&EPA
United States Office of Water (WH-550) EPA 810-B-92-012
Environmental Protection Office of Pesticides and February 1992
Agency Toxic Substances (H-7501C)
QUALITY ASSURANCE PROJECT PLAN
FOR THE
NATIONAL PESTICIDE SURVEY OF DRINKING WATER WELLS
ANALYTICAL METHOD 6 - ETHYLENE TH1OUREA
Prepared by:
BATTELLE
Columbus Division
505 King Avenue
Columbus, Ohio 43201-2693
Prepared for:
U.S. Environmental Protection Agency
Technical Support Division
Office of Drinking Water
26 W. Martin Luther King Drive
Cincinnati, Ohio 45268
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
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Section No. 1
Revision No. 3
Date: April 29, 1988
Page 2 of 2
APPROVAL PAGE
o-
r-
Date
<>BCD Project Manager
Date
BCD QAU Manager
Date
EPA Contract Technical Officer
Date
EPA Contract Project Officer
Date
EPA QA Officer
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Section No 2
Revision No 3
Date: April 29, 1988
Page 1 of 3
NATIONAL PESTICIDE SURVEY
QUALITY ASSURANCE PROJECT PLAN FOR
ANALYTICAL METHOD 6 - ETHYLENE THIOUREA
2. TABLE OF CONTENTS
Section Pages Revisions Date
1. TITLE AND APPROVAL PAGE 2 3 4/29/88
2. TABLE OF CONTENTS 3 3 4/29/88
3. PROJECT DESCRIPTION 2 3 4/29/88
4. PROJECT ORGANIZATION AND RESPONSIBILITY 6 3 4/29/88
4.1 Project Organization
4.2 Authority, Responsibilities, and
Communication
4.2.a NPS Contract Technical Monitor
4.2.b NPS Contract Project Officer
4.2.c Battelle Project Manager
4.2.d CSC
4.2.e Battelle Sample Receipt
Personnel
4.3 Position of the QA Function within the
Project Organization
5. QA OBJECTIVES FOR MEASUREMENT DATA 6 3 4/29/88
5.1 Initial Demonstration of Capabilities --
Determining Reporting Limits
5.2 Initial Demonstration of Capabilities --
Determining MS Detection Limits
5.3 Assessing Laboratory Performance
5.3.a Control Charts
5.3.b Laboratory Control Standards
5.4 Assessing Surrogate Recovery
5.5 Assessing the Internal Standard
5.6 Assessing Analyte Recovery
5.7 Assessing Laboratory Contamination
5.8 Assessing Instrument Performance
5.9 Analyte Confirmation
5.10 Treatment of Unidentified Peaks
5.11 Performance Evaluation Samples
6. SAMPLING PROCEDURES 4 3 4/29/88
7. SAMPLE CUSTODY 6 3 4/29/88
8. CALIBRATION PROCEDURES AND FREQUENCY 3 3 4/29/88
8.1 Instrumentation
8.2 Calibration Procedures
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Page 2 of 3
2. TABLE OF CONTENTS (continued)
Section Pages Revisions Date
9. ANALYTICAL PROCEDURES 2 3 4/29/88
10. DATA REDUCTION, VALIDATION AND REPORTING 7 3 4/29/88
10.1 Data Reduction and Storage
10.1.a Primary and Confirmatory
GC-NPD Analyses
10.1.b GC-MS Identification or
Confirmation
10.1.C Datastorage
10.2 Data Validation
10.3 Data Reporting
10.3.a ASCII Data Packets
10.3.b Monthly Reports
11. INTERNAL QUALITY CONTROL CHECKS 2 3 4/29/88
12. PERFORMANCE AND SYSTEM AUDITS 4 3 4/29/88
12.1 System Audits
12.1.a Sample Receiving/Storage
12.1.b Labwsre
12.1.C Materials, Reagents, Solvents,
and Gases
12.1.d Chemical Solutions/Performance
Standards
12.1.e Analytical Methods
12.1 .f Analyst Training
12.1.g Equipment Calibration/
Maintenance
12.1.h Facilities
12.1.i Standard Operating Procedures
12.1.J Data Records/Reports
12.2 Performance Audits
12.3 Audits Conducted by the USEPA
13. PREVENTIVE MAINTENANCE 4 3 4/29/88
14. SPECIFIC ROUTINE PROCEDURES USED TO
ASSESS DATA PRECISION, ACCURACY AND
COMPLETENESS 2 3 4/29/88
14.1 Standsrd Devistion
14.2 Percent Recovery
14.3 Relstive Standard Deviation
14.4 Peak Symmetry snd Peak Gaussian
Factors
14.5 Minimum Detectsble Level
14.6 Estimated Detection Limit
14.7 Minimum Reporting Level
14.8 Control Limits
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2. TABLE OF CONTENTS (continued)
Section
14.9 Dixon's Test
14.10 Rounding Numbers and Significant
Figures
15. CORRECTIVE ACTION
16. QUALITY ASSURANCE REPORTS TO
MANAGEMENT
Section No 2
Revision No 3
Date- April 29, 1988
Page 3 of 3
Pages Revisions Date
4/29/88
4/29/88
Appendices
A. METHOD 6. DETERMINATION OF ETHYLENE
THIOUREA (ETU) IN GROUND WATER BY GAS
CHROMATOGRAPHY WITH A NITROGEN-
PHOSPHORUS DETECTOR
B. DIXON'S TEST FOR OUTLIERS
C. ETU CONFIRMATION BY LOW-RESOLUTION
GC-MS
D. STANDARD OPERATING PROCEDURE FOR USE
OF ADMIRAL FREEZERS
E. STANDARD OPERATING PROCEDURE FOR USE
OF HOTPOINT REFRIGERATORS
F. STANDARD OPERATING PROCEDURE FOR
WEIGHT DETERMINATIONS USING AN
ELECTRONIC ANALYTICAL BALANCE
G. STANDARD OPERATING PROCEDURE FOR
THE USE OF TOP LOADING BALANCES
H. DATA ENTRY FORMATS FOR ASCII REPORTS
I. STANDARD OPERATING PROCEDURE FOR
QUALITY ASSURANCE UNIT PERFORMANCE
AND SYSTEM AUDITS FOR NPS SURVEY
J. STANDARD OPERATING PROCEDURE FOR
PROPER USE OF SIGNIFICANT FIGURES
AND ROUNDING
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5
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3
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6
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Section No 3
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Page 1 of 2
3. PROJECT DESCRIPTION
The U.S. Environmental Protection Agency will conduct a National Pesticide Survey to locate
and define the type and extent of pesticide contamination of national ground water and to aid in
predicting causes and trends in ground water contamination. There will be eight methods used for
the Survey, seven for the determination of pesticides and pesticide degradates and one for nitrate, for
determination of trace levels of over 120 analytes of interest in ground water samples collected for the
NPS. Approximately 1500 domestic and community water system wells will be sampled.
During implementation of Contract No. 68-03-3525, Battelle will conduct National Pesticide
Survey (NPS) Method 6 to detect, quantify, and confirm the presence or absence of ethylene thiourea
(ETU) in ground water by gas chromatography using a nitrogen-phosphorus detector (GC-NPD).
Commitment to quality is an integral part of every staff member's job at Battelle. The Project Team
recognizes the formal functions necessary to assure clients that the work meets their needs and to
define and control the quality of data and products. These functions are quality assurance (QA) and
quality control (QC). Quality assurance functions are a management tool independent of the technical
organization of projects, including all systems designed to assure both Battelle's administrative and
project management and the client of the quality of our research and products. Quality control
functions are integral activities within technical support projects that are designed to assess or control
data precision and accuracy. These functions deal with establishing procedures for attaining
prescribed standards of performance in the monitoring and measurement processes. Specific QA
goals for Contract No. 68-03-3525 include:
Fulfillment of every commitment to quality, integrity, and propriety,
• Identification, anticipation, and avoidance of potential risks,
Assurance of credentials of technical personnel,
• Quality assurance training,
• Inspections and audits for adherence to the QA Project Plan and completeness and
accuracy of reporting, and
Assurance that any problems are promptly assessed and appropriate corrective
actions are implemented.
Specific QC goals include:
Assurance that all data are scientifically valid, defensible, and of known and
acceptable precision and accuracy, and
Maintenance of the QA Project Plan after consultation with EPA to reflect all
available information for NPS Method 6.
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Section No 3
Revision No. 3
Date: April 29, 1988
Page 2 of 2
This document describes quality assurance and quality control procedures to be enacted during the
project. Each of the components listed below is considered an integral part of the entire Quality
Assurance Project Plan, and each component is necessary to assure defendable analytical results:
Both data and product quality are vitally important. Data quality includes all features and
characteristics that bear on given objectives, particularly accuracy, precision, completeness,
representativeness, and comparability. Product quality encompasses the means of ensuring the
quality of the data and the ability to respond to EPA needs in an efficient and responsive manner.
These goals of data and product quality are reflected in this QA Project Plan.
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Section No 4
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Page 1 of 6
4. PROJECT ORGANIZATION AND RESPONSIBILITY
Three major activities are key to efficient, high-quality projects: planning, performance, and
assurance. High-quality products are realized through Battelle's project management system.
High-quality performance is achieved through the skills and competence of Battelle's technical staff
following carefully designed QC procedures. QA is the responsibility of the technical staff with
assistance from Battelle's independent QA organization that verifies compliance with regulations and
project plans.
4.1 Project Organization
The organization of this project, shown in Figure 1, has been structured to provide the planning,
control, accountability, technical quality, responsiveness and flexibility needed to achieve EPA's
objectives for the NPS. This organization will also ensure that the project will have the attention and
commitment of Battelle management to provide responsiveness and quick resolution of any conflicts.
Ms. Tina Engel will serve as Project Manager on Contract No. 68-03-3525 because of her direct
involvement with the development of NPS Method 6. Ms. Engel has been Battelle's focal point for
interaction with EPA personnel during the development and validation of NPS Method 6. Her
management of this project will assure a smooth transition into the NPS analytical contract.
Ms. Engel reports directly to Dr. Judith Gebhart, the Manager of the Analytical Chemistry
Section. Dr. Gebhart will review the progress of the project and, as needed, provide management
guidance and assistance to Ms. Engel. Dr. Gebhart reports to Dr. Ronald L Joiner, the Vice President
of the Chemistry and Biomedical Sciences Department; Dr. Joiner is also available to provide
additional management assistance. The relationship of the project to the overall Battelle organization
is shown in Figure 2.
Also key to the project are the following personnel:
• Ms. Ramona Mayer, Manager of the Quality Assurance Unit (QAU) -Ms. Mayer
directed QAU activities during the NPS Pilot Study. Ms. Mayer will coordinate QA
activities and report directly to Battelle senior management.
Ms. Sandy Anderson -- Ms. Anderson is the QA Specialist assigned to conduct
audits and review data for this project. Ms. Anderson has chemistry training and
years of experience auditing data generated by the Analytical Chemistry
Department.
Mr. David Zimmerman, Method Leader - Mr. Zimmerman performed all aspects of
Method 6 during the NPS Pilot Survey. He will be responsible for overseeing daily
laboratory activities, reviewing results, and performing all GC analyses.
Mr. Thomas Danison, Sample/Data Manager - Mr. Danison developed and will
maintain the Method 6 database during the NPS Pilot Study. Mr. Danison will
oversee sample receipt and generation of analysis results.
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FIGURE 1
PROJECT ORGANIZATION
Section No. 4
Revision No. 3
Date: April 29, 1988
Page 2 of 6
Vice Presiaen-
-. D.Barker
h
•iirtU P"!«.
R . A . M<
..s
Enaei
fietnod Leaner
I . - . I: .•nffi&r.T.sn
E. A. •- ircher
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Date: April 29, 1988
Page 3 of 6
FIGURE 2
RELATIONSHIP OF PROJECT TO OVERALL BATTELLE ORGANIZATION
Battelle
Columbus Division
W.J.Madia,President
Manufac & Adv Materials
Elect & Defense Systems
Inform & Engin Systems
Biological and Chemical
Sciences Technical Center
A.D.Barker, Sr. Vice Pres
Ocean Sciences & Tech
Toxicology
Environmental Sciences
Chemistry and Biomedical
Sciences Department
R.L.Joiner, Vice Pres
Medical & Chem Sciences
— Chemistry & Spectroscopy
Hazardous Materials Lab
Analytical Chemistry
Section
J.E.Gebhart,Manager
Project Team
T.M.Engel, Manager
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Section No 4
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Page 4 of 6
• Mr. Bruce Hidy, MS Confirmation Coordinator -- Mr. Hiay will provide mass
spectrometry (MS) support.
• Ms. Elizabeth Kircher -- Ms. Kircher will be trained by Mr. Zimmerman and
subsequently perform laboratory functions required by Method 6.
4.2 Authority, Responsibilities, and Communication
Final responsibility for QA/QC for this project rests with the Project Manager, Ms. Tina M. Engel.
Ms. Engel will communicate results, progress, and other pertinent information to the NPS Contract
Technical Monitor. Ms. Engel will be the primary contact at Battelle for the NPS Contract Technical
Monitor.
Mr. David Zimmerman, the Method Leader, will have primary responsibility for quality. Mr.
Zimmerman will direct all daily laboratory activities and perform required GC analyses. Mr.
Zimmerman will also be responsible for training laboratory personnel (Ms. Kircher) in the use of
Method 6. Mr. Zimmerman will evaluate Method 6 analytical and QC results, initiate corrective actions
when necessary, and report corrective actions to Ms. Engel. Mr. Zimmerman will be responsible to
Ms. Engel for completing all work in accordance with the defined QA requirements of the project and
the specific QA requirements for NPS Method 6. Mr. Zimmerman will eventually be responsible for
sample receipt and generation of results from the Method 6 database.
Mr. Thomas Danison, the Sample/Data Manager, will be responsible for receipt of samples and
for other computerized sample tracking and data reporting functions. Mr. Danison will continue to
maintain the Method 6 database, but will train Mr. Zimmerman to take over sample receipt and results
generation duties. Mr. Danison will report directly to Ms. Engel.
Mr. Bruce Hidy will be responsible for conducting MS confirmations of ETU when required. Mr.
Hidy will report progress and results directly to Ms. Engel.
The QA program, designed to assure Ms. Engel, her line management, and EPA that data are
complete, defensible, and traceable, will function in parallel to the technical leadership. The Project
Team and the QA team will have comparable authority and responsibility to the Project Manager for
final approval of work and resolution of conflicts.
Responsibilities of the QA Manager and the QA team include:
Coordination of QA/QC matters with EPA to ensure that all policies and procedures
are in accordance with EPA guidelines,
• Overseeing all QA procedures for the project,
Identifying and responding to quality needs and problems, answering questions for
guidance and assistance, and training project staff in QA/QC requirements and
procedures,
• Ensuring that the QA Project Plan includes sufficient and appropriate specifications
for QA/QC,
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• Interacting with the Project Manager to ensure that QA/QC procedures are
understood by technical personnel,
• Developing SOPs or protocols for performing system inspections and audits,
Auditing all data before release to EPA,
• Performing system and performance audits as required, and
Preparing periodic reports of progress and QA inspection/audit findings to Battelle
management and the Project Manager.
4.2.a NPS Contract Technical Monitor
All analytical results and relevant technical information will be communicated to the NPS Method
6 Contract Technical Monitor:
Dr. Aubry Dupuy, Jr. [Telephone # (601) 688-3212]
U.S. EPA
Environmental Chemistry Laboratory
NASA/NSTL
Building 1105
NSTL, MS 39529
4.2.b NPS Contract Project Officer
All contractual information will be communicated to the NPS Method 6 Contract Project Officer:
Mr. Robert A. Maxey [Telephone # (601) 688-1225]
U.S. EPA
Environmental Chemistry Laboratory
NASA/NSTL
Building 1105
NSTL, MS 39529
4.2.c Battelle Project Manager
Inquiries from EPA personnel regarding this project should be directed to the Battelle Project
Manager:
Ms. Tina M. Engel [Telephone # (614) 424-4149]
Battelle Columbus Division
505 King Avenue
Columbus, OH 43201
4.2.d CSC
Analytical results will be submitted to Mr. Chris Frebis at CSC:
Mr. Chris Frebis
USEPA/CSC
26 West Martin Luther King Dr.
Cincinnati, OH 45268
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4.2.e Battelle Sample Receipt Personnel
Federal Express shipments of samples should be addressed to the Battelle Sample/Data
Manager:
Mr. Thomas Danison [Telephone # (614) 424-5599]
Battelle Columbus Division
505 King Avenue
Columbus, OH 43201
The Battelle Receiving Department will be provided with a list of alternate personnel in the event that
Mr. Danison is not available to take possession of samples.
4.3 Position of the QA Function within the Project Organization
In accordance with EPA guidelines, QA personnel for this project will function independently of
the technical groups that generate, process, interpret, and report data. Implementation of the QA
program relies on strong management and well-defined organization. Overall management
responsibility for the QA program rests with Ms. Ramona Mayer, Manager of the QAU. Ms. Mayer
reports directly to Dr. Ann D. Barker, Senior Vice President of Biological and Chemical Sciences. An
organizational chart showing the position of the QA function within Battelle Columbus Division and its
relationship to the project is shown in Figure 1. The QA Manager and her staff will interact with
project management throughout the project by conducting audits and inspections and working with
the Project Team to implement and/or correct required QA procedures. The QAU will assure the
Battelle project management that QC procedures outlined in this QA Project Plan are properly
implemented and documented.
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5. QA OBJECTIVES FOR MEASUREMENT DATA
The purpose of this project is to provide EPA with analytical support necessary to implement the
National Pesticide Survey. Battelle will perform the organic analysis procedure defined in NPS
Methods 6. Battelle's objective is to perform Method 6 as written, incorporating any modifications
specified by EPA, and to yield results fully acceptable to both EPA and Battelle. NPS Method 6 is
included for reference as Appendix A.
The following capability demonstration procedures and QC requirements will be followed.
Samples failing any QC criteria will be reanalyzed at Battelle's expense. Deviations from analytical
procedures and/or QC requirements must be approved by the EPA Technical Monitor and
subsequently documented in writing.
5.1 Initial Demonstration of Capabilities •- Determining Reporting Limits
Prior to analysis of NPS samples, Battelle will determine the ETU minimum reporting level (MRL)
using the following procedure:
(1) After optimization of primary analytical instrumentation, the concentration of ETU in
the final extract, in ^g/mL, necessary to produce an instrument detector response
with a 5:1 signal-to-noise ratio (S/N) will be determined. The equivalent ETU
concentration in the original water sample, assuming quantitative recoveries and a
1 0-fold concentration factor, will be calculated.
(2) Eight reagent water samples will be spiked at the concentration level determined in
Step (1); the eight spiked water samples will be processed and analyzed in a single
day using the primary column.
(3) The Minimum Detectable Level (MDL) will be calculated using the equation given in
Section 14.5.
(4) The estimated detection limit (EDL) will be calculated as described in Section 14.6.
(5) If the calculated EDL is greater than 10 ng/L (two times the value given in NPS
Method 6), the results will be reported to the NPS Contract Technical Monitor for
resolution.
(6) The eight extracts generated in step (2) will be analyzed using the confirmation
column, and the EDL will be recalculated as described in steps (3) and (4). If the
calculated EDL determined using the confirmation column is greater than the EDL
determined using the primary column, the higher EDL will prevail to assure that
minimal criteria are met on both columns.
(7) The ETU MRL is defined as three times the EDL calculated using primary analytical
conditions (Section 14.7).
Results from the initial determination of MRLs will be reported to the NPS Contract Technical
Monitor for approval prior to analysis of NPS samples.
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5.2 Initial Demonstration of Capabilities - Determining MS Detection Limits
Battelle performed analyses by low-resolution gas chromatography-mass spectrometry (GC-MS)
to determine the estimated MS detection limit for ETU. Battelle obtained a mass spectrum for ETU
and selected three characteristic ions for subsequent use during selected ion monitoring analyses.
Solutions containing low levels of ETU were analyzed with and without preconcentration to determine
the concentration at which a 5:1 S/N for the least intense characteristic ion is obtained.
Results from initial MS detection limit studies were reported to the NFS Contract Technical
Monitor for approval; MS confirmation procedures to be used in the NPS project are given in
Appendix C.
5.3 Assessing Laboratory Performance
5.3.a Control Charts
Control of the measurement system will be accomplished via use of control charts. Control
must be demonstrated for ETU and the surrogate, propylene thiourea (PTU). Prior to analysis of NPS
samples, Battelle will generate control charts. These control charts will be continuously updated and
used to determine when the analyses being performed using Method 6 are "in control." Samples or
sample sets will be reanalyzed at Battelle's expense if judged out of control.
Five reagent water samples will be spiked at 10 times the MRL for the method and carried
through extraction and analysis using primary conditions. An additional 15 samples will be spiked and
analyzed, five on each of three different days. The results from these 20 spiked samples will be used
to construct control charts using the following criteria for accuracy and precision:
(1) The relative standard deviations (RSDs) for ETU and PTU must be <20 percent.
(2) The mean recoveries for ETU and PTU (x) must lie between the mean recovery ±3
times the RSD listed in Method 6 (at the corresponding concentration level), but no
greater than Battelle's mean recovery ±30 percent.
Failure to meet the above criteria will be reported to the NPS Contract Technical Monitor.
Control charts will be generated containing both warning limits (±2RSD) and control limits
(±3RSD) about the mean. Dixon's test (see Appendix B) will be used to determine outliers using a
one percent risk of false rejection. Up to three outliers can be removed from the data set generated
from the 20 spiked samples prior to compiling the control charts. During analysis of NPS samples, a
spiked control is included in each sample set. When five spiked controls have been analyzed, the
results from these controls will be incorporated into the control charts, and up to five of the earliest
plotted points will be dropped from the control chart; a total of 20 points will be included on each
control chart at all times after initial generation of the control chart. Accuracy and precision will be
recalculated and the chart will be redrawn. The updated control chart will be applied to all data in
sample sets subsequent to the last one used to update the chart.
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The original control charts will be submitted to the NPS Contract Technical Monitor for approval
and inclusion in the EPA Project Plan prior to analysis of NPS samples; updated control charts will be
provided to the NPS Contract Technical Monitor upon request.
5.3.b Laboratory Control Standards
A laboratory control standard (LCS) will be processed and analyzed with each set of samples.
A sample set is defined as all samples extracted by the same analyst on the same day within 12
hours. The laboratory control standard is prepared by spiking reagent water containing 10 mg/L
mercuric chloride with surrogate and ETU at 10 times the MRL The recoveries of ETU and PTU must
be within the control limits (±3RSD) of the current control chart. If the recovery of ETU or PTU is not
within the control chart control limits, the measurement system is "out of control", all samples
associated with the laboratory control standard are invalidated, and work will be stopped until the
problem is resolved. However, a laboratory control standard in which the PTU surrogate compound
recovery has failed to meet the quality control limits is validated if the laboratory control standard
meets all other required quality control elements, and the PTU recovery observed for the method
blank associated with that same sample set meets the control limits determined using the current PTU
control chart. Sample sets will be reanalyzed at Battelle's expense if deemed "out of control." Out of
control situations will be reported to the NPS Contract Technical Monitor. The following observations
indicate an "alert" situation:
Three or more consecutive ETU or PTU recoveries outside the warning limits
(±2RSD) but within the control limits (±3RSD),
A run of seven consecutive points for ETU or PTU above or below the mean, or
A run of seven consecutive points for ETU or PTU in increasing or decreasing order.
An alert situation will warrant close evaluation to avoid deterioration to an out of control situation.
5.4 Assessing Surrogate Recovery
All samples and blanks will be fortified with the surrogate standard, PTU, prior to extraction. The
PTU recovery must be within ±30 percent of the mean recovery indicated on the current control chart
for PTU. Samples in which PTU recoveries do not meet these requirements will be reanalyzed at
Battelle's expense.
5.5 Assessing the Internal Standard
The internal standard, 3,4,5,6-tetrahydro-2-pyrimidinethiol (THP), is added to every sample
extract before analysis. The internal standard peak area for any sample must not deviate by more
than ±20 percent from the mean peak area for the calibration standards. A sample set for this
purpose is defined as all sample extracts and calibration samples analyzed using the same instrument
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in a continuous period. If an internal standard deviates from the mean by more than 20 percent, the
analysis is out of control, and actions as described in Section 10.4 of Method 6 will be taken.
5.6 Assessing Analyte Recovery
EPA will provide a duplicate ground water sample for use as a Laboratory Sample Spike (LSS)
for 10 percent of all samples collected. Battelle will spike the duplicate water sample with ETU at 2, 10
or 20 times the ETU MRL, as specified by EPA, prior to sample preparation and analysis.
5.7 Assessing Laboratory Contamination
A laboratory method blank, consisting of 50 mL of reagent water containing 10 mg/L of mercuric
chloride preservative and spiked with the surrogate, will be analyzed with each set of samples. If the
method blank exhibits a peak within the retention window of ETU and is greater than or equal to
one-half the MRL for that analyte, an out of control situation has developed and will be reported to the
NPS Contract Technical Monitor. If the method blank exhibits a PTU surrogate recovery that is not
within the PTU control chart, that sample is invalidated unless a field sample in the same sample set
meets all of the quality control requirements for a method blank.
5.8 Assessing Instrument Performance
Instrument performance will be monitored daily by analysis of the Method 6 instrument QC
standard as described in Section 10.9 of Method 6. The instrument QC standard contains
compounds designed to indicate appropriate instrument sensitivity, column performance, and
chromatographic performance. The instrument QC standard described in Section 10.9 of Method 6
may be modified to reflect MRL requirements as described in that section.
5.9 Analyte Confirmation
If ETU is observed at a concentration greater than or equal to half the MRL using primary
GC-NPD analytical conditions, the sample will be reanalyzed using confirmatory GC-NPD conditions
and compared to a standard containing ETU at a concentration within ±20 percent of that expected
from primary analysis results. If primary and confirmatory calculated ETU concentrations vary by more
than 25 percent, the NPS Contract Technical Monitor will be informed for resolution of the
discrepancy. If the presence of ETU is confirmed using the second set of GC-NPD conditions, Battelle
will inform the EPA Contract Technical Monitor by phone and followup letter, and the presence of ETU
in the sample will be confirmed by GC-MS.
Confirmation by GC-MS will be done by comparison to a standard containing ETU at a
concentration near that expected in the sample extract. If additional sample treatment is performed to
allow GC-MS confirmation, the standard and sample must both undergo the same treatment. GC-MS
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results will be reported as qualitative (presence or absence), not quantitative, and the ETU
concentration determined using primary GC-NPD conditions will be reported to the EPA Contract
Technical Monitor. Low-resolution GC-MS calibration procedures and operating conditions are given
in Appendix C.
If confirmation can not be performed by low-resolution GC-MS, the sample extract or extracts will
be sent weekly, at EPA's expense under iced conditions by next-day air, to the Environmental
Chemistry Laboratory, NASA/NSTL for confirmation by high-resolution GC-MS. Sample extracts will be
sealed in glass ampules or vials with Teflon-faced closures such that a tight seal and
noncontaminating conditions are provided. The volume level of the sample extracts will be marked on
the outside of the containers. Copies of chromatograms and all pertinent sample information will be
sent along with the extracts.
Following either two successful or two unsuccessful GC-MS confirmation attempts, discussions
with the EPA Contract Technical Monitor will be initiated before continuation of low-level GC-MS
confirmation work. Only ETU concentrations positively confirmed by GC-MS will be reported by the
EPA Contract Technical Monitor to the Method and Analytical Coordinators. Unconfirmed results will
not be reported outside the NPS analytical system.
5.10 Treatment of Unidentified Peaks
During the course of the ETU analyses, unidentified peaks may be detected using the primary
GC-NPD analytical conditions. If the response of an extraneous peak on the primary column is equal
to or greater than the response of the ETU at ten times the MRL, Battelle will attempt to identify that
unknown peak by low-resolution GC-MS. If possible, a full scan spectra will be generated for the
unknown component, and the spectra will be evaluated by comparison to available library spectra. If
possible, the spectra will be compared to a spectra generated at Battelle from an authentic standard
of the suspected compound. Successful as well as unsuccessful identification attempts will be
reported to the EPA Contract Technical Monitor.
Battelle will attempt to identify unknowns as soon as they are detected in an extract. If
identification of the unknown is not possible by low-resolution GC-MS, Battelle will package and send
the extracts from the sample in question and its method blank to EPA as described in Section 5.9. for
identification by high-resolution GC-MS. Sample and analytical information will be sent with the
extracts, including the sample ID No., weight of the sample matrix contained in the ampule or vial, and
copies of chromatograms from the primary GC column with the unknown(s) clearly marked.
If an unidentified compound displaying the same retention time is successfully or unsuccessfully
identified twice, the situation will be discussed with EPA Contract Technical Monitor before
continuation of identification work with that peak. Only compounds positively confirmed by GC-MS will
-------
Section No 5
Revision No 3
Date. April 29, 1988
Page 6 of 6
be reported by the EPA Contract Technical Monitor to the Method and Analytical Coordinators. No
unconfirmed results will be reported outside the NFS analytical system.
5.11 Performance Evaluation Samples
EPA may provide Battelle with blind performance evaluation samples. Performance evaluation
samples will be analyzed with NPS samples and the results will be reported to the NPS Contract
Technical Monitor.
-------
Section No 6
Revision No 3
Date: April 29, 1988
Page 1 of 4
6. SAMPLING PROCEDURES
Battelle will conduct NPS Method 6 on ground water samples submitted by EPA. Sample bottle
preparation, sample collection, and sample shipping will be performed by EPA's implementation
contractor (ICF). NPS Method 6 involves the extraction and analysis of a 50-mL water sample.
Samples will be collected in 60-mL bottles each containing 0.6 ml_ of 1 g/L mercuric chloride
(preservative) in deionized water. Samples from a site will be shipped as a kit. The composition of a
kit is demonstrated in Figure 3. Samples will be iced immediately after collection and shipped iced for
overnight delivery. Samples that are not iced at receipt will not be analyzed and the problem will be
reported to the EPA Contract Technical Monitor. Samples will be stored at 4±2°C away from light
until processed.
Sample bottles will be labeled by field collection personnel. Labels will include the following
information:
National Pesticide Survey - NPS,
• Sample number,
Sampling date,
• Sample description, and
• Sampler.
An example of the label used by ICF is given as Figure 4.
Field personnel will also record pertinent information such as sampling date and time and
sample temperature at collection onto field sample tracking sheets. These sheets will be transferred
to the analytical laboratories with the samples. An example of a field sample tracking sheet
used by ICF is included as Figure 5.
-------
Section No 6
Revision No 3
Date. April 29, 1988
Page 2 of 4
FIGURE 3
COMPOSITION OF METHOD 6 SAMPLE KIT
LAB NAME
BCD
KIT TYPE
Sample Types
BOTTLE TYPE
ANAL METHOD
Primary
Referee
Shipping Blank
Backup Sample
Lab Spikes
Time Storage
T/S Dups @ 30
Totals
No. of Sites
TOTAL REQ'D
BCD #1
Regular
60 mL
6
1
1
2
1,275
2.550
BCD #2
Reg. + LS
60 mL
6
1
1
1
3
150
450
BCD #3
Reg. + LS+T/S
60 mL
6
1
1
1
2
2
7
75
525
Total Bottles:
1,OOOmL= 0
250 mL = 0
60 mL = 3,525
-------
Section No 6
Revision No. 3
Date: April 29, 1988
Page 3 of 4
FIGURE 4
SAMPLE NPS LABEL
NATIONAL PESTICIDE SURVEY
SAMPLE #: PD-0005-5-6-01
BCD - METHOD* 6 KIT: 521
FIELD SAMPLE
PRESERVATIVE: HgCI2
DATE I TIME I SAMPLER
Legend: - R = resample
B = performance evaluation
Well type - D = domestic
C = commercial
Sample type identifier -
01 = field sample
03 = backup sample
04 = lab spike (A1)
06 = lab spike (A3)
Sample Number Explanation:
PD-0005-5-6-01
| Sample Type Identifier
i Method # (6)
| [ Lab # (5)
! Site #
Well Type
NPS Designation
-------
FIGURE 5
NPS FIELD SAMPLE TRACKING SHEET
HELL. i.O. NO.: 0000
FRDS I.D. No. (CHS HELL ONLY):
SAMPLE COLLECTION DATE: /
TRACKING FORM COMPLETED BY:
Section No. 6
Revision No. 3
Date: April 29, 1988
Page 4 of 4
LAB: BSL.
SCENARIO: _l_
HT !£.: PM-000-6U
£01 1 o: 1
TO 3£ COMPLETED BY:
ICF
SAMPLE
NUMBER
f 5-0000-6- 1-01
FD-(JUOO-6-3-01
PD-OOOO-fc-e-01
PI-vOOO-6-1-03
i
BOTTLE
SIZE
1000
1000
t>0
1000
SAMPLE
DESCRIPTION
FIELD SAMPLE
FIELD SAMPLE
FIELD SAMPLE
BACKUP SAMPLE
FIELD TEAM , L«3
SAMPLER 1 TIRE : COMMENTS til '.RECEIVE; ; COHHENIS sli
(INITIAL) i SAMPLED , ;
: : ; : : u;
: : : HI
; : . : : *:
: : ; : • N;
LHLQRiNE TEST:
! SHIPPED BY:
: RECEIVE; AT LAB sv:
1 DATE
! SENT TO:
TIME
LAB ADDRESS:
BAY St. u;j-3
CHEMIST*' .Ai.
NSTL. C.S -3'5:s
t'+'.s. 11. •*
; :-ATE
. -li For. ciAHPLE: B3TT.E BROKEN, BOTTLE MsSSi.15, OVERFL.Ei ?CTTi£. CAP »»i :?.uFF£S
: ii) F3R EXAMPLE: 3QTTLE BROKEX, BOTTLE HISSING. S3TTLE ICkTWlMTES. TE«£t.AT'jF.E CRITERIA KCT -£T
: -" FLR EiAMPLE: SC£ MELTED, SOI LEAKING
: i Lib comnts should concur nth NPS 13 SAMPLE RECEIPT i
-------
Section No 7
Revision No. 3
Date: April 29, 1988
Page 1 of 6
7. SAMPLE CUSTODY
The EPA implementation contractor, ICF, will notify Battelle about sample shipments using a
computerized bulletin board system. Battelle will access this bulletin board system via phone lines
using an IBM-compatible computer equipped with a modem. Battelle will check the bulletin board
weekly to obtained updated information regarding on-going and projected sampling efforts being
coordinated by ICF. Battelle will check the bulletin board daily if sampling efforts are underway or
imminent. Battelle will report routine sample receipt information such as time of receipt and
temperature of samples at receipt to ICF using the same bulletin board system.
Samples should be sent to the attention of Mr. Thomas Danison at the address listed in Section
4.2.d. The Battelle Receiving department will be supplied with names of two alternative staff members
to be called in the event that Mr. Danison is not available to take immediate receipt of the samples.
Mr. Danison will check the samples for general condition (temperature and breakage)
immediately upon receipt. Samples that are not iced at receipt will not be analyzed, and the problem
will be reported to the EPA Contract Technical Monitor for subsequent resolution of the situation with
ICF. Samples will be immediately stored at 4±2°C away from light until they are processed.
All information on the ICF field sample tracking sheets (Figure 5) and a description of the
general condition of the samples upon receipt will be entered into a computer database (Beckman
LABManager®) using a terminal. An example of the sample login screen is given in Figure 6. At this
time, a nine-digit Battelle identification number (BCD ID) and two-digit Sample Type code will be
assigned using the system described in Figure 7. Samples can subsequently be tracked using either
the EPA identification code or the BCD ID. Photocopies of the ICF field sample tracking sheets,
Federal Express shipping lists, and a hardcopy log of samples in the database will be filed. An
example of the hardcopy log of samples contained in the database is shown in Figure 8.
Samples will be processed within 14 days of collection. Sample extracts will be immediately
analyzed or stored at -70±2°C and protected from light. Stored sample extracts will be allowed to
warm to room temperature before analyses. Sample extracts will be analyzed and, if necessary,
confirmed by the alternative GC-NPD conditions and by low-resolution GC-MS within 14 days of
extraction. The holding time for GC-MS analysis may be extended an additional 14 days upon
approval of the EPA Contract Technical Monitor.
Time storage samples will be extracted within ±4 days of the proper date and analyzed within
four days of extraction. Day 0 time storage samples will be spiked and immediately extracted within
the 14-day holding time for samples and will be analyzed within four days of extraction. Day 14 time
storage samples will be spiked at the same time as the corresponding Day 0 time storage samples
and stored at 4±2°C until extraction. Day 14 time storage samples will be extracted no sooner than
10 days and no later than 18 days after spiking and will be analyzed within four days of extraction.
-------
FIGURE 6
SAMPLE LOGG1N SCREEN
Section No. 7
Revision No. 3
Date: April 29, 1988
Page 2 of 6
> — — — •— •
^ - a - s «* •
-------
Section No 7
Revision No. 3
Date: April 29, 1988
Page 3 of 6
FIGURE 7
BCD LAB IDs AND BCD NOT IDs
Sample Code
XX = Sample code (SA = sample, BS = backup sample, LS = laboratory spike, TS = time
storage, LC = laboratory control, BL = laboratory method blank, PE = performance
evaluation sample, 1C = instrument control standard, ST = stock/reagent, and CS =
calibration standard)
Battelle Laboratory Identification Number (BCD ID)
YY = year (88, 89,...)
B = fixed; indicates an NPS sample
X = incremented letter
xxxxx = incremented number (0001, 0002,...)
Battelle Notebook Identification Number (BCD Not ID)
xxxxx = Battelle laboratory notebook number
yy = Notebook page number containing description of sample
zz = Notebook page line number containing description of sample
-------
Section No 7
Revision No 3
Date: April 29, 1988
Page 4 of 6
FIGURE 8
HARDCOPY OF NFS DATABASE SAMPLE LOG
BCD ID
88BA00014
88BA00015
88BA00016
88BA0001 7
88BA00018
88BA00019
88BA00020
88BA00021
88BA00022
88BA00023
88BA00024
88BA00025
88BA00026
88BA00027
88BA00028
88BA00029
88BA00030
88BA00031
88BA00032
88BA00033
88BA00034
88BA00035
88BA00036
88BA00037
88BA00038
88BA00039
88BA00040
88BA00041
88BA00042
88BA00043
88BA00044
88BA00045
88BA00046
88BA00047
88BA00048
88BA00049
88BA00050
88BA00051
88BA00052
88BA00053
88BA00054
88BA00055
88BA00056
SAMPLE ID
PD-0004-5-6-01
PD-0004-5-6-03
PD-0008-5-6-01
PD-0008-5-6-03
PD-0007-5-6-01
PD-0007-5-6-03
PD-0007-5-6-06
PD-0005-5-6-01
PD-0005-5-6-03
PD-0005-5-6-04
PD-0003-5-6-01
PD-0003-5-6-03
PD-0003-5-6-06
PD-0006-5-6-01
PD-0006-5-6-03
PD-0001 -5-6-01
PD-0001 -5-6-03
PD-0001 -5-6-04
PD-001 3-5-6-01
PD-001 3-5-6-03
PD-001 3-5-6-06
•
•
•
PD-001 0-5-6-01
PD-001 0-5-6-03
PD-0009-5-6-01
PD-0009-5-6-03
PD-0009-5-6-04
PD-0002-5-6-01
PD-0002-5-6-03
PD-001 1-5-6-01
PD-001 1-5-6-03
PD-001 1-5-6-06
PD-001 2-5-6-01
PD-001 2-5-6-03
PD-001 2-5-6-04
•
•
•
•
*
•
BCD
NOT ID
43307-04-04
- -
43307-05-05
- -
43307-06-06
- -
43307-07-07
43307-08-08
- -
43307-09-09
43307-10-10
- -
43307-11-11
43307-12-12
- -
43307-04-04
- -
43307-05-05
43307-06-06
- -
43307-07-07
43307-23-23
43307-13-13
43307-14-14
43307-08-08
- -
43307-09-09
- -
43307-10-10
43307-04-04
- -
43307-05-05
- -
43307-06-06
43307-07-07
- -
43307-08-08
43307-12-12
43307-11-11
43307-23-23
43307-23-23
43307-09-09
43307-10-10
Date
Rec'd
04/19/88
04/19/88
04/20/88
04/20/88
04/21/88
04/21/88
04/21/88
04/21/88
04/21/88
04/21/88
04/22/88
04/22/88
04/22/88
04/22/88
04/22/88
04/26/88
04/26/88
04/26/88
04/26/88
04/26/88
04/26/88
01/01/60
01/01/60
01/01/60
04/27/88
04/27/88
04/27/88
04/27/88
04/27/88
04/28/88
04/28/88
04/29/88
04/29/88
04/29/88
04/29/88
04/29/88
04/29/88
01/01/60
01/01/60
01/01/60
01/01/60
01/01/60
01/01/60
Sample
Code
SA
BS
SA
BS
SA
BS
LS
SA
BS
LS
SA
BS
LS
SA
BS
SA
BS
LS
SA
BS
LS
1C
LC
BL
SA
BS
SA
BS
LS
SA
BS
SA
BS
LS
SA
BS
LS
BL
LC
1C
1C
LC
BL
Set
#
07
07
07
07
07
07
07
07
07
08
08
08
08
07
07
07
08
08
08
09
09
09
09
09
08
08
08
09
09
09
-------
Section No 7
Revision No 3
Date- April 29, 1988
Page 5 of 6
A laboratory control standard (Section 5.3.b) and a laboratory method blank (Section 5.7) will be
prepared and analyzed with each sample set. BCD IDs will be assigned to the laboratory control
standard and the laboratory method blank using the sample login form (Figure 6) following the criteria
outlined in Figure 7. The laboratory control standard and laboratory method blank can be traced
using the BCD ID.
Samples will be grouped into sets as defined in Section 5.3.b. When samples are processed
using Method 6, all laboratory activities will be described in a Battelle laboratory notebook. When
sample extracts are generated, these extracts will be assigned a Battelle laboratory notebook
identification number (BCD Not ID) following the criteria given in Figure 7. In addition, all stock
solutions, spiking solutions, and calibration solutions generated with the sample set or intended for
use with the sample set will also be assigned BCD Not IDs. BCD Not IDs will be entered into the
database using a Beckman-LABManager® data entry screen (Figure 9) following the criteria outlined in
Figure 7. All sample extracts can be traced using the BCD Not ID.
Unused samples or samples not extracted before the 14-day maximum holding time will be
disposed or returned to EPA or ICF at EPA's expense. The EPA Contract Technical Monitor will be
consulted to determine final disposition of unused samples. Sampling kits will be returned to ICF at
EPA's expense. After analyses, sample extracts will be stored at -20±2°C or lower until disposal is
approved by the EPA Contract Technical Monitor.
The water samples, which contain mercuric chloride, will be solidified with Fixsorb-1000 (sodium
silicate-type clay); solidified water samples and extracts will be buried in a secure chemical
management facility. Sample extracts will be disposed of as hazardous waste.
A refrigerator adjusted to 4±2°C has been designated for storage of samples and a freezer
capable of maintaining temperatures at or below -20±2°C has been designated for storage of sample
extracts. The refrigerator and freezer temperatures are monitored daily and the temperatures are
recorded ^n log sheets displayed on the front of the units. The SOP describing use of the freezer is
included as Appendix D of this QA Project Plan, "Standard Operating Procedure for Use of Admiral
Freezers." The SOP describing use of the refrigerator is included as Appendix E of this QA Project
Plan, "Standard Operating Procedure for Use of Hotpoint Refrigerators." Examples of the
refrigerator/freezer log sheets are included in these two SOPs.
-------
FIGURE 9
DATA ENTRY SCREEN
Section No. 7
Revision No. 3
Date: April 29, 1988
Page 6 of 6
i M C 1 I C P T I I T C * " M
: s c
: j. .-•' c
— »- s e •
-------
Section No 8
Revision No 3
Date: April 29, 1988
Page 1 of 3
8. CALIBRATION PROCEDURES AND FREQUENCY
8.1 Instrumentation
Instrumentation that will be used for this project includes but is not limited to the following:
GC-NPD analyses will be performed using an HP5890 dual capillary gas
chromatograph equipped with an autosampler, a split/splitless injection assembly,
and two NPD assemblies. Each detector will be connected to a chromatography
data system via a Beckman digimetry to allow computerized acquisition of raw
GC-NPD data. The gas chromatograph will be operated as described in Section
11.3 and Table 1 of Method 6. A second dual NPD HP5890 gas chromatograph is
available as backup.
• GC-MS confirmation will be conducted using a low-resolution Finnigan 4500 mass
spectrometer. A Finnigan INCOS® data system equipped with Finnegan software
Revision 5.5 will be used for MS data collection and processing. Other mass
spectrometers are also available for ETU confirmations; detection limit studies will be
conducted with any mass spectrometer used for this study to determine the
minimum level of ETU that can be confirmed with each instrument. Results of the
detection limit studies will be communicated to the EPA Contract Technical Monitor
prior to confirmation of ETU presence in sample extracts. Specific GC-MS
calibration procedures and operating conditions are given in Appendix C.
An HP1000 Series A computer will be used for collection and processing of all
chromatographic data. This computer will also be used for maintaining the Method
6 database. Two Beckman software products will be used. Beckman PeakPro® will
be used for chromatographic data acquisition and processing. Beckman
LABManager® will be used for maintaining the Method 6 database and generating
hardcopy and ASCII reports.
The HP1000 Series A computer will be accessed with IBM XT or IBM PS/2 Model 50
or 60 computers each equipped with Reflections-3+® terminal emulation software.
These IBM computers will also be equipped with a modem to allow access of the
ICF bulletin board system via phone lines. These IBM computers will also be used
for generation of control charts (Section 5.3.a) using Lotus Symphony® software.1
A Mettler AE 240 balance will be used for preparing the ETU stock standard
solution, internal standard spiking solution, and surrogate standard spiking solution
as described in Sections 7.11, 7.12, and 7.13 in Method 6. The calibration and
operation of this balance is described in Appendix F, "Standard Operating
Procedure for Weight Determinations Using an Electronic Analytical Balance."
A Mettler P1200N balance will be used for weighing larger amounts of materials
such as the salts described in Section 11.1.1 of Method 6. The calibration and
operation of this balance is described in Appendix G, "Standard Operating
Procedure for the Use of Top Loading Balances."
1 Ouchi, G. I., "Control Charting with Lotus 1-2-3", American Laboratory, Feb. 1987, 82-95.
-------
Section No 8
Revision No 3
Date: April 29, 1988
Page 2 of 3
8.2 Calibration Procedures
Calibration procedures and frequency are defined in Section 9.2 of Method 6 and can be
summarized as follows:
• ETU stock solutions, prepared as specified in Section 7.11 of Method 6 will be
provided to Mr. Zimmerman monthly by EPA. Mr. Zimmerman will store the ETU
stock solutions at -20±2°C or lower and protected from light and describe the
receipt of the samples in a Battelle laboratory notebook.
• Ms. Kircher will use in-house supplies of the surrogate standard, PTU (prepared at
Battelle), and the internal standard, THP (obtained from Aldrich), to prepare
surrogate and internal standard spiking solutions as described in Sections 7.12 and
7.13 of Method 6. Ms. Kircher will store the surrogate and internal standard spiking
solutions at 4±2°C protected from light as specified in Method 6. Ms. Kircher will
describe preparation of surrogate and internal standard solutions, including
information such as the source of the neat materials, in a Battelle laboratory
notebook and assign the solutions BCD Not IDs as described in Section 7. All stock
solutions can be traced by their BCD Not ID.
Ms. Kircher will prepare calibration solutions using stock ETU solutions obtained
from EPA and surrogate and internal standard stock solutions prepared as
described above; calibration solutions will contain ETU at or slightly below the MRL
specified by EPA and at four additional higher calibration levels spanning the
working range of the detector. One of the calibration standards will contain ETU at
or close to the spiking level of the laboratory control standard. Ms. Kircher will
describe preparation of calibration solutions in a Battelle laboratory notebook and
assign these solutions BCD Not ID as described in Section 7. Since the laboratory
notebook description will contain the date that these calibration solutions were
prepared as well as the source of the materials used to prepare the solution and
preparation procedures, the BCD Not ID will be used to identify which calibration
standards belong to specific sample sets.
• Mr. Zimmerman will optimize the GC-NPD instrumentation and demonstrate
acceptable instrument performance by analysis of instrument QA standards
specified in Method 6; he will analyze the five calibration solutions and generate a
calibration curve as described in Section 9.2 of Method 6 (Appendix A).
Mr. Zimmerman will analyze a minimum of one calibration solution each working
day; the resultant data will be treated as a sample and ETU concentrations will be
calculated. Variation of the calculated ETU concentration from the expected ETU
concentration of more than 20 percent will result in evaluation of the calibration
standard and/or chromatographic system. After identification and correction of the
problem, Mr. Zimmerman will recalibrate the GC-NPD with the five calibration
standards as described earlier. Alternatively, GC-NPD instrumentation will be
recalibrated on each working day.
ETU solutions are known to be relatively unstable at room temperature even in organic solvents
containing dithiothreitol (DTT). Therefore, the integrity of calibration solutions left at room temperature
for analysis more than one time is questionable. In addition, the stability of the NPD is not normally
sufficient to compare detector response from one day to the next. As an alternate approach, new
ETU calibration solutions will be prepared with each set of samples and compared to one of the most
-------
Section No 8
Revision No 3
Date- April 29, 1988
Page 3 of 3
recently prepared calibration solutions as a check on calibration solution integrity. If the two
calibration solutions do not compare within ±20 percent, the new calibration solutions are considered
suspect and calibration solutions will be reprepared and analyzed with the previous calibration
solutions to determine the source of the deviation. If the new calibration solutions are not acceptable,
other possible sources of the problem will be evaluated, such as decomposition of stock solutions or
decomposition of the original calibration solution.
-------
Section No. 9
Revision No. 3
Date: April 29, 1988
Page 1 of 2
9. ANALYTICAL PROCEDURES
Analyses for ETU will be conducted following the procedure outlined in Method 6. Determination
of Ethylene Thiourea in Ground Water by Gas Chromatography with a Nitrogen-Phosphorus Detector.
Equipment that will be used at Battelle to perform Method 6 is described in detail in Section 8. The
ionic strength and pH of a measured 50-mL volume of sample are adjusted by addition of ammonium
chloride and potassium fluoride. The sample is poured onto an Extrelut column. ETU is eluted from
the column in 400 mL of methylene chloride. The extract is solvent exchanged to ethyl acetate and
concentrated to a volume of 5 ml. Primary and confirmatory GC-NPD analytical conditions are
described which permit the separation and measurement of ETU in the extract. The retention times
for ETU, PTU, and the internal standards specified in the method were accurate at the time Method 6
was developed, but are representative of the specific GC columns used during that time. For this
reason, the absolute retention times specified in the method may not always be followed, but it is not
possible to provide alternative retention times in this Quality Assurance Project Plan. Method 6 is
included on this QA Project Plan as Appendix A.
A set of samples is defined by EPA as the number of samples processed by an analyst in one
day within 12 hours. Battelle will use sample sets containing up to 12 samples, including one process
blank, one laboratory control standard, and up to 10 field samples.
Problems encountered and observations made during processing of sample sets that do not
compromise the QC for the entire sample set will be recorded in the Battelle laboratory notebook by
the person performing the task, specifically Ms. Kircher (sample processing) or Mr. Zimmerman
(GC-NPD analyses). Problems requiring corrective action will be documented using a Report of
Deviation form as described in Section 15.
The following variations from Method 6 (Appendix A) are noted:
Change Section 10.7.1.1 to read "The spiking concentration in the sample should be
one to five times the background concentration, or, if it is impractical to determine
background levels before spiking, 10 times the MRL."
Change Section 10.8 to read "...If the method blank exhibits a peak within the
retention time window of ETU which is greater than or equal to one-half the MRL for
ETU, determine the source of contamination before processing samples and
eliminate the interference problem."
• Change Table 1, primary conditions to read:
Column: 5 m long x 0.25 mm I.D. DB-Wax bonded fused silica
column (J&W), 0.25 jim film thickness
Carrier gas: He @ 8.5 mL/min (room temperature)
Detector: Nitrogen-phosphorus
Detector temperature: 250°C
Makeup gas: He @ 30 mL/min
Detector gases: Air @ 70 mL/min; H2 @ 3.5 mL/min
Oven temperature: 205°C
-------
Section No. 9
Revision No. 3
Date: April 29, 1988
Page 2 of 2
Sample: 2 ^L splitless; 0.10 min split delay
Injector temperature: 275°C
Split flow: 60 mL/min
Septum purge: 9 mL/min
Change Table 1, confirmation conditions to read:
Column: 5 m long x 0.25 mm I.D. SPB-35 bonded fused silica column
(Supelco), 0.25 urn film thickness
Carrier gas: He @ 8.5 mL/min (room temperature)
Detector: Nitrogen-phosphorus
Makeup gas: He @ 30 mL/min
Detector gases: Air @ 70 mL/min; H2 @ 3.5 mL/min
Oven temperature: 130°C
Sample: 2 ^L splitless; 0.10 min split delay
Injector temperature: 275°C
Split flow: 60 mL/min
Septum purge: 9 mL/min
Change Section 10.2.1 to read "...prepare a laboratory control (LC) check sample
concentrate in 1000 ng/mL DTT in ethyl acetate approximately 1000 times..."
Change Section 8.3.1 to read "...Extracts should be stored at -70±2°C away from
light."
Change Section 7.11.2 to read "...Store at -70±2°C and protect from light."
Any future method mo'difications in Method 6 will be communicated to the EPA Contract Technical
Monitor and confirmed in writing.
-------
Section No. 10
Revision No. 3
Date. April 29, 1988
Page 1 of 7
10. DATA REDUCTION, VALIDATION, AND REPORTING
Data reduction, validation and reporting schemes have been developed to assure traceability
and easy evaluation and validation of all results. The complete data flow and reporting scheme is
depicted in Figure 10.
10.1 Data Reduction and Storage
10.1.a Primary and Confirmatory GC-NPD Analyses
Raw or initial GC-NPD data are in the form of the voltage readings generated by the detector.
These voltage readings will be collected via a Beckman digimetry and stored initially on the permanent
disk of the HP1000 computer and finally on magnetic tape. The raw data is processed using
Beckman PeakPro® chromatography software. PeakPro® routines use operator designated guidelines
for identification of compounds on the basis of peak retention times and integration of the compound
peaks to provide peak area data. PeakPro® will integrate the ETU, surrogate, and internal standard
peaks and determine peak areas for each compound and peak area ratios for ETU and PTU relative to
the internal standard. PeakPro® will then generate calibration curves for ETU and PTU by plotting
ETU concentration or PTU percent recovery versus the appropriate peak area ratios. PeakPro® uses
the generated calibration curve to calculate ETU concentration or PTU recovery in the sample extracts.
After results are evaluated by an experienced analyst (Mr. Zimmerman), the computerized
results are automatically entered into a computerized database created by Beckman LabManager®
software; this NPS Method 6 database will also contain hand-entered information such as sample
identification, date of receipt, sample condition at receipt, date of extraction, and other relevant
information. The LabManager® program will generate ASCII text reports as described in Section
10.3.a as well as other information such as lists allowing easy comparison of EPA-assigned Sample ID,
the BCD ID, and the BCD Not ID (extract).
10.1.b GC-MS Identification or Confirmation
In the case of mass spectrometry, identification is also made on the basis of the mass spectra
and retention time of the peak. Finnigan INCOS® software will be used to search for ETU on the
basis of expected retention time and characteristic ions. When ETU confirmation is required, the ETU
peak area, relative to the internal standard, will be compared to the area generated from a standard
containing ETU at approximately the level expected in the sample being confirmed. Specific GC-MS
calibration procedures, operating conditions, and confirmation requirements are given in Appendix C.
When identification of an unknown is desired, a full scan spectra will be generated for the unknown
component, and the spectra will be evaluated by comparison to available library spectra. If possible,
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Section No. 10
Revision No. 3
Date: April 29, 1988
Page 2 of 7
FIGURE 10
DATA FLOW AND REPORTING SCHEME
Detector Reading
<
1
r
Permanent Disk Storage |
Magnetic .Tape Storage J
Computer Data Analysis |
Sampling Data (manual) \—* NFS Method 6 Database j
Magnetic Tape Storage \
—* Magnetic Tape Storage \
QAU Audit of Data |
Data Packets (ASCII) |
Monthly Reports |
Yearly Final Reports |
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Section No 10
Revision No 3
Date: April 29, 1988
Page 3 of 7
the spectra will be compared to a spectra generated at Battelle from an authentic standard of the
suspected compound. Procedures used for identification of unknowns are described in Section 5.10.
10.1 .c Data Storage
Raw and finished results are archived in hardcopy and electronic (magnetic tape) forms. The
following information will be filed as hardcopy:
Photocopies of the ICF field sample tracking sheets, Federal Express shipping lists,
and a hardcopy log of samples in the database (see example in Figure 8),
Chromatograms showing computer integration for calibration samples and sample
extracts (GC-NPD and GC-MS),
Printouts showing analysis results for sample extracts (GC-NPD and GC-MS),
Mass spectra generated during GC-MS confirmation, if applicable,
A copy of the PeakPro® analysis method used to analyze the sample extracts; the
method printout includes a description of the calibration curve generated and the
calibration procedure,
Copies of the calibration curves for ETU and PTU,
• A PeakPro® summary report listing peak areas and calculated ETU concentrations
and PTU percent recoveries; the summary report is valuable for evaluating several
QC features such as variability of the internal standard peak area and recovery of
the PTU surrogate standard,
ETU and PTU control charts generated using Lotus Symphony®,
Copies of the ASCII text files generated as described in Section 10.3.a,
A listing of EPA-assigned Sample ID, the BCD ID, and the BCD Not ID (extract) for
each sample, and
• Report of Deviation forms, if any, as described in Section 15.
Hardcopy data will be stored in a locked office and filed by sample set. People with access to these
data include Ms. Engel, Mr. Zimmerman, and the QAU. Mr. Zimmerman will be responsible for
maintaining the project file.
The following information will be stored on magnetic tape.
All raw and processed GC-NPD and GC-MS results, specifically all voltage readings
from the specified detector as well as peak integration information determined by
the relevant software package, and
• The Method 6 database.
Magnetic tapes are stored in locked temperature/humidity controlled facility; only Battelle analytical
laboratory personnel have access to this facility. Specific data files are subject to a security system
which will only allow access to Ms. Engel, Mr. Zimmerman, and Mr. Danison. The QAU will be allowed
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Section No 10
Revision No. 3
Date: April 29, 1988
Page 4 of 7
access for auditing purposes. Mr. Danison and Mr. Zimmerman will be responsible for maintaining the
magnetic media used for this project.
All data reduction and storage procedures will be cross checked by the QAU during data audits
and inspections.
10.2 Data Validation
Prior to submission of results to EPA, all results will be validated initially by Mr. Zimmerman and
the Project Manager, and finally by the QAU.
Results submitted to EPA fall into two categories: results generated by computerized routines
and results entered or calculated by hand. The computerized routines that will be used for Method 6
data reductions are well-characterized. QAU will evaluate these routines during system audits and
establish the validity of these routines. The QAU will perform the same calculations by hand and
establish that the computerized routine is functioning as expected and provides the correct results.
The routines will be rechecked periodically as prompted by a change in computer hardware or
software or other relevant conditions such as a loss of power to the computer prior to analysis of more
NPS ground water samples.
The QAU will be provided with all hardcopy data listed in Section 10.1.C. The QAU will check
any hand-entered information appearing in the ASCII text reports (sample identification, date of
receipt, sample condition at receipt, date of extraction, and other relevant information) against the
original NPS field sample tracking sheet and the Battelle laboratory notebook, prior to submission of
results to EPA. As mentioned earlier, compound quantification calculations are rarely made by hand.
However, any calculations made other than by validated computer routines will be checked and
validated by the QAU prior to release of the results to EPA. All results will be audited by the QAU
prior to submission to EPA.
10.3 Data Reporting
10.3.a ASCII Data Packets
Analytical results and results from the instrument QC standard described in Section 5.7 of this
QA Project Plan will be submitted in the form of an ASCII text file on a floppy disk. The ASCII text file
will contain all information required by EPA in a specified format; the specified report formats for
analytical results and instrument QC standard results for Method 6 are shown in Figures 11 and 12,
respectively. Specific data format requirements are summarized in Appendix H.
The ASCII text file reports will be generated directly from the NPS Method 6 database described
in Section 10.1. Analytical results and related instrument QC standard results from each sample set
will be reported together as a packet in a single ASCII file. Analytical results will be submitted to Mr.
Chris Frebis, CSC (Section 4.2.d) within 57 days of sample receipt. Mr. Frebis will prescreen the
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Section No. 10
Revision No. 3
Date: April 29, 1968
Page 5 of 7
FIGURE 11
ASCII REPORT FORMAT FOR NPS METHOD 6 ANALYTICAL RESULTS
Fld-pH SJTemp Date Sam Date_Shp Date_Rec Time_Sam Time_Ice
04/11/88 04/11/88 04/12/88 00:00 00:00
Receipt Condition
BOTTLES LOOSE IN BOX
Samp # Lab Set # Date Spk Date_Ext Date_Ana Column
PD-9001-5-6-01 BCD 03 04/13/88 04/13/88 04/14/88 PRIM
Type Spiker Extract Analyst Sam_Vol Ext_Vol Int. Std. % Su
SAMP EAK EAK DPZ 50 5 81.0 90.
Comments
Analyte Cone.
ETU -999.0
Fld-pH SJTemp Date_Sam Date_Shp Date_Rec Time_Sam Time_Ice
04/11/88 04/11/88 04/12/88 05:30 00:00
Receipt Condition
ICE OK SAMPLES LOOSE IN BOX FORM FOR PD-9002-5-6-01
Samp # Lab Set # Date_Spk Date_Ext Date_Ana Column
PD-9005-5-6-01 BCD 03 04/13/88 04/13/88 04/14/88 PRIM
Type Spiker Extract Analyst Sam_Vol Ext_Vol Int. Std. % Si
SAMP EAK EAK DPZ 50 5 100.1 85
Comments
Analyte Cone.
ETU 15.3
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Section No. 10
Revision No. 3
Date: April 29. 1988
Page 6 of 7
FIGURE 12
ASCII FORMAT FOR NPS METHOD 6 INSTRUMENT QC RESULTS
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Section No 10
Revision No 3
Date: April 29, 1988
Page 7 of 7
results for QA/QC criteria and completeness and send the results to the EPA Contract Technical
Monitor.
The EPA Contract Technical Monitor will be immediately verbally informed of analytical results
under the following conditions:
• ETU is detected in a sample at or above half the MRL and is subsequently
confirmed using confirmatory GC-NPD conditions, or
ETU is detected in a sample above the reporting level using both primary and
confirmatory GC-NPD conditions, but the quantification results from primary and
confirmation analyses do not agree within 25 percent.
These contacts and actions taken as a result of these contacts will be subsequently confirmed in
writing.
10.3.b Monthly Reports
Six copies of a monthly report will be provided within 15 calendar days after the end of the
period being reported. The monthly reports will be sent to the EPA Contract Technical Monitor, and a
copy of the cover letter will be forwarded to Mona S. Snyder, Contract Specialist for the NPS,
EPA-CMD, Cincinnati, OH 45268.
Monthly reports will contain the following information for the subject reporting period:
• Summary of progress, including samples received, analyzed, and in progress, and
status of data processing for analyzed sets of samples,
Reports on standards, including new dilutions and results of checks before using,
Identification of problems encountered during the subject reporting period,
Summary list of bench-level corrective actions,
Copies of representative and, if applicable, unusual chromatograms,
Information request by the EPA Contract Technical Monitor because of specific
methodology or problems encountered,
• Changes in operational personnel, and
Comments.
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Section No 11
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Date: April 29, 1988
Page 1 of 2
11. INTERNAL QUALITY CONTROL CHECKS
Battelle will institute internal QC checks as a means of providing a quality product. Specific
criteria for acceptable results and corrective action to be undertaken for unacceptable results are
given in Section 5.0. The QC checks that will be conducted during this project are summarized in
Table 1.
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Section No. 11
Revision No. 3
Date: April 29, 1988
Page 2 of 2
TABLE 1
INTERNAL QUALITY CONTROL CHECKS
TABLE 1 INTERNAL QUALITY CONTROL CHECKS
(uility Control Chock
Frequency of Iho
Criteria for Acceptable ROM It*
Correct!TO Action
Control chortt
ETU ind PTU control chirtt iro updated
by including roiulto fro* ono labora-
tor; control atandard run with otch
Mt.
ETU and PTU recoverio* fro* laboratory Stop work and raaolvo probloe b
control »tandarda oust bo vithin evaluating ayatee. An in-contro
control I into. oi tuition ouot bo dooonotrotod t
continue cork.
Aooooo eurrogate recovery
Aeeeee internal *tanderd iroo
Aooooo MO If to recovery
ith blind
porforoanco eta tuition stop loo; the
ochodulo io net provided.
The ourrogato recovery ouot be vlthin
21 percent of the eean recovery
detoreinod for PTU fro* current
control chart.
The internal atandard peek area for
any aaeplo euot not doviote by core
than 21 percent fro* the eeo* peak
area for the calibration aooploo in
that aaople aot.
The ETU recovery io eipected to bo
oithin lint* opocified in updated ETU
control chart; noncoopliance eoy
indicate eatrii effecte.
Tho eothod blank ohould not contain o
peak greater than or eijjel to one half
the M. for ETU.
Acceptance criteria
Table i of khthod t.
are given
fill be eotabliahod by EPA.
Outlined in Sectiono 114.1 and 1» 4
of Uothod I.
Outlined in Section II.i.I ei
Method «.
Outlined in Section II.? of Method •.
Outlined in Section II I of Method *.
Inotrueont ouet be eaintainod o
repaired; apocified criteria ouat a
eot before analyaie of aaoplo*.
lilI be o*tabli*hed by EPA.
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Section No. 12
Revision No. 3
Date: April 29, 1988
Page 1 of 4
12. PERFORMANCE AND SYSTEM AUDITS
The QAU Manager will be responsible for assuring systematic checks to determine the quality of
operation of all functions and activities associated with this project. Checks will consist of system
audits and performance audits. A project-specific SOP entitled "Standard Operating Procedure for
Quality Assurance Unit Performance and System Audits for NPS Survey" contains specific instructions
for performance and system audits and is included as Appendix I of this Quality Assurance Project
Plan.
12.1 System Audits
A system audit will be conducted shortly after laboratory operations are functional and
subsequently half way through the contract or more frequently at the discretion of management.
System audits are on-site inspections and reviews of the QC system. System audits will be repeated
when significant changes are made in procedures due to equipment updates or replacement, software
changes and other variables as they arise. Results of system audits will be reported to the Project
Manager as described in Section 16. The following is a noninclusive list of items to be evaluated and
validated during the system audit:
12.1.a Sample Receiving/Storage
The systematic procedure for receiving samples will be reviewed to ensure the integrity of
samples. This will include noting the time of arrival, the number and condition of samples received
and an examination of the accompanying paper work. Storage facilities will be examined to assure
that appropriate conditions are provided and that samples are properly stored to protect the sample
integrity.
12.1.b Labware
Cleaning, storage and use of labware will be examined to assure that procedures and
equipment are appropriate for the intended use and to determine that no contamination has occurred
that could affect the interpretation of analytical results.
12.1.C Materials, Reagents, Solvents, and Gases
Materials, reagents, solvents, and gases will be checked to assure that they conform to the
specifications defined in the method of analysis. Only those materials with appropriate performance
capabilities and freedom from impurities will be used. Attention will be given to assure that these
items are properly stored to protect them from degradation and contamination. Expiration dates will
be noted so that only viable materials are used in preparations and analysis. If stability is suspect,
retesting will be required. Documentation of lot/batch numbers will be required to provide traceability
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Section No 12
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Page 2 of 4
should questions arise regarding any results where they were used. Method blanks will be used to
determine what bias, if any, these materials might have on the analytical results. These blanks will be
run as frequently as is necessary to reliably establish the bias.
12.1.d Chemical Solutions/Performance Standards
All measuring devices such as volumetric glassware, syringes, analytical balances, meters, etc.,
will be appropriately calibrated and in good working order to capably conduct measurements with the
degree of accuracy required by the analytical method to be followed. Concentrations of prepared
standard solutions will be verified against primary analytical reference standards, if available, or by the
most direct, reliable, approved method of measurement when such standards are not available.
Aliquots will be taken in the largest practical volumes to minimize error associated with such
measurements. All preparations will be labeled to identify solutes and solvents used, concentration,
date of preparation and expiration date (if applicable), and the name of the preparer. The source of
materials will be identified in the laboratory record book. Stored solutions and standards will be
rechecked periodically to assure that their stability isn't suspect and that no contamination has
occurred.
12.1.e Analytical Methods
Only approved, validated methods which meet the requirements for selectivity, accuracy,
precision and range as specified for this program will be used.
12.1.1 Analyst Training
Analysts assigned to work on this program will be selected on the basis of their formal
education and experience to conduct the kinds of analyses required. Special on-the-job training is
done to emphasize the importance of technique and adherence to SOPs. All training is documented
and will be checked to assure that it meets program requirements for the work to be done.
12.1.g Equipment Calibration/Maintenance
Documented procedures are available for care and maintenance of equipment. These
procedures will be reviewed and equipment logs will be checked to assure that operations are
conducted as stated to ensure the performance of equipment. This includes the primary analytical
equipment as well as auxiliary equipment, such as pH meters, balances, gauges, thermometers, etc.
Internal instrument calibration checks will be performed as required and these operations will be
documented. Performance during analysis will be documented by use of performance standards.
Performance criteria will be predetermined and stated in the analytical method. Routine preventative
maintenance will be conducted according to a written schedule. Should problems occur, trouble
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Section No 12
Revision No. 3
Date. April 29, 1988
Page 3 of 4
shooting will be conducted to identify problems and their cause so that appropriate corrective action
can be taken quickly and accurately to avoid more complicated failures.
12.1.h Facilities
Facilities will be inspected periodically, on a monthly basis, to maintain control of the laboratory
environment to eliminate contaminating influences, optimize instrument operating conditions and
maintain good housekeeping and safe working conditions.
12.1.1 Standard Operating Procedures
Written standard operating procedures are available to cover equipment and operations done in
the laboratory. These, along with the Statement of Work and approved Quality Assurance Project
Plan, will be used as the basis for performance review.
12.1.J Data Records/Reports
Documentation and reports generated in connection with this program will be audited
periodically to assure that records and results meet program requirements. This audit will include the
master sample log which shows what samples have been received from and by whom, the date of
receipt, and sample description; any required custody records; analytical instrument and auxiliary
equipment activity logs; laboratory record books that document all operations that have occurred
including sample identification and preparations, transfer of samples, details concerned with analysis,
and deviations from procedure that might have occurred, controls that were run, instrument
identification, and analysts signatures along with the dates of the work, any associated raw data
resulting from the preparation and analysis, all observations, and discussions and conclusions
throughout the progress of the work. In addition, computer printouts and charts will be reviewed, as
necessary to determine that all required work was done and is properly labeled, that results meet
requirements, and that reported observations are in agreement with data that were generated.
Special attention will be given to sample identification, analytical parameters and their limits of
detection, final results, estimation of precision and accuracy, types of corrections applied to the raw
data, references to approved analytical methods, reliability of the data and its interpretation.
12.2 Performance Audits
Scheduled performance audits will be conducted by the QAU. A performance audit is an
independent check by the QAU to evaluate the data produced by the laboratory's analytical system.
Performance audits include:
An on-site analyst work review conducted at a frequency no less than once per
quarter. The on-site audit is a means of evaluating performance that can not be
assessed by evaluation of data. The analyst's techniques, observance of
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Section No 12
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Page 4 of 4
procedures as defined by written methods this QA Project Plan, and general
knowledge of the project objectives will be assessed. On-site work review results
will be reported to the Project Manager.
An audit of all data produced during the NPS analytical effort. QAU will audit all
data for adherence to QA objectives and specified reporting formats prior to release
of the data to EPA.
12.3 Audits Conducted by the USEPA
The USEPA will perform periodic systems and data audits using USEPA-assigned staff. These
audits will be preannounced to BCD; at minimum, the Battelle QAU Manager and the BCD Project
Manager will be present during these audits. Results of USEPA systems and data audits will be
supplied to BCD in writing; BCD will respond to all USEPA systems and data audit results and
describe the responses to USEPA in writing.
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Section No 13
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13. PREVENTATIVE MAINTENANCE
Preventative maintenance will be conducted to minimize occurrences of unpredicted instrument
failure. Necessary spare parts will be kept on hand so that any necessary repairs can be made
quickly. Preventative maintenance steps that will be taken to minimize instrumentation downtime are
summarized in Table 2. Spare parts necessary for routine instrument maintenance are listed in Table
3.
All maintenance performed is recorded in record log books for each instrument. If necessary,
the instrument will be recalibrated after any maintenance operation as described in Section 8.0 of this
QA Project Plan. Whenever instruments are serviced, the record log book will show the part number,
the date, the person doing the maintenance, and the reason for the maintenance work. An example
of a record log book page is shown in Figure 13.
In general, Battelle performs instrument maintenance using in-house personnel. However, if
outside maintenance is required, sufficient additional instrumentation (GC, MS) is available for use to
eliminate downtime.
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Section No 13
Revision No 3
Date: April 29, 1988
Page 2 of 4
FIGURE 13
INSTRUMENT RECORD LOG BOOK
Routine Maintenance Record
Date
1/29
2/10
2/12
2/14
ID
D7
D7
D7
D7
Work Performed and Comments
Changed system
Changed system
Changed system
Installed pressure
regulator on a
eliminate pulsing
3/18 D7 Installed Dual Column system, graphite seal at injection part
Changed bead on Det B
Replaced system
3/22 D7 Installed SPB-5, new system
3/22 D7 Reinstalled dual column
3/23 D7 Installed SPB-5
Replaced system
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Section No 13
Revision No. 3
Date: April 29, 1988
Page 3 of 4
TABLE 2
PREVENTATIVE MAINTENANCE SCHEDULE
Maintenance Operation
Frequency
GC-NPD Primary and Confirmatory
Clean or replace rhubidium bead in NPD
Replace septa
Break off ends of GC column or replace column
Clean injection port liner
MS Confirmation
Replace mechanical pump oil
Replace filament
Replace electron multiplier
Clean ion source
When poor response is observed
Every day
When poor chromatography is observed
When poor chromatography is observed
Every 3 months
When old filment burns out
When multiplier gain is <1x104
When poor tuning is observed
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Section No 13
Revision No 3
Date: April 29, 1988
Page 4 of 4
TABLE 3
SPARE INSTRUMENT PARTS
Gas Chromatography Mass Spectrometry
Fused silica capillary columns Mechanical pump oil
Syringes Filaments
Rhubidium bead assemblies Electron multiplier
Replaceable source components (ceramics)
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Section No 14
Revision No. 3
Date: April 29, 1988
Page 1 of 2
14. SPECIFIC ROUTINE PROCEDURES USED TO ASSESS MEASUREMENT SYSTEM DATA
14.1 Standard Deviation
NPS data precision will be expressed in terms of standard deviation (s) with n-1 degrees of
freedom. The standard deviation is the square root of the variance of a set of values and is calculated
using the equation:
s =
I (Xrx)2
n-1
where: n = the number of data points;
X| = the recovery for sample i in ng/L; and
x = the average recovery for all samples in
14.2 Percent Recovery
Data accuracy is expressed in terms of percent recovery (R) calculated using the equation:
R = (100C)/S
where: C = the calculated level of analyte in the sample, and
S = the level of the analyte spiked into the sample.
14.3 Relative Standard Deviation
The relative standard deviation (RSD) is calculated using the equation:
RSD = (100s)/x
14.4 Peak Symmetry and Peak Gaussian Factors
Acceptable instrument performance is expressed in terms of the peak symmetry factor (PSF)
and peak Gaussian factor (PGF). These calculations are demonstrated in Table 5 and Figure 2 of
Method 6 (Appendix A).
14.5 Minimum Detectable Level
The MDL (Section 5.1) is expressed in ^g/L and is calculated using the equation:
MDL = ((s) t)
where: t = the student's t value appropriate for a 99 percent confidence
level (t = 3.500 for eight measurements and seven degrees of
freedom).
14.6 Estimated Detection Limit
The EDL (Section 5.1) is expressed in ^g/L and equals either the concentration of analyte
yielding a detector response with a 5:1 S/N or the calculated MDL, whichever is greater.
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Section No. 14
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Date: April 29, 1988
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14.7 Minimum Reporting Level
The MRL (Section 5.1) is expressed in ^g/L and is defined as three times the EDL calculated
using primary analytical conditions.
14.8 Control Limits
To construct a control chart (Section 5.3.a), the standard deviation (s) is calculated as described
in Section 14.1 for the measurements (usually 20 total). Warning limits (±2RSD) are calculated using
the equation:
±2RSD = ±2(100s)/x
Control limits (±3RSD) are calculated using the equation:
±3RSD = ±3(100s)/x
14.9 Dixon's Test
Dixon's Test is a criterion used for detecting outliers. Dixon's test is explained in Section
17-3.1.1 and Table A-14 of Appendix B.2 The following assumptions will be made in applying Dixon's
Text:
The probability or risk acceptable for rejecting an observation will be 1% (a = .01),
• The test will be used to reject "extreme observations" in either direction as opposed
to rejecting extreme observations in only one direction (high or low), and
The number of observations (n) will be 20, 19, or 18 since the test will be used to
reject a maximum of three observations.
14.10 Rounding Numbers and Significant Figures
Procedures for rounding numbers and determination of significant figures is described in
Appendix J, "Standard Operating Procedure for Proper Use of Significant Figures and Rounding."
2 Natrella, M. G., Chapter 17. Treatment of Outliers, Experimental Statistics. NBS Handbook 91,
August 1, 1963.
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Section No 15
Revision No. 3
Date: April 29, 1988
Page 1 of 3
15. CORRECTIVE ACTION
The need for correction action occurs when a circumstance arises which threatens the quality of
analytical results. In order for corrective action to be initiated, awareness of a problem must exist. In
this project, the vanguard for early recognition of problems which will affect data quality is the
personnel conducting the laboratory analysis. Each Project Team member is aware of QC procedures
and subtleties associated with each analytical method. These experienced personnel quickly detect
minor instrument changes, changes in method performance, and drifts or malfunctions which can be
corrected, thus preventing major interruptions of method performance. A primary method of detection
of instrumentation problems will arise from analysis of calibration standards periodically during use of
the instruments and by use of internal standard control charts to quickly indicate changes in
instrument performance. A primary method of monitoring method performance is the use of surrogate
standard control charts to quickly indicate changes in analyte recoveries. If major problems arise, the
Project Team will decide upon the proper corrective action and initiate it immediately, thus minimizing
data loss. Therefore, the Project Team, and more specifically Mr. Zimmerman, will have a prime
responsibility for recognizing the need for and initiating corrective action. Decisions on whether to
take corrective action and what action(s) to take will be made in consultation with the Method Leader
(Mr. Zimmerman) and the Project Manager (Mrs. Engel). Such decisions will be based on action limits
discussed in other sections. The Method Leader or Project Manager will apprise the EPA Contract
Technical Monitor of corrective action situations and discuss potential actions with the Technical
Monitor. When a corrective action is taken, the Project Manager will be responsible for notifying the
QAU Manager so that she can, if deemed necessary, intensify the audits of the effected measurement
system. The Method Leader or Project Manager will follow up on corrective action situations to assure
resolution of the situation.
The second level of recognition of the need for corrective action will be the QAU Manager and
the Project Manager. The QAU Manager will determine the need for corrective action from the results
of the system and performance audits described in Section 12.0 and during routine validation of all
Method 6 results. Data inconsistencies and/or invalid data will alert the QAU Manager, Project
Manager and Method Leader to the necessity of corrective action. These individuals will be
responsible for initiating appropriate corrective action.
Each Project Team member will be briefed on the project objectives and data quality required to
meet those objectives. Data quality objectives for this project are listed in Section 5.0. Each individual
will be informed of these objectives and will have responsibility to notify the Method Leader or Project
Manager whenever a measurement system is not yielding data within these objectives.
Situations requiring corrective action will be reported using the Report of Deviation form shown
in Figure 14. The Method Leader and Project Manager are responsible for following up all situations
requiring corrective action. These individuals are responsible for informing the EPA Contract
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Section No. 15
Revision No. 3
Date: April 29, 1988
Page 2 of 3
Technical Monitor of the situation and will assure adequate resolution of such situations. All relevant
information regarding the situation initiating the corrective action and the resolution of the situation are
included on this form. The Report of Deviation form will be included in the project files. Descriptions
of deviations will be included in the Monthly Reports to the EPA Contract Technical Monitor.
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Section No 15
Revision No. 3
Date: April 29, 1988
Page 3 of 3
FIGURE 14
REPORT OF DEVIATION
Project Number:
Title:
Date of Deviation:
Description of Deviation:
Persons Notified:
Samples Involved (include set number):
Description of Remedial Action:
Person Completing Remedial Action:
Description of Resolution of Deviation:
Date of Resolution of Deviation:
Report Prepared by: Date:
Reviewed by: Date:
Study Manager
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Section No 16
Revision No 3
Date- April 29, 1988
Page 1 of 1
16. QUALITY ASSURANCE REPORTS TO MANAGEMENT
The results of periodic activities to assess the quality of the data generated during the project
will be reported to the Project Manager by the QAU Manager. The QAU Manager is responsible for
submission of monthly QA reports in the form of memoranda listing all QAU activities for that month.
Activities include dates of and a summary of results from system or performance audits conducted
during that month, a list of all analysis data approved by the QAU for submission to EPA, periodic
assessment of measurement data accuracy, precision, and completeness, and significant QA
problems and recommended solutions. Results of system audits will be reported to the Project
Manager in memoranda form within one week of the audit. Results of performance audits will be
supplied to the Project Manager within one week of the audit using Battelle's Critical Phase Inspection
Check Sheet shown in Appendix I. The Method Leader or the Project Manager will be responsible for
responding to all issues/concerns referenced in monthly QA reports and results of performance audits.
However, these documents are considered internal Battelle documents and will not be provided to
EPA. EPA will be apprised of QA/QC deviations and issues via phone conversations initiated by the
Project Manager and in Reports of Deviation (Figure 14), which will be summarized in the monthly
progress reports to the EPA Contract Technical Monitor described in Section 10.3.b.
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Appendix A
Revision No 3
Date: April 29, 1988
Page 1 of 27
APPENDIX A
METHOD 6. DETERMINATION OF ETHYLENE THIOUREA
IN GROUND WATER BY GAS CHROMATOGRAPHY
WITH A NITROGEN-PHOSPHORUS DETECTOR
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Method 6. Determination of Ethylene Thiourea (ETU) in Ground
Water by Gas Chromatography with a Nitrogen-Phosphorus Detector
1. SCOPE AND APPLICATION
1.1 This is a gas chromatographic (GC) method applicable to the
determination of ethylene thiourea (ETU, Chemical Abstracts
Registry No. 96-45-7) in ground water.
1.2 This method has been validated in a single laboratory. The
estimated detection limit (EDL) has been determined and is
listed in Table 2. Observed detection limits may vary between
ground waters, depending upon the nature of interferences in the
sample matrix and the specific instrumentation used.
1.3 This method is restricted to use by or under the supervision of
analysts experienced in the use of GC and in the interpretation
of gas chromatograms. Each analyst must demonstrate the ability
to generate acceptable results with this method using the
procedure described in Section 10.2.
1.4 When this method is used to analyze unfamiliar samples for ETU,
identification must be confirmed by at least one additional
qualitative technique.
2. SUMMARY OF METHOD
2.1 The ionic strength and pH of a measured 50-mL volume of sample
are adjusted by addition of ammonium chloride and potassium
fluoride. The sample is poured onto an Extrelut column. ETU is
eluted from the column in 400 mL of methylene chloride. The
extract is solvent exchanged to ethyl acetate and concentrated
to a volume of 5 ml. Chromatographic conditions are described
which permit the separation and measurement of ETU in the
extract by GC with a nitrogen-phosphorus detector (NPD).
3. DEFINITIONS
3.1 Artificial ground water -- an aqueous matrix designed to mimic a
real ground water sample. The artificial ground water should be
reproducible for use by others.
3.2 Calibration standard -- a known amount of a pure analyte,
dissolved in an organic solvent, analyzed under the same
procedures and conditions used to analyze sample extracts
containing that analyte.
3.3 Estimated detection limit (EDL) -- The minimum concentration of
a substance that can be measured and reported with confidence
that the analyte concentration is greater than zero as
determined from the analysis of a sample in a given matrix
72
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containing the analyte. The EDL is equal to the level
calculated by multiplying the standard deviation of replicate
measurements times the students' t value appropriate for a 99
percent confidence level and a standard deviation estimate with
n-1 degrees of freedom or the level of the compound in a sample
yielding a peak in the final extract with signal-to-noise ratio
of approximately five, whichever value is higher.
3.4 Internal standard --a pure compound added to a sample extract
in a known amount and used to calibrate concentration
measurements of other analytes that are sample components. The
internal standard must be a compound that is not a sample
component.
3.5 Instrument quality control (QC) standard --an ethyl acetate
solution containing specified concentrations of specified
analytes. The instrument QC standard is analyzed each working
day prior to the analysis of sample extracts and calibration
standards. The performing laboratory uses this solution to
demonstrate acceptable instrument performance in the areas of
sensitivity, column performance, and chromatographic
performance.
3.6 Laboratory control (LC) standard -- a solution of ETU prepared
in the laboratory by dissolving a known amount of pure ETU in a
known amount of reagent water. In this method, the LC standard
is prepared by adding an appropriate volumes of the ETU standard
solution to reagent water.
3.7 Laboratory reagent blank -- an aliquot of reagent water analyzed
as if it were a sample.
3.8 Performance evaluation sample -- A water-soluble solution of
method analytes distributed by the Quality Assurance Branch,
Environmental Monitoring and Support Laboratory, USEPA, Cincin-
nati, Ohio. A small measured volume of the solution is added to
a known volume of reagent water and analyzed using procedures
identical to those used for samples. Analyte true values are
unknown to the analyst.
3.9 Quality control check sample -- a water soluble solution
containing known concentrations of analytes prepared by a
laboratory other than the laboratory performing the analysis.
The performing laboratory uses this solution to demonstrate that
it can obtain acceptable identifications and measurements with a
method. A small measured volume of the solution is added to a
known volume of reagent water and analyzed with procedures
identical to those used for samples. True values of analytes
are known by the analyst.
3.10 Stock standard solution -- a concentrated solution containing a
certified standard that is a method analyte, or a concentrated
73
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solution of an analyte prepared in the laboratory with an
assayed reference compound.
3.11 Surrogate standard --a pure compound added to a sample In a
known amount and used to detect gross abnormalities during
sample preparation. The surrogate standard must be a compound
that is not a sample component.
4. INTERFERENCES
4.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware and other sample processing apparatus that
lead to discrete artifacts or elevated baselines in gas chrom-
atograms. All reagents and apparatus must be routinely demon-
strated to be free from interferences under the conditions of
the analysis by running laboratory method blanks as described in
Section 10.8.
4.1.1 Glassware must be scrupulously cleaned.1 Clean all
glassware as soon as possible after use by thoroughly
rinsing with the last solvent used in it. Follow by
washing with hot water and detergent and thorough
rinsing with tap and reagent water. Drain dry, and heat
in an oven or muffle furnace at 400*C for 1 hour. Do
not heat volumetric ware. Thermally stable materials
might not be eliminated by this treatment. Thorough
rinsing with acetone and methylene chloride may be
substituted for the heating. After drying and cooling,
seal and store glassware in a clean environment to
prevent any accumulation of dust or other contaminants.
Store inverted or capped with aluminum foil.
4.1.2 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.
4.2 Interfering contamination may occur when a sample containing a
low concentration of ETU is analyzed immediately following a
sample containing a relatively high concentration of ETU.
Between-sample rinsing of the sample syringe and associated
equipment with ethyl acetate can minimize sample cross contamin-
ation. After analysis of a sample containing high concentra-
tions of ETU, one or more injections of ethyl acetate should be
made to ensure that accurate values are obtained for the next
sample.
4.3 Matrix interferences may be caused by contaminants that are
coextracted from the sample. The extent of matrix interferences
will vary considerably from source to source, depending upon the
ground water sampled. Positive identifications must be confirm-
ed using the confirmation column specified in Table 1.
74
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5. SAFETY
5.1 ETU is a cancer suspect agent and teratogen. Primary standards
of ETU should be prepared in a hood. A NIOSH/MESA approved
toxic gas respirator should be worn when the analyst handles
high concentrations of ETU. Each 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 safety data sheets should
also be made available to all personnel involved in the chemical
analysis. Additional references to laboratory safety are
available and have been identified2"4 for the information of the
analyst.
6. APPARATUS AND EQUIPMENT (All specifications are suggested. Catalog
numbers are included for illustration only.)
6.1 SAMPLING EQUIPMENT
6.1.1 Grab sample bottle -- 60-mL screw cap vials (Pierce No.
13075 or equivalent) and caps equipped with a PTFE-faced
silicone septa (Pierce No. 12722 or equivalent). Prior
to use, wash and heat vials and septa as described in
Section 4.1.1.
6.2 GLASSWARE
6.2.1 Concentrator tube, Kuderna-Danish (K-D) -- 10- or 25-mL,
graduated (Kontes K-570050-2525, K-570050-1025 or
equivalent). Calibration must be checked at the volumes
employed in the test. Ground glass stoppers are used to
prevent evaporation of extracts.
6.2.2 Evaporative flask, K-D -- 500-mL (Kontes K-570001-0500
or equivalent). Attach to concentrator tube with
springs.
6.2.3 Snyder column, K-D -- three-ball macro (Kontes K-503000-
0121 or equivalent).
6.2.4 Vials -- Glass, 5- to 10-mL capacity with TFE-fluoro-
carbon lined screw cap.
6.3 Boiling stones -- carborundum, #12 granules (Arthur H. Thomas
Co. #1590-033). Heat at 400'C for 30 min prior to use. Cool
and store in a desiccator.
6.4 Water bath -- Heated, capable of temperature control (±2*C).
The bath should be used in a hood.
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6.5 Balance -- Analytical, capable of accurately weighing to the
nearest 0.0001 g.
6.6 Tube heater -- Capable of holding eight K-D concentrator tubes
and heating the mid-section of the tubes to 35-40*C while
applying a nitrogen stream.
6.7 GAS CHROMATOGRAPH -- Analytical system complete with GC suitable
for use with capillary columns and all required accessories
including syringes, analytical columns, gases, detector and
stripchart recorder. A data system is recommended for measuring
peak areas.
6.7.1 Primary column -- 10 m long x 0.25 mm I.D. DB-Wax bonded
fused silica column, 0.25 pm film thickness (available
from J&W). Validation data presented in this method
were obtained using this column. Alternative columns
may be used in accordance with the provisions described
in Section 10.3.
6.7.2 Confirmation column --5m long x 0.25 mm I.D. DB-1701
bonded fused silica column, 0.25 urn film thickness
(available from J&W).
6.7.3 Detector -- Nitrogen-phosphorus detector (NPD). This
detector has proven effective in the analysis of spiked
reagent and artificial ground waters. A NPD was used to
generate the validation data presented in this method.
Alternative detectors, including a mass spectrometer,
may be used in accordance with the provisions described
in Section 10.3.
7. REAGENTS AND CONSUMABLE MATERIALS
7.1 Reagent water -- Reagent water is defined as water in which an
interferent is not observed at or above the EDL of any analyte.
Reagent water used to generate the validation data in this
method was distilled water obtained from the Magnetic Springs
Water Co., Columbus, Ohio.
7.2 Acetone, methylene chloride, ethyl acetate -- Distilled-in-glass
quality or equivalent.
7.3 Nitrogen gas -- high purity.
7.4 Extraction column, Extrelut QE -- Obtained from EM Science
(Catalog No. 902050-1).
7.5 Ammonium chloride, granular, ACS grade -- for pH and ionic
strength adjustment of samples (available from Baker Chemical
Co.).
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7.6 Potassium fluoride, anhydrous, ACS grade -- for ionic strength
adjustment of sample (available from Baker Chemical Co.).
7.7 Mercuric chloride, granular, ACS grade -- used as sample preser-
vative (available from Mallinckrodt).
7.8 Dithiothreitol (DTT) -- for use as a free-radical scavanger
(available from Aldrich Chemical Co.)*
7.8.1 DTT in ethyl acetate, 1000 ug/mL -- Prepare by adding
1 g DTT to a 1-L volumetric flask and diluting to volume
with ethyl acetate. Store at room temperature.
7.9 Propylene thiourea (PTU) -- for use as a surrogate standard.
Prepared from carbon disulfide and 1,2-d.iaminopropane using the
procedure published by Hardtmann, et. al. (Journal of Medicinal
Chemistry, lfi(5), 447-453, 1975).
7.10 3,4,5,6-Tetrahydro-2-pyrimidinethiol (THP) -- >98% purity, for
use as an internal standard (available from Aldrich Chemical
Co.).
7.11 STOCK STANDARD SOLUTION (0.10 ug/uL) - The stock standard
solution may be purchased as a certified solution or prepared
from pure standard material using the following procedure:
7.11.1 Prepare stock standard solution by accurately weighing
approximately 0.0010 g of pure ETU. Dissolve the ETU in
ethyl acetate containing 1000 M9/mL of DTT and dilute to
volume in a 10-mL volumetric flask. Larger volumes may
be used at the convenience of the analyst. If ETU
purity is certified at 96% or greater, the weight may be
used without correction to calculate the concentration
of the stock standard. Commercially prepared stock
standards may be used at any concentration if they are
certified by the manufacturer or by an independent
source.
7.11.2 Transfer the stock standard solution into a TFE-fluoro-
carbon-sealed screw cap vial. Store at 4'C and protect
from light.
7.11.3 The stock standard solution should be replaced after two
weeks or sooner if comparison with laboratory control
standards indicates a problem.
7.12 INTERNAL STANDARD SPIKING SOLUTION -- Prepare an internal
standard spiking solution by accurately weighing approximately
0.0010 g of pure THP. Dissolve the THP in ethyl acetate
containing 1000 ug/mL of DTT and dilute to volume in a 10-mL
volumetric flask. Transfer the internal standard spiking
solution to a TFE-fluorocarbon-sealed screw cap bottle and store
77
I
\
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at 4'C and protect from light. Addition of 50 ML of the
internal standard spiking solution to 5 ml of sample extract
results in a final internal standard concentration of 1.0
Solution should be replaced when ongoing QC (Section 10)
indicates a problem.
7.13 SURROGATE STANDARD SPIKING SOLUTION -- Prepare a surrogate
standard spiking solution by accurately weighing approximately
0.0010 g of pure PTU. Dissolve the PTU in ethyl acetate
containing 1000 ug/mL of DTT and dilute to volume in a 10-mL
volumetric flask. Transfer the surrogate standard spiking
solution to a TFE-fluorocarbon-sealed screw cap bottle and store
at 4*C and protect from light. Addition of 5 Ml of the
surrogate standard spiking solution to a 50-mL sample prior to
extraction results in a surrogate standard concentration in the
sample of 10 yg/L and, assuming quantitative recovery of PTU, a
surrogate standard concentration in the final extract of
0.10 Mg/mL.
7.14 INSTRUMENT QC STANDARD -• Prepare the instrument QC standard by
adding 10 uL of the ETU stock standard solution, 1.0 mL of the
internal standard spiking solution, and 100 ML of the surrogate
standard spiking solution to a 100-mL volumetric flask and
diluting to volume with ethyl acetate containing 1000 M9/mL °f
DTT. Transfer the instrument QC standard to a TFE-fluorocarbon-
sealed screw cap bottle and store at room temperature.
Solution should be replaced when ongoing QC (Section 10)
indicates a problem.
8. SAMPLE COLLECTION. PRESERVATION. AND STORAGE
8.1 Grab samples must be collected in 60-mL screw cap glass vials
(Section 6.1.1). Conventional sampling practices5 should be
followed; however, the bottle must not be prerinsed with sample
before collection.
8.2 SAMPLE PRESERVATION AND STORAGE
8.2.1 Add mercuric chloride to the sample bottle in amounts to
produce a concentration of 10 mg/L. Add 60 \ii of a
solution containing 10 mg/mL of mercuric chloride in
water to the sample bottle at the sampling site or in
the laboratory before shipping to the sampling site.
Mercuric chloride is a highly toxic chemical. Mercuric
chloride must be handled with caution, and samples
containing mercuric chloride must be properly disposed.
8.2.2 After the sample is collected in the bot+le containing
preservative, seal the sample bottle and shake vigor-
ously for 1 min.
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8.2.3 ETU can degrade quickly in water even when the sample is
refrigerated. Samples should be extracted as soon as
possible and must be extracted within 14 days of
collection. The samples must be iced or refrigerated at
4*C and protected from light from the time of collection
until extraction. Preservation study results given in
Table 4 indicate that samples are stable for 14 days
when stored under these conditions. However, analyte
stability may be affected by the matrix, therefore, the
analyst should verify that the preservation technique is
applicable to the samples under study.
8.3 EXTRACT STORAGE
8.3.1 Extracts should be stored at 70*C away from light.
Preservation study results given in Table 4 indicate
that extracts are stable for at least 28 days when
stored under these conditions. The analyst should
verify appropriate extract holding times applicable to
the samples under study.
9. CALIBRATION
9.1 Establish GC operating parameters equivalent to those indicated
in Table 1. The GC system must be calibrated using the internal
standard technique (Section 9.2).
9.2 INTERNAL STANDARD CALIBRATION PROCEDURE. To use this approach,
the analyst must select one or more internal standards compat-
ible in analytical behavior to the compound of interest. The
analyst must further demonstrate that the measurement of the
internal standard is not affected by method or matrix interfer-
ences. THP has been identified as a suitable internal -standard.
9.2.1 Prepare ETU calibration standards at a minimum of three
(suggested five) concentration levels by adding volumes
of the ETU stock standard to a volumetric flask. To
each calibration standard, add a known constant amount
of one or more internal standards, and dilute to volume
with ethyl acetate containing 1000 pg/mL of DTT. One of
the calibration standards should be representative of an
ETU concentration near, but above, the EDL. The other
concentrations should correspond to the range of concen-
trations expected in the sample concentrates, or should
define the working range of the detector.
9.2.2 Inject 2 \ii of each calibration standard and tabulate
the relative response for ETU to the internal standard
(RRa) using the equation:
79
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where: Aa - the peak area of ETU, and
A-js - the peak area of the internal standard.
Generate a calibration curve of RRa versus ETU concen-
tration in the sample in M9/L.
9.2.3 The working calibration curve must be verified on each
working shift by the measurement of one or more calibra-
tion standards. If the ETU response varies from the
predicted response by more than ±20%, the test must be
repeated using a fresh calibration standard. Alterna-
tively, a new ETU calibration curve must be prepared.
10. QUALITY CONTROL
10.1 Each laboratory using this method is required to operate a
quality control (QC) program. The minimum requirements of this
program consist of the following: an initial demonstration of
laboratory capability; the analysis of surrogate standards in
each and every sample as a continuing check on sample prepara-
tion; the monitoring of internal standard area counts or peak
heights in each and every sample as a continuing check on system
performance; the analysis of QC samples, laboratory control
standards, and performance evaluation (PE) samples as continuing
checks on laboratory performance; the analysis of spiked samples
as a continuing check on recovery performance; the analysis of
method blanks as a continuing check on contamination; and
frequent analysis of the instrument QC standard to assure
acceptable instrument performance.
10.2 INITIAL DEMONSTRATION OF CAPABILITY -- To establish the ability
to perform this method, the analyst must perform the following
operations.
10.2.1 Select a representative spike concentration (suggest
15 times the EDL) for ETU. Using a stock standard that
differs from calibration standard, prepare a laboratory
control (LC) check sample concentrate in methanol 1000
times more concentrated than the selected spike concen-
tration.
10.2.2 Using a syringe, add 50 uL of the LC sample concentrate
to each of a minimum of four 50-mL aliquots of reagent
water. A representative ground water may be used in
place of the reagent water, but one or more unspiked
aliquots must be analyzed to determine background
levels, and the spike level must, at a minimum, exceed
twice the background level for the test, to be valid.
Analyze the aliquots according to the method beginning
in Section 11.
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10.2.3 Calculate the average percent recovery (R) and the
standard deviation of the percent recovery ($R), for the
results. Ground water background corrections must be
made before R and SR calculations are performed.
10.2.4 Tables 2-3 provide single laboratory recovery and
precision data obtained for ETU from reagent and
artificial ground waters, respectively. Similar results
from dosed reagent and artificial ground waters should
be expected by any experienced laboratory. Compare
results obtained in Section 10.2.3 to the single
laboratory recovery and precision data. If the results
are not comparable, review potential problem areas and
repeat the test. Results are comparable if the calcu-
lated percent relative standard deviation (RSD) does not
exceed 2.6 times the single laboratory RSD or
20 percent, whichever is greater, and your mean recovery
lies within the interval R+3S or R+30% whichever is
greater.
10.3 In recognition of the rapid advances occurring in chromato-
graphy, the analyst is permitted to modify GC columns, GC
conditions, or detectors to improve the separations or lower the
cost of measurements. Each time such modifications to the
method are made, the analyst is required to repeat the procedure
in Section 10.2.
10.4 ASSESSING SURROGATE RECOVERY
10.4.1 All samples and blanks must be fortified with the
surrogate spiking compound before extraction. A
surrogate standard determination must be performed on
all samples (including matrix spikes) and blanks.
10.4.2 Determine whether the measured surrogate concentration
(expressed as percent recovery) falls between 70 and 130
percent.
10.4.3 When the surrogate recovery for a laboratory reagent
blank is less than 70 or greater than 130 percent, the
laboratory must take the following actions:
(1) Check calculations to make sure there are no
errors.
(2) Check internal standard and surrogate standard
spiking solutions for degradation, contamination,
or other obvious abnormalities.
(3) Check instrument performance.
81
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Reinject the laboratory method blank extract. If the
reanalysis fails the 70 to 130 percent recovery
criteria, the analytical system must be considered "out
of control." The problem must be identified and
corrected before continuing.
10.4.4 When the surrogate recovery for a sample is less than 70
percent or greater than 130 percent, the laboratory must
establish that the deviation is not due to laboratory
problems. The laboratory shall document deviations by
taking the following actions:
(1) Check calculations to make sure there are no
errors.
(2) Check internal standard and surrogate standard
spiking solutions for degradation, contamination,
or other obvious abnormalities.
(3) Check instrument performance.
Recalculate or reanalyze the extract if the above steps
fail to reveal the cause of the noncompliant surrogate
recoveries. If reanalysis of the sample or extract
solves the problem, only submit the sample data from the
analysis with surrogate spike recoveries within the
required limits. If reanalysis of the sample or extract
fails to solve the problem, then report all data for
that sample as suspect.
10.5 ASSESSING THE INTERNAL STANDARD
10.5.1 An internal standard peak area or peak height check must
be performed on all samples. All sample extracts must
be fortified with the internal standard.
10.5.2 Internal standard recovery must be evaluated for
acceptance by determining whether the measured peak area
or peak height for the internal standard in any sample
deviates by more than 30 percent from the average peak
area or height for the internal standard in the calibra-
tion standards.
10.5.3 When the internal standard peak area or height for any
sample is outside the limit specified in 10.5.2, the
laboratory must investigate.
10.5.3.1 Single occurrence -- Reinject an aliquot of
the extract to ensure proper sample injection.
If the reinjected sample extract aliquot
displays an internal standard peak area or
height within specified limits, quantify and
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report results. If the reinjected sample
extract aliquot displays an internal standard
peak area or height outside the specified
limits, but extract aliquots from other
samples continue to give the proper area or
height for the internal standard, assume an
error was made during addition of the internal
standard to the failed sample extract. Repeat
the analysis of that sample.
10.5.3.2 Multiple Occurrence -- If the internal
standard peak areas or heights for successive
samples fail the specified criteria (10.5.2),
check the instrument for proper performance.
After optimizing instrument performance, check
the calibration curve using a calibration
check standard (Section 9). If the calibra-
tion curve is still applicable and if the
calibration check standard internal standard
peak area or height is within ±30% of the
average internal standard peak area or height
for the calibration standards, reanalyze those
sample extracts whose internal standard failed
the specified criteria. If the internal
standard peak areas or heights now fall within
the specified limits, report the results. If
the internal standard peak areas or heights
still fail to fall within the specified limits
or if the calibration curve is no longer
applicable, then generate a new calibration
curve (Section 9) and reanalyze those sample
extracts whose internal standard failed the
peak area or height criteria.
10.6 ASSESSING LABORATORY PERFORMANCE
10.6.1 The laboratory must, on an ongoing basis, analyze at
least one laboratory control standard per sample set (a
sample set is all those samples extracted within a
24-hour period).
10.6.1.1 The spiking concentration in the laboratory
control standard should be 15 times the EDL.
10.6.1.2 Spike a reagent water aliquot with a labora-
tory control (1C) sample concentrate (the
volume of the spike should be kept to a
minimum so the solubility of the analytes of
interest in water will not be affected) and
analyze it to determine the concentration
after spiking (A) of each parameter. Calcu-
late each percent recovery (Ri) as (lOOxA)VT,
83
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where T
spike.
is the known true concentration of the
10.6.1.3 Compare the percent recovery (Rj) for each
parameter with established QC acceptance
criteria. QC criteria are established by
initially analyzing five laboratory control
standards and calculating the average percent
recovery (R) and the standard deviation of the
percent recovery (SR) using the following
equations:
1-1
and
where: n - number of measurements for each
analyte, and
R.J « individual percent recovery
value.
Calculate QC acceptance criteria as follows:
Upper Control Limit (UCL) • R + 3Sp
Lower Control Limit (LCL) - R - 3Sp
Alternatively, the data generated during the
initial demonstration of capability (Section
10.2) can be used to set the initial upper and
lower control limits.
Update the performance criteria on a contin-
uous basis. After each five to ten new
recovery measurements (RiS), recalculate R and
SR using all the data, and construct new
control limits. When the total number of data
points reach twenty, update the control limits
by calculating R and SR using only the most
recent twenty data points.
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Monitor all data from laboratory control
standards. Analyte recoveries must fall
within the established control limits.
If the recovery of ETU falls outside the
designated range, the laboratory performance
for ETU is judged to be out of control, and
the source of the problem must be immediately
identified and resolved before continuing the
analyses. The analytical result for ETU in
samples is suspect and must be so labeled.
All results for ETU for that sample set must
also be labeled suspect.
10.6.2 Each quarter, it is essential that the laboratory
analyze (if available) QC check standards. If the
criteria established by the U.S. Environmental Protec-
tion Agency (USEPA) and provided with the QC standards
are not met, corrective action needs to be taken and
documented.
10.6.3 The laboratory must analyze an unknown performance
evaluation sample (when available) at least once a year.
Results for each of the target analytes need to be
within acceptable limits established by USEPA.
10.7 ASSESSING ANALYTE RECOVERY
10.7.1 The laboratory must, on an ongoing basis, spike each of
the target analytes into ten percent of the samples.
10.7.1.1 The spiking concentration in the sample should
be one to five times the background concentra-
tion, or, if it is impractical to determine
background levels before spiking, 15 times the
EDL.
10.7.1.2 Analyze one sample aliquot to determine the
background concentration (B) of each para-
meter. Spike a second sample aliquot with a
laboratory control (LC) sample concentrate
(the volume of the spike should be kept to a
minimum so the solubility of the analytes of
interest in water will not be affected) and
analyze it to determine the concentration
after spiking (A) of each parameter. Calcu-
late each percent recovery (R-j) as
100(A-B)%/T, where T is the known true
concentration of the spike.
10.7.1.3 Compare the percent recovery (R-j) for each
parameter with QC acceptance criteria deter-
85
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mined by the analysis of laboratory control
standards.
Monitor all data from dosed samples. Analyte
recoveries must fall within the established
control limits.
10.7.1.4 If the recovery of ETU falls outside the
designated range, and the laboratory perfor-
mance for ETU is judged to be in control, the
recovery problem encountered with the dosed
sample is judged to be matrix-related, not
system-related. The result for ETU in the
unspiked sample is labeled suspect/matrix to
inform the user that the results are suspect
due to matrix effects.
10.8 ASSESSING LABORATORY CONTAMINATION (METHOD BLANKS) -- Before
processing any samples, the analyst must demonstrate that all
glassware and reagent interferences are under control. This is
accomplished by the analysis of a laboratory method blank. A
laboratory method blank is a 50-mL aliquot of reagent water
analyzed as if it was a sample. Each time a set of samples is
extracted or there is a change in reagents, a laboratory method
blank must be processed to assess laboratory contamination. If
the method blank exhibits a peak within the retention time
window of ETU which is greater than or equal to one-half the EDL
for ETU, determine the source of contamination before processing
samples and eliminate the interference problem.
10.9 ASSESSING INSTRUMENT PERFORMANCE (INSTRUMENT QC STANDARD) --
Instrument performance should be monitored on a daily basis by
analysis of the instrument QC standard. The instrument QC
standard contains compounds designed to indicate appropriate
instrument sensitivity, column performance and chromatographic
performance. Instrument QC standard components and performance
criteria are listed in Table 5. Inability to demonstrate
acceptable instrument performance indicates the need for
reevaluation of the GC-NPD system. A GC-NPD chromatogram
generated from the analysis of the instrument QC standard is
shown in Figure 1. The sensitivity requirements are set based
on the EDL published in this method. If the laboratory EDL
differs from that listed in this method, concentrations of the
instrument QC standard compounds must be adjusted to be com-
patible with the laboratory EDL. An instrument QC standard
should be analyzed with each sample set.
10.10 ANALYTE CONFIRMATION - When doubt exists over the identification
of a peak on the chromatogram, confirmatory techniques such as
mass spectrometry or a second gas chromatography column must be
used. A suggested confirmation column is described in Table 1.
86
-------
10.11 ADDITIONAL QC - It is recommended that the laboratory adopt
additional quality assurance practices for use with this
method. The specific practices that are most productive depend
upon the needs of the laboratory and the nature of the samples.
11. PROCEDURE
11.1 SAMPLE EXTRACTION
11.1.1 Add preservative to any samples not previously preserved
(Section 8.2). Pipet 50 mL of water sample into a 60-mL
bottle containing 1.5 g of ammonium chloride and 25 g of
potassium fluoride. Close bottle and shake vigorously
until salts are dissolved. Spike sample with 5 uL of
the surrogate standard spiking .solution.
11.1.2 Pour contents of bottle onto Extrelut column. Allow the
column to stand undisturbed for 15 min.
11.1.3 Add 5 mL of 1000 ug/mL DTT in ethyl acetate to a K-D
concentrator tube equipped with a 500-mL flask.
11.1.4 Add 400 mL of methylene chloride in 50-75 mL portions to
the Extrelut column and collect the eluant in the K-D
apparatus (Section 11.1.3). The water, ammonium
chloride and potassium fluoride remain on the Extrelut
column while the ETU is removed from the column in the
methylene chloride eluate. Discard the Extrelut column.
11.2 EXTRACT CONCENTRATION
11.2.1 Add 1 or 2 clean boiling stones to the K-D apparatus and
attach a macro Snyder column. Prewet the Snyder column
by adding about 1 mL of methylene chloride to the top.
Place the K-D apparatus in a 65-70'C water bath so that
the K-D tube is partially immersed in the hot water, and
the entire lower rounded surface of the flask is bathed
with hot vapor. When the apparent volume of liquid
reaches 5 mL, remove the K-D apparatus and allow it to
drain and cool for at least 10 min.
11.2.2 Reduce the liquid volume in the K-D tube to approximat-
ely 1 mL by placing the sample extract in a tube heater
at 35-40*C under a stream of nitrogen. The tube heater
heats the solvent in the K-D tube at volume markings
between 1 and 10 mL.
11.2.3 Dilute sample extract to 5 mL with ethyl acetate; rinse
walls of K-D tube while adding ethyl acetate. Immed-
iately spike sample extract with 50 uL of internal
standard spiking solution. Agitate sample extract to
disperse internal standard. Transfer sample extract to
37
-------
a GC vial and determine ETU by GC-NPD as described in
Section 11.3. Sample extracts should be protected from
light and analyzed within 24 hours of extraction.
Sample extracts can be stored for up to 28 days, frozen
at -10*C and protected from light.
11.3 GAS CHROMATOGRAPHY
11.3.1 Table 1 summarizes the recommended GC operating condi-
tions. Included in Table 1 are retention times observed
using this method. An example of the separations
achieved using these conditions are shown in Figure 1.
Other GC columns, chromatographic conditions, or
detectors may be used if the requirements of
Section 10.1 are met.
11.3.2 Calibrate the system daily as described in Section 9.
The standards and extracts must be in ethyl acetate
containing 1000 (jg/mL DTT.
11.3.3 Inject 2 ML of the sample extract. Record the resulting
peak size in area units.
11.3.4 The width of the retention time window used to make
identifications should be based upon measurements of
actual retention time variations of standards over the
course of a day. Three times the standard deviation of
a retention time can be used to calculate a suggested
window size for a compound. However, the experience of
the analyst should weigh heavily in the interpretation
of chromatograms.
11.3.5 If the response for the peak exceeds the working range
of the system, dilute the extract with ethyl acetate
containing 1000 \ig/ml DTT and reanalyze.
12. CALCULATIONS -- Calculate the ETU concentration in the sample from the
ETU relative response (RRa) to the internal standard using the
calibration curve described in Section 9.2.2.
13. PRECISION AND ACCURACY
13.1 In a single laboratory, ETU recoveries from reagent water were
determined at five concentration levels. Results were used to
determine the ETU EOL and demonstrate method range. EDL and
method range data are given in Table 2.
13.2 In a single laboratory, ETU recoveries from two artificial
ground waters were determined at one concentration level.
Results were used to demonstrate applicability of the method to
different ground water matrices. ETU recoveries from the two
artificial matrices are given in Table 3.
38
-------
13.3 In a single laboratory, ETU recoveries from a ground water
preserved with mercuric chloride were determined 0, 14, and 28
days after spiking the sample with ETU. Sample extracts were
also reanalyzed after they were stored for 28 days at -10*C and
protected from light. Results were used to predict expected ETU
stability in ground water samples and sample extracts. ETU
recoveries from the preserved, spiked ground water samples and
stored extracts are given in Table 4.
-------
REFERENCES
1. ASTM Annual Book of Standards, Part 11, Volume 11.02, D3694-82,
"Standard Practice for Preparation of Sample Containers and for
Preservation", American Society for Testing and Materials, Philadel-
phia, PA, p. 86, 1986.
2. "Carcinogens - Working with Carcinogens," Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, Aug. 1977.
3. "OSHA Safety and Health Standards, General Industry," (29 CFR 1910),
Occupational Safety and Health Administration, OSHA 2206, (Revised,
January 1976).
4. "Safety in Academic Chemistry Laboratories," American Chemical Society
Publication, Committee on Chemical Safety, 3rd Edition, 1979.
5. ASTM Annual Book of Standards, Part 11, Volume 11.01, 03370-82, "Stan-
dard Practice for Sampling Water," American Society for Testing and
Materials, Philadelphia, PA, p. 130, 1986.
6. Nitz, S., Moz, P. and F. Korte, "A Capillary Gas-Liquid Chromatographic
Method for Determination of Ethylenethiourea and Propylenethiourea in
Hops, Beer, and Grapes," J. Agric. Food Chem., 1982, 3JJ, 593-596.
90
-------
TABLE 1. PRIMARY AND CONFIRMATION CHROMATOGRAPHIC CONDITIONS
Retention Time, min
Analyte Primary column
ETU
THP (internal standard)
PTU (surrogate standard)
3.5
5.1
2.7
Confirmation column
4.5
5.0
2.2
Primary conditions:
Column:
Carrier gas:
Makeup gas:
Detector gases:
Injector temperature:
Detector temperature:
Oven temperature:
Sample:
Detector:
Confirmation conditions;
Column:
Carrier gas:
Makeup gas:
Detector gases:
Injector temperature:
Detector temperature:
Oven temperature:
Sample:
Detector:
10 m long x 0.25 mm I.D. DB-Wax bonded fused
silica column (J&W), 0.25 m film thickness
He 9 30 cm/sec linear velocity
He (? 30 mL/min flow
Air 9 100 mL/min flow; H2 I? 3 mL/min flow
220'C
230'C
220'C isothermal
2 uL splitless; 9 sec split delay
Ni trogen-phosphorus
5 m long x 0.25 mm I.D. DB-1701 bonded fused
silica column (J&W), 0.25 m film thickness
He 9 30 cm/sec linear velocity
He 9 30 mL/min flow
Air 9 100 mL/min flow; H2 9 3 mL/min flow
150'C
270'C
150'C isothermal
2 uL splitless; 9 sec split delay
Nitrogen-phosphorus
91
-------
TABLE 2. RESULTS FROM EDL AND METHOD RANGE STUDIES (a)
Spiking
Level ,
ug/L
5.0
10
25
100
Amt in
Blank,
M9/L
0.492
ND (b)
NO
NO
n(d)
7
7
7
7
R(e)
97 (c)
102
94
97
S(f)
0.845
0.886
1.31
5.96
RSD(g)
17
9
6
6
EDL(h)
5.0
-
-
•
(a) Studies conducted in reagent water; average recovery of PTU
surrogate from seven spiked reagent water samples was 100%
(RSD was 8.5%).
(b) ND - not detected.
(c) Data corrected for amount detected in blank.
(d) n » number of recovery data points.
(e) R - average percent recovery.
(f) S » standard deviation.
(g) RSD - percent relative standard deviation.
(h) EDL - estimated detection limit in sample in ug/L; calculated by
multiplying standard deviation (S) times the students' t value
appropriate for a 99% confidence level and a standard deviation
estimate with n-1 degrees of freedom, or level of compound in
sample yielding a peak in the final extract with signal-to-noise
ratio of approximately 5, whichever value is higher.
92
-------
TABLE 3. RESULTS FROM MATRIX EVALUATION STUDIES (a)
Matrix
Amt in
Blank,
H9/L
n(e) R(f)
S(9)
RSD(h)
Hard (b) ND (d) 7 93 0.372 4
Organic-contaminated (c) ND 7 93 0.253 3
(a) Samples were spiked with at the 10 ug/L level with ETU.
(b) Absopure Natural Artesian Spring Water obtained from the Absopure
Water Company in Plymouth Michigan.
(c) Reagent water spiked with fulvic acid at the 1 mg/L concentration
level. A well-characterized fulvic acid, available from the
International Humic Substances Society (associated with the United
States Geological Survey in Denver, Colorado), was used.
(d) ND - not detected.
(e) n - number of recovery data points.
(f) R « Average percent recovery.
(g) S - standard deviation.
(h) RSD - percent relative standard deviation.
93
-------
TABLE 4. RESULTS FROM PRESERVATION STUDY
Extraction Date
Day 0
Day 0
Day 14
Day 28
Analysis Date
Day 0
Day 28 (c)
Day 14
Day 28
R(a)
86
87
80
45
RSD(b)
2
3
6
10
(a) R « percent recovery; average of triplicate analyses.
(b) RSD - percent relative standard deviation of triplicate
analyses.
(c) Sample extract stored for 28 days at 4"C and protected
from light.
94
-------
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Appendix B
Revision No. 3
Date: April 29, 1988
Page 1 of 3
APPENDIX B
DIXON'S TEST FOR OUTLIERS
-------
DIXON'S TEST
Dixon's test is used to confirm the suspicion of outliers of a set of data
(for example, control chart data points). It is based on ranking the data
points and testing the extreme values for credibility. Dixon's test is based
on the ratios of differences between observations and does not involve the
calculation of standard deviations.
The procedure for Dixon's test is as follows (from Taylor, 1987):
1) The data is ranked in order of increasing numerical value. For
example:
Xi < X2 < X3 < ... < Vl < Xn
2) Decide whether the smallest, X^ or the largest, Xn, is
suspected to be an outlier.
3) Select the risk you are willing to take for false rejection.
For use in this QAPP we will be using a 5X risk of false
rejection.
4) Compute one of the ratios in Table 1. For use in this QAPP we
will be using ratio r22, since we will be using between 20 and
17 points for the control charts.
5) Compare the ratio calculated in Step 4 with the appropriate
values in Table 2. If the calculated ratio is greater than the
tabulated value, rejection may be made with the tbulated risk.
Fort his QAPP we will be using the 5% risk values (bolded).
Example (from Taylor)
Given the following set of ranked data:
10.45, 10.47, 10.47, 10.48, 10.49, 10.50, 10.50, 10.53, 10.58
The value 10.58 is suspected of being an outlier.
1) Calculate rn
10.58 - 10.53 0.05
ru - - - 0.454
10.58 - 10.47 0.11
2) A 5% risk of false rejection (Table 2), ru - 0.477
3) Therefore there is no reason to reject the value 10.58.
4) Note that at a 10% risk of false rejection rn - 0.409, and the value
10.58 would be rejected.
-------
TABLE 1
CALCULATION OF RATIOS
For use if if Xj, is if X: is
Ratio n is between suspect suspect
-------
TABLE 2
VALUES FOR USE WITH THE DIXON TEST FOR OUTLIERS
Risk of False Rejection
n 0.5% 1% 5% 10%
-10
•ii
-21
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
0.994
0.926
0.821
0.740
0.080
0.725
0.677
0.639
0.713
0.675
0.649
0.674
0.647
0.624
0.605
0.589
0.575
0.562
0.988
0.889
0.780
0.698
0.637
0.683
0.635
0.597
0.679
0.642
0.615
0.641
0.616
0.595
0.577
0.561
0.547
0.535
0.524
0.514
0.505
0.497
0.489
0.941
0.765
0.642
0.560
0.507
0.554
0.512
0.477
0.576
0.546
0.521
0.546
0.525
0.507
0.490
0.475
0.462
0.450
0.440
0.430
0.421
0.413
0.406
0.806
0.679
0.557
0.482
0.434
0.479
0.441
0.409
0.517
0.490
0.467
0.492
0.472
0.454
0.438
0.424
0.412
0.401
0.391
0.382
0.374
0.367
0.360
Note that for this QAPjP the 5% risk level will be used for ratio r
22-
-------
Reference:
John K. Taylor, Quality Assurance of Chemical Measurements. Lewis
Publishers, Chelsea, MI, 1987.
-------
Appendix C
Revision No. 3
Date: April 29, 1988
Page 1 of 5
APPENDIX C
ETU CONFIRMATION BY LOW-RESOLUTION GC-MS
-------
ETU CONFIRMATION BY LOW-RESOLUTION GC-MS
1. SCOPE
1.1
Confirmation by gas chromatography-mass spectrometry (GC-MS) will
be conducted on all samples exhibiting a peak with intensity
greater than or equal to half the minimum reporting level (MRL)
occurring at a retention time corresponding to ethylene thiourea
(ETU) under both primary and secondary NPS Method 6 conditions.
1.2 If the ETU concentration is sufficient, this confirmation will be
carried out by low-resolution GC-MS according to the procedure
outlined.
1.3 The detection limit for ETU by low-resolution GC-MS is 0.5 pg/ml in
the analyzed extract, corresponding to a detection limit of 5 ftg/L
in the original water sample. An additional 10:1 concentration of
the extract is required to achieve this detection limit.
2. SUMMARY
2.1 ETU confirmation is performed by low-resolution GC-MS, and results
are compared to analysis of a standared containing ETU at a con-
centration near that expected in the sample extract.
2.2 If required, the sample and standard are further concentrated prior
to analysis by nitrogen blowdown.
2.3 Results of the analysis are reported as the presence or absence of
the analyte.
3. APPARATUS
3.1 Nitrogen Evaporator — Organomation N-Evap Analytical Evaporator
Model 111 or equivalent, capable of maintaining concentrator tubes
at 35-40°C while applying a nitrogen stream over the sample extract
3.2 Low-resolution GC-MS analytical system -- recommended instrumenta-
tion and conditions for low-resolution GC-MS confirmation of ETU
are:
Instrumentation:
MS conditions:
MID description:
Column:
Finnigan 4500 mass spectrometer with a
Finnigan 9610 gas chromatograph
Multiple ion detection (MID), ionizing
energy 70 eV, electron multiplier voltage
2400 V, preamp 10-7 volts/amp
Total scan time 0.6 sec; integration time
0.2 msec; ETU masses monitored 72, 73,
104, and 102 (molecular ion); internal
standard mass monitored 116
5 m long x 0.25 mm I.D. DB-Wax bonded
fused silica capillary column, 0.25 /*m
film thickness
102
-------
Carrier: He @ 80 cm/sec linear flow
Injector temp: 280°C
Injection: 2.0 nL splitless
Oven temperature: 180°C isothermal for 0.5 min; programmed
from 180°C to 250°C at 25°C/min; iso-
thermal at 250°C for 3 min
4. PROCEDURE
4.1 Sample Prepartion
4.1.1 If GC-NPD analyses indicate that the concentration of ETU in
the sample is greater than 50 pg/L (representing an extract
concentration of 0.50 pg/mL), the sample extract should be
analyzed by low resolution GC-MS without any further sample
concentration using the conditions specified in Section 3.2.
4.1.2 If GC-NPD analyses indicate that the concentration of ETU in
the sample is between 5 and 50 /tg/L (representing an extract
concentration of between 0.05 and 0.50 ng/ml), concentrate
the extract by a factor of 10 under a stream of nitrogen
while heating at 35-40°C. Analyze the resulting concentrate
by GC-MS using the conditions specified in Section 3.2.
4.1.3 If GC-NPD analyses indicate that the concentration of ETU in
the sample is less than 5 pg/L, the extract should be
shipped to the EPA referee laboratory for high resolution
GC-MS analysis as described in Section 5.9 of the Quality
Assurance Project Plan.
4.2 Calibration
4.2.1 Prepare a standard containing approximately the concentra-
tion of ETU expected in the sample extract after primary or
secondary GC analysis, whichever determined concentration is
lower.
4.2.2 If additional sample concentration is required for GC-MS
analysis (Section 4.1), concentrate the standard as des-
cribed in Section 4.1.2.
4.2.3 Analyze the standard by GC-MS, using the conditions speci-
fied in Section 3.2, and compare the results to those
obtained for the sample. Representative selective ion
profiles for a 0.5 /tg/mL standard are given in Figure 1.
4.3 Identification and Reporting
4.3.1 ETU identification in the sample is to made on the basis of
mass spectra and retention time after comparison to the GC-
MS results obtained from analysis of the standard.
103
-------
4.3.2 If the sample exhibits a peak at the appropriate retention
time and of similar area (relative to the internal standard)
to the ETU standard for the molecular ion (m/z 102) and two
of the confimation ions (m/z 72,73 or 104) monitored, the
presence of ETU is confirmed.
4.3.3 Report the results of the GC-MS analysis as the presence or
absence of ETU.
104
-------
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-------
Appendix D
Revision No. 3
Date: April 29, 1988
Page 1 of 5
APPENDIX D
STANDARD OPERATING PROCEDURE
FOR USE OF ADMIRAL FREEZERS
-------
Page 1 of 4
Analytical and Structural Chemistry Center
SOP ASCC-20-002-01
September 19, 1986
Kev Words: Refrigeration
Storage
Title:
STANDARD OPERATING PROCEDURE
FOR USE OF ADMIRAL FREEZERS
Originated by:
Approved by:
s<^
Charles V. Sueper
Date:
Date:
Johnl R. Nixon, Manager
Aira/ytical and Structural Chemistry Center
Approved by: //
Date:
Approved by: l
)uane E. Hilmas, "Manager
Chemistry and Biomedical Sciences Department
Date:
Ramona A. Mayer,
Quality Assurance Unit
Approved by:
&*
L
AnnJ I. BarTcer, Director
Biological and Chemical Sciences
Date:
Circulation List:
QAU
QCWG
Record of Reviews:
Date: Reviewed by:
Date
Reviewed by:
&PPROVED
107
-------
Page 2 of 4 Analytical and Structural Chemistry Center
SOP ASCC-20-002-01
September 19, 1986
STANDARD OPERATING PROCEDURE
FOR USE OF ADMIRAL FREEZERS
1. EQUIPMENT DESCRIPTION
1.1. Admiral Freezer or equivalent.
1.2. Manufactured by Rockwell International's Admiral Group.
2. OPERATING PROCEDURE
2.1. Plug the unit into an appropriate electrical outlet.
2.2. Place a thermometer on a shelf near the center of the unit.
2.3. Turn the temperature control to the "C" setting and let the unit
run for 2 hours.
2.4. Turn the temperature control to the "D" setting for operation
below 12 C.
2.4.1. The freezer may be operated in the range of -20 C to 0 C
with the temperature being selected using the temperature
control gauge. A setting of "A" gives a temperature near
0 C while a setting of "E" gives a temperature near -20 C.
2.5. Allow 24 hours for the temperature to stabilize. If the
temperature is not in the desired range, reset the gauges as
stated in Section 2.4 and allow temperature to stabilize before
rechecking.
2.6. Temperatures should be recorded on a log sheet, to be kept on the
door of the unit, by the individuals using the freezer. [See
attachment.]
3. MAINTENANCE AND CLEANING
3.1. The unit should be cleaned as needed, using warm, soapy water.
Take care to prevent contamination from hazardous materials which
may be present (i.e., wear rubber gloves).
3.2. Defrosting the unit should be done when frost has built up to
approximately 1/4" thickness in the freezer compartment.
3.2.1. Remove any temperature sensitive contents to another
freezer/refrigerator.
APPROVED 108
-------
Page 3 of 4 Analytical and Structural Chemistry Center
SOP ASCC-20-002-01
September 19, 1986
STANDARD OPERATING PROCEDURE
FOR USE OF ADMIRAL FREEZERS
3.2.2. Turn off the power to the unit.
3.2.3. Open the door and allow ambient air to melt the frost.
3.2.4. Dry the moisture from the unit.
3.2.5. Turn the unit's power back on.
3.2.6. Check the temperature after a stabilization period.
3.2.7. Replace contents when temperature is satisfactory.
3.3. Maintenance should be performed only by a qualified refrigeration
specialist.
APPROVED
^^
109
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Page 4 of 4
Analytical and Structural Chemistry Center
SOP ASCC-20-002-01
September 19, 1986
STANDARD OPERATING PROCEDURE
FOR USE OF ADMIRAL FREEZERS
ATTACHMENT
Freezer Temperature Log
Location of Freezer:
Temperature
Date
Initials
Temperature
Date
110
Initials
-------
Appendix E
Revision No. 3
Date: April 29, 1988
Page 1 of 4
APPENDIX E
STANDARD OPERATING PROCEDURE
FOR USE OF HOTPOINT REFRIGERATORS
-------
Page 1 of 3 Analytical and Structural Chemistry Center
SOP ASCC-20-003-01
September 22, 1986
Kev Words: Refrigeration
Storage
Title: STANDARD OPERATING PROCEDURE
FOR USE OF HOTPOINT REFRIGERATORS
Originated by: ^>ji ~/...~^ _ Date:
Charles V. Sueper '
Approved by: SW\*~l/f ~ A^t2u>^ Date:
John R. Nixon, Manager
Analytical and Structural Chemistry Center
Approved by: /S\ ,!/,i*~~ J' rtL^-1^,^ „ , ^ Date: £/ /£*r/J''
Duane E. Hilmas, Manager '
Chemistry and Biomedical Sciences Department
_^- *-< ,
s^\/— / / . ~\
Approved by: ^".--^^t-.^- /' '?_'<'•« Date: •'_
Approved by: 7(^7^^f^\ ^^ Date: ////7/&
Anna UT Barker, Director // /
Biological and Chemical Sciences
Circulation List:
QAU
QCWG
Record of Reviews:
Date: Reviewed by: Date Reviewed by:
112
-------
Page 2 of 3 Analytical and Structural Chemistry Center
SOP ASCC-20-003-01
September 22, 1986
STANDARD OPERATING PROCEDURE
FOR USE OF HOTPOINT REFRIGERATORS
1. EQUIPMENT DESCRIPTION
1.1. Hotpoint Refrigerator.
1.2. Manufactured by General Electric Company
2. OPERATING PROCEDURE
2.1. Plug the unit into an appropriate electrical outlet.
2.2. Place a thermometer on a shelf near the center of the unit.
2.3. Set the dual temperature gauges to "5" and "C" to achieve a
temperature near the middle of the 0 C to 10 C operating range.
2.3.1. The refrigerator may be set to the wanner end of the
range, ca. 10 C, or the colder range, ca. 0 C, by setting
the gauges to "1" and "A", or "10" and "E", respectively.
2.3.2. An intermediate temperature may be achieved by varying the
settings on the gauges to give the desired temperature.
2.4. Allow 24 hours for the temperature to stabilize. If the
temperature is not in the desired range, reset the gauges as
stated in Section 2.3 and allow temperature to stabilize before
rechecking.
2.5. Temperatures should be recorded on a log sheet, to be kept on the
door of the unit, by the individuals using the refrigerator. [See
attachment.]
3. MAINTENANCE AND CLEANING
3.1. The unit should be cleaned as needed, using warm, soapy water.
Take care to prevent contamination from hazardous materials which
may be present (i.e., wear rubber gloves).
3.2. Maintenance should be performed only by a qualified refrigeration
specialist.
4. SAFETY PRECAUSTIONS
4.1. If the unit is used for storage of hazardous/toxic materials, this
information should be clearly posted.
113
-------
(<••'«• '1
•** t 4 ^o.i ,i,
., 1-
Page 3 of 3
Analytical and Structural Chemistry Center
SOP ASCC-20-003-01
September 22, 1986
STANDARD OPERATING PROCEDURE
FOR USE OF HOTPOINT REFRIGERATORS
ATTACHMENT
Refrigerator Temperature Log
Location of Refrigerator:
Temperature
Date
Initials
Temperature
Date
•
Initials
114
-------
Appendix F
Revision No 3
Date: April 29, 1988
Page 1 of 5
APPENDIX F
STANDARD OPERATING PROCEDURE FOR WEIGHT
DETERMINATIONS USING AN ELECTRONIC ANALYTICAL BALANCE
-------
- <- Date:
Ramona A. Mayer, Manager
Quality Assurance Unit
Approved by: ^^ ^ ^~- Date:
ATfha'D. Barker, Senior V^ce^President ' '
Biological and Chemical /sciences
Circulation List: APPROVED
QAU
QCWG
Record of Reviews;
D?te: Reviewed by: Date Reviewed by:
116
-------
Page 2 of 4 Analytical and Structural Chemistry Center
SOP ASCC-20-010-02
(Revised)
September 11, 1987
STANDARD OPERATING PROCEDURE
FOR WEIGHT DETERMINATIONS USING
AN ELECTRONIC ANALYTICAL BALANCE
1. SCOPE
1.1. This procedure is applicable for accurate weighing of solid and
liquid materials on self calibrating electronic analytical
balances.
1.2. This procedure may not be applicable for volatile liquids weighed
in open containers or for hot and cold materials.
2. SUMMARY
2.1. Milligram to gram weight determinations are accurately performed
on a properly maintained electronic analytical balance.
3. APPARATUS
3.1. Electronic analytical balance (Mettler Models SAE50, AE100, AE1SO,
AE200, AE240, or equivalent).
4. PROCEDURE
4.1. If the balance is dual range, select the range desired following
instructions in the manual.
4.2. Ensure that the analytical balance calibration check has been
updated as discussed in Section 5.2.
4.3. Select appropriate integration time (compensates for external
vibrations) and stability detection (ensures only stable values
are shown) as instructed in the manual.
4.4. Ensure that the balance pan is clean and empty; also, ensure that
all weight adjustment controls are set to zero.
4.3. With all sliding doors on the instrument closed, zero the
instrument.
4.4. Place the object to be weighed on the pan and close all sliding
doors. Allow the balance to achieve equilibrium.
APPROVED
117
-------
Page 3 of 4 Analytical and Structural Chemistry Center
SOP ASCC-20-010-02
(Revised)
September 11, 1987
STANDARD OPERATING PROCEDURE
FOR WEIGHT DETERMINATIONS USING
AN ELECTRONIC ANALYTICAL BALANCE
4.5. Record the weight determined or tare the weight of the object on
the balance as appropriate. Careful addition of material to tared
containers is permitted without first removing the container from
the balance pan.
4.6. For a tared container with added contents, allow the balance to
achieve equilibrium and record the weight determined.
4.7. After each weight determination is completed, remove the object
which has been weighed; ensure that the balance pan and housing
are clean and dry, then re-zero the instrument with all sliding
doors closed.
5. QUALITY CONTROL
5.1. Annual calibration and service is performed by a manufacturer
service representative or by the Battelle Instrument Laboratory.
The dates of service are recorded in the Balance Maintenance and
Calibration Log Book and a report is submitted to the Quality
Assurance Office.
5.2. Calibration Check and Cleaning
5.2.1. Schedule
5.2.1.1. The calibration of each balance should be
checked prior to using the balance. Should a
particular study require a more stringent
calibration schedule, such information will be
contained in the pertinent study specific SOP or
QA plan.
5.2.2. Since the balance is self-calibrating, only a small brush
and an absorbent material (kleenex, kimwipe, or
equivalent) is needed.
5.2.3. Method
5.2.3.1. Ensure that the balance pan and housing are
clean and dry. Brush any loose material off the
pan and out of the housing with a dusting brush.
Wipe up any liquids with an absorbent material.
118 APPROVED
-------
f •"•*--
L- ' - * ' ' ; -
• t '
•'• -L ' /
Page 4 of 4 Analytical and Structural Chemistry Center
SOP ASCC-20-010-02
(Revised)
September 11, 1987
STANDARD OPERATING PROCEDURE
FOR WEIGHT DETERMINATIONS USING
AN ELECTRONIC ANALYTICAL BALANCE
The balance pan may be removed and cleaned, as
necessary, with an appropriate cleaning solution
(e.g., Alconox in water).
5.2.3.2. Check the balance level indicator to determine
that the balance is level. If necessary, level
the balance using the leveling feet.
5.2.3.3. Calibrate the balance with internal calibration
weights as described in the appropriate manual.
5.2.3.4. Record the date and your initials in the Balance
Maintenance and Calibration Log Book.
6. TROUBLE SHOOTING
Refer to the appropriate balance manual for troubleshooting.
APPROVED
119
-------
Appendix G
Revision No. 3
Date: April 29, 1986
Page 1 of 4
APPENDIX G
STANDARD OPERATING PROCEDURE
FOR THE USE OF TOP LOADING BALANCES
-------
Page 1 of 3 Analytical and Structural Chemistry
SOP ASCC 20-028-01
June 22, 1987
Kev Words:
Title: STANDARD OPERATING PROCEDURE
FOR THE USE OF TOP LOADING BALANCES
-^ ^
Originated by: j -f^ &T _ Date:
Su/arTS. Hetzel (
Approved by: \^^ fJu^ Date: £/ZQ/3O
Johyft. Nixon, Manager '
Chemistry and Spectroscopy Section
Approved by: ^sj*.*^**-^ y~ >. . . - Date:
Ronald L. Joine-r', Vice President
Chemistry and Biomedical Sciences Department
Approved by: t^^f^ ^ J//L^C Date:
Raniona A. Mayer, Manager7
Quality Assurance Unit
Approved by: '^i ^ — Date:
rker, Senior Vice President
Biogical and Chemical Sciences
Circulation List:
QAU
QCWG
Record of Reviews:
Date: Reviewed by: Date Reviewed by:
APPROVED
121
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Page 2 of 3 Analytical and Structural Chemistry Center
SOP ASCC 20-028-01
June 22, 1987
STANDARD OPERATING PROCEDURE
FOR THE USE OF TOP LOADING BALANCES
1. EQUIPMENT DESCRIPTION
1.1. Equipment type - top loading balance
1.2. Manufacturer and Model Number - Mettler P1200N, PC4400, or
equivalent
2. SUMMARY
2.1. The top loading balance can be used to weigh materials up to a
total of 1099 +/- 0-03 grams. The balance calibration check
schedule is defined by study-specific requirements.
3. OPERATING PROCEDURE
3.1. Check to make sure that the balance is level, using the bubble
level located on the front. Adjust the legs to level the'
balance, if necessary.
3.2. Make sure that the balance pan is clean.
3.3. Look in the balance log to ensure that the balance calibration
check has been performed. If not, do so following the
directions in section 4.
3.4. Place a weighing vessel on the balance pan and tare the vessel
with the tare knob and/or weight control knobs-. Record the tare
weight, if the balance does not have tare capability.
3.5. Place the material to be weighed in the tared vessel. Adjust
the weight control knobs until one of the moving weight lines
aligns with the stationary weight marker. If this is an
electronic balance, wait for the readout to stabilize.
Determine the weight of the material directly from the readout
or by difference.
3.6. Clean the balance pan when finished.
4. CALIBRATION
4.1. Annual calibration and service is performed by a service
representative. The dates of service are recorded in the
Balance Maintenance and Calibration Log Book.
APPROVES
122
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Page 3 of 3 Analytical and Structural Chemistry Center
SOP ASCC 20-028-01
June 22, 1987
STANDARD OPERATING PROCEDURE
FOR THE USE OF TOP LOADING BALANCES
4.2. Calibration checks are performed as required for a particular
project. Calibration schedules should be contained in the
pertinent study-specific SOP.
4.2.1. Set the tare knob to "0" and zero the balance with the
zero adjust knob. Check the calibration with standard
weights which bracket the weight range of the materials
to be measured. The range must be within the capacity of
the balance. If any measured mass is different from the
known mass by more than 2.0 percent where
Percent Difference » (known mass - mass measured) X 100
known mass
notify the manufacturer and stop using the balance until
the problem is corrected.
4.2.2. Record the weights determined for the calibrated test
weights in the Balance Maintenance and Calibration Log Book.
123
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Appendix H
Revision No. 3
Date: April 29, 1988
Page 1 of 6
APPENDIX H
DATA ENTRY FORMATS FOR ASCII REPORTS
-------
PCRAT FOR NATICtftL PESTICIDE SURVEY (NFS) DATA
T.TW OCTI3MMS '»•
1 1-6 FldjH
9-14 S_Tenp
17-24 Date_Sam
27-34 Date_Shp
37-44 Datejtec
47-54 Time_Sam
57-64 Time_Ice
[TOR METHODS 5 AND 9 ONLY]
68-69 F«
2 1-6 enter pH OF FIELD SAMPLE
9-14 enter SIMILIZED TEMPERAIURE OF WAIER
17-24 enter EPJE SAMPLED
27-34 enter EME SHIPPED
37-44 enter EPJE REEETVED
47-54 enter TIME SAMPLED
57-64 enter TIME ICED
[FCR METHODS 5 AND 9 CULY]
67-70 enter pH OF LAB SAMPLE
3 BLANK
4 1-17 Receipt Condition
5 1-80 enter COOITTON OF SAMPLE UPCN RZEZIPT AT LABORATORY
6 BLANK
7 1-6 Sanp t
16-18 Lab
21-25 Set f
28-35 Date_Spk
38-45 Date.Ext
48-55 Date. Ana
58-63 Column
enter SAMPLE H3ENTIFICATICN NUMBER
16-18 enter LAB ABBREVIATION
21-25 enter SET NUMBER
28-35 enter DATE SPIKED
38-45 enter DATE EXTRACTED
48-55 enter DATE ANALYZED
58-63 enter AlttLYSIS COLUMM
BLANK
125
-------
POBMftT FOR rWnOWL PFSTICIHR SURVEY (NFS) IMA (cent.)
T.TMF COLIMB nF.qrRTPTI(3J
10 1-4 Type
8-13 SpUcer
16-22 Detract
25-31 Analyst
34-40 Sam_Vbl
43-49 Ext.Vol
52-60 Int. Std.
65-70 % Surr
11 1-5 enter SAMPLE TYPE
8-13 enter SFIKER'S INITIALS
16-22 enter EXTRACTOR'S INITIALS
25-31 enter ANALYST'S INITIALS
34-40 enter VOLUME OF SAMPLE
43-49 enter VOLUME OF EXTRACT
52-62 enter INTETOP^L STAICftRD (as % of calibration standard)
65-70 enter PERCENT RECOVERY OF SURROGATE
12 BLANK
13 1-8 Cements
14 1-80 enter ANY PEKmETT Cd-METTTS ON SAMPLE AND ANALYSIS
15 BLANK
16 1-7 Analyte
29-33 Cone.
39-45 Analyte
67-71 Cone.
1-25 enter ANALYTE'S NAME
28-34 anter CONCENTRATION OR PERCENT RECOVERY
39-63 enter ANALYTE'S NAME
66-72 enter CCTONERATICN CR PERCENT RECOVERY
126
-------
FCR twnaM, PJXL'K• 11IK SURVEY (NFS) QGTRUMENT CCNUCL
T.TMF QOLLM35
1 1-3 Lab
6-11 Mettol
14-21 Date_Ana
24-30 Analyst
35-37 S/N
42-44 PSF
49-51 PGF
55-58 Res.
2 BLANK
3-? 1-3 enter LAB ABBREVI&TICU
6-11 enter MEIHCD NUMBER
14-21 enter EPJE AM^LYZED
24-30 enter ATP^LYST'S INITIALS
33-37 enter SIO^L TO NOISE HATIO
40-44 enter PEAK SYMMETRY FACTOR
47-51 enter PEAK GEOMETRY FACTOR
54-58 enter RESOLOTICN
127
-------
NOTES ON NFS DA3A FCE&KTS
1. The format for any date is mm/dd/yy
A missing date should be entered 01/01/60
2. "me format for any time is hh:mn in military time
A missing time should tie entered 00:00
3. Any other data that is missing should be entered with a period ( . )
4. The number of decimal places should be as follows:
Concentration
Percent Recovery 1
Internal Standard ^ '/
Instrument Controls 2
PH 1
Temperatures 0
Volumes 0
5. The codes for Column are as follows:
Primary PRIM
Confirmatory CCNF
Tnird GCMS
6. The codes for Lab are as follows:
TSD TSD
OPP OPP
WE3L WER
Radian RAD
Battelle BCD
James M. MontgomerY JI-M
Alliance ALL
Sciences and Engineering ESE
7. "Die codes for lype are as follows:
Field Sample SAMP
Shipping Blank SBLK
Method Blank MBLK
Lab Control Standard LCS@
Lab Spike Sample LSS@#
Day 0 Time Storage DTS@
Time Storage for D-xract HTE§
Time Storage for Cample , HTS@
?evib''>M*AACe. c»;o.lwe.Ti «« St-^»K P5V1-
where (§ is the mix letter (A,B or C)
and # is the spiking level (1,2 or 3)
128
-------
NOUS CM NFS EMA FORTIES (cant.)
8. itere should be at least one blank line between samples in the NFS data
file.
9. Hie codes for Concentrations and Percent Recoveries are as follows:
Not Analyzed
Not Detected « 1/2 Reporting Limit) -999
Saturated -777
Other -333
Below Reporting Limit, but above 1/2 Reporting Limit -ill
Above Reporting Limit, but not Quantified 888
10. If a reported value is greater than (» some number in the NFS instrumer
control data, then use a minus sign (-) instead of >
129
-------
Appendix i
Revision No. 3
Date: April 29, 1988
Page 1 ol 19
APPENDIX I
STANDARD OPERATING PROCEDURE FOR QUALITY
ASSURANCE UNIT PERFORMANCE AND SYSTEM
AUDITS FOR NPS SURVEY
-------
Paae 1 of 7 Analytical and Structural Chemistry Center
SOP ASCC 50-083-01
April 29, 1988
>*7
Kev Words: "
Title: STANDARD OPERATING PROCEDURE
FOR QUALITY ASSURANCE UNIT
PERFORMANCE AND SYSTEM AUDITS
FOR NPS SURVEY
Originated by: Jv^ ^ f- C*>s.>j 2* _ Date:
Tina M. Engel
Approved by: ^ £. cs*- _ Date:
Jutfith E. Gebhart, Manager
Analytical Chemistry Section '
s*-.
Approved by: r^-~-' *^ /-<- - _ Date:
Ronald L. Joirter, Vice President
Chemistry and Biomedical Sciences Department
Approved by: /^v-._^^-r^_x •' / J^t^f^A^ Date: ^
n^amona A. Mayer, Manag.er
Quality Assurance Unit
Approved by: / n>U t/l /ArUX/^^A^C-^ Date:
\nna D." Barker, Senior Vice President
Biological and Chemical Sciences
Circulation List:
QAU . APPROVED
QCWG
Record of Reviews:
ate: Reviewed by: Date Reviewed by:
131
-------
Page 2 of 7 Analytical and Structural Chemistry Center
SOP ASCC 50-083-01
April 29, 1988
->
w-'> \.
STANDARD OPERATING PROCEDURE '~.f >
FOR QUALITY ASSURANCE UNIT
PERFORMANCE AND SYSTEM AUDITS
FOR NPS SURVEY
1. SUPPORT AREA
1.1. Quality Assurance Unit
2. SUBJECT
2.1. Performance and System Audits
3. DESIGNATED CONTACT
3.1. Manager, Quality Assurance Unit
4. BACKGROUND
4.1. Requirements
4.1.1. A number of regulatory agencies, including the
Environmental Protection Agency (EPA), require a Quality
Assurance (QA) Program to assure the reliability and
quality of monitoring and measurement data. EPA specifies
that an independent Quality Assurance Unit (QAU) conduct
audits to monitor the capability and performance of a
regulated activity. The audits are of three basic types:
(1) System Audits, that are overall evaluations of the
effectiveness of an activity's QA system in meeting
intended objectives, (2) Performance Audits, that are
determinations of the accuracy of the total measurement
system or a component part thereof, and (3) Data Audits,
that are determinations of the quality of the results
submitted to EPA.
4.2. Purpose
4.2.1. This Standard Operating Procedure (SOP) describes the
procedures that will be followed by the QAU in conducting
Performance, System, and Data Audits on the above
referenced program. This SOP describes the EPA audit
requirements for this program along with current Battelle
QA policy enacted to meet the needs of clients.
132
-------
Page 3 of 7 Analytical and Structural Chemistry Center
SOP ASCC 50-083-01
April 29, 1988
u* - •
STANDARD OPERATING PROCEDURE
FOR QUALITY ASSURANCE UNIT
PERFORMANCE AND SYSTEM AUDITS
FOR NPS SURVEY
5. PERSONNEL REQUIREMENTS
5.1. QA Performance, System, and Data Audits will be performed by
trained QA Specialists. As the need arises, technical personnel
will also participate in audits. In all instances, the QA
Specialists will organize, direct, and lead the audits.
5.2. QA Specialists
5.2.1. QA Specialists have, as a minimum, a college degree in one
of the sciences and/or a minimum of five years' experience
in the field or laboratory and/or in work associated with
QA operations. QA Specialists are assigned to the QAU ana
are supervised by the Manager of the QAU. QA Specialists
report administratively to the Manager of Support Services
and directly to the Senior Vice President for Biological
and Chemical Sciences on technical and quality issues. QA
Specialists operate independently of organizational units
and personnel engaged in conducting the activities to be
audited.
5.3. Technical Personnel
5.3.1. In the event that specialized technical expertise is
needed to adequately assess the quality of an activity,
technical personnel may be asked to participate in
Performance, System, or Data Audits. Technical personnel
may assist the QA Specialists in any or all aspects of the
audit process as needed.
6. PROCEDURE
6.1. Audit Schedule -- Specific audit dates will be established by QAU
personnel and project technical team members. System and Perfor-
mance Audits can be conducted separately or simultaneously.
6.1.1. A System Audit will be conducted shortly after laboratory
operations are functional and subsequently half way
through the contract or more frequently at the discretion
of management.
133 APPROVED
-------
Page 4 of 7 Analytical and Structural Chemistry Center
SOP ASCC 50-083-01
April 29, 1988
STANDARD OPERATING PROCEDURE
FOR QUALITY ASSURANCE UNIT "'*•
PERFORMANCE AND SYSTEM AUDITS
FOR NPS SURVEY
6.1.2. Performance Audits will be conducted quarterly or more
frequently at the discretion of management once systems
are operational and generating data.
6.1.3. Data Audits will be conducted each time a data set is
generated for submission to EPA.
6.2. System and Performance Audits -- System Audits will evaluate all
components of the sample tracking, analytical, and reporting
activities to determine the system's overall effectiveness in
addressing control measures. Implementation and effectiveness of
the requirements contained in the documents listed in Section VI.C
of this SOP will be examined. The System Audit will provide an,
objective means of ensuring that: the necessary procedures for
each element of the project activity are established; records are
being adequately generated and maintained to assure proper
documentation, retrievability, and traceability of information;
the established controls are effective in producing quality,
results; and formal QA/QC measures are being used by all
applicable components of the project. Performance Audits will be
conducted during laboratory activities. Performance Audits will
verify that actual practice is in accordance with preestablished
procedures and other guidelines.
6.2.1. The Audit Team will be composed of a combination of QA
Specialists, technical personnel, and other individuals as
appropriate. The Audit Team will range from upwards of
one individual. The QA Specialist will direct the audit
and be the Audit Team Leader.
6.2.2. The Audit Team will review the following applicable
documents in preparation for the audit: the QA project
plan, project contractual documents, SOPs (included in the
QA project plan), NPS Method 6 (included in the QA project
plan), previously generated data and reports, and Battelle
general policies.
6.2.3. The Critical Phase Inspection Check Sheet (Figure 1) will
be used for System and Performance Audits. The Audit Team
will use the Critical Phase Inspection Check Sheet to
guide the audit and document objective evidence reviewed
during the process. Additional issues can be addressed at
the discretion of the QA Specialist or Audit Team members.
134 APPROVED
-------
Page 5 of 7 Analytical and Structural Chemistry Center
SOP ASCC 50-083-01
April 29, 1988
>•» »
STANDARD OPERATING PROCEDURE V/'Mr/ i.
FOR QUALITY ASSURANCE UNIT ' ' 'it-,: ;
PERFORMANCE AND SYSTEM AUDITS
FOR NPS SURVEY
The Audit Team will have the latitude to pursue a
questionable condition or practice even if the discovered
condition was not specified on the original check sheet.
6.2.4. The results of the evaluation of each check sheet question
will be documented. Documents, files, personnel
qualifications, and other records reviewed and
observations made during the course of the audit will be
listed or attached to the check sheets.
6.2.5. Any significant problems noted that could affect the
integrity of an activity will immediately be brought to
the attention of the person performing the operation and
the Project Manager. A verbal report will be followed by
issuance of an Audit Comment Sheet (Figure 2) at the end
of the audit. At the end of each audit day, the Audit
Team will verbally brief the Project Manager on audit
progress, problems, and subsequent plans to facilitate
prevention of recurrence of any problems that may have
been noted.
6.2.6. At the end of the audit, the Audit Team will meet in
private to review the audit results; review and document
all significant problems on Audit Comment Sheet; and
review the check sheets for completeness.
6.2.7. After the Audit Team's private meeting, the Audit Team
Leader will conduct a post audit briefing with appropriate
personnel and management of the activity being audited to:
present positive aspects of the activity being audited if
applicable and any other positive comments that may be
appropriate to the situation; discuss any significant
problems identified on the Audit Comment Sheet or other
concerns found during the audit; assure the appropriate
personnel fully understand and acknowledge the reported
problems; and document the names, titles, and positions of
those in attendance at the post audit briefing.
6.2.8. Following the audit, Audit Comments Sheets will be
finalized and approved by the QAU Manager. An Audit
•Report briefly describing the following essentials of the
audit will be prepared by the Audit Team Leader: activity
audited, dates of audit, audit team members, type and
135 APPROVED
-------
Page 6 of 7 Analytical and Structural Chemistry Center
SOP ASCC 50-083-01
April 29, 1988
'^ •>
STANDARD OPERATING PROCEDURE ' •-*'••-
FOR QUALITY ASSURANCE UNIT
PERFORMANCE AND SYSTEM AUDITS
FOR NPS SURVEY
scope of audit, personnel contacted, summary of audit
results including positive points, problematic areas, and
references to Audit Comment Sheets, any additional
comments or recommendations, and a statement on the
effectiveness of the QA elements audited. The QAU Manager
will also approve the Audit Report.
6.2.9. The completed Audit Comment Sheets and Audit Report will
then be routed to the Project Manager and persons
responsible for the specific tasks via the QA Inspection
Routing Sheet (Figure 3). The Project Manager and project
personnel will fill out the Corrective Action sections of
the Audit Comment Sheets and forward them to the
management listed in Figure 3. A period of seven days
will be requested for the return of the forms to the QAU.
All Audit Comment Sheets and Audit Reports will be copied
and filed within the QAU before the originals are
circulated to appropriate personnel. These copies will be
destroyed once the original documents with Corrective
Action Descriptions appropriately addressed have been
returned.
6.2.10. The Corrective Action Descriptions will be reviewed by the
QA Specialist who led the audit and the Manager of the QAU
to assure that appropriate measures have been initiated to
resolve noted problems. If the corrective actions are
adequate, the forms will be signed by the QA Specialist
and Manager of the QAU.
6.2.11. If the corrective action responses are unacceptable (do
not meet Battelle Policy or EPA-specified project
requirements) or do not fully address the reported
problems, the QA Specialist and the Manager of the QAU
will fill in the appropriate information at the bottom of
the Audit Comment Sheet. Verbal discussions will then be
held with the Project Manager to come to agreement on a
resolution. If a resolution cannot be reached, the issue
will be taken up with appropriate management for
settlement. The corrective action finally agreed upon
will be documented and retained in the QAU file.
•V-PROYED
136
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Page 7 of 7 Analytical and Structural Chemistry Center
SOP ASCC 50-083-01
April 29, 1988
STANDARD OPERATING PROCEDURE
FOR QUALITY ASSURANCE UNIT
PERFORMANCE AND SYSTEM AUDITS
FOR NPS SURVEY
6.3. Data Audits -- Data Audits will be performed on all data sets
submitted to EPA. Prior to submission to EPA, all finished and
raw data associated with the data set will be submitted to the
QAU. The QAU will audit data to establish that project QA
requirements were met during generation of the data and to
establish the completeness, traceability, accuracy of reported
data. All reported data are reviewed for agreement with raw data.
6.3.1. Data sets submitted to QAU for audit will be accompanied
by a completed Data Package Checklist form (Figure 4).
All materials necessary to complete the Data Audit are
listed in the Data Package Checklist along with comments
designed to aid the QAU in the audit. Each data set will
also be accompanied by an Internal Quality Control
Checklist (Figure 5) listing project QA requirements and
documentation that these QA requirements were met for
submitted data sets.
6.3.2. Data Audit results are reported to the Project Manager
using a Audit Comment Form (Figure 2) which specifies if
the data is approved as submitted or if discrepancies
exist that must be addressed. Discrepancies are addressed
by the Project Manager or project personnel involved in
the specified tasks and the form is routed to management
and the QAU for approvals as described in Sections 6.2.9.
and 6.2.10. of this SOP. If the corrective action
responses are unacceptable, issues are resolved as
described in Section 6.2.11. of this SOP.
APPROVES-
*
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CRITICAL PHASE INSPECTION CHECK SHEET
TEST ARTICLE
STUDY TITLE
PROJECT NUMBER
CRITICAL PHASE(S)
QA AUDITOR
AUDIT TYPE: o SYSTEM a PERFORMANCE
DATE
Sample Receipt and Storage
ITEM
Who is responsible for sample receipt
and storage?
Is portion of QA Project Plan describing
sample receipt procedure available?
Is above sample receipt procedure followed?
Is ICF informed when samples are received?
Is information on ICF Sample Tracking form
transferred to Method 6 database?
What is disposition of ICF Sample Tracking form?
Where are samples stored?
Where are standards and sample extracts stored?
Is the temperature of the cold storage
recorded daily in a permanent record?
Are temperature excursions noted and
appropriate actions taken when required?
YES
NO
COMMENT (S)
Additional Comments:
FIGURE 1. CRITICAL PHASE INSPECTION CHECK SHEET
-------
Sample Preparation
ITEM
Who is responsible for sample preparation?
Are NPS Method 6 and modifications outlined in
the QA Project Plan describing sample prepar-
ation available?
Is above sample preparation procedure followed?
Are SOPs for operation of laboratory equipment
such as balances available?
Are Method 6 and SOPs followed?
Are analytical balances routinely checked before
use? Is documentation available?
Is the laboratory maintained in a clean and
organized manner?
Are safety practices (lab coats, lab glasses,
etc.) consistently used in the laboratory?
Are the hoods in good conditions and functional?
Are chemical waste disposal policies/procedures
well-defined and followed?
Are laboratory reagents and chemicals dated
upon receipt? Are expired reagents present?
Are solutions and reference materials properly
labeled with concentrations, date of
preparation, and identity of person preparing
the sample?
Is a laboratory notebook containing descriptions
of solution preparation and sample preparation
properly maintained (GLP guidelines)?
Are primary standards traceable to neat
materials?
YES
NO
COMMENT (S)
Additional Comments:
FIGURE 1. (Continued)
139
-------
GC-NPD Sample Analysis
ITEM
Who is responsible for GC-NPD analyses?
What instrument is used for 6C-NPO analyses?
Are NPS Method 6 and modifications outlined in
the QA Project Plan describing primary and
confirmatory GC-NPD conditions available?
Are Method 6 and modifications followed?
Is the instrument manual available in the work
area?
Is a permanent instrument service record
maintained in a log book?
Is the Instrument Quality Assurance Standard
analyzed prior to samples?
What data system is used for GC-NPD data
collection?
Are adequate backup supplies available (beads,
injection port liners, columns, etc) for
preventative maintenance?
YES
NO
COMMENT (S)
Additional Comments:
FIGURE 1. (Continued)
-------
GC-MS Sample Analysis
ITEM
Who is responsible for GC-MS analyses?
What instrument is used for GC-MS analyses?
Are NPS Method 6 and modifications outlined in
the QA Project Plan describing GC-MS confirm-
ation conditions available?
Are Method 6 and modifications followed?
Is the MS tuned with DFTPP prior to analyses of
samples?
Is a permanent instrument service record
maintained in a log book?
What data system is used for GC-MS data
collection?
Are adequate backup supplies available for
preventative maintenance?
YES
NO
COMMENT (S)
Additional Comments:
FIGURE 1. (Continued)
141
-------
Data Handling and Review
ITEM
Who is responsible for data handling?
Who is responsible for data review?
What data system is used for calculations, data
compilation, and generation of reports?
Is the operation of the data system validated
with a test set of data?
Are results spot-checked by a second person or
the QAU?
Do records ind-'cate that corrective action is
taken when analytical results fail to meet QC
requirements?
Are all data maintained in a paper file for
on-site inspection?
Chromatograms of raw data?
Calibration curves?
Control charts?
Analysis reports?
Copies of text file reports?
Are raw and finished data stored on magnetic
tape?
YES
NO
COMMENT(S)
Additional Comments:
FIGURE 1. (Continued)
-------
Quality Control
OffJCMLCOl
ITEM
Does this program have a current QA Project
Plan? What revision?
Do project personnel have a copy of the QA
Project Plan?
Are project personnel aware of the contents of
the QA Project Plan?
Does the QA Project Plan adequately address the
Personnel?
Facilities and equipment?
Operation of instruments?
Documentation of procedures?
Preventative maintenance?
EPA's data QC requirements?
Data validation?
Data reporting requirements?
Feedback and corrective action?
YES
NO
COMMENT (S)
Additional Comments:
FIGURE 1. (Continued)
-------
Summary Checksheet
ITEM
Do responses to the evaluation indicate that
project and supervisory personnel are aware
of QA/QC and its application to the project?
Have responses with respect to QA/QC aspects of
the project been open and direct?
Has a cooperative attitude been displayed by all
project and supervisory personnel?
Have any QA/QC deficiencies been discussed?
Is the overall quality assurance adequate to
accomplish the objectives of the project?
Have corrective actions recommended during
previous audits been implemented?
YES
NO
COMMENT (S)
Additional Comments:
FIGURE 1. (Continued)
-------
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145
-------
rce SESST
T2ST A2TICLZ ?EASS_
STUDY TTTLS
SPONSOR PROJECT SO.
Q.A. AUDITOR DAIS
?^
^
sigz &&d dace this Rjsuzlrg Sheec iz rhe scace prsvidcd. beside your &aset a-d
rercrz Che entire set vhes css?ieted tc the Qualir/ Assurance Ccit 20 latir tha:
ROUTS TO SXCXATTRS DATS
Dave Zimmerman
Tom Dam'son
Elizabeth Kircher
Tina Enael
Judy Gebhart
Ron Joiner
Georoe Rogers
Anna Barker
Ramona
FIGURE 3. DUALITY ASSURANCE INSPECTION ROUTING SHEET
146
-------
Name:
DATA PACKAGE CHECKLIST
Date:
QA Reference:
Data Sets:
Project No:
MATERIAL
n ASCII Text Data
n Field Sample Tracking Sheet
D Lab Notebooks
D Calibration Data (Analysis
Method, Calibration Curves,
Raw Calibration Data)
COffOT
n Sample Data (Chromatograms,
Printouts, Summary Report)
D Control Charts
D Internal QC Checklist
FIGURE 4. DATA PACKAGE CHECKLIST
147
4/29/88
-------
Ext net ion Set
Extracted
IKTBWAL QUALITY OJKTROL CHECKLIST
/ / Analyzed / /
Files
Criteria for Aecootaoie Results Acceetaole LIB its
CONTROL CHARTS Control Chart
ETU recovery fro* the LCS and PTU
recovery froe the LCS or Wth Blk PTU liiiU to
aust be within the 3 Std lie it*
of the current control chart. ETU liait* to
Alert conditions occur when:
-Three or sore ETU or PTU recoveries fall outside the 2 Std warning
lieits, but within the 3 Std control liaits.
-Seven consecutive point* for ETU or PTU fall above or below the seen.
-Seven consecutive points for ETU or PTU are in increasing or
decreasing order.
SURROGATE RECOVERY
PTU recovery aust be within 31 Control Chart
percent of the aean recovery
of PTU froe the current control PTU aean
chart. (Uth Blk excluded if a field
saepl* oeets Uth Blk criteria.) PTU lieits U
INTERNAL STANDARD AREA
IS peak area for any saeple aust MS U 1211
not deviate by eore than 21 percent (Expressed as recovery relative
free the eean peak area for the to the aean area of the
calibration standards. calibration standards.)
LABORATORY CONTAMINATION
The eethod blank should not contain < 4.5 ug/L
a peak grater than or equal to
one-half the URL for ETU.
INSTRUMENT PERFORMANCE
Froe Table 6 of Method 8.
S/N: > 3
PSF: I.9C to 1.IC
POP: 1.93 to 1.17
CALIBRATION STANDARD INTEGRITY
If the ayatee is not recalibrated, Level of Ck Std
or ia recalibrated using new Acceptable range
standards, at least one previously
prepared atandard lust be run and to
Actua i Resu i ts Cseeenxs
LCS file Ho.
PTU ( LCS / BUC ) J pass fail
ETU I1M/9M » pass fail
See Control Chart. pas* alert
See Control Chart. pass alert
See Control Chart. pass alert
Fi les: pass
Range: fail
Files: pass
Range: fail
Uth Blk file No.
Aet of ETU found pass fail
Inst QC file No.
S/N pass fail
PSF pass fail
PGF P»»« f*'l
Ck std file No.
Result P*» '»''
analyzed as i saeple, giving a result
within 211 of the expected value.
Prepared by Date / / */2Bj
FIGURE 5. INTERNAL DUALITY CONTROL CHECKLIST
-------
Appendix J
Revision No. 3
Date: April 29, 1988
Page 1 of 5
APPENDIX J
STANDARD OPERATING PROCEDURE FOR PROPER
USE OF SIGNIFICANT FIGURES AND ROUNDING
-------
Page 1 of 4 Analytical and Structural Chemistry Center
SOP ASCC-30-001-01
September 19, 1986
Kev Words; Calculations
Data
Reporting of Results
Title: STANDARD OPERATING PROCEDURE
FOR PROPER USE OF SIGNIFICANT FIGURES AND ROUNDING
Originated by: 'l/VUL{JM\. 1UWJ?L*^-r- Date:
Merl
in K. L. Bicking J'
/ L
Approved by: V*w , , — • _ Date:
John R. Nixon, Manager
Analytical and Structural Chemistry Center
Approved by: \_u~*~~ f ^jr^L. __ Date:
Duane E. Hilmas, Manager '
Chemistry and Biomedical Sciences Department
Approved bv : _ ZZi-^,^ -^L^ /^^£\^/ _ Date:
Ramona A. Mayer, Manager
Qua! itv. Assurap«-TUnit
Approved by: /ȣj >v" Date:
Anna LT. Barker, Director
Biological and Chemical Sciences
Circulation List:
QAU
QCWG
Record of Reviews:
Date: Reviewed by: Date Reviewed by:
150
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OFFICIAL COPY
Page 2 of 4 Analytical and Structural Chemistry Center
SOP ASCC-30-001-01
September 19, 1986
STANDARD OPERATING PROCEDURE
FOR PROPER USE OF SIGNIFICANT FIGURES AND ROUNDING
1. SCOPE
1.1. This Standard Operating Procedure (SOP) is applicable to all
projects which require manipulation of numerical data.
2. SUMMARY
2.1. The number of significant figures reported is dependent on the
number of significant figures in each individual quantity used to
compute the reported number. The number of significant figures
reported cannot be more than the smallest number used in any
related calculations.
Rules are provided for proper rounding of the final answer.
3. PROCEDURE
3.1. Number of Significant Figures
3.1.1. An experimental result should be reported so that it
contains only the digits known with certainty, plus the
first uncertain digit. For example, the number "61.6"
implies that there is uncertainty in the first decimal
place (±0.05).
3.1.2. The number of significant figures will depend on the
particular activity/piece of equipment being used. Most
activities will generate between two and four significant
figures. The analyst must be aware of the number of
significant figures provided by a particular activity.
3.1.3. Zeros to the right of significant digits are used to
indicate the order of magnitude and are not significant.
When necessary, employ scientific notation to avoid
ambiguities. For example, 2000 ml implies from one to as
many as four significant figures. However, 2.0 X 103 ml
or 2.0 L imply only two significant figures.
3.2. Number of Significant Figures in Calculations
3.2.1. Addition and Subtraction
The number of significant figures in the final answer will
be determined by the number with the fewest number of
decimal places. For example,
151
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OFFICIAL 001
Page 3 of 4 Analytical and. Structural Chemistry Center
SOP ASCC-30-001-01
September 19, 1986
I
STANDARD OPERATING PROCEDURE
, FOR PROPER USE OF SIGNIFICANT FIGURES AND ROUNDING
3.4 + 0.02 + 1.31 - 4.7.
i
i The final answer is limited to one decimal place because
of the uncertainty introduced in the first decimal place
j by the "3.4".
3.2.2. Multiplication and Division
1 The number of figures in the result is equal to that of
the quantity with the least number of significant figures.
For example,
The answer is limited to two significant figures because
of the ":4".
3.3. Number of Significant Figures in a Final Reported Result
3.3.1. The number of significant figures in the final reported
result will be determined by the needs of each individual
project. However, the number of significant figures
reported can never be greater than the smallest number of
significant figures in the data.
3.3.2. In performing calculations, carry one extra significant
figure through all calculations. Round to the correct
number of significant figures in the last step.
3.4. Rounding of Numbers
3.4.1. When the first digit discarded is less than "5", the last
digit retained is not changed ("round-down"). For
example,
3.46325 rounded to 4 digits - 3.463, and
3.46325 rounded to 3 digits - 3.46.
3.4.2. When the first digit discarded is greater than "5", or if
it is a "5" followed by at least one non-zero digit, the
last digit retained should be increased by one unit
("round-up"). For example,
8.37652 rounded to 4 digits - 8.377, and
8.37652 rounded to 3 digits - 8.38.
152
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CO
Page 4 of 4 Analytical and Structural Chemistry Center
SOP ASCC-30-001-01
September 19, 1986
STANDARD OPERATING PROCEDURE
FOR PROPER USE OF SIGNIFICANT FIGURES AND ROUNDING
3.4.3. When the first digit discarded is exactly "5", the last
digit retained should be rounded upward if it is an odd
number, but not adjusted if it is an even number (i.e. the
last digit retained will always be an even number). For
example,
4.355 rounded to 3 digits - 4.36, but
4.365 rounded to 3 digits - 4.36.
4. REFERENCES •
"Fundamentals of Analytical Chemistry", D. A. Skoog and D. M. West;
Saunders, Philadelphia, 1982; Chapter 3.
APPROVED
153
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