i in rtoH otato* m !«, nf Publication 9240.1 -22
United States Otttoe Ot
Environmental Protection Solid Waste and
Agency Emergency Response
Superfund _____
xvEPA USEPA CONTRACT
LABORATORY PROGRAM
STATEMENT OF WORK
FOR ANALYSIS OF
POLYCHLORINATED DIBENZO-P-DIOXINS (PCDD)
AND
POLYCHLORINATED DIBENZOFURANS (PCDF)
MULTI-MEDIA, MULTI-CONCENTRATION
DFLM 01.1
-------
9240.1-22
PB95-963520
EPA540/R-94/089
USEPA CONTRACT LABORATORY PROGRAM
STATEMENT OF WORK
FOR ANALYSIS OF
POLYCHLORINATED DIBENZO-P-DIOXINS (PCDD)
AND POLYCHLORINATED DIBENZOFURANS (PCDF)
Multi-Media, Multi-Concentration
Document Number DFLM01.0
Including Revision DFLM01.1 (September 1991)
-------
STATEMENT OF WORK
TABLE OF CONTENTS
EXHIBIT A: SUMMARY OF REQUIREMENTS
EXHIBIT B: REPORTING AND DELIVERABLES REQUIREMENTS
EXHIBIT C: TARGET COMPOUND LIST (TCL) AND CONTRACT REQUIRED QUANTITATION
LIMITS (CRQL)
EXHIBIT D: ANALYTICAL METHODS
»
EXHIBIT E: QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
EXHIBIT F: CHAIN-OF-CUSTODY, DOCUMENT CONTROL, AND STANDARD OPERATING .
PROCEDURES
EXHIBIT G: GLOSSARY
DFLM01.0
-------
EXHIBIT A
SUMMARY OF REQUIREMENTS
DFLM01.0
-------
Table of Contents
Page
SECTION I: General Requirements A- 3
SECTION II: Specific Requirements A-6
SECTION III: Detailed Technical and Management Requirements A-9
A-2 DFLM01.0
-------
SECTION I
GENERAL REQUIREMENTS
A. Purpose of the Statement of Work
Under the legislative authority granted to the U.S. Environmental
Protection Agency (EPA) under the Comprehensive Environmental Response,
Compensation, and Liability Act of 1980 (CERCLA) and the Superfund
Amendments and Reauthorization Act of 1986 (SARA), EPA develops
standardized analytical methods for the measurement of various
pollutants in environmental samples from known or suspected hazardous
waste sites. Polychlorinated dibenzo-p-dioxins and polychlorinated
dibenzofurans (PCDDs/PCDFs) are among the pollutants that are of
concern to EPA at such sites. PCDDs/PCDFs are believed to be among the
most toxic organic compounds ever released into the environment.
With the advent of the Superfund program in 1980, EPA required the
analyses of many more environmental samples than could possibly be
handled through its own laboratories. Therefore, EPA elected to
procure analytical services through commercial laboratories and
established the Contract Laboratory Program (CLP) as a means of
obtaining standardized analyses on a long-term firm, fixed-price basis.
This Statement of Work (SOW) provides a technical and contractual
framework for laboratories to apply EPA analytical methods to the
analysis of PCDDs/PCDFs in environmental samples. The SOW provides not
only the analytical methods to be applied, but also the specific
technical and contractual requirements by which EPA will evaluate the
data.
B. General Requirements
This SOW provides an analytical method for the isolation, detection and
quantitative measurement of PCDDs and PCDFs in water, soil, fly ash,
and chemical waste samples such as oil, sludge, and stillbottoms.
There are 210 possible PCDD/PCDF isomers, and the methods were
developed for the analysis of the 17 PCDDs/PCDFs that bear chlorine
atoms in the 2,3,7 and 8 positions of their respective structures.
These 17 compounds, termed the "2,3,7,8-substituted PCDDs/PCDFs," are
those PCDDs/PCDFs that, based on structure activity relationships, are
believed to pose the greatest risks to human health and the
environment. The SOW also requires determination of the total
concentrations of all PCDDs or PCDFs in a given level of chlorination
(i.e., Total TCDD, Total PecDD, etc.), although complete
chromatographic separation of all 210 PCDDs/PCDFs is not possible under
the instrumental conditions described in the method.
The SOW requires the calculation of the 2378-TCDD toxicity equivalence
using the procedures described in the "Update of Toxicity Equivalency
Factors (TEFs) for Estimating Risks Associated with Exposures to
Mixtures of Chlorinated Dibenzo-p-Dioxins and Dibenzofurans
(CDDs/CDFs)," March 1989, (EPA'625/3-89/016). To aid in the assessment
A-3 DFLM01.1 (9/91)
-------
of risks associated with exposure to these compounds, a factor is
assigned to each of the 17 2,3,7,8-substituted FCDDs and FCDFs that
relates the toxicity of that isomer to a concentration of the most
toxic isomer, 2378-TCDD. The concentrations of any isomers that are
detected in an environmental sample can then be adjusted by the
toxicity equivalency factor (x£7) and summed, yielding a concentration
of 2378-TCDD with an equivalent toxicity.
Because isomer specificity for all 17 2378-substituted PCDDs/PCDFs may
not be achieved using a single gas chromatographic column, the SOW
requires analysis of sample extracts on a second column when the TEF-
adjusted concentration exceeds a specified level. This level varies by
sample matrix.
The sample preparation procedures in the SOW use matrix-specific
extraction techniques and a single set of cleanup techniques. The
sensitivity of this method is dependent upon"the level of interferents
within a given sample. Interferents co-extracted from the sample may
vary considerably from source to source, depending on the origin of the
sample and the matrix type. PCDDs and FCDFs are often associated with
other chlorinated compounds such as PCBs and polychlorinated diphenyl
ethers which may occur at concentrations several orders of magnitude
higher than that of the analytes of interest and may cause interference
problems.
The samples to be analyzed by the Contractor are from known or
suspected hazardous waste sites and may contain hazardous organic
and/or inorganic materials at high concentration levels. The
Contractor should be aware of the hazards associated with the handling
and analysis of these samples. The Contractor is responsible for
taking all necessary measures to ensure the health and safety of its
employees.
The Contractor must be aware of the importance of maintaining the
integrity of the data generated under the contract, as data may be used
to make decisions regarding public health and environmental welfare.
In addition, the data may be used in litigation against potentially
responsible parties in the enforcement of Superfund legislation.
Applications and Limitations of the Statement of Work
This SOW is designed as part of the documentation for a contract
between EPA and a commercial laboratory performing analyses in support
of EPA Superfund programs. The resulting data may be used by EPA for a
variety of purposes, such as determining the nature and extent of
contamination at a hazardous waste site, assigning administrative
priority to such sites based on the risk of exposure, determining
appropriate cleanup actions, and determining when remedial actions are
complete.
The methods described in this SOW are designed for the analysis of
specific analytes in specific environmental matrices and over a limited
concentration range. However, this SOW is not suitable for all
analytical situations and should not be applied to matrices, analytes,
A-4 DFLM01.0
-------
or concentration ranges for which it was not intended. Similarly, the
contractual requirements embodied in the SOW apply only to those
analyses performed by commercial laboratories through the CLP.
Therefore, other organizations wishing to procure analytical services
using the methods in this SOW are advised to develop a contracting
mechanism that explicitly includes both the technical and contractual
requirements contained in this SOW.
D. Organization of the Statement of Work
Exhibit A provides an overview of the SOW and its general requirements.
Exhibit B contains a description of the reporting and deliverables
requirements, in addition to the data reporting forms and the forms
instructions. Exhibit C specifies the target compound list for this
SOW with the contract-required quantitation limits for sample matrices.
Exhibit D details the specific analytical procedures to be used with
this SOW and resulting contracts. Exhibit E provides descriptions of
required quality assurance/quality control (QA/QC) standard operating
procedures and procedures used for the evaluation of analytical
methodologies, QA/QC performance, and the reporting of data. Exhibit F
contains chain-of-custody and sample documentation requirements which
the Contractor shall follow. To ensure proper understanding of the
terms utilized in this SOW, a glossary can be found in Exhibit G.
A-5 DFLM01.0
-------
SECTION II
SPECIFIC
A. Sample shipments to the Contractor's facility will be scheduled and
coordinated by the EPA CLP Sample Management Office (SMO) acting on
behalf of the Administrative Project Officer. The Contractor shall
communicate with SMO personnel by telephone, as necessary throughout the
process of sample scheduling, shipment, analysis and data reporting, to
ensure that samples are properly processed.
If there are problems w__.. 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 in advance regarding sample data that will be delivered late and
shall specify the estimated delivery date.
B. 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 includes one or more field samples
with associated blanks. Samples may be shipped to the Contractor in a
single shipment or multiple shipments over a period of time, depending
on the size of the Case.
A Case consists of one or more Sample Delivery Group(s). A Sample
Delivery Group (SDG) is defined by the following, whichever is most
frequent:
o Each Case of field samples received, OR
o Each 20 field samples within a Case, OR
o Each 14 calendar day period during which field samples in a Case
are received (said period beginning with the receipt of the
first sample in the SDG).
Samples may be assigned to SDGs by matrix (e.g., all soil samples in one
SDG, all water samples a second SDG, and all fly ash samples in a third
SDG), at the discretion of the laboratory. Such assignment must be made
at the time the samples are received and may not be made retroactively.
All data for all samples in a SDG are due concurrently to all data
recipients as stipulated in the Delivery Schedule in Exhibit B, Section
I. Data for all samples in a SDG must be submitted together (in one
package) in the order specified in Exhibit B. The SDG number is the EPA
sample number of the first sample received in the SDG. When several
samples are received together in the first SDG shipment, the SDG number
A-6 DFLM01.0
-------
shall be the lowest sample number (considering both alpha and numeric
designations) in the first group of samples received under the SDG. The
SDG number is reported on all data reporting forms.
The SDG receipt date is the day the last sample in the SDG is received.
Eata for all samples in the SDG ar due as stipulated in thr Delivery
Schedule in Exhibit B.
The Contractor is responsible for identifying each SDG as samples are
received, through proper sample documentation (see Exhibit B) and
communication with SMO personnel.
C. Each sample received by the Contractor will be labeled with an EPA
sample number and will be accompanied by a Traffic Report 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 for each sample container.
The Contractor shall submit signed copies of Traffic Reports for all
samples in a SDG to SMO within three calendar days following receipt of |
the last sample in the SDG. Traffic Reports shall be submitted in SDG
sets (i.e., all Traffic Reports for a SDG shall be clipped together)
with a SDG Cover Sheet containing information regarding the SDG, as
specified in Exhibit B.
D. The Contractor shall use EPA Case numbers (including SDG numbers) and
EPA sample numbers to identify samples received under this contract both
verbally and in reports/correspondence.
E. Samples will be shipped routinely to the Contractor through an overnight
delivery service. However, as necessary, the Contractor shall be
responsible for any handling or processing required for the receipt of
sample shipments, including pick-up of samples at the nearest servicing
airport, bus station or other carrier service within the Contractor's
geographical area. The Contractor shall be available to receive sample
shipments at any time the delivery service is operating, including
Saturdays.
F. The Contractor shall accept all samples scheduled by SMO, provided that
the total number of samples received in any calendar month does not
exceed the monthly limitation expressed in the contract. Should the
Contractor elect to accept additional samples, the Contractor shall
remain bound by all contract requirements for analysis of those samples
accepted.
G. The Contractor shall prepare, extract, cleanup extracts, and analyze
samples according to the analytical procedures outlined in Exhibit D.
The Contractor shall also adhere to the QA/QC requirements specified in
Exhibit D, including the analyses of calibration standards, blanks,
spiked samples, duplicate analyses, etc., as specified in the exhibit.
A-7 DFLM01.1 (9/91)
-------
H. EPA has provided the Contractor with forms for the reporting of data
(Exhibit B). The Contractor shall be responsible for completing and
returning analysis data sheets in the format specified in the Contract
Performance/Delivery Schedule.
Use of formats other than tnose designate ._, c.r*i wo.ll be deemed as
noncompliance. Such data are unacceptable. Resubmission in the
specified format will be required at no additional cost to the
Government.
I. The Contractor shall have sufficient gas chromatograph/mass
spectrometer/data system (GC/MS/DS) capability to meet all the terms and
conditions of the EPA contract. The Contractor shall maintain, at a
minimum, all analytical equipment allocated for this contract at the
time of contract award. (See Section III for instrumentation
requirements.)
J. Certain samples may require sample reruns (reextraction and/or
reanalysis) due to either problems with the sample matrix or Contractor
insufficiencies. Sample reruns may be considered either as billable or
nonbillable as defined in Exhibit D. For the purposes of this contract,
the term "automatic rerun" shall signify only billable rerun analyses.
K. EPA may -provide standards for use in analyses performed under the
contract, subject to availability. However, the SOW identifies specific
solutions that must be purchased from commercial sources, and will not
be provided by EPA. When provided, EPA-supplied materials are intended
for use only on EPA samples, and the Contractor may be asked to
demonstrate during EPA on-site evaluations that separate standards are
maintained for non-EPA work. The Contractor will be instructed how and
where to request EPA standards at time of contract award. The
Contractor is responsible for ensuring that all required standards are
available at the Contractor's facility before accepting any samples from
EPA.
L. The Contractor shall respond within seven days to requests from data
recipients for additional information or explanations that result from
the Government's inspection activities.
M. The Contractor shall preserve all sample extracts after analysis in
bottles/vials with Teflon-lined septa and shall maintain stored extracts
in the dark at room temperature. The Contractor is required to retain
the sample extracts for 365 days after data submission. During that
time, the Contractor shall submit the 'extracts within seven days after
request, as specified in the Contract Performance/Delivery Schedule.
N. The Contractor shall adhere to chain-of-custody procedures described in
Exhibit F. Documentation, as described therein, shall show that all
procedures are being strictly followed. This documentation shall be
reported as the Complete SDG File (see Exhibit B).
A-8 DFLM01.0
-------
SECTION III
DETAILED TECHNICAL AND MANAGEMENT REQUIREMENTS
The Contractor shall have the following technical and management
capabilities. For those technical functions that require a minimum
educational degree and experience, an advanced degree in chemistry or any
scientific/engineering discipline (e.g., Master's or Doctorate) does not
substitute for the minimum experience requirements.
The Contractor shall notify in writing the Technical Project Officer and the
Administrative Project Officer of any changes affecting key personnel listed
in this section within 14 days of the change. The Contractor shall provide a
detailed resume to the Technical Project Officer, Administrative Project
Officer, and EMSL-LV for the replacement personnel within 14 days of the
Contractor's assignment of the personnel. The resume shall include position
description of titles, education (pertinent to this contract), number of
years of experience (pertinent to this contract), month and year hired,
previous experience and publications.
A. TECHNICAL CAPABILITY
1. Technical Functions
a. GC/MS Laboratory Supervisor
(1) Responsible for all technical efforts of the GC/MS
laboratory to meet all terms and conditions of the EPA
contract.
(2) Qualifications:
(a) Education:
Minimum of a Bachelor's degree in chemistry or any
scientific/engineering discipline.
(b) Experience:
Minimum of three years of laboratory experience with
dioxin and furan analyses, including at least one
year of supervisory experience.
b. Sample Preparation Laboratory Supervisor
(1) Responsible for all technical efforts of sample
preparations to meet all terms and conditions of the EPA
contract.
A-9a DFLM01.1 (9/91)
-------
(2) Qualifications:
(a) Education:
Minimum of a Bachelor's degree in chemistry or any
scientific/engineering discipline.
(b) Experience:
Minimum of three years of laboratory experience,
including at least one year of supervisory
experience.
A-9b DFLM01.1 (9/91)
-------
c. Quality Assurance Officer
(1) Responsible for overseeing the QA aspects of data and
reporting directly to upper management to meet all terms
and conditions of the EPA contract.
(2) Qualifications:
(a) Education:
Minimum of a Bachelor's degree in chemistry or any
scientific/engineering discipline.
(b) Experience:
Minimum of three years of laboratory experience,
including at least one year of applied experience
with QA principles and practices in an analytical
laboratory.
d. GC/MS Operator Qualifications
One year of experience in operating and maintaining GC/MS/DS
used, for selected ion monitoring (SIM) with a Bachelor's degree
in chemistry or any scientific/engineering discipline, or in
lieu of the Bachelor's degree, three years of experience in
operating and maintaining the GC/MS and interpreting GC/MS SIM
data.
e. Extract Cleanup Expert Qualifications
One year of experience in extract cleanup with a Bachelor's
degree in chemistry or any scientific/engineering discipline,
or in lieu of the Bachelor's degree, three years 'of experience
in sample extraction and cleanup.
f. Extraction/Concentration Expert Qualifications
(1) Education:
Minimum of high school diploma and a college-level course
in general chemistry.
(2) Experience:
Minimum of one year of experience in
extraction/concentration.
g. Technical Staff Redundancy
The bidder shall have a minimum of one chemist available at any
one time as a back-up technical person with the following
qualifications to ensure continuous operations to accomplish
the required work as specified by the EPA contract.
A-10 DFLM01.0
-------
(1) Education:
Minimum of a Bachelor's degree in chemistry or any
scientific/engineering discipline.
(2) Experience: Min'*?um of one year in each of the following
areas -
o GC/MS operation and maintenance using
selected ion monitoring.
o Dioxin/furan analysis.
o Sample extraction and cleanup.
2. Facilities
The adequacy of the facilities and equipment is of equal importance
as the technical staff to accomplish the required work as specified
by the EPA contract.
a. Sample Receipt Area
Adequate, contamination-free, well-ventilated work space
provided with chemical resistant bench top for receipt and safe
handling of EPA samples.
b. Storage Area
Sufficient space to maintain unused EPA sample volume for 60
days after data submission and sample extracts for 365 days
after data submission. Samples must be stored in an atmosphere
demonstrated to be free from all potential contaminants.
c. Sample Preparation Area
Adequate, contamination-free, well-ventilated work space
provided with:
(1) Benches with chemical resistant tops, exhaust hoods.
NOTE: Standards must be prepared in a glove box or
isolated area.
(2) Source of distilled or demineralized organic-free water.
(3) Analytical balance(s) located away from draft and rapid
change in temperature.
3. Instrumentation
At a minimum, the Contractor shall have the following instruments
operative and committed for the full duration of the contract.
A-11 DFLM01.1 (9/91)
-------
a. Primary Instrument Requirements
(1) GC/MS equipped with GO to MS interface capable of
extending a 60 meter by 0.32 mm ID, bonded DB-5 (or
equivalent), fused silica capillary column into the MS ion
source.
(2) GC/MS computer interfaced by hardware to the MS and
capable of monitoring at least 18 selected ions for the
duration of the chromatographic analysis.
(3) GC/MS computer equipped with mass storage device for
saving all data from GC/MS analyses.
(4) GC/MS computer software capable of searching GC/MS
analyses for specific ions and plotting the intensity of
the ions with respect to time or scan run.
(5) Magnetic tape storage device capable of recording data for
long-term, off-line storage.
b. Secondary Instrument Requirements
The Contractor shall have one back-up instrument, identical to
the requirements above, in place and operational at any time.
This instrument must be included in the bidder's inventory of
equipment. In addition, the Contractor shall have an in-house
stock of instrument parts and circuit boards to ensure
continuous operation to meet contract-specified holding and
turnaround times.
4. Data Handline and Packaging
The Contractor shall have reasonable capacity to submit reports and
data packages as specified in Exhibit B. To complete this task, the
Contractor shall be required to:
a. Provide space, tables and copy machines to meet the contract
requirements.
b. Designate personnel.
B. LABORATORY MANAGEMENT CAPABILITY
The Contractor must have an organization with well-defined
responsibilities for each individual in the management system to ensure
sufficient resources for EPA contract(s) and to maintain a successful
operation. To establish this capability, the Contractor shall designate
personnel to carry out the following responsibilities for the EPA
contract. Functions include, but are not limited to, the following:
1. Technical Staff
Responsible for all technical efforts for the EPA contract.
A-12 DFLM01.0
-------
Project Manager
Responsible for overall aspects of EPA contract(s) (from sample
receipt through data delivery) and the primary contact for the
Administrative Project Officer and Technical Project Officer.
SainDle Custodian
Responsible for receiving EPA samples (logging, handling and
storage) .
A . Quality Assurance Officer
Responsible for o\_^ seeing the QA aspects of the data and reporting
directly to upper management.
»
5 . Document Control Officer
Responsible for ensuring that all documents generated are placed in
the Complete SDG File for inventory and are delivered to the
appropriate EPA Region or other receiver as designated by EPA.
A-13 DFLM01.0
-------
EXHIBIT B
REPORTING AND DELIVERABLES REQUIREMENTS
DFLM01.0
-------
Table of Contents
Page
SECTION I: Contract Reports/Deliverables Distribution B-3
SECTION II: Report Descriptions and Order of Data Deliverables B-6
SECTION III: Form Instruction Guide B-15
SECTION IV: Data Reporting Forms B-32
B-2 DFLM01.0
-------
SECTION I
CONTRACT REPORTS/DELIVERABLES DISTRIBUTION
The following table reiterates the contract reporting and deliverables
requirements specified in the Contract Schedule and specifies the
distribution that is required for each deliverable. NOTE: Specific recipient
names and addresses are subject to change during the term of the contract.
The Administrative Project Officer (APO) will notify the Contractor in
writing of such changes when they occur.
Item
No.
Copies
Delivery
Schedule
Distribution
f4)
A. Updated SOFs
60 days after
contract award.
*B. Sample Traffic 1
Reports (original)
C. Sample Data Summary
Package
***D. Sample Data Package
****E. Complete SDG File
*****F. Quality
Assurance
Plan
G. GC/HS Tapes
Lot
3 days after >
receipt of last
sample in Sample
Delivery Group
(SDG).**
45 days after S
receipt of last
sample in SDG.
45 days after Ji
receipt of last
sample in SDG.
45 days after >
receipt of last
sample in SDG.
60 days after
contract award and
as required in
Exhibit E.
Retain for 365 days
after data submis-
sion, or submit with-
in 7 days after
receipt of written
request by APO and/or
EMSL-LV.
As Directed
As Directed
B-3
DFLM01.1 (9/91)
-------
No. Delivery Distribution
Item Copies Schedule m (2) (3)
H. Extracts Lot Retain for 365 days As Directed
after data submis-
sion, or submit with-
in 7 days after
receipt of written
request by APO or SMO.
Distribution:
(1) Sample Management Office (SMO)
(2) Region-Client (Technical Project Officer (TPO))
(3) Environmental Monitoring Systems Laboratory (£MSL-LV)
(4) National Enforcement Investigations Center (NEIC)
* Copy also required in the Sample Data Summary Package.
** Sample Delivery Group (SDG) is a group of samples within a Case,
received over a period of 14 days or less and not exceeding 20
samples. Data for all samples in the SDG are due concurrently. The
date of delivery of the SDG or any samples within the SDG is the
date that all samples have been delivered. (See Exhibit A for
further description.)
*** Concurrent delivery required. Delivery shall be made such that all
designated recipients receive the item on the same calendar day.
**** Complete SDG File will contain the original sample data package plus
all of the original documents described under Section II, Part E.
***** See Exhibit E for a more detailed description.
NOTE: As specified in the Contract Schedule (G.2 Government Furnished
Supplies and Materials), unless otherwise instructed by SMO, the
Contractor shall dispose of unused sample volume and used sample
bottles/containers no earlier than 60 days following submission of
analytical data.
Distribution Addresses:
(1) USEPA Contract Laboratory Program
Sample Management Office
P.O. Box 818
Alexandria, VA 22314
For overnight delivery service, use street address:
300 North Lee Street
Alexandria, VA 22314
(2) USEPA Regions:
SMO, acting on behalf of the APO, will provide the Contractor with the
list of addressees for the 10 EPA Regions. SMO will provide the
B-4 DFLM01.1 (9/91)
-------
Contractor with updated Regional address/name lists as necessary
throughout the period of the contract and identify other client
recipients on a case-by-case basis.
(3) USEPA Environmental Monitoring Systems Laboratory
P.O. Box 93478
Las Vegas, NV 89193-3478
ATTN: Data Audit Staff
For overnight delivery service, use street address:
944 E. Harmon, Executive Center
Las Vegas, NV 89109
ATTN: Data Audit Staff
(4) USEPA National Enforcement Investigations Center (NEIC)
Attn: CLP Audit Program
Denver Federal Center Building 53
P. 0. Box 25227
Denver, CO 80225
B-5 DFLM01.1 (9/91)
-------
SECTION II
REPORT DESCRIPTIONS AND ORDER OF DATA DELIVERABLES
The Contractor shall provide reports and other deliverables as specified in
the Contract Schedule (Reporting Requirements and Deliverables, F.2). The
required content and form of each deliverable are 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 se'ction.
o Paginated consecutively in ascending order starting from the SDG
Narrative.
If submitted documentation does not conform to the above criteria, the
Contractor shall be required to resubmit such documentation with deficiencies
corrected, at no additional cost to the Government.
Whenever the Contractor is required to submit or resubmit data as a result of
an onsite laboratory evaluation or through an APO/TPO action, the data must
be clearly marked as ADDITIONAL DATA and must be sent to all three
contractual data recipients (SMO, EMSL-LV and the Region). A cover letter
shall be included which describes what data are being delivered, to which EPA
Case(s) the data pertain, and who requested the data.
Whenever the Contractor is required to submit or resubmit data as a result of
contract compliance screening by SMO, the data must be sent to all three
contractual data recipients (SMO, EMSL-LV and the Region). In all three
instances the data must be accompanied by a color-coded Cover Sheet
(Laboratory Response To Results of Contract Compliance Screening) provided by
SMO.
Section III of this exhibit contains forms instructions to assist the
Contractor in accurately providing EPA with all required data. Section IV
contains copies of the required data reporting forms in EPA-specified
formats.
Descriptions of the requirements for each deliverable item cited in Reporting
Requirements and Deliverables (Contract Schedule, Section F) are specified in
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 APO, stating the information requested and signed by
the Laboratory Manager.
B-6 DFLM01.1 (9/91)
-------
A. Quality Assurance Plan and Standard Operating Procedures
See Exhibits E and F for requirements.
B. Sample Traffic Reports
The original Sample Traffic Report (TR) page marked "Lab Copy for Return
to SMO" shall be delivered with laboratory receipt information and
signed in original Contractor signature, for each sample in the SDG.
TRs shall be submitted in SDG sets (i.e., TRs for all samples in a SDG
shall be clipped together) with a SDG Cover Sheet attached.
The SDG Cover Sheet shall contain the following items:
o Laboratory name.
o Contract number.
o Sample analysis price - full sample price from the EPA 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).
B-7 DFLM01.1 (9/91)
-------
NOTE: When more than one sample is received in the first or last SDG
shipment, the "first" sample received would be the lowest sample
number (considering both alpha and numeric designations); the
"last" sample received would be the highest sample number
(considering both alpha and numeric designations).
In addition, each TR must be clearly marked with the SDG number, the
sample number of the first sample in the SDG (as described in the
following paragraph). This information should be entered below the
laboratory 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 SZ/o is the SDG
number. When several &
-------
The Contractor shall retain a copy of the Sample Data Package for 365
days after final acceptance of data. After this time, the Contractor
may dispose of the package.
1. SDG Narrative
This document shall he clearly labeled "SDG Narrative" and shall
contain: laboratory name; Case number; sample numbers in the SDG,
differentiating between initial analyses and reanalyses; 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 reanalyses are submitted, the Contractor
shall state in the SDG Narrative for each reanalysis, whether it
considers the reanalysis to be billable, %and if so, why.
The Contractor must also include any problems encountered, both
technical and administrative, the corrective actions taken and the
resolutions, and an explanation for all flagged edits (i.e., manual
edits) on quantitation lists.
NOTE: If a column is used that has different first and last
eluting isomers than the DB-5 column, the Contractor shall
fully document, in the SDG Narrative, the order of elution
of the isomers and identify the first and last eluting
isomers for that particular column for the window defining
mix and CC3 solution.
The SDG Narrative shall contain the following statement, verbatim:
"I certify that this data package is in compliance with the terms
and conditions of the contract, both technically and for
completeness, for other than the conditions detailed above. Release
of the data contained in this hardcopy data package has been
authorized by the Laboratory Manager or his designee, as verified by
the following signature." This statement shall be directly followed
by the signature of the Laboratory Manager or his designee with a
typed line below it containing the signer's name and title, and the
date of signature. Additionally, the SDG Narrative itself must be
signed in original signature by the Laboratory Manager or his
designee and dated. All copies of the SDG Narrative shall be signed
in original signature.
2. Traffic Reports
A copy of the TRs submitted in Part A for all of the samples in the
SDG shall be delivered. The TRs shall be arranged in increasing EPA
sample numbering order, considering both letters and numbers in
ordering samples. Copies of the SDG Cover Sheet shall be included
with the copies of the TRs.
If samples are received at the laboratory with multi-sample TRs, all
the samples on one multi- sample TR may not necessarily be in the
B-9 DFLM01.0
-------
same SDG. In this instance, the Contractor must make the
appropriate number of photocopies of the TR so that a copy is
submitted with each data package to which the TR applies.
In addition, in any instance where samples from more than one multi-
sample TR are in the a*sae data pa:' , _nj Contractor must submit a
copy of the SDG Cover Sheet with copies of the TRs.
PCDD/PCDF Data
a. Sample Data - in order by EPA sample number
(1) Target Compound List Results (Form I PCDD-1).
(2) Calculation of the Toxicity Equivalence (Form I PCDD-2).
(3) Second Column Confirmation Summary (Form I PCDD-3).
If the TEF is greater than the limits specified in Exhibit
D, analysis on a column capable of resolving all 2378-
substituted PCDDs/PCDFs is required.
(4) Selected Ion Current Profile (SICP) for each sample and
each analysis of each sample. SICPs must contain the
following header information:
o EPA sample number.
o Date and time of analysis.
o GC/MS instrument ID.
o Lab file ID.
(5) Total Congener Concentration Results (Form II PCDD).
b. Quality Control Data
(1) Spiked Sample Results (Form III PCDD-1) - in order by EPA
sample number.
(2) Duplicate Sample Results (Form III PCDD-2) - in order by
EPA sample number.
(3) Method Blank Summary (Form IV PCDD) - in order by EPA
sample number assigned to the blanks.
(4) Window Defining Mix Summary (Form V PCDD-1) - in order by
EPA sample number assigned to the window defining mix.
(5) Chromatographic Resolution Summary (Form V PCDD-2) - in
order by EPA sample number assigned to the standard used
to evaluate the column resolution.
B-10 DFLM01.0
-------
(6) SICP for each analysis above [b.(l) - (5)]. SICPs must
contain the header information described in a. (4) above.
c. Calibration Data
(, Inicial Calibration Dati (Form VI PCDD-1 and Form VI PCDD-
2) - in order by instrument, if more than one instrument
used.
(a) PCDD/PCDF standard(s) SICPs for the initial (five-
point) calibration shall be labeled as stated above.
(b) When more than one initial calibration is performed,
the data must be arranged in chronological order by
instrument.
(2) Continuing Calibration Data (Form VII PCDD-1 and Form VII
PCDD-2) - in order by instrument, if more than one
instrument is used.
(a) PCDD/PCDF standard(s) SICPs for all continuing
calibrations shall be labeled as stated above.
(b) When more than one continuing calibration is
performed, the data must be arranged in chronological
order, by instrument.
d. Raw Quality Control Data
(1) Blank Data - in order by EPA sample number assigned to the
blank. SICPs shall be submitted for each blank analyzed
and labeled as above.
(2) Spiked Sample Data - in order by EPA sample number. SICPs
shall be submitted for each spiked sample analyzed and
labeled as above.
E. Complete SPG File
One Complete SDG File (CSF), including the original Sample Data Package,
shall be delivered to the Region concurrently with delivery of the
Sample Data Package to SMO and EMSL-LV. The contents of the CSF will be
numbered according to the specifications described in Sections III and
IV. The Document Inventory Sheet, Form DC-2, is contained in Section
IV. The CSF will contain all original documents where possible. No
copies will be placed in the CSF unless the originals are bound in a
logbook which is maintained by the laboratory. The CSF will contain all
original documents specified in Sections III and IV, and Form DC-2.
The CSF will consist of the following original documents in addition to
the documents in the Sample Data Package:
1. Original Sample Data Package.
B-ll DFLM01.0
-------
2. A completed and signed Document Inventory Sheet (Form DC-2).
3. All original shipping documents including, but not limited to, the
following:
a. EPA Chain-of-Custody Record.
b. Airbills.
c. EPA Traffic Reports.
d. Sample tags (if present) sealed in plastic bags.
4. All original receiving documents including, but not limited to, the
following:
k
a. Form DC-1.
b. Other receiving forms or copies of receiving logbooks.
c. SDG Cover Sheet.
5. All original laboratory records, not already submitted in the Sample
Data Package, of sample transfer, preparation and analysis
including, but not limited to, the following:
a. Original preparation and analysis forms or copies of
preparation and analysis logbook pages.
b. Internal sample and sample extract transfer chain-of-custody
records.
c. Screening records.
d. All instrument output, including strip charts from screening
activities.
6. All other original SDG-specific documents in the possession of the
laboratory, including, but not limited to, the following:
a. Telephone contact logs.
b. Copies of personal logbook pages.
c. All hand-written Case-specific notes.
d. Any other Case-specific documents not covered by the above.
NOTE: All Case-related documentation may be used or admitted as
evidence in subsequent legal proceedings. Any other SDG-
specific documents generated after the CSF is sent to EPA,
as well as copies that are altered in any fashion, are also
deliverables to EPA (original to the Region, and copies to
SMO and EMSL-LV).
B-12 DFLM01.0
-------
If the laboratory does submit SOG-specific documents to EPA
after submission of the CSF, the documents should be numbered
as an addendum to the CSF, and a revised DC-2 Form should be
submitted, or the documents should be numbered as a new CSF,
and a new DC-2 Form should be submitted to the Regions only.
F. GC/MS Tapes
The Contractor must store all raw and processed GC/MS data on magnetic
tape in appropriate instrument manufacturer's format. This tape must
include data for samples, blanks, initial calibrations and continuing
calibrations, as well as all laboratory-generated quantitation reports
and SICPs required to generate the data package. The Contractor shall
maintain a written reference logbook of tape files to EPA sample number,
calibration data, standards and blanks. The logbook should include EPA
sample numbers and standard and blank IDs, identified by Case and SDG.
The Contractor is required to retain the GC/HS 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 APO or EMSL-LV.
When submitting GC/MS tapes to EPA, the following materials must be
delivered in response to the request:
1. All associated raw data files for samples, blanks, matrix spikes,
initial and continuing calibration standards, and window defining
mix solutions.
2. All processed data files and quantitation output files associated
with the raw data files described above.
3. All associated identifications and calculation files used to
generate the data submitted in the data package.
4. A copy of the Contractor's written reference logbook relating tape
files to EPA sample number, calibration data, standards, blanks and
matrix spikes. The logbook must include EPA sample numbers and lab
file identifiers for all samples, blanks and standards, identified
by Case and SDG.
The laboratory must also provide a statement attesting to the
completeness of the GC/MS data tape submission, signed and dated by the
Laboratory Manager. This statement must be part of a cover sheet that
includes the following information relevant to the data tape submission:
1. Laboratory name.
2. Date of submission.
3. Case number.
4. SDG number.
B-13 DFLM01.1 (9/91)
-------
5. GC/MS make and model number.
6. Software version.
7. Disk drive type (e.g., CDC, PRIAM).
8. File transfer method (e.g., DSD, DTD, FTP, Aquarius).
9. Names and telephone numbers of two laboratory contacts for further
information regarding the submission.
G. Extracts
The Contractor shall preserve sample extracts in the dark at room
temperature in bottles/vials with Teflon-lined septa. Extract
bottles/vials shall be labeled with EPA sample number, Case number and
SDG number. A logbook of stored extracts, listing EPA sample numbers
and associated Case and SDG numbers, shall be maintained.
The Contractor is required to retain extracts for 365 days following
data submission. During that time, the Contractor shall submit extracts
and associated logbook pages within seven days following receipt of a
written request from the APO or SMO.
B-14 DFLM01.0
-------
SECTION III
FORM INSTRUCTION GUIDE
This section includes specific instructions for the completion of all
required forms. These instructions are arranged in the following order:
A. General Information and Header Information
B. PCDD/PCDF Sample Data (Form I PCDD-1, PCDD-2 and PCDD-3)
C. PCDD/PCDF Total Congener Concentration Summary (Form II)
D. PCDD/PCDF Spiked Sample and Duplicate Sample Results (Form III PCDD-1 and
PCDD-2)
E. PCDD/PCDF Method Blank Summary (Form IV)
F. PCDD/PCDF Window Defining Mix Summary, Chromatographic Resolution
Summary, and Analytical Sequence (Form V PCDD-1, PCDD-2 and PCDD-3)
G. PCDD/PCDF Initial Calibration Data Summary (Form VI PCDD-1 and PCDD-2)
H. PCDD/PCDF Continuing Calibration Data Summary (Form VII PCDD-1 and PCDD-
2)
I. Sample Log-In Sheet (Form DC-1)
J. Document Inventory Sheet (Form DC-2)
B-15 DFLM01.0
-------
A. General Information and Header Information
The data reporting forms presented in Section IV have been designed in
anticipation of the development of a computer-readable data format.
Although a "diskette deliverable" is not a requirement at this time, the
design of the data reporting forms have taken such a future requirement
into consideration. Therefore, the specific length of each field on the
forms is the approximate length that would be included in a data element
dictionary, with exceptions made in some instances for additional space
on the hardcopy forms for visual clarity.
All characters which appear on the data reporting forms presented in
Section IV must be reproduced by the Contractor when submitting data,
and the format of the f._js 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 APO. The names
of the various fields and compounds (e.g., "Lab Code," "2378-TCDD") must
appear as they do on the forms in the contract, including the options
specified in the form (i.e., "Matrix: (Soil/Water/Waste/Ash)" must
appear, not just "Matrix"). For items appearing on the uncompleted
forms (Section IV), the use of uppercase and lowercase letters is
optional.
Alphabetic entries made onto the forms by the Contractor shall be in ALL
UPPERCASE letters (e.g., "SOIL," not "Soil" or "soil"). 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. However, do not remove the underscores or
vertical bar characters that delineate "boxes" on the forms. The only
exception would be those underscores at the bottom of a "box" that are
intended as a data entry line. (For instance, on Form II, if data must
be entered on the last line of the box, it will replace the
underscores) .
Six pieces of information are common to the header section of each data
reporting form. They are Lab Name, Contract, Lab Code, Case No., SAS
No., and SDG No. Except as noted below for SAS No., this information
must be entered on every form and must match on every form.
The "Lab Name" shall be the name chosen by the Contractor to identify
the laboratory. It may not exceed 25 characters.
The "Lab Code" is an alpha-numeric abbreviation of up to six letters and
numbers assigned by EPA to identify the laboratory and aid in data
processing. This lab code shall be assigned by EPA at the time a
contract is awarded and shall not be modified by the Contractor, except
at the direction of EPA. If a change of name or ownership occurs at the
laboratory, the lab code will remain the same unless and until the
Contractor is directed by EPA to use another lab code assigned by EPA.
The "Case No." is the EPA-assigned Case number associated with the
sample and reported on the Traffic Report or sample shipping paperwork.
B-16 DFLM01.0
-------
The "Contract" is the number of the EPA contract under which the
analyses were performed.
The "SDG No." 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 b* the lowest sample numbe- (considering
both alpha and numeric designations) in the first group of samples
received under the SDG.
The "SAS No." is the EPA-assigned number for analyses performed under
Special Analytical Services (SAS). If samples are to be analyzed under
SAS only and reported on these forms, then enter "SAS No.," and leave
"Case No." blank. If samples are analyzed according to the Routine
Analytical Services (IFB) protocols and have additional SAS
requirements, enter both "Case No." and "SAS No." on all forms. If the
analyses have no SAS requirements, leave "SAS No." blank. NOTE: Some
samples in a SDG may have a SAS No., while others do not.
The other information common to most of the forms is the "EPA Sample
No." This number appears either in the upper right-hand corner of the
form, or as the left column of a table summarizing data from a number of
samples. When the "EPA Sample No." is entered into the triple-spaced
box in the upper right-hand corner of Form I, III or IV, it should be
entered on the middle line of the three lines that comprise the box.
All samples, spiked samples, duplicate samples, blanks and standards
shall be identified with an EPA sample number. For field samples,
spiked samples, and duplicates samples, the EPA sample number is based
on the unique identifying number given in the Traffic Report or sample
shipping records for that sample.
In order to facilitate data assessment, the following sample suffixes
must be used:
XXXXX - EPA sample number
XXXXXS - Spiked aliquot of sample "XXXXX"
XXXXXD - Duplicate aliquot of sample "XXXXX"
XXXXXRE - Reextracted and reanalyzed aliquot of sample "XXXXX"
XXXXXDL - Diluted analysis of sample "XXXXX"
Form V PCDD-3 requires that all samples analyzed in a given 12-hour
analytical sequence be listed, regardless of whether or not they are
part of the SDG being reported, and regardless of whether or not they
are EPA samples. Therefore, use "ZZZZZ" as the EPA sample number for
any sample analysis not associated with the SDG being reported.
For blanks and standards, the following identification scheme must be
used as the "EPA Sample No."
1. Method blanks shall be identified as DFBLK##.
B-17 DF1M01.1 (9/91)
-------
2. Calibration standards shall be identified as CC1##, CC2##, CC3##,
CC4## and CC5##, corresponding to the calibration solutions
identified in Exhibit D.
3. The window defining mixture shall be identified as WDM##.
4. The column performance solution shall be identified as CPS##.
The "EPA Sample No." must be unique within a SDG. Therefore, the
Contractor must replace the two-character "##" terminator of the
identifier with one or two characters or numbers, or a combination of
both, to create a unique EPA sample number for each blank and standard
within the SDG. For example, possible identifiers for method blanks
would be DFBLK1, DFBLK2, DFBLKAl, DFBLKB2, DFB1KAB, etc.
Several other pieces of information are common to many of the data
reporting forms. These include "Matrix," "LalS Sample ID," "Lab File
ID," "Instrument," and "GC Column."
For "Matrix," enter "SOIL" for a soil/sediment sample, "WATER" for an
aqueous sample, and "WASTE" for a chemical waste sample, including the
matrices of oily sludge, wet fuel oil, stillbottoms, oils, or other
materials significantly contaminated with these matrices. Enter "ASH"
for fly ash samples.
"Lab Sample ID" is an optional laboratory-generated internal identifier.
Up to 12 alpha-numeric characters may be reported here. If the
Contractor does not have a lab sample ID, this field may be left blank.
However, if this identifier is used on any of the forms, or accompanying
hardcopy data deliverables, it must be reported on all the appropriate
forms.
"Lab File ID" is the laboratory-generated name of the GC/MS data system
file containing information pertaining to a particular analysis. Up to
14 alpha-numeric characters may be used here.
"Instrument" is common to many of the forms, particularly those
containing calibration data. The identifier used by the laboratory must
include some indication of the manufacturer and/or model of the
instrument, and contain additional characters or numbers that
differentiate between all instruments of the same type in the
laboratory. The instrument identifier must be consistent on all forms
within the SDG.
"GC Column" and "ID (mm)" are common to various other forms. These two
fields are to be used to identify the stationary phase of the GC column
(previously called GC Column ID), and the internal diameter of the GC
column in millimeters (mm). For packed columns, convert the ID from
inches to millimeters as necessary, and enter in the "ID" field.
For rounding off numbers to the appropriate level of precision, observe
the following common rules. If the figure following those to be
retained is less than 5, drop it (round down). If the figure is greater
than 5, drop it and increase the last digit to be retained by 1 (round
B-18 DFLM01.0
-------
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.
PCDD/PCDF Sample Data
1. Form I PCDD-1
This form is used for tabulating and reporting the sample analysis
results for target analytes. It is related to Form I PCDD-2, and
for each sample for which there is a Form I PCDD-1, there must be a
corresponding Form I PCDD-2.
Complete all header information according to the instructions in
Part A and as follows:
Enter the "Matrix" of the sample being analyzed. The designation
of matrix must reflect which one of the matrix-specific extraction
procedures in Exhibit D was used for extraction of the sample.
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 water samples, indicate the extraction procedure used by
entering "SEPF" for separatory funnel extraction or "CONT" for
continuous liquid-liquid extraction in the field labeled "Water
Sample Prep."
Enter the actual volume of the most concentrated sample extract, in
microliters, under "Cone. Extract Volume:" This volume will
typically be 100 microliters, although this volume is split into
two aliquots before analysis.
Enter "GC Column," "Instrument," "Lab Sample ID," and "Lab File ID"
as described in Part A.
"Date Received" is the date of sample receipt at the laboratory, as
noted on the Traffic Report (i.e., the validated time of sample
receipt, VTSR) for that sample. It must be entered as MM/DD/YY.
"Date Extracted" and "Date Analyzed" must also be entered as
MM/DD/YY. If continuous liquid-liquid extraction procedures are
used for water samples, enter the date on which the procedure was
started as the "Date Extracted." If separatory funnel procedures
are used for water samples, enter the date on which the procedure .
was completed. The "Date Analyzed" must be the date of the
analysis for which the results are reported on Form I. (If the
sample requires a second column confirmation and is reported on
Form I PCDD-3, the "Date Analyzed" on Form I PCDD-3 must be the
date of the second analysis, while the date on Form I PCDD-1 and
PCDD-2 will be the date of the first analysis.)
B-19 DFLM01.0
-------
If the sample has been diluted for analysis, enter the "Dilution
Factor" as a single number, not a fraction. For example, enter
"100.0" for a 1 to 100 dilution of the extract. Enter "0.1" for a
concentration of 10 to 1. If the sample was not diluted, enter
"1.0."
NOTE: "Dilution" refers to sample handling steps other than those
outlined in Exhibit D. If the weight or volume of the
sample taken for extraction is not the weight or volume
specified in the protocol, this is not a dilution but is
accounted for in the weight/volume term. A dilution refers
specifically to the addition of clean solvent to a measured
volume of the most concentrated sample extract.
The appropriate concentration units, "NG/L" for water samples or
"UG/KG" for all other matrices, must be entered in the field for
"CONCENTRATION UNITS:"
For each analyte detected in a sample, enter the absolute retention
time of the detected peak under "PEAK RT." Enter the retention
time in minutes .and decimal minutes, not seconds or minutes and
seconds. The retention time must be entered even if the peak did
not meet all of the identification criteria in Exhibit D.
Enter the ion abundance ratio for the two m/z's. (listed under
"Selected Ions") in the column labeled "ION RATIO." If the ion
abundance ratio falls outside the acceptance limits listed in
Exhibit D, place an asterisk (*) in the column under the number (#)
symbol.
For target analytes that meet all the identification criteria in
Exhibit D, the Contractor shall report the concentrations detected
as uncorrected for blank contaminants in the column in the lower
portion of the form labeled "CONCENTRATION." Report all results to
two significant figures.
Under the column labeled "Q" for qualifier, flag each result with
the specific data reporting qualifiers listed below. The
Contractor is encouraged to use additional flags as needed, but the
definition of such flags must be explicit, must not contradict the
qualifiers listed below, and must be included in the accompanying
Narrative.
For reporting results to EPA, the following contract-specific
qualifiers are to be used. The seven qualifiers listed below are
not subject to modification by the laboratory. Up to five
qualifiers may be reported on Form I for each analyte.
The seven EPA-defined qualifiers to be used are as follows:
U - Indicates compound was analyzed for but not detected. The
CONCENTRATION column is left blank in this instance, and an
estimated detection limit (EDL) must be calculated based on
the signal-to-noise ratio, as described in Exhibit D. This
B-20 DFLM01.0
-------
calculation takes into account the sample weight/volume
extracted, the volume of the most concentrated extract, the
injection volume, and dilution of the most concentrated
extract prior to analysis. The calculation does not consider
the percent solids content of the sample, as all results are
reported on a wet weight basis.
J - Indicates an estimated value. This flag is used when the mass
spectral data indicate presence of an analyte meeting all the
identification criteria in Exhibit D, but the result is less
than the sample quantitation limit, but greater than zero.
fi - This flag is used when the analyte is found in the associated
blank as well as in the sample. It indicates
possible/probable blank contamination and warns the data user
to take appropriate action.
E- This flag identifies analytes whose concentrations exceed the
calibration range of the GC/MS instrument for that specific
analysis. If one or more compounds have a response greater
than full scale, except as noted in Exhibit D, the sample
extract must be diluted and reanalyzed according to the
specifications in Exhibit D. All such compounds with a
response greater than full scale should have the concentration
flagged "E" on the Form I for the original analysis. If the
dilution of the extract causes any compounds identified in the
first analysis to be below the calibration range in the second
analysis, the results of both analyses shall be reported on
separate copies of Form I. The Form I for the diluted sample
shall have the "DL" suffix appended to the EPA sample number.
D - This flag indicates all compounds identified in an analysis at
a secondary dilution factor. If a sample extract is
reanalyzed at a higher dilution factor, as in the "E" flag
above, the "DL" suffix is appended to the EPA sample number on
the Form I for the diluted sample, and all concentration
values reported on that Form I are flagged with the "D" flag.
This flag alerts data users that any discrepancies between the
concentrations reported may be due to dilution of the sample
extract.
S- This flag indicates that the analyte in question is, in the
opinion of the GC/MS Interpretation Specialist, a PCDD/PCDF,
even though the M-[COC1]+ ion did not meet the requirement of
2.5 times signal-to-noise (see Exhibit D, Section 11.3).
H - This flag indicates that the analyte in question was
quantitated using peak heights rather than peak areas for both
the analyte and its internal standard (see Exhibit D, Section
11.4).
X - Other specific flags may be required to properly define the
results. If used, they must be fully described, and such
description must be attached to the Sample Data Summary
B-21 DFLM01.0
-------
Package and the SDG Narrative. Begin using "X." If more than
one flag is needed, use "Y" and "Z" as needed. The
laboratory-defined flags are limited to the letters "X," "Y,"
and "Z."
The combination of flags "BU" or "UB" is expressly prohibited.
Blank contaminants are flagged "B" only when they are detected in
the sample associated with the blank.
If a peak detected in the sample meets all of the identification
criteria except the ion abundance ratio, flag the ion ratio as
indicated above, and report the "Estimated Maximum Possible
Concentration" as calculated in Exhibit D under the "EMPC/EDL"
column. Do not report the value of the EMPC under the column
labeled "CONCENTRATION," as that column is only for analytes
meeting all the identification criteria.
If an analyte was not detected in the sample, enter "U" in the
qualifier column, as described above, and report the Estimated
Detection Limit" as calculated in Exhibit D under the "EMPC/EDL"
column. Do not report the value of the EDL if there is an entry
under "CONCENTRATION." The presence of the "U" alerts the data
user that the reported value is an EDL, otherwise it is assumed to
be -an EMPC.
The bottom portion of Form I PCDD-1 contains the fields for
reporting the recoveries of the internal standard and the cleanup
standard. The recoveries of these standards are crucial in
evaluating the effectiveness of this isotope dilution method. For
each internal standard and the cleanup standard, enter the absolute
retention time of the standard in the sample in minutes and decimal
minutes, as above. Report the ion abundance ratio of each of the
five internal standards under the "ION RATIO" column. Flag any ion
ratios that fall outside the ion ratio limits listed on the form by
placing an asterisk (*) in the column under the number (#) symbol.
There is no ion abundance ratio for the cleanup standard, as only
one ion is monitored.
Report the percent recovery of the internal standards and the
cleanup standard, calculated according to Exhibit D, under the
"%REC" column. The quality control limits for recovery are listed
on the form. Flag any recovery outside those limits by placing an
asterisk (*) under the number (#) symbol in the recovery column.
Requirements for reanalysis of samples due to poor recoveries are
given in Exhibit D.
2. Form I PCDD-2, Toxicity Equivalence Summary
This page of Form I is used to report the results of the toxicity
equivalence calculations for each sample analyzed. The
concentration of each of the 2,3,7,8-substituted PCDD and PCDF
isomers is multiplied by a toxicity equivalence factor (TEF), as
described in Exhibit D, to arrive at a concentration of 2,3,7,8-
TCDD with an equivalent toxicity. The total of all the toxic
B-22 DFLM01.0
-------
equivalents determines whether or not the sample needs to be
analyzed on a second GC column to more completely separate the
2378-TCDF from all other TCDD and TCDF isomers (see Exhibit D).
Complete the header information as above. ThQ header of Form I
PCDD-2 must match the header of Form I PCDD-1 for the same sample.
For each 2,3,7,8-substituted isomer positively identified in the
sample, enter the concentration found in the column labeled
"CONCENTRATION." If an isomer was not detected, i.e., flagged "U"
on Form I PCDD-1, for the purposes of this calculation, enter 0.0
(zero) as the concentration. EMPC values are not included in the
TEF calculations under this SOW.
Multiply each concentration times the TEF listed on the form for
that isomer, and enter the product of the two in the column labeled
"TEF-ADJUSTED CONCENTRATION." Add all 17 TEF-adjusted
concentrations together, including any zeros, and enter the total
on the line at the bottom of the form.
If the total TEF-adjusted concentration is greater than the values
listed at the bottom of the form and in Exhibit D, then a second
column confirmation analysis is required (see Exhibit D).
3. Form I PCDD-3, Second Column Confirmation Results
This page of Form I is used to report the results of all second
column confirmation analyses performed. The requirements for
second column confirmation are discussed above and in Exhibit D.
Each time a second column confirmation is performed, the results
are reported on Form I PCDD-3.
Complete the header information as above, except note that the
fields for "GC Column" and "Date Analyzed" must correspond to the
second column confirmation analysis, i.e., they must not match
those fields in the header of Form I PCDD-1 or PCDD-2. Other
fields such as "Instrument," "Dilution Factor," and "Lab File ID"
may also differ and must correspond to the second column
confirmation analysis.
Complete the information in the lower portion of the form in a
fashion similar to that for Form I PCDD-1, but entering the results
of the second column confirmation.
Enter the data on recovery of the internal standards and cleanup
standard from the second column confirmation analysis in a fashion
similar to that for the original analysis.
C. PCDD/PCDF Total Congener Concentration Summary (Form II)
This form is used to report the total concentration of all PCDD/PCDF
isomers in a given homologue that are detected in the sample, including
those isomers that do not represent the 2,3,7,8-substituted isomers of
greatest toxicological concern. Because there are many isomers in each
B-23 DFLM01.0
-------
homologue, it is necessary to indicate the number of peaks that
represent isomers within the homologue. Enter the number of peaks
detected in each homologue under "PEAKS." For instance, if three FeCDD
peaks are detected and summed together, enter "3" under "PEAKS."
Lncer the concentration of the total homologue, as calculated in Exhibit
D, under "CONCENTRATION." Enter qualifiers under the "Q" column, as
described above. If no isomers in a homologue were detected, enter "U"
as the qualifier, and enter the lowest EDL of any of the 2,3,7,8-
substituted isomers under the "EMPC/EDL" column.
If any of the peaks in a homologue meet all the identification criteria
except the ion abundance ratio, then.report the total concentration as
an EMPC under the "EMPC/EDL" column.
D. PCDD/PCDF Spiked Sample and Duplicate Sample Results (Form III)
1. PCDD/PCDF Spiked Sample Summary (Form III PCDD-1)
This page of Form III is used to report the accuracy of the spiked
sample analysis, measured as recovery of the 10 spiked analytes.
Because some of the analytes may also be present in the unspiked
aliquot of the sample, results for both the unspiked and spiked
analyses are reported on Form III.
Complete the header information as in Part A. Enter the EPA sample
number for the spiked sample aliquot in the box at the top of the
form. Similarly, the lab sample ID and lab file ID must refer to
the spiked sample analysis.
Enter the "Spike Added" of each of the 10 analytes in picograms
(pg). In the column labeled "Spiked Sample Result," enter the
concentration (or EMPC) of each analyte detected in the spiked
sample aliquot. The concentration units must be those indicated at
the top of the form and be appropriate to the sample matrix listed
in the header. Enter the concentration (or EMPC) of each analyte
detected in the original analysis of the unspiked sample aliquot.
If an analyte was not detected in the unspiked aliquot, enter zero
in place of the concentration, and use this value in the
calculations described in Exhibit D. Calculate the recovery of
each spiked analyte as described in Exhibit D, and enter this value
to the nearest whole percentage point in the column labeled "%REC.n
Flag any recoveries outside the quality control limits listed on
the form by placing an asterisk (*) in the column under the number
(#) symbol.
In addition to Form III PCDD-1, a copy of Form I must be completed
for the spiked sample analysis as well, following the procedures
described above.
2. PCDD/PCDF Duplicate Sample Summary (Form III PCDD-2)
This page of Form III is used to report the precision of the
duplicate sample analysis, measured as the relative percent
B-24 DFLM01.0
-------
difference (RFD) between the results of the original and duplicate
analyses of one sample of each matrix in each SDG. In order to
allow direct comparison of the results of both the analyses, the
concentration results from the original and duplicate analyses are
reported on a single copy of Form III PCDD-2.
Complete the header information as described in Fart A above, but
enter the EPA sample number, lab sample ID, and lab file ID of the
duplicate aliquot in these fields on Form III PCDD-2. Enter the
concentration units.
For each target analyte, enter the results from both the analyses
under the columns "Sample Concentration" and "Duplicate
Concentration." These values must match those on Form I for these
aliquots, except that undetected analytes (flagged "U" on Form I)
are reported as zero on Form III PCDD-2. If either or both the
analyses resulted in an EMPC for any analyte, enter the EMPC as the
concentration, and use that value in the calculations.
Calculate the relative percent difference between the two
concentrations or EMPCs, as described in Exhibit D, using zero for
undetected analytes, and report this value to the nearest whole
percentage point under "RPD." If the analyte was not detected in
either aliquot, enter zero for both concentrations, and report the
RPD as zero as well. Flag all values outside the quality control
limits listed on the forms by entering an asterisk (*) under the
number (#) symbol.
PCDD/PCDF Method Blank Summary (Form IV)
This form summarizes the samples associated with each method blank
analysis. A copy of Form IV is required for each blank.
Complete the header information as described in Part A. The EPA sample
number entered in the box at the top of the form shall be the number
assigned to the method blank. The matrix entered on this form refers to
the matrix of the associated samples, as one blank is required each time
that samples of a similar matrix are extracted together. Therefore,
samples of differing matrices cannot be mixed together on a single Form
IV.
Summarize the samples associated with a given method blank in the box in
the lower portion of the form, entering the EPA sample number, lab
sample ID, lab file ID, and date of analysis of each sample. Include
spiked samples and duplicate samples as well.
F. PCDD/PCDF Window Defining VU* Summary. Chromatographic Resolution
Summary, and Analytical Sequence (Form V)
1. PCDD/PCDF Window Defining Mix Summary (Form V PCDD-1)
This page of Form V is used to report the results of the analysis
of the window defining mixture that precedes each initial
B-25 DFLM01.0
-------
calibration on each GC column and instrument used for analysis.
The analysis of this mixture is used to document the retention time
window for the PCDD/PCDF homologue.
Complete the header information as descr-^M :n Part A, entering
the EPA sample number of the window -opining mixture injection in
the box at the top of the form. The header information must
correspond to the analysis of the window defining mixture.
In the box in the lower portion of the form, enter the absolute
retention times of the first and last eluting isomers in each
homologue. Enter the retention times in minutes and decimal
minutes, not minutes and seconds, nor seconds.
NOTE: As there is only one possible octachlorinated dioxin and
furan, the retention times of these analytes are not
contained in the window defining mixture, and are not
reported here.
2. PCDD/PCDF Chromatographic Resolution Summary (Form V PCDD-2)
This page of Form V is used to report the Chromatographic
resolution of selected analytes in one of two solutions, depending
on the GC column. The Chromatographic resolution of these analytes
is crucial to evaluating the results for the PCDDs/PCDFs reported
in the samples. This evaluation is made every 12 hours during
which samples or standards are analyzed.
For the DB-5 (or equivalent) column, the Chromatographic resolution
is judged from the analysis of the CC3 standard during initial or
continuing calibration. For the SP-2331 (or equivalent) column,
the Chromatographic resolution is judged from the analysis of the
column performance solution that precedes the analysis of the CC3
standard on this column (see Exhibit D).
Complete one copy of Form V PCDD-2 for each GC column used for
analysis. Complete the header information as described in Part A,
entering the EPA sample number of the CC3 standard or the column
performance solution in the box at the top of the form. Enter the
date and time of analysis of the standard in the header.
Calculate the Chromatographic resolution for the GC column
identified in the header according to the procedures in Exhibit D.
For the DB-5 (or equivalent) column, enter only the results from
the CCS analysis. For the SP-2331 (or equivalent) column, enter
only the results from the column performance solution analysis.
The GC column chosen for the confirmation analysis must meet the
resolution criteria for the other specified column. If the
Contractor chooses a single column for analysis that is designed
such that a second column confirmation analysis is not required,
then the Contractor must demonstrate that the resolution criteria
for both of the specified columns have been met (see Exhibit D).
B-26 DFLM01.0
-------
3. PCDD/PCDF Analytical Sequence (Form V PCDD-3)
This page of Form V is used Co report the sequence of analyses,
including the analysis of the window defining mixture, the
calibration ^andards, blanks, samples, duplicates, and spiked
sample-. One copy of Form V PCDD 2 is required for each 12-hour
period during which samples, blanks, standards, etc. associated
with the SDG are analyzed.
Complete the header information as described in Part A. Enter the
inclusive dates and times of the analyses of the first and last
initial calibration standards in the fields for "Init. Calib.
Date(s)" and "Init. Calib. Times." Dates must be in the format
MM/DD/YY, and all times are expressed as HHMM, in military time
(i.e., a 24-hour clock).
In the box in the lower portion of the form, enter the EPA sample
number, lab sample ID, lab file ID, and date and time of analysis
of all standards, samples, blanks, duplicates, spiked samples,
dilutions, reanalyses, etc. All analyses in the 12-hour period
must be listed on Form V. If analysis is not associated with the .
SDG being reported, enter the EPA sample number as "ZZZZZ," as
described in Part A. The 12-hour sequence must end with the
. - analysis of the appropriate calibration standard, as described in
Exhibit D. In order to meet the requirements of the 12-hour
sequence, the standard must be injected within 12 hours of the
injection of the standard that began the sequence (CCS on the DB-5,
and the column performance solution on the SP-2331).
If the analytical sequence includes the analysis of the initial
calibration standards, these standards and the window defining mix
must be included on that copy of Form V, identified by the EPA
sample numbers described in Part A. A copy of the analytical
sequence that includes these initial calibration standards and the
window defining mix must be submitted with each data package to
which the initial calibration applies, but the Case number and SAS
number must match those of each data package in which these initial
calibration data are reported.
G. PCDD/PCDF Initial Calibration Data Summary (Form VI}
1. PCDD/PCDF Initial Calibration Response Factor Summary (Form VI
PCDD-1)
This form is used to summarize the response factors for each target
analyte, internal standard and cleanup standard calculated from the
initial calibration. Complete the header information as described
in Part A. Enter the inclusive initial calibration date(s) and
times, as described for Form V PCDD-2. One copy of Form VI PCDD-1
must be completed for each initial calibration, for each instrument
and GC column used for analysis of samples, and must be accompanied
by a corresponding Form VI PCDD-2.
B-27 DFLM01.0
-------
Enter the relative response factors (RRF) determined from the
analysis of each of the calibration standards (CC1 through CC5).
Enter RRF values to three decimal places. Calculate the mean RRF,
as described in Exhibit D, and enter in the column "MEAN RRF."
Calculate the relative standard deviation as a percentage of the
mean (%RSD), and enter under "%RSD." Note that seven of the native
analytes and the cleanup standard occur only in the CC3 standard,
and therefore, %RSD calculations are not possible and are not
reported on this form. However, for these analytes, enter the
single point RRF as the "MEAN RRF." Also note that as the recovery
standards are used to determine the RRFs of the internal standards,
no RRF values can be calculated for the recovery standards, and .
therefore, they do not appear on Form VI PCDD-1.
All initial calibrations must meet the quality control limits for
%RSD listed on the form.
2. PCDD/PCDF Initial Calibration Ion Abundance Ratio Summary (Form VI
PCDD-2)
This page of Form VI is used to report the ion abundance ratios for
each of the initial calibration standards. Because the ratio of
the abundances of the two ions monitored for each analyte is
crucial to the identification of these analytes, the ion abundance
ratios must meet the quality control limits.
For each native analyte, internal standard and recovery standard,
the two ions monitored for each analyte are listed in the column
labeled "Selected Ions." Calculate the ratio of the abundances of
these two ions according to the procedures in Exhibit D, and enter
the ion abundance ratio of each analyte in each of the initial
calibration standards to two decimal places.
Compare the ion abundance ratios to the quality control limits
shown on the form, and flag any analyte which did not meet these
limits in one or more of the standards.
Note that the cleanup standard does not appear on Form VI PCDD-2,
as only one ion is monitored for this analyte, and therefore, no
ion abundance ratio can be calculated.
One copy of Form VI PCDD-2 must be completed for each initial
calibration, for each instrument and GC column used for analysis of
samples, and must accompany a corresponding copy of Form VI PCDD-1.
H. PCDD/PCDF Continuing Calibration Data Summary
1. PCDD/PCDF Continuing Calibration Summary (Form VII PCDD-1)
This page of Form VII is used to summarize the results of the
continuing calibration that must occur in each 12-hour analytical
sequence. The form is used to report the RRF values and ion
abundance ratios of each analyte in the CC3 standard, and to
compare these values to the initial calibration data reported on
B-28 DFLM01.0
-------
Form VI. One copy of Form VII PCDD-1 must be completed for each
continuing calibration performed, and must be accompanied by a
corresponding copy of Form VII PCDD-2.
Complete the header information as described in Part A. The date
and time ot analysis and lab fi'e ID in the header must correspond
to the analysis of the CC3 standard. Enter the date of the
associated initial calibration in the field for "Init. Calib.
Date(s):" If the calendar date changed during the initial
calibration, enter the inclusive dates of the first and last
standards in the associated initial calibration in the fields for
"Init. Calib. Date(s)."
For each of the native analytes, internal standards, and the
cleanup standard, enter the relative response factor (RRF)
determined from the analysis of the continuing calibration standard
in the column labeled "RRF." Enter the mean RRF for each analyte
from the associated initial calibration, in the column labeled
"MEAN RRF." For the seven native analytes and the cleanup standard
that undergo only a single-point calibration, enter the CCS RRF
from the initial calibration, which is also entered as the mean RRF
on Form VI. The values reported in this column must match those
reported on the Form VI for the associated initial calibration.
Calculate the percent difference (%D) between the RRF and the mean
RRF for each analyte, and report under "%D." If the percent
difference exceeds the quality control limits shown on the form
(±30%), flag that analyte by placing an asterisk (*) in the "RRF
FLAG" column. Report the ion abundance ratio of each analyte under
the "ION RATIO" column. Flag any ion ratio that fails outside the
quality control limits shown on the form by placing as asterisk (*)
in the "ION FLAG" column.
Note that because only one ion is monitored for the cleanup
standard, no ion ratio is determined for this analyte. For the
recovery standards, relative response factors are not calculated or
reported on Form VII, but the ion abundance ratios for these
standards must be reported on Form VII.
2. PCDD/PCDF Continuing Calibration Summary (Form VII PCDD-2)
This page of Form VII is used to summarize the absolute and
relative retention times of the analytes in the continuing
calibration standard that must be analyzed in each 12-hour
analytical sequence. Absolute retention times and relative
retention times are critical to the identification of PCDDs/PCDFs
by this method. One copy of Form VII PCDD-2 must be completed for
each continuing calibration performed and must be accompanied by a
corresponding copy of Form VII PCDD-1.
Complete the header information as described in Part A. The date
and time of analysis and lab file ID in the header must correspond
to the analysis of the CCS standard. Enter the date of the
associated initial calibration in the field for "Init. Calib.
Date(s):" If the calendar date changed during the initial
B-29 DFLM01.0
-------
calibration, enter the inclusive dates of the analyses of the first
and last standards in the associated initial calibration in the
fields for "Init. Calib. Date(s)."
For each of the native analytes and the cleanup standard, enter the
relative retention time (RRT) and absolute retention time (RT) of
the analyte in the calibration standard. RRT is calculated
according to the procedures in Exhibit D, as the RT of the native
analyte divided by the RT of appropriate internal standard. For
the internal standards and recovery standards, report the only the
absolute retention times. Enter all RTs in minutes and decimal
minutes. RRTs are reported to two decimal places.
I. Sample Log-In Sheet (Form DC-1)
This form is used to document the receipt and inspection of sample
containers and samples. One original of Form DC-1 is required for each
sample shipping container. If the samples in a single sample shipping
container must be assigned to more than one SDG, the original Form DC-1
shall be placed with the deliverables for the SDG of the lowest Arabic
number, and a copy of Form DC-1 must be placed with the deliverables for
the other SDG(s). The copies should be identified as "copy(ies)," and
the location of the original should be noted on the copies.
Sign and date the airbill (if present). Examine the shipping container
and record the presence/absence of custody seals and their condition
(e.g., intact, broken) in item 1 of Form DC-1. Record the custody seal
numbers in item 2.
Open the container, remove the enclosed sample documentation, and record
the presence/absence of chain-of-custody record(s), SMO forms (e.g.,
Traffic Reports, Packing Lists), and airbills or airbill stickers in
items 3-5. Specify if there is an airbill present or an airbill sticker
in item 5. Record the airbill or sticker number in item 6.
Remove the samples from the shipping container(s), examine the samples
and the sample tags (if present), and record the condition of the sample
bottles (e.g., intact, broken, leaking) and presence of absence of
sample tags in items 7 and 8.
Review the sample shipping documents and complete the header information
described in Instruction A. Compare the information recorded on all the
documents and samples and circle the appropriate answer in item 9.
If there are no problems observed during receipt, sign and date (include
time) Form DC-1, the chain-of-custody record, and Traffic Report, and
write the sample numbers on Form DC-1. Record the appropriate sample
tags and assigned laboratory numbers if applicable. The log-in date
should be recorded at the top of Form DC-1 and the date and time of
cooler receipt at the laboratory should be recorded in items 10 and 11.
Record the fraction designation (if appropriate) and the specific area
designation (e.g., refrigerator number) in the Sample Transfer block
located in the bottom left corner of Form DC-1. Sign and date the
Sample Transfer block. Cross out unused columns and spaces.
B-30 DFLM01.0
-------
If there are problems observed during receipt or an answer marked with
an asterisk (e.g., "absent*") was circled, contact SMO and document the
contact as well as resolution of the problem on a CLP Communication Log.
Following resolution, sign and date the forms as specified in the
preceding paragraph and note, where appropriate, t^e resolution of the
problem.
J. CSF Inventory Sheet (Form DC-2)
This form is used to record the inventory of the CSF purge documents and
count of documents in the original Sample Data Package that is sent to
the Region.
Organize all EPA-CSF documents as described in Section II and Section
III. Assemble the documents in the order specified on Form DC-2 and
Section II and III, and stamp each page with a consecutive number. (Do
not number the DC-2 form.) Inventory the CSF by reviewing the document
numbers and recording page number ranges in the columns provided in the
Form DC-2. If there are no documents for a specific document type,
enter "NA" in the empty space.
Certain laboratory-specific documents related to the CSF may not fit
into a clearly defined category. The laboratory should review Form DC-2
to determine if it is most appropriate to place them under item 5, 6, 7,
or 8. Item 10 should be used if there is no appropriate previous item.
These types of documents should be described or listed in the blanks
under each appropriate item.
B-31 DFLM01.0
-------
SECTION IV
DATA REPORTING FORMS
B-32 DFLM01.0
-------
Lab Name:
Lab Code:
Matrix:
1DFA
PCDD/PCDF SAMPLE DATA SUMMARY
Contract:
SAS No.:
EPA SAMPLE NO.
Case No.:
SDG No.:
(Soil/Water/Waste/Ash)
Sample wt/vol: (g/mL)
Water Sample Prep.: (Sepf/Cont)
Concentrated Extract Volume: (uL)
Injection Volume:
GC Column:
(uL) % Solids: _
ID: _ (mm)
Lab Sample ID:
Lab File ID:
Date Received:
Date Extracted:
Date Analyzed:
Dilution Factor:
ANALYTE
CONCENTRATION UNITS: (ng/L or ug/Kg)
Q
SELECTED PEAK ION
IONS RT RATIO # CONCENTRATION
EMPC/EDL
2378-TCDD
2378 -TCDF
12378-PeCDF
12378-PeCDD
23478-PeCDF
123478-HXCDF
123678-HxCDF
123478-HXCDD
123678-HXCDD
123789-HxCDD
234678-HXCDF
123789-HxCDF
1234678-HpCDF
1234678-HpCDD
1234789-HpCDF
OCDD
OCDF
320/322
304/306
340/342
356/358
340/342
374/376
374/376
390/392
390/392
390/392
374/376
374/376
408/410
424/426
408/410
458/460
442/444
NOTE: Concentrations, EMPCs, and EDLs are calculated on a wet weight basis.
INTERNAL
STANDARD
SELECTED PEAK ION ION RATIO % RECOVERY
IONS RT RATIO # LIMITS REC # LIMITS
13C-2378-TCDF
13C-2378-TCDD
13C-123678-HXCDD
13C-1234678-HpCDF
13C-OCDD
37C1-2378-TCDD
316/318
332/334
402/404
420/422
470/472
328/NA
NA
0.65-0.89
0.65-0.89
1.05-1.43
0.88-1.20
0.76-1.01
NA
25-150
25-150
25-150
25-150
25-150
25-150
# Column to be used to flag values outside QC limits
FORM I pcnn-i
-------
1DFB
PCDD/PCDF TOXICITY EQUIVALENCE SUMMARY
EPA SAMPLE NO.
Lab Name:
Lab Code:
Matrix:
Case No.:
Contract:_
SAS No.:
SDG No.:
(Soil/Water/Waste/Ash)
Sample wt/vol: (g/mL)
Water Sample Prep.: (Sepf/Cont)
Concentrated Extract Volume: (uL)
Injection Volume:
GC Column:
(uL) % Solids: _
ID: (mm)
Lab Sample ID:
Lab File ID:
Date Received:
Date Extracted:
Date Analyzed:
Dilution Factor:
ANALYTE
CONCENTRATION UNITS: (ng/L or ug/Kg)
CONCENTRATION TEF
TEF-ADJUSTED
CONCENTRATION
2378-TCDD
2378-TCDF
12378-PeCDF
12378-PeCDD
23478-PeCDF
123478-HxCDF
123678-HXCDF
123478-HxCDD
123678-HxCDD
123789-HXCDD
234678-HXCDF
123789-HxCDF
1234678-HpCDF
1234678-HpCDD
1234789-HpCDF
OCDD
OCDF
X 1.0
X 0.1
X 0.05 =
X 0.5
X 0.5
X 0.1
X 0.1
X 0.1 =
X 0.1
X 0.1
X 0.1
X 0.1
x 0.01 =
X 0.01 =
X 0.01 =
X 0.001 =
X 0.001 =
Total =
-
NOTE: Do not include EMPC or EDL values in the TEF-adjusted Concentration.
If the Total Toxic Equivalent Concentration of the sample is greater than
7 ng/L for an aqueous sample, greater than 0.7 ug/Kg for any solid matrix,
or greater than 7 ug/Kg for a chemical waste sample, then second column
confirmation of the results may be required.
FORM I PCDD-2
10/90
-------
1DFC
PCDD/PCDF SECOND COLUMN CONFIRMATION SUMMARY
EPA SAMPLE NO.
Lab Name:
Lab Code:
Matrix:
Case No.:
Contract:
SAS No.:
(Soil/Water/Waste/Ash)
Sample wt/vol: (g/mL)
Water Sample Prep.: (Sepf/Cont)
(uL)
Concentrated Extract Volume:
Injection Volume: (uL) % Solids:
GC Column:
Lab Sample ID:
Lab File ID:
Date Received:
Date Extracted:
Date Analyzed:
ID:
(mm)
Dilution Factor:
ANALYTE
CONCENTRATION UNITS: (ng/L or ug/Kg)
Q
SELECTED PEAK ION
IONS RT RATIO # CONCENTRATION
SDG No.:
EMPC/EDL
2378-TCDD
2378-TCDF
12378-PeCDF
12378-PeCDD
23478-PeCDF
123478-HxCDF
123678-HxCDF
123478-HXCDD
123678-HXCDD
1 O *3 *7 Q Q II v/Tlf^
J.<£ J /oy~rlXv-lJlJ
O "5 A £*7 Q TTv/"tTMr
£ J4o / o~n.XL.Ur
123789-HxCDF
1234678-HpCDF
1234678-HpCDD
1234789-HpCDF
OCDD
OCDF
•
320/322
304/306
340/342
356/358
340/342
374/376
374/376
390/392
390/392
i on / 1 QO
jy u/ jyz
0*7 >l / fj C.
J /4/ O /O
374/376
408/410
424/426
408/410
458/460
442/444
NOTE: Concentrations, EMPCs, and EDLs are calculated on a wet weight basis.
INTERNAL
STANDARD
SELECTED PEAK ION ION RATIO
IONS RT RATIO # LIMITS
% RECOVERY
REG # LIMITS
13C-2378-TCDF
13C-2378-TCDD
13C-123678-HXCDD
13C-1234678-HpCDF
13C-OCDD
37C1-2378-TCDD
•-
316/318
332/334
402/404
420/422
470/472
328/NA
NA
0.65-0.89
0.65-0.89
1.05-1.43
0.88-1.20
07e_i ni
NA
25-150
25-150
25-150
25-150
o c T c n
25-150
# Column to be used to flag values outside QC limits
FORM I PCDD-3
i n
-------
2DF
PCDD/PCDF TOTAL HOMOLOGUE CONCENTRATION SUMMARY
EPA SAMPLE NO.
Lab Name:
Lab Code:
Matrix:
Case No.:
Contract:
SAS No.:
SDG No.:
(Soil/Water/Waste/Ash)
Sample wt/vol: (g/mL)
Water Sample Prep.: (Sepf/Cont)
Concentrated Extract Volume: (uL)
Injection Volume:
GC Column:
(uL) % Solids: _
ID: (mm)
Lab Sample ID: _
Lab File ID: _
Date Received: _
Date Extracted:_
Date Analyzed: _
Dilution Factor:
CONCENTRATION UNITS: (ng/L or ug/Kg)
HOMOLOGUE
PEAKS CONCENTRATION
EMPC/EDL
DIOXINS
Total TCDD
Total PeCDD
Total HXCDD
Total HpCDD
FURANS
Total TCDF
Total PeCDF
Total HxCDF
Total HpCDF
NOTE: Concentrations, EMPCs, and EDLs are calculated on a wet weight basis.
The total congener concentrations do not affect the TEF calculations.
FORM II PCDD
10/90
-------
Lab Name:
Lab Code:
Matrix:
3DFA
PCDD/PCDF SPIKED SAMPLE SUMMARY
Contract:
SAS No.:
EPA SAMPLE NO.
Case No.:
SDG No.:
(Soil/Water/Waste/Ash)
ANALYTE
CONCENTRATION UNITS: (ng/L or ug/Kg)
SPIKE SPIKED
ADDED SAMPLE SAMPLE % QC
(PG) CONCENTRATION CONCENTRATION REC # LIMITS
2378-TCDD
2378-TCDF
12378-PeCDF
12378-PeCDD
123678-HXCDF
123678-HXCDD
1234678-HpCDF
1234678-HpCDD
OCDD
OCDF
50-150
50-150
50-150
50-150
50.-150
50-150
50-150
50-150
50-150
50-150
If an analyte is not detected in the unspiked sample, enter 0 (zero) as the
"SAMPLE CONCENTRATION."
# Column to be used to flag values outside QC limits.
QC limits are advisory.
FORM III PCDD-1
10/90
-------
3DFB
PCDD/PCDF DUPLICATE SAMPLE SUMMARY
Matrix: (Soil/Water/Waste/Ash)
EPA SAMPLE NO,
Lab Name:
Lab Code:
Contract :
Case No.: SAS No.: SDG No.:
CONCENTRATION UNITS: (ng/L or ug/Kg)
ANALYTE
SAMPLE DUPLICATE QC
CONCENTRATION CONCENTRATION RPD # LIMITS
2378-TCDD
2378-TCDF
12378-PeCDF
12378-PeCDD
23478-PeCDF
123478-HXCDF
123678-HXCDF
123478-HXCDD
123678-HxCDD
123789-HXCDD
234678-HXCDF
123789-HXCDF
1234678-HpCDF
1234678-HpCDD
1234789-HpCDF
OCDD
OCDF
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
If an analyte is not detected in either analysis, enter 0 (zero) as
the concentration.
# Column to be used to flag values outside QC limits.
QC limits are advisory
FORM III PCDD-2
10/90
-------
Lab Name:
Lab Code:
Matrix:
4DF
PCDD/PCDF METHOD BLANK SUMMARY
Contract:_
SAS No.:
EPA SAMPLE NO.
Case No.:
SDG No.:
(Soil/Water/Waste/Ash)
Sample wt/vol: (g/mL)
Water Sample Prep.: (Sepf/Cont)
Lab Sample ID: _
Lab File ID:
Date Extracted:
Date Analyzed:
THIS METHOD BLANK APPLIES TO THE FOLLOWING SAMPLES, SPIKES, AND DUPLICATES:
EPA
SAMPLE NO.
LAB
SAMPLE ID
LAB
FILE ID
DATE
ANALYZED
FORM IV PCDD
10/90
-------
5DFA
PCDD/PCDF WINDOW DEFINING MIX SUMMARY
EPA SAMPLE NO.
Lab Name:_
Lab Code:
GC Column:
Instrument ID:
Case No.:
ID:
Contract:
SAS No.:
SDG No.:
(nan)
wile ID: .
Date Analyzed:
Time Analyzed:
RT RT
FIRST LAST
CONGENER ELUTING ELUTING
TCDD
TCDF
PeCDD
PeCDF
HxCDD
HxCDF
HpCDD
HpCDF
FORM V PCDD-1
10/90
-------
5DFB EPA SAMPLE NO.
PCDD/PCDF CHROMATOGRAPHIC RESOLUTION SUMMARY
Lab Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
oc Column: ID: (mm) Lab File ID:
Instrument ID: Date Analyzed:
Time Analyzed:
Percent Valley determination for DB-5 (or equivalent) column -
For the CC3 standard beginning the 12-hour period:
13C-2378-TCDD/13C-1234-TCDD:
123478-HXCDD/123678-HXCDD:
QC LIMITS:
Percent Valley between.the TCDD isomers must be less than or equal to 25%
Percent Valley between the HxCDD isomers must be less than or equal to 50%
Percent Valley Determination for SP-2331 (or equivalent) Column -
For the Column Performance Solution beginning the 12-hour period:
1478-TCDD/2378-TCDD:
2378-TCDD/(1237/1238)-TCDD:
QC LIMITS:
Percent Valley between the TCDD isomers must be less than or equal to 25%.
FORM V PCDD-2 10/90
-------
5DFC
PCDD/PCDF ANALYTICAL SEQUENCE SUMMARY
Lab Name:_
Lab Code:
GC Column:
Case No.:
ID:
Contract:
SAS No.:
SDG No.
(nun)
Instrument ID:
Init. Calib. Date(s):
Init. Calib. Times:
THE ANALYTICAL SEQUENCE OF STANDARDS, SAMPLES, BLANKS, SPIKES, AND
DUPLICATES IS AS FOLLOWS:
EPA
SAMPLE NO.
LAB
SAMPLE ID
LAB
FILE ID
DATE
ANALYZED
TIME
ANALYZED
FORM V PCDD-3
10/9C
-------
6DFA
PCDD/PCDF INITIAL CALIBRATION RESPONSE FACTOR SUMMARY
Lab Name:_
Lab Code:
GC Column:
Case No.:
ID:
Init. Calib. Date(s):
Init. Calib. Times:
Contract:
SAS No.:
SDG No.:
(mm)
Instrument ID:
NATIVE ANALYTES
VS. INTERNAL STDS.
2378-TCDD
. 2378-TCDF
12378-PeCDF
12378-PeCDD
23478-PeCDF
123478-HXCDF
123678-HxCDF
123478-HxCDD
123678-HxCDD
123789-HXCDD
234678-HxCDF
123789-HxCDF
1234678-HpCDF
1234678-HpCDD
1234789-HpCDF
OCDD
OCDF
INTERNAL STANDARDS
VS. RECOVERY STDS.
13C-2378-TCDD
13C-2378-TCDF
13C-123678-HXCDD
13C-1234678-HpCDF
13C-OCDD
37C1-2378-TCDD
CC1
CC2
RRF (N)
CC3
CC4
CCS
MEAN
RRF
%RSD
A single point calibration is performed for seven of the native analytes and
the cleanup standard. Therefore, no %RSD is reported for these compounds.
QC Limits: %RSD must be less than or equal to 15.0%.
FORM VI PCDD-1
10/90
-------
6DFB
PCDD/PCDF INITIAL CALIBRATION ION ABUNDANCE RATIO SUMMARY
Lab Name:_
Lab Code:
GC Column:
Case No.:
ID:
Init. Calib. Date(s):
Init. Calib. Times:
Contract:
SAS No.:
SDG No.:
(mm)
Instrument ID:
NATIVE ANALYTES
2378-TCDD
' 2378-TCDF
12378-PeCDF
12378-PeCDD
23478-PeCDF
123478-HxCDF
123678-HXCDF
123478-HXCDD
123678-HxCDD
123789-HXCDD
234678-HxCDF
123789-HxCDF
1234678-HpCDF
1234678-HpCDD
1234789-HpCDF
OCDD
OCDF
INTERNAL STANDARDS
13C-2378-TCDD
13C-2378-TCDF
13C-123678-HXCDD
13C-1234678-HpCDF
13C-OCDD
RECOVERY STANDARDS
13C-1234-TCDD
13C-123789-HXCDD
SELECTED
IONS
320/322
304/306
340/342
356/358
340/342
374/376
374/376
390/392
390/392
390/392
374/376
374/376
408/410
424/426
408/410
458/460
442/444
332/334
316/318
402/404
420/422
470/472
332/334
402/404
ION ABUNDANCE RATIO
CC1
CC2
CC3
CC4
CCS
FLAG
QC
LIMITS
0.65-0.89
0.65-0.89
1.24-1.86
1.24-1.86
1.24-1.86
1.05-1.43
1.05-1.43
1.05-1.43
1.05-1.43
1.05-1.43
1.05-1.43
1.05-1.43
0.88-1.20
0.88-1.20
0.88-1.20
0.76-1.02
0-7 /r T /i*>
. / D i. • UZ
0.65-0.89
0.65-0.89
1.05-1.43
0.88-1.20
0.76-1.02
0.65-0.89
1.05-1.43
QC limits represent + 15% window around the theoretical ion abundance ratio.
A single point calibration is performed for seven of the native analytes
and the cleanup standard.
The laboratory must flag any analyte in any calibration solution which does
not meet the ion abundance ratio QC limit by placing an asterisk in the flag
column.
FORM VI PCDD-2
10/90
-------
7DFA
PCDD/PCDF CONTINUING CALIBRATION SUMMARY
Lab Name:_
Lab Code:
GC Column:
Date Analyzed:
Lab File ID:
Case No.
ID:
Contract:
SAS No.:
SDG No.
(mm)
Instrument ID:
Time Analyzed:
Init. Calib. Date(s):
NATIVE ANALYTES
2378-TCDD
2378-TCDF
' 12378-PeCDF
12378-PeCDD
23478-PeCDF
123478-HxCDF
123678-HxCDF
123478-HxCDD
123678-HxCDD .
123789-HxCDD
234678-HXCDF
123789-HxCDF
1234678-HpCDF
1234678-HpCDD
1234789-HpCDF
OCDD
OCDF
INTERNAL STANDARDS
VS. RECOVERY STDS.
13C-2378-TCDD
13C-2378-TCDF
13C-123678-HXCDD
13C-1234678-HpCDF
13C-OCDD
37C1-2378-TCDD
RECOVERY STANDARDS
13C-1234-TCDD
13C-123789-HXCDD
SELECTED
IONS
320/322
304/306
340/342
356/358
340/342
374/376
374/376
390/392
390/392
390/392
374/376
374/376
408/410
424/426
408/410
458/460
442/444
332/334
316/318
402/404
420/422
470/472
328/NA
332/334
402/404
RRF
NA
NA
MEAN
RRF
NA
NA
%D
NA
NA
RRF
FLAG
NA
NA
ION
RATIO
NA
ION
FLAG
NA
QC
LIMITS
0.65-0.89
0.65-0.89
1.24-1.86
1.24-1.86
1.24-1.86
1.05-1.43
1.05-1.43
1.05-1.43
1.05-1.43
1.05-1.43
1.05-1.43
1.05-1.43
0.88-1.20
0.88-1.20
0.88-1.20
0.76-1.02
0.76-1.02
0.65-0.89
0.65-0.89
1.05-1.43
0.88-1.20
0.76-1.02
NA
0.65-0.89
1.05-1.43
QC limits shown are for ion abundance ratios. Maximum %D for RRF is + 30.0%
The laboratory must flag any analyte which does not meet criteria for %D or
ion abundance ratio by placing an asterisk in the appropriate flag column.
FORM VII PCDD-l
10/90
-------
7DFB
PCDD/PCDF CONTINUING CALIBRATION RETENTION TIME SUMMARY
Lab Name:_
Lab Code:
GC Column:
Date Analyzed:
Lab File ID:
Case No.
ID:
Contract:
SAS No.:
SDG No.
(mm)
Instrument ID:
Time Analyzed:
Init. Calib. Date(s):
NATIVE ANALYTES
2378-TCDD
2378-TCDF
12378-PeCDF
12378-PeCDD
23478-PeCDF
123478-HxCDF
123678-HxCDF
123478-HxCDD
123678-HxCDD
123789-HxCDD
234678-HXCDF
123789-HXCDF
1234678-HpCDF
1234678-HpCDD
1234789-HpCDF
OCDD
OCDF
INTERNAL STANDARDS
VS. RECOVERY STDS.
13C-2378-TCDD
13C-2378-TCDF
13C-123678-HXCDD
13C-1234678-HpCDF
13C-OCDD
37C1-2378-TCDD
RECOVERY STANDARDS
13C-1234-TCDD
13C-123789-HXCDD
RRT
NA
NA
NA
NA
NA
NA .
NA
RT
RRT = (RT of analyte)/(RT of appropriate internal standard)
FORM VII PCDD-2
10/90
-------
SAMPLE LOG-IN SHEET
Lab Name
Received By (PrruNme)
Paoe of
Log-in Date
Received By (Signaure)
Case Number
Remarks:
1. Custody Seal(s)
Z Custody Seal NOSJ
3. Chain-of-Custody
Records
<. Traffic Reports or Padu
Lists
S Airbffl
a AMdlNo.-
7. Sample Tags
Sample Tag Numbers
a Sample Condition:
9l Does information on
custody records, traffic
reports, and sample tags
agree?
10. Date Received at Lab:
11. Time Received:
Sample
Fraction
Area*
By
On
Sample Delivery Group No. SASNumber
i
PresemMbsem*
kitacVBroken
PresentfAbsent*
xj PresenVAbsent*
AirbilVSlicker
Present/Absent*
PresentfAbsenT
Listed/Not Listed
on Chain-of-Custody
IntactfSrokenVLeaking
YesMo*
Transfer
Fraction
Area*
By
On
EPA
'Sample*
Corresponding
Sample
Tag*
Assigned
Lab*
Remarks:
Condition of Sample Shipment, etc.
* Contact SMO and anach record of resolution. ~~1
Received By
Dale
Logbook No.
Logbook Page No.
FORM DC-1
10/90
-------
PCDD/PCDF COMPLETE SDG FILE (CSF) INVENTORY SHEET
LABORATORY NAME CITY/STATE
CASE NO. SOG NO. SDG NOS. TO FOLLOW SAS MO.
CONTRACT NO. <•••••_ '.. .
All documents delivered in the complete SDG file must be original documents
where possible. (REFERENCE EXHIBIT B, SECTION II and SECTION III.)
PACE NOs CHECK
FROM TO LAB EPA
1. Inventory Sheet (Form DC-2) (Do not number)
2. SDG Narrative
3.. Traffic Report
4. PCDD/PCDF Data
a. Sample Data
TCL Results (Form I PCDD-1)
Calculation of the Toxicity Equivalence
(Form I PCDD-2)
Second Column Confirmation Summary (Form I PCDD-3)
Selected Ion Current Profile (SICP) for each
sample and each analysis of each sample
Total Congener Concentration Results (Form II PCDD)
b. Quality Control Data
Spiked Sample Results (Form III PCDD-1)
Duplicate Sample Results (Form III PCDD-2)
Method Blank Summary (Form IV PCDD)
Window Defining Mix Summary (Form V PCDD-1)
Chromatographic Resolution Summary (Form V PCDD-2)
SICP for each QC analysis
c. Calibration Data
Initial Calibration Data (Form VI PCDD-1 and
Form VI PCDD-2) and PCDD/PCDF standard(s) SICPs
for the initial (five-point) calibration
Continuing Calibration Data (Form VII PCDD-1 and
Form VII PCDD-2) and PCDD/PCDF standard(s) SICPs
for all continuing calibrations
d. Raw Quality Control Data
Blank Data and SICPs for each blank analyzed
Spiked Sample Data and SICPs for each
spiked sample analyzed
FORM DC-2-1 10/90
-------
PCDD/PCDF COMPLETE SDG FILE (CSF) INVENTORY SHEET (Cont.)
CASE HO.
SDK NO.
SOG NOS. TO FOLLOU
SAS NO.
PAGE NOs
FROM TO
CHECK
LAB EPA
5. Miscellaneous Data
Original preparation and analysis forms or copies of
preparation and analysis logbook pages
Internal sample and sample extract transfer
chain-of-custody records
Screening records
All instrument output, including strip charts
from screening activities (describe or list)
6. EPA Shiopine/Receivine Documents
Airbills (No. of shipments )
Chain-of-Custody Records
Sample Tags
Sample Log-In Sheet (Lab & DC1)
SDG Cover Sheet
Miscellaneous Shipping/Receiving Records
(describe or list)
7. Internal Lab Sample Transfer Records and Tracking Sheets
(describe or list)
8. Other Records (describe or list)
Telephone Communication Log
FORM DC-2-2
10/90
-------
PCDD/PCDF COMPLETE SDG FILE (CSF) INVENTORY SHEET (Cont.)
CASE NO.
SDG NO.
SDG NOS. TO FOLLOW
SAS NO.
9. Comments:
Completed by:
(CLP Lab)
(Signature)
(Printed Name/Title)
(Date)
Audited by:
(EPA)
(Signature)
(Printed Name/Title)
(Date)
-------
EXHIBIT C
TARGET COMPOUND LIST (TCL) AND
CONTRACT REQUIRED QUANTITATION LIMITS (CRQL)
NOTE: The values in these tables are quantitation limits. not absolute
detection limits. The amount of material necessary to produce a detector
response that can be identified and reliably quantified is greater than that
needed to be simply detected above the background noise. The quantitation
limits in these tables are set at the concentrations in the sample equivalent
to the concentration of the lowest calibration standard analyzed for each
analyte.
Specific quantitation limits are highly matrix-dependent. The quantitation
limits listed herein are provided for guidance and may not always be
achievable.
The CRQL values listed on the following pages are based on the analysis of
samples according to the specifications given in Exhibit D. All CRQL values
are reported on a wet weight basis, as are sample data produced using the
specifications in Exhibit D.
DFLM01.1 (9/91)
-------
TARGET COMPOUND LIST (TCL) AND CONTRACT REQUIRED QUANTITATION LIMITS (CRQL)
Quantitation I imits
PCDD/PCDF
2378 -TCDD
2378-TCDF
12378-PeCDF
12378-PeCDD
23478 -PeCDF
123478 -HxCDF
123678 -HxCDF
123478 -HxCDD
123678-HxCDD
123789 -HxCDD
234678 -HxCDF
123789 -HxCDF
1234678 -HpCDF
1234678 -HpCDD
1234789 -HpCDF
OCDD
OCDF
CAS Number
1746-01-6
51207-31-9
57117-41-6
40321-76-4
57117-31-4
70648-26-9
57117-44-9
39227-28-6
57653-85-7
19408-74-3
60851-34-5
72918-21-9
67562-39-4
35822-46-9
55673-89-7
3268-87-9
39001-02-0
Water
(ng/L)
10
10
25
25
25
25
25
25
25
25
25
25
25
25
25
50
50
Soil
(ug/Kg)
1.0
1.0
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
5.0
5.0
Fly
Ash
(ug/Kg)
1.0
1.0
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
5.0
5.0
Chemical
Waste2
(ug/Kg)
10
10
25
25
25
25
25
25
25
25
25
25
25
25
25
50
50
All CRQL values listed here are based on the wet weight of the sample.
o
Chemical waste includes the matrices of oils, stillbottoms, oily sludge, wet
fuel oil, oil-laced soil, and surface water heavily contaminated with these
matrices.
C-2
DFLM01.0
-------
In addition, data are reported for the total concentration of all detected
PCDDs or PCDFs in the following horaologues. However, because the number of
non-2,3,7,8-substituted isomers that might be detected in a sample is
unpredictable, it is not possible to assign CRQL values to the total homologue
concentrations.
Homologue
CAS Number
Number of
Possible
Isomers
Number of
2,3,7,8-Substituted
Isomers
Total
Total
Total
Total
Total
Total
Total
Total
TCDD
TCDF
PeCDD
PeCDF
HxCDD
HxCDF
HpCDD
HpCDF
41903-57-5
55722-27-5
36088-22-9
30402-15-4
34465-4608
55684-94-1
37871-00-4
38998-75-3
22
38
14
28
10
16
2
4
1
1
1
2
3
4
1
2
There is only one isomer in both the OCDD and OCDF homologues, hence the total
concentration is the same as the 2,3,7,8-substituted concentration listed on
the previous page.
TCDD - Tetrachlorinated dibenzo-p-dioxin
TCDF - Tetrachlorinated dibenzofuran
PeCDD - Pentachlorinated dibenzo-p-dioxin
PeCDF - Pentachlorinated dibenzofuran
HxCDD - Hexachlorinated dibenzo-p-dioxin
HxCDF = Hexachlorinated dibenzofuran
HpCDD - Heptachlorinated dibenzo-p-dioxin
HpCDF = Heptachlorinated dibenzofuran
OCDD — Octachlorinated dibenzo-p-dioxin
OCDF - Octachlorinated dibenzofuran
C-3
DFLM01.0
-------
EXHIBIT D
ANALYTICAL METHODS
DFLM01.0
-------
Table of Contents
Page
1. Scope and Application D-4
2. Summary of Method D-5
3. Interferences D- 8
4. Apparatus and Equipment D-9
5. Reagents and Consumable Materials D-13
6. Mass Calibration D-16
7. Retention Time Windows and Calibration
of Target Analytes D-16
8. Sample Homogenization, Preservation and Handling D-27
9. Extraction Procedures D-29
9.1. Chemical Waste Sample Extraction D-29
9.2. Soxhlet-Dean Stark (SDS) Apparatus D-30
9.3. Fly Ash Sample Extraction D-32
9.4. Soil/Sediment Sample Extraction D-32
9.5. Water Sample Extraction D-33
9.6. Macro-Concentration Procedures D- 34
9.7. Extract Cleanup Procedures D-37
9.8. Micro-Concentration of Extracts D-38
9.9. Silica Gel and Alumina Column
Chromatographic Procedure D-38
9.10. Carbon Column Chromatographic Procedure D-39
9.11. Final Concentration D-40
10. GC/MS Analysis D-41
11. Identification Criteria D-42
12. Method Blanks D-43
13. Spiked Sample Analysis D-44
14. Duplicate Sample Analysis D-45
15. Calculations D-46
16. Isomer Specificity D-51
17. Required Sample Reruns D-52
D-2 DFLM01.0
-------
LIST OF TABLES
Table 1 Suggested Operating Conditions for a Dfi-5 (or Equivalent) Column
Table 2 2378-TCDD Toxicity Equivalency Factors (TEFs) for PCDDs/PCDFs
Table 3 Concentration Calibration Solutions
Table 4 Internal Standard, Recovery Standard, and Cleanup Standard Solutions
Table 5 Ions Specified for Selected Ion Monitoring for PCDDs/PCDFs
Table 6 Criteria for Isotopic Ratio Measurements for PCDDs/PCDFs
Table 7 Recommended Selected Ion Monitoring Descriptors
Table 8 Relationship of Internal Standards to Analytes, and Relationship of
Recovery Standards to Analytes, Internal Standard and Cleanup
Standards
Table 9 PCDD/PCDF Isomers in the Window Defining Mix for a 60 m DB-5 (or
Equivalent) Column
Table 10 Supplemental Calibration Solution
Table 11 Matrix Spiking Solution
Table 12 Column Performance Solution for a SP-2331 (or Equivalent) Column
Table 13 Example Analytical Sequences
LIST OF FIGURES
Figure 1 Flow Chart for Sample Extraction and Cleanup for the Analysis of
PCDDs and PCDFs in Complex Waste Samples
Figure 2 General Structures of PCDDs and PCDFs
Figure 3 Measurement of Signal-To-Noise Ratio
Figure 4 Soxhlet/Dean-Stark Extractor
Figure 5 Valley Between 2378-TCDD and Other Closely Eluting Isomers on a SP-
2331 (or Equivalent) Column
D-3 DFLM01.0
-------
1. Scope and Application
1.1 This method is appropriate for the detection and quantitative
measurement of 2378-tetrachlorinated dibenzo-p-dioxin (2378-TCDD),
2378-tetrachlorinated dibenzofuran (2378-TCDF), and the 2,3,7,8-
substituted penta-, hexa-, hepta- and octachlorinated dibenzo-p-dioxins
(PCDDs) and dibenzofurans (PCDFs) in water, soil, fly ash, and chemical
waste samples including stillbottom, fuel oil, and sludge matrices.
The analytical method requires the use of high resolution gas
chromatography and low resolution mass spectrometry (HRGC/LRMS) on
sample extracts that have been subjected to specified cleanup
procedures. The calibration range is dependent on the compound and the
sample size. The sample size varies by sample matrix. The Contract
Required Quantitation Limits (CRQLs) for each matrix and compound are
listed in Exhibit C. The upper limit of the calibration range for each
compound is 20 times the CRQL. Samples in which any target compound is
found above the calibration range must be diluted and reanalyzed.
1.2 The protocol requires the calculation of the 2378-TCDD toxicity
equivalence according to the procedures given in the U.S. Environmental
Protection Agency "Update of Toxicity Equivalency Factors (TEFs) for
Estimating Risks Associated with Exposures to Mixtures of Chlorinated
Dibenzo-p-Dioxins and Dibenzofurans (CDDs/CDFs)" March 1989 (EPA 625/3-
89/016). This procedure recognized that structure-activity
relationships exist between the chemical structure of a particular
PCDD/PCDF "and its ability to elicit a biological/toxic response in
various in vivo and in vitro test systems." Of the 210 possible
chlorinated dibenzo-p-dioxins and chlorinated dibenzofurans, the 17
isomers that bear chlorine atoms in the 2,3,7 and 8 positions of their
respective structures are the compounds of greatest concern. To aid in
the assessment of risks to human health and the environment, a factor
is assigned to each of these 17 2,3,7,8-substituted PCDDs and PCDFs
that relates the toxicity of that isomer to a concentration of the most
toxic isomer, 2378-TCDD. These factors are called TEFs. The
concentrations of any of the 17 isomers that are detected in an
environmental sample can then be adjusted by the TEF and summed,
yielding a concentration of 2378-TCDD with an equivalent toxicity.
1.3 If the toxicity equivalence is less than 0.7 parts per billion (ppb)
for a soil or fly ash sample, less than 7 parts-per-trillion (ppt) for
an aqueous sample, or less than 7 ppb for a chemical waste, no further
analysis is required. If the toxicity equivalence is greater than or
equal to 0.7 ppb (soil or fly ash), 7 ppt (aqueous), or 7 ppb (chemical
waste), analysis on a column capable of resolving all 2,3,7,8-
substituted PCDDs/PCDFs is required.
For any sample analyzed on a DB-5 (or equivalent) column in which
either 2378-TCDD or 2378-TCDF is reported as an "Estimated Maximum
Possible Concentration" (see Section 15.7), regardless of TEF-adjusted
concentration or matrix, analysis of the extract is required on a
second GC column which provides better specificity for these two
isomers.
D-4 DFLM01.0
-------
1.4 This method is also capable of determining the total concentration of
all PCDDs/FCDFs in a given level of chlorination (i.e., Total TCDD,
Total FeCDF, etc.), although complete chromatographic separation of all
210 possible FCDDs/PCDFs is not possible under the instrumental
conditions described here. The "Total" concentrations are not assigned
TEF values in the February 1989 TEF procedure, and therefore are not
included in the toxicity equivalence calculations.
1.5 The qualitative identification criteria (see Section 11) include
requirements for retention times, simultaneous detection of three ions
per compound, and limits on the ratio of the abundances of the two most
intense ions produced by each compound. In instances where a signal is
detected that meets all of the qualitative identification criteria
except the ion abundance ratio, the method requires calculation of an
"Estimated Maximum Possible Concentration" (EMPC). The presence of
interferences that coelute with the compounds of interest may cause the
ion abundance ratio to fall outside the limits for qualitative
identification and would also affect the quantitative results. The
EMPC is a worst case estimate of the sample concentration that the
signal would represent if it did meet all the identification criteria
(see Section 15.7). Because of the quantitative uncertainty associated
with the EMPC values, they are not included in the TEF calculations
performed in the method.
1.6 The data that result from these analyses are reported based on the wet
weight of the sample. However, for solid matrices such as
soil/sediments, the percent solid content of the sample is also
reported, if needed by the data user. The percent solids content of
fly ash samples is not reported because the fly ash is treated with an
aqueous acid solution prior to extraction.
1.7 This method is designed for use only by analysts experienced with
residue analysis and skilled in HRGC/LRMS..
1.8 Because of the extreme toxicity of these compounds, the analyst must
take necessary precautions to prevent exposure of personnel to
materials known or believed to contain PCDDs/PCDFs.
2. Summary of Method
2.1 Soil/Sediment Extraction
For the purposes of this method, a soil/sediment sample is defined as a
portion of wet soil/sediment which does not contain oil, but which may
contain other solids such as stones, vegetation, etc. The sample
should not contain an obvious liquid phase (see Section 8.4). A 10 g
aliquot of the soil/sediment sample is spiked with the internal
standard solution and extracted with toluene in a combination of a
Soxhlet extractor and a Dean Stark water separator (SDS).
2.2 Water Extraction
For the purposes of this method, a water sample is defined as a single
phase,.system that is primarily clear water but may contain very small
D-5 DFLM01.0
-------
amounts of floating, suspended and settled particulate matter.
Multiple phases should not be present (see Section 8.4). Approximately
1 L of the water sample is spiked with the internal standard solution
and filtered to separate the aqueous and particulate fractions. The
filtered aqueous fraction is extracted with methylene chloride using a
separatory funnel or continuous liquid-liquid extractor. The
particulate fraction is extracted with toluene in a SDS extractor. The
extracts of the two fractions are then combined for cleanup.
2.3 Fly Ash Extraction
For the purposes of this method, a fly ash sample is defined as a solid
matrix from an incineration or other combustion process which may
contain water and other solids. It should not contain an obvious
liquid phase. A 10 g aliquot of the fly ash is washed with dilute
hydrochloric acid, spiked with the internal standard solution, and
extracted with toluene in a SDS extractor.
2.4 Chemical Waste Sample Extraction
For the purposes of this method, a chemical waste sample includes
sample matrices of oils, stillbottoms, oily sludge, oil-laced soil, and
surface water heavily contaminated with the matrices listed above (see
Section 8.2). Internal standards are added in the concentrations
listed in Table 4 to a 1 or 10 g aliquot of chemical waste. Wet fuel
oil and oily sludge samples, showing signs of water, are spiked with
the internal standard solution, fitted with a reflux condenser and a
Dean Stark water separator to remove the water, and extracted with
toluene. Stillbottom samples are spiked with the internal standard
solution, refluxed with toluene, and filtered.
2.5 Cleanup and Analysis
07
Immediately prior to cleanup, all extracts are spiked with a Cl-2378-
TCDD standard. Because it is added after extraction, the recovery of
this standard may be used to differentiate between losses of analytes
or internal standards during extraction and losses that occur during
the various cleanup procedures. The extracts are subjected to an acid-
base washing treatment and dried. Following a solvent exchange step,
the extract is cleaned up by column chromatographic procedures,
including silica gel, acid alumina, and carbon on celite columns, to
eliminate sample components that may interfere with the detection and
measurement of FCDDs/FCDFs. The extracts are concentrated and the
solvent is exchanged to tridecane. The recovery standards are added to
an aliquot (50 uL) of the extract and the aliquot is reduced to the
final volume of 50 uL. The remaining 50 uL of extract is retained in
the event that dilutions or reanalyses are required. One or two uL of
the concentrated aliquot containing the recovery standards are injected
onto a fused silica capillary column in a gas chromatograph (GC)
interfaced to a mass spectrometer (MS) (see Paragraph 4.1.1).
The identification of PCDD/FCDF isomers is based on the simultaneous
detection of the two most abundant ions in the molecular ion regions
and^the M-COC1 ion. In addition, the identification of OCDD and five
D-6 DFLM01.0
-------
of the 2,3,7,8-substituted isomers, for which a 13C-labeled standard is
available in the internal standard and recovery standard solutions, is
based on their exact retention time (-1 to 3 seconds from the
respective internal or recovery standard signal). The 2,3,7,8-
substituted isomers for which C-labeled standards are not available
in the sample extracts are identified by the relative retention times
of the isomer in the daily standard as compared to the appropriate
internal standard.
The identification of all other PCDD/PCDF isomers is based on their
retention times falling within their respective PCDD/PCDF retention
time windows as established by a window defining mix. Confirmation of
all PCDDs/PCDFs is based on a comparison of the ratio of the integrated
ion abundance of the molecular ion species to the theoretical ion
abundance ratio.
The PCDDs/PCDFs are quantitated by comparing the MS response of the
detected analyte relative to the MS response of the appropriate C-
labeled internal standard (Table 2). The responses of both the ions
monitored for each analyte are used for quantitation. The labeled
internal standards are added prior to sample extraction. Thus, the
quantitative results for the native analytes are corrected for the
recovery of the internal standards, based on the assumption that losses
of the internal standards during sample preparation and analysis are
equal to the losses of the unlabeled PCDDs/PCDFs.
2.6 The recovery of the internal standards is determined by comparing the
MS response of the internal standard to the MS response of the
appropriate recovery standard (Table 2). The recovery standards are
also isotopically labeled compounds, and are added to each sample
extract and blank aliquot just prior to injection.
Because the ability to quantify the concentrations of the unlabeled
analytes and the p'recision of the measurements are related to the
recovery of the internal standards, upper and lower limits are placed
on the percent recovery of the internal standards (see Paragraphs
15.5.2 and 17.1.1).
2.7 If the concentration of any PCDD/PCDF exceeds the calibration range of
the instrument, a dilution must be performed to bring that
.concentration within range. Additional recovery standard solution is
added to the diluted sample extract immediately prior to reanalysis
(see Section 10.4).
If the MS response of any internal standard in the diluted sample is
less than 10% of its MS response in the continuing calibration
standard, the unlabeled PCDD/PCDF concentrations in the sample are
estimated using the MS responses of the recovery standards (see
Paragraph 15.3). The purpose of this requirement is to ensure that
there is an adequate MS response for quantitation.
2.8 In order to provide information on recovery of the analytes of interest
from the sample matrix, the laboratory must prepare a second aliquot of
one ^sample of each matrix in each Sample Delivery Group (SDG) and spike
D-7 DFLM01.0
-------
it with the analytes at concentrations specified in Section 13. This
aliquot is analyzed and the recovery of the spiked analytes is
determined.
2.9 In order to provide information on the precisio- of the analysis in the
sample matrix, the laboratory must perform a duplicate analysis on one
sample of each matrix in each SDG. The samples to be analyzed in
duplicate may be specified by the Region in advance; however, if no
samples are so specified, the laboratory must select a sample of each
matrix for duplicate analyses. The precision of the analysis is
determined as the relative percent difference of the concentrations as
specified in Section 14.
2.10 Due to a variety of situations that may occur during contract
performance, the laboratory shall be required to reextract and
reanalyze certain samples or groups of samples. As used hereafter,
except in the case of dilutions, the term "rerun" shall indicate sample
reextraction, cleanup and reanalysis. When dilutions are required, the
original extract shall be diluted and reanalyzed (see Section 10.4).
When the rerun is required due to matrix effects, interferences or
other problems encountered, the Government will pay the Contractor for
the reruns. Such reruns shall be billable and accountable under the
specified contract allotment of automatic reruns. When the rerun is
required due to Contractor materials, equipment or instrumentation
problems or lack of Contractor adherence to specified contract
procedures, the rerun shall not be billable nor accountable under the
terms of this contract. The Contractor's failure to perform any of the
sample reruns specified herein, either billable or nonbillable, shall
be construed as Contractor nonperformance and may result in the
termination of the contract for default. Specific requirements for
reextraction and reanalysis are given in Section 17.
NOTE: A contaminated method blank is the only circumstance that may
require more than one rerun per sample.
3. Interferences
3.1 Any compound that yields ions listed in Table 5 and also elutes within
the retention time window of the corresponding homologue is a potential
interference. PCDDs/FCDFs are often associated with other chlorinated
compounds such as polychlorinated biphenyls (PCBs) and polychlorinated
diphenyl ethers (FCDPEs). These compounds may be found at
concentrations several orders of magnitude higher than that of the
analytes of interest and may otherwise interfere with the analysis of
PCDDs/PCDFs. Therefore, the retention time of the target analytes must
be verified using reference standards and compared to retention time
windows established during the calibration. While the cleanup
procedures specified in this method are designed to minimize these
interferences, some samples may ultimately require additional cleanup
steps to achieve the detection limits.
3.2 Solvents, reagents, glassware, and other sample processing hardware may
yield discrete artifacts and/or elevated baselines which may cause
D-8 DFLM01.0
-------
misinterpretation of chromatographic data. All of these materials
shall be demonstrated to be free from interferents under the conditions
of analysis by running laboratory method blanks.
NOTE: Because of the possibility of contamination, analvsts should
avoid using PVC gloves. However, latex gloves may be adequate.
3.3 The use of high purity reagents and solvents helps to minimize
interference problems. Purification of solvents by distillation in all
glass systems may be necessary.
3.4 High resolution capillary columns are used to resolve as many PCDD/PCDF
isomers as possible. No single column is known to resolve all 210 of
the isomers. The columns employed by the laboratory in these analyses
must be capable of resolving the 17 2,3,7,8-substituted PCDDs/PCDFs
sufficiently to meet the method specifications (see Section 7.1).
4. Apparatus and Equipment
Brand names and catalog numbers are for illustrative purposes only and
do not imply an endorsement by EPA. Equivalency of materials from
other suppliers may be demonstrated by performing analyses that meet
the specifications of this method.
4.1 Gas Chromatograph/Mass Spectrometer/Data System (GC/MS/DS)
4.1.1 The GC shall be capable of temperature programming and be
equipped with all required accessories, such as syringes,
gases, and a capillary column. The GC injection port shall be
designed for capillary columns; a splitless or an on-column
injection technique is recommended. A 2 uL injection volume is
assumed throughout this method; however, with some GC injection
ports, other volumes may be more appropriate. A 1 uL injection
volume may be used if adequate sensitivity and precision can be
demonstrated.
NOTE: The injection volume for all sample extracts, blanks,
quality control (QC) samples and calibration solutions
shall be the same.
4.1.2 Mass spectral data shall be obtained using a low resolution
instrument that utilizes 70 volts (nominal) electron energy in
the electron impact mode. The system shall be capable of
selected ion monitoring (SIM) for at least 18 ions per cycle,
with a cycle time of 1 second or less. Minimum integration
time for SIM is 25 milliseconds per m/z. The integration time
used to analyze samples shall be identical to the time used to
analyze the initial and continuing calibration solutions and QC
samples. Total data acquisition time per cycle (18 ions) must
not exceed 1 second.
4.1.3 An interfaced data system is required to acquire, store, reduce
and output mass spectral data.
D'9 DFLM01.0
-------
4.1.4 GC/MS interfaces constructed of all glass or glass-lined
materials are required. Glass can be deactivated by silanizing
with dichlorodimethylsilane. Inserting a fused silica column
directly into the MS source is recommended; care must be taken
not to expose the end of the column to the electron beam.
4.1.5 The Contractor shall use a magnetic media storage device
capable of recording data suitable for long-term off-line
storage. The Contractor shall record all raw GC/MS data
acquired during the entire contract period on magnetic media in
appropriate instrument manufacturer format.
4.2 GC Column
Fused silica capillary columns are required. The columns shall
demonstrate the required separation of all 2378-specific isomers
whether a dual column or a single column analysis is chosen. Column
operating conditions shall be evaluated at the beginning and end of
each 12-hour period during which samples or concentration calibration
solutions are analyzed (see Section 7.4).
Isomer specificity for all 2,3,7,8-substituted PCDDs/PCDFs cannot be
achieved on the 60 m DB-5 column. In order to determine the
concentration of the individual 2,3,7,8-substituted isomers, if the
toxicity equivalence is greater than 0.7 ppb (solids), 7 ppt (aqueous),
or 7 ppb (chemical waste), the sample extract shall be reanalyzed on a
60 m SP-2330 or SP-2331 (or equivalent) GC column.
For any sample analyzed on a DB-5 (or equivalent) column in which
either 2378-TCDD or 2378-TCDF is reported as an Estimated Maximum
Possible Concentration (see Section 15.7), regardless of TEF-adjusted
concentration or matrix, analysis of the extract is required on a
second GC column which provides better specificity for these two
isomers.
Analysis on a single column is acceptable if the required separation of
all the 2378-specific isomers is demonstrated and the minimum
acceptance criteria outlined in Sections 7.1, 7.2 and 7.3 are met. See
Section 11 for the specifications for the analysis of the 2378-specific
isomers using both dual columns and single columns.
4.3 Miscellaneous Equipment
The following list of items does not necessarily constitute an
exhaustive compendium of the equipment needed for this analytical
method.
4.3.1 Nitrogen evaporation apparatus (N-Evap* Analytical Evaporator
Model 111. Organomation Association Inc., Northborough, MA, or
equivalent).
4.3.2 Balance capable of accurately weighing + 0.01 g.
D-10 DFLM01.0
-------
4.3.3 Water bath. Equipped with concentric ring cover and
temperature controlled within ± 2s C.
4.3.4 Stainless steel (or glass) pan large enough to hold contents of
1-pint sample containers.
4.3.5 Glove box. For use in preparing standards from neat materials
and in handling soil/sediment samples containing fine
particulates that may pose a risk of exposure.
4.3.6 Rotary evaporator, R-110. Buchi/Brinkman - American Scientific
No. E5045-10 or equivalent.
4.3.7 Centrifuge. Capable of operating at 400 x G with a 250-300 mL
capacity.
4.3.8 Drying oven.
4.3.9 Vacuum oven. Capable of drying solvent-washed solid reagents
at 110°C.
4.3.10 Mechanical shaker. A magnetic stirrer, wrist-action or
platform-type shaker, that produces vigorous agitation. Used
for pre-treatment of fly ash samples.
4.4 Glassware
4.4.1 Extraction jars. Amber glass with Teflon-lined screw cap;
minimum capacity of approximately 200 mL; must be compatible
with mechanical shaker to be used.
4.4.2 Kuderna-Danish (KD) Apparatus. 500 mL evaporating flask, 10 mL
graduated concentrator tubes with ground glass stoppers, three
ball macro-Synder column.
4.4.3 Disposable Pasteur pipets, 150 mm long x 5 mm ID.
4.4.4 Disposable serological pipets, 10 mL for preparation of the
carbon column specified in Section 9.10.
4.4.5 Vials. 0.3 mL and 2 mL amber borosilicate glass with conical
shaped reservoir and screw caps lined with Teflon-faced
silicone disks.
4.4.6 Funnels. Glass; appropriate size to accommodate filter paper
(12.5 cm).
4.4.7 Chromatography Columns. 300 mm x 10.5 mm glass chromatographic
column fitted with Teflon stopcock.
4.4..8 Soxhlet Apparatus, 500 mL flask, all glass. Complete with
glass extractor body, condenser, glass extraction thimbles,
heating mantle, and variable transformer for heat control.
D-ll DFLM01.0
-------
NOTE: Extraction thimbles must be of stifficient size to hold
100 g of sand, 5 g of silica gel, and at least 10 g of
solid sample, with room to mix the sand and sample in
the thimble.
4.4.9 Dean Stark Water Separator Apparatus, with a Teflon stopcock.
Must fit between Soxhlet extractor body and condenser.
4.4.10 Concentrator tubes. 15 mL conical centrifuge tubes.
4.4.11 Separatory funnels. 125 mL and 2 L separatory funnels with a
Teflon stopcock.
4.4.12 Continuous Liquid-Liquid Extractor. 1 L sample capacity,
suitable for use with heavier than water solvents.
4.4.13 Boiling chips. Teflon boiling chips washed with hexane prior
to use.
4.4.14 Buchner funnel. 15 cm.
4.4.15 Filtration flask. For use with Buchner funnel, 1 L capacity.
4.5 Glassware Cleaning Procedures
Reuse of glassware should be minimized to avoid the risk of using
contaminated glassware. All glassware that is reused shall be
scrupulously cleaned as soon as possible after use, applying the
following procedure.
4.5.1 Rinse glassware with the last solvent used in it.
4.5.2 Wash with hot water containing detergent.
4.5.3 Rinse with copious amounts of tap water and several portions of
distilled water. Drain dry.
4.5.4 Rinse with high purity acetone and hexane.
4.5.5 After glassware is dry, store inverted or capped with aluminum
foil in a clean environment.
Do not bake reusable glassware as a routine part of cleaning. Baking
may be warranted after particularly dirty samples are encountered, but
should be minimized, as repeated baking may cause active sites on the
glass surface that will irreversibly adsorb PCDDs/PCDFs.
CAUTION: The analysis for PCDDs/PCDFs in water samples is for much
lower concentrations than in soil/sediment, fly ash, or
chemical waste samples. Extreme care must be taken to prevent
cross-contamination between soil/sediment, fly ash, chemical
waste and water samples. Therefore, it is strongly
recommended that separate glassware be reserved for analyzing
,_ water samples.
D-12 DFLM01.0
-------
4.6 Freextraction of Glassware
It is required that all glassware be rinsed or preextracted with
solvent immediately before use. The SDS apparatus and continuous
liquid-liquid extractors must be preextracted for approximately three
hours immediately prior to use. The pooled waste solvent for a set of
extractions may be concentrated and analyzed as a method of
demonstrating that the glassware was free of contamination.
It is recommended that each piece of reusable glassware be numbered in
such a fashion that the laboratory can associate all reusable glassware
with the processing of a particular sample. This procedure will assist
the laboratory in tracking down possible sources of contamination for
individual samples, identifying glassware associated with highly
contaminated samples that may require extra cleaning, and determining
when glassware should be discarded.
5. Reagents and Const
Brand names and catalog numbers are for illustrative purposes only and
do not imply an endorsement by EPA. Equivalency of materials from
other suppliers may be demonstrated by performing analyses that meet
the specifications of this method.
5.1 " Solvents. High purity, distilled-in-glass: hexane, methanol,
methylene chloride, toluene, isooctane, cyclohexane, acetone, tridecane
(or nonane).
5.2 Filters
5.2.1 Filter paper. Whatman No. 1 or equivalent.
5.2.2 Glass fiber filter. 15 cm, for use with Buchner funnel.
5.2.3 0.45 micron, Millipore or equivalent, PTFE or other material
compatible with toluene. Rinse with toluene.
5.3 White quartz sand. 60/70 mesh, for use in the SDS extractor. Bake at
450°C for 4 hours minimum.
5.4 Glass wool, silanized. Extract with methylene chloride and hexane
before use.
5.5 Sodium Sulfate. Granular, anhydrous. Before use, heat to 400°C in a
shallow tray for approximately 4 hours, cool in a desiccator, and store
in a glass jar.
5.6 Potassium Hydroxide. ACS grade, prepare a 20% (w/v) solution in
distilled water.
5.7 Sulfuric Acid, concentrated. ACS grade, specific gravity 1.84.
5.8 Sodium Chloride. ACS grade, prepare a 5% (w/v) solution in distilled
water.
D-13 DFLM01.0
-------
5.9 Hydrochloric Acid, concentrated. ACS grade, specific gravity 1.17.
Prepare a IN solution in distilled water for pretreatment of fly ash
samples.
5.10 Column Chromatography Reagents
5.10.1 Alumina, acidic AG4, Bio Rad Laboratories (catalogue #132-1240)
or equivalent. Soxhlet extract with methylene chloride for 21
hours and activate by heating in a foil-covered glass container
for 24 hours at 190°C.
5.10.2 Charcoal Carbon. Active carbon AX-21 (Anderson Development
Company, Adrian, HI, or equivalent), prewashed with methanol
and dried in vacuo at 110°C.
5.10.3 Celite 545 (Supelco or equivalent).
5.10.4 Silica gel. High purity grade, type 60, 70-230 mesh; Soxhlet
extract with methylene chloride for 21 hours and activate by
heating in a foil-covered glass container for 24 hours at
190'C.
5.10.5 Silica gel impregnated with 2% (w/w) sodium hydroxide. Add 1
part by weight of 1 M NaOH solution to 2 parts silica gel
(extracted and activated) in a screw-cap bottle and mix with a
glass rod until free of lumps.
5.10.6 Silica gel impregnated with 40% (w/w) sulfuric acid. Add 2
parts by weight concentrated sulfuric acid to 3 parts silica
gel (extracted and activated), mix with a glass rod until free
of lumps, and store in a screw-cap glass bottle.
5.11 Calibration Solutions (Table 3)
Five tridecane (or nonane) solutions (CC1-CC5) containing 10 unlabeled
and 7 carbon-labeled PCDDs/PCDFs at known concentrations which are used
to calibrate the instrument. One of these five solutions (CC3) is used
as the continuing calibration solution and contains 7 additional
unlabeled 2,3,7,8-substituted isomers that are commercially supplied
(see Paragraph 7.3.2.1). The concentration ranges are homologue-
dependent with the lowest concentrations associated with tetra- and
pentachlorinated dioxins and furans (0.1-2.0 ng/uL), and the higher
concentrations associated with the hexa- through octachlorinated
homologues (0.5-10.0 ng/uL). Depending on the availability of
materials, the Environmental Monitoring Systems Laboratory (EMSL-LV)
will provide these solutions, with the exception of the additional
2,3,7,8-substituted isomers for the CC3 solution.
5.12 Internal Standard Solution (Table 4)
The solution contains the five internal standards in tridecane (or
nonane) at the nominal concentrations listed in Table 4. Depending on
the availability of materials, EMSL-LV will provide the solution. Mix
10 uL^with 1.0 mL of acetone before adding to each sample and blank.
D-14 DFLM01.0
-------
5.13 Recovery Standard Solution
The hexane solution contains the recovery standards, Ci2-1234-TCDD
and 13Ci2' 123789 -HxCDD, at concentrations of 5.0 ng/uL, in a solvent
other than tridecane or nonane (see Section 10.2). Depending upon the
availability of materials, EMSL-LV will provide the solution.
5.14 Continuing Calibration Solution
This solution contains standards to be used for identification and
quantitation of target analytes. In order to have all 2,3,7,8-
substituted isomers and the cleanup standard present for quantitation
purposes, a commercially supplied supplemental standard and the cleanup
standard solution are combined with the EPA- supplied CC4 solution to
produce the CC3 solution (see Paragraph 7.4.1). This solution is
identified in Table 3.
5.15 Window Defining Mix
This solution is to be obtained by the laboratory through commercial
vendors. The solution contains the first and last eluting isomer of
each homologue (see Table 9) and is used to verify that the switching
times between the descriptors have been appropriately set.
The window defining mix need not contain any of the labeled internal or
recovery standards, as no quantitative measurements are based on this
mixture. However, these standards and other isomers may be added to
the mixture listed in Table 7 at the discretion of the laboratory, so
long as the additional contents of the mixture are clearly specified in
every SDG Narrative.
If the laboratory employs a GC column that has a different elution
order than those specified here, the laboratory must ensure that the
first and last eluting isomers in each homologue are represented in the
window defining mix used to evaluate that column. The concentrations
of any additional isomers should be approximately the same as those
listed in Table 9.
EMSL-LV does not supply the window defining mix (see Table 9) .
5.16 Supplemental Calibration Solution
This solution contains seven 2, 3, 7, 8 -substituted PCDD/PCDF isomers to
be added to the CC4 solution to produce the CC3 solution that is used
for identification and quantitation of target analytes. EMSL-LV does
not supply this solution (see Table 10) .
5 . 17 Cleanup Standard
Q-7
This solution contains -"C14-2378-TCDD at a concentration of 5 ng/uL (5
ug/mL) in tridecane (or nonane) and is added to all sample extracts
prior to cleanup. The solution may be added at this concentration or
D-15 DFLM01.0
-------
diluted into a larger volume of solvent (see Paragraph 9.7.1). The
recovery of this compound is used to judge the efficiency of the
cleanup procedures.
5.18 Matrix Spiking Standard
This solution contains 10 of the 2,3,7,8-substituted isomers, at the
concentrations listed in Table 11 in tridecane (or nonane), and is used
to prepare the spiked sample aliquot (see Section 13). Dilute 10 uL of
this standard to 1.0 mL with acetone and add to the aliquot chosen for
spiking.
5.19 Column Performance Solution
The laboratory must obtain this solution through commercial vendors.
The solution contains 2378-TCDD and the other TCDD isomers (1478-TCDD
and the 1237/1238-TCDD pair) that elute closest to 2378-TCDD on the SP-
2331 (or equivalent) column. The solution is used to verify the
chromatographic resolution of the SP-2331 (or equivalent) GC column.
The concentrations of these isomers should be approximately 0.5 ng/uL
in tridecane (or nonane).
If the laboratory employs a GC column that has a different elution
order than those specified here, the laboratory must ensure that the
isomers eluting closest to 2378-TCDD are represented in the column
performance solution.
EMSL-LV does not supply the column performance solution.
6. Mass Calibration
Mass calibration of the MS is recommended prior to analyzing the
calibration solutions, blanks, samples and QC samples. It is
recommended that the instrument be tuned to greater sensitivity in the
high mass range in order to achieve better response for the later
eluting compounds. Optimum results using FC-43 for mass calibration
may be achieved by scanning from 222-510 amu every one second or less,
utilizing 70 volts (nominal) electron energy in the electron ionization
mode. Under these conditions, m/z 414 and m/z 502 should be 30-50% of
m/z 264 (base peak).
7. Retention Time Windows and Calibration of Target Analytes
Prior to the calibration of the GC/MS system, it is necessary to
establish the appropriate switching times for the SIM descriptors (see
Table 7) and to verify the chromatographic resolution. The switching
times are determined by the analysis of the window defining mix,
containing the first and last eluting isomers in each homologue (see
Table 9) . Chromatographic resolution is verified by the analysis of
one of two solutions, depending on the GC column used for analysis.
Two types of calibration procedures, initial and continuing, are
required. The initial calibration is required before any samples are
analyzed^for PCDDs/PCDFs, and intermittently throughout sample
D-16 DFLM01.0
-------
analysis, as dictated by the results of the continuing calibration (see
Section 7.4). The continuing calibration is required at the beginning
of each 12-hour time period during which samples are analyzed.
Samples shall not be analyzed until acceptable descriptor switching
times, chromatographic resolution, and calibrations, as Described in
Sections 7.1, 7.2, 7.3 and 7.4, are achieved and documented. The
sequence of analyses is shown in Table 13.
7.1 Window Defining Mix
The window defining mix shall be analyzed before any calibration
standards in order to evaluate the descriptor switching times. The
commercially available mix (see Section 5.15) contains the first and
last eluting isomers in each homologue. Mixes are available for
various columns. The mix for the DB-5 (or equivalent) column may not
be appropriate for the SP-2331 or other columns.
The ions in each of the four recommended descriptors are arranged so
that there is overlap between the descriptors. The ions for the TCDD,
TCDF, PeCDD and PeCDF isomers are in the first descriptor, the ions for
the PeCDD, PeCDF, HxCDD and HxCDF isomers are in the second descriptor,
the ions for the HxCDD, HxCDF, HpCDD and HpCDF isomers are in the third
descriptor, and the ions for the HpCDD, HpCDF, OCDD and OCDF isomers
are in the fourth descriptor.
The descriptor switching times are set such that the isomers that elute
from the GC during a given retention time window will also be those
isomers for which the ions are monitored. For the homologues that
overlap between descriptors, the laboratory may use discretion in
setting the switching times. However, do not set descriptor switching
times such that a change in descriptors occurs at or near the expected
retention time of any of the 2,3,7,8-substituted isomers.
The window defining mix need not contain any of the labeled internal or
recovery standards, as no quantitative measurements are based on this
mixture. However, these standards and other isomers may be added to
the mixture listed in Table 7 at the discretion of the laboratory, so
long as the additional contents of the mixture are clearly specified in
every SDG Narrative.
7.1.1 Analyze a 2 uL aliquot of the window defining mix, using the GC
column conditions in Table 1.
7.1.2 Adjust the descriptor switching times and the GC column
conditions as needed to ensure that the isomers elute in the
appropriate ion descriptors (see Table 7).
7.1.3 The window defining mix must be analyzed at the following
frequency:
7.1.3.1 Before initial calibration on each instrument and GC
column used for analysis.
D-17 DFLM01.0
-------
7.1.3.2 Each time a new initial calibration is performed,
regardless of reason.
7.1.3.3 Each time adjustments or instrument maintenance
activities are performed that may affect retention
times .
7.1.3.4 .Any time the retention time of either the
1234-TCDD or 13C12- 123789 -HxCDD recovery standards
in any analysis varies by more than 10 seconds from
its retention time in the most recent continuing
calibration standard (see Paragraphs 7.3.2.3,
7.5.2.1 and 11.1.4)
7.1.4 If the laboratory employs a GC column that has a different
elution order than those columns specified here, the laboratory
must ensure that the first and last eluting isomers in each
homologue are represented in the window defining mix used to
evaluate that column. The concentrations of any additional
isomers should be approximately the same as those listed in
Table 9.
7.1.5 Analysis on a single GC column (as opposed to situations
requiring a second column confirmation) is acceptable if the
required separation of all of the 2, 3, 7, 8 -substituted isomers
is demonstrated and the resolution criteria for both the DB-5
and SF-2331 (or equivalent) columns are met (see Paragraphs
7.3.2.1 and 7.2.3).
7.2 Chromatographic Resolution
7.2.1 For analyses on a DB-5 (or equivalent) GC column, the
Chromatographic resolution is evaluated by the analysis of the
CC3 standard during both the initial and continuing calibration
procedures (see Paragraphs 7.3.2.1 and 7.4.2).
7.2.2 For analyses on a SP-2331 (or equivalent) GC column, the
Chromatographic resolution is evaluated before the analysis of
any calibration standards by the analysis of a commercially
available column performance mixture (see Section 5.19) that
contains the TCDD isomers that elute most closely with 2378-
TCDD on this GC column (1478-TCDD and the 1237/1238-TCDD pair).
Analyze a 2 uL aliquot of this solution, using the column
operating conditions and descriptor switching times previously
established.
Note: The column performance mixture may be combined with the
window defining mix into a single solution, provided
that the combined solution contains the isomers needed
to determine that the criteria for both analyses can be
met.
D-18 DFLM01.0
-------
7.2.3 GC Resolution Criteria for SP-2331 or Equivalent Column. The
chromatographic peak separation between unlabeled 2378-TCDD and
the peaks representing all other unlabeled TCDD isomers shall
be resolved with a valley of < 25 percent, where:
Valley - (x/y)(100).
y - the peak height of any TCDD isomer.
x - the distinction from the baseline to the bottom of the
valley between adj acent peaks, measured as shown in
Figure 5.
The resolution criteria must be evaluated using measurements
made on the selected ion current profile (SICP) for the
appropriate ions for each isomer. Measurements are not made
from total ion current profiles.
Further analyses may not proceed until the GC resolution
criteria have been met.
7.2.4 If the laboratory uses a GC column other than those specified
here, the laboratory must ensure that the isomers eluting
closest to 2378-TCDD on that column are used to evaluate GC
column resolution. The chromatographic peak separation between
unlabeled 2378-TCDD and the peaks representing all other
unlabeled TCDD isomers shall be resolved with a valley of < 25
percent.
7.2.5 Analysis on a single GC column (as opposed to situations
requiring a second column confirmation) is acceptable if the
required separation of all of the 2,3,7,8-substituted isomers
is demonstrated and the resolution criteria for both the DB-5
and SP-2331 (or equivalent) columns are met (see Paragraphs
7.3.2.1 and 7.2.3).
7.3 Initial Calibration
Once the window defining mix has been analyzed and the descriptor
switching times have been verified (and after the analysis of the
column performance solution if using a GC column other than DB-5), the
five concentration calibration solutions (CC1-CC5), described in Table
3, shall be analyzed prior to any sample analysis. The CC1, CC2, CC4
and CCS solutions shall be used as provided by EPA. The CC3 solution
is prepared by combining CC4 solution, the supplemental calibration
solution, and the internal, cleanup, and recovery standard solutions as
described in Paragraph 7.4.1.
7.3.1 Analyze a 2 uL (see Paragraph 4.1.1) aliquot of each of the
five concentration calibration solutions, beginning with CCS
solution (see Paragraph 7.4.1). The following MS/DS conditions
shall be used:
D-19 DFLM01.0
-------
7.3.1.1 Acquire SIM data for each of the ions listed in
Table 5 including the ions to monitor interfering
compounds. See Table 7 for the recommended US
descriptors.
7.3.1.2 The total cycle time for data acquisition must be
less than one second. Acquire at least five data
points for each ion during the elution of the GC
peak.
7.3.2 The Contractor shall not proceed with the sample analysis until
an acceptable initial calibration has been performed and
documented according to the following criteria: GC resolution,
ion abundance ratios, retention times, and instrument
sensitivity.
7.3.2.1 GC Resolution Criteria for DB-5 or Equivalent
Column. The chromatographic peak separation between
the 13C12-2378-TCDD peak and 13C12-1234-TCDD isomers
shall be resolved with a valley of < 25 percent, in
all calibration standards, where:
Valley - (x/y)(100).
y - the peak height of f^C12-2378-TCDD.
x - measured using the C^2-1234-TCDD peak as shown
in Figure 5.
In addition, the chromatographic peak separation
between the 123478-HxCDD and 123678-HxCDD in the CC3
solution shall be resolved with a valley of < 50
percent, calculated in a similar fashion as above.
The resolution criteria must be evaluated using
measurements made on the SICP for the appropriate
ions for each isomer. Measurements are not made
from total ion current profiles.
7.3.2.2 The relative ion abundance criteria for PCDDs/PCDFs
listed in Table 6 must be met for all PCDD/PCDF
peaks, including the labeled internal and recovery
standards, in all solutions. The lower and upper
limits of the ion abundance ratios represent a + 15
percent window around the theoretical abundance
ratio for each pair of selected ions. The Cl-
2378-TCDD cleanup standard contains no 35C1, thus
the ion abundance ratio criterion does not apply to
this compound.
7.3.2.3 For all calibration solutions, the retention times
of the isomers must fall within the appropriate
retention time windows established by the window
defining mix analysis. In addition, the absolute
retention times of the recovery standards,
D-20 DFLM01.0
-------
1234-TCDD and 13C12- 123678 -HxCDD, shall not change
by more than 10 seconds between the initial CCS
analysis and the analysis of any other standard.
7.3.2.4 MS Sensitivity. For all calibration solutions,
including the CC1 solution, the signal-to-noise
ratio (S/N) must be greater than 2.5 for the
unlabeled PCDD/PCDF ions , and greater than 10 for
the internal standard and recovery standard ions.
7.3.3 Calculate the relative response factors (RRFs) for the 17
unlabeled target analytes relative to their appropriate
internal standards (RRFn) (see Table 8) , according to the
formulae below. For the seven unlabeled analytes and the
37Cl4-2378-TCDD cleanup standard that are found only in the CC3
solution, only one RRF is calculated for. each analyte. For the
other 10 unlabeled analytes , calculate the RRF of each analyte
in each calibration standard.
Calculate the RRFs for the five labeled internal standards and
the cleanup standard relative to the appropriate recovery
standard (RRF^g) (see Table 8) , in each calibration standard,
according to the following formulae:
RRFn -
(An1 t- Q x Qis
x Qn
(A,...1 + Ars2) x Qi
where :
tdAn2 -
of the isomer of interest (Table 5) .
1 2
and A^ - integrated areas of the two quantitation ions
1 2
Ais an<* Ais ~ integrated areas of the two quantitation ions
of the appropriate internal standard (Table
5).
1 2
Ars and Ars — integrated areas of the two quantitation ions
of the appropriate recovery standard (Table
5).
Qn - quantity of unlabeled PCDD/PCDF analyte inj ected (ng).
Qis " quantity of appropriate internal standard injected (ng).
Qrs - quantity of appropriate recovery standard injected (ng).
For quantitations involving the use of peak heights instead of
peak areas, see Section 11.4.
D-21 DFLM01.0
-------
There is only one quantitation ion for the Cl cleanup
standard. Calculate the relative response factor as described
for RRF^s, using one area for the cleanup standard and the sum
of the areas of the ions from the recovery standard.
The RRFn and RRF^g are dimensionless quantities; therefore, the
units used to express the Qn, Q£S and Qrs must be the same.
NOTE: This protocol is based on the assumption that if the 10
unlabeled 2,3,7,8-substituted isomers provided in the
EPA standard solutions meet linearity criteria, then the
seven additional 2,3,7,8-substituted isomers and the
cleanup standard in the CC3 solution may be assumed to
have a sufficiently linear response to be used for
quantitation. These eight RRFs cannot be used to
determine percent relative standard deviation, but are
used for percent difference determinations (as described
in Paragraph 7.4.6.4) and quantitation of target
analytes.
7.3.4 Calculate the relative response factors for the native
PCDDs/PCDFs relative to the recovery standards (RRFrs) where:
RRFrs - RRFn x RRFis
This relative response factor is necessary when the sample is
diluted to the extent that the MS response of the internal
standard is less than 10 percent of its MS response in the
continuing calibration standard (see Section 15.3).
7.3.5 Relative Response Factor Criteria. Calculate the mean RRF and
percent relative standard deviation (%RSD) of the five RRFs
(CC1-CC5) for each unlabeled PCDD/PCDF and labeled internal
standards present in all five concentration calibration
solutions.
No mean RRF or %RSD calculations are possible for the 2,3,7,8-
substituted isomers or the cleanup standard found only in the
CC3 solution.
Standard Deviation
%RSD - x 100
Mean RRF
The %RSD of the five RRFs (CC1-CC5) for the unlabeled
PCDDs/PCDFs and the internal standards must not exceed 15.0
percent.
7.3.6 The response factors to be used for determining the total
homologue concentrations are described in Section 15.2.
D-22 DFLM01.0
-------
7.3.7 If any of the requirements listed in Paragraphs 7.3.2 or 7.3.5
are not met, the Contractor is responsible for taking
corrective action before sample analyses are performed. The
following suggestions may be useful.
7.3.7.1 Check and adjust the GC and/or MS operating
conditions.
7.3.7.2 Replace the GC column.
7.3.7.3 Adjust the MS for greater or lesser resolution using
FC-43 (see Section 6).
7.3.7.4 Recalibrate the mass scale.
Once the corrective actions have been completed, the Contractor
must perform a new initial calibration that does meet all the
QC requirements, beginning with analysis of the window defining
mix, before sample analyses may proceed.
7.4 Continuing Calibration
The continuing calibration consists of two parts: evaluation of the
chromatographic resolution and verification of the RRF values to be
used for quantitation. At the beginning of each 12-hour period, the
chromatographic resolution is verified in the same fashion as in the
initial calibration: through the analysis of the CC3 solution on the
DB-5 (or equivalent) column or through the analysis of the column
performance solution on the SP-2331 (or equivalent) column.
NOTE: The 12-hour time period is defined as beginning with the
injection of the CC3 solution on the DB-5 (or equivalent) column
or the injection of the column performance solution on the SP-
2331 (or equivalent) column. The 12-hour period continues until
12:00 hours have elapsed according to the system clock. To be
included in a given 12-hour time period, a sample or standard
must be inj ected within 12:00 hours of the CC3 solution or the
column performance solution.
7.4.1 Prepare the CC3 solution by combining the following volumes of
the solutions listed in Section 5:
500 uL CC4 Solution
125 uL Supplemental Calibration Solution
50 uL Internal Standard Solution
50 uL Recovery Standard Solution
50 uL Cleanup Standard Solution
225 uL Tridecane (or nonane)
to yield a final volume of 1.0 mL at the concentrations
specified for the CC3 solution in Table 3.
D-23 DFLM01.0
-------
7.4.2 For the DB-5 (or equivalent) column, begin the 12-hour period
by analyzing the CCS solution. Inject a 2 uL aliquot of the
continuing calibration solution (CCS) into the GC/MS. The
identical GC/MS/DS conditions used for the analysis of the
initial calibration solutions must be ved for the continuing
calibration solution (see Paragraph 7.3.1). Evaluate the
chromatographic resolution using the QC criteria in Paragraph
7.3.2.1.
7.4.3 For the SP-2331 (or equivalent) column, or other columns with
different elution orders, begin the 12-hour period by analyzing
a 2 uL aliquot of the appropriate column performance solution.
Evaluate the chromatographic resolution using the QC criteria
in Paragraph 7.2.3 or 7.2.4. If this solution meets the QC
criteria, proceed with the analysis of a 2 uL aliquot of the
CC3 solution. The identical GC/MS/DS conditions used for the
analysis of the initial calibration solutions must be used .for
the continuing calibration solution (see Paragraph 7.3.1).
7.4.4 Calculate the RRFs for the 17 unlabeled target analytes
relative to their appropriate internal standards (RPxFn) and the
response factors for the five labeled internal standards and
the cleanup standard relative to the appropriate recovery
standard (RRF^S), according to the following formulae:
+ An2) * Qis
Ais
Ais2) x Qrs
+ Ars*) x Qis
An1, An2, A^1, Ais2. A^1, Ars2, Qn> Qis and Qrs
are defined in Paragraph 7.3.3.
There is only one quant i tat ion ion for the Cl cleanup
standard. Calculate the relative response factor as described
for RRFis, using one area for the cleanup standard and the sum
of the areas of the ions from the recovery standard.
The RRFn and RRFis are dimensionless quantities; therefore, the
units used to express the Qn, Q^s and Qrs must be the same.
7.4.5 Calculate the RRFs for the native PCDDs/PCDFs relative to the
recovery standards (RRFrs) , where RRFrs - RRFn x RRFis. This
relative response factor is necessary for calculations when the
sample is diluted (see Section 15.3).
7.4.6 Continuing Calibration Criteria. The Contractor shall not
proceed with sample analysis until an acceptable continuing
D-24 DFLM01.0
-------
calibration has been performed and documented according to the
following criteria: GO resolution, ion abundance ratios,
retention times, instrument sensitivity, and response factors.
7.4.6.1 GC Column. Resolutior Criteria. The c^^oma to graphic
resolution on the DB-5 (or equivalent) column must
meet the QC criteria in Paragraph 7.3.2.1. The
chromatographic resolution on the SP-2331 (or
equivalent) column must meet the QC criteria in
Paragraph 7.2.3. In addition, the chromatographic
peak separation between the 123478 -HxCDD and the
123678 -HxCDD in the CC3 solution shall be resolved
with a valley of < 50 percent.
7.4.6.2 Ion Abundance Criteria. The relative ion abundances
listed in Table 6 shall be met for all PCDD/PCDF
peaks, including the labeled internal and recovery
standards .
7.4.6.3 Instrument Sensitivity Criteria. For the CC3
solution, the S/N ratio shall be greater than 2.5
for the unlabeled PCDD/PCDF ions, and greater than
10.0 for the labeled internal and recovery
standards.
7.4.6.4 Response Factor Criteria. The measured RRFs of each
analyte and internal standard in the CC3 solution
must be within ±30.0 percent of the mean RRFs
established during initial calibration for the EPA-
supplied standards and within +30.0 percent of the
single point RRFs established during initial
calibration for the supplemental calibration
standards and the cleanup standards.
% Difference - (RRFi - RRFC) x 100
RRFi
where :
RRFj^ - Relative response factor established during
initial calibration.
RRFC - Relative response factor established during
continuing calibration.
7.4.7 If any of the criteria listed in Paragraph 7.4.6 are not met,
the Contractor must take corrective actions and reanalyze the
continuing calibration standard (CC3) . If the criteria in
Paragraph 7.4.6 are met after the corrective action, then
sample analysis may begin, as described in Section 10.
If the criteria in Paragraph 7.4.6 are not met after the
corrective action, then the Contractor must perform a new
initial calibration, beginning with the analysis of the window
D-25 DFLM01.0
-------
defining mix. This new initial calibration must meet all of
the QC criteria in Sections 7.1, 7.2 and 7.3 before sample
analysis may begin.
7 . 5 Instrument Sensitivity Check
In order to demonstrate that the GC/MS/DS system has retained adequate
sensitivity during the course of sample analyses, the Contractor must
analyze the lowest of the standards (CC1) at the end of each 12 -hour
period during which samples and standards are analyzed.
7.5.1 Analyze a 2 uL aliquot of the CC1 solution, using the identical
instrumental conditions used for analysis of samples and
standards .
7.5.2 The CC1 solution analyzed at the end of the 12 -hour period must
meet the following QC criteria:
7.5.2.1 Retention Time Criteria. The absolute retention
time of the recovery standards, 13Ci2-1234-TCDD atld
- 123678 -HxCDD, shall not change by more than 10
seconds between the initial CC3 analysis and the
ending CC1 analysis. If the retention times of
either of these standards changes by more than + 10
seconds, the Contractor must adjust the switching
times of the descriptors and analyze the window
defining mix before proceeding with further
analyses .
7.5.2.2 All the analytes in the CC1 solution must meet the
ion abundance ratio criteria in Table 6 .
7.5.2.3 Instrument Sensitivity Criteria. For the CC1
solution, the S/N ratio shall be greater than 2.5
for the unlabeled PCDD/PCDF ions and greater than
10 . 0 for the labeled internal and recovery
standards .
7.5.3 If the analysis of the CC1 solution at the end of the 12 -hour
period fails either the ion abundance ratio or S/N criteria
above, the Contractor must:
7.5.3.1 Take corrective action.
7.5.3.2 Perform a new initial calibration, beginning with
the analysis of the window defining mix.
7.5.3.3 Start a new analytical sequence (see Table 13).
7.5.3.4 Reanalyze all samples originally analyzed in the
preceding 12 -hour time period in which:
7.5.3.4.1 No PCDDs/PCDFs were detected.
D-26 DFIM01.0
-------
7.5.4.3.2 Neither 2378-TCDD or 2378-TCDF were
detected, even if other PCDDs or PCDFs
were detected.
7.5.4.3.3 Any 2,3,7,8-substituted PCDD or PCDF is
reported as an Estimated Maximum
Possible Concentration (see Section
15.7).
These reanalyses are necessary because poor S/N
ratios indicate a loss of sensitivity that could
lead to false negative results, underestimation of
concentrations, or could cause ion abundance ratios
to fall outside the QC limits.
8. Sample Homogenization. Preservation and Handling
8.1 Homogenization
Although sampling personnel will attempt to collect homogeneous
samples, the Contractor shall examine each sample and determine if the
sample needs phase separation or mixing. The extent to which phase
separation or mixing is required will depend on the sample type.
The Contractor is responsible for taking a representative sample
aliquot from the phase or phases to be analyzed. This responsibility
entails efforts to make the sample phase as homogeneous as possible.
Stirring is recommended when possible.
8.2 Sample Types
8.2.1 For the purpose of this method, a chemical waste sample
includes the sample matrices of oils, oily sludge, stillbottom,
oil-laced soil, and surface water heavily contaminated with any
of the above matrices. The sample may contain particulates and
an obvious non-aqueous liquid phase.
8.2.2 For the purpose of this method, a soil/sediment sample is
defined as a single phase solid system composed of soil or
sediment. The sample may contain stones and vegetation, but
should not contain an obvious aqueous or non-aqueous liquid
phase.
CAUTION: Finely divided soils contaminated with PCDDs/PCDFs
are hazardous because of the potential for
inhalation or ingestion of particles containing the
analytes. Such samples should be handled in a
confined environment (e.g., a closed hood or a glove
box).
8.2.3 For the purpose of this method, a water sample is defined as a
single phase system, the primary component of which is water.
D-27 DFLM01.0
-------
The sample may include floating, suspended and settled
particulate matter in quantities that do not cause severe
problems with filtration or extraction.
8.3 Sample Preservation
8.3.1 Water Samples. Each water sample received will consist of at
least two 1-liter (or quart) amber glass bottles. Store at 4 +
2°C from collection until extraction. Do not freeze. After a
portion of the sample is removed for analysis, the unused
portion of the sample is stored at 4 ± 2*C in a locked, limited
access area for at least 60 days from the date of data
submission.
8.3.2 Soil/Fly Ash/Chemical Waste Samples. Each soil/fly
ash/chemical waste sample received will be contained in a 1-
pint glass jar surrounded by vermiculite in a sealed metal
paint can. Until a portion is removed for analysis, the sealed
sample must be stored in a locked, limited access area at room
temperature. Do not freeze. After a portion is removed for
analysis, the unused portion of the sample is returned to its
original container and stored at room temperature for at least
60 days from the date of data submission.
8.3.3 To minimize the potential for photodecomposition, all samples
must be protected from light from the time of receipt until
extraction.
8.4 Sample Handling and Freextraction Treatment
8.4.1 If a soil/sediment sample contains an obvious aqueous liquid
phase, decant or centrifuge the sample to separate the phases
(see Paragraph 8.4.7).
8.4.2 If a soil/sediment sample does not contain an obvious liquid
phase, homogenize the sample by careful stirring with a clean
glass rod or spatula.
8.4.3 If a soil/sediment sample contains an obvious non-aqueous
liquid phase, or contains more than two phases (i.e. non-
aqueous liquid/aqueous liquid/solid), contact the Sample
Management Office (SMO) in order to determine which phase(s)
should be analyzed.
8.4.4 All water samples are filtered prior to extraction, and the
filtered liquid and the particulates are extracted separately
(see Section 9.5). If a water sample contains significant
amounts of suspended particulates, centrifuge the sample and
decant the water from the particulates before filtering
(Paragraph 8.4.7).
8.4.5 If a water sample contains an obvious non-aqueous liquid phase
or a non-particulate solid phase, contact SMO in order to
-<- determine which phase (s) should be analyzed.
D-28 DFLM01.0
-------
8.4.6 If a water sample does not contain significant amounts of
suspended particulates, homogenize the sample by carefully
shaking the capped sample bottle.
8.4.7 Centrifugation. If centrifugation of a sample is necessary,
place the entire sample in a suitable centrifuge bottle(s) with
a 250-300 mL capacity, and centrifuge for 30 minutes at 400 x
G. Decant the liquid phase into a clean container. Remove the
solid phase by careful pouring or using a clean spatula or
glass rod. Proceed with the analysis of the appropriate phase
or phases.
CAUTION: A phase that is not analyzed may contain PCDDs/PCDFs
and should be handled and disposed of appropriately.
9. Extraction Procedures
Four types of extraction procedures are employed in these analyses
depending on the sample matrix. Chemical waste samples are extracted
by refluxing with a Dean Stark water separator. Fly ash samples and
soil/sediment samples are extracted in a combination of a Soxhlet
extractor and a Dean Stark water separator. Water samples are filtered
and then the filtrate is extracted using either a separatory funnel
procedure or a continuous liquid-liquid extraction procedure. The
filtered particulates are extracted in a combination of a Soxhlet
extractor and a Dean Stark water separator.
9.1 Chemical Waste Sample Extraction
9.1.1 Assemble a flask (50 mL or 125 mL, see below), a Dean Stark
trap, and a condenser, and preextract with toluene for three
hours. Preextraction will ensure that the glassware is as clean
as possible and minimize cross-contamination problems. Discard
the used toluene, or pool it for later analysis to verify the
cleanliness of the glassware.
9.1.2 Oily Sludge/Wet Fuel Oil. Weigh about 1 g of sample to two
decimal places into a tared preextracted 125-mL flask. Add 1
mL of the acetone-diluted internal standard solution (see
Section 5.12) to the sample in the flask. Attach the
preextracted Dean Stark water separator and condenser to the
flask, and extract the sample by refluxing it with 50 mL of
toluene for at least three hours.
Continue refluxing the sample until all the water has been
removed. Cool the sample, and filter the toluene extract
through a rinsed glass fiber filter into a 100 mL round bottom
flask. Rinse the filter with 10 mL of toluene, and combine the
extract and rinsate. Concentrate the combined solution to
approximately 10 mL using a rotary evaporator as described in
Section 9.6.
9.1.3 Stillbottom/Oil. Weigh about 1 g of sample to two decimal
places into a tared preextracted 50-mL flask. Add 1 mL of the
D-29 DFLM01.0
-------
acetone-diluted internal standard solution (see Section 5.12)
to the sample in the flask. Attach the preextracted Dean Stark
water separator and condenser to the flask, and extract the
sample by refluxing it with 50 mL of toluene for at least three
hours.
Cool the sample, and filter the toluene extract through a
rinsed glass fiber filter into a 100 mL round bottom flask.
Rinse the filter with 10 mL of toluene, and combine the extract
and rinsate. Concentrate the combined solution to
approximately 10 mL using a rotary evaporator as described in
Section 9.6.
9.1.4 Prepare a sample aliquot for the duplicate sample analysis and
a sample aliquot for the spiked sample analysis, using the
procedures in Sections 13 and 14 and at the frequency given in
those sections.
9.2 Soxhlet-Dean Stark (SDS) Apparatus
The combination of a Soxhlet extractor and a Dean Stark moisture trap
is used for the removal of water and extraction of PCDDs/PCDFs from
samples of fly ash, soil/sediment, and the particulate fraction of
water samples. The combination consists of a Soxhlet extractor body
with a Dean Stark moisture trap fitted between the extractor and the
condenser (see Figure 4).
Procedures for the use of this apparatus were developed by the Dow
Chemical Company and have been tested by the EPA Industrial Technology
Division, Office of Water Regulations and Standards. Those tests
indicate that based on the recovery of labeled analytes, the extraction
by SDS apparatus is as good, or better, than extraction by Soxhlet
alone.
For soil/sediment samples, the results of these analyses are reported
based on the wet weight of the sample. However, use of the SDS
apparatus allows the water content of a sample to be determined from
the same aliquot of sample that is also extracted for analysis. The
amount of water evolved from the sample during extraction is used to
approximate the percent solids content of the sample. The percent
solids data may be employed by the data user to approximate the dry
weight concentrations. The percent solids determination does not apply
to the extraction of particulates from the filtration of water samples
or to the extraction of fly ash samples which are treated with an HCl
solution prior to extraction.
Further, as described here, the SDS apparatus allows the extraction of
sample matrices containing water without the addition of drying agents
such as sodium sulfate. The use of sodium sulfate during extraction
may be responsible for the loss of analytes, through adsorption onto
carbon particles produced by baking this reagent at high temperatures
in order to remove organic contaminants, and by trapping analytes in
pores in the sodium sulfate as moisture is adsorbed.
D-30 DFLM01.0
-------
The following procedures apply to all uses of the SDS apparatus for
extracting matrices covered by this protocol.
NOTE: It may be necessary to wrap portions of the SDS apparatus with
aluminum foil or glass wool to obtain proper operation.
9.2.1 Refer to Section 4.5 for detailed instructions on cleaning
glassware such as the SDS apparatus. In particular, do not
bake the components of the SDS apparatus as part of routine
cleaning, as repeated baking of glassware can cause active
sites on the glass surface that will adsorb PCDDs/PCDFs and
other analytes. All glass parts of the SDS apparatus,
including the thimbles, must be preextracted with toluene for
approximately three hours immediately prior to use.
Freextraction will ensure that the glassware is as clean as
possible and minimize cross-contamination problems. Discard
the used toluene, or pool it for later analysis to verify the
cleanliness of the glassware.
9.2.2 The extraction of soil/sediment, fly ash, and particulates from
water samples will require the use of a Soxhlet thimble. Prior
to preextraction, prepare the thimble by adding 5 g of 70/230
mesh silica gel to the thimble to produce a thin layer in the
bottom of the thimble. This layer will trap fine particles in
the thimble. Add 80-100 g of quartz sand on top of the silica
gel, and place the thimble in the extractor.
9.2.3 After preextraction for three hours, allow the apparatus to
cool and remove the thimble. Mix the appropriate weight of
sample with the sand in the thimble, being careful not to
disturb the silica gel layer.
If the sample aliquot to be extracted contains large lumps or
is otherwise not easily mixed in the thimble, the sand and
sample may be mixed in another container. Transfer
approximately 2/3 of the sand from the thimble to a clean
container, being careful not to disturb the silica gel layer
when transferring the sand. Thoroughly mix the sand and the
sample with a clean spatula, and transfer the sand/sample
mixture to the thimble.
If a sample with particularly high moisture content is to be
extracted, it may be helpful to leave a. small conical
depression in the material in the thimble. This procedure will
allow the water to drain through the thimble more quickly
during the early hours of the extraction. As the moisture is
removed during the first few hours of extraction, the
depression will collapse, and the sample will be uniformly
extracted.
D-31 DFLM01.1 (9/91)
-------
9.3 Fly Ash Sample Extraction
9.3.1 Weigh about 10 g of the fly ash to two decimal places, and
transfer to an extraction jar (Paragraph 4.4.1). Add 1 mL of
the acetone-diluted internal standard solution (Section 5.12)
to the sample.
9.3.2 Add 150 mL of 1 N HC1 to the fly ash sample in the jar. Seal
the jar with the Teflon-lined screw cap, place on a mechanical
shaker, and shake for three hours at room temperature.
9.3.3 Rinse a Whatman #1 (or equivalent) filter paper with toluene,
and then filter the sample through the filter paper in a
Buchner funnel into a 1 L receiving flask. Wash the fly ash
with approximately 500 mL distilled water.
9.3.4 Mix the fly ash with the sand in a preextracted thimble, and
place the filter paper on top of the sand. Place the thimble
in a SDS extractor, add 200 mL toluene, and extract for 16
hours.
The solvent must cycle completely through the system 5-10 times
per hour. Cool and filter the toluene extract through a rinsed
glass fiber filter into a 500 mL round-bottom flask. Rinse the
filter with 10 mL of toluene. Concentrate the extract as
described in Section 9.6.
NOTE: A blank must be analyzed using a piece of filter paper
handled in the same manner as the fly ash sample.
9.3.5 Prepare a sample aliquot for the duplicate sample analysis and
a sample aliquot for the spiked sample analysis, using the
procedures in Sections 13 and 14 and at the frequency given in
those sections.
9.4 Soil/Sediment Sample Extraction
NOTE: Extremely wet samples may require centrifugation to remove
standing water before extraction (see Paragraph 8.4.7).
9.4.1 Weigh about 10 grams of the soil to two decimal places and
transfer to a preextracted thimble (see Paragraph 9.2.2). Mix
the sample with the quartz sand, and add 1 mL of the acetone-
diluted internal standard solution (see Section 5.12) to the
sample/sand mixture. Add small portions of the solution at
several sites on the surface of the sample/sand mixture.
9.4.2 Place the thimble in the SDS apparatus. Add 200 to 250 mL
toluene to the SDS apparatus, and reflux for 16 hours. The
solvent must cycle completely through the system 5-10 times per
hour.
9.4.3 Estimate the percent solids content of the soil/sediment sample
by measuring the volume of water evolved during the SDS
D-32 DFLM01.0
-------
extraction procedure. For extremely wet samples, the Dean
Stark trap may need to be drained one or more times during the
16-hour extraction. Collect the water from the trap, and
measure its volume to the nearest 0.1 mL. Assume a density of
1.0 g/mL, and calculate the percent solids content according to
the formula below:
(Wet weight of sample - Weight of water)
Percent Solids - x 100
Wet weight of sample
9.4.4 Concentrate this extract as described in Section 9.6.
9.4.5 Prepare a sample aliquot for the duplicate sample analysis and
a sample aliquot for the spiked sample analysis, using the
procedures in Sections 13 and 14 and at the frequency given in
those sections.
9.5 Water Sample Extraction
9.5.1 Allow the sample to come to ambient temperature, then mark the
water meniscus on the side of the 1-L sample bottle for
determination of the exact sample volume. Add 1 mL of the
acetone-diluted internal standard solution (see Section 5.12)
to the sample bottle. Cap the bottle, and mix the sample by
gently shaking for 30 seconds. Filter the sample through a
0.45 micron filter that has been rinsed with toluene.
NOTE: Reagent water used as a blank must also be filtered in a
similar fashion and subjected to the same cleanup and
analysis as the water samples.
If the total dissolved and suspended solids contents are too
much to filter through the 0.45 micron filter, centrifuge the
sample, decant, and then filter the aqueous phase (see
Paragraph 8.4.7). Combine the solids from the centrifuge
bottle(s), the particulate on the filter and the filter itself,
and proceed with the SDS extraction in Paragraph 9.5.4.
9.5.2 The filtered aqueous sample is poured into a 2-L separatory
funnel. Add 60 mL methylene chloride to the sample bottle,
seal, and shake for 60 seconds to rinse the inner surface.
Transfer the solvent to the separatory funnel and extract the
sample by shaking the funnel for two minutes with periodic
venting. 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 Contractor shall employ mechanical techniques to
complete the phase separation (i.e., glass stirring rod).
Drain the methylene chloride extract into a 500-mL KD
concentrator (mounted with a 10-mL concentrator tube) by
passing the extract through a funnel packed with a glass wool
plug and half-filled with anhydrous sodium sulfate. Extract
the water sample two more times using 60 mL of fresh methylene
D-33 DFLM01.0
-------
chloride each time. Drain each extract through the funnel into
the KD concentrator. After the third extraction, rinse the
sodium sulfate with at least 30 mL of fresh methylene chloride.
Concentrate this extract as described in Section 9.6.
9.5.3 A continuous liquid-liquid extractor may be used in place of a
separatory funnel when experience with a sample from a given
source indicates that a serious emulsion problem will result or
an emulsion is encountered using a separatory funnel. The
following procedure is used for a continuous liquid-liquid
extractor.
Preextract the continuous liquid-liquid extractor for three
hours with methylene chloride and reagent water. Filter the
sample as in Paragraph 9.5.1. Allow the extractor to cool,
discard the methylene chloride, and add the filtered aqueous
sample to the continuous liquid-liquid extractor. Add 60 mL of
methylene chloride to the sample bottle, seal and shake for 30
seconds.
Transfer the solvent to the extractor. Repeat the sample
bottle rinse with an additional 50 to 100 mL portion of
methylene chloride and add the rinse to the extractor. Add 200
to 500 mL methylene chloride to the distilling flask and
sufficient reagent water to ensure proper operation. Extract
for 16 hours. Allow to cool, then detach the flask and dry the
sample by running it through a rinsed funnel packed with a
glass wool plug and 5 g of anhydrous sodium sulfate into a 500
mL KD flask. Proceed to Section 9.6.
9.5.4 Combine the filtered particulate portion of the sample with the
quartz sand in the extraction thimble. Add the filter on top
of the particulate/sand mixture, and place the thimble into a
preextracted SDS apparatus.
Add 200 to 250 mL of toluene to the SDS apparatus and reflux
for 16 hours. The solvent must cycle completely through the
system 5-10 times per hour. Concentrate this extract as
described in Section 9.6.
9.5.5 Determine the original sample volume by refilling the sample
bottle to the mark and transferring the liquid to a 1-L
graduated cylinder. Record the sample volume to the nearest 5
mL.
9.5.6 Prepare a sample aliquot for the duplicate sample analysis and
a sample aliquot for the spiked sample analysis, using the
procedures in Sections 13 and 14 and at the frequency given in
those sections.
9.6 Macro-Concentration Procedures (All Matrices)
Prior to cleanup, extracts from all matrices must be concentrated to
approximately 10 mL. In addition, the concentrated extracts from the
D-34 DFLM01.0
-------
aqueous filtrate and the filtered particulates must be combined prior
to cleanup. Two procedures may be used for macro-concentration,
Kuderna-Danish (K-D) or rotary evaporator. Concentration of toluene by
K-D requires the use of a heating mantle, as toluene boils above the
temperature of a water bath. The two procedures are described in
general terms below.
9.6.1 Concentration by K-D
9.6.1.1 Add one or two clean boiling chips to the round
bottom flask from the SDS extractor or the reflux
flask. Attach a three-ball macro Snyder column.
9.6.1.2 Pre-wet the column by adding approximately 1 mL of
toluene through the top. Place the round bottom
flask in a heating mantle and apply heat as required
to complete the concentration in 15-20 minutes. At
the proper rate of distillation, the balls of the
column will actively chatter but the chambers will
not flood.
9.6.2 Concentration by Rotary Evaporator
9.6.2.1 Assemble the rotary evaporator according to
manufacturer's instructions, and warm the water bath
to 45°C. On a daily basis, preclean the rotary
evaporator by concentrating 100 mL of clean
extraction solvent through the system. Archive both
the concentrated solvent and the solvent in the
catch flask for contamination check if necessary.
Between samples, three 2-3 mL aliquots of toluene
should be rinsed down the feed tube into a waste
beaker.
9.6.2.2 Attach the round bottom flask containing the sample
extract to the rotary evaporator. Slowly apply
vacuum to the system, and begin rotating the sample
flask.
9.6.2.3 Lower the flask into the water bath and adjust the
speed of rotation and the temperature as required to
complete the concentration in 15-20 minutes. At the
proper rate of concentration, the flow of solvent
into the receiving flask will be steady, but no
bumping or visible boiling of the extract will
occur.
NOTE: If the rate of concentration is too fast,
analyte loss may occur.
9.6.2.4 When the liquid in the concentration flask has
reached an apparent volume of 2 mL, remove the flask
from the water bath, and stop the rotation. Slowly
and carefully, admit air into the system. Be sure
D-35 DFLM01.0
-------
not to open the valve so quickly that the sample is
blown out of the flask. Rinse the feed tube with
approximately 2 mL of hexane.
9.6.3 Extracts of Chemical Waste, Fly Ash, and Soil/Sediment Samples
9.6.3.1 For chemical waste, fly ash, and soil/sediment
samples, the extract must be concentrated to
approximately 10 mL prior to acid-base washing
treatment. Concentrate the extract by either of the
two procedures listed above.
9.6.3.2 Transfer the concentrated extract to a 125 mL
separately funnel. Rinse the flask with toluene and
add the rinse to the separatory funnel. Proceed
with acid-base washing treatment per Section 9.7.
9.6.4 Extracts of Aqueous Filtrates
9.6.4.1 Extracts of the aqueous filtrate of water samples
are in methylene chloride which is concentrated to
approximately 10 mL by K-D or rotary evaporator
. prior to combining with the toluene extract of the
particulates. If using K-D, the methylene chloride
can be concentrated in a water bath instead of a
heating mantle.
9.6.4.2 Combine the extract of the filtrate with the extract
of the particulates as described in Section 9.6.
9.6.5 Extracts of Particulates from Aqueous Samples
9.6.5.1 If the extract is from the particulates from an
aqueous sample, it must be concentrated to
approximately 10 mL by either K-D or rotary
evaporator, and combined with the concentrated
extract of the filtrate (Paragraph 9.6.4.1) prior to
acid-base washing treatment.
9.6.5.2 Assemble a glass funnel filled approximately one-
half full with sodium sulfate such that the funnel
will drain into the K-D concentrator or round bottom
flask from Paragraph 9.6.4.1 containing the
concentrated methylene chloride extract of the
filtrate. (You may use the same funnel from
Paragraph 9.5.2 or 9.5.3.) Pour the concentrated
toluene extract of the particulates through the
sodium sulfate into the K-D concentrator or round
bottom flask. Rinse the flask from the particulate
extract with three 15-20 mL volumes of hexane, and
pour each rinse through the sodium sulfate into the
K-D concentrator or round bottom flask.
D-36
DFLM01.0
-------
9.6.5.3 Concentrate the combined extract to approximately 10
mL (the volume of the toluene) by either K-D or
rotary evaporator.
9.6.5.4 Transfer the concentrated combined extract to a 125
mL separatory funnel. Rinse the concentrator with
three 5 mL volumes of hexane, and add each rinse to
the separatory funnel. Proceed with acid-base
washing treatment per Section 9.7.
9.7 Extract Cleanup Procedures (All Matrices)
9.7.1 Prior to. cleanup, all extracts are spiked with the 37Cl4-2378-
TCDD cleanup standard (Section 5.17). The recovery of this
standard is used to monitor the efficiency of the cleanup
procedures. Spike 5 uL of the cleanup standard (or a larger
volume of diluted solution containing 25 ng of 37Cl4-2378-TCDD)
into each separatory funnel containing an extract, resulting in
a concentration of 0.25 ng/uL in the final extract analyzed by
GC/MS.
9.7.2 Partition the concentrated extract against 40 mL of
concentrated sulfuric acid. Shake for two minutes. Remove and
discard the acid layer (bottom). Repeat the acid washing until
no color is visible in the acid layer. (Perform acid washings
a maximum of four times.)
CAUTION: Concentrated sulfuric acid is hazardous and should
be handled with care.
9.7.3 Partition the concentrated extract against 40 mL of 5 percent
(w/v) sodium chloride. Shake for two minutes. Remove and
discard the aqueous layer (bottom).
9.7.4 Partition the concentrated extract against 40 mL of 20 percent
(w/v) potassium hydroxide (KOH). Shake for two minutes.
Remove and discard the base layer (bottom). Repeat the base
washes until color is not visible in the bottom layer (perform
base washes a maximum of four times). Strong base (KOH) is
known to degrade certain PCDDs/PCDFs; therefore, contact time
should be minimized.
9.7.5 Partition the concentrated extract against 40 mL of 5 percent
(w/v) sodium chloride. Shake for two minutes. Remove and
discard the aqueous layer (bottom). Dry the organic layer by
pouring it through a funnel containing a rinsed filter half-
filled with anhydrous sodium sulfate. Collect the extract in
an appropriate size (100-250 mL) round bottom flask. Wash the
separatory funnel with two 15-mL portions of hexane, pour
through the funnel and combine the extracts. Concentrate the
extracts to 1.0 mL using the procedures described in Section
9.8.
D-37 DFLM01.0
-------
9.8 Micro-Concentration of Extracts
Prior to column Chromatographic cleanup procedures, the extracts from
all matrices must be concentrated to approximately 1.0 mL. This
concentration may be accomplished using either K-D or rotary
evaporator, followed by nitrogen evaporation.
9.8.1 Concentrate the extracts to approximately 1 mL, using the
procedures in Paragraph 9.6.1 or 9.6.2.
9.8.2 When the liquid in the concentration flask has reached an
apparent volume of 1 mL, transfer the extract to a conical
centrifuge tube using three 2-3 mL rinses of hexane.
9.8.3 Transfer the centrifuge tube containing the sample extract to a
nitrogen evaporation device. Adjust the flow of nitrogen so
that the surface of the solvent is just visibly disturbed.
NOTE: A large vortex in the solvent may cause analyte loss.
9.8.4 Lower the tube into a 45*C water bath and continue
concentrating. When the volume of the liquid is approximately
100 uL, add 2-3 mL of the hexane and continue concentration to
a final volume of 1.0 mL. Proceed with column chromatography
as described in Section 9.9.
9.9 Silica Gel and Alumina Column Chromatographic Procedure
9.9.1 Column 1. Insert a glass wool plug onto the bottom of a
gravity column (1 cm x 30 cm glass column) fitted with a Teflon
stopcock. Add 1 g silica gel and tap the column gently to
settle the silica gel. Add 2 g sodium hydroxide-impregnated
silica gel, 1 g silica gel, 4 g sulfuric acid-impregnated
silica gel, and 2 g silica gel (see Section 5.10). Tap the
column gently after each addition. A small positive pressure
(5 psi) of clean nitrogen may be used if needed.
9.9.2 Column 2. Insert a glass wool plug onto the bottom of a
gravity column (1 cm x 30 cm glass column) fitted with a Teflon
stopcock. Add 6 g of the activated acid alumina (see Paragraph
5.10.1). Tap the top of the column gently.
Check each new batch of silica gel and alumina and maintain the
results of the analyses on file for examination during EPA on-
site evaluations. To accomplish this, combine 50 uL of the
continuing calibration solution (CC3) with 950 uL of hexane.
Process this solution through both columns in the same manner
as a sample extract (Paragraphs 9.9.3 through 9.9.9).
Concentrate the continuing calibration solution to a final
volume of 50 uL. Proceed to Section 10. If the recovery of
any of the analytes is less than 80%, the batch of alumina or
silica gel must not be used.
D-38 DFLM01.0
-------
9.9.3 Add hexane to each column until the packing is free of air
bubbles. A small positive pressure (5 psi) of clean dry
nitrogen may be used if needed. Check the columns for
channeling. If channeling is present, discard the column.
CAUTION: Do not tap a wetted column.
9.9.4 Assemble the two columns such that the eluate from Column 1
(silica gel) drains directly into Column 2 (alumina).
9.9.5 Apply the hexane solution from Paragraph 9.8.4 to the top of
the silica gel column. Rinse the vial with enough hexane (1-2
mL) to complete the quantitative transfer of the sample to the
surface of the silica.
9.9.6 Using 90 mL of hexane, elute the extract from Column 1 directly
onto Column 2 which contains the alumina.
CAUTION: Do not allow the alumina column to run dry.
9.9.7 Add 20 mL of hexane to Column 2, and elute until the hexane
level is just below the top of the alumina. Do not discard the
eluted hexane, but collect in a separate flask and store it for
later use, as it may be useful in determining where the labeled
analytes are being lost if recoveries are less than 50 percent.
9.9.8 Add 20 mL of 20% methylene chloride/80% hexane (v/v) to Column
2 and collect the eluate.
9.9.9 Concentrate the extract to approximately 2 to 3 mL using the
procedures in Section 9.8.
CAUTION: Do not concentrate the eluate to dryness. The
sample is now ready to be transferred to the carbon
column.
9.10 Carbon Column Chromatographic Procedure
9.10.1 Thoroughly mix 5.35 g active carbon AX-21 and 62.0 g Celite 545
to produce a 7.9% w/w mixture. Activate the mixture at 130°C
for six hours, and store in a desiccator.
Check each new batch of the Carbon/Celite and maintain the
results from the analyses for examination during EPA on-site
evaluations. To accomplish this, add 50 uL of the continuing
calibration solution to 950 uL of hexane. Process the spiked
solution in the same manner as a sample extract (Paragraphs
9.10.2 through 9.10.6). Concentrate the continuing calibration
solution to 50 uL and proceed with Section 9.10. If the
recovery of any of the analytes is less than 80%, this batch of
Carbon/Celite mixture may not be used.
9.10.2 Prepare a 4-inch glass column by cutting off each end of a 10-
mL disposable serological pipet. Fire polish both ends and
D-39 DFLM01.0
-------
flare if desired. Insert a glass wool plug at one end of the
column, and pack it with 1 g of the Carbon/Celite mixture.
Insert an additional glass wool plug in the other end.
CAUTION: It is very important that the column be packed
properly to ensure that carbon fines are not carried
into the eluate. PCDDs/PCDFs will adhere to the
carbon fines and greatly reduce recovery. If carbon
fines are carried into the eluate in Paragraph
9.10.5, filter the eluate using a 0.45 micron filter
(pre-rinsed with toluene), then proceed to Section
9.11.
9.10.3 Rinse the column with:
9.10.3.1 4 mL Toluene.
9.10.3.2 2 mL of Methylene Chloride/Methanol/Toluene (75:20:5
v/v).
9.10.3.3 4 mL of Cyclohexane/Methylene Chloride (50:50 v/v).
Discard all the column rinsates.
9.10.4 While the column is still wet, transfer the concentrated eluate
from Paragraph 9.9.9 to the prepared carbon column. Rinse the
eluate container with two 0.5 mL portions of hexane and
transfer the rinses to the AX-21 carbon column. Elute the
column with the following sequence of solvents.
9.10.4.1 10 mL of Cyclohexane/Methylene Chloride (50:50 v/v).
9.10.4.2 5 mL of Methylene Chloride/Methanol/Toluene (75:20:5
v/v).
NOTE: The above two eluates may be collected, combined and
used as a check on column efficiency.
9.10.5 Once the solvents have eluted through the column, turn the
column over, elute the PCDD/PCDF fraction with 20 mL of
toluene, and collect the eluate.
9.11 Final Concentration
9.11.1 Evaporate the toluene fraction from Paragraph 9.10.5 to
approximately 1.0 mL in a rotary evaporator (see Section 9.8).
Transfer the extract to a 2.0 mL conical vial using a toluene
rinse.
CAUTION: Do not evaporate the sample extract to dryness.
9.11.2 Add 100 uL tridecane (or nonane) to the extract and reduce the
volume to 100 uL using a gentle stream of clean dry nitrogen.
D-40 DFLM01.0
-------
The final extract volume should be 100 uL of tridecane (or
nonane). Seal the vial and store the sample extract in the
dark at ambient temperature until just prior to GC/MS analysis.
10. GC/MS Analysis
10.1 Remove the extract of the sample or blank from storage. Gently swirl
the solvent on the lower portion of the vial to ensure complete
dissolution of the PCDDs/PCDFs.
10.2 Transfer a 50 uL aliquot of the extract to a 0.3 mL vial, and add
sufficient recovery standard solution to yield a concentration of 0.5
ng/uL in a 50 uL volume. Reduce the volume of the extract back down to
50 uL using a gentle stream of dry nitrogen.
Inject a 2 uL aliquot of the extract into the GC/MS instrument (see
Paragraph 4.1.1). Reseal the vial from Paragraph 9.11.2, containing
the original concentrated extract.
10.3 Analyze the extract by GC/MS, and monitor all of the ions listed in
Table 7. The same MS parameters used to analyze the calibration
solutions shall be used for the sample extracts.
10.4 Dilutions
10.4.1 If the concentration of any PCDD/PCDF in the sample has
exceeded the calibration range or the detector has been
saturated, a dilution shall be performed.
An appropriate dilution will result in the largest peak in the
diluted sample falling between the mid-point and high-point of
the calibration range.
10.4.2 Dilutions are performed using an aliquot of the original
extract, of which approximately 50 uL remain from Paragraph
9.11.2. Remove an appropriate size aliquot from the vial and
add it to a sufficient volume of tridecane (or nonane) in a
clean 0.3 mL conical vial. Add sufficient recovery standard
solution to yield a concentration of 0.5 ng/uL (1.0 ng/uL C-
OCDD). Reduce the volume of the extract back down to 50 uL
using a gentle stream of dry nitrogen.
10.4.3 The dilution factor is defined as the total volume of the
sample aliquot and clean solvent divided by the volume of the
sample aliquot that was diluted.
10.4.4 Inject 2 uL of the diluted sample extract into the GC/MS, and
analyze according to Section 10.3.
10.4.5 Diluted samples in which the MS response of any internal
standard is > 10% of the MS response of that internal standard
in the most recent continuing calibration standard are
quantified using the internal standards.
D-41 ' DFLM01.0
-------
Diluted samples in which the MS response of any internal
standard is < 10% of the MS response of that internal standard
in the most recent continuing calibration standard are
quantified using the recovery standards (see Section 15.3).
11. Identification Criteria
For a gas chromatographic peak to be unambiguously identified as a FCDD
or PCDF, it must meet all of the following criteria.
11.1 Retention Times
Retention times are required for all chromatograms; scan numbers are
optional. Retention times shall either be printed at the apex of each
peak on the chromatogram, or each peak shall be unambiguously labeled
with an identifier that refers to the quantitation report. The
chromatogram, the quantitation report, or a combination of both shall
contain the retention time of each peak and its area.
11.1.1 In order to make a positive identification of the 2,3,7,8-
substituted isomers for which an isotopically labeled internal
or recovery standard is present in the sample extract, the
absolute retention time (RT) at the maximum peak height of the
analyte must be within -1 to 3 seconds of the retention time of
the corresponding labeled standard.
11.1.2 In order to make a positive identification of the 2,3,7,8-
substituted isomers for which a labeled standard is not
available, the relative retention time (RRT) of the analyte
must be within 0.05 RRT units of the RRT established by the
continuing calibration. The RRT is calculated as follows:
retention time of analyte
RRT
retention time of corresponding internal standard
11.1.3 For non-2,3,7,8-substituted compounds (tetra through hepta),
the retention time must be within the retention time windows
established by the window defining mix for the corresponding
homologue (see Section 7.1).
11.1.4 In order to assure that retention time shifts do not adversely
affect the identification of PCDDs/PCDFs, the absolute
retention times of the two recovery standards added to every
sample extract immediately prior to analysis may not shift by
more than + 10 seconds from their retention times in the
continuing calibration standard (see Paragraph 17.1.4).
11.2 Peak Identification
All of the specified ions listed in Table 5 for each PCDD/PCDF
homologue and labeled standards must be present in the SICP. The ion
current response for the two quantitation ions and the M-[COC1]+ ions
D-42 DFLM01.0
-------
for the analytes must maximize simultaneously (+ 2 seconds). This
requirement also applies to the internal standards and recovery
standards. For the cleanup standard, only one ion is monitored.
11.3 Signal-To-Noise Ratio
The integrated ion current for each analyte ion listed in Table 5 must
be at least 2.5 times background noise and must not have saturated the
detector. The internal standard ions must be at least 10.0 times
background noise and must not have saturated the detector. However, if
the M-[COC1]+ ion does not meet the 2.5 times S/N requirement but
meets all the other criteria listed in Section 11 and, in the judgement
of the GC/MS Interpretation Specialist the peak is a PCDD/PCDF, the
peak may be reported as positive and the data flagged on Form I. See
the instructions in Exhibit B for Form I.
11.4 Ion Abundance Ratios
The relative ion abundance criteria listed in Table 6 for native
analytes and internal standards must be met using peak areas to
calculate ratios.
11.4.1 If interferences are present and ion abundance ratios are not
met using peaks areas, but all other qualitative identification
criteria are met (RT, S/N, presence of all three ions), then
• • the Contractor may use peak heights to evaluate the ion ratio.
11.4.2 If, in the judgement of the GC/MS Interpretation Specialist the
peak is a PCDD/PCDF, then report the ion abundance ratios
determined using peak heights, quantitate the peaks using peak
heights rather than areas for both the target analyte and the
internal standard, and flag the data on Form I.
11.5 Polychlorinated Diphenyl Ether (PCDPE) Interferences
The identification of a GC peak as a PCDF cannot be made if a signal
having S/N greater than 2.5 is detected at the same retention time (• 2
seconds) in the corresponding PCDPE channel (see Table 5). If a PCDPE
is detected, it shall be documented in the SDG Narrative, and an
Estimated Maximum Possible Concentration (EMPC) shall be calculated for
this GC peak according to Section 15.7, regardless of the ion abundance
ratio, and reported on Form I.
12. Method Blanks
12.1 A minimum of one blank per matrix shall be analyzed with each SDG. If
samples of the same matrix are extracted in different episodes (i.e.,
different shifts or days), one blank per matrix must be prepared for
each episode. When water samples in a SDG are extracted using both the
separatory funnel and continuous liquid-liquid extraction procedures,
at least one blank must be prepared by each procedure.
DFLM01.0
-------
12.2 Method Blank Criteria
12.2.1 Acceptable laboratory method blanks must not contain any
chemical interference or electronic noise at the m/z of the
specified unlabeled PCDD/PCDF ions that is greater than 5
percent of the signal of the appropriate internal standard
quantitation ion.
12.2.2 A peak that meets identification criteria as a PCDD/PCDF in the
method blank must not exceed 2 percent of the signal of the
appropriate internal standard.
12.2.3 If the method blank extracted along with a group of samples is
contaminated per Paragraph 12.2.1 or 12.2.2, then the
associated positive samples and any samples containing peaks
that do not meet all of the identification criteria in Section
11 must be rerun.
12.2.4 If all the criteria listed above are not met, check solvents,
reagents, apparatus and glassware to locate and eliminate the
source of contamination before any more samples are extracted
and before any positive samples are reextracted.
12.2.5 Test each new lot of reagents or solvents by using them to
prepare a method blank and analyze it according the procedures
in this exhibit. If new lots of reagents or solvents contain
interfering contaminants, purify or discard them. Maintain
records of all such blanks on file for examination during EPA
on-site evaluations.
13. Spiked Sample Analysis
In order to provide data on the accuracy of the analytical method, the
laboratory is required to prepare and analyze a spiked sample for each
matrix being analyzed. For each SDG, the laboratory must prepare a
spiked sample for all of the following matrix types that occur in the
SDG:
o Water
o Soil/Sediment
o Chemical Waste
o Fly Ash
If a matrix is not represented in a SDG, then no spiked sample is
required for that matrix. If the Region or samplers have identified a
particular sample to be used for the spike, the laboratory must use an
aliquot of that sample. If the Region or samplers have not identified
a specific sample for spiking, then the laboratory may choose a sample
from the SDG; however, the sample chosen must not be a sample
identified by the Region as a field or trip blank.
D-44 DFLM01.0
-------
13.1 Prepare the spiked sample aliquot by taking the same weight (or volume)
of the representative matrix as is indicated in Sections 9.1 to 9.5 and
placing it in a clean container of suitable size.
13.2 Add 1.0 mL of the spiking solution in Section 5.18 and Table 11 to the
aliquot. Manually mix the sample to distribute the spiking solution,
and let the aliquot equilibrate for one hour.
13.3 Prepare and extract the spiked sample aliquot in the same fashion as is
used for field samples, and carry the aliquot through the entire
analytical procedure including cleanup.
13.4 Calculate the concentration of each analyte according to the procedures
in Section 15.
13.5 Calculate the recovery of each spiked analyte, using the following
equation:
Amount found - Amount in unspiked sample x J_QQ
^•spike ~ Amount spiked
where the recovery (R) is expressed as a percentage
13.6 The recovery of each spiked analyte must be in the range of 50-150
percent. If the recovery of any analyte falls outside this range, the
laboratory must recheck all calculations, and confirm that the spiking
solutions were added and were at the correct concentrations, but no
further action is necessary by the laboratory at this time. Recovery
limits for these analytes will be developed at a later date.
14. Duplicate Sample Analysis
In order to provide data on the precision of the analytical method, the
laboratory is required to prepare and analyze a duplicate of one sample
for each matrix being analyzed. For each SDG, the laboratory must
prepare a duplicate sample for all of the following matrix types that
occur in the SDG:
o Water
o Soil/Sediment
o Chemical Waste
o Fly Ash
If a matrix is not represented in a SDG, then no duplicate sample is
required for that matrix. If the Region or samplers have identified a
particular sample to be used for the duplicate, the laboratory must use
an aliquot of that sample. If the Region or samplers have not
identified a specific sample for use as the duplicate, then the
laboratory may choose a sample from the SDG; however, the sample chosen
must not be a sample identified by the Region as a field or trip blank.
D-45 DFLM01.0
-------
14.1 Prepare the duplicate sample aliquot by taking the same weight (or
volume) of the representative matrix as is indicated in Sections 9.1 to
9.5 and carrying it through the entire analytical procedure including
extraction, cleanup and analysis.
14.2 Calculate the concentration of each analyte detected in the duplicate
sample according the procedures in Section 15.
14.3 Calculate the precision of each detected analyte in the original and
duplicate analyses, expressed as the Relative Percent Difference (RPD),
according to the following equation:
| Sample Result - Duplicate Result | x IQO
RPD - (Sample Result + Duplicate Result)/2
14.4 The RPD of any detected analyte must be less than or equal to 50
percent. If the RPD of any detected analyte falls above this limit,
the laboratory must recheck all calculations, but no further action is
necessary by the laboratory at this time. RPD limits for these
analytes will be developed at a later date.
15. Calculations
15.1 For GC peaks that have met all the identification criteria outlined in
Section 11, calculate the concentration of the individual PCDD or PCDF
isomers using the following formulae:
ALL MATRICES OTHER THAN WATER
Qis x (An1 + An2)
Cn (ugAg) ^ 2
W x (Aisx + Ais ) x RRFn
WATER
" + An2)
Where:
. 1
V x (Ais1 + Ais ) x RRFn
and An - integrated ion abundances (peak areas) of the
quantitation ions of the isomer of interest
(Table 5).
2
an^ Ais "" integrated ion abundances (peak areas) of the
quantitation ions of the appropriate internal
standard (Table 5).
NOTE: In instances where peak heights are used to evaluate ion
abundance ratios due to interferences (see Section
11.4), substitute peak heights for areas in the
formulae above.
D-46 DFLM01.0
-------
W - weight of sample extracted, in grams.
V — volume of sample extracted, in liters.
Q^s — quantity (ng) of the appropriate internal standard
added to the sample prior to extraction.
RRFn - calculated relative response factor from continuing
calibration (see Section 7.3).
For solids matrices, the units of ng/g that result from the formula
above are equivalent to ug/Kg. Using isotope dilution techniques for
quantitation, the concentration data are recovery corrected, and
therefore, the volume of the final extract and the injection volume are
implicit in the value of Q£S.
15.1.1 For homologues that contain only one 2,3,7,8-substituted isomer
(TCDD, PeCDD, HpCDD and TCDF), the RRF of the 2,3,7,8-
substituted isomer from the continuing calibration (see
Paragraph 7.3.2.3) will be used to quantitate both the 2,3,7,8-
substituted isomers and the non-2,3,7,8-substituted isomers.
15.1.2 For homologues that contain more than one 2,3,7,8-substituted
isomer (HxCDD, PeCDF, HxCDF and HpCDF), the RRF used to
calculate the concentration of each 2,3,7,8-substituted isomers
will be the RRF determined for that isomer during the
continuing calibration (see Paragraph 7.3.2.3).
15.1.3 For homologues that contain one or more non-2.3.7.8-substituted
isomers, the RRF used to calculate the concentration of these
isomers will be the lowest of the RRFs determined during the
continuing calibration (see Paragraph 7.3.2.3) for the 2,3,7,8-
substituted isomers in that homologue. This RRF will yield the
highest possible concentration for the non-2,3,7,8-substituted
isomers.
NOTE: The relative response factors of given isomers within
any homologue may be different. However, for the
purposes of these calculations, it will be assumed that
every non-2,3,7,8-substituted isomer for a given
homologue has the same relative response factor. In
order to minimize the effect of this assumption on risk
assessment, the 2,3,7,8-substituted isomer with the
lowest RRF was chosen as representative of each
homologue. All relative response factor calculations
for the non-2378-substituted isomers in a given
homologue are based on that isomer.
15.2 In addition to the concentrations of specific isomers, the total
homologue concentrations are also reported. Calculate the total
concentration of each homologue of PCDDs/PCDFs as follows:
Total concentration - sum of the concentrations of every
positively identified isomer of each
PCDD/PCDF homologue.
D-47 DFLM01.0
-------
The total must include the non-2,3,7,8-substituted isomers as well as
the 2,3,7,8-substituted isomers that are also reported separately. The
total number of GC peaks included in the' total homologue concentration
must be specified (see Exhibit B).
15.3 If the area of any internal standard in a diluted sample is less than
10 percent of the area of that internal standard in the continuing
calibration standard, then the unlabeled PCDD/PCDF concentrations in
the sample shall be estimated using the recovery standard, using the
formulae that follow. The purpose is to ensure that there is an
adequate MS response for quantitation in a diluted sample. While use
of a smaller aliquot of the sample might require smaller dilutions and
therefore yield a larger area for the internal standard in the diluted
extract, this practice leads to other concerns about the homogeneity of
the sample and the representativeness of the aliquot taken for
extraction.
ALL MATRICES OTHER THAN WATER
Cn <"J
WATER
Cn
W x (Aj-s1 + Ars2) x RRFrs
V x (Ays1 + Ars2) x RRFrs
D - dilution factor (see Paragraph 10.4.3).
An1, An2, Arsl, Ars2, Qrs, RRFrs, W and V
are defined in Paragraphs 7.3.3 and 7.3.4 and Section 15.1.
15.4 Report results for soil/sediment, fly ash, and chemical waste samples
in micrograms per kilograms (ug/kg) and water samples in nanograms per
liter (ng/L), as described in Exhibit B.
15.5 Calculate the percent recovery for each internal standard and the
cleanup standard in the sample extract, Ris, using the formula:
Ais2) x Qrs
x 100%
1 + Ars2) x RRFis x Qis
, Ars1. Ars2, Qis, Qrs a
are defined in Paragraph 7.3.3 and Section 15.1.
When calculating the recovery of the 37Cl4-2378-
standard, only one m/z is monitored for this standard;
D-48 DFLM01.0
-------
therefore, only one peak area will be used in the numerator of
this formula. Use both peak areas of the 13C12-1234-TCDD
recovery standard in the denominator.
15.5.1 The 13C12-1234-TCDD is used to quantitate the tetra internal
standards and the cleanup standard, and 13Ci2-123789-HxCDD is
used to quantitate the HxCDD, HpCDF and OCDD internal standards
(see Table 8).
15.5.2 If the original sample, prior to any dilutions, has any
internal standard with a percent recovery of less than 25% or
greater than 150%, reextraction and reanalysis of that sample
is required (see Section 17).
15.6 Sample Specific Estimated Detection Limit
The sample specific Estimated Detection Limit (EDL) is the estimate
made by the laboratory of the concentration of a given analyte required
to produce a signal with a peak height of at least 2.5 times the
background signal level. The estimate is specific to a particular
analysis of the sample and will be affected by sample size, dilution,
etc.
An EDL is calculated for each 2,3,7,8-substituted isomer that is not
identified, regardless of whether or not non-2,3,7,8-substituted
isomers in that homologue are present. The EDL is also calculated for
2,3,7,8-substituted isomers giving responses for both the quantitation
ions that are less than 2.5 times the background level.
Use the formulae below to calculate an EDL for each absent 2,3,7,8-
substituted PCDD/PCDF. The background level (Hx) is determined by
measuring the height of the noise at the expected retention times of
both the quantitation ions of the particular 2,3,7,8-substituted
isomer. The expected retention time is determined from the most recent
analysis of the CCS standard on the same GC/MS system.
ALL MATRICES OTHER THAN WATER
2.5 x Qis x (Hx1 + Hx2) x D
EDL (ugAg) i?
W x (His1 + His2) x
WATER
2.5 x Qis x (Hx1 + Hx2) x D
EDL (ng/L) 1S X X
V x (His1 + His2) x
Where:
12 '
Hx and Hx - Peak heights of the noise for
both of the quantitation ions of the
2,3,7,8-substituted isomer of
interest.
D-49 DFLM01.0
-------
1 2
His and H£S - Peak heights of both the quantitation
ions of the appropriate internal
standards.
D - dilution factor (see Paragraph 10.4.3).
Qis, RRFn, W and V are defined in Paragraph 7.3.3 and Section
15.1.
15.7 Estimated Maximum Possible Concentration
An estimated maximum possible concentration (EMPC) is calculated for
2,3,7,8-substituted isomers that are characterized by a response with a
S/N of at least 2.5 for both the quantitation ions, but that do not
meet all the identification criteria in Section 11.
Calculate the EMPC according to the following formulae:
ALL MATRICES OTHER THAN WATER
EMPC (ug/L) -
WATER
EMPC (ng/L)
(Ax1 + Ax2) x Qis x D
+ Ais2) x RRFn x W
(A,,1 + Ax2) x Qis x D
Ais2)
Where:
1 2
AX and AX - areas of both quantitation ions.
Aig1, Ais2« °-is' RR*1' D' w> and v are defined in Paragraph
7.3.3 and 10.4.3 and Section 15.1.
15.8 Toxicity Equivalency Factor (TEF) Calculation
The 2378-TCDD toxicity equivalence of PCDDs/PCDFs present in the sample
is calculated according to the method recommended by the Chlorinated
Dioxins Workgroup (CDWG) of the EPA and the Centers for Disease Control
(CDC). This method assigns a 2378-TCDD toxicity equivalency factor
(TEF) to each of the 17 2,3,7,8-substituted PCDDs/PCDFs shown in Table
11 ("Update of Toxicity Equivalency Factors (TEFs) for Estimating Risks
Associated with Exposures to Mixtures of Chlorinated Dibenzo-p-Dioxins
and Dibenzofurans (CDDs/CDFs)" March 1989 (EPA 625/3-89/016)). The
2378-TCDD toxicity equivalence of the PCDDs/PCDFs present in the sample
is calculated by summing the product of the TEF and the concentration
for each of the compounds listed in Table 11.
D-50 DFLM01.0
-------
The exclusion of homologues such as mono-, di-, tri- and the non-
2,3 ,7,8-substituted isomers in the higher homologues does not mean that
they are not toxic. Their toxicity, as estimated at this time, is much
less than the toxicity of the compounds listed in Table 11. Hence,
only the 2,3,7,8-substituted isomers are included in the TEF
calculations. The procedure for calculating the 2378-TCDD toxic
equivalence cited above is not claimed by the CDWG to be based on a
thoroughly established scientific foundation. Rather, the procedure
represents a "Consensus Recommendation on Science Policy."
When calculating the 2378-TCDD toxicity equivalence of a sample, the
Contractor shall include only those 2,3,7,8-substituted isomers that
were detected in the sample and met all of the qualitative
identification criteria in Section 11. Do not include EMPC or EDL
values in the TEF calculations. Further instructions regarding the
calculation of the 2378-TCDD toxicity equivalence may be found in
Exhibit B.
The 2378-TCDD toxicity equivalence of a sample is used in Sections 16
and 17 of this procedure to determine when second column confirmation
or reextractions and reanalyses may be required.
16. Isomer Specificity
Isomer specificity for all 2,3,7,8-substituted PCDDs/PCDFs cannot be
achieved on the 60 m DB-5 column alone. Historically, problems have
been associated with the separation of 2378-TCDD from 1237-TCDD and
1268-TCDD, and separation of 2378-TCDF from 2347-TCDF. Because of the
toxicologic concern associated with 2378-TCDD and 2378-TCDF, additional
analyses may be required for some samples, as described below.
16.1 If the toxicity equivalence calculated in Section 15 is greater than
0.7 ppb (soil/sediment or fly ash), 7 ppb (chemical waste), or 7 ppt
(aqueous), better isomer specificity is required than can be achieved
on the DB-5 column. The Contractor may utilize either of the two
options listed below to achieve adequate isomer specificity.
16.1.1 The sample extract may be reanalyzed on a 60 m SP-2330 or SP-
2331 (or equivalent) GC column in order to achieve better GC
resolution, and therefore, better identification and
quantitation of the individual 2,3,7,8-substituted isomers.
16.1.2 The sample extract may be analyzed on a single GC column
capable of resolving all 2,3,7,8-substituted PCDDs/PCDFs from
other isomers, but not necessarily resolving all the non-
2,3, 7, 8 -substituted isomers from one another.
Regardless of GC column used, for a gas chromatographic peak to be
identified as a 2,3,7,8-substituted PCDD/PCDF isomer, it must meet the
ion abundance, -signal-to-noise, and retention time criteria listed in
Section 11. In addition, when using any GC column other than those
specified here (DB-5, SP-2330 or SP-2331), the Contractor shall clearly
document, in the SDG Narrative, the elution order of all the analytes
of interest on any such column.
D-51 DFLM01.0
-------
16.2 For any sample analyzed on a DB-5 (or equivalent) column in which
either 2378-TCDD or 2378-TCDF is reported as an EMPC, regardless of
TEF-adjusted concentration or matrix, analysis of the extract is
required on a second GC column which provides better specificity for
these two isomers.
17. Required Sample Reruns
Due to a. variety of situations that may occur during contract
performance, the laboratory shall be required to reextract and
reanalyze certain samples or groups of samples. Except in the case of
dilutions, the term "rerun" shall indicate sample reextraction, cleanup
and reanalysis. When dilutions are required, the original extract
shall be diluted and reanalyzed.
When the rerun is required due to matrix effects, interferences, or
other problems encountered, the Government will pay the Contractor for
the reruns. Such reruns shall be billable and accountable under the
specified contract allotment of automatic reruns. When the rerun is
required due to Contractor materials, equipment or instrumentation
problems, or lack of Contractor adherence to specified contract
procedures, the rerun shall not be billable nor accountable under the
terms of this contract.
17.1 The following sample reruns may be billable as such under the contract,
as defined below.
17.1.1 If the original sample has a percent recovery of any internal
standard or the cleanup standard outside of the range of 25-150
percent, then reextraction and reanalysis are required.
NOTE: This rerun is billable only if the Contractor can
demonstrate that the internal standards or cleanup
standard were added to the original sample in accordance
with contract specifications, and that the same
standards are out of criteria in the reextraction and
reanalysis.
17.1.2 If the internal standards are not present with at least a 10/1
S/N ratio at their respective m/z's (316, 318, 332, 334, 402,
404, 420, 422, 470 and 472), then reextraction and reanalysis
are required. If the 'C14-2378-TCDD is not present with at
least a 10/1 S/N ratio at m/z 328, then reextraction and
reanalysis are required.
NOTE: This rerun is billable only if the Contractor can
demonstrate that the internal standards or cleanup
standard were added to the original sample in accordance
with contract specifications, and that the same
standards are out of criteria- in the reextraction and
reanalysis.
17.1.3 If any of the internal standard ion abundance ratios as
specified in Table 6 are outside the contract specified control
D-52 DFLM01.0
-------
limits, the Contractor must reanalyze the sample extract on a
second GC column with different elution characteristics, as
discussed in Section 16. No reextraction is required for such
an analysis. This reanalysis is only billable if the same
internal standard ion abundance ratios are outside the control
limits on the second column, indicating matrix effects may have
occurred.
17.1.4 If the absolute retention time of either the 13Ci2-1234-TCDD or
Ci2-123789-HxCDD recovery standard in a sample extract shifts
by greater than 10 seconds from the retention time of that
standard in the continuing calibration standard, then the
sample extract must be reanalyzed after the Contractor has
investigated the cause of the retention time shift and taken
corrective action. No reextraction is required for such an
analysis. This reanalysis is only billable if the same
recovery standard retention time shifts by greater than 10
seconds in the second analysis, indicating matrix effects may
have occurred.
17.2 If the calculated concentration of the unlabeled PCDDs/PCDFs exceeded
the initial calibration range, the sample extract shall be diluted and
reanalyzed (see Section 10.4). Such sample dilutions are billable
under the contract.
NOTE: Only one dilution shall be billable per sample and only as an
additional analysis with no extraction.
17.3 The following sample reruns shall be performed at the Contractor's
expense and shall not be billable under the terms of the contract.
17.3.1 All positive samples associated with a contaminated method
blank and any samples which contain peaks that do not meet all
of the qualitative identification criteria in Section 11
associated with a contaminated method blank must be reextracted
and reanalyzed. Acceptable laboratory method blanks must not
contain any chemical interference or electronic noise at the
m/z of the specified unlabeled PCDD/PCDF ions that is greater
than five percent of the signal of the appropriate internal
standard quantitation ion. A peak that meets identification
criteria in the method blank must not exceed two percent of the
signal of the appropriate internal standard.
17.3.2 If the chromatographic peak separation between C^2"2378-TCDD
and 13Ci2-1234-TCDD is not resolved with a valley of < 25% on
the DB-5 (or equivalent) column, or 2378-TCDD is not resolved
from the closest eluting isomer with a valley of < 25% on the
SP-2331 (or equivalent) column, then the Contractor shall
adjust the GC/MS operating conditions and rerun the affected
sample. This criterion applies to sample analyses. If this
criterion is not met for a calibration standard, all associated
samples must be rerun.
D-53 DFLM01.0
-------
17.3.3 If a false positive is reported for a blind QC sample submitted
by the Region, the Contractor shall reextract and reanalyze the
entire SDG upon notification by SMO.
17.3.4 If the analysis results for a blind QC sample do not fall
within the acceptance windows established by EPA, the
Contractor shall resxtract and reanalyze tt._ entire SDG upon
notification by SMO.
17.4 A native spike and duplicate shall be performed for each group of
samples reextracted and reanalyzed under Section 17.3.
17.4.1 If a concurrent PCDD/PCDF SDG is being processed, the native
spike and duplicate from that SDG may be shared with the rerun
samples if the total number of samples does not exceed 20. The
native spike and duplicate data shall be reported in the data
packages for both SDGs, but are only billable once, under the
original SDG for which they were prepared. If the total number
of samples exceeds 20, an additional native spike and duplicate
must be analyzed.
17.4.2 If no other PCDD/PCDF SDG is being processed at the time of
reanalysis, the native spike and duplicate shall be chosen from
the SDG for which the rerun samples are required. The native
spike and duplicate analyses are only billable in instances
where one or more of the associated rerun samples are also
billable.
D-54 ' DFLM01.0
-------
TABLE 1. SUGGESTED OPERATING CONDITIONS FOR A DB-5 (OR EQUIVALENT) COLUMN
Stationary Phase
Film Thickness
Column Dimensions
Helium Linear Velocity
Initial Temperature
Initial Time
Temperature Program
Hold Time
Total Time
DB-5 (or equivalent)
0.25 urn
60 m x 0.32 mm
35 - 40 cm/sec at 240°C
170'C
10 minutes
increase to 320°C at 8'/minute
until OCDF elutes
40-45 minutes
D-55
DFLM01.0
-------
TABLE 2. 2378-TCDD TOXICITY EQUIVALENCY FACTORS (TEFs) FOR PCDDs/PCDFs
Analvte TEF
2378-TCDD 1.00
2378-TCDF 0.10
12378-PeCDF 0.05
12378-PeCDD 0.50
23478-PeCDF 0.50
123478-HxCDF 0.10
123678-HxCDF 0.10
123478-HxCDD 0.10
123678-HxCDD 0.10
123789-HxCDD 0.10
234678-HxCDF 0.10
1234678-HpCDF 0.01
1234678-HpCDD 0.01
1234789-HpCDF 0.01
OCDD 0.001
OCDF 0.001
Reference: "Update of Toxicity Equivalency Factors (TEFs) for Estimating
Risks Associated with Exposures to Mixtures of Chlorinated
Dibenzo-p-Dioxins and Dibenzofurans (CDDs/CDFs)," March 1989,
(EPA 625/3-89/016)
D-56 ' DFLM01.0
-------
TABLE 3. CONCENTRATION CALIBRATION SOLUTIONS
Analyte
2-378-TCDD
2378 -TCDF
12378 -PeCDF
12378-PeCDD
*23478-PeCDF
*123478-HxCDF
123678 -HxCDF
*123478-HxCDD
123678 -HxCDD
*123789-HxCDD
*234678 -HxCDF
*123789 -HxCDF
*1234789-HpCDF
1234678 -HpCDF
1234678 -HpCDD
OCDD
OCDF
Hcj^-2378-TCDD
J-,C12- 2378 -TCDF
^C12-123678-HxCDD
r,C12- 1234678 -HpCDF
13c12-°CDD
;j-3C12-1234-TCDD
C12- 123789 -HxCDD
37Cl4-2378-TCDD
CC1
0.1
0.1
0.1
0.1
0.25
—
0.25
—
0.25
0.25
0.5
0.5
0.5
0.5
0.5
1.0
1.0
0.5
0.5
—
CC2
0.25
0.25
0.25
0.25
0.625
—
0.625
—
—
—
0.625
0.625
1.25
1.25
0.5
0.5
0.5
1.0
1.0
0.5
0.5
...
CCS
0.5
0.5
0.5
0.5
0.5
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
1.25
2.5
2.5
0.5
0.5
0.5
1.0
1.0
0.5
0.5
0.25
CC4
1.0
1.0
1.0
1.0
2.5
2.5
2.5
2.5
5.0
5.0
0.5
0.5
0.5
1.0
1.0
0.5
0.5
CCS
2.0
2.0
2.0
2.0
...
...
5.0
—
5.0
5.0
5.0
10.0
10.0
0.5
0.5
0.5
1.0
1.0
0.5
0.5
- - -
All concentrations are in ng/uL.
Supplemental commercial standard. Do not perform %RSD calculations on these
analytes. (See Paragraph 7.4.1 for CC3 standard preparation.)
D-57
DFLM01.0
-------
TABLE 4. INTERNAL STANDARD, RECOVERY STANDARD, AND
CLEANUP STANDARD SOLUTIONS
INTERNAL STANDARD SOLUTION
Internal Standards Concentration
5
c12-2378-TCDF 5 ns/uL
7.C12- 123678 -HxCDD 5 ns/«L
r-;:Ci2- 1234678 -HpCDF 10 ng/uL
13C12-OCDD 10 ng/uL
RECOVERY STANDARD SOLUTION
Recovery Standards Concentration
J-3C12-1234-TCDD 5 ng/uL
13Ci2-l23789-HxCDD 5 ng/uL
CLEANUP STANDARD SOLUTION
Cleanup Standards Concentration
37Cl4-2378-TCDD 5 ng/uL
D-58 DFLM01.0
-------
TABLE 5. IONS SPECIFIED FOR SELECTED ION MONITORING FOR PCDDs/PCDFs
Analvte Ouantitation Ions M-fCOCll+
TCDD 320 322 259
PeCDD 356 358 293
HxCDD 390 392 327
HpCDD 424 426 361
OCDD 458 460 395
TCDF 304 306 243
PeCDF 340 342 277
HxCDF 374 376 311
HpCDF 408 4lO 345
OCDF 442 444 379
Internal Standards
13C12-2378-TCDD 332 334
13C12-123678-HxCDD 402 404
13Ci2-OCDD 470 472
13C12-2378-TCDF 316 318
13Ci2-1234678-HPCDF 420 422
Recovery Standards
13C12-1234-TCDD 332 334
13C12-123789-HxCDD 402 404
Cleanup Standard
37C14-2378-TCDD 328 (1) 263
Polychlorinated
diphenyl ethers
HxCDPE 376
HpCDPE 410
OCDPE 446
NCDPE 480
DCDPE 514
(1) There is only one quantitation ion monitored for the cleanup standard.
D-59 DFLM01.1 (9/91)
-------
TABLE 6. CRITERIA FOR ISOTOPIC RATIO MEASUREMENTS FOR PCDDs/PCDFs
Analyte
;.CDD
PeCDD
HxCDD
HpCDD
OCDD
TCDF
PeCDF
HxCDF
HpCDF
OCDF
Internal Standards
13
13
13
13
13
C12-1234-TCDD
C12-123678-HxCDD
G12-2378-TCDF
C12- 1234678 -HPCDF
Recovery Standards
j'3C12-1234-TCDD
13C12-123789-HxCDD
Selected
Ions
320/322
356/358
390/392
424/426
458/460
304/306
340/342
374/376
408/410
442/444
332/334
402/404
470/472
316/318
420/422
332/334
402/404
Theoretical
Ion Abundance
0.77
1.55
1.24
1.04
0.89
0.77
1.55
1.24
1.04
0.89
0.77
1.24
0.89
0.77
1.04
0.77
1.24
Control
Limits
0.65
1.24
1.05
0.88
0.76
0.65
1.24
1.05
0.88
0.76
0.65
1.05
0.76
0.65
0.88
0.65
1.05
- 0.89
- 1.86
- 1.43
- 1.20
-1.02
- 0.89
- 1.86
- 1.43
-1.20
- 1.02
- 0.89
- 1.43
-1.01
- 0.89
-1.20
- 0.89
- 1.43
D-60
DFLM01.0
-------
TABLE 7. RECOMMENDED SELECTED ION MONITORING DESCRIPTORS
Descriptor 1
Descriptor 2
Descriptor 3
Descriptor 4
2.43
259
277
293
304
306
316
318
320
322
328
332
334
340
342
356
358
376
277
293
311
327
338
340
342
354
356
358
374
376
390
392
402
404
410
446
311
327
345
361
374
376
390
392
402
404
408
410
420
422
424
426
446
480
345
361
379
395
408
410
420
422
424
426
442
444
458
460
470 .
472
480
514
The ions at m/z 376 (HxCDPE), 410 (HpCDPE), 446 (OCDPE), 480 (NCDPE) and 514
(DCDPE) represent the polychlorinated diphenyl ethers.
The ions in each of the four recommended descriptors are arranged so that
there is overlap between the descriptors. The ions for the TCDD, TCDF, PeCDD
and PeCDF isomers are in the first descriptor, the ions for the PeCDD, PeCDF,
HxCDD and HxCDF isomers are in the second descriptor, the ions for the HxCDD,
HxCDF, HpCDD and HpCDF isomers are in the third descriptor, and the ions for
the HpCDD, HpCDF, OCDD and OCDF isomers are in the fourth descriptor.
NOTE: The descriptors used by the laboratory must be documented, and this
information must be available for examination during the EPA on-site
evaluations.
D-61
DFLM01.0
-------
TABLE 8. RELATIONSHIP OF INTERNAL STANDARDS TO ANALYTES, AND RELATIONSHIP OF
RECOVERY STANDARDS TO ANALYTES, INTERNAL STANDARDS AND CLEANUP STANDARD
INTERNAL STANDARDS VS. ANALYTES
13
C-L2-TCDD
TCDD
PeCDD
13
C12-HxCDD
HxCDD
HpCDD
13,
OCDD
OCDF
13
C12-TCDF
TCDF
PeCDF
13
C12-HpCDF
HxCDF
HpCDF
RECOVERY STANDARDS VS. ANALYTES, INTERNAL STANDARDS AND CLEANUP STANDARD
13C12-1234-TCDD
13
TCDD
TCDF
PeCDD
PeCDF
13
13
37
-2378-TCDD
C12-2378-TCDF
Cl4-2378-TCDD
13
13
13
C12-123789-HxCDD
HxCDD
HxCDF
HpCDD
HpCDF
OCDD
OCDF
c12-123678-HxCDD
C12-1234678-HpCDF
C^-OCDD
D-62
DFLM01.0
-------
TABLE 9. PCDD/PCDF ISOMERS IN THE WINDOW DEFINING MIX FOR A 60 M DB-5 (OR
EQUIVALENT) COLUMN
Homologue
TCDD
TCDF
PeCDD
PeCDF
HxCDD
HxCDF
HpCDD
HpCDF
First
Eluted
1368-
1368-
12479-
13468-
124679-
123468-
1234679-
1234678-
Last
Eluted
1289-
1289-
12389-
12389-
123467-
123489-
1234678-
1234789-
Approximate
Concentration
0.5
0.5
0.5
0.5
1.25
1.25
1.25
1.25
D-63
DFLH01.0
-------
TABLE 10. SUPPLEMENTAL CALIBRATION SOLUTION
Analvte Concentration Cng/uL)
23478-PeCDF 4
123789-HxCDD 10
123478-HxCDD 10
123478-HxCDF 10
123789-HxCDF 10
234678-HxCDF 10
1234789-HpCDF 10
The supplemental calibration solution is commercially
supplied and is used for preparation of the CC3 solution.
(See Paragraph 7.4.1 for CC3 preparation.)
D-64 DFLM01.0
-------
TABLE 11. MATRIX SPIKING SOLUTION
Analyte Concentration fng/uL')
2378-TCDD 2.5
2378-TCDF 2.5
12378-PeCDF 6.25
12378-PeCDD 6.25
123678-HxCDF 6.25
123678-HxCDD 6.25
1234678-HpCDF 6.25
1234678-HpCDD 6.25
OCDD 12.5
OCDF 12.5
This solution is prepared in tridecane (or nonane) and diluted with
acetone prior to use (see Section 5.18).
D-65 DFLM01.0
-------
TABLE 12. COLUMN PERFORMANCE SOLUTION FOR A SP-2331 (OR EQUIVALENT) COLUMN
Approximate
Isomer Concentrations fng/uL')
1478-TCDD 0.5
2378-TCDD 0.5
1237/1238-TCDD 0.5
The commercially supplied column performance solution may be combined with
the window defining mix, provided that the combined soultion contains the
isomers needed to determine that the criteria for both analyses can be met
(see Paragraph 7.2.2).
D-66 DFLM01.0
-------
TABLE 13. EXAMPLE ANALYTICAL SEQUENCES
Time
Hour 0
Hour 12
Hour 0
Analysis
Window Defining Mix
Column Performance Solution (SP-2331)
CC3
CC1 (Initial Calibration)
CC2
CC4
CCS
Blanks and Samples
o
o
o
o
CGI
Column Performance Solution (SP-2331)
CC3
Blanks and Samples
o
o
o
o
Hour 12
Hour 0
CC1
Column Performance Solution (SP-2331)
CC3
Blanks and Samples
o
o
o
etc.
NOTE:
CC1 (whenever the sequence does end)
Matrix spike and duplicate samples may be analyzed in
place of any "sample" listed above.
D-67
DFLM01.0
-------
Complex Waste
Sample
(including waters,
soils, stillbottoms,
oils, sludges,
etc.)
Sample
Extract
60% CH2CI2/hexane
fraction
Analyze by GC/MS
(1) Add internal standards
(2) Perform matrix-specific extraction
(1) Wash with concentrated H2SO4
(2) Wash with 5% NaCI
(3) Wash with 20% KOH
(4) Wash with 5% NaCI
(5) Dry extract
(6) Solvent exchange
(7) Silica gel column cleanup
(8) Alumina column cleanup
(1) Concentrate eluate
(2) Carbon column cleanup
(3) Add recovery standard(s)
Figure 1: Flow Chart for Sample Extraction and Cleanup for the Analysis of
PCDDs and PCDFs in Complex Waste Samples
-------
2
3
O
8
7
2
3
Polychlorinated Dibenzo-p-Dioxin
Polychlorinated Dibenzofuran
8
7
where x + y < 8
Figure 2: General Structures of PCDDs and PCDFs
-------
lonCurrent(x 10-2)
2.5 -
1.5 -
0.5
0
11 16 21
26 31 36 41 46 51
Scan Number
Figure 3: Measurement of Signal-To-Noise Ratio
-------
Figure 4: Soxhiet/Dean-Stark Extractor
-------
^
"w
CD
DC
1237/1238-TCDD
2378-TCDD
1478-TCDD
Time
Figure 5: Valley Between 2378-TCDD and Other Closely Eluting Isomers on an
SP-2331 (or Equivalent) Column
-------
EXHIBIT E
QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
DFLM01.0
-------
Table of Contents
OVERVIEW
Page
E-3
SECTION I: Introduction E-4
SECTION II: Quality Assurance Plan E-6
SECTION III: Standard Operating Procedures E-8
SECTION IV: QA/QC Requirements E-ll
SECTION V: Analytical Standards Requirements E-18
SECTION VI: Contract Compliance Screening E-23
SECTION VII: Regional Data Review E-24
SECTION VIII: Laboratory Evaluation Samples E-25
SECTION IX: GC/MS Tape Audits E-27
SECTION X: On-site Laboratory Evaluations E-28
SECTION XI: Quality Assurance and Data Trend Analysis E-31
SECTION XII: Data Management E-32
REFERENCES E-34
E-2
DFLM01.0
-------
OVERVIEW
Quality assurance (QA) and quality control (QC) are integral parts of the
CLP. ' ' ' ' The QA process consists of management review and oversight at
the planning, implementation, and completion stages of the environmental data
collection activity to ensure that data provided are of ...ie quality required.
The QC process includes those activities required during data collection to
produce the data quality desired and to document the quality of the collected
data.1
During the planning of an environmental data collection program, QA
activities focus on defining data quality criteria and designing a QC system
to measure the quality of data being generated. During the implementation of
the data collection effort, QA activities ensure that the QC system is
functioning effectively, and that the deficiencies uncovered by the QC system
are corrected. After environmental data are collected, QA activities focus
on assessing the quality of data obtained to determine its suitability to
support enforcement or remedial decisions. ''
This exhibit describes the overall QA/QC operations and the processes by
which the CLP meets the QA/QC objective defined above. This contract
requires a variety of QA/QC activities. These contract requirements are the
minimum QC operations necessary to satisfy the analytical requirements
associated with the determination of the different method analytes. These QC
operations are designed to facilitate laboratory comparison by providing the
EPA with comparable data from all Contractors. These requirements do not
release the analytical Contractor from maintaining their own QC checks on
method and instrument performance.
E-3 DFLM01.0
-------
SECTION I
INTRODUCTION
Appropr..ji;e use of data generated under the great range of analytical
conditions encountered in environmental analyses requires reliance on the QC
procedures and criteria incorporated into the methods. The methods in this
contract have been validated on samples typical of those received by the
laboratories in the CLP. However, the validation of these methods does not
guarantee that the methods perform equally well for all sample matrices
encountered. Inaccuracies can also result from causes other than
unanticipated matrix effects, such as sampling artifacts, equipment
malfunctions, and operator error. Therefore, the QC component of each method
is indispensable.
The data acquired from QC procedures are used to estimate and evaluate the
information content of analytical results and to determine the necessity for
or the effect of corrective action procedures. The means used to estimate
information content include precision, accuracy, detection limit, and other
quantitative and qualitative indicators. In addition, the QC component gives
an overview of the activities required in an integrated program to generate
data of known and documented quality required to meet defined objectives.
The necessary components of a complete QA/QC program include internal QC
criteria that demonstrate acceptable levels of performance, as determined by
QA review. External review of data and procedures is accomplished by the
monitoring activities of the National Program Office (NPO), Regional data
users, the Sample Management Office (SMO), the National Enforcement
Investigations Center (NEIC), and the Environmental Monitoring Systems
Laboratory (EMSL-LV). Each external review accomplishes a different purpose.
These reviews are described in specific sections of this exhibit.
Performance evaluation (PE) samples and magnetic tape audits provide an
external QA reference for the program. A laboratory on-site evaluation
system is also part of the external QA monitoring. A feedback loop provides
the results of the various review functions to the contract laboratories
through direct communications with the Administrative Project Officer (APO)
and Technical Project Officer (TPO).
This exhibit is not a guide to constructing QA project plans, QC systems, or
a QA organization. However, the exhibit does explain the QA/QC requirements
of the program, outlines some minimum standards for QA/QC programs, and
includes specific items that are required in a QA Plan and QA/QC
documentation detailed in this contract. Delivery of this documentation
provides EPA with a complete data package which will stand alone, and limits
the need for contact with the Contractor or with an analyst, at a later date,
if some aspect of the analysis is questioned.
In order to assure that the product delivered by the Contractor meets the
requirements of the contract, and to improve interlaboratory data comparison,
EPA requires the following from the Contractor:
E-4 DFLM01.0
-------
A written QA Plan, the elements of which are designated in Section
II.
Written preparation of and adherence to QA/QC standard operating
procedures (SOPs) as described in Section III.
Adherence to the analytical methods and associated QC requirements
specified in the contract.
Verification of an analytical standard and documentation of the
purity of neat materials and the purity and accuracy of solutions
obtained from private chemical supply houses.
Submission of all raw data and pertinent documentation for Regional
review.
Participation in the analysis of laboratory evaluation samples,
including adherence to corrective action procedures.
Submission, upon request, of GC/MS tapes and applicable
documentation for tape audits.
Participation in on-site laboratory evaluations, including adherence
to corrective action procedures.
Submission of all original documentation generated during sample
analyses for EPA review.
E-5 DFLM01.0
-------
SECTION II
QUALITY ASSURANCE PLAN
The Contractor shall establish a QA program with the objective of providing
sound analytical chemical measurements. This program shall incorporate the
QC procedures, any necessary corrective action, and all documentation
required during data collection as well as the quality assessment measures
performed by management to ensure acceptable data production.
As evidence of such a program, the Contractor shall prepare a written QA Plan
(QAP) which describes the procedures that are implemented to achieve the
following:
o Maintain data integrity, validity, and usability.
o Ensure that analytical measurement systems are maintained in an
acceptable state of stability and reproducibility.
o Detect problems through data assessment and establish corrective
action procedures which keep the analytical process reliable.
o Document all aspects of the measurement process in order to provide
data which are technically sound and legally defensible.
The QAP must present, in specific terms, the policies, organization,
objectives, functional guidelines, and specific QA and QC activities designed
to achieve the data quality requirements in this contract. Where applicable,
SOPs pertaining to each element shall be included or referenced as part of
the QAP. The QAP must be available during an on-site laboratory evaluation.
Additional information relevant to the preparation of a QAP can be found in
EPA and ASTM publications. 2>^
The elements of a QAP are as follows:
A. Organization and Personnel
1. QA Policy and Objectives
2. QA Management
a. Organization
b. Assignment of QC and QA Responsibilities
c. Reporting Relationships
d. QA Document Control Procedures
e. QA Program Assessment Procedures
3. Personnel
a. Resumes
b. Education and Experience Pertinent to this Contract
c. Training Progress
E-6 DFLM01.1 (9/91)
-------
B. Facilities and Equipment
1. Instrumentation and Backup Alternatives
2. Maintenance Activities and Schedules
C. Document Control
1. Laboratory Notebook Policy
2. Samples Tracking/Custody Procedures
3. Logbook Maintenance and Archiving Procedures
4. Case File Organization, Preparation and Review Procedures
5. Procedures for Preparation, Approval, Review, Revision, and
Distribution of SOPs
6. Process for Revision of Technical or Documentation Procedures
D. Analytical Methodology
1. Calibration Procedures and Frequency
2 . Sample Preparation/Extraction Procedures
3. Sample Analysis Procedures
4. Standards Preparation Procedures
5. Decision Processes, Procedures, and Responsibility for Initiation of
Corrective Action
E. Data Generation
1. Data Collection Procedures
2. Data Reduction Procedures
3. Data Validation Procedures
4. Data Reporting and Authorization Procedures
F. Quality Control
1. Solvent, Reagent and Adsorbent Check Analysis
2. Reference Material Analysis
3. Internal Quality Control Checks
4. Corrective Action and Determination of QC Limit Procedures
5. Responsibility Designation
G. Quality Assurance
1. Data Quality Assurance
2. Systems/Internal Audits
3. Performance/External Audits
4. Corrective Action Procedures
5. Quality Assurance Reporting Procedures
6. Responsibility Designation
•"- E-7a DFLM01.0
-------
Updating and Submission of the OAF:
Within 60 days of contract award:
During the contract solicitation process, the Contractor was required to
submit their QAP to EMSL-LV and NEIC. Within sixty (60) days after contract
award, the Contractor shall send a revised QAP, fully compliant with the
requirements of this contract, to the TPO, EMSL-LV and NEIC. The revised QAP
will become the official QAP under the contract. The revised QAP must
include:
1. Changes resulting from the Contractor's internal review of their
organization, personnel, facility, equipment, policy and procedures
and the Contractor's implementation of the requirements of the
contract; and
2. Changes resulting from the Agency's review of the laboratory
evaluation sample data, bidder-supplied documentation, and
recommendations made during the preaward laboratory site evaluation.
Subsequent submissions:
During the term of contract, the Contractor shall amend the QAP when the
following circumstances occur:
1. The Agency modifies the contract,
2. The Agency notifies the Contractor of deficiencies in the QAP,
3. The Agency notifies the Contractor of deficiencies resulting from
the Agency's review of the Contractor's performance,
4. The Contractor identifies deficiencies resulting from the internal
review of the QAP,
5. The Contractor's organization, personnel, facility, equipment,
policy or procedures change, or
6. The Contractor identifies deficiencies resulting from the internal
review of their organization, personnel, facility, equipment, policy
or procedures.
The Contractor shall amend the QAP within 30 days of when the circumstances
listed above result in a discrepancy between what was previously described in
the QAP and what is presently occurring at the Contractor's facility. When
the QAP is amended, all changes in the QAP must be clearly marked (i.e.,
indicating where the change is in the document with a bar in the margin,
underlining the change, printing the change in bold, or using a different
print font). The amended pages must have the date on which the changes were
implemented.
E-7b
DFLM01.1 (9/91
-------
The Contractor shall incorporate all amendments to the current QAP. The
Contractor shall archive all amendments to the QAP for future reference by
the Agency. The Contractor shall send a copy of the current QAP within 14
days of a request by the TPO or APO to the designated recipients.
Corrective action:
If the Contractor fails to adhere to these requirements, the Contractor may
expect, but the Agency is not limited to, the following actions: reduction
of numbers of samples sent under this contract, suspension of sample shipment
to the Contractor, GC/MS tape audit, data package audit, on-site laboratory
evaluation, remedial laboratory evaluation sample, and/or contract sanctions,
such as a Cure Notice.
E-7c DFLM01.1 (9,
-------
SECTION III
STANDARD OPERATING PROCEDURES
In order to obtain reliable results, adherence to prescribed analytical
methodology is imperative. In any operation that is performed on a repetitive
basis, reproducibility is best accomplished through the use of SOPs. As
defined by EPA, a SOP is a written document which provides directions for the
step-by-step execution of an operation, analysis or action which is commonly
accepted as the method for performing certain routine or repetitive tasks.
SOPs prepared by the Contractor must be functional, i.e., clear,
comprehensive, up-to-date, and sufficiently detailed to permit duplication of
results by qualified analysts. All SOPs, as presented to EPA, must reflect
activities as they are currently performed in the laboratory. In addition,
all SOPs must meet the following criteria:
o Be consistent with current EPA regulations, guidelines, and the
contract's requirements.3'*'5'6''
o Be consistent with instrument manufacturers' specific instruction
manuals.
o Be available to the EPA during an on-site laboratory evaluation. A
complete set of SOPs shall be bound together and available for
inspection at such evaluations. During on-site evaluations,
laboratory personnel may be asked to demonstrate the application of
the SOPs.
o Provide for the development of documentation that is sufficiently
complete to record the performance of all tasks required by the
protocol.
o Demonstrate the validity of data reported by the Contractor and
explain the cause of missing or inconsistent results.
o Describe the corrective measures and feedback mechanism utilized
when analytical results do not meet protocol requirements.
o Be reviewed regularly and updated as necessary when contract,
facility or Contractor procedural modifications are made.
o Be archived for future reference in usability or evidentiary
situations.
o Be available at specific work stations as appropriate
o Be subject to a document control procedure which precludes the use
of outdated or inappropriate SOPs.
A. SOP Format
The format for SOPs may vary depending upon the kind of activity for
which they are prepared; however, at a minimum, the following sections
must be included:
E-8 DFLM01.0
-------
o Title page.
o Scope and application.
o Definitions.
o Procedures.
o QC limits.
o Corrective action procedures, including procedures for secondary
review of information being generated.
o Documentation description and example forms.
o Miscellaneous notes and precautions.
o References.
B. Required SOPs
The following SOPs are required by EPA:
1. Evidentiary SOPs (see Exhibit F).
2. Sample receipt and storage.
3. Sample preparation.
4. Calibration.
5. Standards purity/preparation.
6. Maintaining instrument records and logbooks.
7. Sample analysis and data control systems.
8. Glassware cleaning.
9. Technical and managerial review of laboratory operation and
data package preparation.
10. Internal review of contractually required QA/QC data for each
individual data package.
11. Chain-of-custody procedures and document control including
Complete Sample Delivery Group (SDG) File preparation.
12. Laboratory data validation/laboratory self-inspection.
a. Data flow and chain-of-command for data review.
b. Procedures for measuring precision and accuracy.
c. Evaluation parameters for identifying systematic errors.
d. Procedures to assure that hardcopy deliverables are
complete and compliant with the requirements in Exhibit B.
3*-
E-9 DFLM01.0
-------
e. Demonstration of internal QA inspection procedures
(demonstrated by supervisory sign-off on personal
notebooks, internal PE samples, etc.).
f. Frequency and type of internal audits (e.g., random,
quarterly, spot checks, perceived trouble areas).
g. Demonstration of problem identification-corrective actions
and resumption of analytical processing and sequence
resulting from internal audit (i.e., QA feedback).
h. Documentation of audit reports (internal and external),
response, corrective action, etc.
13. Data management and handling.
a. Procedures for controlling and estimating data entry
errors.
b. Procedures for reviewing changes to data and deliverables
and ensuring traceability of updates.
c. Lifecycle management procedures for testing, modifying and
implementing changes to existing computing systems
including hardware, software, and documentation or
installing new systems.
d. Database security, backup and archival procedures
including recovery from system failures.
e. System maintenance procedures and response time.
f. Individuals(s) responsible for system operation,
maintenance, data integrity and security.
g. Specifications for staff training procedures.
C. SOP Delivery Requirements
Updating and submission of SOPs:
During the contract solicitation process, the Contractor was required
to submit their SOPs to EMSL-LV and NEIC. Within sixty (60) days after
contract award, the Contractor shall send a complete revised set of
SOPs, fully compliant with the requirements of this contract, to the
TPO, EMSL-LV and NEIC. The revised SOPs will become the official SOPs
under the contract. The revised SOPs must include:
1. Changes resulting from the Contractor's internal review of
their procedures and the Contractor's implementation of the
requirements of the contract;
E-lOa DFLM01.1 (9/91]
-------
2. Changes resulting from the Agency's review of the laboratory
evaluation sample data, bidder-supplied documentation, and
recommendations made during the preaward laboratory site
evaluation.
Subsequent submissions:
During the term of contract, the Contractor shall amend the SOPs when
the following circumstances occur:
1. The Agency modifies the contract,
2. The Agency notifies the Contractor of deficiencies in their
SOPs documentation,
3. The Agency notifies the Contractor of deficiencies resulting
from the Agency's review of the Contractor's performance,
4. The Contractor's procedures change,
5. The Contractor identifies deficiencies resulting from the
internal review of their SOPs, or
6. The Contractor identifies deficiencies resulting from the
internal review of their procedures.
The SOPs must be amended or new SOPs must be written within 30 days of
when the circumstances listed above result in a discrepancy between
what was previously described in the SOPs and what is presently
occurring at the Contractor's facility. All changes in the SOPs must
be clearly marked (i.e, indicating where the change is in the document
with a bar in the margin, underlining the change, printing the change
in bold, or using a different print font). The amended/new SOPs must
have the date on which the changes were implemented.
When the SOPs are amended or new SOPs are written, the Contractor shall
document in a letter the reasons for the changes, and submit the
amended SOPs or new SOPs to the TPO, EMSL-LV (quality
assurance/technical SOPs) and NEIC (evidentiary SOPs). The Contractor
shall send the letter and the amended sections of the SOPs or new SOPs
within 14 days of the change. An alternate delivery schedule for the
submittal of the letter and amended/new SOPs may be proposed by the
Contractor, but it is the sole decision of the Agency, represented
either by the TPO or APO, to approve or disapprove the alternate
delivery schedule. If an alternate delivery schedule is proposed, the
Contractor shall describe in a letter to the TPO, APO, and the
Contracting Officer why he/she is unable to meet the delivery schedule
listed in this section. The TPO/APO will not grant an extension for
greater than 30 days for amending/writing new SOPs. The TPO/APO will
not grant an extension for greater than 14 days for submission of the
letter documenting the reasons for the changes and for submitting
amended/new SOPs. The Contractor shall proceed and not assume that an
extension will be granted until so notified by the TPO and/or APO.
E-lOb
DFLM01.1 (9/91)
-------
The Contractor shall send a complete set of current SOPs within 14 days
of a request by the TPO or APO to the recipients he/she designates.
Corrective action:
If the Contractor fails to adhere to these requirements, the Contractor
may expect, but the Agency is not limited to, the following action:
reduction of number of samples sent under this contract, suspension of
sample shipment to the Contractor, GC/MS tape audit, data package
audit, on-site laboratory evaluation, remedial laboratory evaluation
sample, and/or contract sanction, such as a Cure Notice.
E-lOc DFLM01.1 (9/
-------
SECTION IV
QA/QC REQUIREMENTS
..^^ ..ec^on out1.: - cue minimum QC operations necessary to satisfy the
analytical requirements associated with the detection and quantitative
measurement of 2378-tetrachlorinated dibenzo-p-dioxin and total tetra-,
penta-, hexa-, hepta- and octachlorinated dibenzo-p-dioxins (PCDDs) and
dibenzofurans (PCDFs), by using the procedures outlined in Exhibit D. This
section is not intended as a comprehensive QC document, but rather as a guide
to the specific QC operations that must be considered for PCDD/PCDF analysis.
The QC operations that must be considered include the following:
o Mass Calibration.
o Window Defining Mix.
o Chromatographic Resolution.
o GC/MS Initial Calibration.
o GC/MS Continuing Calibration.
o Instrument Sensitivity.
o Identification Criteria.
o Method Blank Analysis.
o Spiked Sample Analysis.
o Duplicate Sample Analysis.
o Toxicity Equivalency Factor and Isomer Specificity.
o Dilutions.
o Reanalyses.
1. Mass Calibration
1.1 Mass calibration of the mass spectrometer is recommended prior to
analyzing the calibration solutions, blanks, samples and QC samples.
It is recommended that the instrument be tuned to greater sensitivity
in the high mass range in order to achieve better response for the
later eluting compounds.
1.2 Optimum results using FC-43 for mass calibration can be achieved by
scanning from 222-510 amu every one second or less, utilizing 70 volts
(nominal) electron energy in the electron ionization mode (see Exhibit
D, Section 6).
1.3 m/z 414 and m/z 502 should be 30-50 percent of m/z 264 base peak (see
Exhibit D, Section 6).
E-ll DFLM01.0
-------
2. Window Defining Mix
2.1 The window defining mix is analyzed to verify that the switching times
between the descriptors have been appropriately set.
2.2 The window defining mix is obtained from commercial sources and must
contain the first and last eluting isomers in each homologue on the GC
column chosen for analyses (see Exhibit D, Section 5.12 and Table 9).
2.3 The window defining mix must be analyzed before the initial calibration
on each instrument and GC column used for analysis and at the frequency
found in Exhibit D, Paragraph 7.1.3.
3. Chromatographic Resolution
3.1 Chromatographic resolution is evaluated using one of two standard
solutions, depending on the GC column chosen for analyses.
3.2 For analyses on a DB-5 (or equivalent) GC column, the Chromatographic
resolution is evaluated by the analysis of the CCS standard during both
the initial and continuing calibration procedures (see Exhibit D,
Paragraphs 7.3.2.1 and 7.4.2).
3.3 For analyses on a SP-2331 (or equivalent) GC column, the
Chromatographic resolution is evaluated before the analysis of any
calibration standard by the analysis of a commercially available column
performance mixture (see Exhibit D, Section 5.19) that contains the
TCDD isomers that elute most closely with 2378-TCDD on this GC column
(1478-TCDD and the 1237/1238-TCDD pair) (see Exhibit D, Paragraph
7.2.2).
3.4 The Chromatographic resolution criteria are found in Exhibit D,
Paragraphs 7.3.2.1 and 7.2.3.
4. GC/MS Initial Calibration
4.1 Prior to analysis of samples and blanks, the GC/MS system must be
initially calibrated at a minimum of five concentrations to verify
linearity of response.
4.2 The calibration solutions containing the labeled and unlabeled analogs
must be analyzed at five concentrations as described in Exhibit D,
Section 5.11 and Table 3.
4.3 The CC1, CC2, CC4 and CCS solutions shall be used as provided by EPA
(see Exhibit D, Section 7.3). The CC3 solution must be prepared as
explained in Exhibit D, Paragraph 7.4.1.
4.4 The calibration standard must be analyzed using the MS/DS conditions as
described in Exhibit D, Paragraph 7.3.1.
10 10
4.5 The Chromatographic resolution between the C]_2 2378-TCDD and C]^
1234-TCDD isomers must be resolved with a valley of < 25 percent, and
~~ E-12 DFLM01.0
-------
the chromatographic peak separation between the 123478-HxCDD and
123678-HxCDD in the CC3 solution must be resolved with a valley of < 50
percent (see Exhibit D, Paragraph 7.3.2.1).
4.6 The relative ion abundance criteria for PCDDs/PCDFs must be met for all
PCDD/PCDF peaks, including the labeled internal and recovery standards,
in all solutions (see Exhibit D, Table 6).
4.7 For all calibration solutions, the retention times of the isomers must
fall within the appropriate retention time windows established by the
window defining mix (see Exhibit D, Section 7.1).
4.8 For all calibration solutions, the signal-to-noise ratio must meet the
criteria specified in Exhibit D, Paragraph 7.3.2.4.
4.9 The relative response factors for the 17 unlabeled target analytes
relative to their appropriate internal standards, and the relative
response of the five labeled internal standard standards relative to
the appropriate recovery standard are determined according to the
procedures in Exhibit D, Paragraph 7.3.3.
4.10 Calculate the mean RRF and percent relative standard deviation (%RSD)
of the five KRFs (CC1 to CCS) for each unlabeled PCDD/PCDF, and labeled
internal and recovery standards, present in all five concentration
calibration solutions as described in Exhibit D, Paragraph 7.3.5. As
indicated in the referenced paragraph, no %RSD calculation is possible
for the 2,3,7,8-substituted isomers in the CCS supplemental calibration
solution, because they are only present in the one solution.
4.11 The %RSD is calculated for the EPA-supplied unlabeled and labeled
analytes only. To establish linearity, the %RSD of the five RRFs (CC1-
CC5) for the unlabeled PCDDs/PCDFs and the internal standards must not
exceed 15.0% (see Exhibit D, Paragraph 7.3.5).
4.12 If the initial calibration criteria for GC resolution, ion abundance
ratios, retention times, instrument sensitivity and relative response
factors are not met, the Contractor must take the corrective actions as
explained in Exhibit D, Paragraph 7.3.7.
4.13 The response factors to be used for determining the total homologue
concentrations are described in Exhibit D, Section 15.2.
5. GC/MS Continuing Calibration
5.1 Once the GC/MS system has been calibrated, the calibration must be
verified for each 12-hour time period for each GC/MS system.
5.2 The continuing calibration standard is prepared by mixing the
commercially supplied supplemental standard with the EPA supplied CC4
solution (see Exhibit D, Paragraph 7.4.1).
5.3 The continuing calibration consists of two parts: evaluation of the
chromatographic resolution and verification of the RRF values to be
used for quantitation. At the beginning of each 12-hour period, the
*" E-13 DFLM01.0
-------
chromatographic resolution is verified in the same fashion as in the
initial calibration, through the analysis of the CC3 solution on the
DB-5 (or equivalent) column or through the analysis of the column
performance solution on the SP-2331 (or equivalent) column (see Exhibit
D, Section 7.4).
5.4 The continuing calibration standard must be analyzed according to the
procedures given in Exhibit D, Section 7.4, and at the frequency in
that section.
5.5 Calculate the relative response factors for the 17 unlabeled target
analytes relative to their appropriate internal standards and the
response factor for the five labeled internal standard relative to the
appropriate recovery standard, according to the procedure described in
Exhibit D, Paragraph 7.4.4.
5.6 The GC resolution criteria for DB-5 or SP-2331 (or equivalent) column,
as specified in Exhibit D, Paragraph 7.3.2.1 or 7.4.3, must be met
before the analysis of samples may begin. If the separation criteria
for both DB-5 and SP-2331 (or equivalent) column analysis are met, a
single column analysis may be used.
5.7 The relative ion abundance for all PCDD/PCDF peaks, including the
labeled internal and recovery standards, for both beginning and ending
analyses must meet the criteria listed in Exhibit D, Table 6.
5.8 The signal-to-noise ratio for the CC3 and CC1 solutions must meet the
criteria specified in Exhibit D, Paragraph 7.4.6.3.
5.9 The percent difference for the RRFs must be calculated as explained in
Exhibit D, Paragraph 7.4.6.4 and must meet the criteria specified in
that paragraph.
5.10 If the criteria specified in Exhibit D, Paragraph 7.4.6 are not met,
the Contractor must take the corrective actions outlined in Exhibit D,
Paragraph 7.4.7.
6. Instrument Sensitivity
6.1 In order to demonstrate that the GC/MS/DS system has retained adequate
sensitivity during the course of sample analyses, the Contractor must
analyze the lowest of the calibration standards (CC1) at the end of
each 12-hour period during which samples and standards are analyzed.
6.2 Analyze the CC1 solution according to Exhibit D, Paragraph 7.5.1.
6.3 This analysis must meet the retention time criteria in Exhibit D,
Paragraph 7.5.2.1.
6.4 This analysis must meet the ion abundance ratio criteria in Exhibit D,
Table 6.
E-14 DFLM01.0
-------
6.5 For this analysis, the signal-to-noise ratio shall be greater than 2.5
for the unlabeled PCDD/PCDF ions, and greater than 10.0 for the labeled
internal and recovery standards.
7. Identification Criteria
7.1 For a gas chromatographic peak to be unambiguously identified as a
PCDD/PCDF, the peak must meet all of the following criteria.
7.2 The identification of the PCDD/PCDF isomers is based on simultaneous
detection of the two most abundant ions in the molecular ion regions
and the M-COC1 ion. In order to make a positive identification, the
relative retention time criteria specified in Exhibit D, Section 11.1
must be met.
7.3 All of the ions specified for each PCDD/PCDF homologue and labeled
standards must be present in the selected ion current profile. The ion
current response for the analytes and labeled standards must meet the
QC criteria (see Exhibit D, Section 11.2).
7.4 The integrated ion current for each analyte ion listed in Exhibit D,
Table 5 must be at least 2.5 times background noise and must not have
saturated the detector. The internal standard ions must be at least 10
times background noise and must not have saturated the detector (see
Exhibit D, Section 11.3).
7.5 The relative ion abundance criteria for the native analytes and
internal standard must be met (see Exhibit D, Table 6).
7.6 The identification of a GC peak as a PCDF cannot be made if a signal
having a signal-to-noise ratio greater than 2.5 is detected in the
corresponding PCDPE channel (see Exhibit D, Section 11.5).
8. Method Blank Analysis
8.1 A method blank is a volume of clean reference matrix that is carried
through the entire analytical sequence.
8.2 A minimum of one blank per matrix must be analyzed with each SDG at a
frequency described in Exhibit D, Section 12.1.
8.3 An acceptable method blank must not contain any chemical interferences
or electronic noise at the m/z of the specified unlabeled PCDD/PCDF
ions which is greater than 5 percent of the signal of the appropriate
internal standard, or any peak that meets the identifications criteria
as a PCDD/PCDF which is greater than 2 percent of the appropriate
internal standard (see Exhibit D, Section 15.2).
8.4 If the blank is contaminated, the associated positive samples and any
samples containing peaks that do not meet all the identification
criteria must be rerun (see Exhibit D, Paragraph 12.2.3).
E-15 DFLM01.0
-------
9. Spiked Sample Analysis
9.1 In order to provide data on the accuracy of the analytical method, the
Contractor is required to prepare and analyze a spiked sample for each
matrix being analyzed. For each SDG, the Contractor must prepare a
spiked sample for all of the matrix types that occur in th° SDG (see
Exhibit D, Section 13).
9.2 Prepare a spiked sample according to the procedures in Exhibit D,
Sections 13.1 and 13.2.
9.3 Extract and analyze the spiked sample according to the procedures in
Exhibit D, Sections 9 and 10.
9.4 Calculate the recovery of the spiked analytes according to the
procedures in Exhibit D, Section 13.5.
10. Duplicate Sample Analysis
10.1 In order to provide data on the precision of the analytical method, the
Contractor is required to prepare and analyze a duplicate of one sample
for each matrix being analyzed. For each group of samples, the
laboratory must prepare a duplicate sample for all of the following
matrix types that occur in the SDG (see Exhibit D, Section 14).
10.2 Prepare a duplicate sample according to the procedures in Exhibit D,
Section 14.1.
10.3 Extract and analyze the spiked sample according to the procedures in
Exhibit D, Sections 9 and 10.
10.4 Calculate the relative percent difference between the results of the
original analysis and the duplicate analysis according to the
procedures in Exhibit D, Section 14.3.
11. Toxicity Equivalency Factor and Isomer Specificity
11.1 The 2378-TCDD toxicity equivalence of PCDDs/PCDFs present in the sample
must be calculated according to procedures outlined in Exhibit D,
Section 15.8.
11.2 Isomer specificity for all 2,3,7,8-substituted PCDDs/PCDFs cannot be
achieved on the 60-m DB-5 column alone. Historically, problems have
been associated with the separation of 2378-TCDD from 1237-TCDD and
1268-TCDD, and the separation of 2378-TCDF from 2347-TCDF. Because of
the toxicologic concern associated with 2378-TCDD and 2378-TCDF,
additional analyses may be required for some samples as described in
Exhibit D, Section 16.
11.3 If the toxicity equivalence calculated in Section 15 is greater than
0.7 ppb (soil/sediment or fly ash), 7 ppb (chemical waste), or 7 ppt
(aqueous), better isomer specificity is required than can be achieved
E-16 DFLM01.0
-------
on the DB-5 column. The Contractor may utilize either of the two
options listed in Exhibit D, Paragraphs 16.1.1 or 16.1.2 to achieve
adequate isomer specificity.
12. Dilutions
If the concentration of any PCDD/PCDF in the sample exceeds the
calibration range or the detector is saturated, a dilution must be
performed using the procedures given in Exhibit D, Section 10.4.
13. Reanalvses
The requirements for reextraction and for reanalysis of samples are
given in Exhibit D, Section 17.
E-17 DFLM01.0
-------
SECTION V
ANALYTICAL STANDARDS REQUIREMENTS
A. Overview
EPA will not supply all the analytical reference standards required for
performance of this contract. See Exhibit D, Section 5 for the
standards that may be provided by EPA, subject to availability.
Contractors will be required to prepare from neat materials or purchase
from private chemical supply houses the standards not supplied by EPA |
but necessary to successfully and accurately perform the analyses
required in this contract.
B. Preparation of Chemical Standards from the Neat High Purity Bulk
Material
The Contractor may prepare chemical standards from neat materials.
Commercial sources for neat chemical standards pertaining to compounds
listed on the Target Compound List are given in Appendix C of the
"Quality Assurance Materials Bank: Analytical Reference Standards,"
Seventh Edition, January 1988. Laboratories should obtain the highest
purity possible when purchasing neat chemical standards; standards
purchased at less than 97% purity must be documented as to why a higher
purity could not be obtained.
1. Neat chemical standards must be kept refrigerated when not being
used in the preparation of standard solutions. Proper storage of
neat chemicals is essential in order to safeguard them from
decomposition.
2. The purity of a compound can sometimes be misrepresented by a
chemical supply house. Since knowledge of purity is needed to
calculate the concentration of solute in a solution standard, the
Contractor is responsible for having analytical documentation
ascertaining that the purity of each compound is correctly stated.
Purity confirmation, when performed, should use either differential
scanning calorimetry, gas chromatography with flame ionization
detection, high performance liquid chromatography, infrared
spectrometry, or other appropriate techniques. Use of two or more
independent methods is recommended. The correction factor for
impurity when weighing neat materials in the preparation of solution
standards is:
Equation 1
weight of pure compound
weight of impure compound — (percent purity/100)
where "weight of pure compound" is that required to prepare a
specific volume of a solution standard of a specified concentration.
**" E-18 DFLMOL.1 (9/91)
-------
3. Mis-identification of compounds occasionally occurs and it is
possible that a mislabeled compound may be received from a chemical
supply house. The Contractor is responsible for having analytical
documentation ascertaining that all compounds used in the
preparation of solution standards are correctly identified.
Identification confirmation, when performed, should use gas
chromatographic/mass spectrometry analysis on at least two different
analytical columns, or other appropriate techniques.
4. Calculate the weight of material to be weighed out for a specified
volume taking into account the purity of the compound and the
desired concentration. A second person must verify the accuracy of
the calculations. Check balances for accuracy with a set of
standard weights. All weighing should be performed on an analytical
balance to the nearest 0.1 mg and verified by a second person. The
solvent used to dissolve the solute should be compatible with the
protocol in which the standard is to be used; the solute should be
soluble, stable, and nonreactive with the solvent. In the case of a
multicomponent solution, the components must not react with each
other.
5. Transfer the solute to a volumetric flask, and dilute to the
specified solution volume with solvent after ensuring dissolution of
the solute in the solvent. Sonication or warming may be performed
to promote dissolution of the solute. This solution is to be called
the primary standard, and all subsequent dilutions must be traceable
back to the primary standard.
6. Log notebooks are to be kept for all weighing and dilutions. All
subsequent dilutions from the primary standard and the calculations
for determining their concentrations are to be recorded and verified
by a second person. All solution standards are to be refrigerated
when not in use. All solution standards are to be clearly labeled
as to the identity of the compound(s), concentration, date prepared,
solvent, and initials of the preparer.
C. Purchase of Chemical Standards Already in Solution
Solutions of analytical reference standards can be purchased by the
Contractor provided they meet the following criteria:
1. Laboratories must maintain the following documentation to verify the
integrity of the standard solutions they purchase:
a. Mass spectral identification confirmation of the neat material.
b. Purity confirmation of.the neat material.
c. Chromatographic and quantitative documentation that the
solution standard was QC-checked according to the following
section.
2. The Contractor must purchase standards for which the quality is
demonstrated statistically and analytically by a method of the
supplier's choice. One way quality can be demonstrated is to
prepare and analyze three solutions; a high standard, a low
z<-
E-19 DFLM01.0
-------
standard, and a standard at the target concentration (see parts a
and b below) . The supplier must then demonstrate that the
analytical results for the high standard and low standard are
consistent with the difference in theoretical concentrations by
using the Student's t-test in part d. If this consistency is
achieved, the supplier must then demonstrate that the concentration
of the target standard lies midway between the concentrations of the
low and high standards by using the Student's t-test in part e.
Thus, the standard is certified to be within 10 percent of the
target concentration.
If the above procedure is used, the supplier must document that the
following have been achieved:
a. Two solutions of identical concentration must be prepared
independently from neat materials. An aliquot of the first
solution must be diluted to the intended concentration (the
"target standard") . One aliquot is taken from the second
solution and diluted to a concentration 10 percent greater than
the target standard. This aliquot is called the "high
standard." One further aliquot is taken from the second
solution and diluted to a concentration 10 percent less that
the target standard. This aliquot is called the "low
standard. "
b. Six replicate analyses of each standard (a total of 18
analyses) must be performed in the following sequence: low
standard, target standard, high standard, low standard, target
standard, high standard, . . .
c. The mean and variance of the six results for each solution must
be calculated.
Equation 2
MEAN - (Y! + Y2 + Y3 + Y4 + Y5 + Y6 )/6
Equation 3
VARIANCE - (YX2 + Y22 + Y32 + Y42 + Y52 + Y62 - (6*MEAN)2)/5
The values Yj_, Y2, Y3 ..... represent the results of the six
analyses of each standard. The means of the low, target and
high standards are designated M]_, M2 and 113, respectively. The
variances of the low, target and high standards are designated
V^, V2 and V3, respectively. Additionally, a pooled variance,
Vp, is calculated.
Equation 4
vp - (Vi/(0.81) + V2 + V3 /(1.21))/3
If the square root of Vp is less than one percent of M2 , then
M22 /10.000 is to be used as the value of Vp in all subsequent
calculations .
E-20 DFIH01.0
-------
d. The test statistic must be calculated:
Equation 5
TEST STATISTIC - | (M3 /l.l) - (Mj. /0.9)|/(Vp /3)°'5
If the test statistic exceeds 2.13, the supplier has failed to
demonstrate a twenty percent difference between the high and
low standards. In such a case, the standards are not
acceptable.
e. The test statistic must be calculated:
Equation 6
TEST STATISTIC - |M2 - (Hi /I.8) - (M3 /2.2)|/(Vp /4)°'5
If the test statistic exceeds 2.13, the supplier has failed to
demonstrate that the target standard concentration is midway
between the high and low standards. In such a case, the
standards are not acceptable.
f. The 95 percent confidence intervals for the mean result of each
standard must be calculated:
Equation 7
Interval for Low Standard - MX ± (2.13)(Vp /6)°'5
Equation 8
Interval for Target Standard - M2 ± (2.13)(Vp /6)°'5
Equation 9
Interval for High Standard - M3 ± (2.13)(Vp /6)°'5
These intervals must not overlap. If overlap is observed, the
supplier has failed to demonstrate the ability to discriminate
the 10 percent difference in concentrations. In such a case,
the standards are not acceptable.
In any event, the Contractor is responsible for the quality of the
standards employed for analyses under this contract.
D. Requesting Standards From the EPA Standards Repository
Solutions of analytical reference materials can be ordered from the U.S.
EPA Chemical Standards Repository, depending on availability. The
Contractor can place an order for standards only after demonstrating
that these standards are not available from commercial vendors either in
solution or as a neat material.
E. Documentation of the Verification and Preparation of Chemical Standards
Each laboratory is responsible for maintaining the necessary
documentation to show that the chemical standards they have used in the
performance of CLP analysis conform to the requirements previously
listed. Weighing logbooks, calculations, chromatograms, mass spectra,
-}«-
E-21 DFLM01.0
-------
etc, whether produced by the laboratory or purchased from chemical
supply houses, must be maintained by the laboratory and may be subject
to review during on-site inspections. Documentation of standards
preparation may be required to be sent to EPA for verification of
contract compliance. In those cases where the documentation is
supportive of the analytical results of data packages sent to EPA, such
documentation is to be kept o.i file by the laboratory for a period of
one year.
E-22 DFLM01.0
-------
SECTION VI
CONTRACT COMPLIANCE SCREENING
Contract Compliance Screening (CCS) is one aspect of tue Government's
contractual right of inspection of analytical data. CCS examines the
Contractor's adherence to the contract requirements based on the sample data
package delivered to EPA.
CCS is performed by SMO under the direction of the EPA. To assure a uniform
review, a set of standardized procedures have been developed to evaluate the
sample data package submitted by a Contractor against the technical and
completeness requirements of the contract.
CCS results are mailed to the Contractor and all other data recipients. The
Contractor has a period of time to correct deficiencies. The Contractor must
send all corrections to the Regional client, EMSL-LV and SMO.
CCS results are used in conjunction with other information to measure overall
Contractor performance and to take appropriate actions to correct
deficiencies in performance.
E-23 DFLM01.0
-------
SECTION VII
REGIONAL DATA REVIEW
Contract laboratory data are generated to meet the specific needs of the
Regions. In order to verify the usability of data for the intended purpose,
each Region reviews data from the perspective of end-user, based upon
functional aspects of data quality. General guidelines for data review have
been developed jointly by the Region and the NPO. Each Region uses these
guidelines as the basis for data evaluation. Individual Regions may augment
the basic guideline review process with additional review based on Region-
specific or site-specific concerns. Regional reviews, like the sites under
investigation, vary based on the nature of the problems under investigation
and the Regional response appropriate to the specific circumstances.
Regional data reviews, relating usability of the data to a specific site, are
part of the collective assessment process. They complement the review done
at SMO, which is designed to identify contractual discrepancies, and the
review done at EMSL-LV which is designed to evaluate Contractor and method
performance. These individual evaluations are integrated into a collective
review that is necessary for program and laboratory administration and
management and may be used to take appropriate action to correct deficiencies
in the Contractor's performance.
E-24 DFLM01.0
-------
SECTION VIII
LABORATORY EVALUATION SAMPLES
Although intralaboratory QC may demonstrate Contractor and method performance
that can be tracked over time, an external performance evaluation program is
an essential feature of a QA program. As a means of measuring Contractor and
method performance, Contractors participate in interlaboratory comparison
studies conducted by the EPA. Results from the analysis of laboratory
evaluation samples will be used by the EPA to verify the Contractor's
continuing ability to produce acceptable analytical data. The results are
also used to assess the precision and accuracy of the analytical methods for
specific analytes.
Sample sets may be provided to participating Contractors as frequently as on
a SDG-by-SDG basis as a recognizable QC sample of known composition, as a
recognizable QC sample of unknown composition, or not recognizable as a QC
material. Laboratory evaluation samples may be sent either by the Regional
client or the NPO and may be used for contract action.
Contractors are required to analyze the samples and return the data package
and all raw data within the contract required turnaround time.
At a minimum, the results are evaluated for compound identification,
quantification, and sample contamination. Confidence intervals for the
quantification of target compounds are based on reported values using
population statistics. EPA may adjust the scores on any given laboratory
evaluation sample to compensate for unanticipated difficulties with a
particular sample. Normally, a fraction of the compounds spiked into the
sample are not specifically listed in the contract.
A Contractor's results on the laboratory evaluation samples will determine
the Contractor's performance as follows:
1. Acceptable, No Response Required (Score greater than or equal to 90
percent):
Data meets most or all of the scoring criteria. No response is
required.
2. Acceptable, Response Explaining Deficiency(ies) Required (Score greater
than or equal to 75 percent but less than 90 percent):
Deficiencies exist in the Contractor's performance.
Within 14 days of receipt of notification from EPA, the Contractor shall
describe the deficiency(ies) and the action(s) taken to correct the
deficiency(ies) in a letter to the APO, the TPO and EMSL-LV.
E-25 ' DFLM01.0
-------
3. Unacceptable Performance, Response Explaining Deficiency(ies) Required
(Score less than 75 percent):
Deficiencies exist in the Contractor's performance to the extent that
the NPO has determined that the Contractor has not demonstrated the
capability to meet the contract requirements.
Within 14 days of receipt of notification from EPA, the Contractor shall
describe the deficiency(ies) and the action(s) taken to correct the
deficiency(ies) in a letter to the APO, the TPO and EMSL-LV.
The Contractor shall be notified by the APO or TPO concerning the remedy
for their unacceptable performance. A Contractor may expect, but EPA is
not limited to, the following actions: reduction of the number of
samples sent under the contract, suspension of sample shipment to the
Contractor, an on-site audit, a full data audit, analysis of remedial PE
samples, and/or a contract sanction, such as a Cure Notice.
NOTE: A Contractor's prompt response demonstrating that corrective
actions have been taken to ensure the Contractor's capability to
meet contract requirements will facilitate continuation of full
sample delivery.
E-26 DFLM01.0
-------
SECTION IX
GC/MS TAPE AUDITS
Periodically, EPA requests from Contractors the GC/MS magnetic tapes
corresponding to a specific Case in order to accomplish tape audits.
Generally, tape submissions and audits are requested for the following
reasons:
o Program overview.
o Indication of data quality problems from EMSL-LV, SMO, or Regional
data reviews.
o Support for on-site audits.
o Specific Regional requests.
Depending upon the reason for an audit, the tapes from a recent Case, a
specific Case, or a laboratory evaluation sample may be requested. Tape
audits provide a mechanism to assess adherence to contractual requirements
and ensure the consistency of data reported on the hardcopy forms with that
generated on the GC/MS tapes. This function provides external monitoring of
CLP QC requirements and checks adherence of the Contractor to internal QA
procedures. In addition, tape audits enable EPA to evaluate the utility,
precision and accuracy of the analytical methods.
The GC/MS tape shall include raw data and quantitation reports for samples,
blanks, laboratory evaluation samples, initial calibrations, and continuing
calibrations associated with the SDG requested. The specific requirements
for submissions of GC/MS tapes are discussed in Exhibit B.
Upon request of the APO or EMSL-LV, the required tapes and all necessary
documentation shall be submitted to EPA within seven days of notification.
E-27 DFLM01.0
-------
SECTION X
ON-SITE LABORATORY EVALUATIONS
At a frequency dictated by a Contractor's performance, the APO, TPO or their
authorized representative will conduct an on-site laboratory evaluation. On-
site laboratory evaluations are carried out to monitor the Contractor's
ability to meet selected terms and conditions specified in the contract. The
evaluation process incorporates two separate categories: a QA evaluation and
an evidentiary audit.
A. Quality Assurance Evaluation
QA evaluators inspect the Contractor's facilities to verify the
adequacy and maintenance of instrumentation, the continuity of
personnel meeting experience or education requirements, and the
acceptable performance of analytical and QC procedures. The Contractor
should expect that items to be monitored will include, but not be
limited to, the following items:
o Size and appearance of the facility.
o Quantity, age, availability, scheduled maintenance and
performance of instrumentation.
o Availability, appropriateness, and utilization of SOPs.
o Staff qualifications, experience, and personnel training
programs.
o Reagents, standards, and sample storage facilities.
o Standard preparation logbooks and raw data.
o Bench sheets and analytical logbook maintenance and review.
o Review of the Contractor's sample analysis/data package
inspection procedures.
Prior to an on-site evaluation, various documentation pertaining to
performance of the specific Contractor is integrated in a profile
package for discussion during the evaluation. Items that may be
included are previous on-site reports, laboratory evaluation sample
scores, Regional review of data, Regional QA materials, GC/MS tape
audit reports, results of CCS, and date trend reports.
B. Evidentiary Audit
Evidence auditors conduct an on-site laboratory evaluation to determine
if laboratory policies and procedures are in place to satisfy evidence
handling requirements as stated in Exhibit F. The evidence audit is
comprised of the following three activities:
**" E-28 DFLM01.0
-------
1. Procedural Audit
The procedural audit consists of review and examination of actual SOPs
and accompanying documentation for the following laboratory operations:
sample receiving, sample storage, sample identification, sample
security, sample tracking (from receipt to completion of analysis), and
analytical project file organization and assembly.
2. Written SOPs Audit
The written SOPs audit consists of review and examination of the
written SOPs to determine if they are accurate and complete for the
following laboratory operations: sample receiving, sample storage,
sample identification, sample security, sample tracking (from receipt
to completion of analysis), and analytical project file organization
and assembly.
3. Analytical Project File Evidence Audit
The analytical project file evidence audit consists of review and
examination of the analytical project file documentation. The auditors
review the files to determine:
o Accuracy of the document inventory.
o Completeness of the file.
o Adequacy and accuracy of the document numbering system.
o Traceability of sample activity.
o Identification of activity recorded on the documents.
o Error correction methods.
C. Discussion of the On-Site Team's Findings
The QA and evidentiary auditors discuss their findings with the APO/TPO
prior to debriefing the Contractor. During the debriefing, the
auditors present their findings and recommendations for corrective
actions necessary to the Contractor personnel.
D. Corrective Action Reports For Follow-Through to Quality Assurance and
Evidentiary Audit Reports
Following an on-site evaluation, QA and evidentiary audit reports which
discuss deficiencies found during the on-site evaluation will be
forwarded to the Contractor. The Contractor must discuss the
corrective actions taken to resolve the deficiencies discussed during
the on-site visit and discussed in the on-site reports in a letter to
the APO, TPO, EMSL-LV (response to the QA report) and NEIC (response to
the evidentiary report) within 14 days of receipt of the finding or
within the time agreed upon between the APO/TPO and the Contractor. If
SOPs are required to be written or amended, the Contractor must provide
E-29 DFLM01.0
-------
the SOPs to the TPO, EMSL-LV (QA/technical SOPs) and NEIC (evidentiary
SOPs) within 30 days of receipt of the finding or within the time
agreed upon between the APO/TPO and the Contractor.
If the Contractor fails to take appropriate corrective action to
resolve the deficiencies discussed in the on-site reports, a Contractor
may expect, but the Government is not limited to, the following
actions: reduction of the number of samples sent under the contract,
suspension of sample shipment to the Contractor, a follow-up site
visit, a full data audit, analysis of remedial PE samples and/or
contract sanction, such as a Cure Notice.
E-30 , DFLM01.0
-------
SECTION XI
QUALITY ASSURANCE AND DATA TREND ANALYSIS
Data submitted by laboratories are subject to review from several aspects:
compliance with contract-required QC, usability, and full data package
evaluation. Problems resulting from any of these reviews may determine the
need for a GC/MS tape audit, an on-site laboratory evaluation and/or a
remedial laboratory evaluation sample. In addition, QC prescribed in the
methods provides information that is continually used by EPA to assess sample
data quality, Contractor data quality and CLP data quality via data trend
analysis. Trend analysis is accomplished by entering data into a
computerized database. Statistical reports that evaluate specific anomalies
or disclose trends in many areas, including the following, are generated from
this database:
o Internal standard recovery.
o Laboratory evaluation sample.
o Blanks.
o Gas chromatographic resolution of analytes.
o Initial and continuing calibration data.
o Other QC and method parameters.
Program-wide statistical results are used to rank laboratories in order to
observe the relative performance of each Contractor using a given protocol
against its peers. The reports are also used to identify trends within
laboratories. The results of many of these trends analyses are included in
overall evaluation of a Contractor's performance, and are reviewed to
determine if corrective action or an on-site laboratory evaluation is
indicated in order to meet the QA/QC requirements of the contract.
Contractor performance over time is monitored using these trend analysis
techniques to detect departures of Contractor output from required or desired
levels of QC, and to provide an early warning of Contractor QA/QC problems
which may not be apparent from the results of an individual case.
As a further benefit to the CLP, the database provides the information needed
to establish performance-based criteria in updated analytical protocols,
where advisory criteria has been previously used. The vast empirical data
set produced by contract laboratories is carefully analyzed, with the results
augmenting theoretical and research-based performance criteria. The result
is a continuously monitored set of QC and performance criteria specifications
of what is routinely achievable and expected of environmental chemistry
laboratories in mass production analysis of environmental samples. This
information, in turn, assists EPA in meeting its objectives of obtaining data
of known and documented quality.
E-31 DFLM01.0
-------
SECTION XII
DATA MANAGEMENT
Data management procedures are defined as procedures specifying the
acquisition or entry, update, correction, deletion, storage and security of
computer-readable data and files. These procedures should be in written form
and contain a clear definition for all databases and files used to generate
or resubmit deliverables. Key areas of concern include: system organization
(including personnel and security), documentation operations, traceability
and QC.
Data manually entered from hardcopy must be quality controlled and the error
rates estimated. Systems should prevent entry of incorrect or out-of-range
data and alert data entry personnel of errors. In addition, data entry error
rates must be estimated and recorded on a monthly basis by reentering a
statistical sample of the data entered and calculating discrepancy rates by
data element.
The record of changes in the form of corrections and updates to data
originally generated, submitted, and/or resubmitted must be documented to
allow traceability of updates. Documentation must include the following for
each change:
o Justification or rationale for the change.
o Initials of the person making the change or changes. Data changes
must be implemented and reviewed by a person or group independent of
the source generating the deliverable.
o Change documentation must be retained according to the schedule of
the original deliverable.
o Resubmitted deliverables must be reinspected as a part of the
laboratory's internal inspection process prior to resubmission. The
entire deliverable, not just the changes, must be inspected.
o The Laboratory Manager must approve changes to originally submitted
deliverables.
o Documentation of data changes may be requested by laboratory
auditors.
Life cycle management procedures must be applied to computer software systems
developed by the laboratory to be used to generate and edit contract
deliverables. Such systems must be thoroughly tested and documented prior to
utilization.
o A software test and acceptance plan including test requirements,
test results and acceptance criteria must be developed, followed,
and available in written form.
o System changes must not be made directly to production systems
generating deliverables. Changes must be made first to a
development system and tested prior to implementation.
*" E-32 DFLM01.0
-------
o Each version of the production system will be given an
identification number, a date of installation, and a date of last
operation, and will be archived.
o System and operations documentation must be developed and maintained
for each system. Documentation must include a user's manual and an
operations and maintenance manual.
Individual(s) responsible for the following functions must be identified:
o System operation and maintenance including documentation and
training.
o Database integrity, including data entry, data updating and quality
control.
o Data and system security, backup and archiving.
E-33 DFLM01.0
-------
REFERENCES
1. Fisk, J.F. and Manzo, S.M. "Quality Assurance/Quality Control in
Organics Analysis," Proceedings from the Water Pollution Control
Federation Meeting, May 1986.
2. Office of Monitoring Systems and Quality Assurance, U.S. Environmental
Protection Agency, "Interim Guidelines and Specifications for Preparing
Quality Assurance Project Plans," QAMS-005/80, December 1980.
3. Office of Solid Waste and Emergency Response, U.S. Environmental
Protection Agency, Test Methods for Evaluating Solid Waste, Third
Edition, SW-846, November 1986.
4. Laidlaw, R.H., "Document Control and Chain of Custody Considerations for
the National Contract Laboratory Program," Quality Control in Remedial
Site Investigations: Hazardous and Industrial Solid Waste Testing,
Fifth Volume, ASTM STP 925, C.L. Perket, ed., American Society for
Testing and Materials, Philadelphia, 1986.
5. Health Effects Research Laboratory, U.S. Environmental Protection
Agency, Manual of Analytical Methods for the Analysis of Pesticides in
Humans and Environmental Samples, EPA-600/8-80-036, June 1980.
6. Environmental Protection Agency, "Guidelines Establishing Test
Procedures for the Analysis of Pollutants Under the Glean Water Act;
Final Rule and Interim Final Rule and Proposed Rule," 40 CFR Part 136,
Federal Register, Vol. 49, No. 209, pp. 43234-43442, October 26, 1984.
7. Health Effects Research Laboratory, U.S. Environmental Protection
Agency, Manual of Analytical Quality Control for Pesticides and Related
Compounds in Human and Environmental Samples-Second Revision, EPA-600/2-
81-059, April 1981.
8. Environmental Monitoring Systems Laboratory, U.S. Environmental
Protection Agency, Analytical Reference Standards and Supplemental Data:
The Pesticides and Industrial Chemicals Repository, EPA-600/4-84-082,
October 1984.
9. American Chemical Society Committee on Environmental Improvement, and
Subcommittee on Environmental Analytical Chemistry, "Guidelines for Data
Acquisition and Data Quality Evaluation in Environmental Chemistry,"
Analytical Chemistry, Volume 52, Number 14, December 1980.
10. Moore, J.M. and Pearson, J.G. "Quality Assurance Support for the
Superfund Contract Laboratory Program," Quality Control in Remedial Site
Investigation: Hazardous and Industrial Solid Waste Testing, Fifth
Volume, ASTM STP 925, C.L. Perket, ed., American Society for Testing and
Materials, Philadelphia, 1986.
E-34 DFLM01.0
-------
EXHIBIT F
CHAIN-OF-CUSTODY, DOCUMENT CONTROL,
AND STANDARD OPERATING PROCEDURES
DFLM01.0
-------
Table of Contents
Page
1. Sample Chain-of-Custody F-3
2. Document Control Procedures F-5
3. Specifications for Written Standard Operating Procedures F-7
4. Handling of Confidential Information F-9
F-2 DFLM01.0
-------
1. Sample Chain-of-Custodv
A sample is physical evidence collected from a facility or from the
environment. Controlling evidence is an essential part of the
hazardous waste investigation effort. To accomplish this task,
Contractors are required to develop and implement the following sample
identification, chain-of-custody, sample receiving, and sample tracking
procedures.
1.1 Sample Identification
To assure traceability of the samples while in the possession of the
Contractor, the Contractor shall have a specified method for
maintaining identification of samples throughout the laboratory. Each
sample and sample preparation container shall be labeled with the EPA
number or a unique laboratory identifier. If a unique laboratory
identifier is used, it shall be cross-referenced to the EPA number.
1.2 Chain-of-Custody Procedures
Because of the nature of the data being collected, the custody of EPA
samples must be traceable from the time the samples are collected until
they are introduced as evidence in legal proceedings. The Contractor
shall have procedures ensuring that EPA sample custody is maintained
and documented. A sample is under custody if:
o It is in your possession, or
o It is in your view after being in your possession, or
o It was in your possession and you locked it up, or
o It is in a designated secure area. (Secure areas shall be
accessible only to authorized personnel.)
1.3 Sample Receiving Procedures
1.3.1 The Contractor shall designate a sample custodian responsible
for receiving all samples.
1.3.2 The Contractor shall designate a representative to receive
samples in the event that the sample custodian is not
available.
1.3.3 The condition of the shipping containers and sample bottles
shall be inspected upon receipt by the sample custodian or
his/her representative.
1.3.4 The condition of the custody seals (intact/not intact) shall be
inspected upon receipt by the sample custodian or his/her
representative.
1.3.5 The sample custodian or his/her representative shall check for
the presence or absence of the following documents accompanying
the sample shipment:
F-3 DFLM01.0
-------
o Airbills or airbill stickers
o Custody seals
o EPA custody records
o Sample Traffic Reports or SAS Packing Lists
o Sample tags
1.3.6 The sample custodian or his/her representative shall sign and
date all forms (e.g., custody records, Traffic Reports or
Packing Lists, and airbills) accompanying the samples at the
time of sample receipt.
1.3.7 The Contractor shall contact the Sample Management Office (SMO)
to resolve discrepancies and problems such as absent documents,
conflicting information, broken custody seals, and
unsatisfactory sample condition (e.g., leaking sample bottle).
1.3.8 The Contractor shall record the resolution of discrepancies and
problems on Telephone Contact Logs.
1.3.9 The following information shall be recorded on Form DC-1 (see
Exhibit B) by the sample custodian or his/her representative as
samples are received and inspected:
o Condition of the shipping container.
o Presence or absence and condition of custody seals on
shipping and/or sample containers.
o Custody seal numbers, when present.
o Condition of the sample bottles.
o Presence or absence of airbills or airbill stickers.
o Airbill or airbill sticker numbers.
o Presence or absence of EPA custody records.
o Presence or absence of Traffic Reports or SAS Packing
Lists.
o Presence or absence of sample tags.
o Sample tag identification numbers cross-referenced to
the EPA sample numbers.
o Verification of agreement or non-agreement of
information recorded on shipping documents and sample
containers.
o Problems or discrepancies.
1.4 Sample Tracking Procedures
The Contractor shall maintain records documenting all phases of sample
handling from receipt to final analysis.
F-4 DFLM01.0
-------
2. pnfMimt»nt Control Procedures
The goal of the laboratory document control program is to assure that
all documents for a specified Sample Delivery Group (SDG) will be
accounted for when the project is completed. Accountable documents
used by contract laboratories shall include, but not be limited to,
logbooks, chain-of-custody records, sample work sheets, bench sheets,
and other documents relating to the sample or sample analysis. The
following document control procedures have been established to ensure
that all laboratory records are assembled and stored for delivery to
EPA or are available upon request from EPA prior to the delivery
schedule.
2.1 Preprinted Laboratory Forms and Logbooks
2.1.1 All documents produced by the Contractor that are directly
related to the preparation and analysis of EPA samples shall
become the property of EPA and shall be placed in the Complete
SDG File (CSF). All observations and results recorded by the
laboratory but not on preprinted laboratory forms shall be
entered into permanent laboratory logbooks. When all data from
a SDG are compiled, all original laboratory forms and copies of
all SDG-related logbook entries shall be included in the
documentation package.
2.1.2 The Contractor shall identify the activity recorded on all
laboratory documents that are directly related to the
preparation and analysis of EPA samples.
2.1.3 Pre-printed laboratory forms shall contain the name of the
laboratory and be dated (month/day/year) and signed by the
person responsible for performing the activity at the time an
activity is performed.
2.1.4 Logbook entries shall be dated (month/day/year) and signed by
the person responsible for performing the activity at the time
an activity is performed.
2.1.5 Logbook entries shall be in chronological order. Entries in
logbooks, with the exception of instrument run logs and
extraction logs, shall include only one SDG per page.
2.1.6 Pages in both bound and unbound logbooks shall be sequentially
numbered.
2.1.7 Instrument run logs shall be maintained so as to enable a
reconstruction of the run sequence of individual instruments.
Because the laboratory must provide copies of the instrument
run logs to EPA, the laboratory may exercise the option of
using only laboratory or EPA sample identification numbers in
the logs for sample ID rather than government agency or
commercial client names to preserve the confidentiality of
commercial clients.
F-5 DFLM01.0
-------
2.1.8 Corrections to supporting documents and raw data shall be made
by drawing a single line through the error and entering the
correct information. Corrections and additions to supporting
documents and raw data shall be dated and initialed. No
information shall be obliterated or rendered unreadable.
All notations shall be recorded in ink. Unused portions of
documents shall be "z'd" out.
2.2 Consistency of Documentation
The Contractor shall assign a Document Control Officer (DCO)
responsible for the organization and assembly of the CSF. All copies
of laboratory documents shall be complete and legible.
Original documents which include information relating to more than one
SDG shall be filed in the CSF of the lowest SDG number. The copy(ies)
shall be placed in the other CSF(s), and the Contractor shall record
the following information on the copy(ies) in red ink:
"COPY - ORIGINAL IS FILED IN CSF
The Contractor shall sign and date this addition to the copy(ies).
Before releasing analytical results, the DCO shall assemble and cross-
check the information on samples tags, custody records, lab bench
sheets, personal and instrument logs, and other relevant deliverables
to ensure that data pertaining to each particular sample or SDG are
consistent throughout the CSF.
2.3 Document Numbering and Inventory Procedure
In order to provide document accountability of the completed analysis
records, each item in the CSF shall be inventoried and assigned a
serialized number as described in Exhibit B.
All documents relevant to each SDG, including logbook pages, bench
sheets, mass spectra, chromatograms, screening records, re-preparation
records, reanalysis records, records of failed or attempted analysis,
custody records, library research results, etc., shall be inventoried.
The DCO shall be responsible for ensuring that all documents generated
are placed in the CSF for inventory and are delivered to the
appropriate EPA Region or other receiver as designated by EPA. The DCO
shall place the sample tags in plastic bags in the file.
2.4 Storage of EPA Files
The Contractor shall maintain EPA laboratory documents in a secure
location.
F-6 DFLM01.0
-------
2.5 Shipment of Deliverables
The Contractor shall document shipment of deliverables packages to the
recipients. These shipments require custody seals on the containers
placed such that the containers cannot be opened without damaging or
breaking the seal. The Contractor shall document what was sent, to
whom, the date, and the method (carrier) used. A copy of the
transmittal letter for the CSF shall be sent to the National
Enforcement Investigations Center and SMO.
3. Specifications for Written Standard Operating Procedures
The Contractor shall have written standard operating procedures (SOPs)
for receipt of samples, maintenance of custody, sample identification,
sample storage, sample tracking, and assembly of completed data. A SOP
is defined as a written narrative stepwise description of laboratory
operating procedures including examples of laboratory documents. The
SOPs shall accurately describe the actual procedures used in the
laboratory, and copies of the written SOPs shall be available to the
appropriate laboratory personnel. These procedures are necessary to
ensure that analytical data produced under this contract are acceptable
for use in EPA enforcement case preparation and litigation. The
Contractor's SOPs shall provide mechanisms and documentation to meet
each of the following specifications and shall be used by EPA as the
basis for laboratory evidence audits.
3.1 The Contractor shall have written SOPs describing the sample
custodian's duties and responsibilities.
3.2 The Contractor shall have written SOPs for receiving and logging in of
the samples. The procedures shall include, but not be limited to,
documenting the following information:
3.2.1 Presence or absence of EPA chain-of-custody forms.
3.2.2 Presence or absence of airbills or airbill stickers.
3.2.3 Presence or absence of Traffic Reports or SAS Packing Lists.
3.2.4 Presence or absence of custody seals on shipping and/or sample
containers and their condition.
3.2.5 Custody seal numbers, when present.
3.2.6 Airbill or airbill sticker numbers.
3.2.7 Presence or absence of sample tags.
3.2.8 Sample tag ID numbers.
3.2.9 Condition of the shipping container.
3.2.10 Condition of the sample bottles.
*- F-7 DFLM01.0
-------
3.2.11 Verification of agreement or non-agreement of information on
receiving documents and sample containers.
3.2.12 Resolution of problems or discrepancies with SMO.
3.2.13 An explanation of any terms used by the laboratory to describe
sample condition upon receipt (e.g., good, fine, OK).
3.3 The Contractor shall have written SOPs for maintaining identification
of EPA samples throughout the laboratory. If the Contractor assigns
unique laboratory identifiers, written SOPs shall include a description
of the method used to assign the unique laboratory identifier and shall
include a description of the document used to cross-reference the
unique laboratory identifier to the EPA sample number.. If the
Contractor uses prefixes or suffixes in addition to sample
identification numbers, the written SOPs shall include their
definitions.
3.4 The Contractor shall have written SOPs describing all storage areas for
samples in the laboratory. The SOPs shall include a list of authorized
personnel who have access or keys to secure storage areas.
3.5 The Contractor shall have written SOPs describing the method by which
the laboratory maintains samples under custody.
3.6 The Contractor shall have written SOPs describing the method by which
the laboratory maintains the security of any areas identified as
secure.
3.7 The Contractor shall have written SOPs for tracking the work performed
on any particular samples. The tracking SOP shall include:
o A description of the documents used to record sample receipt,
sample storage, sample transfers, sample preparations, and
sample analyses.
o A description of the documents used to record calibration and
QA/QC laboratory work.
o Examples of document formats and laboratory documents used in
the sample receipt, sample storage, sample transfer, and sample
analyses.
o A narrative step-wise description of how documents are used to
track samples.
3.8 The Contractor shall have written SOPs for organization and assembly of
all documents relating to each SDG. Documents shall be filed on a SDG-
specific basis. The procedures shall ensure that all documents
including logbook pages, sample tracking records, chromatographic
charts, computer printouts, raw data summaries, correspondence, and any
other written documents having reference to the SDG are compiled in one
location for submission to EPA. The written SOPs shall include:
o A description of the numbering and inventory method.
— F-8 DFLM01.0
-------
o A description of the method used by the laboratory to verify
consistency and completeness of the CSF.
o Procedures for the shipment of deliverables packages using
custody seals.
4. Handling of Confidential Information
A Contractor conducting work under this contract may receive
confidential information from EPA. Confidential information must be
handled separately from other documentation developed under this
contract. To accomplish this, the following procedures for the
handling of confidential information have been established.
4.1 All confidential documents shall be under the supervision of a
designated DCO.
4.2 Any samples or information received with a request of confidentiality
shall be handled as "confidential." A separate locked file shall be
maintained to store this information and shall be segregated from other
nonconfidential information. Data generated from confidential samples
shall be treated as confidential. Upon receipt of confidential
information, the DCO will log these documents into a Confidential
Inventory Log. The information will then be available to authorized
personnel but only after it has been signed out to that person by the
DCO. The documents shall be returned to the locked file at the
.conclusion of each working day. Confidential information may not be
reproduced except upon approval by the Technical Project Officer and
Administrative Project Officer. The DCO will enter all copies into the
document control system described above. In addition, this information
may not be disposed of except upon approval by the Technical Project
Officer and Administrative Project Officer. The DCO shall remove and
retain the cover page of any confidential information disposed of for
one year and shall keep a record on the disposition in the Confidential
Inventory Log.
F-9 DFLM01.0
-------
EXHIBIT G
GLOSSARY
DFLM01.0
-------
GLOSSARY
ALIQUOT - a measured portion of a sample taken for analysis.
ANALYSIS DATE/TIME - the date and military time of the injection of the
sample, standard or blank into the GC/MS or GC system.
BLANK - see Method Blank.
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.
CONCENTRATION CALIBRATION SOLUTION (Table 3) - solutions (tridecane)
containing known amounts of selected analytes, five internal standards and
two recovery standards that are analyzed prior to sample analysis. The
solutions are used to determine the ratio of the instrument response of the
analytes to that of the appropriate internal standard and the internal
standards to that of the recovery standards.
CONTINUING CALIBRATION SOLUTION - a mixture of known amounts of analytes that
is analyzed every 12 hours to demonstrate continued acceptable GC/MS
performance and establish the retention time windows for each homologue. The
same solution is used for the mid-level concentration calibration solution,
CC3.
DAY - unless otherwise specified, day shall refer to calendar day.
ESTIMATED DETECTION LIMIT (EDL) - the concentration of a analyte required to
produce a signal with peak height of at least 2.5 times the background signal
level. The EDL is calculated for each 2,3,7,8-substituted isomer for which
the response of the quantitation and confirmation ions is less than 2.5 times
the background level.
ESTIMATED MAXIMUM POSSIBLE CONCENTRATION (EMPC) - the concentration of a
given analyte that would produce a signal with a given peak area. The EMPC
is calculated for 2,3,7,8-substituted isomers for which the quantitation
and/or the confirmation ion(s) has signal-to-noise in excess of 2.5 but does
not meet identification criteria.
FIELD BLANK - a portion of chemical waste, soil or water that is not
contaminated with PCDDs/PCDFs and is submitted with the samples. The field
blank is used to check for contamination from the time of sample collection
through the time of sample analysis.
HOMOLOGUE - a member or members of a particular homologous series that has
the same molecular weight but not necessarily the same structural
arrangement. For example, the 28 pentachlorinated dibenzofurans are
homologues.
G-2 DFLM01.0
-------
HOMOLOGOUS SERIES - a series of organic compounds in which each successive
member has one more atom or group of atoms than the preceding member. The
straight chain hydrocarbons and the polychlorinated dibenzo-p-dioxins are
examples of a homologous series.
IN-HOUSE - at the Contractor's facility.
INITIAL CALIBRATION - analysis of analytical standards for a series of
different specified concentrations. The initial calibration used to define
the linearity and dynamic range of the response of the mass spectrometer to
the target compounds.
INTERNAL STANDARDS (Tables 2 and 4) - 13C12-2378-TCDD, 13C12-123678-HxCDD,
13C12-OCDD, 13C12-2378-TCDF atld C12-1234678-HpCDF (in isooctane) are added
to every sample and are present at the same concentration in every blank,
quality control sample, and concentration calibration solution. The internal
standards are added to the sample before extraction and are used to measure
the concentrations of the analytes.
ISOMER - chemical compounds that contain the same number of atoms of the same
elements, but differ in structural arrangement and properties. For example,
1234-TCDD and 2378-TCDD are structural isomers.
LABORATORY - synonymous with the term Contractor.
LOW RESOLUTION MASS SPECTROMETRY - a mass spectrometric technique capable of
achieving unit mass (i.e., 1 amu) resolution between compounds introduced
into the instrument.
MATRIX - the predominant material that comprises the sample to be analyzed.
For the purpose of this contract, a sample matrix may be water, soil or
chemical waste (including stillbottoms, fuel oil, sludge and fly ash). Matrix
is not synonymous with phase (liquid or solid).
METHOD BLANK (previously termed reagent blank) - an analytical control
consisting of all reagents, internal standards and surrogate standards that
is carried through the entire analytical procedure. The method blank is used
to define the level of laboratory background contamination.
NARRATIVE (SDG Narrative) - the portion of the data package which includes
laboratory, contract, Case and sample number identification, and descriptive
documentation of any problems encountered in processing the samples, along
with corrective action taken and problem resolution. Complete SDG Narrative
specifications are included in Exhibit B.
PERCENT MOISTURE - an approximation of the amount of water in a soil/sediment
sample made by drying an aliquot of the sample at 105°C. The percent
moisture determined in this manner also includes contributions from all
compounds that may volatilize at 105°C, including water. Percent moisture is
determined from decanted samples and from samples that are not decanted.
PERFORMANCE EVALUATION (PE) SAMPLE - a chemical waste, soil or water sample
containing known amounts of unlabeled PCDDs/PCDFs.
G-3 DFLM01.0
-------
POLYCHLORINATED DIBENZO-P-DIOXINS (PCDDs) AND POLYCHLORINATED DIBENZOFURANS
(PCDFs) - compounds (Figure 2) that contain from one to eight chlorine atoms.
The 15 2,3,7,8-substituted PCDDs (total PCDDs is 75) and PCDFs (total PCDFs
is 135) are shown in Table 13. The number of isomers at different
chlorination levels is shown in Table 12.
PROTOCOL - describes the exact procedures to be followed with respect to
sample receipt and handling, analytical methods, data reporting and
deliverables, and document control. Synonymous with Statement of Work (SOW).
REAGENT WATER - water in which an interferent is not observed at or above the
minimum quantitation limit of the parameters of interest.
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
%Recovery - -, ? x 100%
J known value
RECOVERY STANDARD (Table 9) - 13Ci2-1234-TCDD and 13Ci2-123789-HxCDD are
added to every blank, quality control sample, and sample extract aliquot just
prior to analysis and are present in all solutions except the internal
standards solutions. Recovery standards are used to measure the recovery of
the internal standards. When a dilution is required (see Exhibit D,
Paragraph 13.2.5), recovery standards are used to quantitate the native
PCDDs/PCDFs; the TCDD recovery standard is used to quantitate the tetra- and
penta- isomers and the HxCDD recovery standard is used to quantitate the
hexa- through octa- isomers.
RELATIVE RESPONSE FACTOR (RRF) - the ratio of the response of the mass
spectrometer to a known amount of an analyte relative to that of a known
amount of an internal standard as measured in the initial and continuing
calibrations. The RRF is used to determine instrument performance and is
used in the quantitation calculations.
RESOLUTION (also termed separation) - the separation between peaks on a
chromatogram. Resolution is calculated by dividing the height of the valley
between the peaks by the peak height of the smaller peak being resolved,
multipled by 100.
RINSATE - a portion of the solvent that is used to rinse sampling equipment.
The rinsate is later analyzed to demonstrate that samples were not
contaminated during collection.
SAMPLE - a portion of material to be analyzed that is contained in single or
multiple containers and identified by a unique sample number.
SAMPLE DELIVERY GROUP (SDG) - a unit within a single Case that is used to
identify a group of samples for delivery. A 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 a SDG are due concurrently. A SDG is defined by one
of the following, whichever occurs first:
G-4 DFLM01.0
-------
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.
Samples may be assigned to SDGs by matrix (i.e., all soils in one SDG, all
waters in another), at the discretion of the laboratory.
SAMPLE NUMBER (EPA Sample Number) - a unique identification number designated
by EPA for each sample. The EPA sample number appears on the sample Traffic
Report which documents information on that sample.
SELECTED ION MONITORING - a mass spectrometric technique whereby ions with
predetermined mass/charge ratios (m/z) are monitored, as opposed to scanning
MS procedures in which all m/z's between two limits are monitored.
SIGNAL-TO-NOISE (S/N) RATIO - the ratio of analyte signal to random
background signal. To determine the ratio, display each characteristic ion
using a window 100 scans wide, and draw a base line from the lowest point in
the 100 scan window. The noise is defined as the height of the .largest
signal (excluding signal due to PCDDs/PCDFs or other chemicals) within the
100 scan window. The signal is defined as the height of the PCDD/PCDF peak.
If the data system determines the ratio, the Contractor shall demonstrate
comparability between the above criteria and the automated S/N determination.
Chemical noise is left to the judgement of the analyst.
SOIL - synonymous with soil/sediment and sediment.
STANDARD ANALYSIS - an analytical determination made with known quantities of
target compounds. The standard analysis is used to determine response
factors.
SURROGATES (Surrogate Standard) - the compounds added to every blank, sample,
matrix spike, matrix spike duplicate, and standard. Surrogates are used to
evaluate analytical efficiency by measuring recovery. Surrogates are
brominated, fluorinated, or isotopically labelled compounds not expected to
be detected in environmental media.
TIME - when recording time on any deliverable item, time shall be expressed
as military time, (i.e., a 24-hour clock).
TOXICITY EQUIVALENCY FACTOR (TEF) - a method of converting concentrations of
PCDDs/PCDFs to an equivalent concentration of 2378-TCDD to obtain an
estimation of the toxicity of the entire sample. (Update of Toxicity
Equivalency Factors (TEFs) for Estimating Risks Associated with Exposures to
Mixtures of Chlorinated Dibenzo-p-Dioxins and Dibenzofurans (CDDs/CDFs),
March 1989, (EPA 625/3-89/016).
TRAFFIC REPORT (TR) - an EPA sample identification form filled out by the
sampler, which accompanies the sample during shipment to the laboratory and
documents sample condition and receipt by the laboratory.
G-5 DFLM01.0
-------
TWELVE-HOUR TIME PERIOD - the 12-hour time period begins with the injection
of the CCS solution on the DB-5 (or equivalent) column or the injection of
the column performance solution on the SP-2331 (or equivalent) column. The
12-hour period continues until 12:00 hours have elapsed according to the
system clock. To be included in a given 12-hour time period, a sample or
standard must be injected within 12:00 hours of the CCS solution or the
column performance solution.
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.
G-6 DFLM01.0
------- |