX A-2Z
6-7 2 RECORD TYPE D4
8 X DELIMITER »
9-10 2 SEQUENCE NUMBER NUMERIC 2
11 1 DELIMITER ,
12-21 10 EPA SAMPLE HO.
22 1 DELIMITER *
23-31 9 IS1 (DCB) AREA NUMERIC 9
32 1 DELIMITER »
33 1 IS1 (DCB) AREA FLA6
34 1 DELIMITER #
35-40 6 RT NUMERIC 6.2
41 1 DELIMITER ,
42-50 9 IS2 (NPT) AREA NUMERIC 9
51 1 DELIMITER ,
52 1 IS2 (NPT) AREA FLAG
53 1 DELIMITER ,
54-59 6 RT NUMERIC 6.2
60 1 DELIMITER
61-69 9 IS3 (ANT) AREA NUMERIC 9
70 1 DELIMITER t
71 1 IS3 (ANT) AREA FLAG
72 1 DELIMITER »
73-78 6 RT NUMERIC 6.2
79 1 DELIMITER »
H - 77
10/86
-------
SEMIVOLATILE
INTERNAL
STANDARD AREA SUMMARY -
(FORM
HEADER RECORD
1 (HI)
COLUMN (S)
LENGTH
CONTENTS
FO
1- 3
3
FORM NUMBER
8C
4- 5
2
FORM SUFFIX
A-
6- 7
2
RECORD TYPE
H1
8
1
DELIMITER
9
9-33
25
LAB NAME
34
1
DELIMITER
9
35-45
11
CONTRACT
46
1
DELIMITER
9
47-52
6
LAB CODE
53
1
DELIMITER
9
00
in
1
<*¦
in
CASE NO.
59
1
DELIMITER
9
60-65
6
SAS NO.
66
1
DELIMITER
9
67-71
5
SDG NO.
72
1
DELIMITER
9
FORMAT/CONTENTS
HEADER RECORD 2 (H2)
COLUMN (S)
LENGTH CONTENTS
FORMAT/CONTENTS
1-
4-
6-
3
5
7
8
9-18
19
20-27
28
29-42
43
44-47
48
49-58
59
3
2
2
1
10
1
8
1
14
1
4
1
10
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
EPA SAMPLE NO. (STANDARD)
DELIMITER
DATE ANALYZED
DELIMITER
LAB FILE ID (STANDARD)
DELIMITER
TIME ANALYZED
DELIMITER
INSTRUMENT ID
DELIMITER
8C
A-ZZ
H2
MM/DD/YY
HHMM
H - 78
10/86
-------
IETAZL RECORD 1 (01)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
8C
4- 3
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
D1
8
1
DELIMITER
»
12 HOUR STANDARD -
9-17
9
IS4 (PHN)
AREA
NUMERIC
9
18
DELIMITER
»
19-24
6
RT
NUMERIC
6.2
25
1
DELIMITER
»
26-34
IS5 (CRY)
AREA
NUMERIC
9
35
1
DELIMITER
»
36-41
6
RT
NUMERIC
6.2
42
1
DELIMITER
»
43-51
9
IS6 (PRY)
AREA
NUMERIC
9
52
1
DELIMITER
#
53-58
6
RT
NUMERIC
6.2
59
DELIMITER
»
ETAIL RECORD
2 (D2 )
OLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
FORM NUMBER
8C
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
D2
8
DELIMITER
i
UPPER LIMIT
9-17
9
IS4 (PHN)
AREA
NUMERIC
9
18
1
DELIMITER
#
19-27
9
IS5 (CRY)
AREA
NUMERIC
9
28
1
DELIMITER
»
29-37
9
IS6 (PRY)
AREA
NUMERIC
9
38
1
DELIMITER
»
ETAIL RECORD
3 (D3)
OLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
8C
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
D3
8
1
DELIMITER
»
LOWER LIMIT
-
9-17
9
IS4 (PHN)
AREA
NUMERIC
9
18
1
DELIMITER
t
19-27
9
IS5 (CRY)
AREA
NUMERIC
9
28
1
DELIMITER
»
29-37
9
IS6 (PRY)
AREA
NUMERIC
9
38
1
DELIMITER
»
H - 79
10/86
-------
DETAIL RECORD 4 (D4)
:OLUMN CS) LENGTH CONTENTS FORMAT/CONTENTS
1- 3 3 FORM NUMBER 8C
4-5 2 FORM SUFFIX A-ZZ
6-7 2 RECORD TYPE D4
8 1 DELIMITER ,
9-10 2 SEQUENCE NUMBER NUMERIC 2
11 1 DELIMITER
12-21 10 EPA SAMPLE NO.
22 1 DELIMITER ,
23-31 9 IS4 (PHN) AREA NUMERIC 9
32 X DELIMITER ,
33 1 IS4 (PHN) AREA FLA6
34 1 DELIMITER ,
35-40 6 RT NUMERIC 6.2
41 1 DELIMITER ,
42-50 9 1S5 (CRY) AREA NUMERIC 9
51 1 DELIMITER ,
52 1 IS5 (CRY) AREA FLAG
53 1 DELIMITER ,
54-59 6 RT NUMERIC 6.2
60 1 DELIMITER ,
61-69 9 IS6 (PRY) AREA NUMERIC 9
70 1 DELIMITER ,
71 1 IS6 (PRY) AREA FLAG
72 1 DELIMITER ,
73-78 6 RT . NUMERIC 6.2
79 1 DELIMITER ,
H - 80
10/86
-------
PESTICIDE EVALUATION STANDARDS SUMMARY - (FORM 80)
HEADER RECORD 1 (HI)
COLUMN (S) LENGTH CONTENTS FORMAT/CONTENTS
I- 3 3 FORM NUMBER 8D
4-5 2 FORM SUFFIX A-ZZ
6-7 2 RECORD TYPE HI
8 1 DELIMITER »
9-33 25 LAB NAME
34 1 DELIMITER ,
35-45 11 CONTRACT
46 1 DELIMITER
47-52 6 LAB CODE
53 1 DELIMITER
54-58 5 CASE NO.
59 1 DELIMITER »
60-65 6 SAS NO.
66 1 DELIMITER ,
67-71 5 SD6 NO.
72 1 DELIMITER #
HEADER RECORD 2 (H2)
LUMN (S)
LENGTH
CONTENTS
1- 3
3
FORM NUMBER
4- 5
2
FORM SUFFIX
6- 7
2
RECORD TYPE
8
1
DELIMITER
9-18
10
INSTRUMENT ID
19
1
DELIMITER
20-29
10
GC COLUMN ID
30
1
DELIMITER
DATES OF ANALYSIS
31-38
8
FROM'
39
1
DELIMITER
40-47
8
TO*
48
1
DELIMITER
FORMAT/CONTENTS
80
A-ZZ
H2
MM/DD/YY
MM/DD/YY
H - 81
10/86
-------
DETAIL RECORD 1 (Dl)
COLUMN
-------
ETAIL RECORD 3 (03)
OLUMH (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
8D
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
D3
8
1
DELIMITER
9
9-10
2
SEQUENCE NUMBER
NUMERIC
2
11
1
DELIMITER
»
12-23
12
LAB SAMPLE ID (STANDARD)
24
1
DELIMITER
9
25-28
4
TIME OF ANALYSIS
HHMM
2?
1
DELIMITER
9
30-34
S
ENDRIN
NUMERIC
5.1
33
1
DELIMITER
»
36-40
5
4»4'-DDT
NUMERIC
5.1
41
1
DELIMITER
t
1st
1
<*
5
COMBINED
NUMERIC
5.1
47
1
DELIMITER
»
H - 83
10/86
-------
'ESTICIDE EVALUATION STANDARDS SUMMARY - (FORM 8E)
•VALUATION OF RETENTION TIME SHIFT FOR DIBUTYL CHLORENDATE
IEAOER RECORD 1 (HI)
OLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
4- 5
2
FORM SUFFIX
6- 7
2
RECORD TYPE
8
1
DELIMITER
9-33
25
LAB NAME
34
1
DELIMITER
35-45
11
CONTRACT
46
1
DELIMITER
47-52
6
LAB CODE
53
1
DELIMITER
54-58
5
CASE NO.
59
1
DELIMITER
60-65
6
SAS NO.
66
1
DELIMITER
67-71
5
SD6 NO.
72
1
DELIMITER
SE
A-ZZ
HI
iEADER RECORD 2 (H2)
:OLUMN (S)
LENGTH CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
8E
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
H2
8
1
DELIMITER
i
9-18
10
INSTRUMENT ID
19
I
DELIMITER
»
20-29
10
GC COLUMN ID
30
1
DELIMITER
»
DATES OF ANALYSIS
31-38
8
FROM:
MM/DD/YY
39
1
DELIMITER
»
40-47
8
TO:
MM/DD/YY
48
1
DELIMITER
»
H - 84
10/86
-------
DETAIL RECORD 1 (Dl)
COLUMN
-------
FORM IX FILE DESCRIPTION
(F0RM9)
H - 86 10/86
-------
PESTICIDE/PCB STANDARDS SUMMARY - (FORM 9)
HEADER RECORD 1 (HI)
COLUMN (S) LENGTH CONTENTS
I- 3
4- 5
6- 7
8
9-33
34
35-45
46
47-52
53
54-58
59
60-65
66
67-71
72
25
1
5
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
LAB NAME
DELIMITER
CONTRACT
DELIMITER
LAB CODE
DELIMITER
CASE NO.
DELIMITER
SAS NO.
DELIMITER
SDG NO.
DELIMITER
FORMAT/CONTENTS
9
A-ZZ
HI
HEADER RECORD 2 (H2)
COLUMN (S) LE.NGTH CONTENTS
1- 3
4- 5
6- 7
8
9-18
19
20-29
30
3
2
2
1
10
1
10
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
INSTRUMENT ID
DELIMITER
GC COLUMN ID
DELIMITER
FORMAT/CONTENTS
9
A-2Z
H2
H - 87
10/86
-------
4EADER RECORD 3 (H3)
:OLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
9
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
H3
8
1
DELIMITER
9
9-16
8
DATE OF ANALYSIS
FROM:
MM/DD/YY
17
1
DELIMITER
9
18-25
8
DATE OF ANALYSIS
MM/DD/YY
26
1
DELIMITER
9
27-34
8
DATE OF ANALYSIS
TO:
MM/DD/YY
35
1
DELIMITER
»
36-39
4
TIME OF ANALYSIS
HHMM
40
1
DELIMITER
9
41-44
4
TIME OF ANALYSIS
FROM:
HHMM
45
1
DELIMITER
9
46-57
12
LAB SAMPLE ID (STANDARD)
58
1
DELIMITER
9
59-62
4
TIME OF ANALYSIS
TO:
HHMM
63
1
DELIMITER
9
JETAIL RECORD 1 (Dl)
COLUMN
-------
DETAIL RECORD 2 (02)
:OLUMN (S) LENGTH CONTENTS FORMAT/CONTENTS
1- 3 3 FORM NUMBER 9
4-5 2 FORM SUFFIX A-Z2
4-7 2 RECORD TYPE 02
8 1 QUANT Y OR N
9 1 DELIMITER ,
10-14 5 X 0 NUMERIC 5.1
15 1 DELIMITER ,
H - 89
10/86
-------
FORM X FILE DESCRIPTION
(FORM10)
H - 90
10/86
-------
PESTICIDE/PCB IDENTIFICATION - (FORM 10)
HEADER RECORD 1 (HI)
COLUMN (S)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3
FORM NUMBER
10
4- 5
2
FORM SUFFIX
A-ZZ
6- T
2
RECORD TYPE
HI
8
1
DELIMITER
>
9-18
10
EPA SAMPLE NO.
19
1
DELIMITER
*
20-44
25
LAB NAME
45
1
DELIMITER
»
46-56
11
CONTRACT
57
1
DELIMITER
»
58-63
6
LAB CODE
64
1
DELIMITER
»
•*>
1
in
>0
5
CASE NO.
70
1
DELIMITER
r
71-76
6
SAS NO.
71
1
DELIMITER
»
HEADER RECORD 2 (H2)
LUMN (S)
LENGTH
CONTENTS
1- 3
3
FORM NUMBER
4- 5
2
.FORM SUFFIX
6- 7
2
RECORD TYPE
8
1
DELIMITER
. 9-13
5
SDG NO.
14
1
DELIMITER
15-24
10
GC COLUMN ID 1
25
1
DELIMITER
26-35
10
GC COLUMN ID 2
36
1
DELIMITER
37-46
10
INSTRUMENT ID 1
47
1
DELIMITER
48-57
10
INSTRUMENT ID 2
58
1
DELIMITER
59-70
12
LAB SAMPLE ID 1
71
1
DELIMITER
FORMAT/CONTENTS
HEADER RECORD 3 (H3)
COLUMN (S) LENGTH CONTENTS
1- 3
4- 5
6- 7
8
9-20
21
22-35
36
3
2
2
1
12
1
14
1
FORM NUMBER
FORM SUFFIX
RECORD TYPE
DELIMITER
LAB SAMPLE ID
DELIMITER
LAB FILE ID
DELIMITER
10
A-ZZ
H2
FORMAT/CONTENTS
10
A-ZZ
H3
H - 91
10/86
-------
ETAIL RECORD 1 (01)
OLUMN CS)
LENGTH
CONTENTS
FORMAT/CONTENTS
1- 3
3 .
FORM NUMBER
10
4- 5
2
FORM SUFFIX
A-ZZ
6- 7
2
RECORD TYPE
D1
8
1
DELIMITER
9
9-10
SEQUENCE NUMBER
NUMERIC 2
11
1
DELIMITER
t
12-24
13
PESTICIDE/PCB
25
1
DELIMITER
9
26-31
6
RETENTION TIME
COLUMN 1
NUMERIC 6.2
32
1
DELIMITER
9
33-38
6
RT WINDOW OF STANDARD
FROM:
NUMERIC 6.2
39
1
DELIMITER
•
40-45
6
TO:
NUMERIC 6.2
46
1
DELIMITER
9
47
1
QUANT?
Y OR N
48
1
DELIMITER
9
49
1
6C/MS?
Y OR N
50
1
DELIMITER
9
ETAIL RECORD 2 (D2)
OLUMN (S)
X- 3
4- 5
6- 7
8
9-10
11
12-24
25
26-31
32
32-38
39
40-45
46
47
48
49
50
LENGTH CONTENTS
FORMAT/CONTENTS
FORM NUMBER
FORM SUFFIX.
RECORD TYPE
DELIMITER
SEQUENCE NUMBER
DELIMITER
PESTICIDE/PCB
DELIMITER
RETENTION TIME
COLUMN 2
DELIMITER
RT WINDOW OF STANDARD
FROM:
DELIMITER
TO:
DELIMITER
QUANT?
DELIMITER
GC/MS?
DELIMITER
10
A-ZZ
D2
NUMERIC 2
NUMERIC 6.2
i
NUMERIC 6.2
>
NUMERIC 6.2
Y OR N
Y OR N
H -
92
10/86
-------
COMMENT RECORD 1 CC1)
COLUMN (S) LENGTH CONTENTS FORMAT/CONTENTS
1-3 3 FORM NUMBER 10
4-5 2 FORM SUFFIX A-2Z
5-7 2 RECORD TYPE CI
8 1 DELIMITER »
9-79 71 COMMENT LINE 1
80 1 DELIMITER ,
COMMENT RECORD 2 CC2)
COLUMN (S) LENGTH CONTENTS FORMAT/CONTENTS
1-3 3 FORM NUMBER 10
"4-5 2 FORM SUFFIX A-ZZ
5-7 2 RECORD TYPE C2
8 1 DELIMITER ,
9-79 71 COMMENT LINE 2
80 1 DELIMITER ,
COMMENT RECORD 3 (C3)
COLUMN (S) LEN6TH CONTENTS FORMAT/CONTENTS
1- 3 3 FORM NUMBER 10
A- 5 2 FORM SUFFIX A-ZZ
5-7 2 RECORD TYPE C3
8 1 DELIMITER
9-79 71 COMMENT LINE 3
80 1 DELIMITER ,
H - 93
10/86
------- |