SERA
United States
Environmental Protection
Agency
Office of
Solid Waste and
Emergency Response
OSWER Document 9240.1-48FS
EPA Publication 540-F-05-003
Final - September 2005
Multi-Media, Multi-Concentration
Dioxin and Furan Analytical Service
for Superfund (DLM02.0)
Office of Superfund Remediation and Technology Innovation (OSRTI)
Analytical Services Branch (ASB) (5102G)
Quick Reference Fact Sheet
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. Among the pollutants that are of
concern to the EPA at such sites are a series of chlorinated dibenzo-p-dioxins (CDDs) and chlorinated dibenzofurans
(CDFs) that are analyzed using High Resolution Gas Chromatography/High Resolution Mass Spectrometry
(HRGC/HRMS). The Analytical Services Branch (ASB) of EPA's Office of Superfund Remediation and Technology
Innovation (OSRTI) offers an analytical service that provides data from the analysis of water, soil, sediment, sludge,
non-human tissue, ash, oil, and oily matrices for use in the Superfund decision-making process. Through a series of
standardized procedures and a strict chain-of-custody, the dioxin and furan analytical service produces data of known
and documented quality.
DESCRIPTION OF SERVICES
The dioxin and furan analytical service provides a
flexible contractual framework for laboratories to apply
EPA analytical methods for the isolation, detection, and
quantitative measurement of seventeen 2,3,7,8-
substituted tetra- through octa- CDDs/CDFs in water,
soil, sediment, sludge, non-human tissue, ash, oil, and
oily matrices. EPA ASB has prequalified laboratories
that use the Dioxin and Furan Statement of Work
(SOW) DLM02.0 to provide this service. Data
evaluation can be performed by the data requestor using
the National Functional Guidelines (NFG) document
provided by EPA ASB. The standard data Turnaround
Time (TAT) for this service is 35 days after laboratory
receipt of the last sample in the Sample Delivery Group
(SDG). This TAT can be changed to meet project-
specific requirements.
REQUESTING THIS FLEXIBLE SERVICE
The dioxin and furan analytical service can be
requested by EPA Regions and other interested parties
by submitting a Task Order (TO) to EPA ASB. These
TOs can modify the SOW to meet project-specific
requirements [e.g., changes in TAT, detection limits, or
the Target Compound List (TCL)]. The DLM02.0
SOW and the NFG document can be accessed at:
http://www.epa.gov/superfund/programs/clp/dlm2.htm
DATA USES
The dioxin and furan analytical service provides data
that EPA uses for a variety of purposes such as:
determining the nature and extent of contamination at
a hazardous waste site; assessing priorities for response
based on risks to human health and the environment;
determining appropriate clean-up actions; and
determining when remedial actions are complete. The
data may be used in all stages in the investigation of
hazardous waste sites, including: site inspections;
Hazard Ranking System (HRS) scoring; remedial
investigation/feasibility studies; remedial design;
treatability studies; and removal actions. In addition,
this service provides data that are available for use in
Superfund enforcement/litigation activities.
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TARGET COMPOUNDS
The applicable target compounds and Contract
Required Quantitation Limits (CRQLs) for this service
are listed in Table 1. For water samples, the lowest
reportable CRQL is 10 pg/L. For solid samples, the
lowest reportable CRQL is 1.0 ng/kg. The specific
CRQLs are highly matrix-dependent. The quantitation
limits listed herein are provided for guidance and may
not always be achievable.
Table 1. Target Compound List (TCP
and CROLs
CDD/CDF
2378-TCDD
12378-PeCDD
123678-HxCDD
123478-HxCDD
123789-HxCDD
1234678-HpCDD
OCDD
2378-TCDF
12378-PeCDF
23478-PeCDF
123678-HxCDF
123789-HxCDF
123478-HxCDF
234678-HxCDF
1234678-HpCDF
1234789-HpCDF
OCDF
Water
(pg/L)
10
50
50
50
50
50
100
10
50
50
50
50
50
50
50
50
100
Solids
(ng/kg)
1.0
5.0
5.0
5.0
5.0
5.0
10
1.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
10
METHODS AND INSTRUMENTATION
For water samples, the stable isotopically-labeled
analogs for fifteen of the 2,3,7,8-substituted
CDDs/CDFs are spiked into a 1 L sample.
Water samples with no visible particles are extracted
with methylene chloride using a separatory funnel or
are vacuum-filtered through a glass-fiber filter on top of
a solid-phase extraction (SPE) disk. The extract is
concentrated for cleanup.
Water samples containing visible particles are vacuum-
filtered through a glass-fiber filter. The particles and
filter are extracted in a Soxhlet/Dean-Stark (SDS)
extractor and the filtrate is extracted with methylene
chloride using a separatory funnel. The methylene
chloride extract is concentrated and combined with the
SDS extract prior to cleanup.
For soil/sediment samples, the labeled compounds are
spiked into a sample containing 10 g (dry weight) of
soil/sediments. Samples containing coarse
soil/sediments are ground or homogenized. The
soil/sediments are then extracted using an SDS
extractor.
For fish and other tissue, a 20 g aliquot of frozen or
non-frozen sample is homogenized and a 10 g aliquot
is spiked with the labeled compounds. The frozen
sample is mixed with sodium sulfate, allowed to dry
overnight, and extracted for 12-24 hours using
methylene chloride:hexane (1:1) in an SDS extractor.
The non-frozen sample is allowed to equilibrate, then
200 mL hydrochloric acid and 200 mL methylene
chloride :hexane (1:1) are added and the bottle is
agitated for 12-24 hours. In both cases, the extract is
evaporated to dryness and the lipid content is
determined.
For all samples, the extracts are cleaned and injected
with two internal standards; one to determine Percent
Recoveries (%R) of tetra- and penta- CDD/CDF
congeners and the other to determine the recoveries of
hexa-, hepta-, and octa- CDD/CDF congeners. An
aliquot of the extract is injected into the HRGC for
separation and the analytes are detected by a HRMS.
Table 2 summarizes the methods and instruments used
in this analytical service.
DATA DELIVERABLES
Data deliverables for the dioxin and furan analytical
service include the hardcopy data reporting forms and
supporting raw data. Certain TOs may require the use
of the Electronic Data Deliverable (EDD) format. The
EDD reporting requirements will be outlined in the TO.
The laboratory must submit data to EPA within 3 5 days
after laboratory receipt of the last sample in the SDG,
or as stated in the TO. The EPA Regions then review
the data, based on proj ect-specific requirements and the
NFG document.
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Table 2. Methods and Instruments
Matrix
Water
(no visible particles)
Water
(visible particles)
Soil/Sediment
Fish and Other Tissue
(frozen)
Fish and Other Tissue
(non-frozen)
Preparation Method
SPE or a separately funnel with methylene
chloride for extraction.
Vacuum filtration with SDS extractor for
particles and filter extraction. Use a separatory
funnel for filtrate extraction with methylene
chloride.
SDS extraction.
Mix with sodium sulfate and allow to dry.
Extract with methylene chloride :hexane (1:1)
using an SDS extractor.
Mix with equal volumes of hydrochloric acid
and methylene chloride : hexane (1:1). Agitate
for 12-24 hours.
Analytical Instrument
HRGC/HRMS analysis
HRGC/HRMS analysis
HRGC/HRMS analysis
HRGC/HRMS analysis
HRGC/HRMS analysis
QUALITY ASSURANCE (QA)
The QA process consists of management review and
oversight at the planning, implementation, and
completion stages of the environmental data collection
activity. This process ensures that the data provided are
of the quality required.
During the planning of the data collection program, QA
activities focus on defining data quality criteria and
designing a Quality Control (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 the deficiencies uncovered by the QC
system are corrected.
After environmental data are collected, QA activities
focus on assessing the quality of data to determine its
suitability to support enforcement or remedial
decisions.
Each contract laboratory prepares a Quality Assurance
Plan (QAP) with the objective of providing sound
analytical chemical measurements. The QAP must
specify the policies, organization, objectives, and
functional guidelines, as well as the QA/QC activities
designed to achieve the data quality requirements for
this analytical service.
QUALITY CONTROL (QC)
The QC process includes those activities required
during analytical data collection to produce data of
known and documented quality. The analytical data
acquired from QC procedures are used to estimate and
evaluate the analytical results and to determine the
necessity for, or the effect of, corrective action
procedures. The QC procedures required for this
analysis are shown in Table 3. A number of optional
cleanup procedures are also available in this SOW.
PERFORMANCE MONITORING ACTIVITIES
Laboratory performance monitoring activities are
provided primarily by ASB and the Regions to ensure
that contract laboratories are producing data of the
appropriate quality. EPA performs on-site laboratory
evaluations, electronic data audits, data package audits,
HRGC/HRMS tape audits, and evaluates laboratory
performance through the use of blind Performance
Evaluation (PE) samples.
CONTACTING USEPA
For more information, or to submit suggestions to
improve this analytical service, please contact:
Elizabeth Holman
USEPA/ASB
Ariel Rios Building (5102G)
1200 Pennsylvania Ave, N.W.
Washington, DC 20460
Phone: 703-603-8761
FAX: 703-603-9116
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Table 3. Quality Control (QC)
QC Operation
Frequency
ANALYSES
HRMS System Tune
Window Defining Mixture (WDM)
NOTE : The WDM and Isomer Specificity Check (see
below) solutions may be combined into a single
solution [Column Performance Solution (CPS)],
provided that the combined solution contains the
isomers needed to determine that the criteria for
analysis are met.
Isomer Specificity Check
NOTE: The WDM and Isomer Specificity Check solutions
may be combined into a single solution (CPS),
provided that the combined solution contains the
isomers needed to determine that the criteria for
analysis are met.
Initial Calibration
Calibration Verification [Mid-Point Calibration Standard
(CSS) Relative Response (RR) and Relative Response Factor
(RRF)]
Every 12 hours prior to analysis of calibration standards,
samples, blanks, and QC samples, and at the end of each 12-
hour shift or analytical sequence.
Every 12 hours for each instrument used for analysis and
whenever adjustments or instrument maintenance activities
are performed that may affect Retention Times (RTs).
Precedes Initial Calibration and Calibration Verification;
follows the HRMS System Tune.
Every 12 hours for each instrument used for analysis and
whenever adjustments or instrument maintenance activities
are performed that may affect RTs. Performed after or
simultaneously with the WDM and before any Initial
Calibration.
Upon contract award, upon initial setup of instruments, prior
to analysis of samples and required blanks, whenever any
corrective action is taken that may change or affect the initial
calibration criteria, and each time Calibration Verification
fails to meet the technical acceptance criteria.
Prior to the beginning of every 12-hour period during which
sample data are collected, but following each injection of
Column Performance Solution (CPS), and at the end of each
12-hour period or analytical sequence.
STANDARDS
Internal Standards
Cleanup Standard
Added to all extracts prior to analysis.
Added to all extracts prior to cleanup.
BLANKS
Performance Evaluation (PE) Samples
Laboratory Control Sample (LCS)
Method Blank
Prepared and analyzed (if provided) with each set of 20 field
samples.
Prepared and analyzed with each group of 20 field samples
or less of a similar matrix in an SDG. LCS analysis precedes
analysis of samples from the same SDG.
Prepared and analyzed with each group of 20 field samples
or less, or each time samples are extracted to determine the
level of contamination associated with the processing and
analysis of samples. Method Blank analysis precedes
analysis of samples from the same SDG.
INSTRUMENT CALIBRATION
Gel Permeation Chromatography (GPC) Calibration
(optional)
Upon contract award, upon initial setup of instruments, when
the Gas Chromatography (GC) column is changed, when
channeling occurs, and once every 7 days when samples are
cleaned using GPC.
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