United States
Environmental Protection
Agency
Office of
Solid Waste and
Emergency Response
OSWER Document 9200.5-170-FS
EPA Publication 540-FS-07-004
January 2007
Multi-Media, Multi-Concentration,
Inorganic Analytical Service for
Superfund (ILM05.4)
Office of Superfund Remediation & Technology Innovation
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 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 include, but are not limited to, additional analytes
and modified quantitation limits.
The ILM05.4 analytical service is based on the previous
ILM05.3 analytical service. The update to ILM05.4
includes a change to the Contract Required Quantitation
Limits (CRQL) for the Inductively Coupled Plasma-
Mass Spectrometry (ICP-MS) analysis for vanadium in
water matrices from 1 y.g/L to 5 jig/L.
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 for this 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.
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Table 1. Inorganic Target Analyte List and Contract Required Quantitation Limits (CRQLs)
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
Analvte
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 (mg/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
5
2
--
METHODS AND INSTRUMENTATION
The Contractor 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). 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 water types, 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)
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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 (C VAA)
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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review to provide EPA Regions 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 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:
JohnD. Nebelsick
Inorganic Program Manager
USEPA/ASB
Ariel Rios Building (5203P)
1200 Pennsylvania Avenue, NW
Washington, DC 20460
Tel: 703-603-8845
Fax: 703-603-9135
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