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EXHIBIT A
SUMMARY OF REQUIREMENTS
PAGE
SECTION I GENERAL REQUIREMENTS A-l
SECTION II SPECIFIC REQUIREMENTS A-3
SECTION III TECHNICAL AND MANAGEMENT REQUIREMENTS A-9
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SECTION I
GENERAL REQUIREMENTS
The Contractor shall employ procedures specified in this Statement of Work
(SOW) in the preparation and analysis of aqueous (water) and solid
(soil/sediment) samples for the presence and quantisation of 23 indicated
elements and cyanide.
The Contractor shall use proven instruments and techniques to identify and
measure the elements and inorganic species presented in the Target Analyte
List (Exhibit C). The Contractor shall perform sample preparation and
analysis procedures as prescribed in Exhibit D, meeting specified sample
preservation and holding time requirements.
If dissolved metals are requested by the EPA Regional offices, the
Contractor shall follow the instructions provided on the Traffic Reports.
If there are no instructions on the Traffic Report, the Contractor shall
contact SMO for resolution.
The Contractor shall adhere to the quality assurance/quality control
protocol specified in Exhibit E for all samples analyzed under this
contract.
Following sample analysis, the Contractor shall perform data reduction and
shall report analytical activities, sample data, and quality control
documentation as designated in Exhibit B.
Exhibit F.contains chain-of-custody and document control requirements which
the Contractor must follow in processing samples and specifies requirements
for written laboratory standard operating procedures.
To ensure proper understanding of language utilized in this contract,
Exhibit G contains a glossary of terms. When a term is used in the text
without explanation, the glossary meaning shall be applicable. Glossary
definitions do not replace or take precedence over specific information
included in the SOW text.
Exhibit H contains the Agency Standard implementation for reporting data
electronically.
The samples to be analyzed by the Contractor are from known or suspected
hazardous waste sites and, potentially, may contain hazardous inorganic
and/or organic materials at high concentration levels. The Contractor
should be aware of the potential hazards associated with the handling and
analyses of these samples. It is the Contractor's responsibility to take
all necessary measures to ensure the health and safety of its employees.
In addition, the Contractor must be aware of the importance of maintaining
the integrity of the data generated under the contracts as it is used to
make major decisions regarding public health and environmental welfare.
The data may also be used in litigation against Potentially Responsible
Parties in the enforcement of Superfund legislation.
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Exhibit C. aPPr°Prlate Standards for *U '-get analytes lls^d in
A-2
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SECTION II
SPECIFIC REQUIREMENTS
A. FOR EACH SAMPLE, THE CONTRACTOR SHALL PERFORM THE FOLLOWING TASKS:
Task I: Receive and Prepare Hazardous Waste Samples.
1. The Contractor shall receive and handle samples under the chain-
of-custody and sample documentation procedures described in
Exhibit F. A sample consists of all components, perhaps more than
one phase, contained inside appropriate receptacles. More than
one container may be used for a single sample; individual
containers may contain preservatives for different analysis
portions. Containers may be glass or plastic.
2. The Contractor shall provide the required analytical expertise and
Instrumentation for analyses of Target Analyte List (TAL) elements
and cyanide equal to or lower than the detection limits specified
in Exhibit C. In Exhibit D, EPA provides the Contractor with the
specific sample preparation techniques for water and soil/sediment
samples and the analytical procedures which must be used. A
schematic flow chart depicting the complete low level-medium level
inorganics analytical scheme is presented in Section I of Exhibit
D.
3. The Contractor shall prepare and analyze samples within the
maximum holding time specified in Section II of Exhibit D even if
these times are less than the maximum data submission time allowed
in this contract.
4. The Contractor is advised that the samples received under this
contract are usually from known or suspected hazardous waste sites
and may contain high (greater than 15%) levels of organic and
inorganic materials of a potentially hazardous nature and of
unknown structure and concentration, and should be handled
throughout the analysis with appropriate caution. It is the
Contractor's responsibility to take all necessary measures to
ensure laboratory safety.
Task II: Analyze Samples for Identity and Quantitation of Specific
Inorganic Constituents.
1. For each sample received, the Contractor may be required to
perform the analyses described in the following paragraphs 2., 3.
and 4. The documentation that accompanies the sample(s) to the
Contractor facility shall indicate specific analytical
requirements for that sample or set of samples.
2. Exhibit D specifies the analytical procedures that must be used.
Exhibit D contains instructions and references for preparation of
samples containing low-to-medium concentrations of inorganics for
ICP analysis; flame, graphite furnace and cold vapor AA analysis
and cyanide analysis. The identification and quantitation of
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analytes other than cyanide shall be accomplished using the ICP or
AA methods specified in Exhibit D and achieves the Contract
Required Detection Limit (CRDL) specified in Exhibit C. Cyanide
shall be analyzed by the individual procedures specified in
Exhibit D.
3. All samples must initially be run undiluted (i.e., the final
product of sample preparation procedure). When an analyte
concentration exceeds the calibrated or linear range, appropriate
dilution (but not below the CRDL) and reanalysis of the prepared
sample is required, as specified in Exhibit D.
4. For the purpose of this contract, a full sample analysis is
defined as the analysis for ALL of the target constituents
identified in Exhibit C in accordance with the methods in Exhibit
D and performance of related QA/QC as specified in Exhibit E.
Duplicate sample, laboratory control sample, and spike sample
analyses shall each be considered a separate full sample analysis.
All other QA/QC requirements are considered an inherent part of
this contract Statement of Work and are included in the contract
sample unit price.
Task III: Perform Required Quality Assurance/Quality Control
Procedures
1. All specific QA/QC procedures prescribed in Exhibit E shall be
strictly adhered to by the Contractor. Records documenting the
use of the protocol shall be maintained in accordance with the
document control procedures prescribed in Exhibit F, and shall be
reported in accordance with Exhibit B requirements.
2. The Contractor shall establish and use on a continuing basis QA/QC
procedures including the daily or (as required) more frequent use
of standard reference solutions from EPA, the National Institute
of Standards and Technology or secondary standards traceable
thereto, where available at appropriate concentrations (i.e.,
standard solutions designed to ensure that operating parameters of
equipment and procedures, from sample receipt through
identification and quantitation, produce reliable data). Exhibit
E specifies the QA/QC procedures required.
3. The Contractor shall establish a Quality Assurance Plan (QAP) as
defined in Exhibit E with the objective of providing sound
analytical chemical measurements. This program shall incorporate
the quality control 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.
4. Additional quality assurance and quality control shall be required
in the form of Performance Evaluation Samples submitted by EPA for
Contractor analysis, and in the form of verification of instrument
parameters, as described in Exhibit E.
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5. Laboratory Control Sample (LCS) - This standard solution is
designed to assure that the operating parameters of the analytical
instrumentation and analytical procedures from sample preparation
through identification and quantitation produce reliable data.
The Contractor must analyze the LCS concurrently with the analysis
of the samples in the Sample Delivery Group (see Exhibit A, Part
I).
B. EPA has provided to the Contractor formats for the reporting of data
(Exhibits B and H). The Contractor shall be responsible for completing
and returning analysis data sheets and submitting computer-readable
data on diskette in the format specified in this SOW and within the
time specified in the Contract Performance/Delivery Schedule (see
Exhibit B).
1. Use of formats other than that designated by EPA will be deemed as
noncompliant. Such data are unacceptable. Resubmission in the
specified format at no additional cost to the government will be
required.
2. Computer generated forms may be submitted in the hardcopy data
package(s) provided that the forms are in EXACT EPA FORMAT. This
means that the order of data elements is the same as on each EPA
required form, including form numbers and titles, page numbers and
header information, columns and lines.
3. The data reported by the Contractor on the hardcopy data forms and
the associated computer-readable data submitted by the Contractor
on diskette must contain identical information. If during
government inspection discrepancies are found, the Contractor
shall be required to resubmit either or both sets of data at no
additional cost to the Government. The resubmitted diskette
and/or hardcopy must contain all of the initially correct
information previously submitted for all samples including the
Laboratory Control Sample, standards, and blanks in the SDG in
addition to the corrections replacing the variables which were
incomplete or incorrect according to the requirements in the SOW.
C. The Contractor shall provide analytical equipment and technical
expertise for this contract as specified by the following:
1. Inductively coupled plasma (ICP) emission spectrometer with the
capability to analyze metals sequentially or simultaneously.
2. Atomic absorption (AA) spectrometer equipped with graphite
furnace, flame, and cold vapor AA (or a specific mercury analyzer)
analysis capabilities.
3. Analytical equipment/apparatus for analysis of cyanide as
described in Exhibit D.
D. The minimum functional requirements necessary to meet the terms and
conditions of this contract are listed in items 1-7 below. The
Contractor shall designate and utilize qualified key personnel to
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perform these functions. The EPA reserves the right to review
personnel qualifications and experience. See Section III, Technical &
Management Requirements.
1. Inorganic Laboratory Supervisor
2. Quality Assurance Officer
3. Systems Manager
4. Programmer Analyst
5. ICP Spectroscopist
6. ICP Operator
7. Atomic Absorption (AA) Operator
8. Inorganic Sample Preparation Specialist
9. Classical Techniques (Cyanide) Analyst
. 10. Inorganic Chemist (Backup)
E. The Contractor shall respond (within seven days) to written requests
from data recipients for additional information or explanations that
result from the Government's inspection activities unless otherwise
specified in the contract (see Exhibit E for details on Government
inspection activities).
F. The Contractor is required to retain unused sample volume and used
sample containers for a period of 60 days after data submission. From
time of receipt until analysis, the Contractor shall maintain
soil/sediment samples at 4°C (±2°C).
G. The Contractor shall adhere to chain-of-custody and document control
procedures described in Exhibit F. Documentation, as described
therein, shall be required to show that all procedures are being
strictly followed. This documentation shall be reported in the
Complete SDG File (see Exhibit B).
H. 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 with the samples (e.g., mixed media, containers
broken or leaking) or sample documentation/paperwork (e.g., Traffic
Reports not with shipment, or 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/or laboratory conditions that affect the timeliness of
analyses and data reporting. In particular, the Contractor shall
immediately notify SMO personnel in advance regarding sample data that
will be delivered late and shall specify the estimated delivery date.
I. 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
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area over a finite time period, and will include 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 Groups (SDG). An 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 (seven calendar day period for 14-day data
turnaround contracts), said period begins with the receipt of
the first sample in the SDG.
Samples may be assigned to Sample Delivery Groups by matrix (i.e., all
soils in one SDG, all waters in another), at the discretion of the
laboratory. Such assignment must be made at the time the samples are
received, and may not be made retroactively.
Data for all samples in an 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 is 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 that the last sample in the SDG is received.
The Contractor is responsible for identifying each SDG as samples are
received, through proper sample documentation (see Exhibit B) and
communication with SMO personnel.
Each sample received by the Contractor will be labeled with an EPA
sample number, and accompanied by a Traffic Report form bearing the
sample number and descriptive information regarding the sample. EPA
field sample numbers are six digits in length. If the Contractor
receives a sample number of any other length, contact SMO immediately.
The Contractor shall complete and sign the Traffic Report, recording
the date of sample receipt and sample condition on receipt for each
sample container. The Contractor must also follow the instructions
given on the Traffic Report in choosing the PC samples when such
information is provided.
The Contractor shall submit signed copies of Traffic Reports for all
samples in a Sample Delivery Group 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 an SDG
shall be clipped together) with an SDG Cover Sheet containing
information regarding the Sample Delivery Group, as specified in
Exhibit B.
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K. EPA Case numbers (including SDG numbers) and EPA sample numbers shall
be used by the Contractor in identifying samples received under this
contract both verbally and in reports/correspondence.
L. Samples will routinely be shipped directly to the Contractor through a
delivery service. The Contractor shall be available to receive sample
shipments at any time the delivery service is operating, including
Saturdays and holidays. 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.
M. The Contractor shall accept all samples scheduled by SHO, 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.
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SECTION III
TECHNICAL AND MANAGMENT REQUIREMENTS
I. TECHNICAL CAPABILITY
As cited in Section II the Contractor shall have the following technical
and management capabilities. Note: For those technical functions which
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.
Any personnel changes affecting the key personnel s.s stated in Exhibit A,
Section III, Items I and II, shall require the Contractor to notify in
writing the Technical Project Officer and the Administrative Project
Officer within 14 days of the personnel 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 Supervisory Personnel/Key Personnel
1. Inorganics Laboratory Supervisor
a. Responsible for all technical efforts of the Inorganics
Laboratory to meet all terms and conditions of the EPA
contract.
b. Qualifications
(1) Education:
Minimum of Bachelor's degree in chemistry or any
scientific/engineering disc ipline.
(2) Experience:
Minimum of three years of laboratory experience,
including at least one year in a supervisory
position.
2. Quality Assurance Officer
a. Responsible for overseeing the quality assurance aspects
of the data and reporting directly to upper management
to meet all terms and condition!; of the EPA contract.
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b. Qualifications:
(1) Education:
Minimum of Bachelor's degree in chemistry or any
scientific/engineering discipline.
(2) 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.
3. Systems Manager
a. Responsible for the management and quality control of
all computing systems (hardware, software, documentation
and procedures), generating, updating, and performing
quality control reviews of autonated deliverables to
meet all terms and conditions oJ: the EPA contract.
b. Qualifications:
(1) Education:
Minimum of Bachelor's degree with four or more
intermediate courses in programming, information
management, database management systems, or systems
requirements analysis.
(2) Experience:
Minimum of three years experience in data or
systems management or programming including one
year experience with the software being utilized
for data management and generation of deliverables.
4. Programmer Analyst
a. Responsible for the installation, operation and
maintenance of software and programs, generating,
updating and performing quality control reviews of
analytical databases and automated deliverables to meet
all terms and conditions of the EPA contract.
b. Qualifications:
(1) Education:
Minimum of Bachelor's degree with four or more
intermediate courses in programming, information
management, information systems, or systems
requirements analysis.
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(2) Experience:
Minimum of two years experience in systems or
applications programming including one year of
experience with the software being utilized for
data management and generation of deliverables.
B. Technical Staff
1. ICP Spectroscopist Qualifications
a. Education:
Minimum of Bachelor's degree in chemistry or any
scientific/engineering discipline.
Specialized training in ICP Speotroscopy.
b. Experience:
Minimum of two years of applied experience with ICP
analysis of environmental samples.
2. ICP Operator Qualifications
Minimum of Bachelor's degree in chemistry or any
scientific/engineering discipline with one year of
experience in operating and maintaining ICP
instrumentation, or, in lieu of the educational
requirement, three additional years of experience in
operating and maintaining ICP instrumentation.
3. Atomic Absorption (AA) Operator Qualifications
Minimum of Bachelor's degree in chemistry or any
scientific/engineering discipline with one year of
experience in operating and maintaining AA
instrumentation for graphite furnace, flame, and cold
vapor AA, or, in lieu of the edxicational requirement,
three additional years of experience in operating and
maintaining AA instrumentation, including graphite
furnace, flame, and cold vapor techniques.
4. Inorganic Sample Preparation Specialist Qualifications
a. Education:
Minimum of high school diploma and a college level
course in general chemistry or equivalent.
b. Experience:
Minimum of 1 year of experience in sample preparation in
an analytical laboratory.
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c. Experience (Required if microwave digestion is used):
Minimum of six months experience! in an analytical
laboratory and six months experience in sample
dissolution using microwave digestion techniques.
5. Classical Techniques (Cyanide) Analyst Qualifications
a. Education:
Minimum of Bachelor's degree in chemistry or any
scientific/engineering discipline.
b. Experience:
Minimum of 1 year of experience with classical chemistry
laboratory procedures, in conjunction with the
educational qualifications; or, in lieu of educational
requirement, two years of additional equivalent
experience.
6. Technical Staff Redundancy
In order to ensure continuous operations to accomplish the
required work as specified by the EPA contract, the bidder
shall have a minimum of one (1) chemist available at all
times as a back-up technical person with the following
qualifications.
a. Education:
Minimum of Bachelor's degree-in chemistry or any
scientific/engineering discipline.
b. Experience:
Minimum of one year of experience in each of the
following areas —
o ICP operation and maintenance
o AA operation and maintenance
o Classical chemistry analytical procedures
o Sample preparation for inorganics analysis
C. Facilities
The adequacy of the facilities and equipment is of equal
importance for the technical staff to accomplish the required work
as specified by the EPA contract.
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1. Sample Receipt Area
Adequate, contamination-free, well-ventilated work space
provided with chemical resistant bench top for receipt and
safe handling of EPA samples.
2. Storage Area
Sufficient refrigerator space to maintain unused EPA sample
volume for 60 days after data submission. Soil samples must
be stored in a refrigerator at 4°C (;t2°C) . Samples and
standards must be stored separately to prevent cross-
contamination.
3. Sample Preparation Area
Adequate, contamination-free, well-ventilated work space
provided with:
a. Benches with chemical resistant tops.
b. Exhaust hoods. Note: Standards; must be prepared in a
glove box or isolated area.
c. Source of distilled or demineralized organic-free water.
d. Analytical balance(s) located away from draft and rapid
change in temperature.
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D. Instrumentation
At a minimum, the Contractor shall have the following instruments
operative at the time of the Preaward Site Evaluation and
committed for the full duration of the contract.
1. Primary Instrument Requirements for 200 Samples/Month
Capacity Requirements
Fraction
ICP Metals
GFAA Metals
Mercury
Cyanide
No. of
Ins trument ( s )
1
2
2
12 distillation
units + 1
photometer
Type of
Instrument
ICP Emission
Spectrophotometer
Atomic Absorption
Spectrophotometer
with Graphite
Furnace Atomizer
Mercury Cold Vapor
AA Analyzer or AA
instrument
modified for Cold
Vapor Analysis
See Cyanide
Methods, Statement
of Work Exhibit D,
Section IV, Part E
1
There are no Secondary Instrument Requirements for 200 Samples/Month
Capacity.
A-14
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2. 300 Samples/Month Capacity Requirements
Fraction
ICP Metals
GFAA Metals
Mercury
Cyanide
No. of
Instrument (s)
1
3
2
18 distillation
units + 1
photometer
Type of
Instrument
ICP Emission
Spec t ropho tome ter
Atomic Absorption
Spectrophotometer
with Sraphite
Furnace Atomizer
Mercury Cold Vapor
AA Analyzer or AA
instrument
modified for Cold
Vapor Analysis
See Cyanide
Me tho ds , S tatement |
of Work Exhibit D,
Section IV, Part E
Secondary Instrument Requirements for 300 Samples/Month Capacity
The Contractor shall have the following instruments in place
and operational at any time as a back-up system:
Quantity
One
Instruments
GFAA
3. Additional Instrument Requirements for greater than 300
Samples/Month Capacity
Quantity
One
One
Instruments
GFAA
ICP Emission Spectrophotometer
4. Instrument Specifications
Further information on instrument specifications and required
ancillary equipment may be found in the Statement of Work.
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E. Data Management and Handling
1. Hardware - Contractor will have an 13M or IBM-compatible
mini-computer or PC capable of recording required sample data
on 5.25 inch double-sided, double-density 360 K-byte or high
density 1.2 M-byte diskettes; or a 3.5 inch double-sided,
double-density 720 K-byte or 1.44 M-byte diskettes in ASCII
text file format and in accordance with the file, record and
field specifications listed in the SOW, Exhibit H.
Other minimum requirements include:
Hard disk of at least 20 M-byte«.
Asynchronous, Hayes-compatible uodem capable of at least
2,400 baud transmission speed. In addition, MNP level 5
compatibility or compatibility with EPA V.32/V.42bis
equipment is recommended.
2. Software - Software, utilized in generating, updating and
providing quality control for analytical databases and
automated deliverables shall have the following additional
capabilities:
Editing and updating databases.
Controlled access using user ID and file password
protection.
3. The Contractor shall also be able to submit reports and data
packages as specified in the SOW Exhibit B. To complete this
task, the Contractor shall be required to provide space,
tables and adequate copy machines to meet the contract
requirements.
II. 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:
A. Technical Staff
Responsible for all technical efforts for the EPA contract.
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B. Project Manager
Responsible for overall aspects of EPA contract(s) (from sample
receipt through data delivery), and shall serve as the primary
contact for EPA Headquarters Administrative Project Officer and
Regional Technical Project Officers.
C. Sample Custodian
Responsible for receiving the EPA samples (logging, handling and
storage).
D. Quality Assurance Officer
Responsible for overseeing the quality assurance aspects of the
data and reporting directly to upper management.
E. Document Control Officer
Responsible for all aspects of data deliverables: organization,
packaging, copying, and delivery. Responsible for ensuring that
all documents generated are placed in the complete SDG file for
inventory and are delivered to the appropriate EPA Regional
personnel or other receiver.
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EXHIBIT B
REPORTING AND DELIVERABLES REQUIREMENTS
Page No.
SECTION I: Contract Reports/Deliverables Distribution .... B-2
SECTION II: Report Descriptions and Order of Data
Deliverables B-4
SECTION III: Form Instruction Guide B-13
SECTION IV: Data Reporting Forms B-39
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Exhibit B Section I
SECTION I
CONTRACT REPORTS/DELIVERABLES DISTRIBUTION
(For 35-Day Turnaround Contracts)
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 will
notify the Contractor in writing of such changes when they occur.
| No.
Item (Copies
*****A. .Standard
Operating
Procedures
B. Sample Traffic
Reports
***C. Sample Data
Package
D. Data in Computer
Readable Format
****E. Complete SDG File
*F. Quarterly /Annual
Verification
of Instrument
Parameters
*****G. Quality
Assurance
Plan
3
1
2
1
1
2
3
Delivery
Schedule
60 days after
contract award
and as required
in Exhibit E.
3 days after
receipt of last
sample in Sample
Delivery Group
(SDG)***
35 days after
receipt of last
sample in SDG
35 days after
receipt of last
sample in SDG
35 days after
receipt of last
sample in SDG**
Quarterly:
15th day of
J anuary , Ap r i 1
July, October
60 days after
contract award
and as required
in Exhibit E.
(D
X
X
X
X
A
Distri
(2)
X
X
5 dire
.but i or
(3)
X
X
X
:ted
i
(4)
X
Distribution:
(1) Sample Management Office (SMO)
(2) Region-Client
(3) Environmental Monitoring Systems Laboratory (EMSL/LV)
(4) NEIC
B-2A
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Exhibit B Section I
SECTION I
CONTRACT REPORTS/DELIVERABLES DISTRIBUTION
(For 14-Day Turnaround Contracts)
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 will
notify the Contractor in writing of such changes when they occur.
| No.
Item (Copies
*****A. Standard
'Operating
Procedures
B. Sample Traffic
Reports
***C. Sample Data
Package
D. Data in Computer
Readable Format
****E. Complete SDG File
*F . Quarterly /Annual
Verification
of Instrument
Parameters
*****G. Quality
Assurance
Plan
3
1
2
1
1
2
3
Delivery
Schedule
60 days after
contract award
and as required
in Exhibit E.
3 days after
receipt of last
sample in Sample
Delivery Group
(SDG)***
14 days after
receipt of last
sample in SDG
14 days after
receipt of last
sample in SDG
14 days after
receipt of last
sample in SDG**
Quarterly:
15th day of
January, April
July, October
60 days after
contract award
and as required
in Exhibit E.
(D
X
X
X
X
A.
DistrJ
(2)
X
X
3 dire<
Lbutior
(3)
X
X
X
:ted
*
(4)
X
Distribution:
(1) Sample Management Office (SMO)
(2) Region-Client
(3) Environmental Monitoring Systems Laboratory (EMSL/LV)
(4) NEIC
B-2B
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Exhibit B Section I
* Also required in each Sample Data Package.
** Concurrent delivery of these items to all recipients is required.
*** Sample Delivery Group (SDG) is a group of samples within a Case, received over a
period of 14 days or less (seven days or less for 14-day data turnaround contracts)
and not exceeding 20 samples. Data for all samples in the SDG are due
concurrently. (See SOW Exhibit A, for further description).
**** Complete SDG file will contain the original sample data package plus all of the
original documents described in Exhibit B of the Statement of Work under Complete
SDG File.
*****See Exhibit E for description
NOTE: As specified in the Contract Schedule (Government Furnished Supplies and
Materials), unless otherwise instructed by the CLP Sample Management Office, the
Contractor shall dispose of unused sample volume and used sample bottles/containers no
earlier than sixty (60) days following submission of analytical data.
Distribution Addresses:
(1) USEPA Contract Laboratory Program (CLP)
Sample Management Office (SMO)
P. 0. Box 818
Alexandria, VA 22313
For overnight delivery service, use street address:
300 N. Lee Street
Alexandria, VA 22313
(2) USEPA REGIONS: The CLP Sample Management Office, acting on behalf of the Administrative
Project Officer, will provide the Contractor with the list of addressees for the ten EPA
Regions. SMO will provide the 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 (EMSL/LV)
944 E. Harmon Avenue
Las Vegas, NV 89109
Attn: Data Audit Staff
(4) USEPA National Enforcement Investigations Center (NEIC)
Attn: CLP Audit Program
Denver Federal Center Bldg. 53
P.O. Box 25227
Denver, CO 80225
B-3 ILM02.0
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Exhibit B Section II
SECTION II
REPORT DESCRIPTIONS AND ORDER OF DATA DELIVERABLES
The Contractor laboratory shall provide reports and other deliverables as
specified in the Contract Performance/Delivery Schedule (see Contract Schedule,
Section F). The required content and form of each deliverable is described in this
Exhibit.
All reports and documentation MUST BE as follows:
o Legible,
o Clearly labeled and completed in accordance with instructions in
this Exhibit,
o Arranged in increasing alphanumeric EPA sample number order
o Paginated sequentially according to instructions in this Exhibit, and
o Single-sided.
If submitted documentation does not conform to the above criteria, the
Contractor will be required to resubmit such documentation with deficiency(ies)
corrected, at no additional cost to the government.
The Contractor must be prepared to receive the full monthly sample contract
requirement at the time of contract award.
Whenever the Contractor is required to submit or resubmit data as a result of
an on-site laboratory evaluation or through an Administrative Project Officer
(APO)/Technical Project Officer (TPO) action, or through a Regional data reviewer's
request, the data must be clearly marked as ADDITIONAL DATA and must be sent to all
three contractual data recipients (SMO, EMSL/LV, and Region). A cover letter shall
be included which describes what data is being delivered, to which EPA Case(s) the
data pertains, and who requested the data.
whenever the Contractor is required to submit or resubmit data as a result of
Contract Compliance Screening (CCS) review by SMO, the data must be sent to all
three contractual data recipients (SMO, EMSL/LV and Region), and in all three
instances must be accompanied by a color-coded COVER SHEET (Laboratory Response To
Results of Contract Compliance Screening) provided by SMO. Diskette deliverables
need only be submitted or resubmitted to SMO. Revised DC-1 and DC-2 forms shall be
resubmitted to SMO.
Section IV of this Exhibit contains the required Inorganic Analysis Data
Reporting Forms in Agency-specified formats; Section III of this Exhibit contains
instructions to the Contractor for properly completing all data reporting forms to
provide the Agency with all required data. Data elements and field descriptors for
reporting data in computer-readable format are contained in Exhibit H.
Descriptions of the requirements for each deliverable item cited in the
Contract Performance/Delivery Schedule (see Contract Schedule, Section F) are
specified in parts A-G of 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 herein when the item is submitted.
B-4 ILM02.0
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Exhibit B Section II
A. Quality Assurance Plan and Standard Operating Procedures
See Exhibits E and F for requirements.
B. Sample Traffic Reports
Original Sample Traffic Report page marked "Lab Copy for Return to SMO" with
lab receipt information and signed with original Contractor signature, shall
be submitted for each sample in the Sample Delivery Group.
Traffic Reports (TRs) shall be submitted in Sample Delivery Group (SDG) sets
(i.e., TRs for all samples in an SDG shall be clipped together), with an SDG
Cover Sheet attached.
The SDG Cover Sheet shall contain the following items:
o Lab name
o Contract number
o Sample Analysis Price - full sample price from 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.
NOTE: When more than one sample is received in the first 01 last SDG shipment,
the "first" sample received would be the sample with the lowest sample number
(considering both alpha and numeric designations); the "last" sample received
would be the sample with the highest sample number (considering both alpha and
numeric designations).
In addition, each Traffic Report 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 Lab
Receipt Date on the TR.
EPA field sample numbers are six digits in length. If the Contractor receives
sample numbers of any other length, contact SMO immediately. The EPA sample
number of the first sample received in the SDG is the SDG number. When
several samples are received together in the first SDG shipment, the SDG
number 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 also reported on all data reporting forms. See Section III, Form
Instruction Guide.)
If samples are received at the laboratory with multi-sample Traffic Reports
(TRs), all the samples on one multi-sample TR may not necessarily be in the
same SDG. In this instance, the laboratory must make the appropriate number
of photocopies of the TR, and submit one copy with each SDG cover sheet.
C. Sample Data Package
The sample data package shall include data for analysis of all samples in one
Sample Delivery Group (SDG), including field and analytical samples,
reanalyses, blanks, spikes, duplicates, and laboratory control samples.
B-5 ILM02.0
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Exhibit B Section II
The sample data package must be complete before submission, must be
consecutively paginated (starting with page number one and ending with the
number of all pages in the package), and shall include the following:
1. Cover Page for the Inorganic Analyses Data Package, (COVER PAGE --
Inorganic Analyses Data Package), including: laboratory name; laboratory
code; contract number; Case No.; Sample Delivery Group (SDG) No.; SAS
Number (if appropriate); EPA sample numbers in alphanumeric order showing
EPA sample numbers cross-referenced with lab ID numbers; comments,
describing in detail any problems encountered in processing the samples in
the data package; and, completion of the statement on use of ICP
background and interelement corrections for the samples.
The Cover Page 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 and in the computer-readable data submitted
on diskette has been authorized by the Laboratory Manager or the Manager's
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 signers name and title,
and the date of signature.
In addition, on a separate piece of paper, the Contractor must also
include any problems encountered; both technical and administrative, the
corrective action taken, and the resolution.
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.
2. Sample Data
Sample data shall be submitted with the Inorganic Analysis Data Reporting
Forms for all samples in the SDG, arranged in increasing alphanumeric EPA
sample number order, followed by the QC analyses data, Quarterly
Verification of Instrument Parameters forms, raw data, and copies of the
digestion and distillation logs.
a. Results -- Inorganic Analysis Data Sheet [FORM I - IN]
Tabulated analytical results (identification and quantitation) of the
specified analytes (Exhibit C). The validation and release of these
results is authorized by a specific, signed statement on the Cover
Page. If the Laboratory Manager cannot verify all data reported for
each sample, he/she must provide a detailed description of the
problems associated with the sample(s) on the Cover Page.
Appropriate concentration units must be specified and entered on Form
I. The quantitative values shall be reported in units of micrograms
per liter (ug/L) for aqueous samples and milligrams per kilogram
(mg/kg) for solid samples. No other units are acceptable. Results
for solid samples must be reported on a. dry weight basis. Analytical
results must be reported to two significant figures if the result
value is less than 10; to three significant figures if the value is
B-6 ILM02.0
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Exhibit B Section II
greater than or equal to 10. Results for percent solids must be
reported to one decimal place. The preceding discussion concerning
significant numbers applies to Forms I and X only. For other Forms,
follow the instructions specific to those forms as contained in this
exhibit.
b. Quality Control Data
1) Initial and Continuing Calibration Verification [FORM II (PART
1) - IN]
2) CRDL Standard for AA and ICP [FORM II (PART 2) - IN]
3) Blanks [FORM III - IN]
4) ICP Interference Check Sample [FORM IV - IN]
5) Spike Sample Recovery [FORM V (PART 1) - IN]
6) Post Digest Spike Sample Recovery [FORM V (PART 2) - IN]
7) Duplicates [FORM VI - IN]
8) Laboratory Control Sample [FORM VII - IN]
9) Standard Addition Results [FORM VIII - IN]
10). ICP Serial Dilutions [FORM IX - IN]
11) Preparation Log [Form XIII - IN]
12) Analysis Run Log [Form XIV - IN]
c. Quarterly Verification of Instrument Parameters
1) Instrument Detection Limits (Quarterly) [FORM X - IN]
2) ICP Interelement Correction Factors (Annually) [FORM XI (PART 1)
- IN]
3) ICP Interelement Correction Factors (Annually) [FORM XI (PART 2)
- IN]
4) ICP Linear Ranges (Quarterly) [FORM XII - IN]
(Note that copies of Quarterly Verification of Instrument Parameters
forms for the current quarter must be submitted with each data
package.)
d. Raw Data
For each reported value, the Contractor shall include in the data
package all raw data used to obtain that value. This applies to all
required QA/QC measurements, instrument standardization, as well as
all sample analysis results. This statement does not apply to the
Quarterly Verification of Instrument Parameters submitted as a part
B-7 ILM02.0
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Exhibit B Section II
of each data package. Raw data must contain all instrument readouts
used for the sample results. Each exposure or instrumental reading
must be provided, including those readouts that may fall below the
IDL. All AA and ICP instruments must provide a legible hard copy of
the direct real-time instrument readout (i.e., stripcharts, printer
tapes, etc.). A photocopy of the instruments direct sequential
readout must be included. A hardcopy of the instrument's direct
instrument readout for cyanide must be included if the
instrumentation has the capability.
The order of raw data in the data package shall be: ICP, Flame AA,
Furnace AA, Mercury, and Cyanide. All raw data shall include
concentration units for ICP and absorbances or concentration units
for flame AA, furnace AA, Mercury and Cyanide. All flame and furnace
AA data shall be grouped by element.
Raw data must be labeled with EPA sample number and appropriate
codes, shown in Table 1 following, to unequivocally identify:
1) Calibration standards, including source and prep date.
2) Initial and continuing calibration blanks and preparation
blanks.
3) Initial and continuing calibration verification standards,
interference check samples, ICP serial dilution samples, CRDL
Standard for ICP and AA, Laboratory Control Sample and post
digestion spike.
4) Diluted and undiluted samples (by EPA sample number) and all
weights, dilutions and volumes used to obtain the reported
values. (If the volumes, weights and dilutions are consistent
for all samples in a given SDG, a general statement outlining
these parameters is sufficient).
5) Duplicates.
6) Spikes (indicating standard solutions used, final spike
concentrations, and volumes involved). If spike information
(source, concentration, volume) is consistent for a given SDG, a
general statement outlining these parameters is sufficient.
7) Instrument used, any instrument adjustments, data corrections or
other apparent anomalies on the measurement record, including
all data voided or data not used to obtain reported values and a
brief written explanation.
8) All information for furnace analysis clearly and sequentially
identified on the raw data, including EPA sample number, sample
and analytical spike data, percent recovery, coefficient of
variation, full MSA data, MSA correlation coefficient, slope and
intercepts of linear fit, final sample concentration (standard
addition concentration), and type of background correction used:
BS for Smith-Heiftje, BD for Deuterium Arc, or BZ for Zeeman.
B-8 ILM02.0
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Exhibit B Section II
9) Time and date of each analysis. Instrument run logs can be
submitted if they contain this information. If the instrument
does not automatically provide times of analysis, these must be
manually entered on all raw data J:or initial and continuing
calibration verification and blanks, as well as interference
check samples and the CRDL standard for ICP.
10) Integration times for AA analyses.
e. Digestion and Distillation Logs
Logs shall be submitted in the following order: digestion logs for
ICP, flame AA, furnace AA and mercury preparations, followed by a
copy of the distillation log for cyanide. These logs must include:
(1) date, (2) sample weights and volumes, (3) sufficient information
to unequivocally identify which QC samples (i.e., laboratory control
sample, preparation blank) correspond to each batch digested, (4)
comments describing any significant sample changes or reactions which
occur during preparation, and (5) indication of pH <2 or >12, as
applicable.
f. Properly completed Forms DC-1 and DC-2.
3. A copy of the Sample Traffic Reports submitted in Item A for all of the
samples in the SDG. The Traffic Reports shall be arranged in increasing
EPA Sample Number order, considering both alpha and numeric designations.
A legible photocopy of the SDG cover sheet must also be submitted.
D. Data in Computer Readable Form
The Contractor shall provide a computer-readable copy of the data on reporting
Forms I-XIV for all samples in the Sample Delivery Group, as specified in the
Contract Performance/Delivery Schedule. Computer-readable data deliverables
shall be submitted on an IBM or IBM-compatible, 5.25 inch floppy double-sided,
double density 360 K-byte or a high density 1.2 M-byte diskette or on an IBM
or IBM-compatible, 3.5 inch double-sided, double density 720 K-byte or a high
density 1.44 M-byte diskette. The data shall be recorded in ASCII, text file
format, and shall adhere to the file, record and field specifications listed
in Exhibit H, Data Dictionary and Format for Data Deliverables in Computer-
Readable Format.
When submitted, diskettes shall be packaged and shipped in such a manner that
the diskette(s) cannot be bent or folded, and will not be exposed to extreme
heat or cold or any type of electromagnetic radiation. The diskette(s) must
be included in the same shipment as the hardcopy data and shall, at a minimum,
be enclosed in a diskette ™.3.5.1er.
B-9 ILM02.0
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Exhibit B Section II
Table 1
Codes for Labelling Data
Sample XXXXXX
Sample not part of the SDG ZZZZZZ
Duplicate XXXXXXD
Matrix Spike XXXXXXS
Serial Dilution XXXXXXL
Analytical Spike XXXXXXA
Post Digestion/Distillation Spike XXXXXXA
MSA:
Zero Addition XXXXXXO
First Addition XXXXXX1
Second Addition XXXXXX2
Third Addition XXXXXX3
Instrument Calibration Standards:
ICP S or SO for blank standard
Atomic Absorption and Cyanide SO, S10,...etc.
Initial Calibration Verification ICV
Initial Calibration Blank ICB
Continuing Calibration Verification CCV
Continuing Calibration Blank CCB
Interference Check Samples:
Solution A ICSA
Solution AB ICSAB
CRDL Standard for AA CRA
CRDL Standard for ICP CRI
Laboratory Control Samples:
Aqueous (Water) LCSW
Solid (Soil/Sediment) LCSS
Preparation Blank (Water) PBW
Preparation Blank (Soil) PBS
Linear Range Analysis Standard LRS
Notes:
1. When an analytical spike or MSA is performed on samples other than field
samples, the "A", "0", "1", "2" or "3" suffixes must be the last to be added to
the EPA Sample Number. For instance, an analytical spike of a duplicate must
be formatted "XXXXXXDA."
2. The numeric suffix that follows the "S" suffix for the standards indicates the
true value of the concentration of the standard in ug/L.
3. ICP calibration standards usually consist of several analytes at different
concentrations. Therefore, no numeric suffix can follow the ICP calibration
standards unless all the analytes in the standard are prepared at the same
concentrations. For instance, the blank for ICP must be formatted "SO."
4. Use suffixes of "0", "1", "2", "3" as appropriate for samples identified with
ZZZZZZ on which MSA has been performed to indicate single injections.
B-10 ILM02.0
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Exhibit B Section II
E. Results of Intercomparison/Performance Evaluation (PE) Sample Analyses
Tabulation of analytical results for Intercomparison/PE Sample analyses
include all requirements specified in items C. and D., above.
F. Complete SPG File (CSF)
As specified in the Delivery Schedule, one Complete SDG File (CSF) including
the original Sample Data Package shall be delivered to the Region concurrently
with delivery of a copy 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 of Exhibit B. The Document Inventory Sheet, Form DC-2,
is contained in Section IV. The CSF will contain all original documents where
possible. No copies of original documents will be placed in the CSF unless the
originals are bound in a logbook maintained by the laboratory. The CSF will
contain all original documents specified in Sections III and IV, and Form DC-2
of Exhibit B of the SOW.
The CSF will consist of the following original documents in addition to the
documents in the Sample Data Package:
1. Original Sample Data Package
2. A completed and signed Document Inventory Sheet (Form DC-2)
3. All original shipping documents, including, but not limited to, the
following documents:
a. EPA Chain-of-Custody Record
b. Airbills
c. EPA (SMO) Traffic Reports
d. Sample Tags (if present) sealed in plastic bags.
4. All original receiving documents, including, but not limited to, the
following documents:
a. Form DC-1
b. Other receiving forms or copies of receiving logbooks.
c. SDG Cover Sheet
5. All original laboratory records of sample transfer, preparation, and
analysis, including, but not limited to, the following documents:
a. Original preparation and analysis forms or copies of preparation and
analysis logbook pages.
b. Internal sample and sample digestate/distillate transfer chain-of-
custody records.
B-ll ILM02.0
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Exhibit B Section II
6. All other original case-specific documents in the possession of the
laboratory, including, but not limited to, the following documents:
a. Telephone contact logs.
b. Copies of personal logbook pages.
c. All handwritten 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 case-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).
If the laboratory does submit case-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.
G. Quarterly and Annual Verification of Instrument Parameters
The Contractor shall perform and report quarterly verification of instrument
detection limits and linear range by the methods specified in Exhibit E for
each instrument used under this contract. For the ICP instrumentation, the
Contractor shall also perform and report annual interelement correction factors
(including method of determination), wavelengths used and integration times.
Forms for Quarterly and Annual Verification of Instrument Parameters for the
current quarter and year shall be submitted in each SDG data package, using
Forms X, XIA, XIB, and XII. Submission of Quarterly/Annual Verification of
Instrument Parameters shall include the raw data used to determine those values
reported.
H. Corrective Action Procedures
If a Contractor fails to adhere to the requirements detailed in this SOW, a
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, data package audit, an on-site laboratory
evaluation, remedial performance evaluation sample, and/or contract sanctions,
such as a Cure Notice (see Exhibit E for additional details).
B-12 ILM02.0
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Exhibit B Section III
SECTION III
FORM INSTRUCTION GUIDE!
This section contains specific instructions for the completion of all required
Inorganic Data Reporting Forms. This section is organized'into the following Parts:
A. General Information and Header Information
B. Cover Page -- Inorganic Analyses Data Package [COVER PAGE - IN]
C. Inorganic Analysis Data Sheet [FORM I - IN]
D. Initial and Continuing Calibration Verification [FORM II (PART 1) - IN]
E. CRDL Standard for AA and ICP [FORM II (PART 2) - IN]
F. Blanks [FORM III - IN]
G. ICP Interference Check Sample [FORM IV - IN]
H. Spike Sample Recovery [FORM V (PART 1) - IN]
I. Post Digest Spike Sample Recovery [FORM V (PART 2) - IN]
J. Duplicates [FORM VI - IN]
K. Laboratory Control Sample [FORM VII - IN]
L. Standard Addition Results [FORM VIII - IN]
M. ICP Serial Dilutions [FORM IX - IN]
N. Instrument Detection Limits (Quarterly) [FORM X - IN]
0. ICP Interelement Correction Factors (Annually) [FORM XI
(PART 1) - IN]
P. ICP Interelement Correction Factors (Annually) [FORM XI
(PART 2) - IN]
Q. ICP Linear Ranges (Quarterly) [FORM XII - IN]
R. Preparation Log [Form XIII - IN]
S. Analysis Run Log [Form XIV - IN]
T. Sample Log-In Sheet [Form DC-1]
U. Document Inventory Sheet [Form DC-2]
B-13 ILM02.0
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Exhibit B Section III
A. General Information and Header Information
The data reporting forms presented in Section IV in this Exhibit have been
designed in conjunction with the computer-readable data format specified in
Exhibit H, Data Dictionary and Format for Data Deliverables in Computer-
Readable Format. The specific length of each variable for computer-readable
data transmission purposes is given in Exhibit H. Information entered on these
forms must not exceed the size of the field given on the form, including such
laboratory-generated items as Lab Name and Lab Sample ID.
Note that on the hardcopy forms (see Section IV), the space provided for
entries is greater in some instances than the length prescribed for the
variable as written to diskette (see Exhibit H). Greater space is provided on
the hardcopy forms for the sake of visual clarity.
Values must be reported on the hardcopy forms according to the individual form
instructions in this section. Each form submitted must be filled out
completely for all analytes before proceeding to the next form of the same
type. Do not submit multiple forms in place of one form if the information on
those forms can be submitted on one form.
All characters which appear on the data reporting forms presented in the
contract (Exhibit B, Section IV) must be reproduced by the Contractor when
submitting data, and the format of the forms 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 EPA
Administrative Project Officer. The names of the various fields and analytes
(i.e., "Lab Code," "Aluminum") must appear as they do on the forms in the
contract, including the options specified in the form (i.e., "Matrix
(soil/water):" must appear, not just "Matrix").
All alphabetic entries made onto the forms by the Contractor must be in
UPPERCASE letters (i.e., "LOW", not "Low" or "low"). If an entry does not fill
the entire blank space provided on the form, null characters must be used to
remove the remaining underscores that comprise the blank line. (See Exhibit H
for additional instructions.) However, do not remove the underscores or
vertical bar characters that delineate "boxes" on the forms.
Six pieces of information are common to the header sections of each data
reporting form. These are: Lab Name, Contract, Lab Code, Case No., SAS No.,
and SDG No. This information must be entered on every form and must match on
all forms.
The "Lab Name" must be the name chosen by the Contractor to identify the
laboratory. It may not exceed 25 characters.
The "Contract" is the number of the EPA contract under which the analyses were
performed.
The "Lab Code" is an alphabetic abbreviation of up to 6 characters, 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 must not be
modified by the Contractor, except at the direction of EPA.
B-14 ILM02.0
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Exhibit B Section III
The "Case No." is the EPA-assigned Case number (to 5 spaces) associated with
the sample, and reported on the Traffic Report.
The "SAS No." is the EPA-assigned number for analyses performed under Special
Analytical Services. 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 this SOW (Routine Analytical Services
protocol) and have additional SAS requirements, list both Case No. and SAS No.
on all forms. If the analyses have no SAS requirements, leave "SAS No." blank.
(NOTE: Some samples in an SDG may have a SAS No., while others do not.)
The "SDG No." is the Sample Delivery Group (SDG) number. 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 must be
the lowest sample number (considering both alpha and numeric designations) in
the first group of samples received under the SDG.
The other information common to several of the forms is the "EPA Sample No.".
This number appears either in the upper righthand corner of the form, or as the
left column of a table summarizing data from a number of samples. When "EPA
Sample No." is entered into the triple-spaced box in the upper righthand corner
of a form, it must be centered on the middle line of the three lines that
comprise the box.
All samples, matrix spikes and duplicates must be identified with an EPA Sample
Number. For samples, matrix spikes and duplicates, the EPA Sample Number is
the unique identifying number given in the Traffic Report that accompanied that
sample.
In order to facilitate data assessment, the sample suffixes listed in Table 1
must be used.
Other pieces of information are common to many of the Data Reporting Forms.
These include: Matrix and Level.
For "Matrix", enter "SOIL" for soil/sediment samples, and enter "WATER" for
water samples. NOTE: The matrix must be spelled out. Abbreviations such as
"S" or "W" must not be used.
For "Level", enter the determination of concentration level. Enter as "LOW" or
"MED", not "L" or "M".
Note: All results must be transcribed to Forms II-XIV from the raw data to the
specified number of decimal places that are described in Exhibits B and H. The
raw data result is to be rounded only when the number of figures in the raw
data result exceeds the maximum number of figures specified for that result
entry for that form. If there are not enough figures in the raw data result to
enter in the specified space for that result, then zeros must be used for
decimal places to the specified number of reporting decimals for that result
for a specific form. The following examples are provided:
B-15 ILM02.0
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Exhibit B Section III
Raw Data Result
95.99653
95.99653
95.99653
95.996
95.9
Specified Format
5.4 (to four decimal places)
5.3 (to three decimal places)
5.2 (to two decimal places)
5.4 (to four decimal places)
5.4 (to four decimal places)
Correct Entrv on Form
95.9965
95.997
96.00
95.9960
95.9000
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 up). If the figure
following the last digit to be retained equals 5 and there are no digits to the
right of the 5 or all digits to the right of the 5 equal zero, then round up if
the digit to be retained is odd, or round down if that digit is even. See also
Rounding Rules entry in Glossary (Exhibit G).
Before evaluating a number for being in control or out of control of a certain
limit, the number evaluated must be rounded using EPA rounding rules to the
significance reported for that limit. For instance, the control limit for an
ICV is plus or minus 10% of the true value. A reported percent recovery value
of 110.4 would be considered in control while a reported value of 110.6 would
be considered out of control. In addition, a calculated value of 110.50 would
be in control while a calculated value of 110.51 would be out of control.
B. Cover Page - Inorganic Analyses Data Package [COVER PAGE-IN]
This form is used to list all samples analyzed within a Sample Delivery Group,
and to provide certain analytical information and general comments. It is also
the document which is signed by the Laboratory Manager to authorize and release
all data and deliverables associated with the SDG.
Complete the header information according to the instructions in Part A.
For samples analyzed using this SOW, enter " ILM02.0" for SOW No.
Enter the EPA Sample No. (including spikes and duplicates) (to seven spaces) of
every sample analyzed within the SDG. Spikes must contain an "S" suffix and
duplicates a "D" suffix. These sample numbers must be listed on the form in
ascending alphanumeric order. Thus, if MAB123 is the lowest (considering both
alpha and numeric characters) EPA Sample No. within the SDG, it would be
entered in the first EPA Sample No. field. Samples would be listed below it,
in ascending sequence - MAB124, MAB125, MAClll, MA1111, MA1111D, etc.
A maximum of twenty (20) sample numbers can be entered on this form. Submit
additional Cover Pages, as appropriate, if the total number of samples,
duplicates, and spikes in the SDG is greater than twenty (20).
A Lab Sample ID (to ten spaces) may be entered for each EPA Sample No. If a Lab
Sample ID is entered, it must be entered identically (for each EPA Sample No.)
on all associated data.
B-16 ILM02.0
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Exhibit B Section III
Enter "YES" or "NO" in answer to each of the two questions concerning ICP
corrections. Each question must be explicitly answered with a "YES" or a "NO."
The third question must be answered with a "YES" or "NO" if the answer to the
second question is "YES." It should be left blank if the answer to the second
question is "NO."
Under "Comments," enter any statements relevant to the analyses performed under
the SDG as a whole.
Each Cover Page must be signed, in original, by the Laboratory Manager or the
Manager's designee and dated, to authorize the release and verify the contents
of all data and deliverables associated with an SDG.
C. Inorganic Analysis Data Sheet [FORM 1-IN]
This form is used to tabulate and report sample analysis results for target
analytes (Exhibit C).
Complete the header information according to the instructions in Part A and as
follows.
"Date Received" is the date (formatted MM/DD/YY) of sample receipt at the
laboratory, as recorded on the Traffic Report, i.e., the Validated Time of
Sample Receipt (VTSR).
"% Solids" is the percent of solids on a weight/weight basis in the sample as
determined by drying the sample as specified in Exhibit D. Report percent
solids to one decimal place (i.e., 5.3%). If the percent solids is not
required because the sample is fully aqueous or less than 1% solids, then enter
"0.0."
Enter the appropriate concentration units (UG/L for water or MG/KG dry weight
for soil). Entering "MG/KG" means "mg/Kg dry weight" on this form.
Under the column labeled "Concentration," enter for each analyte either the
value of the result (if the concentration is greater than or equal to the
Instrument Detection Limit) or the Instrument Detection Limit for the analyte
corrected for any dilutions (if the concentration is less than the Instrument
Detection Limit). The concentration result must be reported to two significant
figures if the result is less than 10; to three sig figures if the value is
greater than or equal to 10.
Under the columns labeled "C," "Q," and "M," enter result qualifiers as
identified below. If additional qualifiers are used, their explicit
definitions must be included on the Cover Page in the Comments section.
FORM I-IN includes fields for three types of result qualifiers. These
qualifiers must be completed as follows:
o C (Concentration) qualifier -- Enter "B" if the reported value was obtained
from a reading that was less than the Contract Required Detection Limit
(CRDL) but greater than or equal to the Instrument Detection Limit (IDL).
If the analyte was analyzed for but not detected, a "U" must be entered.
B-17 ILM02.0
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Exhibit B Section III
o Q qualifier -- Specified entries and their meanings are as follows:
E - The reported value is estimated because of the presence of
interference. An explanatory note must be included under Comments
on the Cover Page (if the problem applies to all samples) or on the
specific FORM I-IN (if it is an isolated problem).
M - Duplicate injection precision not met.
N - Spiked sample recovery not within control limits.
S - The reported value was determined by the Method of Standard
Additions (MSA).
W - Post-digestion spike for Furnace AA analysis is out of control
limits (85-115%), while sample absorbance is less than 50% of spike
absorbance. (See Exhibit E.)
* - Duplicate analysis not within control limits.
+ - Correlation coefficient for the MSA is less than 0.995.
Entering "S," "W," or "+" is mutually exclusive. No combination of these
qualifiers can appear in the same field for an analyte.
o M (Method) qualifier -- Enter:
»pn for Icp
"A" for Flame AA
"F" for Furnace AA
"PM" for ICP when Microwave Digestion is; used
"AM" for flame AA when Microwave Digestion is used
"FM" for Furnace AA when Microwave Digestion is used
"CV" for Manual Cold Vapor AA
"AV" for Automated Cold Vapor AA
"CA" for Midi-Distillation Spectrophotorietric
"AS" for Semi-Automated Spectrophotometric
"C" for Manual Spectrophotometric
"T" for Titrimetric
" " where no data has been entered
"NR" if the analyte is not required to be analyzed.
A brief physical description of the sample, both before and after digestion,
must be reported in the fields for color (before and after), clarity (before
and after), texture and artifacts. For water samples, report color and
clarity. For soil samples, report color, texture and artifacts.
The following descriptive terms are recommended:
Color - red, blue, yellow, green, orange, violet, white,
colorless, brown, grey, black
Clarity - clear, cloudy, opaque
Texture - fine (powdery), medium (sand), coarse (large crystals or
rocks)
B-18 ILM02.0
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Exhibit B Section III
If artifacts are present, enter "YES" in the artifacts field and describe the
artifacts in the Comments field. If artifacts are not present, leave this
field blank.
Note any significant changes that occur during sample preparation (i.e.,
emulsion formation) in the Comments field. Enter any sample-specific comments
concerning the analyte results in the Comments field.
D. Initial and Continuing Calibration Verification [FORM II(PART 1)-IN]
This form is used to report analyte recoveries from calibration solutions.
Complete the header information according to the instructions in Part A and as
follows.
Enter the Initial Calibration Source (12 spaces maximum) and the Continuing
Calibration Source (12 spaces maximum). Enter "EPA-LV" or "EPA-CI" to indicate
EPA EMSL Las Vegas or Cincinnati, respectively, as the source of EPA standards.
When additional EPA supplied solutions are prepared in the future, the
Contractor must use the codes supplied with those solutions for identification.
If other sources were used, enter sufficient information in the available 12
spaces to identify the manufacturer and the solution used.
Use additional FORMs II(PART 1)-IN if more calibration sources were used.
Under "Initial Calibration True," enter the value (in ug/L, to one decimal
place) of the concentration of each analyte in the Initial Calibration
Verification Solution.
Under "Initial Calibration Found," enter the most recent value (in ug/L, to two
decimal places), of the concentration of each analyte measured in the Initial
Calibration Verification Solution.
Under "Initial Calibration %R," enter the value (to one decimal place) of the
percent recovery computed according to the following equation:
%R = Found(ICV) x 100 (2.1)
True(ICV)
Where, True(ICV) is the true concentration of the analyte in the Initial
Calibration Verification Solution and Found(ICV) is the found concentration of
the analyte in the Initial Calibration Verification Solution.
The values used in equation 2.1 for True(ICV) and Found(ICV) must be exactly
those reported on this form.
Under "Continuing Calibration True," enter the value (in ug/L, to one decimal
place) of the concentration of each analyte in the Continuing Calibration
Verification Solution.
Under "Continuing Calibration Found," enter the value (in ug/L, to two decimal
places) of the concentration of each analyte measured in the Continuing
Calibration Verification Solution.
B-19 ILM02.0
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Exhibit B Section III
Note that the form contains two "Continuing Calibration Found" columns. The
column to the left must contain values for the first Continuing Calibration
Verification, and the column to the right must contain values for the second
Continuing Calibration Verification. The column to the right should be left
blank if no second Continuing Calibration Verification was performed.
If more than one FORM II(PART 1)-IN is required to report multiple Continuing
Calibration Verifications, then the column to the left on the second form must
contain values for the third Continuing Calibration Verification, the column to
the right must contain values for the fourth Continuing Calibration
Verification, and so on.
Under "Continuing Calibration %R," enter the value (to one decimal place) of
the percent recovery computed according to the following equation:
%R - Found(CCV) x 10Q (2.2)
True(CCV)
where, True(CCV) is the true concentration of each analyte, and Found(CCV) is
the found concentration of the analyte in the Continuing Calibration
Verification Solution.
The values used in equation 2.2 for True(CCV) and Found(CCV) must be exactly
those reported on this form.
Note that the form contains two "Continuing Calibration %R" columns. Entries
to these columns must follow the sequence detailed above for entries to the
"Continuing Calibration Found" columns.
Under "M," enter the method used or "NR," as explained in Part C.
If more than one wavelength is used to analyze an analyte, submit additional
FORMs II(PART 1)-IN as appropriate.
The order of reporting ICVs and CCVs for each analyte must follow the temporal
order in which the standards were run starting with the first Form HA and
moving from the left to the right continuing to the following Form IIA's as
appropriate. For instance, the first ICV for all analytes must be reported on
the first Form HA. In a run where three CCVs were analyzed, the first CCV
must be reported in the left CCV column on the first Form HA and the second
CCV must be reported in the right column of the same form. The third CCV must
be reported in the left CCV column of the second Form HA. On the second Form
IIA, the ICV column and the right CCV column must be left empty in this
example. In the previous example, if a second run for an analyte was needed,
the ICV of that run must be reported on a third Form IIA and the CCVs follow in
the same fashion as explained before. In the case where two wavelengths are
use used for an analyte, all ICV and CCV results of one wavelength from all
runs must be reported before proceeding to report the results of the second
wavelength used.
B-20 ILM02.0
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Exhibit B Section III
CRDL Standard for AA and ICP [FORM II(PART 2) -IN]
This form is used to report analyte recoveries from analyses of the CRDL
Standards for AA (CRA) and 2x the CRDL Standards for ICP (CRI) .
Complete the header information according to the instructions in Part A and as
follows .
Enter the AA CRDL Standard Source (12 spaces maximum) and the ICP CRDL Standard
Source (12 spaces maximum), as explained in Part D.
Under "CRDL Standard for AA True," enter the value (in ug/L, to one decimal
place) of the concentration of each analyte in the CRDL Standard Source
Solution that was analyzed.
Under "CRDL Standard for AA Found," enter the value (in ug/L, to two decimal
places) of the concentration of each analyte measured in the CRDL Standard
Solution.
Under "CRDL Standard for AA %R," enter the value (to one decimal place) of the
percent recovery computed according to the following equation:
Found CRDL Standard for AA
True CRDL Standard for AA
(2.3)
Under "CRDL Standard for ICP Initial True," enter the value (to one decimal
place) of the concentration of each analyte in the CRDL Standard Solution that
was analyzed by ICP for analytical samples associated with the SDG.
Concentration units are ug/L.
Under "CRDL Standard for ICP Initial Found," enter the value (to two decimal
places) of the concentration of each analyte measured in the CRDL Standard
Soluti6n analyzed at the beginning of each run. Concentration units are ug/L.
Under "CRDL Standard for ICP, Initial %R," enter the value (to one decimal
place) of the percent recovery computed according to the following equation:
%R _ CRDL Standard for ICP Initial Found x IQQ (2.4)
CRDL Standard for ICP True
Under "CRDL Standard for ICP Final Found," enter the value (in ug/L, to two
decimal places) of the concentration of each analyte measured in the CRDL
Standard Solution analyzed at the end of each run.
Under "CRDL Standard for ICP Final %R," enter the value (to one decimal place)
of the percent recovery computed according to the following equation:
%R _ CRDL Standard for ICP Final Found x ^QQ /2 5)
CRDL Standard for ICP True
All %R values reported in equations 2.3, 2.4, and 2.5 must be calculated using
the exact true and found values reported on this form.
B-21 ILM02:0
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Exhibit B Section III
Note that for every initial solution reported there must be a final one.
However, the opposite is not true. If a CRDL Standard for ICP (CRI) was
required to be analyzed in the middle of a run (to avoid exceeding the 8-hour
limit), it must be reported in the "Final Found" section of this form.
If more CRI or CRA analyses were required or analyses were performed using more
than one wavelength per analyte, submit additional FORMs II(PART 2)-IN as
appropriate.
The order of reporting CRAs and CRIs for each analyte must follow the temporal
order in which the standards were run starting with the first Form IIB and
continuing to the following Form IIBs as appropriate. The order of reporting
CRA and CRI is independent with respect to each other. When multiple
wavelengths are used for one analyte, all the results of one wavelength must be
reported before proceeding to the next wavelength.
F. Blanks [FORM III-IN]
This form is used to report analyte concentrations found in the Initial
Calibration Blank (ICB), in Continuing Calibration Blanks (CCB), and in the
Preparation Blank (PB).
Complete the header information according to the instructions in Part A and as
follows.
Enter "SOIL"r~or "WATER" as appropriate as the matrix of the Preparation Blank.
No abbreviations or other matrix descriptors may be used.
According to the matrix specified for the Preparation Blank, enter "UG/L" (for
water) or "MG/KG" (for soil) as the Preparation Blank concentration units.
Under "Initial Calib. Blank," enter the concentration (in ug/L, to one decimal
place) of each analyte in the most recent Initial Calibration Blank.
Under the "C" qualifier field, for any analyte enter "B" if the absolute value
of the analyte concentration is less than the CRDL but greater than or equal to
the IDL. Enter "U" if the absolute value of the analyte in the blank is less
than the IDL.
Under "Continuing Calibration Blank 1," enter the concentration (in ug/L, to
one decimal place) of each analyte detected in the first required Continuing
Calibration Blank (CCB) analyzed after the Initial Calibration Blank. Enter
any appropriate qualifier, as explained for the "Initial Calibration Blank," to
the "C" qualifier column immediately following the "Continuing Calibration
Blank 1" column.
If only one Continuing Calibration Blank was analyzed, then leave the columns
labeled "2" and "3" blank. If up to three CCBs were analyzed, complete the
columns labeled "2" and "3," in accordance with the instructions for the
"Continuing Calibration Blank 1" column. If more than three Continuing
Calibration Blanks were analyzed, then complete additional FORMs III-IN as
appropriate.
B-22 ILM02.0
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Exhibit B Section III
Under "Preparation Blank," enter the concentration in ug/L (to three decimal
places) for a water blank or in mg/Kg (to three decimal places) for a soil
blank, of each analyte in the Preparation Blank. Enter any appropriate
qualifier, as explained for the "Initial Calibration Blank," to the "C"
qualifier column immediately following the "Preparation Blank" column.
For all blanks, enter the concentration of each analyte (positive or negative)
measured above the IDL or below the negative value of the IDL.
Under "M," enter the method used, as explained in Part C.
If more than one wavelength is used to analyze an analyte, submit additional
FORMs III -IN as appropriate.
The order of reporting ICBs and CCBs for each analyte must follow the temporal
order in which the blanks were run starting with the first Form III and moving
from left to right and continuing to the following Form Ills as explained in
Part D. When multiple wavelengths are used for the analysis of one analyte,
all the results of one wavelength must be reported before proceeding to the
next wavelength.
G. ICP Interference Check Sample [FORM IV- IN]
This form is used to report Interference Check Sample (ICS) results for each
ICP instrument used in Sample Delivery Group analyses.
Complete the header information according to the instructions in Part A and as
follows:
For "ICP ID Number," enter an identifier that uniquely identifies a specific
instrument within the Contractor laboratory. No two ICP instruments within a
laboratory may have the same ICP ID Number.
Enter "ICS Source" (12 spaces maximum) as explained in Part D. For EPA
solutions, include in the source name a number identifying it (e.g., EPA-LV87) .
Under "True Sol. A," enter the true concentration (in ug/L, to the nearest
whole number) of each analyte present in Solution A.
Under "True Sol. AB," enter the true concentration (in ug/L, to the nearest
whole number) of each analyte present in Solution AB.
Under "Initial Found Sol. A," enter the concentration (in ug/L, to the nearest
whole number) of each analyte found in the initial analysis of Solution A as
required in Exhibit E.
Under "Initial Found Sol. AB," enter the concentration (in ug/L, to one decimal
place) of each analyte in the initial analysis of Solution AB as required in
Exhibit E.
Under "Initial Found %R," enter the value (to one decimal place) of the percent
recovery computed for true solution AB greater than zero according to the
following equation:
B-23 ILM02.0
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Exhibit B Section III
%R - Initial Found Solution AB x IQQ (2.6)
True Solution AB
Leave the field blank if true solution AB equals zero.
Under "Final Found Sol. A," enter the concentration (in ug/L, to the nearest
whole number) of each analyte found in the final analysis of Solution A as
required in Exhibit E.
Under "Final Found Sol. AB," enter the concentration (in ug/L, to one decimal
place) of each analyte found in the final analysis of Solution AB as required
in Exhibit E.
For All Found values of solutions A and AB, enter the concentration (positive,
negative, or zero) of each analyte at each wavelength used for analysis by ICP.
Under "Final Found %R," enter the value (to one decimal place) of the percent
recovery computed according to the following equation:
%R - Final Found Solution AB x IQQ (2.7)
True Solution AB
All %R values reported must be calculated using the exact true and found values
reported on this form.
Note that for every initial solution reported there must be a final one.
However, the opposite is not true. If an ICS was required to be analyzed in
the middle of a run (to avoid exceeding the 8-hour limit), it must be reported
in the "Final Found" section of this form.
If more ICS analyses were required, submit additional FORMs IV-IN as
appropriate.
The order of reporting ICSs for each analyte must follow the temporal order in
which the standards were run starting with the first Form IV and continuing to
the following Form IVs as appropriate. When multiple wavelengths are used for
one analyte, all the results of one wavelength must be reported before
proceeding to the next wavelength.
H. Spike Sample Recovery [FORM V(PART 1)-IN]
This form is used to report results for the pre-digest spike.
Complete the header information according to the instructions in Part A and as
follows.
Indicate the appropriate matrix, level and concentration units (ug/L for water
and mg/Kg dry weight for soil) as explained in Parts A and C.
For "%Solids for Sample," enter the percent solids (as explained in Part C) for
the original sample of the EPA Sample Number reported on the form. Note that
this number must equal the one reported on Form I for that sample.
B-24 ILM02.0
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Exhibit B Section III
In the "EPA Sample No." box, enter the EPA Sample Number (7 places maximum) of
the sample from which the spike results on this form were obtained. The number
must be centered in the box.
Under "Control Limit %R," enter "75-125" if the spike added value was greater
than or equal to one-fourth of the sample result value. If not, leave the
field empty.
Under "Spiked Sample Result (SSR)," enter the measured value (to four decimal
places), in appropriate units, for each relevant analyte in the matrix spike
sample. Enter any appropriate qualifier, as explained in Part C, to the "C"
qualifier column immediately following the "Spiked Sample Result (SSR)" column.
Under "Sample Result (SR)," enter the measured value (to four decimal places)
for each required analyte in the sample (reported in the EPA Sample No. box) on
which the matrix spike was performed. Enter any appropriate qualifier, as
explained in Part C, to the "C" qualifier column immediately following the
"Sample Result (SR)" column.
Under "Spike Added (SA)," enter the value (to two decimal places) for the
concentration of each analyte added to the sample. The same concentration
units must be used for spiked sample results, unspiked (original sample)
results, and spike added sample results. If the "spike added" concentration is
specified in the contract, the value added and reported must be that specific
concentration in appropriate units, corrected for spiked sample weight and %
solids (soils) or spiked sample volume (waters).
Under "%R," enter the value (to one decimal place) of the percent recovery for
all spiked analytes computed according to the following equation:
%R - (SSR ' SR) x 100 (2.8)
SA
%R must be reported, whether it is negative, positive or zero.
The values for SSR, SR, and SA must be exactly those reported on this form. A
value of zero must be used in calculations for SSR or SR if the analyte value
is less than the IDL.
Under "Q," enter "N" if the Spike Recovery (%R) is out of the control limits
(75-125) and the Spike Added (SA) is greater than or equal to one-fourth of the
Sample Result (SR).
Under "M," enter the method used (as explained in Part C) or enter "NR" if the
analyte is not required in the spike.
If different samples were used for spike sample analysis of different analytes,
additional FORMs V(PART 1)-IN must be submitted for each sample as appropriate.
Post Digest Soike Sample Recovery [FORM V(PART 2)-IN]
This form is used to report results for the post-digest spike recovery which is
based upon the addition of a known quantity of analyte to an aliquot of the
digested sample.
B-25 ILM02.0
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Exhibit B Section III
Complete the header information according to the instructions in Part A and as
follows.
In the "EPA Sample No." box, enter the EPA Sample Number (7 spaces maximum) of
the sample from which the spike results on this form were obtained. The number
must be centered in the box.
The "Control Limit %R" and "Q" fields must be left blank until limits are
established by EPA. At that time, the Contractor will be informed how to
complete these fields.
Under "Spiked Sample Result (SSR)," enter the measured value (in ug/L, to two
decimal places) for each analyte in the post-digest spike sample. Enter any
appropriate qualifier, as explained in Part C, to the "C" qualifier column
immediately following the "Spiked Sample Result (SSR)" column.
Under "Sample Result (SR)," enter the measured value (in ug/L, to two decimal
places) for the concentration of each analyte in the sample (reported in the
EPA Sample No. box) on which the spike was performed. Enter any appropriate
qualifier, as explained in Part C, to the "C" qualifier column immediately
following the "Sample Result (SR)" column.
Under "Spike Added (SA)," enter the value (in ug/L, to one decimal place) for
each analyte added to the sample. The same concentration units must be used
for spiked sample results, unspiked (original sample) results, and spike added
sample results. If the spike added concentration is specified in the contract,
the value added and reported must be that specific concentration in appropriate
units.
Under "%R," enter the value (to one decimal place) of the percent recovery for
all spiked analytes computed according to Equation 2.8 in Part H
%R must be reported, whether it is negative, positive or zero.
The values for SSR, SR, and SA must be exactly those reported on this form. A
value of zero must be substituted for SSR or SR if the analyte value is less
than the IDL.
Under "M," enter the method used as explained in Part C, or enter "NR" if the
spike was not required.
If different samples were used for spike sample analysis of different analytes,
additional FORMS V(PART 1)-IN must be submitted.
Duplicates [FORM VI-IN]
The duplicates form is used to report results of duplicate analyses. Duplicate
analyses are required for % solids values and all analyte results.
Complete the header information according to the instructions in Part A and as
follows.
Indicate the appropriate matrix, level and concentration units (ug/L for water
and mg/Kg dry weight for soil) as explained in Parts A and C.
B-26 ILM02.0
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Exhibit B Section III
For "% Solids for Sample," enter the percent solids (as explained in Part C)
for the original sample of the EPA Sample Number reported on the form. Note
that this number must equal the one reported on Form I for that sample.
For "% Solids for Duplicate," enter the percent solids (as explained in Part C)
for the duplicate sample of the EPA Sample Number reported on the form.
In the "EPA Sample No." box, enter the EPA Sample Number (7 spaces maximum) of
the sample from which the duplicate sample results on this form were obtained.
The number must be centered in the box.
Under "Control Limit," enter the CRDL (in appropriate units, ug/L for water or
mg/kg dry weight basis compared to the original sample weight and percent
solids) for the analyte if the sample or duplicate values were less than 5x
CRDL and greater than or equal to the CRDL. If the sample and duplicate values
were greater than or equal to 5x CRDL, leave the field empty.
Under Sample (S), enter the original measured value (to four decimal places)
for the concentration of each analyte in the sample (reported in the EPA Sample
No. box) on which a Duplicate analysis was performed. Concentration units are
those specified on the form. Enter any appropriate qualifier, as explained in
Part C, to the "C" qualifier column immediately following the "Sample (S)"
column.
Under Duplicate (D), enter the measured value (to four decimal places) for
each analyte in the Duplicate sample. Concentration units are those specified
on the form. Enter any appropriate qualifier, as explained in Part C, to the
"C" qualifier column immediately following the "Duplicate (D)" column.
For solid samples, the concentration of the original sample must be computed
using the weight and % solids of the original sample. The concentration of the
duplicate sample must be computed using the weight of the duplicate sample, but
the % solids of the original sample.
Under RPD, enter the absolute value (to one decimal place) of the Relative
Percent Difference for all analytes detected above the IDL in either the sample
or the duplicate, computed according to the following equation:
PPH- Is - D I v 100 (2.9)
(S + D)/2
The values for S and D must be exactly those reported on this form. A value of
zero must be substituted for S or D if the analyte concentration is less than
the IDL in either one. If the analyte concentration is less than the IDL in
both S and D, leave the RPD field empty.
Under "Q," enter "*" if the duplicate analysis for the analyte is out of
control. If both sample and duplicate values are greater than or equal to 5x
CRDL, then the RPD must be less than or equal to 20% to be in control. If
either sample or duplicate values are less than 5x CRDL, then the absolute
difference between the two values must be less than the CRDL to be in control.
If both values are below the CRDL, then no control limit is applicable.
Under "M," enter method used as explained in Part C.
B-27 ILM02.0
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Exhibit B Section III
K. Laboratory Control Sample [FORM VII-IN]
This form is used to report results for the solid and aqueous Laboratory
Control Samples.
Complete the header information according to the instructions in Part A and as
follows.
For the Solid LCS Source (12 spaces maximum), enter the appropriate EPA sample
number if the EPA provided standard was used. Substitute an appropriate number
provided by the EPA for LCS solutions prepared in the future. If other sources
were used, identify the source as explained in Part D. For the Aqueous LCS
Source, enter the source name (12 spaces maximum) as explained in Part D.
Under "Aqueous True," enter the value (in ug/L, to one decimal place) of the
concentration of each analyte in the Aqueous LCS Standard Source.
Under "Aqueous Found," enter the measured concentration (in ug/L, to two
decimal places) of each analyte found in the Aqueous LCS solution.
Under "Aqueous %R," enter the value of the percent recovery (to one decimal
place) computed according to the following equation:
%R - Aqueous LCS Found x 10Q (2 10)
Aqueous LCS True
Under "Solid True," enter the value (in mg/Kg, to one decimal place) of the
concentration of each analyte in the Solid LCS Source.
Under "Solid Found," enter the measured value (in mg/Kg, to one decimal place)
of each analyte found in the Solid LCS solution.
Under "C," enter "B" or "U" or leave empty, to describe the found value of the
solid LCS as explained in Part C.
Under "Limits," enter the lower limit (in mg/Kg, to one decimal place) in the
left column, and the upper limit (in mg/Kg, to one decimal place) in the right
column, for each analyte in the Solid LCS Source solution.
Under "Solid %R," enter the value of the percent recovery (to one decimal
place) computed according to the following equation:
%R - Solid LCS Found x 100 (2 U)
Solid LCS True
The values for true and found aqueous and solid LCSs used in equations 2.10 and
2.11 must be exactly those reported on this form. If the analyte concentration
is less than the IDL, a value of zero must be substituted for the solid LCS
found.
Submit additional FORMs VII-IN as appropriate, if more than one aqueous LCS or
solid LCS was required.
B-28 ILM02.0
-------
Exhibit B Section III
L. Standard Addition Results [FORM VIII-IN]
This form is used to report the results of samples analyzed using the Method of
Standard Additions (MSA) for Furnace AA analysis.
Complete the header information according to the instructions in Part A.
Under "EPA Sample No.," enter the EPA Sample Numbers (7 spaces maximum) of all
analytical samples analyzed using the MSA. This includes reruns by MSA (if the
first MSA was out of control) as explained in Exhibit E.
Note that only field samples and duplicates may be reported on this form, thus
the EPA Sample Number usually has no suffix or a "D."
A maximum of 32 samples can be entered on this form. If additional samples
required MSA, submit additional FORMs VIII-IN. Samples must be listed in
alphanumeric order per analyte, continuing to the next FORM VIII-IN if
applicable.
Under "An," enter the chemical symbol (2 spaces maximum) for each analyte for
which MSA was required for each sample listed. The analytes must be in
alphabetic listing of the chemical symbols.
Results for different samples for each analyte must be reported sequentially,
with the analytes ordered according to the alphabetic listing of their chemical
symbols. For instance, results for As (arsenic) in samples MAA110, MAAlll, and
MAA112 would be reported in sequence, followed by the result for Pb (lead) in
MAA110 etc.
»
Under "0 ADD ABS," enter the measured value in absorbance units (to three
decimal places) for the analyte before any addition is performed.
Under "1 ADD CON," enter the final concentration in ug/L (to two decimal
places) of the analyte (excluding sample contribution) after the first addition
to the sample analyzed by MSA.
Under "1 ADD ABS," enter the measured value (in the same units and decimal
places as "0 ADD ABS") of the sample solution spiked with the first addition.
Under "2 ADD CON," enter the final concentration in ug/L (to two decimal
places) of the analyte (excluding sample contribution) after the second
addition to the sample analyzed by MSA.
Under "2 ADD ABS," enter the measured value (in the same units and decimal
places as "0 ADD ABS") of the sample solution spiked with the second addition.
Under "3 ADD CON," enter the final concentration in ug/L (to two decimal
places) of the analyte (excluding sample contribution) after the third addition
to the sample analyzed by MSA.
Under "3 ADD ABS," enter the measured value (in the same units and decimal
places as "0 ADD ABS") of the sample solution spiked with the third addition.
B-29 ILM02.0
-------
Exhibit B Section III
Note that "0 ADD ABS," "1 ADD ABS" "2 ADD ABS," and "3 ADD ABS" must have the
same dilution factor.
Under "Final Cone.," enter the final analyte concentration (in ug/L, to one
decimal place) in the sample as determined by MSA computed according to the
following formula:
Final Cone. - - (x-intercept) (2.12)
Note that the final concentration of an analyte does not have to equal the
value for that analyte which is reported on FORM I-IN for that sample.
Under "r," enter the correlation coefficient (to four decimal places) that is
obtained for the least squares regression line representing the following
points (x,y):(0.0, "0 ADD ABS"), ("1 ADD CON," "1 ADD ABS"), ("2 ADD CON," "2
ADD ABS"), ("3 ADD CON," "3 ADD ABS").
Note that the correlation coefficient must be calculated using the ordinary
least squares linear regression (unweighted) according to the following
formula:
N Z
r vr V 2 / V \ 2 l 1 rn ?• 2 / V
[N X xi - ( L xi> I1* [N Z yi - < Z
Under "Q," enter "+" if r is less than 0.995. If r is greater than or equal to
0.995, then leave the field empty.
M. ICP Serial Dilutions [FORM IX-IN]
This form is used to report results for ICP serial dilution.
Complete the header information according to the instructions in Part A and as
follows.
In the "EPA Sample No." box, enter the EPA Sample Number (7 places maximum) of
the sample for which serial dilution analysis results on this form were
obtained. The number must be centered in the box.
Under "Initial Sample Result (I)," enter the measured value (in ug/L, to two
decimal places) for each ICP analyte in the undiluted sample (for the EPA
sample number reported on this form). Enter any appropriate qualifier, as
explained in Part C, to the "C" qualifier column immediately following the
"Initial Sample Result (I)" column.
Note that the Initial Sample Concentration for an analyte does not have to
equal the value for that analyte reported on FORM I-IN for that sample. It is
the value of the analyte concentration (uncorrected for dilution) that is
within the linear range of the instrument.
B-30 ILM02.0
-------
Exhibit B Section III
Under "Serial Dilution Result (S)", enter the measured concentration value (in
ug/L, to two decimal places) for each ICP analyte in the diluted sample. The
value must be adjusted for that dilution. Enter any appropriate qualifier, as
explained in Part B, to the "C" qualifier column immediately following the
"Serial Dilution Result (S)" column.
Note that the Serial Dilution Result (S) is obtained by multiplying by five the
instrument measured value (in ug/L) of the serially diluted sample and that the
"C" qualifier for the serial dilution must be established based on the serial
dilution result before correcting it for the dilution regardless of the value
reported on the form.
Under "% Difference," enter the absolute value (to one decimal place) of the
percent difference in concentration of required analytes, between the original
sample and the diluted sample (adjusted for dilution) according to the
following formula:
% Difference - I * " S I x 10° (2.14)
I
The values for I and S used to calculate % Difference in equation 2.14 must be
exactly those reported on this form. A value of zero must be substituted for S
if the analyte concentration is less than the IDL. If the analyte
concentration in (I) is less than the IDL, concentration leave "% Difference"
field empty.
Under "Q," enter "E" if the % Difference is greater than 10% and the original
sample concentration (reported on FORM I-IN) is greater than 50x the IDL
reported on FORM X-IN.
Under "M," enter the method of analysis for each analyte as explained in Part
C.
N. Instrument Detection Limits (Quarterly) [FORM X-IN]
This form documents the Instrument Detection Limits for each instrument that
the laboratory used to obtain data for the Sample Delivery Group. Only the
instrument and wavelengths used to generate data for the SDG must be included.
Although the Instrument Detection Limits (IDLs) are determined quarterly (every
three calendar months) a copy of the quarterly instrument detection limits must
be included with each SDG data package on FORM(s) X-IN.
Complete the header information according to the instructions in Part A and as
follows.
Enter the date (formatted MM/DD/YY) on which the IDL values were obtained (or
became effective).
Enter ICP ID Number, Flame AA ID Number, and Furnace AA ID Number (12 spaces
maximum each). These ID Numbers are used to uniquely identify each instrument
that the laboratory uses to do CLP work.
Enter the Mercury instrument ID number in the Flame AA ID Number field.
B-31 ILM02.0
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Exhibit B Section III
Under "Wavelength," enter the wavelength in nanometers (to two decimal places)
for each analyte for which an Instrument Detection Limit (IDL) has been
established and is listed in the IDL column. If more than one wavelength is
used for an analyte, use other FORMs X-IN as appropriate to report the
Instrument Detection Limit.
Under "Background," enter the type of background correction used to obtain
Furnace AA data. Enter "BS" for Smith Hieftje, "BD" for Deuterium Arc, or "BZ"
for Zeeman background correction.
Contract Required Detection Limits (in ug/L) as established in Exhibit C, must
appear in the column headed "CRDL."
Under "IDL," enter the Instrument Detection Limit (ug/L, to one decimal place)
as determined by the laboratory for each analyte analyzed by the instrument for
which the ID Number is listed on this form. The IDL results must be reported
to two significant figures if the result value is less than 10, and to three
significant figures if the value is greater than or equal to 10. When
calculating IDL values, always round up to the appropriate significant figure.
This deviation from the EPA rounding rule is necessary to prevent the reporting
of detected values for results that fall in the noise region of the calibration
curve.
Under "M," enter the method of analysis used to determine the instrument
detection limit for each wavelength used. Use appropriate codes as explained
in Part C.
Use additional FORMs X-IN if more instruments and wavelengths are used. Note
that the date on this form must not exceed the analysis dates in the SDG data
package or precede them by more than three months.
Use the Comments section to indicate alternative wavelengths and the conditions
under which they are used.
ICP Interelement Correction Factors (Annually) [FORM XI(PART 1)-IN]
This form documents for each ICP instrument the interelement correction factors
applied by the Contractor laboratory to obtain data for the Sample Delivery
Group.
Although the correction factors are determined annually (every twelve calendar
months), a copy of the results of the annual interelement correction factors
must be included with each SDG data package on FORM XI(PART 1)-IN.
Complete the header information according to instructions in Part A and as
follows.
Enter the ICP ID Number (12 spaces maximum), which is a unique number
designated by the laboratory to identify each ICP instrument used to produce
data in the SDG package. If more than one ICP instrument is used, submit
additional FORMs XI(PART 1)-IN as appropriate.
B-32 ILM02.0
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Exhibit B Section III
Report the date (formatted as MM/DD/YY) on which these correction factors were
determined for use. This date must not exceed the ICP analysis dates in the
SDG data package or precede them by more than twelve calendar months.
Under "Wavelength," list the wavelength in nanometers (to two decimal places)
used for each ICP analyte. If more than one wavelength is used, submit
additional FORMs XI(PART 1)-IN as appropriate.
Under "Al," "Ca," "Fe," "Mg, enter the correction factor (negative, positive or
zero, to seven decimal places, 10 spaces maximum) for each ICP analyte. If
correction factors for another analyte are applied, use the empty column and
list the analyte's chemical symbol in the blank two-space header field provided
for that column.
If corrections are not applied for an analyte, a zero must be entered for that
analyte to indicate that the corrections were determined to be zero. If
correction factors are applied for more than one additional analyte, use FORM
XI(PART 2)-IN.
P. ICP Interelement Correction Factors (Annually) [FORM XI(PART 2)-IN]
This form is used if correction factors for analytes other than Al, Ca, Fe, Mg,
and one more analyte of the Contractor's choice, were applied to the analytes
analyzed by ICP. Complete this form as for FORM XI(PART 1)-IN by listing the
chemical symbol for additional analytes in the heading of the empty columns in
the two-space fields provided.
Columns of correction factors for additional analytes must be entered left to
right starting on FORM XI(PART 1)-IN and proceeding to FORM XI(PART 2)-IN,
according to the alphabetic order of their chemical symbols. Note that
correction factors for Al, Ca, Fe, and Mg are all required and are to be listed
first (as they appear on FORM XI(PART 1)-IN).
Q. ICP Linear Ranges (Quarterly) [FORM XII-IN]
This form documents the quarterly linear range analysis for each ICP instrument
that the laboratory used to obtain data for the SDG.
Complete the header information according to the instructions in Part A and as
follows.
Enter the ICP ID Number (12 spaces maximum), which is a unique number
designated by the Contractor to identify each ICP instrument used to produce
data for the SDG. If more than one ICP instrument is used, submit additional
FORMs XII-IN as appropriate.
Report the date (formatted as MM/DD/YY) on which these linear ranges were
determined for use. This date must not exceed the dates of analysis by ICP in
the SDG data package and must not precede the analysis dates by more than three
calendar months.
Under "Integ. Time (Sec.)," enter the integration time (in seconds to two
decimal places) used for each measurement taken from the ICP instrument.
B-33 ILM02.0
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Exhibit B Section III
Under "Concentration," enter the concentration (in ug/L) that is the upper
limit of the ICP instrument linear range as determined in Exhibit E. Any
measurement in the SDG data package at or below this concentration is within
the linear range. Any measurement above it is out of the linear range, and
thus, is an estimated value and must be diluted into the linear range.
Under "M," enter the method of analysis for each analyte as explained in Part
C.
If more instruments or analyte wavelengths are used, submit additional FORMs
XII-IN as appropriate.
R. Preparation Log [Form XIII-IN]
This Form is used to report the preparation run log.
All field samples and all quality control preparations (including duplicates,
matrix spikes, LCSs, PBs and repreparations) associated with the SDG must be
reported on Form XIII.
Submit one Form XIII per batch, per method, if no more than thirty-two
preparations, including quality control preparations, were performed. If more
than thirty-two preparations per batch, per method, were performed, then submit
additional copies of Form XIII as appropriate. Submit a separate Form XIII for
each batch.
The order in which the Preparation Logs are submitted is very important. Form
XIII must be organized by method, by batch. Later batches within a method must
follow earlier ones. Each batch must start on a separate Form XIII.
Complete the header information according to the instructions in Part A, and as
follows:
For "Method," enter the method of analysis (two characters maximum) for which
the preparations listed on the Form were made. Use appropriate method codes as
specified in Part C.
Under "EPA Sample No.," enter the EPA Sample Number of each sample in the SDG,
and of all other preparations such as duplicates, matrix spikes, LCSs, PBs, and
repreparations (all formatted according to Table 1). All EPA Sample Numbers
must be listed in ascending.alphanumeric order, continuing to the next Form
XIII if applicable.
Under "Preparation Date," enter the date (formatted MM/DD/YY) on which each
sample was prepared for analysis by the method indicated in the header section
of the Form.
Note that the date never changes on a single Form XIII because the form must be
submitted per batch.
Under "Weight," enter the wet weight (in grams, to two decimal places) of each
soil sample prepared for analysis by the method indicated in the header section
of the Form. If the sample matrix is water, then leave the field empty.
B-34 ILM02.0
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Exhibit B Section III
Under "Volume," enter the final volume (in mL, to the nearest whole number) of
the preparation for each sample prepared for analysis by the method indicated
in the header section of the Form. This field must have a value for each
sample listed.
S. Analysis Run Log [Form XIV-IN]
This Form is used to report the sample analysis run log.
A run is defined as the totality of analyses performed by an instrument
throughout the sequence initiated by, and including, the first SOW-required
calibration standard and terminated by, and including, the continuing
calibration verification and blank following the last SOW-required analytical
sample.
All field samples and all quality control analyses (including calibration
standards, ICVs, CCVs, ICBs, CCBs, CRAs, CRIs, ICSs, LRSs, LCSs, PBs,
duplicates, serial dilutions, pre-digestion spikes, post-digestion spikes,
analytical spikes, and each addition analyzed for the method of standard
addition determination) associated with the SDG must be reported on Form XIV.
The run must be continuous and inclusive of all analyses performed on the
particular instrument during the run.
Submit one Form XIV per run if no more than thirty-two (32) analyses, including
instrument calibration, were analyzed in the run. If more than thirty-two
analyses were performed in the run, submit additional Forms XIV as appropriate.
The order in which the Analysis Run Logs are submitted is very important. Form
XIV must be organized by method, by run. Later runs within a method must
follow earlier ones. Each analytical run must start on a separate Form XIV.
Therefore, instrument calibration must be the first entry on the form for each
new run. In addition, the run is considered to have ended if it is interrupted
for any reason, including termination for failing QC parameters.
Complete the header information according to the instructions in Part A, and as
follows:
For "Instrument ID Number," enter the instrument ID number, (12 spaces
maximum), which must be an identifier designated by the laboratory to uniquely
identify each instrument used to produce data which are required to be reported
in the SDG deliverable. If more than one instrument is used, submit additional
Forms XIV as appropriate.
For "Method," enter the method code (two characters maximum) according to the
specifications in Part C.
For "Start Date," enter the date (formatted MM/DD/YY) on which the analysis run
was started.
For "End Date," Enter the date (formatted MM/DD/YY) on which the analysis run
was ended.
B-35 ILM02.0
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Exhibit B Section III
Under "EPA Sample No.," enter the EPA sample number of each analysis, including
all QC operations applicable to the SDG (formatted according to Table 1). All
EPA Sample Numbers must be listed in increasing temporal (date and time) order
of analysis, continuing to the next Form XIV for the instrument run if
applicable. The analysis date and time of other analyses not associated with
the SDG, but analyzed by the instrument in the reported analytical run, must be
reported. Those analyses must be identified with the EPA Sample No. of
"ZZZZZZ."
Under "D/F," enter the dilution factor (to two decimal places) by which the
final digestate or distillate needed to be diluted for each analysis to be
performed. The dilution factor does not include the dilution inherent in the
preparation as specified by the preparation procedures in Exhibit D.
The dilution factor is required for all entries on Form XIV.
Note that for a particular sample a dilution factor of "1" must be entered if
the digestate or distillate were analyzed without adding any further volume of
dilutant or any other solutions to the "Volume" or an aliquot of the "Volume"
listed on Form XIII for that sample.
For EPA supplied solutions such as ICVs, ICSs, and LCSs, a dilution factor must
be entered if the supplied solution had to be diluted to a dilution different
from that specified by the instructions provided with the solution. The
dilution factor reported in such a case must be that which would make the
reported true values on the appropriate form for the solution equal those that
were supplied with the solution by the EPA. For instance, ICV-2(0887) has a
true value of 104.0 ug/L at a 20 fold dilution. If the solution is prepared at
a 40 fold dilution, a dilution factor of "2" must be entered on Form XIV and
the uncorrected instrument reading is compared to a true value of 52 ug/L. In
this example, Form II will have a true value of 104.0 regardless of the
dilution used. The found value for the ICV must be corrected for the dilution
listed on Form XIV using the following formula:
Found value on Form II - Instrument readout in ug/L x D/F
Under "Time," enter the time, (in military format - HHMM), at which each
analysis was performed. If an auto sampler is used with equal analysis time
and intervals between analyses, then only the start time of the run (the time
of analysis of the first calibration standard) and end time of the run (the
time of analysis of the final CCV or CCB, which ever is later) need to be
reported.
Under "% R," enter the percent recovery (to one decimal place) for each Furnace
AA analytical spike analyzed. If the analytical spike was performed on more
than one analyte, use additional Forms XIV as appropriate. Leave the "% R"
field empty if the analysis reported is not for an analytical spike. %R must
be recorded even if the result is not used.
A %R value of "-9999.9" must be entered for the analytical spike if either the
sample or analytical results is greater than the calibration range of the
instrument.
B-36 ILM02.0
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Exhibit B Section III
Under "Analytes," enter "X" in the column of the designated analyte to indicate
that the analyte value was used from the reported analysis to report data in
the SDG. Leave the column empty for each analyte if the analysis was not used
to report the particular analyte.
Entering "X" appropriately is very important. The "X" is used to link the
samples with their related QC. It also links the dilution factor with the
appropriate result reported on Forms I-IX. For each analyte result reported on
any of the Forms I-IX, there must be one, and only one, properly identified
entry on Form XIV for which an "X" is entered in the column for that analyte.
T. Sample Log-In Sheet [Form DC-1]
This form is used to document the receipt and i.nspection of samples and
containers. One original of Form DC-1 is required for each sample shipping
.container, e.g., cooler. If the samples in a single sample shipping container
must be assigned to more than one Sample Delivery Group, the original Form DC-
1 shall be placed with the deliverables for the. Sample Delivery Group of the
lowest Arabic number and a copy of Form DC-1 must be placed with the
deliverables for the other Sample Delivery Group(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 (i.e.,
intact, broken) in item 1 on 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 (i.e., Traffic
Reports, Packing Lists), and airbills or airbill stickers in items 3-5 on Form
DC-1. Specify if there is an airbill present or an airbill sticker in item 5
on Form DC-1. 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
(i.e., intact, broken, leaking) and presence or absence of sample tags in
items 7 and 8 on Form DC-1.
Review the sample shipping documents and comple.te the header information
described in Part A. Compare the information recorded on all the documents
and samples and mark the appropriate answer in item 9 on Form DC-1.
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 elate 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. Cross out unused columns and spaces.
If there are problems observed during receipt, 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 s.s specified in the preceding
paragraph and note, where appropriate, the resolution of the problem.
B-37 ILM02.0
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Exhibit B Section III
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 a.nd date the sample transfer
block.
U. Document Inventory Sheet (Form DC-2)
This form is used to record the inventory of the Complete SDG File (CSF)
documents which are sent to the Region.
Organize all EPA-CSF documents as described in Exhibit B, Section II and
Section III. Assemble the documents in the order specified on Form DC-2 and
Sections II and III, and stamp each page with the consecutive number. (Do not
number the DC-2 form). Inventory the CSF by reviewing the document numbers
and recording page numbers ranges in the column provided on the Form DC-2. If
.there are no documents for a specific document type, enter an "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 DC-2 to determine if
it is most appropriate to place them under No. 29, 30, 31, or 32. Category 32
should be used if there is no appropriate previous category. These types of
documents should be described or listed in the blanks under each appropriate
category.
fi-38 ILM02.0
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SECTION IV
DATA REPORTING FORMS
B'39 ILM02.0
-------
Lab Name:
Lab Code:
SOW No.:
U.S. EPA - CLP
COVER PAGE - INORGANIC ANALYSES DATA PACKAGE
Contract:
SAS No.:
Case No.:
SDG No.
EPA Sample No.
Lab Sample ID.
Were ICP interelement .corrections applied?
Were ICP background corrections applied?
If yes-were raw data generated before
application of background corrections?
Comments:
Yes/No
Yes/No
Yes/No
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 and in the computer-readable data submitted on
diskette has been authorized by the Laboratory Manager or the Manager's
designee, as verified by the following signature.
Signature:
Date:
Name:
Title:
COVER PAGE - IN
ILM02.0
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U.S. EPA - CLP
EPA SAMPLE NO.
Lab Name:
Lab Code:
INORGANIC ANALYSIS DATA SHEET
Contract:
I'
Case No.:
SAS No.:
SDG No.:
Matrix (soil/water):
Level (low/med):
% Solids:
Lab Sample ID:
Date Received:
Concentration Units (ug/L or mg/kg dry weight):
Color Before:
Color After:
Comments:
1 1
(CAS No. | Analyte
1 1
|7429-90-5 (Aluminum
(7440-36-0 (Antimony
(7440-38-2 (Arsenic
(7440-39-3 (Barium
j 7440-41-7 (Beryllium
(7440-43-9 (Cadmium
(7440-70-2 (Calcium
(7440-^47-3 (Chromium
(7440-48-4 (Cobalt
(7440-50-8 (Copper
(7439-89-6 (Iron
(7439-92-1 (Lead
(7439-95-4 (Magnesium
(7439-96-5 (Manganese
(7439-97-6 (Mercury
(7440-02-0 (Nickel
(7440-09-7 (Potassium
(7782-49-2 (Selenium
(7440-22-4 (Silver
(7440-23-5 (Sodium
(7440-28-0 (Thallium
(7440-62-2 (Vanadium
(7440-66-6 (Zinc
| | Cyanide
1 1
Concentration
1
C|
Q
M
—
Clarity Before:
Clarity After:
Texture:
Artifacts:
FORM I - IN
ILM02.0
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U.S. EPA - CLP
2A
INITIAL AND CONTINUING CALIBRATION VERIFICATION
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
Initial Calibration Source:
Continuing Calibration Source:
SDG No.:
Concentration Units: ug/L
1
1
| Analyte
1
| Aluminum_
j Antimony
(Arsenic
| Barium
[Beryllium
| Cadmium
| Calcium
j Chromium
j Cobalt
| Copper
[Iron
[Lead
(Magnesium
j Manganese
j Mercury
| Nickel
j Potassium
| Selenium
[Silver
| Sodium
|Thallium_
| Vanadium
[Zinc
| Cyanide
1
Initial Calibration
True Found %R(1)
Continuing Calibration
True Found %R(1) Found %R(1)
M
(1) Control Limits: Mercury 80-120; Other Metals 90-110; Cyanide 85-115
FORM II (PART 1) - IN
ILM02.0
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U.S. EPA - CLP
2B
CRDL STANDARD FOR AA AND ICP
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.:
AA CRDL Standard Source:
ICP CRDL Standard Source:
Concentration Units: ug/L
1
1
1
| Analyte
1
| Aluminum
| Antimony
| Arsenic
| Barium
| Beryllium
| Cadmium
| Calcium
| Chromium
| Cobalt
| Copper
I Iron
(Lead
| Magnesium
| Manganese
| Mercury
[Nickel
| Potassium
| Selenium
| Silver
| Sodium
| Thallium
| Vanadium
I Zinc
1
CRDL S
True
tandard fo
Found
r AA
%R
True
CRDL Star
Initial
Found
idard i
%R
for ICP
Fina]
Found
%R
.
FORM II (PART 2) - IN
ILM02.0
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U.S. EPA - CLP
3
BLANKS
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
SDG No.
Preparation Blank Matrix (soil/water):
Preparation Blank Concentration Units (ug/L or mg/kg):
1
1
1
1
| Analyte
1
| Aluminum
| Antimony
| Arsenic
| Barium
| Beryllium
| Cadmium
| Calcium
| Chromium
| Cobalt
| Copper
| Iron
(Lead
| Magnesium
j Manganese
| Mercury
| Nickel
| Potassium
j Selenium
(Silver
| Sodium
(Thallium
| Vanadium
| Zinc
| Cyanide
1
Initial
Calib.
Blank
(ug/L) C
—
Continuing Calibration
Blank (ug/L)
1 C 2 C 3 C
~
—
•
Prepa-
ration
Blank C
M
FORM III - IN
ILM02.0
-------
U.S. EPA - CLP
ICP INTERFERENCE CHECK SAMPLE
Lab Name:
Lab Code:
Case No.
Contract:
SAS No.:
SDG No,
ICP ID Number:
ICS Source:
Concentration Units: ug/L
1
1
1
| Analyte
1
| Aluminum
| Antimony
| Arsenic
| Barium
[Beryllium
j Cadmium
| Calcium
| Chromium
I Cobalt
| Copper
I Iron
| Lead
j Magnesium
j Manganese
j Mercury
| Nickel
| Potassium
j Selenium
(Silver
| Sodium
(Thallium
| Vanadium
IZinc
1
True
Sol. Sol.
A AB
Initial Found
Sol. Sol.
A AB %R
Final Found
Sol. Sol.
A AB %R
FORM IV - IN
ILM02.0
-------
U.S. EPA - CLP
5A
SPIKE SAMPLE RECOVERY
EPA SAMPLE NO.
Lab Name:
Lab Code:
Contract:
Case No.:
SAS No.:
SDG No.:
Matrix (soil/water):
% Solids for Sample:
Level (low/med):
Concentration Units (ug/L or mg/kg dry weight):
1
1
1
| Analyte
1
| Aluminum
| Antimony
| Arsenic
| Barium
| Beryllium
| Cadmium
| Calcium
| Chromium
| Cobalt
I Copper
I Iron
|Lead
| Magnesium
| Manganese
| Mercury
I Nickel
| Potassium
(Selenium
| Silver
| Sodium
(Thallium
| Vanadium
| Zinc
| Cyanide
1
Control
Limit
%R
Spiked Sample
Result (SSR)
Sample
Result (SR) C
Spike
Added (SA)
%R
M
Comments:
FORM V (PART 1) - IN
ILM02.0
-------
U.S. EPA - CLP
5B
POST DIGEST SPIKE SAMPLE RECOVERY
EPA SAMPLE NO.
r
Lab Name:
Lab Code:
Matrix (soil/water):
Contract:
Case No.:
SAS No.:
SEX; No. :
Level (low/med):
Concentration Units: ug/L
1
1
1
| Analyte
1
| Aluminum
| Antimony
| Arsenic
| Barium
(Beryllium
| Cadmium
| Calcium
| Chromium
| Cobalt
| Copper
llron
| Lead
| Magnesium
| Manganese
| Mercury
| Nickel
| Potassium
| Selenium
| Silver
| Sodium
| Thallium
| Vanadium
| Zinc
| Cyanide
1
Control
Limit
%R
Spiked Sample
Result (SSR)
.
C
Sample
Result (SR)
C
Spike
Added (SA)
%R
Q
M
Comments:
FORM V (PART 2) - IN
ILM02.0
-------
U.S. EPA - CLP
EPA SAMPLE NO.
Lab Name:
Lab Code:
DUPLICATES
Contract:
r
Case No.:
SAS No.:
SDG No.:
Matrix (soil/water):
% Solids for Sample:
Level (low/med):
% Solids for Duplicate:
Concentration Units (ug/L or mg/kg dry weight):
1
1
| Analyte
1
| Aluminum
| Antimony
| Arsenic
| Barium
(Beryllium
| Cadmium
| Calcium
| Chromium
I Cobalt
I Copper
| Iron
(Lead
(Magnesium
| Manganese
| Mercury
| Nickel
| Potassium
| Selenium
(Silver
| Sodium
(Thallium
| Vanadium
| Zinc
| Cyanide
1
Control
Limit
Sample (S)
C
Duplicate (D)
c
RPD
Q
M
FORM VI - IN
ILM02.0
-------
Lab Name:
Lab Code:
U.S. EPA - CLP
7
LABORATORY CONTROL SAMPLE
Contract:
Case No.: SAS No.:
SDG No.:
Solid LCS Source:
Aqueous LCS Source:
1
1
| Analyte
1
| Aluminum
| Antimony
| Arsenic
| Barium
| Beryllium
j Cadmium
| Calcium
| Chromium
I Cobalt
I Copper
|Iron
| Lead
| Magnesium
| Manganese
j Mercury
| Nickel
j Potassium
j Selenium_
| Silver
| Sodium
(Thallium
| Vanadium_
j Zinc
| Cyanide
1
Aqueous (ug/L) Sol
True Found %R True Found
Solid (mg/kg)
C Limits
%R
FORM VII - IN
ILM02.0
-------
U.S. EPA - CLP
8
STANDARD ADDITION RESULTS
Lab Name:
Lab Code:
Case No.
•
•
Contract :
SAS No . :
SDG
No. :
Concentration Units: ug/L
EPA
Sample
No.
An
0 ADD
ABS
1 ADD
CON ABS
2 ADD
CON ABS
3 ADD
CON ABS
Final
Cone.
r
Q
FORM VIII - IN
ILM02.0
-------
Lab Name:
Lab Code:
Case No.:
U.S. EPA - CLP
9
ICP SERIAL DILUTIONS
Contract: _
SAS No.:
EPA SAMPLE NO.
SDG No.:
Matrix (soil/water):
Level (low/med):
Concentration Units: ug/L
1
1
| Analyte
1 •
| Aluminum
| Antimony
| Arsenic
| Barium
| Beryllium
| Cadmium
| Calcium
| Chromium
I Cobalt
| Copper
I Iron
[Lead
(Magnesium
| Manganese
| Mercury
| Nickel
| Potassium
| Selenium
(Silver
| Sodium
(Thallium
| Vanadium
(Zinc
1
Initial Sample
Result (I)
c
Serial
Dilution
Result (S)
.
c
%
Differ-
ence
Q
M
FORM IX - IN
ILM02.0
-------
U.S. EPA - CLP
10
INSTRUMENT DETECTION LIMITS (QUARTERLY)
Lab Name:
Lab Code:
Case No.
ICP ID Number:
Flame AA ID Number:
Furnace AA ID Number:
Contract:
SAS No.:
Date:
SDG No.
1
1
1
| Analyte
1
| Aluminum
| Antimony
(Arsenic
| Barium
| Beryllium
| Cadmium
| Calcium
| Chromium
I Cobalt
I Copper
| Iron
(Lead
(Magnesium
| Manganese
| Mercury
| Nickel
| Potassium
| Selenium
(Silver
| Sodium
(Thallium
| Vanadium
(Zinc
1
Wave-
length
(nm)
Back-
ground
CRDL
(ug/L)
200
60
10
200
5
5
5000
10
50
25
100
3
5000
15
0.2
40
5000
5
10
5000
10
50
20
IDL
(ug/L)
M
Comments:
FORM X - IN
ILM02.0
-------
U.S. EPA - CLP
11A
ICP INTERELEMENT CORRECTION FACTORS (ANNUALLY)
Lab Name:
Lab Code:
Case No.
ICP ID Number:
Contract:
SAS No.:
Date:
SDG No.
1
1
1
| Analyte
1
| Aluminum
| Antimony
| Arsenic
| Barium
| Beryllium
| Cadmium
| Calcium
| Chromium
I Cobalt
I Copper
I Iron
(Lead
| Magnesium
| Manganese
| Mercury
| Nickel
| Potassium
| Selenium
| Silver
| Sodium
| Thallium
| Vanadium
| Zinc
1
Wave-
length
(nm)
Ir
Al
iterelement
Ca
Correction
Fe
Factors foi
Mg
* •
Comments:
FORM XI (PART 1) - IN
ILM02.0
-------
U.S. EPA - CLP
11B
ICP INTERELEMENT CORRECTION FACTORS (ANNUALLY)
Lab Name:
Lab Code:
Case No.:
ICP ID Number:
Contract:
SAS No.:
Date:
SDG No.
1
1
1
| Analyte
1
| Aluminum
| Antimony
| Arsenic
| Barium
| Beryllium
| Cadmium
| Calcium
| Chromium
I Cobalt
| Copper
| Iron
(Lead
| Magnesium
| Manganese
| Mercury
(Nickel
| Potassium
| Selenium
[Silver
| Sodium
| Thallium
| Vanadium
| Zinc
1
Wave-
length
(run)
Ir
iterelement
Correction
Factors foi
•
• •
Comments:
FORM XI (PART 2) - IN
ILM02.0
-------
U.S. EPA - CLP
12
ICP LINEAR RANGES (QUARTERLY)
Lab Name:
Lab Code:
ICP ID Number:
Case No.:
Contract:
SAS No.:
Date:
SDG No.:
1
1
1
| Analyte
1
| Aluminum
| Antimony
| Arsenic
| Barium
[Beryllium
| Cadmium
| Calcium
| Chromium
I Cobalt
| Copper
I Iron
(Lead
[Magnesium
| Manganese
| Mercury
| Nickel
| Potassium
{Selenium
| Silver
| Sodium
| Thallium
| Vanadium
| Zinc
1
Integ .
Time
(Sec.)
Concentration
(ug/L)
M
Comments:
FORM XII - IN
ILM02.0
-------
U.S. EPA - CLP
13
PREPARATION LOG
Lab Name:
Lab Code:
Method:
Case No.:
Contract:
SAS No.:
SDG No.
EPA
Sample
No.
Preparation
Date
Weight
(gram)
Volume
(mL)
FORM XIII - IN
ILM02.0
-------
U.S. EPA - CLP
14
ANALYSIS RUN LOG
Lab Name:
Lab Code:
Case No.:
Instrument ID Number:
Start Date:
Contract:
SAS No.:
Method: _
End Date:
SDG No.
EPA
Sample
No.
D/F
Time
% R
,
Analytes
A
L
s
B
A
s
B
A
B
E
c
D
c
A
c
R
c
0
c
u
F|
E
P
B
M
G
M
N
H
G
N
I
K
S
E
A
G
N
A
T|
L|
V
z
N
C
N
J
FORM XIV - IN
ILM02.0
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SAMPLE LOG-IN SHEET
Lab Name
Paae of
Received By (Print Name) Log-in Date
Received By (Signature)
Case Number Sample Delivery Group No. SAS Number
Remarks:
1. Custody Seal(s) Present/ Absent'
Intact/Broken
2 Custody Seal Nos.:
3. Chain-of-Custody Present/Absent'
Records
4. Traffic Reports or Packing Present/Absent'
Lists
5. Airbill Airbill/Sticker
Present/ Absent'
6. Airbill No.:
7. Sample Tags Present/Absent'
Sample Tag Numbers Listed/Not Listed
on Chain-of-Custody
8. Sample Condition: Imact/BrokenVLeaking
9. Does information on Yes/No'
custody records, traffic
reports, and sample tags
agree?
10. Date Received at Lab:
11. Time Received: __ __.
Sample Transfer
Fraction Fraction
Area # Area tt
By By
On On
EPA
Sample tt
Corresponding
Sample
Tag*
Assigned
Lab#
Remarks:
Condition of Sample Shipment, etc.
• Contact SMO and attach record of resolution.
Received By
Date
Logbook No.
Logbook Page No.
FORM DC-1
ILM02.0
-------
FULL INORGANICS
COMPLETE SDG FILE (CSF)
INVENTORY SHEET
Lab Name: City/State:
Case No. SDG No. SDG Nos. to Follow:
SAS No. Contract No. SOW No.
All documents delivered in the Complete SDG File must be original documents
where possible. (Reference Exhibit B, Section II D and Section III V)
Page Nos . (Please Check:)
From To Lab Region
1. Inventory Sheet (DC-2) (Do not number)
2. 'Cover Page
3. Inorganic Analysis
Data Sheet (Form I-IN)
4. Initial & Continuing Calibration
Verification (Form IIA-IN)
5. CRDL Standards For AA and ICP
(Form IIB-IN)
6. Blanks (Form III-IN)
7. ICP Interference Check
Sample (Form IV-IN)
8. Spike Sample Recovery (Form VA-IN)
9. Post Digest Spike
Sample Recovery (Form VB-IN)
10. Duplicates (Form VI-IN)
11. Laboratory Control Sample
(Form VII-IN)
12. Standard Addition Results
(Form VIII-IN)
13. ICP Serial Dilutions (Form IX-IN)
14. Instrument Detection Limits
(Form X-IN)
15. ICP Interelement Correction Factors
(Form XIA-IN)
16. ICP Interelement Correction Factors
(Form XIB-IN)
17. ICP Linear Ranges (Form XII-IN)
18. Preparation Log (Form XIII-IN)
19. Analysis Run Log (Form XIV-IN)
20. ICP Raw Data
21. Furnace AA Raw Data
22. Mercury Raw Data
Form DC-2 ILM02.0
-------
23.
24.
25.
26.
27.
28.
29.
30.
31.
Page Nos.
From To
(Please Check:)
Lab Region
Cyanide Raw Data
Preparation Logs Raw Data
Percent Solids Determination Log
Traffic Report
EPA Shipping/Receiving Documents
Airbill (No. of Shipments )
Chain-of-Custody Records
Sample Tags
Sample Log-In Sheet (Lab & DC1)
SDG Cover Sheet
Misc. Shipping/Receiving Records
'(list all individual records)
Telephone Logs
Internal Lab Sample Transfer Records &
Tracking Sheets (describe or list)
Internal Original Sample Prep & Analysis Records
(describe or list)
Prep Records
Analysis Records
Description
Other Records (describe or list)
Telephone Communication Log
32. Comments:
Completed by (CLP Lab):
(Signature)
Audited by (EPA):
(Signature)
(Print Name & Title)
(Print Name & Title)
(Date)
(Date)
Form DC-2 (continued)
ILM02.0
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EXHIBIT C
INORGANIC TARGET ANALYTE LIST
ILM02.0
-------
INORGANIC TARGET ANALYTE LIST (TAL)
Contract Required
Detection Limit
Analyte (ug/L)
Aluminum 200
Antimony 60
Arsenic 10
Barium 200
Beryllium 5
Cadmium 5
Calcium 5000
Chromium 10
Cobalt 50
Copper 25
Iron 100
Lead 3
Magnesium 5000
Manganese 15
Mercury 0.2
Nickel 40
Potassium 5000
Selenium 5
Silver 10
Sodium 5000
Thallium 10
Vanadium 50
Zinc 20
Cyanide 10
(1) Subject to the restrictions specified in the first page of Part G,
Section IV of Exhibit D (Alternate Methods - Catastrophic Failure) any
analytical method specified in SOW Exhibit D may be utilized as long as
the documented instrument or method detection limits meet the Contract
Required Detection Limit (CRDL) requirements. Higher detection limits
may only be used in the following circumstance:
If the sample concentration exceeds five times the detection
limit of the instrument or method in use, the value may be
reported even though the instrument or method detection limit
may not equal the Contract Required Detection Limit. This is
illustrated in the example below:
For lead:
Method in use = ICP
Instrument Detection Limit (IDL) = 40
Sample concentration = 220
Contract Required Detection Limit (CRDL) = 3
C-l ILM02.0
-------
The value of 220 may be reported even though the instrument
detection limit is greater than CRDL. The instrument or
method detection limit must be documented as described in
Exhibits B and E.
(2) The CRDLs are the instrument detection limits obtained in pure water
that must be met using the procedure in Exhibit E. The detection
limits for samples may be considerably higher depending on the sample
matrix.
C-2 ILM02.0
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EXHIBIT D
ANALYTICAL METHODS
Page No.
SECTION I - INTRODUCTION D-l
Figure 1-Inorganic Methods Flow Chart D-3
SECTION II - SAMPLE PRESERVATION AND HOLDING TIMES D-4
Part A - Sample Preservation D-4
Part B - Holding Times D-4
SECTION III - SAMPLE PREPARATION D-5
Part A - Water Sample Preparation D-5
Part B - Soil/Sediment Sample Preparation D-5
Part C - Microwave Digestion Method D-8
Part D - Mercury and Cyanide Preparation D-14
SECTION IV - SAMPLE ANALYSIS D-15
Part A - Inductively Coupled Plasma-Atomic
Emission Spectrometric Method D-16
Part B - Atomic Absorption Methods, Furnace Technique D-28
Part C - Atomic Absorption Methods, Flame Technique D-40
Part D - Cold Vapor Methods for Mercury Analysis D-45
Part E - Methods for Total Cyanide Analysis D-62
Part F - Percent Solids Determination Procedure D-89
Part G - Alternate Methods (Catastrophic ICP Failure) D-90
ILM02.0
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Exhibit D Section I
SECTION I
INTRODUCTION
Inorganic Methods Flow Chart: Figure I outlines the general analytical scheme the
Contractor will follow in performing analyses under this contract.
Permitted Methods: Subject to the restrictions specified in Section IV, Part G -
Alternate Methods (Catastrophic ICP Failure), any analytical method specified in
Exhibit D may be used as long as the documented instrument or method detection
limits meet the Contract Required Detection Limits (Exhibit C). Analytical methods
with higher detection limits may be used only if the sample concentration exceeds
five times the documented detection limit of the instrument or method.
Initial Run Undiluted: All samples must initially be; run undiluted (i.e., final
product of the sample preparation procedure). When an analyte concentration exceeds
the calibrated or linear range (as appropriate), re-analysis for that analyte(s) is
required after appropriate dilution. The Contractor must use the least dilution
necessary to bring the analyte(s) within the valid analytical range (but not below
the CRDL) and report the highest valid value for each analyte as measured from the
undiluted and diluted analyses. Unless the Contractor can submit proofthat dilution
was required to obtain valid results, both diluted arid undiluted sample measurements
must be contained in the raw data. ICP data showing a high concentration for a
particular analyte, combined with an analyte result that is close to the middle
range of the calibration curve in the diluted sample, constitute sufficient proof
that the sample had to initially be run diluted for that analyte on a furnace AA
instrument. All sample dilutions shall be made with deionized water appropriately
acidified to maintain constant acid strength.
Quality Assurance/Quality Control Measurements: The Contractor is reminded and
cautioned that Exhibit D is a compendium of required and/or permitted analytical
methods to be used in the performance of analyses under this contract. The quality
assurance/quality control procedures or measurements to be performed in association
with these methods or analyses are specified in Exhibit E. In the event references
to quality assurance measurements in any of the methods appear to be in conflict
with or to be less stringent than the requirements of Exhibit E, the requirements of
Exhibit E will prevail.
Raw Data Requirements: The Contractor is reminded and cautioned that the collection
and provision of raw data may or may not be referred to within the individual
methods of Exhibit D or the Quality Assurance Protocol of Exhibit E. The Raw Data
Deliverables requirements are specified in Exhibit B, Section II.D.2.d. Raw data
collected and provided in association with the performance of analyses under this
contract shall conform to the appropriate provisions of Exhibit B.
Glassware Cleaning: Lab glassware to be used in metals analysis must be acid
cleaned according to EPA's manual "Methods for Chemical Analysis of Water and
Wastes" or an equivalent procedure.
Standard Stock Solutions: Stock solutions to be used for preparing instrument or
method calibration standards may be purchased or prepared as described in the
individual methods of Exhibit D. All other solutions: to be used for Quality
Assurance/Quality Control measurements shall conform to the specific requirements of
Exhibit E.
D-l ILM02.0
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Exhibit D Section I
Aqueous Sample pH Measurement: Before sample preparation is initiated on an aqueous
sample received in shipment, the Contractor must check the pH of the sample and note
in a preparation log if the pH is <2 for a metals sample or if the pH is >12 for a
cyanide sample. The Contractor shall not perform any pH adjustment action if the
sample has not been properly preserved. If the sample has not been preserved,
contact SMO before proceeding with the preparation and analysis for further
instructions.
Sample Mixing: Unless instructed otherwise by the EPA Administrative Project
Officer or Technical Project Officer, all samples shall be mixed thoroughly prior to
aliquoting for digestion. No specific procedure is provided herein for
homogenization of soil/sediment samples; however, an effort should be made to obtain
a representative aliquot.
Background Corrections: Background corrections are required for Flame AA
measurements below 350 run and for all Furnace AA measurements. For ICP background
correction requirements, see Exhibit D Section IV, Part A, paragraph 2.1.
Replicate Injections/Exposures: Each furnace analysis requires a minimum of two
injection (burns), except for full method of standard addition (MSA). All ICP
measurements shall require a minimum of two replicate exposures. Appropriate hard
copy raw data for each exposure/injection shall be included in the data package in
accordance with Exhibit B, Section II, Part D, paragraph 2.d. The average of each
set of exposures/injections shall be used for standardization, sample analysis, and
reporting as specified in Exhibit D.
D-2 ILM02.0
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Figure 1
INORGANICS METHODS FLOW CHART
I
I
| Field Sample |
I I
I
Traffic Report or SMO
Specifies Parameters
1
Water
Matrix
1
1
1
1
1
| Cyanide | (Acid Digestion)
| Analysis | | for Metals |
| in Water | | Analysis |
| | | in Water |
1
1
1
| Metal Anal. |
| ICP/AAS |
1
Soil/Sediment
Matrix
|Acid Digestion | |% Solids | (Cyanide |
j for Metals j |Determin-j (Analysis!
(Analysis in j j ation j (in Soil/j
(Soil/Sediment j j j j Sediment j
(Metals Anal. |
| ICP/AAS |
1
1
1
1
I Data Reports
1
1
1
D-3
ILM02.0
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Exhibit D Section II
SECTION II
SAMPLE PRESERVATION AND HOLDING TIMES
A. SAMPLE PRESERVATION
1. Water Sample Preservation
Measurement
Parameter Container^ ' Preservative' '
Metals P,G HN03 to pH <2
Cyanide, total P,G 0.6g ascorbic acid(3)
and amenable NaOH to pH >12
to chlorination Cool, maintain at 4°C(±2°C)
until analysis
FOOTNOTES:
(1) Polyethylene (P) or glass (G).
(2) Sample preservation is performed by the sampler immediately upon
sample collection.
(3) Only used in the presence of residual chlorine.
2. Soil/Sediment Sample Preservation
The preservation required for soil/sediment samples is maintenance at 4°C
(± 2°) until analysis.
B. HOLDING TIMES FOR WATER AND SOIL/SEDIMENT SAMPLES
Following are the maximum sample holding times allowable under this contract.
To be compliant with this contract, the Contractor must analyze samples within
these times even if these times are less than the maximum data submission times
allowed in this contract.
No. of Days Following
Analyte Sample Receipt
by Contractor
Mercury 26 days
Metals (other than mercury) 180 days
Cyanide 12 days
D-4 ILM02.0
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Exhibit D Section III
SECTION III
SAMPLE PREPARATION
A. WATER SAMPLE PREPARATION
1. Acid Digestion Procedure for Furnace Atomic Absorption Analysis
Shake sample and transfer 100 mL of well-mixed sample to a 250-mL beaker,
add 1 mL of (1+1) HN03 and 2 mL 30% H202 to the sample. Cover with watch
glass or similar cover and heat on a steam bath or hot plate for 2 hours
at 95°C or until sample volume is reduced to between 25 and 50 mL, making
certain sample does not boil. Cool sample and filter to remove insoluble
material. (NOTE: In place of filtering, the sample, after dilution and
mixing, may be centrifuged or allowed to settle by gravity overnight to
remove insoluble material.) Adjust sample volume to 100 mL with deionized
distilled water. The sample is now ready for analysis.
Concentrations so determined shall be reported as "total."
If Sb is to be determined by furnace AA, use the digestate prepared for
ICP/flame AA analysis.
2. Acid Digestion Procedure for ICP and Flame AA Analyses
Shake sample and transfer 100 mL of well-mixed sample to a 250-mL beaker,
add 2 mL of (1+1) HN03 and 10 mL of (1+1) HC1 to the sample. Cover with
watch glass or similar cover and heat on a steam bath or hot plate for 2
hours at 95°C or until sample volume is reduced to between 25 and 50 mL,
making certain sample does not boil. Cool sample and filter to remove
insoluble material. (NOTE: In place of filtering, the sample, after
dilution and mixing, may be centrifuged or allowed to settle by gravity
overnight to remove insoluble material.) Adjust sample volume to 100 mL
with deionized distilled water. The sample is now ready for analysis.
Concentrations so determined shall be reported as "total."
B. SOIL/SEDIMENT SAMPLE PREPARATION
1. Acid Digestion Procedure for ICP, Flame AA and Furnace AA Analyses
a. Scope and Application
This method is an acid digestion procedure used to prepare sediments,
sludges, and soil samples for analysis by flame or furnace atomic
absorption spectroscopy (AAS) or by inductively coupled plasma
spectroscopy (ICP). Samples prepared by this method may be analyzed
by AAS or ICP for the following metals:
D-5 ILM02.0
-------
Exhibit D Section III
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
b. Summary of Method
A representative 1 g (wet weight) sample is digested in nitric acid
and hydrogen peroxide. The digestate is then refluxed with either
nitric acid or hydrochloric acid. Hydrochloric acid is used as the
final reflux acid for the furnace AA analysis of Sb, the Flame AA or
ICP analysis of Al, Sb, Ba, Be, Ca, Cd, Cr, Co, Cu, Fe, Pb, Mg, Mn,
Ni, K, Ag, Na, Tl, V and Zn. Nitric acid is employed as the final
reflux acid for the Furnace AA analysis of As, Be, Cd, Cr, Co, Cu,
Fe, Pb, Mn, Ni, Se, Ag, Tl, V, and Zn. A separate sample shall be
dried for a percent solids determination (Section IV,Part F).
c. Apparatus and Materials
(1) 250 mL beaker or other appropriate vessel
(2) Watch glasses
(3) Thermometer that covers range of 0° to 200°C
(4) Whatman No. 42 filter paper or equivalent
d. Reagents
(1) ASTM Type II water (ASTM D1193): Water must be monitored.
(2) Concentrated nitric acid (sp. gr. 1.41)
(3) Concentrated hydrochloric acid (sp. gr. 1.19)
(4) Hydrogen Peroxide (30%)
e. Sample Preservation and Handling
Soil/sediment (nonaqueous) samples must be refrigerated at 4°C (±2°)
from receipt until analysis.
D-6 ILM02.0
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Exhibit D Section III
f. Procedure
(1) Mix the sample thoroughly to achieve homogeneity. For each
digestion procedure, weigh (to th« nearest O.Olg) a 1.0 to 1.5 g
portion of sample and transfer to a beaker.
(2) Add 10 mL of 1:1 nitric acid (HNO;j) , mix the slurry, and cover
with a watch glass. Heat the sample to 95°C and reflux for 10
minutes without boiling. Allow the sample to cool, add 5 mL of
concentrated HN03, replace the watch glass, and reflux for 30
minutes. Do not allow the volume to be reduced to less than 5
mL while maintaining a covering of solution over the bottom of
the beaker.
(3) After the second reflux step has been completed and the sample
has cooled, add 2 mL of Type II water and 3 mL of 30% hydrogen
peroxide (H2(>2). Return the beaker to the hot plate for warming
to start the peroxide reaction. Care must be taken to ensure
that losses do not occur due to excessively vigorous
effervescence. Heat until effervescence subsides, and cool the
beaker.
(4) Continue to add 30% H202 in 1 mL uliquots with warming until the
effervescence is minimal or until the general sample appearance
is unchanged. (NOTE: Do not add more than a total of 10 mL
30% H202.)
(5a) If the sample is being prepared for the furnace AA analysis of
Sb, the flame AA or ICP analysis of Al, Sb, Ba, Be, Ca, Cd, Cr,
Co, Cu, Fe, Pb, Mg, Mn, Ni, K, AJ;, Na, Tl, V, and Zn, add 5 mL
of 1:1 HCl and 10 mL of Type II water, return the covered beaker
to the hot plate, and heat for an additional 10 minutes. After
cooling, filter through Whatman No. 42 filter paper (or
•equivalent) and dilute to 100 mL with Type II water. NOTE: In
place of filtering, the sample (after dilution and mixing) may
be centrifuged or allowed to settle by gravity overnight to
remove insoluble material. The diluted sample has an
approximate acid concentration of 2.5% (v/v) HCl and 5% (v/v)
HN03. Dilute the digestate 1:1 (200 mL final volume) with
acidified water to maintain constant acid strength. The sample
is now ready for analysis.
(5b) If the sample is being prepared for the furnace analysis of As,
Be, Cd, Cr, Co, Cu, Fe, Pb, Mn, N:., Se, Ag, Tl, V, and Zn,
continue heating the acid-peroxide digestate until the volume
has been reduced to approximately 2 mL, add 10 mL of Type II
water, and warm the mixture. After cooling, filter through
Whatman No. 42 filter paper (or equivalent) and dilute the
sample to 100 mL with Type II water (or centrifuge the sample).
NOTE: In place of filtering, the sample (after dilution and
D-7 ILM02.0
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Exhibit D Section III
mixing) may be centrifuged or allowed to settle by gravity
overnight to remove insoluble material. The diluted digestate
solution contains approximately 2% (v/v) HN03. Dilute the
digestate 1:1 (200 mL final volume) with acidified water to
maintain constant acid strength. For analysis, withdraw
aliquots of appropriate volume, and add any required reagent or
matrix modifier. The sample is now ready for analysis.
g. Calculations
(1) A separate determination of percent solids must be performed
(Section IV, Part F).
(2) The concentrations determined in the digest are to be reported
on the basis of the dry weight of the sample.
Concentration (dry wt.) (mg/kg) - C x V
W x S
Where,
C - Concentration (mg/L)
V - Final volume in liters after sample
preparation
W - Weight in kg of wet sample
S - % Solids/100
C. TOTAL METALS SAMPLE PREPARATION USING MICROWAVE DIGESTION
1. SCOPE AND APPLICATION
This method is an acid digestion procedure using microwave, energy to prepare
water and soil samples for analysis by GFAA, ICP, or Flame AA for the
following metals:
Aluminum
*
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
NOTE: This microwave digestion method is not appropriate
for the quantitative recovery of Antimony from soil and
sediment samples.
D-8 ILM02.0
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Exhibit D Section III
2. SUMMARY OF METHOD
a. Water Sample Preparation
A representative 45 mL water sample is digested in 5 mL of
concentrated nitric acid in a Teflon PFA vessel for 20 minutes using
microwave heating. The digestate is then filtered to remove
insoluble material. The sample may be centrifuged or allowed to
settle by gravity overnight to remove insoluble material.
b. Soil Sample Preparation
A representative 0.5 g (wet weight) sample is digested in 10 mL of
concentrated nitric acid in a Teflon PFA vessel for 10 minutes using
microwave heating. The digestate is then filtered to remove
insoluble material. The sample may be centrifuged or allowed to
settle by gravity overnight to remove insoluble material. NOTE: This
microwave digestion method is not appropriate for the quantitative
recovery of Antimony from soil and sediment samples.
3. APPARATUS AND MATERIALS
a. Commercial kitchen or home-use microwave ovens shall not be used for
the digestion of samples under this contract. The oven cavity must
be corrosion resistant and well ventilated. All electronics must be
protected against corrosion for safe operation.
b. Microwave oven with programmable power settings up to at least 600
Watts.
n
c. The system must use PFA Teflon digestion vessels (120 mL capacity)
capable of withstanding pressures of up to 110 +10 psi (7.5 +0.7
atm). These vessels are capable of controlled pressure relief at
pressures exceeding 110 psi.
d. A rotating turntable must be used to ensure homogeneous distribution
of microwave radiation within the oven. The speed of the turntable
must be a minimum of 3 rpm.
D
e. Polymeric volumetric ware in plastic (Teflon or polyethylene) 50 mL
or 100 mL capacity.
f. Whatman No. 41 filter paper (or equivalent).
g. Disposable polypropylene filter funnel.
h. Analytical balance, 300 g capacity, and minimum +0.01 g.
i. Polyethylene bottles, 125 mL, with caps.
4. REAGENTS
a. ASTM Type II water (ASTM D1193): water must be monitored.
b. Sub-boiled, concentrated nitric acid (sp. gr. 1.41).
c. Concentrated hydrochloric acid (sp. gr. 1.19).
D-9 ILM02.0
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Exhibit D Section III
5. MICROWAVE CALIBRATION PROCEDURE
a. The calibration procedure is a critical step prior to the use of any
microwave unit. The microwave unit must be calibrated every six
months. The calibration data for each calibration must be available
for review during on-site audits. In order that absolute power
settings may be interchanged from one microwave unit to another, the
actual delivered power must be determined.
Calibration of a laboratory microwave unit depends on the type of
electronic system used by the manufacturer. If the unit has a
precise and accurate linear relationship between the output power and
the scale used in controlling the microwave unit, then the
calibration can be a two-point calibration at maximum and 40% power.
If the unit is not accurate or precise for some portion of the
controlling scale, then a multiple-point calibration is necessary.
If the unit power calibration needs a multiple point calibration,
then the point where linearity begins must be identified. For
example: a calibration at 100, 99, 98, 97, 95, 90, 80, 70, 60, 50
and 40% power settings can be applied and the data plotted. The non-
linear portion of the calibration curve can be excluded or restricted
in use. Each percent is equivalent to approximately 5.5 - 6 watts
and becomes the smallest unit of power that can be controlled. If 20
- 40 watts are contained from 99-100%, that portion of the microwave
calibration is not controllable by 3-7 times that of the linear
portion of the control scale and will prevent duplication of precise
power conditions specified in that portion of the power scale.
The power available for heating is evaluated so that the absolute
power setting (watts) may be compared from one microwave to another.
This is accomplished by measuring the temperature rise in 1 Kg of
water exposed to microwave radiation for a fixed period of time. The
water is placed in a Teflon beaker (or a beaker that is made of some
other material that does not adsorb microwave energy) and stirred
before measuring the temperature. Glass beakers adsorb microwave
energy and may not be used. The initial temperature of the water
must be between 19 and 25 °C. The beaker is circulated continuously
through the field for at least two (2) minutes at full power. The
beaker is removed from the microwave, the water is stirred
vigorously, and the final temperature recorded. The final reading is
D-10 ILM02.0
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Exhibit D Section III
the maximum temperature reading after each energy exposure. These
measurements must be accurate to ± 0.1 °C and made within 30 seconds
of the end of heating. If more measurciments are needed, do not use
the same water until it has cooled down to room temperature.
Otherwise, use a fresh water sample.
The absorbed power is determined by the following formula:
p _ (K) (Co) Cm) (DT)
t
Where:
P - The apparent power absorbed by the sample in watts (joules per second),
K - The conversion factor for thermochemical calories per second to watts
(-4.184),
Cp - The heat capacity, thermal capacity, or specific heat (cal. g ."C ) of
water (-1.0),
m - The mass of the sample in grams (g),
DT - the final temperature minus the initial temperature (°C), and
t - the time in seconds (s)
Using 2 minutes and 1 Kg of distilled water, the calibration equation
simplifies to:
P - (DT) (34.87).
The microwave user can now relate power in watts to the percent power setting
of the microwave
6. CLEANING PROCEDURE
a. The initial cleaning of the PFA vessels:
(1) Prior to first use - new vessels must be annealed before they are used. A
pretreatment/cleaning procedure must be followed. This procedure calls for
heating the vessels for 96 hours at 200°C. The vessels must be disassembled
during annealing and the sealing surfaces (the top of the vessel or its rim)
must not be used to support the vessel during annealing.
(2) Rinse in ASTM Type I water.
ILM02.0
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Exhibit D Section III
(3) Immerse in 1:1 HC1 for a minimum of 3 hours after the cleaning bath has
reached a temperature just below boiling.
(4) Rinse in ASTM Type I water.
(5) Immerse in 1:1 HN03 for a minimum of 3 hours after the cleaning bath has
reached a temperature just below boiling.
(6) The vessels are then rinsed with copious amounts of ASTM Type I water prior to
use for any analyses under this contract.
b. cleaning procedure between sample digestions
(1) Wash entire vessel in hot water using laboratory-grade nonphosphate detergent.
(2) Rinse with 1:1 nitric acid.
(3) Rinse three times with ASTM Type I water. If contaminants are found in the
preparation blank, it is mandatory that steps a(2) through a(6) be strictly
adhered to.
7. DIGESTION PROCEDURE
a. Water Sample Digestion Procedure
P
(1) A 45 mL aliquot of the sample are measured into Teflon digestion vessels
using volumetric glassware.
(2) 5 mL of high purity concentrated HN03 is added to the digestion vessels.
(3) The caps with the pressure release valves are placed on the vessels hand tight
and then tightened, using constant torque, to 12 ft./lbs. The weight of each
vessel is recorded to 0.02 g.
(4) Place 5 sample vessels in the carousel, evenly spaced around its periphery in
the microwave unit. Venting tubes connect each sample vessel with a
collection vessel. Each sample vessel is attached to a clean, double-ported
vessel to collect any sample expelled from the sample vessel in the event of
over pressurization. Assembly of the vessels into the carousel may be done
inside or outside the microwave.
(5) This procedure is energy balanced for five 45 mL water samples (each with 5 mL
of acid) to produce consistent conditions. When fewer than 5 samples are
digested, the remaining vessels must be filled with 45 mL of tap, DI or Type
II water and 5 mL of concentrated nitric acid.
Newer microwave ovens may be capable of higher power settings which may allow
D-12 ILM02.0
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Exhibit D Section III
a larger number of samples. If the analyst wishes to digest more than 5
samples at a time, the analyst may use different power settings as long as
they result in the same time temperature conditions defined in the power
programming for this method.
The initial temperature of the samples should be 2A. ± 1°C. The preparation
blank must have 45 mL of deionized water and the same amount (5 mL) of acid
that is added to the samples.
The microwave unit first-stage program must be set to give 545 watts for 10
minutes and the second-stage program to give 344 watts for 10 minutes. This
sequence brings the samples to 160 +4°C in ten minutes and permits a slow rise
to 165-170 °C during the second 10 minutes.
(6) Following the 20 minute program, the samples are left to cool in the microwave
unit for five minutes, with the exhaust fan ON. The samples and/or carousel
•may then be removed from the microwave unit. Before opening the vessels, let
cool until they are no longer hot to the touch.
(7) After the sample vessel has cooled, weigh the sample vessel and compare to the
initial weight as reported in the preparation log. Any sample vessel
exhibiting a < 0.5 g loss must have any excess sample from the associated
collection vessel added to the original sample vessel before proceeding with
the sample preparation. Any sample vessel exhibiting a > 0.5 g loss must be
identified in the preparation log and the sample redigested.
(9) Sample Filtration:
The digested samples are shaken well to mix in any condensate within the
digestion vessel before being opened. The digestates are then filtered into
50 mL glass volumetric flasks through ultra-clean filter paper and diluted to
50 mL (if necessary). The samples are now ready for analysis. The sample
results must be corrected by a factor of 1.11 in order to report final
concentration values based on an initial volume of 45 ml. Concentrations so
determined shall be reported as "total."
b. Soil Sample Digestion Procedure
(1) Add a representative 0.5 ±0.050 grams of sample to the TeflonR PFA vessel.
(2) Add 10 ±0.1 mL of concentrated nitric acid. If a vigorous reaction occurs,
allow the reaction to stop before capping the vessel.
(3) Cap the vessel, then tighten using constant torque to 12 ft/lbs, according to
the manufacturer's direction.
(4) Connect the sample vessel to the overflow vessel using TeflonR PFA tubing.
(5) Weigh the vessel assembly to the nearest O.Olg.
°-13 ILM02.0
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Exhibit D Section III
(6) Place sample vessels in groups of 2 sample vessels or 6 sample vessels in the
carousel, evenly spaced around its periphery in the microwave unit. If fewer
than the recommended number of samples are to be digested, i.e. 3 samples plus
1 blank then the remaining vessels must be filled with 10 mL of nitric acid to
achieve the full complement of vessels.
Each sample vessel must be attached to a clean, double-ported vessel to
collect any sample expelled from the sample vessel in the event of over
pressurization. Assembly of the vessels into the carousel may be done inside
or outside the microwave. Connect the overflow vessel to the center well of
the oven.
(7) The preparation blank must have 0.5 mL of deionized water and the same amount
(10 mL) of acid that is added to the samples. The preparation blank must
later be diluted to 50 mL in the same manner as the samples.
(8) -Irradiate the 2 sample vessel group at 344 watts for 10 minutes, or the 6-
sample vessel group at 574 watts for 10 minutes.
This program brings the samples to 175°C in 5.5 minutes, and remains between
170-180°C for the balance of the 10 minute irradiation period. The pressure
should peak at less than 6 atm for most samples. The pressure may exceed
these limits in the case of high concentrations of carbonate or organic
compounds. In these cases, the pressure will be limited by the relief
pressure of the vessel to 7.5 ±0.7 atm.
(9) Allow the vessels to cool for a minimum of five minutes before removing them
from the microwave unit, with exhaust fan ON. Allow the vessels to cool to
room temperature before opening. The vessels must be carefully vented and
uncapped in a fume hood.
(10) Weigh each vessel assembly. If the weight of acid plus the sample has
decreased by more than 10% from the original weight, discard the digests.
Determine the reason for the loss. Losses typically are attributed to use of
digestion time longer than ten minutes, using too large of a sample, or having
improper heating conditions. Once the source of the losses has been
corrected, prepare a new set of samples for digestion.
(11) Sample Filtration:
Shake the sample well to mix in any condensate within the digestion vessel
before being opened. Filter the digestion vessel into a 50 mL glass
volumetric flask through ultra-clean filter paper. Rinse the sample digestion
vessel, cap, connecting tube, and (if venting occurred) the overflow vessel
D-14 ILM02.0
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Exhibit D Section III
into the 50 mL glass flask. Dilute to 50 mL. The samples are now ready for
analysis. Concentrations so determined shall be reported as "total."
(12) Calculations:
The concentrations determined in the digest are: to be reported on the basis of
the dry weight of the sample.
Concentration (dry wt.) (mg/Kg) - C x V
W x S
Where
C - Concentration (mg/L)
V - Final volume in liters after sample
preparation
W - Weight in kg of wet seunple
S - % Solids/100
D. MERCURY AND CYANIDE PREPARATION
Refer to each specific method in this Exhibit for mercury and cyanide
preparations.
D-15 ILM02.0
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Exhibit D ICP-AES
PART A - INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION SPECTROMETRIC METHOD"1"
Method 200.7 CLP-M*
INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION SPECTROMETRIC METHOD
FOR TRACE ELEMENT ANALYSIS OF WATER AND WASTES
1. Scope and Application
1.1 Dissolved elements are determined in filtered and acidified samples.
Appropriate steps must be taken in all analyses to ensure that potential
interferences are taken into account. This is especially true when dissolved
solids exceed 1500 mg/L. (See 5.)
1.2 Total elements are determined after appropriate digestion procedures are
performed. Since digestion techniques increase the dissolved solids content
of the samples, appropriate steps must be taken to correct for potential
interference effects. (See 5.)
1.3 Table 1 lists elements along with recommended wavelengths and typical
estimated instrumental detection limits using conventional pneumatic
nebulization. Actual working detected limits are sample dependent and as the
sample matrix varies, these concentrations may also vary. In time, other
elements may be added as more information becomes available and as required.
1.4 Because of the differences between various makes and models of satisfactory
instruments, no detailed instrumental operating instructions can be provided.
Instead, the analyst is referred to the instructions provided by the
manufacturer of the particular instrument.
2. Summary of Method
The method describes a technique for the simultaneous or sequential
multielement determination of trace elements in solution. The basis of the
method is the measurement of atomic emission by an optical spectroscopic
technique. Samples are nebulized and the aerosol that is produced is
transported to the plasma torch where excitation occurs. Characteristic
atomic-line emission spectra are produced by a radio-frequency inductively
coupled plasma (ICP). The spectra are dispersed by a grating spectrometer and
the intensities of the line are monitored by photomultiplier tubes. The
photocurrents from the photomultiplier tubes are processed and controlled by a
computer system. A background correction technique is required to compensate
for variable background contribution to the determination of trace elements.
Background must be measured adjacent to analyte lines on samples during
analysis. The position selected for the background intensity measurement, on
either or both sides of the analytical line, will be determined by the
complexity of the spectrum adjacent to the analyte line. The position used
must be free of spectral interference and reflect the same change in
background intensity as occurs at the analyte wavelength measured. Background
"*"A bibliography citing method references appears in paragraph 11 of the method.
CLP-M modified for the Contract Laboratory Program.
D-16 ILM02.0
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Exhibit D ICP-AES
correction is not required in cases of line broadening where a background
correction measurement would actually degrade the analytical result. The
possibility of additional interferences named in 5.1 (and tests for their
presence as described in 5.2) should also be recognized and appropriate
corrections made.
3.
The toxicity or carcinogenicity of each reagent: used in this method has not
been precisely defined; however, each chemical compound should be treated as a
potential health hazard. The laboratory is responsible for maintaining a
current awareness file of OSHA regulations regarding the safe handling of the
chemicals specified in this method. A reference file of material handling
data sheets should be made available to all personnel involved in the chemical
analysis.
4. Interferences
4.1 Several types of interference effects may contribute to inaccuracies in the
determination of trace elements. They can be summarized as follows:
4.1.1 Spectral interferences can be categorized as 1) overlap of a spectral
line from another element; 2) unresolved overlap of molecular band
spectra; 3) background contribution from continuous or recombination
phenomena; and 4) background contribution from stray light from the
line emission of high concentration elements. The first of these
effects can be compensated by utilizing a computer correction of the
raw data, requiring the monitoring and measurement of the interfering
element. The second effect may require selection of an alternate
wavelength. The third and fourth effects can usually be compensated
by a background correction adjacent to the analyte line. In
addition, users of simultaneous multi-element instrumentation must
assume the responsibility of verifying the absence of spectral
interference from an element that could occur in a sample but for
which there is no channel in the instrument array.
Listed in Table 2 are some interference effects for the recommended
wavelengths given in Table 1. The data in Table 2 are intended for
use only as a rudimentary guide for the indication of potential
spectral interferences. For this purpose, linear relations between
concentration and intensity for the analytes and the interferents can
be assumed. The interference information, which was collected at the
Ames Laboratory , is expressed as analyte concentration equivalents
(i.e., false analyte concentrations) arising from 100 mg/L of the
interferent element.
The suggested use of this information is as follows: Assume that
arsenic (at 193.696 nm) is to be determined in a sample containing
approximately 10 mg/L of of aluminum. According to Table 2, 100 mg/L
of aluminum would yield a false signal for arsenic equivalent to
approximately 1.3 mg/L. Therefore, 10 mg/L of aluminum would result
in a false signal for arsenic equivalent to approximately 0.13 mg/L.
Ames Laboratory, USDOE, Iowa State University, Ames, Iowa 50011.
D-17 ILM02.0
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Exhibit D ICP-AES
The reader is cautioned that other analytical systems may exhibit
somewhat different levels of interference than those shown in Table
2, and that the interference effects must be evaluated for each
individual system. Only those interferents listed were investigated
and the blank spaces in Table 2 indicate that measurable
interferences were not observed from the interferent concentrations
listed in Table 3. Generally, interferences were discernible if they
produced peaks or background shifts corresponding to 2-5% of the
peaks generated by the analyte concentrations also listed in Table 3.
At present, information on the listed silver and potassium
wavelengths are not available but it has been reported that second
order energy from the magnesium 383.231 nm wavelength interferes with
the listed potassium line at 766.491 nm.
4.1.2 Physical interferences are generally considered to be effects
associated with the sample nebulization and transport processes.
Such properties as change in viscosity and surface tension can cause
significant inaccuracies especially in samples which may contain high
dissolved solids and/or acid concentrations. The use of a
peristaltic pump may lessen these interferences. If these types of
interferences are operative, they must be reduced by dilution of the
sample and/ or utilization of standard addition techniques. Another
problem which can occur from high dissolved solids is salt buildup at
the tip of the nebulizer. This affects aerosol flow rate causing
instrumental drift.
Wetting the argon prior to nebulization, the use of a tip washer, or
sample dilution have been used to control this problem. Also, it has
been reported that better control of the argon flow rate improves
instrument performance. This is accomplished with the use of mass
flow controllers.
4.1.3 Chemical interferences are characterized by molecular compound
formation, ionization effects and solute vaporization effects.
Normally these effects are not pronounced with the ICP technique,
however, if observed they can be minimized by careful selection of
operating conditions (that is, incident power, observation position,
and so forth), by buffering of the sample, by matrix matching, and by
standard addition procedures. These types of interferences can be
highly dependent on matrix type and the specific analyte element.
4.2 Prior to reporting concentration data for the analyte elements, the Contractor
must analyze and report the results of the ICP Serial Dilution Analysis. The
ICP Serial Dilution Analysis must be performed on a sample from each group of
samples of a similar matrix type (i.e., water, soil) and concentration (i.e.,
low, medium) or for each Sample Delivery Group, whichever is more frequent.
Samples identified as field blanks cannot be used for Serial Dilution Analysis.
If the analyte concentration is sufficiently high (minimally a factor of 50
above the instrumental detection limit in the original sample), the serial
dilution (a five fold dilution) must then agree within 10% of the original
determination after correction for dilution. If the dilution analysis for one
or more analytes is not within 10%, a chemical or physical interference effect
D-18 ILM02.0
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Exhibit D ICP-AES
must be suspected, and the data for all affected analytes in the samples
received associated with that serial dilution must be flagged with an "E" on
FORM IX-IN and FORM I-IN.
5. Apparatus
5.1 Inductively Coupled Plasma-Atomic Emission Spectrometer.
5.1.1 Computer controlled atomic emission spectrometer with background
correction.
5.1.2 Radio frequency generator.
5.1.3 Argon gas supply, welding grade or better.
5.2 Operating conditions - - Because of the differences between various makes and
models of satisfactory instruments, no detailed operating instructions can be
provided. Instead, the analyst should follow the instructions provided by the
manufacturer of the particular instrument. Sensitivity, instrumental
detection limit, precision, linear dynamic range, and interference effects
must be investigated and established for each individual analyte line on that
particular instrument. All measurements must be within the instrument linear
range where correction factors are valid. It is the responsibility of the
analyst to verify that the instrument configuration and operating conditions
used satisfy the analytical requirements and to maintain quality control data
confirming instrument performance and analytical results.
6. Reagents and Standards
6.1 Acids used in the preparation of standards and for sample processing must be
ultra-high purity grade or equivalent. Redistilled acids are acceptable.
6.1.1 Acetic acid, cone. (sp gr 1.06).
6.1.2 Hydrochloric acid, cone. (sp gr 1.19).
6.1.3 Hydrochloric acid, (1+1): Add 500 mL cone. HC1 (sp gr 1.19) to 400
mL deionized, distilled water and dilute to 1 liter.
6.1.4 Nitric acid, cone, (sp gr 1.41).
6.1.5 Nitric acid, (1+1): Add 500 mL cone. HN03 (sp gr 1.41) to 400 iaL
deionized, distilled water and dilute to 1 liter.
6.2 Deionized, distilled water: Prepare by passing distilled water through a
mixed bed of cation and anion exchange resins. Use deionized, distilled water
for the preparation of all reagents, calibration standards and as dilution
water. The purity of this water must be equivalent to ASTM Type II reagent
water of Specification D 1193.
6.3 Standard stock solutions may be purchased or prepared from ultra high purity
grade chemicals or metals. All salts must be dried for 1 hour at 105° unless
otherwise specified.
D-19 ILM02.0
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Exhibit D ICP-AES
(CAUTION: Many metal salts are extremely toxic and may be fatal if swallowed.
Wash hands thoroughly after handling.) Typical stock solution preparation
procedures follow:
6.3.1 Aluminum solution, stock, 1 mL - 100 ug Al: Dissolved 0.100 g of
aluminum metal in an acid mixture of. 4 mL of (1+1) HC1 and 1 mL of
cone. HN03 in a beaker. Warm gently to effect solution. When
solution is complete, transfer quantitatively to a liter flask, add
an additional 10 mL of (1+1) HC1 and dilute to 1000 mL with
deionized, distilled water.
6.3.2 Antimony solution stock, 1 mL - 100 ug Sb: Dissolve 0.2669 g
K(SbO)C4H40g in deionized distilled water, add 10 mL (1+1) HC1 and
dilute to 1000 mL with deionized, distilled water.
6.3.3 Arsenic solution, stock, 1 mL - 100 ug As: Dissolve 0.1320 g of
As2(>3 in 100 mL of deionized, distilled water containing 0.4 g NaOH.
Acidify the solution with 2 mL cone. HN03 and dilute to 1,000 mL
with deionized, distilled water.
6.3.4 Barium solution, stock, 1 mL - 100 ug Ba: Dissolve 0.1516 g BaCl2
(dried at 250°C for 2 hrs) in 10 mL deionized, distilled water with 1
mL (1+1) HC1. Add 10.0 mL (1+1) HC1 and dilute to 1,000 mL with
deionized, distilled water.
6.3.5 Beryllium solution, stock, 1 mL - 100 ug Be: Do not dry. Dissolve
1.966 g BeS04'4H20, in deionized, distilled water, add 10.0 mL cone.
HN03 and dilute to 1,000 mL with deionized, distilled water.
6.3.6 Boron solution, stock, 1 mL - 100 ug B: Do not dry. Dissolve 0.5716
g anhydrous 113603 in deionized, distilled water and dilute to 1,000
mL. Use a reagent meeting ACS specifications, keep the bottle
tightly stoppered and store in a desiccator to prevent the entrance
of atmospheric moisture.
6.3.7 Cadmium solution, stock, 1 mL - 100 ug Cd: Dissolve 0.1142 g CdO in
a minimum amount of (1+1) HN03- Heat to increase rate of
dissolution. Add 10.0 mL cone. HN03 and dilute to 1,000 mL with
deionized, distilled water.
6.3.8 Calcium solution, stock, 1 mL - 100 ug Ca: Suspend 0.2498 g CaC03
dried at 180°C for 1 h before weighing in deionized, distilled water
and dissolve cautiously with a minimum amount of (1+1) HN03. Add
10.0 mL cone. HN03 and dilute to 1,000 mL with deionized, distilled
water.
6.3.9 Chromium solution, stock, 1 mL - 100 ug Cr: Dissolve 0.1923 g of
Cr03 in deionized, distilled water. When solution is complete
acidify with 10 mL cone. HN03 and dilute to 1,000 mL with deionized,
distilled water.
6.3.10 Cobalt solution stock, 1 mL - 100 ug Co: Dissolve 0.1000 g of cobalt
metal in a minimum amount of (1+1) HNO}. Add 10.0 mL (1+1) HC1 and
dilute to 1,000 mL with deionized, distilled water.
D-20 ILM02.0
-------
Exhibit D ICP-AES
6.3.11 Copper solution, stock, 1 mL - 100 ug Cu: Dissolve 0.1252 g CuO in a
minimum amount of (1+1) HNC>3. Add 10.0 mL cone. HNC>3 and dilute to
1,000 mL with deionized, distilled water.
6.3.12 Iron solution, stock, 1 mL - 100 ug Fe : Dissolve 0.1430 g Fe203 in a
warm mixture of 20 mL (1+1) HC1 and 2 mL of cone. HN03- Cool, add
an additional 5 mL of cone. HN03 and dilute to 1,000 mL with
deionized, distilled water.
6.3.13 Lead solution, stock, 1 mL - 100 ug Pb: Dissolve 0.1599 g Pb(N03)2
in a minimum amount of (1+1) HN03. Add 10.0 mL of cone. HN03 and
dilute to 1,000 mL with deionized, distilled water.
6.3.14 Magnesium solution, stock, 1 mL - 100 ug Mg: Dissolve 0.1658 g MgO
in a minimum amount of (1+1) HN03. Add 10.0 mL cone. HN03 and
dilute to 1,000 mL with deionized, distilled water.
6.3.15 Manganese solution, stock, 1 mL - 100 ug Mn: Dissolve 0.1000 g of
manganese metal in the acid mixture, 10 mL cone. HCl and 1 mL cone.
HN03, and dilute to 1,000 mL with deionized, distilled water.
6.3.16 Molybdenum solution, stock, 1 mL - 100 ug Mo: Dissolve 0.2043 g
in deionized, distilled water and dilute to 1,000 mL.
6.3.17 Nickel solution, stock, 1 mL - 100 ug Ni: Dissolve 0.1000 g of
nickel metal in 10 mL hot cone. HNC>3, cool and dilute to 1,000 mL
with deionized, distilled water.
6.3.18 Potassium solution, stock, 1 mL - 100 ug K: Dissolve 0.1907 g KC1,
dried at 110°C, in deionized, distilled water. Dilute to 1,000 mL.
6.3.19 Selenium solution, stock, 1 mL - 100 ug Se: Do not d.ry. Dissolve
0.1727 g H2Se03 (actual assay 94.6%) in deionized, distilled water
and dilute to 1,000 mL.
6.3.20 Silica solution, stock, 1 mL - 100 ug SiC>2: Do not dry. Dissolve
0.4730 g Na2Si03'9H20 in deionized, distilled water. Add 10.0 mL
cone. HN03 and dilute to 1,000 mL with deionized, distilled water.
6.3.21 Silver solution, stock, 1 mL - 100 ug Ag: Dissolve 0.1575 g AgN03 in
100 mL of deionized, distilled water and 10 mL cone. HNC>3 . Dilute
to 1,000 mL with deionized, distilled water.
6.3.22 Sodium solution, stock, 1 mL - 100 ug Wa: Dissolve 0.2542 g NaCl in
deionized, distilled water. Add 10.0 mL cone. HNC>3 and dilute to
1,000 mL with deionized, distilled wat»jr.
6.3.23 Thallium solution, stock, 1 mL - 100 ug Tl: Dissolve 0.1303 g T1N03
in deionized, distilled water. Add
10.0 mL cone. HN03 and dilute to 1,000 mL with deionized, distilled
water.
D-21 ILM02.0
-------
Exhibit D ICP-AES
6.3,24 Vanadium solution, stock, 1 mL - 100 ug V: Dissolve 0.2297 NH4V03 in
a minimum amount of cone. HNC>3. Heat to increase rate of
dissolution. Add 10.0 mL cone. HNC>3 and dilute to 1,000 mL with
deionized, distilled water.
6.3.25 Zinc solution, stock, 1 mL - 100 ug Zn: Dissolve 0.1245 g ZnO in a
minimum amount of dilute HN03- Add 10.0 mL cone. HNC>3 and dilute to
1,000 mL with deionized, distilled water.
6.4 Mixed calibration standard solutions -- Prepare mixed calibration standard
solutions by combining appropriate volumes of the stock solutions in
volumetric flasks. (See 7.4.1 thru 7.4.5.) Add 2 mL of (1+1) HN03 and 10 mL
of (1+1) HC1 and dilute to 100 mL with deionized, distilled water. (See NOTE
in 7.4.5) Prior to preparing the mixed standards, each stock solution should
be analyzed separately to determine possible spectral interference or the
presence of impurities. Care should be taken when preparing the mixed
standards that the elements are compatible and stable. Transfer the mixed
standard solutions to a FEP fluorocarbon or unused polyethylene bottle for
storage. Fresh mixed standards should be prepared as needed with the
realization that concentration can change on aging. Calibration standards
must be initially verified using a quality control sample and monitored weekly
for stability (see 7.6.3). Although not specifically required, some typical
calibration standard combinations follow when using those specific wavelengths
listed in Table 1.
6.4.1 Mixed standard solution I -- Manganese, beryllium, cadmium, lead, and
zinc.
6.4.2 Mixed standard solution II -- Barium, copper, iron, vanadium, and
cobalt.
6.4.3 Mixed standard solution III -- Molybdenum, silica, arsenic, and
selenium.
6.4.4 Mixed standard solution IV -- Calcium, sodium, potassium, aluminum,
chromium and nickel.
6.4.5 Mixed standard solution V -- Antimony, boron, magnesium, silver, and
thallium.
NOTE: If the addition of silver to the recommended acid combination
results in an initial precipitation add 15 mL of deionized distilled
water and warm the flask until the solution clears. Cool and dilute
to 100 mL with deionized, distilled water. For this acid combination
the silver concentration should be limited to 2 mg/L. Silver under
these conditions is stable in a tap water matrix for 30 days. Higher
concentrations of silver require additional HC1.
6.5 Two types of blanks are required for the analysis. The calibration blank
(3.13) is used in establishing the analytical curve while the reagent blank
(preparation blank, 3.12) is used to correct for possible contamination
resulting from varying amounts of the acids used in the sample processing.
D-22 ILM02.0
-------
Exhibit D ICP-AES
6.5.1 The calibration blank is prepared by diluting 2 mL of (1+1) HN03 and
10 mL of (1+1) HC1 to 100 mL with deionized, distilled water.
Prepare a sufficient quantity to be used to flush the system between
standards and samples.
6.5.2 The reagent blank (or preparation blank - See Exhibit E) must contain
all the reagents and in the same volumes as used in the processing of
the samples. The reagent blank must be carried through the complete
procedure and contain the same acid concentration in the final
solution as the sample solution used for analysis.
6.6 In addition the calibration standards, an instrument check standard (3.6), an
interference check sample (3.7) and a quality control sample (3.8) are also
required for the analyses.
6.6.1 The instrument check standard for continuing calibration verification
is prepared by the analyst by combining compatible elements at a
concentration equivalent to the mid-points of their respective
calibration curves. (See 10.1.3.)
6.6.2 The interference check sample is prepared by the analyst, or obtained
from EPA if available (Exhibit E).
6.6.3 The quality control sample for the initial calibration verification
should be prepared in the same acid matrix as the calibration
standards and in accordance with the instructions provided by the
supplier. EPA will either supply a quality control sample or
information where one of equal quality can be procured. (See
10.1.1.)
7. Procedure
7.1 Set up instrument with proper operating parameters established in Section 6.2.
The instrument must be allowed to become thermally stable before beginning.
This usually requires at least 30 min. of operation prior to calibration.
7.2 Initiate appropriate operating configuration of computer.
7.3 Profile and calibrate instrument according to instrument manufacturer's
recommended procedures, using mixed calibration standard solutions such as
those described in Section 7.4. Flush the system with the calibration blank
(7.5.1) between each standard. (NOTE: For boron concentrations greater than
500 ug/L extended flush times of 1 to 2 minutes may be required.)
7.4 Begin the sample run flushing the system with the calibration blank solution
(7.5.1) between each sample. (See NOTE in 8.3.) Analyze the instrument check
standard (7.6.1) and the calibration blank (7.5.1) each 10 analytical samples.
7.5 A minimum of two replicate exposures are required for standardization and all
QC and sample analyses. The average result of the multiple exposures for the
standardization and all QC and sample analyses shall be used.
D-23 ILM02.0
-------
Exhibit D ICP-AES
8. Calculation
8.1 Reagent blanks (preparation blanks) should be treated as specified in Exhibit
E.
8.2 If dilutions were performed, the appropriate factor must be applied to sample
values.
8.3 Units must be clearly specified.
9. Quality Control (Instrumental)
9.1 Quality control must be performed as specified in Exhibit E.
D-24 ILM02.0
-------
Exhibit D ICP-AES
TABLE 1 - RECOMMENDED WAVELENGTHS(2) AND ESTIMATED
INSTRUMENTAL DETECTION LIMITS
Element
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Potassium
Selenium
Silica (Si02)
Silver
Sodium
Thallium
Vanadium
Zinc
Wavelength, nm(l)
308.215
206.833
193.696
455.403
313.042
249.773
226.502
317.933
267.716
228.616
324.754
259.940
220.353
279.079
257.610
202.030
231.604
766.491
196.026
288.158
328.068
588.995
190.864
292.402
213.856
Estimated Detection
Limit, ug/L(2)
45
32
53
2
0.3
5
4
10
7
7
6
7
42
30
2
8
15
See(3)
75
58
2
29
40
8
2
(1) The wavelengths listed are recommended because of their sensitivity and overall
acceptance. Other wavelengths may be substituted if they can provide the
needed sensitivity and are treated with the same corrective techniques for
spectral interference. (See 5.1.1). The use of alternate wavelengths must be
reported (in nm) with the sample data.
(2) The estimated instrumental detection limits as shown are taken from
"Inductively Coupled Plasma-Atomic Emission Spectroscopy-Prominent Lines," EPA-
600/4-79-017. They are given as a guide for an instrumental limit. The actual
method detection limits are sample dependent and may vary as the sample matrix
varies.
(3) Highly dependent on operating conditions and plasma position.
D-25 ILM02.0
-------
TABLE 2. EXAMPLE OF ANALYTE CONCENTRATION EQUIVALENTS (MG/L) ARISING FROM
INTERFERENTS AT THE 100 MG/L LEVEL
o
to
Oi
M
s
O
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Selenium
Silicon
Sodium
Thallium
Vanadium
Zinc
Wavelength,
run
308.215
206.833
193.696
455.403
313.042
249.773
226.502
317.933
267.716
228.616
324.754
259.940
220.353
279.079
257.610
202.030
231.604
196.026
288.158
588.995
190.864
292.402
213.856
Al
—
0.47
1.3
__
—
0.04
__
—
—
— —
—
— —
0.17
—
0.005
0.05
—
0.23
—
—
0.30
__
—
Ca Cr Cu
— — — — __
2.9
0.44
— — — — _.
— — — — __
— — .... _.
0.08
— — —
0.03
— — —
— — —
__ __ __
0.02 0.11
0.01
— — _ —
__ __ __
— — —
0.07
— f — —
— — —
0.05
0.14
Interferent
Fe Mg Mn Ni
0.21
0.08
— — — —
._ .»••• — — — —
— — — —
0.32
0.03 — — 0.02
0.01 0.01 0.04
0.003 — 0.04
0.005 — — 0.03
0.003
0.12
__ __ __ — —
0.13 — 0.25
0.002 0.002
0.03
__ __ __ — —
0.09
__ __ __ — —
— — — —
— — — —
0.005
0.29
Ti
—
.25
—
__
0.04
—
__
0.03
—
0.15
0.05
— —
—
0.07
— —
—
—
—
—
0.08
—
0.02
—
V
1.4
0.45
1.1
__
0.05
—
— —
0.03
0.04
—
0.02
— —
—
0.12
— —
—
—
—
0.01
—
—
—
-------
TABLE 3. INTERFERENT AND ANALYTE ELEMENTAL CONCENTRATIONS USED
FOR INTERFERENCE MEASUREMENTS IN T^3LE 2
Analytes
Al
As
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Mg
Mn
Mo
Na
Ni
Pb
Sb
Se
Si
Tl
V
Zn
(mg/L)
10
10
10
1
1
1
10
1
1
1
1
1
1
10
10
10
10
10
10
1
10
1
10
Interferents
Al
Ca
Cr
Cu
Fe
Mg
Mn
Ni
Ti
V
(mg/L)
1000
1000
200
200
1000
1000
200
200
200
200
D-27 ILM02.0
-------
PART B - ATOMIC ABSORPTION METHODS. FURNACE TECHNIQUE"1"
Analyte/Method Page No.
Antimony - Method 204.2 CLP-M* D-29
Arsenic - Method 206.2 CLP-M D-30
Beryllium - Method 210.2 CLP-M D-31
Cadmium - Method 213.2 CLP-M D-32
Chromium - Method 218.2 CLP-M D-33
Lead - Method 239.2 CLP-M D-34
Selenium - Method 270.2 CLP-M D-36
Silver - Method 272.2 CLP-M D-38
Thallium - Method 279.2 CLP-M D-39
+From "Methods for Chemical Analysis of Water and Wastes" (EPA-600/4-79-
020), Metals-4, as modified for use in the Contract Laboratory Program).
CLP-M modified for the Contract Laboratory Program.
D-28 ILM02.0
-------
Exhibit D Method 204.2
ANTIMONY
Method 204.2 CLP-M* (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 20-300 ug/L
Approximate Detection Limit: 3 ug/L
Preparation of Standard Solution
1. Stock solution: Carefully weigh 2.7426 g of antimony potassium tartrate
(analytical reagent grade) and dissolve in deionized distilled water. Dilute
to 1 Liter with deionized water. 1 mL - 1 mg Sb (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. These solutions are also to be used for "standard
additions".
3. The calibration standards must be prepared using the same type of acid and at
the same concentration as will result in the sample to be analyzed after sample
preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 800°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 217.6 nm
6. Other operating parameters should be set as specified by the particular
ins trument manufacturer.
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, contin- uous flow purge gas
and non-pyrolytic graphite and are to be used as guidelines only. Smaller size
furnace devices or those employing faster rates of atomization can be operated
using lower atomization temperatures for shorter time periods than the above
recommended settings.
2. The use of background correction is required.
3. Nitrogen may also be used as the purge gas.
4. If chloride concentration presents a matrix problem or causes a loss previous
to atomization, add an excess 5 mg of ammonium nitrate to the furnace and ash
using a ramp accessory or with incremental steps until the recommended ashing
temperature is reached.
5. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (see Exhibit E).
6. If method of standard addition is required, follow the procedure given in
Exhibit E.
CLP-M modified for the Contract Laboratory Program.
D-29 ILM02.0
-------
Exhibit D Method 206.2
ARSENIC
Method 206.2 CLP-M* (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L
Approximate Detection Limit: 1 ug/L
Preparation of Standard Solution
1. Stock solution: Dissolve 1.320 g of arsenic trioxide, AS203 (analytical
reagent grade) in 100 mL of deionized distilled water containing 4 g NaOH.
Acidify the solution with 20 mL cone. HN(>3 and dilute to 1 Liter. 1 mL - 1 mg
As (1000 mg/1) .
2. Nickel Nitrate Solution, 5%: Dissolve 24.780 g of ACS reagent grade
in deionized distilled water and make up to 100 mL.
3. Nickel Nitrate Solution, 1%: Dilute 20 mL of the 5% nickel nitrate to 100 mL
with deionized distilled water.
4. Working Arsenic Solution: Prepare dilutions of the stock solution to be used
as calibration standards at the time of analysis. Withdraw appropriate aliquots
of the stock solution, add 1 mL of cone. HN03, 2 mL of 30% ^02 and 2 mL of the
5% nickel nitrate solution. Dilute to 100 mL with deionized distilled water.
Sample Preparation
1. Add 100 uL of the 5% nickel nitrate solution to 5 mL of the digested sample.
The sample is now ready for injection into the furnace.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 1100°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 193.7 nm
6. Other operating parameters should be set as specified by the particular
ins trument manuf ac tur e r .
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, purge gas interrupt and non-
pyrolytic graphite. Smaller size furnace devices or those employing faster
rates of atomization can be operated using lower atomization temperatures for
shorter time periods than the above recommended settings.
2. The use of background correction is required. Background correction made by the
deuterium arc method does not adequately compensate for high levels of certain
interferents (ie., Al, Fe) . If conditions occur where significant interference
is suspected, the lab must switch to an alternate wavelength or take other
appropriate actions to compensate for the interference effects .
3. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (see Exhibit E) .
4. If method of standard addition is required, follow the procedure given in
Exhibit E).
5. The use of the Electrodeless Discharge Lamps (EDL) for the light source is
recommended.
CLP-M modified for the Contract Laboratory Program.
D-30 ILM02.0
-------
Exhibit D Method 210.2
BERYLLIUM
Method 210.2 CLP-M* (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 1-30 ug/L
Approximate Detection Limit: 0.2 ug/L
Preparation of Standard Solution
1. Stock solution: Dissolve 11.6586g of beryllium sulfate, BeSC>4, in deionized
distilled water containing 2 mL concentrated nitric acid and dilute to 1 Liter.
1 mL - 1 mg Be (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. These solutions are also to be used for "standard
additions".
3. The calibration standards must be prepared using the same type of acid and at
the same concentration as will result in the sample to be analyzed after sample
preparation.
Instr^""ent Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 1000°C.
3. Atomizing Time and Temp: 10 sec @ 2800°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 234.9 nm
6. The operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-
Elmer HGA-2100, based on the use of a 20 uL injection, con-tinuous flow purge
gas and non-pyrolytic graphite and are to be used as guidelines only. Smaller
size furnace devices or those employing faster rates of atomization can be
operated using lower atomization temperatures for shorter time periods than
the above recommended settings.
2. The use of background correction is required.
3. Because of possible chemical interaction, nitrogen should not be used as a
purge gas.
4. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (see Exhibit E)
5. If method of standard addition is required, follow the procedure given in
Exhibit E.
CLP-M modified for the Contract Laboratory Program.
D-31 ILM02.0
-------
Exhibit D Method 213.2
CADMIUM
Method 213.2 CLP-M* (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 0.5-10 ug/L
Approximate Detection Limit: 0.1 ug/L
Preparation of Standard Solution
1. Stock solution: Carefully weigh 2.282g of cadmium sulfate, 3 CdSO^ 8
(analytical reagent grade) and dissolve in deionized distilled water. Make up
to 1 Liter with deionized distilled water. 1 mL - 1 mg Cd (1000 mg/L).
2. Ammonium Phosphate solution (40%): Dissolve 40 grams of ammonium phosphate,
(NH4)2HP04 (analytical reagent grade) in deionized distilled water and dilute
to 100 mL.
3. Prepare dilutions of stock cadmium solution to be used as calibration standards
at the time of analysis. To each 100 mL of standard and sample alike add 2.0
mL of the ammonium phosphate solution. The calibration standards must be
prepared using the same type of acid and at the same concentration as will
result in the sample to be analyzed after sample preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 500°C.
3. Atomizing Time and Temp: 10 sec @ 1900°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 228.8 nm
6. The operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, continuous flow purge gas and
non-pyrolytic graphite and are to be used as guidelines only. Smaller size
furnace devices or those employing faster rates of atomization can be operated
using lower atomization temperatures for shorter time periods than the above
recommended settings.
2. The use of background correction is required.
3. Contamination from the work area is critical in cadmium analysis. Use pipette
tips which are free of cadmium.
4. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (see Exhibit E).
5. If method of standard addition is required, follow the procedure given in
Exhibit E.
CLP-M modified for the Contract Laboratory Program.
D-32 ILM02.0
-------
Exhibit D Method 218.2
CHROMIUM
Method 218.2 CLP-M (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L
Approximate Detection Limit: 1 ug/L
Preparation of Standard Solution
1. Stock solution: Prepare as described under Part C methods, AA Flame Technique.
2. Calcium Nitrate solution: Dissolve 11.8 grams of calcium nitrate,
Ca(N03)2'4H20 (analytical reagent grade) in deionized distilled water and
dilute to 100 mL. 1 mL - 20 mg Ca.
3. Prepare dilutions of the stock chromium solution to be used as calibration
standards at the time of analysis. The calibration standards must be prepared
using the same type of acid and at the same concentration as will result in the
sample to be analyzed after sample preparation. To each 100 mL of standard and
sample alike, add 1 mL of 30% H202 and 1 mL of the calcium nitrate solution.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 1000°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 357.9 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin Elmer
HGA-2100, based on the use of a 20 uL injection, continuous flow purge gas and
non-pyrolytic graphite and are to be used as guidelines only.
2. Hydrogen peroxide is added to the acidified solution to convert all chromium to
the trivalent state. Calcium is added to a level above 200 mg/L where its
suppressive effect becomes constant up to 1000 mg/L.
3. Background correction is required.
4. Nitrogen should not be used as a purge gas because of possible CN band
interference.
5. Pipette tips have been reported to be a possible source of contamination.
6. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (see Exhibit E).
7. If method of standard addition is required, follow the procedure given in
Exhibit E.
CLP-M modified for the Contract Laboratory Program.
D-33 ILM02.0
-------
Exhibit D Method 239.2
LEAD
•&•
Method 239.2 CLP-M (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L
Approximate Detection Limit: 1 ug/L
Preparation of Standard Solution
1. Stock solution: Carefully weigh 1.599 g of lead nitrate, Pb(N03>2 (analytical
reagent grade), and dissolve in deionized distilled water. When solution is
complete, acidify with 10 mL redistilled HNC-3 and dilute to 1 Liter with
deionized distilled water. 1 mL - 1 mg Pb (lOOOmg/L).
2. Lanthanum Nitrate solution: Dissolve 58.64 g of ACS reagent grade La2°3 in 100
mL cone. HNC-3 and dilute to 1000 mL with deionized distilled water. 1 mL - 50
mg La.
3. Working Lead solution: Prepare dilutions of stock lead solution to be used as
calibration standards at the time of analysis. The calibration standards must
be prepared using the same type of acid and at the same concentration as will
result in the sample to be analyzed after sample preparation. To each 100 mL
of diluted standard add 10 mL of the lanthanum nitrate solution.
Sample Preparation
1. To each 100 mL of prepared sample solution add 10 mL of the lanthanum nitrate
solution.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 500°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 283.3 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, continuous flow purge gas and
non-pyrolytic graphite and are to be used as guidelines only. Smaller size
furnace devices or those employing faster rates of atomization can be operated
using lower atomization temperatures for shorter time periods than the above
recommended settings.
The use of background correction is required.
CLP-M modified for the Contract Laboratory Program.
D-34 ILM02.0
-------
Exhibit D Method 239.2
3. Greater sensitivity can be acheived using the 217.0 nm line, but the optimum
concentration range is reduced. The use of a lead electrodeless discharge lamp
at this lower wavelength has been found to be advantageous. Also a lower
atomization temperature (2400°C) may be preferred.
4. To suppress sulfate interference (up to 1500 ppm) lanthanum is added as the
nitrate to both samples and calibration standards. (Atomic Absorption
Newsletter Vol. 15, No. 3, p. 71, May-June 1976).
5. Since glassware contamination is a severe problem in lead analysis, all
glassware should be cleaned immediately prior to use, and once cleaned, should
not be open to the atmosphere except when necessary.
6. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (see Exhibit E).
7. If method of standard addition is required, follow the procedure given in
Exhibit E.
D-35 ILM02.0
-------
Exhibit D Method 270.2
SELENIUM
Method 270.2 CLP-M (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L
Approximate Detection Limit: 2 ug/L
Preparation of Standard Solution
1. Stock Selenium solution: Dissolve 0.3453 g of selenous acid (actual assay
94.6% H2Se03> in deionized distilled water and make up to 200 mL. 1 mL - 1 mg
Se (1000 mg/L).
2. Nickel Nitrate solution, 5%: Dissolve 24.780 g of ACS reagent grade
in deionized distilled water and make up to 100 mL.
3. Nickel Nitrate solution, 1%: Dilute 20 mL of the 5% nickel nitrate to 100 mL
with deionized distilled water.
4. Working Selenium solution: Prepare dilutions of the stock solution to be used
as calibration standards at the time of analysis. The calibration standards
must be prepared using the same type of acid and at the same concentration as
will result in the sample to be analyzed after sample preparation. Withdraw
appropriate aliquots of the stock solution, add 1 mL of cone. HN03, 2 mL of 30%
H202 and 2 mL of the 5% nickel nitrate solution. Dilute to 100 mL with
deionized distilled water.
Sample Preparation
1. Add 100 uL of the 5% nickel nitrate solution to 5 mL of the digested sample.
The sample is now ready for injection into the furnace.
Instrument Parameters
1. Drying Time and Temp: 30 sec @ 125°C.
2. Charring Time and Temp: 30 sec @ 1200°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4 . Purge Gas Atmosphere : Argon
5. Wavelength: 196.0 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin- Elmer
HGA-2100, based on the use of a 20 uL injection, purge gas interrupt and non-
pyrolytic graphite and are to be used as guidelines only. Smaller size furnace
devices or those employing faster rates of atomization can be operated using
lower atomization tempera- tures for shorter time periods than the above
recommended settings .
2. The use of background correction is required. Background correction made by
the deuterium arc method does not adequately compensate for high levels of
certain interferents (i.e., Al, Fe) .
CLP-M modified for the Contract Laboratory Program.
D-36 ILM02.0
-------
Exhibit D Method 270.2
If conditions occur where significant interference is suspected, the lab must
switch to an alternate wavelength or take other appropriate actions to
compensate for the interference effects.
3. Selenium analysis suffers interference from chlorides (>800 mg/L) and sulfate
(>200 mg/L). For the analysis of industrial effluents and samples with
concentrations of sulfate from 200 to 2000 mg/L, both samples and standards
should be prepared to contain 1% nickel.
4. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (see Exhibit E).
5. If method of standard addition is required, follow the procedure given in
Exhibit E.
6. The use of the Electrodeless Discharge Lamp (EDL) for the light source is
recommended.
D-37 ILM02.0
-------
Exhibit D Method 272.2
SILVER
Method 272.2 CLP-M* (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 1-25 ug/L
Approximate Detection Limit: 0.2 ug/L
Preparation of Standard Solution
1. Stock solution: Dissolve 1.575 g of AgN03 (analytical reagent grade) in
deionized distilled water. Add 10 mL of concentrated HN03 and make up to 1
Liter. 1 mL - 1 mg Ag (1000 mg/L).
2. Prepare dilutions of the stock solution to be used -as calibration standards at
the time of analysis. These solutions are also to be used for "standard
additions".
3. The calibration standards must be prepared using the same type of acid and at
the same concentration as will result in the sample to be analyzed after sample
preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 400°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 328.1 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, continuous flow purge gas and
non-pyrolytic graphite and are to be used as guidelines only. Smaller size
furnace devices or those employing faster rates of atomization can be operated
using lower atomization temperatures for shorter time periods than the above
recommended settings.
2. The use of background correction is required.
3. The use of halide acids should be avoided.
4. If absorption to container walls or formation of AgCl is suspected, see Part G,
AA methods Flame Technique.
5. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (see Exhibit E).
6. If method of standard addition is required, follow the procedure given in
Exhibit E.
CLP-M modified for the Contract Laboratory Program.
D-38 ILM02.0
-------
Exhibit D Method 279.2
THALLIUM
Method 279.2 CLP-M* (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L
Approximate Detection Limit: 1 ug/L
Preparation of Standard Solution
1. Stock solution: Dissolve 1.303g of thallium nitrate, T1N03 (analytical reagent
grade) in deionized distilled water. Add 10 mL of concentrated nitric acid and
dilute to 1 Liter with deionized distilled water. 1 mL - 1 mg Tl (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. These solutions are also to be used for "standard
additions".
3. The calibration standards must be prepared using the same type of acid and at
the same concentration as will result in the sample to be analyzed after sample
preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 400°C.
3. Atomizing Time and Temp: 10 sec @ 2400°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 276.8 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-
Elmer HGA-2100, based on the use of a 20 uL injection, continuous flow purge
gas and non-pyrolytic graphite and are to be used as guidelines only. Smaller
size furnace devices or those employing faster rates of atomization can be
operated using lower atomization temperatures for shorter time periods than
the above recommended settings.
2. The use of background correction is required.
3. Nitrogen may also be used as the purge gas.
4. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (see Exhibit E).
5. If method of standard addition is required, follow the procedure given in
Exhibit E.
CLP-M modified for the Contract Laboratory Program.
D-39 ILM02.0
-------
PART C - ATOMIC ABSORPTION METHODS. FLAME TECHNIQUE'*'
Analyte/Method Page No,
Calcium - Method 215.1 CLP-M* D-41
Magnesium - Method 242.1 CLP-M D-42
Potassium - Method 258.1 CLP-M D-43
Sodium - Method 273.1 CLP-M D-44
From "Interim Methods for the Sampling and Analysis of Priority Pollutants
in Sediments and Fish Tissue", USEPA EMSL, Cincinnati, Ohio, August 1977,
Revised October 1980, as modified for use in the Contract Laboratory
Program.
CLP-M modified for the Contract Laboratory Program.
D-40 ILM02.0
-------
Exhibit D Method 215.1
CALCIUM
Method 215.1 CLP-M* (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.2-7 mg/L using a wavelength of 422.7 run
Sensitivity: 0.08 mg/L
Detection Limit: 0.01 mg/L
Preparation of Standard Solution
1. Stock Solution: Suspend 1.250 g of CaC03 (analytical reagent grade), dried at
180°C for 1 hour before weighing, in deionized distilled water and dissolve
cautiously with a mimimum of dilute HC1. Dilute to 1000 mL with deionized
distilled water. 1 mL - 0.5 mg Ca (500 mg/L).
2. Lanthanum chloride solution: Dissolve 29 g of La£03 , slowly and in small
portions, in 250 mL cone. HC1 (Caution: Reaction is violent) and dilute to
500 mL with deionized distilled water.
3 . Prepare dilutions of the stock calcium solutions to be used as calibration
standards at the time of analysis. To each 10 mL of calibration standard and
sample alike add 1.0 mL of the lanthanum chloride solution, i.e., 20 mL of
standard or sample + 2 mL LaCl3 - 22 mL.
Instrumental Parameters (General)
1 . Calcium hollow cathode lamp
2. Wavelength: 422.7 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Reducing
Notes
1. Phosphate, sulfate and aluminum interfere but are masked by the addition of
lanthanum. Because low calcium values result if the pH of the sample is above
7, both standards and samples are prepared in dilute hydrochloric acid
solution. Concentrations of magnesium greater than 1000 mg/L also cause low
calcium values. Concentrations of up to 500 mg/L each of sodium, potassium and
nitrate cause no interference.
2. Anionic chemical interferences can be expected if lanthanum is not used in
samples and standards.
3. The nitrous oxide -acetylene flame will provide two to five times greater
sensitivity and freedom from chemical inteferences . lonizatlon interferences
should be controlled by adding a large amount of alkali to the sample and
standards. The analysis appears to be free from chemical suppressions in the
nitrous oxide -acetylene flame. (Atomic Absorption Newsletter 14, 29 [1975]).
4. The 239.9 nm line may also be used. This line has a relative sensitivity of
120.
CLP-M modified for the Contract Laboratory Program.
D-41 ILM02.0
-------
Exhibit D Method 242.1
MAGNESIUM
Method 242.1 CLP-M* (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.02-0.5 mg/L using a wavelength of 285.2 nm
Sensitivity: 0.007 mg/L
Detection Limit: 0.001 mg/L
Preparation of Standard Solution
1. Stock Solution: Dissolve 0.829 g of magnesium oxide, MgO (analytical reagent
grade), in 10 mL of redistilled HN03 and dilute to 1 liter with deionized
distilled water. 1 mL - 0.50 mg Mg (500 mg/L).
2. Lanthanum chloride solution: Dissolve 29 g of 1.3203, slowly and in small
portions in 250 mL concentrated HC1 (Caution: Reaction is violent), and dilute
to 500 mL with deionized distilled water.
3. Prepare dilutions of the stock magnesium solution to be used as calibration
standards at the time of analysis. To each 10 mL volume of calibration
standard and sample alike add 1.0 mL of the lanthanum chloride solution, i.e.,
20 mL of standard or sample + 2 mL LaCl3 - 22 mL.
Instrumental Parameters (General)
1. Magnesium hollow cathode lamp
2. Wavelength: 285.2 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Notes
1. The interference caused by aluminum at concentrations greater than 2 mg/L is
masked by addition of lanthanum. Sodium, potassium and calcium cause no
interference at concentrations less than 400 mg/L.
2. The following line may also be used: 202.5 nm Relative Sensitivity 25.
3. To cover the range of magnesium values normally observed in surface waters
(0.1-20 mg/L), it is suggested that either the 202.5 nm line be used or the
burner head be rotated. A 90° rotation of the burner head will produce
approximately one-eighth the normal sensitivity.
*
CLP-M modified for the Contract Laboratory Program.
D-42 ILM02.0
-------
Exhibit D Method 258.1
POTASSIUM
Method 258.1 CLP-M* (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.1-2 mg/L using a wavelength of 766.5 nm
Sensitivity: 0.04 mg/L
Detection Limit: 0.01 mg/L
Preparation of Standard Solution
1. Stock Solution: Dissolve 0.1907 g of KC1 (analytical reagent grade), dried at
110°C, in deionized distilled water and make up to 1 liter. 1 mL - 0.10 mg K
(100 mg/L). •
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. The calibration standards should be prepared using the
same type of acid and at the same concentration as will result in the sample to
be analyzed either directly or after processing.
Instrumental Parameters (General)
1. Potassium hollow cathode lamp
2. Wavelength: 766.5 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Slightly oxidizing
1. In air-acetylene or other high temperature flames (>2800°C), potassium can
experience partial ionization which indirectly affects absorption sensitivity.
The presence of other alkali salts in the sample can reduce this ionization and
thereby enhance analytical results. The ionization suppressive effect of
sodium is small if the ratio of Na to K is under 10. Any enhancement due to
sodium can be stabilized by adding excess sodium (1000 ug/mL) to both sample
and standard solutions. If more stringent control of ionization is required,
the addition of cesium should be considered. Reagent blanks must be analyzed
to correct for potassium impurities in the buffer zone.
2. The 404.4 nm line may also be used. This line has a relative sensitivity of
500.
3. To cover the range of potassium values normally observed in surface waters
(0.1-20 mg/L), it is suggested that the burner head be rotated. A 90° rotation
of the burner head provides approximately one-eighth the normal sensitivity.
*
CLP-M modified for the Contract Laboratory Program.
D-43 ILM02.0
-------
Exhibit D Method 273.1
SODIUM
Method 273.1 CLP-M (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.03-1 mg/L using a wavelength of 589.6 nm
Sensitivity: 0.015 mg/L
Detection Limit: 0.002 mg/L
Preparation of Standard Solutions
1. Stock Solution: Dissolve 2.542 g of NaCl (analytical reagent grade), dried at
140°C, in deionized distilled water and make up to 1 liter. 1 mL - 1 mg Na
(1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. The calibration standards should be prepared using the
same type of acid and at the same concentration as will result in the sample to
be analyzed either directly or after processing.
Instrumental Parameters (General)
1. Sodium hollow cathode lamp
2. Wavelength: 589.6 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Notes
1. The 330.2 nm resonance line of sodium, which has a relative sensitivity of 185,
provides a convenient way to avoid the need to dilute more concentrated
solutions of sodium.
2. Low-temperature flames increase sensitivity by reducing the extent of
ionization of this easily ionized metal. lonization may also be controlled by
adding potassium (1000 mg/L) to both standards and samples.
CLP-M modified for the Contract Laboratory Program.
D-44 ILM02.0
-------
PART D - COLD VAPOR METHODS FOR MERCURY ANALYSIS
Method Page No.
Mercury Analysis in Water by Manual Cold Vapor Technique D-46
Method 245.1 CLP-M*
Mercury Analysis in Water by Automated Cold Vapor Technique D-52
Method 245.2 CLP-M
Mercury Analysis in Soil/Sediment by Manual Cold Vapor Technique D-58
Method 245.5 CLP-M
CLP-M modified for the Contract Laboratory Program.
D-45 ILM02.0
-------
Exhibit D Method 245.1
MERCURY ANALYSIS IN WATER BY MANUAL COLD VAPOR TECHNIQUE
MERCURY
Method 245.1 CLP-M* (Manual Cold Vapor Technique)
1. Scope and Application
1.1 In addition to inorganic forms of mercury, organic mercurials may also be
present. These organo-mercury compounds will not respond to the cold vapor
atomic absorption technique unless they are first broken down and converted to
mercuric ions. Potassium permanganate oxidizes many of these compounds, but
recent studies have shown that a number of organic mercurials, including
phenyl mercuric acetate and methyl mercuric chloride, are only partially
oxidized by this reagent. Potassium persulfate has been found to give
approximately 100% recovery when used as the oxidant with these compounds.
.Therefore, a persulfate oxidation step following the addition of the
permanganate has been included to insure that organo-mercury compounds, if
present, will be oxidized to the mercuric ion before measurement. A heat step
is required for methyl mercuric chloride when present in or spiked to a
natural system.
1.2 The range of the method may be varied through instrument and/or recorder
expansion. Using a 100 mL sample, a detection limit of 0.2 ug Hg/L can be
achieved (See 10.2).
2 . Summary of .Method
2.1 The flameless AA procedure is a physical method based on the absorption of
radiation at 253.7 nm by mercury vapor. Organic mercury compounds are
oxidized and the mercury is reduced to the elemental state and aerated from
solution in a closed system. The mercury vapor passes through a cell
positioned in the light path of an atomic absorption spectrophotometer.
Absorbance (peak height) is measured as a function of mercury concentration
and recorded in the usual manner.
3. Sample Handling and Preservation
3.1 Until more conclusive data are obtained, samples are preserved by
acidification with nitric acid to a pH of 2 or lower immediately at the time
of collection (Exhibit D, Section II).
4. Interference
4.1 Possible interference from sulfide is eliminated by the addition of potassium
permanganate. Concentrations as high as 20 mg/1 of sulfide as sodium sulfide
do not interfere with the recovery of added inorganic mercury from distilled
water (Exhibit D, Section II).
4.2 Copper has also been reported to interfere; however, copper concentrations as
high as 10 mg/L had no effect on recovery of mercury from spiked samples.
*
CLP-M modified for the Contract Laboratory Program.
D-46 ILM02.0
-------
Exhibit D Method 245.1
4.3 Sea waters, brines and industrial effluents high in chlorides require
additional permanganate (as much as 25 mL). During the oxidation step,
chlorides are converted to free chlorine which will also absorb radiation of
253 nm. Care must be taken to assure that free chlorine is absent before the
mercury is reduced and swept into the cell. This may be accomplished by using
an excess of hydroxylamine sulfate reagent (25 mL). Both inorganic and
organic mercury spikes have been quantitatively recovered from the sea water
using this technique.
5. Apparatus
5.1 Atomic Absorption Spectrophotometer: (See Note 1) Any atomic absorption unit
having an open sample presentation area in which to mount the absorption cell
is suitable. Instrument settings recommended by the particular manufacturer
should be followed.
'NOTE 1: Instruments designed specifically for the measurement of mercury
using the cold vapor technique are commercially available and may be
substituted for the atomic absorption spectrophotometer.
5.2 Mercury Hollow Cathode Lamp: Westinghouse WL-22847, argon filled, or
equivalent.
5.3 Recorder: Any multi-range variable speed recorder that is compatible with the
UV detection system is suitable.
5.4 Absorption Cell: Standard spectrophotometer cells 10 cm long, having quartz
end windows may be used. Suitable cells may be constructed from plexiglass
tubing, 1" O.D. X 4-1/2". The ends are ground perpendicular to the
longitudinal axis and quartz windows (1" diameter X 1/16" thickness) are
cemented in place.
The cell is strapped to a burner for support and aligned in the light beam by
use of two 2" by 2" cards. One inch diameter holes are cut in the middle of
each card; the cards are then placed over each end of the cell. The cell is
then positioned and adjusted vertically and horizontally to find the maximum
transmittance.
5.5 Air Pump: Any peristaltic pump capable of delivering 1 liter of air per
minute may be used. A Masterflex pump with electronic speed control has been
found to be satisfactory.
5.6 Flowmeter: Capable of measuring an air flow of 1 liter per minute.
5.7 Aeration Tubing: A straight glass frit having a coarse porosity. Tygon
tubing is used for passage of the mercury vapor from the sample bottle to the
absorption cell and return.
5.8 Drying Tube: 6" X 3/4" diameter tube containing 20 g of magnesium perchlorate
(see Note 2). The apparatus is assembled as shown in Figure 1.
NOTE 2: In place of the magnesium perchlorate drying tube, a small reading
lamp with 60W bulb may be used to prevent condensation of moisture inside the
cell. The lamp is positioned to shine on the absorption cell maintaining the
air temperature in the cell about 10°C above ambient.
D-47 ILM02.0
-------
Exhibit D Method 245.1
Figure 1. Apparatus for Flameless Mercury Determination
ABSORPTION
BUBBLER CELL
SAMPLE SOLUTION
IN BOO BOTTLE
SCRUBBER
CONTAINING
A MERCURY
ABSORBING
MEDIA
D-48
ILM02.0
-------
Exhibit D Method 245.1
6. Reagents
6.1 Sulfuric Acid, Cone: Reagent grade.
6.1.1 Sulfuric acid, 0.5 N: Dilute 14.0 mL of cone. sulfuric acid to 1.0
liter.
6.2 Nitric Acid, Cone: Reagent grade of low mercury content (see.Note 3).
NOTE 3: If a high reagent blank is obtained, it may be necessary to distill
the nitric acid.
6.3 Stannous Sulfate: Add 25 g stannous sulfate to 250 mL of 0.5 N sulfuric acid.
This mixture is a suspension and should be stirred continuously during use.
(Stannous chloride may be used in place of stannous sulfate.)
6.4 Sodium Chloride-Hyroxylamine Sulfate Solution: Dissolve 12 g of sodium
chloride and 12 g of hydroxylamine sulfate in distilled water and dilute to
100 mL. (Hydroxylamine hydrochloride may be used in place of hydroxylamine
sulfate.)
6.5 Potassium Permanganate: 5% solution, w/v. Dissolve 5 g of potassium
permanganate in 100 mL of distilled water.
6.6 Potassium Persulfate: 5% solution, w/v. Dissolve 5 g of potassium persulfate
in 100 mL of distilled water.
6.7 Stock Mercury Solution: Dissolve 0.1354 g of mercuric chloride in 75 mL of
distilled water. Add 10 mL of cone, nitric acid and adjust the volume to
100.0 mL. 1 mL - 1 mg Hg.
6.8 Working Mercury Solution: Make successive dilutions of the stock mercury
solution to obtain a working standard containing 0.1 ug per mL. This working
standard and the dilutions of the stock mercury solution should be prepared
fresh daily. Acidity of the working standard should be maintained at 0.15%
nitric acid. This acid should be added to the flask as needed before the
addition of the aliquot.
7. Calibration
7.1 Transfer 0, 0.5, 1.0, 5.0 and 10.0 mL aliquots of the working mercury solution
containing 0 to 1.0 ug of mercury to a series of 300 mL BOD bottles. Add
enough distilled water to each bottle to make a total volume of 100 mL. Mix
thoroughly and add 5 mL of cone, sulfuric acid (6.1) and 2.5 mL of cone.
nitric acid (6.2) to each bottle. Add 15 mL of KMn04 (6.5) solution to each
bottle and allow to stand at least 15 minutes. Add 8 mL of potassium
persulfate (6.6) to each bottle and heat for 2 hours in a water bath
maintained at 95°C. Alternatively, cover the BOD bottles with foil and heat
in an autoclave for 15 minutes at 120°C and 15 Ibs. Cool and add 6 mL of
sodium chloride-hydroxylamine sulfate solution (6.4) to reduce the excess
permanganate. When the solution has been decolorized wait 30 seconds, add 5
mL of the stannous sulfate solution (6.3) and immediately attach the bottle to
the aeration apparatus forming a closed system. At this point the sample is
allowed to stand quietly without manual agitation.
D-49 ILM02.0
-------
Exhibit D Method 245.1
The circulating pump, which has previously been adjusted to a rate of 1 liter
per minute, is allowed to run continuously (see Note 4). The absorbance will
increase and reach maximum within 30 seconds. As soon as the recorder pen
levels off, approximately 1 minute, open the bypass valve and continue the
aeration until the absorbance returns to its minimum value (see Note 5).
Close the bypass valve, remove the stopper and frit from the BOD bottle and
continue the aeration. Proceed with the standards and construct a standard
curve by plotting peak height versus micrograms of mercury.
NOTE 4: An open system where the mercury vapor is passed through the
absorption cell only once may be used instead of the closed system.
NOTE 5: Because of the toxic nature of mercury vapor precaution must be taken
to avoid its inhalation. Therefore, a bypass has been included in the system
to either vent the mercury vapor into an exhaust hood or pass the vapor
through some absorbing media, such as: a) equal volumes of 0.1 M KMn04,
'and 10% H2S04 or
b) 0.25% iodine in a 3% a KI solution. A specially treated charcoal that will
adsorb mercury vapor is available.
8. Procedure
8.1 Transfer 100 mL, or an aliquot diluted to 100 mL, containing not more than 1.0
ug of mercury, to a 300 mL BOD bottle. Add 5 mL of sulfuric acid (6.1) and
2.5 mL of cone, nitric acid (6.2) mixing after each additon. Add 15 mL of
potassium permanganate solution (6.5) to each sample bottle (see Note 6). For
sewage samples additional permanganate may be required. Shake and add
additional portions of potassium permanganate solution, if necessary, until
the purple color persists for at least 15 minutes. Add 8 mL of potassium
persulfate (6.6) to each bottle and heat for 2 hours in a water bath at 95°C.
NOTE 6: The same amount of KMn04 added to the samples should be present in
standards and blanks.
Cool and add 6 mL of sodium chloride-hydroxylamine sulfate (6.4) to reduce the
excess permanganate (see Note 7). Purge the head space in the BOD bottle for
at least 1 minute and add 5 mL of Stannous Sulfate (6.3) and immediately
attach the bottle to the aeration apparatus. Continue as described under
Calibration.
NOTE 7: Add reductant in 6 mL increments until KMn04 is completely reduced.
9. Calculation
9.1 Determine the peak height of the unknown from the chart and read the mercury
value from the standard curve.
9.2 Calculate the mercury concentration in the sample by the formula:
ug Hg in 1,000
ug Hg/L - aliquot x
volume of aliquot in mL
D-50 ILM02.0
-------
Exhibit D Method 245.1
10. Appendix
10.1 If additional sensitivity is required, a 200 ml. sample with recorder expansion
may be used provided the instrument does not produce undue noise. Using a
Coleman MAS-50 with a drying tube of magnesium perchlorate and a variable
recorder, 2 mv was set to read full scale. With these conditions, and
distilled water solutions of mercuric chloride at concentrations of 0.15,
0.10, 0.05 and 0.025 ug/L the standard deviations were ±0.027, +0.0006, ±0.01
and ±0.004. Percent recoveries at these levels were 107, 83, 84 and 96%,
respectively.
10.2 Directions for the disposal of mercury-containing wastes are given in ASTM
Standards, Part 31, "Water", p. 349, Method D3223 (1976).
D-51 ILM02.0
-------
Exhibit D Method 245.2
MERCURY ANALYSIS IN WATER BY AUTOMATED COLD VAPOR TECHNIQUE
MERCURY
Method 245.2 CLP-M* (Automated Cold Vapor Technique)
1. Scope and Application
1.1 The working range is 0.2 to 20.0 ug Hg/L.
2. Summary of Method
2.1 The flameless AA procedure is a physical method based on the absorption of
radiation at 253.7 nm by mercury vapor. The mercury is reduced to the
elemental state and aerated from solution. The mercury vapor passes through a
cell positioned in the light path of an atomic absorption spectrophotometer.
•Absorbance (peak height) is measured as a function of mercury concentration
and recorded in the usual manner.
2.2 In addition to inorganic forms of mercury, organic mercurials may also be
present. These organo-mercury compounds will not respond to the flameless
atomic absorption technique unless they are first broken down and converted to
mercuric ions. Potassium permanganate oxidizes many of t-.hese compounds, but
recent studies have shown that a number of organic mercurials, including
phenyl mercuric acetate and methyl mercuric chloride, are only partially
oxidized by this reagent. Potassium persulfate has been found to give
approximately 100% recovery when used as the oxidant with these compounds.
Therefore, an automated persulfate oxidation step following the automated
addition of the permanganate has been included to insure that organo-mercury
compounds, if present, will be oxidized to the mercuric ion before
measurement.
3. Sample Handling and Preservation
3.1 Until more conclusive data are obtained, samples are preserved by
acidification with nitric acid to a pH of 2 or lower immediately at the time
of collection (Exhibit D, Section II).
4. Interferences (see NOTE 1)
4.1 Some sea waters and waste-waters high in chlorides have shown a positive
interference, probably due to the formation of free chlorine.
4.2 Formation of a heavy precipitate, in some wastewaters and effluents, has been
reported upon addition of concentrated sulfuric acid. If this is encountered,
the problem sample cannot be analyzed by this method.
4.3 Samples containing solids must be blended and then mixed while being sampled
if total mercury values are to be reported.
NOTE 1: All of the above interferences can be overcome by use of the Manual
Mercury method.
CLP-M modified for the Contract Laboratory Program.
D-52 ILM02.0
-------
Exhibit D Method 245.2
5. Apparatus
5.1 Technicon Auto Analyzer or equivalent instrumentation consisting of:
5.1.1 Sampler II with provision for sample mixing.
5.1.2 Manifold.
5.1.3 Proportioning Pump II or III.
5.1.4 High temperature heating bath with two distillation coils (Technicon
Part #116-0163) in series.
5.2 Vapor-liquid separator (Figure 1).
5.3 Absorption cell, 100 mm long, 10 mm diameter with quartz windows.
5.4 Atomic Absorption Spectrophotometer (see Note 2): Any atomic absorption unit
having an open sample presentation area in which to mount the absorption cell
is suitable. Instrument settings recommended by the particular manufacturer
should be followed.
NOTE 2: Instruments designed specifically for the measurement of mercury
using the cold vapor technique are commercially available and may be
substituted for the atomic absorption spectrophotometer.
5.5 Mercury Hollow Cathode Lamp: Westinghouse WL-22847, argon filled, or
equivalent.
5.6 Recorder: Any multi-range variable speed recorder that is compatible with the
UV detection system is suitable.
6. Reagents
6.1 Sulfuric Acid, Cone: Reagent grade
6.1.1 Sulfuric acid, 2 N: Dilute 56 mL of cone, sulfurlc acid to 1 liter
with distilled water.
6.1.2 Sulfuric acid, 10%: Dilute 100 mL cone, sulfuric acid to 1 liter
with distilled water.
6.2 Nitric acid, Cone: Reagent grade of low mercury content.
6.2.1. Nitric Acid, 0.5% Wash Solution: Dilute 5 mL of concentrated nitric
acid to 1 liter with distilled water.
6.3 Stannous Sulfate (See Note 3): Add 50 g stannous sulfate to 500 mL of 2 N
sulfuric acid (6.1.1). This mixture is a suspension and should be stirred
continuously during use.
NOTE 3: Stannous chloride may be used in place of stannous sulfate.
D-53 ILM02.0
-------
Exhibit D Method 245.2
6.4 Sodium Chloride-Hydroxylamine Sulfate (See Note 4) Solution: Dissolve 30 g of
sodium chloride and 30 g of hydroxylamine sulfate in distilled water to 1
liter.
NOTE 4: Hydroxylamine hydrochloride may be used in place of hydroxylamine
sulfate.
6.5 Potassium Permanganate: 0.5% solution, w/v. Dissolve 5 g of potassium
permanganate in 1 liter of distilled water.
6.6 Potassium Permanganate, 0.1 N: Dissolve 3.16 g of potassium permanganate in
distilled water and dilute to 1 liter.
6.7 Potassium Persulfate: 0.5% solution, w/v. Dissolve 5 g potassium persulfate
in 1 liter of distilled water.
6.8 .Stock Mercury Solution: Dissolve 0.1354 g of mercuric chloride in 75 mL of
distilled water. Add 10 mL of cone, nitric acid and adjust the volume to
100.0 mL. 1.0 mL - 1.0 mg Hg.
6.9 Working Mercury Solution: Make successive dilutions of the stock mercury
solution (6.8) to obtain a working standard containing 0.1 ug per mL. This
working standard and the dilutions of the stock mercury solution should be
prepared fresh daily. Acidity of the working standard should be maintained at
0.15% nitric acid. This acid should be added to the flask as needed before
the addition of the aliquot. From this solution prepare standards containing
0.2, 0.5, 1,0, 2.0, 5.0, 10.0, 15.0 and 20.0 ug Hg/L.
6.10 Air Scrubber Solution: Mix equal volumes of 0.1 N potassium permanganate
(6.6) and 10% sulfuric acid (6.1.2).
7. Procedure (See Note 5)
7.1 Set up manifold as shown in Figure 2.
7.2 Feeding all the reagents through the system with acid wash solution (6.2.1)
through the sample line, adjust heating bath to 105°C.
7.3 Turn on atomic absorption spectrophotometer, adjust instrument settings as
recommended by the manufacturer, align absorption cell in light path for
maximum transmittance and place heat lamp directly over absorption cell.
7.4 Arrange working mercury standards from 0.2 to 20.0 ug Hg/L in sampler and
start sampling. Complete loading of sample tray with unknown samples.
7.5 Prepare standard curve by plotting peak height of processed standards against
concentration values. Determine concentration of samples by comparing sample
peak height with standard curve.
7.6 After the analysis is complete put all lines except the H2S04 line in
distilled water to wash out system. After flushing, wash out the H2S04 line.
Also flush the coils in the high temperature heating bath by pumping stannous
sulfate (6.3) through the sample lines followed by distilled water. This will
prevent build-up of oxides of manganese.
D-54 ILM02.0
-------
Exhibit D Method 245.2
NOTE 5: Because of the .toxic nature of mercury vapor, precaution must be
taken to avoid its inhalation. Venting the mercury vapor into an exhaust hood
or passing the vapor through some absorbing media such as: a) equal volumes
of 0.1 N KMn04(6.6) and 10% H2S04 (6.1.2), or b) 0.25% iodine in a 3% KI
solution, is recommended. A specially treated charcoal that will absorb
mercury vapor is also available.
D-55 ILM02.0
-------
Exhibit D Method 245.1
AIR AND
SOLUTION
IN
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7/25 Y
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Kcm
SOLUTION
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D-56
ILM02.0
-------
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-------
Exhibit D Method 245.5
MERCURY ANALYSIS IN SOIL/SEDIMENT BY MANUAL COLD VAPOR TECHNIQUE
MERCURY (in Sediments)
Method 245.5 CLP-M* (Manual Cold Vapor Technique)
1. Scope and Application
1.1 This procedure measures total mercury (organic and inorganic) in soils,
sediments, bottom deposits and sludge type materials
1.2 The range of the method is 0.2 to 5 ug/g. The range may be extended above or
below the normal range by increasing or decreasing sample size or through
instrument and recorder control
2. Summary of Method
2.1 .A weighed portion of the sample is acid digested for 2 minutes at 95°C,
followed by oxidation with potassium permanganate and potassium persulfate.
Mercury in the digested sample is then measured by the conventional cold vapor
technique
2.2 An alternate digestion involving the use of an autoclave is described in (8.2)
3. Sample Handling and Preservation
3.1 Because of the extreme sensitivity of the analytical procedure and the
omnipresence of mercury, care must be taken to avoid extraneous contamination.
Sampling devices and sample containers should be ascertained to be free of
mercury; the sample should not be exposed to any condition in the laboratory
that may result in contact or air-borne mercury contamination
3.2 Refrigerate solid samples at 4°C (±2°) upon receipt until analysis (see
Exhibit D, Section II).
3.3 The sample should be analyzed without drying. A separate percent solids
determination is required, (Part F).
4. Interferences
4.1 The same types of interferences that may occur in water samples are also
possible with sediments, i.e., sulfides, high copper, high chlorides, etc.
4.2 Samples containing high concentrations of oxidizable organic materials, as
evidenced by high chemical oxygen demand values, may not be completely
oxidized by this procedure. When this occurs, the recovery of organic mercury
will be low. The problem can be eliminated by reducing the weight of the
original sample or by increasing the amount of potassium persulfate (and
consequently stannous chloride) used in the digestion.
CLP-M modified for the Contract Laboratory Program.
D-58 ILM02.0
-------
Exhibit D Method 245.5
5. Apparatus
5.1 Atomic Absorption Spectrophotometer (see Note 1): Any atomic absorption unit
having an open sample presentation area in which to mount the absorption cell
is suitable. Instrument settings recommended by the particular manufacturer
should be followed
NOTE 1: Instruments designed specifically for the measurement of mercury
using the cold vapor technique are commercially available and may be
substituted for the atomic absorption spectrophotometer
5.2 Mercury Hollow Cathode Lamp: Westinghouse WL-22847, argon filled, or
equivalent
5.3 Recorder: Any multi-range variable speed recorder that is compatible with the
UV detection system is suitable.
5.4 Absorption Cell: Standard spectrophotometer cells 10 cm long, having quartz
end windows may be used. Suitable cells many be constructed from pexiglass
tubing, 1" O.D. X 4-1/2". The ends are ground perpendicular to the
longitudinal axis and quartz windows (1" diameter X 1/16" thickness) are
cemented in place. Gas inlet and outlet ports (also of plexiglass but 1/4"
O.D.) are attached approximately 1/2" from each end. The cell is strapped to
a burner for support and aligned in the light beam to give the maximum
transmittance. Two 2" X 2" cards with one inch diameter holes may be placed
over each end of the cell to assist in positioning the cell for maximum
transmittance.
5.5 Air Pump: Any peristaltic pump capable of delivering 1 liter of air per
minute may be used. A Masterflex pump with electronic speed control has been
found to be satisfatory. (Regulated compressed air can be used in an open
one-pass system.)
5.6 Flowmeter: Capable of measuring an air flow of 1 liter per minute
5.7 Aeration Tubing: Tygon tubing is used for passage of the mercury vapor from
the sample bottle to the absorption cell and return. Straight glass tubing
terminating in a coarse porous frit is used for sparging air into the sample
5.8 Drying Tube: 6" X 3/4" diameter tube containing 20 g of magnesium perchlorate
(see Note 2).
NOTE 2: In place of the magnesium perchlorate drying tube, a small reading
lamp with 60W bulb may be used to prevent condensation of moisture inside the
cell. The lamp is positioned to shine on the absorption cell maintaining the
air temperature in the cell about 10°C above ambient.
6. Reagents
6.1 Sulfuric acid, cone.: Reagent grade of low mercury content
6.2 Nitric acid, cone.: Reagent grade of low mercury content
D-59 ILM02.0
-------
Exhibit D Method 245.5
6.3 Stannous Sulfate: Add 25 g stannous sulfate to 250 mL of 0.5 N sulfuric acid
(6.2). This mixture is a suspension and should, be stirred continuously during
use
6.4 Sodium Chloride-Hydroxylamine Sulfate (See Note 3) Solution: Dissolve 12 g of
sodium chloride and 12 g of hydroxylamine sulfate in distilled water and
dilute to 100 mL
NOTE 3: A 10% solution of stannous chloride may be substituted for (6.3)
and hydroxylamine hydrochloride may be used in place of hydroxylamine sulfate
in (6.4)
6.5 Potassium Permanganate: 5% solution, w/v. Dissolve 5 g of potassium
permanganate in 100 mL of distilled water
6.6 Potassium Persulfate: 5% solution, w/v. Dissolve 5 g of potassium persulfate
in 100 mL of distilled water
6.7 Stock Mercury Solution: Dissolve 0.1354 g of mercuric chloride in 75 mL of
distilled water. Add mL of cone, nitric acid and adjust the volume to 100.0
mL. 1.0 = 1.0 mg Hg
6.8 Working Mercury Solution: Make successive dilutions of the stock mercury
solution (6.7) to obtain a working standard containing 0.1 ug/mL. This
working standard and the dilution of the stock mercury solutions should be
prepared fresh daily. Acidity of the working standard should be maintained at
0.15% nitric acid. This acid should be added to the flask as needed before
the addition of the aliquot
7. Calibration
7.1 Transfer 0, 0.5, 1.0, 5.0 and 10 mL aliquots of the working mercury solutions
(6.8) containing 0 to 1.0 ug of mercury to a series of 300 mL BOD bottles.
Add enough distilled water to each bottle to make a total volume of 10 mL.
Add 5 mL of cone. 1*2804 (6.1) and 2.5 mL of cone. HN03 (6.2) and heat 2
minutes in a water bath at 95°C. Allow the sample to cool and add 50 mL
distilled water, 15 mL of KMnO^ solution (6.5) and 8 mL of potassium
persulfate solution (6.6) to each bottle and return to the water bath for 30
minutes. Cool and add 6 mL of sodium chloride-hydroxylamine sulfate solution
(6.4) to reduce the excess permanganate. Add 50 mL of distilled water.
Treating each bottle individually, add 5 mL of stannous sulfate solution (6.3)
and immediately attach the bottle to the aeration apparatus. At this point
the sample is allowed to stand quietly without manual agitation. The
circulating pump, which has previously been adjusted to a rate of 1 liter per
minute, is allowed to run continuously. The absorbance, as exhibited either
on the spectrophotometer or the recorder, will increase and reach maximum
within 30 seconds. As soon as the recorder pen levels off, approximately 1
minute, open the bypass valve and continue the aeration until the absorbance
returns to its minimum value (see Note 4). Close the bypass valve, remove the
fritted tubing from the BOD bottle and continue the aeration. Proceed with
the standards and construct a standard curve by plotting peak height versus
micrograms of mercury
D-60 ILM02.0
-------
Exhibit D Method 245.5
NOTE 4: Because of the toxic nature of mercury vapor, precaution must be
taken to avoid its inhalation. Therefore, a bypass has been included in the
system to either vent the mercury vapor into an exhaust hood or pass the vapor
through some absorbing media, such as: a) equal volumes of 0.1 N KMn04 and
10% H2S04, or b) 0.25% iodine in a 3% KI solution. A specially treated
charcoal that will absorb mercury vapor is also available.
8. Procedure
8.1 Weigh a representative 0.2 g portion of wet sample and place in the bottom of
a BOD bottle. Add 5 mL of sulfuric acid (6.1) and 2.5 mL of concentrated
nitric acid (6.2) mixing after each addition. Heat two minutes in a water
bath at 95°C. Cool, add 50 mL distilled water, 15 mL potassium permanganate
solution (6.5) and 8 mL of potassium persulfate solution (6.6) to each sample
bottle. Mix thoroughly and place in the water bath for 30 minutes at 95°C.
Cool and add 6 mL of sodium chloride-hydroxylamine sulfate (6.4) to reduce the
•excess permanganate. Add 55 mL of distilled water. Treating each bottle
individually, purge the head space of the sample bottle for at least one
minute and add 5 mL of stannous sulfate (6.3) and immediately attach the
bottle to the aeration apparatus. Continue as described under (7.1)
8.2 An alternate digestion procedure employing an autoclave may also be used. In
this method 5 mL of cone. H2S04 and 2 mL of cone. HN03 are added to the 0.2
g of sample. 5 mL of saturated KMn04 solution and 8 mL of potassium
persulfate solution are added and the bottle is covered with a piece of
aluminum foil. The sample is autoclaved at 121°C and 15 Ibs. for 15 minutes.
Cool, make up to a volume of 100 mL with distilled water and add 6 mL of
sodium chloride-hydroxylamine sulfate solution (6.4) to reduce the excess
permanganate. Purge the head space of the sample bottle for at least one
minute and continue as described under (7.1)
9. Calculations
9.1 Measure the peak height of the unknown from the chart and read the mercury
value from the standard curve
9.2 Calculate the mercury concentration in the sample by the formula:
ug Hg in the aliquot
ug Hg/g - wt of the aiiquot ln ^3
(based upon dry wt of the sample)
9.3 Report mercury concentrations as described for aqueous mercury samples
converted to units of mg/kg. The sample result or the detection limit for
each sample must be corrected for sample weight and % solids before reporting.
D-61 ILM02.0
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PART E - METHODS FOR CYANIDE ANALYSIS
Method Page No.
Method for Total Cyanide Analysis in Water
Method 335.2 CLP-M D-63
Method for Total Cyanide Analysis in Soil/Sediment
Method 335.2 CLP-M D-71
Method for Total Cyanide Analysis by Midi Distillation
Method 335.2 CLP-M D-82
CLP-M Modified for the Contract Laboratory Program.
D-62 ILM02.0
-------
Exhibit D Method 335.2
METHOD FOR TOTAL CYANIDE ANALYSIS IN WATER
CYANIDE, TOTAL (in Water)
Method 335.2 CLP-M* (Titrimetric; Manual Spectrophotometric; Semi-Automated
Spectrophotometric)
1. Scope and Application
1.1 This method is applicable to the determination of cyanide in drinking, surface
and saline waters, domestic and industrial wastes.
1.2 The titration procedure using silver nitrate with p-
dimethylaminobenzalrhodanine indicator is used for measuring concentrations of
cyanide exceeding 1 mg/L (0.25 mg/250 mL of absorbing liquid). (Option A,
8.2).
1.3 The manual colorometric procedure is used for concentrations below 1 mg/L of
cyanide and is sensitive to about 0.01 mg/L. (Option B, 8.3).
1.4 The working range of the semi-automated Spectrophotometric method is 0.020 to
0.200 mg/L. Higher level samples must be diluted to fall within the working
range. (Option C, 8.4).
2. Summary of Method
2.1 The cyanide.as (HRN) hydrocyanic acid (HCN) is released from cyanide complexes
by means of a reflux-distillation operation and absorbed in a scrubber
containing sodium hydroxide solution. The cyanide ion in the absorbing
solution is then determined by volumetric titration or colorimetrically.
2.2 In the colorimetric measurement the cyanide is converted to cyanogen chloride,
CNC1, by reaction with chloramine-T at a pH less than 8 without hydrolyzing to
the cyanate. After the reaction is complete, color is formed on the addition
of pyridine-pyrazolone or pyridinebarbituric acid reagent. The absorbance is
read at 620 nm when using pyridine-pyrazolone or 578 nm for pyridine-
barbituric acid. To obtain colors of comparable intensity, it is essential to
have the same salt content in both the sample and the standards.
2.3 The titimetric measurement uses a standard solution of silver nitrate to
titrate cyanide in the presence of a silver sensitive indicator.
3. Definitions
Cyanide is defined as cyanide ion and complex cyanides converted to
hydrocyanic acid (HCN) by reaction in a reflux system of a mineral acid in the
presence of magnesium ion.
4. Sample Handling and Preservation
4.1 All bottles must be thoroughly cleansed and rinsed to remove soluble material
from containers.
CLP-M Modified for the Contract Laboratory Program.
D-63 ILM02.0
-------
Exhibit D Method 335.2
4.2 Oxidizing agents such as chlorine decompose most of the cyanides. Test a drop
of the sample with potassium iodide-starch test paper (Kl-starch paper); a
blue color indicates the need for treatment. Add ascorbic acid, a few
crystals at a time, until a drop of sample produces no color on the indicator
paper. Then add an additional 0.6 g of ascorbic acid for each liter of sample
volume.
4.3 Samples are preserved with 2 mL of 10 N sodium hydroxide per liter of sample
(pH> 12) at the time of collection (Exhibit D, Section II).
4.4 Samples must be stored at 4°C(+2°C) and must be analyzed within the holding
time specified in Exhibit D, Section II.
5. Interferences
5.1 Interferences are eliminated or reduced by using the distillation procedure
•described in Procedure 8.1.
5.2 Sulfides adversely affect the colorimetric and titration procedures. If a
drop of the distillate on lead acetate test paper indicates the presence of
sulfides, treat 25 mL more of the sample than that required for the cyanide
determination with powdered cadmium carbonate. Yellow cadmium sulfide
precipitates if the sample contains sulfide. Repeat this operation until a
drop of the treated sample solution does not darken the lead acetate test
paper. Filter the solution through a dry filter paper into a dry beaker, and
from the filtrate measure the sample to be used for analysis. Avoid a large
excess of cadmium carbonate and a long contact time in order to minimize a
loss by complexation or occlusion of cyanide on the precipitated material.
Sulfides should be removed prior to preservation with sodium hydroxide as
described in 4.3.
5.3 The presence of surfactants may cause the sample to foam during refluxing. If
this occurs, the addition of an agent such as Dow Corning 544 antifoam agent
will prevent the foam from collecting in the condenser. Fatty acids will
distill and form soaps under alkaline titration conditions, making the end
point almost impossible to detect. When this occurs, one of the
spectrophotometric methods should be used.
6. Apparatus
6.1 Reflux distillation apparatus such as shown in Figure 1 or Figure 2. The
boiling flask should be of 1 liter size with inlet tube and provision for
condenser. The gas absorber may be a Fisher-Milligan scrubber.
6.2 Microburet, 5.0 mL (for titration)
6.3 Spectrophotometer suitable for measurements at 578 ran or 620 nm with a 1.0 cm
cell or larger (for manual spectrophotometric method).
6.4 Technicon AA II System or equivalent instrumentation, (for automated
spectrophotometric method) including:
6.4.1 Sampler
6.4.2 Pump III
D-64 ILM02.0
-------
Exhibit D Method 335.2
6.4.3 Cyanide Manifold (Figure 3)
6.4.4 SCIC Colorimeter with 15 nun flowcells and 570 run filters
6.4.5 Recorder
6.4.6 Data System (optional)
6.4.7 Glass or plastic tubes for the sampler
7. Reagents
7.1 Distillation and Preparation Reagents
7.1.1 Sodium hydroxide solution, 1.25N: Dissolve 50 g of NaOH in distilled
water, and dilute to 1 liter with distilled water.
7.1.2 Cadmium carbonate: powdered
7.1.3 Ascorbic acid: crystals
7.1.4 Sulfuric acid: concentrated
7.1.5 Magnesium chloride solution: Weight 510 g of MgCl2'6H20 into a 1000
mL flask, dissolved and dilute to 1 liter with distilled water.
7.2 Stock Standards and Titration Reagents
7.2.1 Stock cyanide solution: Dissolve 2.51 g of KCN and 2 g KOH in 1
liter of distilled water. Standardize with 0.0192 N AgN03-
7.2.2 Standard cyanide solution, intermediate: Dilute 50.0 mL of stock (1
mL - 1 mg CN) to 1000 mL with distilled water.
7.2.3 Standard cyanide solution: Prepare fresh daily by diluting 100.0 mL
of intermediate cyanide solution to 1000 mL with distilled water and
store in a glass stoppered bottle. 1 raL - 5.0 ug CN (5.0 mg/L).
7.2.4 Standard silver nitrate solution, 0.0192 N: Prepare by crushing
approximately 5 g AgN03 crystals and drying to constant weight at
405C. Weight out 3.2647 g of dried AgN03, dissolve in distilled
water, and dilute to 1000 mL (1 mL = 1 mg CN).
7.2.5 Rhodanine indicator: Dissolve 20 mg of p-dimethyl-
aminobenzalrhodanine in 100 mL of acetone.
7.2.6 Sodium hydroxide solution, 0.25 N: Dissolve 10 g or NaOH in
distilled water and dilute to 1 liter.
7.3 Manual Spectrophotometric Reagents
7.3.1 Sodium dihydrogenphosphate, 1 M: Dissolve 138 g of NaH2P04'H20 in a
liter of distilled water. Refrigerate this solution.
D-65 ILM02.0
-------
Exhibit D Method 335.2
7.3.2 Chloramine-T solution: Dissolve 1.0 g of white, water soluble
chloramine-T in 100 mL of distilled water and refrigerate until ready
to use. Prepare fresh weekly.
7.3.3 Color Reagent-One of the following may be used:
7.3.3.1 Pyridine-barbituric acid reagent: Place 15 g of
barbituric acid in a 250 mL volumetric flask and add just
enough distilled water to wash the sides of the flask and
wet the barbituric acid. Add 75 mL of pyridine and mix.
Add 15 mL of HC1 (sp gr 1.19), mix, and cool to room
temperature. Dilute to 250 mL with distilled water and
mix. This reagent is stable for approximately six months
if stored in a cool, dark place.
7.3.3.2 Pyridine-pyrazolone solution:7.3.3.2.1 3-Methyl-1-phenyl-
2-pyrazolin-5-one reagent, saturated solution: Add 0.25 g
of 3-methyl-l-phenyl-2-pyrazolin-5-one to 50 mL of
distilled water, heat to 60°C with stirring. Cool to room
temperature.
7.3.3.2.1 3-Methyl-lphenyl-2-pyrazolin-5-one reagent,
saturated solution: Add 0.25 g of "*-methyl-1-
phenyl-2-pyrazolin-5-one to 50 mL of distilled
water, heat to 60°C with stirring. Cool to
room temperature.
7.3.3.2.2 3,3'Dimethyl-l,l'-diphenyl [4,4'-bi-2
pyrazolin]-5,5'dione (bispyrazolone):
Dissolve 0.01 g of bispyrazolone in 10 mL of
pyridine.
7.3.3.2.3 Pour solution (7.3.3.2.1) through nonacid-
washed filter paper. Collect the filtrate.
Through the same filter paper pour solution
(7.3.3.2.2) collecting the filtrate in the
same container as filtrate from (7.3.3.2.1).
Mix until the filtrates are homogeneous. The
mixed reagent develops a pink color but this
does not affect the color production with
cyanide if used within 24 hours of
preparation.
7.4 Semi-Automated Spectrophotometrie Reagents
7.4.1 Chloramine-T solution: Dissolve 0.40 g of chloramine-T in distilled
water and dilute to 100 mL. Prepare fresh daily.
7.4.2 Phosphate buffer: Dissolve 138 g of Nal^PO^i^O in distilled water
and dilute to 1 liter. Add 0.5 mL of 3rij-35 (available from
Technicon). Store at 4°C(+2°C).
7.4.3 Pyridine-barbituric acid solution: Transfer 15 g of barbituric acid
into a 1 liter volumetric flask. Add about 100 mL of distilled water
and swirl the flask. Add 74 mL of pyridine and mix. Add 15 mL of
D-66 ILM02.0
-------
Exhibit D Method 335.2
concentrated HC1 and mix. Dilute to about 900 mL with distilled
water and mix until the barbituric acid is dissolved. Dilute to 1
liter with distilled water. Store at 4°C(±2°C).
7.4.4 Sampler wash: Dissolve 10 g of NaOH in distilled water and dilute to
1 liter.
8. Procedure
8.1 Distillation
8.1.1 Place 500 mL of sample in the 1 liter boiling flask. Add 50 mL, of
sodium hydroxide (7.1.1) to the absorbing tube and dilute if
necessary with distilled water to obtain an adequate depth of liquid
in the absorber. Connect the boiling flask, condenser, absorber and
trap in the train.
8.1.2 Start a slow stream of air entering the boiling flask by adjusting
the vacuum source. Adjust the vacuum so that approximately one
bubble of air per second enters the boiling flask through the air
inlet tube.
NOTE: The bubble rate will not remain constant after the reagents
have been added and while heat is being applied to the flask. It
will be necessary to readjust the air rate occasionally to prevent
the solution in the boiling flask from backing up into the air
inlet tube.
8.1.3 Slowly add 25 mL concentrated sulfuric acid (7.1.4) through the air
inlet tube. Rinse the tube with distilled water and allow the
airflow to mix the flask contents for 3 minutes. Pour 20 mL of
magnesium chloride solution (7.1.5) into the air inlet and wash down
with a stream of water.
8.1.4 Heat the solution to boiling, taking care to prevent the solution
from backing up into and overflowing from the air inlet tube. Reflux
for one hour. Turn off heat and continue the airflow for at least 15
minutes. After cooling the boiling flask, disconnect absorber and
close off the vacuum source.
8.1.5 Drain the solution from the absorber into a 250 mL volumetric flask
and bring up to volume with distilled water washings from the
absorber tube.
8.2 Titrimetric Determination (Option A)
8.2.1 If the sample contains more than 1 mg of CN, transfer the distillate,
or a suitable aliquot diluted to 250 mL, to a 500 mL Erlenmeyer
flask. Add 10-12 drops of the benzalrhodanine indicator.
8.2.2 Titrate with standard silver nitrate to the first change in color
from yellow to brownish-pink. Titrate a distilled water blank using
the same amount of sodium hydroxide and indicator as in the sample.
D-67 ILM02.0
-------
.Exhibit D Method 335.2
8.2.3 The analyst should familiarize himself with the end point of the
titration and the amount of indicator zo be used before actually
titrating the samples. A 5 or 10 mL microburet may be conveniently
used to obtain a more precise titration.
8.3 Manual Spectrophotometric Determination (Option B)
8.3.1 Withdraw 50 mL or less of the solution from the flask and transfer to
a 100 mL volumetric flask. If less than 50 mL is taken, dilute to 50
mL with 0.25 N sodium hydroxide solution (7.2.6). Add 15.0 mL of
sodium phosphate solution (7.3.1) and mix. The dilution factor must
be reported on Form XIV.
8.3.1.1 Pyridine-barbituric acid method: Add 2 mL of chloramine-T
(7.3.2) and mix. After 1 to 2 minutes, add 5 mL of
pyridine-barbituric acid solution (7.3.3.1) and mix.
Dilute to mark with distilled water and mix again. Allow
8 minutes for color development then read absorbance at
578 nm in a 1 cm cell within 15 minutes.
8.3.1.2 Pyridine-pyrazolone method: Add 0.5 mL of chloramine-T
(7.3.2) and mix. After 1 to 2 minutes, add 5 mL of
pyridine-pyrazolone solution (7.3.3.2) and mix. Dilute to
mark with distilled water and mix again. After 40
minutes, read absorbance at 620 nm in a 1 cm cell. NOTE:
More than 0.5 mL of chloramine-T will prevent the color
from developing with pyridine-pyrazolone.
8.3.2 Prepare a minimum of 3 standards and a blank by pipetting suitable
volumes of standard solution into 250 mL volumetric flasks. NOTE:
One calibration standard must be at the Contract Required Detection
Limit (CRDL). To each standard, add 50 mL of 1.25 N sodium hydroxide
and dilute to 250 mL with distilled wa~er. Standards must bracket
the concentration .of the samples. If dilution is required, use the
blank solution.
As an example, standard solutions could be prepared as follows:
mL of Standard Solution Cone, ug CN
(1.0 - 5 ue CN) per 250 mL
0 Blank
1.0 5
2.0 10
5.0 25
10.0 50
15.0 75
20.0 100
8.3.2.1 It is not imperative that all standards be distilled in
the same manner as the samples. At least one standard
(mid-range) must be distilled and compared to similar
values on the curve to ensure that the distillation
technique is reliable. If the distilled standard does not
D-68 ILM02.0
-------
Exhibit D Method 335.2
agree within +15% of the undistilled standards, the
operator should find and correct the cause of the apparent
error before proceeding.
8.3.2.2 Prepare a standard curve by plotting absorbpnce of
standard vs. cyanide concentrations (per 250 mL).
8.4 Semi-Automated Spectrophotometric Determination (Option C)
8.4.1 Set up the manifold as shown in Figure 3. Pump the reagents through
the system until a steady baseline is obtained.
8.4.2 Calibration standards: Prepare a blank and at least three
calibration standards over the range of the analysis. One
calibration standard must be at the CRDL. For a working range of 0-
200 ug/L, the following standards may be used:
mL Standard Solution Concentration
(7.2.3) diluted to 1 liter ug CN/L
0 0
4.0 20
10.0 50
20.0 100
30.0 150
40.0 200
Add 10 g of NaOH to each standard. Store at 4°C(±2°C)
8.4.3 Place calibration standards, blanks, and control standards in the
sampler tray, followed by distilled samples, distilled duplicates,
distilled standards, distilled spikes, and distilled blanks.
8.4.4 When a steady reagent baseline is obtained and before starting the
sampler, adjust the baseline using the appropriate knob on the
colorimeter. Aspirate a calibration standard and adjust the STD CAL
dial on the colorimeter until the desired signal is obtained. Record
the STD CAL value. Re-establish the baseline and proceed to analyze
calibration standards, blanks, control standards, distilled samples,
and distilled QC audits.
9. Calculations
9.1 Using the titrimetric procedure, calculate concentration of CN as follows:
(A-B) 1.000 mL/L 250 mL
CN, mg/L - mL orig. sample x mL of aliquot titrated
D-69 ILM02.0
-------
Exhibit D Method 335.2
WHERE: A - volume of AgN03 for titration of sample
(1 mL - 1 mg Ag)
B - volume of AgN03 for titration of blank
(1 mL - 1 mg Ag)
AND: 250 mL - distillate volume (See 8.1.5)
1000 mL - conversion mL to L
mL original sample (See 8.1.1)
mL of aliquot titrated (See 8.2.1)
9.2 If the semi-automated method is used, measure the peak heights of the
calibration standards (visually or using a data system) and calculate a linear
regression equation. Apply the equation to the samples and QC audits to
determine the cyanide concentration in the distillates. To determine the
concentration of cyanide in the original sample, MULTIPLY THE RESULTS BY ONE-
.HALF (since the original volume was 500 mL and the distillate volume was 250
inL). Also, correct for, and report on Form XIV, any dilutions which were made
before or after distillation.
The minimum concentration that can be reported from the calibration curve is
20 ug/L that corresponds to 10 ug/L in a sample that has been distilled.
9.3 If the colorimetric procedure is used, calculate the cyanide, in ug/L, in the
original sample as follows:
A x 1.000 mL/L x 50 mL
CN, ug/L B C
WHERE: A - ug CN read from standard curve (per 250 mL)
B - mL of original sample for distillation (See 8.1.1)
C - mL taken for colorimetric analysis (See 8.3.1)
AND: 50 mL - volume of original sample aliquot (See 8.3.1)
1000 mL/L - conversion mL to L
The minimum value that can be substituted for A is 5 ug per 250 mL. That
yields a concentration of 10 ug/L in the distilled sample.
D-70 ILM02.0
-------
Exhibit D Method 335.2
METHOD FOR TOTAL CYANIDE ANALYSIS IN SOIL/SEDIMENT
CYANIDE, TOTAL (in Sediments)
,P-M* (Titrimetric; Manual Spec
Semi-Automated Spectrophotometrie)
Method 335.2 CLP-M* (Titrimetric; Manual Spectrophotometric;
1. Scope and Application
1.1 This method is applicable to the determination of cyanide in sediments and
other solids.
1.2 The detection limit is dependent upon the weight of sample taken for analysis.
2. Summary of Method
2.1 'The cyanide as hydrocyanic acid (HCN) is released from cyanide complexes by
means of a reflux-distillation operation and absorbed in a scrubber containing
sodium hydroxide solution. The cyanide ion in the absorbing solution is then
determined by volumetric titration or colorimetrically.
2.2 In the colorimetric measurement the cyanide is converted to cyanogen chloride,
CNC1, by reaction with chloramine-T at a pH less than 8 without hydrolyzing to
the cyanate. After the reaction is complete, color is formed on the addition
of pyridine-pyrazolone or pyridine-barbituric acid reagent. The absorbance is
read at 620 nm when using pyridine-pyrazolone for 578 nm for pyridine-
barbituric acid. To obtain colors of comparable intensity, it is essential to
have the same salt content in both the sample and the standards.
2.3 The titrimetric measurement uses a standard solution of silver nitrate to
titrate cyanide in the presence of a silver sensitive indicator.
3. Definitions
3.1 Cyanide is defined as cyanide ion and complex cyanides converted to
hydrocyanic acid (HCN) by reaction in a reflux system of a mineral acid in the
presence of magnesium ion.
4. Sample Handling and Preservation
4.1 Samples must be stored at 4°C(±2°C) and must be analyzed within the holding
time specified in Exhibit D, Section II.
4.2 Samples are not dried prior to analysis. A separate percent solids
determination must be made in accordance with the procedure in Part F.
5. Interferences
5.1 Interferences are eliminated or reduced by using the distillation procedure
described in Procedure 8.1.
5.2 Sulfides adversely affect the colorimetric and titration procedures.
*&
CLP-M Modified for the Contract Laboratory Program.
D-71 ILM02.0
-------
Exhibit D Method 335.2
5.3 The presence of surfactants may cause the sample to foam during refluxing. If
this occurs, the addition of an agent such as DOW Corning 544 antifoam agent
will prevent the foam from collecting in the condenser. Fatty acids will
distill and form soaps under the alkaline titra.tion conditions, making the end
point almost impossible to detect. When this occurs, one of the
spectrophotometric methods should be used. .
6. Apparatus
6.1 Reflux distillation apparatus such as shown in Figure 1 or Figure 2. The
boiling flask should be of 1 liter size with inlet tube and provision for
condenser. The gas absorber may be a Fisher-Milligan scrubber.
6.2 Microburet, 5.0 mL (for titration)
6.3 Spectrophotometer suitable for measurements at 578 nm or 620 nm with a 1.0 cm
'cell or larger.
6.4 Technicon AA II System or equivalent instrumentation (for automated
spectrophotometric method) including:
6.4.1 Sampler
6.4.2 Pump III
6.4.3 Cyanide Manifold (Figure 3)
6.4.4 SCIC Colorimeter with 15 mm flowcells and 570 nm filters
6.4.5 Recorder
6.4.6 Data System (optional)
6.4.7 Glass or plastic tubes for the sampler
7. Reagents
7.1 Distillation and Preparation Reagents
7.1.1 Sodium hydroxide solution, 1.25N: Dissolve 50 g of NaOH in distilled
water, and dilute to 1 liter with distilled water.
7.1.2 Cadmium carbonate: powdered
7.1.3 Ascorbic acid: crystals
7.1.4 Sulfuric acid: concentrated
7.1.5 Magnesium chloride solution: Weigh 510 g of MgC12.6H20 into a 1000
mL flask, dissolve and dilute to 1 liter with distilled water.
7.2 Stock Standards and Titration Reagents
7.2.1 Stock cyanide solution: Dissolve 2.51 g of KCN and 2 g KOH in 1
liter of distilled water. Standardize with 0.0192 N AgN03-
D-72 ILM02.0
-------
Exhibit D Method 335.2
7.2.2 Standard cyanide solution, intermediate: Dilute 50.0 mL of stock (1
mL - 1 mg CN) to 1000 mL with distilled water (1 mL - 50.0 ug).
7.2.3 Standard cyanide solution: Prepare fresh daily by diluting 100.0 mL
of intermediate cyanide solution to 1000 mL with distilled water and
store in a glass stoppered bottle. 1 mL - 5.0 ug CN (5.0 mg/L).
7.2.4 Standard silver nitrate solution, 0.0192 N: Prepare by crushing
approximately 5 g AgN03 crystals and drying to constant weight at
406C. Weigh out 3.2647 g of dried AgN03, dissolve in distilled
water, and dilute to 1000 mL (1 mL - 1 mg CN).
7.2.5 Rhodanine indicator: Dissolve 20 mg of p-dimethy1-amino-
benzalrhodanine in 100 mL acetone.
7.3 Manual Spectrophotometric Reagents
7.3.1 Sodium dihydrogenphosphate, 1 M: Dissolve 138 g of Nal^PCV^O in 1
liter of distilled water. Refrigerate this solution.
7.3.2 Chloramine-T solution: Dissolve 1.0 g of white, water soluble
Chloramine-T in 100 mL of distilled water and refrigerate until ready
to use. Prepare fresh weekly.
7.3.3 Color reagent - One of the following may be used:
1.3.3.1 Pyridine-barbituric acid reagent: Place 15 g of
barbituric acid in a 250 mL volumetric flask and add just
enough distilled water to wash the sides of the flask and
wet the barbituric acid. Add 75 mL of pyridine and mix.
Add 15 mL of HC1 (sp gr 1.19), mix, and cool to room
temperature. Dilute to 250 mL with distilled water and
mix. This reagent is stable; for approximately six months
if stored in a cool, dark place.
7.3.3.2 Pyridine-pyrazolone solution:
7.3.3.2.1 3-Methyl-l-phenyl-2-pyrazolin-5-one reagent,
saturated solution: Add 0.25 g of 3-methyl-l-
phenyl-2-pyrazolin-5-one to 50 mL of distilled
water, heat to 60°C with stirring. Cool to
room temperature.
7.3.3.2.2 3,3'Dimethyl-l,l'-diphenyl-[4,4'-bi-2-
pyrazolin]-5,5'dione (bispyrazolone):
Dissolve 0.01 g of bispyrazolone in 10 mL of
pyridine.
7.3.3.2.3 Pour solution (7.3.3.2.1) through non-acid-
washed filter paper. Collect the filtrate.
Through the same filter paper pour solution
(7.3.3.2.2) collecting the filtrate in the
same container as filtrate from (7.3.3.2.1).
Mix until the filtrates are homogeneous. The
mixed reagent develops a pink color but this
D-73 . ILM02.0
-------
Exhibit D Method 335.2
does not affect the color production with
cyanide if used within 24 hours of
preparation.
7.4 Semi-Automated Spectrophotometrie Reagents
7.4.1 Chloramine-T solution: Dissolve 0.40 g of chloramine-T in distilled
water and dilute to 100 mL. Prepare fresh daily.
7.4.2 Phosphate Buffer: Dissolve 138 g of Nat^PCV^O in distilled water
and dilute to 1 liter. Add 0.5 mL of Brij-35 (available from
Technicon). Store at 4°C.
7.4.3 Pyridine-barbituric acid solution: Transfer 15 g of barbituric acid
into a 1 liter volumetric flask. Add about 100 mL of distilled water
and swirl the flask. Add 74 mL of pyridine and mix. Add 15 mL of
cone. HC1 mix until the barbituric acid is dissolved. Dilute to 1
liter with distilled water. Store at 4°C.
7.4.4 Sampler Wash: Dissolve 10 g of NaOH in distilled water and dilute to
1 liter.
8. Procedure
8.1 Distillation
8.1.1 Accurately weigh a representative 1-5 g portion of wet sample and
transfer it to a boiling flask. Add 500 mL of distilled water.
Shake or stir the sample so that it is dispersed.
8.1.2 Add 50 mL of sodium hydroxide (7.1.1) to the absorbing tube and
dilute if necessary with distilled water to obtain an adequate depth
of liquid in the absorber. Connect the boiling flask, condenser,
absorber, and trap in the train.
8.1.3 Start a slow stream of air entering the boiling flask by adjusting
the vacuum source. Adjust the vacuum so that approximately one
bubble of air per second enters the boiling flask through the air
inlet tube.
NOTE: The bubble rate will not remain constant after the reagents
have been added and while heat is being applied to the flask. It
will be necessary to readjust the air rate occasionally to prevent
the solution in the boiling flask from backing up into the air
inlet tube.
8.1.4 Slowly add 25 mL of cone, sulfuric acid (7.1.4) through the air inlet
tube. Rinse the tube with distilled water and allow the airflow to
mix the flask contents for 3 minutes. Pour 20 mL of magnesium
chloride solution (7.1.5) into the air inlet and wash down with a
stream of water.
D-74 ILM02.0
-------
Exhibit D Method 335.2
8.1.5 Heat the solution to boiling, taking care to prevent the solution
from backing up and overflowing into the air inlet tube. Reflux for
one hour. Turn off heat and continue ~he airflow for at least 15
minutes. After cooling the boiling flask, disconnect absorber and
close off the vacuum source.
8.1.6 Drain the solution from the absorber into a 250 mL volumetric flask
and bring up to volume with distilled water washings from the
absorber tube.
8.2 Titrimetric Determination (Option A)
8.2.1 If the sample contains more than 1 mg of CN, transfer the distillate,
or a suitable aliquot diluted to 250 mL, to a 500 mL Erlenmeyer
flask. Add 10-12 drops of the benzalrhodanine indicator.
'8.2.2 Titrate with standard silver nitrate to the first change in color
from yellow to brownish-pink. Titrate a distilled water blank using
the same amount of sodium hydroxide and indicator as in the sample.
8.2.3 The analyst should familiarize himself with the end point of the
titration and the amount of indicator to be used before actually
titrating the samples. A 5 or 10 mL microburet may be conveniently
used to obtain a more precise titration.
8.3 Manual Spectrophotometric Determination (Option B)
8.3.1 Withdraw 50 mL or less of the solution from the flask and transfer to
a 100 mL volumetric flask. If less than 50 mL is taken, dilute to 50
mL with 0.25 N sodium hydroxide solution (7.2.6). Add 15.0 mL of
sodium phosphate solution (7.3.2) and mix.
8.3.1.1 Pyridine-barbituric acid mef.hod: Add 2 mL of Chloramine-T
(7.3.2) and mix. After 1 to 2 minutes, add 5 mL of
pyridine-barbituric acid solution (7.3.3.1) and mix.
Dilute to mark with distilled water and mix again. Allow
8 minutes for color development then read absorbance at
578 nm in a 1 cm cell within 15 minutes.
8.3.1.2 Pyridine-pyrazolone method: Add 0.5 mL of chloramine-T
(7.3.2) and mix. After 1 to 2 minutes add 5 mL of
pyridine-pyrazolone solution (7.3.3.2) and mix. Dilute to
mark with distilled water and mix again. After 40 minutes
read absorbance at 620 nm in a.1 cm cell.
NOTE: More than 0.5 mL of ohloramine-T will prevent the
color from developing with pyridine-pyrazolone.
8.3.2 Prepare a minimum of three standards and a blank by pipetting
suitable volumes of standard solution into 250 mL volumetric flasks.
NOTE: One calibration standard, must be made at the CRDL. To each
standard add 50 mL of 1.25 N sodium hydroxide and dilute to 250 mL with
distilled water. Standards must bracket the concentrations of the sample.
If dilution is required, use the blank solution.
D-75 ILM02.0
-------
Exhibit D Method 335.2
As an example, standard solutions could be prepared as follows:
mL of Standard Solution Cone, ug CN
d.O - 5 ug CN) per 250 mL
0 Blank
1.0 5
2.0 10
5.0 25
10.0 50
15.0 75
20.0 100
8.3.2.1 It is not imperative that all standards be distilled in
the same manner as the samples. At least one standard
(mid-range) must be distilled and compared to similar
values on the curve to insure that the distillation
technique is reliable. If the distilled standard does not
agree within +15% of the undistilled standards the
operator should find and correct the cause of the apparent
error before proceeding.
8.3.2.2 Prepare a standard curve by plotting absorbance of
standard vs. cyanide concentrations (per 250 mL)
8.4 Semi-Automated Spectrophotometrie Determination (Option C)
8.4.1 Set up the manifold as shown in Figure 3. Pump the reagents through
the system until a steady baseline is obtained.
8.4.2 Calibration standards: Prepare a blank and at least three
calibration standards over the range of the analysis. One
calibration standard must be at the CRDL. For a working range of 0-
200 ug/L, the following standards may be used:
mL Standard Solution Concentration
(7.2.3) diluted to 1 liter ug CN/L
0 0
4.0 20
10.0 50
20.0 100
30.0 150
40.0 200
Add 10 g of NaOH to each standard. Store at 4°C(±2°C).
8.4.3 Place calibration standards, blanks, and control standards in the
sampler tray, followed by distilled samples, distilled duplicates,
distilled standards, distilled spikes, and distilled blanks.
8.4.4 When a steady reagent baseline is obtained and before starting the
sampler, adjust the baseline using the appropriate knob on the
colorimeter. Aspirate a calibration standard and adjust the STD CAL
dial on the colorimeter until the desired signal is obtained. Record
D-76 ILM02.0
-------
Exhibit D Method 335.2
the STD CAL value. Reestablish the baseline and proceed to analyze
calibration standards, blanks, control standards, distilled samples,
and distilled QC audits.
9. Calculations
9.1 A separate determination of percent solids must, be performed (see Part F).
9.2 The concentration of cyanide in the sample is determined as follows.
9.2.1 (Titration)
(A - B) x 250 mL x XQOO gAg
mL aliquot titrated
CN, mg/kg -
c x %solids
100
WHERE: A - mL of AgN(>3 for titration of sample
(1 mL - 1 mg Ag)
B - mL of AgN03 for titration of blank
(1 mL - 1 mg Ag)
C - wet weight of original sample in g
(See 8.1.1)
AND: 250 mL - volume of distillate (See 8.1.6)
1000 g/kg = conversion factor g to kg
mL aliquot titrated (See 8.2.1)
% solids (see Part F)
9.2.2 (Manual Spectrophotometric)
50 mL
CN, mgAg - A X B
C x % solids
100
WHERE: A - ug CN read from standard curve (per 250 mL)
B - mL of distillate taken for colorimetric
determination (8.3.1)
C - wet weight of origins.! sample in g
(See 8.1.1)
The minimum value that can be substituted for A is 5 ug/250 mL.
That yields a concentration of 10 ug/L in the distilled sample.
AND: 50 mL - volume of standard taken for colorimetric
determination (See 8.3.1)
% solids (see Part F)
D-77 ILM02.0
-------
^Exhibit D Method 335.2
9.2.3 (Semi-Automated Spectrophotometric)
If the semi-automated method is used, measure the peak heights of
the calibration standards (visually or using a data system) and
•• •'•••'••>.•''• calculate a linear regression equation. Apply the equation to the
samples and QC audits to determine the cyanide concentration in
the distillates.
A x .25
CN, mg/kg - c x % solids
100
WHERE: A - ug/L determined from standard curve
C - wet weight of original sample in g
(See 8.1.1)
AND: .25 - conversion factor for distillate final
volume (See 8.1.6)
% solids (see Part F)
The minimum value that can be substituted for A is 5 ug/250 mL.
D-78 ILM02.0
-------
Exhibit D Method 335.2
COOLING WATER
INLET TUBE"
SCREW CLAMP
HEATER -
TO LOW VACUUM
SOURCE
- ABSORBER
** DISTILLING FLASK
O
Figure 1. Cyanide distillation apparatus
D-79
ILM02.0
-------
Exhibit D Method 335.2
ALIIHN CONDENSER
AIR INLET TUBE
— CONNECTING TUBING
ONE LITER
BOILING FLASK
SUCTION
Figure 2. Cyanide distillation apparatus
D-80
ILM02.0
-------
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-------
Exhibit D Method 335.2
. METHOD FOR TOTAL CYANIDE ANALYSIS BY MIDI DISTILLATION
CYANIDE, TOTAL (water and soils)
Method 335.2 CLP-M (Semi-automated Spectrophotometric)
1. Scope and Application
1.1 Cyanide determined by this method is defined as cyanide ion and complex
cyanides converted to hydrocyanic acid by reaction in a reflux system with
mineral acid in the presence of magnesium ion.
1.2 This method covers the determination of cyanide by midi distillation with a
semi-automated colorimetric analysis of the distillate.
1.3 The detection limit for the semi-automated colcrimetric method is
.approximately 10 ug/L.
2. Summary of Method
2.1 The cyanide as hydrocyanic acid (HCN) is released from cyanide complexes by
means of a midi reflux-distillation operation and absorbed in a scrubber
containing sodium hydroxide solution. The cyanide ion in the absorbing
solution is then determined colorimetrically.
2.2 In the colorimetric measurement, the cyanide is converted to cyanogen
chloride, CNC1, by reaction with chloramine-T at pH less than 8 without
hydrolysis to the cyanate. After the reaction is complete, color is formed on
the addition of pyridinebarbituric acid reagent. The absorbance is read at
580 nm. To obtain colors of comparable intensity, it is essential to have the
same salt content in both the samples and the standards.
3. Sample Handling and Preservation
3.1 All bottles must be thoughly cleansed and rinsed to remove soluble materials
from containers.
3.2 Oxidizing agents such as chlorine decompose most cyanides. Test a drop of the
sample with potassium iodide-starch test paper (Kl-Starch paper); a blue color
indicates the need for treatment. Add ascorbic acid, a few crystals at a
time, until a drop of sample produces no color on the indicator paper. Then
add additional 0.6 g of ascorbic acid for each liter of sample volume.
3.3 Samples are preserved with 2 mL of 10 N sodium hydroxide per liter of sample
(pH > 12) at the time of collection.
3.4 Samples must be stored at 4°C (±2°C) and must be analyzed within the holding
time specified in Exhibit D, Section II.
4. Interferences
4.1 Interferences are eliminated or reduced by using the distillation procedure.
D-82 ILM02.0
-------
Exhibit D Method 335.2
4.2 Sulfides adversely affect the colorimetric procedures. If a drop of
distillate on lead acetate test paper indicates the presence of sulfides,
treat the sample with powdered cadmium carbonate. Yellow cadmium sulfide
precipitates if the sample contains sulfide. Repeat this operation until a
drop of the treated sample solution does not darken the lead acetate test
paper. Filter the solution through a dry filter paper into a dry beaker, and
from the filtrate, measure th'e sample to be used for analysis. Avoid a large
excess of cadmium carbonate and long contact time in order to minimize loss by
complexation or occlusion of cyanide on the precipitated material.
4.3 The presence of surfactants may cause the sample to foam during refluxing. If
this occurs, the addition of an agent such as Dow Corning 544 antifearning
agent will prevent the foam from collecting in the condenser.
5. Apparatus
5.1 Midi reflux distillation apparatus as shown in figure 1.
5.2 Heating block - Capable of maintaining 125°C ±5°C.
5.3 Auto analyzer system with accessories:
5.3.1 Sampler
5.3.2 Pump
5.3.3 Cyanide cartridge
5.3.4 Colorimeter with 50 mm flowcells and 530 nm filter
5.3.5 Chart recorder or data system.
5.4 Assorted volumetric glassware, pipets, and micropipets.
6. Reagents
6.1 Distillation and Preparation Reagents
6.1.1 Sodium hydroxide absorbing solution, and sample wash solution, 0.25
N. Dissolve 10.0 g NaOH in ASTM Type II water and dilute to one
liter.
6.1.2 Magnesium chloride solution, 51% (w/v). Dissolve 510 g of MgCl
in ASTM Type II water and dilute to one liter.
6.1.3 Sulfuric acid, 50% (v/v). Carefully add a portion of concentrated
H2SC-4 to an equal portion of ASTM Type II water.
6.1.4 Sodium hydroxide solution, 1.25 N. Dissolve 50 g of NaOH in ASTM
Type II water and dilute to one liter.
D-83 ILM02.0
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Exhibit D Method 335.2
6.2 Standards
6.2.1 Stock cyanide solution, 1000 mg/L CN. Dissolve 2.51 g of KCN and 2.0
g KOH in ASTM Type II water and dilute one liter. Standardize with
0.0192 N AgN03.
6.2.2 Intermediate cyanide standard solution, 10 mg/L CN. Dilute 1.0 mL of
stock cyanide solution (6.2.1) plus 20 mL of 1.25 N NaOH solution
(6.1.4) to 100 mL with ASTM Type II water. Prepare this solution at
time of analysis.
6.2.3 Rhodamine indicator. Dissolve 20 mg of p-dimethylamino-benzal-
rhodamine in 100 mL acetone.
6.2.4 Silver nitrate solution, 0.0192 N. Prepare by crushing approximately
5 g AgN03 crystals and drying to a constant weight at 104 C. Weigh
out 3.2647 g of dried AgNC>3 and dissolve in ASTM Type II water.
Dilute to one liter ( 1 mL corresponds to 1 mg CN).
6.2.5 Potassium chromate indicator solution. Dissolve 50 g K2CRC>4 in
sufficient ASTM Type II water. Add silver nitrate solution until a
definite red precipitate is formed. Let stand for at least 12 hours,
filter, and dilute to one liter with ASTM Type II water.
6.2.6 Primary standard sodium chloride, 0.0141 N. Dissolve 824.1 mg NaCl
(NBS-dried 20 minutes at 104°C) in ASTM Type II water and dilute to
one liter.
6.2.7 Sodium hydroxide solution, 0.1 N. Dissolve 4 g of NaOH in ASTM Type
II water and dilute to one liter.
6.3 Semi-Automated Spectrophotometrie Reagents
6.3.1 Phosphate buffer solution, 1 M. Dissolve 138 g of NaH2P04-H20 in
ASTM Type II water and dilute to one liter. Add 0.5 mL of Brij-35
(available from Technicon). Store at 4°C.
6.3.2 Chloramine-T solution, 0.4% (w/v). Dissolve 0.4 g of chloramine-T in
ASTM Type II water and dilute to 100 mL. Prepare fresh at time of
analysis.
6.3.3 Color Reagent Solution, Pyridine barbiruric acid color reagent
solution. Prepare this solution in the hood. Transfer 15 g of
barbituric acid into a one liter Erlenmeyer flask. Add about 100 mL
of ASTM Type II water and swirl the flask to mix. Add 75 mL of
pyridine and 15 mL concentrated HCL and mix until all the barbituric
acid is dissolved. Dilute to one liter with ASTM Type II water and
store at 4°C.
D-84 ILM02.0
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Exhibit D Method 335.2
7 . Procedure
7.1 Distillation
7.1.1 The procedure described here utilizes A midi distillation apparatus
and requires a sample aliquot of 50 mL:s or less for aqueous samples
and one gram for solid materials. NOTE: All samples must initally
be run undiluted (i.e., aqueous samples must first be run with a 50
mL aliquot and solid samples using a one gram sample) . When the
cyanide concentration exceeds the highest calibration standard,
appropriate dilution (but not below the CRDL) and reanalysis of the
sample is required. The dilution factor must be reported on Form
XIV.
7.1.2 For aqueous samples: Pipet 50 mL of sample, or an aliquot diluted to
50 mL, into the distillation flask along with 2 or 3 boiling chips.
7.1.3 For solid samples: Weigh 1.0 g of sample (to the nearest 0.01 g)
into the distillation flask and dilute to 50 mL with ASTM Type II
water. Add 2 or 3 boiling chips.
7.1.4 Add 50 mL of 0.25 N NaOH (6.1.1) to the gas absorbing impinger.
7.1.5 Connect the boiling flask, condenser, and absorber in the train as
shown in figure 2. The excess cyanide trap contains 0.5 N NaOH.
7.1.6 Turn on the vacuum and adjust the gang (Whitney) values to give a
flow of three bubbles per second from the impingers in each reaction
vessel.
7.1.7 After five minutes of vacuum flow, inject 5 mL of 50% (v/v)
(6.1.3) through the top air inlet tube of the distillation head into
the reaction vessel. Allow to mix for 5 minutes. (NOTE: The acid
volume must be sufficient to bring the sample/solution pH to below
2.0.)
7.1.8 Add 2 mL of magnesium chloride solution (6.1.2) through the top air
inlet tube of the distillation head into the reaction flask.
Excessive foaming from samples containing surfactants may be quelled
by the addition of another 2 mL of magnesium chloride solution.
7.1.9 Turn on the heating block and set for 123-125°C. Heat the solution
to boiling, taking care to prevent solution backup by periodic
adjustment of the vacuum flow.
7.1.10 After one and a half hours of refluxing, turn off the heat and
continue the vacuum for an additional 15 minutes . The flasks should
be cool at this time .
7.1.11 After cooling, close off the vacuum at the gang valve and remove the
absorber. Seal the receiving solutions and store them at 4°C until
analyzed. The solutions must be analysed for cyanide within the 12
day holding time specified in Section II.
D-85 ILM02.0
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Exhibit D Method 335.2
7.2 Semi-Automated Spectrophotometric Determination
7.2.1 Operating conditions: Because of the difference between various
makes and models of satisfactory instruments, no detailed operating
instructions can be provided. The analyst should follow the
instructions provided by the manufacturer of the particular
instrument. It is the responsibility of the analyst to verify that
the instrument configuration and operating conditions used satisfy
the analytical requirements and to maintain quality control data
confirming instrument performance and analytical results.
The following general procedure applies to most semi-automated
colorimeters. Set up the manifold and complete system per
manufacturer's instructions. Allow the colorimeter and recorder warm
up for at least 30 minutes prior to use. Establish a steady reagent
baseline feeding ASTM Type II water through the sample line and
appropriate reagents (6.3) through reagent lines. Adjust the
baseline using the appropriate control on the colorimeter.
7.2.2 Prepare a minimum of 3 standards and a blank by pipetting suitable
volumes of standard solution into 50 mL volumetric flasks. NOTE:
One calibration standard must be at the Contract Required Detection
Limit (CRDL).
As an example, standard solutions could be prepared as follows:
Total ug CN
standard solution mL 10 me/L CN mL 0.05 N NaOH
0.00 0.000 20
0.10 0.010 20
0.25 0.025 20
0.50 0.050 20
1.00 0.100 20
2.00 0.200 20
5.00 0.500 20
7.2.2.1 Dilute standards to 50 mL using ASTM Type II water. It is
not imperative that all standards be distilled in the same
manner as the samples. At least one standard (mid-range)
must be distilled and compared to similar values on the
curve for each SDG to ensure the distillation technique is
reliable. If the distilled standard does not agree within
+15% of the undistilled standards, the operator must find
and correct the cause of the error before proceeding.
7.2.3 Aspirate the highest calibration standard and adjust the colorimeter
until the desired (maximum) signal-range is obtained.
7.2.4 Place calibration standards, blanks, control standards in the sampler
tray, followed by distilled samples, distilled duplicates, distilled
standards, distilled spikes, and distilled blanks.
7.2.5 Switch sample line from the ASTM Type II water to sampler, set the
appropriate sampling rate and begin the analysis.
D-86 ILM02.0
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Exhibit D Method 335.2
8. Calculations
8.1 Calculations for Semi-automated Colorimetric Determination
8.1.1 Prepare a standard curve by plotting absorbance (peak heights,
determined visually or using a data system) of standards (y) versus
cyanide concentration values (total ug CN/L) (x). Perform a linear
regression analysis.
8.1.2 Multiply all distilled values by the standardization value to correct
for the stock cyanide solution not being exactly 1000 mg/L (See
6.2.1).
8.1.3 Using the regression analysis equation, calculate sample receiving
solution concentrations from the calibration curve.
•8.1.4 Calculate the cyanide of aqueous samples in ug/L of original sample,
as follows:
A x D x F
CN, ug/L - B
where: A - ug/L CN of sample from regression analysis
B - Liter of original sample for distillation (0.050 L)
(See 7.1.2)
D - any dilution factor necessary to bracket sample
value within standard values
F - sample receiving solution volume (0.050 L)
The minimum value that can be substituted for A is 10 ug/L.
8.1.5 Calculate the cyanide of solid samples in mg/kg of original sample,
as follows:
8.1.5.1 A separate determination of percent solids must be
performed (See Part F).
8.1.5.2 The concentration of cyanides in the sample is determined
as follows:
A x D x F
CN, mgAg - B x E
where: A - ug/L CN of sample from regression analysis
curve
B - wet weight of original sample in g (See
7.1.3)
D-87 ILM02.0
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Exhibit D Method 335.2
D - any dilution factor necessary to bracket
sample value within standard values
E - % solids (See Part F)/100.
F - sample receiving solution volume (0.050 L)
The minimum value that can be substituted for A is 10 ug/L
D-88 ILM02.0
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Exhibit D Part F
PART F - PERCENT SOLIDS DETERMINATION PROCEDURE
1. Immediately following the weighing of the sample to be processed for analysis
(see Section III, Part B- Soil/Sediment Sample Preparation), add 5-10 g of
sample to a tared weighing dish. Weigh and record the weight to the nearest
0.01 g.
2. Place weighing dish plus sample, with the cover tipped to allow for moisture
escape, in a drying oven maintained at 103-105
should be conducted in a well-ventilated area.
escape, in a drying oven maintained at 103-105°C. Sample handling and drying
3. Dry the sample overnight (12-24 hours) but no longer than 24 hours. If dried
less than 12 hours, it must be documented that constant weight was attained.*
Remove the sample from the oven and cool in a dessicator with the weighing dish
cover in place before weighing. Weigh and record weight to nearest 0.01 g. Do
not analyze the dried sample.
4. Duplicate percent solids determinations are required at the same frequency as
are other analytical determinations. Duplicate results are to be recorded on
FORM VI-IN.
5. For the duplicate percent solids determination, designate one sample aliquot as
the "original" sample and the other aliquot as the "duplicate" sample.
Calculate dry weight using the results of the "original" sample aliquot.
6. Calculate percent solids by the formula below. The value thus obtained will be
reported on the appropriate FORM I-IN and, where applicable, FORM VI-IN . This
value will be used for calculating analytical concentration on a dry weight
basis.
% Solids - Sample Dry Weight x 10o
Sample Wet Weight.
*For the purpose of paragraph 3, drying time is defined as the elapsed time in the
oven; thus raw data must record time in and out of t:he oven to document the 12
hour drying time minimum. In the event it is necessary to demonstrate the
attainment of constant weight, data must be recorded for a minimum of two
repetitive weigh/dry/dessicate/weigh cycles with a ninimum of 1 hour drying time
in each cycle. Constant weight would be defined as a loss in weight of no greater
than 0.01 g between the start weight and final weight of the last cycle.
D-89 ILM02.0
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PART G - ALTERNATE METHODS (CATASTROPHIC ICP FAILURE)'1'
Analyte Page No.
Aluminum - Method 202.2 CLP-M*. Furnace AA D-92
Barium - Method 208.2 CLP-M, Furnace AA D-93
Cobalt - Method 219.2 CLP-M, Furnace AA D-94
Copper - Method 220.2 CLP-M, Furnace AA D-95
Iron - Method 236.2 CLP-M, Furnace AA D-96
Manganese - Method 243.2 CLP-M, Furnace AA D-97
Nickel - Method 249.2 CLP-M, Furnace AA D-98
Vanadium - Method 286.2 CLP-M, Furnace AA D-99
Zinc - Method 289.2 CLP-M, Furnace AA D-100
Aluminum - Method 202.1 CLP-M, Flame AA D-102
Antimony =• Method 204.1 CLP-M, Flame AA D-104
Barium - Method 208.1 CLP-M, Flame AA D-105
Beryllium - Method 210.1 CLP-M, Flame AA D-106
Cadmium - Method 213.1 CLP-M, Flame AA D-107
Chromium - Method 218.1 CLP-M, Flame AA D-108
Cobalt - Method 219.1 CLP-M, Flame AA D-109
Copper - Method 220.1 CLP-M, Flame AA D-110
Iron - Method 236.1 CLP-M, Flame AA D-lll
Lead - Method 239.1 CLP-M, Flame AA D-112
Manganese - Method 243.1 CLP-M, Flame AA D-113
Nickel - Method 249.1 CLP-M, Flame AA D-114
Silver - Method 272.1 CLP-M, Flame AA D-115
Thallium - Method 279.1 CLP-M, Flame AA D-117 .
Vanadium - Method 286.1 CLP-M, Flame AA D-118
Zinc - Method 289.1 CLP-M, Flame AA D-119
+Furnace AA Methods are from "Methods for Chemical Analysis of Water and
Wastes", (EPA-600/4-79-02), March 1979, as modified for use in the
Contract Laboratory Program (CLP). Flame AA (Flame Technique) Methods are
from "Interim Methods for the Sampling and Analysis of Priority Pollutants
in Sediments and Fish Tissue," USEPA Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio, August 1977, Revised October 1980, as
modified for use in the CLP.
*CLP-M Modified for the Contract Laboratory Program.
D-90 ILM02.0
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Exhibit D Part G
CONDITIONS FOR USE OF ALTERNATE METHODS
The methods contained in Part G may be used only if all of the following conditions
are met:
1) Catastrophic failure of ICP occurs,
2) Administrative Project Officer authorization for use of alternate methods
is granted, and
3) The IDLs for the instrumentation have been determined, as per Exhibit E,
within the current calendar quarter.
D-91 ILM02.0
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Exhibit D Method 202.2
ALUMINUM*
Method 202.2 CLP-M** (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 20-200 ug/L
Approximate Detection Limit: 3 ug/L
Preparation of Standard Solution
1. Stock solution: Prepare as described under AA Flame Technique (Method 202.1
CLP-M).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. These solutions are also to be used for "standard
additions".
3. The calibration standards must be prepared using the same type of acid and at
the same concentration as will result in the sample to be analyzed after sample
preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 1300°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 309.3 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, continuous flow purge gas and
non-pyrolytic graphite and are to be used as guidelines only.
2. Background correction is required.
3. It has been reported that chloride ion and that nitrogen used as a purge gas
suppress the aluminum signal. Therefore the use of halide acids and nitrogen
as a purge gas should be avoided.
4. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (Exhibit E).
5. If method of standard addition is required, follow the procedure given in
Exhibit E.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-92 ILM02.0
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Exhibit D Method 208.2
BARIUM*
Method 208.2 CLP-M** (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 10-200 ug/L
Approximate Detection Limit: 2 ug/L
Preparation of Standard Solution
1. Stock solution: Prepare as described under AA Flame Technique (Method 208.1
CLP-M).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. These solutions are also to be used for "standard
additions".
3. The calibration standards must be prepared using the same type of acid and at
the same concentration as will result in the sample to be analyzed after sample
preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°.
2. Ashing Time and Temp: 30 sec @ 1200°C.
3. Atomizing Time and Temp: 10 sec @ 2800°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 553.6 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, continuous flow purge gas and
pyrolytic graphite and are to be used as guidelines only.
2. The use of halide acid should be avoided.
3. Because of possible chemical interaction, nitrogen should not be used as a
purge gas.
4. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (see Exhibit E).
5. If method of standard addition is required, follow the procedure given in
Exhibit E.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-93 ILM02.0
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Exhibit D Method 219.2
COBALT*
Method 219.2 CLP-M** (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L
Approximate Detection Limit: 1 ug/L
Preparation of Standard Solution
1. Stock solution: Prepare as described under AA Flame Technique (Method 219.1
CLP-M).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. These solutions are also to be used for "standard
additions".
3. The calibration standards must be prepared using the same type of acid and at
the same concentration as will result in the sample to be analyzed after sample
preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 900°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 240.7 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, continuous flow purge gas and
non-pyrolytic graphite and are to be used as guidelines only. Smaller size
furnace devices or those employing faster rates of atomization c furnace
using lower atomization temperatures for shorter time periods than the above
recommended settings.
2. The use of background correction is required.
3. Nitrogen may also be used as the purge gas but with reported low sensitivity.
4. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (see Exhibit E).
5. If method of standard addition is required, follow the procedure given in
Exhibit E.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-94 ILM02.0
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Exhibit D Method 220.2
COPPER*
Method 220.2 CLP-M** (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L
Approximate Detection Limit: 1 ug/L
Preparation of Standard Solution
1. Stock solution: Prepare as described under AA Flame Technique (Method 220.1
CLP-M).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. These solutions are also to be used for "standard
additions".
3. The calibration standards must be prepared using the same type of acid and at
the same concentration as will result in the sample to be analyzed after sample
preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 900°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 324.7 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use cf a 20 uL injection, continuous flow purge gas and
non-pyrolytic graphite and are to be used as guidelines only. Smaller size
furnace devices or those employing faster rates of atomization can be operated
using lower atomization temperatures for shorter time periods than the above
recommended settings.
2. Background correction is required.
3. Nitrogen may also be used as the purge gas.
4. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (see Exhibit E).
5. If method of standard addition is required, follow the procedure given in
Exhibit E.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-95 ILM02.0
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Exhibit D Method 236.2
IRON*
Method 236.2 CLP-M** (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L
Approximate Detection Limit: 1 ug/L
Preparation of Standard Solution
1. Stock solution: Prepare as described under AA Flame Technique (Method 236.1
CLP-M).
2. Prepare dilutions of the stock solution to be used as calibration standards at •
the time of analysis. These solutions are also to be used for "standard
additions".
3. The calibration standards must be prepared using the same type of acid and at
the same concentration as will result in the sample to be analyzed after sample
preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 1000°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 248.3 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, continuous flow purge gas and
non-pyrolytlc graphite and are to be used as guidelines only. Smaller size
furnace devices or those employing faster rates of atomization can be operated
using lower atomization temperatures for shorter time periods than the above
recommended settings.
2. The use of background correction is required.
3. Nitrogen may also be used as the purge gas.
4. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (see Exhibit E).
5. If method of standard addition is required, follow the procedure given in
Exhibit E.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-96 ILM02.0
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Exhibit D Method 243.2
MANGANESE*
Method 243.2 CLP-M** (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 1-30 ug/L
Approximate Detection Limit: 0.2 ug/L
Preparation of Standard Solution
1. Stock solution: Prepare as described under AA Flame Technique (Method 243.1
CLP-M).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. These solutions are also to be used for "standard
additions".
3. The calibration standards must be prepared using the same type of acid and at
the same concentration as will result in the sample to be analyzed after sample
preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 1000°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 279.5 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, continuous flow purge gas and
non-pyrolytic graphite and are to be used as guidelines only. Smaller size
furnace devices or those employing faster rates of atomization can be operated
using lower atomization temperatures for shorter time periods than the above
recommended settings.
2. The use of background correction is required.
3. Nitrogen may also be used as the purge gas.
4. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (see Exhibit E).
5. If method of standard addition is required, follow the procedure given in
Exhibit E.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-97 ILM02.0
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Exhibit D Method 249.2
NICKEL*
Method 249.2 CLP-M** (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L
Approximate Detection Limit: 1 ug/L
Preparation of Standard Solution
1. Stock solution: Prepare as described under AA Flame Technique (Method 249.1
CLP-M).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. These solutions are also to be used for "standard
additions".
3. The calibration standards must be prepared using the same type of acid and at
the same concentration as will result in the sample to be analyzed after sample
preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 900°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 232.0 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, continuous flow purge gas and
non-pyrolytic graphite and are to be used as guidelines only. Smaller size
furnace devices or those employing faster rates of atomization can be operated
using lower atomization temperatures for shorter time periods than the above
recommended settings.
2. The use of background correction is required.
3. Nitrogen may also be used as the purge gas.
4. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (see Exhibit E).
5. If method of standard addition is required, follow the procedure given in
Exhibit E.
*This method may only be used under specified conditions,
**CLP-M Modified for the Contract Laboratory Program.
D-98 ILM02.0
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Exhibit D Method 286.2
VANADIUM*
Method 286.2 CLP-M** (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 10-200 ug/L
Approximate Detection Limit: 4 ug/L
Preparation of Standard Solution
1. Stock solution: Prepare as described under AA Flame Technique (Method 286.1
CLP-M).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. These solutions are also to be used for "standard
additions."
3. The calibration standards must be prepared using the same type of acid and at
the same concentration as will result in the sample to be analyzed after sample
preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 1400°C.
3. Atomizing Time and Temp: 15 sec @ 2800°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 318.4 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, continuous flow purge gas and
pyrolytic graphite and are to be used as guidelines only. Smaller size furnace
devices or those employing faster rates of atomization can be operated using
lower atomization temperatures for shorter time periods than the above
recommended settings.
2. The use of background correction is required.
3. Because of possible chemical interaction, nitrogen should not be used as the
purge gas.
4. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (see Exhibit E).
5. If method of standard addition is required, follow the procedure given in
Exhibit E.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-99 ILM02.0
-------
Exhibit D Method 289.2
ZINC*
Method 289.2 CLP-M** (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 0.2-4 ug/L
Approximate Detection Limit: 0.05 ug/L
Preparation of Standard Solution
1. Stock solution: Prepare as described under AA Flame Technique (Method 289.1
CLP-M).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. These solutions are also to be used for "standard
additions".
3. The calibration standards must be prepared using the same type of acid and at
the same concentration as will result in the sample to be analyzed after sample
preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 400°C.
3. Atomizing Time and Temp: 10 sec @ 2500°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 213.9 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer
HGA-2100, based on the use of a 20 uL injection, continuous flow purge gas and
non-pyrolytic graphite and are to be used as guidelines only. Smaller size
furnace devices or those employing faster rates of atomization can be operated
using lower atomization temperatures for shorter time periods then the above
recommended settings.
2. The use of background correction is required.
3. Nitrogen may also be used as the purge gas.
4. The analysis of zinc by the graphite furnace is extremely sensitive and very
subject to contamination from the work area, reagents, and pipette tips. Since
all these factors affect the precision and accuracy, zinc should be analyzed by
the direct aspiration procedure whenever possible.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-100 ILM02.0
-------
Exhibit D Method 289.2
5. For every sample analyzed, verification is necessary to determine that method
of standard addition is not required (see Exhibit E).
6. If method of standard addition is required, follow the procedure given in
Exhibit E.
D-101 ILM02.0
-------
Exhibit D Method 202.1
ALUMINUM*
Method 202.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 5-50 mg/L using a wavelength of 309.3 nm
Sensitivity: 1 mg/L
Approximate Detection Limit: 0.1 mg/L
Preparation of Standard Solution
1. Stock Solution: Carefully weigh 1,000 g of aluminum metal analytical reagent
grade). Add 15 mL of cone. HC1 and 5 mL cone. HNC>3 to the metal, cover the
beaker and warm gently. When solution is complete, transfer quantitatively to
a liter volumetric flask and make up to volume with deionized distilled water.
1 mL - 1 mg Al (1000 mg/L).
2. Potassium Chloride Solution: Dissolve 95 g potassium chloride (KC1) in
deionized distilled water and make up to 1 liter.
3. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. The calibration standards must be prepared using the
same type of acid and at the same concentration as will result in the sample to
be analyzed after sample preparation. To each 100 mL of standard and sample
alike add 2.0 mL potassium chloride solution.
Instrument Parameters (General)
1. Aluminum hollow cathode lamp
2. Wavelength: 309.3 nm
3. Fuel: Acetylene
4. Oxidant: Nitrous oxide
5. Type of flame: Fuel rich
Interferences
1. Aluminum is partially ionized in the nitrous oxide-acetylene flame. This
problem may be controlled by the addition of an alkali metal (potassium, 1000
ug/mL) to both sample and standard solutions.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-102 ILM02.0
-------
Exhibit D Method 202.1
1. The following may also be used:
308.2 nm Relative Sensitivity 1
396.2 nm Relative Sensitivity 2
394.4 nm Relative Sensitivity 2.5
2. For concentrations of aluminum below 0.3 mg/L, use of
Furnace Technique (Method 202.2 CLP-M) is recommended.
D-103 ILM02.0
-------
Exhibit D Method 204.1
ANTIMONY*
Method 204.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 1-40 mg/L using a wavelength of 217.6 run
Sensitivity: 0.5 mg/L
Approximate Detection Limit: 0.2 mg/L
Preparation of Standard Solution
1. Stock Solution: Carefully weigh 2.7426 g of antimony potassium tartrate
(analytical reagent grade) and dissolve in deionized distilled water. Dilute
to 1 liter with deionized distilled water. 1 mL - 1 mg Sb (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. The calibration standards must be prepared using the
same type of acid and at the same concentration as will result in the sample to
be analyzed after sample preparation.
Instrumental Parameters (General)
1. Antimony hollow cathode lamp
2. Wavelength: 217.6 nm
3. Fuel: Acetylene
4. Oxidant;.. Air
5. Type of flame: Fuel lean
Interferences
1. In the presence of lead (1000 mg/L), a special interference may occur at the
217.6 nm resonance line. In this case the 231.1 nm antimony line should be
used.
2. Increasing acid concentrations decrease antimony absorption. To avoid this
effect, the acid concentration in the samples and in the standards must be
matched.
Notes
1. For concentrations of antimony below 0.35 mg/L, use of the Furnace Technique
(Method 204.2 CLP-M) is recommended.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-104 ILM02.0
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Exhibit D Method 208.1
BARIUM*
Method 208.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 1-20 mg/L using a wavelength of 553.6 nm
Sensitivity: 0.4 mg/L
Approximate Detection Limit: 0.1 mg/L
Preparation of Standard Solution
1. Stock Solution: Dissolve 1.7787 g of barium chloride (BaCl2'2H20, analytical
reagent grade) in deionized distilled water and dilute to liter. 1 mL - 1 mg
Ba (1000 mg/L).
2. Potassium chloride solution: Dissolve 95 g potassium chloride, KC1, in
deionized distilled water and make up to 1 liter.
3. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. To each 100 mL of standard and sample alike add 2.0 mL
potassium chloride solution. The calibration standards must be prepared using
the same type of acid and at the same concentration as will result in the
sample to be analyzed after sample preparation.
Instrumental Parameters (General)
1. Barium hollow cathode lamp
2. Wavelength: 553.6 nm
3. Fuel: Acetylene
4. Oxidant: Nitrous oxide
5. Type of flame: Fuel rich
Interferences
1. The use of a nitrous oxide-acetylene flame virtually eliminates chemical
interference; however, barium is easily ionized in this flame and potassium
must be added (1000 mg/L) to standards and samples alike to control this
effect.
2. If the nitrous oxide flame is not available and acetylene-air is used,
phosphate, silicon and aluminum will severely depress the barium absorbance.
This may be overcome by the addition of 2000 mg/L lanthanum.
Notes
1. For concentrations of barium below 0.2 mg/L, use of the Furnace Technique
(Method 208.2 CLP-M) is recommended.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-105 ILM02.0
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Exhibit D Method 210.1
BERYLLIUM*
Method 210.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.052 mg/L using a wavelength of 234.9 run
Sensitivity: 0.025 mg/L
Approximate Detection Limit: 0.005 mg/L
Preparation of Standard Solution
1. Stock Solution: Dissolve 11.6586 g of beryllium sulfate, BeS04, in deionized
distilled water containing 2 mL cone, nitric acid and dilute to 1 liter. 1 mL
- 1 mg Be (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. The calibration standards should be prepared using the
same type of acid and at the same concentration as will result in the sample to
be analyzed after sample preparation.
Instrumental Parameters (General)
1. Beryllium hollow cathode lamp
2. Wavelength: 234.9 nm
3. Fuel: Acetylene
4. Oxidant: Nitrous oxide
5. Type of flame: Fuel rich
Interferences
1. Sodium and silicon at concentrations in excess of 1000 mg/L have been found to
severely depress the beryllium absorbance.
2. Bicarbonate ion is reported to interfere; however, its effect is eliminated
when samples are acidified to a pH of 1.5.
3. Aluminum at concentrations of 500 ug/L is reported to depress the sensitivity
of beryllium [Spectrochim Acta 22, 1325 (1966)].
Notes
1. For concentrations of beryllium below 0.02 mg/L, use of the Furnace Technique
(Method 210.2 CLP-M) is recommended.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-106 ILM02.0
-------
Exhibit D Method 213.1
CADMIUM*
Method 213.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.052 mg/L using a wavelength of 228.8 nm
Sensitivity: 0.025 mg/L
Approximate Detection Limit: 0.005 mg/L
Preparation of Standard Solution
1. Stock Solution: Carefully weigh 2.282 g of cadmium sulfate (3CdS04-8H20,
analytical reagent grade) and dissolve in deionized distilled water. Make up
to 1 liter with dionized distilled water. 1 mL - 1 mg Cd (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. The calibration standards must be prepared using the
same type of acid and at the same concentration as will result in the sample to
be analyzed after sample preparation.
Instrumental Parameters (General)
1. Cadmium hollow cathode lamp
2. Wavelength: 228.8 nm
3. Fuel: Acetylene
4. Oxidant:- Air
5. Type of flame: Oxidizing
Notes
1. For concentrations of cadmium below 20 ug/L, use of the Furnace Technique,
Method 213.2 CLP-M is recommended.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-107 ILM02.0
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Exhibit D Method 218.1
CHROMIUM*
Method 218.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.5-10 mg/L using a wavelength of 357.9 nm
Sensitivity: 0.25 mg/L
Approximate Detection Limit: 0.05 mg/L
Preparation of Standard Solution
1. Stock Solution: Dissolve 1.923 g of chromium trioxide (Cr03, reagent grade) in
deionized distilled water. When solution is complete, acidify with redistilled
HN03 and dilute to 1 liter with deionized distilled water. 1 mL - 1 mg Cr
(1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. The calibration standards must be prepared using the
same type of acid and at the same concentration as will result in the sample to
be analyzed after sample preparation.
Instrument Parameters (General)
1. Chromium hollow cathode lamp
2. Wavelength: 357.9 nm
3. Fuel: Acetylene
4. Oxidant: Nitrous oxide
5. Type of flame: Fuel rich
Notes
1. The following wavelengths may also be used:
359.3 nm Relative Sensitivity 1.4
425.4 nm Relative Sensitivity 2
427.5 nm Relative Sensitivity 3
428.9 nm Relative Sensitivity 4
2. The fuel rich air-acetylene flame provides greater sensitivity but is subject
to chemical and matrix interference from iron, nickel, and other metals. If
the analysis is performed in a lean flame the interference can be lessened but
the sensitivity will also be reduced.
3. The suppression of both Cr (III) and Cr (VI) absorption by most interfering
ions in fuel rich air-acetylene flames is reportedly controlled by the addition
of 1% ammonium bifluoride in 0.2% sodium sulfate [Talanta 20, 631 (1973)]. A
1% oxine solution is also reported to be useful.
4. For concentrations of chromium between 50 and 200 ug/L where the air-acetylene
flame cannot be used or for concentrations below 50 ug/L, use of the Furnace
Technique (Method 218.2 CLP-M) is recommended.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-108 ILM02.0
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Exhibit D Method 219.1
COBALT*
Method 219.1** CLP-M (Atomic Absorption, Flame Technique)
Optimum Concentration Range: .0.5-5 mg/L using a wavelength of 240.7 nm
Sensitivity: 0.2 mg/L
Approximate Detection Limit: 0.05 mg/L
Preparation of Standard Solution
1. Stock Solution: Dissolve 4.307 g of cobaltous chloride (CoC12. 6H20
analytical reagent grade), in deionized distilled water. Add 10 mL of
concentrated nitric acid and dilute to 1 liter with deionized distilled water.
1 mL - 1 mg Co (1000 mg/L).
2. Prepare dilutions of the stock cobalt solution to be used as calibration
standards at the time of analysis. The calibration standards must be prepared
using the same type of acid and at the same concentration as will result in the
sample to be analyzed after sample preparation.
Instrument Parameters (General)
1. Cobalt hollow cathode lamp
2. Wavelength: 240.7 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Notes
1. For concentrations of cobalt below 100 ug/L use of the Furnace Technique
(Method 219.2 CLP-M) is recommended.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-109 ILM02.0
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Exhibit D Method 220.1
COPPER*
Method 220.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.2-5 mg/L using a wavelength of 324.7 nm
Sensitivity: 0.1 mg/L
Approximate Detection Limit: 0.02 mg/L
Preparation of Standard Solution
1. Stock Solution: Carefully weigh 100 g of electrolyte copper (analytical
reagent grade). Dissolve in 5 mL redistilled HN03 and make up to 1 liter with
deionized distilled water. Final concentration is 1 mg Cu per mL (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. The calibration standards must be prepared using the
same type of acid and at the same concentration as will result in the sample to
be analyzed after sample preparation.
Instrumental Parameters (General)
1. Copper hollow cathode lamp
2. Wavelength: 324.7 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Notes
1. For concentrations of copper below 50 ug/L use of the Furnace Technique (Method
220.2 CLP-M) is recommended.
2. Numerous absorption lines are available for the determination of copper. By
selecting a suitable absorption wavelength, copper samples may be analyzed over
a very wide range of concentrations. The following lines may be used:
327.4 nm Relative Sensitivity 2
216.5 nm Relative Sensitivity 7
222.5 nm Relative Sensitivity 20
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-110 ILM02.0
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Exhibit D Method 236.1
IRON*
Method 236.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.3-5 mg/L using a wavelength of 248.3 run
Sensitivity: 0.12 mg/L
Approximate Detection Limit: 0.03 mg/L
Preparation of Standard Solution
1. Stock Solution: Carefully weigh 1.000 g of pure iron wire (analytical reagent
grade) and dissolve in 5 mL redistilled HN03, warming if necessary. When
solution is complete, make up to 1 liter with deionized distilled water. 1 mL
- 1 mg Fe (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. The calibration standards must be prepared using the
same type of acid and at the same concentration as will result in the sample to
be analyzed after sample preparation.
Instrumental Parameters (General)
1. Iron hollow cathode lamp
2. Wavelength: 248.3 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Notes
1. The following wavelengths may also be used:
248.8 nm Relative Sensitivity 2
271.9 nm Relative Sensitivity 4
302.1 nm Relative Sensitivity 5
252.7 nm Relative Sensitivity 6
372.0 nm Relative Sensitivity 10
2. For concentrations of iron below 0.05 mg/L use of the Furnace Technique (Method
236.2 CLP-M) is recommended.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-lll ILM02.0
-------
Exhibit D Method 239.1
LEAD*
Method 239.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 1-20 mg/L using a wavelength of 283.3 run
Sensitivity: 0.5 mg/L
Approximate Detection Limit: 0.1 mg/L
Preparation of Standard Solution
1. Stock Solution: Carefully weigh 1.599 g of lead nitrate, Pb(N03>2 (analytical
reagent grade), and dissolve deionized distilled water. When solution is
complete acidify with 10 mL redistilled HN03 and dilute to 1 liter with
deionized distilled water. 1 mL - 1 nig Pb (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. The calibration standards must be prepared using the
same type of acid and at the same concentration as will result in the sample to
be analyzed after sample preparation.
Instrumental Parameters (General)
1. Lead hollow cathode lamp
2. Wavelength: 283.3 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
1. The analysis of this metal is exceptionally sensitive to turbulence and
absorption bands in the flame. Therefore, some care should be taken to
position the light beam in the most stable, center portion of the flame. To do
this, first adjust the burner to maximize the absorbance reading with a lead
standard. Then, aspirate a water blank and make minute adjustments in the
burner alignment to minimize the signal.
2. The concentrations of lead below 200 ug/L use of the Furnace Technique (Method
239.2 CLP-M) is recommended.
3. The following wavelengths may also be used:
217.0 nm Relative Sensitivity 0.4
261.4 nm Relative Sensitivity 10
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-112 ILM02.0
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Exhibit D Method 243.1
MANGANESE*
Method 243.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.1-3 mg/L using a wavelength of 279.5 run
Sensitivity: 0.05 mg/L
Approximate Detection Limit: 0.01 mg/L
Preparation of Standard Solution
1. Stock Solution: Carefully weigh 1.000 g of manganese metal (analytical reagent
grade), and dissolve in 10 mL redistilled HN03. When solution is complete,
dilute to 1 liter with 1% (v/v) HC1. 1 mL - 1 mg Mn (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. The calibration standards must be prepared using the
same type of acid and at the same concentration as will result in the sample to
be analyzed after sample preparation.
Instrumental Parameters (General)
1. Manganese hollow cathode lamp
2. Wavelength: 279.5 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Notes
1. For concentrations of manganese below 25 ug/L, use of the Furnace Technique
(Method 243.2 CLP-M) is recommended.
2. The following line may also be used: 403.1 nm Relative Sensitivity 10.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-113 ILM02.0
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Exhibit D Method 249.1
NICKEL*
Method 249.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.3-5 mg/L using a wavelength of 232.0 nm
Sensitivity: 0.15 mg/L
Approximate Detection Limit: 0.04 mg/L
Preparation of Standard Solution
1. Stock Solution: Dissolve 4.953 g of nickel nitrate, Ni(N03>2'6H20 (analytical
reagent grade) in deionizing distilled water. Add 10 mL of cone, nitric acid
and dilute to 1 liter deionized distilled water. 1 mL - 1 mg Ni (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. The calibration standards should be prepared using the
same type of acid and at the same concentration as will result in the sample to
be analyzed after sample preparation.
Instrumental Parameters (General)
1. Nickel hollow cathode lamp
2. Wavelength: 232.0 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Interferences
1. The 352.4 nm wavelength is less susceptible to spectral interference and may be
used. The calibration curve is more linear at this wavelength; however, there
is some loss of sensitivity.
Notes
1. For concentrations of nickel below 100 ug/L, use of the Furnace Technique
(Method 249.2 CLP-M) is recommended.
*This method may only be used under specified conditions
**CLP-M Modified for the Contract Laboratory Program.
D-114 ILM02.0
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Exhibit D Method 272.1
SILVER*
Method 272.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.1-4 mg/L using a wavelength of 328.1 nm
Sensitivity: 0.06 mg/L
Approximate Detection Limit: 0.01 mg/L
Preparation of Standard Solution
1. Stock Solution: Dissolve 1.575 g of AgN03, (analytical reagent grade) in
deionized distilled water, add 10 mL cone. HN03 and make up to 1 liter. 1 mL -
1 mg Ag (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. The calibration standards must be prepared using the
same type of acid and at the same concentration as will result in the sample to
be analyzed after sample preparation.
3. Iodine Solution, 1 N: Dissolve 20 grams of potassium iodide, KI (analytical
reagent grade) in 50 mL of deionized distilled water, add 12.7 grams of iodine,
12, (analytical reagent grade) and dilute to 100 mL. Store in a brown bottle.
4. Cyanogen Iodide (CNI) Solution: To 50 mL of deionized distilled water add 4.0
mL cone. NH^H, 6.5 grams KCN, and 5.0 mL of 1.0 N 12 solution. Mix and
dilute to 100 mL with deionized distilled water. Fresh solution should be
prepared every two weeks.(1)
Instrumental Parameters (General)
1. Silver hollow cathode lamp
2. Wavelength: 328.1 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Notes
1. For concentrations of silver below 30 ug/L, use of the Furnace Technique
(Method 272.2 CLP-M) is recommended.
2. Silver nitrate standards are light sensitive. Dilutions of the stock should be
discarded after use as concentrations below 10 mg/L are not stable over long
periods of time.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-115 ILM02.0
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Exhibit D Method 272.1
3. If absorption to container walls or the formation of AgCl is suspected, make
the sample basic using cone. NfyOH and add 1 mL of (CNI) solution per 100 mL of
sample. Mix the sample and allow to stand for 1 hour before proceeding with
the analysis.(1)
4. The 338.2 nm wavelength may also be used. This has a relative sensitivity of
2.
D-116 ILM02.0
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Exhibit D Method 279.1
THALLIUM*
Method 279.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 1-20 mg/L using a wavelength of 276.8 nm
Sensitivity: 0.5 mg/L
Approximate Detection Limit: 0.1 mg/L
Preparation of Standard Solution
1. Stock Solution: Dissolve 1.303 g of thallium nitrate, T1N03 (analytical
reagent grade) in deionized distilled water. Add 10 mL of cone, nitric acid
and dilute to 1 liter with deionized distilled water. 1 mL - 1 mg Tl (1000
mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. The calibration standards must be prepared using nitric
acid and at the same concentration as will" result in the sample to be analyzed
after sample preparation.
Instrumental Parameters (General)
1. Thallium hollow cathode lamp
2. Wavelength: 276.8 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Notes
1. For concentrations of thallium below 0.2 mg/L, use of the Furnace Technique
(Method 279.2 CLP-M) is recommended.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-117 ILM02.0
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- Exhibit D Method 286.1
VANADIUM*
Method 286.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 2-100 mg/L using a wavelength of 318.4 nm
Sensitivity: 0.8 mg/L
Approximate Detection Limit: 0.2 mg/L
Preparation of Standard Solution
1. Stock Solution: Dissolve 1.7854 g of vanadium pentoxide, V205 (analytical
reagent grade) in 10 mL of cone, nitric acid and dilute to 1 liter with
deionized distilled water. 1 mL - 1 mg V (1000 mg/L).
2. Aluminum nitrate solution: Dissolve 139 g aluminum nitrate, A1(N03)3'9H20, in
150 mL of deionized distilled water; heat to effect solution. Allow to cool
and make up to 200 mL.
3. Prepare dilutions of the stock vandium solution to be used as calibration
standards at the time of analysis. The calibration standards must be prepared
using the same type of acid and at the same concentration as will result in the
sample to be analyzed after sample preparation. To each 100 mL of standard and
sample alike, add 2 mL of the aluminum nitrate solution.
Instrumental Parameters (General)
1. Vanadium hollow cathode lamp
2. Wavelength: 318.4 nm
3. Fuel: Acetylene
4. Oxidant: Nitrous Oxide
5. Type of flame: Fuel rich
Interferences
1. It has been reported that high concentrations of aluminum and titanium increase
the sensitivity of vanadium. This interference can be controlled by adding
excess aluminum (1000 ppm) to both samples and standards. [Talanta 15, 871
(1968)].
Notes
1. For concentrations of vanadium below 0.5 mg/L, use of the Furnace Technique
(Method 282.6 CLP-M) is recommended.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-118 ILM02.0
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Exhibit D Method 289.1
ZINC*
Method 289.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.05-1 mg/L using a wavelength of 213.9 nm
Sensitivity: 0.02 mg/L
Approximate Detection Limit: 0.005 mg/L
Preparation of Standard Solution
1. Stock Solution: Carefully weigh 1.00 g of zinc metal (analytical reagent
grade) and dissolve cautiously in 10 mL HN03- When solution is complete make
up to 1 liter with deionized distilled water. 1 mL - 1 mg Zn (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration standards at
the time of analysis. The calibration standards must be prepared using the
same type of acid and at the same concentration as will result in the sample to
be analyzed after sample preparation.
Instrumental Parameters (General)
1. Zinc hollow cathode lamp
2. Wavelength: 213.9 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Notes
1. High levels of silicon may interfere.
2. The air-acetylene flame absorbs about 25% of the energy at the 213.9 nm line.
3. The sensitivity may be increased by the use of low-temperature flames.
4. Some container cap liners can be a source of zinc contamination. To circumvent
or avoid this problem, the use of the polypropylene caps is recommended.
5. For concentrations of zinc below 0.01 mg/L, use of the Furnace Technique
(Method 289.2 CLP-M) is recommended.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-119 ILM02.0
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EXHIBIT E
QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
SECTION I
SECTION II
SECTION III
SECTION IV
SECTION V
SECTION VI
SECTION VII
SECTION VIII
SECTION . IX
SECTION X
SECTION XI
- GENERAL QA/QC PRACTICES
- SPECIFIC QA/QC PROCEDURES
- QUALITY ASSURANCE PLAN
- STANDARD OPERATING PROCEDURES
- REQUIRED QA/QC OPERATIONS
- CONTRACT COMPLIANCE SCREENING
- ANALYTICAL STANDARDS REQUIREMENTS
- DATA PACKAGE AUDITS
- PERFORMANCE EVALUATION SAMPLES
- ON-SITE LABORATORY EVALUATIONS
- DATA MANAGEMENT
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SECTION I
GENERAL QA/QC PRACTICES
Standard laboratory practices for laboratory cleanliness as applied to
glassware and apparatus must be adhered to. Laboratory practices with
regard to reagents, solvents, and gases must also be adhered to. For
additional guidelines regarding these general laboratory procedures, see
Sections 4 and 5 of the Handbook for Analytical Quality Control in Water
and Wastewater Laboratories EPA-600/4-79-019, USEPA Environmental
Monitoring and Support Laboratory, Cincinnati, Ohio, September 1982.
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SECTION II
SPECIFIC QA/QC PROCEDURES
The quality assurance/quality control (QA/QC) procedures defined herein
must be used by the Contractor when performing the methods specified in
Exhibit D. When additional QA/QC procedures are specified in the methods
in Exhibit D, the Contractor must also follow these, procedures. NOTE: The
cost of performing all QA/QC procedures specified in this Statement of Work
is included in the price of performing the bid lot, except for duplicate,
spike, and laboratory control sample analyses, which shall be considered
separate sample analyses.
The purpose of this document is to provide a uniform set of procedures for
the analysis of inorganic constituents of samples, documentation of methods
and'their performance, and verification of the sample data generated. The
program will also assist laboratory personnel in recalling and defending
their actions under cross examination if required to present court
testimony in enforcement case litigation.
The primary function of the QA/QC program is the definition of procedures
for the evaluation and documentation of sampling and analytical
methodologies and the reduction and reporting of dc.ta. The objective is to
provide a uniform basis for sample collection and handling, instrument and
methods maintenance, performance evaluation, and analytical data gathering
and reporting. Although it is impossible to address all analytical
situations in one document, the approach taken here: is to define minimum
requirements for all major steps relevant to any inorganic analysis. In
many instances where methodologies are available, specific quality control
procedures are incorporated into the method documentation (Exhibit D).
Ideally, samples involved in enforcement actions are analyzed only after
the methods have met the minimum performance and documentation requirements
described in this document.
The Contractor is required to participate in the laboratory Audit and
Intercomparison Study Program run by EPA EMSL-Las Vegas. The Contractor
can expect to analyze at least two samples per calendar quarter during the
contract period.
The Contractor must perform and report to SMO and EMSL as specified in
Exhibit B quarterly verification of instrument detection limits (IDL) by
the method specified in Exhibit E, by type and model for each instrument
used on this contract. All the IDLs must meet the CRDLs specified in
Exhibit C. For ICP methods, the Contractor must also report, as specified
in Exhibit B, linearity range verification, all interelement correction
factors, wavelengths used, and integration times.
In this Exhibit, as well as other places within this Statement of Work, the
term "analytical sample" is used in discussing the required frequency or
placement of certain QA/QC measurements. The term "analytical sample" is
defined in the glossary, Exhibit G. As the term is used, analytical sample
includes all field samples, including Performance Evaluation samples,
received from an external source, but it also includes all required QA/QC
samples (matrix spikes, analytical/post-digestion spikes, duplicates,
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serial dilutions, LCS, ICS, CRDL standards, preparation blanks and linear
range analyses) except those directly related to instrument calibration or
calibration verification (calibration standards, ICV/ICB, CCV/CCB). A
"frequency of 10%" means once every 10 analytical samples. Note:
Calibration verification samples (ICV/CCV) and calibration verification
blanks (ICB/CCB) are not counted as analytical samp>les when determining 10%
frequency.
In order for the QA/QC information to reflect the status of the samples
analyzed, all samples and their QA/QC analysis must: be analyzed under the
same operating and procedural conditions.
If any QC measurement fails to meet contract criteria, the analytical
measurement may not be repeated prior to taking the appropriate corrective
action as specified in Exhibit E.
The•Contractor must report all QC data in the exact: format specified in
Exhibits B and H.
Sensitivity, instrumental detection limits (IDL's), precision, linear
dynamic range and interference effects must be established for each analyte
on a particular instrument. All reported measurements must be within the
instrumental linear ranges. The analyst must maintain quality control data
confirming instrument performance and analytical re suits.
In addition, the Contractor shall establish a quality assurance program
with the objective of providing sound analytical chemical measurements.
This program shall incorporate the quality control 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
Quality Assurance Plan (QAP) (see Section III) which describes the
procedures that are implemented to achieve the following:
Maintain data integrity, validity, and useability.
Ensure that analytical measurement systems are maintained in an
acceptable state of stability and reproducibility.
Detect problems through data assessment and establishes corrective
action procedures which keep the analytical process reliable.
Document all aspects of the measurement process in order to provide
data which are technically sound and legally defensible.
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SECTION III
QUALITY ASSURANCE PLAN
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 on-site laboratory
evaluation and upon written request by the APO. The elements of the QAP
are listed in the following outline.
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
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. SDG File Organization, Preparation and Review Procedures
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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 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 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
G. 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
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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 Technical Project Officer,
EMSL/LV and NEIC. The revised QAP will become the official QAP under the
contract. The revised QAP must include:
1) Changes resulting from A) The Contractor's internal review of their
organization, personnel, facility, equipment, policy and procedures and
B) 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 pre-award On-Site laboratory evaluation
Subsequent submissions:
During the term of contract, the Contractor shall emend the QAP when the
following circumstances occur:
1) The Agency modifies the contract,
2) The Agency notifies the Contractor of deficiencies in the QAP document
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 their internal
review of their QAP document,
5) The Contractor's organization, personnel, facility, equipment, policy
or procedures change,
6) The Contractor identifies deficiencies resulting from the internal
review of their organization, personnel, facility, equipment, policy or
procedures changes.
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
(e.g., a bar in the margin indicating where the change is found in the
document, or highlighting the change by underlining; the change, bold
printing the change, or using a different print font). The amended section
pages must have the date on which the changes were implemented. The
Contractor shall incorporate all amendments to the current QAP document.
The Contractor shall archive all amendments to the QAP document for future
reference by the Agency.
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The Contractor shall send a copy of the current QA? document within 14 days
of a request by the Technical Project Officer or Administrative Project
Officers to the designated recipients.
Corrective Action:
If a Contractor fails to adhere to the requirements listed in this section,
a 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, ds.ta package audit, an On-
Site laboratory evaluation, remedial performance evaluation sample, and/or
contract sanctions, such as a Cure Notice.
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SECTION IV
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
Standard Operating Procedures (SOPs). As defined by the EPA, an 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 the Agency,
must reflect activities as they are currently performed in the laboratory.
In addition, all SOPs must be:
o Consistent with current EPA regulations, guidelines, and the CLP
contract's requirements.
o Consistent with instruments manufacturers's specific instruction
manuals.
o 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 Laboratory evaluations,
laboratory personnel may be asked to demonstrate the application of the
SOPs.
o Capable of providing for the development of documentation that is
sufficiently complete to record the performance of all tasks required by
the protocol.
o Capable of demonstrating the validity of data reported by the Contractor
and explain the cause of missing or inconsistent results.
o Capable of describing the corrective measures and feedback mechanism
utilized when analytical results do not meet protocol requirements.
o Reviewed regularly and updated as necessary when contract, facility, or
Contractor procedural modifications are made.
o Archived for future reference in usability or evidentiary situations.
o Available at specific work stations as appropriate
o Subject to a document control procedure which precludes the use of
outdated or inappropriate SOPs.
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:
o Title Page
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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
SOPS REQUIRED:
The'following SOPs are required by the Agency:
1. Evidentiary SOP
Evidentiary SOPs for required chain-of-custocly and document control
are discussed in Exhibit F
2. Sample Receipt and Storage
a. Sample receipt and identification logbooks
b. Refrigerator temperature logbooks
c. Security precautions
3. Sample preparation
4. Glassware cleaning
5. Calibration (Balances, etc.)
a. Procedures
b. Frequency requirements
c. Preventative maintenance schedule and procedures
d. Acceptance criteria and corrective actions
e. Logbook maintenance authorization
6. Analytical procedures (for each analytical system)
a. Instrument performance specifications
b. Instrument operating procedures
c. Data acquisition system operation
d. Procedures when automatic quantitation algorithms are
overridden
e. QC required parameters
f. Analytical run/injection logbooks
g. Instrument error and editing flag descriptions and resulting
corrective actions
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7. Maintenance activities (for each analytical system)
a. Preventative maintenance schedule and procedures
b. Corrective maintenance determinants and procedures
c. Maintenance authorization
8. Analytical standards
a. Standard coding/identification and inventory system
b. Standards preparation logbook(s)
c. Standard preparation procedures
d. Procedures for equivalency/traceability analyses and
documentat ion
e. Purity logbook (primary standards and solvents)
f. Storage, replacement, and labelling requirements
g. QC and corrective action measures
9. Data reduction procedures
a. Data processing systems operation
b. Outlier identification methods
c. Identification of data requiring corrective action
d. Procedures for format and/or forms for each operation
10. Documentation policy/procedures
a. Laboratory/analyst's notebook policy, including review policy
b. Complete SDG File contents
c. Complete SDG File organization and assembly procedures,
including review policy
d. Document inventory procedures, including review policy
11. Data validation/self inspection procedures
a. Data flow and chain-of-command for dats. review
b. Procedures for measuring precision and accuracy
c. Evaluation parameters for identifying systematic errors
d. Procedures to assure that hardcopy and diskette deliverables
are complete and compliant with the requirements in SOW
Exhibits B and H.
e. Procedures to assure that hardcopy deliverables are in
agreement with their comparable diskette deliverables.
f. Demonstration of internal QA inspection procedure (demonstrated
by supervisory sign-off on personal notebooks, internal
laboratory evaluation samples, etc.).
g. Frequency and type of internal audits (eg., random, quarterly,
spot checks, perceived trouble areas).
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h. Demonstration of problem identification-corrective actions and
resumption of analytical processing. Sequence resulting from
internal audit (i.e., QA feedback).
i. Documentation of audit reports, (internal and external),
response, corrective action, etc.
12. 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.
SOPS DELIVERY REQUIREMENTS:
Updating and submission of SOPs:
Within 60 days of contract award:
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 Technical
Project Officer, EMSL/LV and NEIC. The revised SOPs will become the
official SOPs under the contract. The revised SOPs must include:
1) Changes resulting from A) the Contractor's internal review of their
procedures and B) the Contractor's implementation of the requirements
of the contract;
2) Changes resulting from the Agency's review of the laboratory evaluation
sample data, bidder supplied documentation, and recommendations made
during the pre-award On-Site laboratory evaluation.
Subsequent Submissions:
During the term of contract, the Contractor shall emend 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
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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 documentation, or
6) The Contractor identifies deficiencies resulting form 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
(e.g., a bar in the margin indicating where the change is in the document,
or highlighting the change by underlining the change, bold printing the
change, 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, £.nd submit the amended
SOPs or new SOPs to the Technical Project Officer, 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 Technical Project Officer or Administrative Project Officer, to
approve or disapprove the alternate delivery schedule. If an alternate
delivery schedule is proposed, the Contractor shall describe in a letter to
the Technical Project Officer, Administrative Project Officer, and the
Contracting Officer why he/she is unable to meet the delivery schedule
listed in this section. The Technical Project Officer/Administrative
Project Officer will not grant an extension for greater than 30 days for
amending/writing new SOPs. The Technical Project Officer/Administrative
Project Officer 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.
The Contractor shall send a complete set of current: SOPs within 14 days of
a request by the Technical Project Officer or Administrative Project
Officer to the recipients he/she designates.
Corrective action:
If a Contractor fails to adhere to the requirements listed in this section,
a 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, d£.ta package audit, On-
Site laboratory evaluation, remedial performance evaluation sample, and/or
contract sanction, such as a Cure Notice.
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SECTION V
REQUIRED QA/QC OPERATIONS
This section outlines the minimum QA/QC operations necessary to satisfy the
analytical requirements of the .contract. The following QA/QC operations
must be performed as described in this Exhibit:
1. Instrument Calibration
2. Initial Calibration Verification (ICV) and Continuing Calibration
Verification (CCV)
3. CRDL Standards for AA (CRA) and ICP (CRI)
4. Initial Calibration Blank (ICB), Continuing Calibration Blank
(CCB), and Preparation Blank (PB) Analyses
• 5. ICP Interference Check Sample (ICS) Analyses
6. Spike Sample Analysis (S)
7. Duplicate Sample Analysis (D)
8. Laboratory Control Sample (LCS) Analysis
9. ICP Serial Dilution Analysis (L)
10. Instrument Detection Limit (IDL) Determination
11. Interelement Corrections for ICP (ICP)
12. Linear Range Analysis (LRA)
13. Furnace AA QC Analyses
1. Instrument Calibration
Guidelines for instrumental calibration are given in EPA 600/4-79-020
and/or Exhibit D. Instruments must be calibrated daily or once every 24
hours and each time the instrument is set up. The instrument
standardization date and time must be included in the raw data.
For atomic absorption systems, calibration standards are prepared by
diluting the stock metal solutions at the time of analysis. Date and
time of preparation and analysis must be given in the raw data.
Calibration standards must be prepared fresh daily or each time an
analysis is to be made and discarded after use. For atomic absorption
systems, prepare a blank and at least three calibration standards in
graduated amounts in the appropriate range. One atomic absorption
calibration standard must be at the CRDL. The calibration standards
must be prepared using the same type of acid or combination of acids
and at the same concentration as will result in the samples following
sample preparation.
Beginning with the blank, aspirate or inject the standards and record
the readings. If the AA instrument configuration prevents the required
4-point calibration, calibrate according to instrument manufacturer's
recommendations, and analyze the remaining required standards
immediately after calibration. Results for these standards must be
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within 5% of the true value. Each standards concentration and the
calculations to show that the 5% criterion has been met, must be given
in the raw data. If the values do not fall within this range,
recalibration is necessary.
The 5% criteria does not apply to the atomic absorption calibration
standard at the CRDL.
Calibration standards for AA procedures must be prepared as described
in Exhibit D.
Baseline correction is acceptable as long as it is performed after
every sample or after the continuing calibration verification and blank
check; resloping is acceptable as long as it is immediately preceded
and immediately followed by compliant CCV and CCB. For cyanide and
mercury, follow the calibration procedures outlined in Exhibit D. One
• cyanide calibration standard must be at the CRDL. For ICP systems,
calibrate the instrument according to instrument manufacturer's
recommended procedures. At least two standards must be used for ICP
calibration. One of the standards must be a blank.
2. Initial Calibration Verification (ICV) and Continuing Calibration
Verification (CCV)
a. Initial Calibration Verification (ICV)
Immediately after each of the ICP, AA and cyanide systems have
been calibrated, the accuracy of the initial calibration shall be
verified and documented for every analyte by the analysis of EPA
Initial Calibration Verification Solution(s) at each wavelength
used for analysis. When measurements exceed the control limits of
Table 1-Initial and Continuing Calibration Verification Control
Limits for Inorganic Analyses (in Exhibit E), the analysis must be
terminated, the problem corrected, the instrument recalibrated,
and the calibration reverified.
If the Initial Calibration Verification Solution(s) are not
available from EPA, or where a certified solution of an analyte is
not available from any source, analyses shall be conducted on an
independent standard at a concentration other than that used for
instrument calibration, but within the calibration range. An
independent standard is defined as a standard composed of the
analytes from a different source than those used in the standards
for the instrument calibration.
For ICP, the Initial Calibration Verification Solution(s) must be
run at each wavelength used for analysis. For CN, the initial
calibration verification standard must be distilled. The Initial
Calibration Verification for CN serves as a Laboratory Control
Sample; thus it must be distilled with the batch of samples
analyzed in association with that ICV. This means that an ICV
must be distilled with each batch of samples analyzed and that the
samples distilled with an ICV must be analyzed with that
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particular ICV. The values for the initial and subsequent
continuing calibration verification shall be recorded on FORM II-
IN for ICP, AA, and cyanide analyses, as indicated.
b. Continuing Calibration Verification (CCV)
To ensure calibration accuracy during each analysis run, one of
the following standards is to be used for continuing calibration
verification and must be be analyzed and reported for every
wavelength used for the analysis of each analyte, at a frequency
of 10% or every 2 hours during an analysis run, whichever is more
frequent. The standard must also be analyzed and reported for
every wavelength used for analysis at the beginning of the run and
after the last analytical sample. The analyte concentrations in
the continuing calibration standard must be one of the following
solutions at or near the mid-range levels of the calibration
curve:
1. EPA Solutions
2. NIST Standards
3. A Contractor-prepared standard solution
TABLE 1. INITIAL AND CONTINUING CALIBRATION VERIFICATION
CONTROL LIMITS FOR INORGANIC ANALYSES
Analytical Method
ICP/AA
Cold Vapor AA
Other
Inorganic
Species
Metals
Mercury
Cyanide
% of True
Low Limit
90
80
85
Value (EPA Set)
High Limit
110
120
115
The same continuing calibration standard must be used throughout
the analysis runs for a Case of samples received.
Each CCV analyzed must reflect the conditions of analysis of all
associated analytical samples (the preceding 10 analytical samples
or the preceding analytical samples up to the previous CCV). The
duration of analysis, rinses and other related operations that may
affect the CCV measured result may not be applied to the CCV to a
greater extent than the extent applied to the associated
analytical samples. For instance, the difference in time between
a CCV analysis and the blank immediately following it as well as
the difference in time between the CCV and the analytical sample
immediately preceding it may not exceed the lowest difference in
time between any two consecutive analytical samples associated
with the CCV.
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If the deviation of the continuing calibration verification is
greater than the control limits specified in Table 1-Initial and
Continuing Calibration Verification Control Limits for Inorganic
Analyses, the analysis must be stopped, the problem corrected, the
instrument must be recalibrated, the calibration verified and the
reanalysis of preceding 10 analytical samples or all analytical
samples analyzed since the last compliant calibration verification
must be performed for the analytes affected. Information
regarding the continuing verification of calibration shall be
recorded on FORM II-IN for ICP, AA and cyanide as indicated.
3. CRDL Standards for ICP (CRI) and AA (CRA)
To verify linearity near the CRDL for ICP analysis, the Contractor must
analyze an ICP standard (CRI) at two times the CRDL or two times the
IDL, whichever is greater, at the beginning and end of each sample
• analysis run, or a minimum of twice per 8 hour working shift, whichever
is more frequent, but not before Initial Calibration Verification.
This standard must be run by ICP for every wavelength used for
analysis, except those for Al, Ba, Ca, Fe, Mg, Na and K.
To verify linearity near the CRDL for AA analysis, the Contractor must
analyze an AA standard (CRA) at the CRDL or the IDL, whichever is
greater, at the beginning of each sample analysis run, but not before
the Initial Calibration Verification.
Specific acceptance criteria for the two standards will be set by EPA
in the future. In the interim, the Contractor must analyze and report
these Standards on FORM II(PART 2)-IN.
4. Initial Calibration Blank (ICB). Continuing Calibration Blank (CCB).
and Preparation Blank (PB) Analyses
a. Initial Calibration Blank (ICB) and Continuing Calibration Blank
(CCB) Analyses
A calibration blank must be analyzed at each wavelength used for
analysis immediately after every initial and continuing
calibration verification, at a frequency of 10% or every 2 hours
during the run, whichever is more frequent. The blank must be
analyzed at the beginning of the run and after the last
analytical sample. Note: A CCB must be run. after the last CCV
that was run after the last analytical sample of the run. The
results for the calibration blanks shall be recorded on FORM III-
IN for ICP, AA and cyanide analyses, as indicated. If the
magnitude (absolute value) of the calibration blank result exceeds
the IDL, the result must be so reported in ug/L on FORM III-IN,
otherwise report as IDL-U. If the absolute value blank result
exceeds the CRDL (Exhibit C), terminate analysis, correct the
problem, recalibrate, verify the calibration and reanalyze the
preceding 10 analytical samples or all analytical samples analyzed
since the last compliant calibration blank.
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b. Preparation Blank (PB) Analysis
At least one preparation blank (or reagent blank), consisting of
deionized distilled water processed through each sample
preparation and analysis procedure (See Exhibit D, Section III),
must be prepared and analyzed with every Sample Delivery Group, or
with each batch of samples digested, whichever is more frequent.
The first batch of samples in an SDG is to be assigned to
preparation blank one, the second batch of samples to preparation
blank two, etc. (see FORM III-IN). Each data package must contain
the results of all the preparation blank analyses associated with
the samples in that SDG.
This blank is to be reported for each SDG and used in all analyses
to ascertain whether sample concentrations reflect contamination
in the following manner:
1) If the absolute value of the concentration of the blank is
less than or equal to the Contract Required Detection Limit
(Exhibit C), no correction of sample results is performed.
2) If any analyte concentration in the blank is above the CRDL,
the lowest concentration of that analyte in the associated
samples must be lOx the blank concentration. Otherwise, all
samples associated with the blank with the analyte's
concentration less than lOx the blank concentration and above
the CRDL, must be redigested and reanalyzed for that analyte
(except for an identified aqueous soil field blank). The
sample concentration is not to be corrected for the blank
value.
3) If the concentration of the blank is below the negative CRDL,
then all samples reported below lOx CRDL associated with the
blank must be redigested and reanalyzed.
The values for the preparation blank must be recorded in ug/L for
aqueous samples and in mg/Kg for solid samples on FORM III-IN for
ICP, AA, and cyanide analyses.
5. ICP Interference Check Sample (ICS) Analysis
To verify interelement and background correction factors, the
Contractor must analyze and report the results for the ICP Interference
Check Samples at the beginning and end of each analysis run or a
minimum of twice per 8 hour working shift, whichever is more frequent,
but not before Initial Calibration Verification. The ICP Interference
Check Samples must be obtained from EPA (EMSL/LV) if available and
analyzed according to the instructions supplied with the ICS.
A group of samples prepared at the same time.
E-17 ILM02.0
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The Interference Check Samples consist of two solutions: Solution A and
Solution AB. Solution A consists of the interferents, and Solution AB
consists of the analytes mixed with the interferents. An ICS analysis
consists of analyzing both solutions consecutively (starting with
Solution A) for all wavelengths used for each analyte reported by ICP.
Results for the ICP analyses of Solution AB during the analytical runs
must fall within the control limit of ±20% of the true value for the
analytes included in the Interference Check Samples. If not, terminate
the analysis, correct the problem, recalibrate the instrument, and
reanalyze the analytical samples analyzed since the last good ICS. If
true values for analytes contained in the ICS and analyzed by ICP are
not supplied with the ICS, the mean must be determined by initially
analyzing the ICS at least five times repetitively for the particular
analytes. This mean determination must be made during an analytical run
where the results for the previously supplied EPA ICS met all contract
specifications. Additionally, the result of this initial mean
determination is to be used as the true value for the lifetime of that
solution (i.e., until the solution is exhausted).
If the ICP Interference Check Sample is not available from EPA,
independent ICP Check Samples must be prepared with interferent and
analyte concentrations at the levels specified in Table 2-Interferent
and Analyte Elemental Concentrations Used for ICP Interference Check
Sample. The mean value and standard deviation must be established by
initially analyzing the Check Samples at least five times repetitively
for each parameter on FORM IV-IN. Results must fall within the control
limit of +20% of the established mean value. The mean and standard
deviation must be reported in the raw data. Results from the
Interference Check Sample analyses must be recorded on FORM IV-IN for
all ICP parameters.
TABLE 2. INTERFERENT AND ANALYTE ELEMENTAL CONCENTRATIONS USED FOR ICP
INTERFERENCE CHECK SAMPLE
Analytes
(mg/L)
Interferents
(mg/L)
Ag
Ba
Be
Cd
Co
Cr
Cu
Mn
Ni
Pb
V
Zn
1.0
0.5
0.5
1.0
0.5
0.5
0.5
0.5
1.0
1.0
0.5
1.0
A]. 500
Ca 500
F« 200
M{; 500
E-18
ILM02.0
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6. Spike Sample Analysis (S)
The spike sample analysis is designed to provide information about the
effect of the sample matrix on the digestion and measurement
methodology. The spike is added before the digestion (i.e., prior to
the addition of other reagents) and prior to any distillation steps
(i.e., CN-). At least one spike sample analysis must be performed on
each group of samples of a similar matrix type (i.e., water, soil) and
concentration (i.e., low, medium) or for each Sample Delivery Group.
If the spike analysis is performed on the same sample that is chosen
for the duplicate sample analysis, spike calculations must be performed
using the results of the sample designated as the "original sample"
(see section 7, Duplicate Sample Analysis). The average of the
duplicate results cannot be used for the purpose of determining percent
recovery. Samples identified as field blanks cannot be used for spiked
• sample analysis. EFA may require that a specific sample be used for
the spike sample analysis.
The analyte spike must be added in the amount given in Table 3-Spiking
Levels for Spike Sample Analysis, for each element analyzed. Note:
See Table 3 footnotes for concentration levels and applications. If
two analytical methods are used to obtain the reported values for the
same element within a Sample Delivery Group (i.e. ICP, GFAA), spike
samples must be run by each method used.
If the spike recovery is not at or within the limits of 75-125%, the
data of all samples received associated with that spike sample and
determined by the same analytical method must be flagged with the
letter "N" on FORMs I-IN and V-IN. An exception to this rule is
granted in situations where the sample concentration exceeds the spike
concentration by a factor of four or more. In such an event, the data
shall be reported unflagged even if the percent recovery does not meet
the 75-125% recovery criteria.
For flame AA, ICP, and CN analyses, when the pre-digestion/pre-
distillation spike recovery falls outside the control limits and the
sample result does not exceed 4x the spike added, a post-
digestion/post-distillation spike must be performed for those elements
that do not meet the specified criteria (exception: Ag). Spike the
unspiked aliquot of the sample at 2x the indigenous level or 2x CRDL,
whichever is greater. Results of the post-digestion/post-distillation
spike must be reported on FORM V(PART 2)-IN. Note: No post digest
spike is required for Hg.
In the instance where there is more than one spike sample per matrix
and concentration per method per SDG, if one spike sample recovery is
not within contract criteria, flag all the samples of the same matrix,
level, and method in the SDG. Individual component percent recoveries
(%R) are calculated as follows:
2
EPA may require additional spike sample analysis, upon Administrative
Project Officer request, for which the Contractor will be paid.
E-19 ILM02.0
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%Recovery - (SSR-SR) x 100
SA
Where, SSR - Spiked Sample Result
SR - Sample Result
SA - Spike Added
When sample concentration is less than the instrument detection limit,
use SR - 0 only for purposes of calculating % Recovery. The spike
sample results, sample results and % Recovery (positive or negative)
must be reported on FORM V-IN for ICP, AA and cyanide analyses, as
indicated.
The units for reporting spike sample results will be identical to those
used for reporting sample results in FORM I-IN (i.e., ug/L for aqueous
and mg/Kg dry weight basis for solid).
TABLE 3. SPIKING LEVELS FOR SPIKE SAMPLE ANALYSIS
For ICP/AA
For Furnace AA
Other'1''2)
Element
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Water
(ug/L)
2,000
500
2,000
2,000
50
50
*
200
500
250
1,000
500
*
500
500
*
2,000
50
*
2,000
500
500
Soil'2) Water Soil'2)
(mg/kg) (ug/L) (mg/kg)
*
100 100 20
400 40 8
400
10
10 5 1
*
40
100
50
*
100 20 4
*
100
1
100
*
400 10 2
10
*
400 50 10
100
100
ioo'3)
No spike required. NOTE: Elements without spike levels and not
designated with an asterisk, must be spiked at appropriate levels.
Spiking level reported is for both water and soil/sediment matrices.
2
The levels shown indicate concentrations in the final digestate of the
spiked sample (100 mL for mercury and 200 mL for all other metals) when
the wet weight of 1 gram (for ICP, Furnace, and Flame AA), or 0.2 grams
E-20
ILM02.0
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(for mercury) of sample is taken for analysis. Adjustment must be made
to maintain these spiking levels when the weight of sample taken
deviates by more-than 10% of these-values. Appropriate adjustment must
be made for microwave digestion procedure where 0.5 grams of sample or
50.0 mL (45.0 mL of sample plus 5.0 mL of acid) of aqueous sample are
required for analysis.
The level shown indicates the amount of cyanide that must be added to
the original (undistilled) sample. For instance, 100 ug must be added
per each Liter of aqueous sample. If the sample volume is 500 mL, then
50 ug of cyanide must be added. If the volume is 50 mL, then 5 ug of
cyanide must be added.
For soil samples, 25 ug of cyanide must be added per each gram of solid
sample taken for analysis. The spiking level is dependent on the
weight of the sample taken and the final distillate volume. If one
gram of sample is taken for analysis, and the final distillate volume
is 250 mL, then the distillate must contain cyanide at a concentration
of 100 ug/L. If five grams of sample are taken, then the distillate
must contain cyanide at a concentration of 500 ug/L. Assuming a sample
of one gram, the manual and semi-automated colorimetric methods call
for a cyanide concentration of 25 ug per the 500 mL mixture of the
sample, reagents, and water before distillation. The final distillate,
in this case, contains cyanide at a concentration of 100 ug/L. For the
midi-distillation method, a cyanide concentration of 25 ug must be
added into the 50 mL mixture of sample, reagents, and water before
distillation. This yields a cyanide concentration of 500 ug/L in the
final distillate of 50 mL.
7. Duplicate Sample Analysis (D)
One duplicate sample must be analyzed from each group of samples of a
similar matrix type (i.e., water, soil) and concentration (i.e., low,
medium) or for each Sample Delivery Group. Duplicates cannot be
averaged for reporting on FORM I-IN.
Duplicate sample analyses are required for percent solids. Samples
identified as field blanks cannot be used for duplicate sample
analysis. EPA may require that a specific sample be used for duplicate
sample analysis. If two analytical methods are used to obtain the
reported values for the same element for a Sample Delivery Group (i.e.,
ICP, GFAA), duplicate samples must be run by each method used.
The relative percent differences (RPD) for each component are
calculated as follows:
RPD - IS - D| x 100
(S+D)/2
Where, RPD =• Relative Percent Difference
S - First Sample Value (original)
D =• Second Sample Value (duplicate.)
EPA may require additional duplicate sample analyses, upon Administrative
Project Officer request, for which the Contractor will be paid.
E-21 . ILM02.0
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The results of Che duplicate sample analyses must be reported on FORM
VI-IN in ug/L for aqueous samples and mg/Kg dry weight basis for solid
original and duplicate samples. A control limit of 20% for RPD shall
be used for original and duplicate sample values greater than or equal
to 5x CRDL (Exhibit C). A control limit of (±) the CRDL must be used if
either the sample or duplicate value is less than 5x CRDL, and the
absolute value of the control limit (CRDL) must be entered in the
"Control Limit" column on FORM VI-IN.
If one result is above the 5x CRDL level and the other is below, use
the + CRDL criteria. If both sample values are less than the IDL, the
RPD is not calculated on FORM VI-IN. For solid sample or duplicate
results < 5x CRDL, enter the absolute value of the CRDL, corrected for
sample weight and percent solids, in the "Control Limit" column. If
the duplicate sample results are outside the control limits, flag all
the data for samples received associated with that duplicate sample
with an "*" on FORMs I-IN and VI-IN. In the instance where there is
more than one duplicate sample per SDG, if one duplicate result is not
within contract criteria, flag all samples of the same matrix,
concentration, and method in the SDG. The percent difference data will
be used by EPA to evaluate the long-term precision of the methods for
each parameter. Specific control limits for each element will be added
to FORM VI-IN at a later date based on these precision results.
8. Laboratory Control Sample (LCS) Analysis
Aqueous and solid Laboratory Control Samples (LCS) must be analyzed for
each analyte using the same sample preparations, analytical methods and
QA/QC procedures employed for the EPA samples received. The aqueous
LCS solution must be obtained from EPA (if unavailable, the Initial
Calibration Verification Solutions may be used). One aqueous LCS must
be prepared and analyzed for every group of aqueous samples in a Sample
Delivery Group, or for each batch of aqueous samples digested,
whichever is more frequent. An aqueous LCS is not required for mercury
and cyanide analysis.
The EPA-provided solid LCS must be prepared and analyzed using each of
the procedures applied to the solid samples received (exception:
percent solids determination not required). If the EPA solid LCS is
unavailable, other EPA Quality Assurance Check samples or other
certified materials may be used. One solid LCS must be prepared and
analyzed for every group of solid samples in a Sample Delivery Group,
or for each batch of samples digested, whichever is more frequent.
All LCS results and percent recovery (%R) will be reported on FORM VII-
IN. If the percent recovery for the aqueous LCS falls outside the
control limits of 80-120% (exception: Ag and Sb), the analyses must be
terminated, the problem corrected, and the samples associated with that
LCS redigested and reanalyzed.
If the results for the solid LCS fall outside the control limits
established by EPA, the analyses must be terminated, the problem
corrected, and the samples associated with that LCS redigested and
reanalyzed.
E-22 ILM02.0
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9. IGF Serial Dilution Analysis (L)
-Prior to reporting concentration data for the analyte elements, the
Contractor must analyze and report the results of the ICP Serial
Dilution Analysis. The ICP Serial Dilution Analysis must be performed
on a sample from each group of samples of a similar matrix type (i.e.,
water, soil) and concentration (i.e., low, medium) or for each Sample
Delivery Group, whichever is more frequent. Samples identified as
field blanks cannot be used for Serial Dilution Analysis.
If the analyte concentration is sufficiently high (minimally a factor
of 50 above the instrumental detection limit in the original sample),
the serial dilution (a five fold dilution) must then agree within 10%
of the original determination after correction for dilution. If the
dilution analysis for or«= or more analytes is not at or within 10%, a
chemical or physical interference effect must be suspected, and the
data for all affected analytes in the samples received associated with
that serial dilution must be flagged with an "E" on FORM IX-IN and FORM
I-IN.
The percent differences for each component are calculated as follows:
% Difference - ^ ' S* x 100
I
where, I - Initial Sample Result
S - Serial Dilution Result (Instrument Reading x 5)
In the instance where there is more than one serial dilution per SDG,
if one serial dilution result is not within contract criteria, flag all
the samples of the same matrix and concentration in the Sample Delivery
Group. Serial dilution results and "E" flags must be reported on FORM
IX-IN.
10. Instrument Detection Limit (IDL) Determination
Before any field samples are analyzed under this contract, the
instrument detection limits (in ug/L) must be determined for each
instrument used, within 30 days of the start of contract analyses and
at least quarterly (every 3 calendar months), and must meet the levels
specified in Exhibit C.
The Instrument Detection Limits (in ug/L) shall be determined by
multiplying by 3, the average of the standard deviations obtained on
three nonconsecutive days from the analysis of a standard solution
(each analyte in reagent water) at a concentration 3x-5x the instrument
manufacturer's suggested IDL, with seven consecutive measurements per
day. Each measurement must be performed as though it were a separate
analytical sample (i.e., each measurement must be followed by a rinse
and/or any other procedure normally performed between the analysis of
separate samples). IDL's must be determined and reported for each
wavelength used in the analysis of the samples.
E-23 ILM02.0
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The quarterly determined IDL for an instrument must always be used as
the IDL for that instrument during that quarter. If the instrument is
adjusted in anyway that may affect the IDL, the IDL .for that instrument
must be redetermined and the results submitted for use as the
established IDL for that instrument for the remainder of the quarter.
IDLs must be reported for each instrument used on FORM X-IN submitted
with each data package. If multiple AA instruments are used for the
analysis of an element within a Sample Delivery Group, the highest IDL
for the AAs must be used for reporting concentration values for that
Sample Delivery Group. The same reporting procedure must be used for
multiple ICPs.
11. Interelement Corrections for ICP
Before any field samples are analyzed under this contract, the ICP
• interelement correction factors must be determined prior to the start
of contract analyses and at least annually thereafter. Correction
factors for spectral interference due to Al, Ca, Fe, and Mg must be
determined for all ICP instruments at all wavelengths used for each
analyte reported by ICP. Correction factors for spectral interference
due to analytes other than Al, Ca, Fe, and Mg must be reported if they
were applied.
If the instrument was adjusted in anyway that may affect the ICP
interelement correction factors, the factors must be redetermined and
the results submitted for use. Results from interelement correction
factors determination must be reported on FORM XI(PART 1)-IN and FORM
XI(PART 2)-IN for all ICP parameters.
12. Linear Range Analysis (LRA)
For all ICP analyses, a linear range verification check standard must
be analyzed and reported quarterly (every 3 calendar months) for each
element on FORM XII-IN. The standard must be analyzed during a routine
analytical run performed under this contract. The analytically
determined concentration of this standard must be within 5% of the true
value. This concentration is the upper limit of the ICP linear range
beyond which results cannot be reported under this contract without
dilution of the analytical sample.
13. Furnace Atomic Absorption (AA) QC Analyses
Because of the nature of the Furnace AA technique, the special
procedures summarized in Figure 1-Furnace AA Analysis Scheme ("MSA
Tree") will be required for quantitation. (These procedures do not
replace those in Exhibit D of this SOW, but supplement the guidance
provided therein.)
a. All furnace analyses must fall within the calibration range. In
addition, all analyses, except during full methods of standard
addition (MSA), will require duplicate injections. The absorbance
or concentration of each injection must be reported in the raw
data as well as the average absorbance or concentration values and
the relative standard deviation (RSD) or coefficient of variation
E-24 ILM02.0
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(CV). Average concentration values are used for reporting
purposes. The Contractor must be consistent per method and SDG in
choosing absorbance or concentration to evaluate which route is to
be followed in the MSA Tree. The Contractor must also indicate
which of the two is being used if both absorbance and
concentration are reported in the raw data. For MSA analysis, the
absorbance of each injection must be included in the raw data. A
maximum of 10 full sample analyses to a maximum 20 injections may
be performed between each consecutive calibration verifications
and blanks. For concentrations greater than CRDL, the duplicate
injection readings must agree within 20% RSD or CV, or the
analytical sample must be rerun once (i.e., two additional burns).
If the readings are still out, flag the value reported on FORM I-
IN with an "M". The "M" flag is required for the analytical spike
as well as the sample. If the analytical spike for a sample
requires an "M" flag, the flag must be reported on FORM I- IN for
that sample.
b. All furnace analyses for each analytical sample, including those
requiring an "M" flag, will require at least an analytical spike
to determine if the MSA will be required for quantitation. The
analytical spike will be required to be at a concentration (in
the sample) 2x CRDL (except for lead which must be at 20 ug/L).
This requirement for an analytical spike will include the LCS and
the preparation blank. (The LCS must be quantitated from the
calibration curve and corrective action, if needed, taken
accordingly. MSA is not to be performed on the LCS or preparation
blank, regardless of spike recovery results.) If the preparation
blank analytical spike recovery is out of control (85-115%), the
spiking solution must be verified by respiking and rerunning the
preparation blank once. If the preparation blank analytical spike
recovery is still out of control, correct the problem and
reanalyze all analytical samples associated with that blank. An
analytical spike is not required on the pre-digestion spike
sample.
The analytical spike of a sample must be run immediately after
that sample. The percent recovery (%R) of the spike, calculated
by the same formula as Spike Sample Analyses (see item 6, this
section), will then determine how the sample will be quantitated,
as follows:
1) If the spike recovery is less than 40%, the sample must be
diluted and rerun with another spike. Dilute the sample by a
factor of 5 to 10 and rerun. This step must only be
performed once. If after the dilution the spike recovery is
still <40%, report data and flag with an "E" to indicate
interference problems.
Analytical Spikes are post-digestion spikes to be prepared prior to
analysis by adding a known quantity of the analyto to an aliquot of the
digested sample. The unspiked sample aliquot musi: be compensated for any
volume change in the spike samples by addition of deionized water to the
unspiked sample aliquot. The volume of the spiking solution added must
not exceed 10% of the analytical sample volume; this requirement also
applies to MSA spikes.
E-25 ILM02.0
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2) If the spike recovery is greater than or equal to 40% and the
sample absorbance or concentration is less than 50% of the
"spike"5, report the sample results to the IDL. If the spike
recovery is less than 85% or greater than 115%, flag the
result with a "W".
3) If the sample absorbance or concentration is greater than or
equal to 50% of the spike and the spike recovery is at or
between 85% and 115%, the sample must be quantitated directly
from the calibration curve and reported down to the IDL.
4) If the sample absorbance or concentration is greater than or
equal to 50% of the spike and the spike recovery is less than
85% or greater than 115%, the sample must be quantitated by
MSA.
c. The following procedures will be incorporated into MSA analyses.
1) Data from MSA calculations must be within the linear range as
determined by the calibration curve generated at the
beginning of the analytical run.
2) The sample and three spikes must be analyzed consecutively
for MSA quantitation (the "initial" spike run data is
specifically excluded from use in the MSA quantitation).
Only single injections are required for MSA quantitation.
Each full MSA counts as two analytical samples towards
determining 10% QC frequency (i.e., five full MSAs can be
performed between calibration verifications).
3) For analytical runs containing only MSAs, single injections
can be used for QC samples during that run. For instruments
that operate in an MSA mode only, MSA can be used to
determine QC samples during that run.
4) Spikes must be prepared such that:
a) Spike 1 is approximately 50% of the sample concentration.
b) • Spike 2 is approximately 100% of the sample
concentration.
c) Spike 3 is approximately 150% of the sample
concentration.
5) The data for each MSA analysis must be clearly identified in
the raw data documentation (using added concentration as the
x-variable and absorbance as the y-variable) along with the
slope, x-intercept, y-intercept and correlation coefficient
(r) for the least squares fit of the data. The results must
be reported on FORM VIII-IN. Reported values obtained by MSA
"Spike" is defined as [absorbance or concentration of spike sample] minus
[absorbance or concentration of the sample].
E-26 ILM02.0
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must be flagged on the data sheet (FORM I-IN) with the letter
"S" if the correlation coefficient i:> greater than or equal
to 0.995.
6) If the correlation coefficient (r) for a particular analysis
is less than 0.995, the MSA analysis must be repeated once.
If the correlation coefficient is still less than 0.995,
report the results on FORM I-IN from the run with the best
"r" and flag the result with a "+" on FORM VIII-IN and FORM
I-IN.
E-27 ILM02.0
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Figure 1.
Furnace Atomic Absorption Analysis Scheme
Prepare and Analyze
Sample and One Spike
(2 X CRDL)
(Double Injections Required)
I
Analyses Within
Calibration Range
YES
Recovery of Spike
Less Than 40%
NO
Sample Absorbance or
Concentration Less Than
50% of Spike Absorbance or
Concentration
NO
Spike Recovery
Less Than 85% or
Greater Than 115%
I
YES
Quantitate by MSA with 3
Spikes at 50, 100 & 150% of
Sample Concentration
(Only Single Injections Required)
I
NO
If YES, Repeat Only ONCE
If Still YES
NO
YES
Spike Recovery Less Than
85% or Greater than 115%
YES
NO
Correlation Coefficient Less
Than 0.995
If YES, Repeat Only ONCE
NO
If Still YES
Flag Data with "S"
Dilute Sample and Spike
Flag Data with an "E"
Report Results Down to IDL
Report Results Down to IDL.
Flag with a "W
Quantitate from Calibration
Curve and Report Down to
IDL
Flag Data with a "+"
E-28
ILM02.0
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SECTION VI
CONTRACT COMPLIANCE SCREENING
Contract Compliance Screening (CCS) is one aspect of the 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 the Agency.
CCS is performed by the Sample Management Office (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 Regione.1 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.
The Agency may generate a CCS trend report which summarizes CCS results
over a given period of time. The Agency may send the CCS trend report or
discuss the CCS trend report during an On-Site laboratory evaluation. In a
detailed letter to the Technical Project Officer and Administrative Project
Officer, the Contractor shall address the deficiencies and the subsequent
corrective action implemented by the Contractor to correct the deficiencies
within 14 days of receipt of the report or the On-Site laboratory
evaluation. An alternate delivery schedule may be proposed by the
Contractor, but it is the sole decision of the Agency, represented by the
Technical Project Officer or Administrative Project: Officer to approve or
disprove the alternate delivery schedule. If an alternate delivery
schedule is proposed, the Contractor shall describe in a letter to the
Technical Project Officer, Administrative Project Officer, and Contracting
Officer why he/she is unable to meet the delivery schedule listed in this
section. The Technical Project Officer will not grant an extension for
greater than 14 days for the Contractor's response to. the CCS trend report.
If new SOPs are required to be written or SOPs are required to be amended
because of the deficiencies and the subsequent corrective action
implemented by the Contractor, the Contractor shall write/amend and submit
the SOPs per the requirements listed in Exhibit E, Section IV.
If the Contractor fails to adhere to the requirements listed in this
section, the Contractor may expect, but the Agency is not limited to the
following actions: reduction of number of samples sent under the contract,
suspension of sample shipment to the Contractor, da.ta package audit, an On-
Site laboratory evaluation, a remedial performance evaluation sample,
and/or contract sanctions, such as a Cure Notice.
E-29 ILM02.0
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SECTION VII
ANALYTICAL STANDARD REQUIREMENTS
The U.S. Environmental Protection Agency may be uns.ble to supply analytical
reference standards either for direct analytical measurements or for the
purpose of traceability. In these cases, all contract laboratories will be
required to prepare from materials or purchase from private chemical supply
houses those standards necessary to successfully and accurately perform the
analyses required in this protocol.
A. Preparation of Chemical Standards from the Neat High Purity Bulk
Material
If the laboratory cannot obtain analytical reference data from the
USEPA, the laboratory may prepare their own chemical standards.
• Laboratories should obtain the highest purity possible when purchasing
chemical standards; standards purchased at less than 97% purity must be
documented as to why a higher purity could not be obtained.
1. If required by the manufacturer, the chemical standards must be
kept refrigerated when not being used in the preparation of
standard solutions. Proper storage of 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, it
is the contract laboratory's responsibility to have analytical
documentation ascertaining that the purity of each compound is
correctly stated. Purity confirmation, when performed, should use
appropriate techniques. Use of two or more independant 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.
3. Mis-identification of compounds occasionally occurs and it is
possible that a mislabeled compound may be received from a
chemical supply house. It is the contract laboratory's
responsibility to have analytical documentation ascertaining that
all compounds used in the preparation of solution standards be
correctly identified.
4. 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
E-30 ILM02.0
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are to be refrigerated, if required, when not in use. All
solution standards are to be clearly labeled as to the identity of
the analyte or analytes, concentration, date prepared, solvent,
and initials of the preparer.
B. Purchase of chemical standards already in solution
1. Solutions of analytical reference standards can be purchased by
Contractors provided they meet the following criteria:
Laboratories must maintain documentation of the purity
confirmation of the material to verify the integrity of the
standard solutions they purchase.
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 this can be demonstrated is to prepare
and analyze three solutions; a high standard, a low 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. This is done by the
Student's t-test in part "d". If this 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. This is done by the Student's t-test in part e.
Thus the standard is certified to be within 10 percent of the
target concentration.
If the procedure above 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 ten percent greater
than the target standard. This is called the "high
standard". One further aliquot is taken from the second
solution and diluted to a concentration 10 percent less than
the target standard. This 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, 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 + YS + Y4 + Y5 + Y,5 )/6
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Equation 3 992292
VARIANCE - (¥]/ + Y2^ + ¥3 + Y4Z + Y5Z + Yg^ -
(6*MEAN)2)/5
The values Y]_, Y2, ¥3, .... represent the results of the six
analyses of each standard. The means of the low, target, and
high standards are designated M]_, M2, and M3, respectively.
The variances of the low, target, and high standards are
designated V^, V2, and 73, respectively. Additionally, a
pooled variance, Vp, is calculated.
Equation 4
Vp - (V!/(0.81) + V2 + V3 /(1.21))/3
If the square root of Vp is less, than one percent of M2, then
M2 /10,000 is to be used as the value of Vp in all
subsequent calculations.
d. The test statistic must be calculated:
Equation 5
TEST STATISTIC - |(M3 /l.l) - (MX /0.9)|/(Vp /3)°'5
If the test statistic exceeds 2.13 then 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 - (Mi /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 - M]_ ± (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,
then 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.
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In any event, the laboratory is responsible for the quality of the
standards employed for analyses under this contract.
C. 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.
D. Documentation of the Verification and Preparation of Chemical Standards
It is the responsibility of each laboratory to maintain 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, raw data, 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 inspection visits. In those cases where the
documentation is supportive of the analytical results of data packages
sent to EPA, such documentation is to be kept on file by the
laboratories for a period of one year.
Upon request by the Technical Project Officer or Administrative Project
Officer, the Contractor shall submit their most recent previous year's
documentation (12 months) for the verification and preparation of
chemical standards within 14 days of the receipt of request to the
recipients he/she designates.
The Agency may generate a report discussing deficiencies in the
Contractor's documentation for the verification and preparation of
chemical standards or may discuss the deficiencies during an On-Site
laboratory evaluation. In a detailed letter to the Technical Project
Officer, Administrative Project Officer, and EMSL-LV, the Contractor
shall address the deficiencies and the subsequent corrective action
implemented by the Contractor to correct the deficiencies within 14
days of receipt of the report or the On-Site laboratory evaluation. An
alternate delivery schedule may be proposed by the Contractor, but it
is the sole decision of the Agency, represented either by the Technical
Project Officer or Administrative Project Officer, to approve or
disapprove the alternate delivery schedule. If an alternate delivery
schedule is proposed, the Contractor shall describe in a letter to the
Technical Project Officer, Administrative Project Officer, and the
Contracting Officer why he/she is unable to meet the delivery schedule
listed in this section. The Technical Project Officer/Administrative
Project Officer will not grant an extension for greater than 14 days
for the Contractor's response letter to the standards documentation
report. The Contractor shall proceed and not assume that an extension
will be granted until so notified by the TPO and/or APO.
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If new SOPs are required to be written or SOPs are required to be
amended because of the deficiencies and the subsequent corrective
action implemented by the Contractor, the Contractor shall write/amend
and submit the SOPs per the requirements listed in Exhibit E, Section
IV.
If the Contractor fails to adhere to the requirements listed in Section
VII, a Contractor may expect, but the Agency is not limited to the
following actions: reduction of number of samples sent under the
contract, suspension of sample shipment to Contractor, data package
audit, an On-Site laboratory evaluation, a remedial laboratory
evaluation sample, and/or contract sanctions, such as a Cure Notice.
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SECTION VIII
. DATA PACKAGE AUDITS
Data package audits are performed by the Agency for program overview and
specific Regional concerns. Standardized procedures have been established
to assure uniformity of the auditing process. Date, packages are
periodically selected from recently received cases. They are evaluated for
the technical quality of hardcopy raw data, quality assurance, and the
adherence to contractual requirements. This function provides external
monitoring of program QC requirements.
Data package audits are used to assess the technical quality of the data
and evaluate overall laboratory performance. Audits provide the Agency
with an in-depth inspection and evaluation of the Case data package with
regard to achieving QA/QC acceptability. A thoroug;h review of the raw data
is completed including: all instrument readouts used for the sample
results, chromatograms and other documentation for deviations from the
contractual requirements, a check for transcription and calculation errors,
a review of the qualifications of the laboratory personnel involved with
the Case, and a review of all current SOPs on file.
Responding to the data package audit report:
After completion of the data package audit, the Agency may send a copy of
the data package audit report to the Contractor or may discuss the data
package audit report on an On-Site laboratory evaluation. In a detailed
letter to the Technical Project Officer, Administrative Project Officer,
and EMSL/LV, the Contractor shall discuss the corrective actions
implemented to resolve the deficiencies listed in the data package audit
report within 14 days of receipt of the report. An alternate delivery
schedule may be proposed by the Contractor, but it is the sole decision of
the Agency, represented either by the Technical Project Officer or
Administrative Project Officer, to approve or disapprove the alternate
delivery schedule. If an alternate delivery schedule is proposed, the
Contractor shall describe in a letter to the Technical Project Officer,
Administrative Project Officer, and the Contracting Officer, why he/she is
unable to meet the delivery schedule listed in this section. The Technical
Project Officer/Administrative Project Officer will not grant an extension
for greater than 14 days for the Contractor's response letter to the data
package report. The Contractor shall proceed and not assume that an
extension will be granted until so notified by the TPO and/or APO.
If new SOPs are required to be written or SOPs are required to be amended
because of the deficiencies and the subsequent corrective action
implemented by the Contractor, the Contractor shall write/amend and submit
the SOPs per the requirements listed in Exhibit E, Section IV.
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Corrective Actions
If the Contractor fails to adhere to the requirements listed in this
section, the Contractor may expect, but the Agency is not limited to the
following actions: reduction in the numbers of samples sent under the
contract, suspension of sample shipment to the Contractor, an On-Site
laboratory evaluation, data package audit, remedial performance evaluation
sample, and/or contract sanctions, such as a Cure ISfotice.
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SECTION IX
PERFORMANCE EVALUATION SAMPIES
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 these performance evaluation samples (FES) 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 ans.lytes.
Sample sets may be provided to participating Contractors as frequently as
on an 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. The laboratory evaluation samples may be sent either by the
Regional client or the National Program Office, and may be used for
contract action.
Contractors are required to analyze the samples ancl return the data package
and all raw data within the contract required turnaround time.
In addition to PES preparation and analysis, the Contractor will be
responsible for correctly identifying and quantifying the analytes included
in the PES. The Agency will notify the Contractor of unacceptable
performance.
Contractors are required to analyze the samples and return the data package
and all raw data within the contract required turnaround time.
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 Administrative Project Officer,
the Technical Project Officer and EMSL/LV.
An alternate delivery schedule may be proposed by the Contractor, but
it is the sole decision of the Agency, represented either by the
Technical Project Officer or Administrative Project Officer, to approve
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or disapprove the alternate delivery schedule. If an alternate
delivery schedule is proposed, the Contractor shall describe in a
letter to the Technical Project Officer, Administrative Project
Officer, and the Contracting Officer why he/she is unable to meet the
delivery schedule listed in this section. The Technical Project
Officer /Administrative Project Officer will not grant an extension for
greater than 14 days for the Contractor's response letter to the
laboratory evaluation sample report. The Contractor shall proceed and
not assume that an extension will be granted until so notified by the
TPO and/or APO.
If new SOPs are required to be written or SOPs are required to be
amended because of the deficiencies and the subsequent corrective
action implemented by the Contractor, the Contractor shall write/amend
and submit the SOPs per the requirements listed in Exhibit E, Section
IV.
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 National Program Office 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 Administrative Project Officer,
the Technical Project Officer and EMSL/LV.
••;
An alternate delivery schedule may be proposed by the Contractor, but
it is the sole decision of the Agency, represented either by the
Technical Project Officer or Administrative Project Officer, >to approve
or disapprove the alternate delivery schedule. If an alternate
delivery schedule is proposed, the Contractor shall describe in a
letter to the Technical Project Officer, Administrative Project
Officer, and the Contracting Officer why he/she is unable to meet the
delivery schedule listed in this section. The Technical Project
Officer /Administrative Project Officer will not grant an extension for
greater than 14 days for the Contractor's response letter to the
performance evaluation sample report.
If new SOPs are required to be written or SOPs are required to be
amended because of the deficiencies and the subsequent corrective
action implemented by the Contractor, the Contractor shall write/amend
and submit the SOPs per the requirements listed in Exhibit E, Section
IV.
The Contractor shall be notified by the Technical Project Officer or
Administrative Project Officer concerning the remedy for their
unacceptable performance. A Contractor may expect, but the Agency 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 laboratory evaluation, data package audit,
remedial performance evaluation sample, and/or a contract sanction,
such as a Cure Notice.
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Note: A Contractor's prompt response demonstrating that corrective
actions have been taken to ensure the Contractor's capability to meet
contract requirements may facilitate continuation of full sample
delivery.
If the Contractor fails to adhere to the requirements listed in this
section, a Contractor may expect, but the Agency is not limited to the
following actions: reduction in the number of samples sent under the
contract, suspension of sample shipment to the Contractor, an On-Site
laboratory evaluation, data package audit, a remedial laboratory
evaluation sample and/or contract sanctions, such as a Cure Notice.
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SECTION X
ON-SITE LABORATORY EVALUATIONS
At a frequency dictated by a contract laboratory's performance, the
Administrative Project Officer, Technical Project Officer 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: Quality
Assurance Evaluation, and an Evidentiary Audit.
A. Quality Assurance On-Site Evaluation
Quality assurance 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:
o Size and appearance of the facility
o Quantity, age, availability, scheduled maintenance and performance
of instrumentation
o Availability, appropriateness, and utilization of the QAP and 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/data management 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, performance evaluation sample
scores, Regional review of data, Regional QA materials, data audit
reports, results of CCS, and data 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:
1. Procedural Audit
The procedural audit consists of review and examination of actual
standard operating procedures and accompanying documentation for
the following laboratory operations: sample receiving, sample
E-40 ILM02.0
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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 The accuracy of the document inventory
o The completeness of the file
o The 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
Discussion of the On-Site Team's Findings
The quality assurance and evidentiary auditors discuss their findings
with the Administrative Project Officer/Technical Project Officer prior
to debriefing the Contractor. During the debriefing, the auditors
present their findings and recommendations for corrective actions
necessary to the Contractor personnel.
Corrective Action Reports For Follow-Through to Quality Assurance and
Evidentiary Audit Reports
On-site laboratory evaluation:
Following an On-Site laboratory evaluation, quality assurance and/or
evidentiary audit reports which discuss deficiencies found during the
On-Site evaluation may be sent to the Contractor. In a detailed
letter, the Contractor shall discuss the corrective actions implemented
to resolve the deficiencies discussed during the On-Site evaluation and
discussed in the report(s) to the Technical Project Officer,
Administrative Project Officer, and EMSL/LV (response to quality
assurance/technical report) and NEIC (response to the evidentiary
report), within 14 days of receipt of the report. An alternate
delivery schedule may be proposed by the Contractor, but it is the sole
decision of the Agency, represented either by the Technical Project
Officer or Administrative Project Officer, to approve or disapprove the
alternate delivery schedule. If an alternate delivery schedule is
proposed, the Contractor shall describe in a letter to the Technical
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Project Officer, Administrative Project Officer, and the Contracting
Officer why he/she is unable to meet the delivery schedule listed in
this section. The Technical Project .Officer/Administrative Project
Officer will not grant an extension for greater than 14 days for the
Contractor's response letter to the quality assurance and evidentiary
audit report. The Contractor shall proceed and not assume that an
extension will be granted until so notified by the TPO and/or APO.
If new SOPs are required to be written or SOPs are required to be
amended because of the deficiencies and the subsequent corrective
action implemented by the Contractor, the Contractor shall write/amend
and submit the SOPs per the requirements listed in Exhibit E, Section
IV.
Corrective actions
If the Contractor fails to adhere to the requirements listed in this
section, the Contractor may expect, but the Agency is not limited to
the following actions: reduction in the number of samples sent under
the contract, suspension of sample shipment to the Contractor, an On-
Site laboratory evaluation, data package audit, a remedial performance
evaluation sample, and/or contract sanctions, such as a Cure Notice.
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SECTION XI
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 quality control.
Data manually entered from hard-copy 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 resubmittecl must be documented to
allow traceablilty 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 independant of the
source generating the deliverable.
o Change documentation must be retained according to the schedule of the
original deliverable.
o Resubmitted diskettes or other deliverables must be reinspected as a
part of the laboratories' 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.
Lifecycle 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.
o Each version of the production system will be given an identification
number, date of installation, date of last operation and archived.
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o System and operations documentation must be developed and maintained for
each system. Documentation must include a users 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.
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EXHIBIT F
CHAIN-OF-CUSTODY, DOCUMENT CONTROL,
AND STANDARD OPERATING PROCEDURES
F-l ILM02.0
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1. SAMPLE CHAIN-OF-CUSTODY
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, 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 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:
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o Airbills or airbill stickers
o Custody seals
o EPA custody records
o EPA 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 EPA 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.
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2. DOCUMENT 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 analyses. The
following document control procedures have been established to assure
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 which are directly
related to the preparation and analysis of EPA samples shall
become the property of the EPA and shall be placed in the
complete sample delivery group 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 is 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 which 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.
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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 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(s)
shall be placed in the other CSF(s) and the Contractor shall record the
following information on the copy(s) in red ink:
"COPY
ORIGINAL IS FILED IN CSF "
The Contractor shall sign and date this addition to the copy(s).
Before releasing analytical results, the document control officer 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 sample delivery group is 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 sample delivery group, including logbook
pages, bench sheets, mass spectra, chromatograms, screening records,
re-preparation records, re-analysis records, records of failed or
attempted analysis, custody records, library research results, etc.
shall be inventoried.
The Document Control Officer (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.
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2.4 Storage of EPA Files
The Contractor shall maintain EPA laboratory documents in a secure
location.
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 they 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
NEIC/CEAT and the 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.
An 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
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3.2.8 Sample tag ID numbers
3.2.9 Condition of the shipping container
3.2.10 Condition of the sample bottles
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 the 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.
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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
sample delivery group-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.
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 EPA-
designated confidential information from the agency. 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 Document Control Officer (DCO).
4.2 Confidential Information
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 EPA Administrative or Technical
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 EPA Administrative or
Technical 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.
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EXHIBIT G
GLOSSARY OF TERMS
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GLOSSARY OF TERMS
ABSORBANCE - a measure of the decrease in incident light passing through a
sample into the detector. It is defined mathematically as:
A - I(solvent) „ log lo
I(solution) I
Where, I - radiation intensity
ALIQUOT - a measured portion of a field sample taken for analysis.
ANALYSIS DATE/TIME - the date and military time (24-hour clock) of the
introduction of the sample, standard, or blank into the analysis system.
ANALYTE - the element or ion an analysis seeks to determine; the element of
interest.
ANALYTICAL SAMPLE - Any solution or media introduced into an instrument on
which an analysis is performed excluding instrument, calibration, initial
calibration verification, initial calibration blank, continuing calibration
verification and continuing calibration blank. Note the following are all
defined as analytical samples: undiluted and diluted samples (EPA and non-
EPA), predigestion spike samples, duplicate samples, serial dilution
samples, analytical spike samples, post-digestion spike samples,
interference check samples (ICS), CRDL standard for AA (CRA), CRDL standard
for ICP (CRI), laboratory control sample (LCS), preparation blank (PB) and
linear range analysis sample (LRS).
ANALYTICAL SPIKE - The furnace post-digestion spike. The addition of a
known amount of standard after digestion.
AUTOZERO - zeroing the instrument at the proper wavelength. It is
equivalent to running a standard blank with the absorbance set at zero.
AVERAGE INTENSITY - The average of two different injections (exposures).
BACKGROUND CORRECTION - a technique to compensate for variable background
contribution to the instrument signal in the determination of trace
elements.
BATCH - a group of samples prepared at the same time in the same location
using the same method.
CALIBRATION - the establishment of an analytical curve based on the
absorbance, emission intensity, or other measured characteristic of known
standards. The calibration standards must be prepared using the same type
of acid or concentration of acids as used in the sample preparation.
CALIBRATION BLANK - a volume of acidified deionizecl/distilled water.
CALIBRATION STANDARDS - a series of known standard solutions used by the
analyst for calibration of the instrument (i.e., preparation of the
analytical curve).
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CASE - a finite, usually predetermined number of ssjnples 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.
COEFFICIENT OF VARIATION (CV) - the standard deviation as a percent of the
arithmetic mean.
CONCENTRATION LEVEL (low or medium) - for inorganics analysis, low or
medium level is defined by the appropriate designation checked by the
sampler on the Traffic Report.
CONTINUING CALIBRATION - analytical standard run every 10 analytical
samples or every 2 hours, whichever is more frequent, to verify the
calibration of the analytical system.
CONTRACT REQUIRED DETECTION LIMIT (CRDL) - minimum level of detection
acceptable under the contract Statement of Work.
CONTROL LIMITS - a range within which specified measurement results must
fall to be compliant. Control limits may be mandatory, requiring
corrective action if exceeded, or advisory, requiring that noncompliant
data be flagged.
CORRELATION COEFFICIENT - a number (r) which indicates the degree of depen-
dence between two variables (concentration - absorbance). The more
dependent they are the closer the value to one. Determined on the basis of
the least squares line.
DAY - unless otherwise specified, day shall mean calendar day.
DIGESTION LOG - an official record of the sample preparation (digestion).
DISSOLVED METALS - analyte elements which have not been digested prior to
analysis and which will pass through a 0.45 urn filter.
DRY WEIGHT - the weight of a sample based on percent solids. The weight
after drying in an oven.
DUPLICATE - a second aliquot of a sample that is treated the same as the
original sample in order to determine the precision of the method.
FIELD BLANK - any sample submitted from the field identified as a blank.
FIELD SAMPLE - a portion of material received to be analyzed that is
contained in single or multiple containers and identified by a unique EPA
Sample Number.
FLAME ATOMIC ABSORPTION (AA) - atomic absorption which utilizes flame for
excitation.
GRAPHITE FURNACE ATOMIC ABSORPTION (GFAA) - atomic absorption which
utilizes a graphite cell for excitation.
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HOLDING TIME - the elapsed time expressed in days from the date of receipt
of the sample by the Contractor until the date of its analysis.
Holding time — (sample analysis date - sample-, receipt date)
INDEPENDENT STANDARD - a Contractor-prepared standc.rd solution that is
composed of analytes from a different source than those used in the
standards for the initial calibration.
INDUCTIVELY COUPLED PLASMA (ICP) - a technique for the simultaneous or
sequential multi-element determination of elements in solution. The basis
of the method is the measurement of atomic emission by an optical
spectroscopic technique. Characteristic atomic line emission spectra are
produced by excitation of the sample in a radio frequency inductively
coupled plasma.
IN-HOUSE - at the Contractor's facility.
INJECTION - introduction of the analytical sample i.nto the instrument
excitation system for the purpose of measuring absorbance, emission or
concentration of an analyte. May also be referred to as exposure.
INSTRUMENT CALIBRATION - analysis of analytical standards for a series of
different specified concentrations; used to define the quantitative
response, linearity, and dynamic range of the instrument to target
analytes.
INSTRUMENT DETECTION LIMIT (IDL) - determined by multiplying by three the
standard deviation obtained for the analysis of a standard solution (each
analyte in reagent water) at a concentration of 3x-5x IDL on three
noneonsecutive days with seven consecutive measurements per day.
INSTRUMENT CHECK SAMPLE - A solution containing both interfering and
analyte elements of known concentration that can be used to verify
background and interelement correction factors.
INSTRUMENT CHECK STANDARD - a multi-element standard of known
concentrations prepared by the analyst to monitor £.nd verify instrument
performance on a daily basis.
INTERFERENTS - substances which affect the analysis for the element of
interest.
INTERNAL STANDARDS - in-house compounds added at a known concentration.
LABORATORY - synonymous with Contractor as used herein.
LABORATORY CONTROL SAMPLE (LCS) - a control sample of known composition.
Aqueous and solid laboratory control samples are analyzed using the same
sample preparation, reagents, and analytical methods employed for the EPA
samples received.
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LABORATORY RECEIPT DATE - 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. Also referred to as VTSR (validated time of sample
receipt).
LINEAR RANGE, LINEAR DYNAMIC RANGE - the concentration range over which the
ICP analytical curve remains linear.
MATRIX - the predominant material of which the sample to be analyzed is
composed. For the purpose of this SOW, a sample ms.trix is either water or
soil/sediment. Matrix is not synonymous with phase (liquid or solid).
MATRIX MODIFIER - salts used in AA to lessen the effects of chemical
interferents, viscosity, and surface tension.
MATRIX SPIKE - aliquot of a sample (water or soil) fortified (spiked) with
known quantities of specific compounds and subjected to the entire
analytical procedure in order to indicate the appropriateness of the method
for the matrix by measuring recovery.
METHOD OF STANDARD ADDITIONS (MSA) - the addition of 3 increments of a
standard solution (spikes) to sample aliquots of the same size.
Measurements are made on the original and after each addition. The slope,
x-intercept and y-intercept are determined by least-square analysis. The
analyte concentration is determined by the absolute: value of the x-
intercept. Ideally, the spike volume is low relative to the sample volume
(approximately 10% of the volume). Standard additi.on may counteract matrix
effects; it will not counteract spectral effects. Also referred to as
Standard Addition.
PERCENT SOLIDS - the proportion of solid in a soil sample determined by
drying an aliquot of the sample.
PERFORMANCE EVALUATION (PE) SAMPLE - a sample of known composition provided
by EPA for Contractor analysis. Used by EPA to evaluate Contractor
performance.
PREPARATION BLANK (reagent blank, method blank) - s.n analytical control
that contains distilled, deionized water and reagents, which is carried
through the entire analytical procedure (digested s.nd analyzed). An
aqueous method blank is treated with the same reagents as a sample with a
water matrix; A solid method blank is treated with the same reagents as a
soil sample.
PROTOCOL - a compilation of the procedures to be followed with respect to
sample receipt and handling, analytical methods, 6.£.ta reporting and
deliverables, and document control. Used synonymously with Statement of
Work (SOW).
QUALITY CONTROL SAMPLE - a solution obtained from =.n outside source having
known concentration values to be used to verify the; calibration standards.
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REAGENT BLANK - a volume of deionized, distilled Wc.ter containing the same
acid matrix as the calibration standards carried through the entire
analytical scheme.
ROUNDING RULES - If the figure following those to be retained is less than
5, the figure is dropped, and the retained figures are kept unchanged. As
an example, 11.443 is rounded off to 11.44.
If the figure following those to be retained is greater than 5, the figure
is dropped, and the last retained figure is raised by 1. As an example,
11.446 is rounded off to 11.45.
If the figure following those to be retained is 5, and if there are no
figures other than zeros beyond the five, the figure 5 is dropped, and the
last-place figure retained is increased by one if it is an odd number or it
is kept unchanged if an even number. As an example;, 11.435 is rounded off
to 11.44, while 11.425 is rounded off to 11.42.
If a series of multiple operations is to be performed (add, subtract,
divide, multiply), all figures are carried through the calculations. Then
the final answer is rounded to the proper number of significant figures.
See forms instructions (Exhibit B) for exceptions.
RUN - a continuous analytical sequence consisting of prepared samples and
all associated quality assurance measurements as required by the contract
Statement of Work.
SAMPLE DELIVERY GROUP (SDG) - a unit within a sample Case that is used to
identify a group of samples for delivery. An 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 an SDG are due concurrently. A Sample Delivery
Group is defined by one of the following, whichever occurs first:
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 Sample Delivery Groups 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.
SENSITIVITY - the slope of the analytical curve, i.e., functional
relationship between emission intensity and concentration.
SERIAL DILUTION - the dilution of a sample by a factor of five. When
corrected by the dilution factor, the diluted sample must agree with the
original undiluted sample within specified limits. Serial dilution may
reflect the influence of interferents.
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SOIL - synonymous with soil/sediment or sediment as used herein.
STOCK SOLUTION - a standard solution which can be diluted to derive other
standards.
SUSPENDED - those elements which are retained by a 0.45 urn membrane filter.
TOTAL METALS - analyte elements which have been digested prior to analysis.
TRAFFIC REPORT (TR) - an EPA sample identification form filled out by the
sampler, which accompanies the sample during shipment to the laboratory and
which is used for documenting sample condition and receipt by the
laboratory.
WET WEIGHT - the weight of a sample aliquot including moisture (undried).
10% FREQUENCY - a frequency specification during an analytical sequence
allowing for no more than 10 analytical samples between required
calibration verification measurements, as specified by the contract
Statement of Work.
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EXHIBIT H
DATA DICTIONARY AND FORMAT FOR DATA
DELIVERABLES IN COMPUTER-READABLE FORMAT
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AGENCY STANDARD IMPLEMENTATION FOR INORGANICS ILM02.0
1. Format Characteristics
1.1 This constitutes an implementation of the EPA Agency Standard for
Electronic Data Transmission based upon analytical results and ancillary
information required by the contract. All data generated by a single
analysis are grouped together, and the groups are aggregated to produce
files that report data from an SDG. Because this implementation is only
a subset of the Agency Standard, some fields have been replaced by a
series of delimiters as place holders for non-CLP data elements.
1.2 This implementation includes detailed specifications for the required
format of each record. The position in the record where each field is to
be contained relevant to other fields is specified, as well as the
maximum length of the field. Each field's required contents are
specified as literal (contained in quotes) which must appear exactly as
shown (without quotes), or as a variable for which format and/or
descriptions are listed in the format/contents column. Options and
examples are listed for most fields. For fields where more than three
options are available, a list and description of options are supplied on
a separate page following the record descriptions. Fields are separated
from each other by the delimiter "|" (ASCII 124). Fields that do not
contain data should be zero length with the delimiter as place holder.
1.3 Numeric fields may contain numeric digits, a decimal place, and a leading
minus sign. A positive sign is assumed if no negative sign is entered in
a numeric field and must not be entered into any numeric field.
Requirements for significant figures and number of decimal places are
specified in Exhibit B. The numeric field lengths are specified such
that all possible numeric values can be written to the file. The size of
the numeric field indicates the maximum number of digits, decimal, and
negative sign if appropriate that can appear in the field at the same
time. Therefore, the number reported may need to be rounded (using EPA
Rounding Rules) to fit into the field. The rounding must maintain the
greatest significance possible providing the field length limitation. In
addition, the rounded number that appears on the form, and therefore the
field in the diskette file, must be used in any calculation that may
result in other numbers reported on the same form or other forms in the
SDG. Field lengths should only be as long as necessary to contain the
data packing; with blanks is not allowed.
2. Record Types
2.1 The Agency Standard consists of variable length ASCII records. Maximum
field length specifications match the reporting requirements in Exhibit
B. The last two bytes of each record must contain "carriage return" and
"line feed", respectively.
2.2 There are four groups of record types in the reporting format, as shown
below. Detailed record formats follow.
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Type . Type ID Contents
Run Header 10 Information pertinent to a. group of
samples processed in a continuous sequence;
usually several per SDG
Sample Header 20 Sample identifying, qualifying, and linking
information
Results Record 30 Analyte results and qualifications
Comments Record 90 Free form comments
2.3 All record types given are mandatory. Type 10 representing the
analytical run, contains the instrument and run IDs which act as an
identifying label for the run. All 10, 20, 30, and 90 series records
following that record pertain to the same analytical run. Type 20,
representing the sample, contains the EPA Sample ID which acts as an
identifying label for the sample. The QC code indicates whether the data
is from an environmental sample, calibration, or QC sample. All 20, 30,
and 90 series records following that record pertain to the same sample.
Type 30, representing an individual analyte, contains an identifier to
identify the analyte. All 30 series records following that record
pertain to the same analyte.
3. Production Runs
A production run represents a "group" or "batch" of samples that are
processed in a continuous sequence under relatively stable conditions.
Specifically:
Calibration - All samples in a run use the same initial calibration data.
Method - Constant.
Instrument conditions - Constant throughout a run. Results obtained on
different instruments cannot be combined in one run.
Thus, each separate group of analyses on each instrument will consist of
a separate production run, and must be reported in a separate file.
Example of the Sequence of Record Types in a Production Run
10 Contains run header information. Occurs once per run.
16 Contains additional run header information. Occurs once per run.
20 Acts as a header for the following instrument parameters information.
Occurs once per run. EPA SAMPLE NUMBER equals "SIDICF". WAVELENGTH
COUNTER equals the number of the type 32, 34, and 35 groups that follow.
32 Contains integration time information for the wavelength on the type
34 and 35 records that follow. Occurs once for each wavelength used
in the run.
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34 Contains the IDL and Linear range information for the first
wavelength used in the run.
35 Contains the background and interelement correction information for
the first wavelength used in the run.
32 Contains integration time information for the wavelength on the type
34 and 35 records that follow. Occurs once for each wavelength used
in the run.
34 Contains the IDL and Linear range information for second wavelength
used in the run.
35 Contains the background and interelement correction information for
second wavelength used in the run.
32
34
35
Continues as many times as the value of the WAVELENGTH COUNTER on the
previous type 20 record.
20 Contains header information for sample and QC data. Occurs as many times
as there are entries on Form XIV for the run.
21 Contains additional information for analytical and instrument QC samples.
Will always follow type 20 record.
22 Contains additional information for analytical samples. Will usually
follow type 21 record. It is not required for instrument QC samples such
as Instrument Calibration Standards (S), ICV, ICB, CCV, CCB, ICSA, ICSAB,
CRI, and CRA.
30 Contains the sample level concentration, true or added value and QC
value for each analyte. Occurs once for each analytical result for
the EPA Sample Number of the previous type 20 record.
31 Reports any instrumental data necessary to obtain the result reported
on the previous type 30 record. Will always follow type 30 record.
Occurs once per type 30 record.
30 Values for the next analyte wavelength being measured.
31 Values for the next analyte wavelength being measured.
30
31
Continues as many times as the value of the WAVELENGTH COUNTER on the
previous type 20 record.
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20 Next Sample Header record - The following applies to the next sample data.
21
22
30
31
33
30
31 etc.
20
21
22
30
31
etc.
4. Record Sequence
4.1 A Run Header (type 10) record must be present as the first record in the
file. Further occurrences of the type 10 record in the file are not
allowed.
A type 16 record must immediately follow the type 10 record. Further
occurrences of the type 16 record in the file are not allowed.
A type 20 record must immediately follow the type 16 record as a header
for the calculated run-wide instrument parameters (the quarterly and
annual instrument parameters). This is the only occurrence of type 20
record that does not correspond to an actual analysis in the run.
Therefore, the only fields that are not blank in this occurrence of type
20 record are the RECORD TYPE ("20"), EPA SAMPLE NUMBER ("S1DICF"), and
WAVELENGTH COUNT.
A minimum of one group of type 32, 34, and 35 records must immediately
follow the type 20 record. Each group consists of a type 32 record
immediately followed by a type 34 record immediately followed by a type
35 record. The information in each group must pertain to one and only
one analyte's wavelength. The number of groups must be equivalent to the
WAVELENGTH COUNT value and the number of wavelengths used for analysis in
the run. The last group must immediately be followed by the first type
20 record which corresponds to an actual analysis of an instrument
calibration standard. After the appearance of the second type 20 record
in the file, further occurrences of the type 32, 34, and 35 records in
that file are not allowed.
'4.2 Each environmental sample, calibration, or quality control sample is
represented by a group composed of a type 20, 21, and 22 records, which
holds sample level identifying information, followed by a minimum of one
group composed of type 30 and 31 records for each analyte's wavelength.
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The type 20 record holds a count for the number of analyte wavelengths
being used to determine results. The WAVELENGTH COUNTER must have a
value equivalent to the number of type 30 groups associated with each
type 20 record.
Except for the first type 20 record, all type 20 records should occur in
the order of sample analysis. Excluding the first type 20 record, the
number of type 20 records in a file (run) must be equivalent to the
number of entries reported on Form XIV for that run.
4.3 Type 90 comment records may be defined to occupy any position except
before the type 10 (header) record. Comments pertaining to the whole run
such as ones on Cover Page must appear before the first type 20 record.
Comments pertaining to a particular sample such as ones on Form I must
appear after the type 20 record for that sample, but before the first
type 30 record associated with that sample. Comments pertaining to a
particular analyte or wavelength must appear after the type 30 record of
that wavelength, but before the type 30 record of the following
wavelength.
5. File/Record Integrity
All record types must contain the following check fields to ensure file
and record integrity:
Record Field
Position Length Contents Remarks
I
1 First Field 2 Record type or identifier "10" or as appropriate
I
, ( Last Field 5 Record sequence number 00000-99999, repeated as
within file necessary
4 Record checksum Four hexadecimal digits ;
2 Contains CR and LF
The checksum is defined to be the sum of the ASCII representation of the data
on the record up to the Record Sequence Number plus the checksum of the previous
record. The sum is taken modulo 65536 (2 ) and represented as four (4)
hexadecimal digits.
6. Dates and Times
Date or time-of-day information consists of successive groups of one or
two decimal digits, each separated by delimiters. Dates are given in the
order YY MM DD, and times as HH MM. All hours must be given as 0 to 23
using a 24 hour clock and must be local time.
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-7. Multiple Volume Data
There is no requirement under this format that all the data from an
entire sample delivery group fit onto a single diskette. However, each
single production run must fit onto a single diskette if possible.
However, if that is not possible, then it is necessary that all files
start with a type 10 record, and that the multiple type 10 records for
each file of the same production run be identical. If it is necessary to
split the data from a single sample onto multiple diskettes, then the
type 20 and following type records for that sample must be repeated. In
this situation, it is mandatory that columns 7-30, which collectively
identify the sample, be identical in each diskette.
8. Record Listing
The remainder of this section contains detailed specifications for every
record required for a full run.
9. Deliverable
9.1 The file or files must be submitted on a 5-1/4 inch floppy diskette,
which may be either a double-sided, double density, 360 K-byte or a high
capacity 1.2 M-byte, or 3.5 inch double-sided, double-density 720 K-bvte
or 1.44 M-byte. diskette. The diskette must be formatted and recorded
using the MS-DOS Operating System. The diskette or diskettes must
contain all information relevant to one and only one SDG, and must
accompany the hardcopy package for the SDG submitted to the Sample
Management Office (see Exhibit B). Information on the diskette or
diskettes must correspond exactly with information submitted in the
hardcopy data package and on the hardcopy data package forms. Blank or
unused records should not be included on the diskettes.
9.2 Each diskette must be identified with an external label containing (in
this order) the following information:
Disk Density
File Name(s)
Laboratory Name (optional)
Laboratory Code
Case Number (where applicable)
SAS Number (where applicable)
The format for the File Name(s) must be XXXXXX.INY
where XXXXXX is the SDG identifier
I indicates Inorganics analysis
H-6 ILM02.0
-------
N is a continuation number used to identify
multiple files corresponding to the same SDG.
For Format A, "N" must be "1". For Format B, "N"
must be "1" for the only, or first file jf the
SDG, and must be incremented to "2", "3", etc.,
for subsequent files of the SDG. "N" cannot be
greater than 9. If "N" is greater than 9 then
replace Y with a digit to continue incrementing.
The files must be incremented in chronological
order.
Y is "A" for Format A
is "B" for Format B, or a digit (0 to 9) if more
than 9 Format B files are used.
Examples:
Format A ABC123.I1A
Format B ABC123.I1B
ABC123.I2B
ABC123.I3B
ABC123.I9B
ABC123.I10
ABC123.I11
ABC123.I99
Dimensions of the label must be in the range 4-3/4" to 5" long by 1-1/4
to 1-1/2" wide.
H-7 ILM02.0
-------
FORMAT OF THE PRODUCTION RUN FIRST HEADER RECORD (TYPE 10)
MAXIMUM
LENGTH
2
1
2
1
2
1
2
1
2
1
2
1
5
1
8
1
3
1
6
4
11
1
10
2
25
1
2
1
5
4
CONTENTS
RECORD TYPE
Delimiter
ANALYSIS START YEAR
Delimiter
ANALYSIS START MONTH
Delimiter
ANALYSIS START DAY
Delimiter
ANALYSIS START HOUR
Delimiter
ANALYSIS START MINUTE
Delimiter
METHOD TYPE
Delimiter
METHOD NUMBER
Delimiter
MANAGER'S INITIALS
Delimiter
LAB CODE
Delimiter
CONTRACT NUMBER
Delimiter
INSTRUMENT ID
Delimiter
LABORATORY NAME
Delimiter
RUN NUMBER
Delimiter
RECORD SEQUENCE NUMBER
CHECKSUM
FORMAT/CONTENTS
"10"
I
YY
I
MM
I
DD
I
HH
I
MM
CHARACTER1
I
"ILM02.0" (SOW)
I
CHARACTER
I
CHARACTER
MM
CHARACTER
I
CHARACTER
II
CHARACTER
I
NUMERIC
I
NUMERIC
CHARACTER
Method Types are "P"/"F"/"A"/"PM"/"FM17
"AM"/"CV"/"AV"/"C1Y
"CA"/"AS"/"T"
H-8
ILM02.0
-------
FORMAT OF THE PRODUCTION-RUN SECOND HEADER RECORD (TYPE 16)
MAXIMUM
LENGTH
2
1
2
1
2
1
2
1
2
1
2
1
1
1
1
1
1
1
1
1
5
4
CONTENTS
RECORD TYPE
Delimiter
ANALYSIS END YEAR
Delimiter
ANALYSIS END MONTH
Delimiter
ANALYSIS END DAY
Delimiter
ANALYSIS END HOUR
Delimiter
ANALYSIS END MINUTE
Delimiter
AUTO-SAMPLER USED
Delimiter
INTERELEMENT CORRECTIONS APPLIED
Delimiter
BACKGROUND CORRECTIONS APPLIED
Delimiter
RAW DATA GENERATED
Delimiter
RECORD SEQUENCE NUMBER
CHECKSUM
FORMAT/CONTENTS
"16"
I
YY
I
MM
I
DD
I
HH
I
MM
"Y" or "N"1
I ,
"Y" or "Nn/
1 2
"Y" or "N"^
"Y" or "N"3
I
NUMERIC
CHARACTER
Enter "Y" if an auto-sampler is used with equal analysis time and intervals between
analysis.
These are the answers to the first two questions on the Cover Page. "Y" equals "YES",
and "N" equals "NO".
This is the answer to the third question on the Cover Page. "Y" equals "YES", and "B"
equals BLANK.
H-9
ILM02.0
-------
FORMAT FOR THE MANDATORY SAMPLE HEADER DATA RECORD (TYPE 20)
MAXIMUM
LENGTH
2
1
2
1
12
1
5
1
3
1
3
1 -
5
1
6
1
2
1
2
1
2
1
2
1
2
2
2
1
5
1
3
1
5
4
CONTENTS
RECORD TYPE
Delimiter
REGION
Delimiter
EPA SAMPLE NUMBER
Delimiter
MATRIX
Delimiter
QC CODE
Delimiter
SAMPLE QUALIFIER
Delimiter
CASE NUMBER
Delimiter
SDG NUMBER
Delimiter
ANALYSIS YEAR
Delimiter
ANALYSIS MONTH
Delimiter
ANALYSIS DAY
Delimiter
ANALYSIS HOUR
Delimiter
ANALYSIS MINUTE
Delimiter
SAMPLE WT/VOL UNITS
Delimiter
SAMPLE WT/VOL
Delimiter
ANALYTE COUNT
Delimiter
RECORD SEQUENCE NUMBER
CHECKSUM
FORMAT/CONTENTS
"20"
I
NUMERIC
CHARACTER1
1 2
CHARACTER^
I
CHARACTER
CHARACTER
I
CHARACTER
I
CHARACTER
I
YY
MM
I
DD
I
HH
MM
II
,,3
"G"/ "ML
I
NUMERIC
I
NUMERIC
I
NUMERIC
CHARACTER
EPA Sample Number as appears on Form XIV except for the first type 20 record.
type 20 record must have an EPA Sample Number of "SIDICF".
For matrix, "1" equals "WATER", and "F" equals "SOIL".
"G" equals grams, and "ML" equals milliliter.
The first
H-10
ILM02.0
-------
FORMAT OF THE SAMPLE HEADER RECORD (TYPE 21)
MAXIMUM
LENGTH
2
2
3
3
6
I
14
1
2
1
2
1
2
2
2
1
2
1
2
1
9
1
8
1
2
1
5
4
CONTENTS
RECORD TYPE
Delimiter
LEVEL
Delimiter
SAS NUMBER
Delimiter
LAB SAMPLE ID
Delimiter
PREPARATION YEAR
Delimiter
PREPARATION MONTH
Delimiter
PREPARATION DAY
Delimiter
YEAR RECEIVED
Delimiter
MONTH RECEIVED
Delimiter
DAY RECEIVED
Delimiter
COMPOUND SOURCE
Delimiter
INJECTION/ALIQUOT VOLUME
Delimiter
PREPARATION START HOUR
Delimiter
RECORD SEQUENCE NUMBER
CHECKSUM
FORMAT/CONTENTS
"21"
II
"LOW"/"MED"
III
CHARACTER
I
CHARACTER
I
YY
I
MM
I
DD
II
YY
I
MM
I
DD
I
CHARACTER
I
NUMERIC
HH1
I
NUMERIC
CHARACTER
This is the hour at which the preparation is started.
between different batches on the same day.
It is used to differentiate
H-ll
ILM02.0
-------
FORMAT OF THE ASSOCIATED INJECTION AND COUNTER RECORD (TYPE 22)
MAXIMUM
LENGTH CONTENTS FORMAT/CONTENTS
2 RECORD TYPE "22"
10 Delimiter I I I I I I I I I I
8 EXTRACT VOLUME NUMERIC
1 Delimiter |
8 DILUTION FACTOR NUMERIC
3 Delimiter | | |
5 PERCENT SOLIDS NUMERIC
1 Delimiter |
5 RECORD SEQUENCE NUMBER NUMERIC
4 CHECKSUM CHARACTER
H-12 ILM02.0
-------
FORMAT OF THE RESULTS DATA RECORD (TYPE 30)
MAXIMUM
LENGTH
2
1
1
1
9
2
5
1
3
1
10
1
1
1
10
1
1
1
10
1
2
1
10
1
10
1
1
1
10
1
1
1
10
1
1
1
10
1
1
1
10
1
5
4
CONTENTS
RECORD TYPE
Delimiter
ANALYTE IDENTIFIER
Delimiter
ANALYTE CAS NUMBER
Delimiter
CONCENTRATION UNITS
Delimiter
CONCENTRATION QUALIFIER
Delimiter
CONCENTRATION
Delimiter
VALUE DESCRIPTOR
Delimiter
AMOUNT ADDED OR TRUE VALUE
Delimiter
QC VALUE DESCRIPTOR
Delimiter
QC VALUE
Delimiter
QC LIMIT QUALIFIER
Delimiter
QC LOWER LIMIT
Delimiter
QC UPPER LIMIT
Delimiter
IDL LABEL
Delimiter
IDL
Delimiter
RAW DATA AVERAGE QUALIFIER
Delimiter
RAW DATA AVERAGE
Delimiter
RAW DATA %RSD QUALIFIER
Delimiter
RAW DATA %RSD
Delimiter
RAW DATA "MSA-TREE" QUALIFIER
Delimiter
RAW DATA ANALYTICAL SPIKE %R
Delimiter
RECORD SEQUENCE NO.
CHECKSUM
,
"
FORMAT/CONTENTS
"30"
! . - .1
I
CHARACTER
II
"UG/L"/"MG/KG"
1 2
CHARACTER^
I
NUMERIC
nT/"Fn
I
NUMERIC
! . . .
I
NUMERIC
I n n 5
I
NUMERIC
I
NUMERIC
I
"U" for undetected
NUMERIC6
I
NUMERIC
I
"MVBLANK
I
NUMERIC
I
"E"/"W"/BLANK
I
NUMERIC
I
NUMERIC
CHARACTER
H-13
ILM02.0
-------
SAMPLE QC CODES LISTING FOR TYPE 20
OCC
Name
LRB LABORATORY (REAGENT)
BLANK
LCB LABORATORY CALIBRATION
BLANK
Definition
The Preparation or Method Blank (See Exhibit G)
The Initial (ICB) and Continuing Calibration
Blanks (CCB) (See Exhibit G).
LCM LABORATORY CONTROL The Laboratory Control Sample (LCS)
SOLUTION (See Exhibit G).
LD1 LABORATORY DUPLICATE This is the same as the Sample Result "(S)"
FIRST MEMBER that is reported on the Duplicate Form of hardcopy
LD2 LABORATORY DUPLICATE This is the Second aliquot and is identified
SECOND MEMBER as "D" on the Duplicate Form of hardcopy
LVM LABORATORY CALIBRATION See "Continuing Calibration" in Exhibit G.
VERIFICATION SOLUTION Note thate the first Calibration is called the
"Initial Calibration Verification" (ICV),
and those that follow are called the
"Continuing Calibration Verification (CCV).
LIM LABORATORY INTERFERENCE This results of this solution analyses
CHECK SOLUTION are reports on the "Interference Check Sample"
(ICS) Form of hardcopy
LSO LABORATORY SPIKED SAMPLE These values are identified as "Sample Result (SR)"
BACKGROUND (ORIGINAL) on the Spike Sample Recovery Form of Hardcopy.
VALUES
LSF LABORATORY SPIKED SAMPLE- These are the "Spiked Sample Result (SSR)"
FINAL VALUES values on the Spike Sample Recovery Form of hardcopy
LDO LABORATORY DILUTED SAMPLE These Values are the "Initial Sample Result (I)"
SAMPLE BACKGROUND values on the "Serial Dilution" Form of hardcopy
(ORIGINAL) VALUES
LDF LABORATORY DILUTED These are the "Serial Dilution Result(s)"
SAMPLE - FINAL VALUES values on the "Serial Dilution Form of hardcopy.
H-14
ILM02.0
-------
FORMAT OF THE RESULTS DATA RECORD (TYPE 30) FOOTNOTES
"C" (CAS Registry Number) is used for all analytes except cyanide. "I" is used for
cyanide .
"BDL" means below detection limit.
"NSQ" means there is not sufficient quantity to analyze sample according to the
protocol.
"NAI" not analyzed due to interference, "NAR" no analysis result required.
Note that there is no absolute equivalent to the final concentration on Form VIII in
Standard EPA Format.
"LTC" -means less than the CRDL but greater than or equal to the IDL.
"FQC" means failed quality control criteria.
"GTL" means greater than the linear range.
"RIN" means that the analysis result were not used to report data in the SDG. The
results are reported from a later reanalysis of the same sample aliquot.
"REX" means that the analysis result were not used to report data in the SDG. The
results are reported from a later reanalysis of a repreparation of same sample.
Note that, except for "NAR", none of these codes relief the contractor from reporting a
valid result. They only explain why or if the result is qualified.
"T" stands for a true value of the solution. This includes the concentration of all
(ICP as well) instrument calibration standards. "F" stands for an added concentration
to a sample such as a pre or post digestion spike, or MSA additions.
"P" equals percent, "C" equals correlation coefficient, and "L" equals control limit.
"N" equals spiked sample recovery not within control limits, "*" equals duplicate
analysis not within control limits, "+" equals correlation coefficient for the MSA less
than 0.995, "E" equals the estimated reported value because of the presence of
interference. "S" flag is not applicable for Standard EPA Format.
The IDL must be a whole number for all analytes except for mercury. Mercury must be
reported to one decimal place.
"U" means less than the IDL, "B" means less than the CRDL and greater than or equal to
the IDL, "L" means greater than the linear range.
H-15 ILM02.0
-------
FORMAT FOR THE INSTRUMENTAL DATA READOUT (TYPE 31)
MAXIMUM
LENGTH
2
1
1
1
1
2
8
1
10
2
10
2
10
1
5
4
CONTENTS
RECORD TYPE
Delimiter
TYPE OF DATA
Delimiter
TYPE OF VALUE
Delimiter
ANALYTE WAVELENGTH
Delimiter
FIRST INSTRUMENT VALUE
Delimiter
SECOND INSTRUMENT VALUE
Delimiter
THIRD INSTRUMENT VALUE
Delimiter
RECORD SEQUENCE NUMBER
CHECKSUM
FORMAT/CONTENTS
"31"
"W"1
1 2
CHARACTER-*
II
NUMERIC (TO 2 DECIMAL PLACES)
I
NUMERIC
II
NUMERIC
II
NUMERIC
I
NUMERIC
CHARACTER
"W" equals wavelength.
"C" equals concentration in ug/L, "T" equals concentration in ug/250ml, "F" equals
concentration in ug/50 ml, "B" equals absorbance, "I" equals intensity, "A" equals peak
area in cm square, and "H" equals peak height in cm.
This is used to report replicate injections or exposures. If a single instrument
measurement is used, then enter it in the first instrument value field, and leave the
second and third empty. If duplicate instrument measurements are used, then enter them
in the first and second instrument value fields in the order of their analyses, and
leave the third field empty. If triplicate instruments were taken, then enter the
values in the order of their analyses.
H-16
ILM02.0
-------
FORMAT OF THE AUXILLIARY DATA RECORD (TYPE 32)
MAXIMUM
LENGTH CONTENTS • FORMAT/CONTENTS
2 RECORD TYPE "32"
10 Delimiter I I I I I I I I I I
2 INTEGRATION TIME CODE "IT"
1 Delimiter |
10 INTEGRATION TIME IN SECONDS
4 Delimiter ||||
5 RECORD SEQUENCE NUMBER NUMERIC
4 CHECKSUM CHARACTER
H-17 ILM02.0
-------
FORMAT OF THE PC LIMIT RECORD (TYPE 34")
MAXIMUM
LENGTH
2
4
8
1
10
1
10
3
2
1
2
1
2
1
5
4
CONTENTS
RECORD TYPE
Delimiter
ANALYTE WAVELENGTH
Delimiter
CRDL
Delimiter
LINEAR RANGE
Delimiter
YEAR COMPUTED
Delimiter
MONTH COMPUTED
Delimiter
DAY COMPUTED
Delimiter
RECORD SEQUENCE NO.
CHECKSUM
FORMAT/CONTENTS
"34"
MM
NUMERIC
I
NUMERIC
I
NUMERIC
Ml
YY
I
MM
DD
I
NUMERIC
CHARACTER
(TO 2 DECIMAL PLACES)
H-18
ILM02.0
-------
-FORMAT OF THE-CORRECTION DATA.RECORD (TYPE 35)
MAXIMUM
LENGTH
2
1
3
1
5
1
2
1
2
1
2
1
9
1
8
1
10
1
5
4
CONTENTS
RECORD TYPE
Delimiter
TYPE OF CORRECTION
Delimiter
TYPE OF BACKGROUND
Delimiter
YEAR COMPUTED
Delimiter
MONTH COMPUTED
Delimiter
DAY COMPUTED
Delimiter
INTERFERING ANALYTE
Delimiter
ANALYTE WAVELENGTH
Delimiter
CORRECTION FACTOR
Delimiter
RECORD SEQUENCE NO.
CHECKSUM
FORMAT/CONTENTS
"35"
"
I
"BS"/"BD"/"BZ"
I
YY
I
MM
I
DD
I
CHARACTER
I
NUMERIC (TO 2 DECIMAL PLACES)
I
NUMERIC
I
NUMERIC
CHARACTER
"ICP" indicates interelement correction, while "BG" indicates a background correction.
H-19
ILM02.0
-------
FORMAT OF THE COMMENT RECORD (TYPE 90)
MAXIMUM
LENGTH CONTENTS FORMAT/CONTENTS
2 RECORD TYPE "90"
1 Delimiter |
67 ANY COMMENT CHARACTER
1 Delimiter |
5 RECORD SEQUENCE NUMBER NUMERIC
4 CHECKSUM CHARACTER
H-20 ILM02.0
-------
FORMAT OF THE SAMPLE ASSOCIATED DATA RECORD (TYPE 92)
MAXIMUM
LENGTH CONTENTS FORMAT/CONTENTS
2 RECORD TYPE "92"
1 Delimiter |
9 COLOR BEFORE CHARACTER
1 Delimiter |
9 COLOR AFTER CHARACTER
1 Delimiter |
6 CLARITY BEFORE CHARACTER
1 Delimiter |
6 CLARITY AFTER CHARACTER
1 Delimiter |
6 TEXTURE CHARACTER
1 Delimiter |
3 ARTIFACTS "YES"/BLANK
1 Delimiter |
5 RECORD SEQUENCE NUMBER NUMERIC
4 CHECKSUM CHARACTER
H-21 ILM02.0
-------
9. Example of the Sequence of Record Types in a Production Run
10 Contains run header information. Occurs once per run.
16 Contains additional run header information. Occurs once per run.
20 Acts as a header for the following instrument parameters information. Occurs
once per run. EPA SAMPLE NUMBER equals "SIDICF". WAVELENGTH COUNTER equals
the number of the type 32, 34, and 35 groups that follow.
32 Contains integration time information for the wavelength on the type 34
and 35 records that follow. Occurs once for each wavelength used in the
run.
34 Contains the IDL and Linear range information for the first wavelength
used in the run.
35 Contains the background and interelement correction information for the
first wavelength used in the run.
32 Contains integration time information for the wavelength on the type 34
and 35 records that follow. Occurs once for each wavelength used in the
run.
34 Contains the IDL and Linear range information for second wavelength used
in the run.
35 Contains the background and interelement correction information for
second wavelength used in the run.
32
34
35
Continues as many times as the value of the WAVELENGTH COUNTER on the
previous type 20 record.
20 Contains header information for sample and QC data. Occurs as many times as
there are entries on Form XIV for the run.
21 Contains additional information for analytical and instrument QC samples.
Will always follow type 20 record.
22 Contains additional information for analytical samples. Will usually follow
type 21 record. It is not required for instrument QC samples such as
Instrument Calibration Standards (S), ICV, ICB, CCV, CCB, ICSA, ICSAB, CRI,
and CRA.
28 Contains additional information for analytical samples. Will usually follow
type 22 record. It is not required for instrument QC samples such as
Instrument Calibration Standards (S), ICV, ICB, CCV, CCB, ICSA, ICSAB, CRI,
and CRA.
30 Contains the sample level concentration, true or added value and QC
value for each analyte. Occurs once for each analytical result for the
EPA Sample Number of the previous type 20 record.
31 Reports any instrumental data necessary to obtain the result reported on
the previous type 30 record. Will always follow type 30 record. Occurs
once per type 30 record.
H-22 ILM02.0
-------
33 Reports the average of-instrumental data, instrument related qualifier,
and the QC limits and qualifier for the QC VALUE reported on previous
type 30 record. Will always follow type 31 record. Occurs once per
type 30 record.
30 Values for the next analyte wavelength being measured.
31 Values for the next analyte wavelength being measured.
33 Values for the next analyte wavelength being measured.
30
31
33
Continues as many times as the value of the WAVELENGTH COUNTER on the
previous type 20 record.
20 Next Sample Header record - The following applies to the next sample data.
21
22
28
30
31
33
30
31
33 etc.
20
21
22
28
30
31
32
etc.
H-23 ILM02.0
------- |