United States
Environmental Protection
Agency
Office of
Solid Waste and
Emergency Response
OSWER Document 9240.1-43FS
EPA Publication 540-F-04-001
February 2004
Multi-Media, Multi-Concentration,
Inorganic Analytical Service for
Superfund (ILM05.3)
Office of Superfund Remediation and Technology Innovation
Analytical Services Branch (5204G)
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 EPA at such sites is a series of inorganic analytes and cyanide that are analyzed using Inductively Coupled
Plasma-Atomic Emission Spectroscopy (ICP-AES), Inductively Coupled Plasma-Mass Spectrometry (ICP-MS), Cold
Vapor Atomic Absorption (CVAA), and colorimetric techniques. The Analytical Services Branch (ASB) of the Office
of Superfund Remediation and Technology Innovation (OSRTI) offers an analytical service that provides data from the
analysis of water/aqueous and soil/sediment samples for inorganic analytes for use in the Superfund and other decision
making processes. Through a series of standardized procedures and a strict chain-of-custody, the inorganic analytical
service produces data of known and documented quality. This service is available through the Superfund Contract
Laboratory Program (CLP).
DESCRIPTION OF SERVICES
The inorganic analytical service provides a technical
and contractual framework for laboratories to utilize
EPA/CLP analytical methods. These methods are used
in the isolation, detection and quantitative measurement
of 23 target analyte metals (including mercury) and
cyanide in both water and soil/sediment environmental
samples. The CLP provides the methods to be used and
the specific technical, reporting, and contractual
requirements, including Quality Assurance (QA),
Quality Control (QC), and Standard Operating
Procedures (SOPs), by which EPA evaluates the data.
Three data delivery turnaround times are available to
CLP customers: 7, 14, and 21-day turnaround after
receipt of the last sample in the set. A 72-hour
preliminary data submission option also is available for
all turnaround times. The data associated with these
Preliminary Results is due within 72 hours after receipt
of each sample at the laboratory. In addition, data users
may request modifications to the SOW that may
include, but are not limited to, additional analytes and
modified quantitation limits.
DATA USES
This analytical service provides data that EPA uses for
a variety of purposes. Examples include 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 a hazardous waste
site including: site inspections, Hazard Ranking System
scoring, remedial investigations/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 ANALYTES
The inorganic analytes and quantitation limits for which
this service is applicable are listed in Table 1. Specific
detection limits are method and matrix dependent.
The list of target analytes forthis service was originally
derived from the EPA Priority Pollutant List of 129
compounds. In the years since the inception of the
CLP, analytes have been added to and deleted from the
Target Analyte List (TAL), based on advances in
analytical methods, evaluation of method performance
data, and the needs of the Superfund program.
METHODS AND INSTRUMENTATION
The Contractor laboratories will demonstrate the ability
to meet certain program data quality objectives prior to
analyzing field samples. The laboratories must
document methods used to generate analytical results
and determine Method Detection Limits (MDLs).
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Table 1. Inorganic Target Analyte List and Contract Required Quantitation Limits (CRQLs)
Analyte
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
ICP-AES CROL for
Water (ug/L)
200
60
10
200
5
5
5000
10
50
25
100
10
5000
15
0.2
40
5000
35
10
5000
25
50
60
10
ICP-AES CROL for
Soil tog/kg)
20
6
1
20
0.5
0.5
500
1
5
2.5
10
1
500
1.5
0.1
4
500
3.5
1
500
2.5
5
6
2.5
ICP-MS CROL for
Water (ug/L)
—
2
1
10
1
1
2
1
2
1
--
1
--
1
5
1
1
1
2
--
ICP-Atomic Emission Spectroscopy (ICP-AES) is used
to analyze water, sediment, sludge, and soil samples.
Water and soil samples are treated with acids and
heated. The digestates are then analyzed for trace
metals by an atomic emission optical spectroscopic
technique. The samples are nebulized and the aerosol
is transported to a plasma torch. The atomic-line
emission spectra are dispersed and a photosensitive
device monitors line intensities.
ICP-Mass Spectrometry (ICP-MS) is used to determine
the concentration of dissolved and total recoverable
elements in water/aqueous samples. The sample
material is introduced, by nebulization, into radio
frequency plasma where desolvation, atomization, and
ionization take place. The ions are extracted from the
plasma through a differentially pumped vacuum
interface and separated based on their mass-to-charge
ratio.
Cold Vapor Atomic Absorption (CVAA) is used to
analyze water, sediment, sludge, and soil samples for
total mercury. Organo-mercury compounds may also
be present and will need to be broken down and
converted to mercuric ions to respond to the CVAA
techniques. For water samples, organic compounds are
oxidized and then reacted with a strong reducing agent.
The volatile free mercury is then driven from the
reaction flask by bubbling air through the solution. The
air stream carries the mercury atoms to an absorption
cell, which is then placed in the light path of the AA
spectrophotometer. For soil/sediment, the samples
undergo acid digestion/oxidation followed by reduction
and measurement by conventional cold vapor
technique.
Various watertypes, sediment, sludge, and soil samples
are also analyzed for total cyanide. Hydrocyanic acid
(HCN) is released through a reflux-distillation and
absorbed in a scrubber containing sodium hydroxide
solution. The cyanide ion is determined
colorimetrically by converting it to cyanogen chloride
(CNC1).
Table 2 summarizes the methods and instruments used
in this analytical service.
DATA DELIVERABLES
Data deliverables for this service include both
hardcopy/electronic data reporting forms and
supporting raw data. The laboratory must submit data
to EPA within 7-, 14- or 21-days, or preliminary data
must be submitted within 72 hours after laboratory
receipt of each sample in the set, if requested. EPA
then processes the data through an automated Data
Assessment Tool (DAT). DAT is a complete CLP data
assessment package. DAT incorporates Contract
Compliance Screening (CCS) and Computer-Aided
Data Review and Evaluation (CADRE) review to
provide EPA Regions and other data users with
electronic reports (PC-compatible reports, spreadsheets,
and electronic files) within 24 to 48 hours from the
receipt of the data. This automated tool facilitates the
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Table 2. Methods and Instruments
Analyte
Al, Sb, As, Ba, Be, Cd, Ca, Cr, Co, Cu,
Fe, Pb, Mg, Mn, Ni, K, Se, Ag, Na, Tl,
V,Zn
Sb, As, Ba, Be, Cd, Cr, Co, Cu, Pb,
Mn, Ni, Se, Ag, Tl, V, Zn
Mercury (Hg)
Cyanide (CN)
Instrument
Inductively Coupled Plasma - Atomic
Emission Spectroscopy (ICP-AES)
ICP - Mass Spectrometry (ICP-MS)
Cold Vapor Atomic Absorption
(CVAA)
Colorimeter or Spectrophotometer
Method
ICP analysis of atomic-line emission
spectra.
ICP analysis of ions separated on basis
of mass-to-charge ratio.
Acid digestion/oxidation followed by
reduction and CVAA analysis.
Distillation followed by colorimetric
analysis.
Table 3. Quality Control
QC Operation
Instrument Calibration
Initial Calibration Verification
Initial Calibration Blank
Continuing Calibration
Verification
Continuing Calibration Blank
CRQL Check Standard (CRI)
Interference Check Sample
Serial Dilution for ICP
Preparation Blank
Laboratory Control Sample
Spike Sample
Post Digestion/Distillation Spike
Duplicate Sample Analysis
ICP-MS Tune
Method Detection Limit
Determination
Interelement Corrections
Linear Range Analysis
Frequency
Daily or each time instrument is set up.
Following each instrument calibration for each wavelength or mass used.
Following each instrument calibration, immediately after the Initial Calibration
Verification (ICV).
For each wavelength or mass used, at a frequency of 10% or every two hours of a run,
whichever is more frequent, and at the beginning and end of each run.
10% or every two hours of a run, whichever is more frequent, and at the beginning and
end of each run. Performed immediately after the last Continuing Calibration
Verification (CCV).
Every 20 analytical samples and at the beginning and end of each run, but not before
the ICV. Performed before the Interference Check Sample.
For ICP-AES, every 20 analytical samples and at the beginning and end of each run,
immediately after the CRI. For ICP-MS, at the beginning of the run.
For each matrix type or for each SDG, whichever is more frequent.
For each SDG or each sample preparation and analysis procedure per batch of prepared
samples.
For each SDG or each sample preparation and analysis procedure per batch of prepared
samples, except aqueous mercury and cyanide.
For each matrix type or for each SDG, whichever is more frequent.
Each time Spike Sample Recovery is outside QC limits.
For each matrix type or for each SDG, whichever is more frequent.
Prior to calibration.
Prior to contract, annually thereafter, and after major instrument maintenance.
Prior to contract, quarterly thereafter, and after major instrument adjustment.
Prior to contract, and quarterly thereafter.
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transfer of analytical data into Regional databases.
DAT can also be used to assist in the data validation
process at the Region. In addition to the Regional
electronic reports, the CLP laboratories are provided
with a data assessment report that documents the
instances of noncompliance. The laboratory has four
business days to reconcile defective data and resubmit
the data to EPA. EPA then reviews the data for
noncompliance and sends a final data assessment report
to the CLP laboratory and the Region.
QUALITY ASSURANCE
The Quality Assurance (QA) process consists of
management review and oversight at the planning,
implementation, and completion stages of the
environmental data collection activity and ensures that
the data provided are of the quality required. During
the data collection effort, QA activities ensure that the
Quality Control (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. Each contract
laboratory will establish a Quality Assurance Plan
(QAP) with the objective of providing sound analytical
chemical measurements. The QAP must specify the
policies, organization, objectives, functional guidelines,
and specific QA/QC activities designed to achieve the
data quality requirements for this analytical service.
QUALITY CONTROL
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 analytical service are shown in
Table 3.
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
audits, data package audits, and evaluates laboratory
performance with blind performance evaluation
samples.
For more information, or for suggestions to improve
this analytical service, please contact:
Anand R. Mudambi
Inorganic Program Manager
USEPA/ASB
Ariel Rios Building (5204G)
1200 Pennsylvania Avenue, NW
Washington, D.C. 20460
Tel: 703-603-8796
Fax:703-603-9112
JohnD. Nebelsick
Deputy Inorganic Program Manager
USEPA/ASB
Ariel Rios Building (5204G)
1200 Pennsylvania Avenue, NW
Washington, D.C. 20460
Tel: 703-603-8845
Fax:703-603-9112
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