United States
Environmental Protection
Agency
Office of
Solid Waste and
Emergency Response
Publication 9240.1-24
EPA/540/R/94/091
December 1994
Superfund
&EPA USEPA CONTRACT
LABORATORY PROGRAM
STATEMENT OF WORK FOR
RAPID TURNAROUND DIOXIN
ANALYSIS, MULTI-MEDIA
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0.1-24
5-963518
¦540/R- 94/091
USEPA CONTRACT LABORATORY PROGRAM
STATEMENT OF WORK
FOR
RAPID TURNAROUND DIOXIN ANALYSIS
MULTI-MEDIA
S
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TABLE OF CONTENTS
EXHIBIT A:
Summary of Requirements
EXHIBIT B:
Reporting and Deliverables Requirements
EXHIBIT C: Analytical Methods and Quality Assurance
Quality Control (QA/QC) Procedures
EXHIBIT D: Quality Assurance/Quality Control Requirements
EXHIBIT E; Specifications for Chain-of-Custody, Document Control
and Standard Operating Procedures
APPENDIX A; Users Guide to the Computer Data Entry Program
for the Evaluation of 2,3,7,8-TCDD by GC/MS/MS
and LR/GC/MS and Examples of Required Data Reporting Format
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EXHIBIT A
SUMMARY OF REQUIREMENTS
SECTION I: GENERAL REQUIREMENTS
SECTION II: SPECIFIC REQUIREMENTS
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SECTION I
GENERAL REQUIREMENTS
Under the Superfund Program, the US EPA is conducting extens iv® rsMdisl
activities at identified dioxin sites throughout the United States. Thass
labor and equipment-Intensive efforts often involve enormous daily operating
costs. The removal aspect, combined with this cost factor, necessitates
accurate and time-critical decision-making. Therefore, proper support of
these activities requires the services of contract analytical laboratories to
analyze materials potentially contaminated with dioxlns, and provide rapid
turnaround of reliable data from which accurate and cost-effective decisions
can be made.
The requirement of this contract is for the extraction and analysis of
samples to determine the presence and concentration of 2,3,7,8-TCDD in solid
samples (soil/sediraent, dust, wood fiber, vegetation, insulation, clothing), water
air aad wipe samples by either High Resolution Gas Chromatography/Tandem
nass Spectrometry (HRGC/MS./MS) or High Resolution Gas Chromatography/Low
Resolution Mass Spectrometry (HRGC/LRMS), This contract requires rapid data
turnaround via electronic data submission, followed by submission of hardcopy
data. The Contractor shall be required to use proven instruments and
approved analytical methods and techniques, to follow strict quality control
procedures, and to submit analytical data in a standardized format, as
outlined in this SOW.
This SOW is divided into two main task areas. Samples identified for
analysis under Task 1 will be analyzed by strictly adhering to the methods
contained in tha SOU, Exhibit C. Task 1 will consist of samples considered
routine in nature where no problems in analysis are anticipated based on
previous analysis of the sample, sample area, or sample type. It is
anticipated that approximately 5% of samples identified for Task 1 will not
be analyzable using the prescribed routine methods because of matrix
interference problems.
These samples along with other samples suspected as having matrix
problems will be handled under Task 2. Samples under Task 2 will be analyzed
using methods proposed by the laboratory and approved by the TPO. Generally,
these will consist of modified Task 1 methods.
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SECTION XI
SPECIFIC REQUIREMENTS
The majority of staples to be analyzed under this contract will be collected
from dioxin sites in eastern Missouri, for the purpose of enforcement and
remedial actions. The Contractor shall use its analytical experience and
equipment in the determination of 2,3,7,8-Tetrachlorodibenzo-p-dioxin
(2,3,7,8-TCDD) in samples where 2,3,7,8-TCDD is known to be the principal or
only isomer present. The Contractor shall follow the protocols provided by
the USEPA herein for sample preparation, analysis, storage and preservation
before and after the analysis. During preparation, the Contractor shall
fortify all samples, blanks, and matrix spikes with a surrogate spiking
compound (sea Exhibit C).
1- SAttfLE PEHTERI
Samples to be analyzed under this contract shall be shipped to the
Contractor through commercial delivery service for arrival by 2:00 p.m.
on a given day.
2- DATA SUBMISSION
2.1 Task 1:
Data are to be electronically submitted to the designated recipients by
6:00 a.m. (central time) the day following sample receipt for all
samples excluding air samples, and by 6:00 a.m. (central time) on the
second day following sample receipt for air samples.
Task 2:
Data are to be electronically submitted to the designated recipients by
6:00 a.m. (CT) the second day following approval of the Task 2
proposal submitted by the laboratory.
See Contract Reporting Schedule (Clause F.5).
2.2 The Government will supply the Contractor with a software package to be
used to transmit required data electronically and to generate printouts
for the sample data package. A users guide to the software package is
provided in Appendix B. The Contractor is required to provide the
following computer software and hardware to support the electronic data
transmission requirement:
Hardware:
IBM Personal Computer (IBM AT, COMPAQ, or other 100%
compatible computer)
Minimum of 1 megabyte of memory
MS-DOS or PC-DOS, version 3.1 or higher
One 1.2 meg 5.5 inch floppy disk drive and a hard disk drive of 20 meg.
Printer with at least 80 column capacity
2400 baud Hayes-compatible modem
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Software
XTALK XVI - Version 3.61 or higher
PC Anywhere III
dBase III+. Version 1.1
3- LABORATORY PERSONNEL
The Contractor shall designate and utilize key personnel meeting the
minimum requirements as set forth in items 3.1 through 3.3 below, to
meet all the terms and conditions of the contract. The EPA reserves
the right to review personnel qualifications.
3.1 The laboratory manager shall have at least 2 years of experience in the
management of projects of comparable complexity.
.3.2 The Contractor's GC/MS/MS (or CC/MS) operators performing work in this
contract shall each have at least 9 months experience in the operation
of the GC/MS/MS/DS (or CC/M5/DS) on environmental samples and have a BS
in Chemistry or equivalent.
3.'3 The Contractor's extraction and concentration specialist performing
work on this contract shall have at least 6 months experience in
preparation of extracts from environmental or hazardous waste samples.
In addition, they must have a high school diploma or equivalent and
have 10 hours college credit in chemistry or equivalent.
NOTE: "Experience" is defined as more than 50% of the person's work
time.
4. ANALYTICAL PROCEDURES
4.1 Task 1
In Exhibit C, the EPA provides the Contractor with the specific
analytical procedures to be used along with the definition of the
specific application of these methods to this contract. This Includes
instructions for sample preparation, gas chromatographic/mass
spectrometrlc identification and data evaluation. Specific Ions used
for searching the mass spectral data are included.
For each sample, the Contractor shall perform the following:
4.1.1 Handle samples as specified in the chain-of-custody procedures
described in Exhibit E .
4.1.2 Prepare the samples as described in Exhibit C.
4.1.3 Extract the samples as described in Exhibit C.
4.1.4 Analyze the samples as described In Exhibit C.
4.1.5 Confirm or negate the presence of 2,3,7,8-TCDD In each sample
using criteria specified In Exhibit C. If present, calculate
the concentration; if absent, estimate the detectable limit.
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4.1.6
Measure che concentration of the surrogate compound and
calculate the accuracy as measured by percent recovery for each
sample and blank (see Exhibit C for calculations).
4.1.7 Analyze as prescribed performance check solution and
appropriate QC samples (blanks, fortified samples and
performance evaluation samples).
4.2 Task 2
Samples known or suspected of being difficult to analyze because of
matrix interferences and those samples exhibiting matrix interferences
from Task 1 shall be analyzed under Task 2. The purpose of Task 2 is
to allow optimization of existing methods to overcome these
interference problems and get useable data. (See flow charts at the
end of this section.)
4.2.1 Specifically, non-consumed samples analyzed under Task 1 which
do not yield acceptable results initially and upon re-
extraction/reanalysis shall immediately be scheduled for Task 2
analysis after coordination with and approval by the TPO. In
these instances the laboratory shall be responsible for
initiating a Task 2 proposal form (T-2 Form). Samples may also
be submitted directly from the Region which are identified for
Task 2 analysis. In these instances the Region will generate
the T-2 Form which the laboratory shall return when the form is
completed.
4.2.2 Upon receipt of any sample(s) identified for Task 2 analysis
(or based on Task 1 results), the laboratory shall prepare a
proposal to analyze the samples. The proposal will be based on
background information available to the laboratory and their
experience in dealing with similar types of samples. In most
instances it is anticipated that the Task 2 analysis will
consist of minor modifications of the Task 1 methods. Such
modifications may include a more intensive sample cleanup or
other derivations of the method. Proposals may be based on
methods in scientific literature or other documents. The
proposal may specify different procedures for different samples
in order to achieve the optimal analysis for each sample. The
exact detailed procedure used by the Contractor in the
performance of Task 2 analyses shall be made available in
writing to the Region (if requested by the Region) within 7
days of written request.
4.2.3 The laboratory shall submit their proposal within twenty-four
(24) hours from the date/time of sample receipt. In the case
of Task 1 samples being converted to Task 2, the proposal shall
be submitted within one day of identifying the sample for Task
2 analysis (for standardization this will be the date/time that
the Task 1 analysis was due). The laboratory shall submit
their proposal on a T-2 Form. The T-2 Form shall be submitted
via Facsimile (FAX) to the TPO for approval. The TPO will
promptly evaluate the Laboratory proposal for analysis and
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respond to the laboratory as follows; 1) APPROVE; 2) APPROVE
WITH MODIFICATIONS NOTED; 3) DISAPPROVE, 4) STOP REQUEST. The
T-2 Form with the IPO's response will be returned co the
laboratory via FAX. 1) APPROVE, the laboratory should initiate
sample analysis. If the TPO response Is 2) APPROVE WITH
MODIFICATIONS NOTED, the laboratory must then agree to the
modifications by signing the T-2 Font in the space provided.
The T-2 Form shell then be returned to the TPO and the TPO will
Indicate the reporting schedule based on the date/time the
laboratory agreed to the modifications. If the TPO response is
3) DISAPPROVE, the laboratory should submit another proposal.
If the TPO response Is 4) STOP REQUEST, the laboratory should
take no further action and the case/batch will be considered
closed.
4.2.4 The sample analysis start time begins when the TPO notifies the
laboratory of his approval of their proposal. For clarity the
TPO will note the official start date/time and due date/time on
the T-2 Form. (In the case of modifications, the TPO will note
the start and due date/time after acceptance of the
modifications by the laboratory.) The reporting time for
electronic data submission (EDS) is as follows: For proposals
approved prior to 2:00 pm (CST) the reporting date/time will be
6:00 as (CST) of the second day (40+ hours). Proposals
approved after 2:00 pm (CST) will be considered received the
next day and will be due by 6:00 am (CST) of the second day
following it. Hardcopy data packages will be due seven (7)
days from EDS.
4.2.5 For each sample, the Contractor shall perform the following;
4.2.5.1 Handle samples as specified in the chain-of-custody
procedures described in Exhibit £.
4.2.5.2 Prepare the samples as described in the proposal
section of the approved T-2 Farm.
4.2.5.3 Extract the samples as described in the proposal
section of the approved T-2 Form.
4.2.5.4 Analyze the samples as described in the proposal
section of the approved T-2 Form.
4.2.5.5 Confirm or negate the presence of 2,3,7,8-TCDD In
each sample using criteria specified in Exhibit C.
If present, calculate the concentration present; if
absent, estimate the detection limit.
4.2.5.6 Measure the concentration of the surrogate compound
and calculate the accuracy as measured by percent
recovery for each sample and any blanks (see Exhibit
C for calculations.)
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4.2.5.7 Analyze as prescribed performance check solutions
and appropriace QC samples (blanks, matrix spike
samples, duplicates and performance evaluation
samples).
4.2.5.8 Provide all reports and documentation within the
applicable delivery requirements as specified in
Exhibit B.
4.2.5.9 Upon completion of analysis contained in the
proposal, the laboratory should provide Electronic
Data Submission (EOS) and hardcopy data submittals
in a manner similar to Task 1 analysis using the
same software and hardcopy formats.
4.2.5.10 Perform all required sample rerun extractions and
analyses, as specified in Exhibit C.
4.2.5.11 Provide all reports and documentation within the
applicable delivery requirements as specified in
Exhibit B.
5. SAFETY
The samples to be analyzed by the Contractor are from known or
suspected dioxin waste sices and may contain dioxins and other
potentially hazardous organic and/or inorganic materials at potentially
hazardous concentration levels. The Contractor should be aware of the
potential hazards associated with Che handling and analyses of these
samples. It is the Contractor's responsibility to take all necessary
safety measures Co ensure his employees safety.
6. SAMPLES
6.1 Samples will be grouped ir. batches, with up Co twenty-four (24) samples
per batch. A sample is defined as one or more collection receptacle(s)
containing soil/sediment, water, dust, wood fiber, vegetation, clothing,
insulation, polyurechane foam plugs in air sampling cartridges, or
filter paper wipes.
6.2 One or more blank sair.ples may be included in each sample batch (at the
discretion of the field samplers). One blank may be designated for
spiking. The Contraccor shall forcify chis blank with 2,3,7,8-TCDD.
This fortified field blank shall be analyzed only after spiking and not
before. Other blanks, if any are included in the batch received, shall
be extracted and analyzed as routine samples per contract requirements.
6.3 In addition to blanks provided by the samplers, the Contractor shall
extract and analyze a laboracory reagenc blank for each bacch of 24 or
fewer samples per matrix cype using Che contract-specified procedures
herein. Reagent blank analyses are considered part of the required
internal laboracory QA/QC and are not a separate sample analysis for
contract accounting or billing purposes. Matrices ucilizing identical
extraction techniques rr.av snare a common reagenc blank. For example, a
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sample batch consisting of soil, vegetation, insulation, dust, and wood
fiber all use a jar extraction and could share a common reagent blank;
however, a separate reagent blank would be required for water, wipe or
air samples if included in the same shipment/batch.
7. SAMPLE RERUN REQUIREMENTS
7.1 Certain samples under Task 1 will require sample reruns (cleanup and
reanalyses and/or re-extraction and reanalyses) as specified in each
method in Exhibit C, A maximum of one automatic rerun analysis may be
required per sample. A sample rerun analysis performed in compliance
with the automatic rerun criteria in the methods is considered part of
the principal sample analysis and is not billable as a separate sample
unless matrix effects, interferences or other problems due to difficult
samples, that are beyond the scope of the methods, are established. If
the presence of such problems is established, then the rerun sample
will be considered a separate, billable sample. If the contractor
establishes that a matrix effect is responsible for the inability to
achieve acceptable results, the sample should immediately be scheduled
for re-analyses under Task 2. The Contractor shall adhere to the
following rerun reporting procedures.
7.2 In the case where the original sample analysis did not meet criteria
and an automatic rerun analysis is required, if the automatic rerun
analysis meets criteria, then report only the rerun analysis. Report
it as the original analysis (no sample number code is utilized and the
Rerun Code field will be blank). These automatic reruns are considered
to be part of the principal analysis and are included in the original
sample analysis price (i.e., these automatic reruns are not billable as
separate samples).
7.3 If after two analyses (original analysis and one rerun) all contract
criteria are not met, report both original and rerun analyses, as
follows. Report the original analysis with no sample number code;
report the rerun analysis with an "R" (rerun) code at the end of the
SMO sample number; Automatic rerun samples are not billable unless the
presence of matrix effects, interferences, or other problems
encountered due to difficult samples, that are beyond the scope of the
methods, can be established.
7.4 If the Contractor suspects that the rerun was necessary due to matrix
effects, interferences, or other problems due to difficult samples,
that are beyond the scope of the methods, the Contractor must
immediately notify the EPA Technical Project Officer and the Sample
Management Office, identifying the affected sample number(s) and the
rationale for suspecting such problems. This information must be noted
in the data report SDG Narrative for the sample batch. These
situations will be reviewed on a case-by-case basis by the EPA
Technical Project Officer and the Project Officer. If the presence of
such problems is established, then the rerun analysis will be billable
as a separate sample. When this occurs, the Technical Project Officer
will obtain Project Officer approval of the decision and will notify
the Sample Management Office that the subject rerun(s) is to be
considered a separate, billable sample. NOTE: When Invoicing for
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samples where the Contractor is billing for an automatic rerun due to
the suspected presence of matrix effects, the Contractor must note this
fact on the sample invoice. In this situation, after the Contractor
has requested and received TPO/PO approval per the above-described
process, automatic rerun analyses vould be paid as separate samplea.
7.5 If automatic reruns performed In association with Performance
Evaluation (PE) samples do not meet the required criteria, the EVA
Technical Project Officer will notify the Contractor that a particular
PE sample(s) and, hence, all samples in the associated sample batch
shall be rerun. For purposes of data delivery, the time of thla
notification shall be considered equivalent to the time of saspla
receipt (i.e., the data is due at 6:00 a.m. either one or two days
following notification when notification occurs prior to 2:00 p.m. See
Contract Reporting Schedule, Clause F.4.) NOTE: If data for automatic
rerun analyses associated with PE samples are submitted late per the
above requirement, the rerun analyses us subject to liquidated
damages. Automatic reruns associated with PE sample analyses must be
reported with a "P" (PE sample rerun) following the SMO sample number.
PE sample reruns are automatic reruns and are not billable as separate
samples. Automatic reruns are considered to be part of the principal
analysis and are included in the original sample analysis price.
7.6 The EPA Technical Project Officer may request rerun analyses (aa
approved by the EPA Project Officer) for any particular sample(s). For
purposes of data delivery, the time of ths reanalysis request shall be
considered equivalent to the time of sample receipt (i.e., the data Is
due at 6:00 a.m. either one or two days following notification when
notification occurs prior to 2:00 p.m. See Contract Reporting
Schedule). Such requested reruns are considered separate, billable
samples. As such, they are subject to liquidated damages. Requested
reruns shall be reported with a "Q" (requested rerun) following the SMO
sample number.
8. CARTRIDGE AND ICE CHEST RETURN
The Contractor shall be required to return air sampling cartridges and
ice chests to the return addressee indicated on or within the
container, within a period of seven (7) days following sample receipt.
The Government will pay reasonable costs for the return of air sampling
cartridges and ice chests. The Contractor will be provided an account
number with a carrier to be used for such purposes.
9. gOWWICATIW
The Contractor shall communicate with EPA CLP Sample Management Office
(SMO) personnel and designated Regional personnel by telephone as
needed throughout the process of sample scheduling, analyses and data
reporting to ensure that samples are properly processed. This shall
include immediately notifying SMO and the Region of any irregularities
with samples or paperwork received, problems encountered in sample
analyses that will affect the data produced, and laboratory conditions
that impact on timeliness of analyses and data reporting. In
particular, che Contractor shall notify SMO and Regional personnel in
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advance regarding sample data that will be late and shall specify or
estimate delivery time and date.
10. SAKPLE IDENTIFICATION
10.1 Samples received each day for analysis will be assigned a Case* number
and will be prearranged into batches (i.e., group of 24 or fewer
samples). Each batch of samples within each SDG will be assigned a
unique batch number as the designator for that specific set of samples.
Each batch may Include samples of any or all of the matrices described
herein.
10.2 Each sample in a batch will be labeled with a SMO sample number and
each batch will be accompanied by a Dioxin Shipment Record (DSR) form
bearing the Case and batch numbers for that sample set. EPA Sample
Numbers and descriptive Information regarding each sample in the batch
will appear on the DSR. The Contractor shall complete and sign the DSR
for each sample container, recording the date and time of sample
receipt and the condition of each sample on receipt. The Contractor
shall submit the signed copy of each DSR to SMO according to the
contract delivery schedule. If there are problems with the samples
(e.g., mixed media, containers broken or leaking) or paperwork (e.g.,
DSR not with samples, DSR sample number discrepancies), the Contractor
shall immediately contact SMO or a designated Regional EPA personnel
for resolution.
10.3 The Case No., Batch No., Sample Number, and Sample Matrix Type and Task
No. shall be used by the Contractor In all verbal or written
reports/correspondence, to Identify samples received under this
contract. All samples within the same batch shall be reported under
the Case and batch number assigned to that batch. Each batch of
samples analyzed shall be reported separately.
U- CONTRACTOR RESPONSIBILITY
11.1 The Contractor shall be required to receive and analyze samples seven
(7) days a week, including Saturdays, Sundays and holidays.
11.2 The Contractor shall accept all samples scheduled and delivered for
analyses provided that the total number of samples does not exceed a
maxlima of 60 full sample analyses per day per bid lot awarded
(excluding required automatic rerun analyses). Should the Contractor
elect to accept additional samples beyond the maximum required, the
Contractor shall remain bound by all contract requirements for analysis
of all samples accepted. The laboratory shall notify EPA of all Task 1
samples which become Task 2 so that this may be taken into
consideration when scheduling samples.
1 A Case consists of a finite, usually predetermined number of samples, collected over a
given period of time from a particular site.
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12. LABORATORY EVALPATION
12.1 The EFA Project Officer and/or designated representatives may conduct
an evaluation of the Contractor laboratory to ascertain that the
laboratory is meeting contract requirements. The following information
outlines the procedures which may be used by the Contract Officer or
his authorized representative in order to conduct a successful
evaluation of laboratories conducting dioxin analyses according to this
protocol. The evaluation process may consist of one or both of the
following: 1) analysis of a performance evaluation (PE) sample, and 2)
on-site evaluation of the laboratory to verify continuity of personnel,
instrumentation, and quality assurance/quality control functions.
12.2 An on-site laboratory evaluation is performed to verify that the
laboratory is maintaining the necessary minimum level in
instrumentation and levels of experience in personnel committed to the
contract and that the necessary quality control/quality assurance
activities are being carried out. It also serves as a mechanism for
discussing laboratory weaknesses identified through routine data
audits, PE sample analyses results, and prior on-site evaluation. The
Government will perform all such on-site inspections/evaluations in a
manner that will not unduly delay work the Contractor may have in
progress. Such inspections may or may not be prearranged with the
Contractor. A typical sequence of events for the on-site evaluations
is shown below.
12.3 Event Sequence for On-Site Laboratory Evaluation
12.3.1 Meeting with Laboratory Manager and Project Manager
Introduction; discuss purpose of visit; discuss problems with
data submitted by the laboratory.
12.3.2 Verification of Personnel
Review qualification of contractor personnel in place and
committed to project.
12.3.3 Verification of Instrumentation
Review equipment in place and committed to project. The
Contractor must demonstrate adequate equipment to ensure
capability to perform required analyses in the required time.
12.3.4 Quality Control Procedures
Walk through laboratory to review:
a. Sample receiving and logging procedures.
b. Sample and extract storage area.
c. Procedures to prevent sample contamination.
d. Security procedure for laboratory and samples.
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e. Safety procedures.
f. Conformance to written SOPs.
g. Instrument records and logbooks.
h. Sample and data control systems.
i. Procedures for handling and disposing of hazardous
materials.
j. Glassware cleaning procedures.
k. Status of equipment and its availability.
1. Technical and managerial review of laboratory operation and
data package preparation.
m. Procedures for data handling, analysis, reporting and case
file preparation.
n. Chain-of-custody procedures.
12.3.5 Identification of Needed Corrective Actions
Discuss with Project Manager the actions needed to correct
weaknesses identified during site inspection, PE sample
analysis or production of reports and documentation. Determine
how and when corrective actions will be documented, how and
when improvements will be demonstrated, and the contractor
employee responsible for corrective actions.
12.3.6 Review of Standard Operating Procedures (SOPs)
Review SOPs with Project Manager to assure that the laboratory
understands the dimensions and requirements of the program.
12.3.7 Previously Identified Problems
Check the most recent site evaluation results to verify that
all previously identified problems have been corrected.
12.3.8 Identification of New Problems
a. Discuss any weaknesses identified in the performance
evaluation sample analyses and reports.
b. Discuss any weaknesses identified in this site inspection.
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Task 1
Decision Tree for Samples
Identified for Task 1 Analysis
Task 1
Analysis
OK
QC Criteria
Report
Cleanup/
Reanalysis
Re-extraction/
Reanalysis
OK
QC Criteria
Report
OK
QC Criteria
Report Both Analyses
(Initiate Task 2 Analysis)
Report
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Task 2
Decision Tree for Samples
Identified for Task 2 Analysis
Task 2
Analysis
Lab Does Not
Accept
Not
Approved
Approval w/
Modification
Approved
Lab Accepts
Modification
TPO
Analysis
Report
Data
No
Action
QC Criteria
Stop Request
Lab Proposes
Analytical
Scheme
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TASK 2
PROPOSAL FORK
LABORATORY: PROPOSAL NO.:
DATE/TIME TASK 2 REQUEST:
CASE/BATCH:
SAMPLE ID: .
SUSPECTED PROBLEM:
LABORATORY PROPOSAL
PROPOSED ANALYTICAL SCHEME (attach any non-routine methods):
QA/QC (if different from TASK 1):
LAB MANAGER SIGNATURE:
DATE/TIME:
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TFO APPROVAL
APPROVE
APPROVE WITH MODIFICATIONS NOTED
DISAPPROVE
STOP REQUEST
MODIFICATIONS:
TPO SIGNATURE:
DATE/TIME:
LAB ACCEPTANCE OF MODIFICATIONS
(fill out only in instances where TPO has made modifications)
LAB MANAGERS SIGNATURE:
DATE/TIME:
*If modifications not accepted, the lab must submit a new proposal.
REPORTING SCHEDULE
ACCEPT MODIFICATIONS NOTED ABOVE
DO NOT ACCEPT MODIFICATIONS NOTED ABOVE*
START
DUE
DATE:
DATE:
TIME:
TIME:
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EXHIBIT B
REPORTING AND DELIVERABLES REQUIREMENTS
Page No.
Section I: Report and Data Deliverable Descriptions B-2
Section II: Contract Reports/Deliverable Distribution B-8
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SECTION I
REPORT AND DATA DELIVERABLE DESCRIPTIONS
The Contractor shall provide reports and other deliverables as specified In
the Contract Reports/Deliverable Distribution schedule In Section II. These
reports are described below and apply to both Task 1 and Task 2 deliverables.
All reports shall be submitted in legible form or resubmission shall be
required. All reports and documentation required, including chromatograms
and mass spectra, shall be clearly labeled with the Contractor's name, EPA
Contract number, EPA Case number, batch number and its associated EPA Sample
Nuaber(s) and applicable codes. If documentation is submitted without the
required identification, as specified above, resubmission shall be required
at no additional cost to the Agency.
The Contractor shall provide all reports and deliverables as described below.
The Contract Reporting Schedule specifies the number of copies required,
delivery schedule and distribution of all required deliverables.
1. ELECTRONIC DATA SUBMISSION (EDS')
1.1 HRGC and Tandem MS
The electronic data submission must be in the format provided by the
EDS software and include the following information:
1.1.1 Raw area response for ions 257, 259, 263, 268 for each of the
calibration standards.
1.1.2 Individual; mean; and overall mean relative response factors
for the 3-point calibration of unlabeled 2,3,7,8-TCDD.
1.1.3 Individual; mean; and overall mean relative response factors
for the isotopic surrogate standard (calculations based on high
level standard only).
1.1.4 Ion ratio for 257/259 for each calibration standard as well as
acceptable ion ratio range (+ 10%).
1.1.5 Raw area response for ions 257, 259, and 268 for the 20
replicate measurements of the blank (I.e., dilute sample
spiking solution), with the blank response, equivalent
concentration of native 2,3,7,8-TCDD, and Correction Factor
calculations.
1.1.6 The empirical limit of detection based on the above 20 blank
measurements.
1.1.7 The daily verification of the calibration, to include: raw
area response for ion 257, 259, 263, and 268; the mean RRF for
2,3,7,8-TCDD and the isotopic surrogate; and the % Difference
between the RRF of the daily verification and the initial
calibration for 2 , 3 , 7,8-TCDD.
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1.8 The laboratory data filename (to facilitate data retrieval).
1.9 The assigned Case and batch numbers for the sample set
reported.
1.10 The assigned sample number with corresponding code, as
appropriate, and the rerun code (A-automatic) appearing in the
Rerun Code field, if applicable.
o If more than one analysis is reported for one sample
number, a code shall be added to the end of the SHO sample
number on the data report for the rerun sample. This is
required to avoid duplicate sample numbers.
o Any automatic rerun analysis that is reported must have
either an "R" (rerun) or a "P" (PE sample rerun) code at
the end of the sample number, and requested reruns must
have a "Q" (requested rerun) code at the end of the sample
number, as described in Exhibit A, Sample Rerun
Requirements section.
1.11 The Regional sample identification number (as assigned by the
field sampling team).
1.12 The matrix of each sample.
1.13 The date and time of sample (batch) receipt.
1.14 Analytical date and time.
1.15 The raw area responses for ions 257, 259, 263, and 268 for each
sample.
1.16 Aliquot (in appropriate units per matrix) of sample analyzed.
Units are as follows: all solids - grams; water - liter; air -
cubic meter; and wipe - square centimeter.
1.17 The ion ratio for 257/259 for each sample.
1.18 The percent accuracy (i.e., analytical percent recovery) for
the surrogate standard.
1.19 The calculated value for native 2,3,7,8-TCDD, or detection
limit.
1.20 The result for the reagent blank(s).
1.21 The percent recovery of native 2,3,7,8-TCDD from any fortified
field blank samples.
1.22 The results for any PE samples.
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1.1.23 The results for any field blank(s).
1.1,24 The resulcs of all contractually required automatic rerun
analyses.
1.2 HRGC/LRMS
The electronic data submission must be In the format provided by the
EDS software and include the following Information:
1.2.1 Raw area response for ions 320, 322, 328, 332, and 334 for each
calibration standard.
1.2.2 Individual; mean; and overall mean relative response factors
for the 3-point initial calibration of native 2,3,7,8-TCDD and
the isotopic surrogate standard.
1.2.3 Ion ratio for 320/322 and 332/334 for each of the calibration
standards.
1.2.4 The daily or shift verification of the calibration to include:
raw area responses for ions 320, 322, 328, 332, and 334; mean
relative response factor for 2,3,7,8-TCDD and the surrogates;
and the % Difference between the RRF of the daily verification
and the initial calibration.
1.2.5 The laboratory file name (to facilitate data retrieval).
1.2.6 The Case and batch numbers for the sample set reported.
1.2.7 The sample number with corresponding code, as appropriate, and
the rerun code (A-automatic) appearing in the Renin Code field,
if applicable.
o Whenever more than one analysis is reported for one sample
number, for the rerun sample a code must be added to the
end of the sample number on the data report. This is
required to avoid duplicate sample numbers.
o Any automatic rerun analysis that is reported must have
either an "R" (rerun) or a "P" (PE sample rerun) code at
the end of the sample number, and requested reruns must
have a "Q" (requested rerun) code at the end of the sample
number, as described in Exhibit A, Sample Rerun
Requirements section.
1.2.8 The Regional sample identification number (as assigned by the
field sampling team).
1.2.9 The matrix of each sample.
1.2.10 The date and time of sample (batch) receipt.
1.2.11 Analytical date and time.
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1,2.12
The raw area responses for ions 320, 322, 328, 332, and 334 for
each sample.
1.2.13 Aliquot (in appropriate units per matrix) of sample analyzed.
Units are as follows: All solids - grams; water - liter; air -
cubic meter; and wipe- square centimeter.
1.2.14 The ion ratio for 320/322 and 332/334 for each sample.
1.2.15 The percent accuracy (i.e., analytical percent recovery) for
the surrogate standard.
1.2.16 The calculated value for native 2,3,7,8-TCDD for all positive
samples, and the detection limit or estimated maximum for all
non-detect samples.
1.2.17 The result for the reagent blank(s).
1.2.18 The percent recovery of native 2,3,7,8-TCDD from any fortified
field blank sample(s).
1.2.19 The results for any field blank(s).
1.2.20 The results for any PE samples.
1.2.21 The results of all contractually required automatic rerun
analyses.
2. SAMPLE DATA PACKAGE
Deliverables are identical to those listed under "Electronic Data
Submission," but must be submitted in hardcopy form (example of format
provided in Appendix A) along with the following supporting
documentation:
2.1 HRGC and Tandem HS
2.1.1 A sample delivery group (SDG) narrative (laboratory cover
letter) which contains the Case number, Batch number, EPA
Sample Numbers, Contract number and detailed documentation of
any quality control, sample, shipment and/or analytical
problems encountered in an SDG. Also included should be
documentation of any internal decision tree process used along
with a summary of corrective actions taken. The SDG narrative
must be signed in original signature by the Laboratory Manager
or his designate.
2.1.2 The mass chromatograms for all samples and standards. Include
both the real-time display data and reduced data showing limits
of integration. Include any computer generated response
tables. Also include mass chromatograms for daily column
performance check, if required.
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2.1.3 Documentation on the source and history of the native and
labeled 2,3,7,8-TCDD standards used.
2.1.4 Copy of the Dioxin Shipment Record and a copy of the
signed/dated chain-of-custody record.
2.1.5 Any other supporting documentation (i.e. , logbook records,
bench sheets, extraction notes or run logs).
2.2 HRCC/LRMS
2.2.1 An SDG narrative (laboratory cover letter) which contains the
Case number, Batch number, Sample Numbers, Contract number and
detailed documentation of any quality control, sample, shipment
and/or analytical problems encountered in an SDG, Also
included should be documentation of any internal decision tree
process used along with a summary of corrective actions taken.
The SDG narrative must be signed in original signature by the
Laboratory Manager or his designate.
2.2.2 The mass chromatograms far all samples and standards. Include
any computer generated response tables.
2.2.3 The mass chromatograms for the daily column performance check
(if required).
2.2.4 Documentation on the source of the native and labeled 2,3,7,8-
TCDD standards used.
2.2.5 Copy of the Dioxin Shipment Record and a copy of the
signed/dated chain-of-custody record.
2.2.6 Any other supporting documentation (i.e., logbook records,
bench sheets, extraction notes, or run logs).
3. SAMPLE EXTRACTS AND UNUSED SAMPLE PORTIONS
Unused portions of samples shall be retained by the Contractor 60 days
following electronic submission of data. Sample extracts shall be
retained by Contractor for a period of 28 days following electronic
submission of analytical data for water, solid, air and wipe samples.
The Contractor shall dispose of sample extracts and unused sample
portions after the above specified periods unless directed otherwise in
writing by the Administrative or Technical Project Officer or Sample
Management Office. When directed, the Contractor shall ship (at
Government's expense and in accordance with Department of
Transportation regulations) specific samples and/or extracts to a
specified location and person within 7 days of written request.
Remaining sample volume and extracts shall be disposed of by the
Contractor at Contractor's expense, in accordance with applicable
regulations concerning the disposal of such materials.
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4. WEEKLY SAMPLE STATUS REPORT
The Weekly Sample Status Report shall provide the status of all samples
the Contractor has received or has had in-house during the calendar
week. Required status information includes: samples received, samples
extracted, samples analyzed, samples rerun, Task number and samples
which required special cleanup. All samples shall be identified by
appropriate EPA Sample Number and Case/Batch numbers.
5. DAILY SAMPLE STATUS REPORT
In response to verbal request from the Sample Management Office or the
Project Officer, the Contractor must verbally provide sample status
information on a same-day basis. Should written confirmation be
requested, the Contractor must send daily sample status information in
a written form that same day using first-class mail service. Required
Daily Sample Status information shall include the items noted for the
Weekly Sample Status Report and, in addition, shall require information
on sample analysis reports in progress and analysis reports
submitted/mailed.
In accordance with applicable delivery requirements, the Contractor
shall deliver specified items per the following Contract Reporting
Schedule. Recipients include the CLP Sample Management Office, EMSL/LV
QA Division, USEPA Region/client, and NEIC Contract Evidence Audit
Team. Recipient addresses are given following the schedule.
6. DIOXIN SHIPMENT RECORD
Copy of Dioxin Shipment Record with lab receipt information and
original Contractor signature.
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SECTION II
CONTRACT REPORTS/DELIVERABLE DISTRIBUTION
lies Description
A. Electronic Data
Submission (EDS)
No. of
Copies Delivery Schedule
Task 1
2 By 6:00 a.a. (central time)
on the day following sample
receipt, except for air
samples; and by 6:00 a.m.
(central time) on the
second day following sample
receipt for air samples
Task 2
By 6:00 a.m. (CST) on the
second day following TPO
approval of the laboratory's
analytical proposal.
B, Sample Data Package 3
C. Sample Extracts Bid
Lot
liliitr Ibut ton
EMSL/ Region/
m _LX CUtnt HEI£
Unused Sample Bid
Portion Lot
7 days after EDS delivery
package deadline
Retain for 28 days after
EDS or submit within 7 days
after receipt of written
request by Project Officer
(P0) or Sample Management
Office (SM0) during that time
Retain for 60 days after
EDS or submit within 7 days
after receipt of written
request by P0 or SM0 during
that time
X X X
As Directed
As Directed
E. Weekly Sample
Status Report
F. Daily Sample
Status Report
G. Dioxln Shipment
Record
H. QA Plan
Within 5 days following X
end of each calendar week
As Directed As Directed
Within 3 days after sample X
receipt
Submit within 7 days after As Directed
receipt of written request
by the APO
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Item Description
No. of
Copies Delivery Schedule
Distribution
EMSL/ Region/
SMO LV Client NEIC
I Project Specific
SOPs
receipt
1 Within 7 days of contract
1 award. Amended or new SOPs
1 shall be submitted within
2 45 days after contract
1. Complete Set
2. QA SOPs
X
X
3. Evidentiary
SOPs
30 days
X
Note 1: Items A and B must include all contractually required automatic rerun results.
Note 2: EDS delivery schedule is based on sample receipt by the Contractor by 2:00 p.m.
(central time) on a given day. If the samples are shipped commercially and are
not delivered to the Contractor's facility by 2:00 p.m. on a given day, the
Contractor may accept the samples and be granted an hour-for-hour extension of
the EDS data delivery deadline to compensate for the delay in sample
availability. .
Note 3: All results are to be reported total and complete.
Note 4: Delivery shall be made such that all designated recipients (see Statement of
Work Exhibit B) receive the items on the same calendar day and, for Item A, at
the same time on the same calendar day.
Note 5: Time is cited in calendar days.
Note 6: For information on the QA Plan, refer to Exhibit D of this SOW.
Distribution Addresses:
(1) CLP Sample Management Office
P. 0. Box 818
Alexandria, VA 22313
For overnight delivery service, use street address:
300 N. Lee Street, Suite 200
Alexandria, VA 22314
(2) USEPA EMSL-LV QA Division
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
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(3) USEPA Region VII
Environmental Services Division
25 Funston Road
Kansas City, KS 66115
ATTN: Nicole Roblez
Telephone Number for Electronic Data Submission (913) 236-3986
The CLP Saaple Management Office, acting on behalf of the Project Officer, will
identify other Regions/Clients at the time sample analysis is scheduled.
(4) NEIC
Contract Evidence Audit Team (CEAT)
12600 West Colfax, Suite C310
Lakevood, CO 80215
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EXHIBIT C
ANALYTICAL METHODS AND QUALITY ASSURANCE
QUALITY CONTROL (QA/QC) PROCEDURES
-------
SECTION I
PART A - HRGC AND TANDEM MS METHOD (GC/MS/MS)
1. Scone and Application
1.1 This method is for use in the rapid determination of 2,3,7,8-
Tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) in water solids (soil,
sediment, dust, wood fiber, vegetation, and insulation), wipe, and air
samples when 2,3,7,8-TCDD is known to be the principal or only
tetrachlorodibenzo-p-dloxin isomer present. The method is not specific
for the 2,3,7,8-TCDD isomer, unless a capillary column which separates
that Isomer from the other 21 TCDD Isomers is employed. Co-eluting
tetrachlorodibenzodioxin isomers, if present, may present a positive
bias.
1.2 The method employs a tandem quadrupole mass spectrometer (MS/MS) as the
final detector. This method has been written for the conditions of the
Sciex TAGA or TCA 6000E instrument. Other MS/MS instruments are also
acceptable, as long as the quality control and detection limit
requirements are met.
1.3 The method incorporates isotope dilution techniques utilizing an
isotopically labeled TCDD congener which corrects for losses in the
analytical processing of the samples.
1.4 This method Is restricted to use only by or under the supervision of
analysts experienced in the use of gas chromatography/tandem mass
spectrometry.
1.5 The analytical range of analysis is 1-25 ng. However, this range can be
expanded on the upper end by analysis of additional calibration
standards.
Analvte CAS Number
2,3,7,8-Tetrachlorodibenzo-p-dioxin 1746-01-6
2. Summary of Methods
2.1 Water Samples
A one (1) liter aliquot of water is spiked with internal and surrogate
standards of isotopically labeled 2,3,7,8-TCDD. The spiked sample is
then extracted with 3 (60 mL) portions of methylene chloride using
separatory funnel techniques.
2.2 Solid Samples
A ten (10) gram aliquot of the solid sample is spiked with internal and
surrogate standards of isotopically labeled 2,3,7,8-TCDD. Anhydrous
sodium sulfate is added to any wet samples to form a free flowing sample
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prior to extraction with acetone/hexane using a jar extraction
technique.
2.3 Wipe Samples
The absorbent pads (consisting of a cotton gauze pad or filter paper)
are placed in an extraction jar. The pads are spiked with internal and
surrogate standards of isotopically labeled 2,3,7,8-TCDD. The sample
container is rinsed with an aliquot of the extraction solvent,
acetone/hexane, which is added to the extraction jar. The sample is
sonicated and then stirred using a magnetic stirrer for 30 minutes.
2.4 Air Samples
The sample (consisting of a glass fiber filter and PUF in a glass
cartridge) is spiked with internal and surrogate standards of
isotopically labeled 2,3,7,8-TCDD. The sample is then extracted in a
Soxhlet apparatus for 16 cycles with benzene (or dichloromethane).
2.5 A column chromatography cleanup procedure is provided which is
applicable to all methods as needed. However, it will usually be
possible to analyze the concentrated extract directly using capillary
column GC/MS/MS. Capillary column GC/MS/MS conditions are described
which allow for separation of TCDD from the bulk of the sample matrix
and allow for measurement of the TCDD in the sample extract.
Quantitation is based on the response of native TCDD relative to the
isotopically labeled TCDD internal standard. Performance is assessed
based on the results for the surrogate standard recoveries, EPA
performance evaluation (PE) samples, spike recoveries, method and field
blanks.
3. Interferences
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware and other sample processing hardware that lead to
discrete artifacts and/or elevated backgrounds at the ions monitored.
All of these materials must be routinely demonstrated to be free from
interferences under the conditions of the analysis by running laboratory
reagent (also referred to as method) blanks as described in Section 8.
3.2 The use of high purity reagents and solvents helps to minimize
interference problems, purification of solvents by distillation in all-
glass systems may be required along with Soxhlet extraction of certain
reagents.
3.3 Matrix interferences may be caused by contaminants that are co-extracted
from the sample. The extent of matrix interferences will vary
considerably from source to source, depending upon the nature and
diversity of the sample and matrix. 2,3,7,8-TCDD is often associated
with other interfering chlorinated compounds which are at concentrations
several magnitudes higher than that of 2,3,7,8-TCDD and may present
problems in analysis. Fine dust, insulation, and asphaltic containing
matrices contain the most interferences and may require more extensive
cleanup procedures for successful analysis. In some instances, the
quantity of internal standard added before analysis may need to be
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increased to accommodate the more extensive cleanup and dilutions
required.
3.4 The use of a tandem quadrupole mass spectrometer as the detector serves
to minimize the influence of many of these interferents.
4.0 Safety (Note: Information in this section on Safety is general guidance
rather than requirements of the contract)
It is not within the scope of the Statement of Work to require specific
safety procedures. General guidance has been included for informational
purposes only. The guidance does not exempt the contractor from
knowing or following any other State and/or Federal regulations
applicable to the handling and disposal of dioxin wastes. The following
safety practices are excerpted directly from EPA Method 613, Section 4
(July 1982 version).
4.1 The toxicity or carcinogenicity of each reagent used in this method has
not been precisely defined; however, each chemical compound should be
treated as a potential health hazard. From this viewpoint, exposure to
these chemicals must be reduced to the lowest possible level by whatever
means available. The laboratory is responsible for maintaining a
current awareness file of OSHA regulations regarding the safe handling
of the chemicals specified in this method, A reference file of material
data handling sheets should also be made available to all personnel
involved in the chemical analysis. Benzene and 2,3,7,8-TCDD have been
identified as suspected human or mammalian carcinogens.
4.2 Each laboratory shall develop a strict safety program for handling of
2,3,7,8-TCDD. The following laboratory practices are recommended:
4.2.1 Contamination of the laboratory will be minimized by conducting
all manipulations in a hood.
4.2.2 The effluents of sample splitters for the gas chromatograph and
roughing pumps on the GC/HS should pass through either a column
of activated charcoal or be bubbled through a trap containing
oil or high boiling point alcohols,
4.2.3 Liquid waste should be dissolved in methanol or ethanol and
irradiated with ultraviolet light with wavelength greater than
290 run for several days.(Use F 40 BL lamps or equivalent).
Analyze liquid wastes and dispose of the solutions when
2,3,7,8-TCDD can no longer be detected.
4.3 Dow Chemical U.S.A. has issued the following precautions (revised 11/78)
for safe handling of 2,3,7,8-TCDD in the laboratory:
4,3.1 The following statements on safe handling are as complete as
possible on the basis of available toxicological information.
The precautions for safe handling and use are necessarily
general in nature since detailed, specific recommendations can
be made only for the particular exposure and circumstances of
each individual use. Inquiries about specific operations or
uses may be addressed to the Dow Chemical Company. Assistance
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in evaluating the health hazards of particular plant conditions
may be obtained from certain consulting laboratories and from
State Departments of Health or of Labor, many of which have an
industrial health services. 2,3,7,8-TCDD is extremely toxic to
laboratory animals. However, it has been handled for years
without injury in analytical and biological laboratories.
Techniques used in handling radioactive and infectious
materials are applicable to 2,3,7,8-TCDD.
4.3.1.1 Protective Equipment: Throw-away plastic gloves,
apron or lab coat, safety glasses, and lab hood
adequate for radioactive work.
4.3.1.2 Training: Workers must be trained in the proper
method of removing contaminated gloves and clothing
without contacting the exterior surfaces.
4.3.1.3 Personal Hygiene: Thorough washing of hands and
forearms after each manipulation and before breaks
(coffee, lunch and shift).
4.3.1.4 Confinement: Isolated work area (posted with
signs), segregated glassware and tools plastic-
backed absorbent paper on benchtops.
4.3.1.5 Waste: Good technique includes minimizing
contaminated waste. Plastic bag liners should be
used in waste cans. Janitors must be trained in
safe handling of waste.
4.3.1.6 Disposal of Wastes: 2,3,7,8-TCDD decomposes above
800*C. Low-level waste such as the absorbent paper,
tissues, animal remains and plastic gloves may be
burned in a good incinerator. Gross quantities
(milligrams) should be packaged securely and
disposed of through commercial or governmental
channels which are capable of handling high-level
radioactive wastes or extremely toxic wastes.
Liquids should be allowed to evaporate in a good
hood and in a disposable container. Residues may
then be handled as above.
4.3.1.7 Decontamination: Personal - any mild soap with
plenty of scrubbing action: Glassware, Tools, and
Surfaces- Chlorothene NU Solvent(Trademark of the
Dow Chemical Company) is the least toxic solvent
shown to be effective. Satisfactory cleaning may be
accomplished by rinsing with Chlorothene, then
washing with any detergent and water. Dish water
may be disposed to the sewer. It is prudent to
minimize solvent wastes because they may require
special disposal through commercial sources which
are expensive.
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4.3.1.8 Laundry: Clothing known to be contaminated should
be disposed of with the precautions described under
"Disposal of Wastes." Lab coats or other clothing
worn in 2,3,7,8-TCDD work area may be laundered.
Clothing should be collected in plastic bags.
Persons who handle the bags and launder the clothing
should be advised of the hazard and trained in
proper handling. The clothing may be put into a
washer without contact if the launderer knows the
problem. The washer should be run through a cycle
before being used again for other clothing.
4.3.1.9 Wipe Tests: A useful method of determining
cleanliness of work surfaces and instruments is to
wipe the surface with a piece of filter paper.
Extraction and analysis by GC/MS can achieve a limit
of sensitivity of 0.1 ug per wipe. Less than 1 ug
•2,3,7,8-TCDD per sample indicates acceptable
cleanliness; anything higher warrants further
cleaning. More than 10 ug on a wipe sample
indicates an acute hazard and requires prompt
cleaning before further use of the equipment or work
space and indicates further that unacceptable work
practices have been employed in the past.
4.3.1.10 Inhalation: Any procedure that may produce airborne
contamination must be done with good ventilation.
Gross losses to a ventilation system must not be
allowed. Handling of the dilute solutions normally
used in analytical and animal work presents no
inhalation hazards except in case of an accident.
4.3.1.11 Accidents: Remove contaminated clothing
immediately, taking precautions not to contaminate
skin or other articles. Wash exposed skin
vigorously and repeatedly until medical attention is
obtained.
5. REQUIRED MATERIALS/APPARATUS. AND INSTRUMENTATION
5.1 Materials/Apparatus: All glassware shall be initially cleaned with
aqueous detergent and then rinsed with tap water, deionized water,
acetone, toluene, and methylene chloride. Other cleaning procedures may
be used as long as acceptable reagent blanks are obtained.
5.1.1 Sample Extraction
5.1.1.1 Water Samples
a. Separatory funnels, 2 L with Teflon stopcocks
b. Erlenmeyer flasks, 250 mL
c. Glass funnels
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d. Graduated cylinder, 1 L
5.1.1.2 Solid Samples
a. Electronic balance, capable of weighing wich an
accuracy of at least +/- 0.05 g
b. Ultrasonic bath
c. Magnetic Stir Plates
d. Teflon magnetic stir bars
e. Stainless steel spatulas
f. Anhydrous sodium sulfate
g. Glass jars with teflon lined lids, 8 oz.
5.1.1.3 Vipe Samples
a. Glass extraction jars, 500 mL beakers
b. Ultrasonic water bath, Bransonic 220 (or
equivalent)
c. Magnetic stirrer with teflon stir bar
5.1.1.4 Air Samples
a. Soxhlet extractors with large Friedricks-type
Pyrex brand glass condensers, or equivalent.
Improved Design extractors with a No. 71/60
female ground glass joint at the top and a No.
24/40 male ground glass joint at the bottom, a
No. 55/50 female ground glass joint Co a No.
71/60 male ground glass joint adaptor for
coupling the condenser to the extractor, and a
1.0 L flask with a No. 24/40 ground glass joint
as the receiving vessel. The extractor should
accommodate a 6.5 cm o.d. x 12.7 cb length glass
cartridge unit.
b. Heating mantle or block heater designed to
accommodate 1 L solvent flask
c. Refrigerated Water Recirculating Unit
5.1.2 Sample Concentration
a. Kuderna-Danish (K-D) concentrator tubes, 10 oL (Kontes K-
57005Q-1025 or equivalent); evaporation flasks, 500 bL
(Kontes K570001- 0500 or equivalent); and Snyder columns,
three-ball macro (Kontes K-503000-0121 or equivalent)
Rotary evaporation unit.
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b. Nitrogen blowdown apparatus, N-Evap Analytical Evaporator
Model 111 (or equivalent)
c. Water bath, heated, with concentric ring cover (if K-D
evaporation used)
5.1.3 Sample Cleanup
a. Disposable Pasteur pipets, 5 3/4" x 7 mm o.d.
b. Glass chromatography columns, 1cm X 20cm
c. Glass wool, silanized
d. Vacuum aspirator
5.1.4 Miscellaneous
a. Stainless steel spatulas
b. Vials, amber glass, 10 mL with Teflon-lined screw caps
c. Serum vials, 1.0 and 2.0 nL vials; cone shaped inside to
enable removing very small samples; heavy wall borosilicate
glass; with Teflon faced rubber septa and screw caps
d. 1-10 uL syringes
e. Disposable Teflon filters, 0.45 micron
f. Boiling chips, approximately 10/40 mesh
5.2 Instrumentation
5.2.1 Gas chromatograph, analytical system complete with all required
accessories including syringes, analytical columns, and gases.
The injection port must be designed for capillary columns.
Either split, splitless, or on-column injection technique may
be employed.
5.2.2 Tandem quadrupole mass spectrometer with GC transfer line and
glow discharge ion source (TAGA 6000, SCIEX, or equivalent.
5.2.3 Mass spectrometer, low resolution mass spectrometers (LRMS).
The mass spectrometer must be equipped with an electron
impaction source operated at 70 eV and be capable of acquiring
ion abundance data in real time Selected Ion Monitoring (SIM)
for groups of six or more ions.
5.2.4 GC/MS interface, any gas chromatograph to mass spectrometer
interface can be used that achieves the requirements of Section
8. Glass or glass-lined materials are recommended. Glass
surfaces can be deactivated by silanizing with
dichlorodimethylsilane. To achieve maximum sensitivity, the
exit end of the capillary column should be placed in the ion
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source. A short piece of fused silica capillary can be used as
the interface to overcome problems associated with
straightening the exit end of glass capillary columns.
5.2.5 Columns: 15 m long x 0.32 mm I.D. standard bore fused silica
capillary DB-5 with 1.0 micron film thickness
5.2.6 Compressed Gases: Zero grade air (from distillation, not water
hydrolysis), Ultra high purity nitrogen, and Ultra high purity
argon.
6. Standards. Solvents, and Reagents
6.1 Standards
6.1.1 Calibration Standard Solutions
The calibration standard solutions correspond to three toluene
or isooctane solutions containing unlabeled 2,3,7,8-TCDD at
varying concentrations and C^-2 , 3, 7,8-TCDD (the internal
standard, CAS RN 80494-19-5) at a constant concentration.
These solutions also contain CI4-2,3,7,8-TCDD (the surrogate
compound CAS RN 85508-50-5) at varying concentrations. These
are to be obtained from the Quality Assurance Materials Bank.
However, if not available, standards shall be obtained from
commercial sources and solutions prepared in the contractor
laboratory. Documentation of the source of standards shall be
provided, along with a demonstration, to the satisfaction of
the TPO, that these standards are equivalent to those provided
by EPA. (See Section IV).
As the stock supply of these solutions are exhausted, new
standard solutions will be made available by the Quality
Assurance Materials Bank. Replacement batches of the
calibration and sample spiking solutions may be at a slightly
different concentration. The laboratory shall notify SMO and
the Region prior to using any new calibration or sample spiking
solution whose concentration is different than the
concentrations listed in the contract. All opened calibration
standard solutions, spiking solutions and check mixtures must
be stored in a refrigerator/freezer and protected from light.
These standard solutions shall be checked frequently for signs
of evaporation. Standard solutions shall be removed and
allowed to equilibrate for approximately 30 minutes prior to
taking any aliquots.
6.1.1.1 The calibration standard solutions will have the
stated concentrations of unlabeled, internal, and
surrogate standards:
Calibration Solution 1 (CC1)
Unlabeled 2,3,7,8-TCDD - 0.2 ng/uL
13Cl4-2,3,7,8-TCDD - 1.05 ng/uL
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37Cl4-2,3,7,8-TCDD - 0.06 ng/uL
Calibration Solution 2 (CC2)
Unlabeled 2,3,7,8-TCDD - 1.0 ng/uL
13C12-2i3,7,8-TCDD - 1.05 ng/uL
37Cl£-2,3,7,8-TCDD - 0.11 ng/uL
Calibration Solution 3 (CC3)
Unlabeled 2,3,7,8-TCDD - 5.0 ng/uL
1^C12"2.3,7,8-TCDD - 1.05 ng/uL
37ClA-2,3,7,8-TCDD - 0.2 ng/uL
6.1.2 Sample Spiking Solution
6.1.2.1 The sample spiking solution shall be obtained from
the Quality Assurance Materials Bank. The toluene
or isooctane spiking solution will have the
following concentrations of internal and surrogate
standards:
13C12-2,3,7.8-TCDD " 0 61 fig/uL
37Cl4-2,3,7,8-TCDD - 0.1 ng/uL.
6.1.2.2 It is recommended that the spiking solution be
transferred to 1 mL serum vial(s) and sealed with a
septum and cap prior to each day's work for use in
spiking samples for that day. A new vial of Sample
Spiking Solution should be opened each day.
Leftover Sample Spiking Solution should not be
stored and re-used since evaporation of the spiking
solution may occur and the accuracy of results are
directly dependent on the addition of a known amount
of internal standard.
6.1.3 Column Performance Check Solution
6.1.3.1 The column performance check solution shall be
obtained from the Quality Assurance Materials Bank.
The mixture will contain: unlabeled 2,3,7,8-TCDD;
1,2,3,4-TCDD (CASRN 3074658-8); 1,4,7,8- TCDD (CASRN
40581-94-0); 1,2,3,7-TCDD (CASRN 67028-18-6);
1,2,3,8-TCDD (CASRN 53555-02-5); 1,2,7,8-TCDD (CASRN
34816-53-0); and 1,2,6,7-TCDD (CASRN 40581-90-6).
6.1.3.2. The column performance check solution will
only be necessary when tetra- dioxin isomer
specificity is required. (Section 8.13)
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6.1.4 Fortified Field Blank Spiking Solution
6.1.4.1 The fortified field blank spiking solution shall be
obtained from the Quality Assurance Materials Bank.
The toluene or iso-octane spiking solution will have
the following concentrations of unlabeled, internal,
and surrogate standards:
Unlabeled 2,3,7,8-TCDD - 0.1 ng/uL
13C12-2'3'7-8-tcdd - 0.61 ng/uL
37Cl4-2,3,7,8-TCDD - 0.1 ng/uL
6.2 Solvents
6.2.1 All solvents shall be pesticide grade or equivalent. The
following solvents are required:
Acetone Hexane
Acetonitrile Isooctane
Benzene Methyl Alcohol
Cyclohexane Toluene
Dichloromethane (Methylene Chloride)
6.3 Reagents
Sodium sulfate (ACS), granular, anhydrous (purified by heating
at 400*C for 4 hours in a shallow tray or methylene chloride
extraction).
Glass wool, silanized- extracted with methylene chloride or
benzene before use.
Silica gel for column chromatography, type 60, EM Reagent. 70-
230 mesh, or equivalent. Soxhlet extract with methylene
chloride for 21 hours, and activate in a foil covered glass
container for 24 hours at 130"C.
6.3.1
6.3.2
6.3.3
6.3.4 Activated alumina, acidic, form AG-4, 100-200 mesh, Soxhlet
extract for 21 hours with methylene chloride. Activate by
heating in a foil covered glass container for 24 hours at
190*C.
6.3.5 Carbopak C, 80/100 mesh, or equivalent.
6.3.6 Celite 545, not acid washed, or equivalent.
6.3.7 Carbopak C/Celite mixture - A mixture by weight of 18% Carbopak
C on Celite shall be prepared. This shall be mixed thoroughly
on a vortex mixer to break up large lumps. Check visually to
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assure that the mixture is uniform. Dry the mixture at 130*C
for 6 hours.
6.3.8 Reagent Water - Defined as water in which an interferent is not
observed at the method detection limit (MDL) of 2,3,7,8-TCDD.
7. Calibration
7.1 Calibration shall be done using the internal standard technique. In
this case, the internal standard is an isotope of the compound of
interest, and shall be used to determine the concentration of dioxin.
This technique is therefore, referred to as an isotope dilution GC/MS
method.
7.2 Inject 1-2 uL of each of the calibration standard solutions and acquire
selected reaction monitoring data for the following parent-daughter
transitions:
m/e - 320 -> 257
m/e - 322 -> 259
m/e - 328 -> 263
m/e - 332 -> 268
7.3 Relative response factors (RRF) for unlabeled 2,3,7,8-TCDD vs. the
Internal standard for triplicate determinations of each of the three
calibration standard solutions are calculated by Equation 1.
Equation 1: RRF for Native 2,3,7,8-TCDD
RRFn - (As)(Cis)/(Ais)(Cs)
where:
As - SIM response for 2,3,7,8-TCDD (m/e 257 + 259)
A^s - SIM response for ^C^" 2, 3, 7,8-TCDD internal standard
(m/e 268)
Cs - Concentration of 2,3,7,8-TCDD (ng/uL)
Cis - Concentration of the internal standard (ng/uL)
7.4 Relative response factors for the surrogate standard vs. the internal
standard for the triplicate determinations of the high level calibration
solution (CC3) are calculated by Equation 2.
Equation 2 : RRF for Surrogate Standard ^Cl^.-2 , 3 , 7 , 8-TCDD
R*FSS - (Asscis/^Ais^ss)
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where:
17
Ass - SIM response for Cl^-2,3,7,8-TCDD surrogate standard
(m/e 263)*
A^s - SIM response for ^^C|2"2,3,7,8-TCDD internal standard
(m/e 268)
Cjs - Concentration of internal standard (ng/uL)
Css - Concentration of surrogate standard (ng/uL)
7.5 Each of the calibration standard solutions shall be analyzed in
triplicate, and the variation of the RRF values for each concentration
level shall not exceed 10% relative standard deviation (RSD) for TCDD,
If the three mean RRF values for each compound do not differ by more
than + 10% RSD, the RRF can be considered to be independent of analyte
quantity for the calibration concentration range, and the mean of the
three RltF's shall be used for the concentration calculations. The
overall mean is termed the calibration factor.
7.6 In the case of the surrogate standard ^C^-2,3,7,8-TCDD, the variation
of the three RRF values for the high level calibration solution (CC3)
shall not exceed 10* RSD. The mean of the three RRFs shall be used for
concentration calculations. The overall mean is termed a calibration
factor.
7.7 The calibration factor for unlabeled 2,3,7,8-TCDD must be verified on
each work shift of 12 hours or less by the analysis of the calibration
standard solution 1 (CC1). If the RRF for the standard differs from
the calibration factor by more than 10%, the entire calibration must be
repeated and a new calibration factor determined. The overall mean
RRF determined during the initial calibration is used in all
calculations.
The verification is only required for 2,3,7,8-TCDD. The lab should,
however, monitor the response of the surrogate compound as a
preventative action measure.
7.8 The theoretical ratio of the m/e 257 to 259 ions for native 2,3,7,8-TCDD
Is 1.02. However, in practice this ratio will differ from the
theoretical due to the very low resolution used in both analyzing
quadrupoles for this type of analysis. The ratio shall therefore, be
determined empirically by Equation 3.
Subtract 0.0108 of any 257 response from the 263 response to correct for
contribution of 2,3,7,8-TCDD to the 263 response.
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Equation 3: Ion Ratio of 2,3,7,8-TCDD
Ratio — ^257/^259
where:
a257 " Area response for ion m/e 257
A259 — Area response for ion m/e 259
7.9 The mean of the 257/259 ratios calculated for each of the nine
calibration solutions shall be used for comparison purposes for
qualitative identification of 2,3,7,8-TCDD. An acceptable ion ratio
range is determined by taking + 10% of the mean.
7.10 It has been found that the Sample Spiking Solution also gives responses
for the 257 and 259 daughter ions corresponding to 2,3,7,8-TCDD. These
contributions shall be subtracted out for each sample. In order to
determine this correction factor, twenty 1-2 uL injections of the Sample
Spiking Solution shall be made and the ratio of the area responses for
the sum of the m/e 257 and m/e 259 ions vs. the m/e 268 ion shall be
calculated. Twenty separate ratios shall be determined. This ratio
will change with each lot provided and shall be determined each time a
new spiking solution lot is introduced.
Equation 4: Blank Response (B) of Sample Spiking Solution
B - Afc/Als
where:
Afc - SIM response for spiking solution (m/e 257 + m/e 259)
A^s - SIM response for internal standard in spiking
solution (m/e 268)
The correction factor for the blank contribution to sample response is
then calculated as the mean of the 20 blank responses as follows:
Equation 5: Correction Factor (C.F.) for Blank
Contamination
C.F. - V £
n-1 n
where:
B - Sum of the individual blank response determined in
Equation 4
n - Number of replicate measurements of the blank response
(20 are required for initial determination)
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7.11 Empirical Detection Limit
The empirical limit of detection shall be calculated based on the
variability of the blank responses. The blank responses correspond to
those obtained from repeat injections of the Sample Spiking Solution.
Each blank response must be converted to an equivalent concentration of
2,3,7,8-TCDD. If necessary, the Sample Spiking Solution can be diluted
before injection. The ratio of responses should not be affected by
dilution.
Equation 6: Conversion of Blank Response to an Equivalent
Concentration of 2,3,7,8-TCDD
Cfc - Equivalent concentration of 2,3,7,8-TCDD in blank
(Sample Spiking Solution) (ng/g)
Ab - SIM response for the blank (m/e 257 + m/e 259)
A^s - SIM response for internal standard (m/e 268)
RRFn - Relative response factor previously determined for
2,3,7,8-TCDD (Equation 1)
Qis ~ Quantity of internal
standard added to each sample, ng
W - Equivalent amount of sample routinely analyzed, g
The standard deviation of the blank response (in concentration units)
must then be calculated.
Equation 7: Standard Deviation of the Blank Responses
S^ - Standard deviation of the blank responses (ng/g)
- Blank response in concentration units (calculated
using Equation 6
Cjj - Average blank response
n - Number of replicate blank results used (20 are
required)
Cb " (Ab)(Qis)/(Als)(RRFn)(U)
where:
1/2
where:
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Finally, the limit of detection shall be calculated for the standard
deviation of the blank.
Equation 8: Limit of Detection Based on "Well-Known" Blank
LOD - 2(t)(Sb)
where:
LOD - Limit of detection
t - The 10% point of the t statistic for a double-sided
table with n-1 degrees of freedom (where n is equal to
the number of blank results used). The LOD shall be
calculated based on at least 20 replicate blank (i.e.,
Sample Spiking Solution) analyses. For n-20, t-1.72.
The detection limit calculated from Equation 8 shall be less than the
required detection limit of 1.0 ng for water, wipe, and air samples and
0.3 ng/g for solid samples.
8. Quality Control Requirements
8.1 The following quality control (QC) requirements are listed in the order
that they shall be run. Section 8.2 and 8.3 shall be met prior to the
analysis of the samples. Section 8.4 shall be included with each batch
of real samples that is run in one 12-hour time period or each shift.
Sections 8.S - 8.11 shall be met for each set of samples analyzed.
Sections 8.6 - 8.8 shall be met for each set of samples if submitted by
the sampling team. For Sections 8.12 and 8.13, the laboratory will be
given 48 hours prior notice if these requirements are to be implemented.
NOTE: If any of these criteria (except for sample Identification) are
not met, it shall be considered an automatic rerun, and therefore, part
of the principal sample analysis and not billable as a separate
analysis. In the case of Section 8.8, the TPO will notify the
laboratory of any non-acceptable performance evaluation sample results
and the laboratory will be given additional time (another reporting
period) to perform the reanalysis. These reanalyses will also be
considered non-billable. See Exhibit A for specific requirements
regarding reruns.
8.2 An initial calibration must be performed using calibration standard
solutions with varied amounts of native TCDD. Calibration for the
surrogate standard will be based on the high level calibration standard.
The criteria given in Section 7 shall be met or the calibration must be
repeated ( % RSD <10 %). All samples associated with an unacceptable
initial calibration shall be reanalyzed. All calibration standard
solution analysis shall meet the positive identification criteria
outlined in item Section 8.10 for TCDD.
Reference - Currie, Lloyd A. "Limits for Qualitative Detection and
Quantitative Determination" Anal. Chem. 40, 3, 586-593, 1968.
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8.3 Initially, 20 replicate determinations of the Sample Spiking Solution
shall be analyzed and a correction factor calculated. Twenty separate
ratios shall be determined (Equation 4) and used in calculating the
correction factor (Equation 5).
8.4 A 1-point calibration check using calibration standard solution 1 (CC1)
shall be run once every 12 hours or every shift, whichever is more
frequent. If the RRF values from the calibration check differ by more
than + 10% from that of the overall mean RRF previously determined from
the initial 3-point calibration, then a new initial calibration shall be
performed. The calibration check for the surrogate is not necessary
unless the surrogate recoveries appear biased and/or consistently fall
outside the 60-140% control limits. All calibration check standard
analysis shall meet the positive identification criteria outlined in
Section 8.10 for TCDD,
8.5 A laboratory "reagent blank" shall be prepared and analyzed along with
every batch of 28 or fewer samples and for each matrix. A reagent blank
is performed by executing all of the specified extraction steps, except
for the introduction of a real sample (In the case of water analysis 1 L
of pure deionized water shall be used), The reagent blank shall also be
dosed with the internal standard and surrogate standard. Results for
the reagent blank shall be calculated the same way as samples. This
includes correction for the Sample Spiking Solution contribution as
indicated in Equation 9. A positive response of > 1.0 ng for water,
wipe, and air samples, 0.3 ng/g for solid samples not containing
asphalt, and 0.7 ng/g for solid samples containing asphalt of native
TCDD must be followed by reinjection. If still positive, re-extraction
and reanalysis of all associated positive samples including the reagent
blank shall be performed.
8.6 Field blanks may be submitted for analysis. The field blank will
consist of a TCDD free media and shall be analyzed as a regular sample
using the same spiking solution and sample preparation procedures. A
positive response of > 1.0 ng for water, wipe, and air samples, 0.3 ng/g
for solid samples not containing asphalt, and 0.7 ng/g for solid samples
containing asphalt of native TCDD must be followed by reinjection. If
still positive, all positive samples associated with the field blank,
must be re-extracted and reanalyzed including the field blank
8.7 A sample may be provided by EPA designated to be spiked by the
laboratory with native TCDD(matrix spike). The Fortified Field Blank
Spiking Solution should be used to spike the designated sample. The
recovery shall be within 60-140% or the analysis is stopped and all
related samples and the matrix spike sample shall be re-extracted and
reanalyzed. The following spiking levels shall be used: water, 10 ng/L;
solids, 1 ng/g; wipe, 5 ng/sample; and air, 10 ng/sample.
8.8 The laboratory may be given performance evaluation (PE) samples by EPA
to run with each batch of samples. The results from these performance
evaluation samples will be evaluated by EPA. If a result is not within
the acceptance criteria set by EPA, the laboratory will be notified and
all samples in the batch associated with the PE sample must be
reanalyzed.
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8.9 Each sample shall be dosed with the Sample Spiking Solution containing
internal standard and surrogate standard. The specific amount is listed
in Section 10. The surrogate recovery must be within 60-140% or the
sample shall be re-extracted and reanalyzed.
8.10 The following qualitative requirements shall be met in order to confirm
the presence of native 2,3,7,8-TCDD.
8.10.1 The retention time of the peak shall be within ±3 seconds of
the retention time for the internal standard.
8.10.2 The 257/259 ratio shall be within the range (±10) established
in Section 7 based on the initial calibration ratios.
8.10.3 The ion response at 257 and 259 shall be present and maximize
together. The signal to noise (S/N) ratio shall be 2.5 to 1 or
better for both daughter ions. (Determine the noise level by
measuring the random peak to valley signal present on either
side within 20 scans of the 2,3,7,8-TCDD retention window. The
2,3,7,8-TCDD signal shall be at least 2.5 times larger than
this). Example of the S/N measurement is given in Figure 1.
8.10 For those samples giving non-detect results, the result shall be less
than the required limit of detection. Otherwise the analysis shall be
stopped and interferences Identified and corrected using specified
sample cleanup procedures until the detection limit is met. Likewise,
those samples for which a peak is present but does not meet
identification criteria are calculated, are subject to the same
detection limit requirement. The required detection limits are 1.0 ng
for water, wipe, and air samples; 0.3 ng/g for all solid samples not
containing asphalt; and 0.7 ng/g for solid samples containing asphalt.
8.11 For each sample and standard solution analyzed, the internal standard
shall be present with a S/N ratio of at least 10 to 1 based on the m/e
268 ion response.
8.12 A laboratory duplicate analysis may be designated by EPA for a specific
sample. When designated, the laboratory shall prepare and analyze the
samples in duplicate. The relative percent difference for the
laboratory duplicate cannot exceed 40%.
8.13 Isomer Specificity: The contractor will be given 48 hours prior notice
when isomer specificity is needed. Isomer specificity shall be
demonstrated initially and verified once per 12-hour work shift. The
verification consists of injecting a mixture containing TCDD isomers
which elute close to 2,3,7,8- TCDD. This mixture will be provided by
EPA. It contains seven TCDD isomers (2378, 1478, 1234, 1237, 1238,
1278, and 1267), including those isomers which are known to be the most
difficult to separate on SP2330/SP2340 columns and similar columns
containing cyanoalkyl type liquid phases. The Column Performance Check
Solution shall also contain both isotopically labeled 2,3,7,8-TCDD
standards. The solution shall be analyzed using the same chromatographic
conditions and mass spectrometric conditions as is used for the samples
and standards. The 2,3,7,8-TCDD shall be separated from interfering
isomers, with no more than a 25% valley relative to the 2,3,7,8-TCDD
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peak. An example of Che expected chromatogram for the TCDD column
performance check solution is given in Figures 2 and 3.
8.13a Draw a baseline for the isomer cluster representing 1478, 2378, 1237,
1238, and 1234-TCDD. Measure the distance x from the baseline to the
valley following the 2,3,7,8-TCDD peak (use the valley preceding the
2,3,7,8-TCDD peak if it is the least resolved). Measure the distance y
from the baseline to the apex of the 2,3,7,8-TCDD peak. Distance x
divided by distance y times 100 is the percent valley which shall not
exceed 25%. An example is given in Figures 2 and 3.
9. Preservation and Handling
9.1 Water Samples (Note: This section (9.1) on collecting water samples is
provided as information only to the Contract Laboratory)
9.1.1 Two 1 L containers of sample should be collected. 1 L will be
used for the primary analysis and the second liter shall be
reserved for duplicate analysis and sample reanalysis. In some
instances this amount of sample may not be available. The
laboratory shall use the entire sample if less than 1 L. All
samples shall be iced or refrigerated at 4*C and protected from
light.
9.1.2 If residual chlorine is present in the water, the field sampler
should add 80 mg of sodium thiosulfate per liter of sample and
mix well.
9.1.3 All water samples should be collected in duplicate to allow for
duplicate sample analysis and sample reruns.
9.2 Solid Samples
9.2.1 All solid samples will be provided in an 8 ounce jar or
Whirlpak bag. When received in the laboratory, the sample
shall be thoroughly mixed in the jar using a stainless steel
spatula. The spatula shall be used to break up large clumps of
solids while mixing to achieve a homogeneous sample.
9.2.2 A 10 gram aliquot sample shall be taken and mixed with sodium
sulfate. The 10 gram aliquot shall be representative of the
entire sample. Thus, large stones or other particles which are
uncharacteristic of the sample shall not be included in the
aliquot.
9.2.3 Solid samples may be stored at ambient conditions as long as
temperature extremes (below freezing or above 90*C) are
avoided. Samples shall be protected from light to avoid
photodecomposition.
9.3 Wipe Samples
9.3.1 Wipe samples will consist of 1 or 2 absorbent pads in a 240 mL
jar. The absorbent pads may be either cotton gauze or Whatman
filter paper.
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9.2.3 Wipe samples may be stored at ambient conditions as long as
temperature extremes (below freezing or above 90*C) are
avoided. Samples shall be protected from light to avoid
photodecomposition.
9.4 Air Samples
9.4.1 Air samples will consist of two parts: 1) a 2-inch diameter
polyurethane foam plug (FUF) contained in a borosilicate glass
tube with a coarse stainless steel support screen and 2) a 4-
inch glass or quartz fiber filter. The two parts will be
placed together and wrapped in aluminum foil.
9.4.2 Air samples may be stored under ambient conditions as long as
temperature extremes (below freezing or above 9Q*F) are
avoided. Samples shall be protected from light to avoid
photodecomposition.
10. Sample Extraction
10.1 Water Samples
10.1.1 Mark the meniscus on the side of the sample bottle for later
determination of sample volume. Pour the sample into a 2-L
separatory funnel.
10.1.2 Dilute 50 uL of Sample Spiking solution (containing both
internal and surrogate standards) in 1 mL of acetone. Then
quantitatively transfer the dilute spiking solution to the
sample in the separatory funnel. (Add the Fortified Field
Blank Spiking Solution to the matrix spike sample if a matrix
spike sample has been included in the batch).
10.1.3 Add 60 mL methylene chloride to the sample bottle, seal, and
shake 30 seconds to rinse the inner surface. Transfer the
solvent to the separatory funnel and extract the sample by
shaking the funnel for two minutes with periodic venting to
release excess pressure. Allow the organic layer to separate
from the water phase for a minimum of 10 minutes. If the
emulsion interface between layers is more than one-third the
volume of the solvent layer, the analyst shall employ
mechanical techniques to complete the phase separation. The
optimum technique depends upon the sample but may include
stirring, filtration of the emulsion through glass wool,
centrifugation, or other physical methods. Collect the
methylene chloride extract in a 250-mL Erlenmeyer flask.
10.1.4 Add a second 60-mL volume of methylene chloride to the sample
bottle and repeat the extraction procedure a second time,
combining the extracts in the Erlenmeyer flask. Perform a
third extraction in the same manner.
10.1.5 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-
mL concentrator tube to a 500-mL evaporative flask. Other
concentration devices or techniques nay be used in place of the
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K-D if the quality control and detection limit requirements are
met.
10.1.6 Dry the extract by passing it through a funnel containing
anhydrous sodium sulfate on top of glass wool. Collect the dry
extract in the K-D concentrator. Rinse the Erlenmeyer flask
with 3 (10 mL) portions of methylene chloride to assure
quantitative transfer.
10.1.7 Add one or two clean boiling chips to the evaporation flask and
attach a three-ball Snyder column. Prewet the Snyder column by
adding about 1-mL methylene chloride to the top. Place the K-
D apparatus on a hot water bath (60° to 65*C) so that the
concentrator tube is partially Immersed in the hot water, and
the entire lower rounded surface of the flask is bathed with
hot vapor. Adjust the vertical position of the apparatus and
the water temperature as required to complete the concentration
in 15 to 20 minutes. At the proper rate of distillation the
balls of the column will actively chatter but the chambers will
not flood with condensed solvent. When the apparent volume of
liquid reaches 1 -2 mL remove the K-D apparatus from the water
bath and allow it to drain and cool for at least 10 minutes.
10.1.8 Concentrate the extract to 1-2 mL on the steam bath.
10.1.9 Quantitatively transfer the extract to a vial and concentrate
using a gentle stream of nitrogen. Evaporate the solvent until
the volume of the solution is 0.5-1 mL.
10.1.10 Determine the original sample volume by refilling the sample
bottle to the mark with water and measuring the volume in a
1000 mL graduated cylinder. Record the sample volume to two
significant figures.
10.2 Solid Samples
10.2.1 Transfer a representative 10-gram (weighed to 3 significant
figures) aliquot of sample directly into the extraction jar.
In the case of those samples known or suspected of containing
asphalt, weigh a 1-2 gram aliquot of sample. Each sample shall
be scooped with an individual stainless steel spatula to avoid
cross contamination. An attempt shall be made to weigh out an
aliquot representative of the whole sample and may involve
physical nixing of the sample. Excessively wet samples shall
be centrifuged and moisture decanted, prior to weighing,
10.2.2 Crush the larger pieces of solid with the spatula. Leaving
the spatula in the jar, cover the mouth of the jar with
teflon-lined lid.
10.2.3 Add 100 uL of Sample Spiking Solution (containing both internal
and surrogate standards.) This will result in the addition of
61 ng of internal standard and 10 ng of surrogate standard. For
those samples known or suspected of containing asphalt, add 200
uL of the Sample Spiking Solution (122 ng internal standard and
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20 ng surrogate standard). Add the spiking solution directly
to the solid spreading it over several sites on the surface of
the solid. Hake certain that the standard has absorbed into
the solid before continuing the procedure. (Add the Fortified
Field Blank Spiking Solution to the matrix spike sample if a
matrix spike sample has been included with the batch).
10.2.4 Add 20 grams of purified anhydrous sodium sulfate to the sample
after the spiking solution has dried in the sample. Mix
thoroughly using a stainless steel spatula. Allow the mixture
to stand for 5 minutes then continue with the procedure.
10.2.5 Add SO mL of 10% acetone/hexane solvent solution to each jar.
Allow the solvent to wash down over the spatula. Remove the
spatula from the jar. Add a magnetic stir bar and cap the jar
tightly. Place the jar in an ultrasound water bath (Bransonic
220 or equivalent). The bath shall be at room temperature.
Adjust water level to above the level of the solvent. Sonicate
for 30 seconds. Remove for 30 seconds. Repeat this
alternating procedure two more times being certain that the
temperature does not rise above room temperature.
10.2.6 Place the sample on a stirring plate. Adjust the speed of the
stir bar to obtain a moderate mixing of the solid sample and
solvent. Stir all samples for 1 hour. Other mixing/stirring
devices are acceptable as long as all quality control and
detection limit requirements are met.
10.2.7 Assemble the Kuderna-Danish (K-D) concentrator by attaching a
10-mL concentrator tube to 500 mL evaporation flask. Other
concentration devices or techniques may be used in place of the
K-D concentrator if quality control and detection limit
requirements are met.
10.2.8 Remove the jars from the stirrer. Remove each of the caps and
rinse the inner surface with hexane so that the solvent washes
back into the sample container. Remove the magnetic stir bar
and rinse with hexane so that the solvent washes back into the
jar.
10.2.9 Place a glass funnel containing #4 Whatman filter paper in each
K-D flask. Place anhydrous sodium sulfate in each funnel.
Carefully decant the extract through the funnel into the
Kuderna-Danish flask. Rinse the sample jar with a small volume
of hexane. Decant the rinse into the funnel. Rinse the funnel
and paper with hexane and remove both after rinsing.
10.2.10 Add 1-2 mL of isooctane to the extract in the K-D flask.
10.2.11 Add one or two clean boiling chips to the evaporation flask and
attach a three-ball Snyder Column by adding about 1 mL hexane.
Place the K-D apparatus on a hot water bath (60° - 65°C) so
that the concentrator tube is partially immersed in the hot
water, and the entire lower rounded surface of the flask is
bathed in hot vapor. Adjust the vertical position of the
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apparatus and the water temperature as required to complete the
concentration in 15 to 20 minutes. At the proper rate of
distillation the balls of the column will actively chatter but
the chambers will not flood with condensed solvent. When the
apparent volume of liquid reaches 1-2 mL remove the K-D flask
from the water bath and allow it to drain and cool for at least
10 minutes.
10.2.12 Concentrate the extract to 1-2 mL on the steam bath.
10.2.13 Quantitatively transfer the extract to a vial and concentrate
using a gentle stream of nitrogen. Evaporate the solvent until
the volume of the solution is 0.5 - 1 mL.
10.3 Wipe Samples
10,3.1 Transfer the absorbent pad(s) (cotton gauze pad or filter
paper) to the extraction jar.
10.3.2 Add 50 mL of Sample Spiking Solution to the absorbent pads over
several sites on the surface. (Use Fortified Field Blank
Spiking Solution for the matrix spike if a matrix spike sample
has been included with the batch).
10.3.3 Rinse out the sample container with two 10-mL portions of
extraction solvent (10% acetone in hexane v/v) and transfer
each portion to the extraction jar.
10.3.4 Add to the extraction jar 30 mL of extraction solvent while
rinsing the spatula. Be certain that the absorbent pad(s) are
completely covered by solvent. Add more solvent if necessary.
Place the jar in an ultrasound water bath (Bransonic 220 or
equivalent). (Caution: This operation should be performed in a
hood.) Bath should be at room temperature. Adjust the water
level to above the level of the solvent. Sonicate for 30
seconds. Remove for 30 seconds. Repeat this alternating
procedure two more times, being certain that the water
temperature does not rise above room temperature.
10.3.5 Stir on magnetic stirrer for 30 minutes.
10.3.6 Decant extract through a glass funnel fitted with hexane-rinsed
filter paper (Whatman #4) into a Kudema-Danish reservoir. Add
1 mL isooctane and teflon boiling chips. Other concentration
devices may be used in place of the K-D concentrator if quality
control and detection limit requirements are met.
10.3.7 Concentrate the extract volume to 1-2 mL on a steam bath.
10.3,8 Quantitatively transfer the extract to a vial and concentrate
using a gentle stream of nitrogen. Evaporate the solvent until
the volume of the solution remaining is 0.5-1 mL.
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10.4 Air Samples
Place the entire glass cartridge containing the polyurethane
foam plug (PUF) and filter paper into the Soxhlet extractor.
Add SO uL of Sample Spiking Solution depositing the spiking
solution In several spots on both the filter paper and PUF.
(Use Fortified Field Blank Spiking Solution for the matrix
spike if a matrix spike sample has been included with the
batch).
Introduce enough benzene (methylene chloride nay be substituted
if comparability data indicates acceptable results) into the
extractor until the cartridge is completely immersed and the
solvent begins to siphon down. Add an additional 100- 200 mL
of benzene. Extract for 24 hours or until 16 complete cycles
have been achieved. The extraction rate should be such that
the solvent vapor (condensation line) does not exceed one-
fourth the way up the condenser.
Remove benzene in a rotary evaporator. (If methylene chloride
has been used, the laboratory may concentrate the sample using
K-D concentration techniques.) When the volume is reduced to
about 2-3 mL, quantitatively transfer the extract to a vial.
Use hexane to rinse the walls of the flask for quantitative
transfer of the extract. Exchange the solvent to hexane using
the evaporator prior to the column cleanup.
11• Cleanup Procedures
11.1 The need for cleanup is indicated when a particular extract does not
meet the quality control or detection limit requirements. It has been
noted that dust and asphalt samples often contain matrix interferences
which co-elute with native TCDD and should be processed using both
cleanup procedures. In the case of asphalt-containing solid samples,
successive columns of the same type may be required to remove all
interferents. Two cleanup procedures are given below.
11.2 Packing of the columns shall be done less than 1 1/2 hours prior to
sample elution. Absorbent materials in the columns will remain
^relatively inert (i.e. unreactive) for that time period if the solvent,
hexane, has been added immediately after packing. Note, however, that
the silica gel columns are most reactive and they shall be prepared
last. Special attention shall be paid to removing bubbles from the
solvent soaked absorbent. Columns are efficiently handled on two tiered
multi-clamp racks.
11.3 It is also acceptable to use the modified Option A and D cleanup
procedures outlined in Section 11 of the HRGC and Tandem MS method.
Note, however, that the modified cleanup procedures are not as rigorous
and may not remove enough of the interferences to meet required quality
control and detection limit requirements.
10.4.1
10.4.2
10.4.3
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11.4 OPTION A (Silica Gel/Aluraina)
Column 1: Place 1.0 g of silica gel into a 1 cm x 20 cm glass column
and tap the column gently to settle the silica gel. Add 4 g sulfuric
acid impregnated silica gel, and top off with 0.5 - lg sodium sulfate.
Tap column gently after each addition.
Column 2: Place 4 g of acidic alumina into a 1 cm x 20 cm glass column
and tap the column gently to settle the alumina. Add a 1 cm layer of
purified sodium sulfate to the top of the alumina.
11.4.1 Add hexane to each column until the packing is free of channels
and air bubbles. A small pressure (5 psi) of clean nitrogen
can be used if needed. Do not let columns dry before using.
11.4.2 Quantitatively transfer the hexane sample extract from the
concentrator tube to the top of the silica gel in Column 1.
Rinse the concentrator tube with three 1-mL portions of hexane
and transfer them to the column.
11.4.3 With 40 mL of hexane, elute the extract from Column 1 directly
into Column 2 containing the alumina.
11.4.4 Add 25 mL of hexane to Column 2 and elute until the hexane
level is just below the top of the sodium sulfate; discard the
eluted hexane.
11.4.5 Add two 20-mL aliquots of 20% methylene chloride/ 80% hexane
(v/v) to Column 2 and collect the eluate.
11.4.6 Reduce the volume of the eluate with a gentle stream of
filtered dry nitrogen to 1-2 mL.
11.4.7 Proceed to Option D cleanup or store for GC/MS analysis. Seal
the vial with a Teflon-lined septum and cap prior to storing.
11.5 OPTION D (Carbopak)
11.5.1 Thoroughly mix 3.6 g of Carbopak C (or equivalent) with 16.4 g
of Celite 545 (or equivalent) in a 40 mL vial and activate by
heating in an oven at 130°C for 6 hours. Store in a
dessicator. CAUTION: Check each new batch.of mixed
Carbopak/Celite to ensure recovery of > 50%.
11.5.2 Insert a small plug of glass wool into a disposable Pasteur
pipet approximately 15 cm x 7 mm. Apply suction with a vacuum
aspirator attached to the pointed end of the pipet, and add the
Carbopak/Celite mixture until 2 cm of packing is obtained.
11.5.3 Pre-elute the column with successive additions of the following
solvents:
-2 mL toluene
-1 mL of 75:20:5 methylene chloride/methanol/benzene (v/v/v)
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•1 mL 50:50 cyclohexane/methylene chloride (v/v)
While the column Is still wet with hexane, add the sample
extract. Elute the column with the following sequence of
solvents and discard the eluates:
-2 mL hexane
-1 mL 50:50 cyclohexane/methylene chloride (v/v)
-1 mL 75:20:5 methylene chloride/methanol/benzene (v/v/v).
Elute with 2 mL of toluene and collect the eluate, which
contains the TCDD, Transfer to a 1 mL amber mini-vial and
concentrate further as necessary.
Proceed to GC/MS analysis or store in refrigerator. Seal the
vial with a Teflon-lined septum and cap prior to storing.
12. GC/MS/MS Analysis
12.1 Table 1 provides guidelines for operating conditions using capillary
columns. The 15 m DB-5 column has been used for chromatography which is
not isomer specific. Other GC columns may be used which are isomer
specific, as long as all quality control and detection limit
requirements are met. Use Isomer specific GC columns such as CF-SIL88
or SP2330 when isomer specificity is required.
12.2 Analyze standards and samples under identical conditions with the mass
spectrometer operating in the Selected Ion Monitoring (SIM) mode using a
scan time to give at least five points per peak. Recommended MS/MS
conditions are given in Table 2.
12.3 Check the calibration every 12 hours as described in Section 8.4, The
volume of calibration standard injected shall be approximately the same
as sample injection volumes. The identification requirements described
in Section 8 shall be met for all calibration standards,
12.4 If lower detection limits are required, the extract may be carefully
evaporated under a gentle stream of nitrogen with the concentrator tube
in a water bath at about 40 C. Concentration is recommended for all
samples which have required column cleanup. Conduct this operation
immediately before GC/MS/MS analysis.
12.5 Inject a 1 to 2 uL aliquot of the sample extract.
12.6 The presence/absence of 2,3,7,8-TCDD is qualitatively confirmed if the
criteria in Section 8.10 are achieved.
12.7 For quantitation, measure the response of the m/e 257 and 259 peaks for
2,3,7 8-TCDD, the m/e 268 peak for 13C12-2.3,7,8-TCDD, and the 263 peak
for CI4-2,3,7,8-TCDD. Calculate the concentrations of 2,3,7,8-TCDD
and surrogate standards using the following equations:
11.5.4
11.5.5
11.5.6
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Equation 9: Calculation of Concentration of Native
2,3,7,8-TCDD
Cs - (As/Als - C.F.)(Qis)/(RRFn)(A)
where:
Cs - Concentration of native TCDD
As - SIM response for 2,3,7,8-TCDD ion at m/e 257 + 259
A£s - SIM response for the internal standard ion at m/e 268
C.F. - Correction factor for Sample Spiking Solution (blank)
previously determined (Equation 5)
Q|s - Amount of internal standard (ng) added to each sample
RRFn - Overall mean relative response factor for
2,3,7,8-TCDD calculated previously (Equation 1) for the
initial calibration.
A - Volume, weight, or area of sample analyzed (water
samples in mL; solid samples in g; wipe samples in cm ;
and air samples in m .
Equation 10: Calculation of Concentration of Surrogate
Standard
Css ~ (Ass)(Qls)/(Ais)(RAFn)
where:
Css - Concentration of surrogate standard (ng)
Ass - SIM response for surrogate ion at m/e 263 (corrected)
A^s - SIM response for the internal standard ions at m/e 268
Q^s ~ Amount of internal standard (ng) added to each sample
RRFn - Overall mean relative response factor for the surrogate
calculated previously (Equation 11) for the Initial
calibration
Note: Native 2,3,7,8-TCDD contains an innate quantity of
CI4-2,3,7,8-TCDD. Except at high concentrations of native
2,3,7,8-TCDD, this contribution is too small to significantly
affect the calculated concentration of surrogate Cl^-2,3,7,8-
TCDD. The theoretical correction is calculable on the basis of
isotope distribution and amounts to 1.08% of the m/e 257 peak.
(This correction shall be checked at low resolution by
analyzing about 200 pg/uL of unlabeled 2,3,7,8-TCDD.) On this
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basis, the correction to the area count of the surrogate is
made as follows:
a263 (corrected) " A263 (observed) * (0.0108)(A257)
12.8 In evaluating the results, a distinction shall be made between
quantitative measurement and qualitative identification of 2,3,7,8-TCDD
The following steps shall be taken in the treatment of all sample
results.
12.8.1 Determine if all of the qualitative identification criteria are
met.
12.8.2 Calculate the concentration of native 2,3,7,8-TCDD using
Equation 9.
12.8.3 If all qualitative identification criteria are met, report the
concentration found by Equation 9, regardless of concentration.
12.8.4 If the qualitative identification criteria are not met, and the
concentration calculated by Equation 3 is less than the
required detection limit, then report the concentration as the
detection limit.
12.8.5 If the qualitative identification criteria are not met, and the
concentration calculated by Equation 9 is greater than the
required limit of detection, the extract must be cleaned up and
reinjected. If the qualitative identification criteria are
still not met and the detection limit is still greater than the
limit of detection, the sample must be re-extracted and
reanalyzed. For consumable matrices (wipe; air) complete
reprocessing is not possible. If upon complete reprocessing,
detection limits are still exceeded, then the sample may not be
amenable to the method or a matrix effect exists. The
laboratory shall report both sets of results using the
reporting codes identified in Exhibit B. A modification to the
standard method under Task 2 shall be attempted (See Task 2).
The TPO will advise the laboratory about recollection of
consumed samples that will need Task 2 analysis.
12.10 Calculate the recovery (accuracy) of the surrogate using the amount
found in Equation 10 divided by the amount added multiplied by 100.
•17
Equation 11: Calculation of Surrogate CI4 -2,3,7,8-TCDD,
Recovery
%Recovery - Amount found (ng)(100)/Amount Added (ng)
13. Method Performance
13.1 The required detection limits for these methods are as follows: water,
1.0 ng/sample; solids, 0.3 ng/g; asphalt containing solids, 0.7 ng/g;
wipe, 1.0 ng/sample; and air, 1.0 ng/sample. Samples not meeting the
detection limit shall be subjected to the cleanup procedures described
C- 27
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herein and automatically reanalyzed. If necessary, the sample shall be
re-extracted and reanalyzed,
14. Data Reporting
14.1 Report all data in the following units: water, pg/mL; solids, ng/g;
wipe, pg/cm ; and air, pg/m . All raw data and final results shall be
entered using the software programs provided for this contract.
15. Sample Reruns
15.1 Sample reruns shall be done if any of the quality control or detection
limit requirements of this method are not met. In all cases these are
considered automatic reruns and shall be completed within the reporting
period. The only exception to this will be for the performance
evaluation sample, for which the laboratory will be given the reporting
period from the time of notification until the reanalysis must be
reported. Depending on the criteria missed, sample reruns may include
the entire reprocessing of the sample or just additional cleanup and
reinjection.
15.2 Sample reruns include the re-extracting and reprocessing of the entire
sample batch (or selected portion) if the reagent blank, field blank,
matrix spike, or performance evaluation sample is non-compliant, or if
the batch was run with a non-compliant calibration. Entire reprocessing
of a sample is required if the surrogate recovery is out of control.
15.3 Cases where reanalysis may be limited to just cleanup and reinjection
include instances where signal to noise criteria were not met, ion
ratios were not met, and detection limit requirements were not met.
However, if cleanup and reinjection does not solve the problem, the
laboratory shall completely reprocess the sample.
15.4 In those cases where a reanalysis is required, and similar results are
obtained on the reanalysis (complete reprocessing), there may be a
matrix effect or the sample may not be amenable to the standard method.
In these Instances the sample should be considered for analysis under
Task 2 (see Task 2).
15.5 In all cases automatic reruns shall be considered part of the initial
sample analysis and shall be deemed non-billable unless the laboratory
data supports a matrix effect.
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TABLE 1
RECOMMENDED GC CAPILLARY CONDITIONS
CfilMin £!^5 Sf-2330
Length 15 m 60 a
I.D. 0.32 mm 0.24 mm
Film Thickness 1.0 micron 0.2 micron
2,3,7,8-TCDD Retention Tine 5-6 min. 24 min.
Carrier Gas Nitrogen
Initial Oven Temperature 150*C
Initial Hold Times 1.0 min.
Splitless Time 1.0 min.
Temp. Program Rate 20*C/min,
Final Oven Temperature 240*C
Split Flow 20 mL/min.
Septum Purge Flow 0.6 mL/min,
Capillary Head. Pressure 8 psi
Transfer Line Temperature 240*C
Helium
70*C
4.0 min.
Rapid to 200*C
240* C
CP-SIL 88
50 m
0.22 sua
0.22 micron
26 min.
Helium
45*C
3.0 min.
Rapid to 200*C
240* C
**
**
then 4*C/min. to 240°C
then 5*C/min. to 240°C
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TABLE 2
Instrument
Ion Source
CI Reagent Cas
Reagent Gas Flow
Source Temperature
Discharge Current
Q1 Resolution
Q3 Resolution
Collision Energy (LAB)
Collision Gas
Collision Gas Thickness
Ions Monitored
MS/MS OPERATING CONDITIONS
TAGA or TAGA 6000E
Townsend/glow discharge CI
Zero grade air (H2 and He free)
35+1 mL/min.
200"C
-1 mA
3 amu at 50% peak height at m/e 320 (single MS)
3 amu at 50% peak height at m/e 320 (single MS)
55 eV [(OR + GR)/2 - R2] or 55 eV (OR - R2)
Argon
400 x 10^ molecules/cm^
03
257 (native-TCDD)
259 (native-TCDD)
263 (surrogate standard)
268 (internal standard)
Q2_
320
322
328
332
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C-31
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PART B - HRGC/LRMS METHOD (LR/GC/MS)
1. Scope and Application
1.1 This method shall be used in the rapid determination of 2,3,7,8-
Tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) in water, solids (soil,
sediment, dust, wood fiber, vegetation, and insulation), wipe, and air
samples, when 2,3,7,8-TCDD is known to be the principal or only
tetrachlorodibenzo-p-dioxin isomer present. The method is not specific
for the 2,3,7,8-TCDD isomer, unless a capillary column which separates
that isomer from the other 21 TCDD isomers is employed. Co-eluting
tetrachlorodibenzodioxin isomers, if present, may present a positive
bias.
1.2 The method employs a quadrupole mass spectrometer as the final detector.
Any GC/MS instruments meeting the quality control and detection limit
requirements are acceptable.
1.3 The method incorporates isotope dilution techniques utilizing an
isotopically labeled TCDD congener which corrects for losses in the
analytical processing of the samples.
1.4 This method is restricted to use only by or under the supervision of
analysts experienced in the use of gas chromatography/mass spectrometry.
1.5 The analytical range of analysis is 1-25 ng. However, this range can be
expanded on the upper end by analysis of additional calibration
standards.
Analvte CAS Number
2,3,7,8-Tetrachlorodibenzo-p-dioxin 1746-01-6
2. Summary of Method
2.1 Water Samples
A one (1) liter aliquot of water is spiked with internal and surrogate
standards of isotopically labeled 2,3,7,8-TCDD. The spiked sample is
then extracted with 3 (60 mL) portions of methylene chloride using
separatory funnel techniques.
2.2 Solid Samples
A ten (10) gram aliquot of the solid sample is spiked with internal and
surrogate standards of isotopically labeled 2,3,7,8-TCDD. Anhydrous
sodium sulfate is added to any wet samples to form a free flowing sample
prior to extraction with acetone/hexane using a jar extraction
technique.
2.3 Wipe Samples
The absorbent pads (consisting of a cotton gauze pad or filter paper)
are placed in an extraction jar. The pads are spiked with internal and
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surrogate standards of isotopically labeled 2,3,7,8-TCDD. The sample
container is rinsed with an aliquot of the extraction solvent,
acetone/hexane, which is added to the extraction jar. The sample is
sonicated and then stirred using a magnetic stirrer for 30 minutes,
2.4 Air Samples
The sample (consisting of a glass fiber filter and PUF in a glass
cartridge) is spiked with internal and surrogate standards of
isotopically labeled 2,3,7,8-TCDD. The sample is then extracted in a
Soxhlet apparatus for 16 cycles with benzene (or dichloromethane),
2.5 A column chromatography cleanup procedure is provided which is
applicable to all methods as needed. However, it will usually be
possible to analyze the concentrated extract directly using capillary
column GC/MS. Capillary column GC/MS conditions are described which
allow for separation of TCDD from the bulk of the sample matrix and
allow for measurement of 2,3,7,8-TCDD in the extract. Quantitation is
based on the response of native TCDD relative to the isotopically
labeled TCDD internal standard. Performance is assessed based on the
results for surrogate standard recoveries, EPA performance evaluation
(PE) samples, spike recoveries, and method and field blanks.
3• Interferences
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that lead to
discrete artifacts and/or elevated backgrounds at the ions monitored.
All of these materials shall be routinely demonstrated to be free from
interferences under the conditions of the analysis by running laboratory
reagent (also referred to as method) blanks as described in Section 8.
3.2 The use of high purity reagents and solvents helps to minimize
interference problems. Purification of solvents by distillation in all-
glass systems may be required along with Soxhlet extraction of certain
reagents.
3.3 Matrix Interferences may be caused by contaminants that are co-extracted
from the sample. The extent of matrix interferences will vary
considerably from source to source, depending upon the nature and
diversity of the sample and matrix. 2,3,7,8-TCDD is often associated
with other interfering chlorinated compounds which are at concentrations
several magnitudes higher than that of 2,3,7,8-TCDD and may present
problems in analysis. Fine dust, insulation, and asphaltic containing
matrices contain the most interferences and may require more extensive
cleanup procedures for successful analysis. In some instances, the
quantity of internal standard added before analysis may need to be
increased to accommodate for more extensive cleanup and dilutions
required.
3.4 The use of a quadrupole mass spectrometer as the detector serves to
minimize the influence of many of these interferents.
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4. Safety (Note: Information in this section on Safety is general
guidance rather than requirements of the contract).
It is not within the scope of the Statement of Work to require specific
safety procedures. General guidance has been Included for informational
purposes only. The guidance does not exempt the contractor from knowing
or following any other State and/or Federal regulations applicable to
the handling and disposal of dioxin wastes. The following safety
practices are excerpted directly from EPA Method 613, Section 4 (July
1982 version).
4.1 The toxicity or carcinogenicity of each reagent used in this method has
not been precisely defined; however, each chemical compound should be
treated as a potential health hazard. From this viewpoint, exposure to
these chemicals must be reduced to the lowest possible level by whatever
means available. The laboratory is responsible for maintaining a
current awareness file of OSHA regulations regarding the safe handling
of the chemicals specified in this method. A reference file of material
data handling sheets should also be made available to all personnel
involved in the chemical analysis. Benzene and 2,3,7,8-TCDD have been
identified as suspected human or mammalian carcinogens.
4.2 Each laboratory must develop a strict safety program for handling of
2,3,7,8-TCDD. The following laboratory practices are recommended:
4.2.1 Contamination of the laboratory will be minimized by conducting
all manipulations in a hood.
4.2.2 The effluents of sample splitters for the gas chromatograph and
roughing pumps on the GC/MS should pass through either a column
of activated charcoal or be bubbled through a trap containing
oil or high boiling point alcohols.
4.2.3 Liquid waste should be dissolved in methanol or ethanol and
irradiated with ultraviolet light with wavelength greater than
290 nm for several days. (Use F 40 BL lamps or equivalent.)
Analyze liquid wastes and dispose of the solutions when
2,3,7,8-TCDD can no longer be detected.
4.3 Dow Chemical, U.S.A. has issued the following precautions (revised 11/78)
for safe handling of 2,3,7,8-TCDD in the laboratory:
4.3.1 The following statements on safe handling are as complete as
possible on the basis of available toxicological information.
The precautions for safe handling and use are necessarily
general in nature since detailed, specific recommendations can
be made for only for the particular exposure and circumstances
of each individual use. Inquiries about specific operations or
uses may be addressed to the Dow Chemical Company. Assistance
in evaluating the health hazards of particular plant conditions
may be obtained from certain consulting laboratoriss and from
State Departments of Health or of Labor, many of which have an
industrial health services. 2,3,7,8-TCDD is extremely toxic to
laboratory animals. However, it has been handled for years
without injury in analytical and biological laboratories.
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Techniques used in handling radioactive and infectious
materials are applicable to 2,3,7,8-TCDD.
4.3.1.2
4.3.1.3
4.3.1.4
4.3.1.5
4.3.1.6
4.3.1.7
Protective Equipment: Throw-away plastic gloves,
apron or lab coat, safety glasses, and lab hood
adequate for radioactive work.
Training: Workers must be trained in the proper
method of removing contaminated gloves and clothing
without contacting the exterior surfaces.
Personal Hygiene: Thorough washing of hands and
forearms after each manipulation and before breaks
(coffee, lunch, and shift).
Confinement: Isolated work area (posted with signs),
segregated glassware and tools, plastic-backed
absorbent paper on benchtops.
Waste: Good technique includes minimizing
contaminated waste, Plastic bag liners should be
used in waste cans. Janitors must be trained in
safe handling of waste.
Disposal of Wastes: 2,3,7,8-TCDD decomposes above
800*C. Low level waste such as the absorbent paper,
tissues, animal remains and plastic gloves may be
burned in a good incinerator. Gross quantities
(milligrams) should be packaged securely and
disposed of through commercial or governmental
channels which are capable of handling high-level
radioactive wastes or extremely toxic wastes.
Liquids should be allowed to evaporate in a good
hood and in a disposable container. Residues may
then be handled as above.
Decontamination: Personal - any mild soap with
plenty of scrubbing action: Glassware, Tools, and
Surfaces - Chlorothene NU Solvent (Trademark of the
Dow Chemical Company) is the least toxic solvent
shown to be effective. Satisfactory cleaning may be
accomplished by rinsing with Chlorothene, then
washing with any detergent and water. Dish water
may be disposed to the sewer. It is prudent to
minimize solvent wastes because they may require
special disposal through commercial sources which
are expensive.
Laundry: Clothing known to be contaminated should be
disposed of with the precautions described in
4.3.1.6. Lab coats or other clothing worn in
2,3,7,8-TCDD work area may be laundered and should
be collected in plastic bags. Persons who handle
the bags and launder the clothing should be advised
of the hazard and trained in proper handling. The
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clothing may be put into a washer without contact if
the launderer knows the problem. The washer should
be run through a cycle before being used again for
other clothing.
4.3.1.9 Wipe Tests: A useful method of determining
cleanliness of work surfaces and instruments is to
wipe the surface with a piece of filter paper.
Extraction and analysis by GC/MS can achieve a limit
of sensitivity of 0.1 ug per wipe. Less than 1 ug
2,3,7,8-TCDD per sample indicates acceptable
cleanliness; anything higher warrants further
cleaning. More than 10 ug on a wipe sample
indicates an acute hazard and requires prompt
cleaning before further use of the equipment or work
space and indicates further that unacceptable work
practices have been employed in the past.
4.3.1.10 Inhalation: Any procedure that may produce airborne
contamination must be done with good ventilation.
Gross losses to a ventilation system must not be
allowed. Handling of the dilute solutions normally
used in analytical and animal work presents no
inhalation hazards except in case of an accident.
4.3.1.11 Accidents: Remove contaminated clothing immediately,
taking precautions not to contaminate skin or other
articles. Wash exposed area vigorously and
repeatedly until medical attention is obtained.
5. Required Materials/Apparatus, and Instrumentation
5.1 Materials/ Apparatus: All glassware shall be initially cleaned with
aqueous detergent and then rinsed with tap water, deionized water,
acetone, toluene, and methylene chloride.
Other cleaning procedures may be used as long as acceptable reagent
blanks are obtained.
5.1.1 Sample Extraction
5.1.1.1 Vater Samples
a. Separatory funnels, 2 L with Teflon stopcocks
b. Erlenmeyer flasks, 250 mL
c. Glass funnels
d. Graduated cylinder, 1 L
5.1.1.2 Solid Samples
a. Electronic balance, capable of weighing with an
accuracy of at least +/- 0.05 g
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b. Ultrasonic bath
c. Magnetic Stir Plates
d. Teflon magnetic stir bars
e. Stainless steel spatulas
f. Anhydrous sodium sulfate
g. Glass jars with teflon lined lids, 8 oz.
5.1.1.3 Wipe Samples
a. Glass extraction jars, 500 mL beakers
b. Ultrasonic water bath, Bransonic 220 (or
equivalent)
c. Magnetic stirrer with teflon stir bar
5.1.1.4 Air Samples
a. Soxhlet extractors with large Friedricks-type
Pyrex brand glass condensers, or equivalent.
Improved Design extractors with a No. 71/60
female ground glass joint at the top and a No.
24/40 male ground glass joint at the bottom, a
No. 55/50 female ground glass joint to a No.
71/60 male ground glass joint adaptor for
coupling the condenser to the extractor, and a
1.0 L flask with a No. 24/40 ground glass joint
as the receiving vessel. The extractor should
accommodate a 6.5 cm o.d. x 12.7 cm length glass
cartridge unit.
b. Heating mantle or block heater designed to
accommodate 1 L solvent flask
c. Refrigerated Water Recirculating Unit
5.1.2 Sample Concentration
a. Kuderna-Danish concentrator tubes, 10 mL (Kontes K-57005Q-
1025 or equivalent); evaporation flasks, 500 mL (Kontes
K570001-0500 or equivalent); and Snyder columns, three-ball
macro (Kontes K-503000-0121 or equivalent) o£ Rotary
evaporation unit.
b. Nitrogen blowdown apparatus, N-Evap Analytical Evaporator
Model 111 (or equivalent)
c. Water bath, heated, with concentric ring cover (if K-D
evaporation used)
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5.1.3 Sample Cleanup
a. Disposable Pasteur pipets, 5 3/4" x 7 mm o.d.
b. Glass chromatography columns, 1cm X 20cm
c. Glass wool, stlanized
d. Vacuum aspirator
5.1.4 Miscellaneous
a. Stainless steel spatulas
b. Vials, amber glass, 10 mL with Teflon-lined screw caps
c. Serum vials, 1.0 and 2.0 mL vials; cone shaped Inside to
enable removing very small samples; heavy wall borosilicate
glass; with Teflon faced rubber septa and screw caps
d. 1-10 uL syringes
e. Disposable Teflon filters, 0.45 micron
f. Boiling chips, approximately 10/40 mesh
5.2 Instrumentation
5.2.1 Gas chromatograph, analytical system complete with all required
accessories including syringes, analytical columns, and gases.
The injection port shall be designed for capillary columns.
Either split, splitless, or on-column injection technique may
be employed.
5.2.2 Mass spectrometer, low resolution mass spectrometers (LRMS).
The mass spectrometer shall be equipped with an electron
impaction source operated at 70 eV and be capable of acquiring
Ion abundance data in real time Selected Ion Monitoring (SIM)
for groups of six or more ions.
5.2.3 GC/MS interface, any gas chromatograph to mass spectrometer
interface can be used that achieves the requirements of Section
8. Glass or glass-lined materials are recommended. Glass
surfaces can be deactivated by silanizing with
dichlorodimethylsilane. To achieve maximum sensitivity, the
exit end of the capillary column should be placed in the ion
source. A short piece of fused silica capillary can be used as
the interface to overcome problems associated with
straightening the exit end of glass capillary columns.
5.2.4 The SIM data acquired during the chromatographic program can be
acquired under computer control or as real time analog output.
If computer control is used, there shall be software available
to plot the SIM data and report peak height or area for any ion
between specified time or scan number limits.
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5,2.5 Columns: 30 m long x 0.32 mm I.D. fused silica capillary DB-S
with 0.25 micron film thickness.
Other columns can be used as long as the quality control and
detection limit requirements are met, including isomer
specificity if necessary.
5.2.6 Compressed Gases: Ultra high purity helium.
6. Standards. Solvents, and Reagents
6.1 Standards
6.1.1 Calibration Standard Solutions
The calibration standard solutions correspond to three toluene
or isooctane solutions containing unlabeled 2,3,7,8-TCDD at
varying concentrations and C|2*2,3, 7,8,-TCDD (the internal
standard, CASRN 80494-19-5) at a constant concentration. These
solutions also contain CI4-2,3,7,8-TCDD (the surrogate
compound CASRN 85508-50-5) at varying concentrations.
These are to be obtained from commercial sources or prepared
in the contractor laboratory. Documentation of the source of
standards shall be provided.
The laboratory shall notify SMO and the Region prior to using
any new calibration or sample spiking solution whose
concentration is different than the concentrations listed in
the contract. All opened calibration standard solutions,
spiking solutions and check mixtures must be stored in a
refrigerator/freezer and protected from light. These
standard solutions shall be frequently checked for signs of
evaporation. Standard solutions shall be removed and allowed
to equilibrate for approximately 30 minutes prior to taking
any aliquots.
6.1.1.1 The calibration standard solutions will have the
stated concentrations of unlabeled, internal, and
surrogate standards:
Calibration Solution 1 (CC1)
Unlabeled 2,3,7,8-TCDD - 0.2 ng/uL
13Cl4-2,3.7,8-TCDD - 1.05 ng/uL
37Cl4-2,3,7,8-TCDD - 0.06 ng/uL
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Calibration Solution 2 (CC2)
Unlabeled 2,3,7,8-TCDD - 1.0 ng/uL
13C12-2.3,7.8-TCDD - 1.05 ng/uL
37Cl4-2,3,7,8-TCDD - 0.11 ng/uL
Calibration Solution 3 (CC3)
Unlabeled 2,3,7,8-TCDD - 5.0 ng/uL
13C12-2,3,7,8-TCDD - 1.05 ng/uL
37Cl4-2,3,7,8-TCDD - 0.2 ng/uL
6.1.2 Sample Spiking Solution
6.1.2.1 The sample spiking solution shall be obtained from
commercial sourcea or prepared by the contractor
from neat materials. The toluene or isooctane spiking
solution will have the following concentrations of
internal and surrogate standards:
13C12-2,3,7,8-TCDD - 0.61 ng/uL
37Cl4-2,3,7,8-TCDD - 0.1 ng/uL.
6.1.2.2 The spiking solution shall be transferred to 1 mL
serum vial(s) and sealed with a septum and cap prior
to each day's work for use in spiking samples for
that day, A new vial of Sample Spiking Solution
shall be opened each day. Leftover Sample Spiking
Solution shall not be stored and re-used since
evaporation of the spiking solution may occur and
the accuracy of results are directly dependent on
the addition of a known amount of internal standard.
6.1.3 Column Performance Check Solution
6.1.3.1 The column performance check solution shall be
obtained from commercial sources or prepared by the
contractor from neat materials. The mixture will
contain: unlabeled 2,3,7,8-TCDD; 1,2,3,4-TCDD
(CASRN 3074658-8),• 1,4,7,8-TCDD (CASRN 40581-94-0) ;
1,2,3,7-TCDD (CASRN 67028-18-6); 1, 2, 3-, 8-TCDD
(CASRN 53555-02-5); 1,2,7,8-TCDD (CASRN 34816-53-0);
and 1,2,6,7-TCDD (CASRN 40581-90-6).
6.1.3.2 The column performance check solution shall only be
necessary when tetradioxln isomer specificity is
required. (Section 8.13)
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6.1.A Fortified Field Blank Spiking Solution
6.1.4.1 Tho ?°ftlfi*d field blank spiking aolution shall be
obtained from commercial sources or prepared by the
contractor from neat materials. The toluene or
isooctane spiking solution will have the following
concentrations of unlabeled, internal, and surrogate
standards:
Unlabeled 2,3.7.8-TCDD - 0.1 ng/uL
13C12-2,3,7,8-TCDD - 0.61 ng/uL
37,
CI4-2,3,7,8-TCDD - 0.1 ng/uL
6.2 Solvents
6.2.1 All solvents shall be pesticide grade or equivalent. The
following solvents will be needed:
Acetone Hexane
Acetonitrile Isooctane
Benzene Methyl Alcohol
Cyclohexane Toluene
Dichloromethane (Methylene Chloride)
6.3 Reagents
6.3.1 Sodium sulfate (ACS), granular, anhydrous (purified by heating
at 400*C for 4 hours in a shallow tray or methylene chloride
extraction)
6.3.2 Glass wool, sllanlzed - extracted with methylene chloride or
benzene before use.
6.3.3 Silica gel for column chromatography, type 60, EM Reagent, 100-
200 mesh, or equivalent. Soxhlet extract with methylene
chloride for 21 hours, and activate in a foil covered glass
container for 24 hours at 130*C.
6.3.4 Activated alumina, acidic, form AG-4, 100-200 mesh, Soxhlet
extract for 21 hours with methylene chloride. Activate by
heating in a foil covered glass container for 24 hours at
190*C.
6.3.5 Carbopak C, 80/100 mesh, or equivalent.
6.3.6 Cellte 545, not acid washed, or equivalent.
6.3.7 Carbopak C/Celite mixture - A mixture by weight of 18% Carbopak
C on Cellte Is prepared. This is mixed thoroughly on a vortex
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mixer to break up large lumps. Check visually to assure that
the mixture is uniform. Dry the mixture at 130*C for 6 hours.
6.3.8 Reagent Water - Defined as water in which an interferent is not
observed at the method detection limit (MDL) of 2,3,7,8-TCDD.
6.3.9 Sulfuric Acid (Cone.), (ACS) sp. gr. 1.84.
6.3.10 Sodium hydroxide solution (ACS), 10 N. Dissolve 400 g NaOH in
reagent grade water and dilute to 1 L. Wash the solution with
methylene chloride and with hexane before use.
6.3.11 Sulfuric acid impregnated silica gel (40% w/w). Add two parts
concentrated sulfuric acid to three parts silica gel in a screw
cap bottle and mix until lump free.
6.3.12 Sodium hydroxide impregnated silica gel. Add one part of 1 M
NaOH solucion to Cwo parts silica gel (extracted and activated)
in a screw cap bottle and mix until lump free,
7• Calibration •
7.1 In this case, the internal standard is an isotope of the compound of
interest and will be used to determine the concentration of dioxin.
This technique is, therefore, referred to as an isotope dilution GC/MS
method. Three calibration standards will be analyzed and the response
of TCDD to the internal standard established.
7.2 Inject 1 to 2 uL of each of the calibration standard solutions and
acquire Selected Ion Monitoring (SIM) data for the following ions:
257
320 2 ,3,7,8-TCDD
322 2,3,7,8-TCDD
328 surrogate
332 internal standard
334 internal standard
7.3 Relative response factors (RRF) for unlabeled 2,3,7,8-TCDD vs. the
internal standard for triplicate determinations of each of the three
calibration standard solutions are calculated by Equation 1.
Equation 1: RRF for Native 2,3,7,8-TCDD
RRFn - (As)(Cis)/(Ais)(Cs)
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where:
As - SIM response for 2,3,7,8-TCDD (m/e 320 + 322)
Ajs - SIM response for -?.3,7,8-TCDD internal standard (m/e 332 +
334)
Cs - Concentration of 2,3,7,8-TCDD (ng/uL)
C^s ~ Concentration of the internal standard (ng/uL)
7.4 Relative response factors for the surrogate standard vs. the internal
standard for the triplicate determinations of each of the three
calibration standards are calculated by Equation 2.
Equation 2: RRF for Surrogate Standard ^^Cl^-2,3,7,8-TCDD
RRFSS - (AggCj^g)/(A^sCss)
where:
Ass - SIM response for ^Cl^-2,3,7,8-TCDD surrogate standard (m/e 328)*
A^s - SIM response for ^C]_2"2.3,7,8-TCDD internal standard
(m/e 332 + 334)
Cis - Concentration of internal standard (ng/uL)
Css - Concentration of surrogate standard (ng/uL)
7.5 Each of the calibration standard solutions shall be analyzed in
triplicate, and the variation of the RRF values for each concentration
level shall not exceed 10% relative standard deviation (RSD) for both
TCDD and the surrogate compound. If the three mean RRF values for each
compound do not differ by more than + 10% RSD, the RRF can be considered
to be independent of analyte quantity for the calibration concentration
range, and the mean of the three RRF's shall be used for the
concentration calculations. The overall mean is termed the calibration
factor.
7.6 The calibration factor shall be verified on each work shift of 12 hours
or less by the analysis of the calibration standard solution 1 (CC1).
If the RRF for the standard differs from the calibration factor by more
than 10%, the entire calibration shall be repeated and a new calibration
factor determined. The overall mean RRF determined during the initial
calibration is used for all calculations. The verification is only
required for 2,3,7,8-TCDD. The lab shall, however, monitor response of
the surrogate compound as a preventative action measure.
* When using ^Cl4-2,3,7,8-TDCC, correct the 328 response by subtracting
0.009 of the 322 response.
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7.7 Calculate the ion ratio for 2,3,7,8-TCDD for each of the standards
analyzed using Equation 3.
Equation 3: Ion Ratio of 2,3,7,8-TCDD
Ratio - A320/A322
and
Ratio - A332/A334
where,
A320 ~ Area response for ion tn/e 320
A322 " Area response for ion m/e 322
A332 ~ Area response for ion m/e 332
A334 - Area response for ion m/e 334
8. Quality Control Requirements
8.1 The following quality control (QC) requirements are listed In the order
that they shall be run. Section 8.2 is to be met prior to the analysis
of the samples. Section 8.3 shall be included with each batch of real
samples that is run in one 12-hour time period or each shift. Sections
8.4- 8.12 are to be met for each set of samples analyzed. For Sections
8.13 and 8.14, the laboratory will be given 48 hours prior notice if
this requirement is to be implemented. NOTE; If any of these criteria
(except for sample identification) are not met, it is considered an
automatic rerun, and therefore, part of the principal sample analysis
and not billable as a separate analysis. In the case of Section 8.7,
the TPO will notify the laboratory of any non-acceptable performance
evaluation sample results and the laboratory will be given additional
time (another reporting period) to perform the reanalysts. These
reanalyses shall also be considered non-billable. See Exhibit A for
specific requirements regarding reruns.
8.2 An initial calibration shall be performed using calibration standard
solutions with varied amounts of native TCDD. The criteria given in
Section 7 shall be met or the calibration shall be repeated (%RSD <10%).
All samples associated with an unacceptable initial calibration shall be
reanalyzed. The 320/322 (TCDD) and 332/334 (internal standard) ion
ratios shall be within 0.67 - 0.90 for all solutions. All calibration
standard solution analysis shall meet the positive identification
criteria outlined in item 8.9 for TCDD.
8.3 A 1-point calibration check using calibration standard solution 1 (CC1)
shall be run once every 12 hours, or every shift, whichever is more
frequent. If the RRF differs by more than ± 10% from that of the
overall mean RRF previously determined from the initial 3-point
calibration, then a new initial calibration shall be performed. The
calibration check for the surrogate is not necessary unless the
surrogate recoveries appear biased and/or consistently fall outside the
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60-140% control limits. All calibration check standard analysis shall
meet the positive identification criteria outlined in Section 8.9 for
TCDD.
8.4 A laboratory "reagent blank" shall be prepared and analyzed along with
every batch of 28 or fewer samples and for each matrix. A reagent blank
shall be performed by executing all of the specified extraction steps,
except for the introduction of a real sample (In the case of water
analysis 1 L of pure deionized water shall be used). The reagent blank
shall be dosed with the internal standard and surrogate standard.
Results for the reagent blank shall be calculated the same way as
samples. A positive response of > 1.0 ng for water, wipe, and air
samples, 0.3 ng/g for solid samples not containing asphalt, and 0.7 ng/g
for solid samples containing asphalt of native TCDD shall be followed by
reinjection. If still positive, re-extractior. and reanalysis of all
associated positive samples including the reagent blank shall be
performed.
8.5 Field blanks may be submitted for analysis. The field blank shall
consist of a TCDD free media and shall be analyzed as a regular sample
using the same spiking solution and sample preparation procedures. A
positive response of > 1.0 ng for water, wipe, and air samples, 0.3 ng/g
for solid samples not containing asphalt, and 0.7 ng/g for solid samples
containing asphalt of native TCDD shall be followed by reinjection. If
still positive, all positive samples associated with the field blank
shall be re-extracted and reanalyzed including the field blank.
8.6 A sample may be provided by EPA designated to be spiked by the
laboratory with native TCDD(matrix spike). The Fortified Field Blank
Spiking Solution shall be used to spike the designated sample. The
recovery shall be within 60-140% or the analysis is stopped and all
related samples and the matrix spike sample shall be re-extracted and
reanalyzed. The following spiking levels shall be used: water, 10 ng/L;
solids, 1 ng/g; wipe, 5 ng/sample; and air, 10 ng/sample.
8.7 The laboratory may be given performance evaluation (PE) samples by EPA
to run with each batch of samples. The results from these performance
evaluation samples will be evaluated by EPA. If a result is not within
the acceptance criteria set by EPA, the laboratory will be notified and
all samples in the batch associated with the PE sample shall be
reanalyzed.
8.8 Each sample shall be dosed with the Sample Spiking Solution containing
internal standard and surrogate standard. The specific amount is listed
in Section 10. The surrogate recovery shall be within 60-140% or the
sample shall be re-extracted and reanalyzed.
8.9 The following qualitative requirements shall be met in order to confirm
the presence of native 2,3,7,8-TCDD:
8.9.1 The retention time of the peak shall be within + 3 seconds of
the retention time for the internal standard.
8.9.2 The 320/322 ratio shall be within the range of 0.67-0.90.
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8.9.3 The ion response at 320, 322, and 257 shall be present and
maximize together. The signal to noise (S/N) ratio shall be
2.5 to 1 or better for each of the ions. (Determine the noise
level by measuring the random peak to valley signal present on
either side within 20 scans of the 2,3,7,8-TCDD retention
window. The 2,3,7,8-TCDD signal shall be at least 2.5 times
larger than this). Example of the S/N measurement is given in
Figure 1.
8.10 For those samples giving non-detect results, the result shall be less
than the required limit of detection. Otherwise the analysis shall be
stopped and interferences identified and corrected using specified
sample cleanup procedures until the detection limit is met. Likewise,
those samples for which a peak is present but does not meet
identification are subject to the same detection limit requirement. The
required detection limits are 1.0 ng for water, wipe, and air samples;
0.3 ng/g for all solid samples not containing asphalt; and 0.7 ng/g for
solid samples containing asphalt.
8.11 For each sample and standard solution analyzed, the internal standard
ion ratio for m/e 332/334 shall be between 0.67-0.90 and have a S/N
ratio of at least 10 to 1 for both m/e 332 and 334.
8.12 A laboratory duplicate analysis may be designated by EPA for a specific
sample. When designated, the laboratory shall prepare and analyze the
sample in duplicate. The relative percent difference for the laboratory
duplicate cannot exceed 40% for solid samples and 25% for water samples.
8.13 Isomer Specificity: The contractor will be given 48 hours prior notice
when isomer specificity is needed. Isomer specificity shall be
demonstrated initially and verified once per 12-hour work shift. The
verification consists of injecting a mixture containing TCDD isomers
which elute close to 2,3,7,8- TCDD. This mixture will be provided by
EPA. It contains seven TCDD isomers (2378, 1478, 1234, 1237, 1238,
1278, and 1267), including those isomers which are known to be the most
difficult to separate on SP2330/SP2340 columns and similar columns
containing cyanoalkyl type liquid phases. The Column Performance Check
Solution shall also contain both isotopically labeled 2,3,7,8-TCDD
standards. The solution shall be analyzed using the same chromatographic
conditions and mass spectrometric conditions as is used for the samples
and standards. The 2,3,7,8-TCDD shall be separated from interfering
isomers, with no more than a 25% valley relative to the 2,3,7,8-TCDD
peak. An example of the expected chromatogram for the TCDD Column
Performance Check Solution is given in Figures 2 and 3.
8.14 Draw a baseline for the isomer cluster representing 1478, 2378, 1237,
1238, and 1234-TCDD. Measure the distance x from the baseline to the
valley following the 2,3,7,8-TCDD peak (use the valley preceding the
2,3,7,8-TCDD peak if it is the least resolved). Measure the distance y
from the baseline to the apex of the 2,3,7,8-TCDD peak. Distance x
divided by distance y times 100 is the percent valley which must not
exceed 25%. An example is given in Figures 2 and 3.
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9. Preservation and Handling
9.1 Water Samples (Note: This Section (9.1) on collecting water sample is
provided as information only to the Contract Laboratory.)
9.1.1 Two 1 L containers of sample shall be collected. 1 L shall be
used for the primary analysis and the second liter shall be
reserved for duplicate analysis and sample reanalysis. In some
instances this amount of sample may not be available. The
laboratory shall use the entire sample if less than 1 L. All
samples shall be iced or refrigerated at 4*C and protected from
light.
9.1.2 If residual chlorine is present in the water, the field sampler
should add 80 mg of sodium thiosulfate per liter of sample and
mix well.
9.1.3 All water samples should be collected in duplicate to allow for
duplicate sample analysis and sample reruns.
9.2 Solid Samples
9.2.1 All solid samples will be provided in an 8 ounce jar or
Whirlpak bag. When received in the laboratory, the sample
shall be thoroughly mixed in the jar using a stainless steel
spatula. The spatula should be used to break up large clumps
of solids while mixing to achieve a homogeneous sample.
9.2.2 A 10 gram aliquot sample shall be taken and mixed with sodium
sulfate. The 10 gram aliquot shall be representative of the
entire sample. Thus, large stones or other particles which are
uncharacteristic of the sample shall not be included in the
aliquot.
9.2.3 Solid samples may be stored at ambient conditions as long as
temperature extremes (below freezing or above 90®C) are
avoided. Samples shall be protected from light to avoid
photodecomposition.
9.3 Wipe Samples
Wipe samples will consist of 1 or 2 absorbent pads in a 240 mL
jar. The absorbent pads may be either cotton gauze or Whatman
filter paper.
Wipe samples may be stored at ambient conditions as long as
temperature extremes (below freezing or above 90*C) are
avoided. Samples shall be protected from light to avoid
photodecomposition.
9.4 Air Samples
9.4.1 Air Samples will consist of two parts: 1) a 2-inch diameter
polyurethane foam plug (PUF) contained in a borosilicate glass
tube with a coarse stainless steel support screen and 2) a 4-
9.3.1
9.3.2
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inch glass or quartz fiber filter. The two parts will be
placed together and wrapped in aluminum foil.
9.4.2 Air samples may be stored under ambient conditions as long as
temperature extremes (below freezing or above 90'F) are
avoided. Samples shall be protected from light to avoid
photodecomposition.
10. Samnlo Extraction
10.1 Water Samples
10.1.1 Mark the meniscus on the side of the sample bottle for later
determination of sample volume. Pour the sample into a 2-L
separatory funnel.
10.1.2 Dilute 100 uL of Sample Spiking solution (containing both
internal and surrogate standards) in 1 mL of acetone. Then
quantitatively transfer the dilute spiking solution to the
sample in the separatory funnel. (Add the Fortified Field
Blank Spiking Solution to the matrix spike sample if a matrix
spike sample has been included with the batch).
10.1.3 Add 60 mL methylene chloride to the sample bottle, seal, and
shake 30 seconds to rinse the inner surface. Transfer the
solvent to the separatory funnel and extract the sample by
shaking the funnel for two minutes with periodic venting to
release excess pressure. Allow the organic layer to separate
from the water phase for a minimum of 10 minutes. If the
emulsion interface between layers is more than one-third the
volume of the solvent layer, the analyst shall employ
mechanical techniques to complete the phase separation. The
optimum technique depends upon the sample but may include
stirring, filtration of the emulsion through glass wool,
centrifugation, or other physical methods. Collect the
methylene chloride extract in a 250-mL Erlenmeyer flask.
10.1.4 Add a second 60-mL volume of methylene chloride to the sample
bottle and repeat the extraction procedure a second time,
combining the extracts in the Erlenmeyer flask. Perform a
third extraction in the same manner.
10.1.5 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-
mL concentrator tube to a 500-mL evaporative flask. Other
concentration devices or techniques may be used in place of the
K-D if the quality control and detection limit requirements are
met.
10.1.6 Dry the extract by passing it through a funnel containing
anhydrous sodium sulfate^ on top of glass wool. Collect the dry
extract in the K-D concentrator. Rinse the Erlenmeyer flask
with 3 (10 mL) portions of methylene chloride to assure
quantitative transfer.
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10.1.7 Add one or two clean boiling chips to the evaporative flask and
attach a three-ball Snyder column. Prewet the Snyder column by
adding about 1-mL methylene chloride to the top. Place the K-D
apparatus on a hot water bath (60° to 65°C) so that the
concentrator tube is partially immersed in the hot water, and
the entire lower rounded surface of the flask is bathed with
hot vapor. Adjust the vertical position of the apparatus and
the water temperature as required to complete the concentration
in 15 to 20 minutes. At the proper rate of distillation the
balls of the column will actively chatter but the chambers will
not flood with condensed solvent. When the apparent volume of
liquid reaches 1 mL, remove the K-D apparatus from the water
bath and allow it to drain and cool for at least 10 minutes.
10.1.8 Momentarily remove the Synder column, add 50 mL hexane and a
new boiling chip and replace the column. Raise the temperature
of the water bath to 85°to 90°C. Concentrate the extract as in
Section 10.1.7, except using hexane to prewet the column.
Remove the Synder column and rinse the flask and its lower
joint into the concentrator tube with 1 to 2 mL hexane. Set
aside a K-D glassware for reuse in Section 10.1.14.
10.1.9 Pour the hexane from the concentrator tube into a 125-mL
separatory funnel. Rinse the concentrator tube 4 times with
10-mL aliquots of hexane'. Combine all rinses in the 125-mL
separatory funnel.
10.1.10 Add 50 mL of 10 N sodium hydroxide solution to the funnel and
shake for 30 to 60 seconds. Discard the aqueous phase.
10.1.11 Perform a second wash of the organic layer with 50 mL of
reagent water. Discard the aqueous phase.
10.1.12 Wash the hexane layer with at least two 50-mL aliquots of
concentrated sulfuric acid. Continue washing the hexane layer
with 50-mL aliquots of concentrated sulfuric acid until the
acid layer remains colorless. Discard all acid fractions.
10.1.13 Wash the hexane layer with two 50-mL aliquots of reagent water.
Discard the aqueous phase.
10.1.14 Transfer the hexane layer into a 125-mL Erlenmeyer flask
containing 1 to 2 g anhydrous sodium sulfate. Swirl the flask
for 30 seconds and decant the hexane into the reassembled K-D
apparatus. Complete the quantitative transfer with two 10-mL
hexane rinses of the Erlenmeyer flask.
10.1.15 Add one or two clean boiling chips and concentrate the extract
to 1-5 mL.
10.1.16 Quantitatively transfer the extract to a vial and concentrate
using a gentle stream of nitrogen. Evaporate the solvent until
the volume of the solution is 0.5 - 1 mL.
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10.1.17 Determine the original sample volume by refilling the sample
bottle to the mark with water and measuring the volume in a
1000-nL graduated cylinder. Record the sample volume to two
significant figures.
10.2 Solid Samples
10.2.1 Transfer a representative 10-gram (weighed to 3 significant
figures) aliquot of sample directly into the extraction jar.
In the case of those samples known or suspected of containing
asphalt, weigh a 1-2 gram aliquot of sample. Each saaple shall
be scooped with an individual stainless steel spatula to avoid
cross contamination. An attempt shall be made to weigh out an
aliquot representative cf the whole sample and may involve
physical mixing of the sample. Excessively wet samples shall
be centrifuged and moisture decanted, prior to weighing.
10.2.2 Crush the larger pieces of solid with the spatula. Leaving
the spatula in the jar, cover the mouth of the jar with
teflon-lined lid.
10.2.3 Add 100 uL of Sample Spiking Solution (containing both internal
and surrogate standards.) This will result in the addition of
61 ng of internal standard and 10 ng of surrogate standard. For
those samples known or suspected of containing asphalt, add 200
uL of the Sample Spiking Solution (122 ng internal standard and
20 ng surrogate standard). Add the spiking solution directly
to the solid spreading it over several sites on the surface of
the solid. Make certain that the standard has absorbed into
the solid before continuing the procedure. (Add the Fortified
Field Blank Spiking Solution to the matrix spike sample if a
matrix spike sample has been included with the batch).
10.2.4 Add 20 grams of purified anhydrous sodium sulfate to the sample
after the spiking solution has dried in the sample. Mix
thoroughly using a stainless steel spatula. Allow the mixture
to stand for 5 minutes then continue with the procedure.
10.2.5 Add 50 mL of 10% acetone/hexane solvent solution to each jar.
Allow the solvent to wash down over the spatula. Remove the
spatula from the jar. Add a magnetic stir bar and cap the Jar
tightly. Place the jar in an ultrasound water bath (Bransonic
220 or equivalent). The bath shall be at room temperature.
Adjust water level to above the level of the solvent. Sonicate
for 30 seconds. Remove for 30 seconds. Repeat this
alternating procedure two more times being certain that the
temperature does not rise above room temperature.
10.2.6 Place the sample on a stirring plate. Adjust the speed of the
stir bar to obtain a moderate mixing of the solid sample and
solvent. Stir all samples for 1 hour. Other mixing/stirring
devices are acceptable as long as all quality control and
detection limit requirements are met.
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10.2.7 Assemble the Kuderria-Danish (K-D) concentrator by attaching a
10-mL concentrator tube to 500 mL evaporation flask. Other
concentration devices or techniques may be used in place of the
K-D concentrator if quality control and detection limit
requirements are met,
10.2.8 Remove the jars from the stirrer. Remove each of the caps and
rinse the inner surface with hexane so that the solvent washes
back into the sample container. Remove the magnetic stir bar
and rinse with hexane so that the solvent washes back into the
jar.
10.2.9 Place a glass funnel containing #4 Whatman filter paper in each
K-D flask. Place anhydrous sodium sulfate in each funnel.
Carefully decant the extract through the funnel into the
Kuderna-Danish flask. Rinse the sample jar with a small volume
of hexane. Decant the rinse into the funnel. Rinse the funnel
and paper with hexane and remove both after rinsing.
10.2.10 Add 1-2 mL of isooctane to the extract in the K-D flask.
10.2.11 Add one or two clean boiling chips to the evaporation flask and
attach a three-ball Snyder Column by adding about 1 mL hexane.
Place the K-D apparatus on a hot water bath (60 - 65°C) so that
the concentrator tube is partially immersed in the hot water,
and the entire lower rounded surface of the flaskis bathed in
hot vapor. Adjust the verticalposition of the apparatus and
the water temperature as required to complete the concentration
in 15 to 20 minutes. At the proper rate of distillation the
balls of the.column will actively chatter but the chamberswill
not flood with condensed solvent. When the apparent volume of
liquid reaches 1-2 mLremove the K-D flask from the water bath
and allow it to drain and cool for at least 10 minutes.
10.2.12 Concentrate the extract to 1 -2 mL on the steam bath.
10.2.13 Quantitatively transfer the extract to a vial and concentrate
using a gentle stream ofnitrogen. Evaporate the solvent until
the volume of the solution is 0.5 - 1 mL.
10.3 Wipe Samples
10.3.1 Transfer the absorbent pad(s) (cotton gauze pad or filter
paper) to the extraction jar.
10.3.2 Add 50 mL of Sample Spiking Solution to the absorbent pads over
several sites on the surface. (Use Fortified Field Blank
Spiking Solution for the matrix spike if a matrix spike sample
has been included with the batch).
10.3.3 Rinse out the sample container with two 10-mL portions of
extraction solvent (10% acetone in hexane v/v) and transfer
each portion to the extraction jar.
C- 52
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10.3.4 Add to the extraction jar 30 mL of extraction solvent while
rinsing the spatula. Be certain that the absorbent pad(s) are
completely covered by solvent. Add more solvent if necessary.
Place the jar in an ultrasound water bath (Bransonic 220 or
equivalent). (Caution: This operation should be performed in a
hood.) Bath shall be at room temperature. Adjust the water
level to above the level of the solvent. Sonicate for 30
seconds. Remove for 30 seconds. Repeat this alternating
procedure two more times, being certain that the water
temperature does not rise above room temperature.
10.3.5 Stir on magnetic stirrer for 30 minutes.
10.3.6 Decant extract through a glass funnel fitted with hexane-rinsed
filter paper (Whatman #4) into a Kuderna-Danish reservoir. Add
1 mL isooctane and teflon boiling chips. Other concentration
devices may be used in place of the K-D concentrator if quality
control and detection limit requirements are met.
10.3.7 Concentrate the extract volume to 1-2 mL on a steam bath.
Follow the K-D concentration technique outlined in 10.2.11.
10.3.8 Quantitatively transfer the extract to a vial and concentrate
using a gentle stream of nitrogen. Evaporate the solvent until
the volume of the solution remaining is 0.5 - 1 mL.
10.4 Air Samples
10.4.1 Place the entire glass cartridge containing the polyurethane
foam plug (PUF) and filter paper into the Soxhlet extractor.
Add 50 uL of Sample Spiking Solution depositing the spiking
solution in several spots on both the filter paper and PUF.
(Use Fortified Field Blank Spiking Solution for the matrix
spike if a matrix spike sample has been included with the
batch).
10.4.2 Introduce enough benzene (methylene chloride may be substituted
if comparability data indicates acceptable results) into the
extractor until the cartridge is completely immersed and the
solvent begins to siphon down. Add an additional 100-200 mL of
benzene. Extract for 24 hours or until 16 complete cycles have
been achieved. The extraction rate shall be such that the
solvent vapor (condensation line) does not exceed one-fourth
the way up the condenser.
10.4.3 Remove benzene in a rotary evaporator.(If methylene chloride
has been used, the laboratory may concentrate the sample using
K-D concentration techniques). When the volume is reduced to
about 2-3 mL, quantita tively transfer the extract to a vial.
Use hexane to rinse the walls of the flask for quantitative
transfer of the extract. Exchange the solvent to hexane using
the evaporator prior to the column cleanup.
C-53
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11.
Cleanup Procedures
11.1 The need for cleanup is indicated when a particular extract does not
meet the quality control or detection limit requirements. It has been
noted that dust and asphalt samples often contain matrix interferences
which co-elute with native TCDD and should be processed using both
cleanup procedures. In the case of asphalt-containing solid samples,
successive columns of the same type may be required to remove all
interferents. Two cleanup procedures are given below.
11.2 Packing of the columns shall be done less than 1 1/2 hours prior to
sample elution. Absorbent materials in the columns will remain
relatively inert (i.e. unreactive) for that time period if the solvent,
hexane, has been added immediately after packing. Note, however, that
the silica gel columns are most reactive and they shall be prepared
last. Special attention shall be paid to removing bubbles from the
solvent soaked absorbent. Columns are efficiently handled on two tiered
multi-clamp racks.
11.3 It is also acceptable to use the modified Option A and D cleanup
procedures outlined in Section 11 of the HRGC and Tandem MS method.
Note, however, that the modified cleanup procedures are not as rigorous
and may not remove enough of the interferences to meet required quality
control and detection limit requirements.
11.4 OPTION A (Silica Gel/Alumina)
Column 1: Place 1.0 g of silica gel into a 1 cm x 20 cm glass column
and tap the column gently to settle the silica gel. Add 4 g sulfuric
acid impregnated silica gel, and top off with 0.5 - lg sodium sulfate.
Tap column gently after each addition.
Column 2: Place 4 g of acidic alumina into a 1 cm x 20 cm glass column
and tap the column gently to settle the alumina. Add a 1 cm layer of
purified sodium sulfate to the top of the alumina.
11.4.1 Add hexane to each column until the packing is free of channels
and air bubbles. A small pressure (5 psi) of clean nitrogen
can be used if needed. Do not let columns dry before using.
11.4.2 Quantitatively transfer the hexane sample extract from the
concentrator tube to the top of the silica gel in Column 1.
Rinse the concentrator tube with three 1-mL portions of hexane
and transfer them to the column.
11.4.3 With 40 mL of hexane, elute the extract from Column 1 directly
into Column 2 containing the alumina.
11.4.4 Add 25 mL of hexane to Column 2 and elute until the hexane
level is just below the top of the sodium sulfate; discard the
eluted hexane.
11.4.5 Add two 20-mL aliquots of 20% methylene chloride/ 80% hexane
(v/v) to Column 2 and collect the eluate.
C- 54
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11.4.6 Reduce the volume-of the eluate with a gentle stream of
filtered dry nitrogen to 1-2 mL,
11.4.7 Proceed to Option D cleanup or store for GC/MS analysis. Seal
the vial with a Teflon-lined septum and cap prior to storing.
11.5 OPTION D (Carbopak)
11.5.1 Thoroughly mix 3.6 g of Carbopak C (or equivalent) with 16.4 g
of Celite 545 (or equivalent) in a 40 mL vial and activate by
heating in an oven at 130°C for 6 hours. Store In a
dessicator. CAUTION: Check each new batch of mixed
Carbopak/Celite to ensure recovery of > 50%.
11.5.2 Insert a small plug of glass wool into a disposable Pasteur
pipet approximately 15 cm x 7 mm. Apply suction with a vacuum
aspirator attached to the pointed end of the pipet, and add the
Carbopak/Celite mixture until 2 cm of packing is obtained.
11.5.3 Pre-elute the column with successive additions of the following
solvents;
-2 mL toluene
-1 mL of 75:20:5 methylene chloride/methanol/benzene (v/v/v)
-1 mL 50:50 cyclohexane/methylene chloride (v/v)
11.5.4 While the column is still wet with hexane, add the sample
extract. Elute the column with the following sequence of
solvents and discard the eluates:
-2 mL hexane
-1 mL 50:50 cyclohexane/methylene chloride (v/v)
-1 mL 75:20:5 methylene chloride/methanol/benzene (v/v/v)
11.5.5 Elute with 2 mL of toluene and collect the eluate, which
contains the TCDD. Transfer to a 1 mL amber mini-vial and
concentrate further as necessary.
11.5.6 Proceed to GC/MS analysis or store in refrigerator. Seal the
vial with a Teflon-lined septum and cap prior to storing.
12. LR/GC/MS Analysis
12.1 Table 1 provides guidelines for operating conditions using capillary
columns. The 30 m DB-5 column has been used for chromatography which is
not isomer specific. Other GC columns may be used which are isomer
specific, as long as all quality control and detection limit-
requirements are met. Use isomer specific GC columns such as CP-SIL88
or SP2330 when isomer specificity is required.
12.2 Analyze standards and samples under identical conditions with the mass
spectrometer operating in the Selected Ion Monitoring (SIM) mode using a
scan time to give at least five points per peak. For LRGCMS,use ions at
C-55
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m/e 320, 322, and 257 for 2 , 3 , 7 , 8-TCDD ; m/e 328 for 37Cl4-2 , 3 , 7 , 8,-TCDD;
and m/e 332 and 334 for 13C12-2,3,7,8-TCDD,
12.3 Check the calibration every 12 hours as described in Section 7.4 The
volume of calibration standard injected should be approximately the same
as sample injection volumes. The identification requirements described
in Section 8 shall be met for all calibration standards.
12.4 If lower detection limits are required, the extract may be carefully
evaporated under a gentle stream of nitrogen with the concentrator tube
in a water bath at about 40°C. Concentration is recommended for all
samples which have required column cleanup. Conduct this operation
immediately be fore LR/GC/MS analys is.
12.5 Inject a 1 to 2 uL aliquot of the sample extract.
12.6 The presence of 2,3,7,8-TCDD is qualitatively confirmed if the criteria
in Section 8 are achieved.
12.7 For quantitation, measure the response of the m/e 320 and 322 peaks for
2,3,7,8-TCDD, the m/e 332 and 334 peaks for 13C12-2,3,7,8-TCDD, and the
328 peak for Cl^-2,3,7,8-TCDD. A correction shall be made for
contribution to m/e 328 by any native TCDD which may be present. To do
this, subtract 0.009 of the 322 response from the 328 response.
Calculate the concentration of 2,3,7,8-TCDD and surrogate standards by
Equations 3 and 4, respectively. If native TCDD is not present,
calculate the detection limit by Equation 5a or 5b.
Equation 3: Calculation of Concentration of 2,3,7,8-TCDD
Cs -
-------
where:
Css ~ Concentration of surrogate standard
Ass - SIM response for surrogate ion at m/e 328 (corrected)
A^s - SIM response for the internal standard ions at m/e 332 + 334
Q£S - Amount of Internal standard (ng) added to each sample
RRFn - Overall mean relative response factor for the surrogate
calculated previously (Equation 2) for the initial calibration.
Note: Native 2,3,7,8-TCDD contains an innate quantity of ^Cl^.-2 , 3 , 7 , 8-
TCDD. Except at high concentrations of native 2,3,7,8-TCDD, this
contribution is too small to significantly affect the calculated
concentration of surrogate Cl^-2,3,7,8-TCDD. The theoretical
correction is calculable on the basis of isotope distribution and
amounts of 1.08% of the m/e 320 ion. On this basis, the correction to
the area count of the surrogate is made as follows:
^328(Corrected) ~ ^328(observed) " •0108)(A320)
12.8 In evaluating the results, a distinction shall be made between
quantitative measurement and qualitative identification of 2,3,7,8-TCDD.
The following steps must be taken in the treatment of all sample
results:
12.8.1 Determine if all of the qualitative identification criteria are
met.
12.8.2 Calculate the concentration of native 2,3,7,8-TCDD using
Equation 3 for all positive samples.
12.8.3 If all qualitative identification criteria are met, report the
concentration found by Equation 3, regardless of concentration.
12.8.4 If the qualitative identification criteria are not met,
calculate the detection limit by either 5a, or 5B as
appropriate.
12.9 A detection limit shall be calculated for every sample not giving a
positive result meeting all criteria for qualitative identification.
The detection limit is used to estimate a concentration above which
2,3,7,8-TCDD is probably not present. Two cases may arise, each
requiring a different procedure to calculate the detection limit. The
background noise level shall be determined in both cases, and is defined
as the SIM response for either the m/e 320 ion or m/e 322 ion, depending
on which one is chosen.
12.9.1 For samples in which no unlabeled 2,3,7,8-TCDD was detected,
calculate the detection limit as the concentration required to
produce a signal with an area of 2.5 times the background
signal, Equation 5a.
C- 57
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Equation 5a: Detection Limit Calculation when no 2,3,7,8-TCDD
is Present
Detection Limit = (2.5)(As)(Q£s)/(RRFn)(A)(A£S)
where:
As = SIM response for either m/e 320 or 322
A^s = SIM response for m/e 332 when As is 320 or
SIM response for m/e 334 when As is 322
Qis - Amount of internal standard (ng) added to each sample
RRFn = Overall mean RRF calculated during the initial
calibration
A — Volume, weight, or area of sample analyzed (water sampl
in mL; solid samples in g; wipe samples in cm ; and air
samples in m^.
12.9.2 For samples having interferences in the responses for either or
both m/z 320 and 322, or when all qualitative criteria for
identifying 2,3,7,8-TCDD were met except the ion ratio, the
detection limit is calculated by Equation 5b.
Equation 5b: Detection Limit Calculation when Interferents are Present
Estimated Maximum Concentration = (As)(Q^S)/(A£5)(RRFn)(A)
where: Variables are the same as for Equation 5a
12.9.3 If the detection limit calculated by Equation 5a or 5b is
greater than the required limit of detection, the extract shall
be cleaned up and reinjected. If the qualitative
identification criteria are still not met and the detection
limit is still greater than the limit of detection, the sample
shall be re-extracted and reanalyzed. For consumable matrices
(wipe; air) complete reprocessing is not possible. If upon
complete reprocessing, detection limits are still exceeded,
then the sample may not be amenable to the method or a matrix
effect exists. The laboratory shall report both sets of
results using the reporting codes identified in Exhibit B. A
modification to the standard method under Task 2 shall be
attempted (See Task 2). The TPO will advise the laboratory
about recollection of consumed samples that will need Task 2
analysis.
.10 Calculate the recovery (accuracy) of the surrogate using the amount
found in Equation 4 divided by the amount added multiplied by 100.
Equation 6: Calculation of Surrogate Cl^-2,3,7,8-TCDD, Recovery
% Recovery - Amount found (ng)(100)/Amount added (ng)
C-58
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13.
Method Performance
13.1 The required detection limits for these methods are as follows: water,
1.0 ng/sample; solids, 0.3 ng/g; asphalt containing solids, 0.7 ng/g;
wipe, 1.0 ng/sample; and air, 1.0 ng/sample. Samples not meeting the
detection limit shall be subjected to the cleanup procedures described
herein and automatically reanalyzed. If necessary, the sample shall be
re-extracted and reanalyzed.
14. Data Reporting
14.1 Report all data in the following units: water, pg/mL; solids, ng/g;
wipe, pg/cm ; and air, pg/m . All raw data and final results shall be
entered using the software programs provided for this contract.
15. Sample Reruns
15.1 Sample reruns shall be done if any of the quality control or detection
limit requirements of this method are not met. In all cases these are
considered automatic reruns and shall be completed within the reporting
period. The only exception to this shall be for the performance
evaluation sample, for which the laboratory will be given one reporting
period from the time of notification until the reanalysis must be
reported. Depending on the criteria missed, sample reruns shall include
the entire reprocessing of the sample or just additional cleanup and
reinj ection.
15.2 Sample reruns include the re-extracting and reprocessing, of the entire
sample batch (or selected portion) if the reagent blank, field blank,
matrix spike, or performance evaluation sample is non-compliant, or if
the batch was run with a non-compliant calibration. Entire reprocessing
of a sample is required if the surrogate recovery is out of control.
15.3 Cases where reanalysis" may be limited to just cleanup and reinjection
include instances where signal to noise criteria were not met, ion
ratios were not met, and detection limit requirements were not met.
However, if cleanup and reinjection does not solve the problem, the
laboratory shall completely reprocess the sample.
15.4 In those cases where a reanalysis is required, and similar results are
obtained on the reanalysis (complete reprocessing), there may be a
matrix effect or the sample may not be amenable to the standard method.
In these instances the sample shall be considered for analysis under
Task 2 (see Task 2).
15.5 In all cases automatic reruns shall be considered part of the initial
sample analysis and shall be deemed non-billable unless the laboratory
data supports a matrix effect.
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TABLE 1
RECOMMENDED GC CAPILLARY CONDITIONS
Column
30 m DB-5
Silar 10C
SP-2340
2,3,7,8-TCDD Retention Time
14 min.
34.5 min.
22 rain.
Helium Linear Velocity
1 mL/min.
30 cm/sec.
0.7 mL/min
Initial Oven Temperature
75°C
100°C
60° C
Initial Hold Times
1.0 min.
'3.0 min.
3.0 min.
Splitless Time
2.0 min.
1.0 min.
Temp. Program Rate
25°C/min.
20°C/min.
25 *C/min.
Final Oven Temperature
200°C*
180°C**
250° C
Final Oven Hold Time
15 min.
15 min.
15 min.
Split Flow
15 mL/min.
30 mL/min.
Septum Purge Flow
15 mL/min.
5 mL/min.
Capillary Head Pressure
12 psi
30 psi
or 195'C and second ramp at
2°C/rain. to 215
°C
** then 2°C/min. to 250"C
C-60
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C-61
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-------
EXHIBIT D
QUALITY ASSURANCE/QUALITY CONTROL REQUIREMENTS
/
D-l
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TABLE OF CONTENTS
SECTION PAGE
I INTRODUCTION D-4
II QUALITY ASSURANCE PLANS D-6
III STANDARD OPERATING PROCEDURES D-9
IV ANALYTICAL STANDARDS REQUIREMENTS D-14
V CONTRACT COMPLIANCE SCREENING D-18
VI REGIONAL DATA REVIEW D-19
VII LABORATORY EVALUATION SAMPLES D-20
VIII GC/MS TAPE AUDITS D-22
IX ON-SITE LABORATORY EVALUATIONS D-23
X QUALITY ASSURANCE AND DATA TREND ANALYSIS D-26
REFERENCES D-27
D-2 8/90
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OVERVIEW
Quality assurance and quality control are integral parts of the Environmental
Protection Agency's (EPA) Contract Laboratory Program (CLP)' •••>)_ The
quality assurance (QA) process consists of management review and oversight at
the planning, implementation, and completion stages of the environmental data
collection activity, to ensure that data provided are of the quality
required. The quality control (QC) process includes those activities required
during data collection to produce the data quality desired and to document
the quality of the collected data^ '.
During the planning of an environmental data collection program, QA
activities focus on defining data quality criteria and designing a QC system
to measure the quality of data being generated. During the implementation of
the data collection effort, QA activities ensure that the QC system is
functioning effectively, and that the deficiencies uncovered by the QC system
are corrected. After environmental data are collected, QA activities focus
on assessing the quality of data obtained to determine its suitability to
support enforcement or remedial decisions^ ' ' \
The purpose of this Exhibit is to describe the overall quality
assurance/quality control operations and the processes by which the Program
meets the QA/QC objective defined above. This contract requires a variety of
QA/QC activities. These contract requirements are the minimum QC operations
necessary to satisfy the analytical requirements associated with the
determination of the different method analytes. These QC operations are
designed to facilitate laboratory comparison by providing the EPA with
comparable data from all Contractors. These requirements do not release the
analytical Contractor from maintaining their own QC checks on method and
instrument performance.
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SECTION I
INTRODUCTION
Appropriate use of data generated under the great range of analytical
conditions encountered in environmental analyses requires reliance on the
quality control procedures and criteria incorporated into the methods. The
methods in this contract have been validated on samples typical of those
received by the laboratories in the Contract Laboratory Program (CLP).
However the validation of these methods does not guarantee that they perform
equally well for all sample matrices encountered. Inaccuracies can also
result from causes other than unanticipated matrix effects, such as sampling
artifacts, equipment malfunctions, and operator error. Therefore, the
quality control component of each method is indispensable.
The data acquired from quality control procedures are used to estimate and
evaluate the information content of analytical results and to determine the
necessity for or the effect of corrective action procedures. The means used
to estimate information content include precision, accuracy, detection limit,
and other quantitative and qualitative indicators. In addition, it gives an
overview of the activities required in an integrated program to generate data
of known and documented quality required to meet defined objectives.
The necessary components of a complete QA/QC program include internal QC
criteria that demonstrate acceptable levels of performance, as determined by
QA review. External review of data and procedures is accomplished by the
monitoring activities of the National Program Office, Regional data users,
Sample Management Office, NEIC, and EMSL/LV. Each external review
accomplishes a different purpose. These reviews are described in specific
sections of this Exhibit. Performance evaluation samples and magnetic tape
audits provide an external QA reference for the program, A laboratory on-
site evaluation system is also part of the external QA monitoring. A
feedback loop provides the results of the various review functions to the
contract laboratories through direct communications with the Project Officers
and Deputy Project Officers.
This Exhibit is not a guide to constructing quality assurance project plans,
quality control systems, or a quality assurance organization. It is,
however, an explanation of the quality control and quality assurance
requirements of the program. It outlines some minimum standards for QA/QC
programs. It also includes specific items that are required in a QA Plan and
by the QA/QC documentation detailed in this contract. Delivery of this
documentation provides the Agency with a complete data package which will
stand alone, and limits the need for contact with the Contractor or with an
analyst, at a later date, if some aspect of the analysis is questioned.
In order to assure that the product delivered by the Contractor meets the
requirements of the contract, and to improve interlaboratory data comparison,
the Agency requires the following from the Contractor:
o A written Quality Assurance Plan, the elements of which are designated in
Section II,
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Written preparation of and adherence to QA/QC Standard Operating
Procedures (SOPs) as described in Section III.
Adherence to the analytical methods and associated QC requirements
specified in the contract.
Verification of analytical standard and documentation of the purity of
neat materials and the purity and accuracy of solutions obtained from
private chemical supply houses.
Submission of all raw data and pertinent documentation for Regional
review.
Participation in the analysis of Laboratory Evaluation Samples, including
adherence to corrective action procedures.
Participation in On-Site Laboratory Evaluations, including adherence to
corrective action procedures.
Submission of all original documentation generated during sample analyses
for Agency review.
Must receive prior written approval of any analytical procedural
modification, no matter how minor, from the Technical Project Officer.
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SECTION II
QUALITY ASSURANCE PLAN
The Contractor shall establish a quality assurance program with the objective
of providing sound analytical chemical measurements. This program shall
incorporate the quality control procedures, any necessary corrective action,
and all documentation required during data collection as well as the quality
assessment measures performed by management to ensure acceptable data
production. As evidence of such a program, the Contractor shall prepare and
submit for approval a written Quality Assurance Plan (QAP) which describes
the procedures that are implemented to achieve the following:
o Maintain data integrity, validity, and useability.
o Ensure that analytical measurement systems are maintained in an
acceptable state of stability and reproducibility.
o Detect problems through data assessment and establishes corrective action
procedures which keep the analytical process reliable,
o 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 and QC activities designed
to achieve the data quality requirements in this contract. Where applicable,
SOPs pertaining to each element shall be included or referenced as part of
the QAP. A copy of the approved QAP must be available during on-site
laboratory evaluation and within 7 days of written request by the APO/TPO.
Additional information relevant to the preparation of a QAP can be found in
EPA and ASTM publication^ * ^.
Required Elements of a Quality Assurance Plan
A. Organization and Personnel
1. QA Policy and Objectives
2. QA Management
a. Organization
b. Assignment of QC and QA Responsibilities
c. Reporting Relationships
d. QA Document Control Procedures
e. QA Program Assessment Procedures
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3. Personnel
a. Resumes
b. Education and Experience Pertinent to This Contract
c. Training Progress
Facilities and Equipment
1. Instrumentation and Backup Alternatives
2. Maintenance Activities and Schedules
Document Control
1. Laboratory Notebook Policy
2. Samples Tracking/Custody Procedures
3. Logbook Maintenance and Archiving Procedures
4. Case File Organization, Preparation and Review Procedures.
5. Procedures for Preparation, Approval, Review, Revision, and
Distribution of SOPs.
6. Process for Revision of Technical or Documentation Procedures
Analytical Methodology
1. Calibration Procedures and Frequency
2. Sample Preparation/Extraction Procedures
3. Sample Analysis Procedures
4. Standards Preparation Procedures
5. Decision Processes, Procedures, and Responsibility for Initiation
Corrective Action
Data Generation
1. Data Collection Procedures
2. Data Reduction Procedures
3. Data Validation Procedures
4. Data Reporting and Authorization Procedures
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F. Quality Control
1. Solvent, Reagent and Adsorbent Check Analysis
2. Reference Material Analysis
3. Internal Quality Control Checks
4. Corrective Action and Determination of QC Limit Procedures
5. Responsibility Designation
G. Quality Assurance
1. Data Quality Assurance-
2. Systems/Internal Audits
3. Performance/External Audits
4. Corrective Action Procedures
5. Quality Assurance Reporting Procedures
6. Responsibility Designation
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SECTION III
STANDARD OPERATING PROCEDURES
In order to obtain reliable results, adherence to prescribed analytical
methodology is imperative. In any operation that is performed on a repetitive
basis, reproducibility is best accomplished through the use of Standard
Operating Procedures (SOPs). As defined by the EPA, an SOP is a written
document which provides directions for the step-by-step execution of an
operation, analysis, or action which is commonly accepted as the method for
performing certain routine or repetitive tasks^ K
SOPs prepared by the Contractor shall be functional: i.e., clear,
comprehensive, up-to-date, and sufficiently detailed to permit duplication of
results by qualified analysts. All SOPs, as presented to the Agency, shall
reflect activities as they are currently performed in the laboratory. In
addition, all SOPs shall:
o Be consistent with current EPA regulations, guidelines, and the CLP
contract's requirements^ '^^• ' .
o Be consistent with instruments manufacturers's specific instruction
manuals.
o Be available to the EPA during an On-Site Laboratory Evaluation. A
complete set of SOP's shall be bound together and available for inspection
at such evaluations. During on-site evaluations, laboratory personnel may
be asked to demonstrate the application of the SOPs.
o Provide for the development of documentation that is sufficiently complete
to record the performance of all tasks required by the protocol.
o Demonstrate the validity of data reported by the Contractor and explain
the cause of missing or inconsistent results.
o Describe the corrective measures and feedback mechanism utilized when
analytical results do not meet protocol requirements.
o Be reviewed regularly and updated as necessary when contract, facility, or
Contractor procedural modifications are made.
o Be archived for future reference in usability or evidentiary situations.
o Be available at specific work stations as appropriate
o Be subject to a document control procedure which precludes the use of
outdated or inappropriate SOPs.
SOP FORMAT:
The format for SOPs may vary depending upon the kind of activity for which
they are prepared, however, at a minimum, the following sections must be
included:
o Title Page
o Scope and Application
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o Definitions
o Procedures
o QC Limits
o Corrective Action Procedures, Including Procedures for Secondary Review
Information Being Generated
o Documentation Description and Example Forms
o Miscellaneous Notes and Precautions
o References
SOPs Required:
The following SOPs are required by the Agency:
1. Evidentiary SOP
Evidentiary SOPs required are discussed in Exhibit F, "Specification fo
Written Standard Operating Procedures"
2. Sample Receipt and Storage
a. Sample Receipt and Identification Logbooks
b. Refrigerator Temperature Logbooks
c. Extract Storage Logbooks
d. Security Precautions
3. Sample Preparation
a. Reagent Purity Check Procedures and Documentation
b. Extraction Procedures
c. Extraction Bench Sheets
d. Extraction Logbook Maintenance
4. Glassware Cleaning
5. Calibration (Balances, GPCs)
a. Procedures
b. Frequency Requirements
c. Acceptance Criteria and Corrective Actions
d. Logbook Maintenance
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6. Analytical Procedures (for each Analytical System)
a. Instrument Performance Specifications
b. Instrumental Operating Procedures
c. Data Acquisition System Operation
d. Procedures When Automatic Quantitation Algorithms Are Overridden
e. QC Required Parameters
f. Analytical Run/Injection Logbooks
g. Instrumental Error and Editing Flag Descriptions and Resulting
Corrective Actions
7. Maintenance Activities (for each Analytical System)
a. Preventive Maintenance Schedule and Procedures,
b. Corrective Maintenance Determinants and Procedures
c. Maintenance Authorization
8. Analytical Standards
a. Standard Coding/Identification and Inventory System
b. Standards Preparation Logbook(s)
c. Standard Preparation Procedures
d. Procedures for Equivalency/Traceability Analyses and Documentation
e. Purity Logbook (Primary Standards and Solvents)
f. Storage, Replacement, and Labeling Requirements
g. QC and Corrective Action Measures
9. Data Reduction Procedures
a. Data Processing Systems Operation
b. Outlier Identification Methods
c. Identification of Data Requiring Corrective Action
d. Procedures for Format and/or Forms for each Operation
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10. Documentation Policy/Procedures
a. Laboratory/Analysts' Notebook Policy, including Review Policy
b. Complete SDG File Contents
c. Complete SDG File Organization and Assembly Procedures, including
Review Policy
d. Document Inventory Procedures, including Review Policy
11. Data Validation Procedures
a. Data Flow and Chain-of-Command for Data Review
b. Procedures for Measuring Precision and Accuracy
(91
c. Evaluation Parameters for Identifying Systematic Errors^ '
d. Procedures to Assure that Hardcopy and Electronic Data Deliverables
Are Complete and Compliant With the Requirements in Exhibits B and
H.
e. Procedures to Assure that Hardcopy Deliverables are in Agreement
with Their Comparable Electronic Data Deliverables.
f. Demonstration of internal QA inspection procedure (demonstrated
by supervisory sign-off on personal notebooks, internal PE
samples, etc.).
g. Frequency and type of internal audits (eg., random, quarterly,
spot checks, perceived trouble areas).
h. Demonstration of problem identification-corrective actions and
resumption of analytical processing. Sequence resulting from
internal audit (i.e., QA feedback).
i. Documentation of audit reports (internal and external), audit
responses, corrective action, etc.
12. Data Management and Handling
a. Procedures for controlling and estimating data entry errors.
b. Procedures for reviewing changes to data and deliverables and
ensuring traceability of updates.
c. Lifecycle management procedures for testing, modifying and
implementing changes to existing computing systems including
hardware, software, and documentation or installing new systems.
d. Database security, backup and archival procedures including
recovery from system failures.
e. System maintenance procedures and response time.
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f. Individuals(s) responsible for system operation, maintenance,
data integrity and security.
g. Specifications for staff training procedures.
SOPs Delivery Requirements:
Within seven (7) days of contract receipt, a complete set of SOPs, relevant
to this contract shall be sent to the Technical Project Officer, EMSL/LV
(quality assurance SOPs) and NEIC (evidentiary SOPs). Also, during the term
of performance of the contract, copies of SOPs which have been amended or new
SOPs which have been written shall be sent to the Technical Project Officer,
EMSL/LV (quality assurance SOPs) and NEIC (evidentiary SOPs).
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SECTION IV
ANALYTICAL STANDARDS REQUIREMENTS
Overview
"the U.S. Environmental Protection Agency will not supply the analytical reference
standards under thia contract. Contract laboratories shall be required to
prepare from neat materials or purchase from private chemical supply houses those
standards necessary to successfully and accurately perform the analyses required
in this protocol.
A. Preparation of Chemical Standards from the Neat High Purity Bulk
Material
A laboratory nay prepare their chemical standards from neat materials.
Laboratories shall obtain the highest purity possible when purchasing
neat chemical standards; standards purchased at less than 97% purity
shall be documented as to why a higher purity could not be obtained.
1. Neat chemical standards shall be kept refrigerated when not being
used in the preparation of standard solutions. Proper storage of
neat chemicals is essential in order to safeguard them from
decomposition.
2. The purity of a compound can sometimes be misrepresented by a
chemical supply house. Since knowledge of purity is needed to
calculate the concentration of solute in a solution standard, it is
the contract laboratory's responsibility to have analytical
documentation ascertaining that the purity of each compound is
correctly stated. Purity confirmation, when performed, shall use
either differential scanning calorimetry, gas chromatography with
flame ionization detection, high performance liquid chromatography,
infrared spectrometry, or other appropriate techniques. Use of two
or more independant methods is recommended. The correction factor
for impurity when weighing neat materials in the preparation of
solution standards is;
Equation 1
weight of pure compound
weight of impure compound - (percent purity/100)
where "weight of pure compound" is that required to prepare a
specific volume of a solution standard of a specified concentration.
3. Mis-identification of compounds occasionally occurs and it is
possible that.a mislabeled compound may be received from a chemical
supply house. It is the contract laboratory's responsibility to
have analytical documentation ascertaining that all compounds used
in the preparation of solution standards be correctly identified.
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Identification confirmation, when performed, shall use mass
spectrometry, gas chromatographic analysis on at least two different
analytical columns, or other appropriate techniques.
4. Calculate the weight of material to be weighed out for a specified
volume taking into account the purity of the compound and the
desired concentration. A second person shall verify the accuracy of
the calculations. Check balances for accuracy with a set of
standard weights. All weighing shall be performed on an analytical
balance to the nearest 0.1 mg and verified by a second person. The
solvent used to dissolve the solute shall be compatible with the
protocol in which the standard is to be used; the solute shall be
soluble, stable, and nonreactive with the solvent. In the case of a
multicomponent solution, the components shall not react with each
other.
5. Transfer the solute to a volumetric flask and dilute to the
specified solution volume with solvent after ensuring dissolution of
the solute in the solvent. Sonication or warming may be performed
to promote dissolution of the solute. This solution shall be called
the primary standard and all subsequent dilutions shall be traceable
back to the primary standard.
6. Log notebooks are to be kept for all weighing and dilutions. All
subsequent dilutions from the primary standard and the calculations
for determining their concentrations shall be recorded and verified
by a second person. All solution standards shall be refrigerated
when not in use. All solution standards shall be clearly labeled as
to the identity of the compound or compounds, concentration, date
prepared, solvent, and initials of the preparer.
B. Purchase of chemical standards already in solution
Solutions of analytical reference standards can be purchased by
Contractors provided they meet the following criteria:
1. Laboratories shall maintain the following documentation to verify
the integrity of the standard solutions they purchase:
a. mass spectral identification confirmation of the neat material
b. purity confirmation of the neat material
c. chromatographic and quantitative documentation that the
solution standard was QC checked according to the following
section
2. The Contractor shall purchase standards from chemical suppliers that
demonstrate statistically and analytically the quality of their
prepared standards. The supplier is therefore required to prepare
and analyze three solutions; a high standard, a low standard, and a
standard at the target concentration (see parts a and b below). The
supplier must then demonstrate that the analytical results for the
high standard and low standard are consistent with the difference in
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theoretical concentrations. This is done by the Student's t-test in
part "d". If this is achieved, the supplier must then demonstrate
that the concentration of the target standard lies midway between
the concentrations of the low and high standards. This is done by
the Student's t-test in part e. Thus the standard is certified to
be within 10 percent of the target concentration.
In detail, the supplier must document that the following have been
achieved:
a. Two solutions of identical concentration must be prepared
independently from neat materials. An aliquot of the first
solution must be diluted to the intended concentration (the
"target standard"). One aliquot shall be taken from the second
solution and diluted to a concentration ten percent greater
than the target standard. This is called the "high standard".
One further aliquot shall be taken from the second solution and
diluted to a concentration 10 percent less that the target
standard. This shall be called the "low standard".
b. Six replicate analyses of each standard (a total of 18
analyses) shall be performed in the following sequence: low
standard, target, high standard, low standard, target standard,
high standard, ...
c. The mean and variance of the six results for each solution
shall be calculated.
Equation 2
MEAN - (Yx + Y2 + Y3 + Y4 + Y5 + Yg )/6
Equation 3
VARIANCE - (Y]_ + Y22 + Y32 + Y42 + Y52* + Yg2 - (6*MEAN2))/5
The values Yj, Y2, Y3 represent the results of the six
analyses of each standard. The means of the low, target, and
high standards shall be designated M]_, M2, and M3,
respectively. The variances of the low, target, and high
standards shall be designated V]_, V2, and V3, respectively.
Additionally, a polled variance, Vp, shall be calculated.
Equation 4
Vp - (Vx/(0.81) + V2 + V3 /(I.21))/3
If the square root of Vp is less than one percent of M2, then
M2 /1Q,000 is to be used as the value of Vp in all subsequent
calculations.
d. The test statistic must be calculated:
Equation 5
TEST STATISTIC - |(M3 /l.l) - (Mx /0.9)|/(Vp /3)0'5 -
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If the test statistic exceeds 2.13 then the supplier has failed
to demonstrate a twenty percent difference between the high and
low standards. In such a case, the standards are not
acceptable.
e. The test statistic must be calculated:
Equation 6
TEST STATISTIC - |M2 - (ML /1.8) - (M3 /2.2)|/(Vp /4)0'5
If the test statistic exceeds 2.13, the supplier has failed to
demonstrate that the target standard concentration is midway
between the high and low standards. In such a case, the
standards are not acceptable.
f. The 95 percent confidence intervals for the mean result of each
standard shall be calculated:
Equation 7
Interval for Low Standard = M]_ + (2.13) (Vp
Equation 8
Interval for Target Standard = M2 ± (2.13)(Vp /6)®'^
Equation 9
Interval for High Standard = M3 + (2.13)(Vp /6)®"^
These intervals shall not overlap. If overlap is observed,
then the supplier has failed to demonstrate the ability to
discriminate the 10 percent difference in concentrations. In-
such a case, the standards are not acceptable.
C. Requesting Standards From the EPA Standards Repository
Solutions of analytical reference can be ordered from the U.S. EPA
Chemical Standards Repository, depending on availability. The
Contractor can place an order for standards only after demonstrating
that these standards are not available from commercial vendors either in
solution or as a neat material.
D. Documentation of the Verification and Preparation of Chemical Standards
It is the responsibility of each laboratory to maintain the necessary
documentation to prove the chemical standards they have used in the
performance of CLP analysis conform to the requirements previously
listed. Weighing logbooks, calculations, chromatograms, mass spectra,
etc, whether produced by the laboratory or purchased from chemical
supply houses, shall be maintained by the laboratory and may be subject
to review during on-site inspection visits. Documentation of standards
preparation may be required to be sent to EPA for verification of
contract compliance. In those cases where the documentation is
supportive of the analytical results of data packages sent to EPA, such
documentation shall be kept on file by the laboratories for a period of
one year from the analysis date of any associated sample.
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SECTION V
CONTRACT COMPLIANCE SCREENING
\
Contract Compliance Screening (CCS) is one aspect of the Government's
contractual right of inspection of analytical data, CCS examines the
Contractor's adherence to contract requirements based on the hardcopy sample
data package and the electronic data deliverable to the Agency.
CCS is performed by the Sample Management Office (SMO) under the direction of
the Agency. To assure a uniform review, a set of standardized procedures
have been developed to evaluate the hardcopy sample data package and
electronic data deliverable submitted by the Contractor against the
completeness requirements of the contract.
CCS results are used in conjunction with other information to measure overall
Contractor performance and to take appropriate actions to correct
deficiencies in performance.
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SECTION VI
REGIONAL DATA REVIEW
Contract laboratory data are generated to meet the specific needs of the
Regions. In order to verify the usability of data for the intended purpose,
each Region reviews data from the perspective of end-user, based upon
functional aspects of data quality. General guidelines for data review have
been developed jointly by the Region and the National Program Office. Each
Region uses these guidelines as the basis for data evaluation. Individual
Regions may augment the basic guideline review process with additional review
based on Region-specific or site-specific concerns. Regional reviews, like
the sites under investigation, vary based on the nature of the problems under
investigation and the Regional response appropriate to the specific
circumstances.
Regional data reviews, relating usability of the data to a specific site, are
part of the collective assessment process. They complement the review done
at the Sample Management Office, which is designed to identify contractual
discrepancies and the review done at EMSL/LV which is designed to evaluate
Contractor and method performance. These individual evaluations are
integrated into a collective review that is necessary for program and
laboratory administration and management and may be used to take appropriate
action to correct deficiencies in the Contractor's performance.
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SECTION VII
LABORATORY EVALUATION SAMPLES
Although intralaboratory QC nay demonstrate Contractor and method performance
that can be tracked over time, an external performance evaluation program is
an essential feature of a QA program. As a means of measuring Contractor and
method performance, Contractors participate in interlaboratory comparison
studies conducted by the EPA. Results from the analysis of these laboratory
evaluation samples will be used by the EPA to verify the Contractor's
continuing ability to produce acceptable analytical data. The results are
also used to assess the precision and accuracy of the analytical methods for
specific analytes.
Sample sets may be provided to participating Contractors as frequently as on
an SDG-by-SDG basis as zero blind (recognizable as a QC sample and of known
composition); single blind (recognizable as QC sample and of unknown
composition); or double blind (not recognizable as QC material and of unknown
composition) samples.
Contractors are required to analyze the samples and return the data package
and all raw data within the contract required turnaround time.
Performance Evaluation Samples
Performance evaluation samples (PEs) shall be prepared and analyzed with each
SDG, when provided by EPA. The PEs may be a single blind QC material. The
PEs will be provided as ampules to the Contractor along with directions for
spiking reagent water to generate the actual samples for analysis. The PEs
may be a double blind QC. The PEs may be introduced as a full volume sample
along with other environmental samples sent to the Contractor.
At a minimum, the results are evaluated for compound identification,
quantification, and sample contamination. Confidence intervals for the
quantification of target compounds are based on reported values using
population statistics. EPA may adjust the scores on any given PEs sample to
compensate for unanticipated difficulties with a particular sample.
A Contractor's results on the PEs set will determine the Contractor's
performance as follows:
1. Acceptable, No Response Required (Score greater than or equal to 90
percent):
Data meets most or all of the scoring criteria. No response is
required.
2. Acceptable, Response Explaining Deficiency(ies) Required (Score greater
than or equal to 75 percent but less than 90 percent):
Deficiencies exist in the Contractor's performance.
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Within 14 days of receipt of notification from EPA, the Contractor shall
describe the deficiency(ies) and the action(s) taken to correct the
deficiency(ies) in a letter to the Administrative Project Officer, the
Technical Project Officer and EMSL/LV.
3. Unacceptable Performance, Response Explaining Deficiency(ies) Required
(Score less than 75 percent):
Deficiencies exist in the Contractor's performance to the extent that
the National Program Office has determined that the Contractor has not
demonstrated the capability to meet the contract requirements.
Within 14 days of receipt of notification from EPA, the Contractor shall
describe the deficiency(ies) and the action(s) taken to correct the
deficiency(ies) in a letter to the Administrative Project Officer, the
Technical Project Officer and EMSL/LV.
The Contractor will be notified by the Administrative Project Officer or
Technical Project Officer concerning the remedy for their unacceptable
performance. A Contractor may expect, but EPA is not limited to, the
following actions: Reduction of the number of samples sent under the
contract, suspension of sample shipment to the Contractor, a site visit,
a full data audit, analysis of remedial PE samples, and/or a contract
sanction, such as a Cure Notice.
Note: A Contractor's prompt response demonstrating that corrective
actions have been taken to ensure the Contractor's capability to meet
contract requirements will facilitate continuation of full sample
delivery.
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SECTION VIII
GC/MS TAPE AUDITS
Periodically, EPA requests from Contractors the GC/MS magnetic tapes
corresponding to a specific case in order to accomplish tape audits.
Generally, tape submissions and audits are requested for the following
reasons:
o Program overview
o Indication of data quality problems from EMSL/LV, SMO, or Regional data
reviews
o Support for on-site audits
o Specific Regional requests
Depending upon the reason for an audit, the tapes from a recent case, a
specific case, or a performance sample may be requested. Tape audits provide
a mechanism to assess adherence to contractual requirements and to ensure the
consistency of data reported on the hardcopy/floppy diskettes with that
generated on the GC/MS tapes. This function provides external monitoring of
Program QC requirements and checks adherence of the Contractor to internal QA
procedures. In addition, tape audits enable EPA to evaluate the utility,
precision, and accuracy of the analytical methods.
The GC/MS tape shall include raw data and quantitation reports for samples,
blanks, performance evaluation samples, initial calibrations and continuing
calibration associated with the case requested.
In order to reference raw data to the delivered hard copy, the GC/MS tape
submission shall also include all the following items associated with the
case:
o User-generated spectral libraries
o Extraction laboratory bench sheets
o Analysts' laboratory notebook pages
o Instrument reference logbook pages associating the tape files to the raw
data files. The logbook shall include EPA sample numbers and standard and
blank ID's identified by Case and Sample Delivery group.
Upon request of the Project Officer or EMSL/LV, the required tapes and all
necessary documentation shall be submitted to EPA within seven (7) days of
notification.
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SECTION IX
ON-SITE LABORATORY EVALUATIONS
At a frequency dictated by a contract laboratory's performance, the
Administrative Project Officer, Technical Project Officer and/or authorized
representatives will conduct an on-site laboratory evaluation. On-site
laboratory evaluations are carried out to monitor the Contractor's ability to
meet selected terms and conditions specified in the contract. The evaluation
process Incorporates two separate categories: Quality Assurance Evaluation,
and an Evidentiary Audit.
A. Quality Assurance On-Site Evaluation
o Quality assurance evaluators inspect the Contractor's facilities to
verify the adequacy and maintenance of instrumentation, the
continuity of personnel meeting experience or education requirements,
and the acceptable performance of analytical and QC procedures. The
Contractor should expect that items to be monitored will include, but
not be limited to the following items.
o Size and appearance of the facility
o Quantity, age, availability, scheduled maintenance and performance of
instrumentation
o Availability, appropriateness, and utilization of SOPs
o Staff qualifications, experience, and personnel training programs
o Reagents, standards, and sample storage facilities
o Standard preparation logbooks and raw data
o Bench sheets and analytical logbook maintenance and review
o Review of the Contractor's sample analysis/data package inspection
procedures
Prior to an on-site evaluation, various documentation pertaining to
performance of the specific Contractor is integrated in a profile
package for discussion during the evaluation. Items that may be
included are previous on-site reports, PES scores, Regional review of
data, Regional QA materials, GC/MS tape audit reports, results of CCS,
and data trend reports.
B. Evidentiary Audit
Evidence auditors conduct an on-site laboratory evaluation to determine
if laboratory policies and procedures are in place to satisfy evidence
handling requirements as stated in Exhibit E. The evidence audit is
comprised of the following three activities
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1
Procedural Audit
The procedural audit consists of review and examination of actual
standard operating procedures and accompanying documentation for the
following laboratory operations: sample receiving, sample storage,
sample identification, sample security, sample tracking (from
receipt to completion of analysis) and analytical project file
organization and assembly.
2. Written SOPs Audit
The written SOPs audit consists of review and examination of the
written SOPs to determine if they are accurate and complete for the
following laboratory operations: sample receiving, sample storage,
sample identification, sample security, sample tracking (from
receipt to completion of analysis) and analytical project file
organization and assembly.
3. Analytical Project File Evidence Audit
The analytical project file evidence audit consists of review and
examination of the analytical project file documentation. The
auditors review the files to determine:
o The accuracy of the document inventory
o The completeness of the file
o The adequacy and accuracy of the document numbering system
o Traceability of sample activity
o Identification of activity recorded on the documents
o Error correction methods
C. Discussion of the On-Site Team's Findings
The quality assurance and evidentiary auditors discuss their findings
with the Administrative Project Officer/Technical Project Officer prior
to debriefing the Contractor. During the debriefing, the auditors
present their findings and recommendations for corrective actions
necessary to the Contractor personnel.
D. Corrective Action Reports For Follow-Through to Quality Assurance and
Evidentiary Audit Reports
o Following an on-site evaluation, quality assurance and evidentiary
audit reports which discuss deficiencies found during the on-site
will be forwarded to the Contractor. The Contractor shall discuss
the corrective actions taken to resolve the deficiencies discussed
during the on-site visit and discussed in the on-site reports in a
letter to the Administrative Project Officer, Technical Project
Officer, EMSL/LV (response to the quality assurance report) and NEIC
(response to the evidentiary report) within 14 days of receipt of the
finding or within the time agreed upon between the Administrative
Project Officer/Technical Project Officer and the Contractor. If
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SOPs are required to be written or SOPs are required to be amended,
the Contractor must provide the SOPs to the Technical Project
Officer, EMSL/LV (quality assurance/technical SOPs) and NEIC
(evidentiary SOPs) within 30 days of receipt of the finding or within
the time agreed upon between the Project Officer/Deputy Project
Officer and the Contractor.
If the Contractor fails to take appropriate corrective action to
resolve the deficiencies discussed in the on-site reports, a
Contractor may expect, but the Agency is not limited to, the
following actions: reduction of the number of samples sent under the
contract, suspension of sample shipment to the Contractor, a follow-
up site visit, a full data audit, analysis of remedial PE samples
and/or contract sanction, such as a Cure Notice.
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SECTION X
QUALITY ASSURANCE AND DATA TREND ANALYSIS
Data submitted by laboratories are subject to review from several aspects:
compliance with contract-required QC, usability, and full data package
evaluation. Problems resulting from any of these reviews may determine the
need for a GC/MS tape audit, an on-site laboratory evaluation and/or a
remedial PE sample. In addition, QC prescribed in the methods provides
information that is continually used by the Agency to assess sample data
quality, Contractor data quality and Program data quality via data trend
analysis. Trend analysis is accomplished by entering data into a
computerized data base. Statistical reports that evaluate specific anomalies
or disclose trends in many areas, including the following, are generated from
this data base:
o Surrogate Spike Recovery
o Performance Evaluation Sample
o Blanks
o Initial and Continuing Calibration Data
o Other QC and Method Parameters
Program-wide statistical results are used to rank laboratories in order to
observe the relative performance of each Contractor using a given protocol
against its peers. The reports are also used to identify trends within
laboratories. The results of many of these trends analyses are included in
overall evaluation of a Contractor's performance, and are reviewed to
determine if corrective action or an on-site laboratory evaluation is
indicated in order to meet the QA/QC requirements of the contract.
Contractor performance over time is monitored using these trend analysis
techniques to detect departures of Contractor output from required or desired
levels of quality control, and to provide an early-warning of Contractor
QA/QC problems which may not be apparent from the results of an individual
case.
As a further benefit to the Program, the data base provides the information
needed to establish performance-based criteria in updated analytical
protocols, where advisory criteria has been previously used. The vast
empirical data set produced by contract laboratories is carefully analyzed,
with the results augmenting theoretical and research-based performance
criteria. The result is a continuously monitored set of quality control and
performance criteria specifications of what is routinely achievable and
expected of environmental chemistry laboratories in mass production analysis
of environmental samples. This, in turn, assists the Agency in meeting its
objectives of obtaining data of known and documented quality.
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REFERENCES
1. Fisk, J.F. and Manzo, S.M. "Quality Assurance/Quality Control in
Organics Analysis", Proceedings from the Water Pollution Control
Federation Meeting, May 1986.
2. Office of Monitoring Systems and Quality Assurance, U.S. Environmental
Protection Agency, "Interim Guidelines and Specifications for Preparing
Quality Assurance Project Plans", QAMS-005/80, December 1980.
3. Office of Solid Waste and Emergency Response, U.S. Environmental
Protection Agency, Test Methods for Evaluating Solid Waste, Third
Edition, SW-846, November 1986.
4. Laidlaw, R.H., "Document Control and Chain of Custody Considerations for
the National Contract Laboratory Program," Quality Control in Remedial
Site Investigations: Hazardous and Industrial Solid Waste Testing,
Fifth Volume, ASTM STP 925, C.L. Perket, ed., American Society for
Testing and Materials, Philadelphia, 1986.
5. Health Effects Research Laboratory, U.S. Environmental Protection
Agency, Manual of Analytical Methods for the Analysis of Pesticides in
Humans and Environmental Samples, EPA-600/8-80-036, June, 1980.
6. Environmental Protection Agency, "Guidelines Establishing Test
Procedures for the Analysis of Pollutants Under the Clean Water Act;
Final Rule and Interim Final Rule and Proposed Rule", 40 CFR Part 136,
Federal Register, Vol. 49, No. 209., pp 43234-43442, October 26, 1984.
7. Health Effects Research Laboratory, U.S. Environmental Protection
Agency, Manual of Analytical Quality Control for Pesticides and Related
Compounds In Human and Environmental Samples-Second Revision, EPA-600/2-
81-059, April 1981.
8. Environmental Monitoring Systems Laboratory, U.S. Environmental
Protection Agency, Analytical Reference Standards and Supplemental Data:
The Pesticides and Industrial Chemicals Repository, EPA-600/4-84-082,
October 1984.
9. American Chemical Society Committee on Environmental Improvement, and
Subcommittee on Environmental Analytical Chemistry, "Guidelines for Data
Acquisition and Data Quality Evaluation in Environmental Chemistry",
Analytical Chemistry, Volume 52, Number 14, December 1980.
10. Moore, J.H. and Pearson, J.G. "Quality Assurance Support for the
Superfund Contract Laboratory Program", Quality Control in Remedial Site
Investigation: Hazardous and Industrial Solid Waste Testing, Fifth
Volume, ASTM STP 925, C.L. Perket, ed., American Society for Testing and
Materials, Philadelphia, 1986.
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EXHIBIT E
CHAIN-OF-CUSTODY, DOCUMENT CONTROL AND
STANDARD OPERATING PROCEDURES
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1. CHAIN-OF-CUSTODY PROCEDURES
A sample is physical evidence collected from a facility or from the
environment. Controlling evidence is an essential part of the
hazardous waste investigation effort. To accomplish this, Contractors
are required to develop and implement the following sample
identification, chain-of-custody, sample receiving, and sample tracking
procedures.
1.1 Sample Identification
To assure traceability of the samples while in possession of the
Contractor, the Contractor shall have a specified method for
maintaining identification of samples throughout the laboratory.
Each sample and sample preparation container shall be labeled with the
EPA number or a unique laboratory identifier. If a unique laboratory
identifier is used, it shall be cross-referenced to the EPA number.
1.2 Chain-of-Custody
Because of the nature of the data being collected, the custody of EPA
samples must be traceable from the time the samples are collected until
they are introduced as evidence in legal proceedings. The Contractor
shall have procedures ensuring that EPA sample custody is maintained
and documented. A sample is under custody if:
o It is in your possession, or
o It is in your view after being in your possession, or
o It was in your possession and you locked it up, or
o It is in a designated secure area. (Secure areas shall be
accessible only to authorized personnel.)
1.3 Sample Receiving
1.3.1 The Contractor shall designate a sample custodian responsible
for receiving all samples.
1.3.2 The Contractor shall designate a representative to receive
samples in the event that the sample custodian is not
available.
1.3.3 The condition of the shipping containers and sample bottles
shall be inspected upon receipt by the sample custodian or
his/her representative.
1.3.4 'The condition of the custody seals (intact/not intact) shall be
inspected upon receipt by the sample custodian or his/her
representative.
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1.3.5 The sample custodian or his/her representative shall check for
the presence or absence of the following documents accompanying
the
sample shipment:
o
Airbills or airbill
stickers
0
Custody seals
0
EPA custody records
o
EPA traffic reports
or SAS packing lists
o
Sample tags
1.3.6 The sample custodian or his/her representative shall sign and
date all forms (e.g., custody records, traffic reports or
packing lists, and airbills) accompanying the samples at the
time of sample receipt.
1.3.7 The Contractor shall contact the Sample Management Office (SMO)
to resolve discrepancies and problems such as absent documents,
conflicting information, broken custody seals, and
unsatisfactory sample condition (e.g., leaking sample bottle).
1.3.8 The Contractor shall record the resolution of discrepancies and
problems on Telephone Contact Logs.
1.3.9 The following information shall be recorded on Form DC-l (See
Exhibit B) by the sample custodian or his/her representative as
samples are received and inspected:
o Condition of the shipping container
o Presence or absence and condition of custody seals on
shipping and/or sample containers
o Custody seal numbers, when present
o Condition of the sample bottles
o Presence or absence of airbills or airbill stickers
o Airbill or airbill sticker numbers
o Presence or absence of EPA custody records
o Presence or absence of EPA traffic reports or SAS packing
lists
o Presence or absence of sample tags
o Sample tag identification numbers cross-referenced to the
EPA sample numbers
o Verification of agreement or non-agreement of information
recorded on shipping documents and sample containers
o Problems or discrepancies
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1.4 Sample Tracking
The Contractor shall maintain records documenting all phases of sample
handling from receipt to final analysis.
2. DOCUMENT CONTROL PROCEDURES
The goal of the laboratory document control program is to assure that
all documents for a specified Sample Delivery Group (SDG) will be
accounted for when the project is completed. Accountable documents
used by contract laboratories shall include, but not be limited to,
logbooks, chain-of-custody records, sample work sheets, bench sheets,
and other documents relating to the sample or sample analyses. The
following document control procedures have been established to assure
that all laboratory records are assembled and stored for delivery to
EPA or are available upon request from EPA prior to the delivery
schedule.
2.1 Preprinted Laboratory Forms and Logbooks
2.1.1 All documents produced by the Contractor which are directly
related to the preparation and analysis of EPA samples shall
become the property of the EPA and shall be placed in the
complete sample delivery group file (CSF). All observations
and-results recorded by the laboratory but not on preprinted
laboratory forms shall be entered into permanent laboratory
logbooks. When all data from a SDG is compiled, all original
laboratory forms and copies of all SDG-related logbook entries
shall be included in the documentation package.
2.1.2 The Contractor shall identify the activity recorded on all
laboratory documents which are directly related to the
preparation and analysis of EPA samples.
2.1.3 Pre-printed laboratory forms shall contain the name of the
laboratory and be dated (month/day/year) and signed by the
person responsible for performing the activity at the time an
activity is performed.
2.1.4 Logbook entries shall be dated (month/day/year) and signed by
the person responsible for performing the activity at the time
an activity is performed.
2.1.5 Logbook entries shall be in chronological order. Entries in
logbooks, with the exception of instrument run logs and
extraction logs, shall include only one SDG per page.
2.1.6 'Pages in both bound and unbound logbooks shall be sequentially
numbered.
2.1.7 Instrument run logs shall be maintained so as to enable a
reconstruction of the run sequence of individual instruments.
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Because the laboratory must provide copies of the instrument
run logs to EPA, the laboratory may exercise the option of
using only laboratory or EPA sample identification numbers in
the logs for sample ID rather than government agency or
commercial client names to preserve the confidentiality of
commercial clients.
2.1.8 Corrections to supporting documents and raw data shall be made
by drawing a single line through the error and entering the
correct information. Corrections and additions to supporting
documents and raw data shall be dated and initialed. No
information shall be obliterated or rendered unreadable.
All notations shall be recorded in ink.
Unused portions of documents shall be "z'd" out.
2.2 Consistency of Documentation
The Contractor shall assign a Document Control Officer (DCO)
responsible for the organization and assembly of the CSF.
All copies of laboratory documents shall be complete and legible.
Original documents which include information relating to more than one
SDG shall be filed in the CSF of the lowest SDG number. The copy(s)
shall be placed in the other CSF(s) and the Contractor shall record the
following information on the copy(s) in red ink:
"COPY
ORIGINAL IS FILED IN CSF "
The Contractor shall sign and date this addition to the copy(s).
Before releasing analytical results, the DCO shall assemble and cross-
check the information on samples tags, custody records, lab bench
sheets, personal and instrument logs, and other relevant deliverables
to ensure that data pertaining to each particular sample or sample
delivery group is consistent throughout the CSF.
2.3 Document Numbering and Inventory Procedure
In order to provide document accountability of the completed analysis
records, each item in the CSF shall be inventoried and assigned a
serialized number as described in Exhibit B).
All documents relevant to each sample delivery group, including logbook
pages, bench sheets, mass spectra, chromatograms, screening records,
re-preparation records, re-analysis records, records of failed or
attempted analysis, custody records, library research results, etc.
shall be inventoried.
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The DCO shall be responsible for ensuring that all documents generated
are placed in the CSF for inventory and are delivered to the
appropriate EPA region or other receiver as designated by EPA. The DCO
shall place the sample tags in plastic bags in the file.
2.4 Storage of EPA Files
The Contractor shall maintain EPA laboratory documents in a secure
location.
2.5 Shipment of Deliverables
The Contractor shall document shipment of deliverables packages to the
recipients. These shipments require custody seals on the containers
placed such that they cannot be opened without damaging or breaking the
seal. The Contractor shall document what was sent, to whom, the date,
and the method (carrier) used.
A copy of the transmittal letter for the CSF shall be sent to NEIC/CEAT
and SMO.
3. SPECIFICATIONS FOR WRITTEN STANDARD OPERATING PROCEDURES
The Contractor shall have written standard operating procedures (SOPs)
for receipt of samples, maintenance of custody, sample identification,
sample storage, sample tracking, and assembly of completed data.
An SOP is defined as a written narrative stepwise description of
laboratory operating procedures including examples of laboratory
documents. The SOPs shall accurately describe the actual procedures
used in the laboratory, and copies of the written SOPs shall be
available to the appropriate laboratory personnel. These procedures
are necessary to ensure that analytical data produced under this
contract are acceptable for use in EPA enforcement case preparation and
litigation. The Contractor's SOPs shall provide mechanisms and
documentation to meet each of the following specifications and shall be
used by EPA as the basis for laboratory evidence audits.
3.1 The Contractor shall have written SOPs describing the sample
custodian's duties and responsibilities.
3.2 The Contractor shall have written SOPs for receiving and logging in of
the samples. The procedures shall include but not be limited to
documenting the following information:
3.2.1 Presence or absence of EPA chain-of-custody forms
3.2.2 Presence or absence of airbills or airbill stickers
3.2.3 Presence or absence of traffic reports or SAS packing lists
3.2.4 Presence or absence of custody seals on shipping and/or sample
containers and their condition
3.2.5 Custody seal numbers, when present
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3.2.6
Airbill or airbill sticker numbers
3.2.7 Presence or absence of sample cags
3.2.8 Sample cag ID numbers
3.2.9 Condition of the shipping container
3.2.10 Condition of the sample bottles '
3.2.11 Verification of agreement or non-agreement of information on
receiving documents and sample containers
3.2.12 Resolution of problems or discrepancies with SMO
3.2.13 An explanation of any terms used by the laboratory to describe
sample condition upon receipt (e.g., good, fine, OK)
3.3 The Contractor shall have written SOPs for maintaining identification
of EPA samples throughout the laboratory.
If the Contractor assigns unique laboratory identifiers, written SOPs
shall include a description of the method used to assign the unique
laboratory identifier and shall include a description of the document
used to cross-reference the unique laboratory identifier to the EPA
sample number.
If the Contractor uses prefixes or suffixes in addition to sample
identification numbers, the written SOPs shall include their
definitions.
3.4 The Contractor shall have written SOPs describing all storage areas for
samples in the laboratory. The SOPs shall include a list of authorized
personnel who have access or keys to secure storage areas.
3.5 The Contractor shall have written SOPs describing the method by which
the laboratory maintains samples under custody.
3.6 The Contractor shall have written SOPs describing the method by which
the laboratory maintains the security of any area identified as secure.
3.7 The Contractor shall have written SOPs for tracking the work performed
on any particular sample. The tracking SOP shall include:
o A description of the documents used to record sample receipt,
sample storage, sample transfers, sample preparations, and
sample analyses.
o A description of the documents used to record calibration and
QA/QC laboratory work.
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o Examples of document formats and laboratory documents used In
the sample receipt, sample storage, sample transfer, and sample
analyses,
o A narrative step-wise description of how documents are used to
track samples.
3.8 The Contractor shall have written SOPs for organization and assembly of
all documents relating to each SDG. Documents shall be filed on a
sample delivery group-specific basis. The procedures shall ensure that
all documents including logbook pages, sample tracking records,
chromatographic charts, computer printouts, raw data summaries,
correspondence, and any other written documents having reference to the
SDG are compiled in one location for submission to EPA. The written
SOPs shall include;
o A description of the numbering and inventory method.
o A description of the method used by the laboratory to verify
consistency and completeness of the CSF.
o Procedures for the shipment of deliverables packages using
custody seals.
4, HANDLING OF CONFIDENTIAL INFORMATION
A Contractor conducting work under this contract may receive EPA-
designated confidential information from the Agency. Confidential
information must be handled separately from other documentation
developed under this contract. To accomplish this, the following
procedures for the handling of confidential information have been
established.
4.1 All confidential documents shall be under the supervision of a
designated document control officer (DCO).
4.2 Confidential Information
Any samples or information received with a request of confidentiality
shall be handled as "confidential." A separate locked file shall be
maintained to store this information and shall be segregated from other
nonconfidential information. Data generated from confidential samples
shall be treated as confidential. Upon receipt of confidential
information, the DCO will log these documents into a Confidential
Inventory Log. The information will then be available to authorized
personnel but only after it has been signed out to that person by the
DCO. The documents shall be returned to the locked file at the
conclusion of each working day. Confidential information may not be
reproduced except upon approval by the EPA Technical and Administrative
Project Officer. The DCO will enter all copies into the document
control 'system described above. In addition, this information may not
be disposed of except upon approval by the EPA Administrative Project
Officer. The DCO shall remove and retain the cover page of any
confidential information disposed of for one year and shall keep a
record on the disposition in the Confidential Inventory Log.
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USERS GUIDE
Laboratory Computer Data Entry Program
for the Evaluation of
2,3,7,8 - TCDD
by
QC/MS/MS and LR/GC/MS
Revised
April 1991
by
Peggy Gox
ManTech Environmental Technology, Inc.
by
Debra Horey
Mary Gerken
U.S. Environmental Protection Agency, Region 7
Environmental Services Division
25 Funston Road
Kansas City, Kansas 66115
\
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TABLE OF CONTENTS
Introduction 3
TCDD Data Entry Program 3
GC/MS/KS
GC/MS/MS Initial Calibration 5
GC/MS/HS Blank Response Summary 9
GC/MS/MS Daily Calibration Check 12
GC/MS/MS Worksheet Report 14
GC/MS/MS Final TCDD Report 18
LR/GC/MS
LR/GC/MS Initial Calibration 20
LR/GC/MS Daily Calibration Check 26
LR/GC/MS Worksheet Report 28
LR/GC/MS Final TCDD Report 33
APPENDIX A - Editing Files
APPENDIX B - Example of Completed Report for GC/MS/MS
APPENDIX C - Example of Completed Report for LR/GC/MS
APPENDIX D - Communications and File Transfer
-------
TMTRODPCTIOH
The GC/M5/MS and LR/GC/MS computer programs presented in
this Users Guide vere developed in response to the need for a
method to quickly evaluate and review dioxin data when large
numbers of dioxin samples would be involved. With this objective
in mind, a user friendly computer program was developed using the
dBASE III software.
This guide discusses the input of data by the laboratory
only and is not a comprehensive guide to the whole dioxin
database network. Data entry and evaluation are provided for the
initial calibration through a final TCDD sample report. Each
section was designed as a separate dBASE file and are linked
together through the use of a unique file name. The system is
designed to facilitate data entry through the use of screen
driven monitor prompts.
ac/HB/na amp lr/qc/ms tcdd data entry program
The GC/MS/HS and LR/GC/MS TCDD Data Entry Programs are
designed to work on any IBM portable, XT, AT, or compatible
computers. The computer must be equipped with dBASE III, version
1.1. to operate the dioxin programs.
To use the TCDD Data Entry Program follow the instructions
provided in this Users Guide. Instructions will usually be given
in BOLD print preceded or followed by a narrative explanation
for the command. For the most part, the program will automatically
display either a menu selection to choose from or a screen which
must be filled in.
Since there are a variety of computer models which may be
used in conjunction with this software, no discussion will be
made as to the initial computer startup. The instructions in
this manual are presented assuming the computer has already been
turned on and dBASE III loaded according to the instructions of
the model being used. The TCDD Data Entry Program is contained
on a 5-1/4 inch or a 3.5 inch diskette which can either be copied
onto the fixed disk or accessed from drive A or B. The default
drive should be specified to concur with which ever drive the
computer software is on.
NOTE: To eliminate confusion between upper and lower
case commands the user should set the CAPS
LOCK key to all upper case letters. Also,
printer must be set in condensed print mode.
To access the TCDD Data Entry Program, at the dBASE prompt
[.] type either,
. DO GCMSMS [For GC/MS/MS users]
OR
. DO LRGCMS [For low resolution GC/MS users]
3
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The Users Guide is divided into two parts, one outlines the
input of the GC/MS/MS data and the other input for the LR/GC/MS
data. The Users Guide will discuss data entry for GC/MS/MS users
first. Low resolution GC/MS Users should turn to page 19 for a
discussion of the LR/GC/MS entry.
GC/MS/MS MAIN MENU:
••• WELCOME TO THE GC/MS/MS DIOXIM PROGRAM •••
************** menu *************
1> INITIAL CALIBRATION
2> BLANK RESPONSE SUMMARY
3> DAILY CALIBRATION CHECK
4> WORKSHEET
S> PRINT FINAL REPORT
C> VALIDATE DATA (EPA DATA REVIEW STAFF ONLY)
7> COPY INITIAL CALIBRATION AND BLANK RESPONSE SUMMARY FILES TO
RE-USE WITH NEW DATA
•> PRINT ALL REPORTS
9> EXIT
CH008B A NUMBER FROM 1 TO 9:
Data are entered into the program stepwise starting with the
Initial Calibration, then Blank Response Summary, Daily Calibration
Check, and Worksheet calculations. From these, a Final TCDD
Report is generated and printed out. Option C of the menu is
used by the EPA Regional personnel to validate the data submitted
and is not intended for use by the user(s) who input the data.
Option 7 is used to copy and rename the Initial Calibration and
Blank Response Summary files so that they may be used with a number
of data files. Using this option relieves the user of the necessity
of re-entering this data each time a submittal is made. Option •
allows the user to print all reports generated under options 1-5,
Option 9 exits the program and return to dBASE III.
4
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re/KB/Mg IHIXIAL CALIBRATION
The Initial Calibration section of this program allows for
the input of raw GC/MS/MS calibration data in triplicate at each of
the three concentration levels required by the method. At the end
of data input for each of the analyses, the program will calculate
the RF values for native and surrogate TCDD as well as the 257/259
ion ratio. At the conclusion of the data entry for each concentration
level, the program will calculate the Mean RRF, Standard Deviation,
and %RSD. At the end of all initial calibration data input, the
program will calculate the Overall Mean RRF, Standard Deviation,
and %RSD for native and surrogate TCDD, in addition, it will
determine the overall mean 257/259 ion ratio and acceptable ion
ratio range. If the %RSD for native TCDD does not meet the criteria
set forth in the method, the program will flag this data with an
asterisk.
An Initial Calibration file must be completed for all sets
of data submitted. If no valid initial calibration file currently
exists, the user must select OPTION 1 and enter this data before
attempting to enter sample data. If a valid initial calibration
file already exists, then it may be used by selecting OPTION 7
which will allow the user to copy and rename it, thereby,
alleviating the need to re-enter the initial calibration data.
At the main menu screen, select the appropriate option. If
OPTION l is selected, then the following screen will appear. (Use
of Option 7 will be explained later in the Users Guide.)
*** INITIAL CALIBRATION PROGRAM ***
OPTIONS: 1>ENTER DATA 2>EDIT DATA 3>PRINT REPORT 4>EXIT
The first question regards whether you want to l>enter data,
2>edit data, 3>print report, or 4>exit. If no data have been
entered thus far, the user would want to choose OPTION 1 and
enter data (i.e., no data could be edited yet since none has
previously been entered). However; if data have already been
entered, the user may just want to edit selected entries. In
that case, the user should select OPTION 2. OPTION 3 would be
chosen if just a copy of a report from previously entered data
was needed, and OPTION 4 would be chosen if the user had
erroneously entered the selection and just wanted to get out and
return to the main menu selections.
After an option (except 4) is chosen, the next screen to
appear asks the user to input a file name. Six parts go to make
up the file name: Lab identifier, case number, batch code,
instrument ID , transmittal sequence code, and the calibration
date (MM/DD/YY). This file nomenclature assists the Region in
tracking and identifying the files.
5
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EXAMPLE FILE NOMENCLATURE:
01234 A A B
\ \ \ \ Transmittal Code
\ \ \ Instrument ID
\ \ Batch Code
\ Case Number
Note that the computer program will ask the user to designate
a file name for the Initial Calibration, Blank Response Summary,
Daily Calibration Check, and Worksheet. These files are linked
together through the use of a unique file name, therefore, the
user must give each of them the same name for a data set. Because
of this file naming system it is possible to have several file sets
going simultaneously which have different initial calibrations, etc...
The screen display for entering the file name will be as follows:
INTER YOUR LAB IDENTIFIER:
VtFPCD ipm fimcv lamiDVttf
ENTER THE BATCH NUMBER:
INSTRUMENT IDS
TRANSMITTAL CODE~~(A,B,C,ETC. ) S
CALIBRATION DATE: / /
After the last response has been entered, if OPTION l was
chosen to enter new data, the following screen will be displayed.
ENTER RESULTS 70S EACH CALIBRATION WHEN SHOWN
CALIBRATION SOLUTION CC1--1
ION 257
ION 259
10* 2«3
ION 2€S
NATIVE CONCENTRATION ISI 0.2
SURROGATE CONCENTRATION ISi 0.080
INTERNAL 8TD. CONC. ISl 1.05
Follow the cursor prompts and enter the raw data for CCl,
analysis 1. After each numerical entry, you must hit the enter or
key.
6
-------
After each of the ion area responses are entered, the
program will calculate the 257/259 ion ratio and RF for native
TCDO. These values will be displayed at the bottom of the
terminal screen for your review. The program will ask if all
entries look acceptable. The user should respond with a "N" if
MO and repeat the raw data input. The program will interpret a
<&«turn> to mean that the data were acceptable and sequence you
on to the next initial calibration replicate. Continue entering
raw data in a like manner for replicates two and three of the
CC1 concentration level. At the conclusion of data entry for all
three replicates of the CC1 level, the program will calculate the
Mean RF, Standard Deviation, and %RSD for the level.
Repeat the above entry sequence for the three replicate
analyses of CC2 and CC3. Note that on the CC3 analysis, the
program will also calculate the RF for the surrogate compound in
addition to that of native TCDD.
At the conclusion of the initial calibration data entry, the
program will calculate the Overall Mean RF for native TCDD and
the surrogate compound (for the surrogate only the CC3 level is
used); Overall Standard Deviation; Overall %RSD; mean 257/259
ratio; and acceptable ion ratio range.
A message will be displayed when the computer is done and
signal the user to start the Initial Calibration printout.
An example of a completed Initial Calibration form printout
is attached in APPENDIX C. The printout includes all raw data;
tabulated RFs for native TCDD and the surrogate compound for
CC1, CC2, CC3; Mean RRFs, Standard Deviations, and %RSD for each
CC level as well as the Overall Mean RF, Standard Deviation and
%RSD. The program also tabulates the Mean 257/259 ion ratio and
calculates the acceptable (+/~ 10%) range. The program will flag
(asterisk) any data point which is out of specifications as
indicated at the bottom of the Initial Calibration printout. In
accordance with the analytical methodology, all initial
calibration data must be within limits or else another initial
calibration must be performed until criteria are met. No
analysis should be conducted without an accompanying acceptable
initial calibration.
The user should review the Initial Calibration printout for
errors. If errors are discovered, the user should re-enter the
program (at the end of the printout the program returned to the
main menu) and edit the file by choosing OPTION 2 [edit data].
The edit data option will request the file name, whereupon, the
requested file will be pulled back up and the calibration date
associated with the file will appear. If the date appears wrong,
the user may have inadvertently requested the wrong file and has
a chance to exit the program and re-enter it specifying the
correct file for editing. If the correct file name was entered
hit any key to continue and the following screen should appear:
7
-------
SOLUTION ID *00 WANT TO 1DZT CC_ (ENTER 1,2, OR 3)
After entering the appropriate concentration level which
requires correction, the program will ask what replicate.
80LUTI0N ID YOU WANT TO EDIT CC (ENTER 1,2, OR 3)
ENTER THE REPLICATE #— (ENTER l72, OR 3)
The program will pull up to the screen the data already
entered for the CC solution and replicate indicated. Move the
cursor down to the entry which requires correction and type in
the correct information. At the end of all corrections, the
program will ask if "DATA OK?". If the data as entered are not
OK, then respond "N" for NO. The program will interpret a
to mean YES and continue on. The program then ask if
you would like to edit another record. Again respond "YM or "N".
The entire edit screen at this point should look similar to the
following:
ENTER RE8ULT8 TOR BACH CALIBRATION WHEN SHOWN
ION 257 15047
ION 259 12098
ION 263 Mil
ION 268 79173
NATIVE CONCENTRATION 18I 0.2
SURROGATE CONCENTRATION 18t 0.060
INTERNAL 8TD. CONC. I8t 1.05
RATIO Of 257/259 18 1.244
Rr NATIVE IS 1.714
DATA 01? TYPE «N" IF MOT,
-------
QC/Mg/Mg BLAKE response summary
The Blank Response Summary file allows for the input of data
for twenty (20) replicate analyses of a dilute solution
containing the sample spiking solution. It has been determined
that the spiking solution contains a small percentage of non-
isotopically labeled TCDD. This small amount of TCDD is usually
considered negligible; however, when dealing with the detection
limits in the GC/MS/MS methods, these amounts become significant
and must be accounted for. The Blank Response Summary portion of
this program calculates the blank response and equivalent
concentration of TCDD for each sample and then determines the
Overall Blank Correction Factor which will be applied to all
sample results. In addition, this section computes the Empirical
Limit of Detection as defined in the GC/MS/MS methodology.
To determine the blank response, at the GC/MS/MS main menu
select OPTION 2, BLANK RESPONSE SUMMARY. A screen similar to
that of the Initial Calibration will be displayed.
********** BLANK SUMMARY PROGRAM ****•*•***
OPTIONS: 1>ENTER/ADD BLANKS 2>EDIT BLANKS 3>PRINT WORKSHEET 4>EXIT
The user should respond to the monitor prompt choosing
OPTION 1 for data entry, OPTION 2 to edit existing data, OPTION 3
print the report out only, or OPTION 4 to exit back to the
GC/MS/MS main menu. After an option has been selected, the user
must follow the monitor prompts and fill in the file name.
Remember that the file name must be consistent with the file name
given to the associated initial calibration file.
If OPTION 1 is chosen to enter data, the program will
display one screen at a time for each of the 20 blank replicates.
For each replicate, enter the raw area counts for ion 257, 259,
and 268. The screen will appear as follows:
ENTER RE8ULTS FOR EACH BLANK
SOLUTION 1
ION 257
ION 259
ION 268
9
-------
Once the raw data have been entered, the program will
respond with the blank response calculation and an equivalent
concentration of native TCDD. If an incorrect value was input,
you have an opportunity at this time to correct it (repeat the
entry) by responding "N" [NO] to the question "Data OK?" which
will appear at the bottom of the screen. If a "N" is entered,
simply repeat the entry. The program will interpret a
to mean that the data are OK and continue on to the next replicate
entry. The completed screen will appear similar to the following
display.
ENTER RESULTS TOR BACH BLANK
SOLUTION 1
ION 257 189
ION 259 22
ION 268 21999
BLANK RESPONSE IS 0.012
NATIVB CONCENTRATION IS 0.034
DATA OK? (TYPE "N" IF NOT, RETURN IF OK)
Continue entering the raw data for each of the 20 replicates
until all data have been entered. After the last entry, the
program will calculate the Correction Factor and Empirical Limit
of Detection. (If the limit of detection does not meet criteria,
the user must determine if there were any input errors or rerun
some or all of the blanks and redetermine the Empirical Limit of
Detection.)
The computer will automatically print out the Blank Response
Summary.
An example of a completed Blank Response Summary is attached
in APPENDIX C. The printout includes all raw data; tabulated
blank response and equivalent concentration of TCDD for each of
the 20 replicates; the calculated correction factor; and
empirical limit of detection. The computer program will flag
(asterisk) the empirical limit of detection if it does not meet
criteria.
The user should review the completed Blank Response Summary
for errors. If errors are discovered, the user should reenter the
program and edit the file by choosing OPTION 2 [edit data] of the
Blank Response Summary menu. The edit data option will display
the following screen.
10
-------
MITER THB NUMBER OF THB BLANK YOU WANT TO EDIT
After entering the appropriate blank replicate which
requires correction, the program will pull up to the screen the
data thus far entered for that replicate. Simply move the cursor
down to the wrong entry and correct it. After the correction has
been made, the program will calculate the blank response and
equivalent concentration of native TCDD. It then asks if the
data are OK. The user should respond "H" for NO or a
for YES. The program then asks if you would like to edit another
record. The entire editing screen will appear similar to that of
the original entry at this same stage. After all editing has
been completed, a new Blank Response Summary page will be printed.
D8B OPTION 7 TO COPY INITIAL CALIBRATION/BLANK RESPON8E SUMMARY PILES
The initial calibration and the blank response summary are
usually done only once and may not have to be repeated unless
criteria fail to be met. It is, therefore, in the best interest
of the user to input this data into the system only one time.
This is accomplished through OPTION 7 which allows the user to
copy and rename the two files. These files must be renamed so that
they will be linked to the new daily calibration check and worksheet
files.
From the GC/MS/MS main menu select OPTION 7. The program
will display the following screen.
THIS PR0QRAM LETS YOU COPY YOUR INITIAL CALIBRATION AND BLANK
RESPONSE SUMMARY FILES TO BE RE-USED FOR ANOTHER SET OF DATA
OPTIONS: 1> CONTINUE WITH PROGRAM 2> EXIT TO MENU
FIRST ENTER INFORMATION ON FILE TO BE COPIED:
ENTER THE CASE NUMBER:
ENTER THE BATCH NUMBER:
INSTRUMENT ID:
OLD TRANSMITTAL CODE (A*B«C,ETC.)t
NOV ENTER THE NAME FOR THE NEW FILE:
NEW CASE NUMBER:
NEW BATCH NUMBER:
NEK INSTRUMENT CODE?
NEW TRANSMITTAL CODB (A,B,C,ETC.):
11
-------
OPTION 1 allows you to continue with the program and rename
the Initial Calibration and Blank Response files. OPTION 2
should be selected if you want to exit back to the GC/MS/MS main
menu. If OPTION 1 was chosen simply fill in the necessary
information and a new file for both the initial calibration and
blank response summary will be created.
The program will take you back to the GC/KS/MS main menu at
the conclusion of this screen. To use the renamed files just
specify the new name whenever you are asked for the file name.
For example., on January 1, 1986 Deb's Lab generated their Initial
Calibration and Blank Response Summary files which were named
01298AAA. Samples and a daily calibration standard were
analyzed on January 2 and recorded on Worksheet and Daily
Calibration Check files, respectively. These files were also
named 01298AAA. On January 4 another set of samples were
analyzed as well as a daily calibration standard. Since the
initial calibration and blank response were still valid (still
met criteria), Deb's Lab used OPTION 7 to copy and rename the
two files so that data generated on January 4 could be associated
with them. The new name used was 01299AAA. Note that OPTION 7
will copy and rename the files, that means that they still exist
under the old name and can be retrieved under that name as well
as the new name.
enter data, 2> edit data, 3> print report, or 4> exit.
To enter data choose OPTION 1 and input the file name. This
input is similar to that done in both the initial calibration and
blank response files. Once this information has been entered, the
following screen will be displayed.
12
-------
BNTER RESULTS FOR DAILY CALIBRATION
ANALYSIS DATE
ANALYSIS TIKE
ION 25?
ION 259
ION 283
ION 268
Follow the cursor prompt and enter the analysis date;
analysis tine; and area response for ions 257, 259, 263, and 268.
Please note that the time should be entered using the Military
format and with no colon. After the entries have been made, the
calculations for the 257/259 ion ratio; RF for native TCDD and
surrogate; and tD vill be displayed at the bottom of the
screen for the users review. The program will ask you "Data Ok?"
If the data are not correct, the user should respond "N" for NO
and repeat the entry. The program will interpret a to
mean that data are OK and will continue on. The user should
continue to enter any additional daily calibration checks in a
like manner until all standard runs associated with the data set
have been entered.
At the end of all entries, the program will signal that it
is ready to print out the Daily Calibration Check form. If upon
review, the user notices errors, the file may be edited by re-
entering the Daily Calibration Check file (OPTION 3 of the
GC/MS/MS main menu) and this time selecting OPTION 2 [edit data],
BNTER THE RECORD NUMBER OP TEE ITEM TO EDIT (1,2,3,ETC.)
Inter the number of the record you want to edit. (The first
continuing calibration you entered would be considered entry
number 1, etc...) The program will pull to the screen the
entries you have made for that record. Move the cursor to the
entry which needs changed and simply correct it. The completed
screen should appear similar to the following:
13
-------
ENTER RESULTS FOR DAILY CALIBRATION
ANALYSIS DATE 05/21/88
ANALYSIS TIME 1700
ION 257 51934
ION 259 47889
ION 263 21122
ION 2C8 297016
RATIO or 257/2S9 IS 1.100
RR7 NATIVE IB 1.669
RRF SURROGATE IS 1.642
% DIFFERENCE NATIVE 2.97
% DIFFERENCE SURR. 20.38
DATA OK (TYPE «N" IF NOT, IF OK)
DO YOU HAVE ANOTHER ITEM TO EDIT (Y OR N)
After editing, the file will be reprinted and then return to
the GC/KS/MS main menu.
QQ/mm WORKSHEET
The Worksheet section of this program allows for the input
of raw GC/MS/MS sample data of any matrix. There is no limit to
the number of samples including QC and method blanks that may be
input into any one Worksheet file. The program calculates the
results for each sample based on this information plus previous
information which was entered in the Initial Calibration and Blank
Response sections of the program. At the conclusion of the raw
sample data entry, the program calculates the 257/259 ion ratioi
surrogate * accuracy? and amount of TCDD present and/or detection
limits. From this report a Final Report will be printed. This
sheet will contain the final qualified data results. When
transferring data from the Worksheet to the Final Report the
program will automatically "U" code any data which does not have
a 257/259 ion ratio in the acceptable range. The program will
also automatically raise all detection limits to a predesignated
level for each matrix. When any QC criteria specified in the
contract are not met, the program will flag that item with an
asterisk. The user can look at the bottom of the Final Report
for an explanation of each asterisk. The user should be aware
that this program does not flag the field blank, matrix spike, or
performance evaluation samples out of criteria. The lab will
receive verbal notification from the TPO of non-compliant results
for the PS samples.
14
-------
From the GC/MS/MS main menu, select OPTION 4. The first
screen displayed asks whether the user wants to 1> enter/add
samples, 2> edit samples, 3> print worksheet, or 4> exit.
DIOXIN WORKSHEET DATA ENTRY PROGRAM ***
OPTION8I 1> ENTER/ADD SAMPLES 2> EDIT SANPLE8 3> PRINT
WORKSHEET 4> EXIT
ENTER THE CASE NUMBERt
ENTER THE BATCH NUMBER:
INSTRUMENT ID:
TRANSMITTAL CODE~(A,B,C,ETC.):
For entry of new data, choose OPTION l. The computer then
asks for the file name. Remember to keep the name consistent
with that used for the other files which are associated with this
sample set. After this entry has been completed, the program
will ask for the matrix type.
PIRST CHOOSE THE MEDIUM:
1=WATBR 2=SOIL 3=WIPE 4=INSULATION 5=AIR 6=ASPHALT
7=GRAVEL OPTION-1 8=GRAVEL OPTION-2:
Enter the number which corresponds to the matrix type for
the sample to be entered. The program will ask this same
question for each sample entry such that samples of different
matrices may be reported in the same file. Next enter the
specific sample data.
LAB SAMPLE NUMBER
SMO SAMPLE NUMBER 8M0 QC CODE
EPA SAMPLE NUMBER EPA QC CODE
ANALYSIS DATE / / ANALYSIS TIME
SAMPLE AMOUNT IN GRAMS*
ION
257
8/N RATIO OK—ION
257
>
2.5
(Y
OR
N)
ION
259
8/N RATIO OX—ION
259
>
2.5
(Y
OR
N)
ION
263
8/N RATIO OK—ION
263
>
2.5
(Y
OR
N)
ION
268
8/N RATIO OK—ION
268
>
10
(Y
OR
N)
* Units depend on matrix specified.
15
-------
At the conclusion of all entry, the calculation for the
257/259 ion ratio; surrogate t accuracy; and raw value of TCDD
will appear at the bottom of the screen. The user should review
the data presented. The completed data entry screen appears
similar to the following:
IAS SAMPLE NUMBER a?BWl
8X0 SAMPLE NUMBER 221200001 SMO QC CODE
EPA SAMPLE NUMBER JKDB4001 EPA QC CODS ~
ANALYSIS DATE 04/08/86 ANALYSIS TIME 2112
SAMPLE AMOUNT IN GRAMS
ION
257
S/N RATIO
OK—ION
257
>
2.5
(Y
OR
N)
I
ION
259
197423
S/N RATIO
OK—ION
259
>
2.5
2.5
CY
OR
M>
X
ION
268
4219?!
S/N RATIO
OK—ION
268
>
10
TO KEEP ADDING VALUES
ENTER C,F, OR
At this time the user has the following options: type a ,fC»
to CHANGE the entry; type a "F« to FINISH the file; or press a
which cycles the user on to the next sample that
requires input. Continue entering sample results in a like
manner until all raw data have been entered.
At the end of all entry, type "F" [FINISHED]. The program
will signal that it is ready to print the Worksheet. The user
should review the Worksheet form for errors keeping in mind that
qualifications will appear only on the Final Report.
NOTE: It may be helpful to printout a copy of the Final
Report (OPTION S of the GC/HS/MS main menu) at this time since it
will alert the user to data not meeting criteria due to either an
erroneous entry or need for reanalysis.
16
-------
If errors are found, the user can edit the file by
reentering the Worksheet program (OPTION 4 of the GC/MS/MS main
menu) and choosing OPTION 2 [edit data]. After the file name has
been specified, the program will pull to the screen a listing of
all samples in that file. This listing vill be by EPA Sample
Number. The editing screen vill appear as follows:
HERB ARE ALL THE 8AMPLES IN THE TILES
1 JKDB4001
2 JKDB4002
3 JXDB4003
4 JKDB4004
5 JXDB4005
ENTER THE NUMBER OF THE ITEM TO EDITI
Enter the number of the record you want to edit. The
program vill ask the matrix (same screen as vas displayed for
initial entry). Once that is entered, the program vill pull up
to the screen the data already entered. Simply move the cursor
down to the entry vhich needs correction and make the change.
When all corrections have been made, the program vill redo the
calculations and print them at the bottom of the screen. It then
ask if the data are Ok. An example of a completed screen should
look as follows:
LAB 8AMPLE NUMBER APR0812
8M0 SAMPLE NUMBER 2212Q0001 8M0 QC CODE
EPA SAMPLE NUMBER JKDB4001 EPA QC CODE
ANALYSIS DATE 04/08/86 ANALY8I8 TIME 2147
SAMPLE AMOUNT IN GRAMS 1^.99
ION
257
236061
8/N RATIO OK—ION
257
>
2.5
(Y
OR
N)
X
ION
259
19742?
8/N RATIO OK—ION
259
>
2.5
(Y
OR
N)
X
ION
263
1?9?45
8/N RATIO OK—ION
263
>
2.5
(Y
OR
N)
X
ION
268
8/N RATIO OK—ION
268
>
10
(Y
OR
N)
X
RATIO OF 257/259 IS 1.20
SURROGATE ACCURACY 118.82
RAW VALUE IS 2.956
DATA OK? (TYPE "N" IF NOT, IF OK)
DO YOU HAVE ANOTHER ITEM TO EDIT (Y OR N)
After all editing is complete, the program vill signal that
it is ready to reprint the Worksheet form. At the end of
printing, the program vill return to the GC/MS/MS main menu.
17
-------
qg/Mg/Mfi final report
As previously mentioned, at the completion of the Worksheet
section, data go through a qualification process. Qualified data
are placed on the Final Report. Qualification footnotes are
located at the bottom left of the report form. The Final Report
may be printed by selecting OPTION 5 of the GC/MS/MS main menu
and specifying the file name.
The user should check this report to see that all data of
the set meet the required criteria. Data should not be reported
by the laboratory which do not meet the criteria set forth in
Section VIII of the methods, except for item 7 (Performance
Sample) for which the laboratory may not be aware that they have
failed the above criteria. The laboratory should reanalyze (or
cleanup/reinject depending on matrix) any sample which does not
meet criteria.
In the case where the original sample analysis does not meet
criteria and an automatic rerun is required, if the automatic
rerun meets criteria, then report only the rerun. It should be
reported as the original sample result. If after two analyses
(original and one rerun) all contract criteria are not met,
report both the original and rerun analyses, as follows: Report
the original analysis with no code. Report the rerun analysis
with a "R" code at the end of the SMO#.
Data from automatic reruns which are reported due to a
performance evaluation sample out of criteria should be reported
with a "P" code after the SMO#.
Data from requested renins should be reported with a "Q"
code after the SMO#.
18
-------
LR/GC/MS MAIN MENU:
**• WELCOME TO THE DIOXIN ENTRY AND CALCULATION PROGRAM **•
(LOW RESOLUTION)
************** menxj **************
1> INITIAL CALIBRATION
2> DAILY CALIBRATION CHECK
3> WORKSHEET
4> PRINT PINAL REPORT
5> VALIDATE DATA (EPA DATA REVIEW 0TAFP ONLY)
«> COPY INITIAL CALIBRATION PILE TO RE-USE WITH NEW DATA
7> PRINT ALL REPORTS
8> EXIT
CHOOSE A NUMBER PROM 1 TO 8:
Data are entered into the program stepwise starting with the
Initial Calibration, Daily Calibration Check, and Worksheet
calculations. From these, a Final TCDD Report is generated and
printed out. Option 5 of the menu is used by the EPA Regional
personnel to validate the data submitted and is not intended for
use by the user(s) who input the data. Option 6 is used to copy
and rename the Initial Calibration file so that it may be used
with a number of data files. Using this option relieves the user
of the necessity of re-entering this data each time a submittal
is made. Option 7 allows the user to print out a copy of all
reports for a given file, and Option 8 allows the user to exit
the program and return to dBASE III.
19
-------
ItR/gC/MP INITIAL CALIBRATION
The Initial Calibration section of this program allows for
the input of raw LR/GC/MS calibration data in triplicate at each of
the three concentration levels required by the method. At the end
of data input for each of the analyses, the program will calculate
the RF values for native and surrogate TCDD as well as the 320/322
and 332/334 ion ratios. At the conclusion of the data entry for
each concentration level, the program will calculate the Mean RF,
Standard Deviation, and %RSD. At the end of all initial calibration
data input, the program will calculate the Overall Mean RFs,
Standard Deviation, and %RSD for native and surrogate TCDD. If the
%RSD for native TCDD or the surrogate do not meet the criteria set
forth in the method, the program will flag this data with an asterisk.
An Initial Calibration file must be completed for all sets
of data submitted. If no valid initial calibration file
currently exists, the user must select OPTION 1 and enter this
data before attempting to enter sample data. If a valid initial
calibration file already exists, then it may be used by selecting
OPTION 6 which will allow the user to copy and rename it,
thereby, alleviating the need to re-enter the initial calibration
data.
At the main menu screen, select the appropriate option. If
OPTION 1 is selected, then the following screen will appear.
(Use of OPTION 6 will be explained later in the Users Guide.)
**» INITIAL CALIBRATION PROGRAM *•*
OPTIONSt CENTER DATA 2>BDIT DATA 3>PRINT REPORT 4>SXIT
The first question regards whether you want to l>enter data,
2>edit data, 3>print report, or 4>exit. If no data have been
entered thus far, the user would want to choose OPTION 1 and
enter data (i.e., no data could be edited yet since none has
previously been entered}. However, if data have already been
entered, the user may just want to edit selected entries. In
that case, the user should select OPTION 2. OPTION 3 would be
chosen if just a copy of the report from previously entered data
was needed, and OPTION 4 would be chosen if the user had
erroneously entered the selection and just wanted to get out and
return to the main menu selections.
After an option (except 4) is chosen, the next screen to
appear asks the user to input a file name. Six parts go to make
up the file name: Lab identifier, case number, batch code,
instrument ID, transmittal sequence code, and the calibration
date (MM/DD/YY). This file nomenclature assists the Region in
tracking and identifying the files.
20
-------
EXAMPLE FILE NOMENCLATURE:
01234 A A B
\ \ \ \ Transmittal Code
\ \ \ Instrument ID
\ \ Batch code
\
\ Case Number
Note that the computer program will ask the user to
designate a file name for the Initial Calibration, Daily
Calibration Check, and Worksheet. These files are linked
together through the use of a unique file name, therefore, the
user must give each of them the same name for a data set.
Because of this file naming system it is possible to have several
file sets going simultaneously which have different initial
calibrations, etc... The screen display for entering the file
name vill be as follows:
ENTER YOUR LAB IDENTIFIER:
ENTER THE CASE NUMBER:
ENTER THE BATCH NUMBER:
INSTRUMENT ID: _
TRANSMITTAL CODE (A,B,C,ETC.):
CALIBRATION DATE: / /
After the last response has been entered, if OPTION 1 was
chosen to enter data, the following screen will be displayed.
ENTER RESULTS FOR EACH CALIBRATION WHEN SHOWN
CALIBRATION 80LUTI0N CC1—1
ION 320
ION 322
ION 328
ION 332
ION 334
NATIVE CONCENTRATION 18: 0.2
SURROGATE CONCENTRATION 18: 0.060
INTERNAL 8TD. CONC. 18: 1.05
21
-------
Follow the cursor prompts and enter the raw data for CC1,
analysis 1. After each numerical entry, you must hit the enter
or key. After each of the ion area responses are
entered, the program will calculate the 320/322 and 332/334 ion
ratios and RFs for native TCDD and the surrogate. These values
will be displayed at the bottom of the terminal screen for your
review. The program will ask if all entries look acceptable.
The user should respond with a "H" if NO and repeat the raw data
input. The program will interpret a to mean that the
data were acceptable and sequence you on to the next initial
calibration replicate.
BNTBR RESULTS TOR BACH CALIBRATION WHEN SHOWN
CALIBRATION SOLUTION CC1—1
ION 320 13357
ION 322 141M
ION 328 MM!
ION 332 70783
ION 334 90822
NATIVE CONCENTRATION IS: 0.2
SURROGATE CONCENTRATION 18: 0.0CO
INTERNAL 8TD. CONC. IS: 1.05
RATIO OF 320/322 IS 0.787
RATIO OF 332/334 IS 0.779
RF NATIVE IS 0.939
RF SURROGATE IS 1.109
DATA OI7 (TYPB «N" IF NOT,
-------
A message will be displayed vhen the computer is done and
signal the user to start the Initial Calibration printout. An
example of a completed Initial Calibration form printout is
attached in APPENDIX D. The printout includes all raw data;
tabulated RRFs for native TCDD and the surrogate compound for
CC1, CC2, CC3; Mean RFs, Standard Deviations, and %RSD for each
CC level as veil as the Overall Mean RF, Standard Deviation and
%RSD. The program will flag (asterisk) any data point which is
out of specifications as indicated at the bottom of the Initial
Calibration printout. In accordance with the analytical
methodology, all initial calibration data must be within limits
or else another initial calibration must be performed until
criteria are met. No analysis should be conducted without an
accompanying acceptable initial calibration.
The user should review the Initial Calibration printout for
errors. If errors are discovered, the user should re-enter the
program (at the end of the printout the program returned to the
main menu) and edit the file by choosing OPTION 2 [edit data].
The edit data option will request the file name, whereupon, the
requested file will be pulled back up and the calibration date
associated with the file will appear. If this date appears
wrong, the user may have inadvertently requested the wrong file
and has a chance to exit the program and re-enter it specifying
the correct file for editing. If the correct file name was
entered, hit any key to continue and the following screen should
appear:
SOLUTION ID YOU WANT TO EDIT CC_ (ENTER 1,2, OR 3)
After entering the appropriate concentration level which
requires correction, the program will ask what replicate.
SOLUTION ID YOU WANT TO EDIT CC (ENTER 1,2, OR 3)
ENTER THE REPLICATE #— (ENTER l72, OR 3)
The program will pull up to the screen the data already
entered for the CC solution and replicate indicated. Move the
cursor down to the entry which requires correction and type in
the correct information. At the end of all corrections, the
program will ask if "DATA OK?". If the data as entered are not
OK, then respond "N" for NO. The program will interpret a
to mean YES and continue on. The program then ask if
you would like to edit another record. Again respond "Y" or
"N". The entire edit screen at this point should look similar to
the following:
23
-------
ENTER RESULTS FOR EACH CALIBRATION WHEN SHOWN
ION 320 13357
ION 322 16980
ION 328 10906
ION 332 70783
ION 334 90822
NATIVE CONCENTRATION IS: 0.2
SURROGATE CONCENTRATION IS: 0.060
INTERNAL STD. CONC. IS: 1.05
RATIO OF 320/322 18 0.787
RATIO OF 332/334 IS 0.779
RF NATIVE IS 0.939
RF SURROGATE IS 1.109
DATA OK? TYPE "N" IF NOT,
-------
THIS PROGRAM LETS YOU COPY YOUR INITIAL CALIBRATION
PILE TO BE RB-USBO TOR ANOTHER SET OP DATA
OPTIONS: 1> CONTINUE WITH PROGRAM 2> EXIT TO MENU 1
PIRST ENTER INFORMATION ON PILE TO BE COPIEDI
ENTER THE CASE NUMBER!
ENTER THE BATCH NUMBERS
INSTRUMENT ID:
OLD TRANSMITTAL CODE (A,B,C,ETC.)t _
NOV ENTER THE NAME POR THE NEW PILE:
NEW CASE NUMBER:
NEW BATCH NUMBER:
NEW INSTRUMENT ID: _
NEW TRANSMITTAL CODE (A,B,C,ETC.):
OPTION 1 allows you to continue with the program and rename
the Initial Calibration file. OPTION 2 should be selected if you
want to exit back to the LR/GC/MS main menu. If OPTION 1 vas
chosen simply fill in the necessary information and a new file
will be created containing the initial calibration information.
The program will take you back to the LR/GC/MS main menu at the
conclusion of this screen. To use the renamed files just specify
the new name whenever you are asked for the file name. For
example, on January 1, 1986 Deb's Lab generated their Initial
Calibration file which was named 01298AAB. Samples and a daily
calibration standard were analyzed on January 2 and recorded on
Worksheet and Daily Calibration Check files, respectively. These
files were also named 01298AAB. On January 4 another set of
samples were analyzed as well as a daily calibration standard.
Since the initial calibration was still valid (still met
criteria), Deb's Lab used OPTION 6 to copy and rename the file so
that data generated on January 4 could be associated with them.
The new name used was 01298AAB. Note that OPTION 6 will copy and
rename the file. That means that they still exist under the old
name and can be retrieved under that name as well as the new
name.
25
-------
LR/gC/M9 £&IM CALIBRATION CHECK
Verification of the initial calibration must be done every
12 hours that samples are analyzed by analyzing a standard
solution. The Daily Calibration Check section of this program
allows for the entry of raw data results for all calibration
standards which are associated with the set of sample data. At
the end of the raw data entry, the computer will calculate the
320/322 and 332/334 ion ratios; RRFs for native TCDD and the
surrogate; and the % Difference between the RRF of the daily
calibration and that of the initial calibration. If any of
these items do not meet the criteria set forth in the method (+/-
10%), they will be flagged (asterisk). To enter the Daily
Calibration Check choose OPTION 2 from the LR/GC/MS main menu.
The first screen displayed will be similar to that seen for
the initial calibration. It asks the user to, 1> enter data, 2>
edit data, 3> print report, or 4> exit. To enter data choose
OPTION 1 and input the file name. This input is similar to that
done for the initial calibration. Once this information has been
entered, the following screen will be displayed.
ENTER RESULTS FOR DAILY CALIBRATION
ANALYSIS DATE
ANALYSIS TIKE
ION 320
ION 322
ION 328
ION 332
ION 334
Follow the cursor prompt and enter the analysis date;
analysis time; and area response for ions 320, 322, 328, 332, and
334. Please note that the time should be entered using the
Military format and with no colon. After the entries have been
made, the calculations for the 320/322 and 332/334 ion ratios;
RRFs for native TCDD and surrogate; and %D will be displayed at
the bottom of the screen for the users review. The program will
ask you "Data Ok?". If the data are not correct, the user
should respond "N" for NO and repeat the entry. The program will
interpret a to mean that data are OK and will
continue on.
26
-------
ENTER RESULTS FOR DAILY CALIBRATION
ANALYSIS DATS 08/29/8C
ANALYSIS TIME 1650
ION 320
ION 322
ION 328
ZON 332
ION 334
Mill
M11S.
inn
Mllll
1MMI
RATIO OF 320/322 IS
RATIO OF 332/334 IS
RF NATIVE IS
RF SURROGATE IS
&*-222
It?*?
% DIFFERENCE NATIVE 1.38
% DIFFERENCE SURR. 3.39
DATA OK? (TYPE "N» IF NOT,
-------
ENTER RESULTS FOR DAILY CALIBRATION
ANALYSI8 DATE 08/29/86
ANALYSIS TINE 1700
ION 320
ION 322
ION 328
ION 332
ION 334
49153
62978
4019?
2 65618
215123.
RATIO OF 320/322 18
RATIO OF 332/334 IS
RF NATIVE IS
RF SURROGATE IS
0-780
0.790
0.932
1.098
% DIFFERENCE NATIVE 1.38
% DIFFERENCE BURR. 3.39
DATA OK? (TYPE "N" IF NOT, IF OK)
DO YOU HAVE ANOTHER ITEM TO EDIT (Y OR N)
After editing, the file will be reprinted and then return to
the LR/GC/MS main menu.
LR/QC/MS WORKSHEET
The Worksheet section of this program allows for the input
of raw LR/GC/MS sample data of any matrix. There is no limit to
the number of samples including QC and method blanks that may be
input into any one Worksheet file. The program calculates the
results for each sample based on this information plus previous
information which was entered in the Initial Calibration section
of the program. At the conclusion of the raw sample data entry,
the program calculates the 320/322 and 332/334 ion ratios; surrogate
% accuracy; and amount of TCDD present and/or detection limits.
From this report a Final Report will be printed. The Final
Report will contain the final qualified data results. When
transferring data from the Worksheet to the Final Report the
program will automatically nUn code any data which does not have
a 320/322 ion ratio in the acceptable range. The program will
also automatically raise all detection limits to a predesignated
level for each matrix. When any QC criteria specified in the
contract are not met, the program will flag that item with an
asterisk. The user can look at the bottom of the Final Report
for an explanation of each asterisk. The user should be aware
that this program does not flag the field blank, matrix spike, or
performance evaluation samples out of criteria. The lab will
receive verbal notification from the TPO of non-compliant results
for the PE samples.
From the LR/GC/MS main menu, select OPTION 3. The first
screen displayed asks whether the user wants to 1> enter/add
samples, 2> edit samples, 3> print worksheet, or 4> exit.
28
-------
*** DIOXIN WORKSHEET DATA ENTRY PROGRAM ***
OPTIONS: 1> ENTER/ADD SAMPLES 2> EDIT SAMPLES 3> PRINT
WORKSHEET 4> EXIT
ENTER THE CASE NUMBER:
ENTER THE BATCH NUMBER: _
INSTRUMENT ID:
TRANSMITTAL CODE~(A,B,C,ETC.) :
For entry of data, choose OPTION 1. The computer then asks
for the file name. Remember to keep the name consistent with
that used for the other files which are associated with this
sample set. After this entry has been completed, the program
will ask for the matrix type.
FIRST CHOOSE THE MEDIUM:
1=WATER 2=S0IL 3=WIPE 4=IN8ULATI0N 5=AIR 6=ASPHALT
7=GRAVEL OPTION-1 8=GRAVEL OPTION-2:
Enter the number which corresponds to the matrix type for
the sample to be entered. The program will ask this same
question for each sample entry such that samples of different
matrices may be reported in the same file. Next enter the
specific sample data.
LAB 8AMPLE NUMBER
SMO SAMPLE NUMBER 8MO QC CODE
EPA SAMPLE NUMBER EPA QC CODE
ANALYSIS DATE / / ANALYSIS TIME
8AMPLB AMOUNT IN GRAMS* .
ION
320
8/N RATIO OK—ION
320
>
2.5
(Y
OR
N)
ION
322
8/N RATIO OK—ION
322
>
2.5
(Y
OR
N)
ION
328
8/N RATIO OK—ION
328
>
2.5
(Y
OR
N)
ION
332
8/N RATIO OK—ION
332
>
10
(Y
OR
N)
ION
334
8/N RATIO OK—ION
334
>
10
-------
LAB SAMPLE NUMBER APR0812
SMO SAMPLE NUMBER 2212G0001 SMO QC CODE
EPA SAMPLE NUMBER JKDB4001 EPA QC CODE
ANALYSIS DATE 09/29/86 ANALYSIS TIME 2147
SAMPLE AMOUNT IN GRAMS 4.99
ION
320
1400
S/N RATIO OK—ION
320
>
2.5
(Y
OR
N)
1
ION
322
*80?
S/N RATIO OK—ION
322
>
2.5
CY
OR
H>
1
ION
328
40Q90
S/N RATIO OK—ION
328
>
2.5
CY
OR
N)
1
ION
332
77000
S/N RATIO OK—ION
332
>
10
(Y
OR
H)
I
ION
334
190009
S/N RATIO OK—ION
334
>
10
(Y
OR
N)
2
RATIO OF
320/322
IS 9.78 RATIO OF 332/334
IS
9-
.77
SURROGATE ACCURACY 137.46
RAW VALUE IS: 1236.291
VALUB ISs RERUN CODE IS:
C TO CHANGE ENTRY
7 FOR FINISHED
If the S/N (signal to noise) criteria for ions 320 or 322
were not met, the program will calculate the detection limit
value. The program will ask the user to select either ion 3 20 or
322 for this calculation.
LAS SAMPLE NUMBER APR0812
8MO SAMPLE NUMBER 2212G0001 SMO QC CODE
EPA SAMPLE NUMBER JKDB4001 EPA QC CODE
ANALYSIS DATE 09/29/86 ANALYSIS TIME 2147
SAMPLE AMOUNT IN GRAMS 4.99
ION
320
1400
S/N
RATIO
OK--ION
320 >
2.5
(Y
OR
N)
M
ION
322
1999
S/N
RATIO
OK—ION
322 >
2.5
(Y
OR
N)
E
ION
328
49099
S/N
RATIO
OK—ION
328 >
2.5
CY
OR
N)
X
ION
332
77000
S/N
RATIO
OK—ION
332 >
10
(Y
OR
m
I
ION
334
199999
S/N
RATIO
OK—ION
334 >
10
CY
OR
N)
X
RATIO OF
320/322
IS
0.78
RATIO OF 332/334
IS
9,
77
SURROGATE ACCURACY 137.46
S/N IS OUT—SELECT ION FOR DL CALCULATION: 1> ION 320
2> ION 322
30
-------
At the end of sample entry, the user has the following
options! type a «C» to CHANGE the entry? type a «F« to FINISH
the file; or press a which cycles the user on to the
next sample that requires input. Continue entering sample
results in a like manner until all raw data have been entered.
At the end of all entry, type "F" [FINISHEDJ. The program
will signal that it is ready to print the Worksheet. The user
must input the file name in response to the computer prompts
before the form will print. The user should review the Worksheet
form for errors keeping in mind that qualifications will appear
only on the Final Report.
NOTE: It may be helpful to printout a copy of the Final
Report (OPTION 4 of the LR/GC/MS main menu) at this time since it
may alert the user to data not meeting criteria due to either an
erroneous entry or need for reanalysis.
If errors are found, the user can edit the file by re-
entering the Worksheet program (OPTION 3 of the LR/GC/MS main
menu) and choosing OPTION 2 [edit data].
*** DIOXIN WORKSHEET DATA EDITOR PROGRAM
OPTIONS: 1> EDIT SAMPLES 2> PRINT WORKSHEET 3> EXIT
ENTER THE CASE NUMBER:
ENTER THE BATCH NUMBER:
INSTRUMENT ID:
TRANSMITTAL CODE (A,B,C,ETC.):
After the file name has been specified, the program will
pull to the screen a listing of all samples in that file. This
listing will be by EPA Sample Number. The editing screen will
appear as follows:
HERS ARB ALL THE SAMPLES IN THB PILE:
1 JKDB4001
2 JKDB4002
3 JKDB4003
4 JKDB4004
5 JKDB4005
ENTER THE NUMBER OF THE ITEM TO EDIT (1,2,3,ETC):
31
-------
/
Enter the number of the record you want to edit. The
program will ask the matrix (same screen as was displayed for
initial entry). Once that is entered, the program will pull up
to the screen the data already entered. Simply move the cursor
down to the entry which needs correction and make the change.
When all corrections have been made, the program will redo the
calculations and print them at the bottom of the screen. It
then asks if the data are OK. An example of a completed screen
should look as follows:
LAB SAMPLE NUMBER APR0812
8MO SAMPLE NUMBER 2212G0001 BMO QC CODE
EPA 8AMPLE NUMBER JKDB4001 EPA QC CODE
ANALYSIS DATE 09/29/86 ANALYSIS TIME 2147
SAMPLE AMOUNT IN GRAMS 4.99
ION
320
1499
8/N
RATIO
OK—ION
320
>
2.5
(Y
OR
N)
X
ION
322
1899
S/N
RATIO
OK—ION
322
>
2.5
(Y
OR
N)
X
ION
328
49999
8/N
RATIO
OK—ION
328
>
2.5
(Y
OR
N)
X
ION
332
77999
8/N
RATIO
OK—ION
332
>
10
10
(Y
OR
N)
X
RATIO OF 320/322 IS 0.78 RATIO 07 332/334 18 1.28
SURROGATE ACCURACY 137.46
RAW VALUE 18 1236.291
VALUE IS: RERUN CODE IS:
DATA OK? (TYPE "N" IF NOT, IF OK)
DO YOU HAVE ANOTHER ITEM TO EDIT (Y OR N)
After all editing is complete, the program vill signal that
it is ready to reprint the Worksheet form. At the end of
printing, the program will return to the LR/GC/MS main menu.
LR/QC/MS zuaIt fiOSBX
As previously mentioned, at the completion of the Worksheet
section, data go through a qualification process. Qualified data
are placed on the Final Report. Qualification footnotes are
located at the bottom left of the report form. The Final Report
may be printed by selecting OPTION 4 of the LR/GC/MS main menu
and specifying the file name.
32
-------
The user should check this report to see that all data of
the set meet the required criteria. Data should not be reported
by the laboratory which do not meet the criteria set forth in
Section VIII of the methods, except for item 7 (Performance
Sample) for which the laboratory may not be aware that they have
failed the above criteria. The laboratory should reanalyze (or
cleanup/reinject depending on matrix) any sample which does not
meet criteria.
In the case where the original sample analysis does not meet
criteria and an automatic rerun is required, if the automatic
rerun meets criteria, then report only the rerun. It should be
reported as the original sample result. If after two analyses
(original and one rerun) all contract criteria are not met,
report both the original and rerun analyses, as follows: Report
the original analysis with no code. Report the rerun analysis
with an "R" code at the end of the SMO#.
Data from automatic reruns which are reported due to a
performance evaluation sample our of criteria should be reported
with a "P" code after the SMO#.
Data from requested reruns should be reported with a nQ"
code after the SMO#.
-------
APPENDIX A
EDITING FILES
There are three main ways of editing the files created in
this program with each method having its own limitations. The
choice of which editing method the user wishes to utilize depends
primarily on the level the user is at in the file, and the degree
of editing required. This will become apparent as each method is
explained.
METHOD 1
This method can be used for simple editing. On each screen
there are a number of highlighted blocks which the cursor moves
to and which the user must fill in. If when filling in these
blocks a wrong key was punched, the user may use the backspace
key [<—] to erase the entry. The user can then repeat the entry
correctly. The limitation for this type of editing is that the
backspace key will only go back a limited number of blocks
before an error message is displayed. No problems will be
encountered if the user stays within a block, but an error
message may appear if the user tries too many blocks. The user
should do so with caution and may want to consider editing
Methods 2 or 3 for more extensive editing. This method of editing
only works on data currently being displayed on the screen.
METHOD 2
Each of the sections have been written such that after the
data have been entered, the user has an opportunity to review it.
The program usually asks a question such as "DATA OK?" If the
user responds "N" [NO] to this question, then the program will
allow re-entry of the data. For the Worksheet section, the
program ask if you want to CHANGE an entry for which the user
would respond with a "C". The limitation of this method of
editing is that once you have passed the question and started
another entry, you cannot go back and edit the previous one.
METHOD 2
This is by far the most versatile method of editing and
probably the method that will most often be used by the user.
For each section of the program, the first screen that appears
gives the user three options. These options are the same for
each section. OPTION 2 allows the user to edit data. Whenever
this option is selected the program will ask the file name and
what exactly the user wants to edit (i.e, for the Initial
Calibration the program asks what CC and replicate number; for
the Worksheet the program asks what sample number). The user
should follow the prompts answering each question. The editor
program will pull up to the screen a copy of what the user has
already entered. The user simply has to move the cursor to
the entry which needs correction, make the correction, then hit
a to the bottom of the screen.
-------
APPENDIX B
OC/MS/KS COMPLETED REPORT
-------
LAB:
CASE: 56912 BATCH: A
INSTRUMENT ID: A
TRANSMISSION: A DATE: 04/23/91
GC/MS/HS FINAL DATA REPORT
JLE RECEIVED DATE: 12/03/90
TIME: 1610
SMQ
EPA
ANALYSIS
RATIO
SURROGATE
mo
RERUN
VALID
UNITS
UPLE •
SAMPLE 1
DATE TIMi
257/259
ACC
CONC.
CODE
CODE
<8 LANK
BLANK524N
12/03/90
1508
0.01*
120.65
0.300 U
NG/GM
151121
BU20P910P
12/03/90
1513
1.05
121.94
1.549
NG/GM
151122
8U2DP911F
12/03/90
1520
0.86*
117.42
0.300 U
NG/GM
151214
BU2DP752
12/03/90
1527
0.95*
117.59
0.300 U
NG/GM
151215
SU2DP753
12/03/90
1608
1.10
121.62
0.484
NG/GM
151216
BU2DP734
12/03/90
1615
1.08
120.05
0.370 U
*** A
NG/GM
15121?
BU2DP755
12/01/90
1600
1.03
118.80
0.439
NG/GM
151218
8U2DP756
12/03/90
1622
0.98*
118.70
0.100 U
NG/GM
151219
BU2DP757
12/03/90
1629
0,94*
118.10
0.300 U
HG/SN
<51220
BU2CP758
12/03/90
1639
0.94*
118.67
0.300 U
NG/GM
151221
BU2DP759
12/01/90
1647
1.02
117.09
0.476
NG/GN
51222
BU2DP760
12/03/90
1653
0.97*
118.15
0.300 U
NG/GM
:51223
BU2DP761
12/03/90
1659
0.59*
118.76
0.300 U
NG/GM
51224
SU2DP762
12/03/90
1705
1.09
11B.76
0.300 U
NG/GM
151301
BU2DP763
12/03/90
1711
1.00
117.04
0.477
NG/GM
.ALIFICAIION FUGS:
257/259 RAT 10 OUTSIDE OF ACCEPTABLE RANGE
• SURROGATE OUTSIDE OF ACCEPTABLE RANGE
•* NIGH DETECTION LIMIT
SIGNAL TO NOISE RATIO OUT ON INTERNAL STO
0 QUALITY CONTROL SAMPLE COOES:
RERUN DUE TO PERFORMANCE SAMPLE
REOUESTED RERUN
AUTOMATIC RERUN
A QUALITY CONTROL SAMPLE COOES:
DUPLICATE SAMPLE
METHOD BLANK
FIELD (LANK
SPIKE
PERFORMANCE EVALUATION SAMPLE
A RERUN COOES:
AUTOMATIC RERUN
-------
LAS:
CASE: 56912 MICH: A
INSTRUMENT ID: A
TRANSMISSION: A DATE: 04/23/91
CC/NS/MS WORKSHEET REPORT FORM
SURROGATE CMC 0.1 RF NATIVE 2.286 ION RATIO: 0.991 TO 1.214
INTERNA). SID CONC 1.05 RF SURROGATE 2.11 CORRECTION FACTOR: 0.005
LAI
SMO
EPA
ANALYSIS
SAMPLE
ION 257
ION 259
ION 263
ION 268
RATIO
SURR
RAW
UNI1
SAMPLE •
SAMPLE »
SAMPLE «
DATE
TIME
AMOUNT
257/259
ACC
VALUE
OEC0320
OGMBLANK
BLANK524N
12/03/90
150S
5.20
1
131
4230S
85360
0.01*
120.65
¦0.010
NG/GM
DEC0321
00151121
•U20P910P
12/03/90
1513
5.17
58563
56054
95418
18Sj235
1.05
121.94
1.549
NG/GM
DEC0322
0C151122
¦U2DP911F
12/03/90
1520
5.14
520
607
47157
97761
0.86*
117.42
0.016
NG/GM
DEC0323
0G151214
BU2DP752
12/03/90
1527
5.02
4509
4726
62437
129166
0.95*
117.59
0.176
NG/GN
6EC0327
0B1S1215
BU2DP753
12/03/90
1605
5.18
12324
11172
60890
121622
1.10
121.62
0.484
KG/GM
0EC0328
0G151216
8U20P754
12/03/90
1615
5.11
6903
6392
44584
90259
1.08
120.05
0.370
NG/GM
0EC0326
0015121?
RU2BP755
12/03/90
1600
5.13
20399
19580
113047
231198
1.03
118.80
0.439
KG/GM
DEC0329
DG15121S
IU2DP756
12/03/90
1622
5.06
7036
7217
63112
129432
0.98*
118.70
0.276
NG/GM
OEC0330
DG1S1219
8U2DP757
12/03/90
1629
5.17
5377
5712
60353
124292
0.94*
118.10
0.216
NG/GM
DEC0331
00151220
8U2DP75B
12/03/90
1639
5.18
8788
9307
226231
463928
0.94*
118.67
0.086
NG/GM
DEC0332
0G151221
BU2DP759
12/03/90
1647
5.04
31649
31072
163146
338481
1.02
117.09
0.476
NG/GM
0EC0333
DC151222
BU2DP760
12/03/90
1653
5.16
2946
3033
116224
239421
0.97*
118.15
0.050
NG/GM
DEC0334
00151223
BU20P761
12/03/90
1659
5.09
1300
2209
293978
602593
0.59*
118.76
0.001
NG/GM
DEC0335
BG151224
BU2DP762
12/03/90
1705
5.14
7849
7199
107492
220167
1.09
118.76
0.163
NG/GM
DIC0336
OG151301
BU20P763
12/03/90
1711
5.13
27749
27881
141817
294353
1.00
117.04
0.477
NG/GM
-------
LAB:
CASE: 56912 BATCH: A
INSTRUMENT ID: A
TRANSMISSION: A DATE: 04/23/91
TABLE 3 CC/MS/HS DAILY CALIBRATION CHECK
MEAN NATIVE RF 2.286
MEAN SURROGATE RF 2.506
JON RATIO RANGE 0.993 TO
1.214
NATIVE C«C. 0.2
SURROGATE CONC. .060
INTERNAL STO. COKC . 1.0S
ANALTSIS ANAITSIS ION 257 IOM 259 ION 263 ION 266 RATIO
TIME
RF
NATIVE RF
OATI
12/03/90
till
180681
187035
146311
257/259 NATIVE %OIFF.
819976 1.009 2,406 5.25
RF SURROGATE RF COMMENTS
SURROGATE X DIFFERENCE
3.079
22.87
• IOM RATIO MUST IE WITHIN ACCEPTABLE RANGE OF INITIAL CALIBRATION
•• NATIVE X DIFFERENCE MUST BE LESS THAN 10% FROM INITIAL CALIBRATION
-------
IAS:
USE: 56912 BATCH: A
INSTRUMENT 10: A
TRANSMISSION: A DATE: 04/23/91
TABLE 1 GC/NS/MS INITIAL CALIBRATION RUN 10/12/90
SOLUTION ION 257
ION 259
ION 263
ION 268
NATIVE
SURROGATE
INT. STD
IF
IF
RATIO
ID
CONC
CONC
CMC
NATIVE
SUBROGATE
257/251
CC1-1
49187
45283
31411
215353
0.2
.060
1.05
2.303
2.509
1.086
CC1-2
88517
79292
55638
384995
0.2
.060
1.05
2.288
2.486
1.116
CC1-J
86809
78089
54403
385121
0.2
.060
1.05
2.248
2.429
1,112
ME AM
2.280
STO OEV
0.028
S ISO
1,23
CC2-1
655JJ
58507
17013
56797
1.0
.110
1.05
2.293
2.740
1.120
CC2-2
71954
64866
19564
62630
1.0
.110
1,05
2.294
2.863
1.109
CC2-3
102925
93663
27257
89090
1.0
.110
1.05
2.317
2.801
1.099
MEAN
2.301
STO OEV
0.014
X (SO
0.61
CCJ-1
1627358
1478756
154384
284084
5.0
.200
1.05
2.296
2.528
1.100
CCS-2
1228175
1115331
115334
216106
5.0
.200
1.05
2.277
2.480
1.101
CC3-3
1788480
1638567
171895
319258
5.0
.200
1.05
2.254
2.509
1.091
COMMENTS
HEAM 2.276 2.506
STD OEV 0.021 0.024
* (SO 0.92 0.96
If NATIVE OVERALL MEAN 2.286
STB DEV 0.014
1 ISO 0.604
IF SURROGATE OVERALL MEAN 2.506
STD OEV 0.024
% ISO 0.958
OVERALL BATEO 257/259 MEAN: 1.104
MMGE: 0.993 TO 1.214
* IF NATIVE X RELATIVE STAKOARD OEVIATION MUST BE IESS THAN 10*
•• IATIO OF 257/259 OUTSIDE OF ACCEPTABLE RANGE
-------
LAB:
CASE: 56912 BATCH: A
INSTRUMENT ID: A
TRANSMISSION: A DATE: 04/23/91
TABLE
2
BLANK
SUMMARY
RUN 04/05/90
SOLUTION
ION 257
ION 259
ION 266
BLANK
NATIVE
ID
RESPONSE
CONC
1
69
971
140360
0.007
0.016
2
332
47
151343
0.003
0.005
3
723
15
165426
0.004
0.010
4
231
1
164281
0.001
0.003
S
467
142
212921
0.003
0.006
6
1
47
143431
0.000
0.001
7
45
1
189640
0.000
0.001
8
938
304
123310
0.010
0.022
9
1628
2292
217698
0.019
0.041
10
1079
1198
142324
0.016
0.035
11
1
94
162376
0.001
0.001
12
1
704
151592
0.005
0.010
13
304
1424
167222
0.010
0.023
14
1
139
155590
0.001
0.002
15
1
1
176878
0.000
0.000
16
1
63
137631
0.000
0.001
17
265
1
64750
0.004
0.009
IB
1
1872
152315
0.012
0.027
19
1
87
197529
0.000
0.001
20
904
1031
152472
0.013
0.028
ERECTION FACTOR • 0.005
HIT Of DETECTION ¦ 0.044
LIMIT OF DETECTION MUST BE LESS TKAN 0.3
-------
APPENDIX C
LR/QC/MB COMPLETED REPORT
-------
FILE RECEIVED DATE: 03/05/91
TINE: 2210
LR/GC/MS FINAL DATA REPORT
LAS:
CASE: 5691J BATCH: A
INSTRUMENT ID: G
TRANSMISSION: A DATE: 04/23/91
SMO
EPA
ANALTSIS
RATIO
RATIO
SURROGATE
7 COO RERUN
VALID UNITS
SAMPLE I
SAMPLE f
DATE
TINE
320/322
332/334
ACC
CONC. CGOE
COOE
METHB161
METHI161M
03/05/91
1859
0.00'
0.7V
97.37
0.300 U
NG/GM
DG141612
0BN57429P
03/05/91
1908
0.77
0.79
102.91
7.399
NG/GM
0G1416O1
ZU10P7Z5
03/05/91
1928
0.81
0.79
99.53
0.720
NG/GM
DG141603
ZU1DP727
03/05/91
1949
0.77
0.80
92.28
2.468
NG/GM
DG141604
ZU10P728
03/05/91
1959
0.78
0.79
104.59
2.781
NG/GM
DG141605
ZU1DP751
03/05/91
2009
0.77
0.79
97.09
4.415
NG/GM
DGH1606
ZU1DP752
03/05/91
2019
0.77
0.79
106.66
2.637
NG/GM
DG141608
BU2DP041
03/05/91
2030
0.76
0.80
102.14
6.534
NG/GM
0GK1609
BU2DP042
03/05/91
2041
0.76
0.78
99.83
30.191
NG/GM
DGK1610
BU20P043
03/05/91
2051
0.77
0.79
93.51
11.984
NG/GM
0G141607
ZU1DP773
03/05/91
2101
0.78
0.79
93.25
2.295
NG/GM
DG141602
ZU10P724
03/05/91
2142
0.78
0.80
99.92
1.471
NG/GM
QUALIFICATION FLAGS:
• 320/322 0* 332/33* RATIO OUTSIDE OF ACCEPTABLE RANGE
•• SURROGATE OUTSIDE OF ACCEPTABLE RANGE
••• HIGH DETECTION LIMIT
f SIGNAL TO NOISE RATIO OUT ON SURROGATE 08 INTERNAL STD
SMO OUALITT CONTROL SAMPLE CODES:
P RERUN DUE TO PERFORMANCE SAMPLE
Q REQUESTED RERUN
¦ AUTOMATIC RERUN
EPA OUALITT CONTROL SMVU CODES:
D DUPLICATE SAMPLE
E WTNOO BLANK
F FIELD BLANK
I SPIKE
P PERFORMANCE EVALUATION SAMPLE
CPA RERLH COOES:
A AUTOMATIC RERUN
SPECIAL INSTRUCTIONS (IF ANT):
-------
LAS:
CASE: 56913 BATCH: A
INSTRUMENT 10: C
TRANSMISSION: A DATE: 04/23/91
IR/GC/MS WORKSHEET REPORT FORM
SJRROCATE CONC 0.060 RRF NATIVE 0.960 INTERNAL STD CONC 1.05 RRF SURROGATE 1.U
LAI
SMO
EPA
SAMPLE
ION 320
ION 322
ION 328
ION 332
ION 334
RATIO
RATIO
SURR
RAW
SAM>LE
f SAMPLE f
SAMPLE f
AMOUNT
320/322
332/334 ACC
VALUE
NETHI161 NETNS161
METM8161M
10.00
0
115
83355
201859
254763
0.00*
0.79
97.37
0.007
NG/0
525312
DG141612
0SN57429P
5.00
160217
209446
124422
279983
355202
0.77
0.79
102.91
7.399
NC/GM
525301
DGU1601
2U1DP725
10.00
22372
27791
82870
195399
247413
0.81
0.79
99.53
0.720
NG/GM
525303
DG141603
ZU10P727
10.00
69516
90801
72257
183586
229387
0.77
0.80
92.28
2.468
NG/GM
525304
DG141604
2U1DP728
10.00
66976
86085
69373
154701
195146
0.78
0.79
104.59
2.781
NG/GM
525305
DCH1605
ZU10P751
10.00
132S61
172169
81491
193501
245713
0.77
0.79
97.09
4.415
NG/GM
525306
0CU16O6
ZU1DP752
10.00
74567
96866
83524
182813
230525
0.77
0.79
106.66
2.637
NG/GM
525soa
DG141608
8U2DP041
10.00
K8855
194967
65806
148308
186196
0.76
0.80
102.14
6.534
NG/GM
S2S309
0G1416O9
BU20P042
10.00
734208
962116
755 06
156768
200414
0.76
0.78
99.83
30.191
NG/GM
525310
DCH1610
BU2DP043
10.00
262305
339612
59032
140819
178479
0.77
0.79
93.51
11.984
NG/GM
525307
DG141607
ZU1DP773
10.00
64934
83650
72716
181495
230164
0.78
0.7V
93.25
2.295
NG/GM
525302
DGH1602
ZU1DP726
10.00
34814
44794
64867
152681
191448
0.78
0.80
99.92
1.471
NG/GM
-------
LAS:
CASE: S6913 BATCH: A
INSTRLMENT ID: C
TRANSMISSION: A DATE: OA/21/91
TAKE 2 U/CC/NS OAllT CALIIRATION CHECK
MIAN NATIVE IF 0.960
MEAN SURROGATE *F 1.144
NATIVE CONC. 0.2 INTERNAL STO. COMC.i 1.05
SURROGATE CONC. 0.060
ANALYSTS ANALYSIS ION 320 ION 322 ION 328 ION 332 I0N334 RATIO RATIO RRF NATIVE RRF RRF SURROGATE RRF
BATE TIME
320/322 332/334 NATIVE XDIFF. SURROGATE * DIFFERENCE
03/05/91 1800 32942 42364 27254 187473 235420 0.778 0.796 0.935 2.60 1.112
2.80
• ION RATIO MUST IE WITHIN ACCEPTABLE RANGE OF INITIAL CALIIRATION
*• NATIVE X DIFFERENCE MUST IE LESS THAN IDS FROM INITIAL CALIIRATION
-------
LAB:
CASE: 56913 BATCH: A
INSTRUMENT ID: 6
TRANSMISSION: A DATE: 04/23/91
TABLE 1 ll/GC/HS INITIAL CALIBRATION HUN 03/05/91
SOLUTION ION 320
ID
ION 322 ION 328 ION 332 ION 334
NATIVE SUMOGATE INT. STB RRf RRf RATIO RATIO
CONC CONC CONC NATIVE SUMOGATE 320/322 . 312/334
CC1-1
CC1-2
CG1-3
40010
39416
35134
52757
51458
45373
33656
31836
30248
230035
215269
206853
291613
271531
260182
0.20
0.20
0.20
0.060
0.060
0.060
1.05
1.0S
1.05
0.934
0.980
0.905
1.113
1.128
1.118
0.758
0.766
0,774
0.789
0.793
0.795
MEAN
STO DEV
1 ISO
0.940
0.038
4.04
1.120
0.008
0.71
CC2-1
CC2-2
CC2 3
174545 227843
167594 220871
165806 215718
58350
54730
53623
19J710
187402
184372
243730
235534
232471
1.00
1.00
1.00
0.110
0.110
0.110
1.05
1.05
1.05
0.966
0.964
0.961
1.229
1.190
1.181
0.766
0.759
0.769
0.795
0.796
0.793
MEAN
STO OEV
S ISO
0.964
0.003
0.31
1.201
0.025
2.08
CCJ-1
CC3-2
CCS-3
885419 1156059
890707 1156941
840306 1091313
103067
102114
99569
189179
193163
191121
237401
244584
240696
5.00
5.00
5.00
0.200
0.200
0.200
1.05
1.05
1.05
1.005
0.982
0.939
1.140
1.100
1.091
0.766
0.770
0.770
0.797
0.790
o.m
MEAN
STD OEV
S ISO
0.975
0.034
3.43
1.110
0.026
2.3*
«f NATIVE OVERALL MEAN 0.960
STD DEV 0.018
X BSC 1.895
•F SURROGATE OVERALL MEAN 1.144
STD DEV 0.050
% RSO 4,344
• RF NATIVE X RELATIVE STANOARO DEVIATION MUST BE LESS THAN 10S
•• RATIO OF 320/322 OS RATIO OF 332/334 OUTSIOi OF ACCEPTABLE RANGE
-------
APPENDIX D
COMMUNICATIONS AND FILE TRAN8FER
-------
File Transfer and Communications with EPA Region 7 Environmental
Services Division.
I. Installation and configuration of OnLAN/PC software
Files will be sent to the division*s LAN fileserver through the
OnLAN/PC software provided on the prograa disks. To install and
set up OnLAN/PC on your hard drive, do the following:
1. At the DOS prompt, enter the name of the hard drive on which
you wish to install the software (usually this is the C
drive).
Cl
Create a directory for the software,
create a directory called ONLAN:
MD ONLAN
The following will
3. Change to the directory you made in Step 2.
CD ONLAN
4. Insert the diskette containing OnLAN/PC in either you A or B
diskette drive.
5. Copy the OnLAN software from the diskette. If the diskette
is in the A drive, the command will be:
COPY A:\ONIAN\*.* C:
6. You will now need to start OnLAN PC to set it up for your
system. Do this with the following command:
ONLAN
7. We have configured OnLAN/PC as follows:
Data rate AUTO
Comm port C0M1
Connect type Modem: Hayes compatible
Phone # / description 913,551,5223
If you need to change any of these, move the arrow to that
option and press RETURN. This will bring up a menu with the
available choices for that option.
Generally, only the Connect type will require change. Moving
the arrow to this option and pressing RETURN will bring up a
menu with three options: Automatic Modem, Manual Modem and
Direct Connect. Select Automatic Modem, and then the type of
modem connected to your system. If your modem is connected
to COM2 or COM3 instead of COMl, you will also have to select
and change the Comm port setting.
8.
If you have made any changes to the OnLAN/PC configuration,
you must save them by pressing Ft.
-------
II. Transferring files
To transfer a file, do the following:
1. Change to the directory which holds the OnLAN/PC software.
If that directory is called ONLAN, the command from DOS would
be the following:
CD \ONLAN
2. Once in the ONLAN directory you may type in ONLAN GO
or
ONLAN and then press 72 from the OnLAN main menu to initiate
a call to the division.
3. When the connection is established, you will be prompted for
the global password to the LAN. Contact EPA Lab for this
password.
4. The next prompt will be for your Login Name. Type in
LABDATA
5. A menu will then appear with three options:
F1 SEND A FILE
F2 RECEIVE A FILE
F3 EXIT THIS LAN (LOGOUT)
To transfer a file from your PC to the division's fileserver,
Press 71.
6. At the bottom of the screen you will be prompted first to
enter the name of the file to be transferred. Enter the
complete path and filename to be certain of your PC's access
to the file. If, for example, the file is called FILENAME on
a directory called DIRNAME on a diskette in your A drive,
answer A:\DIRNAME\FILENAME.
7. You will then be prompted for a name to be given this file on
the fileserver. DO NOT include any path names here. Merely
provide a name up to 8 characters in length and a 3 letter
extension if needed (check with lab personnel for a naming
convention.) A carriage return starts the transfer.
8. After the transfer is completed, log off the LAN, by choosing
73 EXIT THIS LAN
9. To disconnect press the CTRL and the RIGHT SHIFT. This
brings up an OnLAN/PC menu. Select
END ONLAN/FC 8ession.
10. Once you have disconnected from the laboratory file server,
press F10 to exit the OnLAN program.
------- |