United States Office of
Environmental Protection Solid Waste and
Agency Emergency Response
OSWER Document 9200.3-73FS
EPA Publication 540-FS-l 1-04
November 2011
&EPA Multi-Media, Multi-Concentration
Dioxin and Furan Analytical Service
for Superfund (DLM02.2)
Office of Superfund Remediation and Technology Innovation (OSRTI)
Analytical Services Branch (5203P)
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
and total homologues 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) DLM02.2 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 DLM02.2 SOW and the NFG document
can be accessed at:
http: //www. epa. go v/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 cleanup
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.
-------
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
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,6,7,8-HxCDD
1,2,3,4,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-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 separately 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 separately 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 this service include hardcopy
data reporting forms and supporting raw data.
Laboratories must also submit the data electronically,
referred to as an Electronic Data Deliverable (EDD),
within the contract required TAT. Additional
information about EDD requirements are provided in
Exhibit H of the SOW, located at:
http://www.epa.gov/superfund/programs/clp/dlm2.htm.
EPA then processes the EDD through a web-based
data assessment tool - the Electronic Data exchange
and Evaluation System (EXES). EXES provides data
users with electronic data assessment/usability
reports and spreadsheets within 24 to 48 hours of data
-------
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 separately
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
HRGC/HRMS
HRGC/HRMS
HRGC/HRMS
HRGC/HRMS
receipt. EXES reports also facilitate the transfer of
analytical data into client databases. In addition to the
data assessment/usability reports, laboratories are
provided with a data assessment report documenting
instances of noncompliance.
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 EPA
For more information, or to submit suggestions to
improve this analytical service, please contact:
Charlie Appleby
USEPA, OSWER/OSRTI/TIFSD/ASB
Ariel Rios Building (5203P)
1200 Pennsylvania Ave, N.W.
Washington, DC 20460
Phone (ASB): 703-347-0266
Phone (mobile): 703-405-0057
FAX: 703-603-9135
-------
Table 3. Quality Control (PC)
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
Labeled Compound Standards
Cleanup Standard
Internal Standards
Added to all samples prior to extraction.
Added to all extracts prior to cleanup.
Added to all extracts prior to analysis.
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.
------- |