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nSEPA CONTRACT LABORATORY PROGRAM
STATEMENT OF WORK
FOR
INORGANIC ANALYSIS
Multi-Media
High-Concentration
(HCIN)
Document Number IHC01.2
cr>
CO
HEADQUARTERS LIBRARY
ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
a
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STATEMENT OF WOPK
TABLE OF CONTENTS
PREFACE:
EXHIBIT A:
EXHIBIT B:
EXHIBIT C:
EXHIBIT D:
EXHIBIT E:
EXHIBIT F:
SUMMARY OF REQUIREMENTS 1
I. Summary of Method 2
II. General Requirements 4
III. Specific Requirements 5
REPORTING AND DELIVERABLES REQUIREMENTS 12
I. Contract Reports/Deliverables Distribution .... 13
II. Report Descriptions and Order of Data Deliverables 15
III. Form Instruction Guide 26
17. Data Reporting Forms ...,-.... 58
INORGANIC ANALYTE TABLES
78
PREPARATION AND ANALYSIS METHODS 84
I. Introduction 86
II. Holding Times and Storage Requirements 88
III. Methodology and Data User Guide 89
IV. Sample Preparation 92
V. Sample Analysis ........ 95
QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS .... 227
I. General QA/QC Practices 229
II. Specific QA/QC Procedures 230
III. Laboratory Evaluation Process 253
CHAIN-OF-CUSTODY, DOCUMENT CONTROL, AND
STANDARD OPERATING PROCEDURES 255
I. Chain-of-Custody 257
II. Document Control 260
III. Standard Operating Procedures 264
EXHIBIT G:
GLOSSARY OF TERMS
267
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PREFACE
The purpose of this contract is to provide the U.S. Environmental
Protection Agency (EPA) with inorganic chemical analytical services using
direct nebulization, inductively coupled plasma and hydride inductively
coupled plasma emission spectroscopy (TCP and HYICP), graphite furnace and
cold vapor atomic absorption spectroscopy (GFAA and CVAA), and specified
cyanide, conductivity, and pH techniques for the analysis of high
concentration field samples. The majority of these samples to be analyzed are
from known or suspected hazardous waste sites and may contain potentially
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 and precautions to ensure the health and safety
of its employees. The Contractor is responsible for providing a safe working
environment and making its employees aware of the potential hazards of working
with and analyzing these samples.
Procedures specified herein shall be used in the preparation and
analysis of liquid, solid, and multiphase samples for the presence and
quantitation of 22 metals, cyanide, conductivity, and pH. The-Contractor
shall employ safe handling procedures and generally accepted good laboratory
practices in the performance of contract requirements and shall follow the
quality assurance/quality control (QA/QC) program specified herein.
The data obtained under this contract will be used by the EPA to
determine the existence and extent of threats to the public and the
environment posed by hazardous waste disposal sites. The data may be used in
civil and/or criminal litigation which requires the strictest adherence to
chain-of-custody protocol, document control, and quality assurance procedures.
IHC01.2
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EXHIBIT A
SUMMARY OF REQUIREMENTS
SECTION I: SUMMARY OF METHOD
SECTION II: GENERAL REQUIREMENTS
SECTION III: SPECIFIC REQUIREMENTS
Page
2
4
5 _
IHC01.2
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SECTION I
SUMMARY OF METHOD
1. Purpose
1.1 Samples of industrial waste materials gathered in support of EPA
investigations of disposal, handling and storage practices are subjected to
limited chemical characterization using the procedures and methods prescribed
herein. This characterization is not designed to define the total composition
of the samples, but is designed essentially to look for specific constituents.
The characterization is targeted to the analysis of the priority pollutants.
and additional inorganic parameters.
1.2 Samples may be obtained from drummed materials, waste pits or lagoons,
piles of waste, tanker trucks, onsite tanks, or apparent contaminated soil
areas.
1.3 The waste materials usually are industrial process waste, byproducts,
raw materials, intermediates and contaminated products. Many of the samples
may be spent oil, spent solvents, paint wastes, metal treatment wastes, and
polymer formulations.
1.4 The methods are included for the determination of 22 metals, cyanide,
conductivity, and pH. Also included is a phase separation method that is
applied to samples prior to digestion and analysis. Each individual phase is
digested and analyzed by the specific methods. (A phase being either water
miscible, non-water miscible, or solid.)
2. Limitations
2.1 A detailed knowledge of the chemical and physical properties of samples
submitted for analysis, as well as the behavior of analytes under specific
conditions, are not available with the wide variety of materials that are
submitted under this contract. Although the analytical methods contained
herein have been shown to be quantitative for a large number of sample
matrices, the unknown nature of the samples prior to characterization can
cause problems in certain instances.
2.2 The elemental constituent analysis approach only analyzes 22 metals.
Interferences from metals not included in this analysis which may cause either
positive or negative biases will not be corrected by this approach. The
recovery of certain metals from a sample matrix may be affected by the
presence of other metals or by the form of the metal, which may not be readily
detected.
IHC01.2 Page 2
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Summary of Method
Exhibit A
3.
Characterization
3.1 Corrosivity of a waste may be determined by testing for either pH or
rate of steel corrosion. The pH of water extracted samples as determined
herein does not classify a waste as a RCRA waste but instead is determined for
informative purposes such as to aid in waste segregation.
3.2 Reactive wastes may be wastes from one of many groups including unstable
materials (explosives), materials that undergo violent reactions with water
(sodium metal) or without water (pyrophorics), and materials that generate
toxic vapors/gases upon reaction with water (phosphides) or mildly acidic
conditions (cyanide). The methods for cyanide included here are "total"
methods for cyanide amenable to distillation under strongly acidic conditions.
3.3 The identification of metal constituents, including priority pollutants,
is part of the EPA determination of a toxic waste. This material is not a
"toxic" waste in the normal usage of the word but instead is based on the
potential for the hazardous constituents of the waste to leak out of the waste
site (landfill, pond, etc.) and contaminate the soil and/or ground water.
IHC01.2
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SECTION II
GENERAL REQUIREMENTS
The Contractor shall employ procedures specified in this Statement of
Work (SOW) for the preparation and analysis of high concentration samples that
may or may not contain more than one phase (i.e., water raiseible, non-water
miscible, and solid) for the presence and quantitation of 22 metals, cyanide,
conductivity, and pH.
Exhibit B contains all reporting and deliverables requirements for the
contract, including copies of the data reporting forms and a Form Instruction
Guide. Exhibit C contains the Contract Required Quantitation Limits (CRQLs)
for all target analytes. Exhibit D contains the specific analytical
procedures required, defines the specific application of these procedures, and
contains the method specific QA/QC requirements of this contract. Exhibit E
contains general and specific laborator-y QA/QC requirements. Exhibit F
contains chain-of-custody and document control requirements that the
Contractor must follow in processing samples under this contract, and
specifies requirements for written laboratory Standard Operating Procedures
(SOFs). 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 definition, the glossary meaning shall be applicable.
A full sample analysis is defined as identification and quantitation of
specific inorganic analytes in Exhibit C, in accordance with the methods in
Exhibit D and the performance of related QA/QC procedures in Exhibits D and E.
The samples to be analyzed by the Contractor are from known or suspected
hazardous waste sites and may contain potentially hazardous inorganic and/or
organic materials at high concentration levels. The Contractor should be
aware of the potential hazards associated with the handling and analysis of
these samples. It is the Contractor's responsibility to take all necessary
measures and precautions to ensure the health and safety of its employees.
IHC01.2
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SECTION III
SPECIFIC REQUIREMENTS
For each sample, the Contractor shall perform the following tasks:
1.
Task I;
Receive and Prepare Hazardous Waste Samples.
1.1 The Contractor shall receive and handle samples under the
chain-of-custody and document control procedures described in Exhibit F.
Sample receiving procedures listed in Task III (3.) shall also be followed.
1.2 The Contractor shall separate multi-phase samples into single phase
units and prepare each unit for analysis. If a sample consists of more than
three phases, the Contractor shall contact the Sample Management Office (SMO)
for further direction. The Contractor shall note that the identifiers for the
phases shall follow a lowercase letter system in which the particular phase
type is given a direct letter identifier and assigned a letter for each phase
of that type. The Contractor shall use the following identifiers for this
contract: water miscible, a "w" (e.g., wa, wb, we); solid, a "c" (e.g., ca,
cb, cc); and non-water miscible, an "n" (e.g., na, nb, nc). In the example
above, the second letter of this system is used to identify the number of
phases of this type for the sample (e.g., a equals 1, b equals 2, c equals 3).
Each phase shall be considered a full sample analysis.
1.3 Exhibit D contains instructions and references for preparation and
analyses of high concentration inorganic samples by ICP, HYICP, GFAA, CVAA,
cyanide, conductivity, and pH methods. A schematic flow chart depicting the
complete high concentration inorganics analytical scheme is presented in
Section I of Exhibit D.
1.4 The Contractor shall prepare and analyze samples within the maximum
holding times specified in Section II of Exhibit D, even if these times are
less than the maximum data submission time allowed in this contract.
1.5 The Contractor shall be responsible for all necessary measures and
precautions to ensure the health and safety of laboratory employees. The
Contractor is advised that the samples received under this contract are
usually from known or suspected hazardous waste sites and may contain high
(e.g., greater than 15%) levels of inorganic and/or organic materials of a
potentially hazardous nature and of unknown structure and concentration. All
samples should be handled throughout the analysis with appropriate safety
precautions.
2. Task II: Analyze Samples for the Identification and Quantitation of
Specific Inorganic Analytes.
2.1 Samples prepared in Task I shall be analyzed by methods specified in
Exhibit D for the target analytes listed in Exhibit C. The Contractor shall
IHC01.2
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Specific Requirements
Exhibit A
provide the required analytical expertise and instrumentation for analyses of
target metals, cyanide, conductivity, and pH equal to or lower than the
quantitation limits specified in Exhibit C. The Contractor shall meet the
control limits also provided in Exhibit C for analysis of various QC samples
and their specified methods.
2.2 The Contractor shall have sufficient analytical equipment and capability
to meet all terms and conditions of the contract as specified by the
following:
Inductively coupled plasma (ICP) emission spectrophotometer with the
capability to analyze metals sequentially or simultaneously, and hydride
generation and analysis capabilities;
Atomic absorption (AA) spectrophotometer equipped with a graphite
furnace and cold vapor AA (or a specific mercury analyzer) analysis
capabilities; and
Analytical equipment/apparatus for analysis of cyanide, conductivity,
and pH as described in Exhibit D.
2.3 At a minimum, the Contractor shall have the following instruments
operative at the time of the Preaward Site Evaluation and committed for the
full duration of the contract.
100 Samples/Month Capacity Requirements
Fraction
No. of
Ins trument(s)
Type of
Instrument
ICP Metals
GFAA Metals
(if necessary)
Mercury
ICP Emission
Spectrophotometer;
with Hydride Manifold
Accessory (if necessary)
Atomic Absorption
Spec tropho tome te r
with Graphite Furnace
Atomizer
Mercury Cold Vapor AA
Analyzer or AA
instrument modified
for Cold Vapor Analysis
IHC01.2
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Specific Requirements
Exhibit A
Fraction
No. of
Instrument(s)
Type of
Instrument
Cyanide
6 distillation
units + 1
photometer
pH
Conductivity
See Cyanide
Methods, Statement
of Work Exhibit D;
Section IV, Part G
See pH Methods,
Statment of Work
Exhibit D, Section
IV, Part A
See Conductivity
Methods, Statement
of Work Exhibit D
Section IV, Part B
2.4 All samples shall be carried through the sample preparation procedure
and then run undiluted. When an analyte concentration exceeds the calibrated
or linear range, appropriate dilution and reanalysis of the prepared sample is
required, as specified in Exhibit D. The dilution factor shall not bring the
concentration below the CRQL. All dilutions must be taken from the original
sample. Diluting previously diluted samples is not acceptable.
2.5 Exhibit D specifies the analytical procedures that shall be used. The
identification and quantitation of all metals except mercury shall be
accomplished using either ICP, HYICP, or GFAA methods specified in Exhibit D.
The appropriate method must be selected to achieve the CRQL in Exhibit C.
Mercury, cyanide, conductivity, and pH shall be analyzed by the individual
procedures specified in Exhibit D.
2.6 For the purpose of this contract, a full sample analysis is defined as
identification and quantitation of specific inorganic analytes in Exhibit C,
in accordance with the methods in Exhibit D and the performance of related
QA/QC procedures in Exhibits D and E. Duplicate sample, laboratory control
sample, and spike sample analyses shall each be considered a separate full
sample analysis. A sample may consist of more than one phase (e.g., water
miscible, non-water miscible, and solid) contained inside appropriate
receptacles. More than one container may be received for a single sample.
All other QA/QC requirements are considered an inherent part of this contract
and are included in the contract sample unit price.
IHC01.2
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Specific Bequirements
Exhibit A
3. Task III: Perform Required Quality Assurance/Quality Control
Procedures
3.1 All QA/QC procedures prescribed in Exhibits D and E shall be strictly
adhered to by the Contractor, including daily or (as required) more frequent
use of standard reference solutions from EPA, the National Institute of
Standards and Technology (HIST), or secondary standards traceable thereto.
Records documenting the use of the procedures shall be maintained in
accordance with the document control procedures in Exhibit F, and shall be
reported in accordance with Exhibit B requirements.
3.2 The Contractor shall establish a Quality Assurance Program (QAP) with
the objective of providing sound analytical chemical measurements. This
program shall incorporate QC procedures, any necessary corrective action
taken, all documentation required during data collection, and the quality
assessment measures performed by management to ensure acceptable data
production.
3.3 Additional QA/QC shall be required on a preaward basis and with each SDG
in the form of a Performance Evaluation (PE) samples submitted by EPA for
Contractor analysis, and in the form of verification of instrument parameters,
as described in Exhibit E.
3.4 A Laboratory Control Sample (LCS) shall be designed to assure that the
operating parameters of the analytical instrumentation and analytical
procedures from sample receipt through identification and quantitation are
capable of producing reliable data. The Contractor shall analyze the LCS
concurrently with the analysis of the samples in the SDG.
3.5 EPA has provided formats to>the Contractor for the reporting of data
(Exhibit B). The Contractor shall be responsible for completing and returning
analysis data sheets in the format specified in this SOW within the time
specified in the Contract Performance/Delivery Schedule.
3.5.1 Use of formats other than those designated by EPA will be deemed as
noncompliant. Such data are unacceptable. Resubmission in the specified
format shall be required at no additional cost to the Government.
3.5.2 Computer generated forms may be submitted in the hardcopy data
.package(s) provided that the forms are identical to the EPA FORMAT. This -
means that the order of data elements is the same as on each EPA required
form, including form numbers,.titles, page numbers, header information,
columns, and lines. The only exception to this requirement shall be the use
of a different font to conform to a laboratory's printer configuration.
IHC01.2
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Specific Requirements
Exhibit A
3.6 The Contractor shall designate and utilize key personnel listed below to
perform the minimum functional requirements necessary to meet the terms and
conditions of this contract. The minimum education and experience
requirements for these functions are identified in Bidder Responsibility,
Attachment C of this contract. The Contractor must report changes in key
personnel by submitting resumes for replacement personnel along with quarterly
delivery of Quarterly Verification of. Instrument Parameters Report to the
Environmental Monitoring Systems Laboratory-Las Vegas (EMSL-LV) and SMO. The
EPA reserves the right to review personnel qualifications and expertise. The
following positions are considered key personnel for this contract:
Laboratory Supervisor;
QA Officer;
Inductively Coupled Plasma (ICP) Spectroscopist;
Inductively Coupled Plasma (ICP) Operator;
* Atomic Absorption (AA) Operator;
.-
Inorganic Sample Preparation Specialist;
Classical Techniques (Cyanide) Analyst; and (
Inorganic Chemist (Backup).
NOTE: The Contractor shall also designate a sample custodian and a document
control officer.
3.7 The Contractor shall respond within 10 days to requests from data
recipients for additional information or explanations that result from the
Government's inspection activities.
3.8 The Contractor shall retain unused sample volumes and used sample
containers for a period of 60 days after data submission.
3.9 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 strictly being followed. This
documentation shall be reported in the Complete SDG File (see Exhibit B).
3.10 Sample shipments to the Contractor's facility will be scheduled and
coordinated by SMO, acting on behalf of the EPA Administrative Project
Officer. The Contractor shall communicate with SMO personnel by telephone as
necessary throughout the process of sample scheduling, shipment, analysis, and
data reporting, to ensure that samples are properly processed.
IHC01.2
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Specific Requirements
Exhibit A
3.10.1 If there are problems with samples (e.g., broken or leaking
containers) or sample documentation/paperwork (e.g., missing, incomplete, or
conflicting Traffic Reports), then the Contractor shall contact SMO
immediately for resolution. The Contractor shall notify SMO immediately
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.
3.11 Sample analyses will be scheduled by groups of samples, each defined as
a Case and identified by a unique EPA Case number assigned by SMO. A Case
signifies a group of samples collected at one site or geographical area over a
finite time period. Samples may be shipped to the Contractor in a single
shipment or multiple shipments over a period of time, depending on the size of
the Case. A Case consists of one or more Sample Delivery Groups (SDGs). A
SDG is defined by the following, whichever is most frequent:
Each Case of field samples received, or
Each 20 field samples within a Case, or
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 SDG).
3.12 Data for all samples in a SDG must be submitted together (in one
package) in the order specified in Exhibit B. The SDG number is the EPA
sample number of the first sample received in the SDG. When several samples
are received together in the first SDG shipment, the SDG number is the lowest
sample number (considering both alpha and numeric designations) in the first
group of samples received under the SDG. The SDG number is reported on all
data reporting forms. The SDG Receipt Date is the date that the last sample
in the SDG is received.
3.13 The Contractor is responsible for identifying each SDG as samples are
received, and properly documenting samples (see Exhibit B) and communicating
with SMO personnel.
3.14 Each sample received by the Contractor will be labeled with an EPA
sample number and accompanied by a Traffic Report (TR) form bearing the sample
number and descriptive information regarding the sample. The Contractor shall
complete and sign the TR, recording the date of sample receipt and sample
condition upon receipt for each sample container.
3.15 The Contractor shall submit signed copies of TRs for all samples in a
SDG to SMO within 3 calendar davs following receipt of the last sample in the
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Specific Requirements
Exhibit A
SDG, TRs shall be submitted in SDG sets (i.e., all TRs for a SDG shall be
clipped together) with a SDG cover sheet containing information regarding the
SDG, as specified in Exhibit B.
3.16 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 and correspondence.
3.17 Samples will be routinely 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.
3.18 The Contractor shall accept all samples scheduled by SMO, provided that
the total number of samples received in any calendar month does not exceed the
monthly limitation expressed in the contract. Should she Contractor elect to
accept additional samples, the Contractor shall remain bound by all contract
requirements for analysis of those samples accepted.
IHC01.2
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EXHIBIT B
REPORTING AND DELIVERABLES REQUIREMENTS
SECTION I:
Contract Reports/Deliverables Distribution
13
SECTION II: Report Descriptions and Order of Data Deliverables ... L5
SECTION III: Form Instruction Guide
26
SECTION IV: Data Reporting Forms
58
IHC01.2
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SECTION I
CONTRACT REFORTS/DELIVERABLES DISTRIBUTION
The following table summarizes the contract reporting and deliverables
requirements specified in the Contract Schedule and includes the distribution
of each deliverable. NOTE: Specific recipient names and addresses are subject
to change during the term of the contract. The EPA Administrative Project
Officer (APO) or SMO will notify the Contractor in writing of such changes
when they occur.
Item
Updated SOPs
*Sample Traffic Reports
**Sample Data Package
including the Performance
Evaluation Sample (PES)
Analysis
Complete SDG File
*Quarterly and Annual
Verification of Parameters
****Quality Assurance Plan
No. of
Copies
2
1
2
1
2
1
Schedule
and
Delivery
45 days after contract
award
***3 days after receipt
of last sample in
Sample Delivery Group
(SDG)
35 days after receipt
of last sample in SDG
35 days after data
receipt of last sample
in SDG
15th day of January,
April, July, October
Submit copy within 7
days of written request
by APO
Distribution
(1)
X
X
X
As
(2)
X
X
X
3 dire<
(3)
X
X
:ted
Distribution
(1) Sample Management Office (SMO)
(2) Environmental Monitoring Systems Laboratory-Las Vegas (EMSL-LV)
(3) USEPA Region
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Contract Reoorts/Deliverables Distribution
Exhibit B
* 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 Exhibit A,
Task III, for further description.)
**** See Exhibit E for description.
NOTE: As specified in the Contract Schedule (Government Furnished Supplies
and Materials), unless otherwise instructed by SMO, the Contractor shall
dispose of unused sample volumes and used sample bottles/containers no earlier
than sixty (60) days following submission of analytical data.
Distribution Addresses
(1) USEPA Contract Laboratory Program (CLP)
Sample Management Office (SMO)
P. 0. Box 818
Alexandria, VA 22313
For overnight delivery service, use street address:
300 N. Lee Street
Alexandria, VA 22314
(2) USEPA Environmental Monitoring
Systems Laboratory (EMSL-LV)
P. 0. Box 15027
Las Vegas, NV 89114
ATTN: Data Audit Staff
For overnight delivery service, use street address:
944 E. Harmon, Executive Center
Las Vegas, NV 89109
ATTN: Data Audit Staff
(3) USEPA REGIONS:
SMO, acting on behalf of the EPA APO, will provide the Contractor with
the list of addressees for the ten EPA Regions. SMO will provide the
Contractor with updated Regional address/name lists as necessary
throughout the period of the contract and identify other client
recipients on a case-by-case basis.
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SECTION II
REPORT DESCRIPTIONS AND ORDER OF DATA DELIVERABLES
The Contractor shall provide reports and other deliverables according to
the schedule specified in Section F of the contract, Deliveries or
Performance. .The required content and form of each deliverable is described
in this Exhibit.
All reports and documentation must be:
Legible;
Clearly labeled and completed in accordance with instructions in
this Exhibit;
Arranged in the order specified in this Section;
Paginated; and
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 an Administrative
Project Officer (APO)/Technical Project Officer (TPO) action, the data shall
be clearly marked as "ADDITIONAL DATA" and shall be sent to all three
contractual data recipients (SMO, EMSL-LV, and Region). A cover letter shall
be included that describes what data are being delivered, to which EPA Case(s)
the data pertain, 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). In
all three instances, the data must be accompanied by a color-coded Cover Sheet
(Laboratory Response To Results of Contract Compliance Screening) provided by
SMO.
Section III of this Exhibit contains instructions to the Contractor for
properly completing all data reporting forms to provide the EPA with all
required data. Section IV of this Exhibit contains the required Inorganic
Analysis Data Reporting Forms in EPA-specified formats.
Descriptions of the requirements for each deliverable item cited in the
Contract Performance/Delivery Schedule (Section F.I) are specified as follows
in 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.
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Report Descriptions and Order of Data Deliverables Fxhibit B
1. Updated Standard Operating Procedures
1.1 The Contractor shall submit updated copies of all required Standard
Operating Procedures (SOPs). that were submitted with the preaward Performance
Evaluation (PPE) sample results. The updated SOPs must address any and all
issues of laboratory performance and operation identified through the review
of the Performance Evaluation sample data and the evaluation of Bidder-
Supplied Documentation.
1.2 The Contractor must supply SOPs for the following:
. Sample receipt and logging;
Sample and extract storage area;
Evidentiary SOPs;
Preventing sample contamination;
Security for laboratory and samples;
Traceability/equivalency of standards;
Maintaining instrument records and bound logbooks;
Glassware cleaning;
Technical and managerial review of laboratory operation and data package
preparation;
Internal review of contractually required QA/QC data for each individual
data package;
Sample analysis, data handling, and data reporting;
Chain-of-custody and document control, including SDG file preparation;
Sample data validation/self-inspection system; and
Data flow and chain-of-command for data review;
Procedures for measuring precision and accuracy;
Evaluation parameters for identifying systematic errors;
Procedures to assure that hardcopy data are complete and compliant
with the requirements in Exhibit B;
Demonstration of internal QA inspection procedure (demonstrated by
supervisory sign-off on personal notebooks, internal PE samples,
etc.);
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Peoort Descriptions and Order of Data Deliverables Exhibit B
Frequency and. type of internal audits (e.g., random, quarterly, spot
checks, perceived trouble areas);
Demonstration of problem identification, corrective actions, and
resumption of analytical processing resulting from internal audit
(i.e., QA feedback); and
Documentation of audit reports (internal and external), response,
corrective action, etc.
Data Handling.
Data Management
a. Data Management procedures defined as written procedures that are
clearly defined for all databases and files used to generate or
re-submit deliverables specifying the acquisition or entry,
update, correction, deletion, storage, and security of computer
readable data and files. Key areas of concern include: system
organization including personnel and security, documentation,
operations, traceability, and quality control.
Data manually entered from hardcopy must be quality controlled and
error rates estimated.
Data entry rates must be estimated and recorded on a monthly basis by
re-entering a statistical sample of the data entered calculating
discrepancy rates by data element.
The record of changes in the form of corrections and updates to data
originally generated, submitted, and/or re-submitted must be
documented to allow traceability of updates. Documentation must
include the following information for each change:
a. Justification or rationale for the change;
b. Initials of the person making the change or changes. Data
changes must be implemented and reviewed by a person or group
independent of the source generating the deliverables;
c. Change documentation must be retained according to the schedule
of the original deliverable;
d. Resubmitted deliverables must be re-inspected as a part of the
laboratory's internal inspection process prior to submission.
The entire deliverable and not just the changes must be re-
inspected;
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Report Descriptions and Order of Data Deliverables
Exhibit B
e. The laboratory manager must approve changes Co originally
submitted deliverables; and
£. Documentation of data changes may be requested by laboratory
auditors.
Life Cycle Management procedures must be applied to computer systems
used to generate and edit contract deliverables. Such systems must
be thoroughly tested and documented prior to utilization;
A software test and acceptance plan including test requirements, test
results, and acceptance criteria must be developed, followed, and
available in written form;
System changes must not be made directly to production systems
generating deliverables. Changes must be made first to a development
system and tested prior to implementation;
Each version of the production system will be given an identification
number, date of installation, date of last operation, and archived;
System and operations documentation must be developed and maintained
for each system. Documentation must include a user's manual and an
operations and maintenance manual;
Individual(s) responsible for the following functions must be
identified:
a. System operation and maintenance including documentation and
-training; and
b. Database integrity including data entry, data updating and QC.
Data and system security, backup, and archiving.
2. Sample Traffic Reports
2.1 The original Sample Traffic Report (TR) page marked "Lab Copy for Return
to SHO" shall be submitted to SMO with laboratory receipt information and
signed in original Contractor signature, for each sample in the SDG.
2.2 TRs shall be submitted in SDG sets (i.e., TRs for all samples in a SDG
shall be clipped together), with a SDG Cover Sheet attached.
2.3 The SDG Cover Sheet shall contain the following items:
Lab name;
IHC01.2
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Report Descriptions and Order of Data Deliverables
ExhibitB
Contract number;
Sample Analysis Price - full sample price from contract;
Case Number; and
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), and the "last" sample received would be the
highest sample number (considering both alpha and numeric designations). For
example, AH230 is a lower sample number than AI200, as H precedes I in the
alphabet.
.
2.4 Each TR shall be clearly marked with the SDG Number, the sample number of
the first sample in the SDG. This information should be entered below the Lab
Receipt Date on the TR. The TR for the last sample received in the SDG shall be
clearly marked "SDG - FINAL SAMPLE."
2.5 If samples are received at the laboratory with multi-sample TRs, all the
samples on one multi-sample TR may not necessarily be in the same SDG. In this
instance, the laboratory shall make the appropriate number of photocopies of the
TR, and submit one copy with each SDG cover sheet.
3.
Sample Data Package
3.1 The sample data package shall be complete and consecutively paginated, and
shall include data for analysis of all samples in one SDG, including analytical
and field samples, performance evaluation sample ,(PES), sample reanalyses,
blanks, spikes, duplicates, and laboratory control samples. The sample data
package is divided into 6 units as follows:
Cover Page;
Sample Data (Sample results including the PES);
Quality Control Summary;
Raw Data;
Preparation Logs; and
Sample Traffic Reports.
3.1.1 Cover Page
3.1.1.1 This document shall be clearly labeled "Cover Page". The Cover
Page shall contain: laboratory name; laboratory code; contract number; Case No.
SDG No.; SOW number (appears on cover page of SOW); EPA sample numbers in
alphanumeric order, showing EPA sample numbers cross-referenced with lab ID
IHC01.2
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Report Descriptions and Order of Data Deliverables Exhibit_B
numbers: comments, describing in detail any problems encountered both technical
and administrative, the corrective action taken, and resolution performed for all
of Che samples in the SDG; and completion of the statement on use of ICP
background and interelement corrections for the samples.
3.1.1.2 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,
excluding the conditions detailed above. Release of the data contained in
this hardcopy data package has been authorized by the Laboratory Manager or
the Manager's designee, as verified by the following signature." This
statement shall be followed by the signature of the Laboratory Manager or
the Manager's designee with a typed line below it containing the signator's
name and title and the date of signature.
3.1.1.3 In the event that the Laboratory Manager cannot verify all
data reported for each sample, he/she must provide a detailed description of
the problems associated with the sample(s) on the Cover Page.
3.1.2 Sample data shall be submitted with FORM I-HCIN, the High ,
Concentration Inorganic Analysis Data Sheet, for all samples in the SDG
including the PES, arranged in increasing alphanumeric EPA sample number
order.
3.1.3 Quality Control Summary
3.1.3.1 The quality control summary shall contain the following forms:
NOTE: If more than one form is necessary, duplicate forms must be arranged in
chronological order.
Initial and Continuing Calibration Verification (FORM II - HCINJ
CRQL Standards/Linear Range Standards [FORM III - HCIN]
Blanks [FORM IV - HCIN]
ICP Interference Check Sample [FORM V - HCIN]
Spike Sample Recovery [FORM VI - HCIN]
Analytical Spike Sample Recovery [FORM VII - HCIN]
i
Duplicates [FORM VIII - HCINJ
Laboratory Control Sample [FORM IX - HCIN]
IHC01.2 - - Page 20
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Reporc Descriptions and Order of Data Deliverables Exhibit B
Standard Addition Results [FORM X - HCIN]
Method Detection Limits [FORM XI - HCIN]
ICP Interelement Correction Factors (Annual) (FORM XII - HCIN]
Phase Separation Log [FORM XIII - HCIN]
Preparation Separation Log [FORM XIV - HCIN]
Analysis Run Log [FORM XV - HCIN]
3.1.4 Raw Data
3.1.4.1 For each reported value, the Contractor shall include all raw
data from the instrument used to obtain the sample values (except for raw data
for quarterly verifications of instrument parameters). Raw data shall contain
all instrument readouts used for the sample results, including those readouts
that may fall below the Method Detection Limit (MDL) . All AA and ICP
instruments must provide a legible hardcopy of the direct real-time instrument
readout (i.e., stripcharts, printer tapes, etc.). A photocopy of the direct
sequential instrument readout must be included. A hardcopy of the direct
instrument readout for cyanide must be included if the instrumentation has the
capability. A stripchart is required for mercury.
3.1.4.2 The order of raw data in the data package shall be as follows:
ICP, HYICP, GFAA, mercury, cyanide, conductivity, and pH. The raw data shall
be arranged in alphabetical order per element (excluding ICP analysis) and in
chronological order as listed in section 3.1.3.1 for each method used. All
raw data must include intensities for ICP and absorbances for AA, wherever
possible.
3.1.4.3 Raw data must be labeled with EPA sample number and
appropriate codes, shown in Table 1, to identify unequivocally the following:
Calibration standards, including source and preparation date.
Initial and continuing calibration blanks and preparation blanks.
Initial and continuing calibration verification standards, interference
check samples, CRQL standard, and linear range standard.
Diluted and undiluted samples (by EPA sample number) and all weights,
dilutions and volumes used to obtain the reported values. If the
volumes, weights and dilutions are consistent for all samples in a given
SDG, then a general statement outlining these parameters is sufficient.
Duplicates.
IHC01.2 Page 21
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Report Descriptions and Order of Data Deliverables
Exhibit B
Table 1
Codes for Labeling Raw Data
Sample
Duplicate
Sample Spike
Serial Dilution
Analytical Spike
MSA:
Zero Addition
First Addition
Second Addition ^
Third Addition
Instrument Calibration Standards:
ICP . S
Atomic Absorption and Cyanide
Initial Calibration Verifications
Initial Calibration Blank
Continuing Calibration Verifications
Continuing Calibration Blanks
Interference Check Samples:
Solution A
Solution AB
CRQL Standard for ICP
Laboratory Control Samples
Preparation Blank
Linear Range Analysis Standard
XXXXXXyy
XXXXXXyyD
XXXXXXyyS
XXXXXXyyL
XXXXXXyyA
XXXXXXyyO
XXXXXXyyl
XXXXXXyy2
XXXXXXyy3
or SO for blank standard
SO, S10,...etc.
ICV
. ICB
CCV
CCB
ICSA
ICSAB
CRI
LCS
PB
LRS
Notes:
1. When an analytical spike or MSA is performed on a sample, 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 "XXXXXXyyDA".
2. The numeric suffix that follows the "S" suffix for the standards
indicates the true value for the concentration of the standard in
MS/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".
^- yy " phase identifier.
IHC01.2
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Report Descriptions and Order of Data Deliverable Exhibit B
Spikes (indicating standard solutions used, final spike concentrations,
volumes involved). If spike information (source, concentration, volume)
is consistent for a given SDG, then a general statement outlining these
parameters is sufficient.
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.
Date and EPA Sample Number for ICP, HYICP, and GFAA analyses clearly and
sequentially identified on the raw data.
All calculations for sample and analytical spike data, including percent
recovery, coefficient of variation, full MSA data, MSA correlation
coefficient, slope and y intercept of linear fit, and final sample
concentration (standard addition concentration).
» Time and date of each analysis. Instrument run logs can be submitted if
they cont-in this information. If the instrument does not automatically
provide time of analysis, the time and date must be manually entered on
all raw data for initial and continuing calibration verification and
blanks, as well as interference check samples and linear range analysis
standards.
Integration times for CVAA analysis.
3.1.5 Fusion, Digestion and Distillation Logs
3.1.5.1 Logs shall be submitted in the following order: fusion logs,
digestion logs for ICP, HYICP, GFAA and mercury preparations, followed by a
copy of the distillation logs for cyanide. These logs must include the
following:
Date of preparation;
Sample weights and volumes;
Sufficient information to identify unequivocally which QC samples (i.e.,
laboratory control sample, preparation blank) correspond to each batch
prepared; and
Comments describing any significant sample changes or reactions which
occur during preparation.
IHC01.2 page 23
L
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Report Descriptions and Ordey of Data Deliverables
Exhibit B
3.1.6 Sample Traffic Report
3.1.6.1 A legible copy of the Sample TRs and SDG Cover Sheet shall be
submitted as described in Section 2 of this Exhibit for-all of the samples in
the SDG. The TRs shall be arranged in increasing EPA sample number order,
considering both alpha and numeric designations.
4. Results of Intercomparison Study/Preaward Performance Evaluation fPPE)
Sample Analyses
4.1 The reporting of analytical results for Intercomparison Study/Preaward
Performance Evaluation (PPE) sample analyses includes all requirements
specified in item 3.1.1 for reporting of sample data. The PPE sample shall be
carried through the exact same process as an analytical and field sample.
5.
Complete SDG File
5.1 The Complete SDG File (CSF) 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 Document Inventory Sheet FORM HOC-2 (see Exhibit F 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.
5.2 Shipment of the CSF package by first class mail, overnight courier,
priority mail or equivalent is acceptable. Custody seals, which are provided
by EPA, shall be placed on shipping containers, and a document inventory and
transmittal letter shall be included. The Contractor is not required to
maintain any documents for a sample Case after submission of the Complete SDG
File package; however, the Contractor should maintain a copy of the document
inventory and transmittal letter.
6.
Quarterly and Annual Verification of Instrument Parameters
6.1 The Contractor shall perform and report quarterly verification of MDLs
by methods specified in Exhibits D and E for each type and model number of
instrument used under this contract. For the ICP instrumentation and methods,
the Contractor shall also perform and report annual interelement correction
factors (including method of determination), wavelengths used and integration
times. Annual Verification of Instrument Parameters forms for the current
year shall be submitted in each sample data package, using FORM XII-HCIN.
Submission of Quarterly Verification of Instrument Parameters shall include
the raw data used to determine those values reported.
IHC01.2
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Report Descriptions and Order of Data Deliverables Fxhibit B
7. Quality AssurancePlan (QAP)
7.1 The Contractor shall prepare a written Quality Assurance Plan (QAP)
which describes the procedures that are implemented to achieve the following:
maintain data integrity, validity, and useability; ensure that analytical
measurement systems are maintained in an acceptable state of stability and
reproducibility; detect problems through data assessment and established
corrective action procedures which keep the analytical process reliable; and
document all aspects of the measurement process in order to provide data which
are technically sound and legally defensible.
7.2 The QAP must present, in specific terms, the policies, organization,
objectives, functional guidelines, and specific QA/QC activities designed to
achieve the data quality requirements, in this contract. Where applicable,
SOPs pertaining to each element shall be included or referenced as part of the
QAP. The QAP must be available during on-site laboratory evaluation and upon
written request by the APO.
IHC01.2 Page 25
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SECTION III
FORM INSTRUCTION GUIDE
This section contains specific instructions for the completion of all
required High Concentration Inorganic Data Reporting Forms. This section is
organized into the following parts:
General Information and Header Information
Cover Page - [COVER PAGE - HCIN]
Analysis Data Sheet [FORM I - HCIN]
Initial and Continuing Calibration Verification [FORM II - HCIN]
CRQL Standards/Linear Range Standards [FORM III - HCIN]
Blanks [FORM IV - HCIN]
ICP Interference Check Sample [FORM V - HCIN]
Spike Sample Recovery [FORM VI - HCIN]
Analytical Spike Sample Recovery (FORM VII - HCIN]
Duplicates [FORM VIII - HCIN]
Laboratory Control Sample [FORM IX - HCIN]
Standard Addition Results [FORM X - HCIN]
Method Detection Limits (Quarterly) (FORM XI - HCIN]
ICP Interelement Correction Factors (Annual) [FORM XII - HCIN]
Phase Separation Log [FORM XIII - HCIN]
Preparation Log [FORM XIV - HCIN]
' Analysis Run Log [FORM XV - HCIN]
Sample Log-In Sheet [FORM HDC-1]
Document Inventory Sheet [FORM HOC-2]
1. General Information and Header Information
1.1 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. Multiple forms cannot be submitted in
place of one form if the information on those forms can be submitted on one
form.
1.2 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
follbwing the last digit to be retained equals 5 and there are no digits to
IHC01.2 Page 26
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Form Instruction Guide ; Exhibit B
the right of the 5 or all digits to the right of the 5 equal zero, then round
up if the digit to be retained is odd, or round down if that digit is even.
See also Rounding Rules entry in Glossary of Terms (Exhibit G).
1.3 All characters which appear on the data reporting forms presented in the
contract 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") on the forms must
appear as they do on the forms (Section IV), except that the use of uppercase
and lowercase letters is optional.
1.4 All alphabetic entries made onto the forms by the Contractor must be in
ALL UPPERCASE letters (i.e., "LOW", not "Low" or "low") except phase
identifiers (i.e., "wa", not "Wa" or "WA").
1.5 Six pieces of information are common to the header sections of each data
reporting form. These are: Lab Name, Contract, Lab Code, Case No., SAS No.,
and SDG No. This information must be entered on every form and must match on
all forms. " ..
1.5.1 The "Lab Name" is be the name chosen by the Contractor to identify
the laboratory. It may not exceed 25 characters.
1.5.2 The "Contract" is the number of the EPA contract, including hyphens,
under which the analyses were performed.
1.5.3 The "Lab Code" is an alphabetic abbreviation of up to 6 characters,
assigned by the EPA, to identify the laboratory and aid in data processing.
This lab code shall be assigned by the EPA at the time a contract is awarded,
and must not be modified by the Contractor, except at the direction of EPA.
If a change of name or ownership occurs at the laboratory, the lab code will
remain the same until the Contractor is directed by the EPA to use another lab
code assigned by the EPA.
1.5.4 The "Case No." is the EPA-assigned Case number (up to 5 characters)
associated with the sample and recorded on the TR. * :
1.5.5 The "SAS No." is the EPA-assigned number for analyses performed under
Special Analytical Services (SAS). 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, then 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 a SDG may have a SAS No., while others may
not.
IHC01.2 Page 27
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Form Instruction Guide
Exhibit B
1.5.6 The "SDG No." is Che Sample Delivery Group (SDG) number. The ,SDG
number is the EPA Sample Number of the first sample received in the SDG. When
several samples are received together in the first SDG shipment, the SDG
number must be the lowest sample number (considering both alpha and numeric
designations) in the first group of samples received under the SDG.
1.6 EPA Sample Number
1.6.1 The EPA Sample Number is the unique identifying number given in the
TR that accompanied that sample. This number is assigned by the EPA and it
must be used exactly as assigned.
1.6.2 The "EPA SAMPLE NO." must be entered on several of the forms. 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 the
"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.
1.6.3 All field samples and quality control samples associated with field
samples must be identified with an EPA Sample Number.
1.6.4 The phase suffix is assigned to each phase by appending a unique two
letter identifier with the first letter identifying the phase, and the second
identifying the number of phases of that type. These identifiersshall be
only in lower case letters. These identifiers are as follows: a "w" for
water miscible, "c" for solid, and "n" for non-water miscible with the second
values ranging from a through z. If the sample consists of a water miscible
phase, then the phase suffix must be a "wa". If the sample consists of more
than one phase such as a water miscible phase, a solid phase, and a non-water
miscible phase, then the water miscible phase suffix must be a "wa", the solid
phase suffix must be a "ca", and the non-water miscible must be a "na".
1.6.5 In addition, the sample suffix and quality control sample
abbreviations listed in Table 1, Section II of this Exhibit, must be used as
appropriate.
1.7 All results must be transcribed to FORMs II-XIII from the raw data with
the specified number of decimal places that are described in this Exhibit.
The raw data result is to be rounded only when the number of figures in the
raw data result exceeds the maximum number of figures specified for that
result entry for that form. If there are not enough figures in the raw data
result to enter in the specified space for that result, then zeros must be
used for decimal places to the specified number of reporting decimals for that
result for a specific form. The following examples are provided:
IHC01.2
Page 28
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Form Instruction Guide- - Exhibit B
Raw Data Result Specified Format Correct Entry on Form
5.9
5.99653
95.99653
995.99653
9995.996
99995.9
999995.9
6.3
6.3
6.3
6.3
6.3
6.3
6.3
5.900
5.997
95.997 . .
996.00
9996.0
99996.
invalid
NOTE: 6.3 stands for a maximum of six significant figures and up to three
decimal places.
1.8 Before evaluating a number for being in control or out of control in
relationship to 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 ± 10 percent of the true value. A percent
recovery value of 110.4 would be considered in control while a'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 110.55 would be out of
control.
2. Cover Page [Cover Page - HCIN]
2.1 This form is used to list all billable sample phases analyzed within an
SDG, 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.
2.2 Complete the header information according to the previous instructions.
2.3 The "SOW No." is the EPA-designated number that indicates the Statement
of Work (SOW) under which analyses in the data package have been performed.
The SOW No. appears on the cover of the contract Statement of Work. For
samples analyzed using this SOW, enter IHC01.1 for "SOW No."
2.4 Under "EPA Sample No.", enter up to 10 characters for the EPA Sample No.
(including spikes and duplicates) for each phase that required analysis within
the SDG. Spikes must contain an "S" suffix and duplicates a "D" suffix.
These sample numbers must be listed on the form in ascending alphanumeric
order using the EBCDIC convention. Thus, if MAB123A is the lowest
(considering both alpha and numeric characters) EPA Sample No. within the SDG,
it would be entered in the first EPA Sample No. field. Samples listed below
it would be in ascending sequence - MAB124A, MAB124B, MAB125A, MAC111A,
MA1111A, MA1111AD, etc.
2.5 All EPA Sample Numbers must be listed in ascending alphanumeric order,
continuing to the following Cover Page if applicable.
IHC01.2 Page 29
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Form Instruction Guide
Exhibit B
2.6 Under "Lab Sample ID", a Lab Sample ID (up to 10 characters) may be
entered for each associated EPA Sample No. If a Lab Sample ID is entered, it
must be entered identically (for each EPA Sample No.) on all associated data.
2.7 Enter "Y" or "N" for "YES" or "NO", respectively, in answer to each of
the two questions concerning ICP corrections. Each question must be
explicitly answered with a "Y" or an "N". The third question must be answered
with a "Y" or "N" if the answer to the second question is
left blank if the answer to the second question is "N".
It should be
2.8 Under "Comments", enter any problems encountered, both technical and
administrative, the corrective action taken, and resolution performed for all
of the samples in the SDG.
2.9 Each-.Coyer 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 wi.th an SDG.
3.
Analysis Data Sheet [FORM I - HCIN]
3.1 This form is used to tabulate and report sample analysis results for
target analytes (Exhibit C).
3.2 Complete the header information according to the header instructions and
as follows.
3.3 For "Phase", enter the phase that describes the sample. The phase may
be only "SOLID", "WATER MISCIBLE", or "NON-WATER MISCIBLE". Additional
descriptions that can better characterize the sample may be listed in the
comments section.
3.4 For "Water Miscibility", enter "YES" if the phase of the sample listed
is water miscible, "NO" if the phase is non-water miscible and "PART" if the
phase is partially water miscible. If the sample phase is not a liquid, then
leave the field empty.
3.5 For "Percent", enter the percent (to two decimal places) of total sample
that the phase reported constitutes of the total sample weight calculated as
follows:
Percent -
Phase Weight in Grams
Total Sample Weight in Grams
x 100
NOTE: The percent listed on the form for a phase of a sample must equal that
which is listed for that phase on FORM XIII-HCIN.
4ft
IHC01.2
Page 30
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Form Instruction Guide
Exhibit B
3.6 For "pH", enter the pH value obtained (to the nearest tenth of a whole
number) for the water miscible phase listed on the form.
3.7 For "Conductivity", enter the conductivity value (to the nearest whole
number) for the water miscible phase listed on the form.
3.8 For "Lab Sample ID", enter the lab sample ID for the phase listed on the
form, as listed on the Cover Page.
3.9 For "Date Received" enter the date (formatted MM/DD/YY) the sample was
received at the laboratory, as recorded on the TR, i.e., the Validated Time of
Sample Receipt (VTSR).
3.10 Under the column labeled "CONCENTRATION", if the analytical result is
greater than or equal to the Kethod Detection Limit (MDL), report the result.
If the result is lower than the MDL, report the MDL value.
3.11 Analytical results must be reported to two significant figures in mg/Kg
if the result value is less than 10, and to three significant figures if the
result value is greater than or equal to 10.
3.12 The requirement for reporting results to two or three significant
figures applies to FORM I-HCIN only. Follow the specific instructions for
reporting all other results on required forms as described in this Exhibit.
3.13 Under the columns labeled "C", "Q", and "M", enter result qualifiers as
identified in items 3.14.1, 3.14.2, and 3.14.3. If additional qualifiers are
used, their explicit definitions must be included on the Cover Page in the
Comments section.
3.14 FORM I-HCIN includes fields for three types of result qualifiers.
qualifiers must be completed as follows:
These
3.14.1 C (Concentration) qualifier: Enter "B" if the reported value was
obtained from a reading that was less than the Contract Required Quantitation
Limit (CRQL) but greater than or equal to the MDL. Enter "U" if the reported
value was obtained from a reading that was less than the MDL.
3.14.2 Q (Quality Control) qualifier: Specified entries and their meanings
are as follows:
E - The reported value is estimated because of the presence of
interference.
I The sum of the values of the interference correction(s) is
greater than the result concentration.
M - Duplicate injection/exposure precision not met.
IHC01.2
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Form Instruction Guide
Exhibit B
N - Spiked sample recovery not within control limits.
S - The reported value was determined by the Method of Standard
Additions (MSA).
* * - Duplicate analysis not within control limits.
+ - Correlation coefficient for the MSA is less than 0.995.
NOTE: Entering "S" or "+" is mutually exclusive. No combination of these
qualifiers can appear in the same field for an analyte.
3.14.3 M (Method) qualifier: Enter, as appropriate, the following:
"P" for ICP;
"H" for HYICP;
"F" for Graphite Furnace AA;
"CV" for Manual Cold Vapor AA;
«AV" for Automated Cold Vapor AA;
"AS" for Semi-automated Spectrophotometric;
"C" for Manual Spectrophotometric; and
"NR" if the analyte is not required to be analyzed.
3.IS A'brief physical description of the sample must be reported in the
fields for "Color", "Clarity", "Texture", "Viscosity", and "Artifacts". For
liquid samples, report color, clarity, and viscosity. For solid samples,
report color, texture and artifacts.
3.16 Listed below are the only descriptive terms available for the specified
criteria:
Color
red, blue, yellow, green, orange,-violet, white, colorless,
brown, grey, or black.
Clarity - clear, cloudy, or opaque.
Viscosity - nonviscous (similar to water) or viscous.
Texture - fine (powdery), medium (sand), or coarse (large crystals or
rocks).
3.17 If artifacts are present, enter "YES" in the artifacts field and '
describe the artifacts in the Comments field. If artifacts are not present,
enter "NO".
IHC01.2
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Form Instruction Guide : Exhibit B
3.18 Under "Comments", enter any sample-specific comments concerning the
analyte results and note any significant changes that occurred during sample
analysis (i.e., MSA determination, interferences), both technical and
administrative, the corrective action taken, and resolution performed for t.;e
sample in the SDG.
4. Initial and ContinuingCalibration Verification [FORM II - HCIN]
4.1 This form is used to report analyte recoveries from analyses of
calibration solutions.
4.2' Complete the header information according to the header instructions and
as follows,
4.3 Enter the "Initial Calibration Source" (12 characters maximum) and the
"Continuing Calibration Source" (12 characters maximum). Enter "EPA-LV" or
"EPA-CI" to indicate EPA EMSL-Las Vegas or EMSL-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.
4.4 , Use additional copies of FORM II-HCIN if more calibration sources were
used.
4,5 Under "WAVE", enter the number of the wavelength for which the results
of each analyte are reported on the form. The wavelength number is a number
assigned to each wavelength used when more than one wavelength is used to
obtain data for an analyte in the SDG. A wavelength number of "1" is assigned
to the longest wavelength used for the analyte in the SDG. A wavelength
number of "2" is assigned to the second longest wavelength and so on. The
field must be left blank if a single wavelength is used to obtain data for an
analyte in the SDG.
4.6 Under "INITIAL CALIBRATION True", enter the true concentration (in mg/L,
to three decimal places) of each analyte in the Initial Calibration
Verification Solution.
4.7 Under "INITIAL CALIBRATION Found", enter the most recent found
concentration (in mg/L, to three decimal places), of each analyte measured in
the Initial Calibration Verification Solution.
4.8 Under "INITIAL CALIBRATION %R", enter the value (to the nearest whole
number) of the percent recovery computed according to the following equation:
IHC01.2 Page 33
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Form Instruction Guide
Exhibit B
%R -
Found (ICV)
True (ICV)
x 100
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.
4.9 Under "CONTINUING CALIBRATION True", enter the true concentration (in
mg/L, to three decimal places) of each analyte in the Continuing Calibration
Verification Solution.
4.10 Under "CONTINUING CALIBRATION Found", enter the found concentration (in
mg/L, to three decimal places) of each analyte measured in the Continuing
Calibration Verification Solution.
NOTE: 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.
4.11 If more than one FORM II-HCIN 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.
4.12 Under "CONTINUING CALIBRATION %R", enter the value (to the nearest whole
number) of the percent recovery computed according to the following equation:
%R -
Found (ICV)
True (ICV)
x 100
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.
NOTE: The form contains two "CONTINUING CALIBRATION XR" columns. Entries to
these columns must follow the sequence detailed above for entries to the
"Continuing Calibration Found" columns.
4.13 Under "M" , enter the method used as in item 3.14.3.
4.14 If more than one wavelength is used to analyze an analyte, then submit
additional copies of FORM II-HCIN as appropriate.
IHC01.2
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Form InstructionGuide
Exhibit B
4.15 The order of reporting ICVs and CCVs for each analyte must follow the
chronological order in which the standards were run starting with the first
FORM II-HCIN and moving from the left to the right continuing to the following
FORM II-HCIN as appropriate. For instance, the first ICV for all analytes
must be reported on the first FORM II-HCIN. In a run where three CCVs were
analyzed, the first CCV must be reported in the left CCV column on the first
FORM II-HCIN 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 II-HCIN. On the second FORM II-HCIN, the ICV column and the right
CCV column must be left empty in this example. In the previous example, if a
second run for an analyte was needed, the ICV of that run must be reported on
a third FORM II-HCIN and the CCVs follow in the same fashion as explained
before.
4.16 In the case where more than one wavelength is used for an analyte in the
SDG, all ICV and CCV results of the longest wavelength from all runs must be
reported before proceeding to report the results of the second wavelength used
and so on.
4.17 Under "Comments", enter any ICV and CCV specific comments concerning the
analyte results, any significant problems encountered during the ICV and CCV
analysis (i.e., percent recovery outside the control limits, interferences),
both technical and administrative, the corrective action taken, and resolution
performed for the ICV and CCV.
5. Contract Required Quantitation Limit Standards/Linear Range Standards
[FORM III-HCIH]
5.1 Contract Required Quantitation Limit Standard
5.1.1 This form is used to report analyte recoveries from analyses of the
Contract Required Quantitation Limit (CRQL) Standards.
5.1.2 Complete the header information according to the header instructions
and as follows.
5.1.3 Under "CRQL", enter the source of the CRQL Standard for TCP, HYICP,
GFAA, cyanide, and mercury analyses in their respective fields (12 characters
maximum each), as explained in item 4.3.
5.1.4 Under "WAVE", enter the wavelength number as explained in item 4.5.
5.1.5 Under "INITIAL Trv ", enter the true concentration (in mg/L, to three
decimal places) of each analyte in the CRQL Standard Source Solution that was
analyzed for analytical samples associated with the SDG.
IHC01.2
Page 35
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Fori" Instruction Guide
Exhibit B
5.1.6 Under "INITIAL Found", enter the found concentration (in mg/L, to
three decimal places) of each analyte measured in the CRQL Standard Solution
analyzed at the beginning of each run.
5.1.7 Under "INITIAL XR", enter the value (to the nearest whole number) of
the percent recovery computed according to the following equation:
%R -
CROL Standard InitialFound
CRQL Standard True
x 100
5.1.8 Under "FINAL Found", enter the found concentration (in mg/L, to three
decimal places) of each analyte measured in the CRQL Standard Solution
analyzed at the end of each run.
5.1.9 Under "FINAL %R", enter the value (to the nearest whole number) of
the percent recovery computed according to the following equation:
%R -
CROL
Standard Final Found
CRQL Standard True
x 100
NOTE: For every initial solution reported there must b'e a final one.
However, the opposite is not true. If a CRQL Standard 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.
5.1.10 If more CRQL standards analyses were required or analyses were
performed using more than one wavelength per analyte, submit additional copies
of FORM II-HCIN in the appropriate order.
5.1.11 The order of reporting CRQL standards for each analyte must follow
the chronological order in which the standards were run starting with the
first FORM III-HCIN and continuing to the following FORM III-HCIN as
appropriate. When multiple wavelengths are used for one analyte, all the
results of one wavelength must be reported before proceeding to the next
wavelength.
5.1.12 Under "Comments", enter any CRQL-specific comments concerning the
analyte results, any significant problems encountered during the CRQL standard
analysis (i.e., percent recovery outside -the control limits), both technical
and administrative, the corrective action taken, and resolution performed for
the standard.
5.2 Linear Range Standard.
5.2.1 -This form is used to report analyte recoveries from analyses of the
Linear Range Standards (LRSs).
IHC01.2
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Form Instruction Guide Exhibit B
5.2.2 Complete the header information according to the header instructions
and as follows.
5.2.3 Under "LRS", enter the source of the Linear Range Standards for ICP,
HYICP, GFAA, cyanide and mercury analyses in their respective fields (12
characters maximum each), as explained in item 4.3.
5.2.4 Under "WAVE", enter the wavelength number as explained in item 4.5.
5.2.5 Under "INITIAL True", enter the true concentration (in mg/L, to three
decimal places) of each analyte in the LRS Source Solution that was analyzed
for the analytical samples associated with the SDG.
5.2.6 Under "INITIAL Found", enter the found concentration (in mg/L,- to
three decimal places) of each analyte measured in the LRS Solution analyzed at
the beginning of each run.
5.2.7 Under "INITIAL ZR", enter the value (to the nearest whole number) of
the percent recovery computed according to the following equation:
LRS Initial Found ., AA
%R ' LRS True X 10°
5.2.8 Under "FINAL Found", enter the found concentration (in mg/L, to three
decimal places) of each analyte measured in the LRS Solution analyzed at the
end of each run.
5.2.9 Under "FINAL %R", enter the value (to the nearest whole number) of
the percent recovery computed according to the following equation:
_ LRS Final Found ,nn
%R - , __ _ x 100
LRS True
NOTE: For every initial solution reported there must be a final one.
However, the opposite is not true. If an LRS 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.
5.2.10 If more LRS analyses were required or analyses were performed using
more than one wavelength per analyte, submit additional copies of FORM
III-HCIN in-the appropriate order.
5,2.11 The order of reporting the LRS for each analyte must follow the
chronological order in which the standards were run starting with the first
FORM III-HCIN and continuing to the following FORM III-HCIN as appropriate.
If multiple wavelengths are used for one analyte, all the results of one
wavelength must be reported before proceeding to the next wavelength.
IHC01.2 Page 37
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Form Instruction Guide
Exhibit B
5.2.12 Under "Comments", enter any LRS-specific comments concerning the
analyte results, any significant problems encountered during the LRS analysis
(i.e., percent recovery outside the control limits), both technical and
administrative, the corrective action taken, and resolution performed for the
standard.
6.
Blanks [FORM IV - HCIN]
6.1 This form is used to report analyte concentrations found in the Initial
Calibration Blank (ICB), the Continuing Calibration Blanks (CCB), and the
Preparation Blank (PB).
6.2 Complete the header information according to the header instructions and
as follows.
6.3 Under "WAVE", enter the wavelength number for which the results of each
analyte are reported on the form. The wavelength number is a number assigned
to each wavelength used when more than one wavelength is used to obtain data
for an analyte in the SDG. A wavelength number of "1" is assigned to the
longest wavelength used for the analyte in the SDG. A wavelength number of
"2" is assigned to the second longest wavelength and so on. The field must be
left blank if a single wavelength is used to obtain data for an analyte in the
SDG.
6.4 Under "INITIAL CALIB. BLANK", enter the concentration (in mg/L, to three
decimal places) of each analyte in the most recent Initial Calibration Blank
(ICB).
6.5 For all blanks, enter the concentration of each analyte (positive or
negative) measured above the MDL or below the negative value of the MDL.
6.6 Under the "C" qualifier field, for any analyte enter "B" if the absolute
value of the analyte concentration is less than the CRQL but greater than or
equal to the MDL. Enter "U" if the absolute value of the analyte in the blank
is less than the MDL.
6.7 Under "CONTINUING CALIBRATION BLANK 1", enter the concentration (in
mg/L, to three decimal places) of each analyte detected in the first required
Continuing Calibration Blank (CCB) analyzed after the Initial Calibration
Blank (ICB). Enter any appropriate qualifier, as explained for the "Initial
Calibration Blank", in the "C" qualifier column immediately following the
"CONTINUING CALIBRATION BLANK 1" column.
6.8 If only one Continuing Calibration Blank was analyzed, then leave the
columns labeled "2" and "3" blank. If up to three CCBs were analyzed,
complete the columns labeled "2" and "3", in accordance with the instructions
IHC01.2
Page 38
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Form Instruction Guide Exhibit B
for Che "CONTINUING CALIBRATION BLANK 1" column. If more than three
Continuing Calibration Blanks were analyzed, then complete additional copies
of FORM IV-HCIN as appropriate.
6.9 Under "PREPARATION BLANK", enter the concentration (in mg/Kg, to three
decimal places) of each analyte in the Preparation Blank. Enter any
appropriate qualifier, as explained for the Initial Calibration Blank, in the
"C" qualifier column immediately following the "PREPARATION BLANK" column.
6.10 Under "M", enter the method used, as explained in item 3.14.3. .
6.11 If more than one wavelength is used to analyze an analyte, submit
additional copies of FORM IV-HCIN as appropriate.
6.12 The order of reporting ICBs and CCBs for each analyte must follow the
chronological order in which the blanks were run starting with the first FORM
IV-HCIN and moving from left to right and continuing to the following FORK IV-
HCIN as explained previously. When multiple wavelengths are used for the
analysis of one analyte, all the results of one wavelength must be reported
before proceeding to the next wavelength.
6.13 Under "Comments", enter any ICB and CCB specific comments concerning the
analyte results, any significant problems encountered during the ICB, CCB and
PB analysis (i.e., blanks outside the control limits), both technical and
administrative, the .corrective action taken, and resolution performed for the
sample.
7. ICP Interference Check Sample [FORM V - HCIN]
7.1 This form is used to report ICP Interference Check Sample (ICS) results
for each ICP instrument used in SDG analyses.
7.2 Complete the header information according to the header instructions and
as follows.
7.3 For "ICP ID No.", enter an identifier that uniquely identifies the
specific instrument within the Contractor laboratory. No two ICP instruments
within a laboratory may have the same ICP ID Number.
7.4 For "ICS Source", enter the ICS source (12 characters maximum each), as
previously explained in item 4.3. For EPA solutions, include the name and
number identifying it (e.g., EPA-LV87). The laboratory must use the
identification supplied by the EPA.
7.5 Under "WAVE", enter the wavelength number for which the results of each
analyte are reported on the form. The wavelength number is a number assigned
IHC01.2 . Pag3 39
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Form Instruction Guide
Exhibit B
to each wavelength used when more than one wavelength is used to obtain data
for an analyte in the SDG. A wavelength number of "1" is assigned to the
longest wavelength used for the analyte in the SDG. A wavelength number of
"2" is assigned to the second longest wavelength and so on. the field must be
left blank if a single wavelength is used to obtain data for an analyte in the
SDG.
7.6 Under "TRUE Sol. A", enter the true concentration (in. mg/L, to three
decimal places) of each analyte present in Solution A.
7.7 Under "TRUE Sol. AB" , enter the true concentration (in mg/L, to three
decimal places) of each analyte present in Solution AB.
7.8 Under "INITIAL FOUND Sol, A", enter the found concentration (in mg/L, to
three decimal places) of each analyte measured in the initial analysis 'of
Solution A as required in Exhibit E,
7.9 Under "INITIAL FOUND Sol. AB", enter the found concentration (in mg/L,
to three decimal places) of each analyte measured in the initial analysis of
Solution AB as required in Exhibit E.
7.10 Under "INITIAL FOUND ZR", enter the value (to the nearest whole number)
of the percent recovery computed according to the following equation:
Initial Found Solution AB
m t * n
True Solution AB
inn
JLUU
7.11 Under "FINAL FOUND Sol. A", enter the found concentration (in mg/L, to
three decimal places) of each analyte measured in the final analysis of
Solution A as required in Exhibit E.
7.12 Under "FINAL FOUND Sol. AB" , enter the found concentration (in mg/L, to
three decimal places) of each analyte measured in the final analysis of
Solution AB as required in Exhibit E.
7.13 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.
7.14 Under "FINAL FOUND %R" , enter the value (to the nearest whole number) of
the percent recovery computed according to the following equation:
Final Found Solution AB
' m MI* ..n
True Solution AB
, nn
J.UU
IHC01.2
Page 40
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Form Instruction Guide Exhibit B
NOTE: 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.
7.15 If more ICS analyses were required, submit additional copies of FORM
V-HCIN as appropriate.
7.16 The order of reporting ICSs for each analyte must follow the temporal
order in which the standards were run starting with the first FORM V-HCIN and
continuing to the following FORM V-HCIN as appropriate. When multiple
wavelengths are used for one analyte, all the results of one wavelength must
be reported before proceeding to the next wavelength in the same manner.
7.17 Under "Comments", enter any ICS specific comments concerning the analyte
results, any significant problems encountered during the ICS analysis (i.e.,
percent recovery outside the control limits), both technical and
administrative, the corrective action taken, and resolution performed for the
sample.
8- Soike Sample Recovery [FORM VI - HCIN]
8.1 This form is used to report results for the spike sample recovery which
is based on the addition of a known quantity of analyte to the pre-digest
sample.
8.2 Complete the header information according to the header instructions and
as follows.
8.3 In the "EPA SAMPLE NO." box, enter the EPA Sample Number (10 characters
maximum) of the sample from which the spike results on this form were
obtained. The number must be centered in the box. Note that the EPA Sample
No. must include the phase suffix and spike sample suffix for which the spike
analyses are reported.
8.4 For "Phase", enter the phase identifier that describes the sample listed
on this form.
8.5 For "Percent", enter the percent of the phase that constitutes the
sample listed on this form.
NOTE: The entries for both "Phase" and "Percent" on this form must be
identical to the entries made on FORM I-HCIN for the same sample.
8.6 Under "WAVE", enter the wavelength number for which the results of each
analyte are reported on the form. The wavelength number is a number assigned
IHC01.2 Page 41
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Form Instruction Guide
Exhibit B
Co each wavelength used when more than one wavelength is used to obtain data
for an analyte in the SDG. A wavelength number of "1" is assigned to the
longest wavelength used for the analyte in the SDG. A wavelength number of
"2" is assigned to the second longest wavelength and so on. The field must be
left blank if a single.wavelength is used to obtain data for an analyte in the
SDG.
\
8.7 Under "CONTROL LIMIT %Rn, enter "75-125" if the spike added value was
greater than or equal to one-fourth of the sample result value. If not, leave
the field empty.
8.8 Under "SPIKED SAMPLE RESULT (SSR)", enter the concentration (in mg/Kg,
to three decimal places) of each analyte in the spike sample. Enter any
appropriate qualifier in the "C" qualifier column immediately following the
Spiked Sample Result (SSR) column.
8.9 Under "SAMPLE RESULT (SR)", enter the concentration (in mg/Kg, to three
decimal places) of each analyte measured in the sample (reported in the EPA
Sample No. box) on which the matrix spike was performed. Enter any
appropriate qualifier in the "C" qualifier column immediately following the
Sample Result (SR) column.
8.10 Under "SPIKE ADDED (SA)", enter the concentration (in mg/Kg, to three
decimal places) of each analyte added to the sample. If the "Spike Added"
concentration is specified in the contract, the value added and reported must
be that specific concentration in mg/Kg.
8.11 Under "%R", enter the value (to the nearest-whole number) of the percent
recovery computed according to'the following equation:
(SSR -
SA
x 100
NOTE: %R must be reported, whether it is negative, positive or zero. A
value of zero must be used for SSR or SR if the analyte value is less than the
MDL.
8.12 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).
8.13 Under "M", enter the method used or enter "NR" if the analyte is not
required in the spike.
NOTE: If different samples (of the same phase) were used for spike sample
analysis of different analytes, additional copies of FORM VI-HCIN must be
submitted for each sample as appropriate.
IHC01.2
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Form Instruction Guide
Exhibit B
8.14 Use additional copies of FORM VI-HCIN for each sample phase type on
which a required spike sample analysis was performed.
8.15 Under "Comments", enter any spike sample specific comments concerning
the analyte results, any significant problems encountered during the spike
sample analysis (i.e., percent recovery outside the control limits), both
technical and administrative, the corrective action taken, and resolution
performed for the sample.
9. Analytical Spike Sample Recovery [FORM VII - HCIH]
9.1 This form is used to report results for the analytical spike recovery
which is based upon the addition of a known quantity of analyte to an aliquot
of the digested sample.
9.2 Complete the header information according to the header instructions and
as follows.
9.3 For "Phase",
on this form.
enter the phase identifier that describes the sample listed
9.4 For "Percent", enter the percent of the phase that constitutes the
sample listed on this form.
NOTE: The entries for both "Phase" and "Percent" on this form must be
identical to the entries made on FORM I-HCIN for the same sample.
9.5 Under "WAVE", enter the wavelength number for which the results of each
analyte are reported on the form. The wavelength number is a number^assigned
to each wavelength used when more than one wavelength is used to obtain data
for an analyte in the SDG. A wavelength number of "1" is assigned to the
longest wavelength used for the analyte in the SDG. A wavelength number of
"2" is assigned to the second longest wavelength and so on. The field must be
left blank if a single wavelength is used to obtain data for an analyte in the
SDG.
9.6 In the "EPA SAMPLE NO." box, enter the EPA Sample Number (10 characters
maximum) of the sample from which the spike results on this form were
obtained. The number must be centered in the box. Note that the EPA Sample
No. must include the phase suffix and spike sample suffix for which the spike
analyses are reported.
9.7 Under "CONTROL LIMIT %R" and "Q", the fields must be left blank until
limits are established by the EPA. At that time, the Contractor will be
informed on how to complete these fields.
IHC01.2
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Form Instruction Guide
Exhibit B
9.8 Under "SPIKED SAMPLE RESULT (SSR)", enter the concentration (in mg/L, to
three decimal places), for each analyte in the analytical spike sample. Enter
any appropriate qualifier in the "C" qualifier column immediately following
the Spiked Sample Result (SSR) column.
9.9 Under "SAMPLE RESULT (SR)n, enter the concentration (in mg/L, to three
decimal places) , for each analyte measured in the sample (reported in the EFA
Sample No. box) on which the analytical spike was performed. Enter any
appropriate qualifier in the "C" qualifier column immediately following the
"SAMPLE RESULT (SR)" column.
9.10 Under "SPIKE ADDED (SA)", enter the concentration (in mg/L, to three
decimal places) of each analyte added to the sample. If the spike added
concentration is specified in the contract, the concentration added and
reported must be that specific concentration in mg/L.
9.11 Under "2R", enter the value (to the nearest whole number) of the percent
recovery for all spiked analytes computed according to the tol1 owing equation:
%R -
x 100
9.12 ZR must be reported, whether it is negative, positive, or zero.
9.13 A value of zero must be substituted for SSR or SR if the analyte
.concentration is less than the MDL.
9.14 Under "M" , enter the method used or enter "NR" if the analyte is not
required in the spike.
9.. 15 If different samples (of the same phase) were used for spike sample
analysis of different analytes, additional copies of FORM VII-HCIN must be
submitted for each sample as appropriate .
9.16 Use additional copies of FORM VII-HCIN for each sample phase type on
which a required spike sample analysis was performed.
9.17 Under "Comments", enter any analytical spike sample specific comments
concerning the analyte results, any significant problems encountered during
the analytical spike sample analysis (i.e., percent recovery outside the
control limits), both technical and administrative, the corrective action
taken, and resolution performed for the sample.
10. Duplicates [FORM VIII - HCIN]
10.1 This form is used to report results of duplicate analyses for
determining the precision of the method. '\ . . .
IHC01.2
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Form Instruction Guide Exhibit B
10.2 Complete the header'information according to the header instructions and
as follows.
10.3 In the "EPA SAHPLE NO." box, enter the EPA Sample Number (10 characters
maximum) of the sample from which the duplicate results on this form were
obtained. The number must be centered in the box. NOTE: The EPA Sample No.
must include the phase suffix and duplicate sample suffix for which the
duplicate analyses are reported.
10.4 For "Phase", enter the phase description of the sample reported on this
form.
10.5 For "Sample Percent", enter the percent of the phase that constitutes
the sample reported on this form. Note that this' percent must be identical to
the entry made on FORM I-HCIN on which the initial analysis is made.
10.6 For "Duplicate Percent", enter the percent of the phase that constitutes
the duplicate sample reported on this form.
10.7 Under "WAVE", enter the wavelength number for which the results of each
analyte are reported on the form. The wavelength number is a number assigned
to each wavelength used when more than one wavelength is used to obtain data
for an analyte in the SDG. A wavelength number of "1" is assigned to the
longest wavelength used for the analyte in the SDG. A wavelength number of
"2" is assigned to the second longest wavelength and so on. The field must be
left blank if a single wavelength is used to obtain data for an analyte in the
SDG.
10.8 Under "CONTROL LIMIT XR", enter the numerical value of the CRQL (in
mg/Kg) for the analyte if the sample or duplicate values were less than 5x
CRQL. If the sample and duplicate values were less than the CRQL or greater
than or equal to 5x CRQL, leave the field empty.
10.9 Under "SAMPLE (S)", enter the concentration (in mg/Kg, to three decimal
places) of each analyte in the original sample (reported in the EPA Sample No.
box) on which a duplicate analysis was performed. Enter any appropriate
qualifier in the "C" qualifier column immediately following the "SAMPLE (S)"
column,
10.10 Under "DUPLICATE (D)", enter the concentration (in mg/Kg, to three
decimal places) of each analyte measured in the Duplicate sample (reported in
the EPA Sample No. box). Enter any appropriate qualifier in the "C" qualifier
column immediately following the "DUPLICATE (D)" column.
10.12 For all samples, the concentration of the original sample must be
computed using the weight and "Sample Percent" of the original sample. The
concentration of the duplicate sample must be computed using the weight and
"Duplicate Percent" of the duplicate sample.
IHC01.2 Page 45
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Form Instruction Gufde,
10.13 Under "RF.D" , enter the absolute value (to the nearest whole number) of
the Relative Percent Difference for all analytes detected above the MDL in
either the sample or the duplicate, computed according to the following
equation:
10.14 A value of zero must be substituted for S or D if the analyte
concentration is less than the MDL in either one. If the analyte
concentration is less than the MDL in both S and D, leave the RPD field empty.
10.15 Under "Q", enter "*" if the duplicate analysis for the analyte is out of
the control limits. If both sample and duplicate values are greater than or
equal to 5x CRQL, then the RPD must be less than or equal to 20X to be in
control. If either sample or duplicate values are less than 5x CRQL, then the
absolute difference between the two values must be less than or equal to the
CRQL to be in control. If both values are below the CRQL, then no control
limit is applicable.
10.16 Under "M" , enter the method used.
10.17 If different samples (of the same phase) were used for duplicate sample
analysis of different analytes, then additional copies of FORM VIII -HCIN must
be submitted for each sample as appropriate.
10.18 Use additional copies of FORM VII I -HCIN for each sample phase type on
which a required duplicate sample analysis was performed.
10.19 Under "Comments", enter any duplicate sample- specif ic comments
concerning the analyte results, any significant problems encountered during
the duplicate sample analysis (i.e., percent recovery outside the control
limits), both technical and administrative, the corrective action taken, and
resolution performed for the sample.
11. Laboratory Control Sample [FORM IX - HCIN]
11.1 This form is used to report results for the specified High Concentration
Laboratory Control Sample (LCS).
11.2 Complete the header information according to the header instructions and
as follows.
11.3 For "ICP Source", enter the appropriate identifier (12 characters
maximum) provided by the EPA for the LCS solution that was analyzed by ICP.
The same criteria applies to the sources of the standards for the other
methods such as HYICP, GFAA, cyanide and mercury.
IHC01.2
Page 46
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Form Instruction Guide _ Exhibit B
11.4 If no analytes were analyzed by a certain method or if the analyte was
not required to be analyzed, then leave the appropriate spaces empty.
11.5 Under "WAVE", enter the wavelength number for which the results of each
analyte are reported on the form. The wavelength number is a number assigned
to each wavelength used when more than one wavelength is used to obtain data
for an analyte in the SDG. A wavelength number of "1" is assigned to the
longest wavelength used for the analyte in the SDG. A wavelength number of
"2" is assigned to the second longest wavelength and so on. The field must be
left blank if a single wavelength is used to obtain data for an analyte in the
SDG..
11.6 Under "LIMITS", enter the lower limit (in mg/Kg, to the nearest whole
number) in the left column, and the upper limit (in mg/Kg, to the nearest
whole number) in the right column for each analyte in the High Concentration
LCS.
11.7 Under "TRUE", enter the true concentration (in mg/Kg, to three decimal
places) of each analyte in the High Concentration LCS.
11.8 Under "FOUND", enter the found concentration (in mg/Kg, to three decimal
places) of each analyte measured in the High Concentration LCS.
11.9 Under "C" ," enter "B" or "U" or leave empty to describe the found value
of the LCS.
11.10 Under "XR", enter the value (to the nearest whole number) of the percent
recovery computed according to the following equation:
LCS True
11.11 If the analyte concentration is less than the MDL, a value of zero must
be substituted for the LCS Found.
11.12 Submit additional copies of FORM IX-HCIN as appropriate, if more than
one LCS was required. In addition, submit additional copies of FORM IX-HCIN
if more than one wavelength was used to determine an analyte for a sample
phase type.
11.13 Under "Comments", enter any LCS specific comments concerning the analyte
results, any significant problems encountered during the LCS analysis (i.e.,
percent recovery outside the control limits) , both technical and
administrative, the corrective action taken, and resolution performed for the
sample .
IHC01.2 Page 47
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Form Instruction Guide
Exhibit B
12. Standard Addition Results [FORM X - HCIN]
12.1 This form is used to report the results of samples analyzed using the
Method of Standard Additions (MSA).
12.2 Complete the header information according to the header instructions and
as follows.
12.3 Under "EPA SAMPLE NO.", enter the EPA Sample Numbers (10 characters
maximum) of the analytical or field sample analyzed by MSA. The number must
be centered in the box. Note that the EPA Sample No. must include the phase
suffix and duplicate sample suffix (if applicable) of all analytical samples
analyzed by MSA. This includes reruns by MSA (if the first MSA was out of
control), as explained in Exhibits D and E.
12.4 A maximum of 32 samples can be entered on this form. If additional
samples required MSA, submit additional copies of FORM X-HCIN. Samples must
be listed in alphanumeric order per analyte, continuing to the next FORK X-
HCIN if applicable.
12.5 Under "An", enter the chemical symbol (2 characters maximum) for each
analyte on which MSA was required for each sample reported. The analytes must
be in an alphabetic listing of the chemical" symbols. .
12.6 Under "M", enter the method used.
NOTE: Results for different samples for each analyte must be reported
sequentially, with the analytes listed according to the alphabetic listing of
their chemical symbols. For instance, results for As (arsenic) in samples
MAA110, MAAlll, and MAA112 would be reported, in sequence, followed by the
result for Pb (lead) in MAAllO, etc.
12.7 Under "ZERO Found", enter the measured value in absorbance units (to
three decimal places) for the analyte before any addition is performed.
12.8 Under "FIRST Added", enter the final concentration (in mg/L, to three
decimal places) of the analyte (excluding sample contribution) after the first
addition to the sample analyzed by MSA.
12.9 Under "FIRST Found", enter the measured value in absorbance units (to
three decimal places) for the analyte in the sample solution spiked with the
first addition.
12.10 Under "SECOND Added", enter the final concentration (in mg/L, to three
decimal places) of the analyte (excluding sample contribution) after the
second addition to the sample analyzed by MSA.
IHC01.2
Page 48
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Form InstructionGuide
Exhibit B
12.11 Under "SECOND Found", enter the measured value in absorbance units (to
three decimal places) for the analyte in the sample solution spiked with the
second addition.
12.12 Under "THIRD Added", enter the final concentration (in mg/L, to three
decimal places) of the analyte (excluding sample contribution) after the third
addition to the sample analyzed ;. MSA.
12.13 Under "THIRD Found", enter the measured value in absorbance units (to
three decimal places) for the analyte in the sample solution spiked with the
third addition.
NOTE: "ZERO Found", "FIRST Found", "SECOND Found", and "THIRD Found" must
have the same dilution factor.
12.14 Under "FINAL CONC.", enter the final analyte concentration (in mg/L, to
three decimal places) in the sample as determined' by MSA computed according to
the following formula:
Final Cone. = (-1) x (x-intercept)
NOTE: The final concentration of an analyte does not have to equal the value
for that analyte which is reported on FORM I-HCIN for that sample.
12.15 Under "r", enter the correlation coefficient (to three decimal places)
that is obtained for the least squares regression line representing the
following points (x,y):(0.0, "ZERO Found"), ("FIRST Added", "FIRST Found"),
("SECOND Added", "SECOND Found"), ("THIRD Added", "THIRD Found").
12.16 The correlation coefficient must be calculated using the ordinary least
squares linear regression (unweighted) according to the following formula:
N S
r --
[N S Xi2 - (S Xi)2]* [N S Yi2 - (S yi)
12.17 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.
12.18 Under "Comments", enter any MSA specific comments concerning the analyte
results, any significant problems encountered during the MSA analysis (i.e.,
percent recovery outside the control limits), both technical and
administrative, the corrective action taken, and resolution performed for the
sample.
IHC01.2
Page 49
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Form Instruction Guide
.Exhibit B
13. Method Detection Limit {FORM XI - HCIN]
13.1 This form documents the Method Detection Limits for each instrument that
the laboratory used to obtain data for the SDG. Only the instrument and
wavelengths used to generate data for the SDG must be included.
13.2 Complete the header information according to the header instructions and
as follows.
13.3 For "DATE", enter the date (formatted MM/DD/YY) on which the MDL values
were determined (or became effective).
13.4 Enter the instrument ID numbers for the fields "ICP ID Number", "HYICP
ID Number", "GFAA ID Number", "Mercury ID Number", and "Cyanide ID Number" (12
characters maximum each). These ID Numbers are used to uniquely identify each
instrument that the laboratory uses for CLP analyses.
13.5 Under "Wavelength", enter the wavelength in nanometers (to two decimal
places) for each analyte for which a Method Detection Limit (MDL) has been
established and is listed in the MDL column. If more than one wavelength is
used for an analyte, use other copies of FORM XI-HCIN as appropriate to report
the Method Detection Limit used, submit additional copies of FORM XII-HCIN as
appropriate.
13.6 Under "WAVE", enter the wavelength number for which the results of each
analyte are reported on the form. The wavelength number is a. number assigned
to each wavelength used when more than one wavelength is used to obtain data
for an analyte in the SDG. A wavelength number of "1" is assigned to the
longest wavelength used for the analyte in the SDG. A wavelength number of
"2" is assigned to the second longest wavelength and. so on. The field must be
left blank if a single wavelength is used to obtain data for an analyte in the
SDG.
13.7 Under "INTEG. TIME", enter the integration time (in seconds, to two
decimal places) used for each measurement taken from each instrument.
13.8 The Contract Required Quantitation Limits (in rag/Kg), as established in
Exhibit C, must appear in the column headed "CRQL".
13.9 Under "MDL", enter the Method Detection limit (in mg/L, to'three decimal
places) as determined by the laboratory for each analyte analyzed by the
instrument for which the ID number is reported on this form.
13.10 Under "M", enter the method used to determine the method detection .limit
for each wavelength used.
IHC01.2
Page SO
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Form Instruction Guide
Exhibit B
13.11 Use additional copies of FORM XI-HCIN 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 precedetthem by more than three
months.
14. ICP Interelement Correction Factors (Annual') [FORM XII - HCIN]
14.1 This form documents for each ICP instrument the interelement correction
factors applied by the Contractor laboratory to obtain data for the SDG.
14 ..2 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 XII-HCIN.
14.3 Complete the header information according to the header instructions and
as follows.
14.4 For "ICP ID Number", enter the ICP ID Number (12 characters 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 copies of FORM XII-HCIN as appropriate.
14.5 For "Date", enter the date (formatted as MM/DD/YY) on which these
correction factors were determined for use. This date must not exceed the ICP
analysis dates in the SDG data package. Also, it must not precede them by
more than twelve calendar months.
14.6 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 copies of FORM XII-HCIN as appropriate.
14.7 Under "INTERELEMENT CORRECTION FACTORS FOR:", enter the chemical symbol
in the two space header field provided to indicate the analyte for which the
corrections in that column were applied.
14.8 In the "INTERELEMENT CORRECTION FACTORS FOR:" column, enter the
correction factor (negative, positive or zero, to seven decimal places, 10
characters maximum) for each corrected analyte analyzed by ICP. If an analyte
was not corrected for an analyte that is listed in the header of a column, a
zero must be entered to indicate that the correction was determined to be
zero.
14.9 Use additional copies of FORM XII-HCIN as appropriate if correction
factors for more than five analytes were applied.
IHC01.2
Page 51
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Form Instruction Guide
Exhibit B
14.10 Columns of correction factors for analytes requiring interelement
correction must be entered left to right starting on FORM XII-HCIN according
to the alphabetic order of their chemical symbols starting on the first FORM ~.
XII-HCIN and proceeding to the following FORM XII-HCIN as appropriate.
14.11 Under "Comments1', enter alternative wavelengths and the conditions under
which they are used, any significant problems encountered during the
interelement correction analysis, both technical and administrative, the
corrective action taken, and resolution performed for the sample.
15. Phase Separation Log [FORM XIII - HCINJ
15.1 This form is used to report the separation of the phases.
15.2 All samples that are phase separated in association with the SDG must be
reported on a FORM XIII-HCIN. One CD FORM XIII-HCIN must be submitted if no
more than 32 phases were separated for the data deliverables required by the
SDG. If more than 32 samples were separated, then submit additional copies of
FORM XIII-HCIN as appropriate.
15.3 Complete the header information according to the header instructions and
as follows.
15.4 For "Separation Date", enter the dates (formatted MM/DD/YY) on which the
phase separation for the samples listed on the form were performed. If phase
separation for the samples in the SDG were performed on different dates,
submit additional copies of FORM XIII-HCIN for each date as appropriate.
15.5 Under "EPA SAMPLE NO.", enter the EPA Sample Number for each phase
separated in the SDG. All EPA Sample Numbers must be listed in ascending
alphanumeric order, continuing to the next FORM XIII-HCIN if applicable. If a
sample consists of more than one phase, enter the EPA Sample Number in the
order of increasing phase suffix.
15.6 Under "PHASE", enter the phase for each sample reported on the form.
15.7 Under "WATER MISCIBILITY", enter "YES" if the phase of the sample listed
is water miscible, "NO" if the phase is non-water miscible, and "PART" if the
phase is partially water miscible. If the sample phase is not liquid, then
leave the field empty.
15.8 Under "WEIGHT", enter the weight (in-grams, to two decimal places) of
each phase reported on the form.
15.9 Under "PERCENT OF TOTAL SAMPLE", enter the percent of total sample (to
two decimal places), that the phase reported constitutes of the total sample
weight calculated as follows:
IHC01.2
Page 52
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Form Ins true t ion Guide Exhibit B
«, _ _ _ . _ , Phase Weight in Erams , _
% of Total Sample - 7; :* . *? x 100
r Total Sample Weight in grams
15.10 Under "CENTRIFUGE TIKE", enter the total centrifuge time (in minutes)
for each phase listed.
16. Preparation Log [FORM XIV - HCIN] .
16.1 This form is used to report the sample preparation.
16.2 All field samples (including all phases of each sample) and all quality
control preparations (including duplicates, spikes, LCSs, PBs and reprepared
samples) associated with the SDG must be reported on FORM XIV-HCIN. Only the
preparations associated with the SDG may be submitted on this form.
16.3 Submit one FORM XV-HCIN per method if no more than 32 preparations,
including quality control preparations, were performed. If more than 32
preparations per method were performed, then submit additional copies of FORM
XV-HCIN as appropriate.
16.4 Complete the header information according to the header instructions and
as follows.
16.5 For "Method", enter the method of analysis (2 characters maximum) for
which the preparations listed on the form were made.
16.6 Under "EPA SAMPLE NO.", enter the EPA Sample Number (including phase
suffix) of each sample in the SDG and of all other preparations, such as
duplicates, spikes, LCSs, PBs, and repreparations (all formatted according to
Table 1, Section II of this exhibit). All EPA Sample Numbers must be listed
in ascending alphanumeric order, continuing to the next FORM XIV-HCIN if
applicable. If a sample was reprepared, list the same EPA Sample Number in
the order of increasing preparation date.
16.7 Under "PREPARATION DATE", enter the date (formatted MM/DD/YY) on which
each sample was prepared for analysis by the method indicated in the header
section of the form.
16.8 Under "WEIGHT", enter the weight (in grams, to two decimal places) of
each sample prepared for analysis by the method indicated in the header
section of the form.
16.9 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.
IHC01.2 Page 53
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Form Instruction Guide
Exhibit B
16.10 Under "COLOR" and "CLARITY", enter the description of the sample after
preparation in accordance with the descriptive terms used on FORM I-HCIN.
17. Analysis Run Log [FORM XV - HCIN]
17,.1 This form is used to report the analysis run.
17.2 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 analyses following the last SOW-required
field sample.
17.3 All field samples (including all phases of each sample) and all quality
control preparations (including calibration standards, ICVs, CCVs, ICBs, CCBs,
ICSs, LRSs, LCSs, PBs, duplicates, pre-digestion spikes, analytical spikes,
and spike addition analyzed by the method of standard addition) associated
with the SDG must be reported on FORM XV-HCIN. The run must be continuous and
inclusive of all analyses performed on the particular instrument during the
run.
17.4 Submit one FORM XV-HCIN per run if no more than 32 analyses, including
instrument calibration, were analyzed in the run. If more than 32 analyses
were performed in the run, submit additional copies of FORM XV-HCIN as
appropriate.
17.5 Complete the header information according to the header instructions and
as follows.
17.6 For "Instrument ID Number", enter the instrument ID number (12
characters maximum) which is the identifier that distinguishes each instrument
used for analysis in the SDG. If more than one instrument is used, submit
additional copies of FORM XV-HCIN .as appropriate.
17.7 For "Method", enter the method code (2 characters maximum).
17.8 For "Start Date", enter the date (formatted MM/DD/YY) on which the
analysis run was started.
17.9 For "End Date", enter the date (formatted MM/DD/YY) on which the
analysis run was ended.
17.10 Under "EPA SAMPLE NO.", enter the EPA Sample Number, including phase and
QC suffix of each sample (formatted according to Table 1, Section II of this
Exhibit), All EPA Sample Numbers must be listed in increasing temporal (date
and time) order of analysis, continuing to the next FORM XV-HCIN for the
IHC01.2
Page 54
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Form Instruction Guide Exhibit B
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
SPA Sample No. of "ZZZZZ".
17.11 Under "D/F", enter the dilution factor (to three decimal places) by
which the final product of the preparation procedure (digestate or distillate)
can be analyzed within the instrument standard range. The dilution factor
does not include the dilution inherent in the preparation as specified by the
preparation procedures in Exhibit D. NOTE: A "1" must be entered if the
preparation product was analyzed without adding any further volume of dilutant
or any other solutions to the "Volume" or an aliquot of the "Volume" listed on
FORM XV-HCIN for that sample.
V
17.12 For EPA supplied solutions such as ICVs, ICSs, and LCSs, a dilution
factor must be entered if. the supplied solution was used at 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, the ICV-2(0887) has
a true value of 104.0 fig/L for selenium at a 20 fold dilution. If the
solution is prepared at a 40 fold dilution, a dilution factor of "2" must be
entered on FORM XV-HCIN and the uncorrected instrument reading is compared to
a true value of 52 /ig/L. In this example, FORM II-HCIN 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 XV-HCIN using the following formula:
Found value on FORM II-HCIN = Instrument readout in mg/L x D/F
17.13 Under "TIME", enter the time (in military format - HHMM), at which each
analysis was performed. If an autosampler is used with equal analysis time
and intervals between analyses, then only the start time of the run (the time
of analysis of the final CCV or CCB, whichever is later) needs to be reported.
17.14 Under "ANALYTES", enter "X" in the column of the designated analyte to
indicate that the analyte value was used from the reported analysis to report
data in the SDG. Leave the column empty for each analyte if the analysis was
not used to report the particular analyte.
18. Sample Log-in Sheet [FORM HDC-1]
18.1- This form is used to document the receipt and inspection of shipping
containers and samples. One (1) original FORM HDC-1 is required for each
shipping container.
18.2 If the samples in a single shipping container must be assigned to more
than one SDG, then the original FORM HDC-1 shall be placed with the
deliverables for the SDG of the lowest alphanumeric number and a copy of FORM
IHC01.2 Page 55
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Form Instruction Guide . Exhibit B
HDC-1 must be placed with the deliverables for the other SDG(s). The copies
should be identified as "copy(ies)," and- the location of the original should
be noted on the copies.
18.3 Sign and date the airbill (if present). Examine the shipping container
I and record the presence/absence of custody seals and their condition (i.e.,
intact, broken) in item 1 on FORM HDC-1. Record the custody seal numbers in
item 2.
18.4 Open the shipping container, remove the enclosed sample documentation,
and record on FORM HDC-1, items 3-5, the presence/absence of chain-bf-custody
rec'ord(s), SMO forms (i.e., Traffic Reports, Packing Lists), and airbills or
airbill stickers. Specify if there is an airbill or an airbill sticker
present in item 5 on FORM HDC-1. Record the airbill or sticker number in item
6.
18.5 Remove the samples from the shipping container(s), examine the samples
and the sample tags (if present), and record the condition of the sample
bottles (i.e., intact, broken, leaking), and the presence or absence of sample
tags in items 7 and 8 on FORM HDC-1.
18.6 Review the sample shipping documents and complete the header
information. Compare the information recorded on all the documents and
samples, and circle the appropriate answer in item 9 on FORM HDC-1.
18.7 If there are no problems observed during receipt, sign and date (include
time) FORM HDC-1, the chain-of-custody record, and TR, and write the sample
numbers on FORM HDC-1. Record the appropriate sample tags and assigned
laboratory numbers if applicable. The log-in date should be recorded at the
top of FORM HDC-1, and the date and time of cooler receipt at the laboratory
should be recorded in items 10 and 11. Cross' out unused columns and spaces.
18.8 If there are problems observed during receipt or if an answer marked
with an asterisk (i.e., "absent*") was circled, then contact SMO and document
the resolution of the problem on a CLP Communication Log. Following
resolution, sign and date the forms as specified in the preceding paragraph
and note, where appropriate, the resolution of the problem.
j 18.9 For "Sample Transfer", enter the fraction designation (if appropriate)
j and the specific area designation (e.g., refrigerator number) in the sample
! transfer block located in the bottom left corner of FORM HDC-1. Sign and date
j the sample transfer block,
19. Document Inventory Sheet [FORM HDC-2]
19.1 This form is used to record the inventory of the Complete Sample
Delivery Group Case file (CSF) documents which are sent to the Region.
IHC01.2 Page 56
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Form Instruction Guide
Exhibit B
19.2 Organize all EPA-CSF documents as described in Exhibit B, Section II and
Section III. Assemble the documents in the order specified on FORM HDC-2 and
Section II and III, and stamp each page with the consecutive numbers (Do not
number the DC-2 form). Inventory the CSF by reviewing the document numbers
and recording page number ranges in the column provided on the FORM HDC-2. If
there are no documents for a specific document type, enter "NA" in the empty
space,.
19.3 Certain laboratory specific documents related to the CSF may not fit
into a clearly defined category. The laboratory should review FORM HDC-2 to
determine if it is most appropriate to place them under No. 28, 29, 30, or 31.
Category 31 should, be used if there is no appropriate previous category.
These types of documents should be described or listed in the blanks under
each appropriate category.
IHC01.2
Page 57
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SECTION IV
DATA REPORTING FORMS
IHC01.2
Page 58
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U. S. ENVIRONMENTAL PROJECTION AGENCY
CONTRACT LABORATORY PROGRAM
High Concentration Inorganics
COVER PAGE
Lab Name: Contract:
Lab Code: SAS No.:
Case No.: SDG No.:
SOW No.:
EPA Sample No. Lab Sample ID
Enter a Y for Yes or an "N" for No
ICP interelement corrections applied?
ICP background corrections applied?
If yes, were raw data generated before
application of background corrections?
Comments:
1 certify that this data package is in compliance with the terms and
conditions of the contract, both technically and for completeness, excluding
the conditions detailed above. Release of the data contained in this
hardcopy data package has been authorized by the Laboratory Manager
or the Manager's designee, as verified by the following signature.
Signature: Name:
Date: Title:
HCOI.2 COVER PAGE - HCIN 5/91
-------
Lab Name:
Lab Code:
Case No.:
SAS No.: _
SDG No.:
U. S. ENVIRONMENTAL PROTECTION AGENCY
CONTRACT LABORATORY PROGRAM
High Concentration Inorganics
ANALYSIS DATA SHEET
Contract:
Water Miscibility:
Texture:
Artifacts:
' Comments:
EPA SAMPLE NO.
Lab Sample ID:
Date Received:
Phase:
Percent:
Color:
Clarity:
Viscosity:
Concentration Units: ing/Kg
Conductivity:
CAS NO.
7429-90-5
7440-36-0
7440-38-2
7440-39-3
7440-41-7
7440-43-9
7440-70-2
7440-47-3
7440-48-4
7440-50-8
7439-89-6
7439-92-1
7439-95-4
7439-96-5
7439-97-6
7440-02-0
7882-49-2
7440-22-4
7440-23-5
7440-28-0
7440-62-2
7440-66-6
.
ANALYTE
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
CONCENTRATION
-
C
Q
M
rJ1.2
FORM I - HCIN
5/91
-------
U. S. ENVIRONMENTAL PROTECTION AGENCY
CONTRACT LABORATORY PROGRAM
High Concentration Inorganics
INITIAL AND CONTINUING CALIBRATION VERIFICATION
.b Name:
b Code:
ise No.:
\S No.:
)C No.:
Contract:
Initial Calibration Source:
Continuing Calibration Source:
Concentration Units: mg/L
ANALYTE
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
iron
Lead
Magnesium
Manganese
Mercury
Nickel
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
W
A
V
E
INITIAL CALIBRATION
True
>
Found
%R
CONTINUING CALIBRATION
FIRST
True
-
Found
%R
SECOND
True
Found
%R
M
>
omments:
ICOL2
FORM I! - HCIN
5/91
-------
Lab Name:_
Lab Code:
Case No.:
CRQL:
ICP Source: _
HYICP Source: _
; GFAA Source: _
, Cyanide Source:
Mercury Source:
U. S. ENVIRONMENTAL PROTECTION AGENCY
CONTRACT LABORATORY PROGRAM
High Concentration Inorganics
CRQL STANDARDS / LINEAR RANGE STANDARDS
Contract:
SAS No.:
SDG No.:
LRS:
ICP Source: '
HYICP Source:
GFAA Source:
Cyanide Source:
Mercury Source:
Concentration Units: mg/L
ANALYTE
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Pbalcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cvanide
W
A
V
E
CRQL STANDARDS
INITIAL
True
Found
%R
FINAL
Found
%R
M
LINEAR RANGE STANDARDS
INITIAL
True
Found
%R
FINAL
Found
%R
*
M
Comments:
FORM 111 - HCIN
5/91
-------
Lab Name:
Lab Code:
Case No.:
SAS No.:
U. S. ENVIRONMENTAL PROTECTION AGENCY
CONTRACT LABORATORY PROGRAM
High Concentration Inorganics
BLANKS
Contract:
SDG No.:
Preparation Blank Phase:
Concentration Units: mg/L
ANALYTE
Aluminum
Antimony
Arsenic
Barium
Beryllium . .
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
pH
Conductivity
W
A
V
E
'
INITIAL
CALIB.
BLANK
C
CONTINUING CALIBRATION BLANK
1
.
C
2
C
3
- '
C
...
PREPARATION
BLANK
mg/Kg
C
M
&'*?
iJC
Comments:
HC01.2
FORM IV - HCIN
5/91
-------
Lab Name:
Lab Code: _
Case No.: _
SAS No.: _
SDG No.:
U. S. ENVIRONMENTAL PROTECTION AGENCY
CONTRACT LABORATORY PROGRAM
High Concentration Inorganics
ICP INTERFERENCE CHECK SAMPLE
Contract:
Comments:
ICP ID No.:_
ICS Source:
Concentration Units: mg/L
ANALYTE
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Ch fQ ntiMiii
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
W
A
V
E
TRUE
Sol.
A
Sol.
AB
INITIAL FOUND
Sol.
A
Sol.
AB
.
%R
FINAL FOUND
Sol.
A
Sot.
AB
%R
M
FORM V - IN
5/91
-------
U. S. ENVIRONMENTAL PROTECTION AGENCY
CONTRACT LABORATORY PROGRAM EPA SAMPLE NO.
High Concentration Inorganics
SPIKE SAMPLE RECOVERY
Lab Name:
Lab Code:
Case No.:
SAS No.:
SDG No.:
Contract:
Phase:
Percent:
Concentration Units: mg/Kg
ANALYTE
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium .
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Selenium
Silver
[Sodium
[Thallium
Vanadium
Zinc
| Cyanide
W
A
V
E
CONTROL
LIMIT
%R
SPIKED SAMPLE
RESULT
(SSR)
C
SAMPLE
RESULT
(SR)
C
SPIKE
ADDED
(SA)
%R
Q
M
Comments:
IHC01.2
FORM VI - HC1N
5/91
-------
Uab Name:
liab'Code:
Case No.:
'i
SAS No.:
SDG No.:
U. S. ENVIRONMENTAL PROTECTION AGENCY
CONTRACT LABORATORY PROGRAM EPA SAMPLE NO.
High Concentration Inorganics
ANALYTICAL SPIKE SAMPLE RECOVERY
Contract:
Phase:
Percent:
Concentration Units: mg/L
ANALYTE.
Aluminum
1 Antimony
Arsenic
1 Barium
| Beryllium
Cadmium
Calcium
'Chromium
Cobalt
Copper
Iron
liead
Magnesium
Manganese
Mercury
Nickel
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cvanide
W
A
V
E
CONTROL
LIMIT
%R
SPIKED SAMPLE
RESULT
(SSR)
.'
C
SAMPLE
RESULT
(SR)
C
SPIKE
ADDED
-------
U. S. ENVIRONMENTAL PROJECTION AGENCY
CONTRACT LABORATORY PROGRAM
High Concentration Inorganics
DUPLICATES
EPA SAMPLE NO.
Lab Name:
Lab Code:
Case No.:
SAS No.:
SDG No.:
Contract:
Phase:
Sample Percent:
Duplicate Percent:
Concentration Units:
nig/Kg
Comments:
ANALYTE
i Aluminum
1 Antimony
i Arsenic
i Barium
1 Beryllium
! Cadmium
[Calcium
j Chromium
i Cobalt
! Copper
[Iron
|Lead
i Magnesium
! Manganese
| Mercury
| Nickel
{Selenium
[Silver
1 Sodium
| Thallium
(Vanadium
(Zinc
[Cyanide
i
i
W
A
V
"E
"
CONTROL
. LIMIT
SAMPLE
(S)
C
DUPLICATE
(D)
C
RPD
Q
M
FORM VIII - HCIN
5/91
.
-------
U. S. ENVIRONMENTAL PROTECTION AGENCY
CONTRACT LABORATORY PROGRAM
High Concentration Inorganics
LABORATORy CONTROL SAMPLE
Lab Name: Contract:
Lab-Code: SAS No.:
Case No.: " SDG No.:
i
ICPiSource: Cyanide Source:
HYICP Source: Mercury Source:
GFAA Source: Concentration Units: rug/Kg
li
W '
A
1 ANALYTE V LIMITS TRUE FOUND
E
C
1 Aluminum ! 1
i Anumony '
., 1 Arsenic >
iBarium !
i Beryllium ''
' Cadmium ! ! !
^ ! I Calcium i
^B ' I Chromium i
^ " Cobalt !
Copper ; . i j
|Iron : ;
1 Itead- |- ' ;
: | Magnesium <
i 1 Manganese :
IMercur>-
'' INickel > . i
{Selenium :
: ISilver ' ;
!' 1 Sodium i I <
i Thallium !
' i Vanadium 1 '
Zinc j [
Cyanide tall |
' 'pH mm ''
, [Conductivity ^^1 ' I
%R M
f
1
i i
1 {
i
I
!
1
I
i
1
i ;
1
M
H
B
'
Comments:
._
FORM IX - HC1N
5/91
-------
Lab Name:
Lab Code:
Case No.:
U. S. ENVIRONMENTAL PROTECTION AGENCY
CONTRACT LABORATORY PROGRAM
High Concentration Inorganics
STANDARD ADDITION RESULTS
__ Contract:
SDG No.:
Concentration Units: mg/L
EPA : j
SAMPLE iAniM
i NO, ! !
A D D I
ZERO FIRST
Found
i i i i i
2 : , i
31 i !
4 ; if!
5 i ! i
61 i j .
71 : i :
8 i i
9 i :
Added
10 ! , i ! I
11 ! 1 ;
Found
1
12 i I i !
13 i ; i
14 | ! i
is i j i i-
16 1 ! :
17 j ' ill
18j ! !'
19 | ; :
i
T I O N
S
SECOND THIRD
Added
Found Added
Found
FINAL
CONG.
i
-
!
1
!
j
|
j
.
1
! i
1 !
j i
i
!
i !
1 ! i i
i i
j
20 i ! : !
21 i . i i
22 i ' :
23 ! ' I
24 | ! i
t
i 1
i 1
i
i
25 i !!i
26! j !
27 i | j
I
i
28 i i ; I
291 i !
30 i 1 !
i
t
i
i
i
!
.
i
)
i '
1
31 i i i ; i
1
j
i
i
I
i
32 ! i ' j . ' !
i
r j Q
j
i
i
,
1 .
i
i
!
i '
i
I
i
i
i
i
i !
i
i 1
i
i
I i
;
Comments:
IHC01.2
FORM X - HCIN
5/91
-------
Lab Name:
< Lab Code:
Case No.:
SASNo.:
SDGNo.:_
Date:
U. S. ENVIRONMENTAL PROTECTION AGENCY
CONTRACT LABORATORY PROGRAM
High Concentration Inorganics
METHOD DETECTION LIMIT
Contract:
ICP ID Number:
HYICP ID Number:
GFAA ID Number:
Cyanide ID Number:
Mercury ID Number:
Concentration Units: mg/L
4»
ANALYTE
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
WAVE-
LENGTH
(nm)
W
A
V
E
INTEG.
TIME
(SEC)
^
CRQL
(mgflCg)
80
20
5
80
5
10
80
10
20
40
20
10
80
10
0.3
20
5
10
80
20
20
10
1.5
MDL
M
Comments:
FORM XI - HC1N
5/91
-------
U. S. ENVIRONMENTAL PROTECTION AGENCY
CONTRACT LABORATORY PROGRAM
High Concentration Inorganics
ICP INTERELEMENT CORRECTION FACTORS (ANNUAL)
Lab Name:
Lab Code:
Case No.:
SDG No.:
Contract:
ICP ID Number:
Date:
ANALYTE
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cvanide
WAVE-
LENGTH
(nm)
INTERELEMENT CORRECTION FACTORS FOR:
Comments:
C01.2
FORM XII - HC1N
5/91
-------
U. S. ENVIRONMENTAL PROTECTION AGENCY
CONTRACT LABORATORY PROGRAM
High Concentration Inorganics
PHASE SEPARATION LOG
Lab Name:
Lab Code:_
Case No.:
Contract:
SDG No.:
Separation Date:
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
I?
IS
19
20
21
22
23
24
25
26
27
28
29
30
31
32
EPA
SAMPLE
NO.
PHASE
-
WATER
MISCmiLITY
WEIGHT
(grams)
PERCENT
OF TOTAL
SAMPLE
CENTRIFUGE
TIME
FORM XIII - HCIN
5/91
-------
Lab Name:
Lab Code:
Case No.:
U.S. ENVIRONMENTAL PROTECTION AGENCY
CONTRACT LABORATORY PROGRAM
High Concentration Inorganics
PREPARATION LOG
Contract:
SDG No.:
Method:
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
EPA
SAMPLE
NO.
PREPARATION
DATE
WEIGHT
(grams)
VOLUME
COLOR
CLARITY
HC01.2
FORM XIV - HC1N
5/91
-------
, Lab Name:
Lab Code:
Case No.:
Start Date:_
End Date:
U.S. ENVIRONMENTAL PROTECTION AGENCY
CONTRACT LABORATORY PROGRAM
High Concentration Inorganics
ANALYSIS RUN LOG
Contract:
. SDG No.:
SASNo.:
Method:
Instrument ID Number:
" EPA
SAMPLE
NO.
TIME
D/F
ANALYTES
A
L
I
S
B
-
A
S
B
A
B
E
C
D
C
A
C
R
C
O
C
u
F
E
P
B
M
G
M
N
H
G
N
I
S
E
A
G
N
A
T
L
V
Z
N
C
N
riCOl.2
FORM XV - HCIN .
5/91
-------
SAMPLE LOG-IN SHEET
Lab Name:
Received By (Print Name):
'Received By (Signature):
Log-in Date:
Page of
iCase Number:
Sample Delivery
Group No.:
SAS Number:
CIRCLE THE APPROPRIATE
RESPONSE:
1 . Custody Seal(s) Present/ Absent*
Intact/Broken
2. Custody Seal Nos.:
3. Chain-of-Cuslody Present/ Absent*
Records
4. Traffic Reports or Present/ Absent*
Packing List
5. Airbill AirbUl/Sticker
Present/ Absent*
+
6. Airbill No.:
7. Sample Tags Present/ Absent*
Sample Tag Listed/Not Listed
Numbers on Chaiii-of-Cii«cxty
8. Sample Condition: Intact/Broken*/
Leaking
9. Does information on custody records
traffic reports, an sample tags
agree. Yes/No*
10. Date Received at Lab:
1 1 . Time Received:
Sample Transfer
Fraction:
Area #:
By:
On:
!
EPA
SAMPLE
#
SAMPLE
TAG
* *
ASSIGNED
LAB
#
REMARKS:
CONDITION
OF SAMPLE
SHIPMENT
ETC.
*lf circled, contact SMO nnd attach record of resolution.
Reviewed by:
Date:
Logbook No.:
Logbook Page No.:
1HC01.2 .
FORM HOC-1
5/91
-------
HIGH CONCENTRATION INORGANIC ANALYTES
COMPLETE SDG PILE (CSF)
INVENTORY SHEET
Lab Name:
Case No.:
SAS No.:
SDG No.:
Contract No.:
City/State:
SDG Nos. to Follow:
SOW No.: IFB No.:
All documents delivered in the complete SDG file must be original documents where possible.
(Reference Exhibit B, Section 111)
Page Nos. (Please Check:)
From To Lab Region
I 1. Inventory Sheet (HOC-2) (Do not number)
1 2. Cover Page
j 3. Inorganic Analysis Data Sheet (FORM I-HCIN)
I 4. Initial & Continuing Calibration
I Verification (FORM H-HCIN)
' . 5. CRQL Standards/Linear Range Standards (FORM III-HCIN)
I . 6. Blanks (FORM JV-HC1N)
i 7. ICP Interference Check Sample (FORM V-HCIN)
8. Spike Sample Recovery (FORM VI-HCIN)
9. Analytical Spike Sample Recovery (FORM VII-HCIN)
10, Duplicates (FORM VIII-HCIN)
11. Laboratory Control Sample (FORM IX-HCIN)
12. Standard Addition Results (FORM X-HCIN)
13, Method Detection Limit (FORM XI-HCIN)
14. ICP Interelement Correction Factors
(Annual) (FORM XII-HCIN)
15. Phase Separation Log (FORM XIII-HCIN)
16. Preparation Log (FORM XIV-HCIN)
17. Analysis Run Log (FORM XV-HCIN)
18. ICP Raw Data
19. HYICP Raw Data
20. Graphite Furnace AA Raw Data
21. Mercury Raw Data
22. Cyanide Raw Data
23. pH Raw Data
24. Conductivity Raw Data
25. Traffic Report
IHCOI.2 FORM HDC-2 5/91
-------
Page Nos.
From
To
(Please Check:)
Lab Region
26, EPA Shipping/Receiving Documents
Airbill (No. of Shipments )
Chain-of-custody Records
Sample Tags
Sample Log-In Sheet (Lab &. HDC-1)
SDG Cover Sheet
27. Misc. Shipping/Receiving Records
(list alt individual records)
Telephone Logs
28.
29.
30.
internal Lab Sample Transfer Records &.
Tracking Sheets (describe or list)
Internal Originial Sample Preparation & Analysis Records
(describe or list)
Preparation Records
Analysis Records
Description
Other Records (describe or Hst)
Telephone Communication Log
31. Comments:
Completed by (CLP Lab):
(Signature)
Audited by (EPA):
(Print Name & Title)
(Date)
(Signature)
(Print Name & Title)
(Date)
1HC01.2
FORM HDC-2 (continued)
5/91
-------
EXHIBIT C
INORGANIC ANALYTE TABLES
IHC01.2
Page 78
-------
TABLE 1.
HIGH CONCENTRATION INORGANIC
TARGET ANALYTE LIST (TAL)
Analyte
Contract Required
Quantitation Limit1,2
(mg/Kg)
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Cyanide
Conductivity
pH
80
20
5
80
5
10
80
10
20
40
20
10
80
10
0.3
20
5
10
80
20
20
10
1.5
3 . 0 (/imhos/cm)
NA
(1) The analytical methods specified in SOW Exhibit D must be utilized and
the achieved method detection limits must meet the Contract Required
Quantitation Limits (CRQL) requirements. Higher detection levels may
only be used in the following circumstance:
If the sample concentration exceeds two times the detection limit of the
instrument or method in use, the value may be reported even though the
instrument or method detection limit may not equal the contract required
quantitation limit.- The method detection limit must be documented as
described in Exhibits D and E.
(2) These CRQLs are the method detection limits (for metals) and the maximum
allowable method blank values (for all other parameters) obtained from
actual method blank preparations that must be met using the procedure in
Exhibits D and E.
IHC01.2
Page 79
-------
TABLE 2,
INTERFERENCE CHECK SAMPLE
Solution A
Elements (mg/L)
Solution AB
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.
500.
500.
IHC01.2
Page 80
-------
TABLE 3.
INITIAL AND CONTINUING CALIBRATION VERIFICATION
CRQL STANDARD CONTROL LIMITS, AND LCS STANDARD CONTROL LIMITS
FOR INORGANIC ANALYSES
INITIAL AND CONTINUING CALIBRATIf " VERIFICATION LIMITS
Analytical Method
ICF '
HYICP
GFAA
Cold Vapor AA
Other:
Inorganic
Species
Metals
Metals
Metals
Mercury
Cyanide
Low Limit
90
90
90
80
85
High Limit
110
110
110
120
115
CRQL STANDARD CONTROL LIMITS
% of True Value fEPA Set)
Analytical Method Inorganic Low Limit High Limit
Species
ICP Metals 85 115
HYICP Metals 85 115
GFAA Metals 85 115
Cold Vapor AA Mercury 75 125
Other: Cyanide 80 120
LCS STANDARD CONTROL LIMITS
The LCS Standard Control Limits are the same for all inorganics species. The
limits are 80 - 120 percent.
IHC01.2 Page 81
-------
TABLE 4.
SPIKING LEVELS AND FORMS OF ANALYTE IN THE SOLID SPIKING MIXTURE
Analyte
Form
Spike Level (mg/Kg)
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Cobalt
Copper
Lead
Manganese
Nickel
Selenium
Silver
Thallium
Vanadium
Zinc
SbO
AsO
Be(C2H302)2
CdO
CrO
CoC03
CuO
PbO
MnO
NiO
SeO
AgO
T10
VO
ZnO
1600
1600
1600
1600
1600
1600
1600
1600
1600
1600
1600
1600
1600
1600
1600
NOTE: The spike concentration in solution after the potassium hydroxide
fusion will be 4.0 mg/L.
IHC01.2
Page 82
-------
TABLE 5.
LCS CONCENTRATION
Analyte
Concentration (rag/Kg)
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
2870
164
1954
10
91
194
76505
315
346
8727
89020
86650
41318
184
2
413
160
91
94
359
91
23647
36764
IHC01.2
Page 8-3
-------
EXHIBIT D
PREPARATION AND ANALYSIS METHODS
IHC01.2
Page 84
-------
EXHIBIT D
ANALYTICAL METHODS
Page
SECTION I INTRODUCTION 86
Figure 1 High Concentration Inorganic Methods Flow Chart . 87
SECTION II HOLDING TIMES AND STORAGE REQUIREMENTS 88
SECTION III METHODOLOGY AND DATA USER GUIDE ' . . 89
SECTION IV SAMPLE PREPARATION
Phase Separation and Aliquoting
(Method 50.60-CLP) . 92
SECTION' V SAMPLE ANALYSIS
Potentiometric and Colorimetric Determination
of the pH of Industrial Waste Materials (Method
150.20-CLP) 95
Determination of Conductivity in Industrial
Waste Material (Method 120.1-CLP) 103
Dissolution of Industrial Waste Materials for
Elemental Analysis by Potassium Hydroxide
Fusion (Method 200.62-A-CLP) 110
Pneumatic Nebulization Inductively Coupled
Argon Plasma Optical Emission Spectroscopic
(ICP) Analysis (Method 200.62-B-CLP) 115
Hydride Generation Inductively Coupled Argon
Plasma Optical Emission Spectroscopic (HYICP) Analysis
(Method 200.62-C-CLP) 142
Determination of Potassium Hydroxide Fusion
Samples by Graphite Furnace Atomic Absorption (GFAA)
Technique 166
Atomic Absorption Spectroscopic Determination
of Mercury in Industrial Waste Materials (CVAA)
(Method 202.62-CLP) 186
Colorimetric Determination of Cyanide in
Industrial Waste Materials (Method 335.63-CLP) 204
IHC01.2
Page 85
-------
SECTION I
4»
INTRODUCTION
The analytical scheme that the Contractor will follow in performing
sample analyses under this contract is outlined in Figure 1, the High
Concentration Inorganics Methods Flow Chart.
All analytical methods specified in Exhibit D may be utilized as long as
the documented method quantitation limits meet the CRQLs listed in Exhibit C,
All samples shall be carried through the sample preparation procedure
and then run undiluted. When an analyte concentration exceeds the calibrated
or linear range, reanalysis of the prepared sample is required after
appropriate dilution. For the sample dilution, the Contractors must use the
lowest dilution factor necessary to bring each analyte within the valid
analytical range and report the highest valid value for each analyte. Both
diluted and undiluted sample measurements must be contained in the raw data.
Samples must be opened and digested in a hood. Stock solutions for
standards may be purchased or made up as specified in the analytical methods.
All sample dilutions shall be made with acidified water to maintain constant
acid strength. Unless otherwise instructed by the EPA APO or TPO, all samples
must be mixed thoroughly prior to aliquoting for digestion.
For all ICP measurements, use the average intensity of multiple
exposures for both standardization and all other analyses. A minimum of two
replicate exposures are required. All standards .with analyte concentrations
made up for less than 1 mg/L are low level standards.
For HYICP, GFAA, and CVAA systems, calibration standards are prepared by
diluting the stock metal solutions. Calibration standards must be prepared
fresh each time an analysis is.to be made and discarded after use. The date
and time of preparation and analysis shall be given in the raw data.
IHC01.2
Page 86
-------
FIGURE 1
High, Concentration Inorganic Methods Flow Chart
Field Sample
T
Traffic Report of SMO
Specifies Parameters
T
Phase Separation
1 1
T T
Dilution KOH Fusion
Analyses
1 II
T T T
pH, Metals Metals
Conductivity Analysis Analysis
by by
ICP HY1CP
1 1 1
T T T
J
Acid
Digestion D
for Hg.
1
Hg
Analysis
by
Cold Vapor
j
V
CN
istill-
ation
1
CN
Analysis
by
Color-
metric
j
Data Reports
IHC01.2
Page 87
-------
SECTION II
HOLDING TIMES AND STORAGE REQUIREMENTS
1.
HOLDING TIMES
Under this contract, the following are the maximum sample holding times
allowable. These holding time supersede any contract required delivery
schedule.
Analvte
No. of Days Following
Sample Receipt
by Contractor
Mercury
Metals' (other than Mercury)
Cyanide
PH
Conductivity
2.
STORAGE REQUIREMENTS
26 days
180 days.
12 days
24 hours
24 hours
The samples shall be stored in'either glass or plastic polyethylene
bottles in a secure location.
For liquid samples, the sample custodian shall store the material in an
refrigerator at 4 ± 2°C.
For solid samples, the sample custodian shall store the material in an
designated area'in which to avoid possible contamination and endangerment to
the health and safety of the employees.
IHC01.2
Page 88
-------
SECTION III
METHODOLOGY AND DATA USER GUIDE
1.
Scope
1.1 Samples of industrial waste materials gathered in support of EPA
investigations of disposal, handling and storage practices are subjected to
limited chemical characterization using the procedures and methods prescribed
herein. This characterization is not designed to define the total composition
of the samples, but,is designed essentially to look for specific constituents.
The characterization is targeted to the analysis of the priority pollutants
and additional inorganic parameters.
1.2 Samples may be obtained from drummed materials, waste pits or lagoons,
piles of waste, tanker trucks, onsite tanks, or apparent contaminated soil
areas.
1.3 The waste materials usually are industrial process waste, byproducts,
raw materials, intermediates and contaminated products. Many of the samples
may be spent oil, spent solvents, paint wastes, metal treatmejit wastes, and
polymer formulations.
1.4 The methods are included for the determination .of 22 metals, cyanide,
conductivity, and pH. Also included is a phase separation method that is
applied to samples prior to digestion and analysis. Each individual phase is
digested and analyzed by the specific methods. (A phase being either water
miscible, non-water miscible, or solid.)
2.
Limitations
2.1 A detailed knowledge of the chemical and physical properties of samples
submitted for analysis, as well as the behavior of analytes under specific
conditions, are not available with the wide variety of materials that are
submitted under this contract. Although the analytical methods contained
herein have been shown to be quantitative for a large number of sample
matrices, the unknown nature of the samples prior to characterization can
cause problems in certain instances.
2-2 The elemental constituent analysis approach only analyzes 22 metals.
Interferences from metals not included in this analysis which may cause either
positive or negative biases will not be corrected by this approach. The
recovery of certain metals from a sample matrix may be affected by the
presence of other metals or by the form of the metal, which may not be readily
detected.
3.
Characterization
3.1 Corrosivity of a waste may be determined by testing for either pH or
rate of steel corrosion. The pH of water extracted samples as determined
IHC01.2
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Methodology and Data jJser Guide Exhibit D
I herein does not classify a waste as a RCRA waste but instead is determined for
i informative purposes such as to aid in waste segregation.
i
j 3.2 Reactive wastes may be wastes from one of many groups including unstable
: ' materials (explosives), materials that undergo violent reactions with water
(sodium metal) or without water (pyrophorics), and materials that generate
toxic vapors/gases upon reaction with water (phosphides) or mildly acidic
1 conditions (cyanide). The methods for cyanide included here are "total"
methods for cyanide amenable to distillation under strongly acidic conditions.
I , 3.3 The identification of metal constituents, including priority .pollutants,
is part of the EPA determination of a toxic waste. This material is not a
] "toxic" waste in the normal usage of the word but is instead based on the
I potential for the hazardous constituents of the waste to leak out of the waste
I site (landfill, pond, etc.) and contaminate the soil and/or ground water.
| 4. Summary of Methodology
i
j 4.1 Phase separation is performed on the samples in an effort to improve
: both precision and accuracy. Precision is improved because once the sample is
j - separated using standard protocols, the individual phases may be weighed and
; aliquoted without subjective decision making on the part of the technician as
to what percentage of the sample each phase represents. Separation also
improves precision in cases where different technicians may make an additional
or repeat aliquots. Accuracy is improved with phase separation because by
phase separating the sample, all phases are accounted for and included in the
total sample concentration. Even if there is insufficient phase to aliquot
all preparations, the examination of the separated phase will enable a more
! educated decision to be made as to which analysis is most appropriate. Also,
! obvious artifacts (see Method 50.60-CLP) can be more easily identified and
eliminated from the analytical scheme.
1 4.2 The pH is determined by the use of a low sodium glass combination pH
electrode or by an indicator test strip (colorimetric method).
i
i 4.3 The conductivity of a diluted or an undiluted sample is measured by use
of a self-contained conductivity meter, Wheatstone bridge-type, or equivalent.
The results of direct analyses of water miscible liquids are preferable to be
' analyzed at 25°C. If not, temperature corrections are made and results
reported at 25 °C. The results of measuring for conductivity can aid in
[ estimating sample size to be used for common chemical determinations, check
i . results of a chemical analysis, estimate total filtrable residue in a sample,
;, and measure the corrosion rate.
4.4 The potassium hydroxide fusion technique is used'to dissolve inorganic
metals from a wide variety of industrial waste materials. In particular,
organic matter is largely destroyed and silica matrices are dissolved. This
procedure takes an aliquot of sample and fuses it with 2 g of potassium
hydroxide in a pyrolytically-coated graphite crucible. The mixture is then
IHC01.2 , Page 90
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Methodology and Data User Guide
Exhibit D
carried through various heacing stages, cooled, rinsed with acid, mixed with
hydrogen peroxide, and allowed to mix overnight to aid in dissolution and.to
outgas the peroxide.
4.5 The analytical methods provided for the determinations of the 22 metals
and cyanide include ICP, HYICP, GFAA, CVAA, and colorimetric techniques.
5. Required Quantitation Limits
5.1 The required quantitation limits can be found in Exhibit C, Table 1.
6. Documentation and Reporting Forms
6,1 All raw analysis data including calibration and analysis printouts,
'associated notebook entries and laboratory bench and calculation sheets must
be clearly labeled. Reanalysis of samples must be documented and clear
identification of the various analytical runs must be present with the
required submission of raw data. Reporting forms are found in Exhibit B.
7.
Glassware Cleaning for Metals Determination
7.1 For the determination of metals in high concentration, high hazard
samples, the problem of sample carry-over is a prime concern. Since the
levels of metals in individual samples may vary significantly, all glassware
should be treated on a worst-case basis. The following protocol must be used
for glassware cleaning:
» Prior to removal from the hood, wash all glassware with hot, soapy water
followed by a tap water rinse. Remove any remaining sample with the use
of organic solvents followed by a hot, soapy wash and tap water rinse.
Thoroughly rinse the glassware with 50% nitric acid.
Thoroughly rinse with tap water.
Thoroughly rinse with 50% hydrochloric acid.
Thoroughly rinse with tap water.
Soak the glassware for 24 hours in 25% nitric acid.
Rinse all glassware with sufficient ASTM Type I water (at lease three
rinses) to remove all traces of acid.
NOTE: Chromic acid may be useful to remove organic deposits from glassware;
however, the glassware must be thoroughly rinsed with water to remove the last
traces of chromium. The glassware must ^be carried through the entire
glassware cleaning protocol after the use of chromic acid.
IHC01.2
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Methodology and Data UserGuide
Exhibit D
SECTION IV
1.
SAMPLE PREPARATION
Method S0.60-CLP
Phase Separation and Aliquoting
Scope and Application
1.1 This is a general purpose method that provides procedures for phase
separating industrial waste samples taken from drums, lagoons, tanks,
landfills, and other uncontrolled hazardous waste sites.
2. Summary of Method
2.1 Individual phases are separated by decanting and centrifuging. After
separation, individual phases are measured to meet the total weight, specified
in the individual methods.
2.2 Phase separation is performed in order to obtain representative aliquots
from the original sample and to characterize the different phases present in
the sample.
3.
Sample Characteristics
3.1 The characteristics of the samples defined below are the only
descriptions to be used in describing the physical attributes of the samples
(specific comments may be used when appropriate):
Phase A solid (gel or paste) or liquid ( water miscible or non-
water miscible).
Paste Inseparable solid and liquid.
Viscosity Nonviscous (similar to water) or viscous.
Color Colorless, light, medium or dark in color. Use only primary
and secondary colors - red, blue, yellow, green, violet,
orange, brown, white, gray, or black.
Texture Fine (powdery), medium (sand) or coarse (large crystals or
-, rocks).
Clarity Clear, cloudy (transmits light) or opaque.
Minor
Phase
Phases that represent less than or.equal to 1% by weight of
the total sample.
IHC01.2
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Method 50.60-CLP
Phase Separation
4.
Artifacts
4.1 Artifacts may occur in the sample depending on the nature of the waste
and how it was obtained, Artifacts are not minor phases but are due to
extraneous agents not of the waste. When excluding a portion of a sample from
aliquoting based on the apparent presence of an artifact, the decision should
be fully documented on the cover page.
5 . Apparatus and Equipment
5.1 Centrifuge, explosion-proof
Large process type for 8 oz. j ars
Small type for vials
5.2 Vials and jars with teflon lined caps
2 dram vials
40"rnL vials
20 mL vials
8 oz. j ars
4 oz. j ars
5.3 Pipets, various sizes
5.4 Balance, four place
5.5 Spatulas, various types
5.6 Miscellaneous
Absorbent toweling
Soap and water squirt bottles
Solvent squirt bottles (methanol, acetone, methylene chloride)
Plastic bags, various sizes
Stainless steel trays
Teflon cap liners, various sizes.
6. Procedure
6.1 Place the sample can inside a plastic trash bag. Remove the sample
container(s) from the can and record the type and number of containers
present. Wipe down the sample container(s) with a towel moistened with soapy
water.
6.2 Record any other sample information present.
IHC01.2
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1
»
Method 5Q.60^CLP Phase Separation
| 6.3 Phase Separation
I
j 6.3.1 If the sample is multi-phase, split the sample into two jars, place
1 I1 the jars in plastic bags and centrifuge them at 3000 rpm. Centrifuge the
i sample containers for not less than five minutes but no longer than ten
minutes. Check for separation completeness. If incomplete, centrifuge for an
additional five minutes. Record the total centrifugation time.
1 :|
i 6.3.2 Transfer each individual phase to an appropriate tared and labeled
vial or jar and record the individual phase weights, the phase weight
j percentages and the total sample weight for each phase.
6.3'.3 For each liquid phase", test for water miscibility by adding several
i drops of sample to a 2 dram vial containing 0.5 mL of ASTM Type II water.
Record the results as water miscible, partially water miscible or non-water
' miscible. Transfer 35 mL of the liquid to a labeled 40 mL vial or 2 oz.
bottle. Recap original sample.
! . .6.3.4 For each solid or paste phase, transfer approximately 35 g into a
i labeled container.
i
! 6.4 Record description of each phase on the phase log form using phase
descriptions described in Exhibit B. .
f~ 6.5 Remove any material from the outside of vials and jars with toweling and
I soap and water. (Solvents may be necessary, but use only on sealed
! containers.) Place container, separated phases into one plastic autoclave bag
! and store for future aliquoting.
j , 6.6 Aliquoting
l 6.6.1 Weigh a predetermined amount of each phase into an appropriate test
: vial and record the weight of each phase. Refer to individual methods for
; specific weights.
j 6.6.2 Unless requested, minor phases are not aliquoted. For samples with
; , phases of less than 10% but greater than 1%, it will be necessary to contact
I SMO to prioritize the preparations and analyses to be performed, as
; ' insufficient sample may be present to perform all testing requested.
IHC01.2 ' Page 94
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SECTION V
SAMPLE ANALYSIS
Method 150.20-CLP
Potentiometric and Colorimetric Determination of the
pH of Industrial Waste Materials
1. Scope and Application
1.1 This method may be used to directly determine the pH of water miscible
liquids or water extracted wastes. Non-water miscible phases are not
analyzed.
1.2 The pH of,a diluted or undiluted sample is measured by an electrode
response (potentiometric method) or by an indicator test strip (colorimetric
method).
1.3 The results of the direct analysis of water miscible Liquids may be used
for corrosivity characterization. . > _
2. Summary of Method
2.1 Two methods are provided for the determination of the pH of wastes. The
potentioraetric measurement of pH by the use of a low sodium glass combination
pH electrode is to be performed first. If the potentiometric measurement
proves unsatisfactory due to fouling of the electrode, erratic electrode
response or other sample related problems, then the colorimetric method is to
be employed.
3. Interferences
3.1 The glass electrode, in general, is not subject to solution
interferences from color, turbidity, colloidal matter, oxidants or reductants.
3.2 Presence of organic materials in samples can impair electrode response.
These materials can usually be removed from the electrode by detergent washing
followed by water rinsing. Additional treatment with a organic solvent
(methanol or acetone) may be necessary to remove any remaining residue.
3.3 Temperature effects on the potentiometric measurements of pH arise from
two sources. The first source is caused by the change in electrode output at
various temperatures. This interference can be controlled with instruments
having temperature compensation or by calibrating the electrode-instrument
system at the temperature of the samples. The second source is the change of
pH inherent in the sample at various temperatures. This effect is sample
dependent and cannot be controlled. Therefore, both the pH and the ambient
temperature at the time of analysis should be recorded.
IHC01.2 . Page 95
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Method 150.20-CLP
pH Determination
4.
Apparatus and Equipment
4.1 pH meter - capable of response to 0.05 pH units.
4.2 Low sodium glass combination pH electrode.
4.3 Magnetic stirrer and teflon-coated stirring bar.
4.4 pH paper - capable of distinguishing 0.5 pH units over pH range 0-14.
4.5 Box shaker.
4.6 Plastic disposable beakers with lids.
4.7 Disposable filter apparatus (0.45 0m).
5. Reagents
5.1 pH buffers pH-4, pH-7, pH=10
6. Quality Control
6.1 Preparation Blank
6.1.1 Summary
To ensure against contamination during sample preparation, a preparation
blank (PB) is analyzed.
6.1.2 Frequency
At least one PB must be prepared and analyzed with every SDG, or with
each batch1 of samples prepared, whichever is more frequent.
tj.. 6.1.3 Procedure
The PB shall consist of ASTM Type II water.
The first batch of samples in an SDG is to be assigned to PB one, the
second batch of samples to PB two, etc.
Compare the blank value obtained with the limit specified for ASTM Type
II water ± 0.2 pH units.
6.1.4 Calculations
Not applicable.
*A group of samples prepared at the same time.
IHC01.2
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Method 150.20-01^ : pH Determination
6.1.5 Technical Acceptance Criteria
The value obtained for the blank must be within ± 0.2 pH units of the
value specified for the ASTM Type II water.
6.1.6 Corrective Action
If the value obtained is not within the required limit, all samples
prepared with the blank must be reprepared and reanalyzed.
/
6.1.7 Documentation
Report the value obtained on FORM I-HCIN.
6.2 Duplicate Sample Analysis
6.2.1 Summary
Duplicate aliquots of a sample are carried through the preparation and
analysis steps to provide information about the precision of the analytical
methods and the matrix effects.
6.2.2 Frequency
At least one duplicate sample analysis must be performed on each group
of samples of a similar phase for each SDG.2
6.2.3 Procedure
Samples identified as field blanks cannot be used for duplicate sample
analysis.
EPA may require that a specific sample be used for the duplicate sample
analysis.
In the instance where there is more than one duplicate sample per matrix
and concentration per method per SDG, if one duplicate result is not within
contract criteria, flag all the samples of the same phase and method in the
SDG.
Duplicate sample analyses are required for calculation of relative
percent difference.
2EPA'may require additional duplicate sample analysis upon special request by the
Project Officer, for which the Contractor will be paid.
IHC01.2 Page 97
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Method 150.20-CLP
pH Determination
ni
6,2.4 Calculations
RPD
IS -Dl
(S + D)/2
x 100
Where:
RPD - Relative Percent Difference;
S - First Sample Value (original); and
D «* Second Sample Value (duplicate).
Duplicates cannot be averaged for reporting on FORM I-HCIN.
6.2.5 Technical Acceptance Criteria
Compare results of the replicates to the limits ± 0.2 pH units.
6.2.6 Corrective Action
If the value for the replicates exceeds this limit, samples in that
analysis group will not need to be repeated, but the results should be
considered suspect and the analyst should repeat the measurements and take the
appropriate steps to eliminate any problems.
6.2.7 Documentation
The results of the duplicate sample analyses must be reported on FORM
VIII-HCIN.
6.3 Laboratory Control Sample
6.3.1 Summary
A LCS is prepared and analyzed to ensure against analyte loss in the
sample preparation.
6.3.2 Frequency
A reference sample (EPA, pH concentrate) will be prepared according to
the instructions sent with the concentrate and will be analyzed with every set
of analytical sample dilutions.
6.3.4 Procedure
The LCS must be analyzed for each analyte using the same sample
preparations, analytical methods and QA/QC procedures employed for the EPA
samples received.
IHC01.2
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Method 150.20-CLP
pH Determination
The LCS must be obtained from EPA. (If unavailable, other EPA Quality
Assurance Check samples or other certified materials may be used.) EPA pH
concentrates are available from:
EMSL/Cincinnati
Quality Assurance Branch
26 Martin Luther King Avenue
Cincinnati, OH 45268
Phone: (513/FTS) 684-7325
6.3.5 Calculations
%Recovery - "
Found Concentration
True Concentration
100
6.3.6 Technical Acceptance Criteria
Recovery for the LCS must be within the 95 percent confidence interval
(also sent with the concentrate).
6.3.7 Corrective Action
If the percent recovery for the LCS is outside the 95 percent confidence
interval established by EPA, then the analyses must be terminated, the problem
corrected, and the samples associated with that LCS must be reprepared and
reanalyzed.
6.3.8 Documentation
Report the LCS found concentration, true concentration, and percent
recovery on FORM VIII-HCIN. "
7.
Sample Preparation
7.1 Aliquot 1.00 g ± 0.1 g of sample into a disposable beaker. Dilute each
one gram aliquot to 100 mL total volume with ASTM Type II water.
7.2 For water miscible phase samples, aliquot approximately 10 mL of the
phase (if available) into a vial suitable for potentiometric measurement of
the pH. (Do not dilute the 10 mL water miscible phase.)
7.3 Place all diluted samples on a box shaker and shake for one hour at a
medium setting.
7.4 Filter all sample dilutions through disposable filter units. For
dilutions with more than one phase, allow the sample dilution to settle before
apr-lying the vacuum.
IHC01.2
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Method 150.20-CLF
oH Determination
7.5 Store samples at room temperature and analyze within the 2k hour time
period.
NOTE: This sample can also be used for the determination of conductivity.
8. Calibration and Sample Analysis
8.1 Calibration
8.1.1 Because of the wide variety of pH meters and accessories, detailed
operating procedures cannot be incorporated into this method. The analyst
must be acquainted with the operation of each system and be familiar with all
instrument functions. Special attention to care of the electrodes is
recommended.
8.1.1.1 The stability of the calibration curve will vary with both
temperature fluctuations and the sample matrices being analyzed. Therefore, a
calibration check must be performed at least once every 10 sample analyses.
Increasing the frequency of checking the calibration is left to the discretion
of the operator.
8.1.1.2 Each instrument/electrode system must be calibrated with two
buffers that bracket the expected pH of the samples.
8.1.1.2.1 The instrument is to be calibrated as outlined in the
manufacturer's instructions. Repeat adjustments on successive portions of the
two buffer solutions until readings are stable (less than 0.1 units change in
one minute)' and within 0.1 pH units of the buffer solution value. On the
bench sheet record the pH range, slope (if available) and actual buffer
readings to the nearest 0.1 pH unit.
8.1.1.3 When checking the calibration, both buffers that bracket the
sample value used for calibration shall be checked and readings should agree
within 0.1 units of the value sought. If the readings are not acceptable,
steps shall be taken to correct the problem (e.g., recalibration, and cleaning
the electrode).
8.1.1.4 When calibrating the instrument the analyst should become
cognizant of the "typical" response time required for the electrode/instrument
set-up in use. This is extremely important when analyzing industrial waste
samples due to the possibility of sample related impairment of electrode
response. The extreme pH ranges encountered in industrial waste samples can
cause memory effects and other electronic problems. Also, due to the presence
of organic materials in the samples, physical coating of the electrode may
occur.,that is masked by the high ionic strength buffer measurements taken in
between sample measurements.
IHC01.2
Page 1-00
-------
Method 150.20-CLP
pH Determination
8.2 Recalibration
8.2.1 Recalibration of the pH meter includes checking the buffers at both
ends of the bracketed calibration range and adjusting the instrument if
necessary. Any changes in instrument parameters (i.e., slope) should be
thoroughly documented on the bench sheet along with which sample measurements
correspond to which calibration.
8.2.2 If upon checking the buffer solutions the buffer value fails to.read
the .expected pH ± 0.1 units, then all samples past the last acceptable buffer
check must be reanalyzed. An exception to this rule is for a single sample
analysis where, upon repeating the sample analysis and immediately checking
the buffer, the buffer fails to be ±0.1 units of the expected value. This
problem may occur with samples of extreme pH or samples containing organic
material.
8.3 Sample Analysis - Potentiometric Method
8.3.1 Record on the bench sheet the ambient temperature in the
laboratory. It is best to perform measurements on the diluted sample phases
first and then measure the pH of the undiluted water miscible phase samples.
* . -
8.3.2 Place the electrode into the sample and make certain there is
sufficient volume to cover the sensing elements of the electrode.
8.3.3 Swirl the sample preparation using a stir bar while watching
readout of pH meter. Continue swirling until the pH stabilizes (pH changes
less than 0.1 units in one minute). Stop swirling and allow pH to stabilize
again.
8.3.4 Record on the bench sheet the observed pH to a tenth of a unit
(i.e., 4.0, 4.1, etc;.) for pH greater than 1.0 and less than 13.0. For pH
less than 1.0 or greater than 13.0, report results as < 1.0 and > 13.0,
respectively. Rinse probe (see Section 8.6).
8.3.5 If for some reason the potentiometric measurement is questionable
(i.e., erratic response, QC limits are exceeded, etc.), then repeat the
measurement using the colorimetric method (Section 8.5). Document on the
bench sheet the method of pH measurement.
8.4 Sample Analysis 7 Colorimetric Method
'8.4.1 Immerse pH paper directly into a portion of the sample preparation
sufficient to wet the paper thoroughly, or wet the paper by dropping the
sample preparation onto the paper from a pipette.
8.4.2 Read the re~v.lt of the test according to the manufacturer's
instructions and record the result on the bench sheet.
IHC01.2
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Method 150.20-CLP
pH Determination
8.5 Rinsing Probe
8.5.1 A slow response of the probe indicates .the possibility of a fouled
probe. If cleanliness is in doubt based on response time (Section 8.1.1.4),
then place the probe in a calibration buffer solution and note response time.
If response time is greater than usual, see Section 8.5.2.
8.5.2 Rinse the probe with a detergent solution followed by ASTM Type II
water and recheck the response time. If normal, calibrate and proceed to next
sample; if not see Section 8.5.3.
8.5.3 Rinse the probe with methanol or acetone followed by ASTM Type II
water and check response time. If normal, calibrate and go to next sample; if
not discontinue analysis until the problem is corrected. Recalibration may be
required if solvents are used to clean the probe.
9.
Documentation
9.1 Report the recorded pH value (to one tenth of a whole number) on FORM I-
HCIN under pH.
IHC01.2
Page 102
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Method 120.1-CLP
Determination of Conductivity in
Industrial Waste Material
1. Scope and Application
1.1 This method can be used to directly determine the specific conductance,
in /imhos at 25°C, of water miscible liquid phases or water extracted solid
phases. Non-water miscible phases are not analyzed.
1.2 The results of measuring the specific conductance can aid in estimating
sample size to.be used for common chemical determinations, check results of a
chemical analysis, estimate total filtrable residue in a sample, and measure
the corrosion rate.
2, Summary of Method
2.1 The specific conductance of a diluted qr an undiluted sample is measured
by use of a self-contained conductivity meter, Wheatstone bridge type, or
equivalent.
2.2 The results of direct analyses of water miscible liquid are preferably
analyzed at 25°C. If not, temperature corrections are made and results
reported at 25°C.
3. Interferences
3.1 Instrument must be standardized with KC1 solution before daily use.
3.2 Conductivity cells must be kept clean. If not follow manufacturers
instructions for cleaning cell to maintain a cell constant of 1.0 /imho or
micro dipping type cell with 1.0 /imho constant.
3.3 Temperature variations and corrections represent the largest source of
potential error. This can be controlled by allowing the sample to come to
room temperature.
4. Apparatus and Equipment
4.1 Conductivity bridge, range 1 to 1000 fimho per centimeter.
4.2 Conductivity cell, cell constant 1.0 or micro dipping type cell with 1.0
constant.
4.3 Thermometer, reading in degree °C at 0.1 intervals.
4.4 Plastic disposable beakers, 100 mL.
IHC01.2
Page 103
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Method 120.1-CLP
Conduct iyity
4.5 Disposable filter apparatus (0.45
5. Reagents
5.1 Standard potassium chloride solutions, 0.01 M: Dissolve 0.7456 g of
pre-dried (2 hours at 105 ± 5°C) KC1 in reagent grade water and dilute to 1 L
at 25°C.
6. Quality Control
6.1 Preparation Blank
6.1.1 Summary
To ensure against contamination during sample preparation, a preparation
blank (PB) is analyzed.
6.1.2 Frequency
A least one PB must be prepared and analyzed with every SDG, or with
each batch3 of samples prepared, whichever is more frequent.
6.1.3 Procedure
The PB shall consist of ASTM Type II water.
The first batch of samples in an SDG is to be assigned to PB one, the
second batch of samples to PB two, etc.
Compare the blank value obtained with the limit specified for ASTM Type
II water ± 6 /imhos for conductivity at 25°C.
6.1.4 Calculations
Not applicable.
6.1.5 Technical Acceptance Criteria
The value obtained by the blank must be with ± 6 /zmhos specified for
ASTM Type II water at 25°C.
3A group of samples prepared at the same time.
IHC01.2
Page 104
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Method 120.1-CLP
Conductivity
6.1.6 Corrective Action
If the value obtained is not within the required limit, all samples
preoared with the blank must be reprepared and reanalyzed.
6.^.7 Documentation
Report the value obtained on FORM I-HCIN.
6.2 Duplicate Sample Analysis
6 .2.. 1 Summary
Duplicate aliquots of a sample are carried through the preparation and
analysis steps to provide information about the precision of the analytical
methods and the matrix effects.
6.2.2 Frequency
At least one duplicate sample analysis must be performed on each group
of samples of a similar phase for each SDG.*
6.2.3 Procedure
Samples identified as field blanks cannot be used for duplicate sample
analysis.
EPA may require that a specific sample be used for the duplicate sample
analysis.
In the instance where there is more than one duplicate sample per matrix
and concentration per method per SDG, if one duplicate result is not within
contract criteria, flag all the samples of the same phase and method in the
SDG.
Duplicate sample analyses are required for calculation of relative
percent difference.
6.2.4 Calculations
RPD -
IS - Dl
(S + D)/2
x 100
4EPA may require additional duplicate sample analysis upon special request by
the Project Officer, for which the Contractor will be paid.
IHC01.2
Page 105
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Method 120.1-CLP ' Conductivity
J ; Where:
i ; RPD - Relative Percent Difference;
| S - First Sample Value (original); and
: " D Second Sample Value (duplicate).
i
| ;: Duplicates cannot be averaged for reporting on FORM I-HCIN.
I
6.2.5 Technical Acceptance Criteria
i
' Compare results of the replicates to the limits ± 6 ^mhos at 25°C.
: 6.2.6 Corrective Action
i If the value for the replicates exceeds this limit, samples in that
analysis group will not need to be repeated, but the results should be
i considered suspect and the analyst should repeat the measurements and take the
; ;; appropriate steps to eliminate any problems.
l '
| 6.2.7 Documentation
i
[ The results of the duplicate sample analyses must be reported on FORM
VIII-HCIN.
6.3 Laboratory Control Sample
: 6.3.1 'Summary
A LCS is prepared and analyzed to ensure against analyte loss in the
sample preparation.
; 6.3.2 Frequency
i
A reference sample (EPA, conductivity) will be prepared according to the
instructions sent with the concentrate and will be analyzed with every set of
analytical sample dilutions.
'. 6.3.4 Procedure .
' The-LCS must be analyzed for each analyte using the same sample
preparations, analytical methods and QA/QC procedures employed for the EPA
: samples received.
i1
The LCS must be obtained from EPA. (If unavailable, other EPA Quality
' Assurance Check samples or other certified materials may.be used.) EPA
conductivity concentrates are available from:
i
i
IHC01.2 Page 106
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Method 120.1-CLP Conductivity
EMSL/Cincinnati
Quality Assurance Branch
26 Martin Luther King Avenue - *
Cincinnati, OH 45268
Phone: (513/FTS) 684-7325
6.3.5 Calculations
_ Found Concentration , A
%Recovery = ~ ~ ~ : x 100
J True Concentration
6.3.6 Technical Acceptance Criteria
Recovery for the LCS must be within the 95 percent confidence interval
(also sent with the concentrate).
6.3.7 Corrective Action
If the percent recovery for the LCS falls outside the 95 percent
confidence interval established by EPA, then the analyses must be terminated,
the problem corrected, and the samples associated with that LCS reprepared and
reanalyzed.
6.3.8 Documentation
Report the LCS found concentration, true concentration, and percent
recovery on FORM VIII-HCIN.
7. Sample Preparation
7.1 Aliquot 1.00 ± 0.1 g of solid phase sample into a disposable beaker.
NOTE: Save water miscible phase sample aliquot for analysis, if needed.
7,2 Dilute one gram aliquot to 100 mL total volume with ASTM Type II water.
7.3 Place all diluted samples on a box shaker for one hour at a medium
setting. If a sample yielded 100 mL of the water miscible phase dilutions,
then there is no need to shake the sample unless a. precipitate forms upon
dilution. In this case, mix the non-precipitating water miscible phase
dilutions thoroughly using a glass stirring rod. Treat precipitating water
miscible phase sample as solids. Do not shake undiluted water miscible
phases.
7.4 Filter all sample .dilution through disposable filter units that have
been pretreated by washing with high quality reagent water and pre-rinsed with
sample before use. For dilutions with more than one phase, allow the sample
IHC01.2 Page 107
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Method 120.1-CLP
Conductivity
to settle before applying the vacuum. Store samples at room temperature and
analyze promptly.
NOTE: This sample preparation can also be used for the determination of pH.
8. Calibration and Sample Analysis
8.1 Calibration
8.1.1 Because of the wide variety of conductivity meters and accessories,
detailed operating procedures cannot be incorporated into this method. The
analyst must be acquainted with the operation of each system and be familiar
with all instrument functions. Special attention to the care of the cell is
vitally important!
8.1.1.1 The analyst should use the standard potassium chloride solution
(5.1) and the table below to check the accuracy of the cell constant and
conductivity bridge.
Conductivity 0.01M KC1
degree "C
21
22
23
24
25
26
27
28
mnhos/cm
1305
1332
1359
1386
1413
- 1441
1468
1496
8.1.2 When checking the cell calibration, the readings should agree within ±
1.0% or 1 /imhos/cm, whichever is greater. If the readings are not acceptable,
then steps should be taken to correct the problem and recalibrate.
8.1.3 When calibrating the instrument, the analyst should become familiar
with the overall response time and the manufacturer directions for operation
and maintenance of the instrument.
8.2 Sample Analysis
8.2.1 Follow the direction of the manufacturer for the operation of the
instrument.
8.2.2 Allow samples to come to room temperature approximately between 23 to
27"C, if possible.
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Method 120,1-CLP
Conduct ivity
8.2.3 Determine the temperature of samples within ± 0.5°C. NOTE: If the
temperature of the samples is not 25°C, make temperature correction in
accordance with the instructions in Section 9 to convert readings to 25"C.
8.2.4 Place probe in solution to be measured and obtain reading as
instructed by the manufacturer. Record the reading on the benchsheet.
9. Calculations
9.1 These temperature corrections are based on the standard KC1 solution.
9.1.1 If the temperature is below 25'C, add 2% of the reading per degree.
9.1.2 If the temperature is above 25CC, subtract 2% of the reading per
degree.
10. Documentation
10.1 Report results as Conductivity, in ^mhos/cm at 25°C, on FORM I-HCIN.
IHC01.2
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Method 200.62-A-CLP
Dissolution of Industrial Waste Materials For
Elemental Analysis by Potassium Hydroxide Fusion
1. Scope and Application
1.1 This method offers a vehicle to dissolve inorganic metals from a wide
variety of industrial waste materials. In particular, organic matter is
largely destroyed and silica matrices are dissolved.
1.2 The method has been successfully used to prepare solutions for metals
analysis of oils, fats, polymers, pigments and paint, soil, sludge, sediment,
fly ash, glass, and inorganic salts.
1.3 The recovery of 30 metals has been verified by this method in a number of
standard reference materials.
1.4 For routine use of the method, HN03 is recommended although HC1 may also
be use for special situations (e.g., quantitative results for silver above 100
mg/Kg), if the analysis laboratory can demonstrate that the use of HCl results
in meeting the QC requirements.
1.5 All samples shall be carried through the sample preparation procedure
and then run undiluted. When an analyte concentration exceeds the calibrated
or linear range, appropriate dilution and reanalysis of the prepared sample is
required. The dilution factor shall not bring the concentration below the
CRQL. All dilutions shall be taken from the original sample, diluting
previously diluted samples are not acceptable.
2.
Summary of Method
2.1 A 0.25 g aliquot of sample is fused with 2 g potassium hydroxide in a
pyrolytically-coated graphite crucible. Commercial potassium hydroxide
usually contains about 15% by weight of water. Water appears to help destroy
organic matter by hydrolysis reactions. In addition, the water appears to
lower the melting point of the mixture to about 125"C although the KOH may be
dissolving in the residual water at this temperature to mimic melting. The
water-potassium hydroxide melt is formed during heating in a block digester.
The temperature of the melt is increased slowly so that vigorous oxidation
reactions between organic matter and the fusion matrix can be controlled. The
temperature is increased to 360'C, and the melt solidifies as the water
evaporates. The crucibles are then heated in an electric furnace in which
anhydrous KOH (and K2C03 from absorbed C02) melts at around 400°C, depending
upon the amount of K2C03 and other dissolved matter from the sample. The
higher temperatures of the melt subject the sample to an oxidizing
environment, perhaps due to the partial transformation of KOH to K20. The
final temperature of the melt should be 525°C.
IHC01..2 - Page 110
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Method 200.62-A-CLP
Potassium Hydroxide Fusion
2.2 The cooled fusion mass is rinsed from the crucible into a beaker. Nitric
acid is warmed in the crucible and then rinsed into the beaker. Hydrogen
peroxide reduces Cr (VI) to Cr (III), in order to avoid precipitation of
insoluble metal chromates. When titanium is present in high concentrations,
an -range peroxide [Ti(02)(OH)ag] + complex is formed with the peroxide. The
peroxide addition may also aid in the dissolution or stabilization of B, Co,
Mn, Mo, Si, W, and other elements. The solution is mixed overnight to aid
dissolution and to outgas the peroxide. The final dilution volume is 100 mL.
2.3 The spike sample is prepared by adding 0.0125 g of the solid spiking
mixture to a 0.25 g aliquot of sample which is then carried through the sample
preparation procedure.
2.4 A preparation blank is prepared for each sample phase as follows:
2.4.1 Water miscible phase: The preparation blank for the water miscible
phase consists of 0.25 g of ASTM Type II water which is carried through the
sample preparation procedure.
2.4.2 Non-water miscible phase: The preparation blank for the non-water
miscible phase is a reagent blank.
2.4.3 Solid phase: The preparation blank for the solid phase is a reagent
blank.
3. Apparatus and Equipment
3.1 Electric furnace - temperature controlled to at least 550°C.
3.2 Block digester - temperature controlled to at least 360°C; hole size 25
mm diameter.
3.3 Exhaust hood or suitable venting system.
3.4 Rotary shakers (two), variable speed.
3.5 Pyrolytically-coated graphite crucibles (Ultra Carbon, Bay City,
Michigan, #UF-45 with PT-101 coating, or equivalent).
3.6 Handling tongs - platinum tipped.
3.7 Hot plate - preferably ceramic top.
3.8 Disposable biological membrane filters (0.45 /zm) or membrane filter
apparatus and'filters (0.45 /im) .
3. Disposable plastic 8 oz. bottles with lids.
IHC01.2
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Method 200 62-A-CLP
Potassium Hydroxide Fusion
4. Reagents
4.1 Potassium hydroxide, reagent grade.
4.2 Nitric acid, concentrated, reagent grade.
4.3 Hydrochloric acid, concentrated, reagent grade,
4.4 Hydrogen peroxide, 30%.
5. Sample Preparation and Handling .
5.1 Samples are processed through the phase separation procedure (Method
50.60-CLP). Waste samples are not generally dried; results will be. reported
on a wet weight basis. Phases of a sample will be prepared and analyzed
individually. .
6.
Procedure
6.1 Preheat block digester to 160°C. To facilitate placement or removal of
the crucibles in or from a standard total nitrogen block digester, drop old
empty crucibles in the holes (crucibles open side up) to make up extra space.
The digester sits on the rotary shaker.
6.2 Place a new crucible on clean paper on an analytical balance; tare the
crucible.
6.3 Weigh 0.250 ± 0.015 g of an analytical sample into a crucible. If the
sample should get"on the crucible lip or outside walls, a new sample aliquot-
should be weighed into a new crucible.
6.4 Add 2.0 ± 0.1 g of KOH to the crucible. . , .
6.5 When all the crucibles contain sample and KOH, place the crucibles in
the block digester.
6.6 Heat the sample preparations at 160°C in the block digester, for thirty
minutes, with constant swirling provided by the rotary shaker moving at 100
RPM. Samples containing high concentrations of organic matter may evolve C02
and cause bubbling over of the fusion. To prevent this from occurring,
manually swirl each crucible at least once every 15 minutes using the platinum
tongs. (Turn off shaker to remove crucibles.)
6.7 After heating the preparations at 160eC for thirty minutes, set the
block controller to 366*0 and continue heating the preparations until they are
dry. This step usually takes at least ninety minutes. NOTE: The sample must
be mixed every 15 minutes by gently swirling the crucible to avoid possible
creeping or spattering of .the sample.
IHC01.2
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Method 200.62-A-CLP
Potassium Hydroxide Fusion
6.8 During the latter part of the
furnace to 425"C.
360°C heating step, preheat the electric
6.9 After the fusion melts have dried and solidified, transfer the crucibles
to the furnace (which also sits upon a rotary shaker moving at 100 RPM). Heat
the samples for 15 minutes at 425°C, followed by heating for 20 minutes at
525"C. Make sure that the crucibles do not touch each other. The required
temperature setting is critical and may vary from furnace to furnace. The
temperature should be high enough to allow Cr recovery from the NIST LCS --to be
within the contract acceptance limits, but low enough to minimize sample from
creeping. The contractor shall maintain a record demonstrating that the
furnace has been properly calibrated prior to use.
6.10 Remove the crucibles from the furnace.
6.11 When the crucibles are removed, it may be evident that some of the
fusion melts have crept up and over the lip of the crucible. If the creeping
has progressed to within one half inch of the outside bottom of the crucible,
the preparation must be discarded and another fusion shall be performed on the
analytical sample. If the-creeping persists for a certain sample, the fusion
time at 525°C may be shortened, or the high -furnace temperature lowered to
475-500°C. Another option is to top the crucible with a lid made from the
bottom of another crucible. If any options are used, a set of quality control
samples must be prepared under the same conditions.
6.12 Using ASTM Type II water, rinse all deposits from the outside and lip of
the crucible into an 8 oz. plastic beaker. Fill the crucible with reagent
water. This often loosens the fusion product so that it falls out as one
piece. After the ASTM Type II water has been in the crucible for a few
minutes, rinse all the fusion product out of the crucible and into the cup
with ASTK Type II water. Do not use more than 70 raL ASTM Type II water. If
it appears that the fusion product is not going to be removed with 70 mL of
ASTM Type II water, then crush the fusion product in the crucible with a
teflon or glass rod and rinse the pieces of the fusion product in the crucible
and on the rod into the beaker. Record on the bench sheet the color of the
solution in the beaker.
6.13 Fill the crucibles with approximately 7 mL concentrated nitric acid and
place the empty crucibles on a hot plate set at 95°C. Heat until acid fumes
are apparent. ,
6.14 Carefully pour the nitric acid from the crucibles into the disposable
beakers. Carbon dioxide may be released, so be cautious. Rinse the crucible
with a minimum of reagent water and combine the rinse with the solution in the
disposable beaker.
6.15 Add an additional 3 mL of concentrated nitric acid to each beaker.
Record on the bench sheet the color of the solution in each beaker.
IHC01.2
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Method 200.62-A-CLP Potassium Hydroxide Fusion
NOTE: The high concentration of acid in the solution at this point may cause
some metals to become insoluble. Therefore, sufficient ASTM Type II water
must be added at this time to bring the total volume to a minimum of 50 mL.
6.16 If the fusion product does not readily dissolve, cap the beaker and
shake it on the shaker at 100 RPM for a maximum of 30 minutes, or until it is
dissolved.
6.17 Add 1 mL of 30% hydrogen peroxide to each solution. Record on the bench
sheet the color change of the solution in each beaker when peroxide is added.
Cap and shake the solutions on the shaker at 100 RPM overnight. During the
first few hours, vent the beakers periodically.
6.18 Quantitatively transfer each solution to a disposable filter apparatus
and apply a vacuum. After the solution has been filtered into a graduated
vessel, rinse the filter with ASTM .Type II water and add the rinse to the
filtered solution. Record on the, bench sheet the presence of any residue on
the filter and describe it.
6.19 Using ASTM Type II water, dilute the filtered solution to 100 mL using
the marks on the graduated cylinder. If prior to the volume adjustment the
volume is greater than 100 mL, dilute the solution to 115 mL. Record the
final volume of each solution on the bench sheet.
6.20 If the solution requires shipment for analysis, transfer the solution to
an acid-washed shipping container and label appropriately. Solutions are now
i ; ready for analysis.
(
! . 7. Documentation
7.1 Report the EPA Sample number, preparation date, sample weight (in
grams), volume (in mLs), color and clarity on FORM XIV-HCIN.
IHC01.2 Page 114
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Method 200.62-B-CLP
Pneumatic Nebulization Inductively Coupled Argon
Plasma Optical Emission Spectroscopic (ICP) Analysis
1. Scope and Application
1.1 This method is applicable to the ICP determination of eighteen metals
dissolved by the potassium hydroxide (KOH) fusion (Method 200.62-A-CLP) at all
concentrations.
1.2 The eighteen metals to be determined include: aluminum, barium,
beryllium, cadmium, calcium, chromium, cobalt, copper, iron, lead, magnesium,
manganese, nickel, silver, sodium, thallium, vanadium, and zinc.
2. Summary of Method
2.1 Eighteen metals are determined by Inductively Coupled Argon Plasma
Optical Emission Spectroscopic (ICP) Analysis. The potassium hydroxide fusion
dissolutions of the samples are pumped into a pneumatic nebulizer. The
aerosol formed is transported into an inductively coupled plasma and the
metals are excited into higher electronic states. Atomic and ionic line
emission spectra characteristic of the particular metals are produced when the
electrons decay back to the lower energy levels. The spectra are dispersed by
a spectrometer and the intensity of specific line radiation(s) are monitored
simultaneously or sequentially by a photomultiplier tube(s). The photocurrent
produced by the photomultiplier tube will increase in direct proportion to the
concentration of the element in the sample within the linear range of a
specific emission line. The photocurrent is processed by a computer system
and related to concentration through a calibration procedure.
2.2 Calibration is performed by standardizing the instrument with a series
of mixed element standards and a blank that are matrix matched to the
potassium hydroxide fusion dissolution. Every solution analyzed, such as a
dilution, calibration stability standard, or reference sample must be matrix
matched to the fusion dissolution.
2.3 Appropriate steps must be taken to insure that potential interferences
are corrected. This is especially important for spectral interferences.
Recommendations for correcting for interferences are briefly summarized below
under headings that categorize the type of interference that is being
considered. Section 7 contains requirements for the operation of the ICP.
2.3.1 Physical Interferences
The use of peristaltic pump to introduce the fusion solution into the
nebulizer.
Frequent (20% or better) analysis of the calibration stability standard.
IHC01.2 Page 115
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Method 200.62-B-CLP
Inductively Coupled Plasma
Adequate rinsing (one minute or more) between sample analyses using 10%
HN03 or 10% HC1, and optional use of humidified argon or a nebulizer tip
washer as necessary.
2.3.2 Chemical Interferences
* Matrix matching between fused samples and all standards and sample
dilutions is used in sample analysis. The high potassium concentration
of the fusion matrix helps to eliminate ionization interferences.
2.3.3 Spectral Interferences
Use of calculated interelement corrections in the form of factors or
first or second order equations that describe the interference function
(on-peak correction).
Optional use of measurement of background shift on either side or both
sides of the analyte line (off-peak correction).
Optionally, wavelength" scans (for each of the analyte element
wavelengths) for each of the samples simultaneously plotted with a
calibration blank scan and a calibration standard scan may be performed.
2.4 Every solution, including calibration standards, calibration and method
blanks, reference samples, and fused samples must be analyzed using two full
exposures (peak scan), each of which is sufficient to meet the method
detection limit for each analyte emission line. All exposure times must be "
the same for all analyses and all quarterly analyses (i.e., method detection
limit and interelement correction factor).
2.5 Both the off-peak (background) and on-peak (interelement correction
coefficients or equations) interference corrections made for all metals must
be calculated and reported with the analysis results.
2.6 If the sum of the values of the interference correction(s) made on any
metal is greater than the resulting metal concentration, the metal value is to
be flagged with an "I" on FORM I-HCIN.
2.7 If the analyte requiring dilution interferes on with another metal, the
interference corrections) must reflect the actual concentration of the
interferant in the undiluted samples.
2.8 , The specific spectral lines that are employed must be reported.
2.9 All reported analyte data must have been obtained within the linear
range of the respective analyte emission line. If any analyte concentration
results in the linear range of the spectral line being exceeded, the sample
IHC01..2
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Method J!00.62-B-CLP Inchictivelv Coupled Plasma
must be diluted such 'that the resulting solution concentration falls within
the linear range, but not below the CRQL.
2.10 If a value for silver found; in the HN03 preparation is greater than 100
rag/Kg, the sample must be reprepared and reanalyzed using HC1 in place of the
HN03 for sample dissolution.
3. Interferences
3.1 Inductively coupled argon plasma emission spectroscopy is prone to
interelement effects, which in practice are experienced in two main forms.
Interferences that cause a translation of the analytical curve are caused by
spectral line overlap or increase in background due to an electron/metal ion
recombination continuum and/or scattered light within the spectrometer. For a
given matrix and spectral line, a constant additive interference is produced
that is independent of the analyte concentration. Rotational interference of
the analytical curve, experienced essentially as a change in sensitivity, is
due to the combined effects of variations in nebulizer performance produced by
the physical properties of the sample solution and changes in the excitation
conditions in the plasma caused by -the matrix metals. Both forms of
interference can operate simultaneously .for a particular sample matrix.
3.2 Spectral interference from poorly resolved metal spectral lines, such as
scattered light, or broad continuum spectral background, will lead to
systematic error in the analytical results unless proper corrections are made.
Molecular band emission will lead to a deterioration of the detection limit
and will increase the difficulty of off-peak background correction. Methods
of correcting translational interference (other than exact matrix matching of
the standards to the sample) include the on-peak correction technique. This
method can be applied to both spectral line overlap and background
enhancement, but it requires specific knowledge of the metals causing the
interference. On-peak correction can only be performed on a quantitative
basis if the interfering metals are included in the multi-metal analysis,
although uncertainties may still exist in whether the correction coefficients
employed match those required for the particular sample matrix.
3.3 Rotational calibration curve interference manifests itself for a given
matrix and spectral line as a change in the slope of the analyte calibration.
Included in this type of interferences are: sample nebulization and transport
effects, often called "physical interference" including "lateral diffusion
interferences;" and "chemical interferences" such as "solute vaporization
interference" and "ionization interferences." Such interferences can be
reduced by matrix matching of the standards and samples and by the method of
standard additions, although standard additions can become quite lengthy and
impracticable for multi-metal analyses. Matrix matching can correct for any
of these interferences but the correction is dependent on the accuracy of the
matching. Variations in the matrix from sample to sample will cause
IHC01.2 Page 117
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Method 200.62-B-CLP
Inductively Coupled Plasma
corresponding inaccuracies in the analyte results. However, since an
abundance of potassium is present in both samples and standards, rotational
interferences are largely eliminated by matrix matching.
4. Apparatus and Equipment
4.1 Computer-controlled inductively coupled argon plasma optical emission
spectrophotometer system with:
4.1.1 Folychromator with associated dispersion and detector system such
that the metals can be determined simultaneously, or a sequential scanning
instrument that allows achievement of the quality control requirements for
this method.
4.1.2 Radiofrequency generator and coupling system.
4.1.3 Pneumatic nebulizer.
4.1.4 Software capable of performing both off-peak (background correction)
and on-peak (coefficients of first or second order regression equations
describing expected interference) spectral interference corrections. In
addition, the software must be capable of creating a hard copy output of both
types of corrections in either concentration units or analyte raw intensity
data along with net calculated concentrations.
4.2 Argon gas supply, welding grade or better,.
4.3 Assorted laboratory volumetric glassware, pipets and micropipets.
4.4 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.
5. Reagents and Standards
5.1 Nitric acid and hydrochloric acid used in the preparation of standards
and for sample processing must be of high purity.
5.2 Potassium hydroxide, ACS reagent grade.
IHC01.2
Page 118
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Method 200.62-B-CLP
Inductively Coupled Plasma
5.3 Water equivalent to ASTK Type II is used throughout.
5.4 Stock standard solutions: Standards must be made from ultrapure
materials. The stock standard solutions may be the same as the spiking
standard solutions, if desired.
5.5 Spiking standard solutions: Standards must be made from ultrapure
materials. Both multi-metal and single metal solutions will be needed.
Because of the limited sample volume (100 mL), multi-metal solutions will be
needed to maintain the sample matrix at 952 original strength-after the
addition of the spike volume.
5.5.1 No more than five multi-metal stock standards will be required
containing metals in the following concentrations:
Metals
Cone. (me/L)
Na
Al, Ca, Fe, Mg
Ba, Co, Mn, Ni, Pb, Ag, Tl, V
Be, Cd, Cu, Cr, Zn
10000
1000
500
100
5.5.2 Using the appropriate metal salts and solution matrices, the
following standards have been found to be stable for one year.
Metal Mixes
Al, Ba, Be, Fe, Ni, Ag, Na, Tl
Ca, Cd, Co, Cu, Pb, Mg, Mn, Zn
Cr
V
Matrix
20% cone. HC1
10% cone. HN03
Water
2% cone. HN03
5.5.3 A single metal standard at 10,000 mg/L will be needed for Na and at
1,000 mg/L for the remaining metals.
5.6 Calibration standards: Prepare calibration standards by dilution of
stock or spiking standard solutions. All calibration standards must contain 2
g of KOH and 10 mL of concentrated HN03 per 100 mL. Concentrated hydrochloric
acid can be used instead of HN03 if required for stabilization of a metal(s).
It is convenient to prepare a solution containing 4 g of KOH and 20 mL of HN03
per 100 mL, using 50 mL of this solution per 100 mL in the preparation of the
s tandards.
5.7 Calibration blank: Prepare calibration blanks such that the resulting
solution contains 2 g of KOH and 10 mL of concentrated HN03 per 100 mL.
5.8 Calibration stability standard(s): Calibration stability standards must
be traceable to NIST certified standards and must be made from ultrapure
IHC01.2
Page 119
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Method 200.62-B-CLF
Inductively Coupled Plasma
materials. The resulting solution(s) must contain 2 g of KOH and _0 raL of
concentrated HN03 per 100 mL with the following metals present at the given
concentrations:
Metals
Na
Al, Ca, Fe, Mg
Ba, Co, Mn, Ni, Pb, Ag, V, Tl
Be, Cd, Cu, Cr, Zn
Cone.(mg/L)
100
10
5
1
5.9 Initial calibration verification: The initial calibration verification
solution must be from a different source than that used for the calibration
standards and must be approximately in the middle of the respective
calibration curve.
5.10 ICP interference check sample: Prepare by dilution of the stock
standards if it is not available from the EPA. If the solution is prepared by
the analyst, it must be made using the concentrations in Table 2 of Exhibit C.
It must be run at least 5 times and the mean standard deviation must be
reported in the raw data.
6. Quality Control
6.1 Instrument Calibration
6.1.1 Summary
Prior to the analysis of samples and required QC, each ICP system must
be initially calibrated to determine instrument sensitivity.
6.1.2 Frequency
Instruments must be calibrated daily or once every 24 hours and each
time the instrument is set up.
6.1.3 Procedure
Calibration standards must be prepared using the same type of matrix and
at the same concentration as the preparation blank following sample
preparation,
Calibrate according to instrument manufacturers recommended procedures
using at least two standards, one being a blank.
Before beginning the sample run, reanalyze the highest mixed calibration
standard as if it were a sample.
IHC01.2
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Method 200.62-B-CLP
Inductively Coupled Plasma
6.1.4 Calculations
v n Found Concentration ,--
% Recovery = ~ ~ : x 100
J True Concentration
6.1.5 Technical Acceptance Criteria
Recovery for the highest mixed calibration standard must be within ± 5
percent of the true value (i.e., 95-105%).
6.1.6 Corrective Action
Follow instrument manufacturers recommendations to correct the problem.
Also, 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 a CCV and a CCB.
6.1.7 Documentation
The instrument standardization date and time must be included in the raw
data.
6.2 Initial Calibration Verification
6.2.1 Summary
Immediately after the ICP system has 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) (ICV) at each
wavelength used for analysis.
6.2.2 Frequency
Each time the instrument is calibrated, the ICV must be run immediately
following the calibration, before any samples are analyzed.
6.2.3 Procedure
If the ICV solution(s) are not available froni 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 linear 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.
IHC01.2
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Method 200.62-B-CLP Inductively Coupled Plasma
j 6.2.4 Calculations
! » Found Concentration , nf.
% Recovery - r : x 100
! . J True Concentration
' 6.2.5 Technical Acceptance Criteria
!l
,, Recovery for the ICV must be within ± 10 percent of the true value
! (i.e., 90-1107.) . (See Table 2, Exhibit C)
6.2.6 Corrective Action
When recoveries of the ICV exceed the technical acceptance criteria, the
analysis must be terminated, the problem corrected, the instrument
recalibrated, and the calibration reverified.
6.2.7 Documentation
Report the ICV found concentration, true concentration, and percent
recovery on FORM II-HCIN.
6.3 Continuing Calibration Verification
6.3.1 Summary
j To ensure calibration accuracy during an analysis run, a continuing
I , calibration verification solution (CCV) is analyzed and reported for every
j ; wavelength used for the analysis of each analyte.
i
I 6.3.2 Frequency
i The CCV is run at a frequency of 10 percent or every two hours during an
analysis run, whichever is more frequent.
i
, The CCV is also run after the last analytical sample in the analysis
! !' run.
I ' 6.3.3' Procedure
! " The same CCV must be used throughout the analysis runs for a Case of
i ' samples received.
| The analyte concentrations in the continuing calibration standard must
: be one of the following solutions and should be at or near ± 10 percent the
; mid-range levels of the calibration curve:
i i
| EPA solutions; or
A Contractor prepared standard solution.
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Method 200.62-B-CLP Inductively Coupled Plasma
Each CCV analyzed must reflect the conditions of analysis for all of the
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.
6.3.4 Calculations
Found Concentration , nn - ,
% Recovery - : x 100
True Concentration
6.3.5 Technical Acceptance Criteria
Recovery for the CCV must be within ± 10 percent of the true value
(i.e., 90-110%).
6.3.6 Corrective Action
When recoveries of the CCV exceed the technical acceptance criteria, the
analysis must be stopped, the problem corrected, the instrument recalibrated,
the calibration reverified, and the preceding 10 analytical samples reanalyzed
(or all analytical samples 'since the last "acceptable" CCV analyzed).
6.3.7 Documentation
Report the CCV found concentration, true concentration, and percent
recovery on FORM II-HCIN.
6.4 CRQL Standard
6.4.1 Summary
To verify linearity near the CRQL, the Contractor must analyze an ICP
standard at two times the CRQL or two times the MDL, whichever is greater.
This standard must be run for every wavelength used for analysis.
6.4.2 Frequency
The CRQL standard must be run at the beginning and end of each sample
analysis run, or a minimum of twice per eight hours, whichever is more
frequent.
IHC01.2 " Page 123
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Method 200.62-B-CLP
Inductively Coupled Plasma
6.4.3 Procedure
The CRQL standard is not to be run before the ICV solution.
6.4.4 Calculations
Found Concentration -,**
% Recovery - : * x 100
J True Concentration
6.4.5 Technical Acceptance Criteria
Recovery of the CRQL standard must be within ± 15 percent of the true
value (i.e., 85-1152) for each wavelength used for analysis. (See Table 3,
Exhibit C)
6.4.6 Corrective Action
If the CRQL standard does not fall within the control limit, the
analysis must be terminated and the problem corrected and the analytical
samples since the last acceptable CR1 must be reanalyzed.
6.4.7 Documentation
Report the CRQL standards found concentration, true concentration, and
percent recovery on FORM III-HCIN.
6.5 Linear Range Analysis
6.5.1 Summary
The concentration range over which the ICP calibration curve remains
linear must be determined and any values above this linear range, must be
diluted and reanalyzed.
6.5.2 Frequency
For all ICP analyses, a linear range verification check standard must be
analyzed at the beginning and end of each sample analysis run, or a minimum of
twice per eight hour working shift, whichever is more frequent, but not before
the ICV. This standard must be run for all wavelengths used for each analyte
reported by ICP.
6.5.3 Procedure
The standard must be analyzed 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).
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Method 200. 62-B-CLP Inductively Coupled Plasma
6.5.4 Calculations
Found Concentration , _
% Recovery = ~ ~ : x 100
J True Concentration
6,5.5 Technical Acceptance Criteria
Recovery for the linear range standard must be within ± 10 percent of
the true value (i.e., 90-110%).
6.5.6 Corrective Action
If the recovery of the linear range standard does not meet the technical
acceptance criteria, then the analysis must be terminated and successive
dilutions of the standard must be reanalyzed until the control limits are met.
The concentration of this standard that meets the control limits is the upper
limit of the instrument linear range beyond which results cannot be reported
under this contract without dilution of the analytical sample.
6.5.7 Documentation
Report the linear range standards found concentration (in mg/L), true
concentration (in mg/L) and percent recovery for each metal on FORM III-HCIN.
Where:
Mean - x - § x,/n
i-l
Standard Deviation - a - -/££=!(xi-x)2/(n-l)
6.6 Initial Calibration Blank
6.6.1 Summary
To verify that the ICP system is not contaminated, an initial
calibration blank (ICB) must be analyzed after calibration.
6 .6.. 2 Frequency
The ICB must be analyzed each time the system is calibrated and
immediately after the ICV.
6.6.3 Procedure
If the absolute value of the ICB is greater than the MDL, the result
must be reported.
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Method 200.62-B-CLP
Inductively Coupled Plasma
6.6.4 Calculations
Not applicable.
6.6.5 Technical Acceptance Criteria
The absolute value of the ICB must be less than the CRQL.
6.6.6 Corrective Action
When the ICB concentration does not meet the technical acceptance
criteria, terminate analysis, correct the problem, recalibrate, verify the
calibration, and reanalyze the ICB.
6.6.7 Documentation
Report the ICB values in mg/L on FORM IV-HCIN.
6.7 Continuing Calibration Blanks
6.7.1 Summary
To ensure that the system is not contaminated during the analysis run,
continuing calibration blanks (CCB) are analyzed.
6.7.2 Frequency
Analyze the CCB at a frequency of 10 percent or every two hours,
whichever is more frequent.
Analyze the CCB after every CCV.
6.7.3 Procedure
A CCB .must be run after the last CCV in the analysis run.
If the absolute value of the CCB is greater than the MDL, the result
must be reported.
6.7.4 Calculations
Not applicable.
6.7.5 Technical Acceptance Criteria
The absolute value of the CCB must be less than the CRQL.
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Method 200.62-B-CLP Inductively Coupled Plasma
6,7.6 Corrective Action
When the CCB concentration does not meet the technical acceptance
criteria, terminate analysis, correct the problem, recalibrate, verify the
calibration, and reanalyze the preceding 10 analytical samples (or all
analytical samples since the last "acceptable" CCB analyzed).
6.7.7 Documentation
Report the ICB values in mg/L on FORM IV-HCIN.
6.8 . Preparation Blanks
6.8.1 Summary
To ensure against contamination during sample preparation, a preparation
blank (PB) is analyzed.
6.8.2 Frequency
At least one PB, must be prepared and analyzed with every SDG, or with
each batch5 of samples digested, whichever is more frequent.
6.8.3 Procedure
The PB shall consist of ASTM Type II water processed through each sample
preparation and analysis procedure step (See Exhibit D, Section III).
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.
6.8.4 Calculations
Not applicable.
6.8.5 Technical Acceptance Criteria
The absolute value of the PB must be less than the CRQL.
6.8.6 Corrective Action
If the absolute value of the concentration of the blank is less than or
equal to the CRQL, no correction of sample results is performed.
5A group of samples prepared at the same time.
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Method 200.62-B-CLP Inductively Coupled Plasma
If any analyte concentration in the blank is above the CRQL, £.11
associated samples containing less than lOx the blank concentration must be
redigested and reanalyzed for that analyte. The sample concentration is not
to be corrected for the blank value.
If an analyte concentration in the blank is below the negative CRQL,
i then all samples reported below lOx CRQL associated with the blank must be
redigested and reanalyzed.
6.8.7 Documentation
The values for the preparation blank must be recorded in mg/Kg on FORM
IV-HCIN.
! 6,9 ICP Interference Check Sample
I
i
6.9.1 Summary
To verify interelement and background correction factors, an ICP
Interference Check Sample (ICS) is analyzed.
6.9.2 Frequency
Analyze the ICS 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 the ICV.
t
i
j ' 6.9.3 Procedure
I !
i The ICS consists of two solutions: Solution A and Solution AB. Solution
i i A consists of the interferants, and Solution AB consists of the.analytes mixed
| with the interferants. An ICS analysis consists of analyzing both solutions
. consecutively (starting with Solution A) for all wavelengths used for each
i !; analyte reported by ICP.
i
The ICP ICS must be obtained from EPA (EMSL-LV) if available and
: analyzed according to the instructions supplied with the ICS.
1 > If the ICP ICS is not available from EPA, independent ICP check samples
I must be prepared with interferant and analyte concentrations at the levels
: L specified in Table 2 - ICP Interference Check Sample (see Exhibit C). The
1 mean value and standard deviation must be established by initially analyzing
! ' the check samples at least five times repetitively for each parameter
]
I | 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
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Method 200.62-B-CLP - - - Inductive!v Coupled Plasma
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).
6.9.4 Calculations
% Recovery - Found Concentration
7 True Concentration
Where:
Mean - x - 2 x,/n
Standard Deviation - a - JZ%*i (Xi-x)2/(n-l)
6.9.5 Technical Acceptance Criteria
Recovery for the ICS must be within ± 20 percent of the true value
(i.e. , 80-120%).
6.9.6 Corrective Action
If the ICS recoveries do not meet the technical acceptance criteria,
terminate the analysis, correct the problem,, recalibrate the instrument,
verify the calibration, and reanalyze all of the analytical samples analyzed
since the last acceptable ICS.
6.9.7 Documentation
Report the ICS found concentration, true concentration, percent
recovery, mean and standard deviation on FORM V-HCIN.
The mean and standard deviation must be reported in the raw data.
6.10 Spike Sample Analysis
6.10.1 Summary
To provide information about the effect of the sample matrix on the
digestion, a known amount of analyte is added (spiked) into a sample.
6.10.2 Frequency
At least one spike sample analysis must be performed on each group of
samples of a similar phase for each SDG.6
6 EPA may require additional spike sample analysis upon special request by the
Project Officer, for which the Contractor will be paid.
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Method 200.62-B-CLP _^___ Inductively Cotioled Plasma
If two analytical methods are used to obtain the reported values for the
same metal within a SDG (i.e., ICP, HYICP, GFAA, etc.), Chen the spike samples
must be run by each method used.
6.10.3 Procedure
The spike is added before the sample preparation (i.e., prior to fusion,
digestion or distillation).
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.
In the instance where there is more than one spike sample per phase per
method per SDG, if one spike sample recovery is not within contract criteria,
flag all the samples of the same matrix, level, and method in the SDG.
6.10.4 Calculations
<
"SA
D fSSR-SR) ,__
Recovery - v " fc x 100.
Where:
SSR - Spiked Sample Result;
SR « Sample Result; and
SA - Spike Added.
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 6.12, Duplicate
Sample Analysis). The average of the duplicate results cannot be used for the
purpose of determining percent recovery.
When the sample concentration is less than the instrument detection
limit, use SR - 0 only for purposes of calculating percent recovery.
6.10.5 Technical Acceptance Criteria
Recovery for the spike should be within ± 25 percent of the spiked
"amount (i.e., 75-125%).
6.10.6 Corrective Action
If the spike recovery is not 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-HCIN and
VII-HCIN.
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Method 200.62-B-CLP
Inductively Coupled Plasma
An exception to this rule is granted in situations where the sample
concentration exceeds the spike concentration by a factor of four or more. In
such an event, the data shall be reported unflagged even if the percent
recovery does not meet the 75-125% recovery criteria.
6,10.7 Documentation
Report the spiked sample results, sample results, spike added and
percent recovery for the spike sample analysis on FORM VI-HCIN.
The units for reporting spike sample results will be in rag/Kg.
6.11 Analytical Spike Sample Analysis
6.11.1 Summary
To provide information about the effect of the sample matrix on the
measurement system.
6.11.2 Frequency
At least one spike sample analysis must be performed on each group of
samples of a similar phases for each SDG.7
If two analytical methods are used to obtain the reported values for the
same metal within a SDG (i.e., ICP, HYICP, GFAA, etc.), then spike samples
must be run by each method used.
6.11.3 Procedure
The analytical spike sample analysis must be performed on a sample
containing measurable amounts of the analytes or at least a representative
sample of the phases associated with it.
The spike is added after the sample preparation and prior to analysis.
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 spiked with a concentration equal to 30% of
the. analytes linear range.
7 EPA may require additional spike sample analysis upon special request by the
Project Officer, for which the Contractor will be paid.
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Method 200.62-B-CIP
Inductively Coupled Plasma
The sample and spiked sample must be at the same dilution.
In the instance where there is more than one spike sample per phase per
method per SDG, if one spike sample recovery is not within contract criteria,
flag all the samples of the same matrix, level, and method in the SDG.
6.11.4 Calculations
fSSR-SR)
% Recovery =
SA
x 100
Where:
SSR - Spiked Sample Result;
SR - Sample Result; and
SA - Spike'Added.
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 6.12, Duplicate
Sample Analysis). The average of the duplicate results cannot be used for the
purpose of determining percent recovery.
When sample concentration is less than the method detection limit, use
SR 0 only for purposes of calculating percent recovery.
6,11.5 Technical Acceptance Criteria
Recovery for the analytical spike should be within ± 15 percent of the
spiked amount (i'.e., 85-115%).
6.11.6 Corrective Action
If the spike recovery is not at or within the limits of 85-115%, a
second analytical spike must be performed. If the second analytical spike is
out of control, then the preparation blank must be spiked with the same
spiking solution. If spiking the blank yields a recovery that is out of
control, the spiking solution must be reprepared and the previous spiking
procedure repeated. If not, then flag all samples received associated with
that spike sample and determined by the same analytical method with the letter
"E" on FORMs I-HCIN and VII-HCIN.
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Method 200.62-B-CLP
Inductively Coupled Plasma
6,11.7 Documentation
Report the spiked sample results, sample results, spike added and
percent recovery (positive, negative, or zero) for the analytical spike sample
analysis on FORM VII-HCIN.
The units for reporting analytical spike sample results will be in mg/L.
6.12 Duplicate Sample Analysis
6.12.1 Summary
Duplicate aliquots of a sample are carried through the preparation and
analysis steps to provide information about the precision of the analytical
methods as well as matrix effects.
6.12.2 Frequency
At least one duplicate sample analysis must be performed on each group
of samples of a similar phase for each SDG.8
If two analytical methods are used to obtain the reported values for the
same metal within a SDG (i.e., HYICP, GFAA, etc.,), then duplicate samples
must be run by each method used.
6.12.3 Procedure
Samples identified as field blanks cannot be used for duplicate sample
analysis.
EPA may require that a specific sample be used for the duplicate sample
analysis.
In the instance where there is more than one duplicate sample per matrix
and concentration per method per SDG, if one duplicate result is not within
contract criteria, flag all the samples of the same phase and method in the
SDG.
Duplicate sample analyses are required for calculations of relative
percent difference.
6.12.4 Calculations
IS-Dl
RPD
(S+D)/2
x 100
8 EPA may require additional duplicate sample analysis upon special request by
the Project Officer, for which the Contractor will be paid.
IHC01.2
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Method 200.62-B-CLP
JEnd-actlvely Coupled Plasma
Where:
RPD .Relative Percent Difference;
S - First Sample Value (original); and
D - Second Sample Value (duplicate).
Duplicates cannot be averaged for reporting on FORM I-HCIN.
6.12.5 Technical Acceptance Criteria
A control limit of ± 20 percent for RPD shall be used for original and
duplicate sample values greater than or equal to 5x CRQL (Exhibit C). A
control limit of ± the CRQL must be used for sample values less than 5x CRQL.
If one result is above the 5x CRQL level and the other is below, use the
± CRQL criteria. .
If both sample values are less than the HDL, the RPD is not calculated.
Specific control limits for each metal will be added to FORM IX-HCIN at
a later date based on precision results.
6.12.6 Corrective Action
If the duplicate sample results are outside the control limits, flag all
the data for samples received associated with that duplicate sample with an
asterisk "*".
6.12.7 Documentation
The results of the duplicate sample analyses must be reported on FORM
VIII-HCIN in mg/Kg. '
The absolute value of the control limit (CRQL) must be entered in the
"CONTROL LIMIT" column on FORM VIII-HCIN.
6.13 Laboratory Control Samples
6,13.1 Summary
A LCS is digested arid analyzed to ensure against analyte loss in the
sample preparation.
6.13.2 Frequency
One LCS must be prepared and analyzed for every group of samples in a
SDG, or for each batch of samples, whichever is more frequent.
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Method 200.62-B-CLP
Inductively Coupled Plasma
6.13.3 Procedure
The 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 LCS must be obtained from EPA. (If unavailable,, other EPA Quality
Assurance Check samples or other certified materials may be used.)
6.13.4 Calculations
., Found Concentration '
% Recovery - ~ ~ x 100
J True Concentration
6.13.5 Technical Acceptance Criteria
Recovery for the LCS must be within ± 20% of the true value (i.e., 80-
120%).
6.13.6 Corrective Action
If the percent recovery for the LCS falls outside the limit established
by EPA, then the analyses must be terminated, the problem corrected, and the
samples associated with that LCS reprepared and reanalyzed.
6.13.7 Documentation
Report the LCS found concentration (in mg/Kg), true concentration (in
mg/Kg), and percent recovery on FORM IX-HCIN.
6.14 Method Detection Limits
6.14.1 Summary
The method detection limit (MDL) must be determined before any samples
are analyzed for every instrument that will be used.
6.14.2 Frequency
MDLs must be determined within 30 days of the start of the contract and
at least quarterly (every three calendar months) until the end of the
contract.
6.14.3 Procedure
The Method Detection Limits (in mg/L) shall be determined by multiplying
by 3, the average of the standard deviations (an.i~) obtained on three
nonconsecutiye days from the consecutive analysis of seven different
preparation blank dissolutions. Each measurement must be performed as though
it were a separate analytical sample (i.e., each measurement must be followed
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Method 200.62-B-CLP
Inductively Coupled Plasma
by a rinse and/or any other procedure normally performed between the analysis
of separate samples). MDLs must be determined and reported for each
wavelength used in the analysis of the samples.
The quarterly determined MDL for an instrument must always be used as
the MDL for that instrument during that quarter. If the instrument is
adjusted in anyway that may affect the MDL, the MDL for that instrument must
be redetermined and the results submitted for use as the established MDL for
that instrument for the remainder of the quarter.
MDLs must be determined in mg/L.
6.14.4 Calculations
MDL - (on_i) x 3
6.14.5 Technical Acceptance Criteria
The MDLs must be able to meet the CRQL's established in Exhibit C.
6.14.6 Corrective Action
If an instrument's MDL cannot meet the CRQL for an analyte, that
instrument cannot be used to quantitate an analysis unless the analyte
concentration is greater than or equal to two times the reported MDL.
6.14.7 Documentation
MDLs must be reported for each instrument used on FORM XI-HCIN submitted
with each data package. If multiple instruments are used for the analysis of
an analyte within a SDG, the highest MDL for the analyte must be used for
reporting concentration values for that SDG.
6.15 Interelement Correction Factors
6.15.1 Summary
To ensure against spectral interferences, interelement correction
factors are determined for all wavelengths used for each analyte reported by
ICP."
6.15.2 Frequency
Before any field samples are analyzed under this contract, the ICP
interelement correction factors must be determined within 3 months prior to
the start of contract analyses and at least annually thereafter.
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Method 200.62-B-CLP
Inductively Coupled Plasma
6.15.3 Procedure
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.
Follow the instrument manufacturer's recommendations for applying
interelement correction factors.
6.15.4 Calculations
Not applicable.
6,15.5 Technical Acceptance Criteria
Not applicable.
6.15.6 Corrective Action
Not applicable.
6.15.7 Documentation
Results from interelement correction factors determination must be
reported on FORM XII-HCIN for all ICP parameters.
7.
Instrument Operation
7.1 No detailed operating instructions as to the optimization of the plasma
power, argon flows, torch and coil configuration, etc. will be given. The
analyst should follow the instructions provided by the manufacturer of the
particular instrument.
7.2 The sample introduction system is to be of a pneumatic type. The use of
a peristaltic pump instead of direct aspiration is required because of the
high salt content of the fusion dissolutions. A tip washer is a very useful
aid and can be easily inserted into the sample flow system by placing a "tee
connector" on the carrier argon flow line just before entering the nebulizer.
One arm of the "tee connector" runs to the nebulizer, another to the carrier
argon flow line and the third is connected to a line from the peristaltic
pump. When a drop in the carrier flow is observed, a small pulse of water is
pumped into the carrier argon flow and blown through the nebulizer orifice,
dissolving the salt buildup and restoring the original carrier argon flow.
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Method 200 62-B-CLF Inductively Coupled Plasma
i
( 7.3 Changes in the carrier argon flow may change the emission
characteristics of the analyte. The use of a digital mass flow controller on
the carrier argon flow is recommended to control the flow, rather than the use
I of a rotometer.
I :
j 7.4 For direct reading instruments, every solution, including calibration
> standards, calibration and method blanks, reference samples, and fused samples
I | must be analyzed using two full exposures (peak scan), each of which is
! sufficient to meet the method detection limit (at each analyte emission line).
! . All exposure times must be the same for all analyses and all quarterly
analyses (i.e., method detection limit and interelement correction factor.)
] : Each' background spectral region must have an exposure time equivalent to a
j i full exposure time for direct reading instruments.
i 7.5 Selection of the appropriate background spectral region for each analyte
i must account for the major interferants within that region and for the
| ! possibility of analyte line broadening at high concentrations.
j -
I 7.5.1 One of the best ways to select the appropriate background spectral
| region is to perform a wavelength scan around the analyte wavelengths in the
j presence of metals frequently encountered at high levels in the samples.
Alternately, if the instrument does not have automatic scanning capability,
selection of the background spectral region will have to be determined on the
basis of manual scans and experience.
: 7.5.2 It is possible, if the background correction wavelength is too close
! to the analyte line, to observe either a net intensity of zero or other
' erroneous net intensity readings, to aid in circumventing this error, it is
I required, at a minimum, that uncorrected analyte concentrations can be derived
i from the submitted raw data package. In addition, the equivalent
concentration correction determined at the background correction wavelength
| must be reported. Finally, all uncorrected intensity data for all analyte
I lines and background correction wavelengths must be reported. The analyst
i must review this data prior to submission to assure that reported values do
! not reflect this type of error.
7.6 Rinsing between sample/standard solutions is extremely important to help
, alleviate salt build-up at various points in the sample introduction system
', and to eliminate carry-over between samples. A high level of potassium may
j cause salting out at various points in the nebulizer or torch. This problem
j ' is intensified when the solutions are nebulized for extended periods of time.
i Rinse with 10% HN03 and 10% HC1. Do not aspirate the calibration blank
i between sample aspirations as a "wash" mechanism. A minimum rinse time of at
! least one minute between samples must be used.
i 7.7 The determination of the linear range of each analyte line, interference
effects, and any type of detection limit or precision measurement must be
established under the same conditions used for the analysis of the samples,
including the background correction scheme.
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Method 200.62-B-CLF
InductivelvCoupled Plasma
8, Sample Analysis
8.1 Calibration
8.1.1 Set up the instrument with proper operating parameters. The
instrument must be allowed to become thermally stable before beginning
analysis. This requires at least 30 minutes of operation with the plasma lit
prior to calibration.
8.1.2 Initiate appropriate operating configuration of the instrument
computer.
8.1.3 Perform the appropriate steps recommended by the manufacturer to
align the exit slits with the entrance slit. These steps are commonly called
the profile or wavelength calibration procedure.
8.1.4 Calibrate the instrument using the appropriate matrix matched
calibration standard solution(s). The number of standards utilized is left to
the discretion of the operator but must include a calibration blank and at
least one calibration standard. The operator should be aware of the
requirements in Exhibits D and E that provide for the assurance that all
sample values are within the linear range of the initial calibration.
8.2 Analysis Sequence
8.2.1 Before beginning the sample analysis run, analyze the initial
calibration blank (ICB), initial calibration verifications (ICV), interference
check-sample, CRQL standard (CRI) and the linear range standard (LRS). The
ICV, CRI and LRS concentration values must not deviate from the actual values
by more than 10%. The calibration blank values may not exceed the CRQL. The
interference check sample found values may not deviate by more than 20% of the
true values. If these conditions are not met for any metal, the analysis
shall be discontinued (see Exhibits D (Quality Control- Initial and Continuing
Calibration Blanks) and E for additional information).
8.2.2 Upon successful analysis of the ICV, ICB, CRI, LRS and ICS, analyze
all method blank dissolution(s) prepared with the fused samples. If any of
the blank(s) values are not less than or equal to the CRQL, see Exhibits D.and
E for the appropriate action.
8.2.3 If the method blank(s) values are acceptable, analyze the Laboratory
Control Sample (LCS). If any of the reference sample values deviate from the
acceptable ranges, see Exhibits D and E for the appropriate action.
8.2.4 If the preparation blank and LCS values are within the acceptable
ranges, analyze the spike sample and also the analysis spike.sample. If the
recovery of any metal deviates from the acceptable ranges, see Exhibit E for
the appropriate action. Proceed to the analysis of samples if the recoveries
are acceptable or after consulting Exhibits D and E.
IHC01.2
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Method 200.62-B-CLP
Inductively Coupled Plasma
8.2.5 The continuing calibration verification standard (CCV) and the
continuing calibration blank (CCB) must be analyzed after every ten analytical
sample analyses. It is required that the analyst run the CCV and CCB after
the analysis of the previous sample, but prior to use of a tip wash or other
clean out device. CCV concentration values must not deviates from the actual '
values by more than 10%. In addition, the absolute values for the CCB must be
lower than the CRQLs. If these conditions are not met at any time during
samples analysis, discontinue the analysis and see Exhibits D and E for the
appropriate action-.
8.2.6 At the end of the sample analysis run, analyze the ICS, CRI, LRS, CCV
and CCB. If the values for any of these samples deviates from the required
limits, see Exhibits D and E for additional information.
8.3 Sample Analyses
8.3.1 All sample dissolutions must first be analyzed without any dilution.
Diluting sample dissolutions is permissible if necessary, provided that the
CRQL is not exceeded.
8.3.2 All concentrations within the linear range of the analyte are to be
reported. All concentrations reported must be obtained within the established
linear range for that analysis run, and interference corrections must be made
based on the actual concentration of the interferant and not the apparent
concentration obtained when the interferant concentration is above the linear
range.
8.4 Ca1culations
8.4.1 To obtain the analyte concentration (in mg/Kg), multiply the
interference corrected analyte values (in mg/L) by the appropriate volume (in
liters) used in the fusion and divide by the weight (in Kg) of sample fused.
8.5 Documentation
Report the values in mg/Kg on FORM I-HCIN.
9. Bibliography
9.1 Winge, R.K., V.J. -Peterson, and V.A. Fassel, "Inductively Coupled
Plasma-Atomic Emission Spectroscopy Prominent Lines", EPA-600/4-79-017.
9.2 Winefordner, J.D., "Trace Analysis: Spectroscopic Methods for
Elements", Chemical Analysis, Vol. 46, pp. 41-42.
9.3 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.
IHC01.2
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Method 200.62-B-CLP
Inductively Coupled Plasma
9.4 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). .
9.5 Methods for ChemicalAnalysis of Water and Wastes. EPA-600/4-79-020.
9.6 Annual Book of ASTM Standards. Part 31. .
9.7 "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.
i
9.8 "OSHA Safety and Health Standards, General Industry", (29 CFR 1910),
Occupational Safety and Health Administration, OSHA 2206, (Revised, January
1976).
9.9 "Safety in Academic Chemistry Laboratories", American Chemical Society
Publications, Committee on Chemical Safety, 3rd .Edition, 1979.
9.10 "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.
IHC01.2
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Method 200.62-C-CLP '
Hydride Generation Inductively Coupled Argon
Plasma Optical Emission Spectroscopic Analysis
1. Scope and Application
1.1 This method covers the determination of all concentrations of antimony,
arsenic and selenium dissolved by the potassium hydroxide fusion method.
1.2 The method.is optimized for selenium, the least sensitive element, which
compromises the achievable sensitivities of antimony and arsenic.
1.3 The hydride generation system uses a high sodium borohydride to sample
ratio to minimize interferences.
1.4 Many spectral interferences common to the pneumatic nebulization ICP
analysis are eliminated.
1.5 Detection limits are lowered generally by a factor of ten over pneumatic
nebulization ICP analysis.
2. Summary of Method
2.1 Aliquots of the fusion dissolutions are heated after the addition of an
equal volume of concentrated hydrochloric acid. The chloride-chlorine couple
developed reduces any selenium (VI) present to the selenium (IV) oxidation
{ state. Selenium must be present in the lower oxidation state to form a
i hydride.
2.2 In a continuous flow system, the digests are reacted with sodium
borohydride, followed by potassium iodide, to produce the volatile hydrides.
The iodide-iodine couple reduces any arsenic (V) and antimony (V) to their
1 plus three oxidation states. This circumvents the effect of different hydride
j formation reaction rates on different oxidation states. The addition of
I potassium iodide after the addition of the sodium borohydride eliminates the
! formation of elemental selenium by the iodide-iodine couple.
j 2.3 The hydrides are stripped from the sample by argon gas and swept into
< the plasma of an Inductively Coupled Argon Plasma Optical Emission
; Spectrophotometer. The resulting free atoms are excited into higher
', electronic states. Atomic and ionic line emission spectra characteristic of
j the particular metals are produced when the electrons decay back to lower
' energy levels. The spectra are dispersed by a spectrometer and the intensity
\ of specific line radiation(s) are monitored simultaneously or sequentially by
" photomultiplier tubes. The photocurrents produced by the photomultiplier
> tubes will increase in direct proportion to the concentration of the metals in
i the sample within the linear range of a specific emission line. The
! photocurrents are processed and controlled by a computer system and related to
concentration through a calibration procedure.
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Method 200.62-C-CLP
Hydride Inductively Coupled Plasma
2.4 The Method of Standard Additions may be needed to compensate for
chemical interferences in the hydride formation reactions.
3.
Interferences
3.1 As discussed in Sections 2.1 and 2.2, proper adjustment of the oxidation
states of the metals is important in obtaining accurate results.
3.2 Some of the transition metals, especially copper, cause suppression of
the hydride formation by reacting to form insoluble salts. Selenium is
affected more than the other metals because transition metal selenides are
very insoluble. The high acid strength and high sodium borohydride
concentration help to temper these effects. The use of the method of standard
additions compensates for these effects.
3,3 Spectral interferences common to the pneumatic nebulization analysis of
these three metals are eliminated because the interfering metals do not form
hydrides and thus are not introduced into the plasma.
4. Apparatus and Equipment
4.1 Computer-controlled inductively coupled argon plasma optical emission
spectrometer system with:
4.1.1 Polychromator with associated dispersion and detector system such that
the three metals can be determined simultaneously. A fast sequential scanning
instrument may be used if the QC requirements set forth in this method can be
met.
4.1.2 Radiofrequency generator and coupling system.
4.2 Argon gas supply, welding grade or better.
4.3 Variable speed four channel peristaltic pump and pump tubing.
4.4 Hydride Manifold.
4.5 Phase Separator.
4.6 Screw cap test tubes, 10 mL, with teflon lined caps.
4.7 Water bath or test tube heating block.
4.8 Vortex mixer.
4.9 Assorted laboratory volumetric glassware, pipets and micropipets.
5. Reagents and Standards
5.1 Hydrochloric acid, better than reagent grade.
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Method 200.62-C-CLP
Hydride Inductively Coupled Plasma
5.2 Sodium borohydride solution (4.82 w/v in 0.25 N NaOH) and potassium
iodide solution (8% w/v) are prepared from ACS reagent grade chemicals.
5.3 Water equivalent to ASTM Type II is used throughout.
5.4 Stock standard solutions are to be made from ultrapure materials.
5.5 Mixed spiking solutions are made at appropriate concentrations by
dilution of the Stock Standard Solution(s). The final solution should contain
all three metals at the same concentration in 50% v/v HC1. Selenium must be
in the plus four oxidation state. To determine the oxidation state of
selenium, use the procedure given in Section 5.6.2.
5.6 Calibration Standard Stock Solutions are prepared by dilution of the
stock or spiking standard solutions. The final solution must contain all
three metals at the same concentration in 50% HC1.
5.6.1 The concentration of the metals required in the calibration
standard(s) will be dependent upon the instrumentation and so the
concentration used as well as the number of standards used is left to the
discretion of the analyst, although at least one calibration standard and a
calibration blank are required for calibration of the instrument. As a
starting point, try calibrating with a mixed standard containing 0.1 mg/L of
each of the three metals.
5.6.2 Consideration must be made to assure that selenium is in its plus four
oxidation state. Check this by heating one of two portions of the standard(s)
in accordance with the procedure given in Section 8.1 and compare the heated
versus unheated concentrations obtained. If the heated selenium value is more
than 5% higher than the unheated value, some of the selenium is present in the
plus six oxidation state. If it is determined that greater than 5% of the
selenium is present in the higher oxidation state, then all standards must be
heated in accordance with the procedure given in Section 8.1.
5.7 Blank Solution, 50% (v/v) HC1. This acid must be from the same lot of
HC1 as that used for the calibration standard stock solution.
5.8 The continuing calibration verification standard is to be made from
ultrapure materials. If it is also used as the Initial Calibration
Verification, it must be made from a standard of a different source than the
calibration standards. If not, it may be the same as one of the calibration
standards. The concentrations of the metals are to be at the mid range of the
calibration curve. The final solution must contain all three metals at the
same concentration in 50% (v/v) HC1.
5.9 Rinse Solution, 50% (v/v) HC1.
grade or better concentrated HC1.
The rinse solution must.be made from ACS
IHC01.2
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Method 200.62-C-CLF
Hydride Inductively Coupled Plasma
6. Quality Control
6.1 Instrument Calibration
6.1.1 Summary
Prior to the analysis of samples and required QC, each HYICP system must
be initially calibrated to determine instrument sensitivity.,
6.1.2 Frequency
Instruments must be calibrated daily or once every 24 hours and each
time the instrument is set up.
6.1.3 Procedure
Calibration standards must be prepared using the same type of matrix and
at the same reagent concentration as the preparation blank following' sample
preparation.
Calibrate according to instrument manufacturers recommended procedures
using at least two standards, one being a blank.
Before beginning the sample run, reanalyze the highest mixed calibration
standard as if it were a sample.
6.1.4 Calculations
% Recovery -
Found Concentration
True Concentration
6.1.5 Technical Acceptance Criteria
x 100
Recovery for the highest mixed calibration standard must be within ± 5
percent of the true value (i.e., 95-105%).
6.1.6 Corrective Action
Follow instrument manufacturers recommendations to correct the problem.
Also, 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 a CCV and a CCB, respectively.
6.1.7 Documentation
The instrument standardization date and time must be included in the raw
data.
IHC01.2
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Method 200.62-C-CLP Hydride Inductively Coupled Plasma
| 6.2 Initial Calibration Verification
i 6.2.1 Summary
j ;,
j Immediately after the HYICP system has been calibrated, the accuracy of
j ' the initial calibration shall be verified and documented for every analyte by
! the analysis of EPA Initial Calibration Verification Solution(s) (ICV) at each
I wavelength used for analysis.
1 6.2.2 Frequency
' Each time the instrument is calibrated, the ICV must be run immediately
follow
i
' following the calibration, before any samples are analyzed.
6.2-3 Procedure
If the ICV 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 linear 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.
6.2.4 Calculations
: Found Concentration ,_.
% Recovery - ± rt; ~ f x 100
i J True Concentration
I 6.2.5 Technical Acceptance Criteria
I
i i Recovery for the ICV must be within ± 10 percent of the true value
| (i.e., 90-1102).
6.2.6 Corrective Action
ii
] When recoveries of the ICV exceed the technical acceptance criteria, the
! ; analysis must be terminated, the problem corrected, the instrument
! recalibrated, and the calibration reverified.
i |
j 6.2.7 Documentation
Report the ICV found concentration, true concentration, and percent
recovery on FORM II-HCIN.
6.3 Continuing Calibration.Verification
6.3.1 Summary
To ensure calibration accuracy during an analysis run, a continuing
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Method 200.62-C-CLP
Hydride Inductively Coupled Plasma
calibration verification solution (CCV) is analyzed and reported for every
wavelength used for the analysis of each analyte.
6.3.2 Frequency
The CCV is run at a frequency of 10 percent or every two hours during an
analysis run, whichever is more frequent.
The CCV is also run after the last analytical sample in the analysis
run.
6.3.3 Procedure
The same CCV must be used throughout the analysis runs for a Case of
samples received.
The analyte concentrations in the continuing calibration standard must
be one of the following solutions and should be at or near ± 10 percent of the
mid-range levels of the calibration curve:
EPA Solutions; or
A Contractor prepared standard solution.
Each CCV analyzed must reflect the conditions of analysis for all of the
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.
6.3.4 Calculations
Found Concentration .. _.
% Recovery - ' x 100
J True Concentration
6.3.5 Technical Acceptance Criteria
Recovery for the CCV must be within ± 10 percent of the true value
(i.e., 90-110%).
6.3.6 Corrective Action
When recoveries of the CCV exceed the technical acceptance criteria, the
analysis must be stopped, the problem corrected, the instrument recalibrated,
the calibration reverified, and reanalyze the preceding 10 analytical samples
(or all analytical samples since the last "acceptable" CCV analyzed).
IHC01.2
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Method 200.62-C-CLP Hydride Inductively Coupled Plasma
I 6.3.7 Documentation
I
| Report the CCV found concentration, true concentration, and percent
| ' recovery, on FORM II-HCIN.
| 6.4 CRQL Standard
6.4.1 Summary
! To verify linearity near the CRQL, the Contractor must analyze an HYICP
standard at two times the CRQL or two times the MDL, whichever is greater.
This, standard must be run for every wavelength used for analysis.
I 6.4.2 Frequency
i The CRQL standard must be run at the beginning and end of each sample
analysis run, or a minimum of twice per eight hours, whichever is more
i !: frequent.
j ii
1 6.4.3 Procedure
j The CRQL standard is not to be run before the ICV solution.
6.4.4 Calculations
., _ Found Concentration ,_,.
Z Recovery - x 100
J True Concentration
6.4.5 Technical Acceptance Criteria
Recovery of the CRQL standard must be within ± 15 percent of the true
value (i.e., 85-115%) for each wavelength used for analysis. (See Table 3,
Exhibit C)
6.4.6 Corrective Action
If the CRQL standard does not fall within the control limit, the
analysis must be terminated and the problem corrected and the analytical
samples since the last acceptable CRI must be reanalyzed.
6.4.7 Documentation
Report the CRQL standards found concentration, true concentration, and
percent recovery on FORM III-HCIN.
6.5 Linear Range Analysis
6.5.1 Summary
The concentration range over which the HYICP calibration curve remains
IHC01.2 Page 148
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Method 20Q.62-C-CLP
Hydride Inductively Coupled Plasma
linear must be determined and any values above this linear range, must be
diluted and reanalyzed.
6.5.2 Frequency
For all HYICP analyses, a linear range verification check standard must
be analyzed at the beginning and end of each sample analysis run, or a minimum
of twice per eight hour working shift, whichever is more frequent, but not
before the ICV. This standard must be run for all wavelengths used for each
analyte reported by HYICP.
6.5.3 Procedure
The standard must be analyzed 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).
6.5.4 Calculations
% Recovery =
Found Concentration
True Concentration
6.5.5 Technical Acceptance Criteria
X 100
Recovery for the linear range standard must be within ± 10 percent of
the true value (i.e., 90-110X).
6.5.6 Corrective Action
If the recovery of the linear range standard does not meet the technical
acceptance criteria, then the analysis must be terminated and successive
dilutions of the standard must be reanalyzed until the control limits are met.
The concentration of this standard that meets the control limits is the upper
limit of the instrument linear range beyond which results cannot be reported
under this contract without dilution of the analytical sample.
6.5.7 Documentation
Report the linear range standards found concentration (in mg/L), true
concentration (in mg/L), and percent recovery for each metal on FORM III-HCIN.
Where:
Mean -
i-l
Standard Deviation - a - 7^=1 (Xi-x)2/(n-l)
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Method 200.62-C-CLP Hydride Inductively Coupled Plasma
6.6 Initial Calibration Blank
6.6.1 Summary
To verify that the HYICP system is not contaminated, an initial
calibration blank (ICB) must be analyzed after calibration.
6.6.2 Frequency
The ICB must be analyzed each time the system is calibrated and
immediately after the ICV.
6.6.3 Procedure
I
j If the absolute value of the ICB is greater than the MDL, the result
I must be reported.
| . 6.6.4 Calculations
Not applicable.
6.6.5 Technical Acceptance Criteria
The absolute value of the ICB must be less than the CRQL.
6.6.6 Corrective Action
When the ICB concentration does not meet the technical acceptance
criteria, terminate analysis, correct the problem, recalibrate, verify the
calibration, and reanalyze the ICB.
6.6.7 Documentation
Report the ICB values in m'g/L on FORM IV-HCIN.
6.7 Continuing Calibration Blanks
6.7.1 Summary
To ensure that the system is not contaminated during the analysis run,
continuing calibration blanks (CCB) are analyzed.
6.7.2 Frequency
Analyze the CCB at a frequency of 10 percent or every two hours,
whichever is more frequent.
Analyze the CCB after every CCV.
IHC01.2 Page 150
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Method 200.62-C-GLP
Hydride Inductively Coupled Plasma
6.7.3 Procedure
A CCB must be run after the last CCV in the analysis run.
If the absolute value of the CCB is greater than the MDL, che result
must be reported.
6.7.4 Calculations
Not applicable.
6.7.5 Technical Acceptance Criteria
The absolute value of the CCB must be less than the CRQL.
6.7.6 Corrective Action
When the CCB concentration does not meet the technical acceptance
criteria, terminate analysis, correct the problem, recalibrate, verify the
calibration, and reanalyze the preceding 10 analytical samples (or all
analytical samples since the last "acceptable" CCB analyzed).
6.7.7 Documentation
Report the ICB values in mg/L on FORM IV-HCIN.
6.8 Preparation Blanks
6.8.1 Summary
To ensure against contamination during sample preparation, a preparation
blank (PB) is analyzed.
6.8.2 Frequency
At least one PB, must be prepared and analyzed with every SDG, or with
each batch9 of samples digested, whichever is more frequent.
6.8.3 Procedure
The PB shall consist of deionized distilled water processed through each
sample preparation and analysis procedure step (See Exhibit D, Section III).
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.
9A group of samples prepared at the same time.
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Method 200.62-C-CLP
Hydride Inductively Coupled Plasma
41
6.8.4 Calculations
Not applicable.
6.8.5 Technical Acceptance Criteria
The absolute value of the PB must be less than the CRQL.
6.8.6 Corrective Action
If the absolute value of the concentration of the blank is less than or
equal to the CRQL, no correction of sample results is performed.
If any analyte concentration in the blank is above the CRQL, all
associated samples containing less than lOx the blank concentration must be
redigested and reanalyzed for that analyte. The sample concentration is not
to be corrected for the blank value.
If an analyte concentration in the blank is below the negative CRQL,
then all samples reported below lOx CRQL associated with the blank must be
redigested and reanalyzed.
6.8.7 Documentation
The values for the preparation blank must be recorded in rag/Kg on FORM
IV-HCIN.
6.9. Spike Sample Analysis
6.9.1 Summary
To provide information about the effect of the sample matrix on the
digestion, a known amount of analyte is added (spiked) into a sample.
6.9.2 Frequency
At least one spike sample analysis must be performed.on each group of
samples of a similar phases for each SDG.10
If two analytical methods are used to obtain the reported values for the
same element within a SDG (i.e., ICP, HYICP, GFAA, etc.), then a spike samples
must be run by each method used.
10
EPA may require additional spike sample analysis upon special request by the
Project Officer, for which the Contractor will be paid. ' . '
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Method 200.62-C-CLP Hydride Inductively Coupled Plasma
6.9.3 Procedure
The spike is added before the sample preparation (i.e., prior to fusion,
digestion or distillation).
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.
' In the instance where there is more than one spike sample per phase per
method per SDG, if one spike sample recovery is not within contract criteria,
flag all the samples of the same matrix, level, "and method in the SDG.
6.9.4 Calculations
_ CSSR-SR)
% Recovery - JL x 100
.oA "*
Where:
SSR - Spiked Sample Result;
SR - Sample Result; and
SA - Spike Added.
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 6.11, Duplicate
Sample Analysis). The average of the duplicate results cannot be used for the
purpose of determining percent recovery.
When sample concentration is less than the instrument detection limit,
use SR - 0 only for purposes of calculating percent recovery.
6.9.5 Technical Acceptance Criteria
Recovery for the spike should be within ± 25 percent of the spiked
amount (i.e., 75-125%).
6.9.6 Corrective Action
If the spike recovery is not 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-HCIN and
VII-HCIN.
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
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Method 200.62-C-CLP
Hvdrlde Inductively Coupled Plasma
such an event, the data shall be reported unflagged even if the percent
recovery does not meet the 75-125% recovery criteria.
6.9.7 Documentation
Report the spiked sample results, sample results, spike added and
percent recovery for the spike sample analysis on FORM VI-HCIN.
The units for reporting spike sample results will be in mg/Kg.
6.10 Analytical Spike Sample Analysis/Method of Standard Additions
6.10.1 Summary
To ensure against bias resulting from interference effects in HYICP
analyses, the Method of Standard Additions (MSA) is utilized.
6.10.2 Frequency
All HYICP analyses for each analytical sample will require at least an
analytical spike.
The frequency of MSA will depend on the recovery of the analytical
spike.
6.10.3 Procedure
All HYICP analyses, including "MSA, must fall within the calibration
range.
All analyses, except during full MSA require duplicate exposures. Only
single exposures are required for MSA quantitation. Average concentration
values are used for reporting purposes.
The analytical spike (at 30% the linear range) for a sample must be run
immediately after that sample. The percent recovery of the analytical spike
will determine the method of quantitation for the sample.
An analytical spike is not required for the pre-digestion spike sample.
A maximum of 10 full sample analyses to a maximum of 20 exposures may be
performed between each consecutive calibration verifications and blanks. Each
full MSA counts as two analytical samples towards determining 107 CCV/CCB
frequency (i.e., five full MSAs can be performed between calibration
verifications).
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Method 200.62-C-CLP . Hydride Inductively Coupled Plasma
For analytical runs containing only MSAs, single exposures can be used
for QC samples during that run. For instruments that operate in an MSA mode
only, MSA can be used to determine QC samples during that run.
The sample and three s: -res must be analyzed consecutively for MSA
quantitation (the "initial" spike run data is specifically excluded from use
in the MSA quantitation).
MSA spikes must be prepared such that:
a> Spike 1 is approximately 20% of the linear range in rag/L;
, b) Spike 2 is approximately 40% of the linear range in mg/L; and
c) Spike 3 is approximately 60% of the linear range in mg/L.
6.10.4 Calculations
i t> (SSR-SR> .nn
% Recovery - »_- <- x iQO
kDcV
Where:
SSR - Spiked Sample Result;
SR - Sample Result; and
SA f Spike Added.
RSD - (crn.,/x) x 100
Where:
ffn-jL ** Standard deviation; and
x Mean '
6.10.5 Technical Acceptance Criteria
For concentrations £ CRQL, the duplicate exposures must agree within
± 20 percent RSD or CV.
The analytical spike recoveries for the LCS and PB MUST be within
control limits of ± 15 percent (i.e., MSA is NOT performed on the LCS or PB).
6.10.6 Corrective Action
If the %RSD (CV) technical acceptance criteria are not met, rerun the
sample once. If the criteria are still not met, flag the value reported on
FORM I-HCIN with the letter "M" . NOTE: The "M" flag is required 'for the
analytical spike as well as the sample.
If the PB analytical spike technical acceptance criteria are not met,
verify the spiking solution by respiking and rerunning the PB once. If the
criteria are still not met, correct the problem and reanalyze all analytical
-samples associated with that blank.
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Method 200.62-C-CLP
Hydride Inductively Coupled Plasma
If.the LCS analytical spike technical acceptance criteria are not met,
correct the problem and reanalyze all analytical samples associated with that
LCS.
1
6.10.7 Documentation
The raw data package must include absorbance and concentration values
for both exposures, the average value, and the coefficient of variation (or
relative standard deviation, RSD).
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.
Reported values obtained by MSA must be flagged with the letter "S" on
FORM I-HCIN if the correlation coefficient is £ 0.995. If the correlation
coefficient is < 0.995, flag the data on FORHs I-HCIN and X-HCIN with a "+".
NOTE: No combination of these qualifiers can appear in the same field for an
analyte.
6.11 Duplicate Sample Analysis
6.11.1 Summary
Duplicate aliquots of a sample are carried through the preparation and
analysis steps to provide information about the precision of the analytical
methods as well as matrix effects.
6.11.2 Frequency
At least one duplicate sample analysis must be performed on each group
of samples of a similar phase for each SDG.11
If two analytical methods are used to obtain the reported values for the
same metal within a SDG (i.e., ICP, GFAA), duplicate samples must be run by
each method used.
6.11.3 Procedure
Samples identified as field blanks cannot be used for duplicate sample
analysis.
11 EPA may require additional duplicate sample analysis upon special request by
the Project Officer, for which the Contractor will be paid.
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Method 200.62-C-CLP Hydride Inductively Coupled Plasma
EPA may require that. a specific sample be used for the duplicate sample
analysis. *
In the instance where there is more than one duplicate sample per matrix
and concentration per method per SDG, if one duplicate result is not. within
contract criteria, flag all the samples of the same phase and method in the
SDG .
Duplicate sample analyses are required for calculation of relative
percent difference .
6.11.4 Calculations
R?D ' '
Where:
RPD - Relative Percent Difference ; *
S =» First Sample Value (original); and
D - Second Sample Value (duplicate). . .
Duplicates cannot be averaged for reporting on FORM I-HCIN.
6.11.5 Technical Acceptance Criteria
A control limit of ± 20 percent for RPD shall be used for original and
duplicate sample values greater than or equal to 5x CRQL (Exhibit C) . A
control limit of ± the CRQL must be used for sample values less than 5x CRQL.
If one result is above the 5x CRQL level and the other is below, use the
± CRQL .criteria.
If both sample values are less than the MDL, the RPD is not calculated.
Specific control limits for each element will be added to FORK VIII-HCIN
at a later date based on precision results.
6 . 11 . 6 Corrective Action
If the duplicate sample results are outside the control limits, flag all
the data for samples received associated with that duplicate sample with an
asterisk "*" . .
6.11.7 Documentation
The results of the duplicate sample analyses must be reported on FORM
VIII-HCIN in mg/Kg.
The absolute value of the control limit (CRQL) must be entered in the
"CONTROL LIMIT" column on FORM VIII-HCIN.
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Method 200.62-C-CLP
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6.12 Laboratory Control Samples
6.12.1 Summary
A laboratory control sample is digested and analyzed to ensure against
analyte loss in the sample preparation.
6.12.2 Frequency
One LCS must be prepared and analyzed for every group of samples in a
SDG, or for each batch of samples, whichever is more-frequent.
6.12.3 Procedure
The 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 LCS must be obtained from EPA. (If unavailable, other EPA Quality
Assurance check samples or other certified materials may be used.)
6.12.4 Calculations
_ Found Concentration -nn
% Recovery - * *"*"-***- x ^QQ
J True Concentration
.6.12.5 Technical Acceptance Criteria
Recovery for the LCS must be within ± 20 percent of the true value
(i.e., 80-120Z).
6.12.6 Corrective Action
If the percent recovery for the LCS falls outside the established by
EPA, then the analyses must be terminated, the problem corrected, and the
samples associated with that LCS reprepared and reanalyzed.
6.12.7 Documentation
Report the LCS found concentration (in mg/Kg), true concentration (in
mg/Kg), and percent recovery on FORM IX-HCIN.
6.13 Method Detection Limits .
6.14.1 Summary . .
The method detection limit (MDL) must be determined before any samples
are analyzed for every instrument that will be used.
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6.13.2 Frequency
MDLs must be determined within 30 days of the start of the contract and
at least quarterly (every three calendar months) until the end of the
contract.- .
6.13.3 Procedure
The Method Detection Limits (in mg/L) shall be determined by multiplying
by 3, the average of the standard deviations (an_j) obtained on three
nonconsecutive days' from the consecutive analysis of seven different
preparation blank dissolutions. 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). MDLs must be determined and reported for each
wavelength used in the analysis of the samples.
The quarterly determined MDL for an instrument must always be used as
the MDL for that instrument during that quarter. If the instrument is
adjusted in anyway that may affect the MDL, the MDL for that instrument must
be redetermined and the results submitted for use as the established MDL for
that instrument for the remainder of the quarter.
MDLs must be determined in mg/L.
6.13.4 Calculations
MDL - <*_,) x 3
6.13.5 Technical Acceptance Criteria
The MDLs must be able to meet the CRQLs established in Exhibit C.
6.13.6 Corrective Action
If an instrument's MDL cannot meet the CRQL for an analyte, that
instrument cannot be used to quantitate an analysis unless the analyte
concentration is greater than or equal to two times the reported MDL.
6.13.7 Documentation
MDLs must be reported for each instrument used on FORM XI-HCIN submitted
with each data package. If multiple instruments are used for the analysis of
an analyte within a SDG, the highest MDL for the analyte must be used for
reporting concentration values for that SDG.
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Method 200.62-C-CLP Hvdride Inductively Coupled Plasma
7. Instrument Operation
7.1 System Configuration
7.1.1 The variable parameters such as incident power, coolant and auxiliary
argon flows should be similar to those used for the analysis of water samples
with a pneumatic nebulizer. The carrier argon flow and the observation height
may have to be changed from that normally used for water samples to obtain the
optimum signal for the hydride analyses.
7.1.2 The appropriate cycle times for sampling and rinsing must be
determined for each system. These criteria are to be documented and reported
in accordance with Exhibits D and E of this contract. Direct monitoring of
the photocurrent from the detector system for one of the analytes should be
conducted to establish when the signal is at steady state, both for the sample
response and in rinsing the sample from the system. Alternatively, sequential
exposures of about 5 to 10 seconds during a cycle can establish the
appropriate time intervals. Typically, the sample signal will reach a maximum
in 30 to 45 seconds after the sample has entered the phase separator. Rinse
times of at least one minute are required between samples. It is required
that the contractor document these parameters quarterly in the form of raw
data results for this optimization. To test for sample carry-over, the
analyst should analyze a high standard (greater than 10 mg/L) containing all
the analytes followed by the continuous aspiration of the blank solution. The
blank solution is to be continuously monitored (in intensity units) until the
intensity becomes stable at the background level. The time required to
completely remove all traces of any analyte is the required wash time. If any
sample solution analyzed contains any analyte at a concentration greater than
the high standard solution analyzed above (prior to dilution correction), the
sample following that solution must be reanalyzed. Alternately, the wash
check above may be repeated and documented at a higher concentration than the
sample.
7.1.3 Every solution, including calibration standards, calibration and
method blanks, reference samples, and fused samples, must be analyzed using
two full exposures (peak scan) each of which is sufficient to meet the method
detection limit for each analyte emission line. All exposure times must be
the same for all analyses and all quarterly analyses (i.e., Method Detection
Limit, Linear Range, and Interelement Correction Factor).
7.1.4 The phase separator can be easily connected to most instruments by
connecting the carrier argon flow to the gas inlet tube of the separator. The
gas outlet of the phase separator must contain a glass wool packing and is
connected to the nebulizer. The usual sample introduction fitting of the
nebulizer will have to be plugged or the connecting tubing pinched shut.
7.1.5 The use of a mass flow controller on the carrier argon flow is
recommended in place of a rotometer.
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7.1.6 In practice, the carrier argon flow and the sample and reagent flows
may have to be adjusted to maintain a stable plasma. The hydride generation
reaction evolves a considerable amount of hydrogen, which can destabilize a
plasma under normal operating conditions. The flows may be decreased or
increased as the analyst sees fit. The ratio of the sample flow to the
reagent flows should be maintained.
7.1.7 The flow of the waste line from the phase separator returning to the
pump will need to be optimized for each particular system. This is necessary
to prevent sample carry-over and must be checked and documented by
continuously analyzing a blank solution after a high (greater than 10 mg/L)
standard for each element.
7.1.9 The sodium borohydride solution is essentially at saturation and will
require stirring with a magnetic stirrer during the analysis.
7.2 System Startup (Recommended)
7.2.1 All pump lines should be pumping only ASTM Type II water.
7.2.2 Set up the instrument with the proper operating parameters as
established in Section 7.1. The instrument must be allowed to become
thermally stable before beginning the analysis. This requires at least 30
minutes of operation with the plasma lit prior to calibration.
7.2.3 Initiate appropriate operating configuration of the instrument
computer.
7.2.4 Perform the appropriate steps recommended by the manufacturer to
align the exit slits with the entrance slit.
7.2.5 Place the sample pump line in the acid rinse solution and start the
potassium iodide flow.
7.2.6 After the acid has entered the phase separator, start the sodium
borohydride flow. Just before the sodium borohydride comes in contact with
the rinse solutions, slow the pump down to about half of its normal flow. As
soon as the borohydride comes in contact with the acid rinse, a violent
reaction starts that evolves hydrogen. Be ready to make adjustments on the
flow controls to help stabilize the plasma.
7.2.7 As the plasma stabilizes, slowly increase the flow of the pump to the
appropriate level, making adjustments to stabilize the plasma as the amount of
hydrogen increases. Hereafter, do not let the sample line remain out of the
rinse solution or a digested sample too long. If the borohydride is allowed
to build up in the separator without constant acid introduction, the plasma
will be extinguished once acid is introduced. If one wants to stop the
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Method 200.62 - C - CLP Hydride Inductively Coupled Plasma
analysis, place the borohydride line in water and continue pumping the acid
until hydrogen evolution ceases. As the hydrogen evolution decreases,
adjustments will be needed to stabilize the plasma.
7.3 Linear Range Determination
7.3.1 The linear range of each analyte line must be" determined under the
same operating conditions used for sample analysis in accordance with Exhibits
D and E of this contract. Changes in the operational parameters will change
the emission characteristics and will require the re-establishment of the
linear range,
7.3.2 The upper limit of the linear range is defined as the highest
standard concentration that does not deviate from the calibration curve fit of
the lower concentration standards by more than 10% from the known
concentration.
7.3.3 All sample values reported shall be based on measurements that are
within the linear range of the instrument.
7.4 Method Detection Limit(s) Determination
7.4.1 The method detection limit (MDL) for all metals must be determined
using the same operating conditions and/or instrument hardware used for sample
analyses and at the frequency required by Exhibits D and E of this contract.
8. Calibration and Sample Analysis
8.1 Sample Preparation
8.1.1 The day that the sample is to be analyzed, transfer 5.0 mL of the
fusion dissolution to1 a 10 mL screw cap test tube. Add 5.0 mL of high purity
HC1 to the test tube-. Volumes for each can be scaled up if 10 mL is found, to
be inadequate.
8.1.2 Place the cap on the test tube, tighten the cap and mix the solution
either on a vortex mixer or by inverting the tube a number of times.
8.1.3 Heat the test tube for 20 minutes at 90 ± 2°C, either in a water bath
or block heater.
8.1.4 Cool the solution to room temperature.
' ' '
8.2 Calibration
8.2.1 Set up the instrument with proper operating parameters as established
in Section 7.1. The instrument must be allowed to become thermally stable
before beginning analysis. This requires at least 30 minutes of operation
with the plasma lit prior to calibration. '
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Method 200.62-C-CLP " Hydride Inductively Coupled Plasma
8.2.2 Initiate appropriate operating configuration of the computer.
8.2.3 Calibrate the instrument using the appropriate matrix matched
calibration standard solution(s). The number of standards utilized is left to
the discretion of the operator but must include a calibration blank and at
least one standard. The operator should be aware of the requirements in
Exhibits D and E that provide for the assurance that all sample values are
within the linear range of the initial calibration.
8.2,.A All standards, blanks, and sample solutions must, contain 50% (v/v)
HC1. A change in the acid strength changes the slope of the calibration curve
and can cause inaccurate results
8.3 Analysis Sequence
8.3.1 Before beginning the sample analysis run, analyze under the same
operating conditions intended for sample analyses the initial calibration
blank (ICB), initial calibration verification (ICV), two times the CRQL
standard (CRI) and the linear range standard (LRS). The ICV, CRI and LRS
found concentration values must not deviate from the true values by more than
10%. The calibration blank values may not exceed the CRQL. If these
conditions are not met for any analyte, the analysis shall be discontinued and
corrective action applied until the conditions are met (see Exhibits D and E
for additional information).
8.3.2 Upon successful analysis of the ICV, ICB and LRS, analyze all method
preparation blank (PB) dissolution^) prepared with the fused samples. If any
of the blank(s) values are not less than or equal to the CRQL, see Exhibits D
and E for the appropriate action.
8.3.3 If the method blank(s) values are acceptable, analyze the Laboratory
Control Sample (LCS). If any LCS values deviate from the acceptable ranges,
see Exhibits D and E for the appropriate action.
8.3.4 If the LCS values are within the acceptable ranges, analyze the
method spike sample. If the recovery of any element deviates from the
acceptable ranges, see Exhibits D and £ for the appropriate action. Proceed
to the analysis of samples if the recoveries are acceptable or after
consulting Exhibit E.
8.3.5 The Continuing Calibration Verification Standard (CCV) and the
Continuing Calibration Blank (CCB) must be analyzed after every ten analytical
sample analyses. It is required that the analyst run the CCV and CCB after
the analysis of the previous sample, but prior to use of a tip wash or other
clean-out device. CCV values must not deviate from the actual values by more
than ± 10%. In addition, the absolute values for the calibration blank must
be lower than the required quantitation limits. If these conditions are not
met at any time during samples analysis, discontinue the analysis and see
Exhibit E for the appropriate action.
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Method 200.62-C-CLP
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8.3.6 At the end of the sample analysis run, analyze the CRI, U.S, CCB and
CCV. If the values for any of these samples deviates from the required
limits, see Exhibits D and E.
8.4 Sample Analyses
8.4.1 All sample dissolutions must first be analyzed without any dilution.
Diluting sample dissolutions is permissible if necessary provided that the
CRQL is not exceeded.
8.4.2 All concentrations reported must be obtained within the established
linear range for that analysis run. All concentrations within the linear
range of the analyte are to be reported. (See Section 7.3)
8.4.3 In order to determine if the sample result is to be calculated by the
Method of Standard Addition (MSA), an analytical spike at 30% of.the
instrument's linear range must be performed and analyzed immediately after
each sample analysis. The analytical spike recovery must be used to determine
the_need for MSA as explained in Exhibits D and E. The spiking solution
volume must not exceed 10% of the sample volume.
8.5 Method of Standard Additions
8.5.1 The following procedure uses a dilution of the sample digest obtained
from the procedure described in Section 8.1. A dilution is used so that less
than 10 mL of digest will be required for the standard addition set. The
dilution is not required but more than 10 mL of sample will have to be
digested in the Section 8.1 procedure if the dilution method is not used.
8.5.2 Transfer 2 mL aliquots of the sample digest from Section 8.1 plus 2.
mL of the HC1 digested blank solution into each of four 10 mL test tubes or
sample vials.
8.5.3 To the first aliquot add an appropriate volume of the spiking
standard reagent blank solution, mix, and analyze.
8.5.4 Add appropriate volumes of the spiking standard to the remaining
three aliquots that result in concentrations at 20%, 40% and 60% of the
instruments linear range. The spiking standard solution volume added to each
aliquot must not exceed 10% of the volume of the aliquot. Add the appropriate
amount of blank solution to each aliquot to make the total of spike plus blank
volumes added equal.
NOTE: If more than ten minutes has elapsed since the first aliquot was
analyzed, it is suggested, but not required, that the CCV and the CCB be
analyzed to determine whether recalibration is required. Performing the
calibration verification prior to reanalyzing the first aliquot and the spiked
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Hvdride Inductively Coupled Plasma
aliquots may save considerable time in the long run, as it can eliminate-the
repeat analyses required if the CCV or blank values are not within the
acceptable limits post sample analysis.
8.5.5 Using a calculator or a statistical package on a computer, determine
the slope, the intercepts of the ordinate (y-axis) and the abscissa (x-axis),
and the correlation coefficient using the found concentration as the ordinate
and the standard addition concentration as the abscissa. The absolute value
of the intercept of the abscissa is the concentration of the analyte in the
dilute solution. If fhe correlation coefficient (r) is less than 0.995, then
the analyses must be repeated. If the correlation coefficient is stall less
than .0.995, report the results on FORM I-HCIN from the run with the best "r"
and flag that sample data with a "+".
8.6 Calculations
8.6.1 Determine the method detection limit (MDL) from the standard
deviation of the method blank analyte analyses as described in 6.13.
8.6.2 Calculate the method blank(s) concentration (in mg/Kg) by multiplying
the value obtained in Section 8.3.2 for the blank by the dilution factors used
in Sections 8.4 and 8.5. Assume a 0.25 g weight for the blank.
8.6.3 Calculate sample dissolution concentrations (in mg/L) by multiplying
the analyte concentration calculated in Section 8.5 by the appropriate
dilution factors used in Sections 8.4 and 8.5. Calculate the sample
concentration (in mg/Kg) by multiplying the above result by the dissolution
volume (liters) and by dividing by the weight of the fused sample (in Kg).
All concentrations are to be reported in units of mg/Kg. No blank subtraction
is required.
8,6.4 Calculate all method spike levels relative to the corresponding
unspiked sample concentration in units of mg/Kg.
8.6.5 Calculate the relative percent difference (RPD) for both the method
and analysis duplicates. Calculate the RPD by dividing the absolute value of
the difference between the sample value and the duplicate value by their mean
and multiplying by 100.
8.7 Documentation
8.7.1. Record all analyte results on FORM I-HCIN.
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Method 202.62-D-CLP
Determination of Potassium Hydroxide Fusion Samples by
Graphite Furnace Atomic Absorption (GFAA) Methods Technique
1. Scope and Application
1.1 This method is applicable to the determination of metals dissolved by
the potassium hydroxide fusion method (Method 200.62-A-CLP) at all
concentrations by Graphite Furnace Atomic Absorption (GFAA) techniques.
Appropriate steps must be taken in all analyses to ensure that potential
interferences are taken into account.
»
1.2 Because of the difference between various makes and models of
satisfactory instruments, no detailed instrumental operating conditions can be
provided. Instead, the analyst is referred to the instructions provided by
the manufacturer of that instrument.
1.3 Detection limits, sensitivity, and optimum ranges of the metals will
vary with the various makes and models of satisfactory graphite furnace atomic
absorption spectrometers.
2.
Summary of Method
2.1 Using the furnace technique in conjunction with an atomic absorption
spectrometer, a representative aliquot of a sample is placed in a graphite
tube in the furnace, evaporated to dryness, charred, and atomized. Radiation
from a given excited metal is passed through the vapor containing the ground
state atoms of that metal. The intensity of the transmitted radiation
decreases in proportion to the amount of the ground state metal in the vapor;
The'metal atoms to be measured are placed in the beam of radiation by
increasing the temperature of the furnace thereby causing the injected
specimen to be volatilized. A monochromator isolates the characteristic
radiation from the lamp.and a photosensitive device measures the attenuated
transmitted radiation.
3.
Interferences
3.1 The composition, of the sample phase can have a major effect on the
analysis. By modifying the sample phase, either to remove interferences or to
stabilize the analyte, interferences can be minimized. Examples are the
addition of ammonium nitrate to remove alkali chlorides and the addition of
ammonium phosphate to retain cadmium.
3.2 Gases generated in the furnace during atomization may have molecular
absorption bands encompassing the analytical wavelength. Therefore the use of
background correction is required for all furnace analysis.
3.3 Continuum background correction cannot correct for all types of
background interference. The use of Zeeman, or Smith-Hieftje (or equivalent)
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Potassium Hydroxide Fusion by GFAA
background correction is required. When the background interference cannot be
compensated for, choose an alternative wavelength, chemically separate the
analyte from the interferant, or use an alternative-form of background
correction.
3.4 Interferences from a smoke producing sample matrix can sometimes be
reduced by extending the charring time at a higher temperature or utilizing an
ashing cycle in the presence of air. Care must be taken to prevent the loss
of analyte.
4.
Apparatus
4.1 Atomic absorption spectrometer: Single or dual channel,- single or
double beam instrument having a grating monochrometer, photomultiplier
detector, adjustable slits, a wavelength range of 190 to 800 nm, background
correction, and provisions for interfacing with a recording device.
4.2 Graphite furnace: Any furnace device capable of reaching the specified
temperatures is satisfactory.
4.3 Operating conditions: Because of the differences between various makes
and models of satisfactory instruments, no detailed operating conditions 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 on that
particular instrument.
4.4 It is the responsibility of the analyst to verify that the instrument
configuration and operating conditions used satisfy the analytical
requirements set forth in this SOW and to maintain quality control data
confirming instrument performance and analytical results.
5.
Reagents and Standards
5.1 Matrix matching, with the samples is mandatory for all blanks,
standards, and quality control samples to avoid inaccurate concentration
values due to possible standard curve deviations.
5.2 Preparation of. standards - Calibration standards are prepared by
diluting the stock metal solutions at the time of analysis and are discarded
after use. Prepare at least three calibration standards in graduated amounts
in the appropriate range by combining an appropriate volume of stock solution
in a volumetric flask. All calibration standards must contain 2 g of KOH and
10 mL of concentrated HN03 per 100 mL. It is convenient to prepare a solution
containing 4 g of KOH and 20 mL of HN03 per 100 mL, using 50 mL of this
solution per 100 mL in the preparation of the standards.
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Method 202.62-D-CLP Potassium Hydroxide Fusion by GFAA
5.3 Two types of blanks are required for GFAA analysis; the calibration
blank is used in establishing the analytical curve while the preparation .blank
is used to correct for possible contamination resulting from the sample
processing. The calibration blank is prepared by diluting 2 g of KOH and 10
mL of HN03 to 100 mL with ASTM Type II water. The preparation blank is
prepared as specified in section 6.7.3.
6. Quality Control
6.1 Instrument Calibration
6.1.1 Summary
Prior to the analysis of samples and required QC, each GFAA system must
be initially calibrated to determine instrument sensitivity.
6.1.2 Frequency
Instruments must be calibrated daily or once every 24 hours and each
time the instrument is set up.
6.1.3 Procedure
Calibration standards must be prepared by diluting the stock solutions
at the time of analysis, and are discarded after use.
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.
Calibrate according to instrument manufacturers recommended procedures
using at least four standards. Beginning with the calibration blank and
working towards the highest standard, run the standards to calibrate. One
calibration standard must be a blank, and another must be at the CRQL.
Baseline correction is acceptable as long as it is performed after each
and every sample, or after the CCV and CCB, respectively.
Resloping is acceptable as long as it is immediately preceded and
immediately followed by a CCV and CCB.
6.1.4 Calculations
Not applicable.
6.1.5 Technical Acceptance Criteria
Not applicable.
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Method 202.62-D-CLP
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6.1.6 Corrective Action
Not applicable.
6.1.7 Documentation
The instrument standardization date and time must be included in the raw
data.
6.2. Initial Calibration Verification '
-*' »
6.2.1 Summary
Immediately after the GFAA system has 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) (ICV) at each
wavelength used for analysis.
6.2.2 Frequency
Each time the instrument is calibrated, the ICV must be run immediately
following the calibration, before any samples are analyzed.
6.2.3 Procedure
If the ICV 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 linear 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.
6.2.4 Calculations
% Recovery «
Found Concentration
True Concentration
6.2.5 Technical Acceptance Criteria
x 100
Recovery for the ICV must be within + 10 percent of the true value
(i.e. , .90-110%).
6.2.6 Corrective Action
When recoveries of the ICV exceed the technical acceptance criteria, the
analysis must be terminated, the problem corrected, the instrument
recalibrated, and the calibration reverified.
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6.2.7 Documentation
Report the ICV found concentration, true concentration, and percent
recovery on FORM II-HCIN.
6.3 Continuing Calibration Verification
6.3.1 Summary
To ensure calibration accuracy during an analysis run, a continuing
calibration verification solution (CCV) is analyzed and reported for every
wavelength used for the analysis of each analyte.
6.3.2 Frequency
The CCV is run at a frequency of 10 percent or every two hours during an
analysis run, whichever is more frequent.
The CCV is also run after the last analytical sample in the analysis
run.
6.3.3 Procedure
The CCV shall contain the analytes at a concentration at or near the
mid-range of the calibration curve.
The same CCV must be used throughout the analysis runs for a Case of
samples received.
If the ICV 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 linear 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.
Each CCV analyzed must reflect the conditions of analysis for all of the
associated analytical samples (the preceding 10 analytical samples or the
preceding analytical samples up to the previous CCV). The duration of
analysis, rinses and other related operations that may affect the CCV measured
result, may not be applied to the CCV to a greater extent than the extent
applied to the associated analytical samples. For instance, the difference in
time between a CCV analysis and the blank immediately following it as well as
the difference in time between the CCV and the analytical sample immediately
preceding it, may not exceed the lowest difference in time between any two
consecutive analytical samples associated with the CCV.
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Method 202.62-D-CLP
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6.3.4 Calculations
r, Found Concentration
i. Recovery - ~ ~ ~.
True Concentration
6.3.5 Technical Acceptance Criteria
x 100
Recovery for the CCV must be within ± 10 percent of the true value
(i.e., 90-110%).
6.3.6 Corrective Action
When recoveries of the CCV exceed the technical acceptance criteria, the
analysis must be stopped, the problem corrected, the instrument recalibrated,
the calibration reverified, and reanalyze the preceding 10 analytical samples
(or all analytical samples since the last "acceptable" CCV analyzed). .'
6.3.7 Documentation
Report the CCV found concentration, true .concentration, and percent
recovery on FORM II-HCIN.
6.4 CRQL Standard
6.4.1 Summary
To verify linearity near, the CRQL, the Contractor must analyze a GFAA
standard at two times the CRQL or two times the MDL, whichever is greater.
This standard must be run for every wavelength used for analysis.
6.4.2 Frequency
The CRQL standard must be run at the beginning and end of each sample
analysis run, or a minimum of twice per eight hours, whichever is more
frequent.
6.4.3 Procedure
The CRQL standard is not to be run.before the ICV solution.
6.4.4 Calculations
Found Concentration
% Recovery - - -
J True Concentration
6.4.5 Technical Acceptance Criteria
x 100
Recovery of the CRQL standard must be within ± 15 percent of the true
value (i.e., 85-115%) for each wavelength used for analysis. (See Table 3,
Exhibit C).
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Method 202.62-D-CLP
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6.4.6 Corrective Action
If the CRQL standard does not fall within the control limit, the .
analysis must be terminated and the problem corrected and the analytical
samples since the last acceptable CRA must be reanalyzed.
6.4.7 Documentation
Report the CRQL standard's found concentration, true concentration, and
percent recovery on FORM III-HCIN.
6.5 Initial Calibration Blank
6.5.1 Summary
To verify that the GFAA system is not contaminated, an initial
calibration blank (ICB) must be analyzed after calibration.
6.5.2 Frequency
The ICB must be analyzed each time the system is calibrated immediately
after the ICV.
6.5.3 Procedure
If the absolute value of the ICB is greater than the MDL, the result
must be reported.
6.5.4 Calculations
Not applicable.
6.5.5 Technical Acceptance Criteria
The absolute value of the ICB must be less than the CRQL.
6.5.6 Corrective Action
When the ICB concentration does not meet the technical acceptance
criteria, terminate analysis, correct the problem, recalibrate, verify the
calibration, and reanalyze the ICB.
6.5.7 Documentation
Report the ICB values in mg/L on FORM IV-HCIN.
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6.6 Continuing Calibration Blanks
6.6.1 Summary
To ensure that the system is not contaminated during the analysis run,
continuing calibration blanks (CCB) are analyzed.
6.6.2 Frequency
Analyze the CCB at a frequency of 10 percent or every two hours,
whichever is more frequent.
Analyze the CCB after every CCV.
6.6.3 Procedure
A CCB must be run after the last CCV in the analysis run.
If the absolute value of the CCB is greater than the MDL, the result
must be reported.
6.6.4 Calculations
Not applicable.
6.6.5 Technical Acceptance Criteria
The absolute value of the CCB must be less than the CRQL.
6.6.6 Corrective Action
When the CCB concentration does not meet the technical acceptance
criteria, terminate analysis, correct the problem, recalibrate, verify the
calibration, and reanalyze the preceding 10 analytical samples (or all
analytical samples since the last "acceptable" CCB analyzed).
6.6.7 Documentation
Report the CCB values in mg/L on FORM IV-HCIN.
6.7 Preparation Blanks
6.7.1 Summary
To ensure against contamination during sample preparation, a preparation
blank (PB) is analyzed.
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Method 202.62-D-CLP Potassium Hydroxide Fusion by GFAA
6.7.2 Frequency
Ac least one PB, must be prepared and analyzed with every SDG, or with
each batch12 of samples digested, whichever is more frequent.
6.7,3 Procedure
The PB shall consist of ASTM Type II water processed through each sample
preparation and analysis procedure step (See Exhibit D, Section III).
»
The first batch of samples in an SDG is to be assigned to PB one, the
second batch of samples to PB two, etc.
6.7.4 Calculations
Not applicable.
6.7.5 Technical Acceptance Criteria
The absolute value of the PB must be less than the CRQL.
6.7.6 Corrective Action
If the absolute value of the concentration of the blank is less than or
equal to the CRQL, no correction of sample results is performed.
If any analyte concentration in the blank is above the CRQL, the lowest
concentration of that analyte in the associated samples must be lOx the blank
concentration. Otherwise, all samples associated with the blank and with the
analyte"s concentration less than lOx the blank concentration and above the
CRQL, must be redigested and reanalyzed for that analyte. The sample
concentration is not to be corrected for the blank value.
~ If the concentration of the blank is below the negative CRQL, then all
samples reported below lOx CRQL associated with the blank must be redigested
and reanalyzed.
6.7.7 Documentation
The values for the PB must be recorded in mg/Kg on FORM IV-HCIN.
12 A group of samples prepared at the same time.
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Method 202.62-D-CLP
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6.8 Spike Sample Analysis >
6.8.1 Summary
To provide information about the effect of the sample matrix on the
digestion, a known amount of analyte is added (spiked) into a sample.
6.8.2 Frequency
At least one spike sample analysis must be performed on each group of
samples of a similar phases for each SDG.13
If two analytical methods are used to obtain the reported values for the
same metal within a SDG (i.e., ICP, HYICP, etc.), then spike samples must be
run by each method used.
6.8.3 Procedure
The spike is added before the digestion (i.e., prior fusion,
distillation or digestion).
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.
In the instance where there is more than one spike sample per phase per
method per SDG, if one spike sample recovery is not within contract criteria,
flag all the samples-of the same phase, and method in the SDG.
6.8.4 Calculations
(SSR-SRI
Recovery
SA
x 100
Where:
SSR - Spiked Sample Result;
SR = Sample Result; and
SA = Spike Added.
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 6.9,
23 EPA may require additional spike sample analysis upon special request by
the Project Officer, for which the Contractor will be paid.
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Method 202.62-D-CLP
Potassium Hydroxide Fusion byGFAA
Duplicate Sample Analysis). The average of the duplicate results cannot be
used for the purpose of determining percent recovery.
When the sample concentration is less than the instrument detection
limit, use SR - 0 only for purposes of calculating percent recovery.
6.8.5 Technical Acceptance Criteria
Recovery for the spike should be within ± 25 percent of the spiked
amount {i.e., 75-125X).
6.8.6 Corrective Action
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 "R" on FORHs I-
and VII-HCIN.
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.
such an event, the data shall be reported unflagged even if the percent
recovery does not meet the 75-125% recovery criteria.
When the digestion spike recovery falls outside the technical acceptance
criteria and the sample result does not exceed 4x the spike added, a
analytical spike must be performed for those metals that do not meet the
specified criteria (exceptions: Ag and Hg) . Spike the unspiked aliquot of the
sample at 2x the indigenous level or 2x CRQL, whichever is greater.
6.8.7 Documentation
Report the spiked sample results, sample results, spike added and
percent recovery for the digestion spike sample analysis on FORM VI-HCIN.
The units for reporting spike sample results will be in rag/Kg.
6.9 Duplicate Sample Analysis ' '
6.9,1 Summary
Duplicate aliquots of a- sample are carried through the preparation and
analysis steps to provide information about the precision of the analytical
methods as well as matrix effects.
6.9.2 Frequency
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Method 202.62-D-CLP
Potassium Hydroxide Fusion by GFAA
At least one duplicate sample analysis must be performed on each group
of samples of a similar phase for each SDG.1*
If two analytical methods are used to obtain the reported values for the
same ::-.etal within a SDG (i.e., ICP, HYICP, etc.), then duplicate samples must
be run by each method used.
6.9.3 Procedure
Samples identified as field blanks cannot be used for duplicate sample
analysis,
EPA may require that a specific sample be used for the duplicate sample
analysis. .
In the instance where there is more than one duplicate sample per phase
per method per SDG, if one duplicate result is not within contract criteria,
then flag all the samples of the same phase and method in the SDG.
Duplicate sample analyses are required for calculation of relative
percent difference.
Duplicates cannot be averaged for reporting on FORM I-HCIN.
6.9.4 Calculations
JS-Dl
RPD -
Where:
(S+D)/2
x 100
RPD - Relative Percent Difference;
S - First Sample Value (original); and
D - Second Sample Value (duplicate).
6.9.5 Technical Acceptance Criteria
A control limit of + 20 percent for RPD shall be used for original and
duplicate sample values greater than or equal to 5x CRQL (Exhibit C). A
control limit of ± the CRQL must be used for sample values less than 5x CRQL.
If one result is above the 5x CRQL level and the other is below, use the
± CRQL criteria.
14 EPA may require additional duplicate sample analysis upon special request
by the Project Officer, for which the Contractor will be paid.
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Method 202.62-D-CLP Potassitim Hydroxide Fusion bv GFAA
For duplicate results < 5x CRQL, enter the absolute value of the CRQL in
the "CONTROL LIMIT" column of FORM VIII-HCIN.
If both sample values are less than the MDL, the RPD is not calculated.
Specific control limits for each metal will be added to FORM VIII-HCIN
at a later date based on precision results.
6.9.6 Corrective Action
If the duplicate sample results are outside the control limits, flag all
the data for samples received associated with that duplicate sample with an
asterisk "*".
6.9.7 Documentation
The results of the duplicate sample analyses must be reported on FORM
VIII-HCIN in mg/Kg.
The absolute value of the control limit (CRQL) must be entered in the
"CONTROL LIMIT" column on FORM VIII-HCIN.
6.10 Laboratory Control Samples
6.10.1 Summary
A LCS is digested and analyzed to ensure against analyte loss in the
sample preparation.
6.10.2 Frequency
One LCS must be prepared and analyzed for every group of samples in a
SDG, or for each batch of samples, whichever is more frequent.
6.10.3 Procedure
The LCS must be analyzed for each analyte using the same sample
preparations, analytical methods and QA/QC procedures employed for the EPA
samples received.
If the EPA LCS is unavailable, other EPA Quality Assurance Check samples
or other certified materials may be used.
6.10.4 Calculations
% Recovery = Found Concentration
J True Concentration
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Method 202.62-D-CLP PotassIUF Hydroxide Fusion by GFAA
6.10.5 Technical Acceptance Criteria
Recovery for the LCS must be within ± 20 percent of the true value
(i.e., 80-120%) with exception of Ag and Sb. . ...
6.10.6 Corrective Action
If the percent recovery for the LCS falls outside the technical
acceptance criteria, the analyses must be terminated, the problem corrected,
and the samples associated with that LCS reprepared and reanalyzed.
6.1-0.7 Documentation
Report the LCS found concentration (in rag/Kg), true concentration (in
mg/Kg), and percent recovery on FORM IX-HCIN.
6.11 Analytical Spike Sample Analysis/Method of Standard Additions
6.11.1 Summary.
To ensure against bias resulting from interference.effects in GFAA
analyses, the Method of Standard Additions (MSA) is utilized.
6.11.2 Frequency
All furnace analyses for each analytical sample will require at least
one analytical spike.
The frequency of MSA will depend on the recovery of the analytical
spike.
6,11.3 Procedure
All furnace analyses, including MSA, must fall within the calibration
range.
All analyses, except during full MSA, require duplicate injections.
Only single injections are required for MSA quantitation. Average
concentration values are used for reporting purposes.
The analytical spike (at a level 2x CRQL) of a sample must be run
immediately after that sample. The percent recovery of the analytical spike
will determine the method of quantitation for the sample.
An analytical spike is not required for the pre-digestion spike sample.
A maximum of 10 full sample analyses to a maximum of 20 injections may
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Method 202.62-D-CLP
Potassium Hydroxide Fusion by GFAA
be performed between each consecutive calibration verifications and blanks,
Each full MSA counts as two analytical samples towards determining 102 CCV/CCB
frequency (i.e., five full MSAs can be performed between calibration
verifications).
For analytical runs containing only MSAs, single injections can be used
for QC samples during that run. For instruments that operate in an MSA mode
only, MSA can be used to determine QC samples during that run. /
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) .
MSA spikes must be prepared such that:
a) Spike 1 is approximately 50% of the sample concentration in mg/L;
b) Spike 2 is approximately 100% of the sample concentration in mg/L;
and
c) Spike 3 is approximately 150% of the sample concentration in mg/L.
6.11.4 Calculations
(SSSR)
% Recovery -
Where :
SSR
SR
SA
RSD - (cr
Where:
x 100
- Spiked Sample Result;
- Sample Result; and.
- Spike Added.
x 100
t?n-i = Standard deviation; and
x - Mean
6.11.5 Technical Acceptance Criteria
For concentrations > CRQL, the duplicate injections must agree within ±
20 percent of RSD or CV.
The analytical spike recoveries for the LCS and PB MUST be within
control limits of ± 15 percent (i.e., MSA is NOT performed on the LCS or PB) .
6.11.6 Corrective Action
If the RSD (CV) technical acceptance criteria are not met, rerun the
sample once. If the criteria .are still not met, flag the value reported on
FORM I-HCIN with the letter "M" . NOTE: The "M" flag is required for the
analytical spike as well as the sample.
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Method 2Q2.62-D-CLP
Potassium Hydroxide Fusion by GFAA
If the PB analytical spike technical acceptance criteria are not met,
verify the spiking solution by respiking and rerunning the PB once. If the
criteria are still not met, correct the problem and reanalyze all analytical
samples associated with that blank.
If the LCS analytical spike technical -acceptance criteria are not met,
correct the problem and reanalyze all analytical samples associated with that
LCS. '
6.11.7 Documentation
The raw data package must include absorbance and concentration values
for both injections, the average value, and the coefficient of variation (or
relative standard deviation, RSD).
1
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.
Reported values obtained by MSA must be flagged with the letter "S" on
FORM I-HCIN if the correlation coefficient is £ 0.995. If the correlation
coefficient is £ 0.995, flag the data on FORMs I-HCIN and X-HCIN with a "+".
6.12 Method Detection Limits
6.12.1 Summary
The instrument detection limit (MDL) must be determined before any
samples are analyzed for every instrument that will be used.
6.12.2 Frequency
MDLs must be determined within 30 days of the start of the contract and
at least quarterly (every three calendar months).
6.12.3 Procedure
The Method Detection Limits (in mg/L) shall be determined by
multiplying by 3, the average of the standard deviations ( obtained on
three nonconsecutive days from the analysis of a standard solution (each
analytein reagent water) at a concentration 3x-5x the instrument
manufacturer's suggested MDL, 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). MDLs
must be determined and reported for each wavelength used in the analysis of
the samples.
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Method 202.62-D-CLP Potassium Hydroxide Fusion by GFAA
The quarterly determined MDL for an instrument must always be used as
the MDL for that instrument during that quarter. If the instrument is
adjusted in anyway that may affect the MDL, the MDL for that instrument must
be redetermined and the results submitted for use as the established MDL for
that instrument for the remainder of the quarter.
MDLs must be determined in mg/L.
6.12.4 Calculations
MDL - (cv,) * 3
Where:
£Tn,1 - Standard Deviation
6.12.5 Technical Acceptance Criteria
The MDL must be able to meet the CRQL's established in Exhibit C.
6.12.6 Corrective Action
If an instrument's MDL cannot meet the CRQL for an analyte, that
instrument cannot be used to quantitate an analysis unless the sample
concentration exceeds two times the MDL.
6.12.7 Documentation
MDLs must be reported for each instrument used on FORM XI-HCIN submitted
with each data package. If multiple GFAA instruments are used for the
analysis of a metal within a SDG, the highest MDL for the GFAA's must be used
for reporting concentration values for that SDG.
7. Instrument Operation
7.1 Instrument Setup
7.1.1 Set up the instrument with the proper operating parameters
established by the instrument manufacturer. The individual steps; drying,
charring and atomization require careful consideration to ensure each process
is carried out effectively. The instrument must be allowed to become
thermally stable before beginning any analysis. This usually requires at
least 30 minutes of operation prior to calibration. Background correction
must be used.
7.2 Calibration and Sample Analysis
7.2.1 Calibrate the instrument according to the manufacturer's recommended
procedures and as explained in section 6.1, using calibration standard
solutions.
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Method 202.62-D-CLP
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7.2.2 In order to determine if the sample result is to be calculated by
MSA, an analytical spike must be performed and analyzed after each sample
analysis. The analytical spike recovery must be used to determine the need
for MSA as explained in Section 6.11. The spiking solution volume must not
exceed 10 percent of the sample volume.
7.2.3 Dilute and reanalyze samples that are more concentrated than the
linear range (i.e., top calibration standard) for an analyte.
8.
Sample Analysis
8.1 Calibration
8.1.1 Set up the instrument with proper operating parameters as established
in Section 7.1. The instrument must be allowed to become thermally stable
before beginning analysis. This requires at least 30 minutes of operation
with the plasma lit prior to calibration.
8.1.2 Initiate appropriate operating configuration of the computer.
8.1.3 Calibrate the instrument using the appropriate matrix matched
calibration standard solution(s). The number of standards utilized is left to
the discretion of the analyst but must include a calibration blank and at
least three standards. The analyst should be aware of the requirements in
Exhibits D and E that provide for the assurance that all sample values are
within the linear range of the initial calibration.
8.2 Analysis Sequence
8.2.1 Before beginning the sample analysis run, analyze under the same
operating conditions intended for sample analyses the initial calibration
blank (ICB), initial calibration verifications (ICV), the CRQL standard (CRA)
and the linear range standard (LRS). The ICV, CRA and LRS found concentration
values must not deviate from the true values by more than 10%. The
calibration blank values may not exceed the CRQL. If these conditions are not
met for any element, the analysis shall be discontinued and corrective action
applied until the conditions are met '(see Exhibits D and E for additional
information).
8.2.2 Upon successful analysis of the ICV, ICB and LRS, analyze all method
preparation blank (PB) dissolution(s) prepared with the fused samples. If any
of the blank(s) values are not less than or equal to the CRQL, see Exhibits D
and E for. the appropriate action.
8.2.3 If the method blank(s) values are acceptable, analyze the Laboratory
Control Sample (LCS). If any LCS values deviate from the acceptable ranges,
see Exhibits D and E for the appropriate action.
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Method 202.62-D-CLP
Potassium Hydroxide Fusion by GFAA
8.2.4 If the LCS values are within the acceptable ranges, analyze the
method spike sample. If the recovery of any element deviates from the
acceptable ranges, see Exhibits D and E for the appropriate action. Proceed
to the analysis of samples if the recoveries are acceptable or after
consulting Exhibit E.
8.2.5 The Continuing Calibration Verification Standard (CCV) and the
Continuing Calibration Blank (CCB) must be analyzed after every ten analytical
sample analyses. It is required that the analyst run the CCV and CCB after
the analysis of the previous sample, but prior to use of a tip wash or other
clean-out device. CCV values must not deviate from the actual values by more
than ± 10 percent. In addition, the absolute values for the calibration blank
must be lower than the required quan'titation limits. If these conditions are
not met at any time during samples analysis, discontinue the analysis and see
Exhibit £ for the appropriate action.
8.2.6 At the end of the sample analysis run, analyze the CRA, LRS, CCB and
CCV. If the values for any of these samples deviates from the required
limits, see Exhibits D and E.
8.3 Sample Analyses
8.3.1 All sample dissolutions must first be analyzed without any dilution.
Diluting sample dissolutions is permissible if necessary provided that the
CRQL is not exceeded.
8.3.2 All concentrations reported must be obtained within the established
linear range for that analysis run. All concentrations within the linear
range of the analyte are to be reported.
8.3.3 In order to-determine if the sample result is to be calculated by the
Method of Standard Addition (MSA), an analytical spike at 2x the CRQL must be
performedand analyzed immediately after each sample analysis. The analytical
spike recovery must be used to determine the need for MSA as explained in
Exhibits D and E. The spiking solution volume must not exceed 10 percent of
the sample volume.
8.4 Method of Standard Additions
8.4.1 To the first aliquot add an appropriate volume of the spiking
standard reagent blank solution; mix; and analyze.
8.4.2 Add appropriate volumes of the spiking standard to the remaining
three aliquots that result in concentrations at 50%, 100% and 150% of the
sample concentration. The spiking standard solution volume added to each
aliquot must not exceed 10% of the volume of the aliquot. Add the appropriate
amount of blank solution to each aliquot to make the total of spike plus blank
volumes added equal.
IHC01.2.
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Method 202.62-D-CLP
Potassium Hydroxide Fusion bv GFAA
8.4.3 Using a calculator or a statistical package on. a computer,'determine
the slope, the intercepts of the ordinate (y-axis) and the abscissa (x-axis);
and the correlation coefficient using the found concentration as the ordinate
and the standard addition concentration as the abscissa. The absolute value
of the intercept of the abscissa is the concentration of the analyte in the
dilute solution. If the correlation coefficient (r) is less than 0.995, then
the analyses must be repeated. If the correlation coefficient is still less
than 0.995, report the results on FORM I-HCIN from the run with the best "r"
and flag that sample data with a "+".
8.5 Calculations >
8.5.1 Determine the method detection limit (MDL),from the standard
deviation of the method blank analyte analyses.as described in 6.12.
8.5.2 Calculate the method blank(s) concentration (in mg/Kg) by multiplying
the value obtained in Section 8.2.2 for the blank by the dilution factors used
in Sections 8.3 and 8.4. Assume a 0.25 g weight for the blank.
*
8.5.3 Calculate sample dissolution concentrations (in mg/L) by multiplying
the analyte concentration calculated in Section 8.4 by the appropriate
dilution factors used in Sections 8.3 and 8.4. Calculate the sample
concentration (in mg/Kg) by multiplying the above result by the dissolution
volume (in liters) and by dividing by.the weight of the fused sample (in Kg).
All concentrations are to be reported in units of mg/Kg. No blank subtraction
is required.
8.5.4 Calculate all method spike levels relative to the corresponding
unspiked sample concentration in units of mg/Kg. ;
8.5.5 Calculate the relative percent difference (RPD) for both the'method
and analysis duplicates. Calculate the RPD by dividing the absolute value of
the difference between the sample value and the duplicate value by their mean
and multiplying by 100.
8.6 Documentation
8.6.1 Record all analyte results in mg/Kg on FORM I-HCIN.
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Method 202.2-CLP
>
Cold Vapor Atomic Absorption (CVAA) Spectroscopic
Determination of Mercury in Industrial Waste Materials
1. Scope and Application
1.1 This method is applicable to the determination of mercury in all
industrial waste samples.
1.2 All samples are subject to the same dissolution procedure prior to the
measurement of the mercury.
1.3 The method has proven to be accurate for the determination of mercury in
standard reference materials consisting of oil, soil, rock, sediment, water,
gelatin, and sludge. These materials were quite homogeneous and good
precision was obtained.
2.
Summary of Method
2.1 Samples of industrial waste materials are phase separated in accordance
with Method 50.60-CLP, Section III. Aliquots of the individual phases are
digested with a mixture of nitric acid, sulfuric acid, potassium permanganate
and potassium persulfate in a sealed reaction vessel for .two hours at 95 ±
2°C.
2.2 The mercury in the digests is reduced to the elemental state and carried
by nitrogen or air from the solution in a closed system into an optical path
where the absorption of radiation at the 253.7 nm wavelength by the mercury
vapor is.measured. The measured absorbance is related to the concentration of
mercury in the sample through the use of a calibration curve.
3.
Interferences
3.1 Sulfide interference is removed by the addition of potassium
permanganate during sample preparation.
3.2 Volatile organics which absorb at 254 nm shall be at least partially
removed by purging the prepared samples with air or nitrogen before the
addition of the reducing agents to the digested samples. In addition, the use
of background correction techniques can compensate for such non-atomic
absorption. Both flow-through systems and closed loop flow systems (with
internal pump) are acceptable. The use of the former is recommended since its
relatively sharp mercury peak is more easily distinguished from the broader
interference peak. Since many of the samples contain high concentrations of
organic species, it is necessary to compensate for this type of interference.
3.3 Chloride present in the sample preparations may be converted to free
chlorine during the oxidative digestion process and subsequently absorb
radiation at 253.7 nm. To avoid this potential interference, preparations are
IHC01.2
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Method 202.62-CLP . ._ . Mercury by CVAA
purged and an excess of hydroxylamine reagent is added prior to mercury
reduction.
4. Apparatus and Equipment
»
4.1 Atomic absorption spectrophotometer equipped with a cold vapor mercury
determination apparatus and a means of carefully monitoring the flow of
nitrogen or air purge gas.
4.2 Stripchart recorder.
4.3 Water bath: capable of maintaining 95 ± 2°C.
i - -
4.4 800 bottles: 300 mL capacity (or equivalent).
4.5 Nitrogen gas (flow through system) or air recirculation pump with
mercury removal system and drying tube.
4.6 Screw top test cubes: 50 mL capacity (25 x'150 mm) (or equivalent).
4.7 Heating block: for test tubes if applicable.
5. Reagents
5.1 Sulfuric acid, concentrated. Better than reagent grade.
5.1.1 Sulfuric acid, 0.5N. Dilute 14.0 mL of concentrated sulfuric acid
to one liter with ASTM Type II water.
5.2 Nitric acid, concentrated. Better than reagent grade.
5.2.1 Nitric acid, 0.15% (v/v). Dilute 1.5 mL of concentrated nitric
acid to one liter with ASTM Type II water.
5.3 Stannous chloride solution. Add 100 g stannous chloride to one liter of
0.5 N sulfuric acid.
5.4 Sodium chloride-hydroxylamine hydrochloride solution. Dissolve 120 g
sodium chloride and 120 g hydroxylamine hydrochloride in ASTM Type II water
and dilute to one liter.
5.5 Potassium permanganate, 5% (w/v). Dissolve 25 g potassium permanganate
in 500 mL ASTM Type II water.
5.6 Potassium persulfate, 5% (w/v). Dissolve 25 g potassium persulfate in
500 mL ASTM Type II water.
IHC01.2. Page 187
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Method ?02.62-CLP
by CVAA
5.7 Mercury stock solution, 1000 mg/L.
standard is acceptable.
Use of NIST traceable commercial
5.8 Working mercury solution A, 10.0 mg/L. Dilute 1.0 mL of stock mercury
solution to 100 mL with 0.15Z (v/v) nitric acid. This solution should be
freshly prepared each time the instrument is calibrated.
5.9 Working mercury solution B, 0.10 mg/L. Dilute 1.0 mL of working mercury
solution A to 100 mL with 0.15Z (v/v) nitric acid. This solution should be
freshly prepared each time the instrument is calibrated.
6. Sample Handling and Preservation
6.1 Once prepared, the mercury preparations should be refrigerated to avoid
further degradation of potassium permanganate.
6.2 Because of the extreme sensitivity of the analytical procedure and
omnipresence of mercury, care must be taken to avoid extraneous contamination.
Sampling devices and sample containers should be free of mercury; the samples
should not be exposed to any condition in the laboratory that may result in
contact to air borne mercury contamination.
6.3 Because of the toxic nature of mercury vapor, precaution must be taken
to avoid inhalation. Therefore, when the samples are analyzed, the released
mercury vapor should be passed through an absorbing media, such as equal
volumes of 0.1 N KMn04 and 10% H2S04 or 0.25Z iodine in a 32 KI solution. A
specially treated charcoal that will absorb mercury vapor is also available.
7.
Quality Control
7.1 Instrument Calibration
7.1.1 Summary
Prior to the analysis of samples and required QC, each CVAA system must
be initially calibrated to determine instrument sensitivity.
7.1.2 Frequency
Instruments must be calibrated daily or once every 24 hours and each
time the instrument is set up.
7.1.3 Procedure
Calibration standards must be prepared using the same type of matrix and
at the same reagent concentration as the preparation blank following sample
preparation.
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Method 202.62-CLP Mercury by CV4A
Calibrate according to instrument manufacturers recommended procedures
using at least three standards, one being a blank.
Before beginning the sample run, reanalyze the highest mixed calibration
standard as if it were a sample.
7.1.4 Calculations -
.. _ Found Concentration ,._
% Recovery - ~ ~ : ~T- x 100
_ True Concentration
7.1.5 Technical Acceptance Criteria
Recovery for the highest mixed calibration standard must within be ± 5
percent of the true value (i.e., 95-1051).
7.1.6 Corrective Action
Follow instrument manufacturers recommendations to correct the problem.
Also, 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 a CCV and a CCB, respectively.
7.1.7 Documentation
The instrument standardization date and time must be included in the raw
data.
7.2 Initial Calibration Verification
7.2.1 Summary
Immediately after the CVAA system has 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) (ICV) at each
wavelength used for analysis.
7.2.2 Frequency
Each time the instrument is calibrated, the ICV must be run immediately
following the calibration, before any samples are analyzed.
7.2.3 Procedure
If the ICV 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
IHC01.2 Page 189
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Method 202.62-CLP Mercury by CVAA
for instrument calibration, but within the linear 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.
7.2.4 Calculations
% Recovery' - Found Concentration
J True Concentration
7.2.5 Technical Acceptance Criteria
Recovery for the ICV must be within ± 20 percent of the true value
(i.e., 80-120%).
7.2.6 Corrective Action
When recoveries of the ICV exceed the technical acceptance criteria, the
analysis must be terminated, the problem corrected, the instrument
recalibrated, and the calibration reverified.
7.2.7 Documentation
Report the ICV found concentration, true concentration, and percent
recovery on FORM II-HCIN.
7.3 Continuing Calibration Verification
7,3.1 Summary
To ensure calibration accuracy during an analysis run, a continuing
calibration verification solution (CCV) is analyzed and reported for every
wavelength used for the analysis of each analyte.
7.3.2 Frequency
The CCV is run at a frequency of 10 percent or every two hours during an
analysis run, whichever is more frequent.
The CCV is also run after the last analytical sample in the analysis
run.
7.3.3 Procedure
The same CCV must be used throughout the analysis runs for a Case of
samples received.
The analyte concentrations in the continuing calibration standard must
be one of the following -solutions at or near ± 20 percent the mid-range levels
of .the calibration curve:
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Method 202.62-CLP
Mercury by CVAA
EPA Solutions; or
A Contractor prepared standard solution.
Each CCV analyzed must reflect the conditions of analysis for all of the
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.
7.3.4 Calculations
% Recovery -
Found Concentration
True Concentration
7.3.5 Technical Acceptance Criteria
x 100
Recovery for the CCV must be within ± 20 percent of the true value
(i.e., 80-120%). (See Table 3, Exhibit C)
7.3.6 Corrective Action
When recoveries of the CCV exceed the technical acceptance criteria, the
analysis must be stopped, the problem corrected, the instrument recalibrated,
the calibration reverified, and reanalyze the preceding 10 analytical samples
(or all analytical samples since the last "acceptable" CCV analyzed).
7.3.7 Documentation
Report the CCV found concentration, true concentration, and percent
recovery on FORM II-HCIN.
7.4 CRQL Standard
7.4.1 Summary
To verify linearity near the CRQL, the Contractor must analyze an CVAA
standard at two times the CRQL or two times the MDL, whichever is greater.
This standard must be run for every wavelength used for analysis.
7.4.2 Frequency
The CRQL standard must be run at the beginning and end of each sample
analysis run, or a minimum of twice per eight hours, whichever is more
frequent.
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Method 202.62-CLP Herctiry by CVAA
7.4,3 Procedure
' The CRQL standard is not to be run before the ICV solution.
7.4.4 Calculations
n Found Concentration ,_.
;: % Recovery - ~ : x 100
i True Concentration
; 7.4.5 Technical Acceptance Criteria
The results of the CRQL standard must fall within the control limits of
: ± 25'percent of the true value (i.e., 75-125%) for each wavelength used for
analysis.
7.4.6 Corrective Action
If the CRQL standard does not fall within the control limit, the
analysis must be terminated and the problem corrected and the analytical
samples since the last acceptable CRQL standard must be reanalyzed.
7.4.7 Documentation
.1
i Report the CRQL standards found concentration, true concentration, and
'. percent recovery on FORM III-HCIN.
!J 7.5 Initial Calibration Blank
7.5.1 Summary
To verify that the CVAA system is not contaminated, an initial
calibration blank (ICB) must be analyzed" after calibration.
7.5.2 Frequency
; The ICB must be analyzed eacji time the system is calibrated and
immediately after the ICV.
1 7.5.3 Procedure
If the absolute value of the ICB is greater than the MDL, the result
1 must be reported.
H
7.5.4 Calculations
__, Not applicable.
7.5.5 Technical Acceptance Criteria
The absolute value of the ICB must be less than the CRQL.
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Method 202 .62-CLP ; Mercury by CVAA
7.5.6 Corrective Action
When the ICB concentration does not meet the technical acceptance
criteria, terminate analysis, correct the problem, recalibrate, verify the
calibration, and reanalyze the ICB.
7.5.7 Documentation
Report the ICB values in mg/L on FORM IV-HCIN.
7.6 Continuing Calibration Blanks
7.6.1 Summary
To ensure that the system is not contaminated during the analysis run,
continuing calibration blanks (CCB) are analyzed.
7.6.2 Frequency
Analyze the CCB at a frequency of 10 percent or every two hours,
whichever is more frequent.
Analyze the CCB after every CCV.
7.6.3 Procedure
A CCB must be run after the last CCV in the analysis run. '
If the absolute value of the CCB is greater than the MDL, the result
must be reported.
7.6.4 Calculations
Not applicable.
7.6.5 Technical Acceptance Criteria
The absolute value of the CCB must be less than the CRQL.
7.6.6 Corrective Action
When the CCB concentration does not meet the technical acceptance
criteria, terminate analysis, correct the problem, recalibrate, verify the
calibration, and reanalyze the preceding 10 analytical samples (or all
analytical samples since the last "acceptable" CCB analyzed).
IHC01.2 Page 193
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Method 202.62-CLP Mercury bv CVAA
7.6.7 Documentation
Report the ICB values in mg/L on FORM IV-HCIN.
7.7 Preparation Blanks
7.7.1 Summary
To ensure against contamination during sample preparation, a preparation
blank (PB) is analyzed.
7.7.2 Frequency
At least one PB, must be prepared and analyzed with every SDG, or with
each batch15 of samples digested, whichever is more frequent.
7.7.3 Procedure
The PB shall consist of ASTM Type II water processed through each sample
preparation and analysis procedure step (See Exhibit D, Section III).
The first batch of samples in an SDG is to be assigned to PB one, the
second batch of samples to PB two, etc.
7.7.4 Calculations
Not applicable.
7.7.5 Technical Acceptance Criteria
The absolute value of the PB must be less than the CRQL.
7.7.6 Corrective Action
If the absolute value of the concentration of the blank is less than or
equal to the CRQL, no correction of sample results is performed.
If any analyte concentration in the blank is above the CRQL, all
associated samples containing less than lOx the blank concentration must be
redigested and reanalyzed for that analyte. The sample concentration is not
to be corrected for the blank value.
If an analyte concentration in the blank is below the negative CRQL,
then all samples reported below 1Ox CRQL associated with the blank ,aust be
redigested and reanalyzed.
ISA group of samples prepared at the same time.
IHC01.2 Page 194
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Method 202.62-CLP Mercury by GVAA
7.7.7 Documentation
The values for the PB must be recorded in mg/Kg on FORM IV-HCIN.
7.8 Spike Sample Analysis
7.8.1 Summary
To provide information about the effect of the sample matrix on the
digestion, a known amount of analyte is added (spiked) into a sample.
7.8.2 Frequency
At least one spike sample analysis must be performed on each group of
samples of a'similar phases for each SDG.16
7.8.3 Procedure
The spike is added before the sample preparation (i.e., prior to fusion,
digestion or distillation).
The spiking level shall be equal to the CRQL.
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.
In the instance where there is more than one spike sample per phase per
method per SDG, if one spike sample recovery is not within contract criteria,
flag all the samples of the same matrix, level, and method in the SDG.
7.8.4 Calculations
% Recovery - x 1002
wn
Where:
SSR - Spiked Sample Result;
SR - Sample Result; and
SA - Spike Added.
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 7.9, Duplicate
16 EPA may require additional spike sample analysis upon special request by the
Project Officer, for which the Contractor will be paid.
IHC01.2 Page 195
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Method 202.62-CLP
Mercury bv CVAA
Sample Analysis). The average of the duplicate results cannot be used for the
purpose of determining percent recovery.
When sample concentration is less than the instrument detection limit,
use SR - 0 only for purposes of calculating percent recovery.
7.8.5 Technical Acceptance Criteria
Recovery for the spike should be within ± 25 percent of the spiked
amount (i.e., 75-125%).
7.8.6 Corrective Action
If the spike recovery is not 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-HCIN and
VII-KCIN.
An exception to this rule is granted in situations where the sample
concentration exceeds the spike concentration by a factor of four or more. In
such an event, the data shall be reported unflagged even if the percent
recovery does not meet the 75-125% recovery criteria.
7.8.7 Documentation
Report the spiked sample results, sample results, spike added and
percent recovery for the spike sample analysis on FORM VI-HCIN.
The units for reporting spike sample results will be in mg/Kg.
7.9 Duplicate Sample Analysis
7.9.1 Summary
Duplicate aliquots of a sample are carried through the preparation and
analysis steps to provide information about the precision of the analytical
methods as well as matrix effects.
7.9.2 Frequency
At least one duplicate sample analysis must be performed on each group
of samples of a similar phase for each SDG.17
17 EPA may require additional duplicate sample analysis upon special request by
the Project Officer, for which the Contractor will be paid.
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Method 202.62-CLP : ; Mercury by CVAA
7.9.3 Procedure
Samples identified as field blanks cannot be used for duplicate sample
analysis.
EPA may require that a specific sample be used for the duplicate sample
analysis .
/
In the instance where there is more than one duplicate sample per matrix
and concentration per method per SDG, if one duplicate result is not within
contract criteria, flag all the samples of the same phase and method in the
SDG.
Duplicate sample analyses are required for calculation of relative
percent difference . '
7.9.4 Calculations
RPD '
Where : -
RPD - Relative Percent Difference;
S «= First Sample Value (original) ; and
D - Second Sample Value (duplicate) .
Duplicates cannot be averaged for reporting on FORM I-HCIN.
7.9.5 Technical Acceptance Criteria
A control limit of ± 20 percent for RPD shall be used for original and
duplicate sample values greater than or equal to 5x CRQL (Exhibit C). A
control limit of ± the CRQL must be used for sample values less than 5x CRQL.
If one result is above the 5x CRQL level and the other is below, use the
± CRQL criteria.
If both sample values are less than the MDL, the RPD is not calculated.
Specific control limits for each element will be added to FORM VIII -HCIN
at a later date based on precision results.
7.9.6 Corrective Action
If the duplicate sample results are outside the control limits, flag all
the data for samples received associated with that duplicate sample with an
asterisk "*" .
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Method 202,62-CLP ; Mercury by CVAA
7.9.7 Documentation
The results of the duplicate sample analyses must be reported on FORM
VIII-HCIN in mg/Kg.
The absolute value of the control limit (CRQL) must be entered in the
"CONTROL LIMIT" column on FORM VIII-HCIN.
7.10 Laboratory Control Samples
7.10.1 Summary
A LCS is digested and analyzed to ensure against analyte loss in the
sample preparation.
7.10.2 Frequency
One LCS must be prepared and analyzed for every group of samples in a
SDG, or for each batch of samples, whichever-is more frequent.
7.10.3 Procedure
The 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 LCS must be obtained from EPA. (If unavailable, other EPA Quality
Assurance Check samples or other certified materials may be used.)
7.10.4 Calculations
« Found Concentration , -
% Recovery = r r* : x 100
3 True Concentration
7.10.5 Technical Acceptance Criteria
Recovery for the LCS must be within ± 20 percent of the true value
(i.e., 80-120%).
7.10.6 Corrective Action
If the percent recovery for the LCS falls outside the technical
acceptance criteria, then the analyses must be terminated, the problem
corrected, and the samples associated with that LCS reprepared and reanalyzed.
7.10.7 Documentation
Report the LCS found concentration (in mg/Kg), true concentration (in
mg/Kg), and percent recovery on FORM IX-HCIN.
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Method 202.62-CLP
Mercury by CVAA
7.11 Method Detection Limits
7.12.1
Summary
The method detection limit (MDL) must be determined before any samples
are analyzed for every instrument that will be used.
7.11.2
Frequency
MDLs must be determined within 30 days of the start of the contract and
at least quarterly (every three calendar months) until the end of the
contract.
7.11.3
Procedure
The MDLs (in mg/L) shall be determined by multiplying by 3, the average
of the standard deviations (&,,) obtained on three nonconsecutive days from
the consecutive analysis of seven different PB dissolutions. Each measurement
must be performed as thovsh 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). MDLs must be determined
and reported for each wavelength used in the analysis of the samples.
The quarterly determined MDL for an instrument must always be used as
the MDL for that instrument during that quarter.- If the instrument is
adjusted in anyway that may affect the MDL, the MDL for that instrument must
be redetermined and the results submitted for use as the established MDL for
that instrument for the remainder of the.quarter.
MDLs must be determined in mg/L.
7.11.4 Calculations
MDL - (*.,) x 3
7.11.5 Technical Acceptance Criteria
The MDLs must be able to meet the CRQLs established in Exhibit C.
7.11.6 Corrective Action
If an instrument's MDL cannot meet the CRQL for an analyte, that
instrument cannot be used to quantitate an analysis unless the analyte
concentration is greater than or equal to two times the reported MDL.
7.11.7
Documentation
MDLs must be reported for each instrument used on FORM XI-HCIN submitted
with each data package. If multiple instruments are used for the analysis of
IHC01.2
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Method 202.62-CLP Mercury by CVAA
an analyte within a SDG, the highest HDL for the analyte must be used for
reporting concentration values for that SDG.
8 . Sample Preparation Procedure
8.1 Weigh 0.1 g of analytical sample to the nearest milligram into acid
washed screw top test tubes or BOD bottles.
8.2 Add 5.0 mL of concentrated sulfuric acid to each sample and mix. Note
if oxidation (bubbling) of the sample occurs. Such samples may react
vigorously when the permanganate is added. Then add 2.5 mL of concentrated
nitric acid to each sample and mix. Wait 15 minutes.
8.3 Carefully add 50 mL of ASTM Type II water.
8.4 Carefully add 8 mL of 5% KMnO« solution to each sample, mix. After the
first permanganate addition, wait until the preparations are not HOT to the
touch and add another 16 mL; mix. Wait 15 minutes. If the sample solutions
are clear or yellow after the 15 minute wait, add an additional 8 mL
permanganate solution or 0.4 g solid KMnO<, (depending on available space) to
the sample preparation and wait 15 minutes. Repeat this step until the
preparations remain purple after the 15 minute wait. If the sample solutions
remain purple after the 15 minute wait above, add 8 ml 5Z potassium persulfate
solution to each sample, cap and mix.
8.5 Place the sample preparations in a pre-heated block heater or water bath
at a constant temperature of 95 °C for two hours. Remove the samples from the
block or bath at the end of the two hours.
NOTE: Tubes have been known to explode when placed under pressure due to weak
glass and/or caps. Therefore, it is suggested that preparations be enclosed
in a fume hood with the sash down or be surrounded by an explosion shield
during heating.
8.6 Check preparations when cooled to see that they remain purple. If clear
or yellow, add an additional 8 mL 5% KMn04 solution or 0.4 g solid KMnO^ and
heat for one hour. Repeat this step until the preparations remain purple
after cooling.
8.7 When it is determined that the solution remains-purple after, cooling,
either 8 mL of permanganate solution or 0.4 g solid permanganate may be added
to each preparation.
9. Calibration and Sample Analysis
9.1 Preparation of Calibration Standards for Analysis
9.1.1 If the analytical preparations still have the purple color associated
with the KMnOA, proceed to section 9.1.2.. If any of the sample preparations
IHC01.2 Page 200
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Method 202.62-CLP Mercury by CVAA
are clear or yellow, add either 8.0 mL 5% (w/v) KMnO< or 0.4 g solid KMn04;
cap, and heat at 95"C for one hour. .
9.1.2 Transfer 2.0 mL (0.2 pg) , 5.0 mL (0.5 /ng), and 10.0 mL (1.0 /ig) of
working mercury solution B into separate 300 mL BOD bottles or. equivalent.
NOTE: These are recommended standard concentrations and may be changed as
long as the required detection limit is maintained and the number of standards
is not reduced.
9.1.3 Add 5.0 mL concentrated sulfuric acid and 2.5 mL concentrated nitric
acid -to each standard bottle (not the samples) ; mix..
9.1.4 Add 16 mL 5% KMnO^ solution to each standard bottle; mix. Allow to
cool. Wait 15 minutes. . - .
9.1.5 Add 8 mL 5% K2S208 solution to each standard bottle; mix.
9.1.6 Add sufficient ASTM Type II water to the standards to attain a total
volume of approximately 100 mL in.each BOD bottle. The standards are now
ready for analysis;
9.2 Sample/Standard Analysis Procedure
9.2.1 Quantitatively transfer the contents of all analytical sample
preparations to BOD bottles (if tubes were used) and add sufficient ASTM Type
II water to attain a total volume of approximately 100 mL.
9.2.2 First, purge the sample or standard solution in the BOD bottle with
nitrogen or air flowing at 1-4 L/min through an aspirator which is stored in a
BOD bottle containing ASTM Type II water. During the purge cycle, the purge
gas must be vented rather than recirculated. Other purge gas flow rates may
be acceptable if consistent with the manufacturer's instructions. Rinse the
aspirator thoroughly with ASTM Type II water before returning it to tne BOD
bottle containing ASTM Type II water.
9.2.3 Next, add 8 mL hydroxylamine hydrochloride solution to the preparation
or standard being analyzed to reduce excess permanganate (solutions may
require vigorous swirling to clear the solution).
9.2.4 Wait 30 seconds and add 10 mL stannous chloride solution to the
preparation or standard and immediately place the aspirator into the
preparation/standard bottle. Do not agitate the solution. The purge gas flow
rate should be set as described above unless the analyst determines that
system performance would be optimized at another flow rate. Allow the
recorder pen to return to the base line after each deflection and then return
the aspirator to the BOD bottle containing ASTM Type II water for storage
IHC01.2 - Page 201
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Method 202. 62-CLP Mercury by CVAA
prior to the next analysis. Be sure to rinse the aspirator thoroughly with
ASTM Type II water prior to replacing the aspirator into the ASTM Type II
water storage bottle.
9.3 Standard and Sample Analysis Sequence
9.3.1 Analyze a calibration blank, the lowest concentration calibration
standard, the second lowest concentration standard, etc. Scale expansion
should be employed if necessary to obtain measurable readings for the blanks.
Perform a linear regression analysis of the standards according tt> Section 10.
9.3.2 Upon successfully analyzing the ICV, analyze the method blank(s). If
the obtained blank value(s) exceed the quality control limits, discontinue the
analysis and see Exhibit E for appropriate action.
9.3.3 Analyze the samples, the duplicates, and spikes using the flow chart
given in Exhibit E to determine the spike sample and also the method spike
sample. If the spike X recovery for mercury deviates from the acceptable
ranges, see Exhibit E for appropriate action.
9.4 Preparation Dilution
9.4.1 If a preparation is found to contain mercury in a higher concentration
than the highest calibration standard, a new preparation shall be made and
diluted prior to analysis. The total volume of the mercury preparation shall
be decreased by mixing the preparation vigorously and then pipetting an
aliquot of the sample into a BOD bottle (if applicable) and proceeding as per
Section 9.2.1.
NOTE: The solids content of the preparations are quite high and dilution
errors may occur if solids are allowed to settle prior to pipetting.
10. Calculations
10.1 Chart Recorder Peak Measurement: Estimate peak heights to the nearest
0.5 mm for peak heights under 5 mm or to the nearest mm for higher values.
Instrument scale changes or recorder range adjustments to instruments should
be made when necessary to make measurements of otherwise off-scale peaks.
When using a chart recorder in conjunction with an integrator, the area
calculated by the integrator may be used in lieu of the peak height
measurement.
10.2 Construct a calibration solution response curve by using a linear least
squares treatment (regression analysis) of the standard peak height or
absorbance (y) as a function of mass in /ig (x). A correlation coefficient of
greater than or equal to 0.995 is required. If this is not achieved, the
analysis must be repeated after the problem is corrected. Report the
correlation coefficient, slope, and y intercept on the strip chart (see
Exhibit B).
IHC01.2 Page 202
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Method 202.62-CLP Mercury by CVAA
10.2.1 The mercury contained in a sample (in jig) is found by entering the
peak height or absorbance into the regression equation'and obtaining
equivalent jig of mercury. The recorder or instrument range setting must be
taken into account during the calculation.
1C.2.2 The sample concentration of mercury in units of Mg/g is found by
dividing the mass of mercury in /ig, (found from the regression analysis) by
the exact weight of the aliquot (in g) used in the sample preparation. If the
sample was diluted prior to analysis, multiply the pg/g value times the
dilution factor used. Report values down to the required MDL (0.3 Mg/g) or to
lOx the obtained method blank value, as described in Section 7. Record'sample
results on the appropriate form in Exhibit B.
NOTE: Mg/g is proportional to mg/Kg.
11. Documentation
11.1 Report all mercury values in mg/Kg on FORM I-HCIN.
IHC01-.2 Page 203
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Method 335.63-CLP
Colorimetric Determination of Cyanide
in Industrial Waste Materials
1.
Scope and Application
1.1 Cyanide determined by this method is defined as cyanide ion and complex
cyanides converted to hydrocyanic acid by reaction in a reflux system with
mineral acid in the presence of magnesium ion.
1.2 This method covers the determination of cyanide in all phases by
distillation. Either a manual or automated colorimetric analysis of the
distillate may be utilized.
1.3 The detection limit for the automated colorimetric option of this method
is approximately 0.5 Mg/g CN" and for the manual colorimetric option it is
approximately 1.5 ^g/g. The reporting limit for both methods is 1.5 Mg/g-
1.4 The presence of cyanide as determined by this method does not in itself
characterize the waste as a RCRA Reactivity Hazardous Waste.
2.
Summary of Method
2.1 Cyanide is released from most of its complexes and converted to hydrogen
cyanide by means of a reflux distillation. The hydrogen cyanide gas is drawn
by vacuum into a solution of sodium hydroxide where it is absorbed as sodium
cyanide.
2.2 In the colorimetric measurement, the cyanide is converted to cyanogen
chloride by reaction with chloraraine-T at a pH less than 8 without hydrolysis
to cyanate. After the reaction is complete, color is formed on the addition
of pyridine barbituric acid reagent and the absorbance of the color is read at
580 nm. To obtain colors of comparable intensity, it is essential to have the
same salt content in both the samples and the standards.
3. Apparatus
3.1 Reflux distillation apparatus as shown in Figures 1 and 2.
3.2 Heating block - Capable of maintaining 125 ± 5°C.
3.3 Autoanalyzer system or spectrophotometer (580 nm) with accessories:
3.3.1 Sampler
3.3.2 Pump
3.3.3 Cyanide cartridge
3.3.4 Colorimetric with 50 mm flowcells and 570 or 580 nm filters
3.3.5 Chart recorder
IHC01.2
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Method 3 3 5 . 6 3 - CLP . Cyanide by Colorimetric
3.4 Assorted volumetric glassware, pipets, and micropipets.
4. Reagents and Standards (Reagent grade unless otherwise specified)
4.1 Sodium hydroxide absorbing solution," and sample wash solution, 0.25 N.
Dissolve 10.0 g NaOH in ASTM Type II water and dilute to 1 L.
4.2 Sodium hydroxide developing solution, 0.05 N. Dissolve 2.0 g NaOH in
ASTM Type II water and dilute to 1 L. (Manual Colorimetric Method.)
4.3 Sodium hydroxide solution, 0.1N. Dissolve 4 g of NaOH in ASTM Type II
water and dilute to 1 L.
4.4 Sodium hydroxide solution, 1.25 N. Dissolve 50 g of NaOH in ASTM Type
II water and dilute to 1 L.
4.5 Magnesium chloride solution, 51Z (w/v) . Dissolve 510 g of MgCl2-6H20 in
ASTM Type II water and dilute to 1 L.
4.6 Sulfuric acid, 50% (v/y). Carefully add a portion of concentrated HZS04
to an equal portion of ASTM Type II,water.
4.7 Stock cyanide solution, 1000 mg/L GET. Dissolve 2.51 g KCN and 2.0 g
KOH in ASTM Type II water and dilute to 1 L. Standardize in accordance with
Section 7.1.
4.8 Intermediate cyanide standard solution, 10 mg/L CN". Dilute 1.0 mL of
the stock cyanide solution plus 20 mL of 1.25 N NaOH solution to 100 mL with
ASTM Type II water. Prepare this solution at time of analysis.
4.9 Rhodanine indicator. Dissolve 20 mg of p-dimethylamino-benzal-rhodanine
in 100 mL of acetone.
4.10 Silver nitrate solution, 0.0192 N. Prepare by crushing
approximately 5 g AgN03 crystals and drying to constant weight at 104°C.
Weigh out 3.2647 g of dried AgN03 and dissolve in ASTM Type II water. Dilute
to 1 L (1 mL corresponds to 1 mg CN") .
4.11 Potassium chromate indicator solution. Dissolve 50 g K2CR04 in
sufficient ASTM Type II water. Add silver nitrate solution until a definite
red precipitate is formed. Let stand at least 12 hours, filter; and dilute to
1 L with ASTM Type II water.
4.12 Primary standard sodium chloride, 0.0141 N. Dissolve 824.1 mg NaCl
(NIST-dried 20 minutes at 104°C) in ASTM Type II water and dilute to 1 L.
4.13 Phosphate buffer solution, 1 M. Dissolve 138 g of NaH2PO«-H20 in 'ASTM
Type II water and dilute to 1 L. Filter before use and store at 4 ± 2°C.
IHC01.2 Page 205
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Method 335.63-CLP
Cyanide by Colorinmtric
4.14 Chloramine-T solution, 0.4% (w/v).
ASTM Type II water and dilute to 100 mL.
(Automated Colorimetric Method.)
Dissolve 0.4 g of chloramine-T in
Prepare fresh at time of analysis.
4.15 Chloramine-T solution, 12 (w/v). Dissolve 1.0 g of chloramine-T in 100
mL ASTM Type II water. Prepare fresh at time of analysis. (Manual
Colorimetric Method.)
4.16 Pyridine barbituric acid color reagent solution. Prepare this solution
in the hood. Transfer 15 g of barbituric acid into a 1 L Erlenmeyer flask.
Add about 100 mL of ASTM Type II water and swirl the flask to mix. Add 75 mL
of'pyridine and 15 mL of concentrated HC1 and mix until all of the barbituric
acid is dissolved. Dilute to 1 L with ASTM Type II water. Store at 4 ± 2°C.
5.
Sample Handling and Preservation
5.1 Exposure of sample to air may cause oxidation of samples.
5.2 If the cyanide sample is a liquid phase and also suspeuted of containing
oxidants, Na2S203 must be added to prevent further oxidation of the sample.
(See Standard Methods for the Examination of Water and Wastewater. 16th
Edition, 1985.)
5.3 Cyanide samples containing 1002 water miscible phase liquids with no
centrifugable solids will be pretreated with cadmium nitrate Cd(N03)2, and
centrifuged to remove soluble sulfides. Do not attempt to remove sulfides
from samples containing solids, as the centrifugation will remove sample.
Other phase types containing sulfides will be distilled using a two trap
system where the first trap contains a lead acetate solution (see Method
376.63-CLP) to trap the sulfide and the second trap contains sodium hydroxide
to trap the cyanide. (See Standard Methods for the Examination of Water and
Wastewater. 16th Edition, 1985).
6. Quality Control
6.1 Instrument Calibration
6.1.1 Summary
Prior to the analysis of samples and required QC, each CVAA system must be
initially calibrated to determine instrument sensitivity. ' ;
6.1.2 Frequency
Instruments must be calibrated daily or once every 24 hours and each time
the instrument is set up.
IHC01.2
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Me thod 33 5.6 3 - CLP Cyanide by Color imetrlc
6.1.3 Procedure
Calibration standards must be prepared using the same type of matrix and
at the same reagent concentration as the preparation blank following sample
preparation.
Calibrate according to instrument manufacturers recommended procedures
using at least two standards, one being a blank.
Before beginning the sample run, reanalyze the highest mixed calibration
standard as if it were a sample. ; .
6.1.4 Calculations ...
% Recovery = Found Concentration
7 True Concentration
6.1.5 Technical Acceptance Criteria
Recovery for the highest mixed calibration standard must within be ± 5
percent of the true value (i.e., 95-105%).
6.1.6 Corrective Action
Follow instrument manufacturers recommendations to correct the problem.
Also, 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 a CCV and a CCB, respectively.
6.1.7 Documentation
The instrument standardization date and time must be included in the raw
da'ca.
6.2 Initial Calibration Verification
6.2.1 Summary
Immediately after the GVAA system has 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) (ICV) at each
wavelength used for analysis.
6.2.2 Frequency
Each time the instrument is calibrated, the ICV must be run immediately
following the calibration, before any samples are analyzed.
IHC01.2 Page 207
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Method 335.63-CLP
Cyanide by Colorimetric
6.2.3 Procedure
If the ICV 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 linear 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.
6.2.4 Calculations
% Recovery
Found Concentration
True Concentration
6.2.5 Technical Acceptance Criteria
x 100
Recovery for the ICV must be within ±15 percent of the true value
(i.e., 85-115%). (See Table 3, Exhibit C)
6.2.6 Corrective Action
When recoveries of the ICV exceed the technical acceptance criteria, the
analysis must be terminated, the problem corrected, the instrument
recalibrated, and the calibration reverified.
6.2.7 Documentation
Report the ICV found concentration, true concentration, and percent
recovery on FORM II-HCIN.
6.3 Continuing Calibration Verification
6.3.1 Summary
To ensure calibration accuracy during an analysis run, a continuing
calibration verification solution (CCV) is analyzed and reported for every
wavelength used for the analysis of each analyte.
6.3.2 Frequency
The CCV is run at a frequency of 10 percent or every two hours during an
analysis run, whichever is more frequent.
The CCV is also run after the last analytical sample in the analysis
run.
6.3.3 Procedure
The same CCV must be used throughout the analysis runs for a Case of
samples received.
IHC01.2
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Method 33S.63-CT.P
Cyanide by Colorimetric
The analyte concentrations in the continuing calibration standard must
be one of the following solutions at or hear + 10 percent the mid-range levels
of the calibration curve:
EPA Solutions; or
A Contractor prepared standard solution.
Each CCV analyzed must reflect the conditions of analysis for all of the
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.
6.3.4 Calculations
% Recovery
Found Concentration
True Concentration
6.3.5 Technical Acceptance Criteria
x 100
Recovery for the CCV must be within ± 15 percent of the true value
(i.e., 85-115%).
6.3.6 Corrective Action
When recoveries of the CCV exceed the technical acceptance criteria, the
analysis must be stopped, the problem corrected, the instrument recalibrated,
the calibration reverified, and reanalyze the preceding 10 analytical samples
(or all analytical samples since the last "acceptable" CCV analyzed).
6.3.7 Documentation
Report the CCV found concentration, true concentration, and percent
recovery on FORM II-HCIR.
6.4 CRQL Standard
6.4.1 Summary
To verify linearity near the CRQL, the Contractor must analyze an CVAA
standard at two times the CRQL or two times the MDL, whichever is greater.
This standard must be run for every wavelength used for analysis.
IHC01.2
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Method 335.63-CLP
Cyanide by Colorimetric
6.4,2 Frequency
The CRQL standard must be run at the beginning and end of each sample
analysis run, or a minimum of twice per eight hours, whichever is more
frequent.
6,4.3 Procedure
The CRQL standard is not to be run before the ICV solution.
*-
6.4.4 Calculations
., r> Found Concentration , ,, '
X Recovery - z : * x 100
J True Concentration .
6.4.5 Technical Acceptance Criteria
The results of the CRQL standard must fall within the control limits +
20 percent of the true value for each wavelength used for analysis.
6.4.6 Corrective Action
If the CRQL standard does not fall within the control limit, the
analysis must be terminated and the problem corrected and the analytical
samples since the last acceptable CRQL standard must be reanalyzed.
6.4.7 Documentation
Report the CRQL standards found concentration, true concentration, and
percent recovery on FORM III-HCIN.
6.5 Initial Calibration Blank
6.5.1 Summary
To verify that the CVAA system is not contaminated, an initial
calibration blank (ICB) must be analyzed after calibration.
6.5.2 Frequency
The ICB must be analyzed each time the system is calibrated and
immediately after the ICV.
6.5.3 Procedure
If the absolute value of the ICB is greater than the MDL, the result
must be reported.
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Method 335.63-CLP ^___ Cyanide bv Colorimetric
6.5.4 Calculations
Not applicable. '
6.5.5 Technical Acceptance Criteria
The absolute value of the ICB must be less than the CRQL.
6.5.6 Corrective Action
When the ICB concentration does not meet the technical acceptance
criteria, terminate analysis, correct the problem, recalibrate, verify the
calibration, and reanalyze the ICB.-
6.5.7 Documentation
Report the ICB values in mg/L on FORM IV-HCIN.
6.6 Continuing Calibration Blanks
6.6.1 Summary
To ensure that the system is not contaminated during the analysis run,
continuing calibration blanks (CCB) are analyzed.
6.6.2 Frequency
Analyze the CCB at a frequency of 10 percent or every two hours,
whichever is more frequent.
Analyze the CCB after every CCV.
6.6.3 Procedure
A CCB must be run after the last CCV in the analysis run.
If the absolute value of the CCB is greater than the MDL, the result
must be reported.
6.6.4 Calculations
Not applicable.
6.6.5 Technical Acceptance Criteria
The absolute value of the CCB must be less than the CRQL.
IHC01.2 Page 211
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Method 335.63-CLP
Cyanide by Colorimetrlc
6.6.6 Corrective Action
When the CCB concentration does not meet the technical acceptance
criteria, terminate analysis, correct the problem, recalibrate, verify the
calibration, and reanalyze the preceding 10 analytical samples (or all
analytical samples since the last "acceptable" CCB analyzed).
6.6.7 Documentation
Report the CCB values in mg/L on FORM IV-HCIN.
6.7 Preparation Blanks
6.7.1 Summary
To ensure against contamination during sample preparation, a preparation
blank (PB) is analyzed.
6.7.2 Frequency
At least one PB, must be prepared and analyzed with every SDG, or with
each batch18 of samples digested, whichever is more frequent.
6.7.3 Procedure
The PB shall consist of ASTM Type II water processed through each sample
preparation and analysis procedure step (See Exhibit D, Section III).
The first batch of samples in an SDG is to be assigned to PB one, the
second batch of samples to PB two, etc.
6.7.4 Calculations
Not applicable.
6.7.5 Technical Acceptance Criteria
The absolute value of the PB must be less than the CRQL.
6.7.6 Corrective Action
If the absolute value of the concentration of the blank is less than or
equal to the CRQL, no correction of sample results is performed.
ia
A group of samples prepared at the same time.
IHC01.2
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Method 335.63-CLP
Cyanide by ColorImetrie
If any analyte concentration in the blank is above the CRQL, all
associated samples containing less than lOx the blank concentration must be
redigested and reanalyzed for that analyte. The sample concentration is not
to be corrected for the blank value.
If an analyte concentration in the blank is below the negative CRQL,
then all samples reported below lOx CRQL associated with the blank must' be
redigested and reanalyzed.
6.7.7 Documentation
The values for the PB must be recorded in mg/Kg on FORM IV-HCIN.
6.8 Spike Sample Analysis
6.8.1 Summary
To provide information about the effect of the sample matrix on the
distillation, a known amount of analyte is added (spiked) into a sample.
6.8.2 Frequency
At least one spike sample analysis must be performed on each group of
samples of a similar phases for each SDG19
If two analytical methods are used to obtain the reported values for the
same analyte within a SDG, then spike samples must be run by each method used.
6.8.3 Procedure
The spike is added before the sample preparation and prior to analysis.
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 spiked with a concentration equal to 30% of
the analytes linear range.
In the instance where there is more than one spike sample per phase per
method per SDG, if one spike sample recovery is not within contract criteria,
flag all the samples of the same matrix, level, and method in the SDG.-
19 EPA may require additional spike sample analysis upon special request by the
Project Officer, for which the Contractor will be paid.
IHC01.2
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Method 335.63-CLP
Cyanide by rolorimetric
6.8.4 Calculacions
% Recovery - (SS^SR) x 100
Where:
SSR -
SR -
SA -
SA
Spiked Sample Result;
Sample Result; and
Spike Added.
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 6.9, Duplicate
Sample Analysis). The average of the duplicate results cannot be used for the
purpose of determining percent recovery.
When sample concentration is less than the method detection limit, use
SR - 0 only for purposes of calculating percent recovery.
6.8.5 Technical Acceptance Criteria
Recovery for the analytical spike should be within ± 25 percent of the
spiked amount (i.e., 75-125%).
6.8.6 Corrective Action
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-
HCIN and VI-HCIN.
An exception to this rule is granted in situations where the sample
concentration exceeds the spike concentration by a factor of four or more.
such an event, the data shall be reported unflagged even if the percent
recovery does not meet the 75-125% recovery criteria.
In
When the digestion spike recovery falls outside the technical acceptance
criteria and the sample result does not exceed 4x the spike added, a
analytical spike must be performed. Spike the unspiked aliquot of the sample
at 2x the indigenous level or 2x CRQL, whichever is greater.
6.8.7 Documentation
Report the spiked sample results, sample results, spike added and
percent recovery for the spike sample analysis on FORM VI-HCIN.
The units for reporting spike sample results will be in mg/Kg.
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Method 335.63-CLP __ -_^_-: _ Cyanlde^by Color ime trie
6.9 Duplicate Sample Analysis
6.9.1 Summary
Duplicate aliquots of a sample are carried through the preparation and
analysis steps to provide information about the precision of the analytical
methods as well as matrix effects.
6.9,2 Frequency
At least one duplicate sample analysis must be performed on each group
of samples of a similar phase for each SDG.20
If two analytical methods are used to obtain the reported values for the
same metal within a SDG, Chen duplicate samples must be run by each method
used. '
6.9.3 Procedure
Samples identified as field blanks cannot be used for duplicate sample
analysis .
EPA may require that a specific sample be used for the duplicate sample
analysis.
In the instance where there is more than one duplicate sample per matrix
and concentration per method per SDG, if one duplicate result is not within
contract criteria, flag all the samples of Che same phase and method in the
SDG.
Duplicate sample analyses are required for calculations of relative
percent difference.
6.9.4 Calculations
RPD -
Where :
RPD - Relative Percent Difference;
S = First Sample Value (original); and
D = Second Sample Value (duplicate) .
Duplicates cannot be averaged for reporting on FORM I-HCIN.
20 EPA may require additional duplicate sample analysis upon special request by
the Project Officer for which the Contractor will be paid.
IHC01.2 Page 215
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Method 335.63-CLP
Cyanide by Colorimetrle
6.9.5 Technical Acceptance Criteria
A control limit of ± 20 percent for RPD shall be used for original and
duplicate sample values greater than or equal to 5x CRQL (Exhibit C). A
control limit of ± the CRQL must be used for sample values less than 5x CRQL.
If one result is above the 5x CRQL level and the other is below, use the
+ CRQL criteria.
If both sample values are less than the MDL, the RPD is not calculated.
Specific control limits for each element will be added to FORM IX-HCIN
at a later date based on precision results.
6.9.6 Corrective Action
If the duplicate sample results are outside the control limits, flag all
the data for samples received associated with that duplicate sample with an
asterisk "*".
6.9.7 Documentation
The results of the duplicate sample analyses must be reported on FORM
VIII-HCIN in mg/Kg.
The absolute value of the control limit (CRQL) must be entered in the
"CONTROL LIMIT" column on FORM VIII-HCIN.
6.10 Laboratory Control Samples 1
6.10.1 Summary
A LCS is digested and analyzed to ensure against analyte loss in the
sample preparation.
6.10.2
Frequency
One LCS must be prepared and analyzed for every group of samples in a
SDG, or for each batch of samples, whichever is more frequent.
6.10.3
Procedure
The LCS must be analyzed for each analyte using the same sample
preparations, analytical methods and QA/QC procedures employed for the EPA
samples received.
IHC0.1.2
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Method 335.63-CLP
Cyanide by Colorimetrie
The LCS raust.be obtained from EPA. (If unavailable, other EPA Quality
Assurance check samples or other certified materials may be used.)
6.10.4 Calculations
.. t, Found Concentration n _n
!. Recovery - ~ ~ : x 100
1 True Concentration
6.10.5 Technical Acceptance Criteria
Recovery for the LCS must be within ± 20 percent of the true value
(i.e., 80-120X).
6.10.6
Corrective Action
If the percent recovery for the LCS falls outside the technical
acceptance criteria, then the analyses must be terminated, the problem
corrected, and the samples associated with that LCS reprepared and reanalyzed.
6.10.7
Documentation
Report the LCS found concentration (in mg/Kg), true concentration (in
mg/Kg), and percent recovery on FORM IX-HCIN.
6.11 Method Detection Limits
f
6.11.1 Summary
The method detection limit (MDL) must be determined before any samples
are.analyzed for every instrument that will be used.
6.11.2
Frequency
MDLs must be determined within 30 days of the start of the contract and
at least quarterly (every three calendar months) until the end of the
contract.
6.11.3
Procedure
The MDL (in mg/L) shall be determined by multiplying by 3, the average
of the standard deviations (ffn^) obtained on three nonconsecutive days from
the consecutive analysis of seven different preparation blank dissolutions.
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). MDLs
must be determined and reported for each wavelength used in the analysis of
the samples.
The quarterly determined MDL for an instrument must always be used as
the MDL for that instrument during that quarter. If the instrument is
IHC01.2
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Method 335.63-CLP
Cyanide by Colorimetrlc
adjusted in anyway that may affect the MDL, the MDL for that instrument must
be redetermined and the results submitted for use as the established MDL for
that instrument for the remainder of the quarter.
MDLs must be determined in mg/L.
6.11.4 Calculations
MDL - <*_,) * 3
6.11.5 Technical Acceptance Criteria
The MDL1s must be able to meet the CRQL's established in Exhibit C.
6.11.6 Corrective Action
If an instrument's MDL cannot meet the CRQL for an analyte, that
instrument cannot be used to quantitate an analysis unless the analyte
concentration is greater than or equal to two times the reported MDL.
6.11.7 Documentation
MDLs must be reported for each instrument used on FORM XI-HCIN submitted
with each data package. If multiple instruments are used for the analysis of
an analyte within a SDG, the highest MDL for the analyte must be used for
reporting concentration values for that SDG.
7. Sample Preparation -
7.1 The procedure described here utilized a midi distillation apparatus (see
Figure 1 and requires a sample aliquot of one gram or less. Alternatively,
the distillation apparatus pictured in Figure 2 may be used along with the
procedure described for soils and sludges in the appendix to ASTM Method
D-2036, Volume 11.02, 1983.
7.2 Weigh 1.0 g of analytical sample to the nearest 0.01 g into the reaction
vessel and add 10 mL of 0.25 N NaOH and 0.5 mL MgCl2«6H20 solution to each
reaction vessel. For sample weights less than one gram, weigh the sample to
three significant figures. (It is recommended that the analyst pre-fit'the
distillation head to the reaction vessel prior to weighing the sample into the
reaction vessel since the glassware may vary in size.) .
7.3 Add 50 mL of 0.25 N NaOH to the receiving vessels and insert fritted
impingers.
7.4 Connect the apparatus as shown in Figure 1. The excess cyanide trap
contains 0.5 N NaOH.-
IHC01.2
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Method 335.63-CLP ... Cyanide by Colo^imetrlc
7.5 Turn on the vacuum and adjust the gang valves to give a flow of three
bubbles per second from the impingers in each reaction vessel. Seal all
fittings with ASTM Type II water.
7.6 After five minutes of vacuum flow, inject 1.0 mL of 50% (v/v) H2SO«
through the top part of the distillation head into the reaction vessel. After
addition of the H2SOtf the solution should become clear of the Mg(OH)2. If
not, sufficient acid may not have been added.
NOTE: Steps should be taken prior to distillation to assure that the
necessary acid volume is added to the sample to bring the sample/solution pH
to below 2.0.
7.7 Turn on the heating block and set for 123-125°C. Heat the solution to
boiling, taking care to prevent solution backup by periodic adjustment of the
vacuum flow rate. (Impinger may occasionally plug.)
7.8 After two hours of refluxing, turn off the heating block and continue
the vacuum for an additional 15 minutes.
7.9 Seal the receiving solutions and store them at 4 ± 2°C until analyzed.
The solutions will be stable for up to a week.
7.10 If the distillation fails to work properly due to formation of soaps,
liquid carryover, etc., steps must be taken to eliminate these problems.
Possible alternatives include use of a smaller sample aliquot or an additional
receiving vessel in train (all other alternatives must be approved by the
.Administrative or Technical Project Officer). In the latter, a receiving
vessel containing ASTM Type II water acidified to a pH less than 2.0 would be
inserted between the existing reaction and receiving vessels.
8. Calibration, Standardization, and Sample Analysis
8.1 Stock Cyanide Solution Standardization
8.1.1 Fill a 10 mL microburet with the 0.0192 N AgN03 solution.
8.1.2 Pipet'10.0 mL of ASTM Type II water into a well-washed Erlenmeyer
flask. Adjust the pH of the water to between 7.0 and 10.0 with NaOH or t^SOj,.
Add 1.0 niL of the K2CrOjj indicator solution. Titrate with the AgN03 to a
pinkish yellow end point. Be consistent in end point recognition. Record the
mL of titrant used. Titrate three blanks and average the volume of titrant
used; this is equal to A.
8.1.3 Titrate three individual 10.0 mL aliquots of the standard 0.0141 N
NaCl solution in the same manner as the blanks. Average the mL of titrant
used; this is equal to B.
IHC01.2 Page 219
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Method 335.63-CLP
Cyanide by Colorimetric
8.1,4 Calculate the exact normality of the AgN03 solution:
me NaCl raL
N
(B - A)raL
0.0141 N
8.1.5 Add 10.0 mL of ASTM Type II water to a well -washed Erleruneyer flask.
Add 100 mL of 0.1 N NaOH and 0.5 mL of the rhodanine indicator solution.
Titrate with the standard AgN03 titrant to the first change in color from a
canary yellow to a salmon hue. Record the volume of titrant used. Titrate
three blanks and calculate the average volume of titrant used (this is equal
to'C).
8.1.. 6 Titrate three individual 10.0 mL aliquots of the stock cyanide
solution in the same manner as the blanks. Calculate the average volume of
titrant used (this is equal to D) .
8.1.7 Calculate the concentration of cyanide in the stock solution:
1000 mL
mg/L
(D~C)(N.AgN03) 2eq CJT 26 mg CW
x - x
mL stock CN"
leq Ag+
Meq
8.2 Automated Colorimetric Calibration and Analysis
8.2.1 Prepare standard cyanide solutions according to the table in 8.3.3.
8.2.2 Operating conditions: Because of the difference between various makes
and models of satisfactory instruments, no detailed operating instructions can
be provided. The analyst should follow the instructions provided by the
manufacturer of the particular instrument. It is the responsibility of the
analyst to verify that the instrument configuration and operating conditions
used satisfy the analytical requirements and to maintain quality control data
confirming instrument performance and analytical results,
8.2.3 The following general procedure applies to the automated method for
cyanide: Set up the manifold and complete system as per manufacturer's
instructions. Let the colorimeter and recorder warm up for at least 30
minutes. Establish a- steady reagent baseline feeding ASTM Type II water
through the sample line and the appropriate reagents through the reagent
lines. Adjust the baseline using the appropriate control on the colorimeter.
8.2.4 Aspirate the highest calibration standard and adjust the colorimeter
until the desired single-range is obtained.
8.2.5 Place calibration standards, blanks, and control standards in the
sampler tray, followed by distilled samples, distilled duplicates and all
distilled QC audit samples.
IHC01.2
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Method 135.63-CLP
Cyanide by Colorimeeric
8.2.6 Switch sample line from the ASTM Type II water to sampler, set the
appropriate sample rate and begin analysis.
8.3 Manual Colorimetrie Calibration and Analysis
8.3.1 Turn on the spectrophotometer and allow appropriate warm-up time.
8.3.2 Using an opaque object, block the light path -in the spectrophotometer
and set the absorbance to full scale (zero transmittance). Set the absorbance
to zero by placing a calibration blank (see below) in the light path. Do not
repeat the zeroing with the blank prior to each sample analysis.
8.3.3 Prepare a set of standards in 50 mL volumetric flasks using the
following protocol:.
Total fig CN" /
standard solution
0.00
0.20
0.50
00
00
5.00
mL 10 mg/L CN~
0.000
0.020 .
- 0.-050
0.100
0.200
, 0.500
mL 0.05 N NaOH*
20
20
20
20
20
20
* Addition of 20 mL NaOH to each sample will, result in a 2.5% difference
in NaOH concentration between the blank and the highest CN' standard.
This should not appreciably affect standard calibration.
8.3.4 Add 4 mL phosphate buffer to each of the standard solutions prepared
above and mix.
8.3.5 Using the Time Table for Manual Color Development found below, add the
following reagents to each solution in the order given: 2.0 mL chloramine-T
solution, swirl to mix; after 15 seconds add 5.0 mL pyridine barbituric acid
solution, swirl gently to mix; dilute calibration standard to 50 mL using ASTM
Type II water after four minutes.
8.3.6 Measure absorbance or transmittance of calibration standards.
IHC01.2
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Method 335.63-CLP
Cyanide by Colorimetrie
Sample
No,
i
2
3
' 4
5
6
Time Table for Manual Color Development
(Time is in minutes:seconds)
Absorbance
Chlor-T Pvridine Dilution Reading
0:00
0:45
1:30
2:15
3:
0:15
00
00
45
30
15
3:45
4:00
4:15
5:00
5:45
6:30
7:15
8:00
13:00
13:45
14:30
15:15
16:00
16:45
8.3.7 Repeat sections 8.3.4-8.3.5 using 4 mL of sample from the receiving
vessel solution diluted to 20 mL total volume with ASTM Type II water (in
place of the standard solutions). A blank and one of the mid-range standards
will be developed and analyzed with each manual color development of sample
solutions. If any sample solution absorbance reads above the highest
calibration standard, repeat the color development using in appropriate volume
of sample receiving solution to bring the absorbance value below the highest
calibration standard. Be sure to keep salt content constant .in the
development solutions. The mid-range standards will serve as the calibration
stability standard.
9.
Calculations
9.1 Calculations for Automated Colorimetric Determination
9.1.1 Perform a linear regression analysis of the calibration standards
values (/ig/mL) (x) versus absorbance values (y) to determine the correlation.
If the correlation coefficient is less than 0.995, then the calibration curve
analysis should be repeated using new standards if necessary.
9.1,2 Using the regression analysis equation, calculate sample receiving
solution concentrations (as ^g/mL) from the calibration curve.
9.1.3 Calculate Mg/g. CN~, for the samples using the following equation:
(A) (B)-(C)
Mg/g, ON' -
sample wt. in g
'Where:
A /zg/mL from regression analysis;
B - Sample receiving solution volume (mL); and
C - Dilution factor necessary to bracket sample value within
standard values.
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Method 335.63-CLP Cyanide by Colorimetric
9.1.4 Report all sample values greater than the required reporting limit
except as noted in Exhibit E.
9.2 Calculations for Manual Colorimetric Determination
9.2.1 Perform a linear regression analysis of the calibration standard
values (total fig CN" per 50 mL standard volume) (x) versus the absorbance
values (y) to determine correlation. If the correlation coefficient is less
than 0.995, then the calibration curve should be rerun using new standards if
necessary.
9.2.2 Using the regression analysis, calculate sample concentration (total
Mg CN" per 50 mL developed solution) from the calibration curve.
9.2.3 Calculate Mg/g CN~ in the sample using the following equation:
(total Mg CN') x 50 (mL)
Mg/g
10. Documentation
sample wt. (g) x receiving solution volume
; used for color development (mL)
10.1 Report sample results in mg/Kg on FORM I-HCIN. NOTE: Mg/g is
proportional to mg/Kg.
11. Glassware Cleaning for Cyanide Distillations
11.1 Cyanide quantitative determinations require the use of non-disposable
glassware that must be cleaned prior to reuse. Since the levels of cyanide in
individual samples may vary significantly, all glassware should be treated on
a worst-case basis. The following protocol will be used:
11.1.1 Prior to removal from the hood, all glassware will be washed with
soapy water followed by a water rinse. Any sample that remains on glassware
at this stage should be removed with the use of organic solvents followed by a
soapy water, water rinsing. It is important to remember that at this stage
the glassware may be "visually clean" but still may present potential health
hazards.
11.1.2 At this point the glassware should be transferred in the hood to a
bath consisting of 75 mL/gallon microwash (or equivalent ammonia containing
cleaner). The glassware can now be removed from the hood and the glassware
either soaked in microwash for two hours or hand scrubbed using the microwash
solution.
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Method 335.63-CLP
Cyanide by Colorimetrie
11.1.3 after appropriate rinsing to remove detergent, the glassware will
be soaked in 25X HN03 for one hour or thoroughly rinsed with 50% HN03. Rinse
all glassware with sufficient ASTM Type II water and then distilled water to
remove all traces of acid.
11.1.4 Air dry the glassware or use an inert absorbent towel if the
glassware is needed quickly.
11.1.5 Fritted glass impingers may be difficult to rinse. Rinsing may be
aided by the use of compressed gas to blow out residual liquids.
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Method 335.63-CLP
Cyanide bv Colprimetrie
Figure 1
CYANIDE DISTILLATION APPARATUS (MIDI)
Heating Block
gang valve excess Cyanide if ap
A. Micracondansflr
8 Distillation Head
C iffloingir Tubi (30ml)
(fieacitot Vessel)
0 Fritted Glass Impinger
E * imoingef Tuba (70 ml)
(Hsceiving Vessel)
IHCOI:2
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Method 335.63-CLP
Cyanide bv Colori
Figure 2
CYANIDE DISTILLATION APPARATUS (ASTM Method D2036)
COOLING WATER
INLET
SCREW CLAMP
TO LOW VACUUM
SOURCE
- ABSORBER
" DISTILLINfi FLASK
HEATER -
O
J! 'lHCOl.2
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EXHIBIT E
QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
IHC01.2
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EXHIBIT E
QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
SECTION I - GENERAL QA/QC PRACTICES
SECTION II - SPECIFIC QA/QC PROCEDURES
SECTION III - LABORATORY EVALUATION PROCESS
Page
229
230
253
IHC01.2
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SECTION I
GENERAL QA/QC PRACTICES
The Contractor shall adhere to standard laboratory practices for
laboratory cleanliness as applied to glassware and apparatus. The Contractor
shall also adhere to laboratory practices with regard to reagents, solvents,
and gases. 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.
IHC01.2
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SECTION II
SPECIFIC QA/QC PROCEDURES
The quality assurance/quality control (QA/QC) procedures defined herein
shall 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 shall also follow these procedures.
NOTE: The cost of performing all QA/QC procedures specified in this Statement
of Work shall be 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 in samples, documentation of
methods and their performance, and verification of the sample data generated.
The program will also assist laboratory personnel in recalling and defending
their actions under cross-examination if required to present court testimony
in enforcement case litigation.
The primary function of the QA/QC program is the definition of
procedures for the evaluation and documentation of sampling and analytical
methodologies, and the reduction and reporting of data. The objective is to
provide a uniform basis for sample handling, sample analysis, 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 the 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 following QA/QC operations shall be performed as described in this
exhibit:
Instrument Calibration
Initial Calibration Verification (ICV) and Continuing Calibration
Verification (CCV)
CRQL Standards for ICP and HYICP (CRI)
Linear Range Standard (LRS) Analyses
Initial Calibration Blank (ICB), Continuing Calibration-Blank (CCB), and
Preparation Blank (PB) Analyses
ICP Interference Check Sample (ICS) Analyses
Spike Sample Analysis (S)
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Specific QA/QC Procedures
Exhibit E
Analytical Spike Sample Analysis (AS)
Duplicate Sample Analysis (D)
Laboratory Control Sample (LCS) Analysis
Method Detection Limit (MDL) Determination
Interelement Corrections for ICP (ICP)
Hydride ICP (HYICP) QC Analysis
The Contractor is required to participate in the Laboratory Audit and
Intercomparison Study Program run by EPA EMSL-LV. The Contractor can expect
to analyze a preaward performance evaluation (PPE) sample before contract
startup and a performance evaluation sample (PES) with every SDG.
As specified in Exhibit B, the Contractor shall perform Quarterly
Verification of Method Detection Limits (MDL) by the method specified in
Exhibit D for the type and model of each instrument used on this contract, and
shall submit results to SMO and EMSL-LV. All the MDLs shall meet the CRQLs
specified in Exhibit C. For ICP methods, the Contractor shall also report, as
specified in Exhibits B and D, linear range verification, all interelement
correction factors, wavelengths used, and integration times.
In this Exhibit, as well as other places within this SOW, 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, not only do analytical samples
include each of the phases of a field sample, including PE samples received
from an external source, but also all required QA/QC samples (matrix spikes,
analytical/post-digestion spikes, duplicates, LCS, ICS, CRQL standards,
preparation blanks and linear range standards) 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 blanks and calibration verification samples are not counted
as analytical samples when determining 10Z 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 must be repeated after taking the appropriate corrective action as
specified in Exhibits D and E.
All QC measurements must be taken under the same conditions used to
obtain sample measurements (i.e., if a continuing calibration verification is
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Specific QA/QC Procedures
Exhibit E
preceded or followed by a rinse, the sample analyzed must be preceded or
followed by an equivalent rinse).
The Contractor must report all QC data in the exact format specified in
Exhibits B and H.
The Contractor shall establish a QA program with the.'objective of
providing sound analytical chemical measurements. This program shall
incorporate QC procedures, any necessary corrective action taken, all
documentation required during data collection, and the quality assessment
measures performed by management to ensure acceptable data production.
As evidence of such a program, the Contractor shall prepare a written
Quality Assurance Plan (QAP) which describes the procedures that are
implemented to achieve the following:
Maintain data integrity, validity, and useability;
Ensure that analytical measurement systems are maintained in an
acceptable state of stability and reproducibility;
* Detect problems through data assessment and establish corrective action
procedures which keep the analytical process reliable; and
* Document all aspects of the measurement process in order to. provide data
which are technically sound and legally defensible.
The QAP must present, in specific terms, the policies, organization,
objectives, functional guidelines, and specific QA/QC activities designed to
achieve the data quality requirements in this contract. Where applicable,
SOPs pertaining to each element shall be included or referenced as part of the
QAP. The QAP must be available during on-site laboratory evaluation and upon
written request,by the APO.
The elements of QAP are as follows:
Organization and Personnel
QA Policy and objectives;
QA Management;
a. Organization
b. Assignment of QC/QA responsibilities
c. QA document control procedures
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Specific QA/QC Procedures
Exhibit E
d. Reporting relationships
e. QA program assessment procedures
Personnel
a. Resumes
b. Education and experience pertinent to this contract
c. Training progress
Facilities and equipment;
t " -
Instrumentation and backup alternatives
Maintenance activities and schedules
Document Control; ! -
Laboratory notebook policy;
Samples tracking/custody procedures;
Case file organization,' preparation, and review procedures;
» Procedures for preparation, approval, review, revision, and
distribution of SOPs; and
Process for revision of technical 'or documentation procedures.
Analytical methodology;
Calibration procedures and frequency;
Sample preparation/extraction procedures;
Sample analysis procedures;
Standards preparation procedures; and
Decision processes, procedures, and responsibility for initiation of
corrective action.
Data Generation
Data collection procedures;
IHC01.2
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Specific OA/OC Procedures Exhibit _E
Data reduction procedures;
Data validation procedures; and
Data reporting and authorization procedures.
Quality Assurance;
Data QA;
Systems/internal audits;
Performance/external audits;
Corrective action procedures;
QA reporting procedures; and
Responsibility designation.
Data Validation/Self-Inspection Procedures;
Data flov and chain-of-command for data review;
Procedures for measuring precision and accuracy;
Evaluation parameters for identifying systematic errors;
Procedures to assure that hardcopy data are complete and compliant
with the requirements in Exhibit B;
Demonstration of internal QA inspection procedure (demonstrated by
supervisory sign-off on personal notebooks, internal PE samples,
etc.); .
Frequency and type of internal audits (e.g., random, quarterly, spot
checks, perceived trouble areas);
Demonstration of problem identification, corrective actions taken,
resumption of analytical processing resulting from an internal audit
(i.e., QA feedback); and
Documentation of audit reports (internal and external), response,
corrective action, etc.
Data Handling; and
Data Management
IHC01.2 Page 234
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Specific QA/OC Procedures
Exhibit E
a. Data management procedures are written procedures that are
clearly defined for all databases and files used to generate or
re-submit deliverables specifying the acquisition or entry,
update, correction, deletion, storage, and security of computer
readable data and files. Key areas of concern include: system
organization including personnel and security, documentation,
operations, traceability, and QC.
1. Data manually entered from hardcopy must be quality
controlled and error rates estimated;
2. System should prevent entry of incorrect or out-of-range
data and alert data entry personnel of errors;
3. Data entry error rates must be estimated and recorded on a
monthly basis by re-entering a statistical sample of the
data entered and calculating discrepancy rates by data
element;
4. Record of changes in the form of corrections and updates to
data originally generated, submitted, and/or re-submitted
must be documented to allow traceability of updates.
Documentation must include the following information for
each change:
4.1 Justification or rationale for the change;
4.2 Initials of the person making the change or changes.
(Data changes must be implemented and reviewed by a
person or group independent of the source generating
the deliverable);
4.3 Change documentation must be retained according to the
schedule of the original deliverable;
4.4 Resubmitted deliverables must be re-inspected as a
part of the laboratory's internal inspection process
prior to submission. The entire deliverable and not
just the changes must be re-inspected;
4.5 The laboratory manager must approve changes to
originally submitted deliverables;
4.6 Documentation of data changes may be requested by
laboratory auditors;
IHC01.2
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Specific OA/QC Procedures
Exhibit E
4.7 Life cycle management procedures must be applied to
computer systems used to generate and edit contract
deliverables. Such systems must be thoroughly tested
and documented prior to utilization;
4.8 A software test and acceptance plan including test
requirements, test results, and acceptance criteria
must be developed, followed, and available in written
form;
4.9 System changes must not be made directly to production
systems generating deliverables. Changes must be made
first to a development system and tested prior to
implementation;
4.10 Each version of the production system will be given an
identification number, date of installation, date of
last operation, and archived;
4.11 System and operations documentation must be developed
and maintained for each system. Documentation must
include a user's manual and an operations and
maintenance manual.
Individual(s) responsible for the following documentation must be
identified:
a. System operation and maintenance including documentation and
training;
b. Databa'se integrity including data entry, data updating and QC;
and
c. Data and system security, backup, and archiving.
Quality Control.
Solvent, reagent and adsorbent check analysis;
Reference material analysis;
Internal QC checks;
Corrective action and determination of QC limit procedures; and
Responsibility designation.
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Specific OA/QC Procedures
Exhibit E
1.
Instrument Calibration
1.1 Guidelines for instrumental calibration are given in EPA 600/4-79-020
and/or Exhibit D. 'Instruments shall be calibrated daily or once every 24
hours and each time the instrument is set up. The instrument standardization
date and time shall be included in the raw data.
1.2 The calibration standards must be prepared using the same type of matrix
and at the same concentration as the preparation blank following sample
preparation. The Contractor shall aspirate or inject the calibration
solutions as described in the individual methods (see Exhibit D) and record
the readings.
1.3 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 a CCV and a CCB. For cyanide and mercury, follow the calibration
procedures outlined in Exhibit D. One cyanide calibration standard must be at
the CRQL. For ICP systems, calibrate the instrument according to instrument
manufacturer's recommended procedures. At least one blank and one standard
must be used for ICP and HYICP systems.
2.
Initial Calibration Verification and Continuing Calibration Verification
2.1 Initial Calibration Verification
2.1.1 Immediately after each of the ICP, HYICP, GFAA, CVAA, 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 (ICV) solution(s) at each wavelength used for
analysis. When measurements exceed the control limits of Table 3-Initial and
Continuing Calibration Verification (CCV) Control Limits for Inorganic
Analyses (see Exhibit C), the analysis must be terminated, the problem
corrected, the instrument recalibrated, and the calibration reverified.
2.1.2 If the ICV 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.
2.1.3 For ICP, the ICV solution(s) must be run at each wavelength used for
analysis. For cyanide, the initial calibration verification standard must be
distilled with the batch of samples analyzed in association with that ICV
because it serves as a Laboratory Control Sample (LCS). This means that an
IHC01.2.
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Specific OA/QC Procedures
Exhibit E
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 calibration verification shall be recorded on FORM II-HCIN for
ICP, HYICP, GFAA, CVAA, and cyanide analyses, as indicated.
2.2 Continuing Calibration Verification
2.2.1 To ensure calibration accuracy during each analysis run, one of the
following standards is to be used for CCV and must be analyzed and reported
for every wavelength .used for the analysis of each analyte, at a frequency of
10 percent or every 2 hours during an analysis run, whichever is more
frequent. The standard must also be analyzed 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 ± 10 percent of the mid-range levels of
the calibration curve: . . .
EPA solutions; or
A Contractor-prepared standard solution.
2.2.2 The same continuing calibration standard must be used throughout the
analysis runs for a Case of samples received.
2.2.3 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 apply 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 analyses 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.
2.2.4 If the deviation of the continuing calibration verification is greater
than the control limits specified in Table 3 in,Exhibit C, the analysis must
be terminated, the problem corrected, and the CCV reanalyzed. If the
reanalysis yields a CCV value within control limits, then the preceding 10
analytical samples or all analytical samples analyzed since the last
acceptable calibration verification must be analyzed for the analytes
affected. Otherwise, the instrument must be recalibrated, the calibration
verified, and the affected analytical samples rerun. Each analytical sample
must be bracketed by two consecutive CCVs that have been analyzed within two
hours of each other with no more than 10 analytical samples run in between.
In addition, the value for each analyte in those two CCVs must meet the
control limits. Information regarding the continuing verification of
calibration shall be recorded on FORM II-HCIN in Exhibit B for ICP, HYICP,
GFAA, CVAA, and cyanide, as indicated.
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Specific QA/QC Procedures
Exhibit E
3.
CRQL Standards
3.1. To verify linearity near the CRQL 'for ICP, HYICP, GFAA, mercury, and
cyanide analysis, the Contractor must analyze an CRQL standard at two times
the CRQL or two times the MDL, 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 ICV. This standard must be run for
every wavelength used for analysis.
3,2 Results for the analysis of the CRQL standard" must be within ± 15%
(except cyanide at ± 20% and mercury at ± 25%) of the true value for each
wavelength used for analysis. If not, the'analysis must be terminated, the
problem corrected, and the analytical samples since the last acceptable CRI
reanalyzed. - '
3.3 The Contractor must analyze and report these standards on FORM III-HCIN
in Exhibit B for each method.
4.
Linear Ranee Standard Analysis '
4.1 For ICP, HYICP, CVAA, mercury, and cyanide analysis, a linear range
verification check standard (LRS) must be analyzed 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 ICV. This standard must be run for
every wavelength used for analysis.
4.2 -Results for the analysis of the LRS must be within ±10% of the true
value for each 'wavelength used for analysis. If not, the analysis must be
terminated and successive dilutions of the standard must be reanalyzed until
the control limits are met. The concentration of this standard that meets the
control limits is the upper limit of the instrument linear range beyond which
results cannot be reported under this contract without dilution of the
analytical sample.
4.3 The Contractor must analyze and report these standards on FORM III-HCIN
in Exhibit B for each method.
5. Initial Calibration Blank.
Blank Analyses
Continuing Calibration Blank, and Preparation
5.1 Initial Calibration Blank (ICB) and Continuing Calibration Blank (CCB)
Analyses
5.1.1 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 percent or every 2 hours during the run,
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Specific QA/QC Procedures ^ Exhibit E
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 and after the last analytical
sample of the run.
5.1.2 The results for the calibration blanks shall be recorded on FORM
IV-HCIN for ICP, HYICP, GFAA, CVAA, and cyanide analyses, as indicated. If
the absolute value of the calibration blank result exceeds the method
detection limit, the result must be reported in mg/L on FORM IV-HCIN. If the
absolute value blank result exceeds the CRQL (Exhibit C), analysis must be
terminated, the problem corrected, and the CCB reanalyzed. If the, reanalysis
yields a CCB with an absolute value below the CRQL, then all analytical
samples analyzed since the last acceptable calibration blank must be
reanalyzed. Otherwise, the instrument must be recalibrated, -the calibration
verified, and the affected analytical' sample(s) rerun.
5.1.3 Each analytical sample must be bracketed by two consecutive CCBs that
have been analyzed within two hours of each other with no more than 10
analytical samples run in between, and the absolute value for each analyte in
these two CCBs must fall below the CRQL or MDL whichever is greater.
5.1.4 The flush time between any of the samples in a QC set cannot be less
than the flush time between the last sample and the final CCB of that same
set.
5.2 Preparation Blank (PB) Analysis
5.2.1 For each sample phase, at least one PB (or reagent blank), as
described in the potassium hydroxide fusion procedure (Exhibit D, Section V,
paragraph 2.4) must be prepared and analyzed with every SDG, or with each
batch of samples digested, whichever is more frequent.
.5.2.2 The first batch of samples in an SDG shall to be assigned to
preparation blank one, the second batch of samples to preparation blank two,
etc. (see FORM IV-HCIN). Each data.package must contain the results of all
the .preparation blank analyses associated with the samples in that SDG.
5.2.3-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:
If the absolute value of the concentration of the blank is less than or
equal to the Contract Required Quantitation Limit (Exhibit C), no
correction of sample results is performed.
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Specific QA/QC Procedures
Exhibit E
6.
If any analyte concentration in .the blank is above the CRQL, all
associated samples containing less than lOx the blank concentration must
be redigested and reanalyzed for that analyte. The sample concentration
is not to be corrected for the blank value.
If an analyte concentration in the blank is below the negative CRQL, all
samples with a reported analyte value below lOx CRQL and associated with
the blank must be redigested and reanalyzed.
The values for the preparation blank must be recorded in mg/Kg on FORM
IV-HCIN for ICP, HYICP, GFAA, CVAA, and cyanide analyses.
ICP Interference Check Samples (ICS) Analysis
6.1 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.
6.2 The Interference Check Samples consist of two solutions: Solution A and
Solution AB. Solution A contains potential interferants, and Solution AB
contains both analytes and interferants. An ICS analysis consists of
analyzing both solutions consecutively (starting with Solution A) for all
wavelengths used for each analyte reported by ICP.
6.3 Results for the ICP analyses of Solution AB during the analytical runs
must be within ± 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 acceptable 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).
6.4 If the ICP Interference Check Sample (ICS) is not available from EPA,
independent ICP Check Samples must be prepared with interferant and analyte
concentrations at the levels specified in Table 2-Interferant and Analyte
Elemental Concentrations used for ICP ICS (see Exhibit C). 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 V-HCIN.
IHC01.2
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Specifjc QA/QC Procedures
Exhibit E
Results muse be within ± 20 percent of the established mean value. The mean
and standard deviation must be reported in the raw data. Results from the ICS
analyses must be recorded on FORM V-HCIN for all ICP parameters.
7.
Spike Sample Analysis
7.1 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 sample preparation (i.e., prior to fusion, digestion
or distillation). At least one spike sample analysis must be performed on
each group of samples of similar phases for each SDG.21
7.2 The spike sample is prepared by adding 0.0125 g of the solid spiking
mixture to a 0.25 g aliquot of sample which is then carried through the sample
preparation procedure.
7.3 If the spike analysis is performed on the same sample that is chosen for
the duplicate sample analysis, spike calculations must be performed usiug the
results of the sample designated as the "original sample" (see 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.
7.4 If two analytical methods are used to obtain the reported values for the
same metal within a SDG (i.e., ICP, HYICP), spike samples must be run by each
method used.
7.5 If the spike recovery is not within the limits of 75-125Z, the data for
all of the samples received associated with that spike sample and determined
by the same analytical method must be flagged with the letter "N" on FORMs
I-HCIN and VI-HCIN. An exception to this rule is granted in situations where
the sample concentration exceeds the spike .concentration by a factor of four
or more. In such an event, the data shall be reported unflagged even if the
percent recovery does not meet the 75-1252 recovery criteria.
7.6 " In the instance where there is more than one spike sample per phase per
method per SDG, if one spike sample recovery is not within contract criteria,
flag all the samples of the same matrix, level, and method in the SDG.
7.7 Individual component percent recoveries (XR) are calculated as follows:
21EPA may require additional spike sample analysis upon special request by the
Project Officer, for which the Contractor will be paid.
IHC01.2
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Specific QA/OC Procedures
Exhibit E
R =
(SSR -SR )
SA
x 100
Where: '
SSR - Spiked Sample Result;
SR - Sample Result; and
SA - Spike Added.
7.8 When the sample concentration is less than the method detection limit,
use SR - 0 only for purposes of calculating % Recovery. The spike sample
results, sample results and X Recovery (positive or negative) must be reported
on FORM VI-HCIN for ICP, HYICP, GFAA, mercury,'and cyanide analyses, as
indicated.
8.
Analytical Soike Sample Analysis
8.1 The analytical spike sample analysis is designed to provide information
about the effect of the sample matrix on the measurement system. The spike is
added after the sample-has been prepared and prior to analysis. For ICP, AA,
and cyanide, at least one spike sample analysis must be performed on each
group of samples of a similar phase for each SDG.22
8.2 If the analytical 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
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 spike sample analysis. EPA may require that a
specific sample be used for the spike sample analysis.
8.3 The analytical spike sample analysis must be performed on a sample
containing measurable amounts of the analyte or at least a representative
sample of the phases associated with it.
8.4 For the analytical spike sample analysis, each analyte must be spiked
with a concentration equal to 30% of the analyte's linear range for HYICP and
2x the CRQL for GFAA. The sample and spike sample must be at the same
dilution.
i
8.5 If the spike recovery is not within the limits of 85%-115%, a second
analytical spike must be performed. If the second analytical spike is out of
control then the preparation blank must be spiked with the same spiking
22EPA may require additional spike sample analysis upon special request by the
Project Officer, for which the Contractor will be paid.
IHC01.2
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Specific QA/OC Procedures
Exhibit E
solution. If spiking che blank yields a recovery that is out of control, the
spiking solution must be reprepared and the previous spiking procedure
repeated. If not, flag all samples received associated with that spike sample
and determined by the same analytical method flagged with the letter "E" on
FORMs I-HCIN and VII-HCIN (see Figure 3). The percent recovery is calculated
in the same manner as that used for the matrix spike percent recovery
calculation.
8.6 The spike sample results, sample results, spiking level and % Recovery
(positive, negative or zero) must be reported on FORM VII-HCIN for ICP, HYICP,
GFAA, mercury, and cyanide analysis.
9.
Duplicate Sample Analysis
9.1 One duplicate sample must be analyzed from each group of samples of a
similar phase for each SDG.23 Duplicates cannot be averaged for reporting on
FORM I-HCIN.
9.2 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., HYICP and GFAA),
duplicate samples must be run by each method used.
9.3 The relative percent differences (RPD) for each component are calculated
as follows:
RPD -
|S - D|
(S + D)/2
x 100
Where:
RPD
S
D
Relative Percent Difference;
First Sample Value (original); and
Second Sample Value (duplicate)
9.4 The results of the duplicate sample analyses must be reported on FORM
VIII-HCIN in mg/Kg. A control limit of ± 202 for RPD shall be used for
original and duplicate sample values greater than or equal to 5x CRQL (Exhibit
C). A control limit of ± the CRQL must be used for sample values less than 5x
CRQL, and the absolute value of the control limit (CRQL) must be entered in
the "CONTROL LIMIT" column on FORM VIII-HCIN..
23EPA may require additional duplicate sample analyses upon special request by
the Project Officer, for which the Contractor will be paid.
IHC01.2 Page 244
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Specific QA/QC Procedures
Exhibit E
' FIGURE 3
Analytical Spike Analysis Scheme
Spike Sample at 30%
the Linear Range
Analyses within
Calibration Range
YES
Spike Recovery
Greater Than 85% and
Less than 115%
NO
Spike and Analyze a
Second Analytical Sample
Spike Recovery
Greater Than 85% and
Less than 115%
NO
Spike and Analyze
the Preparation Blank
Spike Recovery
Greater Than 85% and
Less than 115%
NO
Reprepare the
Spiking Solution
NO
YES
YES
YES
Dilute Sample
Report Data
Report Data
Report Data
with an "E" Flag
IHC01.2
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Specific QA/QC Procedures Exhibit E
9.5 If one result is above the 5x CRQL level and the other is below, use the
± CRQL criteria. If both sample values are less than the MDL, the RPD is not
reported on FORM VIII-HCIN.
9.6 If the duplicate sample results are outside the control limits, flag all
the data for samples received associated with that duplicate sample with an
asterisk "*" on FORMs I-HCIN and VIII-HCIN. 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 phase 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 VIII-HCIN at a later date based on these
precision results.
10. Laboratory Control Sample Analysis
10.1 The Laboratory Control Sample (LCS) must be analyzed for each analyte
using the same sample preparation, analytical methods and QA/^C procedures
employed for the EFA samples received.
10.2 The EPA-provided LCS must be prepared and analyzed using each of the
procedures applied to the samples received. If the EPA LCS is unavailable,
other EFA Quality Assurance check samples or other certified materials may be
used. One LCS must be prepared and analyzed for every group of samples in a
SDG, or for each batch of samples prepared, whichever is more frequent.
10.3 All LCS results, control limits and percent recovery (ZR) shall be
reported on FORM IX-HCIN.
10.4 If the results of the LCS are not within the control limits established
by EPA, the analyses must be terminated, the problem corrected, and the
samples associated with that LCS reprepared and reanalyzed.
11. Performance Evaluation Sample (FES')
11.1 The Performance Evaluation Sample (PES) will assist the Agency in
monitoring contractor performance. The laboratory will not be informed in
advance of the analytes in the PES or their concentration.
11.2 The Contractor must prepare, analyze and report the results of the PES,
one per each SDG, if available.
11.3 The laboratory will receive the PES in ampules or as full volume samples
from the Agency. The ampules will come with instructions concerning the
preparation procedure required for the PES. The Contractor will use the
ampules in increasing 'alphanumeric order.
11.4 Prepare the PES using the procedure described in the sample preparation
section (Exhibit D) of this Statement of Work, and analyze the PES using the
IHC01.2 Page 246
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Specific QA/QC Procedures
Eyhlblt E
methods described in Exhibit D for the analysis of EPA field samples.
contract required QC must also be met.
All
11.5 In addition to PES preparation and analysis, the Contractor will be
responsible for correctly identifying and quantifying the analytes included in
the PES. The Agency will notify the Contractor of unacceptable performance.
NOTE: Unacceptable performance for identification and quantification of
analytes in the PES is defined as a score of less than 75 percent.
11.6 The Contractor must demonstrate acceptable performance for analyte
identification and quantification. If the Contractor achieves a score of less
than 75 percent, the Agency may take, but is not limited to, the following
actions: Show Cause and/or Cure Notice, reduction of the number of samples
shipped to the laboratory, suspension of sample shipment, a site visit, a full
data audit, and/or require the laboratory to analyze a remedial PES.
11.7 The analysis results for the PES must be recorded on FORM I-HCIN for all
analytes, as indicated in Exhibit B, Section IV.
12. Method Detection Limit (MDL) Determination
12.1 The Method Detection Limits (MDLs) (in mg/L) must be determined for each
instrument used, within 30 days prior to and before the start of any contract
analyses and at least quarterly (every 3 calendar months). The MDL must meet
the CRQLs specified in Exhibit C.
12.2 The MDLs (in mg/L) are determined by multiplying by 3, the average of
the standard deviations (c7n.t) obtained on three nonconsecutive days from the
consecutive analyses of seven different preparation blank dissolutions. 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). MDLs must be
determined and reported for each wavelength used in the analysis of the
samples.
12.3 The quarterly determined-MDL for an instrument must always be used as
the MDL for that instrument during that quarter. If the instrument is
adjusted in anyway that may affect the MDL, the MDL for that instrument must
be redetermined and the results submitted for use as the established MDL for
that instrument for the remainder of the quarter.
12.4 MDLs must be reported for each instrument on FORM XI-HCIN and submitted
with each data package. If multiple instruments are used for the analysis of
an analyte within a SDG, the highest MDL for the analyte must be used for
reporting concentration values for that SDG.
IHC01.2
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Specific QA/OC Procedures Exhibit E
12.5 The MDL for each analyte must be less than or equal to the CRQL. An
exception is granted if the analyte concentration in the samples is greater
than or equal to two times the reported method detection limit.
13. Interelement Corrections for ICP
13.1 The ICP interelement correction factors must be determined within three
months prior to beginning sample analyses under this contract and at least
annually thereafter. Correction factors for spectral interference must be
determined at all wavelengths used for each analyte reported by ICP.
13 .'2 The correction factors must be determined under the same instrument
conditions used for sample analysis. If the instrument was adjusted in any
way that may affect the ICP interelement correction factors, the factors must
be redetermined and the results submitted for use. The interelement factors
determination must be reported on FORM XIII-HCIN for all ICP analytes.
14. Hvdrlde ICP fHYICP) and GFAA PC Analyses
14,1 Because of the nature of the GFAA and HYICP techniques, the special
procedures summarized in Figures 4 and 5 will be required for quantisation.
(These procedures do not replace those in Exhibit D of this SOW, but
supplement the guidance provided therein.)
14.1.1 All analyses must fall within the calibration range. In addition,
all analyses, except during full Methods of Standard Addition (MSA), will
require duplicate exposures/injection to be reported in raw data as well as
the average intensity and concentration values. A maximum of 10 full sample
analyses to a maximum of 20 exposures/injections may be performed between each
consecutive calibration verification and blank. The raw data package must
contain intensity and concentration values for both exposures/injections, the
average value and the relative standard deviation (RSD) or coefficient of
variation (CV). For concentrations greater than CRQL, the duplicate
exposure/injection readings must agree within 20% RSD or CV, or the analytical
sample, must be rerun once (i.e., two additional exposures/injections). If the
readings are still out, flag the value reported on FORM I-HCIN 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-HCIN for that sample.
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, respike and reanalyze
all analytical samples associated with that blank.
14.1.2 All HYICP and GFAA 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
IHC01.2 . Page 248
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Specific QA/QC Procedures
Exhibit E
FIGURE 4
GFAA Spike Analysis Scheme
Spike Sample at 2x
the CRQL
Analyses within
Calibration Range
YES
NO
Dilute Sample
Recovery of Spike
Less Than 40%
NO
If Yes, Repeat Only Once
If Still YES
Sample Absorbance or
Concentration Less Than
50% of Spike Absorbance
or Concentration
YES
Spike Recovery
Less Than 85%,or
Greater than 115%
NO
II
YES
Quantitate by MSA with 3
Spikes at 50, 100, & 150%
of Sample Absorbance
or Concentration
(Only Single Injections Required)
Correlation Coefficient
Less Than 0.995
TT
T
NO
Flag Data with "S"
Spike Recovery
Less Than 85% or
Greater Than 115%
NO
If YES, Repeat Only Once
If Still YES
Flag Data
with an "E"
Report Results
Down to IDL
Report Results
Down to IDL,
Flag with a "W"
Quantitate From
Calibration Curve
and Report Down
to IDL
Flag Data
with a "+'
IHC01.2
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Specific QA/QC Procedures
Exhibit E
FIGURE 5
Hydride IGF Absorption Analyses Scheme
Spike Sample at 302
the Linear Range
(Double Exposures Required)
Analyses within
Calibration Range
YES
'
NO
If YES, repeat only o
Dilute Sample
Recovery of Spike
Less than 40X
If still, YES
Flag Data
with an "E"
NO
Spike Recovery
Greater than 85% and
Less than 115?
YES
NO
Quantitate from
Calibration Curve
Report Undetected
Values as MDL U
Quantitate by MSA with 3
Spike at 20, 40, and 60X
of Linear Range
{Qnlv Single Exposures Required)
If YES, repeat only once
Correlation Coefficient
Less than 0.995
If still YES
Flag Data
with a "+"
NO
Flag Data with "S1
IHC01.2
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Specific QA/QCProcedures
Exhibit E
will be required to be at a concentration (in the sample) of 30% of the linear
range (in mg/L) for HYICP and 2x the CRQL for GFAA. 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. MSAs are 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 the control limits (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 respike and reanalyze all analytical samples
associated with the blank. An analytical spike is not required on the pre-
digestion spike sample.
i
14.1.3 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 Spike Sample Analysis, this exhibit),
will then determine how the-sample will be quantitated, as follows:
If the spike recovery is < 40%, the sample must be diluted by a factor
of 5 and rerun with another spike. This step must only be 'performed
once. If after the dilution the spike recovery Is still < 40%, report
data from the initial undiluted analysis and flag with an "E" to
indicate interference problems.
If 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
MDL. -
If the spike recovery is greater than 40% and less than 85% or greater
than 115%, the sample must be quantitated by MSA.
The following procedures will be incorporated into MSA analyses.
Data from MSA calculations must be within the linear range as
determined by the calibration curve generated at the beginning of the
analytical run.
The sample and three spikes must be analyzed consecutively for MSA
quantitation (the "initial" spike run data are 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).
For analytical runs containing only MSAs, single exposures/injections
can be used for QC samples during that run.
IHC01.2
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Specific QA/QC Procedures
Exhibit E
HYICP Spikes must be prepared such that:
1) Spike 1 is approximately 20% of the linear range in mg/L.
2} Spike 2 is approximately 40% of the linear range in mg/L.
3) Spike 3 is approximately 60% of the linear range in mg/L.
The data for each MSA analysis must be clearly identified in the raw
data documentation (spike concentrations measured intensities or
concentration, x-intercept, y-intercept and correlation coefficient).
The results shall be reported on FORM X-HCIN. Reported values
obtained by MSA must be flagged on FORM I-HCIN with the letter "S" if
the correlation coefficient is greater than or equal to 0.995.
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 X-HCIN, report the results of both MSA analysis and flag
with a "+" for any MSA result that yields a correlation coefficient
less than 0.995.
GFAA Spikes must be prepared such that:
1) Spike 1 is approximately 50% of the sample concentration in
mg/L.
2) Spike 2 is approximately 100X of the sample concentration in
mg/L.
3) Spike 3 is approximately 150% of the sample concentration in
mg/L.
The data for each MSA analysis must be clearly identified in the raw
data documentation (spike concentrations measured intensities or
concentration, x-intercept, y-intercept and correlation coefficient).
The results shall be reported on FORM X-HCIN. Reported values
obtained by MSA must be flagged on FORM I-HCIN with the letter "S" if
the correlation coefficient is greater than or equal to 0.995.
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 X-HCIN, report the results of both MSA analysis and flag
with a "+". for any MSA result that yields a correlation coefficient
less than 0.995.
IHC01.2
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SECTION III
LABORATORY EVALUATION PROCESS
This document outlines the procedures which will be used by the EPA
Administrative or Technical 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:
Evaluation of laboratory performance, and
On-site inspection of the laboratory to verify continuity of personnel,
instrumentation and quality control requirements of the contract.
1.
Evaluation of Laboratory Performance
1.1 Preaward Performance Evaluation (PPE) Sample Analysis
1.1.1 The Preaward Performance Evaluation (PPE) sample set will be sent to a
participating laboratory before the contract award, to verify the laboratory's
ability to produce acceptable analytical results.
1.1.2 When the PPE data are received by EPA, results will be scored for
identification and quantitation. The Contractor will be notified of
accepability/nonacceptability within 45 days.
1.2. Performance Evaluation Sample (PES) Analysis
1.2.1 The Performance Evaluation Sample (PES) will assist the EPA in
monitoring contractor performance. The laboratory will not be informed of the
analytes in the PES or their concentration.
1.2.2 The Contractor shall prepare, analyze and report the results of the
PES one per each SDG (if available).
1.2.3 The laboratory shall receive the PES in ampules or as full volume
samples from the EPA. The ampules shall come with instructions concerning the
preparation procedure required for the PES. The Contractor shall use the
ampules in increasing alphanumeric order.
1.2.4 The Contractor shall prepare and analyze the PES using the procedure
described in the sample preparation and method analysis sections of Exhibit D
of this Statement of Work. All contract-required QC shall also be met.
1.2.5 In addition to PES preparation and analysis, the Contractor shall be
responsible for correctly identifying and quantifying the analytes included in
the PES. The EPA will notify the Contractor of unacceptable performance.
NOTE: Unacceptable performance for identification and quantification of
analytes in the PES is defined as a score less than 75 percent.
IHC01.2
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Laboratory Evaluation Process Exhibit E
1.2.6 The Contractor shall demonstrate acceptable performance for analyte
identification and quantification. If the Contractor achieves a score of less
than 75 percent, the EPA may take, but is not limited to, the following
actions:
Show Cause and/or Cure Notice;
Reduction of the number of samples shipped to the laboratory;
Suspension of sample shipment;
A site visit;
A full data audit; and/or
' Require the-laboratory to analyze a remedial PES.
1.3 Inorganic Data Audit
1.3.1 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 rrgard to
achieving QA/QC acceptability.
2. Qn-Stte Laboratory Evaluation
2.1 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.
2.2 On-site laboratory evaluations allow the evaluators to determine that:
The organization and personnel are qualified to perform assigned tasks;
Adequate facilities and equipment are available;
Complete documentation, including chain-of-custody of samples, is being
implemented;
Proper analytical methodology is being used;
Adequate analytical quality control, including reference samples,
control charts, and documented corrective action measures, is being
provided; and
Acceptable data handling and documentation techniques are being used.
2.3 The on-site visit also serves as a mechanism for discussing weaknesses
identified through PE sample .analysis or through Contract Compliance Screening
or review of other data deliverables.
2.4 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.
IHC01.2 Page 254
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EXHIBIT F
CHAIN-OF-CUSTODY, DOCUMENT CONTROL,
AND STANDARD OPERATING PROCEDURES
"IHC01.2
.Page 255
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EXHIBIT F
CHAIN-OF-CUSTODY, DOCUHENT CONTROL,
AND STANDARD OPERATING PROCEDURES
Page
SECTION I:
CHAIN-OF-CUSTODY
257
SECTION II:
DOCUMENT CONTROL
260
SECTION III: STANDARD OPERATING PROCEDURES
264
IHC01.2
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SECTION I
CHAIN-OF-CUSTODY
A sample is physical evidence collected from a facility or from the
environment. An essential part of a hazardous waste investigation effort is
that the evidence gathered be controlled! To accomplish this, the following
sample identification, chain-of-custody, sample receiving, and sample tracking
procedures have been established. :
1.
Sample Identification
1.1 To ensure traceability of samples while in possession of the Contractor,
the Contractor shall have a specified method for maintaining identification of
samples throughout the laboratory.
1.2 Each sample or sample preparation container shall be labeled with the
EPA number or a unique laboratory identifier. If a unique laboratory
identifier is used, it shall be cross-referenced to the EPA number.
2.
Ghain-of-Custody Procedures
2.1 Because of the nature of the data being collected, the custody of EPA
samples must be traceable from the time the samples are collected until they
are introduced as evidence in legal proceedings. The Contractor shall have
procedures ensuring that EPA sample custody is maintained and documented. A
sample is under custody if:
It is in your possession; or
It is in your view after being in your possession; or
It was in your possession and you locked it up; or
It is in a designated secure area. Secure areas shall be accessible to
authorized personnel only.
3,
Sample Receiving Procedures
3.1 The Contractor shall designate a sample custodian responsible for
receiving all samples.
3.2 The Contractor shall designate a representative to receive samples in
the event that the sample custodian is not available.
3.3 The condition of the shipping containers and sample bottles shall be
inspected upon receipt by the sample custodian or his/her representative.
3.4 The condition of the custody seals (intact/not intact) shall be
inspected upon receipt by the sample custodian or his/her representative.
IHC01.2
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Chain-of-Custody
Exhibit F
3.5 The sample custodian or his/her representative shall check for the
presence or absence of the following documents accompanying the sample
shipment:
Airbills or airbill stickers;
Custody seals;
EPA custody records;
EPA Traffic Reports or SAS packing lists; and
Sample tags.
3.6 The sample custodian or his/her representative shall sign and date all
forms (i.e., custody records, Traffic Reports or packing lists, and airbills)
accompanying the samples at the time of sample receipt.
3.7 The Contractor shall contact SMO to resolve discrepancies and problems
such as absent documents, conflicting information, broken custody seals, and
unsatisfactory sample condition (e.g., leaking sample bottle)
3.8 The Contractor shall record the resolution of discrepancies and problems
on Telephone Contact Logs.
3.9 The following information shall be recorded on FORM HDC-1 by the sample
custodian or his/her representative as samples are received and inspected:
Condition of the shipping container;
Presence or absence and condition of custody seals on shipping and/or
sample containers;
Custody seal numbers, when present;
Condition of the sample bottles;
Presence or absence of airbills or airbills stickers;
Airbill or airbill sticker numbers;
Presence or absence of EPA custody records;
Presence or absence of EPA Traffic Reports or SAS packing lists;
Presence or absence of sample tags;
Sample tag identification numbers cross-referenced to the EPA sample
numbers;
Verification of agreement or non-agreement of information recorded on
shipping documents and sample containers; and
Problems or discrepancies.
IHC01.2
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Chain-of-Custody
Exhibit F
4.
Sample Tracking Procedures
4.1 The Contractor shall maintain records documenting all phases of sample
handling from receipt to final analysis. The records shall include
documentation of the movement of samples and prepared samples into and out of
designated laboratory storage areas.
IHC01.2
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SECTION II
DOCUMENT CONTROL
The goal of the laboratory document control program is to assure that
all documents for a specified SDG will be accounted for when the project is
completed. Accountable documents used by contract laboratories shall include,
but not be limited to, logbooks, chain-of-custody records, sample work sheets,
bench sheets, document control form, and other documents relating to the
sample or sample analyses. The following document control procedures have
been established to assure that all laboratory records are assembled and
stored for delivery to the EPA or are available upon request from the EPA
prior to the delivery schedule.
1.
Preprinted Data Sheets and Logbooks
1.1 All documents produced by the Contractor that are directly related to
the preparation and analysis of EPA samples shall become the property of the
EPA and shall be placed in the Complete Sample Delivery Group File (CSF). All
observations and results recorded by the laboratory but not on preprinted
laboratory forms shall be entered into permanent laboratory logbooks. When
all data from a SDG is complied, all original laboratory forms and copies of
all SDG related logbook entries shall be included in the documentation
package.
1.2 The Contractor shall identify the activity recorded on all laboratory
documents that is directly related to the preparation and analysis of EPA
samples.
1.3 Pre-printed laboratory forms shall contain the name of the laboratory-
and shall be dated (month/day/year) and signed by the person responsible for
performing the activity at the time an activity is performed.
1.4 Logbook entries shall be dated (month/day/year) and signed by the person
responsible for performing the activity at the time an activity is performed.
1.5 Logbook entries shall be in chronological order. Entries in logbooks,
with the exception of instrument run logs and extraction logs, shall include
only one SDG per page.
1.6 Pages in both bound and unbound logbooks shall be sequentially numbered:
1.7 Instrument run logs shall be maintained so as to enable a reconstruction
of the run sequence of individual instruments. Because the laboratory must
provide copies of the instrument run logs to the EPA, the laboratory may
exercise the option of using only laboratory or EPA sample identification
numbers in the logs for sample ID rather than government agency or commercial
client names to preserve the confidentiality of commercial clients.
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Document Control
Exhibit F
1.8 Corrections to supporting documents and raw data shall be made by
drawing a single line through the error and entering the correct information.
Corrections and additions to supporting documents and raw data shall be dated
and initialed. No information shall be obliterated or rendered un readable.
All notations shall be recorded in ink. Unused portions shall be
(i.e., draw a large Z on the unused portion of the page).
'z'd" out
2.
Consistency of Documentation
2.1 The Contractor shall assign a document control officer (DCO) responsible
for the organization and assemblance of the CSF.
2.2 All copies of laboratory documents shall be complete and legible.
2.3 Before releasing analytical results, the DCO 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 sample delivery group is consistent
throughout the CSF.
3.
Document Numbering and Inventory Procedure
3.1 In order to provide document accountability of the completed analysis
records, each item in the CSF shall be inventoried and assigned a serialized
number as described in Exhibit B, Section II.
3.2 All documents relevant to each SDG, including logbook pages, bench
sheets, screening records, re-preparation records, re-analysis records,
records of failed or attempted analysis, custody records, etc., shall be
inventoried.
3.3 The DCO shall be responsible for ensuring that all documents generated
are placed in the CSF for inventory and are delivered to EPA. The DCO shall
place the sample tags in plastic bags in the file. Figure 5 is an example of
a document inventory.
4.
Storage of EPA Files
4.1 The Contractor shall maintain EPA laboratory documents in a secure
location. Access shall be limited to only designated personnel.
5.
Shipping Data Packages and Complete Sample Delivery Group File (CSF)
5.1 The Contractor shall document shipment of deliverables packages to the
recipients. These shipments require custody seals on the containers placed
such that the containers cannot be opened without damaging or breaking the
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Document Control . Exhibit F
:| seal. The Contractor shall document what was sent, to whom, the date, and the
method (carrier) used.
5.2 The Contractor shall purge the CSF deliverable to the appropriate EPA
Region 180 days after the report submission.
5.3 A copy of the transmittal letter for the CSF will be sent to NEIC and
SMO.
' 5.4 Sample Log-In Sheet
5.4.1 This form is used to document the receipt and inspection of shipping
" containers and samples. The Contractor shall submit one (1) original FORM
HDC-1 for each shipping container.
5.4.2 The Contractor shall sign and date the airbill (if present)*, examine
the shipping containers, record the presences or absence of custody seals and
their conditions.
5.4.5 The Contractor shall note any problems with the samples and follow the
instructions explained in Exhibit B, Sample Log-In Sheet.
5.4.6 The Contractor shall submit a completed Sample Log-In Sheet with each
, SDG package.
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Document Control
Exhibit F
Figure 5
Example
DOCUMENT INVENTORY
232-2-0001
Case No.
Region
Document Control
232-2-0001
232-2-0002
232-2-Q003
232-2-0004
232-2-0005
232-2-0006
232-2-0007
232-2-0008
Document Type
Case File Document Inventory Sheet
Chain-of-Custody Records
Shipping Manifests ........
# Pages
1
. 2
2
Sample Tags ; 50
SMO Inorganics Traffic Reports 10
Inorganics Analysis Data Summary Sheets .... 10
Analysts' Notebook Pages 14
ICP and AA Instrument Logbook Pages 12
1This number is to be recorded on each set of documents
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SECTION Til
STANDARD OPERATING PROCEDURES
The Contractor shall have written standard operating procedures (SOPs)
for the following:
Sample receipt and logging;
Sample and extract storage;
. Preventing sample contamination;
Security for laboratory and samples;
Traceability/equivalency of standards;
* Maintaining instrument records and bound logbooks;
Glassware cleaning;
Technical and managerial review of laboratory operation and data package
preparation;
Internal review of contractually-required QA/QC data for each individual
data package;
Sample analysis, data handling, and data reporting;
Chain-of-custody; and
Document control, including Complete SDG File preparation.
1. Specifications for Written Standard Operating Procedures
1.1 An SOP is defined as a written narrative stepwise description of
laboratory operating procedures including examples of laboratory
documentation. The SOPs should describe accurately 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 the EPA as the basis for laboratory
evidence audits.
1.2 The'Contractor shall have written SOPs describing the sample custodian's
duties and responsibilities.
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Standard Operating Procedures
^Exhibit F
1.3 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: -
Presence or absence of EPA chain-of-custody forms;
Presence or absence of airbills or airbill stickers;
. Presence or absence of Traffic Reports or.SAS packing lists;
Presence or absence of custody seals on shipping and/or sample
containers and their condition;
Custody seal numbers, when present; «, -
Airbill or airbill sticker numbers;
* Presence or absence of sample tags;
Sample tag ID numbers; ''
Condition of the shipping container;
Condition of the sample bottles;
Verification of agreement or nonagreement of information on receiving
documents and sample containers;
- Resolution of problems or discrepancies with the Sample Management
Office.
The definition of any terms used to describe sample condition upon
receipt.
1.4 The Contractor shall have written SOPs for maintaining identification of
EPA samples throughout the laboratory.
1.5 If the Contractor assigns unique laboratory identifiers, written SOPs
shall include a description of the method used to assign the unique laboratory
identifier and cross-reference to the EPA sample number.
1.6 If the Contractor uses prefixes or suffixes in addition to sample
identification numbers, the written SOPs shall include their definitions.
1.7 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, 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.
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Standard Operating Procedures
Exhibit F
1.8 The Contractor shall have written SOPs describing all storage areas for
samples in the laboratory. The SOPs shall include a list of authorized
personnel who have access or keys to secure storage areas.
1.9 The Contractor shall have written SOPs describing the method by which
the laboratory maintains samples under custody.
2.
Handling of Confidential Information
2.1 A Contractor conducting work under this contract may receive EPA-desig-
nated 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.
2.2 All confidential documents shall be under the supervision of a desig-
nated Document Control Officer (DCO).
2.3 Any samples or information received with a request of confidentiality
shall be handled as "confidential." A separate locked file shall be
maintained to store this information and shall be segregated from other
nonconfidential information. Data generated from confidential samples shall
be treated as confidential. Upon receipt of confidential information, the DCO
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.
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EXHIBIT G
GLOSSARY OF TERMS
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Glossary ofTerms
ALIQUOT - A measured portion of a fi'eld sample taken for analysis.
ANALYSIS DATE/TIME - The date and military time (24-hour clock) of the
injection of the sample, standard, or blank into the analysis system.
ANALYSIS GROUP - An analysis group is a set,of no more than 20 analytical
samples (as defined below) for the purpose of method Quality Assurance/Quality
Control (QA/QC) , such that the QA/QC required by Exhibit E is, at a minimum,
prepared and analyzed at a frequency of once per 20 analytical samples.
ANALYSIS REPLICATE - A single analytical sample processed through the
analytical preparation method and analyzed in replicate.
ANALYSIS RUN - The actual instrumental analysis of the sample preparations
from the time of instrument calibration through the running of the final
continuing calibration verification (CCV). All sample preparation analyses
during the analysis run are subject to the QC protocols set forth in Exhibit E
of this contract unless otherwise specified in the individual methods,
ANALYSIS SPIKE SAMPLE - An analytical sample taken through the analytical
.preparation method and then spiked prior to analysis.
ANALYTE - The element or ion an analysis seeks to determine; the element of
interest.
ANALYTICAL PREPARATION - An analytical sample taken through the analytical
preparation method. Also referred to as preparation or sample preparation.
ANALYTICAL PREPARATION METHOD - A method (digestion, dilution, extraction,
fusion, etc.) used to dissolve or otherwise release the analyte(s) of interest
from its matrix and provide a final solution containing the analyte which is
suitable-for instrumental or other analysis methods.
ANALYTICAL SAMPLE - Any solution or media introduced into an instrument on
which an analysis is performed excluding instrument calibration, initial
calibration verification, initial calibration blank, continuing calibration
verification and continuing calibration blank. Note the following are all
defined as analytical samples: undiluted and diluted samples (EPA and non-
EPA), predigestion spike samples, duplicate samples, serial dilution samples,
analytical spike samples, post-digestion spike samples, interference check
samples, CRQL standard for ICP (CRI) and AA (CRA), laboratory control sample,
preparation blank, and linear range analysis sample.
ANALYTICAL SPIKE - A post-digestion spike to be prepared prior to analysis by
adding a known quantity of the analyte to an aliquot of the prepared sample.
The unspiked sample aliquot must compensate for any volume change in the spike
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Glossary of Terms
Exhibit G
samples by addition of ASTM Type II .water to the unspiked sample aliquot. The
volume of the spiking solution added must not exceed 10X of the analytical
sample volume.
ASTM TYPE II WATER - Distilled water with a conductivity of less than 1.0
/mho/cm at 25°C. For additional specifications refer to ASTM D1193-77,
"Standard Specification for Reagent Water."
AUTOZERO - Zeroing the instrument at the proper wavelength. It is equivalent
to running a standard blank with the absorbance set at zero.
AVERAGE INTENSITY - The average of two different injections (exposures).
BACKGROUND CORRECTION - A technique to compensate for variable.background
contribution to the instrument .signal in the determination of trace elements.
BATCH - A.group of samples prepared at the same time. -
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
reagents and concentration of acids as used in the sample preparation.
CALIBRATION BLANK - A blank solution containing all of the reagents and in the
same concentration as those used in the analytical sample preparation. This
blank is not subjected to the preparation method but is produced
synthetically.
CONTINUING CALIBRATION VERIFICATION (CCV) - A single element or multi-element
standard solution prepared by the analyst to be used to verify the stability
of the instrument calibration with time and the instrument performance during
the analysis of samples. The CCV can either be one or more of the calibration
standards and/or an initial calibration verification
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Glossary of Terms
Eyhibit G
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.
COEFFICIENT OF VARIATION (CV) - The standard deviation as a percent of the
arithmetic mean.
CONTRACT REQUIRED QUANTITATION LIMIT (CRQL) - 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 b sis of the least
squares line.
DAY - Unless otherwise specified, day shall mean calendar day.
DDI - Deionized distilled water.
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.
EBCDIC - Extended Binary Coded Decimal Interchange Code.
EXPOSURE - A full measurement of an emission line of an analyte from which the
concentration of the analyte can be determined in the excitation system in a
manner that meets the system's detection limit. It is also referred to as a
peak scan.
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.
GEL - A two-phase colloidal system consisting of a solid and a liquid which
behave as elastic solids and retain their characteristic shape.
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 (digestion or
distillation).
Holding time (sample analysis date - sample receipt date)
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Glossary of Terms
Exhibit G
HYICP - Hydride Inductively Coupled Plasma.
INDEPENDENT STANDARD - A contractor-prepared standard solution that is
composed of analytes from a different source than those used in the standards
for the initial calibration.
INDUCTIVELY COUPLED PLASMA (ICP) - A technique for the simultaneous or
sequential multi-element determination of elements in solution. The basis of
the method is the measurement of atomic emission by an optical spectroscopic
technique. Characteristic atomic line emission spectra are produced by
excitation of the sample in a radio frequency inductively coupled plasma.
IN-HOUSE - At the Contractor's facility.
INITIAL CALIBRATION VERIFICATION (ICV) - Solution(s) obtained from the EPA or
prepared from stock standard solutions, metals or salts obtained from a source
separate from that (those) utilized to prepare the calibration standards and
that have known concentration values. The 'ICV is used to verify the
concentration of the calibration standards and the adequacy of the instrument
calibration. The ICV is not restricted to preparations made by official
agencies when EPA sources are not available but should be traceable to the
National Institute of Standards and Technology (NIST) or other certified
standard.
INTERFERENCE CHECK SAMPLE (ICS) - Solution(s) containing both interfering and
analyte elements of known concentrations that can be used to verify background
and interelement correction factors. This solution must also contain the same
matrix as the analytical preparations.
INTERFERANTS - Substances which affect the analysis for the element of
interest.
LABORATORY - Synonymous with Contractor as used herein.
LABORATORY CONTROL SAMPLE (LCS) - A control sample of known composition.
Aqueous and solid laboratory control samples are analyzed using the same
sample preparation, reagents, and analytical methods employed for the EPA
samples received.
LABORATORY RECEIPT DATE - The date on which a sample is received at the
Contractor's facility, as recorded on the shipper's delivery receipt and
sample Traffic Report. Alcn referred to as VTSR (validated time of sample
receipt).
LINEAR RANGE - The concentr.. .ion range over which the analytical curve remains
linear. The range of the instrument for a specific analyte, as determined
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Glossary of Terms
Exhibit G
using calibration standards. The upper limit of this linear range (determined
at each analysis) is the highest concentration calibration standard that has a
determined value within 10X of the known value.
MATRIX - The predominant material of which the sample to be analyzed is
composed. Matrix is not synonymous with phase (liquid or solid).
MATRIX MODIFIER - Salts used in AA to lessen the effects of chemical
interferants, viscosity, and surface tension.
MATRIX SPIKE - Aliquot of a sample 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 BLANK - A solution produced by performing the analytical preparation
method without the addition of a sample. The solution thus contains the same
concentrations of reagents as all other analytical preparations plus any
impurities derived from the preparation process. For preparations containing
reagents of variable concentrations, the method blank should match the maximum
reagent concentration used in the sample preparation(s).
METHOD DETECTION LIMIT (MDL) - The chemical concentration that produces a
signal, due to an analyte, which is equal to the student t 99 times the
standard deviation of a series of measurements on at least seven separate
method blanks. In practice, a method detection limit will be substantially
higher than an instrumental detection limit. The method.detection limit for
metals is t 99 times the standard deviation of seven method blank analyses.
All spectral background techniques must be operative and the same integration
times must be utilized as when actual samples are analyzed.
METHOD OF STANDARD ADDITIONS (MSA) - The addition of three 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.
MISCIBILITY - The ability of a liquid to dissolve uniformly in another liquid.
If equal portions of two liquids are mixed and no interfacial meniscus is
observed, the liquids are miscible. If a meniscus is observed without an
apparent change in volume of the two liquids, the liquids are non-miscible.
If there is an obvious change in the volume of the liquids, and a meniscus is
observed, the liquids are partially miscible.
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Glossary of Terms
Exhibit G
PERFORMANCE EVALUATION SAMPLE (PES) - A sample of known composition provided
by EPA for Contractor analysis. Used by EPA to evaluate Contractor
performance.
PHASE - The physical state of the sample or analytical sample which may be
described as: water miscible (w), non-water'miscible (n) or solid (c) (see
Method 50.60-CLP).
PREPARATION LOG - Ah official record of the sample preparation (digestion).
PRIORITY POLLUTANT - Any substance introduced into the environment that the
EPA classifies as being an immediate danger to the health and welfare of human
life.
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).
QUALITY CONTROL SET - A group of 10 analytical samples plus the CCVs and CCBs
that bracket those samples.
ROUNDING RULES (EPA) - 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.
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:
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Glossary of Terms
Exhibit G
Case; or
Each 20 samples within a Case; or
Each 14-day calendar period during which samples in a Case are
received, beginning with receipt of the first sample in the Case
or SDG.
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 known factor. 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 interferants.
»
STOCK SOLUTION - A standard solution which can be diluted to derive other
standards.
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.
VIEWING AREA ADJUSTMENT STANDARD - A solution containing a standard of a
strong atom line (i.e., Cu) and a weak ion line (i.e., fia) used to verify the
proper adjustment of the observation height in the plasma for metals analysis
by ICP (see Method 200.62-B-CLP for details).
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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