R
EPA-540A
94-094
United States Office of Publication 9240.1 -12
Environmental Protection Solid Waste and EPA/540/R/94/094
Agency Emergency Response ^B95-963515
December 1994
Superfund
&EFA USEPA CONTRACT
LABORATORY PROGRAM
STATEMENT OF WORK
FOR INORGANICS ANALYSIS
MULTI-MEDIA,
MULTI-CONCENTRATION
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9240.1-12
PB95-963515
EPA540/R-94/094
USEPA CONTRACT LABORATORY PROGRAM
STATEMENT OF WORK
FOR
INORGANICS ANALYSIS
Multi-Media
Multi- Concentration
Document Number ILM01.0
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ATTACHMENT A
STATEMENT OF WORK
TABLE OF CONTENTS
EXHIBIT A: SUMMARY OF REQUIREMENTS
EXHIBIT B: REPORTING AND DELIVERABLES REQUIREMENTS
EXHIBIT C: INORGANIC TARGET ANALYTE LIST
EXHIBIT D: ANALYTICAL METHODS
EXHIBIT E: QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
EXHIBIT F: CHAIN-OF-CUSTODY, DOCUMENT CONTROL AND STANDARD OPERATING
PROCEDURES
EXHIBIT G: GLOSSARY OF TERMS
EXHIBIT H: DATA DICTIONARY AND FORMAT FOR DATA DELIVERABLES IN COMPUTER -
READABLE FORMAT
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EXHIBIT A
NUMMARY OF REQUIREMENTS
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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 quantitation 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.
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.
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.
Prior to accepting any samples from the Agency, the Contractor shall have,
in house, the appropriate standards for all target analytes listed in
Exhibit C.
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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 paragraphs 2., 3. and 4.,
following. 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;
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and cyanide analysis. The identification and quantitation of
analytes other than cyanide shall be accomplished using the ICP or
AA methods specified in Exhibit D, whichever method will achieve
the Contract Required Detection Limit (CRDL) 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., 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 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) 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 Co assure that the operating parameters of the analytical
instrumentation and analytical procedures from sample receipt
through identification and quantitation produce reliable data.
The Contractor must analyze the LCS concurrently with the analysis
of the samples in the SDG.
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.
1. Use of formats other than those 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) provide^ that the forms are in EXACT EP«. 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
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 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.
J. The Contractor shall provide analytical equipment and technical
expertise for this contract as specified 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
perform these functions. The EPA reserves the right to review
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personnel qualifications and experience. See Section III, Detailed
Technical & Management Requirements.
1. 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 in a timely manner (within 7 days of the
originator's request) to requests from data recipients for additional
information or explanations that result from the Government's
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 stored 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
proc'ess 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 laboratory conditions that affect the timeliness of
analyses and data reporting. In particular, the Contractor shall
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
area over a finite time period, and will include one or more field
samples with associated blanks. Samples may be shipped to the
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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 Group(s). A Sample Delivery Group (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 (said period beginning with the receipt of
the first sample in the Sample Delivery Group).
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 a Sample Delivery Group must be submitted
together (in one package) in the order specified in Exhibit B. The
Sample Delivery Group 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 Sample Delivery
Group as samples are received, through proper sample documentation (see
Exhibit B) and communication with SMO personnel.
J. 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 QC 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 3 calendar days
following receipt of the last sample in the Sample Delivery Group.
Traffic Reports shall be submitted in Sample Delivery Group sets (i.e.,
all Traffic Reports for a Sample Delivery Group shall be clipped
together) with an SDG Cover Sheet containing information regarding the
Sample Delivery Group, as specified in Exhibit B.
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.
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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 SMO, 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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PERSONNEL REQUIREMENTS
I. TECHNICAL CAPABILITY
A. Technical Supervisory 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 discipline.
(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 conditions of the EPA contract.
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 quality
controlling automated deliverables to meet all terms and
conditions of the EPA contract.
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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 quality controlling 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.
(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 Spectroscopy.
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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 educational 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.
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
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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.
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. Samples and
standards must be stored separately.
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D.
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.
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. 200 Samples/Month Capacity Requirements
Fraction
ICP Metals
GFAA Metals
1
1
Mercury
Cyanide
No. of
Instrument(s)
1
2
2
12 distillation
units + 1
photometer
1
Type of |
Instrument |
1
ICP Emission
Spec tropho tome ter
Atomic Absorption
Spec tropho tome ter
with Graphite
Furnace Atomizer
Mercury Cold Vapor
AA Analyzer or AA
instrument
modified for Cold
Vapor Analysis
See Cyanide
Methods, Staterhent
of Work Exhibit D,
Section IV, Part E
There are no Secondary Instrument Requirements for 200 Samples/Month
Capacity.
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2. 300 Samples/Month Capacity Requirements
Fraction
ICP Metals
GFAA Metals
Mercury
Cyanide
No. of
Instrument(s)
1
3
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
Secondary Instrument Requirements for 300 Samples/Month Capacity
The Contractor shall have the following instruments in place
and operational at any one 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 IBM 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-bytes.
Modem capable of at least 2,400 baud transmission speed
which is compatible with the EPA Telecommunications
Network.
? Software - Software, utilized in generating, updating and
quality controlling analytical databases and automated
deliverables shall have the following additional
capabilities:
Editing and updating databases.
QC of automated deliverables.
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 be 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. Data Reporting and Delivery Officer
Responsible for all aspects of data deliverables: organization,
packaging, copying, and delivery.
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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-L5
SECTION IV: Data Reporting Forms B-42
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SECTION I
CONTRACT REPORTS/DELIVERABLES DISTRIBUTION
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.
Delivery
| Distribution
Item
A. Updated SOPs
B. Sample Traffic
Reports
**C. Sample Data
Package
D. Data in Computer
Readable Format
****£. Complete SDG File
*F. Quarterly/ Annual
Verification
of Instrument
Parameters
*****G . Qua 1 i ty
Assurance
Plan
Copies
2
1
2
1
1
2
t
copy
Schedule
45 days after
contract receipt
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
January, April
July, October
Submit copy
within 7 days
of written
request by APO
(D
X
X
X
X
Ai
(2)
1
X
X
» direct
(3)
X
X
X
;ed
Distribution:
(1) Sample Management Office (SMO)
(2) Region-Client
(3) Environmental Monitoring Systems Laboratory (EMSL)
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* 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 and not exceeding 20
samples. Data for all samples in the SDG are due concurrently.
(See SOW Exhibit A, paragraph I., 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)
944 E. Harmon Avenue
Las Vegas, NV 89109
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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
o Legible,
o Clearly labeled and completed in accordance with instructions in
this Exhibit,
o Arranged in the order specified in this Section,
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 APO/TPO action, the
data must be clearly marked as ADDITIONAL DATA and must be sent to all three
contractual data recipients (SMO, EMSL, 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 and Region), and in
.11 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.
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 ILM01.0
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A. Updated SOPs
The Contractor shall submit updated copies of all required Standard
Operating Procedures (SOPs) that were submitted with the prebid
Performance Evaluation sample results. The updated SOPs must address
any and all issues of laboratory performance and operation identified
through the review of the Performance Evaluation sample data and the
evaluation of Bidder-Supplied Documentation.
The Contractor must supply SOPs for the following:
1. Sample receipt and logging.
2. Sample storage.
3. Preventing sample contamination.
4. Security for laboratory and samples.
5. Standards purity/preparation.
6. Maintaining instrument records and logbooks.
7. Sample analysis and data control systems.
8. Glassware cleaning.
9. Technical and managerial review of laboratory operation and
data package preparation.
10. Internal review of contractually-required quality assurance and
quality control data for each individual data package.
11. Sample analysis, data handling and reporting.
12. Chain-of-custody procedures and document control including SDG
file preparation
13. Sample data validation/Self-inspection system
a. Data flow and chain-of-command for data review
b. Procedures for measuring precision and accuracy
c. Evaluation parameters for identifying systematic errors
d. Procedures to assure that hardcopy and diskette
j deliverables are complete and compliant with the
requirements in Exhibits B and H
e. Procedures to assure that hardcopy deliverables are in
agreement with their comparable diskette deliverables
B-5 ILM01.0
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f. Demonstration of internal QA inspection procedure
(demonstrated by supervisory sign-off on personal
notebooks, etc.)
g. Frequency and type of internal audits (e.g., random,
quarterly, spot checks, perceived trouble areas)
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.
14. Data Management and Handling
a. Procedures for controlling and estimating data entry
errors.
b. Procedures for reviewing changes to data and deliverables
and enduring 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. Individual(s) responsible for system operation,
maintenance, data integrity and security.
g. Specifications for staff training procedures.
B. Sample Traffic Reports
Original Sample Traffic Report page marked "Lab Copy for Return to SMO"
with lab receipt information and signed in 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
B-6 ILM01.0
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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 or last SDG
shipment, the "first" sample received would be the lowest sample number
(considering both alpha and numeric designations); the "last" sample
received would be 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.
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.
B-7 ILM01.0
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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 resolution.
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 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 Form I 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 Linear Range Analysis for ICP
[FORM II (PART 2) - IN]
B-8 ILM01.0
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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 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.
B-9 ILM01.0
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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, 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.
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
B-10 ILM01.0
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for initial and continuing calibration verification and
blanks, as well as interference check samples and 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.
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
data 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
mailer.
B-ll ILM01.0
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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.
B-12 ILM01.0
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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.
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 Section 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 Section 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.
B-13 ILM01.0
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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.
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.
a. 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 ran^e 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.
B-14 ILM01.0
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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 Jor 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-15 ILM01.0
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A. General Information and Header Information
The data reporting forms presented of 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 the Data
Dictionary (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 muse
be filled out completely for all analytes before proceeding to the next
form of the same type. Multiple forms cannot be submitted 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
ALL UPPERCASE letters (i.e., "LOU", 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 more detailed
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.
B-16 ILM01.0
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This lab code shall be assigned by EPA at Che time a contract is
awarded, and must not be modified by the Contractor, except at the
direction of EPA.
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 prder 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 Exhibit
B and Exhibit 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
B-17 ILM01.0
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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:
Raw Data Result Specified Format Correct Entry on Form
95.99653
95.99653
95.99653
95.996
95.9
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)
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 equals 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 Paee - 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 "3/90" 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, MAC111, MAllll, MA1111D, etc.
B-18 ILM01.0
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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.
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 associateu 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).
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.
B-19 ILM01.0
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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.
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:
"P" 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 spectrophotometric.
"AS" for Semi-Automated Spectrophotometric
"C" for Manual Spectrophotometric
"T" for Titrimetric
" " where no data has been entered.
"N"R" 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.
B-20 ILM01.0
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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)
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.
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 1QO (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
B-21 ILM01.0
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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.
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) xlOQ (22)
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 IIA and moving from the left to the right continuing to the
following Form IIA's as appropriate. For instance, the first ICV for
B-22 ILM01.0
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all analytes must be reported on the first Form IIA. In a run where
three CCVs were analyzed, the first CCV must be reported in the left CCV
column on the first Form IIA 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 IIA. 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.
E. 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:
%R = Found CRDL Standard for AA IQQ /o 3-)
True CRDL Standard for AA
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 Solution 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 -^QQ ,~ ,-.
CRDL Standard for ICP True
B-23 ILM01.0
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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 10Q /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.
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 IIB's 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 prodeeding to the next
wavelength.
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" 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
B-24 ILM01.0
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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 I", 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 CCB's 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.
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
HI and moving from left to right and continuing to the following Form
IIIls 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).
B-25 ILM01.0
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Under "True Sol. A", enter Che 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:
%R = Initial Found Solution AB -,QQ (2 61
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 -^QQ (27)
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
B-26 ILM01.0
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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 prodeeding 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.
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
B-27 ILM01.0
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%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 Spike 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.
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.
B-28 ILM01.0
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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, preceding.
%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.
For "% Solids for Sample," enter to 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 less than the CRDL or 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.
B-29 ILM01.0
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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:
RPD - * S ' D * x 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.
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, complete 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.
B-30 ILM01.0
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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 ^ IQQ (2 1Q)
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", er^er 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 ^ IQQ (2
Solid LCS True
The values for true and found aqueous and solid LCS's 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.
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
B-31 ILM01.0
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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.
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
s amp1e.
B-32 ILM01.0
-------
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 £ ^i - I xi X y±
r _ (2.13)
(N £ Xi2 - ( £ x^2]14 [N I Yi2 - ( I yi)2]h
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. TCP Serial Dilution [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.
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:
B-33 ILM01.0
-------
% Difference - \ I - S \ x 100 (2.14)
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.
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".
B-34 ILM01.0
-------
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. Except for
Mercury, the instrument detection limit must be rounded to a whole
number.
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.
0. ICP Interelement Correction Factors (Annually) [FORM XI(PART 1)-IN]
This form documents for each ICP instrument tha i: rerelement 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.
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 muse be entered
for that analyte to indicate that the corrections were determined to be
B-35 ILM01.0
-------
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
ins trument.
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.
B-36 ILM01.0
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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, LCS's, PB's 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 Pajt 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.
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.
B-37 ILM01.0
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S. Analysis Run Log [Form XIV-IN]
This Form is used Co 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.
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 t:o the next Form
XIV for the instrument run if applicable. The analysis date and time of
B-38 ILM01.0
-------
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.
Under "Analytes", enter "X" in the column of the designated analyte to
indicate that the analyte value was used from the reported analysis to
B-39 ILM01.0
-------
report.data in Che SDG. Leave Che column empty for each analyce 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 inspection 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 complete 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 date 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 the SMO and
document the contact as well as resolution of the problem on a CLP
B-40 ILM01.0
-------
Communication Log. Following resolution, sign and date the forms as
specified in the preceding paragraph and note, where appropriate, the
resolution of the problem.
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 and 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 Section 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.
B-41 ILM01.0
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SECTION IV
DATA REPORTING FORMS
B-42 ILM01.0
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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
3/90
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U.S. EPA - CLP
EPA SAMPLE NO.
Lab Name:
Lab Code:
INORGANIC ANALYSIS DATA SHEET
Contract:
Case No.:
SAS No.:
SDG No.:
Matrix (soil/water):
Level (low/med):
% Solids:
Lab Sample ID:
Date Received:
Concentration Units (ug/L or rag/kg dry weight):
Color Before:
Color After:
Comments:
CAS No.
7429-90-5
7440-36-0
7440-38-2
7440-39-3
7440-41-7
7440-43-9
7440-70-2
7440-47-3
7440-48-4
7440-50-8
7439-89-6
7439-92-1
7439-95-4
7439-96-5
7439-97-6
7440-02-0
7440-09-7
7782-49-2
7440-22-4
7440-23-5
7440-28-0
7440-62-2
7440-66-6
1
| Analyte
1
| Aluminum
| Antimony
| Arsenic
| Barium
| Beryllium
| Cadmium
| Calcium
| Chromium
| Cobalt
| Copper
(Iron
[Lead
(Magnesium
| Manganese
| Mercury
| Nickel
[Potassium
| Selenium
| Silver
| Sodium
(Thallium
| Vanadium
| Zinc
| Cyanide
1
Concentration
M
Clarity Before:
Clarity After:
Texture:
Artifacts:
FORM I - IN
3/90
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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
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
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
3/90
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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
| Iron
|Lead
Magnesium
Manganese
| Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
CRL.,., S
True
tandard fc
Found
r AA
%R
True
CRDL Standard for ICP
Initial Final
Found %R Found %R
FORM II (PART 2} - IN
3/90
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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
|:iagnesium
Manganese
I Mercury
I Nickel
| Potassium
I Selenium
I Silver
| Sodium
[Thallium
Initial
Calib.,
Blank
(ug/L) C
[ Vanadium |
Zinc
| Cyanide
—
—
~
Continuing Calibration
Blank (ug/L)
1 C 2 C 3 C
~
~
Prepa-
ration
Blank C
—
—
M
—
FORM III - IN
3/90
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U.S. EPA - CLP
ICP INTERFERENCE CHECK SAMPLE
Lab Name:
Lab Code:
ICP ID Number:
Case No.
Contract:
SAS No.:
ICS Source:
SDG No.:
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
| Zinc
1
Ti
Sol.
A
rue
Sol.
AB
Initial Found
Sol. Sol.
A AB %R
Final Found
Sol. Sol.
A AB
FORM IV - IN
3/90
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U.S. EPA - CLP
Lab Name:
Lab Code:
5A
SPIKE SAMPLE RECOVERY
Contract:
EPA SAMPLE NO.
Case No.:
SAS No.:
SDG No.:
Matrix (soil/water):
% Solids for Sample:
Level (low/med):
Concentration Units (ug/L or mg/kg dry weight):
I
1
1
| Analyte
1
| Aluminum
| Antimony
| Arsenic
| Barium
| Beryllium
I Cadmium
| Calcium
| Chromium
I 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)
C
Sample
Result (SR)
C
Spike
Added (SA)
%R
Q
M
Comments:
FORM V (PART 1) - IN
3/90
-------
U.S. EPA - CLP
5B
POST DIGEST SPIKE SAMPLE RECOVERY
EPA SAMPLE NO.
I
Lab Name:
Lab Code:
Matrix (soil/water):
Contract:
Case No.:
SAS No.:
SDG No.:
Level (low/med):
Concentration Units: ug/L
1
1
1
I Analyte
1
| Aluminum
| Antimony
I Arsenic
I Barium
| Beryllium
| Cadmium
I Calcium
I Chromium
I Cobalt
| Copper
| Iron
j Lead
I Magnesium
| Manganese
I Mercury
I Nickel
I Potassium
I Selenium
I Silver
1 Sodium
1 Thallium
I Vanadium
I Zinc
I Cyanide
1
Control
Limit
%R
Spiked Sample
Result (SSR)
C|
Sample
Result (SR) C|
Spike
Added (SA)
%R
Q
_l
M
Comments:
FORM V (PART 2) - IN
3/90
-------
U.S. EPA - CLP
DUPLICATES
EPA SAMPLE NO,
r
Lab Name:
Lab Code:
Contract:
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
j Arsenic
| Barium
| Beryllium
| Cadmium
| Calcium
| Chromium
| Cobalt
| Copper
| Iron
|Lead
| Magnesium
| Manganese
| Mercury
| Nickel
| Potassium
| Selenium
(silver
| Sodium
| Thallium
j Vanadium
| Zinc
| Cyanide
1
Control
Limit
Sample (S)
C
Duplicate (D)
C
1
1
RPD
*
Q
1
M
FORM VI - IN
3/90
-------
Lab Name:
Lab Code:
U.S. EPA - CLP
LABORATORY CONTROL SAMPLE
Contract:
SAS No.:
Case No.:
SDG No.
Solid LCS Source:
Aqueous LCS Source:
1
1
| Analyte
1
| Aluminum
| Antimony
| Arsenic
| Barium
| Beryllium
j Cadmium
| Calcium
| Chromium
I Cobalt
| Copper
llron
1 Lead
| Magnesium
j Manganese
j Mercury
| Nickel
| Potassium
j Selenium
| Silver
\ Sodium
| Thallium_
j Vanadium_
| Zinc
| Cyanide
1
Aqueous (ug/L)
True Found %R
Sol
True Found
Solid (mg/kg)
C Limits
%R
FORM VII - IN
3/90
-------
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
1
Final
Cone.
-
1
!
r
1
Q
-
"
—
FORM VIII - IN
3/90
-------
Lab Name:
Lab Code:
U.S. EPA - CLP
ICP SERIAL DILUTIONS
Contract:
EPA SAMPLE NO.
Case No.:
SAS No.:
SDG No.:
Matrix (soil/water):
Level (low/med):
Concentration Units: ug/L
1
1
I Analyte
1
| Aluminum
| Antimony
{Arsenic
| Barium
1 Beryllium
| Cadmium
| Calcium
| Chromium
| 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
1
1
1
1
1
I
1
1
i
Q
M
1
FORM IX - IN
3/90
-------
Lab Name:
Lab Code:
ICP ID Number:
Flame AA ID Number:
Furnace AA ID Number:
U.S. EPA - CLP
10
INSTRUMENT DETECTION LIMITS (QUARTERLY)
Contract:
SAS No.:
Date:
Case No.
SDG No.
Comments:
1
1
I
| Analyte
1
| Aluminum
| Antimony
(Arsenic
| Barium
| Beryllium
| Cadmium
j Calcium
| Chromium
| Cobalt
| Copper
| Iron
|Lead
| Magnesium
| Manganese
| Mercury
j Nickel
| Potassium
| Selenium
| Silver
| Sodium
| Thallium
! Vanadium
| Zinc
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
FORM X - IN
3/90
-------
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.
Analyte
Aluminum
Antimony-
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnes ium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Wave-
length
(nm)
Ii
Al
rterelement
Ca
Correction
Fe
Factors foi
Mg
-
<• *
Comments:
FORM XI (PART 1) - IN
3/90
-------
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
| Analyte
1
| Aluminum
| Antimony
| Arsenic
| Barium
| Beryllium
| Cadmium
j Calcium
[ Chromium
I Cobalt
| Copper
| Iron
(Lead
[Magnesium
| Manganese
| Mercury
| Nickel
| Potassium
| S- lenium
[Silver
| Sodium
| Thallium
| Vanadium
| Zinc
1
Wave-
length
(nm)
Interelement Correction Factors for:
-
Comments:
FORM XI (PART 2) - IN
3/90
-------
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
1 Cadmium
| Calcium
| Chromium
| Cobalt
| Copper
llron
[Lead
(Magnesium
| Manganese
| Mercury
| Nickel
| Potassium
| Selenium
| Silver
| Sodium
| Thallium
| Vanadium
| Zinc
1
Integ.
Time
(Sec.)
Concentration
(ug/L)
M
Comments:
FORM XII - IN
3/90
-------
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
3/90
-------
U.S. EPA - CLP
14
ANALYSIS RUN LOG
Lab Name:
Lab Code
•
*
Case No.
i
Instrument ID Number:
Start Date:
EPA
Sample
No.
D/F
Time
% R
Contract
SAS No. :
Method:
End Date
»
i
SDG No. :
Analytes
A
L
s
B
|A
s
IB
|A
B
E
1C
D
1C
A
c
R
1C
o
c
u
F
E
P
B
M
G
|M
N
H
G
|N
I
K
.
IS
E
,
A
G
N T V
A L|
!
z c
N N
1
FORM XIV - IN
3/90
-------
U.S. EPA - CLP
14
ANALYSIS RUN LOG
Lab Name
: Contract:
Lab Code:
Case No . :
Instrument ID Number:
Start Date :
EPA
Sample
No.
D/F
1
1
Time
% R
SAS No.:
SDG No. :
Method:
End Date:
Analytes
A S
L|B
|A
S
IB
IA
1
B
IE
1C
D
1C
|A
.
C
IR
1C
10
1C
|U
IF
IE
P
B
|M
G
|M
N
|H
IG
N
I
K
IS
E
|A
IG
IN
IA
IT
IL
IV
1
12
IN
c
N
FORM XIV - IN
3/90
-------
SAMPLE LOG-IN SHEET
*,
Lab Name: P«RC of
Received BY (Print Nome): I ng-in n««r-
Reccived By (Signature):
Case Number:
Sample Delivery
Group No.:
SAS Number:
REMARKS:
1. Custody Seal(s) Present/Absent*
Intact/Broken
2 Custody Seal Notr
3. Caaim-of-Custody Present/Absent*
4. TruCfic Reports or Present/Absent'
Piciing Lift
: 5. AiibOl Aiibill/Sucter
i Prcsent/Abicol*
•: 6. AiifcOI No-
I 7. Simple T«gs Presea(/Absait*
: S«apIcT«c Listed/Not Listod
=. Numbers oa Ch«in-of-
< Custody
7 g. S^coplr Condiuon: Intact/Broken*/
Leaking
9. Does iafocmaboa oa
icpotte. «ad cample
• 10. DaleRecetvolatLab:
1 1. Tune Received:
Sample Transfer
Arcmft
By:
Oo:
EPA
SAMPLE
#
—
CORRESPONDING
SAMPLE
TAG
#
ASSIGNED
LAB
ff
REMARKS:
CONDITION
OF SAMPLE
SHIPMENT. ETC.
-
* CocUAd SMO wd >cuch irxxxxi of rcsoJoxioa
Rcvic-wed By: _
D«lc:
Logbook No.:
Logbook P«gc No:
TORMOC-J
3/90
-------
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 Secti'on 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 3/90
-------
Page Nos.
From To
(Please Check:)
Lab Region
23.
24.
25.
26.
27.
28.
29.
30.
31.
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):
(Print Name & Title)
(Date)
(Signature)
(Print Name & Title)
(Date)
Form DC-2 (continued)
3/90
-------
EXHIBIT C
INORGANIC TARGET ANALYTE LIST
ILM01.0
-------
INORGANIC TARGET ANALYTE LIST (TAL)
Contract Required
Detection Limit ^ '2'
Analyte (ug/L)
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
200
60
10
200
5
5
5000
10
50
25
100
3
5000
15
0.2
40
5000
5
10
5000
10
50
20
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 ILM01.0
-------
The value of 220 may be reported even though instrument
detection limit is greater than CRDL. The instrument or
method detection limit must be documented as described in
Exhibit E.
(2) The CRDL 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 ILM01.0
-------
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-6
Part C - Microwave Digestion Method D-9
Part D - Mercury and Cyanide Preparation D-16
SECTION IV - SAMPLE ANALYSIS D-17
Part A - Inductively Coupled Plasma-Atomic,
Emission Spectrometric Method . D-18
Part B - Atomic Absorption Methods, Furnace Technique . . . D-32
Part C - Atomic Absorption Methods, Flame Technique .... D-45
Part D - Cold Vapor Methods for Mercury Analysis D-50
Part E - Methods for Total Cyanide Analysis D-69
Part F - Percent Solids Determination Procedure D-98
Part G - Alternate Methods (Catastrophic ICP Failure) . .' . D-99
ILM01.0
-------
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 repo'rt the
highest valid value for each analyte as measured from the undiluted and
diluted analyses. Unless the Contractor can submit proof that dilution was
required to obtain valid results, both diluted and undiluted sample
measurements must be contained in the raw data. 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 ILM01.0
-------
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
take any pH adjustment action if the sample has not been properly
preserved.
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 nm 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 -aplicate
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 ILM01.0
-------
Figure 1
INORGANICS METHODS FLOW CHART
I I
| Field Sample |
.1.
Traffic Report or SMO
Specifies Parameters
Water
Matrix
Soil/Sediment
Matrix
I
Cyanide | |Acid Digestion) |Acid Digestion| |% Solids | | Cyanide
Analysis | | for Metals | | for Metals j |Determin-| | Analysis
in Water | | Analysis | | Analysis in | | ation | | in Soil/
| | in Water | (Soil/Sediment | | | (Sediment
! 1 1
1 1 1
1 1 1
| [Metal Anal.j (Metals Anal.J
j | ICP/AAS | | 1CP/AAS |
1 1 1
1 1 1
I 1 1
! 1 1
I | Data Reports |
1
1
1
1
1
1
!
1
!
D-3
ILM01.0
-------
SECTION II
SAMPLE PRESERVATION AND HOLDING TIMES
Sample Preservation
Water Sample Preservation
Measurement
Parameter
Metals(3)
Cyanide, total
and amenable
to chlorination
FOOTNOTES:
Container' ^
P.G
P,G
Preservative' '
HN03 to pH <2
0.6g ascorbic acid(4)
NaOH to pH >12
Cool, maintain at 4°C(±2°C)
until analysis
(1) Polyethylene (P) or glass (G).
(2) Sample preservation is performed by the sampler immediately
upon sample collection.
(3) Samples are filtered immediately on-site by the sampler
before adding preservative for dissolved metals.
(4) Only used in the presence of residual chlorine.
Soil/Sediment Sample Preservation
The preservation required for soil/sediment samples is maintenance
at 4°C (± 2°) until analysis.
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.
Analvte
Mercury
Metals (other than mercury)
Cyanide
No. of Days Following
Sample Receipt
by Contractor
26 days
180 days
12 days
D-4
ILM01.0
-------
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 (l-i-l) HNO-j 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 dilucion 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".
D-5 ILMOL.O
-------
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:
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Summary of Method
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
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).
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
Reagents
(1) ASTM Type II water (ASTM D1L93): Water must be
monitored.
(2) Concentrated nitric acid (sp. gr. 1.41)
(3) Concentrated Hydrochloric Acid (sp. gr. 1.19)
D-6 ILM01.0
-------
(4) Hydrogen Peroxide (30%)
e. Sample Preservation and Handling
Soil/sediment (nonaqueous) samples muse be refrigerated ac
4°C (±2°) from receipt until analysis.
f. Procedure
(1) Mix the sample thoroughly to achieve homogeneity. For
each digestion procedure, weigh (to the nearest O.Olgms)
a 1.0 to 1.5 gm 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 HNO-j, 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 (1^02). 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% #2®2 ^n ^ mL aliquots 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% t^C^. )
(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, Ag,
Na, Tl, V, and Zn, add 5 mL of 1:1 HC1 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) HC1 and 5% (v/v) HN03. Dilute the digestate
1:1 (200 mL final volume) with acidified water Co
maintain constant acid strength. The sample is now
ready for analysis.
D-7 ILM01.0
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(5b) If the sample is being prepared for the furnace analysis
of As, Be, Cd, Cr, Co, Cu, Fe, Pb, Mn, Ni, Se, Ag, Tl,
V, and Zn, continue heating the acid-peroxide digestate
until the volume has been reduced to approximately 2 raL,
add 10 raL 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 mixing) may be
centrifuged or allowed Co settle by gravity overnight to
remove insoluble material. The diluted digestate
solution contains approximately 2% (v/v) HNO-,. 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
h. Bibliography
Modification (by committee) of Method 3050, SW-846, 2nd ed.,
Test Methods for Evaluating Solid Waste. EPA Office of Solid
Waste and Emergency Response, July 1982.
D-8 ILM01.0
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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
2. SUMMARY OF METHOD
a. Water Sample Preparation
A representative 45 mL water sample is digested in 5 raL 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.
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 zlO
psi (7.5 ±0.7 atm). These vessels are capable of controlled
pressure relief at pressures exceeding 110 psi.
D-9 ILM01.0
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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.
T^
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).
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.
D-10 ILM01.0
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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 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 measurements 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 _ (tO rCo") Cm) (DT)
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),
C = The heat capacity, thermal capacity, or specific heat (cal. g"
1.°C'1) of water (-1.0),
m — The mass of the sample in grams (g),
DT = the final temperature minus the initial tempereture (°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
D-ll ILK01.0
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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.
(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 HNO-j 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 HNO-j is added to the digestion
vessels.
(3) The weight of each vessel is recorded to 0.02 g.
(4) The caps with the pressure release valves are placed on the vessels
hand tight and then tightened, using constant torque, to 12 ft./^bs.
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
D-12 ILM01.0
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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 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 24 + 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
Co report final concentration values based on an initial
volume of 45 ml. Concentrations so determined shall be
reported as "total".
D-13 ILM01.0
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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.
(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 water to achieve to 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.
D-14 ILM01.0
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(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 uncapped and vented
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 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
U = Weight in Kg of wet sample
S = % Solids/100
D-15 ILM01.0
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D. MERCURY AND CYANIDE PREPARATION
Refer Co each specific method in this Exhibit for mercury and cyanide
preparations.
D-16 ILM01.0
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SECTION IV
SAMPLE ANALYSIS
.Page No.
PART A - INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION
SPECTROMETRIC METHOD D-18
PART B - ATOMIC ABSORPTION METHODS, FURNACE TECHNIQUE D-32
PART C - ATOMIC ABSORPTION METHODS, FLAME TECHNIQUE D-45
PART D - COLD VAPOR METHODS FOR MERCURY ANALYSIS D-50
PART E - METHODS FOR CYANIDE ANALYSIS D-69
PART F - PERCENT SOLIDS DETERMINATION PROCEDURE D-98
PART G - ALTERNATE METHODS (CATASTROPHIC ICP FAILURE) D-99
D-17 ILM01.0
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PART A - INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION SPECTROMETRIC METHOD'*'
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 interfere-ce 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
2.1 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
+A bibliography citing method references appears in paragraph 11 of the
method.
~&
CLP-M modified for the Contract Laboratory Program.
D-18 ILM01.0
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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
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. Definitions
3.1 Dissolved -- Those elements which will pass through a 0.45 urn membrane
filter.
3.2 Suspended -- Those elements which are retained by a 0.45 urn membrane
filter.
3.3 Total -- The concentration determined on an unfiltered sample following
vigorous digestion.
3.4 Instrumental detection limits -- See Exhibit E.
3.5 Sensitivity -- The slope of the analytical curve, i.e. functional
relationship between emission intensity and concentration.
3.6 Instrument check standard -- A multi-element standard of known
concentrations prepared by the analyst to monitor and verify instrument
performance on a daily basis. (See 7.6.1.)
3.7 Interference check sample - - A solution containing both interfering and
analyte elements of known concentration that can be used to verify
background and interelement correction factors. (See 7.6.2.)
3.8 Quality control sample -- A solution obtained from an outside source
having known concentration values to be used to verify the calibration
standards. (See 7.6.3.)
3.9 Calibration standards -- A series of known standard solutions used by
the analyst for calibration of the instrument (i.e., preparation of the
analytical curve). (See 7.4.)
3.10 Linear dynamic range - - The concentration range over which the
analytical curve remains linear as determined in Exhibit E.
3.11 Reagent blank -- A volume of deionized, distilled water containing the
same acid matrix as the calibration standards carried through the entire
analytical scheme. (See 7.5.2.)
3.12 Calibration blank -- A volume of deionized, distilled water acidified
with HN03 and HC1. (See 7.5.1.)
D-19 ILM01.0
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3.13 Method of standard addition -- The standard addition technique involves
the use of the unknown and the unknown-plus-a-known amount of standard
by adding known amounts of standard to one or more aliquots of the
processed sample solution.
4. Safety
4.1 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.
5. Interferences
5.1 Several types of interference effects may contribute to inaccuracies in
the determination of trace elements. They can be summarized as follows:
5.1.1 Spectral interferences can be categorized as 1) overl'ap 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
•Jf-jf
Laboratory , is expressed as analyte concentration equivalents
(i.e., false analyte concentrations) arising from 100 mg/L of
the interferent element.
Ames Laboratory, USDOE, Iowa State University, Ames, Iowa 50011.
D-20 IIM01.0
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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. 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.
5.1.2 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.
5.1.3 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.
D-21 ILM01.0
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5.2 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 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.
6. Apparatus
6.1 Inductively Coupled Plasma-Atomic Emission Spectrometer.
6.1.1 Computer controlled atomic emission spectrometer with
background correction.
6.1.2 Radio frequency generator.
6.1.3 Argon gas supply, welding grade or better.
6.2 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 ranee 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.
7. Reagents and Standards
7.1 Acids used in the preparation of standards and for sample processing
must be ultra-high purity grade or equivalent. Redistilled acids are
acceptable.
7.1.1 Acetic acid, cone. (sp gr 1.06).
7.1.2 Hydrochloric acid, cone. (sp gr 1.19).
7.1.3 Hydrochloric acid, (1+1): Add 500 mL cone. HC1 (sp gr 1.19)
to 400 mL deionized, distilled water and dilute to 1 liter.
D-22 ILM01.0
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7.1.4 Nitric acid, cone. (sp gr 1.41).
7.1.5 Nitric acid, (1+1): Add 500 mL cone. HNO3 (sp gr 1.41) to 400
mL deionized, distilled water and dilute to 1 liter.
7.2 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.
7.3 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.
(CAUTION: Many metal salts are extremely toxic and may be fatal if
swallowed. Wash hands thoroughly after handling.) Typical stock
solution preparation procedures follow:
7.3.1 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. HNO-j 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.
7.3.2 Antimony solution stock, 1 mL - 100 ug Sb: Dissolve 0.2669 g
K(SbO)C4H^Og in deionized distilled water, add 10 mL (1+1) HC1
and dilute to 1000 mL with deionized, distilled water.
7.3.3 Arsenic solution, stock, 1 mL - 100 ug As: Dissolve 0.1320 g
of AS20-J in 100 mL of deionized, distilled water containing 0.4
g NaOH. Acidify the solution with 2 mL cone. HNO^ and dilute
to 1,000 mL with deionized, distilled water.
7.3.4 Barium solution, stock, 1 mL •• 100 ug Ba: Dissolve 0.1516 g
BaCl2 (dried at 250°C for 2 hrt.) 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.
7.3.5 Beryllium solution, stock, 1 mL - 100 ug Be: Do not dry.
Dissolve 1.966 g BeSO^'4H20, in deionized, distilled water, add
10.0 mL cone. HNOo and dilute to 1,000 mL with deionized,
distilled water.
7.3.6 Boron solution, stock, 1 mL - 100 ug B: Do not dry. Dissolve
0.5716 g anhydrous H-jBO-j 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.
D-23 ILM01.0
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7.3.7 Cadmium solution, stock, 1 mL - 100 ug Cd: Dissolve 0.1142 g
CdO in a minimum amount of (1+1) HNO-j. Heat to increase rate
of dissolution. Add 10.0 mL cone. HNOo and dilute to 1,000 mL
with deionized, distilled water.
7.3.8 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.
7.3.9 Chromium solution, stock, 1 mL - 100 ug Cr: Dissolve 0.1923 g
of Cr02 in deionized, distilled water. When solution is
complete acidify with 10 mL cone. HN03 and dilute to 1,000 mL
with deionized, distilled water.
7.3.10 Cobalt solution stock, 1 mL - 100 ug Co: Dissolve 0.1000 g of
cobalt metal in a minimum amount of (1+1) HN03. Add 10.0 mL
(1+1) HC1 and dilute to 1,000 mL with deionized, distilled
water.
7.3.11 Copper solution, stock, 1 mL - 100 ug Cu: Dissolve 0.1252 g
CuO in a minimum amount of (1+1) HNO^. Add 10.0 mL cone. HNO-j
and dilute to 1,000 mL with deionized, distilled water.
7.3.12 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.
HNO3. Cool, add an additional 5 mL of cone. HNO-j and dilute
to 1,000 mL with deionized, distilled water.
7.3.13 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.
7.3.14 Magnesium solution, stock, 1 mL - 100 ug Mg: Dissolve 0.1658 g
MgO in a minimum amount of (1+1) HNO-,. Add 10.0 mL cone. HNO^
and dilute to 1,000 mL with deionized, distilled water.
7.3.15 Manganese solution, stock, 1 mL - 100 ug Mn: Dissolve 0.1000 g
of manganese metal in the acid mixture, 10 mL cone. HC1 and 1
mL cone. HN03, and dilute to 1,000 mL with deionized,
distilled water.
7.3.16 Molybdenum solution, stock, 1 mL - 100 ug Mo: Dissolve 0.2043
g (NH4)2Mo04 in deionized, distilled water and dilute to 1,000
mL.
7.3.17 Nickel solution, stock, 1 mL -= 100 ug Ni: Dissolve 0.1000 g of
nickel metal in 10 mL hot cone. HN03, cool and dilute to 1,000
mL with deionized, distilled water.
D-24 ILM01.0
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7.3.18 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.
7.3.19 Selenium solution, stock, 1 mL - 100 ug Se: Do not dry.
Dissolve 0.1727 g l^SeO-j (actual assay 94.6%) in deionized,
distilled water and dilute to 1,000 mL.
7.3.20 Silica solution, stock, 1 mL - 100 ug Si02: Do not dry.
Dissolve 0.4730 g Na2SiO-j'9H20 in deionized, distilled water.
Add 10.0 mL cone. HNO-j and dilute to 1,000 mL with deionized,
distilled water.
7.3.21 Silver solution, stock, 1 mL - 100 ug Ag: Dissolve 0.1575 g
AgN03 in 100 mL of deionized, distilled water and 10 mL cone.
HN03. Dilute to 1,000 mL with deionized, distilled water.
7.3.22 Sodium solution, stock, 1 mL - 100 ug Na: Dissolve 0.2542 g
NaCl in ieionized, distilled water. Add 10.0 mL cone. HNO-j
and dilute to 1,000 mL with deionized, distilled water.
7.3.23 Thallium solution, stock, 1 mL - 100 ug Tl: Dissolve 0.1303 g
TlNO-j in deionized, distilled water. Add
10.0 mL cone. HNO^ and dilute to 1,000 mL with deionized,
distilled water.
7.3.24 Vanadium solution, stock, 1 mL - 100 ug V: Dissolve 0.2297
NH,VOo in a minimum amount of cone. HNO^. Heat to increase
rate of dissolution. Add 10.0 mL cone. HNOo and dilute to
1,000 mL with deionized, distilled water.
7.3.25 Zinc solution, stock, 1 mL - 100 ug Zn: Dissolve 0.1245 g ZnO
in a minimum amount of dilute HNOo. Add 10.0 mL cone. HNO-j and
dilute to 1,000 mL with deionized, distilled water.
7.4 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) HNO3 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.
7.4.1 Mixed standard solution I -- Manganese, beryllium, cadmium,
lead, and zinc.
D-25 ILMOL.O
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7.4.2 Mixed standard solution II -- Barium, copper, iron, vanadium,
and cobalt.
7.4.3 Mixed standard solution III -- Molybdenum, silica, arsenic, and
selenium.
7.4.4 Mixed standard solution IV -- Calcium, sodium, potassium,
aluminum, chromium and nickel.
7.4.5 Mixed standard solution V -- Antimony, boron, aagnesium,
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.
7.5 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.
7.5.1 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.
7.5.2 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.
7.6 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.
7.6.1 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.)
7.6.2 The interference check sample is prepared by the analyst, or
obtained from EPA if available (Exhibit E).
D-26 ILM01.0
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7.6.3 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.)
8. Procedure
8.1 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 SO min. of operation
prior to calibration.
8.2 Initiate appropriate operating configuration of computer.
8.3 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.)
8.4 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.
8.5 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.
9. Calculation
9.1 Reagent blanks (preparation blanks) should be treated as specified in
Exhibit E.
9.2 If dilutions were performed, the appropriate factor must be applied to
sample values.
9.3 Units must be clearly specified.
10. Quality Control (Instrumental)
10.1 Quality control must be performed as specified in Exhibit E.
11. Bibliography
1. Winge, R.K., V.J. Peterson, and V.A. Fassel, "Inductively Coupled
Plasma-Atomic Emission Spectroscopy Prominent Lines," EPA-600/4-79-
017.
D-27 ILM01.0
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2. Winefordner, J.D., "Trace Analysis: Spectroscopic Methods for
Elements," Chemical Analysis, Vol. 46, pp. 41-42.
3. Handbook for Analytical Quality Control in Water and Wastewater
Laboratories, EPA-600/4-79-019.
4. Garbarino, J.R. and Taylor, K.E., "An Inductively-Coupled Plasma
Atomic Emission Spectrometric Method for Routine Water Quality
Testing," Applied Spectroscopy 33, No. 3(1979).
5. "Methods for Chemical Analysis of Water and Wastes," EPA-600/4-79-
020.
6. Annual Book of ASTM Standards, Part 31.
7. "Carcinogens - Working With Carcinogens," Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, Aug. 1977.
8. "OSHA Safety and Health Standards, General Industry," (29 CFR 1910),
Occupational Safety and Health Administration, OSHA 2206, (Revised,
January 1976).
9. "Safety in Academic Chemistry Laboratories, American Chemical
Society Publications, Committee on Chemical Safety, 3rd Edition,
1979.
10. "Inductively Coupled Plasma-Atomic Emission Spectrometric Method of
Trace Elements Analysis of Water and Waste", Method 200.7 modified
by CLP Inorganic Data/Protocol Review Committee; original method by
Theodore D. Martin, EMSL/Cincinnati.
D-28 ILM01.0
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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
7
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-29 ILMOL.O
-------
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-------
TABLE 3. INTERFERENT AND ANALYTE ELEMENTAL CONCENTRATIONS USED
FOR INTERFERENCE MEASUREMENTS IN TABLE 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-31 ILM01.0
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PART B - ATOMIC ABSORPTION METHODS. FURNACE TECHNIQUE'1'
Ana1vte/Method Page No.
Antimony - Method 204.2 CLP-M* D-33
Arsenic - Method 206.2 CLP-M D-34
Beryllium - Method 210.2 CLP-M D-36
Cadmium - Method 213.2 CLP-M D-37
Chromium - Method 218.2 CLP-M D-38
Lead - Method 239.2 CLP-M D-39
Selenium - Method 270.2 CLP-M D-41
Silver - Method 2/2.2 CLP-M D-43
Thallium - Method 279.2 CLP-M D-44
+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-32 ILM01.0
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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
ag/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 run
6. Other operating parameters should be set as specified by the particular
ins trument manufacture r.
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
sett-ings.
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-33 ILM01.0
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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, AS202
(analytical reagent grade) in 100 mL of deionized distilled water
containing 4 g NaOH. Acidify the solution with 20 mL cone. HNO-, 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
Ni(NO-j)2 '6^0 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 aaal^jis. Withdraw
appropriate aliquots of the stock solution, add 1 mL of cone. HNCU, 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 (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
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, 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.
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.
CLP-M modified for the Contract Laboratory Program.
D-34 ILM01.0
-------
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.
D-35 ILM01.0
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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, BeSO^, 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 che 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 @ 2800°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 234.9 nin
6. The operating parameters should be set as specified by the particular
instrument 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, 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-36 ILM01.0
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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
HoO (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, (NH^)2HPO^ (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-37 ILM01.0
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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,
CaCNO^^'^HoO (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% ^02 and 1 mL of che 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.
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 graphits 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-38 ILM01.0
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LEAD
Method 239.2 CLP-M* (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L
Approximate Detection Limic: 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 HNO^ and
dilute to 1 Liter with deionized distilled water. 1 mL - 1 rag Pb
(lOOOmg/L).
2. Lanthanum Nitrate' solution: Dissolve 58.64 g of ACS reagent grade
La203 in 100 mL cone. HN03 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
ins trument manufacture r.
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-39 ILM01.0
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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-40 ILM01.0
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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% J^SeO-j) in deionized distilled water and make up to 200 mL.
1 mL - 1 mg Se (1000 nig/L) .
2. Nickel Nitrate solution, 5%: Dissolve 24.780 g of ACS reagent grade
NiCNO-j^. 6H20 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 standard" must be prepared using the samp, 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. HNO^, 2 mL of 30% 1^02 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
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
ins trument manufacture 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 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). If conditions
CLP-M modified for the Contract Laboratory Program.
ILM01.0
-------
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-42 ILM01.0
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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 HNO^ 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. Astr'ng 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 nni
6. Other operating parameters should be set as specified by the particular
instrument 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,
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-43 ILM01.0
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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, TINO-j (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 atontization can be operated using lower
atomization tempera Cures 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-44 ILM01.0
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PART C - ATOMIC ABSORPTION METHODS... FLAME TECHNIQUE'1'
Analyte/Method Page No,
Calcium - Method 215.1 CLP-M* D-46
Magnesium - Method 242.1 CLP-M D-47
Potassium - Method 258.1 CLP-M D-48
Sodium - Method 273.1 CLP-M D-49
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.
°-45 ILM01.0
-------
CALCIUM
Method 215.1 CLP-M." (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.2-7 mg/L using a wavelength of 422.7 nm
Sensitivity: 0.08 mg/L
Detection Limit: 0.01 mg/L
Preparation of Standard Solution
1. Stock Solution: Suspend 1.250 g of CaCO-j (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 La2°3. 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 -ad sample alike add 1.0 mL of the lanthanum
chloride solution, i.e., 20 mL of standard or sample + 2 mL LaCl-^ - 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
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. lonization
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]).
j
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-46 ILM01.0
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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 HNO-j 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 La2°3» 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 LaCl-j - 2±
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
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-K modified for the Contract Laboratory Program.
D-47 ILM01.0
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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 nin
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Slightly oxidizing
Notes
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-48 ILM01.0
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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 nra
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
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.
CCLP-M modified for the Contract Laboratory Program.
D'A9 1LM01.0
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PART D - COLD VAPOR METHODS FOR MERCURY ANALYSIS4
Method Page No.
Mercury Analysis in Water by Manual Cold Vapor Technique D-50
Method 245.1 CLP-M*
Mercury Analysis in Water by Automated Cold Vapor Technique D-58
Method 245.2 CLP-M
Mercury Analysis in Soil/Sediment by Manual Cold Vapor Technique D-64
Method 245.5 CLP-M
A bibliography citing method references follows each method.
^
CLP-M modified for the Contract Laboratory Program.
D-50 ILM01.0
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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 rim 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 coll.iction (Exhibit D, Section II).
4. Interference
4.1 Possible interference from sulfide is eliminated by the addition of
^otassium'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).
NCLP-M modified for the Contract Laboratory Program.
D-51 ILM01.0
-------
4.2 Copper has also been reported Co interfere; however, copper
concentrations as high as 10 mg/L had no effect on recovery of
mercury from spiked samples.
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.
D-52 ILM01.0
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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 60U' bulb ma'" 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.
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.
D-53 ILM01.0
-------
Figure 1. Apparatus for Flameless Mercury Determination
f
u
AIR PUMP
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r 1 I
" 7 DESICCANT .
r
ARcnp
\ U* BUBBLER CE
k
^
V
M.
1
PTION
LL
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)
1
Iv
D-*
SAMPLE SOLUTION
IN BOD BOTTLE
SCRUBBER
CONTAINING
A MERCURY
ABSORBING
MEDIA
D-54
ILM01.0
-------
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 KMnO^ (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.
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 th<_ vapor through some absorbing media, such as:
a) equal volumes of 0.1 M KMnO*, and 10% HoSO- or
b) 0.25% iodine in a 3% a KI solution. A specially treated charcoal
that will adsorb mercury vapor is available.
D-55 ILM01.0
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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 KMnO^ 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 KMnO^ 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
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-56 ILM01.0
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Bibliography
1. Kopp, J.F., Longbottom, M.C. and Lobring, L.B. "Cold Vapor Method for
Determining Mercury", AWWA, vol. 64, p. 20, Jan. 1972.
2. Annual Book of ASTM Standards, Part 31, "Water", Standard D3223-73, p.
343 (1976).
3. Standard Methods for the Examination of Water and Wastewater 14th
Edition, p. 156 (1975).
D-57 ILM01.0
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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 spectrophoCometer. 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 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, 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.
'CLP-M modified for the Contract Laboratory Program.
D-58 ILM01.0
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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 o£ the ^bove interferences can be overcome by use of the
Manual Mercury method.
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 raL of cone, sulfuric 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.
ILM01.0
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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.
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: Hydroxylaraine 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 I 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.
D-60 ILM01.0
-------
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 t^SO^ line in
distilled water to wash out system. After flushing, wash out the
I^SO^ line. Also flush the coils in the high temperature heating
bath by pumping stannous sulfate (6.3) through the sample lines
followed by distilled vater. This will prevent build-up of oxides of
manganese.
NOTE 5: Because of che 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% I^SO^
(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.
Bibliography
1. Wallace R.A., Fulkerson, W., Shults, W.D., and Lyon, U.S., "Mercury in
the Environment-The Human Element", Oak Ridge National Laboratory,
ORNL/NSF-EP-1 p. 31, (January, 1971).
2. Hatch, W.R. and Ott, W.L., "Determination of Sub-Microgram Quantities
of Mercury by Atomic Absorption Specrophotometry". Anal. Chem. 40,
2085 (1968).
3. Brandenberger, H. and Bader, H. , "The Determination of Nanogram Levels
of Mercury in Solution by a Flameless Atomic Absorption Technique",
Atomic Absorption Newsletter 6, 101 (1967).
4. Brandenberger, H. and Bader, H., "The Determination of Mercury by
Flameless Atomic Absorption II, A Static Vapor Method", Atomic
Absorption Newsletter 7,53 (1968).
5. Goulden, P.O. and Afghan, B.K. "An Automated Method for Determining
Mercury in Water", Technicon, Adv. in Auto. Analy. 2, p. 317 (1970).
6. "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.
7. Op. cit. (#1), Methods 245.1 or 245.2.
D-61 ILM01.0
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AIR AND
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Figure 1. Vapor liquid separator
D-62
ILM01.0
-------
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D-63
ILM01.0
-------
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
I
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 (c.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 i- -mple should be analyzed without drying. A separate percent
solics 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 thisoccurs, the
recovery of organic mercury will be low. The problem can be
eliminated by reducing the v.-eight of the original sample or by
CLP-M modified for the Contract Laboratory Program.
D-64 ILM01.0
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increasing the amount of potassium persulfate (and consequently
stannous chloride) used in the digestion.
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.
D-65 ILM01.0
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6. Reagents
6.1 Sulfuric acid, cone.: Reagent grade of low mercury content
6.2 Nitric acid, cone.: Reagent grade of low mercury content
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
c
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. H2SO^ (6.1) and 2.5 mL of
cone. HNO3 (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 agitacion. 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
D-66 ILM01.0
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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
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 KMnO^ and 10% i^SO^, 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. HoSO^ and 2 mL of cone. HNO^
are added to the 0.2 g of sample. 5 mL of saturated KMnO^ solution
and 8 mL of potassium persulfate solution =>re 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
US g/g = wt of the aliquot in gms
(based upon dry wt of the sample)
ILMOL.O
-------
9.3 Report mercury concentrations as described for aqueous mercury
samples converted to units of rag/kg. The sample result or the
detection limit for each sample must be corrected for sample weight
and % solids before reporting.
Bibliography
1. Bishop, J. N., "Mercury in Sediments", Ontario Water Resources Comm.,
Toronto, Ontario, Canada, 1971
2. Salraa, M., private communication, EPA Cal/Nev. Basin Office, Almeda,
California
3. "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
4. Op. cit. (#3), Methods 245.1 or 245.2
D-68 ILM01.0
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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-70
Method for Total Cyanide Analysis in Soil/Sediment*
Method 335.2 CLP-M D-79
Method for Total Cyanide Analysis by Midi Distillation
Method 335.2 CLP-M D-91
A bibliography citing method references follows the method.
&
CLP-M Modified for the Contract Laboratory Program.
D-69 ILM01.0
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METHOD FOR TOTAL CYANIDE ANALYSIS IN WATER
CYANIDE, TOTAL (in Water)
Method 335.2 CLP-M (Titrimetric; Manual Spectrophotometric; Semi-Automated
Spectrophotometrie)
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
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.
CLP-M Modified for the Contract Laboratory Program.
D-70 ILM01.0
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4. Sample Handling and Preservation
4.1 All bottles must be thoroughly cleansed and rinsed to remove soluble
material from containers.
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 amadditional 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)
D-71 ILM01.0
-------
6.3 Spectrophotometer suitable for measurements at 578 run or 620 nra 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
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: Weight 510 g of MgC^'Sl^O 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 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 40°C. Weight out 3.2647 g of dried AgN03,
D-72 ILM01.0
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dissolve in distilled water, and dilute to 1000 mL (1 mL - 1
rag 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
Nat^PO^'H^O in a 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:
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:?.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.
7.3.3.2.1 3-Methyl-lphenyl-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
nonacid-washed filter paper. Collect
the filtrate. Through the same
filter paper pour solution
(7.3.3.2.2) collecting the filtrate
D-73 ILM01.0
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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 Spectropho tome trie 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^'l^O in distilled
water and dilute to 1 liter. Add 0.5 mL of Brij-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 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. .
D-74 ILM01.0
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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.
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 (7.3.1)
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 I 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 wich pyridine-pyrazolone.
D-75 ILM01.0
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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 water. 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 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
ensure 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 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:
D-76 ILM01.0
-------
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 u^-'.ng 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, rag/L - mL orig. sample x mL of aliquot titrated
WHERE: A - volume of AgNO-j for titration of sample
(1 mL - 1 mg Ag)
B = volume of AgNO-j 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 mL). Also, correct for, and
report on Form XIV, any dilutions which were made before or after
distillation.
D-77 ILM01.0
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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
i
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 i concentration of 10 ug/L in the distilled
sample.
Bibliography
1. Methods for "Chemical Analysis of Water and Wastes", March 1979, EPA
publication #600/4-79-02.
2. "Operation RN Manual for Technicon Auto Analyzer IIC System", 1980.
Technical publication #TA9-0460-00. Technicon Industrial Systems,
Tarrytown, NY, 10591.
3. "Users Guide for the Continuous Flow Analyzer Automation System",
EMSL U.S. EPA, Cincinnati, OH (1981).
4. 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.
5. Op. cit. (#4), Methods 335.2.
D-78 ILM01.0
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METHOD FOR TOTAL CYANIDE ANALYSIS IN SOIL/SEDIMENT
CYANIDE, TOTAL (in Sediments)
P-M* (Titrimetric; Manual Spec
Semi-Automated Spec tropho tome tric)
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
analys is.
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 Handlins 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.
CLP-M Modified for the Contract Laboratory Program.
D-79 ILM01.0
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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.
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 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 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
D-80 ILM01.0
-------
7.1.4 Sulfuric acid: concentrated
7.1.5 Magnesium chloride solution: Weigh 510 g of MgClZ.ei^O 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.
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 AgNOo crystals and drying to
constant weight at 40°C. Weigh out 3.2647 g of dried
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
NaH2P04'H20 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:
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:
D-81 ILM01.0
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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.
7.3.3.2.2 3,3'Dimethyl-1,1'-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 does not affect the color
production with cyanide if used
within 24 hours of preparation.
7.4 Semi-Automated Spectrophotometric 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 NaH2P04'H2O 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
D-82 ILM01.0
-------
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.
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 the
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 raL 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.
D-83 ILM01.0
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8.3.1.1 Pyridlne-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 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.
As an example, standard solutions could be prepared as follows:
mL of Standard Solution Cone, ug CN
(1.0 - 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)
D-84 ILM01.0
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8.4 Serai-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
(1.2. 3") diluted to 1 liter ug CN/L
0 0
4.0 20
10.0 50
20.0 10O
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.
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 25° mL x 1000 g/kg
mL aliquot titrated
CN, mgAg
%solids
X '-- '
100
D-85 . ILM01.0
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WHERE: A - mL of AgNOj for titration of sample
(1 mL - 1 mg Ag)
B - mL of AgNO-j for titraCion of blank
(1 mL - 1 mg Ag)
C — weC 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)
100
WHERE: A - ug CN read from standard curve (per 250 mL)
B - mL of distillate taken for colorime'tric
determination (8.3.1)
C - wet weight of original 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)
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 K % solids
100
D-86 ILM01.0
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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.
Bibliography
1. Modification of Method 335.2: Cyanide, Total
2. Methods for "Chemical Analysis of Water and Wastes", March 1979. EPA
Publication #600/4-79-02.
3. "Operation Manual for Technicon Auto Analyzer IIC System", 1980.
Technical publication #TA9-0460-00. Technicon Industrial Systems,
Tarrytown, NY, 10591.
4. "Users Guide for the Continuous Flow Analyzer Automation System",
ESL, U.S. EPA, Cincinnati, Ohio (1981).
5. "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.
6. Op. cit. (#5), Methods 335.2, modified (by committee).
D-87 ILM01.0
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ALLIHN CONDENSER
AIR INLET TUBE\
ONE LITER
BOILING FLASK
— CONNECTING TUBING
GAS ABSORBER
SUCTION
Figure 1. Cyanide distillation apparatus
D-88
ILM01.0
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COOLING WATER
INLET
HEATER -
TO LOW VACUUM
SOURCE
- ABSORBER
OISTILUHG FLASK
O
Figure 2. Cyanide distillation apparatus
D-89
ILM01.0
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sc —i
o <
o
o
O —
fC
o o
O "C
C
•e o
.o
«: ^-^
o
te «->
o
Figure 3.
Cyanide Manifold
D-90
ILM01.0
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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 colorimetric 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.
D-91 ILM01.0
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4 . Interferences
4.1 Interferences are eliminated or reduced by using the distillation
procedure .
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 the
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 antifoaming 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 580 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
6H20 in ASTM Type II water and dilute to one liter.
6.1.3 Sulfuric acid, 50% (v/v) . Carefully add a portion of
concentrated t^SO^ to an equal portion of ASTM Type II water.
D-92 ILM01.0
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6.1.4 Sodium hydroxide solution, 1.25 N. Dissolve 50 g of NaOH in
ASTM Type II water and dilute to one liter.
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 AgNO^ crystals and dry5~g to a constant
weight at 104°C. Weigh out 3.2647 g of dried AgN03 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 l^CRO^ 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 Spectrophotometric Reagents
6.3.1 Phosphate buffer solution, 1 M. Dissolve 138 g of NaH2P04-H2O
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 barbituric 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 Co mix. Add
75 mL of pyridine and 15 mL concentrated HCL and raix until all
the barbituric acid is dissolved. Dilute to one liter with
ASTM Type II water and store at 4°C.
D-93 ILM01.0
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7. Procedure
7.1 Distillation
7.1.1 The procedure described here utilizes a midi distillation
apparatus and requires a sample aliquot of 50 mLs 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)
^SO^ (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
D-94 ILM01.0
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them at 4°C until analyzed. The solutions must be analyzed for
cyanide within the 12 day holding time specified in Section II.
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 (6.5) 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^lO mg/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.
D-95 ILM01.0
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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.
8. Calculat ions
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
CM, 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) .
D-96 ILM01.0
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8.1.5.2 The concentration of cyanide in the sample is
determined as follows:
A x D x F
CN, ing/kg - B x E
where: A - ug/L CN of sample from regression
analys is curve
B - wet weight of original sample in g
(See 7.1.3)
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-97 ILM01.0
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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 tro 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°C. Sample
handling and drying should be conducted in a well-ventilated area.
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 10Q
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 the oven to
document the 12 hour drying time minimum. In the event it is necessary to
demons crate the attainmenr of constant: weight, da~a masc be recorded for a
minimum of two repetitive weigh/dry/dessicate/weigh cycles with a minimum
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-98 ILM01.0
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PART G - ALTERNATE METHODS ("CATASTROPHIC ICP FAILURE)4"
Analyse Page No-.
Aluminum - Method 202.2 CLP-M*, Furnace AA D-101
Barium - Method 208.2 CLP-M, Furnace AA D-102
Cobalt - Method 219.2 CLP-M, Furnace AA D-103
Copper - Method 220.2 CLP-M, Furnace AA D-104
Iron - Method 236.2 CLP-M, Furnace AA D-105
^anganese - Method 243.2 CLP-M, Furnace AA D-106
Nickel - Method 249.2 CLP-M, Furnace AA D-107 -
Vanadium - Method 286.2 CLP-M, Furnace AA D-108
Zinc - Method 289.2 CLP-M, Furnace AA D-109
Aluminum - Method 202.1 CLP-M, Flame AA D-lll
Antimony - Method 204.1 CLP-M, Flame AA D-113
Barium - Method 208.1 CLP-M, Flame AA D-114
Beryllium - Method 210.1 CLP-M, Flame AA D-115
Cadmium - Method 213.1 CLP-M, Flame AA D-116
Chromium - Method 218.1 CLP-M, Flame AA D-117
Cobalt - Method 219.1 CLP-M, Flame AA D-118
Copper - Method 220.1 CLP-M, Flame AA D-119
Iron - Method 236.1 CLP-M, Flame AA D-120
Lead - Method 239.1 CLP-M, Flame AA D-121
Manganese - Method 243.1 CLP-M, Flame AA D-122
Nickel - Method 249.1 CLP-M, Flame AA D-123
Silver - Method 272.1 CLP-M, Flame AA D-125
Thallium - Method 279.1 CLP-M, Flame AA D-126
Vanadium - Method 286.1 CLP-M, Flame AA D-127
Zinc - Method 289.1 CLP-M, Flame AA D-128
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-99 ILM01.0
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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-100 ILM01.0
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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-101 ILM01.0
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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.
A. Purge Gas Atmosphere: Argon
5. Wavelength: 553.6 run
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-102 ILM01.0
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COBALT*
Method 219.2 CLP-M** (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-LOO 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 run
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 u--d
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 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-103 ILM01.0
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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 che 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.
A. 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 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. 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-104 ILM01.0
-------
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.
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.
Modified for the Contract Laboratory Program.
D-105 ILM01.0
-------
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-106 ILM01.0
-------
NICKEL*
Method 249.2 CLP-M** (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L
Approximate Detection Limi c: 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
-------
VANADIUM*
Method 286.2 CLP-M** (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 10-200 ug/L
Approximate Detection Limit: A 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.
A. Purge Gas Atmosphere: Argon
5. Wavelength: 318.4 run
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 vising 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-108 ILM01.0
-------
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.
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-109 ILM01.0
-------
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-110 ILM01.0
-------
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. HNO^ to the
metal, cover the beakec 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 che 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-lll ILM01.0
-------
Notes
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'112 ILM01.0
-------
ANTIMONY*
Method 204.1 CLP-H** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 1-40 mg/L using a wavelength of 217.6 nm
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 rhe 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-113 ILM01.0
-------
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 Limic: 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 r.he 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 ac^d 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-114 ILM01.0
-------
BERYLLIUM*
Method 210.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.052 mg/L using a wavelength of 234.9 nm
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, BeSO^, 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 i~ 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-115 ILM01.0
-------
CADMIUM*
Method 213.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.052 mg/L using a wavelength of 228.8 ran
Sensitivity: 0.025 mg/L
Approximate Detection Limic: 0.005 mg/L
Preparation of Standard Solution
1. Stock Solution: Carefully weigh 2.282 g of cadmium sulfate
(3CdSO^'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-116 ILM01.0
-------
CHROMIUM*
Method 218.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.5-10 mg/L using a wavelength of 357.9 nra
Sensitivity: 0.25 mg/L
Approximate Detection Limi t: 0.05 tng/L
Preparation of Standard Solution
1. Stock Solution: Dissolve 1.923 g of chromium trioxide (CrO^, reagent
grade) in deionized distilled water. When solution is complete,
acidify with redistilled HNO-j and dilute to 1 liter with deionized
distilled water. 1 mL - 1 mg Cr (1000 tng/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)
Chromium hollow cathode lamp
Wavelength: 357.9 nm
Fuel: Acetylene
Oxidant: Nitrous oxide
Type of flame: Fuel rich
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-117 ILM01.0
-------
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
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 vised under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-118 ILM01.0
-------
COPPER*
Method 220.1 CLP-H** (Atomic Absorption, Flame Technique)
Optimum Concentration Rang^: 0.2-5 mg/L using a wavelength of 324.7 nrn
Sensitivity: 0.1 mg/L
Approximate Detection Limit: 0.02 rag/L
Preparation of Standard Solution
1. Stock Solution: Carefully weigh 100 g of electrolyte copper
(analytical reagent grade). Dissolve in 5 mL redistilled HNOo 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)
Copper hollow ca chode lamp
Wavelength: 324.7 run
Fuel: Acetylene
Oxidant: Air
Type of flame: Oxidizing
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 che Contract Laboratory Program.
D-119 ILM01.0
-------
IRON*
Method 236.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.3-5 mg/L using a wavelength of 248.3 ran
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 HNO-j, wanning 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-120 ILM01.0
-------
LEAD*
Method 239.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 1-20 mg/L using a wavelength of 283.3 nra
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 HNO^ and
dilute to 1 liter with deionized distilled water. 1 mL - 1 mg 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 run
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-121 ILM01.0
-------
MANGANESE*
Method 243.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Ran^e: 0.1-3 mg/L using a wavelength of 279.5 nm
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 HNO-j. 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 ch» 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 ui,ed under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-122 ILM01.0
-------
NICKEL*
Method 249.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.3-5 mg/L using a wavelength of 232.0 run
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-123 ILM01.0
-------
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 AgNO^, (analytical reagent grade)
in deionized distilled water, add 10 mL cone. HNO-j 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 grains of iodine, 1^ (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^OH, 6.5 grams KCN, and 5.0 mL of 1.0 N I2
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-124 ILM01.0
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3. If absorption to container walls or the formation of AgCl is suspected,
make the sample basic using cone. NH^OH 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 run wavelengrh may also be used. This has a relative
sensitivity of 2.
References
1. "The Use of Cyanogen Iodide (CNI) as a Stabilizing Agent for Silver in
Photographic Processing Effluent Sample", Owerbach, Daniel,
Photographic Technology Division, Eastman Kodak Company, Rochester,
N.Y. 14650.
D-125 ILM01.0
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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 rag 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.
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VANADIUM*
Method 286.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 2-100 mg/L using a wavelength of 318.4 run
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, V20c
(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,
Al(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.
Insjtrumental Parameters (General')
1. Vanadium hollow cathode lamp
2. Wavelength: 318.4 run
3. Fuel: Acetylene
4. Oxidant: Nitrous Oxide
5. Type of flame: Fuel rich
Interferences
1. It has been reported chat 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.
ILM01.0
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ZINC*
Method 289.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.05-1 rog/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 HNO^. When solution is
complete make up to 1 liter with deionized distilled water. 1 mL - 1
rag 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 nra
line.
3. The sensitivity may be increased by the use of low-temperature flames.
A. 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.
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EXHIBIT E
QUALITY ASoURANCE/QUALITY CONTROL REQUIREMENTS
Page No.
SECTION I - GENERAL QA/QC PRACTICES E-l
SECTION II - SPECIFIC QA/QC PROCEDURES E-2
SECTION III - QUALITY ASSURANCE PLAN E-5
SECTION IV - DATA MANAGEMENT E-7
SECTION V - REQUIRED QA/QC OPERATIONS E-9
SECTION VI - LABORATORY EVALUATION PROCESS E-25
ILH01.0
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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, March 1979.
E-2 ILM01.0
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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 data. 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,
E-3 ILMOL.O
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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 samples 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 results.
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
5. Procedures for Preparation, Approval, Review, Revision, and
Distribution of SOPs
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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
E-6 ILM01.0
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SECTION IV
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 resubmitted must be documented no
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 independent of the
source generating the deliverable.
o Change documentation must be retained according to the schedule of the
original deliverable.
c 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 Co 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.
E-7 ILM01 0
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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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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
- • 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 each time an analysis is
to be made and discarded after use. 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 except
for mercury. 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
within + 5% of the true value. Each standards concentration and the
E-9 ILM01.0
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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 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 CICV) 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
particular ICV. The values for the initial and subsequent
continuing calibration verifications shall be recorded on FORM II-
IN for ICP, AA, and cyanide analyses, as indicated.
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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 tr.ore
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. NBS SRM 1643a
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.
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
E-ll ILM01.0
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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 A A (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.
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),
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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 1II-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 che 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 isg/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.
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.
A group of samples prepared at Che same time.
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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 ^imes 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)
AS
Ba
Be
- Cd
Co
Cr
Cu
Mn
Ni
Pb
V
Zn
1
0
0
1
0
0
0
0
1
1
0
1
.0
.5
.5
.0
.5
.5
.5
.5
.0
.0
.5
.0
Al
Ca
Fe
Mg
500
500
200
500
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
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ILM01.0
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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. EPA 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. 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
d->ta 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 pose digest
spike is required for Hg.
In the instance where there is more thaa 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:
%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
2
EPA may require additional spike sample analysis, upon Administrative
Project Officer request, for which the Contractor will be paid.
E-15 ILM01.
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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).
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TABLE 3. SPIKING LEVELS FOR SPIKE SAMPLE ANALYSIS
For ICP/AA
For Furnace AA
Other
(1)
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) (rag/kg)
•x
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
10°(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
(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 origin.il (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
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ILM01.0
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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 CD)
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 - PI x 100
(S+D)/2
Where, RPD = Relative Percent Difference
S = First Sample Value (original)
D = Second Sample Value (duplicate)
The,results of the 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
for sample values 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.
o
EPA may require additional duplicate sample analyses, upon Administrative
Project Officer request, for which the Contractor will be paid.
E-18 ILM01.0
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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.
9. ICP Serial Dilution Analysis CD
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
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dilution analysis for one 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:
II - SI
% Difference - L 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.
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.
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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
(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-
E-21 ILM01.0
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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.
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 quantitacion. 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 spifce 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.
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" , 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.
Analytical Spikes are post-digestion spikes to be prepared prior to
analysis by adding a known quantity of the analyte to an aliquot of the
digested sample. The unspiked sample aliquot must 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.
"'"Spike" is defined as [absorbance or concentration of spike sample] minus
[absorbance or concentration of the sample].
E-22 ILM01.0
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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
must be flagged on the data sheet (FORM I-IN) with the letter
"S" if the correlation coefficient is 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-23 ILM01 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)
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%
YES
QUANTITATE BY MSA WITH 3
SPIKES AT 50, 100 £ 1SO\
OF SAMPLE ABSORBANCE
OR CONCENTRATION
(Only Single Injeclioni Rr
CORRELATION COEFFICIENT
LESS THAN 0.995
NO
FLAG DATA WITH "S"
NO
If YES, Repeat Only ONCE
If Still YES
NO
YES
SPIKE RECOVERY
LESS THAN 85% OR
GREATER THAN 115%
YES
NO
DILUTE SAMPLE
AND SPIKE
If YES, Repeat Only ONCE
If Still VES
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 -*••
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ILM01.0
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SECTION VI
LABORATORY EVALUATION PROCESS
This document outlines the procedures which will be used by the
Administrative Project Officer or his/her authorized representative to
conduct laboratory audits to determine the Contractor's ability to meet the
terms and conditions of this contract. The evaluation process incorporates
two major steps: 1) evaluation of laboratory performance, and 2) on-site
inspection of the laboratory to verify continuity of personnel,
instrumentation and quality control requirements of the contract.
I. Evaluation of Laboratory Performance
a. Performance Evaluation Sample Analysis
1) The Performance Evaluation (PE) sample set will be sent to a
participating laboratory on a quarterly basis to verify the
laboratory's continuing ability to produce acceptable
analytical results. These samples will be provided either
single blind (recognizable as a PE material and of unknown
composition), or double blind (not recognizable as PE
material and of unknown composition). If received as a
single blind, the Contractor is required to submit PE sample
data in a separate SDG package in accordance with Delivery
Schedule requirements for PE Sample data. PE samples
received as double blind would be treated as routine samples
and data would be submitted in the SDG deliverables package
per normal procedure.
2) When the PE data are received by EPA, results will be scored
routinely for identification and quantitation. Results of
these scorings will be provided for the Contractor via coded
evaluation spreadsheets by analyte. The Government may
adjust the scores on any given PE sample to compensate for
unanticipated difficulties with a particular sample.
3) If the Contractor laboratory performs unacceptably, the
Contractor will be notified by the Administrative Project
Officer. A laboratory so notified may expect, but the
Government is not limited to, the following actions: a site
visit, a full data audit, cessation of sample shipments,
and/or laboratory analysis of a second PE sample. Failure by
the laboratory to take corrective actions and/or failure of
two successive PE sample analyses is indicative of Contractor
failure to maintain technical competence and will require
that the laboratory discontinue analysis of samples until
such time as the Administrative Project Officer has
determined that the laboratory has corrected the problem and
may resume analyses.
b. Inorganic Data Audit
Inorganic data audits are conducted by EMSL-LV on the Contractor's
sample data packages. The inorganic data audit provides the
Agency with an in-depth inspection and evaluation of the data
packages with regard to achieving QA/QC acceptability.
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2. On-Sice Laboratory Evaluation
The on-site laboratory evaluation helps to ensure that technical
competence is maintained and that all the necessary quality control
is being applied by the Contractor in order to deliver a quality
product.
a. Or.-site laboratory evaluations allow the evaluators to determine
that:
1) The organization and personnel are qualified to perform
assigned tasks;
2) Adequate facilities and equipment are available;
3) Complete documentation, including chain-of-custody of samples
is being implemented;
4) Proper analytical methodology is being used;
5) Adequate analytical quality control, including reference
samples, control charts, and documented corrective action
measure:., is being provided; and
6) Acceptable data handling and documentation techniques are
being used.
b. The on-site visit also serves as a mechanism for discussing
weaknesses identified through Performance Evaluation sample
analysis or through Contract Compliance Screening or other review
of data deliverables. Lastly, the on-site visit allows the
evaluation team to determine if the laboratory has implemented the
recommended and/or required corrective actions, with respect to
quality assurance, that were made during the previous on-site
visit.
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EXHIBIT F
CHAIN-OF-CUSTODY, DOCUMENT CONTROL,
AND STANDARD OPERATING PROCEDURES
F-l ILM01.0
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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 laborcitory.
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:
F-2 ILM01.0
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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
i
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
sr.d 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, pers. -.al ar.l instrument logs, and other
relevant deliverables to ensure :hat 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 accountaoility 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.
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
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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:
, _ 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 - Ar_/ solution or media introduced ir.to 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 (IGS), 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 deionized/distilled water.
CASE - a finite, usually predetermined number of samples collected over a
given time period from a particular site. Case numbers are assigned by the
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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 um 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.
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.
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Holding time — (sample analysis date - sample receipt date)
INDEPENDENT STANDARD - a Contractor-prepared standard 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 into 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
nonconsecutive days with seven consecutive measurements per day.
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.
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 matrix is either water or
soil/sediment. Matrix is not synonymous with phase (liquid or solid).
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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 addition 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) - an analytical control
that contains distilled, deionized water and reagents, which is carried
through the entire analytical procedure (digested and analyzed). An
aqueous method blank is treated with the same reagents as a sample with a
vater 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 no
sample receipt and handling, analytical methods, data reporting and
deliverables, and document control. Used synonymously with Statement of
Work (SOW).
t
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.
G-4 ILM01.0
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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.
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.
SOIL - synonymous with soil/sediment or sediment as used herein.
STOCK SOLUTION - a standard solution which can be diluted to derive other
standards.
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 -t 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
Page No.
SECTION I: Description of Deliverables H-1
SECTION II: Format A Specification H-3
SECTION III: Format B Specification H-26
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SECTION I
DESCRIPTION OF DELIVERABLES
1. Introduction
1.1 Two file formats are specified for delivery of computer-readable data.
Format A is oriented to the structure of the hardcopy reporting forms
required by the contract. Format B is oriented to the general data
required by the contract. Information sufficient to generate required
hardcopy forms is contained in either format. NOTE: Beginning in
March, 1991, all data submitted in electronic form shall be submitted
using the USEPA Standard for Electronic Transmission of Laboratory
Results, EPA Order 2180.2
1.2 The file or files for a Sample Delivery Group (SDG, see Exhibit A,
Section I, B) must be submitted on a diskette or diskettes (see
paragraph, 2.1). Information on a diskette or diskettes for any single
SDG must be in one, and only one, of the two formats. The format used
13 at the option of the laboratory. The option used must be included
in the File Name specification (paragraph 2.2).
1.3 Format A consists of variable length ASCII records, and Format B
consists of fixed-length 80-byte ASCII records.
1.4 All information for one SDG must be in one file if format A is used.
Use of Format B may require information for one SDG to be in a number
of files. Format B may require more than one 360 K diskette for a
valid SDG.
2. Deliverable
2.1 The file or files niust 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-byte 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 in either format should not be included on the
diskettes.
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2.2 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
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 of
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 ASC123.I1A
Format 3 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.
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SECTION II
FORMAT A SPECIFICATION
1. Format Characteristics
1.1 Format A is based upon the structure of the hardcopy reporting forms
required by the contract. With two exceptions, Form Suffix and Record
Type, all fields in the format correspond directly with entries or
i terns on the hardcopy forms.
1.2 Format A includes detailed specifications for the required format of
each Inorganic Reporting Form's HEADER and DETAIL records. The exact
columns in which each field is to be contained are shown, as well as
the length of the field. Each field's required contents are specified
either as a literal (contained in single quotes) which must appear
exactly as shown (without the quotes), or as a variable for which a
format is listed in the format column. Each field's required format is
sp.cified either as an option of two or more choices (divided by
slashes), as MM/DD/YY for a date, as a CHARACTER field, or as a NUMERIC
field.
1.3 Format fields listed as CHARACTER may contain any standard ASCII
characters, and must be left-justified and padded with blanks. Formats
listed as NUMERIC may contain numeric digits, a decimal point, and a
leading plus or minus sign, and must be right-justified and padded with
blanks. The numbers following the word NUMERIC specify the maximum
number of digits which are allowed on either side of the decimal. The
decimal point is not assumed and must be contained in the field in its
correct position. For example, the format "NUMERIC 3.2" allows 3
digits preceding the decimal point and 2 following it (a total length
of 6 characters). The format "NUMERIC S3.2" allows a leading plus or
minus sign (a total length of 7). If a field's format description does
not contain a decimal point, then a decimal point is not allowed in the
field. If a field's format description does not contain an "S", then a
sign is not allowed in the field.
Explanation of NUMERIC fields in Format A.
In the examples below the format NUMERIC 3.2 is described.
(Quotation marks indicate limits of the field described and are not
included in the format.)
If the value of the field is 10.1:
The columns in the format will appear as: "10.10" (six columns).
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The table below demonstrates several examples:
Value Appears oh Format
10.1 "10.10"
10.11 "10.11"
100.11 "100.11"
100 "100.00"
.29 "0.29"
-100.129 Invalid
-10.1 Invalid
The following table presents examples of NUMERIC S3.2:
Value Appears on Format
10.1 " 10.10" (seven columns)
-10.11 " -10.11"
-100.11 "-100.11"
-1000.1 Invalid
100 " 100.00"
-.22 " -0.22"
-.239 " -0.24"
2. Record Types
2.1 Format A consists of variable length ASCII records. The last two bytes
of each record must contain "carriage return" and "line feed",
respectively. Unused bytes in partially filled fields must be blank-
filled.
2.2 Format A has three types of records: Header Records, Detail Records
and Comment Records.
Tvoe Tvpe ID Contents
Header H Nonrepeating fields which
together are unique to the
associated hardcopy form
Detail D A group of fields that are
repeated on a form, and are
uniquely positioned by (e.g.,
Analyte Chemical Symbol)
Comment C Nonrepeating fields containing
text that comments on informa-
tion reported on the form
The format for Comment Records is the same for all forms, and is
described after all other formats.
2.3 The first 5 bytes of each record contain the FORM ID, identifying the
Inorganic Analysis Reporting Form for which the record contains data.
The ID must be left-justified in the field.
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FORM ID FORM NAME
COVER COVER PAGE - INORGANIC ANALYSES DATA PACKAGE
I INORGANIC ANALYSIS DATA SHEET
11(1) INITIAL AND CONTINUING CALIBRATION VERIFICATION
11(2) CRDL STANDARD FOR AA AND ICP
III BLANKS
IV 1C? INTERFERENCE CHECK SAMPLE
V(l) SPIKE SAMPLE RECOVERY
V(2) POST DIGEST SPIKE SAMPLE RECOVERY
VI DUPLICATES
VII LABORATORY CONTROL SAMPLE
VIII STANDARD ADDITION RESULTS
IX ICP SERIAL DILUTIONS
X INSTRUMENT DETECTION LIMITS (QUARTERLY)
XI ICP INTERELEMENT CORRECTION FACTORS (ANNUALLY)
XII ICP LINEAR RANGES (QUARTERLY)
XIII PREPARATION LOG
XIV ANALYSIS RUN LOG
Following the FORM ID is a two-byte, left-justified, FORM SUFFIX, which
must be unique for each set of records that correspond to one hardcopy
form. For example, records for the first occurrence of a form must
contain the suffix AA. Records for the second occurrence must contain
AB, and the twenty-seventh occurrence would contain BA.
The 8th byte of each record contains the TYPE ID, which specifies what
kind of data the record contains (see paragraph 2.2).
Records with the same FORM ID and FORM SUFFIX must be grouped together
in the file. Within each FORM ID/FORM SUFFIX group, there may be only
one HEADER record, and it must come first. DETAIL records must follow
the HEADER record. The COMMENT records, which are optional, must come
last in the group, and be in sequence corresponding to the form.
The FORM ID/FORM SUFFIX group(s) for the COVER PAGE(S) must come first
in .the file. After the COVER PAGE(S), the FORM ID/FORM SUFFIX groups
do not have to be in any specific order. For example, a set of
HEADER/DETAIL/COMMENT records for FORM V could come before records for
FORM I, as long as the records within the group are in the correct
order.
3. Record Length
Table 3.1 summarizes the length (excluding carriage return/line feed) and
(in parentheses) the number of records in Format A. The maximum number
of detail and comment records is shown, corresponding to a submission of
hardcopy foras on which information is written on all possible lines.
H-5 ILM01.0
-------
Table 3.1 Format A Summary
Form Record
Header Detail Comment
Cover 80a(l)b 25(20) 78(4)
I 90(1) 31(24) 73(4)
11(1) 32(1) 65(24)
11(2) 32(1) 66(23)
III 18(1) 59(24)
IV 32(1) 64(23)
V(l) 33(1) 66(24) 78(4)
V(2) 23(1) 62(24) 78(4)
VI 38(1) 56(24)
VII 32(1) 68(24)
VIII 8(1) 69(32)
IX 23(1) 44(23)
X 52(1) 29(23) 78(4)
XI(1) 28(1) 77(23) 78(4)
XI(2) 28(1) 77(23) 78(4)
XII 28(1) 29(23) 78(4)
XIII 10(1) 32(32)
XIV 38(1) 59(32)
a Length of record in bytes (excluding carriage return/line feed).
Maximum number of records required for a form.
Record Listing
The remainder of this section contains detailed specifications for every
record required for a full set of hardcopy forzis.
H-6 ILM01.0
-------
COVER PAGE
INORGANIC ANALYSES DATA PACKAGE COVER PAGE HEADER RECORD:
COLUMN(S)
1-5
6-7
8
9-33
34-43
44-49
50-54
55-60
61-66
67-71
72-74
75-77
78-80
5
2
I
25
10
6
5
6
6
5
3
3
3
CONTENTS
1 COVER'
FORM SUFFIX
'H'
LAB NAME
CONTRACT
LAB CODE
CASE NUMBER
SAS NUMBER
SDG NUMBER
SOW NUMBER
ICP INT CORRECTIONS
ICP BG CORRECTIONS
RAW DATA BEFORE
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
'YES'/'NO'
'YES'/'NO'
'YES'/'NO'/BLANK
NOTE: The LAB NAME, CONTRACT, LAB CODE, CASE NUMBER, SAS NUMBER, AND SDG
NUMBER, which are contained in the COVER PAGE HEADER record, are not
repeated in the HEADER records of the other forms. Each form's
HEADER record contains only data which are unique to the DETAIL
records which follow it.
INORGANIC ANALYSES DATA PACKAGE COVER PAGE DETAIL RECORDS:
COLUMN(S) LENGTH CONTENTS FORMAT
1-5
6-7
8
9-15
16-25
5
2
1
7
10
'COVER'
FORM SUFFIX
'D'
EPA SAMPLE NO.
LAB SAMPLE ID NO.
CHARACTER
CHARACTER
H-7
ILM01.0
-------
INORGANIC ANALYSIS DATA SHEET HEADER RECORD:
COLUMNCS)
CONTENTS
FORMAT
1-5
6-7
.8
9-15
16-20
21-30
31-33
34-41
42-46
47-51
52-60
61-69
70-75
76-31
82-87
88-90
5
2
1
7
5
10
3
8
5
5
9
9
6
6
6
3
'I
FORM SUFFIX
'H'
EPA SAMPLE NO.
MATRIX
LAB SAMPLE ID
LEVEL
DATE RECEIVED
PERCENT SOLIDS
CONCENTRATION UNITS
COLOR BEFORE
COLOR AFTER
CLARITY BEFORE
CLARITY AFTER
TEXTURE
ARTIFACTS
CHARACTER
'WATER'/'SOIL'
CHARACTER
'LOW /'MED'
MM/DD/YY
NUMERIC 3.1
'UG/L '/ 'MG/KG'
CHARACTER
CHARACTER
CHARACTER
CHARACTER
CHARACTER
'YES'/BLANK
INORGANIC ANALYSIS DATA SHEET DETAIL RECORDS:
COLUMN(S) LENGTH CONTENTS
1-5 5 'I
6-7 2 FORM SUFFIX
8 1 'D'
9-10 2 ANALYTE SYMBOL
11-22 - 12 CONCENTRATION
23 1 CONC FLAG (C)
24-29 6 QUALIFIER (Q)
30-31 2 METHOD (M)
FORMAT
CHARACTER
NUMERIC 9.2
'B'/'U'/BLANK
UP TO 6 ONE-CHARACTER
FLAGS (OTHER THAN 'B'
OR 'U')
METHOD CODE/'NR'
H-8
ILM01.0
-------
FORM II (PART 1)
INITIAL AND CONTINUING CALIBRATION VERIFICATION HEADER RECORD:
COLUMN(S) LENGTH CONTENTS FORMAT
'II(l)'
FORM SUFFIX
'H'
INIT CAL SOURCE CHARACTER
CONT CAL SOURCE CHARACTER
1-5
6-7
8
9-20
21-32
5
2
1
12
12
INITIAL AND CONTINUING CALIBRATION VERIFICATION DETAIL RECORDS:
COLUMN fS") LENGTH ONTSNTS 70R.MA1
'IKD'
FORM SUFFIX
'D'
ANALYTE SYMBOL CHARACTER
INITIAL CAL TRUE
INITIAL CAL FOUND
INITIAL CAL %R
CONT CAL TRUE
CONT CAL FOUND 1
CONT CAL %R 1
CONT CAL FOUND 2
CONT CAL %R 2
METHOD (M)
1-5
6-7
8
9-10
11-17
18-25
26-30
31-37
38-45
46-50
51-58
59-63
54-65
5
2
1
2
7
8
5
7
8
5
3
5
2
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
KUMERIC
NUMERIC 3.1
METHOD CODE/'
5.1
5.2
3.1
5.1
5.2
3.1
5.2
H-9
ILM01.0
-------
FORM II (PART 2)
CRDL STANDARD FOR AA AND ICP HEADER RECORD:
COLUMNrS) LENGTH CONTENTS
'11(2)'
FORM SUFFIX
.'H'
AA STANDARD SOURCE
ICP STANDARD SOURCE
1-5
6-7
8
9-20
21-32
5
2
1
12
12
FORMAT
CHARACTER
CHARACTER
CRDL STANDARD FOR AA AND ICP DETAIL RECORDS:
COLUMN (S")
1-5
6-7
8
9-10
11-17
18-26
27-31
32-38
39-47
48-52
53-61
62-66
5
2
1
2
7
9
5
7
9
5
9
5
CONTENTS
'11(2)'
FORM SUFFIX
'D'
ANALYTE SYMBOL
AA TRUE
AA FOUND
AA %R
ICP INIT TRUE
ICP INIT FOUND
ICP INIT %R
ICP FINAL FOUND
1C? FINAL %R
FORMAT
CHARACTER
NUMERIC 5.1
NUMERIC 6.2
NUMERIC 3.1
NUMERIC 5.1
NUMERIC 6.2
NUMERIC 3.1
NUMERIC 6.2
NUMERIC 3.1
H-10
ILM01.0
-------
FORM III
BLANKS HEADER RECORD:
COLUMN CS') LENGTH
1-5
6-7
8
9-13
14-18
5
2
1
5
5
CONTENTS
'III '
FORM SUFFIX
'H'
PREP BLANK MATRIX
PREP BLANK UNITS
'WATER'/'SOIL '
'UG/L '/'MG/KG'
BLANKS DETAIL RECORDS:
COLUMN(SI
LENGTH
1-5
6-7
8
9-10
11-18
19
20-27
28
29-36
37
38-45
46
47-55
57
58-59
5
2
1
2
8
1
8
1
8
1
8
1
10
1
2
CONTENTS
'III '
FORM SUFFIX
'D'
ANALYTE SYMBOL
INITIAL CAL BLANK
INITIAL CAL FLAG (C)
CONT CAL BLANK 1
CC BLANK 1 FLAG (C)
CONT CAL BLANK 2
CC BLANK 2 FLAG (C)
CONT CAL BLANK 3
CC BLANK 3 FLAG (C)
PREPARATION BLANK
PREP BLANK FLAG (C)
METHOD (M)
CHARACTER
NUMERIC S5.1
'B'/'U'/BLANK
NUMERIC S5.1
'B'/'U'/BLANK
NUMERIC S5.1
'B'/'U'/BLANK
NUMERIC S5.1
'B'/'U'/BLANK
NUMERIC S3. 3
'B'/'U'/BLANK
METHOD CODE/'NR'
H-ll
ILM01.0
-------
FORM IV
ICP INTERFERENCE CHECK SAMPLE HEADER RECORD:
COLUMNfS) LENGTH CONTENTS FORMAT
1-5 5 'IV
6-7 2 FORM SUFFIX
8 1 'H'
9-20 12 ICP ID NUMBER CHARACTER
21-32 12 ICS SOURCE CHARACTER
ICP INTERFERENCE CHECK SAMPLE DETAIL RECORDS:
COLUMN CS1) LENGTH CONTENTS FORMAT
1-5 5 'IV
6-7 2 FORM SUFFIX
8 1 'D'
9-10 2 ANALYTE S-fllBOL CHARACTER
11-16 6 TRUE A NUMERIC 6
17-22 6 TRUE AB NUMERIC 6
23-29 7 INITIAL A NUMERIC S6
30-38 9 INITIAL AB NUMERIC S6.1
39-43 5 INITIAL %R NUMERIC 3.1
44-50 7 FINAL A NUMERIC S6
51-59 9 FINAL AB NUMERIC S6.1
60-64 5 FINAL %R NUMERIC 3.1
H-12 ILM01.0
-------
FORM V rPART
SPIKE SAMPLE RECOVERY HEADER RECORD:
COLUMNrs)
1-5
6-7
8
9-15
16-20
21-23
24-28
29-33
5
2
1
7
5
3
5
5
CONTENTS
'V(l) '
FORM SUFFIX
'H'
EPA SAMPLE NO.
MATRIX
LEVEL
CONCENTRATION UNITS
SAMPLE % SOLIDS
FORMAT
CHARACTER
'WATER'/'SOIL '
'LOW /'MED'
'UG/L '/ 'MG/KG'
NUMERIC 3.1
SPIKE SAMPLE RECOVERY DETAIL RECORDS:
COLUMNCS)
1-5
6-7
8
9-10
11-16
17-30
31
32-44
45
46-56
57-63
64
65-66 '
5
2
I
2
6
14
1
13
1
11
7
1
2
CONTENTS
'V(l) '
FORM SUFFIX
'D'
ANALYTE SYMBOL
CONTROL LIMIT %R
SPIKED SAMPLE RESULT
SSR FLAG (C)
SAMPLE RESULT
SR FLAG (C)
SPIKE ADDED
PERCENT RECOVERED
QUALIFIER (Q)
METHOD (M)
FORMAT
CHARACTER
'75-125'/BLANK
NUMERIC 9.4
'B'/'U'/BLANK
NUMERIC 8.4
'B'/'U'/BLANK
NUMERIC 8.2
NUMERIC S4.1
'N'/BLANK
METHOD CODE/'NR'
H-13
ILM01.0
-------
FORM V (PART 2)
POST DIGEST SPIKE SAMPLE RECOVERY HEADER RECORD:
COLUMN(SI
1-5
6-7
8
9-15
16-20
21-23
5
2
1
7
5
3
CONTENTS
'V(2) '
FORM SUFFIX
•H'
EPA SAMPLE NO.
MATRIX
LEVEL
FORMAT
CHARACTER
'WATER'/'SOIL
•LOW'/'MED'
POST DIGEST SPIKE SAMPLE RECOVERY DETAIL RECORDS:
COLUMNCS)
1-5
6-7
8
9-10
11-16
17-28
29
30-41
42
43-52
53-59
60
61-62
5
2
1
2
6
12
1
12
1
10
7
1
2
CONTENTS
'V(2) '
FORM SUFFIX
'D'
ANALYTE SYMBOL
CONTROL LIMIT %R
SPIKED SAMPLE RESULT
SSR FLAG (C)
SAMPLE RESULT
SR FLAG (C)
SPIKE ADDED
PERCENT RECOVERED
QUALIFIER (Q)
METHOD (M)
CHARACTER
BLANK
NUMERIC 9.2
'B'/'IJ'/KLANK
NUMERIC 9.2
•B'/'U'/BLANK
NUMERIC 8.1
NUMERIC S4.1
BLANK
METHOD CODE/'NR'
H-14
ILM01.0
-------
FORM VI
DUPLICATES HEADER RECORD:
COLUMN(S)
LENGTH
1-5
6-7
8
9-15
16-20
21-23
24-28
29-33
34-38
5
2
1
7
5
3
5
5
5
CONTENTS
•VI
FORM SUFFIX
'H'
EPA SAMPLE NO.
MATRIX
LEVEL
CONCENTRATION UNITS
SAMPLE % SOLIDS
DUPLICATE % SOLIDS
CHARACTER
'WATER'/'SOIL '
'LOW'/'MED'
'UG/L '/'MG/KG'
NUMERIC 3.1
NUMERIC 3.1
DUPLICATES DETAIL RECORDS:
COLUMN(S)
LENGTH
1-5
6-7-
8
9-10
11-17
18-31
32
33-46
47
48-53
54
55-56
5
2
1
2
7
14
1
14
1
6
1
2
CONTENTS
'VI '
FORM SUFFIX
'D'
ANALYTE SYMBOL
CONTROL LIMIT
SAMPLE
SAMPLE FLAG (C)
DUPLICATE
DUPLICATE FLAG (C)
RPD
QUALIFIER (Q)
METHOD (M)
FORMAT
CHARACTER
NUMERIC 5.1
NUMERIC 9.4
'B'/'U'/BLANK
NUMERIC 9.4
'B'/'U'/BLANK
NUMERIC 4.1
'*'/BLANK
METHOD CODE/'NR'
H-15
ILM01.0
-------
FORM VII
LABORATORY CONTROL SAMPLE HEADER RECORD:
COLUMNfS) LENGTH CONTENTS FORMAT
1-5 5 'VII '
6-7 2 FORM SUFFIX
8 1 'H'
9-20 12 SOLID LCS SOURCE CHARACTER
21-32 12 AQUEOUS LCS SOURCE CHARACTER
LABORATORY CONTROL SAMPLE DETAIL RECORDS:
COLUMN ("S") LENGTH CONTENTS FORMAT
1-5 5 'VII '
6-7 2 FORM SUFFIX
8 1 'D'
9-10 2 ANALYTE SYMBOL CHARACTER
11-17 7 AQUEOUS TRUE NUMERIC 5.1
18-25 8 AQUEOUS FOUND NUMERIC 5.2
26-30 5 AQUEOUS % RECOVERED NUMERIC 3.1
31-38 8 SOLID TRUE NUMERIC 6.1
39-46 8 SOLID FOUND NUMERIC 6.1
47 1 SOLID FOUND FLAG (C) 'B'/'U'/BLANK
48-55 8 SOLID LOWER LIMIT NUMERIC 6.1
56-63 8 SOLID UPPER LIMIT NUMERIC 6.1
64-68 5 SOLID % RECOVERED NUMERIC 3.1
H-16 ILM01.0
-------
FORM VIII
STANDARD ADDITION RESULTS HEADER RECORD:
COLUMN(S) LENGTH CONTENTS
1-5
6-7
8
FORMAT
5
2
I
'VIII '
FORM SUFFIX
'H'
NOTE: Although there are no fields which occur only once per FORM VIII, the
HEADER record must be included as a place holder, indicating that
DETAIL records follow.
STANDARD ADDITION RESULTS DETAIL RECORDS:
COLUMNCS) LENGTH CONTENTS
1-5
6-7
8
9-15
16-17
18-22
23-28
29-33
34-39
40-44
45-50
51-55
56-62
63-68
69
5
2
1
7
2
5
6
5
6
5
6
5
7
6
1
'VIII '
FORM SUFFIX
'D'
EPA SAMPLE NO.
ANALYTE SYMBOL
0 ADD ABSORBANCE
1 ADD CONCENTRATION
1 ADD ABSORBANCE
2 ADD CONCENTRATION
2 ADD ABSORBANCE
3 ADD CONCENTRATION
3 ADD ABSORBANCE
FINAL CONCENTRATION
CORRELATION COEF (R)
QUALIFIER (Q)
FORMAT
CHARACTER
CHARACTER
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC
NUMERIC 1.3
NUMERIC 5.1
NUMERIC 1.4
'+'/BLANK
1.3
3.2
1.3
3.2
1.3
3.2
H-17
ILM01.0
-------
FORM IX
ICP SERIAL DILUTIONS HEADER RECORD:
COLUMN(S) LENGTH CONTENTS
1-5
6-7
8
9-15
16-20
21-23
5
2
1
7
5
3
'IX
FORM SUFFIX
'H'
EPA SAMPLE NO.
MATRIX
LEVEL
FORMAT
CHARACTER
'WATER'/'SOIL
'LOW/'MED'
ICP SERIAL DILUTIONS DETAIL RECORDS:
COLUMN(S) LENGTH CONTENTS
1-5
6-7
8
9-10
11-22
23
24-35
36
37-41
42
43-44
5
2
1
2
12
1
12
1
5
1
2
'IX
FORM SUFFIX
'D'
ANALYZE STCIBOL
INIT SAMPLE (I)
INIT SAMPLE FLAG (C)
SERIAL DILUTION (S)
DILUTION FLAG (C)
PERCENT DIFFERENCE
QUALIFIER (Q)
METHOD (M)
FORMAT
CHARACTER
NUMERIC 9.2
'B'/'U'/BLANK
NUMERIC 9.2
'B'/'U'/BLANK
NUMERIC 3.1
'E'/BLANK
METHOD CODE/'NR'
H-18
ILM01.0
-------
FORM X
INSTRUMENT DETECTION LIMITS (QUARTERLY) HEADER RECORD:
COLUMNCS) LENGTH CONTENTS FOE
1-5
6-7
8
9-16
17-28
29-40
41-52
5
2
1
8
12
12
12
FORM SUFFIX
'H'
DATE
ICP ID NUMBER
FLAME AA ID NUMBER
FURNACE AA ID NUMBER
MM/DD/YY
CHARACTER
CHARACTER
CHARACTER
INSTRUMENT DETECTION LIMITS (QUARTERLY) DETAIL RECORDS:
COLUMNCS) LENGTH CONTENTS FORMAT
1-5
6-7
8
9-10
11-17
18-19
20-27
28-29
2
1
2
7
2
8
2
'X
FORK SUFFIX
'D'
ANALYTE SYMBOL
WAVELENGTH
BACKGROUND
IDL
METHOD (M)
CHARACTER
NUMERIC 4.2
'BS'/'BD'/'BZ'/BLANK
NUMERIC 6.1
METHOD CODE/'NR'
H-19
ILM01.0
-------
FORM XI (PART 1)
ICP INTERELEMENT CORRECTION FACTORS (ANNUALLY) HEADER RECORD:
COLUMN(S) LENGTH CONTENTS FORMAT
1-5
6-7
8
9-20
21-28
5
2
1
12
8
'XI(l)'
FORM SUFFIX
'H'
ICP ID NUMBER
DATE
CHARACTER
MM/DD/YY
ICP INTERELEMENT CORRECTION FACTORS (ANNUALLY) DETAIL RECORDS:
COLUMN(S) LENGTH CONTENTS FORMAT
1-5
6-7
8
9-10
11-17
18-19
20-29
30-31
32-41
42-43
44-53
54-55
56-65
66-67
68-77
5
2
1
2
7
2
10
2
10
2
10
2
10
2
10
'XI(l)'
FORM SUFFIX
'D'
ANALYTE SYMBOL
WAVELENGTH
ELEMENT
ELEMENT
SYMBOL
FACTOR
ELEMENT 2 SYMBOL
ELEMENT 2 FACTOR
ELEMENT 3 SYMBOL
ELEMENT 3 FACTOR
ELEMENT 4 SYMBOL
ELEMENT 4 FACTOR
ELEMENT 5 SYMBOL
ELEMENT 5 FACTOR
CHAKACTE?.
NUMERIC 4.2
AL
NUMERIC SI.7
CA
NUMERIC SI. 7
FE
NUMERIC SI. 7
MG
NUMERIC SI. 7
CHARACTER
NUMERIC SI.7
NOTE: ELEMENTS 1, 2, 3 and 4 SYMBOL can only be AL, CA, FE and MG
respectively. ELEMENT 5 Symbol can be any other analyte symbol.
H-20
ILM01.0
-------
FORM XI (PART 2)
ICP INTERELEMENT CORRECTION FACTORS (ANNUALLY) HEADER RECORD:
COLUMN(S) LENGTH CONTENTS FORMAT
CHARACTER
MM/DD/YY
1-5
6-7
8
9-20
21-28
5
2
1
12
8
FORM SUFFIX
'H'
ICP ID NUMBER
DATE
FORM SUFFIX
'D'
ANALYTE SYMBOL
WAVELENGTH
ICP INTERELEMENT CORRECTION FACTORS (ANNUALLY) DETAIL RECORDS:
COLUMNSS) LENGTH CONTENTS FORMAT
CHARACTER
NUMERIC 4.2
CHARACTER
NUMERIC SI.7
CHARACTER
NUMERIC SI.7
CHARACTER
NUMERIC SI.7
CHARACTER
NUMERIC SI.7
CHARACTER
NUMERIC SI. 7
1-5
6-7
8
9-10
11-17
18-19
20-29
30-31
32-41
42-43
44-53
54-55
56-65
66-67
68-77
5
2
1
2
7
2
10
2
10
2
10
2
10
2
10
ELEMENT 1
ELEMENT 1
ELEMENT 2
ELEMENT 2
ELEMENT 3
ELEMENT 3
SYMBOL
FACTOR
SYMBOL
FACTOR
SYMBOL
FACTOR
ELEMENT 4 SYMBOL
ELEMENT 4 FACTOR
5
5
ELEMENT
ELEMENT
SYMBOL
FACTOR
H-21
ILM01.0
-------
FORM XII
TCP LINEAR RANGES (QUARTERLY) HEADER RECORD:
COLUMN(S) LENGTH CONTENTS
1-5
6-7
8
9-20
21-28
5
2
1
12
8
'XII '
FORM SUFFIX
'H'
ICP ID NUMBER
DATE
FORMAT
CHARACTER
MM/DD/YY
ICP LINEAR RANGES (QUARTERLY) DETAIL RECORDS:
COLUMN(S) LENGTH CONTENTS
FORMAT
1-5
6-7
8
9-10
11-16
17-27
28-29
5
2
2
6
11
2
'XII '
FORM SUFFIX
'D'
ANALYTE SYMBOL
INTEGRATION TIME
CONCENTRATION
METHOD (M)
(ICP IS ASSUMED
IF BLANK)
CHARACTER
NUMERIC 3.2 (SECONDS)
NUMERIC 9.1
'NR'/BLANK
H-22
ILM01.0
-------
FORM XIII
PREPARATION LOG HEADER RECORD:
COLUMNCS) LENGTH CONTENTS FORMAT
1-5 5 'XIII '
6-7 2 FORM SUFFIX
8 1 'H'
9-10 2 METHOD METHOD CODE
PREPARATION LOG DETAIL RECORDS:
COLUMNCS) LENGTH . CONTENTS FORMAT
1-5 5 'XIII '
6-7 2 FORM SUFFIX
8 :. ' D •
9-15 7 EPA SA11PLE ir.J:.'3ER CHARACTER
16-23 ' PREP DATE MM/DD/YY
24-28 5' WEIGHT NUMERIC 2.2
29-32 4 VOLUME NUMERIC 4
H-23 ILM01.0
-------
FORM XIV
ANALYSIS RUN LOG HEADER RECORD:
COLUMN(S) LENGTH CONTENTS
1-5
6-7
8
9-20
21-22
23-30
31-38
5
2
1
12
2
8
8
'XIV '
FORM SUFFIX
'H'
INSTRUMENT ID NUMBER
METHOD
START DATE
END DATE
CHARACTER
METHOD CODE
MM/DD/YY
MM/DD/YY
ANALYSIS RUN LOG DETAIL RECORDS:
COLUMN(S)
CONTENTS
FORMAT
1-5
6-7
8
9-16
17-24
25-28
29-35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
5
2
1
8
8
4
7
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
' XIV '
FORM SUFFIX
'D'
EPA SAMPLE NUMBER
DILUTION FACTOR
TIME
PERCENT RECOVERED
ANALYTE (AL)
ANALYTE (SB)
ANALYTE (AS)
ANALYTE (BA)
ANALYTE (BE)
ANALYTE (CD)
ANALYTE (CA)
ANALYTE (CR)
ANALYTE (CO)
ANALYTE (CU)
ANALYTE (FE)
ANALYTE (PB)
ANALYTE (MG)
ANALYTE (MN)
ANALYTE (HG)
ANALYTE (NI)
ANALYTE (K)
ANALYTE (SE)
ANALYTE (AG)
ANALYTE (NA)
AiN'ALYTE (TL)
ANALYTE (V)
ANALYTE (ZN)
ANALYTE (CN)
CHARACTER
NUMERIC 5.2
HHMM
NUMERIC S4.1
"X"/BLANK
"X"/BLANK
"X"/BLANK
"X"/BLANK
"X-/BLANK
"X"/BLANK
"X"/BLANK
"X"/BLANK
"X"/BLANK
"XVBLANK
"X"/BLANK
"X"/BLANK
"X"/BLANK
"X"/BLANK
"X"/BLANK
"X"/BLANK
"X"/BLANK
"X-'/BLANK
"X"/BLANK
"X"/BLANK
"/BLANK
X" /BLANK
"X"/BLANK
"X
ii V"
H-24
ILM01.0
-------
COMMENT RECORDS
COMMENT records are optional for any FORM ID/FORM SUFFIX group. There may be
up to 4 COMMENT records per group. They must come after the DETAIL records
and be formatted as follows:
COLUMN(S) LENGTH CONTENTS FORMAT '
1-5 5 FORM ID
6-7 2 FORM SUFFIX
8 1 'C'
9-78 70 COMMENTS FREE FORM TEXT
The text may be in paragraph form if desired, but must be contained in columns
9 through 78 only. The key fields must be repeated in columns 1 through 8 of
each line.
H-25 ILM01.0
-------
SECTION III
FORMAT B SPECIFICATION
1. Introduction
1.1 This constitutes the implementation of the EPA standard for media and
record formats to be used in transmission of analytical results for the
CLP inorganics program. The following points should be noted:
1.1.1 The column border "|" is placed between fields to permit these
records to be prepared by programs written for laboratory and
quality assurance automation systems, and the detection of
possible field shift. They also assist in visual clarity.
1.1.2 Record formats contain sequence numbers and checksums to be
consistent with requirements for a. future error-free
telecommunications format.
2. Record Types
2.1 There are four groups of record types in the reporting format, as shcvr.
below. Detailed record formats follow.
Type Name Contents
10 Run Header Contains information pertinent to the
whole production run. See production
run definition below.
20 Sample Header Contains sample-identifying information,
or corresponding information for calibra-
tions, QC samples, instrument performance
checks, etc.
30 Results Record Contains any final result on a sample,
calibration or QC sample and identifying
information.
90 Comments Record Contains free-form comments and/or other
miscellaneous information.
2.2 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, 20,
and 90 series records following that record pertain to the same sample.
Type 30, representing an individual analyte, contains an indentifier to
H-26 ILM01.0
-------
identify the analyte. All 30 series records following that record
pertain to the same analyte.
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 - Cons tant.
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.
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 15 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 ("SIDICF"), and
WAVELENGTH COUNT.
A r.inimun! of cne group of type 32, 34, and 35 rec~rcc —:~t irj?.3ci.c.tely
follow the type 16 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, 22, 28 records, which
holds sample level identifying information, followed by a ninlir.um of one
group composed of type 30, 31, and 33 records for each analyte's
wavelength. The type 20 record holds a count for the number of analyte
wavelengths being used to determine results. The WAVELENGTH COUNTER must
H-27 ILM01.0
-------
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 ens'ure file
and record integrity:
Record Field
Positior. Length Contents Remarks
1-2 2 Record type or identifier "10" or as appropriate
72-74 3 Record sequence number 000-999, repeated as
within file necessary
.ju
75-78 4 Record checksum Four hexadecimal digits ;
Calculation algorithm to
be supplied
79-80 2 Contains CR and LF
6. Dates and Times
Wherever a date or time-of-day is required, the information consists of
successive groups of two right justified decimal digits each, separated
by "|". Dates are given in the order YY MM DD, and times as HH MM. All
hours will be given as 0 to 23 using a 24 hour clock and will be local
time. Since some computers generating the date and time sequence may
have difficulty producing leading zeros, these will not be required.
7. Field format listed as CHARACTER may contain any standard ASCII character
other than "|". It must be left justified and padded to the right with
blanks. Field format listed as NUMERIC may contain numeric digits, a
decimal point, and a leading plus or minus sign. It must be right
justified and padded to the left with blanks. Except where specified
otherwise, the numeric field must contain the minimum significance
specified in the forms instruction of Exhibit B. If more significance is
used, it must be applied uniformly. Exponent fields are numeric fields
H-28 ILM01.0
-------
that can contain only digits and plus or minus sign. No decimal is
allowed. For field formats that are specified as a choice of stings or
characters, only those choices shown may be used.
8. 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.
The checksum is defined to be the sum of the thirty-five (35) INTEGERS that
make up the data in columns 1 to 70 when the data is represented in the format
35A2 on processors which store the data bytes in left to right order. The sum io
taken module 65536 (2 ) and represented as four (4) hexadecimal digits. For
processors which use an A70 character representation of the data, the checksum is
the sum of all the even character position values plus 256 times the sum of all
odd character position values.
H-29 ILM01.0
-------
FORMAT OF THE PRODUCTION RUN FIRST HEADER RECORD (TYPE
COLUMN'S
LENGTH
1
3
4
6
7
9
10
12
13
15
16
18
19
- 2
- 3
- 5
— 6
- 8
- 9
- 11
- 12
- 14
- 15
- 17
- 18
- 20
2
1
2
1
2
1
2
1
2
1
2
1
2
21
22
"J T
-^ —
32
35
36
42
43
58
59
69
70
71
72
75
- 21
- 30
- 31
- 34
- 35
- 41
- 42
- 57
- 58
- 68
- 69
- 70
- 71
- 74
- 78
1
9
T_
^
1
6
1
15
1
10
1
1
1
3
4
CONTENTS
RECORD TYPE
M I II
ANALYSIS START YEAR
n I it
ANALYSIS START MONTH
n | n
ANALYSIS START DAY
ii I n
ANALYSIS START HOUR
ti I it
ANALYSIS START MINUTE
n I n
METHOD
n I it
BLANK
LAB CODS
it | ii
BLANK
it I ti
INSTRUMENT ID
n | n
BLANK
it I n
RECORD SEQUENCE NUMBER
RECORD CHECKSUM
FORMAT
"10"
YY
MM
DD
HH
MM
"AM"/"CV"/"AV"/"C"/
»CA"/"AS"/"T"
CliASACTER
CHARACTER
NUMERIC
NUMERIC
H-30
ILM01.0
-------
FORMAT OF THE PRODUCTION RUN SECOND HEADER RECORD (TYPE
COLUMNS
LENGTH
1
3
4
6
7
9
10
12
13
15
16
18
19
21
22
23
24
25
26
27
28
53
54
,'1
72
75
- 2
- 3
- 5
- 6
- 8
- 9
- 11
- 12
- 14
- 15
- 17
- 18
- 20
- 21
- 22
- 23
- 24
- 25
- 25
- 27
- 52
- 53
- 70
- 71
- 74
- 78
2
1
2
1
2
1
2
1
2
1
2
1
2
1
1
1
1
1
-
-L
25
1
17
1
3
4
CONTENTS
RECORD TYPE
it I n
ANALYSIS END YEAR
it I N
ANALYSIS END MONTH
it I n
ANALYSIS END DAY
n I n
ANALYSIS END HOUR
n I n
ANALYSIS END MINUTE
n I it
AUTO-SAMPLER USED
n I n
INTERELEMENT CORRECTIONS APPLIED
n | n
BACKGROUND CORRECTIONS APPLIED
n I n
RAW DATA GENERATED
ii I n
LABORATORY NIu-IE
n I n
BLANK
ii I n
RECORD SEQUENCE NUMBER
RECORD CHECKSUM
FORMAT
"16"
YY
MM
DD
HH
MM
"Y"/BLANK
NUMERIC
NUMERIC
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 en the Cover Pacre. "Y"
equals "YES", and "N" equals "NO".
This is the answer to the third question on the Cover Page. "B" equals
"YES", and "A" equals BLANK.
H-31
ILM01.0
-------
FORMAT OF THE SAMPLE HEADER DATA RECORD fTYPE 20)
COLUMNS LENGTH CONTENTS FORMAT
1-2 2 RECORD TYPE "20"
3-3 1 "|"
4-5 2 BLANK
6-6 1 "|"
7-14 8 EPA SAMPLE NUMBER CHARACTER
15-15 1 "| "
16-16 1 MATRIX iiniiii 2
17-17 1 "| "
18-24 7 BLANK
25-25 1 "| "
26-31 6 CASE NUMBER CHARACTER
32-32 1 "|"
33-37 5 BLANK
38-38 1 "|"
39-40 2 ANALYSIS YEAR YY
41 - 41 1 "|"
42-43 2 ANALYSIS MONTH MM
44-^4 1 "|"
-'.5 - -'.6 ;• ANALYSIS T .Y DD
*-r / ~~ *± I __ I
48-49 : ANALYSIS KOUR HH
50-50 1 "|"
51-52 2 ANALYSIS MINUTE MM
53-53 1 "|"
54-54 1 BLANK
55-55 1 "|«
56-56 1 SAMPLE UNIT CODE "G"/"M" 3
57-57 1 "|"
58-65 8 SAMPLE SIZE NUMERIC
(WET WEIGHT OR INITIAL VOLUME)
66-66 I "\"
67-69 2 ANALYTS VCAVELZirGTI-I COUNT NUMERIC
70-70 1 "|"
71-71 1 "|"
72-74 3 RECORD SEQUENCE NUMBER NUMERIC
75-78 4 RECORD CHECKSUM NUMERIC
1 EPA Sample Number as appears on Form XIV except for the first type 20
record. The first type 20 record must have an EPA Sample Number of
"SIDICF"
2 "1" equals "WATER", and "F" equals "SOIL"
3 "G" equals grams, and "M" equals mL.
H-32 ILM01.0
-------
FORMAT OF THE SAMPLE HEADER DATA RECORD (TYPE 21)
COLUMNS LENGTH CONTENTS FORMAT
1-2 2 RECORD TYPE "21"
3-3 1 " | "
4-4 1 BLANK
5-5 1 "|"
6-6 1 CONCENTRATION LEVEL "M"/"L" ^
7-7 1 " | "
8-16 9 BLANK
17-17 1 " | " '
18-23 6 SAS NUMBER CHARACTER
24-24 1 "|"
25-34 10 LAB SAMPLE ID CHARACTER
35-35 1 "|"
36-36 1 "|"
37-38 2 PREPARATION YEAR YY
39-39 1 "|"
40-41 2 PREPARATION MONTH MM
42-42 1 "|"
43-44 2 PREPARATION DAY DD
• 5-45 : <•{<••
-.6-46 1 BLANK
-=7 - 47 I "|"
48-49 2 LAB RECEIPT YEAR YY
50-50 1 "|"
51-52 2 LAB RECEIPT MONTH MM
53 - 53 1 "| "
54-55 2 LAB RECEIPT DAY DD
56-56 1 "|»
57 - 68 12 SOLUTION SOURCE CHARACTER
69-69 1 "| "
70-70 1 BLANK NUMERIC
71-71 1 "| »
~2 - 74 3 RECORD SEQUENCE NUMBER NUMERIC
75-78 4 RECORD CHECKSUM NUMERIC
1 "M" equals "MEDIUM", and "L" equals "LOW".
H-33 ILM01.0
-------
FORMAT OF THE SAMPLE HEADER DATA RECORD fTYPE 221
COLUMNS
1-2
3-3
4-40
41 - 41
42 - 46
47 - 47
48 - 55
56 - 56
57 - 64
65 - 65
66 - 70
71 - 71
72 - 74
75 - 78
2
1
37
1
5
1
8
1
8
1
1
3
4
CONTENTS
RECORD TYPE
n I it
BLANK
n I ii
FINAL VOLUME IN ML
it | n
DILUTION FACTOR
n I n
BLANK
II I Tl
PERCENT SOLIDS
RECORD SEQUENCE NUMBER
RECORD CHECKSUM
FORMAT
"22"
NUMERIC
NUMERIC
NUMERIC
(to one decimal place)
NUMERIC
NUMERIC
H-34
ILM01.0
-------
FORMAT OF THE SAMPLE HEADER DATA RECORD (TYPE 28)
COLUMNS LENGTH CONTENTS FORMAT
1-2 2 RECORD TYPE "28"
3-3 1 " | "
4-13 10 CONTRACT NUMBER CHARACTER
14-14 1 "| "
15-19 5 SOW NUMBER CHARACTER
20-20 1 "|"
21-26 6 SDG NUMBER CHARACTER
27-27 1 »|"
28-29 2 PREPARATION START HOUR HH 1
30-30 1 "|"
31 - 70 40 BLANK
71 - 71 1 «|"
72-74 3 RECORD SEQUENCE NUMBER NUMERIC
75-78 4 RECORD CHECKSUM NUMERIC
This is the hour at which the preparation is started. It is used to
differentiate between different batches on the same
H-35 ILM01.0
-------
FORMAT OF THE SAMPLE HEADER DATA RECORD (TYPE 301
COLUMNS
1
3
4
5
6
15
16
25
26
31
32
2
3
4
5
14
15
24
25
30
31
34
LENGTH
2
1
1
1
9
1
9
1
5
1
3
35
36
42
43
46
47
48
49
55
56
59
60
61
62
67
68
71
72
75
- 35
- 41
- 42
- 45
- 46
- 47
- 48
- 54
- 55
- 58
- 59
- 60
- 61
- 66
- 67
- 70
- 71
- 74
- 78
1
6
1
3
1
1
1
6
1
3
1
1
1
5
1
3
1
3
4
CONTENTS
RECORD TYPE
ii I it
ANALYTE IDENTIFIER TYPE
ii I ii
ANALYTE CAS NUMBER
ii 1«
BLANK
If I H
UNITS
ii I if
CONCENTRATION QUALIFIER
CONCENTRATION
EXPONENT
11 j ii
VALUE DESCRIPTOR
ti I ti
AMOUNT ADDED OR TRUE VALU£
EXPONENT
H I ti
QC VALUE DESCRIPTOR
n | ii
QC VALUE
EXPONENT
it I n
RECORD SEQUENCE NUMBER
RECORD CKECKSUil
FORMAT
"30"
CN FOR CYANIDE
"UG/L"/"MG/KG"
"BDL"/"LTC"/"FQC"/
»GTL"/"NAR"/"RIN"/
"REX "/BLANK 2
NUMERIC
"EVBIANK
NUMERIC
"T"/
NUMERIC
"E"/BLANK
NUMERIC
NUMERIC
"E"/BLANK
NUMERIC
NUMERIC
NUI12RIC
1
2
"C" 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. This is only used for the first, second, and third addition of
MSA. The zero addition must contain the final sample result in ug/L or
mg/Kg, as appropriate, whether the final result is reported on Form I or
not.
Note that there is no absolute equivalent to the final concentration on
Form VIII in Format B.
H-36
ILM01.0
-------
"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 form
reporting a valid result. They only explain why or if the result is
qualified.
3 HTH 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.
4 "P" equals percent, "C" equals correlation coefficient, and "L" equals
control limit
H-37 ILMOl.O
-------
FORMAT OF THE SAMPLE HEADER DATA RECORD (TYPE 31)
COLUMNS
1 -
3 -
4 -
5 -
6 -
2
3
4
5
6
7-7
8-15
15 - 15
16 - 17
18 - 18
19 - 28
29 - 29
30 - 37
38 - 38
39 - 48
49 - 49
50 - 57
58 - 53
59 - o G
69 - 69
70 - 70
71 - 71
72 - 74
75 - 78
LENGTH
2
1
1
1
1
1
8
1
2
1
10
1
8
1
10
1
8
1
10
1
1
1
3
4
CONTENTS
RECORD TYPE
ti I n
TYPE OF DATA
it | it
TYPE OF VALUE
ANALYTE WAVELENGTH
n I ii
BLANK
it I ii
FIRST INSTRUMENT VALUE
ii I it
BLANK
if I n
SECOND INSTRUMENT VALUE
it g n
BLANK
tr | n
THIRD INSTRUinNT VALUE
» I ii
BLANK
n | ii
RECORD SEQUENCE NUMBER
RECORD CHECKSUM
FORMAT
"31"
"W"
"Cn/nUn/n'B"/nF"
NUMERIC
(to two decimal places)
NUMERIC
NUMERIC
NUMERIC 2
NUMERIC
NUMERIC
"C" equals concentration in ug/L, "T" equals concentration in ug/250mL,
"F" equals concentration in ug/50 mL, "B" equals absorbarice, "I" equals
intensity, and "A" equals peak area in cm2.
This is used to report replicate injection 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 analysis, and leave the
third field empty. If triplicate instrument measurements were taken, then
enter the values in the order of their analysis.
H-38
ILM01.0
-------
FORMAT OF THE SAMPLE HEADER DATA RECORD (TYPE 32)
COLUMNS LENGTH CONTENTS FORMAT
1-2 2 RECORD TYPE "32"
3-3 1 " | "
4-7 4 BLANK
8-8 1 " | "
9-10 2 INTEGRATION TIME CODE "IT"
11-11 1 "|"
12-17 6 INTEGRATION TIME IN SECONDS NUMERIC
18-18 1 "E"/BLANK
19-21 3 EXPONENT NUMERIC
22-22 1 «|"
23 - 70 48 BLANK
71-71 1 »|"
72-74 3 RECORD SEQUENCE NUMBER NUMERIC
75-78 4 RECORD CHECKSUM NUMERIC
H-39 ILM01.0
-------
FORMAT OF
COLUMNS
LENGTH
1
3
4
13
14
15
16
26
27
28
29
35
36
39
40
41
42
'48
f. 0
52
53
59
60
63
64
71
72
75
- 2
- 3
- 12
- 13
- 14
- 15
- 25
- 26
- 27
- 28
- 34
- 35
- 38
- 39
- 40
- 41
- 47
- 48
- 51
- 52
- 58
- 59
- 62
- 63
- 70
- 71
- 74
- 78
2
1
9
1
1
1
10
1
1
1
6
1
3
1
1
1
6
1
3
I
6
1
3
1
7
1
3
4
CONTENTS
RECORD TYPE
it I tt
ANALYTE NAME
it | ii
RAW DATA AVERAGE QUALIFIER
ii I (i
RAW DATA AVERAGE
n i ft
RAW DATA %RSD QUALIFIER
N I it
RAW DATA %RSD
EXPONENT
ii j »
QC LIMIT QUALIFIER
n i ti
QC LOWER LIMIT
EXPONENT
.,,.<
QC UPPER LIMIT
EXPONENT
n i ii
CRDL IN UG/L
ii i it
RECORD SEQUENCE NUMBER
RECORD CHECKSUM
FORMAT
"33"
CHARACTER
JL
NUMERIC
"M"/BLAJTK
NUMERIC
"E"/BLANK
NUMERIC
NUMERIC
"E"/BLANK
NUMERIC
NUMERIC
"E"/BLANK
NUMERIC
NUMERIC
NUMERIC
NUMERIC
" ''
"U" means less than the IDL, "B" means less the CRDL and greater than or
-qual to the IDL, "L" means greater than
"S" flag is not applicable for Format B.
-ie nger rane.
H-40
ILM01.0
-------
FORMAT OF THE SAMPLE HEADER DATA RECORD fTYPE
COLUMNS
LENGTH
1
3
4
14
15
23
24
30
31
34
35
41
42
45
46
60
61
/"* t1
64
66
67
69
70
71
72
75
- 2
- 3
- 13
- 14
- 22
- 23
- 29
- 30
- 33
- 34
- 40
- 41
- 44
- 45
- 59
- 60
- 62
- 63
- 65
- 66
- 68
- 69
- 70
- 71
- 74
- 78
2
1
10
1
8
1
6
1
3
1
6
1
3
1
14
1
2
-
2
1
2
1
1
1
3
4
CONTENTS
RECORD TYPE
n I n
BLANK
ii j ti
ANALYTE WAVELENGTH
n I it
IDL
n I n
BLANK
n I n
LINEAR RANGE
EXPONENT
n I n
BLANK
ii I n
YEAR COMPUTED
MONTH COMPUTED
n I n
DAY COMPUTED
ii I ii
BLANK
n I n
RECORD SEQUENCE NUMBER
RECORD CHECKSUM
FORMAT
"34"
NUMERIC
(to two decimal places)
NUMERIC 1
NUMERIC
"E"/BLANK
NUMERIC
NUMERIC
NUMERIC
The IDL must be a whole number for all analytes except for mercury.
Mercury must be reported to one decimal place.
H-41
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FORMAT OF THE SAMPLE HEADER DATA RECORD (TYPE 35)
COLUMNS
1
3
4
7
8
10
11
13
14
16
17
19
20
22
23
32
33
42
48
49
52
53
71
72
75
- 2
- 3
- 6
- 7
- 9
- 10
- 12
- 13
- 15
- 16
- 18
- 19
- 21
- 22
- 31
- 32
- 40
- 47
'- 43
- 51
- 52
- 70
- 71
- 74
- 78
LENGTH
2
1
3
1
2
1
2
1
2
1
2
1
2
1
9
1
8
6
1
3
1
18
1
3
4
CONTENTS
RECORD TYPE
n I ti
TYPE OF CORRECTION
n I ii
TYPE OF BACKGROUND
n I n
BLANK
n I n
YEAR COMPUTED
N I it
MONTH COMPUTED
n I n
DAY COMPUTED
ii I n
CAS # OF INTERFERING ANALYTE
n i »
ANALYTE WAVELENGTH
CORRECTION FACTOR
EXPONENT
ii i ii
BLANK
n i n
RECORD SEQUENCE NUMBER
RECORD CHECKSUM
FORMAT
"35"
"ICP"/"BG
n 1
"ES"/"BD"/"BZ"
YY
MM
DD
CHARACTER
NUMERIC
(to t-.ro decir.^1
NUMERIC
"E"/BLANK
NUMERIC
NUMERIC
NUMERIC
"ICP" indicates interelement correction, while "BG" indicates a backgrounc
correction.
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FORMAT OF THE SAMPLE HEADER DATA RECORD (TYPE 90V
COLUMNS LENGTH CONTENTS FORMAT
1-2 2 RECORD TYPE "90"
3-3 1 " |"
4-70 67 ANY COMMENT CHARACTER
71-71 1 "|»
72-74 3 RECORD SEQUENCE NUMBER NUMERIC
75-78 4 RECORD CHECKSUM NUMERIC
H-43 ILM01.0
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FORMAT OF THE SAMPLE HEADER DATA RECORD fTYPE 92)
COLUMNS LENGTH CONTENTS FORMAT
1-2 2 RECORD TYPE "92"
3-3 1 " | "
4-12 9 COLOR BEFORE CHARACTER
13-13 1 "| "
14-22 9 COLOR AFTER CHARACTER
23-23 1 "| "
24-29 6 CLARITY BEFORE CHARACTER
30-30 1 "|"
31-36 6 CLARITY AFTER CHARACTER
37 - 37 1 "|"
38-43 6 TEXTURE CHARACTER
44-44 1 "| "
45-45 1 ARTIFACTS "YES"/BLANK
46-46 1 "|»
47 - 70 24 BLANK
71 - 71 1 " | "
72-74 3 RECORD SEQUENCE NUMBER NUMERIC
75-78 4 RECORD CHECKSUM NUMERIC
H-44 ILM01.0
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9. Example of the Sequence of Record Types in a Production Run
10 Contains run header information. Occurs once per run.
15 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 interelenient 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 v«»velength used in the
run.
34 Contains the IDL and Linear range information for second wavelength used
in the run.
25 Contains the 1 ackground and i-.^erelement correction information for
second wavelength used in the run.
32
33
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.
'."ill 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-45 ILM01.0
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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
2£
30
31
32
etc.
H-46 ILM01.0
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