United States Office of Publication 9240.1-14
Environmental Protection Solid Waste and EPA/540/R/94/093
Agency Emergency Response PB95-963516
K December1994
Superfund
USEPA CONTRACT
LABORATORY PROGRAM
STATEMENT OF WORK
FOR INORGANICS ANALYSIS
MULTI-MEDIA,
MULTI-CONCENTRATION
SOW No. 788
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9240.1-14
PB95-963516
EPA540/R-94/093
Attachment A
USEPA CONTRACT LABORATORY PROGRAM
STATEMENT OF WORK
FOR
INORGANICS ANALYSIS
Multi-Media
Multi-Concentration
SOW No. 788
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
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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'
SUMMARY OF REQUIREMENTS
SECTION I: GENERAL REQUIREMENTS
SECTION II: SPECIFIC REQUIREMENTS
SECTION III: DETAILED TECHNICAL & MANAGEMENT REQUIREMENTS
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SECTION I
GENERAL REQUIREMENTS
The Contractor shall employ procedures specified in this Statement of
Work (SOW) in the preparation and analysis of aqueous (water) and solid
(soil/sediment) samples for the presence and 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. Specifications for
reporting data in computer-readable format appear in Exhibit H.
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 SOU 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.
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SECTION II
SPECIFIC REQUIREMENTS
A. For each sample, the Contractor shall perform the following tasks:
Task I: Receive and Prepare Hazardous Vaste 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 nay 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 lover 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 quantisation of
analytes other than cyanide shall be accomplished using the ICF 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 TAL 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 Vork 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
oOtandard reference solutions from EPA, the National Bureau of
Standards 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. Additional quality assurance and quality control shall be required
on a quarterly basis in the form of Performance Evaluation Samples
submitted by EPA for Contractor analysis, and in the for* of
verification of instrument parameters, as described in Exhibit E.
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 floppy diskette in the format specified in this SOU and vithin
the time specified in the Contract Performance/Delivery Schedule.
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1. Use of formats other than those designated by EPA will be deemed
as noncompliance. Such data are unacceptable. Resubmission in
the specified format at no additional cost to the government will
be required.
2. Computer generated forms may be submitted in the hardcopy data
package(s) provided that the forms are in EXACT EPA FORMAT. This
means chat 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.
C. 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 Contractor shall have an IBM or IBM-compatible mini-computer or PC
capable of recording required sample data on 5.25 inch floppy double -
sided double-density 360 K-byte or 1.2 M-byte diskettes, in ASCII text
file format and in accordance with the file, record and field
specifications listed in Exhibit H.
E. 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
personnel qualifications and experience. See Section III, Detailed
Technical & Management Requirements.
1. Laboratory Supervisor
2. ICP Spectroscopist
3. ICP Operator
4. Atomic Absorption (AA) Operator
5. Inorganic Sample Preparation Specialist
6. Classical Techniques (Cyanide) Analyst
7. Inorganic Chemist (Backup)
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F. The Contractor shall respond in a timely Banner to requests from data
recipients for additional information or explanations that result from
the Government's inspection activities.
G. 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).
H. 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 Case File Purge (see Exhibit B).
I. Sample shipments to the Contractor's facility will be scheduled and
coordinated by the EPA CLP Sample Management Office (SHO), acting on
behalf of the Project Officer. The Contractor shall communicate with
SMO personnel by telephone as necessary -throughout the process of
sample scheduling, shipment, analysis and data reporting, to ensure
that samples are properly processed.
If there are problems with the samples (e.g., mixed media, containers
broken or leaking) or sample documentation/paperwork (e.g., Traffic
Reports not with shipment, or sample and Traffic Report numbers do not
correspond) the Contractor shall immediately contact SHO for
resolution. The Contractor shall immediately notify SHO 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.
J. Sample analyses will be scheduled by groups of samples, each defined as
a Case and identified by a unique EPA Case number assigned by SHO. 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
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.
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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.
K. Each sample received by the Contractor will be labeled with an EPA
sample number, .and accompanied by a Traffic Report font bearing the
sample number and descriptive information regarding the sample. 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.
L. 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.
H. 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.
N. The Contractor shall accept ail 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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SECTION III
DETAILED TECHNICAL & MANAGEMENT REQUIREMENTS
As cited in Section II, Task III, the Contractor shall have the following
technical and management capabilities:
A. TECHNICAL CAPABILITY
1. Technical Functions
a. Inorganics Laboratory Supervisor
(1) Responsible for all technical efforts of the Inorganics
Laboratory to meet all terms and conditions of the
contract.
(2) Qualifications
(a) Education:
Minimum .of Bachelor's degree in chemistry or any
scientific/engineering discipline.
(b) Experience:
Minimum of three years of laboratory experience,
including at least one year in a supervisory
position.
b. ICP Spectroscopist Qualifications
(1) Education:
o Minimum of Bachelor's degree in chemistry or any
scientific/engineering discipline.
o Specialized training in ICP Spectroscopy.
(2) Experience:
Minimum of two years of applied experience with ICP
analysis of environmental samples.
c. ICP Operator Qualifications
(1) Education:
Minimum of Bachelor's degree in chemistry or any
scientific/engineering discipline.
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(2) Experience:
Minimum of one year of experience in operating and
maintaining ICP instrumentation, in conjunction vith the
educational requirement; or, in lieu of educational
requirement, three additional years of experience in
operating and maintaining ICP instrumentation.
d. Atomic Absorption (AA) Operator Qualifications
(1) Education:
Minimum of Bachelor's degree in chemistry or any
scientific/engineering discipline.
(2) Experience:
Minimum of one year of experience in operating and
maintaining AA instrumentation for each of the following
AA techniques: (a) flame (if flame will be used), (b)
graphite furnace, and (c) cold vapor, in conjunction
vith the educational requirement; or, in lieu of
educational requirement, three additional years of
experience in operating and maintaining AA
instrumentation, including flame, graphite furnace, and
cold vapor techniques.
e. Inorganic Sample Preparation Specialist Qualifications
(1) Education:
Minimum of high school diploma and a college level
course in general chemistry or equivalent.
(2) Experience:
Minimum of six months of•experience in an analytical
laboratory.
f. Classical Techniques (Cyanide) Analyst Qualifications
(1) Education:
Minimum of Bachelor's degree in chemistry or any
scientific/engineering discipline.
(2) Experience:
Minimum of six months of experience with classical
chemistry .laboratory procedures, in conjunction with the
educational qualifications; or, in lieu of educational
requirement, two years of additional equivalent
experience.
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g. Technical Staff Redundancy
In order to ensure continuous operations to accomplish the
required work as specified by EPA contract, the bidder shall
have a minimum of one (1) chemist available at all tines as a
back-up technical person with the following qualifications.
(1) Education:
Minimum of Bachelor's degree in chemistry or any
scientific/engineering discipline.
(2) Experience:
Minimum of one year of experience in each of the
following areas —
o ICF operation and maintenance
o AA operation and maintenance
o Classical chemistry analytical procedures
o Sample preparation for inorganics analysis
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.
a. Sample Receipt Area
Adequate, contamination'free, well ventilated work space
provided with chemical resistant bench top for receipt and
— safe handling of EPA samples.
b. Storage Area
Sufficient refrigerator space to maintain unused EPA sample
volume for 60 days after data submission. Samples and
standards must be stored separately.
c. Sample Preparation Area
Adequate, contamination-free, we11-ventilated work space
provided with:
(1) Benches with chemical resistant tops.
(2) Exhaust hoods. Note: Standards must be prepared in a
glove box or isolated area.
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(3) Source of distilled or demineralized organic-free
water.
(4) Analytical balance(s) located away from draft and rapid
change in temperature.
3.
Instrumentation
At a minimum, the Contractor shall have the following instruments
operative at the tine of the Preaward Site Evaluation and
committed for the full duration of the contract.
a. (1) 100 Samples/Month Capacity Requirements
Fraction
1CP Metals
GFAA Metals
Mercury
Cyanide
No. of
Instrument (s)
1
1
1
6 distillation
units + 1
photometer
Type of
Instrument
ICP Emission
Spectrophotoneter
Atomic Absorption
Spectrophotometer
with Graphite
Furnace Atomizer
Mercury Cold Vapor
AA Analyzer or AA
instrument
modified for Cold
Vapor Analysis
See Cyanide
Me thods , S tatement j
of Work Exhibit D, |
Section IV, Part EJ
1
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(2) Secondary Instrument Requirements for 100 Samples/Month
Capacity
The Contractor shall have the following instruments
available (operational) at all tines as a back-up
system:
Quantity Instruments
one Graphite Furnace AA
one Mercury Cold Vapor AA System
These instruments must be included in the bidder's
inventory of equipment. In addition, the
Contractor shall have an in-house stock of
instrument parts and circuit boards to ensure
continuous operation to meet contract-specified
holding and turnaround times.
b. (1) 200 Samples/Month Capacity Requirements
Fraction
ICP Metals
GFAA Metals
Mercury
Cyanide
No. of
Instrument(s)
1
2
2
12 distillation
units + 1
photometer
Type of
Instrument
ICP Emission
Spe c t r opho tome te r
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 Vork Exhibit D, |
Section IV. Part E|
1
(2) There are no Secondary Instrument Requirements for 200
Samples/Month Capacity.
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c. Secondary Instrument Requirements for 300 or Greater
Samples/Month Capacity
The Contractor shall have the following instruments
available (operational) at all times as a back-up
system:
Quantity Instruments
one ICP Emission Spectrophotometer
one Graphite Furnace AA
These instruments must be included in the bidder's
inventory of equipment. In addition, the Contractor
shall have an in-house stock of instrument parts and
circuit boards to ensure continuous operation to meet
contract-specified holding and turnaround times.
d. Instrument. Specifications
Further information on instrument specifications and required
ancillary equipment may be found in this Exhibit and other
Exhibits in this Statement of Work.
4. Data Handling anU Packaging
The Contractor shall be able to submit reports and data packages
as specified in the Statement of Work Exhibit B. To complete this
task, the Contractor shall be required to:
a. Provide space, tables and copy machines to meet the contract
requirements.
b. Designate personnel.
B. 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:
1. Technical Staff
Responsible for all technical efforts for the EPA contract.
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Project Manager
Responsible for overall aspects of EPA contracC(s) (from sample
receipt to through data delivery) and shall be the primary contact
for EPA Headquarters Project Officer and Regional Deputy Project
Officers.
Sample Custodian
Responsible for receiving the EPA samples (logging, handling and
storage).
Quality Assurance Officer
Responsible for overseeing the quality assurance aspects of the
data and reporting directly to upper management.
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-l
SECTION II: Report Descriptions and Order of Data
Deliverables B-4
SECTION III: Form Instruction Guide B-13
SECTION IV: Data Reporting Forms B-38
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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 Project Officer will notify the Contractor in
writing of such changes when they occur.
Distribution
1
1
|*A.
1
1 B.
1
Item
Contract Start-Up
Plan
Updated SOPs
Copies
2
1
Schedule
7 days after contract
receipt.
120 days after contract
receipt.
(1)
X
X
(2)
X
(A)
X
| No. Delivery Distribution |
Item Copies Schedule (3) (4) (5) (6)
**C. Sample Traffic
Reports
***D. Sample Data
Package
***E. Data in Compute r-
Readable Form
F. Results of Inter -
comparison Study/
PE Sample Analysis
G. Compilation of
Complete Case File
Purge
H. Complete Case
File Purge
1
3
1
2
1
1
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
7 days after
data submission
180 days after
data submission
or 7 days from
receipt of
written request
by PO or SMO
X
X
X
X
X
X
N/
X
A
X
B-l
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1
| I ten
t
i **i. Quarterly
Verification
i of Instrument
j Parameters
1
1
No.
Copies
1 2
1
1
1
1
1
Delivery
Schedule (3)
Quarterly: | X
15th day of |
January, April |
July, October |
1
1
Distribution
(4) (5) (6)
X I
1
1
1
1
1
Distribution:
(1) Project Officer (PO)
(2) Contract Officer (CO)
(3) Sample Management Office (SMO)
(4) EMSL-LV
(5) Region-Client
(6) NEIC
* Contractor must be prepared to receive samples within 30 days of
Contract award. NOTE: EPA can't guarantee £ga££ adherence to
start-up plan that is agreed upon by PO and Contractor, but will
attempt to meet it as close as possible.
** 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 SOV Exhibit A, paragraph J., for further description).
NOTE: As specified in the Contract Schedule (Government Furnished
Supplies and MaCErials), 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 Analytical Operations Branch (UH-548A)
401 M Street, SW
Washington, DC 20460
ATTN: (Project Officer's Name)
(2) USEPA Contracts Management Division (MD-33)
Alexander Drive
Research Triangle Park, NC 27711
ATTN: (Contract Officer's Name)
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(3) USEPA Contract Laboratory Program (CLP)
Sample Management Office (SMO)
P. 0. Box 818
Alexandria, VA 22313
For overnight delivery service, use street address:
209 N. Hadison Street, 2nd Floor
Alexandria. VA 22314
(4) USEPA Environmental Monitoring
Systems Laboratory (EMSL-LV)
P. 0. Box 93478
Las Vegas, NV 89193-3478
ATTN: Data Audit Staff
For overnight delivery service, use street address:
944 E. Harmon, Executive Center
Las Vegas. NV 89109
ATTN: Data Audit Staff
(5) USEPA REGIONS:
The CLP Sample Management Office, acting on behalf of the Project
Officer, will provide the Contractor vith the list of addressees for the
ten EPA Regions. SMO will provide the Contractor vith updated Regional
address/name lists as necessary throughout the period of the contract
and identify other client recipients on a case-by-case basis.
(6) NEIC, Contractor Evidence Audit Team
2600 Vest Coifax, Suite C310
Lakevood, Colorado 80215
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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, 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.
Whenever the Contractor is required to submit or resubmit data as a
result of an on-site laboratory evaluation or through a PO/DPO action, the
data must be clearly marked as ADDITIONAL DATA and must be sent to all three
contractual data recipients (SMO, EMSL-LV, and Region). A cover letter shall
be included which describes what data is being delivered, to which EPA
Case(s) the data pertains, and who requested the data.
Whenever the Contractor is required to submit or resubmit data as a
result of Contract Compliance Screening (CCS) review by SMO, the data must be
sent to all three contractual data recipients (SMO, EMSL/LV and Region), and
in all three instances must be accompanied by a color-coded COVER SHEET
(Laboratory Response To Results of Contract Compliance Screening) provided by
SMO.
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.
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A. Contract Start-Up Plan
The Contractor shall submit a contract start-up plan for EPA approval as
specified in the Contract Performance/Delivery Schedule. The plan shall
set forth the Contractor's proposed schedule for receiving samples
starting with the 30th calendar day after award and ending with the date
the Contractor is capable of receiving the full monthly sample allotment
stipulated in the Contract. The Project Officer will review the
contract start-up plan within 7 days of submission and will notify the
Contractor of the plan's status.
NOTE: The Contractor shall be required to receive samples within 30
days of contract award. EPA can't guarantee exact adherence to start-up
plan that is agreed upon by the PO and Contractor, but will attempt to
meet it as close as possible.
B. 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 Performanc Evaluation sample data and the
evaluation of Bidder-Supplied Documentation.
The Contractor must supply SOPs for:
1. Sample receipt and logging.
2. Sample and extract storage.
3. Preventing sample contamination.
A. Security for laboratory and samples.
5. Traceability/Equivalency of standards.
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.
13. Document control, including case file preparation.
B-5 7/88
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C. 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 Sanple Delivery
Group.
Traffic Reports (TRs) shall be submitted in Sample Delivery Group (SDG)
sets (i.e., TRs for all samples in an SDG shall be clipped together),
with an SDG Cover Sheet attached.
The SDG Cover Sheet shall contain the following items:
o Lab name
o Contract number
o Sample Analysis Price - full sample price from contract.
o Case Number
o List of EPA sample numbers of all samples in the SDG, identifying the
first and last samples received, and their dates of receipt.
NOTE: When more than one sample is received in the first 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.
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
•11 data-jreporting 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.
D. Sample Data Package
The sample data package shall include data for analysis of all samples
in one Sample Delivery Group (SDG), including analytical (field)
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:
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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.; Statement of Work (SOV) number (appears on cover page of
SOW); EPA sample numbers in alphanumeric order, showing EPA sample
numbers cross-referenced with lab ID numbers; comments, describing
in detail any problems encountered in processing the samples in the
data package; and, completion of the statement on use of ICP
background and interelement corrections for the samples.
The Cover Page shall contain the following statement, verbatim: "I
certify that this data package is in compliance with the terms and
conditions of the contract, both technically and for completeness,
for other than the conditions detailed above. Release of the data
contained in this hardcopy data package and in the computer-readable
data submitted on floppy 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
s ignature.
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
validate 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 oust be
reported to one decimal place. The preceding discussion
concerning significant numbers applies to Form I only. For
B-7 7/88
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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]
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 Interelenient Correction Factors (Annually) [FORM XI
_ (PART 1) - IN]
3) ICP Interelament 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
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Raw data must contain all instrument readouts used for the
sample results. Each exposure or instrumental reading must be
provided, including those readouts that may fall below the IDL.
All AA and ICP instruments must provide a legible hard copy of
the direct real-time instrument readout (i.e., stripcharts,
printer tapes, etc.). A photocopy of the instruments direct
sequential readout must be included. A hardcopy of the
instrument's direct instrument readout for cyanide must be
included if the instrumentation has the capability.
The order of raw data in the data package shall be: ICP, Flame
AA, Furnace AA, Mercury, and Cyanide. All raw data shall
include concentration units for ICF and absorbances with
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 SDC, 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
B-9 7/88
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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
for initial and continuing calibration verification and
blanks, as well as interference check samples and CRDL
standard for ICF.
10) Integration tines for AA analyses.
e. Digestion and Distillation Logs
Logs shall be submitted in the following order: digestion logs
for ICP, flane 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 legible 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 oust also be submitted.
E. 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, floppy 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
nailer.
B-10 7/B8
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Table 1
Codes for Labelling Raw Data
Sample XXXXXX
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:
1C? S or SO for blank standard
Atomic Absorption and Cyanide SO, S10,...ecc.
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
CRJDL Standard for AA CRA
CRDL Standard for ICP " CRI
Laboratory Control Samples:
Aqueous (Water) LCSW
Solid (Soil/Sediment) LOSS
Preparation Blank (Water) PBW
Preparation Blank (Soil) PBS
Linear Range Analysis Standard LRS
Notes:
1. When an analytical spike or MSA is performed on samples other than field
samples, the "A", "0", -1", "2" or "3" suffixes must be the last to be
added to the EPA Sample Number. For instance, an analytical spike of a
duplicate must be formatted "XXXXXXDA."
2. The numeric suffix that follows the "S" suffix for the standards
indicates the true value of the concentration of the standard in ug/L.
3. ICP calibration standards usually consist of several analytes at
different concentrations. Therefore, no numeric suffix can follow the
ICP calibration standards unless all the analytes in the standard are
prepared at the same concentrations. For instance, the blank for ICP
must be formatted "SO."
B-ll 7/88
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4. The CRDL standard for AA is considered to be a calibration standard if
it was a part of the calibration curve, thus it oust be formatted like
any other standard. The "CRA* fornat must be used if the CRDL standard
for AA is not used to establish the calibration curve.
F. Results of Interconrparison/Perfonnance EvaluationfPE) Sample Analyses
Tabulation of analytical results for Interconparison/PE Sample analyses
include all requirements specified in items D. and E., above.
G. Compilation of Complete Case File Purge
Within 7 days after data submission, the Contractor shall have compiled
the Complete Case File Purge package described in item H., following.
H. Complete Case File Purge
The Complete Case File Purge package includes all laboratory records
received or generated for a specific Case that have not been previously
submitted to EPA as a deliverable. These items shall be submitted
along with their Case File Document Inventory (see Exhibit F, paragraph
2.4 for description of document numbering and inventory procedure).
These items include, but are not limited to: sample tags, custody
records, sample tracking records, analysts logbook pages, bench sheets,
instrument readout records, computer printouts, raw data summaries,
instrument logbook pages (including instrument conditions),
correspondence, and the document inventory.
Shipment of the Complete Case File Purge package by first class mail,
overnight carrier, priority mail or equivalent is acceptable. Custody
seals, which are provided by EPA, must be placed on shipping containers
and a document inventory and transmittal letter included. The
Contractor is not required to maintain any documents for a sample Case
after submission of the Complete Case File Purge package; however, the
Contractor should maintain a copy of the document inventory and
transmittal letter.
I. Quarterly Verification of Instrument Parameters
The Contractor shall perform and report quarterly verification of
instrument detection limits and linear range by methods specified in
Exhibit E for each instrument used under this contract. For the ICP
instrumentation and methods, the Contractor shall also report quarterly
interelement correction factors (including method of determination),
wavelengths used, and integration times. Quarterly Verification of
Instrument Parameters forms for the current quarter shall be submitted
in aaeh Sample Delivery Group data package. vising Forms X, XI and XII.
Submission of Quarterly Verification of Instrument Parameters shall
include the raw data used to determine those values reported.
B-12 , 7/88
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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 for AA and ICP [FORM II (PART 2) - IN]
F. Blanks [FORM III - IN]
G. ICP Interference Check Sample [FORM IV - IN]
H. Spike Sample Recovery [FORM V (PART 1) - IN]
I. Post Digest Spike Sample Recovery [FORM V (PART 2) - IN]
J. Duplicates [FORM VI - IN]
K. Laboratory Control Sample [FORM VII - IN]
L. Standard Addition Results [FORM VIII - IN]
M. ICP Serial Dilutions [FORM IX - IN]
N. Instrument Detection Limits (Quarterly) [FORM X - IN]
0. ICP Itvterelement 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]
B-13 7/88
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A. General Information and Header Information
The data reporting foms 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 must
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 chose forms can be submitted on one form.
All characters which appear on the data reporting forms presented in the
contract (Exhibit £, 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 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., "LOW", not "Low" or "low"). If an entry
does not_fill the entire blank space provided on the font, null
characters must be used to remove the remaining underscores that
comprise the blank line. (Sea 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 natch 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.
B-14 7/88
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The "Lab Code" is an alphabetic abbreviation of up to 6 characters,
assigned by EPA, to identify the laboratory and aid in data processing.
This lab code shall be assigned by EPA at the time a contract is
awarded, and must not be modified by the Contractor, except at the
direction of EPA.
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 Croup (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 tKat accompanied that sample.
In order to facilitate data assessment, the sample suffixes listed in
Table 1 must be used.
Other pieces of information are common to many of the Data Reporting
Forms. These include: Matrix and Level.
For "Matrix", enter "SOIL" for soil/sediment samples, and enter "WATER"
for water samples. NOTE: The matrix mist be spelled out.
Abbreviations such as "S" or "V" 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
B-15 7/88
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figures specified for that result entry for that form. If there are not
enough figures in the raw data result to enter in the specified space
for that result, then zeros must be used for decimal places to the
specified number of reporting decimals for that result for a specific
form. The following examples are provided:
Raw Data Result Specified Format Corrct 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 th£ 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 Paye - 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.
The "SOW No." is the EPA-designated number that indicates the Statement
of Work (SOU) version under which analyses in the data package have been
performed. The SOU No. appears on the cover of the contract Statement
of Work. For samples analyzed using this SOW. enter "7/88" for SOW No.
B-16 7/88
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Enter the EPA Sample No. (including spikes and duplicates) (to seven
spaces) of every sample analyzed vithin 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 MAE123 is
the lowest (considering both alpha and numeric characters) EPA Sample
No. vithin 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.
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 associated with an SDG.
C. Inorganic Analysis Data Sheet [FORM 1-IN]
. This form is used to tabulate and report sample analysis results for
target analytes (Exhibit C).
Complete the header information according to the instructions in Part A
and as follows.
"Date Received" is the date (formatted MM/DD/YY) of sample receipt at
the laboratory, as recorded on the Traffic Report, i.e., the Validated
Time of Sample Receipt (VTSR).
"% Solids" is the percent of solids on a weight/weight basis in the
sample as determined by drying the sample as specified in Exhibit D.
Report percent solids to one decimal place (i.e., 5.3%). If the percent
solids is not required because the sample is fully aqueous or less than
1% solids, then enter "0.0".
Enter the appropriate concentration units (UC/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
Che 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).
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Under the columns labeled "C", "Q", and "M", enter result qualifiers as
identified below. If additional qualifiers are used, their explicit
definitions must be included on the Cover Page in the Comments section.
FORM I-IN includes fields for three types of result qualifiers. These
qualifiers must be completed as follows:
o C (Concentration) qualifier -- Enter "B" if the reported value vas
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).
H - 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).
U - Post-digestion spike for Furnace AA analysis is out of
control limits (65-115%), 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". "V, 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
"CV" for Manual Cold Vapor AA
"AV" for Automated Cold Vapor AA
"AS" for Semi-Automated Spectrophotometric
"C" for Manual Spectrophotometric
"T" for Titrimetric
"NR" if the analyte is not required to be analyzed.
A brief physical description of the sample, both before and after
digestion, must be reported in the fields for color (before and after),
clarity (before and after), texture and artifacts. For water samples,
report color and clarity. For soil samples, report color, texture and
artifacts.
B-18 7/88
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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.
D. Initial and Continuing Calibration Verification [FORM II(PART 1)-IN]
This form is used to report analyte recoveries from calibration
solutions.
Complete the header information according to the instructions in Part A
and as follows.
Enter the Initial Calibration Source (12 spaces maximum) and the
Continuing Calibration Source (12 spaces maximum). Enter "EPA-LV" or
"EPA-CI" to indicate EPA EMSL Las Vegas or Cincinnati, respectively, as
the source of EPA standards. When additional EPA supplied solutions are
prepared in the future, the Contractor must use the codes supplied with
those solutions for identification. If other sources were used, enter
sufficient information in the available 12 spaces to identify the
manufacturer and the solution used.
Use additional FORMs II(PART 1)-IN if more calibration sources were
used.
Under "Initial Calibration True", enter the value (in ug/L, to one
decimal place) of the concentration of each analyte in Che Initial
Calibration Verification Solution.
Under "Initial Calibration Found", enter the most recent value (in ug/L,
to two decimal places), of the concentration of each analyte measured in
the Initial Calibration Verification Solution.
Under "Initial Calibration %R", enter the value (to one decimal place)
of the percent recovery computed according to the following equation:
%R - Found(ICV) x 100 (2 1}
True(ICV)
B-19 7/88
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Where, True(ICV) is the true concentration of the analyte in the Initial
Calibration Verification Solution and Found(ICV) is the found
concentration of the analyte in the Initial Calibration Verification
Solution.
The values used in equation 2.1 for True(ICV) and Found(ICV) must be
exactly those reported on this form.
Under "Continuing Calibration True", enter the value (in ug/L, to one
decimal place) of the concentration of each analyte in the Continuing
Calibration Verification Solution.
Under "Continuing Calibration Found", enter the value (in ug/L, to two
decimal places) of the concentration of each analyte measured in the
Continuing Calibration Verification Solution.
Note that the form contains two "Continuing Calibration Found" columns.
The column to the left must contain values for the first Continuing
Calibration Verification, and the column to the right must contain
values for the second Continuing Calibration Verification. The column
to the right should be left blank if no second Continuing Calibration
Verification was performed.
If more .than one FORM II(PART 1)-IN is required to report multiple
Continuing Calibration Verifications, then the column to the left on the
second form must contain values for the third Continuing Calibration
Verification, the column to the right must contain values for the fourth
Continuing Calibration Verification, and so on.
Under "Continuing Calibration %R", enter the value (to one decimal
place) of the percent recovery computed according to the following
equation:
%R - Found(CCV) x 10Q (2 2)
_ True(CCV)
where, True(CCV) is the true concentration of each analyte, and
Found(CCV) is the found concentration of the analyte in the Continuing
Calibration Verification Solution.
The values used in equation 2.2 for True(CCV) and Found(CCV) must be
exactly those reported on this form.
Note that the form contains two "Continuing Calibration %R" columns.
Entries to these columns must follow the sequence detailed above for
entries to the "Continuing Calibration Found" columns.
Under "M", enter the method used or "NR", as explained in Part C.
If more than one wavelength is used to analyze an analyte, submit
additional FORMs II(PART 1)-IN as appropriate.
B-20 7/88
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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 IlA's as appropriate. For instance, the first ICV for
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 vas 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 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 x JQQ /2 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.
B-21 ' 7/88
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Under "CRDL Standard for ICP, Initial %R* enter the value (to one
decimal place) of the percent recovery computed according to the
following equation:
^H _ CRDL Standard for ICP Initial Found x ^QQ ^ ^\
CRDL Standard for ICP True
Under "CRDL Standard for ICP Final Found*, enter the value (in ug/L, to
two decimal places) of the concentration of each analyte measured in the
CRDL Standard Solution analyzed at the end of each run.
Under "CRDL Standard for ICP Final %R", enter the value (to one decimal
place) of the percent recovery computed according to the following
equation:
%R - CRDL Standard for ICP Final Found *QQ (25)
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. When multiple
wavelengths are used for one analyte, .all the results of one wavelength
must be reported before prodeeding to the next wavelength.
F. Blanks [FORM III-IN]
This form is used to report analyte concentrations found in the Initial
Calibration Blank (ICB), in Continuing Calibration Blanks (CCB), and in
the Preparation Blank (PB).
Complete the header information according to the instructions in Part A
and as follows.
Enter "SOIL* 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 *MC/KG" (for soil) as the Preparation Blank
concentration units.
B-22 7/88
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Under "Initial Calib. Blank", enter the concentration (in ug/L, to one
decimal place) of each analyte in the most recent Initial Calibration
Blank.
Under the "C" qualifier field, for any analyte enter "B" if the absolute
value of the analyte concentration is less than the CRDL but greater
than or equal to the IDL. Enter "U" if the absolute value of the
analyte in the blank is less than the IDL.
Under "Continuing Calibration Blank 1". enter the concentration (in
ug/L, to one decimal place) of each analyte detected in the first
required Continuing Calibration Blank (CCB) analyzed after the Initial
Calibration Blank. Enter any appropriate qualifier, as explained for
the "Initial Calibration Blank," to the "C" qualifier column immediately
following the "Continuing Calibration Blank 1" column.
If only one Continuing Calibration Blank was analyzed, then leave the
columns labeled "2" and "3" blank. If up to three 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 one
decimal place) 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 BOP* than one wavelength is used to analyze an analyte, submit
additional FORMs III-IN as appropriate.
The order of reporting ICBs and CCBs for each analyte must follow the
temporal order in which the blanks were run starting with the first Form
III and moving from left to right and continuing to the following Form
Ill's as explained in Part D. When mutliple wavelengths are used for
the analysis of one analyte, all the results of one wavelength oust 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:
B-23 7/88
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For "ICP ID Number", enter an identifier that uniquely identifies a
specific instrument within the Contractor laboratory. No two ICP
instruments within a laboratory may have the same ICP ID Number.
Enter "ICS Source" (12 spaces maximum) as explained in Part D. For EPA
solutions include in the source name a number identifying it (e.g., EPA-
LV87).
Under "True Sol. A", enter the true concentration (in ug/L, to the
nearest whole number) of each analyte present in Solution A.
Under "True Sol. AB", enter the true concentration (in ug/L, to the
nearest whole number) of each analyte present in Solution AB.
Under "Initial Found Sol. A", enter the concentration (in ug/L. to the
nearest whole number) of each analyte found in the initial analysis of
Solution A as required in Exhibit E.
Under "Initial Found Sol. AB", enter the concentration (in ug/L, to one
decimal place) of each analyte in the initial analysis of Solution AB as
required in Exhibit E.
Under "Initial Found %R", enter the value (to one decimal place) of the
percent recovery computed according to the following equation:
%R - Initial Found Solution AB x ^QQ /2 6)
True Solution AB
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:
^ _ Final Found Solution AB x ^QQ /2 -j\
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.
B-24 ' 7/88
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If more ICS analyses were required, submit additional FORM* IV-IN as
appropriate.
The order of reporting ICSs for each analyte must follow the temporal
order in which the standards were run starting with the first Form IV
and continuing to the following Form IVs as appropriate. The order of
reporting ICS is independent. When multiple wavelengths are used for
one analyte, all the results of one wavelength must be reported before
prodeeding to the next wavelength.
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 hot,
leave the field empty.
Under "Spiked Sample Result (SSR)", enter the measured value (to four
decimal places), in appropriate units, for each 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, Che value
added and reported must be that specific concentration in appropriate
units.
B-25 7/88
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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 10Q
SA
%R must be reported, whether it is negative, positive or zero.
The values for SSR, SR, and SA must be exactly those reported on this
form. A value of zero must be used for SSR or SR if the analyte value
is less Chan 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 "MR"
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
aaximum) 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,
Co 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 Che 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 Che "C"
qualifier column immediately following the "Sample Result (SR)" column.
B-26 7/88
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Under "Spike Added (SA)", enter the value (in ug/L, to one decimal
place) for each analyte added to the sample. The sane concentration
units must be used for spiked sample results, unspiked (original sample)
results, and spike added sample results. If the spike added
concentration is specified in the contract, the value added and reported
must be that specific concentration in appropriate units.
Under "%R", enter the value (to one decimal place) of the percent
recovery for all spiked analytes computed according Co 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 Sx CRDL. If the sample and duplicate values were less
than the CRDL or greater than or equal to 5x CRDL, leave the field
empty.
B-27 7/88
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Under Sample (S). enter the original measured value (to four decimal
places) for the concentration of each analyte in the sample (reported in
the EPA Sample No. box) on which a Duplicate analysis was performed.
Concentration units are those specified on the form. Enter any
appropriate qualifier, as explained in Part C, to the "C" qualifier
column immediately following the "Sample (S)" column.
Under Duplicate (D), enter the measured value (to four decimal places)
for each analyte in the Duplicate sample. Concentration units are those
specified on the form. Enter any appropriate qualifier, as explained in
Part C, to the "C" qualifier column immediately following the "Duplicate
(D)" column.
For solid samples, the concentration of the original sample must be
computed using the weight and % solids of the original sample. The
concentration of the duplicate sample must be computed using the weight
and % solids of the duplicate 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.
B-28 7/88
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For the Solid LCS Source (12 spaces maximum), enter "EPA0387" 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.
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 ^ 1Q£) ^ 1Q)
Aqueous LCS True
Under "Solid True", enter the value (in mg/Kg, to one decimal place) of
the concentration of each analyte in Che Solid LCS Source.
Under "Solid Found", enter the measured value (in mg/Kg, to one decimal
place) of each analyte found in the Solid LCS solution.
Under "C", enter "B" or "U" or leave empty, to describe the found value
of the solid LCS as explained in Part C.
Under "Limits", enter the lower limit (in mg/Kg. to one decimal place)
in the left column, and the upper limit (in mg/Kg, to one decimal place)
in the right column, for each analyte in the Solid LCS Source solution.
Under "Solid %R", enter the value of the percent recovery (to one
decimal place) computed according to the following equation:
%R ~- Solid LCS Found ^ 1QO
Solid LCS True
The values for true and found aqueous and solid LCS'c 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 fora 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.
B-29 7/88
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Under "EPA. Sample No.", enter the EPA Sample Numbers (7 spaces maximum)
of all aralytical 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 camples and duplicates may be reported on this
form, thus the EPA Sample Number usually has no suffix or a "D."
A maximum of 32 samples can be entered on this form. If additional
samples required MSA, submit additional FORMs VIII-IN. Samples must be
listed in alphanumeric order per analyte, continuing to the next FORM
VIII-IN if applicable.
Under "An", enter the chemical symbol (2 spaces maximum) for each
analyte for which MSA was required for each sample listed. The analytes
must be in alphabetic listing of the chemical.symbols.
Results for different samples for each analyte must be reported
sequentially, with the analytes ordered according to the alphabetic
listing of their chemical symbols. For instance, results for As
(arsenic) in samples MAAllO, MAA111, and MAA112 would be reported in
sequence, followed by the result for Pb (lead) in MAAllO 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 Co 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 Co 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.
B-30 7/88
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Under "Final Cone.", enter the final analyte concentration (in ugA, to
one decimal place) in the sample as determined by MSA computed
according to the following formula:
Final Cone. - - (x- intercept) X DIL <2.12)
Note that the final concentration of an analyte does not have to equal
the value for that analyte which is reported on FORM I -IN for that
sample.
Under "r" , enter the correlation coefficient (to four decimal places)
chat is obtained for the least squares regression line representing the
following points (x,y):(0.0, "OADDABS"). ("1 ADD CON". "lADDABS"),
("2 ADD CON", "2 ADD ABS"), ("3 ADD CON", '3 ADD ABS").
Note that the correlation coefficient oust be calculated using the
ordinary least squares linear regression (unweighted) according to the
following formula:
r -- _ -. (2.13)
(N Ix2 - ( IX)2] [N £y2 - (
Under "Q" , enter "+" if r is less than 0.995. If r is greater than or
equal to 0.995, then leave the field empty.
M. ICP Serial 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)" col turn.
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.
B-31 7/88
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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 Bust be
established based on the serial dilution result before correcting it for
the dilution regardless of the value reported on the form.
Under "% Difference", enter the absolute value (to one decimal place) of
the percent difference in concentration of required analytes, between
the original sample and the diluted sample (adjusted for dilution)
according to the following formula:
% Difference - I I - S I x 10° (2.14)
I
The values for I and S used to calculate % Difference in equation 2.14
must be exactly those reported on this fora. 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 XI-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-Che 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.
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 XI-IN as appropriate
to report the Instrument Detection Limit.
B-32 7/88
-------
Under "Background", enter the type of background correction used to
obtain Furnace AA data. Enter "BS" for Smith Hieftje, "BD" for
Deuterium Arc, or "BZ" for Zeeman background correction.
Contract Required Detection Limits (in ug/L) as established in Exhibit
C, must appear in the column headed "CRDL".
Under "IDL", enter the Instrument Detection Limit (ug/L, to one decimal
place) as determined by the laboratory for each analyte analyzed by the
instrument for which the ID Number is listed on this form. 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 FORHs X-IN if more instruments and wavelengths are used.
Note that the date on this form must not exceed the analysis dates in
the SDG data package or precede them by more than three months.
Use the Comments section to indicate alternative wavelengths and the
conditions under which they are used.
ICP Interelement Correction Factors (Annually) [FORM XI(PART 1)-IN]
This form documents for each ICP instrument the interelement correction
factors applied by the Contractor laboratory to obtain data for the
Sample Delivery Group.
Although the correction factors are determined annually (every twelve
calendar months), a copy of the results of the annual interelement
correction factors must be included with each SDG data package on FORM
XKPART D-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 HM/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.
B-33 7/88
-------
Under "Al", "Ca". "Fe". "Mg", enter the correction factor (negative,
positive or zero, to seven decimal places. 10 spaces maximum) for each
ICF analyte. If correction factors for another analyte are applied, use
the empty column and list the analyte's chemical symbol in the blank
two-space header field provided for that column.
If corrections are not applied for an analyte, a zero must be entered
for that analyte to indicate that the corrections were determined to be
zero. If correction factors are applied for more than one additional
analyte. use FORM XI(PART 2)-IN.
P. ICP Interelement Correction Factors (Annually) [FORM XI(PART 2)-IN]
This form is used if correction factors for analytes other than Al, Ca,
Fe, Mg, and one more analyte of the Contractor's choice, were applied to
the analytes analyzed by ICP. Complete this form as for FORM XI(FART
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
designateiTby the Contractor to identify each ICP instrument used to
produce data for the SDG. If more thah one ICP instrument is used,
submit additional FORMs XII-IN as appropriate.
Report the date (formatted as MM/DD/YY) on which these linear ranges
were determined for use. This date must not exceed the dates of
analysis by ICP in the SDG data package and must not precede the
analysis dates by more than three calendar months.
Under "Integ. Time (Sec.)-,* enter the integration time (in seconds to
two decimal places) used for each measurement taken from the ICP
instrument.
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.
B-34 7/88
-------
Under "M", enter "NR" for analytes analyzed by methods other than ICP.
No entries are required under "M" for analytes analyzed by ICP.
If more instruments or analyte wavelengths are used, submit additional
FORMs XII-IN as appropriate.
R. Preparation Log [Fora XIII-IN]
This Form is used to report the preparation run log.
All field samples and all quality control preparations (including
duplicates, spikes, LCS's, PB's and repreparations) associated with the
SOG must be reported on Form XIII.
Submit one Form XIII per method if no more than thirty-two preparations,
including quality control preparations, were performed. If more than
thirty-two preparations per method were performed, then submit
additional Forms XIII as appropriate.
Complete the header information according to the instructions in Fart 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 SDC, and of all other preparations such as duplicates, 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. If a cample was
reprepared, list the same EPA Sample Number in the order of increasing
preparation date.
Under "Preparation Date", enter the date (formatted MM/DD/YY) on which
each sample was prepared for analysis by the method indicated in Che
header section of the Form.
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-35 7/88
-------
S. Analysis Run Lop [Form XIV-IN]
This Form is used to report the sample analysis run log.
A run is defined as the totality of analyses performed by an instrument
throughout the sequence initiated by. and including, the first SOW-
required calibration standard and terminated by, and including, the
continuing calibration verification and blank following the last SOW-
required analytical sample.
All field samples and all quality control analyses (including
calibration standards, ICVs, CCVs, ICBs, CCBs, CRAs, CRIs, ICSs, LRSs,
LCSs, FBs, 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.
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 to the next Form
XIV for the instrument run if applicable. The analysis date and time of
other analyses not associated with the SDG, but analyzed by the
instrument in the reported analytical run, must be reported. Those
analyses must be identified with the EPA Sample No. of "ZZZZZ".
B-36 7/88
-------
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
be performed. The dilution factor does not include the dilution
inherent in the preparation as specified by the preparation procedures
in Exhibit D.
Note that for a particular sample a dilution factor of "1" oust 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 Fora 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 XA 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.
Under "Analytes", enter "X" in Che column of the designated analyte to
indicate that the analyte value was used from the reported analysis to
report data in the SDG. Leave the column empty for each analyte if the
analysis was not used to report the particular analyte.
B-37 7/88
-------
SECTION IV
DATA REPORTING FORMS
B-38 7/88
-------
U. S. EPA - CLP
COVER PAGE - INORGANIC ANALYSES DATA PACKAGE
ub Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
SOW No.
EPA Sample No. Lab Sample ID
Were ICP interelement corrections applied? Yes/No
Were ICP background corrections applied? Yes/No
If yes, were raw data generated before
application of background corrections? - Yes/No
Comments:
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 floppy diskette has been authorized by the Laboratory Manager or the
Manager's designee, as verified by the following signature.
Signature: Name:
Date: Title:
COVER PAGE - IN
-------
-------
U.S. EPA - CLP
INORGANIC ANALYSIS DATA SHEET
EPA SAMPLE NO.
Lab Name:
Lab Code:
Contract:
Matrix (soil/water):
Level (low/med):
Case No.: SAS No.: SDG No.:
Lab Sample ID:
Date Received:
% Solids:
Concentration Units (ug/L or mg/kg dry weight) :
1
CAS No. | Analyte
1
7429-9O-5 | Aluminum
7440-36-0 j Antimony
7440-38-2 | Arsenic
7440-39-3 | Barium
7440-41-7 | Beryllium
7440-43-9 (Cadmium
7440-70-2 I Calcium
7440-47-3 (Chromium
7440-48-4 (Cobalt
7440-50-8 (Copper
7439-89-6 I Iron
7439-92-1 (Lead
7439-95-4 | Magnesium
7439-96-5 (Manganese
7439-97-6 (Mercury
7440-O2-0 (Nickel
744O-09-7 | Potassium
7782-49-2 | Selenium
744O-22-4 (Silver
7440-23-5 I Sodium
7440-28-0 IThallium
7440-62-2 (Vanadium
744O-66-6 (Zinc .
(Cyanide
I
Concentration
c
Q
M
Color Before:
Color After:
Comments:
Clarity Before:
Clarity After:
Texture:
Artifacts:
FORM I - IN
7/88
-------
U.S. EPA - CLP
2A
INITIAL AND CONTINUING CALIBRATION VERIFICATION
Lab Name:
Lab Code:
Case No.:
Initial Calibration Source:
Continuing Calibration Source:
Contract:
SAS No.:
SDG No.:
Concentration Units: ug/L
1
1
| Analyte
1
|Aluminum_
| Antimony_
| Arsenic
| Barium
| Beryllium
1 Cadmium
Calcium
i Chromium
I Cobalt
I Copper
llron
{Lead
| Magnesium
(Manganese
| Mercury
(Hicfcel^
| Potassium
j Selenium
| Silver
| Sodium
| Thallium
(Vanadium
| Zinc_j
1 Cyanide
1
.
Initial Calibration
True Found %R(1)
Continuing Calibration
True Found *R(1) Found %R(1)
W
•
(1)
Control Limits: Mercury 80-120; Other Metals 90-110; Cyanide 85-115
FORM II (PART 1) - IN
7/88
-------
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
I
| Aluminum
| Antimony
| Arsenic
| Barium
| Beryllium
1 Cadmium
. Calcium
, Chromium
(Cobalt
I Copper
llron
(Lead
| Magnesium
| Manganese
| Mercury
1 Nickel
(Potassium
| Selenium
(Silver
(Sodium
(Thallium
| Vanadium
(Zinc
1
CRDL S
True
tandard fo
Found
r AA
%R
True
CRDL Star
Initial
Found
idard i
*R
:or ICP
Fina;
Found
'
t
. •
%R
FORM II (PART 2) - IN
7/88
-------
U.S. EPA - CLP
3
BLANKS
Lab Name:
Lab Code:
Case No.:
Contract:
SAS No.:
Preparation Blank Matrix (soil/water):
Preparation Blank Concentration Units (ug/L or ng/kg):
SDG No.
1
i
1
1
|Analyte
1
| Aluminum
f Antimony
j Arsenic
j Barium
I Beryllium
j Cadmium
j Calcium
j Chromium
I Cobalt
I Copper
(Iron
ILead
(Magnesium
(Manganese
(Mercury
(Nickel
j Potassium
|Selenium_
(Silver ""
(Sodium
(Thallium
(Vanadium
| Zinc^
| Cyanide
1
Initial
Calib.
Blank
(ug/L) C
~
~
-
Continuing Calibration
Blank (ug/L)
1 C 2 C 3 C
_
~
-
~
-
—
-
~
~
-
—
\
Prepa-
ration
Blank c
t
-
-
_
-
M
—
FORM III - IN
7/88
-------
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
i
1
1
| Analyte
|
| Aluminum
| Antimony
1 Arsenic
| Barium
| Beryllium
| Cadmium
| Calcium
| Chromium
I Cobalt
I Copper
I Iron
[Lead
| Magnesium
| Manganese
1 Mercury
| Nickel
| Potassium
| Selenium
I Silver
| Sodium
(Thallium
(Vanadium
(Zinc
1
True
Sol. Sol.
A AB
Initial Found
Sol. Sol.
A AB %R
Final Found
Sol. Sol.
A AB %R
'
FORM IV - IN
7/88
-------
0. S. EPA - CLP
5A
SPIKE SAMPLE RECOVERY
EPA SAMPLE NO.
Lab Name:
Lab Code:
Matrix:
Case No.:
Contract:
SAS No.:
SDG No.:
Level (low/ned):
% Solids for Sample:
Concentration Units (ug/L or mg/kg dry weight):
Analyte
Aluminum
| Antimony
| Arsenic
1 Barium
(Beryllium
Cadmium
, Calcium
Chromium
1 Cobalt
Copper
llron
ILead
j Magnesium
(Manganese
1 Mercury
1 Nickel
| Potassium
| Selenium
1 Silver ~
Sodium
| Thai Hum
(Vanadium
IZinc
1 Cyanide
Control
Limit
%R
Spiked Sample
Result (SSR)
C
Sample
Result (SR)
C
Spike
Added (SA)
%R
.
Q
M
Comments:
FORM V (Part 1) - IN
-------
U. S. EPA - CLP
SB
POST DIGEST SPIKE SAMPLE RECOVERY
EPA SAMPLE NO.
Lab Name:
Lab Code:
Matrix:
Case No.
Contract:
SAS No.:
SDG No.
Leve 1 (1ow/med)
Concentration Units: ug/L
Analyte
| Aluminum
| Antimony
| Arsenic
I Barium
| Beryllium
| Cadmium
' Calcium
Chromium
I Cobalt
Copper
Iron
Lead
| Magnesium
| Manganese
| Mercury
1 Nickel
Potassium
| Selenium
1 silver
I Sodium
j Thallium
I Vanadium
IZinc
Control
Limit
%R
1
1
Spiked Sample
Result (SSR)
_
c
Sample
Result (SR)
'C
Added (SA)
%R
Q
»
M
Comments:
FORM V (Part 2) - IN
-------
U.S. EPA - CLP
EPA SAMPLE NO.
Lab Name:
Lab Code:
DUPLICATES
Contract:
Case No.:
SAS No.:
Matrix (soil/water) :
% Solids for Sample:
SDG No.:
Level (low/med):
% Solids for Duplicate:
Concentration Units (ug/L or mg/kg dry weight):
1
1
| Analy te
I
| Aluminum
| Antimony
(Arsenic
| Barium
| Beryllium
I Cadmium
j Calcium
j Chromium
| cobalt
I Copper
(Iron
ILead
(Magnesium
| Manganese
| Mercury
| Nickel
j Potassium
j Selenium
j Silver
j Sodium
(Thallium
j Vanadium
|Zinc
j Cyanide
1
Control
Limit
Sample (S)
c
Duplicate (D)
c
RPD
Q
.
1
1 M
FORM VI - IN
7/88
-------
U.S. EPA - CLP
LABORATORY CONTROL SAMPLE
Lab Name:
Lab Code:
Solid LCS Source:
Aqueous LCS Source:
Case No.:
Contract:
SAS No. :
SDG No.:
1
1
| Analyte
1
| Aluminum_
| Antimony
| Arsenic
| Barium
I Beryllium
j Cadmium
| Calcium
Chromium
| Copper
llron
ILead
| Magnesium
| Manganese
1 Mercury
| Nickel^
j Potassium
j Selenium
I Silver
I Sodium
(Thallium
| Vanadium_
j Zinc
1 Cyanide
1
Aqueous (ug/L)
True Found %R
«
Solid
True Found C
-
—
~
_.
~
(mg/kg)
Limits %R
*
.
FORM VII - IN
7/88
-------
U.S. EPA - CLP
8
STANDARD ADDITION RESULTS
ab Name:
ab Code:
EPA
Sample
No.
Case No. :
Contract:
SAS No.: SDG No.:
Concentration Units: ug/L
An
'
0 ADD
ABS
'
1 ADD
CON ABS
2 ADD
CON ABS
•
3 ADD
CON ABS
Final
Cone.
r
•
— :
Q
•
"
~
~
-
-
FORM VIII - IN
7/88
-------
Name:
Lab Code:
U.S. EPA - CLP
ICP SERIAL DILUTIONS
Contract:
EPA SAMPLE NO.
r
Case No.:
SAS No.:
SDG No.:
Matrix (soil/water):
Level (low/med):
Concentration Units: ug/L
1
1
lAnalyte
1
| Aluminum
(Antimony
j Arsenic
I Barium
| Beryllium
I Cadmium
| Calcium
| Chromium
I cobalt
I Copper
llron
(Lead
(Magnesium
| Manganese
| Mercury
(Nickel
| Potassium
(Selenium
(Silver
(Sodium
(Thallium
j Vanadium
(Zinc
1
Initial Sample
Result (I)
c
Serial
Dilution
Result (S)
c
%
Differ-
ence
1
Q
•
M
FORM IX - IN
7/88
-------
Lab Name:
Lab Code:
Case No.:
ICP ID Number:
Flame AA ID Number:
Furnace AA ID Number:
U. S. EPA - CLP
10
Instrument Detection Limits (Quarterly)
Contract:
SAS No.: SDG No.:
Date:
Analyte
| Aluminum
| Antimony
1 Arsenic
Barium
I Beryllium
Cadmium
1 Calcium
I Chromium
1 Cobalt
1 Cooper
llron
Lead
| Magnesium
| Manganese
(Mercury
| Nickel
j Potassium
| Selenium
ISiTver
1 Sodium
(Thallium
j Vanadium"
(Zinc
Wave-
length
(nm)
Back-
ground
CRDL
(ug/L)
__Jl£flL
60
10.
200
5.
5.
5000
12
50.
25_
100
3.
5000
15
OJ
5JJM
1Q
5000
12
SO
20.
IDL
(ug/L)
M
Comments:
FORM X - IN
-------
O. S. EPA - CLP
11A
ICP Interelement Correction Factors (Annually)
Lab Name:
Lab Code:
ICP ID Number:
Case No.:
Contract:
SAS No.:
Date:
SOG No.
Analyte
| Aluminum
| Antimony
| Arsenic
| Barium
| Beryllium
| Cadmium
| Calcium
| Chromium
1 Cobalt
1 Copper
|lron
%ead
Magnesium
| Manganese
| Mercury
| Nickel
j Potassium
| Selenium
(Silver
1 Sodium
j Thallium
| Vanadium
IZinc
1
Wave-
length
(nm)
Int
Al
:erelement (
Ca
:orrection I
Fe
r
'actors for:
Mg
Comments:
FORM XI (Part 1) - IN
-------
U. S. EPA - CLP
11B
ICP Interelement Correction Factors (Annually)
Lab Name:
Lab Code:
ICP ID Number:
Case No.:
Contract:
SAS No.:
Date:
SDG No.
1
1
1
I Analyte
1
| Aluminum
(Antimony
1 Arsenic
I Barium
| Beryllium
1 Cadmium
I Calcium
| Chromium
I Cobalt
I Copper
'Iron
xiad
(Magnesium
(Manganese
(Mercury
(Nickel
I Potassium
| Selenium
I Silver
(Sodium
|ThalliuB_
| Vanadium
(Zinc
1
Wave-
length
(nm)
In
terelement
Correction
Factors for
.
Comments:
FORM XI (Part 2) - IN
-------
U. S. EPA - CLP
Lab Name:
Lab Code:
Case No.:
ICP ID Number:
12
ICP Linear Ranges (Quarterly)
Contract:
SAS No.:
Date:
SDG No.
1
1
1
| Analyte
1
| Aluminum
| Antimony
(Arsenic
I Barium
| Beryllium
| Cadmium
1 Calcium
| Chromium
I Cobalt
1 Copper
I Iron
ILead
| Magnesium
| Manganese
| Mercury
I Nickel
| Potassium
| Selenium
(Silver
1 Sodium
| Thallium
| Vanadium
IZinc
1
Integ.
Time
(sec.)
Concentration
(ug/L)
,
M
Comments:
FORM XII - IN
-------
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
(gran)
Volume
(mL)
FORM XIII - IN
7/88
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U.S. EPA - CLP
14
ANALYSIS RUN LOG
^b Name:
Lab Code:
Case No.:
Instrument ID Number:
Start Date:
Contract:
SAS No.:
Method: _
End Date:
SDG No.
EPA
Sample
No.
D/F
—
Time
% R
Analytes
A
L
S
B
A
S
B
A
B
E
C
D
C
A
C
R
C
O
C
u
F
E
P
B
H
G
M
N
H
G
N
I
K
S
E
A
G
i
N
A
T
L
V
2
N
C
N
FORM XIV - IN
7/88
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EXHIBIT C
INORGANIC TARGET ANALYTE LIST
7/88
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INORGANIC TARGET ANALYTE LIST (TAL)
Contract Required
Detection Limit
Analyte (ug/L)
Aluminum 200
Antimony 60
Arsenic 10
Barium 200
Beryllium 5
Cadmium 5
Calcium 5000
Chromium 10
Cobalt 50
Copper 25
Iron ' 100
Lead 3
Magnesium 5000
Manganese 15
Mercury 0.2
Nickel 40
Potassium 5000
Selenium 5
Silver 10
Sodium 5000
Thallium 10
Vanadium 50
Zinc 20
Cyanide 10
(1) Subject to the restrictions specified in the first page of Part G,
Section~TV of Exhibit D (Alternate Methods - Catastrophic Failure) any
analytical method specified in SOU 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 *~he 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 7/88
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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 7/88
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EXHIBIT D
ANALYTICAL METHODS
Page No.
SECTION I - INTRODUCTION D-l
Figure 1-Inorganic Methods Flow Chart D-3
SECTION II - SAMPLE PRESERVATION AND HOLDING TIMES D-4
Part A - Sample Preservation D-4
Part B - Holding Times D-4
SECTION III - SAMPLE PREPARATION D-5
Part A - Water Sample Preparation D-5
Part B - Soil/Sediment Sample Preparation D-5
SECTION IV - SAMPLE ANALYSIS D-9
Part A - Inductively Coupled Plasma-Atomic
Emission Spectronetrie Method D-10
Part B - Atomic Absorption Methods, Furnace Technique . . . D-24
Part C - Atomic Absorption Methods, Flame Technique .... D-37
Part D - Cold Vapor Methods for Mercury Analysis D-42
Part E - Methods for Total Cyanide Analysis D-61
Part F - Percent Solids Determination Procedure D-83
Part G - Alternate Methods (Catastrophic ICP Failure) . . . D-84
7/88
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SECTION I
INTRODUCTION
Inorganic Methods Flow Chart: Figure I oulines the general analytical
scheme the Contractor will follow in performing analyses under this
contract.
Permitted Methods: Subject to the restrictions specified in Section IV,
Part G - Alternate Methods (Catastrophic ICP Failure), any analytical
method specified in Exhibit D may be used as long as the documented
instrument or method detection limits meet the Contract Required Detection
Limits (Exhibit C). Analytical methods with higher detection limits may be
used only if the sample concentration exceeds five times the documented
detection limit of the instrument or method.
Initial Run Undiluted: All samples must initially be run undiluted (i.e.,
final product of the sample preparation procedure). When an analyte
concentration exceeds the calibrated or linear range (as appropriate), re-
analysis for that analyte(s) is required after appropriate dilution. The
Contractor must use the least dilution necessary to bring the analyte(s)
within the valid analytical range (but not below the CRDL) and report the
highest valid value for each analyte as measured from the undiluted and
diluted analyses. Unless the Contractor can submit 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.Z.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 Vastes" 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 7/88
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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 Project Officer or
Deputy Project Officer, all samples shall be mixed thoroughly prior to
aliquoting for digestion. No specific procedure is provided herein for
homogenization of soil/sediment samples; however, an effort should be made
to obtain a representative aliquot.
Background Corrections: Background corrections are required for Flame AA
measurements below 350 run and for all Furnace AA measurements. For ICP
background correction requirements, see Exhibit D Section IV, Part A,
paragraph 2.1.
Replicate Injections/Exposures: Each furnace analysis requires a minimum
of two injection (burns), except for full method of Standard Addition
(MSA). All ICP measurements shall require a minimum of two replicate
exposures. Appropriate hard copy raw data for each exposure/injection
shall be included in the data package in accordance with Exhibit B, Section
II, Part D, paragraph 2.d. The average of each set of exposures/injections
shall be used for standardization, sample analysis, and reporting as
specified in Exhibit D.
D-2 7/88
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Figure 1
INORGANICS METHODS FLOW CHART
Field Sample
| Traffic Report or SMO |
| Specifies Parameters |
1
Water
Matrix
1
1
1
\ \
I 1
| .Cyanide | (Acid Digestion)
| Analysis j j for Metals |
| in Vater | | Analysis |
| | | in Water |
1
1
1
| Metal Anal. |
| 1CP/AAS |
1
1
1
Soil/Sediment
Matrix
[Acid Digestion | |% So]
| for Metals | JDete:
(Analysis in | | at:
| Soil/Sedinent | |
(Metals Anal. |
| ICP/AAS |
1
\
1
1
I Data Reports
1
1
Lids | (Cyanide |
rmin- | (Analysis)
LOR | Jin Soil/|
| | Sediment |
D-3
7/88
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SECTION II
SAMPLE PRESERVATION AND HOLDING TIMES
Sample Preservation
Water Sample Preservation
Measurement
Parameter
Metals(3)
Cyanide, total
and amenable
to chlorination
Container/ '
P.G
P,G
Preservative'2^
HN03 to pH <2
0.6g ascorbic acid(4)
NaOH to pH >12
Cool, maintain at
until analysis
4°C(±2°C)
FOOTNOTES:
(1) Polyethylene (P) or glass (G).
(2) Sample preservation is performed by Che 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
bv Contractor
26 days
180 days
12 days
7/88
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SECTION III
SAMPLE PREPARATION
A. Water Sample Preparation
1. Acid Digestion Procedure for Furnace Atomic Absorption Analysis
Shake sample and transfer 100 mL of well-mixed sample to a 250-mL
beaker, add 1 mL of (1+1) HN03 and 2 mL 30% H202 to the sample.
Cover with watch glass or similar cover and heat on a steam bath
or hot plate for 2 hours at 95°C or until sample volume is reduced
to between 25 and 50 mL, making certain sample does not boil.
Cool sample and filter to remove insoluble material. (NOTE: In
place of filtering, the sample, after dilution and mixing, may be
centrifuged or allowed to settle by gravity overnight to remove
insoluble material.) Adjust sample volume to 100 mL with deionized
distilled water. The sample is now ready for analysis.
Concentrations so determined shall be reported as "total".
If Sb is to be determined by furnace AA, use the digestate
prepared for ICP/flame AA analysis.
2. Acid Digestion Procedure for ICP and Flame AA Analyses
Shake sample and transfer 100 mL of well-mixed sample to a 250-mL
beaker, add 2 mL of (1+1) HN03 and 10 mL of (1+1) HC1 to the
sample. Cover with watch glass or similar cover and heat on a
steam bath or hot plate for 2 hours at 95°C or until sample volume
is reduced to between 25 and 50 mL, making certain sample does not
boil. Cool sample and filter to remove insoluble material.
(NOTE: In place of filtering, the sample, after dilution and
mixing, may be centrifuged or allowed to settle by gravity
orernight to remove insoluble material.) Adjust sample volume to
100 mL with deionized distilled water. The sample is now ready
for analys is.
Concentrations so determined shall be reported as "total".
B. Soil/Sediment Sample Preparation
1. Acid Digestion Procedure for ICP, Flame AA and Furnace AA Analyses
a. Scope and Application
This method is an acid digestion procedure used to prepare
sediments, sludges, and soil samples for analysis by flame or
furnace atomic absorption spectroscopy (AAS) or by
inductively coupled plasma spectroscopy (ICP). Samples
prepared by this method may be analyzed by AAS or ICP for the
following metals:
D-5 ' 7/88
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Aluminum
Ant imony
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 ICF 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) Vatch 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 D1193): Water nust be
monitored.
(2) Concentrated Nitric Acid (sp. gr. 1.41)
(3) Concentrated Hydrochloric Acid (sp. gr. 1.19)
(4) Hydrogen Peroxide (30%)
Sample Preservation and Handling
Soil/sediment (nonaqueous) samples must be refrigerated at
4°C (±2°) from receipt until ana-lysis.
D-6
7/88
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f. Procedure
(1) Mix the sample thoroughly to achieve homogeneity. For
each digestion procedure, weigh (to the nearest O.Olgres)
a 1.0 to 1.5 gm portion of sample and transfer to a
beaker.
(2) Add 10 mL of 1:1 nitric acid (HN03), 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
Co cool, add 5 mL of concentrated HNO^, 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 (^Oj). 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 in ^ niL 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% HnO^.)
(5) 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) HNO-j. Dilute the digestate
1:1 (200 mL final volume) with acidified water to
maintain constant acid strength. The sample is now
ready for analysis.
(6) 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 mL,
add 10 mL of Type II water, and warm the mixture. After
cooling, filter through Whatman No. 42 filter paper (or
equivalent) and dilute to 100 mL with Type II water (or
centrifuge the sample). NOTE: In place of filtering,
D-7 7/88
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the sample (after dilution and mixing) may be
centrifuged or allowed to settle by gravity overnight to
remove insoluble material. The diluted digestate
solution contains approximately 2% (v/v) HNOj. 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.) (rag/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 • 7/88
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SECTION IV
SAMPLE ANALYSIS
Page No.
PART A - INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION
SPECTROMETRIC METHOD D-10
PART B - ATOMIC ABSORPTION METHODS, FURNACE TECHNIQUE D-24
PART C - ATOMIC ABSORPTION METHODS, FLAME TECHNIQUE D-37
PART D - COLD VAPOR METHODS FOR MERCURY ANALYSIS D-42
PART E - METHODS FOR CYANIDE ANALYSIS ' D-61
PART F - PERCENT SOLIDS DETERMINATION PROCEDURE D-83
PART G - ALTERNATE METHODS (CATASTROPHIC ICP FAILURE) D-84
D-9 7/88
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PART A - INDUCTIVELY COUPLED PLASMA-ATOMIC EHISSION 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 interference effects. (See 5.)
1.3 Table 1 lists elements along with recommended wavelengths and typical
estimated instrumental detection limits using conventional pneumatic
nebulization. Actual working detected limits are sample dependent and
as the sample matrix varies, these concentrations may also vary. In
time, other elements may be added as more information becomes available
and as required.
1.4 Because of the differences between various makes and models of
satisfactory instruments, no detailed instrumental operating
instructions can be provided. Instead, the analyst is. referred to the
instructions provided by the manufacturer of the particular instrument.
2. Summary of Method
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-10 7/88
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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 um membrane
filter.
3.2 Suspended -- Those elements which are retained by a 0.45 um 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-ll 7/88
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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-knovm 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) overlap of a
spectral line from another element; 2) unresolved overlap of
molecular band spectra; 3) background contribution from
continuous or recombination phenomena; and 4) background
contribution from stray light from the line emission of high
concentration elements. The first of these effects can be
compensated by utilizing a computer correction of the raw data,
requiring the monitoring and measurement of the interfering
element. The second effect may require selection of an
alternate wavelength. The third and fourth effects can usually
be compensated by a background correction adjacent to the
analyte line. In addition, users of simultaneous multi-element
instrumentation must assume the responsibility of verifying the
absence of spectral interference from an element that could
occur in a sample but for which there is no channel in the
instrument array.
Listed in Table 2 are some interference effects for the
recommended wavelengths given in Table 1. The data in Table 2
are intended for use only as a rudimentary guide for the
indication of potential spectral interferences. For this
purpose, linear relations between concentration and intensity
for the analytes and the interferents can be assumed. The
interference information, which was collected at the Ames
Laboratory , is expressed as analyte concentration equivalents
(i.e., false analyte concentrations) arising from 100 mg/L of
the interferent element.
**Ames Laboratory, USDOE, Iowa State University, Ames, Iowa 50011.
D-12 7/88
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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.
Vetting 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-13 7/88
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D.2 Prior to reporting concentration data for the snalvt-e elements the
Contractor must anaiyce and report the results ot the ICP Seriai D! L'jt ; or
Analysis The TCP Serial Dilution Analysis must be performed on « yampl-
from e;>'"h group of samples of a sirrrlar matrix ' ype (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 range where correction
factors are valid. It is the responsibility of the analyst to verify
that the instrument configuration and operating conditions used satisfy
the analytical requirements and to maintain quality control data
confirming instrument performance and analytical results.
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).
71.3 Hydrochloric acid, ('.+!): Add 500 mL cone. HC1 (sp gr 1 19)
to AOO mL deionized, distilled water and dilute to 1 liter
D-14 7/E
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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. HN03 (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^ 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)C4H405 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^ 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, stoc-k, 1 mL — 100 ug Ba: Dissolve 0.1516 g
BaCl2 (dried at 250°C for 2 hrs) in 10 mL deionized, distilled
water with 1 mL (1+1) HC1. Add 10.0 mL (1+1) HC1 and dilute to
1,000 mL with deionized, distilled water.
7.3.5 Beryllium solution, stock, 1 mL - 100 ug Be: Do not dry.
Dissolve 1.966 g BeSO^^I^O, in deionized, distilled water, add
10.0 mL cone. HNO-, 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 HjBOj 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-15 7/88
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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^. Heat to increase rate
of dissolution. Add 10.0 mL cone. HNO^ 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
CaCOo 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. HNO-j 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 CrO-j 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) HNO-j. 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-j. Add 10.0 mL cone. HN03
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
Fe20o in a warm mixture of 20 mL (1+1) HC1 and 2 mL of cone.
HN03. Cool, add an additional 5 mL of cone. HN03 and dilute
to 1,000 mL with deionized, distilled water.
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) HN03. Add 10.0 mL cone. HNO-j
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 (NH^)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-16 7/88
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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 I^SeO^ (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 Na2Si03'9H20 in deionized, distilled water.
Add 10.0 mL cone. HN03 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
AgNOj 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 deionized, distilled water. Add 10.0 mL cone. HN03
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
T1N03 in deionized, distilled water. Add
10.0 mL cone. HN03 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^VOj in a minimum amount of cone. HNO-j. Heat to increase
rate of dissolution. Add 10.0 mL cone. HN03 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 HN03. Add 10.0 mL cone. HN03 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) HN03 and 10 mL of (1+1) HC1 and dilute to 100 mL with deionized,
distilled water. (See NOTE in 7.4.5) Prior to preparing the mixed
standards , each stock solution should be analyzed separately to
determine possible spectral interference or the presence of impurities.
Care should be taken when preparing the mixed standards that the
elements are compatible and stable. Transfer the mixed standard
solutions to a FEP fluorocarbon or unused polyethylene bottle for
storage. Fresh mixed standards should be prepared as needed with the
realization that concentration can1 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-17 ' 7/88
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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, magnesium,
silver, and thallium.
NOTE: If the addition of silver to the recommended acid
combination results in an initial precipitation add 15 mL of
deionized distilled water and warm the flask until the solution
clears. Cool and dilute to 100 mL with deionized, distilled
water. For this acid combination the silver concentration
should be limited to 2 mg/L. Silver under these conditions is
stable in a tap water matrix for 30 days. Higher
concentrations of silver require additional HC1.
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-18 7/88
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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 30 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-19 7/88
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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, H.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-20 7/88
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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
Magnes ium
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-21 7/88
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TABLE 2. EXAMPLE OF ANALYTE CONCENTRATION EQUIVALENTS (MG/L) ARISING FROM
INTERFERENTS AT THE 100 MG/L LEVEL
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Selenium
Silicon
Sodium
Thallium
Vanadium
Zinc
Wavelength,
nm
308.215
206.833
193.696
455.403
313.042
249.773
226.502
317.933
267.716
228.616
324.754
259.940
220.353
279.079
257.610
202.030
231.604
196.026
288.158
588.995
190.864
292.402
213.856
Al Ca
_ _ __
0.47
1.3
•»_ *._
—
0.04
_ _
— — __
— — —_
—
— —
0.17
0.02
0.005
0.05
0.23
—
0.30
—
Cr Cu
— — — «.
2.9
0.44
«•• «W ^ M
— -_
—
0.08
0.03
— — —
—
•" ~ «•«•
0.11
0.01
•" « •»
«•*• m~
0.07
— — — —
0.05
0.14
Interferent
Fe Mg Mn Ni
— — 0.21 —
0.08
tip-
— — — — — — _ —
0.32
0 . 03 — — 0 0?
v* • w •-» \J * \J d
0.01 0.01 0.04
0.003 — 0.04
0.005 — — 0.03
0.003
0.12
0.13 — 0.25
0.002 0.002
001 — — — — — —
. V J ~~ — ~
0.09
—
^~" ' *• ^ ™» •• ^M
0.005
0.29
Ti
.25
0.04
0.03
0.15
0.05
0.07
^ _^
Of\ n
. Oo
0.02
V
1 4
-A. • *t
0.45
1.1
0.05
0.03
0.04
0. 02
0. 12
•— — .
0.01
II
--
-------
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
Hi
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-23 7/88
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PART B - ATOMIC ABSORPTION METHODS. FURNACE TECHNIQUE"1"
Analvte/Method Page No.
Antimony - .Method 204.2 CLP-M* D-25
Arsenic - Method 206.2 CLP-M ' D-26
Beryllium - Method 210.2 CLP-M D-28
Cadmium - Method 213.2 CLP-M D-29
Chromium - Method 218.2 CLP-M D-30
Lead - Method 239.2 CLP-M D-31
Selenium - Method 270.2 CLP-M D-33
Silver - Method 272.2 CLP-M D-35
Thallium - Method 279.2 CLP-M D-36
"'"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-24 7/88
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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
mg/L).
2. Prepare dilutions of the stock solution to be used as calibration
• standards at the time of analysis. These solutions are also to be used
for "standard additions".
3. The calibration standards must be prepared using the same type of acid
and at the same concentration as will result in the sample to be
analyzed after sample preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2 . Ashing Time and Temp: 30 sec <§ 800°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 217.6 nm
6. Other operating parameters should be set as specified by the particular
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, 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 jrates of atomization can be operated using lower atomization
temperatures for shorter time periods than the above recommended
settings.
2. The use of background correction is required.
3. Nitrogen may also be used as the purge gas.
4. If chloride concentration presents a matrix- problem or causes a loss
previous to atomization, add an excess 5 mg of ammonium nitrate to the
furnace and ash using a ramp accessory or with incremental steps until
the recommended ashing temperature is reached.
5. For every sample analyzed, verification is necessary to determine that
method of standard addition is not required (see Exhibit E).
6. If method of standard addition is required, follow the procedure given
in Exhibit E.
CLP-M modified for the Contract Laboratory Program
D-25 7/88
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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, As20j
(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(N03)2'6H20 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 Arsenic Solution: Prepare dilutions of the stock solution to
be used as calibration standards at the time of analysis. Withdraw
appropriate aliquots of the stock solution, add 1 mL of cone. HNO^, 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
1. The above concentration values and instrument conditions are for a
Perkin-Elmer HGA-2100, based on the use of a 20 uL injection, purge gas
interrupt and non-pyrolytic graphite. Smaller size furnace devices or
those employing faster rates of atomization can be operated using lower
atomization temperatures for shorter time periods than the above
recommended settings.
2. The use of background correction is required. Background correction
made by the deuterium arc method does not adequately compensate for
high levels of certain interferents (ie., Al, Fe). If conditions occur
where significant interference is suspected, the lab must switch to an
alternate wavelength or take other appropriate actions to compensate
for the interference effects.
3. For every sample analyzed, verification is necessary to determine that
CLP-M modified for the Contract Laboratory Program.
D-26 7/88
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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-27 7/88
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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 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 @ 2800°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 234.9 nm
6. The operating parameters should be set as specified by the .particular
instrument manufacturer.
Notes
1. The above concentration values and instrument condition's 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-28 7/88
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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
H20 (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 arid 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-29 7/88
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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,
Ca(NO-j)2'4H20 (analytical reagent grade) in deionized distilled water
and dilute to 100 mL. 1 mL - 20 mg Ca.
3. Prepare dilutions of the stock chromium solution to be used as
calibration standards at the time of analysis. The calibration
standards must be prepared using the same type of acid and at the same
concentration as will result in the sample to be analyzed after sample
preparation. To each 100 mL of standard and sample alike, add 1 mL of
30% H22 and 1 mL of the calcium nitrate solution.
Instrument Parameters ('General')
1. Drying Time and Temp: 30 sec <§ 125°C.
2. Ashing Time and Temp: 30 sec @ 1000°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 357.9 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a
Perkin Elmer HGA-2100, based on the use of a 20 uL injection,
continuous flow purge gas and non-pyrolytic graphite and are to be used
as guidelines only.'
2. Hydrogen peroxide is added to the acidified solution to convert all
chromium to the trivalent state. Calcium is added to a level above
200 mg/L where its suppressive effect becomes constant up to 1000 mg/L.
3. Background correction is required.
4. Nitrogen should not be used as a purge gas because of possible CN band
interference.
5. Pipette tips have been reported to be a possible source of
contamination.
6. For every sample analyzed, verification is necessary to determine that
method of standard addition is not required (see Exhibit E) .
7. If method of standard addition is required, follow the procedure given
in Exhibit E.
*CLP-M modified for the Contract Laboratory Program.
D-30 7/88
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LEAD
Method 239.2 CLP-M* (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L
Approximate Detection Limit: 1 ug/L
Preparation of Standard Solution
1. Stock solution: Carefully weigh 1.599 g of lead nitrate, Pb(N03)2
(analytical reagent grade), and dissolve in deionized distilled water.
When solution is complete, acidify with 10 mL redistilled HNO^ and
dilute to 1 Liter with deionized distilled water. 1 mL - 1 mg Pb
(lOOOmg/L).
2. Lanthanum Nitrate solution: Dissolve 58.64 g of ACS reagent grade
Lao^s i-n 100 "L cone. HNOg and dilute to 1000 mL with deionized
distilled water. 1 mL - 50 mg La.
3. Working Lead solution: Prepare dilutions of stock lead solution to be
used as calibration standards at the time of analysis. The calibration
standards must be prepared using the same type of acid and at the same
concentration as will result in the sample to be analyzed after sample
preparation. To each 100 mL of diluted standard add 10 mL of the
lanthanum nitrate solution.
Sample Preparation
1* To each 100 mL of prepared sample solution add 10 mL of the lanthanum
nitrate solution.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec (§ 125°C.
2. Ashing Time and Temp: 30 sec @ 500°C.
3. Atomizing Time and Temp: 10 sec <§ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 283.3 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
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.
CLP-M modified for the Contract Laboratory Program.
D-31 7/88
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3. Greater sensitivity can be acheived using the 217.0 run 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-32 ' 7/88
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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% H2SeO,) in deionized distilled water and make up to 200 mL.
1 mL - 1 mg Se (1000 mg/L).
2. Nickel Nitrate solution, 5%: Dissolve 24.780 g of ACS reagent grade
Ni(N03)2-6H20 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 standards must be prepared using the same type of acid and
at the same concentration as will result in the sample to be analyzed
after sample preparation. Withdraw appropriate aliquots of the stock
solution, add 1 mL of cone. HN03, 2 mL of 30% H202 and 2 mL of the 5%
nickel nitrate solution. Dilute to 100 mL with deionized distilled
water.
Sample Preparation
1. Add 100 uL of the 5% nickel nitrate solution to 5 mL of the digested
sample. The sample is now ready for injection into the furnace.
Instrument Parameters
1. Drying Time and Temp: 30 sec @ 125°C.
2. Charring Time and Temp: 30 sec @ 1200°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 196.0 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a
Perkin-Elmer HGA-2100, based on the use of a 20 uL injection, purge gas
interrupt and non-pyrolytic graphite and are to be used as guidelines
only. Smaller size furnace devices or those employing faster rates of
atomization can be operated using lower'atomization tempera- tures for
shorter time periods than the above recommended settings.
2. The use of background correction is required. Background correction
made by the deuterium arc method does not adequately compensate for
high levels of certain interferents (i.e., Al, Fe). If conditions
CLP-M modified for the Contract Laboratory Program.
D-33 7/88
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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-34 7/88
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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 AgNO3 (analytical reagent grade)
in deionized distilled water. Add 10 mL of concentrated HN03 and make
up to 1 Liter. 1 mL - 1 mg Ag (1000 ng/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 lime and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 328.1 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a
Perkin-Elmer HGA-2100, based on the use of a 20 uL injection,
continuous flow purge gas and non-pyrolytic graphite and are to be used
as guidelines only. Smaller size furnace devices or those employing
faster rates of atomization can be operated using lower atomization
temperatures for shorter time periods than the above recommended
settings"
2. The use of background correction is required.
3. The use of halide acids should be avoided.
4. If absorption to container walls or formation of AgCl is suspected, see
Part G, AA methods Flame Technique.
5. For every sample analyzed, verification is necessary to determine that
method of standard addition is not required (see Exhibit E).
6. If method of standard addition is required, follow the procedure given
in Exhibit E.
CLP-M modified for the Contract Laboratory Program.
D-35 7/88
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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, T1N03 (analytical
reagent grade) in deionized distilled water. Add 10 oL of concentrated
nitric acid and dilute to 1 Liter with deionized distilled water. 1 mL
- 1 mg Tl (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration
standards at the time of analysis. These solutions are also to be used
for "standard additions".
3. The calibration standards must be prepared using the same type of acid
and at the same concentration as will result in the sample to be
analyzed after sample preparation.
Instrument Parameters (General')
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 400°C.
3. Atomizing Time and Temp: 10 sec @ 2400°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 276.8 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a
Perkin- Elmer HGA-2100, based on the use of a 20 uL injection,
continuous flow purge gas and non-pyrolytic graphite and are to be
used as guidelines only. Smaller size furnace devices or those
employing- faster rates of atomization can be operated using lower
atomization temperatures for shorter time periods than the above
recommended settings.
2. The use of background correction is required.
3. Nitrogen may also be used as the purge gas.
4. For every sample analyzed, verification is necessary to determine
that method of standard addition is not required (see Exhibit E).
5. If method of standard addition is required, follow the procedure
given in Exhibit E.
CLP-M modified for the Contract Laboratory Program.
D-36 7/88
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PART C - ATOMIC ABSORPTION METHODS. FLAME TECHNIQUE'1'
Analvte/Method Page No.
Calcium - Method 215.1 CLP-M* D-38
Magnesium - Method 242.1 CLP-M D-39
Potassium - Method 258.1 CLP-M D-40
Sodium - Method 273.1 CLP-M D-41
From "Interim Methods for the Sampling and Analysis of Priority Pollutants
in Sediments and Fish Tissue", USEPA EMSL, Cincinnati, Ohio, August 1977,
Revised October 1980, as modified for use in the Contract Laboratory
Program.
*CLP-M modified for the Contract Laboratory Program.
D-37 7/88
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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 CaCOj (analytical reagent grade),
dried at 180°C for 1 hour before weighing, in deionized distilled water
and dissolve cautiously with a mimimuin 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 and sample alike add 1.0 mL of the lanthanum
chloride solution, i.e., 20 mL of standard or sample + 2 mL LaCl-j - 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]).
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-38 7/88
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MAGNESIUM
Method 242.1 CLP-M* (Atonic Absorption, Flame Technique)
Optimum Concentration Range: 0.02-0.5 mg/L using a wavelength of 285.2 nm
Sensitivity: 0.007 mg/L
Detection Limit: 0.001 mg/L
Preparation of Standard Solution
1. Stock Solution: Dissolve 0.829 g of magnesium oxide, MgO (analytical
reagent grade), in 10 ml of redistilled HN03 and dilute to 1 liter with
deionized distilled water. 1 mL - 0.50 mg Mg (500 mg/L).
2. Lanthanum chloride solution: Dissolve 29 g of L^Oj, 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 vised 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 - 22
mL.
Instrumental Parameters (General")
1. Magnesium hollow cathode lamp
2. Wavelength: 285.2 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Notes
1. The interference caused by aluminum at concentrations greater than 2
ng/L is masked by addition of lanthanum. Sodium, potassium and calcium
cause no interference at concentrations less than 400 mg/L.
2. The following line may also be used: 202.5 nm Relative Sensitivity 25.
3. To cover the range of magnesium values normally observed in surface
waters (0.1-20 mg/L), it is suggested that either the 202.5 nm line be
used or the burner head be rotated. A 90° rotation of the burner head
will produce approximately one-eighth the normal sensitivity.
CLP-M modified for the Contract Laboratory Program.
D-39 7/88
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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 ran
Sensitivity: 0.04 mg/L
Detection Limit: 0.01 mg/L
Preparation of Standard Solution
1. Stock Solution: Dissolve 0.1907 g of KC1 (analytical reagent grade),
dried at 110°C, in deionized distilled water and make up to 1 liter. 1
mL - 0.10 mg K (100 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration
standards at the time of analysis. The calibration standards should be
prepared using the same type of acid and at the same concentration as
will result in the sample to be analyzed either directly or after
processing.
Instrumental Parameters (General)
1. Potassium hollow cathode lamp
2. Wavelength: 766.5 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Slightly oxidizing
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-40 7/88
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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 run
Sensitivity: 0.015 mg/L
Detection Limit: 0.002 mg/L
Preparation of Standard Solutions
1. Stock Solution: Dissolve 2.542 g of Nad (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 (Generalj
1. Sodium hollow cathode lamp
2. Wavelength: 589.6 nm
3. Fuel: Acetylene
A. Oxidant: Air
5. Type of flame: Oxidizing
Notes
1. The 330.2 nm resonance line of sodium, which has a relative sensitivity
of 185, provides a convenient way to avoid the need to dilute more
concentrated solutions of sodium.
2. Low-temperature flames increase sensitivity by reducing the extent of
ionization of this easily ionized metal. lonization may also be
controlled by adding potassium (1000 mg/L) to both standards and
samples.
CLP-M modified for the Contract Laboratory Program.
D-41 7/88
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PART D - COLD VAPOR METHODS FOR 'MERCURY ANALYSTS+
Method Page No.
Mercury Analysis in Water by Manual Cold Vapor Technique D-43
Method 245.1 CLP-M
Mercury Analysis in Water by Automated Cold Vapor Technique D-49
Method 245.2 CLP-M
Mercury Analysis in Soil/Sediment by Manual Cold Vapor Technique D-56
Method 245.5 CLP-M
"*A bibliography citing method references follows each method.
CLP-M modified for the Contract Laboratory Program.
D-42 7/88
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MERCURY ANALYSIS IN WATER SY 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. For distilled water
the heat step is not necessary.
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 run by mercury vapor. Organic
mercury compounds are oxidized and the mercury is reduced to the
elemental state and aerated from solution in a closed system. The
mercury vapor passes through a cell positioned in the light path of
an atomic absorption spectrophotometer. Absorbance (peak height) is
measured as a function of mercury concentration and recorded in the
usual manner.
3. Sample Handling and Preservation
3.1 Until more conclusive data are obtained, samples are preserved by
acidification with nitric acid to a pH of 2 or lower immediately at
the time of collection (Exhibit D, Section II).
*CLP-M modified for the Contract Laboratory Program.
D-43 7/88
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A. Interference
A.I Possible interference from sulfide is eliminated by the addition of
potassium permanganate. Concentrations as high as 20 mg/1 of sulfide
as sodium sulfide do not interfere with the recovery of added
inorganic mercury from distilled water (Exhibit D, Section II).
4.2 Copper has also been reported to interfere; however,. copper
concentrations as high as 10 mg/L had no effect on recovery of
mercury from spiked samples.
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.
4.4 While the possibility of absorption from certain organic substances
actually being present in the sample does exist, EMSL has not
encountered such samples. This is mentioned only to caution the
analyst of the possibility.
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.
D-44 7/88
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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 anc
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 fit having a coarse porosity.
- Tygon tubing is used for passage of the mercury vapor from the sample
bottle to the absorption cell and return.
5.8 Drying Tube: 6" X 3/4" diameter tube containing 20 g of magnesium
perchlorate (see Note 2). The apparatus is assembled as shown in
Figure 1.
NOTE 2: In place of the magnesium perchlorate drying tube, a small
reading lamp with 60W bulb may be used to prevent condensation of
moisture inside the cell. The lamp is positioned to shine on the
absorption cell maintaining the air temperature in the cell about
10°C above ambient.
6. Reaeents
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.
D-45 7/88
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6.6 Potassium Persulfate: 5% solution, w/v.
persulfate in 100 mL of distilled water.
Dissolve 5 g of potassium
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.
i
O < BUBBLER
SAMPLE SOLUTION
IN BOD BOTTLE
ABSORPTION
CELL
SCRUBBER
CONTAINING
A MERCURY
ABSORBING
MEDIA
Figure 1. Apparatus for FLameless Mercury Determination
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.
D-46
7/88
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The circulating pump, which has previously been adjusted to a rate of
1 licer per minute, is allowed to run continuously (see Note 4). The
absorbance will increase and reach maximum within 30 seconds. As
soon as the recorder pen levels off, approximately 1 minute, open the
bypass valve and continue the aeration until the absorbance returns
to its minimum value (see Note 5). Close the bypass valve, remove
the stopper and frit from the BOD bottle and continue the aeration.
Proceed with the standards and construct a standard curve by plotting
peak height versus micrograms of mercury.
NOTE 4: An open system where the mercury vapor is passed through the
absorption cell only once may be used instead of the closed system.
NOTE 5: Because of the toxic nature of mercury vapor precaution must
be taken to avoid its inhalation. Therefore, a bypass has been
included in the system to either vent the mercury vapor into an
exhaust hood or pass the vapor through some absorbing media, such as:
a) equal volumes of 0.1 M Kttn04, and 10% H2S04 or
b) 0.25% iodine in a 3% a KI solution. A specially treated charcoal
that will adsorb mercury vapor is available.
8. Procedure
8.1 Transfer 100 mL, or an aliquot diluted to 100 mL, containing not more
than 1.0 ug of mercury, to a 300 mL BOD bottle. Add 5 mL of sulfuric
acid (6.1) and 2.5 mL of cone, nitric acid (6.2) mixing after each
additon. Add 15 mL of potassium permanganate solution (6.5) to each
sample bottle (see Note 6). For sewage samples additional
permanganate may be required. Shake and add additional portions of
potassium permanganate solution, if necessary, until the purple color
persists for at least 15 minutes. Add 8 mL of potassium persulfate
(6.6) to each bottle and heat for 2 hours in a water bath at 95°C.
NOTE 6: The same amount of 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.
D-47 7/88
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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
9.3 Report mercury concentrations as follows: Below 0.20 ug/L, 0.20 u;
between 0.20 and 10.0 ug/L, two significant figures; equal to or
above 10.0 ug/L, three significant figures.
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).
Bibliography
1. Kopp, J.F. , Longbottom, M.C. and Lobring, L.B. "Cold Vapor Method for
Determining Mercury", AWUA, 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-48 7/88
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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 mn by mercury vapor. The mercury is
reduced to the elemental state and aerated from solution. The
mercury vapor passes through a cell positioned in the light path of
an atomic absorption spectrophotometer. Absorbance (peak height) is
measured as a function of mercury concentration and recorded in the
usual manner.
2.2 In addition to inorganic forms of mercury, organic mercurials may
also be present. These organo-mercury compounds will not respond to
the flameless atomic absorption technique unless they are first
broken down and converted to mercuric ions. Potassium permanganate
oxidizes many of 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 ipn 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.
CLP-M modified for the Contract Laboratory Program.
D-49 7/88
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4.2 Formation of a heavy precipitate, in some wastewaters and effluents,
has been reported upon addition of concentrated sulfuric acid. If
this is encountered, the problem sample cannot be analyzed by this
method.
4.3 Samples containing solids must be blended and then mixed while being
sampled if total mercury values are to be reported.
NOTE 1: All of the above interferences can be overcome by use of the
Manual Mercury method.
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 WX-22847, argon filled, or
equivalent.
5.6 Recorder: Any multi-range variable speed recorder that is compatible
with the UV detection system is suitable.
D-50 7/88
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6. Reagents
6.1 Sulfuric Acid, Cone: Reagent grade
6.1.1 Sulfuric acid, 2 N: Dilute 56 mL 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 w5th distilled water.
6.3 Stannous Sulfate (See Note 3): Add 50 g stannous sulfate to 500 mL
of 2 N sulfuric acid (6.1.1). This mixture is a suspension and
should be stirred continuously during use.
NOTE 3: Stannous chloride may be used in place of stannous sulfate.
6.4 Sodium Chloride-Hydroxylamine Sulfate (See Note 4) Solution:
Dissolve 30 g of sodium chloride and 30 g of hydroxylamine sulfate in
distilled water to 1 liter.
NOTE 4: Hydroxylamine hydrochloride may be used in place of
hydroxylamine sulfate.
6.5 . Potassium Permanganate: 0.5% solution, w/v. Dissolve 5 g of
potassium permanganate in 1 liter of distilled water.
6.6 Potassium Permanganate, 0.1 N: Dissolve 3.16 g of potassium
permanganate in distilled water and dilute to 1 liter.
6.7 Potassium Persulfate: 0.5% solution, w/v. Dissolve 5 g potassium
persulrate in 1 liter of distilled water.
6.8 Stock Mercury Solution: Dissolve 0.1354 g of mercuric chloride in 75
mL of distilled water. Add 10 mL of cone, nitric acid and adjust the
volume to 100.0 mL. 1.0 mL - 1.0 mg Hg.
6.9 Working Mercury Solution: Make successive dilutions of the stock
mercury solution (6.8) to obtain a working standard containing 0.1 ug
per mL. This working standard and the dilutions of the stock mercury
solution should be prepared fresh daily. Acidity of the working
standard should be maintained at 0.15% nitric acid. This acid should
be added to the flask as needed before the addition of the aliquot.
From this solution prepare standards containing 0.2, 0.5, 1.0, 2.0,
5.0, 10.0, 15.0 and 20.0 ug Hg/L.
6.10 Air Scrubber Solution: Mix equal volumes of 0.1 N potassium
permanganate (6.6) and 10% sulfuric acid (6.1.2).
D-51 7/88
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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.A Arrange working mercury standards from 0.2 to 20.0 ug Hg/L in sampler
and start sampling. Complete loading of sample tray with unknown
samples.
7.5 Prepare standard curve by plotting peak height of processed standards
against concentration values. Determine concentration of samples by
comparing sample peak height with standard curve.
7.6 After the analysis is complete put all lines except the ^SO^ line in
distilled water to wash out system. After flushing, wash out the
H£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 water. This will prevent build-up of oxides of
manganese.
NOTE 5: Because of the toxic nature of mercury vapor, precaution
must be taken to avoid its inhalation. Venting the mercury vapor
into an exhaust hood or passing the vapor through some absorbing
media such as: a) equal volumes of 0.1 N KMnO^(6.6) and 10% HjSO^
(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, W.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. Branderiberger, 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).
D-52 7/88
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5. Goulden, P.D. 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-53 7/88
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AIR
OUT
AIR AND
SOLUTION
IN
ft
7/25 Y
0.4 cm CO
0.7 cm ID
l
-------
Figure 2. Mercury Manifold AA-1
D-55
7/88
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MERCURY ANALYSIS IN SOIL/SEDIMENT BY MANUAL COLD VAPOR TECHNIQUE
MERCURY (in Sediments)
Method 245.5 CLP-M* (Manual Cold Vapor Technique)
1. Scope and Application
1.1 This procedure measures total mercury (organic and inorganic) in
soils, sediments, bottom deposits and sludge type materials
1.2 The range of the method is 0.2 to 5 ug/g. The range may be extended
above or below the normal range by increasing or decreasing sample
size or through instrument and recorder control
2. Summary of Method
2.1 A weighed portion of the sample is acid-digested for 2 minutes at
95°C, followed by oxidation with potassium permanganate and potassium
persulfate. Mercury in the digested sample is then measured by the
conventional cold vapor technique
2.2 An alternate digestion involving the use of an autoclave is described
in (8.2)
3. Sample Handling and Preservation
3.1 Because of the extreme sensitivity of the analytical procedure and
the omnipresence of mercury, care must be taken to avoid extraneous
contamination. Sampling devices and sample containers should be
ascertained to be free of mercury; the sample should not be exposed
to any condition in the laboratory that may result in contact or air-
borne mercury contamination
3.2 Refrigerate solid samples at 4°C (+2°) upon receipt until analysis
(see Exhibit D, Section II).
3.3 The sample should be analyzed without drying. A separate percent
solids determination is required, (Part F).
4. Interferences
4.1 The same types of interferences that may occur in water samples are
also possible with sediments, i.e., sulfides, high copper, high
chlorides, etc.
4.2 Samples containing high concentrations of oxidizable organic
materials, as evidenced by high chemical oxygen demand values, may
not be completely oxidized by this procedure. When this
*CLP-M modified for the Contract Laboratory Program.
D-56 7/88
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occurs, the recovery of organic mercury will be low. The problem car.
be eliminated by reducing the weight of the original sample or by
increasing the amount of potassium persulfate (and consequently
stannous chloride) used in the digestion.
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 cenented 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 Puap: 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).
D-57 7/88
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NOTE 2: In place of the magnesium perchlorate drying tube, a
small reading lamp with 60W bulb may be used to prevent condensation
of moisture inside the cell. The lamp is positioned to shine on the
absorption cell maintaining the air temperature in the cell about
10°C above ambient.
6. Reagents
6.1 Sulfuric acid, cone.: Reagent grade of low mercury content
6.2 Nitric acid, cone.: Reagent grade of low mercury content
6.3 Stannous Sulfate: Add 25.g stannous sulfate to 250 mL of 0.5 N
sulfuric acid (6.2). This mixture is a suspension and should be
stirred continuously during use
6.4 Sodium Chloride-Hydroxylamine Sulfate (See Note 3) Solution:
Dissolve 12 g of sodium chloride and 12 g of hydroxylamine sulfate in
distilled water and dilute to 100 mL
NOTE 3: A 10% solution of stannous chloride may be substituted
for (6.3) and hydroxylamine hydrochloride may be used in place of
hydroxylamine sulfate in (6.4)
6.5 Potassium Permanganate: 5% solution, w/v. Dissolve 5 g of potassium
permanganate in 100 mL of distilled water
6.6 Potassium Persulfate: 5% solution, w/v. Dissolve 5 g of potassium
persulfate in 100 mL of distilled water
6.7 Stock Mercury Solution: Dissolve 0.1354 g of mercuric chloride in 75
mL of distilled water. Add mL of cone, nitric acid and adjust the
volume to 100.0 mL. 1.0 - 1.0 mg Hg
6.8 Working Mercury Solution: Make successive dilutions of the stock
mercury solution (6.7) to obtain a working standard containing 0.1
ug/mL. This working standard and the dilution of the stock mercury
solutions should be prepared fresh daily. Acidity of the working
standard should be maintained at 0.15% nitric acid. This acid should
be added to the flask as needed before the addition of the aliquot
7. Calibration
7.1 Transfer 0, 0.5, 1.0, 5.0 and 10 mL aliquots of the working mercury
solutions (6.8) containing 0 to 1.0 ug of mercury to a series of 300
mL BOD bottles. Add enough distilled water to each bottle to make a
total volume of 10 mL. Add 5 mL of cane. H2SO^ (6.1) and 2.5 mL of
cone. HNO-j (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
D-58 ' 7/88
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solution (6.3) and immediately attach the bottle to the aeration
apparatus'. At this point the sample is allowed to stand quietly
without manual agitation. The circulating pump, which has previously
been adjusted to a rate of 1 liter per minute, is allowed to run
continuously. The absorbance, as exhibited either on the
spectrophotometer or the recorder, will increase and reach maximum
within 30 seconds. As soon as the recorder pen levels off,
approximately 1 minute, open the bypass valve and continue the
aeration until the absorbance returns to its minimum value (see Note
4). Close the bypass valve, remove the fritted tubing from the BOD
bottle and continue the aeration. Proceed with the standards and
construct a standard curve by plotting peak height versus micrograms
of mercury
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. ^SO^ 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 are added and the bottle is
covered with a piece of aluminum foil. The sample is autoclaved at
121°C and 15 Ibs. for 15 minutes. Cool, make up to a volume of 100
mL with distilled water and add 6 mL of sodium chloride-hydroxylamine
sulfate solution (6.4) to reduce the excess permanganate. Purge the
head space of the sample bottle for at least one minute and continue
as described under (7.1)
D-59 7/88
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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
U6 HS/S ~ wt of the aliquot in gms
(based upon dry vt of the sample)
9.3 Report mercury concentrations as described for aqueous mercury
samples converted to units of mg/kg. The sample result or the
detection limit for each sample must be corrected for sample weight
and % solids before reporting.
Note that the minimum reportable number that can be substituted in
the formula in section 9.2 is 0.02 ug Hg in the aliquot. Therefore a
sample with a weight of 0.2 grams and 100 % solids that has a reading
from the curve of less than 0.02 ug would be reported as 0.10U mg/kg.
Bibliography
1. Bishop, J. N., "Mercury in Sediments", Ontario Water Resources. Comm.,
Toronto, .Ontario, Canada, 1971
2. Salma, 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-60 7/88
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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-62
Method for Total Cyanide Analysis in Soil/Sediment
Method 335.2 CLP-M D-71
A bibliography citing method references follows each method.
CLP-M Modified for the Contract Laboratory Program.
D-61 7/88
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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
Spectrophotometric)
1. Scope and Application
1.1 This method is applicable to the determination of cyanide in
drinking, surface and saline waters, domestic and industrial wastes.
1.2 The titration procedure using silver nitrate with p-
dimethylaminobenzalrhodanine indicator is used for measuring
concentrations of cyanide exceeding 1 mg/L (0.25 mg/250 mL of
absorbing liquid). (Option A, 8.2).
1.3 The manual colorometric procedure is used for concentrations below 1
mg/L of cyanide and is sensitive to about 0.02 mg/L. (Option B,
8.3).
1.4 The working range of the semi-automated Spectrophotometric method is
0.005 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-pyrazclone or
pyridinebarbituric acid reagent. The absorbance is read at 620 run
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-62 7/88
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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
(KI-starch paper); a blue color indicates the need for treatment.
Add ascorbic acid, a few crystals at a time, until a drop of sample
produces no color on the indicator paper. Then add an additional 0.6
g of ascorbic acid for each liter of sample volume.
4.3 Samples are preserved with 2 mL of 10 N sodium hydroxide per liter of
sample (pH> 12) at the time of collection (Exhibit D, Section II).
4.4 Samples must be stored at 4°C(+2°C) and must be analyzed within the
holding time specified in Exhibit D, Section II.
5. Interferences
5.1 Interferences are eliminated or reduced by using the distillation
procedure described in Procedure 8.1.
5.2 Sulfides adversely affect the colorimetric and titration procedures.
If a drop of the distillate on lead acetate test paper indicates the
presence of sulfides, treat 25 mL more of the sample than that
required for the cyanide determination with powdered cadmium
carbonate. Yellow cadmium sulfide precipitates if the sample
contains sulfide. Repeat this operation until a drop of the treated
sample solution does not darken the lead acetate test paper. Filter
the solution through a dry filter paper into a dry beaker, and from
the filtrate measure the sample to be used for analysis. Avoid a
large excess of cadmium carbonate and a long contact time in order to
minimize a loss by complexation or occlusion of cyanide on the
precipitated material. Sulfides should be removed prior to
preservation with sodium hydroxide as described in 4.3.
5.3 The presence of surfactants may cause the sample to foam during
refluxing. If this occurs, the addition of an agent such as Dow
Coming 544 ant if cam 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-63 7/88
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6.3 Spectrophotometer suitable for measurements at 578 nm or 620 nm with
a 1.0 cm cell or larger (for manual spectrophotometric method).
6.4 Technicon AA II System or equivalent instrumentation, (for automated
spectrophotometric method) including:
6.4.1 Sampler
6.4.2 Pump III
6.4.3 Cyanide Manifold (Figure 3)
6.4.4 SCIC Colorimeter with 15 ma flowcells and 570 ran 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 MgCln'S^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).
D-64 7/88
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7.2.4 Standard silver nitrate solution, 0.0192 N: Prepare by
crushing approximately 5 g AgNO^ crystals and drying to
constant weight at 40°C. Weight out 3.2647 g of dried AgN03,
dissolve in distilled water, and dilute to 1COO mL (1 mL - 1
mg CN).
7.2.5 Rhodanine indicator: Dissolve 20 mg of p-dimethyl-
aminobenzalrhodanine in 100 mL of acetone.
7.2.6 Sodium hydroxide solution, 0.25 N: Dissolve 10 g or NaOH in
distilled water and dilute to 1 liter.
7.3 Manual Spectrophotometric Reagents
7.3.1 .Sodium dihydrogenphosphate, 1 M: Dissolve 138 g of
NaH2P04'H20 in a liter of distilled water. Refrigerate this
solution.
7.3.2 Chloramine-T solution: Dissolve 1.0 g of white, water
soluble chloramine-T in 100 mL of distilled water and
refrigerate until ready to use. Prepare fresh weekly.
7.3.3 Color Reagent-One of the following may be used:
7.3.3.1 Pyridine-barbituric acid reagent: Place 15 g of
barbituric acid in a 250 mL volumetric flask and
add just enough distilled water to wash the sides
of the flask and wet the barbituric acid. Add 75
mL of pyridine and mix. Add 15 mL of HC1 (sp gr
1.19), mix, and cool to room temperature. Dilute
to 250 mL with distilled water and mix. This
reagent is stable for approximately six months if
stored in a cool, dark place.
7.3.3.2 Pyridine-pyrazolone solution:7.3 .3.2.1 3-Methyl-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-Iphenyl-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.
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7.3.3.2.3 Pour solution (7.3.3.2.1) through
nonacid-washed filter paper. Collect
the filtrate. Through the same
filter paper pour solution
(7.3.3.2.2) collecting the filtrate
in the sane 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.A 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 NaH2POA'H20 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, or an aliquot diluted to 500 mL, 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.
D-66 7/88
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8.1.3 Slowly add 25 mL concentrated sulfuric acid (7.1.4) through
the air inlet tube. Rinse the tube with distilled water and
allow the airflow to mix the flask contents for 3 minutes.
Pour 20 mL of magnesium chloride solution (7.1.5) into the
air inlet and wash down with a stream of water.
8.1.4 Heat the solution to boiling, taking care to prevent the
solution from backing up into and overflowing from the air
inlet tube. Reflux for one hour. Turn off heat and continue
the airflow for at least 15 minutes. After cooling the
boiling flask, disconnect absorber and close off the vacuum
source.
8.1.5 Drain the solution from the absorber into a 250 mL volumetric
flask and bring up to volume with distilled water washings
from the absorber tube.
8.2 Titrimetric Determination (Option A)
8.2.1 If the sample contains more than 1 mg of CN, transfer the
distillate, or a suitable aliquot diluted to 250 mL, to a 500
mL Erlenmeyer flask. Add 10-12 drops of the benzalrhodanine
indicator.
8.2.2 Titrate with standard silver nitrate to the first change in
color from yellow to brownish-pink. Titrate a distilled
water blank using the same amount of sodium hydroxide and
indicator as in the sample.
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.
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 wate'r and mix again. Allow 8 minutes
for color development then read absorbance at 578
nm in a 1 cm cell within 15 minutes.
D-67 ' 7/88
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8.3.1.2 Pyridine-pyrazolone method: Add 0.5 mL of
chloramine-T (7.3.2) and mix. After 1 to 2
minutes, add 5 mL of pyridine-pyrazolone solution
(7.3.3.2) and mix. Dilute to mark with distilled
water and mix again. After 40 minutes, read
absorbance at 620 nm in a 1 cm cell. NOTE: More
than 0.5 mL of chloramine-T will prevent the color
from developing with pyridine-pyrazolone.
8.3.2 Prepare a minimum of 3 standards and a blank by pipetting
suitable volumes of standard solution into 250 mL volumetric
flasks. NOTE: One calibration standard must be at the
Contract Required Detection Limit (CRDL). To each standard,
add 50 mL of 1.25 N sodium hydroxide and dilute to 250 mL
with distilled 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:
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mL Standard Solution Concentration
(7.2.3) diluted to 1 liter ug CN/L
0 0
4.0 20
10.0 50
20.0 100
30.0 150
40.0 200
Add 10 g of NaOH to each standard. Store at 4°C(±2°C)
8.4.3 Place calibration standards, blanks, and control standards in
the sampler tray, followed by distilled samples, distilled
duplicates, distilled standards, distilled spikes, and
distilled blanks.
8.4.4 When a steady reagent baseline is obtained and before
starting the sampler, adjust the baseline using the
appropriate knob on the colorimeter. Aspirate a calibration
standard and adjust the STD CAL dial on the colorimeter until
the desired signal is obtained. Record the STD CAL value.
Re-establish the baseline and proceed to analyze calibration
standards, blanks, control standards, distilled samples, and
distilled QC audits.
9. Calculations
9.1 Using the titrimetric procedure, calc'ulate concentratipn of CN as
follows:
(A-B) 1.000 mL/L 250 mL
CN, mg/L - mL orig. sample x mL of aliquot titrated
WHERE: A - volume of AgN03 for titration of sample
(1 mL - 1 mg Ag)
B - volume of AgNO^ 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 any
dilutions which were made before or after distillation.
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9.3 If the colorimetric procedure is used, calculate the cyanide, in
ug/L, in the original sample as follows:
Ax 1.000 mL/L 50 mL
CN, ug/L B C
WHERE: A - ug CN read from standard curve (per 250 mL)
B - mL of original sample for distillation (See 8.1.1)
C — mL taken for colorimetric analysis (See 8.3.1)
AND: 50 mL - volume of original sample aliquot (See 8.3.1)
1000 mL/L - conversion mL to L
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-70 7/88
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METHOD FOR TOTAL CYANIDE ANALYSIS IN SOIL/SEDIMENT
CYANIDE, TOTAL (in Sediments)
P-M (Titrimetric; Manual Spec
Semi-Automated Spectrophotometric)
Method 335.2 CLP-M* (Titrimetric; Manual Spectrophotometric;
1. Scope and Application
1.1 This method is applicable to the determination of cyanide in
sediments and other solids.
1.2 The detection limit is dependent upon the weight of sample taken for
analysis.
2. Summary of Method
2.1 The cyanide as hydrocyanic acid (HCN) is released from cyanide
complexes by means of a reflux-distillation operation and absorbed in
a scrubber containing sodium hydroxide solution. The cyanide ion in
the absorbing solution is then determined by volumetric titration or
coLorimetrically.
2.2 In the colorimetric measurement the cyanide is converted to cyanogen
chloride, CNC1, by reaction with chloramine-T at a pH less than 8
without hydrolyzing to the cyanate. After the reaction is complete,
color is formed on the addition of pyridine-pyrazolone or pyridine-
barbituric acid reagent. The absorbance is read at 620 nm when using
pyridine-pyrazolone for 578 nm for pyridine-barbituric acid. To
obtain colors of comparable intensity, it is essential to have the
same salt content in both the sample and the standards.
2.3 The titrimetric measurement uses a standard solution of silver
nitrate to titrate cyanide in the presence of a silver sensitive
indicator.
3. Definitions
3.1 Cyanide is defined as cyanide ion and complex cyanides converted to
hydrocyanic acid (HCN) by reaction in a reflux system of a mineral
acid in the presence of magnesium ion.
4. Sample Handling and Preservation
4.1 Samples must be stored at 4°C(+2°C) and must be analyzed within the
holding time specified in Exhibit D, Section II.
4.2 Samples are not dried prior to analysis. A separate percent solids
determination must be made in accordance with the procedure in Part
F.
CLP-M Modified for the Cortract Laboratory Program.
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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-72 7/88
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7.1.4 Sulfuric acid: concentrated
7.1.5 Magnesium chloride solution: Weigh 510 g of MgC12.6H20 into
a. 1000 mL flask, dissolve and dilute to 1 liter with
distilled water.
7.2 Stock Standards and Titration Reagents
7.2.1 Stock cyanide solution: Dissolve 2.51 g of KCN and 2 g KOH
in 1 liter of distilled water. Standardize with 0.0192 N
AgN03.
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 AgNO-j crystals and drying to
constant'weight at 40°C. Weigh out 3.2647 g of dried AgN03,
dissolve in distilled water, and dilute to 1000 mL (1 mL - 1
mg CN).
7.2.5 Rhodanine indicator: Dissolve 20 mg of p-dimethy1-amino-
benzalrhodanine in 100 mL acetone.
7.3 Manual Spectrophotometric Reagents
7.3.1 Sodium dihydrogenphosphate, 1 M: Dissolve 138 g of
Nal^PO^'^O in 1 liter of distilled water. Refrigerate this
_ solution.
7.3.2 Chloramine-T solution: Dissolve 1.0 g of white, water
soluble Chloramine-T in 100 mL of distilled water and
refrigerate until ready to use. Prepare fresh weekly.
7.3.3 Color reagent - One of the following may be used:
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:
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7.3.3.2.1 3-Methyl-l-phenyl-2-pyrazolin-5-one
reagent, saturated solution: Add
0.25 g of 3-methyl-l-phenyl-2-
pyrazolin-5-one to 50 mL of distilled
water, heat to 60°C with stirring.
Cool to room temperature.
7.3.3.2.2 3,3'Dimethyl -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-H20 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.
D-74 7/88
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8.1.2 Add 50 mL of sodium hydroxide (7.1.1) to the absorbing tube
and dilute if necessary with distilled water to obtain an
adequate depth of liquid in the absorber. Connect the
boiling flask, condenser, absorber, and trap in the train.
8.1.3 Start a slow stream of air entering the boiling flask by
adjusting the vacuum source. Adjust the vacuum so that
approximately one bubble of air per second enters the boiling
flask through the air inlet tube.
NOTE: The bubble rate will not remain constant after the
reagents have been added and while heat is being applied
to the flask. It will be necessary to readjust the air
rate occasionally to prevent the solution in the boiling
flask from backing up into the air inlet tube.
8.1.4 Slowly add 25 mL of cone, sulfuric acid (7.1.4) through the
air inlet tube, Rinse the tube with distilled water and
allow the airflow to mix the flask contents for 3 minutes.
Pour 20 mL of magnesium chloride solution (7.1.5) into the
air inlet and wash down with a stream of water.
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 mL volumetric
flask and bring up to volume with distilled water washings
from the absorber tube.
8.2 Tltrimetric 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)
D-75 7/88
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8.3.1 Withdraw 50 mL or less of the solution from the flask and
transfer to a 100 mL volumetric flask. If less than 50 mL is
taken, dilute to 50 mL with 0.25 N sodium hydroxide solution
(7.2.6). Add 15.0 mL of sodium phosphate solution (7.3.2)
and mix.
8.3.1.1 Pyridine-barbituric acid 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 ran 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
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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:
mL Standard Solution Concentration
C7.2.3) diluted to 1 liter ug CN/L
0 0
4.0 20
10.0 50
20.0 100
30.0 150
40.0 200
Add 10 g of NaOH to each standard. Store at 4°C(±2°C).
8.4.3 Place calibration standards, blanks, and control
standards in the sampler tray, followed by distilled
samples, distilled duplicates, distilled standards,
distilled spikes, and distilled blanks.
8.4.4 — When a steady reagent baseline is obtained and before
starting the sampler, adjust the baseline using the
appropriate knob on the colorimeter. Aspirate a calibration
standard and adjust the STD CAL dial on the colorimeter until
the desired signal is obtained. Record the STD CAL value.
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.
D-7.7 7/88
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9.2.1 (Titration)
(A - B) x _ 25° mL _ x 1000 g/kg
mL aliquot titrated
CN. mg/kg -- _ -
_ %solids
WHERE: A - mL of AgN03 for titration of sample
(1 mL - 1 mg Ag)
B - mL of AgN03 for titration of blank
(1 mL - 1 mg Ag)
C - wet weight of original sample in g
(See 8.1.1)
AND: 250 mL - volume of distillate (See 8.1.6)
1000 g/kg - conversion factor g to kg
mL aliquot titrated (See 8.2.1)
% solids (see Part F)
9.2.2 (Manual Spectrophotometric)
50 mL
CN, mgAg - A X I
r „ % solids
c x 100
WHERE: A - ug CN read from standard curve (per 250 mL)
B - mL of distillate taken for colorimetric
determination (8.3.1)
C - wet weight of original sample in g
(See 8.1.1)
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 x % solids
100
WHERE: A - ug/L determined from standard curve
C - wet weight of original sample in g
(See 8.1.1)
D-78 7/88
-------
AND: .25 - conversion factor for distillate final
volume (See 8.1.6)
% solids (see Part F)
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-79 7/88
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ALllHN CONDENSER —
AIR INLET TUBE
— CONNECTING TUBING
ONE LITER
BOILING FLASK
SUCTION
Figure 1. Cyanide distillation apparatus
D-80
7/88
-------
COOLING WATER
INLET TUBE^
HEATER -
SCREW CLAMP
4
ft
3x
TO LOW VACUUM
SOURCE
- ABSORBER
*- DISTILLING FLASK
O
Figure 2. Cyanide distillation apparatus
D-81
7/88
-------
-
~fc ~
o
o
O O
o
X
.0
o:
o
K
3
u.
^ f
Figure 3. Cyanide Manifold
D-82
7/88
-------
PART F - PERCENT SOLIDS DETERMINATION PROCEDURE
1. Immediately following the weighing of the sample to be processed for
analysis (see Section III, Part B- Soil/Sediment Sample Preparation),
add 5-10 g of sample to a. tared weighing dish. Weigh and record the
weight to the nearest 0.01 g.
2. Place weighing dish plus sample, with the cover tipped to allow for
moisture escape, in a drying oven maintained at 103-105°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.1* 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
demonstrate the attainment of constant weight, data must 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-83 7/88
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PART G - ALTERNATE METHODS (CATASTROPHIC ICP FAILURE^
Analvte Page No.
Aluminum - Method 202.2 CLP-M*, Furnace AA D-86
Barium - Method 208.2 CLP-M, Furnace AA D-87
Cobalt - Method 219.2 CLP-M, Furnace AA D-88
Copper - Method 220.2 CLP-M, Furnace AA D-89
Iron - Method 236.2 CLP-M, Furnace AA D-90
Manganese - Method 243.2 CLP-M, Furnace AA D-91
Nickel - Method 249.2 CLP-M, Furnace AA D-92
Vanadium - Method 286.2 CLP-M, Furnace AA D-93
Zinc - Method 289.2 CLP-M, Furnace AA D-94
Aluminum - Method 202.1 CLP-M, Flame AA D-96
Antimony - Method 204.1 CLP-M, Flame AA D-98
Barium - Method 208.1 CLP-M, Flame AA D-99
Beryllium - Method 210.1 CLP-M, Flame AA D-100
Cadmium - Method 213.1 CLP-M, Flame AA D-101
Chromium - Method 218.1 CLP-M, Flame AA D-102
Cobalt - Method 219.1 CLP-M, Flame AA D-103
Copper - Method 220.1 CLP-M, Flame AA D-104
Iron - Method 236.1 CLP-M, Flame AA D-105
Lead - Method 239.1 CLP-M, Flame AA D-106
Manganese - Method 243.1 CLP-M, Flame AA D-107
Nickel - Method 249.1 CLP-M, Flame AA D-108
Silver - Method 272.1 CLP-M, Flame AA D-110
Thallium - Method 279.1 CLP-M, Flame AA D-lll
Vanadium - Method 286.1 CLP-M, Flame AA D-112
Zinc - Method 289.1 CLP-M, Flame AA . D-113
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-84 7/88
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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) 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-85 7/87
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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 run
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.
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-86 7/87
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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 (General1)
1. Drying Tine and Temp: 30 sec @ 125°.
2. Ashing Time and Temp: 30 sec @ 1200°C.
3. Atomizing Tine and Temp: 10 sec @ 2800°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 553.6 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for. a
Perkin-Elmer HGA-2100, based on the use of a 20 uL injection,
continuous flow purge gas and pyrolytic graphite and are to be used as
guidelines only.
2. The use of halide acid should be avoided.
3. Because of possible chemical interaction, nitrogen should not be used
as a purge gas.
4. For every sample analyzed, verification is necessary to determine that
method of standard addition is not required (see Exhibit E).
5. If method of standard addition is required, follow the procedure given
in Exhibit E.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-87 7/87
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COBALT*
Method 219.2 CLP-M** (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L
Approximate Detection Limit: 1 ug/L
Preparation of Standard Solution
1. Stock solution: Prepare as described under AA Flame Technique (Method
219.1 CLP-M).
2. Prepare dilutions of' the stock solution to be used as calibration
standards at the time of analysis. These solutions are also to be used
for "standard additions".
3. The calibration standards must be prepared using the same type of acid
and at the same concentration as will result in the sample to be
analyzed after sample preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 900°C.
3. Atomizing Time' and Temp: 10 sec (§ 2700°C.
4. . Purge Gas Atmosphere: Argon
5. Wavelength: 240.7 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a
Perkin-Elmer HGA-2100, based on the use of a 20 uL injection,
continuous flow purge gas and non-pyrolytic graphite and are to be used
as guidelines only. Smaller size furnace devices or those employing
faster rates of atomization 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-88 7/87
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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 the stock solution to be used as calibration
standards'at the time of analysis. These solutions are also to be used
' for "standard additions".
3. The calibration standards must be prepared using the same type of acid
and at the same concentration as will result in the sample to be
analyzed after sample preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec <§ 900°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 324.7 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a
Perkin-Elmer HGA-2100, based on the use 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 -tates 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-89 7/87
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IRON*
Method 236.2 CLP-M** (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L
Approximate Detection Limit: 1 ug/L
Preparation of Standard Solution
1. Stock solution: Prepare as described under AA Flame Technique (Method
236.1 CLP-M).
2. Prepare dilutions of the stock solution to be used as calibration
standards at the time of analysis. These solutions are also to be used
for "standard additions".
3. The calibration standards must be prepared using the same type of acid
and at the same concentration as will result in the sample to be
analyzed after sample preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 1000°C.
3. Atomizing Time and Temp: 10 sec (§ 2700°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 248.3 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a
Perkin-Elmer HGA-2100, based on the use of a 20 uL injection,
continuous flow purge gas and non-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
temperarures 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.
A. 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-90 7/87
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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-91 • 7/87
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NICKEL*
Method 249.2 CLP-M** (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 5-100 ug/L
Approximate Detection Limit: 1 ug/L
Preparation of Standard Solution •
1. Stock solution: Prepare as described under AA Flame Technique (Method
249.1 CLP-M).
2. Prepare dilutions of the stock solution to be used as calibration
standards at the time of analysis. These solutions are also to be used
for "standard additions".
3. The calibration standards must be prepared using the same type of acid
and at the same concentration as will result in the sample to be
analyzed after sample preparation.
Parameters (General)
1. Drying Time and Temp: ' 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 900°C.
3. Atomizing Time and Temp: 10 sec @ 2700°C.
4 . Purge Gas Atmosphere : Argon
5. Wavelength: 232.0 nm
6 . Other operating parameters should be set as specified by the particular
instrument manufacturer .
Notes
1 . The above concentration values and instrument conditions are for a
Perkin- Elmer HGA-2100, based on the use of a 20 uL injection,
continuous flow purge gas and non-pyrolytic graphite and are to be used
as guidelines only. Smaller size furnace devices or those employing
faster rates of atomization can be operated using lower atomization
temperatures for shorter time periods than the above recommended
settings .
2. The use of background correction is required.
3. Nitrogen may also be used as the purge gas.
4. For every sample analyzed, verification is necessary to determine that
method of standard addition is not required (see Exhibit E) .
5. If method of standard addition is required, follow the procedure given
in Exhibit E.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-92 7/87
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VANADIUM*
Method 286.2 CLP-M** (Atomic Absorption, Furnace Technique)
Optimum Concentration Range: 10-200 ug/L
Approximate Detection Limit: 4 ug/L
Preparation of Standard Solution
1. Stock solution: Prepare as described under AA Flame Technique (Method
286.1 CLP-M).
2. Prepare dilutions of the stock solution to be used as calibration
standards at the time of analysis. These solutions are also to be used
•for "standard additions."
3. The calibration standards must be prepared using the same type of acid
and at the same concentration as will result in the sample to be
analyzed after sample preparation.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 1400°C.
3. Atomizing Time and Temp: 15 sec @ 2800°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 318.4 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a
Perkin-Elmer HGA-2100, based on the use of a 20 uL injection,
continuous flow purge gas and pyrolytic graphite and are to be used as
guidelines only. Smaller size furnace devices or those employing
faster rates of atomization can be operated using lower atomization
temperatures for shorter time periods than the above recommended
settings.
2. The use of background correction is required.
3. Because of possible chemical interaction, nitrogen should not be used
as the purge gas.
4. For every sample analyzed, verification is necessary to determine that
method of standard addition is not required (see Exhibit E).
5. If method of standard addition is required, follow the procedure given
in Exhibit E.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program
D-93 7/87
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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 (General1)
1. Drying Time and Temp: 30 sec @ 125°C.
2. Ashing Time and Temp: 30 sec @ 400°C.
3. Atomizing Time and Temp: 10 sec @ 2500°C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 213.9 nm
6. Other operating parameters should be set as specified by the particular
instrument manufacturer.
Notes
1. The above concentration values and instrument conditions are for a
Perkin-Elmer HGA-2100, based on the use of a 20 uL injection,
continuous flow purge gas and non-pyrolytic graphite and are to be used
as guidelines only. Smaller size furnace devices or those employing
faster rates of atomization can be operated using lower atomization
temperatures for shorter time periods then the above recommended
settings.
2. The use of background correction is required.
3. Nitrogen may also be used as the purge gas.
4. The analysis of zinc by the graphite furnace is extremely sensitive and
very subject to contamination from the work area, reagents, and pipette
tips. Since all these factors affect the precision and accuracy, zinc
should be analyzed by the direct aspiration procedure whenever
possible.
5. For every sample analyzed, verification is necessary to determine that
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-94 7/87
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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-95 7/87
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ALUMINUM*
Method 202.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 5-50 mg/L using a wavelength of 309.3 run
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. HNOj to the
metal, cover the beaker and warm gently. When solution is complete,
transfer quantitatively to a liter volumetric flask and make up to
volume with deionized distilled water. 1 mL - 1 mg Al (1000 mg/L).
2. Potassium Chloride Solution: Dissolve 95 g potassium chloride (KC1) in
deionized distilled water and make up to 1 liter.
3. Prepare dilutions of the stock solution to be used as calibration
standards at the time of analysis. The calibration standards must be
prepared using the same type of acid and at the same concentration as
will result in the sample to be analyzed after sample preparation. To
each 100 mL of standard and sample alike add 2.0 mL potassium chloride
solution.
Instrument Parameters (General)
1. Aluminum hollow cathode lamp
2. Wavelength: 309.3 nm
3. Fuel: Acetylene
4. Oxidant: Nitrous oxide
5. Type of flame: Fuel rich
Interferences
1. Aluminum is partially ionized in the nitrous oxide-acetylene flame.
This problem may be controlled by the addition of an alkali metal
(potassium, 1000 ug/mL) to both sample and standard solutions.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-96 7/87
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Notes
1. The following may also be used:
308.2 ran Relative Sensitivity 1
396.2 ran Relative Sensitivity 2
394.4 ran 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-97 7/87
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ANTIMONY*
Method 204.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 1-40 mg/L u^ing 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 the stock solution^to be used as calibration
standards at the time of analysis. The calibration standards must be
prepared using the same type of acid and at the same concentration as
will result in the sample to be analyzed after sample preparation.
Instrumental Parameters (General)
1. Antimony hollow cathode lamp
2. Wavelength: 217.6 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Fuel lean
Interferences
1. In the presence of lead (1000 mg/L), a special interference may occur
at the 217.6 nm resonance line. In this case the 231.1 nm antimony
line should be used.
2. Increasing acid concentrations decrease antimony absorption. To avoid
this effect, the acid concentration in the samples and in the standards
must be matched.
Notes
1. For concentrations of antimony below 0.35 mg/L, use of the Furnace
Technique (Method 204.2 CLP-M) is recommended.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-98 7/87
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BARIUM*
Method 208.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 1-20 mg/L using a wavelength of 553.6 nm
Sensitivity: 0.4 mg/L
Approximate Detection Limit: 0.1 mg/L
Preparation of Standard Solution
1. - Stock Solution: Dissolve 1.7787 g of barium chloride (BaCl2'2H20,
analytical reagent grade) in deionized distilled water and dilute to
liter. 1 mL - 1 mg Ba (1000 mg/L).
2. Potassium chloride solution: Dissolve 95 g potassium chloride, KC1, in
deionized distilled water and make up to 1 liter.
3. Prepare dilutions of the stock solution to be used as calibration
standards at the time of analysis. To each 100 mL of standard and
sample alike add 2.0 mL potassium chloride solution. The calibration
standards must be prepared using the same type of acid and at the same
concentration as will result in the sample to be analyzed after sample
preparation.
Instrumental Parameters (General)
1. Barium hollow cathode lamp
2. Wavelength: 553.6 nm
3. Fuel: Acetylene
4. Oxidant: Nitrous oxide
5. Type of flame: Fuel rich
Interferences
1. The use of a nitrous oxide-acetylene flame virtually eliminates
chemical interference; however, barium is easily ionized in this flame
and potassium must be added (1000 mg/L) to standards and samples alike
to control this effect.
2. If the nitrous oxide flame is not available and acetylene-air is used,
phosphate, silicon and aluminum will severely depress the barium
absorbance. This may be overcome by the addition of 2000 mg/L
lanthanum.
Notes
1. For concentrations of barium below 0.2 mg/L, use of the Furnace
Technique (Method 208.2 CLP-M) is recommended.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-99 7/87
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BERYLLIUM*
Method 210.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.052 mg/L using a wavelength of 234.9 run
Sensitivity: 0.025 mg/L
Approximate Detection Limit: 0.005 mg/L
Preparation of Standard Solution
1. Stock Solution: Dissolve 11.6586 g of beryllium sulfate, 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. Wavelengch: 234.9 nm
3. Fuel: Acetylene
4. Oxidant: Nitrous oxide
5. Type of flame: Fuel rich
Interferences
1. Sodium and silicon at concentrations in excess of 1000 mg/L have been
found to severely depress the beryllium absorbance.
2. Bicarbonate ion is reported to interfere; however, its effect is
eliminated-when samples are acidified to a pH of 1.5.
3. Aluminum at concentrations of 500 ug/L is reported to depress the
sensitivity of beryllium [Spectrochim Acta 22, 1325 (1966)].
Notes
1. For concentrations of beryllium below 0.02 mg/L, use of the Furnace
Technique (Method 210.2 CLP-M) is recommended.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program!
D-100 7/87
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CADMIUM*
Method 213.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.052 mg/L using a wavelength of 228.8 run
Sensitivity: 0.025 mg/L
Approximate Detection Limit: 0.005 mg/L
Preparation of Standard Solution
1. Stock Solution: Carefully weigh 2.282 g of cadmium sulfate
(3CdS04'8H20, analytical reagent grade) and dissolve in deionized
distilled water. Make up to 1 liter with dionized distilled water.
1 mL - 1 mg Cd (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration
standards at the time of analysis. The calibration standards must be
prepared using the same type of acid and at the same concentration as
will result in the sample to be analyzed after sample preparation.
Instrumental Parameters (General)
1. Cadmium hollow cathode lamp
2. Wavelength: 228.8 run
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-101 7/87
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CHROMIUM*
Method 218.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.5-10 mg/L using a wavelength of 357.9 na
Sensitivity: 0.25 mg/L
Approximate Detection Limit: 0.05 mg/L
Preparation of Standard Solution
1. Stock Solution: Dissolve 1.923 g of chromium trioxide (CrO^, reagent
grade) in deionized distilled water. When solution is complete,
acidify with redistilled HNO^ and dilute to 1 liter with deionized
distilled water. 1 mL - 1 mg Cr (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration
standards at the time of analysis. The calibration standards must be
prepared using the same type of acid and at the same concentration as
will result in the sample to be analyzed after sample preparation.
Instrument Parameters (General)
1. Chromium hollow cathode lamp
2. Wavelength: 357.9 ran
3. Fuel: Acetylene
4. Oxidant: Nitrous oxide
5. Type of flame: Fuel rich
Notes
1. The following wavelengths may also be used:
359.3 nm Relative Sensitivity 1.4
425.4 nm Relative Sensitivity 2
427.5 nm Relative Sensitivity 3
428.9 ran 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-102 7/87
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COBALT*
Method 219.1** CLP-M (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.5-5 mg/L using a wavelength of 240.7 nm
Sensitivity: 0.2 mg/L
Approximate Detection Limit: 0.05 mg/L
Preparation of Standard Solution
1. Stock Solution: Dissolve 4.307 g of cobaltous chloride (CoC12. 6H20
analytical reagent grade), in deionized distilled water. Add 10 mL of
concentrated nitric acid and dilute to 1 liter with deionized distilled
water. 1 mL - 1 mg Co (1000 mg/L).
2. Prepare dilutions of the stock cobalt solution to be used as
calibration standards at the time of analysis. The calibration
standards must be prepared using the same type of acid and at-the same
concentration as will result in the sample to be analyzed after sample
preparation.
Instrument Parameters (General)
1. Cobalt hollow cathode lamp
2. Wavelength: 240.7 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Notes
1. For concentrations of cobalt below 100 ug/L use of the Furnace
Technique (Method 219.2 CLP-M) is recommended.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-103 7/87
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COPPER*
Method 220.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.2-5 mg/L using a wavelength of 324.7 nm
Sensitivity: 0.1 mg/L
Approximate Detection Limit: 0.02 mg/L
Preparation of Standard Solution
1. Stock Solution: Carefully weigh 100 g of electrolyte copper
(analytical reagent grade). Dissolve.in 5 wL redistilled HNO-j and make
up to 1 liter with deionized distilled water. Final concentration is 1
mg Cu per mL (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration
standards at the time of analysis. The calibration standards must be
prepared using the same type of acid and at the same concentration as
will result in the sample to be analyzed after sample preparation.
Instrumental Parameters (General)
1. Copper hollow cathode lamp
2. Wavelength: 324.7 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Notes '
1. For concentrations of copper below 50 ug/L use of the Furnace Technique
(Method 220.2 CLP-M) is recommended.
2. Numerous absorption lines are available for the determination' of
copper. ~By selecting a suitable absorption wavelength, copper samples
may be analyzed over a very wide range of concentrations. The
following lines may be used:
327.4 nm Relative Sensitivity 2
216.5 nm Relative Sensitivity 7
222.5 nm Relative Sensitivity 20
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-104 7/87
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IRON*
Method 236.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.3-5 mg/L using a wavelength of 248.3 nm
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^, 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 run
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 na-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-105 ' 7/87
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LEAD*
Method 239.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 1-20 mg/L using a wavelength of 283.3 ran
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.
aters (General)
1. Lead hollow cathode lamp
2. Wavelength: 283.3 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Notes
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-106 7/87
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MANGANESE*
Method 243.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.1-3 mg/L using a wavelength of 279.5 run
Sensitivity: 0.05 mg/L
Approximate Detection Limit: 0.01 mg/L
Preparation of Standard Solution
1. Stock Solution: Carefully weigh 1.000 g of manganese metal (analytical
reagent grade), and dissolve in 10 mL redistilled HNO^. When solution
is complete, dilute to 1 liter with 1% (v/v) HC1. 1 mL = 1 mg Mn (1000
mg/L).
2. Prepare dilutions of the stock solution to be used as calibration
standards at the time of analysis. The calibration standards must be
prepared using the same type' of acid and at the same concentration as
will result in the sample to be analyzed after sample preparation.
Instrumental Parameters (General)
1. Manganese hollow cathode lamp
2. Wavelength: 279.5 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Notes
1. For concentrations of manganese below 25 ug/L, use of the Furnace
Technique. (Method 243.2 CLP-M) is recommended.
2. The following line may also be used: 403.1 nm Relative Sensitivity 10.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-107 7/87
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NICKEL*
Method 249.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.3-5 ntg/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, NiCNO^'SHoO
(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-108 . 7/87
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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 AgNOj, (analytical reagent grade)
in deionized distilled water, add 10 mL cone. 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. The calibration standards must be
prepared using Che same type of acid and at the same concentration as
will result in the sample to be-analyzed after sample preparation.
3. Iodine Solution, 1 N: Dissolve 20 grams of potassium iodide, KI
(analytical reagent grade) in 50 mL of deionized distilled water, add
12.7 grams of iodine, I2< (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. NH4OH, 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)
jnstrifgf|ental 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-109 7/87
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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 nm wavelength 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-110
7/87
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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 mg Tl (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration
standards at the time of analysis. The calibration standards must be
prepared using nitric acid and at the same concentration as will result
in the sample to be analyzed after sample preparation.
^nstr""*ental Parameters (General)
1. Thallium hollow cathode lamp
2. Wavelength: 276.8 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Notes
1. For concentrations of thallium below 0.2 mg/L, use of the Furnace
Technique (Method 279.2 CLP-M) is recommended.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-lll 7/87
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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 nm
Sensitivity: 0.8 mg/L
Approximate Detection Limit: 0.2 mg/L
Preparation of Standard Solution
1. Stock Solution: Dissolve 1.7854 g of vanadium pentoxide, VjO^
(analytical reagent grade) in 10 mL of cone, nitric acid and dilute to
1 liter with deionized distilled water. 1 mL - 1 mg V (1000 mg/L).
2. Aluminum nitrate solution: Dissolve 139 g aluminum nitrate,
A1(NO3)3'9H20, in 150 mL of deionized distilled water; heat to effect
solution. Allow to cool and make up to 200 mL.
3. Prepare dilutions of the stock vandium solution to be used as
calibration standards at the time of analysis. The calibration
standards must be prepared using the same type of acid and at the same
concentration as will result in the sample to be analyzed after sample
preparation. To each 100 mL of standard and sample alike, add 2 mL of
the aluminum nitrate solution.
Instrumental Parameters (General)
1. Vanadium hollow cathode lamp
2. Wavelength: 318.4 nm
3. Fuel: Acetylene
4. Oxidant: Nitrous Oxide
5. Type of flame: Fuel rich
Interferences
1. It has been reported that high concentrations of aluminum and titanium
increase the sensitivity of vanadium. This interference can be
controlled by adding excess aluminum (1000 ppm) to both samples and
standards. [Talanta 15, 871 (1968)].
Notes
1. For concentrations of vanadium below 0.5 mg/L, use of the Furnace
Technique (Method 282.6 CLP-H) is recommended.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-112 7/87
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ZINC*
Method 289.1 CLP-M** (Atomic Absorption, Flame Technique)
Optimum Concentration Range: 0.05-1 mg/L using a wavelength of 213.9 nm
Sensitivity: 0.02 mg/L
Approximate Detection Limit: 0.005 mg/L
Preparation of Standard Solution
1. Stock Solution: Carefully weigh 1.00 g of zinc metal (analytical
reagent grade) and dissolve cautiously in 10 mL HNOj. When solution is
complete make up to 1 liter with deionized distilled water. 1 mL - 1
mg Zn (1000 mg/L).
2. Prepare dilutions of the stock solution to be used as calibration
standards at the time of analysis. The calibration standards must be
prepared using the same type of acid and at the same concentration as
will result in the sample to be analyzed after sample preparation.
Instrumental Parameters (General1)
1. Zinc hollow cathode lamp
2. Wavelength: 213.9 nm
3. Fuel: Acetylene
4. Oxidant: Air
5. Type of flame: Oxidizing
Notes
1. High levels of silicon may interfere.
2. The air-acetylene flame absorbs about 25% of the energy at the 213.9 nm
line. ~
3. The sensitivity may be.increased by the use of low-temperature flames.
4. Some container cap liners can be a source of zinc contamination. To
circumvent or avoid this problem, the use of the polypropylene caps is
recommended.
5. For concentrations of zinc below 0.01 mg/L, use of the Furnace
Technique (Method 289.2 CLP-M) is recommended.
*This method may only be used under specified conditions.
**CLP-M Modified for the Contract Laboratory Program.
D-113 7/87
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EXHIBIT E
QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
Page No.
SECTION I - GENERAL QA/QC PRACTICES E-l
SECTION II - SPECIFIC QA/QC PROCEDURES E-2
SECTION III - LABORATORY EVALUATION PROCESS E-19
7/88
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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-l 7/88
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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 vill 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 two samples per calendar quarter during the contract
period.
The Contractor must perform and report to SHO and EMSL/LV 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
E-2 7/88
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spikes,'duplicates, 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.
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 TCP (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. IGP Serial Dilution Analysis (L)
10. Instrument Detection Limit (IDL) Determination
11. Interelement Corrections for ICP (ICP)
12. Linear Range Analysis (LRA)
13. Furnace AA QC Analyses
1. Instrument Calibration
Guidelines for instrumental calibration are given in EPA 600/4-79-020
and/or Exhibit D. Instruments must be calibrated daily or once every 24
hours and each time the instrument is set up. The instrument
standardization date and time must be included in the raw data.
For atomic absorption systems, calibration standards are prepared by
diluting the stock metal solutions at the time of analysis. Date and
time of preparation and analysis must be given in the raw data.
E-3 , 7/88
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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
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 prepare* as described
in Exhibit D.
X
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 (ICV) and Continuing Calibration
Verification (CCV)
a. Initial Calibration Verification'(ICV)
Immediately after each of the ICP, AA and cyanide systems have
been calibrated, the accuracy of the initial calibration shall be
verified and documented for every analyte by the analysis of EPA
Initial Calibration Verification Solution(s) at each wavelength
used for analysis. When measurements exceed the control limits of
Table 1-Initial and Continuing Calibration Verification Control
Limits for Inorganic Analyses (in Exhibit E) r the analysis must be
terminated, the problem corrected, the instrument recalibrated,
and the calibration reverified.
E-A 7/88
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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.
b. Continuing Calibration Verification (CCV)
To ensure calibration accuracy during each analysis run, one of
the following standards is to be used for continuing calibration
verification and must be be analyzed and reported for every
wavelength used for the analysis of each analyte, at a frequency
of 10% or every 2 hours during an analysis run, whichever is more
frequent. The standard must also be analyzed and reported for
every wavelength used for analysis at the beginning of the run and
after the last analytical sample. The analyte concentrations in
the continuing calibration standard must be one of the following
solutions at or near the mid-range levels of the calibration
curve:
1. EPA Solutions
2. NBS SRH 1643a
3. A Contractor-prepared standard solution
TABLE 1. INITIAL AND CONTINUING CALIBRATION VERIFICATION
CONTROL LIMITS FOR INORGANIC ANALYSES
% of True Value (EPA Setl
Analytical Method
ICP/AA
Cold Vapor AA
Other
Inorganic
Species
Metals
Mercury
Cyanide
Low Limit
90
80
85
High Limit
110
120
115
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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
samples analyzed since the last good 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 Standardsjfor LICg (CRJ4^a|id AA (gRA)
To verify linearity near the CRDL for ICP analysis, the Contractor must
analyze an ICP standard (CRI) at two tines 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 CCCB).
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
E-6 • 7/88
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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 good 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),
must be prepared and analyzed with every Sample Delivery Group, or
with each batch of samples digested, whichever is more frequent.
The first batch of samples in an SDG is to be assigned to
preparation blank one, the second batch of samples to preparation
blank two, etc. (see FORM III-IN). Each data package must contain
the results of all the preparation blank analyses associated with
the samples in that SDG.
This blank is to be reported for each SDG and used in all analyses
to ascertain whether sample concentrations reflect contamination
in the following manner:
1) If the absolute value of the concentration of the blank is
less than or equal to the Contract Required Detection Limit
(Exhibit C), no correction of sample results is performed.
2T If any analyte concentration in the blank is above the CRDL,
the lowest concentration of that analyte in the associated
samples must be lOx the blank concentration. Otherwise, all
samples associated with the blank with the analyte's
concentration less than lOx the blank concentration and above
the CRDL, must be redigested and reanalyzed for that analyte
(except for an identified aqueous soil field blank). The
sample concentration is not to be corrected for the blank
value.
3) If the concentration of the blank is below the negative CRDL,
then all samples reported below lOx CRDL associat -d with the
blank must be redigested and reanalyzed.
A group of samples prepared at the same time.
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The values for the preparation blank must be recorded in ug/L for
aqueous samples and in mg/Kg for solid samples on FORM III-IN for
ICP, AA, and cyanide analyses.
5. ICP Interference Check Sample (ICS) Analysis
To verify interelement and background correction factors, the
Contractor must analyze and report the results for the ICP Interference
Check Samples at the beginning and end of each analysis run or a
minimum of twice per 8 hour working shift, whichever is -more frequent,
but not before Initial Calibration Verification. The ICP Interference
Check Samples must be obtained from EPA (EMSL/LV) if available and
analyzed according to the instructions supplied with the ICS.
The Interference Check Samples consist of two solutions: Solution A and
Solution AB. Solution A consists of the interferents, and Solution AB
consists of the analytes mixed with the interferents. An ICS analysis
consists of analyzing both solutions consecutively (starting with
Solution A) for all wavelengths used for each analyte reported by ICP.
Results for the ICP analyses of Solution AB during the analytical runs
must fall within the control limit of ±20% of the true value for the
analytes included in the Interference Check Samples. If not, terminate
the analysis, correct the problem, recalibrate the instrument, and
reanalyze the analytical samples analyzed since the last good ICS. If
true values for analytes contained in the ICS and analyzed by ICP are
not supplied with the ICS, the mean must be determined by initially
analyzing the ICS at least five times repetitively for the particular '
analytes. This mean determination must be made during an analytical run
where the results for the previously supplied EPA ICS met all contract
specifications. Additionally, the result of this initial mean
determination is to be used as the true value for the lifetime of that
solution (i.e., until the solution is exhausted).
If the ICP Interference Check Sample is not available from EPA,
independent ICP Check Samples must be prepared with interferent and
analyte concentrations at the levels specified in Table 2-Interferent
and Analyte Elemental Concentrations Used for ICP Interference Check
Sample. The mean value and standard deviation must be established by
initially analyzing the Check Samples at least five times repetitively
for each parameter on FORM IV-IN. Results must fall within the control
limit of +20% of the established mean value. The mean and standard
deviation must be reported in the raw data. Results from the
Interference Check Sample analyses must be recorded on FORM IV-IN for
all ICP parameters.
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TABLE 2. INTERFERENT AND ANALYTE ELEMENTAL CONCENTRATIONS USED FOR ICP
INTERFERENCE CHECK SAMPLE
Analytes
(mg/L)
Interferents
(mg/L)
Ag
Ba
Be
Cd
Co
Cr
Cu
Mn
Ni
Pb
V
Zn
1.0
0.5
0.5
1.0
0.5
0.5
0.5
0.5
1.0
1.0
0.5
1.0
Al
Ca
Fe
Mg
500
500
200
500
6. Spike Sample Analysis (5}
The spike sample analysis is designed to provide information about the
effect of the sample matrix on the digestion and measurement
methodology. The spike is added before the digestion (i.e., prior to
the addition of other reagents) and prior to any distillation steps
(i.e., CN-). At least one spike sample analysis must be performed on
each group of samples of a similar matrix type (i.e., water, soil) and
concentration (i.e., low, medium) or for each Sample Delivery Group.
If the spike analysis is performed on the same sample that is chosen
for the duplicate sample analysis, spike calculations must be performed
using the results of the sample designated as the "original sample"
(see section 7, Duplicate Sample Analysis). The average of the
duplicate"results cannot be used for the purpose of determining percent
recovery. Samples identified as field blanks cannot be used for spiked
sample analysis. 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.
EPA may require additional spike sample analysis, upon Project Officer
request, for which the Contractor will be paid.
E-9 7/88
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If the spike recovery is not at or within the limits of 75-125%, the
data of all samples received associated with that spike sample and
determined by the same analytical method must be flagged with the
letter "N" on FORMs I-IN and V-IN. An exception to this rule is
granted in situations where the sample concentration exceeds the spike
concentration by a factor of four or more. In such an e
-------
TABLE 3. SPIKING LEVELS FOR SPIKE SAMPLE ANALYSIS
For ICP/AA For Furnace AA Other <-1-1
(UR/L) (UR/L) (UR/L)
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
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^ Water Soil
*
500 100 100
2 , 000 40 40
2,000
50
50 5 5
*
200
500
250
*
500 20 20
.*
500
1
500
*
2rOOO 10 10
50
*
2,000 50 50
500
500
100
NOTE: Elements vithout 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.
o
The levels shown indicate concentrations in the final digestate of the
spiked sample (200 mL final volume).
No spike required.
E-ll
7/88
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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.
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.
EPA may require additional duplicate sample analyses, upon Project Officer
request, for which the Contractor will be paid.
E-12 7/88
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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 (L)
Prior to reporting concentration data for the analyte elements, the
Contractor must analyze and report the results of the ICP Serial
Dilution.Analysis. The ICP Serial Dilution Analysis must be performed
on a sample from each group of samples of a similar matrix type (i.e.,
water, soil) and concentration (i.e., low, medium) or for each Sample
Delivery Group, whichever is more frequent. Samples identified as
field blanks cannot be used for Serial Dilution Analysis.
If the analyte concentration is sufficiently high (minimally a factor
of 50 above the instrumental detection limit in the original sample),
the serial dilution (a five fold dilution) must then agree within 10%
of the original determination after correction for dilution. If the
dilution analysis for 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.
E-13 7/88
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The percent differences for each component are calculated as follows:
II - S I
% Difference - ' 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 noneonsecutive 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
fomultiple ICPs .
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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
NO
DILUTE SAMPLE
AND SPIKE
YES
RECOVERY OF SPIKE
LESS THAN 40%
If YES, Repeat Only ONCE
If Still YES
NO
FLAG DATA
WITH AN "E"
NO
SAMPLE ABSORBANCE
LESS THAN 50% OF
SPIKE ABSORBANCE
YES
REPORT RESULTS
DOWN TO IDL
SP IKE RECOVERY
LESS THAN 85% OR
GREATER THAN 115%
NO
YES
REPORT RESULTS
DOWN TO IDL,
FLAG WITH A "W"
SPIKE RECOVERY
LESS THAN 85% OR
GREATER THAN 115%
NO
YES
QUANTITATE FROM
CALIBRATION CURVE
AND REPORT DOWN
TO IDL
QUANTITATE BY MSA WITH 3
SPIKES AT 50, 100 & 150%
OF SAMPLE ABSORBANCE
(Only Single Injections Required)
CORRELATION COEFFICIENT
LESS THAN 0.995
If YES, Repeat Only ONCE
NO
If Still YES
FLAG DATA WITH "S"
FLAG DATA
WITH A "+"
E-15
7/88
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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
and concentration of each injection must be reported in the raw
data as well as the average absorbance and concentration values.
Average concentration values are used for reporting purposes. A
maximum of 10 full sample analyses to a maximum 20 injections may
be performed between each consecutive calibration verifications
and blanks. The raw data package must contain absorbance and
concentration values for both injections, the average value and
the relative standard deviation (RSD) or coefficient of variation
(CV). For concentrations greater than CRDL, the duplicate
injection readings must agree within 20% RSD or CV, or the
analytical sample must be rerun once (i.e., two additional burns).
If the readings are still out, flag the value reported on FORM I-
IN with an "M". The "M" flag is required for the analytical spike
as well as the sample. If the analytical spike for a sample
requires an "M" flag, the flag must be reported on FORM I- IN for
that sample.
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b. All furnace analyses for each analytical sample, including those
requiring an "M" flag, will require at least an analytical spike
to determine if the MSA will be required for quantitation. The
analytical spike will be required to be at a concentration (in
the sample) 2x CRDL. This requirement for an analytical spike
will include the LCS and the preparation blank. (The LCS must be
quantitated from the calibration curve and corrective action, if
needed, taken accordingly. MSA is not to be performed on' the LCS
or preparation blank, regardless of spike recovery results.) If
the preparation blank analytical spike recovery is out of control
(85-115%), the spiking solution must be verified by respiking and
rerunning the preparation blank once. If the preparation blank
analytical spike recovery is still out of control, correct the
problem and reanalyze all analytical samples associated with that
blank. An analytical spike is not required on the pre-digestion
spike sample.
The analytical spike of a sample must be run immediately after
that sample. The percent recovery (%R) of the spike, calculated
by the same formula as Spike Sample Analyses (see item 6, this
section), will then determine how the sample will be quantitated,
as follows:
1) ' If the spike recovery is less than 40%, the sample must be
diluted and rerun with another spike. Dilute the sample by a
factor of 5 to 10 and rerun. This step must only be
performed once. If after the dilution the spike recovery is
still <40%, report data and flag with an "E" to indicate
interference problems.
2) If the spike recovery is greater than or equal to 40% and the
sample absorbance 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 is greater than or equal to 50% of
~ the spike and the spike recovery is at or between 85% and
115%, the sample must be quantitated directly from the
calibration curve and reported down to the IDL.
4) If the sample absorbance 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.
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 of spike sample] minus [absorbance of
the sample].
E-17 7/88
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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
chat 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 absorbance.
b) Spike 2 is approximately 100% of the sample absorbance.
c) Spike 3 is approximately 150% of the sample absorbance.
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.
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SECTION III
LABORATORY EVALUATION PROCESS
This document outlines the procedures which will be used by the
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.
1. 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 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 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-Site 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. On-site laboratory evaluations allow the evaluators to determine
t;hat:
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
measures, 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
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1. Sample Chain-of-Custody
A sample Is physical evidence collected from a facility or from the
environment. An essential part of hazardous waste investigations is
that samples and data may be used as evidence in EPA enforcement
proceedings. To satisfy enforcement uses of the data, the following
chain-of-custody procedures have been established.
1.1 Sample Identification
To ensure traceability of samples while in possession of the
laboratory, a method for sample identification shall be developed and
documented in laboratory Standard Operating Procedures (SOPs) (see
Section 3). Each sample or sample preparation container shall be
labeled with a unique number identifier (or the EPA Sample Number).
This identifier shall be cross-referenced to the sample tag EPA
Sample Number and the SKO number. There shall be a written
description of the method of assigning this identifier and attaching
it to the sample container included in the laboratory SOPs.
1.2.1 A sample is under custody if:
1.2.1.1 It is in your actual possession,
1.2.1.2 It is in your view after being in your physical
possession,
1.2'. 1.3 It was in your possession and then you locked or
sealed it up to prevent tampering, or
1.2.1.4 It is in a secure area.
1.2.2 Upon receipt of the samples in custody, the Contractor shall
inspect the shipping container and sample bottles and shall
._ document receiving information as specified in section 3.2.
The sample custodian or a designated representative shall
sign and date all appropriate receiving documents at the time
of receipt (i.e., EPA chain-of-custody forms, Traffic
Reports, airbills, etc.). The Contractor shall contact SMO
if documents are absent, if information on receiving
documents does not agree, if custody seals are not intact, or
if the sample is not in good condition. The Contractor shall
document resolution of any discrepancies, and this
documentation shall become a part of the permanent Case file.
1.2.3 Once samples have been accepted by the laboratory, checked,
and logged in, they must be maintained in accordance with
custody and security requirements specified in 3.3.
F-l 7/88
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2. Document Control Procedures
The goal of the laboratory document control program is to ensure that
all documents for a specified Case will be accounted for when the
project is completed. Accountable documents used by Contractor
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 ensure 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 Data Sheets and Logbooks
Preprinted data sheets shall contain the name of the laboratory and
be dated and signed by the analyst or individual performing the work
All documents produced by the laboratory 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 Case file. For that
reason, all observations and results recorded by the laboratory but
not on preprinted data sheets shall be entered into permanent
laboratory logbooks. The person responsible for the work shall sign
and date each entry and/or page in the logbook. When all data from a
case is compiled, copies of all EPA Case-related logbook entries
shall be included in the documentation package. Analysts' logbook
entries must be in chronological order and shall include only one
Case per page. Instrument run logs shall be maintained so as to
enable a reconstruction of the run sequences 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 labora-
tory or EPA sample identification numbers in the logs for sample ID
rather than government agency or commercial client names.
Using laboratory or EPA Sample Number IDs only in the run sequences
will assist the laboratory in preserving the confidentiality of
commercial clients.
2.2 Error Correction Procedure
All documentation in logbooks and other documents shall be in ink.
If an error is made, corrections shall be made by crossing a line
through the error and entering the correct information. Changes
shall be dated and initialed. No information shall be obliterated or
rendered unreadable.
2.3 Consistency of Documentation
Before releasing analytical results, the laboratory shall assemble
and cross-check the information on sample tags, custody records, lab
bench sheets, personal and instrument logs, and other relevant data
to ensure that data pertaining to each particular sample or Case is
consistent throughout the Case file.
F-2 7/88
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2.4 Document Numbering and Inventory Procedure
In order to provide document accountability of the completed analysis
records, each item in a Case shall be inventoried and assigned a
serialized number and identifier associating it to the Case and
Region.
Case # - Region - Serialized number (For example: 75-2-0240)
The number of pages of each item must be accounted for if each page
is not individually numbered. All documents relevant to each Case,
including logbook pages, bench sheets, mass spectra, chromatograms,
custody records, library search results, etc., shall be inventoried.
The laboratory shall be responsible for ensuring that all documents
generated are placed in the file for inventory and are delivered to
EPA in the Case File Purge package (Exhibit B, Paragraph F). Figure
1 is an example of a document inventory.
2.5 Shipping Data Packages and Case Files
The Contractor shall have written procedures to document shipment of
deliverables packages to the recipients. These shipments require
custody seals on the containers placed such that it cannot be opened
without damaging or breaking the seal. The Contractor shall also
document what was sent, to whom, the date, and the method (carrier)
used.
F-3 7/88
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Figure 1
Example
232-2-0001
Case No.
Region
DOCUMENT INVENTORY
Document Control #* Document Type » Pages
232-2-0001 Case File Document Inventory Sheet 1
232-2-0002 Chain-of-Custody Records 2
232-2-0003 Shipping Manifests 2
232-2-0004 Sample Tags 50
232-2-0005 SMO Inorganics Traffic Reports 10
232-2-0006 Inorganics Analysis Data Summary Sheets 10
232-2-0007 Analysts' Notebook Pages 14
232-2-0008 ICP and AA Instrument Logbook Pages 12
etc. etc. etc.
*This number is to be recorded on each set of documents.
F-4 7/88
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3 . Standard Operating Procedures
The Contractor must have written standard operating procedures (SOPs)
for:
a. Sample receipt and logging.
b. Sample storage.
c. Preventing sample contamination.
d. Security for laboratory and samples.
e. Traceability of standards.
f. Maintaining instrument records and logbooks.
g. Sample analysis and data control systems.
h. Glassware cleaning.
i. Technical and managerial review of laboratory operation and
data package preparation.
j. Internal review of contractually-required quality assurance
and quality control data for each individual data package.
k. Sample analysis, data handling and reporting.
1. Chain-of-custody.
m. Document control, including Case file preparation.
An SOP is defined as a written narrative step-by-step description of
laboratory operating procedures including examples of laboratory
documentation. The SOPs must 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 a designated sample custodian responsible
for receipt of samples and have written SOPs describing his/her
duties and responsibilities.
F-5 7/88
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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:
o Presence or absence of EPA chain-of-custody forms
o Presence or absence of airbills
o Presence or absence of EPA Traffic Reports or SAS packing
lists
o Presence or absence of custody seals on shipping and/or sample
containers and their condition
o Presence or absence of sample tags
o Sample tag ID numbers if not recorded on the chain-of-custody
record(s) or packing list(s)
o Condition of the shipping container
o Condition of the sample bottles
o Verification of agreement or nonagreement of information on
receiving documents
o Resolution of problems or discrepancies with the Sample
Management Office
3.3 The Contractor shall have written SOPs for maintenance of the
security of samples after log-in and shall demonstrate security of
the sample storage and laboratory areas. The SOPs shall specifically
include descriptions of all storage areas for EPA samples in the
laboratory, and steps taken to prevent sample contamination. The
SOPs shall include a list of authorized personnel who have access or
keys to secure storage areas.
3.4 The Contractor shall have written SOPs for tracking the work per-
formed on any particular sample. The tracking SOP shall include the
following:
3.4.1 A description of the documentation used to record sample
receipt, sample storage, sample transfers, sample
preparations, and sample analyses.
3.4.2 A description of the documentation used to record instrument
calibration and other QA/QC activities.
3.4.3 Examples of the document formats and laboratory documentation
used in the sample receipt, sample storage, sample transfer,
and sample analyses.
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3.5 The Contractor shall have written SOPs for organization and assembly
of all documents relating to each EPA Case, including technical and
managerial review. Documents shall be filed on a Case-specific
basis. The procedures must ensure that all documents including
logbook pages, sample tracking records, chromatographic charts,
computer printouts, raw data summaries, correspondence, and any other
written documents having reference to the Case are compiled in one
location for submission to EPA. The system must include a document
numbering and inventory procedure.
3.6 The Contractor shall have written SOPs for laboratory safety.
3.7 The Contractor shall have written SOPs for cleaning of glassware used
in preparing and analyzing samples under this contract.
3.8 The Contractor shall have SOPs for traceability of standards used in
sample analysis QA/QC.
4. Handling of Confidential. Information
A Contractor conducting work under this co.ntract 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 desig-
nated 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
maintaTned 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 logs these documents into a
Confidential Inventory Log. The information is then made 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 Contracting
Officer. The DCO will enter all copies into the document control
system. In addition, this information may not be disposed of except
upon approval by the EPA Contracting Officer. The DCO shall remove
and retain the cover page of any confidential information disposed of
for one year and shall keep a record of the disposition in the
Confidential Inventory Log.
F-7 7/88
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EXHIBIT G
GLOSSARY OF TERMS
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GLOSSARY OF TERMS
ABSORBANCE - a measure of the decrease in incident light passing through a
sample into the detector. It is defined mathematically as:
A _ Insolvent) _ log lo
I(solution) I
Where, I - radiation intensity
ALIQUOT - a measured portion of a field sample taken for analysis.
ANALYSIS DATE/TIME - the date and military time (24-hour clock) of the
introduction of the sample, standard, or blank into the analysis system.
ANALYTE - the element or ion an analysis seeks to determine; the element of
interest.
ANALYTICAL SAMPLE - Any solution or media introduced into an instrument on
which an analysis is performed excluding instrument calibration, initi-al
calibration verification, initial calibration blank, continuing calibration
verification and continuing Calibration blank. Note the following are all
defined as analytical samples: undiluted and diluted samples (EPA and non-
EPA), predigestion spike samples, duplicate samples, serial dilution
samples, analytical spike samples, post-digestion spike samples,
interference check samples (ICS), CRDL standard for AA (CRA), CRDL standard
for ICP (CRI), laboratory control sample (LCS), preparation blank (PB) and
linear range analysis sample (LRS).
ANALYTICAL SPIKE - The furnace post-digestion spike. The addition of a
known amount of standard after digestion.
AUTOZERO - zeroing the instrument at the proper wavelength. It is
equivalent to running a standard blank with the absorbance set at zero.
AVERAGE INTENSITY - The average of two different injections (exposures).
BACKGROUND CORRECTION - a technique to compensate for variable background
contribution to the instrument signal in the determination of trace
elements.
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
Sample Management Office. A Case consists of one or more Sample Delivery
Groups.
G-l 7/88
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COEFFICIENT OF VARIATION (CV) - the standard deviation as a percent of the
arithmetic mean.
CONCENTRATION LEVEL (low or medium) - for inorganics analysis, low or
medium level is defined by the appropriate designation checked by the
sampler on the Traffic Report.
CONTINUING CALIBRATION - analytical standard run every 10 analytical
samples or every 2 hours, whichever is more frequent, to verify the
calibration of the analytical system.
CONTRACT REQUIRED DETECTION LIMIT (CRDL) - minimum level of detection
acceptable under the contract Statement of Work.
CONTROL LIMITS - a range within which specified measurement results must
fall to be compliant. Control limits may be mandatory, requiring
corrective action if exceeded, or advisory, requiring that noncompliant
data be flagged.
CORRELATION COEFFICIENT - a number (r) which indicates the degree of depen-
dence between two variables (concentration - absorbance). The more
dependent they are the closer the value to one. Determined on the basis of
the least squares line.
DAY - unless otherwise specified, day shall mean calendar day.
DIGESTION LOG • an official record of the sample preparation (digestion).
DISSOLVED METALS - analyte elements which have not been digested prior to
analysis and which will pass through a 0.45 urn filter.
DRY WEIGHT - the weight of a sample based on percent solids. The weight
after drying in an oven.
DUPLICATE - a second aliquot of a sample that is treated the same as the
original sample in order to determine the precision of the method.
FIELD BLANK - any sample submitted from the field identified as a blank.
FIELD SAMPLE • a portion of material received to be analyzed that is
contained in single or multiple containers and identified by a unique EPA
Sample Number.
FLAKE 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.
Holding time - (sample analysis date - sample receipt date)
G-2 7/88
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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 nrulti-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.
LABORATORYjCONTROL 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 £>OW, a sample matrix is either water or
soil/sediment. Matrix is not synonymous with phase (liquid or solid).
MATRIX MODIFIER - salts used in AA to lessen the effects of chemical
interferents, viscosity, and surface tension.
G-3 7/88
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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
water matrix; A solid method blank is treated with the same reagents as a
soil sample.
PROTOCOL - a. compilation of the procedures to be followed with respect to
sample receipt and handling, analytical methods, data reporting and
deliverables, and document control. Used synonymously with Statement of
Work (SOW).
ROUNDING RULES—- If the figure following those to be retained is less than
5, the figure is dropped, and the retained figures are kept unchanged. As
an example, 11.443 is rounded off to 11.44.
If the figure following those to be retained is greater than 5, the figure
is dropped, and the last retained figure is raised by 1. As an example,
11.446 is rounded off to 11.45.
If the figure following those to be retained is 5, and if there are no
figures other than zeros beyond the five, the figure 5 is dropped, and the
last-place figure retained is increased by one if it is an odd number or it
is kept unchanged if an even number. As an example, 11.435 is rounded off
to 11.44, while 11.425 is rounded off to 11.42.
If a series of multiple operations is to be performed (add, subtract,
divide, multiply), all figures are carried through the calculations. Then
the final answer is rounded to the proper number of significant figures.
See forms instructions (Exhibit B) for exceptions.
C-U 7/88
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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 theVCase
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 - 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
gage No.
SECTION I: Description of Deliverables H-l
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.
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
is 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 must be submitted on a 5-1/4 inch floppy diskette,
which may be either a double-sided, double density, 360 K-byte or a
high capacity 1.2 H-byte diskette. The diskette must be formatted and
recorded using the MS-DOS Operating System. The diskette or diskettes
oust 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.
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
H-l 7/88
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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
Y is "A" for Format A
or "B" for Format B
Dimensions of the label must be in the range 4-3/4" to 5" long by 1-1/4
to 1-1/2"* wide.
H-2 7/88
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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
items 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 welt 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
specified 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 vith 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).
H-3 7/88
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The table below demonstrates several examples:
Value
10.1
10.11
100.11
100
.29
-100.129
-10.1
Appears on Format
"10.10"
"10.11"
"100.11"
"100.00"
"0.29"
Invalid
Invalid
The following table presents examples of NUMERIC S3.2:
Value
10.1
-10.11
-100.11
-1000.1
100
-.22
-.239
Appears on Format
" 10.10" (seven columns)
" -10.11"
"-I'OO.ll"
Invalid
" 100.00"
" -0.22"
" -0.24"
2.
2.1
2.2
Record Types
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.
Format A has three types of records: Header Records, Detail Records
and Comment Records.
Type
Header
Detail
Comment
Type ID
H
Contents
Nonrepeating fields which
together are unique to the
associated hardcopy form
A group of fields that are
repeated on a form, and are
uniquely positioned by (e.g.,
Analyte Chemical Symbol)
Nonrepeating fields containing
text that comments on informa-
tion reported on the form
2.3
The format for Comment Records is the same for all forms, and is
described after all other formats.
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.
H-A
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FORM ID
FORM NAME
3.
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 ICP 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.
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 forms on which information is written on all possible lines.
H-5
7/88
-------
Table 3.1 Format A Summarv
Form
Cover
I
IKD
11(2)
III
IV
V(2)
VI
VII
VIII
IX
X
XI
XII
XIII
XIV
Record
Header
80a(l)b
90(1)
32(1)
32(1)
18(1)
32(1)
33(1)
23(1)
38(1)
32(1)
8(1)
23(1)
52(1)
28(1)
28(1)
10(1)
38(1)
Detail
25(24)
31(24)
65(24)
66(23)
59(24)
64(23)
66(24)
62(24)
56(24)
68(24)
67(32)
44(23)
29(23)
77(23)
29(23)
32(32)
59(32)
Comment
78(4)
78(4)
78(4)
78(4)
78(4)
78(4)
78(4)
a Length of record in bytes (excluding carriage return/line feed).
number of records required for a form.
4. Record Listing
The remainder of chis section contains detailed specifications for every
record required for a full set of hardcopy forms.
H-6 • 7/88
-------
COVER PAGE
INORGANIC ANALYSES DATA PACKAGE COVER PAGE HEADER RECORD:
COLUMNSS) LENGTH CONTENTS FORMAT
1-5 5 'COVER'
6-7 2 FORM SUFFIX
8 1 »H'
9-33 25 LAB NAME CHARACTER
34-43 10 CONTRACT CHARACTER
44-49 6 LAB CODE CHARACTER
50-54 5 CASE NUMBER CHARACTER
55-60 6 SAS NUMBER CHARACTER
61-66 6 SDG NUMBER CHARACTER
67-71 5 SOW NUMBER CHARACTER
72-74 3 ICP INT CORRECTIONS 'YES'/'NO'
75-77 3 ICP BG CORRECTIONS 'YES'/'NO'
78-80 3 RAW DATA BEFORE '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 5 'COVER'
6-7 2 FORM SUFFIX
8 1 'D'
9-15 7 EPA SAMPLE NO. CHARACTER
16-25 10 LAB SAMPLE ID NO. CHARACTER
H-7 7/88
-------
FORM I
INORGANIC ANALYSIS DATA SHEET HEADER RECORD:
COLUMN CS")
LENGTH
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
76-81
82-87
88-90
5
2
1
7
5
10
3
8
5
5
9
9
6
6
6
3
CONTENTS
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
FORMAT
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:
CONTENTS
'I
FORM SUFFIX
'D'
ANALYTE SYMBOL
CONCENTRATION
CONC FLAG (C)
QUALIFIER (Q)
METHOD (M)
1-5
6-7
8
9-10
11-22
23
24-29
^BU^b
5
2
1
2
12
1
6
30-31
FORMAT
CHARACTER
NUMERIC 9.2
'B'/'U'/BLANK
UP TO 6 ONE-CHARACTER
FLAGS (OTHER THAN 'B'
OR 'U')
METHOD CC^E/'NR'
H-8
7/88
-------
FORK II (PART 1)
INITIAL AND CONTINUING CALIBRATION VERIFICATION HEADER RECORD:
COLUMNfS) LENGTH CONTENTS FORMAT
1-5 5 'II(l)',
6-7 2 FORM SUFFIX
8 1 'H'
9-20 12 INIT CAL SOURCE CHARACTER
21-32 12 CONT CAL SOURCE CHARACTER
INITIAL AND CONTINUING CALIBRATION VERIFICATION DETAIL RECORDS:
COLUMN(S) LENGTH CONTENTS FORMAT
1-5 5 'II(l)'
6-7 2 FORM SUFFIX
8 1 'D'
9-10 2 ANALYZE SYMBOL CHARACTER
11-17 7 INITIAL CAL TRUE NUMERIC 5.1
18-25 8 INITIAL CAL FOUND NUMERIC 5.2
26-30 5 INITIAL CAL %R NUMERIC 3.1
31-37 7 CONT CAL TRUE NUMERIC 5.1
38-45 8 CONT CAL FOUND 1 NUMERIC 5.2
46-50 5 CONT CAL %R 1 NUMERIC 3.1
51-58 8 CONT CAL FOUND 2 NUMERIC 5.2
59-63 5 CONT CAL %R 2 NUMERIC 3.1
64-65 2 METHOD (M) METHOD CODE/'NR'
H-9 7/88
-------
FORM II (PART 2)
CRDL STANDARD FOR AA AND ICP HEADER RECORD:
COLUMN/S) LENGTH CONTENTS FORMAT
1-5 5 »II(2)'
6-7 2 FORM SUFFIX
8 1 'H'
9-20 12 AA STANDARD SOURCE CHARACTER
21-32 12 ICP STANDARD SOURCE CHARACTER
CRDL STANDARD FOR AA AND ICP DETAIL RECORDS:
COLUMN(S) LENGTH CONTENTS FORMAT
1-5 5 fll<2)'
6-7 2 FORM SUFFIX
8 1 'D'
9-10 2 ANALYZE SYMBOL CHARACTER
11-17 7 AA TRUE NUMERIC 5.1
18-26 9 AA FOUND NUMERIC 6.2
27-31 5 AA %R NUMERIC 3.1
32-38 7 .ICP INIT TRUE NUMERIC 5.1
39-47 9 ICP INIT FOUND NUMERIC 6.2
48-52 5 ICP INIT %R NUMERIC 3.1
53-61 9 ICP FINAL FOUND NUMERIC 6.2
62-66 5 ICP FINAL %R NUMERIC 3.1
H-10 7/88
-------
FORM, III
BLANKS HEADER RECORD:
COLUMN(S) 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
FORMAT
'WATER'/'SOIL '
'UG/L '/'MG/KG'
BLANKS DETAIL RECORDS:
COLUMNCSI
LENGTH
1-5
6-7
8
9-10
11-18
19
20-27
28
29-36
37
38-45
46
47-56
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)
FORMAT
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 S5.3
'B'/'U'/BLANK
METHOD CODE/'NR'
H-ll
7/88
-------
FORM IV
ICP INTERFERENCE CHECK SAMPLE HEADER RECORD:
COLUMN(S) LENGTH CONTENTS FORMAT
1-5 5 'IV
6-7 2 FORM SUFFIX
8 1 'H'
9-20 12 ICP ID NUMBER CHARACTER
19-32 12 ICS SOURCE CHARACTER
ICP INTERFERENCE CHECK SAMPLE DETAIL RECORDS:
COLUMNSS) LENGTH CONTENTS FORMAT
1-5
6-7
8
9-10
11-16
17-22
23-29
30-38
39-43
44-50
51-59
60-64
5
2
1
2
6
6
7
9
5
7
9
5
'IV
FORM SUFFIX
'D'
ANALYTE SYMBOL
TRUE A
TRUE AB
INITIAL A
INITIAL AB
INITIAL %R
FINAL A
FINAL AB
FINAL %R
CHARACTER
NUMERIC 6
NUMERIC 6
NUMERIC S6
NUMERIC S6.1
NUMERIC 3.1
NUMERIC S6
NUMERIC S6.1
NUMERIC 3.1
H-12 7/88
-------
FORM V (PART 1)
SPIKE SAMPLE RECOVERY HEADER RECORD:
COLUMN(S) LENGTH CONTENTS FORMAT
1-5 5 'V(l) '
6-7 2 FORM SUFFIX
8 1 'H'
9-15 7 EPA SAMPLE NO. CHARACTER
16-20 5 MATRIX 'WATER'/'SOIL '
21-23 3 LEVEL 'LOW'/'MED'
24-28 5 CONCENTRATION UNITS 'UG/L '/ 'MG/KG'
29-33 5 SAMPLE % SOLIDS NUMERIC 3.1
SPIKE SAMPLE RECOVERY DETAIL RECORDS:
COLUMN(S) LENGTH CONTENTS FORMAT
1-5 5 'V(l) '
6-7 2 FORM SUFFIX
8 1 'D' .
9-10 2 ANALYTE SYMBOL CHARACTER
11-16 6 CONTROL LIMIT %R '75-125'/BLANK
17-30 14 SPIKED SAMPLE RESULT NUMERIC 9.4
31 1 SSR FLAG (C) 'B'/'U'/BLANK
32-44 13 SAMPLE RESULT NUMERIC 8.4
45 1 SR FLAG (C) 'B'/'U'/BLANK
46-56 11 SPIKE ADDED NUMERIC 8.2
57-63 7 PERCENT RECOVERED NUMERIC S4.1
64-1 QUALIFIER (Q) 'N'/BLANK
65-66 2 METHOD (M) ' METHOD CODE/'NR'
H-13 7/88
-------
FORM V (PART 2)
POST DIGEST SPIKE SAMPLE RECOVERY HEADER RECORD:
COLUMNSS) LENGTH CONTENTS FORMAT
1-5 5 (V(2) '
6-7 2 FORM SUFFIX
8 1 'H1
9-15 1 EPA SAMPLE NO. CHARACTER
16-20 5 MATRIX 'WATER'/'SOIL
21-23 3 LEVEL 'LOW'/'MED'
POST DIGEST SPIKE SAMPLE RECOVERY DETAIL RECORDS:
COLUMNfS) LENGTH CONTENTS FORMAT
1-5 5 'V(2) '
6-7 2 FORM SUFFIX
8 1 'D'
9-10 2 ANALYTE SYMBOL CHARACTER
11-16 6 CONTROL LIMIT %R BLANK
17-28 12 SPIKED SAMPLE RESULT NUMERIC 9.2
29 1 SSR FLAG.(C) ' 'B'/'U'/BLANK
30-41 12 SAMPLE RESULT NUMERIC 9.2
4'2 1 SR FLAG (C) 'B'/'U'/BLANK
43-52 10 SPIKE ADDED NUMERIC 8.1
53-59 7 PERCENT RECOVERED NUMERIC S4.1
60 1 QUALIFIER (Q) BLANK
61-62 2 METHOD (M) METHOD CODE/'NR'
H-14 7/88
-------
FORM VI
DUPLICATES HEADER RECORD:
COLUMN(SI 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
FORMAT
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 STfMBOL
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'/BIANK
NUMERIC 9.4
'B'/'U'/BLANK
NUMERIC 4.1
'*'/BLANK
METHOD CODE/'NR'
H-15
7/88
-------
FORM VII
LABORATORY CONTROL SAMPLE HEADER RECORD:
COLUMN(S) 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:
COLUMNSS) 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 LOVER LIMIT NUMERIC 6.1
56-63 8 SOLID UPPER LIMIT NUMERIC 6.1
64-68 5 SOLID % RECOVERED NUMERIC 3.1
H-16 7/88
-------
FORM VIII
STANDARD ADDITION RESULTS HEADER RECORD:
COLUMN(S) LENGTH CONTENTS
1-5
6-7
8
FORMAT
5
2
1
'VIII '
FORM SUFFIX
'H'
NOTE: Although there are no fields which occur only once per FORM V^II, the
HEADER record must be included as a. place holder, indicating that
DETAIL records follow.
STANDARD ADDITION RESULTS DETAIL RECORDS:
COLUMNCS)
1-5
6-7
8
9-15
16-17
18-24
25-26
27-33
34-36
37-43
44-46
47-53
54-60
61-66 •
67
5
2
1
7
2
7
2
7
3
7
3
7
7
6
1
CONTENTS
'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
NUMERIC
NUMERIC 1.4
' + YBLANK
3.3
2
3.3
3
3.3
3
3.3
5.1
H-17
7/88
-------
FORM IX
ICP SERIAL DILUTIONS HEADER RECORD:
COLUMN(S) LENGTH CONTENTS FORMAT
1-5 5 'IX
6-7 2 FORM SUFFIX
8 1 'H'
9-15 7 EPA SAMPLE NO. CHARACTER
16-20 5 MATRIX 'WATER'/'SOIL
21-23 3 LEVEL 'LOW'/'MED'
ICP SERIAL DILUTIONS DETAIL RECORDS:
COLUMN(S) LENGTH CONTENTS FORMAT
1-5 5 'IX
6-7 2 FORM SUFFIX
8 1 'D'
9-10 2 ANALYTE SYMBOL CHARACTER
11-22 12 INIT SAMPLE (I) NUMERIC 9.2
23 1 INIT SAMPLE FLAG (C) 'B'/'U'/BLANK
24-35 12 SERIAL DILUTION (S) NUMERIC 9.2
36 1 DILUTION FLAG (C) 'B'/'U'/BLANK
37-41 5 PERCENT DIFFERENCE NUMERIC 3.1
42 1 QUALIFIER (Q) 'E'/BLANK
43-44 2 METHOD (M) METHOD CODE/'NR'
H-18 • 7/88
-------
FORM X
INSTRUMENT DETECTION LIMITS (QUARTERLY) HEADER RECORD:
COLUMN(S) LENGTH CONTENTS FORMAT
1-5 5 'X
6-7 2 FORM SUFFIX
8 1 'H'
9-16 8 DATE MM/DD/YY
17-28 12 ICP ID NUMBER CHARACTER
29-40 12 FLAME AA ID NUMBER CHARACTER
41-52 12 FURNACE AA ID NUMBER CHARACTER
INSTRUMENT DETECTION LIMITS (QUARTERLY) DETAIL RECORDS:
COLUMNSS) LENGTH CONTENTS FORMAT
1-5 5 'X
6-7 2 FORM SUFFIX
8 1 'D'
9-10 2 ANALYTE SYMBOL CHARACTER
11-17 7 WAVELENGTH NUMERIC 4.2
"18-19 2 BACKGROUND 'BSf/'BD'/'BZ'/BLANK
20-27 8 IDL NUMERIC 6.1
28-29 2 METHOD (M) METHOD CODE/'NR'
H-19 7/88
-------
FORM XI (PART 1)
ICP INTERELEMENT CORRECTION FACTORS (ANNUALLY) HEADER RECORD:
COLUMN(SI LENGTH CONTENTS FORMAT
1-5 5 'XI
6-7 2 FORM SUFFIX AA
8 1 'H'
9-20 12 ICP ID NUMBER CHARACTER
21-28 8 DATE MM/DD/YY
ICP INTERELEMENT CORRECTION FACTORS (ANNUALLY) DETAIL RECORDS:
COLUMNSS) LENGTH CONTENTS FORMAT
1-5 5 'XI
6-7 2 FORM SUFFIX
8 1 'D'
9-10 2 ANALYTE SYMBOL CHARACTER
11-17 7 WAVELENGTH NUMERIC 4.2
18-19 2 ELEMENT 1 SYMBOL AL
20-29 10 ELEMENT 1 FACTOR NUMERIC SI.7
30-31 2 ELEMENT 2 SYMBOL ' CA
32-41 10 ELEMENT 2 FACTOR NUMERIC SI.7
42-43 2 ELEMENT 3 SYMBOL FE
44-53 10 ELEMENT 3 FACTOR NUMERIC SI.7
54-55 2 ELEMENT 4 SYMBOL MG
56-65 10 ELEMENT 4 FACTOR NUMERIC SI.7
66-67 2 ELEMENT 5 SYMBOL CHARACTER
68-77 10 ELEMENT 5 FACTOR NUMERIC SI.7
NOTE: FORM XII (Part 1) can only have a FORM SUFFIX of AA. In addition,
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 7/88
-------
FORM XI fPART 21
ICP INTERELEMENT CORRECTION FACTORS (ANNUALLY) HEADER RECORD:
COLUMN(S) LENGTH CONTENTS FORMAT
1-5 5 'XI
6-7 2 FORM SUFFIX AB, AC, etc
8 1 'H'
9-20 12 ICP ID NUMBER CHARACTER
21-28 8 DATE MM/DD/YY
ICP INTERELEMENT CORRECTION FACTORS (ANNUALLY) DETAIL RECORDS:
COLUMN(SI LENGTH CONTENTS FORMAT
1-5 5 'XI
6-7 2 FORM SUFFIX
8 1 'D'
9-10 2 ANALYTE SYMBOL CHARACTER
11-17 7 WAVELENGTH NUMERIC 4.2
18-19 2 ELEMENT 1 SYMBOL CHARACTER
20-29 10 ELEMENT 1 FACTOR NUMERIC SI.7
30-31 2 ELEMENT 2 SYMBOL CHARACTER
32-41 10 ELEMENT 2 FACTOR NUMERIC SI.7
42-43 2 ELEMENT 3 SYMBOL CHARACTER
44-53 10 ELEMENT 3 FACTOR NUMERIC SI.7
54-55 2 ELEMENT 4 SYMBOL CHARACTER
56-65 10 ELEMENT 4 FACTOR NUMERIC SI.7
66-67 _ 2 ELEMENT 5 SYMBOL CHARACTER
68-77 10 ELEMENT 5 FACTOR NUMERIC SI.7
NOTE: The first FORM XII (Part 2) must have a FORM SUFFIX of AB, the second
must have a FORM SUFFIX of AC and so on.
H-21 7/88
-------
FORM XII
ICP LINEAR RANGES (QUARTERLY) HEADER RECORD:
COLUMN(S) LENGTH CONTENTS FORMAT
1-5 . 5 'XII '
6-7 2 FORM SUFFIX
8 1 'H'
9-20 12 ICP ID NUMBER CHARACTER
21-28 8 DATE MM/DD/YY
ICP LINEAR RANGES (QUARTERLY) DETAIL RECORDS:
COLUMN(S) LENGTH CONTENTS FORMAT
1-5 5 'XII '
6-7 2 FORM SUFFIX
8 1 'D'
9-10 2 ANALYTE SYMBOL CHARACTER
11-16 6 INTEGRATION TIME NUMERIC 3.2 (SECONDS)
17-27 11 CONCENTRATION NUMERIC 9.1
28-29 2 METHOD (M) 'NR' /BLANK
(ICP IS ASSUMED
IF BLANK)
H-22 7/88
-------
FORM XIII
PREPARATION LOG HEADER RECORD:
COLUMNSS) 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:
COLUMN(S) LENGTH CONTENTS FORMAT
1-5 5 'XIII '
6-7 2 FORM SUFFIX
8 1 'D'
9-15 7 EPA SAMPLE NUMBER CHARACTER
16-23 8 PREP DATE MM/DD/YY
24-28 5 WEIGHT NUMERIC 2.2
29-32 4 VOLUME . NUMERIC 4
H-23 7/88
-------
FORK XIV
ANALYSIS RUN LOG HEADER RECORD:
COLUMN(S) LENGTH
1-5
6-7
8
9-20
21-22
23-30
31-38
5
2
1
12
2
8
8
CONTENTS
'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:
COLUMNm
LENGTH
CONTENTS
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)
ANALYTE (TL)
ANALYTE (V)
ANALYTE (ZN)
ANALYTE (CM)
FORMAT
CHARACTER
NUMERIC 5.2
HHMM
NUMERIC S4.]
"X" /BLANK
"X"/BLANK
"X" /BLANK
"X" /BLANK
"X" /BLANK
"X" /BLANK
"X" /BLANK
"X" /BLANK
"X" /BLANK
"X" /BLANK
"XVBLANK
"X" /BLANK
"XVBLANK
"X"/BLANK
"XVBLANK
"XVBLANK
"XVBLANK
"X"/BLANK
"XVBLANK
"XVBLANK
"X"/BLANK
"XVBLANK
H-24
7/88
-------
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 7/88
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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 Spaces between fields permit these records to be prepared by
programs written for laboratory automation systems in versions
of BASIC which require this feature, as veil as to be compatible
with Agency standard statistical and database management systems
(e.g. SAS, S2K, ADABAS, etc.).
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 shown
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 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; or other calculated run-wide data such
as instrument detection limits or interelement correction factors (if
determined using a separate injection). Type 30, representing an
individual analyte, contains an indentifier to identify the analyte. All
30 series records following that record pertain to the same analyte. See
section 11 for an example of the sequence of record types.
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3. Production Runs
A production run represents a "group" or "batch" of samples that are
processed in a continuous sequence under relatively stable conditions.
Specifically:
Calibration - All samples in a run use the same initial calibration data.
Method number - Constant.
Instrument conditions - Constant throughout a run. Results obtained on
different instruments cannot be combined in one run.
Thus, each separate group of analyses on each instrument will consist of
a separate production run, and be reported in a separate file.
4. Record Sequence (See section 11)
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.
4.2 Each environmental sample, calibration, or quality control sample is
represented by a group composed of a type 20 and 21 records, which holds
sample level identifying information, followed by one type 30 record for
each analyte. The type 20 record holds a count for the number of
analytes being determined. Type 20 records should occur in the order of
sample analysis. The type 20 records for quality control items have the
additional rule that the LD1 record must occur before the corresponding
LD2 record, but the records need not be adjacent. In addition, a type 20
record is used as a header for any additional run-wide data that must be
reported for each analyte (such as instrument detection limits). Unique
identifiers given in section 9.4 are used in place of "QC codes" to
indicate the type of data that follows. Type 30 records for each
compound must occur in the order specified on Form 5.
4.3 Type 90 comment records may be defined to occupy any position except
before the type 10 (header) record.
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5. File/Record Integrity
All record types must contain the following check fields to ensure file
and record integrity:
Record Field Field
Position 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
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 decimal digits each, separated by blanks. 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 vill not be required.
7. Multiple Volume Tiara
There is no requirement under this format that all the data from an
entire sample delivery group fit onto a single diskette. If a single
production run is being split onto multiple diskettes, 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 aultiple_diskettes, then the type 20 and following type records for
that sample must be repeated. In this situation, it is mandatory that
columns 7-33, which collectively identify the sample, be identical in
each diskette.
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 che format
35A2 on processors which store the data bytes in left to right order. The sum is
taken modulo 65536 (21 ) 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.
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8. Record Listing
8.1 Format of the mandatory Production Run Header Record (Type 10)
Record
Position
1-2
3-18
19-21
22-26
27-30
31
32-34
35
36-41
42
43-50
51
52-61
62
63-68
Field
gngth
2
16
3
5
4
1
3
1
Field
Contents
Record type
blank
Measurement Type
blank
Method Number
blank
Remarks
"10"
•ICP"
"AA
or "CN "
Standard method number^ See
sections 9 and 10 for ekanrples
Person responsible for run 3 initials of Manager.
blank
6 Lab ID
1 blank
8 Date Report Prepared
1 blank
10 Contract Number
1 blank
6 Instrument ID
From EPA standard list or
Project Officer
YY MM DD
Agency standard number
e.g. AA8312; provided by
contract lab; left justi-
fied; must be unique and
permanent within lab
H-29
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8.2 Format of the mandatory Sample Header Data Record (Type 20)
Record
Position
1-2
3-6
7-12
13-15
16
17
18-20
21
22-24
25
26-30
31-39
40-47
48
49-53
54-67
68-70
sample.
Field Field
Length Contents
2
4
Record type
blank
6 EPA Sample No.
3 blank
1 Sample Medium/Matrix Code
1 blank
3 QC code
1 blank
3 Sample Qualifier
1 blank
5 Case number
9 blank
8 Date of Instrumental Anal.
1 blank
5 Hour, Minute of Analysis
14 blank
3 Analyte Count
Remarks
"20"
Left justified. See below
for calibrations and blanks.
See paragraph 9.3
Codes type of data to be
reported; (see section 9)
Code to qualify the results
of the entire sample
analysis (see paragraph 9.4.1)
YY MM DD
HH MM
Numeric; 1-3 decimal digits;
right justified - gives the
number of analytes determined
by this method for this
For unknown samples, use the assigned EPA Sample No. Label standards and
blanks as follows:—
INITIAL CALIBRATION (Form 2A)
CONTINUING CALIBRATION (Form 2A)
AA CRDL STANDARD (Form 2B)
ICP INITIAL LRA STANDARD (Form 2B)
ICP FINAL LRA STANDARD (Form 2B)
INITIAL CALIBRATION BLANK (Form 3)
CONTINUING CALIBRATION BLANK (Form 3)
PREPARATION BLANK (Form 3)
LABORATORY CONTROL SAMPLE (Form 7)
ICP INITIAL INTERFERENCE CHECK SOLUTION A (Form 4)
ICP INITIAL INTERFERENCE CHECK SOLUTION AB (Form 4)
ICP FINAL INTERFERENCE CHECK SOLUTION A (Form 4)
ICP FINAL INTERFERENCE CHECK SOLUTION AB (Form 4)
ICV
CCV1, CCV2, etc.
CRA
CRII
CRIF
ICB
CCB1, CCB2, etc.
PB1, PB2
LCS
ICSAI
ICSABI
ICSAF
ICSABF
H-30
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8.3 Format of the Sample Header Data Record (Type 21)
Use: Continuation of type 20.
Position: Follows the type 20 to which it applies.
Record
Position
1-2
3
4
5
6
Field
Length
2
1
1
1
1
Field
Contents
Record type
blank
Method Varii
blank
Concentratic
7-17
37-44
45-47
48-55
56
57-63
11
blank
18-23
24
25-35
36
6
1
11
1
SAS Number
blank
Laboratory !
blank
8 Date of Beginning of
Sample Prep or Preparation
of Calibration Solution
3 blank
8 Date Sample Received at Lab
1 blank
7 Source of Analyte
(if not unknown sample)
Remarks
"21"
Codes Flame, Furnace, ICP.
See section 10
"L" - low
"M" - medium
(See note)
Alphanumeric; left justified
Left justified
YY MM DD
YY MM DD
Left justified; company
or EPA, that analyte was
obtained from (Abbreviated
if necessary).
NOTE: The concentration level is an estimate of overall level for all
analytes.
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Record
Position
1-2
3-41
42-46
47
48-54
55-64
Field
Length
2
39
5
1
7
10
Field
Contents
Record type
blank
Volume in ml
blank
Dilution Fac
blank
8.4 Format of the Sample Conditions Record (Type 22)
Use: Continuation of type 20. Used to describe additional sample conditions.
Position: Follows the type 20 and 21 to which it applies.
Remarks
"22"
e.g. 1.0 or 0.050
Right justified; e.g. .001
65-70 6 Percent Solids Right justified
8.5 Format of the Associated Injection and Counter Record (Type 23)
Use: Continuation of type 20. Used to describe holding time.
Position: Follows the type 20 and 21 to which it applies.
Record Field Field
Position Length Contents Remarks
1-2 2 Record type "23"
3-61 59 blank
62 1 "H" Identifies holding time in
days (as on Form 10).
63 1 blank
64-65 2 Holding Time In days - only necessary for
Hg and CN.
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8.6 Format of the Results Data Record (Type 30)
Record
Position
1-2
3
4
5-10
11 -1A
15-25
26-30
31
32-34
35
36-41
42
43-45
46
47
48
49-54
55
56-58
59
60
61
62-66
67
68-70
Field
Length
2
1
1
6
4
11
o
5
1
3
1
6
1
3
1
1
1
6 ~
1
3
1
1
1
5
1
3
Field
Contents
Record type
blank
n T n
blank
Identifier Code
blank
Units of measure
blank
Non-numeric result
blank
Numeric analytical result
blank or '£'
Exponent
blank
Calculated Value Descriptor
blank
Related Calculated Value
blank or '£'
Exponent
blank
Limit or QC Value
Descriptor
blank
Related or QC Limit Value
blank or '£'
Exponent
Remarks
"30"
The Method Code (see section
10) for the specific .analyte
(Left justified) "MG/KG" for
solids; "UG/L " for water;
"PERCT" for percenc
See paragraph 9.4.2 also
called a result qualifier
Right justified; fixed
point or scientific
notation
Blank field will be
interpreted as "+00"
Describes following value
(See paragraph 9.5)
Value represents amount
added or other calculated
or theoretical value.
Format same as 36-46.
Describes following value
(See paragraph 9.6)
Value of item described
above .
H-33
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8.7 Format of the Instrumental Data Readout Record (Type 31)
Use: To describe an added concentration and a measured absorbance or
concentration value. Used to report data for Method of Standard
Additions (Form 8).
Position: Follows type 30.
Remarks
"31"
Indicates Concentration in
ug/L
Indicates Absorbance (B) or
Concentration (C).
'0" to "3'
(right justified)
up to 10 decimal digits,
right justified
Record
Position
1-2
3
4
5
6
7
8
9
10-17
18
Field
Length
2
1
1
1
1
1
1
1
8
1
Field
Contents
Record type
blank
"C"
blank
-B" or "C"
blank
Sequence Number
blank
Concentration Ai
blank
19-28
10
Absorbance/Concentration
Value
8.8 Format of the Auxiliary Data Record (Type 32)
Use: To report wavelength values used for instrument detection limit
determinations and integration times for linear range data.
Position: Follows type 30. (Record will only be required for IDLs and LVMs)
1-2
3-8
9-10
11
12-21
«SM«i^a^a«_
2
6
2
1
10
Record type
blank
"IT" or "IW
blank
Wavelength c
Remarks
"32"
Indicates Integration time
(IT) or IDL wavelength (IW)
Fixed or Scientific notation
as in Record Type 30.
H-34
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8.9 Format of the Correction Data Record (Type 35)
Use: To record TCP interelement correction factor data.
Position: Follows type 30.
Record
Position
1-2
3
4-6
7-13
14-21
22-27
28-31
32
33-40
41
Field
Length
2
1
3
7
8
6
4
1
8
1
Field
Contents
Record Type
blank
"TCP"
blank
Date factor was determined
blank
Identifier of interfering
element
blank
Wavelength value
blank
Remarks
"35"
Indicates ICP interelement
correction factors
YY MM DD
from Section 10
42-51
10
Correction factor
Use space as in result
field on type 30; fixed or
scientific notation
H-35
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8.10 Format of the Comment Record (Type 90)
Use: To provide for Operator Entered Comments
Position: May occur anywhere.
Record Field Field
Position Length Contents Remarks
1-2 2 Record Type "90"
3 1 blank
4-70 67 Any Comment
8.11 Format of the Flags Record (Type 91)
Use: To provide for multiple Form 1 Result Qualifier Flags
Position: Immediately follows the type 30 record to which it applies.
Record
Position
1-2
3
4-6
7
8-10
11
12-14
15
16-18
19
20-22
23
24-26
27
Field
Length
2
1
3
1
3
1
3
1
3
1
3
1
3
1
Field
Contents Remarks
Record Type "91"
blank
Second Result Qualifier Flag See paragraph 9.4.2 for
definitions
blank
Third Result Qualifier Flag
blank
Fourth Result Qualifier Flag
blank
Fifth Result Qualifier Flag
blank
Sixth Result Qualifier Flag
blank
Seventh Result Qualifier Flag
blank
28-30 3 Eighth Result Qualifier Flag
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8.12 Format of the Auxiliary Sample Record (Type 92)
Second Use: To provide additional Sample Descriptive Information.
Position: Follows the type 20(-23) record(s) to which it applies.
Record Field
Position Length
1-2
3
A-17
18
19-28
29
30-39
40
41-46
47
48-53
54
55-60
61
62-67'
2
1
14
1
10
1
6
1
Field
Contents
Record Type
blank
Lab Sample ID
blank
Color Before
blank
10 Color After
1 blank
6 Clarity Before
1 blank
6 Clarity After
1 blank
Texture
blank
Artifacts
Remarks
"92"
Use entries from Form 1 for
each sample.
H-37
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9. Definition of Various Codes Used in FormaC B Records
9.1 Structure of the Method Number and Identifier Code
The method number and identifier code is a four character alphanumeric code
which has the form: XXXY
Where: XXX defines one or more target analytes plus the analytical method.
This part of the code is identical with the method numbers
defined in EPA methods manuals and the code of Federal
Regulations. See section 10.
Y is an alphanumeric modifier which specifies that an allowed
option in the method has been implemented, or specifies fractions
of analytes in the method. For example, Y may distinguish total
and dissolved phosphorous measured by the same method, but with
or without the optional method filtration. Another use of Y is
to label results which have been determined by the Method of
Standard Additions.
If Y is not defined in a method, the default value is one.
The method number is validated as ahphanumeric for XXX and Y. It is stored in
the four (4) digit number field. Identifier codes are used to identify each
metal in a run consisting of more than one metal analysis. It is the same as the
method code for a single specific metal.
See section 10 for examples.
9.2 Definition of Various Codes Used
9.2.1 Quality Control and Related Codes (QCC) in Type 20 Records
NOTE: These QCC appear in the QC code fields of type 20 records. They are
used to indicate the type of data that are being reported. See
section 872.
QCC Name Definition
LD1 LABORATORY DUPLICATE The "Sample (S)" from Form 6.
FIRST MEMBER
LD2 LABORATORY DUPLICATE The "Duplicate (D)" from Form 6.
SECOND MEMBER
LCB LABORATORY CALIBRATION The Calibration Blank from Form 3.
BLANK
LRB LABORATORY (REAGENT) The Preparation Blank from Form 3.
BLANK
H-38 7/88
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QCC Name
LCM LABORATORY CONTROL
SOLUTION
Definition
The Laboratory Control Sample from Form 7.
LVM LABORATORY CALIBRATION The samples used for calibration verification,
CRDL VERIFICATION standards, and LRA determinations on Form 2.
SOLUTION
LIM LABORATORY INTERFERENCE The ICP interference check sample from Form 4.
CHECK SOLUTION
LSO LABORATORY SPIKED The original sample [reported as Sample
SAMPLE BACKGROUND Result (SR) ] from Form 5.
(ORIGINAL) VALUES
LSF LABORATORY SPIKED The spiked sample [reported as Spiked
SAMPLE - FINAL VALUES Sample Result (SSR)] from Form 5.
LDO LABORATORY DILUTED The original sample [reported as Initial Sample
SAMPLE BACKGROUND Concentration (I)] from Form 9.
(ORIGINAL) VALUES
LDF LABORATORY DILUTED The diluted sample [reported as Serial Dilution
SAMPLE - FINAL VALUES Result (S)] from Form 9.
LDX LABORATORY DOUBLE An environmental sample which is used for both
PURPOSE PRECISION AND the LSO (background level before spike) and LD1
ACCURACY SAMPLE (first member of a duplicate).
IDL INSTRUMENT DETECTION The solutions used for instrument detection
LIMIT SOLUTION limits as reported on Form 11.
blank
Unknown sample, not associated with any quality
control item.
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The following QCC values do not refer to actual samples or calibrations for which
laboratory results are obtained. Instead they are used on type 20 records which
act as a header, and indicate that additional (usually calculated) analyte
specific data will be present on type 30 (and following type) records. Usually
this data will apply to an entire production run, in which case it -d.11 appear
immediately following the type 10 record. If the data applies to only a portion
of the samples in the run, it should be placed immediately preceding the samples
to which it applies. Much of the rest of the information in the type 20 record
may be blank, indicating that this data does not apply to these results.
QCC
SID
ICF
SDR
SAKPLE INDEPENDENT
(i.e. INSTRUMENT)
DETECTION LIMITS
INTER-ELEMENT
CORRECTION FACTORS
SPIKE/DUPLICATE
CALCULATED RESULTS
Definition
The data following represents sample independent
detection limits for each compound as reported on
Form 11.
The data following represents ICP interelement
correction factor measurements for each compound
as reported on Form 12.
The data following represents calculated QC
results for the QC samples LD1 and LD2 (percent
RSDs), LSO and LSF (percent recoveries), and LDO
and LDF (percent D's); or for all AA post
digestion spikes. Data consist of percent
RSDs,percent recoveries, or percent D's for each
analyte as reported on Forms 5, 6, 9 and 14.
9.3 Codes For Sample Medium (Matrix, Source)
Medium
All Media, Don't Know or Don't Care.
Water
Soil _
Sludge
9.4 List of Samples and Result Qualifiers
Code
0
1
H
I
Definition: A sample qualifier or a result qualifier (also called a non-numeric
result) consists of 3 characters which acts as an indicator of the
fact and the reason that the subject analysis (a) did not produce a
numeric result or (b) produced a numeric result but it is qualified
in some respect relating to the type or validity of the result.
H-40
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9.4.1 Sample Qualifiers
Qualifier Full Name
BAG BACKGROUND CORRECTION
BEF
AFT
BEFORE
AFTER
POS POST DIGESTION SPIKE
9.4.2 Result Qualifiers
Qualifier Full Name
BDL BELOW DETECTABLE LIMITS
NAR NO ANALYSIS RESULT
FQC FAILED QUALITY CONTROL
LLS LESS THAN LOWER STANDARD
EST ESTIMATED VALUE
MSP PERCENT RECOVERY
DPD PERCENT DIFFERENCE
DPR PERCENT RSD
(See paragraph 8.2)
Definition
Background correction has been applied to this
group of values.
Labels ICP corrections that were applied before
generating raw data; or spiked samples (LSF)
that were spiked prior to method-defined
digestion (Form 5A).
Labels ICP corrections that were applied after
generating raw data; or spiked samples (LSF)
that were spiked after method-defined digestion
(Form 5B).
Labels furnace AA post digestion spike percent
recovery data (from Form 14), and also
indicates that measured results from the spiked
analysis will not be present and the sample
results will be reported using QC codes
appropriate to non-spiked samples.
(See paragraph 8.6)
Definition
Indicates analyte was analyzed for but not
detected; ignore value (Form 1 "U" Flag).
There is no analysis result required for this
subject parameter (Form 1 "NR" Flag).
The'analysis result is not reliable because
control limits were exceeded when the analysis
was conducted. Value is estimated. (Form 1
"M", "W", "N", "*", or "+" Flags).
The analysis value is less than the contract
required detection limit (Form 1 [ ] value).
Indicates a value estimated or not reported due
to presence of interference (Form 1 "E" Flag).
The following value represents the percent
recovery for the spiked sample.
The following value represents the percent
difference of the dilution result from the
original.
The following value represents the percent
RSD of the duplicate results.
H-41
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9.5 Calculated Value Descriptors (See paragraph 8.6)
These codes appear in column 47 to identify the value in columns 49-58.
Qualifier Full Sane Definition
AMOUNT ADDED
TRUE VALUE
Identifies the amount of matrix
spike analyte added (for QC code
"LSF").
Indicates Che true value for each
analyte (for QC codes "LCM", "LVM",
and "LIM").
9.6 Limit or QC Value Descriptors (See paragraph 8.6)
These codes appear in column 60 to identify the value in columns 62-70.
Qualifier
Pull Name
Definition
U
UNDETECTED
PERCENT RECOVERY
CORRELATION COEFFICIENT
Value is the corrected sample
quantisation limit (Form 1 "U"
Value).
Value is the Percent Recovery for
each compound (for QC codes "LCM",
"LVM", and "LIM").
Value is the correlation coefficient
(r) for any result obtained by the
Method of Standard Additions (last
digit of identifier is "2").
CONTROL LIMIT
Value is CRDL value from Form 6 if
present (for QC code "SDR").
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10.
Exam-pie Method and Matrix Codes for Inorganic Methods
The codes given below are examples of method number designations for
inorganic analyses. In all of these, the Z position refers to the matrix
code and should be interpreted with the aid of paragraph 9.3. The generic
value of 1, which represents water, type unknown or not specified", is used
for water analysis.
Solid samples are represented by two specific codes, with Z values of H
(soil) and I (sludge).
Each method code shown occurs in a type 10 record and acts as the header
for the appropriate list of compounds.
200 4
200 4
200 4
E It Definition
1 1 Generic code for analysis of total metals in water, after
method-defined digestion, by atomic absorption, flame.
2 1 Generic code for analysis of total metals in water, after
method-defined digestion, by atomic absorption, furnace.
7 1 Generic code for analysis of total metals in water, after
method-defined digestion, by ICF
For specific matrix codes, replace Z with the specific value for the type
of sample (from paragraph 9.3). For Method Identifiers (see section 8.6),
replace XXX with value for the analyte. Change Y- to 2 if the value was
determined by the Method of Standard Additions (Form 1 "S" Flag). Each
identifier shown occurs in a type 30 record and identifies the specific
compound.
202
204
206
208
210
213
215
218
219
220
236
239
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
242
243
249
258
270
272
273
279
282
286
289
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Tin
Vanadium
Zinc
H-43
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NOTE: Exception to above:
XXX Y fi Z. Definition
245 111 Analysis of mercury in water by the manual cold vapor
technique
245 121 Analysis of mercury in wat^r by the automated cold vapor
technique
XXX Y S. i Definition
245 4 5 H Analysis of mercury in soil, after method-defined digestion,
by the manual cold vapor technique
245 451 Analysis of mercury in sludge, after method-defined
digestion, by the manual cold vapor technique
335 121 Analysis of total cyanide in water by titrimetric, manual
spectrophotometric, or semi-automated spectrophotometric
means
NOTES:
1. See paragraph 9.1 for the structure of "XXX" and "Y"
2. If multiple metals are analyzed as part of a single production run, the
method code (paragraph 8.1) is "2004". If only a single metal is analyzed,
then use the value for that metal (i.e. "2064* for arsenic). In all cases
the identifier in paragraph 8.6 is a specific code given in Section 10.
3. The values of "N" and "Z" are sample dependent and may vary within a.
production run. They are reported on type 20 and 21 records (paragraphs 8.2
and 8.3)
H-44 7/88
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of the Sequence of Record Types in a Production" Run
10 Contains Run Header information
20 Occurs once for each sample, calibration, calculated QC results,
instrument detection limits, etc. - Acts as a header.
21 Will usually be present
22 Contains additional information for samples
30 Occurs once for each final analytical result. Will give
whatever value is being determined as defined by the type 20.
31 Reports any instrumental data necessary
32 Reports any auxiliary data necessary
35 Reports corrections to results if necessary
30 Values for the next analyte or parameter being measured.
31 Additional data may vary for each parameter, and records
32 may occur in any order. Multiple occurrences of the
32 same record type, however, must be consecutive.
35
30 Continues for as many as are necessary
31
32
35
30
31
32
35
20 Next Sample Header record - The following applies to the next
21 sample or other group of data.
22
30
31
32
30
31
32 etc. .
20
21
30
31
32
etc.
H-45 7/88
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12 . 1 Format
Record
Position
1-2
3-6
7-10
11-15
16
17
18-20
21-25
26-30
31-66
67-69
12 . 2 Format:
Record
Position
1-2
3
4
5-17
18-23
24-36
37-44
45-56
57-63
of the
Field
Length
2
4
4
5
1
1
3
5
5
36
3
of the
Field
Length
2
1
1 ~
13
6
13
8
12
7
Sample Header Data Record
Field
Contents
Record type
blank
"LRAI" or "LRAF"
blank
"0"
blank
"LVM"
blank
Case number
blank
Analyte Count
Sample Header Data Record
Field
Contents
Record type
blank
"7"
blank
S A S Number
blank
Dace of Preparation of
Calibration Solution
blank
Source of Analyte
(Type 20) for Linear Range Analysis
Remarks
"20"
To indicate initial or final
No matrix code
See paragraph 9.2
*
Numeric; 1-3 decimal digits;
right justified - gives the
number of analytes deter-
mined by this method for
this sample.
(Type 21) for Linear Range Analysis
Remarks
"21"
Codes ICP. See Section 10
Alphanumeric; left justified
YY MM DD
Left justified; company or
EPA, that compound was
obtained from (abbreviated
if necessary).
H-46 7/88
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12.3 Format of the Results Data Record (Type 30) for Linear.Range Analysis
Record
Position
1-2
3
4
5-10
11-14
15-25
26-30
31-35
36-41
42
43-45
46
47
48
49-54
55
56-58
59
60
61
62-66
67
68-70
Field
Length
2
1
1
6
4
11
5
5
6
1
3
1
1
1
6
1
3
1
1
1
5
1
3
Field
Contents
Record type
blank
"I"
blank
Identifier Code
blank
"UG/L "
blank
Found Value
blank or '£'
Exponent
blank
"T"
blank
True Value
blank or '£'
Exponent
blank
ftpfl
blank
Percent Recovery
blank or 'E'
Exponent
Remarks
"30"
The Method Code (section 10)
for the specific compound.
Units
Right justified; fixed point
or scientific notation.
Indicates true value
See paragraph 9.5
Format same as 36-46.
Indicates percent recovery
See paragraph 9.6
H-47
7/88
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12.4 Format of the Auxiliary Data Record (Type 32) for Linear Range Analysis
(only for quarterly submissions)
Remarks
"32"
Indicates Integration tine
Fixed or Scientific notation
Record
Position
1-2
3-8
9-10
11
Field
Length
2
6
2
1
Field
Contents
Record type
blank
'IT"
blank
12-21
10
Integration Time Value
12.5 Format of the Sample Header Data Record (Type 20) for Duplicate Data
Record
Position
1-2
3-6
7-12
13-15
16
17
18-20
21-25
26-30
31-67
Field
Length
2
4
6
3
1
1
3
5
5
37
Field
Contents
Record type
blank
EPA Sample ID
blank
Sample Medium/Matrix Code
blank
"SDR"
blank
Case number
blank
Remarks
"20"
Left justified
See paragraph 9.
3
Identifies calculated
QC results
68-70
3 —
Analyte Count
Numeric; 1-3 decimal digits;
right justified - gives the
number of analyte determined
by this method for this sample.
H-48
7/88
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12.6 Format of the Sample Header Data Record (Type 21) for Duplicate Data
Record
Position
1-2
3
4
5
6
7-17
18-23
24
25-35
Field
Length
2
1
1
1
1
11
6
1
11
12.7 Format of the
Record
Position
1-2
3
4
5-10
11-14
15-25
26-30
31
32-34
35
36-41
42
43-45
Field
Length
2
1
1
6
4
11 ~
5
1
3
1
6
1
3
Field
Contents
Record type
blank
Method Variation Code (N)
blank
Concentration level
blank
SAS Number
blank
Laboratory Sample ID
Results Data Record (Type
Field
Contents
Record type
blank
n T ti
blank
Identifier Code
blank
"PERCT".
blank
"DPR«
blank
Duplicate Percent RSD
blank or '£'
Exponent
Remarks
"21"
Codes flame, furnace, ICF.
See section 10
"L" - low
"M" - medium
Alphanumeric; left justified
Left justified
30) for Duplicate Data
Remarks
"30"
The Identifier Code
(section 10)
for the specific compound.
Units are percent
Indicates Duplicate %RSD
Right justified; fixed point
or scientific notation.
H-49
7/88
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12.8 Format of the Sample Header Data Record (Type 20) for Continuing Checks
Record
Position
1-2
3-6
7-10
11-15
16
17
18-20
21-25
26-30
31-66
67-69
12.9. Format
Record
Position
1-2
3
4
5-17
18-23
24-36
37-44
45-56
57-63
Field
Length
2
4
4
5
1
1
3
5
5
36
3
of the
Field
Length
2
1
1
13
6
13
8
12
7
Field
Contents
Record type
blank
"CCV1" -CCV2" etc
blank
nO-
blank
"LVM"
blank
Case number
blank
Analyte Count
Sample Header Data Record (Type
Field
Contents
Record type
blank
Method Variation Code (N)
blank
S A S Number
blank
Date of Preparation
of Calibration Solution
blank
Source of Analyte
Remarks
"20"
To indicate which check
All matrices
See paragraph 9.4.1
Numeric; 1-3 decimal
digits; right justified -
gives the number of
analytes determined
by this method.
21) for Continuing Checks
Remarks
"21"
Codes Flame, Furnace, 1CF.
See Section 10
Alphanumeric; left justifiei
YY MM DD
Left justified; company or
EPA, that analyte was
obtained from.
NOTE: The Results Data Record (Type 30) for Continuing Checks is identical to
that for Linear Range Data. See paragraph 12.3. Record type 32 is not
present.
H-50 7/88
-------
12.10 Format of the Results Data Record (Type 30) for an Unknown Sample when the
Method of Standard Additions was used.
Record
Position
L-2
3
4
5-10
11-14
15-25
26-30
31
32-34
35
36-41
42
43-45
46
47
48
49-54
55
56-58
59
60
61
62-66
67
68-70
Field
Length
2
1
1
6
4
11
5
1
3
1
6
1
3
1
1
1
6
_
1
3
1
1
1
5
1
3
Field
Concents
Record type
blank
"I"
blank
-2XX2"
blank
Units of measure
blank
Non-numeric result
blank
Numeric analytical result
blank or '£'
Exponent
blank
Calculated Value Descriptor
blank
Related Calculated Value
blank or '£'
Exponent
blank
-C"
blank
r* value
blank or 'E' .
Exponent
Remarks
"30"
See Section 10 "XX" values.
Last character is a^2" .
"MG/KG" for solids; "UG/L"
for water.
See paragraph 9.4.2; also
called a result qualifier
Right justified; fixed point
or scientific notation
Describes following value
See paragraph 9.5
Format sane as 36-46. (Only
present if spiked sample)
Indicates correlation
coefficient.
Give value from Form 8 for
each analyte dete rained.
NOTE: Following each type 30 record where the Method of Standard Additions was
used will be four type 31 records (see paragraph 8.7). Each contains data
for one of the four additions.
H-51 7/88
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12.11 Format of the Sample Header Data Record (Type 20) for Post Digestion Spike
Data
Remarks
"20"
Left justified
See section 9.3
Identifies calculated
QC results
Label this as post
digestion spike data.
Numeric; 1-3 decimal digits;
right Justified - gives
the number of compounds
determined for this sample.
Record
Position
1-2
3-6
7-12
13-15
16
17
18-20
21
22-24
25
26-30
31-67
Field
Length
2
4
6
3
1
1
3
1
3
1
5
37
Field
Contents
Record type
blank
EPA Sample ID
blank
Sample Medium/Matrix Code
blank
"SDR"
blank
"PDS"
blank
Case Number
blank
68-70
Compound Count
H-52
7/88
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12.10 Format of the Results Data Record (Type 30) for Post Digestion Spike Data
Record
Position
1-2
3
4
5-10
11-14
15-25
Field Field
Length Contents
2
1
1
6
11
Record type
blank
II T ft
blank
Identifier Code
blank
26-30
31
32-34
35
36-41
42
43-45
5
1
3
1
6
1
3
"PERCT"
blank
"MSP"
blank
Percent Recovery
blank or "E"
Exponent
Remarks
"30"
The Identifier Code
(see section 10) fqr
the specific compound
Units are percent
Indicates Percent Recovery
Right justified; fixed point
or scientific notation
*U.S. GOVERNMENT PRINTING OFFICE: 1989—517-003/84337
H-53
7/88
------- |