EPA-810/B-92-004
T* mjl UntodStataa Orflca of Watar (WH-650) EPA 810^02-004
WfraHMCal Envtroomental Protection Offlc* oT Pwtiddaa and February 1902
~'k" *» Agancy Tode Subatancaa (H-7S01C)
QUALITY ASSURANCE PROJECT PLAN
FOR THE
NATIONAL PESTICIDE SURVEY OF DRINKING WATER WELLS
ANALYTICAL METHOD 4 - CARBAMATES
Prepared by:
Larry D. Ogle
Radian Corporation
8501 MoPac Boulevard
P.O. Box 201088
Austin, Texas 78720-1088
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) R
77 West Jackson Boulevard, 12th rioot
Chicago, IL 60604-3590
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Section No 1
Revision No. 3
Date: August 1, 1990
Pag« 2 of 2
APPROVAL PAGE
R.L Richardson, Program Manager, Radian Corporation
LD. Ogle, Project Director, Radian Corporation
D.L Lewis, QA Coordinator, Radian Corporation
K.W. Rozacky, QA Officer, Radian Corporation
Kent Sorrell, Technical Monitor, U.S. Environmental Protection Agency
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fr
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REPORTING SYSTEM
METHOD FOR REPORTING BELOW MRL AND
THE ID OF UNKNOWN PEAKS
Section No. 2
Revision No. 3 *
Date: August 1, 1990
Page 2 of 4
2. TABLE OF CONTENTS (continued)
Appendices Pages
A
B.
C.
D.
E.
F.
G.
H.
1.
J.
K.
METHOD 4
INITIAL DEMONSTRATION OF CAPABILITIES DATA
DIXON'S TEST
SURROGATE COMPOUND MONITORING CRITERIA
SPIKING LEVEL CHANGES/DATA REPORTING
FORMATS
ICF SAMPLE RECEIPT SOFTWARE
GUIDELINES FOR RECEIPT OF SAMPLE KITS
NPS METHOD 4 REVISED CONFIRMATIONS
ANALYSIS METHODOLOGY
DATA REPORTING CODES
NPS DATA FORMAT/DATA FORMAT CHANGES
RAPID REPORTING SYSTEM/CHANGES TO RAPID
36
2
5
3
3
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5
10
Revisions
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3
Date
8-1-90
8-1-90
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Section No. 2
Revision No. 3
Date: August 1, 1990
Page 3 of 4
2. LIST OF TABLES
Title
Composition of Spike Mixtures
NFS Analysis Types for Method 4
Summary of Internal Quality Control Procedures
Time Storage Study Schedule
Table No.
5-1
9-1
11-1
11-2
Section
5
9
11
11
Page
2 of 4
3 of 3
2 of 7
7 of 7
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Section No 2
Revision No. 3
Date: August 1, 1990
Page 4 of 4
2. LIST OF FIGURES
Figure
QA Relationships to Corporate and Project Organization
Laboratory Organizational Chart
Field Sampling Tracking Sheet
ICF Sample Label
Sample Receipt Screens
Sample Work Order Sheet
Sample Data Sheets
Sample Workplan
Sample Worksheet
Chromatography Daily Room Check Form
Refrigerator Sample Check-Out Log
Daily QC Form
Project Organization
Format for Method 4 Reporting
Telephone Call Record Form
Laboratory Systems Audit Checklist
Malfunction Report Form
Recommendation for Corrective Action Form
Corrective Action Flow Scheme
Format for Monthly Report
Fiqure No.
4-1
4-2
6-1
6-2
6-3
7-1
7-2
7-3
7-4
7-5
7-6
8-1
10-1
10-2
10-3
12-1
15-1
15-2
15-3
16-1
Section
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2 of 9
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4 Of 9
6 Of 9
8 of 9
9 of 9
4 Of 4
2 Of 6
4 Of 6
5 Of 6
3 of 16
2 of 5
4 Of 5
5 Of 5
2 Of 2
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Section No 3
Revision No. 3
Date: August 1, 1990
Page 1 of 1
3. PROJECT DESCRIPTION
Radian Corporation will provide analytical support for EPA's National Survey of Pesticides in
drinking water wells. The analytical results shall be used to establish an occurrence database in well
waters used as drinking water and to assist in establishing the basis for future regulatory activity. The
survey will also provide a better understanding of how pesticide use and hydrogeology relate to well
contamination.
Radian will receive the water samples into its analytical laboratories for analysis. The samples
will be stored securely at 4 degrees Centigrade until analysis. The samples will be analyzed within
appropriate hold times for the carbamate and urea pesticides by EPA Method 4 (Determination of
Pesticides in Ground Water by High Performance Liquid Chromatography with an Ultraviolet Detector
as described in EPA RFP CI86-W747 and subsequent amendments. See Appendix A.)
3.1 Background
During the planning stages of the NPS, EPA found that no combination of currently approved
methods could satisfy the need of the Survey for analyses of over 100 pesticides, degradation
products, and metabolites. A considerable method development effort was therefore initiated in
cooperation with the EPA Environmental Monitoring Systems Laboratory (EMSL) in Cincinnati. The lab
contracted with Battelle-Columbus for the development of one new method and revisions to five
existing EPA methods. Battelle used both real and simulated groundwaters as test matrices during
the development effort in order to approximate the type of sample that would be encountered during
actual Survey analyses. Prior to the NPS pilot, results of Battelie's efforts were subjected to peer
review by the Agency, States, universities, and commercial labs. During the pilot, the performance of
the methods was evaluated again and further improvements to the methods were made at this time.
Concurrent with the implementation of the Survey, a multilab validation study will be conducted.
3.2 Project Implementation
The analyses of pesticides using Method 4 will be performed according to the strict quality
assurance protocols and precision and accuracy objectives outlined in this quality assurance project
plan (QAPjP).
All generated data, including sample results and QA/QC results, will be input weekly into a
Paradox database in the format specified by EPA The major reporting effort, the analytical results, will
be submitted monthly in an ASCII format. All data for the sample analyses will be delivered within 60
calendar days of collection of the samples in tne
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Section No. 4
Revision No. 3
Date. August 1, 1990
Page 1 of 6
4. ORGANIZATION AND RESPONSIBILITY
This section describes the functional relationships between corporate organization, project
organization, and the quality assurance function. The distinction is made between the corporate
organizational hierarchy which is used in the allocation of resources (equipment and personnel) and
the organization of project teams of technical professionals. The lines of authority and responsibilities
of key project team members are described along with the interactive role of the quality assurance
function. The organizational structure and responsibilities allow for control of quality by those
performing the work and for independent assurance of the adequacy of the quality control program
and verification of its implementation.
4.1 Corporate Organization
Management at Radian is geared to providing quality services for a diverse array of customers
in industry and government. Many programs are interdisciplinary in nature, requiring contributions
from persons with different but complementary technical skills. The Radian management system
allows for the creation of project teams of technical professionals from several disciplines to meet the
specific needs of a program.
Radian has found the matrix organization to be an efficient and economical means of performing
technical service programs. Under Radian's matrix organization, a technical staff member may be
committed to a single project full-time or may simultaneously participate in several projects that require
his/her skills. To avoid the administrative problems that could occur under these circumstances, each
Radian staff member works within one of three functional staffs: Administrative, Technical, or
Operations. These corporate functional staffs, as well as the relationship between management,
quality assurance, and project organizations are illustrated in Figure 4-1.
The primary responsibilities of the Operations Staff are externally (i.e., client) focused. The
primary responsibilities of the Technical Staff are internally focused. These responsibilities include the
development and implementation of effective project management and quality assurance/quality
control procedures. The primary focus of the Administrative Staff is to serve the needs of Operations
and Technical managers in areas such as purchasing, personnel administration, contract execution,
accounting, and facilities management. When Radian begins a project, appropriate members of all
three staffs are selected to serve on the proiect team.
4.1.1 Operations Staff Responsibilities
The Radian Operations Staff is responsible for identifying potential clients, defining their
needs, marketing Radian's capabilities, working with clients to define an appropriate scope, approach,
cost, and schedule for new projects, and serving as the client's in-house representative during the
performance of the work. All Radian projects are managed by a Program Manager who has ultimate
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Section No. 4
Revision No. 3
Date: August 1, 1990
Page 2 of 6
FIGURE 4-1
QA RELATIONSHIPS TO CORPORATE AND PROJECT ORGANIZATION
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Section No 4
Revision No. 3
Date: August 1, 1990
Page 3 of 6
accountability to the client for the quality and responsiveness of the work and ultimate authority within
Radian for making all project decisions. In most cases, the Radian Program Manager is the person
who initially "sold" the project to the client.
4.1.2 Technical Staff Responsibilities
The job of executing projects, including implementation of appropriate quality control and
quality assurance procedures, is the responsibility of the Radian Technical Staff. When a project is
bid, the Program Manager who will direct the work approaches the Technical Staff Managers who are
responsible for the technical personnel who have the skills needed to successfully complete the
project. At this point, a project team is assembled with the proper mix of senior, experienced
professionals and appropriate support personnel. The size and composition of each project team is
thus specifically tailored to meet a particular project's needs.
Radian's Technical Staff is organized into divisions, departments, sections, and groups
according to the disciplines of the personnel who are resident in a given location. Work on the
National Pesticide Survey will be conducted in the Radian, Austin, Texas laboratories in the Analytical
Chemistry Department. Figure 4-2 presents the organizational chart for this laboratory organization.
Final responsibility for the quality of the work produced in each laboratory resides with the laboratory
supervisor responsible for that area and the Technical Director responsible for the laboratory units.
4.1.3 Quality Assurance Organization
Radian has organized the quality assurance function within the company to allow complete
independence in program review and immediate access to top management in quality-related matters.
The Quality Assurance Director for the Research and Engineering Technical Staff, David-L Lewis,
reports in a staff position to Dr. Neal Kocurek, Senior Vice President, Research and Engineering
Technical Staff. Mr. Lewis is a Senior Scientist in the Quality Assurance and Technical
Communications Department, and Section Head of the Quality Assurance Section. Coordination of
quality assurance activities in multiple offices is facilitated through Regional QA Coordinators located
in each of the major Radian offices. The Austin Quality Assurance Section reporting to Mr. Lewis
administers the internal QA program which provides for regular, periodic QC audits of all Radian
analytical chemistry laboratories. Mr. Kenneth W Rozacky, Group Leader of one of the groups in the
QA Section, serves as Quality Assurance Coordinator for the Analytical Chemistry Division. The Austin
QA Section, along with QA staff in the other offices, also provide QA support for Radian projects,
contributing personnel with a wide variety of technical experience and background to serve as Project
Quality Assurance Coordinators. Regional QA Coordinators serve as local focal points for project
quality assurance support.
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Section No. 4
Revision No. 3
Date: August 1, 1990
Page 4 of 6
FIGURE 4-2
LABORATORY ORGANIZATIONAL CHART
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Section No. 4
Revision No. 3
Date: August 1, 1990
Page 5 of 6
The independent nature of the quality assurance function is maintained at the project level
through Project Quality Assurance Coordinators. A Project QA Coordinator, usually drawn from the
local QA staff, is assigned responsibility for coordinating development and execution of QA activities in
all phases of a project. It is the responsibility of the Project QA Coordinator to coordinate preparation
of QA Project Plans, provide independent review of QC activities, and coordinate independent
performance assessment through QA Audits. Thus, the Project QA Coordinator provides assurance
that the overall project quality control system is, in fact, performing effectively.
The organizational relationship of the QA function within the corporate and project structures is
shown in Figure 4-1. This organization allows for a continuing evaluation of the adequacy and
effectiveness of the QC system with a view to having corrective measures initiated where necessary. It
is through this structure that problems are identified and resolved with independent confirmation that
appropriate corrective actions have been implemented and that production of non-conforming items
(e.g., services, data, designs, etc.) is arrested. This organization of the corporate quality assurance
function promotes continuity and consistency of effort in diverse technical areas, provides
independent review at all levels of the Technical Staff, and allows immediate access to Radian's top
management on quality related concerns.
Radian's Project Director assumes technical responsibility for meeting project quality objectives.
Therefore, the Project Director is ultimately responsible for development, implementation, and
documentation of all aspects of the project-specific quality control program. For effective management
of a complex program, this responsibility may be shared with the project QA Coordinator and with
project team members assigned day-to-day QA and QC activities in a multi-disciplinary program, but
in no case is the Project Director absolved of ultimate responsibility for project quality. Continuity of
effort is maintained through the QA Coordinator.
4.2 Project Organization
The responsibilities of the key NPS project members are summarized below.
Robert Richardson will serve as the Program Manager and in this role will have ultimate
authority and accountability for the program He will provide overall supervision of the project to
ensure that the contractual and budget commitments are met and will ensure that the program
objectives of the EPA are being realized. Mr Richardson will coordinate changes in scope with the
EPA if they should occur, and work with the Project Director to communicate those changes to the
Radian Task Leaders.
Mr. Larry Ogle will serve as the Project Director He will provide direction of the technical
program and will ensure that the schedule ana technical goals of the program are met. Mr. Ogle will
interface frequently with the program manager. tn« EPA Technical Monitor, and his task leaders.
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Section No 4
Revision No. 3
Date- August 1, 1990
Page 6 of 6
Supporting the Project Director are the three Task Leaders: Ms. Theresa Shaw, Ms. Caron Smith
and Ms. Jane Lindsey. These individuals will have the responsibility for technical quality, particular
increments of the project, and for completing their assigned tasks on time and within budget.
Responsibilities include identification of staffing needs for their tasks, coordination of task activities,
adherence to task schedules, monitoring of task budgets, compliance with QA/QC procedures, and
problem resolution within their area of responsibility. Each Task Leader will also be responsible for
reviewing data generated within his or her task in a timely manner.
Also supporting the Project Director is the Technical Reviewer, Mr. Fred L. Shore. Mr. Shore will
supply peer review in initial planning and will review all reports prior to submission to the EPA
Technical Monitor.
Mr. David Lewis will serve as the Quality Assurance/Quality Control Director for the program. He
will be responsible for the independent evaluation of the internal QC program, coordination of
performance and systems audits, and documentation of all QA/QC activities. The Quality Assurance
Project Coordinator (QAPC) directly responsible for the execution of the QA program will be Mr.
Kenneth Rozacky.
The EPA Technical Monitor will serve as the primary project contact for technical matters. Mr.
Kent Sorrell will serve in this capacity and can be contacted at the EPA in Cincinnati, Ohio; phone
number (513) 569-7943. Contractual matters will be handled by Ms. Mona S. Synder, Contract
Specialist for the NPS, EPA-CMD, Cincinnati, Ohio, 45268.
Samples will be received by overnight shipment at Radian in Austin by:
Ms. Jane Lindsey
Radian Corporation
8501 MoPac Boulevard
Austin, Texas 78759
(512) 454-4797
The backup person will be:
Ms. Cynthia Zieschang.
Correspondence relating to this project should be addressed to:
Mr. Larry Ogle
Radian Corporation
P.O. Box201088
Austin, Texas 78720-1088
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Section No 5
Revision No. 3
Date: August 1, 1990 l
Page 1 of 4
5. QUALITY ASSURANCE OBJECTIVES
The objectives of the quality assurance efforts for this program are twofold. First, they will
provide the mechanism for ongoing control and evaluation of measurement data quality throughout
the course of the project. Second, quality control data will ultimately be used to define data quality for
the various measurement parameters, in terms of precision and accuracy.
An initial demonstration of capabilities will be performed which will concentrate on the
determination of reporting limits. The reporting limits will be established using the following
procedures:
Using calibration standards, determine the concentration of standard necessary to
produce an instrument detector response with a 5/1 signal to noise ratio;
Spike eight reagent water samples at the concentration determined above and
analyze in a single day;
Compute Minimum Detectable Level (MDL) by multiplying the standard deviation by
the student's t value, appropriate for a 99% confidence level, and a standard
deviation estimate with n-1 degrees of freedom;
The Estimated Detection Limit (EDL) equals either the.concentration of analyte
yielding a detector response with a 5/1 signal to noise ratio, or the calculated MDL,
whichever is greater.
Determined EDLs must be no greater than twice those determined during methods development
and reported in the method;
The acceptability of EDLs exceeding the above limits will be determined by the
Technical Monitor, based on the need to be below health effect values;
EDL extracts were not analyzed on the confirmational column because of problems
with poor resolution and peak shape. It was assumed that the detection limits on
the confirmational column would be equivalent to those observed on the primary
column; and
The minimum reportable levels for Method 4 will be five times the EDL The MRLs
determined during the initial demonstration of capabilities are presented in
Appendix B.
Control charts will be used to demonstrate that the measurement system is in control. The
recovery of each analyte in Method 4 except Metnbuzin DADK and Metribuzin DK spiked into reagent
water will be charted. The surrogate recoveries also will be charted. The charts established during
the initial demonstration of capabilities will establish the initial criteria for accuracy and precision.
For Method 4, the analytes will be divided into two mixtures; designated Mix A and Mix B. The
composition of each mix is provided in Table 5-1
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Section No. 5
Revision No. 3
Date: August 1, 1990
Page 2 of 4
TABLE 5-1
COMPOSITION OF SPIKE MIXTURES
Mixture A Mixture B
Atrazine dealkylated Barban
Diuron Carbofuran phenol
Fenamiphos sulfone Cyanazine
Fenamiphos sulfoxide Fluometuron
Metribuzin DADK 3-Ketocarbofuran phenol
Pronamide metabolite Linuron
Propanil Metribuzin DA
Swep Metribuzin DK
Neburon
Propham
Control charts for each analyte will be established after the determination of the Minimum
Reporting Level (MRL) as previously described. Initially, five reagent water samples will be spiked at
10 times the MRL for both analyte mixtures in Method 4 (a total of 10 samples). These samples will
be carried through the complete extraction and analysis protocol. An additional 15 samples of spike
mix A and 15 samples of spike mix B will be spiked and analyzed by spiking 5 of mix A and 5 of mix B
on each of three consecutive days. In this manner, 20 spiked samples of mix A and 20 of mix B will
be analyzed and used to construct the control charts.
The criteria goals for accuracy and precision will be established as follows:
The relative standard deviations (RSDs) for any analyte will be <20%, except where
data generated by Battelle at the corresponding level indicated poorer precision.'
The RSDs exceeding 20% will be evaluated on a case by case basis by technical
monitors for each method; and
The mean recovery (x) of each analyte is expected to be within the control limits as
determined by Battelle during methods development, (i.e., Battelle's mean recovery
for each analyte at the corresponding level ± 3 times the RSD for that analyte) but
no greater than Battelle's mean recovery +. 30%.
For example:
For an analyte "A":
Battelle demonstrated recovery (x) of 80% for analyte 'A' with RSD of 5%.
Acceptable average recoveries will be 80% ± 3 (5%) = 80% ±15% = 65% -
95%,
or, Battelle demonstrated x of 80% with RSD of 15% for analyte 'A1. The
acceptable recovery would be limited to 80% +. 30% = 50% -110%;
The surrogate is to be spiked into the 20 samples at the level it will be spiked into real samples.
The recovery of the surrogates will be used to construct a control chart and to establish recovery
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Section No. 5
Revision No. 3
Date August 1, 1990
Page 3 of 4
criteria. Dixon's test will be used to determine any outliers. A copy of Dixon's test has been included
in 'Appendix C. There will be no more than three outliers per analyte from the 20 spiked controls per
mix.
Data from this initial demonstration will be used to determine values two times and three times
the relative standard deviation for each compound. The 2x RSD value will be used as an "alert"
marker on the control charts. The 3x RSD value will serve as the outer bound of control.
Once control charts have been established as described above, they will be used to determine if
the analysis is "in control" or "out of control." If the system is determined to be "out of control", all
analytical work must be stopped until an "in control" situation is established. The following instances
are indicative of an "out of control* system:
More than 15% of the analytes for this method are outside +. 3x RSD;
The same analyte is outside +. 3x RSD twice in a row, even through >85% of the
total analytes are in control;
If the "method blank" exhibits a peak within the retention window of any analyte and
is greater than or equal to one-half the MRL for that analyte; and
Unacceptable recoveries or quantitation of the performance evaluation samples
provided by EPA.
An "alert" situation arises when one of the following occurs:
Three or more consecutive points for an analyte are outside ± 2x RSD but inside
the ± 3x RSD;
A run of seven consecutive points above or below the mean; and
A run of seven points for an analyte in increasing or decreasing order.
An "alert" situation implies a trend toward an "out of control" situation. The analytical system will
be evaluated to try to determine the cause and correct it before analyzing additional samples.
Frequent "alert" or "out of control" samples may require re-establishing the control charts before
analytical work can proceed. The decision to re-establish control charts will be at the discretion of the
Technical Monitor.
Following establishment of the control charts, spiked reagent water controls will be a part of
each analytical or "sample set." When five such controls have been analyzed, the recoveries of each
analyte will be incorporated into the control charts by adding these five most recent recoveries to the
20 original points and then deleting the first five of the original points. If the original chart contained
less than 20 points due to outliers, then the number of points deleted will be adjusted such that the
current chart contains a total of 20 points. Accuracy and precision are recalculated and the chart
redrawn. The newly drawn chart will then apply to all data in sample sets subsequent to the last one
used to update the chart.
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Section No 5
Revision No. 3
Date: August 1, 1990
Page 4 of 4
Goals for other quality systems include:
The goal for surrogate recoveries from the method blanks and the samples is to be
within +. 30% of the mean recovery determined for that surrogate during the initial
demonstration of capabilities. Any samples with surrogate recoveries outside these
limits will be reanalyzed;
If the surrogate in the lab control standard fails to meet the above criteria, data are
still valid if two conditions are met: a) lab control standards meet all other QC
requirements, and b) the lab blank meets the surrogate recovery requirements
(Appendix D);
If the surrogate associated with method blank fails to meet the above criteria, data
for the samples are still valid if a field sample meets the QC parameters for a
method blank (assuming all other laboratory quality control requirements are met).
The control charts will be drawn up so as to depict both warning limits (+. 2x RSD)
and control limits (+ 3x RSD) about the mean;
Data completeness is expected to be .>90% for all work areas, in terms of the valid data
percentage of the total analyses performed. Comparability will be ensured by reporting data in the
units and format specified. Representativeness will be ensured by strict adherence to the method
protocols.
Replicate samples will be collected at a number of sites, 10% of the total, for use as matrix spike
samples. Analytes of interest will be spiked into these samples at selected levels to determine
recovery efficiency from a variety of matrices. Analytes from one of the two mixes were spiked into
these samples at concentrations equal to 2, 10, or 20 times the MRL for each analyte during spiking
performed early in the survey. Later spikes were at levels of 2, 5, and 10 times the MRL as requested
in the directive from EPA presented in Appendix E. An equal number of spikes are anticipated for
each mixture and each spiking level throughout the program. Directions for spiking will be provided
with the sample.
During the first year of the NFS program, additional samples will be collected, spiked, and
analyzed as a portion of a time storage study designed to determine the stability of the samples in
water and in the extraction solvent. These samples will be spiked at 10 times the MRL. Samples will
be collected for spiking, immediate extraction and analysis (within 4 days of spiking) and reanalysis
after holding the extract for 14 days. Samples will also be collected for spiking and holding for 14
days before extraction. Samples for the time storage studies will be collected at a frequency of 10%
of the sites.
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Section No 6
Revision No. 3
Date: August 1, 1990
Page 1 of 4
6. SAMPLING PROCEDURES
Field samples will be collected by ICF and various state personnel for the NFS program. ICF
will coordinate the collection and shipment of all samples to Radian. Each shipment of samples will
include a copy of the field sampling tracking sheet describing sampling identification and field
determinations of chlorine made by the sampling personnel. An example of this form is provided in
Figure 6-1.
Samples for Method 4 will be collected in clean one-liter bottles. To each liter of sample, 10 mL
of a 1 g/L solution of mercuric chloride will be added as a preservative. All samples will be chilled in
the field and shipped under ice by overnight express carrier service. The laboratory will check each
shipment upon receipt to verify that the samples were cold and intact.
Three different sample packages will be received by Radian. The regular sample package will
contain two one-liter bottles; one field sample and one backup. The second type of sample package
will be received on a frequency of 10% and contain three one-liter bottles; one field sample, one
backup sample, and one spike sample. The third type of package will also be received at a frequency
of 10% and contain six one-liter bottles; one field sample, one backup sample, one spike sample, and
three time storage samples.
All samples received in the laboratory will be clearly labeled with a standard label supplied by
ICF (Figure 6-2). This label will contain information on the sample type (private well versus community
well), a site designator, an indication of the laboratory to which the sample was sent, the method for
which the sample was collected, the name of the sampler, and information on the use of the sample
(field sample, backup sample, spike sample, or time storage sample).
Radian will check the information on the sample bottle labels described above and the field
sampling sheets for agreement when the samples are received. If all information is correct and the
samples were received intact and cold, Radian will contact ICF via computer modem a"nd input all
sample receipt information into ICF's computer system. A copy of the ICF memo on the NPSIS
sample receipt software for laboratories is provided in Appendix F. The sample receipt screen at ICF
is shown in Figure 6-3. Ms. Andrea Jarma will be the contact point within Radian for the handling of
this information.
If samples from the field sites have been compromised in any way, then ICF and the EPA
Technical Monitor will both be immediately notified. Compromised samples will include samples
received warm (no ice), samples with the wrong field data sheet for the sample labels, samples sent to
the wrong laboratory, broken or leaking bottles, and unusual occurrences such as colored samples-or
heavy sedimentation. Additional clarification on the receipt of warm samples was received from EPA
in November of 1989. Instructions provided in the memorandum (Appendix G) indicated that the
laboratories were to analyze warm samples.
-------
Section No. 6
Revision No. 3
Date: August 1, 1990
Page 2 of 4
FIGURE 6-1
FIELD SAMPLING TRACKING SHEET
tiiiitiiiiifitiiiiitiiiiiiiiitiiiitu
I -Mil "ttkKS "'* I
iiiiiittitiniiiitiiiniiiiiiiiiuiii
;5. i^.
*?3 '7 *7
>7 +*.
ore
rtx
:r-f.r- ii-i-Si :>
girySL'^.
-------
Section No. 6 t
Revision No. 3
Data: August 1, 1990
Page 3 of 4
FIGURE 6-2
ICF SAMPLE LABEL
NATIONAL PESTICIDE SURVEY
SAMPLE tt: PC-2226-1-9-03
JMM - METHOD* 9 KIT: 111
BACKUP SAMPLE
PRESERVATIVE: H2S04
DATE ! TIME ! SAMPLER
NATIONAL PESTICIDE SURVEY
SAMPLE tt: PC-2226-1-9-O1
JMM - METHOD** 9 KIT: ill
FIELD SAMPLE
PRESERVATIVE: H2S04
DATE ! TIME ! SAMPLER
-------
Section No. 6
Revision No. 3
Date: August t, 1990
Page 4 of 4
FIGURE 6-3
SAMPLE RECEIPT SCREENS
If It does
check out ± I f»
Was there any damage to
tho sample kit? (Y/N)
I g^ Ones
DM you redeve these bottles
to tho sample kltt (V/N)
PO-04 1«- 1-3- 1
PO-04 IS- 1-3- 2
PO-04 tt-t-3-3
PO-04 IB- 1-3-4
W Yes C
Was there any damage to
tho bottles? (V/N)
1 If yea. then
* E
If not. Error
»
Try again
If yes. then
complete
If no. then
If no, then ret
maing n
Clt NPS Sa
L
nw ^^^ "
b^. 3. Exit to DOS
Please Indicate tho causa for damage:
Kit Broken (Y/N)
ice Melted (Y/N)
Other Reason (V/N)
Comments:
-
mdtoa
PO-04
PO-04
PO-04
PO-04
Indicate i
urn
to which bottles you received
i*. i.a.i v/n
lft-t-3-2 , ,
14-1-3-3
Ift- 1-3-4
my addtlonal bottles received
Return-to Mam Menu
1
t
Bottle No: Damage Broken Seal Broken Other
y/n y/n y/n y/n
-------
Section No 7
Revision No. 3
Date: August 1. 1990
Page 1 of 9
7. SAMPLE CUSTODY
Sample custody for this program will be executed according to the following procedures. These
procedures are based on EPA guidelines.
Upon receipt of samples, the sample control task leader will supervise the receipt of the
samples, the logging in of the samples using the Radian SAM\ (Sample and Analysis Management)
system, and the proper storage of the samples prior to sample preparation and analysis. Samples
received each day will be assigned to an unique SAM work order number with individual samples
being tracked by unique fraction numbers in the work order. An example of the SAM work order
sheet used to transmit the samples to the laboratory is shown in Figure 7-1.
The SAM system will be used to prepare sample data sheets (Figure 7-2) for each sample
handling step (the laboratories performing the work and the test codes for the preparation and
analysis). The data sheet provided for the Sample Preparation Group indicates the required extraction
conditions and for the Gas Chromatography Group indicates the required analysis to be performed.
A Sample Workplan (Figure 7-3) will be prepared for each set of samples. This workplan will
contain information about the preparation such as. sample volumes, surrogate spiking levels, and the
sample dilutions to be performed. A Sample Worksheet (Figure 7-4) will be prepared for each
individual sample which will serve as a preparation history of that particular sample. The Sample
Worksheet will accompany the samples to the Chromatography Laboratory. The sample control task
leader will be responsible for assuring that all of the required documentation is completed for each
sample.
Samples sent by the EPA under iced conditions will be stored upon receipt in an area free of
organic chemical contamination and capable of maintaining the samples in the dark at 4'C. After the
samples have been properly analyzed, all sampling materials shall be returned collect freight to ICF as
specified by the EPA Technical Monitor.
Radian will be supplied by EPA/ICF a two week advance notice of the sites to be sampled and
the number of samples to be collected at each site. Upon receipt of the samples, Radian will contact
ICF through computer modem and enter the sample receipt information and if the samples were iced
when received. If samples do not contain ice upon receipt, the Technical Monitor and ICF will be
contacted immediately.
Strict adherence to the 14-day holding times for both samples and extracts will be observed for
both the primary and confirmatory analyses Under no circumstances will a sample be extracted after
the 14-day holding time (from time of sampling, not sample receipt) has expired. In addition, any
backup sample which is to be extracted due 10 failed QC must be extracted within the original 14-day
holding time from sample collection. Sample extracts *iil not be analyzed after exceeding the 14-day
holding time for extracts. Both the primary and confirmatory analyses will be performed within the 14-
day window for extracts.
-------
Section No. 7
Revision No. 3
Date: August 1, 1990
Page 2 of 9
FIGURE 7-1
SAMPLE WORK ORDER SHEET
P»GE 1
CLIENT: NPS
PROJ: NPS
COMPANY EPA CINCINNATI
CON: LOOGLE
FACIL 26 W. M.L. KING OR.
CINCINNATI. OH 45268
Austin
OEPTS/
TESTS
HEP ROBERT THOMAS
PHONE NA
WORK ID WELL WATERS FOE METHOD 4
TAKEN WDI.JEJ.8KH.JGa.SH.Bf.JJ.JR
TRAMS FEDX
TYPE DRINKING WATERS
CREATED 10/18/89 TMHSNITTEO 10/18/89
UR1TTEN 10/18/89 P«EV TRAMS CH _13
OUOTEO * FUST TRAMS 10/18V89
SAMPLE S SAMPLES 1$ EX 13
MOTES
OAT* SHEET OBO * 89-10-190-CH
CAT: RCVO: 10/18/89 DUE: 11/13/89
STAT: TRANSMITTED 10/18/89
DASH SAMPLE IDENTIFICATION STORED
01A PC-Z059-3-4-01 117 U-15
018 PC-2059-3-4-03
02A PC-2227-3-4-01
028 PC-222r-3-4-03
03A PC-2607-3-4-01
038 PC-2607-3-4-03
04A PC-260a-3-4-01
048 PC- 2608-3-4-03
05A PC-2610-3-4-01
058 PC-2610-3-4-03
06A PC-2618-3-4-01
068 PC-2618-3-4-03
OTA PC-26S2-3-4-01
078 PC-2652-3-4-03
08A PO-0712-3-4-01
081 PO-0712-3-4-03
09A PO-0721 -3-4-01
098 PO-0721 -3-4 -03
10A PO-0726-3-4-01
108 PO-0726-3-4-03
11A PO-0728-3-4-01
118 PO-0728-3-4-03
12A PO-0785-3-4-01
128 PO-0785-3-4-03
13A PC-2227-3-4-16 LS-A2 -
117 U-1
117 U-15
117 U-1
117 U-15
117 U-1
117 U-15
117 U-1
117 U-15
117 U-1
117 U-15
117 U-1
117 U-15
117 U-1
117 U-15
117 U-1
117 U-15
117 U-1
117 U-15
117 U-1
117 U-15
117 U-1
117 U-15
117 U-1
117 U-15
-------
Section No. 7
Revision No. 3 l
Date: August 1, 1990
Page 3 of 9
FIGURE 7-2
SAMPLE DATA SHEETS
PAGE 2
CLIENT: NPS
PROJ: NPS
OEPT CJJ OASH
CATEGORY
SAMPLE AND WOJ
SHIPPED 10/17
NPSEWN sge^
OEPT CH DASH
CATEGORY
SAMPLE AND WOI
SHIPPED 10/17
NPSEWN sps
RAS Austin
CON: LOOGLE
«01A 10 PC-2059-3-4-01
UHEN COLLECTED 10/17/89
UC DESCRIPTION
«2A ID PC-2227-3-4-01
UHEN COLLECTED 10/17/89
IK DESCRIPTION
t'«L
DATA SHEET
CAT:
STORED 117 U-15
CH NPSEWNOO
EX -351SWNOO
STORED 117 W-15
CH - NPSEWNOO
EX 351SVNOO
-
ORO * 89-10-190-CH
RCVD: 10/18/89 DUE: 11/13/89
STAT: TRANSMITTED 10/18/89
JOB I
',
I
JOB I
I
OEPT CH OASN M3A ID PC-2607-3-4-01
CATEGORY WHEN COLLECTED 10/17/89
SAMPLE AND WORK DESCRIPTION
SHIPPED 10/17
NPSEUN fPttifl.
DEPT CH OASN *MA ID PC-2608-3-4-01
CATEGORY WHEN COLLECTED 10/17/89
SAMPLE AND WORK DESCRIPTION
SHIPPED 10/17
NPSEUN f BKilL.
DEPT CM OASN MSA ID PC-2610-3-* -01
CATEGORY WHEN COLLECTED 10/17/89
SAMPLE AND WORK DESCRIPTION
SHIPPED 10/17
NPSEWN social
STORED 117 U-15 JOB
CH -NPSEWNOO
EX -3S1SWNOO
STORED 117 W-1? JOB
CH -NPSE.VNOO
EX -351SWNOO
STORED 117 U-15 JOB
CH NPSEWNOO
EX -351SWNOO
1
1
1
1
1
1
1
1
1
-------
Section No. 7
Revision No. 3
Data: August 1, 1990
Page 4 of 9
FIGURE 7-3
SAMPLE WORKPLAN
RADIAN CORPORATION
EXTRACTION PROJECT WORKPLAN
SATE
3Y c. SMtTH
FOR CLIENT MPS
PM
APPROVAL
.CHARGE NUMBER 125-001-16-01
_PD
TASKS EXTRACTION OF WATER SAMPLES
CONTACT 130
ANALYSIS HPLC PESTICIEES
EXTRACTION [XJ£] 3510 [ ; 3520 ; ; 3540 [.
BACKGROUND INFORMATION
3550 : I OTHER
NUMBER Of SAMPLES
MATRIX SPIKES
NONE
REAGENT BLANKS i.
OTHER L.
CSMTSOLS
SAMPLE DISPOSITION [ ] USE ALL [ ; RETAIN UNUSED [ J
SAFETY PRECAUTIONS:
ROUTINE SAVE BQTTI.SS
OTHER __________
POTENTIAL ANALYSIS PROBLEMS USE 01 WATER FOR BLANK AMD LAB CONTROLS
USE CORRECT SPIKES AT CORRECT LEVELS IN SAMPLES
STEAM BATH TEMP SHOULD BE 6S TO 70 DEGREES C,f||S.TU,S
INSTRUCTIONS PRE EXTRACT PI WATgB nx 50 all M«C121
LOAD EACH SAMPLE INTO A 2 LITER S%p, FUNNEL
ADD 1 ml HOC12 SOLtJTTQN TO BLANK AND LAB CONTROLS
SHAKE VIGOROUSLY FOR 1 MINUTE
SPIKE EACH ANALYSTS WITH SURROGATE SPIKE AND OTHER APPROPRIATE SPIKES
ADD 50 ml OF PHOSPHATE BUFFER SOLUTION; CHECK FOR BH OF 7
ADD 100 O OF NaCl TO EACH ANALYSIS
SURROGATES SO ul OF SP-2-206 EACH ANALYSIS
OTHER SPIKES SEE PACE 2
SAM*
9910190-OBA
-09A
-10A
-11A
-12A
-13A
8910199-O1A
-02A
-03A
-04A
-OSA
-0«A
CLIENT ID
PO-0712-3-
PD-0721-3-
PO-O72S-3-
PD-0728-3-
PO-O7B3-3-
PC-2227-3-
PC-2625-3-
PC-2635-3-
PO-O739-3-
PD-0740-3-
PO-0765-3-
PD-O76S-3-
-Ol
-01
CLTD SHPD RCVD SIZE
i°A7/89 \Q«il
" / riiQBl
" / If ami
" /CfUml
8/J9 10/19/89 /O^O ml
" / CJC. ml
« [p 7O ml
K lOfO ml
« /««> ml
" {nVS~mL
8910199-Q9A-a REACgMT BLANK
NA
NA
-
lOA-f
11A-S
LAB
LAB
PONT
CON1
mori
SOL
MIX
MIX
A
B
NA
NA
NA
NA
NA
HA
1000 ml
jOOO mi
rOQQ ml
DELIVER TO TLS
-------
Section No. 7
Revision No. 3 «
Data: August 1. 1990
Page 5 of 9
FIGURE 7-3 (continued)
SAMPLE WORKPLAN
RADIAN CORPORATION DATE I'-l BY naa« 2
EXTRACTION PROJECT WORKPLAN 'APPROVAL
FOR CLIENT NPS CHARGE NUMBER 325-OQ1-1S-Q1
PM PD - TL . CCKTACT L2O
TASKS EXTRACTION OF WATER SAMPLES
ANALYSIS HPLC
EXTRACTION !XX.l 3510 :_; 3520 ;__; 3540 [_; 3550 [__; OTHER
BACKGROUND INFORMATION
NUMBER OF SAMPLES REAGENT BLANKS
MATRIX SPIKES OTHER
SAMPLE DISPOSITION [_] USE ALL : ; RETAIN UNUSED [ ]
SAFETY PRECAUTIONS:
ROUTINE
OTHER
POTENTIAL ANALYSIS PROBLEMS STEAM BATH TEMP SHOULD BE AT 6S TO 70
DECREES CELSIUS
INSTRUCTIONS PRE EXTRACT 31 WATER f3x 60 ml M«C12>
DRY AND CONCENTRATE TN K-P TO 2-4 ml
ADD 4.0 ml M«OH TO RECEIVER AND MICBQSMYDER
CONCENTRATE TO 5.0 ml IN M«OH
SURROGATES
OTHER SPIKES SEE 3ELQW
SAM* CLIENT ID CLTD SHPO RCVD SIZE
1 nL CH-2-79 IN 891019O -13A
__>^_-__^___ AND IN 8910199 -1QA-S
1 n>L CH-2-80 IN 8910190 -13A _^__^
__- AND IN 8910199 -10A-S
1 mL CH-2-81 IN 8910199 -11A-S
1 nL CH-2-B2 tM " " ______
DEtlVCT TO
-------
Section No. 7
Revision No. 3
Date: August 1, 1990
Page 6 of 9
FIGURE 7-4
SAMPLE WORKSHEET
SAMPLE WORKSHEET FOR CHROMATOGRAPHY
CONTRACT NAME NPS
CONTRACT NUMBER 32S-001-16-Q1
RADIAN CONTACT LDOGIE
SAM < i
CLIENT ID PD-:
ANALYSIS [ _ ] 8080 [ _ J 8080PE [ _ ] 8080PC [ _ ] 8100 [ _ ' 8140
C _ ] 8150 [ _ : TARGGC [ _ I TCO r _ ] GRAV ' _ ' 8040
OTHER '
SAMPLE TYPE CXX.J AQUEOUS [ _ ; SOLID ' _ ' ORG LIQ [ _ 1 SORBENT
C _ ] OTHER
MATRIX COMMENTS
SAMPLE PREPARATION [JUJ] 3510 SEPFUN ' ; 3520 CONTIN [ ] 3540 SOXHLET
EXTRACTION METHOD [ ] 3550 SONICA [ ; 3580 DILUTE [ I OTHER
SAMPLE SIZE
SURROGATE SPIKING
OTHER SPIKING
ANALYST
DATE
'0
TASKS
EXTRACTION
KD
g
-------
Section No 7
Revision No. 3 ,
Date: August 1, 1990
Page 7 of 9
The backup sample will be held for 14 days and then will be discarded in an environmentally
safe manner. Under no circumstances will a sample or extract be held more than 14 days before
extraction or analysis, respectively. Sample extracts will be stored at 4'C until the results for that
sample have been approved by EPA. The extracts will then be discarded.
All samples and extracts will be kept in secured storage areas. The temperature of the
refrigerators used to store samples and extracts are monitored daily and recorded on laboratory check
sheets as shown in Figure 7-5. In addition, a laboratory sample tracking system at Radian requires
the signing out of samples each time they are removed from the refrigerator and logging back in when
they are returned. The date of sample disposal can also be recorded on this form. A copy of this
form is shown in Figure 7-6.
-------
Section No. 7
Revision No. 3
Date: August 1, 1990
Page 8 of 9
FIGURE 7-5
CHROMATOGRAPHY DAILY ROOM CHECK FORM
:*ce:
AM
:HROKATOCHA?H? LABORATORY
-All? ?J30M CHECK
ROOMS .-;" > -.-136
1} Environment
a) Lignti are working
b) Floor u dry
c) Room has bt«n cltantd
i) Room veil ventiiactd 'no noxieua ooors,
cnperatur* victim noraai rangaj
t) Hood* art ui vorxing oreir
2) All laaplti. cztraecs and ehmeali arc properly
contained and labeled.
3) Refrigerator and frtezer ceaperature cheek
Refrigerator #1: _^ _
Refrigerator tl.: ~I^^^^^^^~~~'"'~~~
Frtezer: ~^~ ~~~ "~^~~~"" "~~^
Coamenta
Prepared by: _^___^^^.^^____^___
PM
1) All «quipeient and heat ing/cool ing device* are turned
off except for thoae which have been properly aet up
for overnight experiment*. Q Q
2) All overnight experiment* have been checked (temp-
erature of operation, proper power tupply. no frayed
cord*, at ability of experimental aetup. etc.) to
naure that they will preaent no tafety hasard*. C3 Q
3) All aamplee and reagent* have been properly atored. Q Q
4) All ga* cylinder* have been checked and contain aufficient
preaaure to iaat until the next working day. All
cylinder* are aecure. O O
5) All gaa cylinder* net to be uaed overnight are turned off. C3 O
6) Printer*) have *uffieieac paper to Iaat until thai
next working day. Q O
f) HFLC* contain auffUieat aolvent to la*t until aorning. Q Q
8) Plea** note any overnight or weekend experiment that will be left
unattended. Liat the aame and hem* phone number of the reaponaibl*
party ao he/ahe may k« contacted in caae of a problem.
int*
Prepared byt
Timai
-------
Section No. 7
Revision No. 3 *
Date: August 1. 1990
Page 9 of 9
FIGURE 7-6
REFRIGERATOR SAMPLE CHECK-OUT LOG
SAMPLE CHECK OUT LOG
Login
Check Out
SamptolO
0«M Tim*
R«lu
-------
Section No 8
Revision No. 3
Date: August 1, 1990
Page 1 of 4
8. CALIBRATION PROCEDURES AND FREQUENCY
Information is presented in this section pertaining to calibration of the instrumentation that will
be used during this project. Included is a description of the procedure {or reference to an applicable
standard operating procedure), the frequency, and the calibration standards to be used.
Calibration procedures for Method 4 will follow those outlined in the method with the exceptions
that all calibrations of the HPLC system will be accomplished using the external standard technique. It
was determined that calibration with ethylbenzene as the internal standard resulted in higher variability
than using the external standard technique. A five-point calibration curve will be determined for each
analyte. One of the standards used to generate the curve will be at 0.5X the method reporting limit
and the other concentrations will define the working range of the detector, generally at 0.5, 2,5, 10
and 25 times the MRL. Acceptability of the calibration will be evaluated using relative standard
deviations from the mean response factor. A relative standard deviation of less than 20 percent will be
used as an acceptance criterion. The average relative response factor (RRF) will be used to calculate
the concentration for each species of interest.
Response factors will be verified on each working shift by the analysis of samples of each mix at
alternating concentrations within the working range of the detector. The response factors obtained for
the calibration check standards must be within +. 20% of the predicted response factors. If repetition
of the check sample does not produce acceptable results, fresh calibration standards will be prepared
as a check for degradation of the standards. The new calibration standards will be compared to the
response from the existing standards. If the response factors do not agree within +. 20% of the
existing standards response factors, then all analytical work will cease until the problem has been
discussed with the Technical Monitor and resolved. If the new calibration standards agree within ±
20% of the existing standards, then analysis will continue.
Calibration solutions for Method 4 will be prepared from dilutions of the primary standards
prepared by Bionetics specifically for NPS. Standards from Bionetics were used on an "as received"
basis. Standards from the same production batch were used throughout the project.
Standards were prepared by delivering a known amount of the stock solution into a volumetric
flask containing methanol using a calibrated micropipette to form secondary standard solutions. The
secondary standards will then be further diluted to provide a range of concentrations covering the
linear range of the instrument and the expected range of concentrations in the field samples. The
lowest standard will be prepared at a concentration equal to 0.5X the MRL
Initially, a second set of secondary standards will be prepared by a different individual as a QC
check of the first set and for use as spiking solutions for the laboratory and field samples. If the two
sets of solutions do not agree within +_ 20% in concentration, both sets will be discarded and two
more sets of secondary standards will be prepared Each time a new set of secondary standards are
-------
Section No. 8
Revision No. 3
Date: August 1, 1990
Page 2 of 4
prepared, they will be checked against the old set as described above. A second set of standards will
not be prepared each time secondary standards are prepared, only during the initial set.
Secondary standards for both mixtures (Table 5-1) will be prepared. They will be logged into a
standards preparation notebook within the Chromatography Laboratory. This notebook will contain
the information on how each standard was diluted, the date of preparation, and the person preparing
the standard. As new solutions are prepared, they will be logged into the standards preparation
notebook and the old standard will be marked as no longer in use. The instrument QC standard will
be prepared as designated in the Method. Preparation will be documented as described above. This
standard will be replaced when it is completely depleted, assuming degradation is not observed.
As previously discussed, a set of secondary standards will be produced which will be used to
spike the laboratory control samples and field spike samples. These solutions will be prepared at a
concentration such that one milliliter or less of the concentrate can be added to the sample to give
concentrations of 2, 10, or 20 times the minimum reporting level for each
analyte (later changed to 2, 5 and 10 times the MRL; see Appendix E). Each field spike sample
received will have a designation on the label which indicates the mixture and the level to be spiked in
the laboratory. As explained in Appendix E, an indication of a Level 0 spike will result in spiking at 2X
MRL, Spike Level 1 will be 5X MRL, Level 2 will be 10X MRL, and Spike Level 3 will be 20X MRL An
equal number of spikes for each mixture will be done at 5, 10, and 20 times the MRL (2, 5 and 10X
MRL).
At the request of the NPS management at EPA, the initial spiking levels of 5, 10 and 20 times
the MRL were dropped and replaced with levels of 2, 5 and 10 times the MRL as shown in the letter
from EPA included in Appendix E. Time storage and LCS samples continued to be spiked at the 10X
MRL level.
Metribuzin DADK and Metribuzin DK will be in the calibration mixtures and spike mixtures.
However, only qualitative data is required for these analytes. Therefore, they will not be subject to any
of the QC requirements determined during the initial demonstration of capabilities.
Equipment to be used for the NPS proiect will conform with that found in the method. A Waters
gradient HPLC system equipped with a Model 680 gradient controller, WISP Autoinjector and Model
490 variable wavelength detector operated at 254 nm, will be used for analysis. Columns and
conditions specified in the method will be used However, since all HPLC columns are not equivalent,
small changes may be necessary in the gradient program in order to improve separation. All changes
will be documented prior to the initial demoosuatton of capabilities. Any changes after this point will
require approval of the Technical Monitor and may require repeating the initial demonstration of
capabilities.
Each day prior to the analysis of any caiitxaion standards or sample extracts, an instrument
quality control standard will be analyzed to determine sensitivity, column performance, and
-------
Section No. 8
Revision No. 3
Date: August 1, 1990
Page 3 of 4
chromatographic performance as specified In Method 4. This will be done for the primary column, but
not for the confirmation column. The sensitivity requirements will be based on the detection limits
established in the method. Column and chromatographic performance will be calculated as specified
in the method. A standard form will be prepared for the daily recording of the calibration check
sample, reagent blank analysis, and the results of the instrument quality control standard. These
forms will be filed with the data from that sample set as a portion of the QC procedures. A copy of
this form is included as Figure 8-1.
-------
Section No. 8
Revision No. 3 *
Data: August 1, 1990
Page 4 of 4
FIGURE 8-1
DAILY QC FORM
NATICNAL PESTICIDE SURVEY
DAILY QUALITY CONTROL
Date
Anaiyit
I. :NSTRUKE!C QC STANDARD
Analyte
Acceptance
Criteria
A. Senmivicy
B. Qiraatograpnic
PerxczDance
S/N =
Sulfona* * 0.3 ug/af.
C. Calm Perform**
II. OAIL? CALIBRATION CKEOC
Mix
« 0.1 ug/at.
« 5 us/at
'I
> 3
0.95 < PS < I.C5
C.93 < PCF < ;.S7
R > 0.5
Concentration Level
Concentration Percentage of
Anaiyce Concentmun (ug/aU Deteaaned (^/oL) Cilniljtert Conceotrmtian
Atraxim deeilcylated
Siuoon
Fe
Prone«ulB eataooiite
Carbofumi
CyvMcuw
Fluai mi 1,11
NtcribuuAK
JO.
-------
Section No 9
Revision No. 3
Date: August 1, 1990
Page 1 of 3
9. ANALYTICAL PROCEDURES
This section presents descriptions of the analytical methods to be employed in this program.
9.1 ANALYTICAL METHODOLOGY
As specified by the EPA Technical Monitor, the following drinking water analytical method will be
employed for this program.
9.1.1 Determination of Pesticides in Ground Water by High Performance Liquid
Chromatography with an Ultraviolet Detector (Method 4)
Samples are extracted using separatory funnels and three aliquots of methylene chloride. The
pH is adjusted to 7 with phosphate buffer and sodium chloride and surrogate standards are added
prior to extraction. The extracts are dried, concentrated, and solvent-exchanged to methanol.
The sample extracts are analyzed using a Waters gradient HPLC system equipped with a WISP
autosampler. The column is a Dupont 25 mm x 4.6 mm I.D., 5 um ODS. Columns produced by other
manufacturers may not give satisfactory separation of the target analytes. End capped Dupont
Zorbax columns will not provide the necessary separation. Only non-end capped Dupont Zorbax
columns have been found to be satisfactory.
The gradient and solvent flow conditions specified in Method 4 are used. Detection is achieved
using a Waters Model 490 UV detector with a primary wavelength of 254 nm. Other wavelengths, 280
nm and 230 nm, were monitored initially in an attempt to determine a response ratio between the
wavelengths. This ratio was to be used as a preliminary means of confirmation. However, monitoring
of more than the primary wavelength caused a decrease in detector sensitivity due to the detector
design. Therefore, only the primary wavelength of 254 nm was monitored during the suryey.
Confirmatory analyses for Method 4 will make use of the same extract as used for the primary
analysis. Confirmatory analyses was attempted utilizing the column and conditions specified in the
method. However, the column and conditions were unsatisfactory for the separation and confirmation
of the target analytes. Confirmational analyses required between the start of the survey and March
1989 were performed by EPA laboratories as per the instructions received from EPA. Iced extracts
were shipped to EPA by overnight express for analysis. The confirmational method received from the
Technical Monitor in March, 1989, is included in Appendix H. This method was used at Radian for
confirmational analyses from that time until the end of the survey.
The analyte requiring confirmational analysis will be quantitated by comparison to a standard at
a concentration within ± 20% of the concentration determined using the primary column. The
concentration determined during confirmation must agree within +. 25% of that determined on the
primary column. If agreement is achieved, then the results are reported as a concentration. If
agreement is not achieved within the +. 25%, then the analyte will not be confirmed.
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Section No. 9
Revision No. 3
Date: August 1, 1990
Page 2 of 3
GC/MS confirmation will not be required for Method 4.
Analyte concentration is determined from the response factor for each analyte based on external
standard calibrations. Quality control activities include an initial demonstration of capability, matrix
blanks at a frequency one per sample set, laboratory control samples, analysis of an instrument
control standard, and determination of surrogate recoveries from each sample. The analysis types
and frequency of analysis are shown in Table 9-1.
It is anticipated that approximately ten samples per week will be received from the field during
the first year. Including the QC samples (lab spikes and time storage), ten field samples result in a
total of 15 samples to be analyzed. Therefore, 15 will be the maximum number of samples to be
included in a sample set. Due to the manner in which the samples will be received, it is anticipated
that most sample sets will consist of six to ten samples including the QC samples.
All procedures outlined in Method 4, with the exceptions which are project specific and are
outlined in this document, will be followed as written. There are no differences from the printed
method for glassware cleaning, reagents, equipment, and analytical procedures. A copy of Method 4
has been appended to this document for reference (Appendix A).
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Section No. 9
Revision No. 3
Date: August 1, 1990
Page 3 of 3
TABLE 9-1
NFS ANALYSIS TYPES FOR METHOD 4
Analysis Type Analysis Frequency Chargeable Analysis
PRIMARY ANALYSIS
Instrument Control Standard 1/day No
Lab Control Standard 1/set No
Method Blank 1/set No
Calibration Standards 1/day No
Field Sample 1/site Yes
Backup Sample as needed Yes/Noa
Spiked Sample 10% Yes
Day 0 Time Storage Sample 10% Yes
Day 14 Time Storage Sample 10% Yes
Day 14 Time Storage Sample 10% Yesb
Performance Evaluation Samples as requested Yes
CONFIRMATIONAL COLUMN
Field Sample as needed Yesb
Calibration Standards as needed No
a Chargeable if requested by the Technical Monitor; not chargeable if due to the QC outside of
defined limits.
b Charged at confirmational analysis costs.
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Section No 10
Revision No. 3
Date: August 1, 1990
Page 1 of 6
10. DATA REDUCTION, VALIDATION, AND REPORTING
This section describes the basic responsibilities and procedures for data reduction, validation,
and reporting as applied to this program.
10.1 DATA REDUCTION
Data reduction procedures for the HPLC analytical technique involves initial integration of the
chromatographic peaks by the integration device or computer associated with the instrument. The
qualitative identification of each compound is based on the retention time (RT) of the peak as
compared to the known retention time obtained for compounds in the calibration mixture.
Quantitative values are computed based on the current calibration RFs determined for each
compound in the calibration mixture. Based on this information, the computer or integration device
prints out a report with preliminary identifications and quantitation for review by the instrument
operator.
10.2 DATA VALIDATION
The computer/integrator system generated analysis reports will be reviewed by the operator for
reasonableness and compliance with quality control requirements (Section 11). The operator may
interact with the computer/integrator system to correct any problems noted with integration or
compound identification. Each report will be reviewed by the laboratory manager who has final
responsibility for the output of the laboratory. The laboratory manager will validate the results and
then release the information for inclusion in the report.
Each of the task leaders will be responsible for the data from their particular area. Figure 10-1
presents the project organization. The Radian Project Director, Larry Ogle, has final validation
responsibilities before the data is sent to the EPA Technical Monitor.
10.3 DATA REPORTING
The reporting responsibilities for this program rest ultimately with the Project Director. The Task
Leaders will provide input to monthly reports that are issued by the Reporting Task Leader. The
Technical Reviewer will review planning documents and reports. The Quality Assurance Officer will be
kept informed as to the work progress and will have the final decision on quality assurance concerns.
All data for a set of samples will be reported as a complete data set, with all QC and
confirmatory data, within two months from the date of sample collection. Data will be reported using
the reporting codes format specified by EPA. A copy of the memo specifying the data reporting
codes and sample designations is included in Appendix I.
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Section No. 10
Revision No. 3
Date: August 1, 1990
Page 2 of 6
FIGURE 10-1
PROJECT ORGANIZATION
EPA Technical Monitor
Kent Sorrell
Program Manager
R.L. Richardson
Project Director
L.D. Ogle
Quality Assurance
Director
David L. Lewis
-K.W. Rozacky (QAC)
Technical Reviewer
F.L. Shore
Task Leader
Sample Control
J.A. Lindsey
Task Leader
Sample Preparation
C.E. Smith
Task Leader
Chromatography
T.L. Shaw
Task Leader
Reports
L.D. Ogle
- C.D. Zieschang - J.K. Purvin
- A.L. Jarma - R. Crider
- R.G. Whit*
- A.E. Jones
- T.L. Shaw
- A.L. Dever
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Section No 10
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Page 3 of 6
Method 4 data will tie recorded in a Paradox database at Radian using an EPA specified data
format (Appendix J). It will then be sent to EPA by transferring the data from the Paradox format to an
ASCII file and sending EPA a personal computer 5.25 inch floppy disk. A copy of the data format for
Method 4 is shown in Figure 10-2. In addition, hard copies of the data will be available for the
Technical Monitor to review, should he decide to do so.
The data will be received by EPA and transferred to a mainframe computer as described in
Appendix J. A hardcopy of the data, with suspect data highlighted, will be printed for the Technical
Monitor to perform a quality control check before the data is finalized.
During the execution of the survey, a rapid reporting system was established to report
concentrations of certain analytes which may have known health effects. Appendix K includes the
documents establishing a rapid reporting system and modifying that system when updated health
effects values were available. Analytes requiring rapid reporting for Method 4 were Cyanazine, Diuron,
Fluometuron, and Propham.
NPS analytes detected at levels below the MRL will be reported as required by EPA (see
Appendix L). Confirmatory analyses will be performed on analytes between the MRL and the.MRL/2.
Discussions will be held with the Technical Monitor about unconfirmed components which occur on a
regular basis to determine if further investigation is necessary. Since Method 4 is a HPLC method,
confirmation and identification by HPLC/MS is possible, but extremely difficult. Each case will be
handled on an individual basis after discussions with the Technical Monitor.
Monthly reports will be prepared which will include a summary of the samples received, the
analytes which were identified and confirmed, changes in personnel working on the project and any
problems associated with the field or QC samples. Copies of the control charts will also be provided
for sample sets reported in that reporting period.
In addition, verbal telephone reports will be provided to the Technical Monitor when confirmed
positives for analytes specified by EPA are observed and when the quantitation on the confirmatory
column does not agree with the primary column within the preset-criteria. The rapid reporting, as
mentioned above, will be done so that the Technical Monitor can arrange LC/MS confirmation or
extraction and analysis of the backup sample within the holding time of the sample. A record of all
rapid reporting will be recorded on Radian telephone call records for later review if necessary. An
example of the call records is shown in Figure 10-3.
Laboratory data (i.e., chromatograms, notebooks, calibration data, and standard preparation
notes) will not be included in the monthly report. However, copies of specific chromatograms may be
requested by the Technical Monitor for the monthly report. This information will be stored in the
chromatography laboratory files. A separate file will be established for the NPS samples. Each file will
be stored according to sample set, field numbers and Radian SAM numbers, i.e., according to sample
receipt. Samples in an individual set will be filed within a folder which will contain all QC data for that
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Section No. 10
Revision No. 3
Date: August 1, 1990
Page 4 of 6
FIGURE
10-2
FORMAT FOR METHOD 4 REPORTING
FLd-pH $_Temp
-
Receipt Condition
Samp # Lab
TSD
Type Spiker
LCSA CM
Comments
NONE.
Analyte
Atrazine dealkytated
Barban
Carbofuran phenol
Carboxin sulfoxide
Cyanazine
Diuron
Fenamiphos sulfone
Fenamiphos sulfoxide
Date_Sam Date_Shp
01/01/60 01/01/60
Set # Date_Spk
01 04/30/87
Extract Analyst
CM CM
Cone.
100.7
95.8
92.1
89.7
Date_Rec Time_Sam Time-Ice
01/01/60
Date_Ext Date_Ana Column
04/30/87 05/03/87 PRIM
Sam_Vol Ext_Vol Int. Std. % Surr
1000 5 31 99.4
Analyte " Cone.
Linuron
Metribuzen DA
Metribuzen DADK 83.1
Metribuzen DK
Neburon
Pronamide metabolite 1*19.1
Propanil 84.5
Propham
Fluometuron
3-Ketocarbofuran phenol
Swep
99.9
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Section No. 10
Revision No. 3 >
Date: August 1. 1990
Page 5 of 6
FIGURE 10-3
TELEPHONE CALL RECORD FORM
DATE
> P O R A T I O N
CONTACT REPORT
ORIGINATOR
CONTACT BY:
NAME. TITLE
TELEPHONE ~ MEETING
& ORGANIZATION
fTTHPR
ADDRESS & TELEPHONE NUMBER
PURPOSE OR
SUBJECT (Give protect numoer if
appropriate)
SUMMARY
ACTION
DISTRIBUTION:
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Section No 10
Revision No. 3
Date: August 1, 1990
Page 6 of 6
sample set. Therefore, retrieval of data will be by sample number with the corresponding calibration
and QC data for that sample set being available in the same folder. QC charts will be filed separately
with a designation of the applicable samples analyzed during that time indicated with each chart.
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Section No 11
Revision No 3
Date. August 1, 1990
Page 1 of 7
11. INTERNAL QUALITY CONTROL
An internal quality control (QC) system is a set of routine internal procedures for assuring that
the data output of a measurement system meets prescribed criteria for data quality. Inherent and
implied in this control function is a parallel function of measuring and defining the quality of the data
output. A well-designed internal QC program must be capable of controlling and measuring the
quality of the data, in terms of precision and accuracy. Precision reflects the influence of the inherent
variability in any measurement system. Accuracy reflects the degree to which the measured value
represents the actual or "true1 value for a given parameter, and is related to the error introduced by
component parts of the measurement system.
This section will describe the internal quality control procedures to be used for this program.
The frequency, acceptance criteria, and corrective action for each check is presented in Table 11-1.
11.1 METHOD 4 QUALITY CONTROL
The quality control procedures to be used for Method 4 analyses will include:
Demonstration of capability;
Daily calibration check;
Surrogate standard spike recoveries;
Reagent blank analyses;
Duplicate injections (not required by EPA);
Laboratory control standards;
Blind performance evaluation samples;
Instrument QC standard; and
Analyte confirmation.
These procedures are described in this section.
11.1.1 Daily Calibration Check
Daily, prior to sample analyses, the instrument calibration will be checked using a standard
containing the compounds of interest at alternating concentrations in the working calibration range.
. Concentrations of analytes used to check the calibration are at 0.5, 2, 5, 10 and 25 times the MRL A
different concentration calibration standard will be used each day to validate the calibration curve.
The response factors (RFs) determined from this analysis must be within ± 20% of the RF obtained
during the last multipoint calibration for each compound of interest. If not, the calibration check is
repeated. Should the second check confirm the first analysis, a multipoint calibration will be required
before sample analysis may proceed.
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Section No 11
Revision No. 3
Date- August 1, 1990
Page 2 of 7
TABLE 11-1
SUMMARY OF INTERNAL QUALITY CONTROL PROCEDURES
Quality Control
Check
Calibration Check
Assess Surrogate
Recovery
Analyze
Laboratory
Control Sample
Blind Performance
Evaluation Sample
Matrix Spiked
Samples
Duplicate
Injections
Laboratory
Reagent Blanks
Instrument QC
Standard
Frequency
Dai ly prior to
analysis
Each sample and
each blank
Each Laboratory
Control Sample
1 per mixture
for each set
Quarterly
10X
10X
1 per sample
set
Daily
Acceptance Criteria
Measured RF within + 20% of
predicted response for each
analyte
Recovery of carbazole within
+30X of mean recovery
established during initial
demonstration of capabilities
Within Control Limits on
Control Charts
Recoveries within the
criteria established during
the initial demonstration of
capabi I i ties
Established by EPA
None established
Report Results
Relative range measurements
within those established by
inter laboratory method
performance study (Not
required by EPA)
Analyte concentration values
of less than one-half MRL
Criteria listed in Table 10
in Method 4
Corrective Action
1. Repeat with a fresh standard
2. Prepare a new calibration
curve
1. Check calculations for errors
2. Check the surrogate standard
solutions for abnormalities
3. Check instrument performance
4. Reanalyze the extract
5. Extract and analyze back-up
sample
1. Check calculations for
errors.
2. Check surrogate recovery in
the blank. If it passes, run
samples.
3. If surrogate recovery in the
blank fails, follow
corrective actions 2 through
5 above.
1. Review calculations and
techniques
2. Repeat test
3. Check instrument performance
it. Re-extract laboratory control
sample and all samples in
that sample set
1. Correct method deficiencies
None needed
1. Repeat analysis
2. Obtain 3rd value
3. Flag data and continue
analyses
1. Check for instrument
contamination
2. Check for reagent
contamination
3. Repeat analysis after
determining source of
contamination
1. Perform instrument
maintenance
2. Repeat standard
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Section No. 11
Revision No. 3
Date: August 1, 1990
Page 3 of 7
TABLE 11-1 (continued)
SUMMARY OF INTERNAL QUALITY CONTROL PROCEDURES
Quality Control
Check
New Calibration
Standards Check
Second Column
Conf irtnation
Instrument Blank
Frequency
Each time
prepared
Each positive
analyte on
primary column
Daily, before
sample analysis
Acceptance Criteria
^20% of existing calibration
standards
Quantitation within ^25% of
that on primary column
No detectable target analytes
Corrective Action
1. Repeat analysis
2. Prepare new standards
3. Call Technical Monitor
1. Repeat analysis
2. Call Technical Monitor
1. Repeat blank
2. Determine source of
contamination and correct
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Section No. 11
Revision No. 3
Date: August 1, 1990
Page 4 of 7
11.1.2 Demonstration of Capability
It must be demonstrated prior to analysis of samples that the instrumentation to be used has
the ability to generate data of acceptable precision and accuracy. This involves analyses of 20
samples spiked with a solution containing the species of interest and surrogate standards. Average
percent recoveries and standard deviations are then calculated for each compound.
The results obtained for recoveries and relative standard deviations are compared to the single
laboratory recovery and precision data contained in the Method. The mean recovery for each analyte
must be between Battelle's mean recovery and ± 3 times the RSD determined by Battelle and
reported in the Method. In addition, the RSD for each analyte must be <20%. If the data are not
comparable, then the calculations should be checked, the sample preparation and analytical
techniques reviewed for problem areas, and the test repeated after correction of the problems.
A set of eight spiked samples spiked at levels equal to a 5/1 signal to noise ratio on the
instrument will be used to determine the minimum reporting levels as described in Section 5. These
samples must be analyzed during the initial demonstration of capabilities before sample analysis
begins.
11.1.3 Surrogate Standard Spike Recoveries
Each sample for Method 4 will be spiked with carbazole as the surrogate. Recoveries of the
surrogate standard must be within +. 30% of the mean recovery determined during the initial
demonstration of capabilities. If the recovery for any surrogate standard does not fall within the
control limits for method performance, the sample must be reanalyzed. Control charts of the
surrogate recoveries will be established and updated every fifth sample set. Both warning limits (+. 2X
RSD) and control limits (+ 3X RSD) will be shown on the charts.
11.1.4 Laboratory Reagent Blank Analyses
Before processing any samples, the analyst must demonstrate through the analysis of a
laboratory reagent blank that all glassware and reagent interferences are under control. Each time a
set of samples is diluted or extracted or there is a change in reagents, a reagent (solvent) blank will
be analyzed to determine the level of laboratory contamination. Detection of any analyte of interest at
a level greater than or equal to one-half of the MRL for that analyte will require isolation and correction
of the problem before proceeding.
11.1.5 Duplicate Samples and Analyses
Duplicate samples will not be required for Method 4. Duplicate injections of extracts from field
samples will be performed at a frequency of 10%. if agreement for the duplicate analyses is not within
the criteria defined in Table 11-1, a third analysis will be performed. The data will be flagged if
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Section No. 11
Revision No 3
Date: August 1, 1990
Page 5 of 7
acceptable agreement is not achieved for the duplicate injections. Duplicate analyses are Radian
internal quality control measures and are not required by EPA.
11.1.6 Laboratory Control Standards
At a frequency of one per sample set, laboratory control samples for each analyte mixture will
be prepared and analyzed. The percent recovery of each analyte will be determined and compared to
the recovery data established during the initial demonstration of capabilities for the first five sample
sets. After the first five sample sets, the control charts will be updated and the LCS values will be
compared to the mean value in the current control chart. Control charts will be updated every five
sample sets. Values obtained outside the range of recoveries in the control charts will signify
problems in sample preparation and/or analytical procedures. The problem must then be isolated,
corrected, and that set of samples re-extracted before sample analysis can continue.
11.1.7 Unknown Performance Evaluation Samples
Quarterly, the laboratory will receive blind performance evaluation samples which will be
received as actual samples. The PE samples will be processed and reported in the same manner as
all other samples. Results for each analyte must be within acceptable limits established by the EPA.
11.1.8 Instrument QC Standard
The instrument QC standard is analyzed each day prior to the analysis of sample extracts and
calibration standards. This solution is used to demonstrate acceptable instrument performance in the
areas of sensitivity, column performance, and chromatographic performance. Unacceptable
performance will require instrument maintenance and the exhibition of acceptable performance before
samples may be analyzed. The criteria for acceptance specified in the method will be, used.
11.1.9 Analyte Confirmation
Method 4 requires the use of a second, dissimilar column to confirm the presence of any
analyte detected on the first column. The original method developed by Battelle did not work for
analyte confirmation, so an alternate confirmatory method was developed by EPA. The confirmation
column was calibrated with a single point calibration standard of the analyte(s) to be confirmed. The
concentration of this analyte in the standard will be within +. 20% of the concentration of the analyte in
the sample being confirmed. Quantitation is to be confirmed by agreement within ± 25% of the
concentration determined on the primary column. Failure to confirm the presence of the analyte will
result in a not detected report. Confirmation of presence and quantitation will result in both analyses
being reported. Failure to confirm the quantitation will result in an immediate call to the Technical
Monitor for further instructions.
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Section No 11
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Page 6 of 7
11.1.10 Matrix Spike Samples
A duplicate sample is spiked with known amounts of the analytes of interest in order to monitor
spike recoveries from that matrix. The frequency of spiked samples will be 10% of all samples.
Samples to be spiked and the concentration to be spiked will be designated on sample receipt
material. Radian will not make the decision of which samples to spike.
11.1.11 Calibration Standards Check
Each time new calibration standards are prepared, they will be checked against the current
calibration curve. Standards must agree within +. 20% of the existing standards or new standards
must be prepared. It should be noted that new standards may be within ± 20% of the old standards,
but cause the LCS recoveries to be outside of the warning or control limits for some analytes. In the
case that the control limits are very tight and LCS analytes are outside of the control limits after
preparation of new standards, the Technical Monitor will be apprised of the situation and analysts will
continue until new control charts are prepared.
11.2 TIME STORAGE SAMPLES
A series of time storage samples will be collected and analyzed during the NFS study to
determine the stability of the compounds in aqueous solution and in the extraction solvent. These
samples will be collected at a frequency of 10% over the period of the study.
Four extra aliquots of the samples for the time storage studies will be collected. Two of the four
replicate aliquots will be spiked, extracted, and analyzed within a four-day time frame. They will then
be reanalyzed 14 +. 4 days after the first analysis. The remaining two duplicates will be spiked at the
same time as the first two duplicates, but will be allowed to sit 14 days before extraction. These
samples will then be analyzed within four days of extraction. Table 11-2 presents the spiking and
analytical scheme for the time storage samples.
Each sample will be spiked with only one mix at the 10X MRL level. Results of the time storage
samples will be reported to EPA along with the corresponding regular sample. Any statistical analysis
of the time storage data will be conducted by EPA.
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Section No 11
Revision No. 3
Date. August 1, 1990'
Page 7 of 7
TABLE 11-2
TIME STORAGE STUDY SCHEDULE
Sample
LSb
TSOb
TSlb
TS2b
Spike Time*
(days)
Within 14 days of
collection
Within 14 days of
collection
Within 14 days of
collection
Within 14 days of
collection
Extraction Time
(days)
Within spike time +
4 days
Within spike time +
4 days
At 14 ±4 days of
spike
At 14 ±4 days of
spike
Analysis Time
(days)
Within spike time
+ 4 days
Within spike time
+ 4 days
Within 4 days of
extraction
Within 4 days of
extraction
Reanalysis
At 14 _+ 4 days
of spike
At 14 +. 4 days
of spike
Not analyzed
Not analyzed
aAII samples are to be spiked the same day.
bEPA designations.
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Section No 12
Revision No. 3
Date: August 1, 1990
Page 1 of 16
12. PERFORMANCE AND SYSTEMS AUDITS
A quality assurance (QA) audit is an independent assessment of a measurement system. It
typically includes performance evaluation using apparatus and/or standards that are different from
those used in calibrating the measurement system. It also may include an evaluation of the potential
of the system to produce data of adequate quality to satisfy the objectives of the measurement efforts.
The independent, objective nature of the audit requires that the auditor be functionally independent of
the sampling/analytical team. Quality assurance audits play an important role in Radian's overall
QA/QC program. Radian has an independent quality assurance group that routinely conducts
systems audits of the various corporate laboratories. Since this program required the preaward
analyses of performance evaluation samples, only one additional internal performance audit is planned
during each year of this work. This section describes the role of the QA auditor and the nature of
both performance and systems audits.
The QA auditor is the person who designs and/or performs QA performance and systems
audits. Since QA audits represent, by definition, independent assessments of a measurement system
and associated data quality, the auditor must be functionally independent of the measurement effort to
ensure objectivity. However, the auditor must be familiar enough with the objectives, principles, and
procedures of the measurement efforts to be able to perform a thorough and effective evaluation of
the measurement system. Especially important is the ability to identify components of the system
which are critical to overall data quality, so that the audit focuses heavily upon these elements. The
auditor's technical background and experience should also provide a basis for appropriate audit
standard selection, audit design, and data interpretation.
The function of the QA audits is to:
Verify the procedures and techniques employed in the various measurement efforts,
including field sampling and laboratory operation;
Check and verify records of calibration;
Assess the effectiveness of and adherence to the prescribed QC
procedures;
Review document control procedures;
Identify and correct any weaknesses in the sampling/analytical approach and
techniques;
Assess the overall data quality of the various sampling/analytical systems; and
Challenge the various measurement systems with audit standards.
Generally, the role of the auditor is to observe and document the overall performance of each of
the various sampling and analytical efforts (systems audits), and use audit standards and test
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Section No 12
Revision No. 3
Date. August 1, 1990'
Page 2 of 16
equipment which are traceable to acceptable reference standards to assess the performance of each
analytical method and/or measurement device (performance audit).
12.1 SYSTEMS AUDIT
A systems audit is an on-site qualitative review of the various aspects of a total sampling and/or
analytical system to assess its overall effectiveness. It represents a subjective evaluation of a set of
interactive systems with respect to strengths, weaknesses, and potential problem areas. The audit
provides an evaluation of the adequacy of the overall measurement system(s) to provide data of
known quality which are sufficient, in terms of quantity and quality, to meet the program objectives.
The systems audit consists of observing the various aspects of the project sampling and
analytical activities. Checklists which delineate the critical aspects of each methodology area are used
by the Radian auditor during the systems audit and serve to document all observations. An example
systems audit checklist used to evaluate a typical laboratory is illustrated in Figure 12-1. This checklist
was designed to evaluate sample handling, analytical procedures documentation, data quality
assessment practices, and data processing procedures. The systems audit emphasizes review of all
recordkeeping and data handling systems including:
Calibration documentation for both instruments and apparatus;
Completeness of data forms;
Data review and validation procedures;
Data storage and filing procedures;
Sample logging procedures;
Sample custody procedures;
Documentation of QC data, for example, control charts;
Documentation of equipment maintenance activities; and
Review of malfunction reporting procedures.
Upon completion of the audit, the auditor discusses any specific weaknesses with the project
team and makes recommendations for corrective action. An audit report is subsequently prepared
and distributed to the Task Leaders and the Project Director. This report outlines the audit approach
and presents a summary of results and recommendations. Systems audits are planned on a regular
basis for the Radian chromatography laboraiory in addition to the regular laboratory audits, a yearly
project specific audit will be performed for the NPS study.
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Section No. 12
Revision No. 3
Date: August 1, 1990
Page 3 of 16
FIGURE 12-1
LABORATORY SYSTEMS AUDIT CHECKLIST
LABORATORY STSTEMS AUDIT CHECKLIST - PART 1 GENERAL PROCZDURZS
Laboratory; Date;
Location: Auditor:
Yea
No
Coi
nc»
Operation
A. Documentation of Procedure*
I. Does tht laboratory maintain
Quality Control SOPs?
2. Does the SOP address ch* important
elements of a QC program including
ch« following:
a. Personnel?
b. Facilitita and equipment?
c. Operations of inatruaanta}
d. InatruMnt calibration?
t. Inatruawnt control aaa««aa*nt
(quality control proctdurca
and acceptance criteria)?
f. Documentation of procedurea?
g. Preventative aaintenance?
h. Reliability of data?
i. Data validation?
j. Feedback and corrective
action?
3. Are all required calculations
documented for each analytical
aecbod employed?
A. la the procedure for determining
significant figures* documented
and applied for each analysis?
5. Is the procedure for "rounding"
documented snd uniformly applied?
6. Are there documented procedures
for determining method detection
limits?
7. Are the guidelines used for deter-
mining precision and bias docu-
aented? (If not. describe the
procedures used.)
GEMPn-O.QO.
Revision 0
9/22/36
Pag* 1
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Section No. 12
Revision No. 3
Date: August 1, 1990
Page 4 of 16
FIGURE 12-1 (continued)
LABORATORY SYSTEMS AUDIT CHECKLIST
LA80RATORT STSTZMS AUDIT CHECKLIST - PART 1 GENERAL PROCEDURES (Cont.)
Tec No Constant* Operation
A. Documentation of Procedures (Cont.)
Additional Comments:
3. Art tht procedure* for identifying
outliers documented and applied?
9. Are the laboratory precision and
accuracy objective* (acceptance
criteria) for each method docu-
aented?
10. Are the procedure* documented for
corrective action when QC results
do not atec establiahed acceptance
criteria?
11. Are the procedure* for daca tran-
scription and processing docu-
mented?
12. Are the documents containing the
procedures listed above accessible
to all laboratory personnel?
13. Are daily logs kept in a non-
erasable medium?
14. Is each, entry dated and signed by
the author?
IS. Are entries concise, complete, and
legible?
16. Are changes to the daily log dated
and initialed by the person making
the change?
17. Are explanations for changes given
when required?
18. Does a supervisor periodically
review daily logs for content and
completeness (evidenced by ini-
tials and date)?
frequency;
GE»Tl-O.Cn. Revision 0 9/22/86 ?« 2
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Section No. 12
Revision No. 3
Date: August 1, 1990
Page 5 of 16
FIGURE 12-1 (continued)
LABORATORY SYSTEMS AUDIT CHECKLIST
LABORATORY STSTEMS AUDIT CHECKLIST - PART 1 GENERAL PROCEDURES (Cone.)
Yes No Comments Operation
B. Sample Receipt and Storage
1. Is a sample custodian designated?
If yes, name of sample custodian?
Name:
2. Arc there written Standard Opera-
ting Procedure* (SOPs) for receipt
and ctorage of samples?
3. Is the appropriate portion of the
SOP available to the analyst at
the cample receipt/storage area?
A. Are the sample chipping containers
opened in a manner which prevents
possible laboratory contamination?
5. Is there a procedure for docu-
menting receipt of samples that
are damaged?
6. Are samples that require preserva-
tion stored in such a way as to
maintain their preservation?
7. Are adequate facilities provided
for storage of samples, including
cold storage?
8. Is the temperature of the cold
storage recorded daily in a log-
book?
9. Are the sample receipt/storage and
temperature logbooks maintained in
a manner consistent with good
laboratory practice?
10. Has the supervisor of the indivi-
dual maintaining the notebook per-
sonally examined and reviewed the
notebook periodically and signed
his/her name therein, together
with the date and appropriate
comments as to whtnar or not the
notebook is being maintained in an
appropriate manner?
Additional Comments:
GXim-O.CKL Revision 0 9/22/8* Page 3
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Section No. 12
Revision No. 3 ,
Date: August 1. 1990
Page 6 of 16
FIGURE 12-1 (continued)
LABORATORY SYSTEMS AUDIT CHECKLIST
LABORATORY STSTZMS AUDIT CHECKLIST - PART 1 GZXERAL PROCEDURES (Cone.)
Tec No Command Operation
C. Sample Preparation
1. Is the laboratory maintained in a
clean and organized Banner?
2. Doe* tbt laboratory appear to have
adequate workspace (120 so. ft.. 6
linear ft. of unencumbered bench
space per analyat)?
3. Are the toxic chemical handling
areaa either a atainleaa cteel
bench or an impervious material
covered with abaorbent material?
A. Are contamination-free areaa pro-
vided for trace level analytical
work?
5. Are exhauat hood* provided to
allow contamination-free vork with
volatile material!?
6. If the air flow of the hooda
periodically checked and recorded?
7. Are chemical waate dispoaal poli-
cies/procedure* adequate?
8. Does the laboratory have a aource
of distilled/deionized water?
9. la the conductivity of diatilled/
deionised water routinely checked
and recorded?
10. la the analytical balance located
away from draft and areaa cubject
to rapid temperature change*?
11. Haa that balance been calibrated
within one year by a certified
technician?
12. la the balance routinely checked
with Claaa S weight* before each
uae and the reaulca recorded in a
logbook?
13. la the «ample preparation portion
of the SOP available to the ana-
lyat ac the sample preparation
area?
GXWT1-O.OI. Reviaion 0 9/22/M ? *
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Section No. 12
Revision No. 3
Date: August 1, 1990
Page 7 of 16
FIGURE 12-1 (continued)
LABORATORY SYSTEMS AUDIT CHECKLIST
LABORATORY STSTZMS AUDIT CHECKLIST - PAST 1 GENERAL PROCEDURES (Cont.)
Yea
No
nta
Operation
C. Sample Preparation (Cont.)
14. Art reagent grade or higher purity
chemical* uaed to prepare ctan
darda?
15. Are freab analytical standarda
prepared at a frequency conaiatent
with maintaining aolution integ-
rity?
16. Are reference material* properly
labeled with concentrationa. date
of preparation, and the identity
of the peraon preparing the sam-
ple?
17. la the standard* preparation and
tracking logbook maintained?
18. Do the analyata record bench data
in a neat and accurate manner?
19. Are standard* atored separately
from samples?
20. la the SOP for glaeevare washing
poated at the cleaning atatio'n?
Additional Comment*:
D. Sample Tracking
1. Can you aelect a sample number
from the maater log and locate the
original sample container*?
2. Are the chain-of-custody scale
properly filled out for samples in
storage?
3. Can you identify and locate sample
extracts, digestion*, and/or dia-
solutiona made from an original
ample?
4. For digeationa. extraction*, and
diaaolutiona. are the date, condi-
tion*, and name of the person
performing the procedure noted on
the sample or chain-of-cuatody
sheet*?
GiHm-o.cn.
Rarviaioa 0
9/22/1
Pag* 5
-------
Section No. 12
Revision No. 3 ,
Date: August 1. 1990
Page 8 of 16
FIGURE 12-1 (continued)
LABORATORY SYSTEMS AUDIT CHECKLIST
LABORATORY STSTZMS AUDIT CHECKLIST - PART 1 GZXERAL PROCEDURES (Cent.)
Yes No Command Operation
D. Sample Tracking (Cont.)
Additional Comment*:
5. Can you find the analytic result*
for on* of the pic* froa the
original sample number?
6. Arc the calibration date* corres-
ponding co sample analysis pro-
perly documented and viebin toler-
ances?
7. Are quality control data for theee
data properly documented and
within tolerance*!
8. Have the data been spot-checked
for calculation errors?
9. Have these data been reviewed
(evidenced by reviewer* initial*
and date of review)7
10. Are problem* and/or control data
anomalies adequately noted on the
data report?
1. Do re*pon*e* to the evaluation
indicate that laboratory and
uperviaory personnel are aware of
QA/QC and it* application to the
laboratory mission?
2. Do laboratory and supervisory per-
sonnel place positive emphasis on
QA/QC?
3. Have re*pon*e* with respect to
QA/QC scpectc of the laboratory
been open and direct?
4. Ha* a cooperative attitude been
displayed by all laboratory and
supervisory personnel?
S. Doe* the laboratory place the
proper emphasis on quality assur-
ance?
CZNPTl-0.cn. Revision 0 9/22/86 Page 6
-------
Section No. 12
Revision No. 3
Date: August 1, 1990
Page9 of 16
FIGURE 12-1 (continued)
LABORATORY SYSTEMS AUDIT CHECKLIST
LABORATORY STSTZMS AUDIT CUSOO.IST - PART 1 GENERAL PROCEDURES (Cone.)
Tt«
Comaent >
Operation
Addition*! Coooents:
E.
6.
ry (Cone.)
Have any QA/QC deficiencies been
discussed before leaving?
7. It the overall quality assurance
adequate to accomplish the objec-
tives of the laboratory?
3. Have corrective aceiona recoar-
nended during previous evaluations
been implemented? If not. provide
detaila.
GBe?Tl^>.C&. lurriaion 0
9/22/86
Pat* 7
-------
Section No. 12(
Revision No. 3
Date: August 1, 1990
Page 10 of 16
FIGURE 12-1 (continued)
LABORATORY SYSTEMS AUDIT CHECKLIST
LABORATORY SYSTEMS AUDIT CHZOaiST - PART 2 INSTRUMENTAL METHODS
Instrument^
Analyst:
Date:
Auditor:
Yes
No
Co:
nts
Op«ration
A. General Instrumentation Procedures
1. Art writttn Standard Operating
Procedures documenting analytical
protocol available?
2. Arc tb« SOP* sufficiently de-
tailed?
3. Are manufacturer's operating
manual* readily available to the
operator?
4. Hae the in«tnu»ent been modified
in any way?
5. Is electronic data storage used?
6. Is the instrument properly vented
or are appropriate traps in place?
7. °Is there a documented preventative
oaintenance program?
8. Is service Maintenance by con-
tract?
9. Is a permanent service record
maintained in a logbook?
10. Are adequate in-house replacement
parts available?
Additional Comments:
Revision 0
9/22/M
Page 1
-------
Section No. 12
Revision No. 3
Date: August 1, 1990
Page 11 of 16
FIGURE 12-1 (continued)
LABORATORY SYSTEMS AUDIT CHECKLIST
LABORATORY STSTTMS AUDIT CHECKLIST - PART 2 INSTRUMENTAL METHODS (Cont.)
Yt«
No
Comaents
Operation
B. Calibration Procedure*
1. Is there a logbook or ochtr per-
manent record documenting prepara-
tion of calibration standard*.
including date, analyit. and
source of standard material*?
2. Can the calibration (tandard* in
uce by traced to the above docu-
mentation?
3. Are calibration procedure* docu-
mented in a written SOP or labora-
tory Manual?
4. Are written procedure* suffi.-
ciently detailed?
5. Are calibration data kept in a
permanent record?
6. I« the calibration frequency
clearly specified?
7. Do record* indicate that calibra-
tion* are typically performed at
the specified frequency?
8. Are definitive calibration accep-
tance criteria clearly specified?
9. Are control chart* used to track
calibration performance (e.g..
slope, intercept, etc.)?
10. Are corrective action procedure*
specified for failure to achieve
calibration acceptance criteria?
11. Are theee corrective action* docu-
mented?
Additional Coaaents:
cnvT2-o.cn.
Reviaion 0
9/Z2/M
Page 2
-------
Section No. 12
Revision No. 3 >
Date: August 1. 1990
Page 12 of 16
FIGURE 12-1 (continued)
LABORATORY SYSTEMS AUDIT CHECKLIST
STSTEMS AUDIT CHECKLIST - PART 2 INSTRUMENTAL METHODS (Cone.)
Tea No Conjunct Operation
C. Internal Quality Control
1. Are specified internal quality
control check* identified for the
analytical procedures such «:
Additional Coowents:
a. Laboratory blanks?
b. Duplicate analyses?
c. Spiked saoples?
d. Analysis of QC check stan-
dards?
«. Other?
Are frequencies clearly specified
for each of the internal QC
checks?
Are acceptance criteria specified
for each of the internal QC
checks?
Are control charts used to track
results for the internal QC
checks?
Are corrective action procedures
specified for QC results which
fail to Met acceptance criteria
(i.e.. fall outside control
liaits)?
Are theae corrective actions docu-
mented?
D. Data Handling Procedures
1. Are hardcopy data available for
each typ« of analysis (strip
chart, printout, etc.)?
2. Is the nethod detection linie for
each Mthod checked on a regular
frequency?
Frequency;
3. Are all data routinely assessed
for precision and bias?
GXWtt-O.Cn. Revision 0 */22/M ?!
-------
Section No. 12
Revision No. 3
Date: August 1. 1990
Page 13 of 16
FIGURE 12-1 (continued)
LABORATORY SYSTEMS AUDIT CHECKLIST
LABORATORY SYSTEMS AUDIT CHECKLIST - PART 2 INSTRUMENTAL METHODS (Cone.)
Tea No Comments Operation
D. Data tUndling Procedures (Cont.)
4- It cbcr* « rtcord of the deter-
aination of precision and bias for
aca rt«ult?
5. Do supervisory personnel review
che data and QC results?
6. Are data reviewed by experienced
personnel for representativeness
nd comparability?
7. Are data calculation* spot-checked
by a second per*on (evidenced by
initial*)7
8. Do record* indicate corrective
action that haa been taken on data
rejected baaed on incorrect calcu-
lation*?
9. Haa the peraon reviewing the data
and- QC results signed his/her name
therein, together with the date
and appropriate comments aa to
whether the data are documented in
a complete and appropriate manner?
10. Are laboratory data recorded in
standard format*?
11. Do data reported indicate proper
units?
12. Are cample dilution* documented?
13. Have report forma been developed
to provide complete data documen-
tation* co facilitate data pro-
ceaaingl
14. la there an individual responsible
for checking data transcription*?
(Can the individual be identi-
fied!)
Name:
IS. la there an individual responsible
for maintaining data files?
Name i
16. Are backup copiea of raw data
kept?
Glira-O.CXX. Raviaion 0 9/22/M Page 4
-------
Section No. 12
Revision No. 3 .
Date: August 1, 1990
Page 14 of 16
FIGURE 12-1 (continued)
LABORATORY SYSTEMS AUDIT CHECKLIST
UUORATORT STSTEMS AUDIT CHECKLIST - PART 2 INSTRUMENTAL HETHODS CCont.)
Ye« No Comment Operation
D. 3ata Handling Procedure* (Cone.)
Additional Cosaant*:
17 . Are backup copie* of data ba*c*
kept in a difftrent location than
the working copy?
18. Are the computer program* uced to
procec* raw data documented and
validated?
19. Are reaaona given for missing
sample* or data?
Revision o 9/22/86 ' 5
-------
Section No 12
Revision No 3
Date: August 1, 1990
Page 15 of 16
12.2 PERFORMANCE AUDITS
Initial
A performance audit will be conducted at the initiation of the NFS project. The QA auditor will
prepare standard samples and submit them to the laboratory as unknown samples. These samples
will be prepared from the stock standard solutions, not secondary standards, so an independent
measure of preparation can be obtained. Results of the QA audit will be submitted to the project
director for review and correction of any problems which were identified during the audit. This audit is
not required by EPA as a part of this project.
On-Going
Performance evaluation (PE) samples will be sent quarterly to the laboratory by the NPS Quality
Assurance Officer (QAO). Each quarter the QAO will consult the Method 4 Technical Monitor for
recommendations on the analytes and on the analyte levels that should be included in the samples.
The samples will be prepared in acetonitrile, verified by the EPA referee lab and then shipped to the
lab in sealed glass ampules with instructions for analysis. Radian will be expected to report their
results to the Technical Monitor in memo form by the study deadline as well as in the standard format
required for all Survey samples. A minimum of three weeks will be allotted for the analysis and
reporting activities associated with participation in the PE study.
The results will be evaluated both qualitatively and quantitatively. Qualitative acceptance criteria
will be based on correct identification of all analytes known to be present in the PE sample and no
false positives.
Quantitative acceptance criteria for the samples will be based on a statistical comparison of
Radian's results with those achieved by the referee lab. -Specifically, the referee lab will be asked to
report seven values for the PE standard, so that using equation 12-1, a 99% confidence interval using
the Student's "T" distribution can be constructed around the mean of the referee laboratory's results.
* ± «(t|^in.1)(s)V( n )) (Equation 12-1)
where: x = mean
t = value from Students T" distribution for an a of .005 and (n-1)
degrees of freedom
s = standard deviation
n = sample size
A confidence interval will likewise be constructed around the single value reported by Radian.
However, rather than requesting multiple analyses to generate a value for standard deviation (s), the
standard deviation will be taken from the control charts that were in effect at the time the PE was
analyzed. Since the control charts are kept in terms of percent recovery, the PE results will be
-------
Section No 12
Revision No. 3
Date: August 1, 1990
Page 16 of 16
converted to a percent recovery based on theoretical true" value. The confidence interval based on
percent recovery will then be converted to a range of concentrations. Criteria for acceptable
performance will be that the confidence intervals generated from the referee analysis must overlap by
at least one point with the confidence intervals generated from Radian's analysis.
A report of Radian's performance will be prepared by the NPS QAO in conjunction with a Survey
statistician. Distribution of the report will include the Radian project manager, the Method 4 Technical
Monitor, the Survey Director, the ODW and OPP QAOs, and the Analytical Coordinator for Method 4.
-------
Section No 13
Revision No. 3
Date: August 1, 1990
Page 1 of 1
13. PREVENTATIVE MAINTENANCE
The primary objective of a comprehensive preventative maintenance program is to help ensure
the timely and effective completion of a measurement effort. The Radian preventative maintenance
(PM) program is designed to minimize the down time of crucial sampling and/or analytical equipment
due to expected or unexpected component failure. In implementing this program, efforts are focused
in three primary areas:
Establishment of maintenance responsibilities;
Establishment of maintenance schedules for major and/or critical
instrumentation and apparatus; and
Establishment of an adequate inventory of critical spare parts and
equipment.
13.1 MAINTENANCE RESPONSIBILITIES
Maintenance responsibilities for permanently assigned equipment is assigned to the laboratory
manager. The laboratory manager then establishes maintenance procedures and schedules for each
major equipment item. Specific responsibilities for specific items may be delegated to laboratory
personnel, although the laboratory managers retain responsibility for ensuring adherence to
prescribed protocol.
13.2 MAINTENANCE SCHEDULES
The effectiveness of any maintenance program depends to a large extent on adherence to
specific maintenance schedules for each major equipment item. A specific schedule is established for
all routine maintenance activities. Other maintenance activities may also be identified as requiring
attention on an as-needed basis. Manufacturer's recommendations provide the primary basis for the
established maintenance schedules. Maintenance activities will be documented in a maintenance log
which indicates the required-frequency for each procedure and provides for dated entries.
13.3 SPARE PARTS
Along with a schedule for maintenance activities, an adequate inventory of spare parts is
required to minimize equipment down time. This inventory emphasizes those parts (and supplies)
which:
Are subject to frequent failure;
Have limited useful lifetimes; or
Cannot be obtained in a timely manner should failure occur.
In addition to maintaining a large inventory of spare parts and supplies, Radian's non-assigned
equipment represents an extensive in-house source of back-up equipment and instrumentation.
-------
Section No 14
Revision No 3
Date. August 1, 1990*
Page 1 of 2
14. ASSESSMENT OF PRECISION, ACCURACY, AND COMPLETENESS
The purpose of this program is to provide EPA with data on the analyses of samples for EPA
National Survey of Pesticides. Successful execution of the analytical program will also involve
determination of laboratory precision and accuracy. For the purposes of this program, Radian will
initially determine precision and accuracy based on results of the initial demonstration of capabilities
according to the criteria outlined in Section 5.
14.1 PRECISION
For this program, the initial accuracy estimates will be based on the recovery of surrogate
spikes and the recovery of known analytes in the initial demonstration of capabilities. If the unspiked
sample contains a response greater than or equal to one-half the MRL, that area will be subtracted
from the spiked sample before calculating percent recovery. The percent recovery will be calculated
where:
The precision of Method 4 was monitored on an on-going basis throughout the project through
the use of control charts for each of the analytes. A total of 20 data points were obtained from the
initial demonstration of capabilities which provided mean recoveries and relative standard deviations
for each analyte. After the initial demonstration, the control charts were updated every five sample
sets by dropping the five oldest points and adding the five most recent recoveries from the laboratory
eontrol samples. New means and relative standard deviations were calculated and used as a
measure of precision during the survey.
14.2 COMPLETENESS
Measurement data completeness is a measure of the extent to which the database resulting
from a measurement effort fulfills objectives for the amount of data required. This is typically
expressed in one of the following two ways:
Valid data percentage of the total tests conducted; or
Valid data percentage of the total tests scheduled.
For this project, completeness will be defined as the percentage of valid data for the total tests
conducted.
-------
Section No. 14
Revision No. 3
Date: August 1, 1990
Page 2 of 2
14.3 CALCULATION FORMULAS FOR INTERNAL QC CHECKS AND STATISTICS
Calculation formulas for percent recovery, standard deviation, peak symmetry factor, and peak
Gaussian factor can be found in Section 10 of Method 4.
Control limits on the control charts will be used as designated in Method 4. A warning limit of ±
2X RSD will be established with a control limit of +. 3X RSD.
-------
Section No. 15
Revision No. 3
Date: August 1, 1990
Page 1 of 5
15. CORRECTIVE ACTION
During the course of a measurement program, the task leaders assume responsibility for
ensuring that all measurement procedures are followed as specified and that measurement data meet
prescribed acceptance criteria. In the event a problem arises, it is imperative that prompt action be
taken to correct the problem. The measurement task leader will initiate corrective action in the event
of QC results which exceed acceptability limits. Acceptability limits and prescribed corrective action
related to the internal QC checks will be clearly specified and documented, as discussed in Section
11. The task leader will initiate a corrective action report form (CAR) describing the problem. A copy
will be sent to all persons involved in the project. The problem will be resolved and the corrective
action recorded on the CAR form. The report form will be filed with the appropriate sample folders.
An example corrective action report form is shown in Figure 15-1.
Corrective action may be initiated by the QA coordinator based upon QC data or audit results.
Problems signaling significant and systematic deficiencies are addressed with a Recommendation for
Corrective Action (RCA, Figure 15-2). RCAs are issued only by members of the Quality Assurance
Group (or by their designee in a specific QA assignment). Each RCA addresses a specific problem or
deficiency, usually as a result of a QA audit.
Each RCA requires a written response from the responsible party (i.e., the party to whom the
RCA was issued). A database is used to track RCAs and responses. On a monthly basis a summary
of the unresolved RCAs is prepared by the QA group and submitted to Radian management. These
reports list all RCAs that have been issued to the work areas that each manager is responsible for,
and the current status of each. Each RCA requires the response and verification by the QA group
that the corrective action has been implemented before trie status is changed on the monthly report.
If there is no response to an RCA within 30 days, or if the proposed corrective action is disputed, the
recommendation and/or conflict is pursued to successively higher management levels until the issue is
resolved. The corrective action scheme is shown in the form of a flow chart in Figure 15-3.
When corrective action is necessary in the course of the project, the problem and corrective
action taken will be reported in the monthly progress reports to the technical monitor. The samples
analyzed immediately prior to and immediately following the corrective action will be identified so that
any anomalies observed in the data may be correlated to the corrective action.
-------
Section No. 15
Revision No. 3
Date: August 1, 1990
Page 2 of 5
FIGURE 15-1
CORRECTIVE ACTION REPORT FORM
Corrective Action Report (CAR)
Pirtl limn \atwmrtn (FuratoiMd by Originator)
Originator Urgency Level:
SAMf: Method*: Hequires retoiution for immediate job
Qto*: Matnx: Requires resolution tor future |00«
Date:
To Person ResponsiWe tor Action:
Sit* / Lib: Type: QC Umrt Z Documcmition Sy««m ~ Other ~
Oat* / Time identified:
Description of Situation: (attacn supporting data if available)
OefcnpooK implemented oy.
-------
Section No. 15
Revision No. 3
Date: August 1, 1990
Page 3 of 5
FIGURE 15-1 (continued)
CORRECTIVE ACTION REPORT FORM
Part II Raply / Btsolutton (FumislMd by Tedmleal Director)
I by: Dlt«: CAR »:
Dncnpoon: SctoduMd impMnwnution:
Part in Imptoanatid Correction Action (by:
DMcnpoon: Oat*
Part IV FoflMMIp lUyrtnrt: Y«s D M> u (byt
VwUtod by: Daw: CommwitK
-------
Section No. 15
Revision No. 3
Date: August 1. 1990
Page 4 of 5
FIGURE 15-2
RECOMMENDATION FOR CORRECTIVE ACTION FORM
ACMAACM 4
RECOMMENDATION FOR CORRECTIVE ACTION
A. Initial IntenmMon
OMAMU0MNMOV10
UMNO OQMCCnvC
ACTON:
C. QA VwtfteMton
Action
URGENCY LEVEL
sin
3«rt
-------
Section No. 15
Revision No. 3*
Date: August 1, 1990
Page 5 of 5
FIGURE 15-3
CORRECTIVE ACTION FLOW SCHEME
TO
rtt MCA Oft
TIAM IXA0CN
MfTIAL
VALUATION
-------
Section No 16
Revision No. 3
Date: August 1, 1990
Page 1 of 2
16. QUALITY ASSURANCE REPORTS TO MANAGEMENT
Radian's corrective action plan is described in Section 15 of this document. An integral part of
the corrective action plan is the corrective action report form which is submitted to the project director
and appropriate task leaders when a problem is identified through audits, control charts, or other QC
checks in place in the laboratory. Use of the CAR is a standard procedure in Radian's laboratories
where it has been found to be an excellent method for alerting management to a problem and
bringing about its swift resolution. Radian conducts periodic systems audits of the laboratories to
qualitatively assess overall system performance. Radian will arrange to perform at least one systems
audit of the laboratory during each year's operations and one project specific audit per year.
Audit reports consist of a completed checklist (Figure 12-1) and a summary of the findings of
the audit in the order of introduction, recommendations for corrective action, discussion, and status of
previous recommendations. Major deficiencies will result in a Recommendation for Corrective Action
(RCAs), as mentioned in Section 15. Minor deficiencies or deviations from SOPs are outlined in the
discussion section of the report.
Strong management coupled with the QA control and reporting mechanism specified in this
QAPP will ensure effective control and interaction between the project director, the task leaders, peer
reviewer, and the QA coordinator. The reporting mechanism to be established to keep the Technical
Monitor informed of problems and progress is also very important. The mechanism for interaction with
the Technical Monitor will be the use of monthly progress reports. The format of the monthly progress
reports has been specified by EPA and a copy is provided as Figure 16-1. These reports will be sent
to the Technical Monitor within 15 days of the end of the reporting period.
-------
Section No. 16
Revision No. 3 i
Date: August 1, 1990
Page 1 of 2
16. QUALITY ASSURANCE REPORTS TO MANAGEMENT
Radian's corrective action plan is described in Section 15 of this document. An integral part of
the corrective action plan is the corrective action report form which is submitted to the project director
and appropriate task leaders when a problem is identified through audits, control charts, or other QC
checks in place in the laboratory. Use of the CAR is a standard procedure in Radian's laboratories
where it has been found to be an excellent method for alerting management to a problem and
bringing about its swift resolution. Radian conducts periodic systems audits of the laboratories to
qualitatively assess overall system performance. Radian will arrange to perform at least one systems
audit of the laboratory during each year's operations and one project specific audit per year.
Audit reports consist of a completed checklist (Figure 12-1) and a summary of the findings of
the audit in the order of introduction, recommendations for corrective action, discussion, and status of
previous recommendations. Major deficiencies will result in a Recommendation for Corrective Action
(RCAs), as mentioned in Section 15. Minor deficiencies or deviations from SOPs are outlined in the
discussion section of the report.
Strong management coupled with the QA control and reporting mechanism specified in this
QAPP will ensure effective control and interaction between the project director, the task leaders, peer
reviewer, and the QA coordinator. The reporting mechanism to be established to keep the Technical
Monitor informed of problems and progress is also very important. The mechanism for interaction with
the Technical Monitor will be the use of monthly progress reports. The format of the monthly progress
reports has been specified by EPA and a copy is provided as Figure 16-1. These reports will be sent
to the Technical Monitor within 15 days of the end of the reporting period.
-------
Section No. 16
Revision No. 3
Date August 1, 1990
Page 2 of 2
FIGURE 16-1
FORMAT FOR MONTHLY REPORTS
Six copies of the monthly report are to be provided within 15 (calendar) days after the end of
the period being reported. The copies are to be sent to the appropriate EPA Technical Monitor.
A copy of the cover letter which transmits the monthly report is to be forwarded to Mona S.
Synder, Contract Specialist for the NPS, EPA-CMD, Cincinnati, Ohio, 45268.
The report format should contain the following information for the report period:
Summary of Progress - samples received, analyzed, in progress
status of data processing for analyzed sets of samples
Reports on Standards - new dilutions and results of check before using
Summary list of bench-level corrective actions
Identification of problems about any phase of the project
Copies of representative and, if applicable, unusual chromatograms. (Check with
Technical Monitor for needs)
Information requested by the Technical Monitor because of specific methodology or
problems encountered
Changes in personnel (analysts)
Comments
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Section No 17
Revision No 3
Date- August 1, 1990
Page 1 of 2
17. DATA ARCHIVAL
The National Pesticide Survey has sampled approximately 1350 drinking water well sites across
the United States. Due to the large amount of data collected, a detailed archival procedure is
necessary so that raw data and other materials generated during the course of this project may be
readily available for reference purposes.
Data archival will be conducted in accordance with the following guidelines:
Scope: All data and other materials that have been generated either through the
analytical effort or the implementation/data synthesis effort will be archived. This
includes hard copy and/or electronic media and any formal documents used for the
Survey.
Accessibility: Materials will be managed so that they can be accessed within 5 to
10 working days. Access to materials will be limited to Radian staff and
representatives of the EPA.
Length of Storage: At a minimum, all materials will be stored until October of 1992.
After this date, the Survey Director (or his designee) will be contacted for permission
to purge Survey data/documents. All Survey materials are subject to surrender to
EPA at any time.
Privacy Act: Radian will manage the Survey records in a manner which will
guarantee confidentiality of recorded information on individuals involved in the
Survey in accordance with the Privacy Act (5 U.S. Code 552a).
Analytical data collected during the analysis of samples under Method 4 will be archived by
sample set. Each set will contain data on the particular samples analyzed in that set, plus any
documentation accompanying the samples. A master sample list will be prepared which will list the
sample set, NPS field sample numbers, Radian internal sample control numbers (SAM designations),
and date of collection. Using this system, data for any particular sample will be traceable through set
number, date collected, field identification or Radian SAM number. Data will be stored in numbered
file boxes marked with the applicable sample set numbers. File boxes will be stored in a Radian
warehouse and will be accessible through the file control number. All data will be stored through
1992 unless EPA either requests the data or requests that it be destroyed. No data will be destroyed
without written permission from the Survey Director.
Additional items to be archived include data from the initial demonstration of capabilities, results
from the PE samples, training records, project notebooks, control charts, copies of computer
programs, NPS correspondence, contractual information, the QAPjP, copies of NPS formatted results
and monthly reports. These documents will be archived in individual files which are not associated
with the sample sets.
For each sample set, the following information will be included in the individual set folders.
Extraction project work plan. (See Figure 7-3)
Sample worksheet for chromatography. (See Figure 7-4)
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Section No 17
Revision No. 3
Date: August 1, 1990
Page 2 of 2
. Sample tracking form (from ICF) and Federal Express Airbill.
« Water WISP automatic sample injection system sample identification
record.
Chromatograms.
Quantitation reports.
Daily quality control checklist (Figure 8-1)
Instrument QC standard chromatogram and calculations.
LAS print-out.
The Radian contact for data retrieval will be Larry Ogle. He will be responsible for maintaining
NFS records and a list of the archived materials and how they can be retrieved. In his absence, the
point of contact will be the Radian Analytical Services Technical Director.
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Appendix A
Revision No. 3
Date- August 1, 1990
Page 1 of 36
APPENDIX A
METHOD 4. DETERMINATION OF PESTICIDES IN GROUND WATER BY
HIGH PERFORMANCE LIQUID CHROMATOGRAPHY WITH AN ULTRAVIOLET DETECTOR
-------
ill!
Method 4. Determination of Pesticides in Ground Water by High
Performance Liquid Chromatography with an Ultraviolet Detector
1. SCOPE AND APPLICATION
1.1 This is a high performance liquid chromatographic (HPLC) method
applicable to the determination of certain analytes in ground
water. Analytes that can be determined by this method are
listed in Table 1.
1.2 This method has been validated In a single laboratory. Esti-
mated detection limits (EDLs) have been determined and art
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 ust by or undtr the supervision of
analysts experienced in the use of liquid Chromatography and in
the interpretation of liquid chromatograms. Each analyst must
demonstrate the ability to generate acceptable results with this
method using the procedure described in Section 10.2. k
1.4 When this method is used to analyze unfa»1!1ar samples for any
or all of the analytes above, analyte Identifications must be
confirmed by at least ont additional qualitative technique.
2. SUMMARY OF METHOD
2.1 A measured volume of sample of approximately 1 L is solvent
extracted with methylene chloride by mechanical shaking in a
separatory funnel or mechanical tumbling in a bottle. The
methylene chloride extract is isolated, dried and concentrated
to a volume of 5 mi after solvent substitution with methanol.
Chromatographic conditions are described which permit the
separation and measurement of the analytes in the extract-by
HPLC with an ultraviolet (UV) detector.1-2
2.2 An alternative manual liquid-liquid extraction method using
separatory funnels 1s also described.
3. DEFINITIONS
3.1 Artificial ground water -- an aqueous matrix designed to mimic
characteristics of a real ground water sample. Artificial
ground waters should be reproducible for validations performed
in other laboratories.
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.
1
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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 deter-
mined from the analysis of a sample in a given matrix containing
the analyte. The EDL is equal to the level calculated by
multiplying the standard deviation of replicate measurements
times the students' value appropriate for a 99 percent con*
fidence level and a standard deviation estimated 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 measure-
ments 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 - a methanol solution
containing specified concentrations of specified analytes. The
instrument QC standard 1s analyzed each working day prior to the
analysis of sample extracts and calibration standards. The
performing laboratory uses this solution to demonstrate accep-
table Instrument performance in the areas of sensitivity, column
performance, and chromatographlc performance.
3.6 Laboratory control (1C) standard - a solution of analytes
prepared in the laboratory by dissolving known amounts of pure
analytes in a known amount of reagent water. In this method,
the LC standard is prepared by adding appropriate volumes of the
appropriate standard solution to reagent water.
3.7 Laboratory method blank -- a portion 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.
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3.10 Stock standard solution -- a concentrated solution containing i
certified standard that is a method analyte, or a concentrated
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 bt caused by contaminants In solvents.
reagents, glassware and other sample processing apparatus that
lead to discrete artifacts or elevated baselines in liquid
chromatograms. All reagents and apparatus must bt routinely
demonstrated to be free from Interferences under the conditions
of the analysis by running laboratory reagent blanks.as describ-
ed in Section 10.8.
4.1.1 Glassware must be scrupulously cleaned.3 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 may be> substituted for the heat-
Ing. 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 Contaminants may be Introduced during sample extract prepara-
tion. Analyses of laboratory reagent blanks provide information
about the presence of contaminants.
4.3 Interfering contamination may occur when a sample containing low
concentrations of analytes Is analyzed immediately following a
sample containing relatively high concentrations of analytes.
Between-sample rinsing of the sample syringe and associated
equipment with methanol can minimize sample cross contamina-
tion. After analysis of a sample containing high concentrations
of analytes, one or tort Injections of methanol should be made
to ensure that accurate values art obtained for the next sample.
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4.4 Matrix interferences may be caused by contaminants that are
coextracted from the sample. The extent of matrix interferences
Mill vary considerably from source to source, depending upon the
ground water sampled. Cleanup of sample extracts may be
necessary. Positive identifications must bt confirmed using the
confirmation column specified in Table 3.
5-
5.1 The toxicity or carcinogenicity of each reagtnt used in this
method has not been precisely defined; however, each chemical
compound must be treated as a potential health hazard. From
this viewpoint, exposure to these chemicals must be reduced to
the lowest possible level by whatever means available. The
laboratory is responsible for maintaining a current awareness
file of OSHA regulations regarding the safe handling of tht
chemicals specified in this method. A reference file of
material safety data sheets should also be mad* available to all
personnel involved in the chemical analysis. Additional
references to laboratory safety are available and have been
identified4'* 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 Borosilicate, 1-L volume with
graduations (Wheat on Media/Lab bottle 219820), fitted
with screw caps lined with TFE-fluorocarbon. Protect
samples from light. The container must be washed and
dried as described in Section 4.1.1 before use to
minimize contamination. Cap liners are cut to fit from
sheets (Pierce Catalog No. 012736) and extracted with
methanol overnight prior to use.
6.2 GLASSWARE
6.2.1 Separatory funnel 2000-mL, with TFE-fluorocarbon
stopcock, ground glass or TFE-fluorocarbon stopper.
6.2.2 Tumbler bottle -- 1.7-L ( Wheat on Roller Culture Vessel),
with TFE-fluorocarbon lined screw cap. Cap liners are
cut to fit from sheets (Pierce Catalog No. 012736) and
extracted with methanol overnight prior to use.
6.2.3 Flasks, Erlenmeyer - 500-ml.
6.2.4 Drying column - Chromatographlc column, 400 mm long x
19 mm 10 with coarse fritted disc.
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6.2.5 Concentrator tube, Kuderna-Danish (K-D) - 10- or 25-mL,
graduated (Kontes K-5700SO-1025 or K-570050-2525 or
equivalent). Calibration must be checked at the volumes
employed in the test. Ground glass stoppers are used to
prevent evaporation of extracts.
6.2.6 , Evaporative flask. K-0 -- 500-mL (Kontes K-570001-0500
or equivalent). Attach to concentrator tube with
springs.
6.2.7 Snyder column. K-0 -- three-ball macro (Kontes K-503000-
0121 or equivalent).
6.2.8 Snyder column, K-0 - two-ball micro (Kontes K-569001-
0219 or equivalent).
6.2.9 Vials -- Glass, 5 to 10-mL capacity with TFE-fluoro-
carbon lined screw cap.
6.2.10 Syringes -- disposible glass, frosted tip, 2.5-mL (8-0
Glaspak No. 5291 or equivalent).
6.3 Separatory funnel shaker -- Capable of holding eight 2-1 separa- t
tory funnels and shaking then with rocking notion to achieve
thorough mixing of separatory funnel contents (available from
Eberbach Co. in Ann Arbor, HI).
6.4 Tumbler -- Capable of holding four to six tumbler bottles and
tumbling them end-over-end at 30 turns/min (Associated Design
and Mfg. Co., Alexandria, VA.).
6.5 Boiling stones Carborundum, 112 granules (Arthur H. Thomas
Co. #1590-033). Heat at 400*C for 30 min prior to use. Cool
and store in a dessicator. .
6.6 Water bath -- Heated, capable of temperature control (±2*C).
The bath should bt used in a hood.
6.7 Balance -- Analytical, capable of accurately weighing to the
nearest 0.0001 g.
6.8 FILTRATION APPARATUS
6.8.1 Macroflltratlon to filter mobile phases used in HPLC.
Recommend using 47 mm filters (H1111 pore Type HA, 0.45
Mm for water and Ml111 pore Typt FH, 0.5 urn for organicj
or equivalent).
6.8.2 Mlcrofiltration -- Solvent resistant filter assemblies,
0.45 M» (GelMit LC3S or equivalent), for filtration of
sample extracts prior to analysis.
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6.9 LIQUID CHROMATOGRAPH - High performance analytical system
complete with high pressure syringes or sample injection loop,
analytical columns, detector and strip chart recorder.
6.9.1 Gradient pumping system, constant flow.
6.9.2 . Primary column -- 250 mm long x 4.6 mm 10 stanless steel
packed with Oupont Zorbax OOS or equivalent. 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.
6.9.3 Confirmation column -- 250 mm long x 4.6 mm 10 stanless
steel packed with Oupont Zorbax Silica (4-6 urn) or
equivalent.
6.9.4 Detector - Ultraviolet, capable of monitoring at
254 nm. This detector has proven effective 1n the
analysis of spliced reagent and artificial ground waters.
The UV detector was used to generate the validation data
presented in this method. Alternative detectors may be
used in accordance with the provisions described in
Section 10.3. l
7. REAGENTS AND CONSUMABLE MATERIALS
7.1 Acetone, methylene chloride, hexane, methanol, water --
D1st111ed-in-glas$ quality or equivalent.
7.2 Phosphate buffer, pH7 -- Prepare by mixing 29.6 mL 0.1 N HC1 and
50 ml 0.1 M dipotassium phosphate.
7.3 Phosphoric acid, reagent -- 85. IX 83^4 assay.
.7.4 Sodium sulfate, granular, anhydrous, ACS grade Heat treat in
a shallow tray at 450*C for a minimum of 4 hours to remove
interfering organic substances.
7.5 Sodium chloride, crystal, ACS gradt -- Heat treat in a shallow
tray at 450*C for a minimum of 4 hours to remove interfering
organic substances.
7.6 Ethy1benzen« >9« purity, for use as internal standard
(available from Aldrlch Chemical Co.).
7.7 Carbazole >98% purity, for usa as surrogate standard (avail-
able from Aldrlch Chemical Co.).
7.3 Reagent water -- Reagent water Is defined as water in which an
interferent Is not observed at or above the COL of any analyte.
Reagent water used to generate the validation data in this
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method Mas distilled water obtained from the Magnetic Springs
Water Co., 1301 Lone Eagle St., Columbus, Ohio 43228.
7.9 HPLC MOBILE PHASE
7.9.1 Primary column
7.9.1.1 Water -- HPLC grade (available from Burdlck and
Jackson) containing 0.1X phosphoric acid (v/v).
7.9.1.2 Organic phase Aceton1tr1le containing 0.1%
phosphoric acid (v/v).
7.9.2 Confirmation column
7.9.2.1 Methylene chloride containing 5X methanol.
7.9.2.2 Hexane
7.10 STOCK STANDARD SOLUTIONS (1.00 ug/uL) -- Stock standard solu-
tions may be purchased as certified solutions or prepared front
purt standard materials using the following procedure:
7.10.1 Prepare stock standard solutions by accurately weighing
approximately 0.0100 g of pure material. Dissolve the
material in methanol and dilute to volume in a 10-ml
volumetric flask. Larger volumes may be used at the
convenience of the analyst. If compound purity is
certified at 96X 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.
7.10.2 Transfer the stock standard solutions into TFE-fluoro-
carbon-sealed screw cap vials. Store at room temper-
ature and protect from light.
7.10.3 Stock standard solutions should be replaced after two
months or sooner if comparison with laboratory control
standards indicates a problem.
7.11 INTERNAL STANDARD SPIKING SOLUTION -- Prepare an internal
standard spiking solution by accurately weighing approximately
0.0050 g of pure ethylbenzene. Dissolve the ethylbenzene in
pesticide quality methanol and dilute to volume In a 10-mL
volumetric flask. Transfer the internal standard spiking
solution to a TFE-fluorocarbon-seiled screw cap bottle and store
at room temperature. Addition of 50 uL of the internal standard
spiking solution to 5 ml of sample extract results in a final
internal standard concentration of 5.0 yg/«l. Solution should
be replaced when ongoing QC (Section 10) indicates a problem.
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7.12 SURROGATE STANDARD SPIKING SOLUTION -- Prepare a surrogate
standard spiking solution by accurately weighing approximately
0.010 g of pure carbazole. Dissolve the carbazole in pesticide
quality methanol and dilute to volume in a 100-ml volumetric
flask. Transfer the surrogate standard spiking solution to a
TFE-fluorocarbon-sealed screw cap bottle and store at room
temperature. Addition of 50 Ml of the surrogate standard
spiking solution to a 1-L sample prior to extraction results in
a surrogate standard concentration in the sample of 5.0 ug/l
and, assuming quantitative recovery of carbazole, a surrogate
standard concentration in the final extract of 1.0 ug/ml.
Solution should be replaced when ongoing QC (Section 10)
indicates a problem.
7.13 INSTRUMENT QC STANDARD -- Prepare Instrument QC standard stock
solutions by accurately weighing 0.0010 g each of carbazole,
neburon, ethylbenzene, fenamlphos sulfoxide, and fluometuron.
Dissolve each analyte in pesticide quality methanol and dilute-
to volume in individual 10-ml volumetric flasks. Combine 100 Ml
of the carbazole stock solution, 5 ml of the ethylbenzene stock
solution, 800 Ml of the fenamlphos sulfoxide stock solution,
100 Ml of the of the neburon stock solution, and 20 Ml of the
fluometuron stock solution to a 100-mi. volumetric flask and
dilute to volume with methanol. Transfer the surrogate standard
spiking solution 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 STQMfig
8.1 Grab samples must be collected In glass containers. Conven-
tional sampling practices7 should be followed; however, the
bottle must not be prerlnsed 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 1 ml of a 10
mg/ml solution of mercuric chloride in water to the
sample bottle at the sampling site or In the laboratory
before shipping to the sampling site. A major dis-
advantage of mercuric chloride Is that it Is a highly
toxic chemical; mercuric chloride must be handled with
caution, and samples containing mercuric chloride must
be disposed of properly.
8.2.2 After adding the sample to the bottle containing
preservative, seal the bottle and shake vigorously for 1
mln.
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3.2.3 The samples must be iced or refrigerated at 4*C from the
time of collection until extraction. Preservation study
results given in Table 11 indicate that samples are
stable under these conditions for at least 28 days.
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 Sample extracts should be stored at 4*C away from light.
Preservation study results presented in Table 11
indicate that extracts are stable under these conditions
for at least 28 days. The analyst should verify
appropriate extract holding times applicable to the
samples under study.
9. CALIBRATION
9.1 Establish HPLC operating conditions equivalent to those indicat-
ed In Table 3. Calibrate the HPLC system using the Internal
standard calibration technique (Section 9.2). l
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 compounds of Interest. The
analyst must further demonstrate that the measurement of the
internal standard is not affected by method or matrix Interfer-
ences. Ethyl benzene has been Identified as a suitable Internal
standard.
9.2.1 Prepare calibration standards at a minimum of three
(suggested five) concentration levels for each analyte
of Interest by adding volumes of one or more stock stan-
dards to a volumetric flask. To each calibration
standard, add a known constant amount of one or more
internal standards, and dilute to volume with methanol.
One of the calibration standards should be represen-
tative of an analyte concentration near, but above, the
EOL. The other concentrations should correspond to the
range of concentrations expected In the sample concen-
trates, or should define the working range of the
detector.
9.2.2 Inject 10 Ml of each calibration standard and tabulate
the relative response for each analyte (RRj) to the
internal standard using the equation:
RRj Aa/*1$
-------
where: Aa the peak area of the analyte, ,nd
Ais » the peak area of the internal standard.
Generate a calibration curve of analyte relative
response, RR«, versus analyte concentration in the
sample in Mg/L.-
9.2.3 The working calibration curve must be verified on each
working shift by the measurement of ont or more calibra-
tion standards. If the response for any analyte varies
from the predicted response by more than ± 20X, the test
must be repeated using a fresh calibration standard.
Alternatively, a new calibration curve must be prepared
for that analyte.
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 samele 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 laboratory control standards, QC
samples, and performance evaluation (PC) 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 COL) for each of the target analytes.
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 concentration.
10.2.2 Using a syringe, add 1 «t of the LC sample concentrate
to each of a minimum of four 1-L allquots of reagent
water. A representative ground water may be used in
place of the reagent water, but one or more unsplked
allquots must be analyzed to determine background
levels, and the spike level must, at a minimum, exceed
twice the background Itvel for tht test to be valid.
Analyze the allquots according to the method beginning
In Section 11.
10
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report results. If tht relnjected sample
extract aliquot displays an internal standard
peak area or height outside the specified
Knits, but extract allquots from other
samples continue to give the proper area or
height for tht 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 tht internal
standard peak areas or heights for successive
samples fail tht 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 tht calibra-
tion curvt 1s still applicable and if tht
calibration check standard Internal standard'
peak area or height 1s within ±30% of tht
average internal standard peak area or height
for the calibration standards, reanalyze those
sample extracts whost Internal standard failed1
the specified criteria. Iftht internal
standard peak areas or heights now fall within
tht specified limits, report tht results. If
the Internal standard peak areas or heights
still fall to fall within tht specified limits
or if the calibration curvt is no longtr
applicable, then gtntratt a new calibration
curvt (Section 9) and reanalyze thost sample
extracts whost inttmal standard failed the
peak area or height criteria.
10.6 ASSESSING LABORATORY PERFORMANCE
10.6.1 Tht laboratory must, on an ongoing basis, analyze at
least one laboratory control standard ptr sample set (a
sample set Is all thost samplts txtracted within a
24-hour period).
10.6.1.1 The spiking concentration In tht laboratory
control standard should bt 15 times tht COL.
10.6.1.2 Spike a 1-L aliquot of reagent water with a
laboratory control (LC) sample concentrate
(the volume of tht splkt should bt kept to a
inIMC so tht solubility of the analytes of
interest in water will not bt affected) and
analyze it to determine tht concentration
after spiking (A) of each analytt. Calculate
aca percent recovery (Rj) as (lOOxA)VT,
13
-------
where 7 is the known true concentration of the
spike.
10.6.1.3 Compare the percent recovery (Rj) for each
analyte 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 (SpJ using the following
equations:
and
' * / -
T «,*: -(£«,
number of measurements for each
analyte, and
individual percent recovery
value.
Calculate QC acceptance criteria as follows:
Upper Control Limit (UCL) - R * 3So
Lower Control Limit (LCL) - R - 3Sg
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 con*
tinuous basis. After each five to ten new
recovery measurements (R<$), recalculate R and
Sg 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 SB. using only the most
recent twenty data points.
Monitor all data from laboratory control
standards. Analyte recoveries must fall
within the established control limits.
14
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If tht recovtry of any such analyte falls
outside tht designated range, the laboratory
performance for that analyte is judged to be
out of control, and the source of the problem
must be immediately identified and resolved
before continuing the analyses. The analyti-
cal result for that analyte In samples is
suspect and must be so labeled. AH results
for that analyte in that sample set must also
bt 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 bt 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 tht samples.
10.7.1.1 The spiking concentration in the sample should
bt one to five times the background concentra-
tion, or, 1f it is impractical to determine
background levels before spiking, 15 times the
EOL.
10.7.1.2 Analyze ont sample aliquot to determine the
background concentration (8) of each analyte.
Spike a second sample aliquot with a labora-
tory control (LC) sample concentrate (tht
volume of the spike should bt kept to a
minimum] so the solubility of the analytes of
interest in water will not bt affected) and
analyze it to determine tht concentration
after spiking (A) of each analyte. Calculate
each percent recovery (Rj) as 100(A-8)VT,
where T Is the known true concentration of the
spike.
10.7.1.3 Compare the percent recovery (Rf) for each
analyte with QC acceptance criteria esta-
blished from the analyses of laboratory
control standards.
15
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Monitor all data from dostd samplts. Analyte
recoveries must fall within tht established
control limits.
10.7.1.4 If tht recovery of any such analyte falls
outside tht designated range, and tht labora-
tory performance for that analyte is judged to
bt in control, tht recovery problem encoun-
tered with tht dostd sample Is judged to bt
matrix-related, not system-related. Tht
result for that analyte In tht unspiked sample
Is labeled susptct/matrlx to inform tht ustr
that tht results art susptet dut to matrix
effects.
10.8 ASSESSING LABORATORY CONTAMINATION (METHOD BLANKS) - Btfort
processing any samples, tht analyst must demonstrate that all
glassware and reagent Interferences art undtr control. This 1s
accomplished by tht analysis of a laboratory method blank. A
laboratory method blank is a 1-L aliquot of reagtnt water
analyzed as if it was a sample. Each t1mt a stt of samples 1s
extracted or there 1s a changt in reagents, a laboratory mtthod
blank must bt processed to assess laboratory contamination. If
tht mtthod blank exhibits a peak within tht retention tlmt
window of any analytt which 1s grtattr than or equal to ont-
half tht EDI for that analytt, determine tht sourct of contam-
ination before processing samplts and eliminate tht Interference
problem.
10.9 ASSESSING INSTRUMENT PERFORMANCE (INSTRUMENT QC STANDARD) --
Instrument performance should bt monitored on a dally basis by
analysis of tht instrumtnt QC standard. Tht Instrument QC
standard contains compounds designed to Indicate approprlatt
Instrumtnt sensitivity, column performance and chromatograpMc
performance. Instrument QC standard components and ptrformanct
criteria art listed In Tablt 10. Inability to demonstrate
acceptablt Instrumtnt ptrformanct Indicates tht need for
revaluation of tht HPLC-UV system. A HPLC-UV chromatogra*
generated from tht analysis of tht Instrumtnt QC standard 1s
shown In Figure 1. Tht sensitivity requirements art stt based
on tht EOls published In this mtthod. If laboratory EDLs differ
from thost listed In this mtthod, concentrations of tht instru-
ment QC standard compounds must bt adjusted to bt compatible
with tht laboratory EOLs. An instrumtnt QC standard should bt
analyzed with each sample set.
10.10 ANALYTE CONFIRMATION - Whtm doubt exists over tht 1dtnt1f1cat1on
of a ptak on tht chroaatograa, confirmatory techniques such as
mass sptctromttry or a second gas chromatography column must be
used. A suggested confirmation column 1s described 1n Tablt 3.
It
-------
10.11 ADDITIONAL QC It is recommended that the laboratory adopt
additional quality assuranct practices for use with this
method. The specific practices that are most productive depend
upon tht needs of the laboratory and the nature of the samples.
11. PROCEDURE
11.1 AUTOMATED EXTRACTION METHOD -- Validation data presented in this
method were generated using the automated extraction procedure
with tht mechanical tumbler.
11.1.1 Add preservative to any samples not previously preserved
(Section 8.2). Mark the water meniscus on the side of
the sample bottle for later determination of sample
volume. Spike sample with SO ML of the surrogate
standard spiking solution. If tht mechanical separatory
funnel shaker is used, pour tht entire sample into a 2-L
separatory funnel. If the mechanical tumbler Is used,
pour the entire sample into a tumbler bottle.
11.1.2 Adjust sample to pH 7 by adding SO mL of phosphate
buffer.
11.1.3 Add 100 g Nad to the sample, seal, and shake to
dissolve salt.
11.1.4 Add 300 mL methylent chlorldt to tht samplt bottTt,
seal, and shake 30 s to rinse tht Inner walls. Transfer
the solvent to tht samplt contained in tht separatory
funnel or tumbler bottle, seal, and shake for 10 s,
venting periodically. Repeat shaking and venting until
pressure releast 1s not observed during venting. Reseal
and place sample container In appropriate mechanical
mixing device (separatory funnel shaker or tumbler).
Shake or tumble tht. samplt for 1 hour. Complete and
thorough mixing of tht organic and aqueous phases should
bt observed at least 2 mln after starting tht mixing
device.
11.1.5 Remove the samplt container from the mixing device. If
tht tumbler is used* pour contents of tumbler bottle
Into a 2-L separatory funnel. Allow tht organic layer
to separate from tht water phast for a minimum of 10
mln. If tht emulsion interface between layers is more
than one third tht volumt of tht solvent layer, the
analyst must employ mechanical techniques to complete
tht phast separation. Tht optimum technique depends
upon the sample, but may Include stirring, filtration
through glass wool, centnfugatlon, or other physical
mtthods. Collect tht methylene chlorldt extract In a
500-ml Erltnmeytr.
17
-------
11.1.6 Determine the original sample volume by refilling the
sample bottle to the mark and transferring the water to
a 1000-ml graduated cylinder. Record the sample volume
to the nearest 5 ml.
11.2 MANUAL EXTRACTION METHOD - Alternative procedure.
11.2.1 Add preservative to any samples not previously preserved
(Section 8.2). Mark the water meniscus on the side of
the sample bottle for later determination of sample
volume. Pour the entire sample into a 2*1 separatory
funnel and spike with 50 uL of the surrogate standard
spiking solution.
11.2.2 Adjust sample to pH 7 by adding 50 ml of phosphate
buffer.
11.2.3 Add 100 g Nad to the sample, seal, and shake to
dissolve salt.
11.2.4 Add 60 ml methylene chloride to the sample bottle, seal,
and shake 30 s to rinse the inner wells. Transfer the
solvent to tht separatory funnel and extract the sample
by vigorously shaking the funnel for 2 m1n with periodic
venting to release excess pressure. Allow the organic
layer to separate fro* the water phase for a minimum of
10 min. If the emulsion Interface between layers is
more than one third the volume of the solvent layer, the
analyst must employ mechanical techniques to complete
the phase separation. The optimum technique depends
upon the sample, but may include stirring, filtration
through glass wool, centrifugalion, or other physical
methods. Collect the methylene chloride extract in a
500-ml Crlenmeyer flask.
11.2.5 Add a second 60-ml volume of methylene chloride to the
sample bottle and repeat the extraction procedure a
second time, combining the extracts in the Erlenneyer
flask. Perform a third extraction in the same manner.
11.2.6 Determine the original sample volume by refilling the
sample bottle to the mark and transferring the water to
a 1000-nL graduated cylinder. Record the sample volume
to the nearest 5 mL.
11.3 EXTRACT DRYING AND CONCENTRATION
11.3.1 Assemble a K-0 concentrator by attaching a 25-ml concen-
trator tube to a 500-ml evaporative flask.
11.3.2 Pass the combined extract fro* step 11.1.5 or step
11.2.5 through a drying column containing about 10 cm of
18
-------
anhydrous sodium sulfate and collect tht extract in the
K-0 concentrator. Rinse the Erlenmtyer flask and column
with 20 to 30 mi. of methylene chloride to complete the
quantitative transfer.
11.3.3 Add 1 to 2 clean boiling stones to the evaporative flask
and attach a macro-Snyder column. Prewtt the Snyder
column by adding about 1 ml mtthylent chloride to the
top. Place the K-0 apparatus on a hot water bath, 65 to
70*C, so that the concentrator tubt is partially
immersed In the hot water, and the entire lower rounded
surface of the flask is bathed with hot vapor. Adjust
the vertical position of the apparatus and the water
temperature as required to complete the concentration in
15 to 20 m1n. At the proper rate of distillation the
balls of the column will actively chatter, but tht
chambers will not flood. When the apparent volume of
liquid reaches 2 mi., remove the K-0 apparatus and allow
it to drain and cool for at least 10 m1n.
11.3.4 Remove the Snyder column and rinse tht flask and Its
lower joint into the concentrator tub* with approxi-
mately 5 ml of methanol. Attach a micro-Snyder column
to the concentrator tub* and prewet tht column by adding
about 0.5 ml of methanol to tht top. PI act tht micro
K-0 apparatus on tht water bath so that tht concentrator
tube is partially immersed in tht hot water. Adjust the
vertical position of tht apparatus and tht water
temperature as required to complete concentration in 5
to 10 min. When tht apparent volumt of liquid reaches
2 ml, remove tht micro K-0 fro* the bath and allow it to
drain and cool. Remove tht mlcro-Snyder column, and
rinse the walls of tht concentrator tubt while adjusting
the volumt to 5.0 ml with methanol.
11.3.5 Add 50 pL of Internal standard spiking solution to the
sample extract, seal, and agitate. Transfer extract to
an appropriate sized TFC-fluoroearbon-staled screw-cap
vial and store, refrigerated at 4*C, until analysis by
HPLC-OV.
11.4 LIQUID CHROHATOGRAPHY
11.4.1 Table 3 summarizes tht recommended HPLC-UV operating
conditions. Included in this table art retention times
observed using this method. Examples of tht separations
achieved using these conditions art shown In Figures 1
and 2. Other HPIC columns, chroMtographfc conditions,
or detectors may be used if tht requirements of
Section 10.2 art net.
19
-------
11.4.2 Calibrate the system daily as described in Section 9.
The standards and extracts must be in methanol.
11.4.3 Filter sample extracts. Draw an appropriate volume of
sample into a disposable glass 2.5-ml syringe. Attach
the filter assembly to the syringe, and push the extract
through the filter assembly into a vial or an auto*
sampler vial.
11.4.4 Inject 10 uL of the sample extract. Record the result-
ing peak sizes in are* units.
11.4.4 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.
11.4.5 If the response for a peak exceeds the working range of
the system, dilute the extract and reanalyze.
12. CALCULATIONS
12.1 Calculate analyte concentrations In the sample from the relative
response for the analyte to the Internal standard (RRa) using
the equation for the calibration curve described 1n Section
9.2.2.
12.2 For samples processed as part of a set where the laboratory
control standard recovery falls outside of the control limits in
Section 10, data for the affected analytes must be labeled as
suspect.
13. PRECISION AND ACCURACY
13.1 In a single laboratory, analyte recoveries fro* reagent water
were determined at five concentration levels. Results were used
to determine analyte EDts and demonstrate method range.
Analytes were divided Into two spiking groups (A and 8) for
recovery studies. COL results art given in Table 2. Method
range results are given In Tables 4-7.
13.2 In a single laboratory, analyte recoveries from two artificial
ground waters wer« determined at one concentration level.
Results were used to demonstrate applicability of the method to
different ground water matrices. Analytes were divided into two
spiking groups (A IA* I) for recovery studies. Analyte recover-
ies from the two artificial matrices art given In Tables 8
and 9.
20
-------
13.3
21
stability in ground
extracts. Analyt.s «tr! Sv i * $amplt
-------
REFERENCES
1. Method 632 -- The Determination of Carbamate and Urea Pesticides in
Industrial and Municipal Wastewater, U.S. Environmental Protection
Agency Environmental Monitoring and Support Laboratory, Cincinnati,
Ohio 45268.
2. Engel, T., "Standardization of Methods for a National Pesticide
Survey", U.S. Environmental Protection Agency, Environmental Monitoring
and Support Laboratory, Cincinnati, Ohio 45268, February 1986.
3. ASTM Annual Book of Standards, Part 11, Volume 11.02, 03694-82,
"Standard Practice for Preparation of Sample Containers and for
Preservation*, American Society for Testing and Materials, Philadel-
phia, PA, p. 86, 1986.
4. "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.
5. "OSHA Safety and Health Standards, General Industry," (29 CFR 1910),
Occupational Safety and Health Administration, OSHA 2206, (Revised,
January 1976).
6. "Safety in Academic Chemistry Laboratories," American Chemical Society
Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. 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.
22
-------
TABLE 1. METHOD AHALWS
Analyte
Atrazlne dealkylated
Barban
Carbofuran phenol
Cyanazine
Oiuron
Fenamlphos sulfone
Fenaohpnos sulfoxlde
Huometuron
3-Ketocarbofuran phenol
Llnuron
MetHbuzIn OA
Mttr1buz1n OAOK
Metrlbuzln OK
Ncburon
Pronaaidt nttibolitc(b)
Propanil
Propha*
Swtp
Chwilcal Abstracts
S«rvict Registry
Numb«r
101-27-9
1563-38-8
21725-46-2
330-54-1
31972-44-8
31972-43-7
2164-17-2
17781-16-7
330-55-2
35045-02-4
36507-37-0
555-37-3
709-98-8
122-42-9
1918-18-9
Ident.
Codt(a)
A-2
8-9
8-5
8-4
A-6
A-5
A-4
B-6
B-2
B-8
8-3
A-l
8-1
B-10
A-8
A-7
8-7
A-9
(b)
(O
Codt used for Idtntlflcatlon of ptaks in figures;
Ittttr Indicates mix (A or B) containing analytt; IS
internal standard and SUR surrogate standard.
N-(l,l-01ntthy1acetony1)-3,5-d1ch1orobenzafllde.
Ron* and Haas number RH 24,580.
23
-------
TABLE 2. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 1) AND EOLs (a)
Arulyte
Spiking Amt in
Level, Blank,
n(b) R(c) S(d) RSQ(e) EDL(f)
Atrazint dealkylated
Barban
Carbofuran phenol
Cyanazlne
Oiuron
Fenamlphos sulfont
Fenamlphos sulf oxide
F1 uometuron
3-Ketocarbofuran phenol
Linuron (h)
Metribuzln OA
Metrlbuzln OAOK (h)
Metribuzin OK
Neburon
Pronanidt mttabolite
Propanll
Prophan
Swep (h)
0.25
O.SO
l.S
0.30
0.070
2.5
1.0
0.10
0.2S
0.25
0.10
2.5
0.10
0.15
0.70
O.OSO
0.75
0.75
NO (g)
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
0.015
NO
NO
8
8
7
7
8
7
8
8
8
3
3
7
8
8
3
8
8
7
87
100
82
89
103
109
67
77
74
83
120
30
72
91
87
94
86
as
0.0784
0.0318
0.585
0.194
0.0228
1.90
0.217
0.0234
0.0690
0.0317
0.0719
0.288
0.0151
0.0198
0.281
0.0230
0.0917
0.244
36
6
48
73
31
69
32
30
37
15
60
38
21
14
46
49
14
38
0.2S
0.50
1.3
0.53
0.070
5.7
1.0
0.10
0.25
0.25
0.21
.2.5
0.10
0.15
0.81
0.067
0.75
0.75
(a) Amounts corrected for levels detected In blank; average recovery of carbazole
surrogate standard fro* eight spiked reagent water samples was 93% (8.1 percent
relative standard deviation).
(b) n number of recovery data points.
(c) R average ptrcent recovery.
(d) S standard deviation.
(e) RSO percent relative standard deviation
(f) EOL - estimated detection limit in sample
standard deviation (S) times the students .. .
levtl and a standard deviation estimate with n 1 degrees of freedom, or alevel of
compound 1n sample yielding a peak In the final extract with signal to noise
ratio of approximately 5, whichever value) is higher.
(g) NO Interfertnce not detected 1n blank.
(h) Data from spiking level 2.
in g/L; calculated by multiplying
t value appropriate for a 99X confidence
24
-------
TABLE 3. PRIMARY AND CONFIRMATION CHROMATOGRAPHIC CONDITIONS
Relative or Absolute Retention Time
Analyte - Primary (a,b) Confirmation (c,e)
Atrazine dealkylated
Barban
Carbazole (SUR)
Carbofuran phenol
Cyanazlne
Oluron
Fenamlphos sulfone
Fenamlphos $u If oxide
Fluometuron
3-Kttocarbofuran phenol
Linuron
Metrlbuzln OA
Hetrlbuzln OAOK
Metrlbuzln OK
Neburon
Pronamlde metabolite
Propanll
Propha«
Swep
0.334
0.898
0.86S
0.514
0.456
0.656
0.488
0.438
0.591
0.350
0.809
0.383
0.297
0.287
0.987
0.76S
0.748
0.688
0.809
(d)
\ f
6.53
(d)
\ ^ f
4.16
8.07
7.31
7.70
8.50
8.54
6.39
6.74
(d)
\ " /
(d)
\ * r
(d) l
\ r
6.81
(d)
\ /
7.12
3.63
5.57
(a) Retention tint relative to ethylbenzent Internal standard. Ethylbenzene
elutes at approximately 17.5 n1n using the primary conditions and at
approximately 3.6 «1n using the confirmation conditions.
(b) Primary conditions:
Column: 2SO mm x 4.6 mm OuPont Zorbax 00$
Mobile phase: Linear gradient from 4:6 water: acetonitrlle with 0.1*
phosphoric add to 2:8 water:acetonitr11e'with 0.1* phos-
phoric add in 20 mln; ramp to acetonltrile with 0.1%
phosphoric add and hold for 8 mln; ramp to original
phase composition and equilibrate for 20 mln.
Flow ratt: 1.0 ml/mln
Injection volumm: 10 uL
Detector: UV at 254 nm
(c) Confirmation conditions:
Column: 250 mm x 4.6 me OuPont Zorbax silica
Mobile phase: Hold at 5:95 5X methanol in methylene chloride:hexane for
3 mln; linear gradient to 85:15 5X methanol in methyltn«
ch1oride:hflxan« in 25 mln; ramo to original phase
composition and equilibrate for 20 mln.
Flow rate: 1.0 ml/ain
Injection volume: 20 ML
Detector: UV at 254 nm
(d) No data available.
(t) Absolute retention time in minutes.
25
-------
TABLE 4. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 2) (a)
.Spiking Amt in
Levtl, Blank,
Analytt pg/L pg/L
Atrazint dtalkylattd 1.3 NO
Barban 2.5 NO
Carbofuran phtnol 7.5 NO
Cyanazint 1.5 NO
Oluron 0.35 NO
Fenamiphos sulfont 12.5 NO
Fenamiphos sulfoxldt 5.0 NO
Fluomtturon O.SO NO
3-Kttocarbofuran phtnol 1.3 NO
Linuron 0.25 NO
Mttnbuzm OA o.so NO
Mttribuztn OAOK 2.5 NO
Mttr1bui1n OK 0.50 NO
Naburon 0.75 NO
Pronaahdt iMtabolItt 3.5 NO
Propanil 0.2S NO
ProphM 3.8 NO
Swtp 0.75 NO
(a) Data corrtcttd for amount found in
(b) n numbtr of rtcovtry data points
(c) R - avtragt ptrcant rtcovtry.
(d) S standard dtvlation.
n(b)
(0 6
6
7
7
6
6
7
7
7
7
7
7
7
7
6
7
7
blank.
R(c)
99
82
99
124
97
96
85
109
86
86
103
35
88
82
91
107
81
97
S(d)
0.192
0.309
0.628
0.126
0.0371
1.09
0.393
0.0282
0.0684
0.0261
0.0320
0.0381
0.0433
0.0404
0.142
0.0302
0.179
0.0337
RSO(d)
15
15
3
7
11
9
9
5
6
12
6
4
10
7
4
11
6
S
(e) RSO ptrctnt rtlatlvt standard dtvlation.
(f) NO inttrftrtnet not dtttcttd in
blank.
.
26
-------
"8U 5.
RECOVERY OF ANAUTES FROM REASEKT WATER (VKIM LEVEl ,
Analytt
Spiking Ant in
L«vtl, Blank,
M9/L pg/L
Atrazlnt dtalkylattd
Sarban
Carbofuran phtnol
Cyanazint
Oluron
Ftnaahphos sulfont
Fenanlpnos sulfoxidt
Fluomtturon
3-Kttocarbofuran phtno)
Llnuron
Mttr1buz1n OA
M«tr1buz1n OAOK
Mttr1buz1n OK
Neburon
Pronaaldc ottabolitt
Propanll
Propha*
Swtp
(O
(b)
(d)
()
(0
Amount corrtcttd for Itvtl dattcttd In blank.
n nu«b«r of rtcovtry data points.
R avtragt ptrcint rtcovtry.
S standard dtvlatlon.
RSO ptrctnt rtlatlvt standard dtvlatlon.
Inttrftrtnet not dtttcttd In blank.
RSD(t)
2.5
5.0
15
3.0
0.70
25
10
1.0
2.5
0.50
1.0
5.0
1.0
1.5
7.0
0.50
7.5
1.5
NO (t)
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
5
6
5
6
7
7
7
6
7
7
7
7
7
7
7
6
7
7
68
98
114
117
105
98
88
10S
95
102
101
35
59
101
95
95
93
96
0.336
0.494
2.60
0.260
0.0603
3.73
0.544
0.0656
0.205
0.0582
0.0898
0.0727
0.0994
0.186
0.285
0.0917
0.532
0.0238
20
10
15
7
3
15
6
6
9
11
9
4
17
12
4
19
8
2
27
-------
TABLE 6. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 4) (a)
.Spiking Amt in
Level, Blank,
Analyte pg/L pg/L
Atrazine dealkylated 6.3 NO (f)
Barban 13 NO
Carbofuran phenol 38 NO
Cyanazlne 7.5 NO
Oluron 1.3 NO
Fenamlphos sulfone 63 NO
Fenamlphos sulfoxlde 25 NO
F1 uometuron 2.5 NO
3-Ketocarbofuran phenol 6.3 NO
Linuron 1.3 NO
Metrlbuzln OA 2.5 NO
Metrlbuzln OAOK 13 NO
Metrlbuzln OK 2.5 NO
Neburon 3.8 NO
Pron amide metabolite 18 NO
Propanll 1.3 NO
Propham 19 NO
Swep 3.8 NO
(a) Amounts corrected for amount found in
(b) n number of recovery data points
(c) R average percent recovery.
(d) S standard deviation.
"(b)
6
7
6
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
blank.
R(c)
89
103
102
101
106
93
92
98
95
100
91
36
50
99
97
98
98
95
S(d)
0.354
1.12
5.09
0.758
0.0241
1.38
0.799
0.308
0.484
0.0926
0.20S
0.112
0.110
0.304
0.369
0.0292
1.53
0.0749
RSO(e)
6
9
13
10
1
2
3
13
3
7
9
2
9
8
2
2
3
2
(e) RSO percent relative standard deviation.
(f) NO Interference not detected in blank.
28
-------
TABU 7. *ECOV«Y OF ANALVTK MOH RH6WT
,
Analyte
Spiking Amt In
l-evtl, Blank,
Atrazine dealkylated
Barban
Carbofuran phtnol
Cyanazlne
Oluron
Fenamiphos sulfone
Fjnamiphos sulfoxldt
Muometuron
3-Ketocarbofuran phtnol
Linuron
Metribuzin OA
MttHbuzIn OAOK
Metribuzin OK
Neburon
Proruaidt mttaboUtt
Propanll
Prophui
Sw«p
Amount corrtcttd for levtl dtttcttd In blank.
n number of rtcovtry data points.
R avtragt ptrccnt recovtry.
S standard deviation.
RSO ptrcint rtlativt standard deviation.
NO interference not detected in blank.
(b)
(c)
(d)
()
(0
RSO(t)
25
50
150
30
7,0
250
100
10
25
5.0
10
50
10
15
70 .
5.0
75
15
NO (f)
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
6
6
6
6
7
7
7
7
6
6
7
7
7
6
7
7
6
7
83
100
104
102
91
98
88
101
94
106
98
34
35
99
91
92
99
90
1.15
3.90
12.9
2.07
0.170
14.1
2.29
0.291
1.56
0.815
0.400
0.458
0.313
0.945
2.48
0.120
5.02
0.366
-^^^^
6
8
8
7
3
6
3
3
7
15
4
3
9
6
4
3
7
3
29
-------
TABLE 8. RECOVERY OF ANALYTES FROM HARD ARTIFICIAL GROUND MATER(a)
Spiking Amt in
Level, Blank,
Analyte M9/L ug/L n(b)
Atrazint dealkylated
Barban
Carbofuran phenol
Cyanazint
Oluron
Fenamiphos sulfont
Fenamlphos sulfoxide
Fluometuron
3-Ketocarbofuran phenol
Llnuron
Metr1buz1n OA
Httrlbuzln OAOK
Mttr1buz1n OK
Neburon
Prona«1de (Mtabolltt
Propanil
Prophaa
Swep
2.5
5.0
IS
3.0
0.70
25
10
1.0
2.5
0.50
i.O
5.0
1.0
1.5
7.0
0.50
7.5
1.5
NO (f)
4.05
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
6
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
R(c)
87
102
88
94
93
101
89
100
90
104
86
29
sa
97
101
103
94
93
S(d) RSO(e)
0.239
0.483
1.94
0.397
0.0199
2.46
1.05
0.0102
0.161
0.0252
0.0384
0.0744
0.0360
0.0700
0.534
0.0221
0.700
0.0636
11
9
15
- 14
3
10
12
1
7
5
4
5
6
5
8
4
10
5
(a) Amounts corrected for amount found 1n blank; hard artificial ground
water used to generate these results was Absopure Natural Artesian
Spring Water obtained from the Alesopure Water Company in Plymouth,
Michigan.
(b) n number of recovery data points
(c) R average percent recovery.
(d) S « standard deviation.
(e) RSO percent relative standard deviation.
(f) NO » interference not detected in blank.
-------
TABLE 9. RECOVERY OF ANALYTES FROM ORGANIC-CONTAMINATED ARTIFICIAL
GROUND WATER (a)
Spiking
Ltvtl ,
Analyte M9/L
Atrazlne dealkylated
Barfaan
Carbofuran phenol
Cyanazlne
Oluron
Fenaoriphos sulfone
Fenaoriphos sulfoxlde
F1 uoiMturon
3-Ketocarbofuran phtnol
Llnuron
MetHbuzIn OA
Metrlbuzln OAOK
Metrlbuzln OK
Ntburon
Prona«1de metabolite
Propanll
Prophaa
Swep
2.5
S.O
IS
3.0
0.70
25
10
1.0
2.5
0.50
1.0
5.0
1.0
1.5
7.0
0.50
7.5
1.5
Ant In
Blank,
M9A
NO (f)
0.368
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
0.0800
NO
NO
NO
NO
n(b)
6
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
R(c)
116
98
107
101
111
87
91
99
98
101
95
34
51
101
97
102
94
93
S(d) RSO(t)
1.16
0.379
2.97
0.436
0.0421
1.97
0.449
0.0767
0.129
0.0411
0.102
0.145
0.0761
0.0992
0.531
0.0385
0.463
0.124
40
8
19
14
5
9
5
8
5
8
11
8
IS
7
a
8
7
9
(a) Amount corrected for level detected 1n blank; organic-contaminated
artificial ground water used to generate these results was reagent water
. spiked with fulvlc add at the 1 mg/L concentration level. A well-
characterized fulvlc add available fro* the International Humlc
Substances Society was used.
(b) n number of recovery data points.
(c) R average percent recovery.
(d) S standard deviation.
(e) RSO percent relative standard deviation.
(f) NO Interference not detected in blank.
31
-------
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-------
Appendix 8
Revision No 3
Date August 1, 1990
Page 1 of 2
APPENDIX B
INITIAL DEMONSTRATION OF
CAPABILITIES DATA
-------
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-------
Appendix C
Revision No 3
Date- August 1. 1990
Page 1 of 5
APPENDIX C
DIXON'S TEST
-------
DIXON'S TEST
Dlxon'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 < ... < X..J < X,
2) Decide whether the smallest, Xx, or the largest, XQ, 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 52 risk of false
rejection.
4) Compute one of the ratios in Table 1. For use in this QAPP we
will be using ratio r^, 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 5X 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 ru
10.58 - 10.53 0.05
ru - - - 0.454
10.58 - 10.47 0.11
2) A 5X 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 10Z risk of false rejection ru - 0.409, and the value
10.58 would be rejected.
-------
TABLE 1
CALCULATION OF RATIOS
Ratio
rio
11
21
r22
For use if if ^ is
n is between suspect
a.7 .
a. in '
(Xn - X2)
U- 1 ^ ...........
-ij
(Xn - X2)
]_4 . 25 ...........
(XB - X3)
if K! is
suspect
(X2 - Xi)
(X2 - Xi)
(X, - X,)
/v v ^
v-**n-l " **!'
(X, - Xt)
(Xn-2 " Xj.)
Note that for use in this QAPjP ratio ru will be used.
-------
TABLE 2
VALUES FOR USE WITH THE DIXON TEST FOR OUTLIERS
Risk of False Rejection
Rat;;o n P_5_x 11 5i IflX
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 QAFjP the 5Z risk level will be used for ratio
-------
Reference:
John K. Taylor, Quality Assurance of Chemical Measurements. Lewis
Publishers, Chelsea, MI, 1987.
-------
Appendix 0
Revision No 3
Date: August 1, 1990
Page 1 of 3
APPENDIX D
SURROGATE COMPOUND MONITORING CRITERIA
-------
? UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
'"i wot*4 CINCINNATI. OHIO 45268
MEHORXNSUH
DATE: March 18, 1988
SUBJECT: Increasing the Flexibility of NFS Surrogate Compound Monitoring
FROM: David J. Munch, Chemist
Drinking Water Quality Assessment Branch
Robert A. Maxey, Chemist
Environmental Chemistry Laboratory
TO: KPS Technical Monitors
Currently, the surrogate recovery observed in the analyses of a
laboratory control standard (LCS) must meet the limits specified by the
control chart maintained for that surrogate. The surrogate recovery
observed in the analyses of samples, spiked samples, method blanks, etc.,
must fall within +/-30% of the mean recovery for that surrogate, as
indicated on the control chart for that surrogate.
Currently if the surrogate compound spiked into a method blank (MB) or
LCS should fail to meet the quality control requirements for the recovery
of that surrogate, this KB or LCS must be invalidated. This would result
in the invalidation of all samples associated with that MB or LCS. In
order to reduce the possibility of this resulting in the loss of otherwise
valid data, wt have determined that the following procedures are
acceptable:
1. A LCS in which the surrogate compound recovery has failed to meet
the quality control limits can be validated, if the following
conditions are met.
a. The LCS meets all other required quality control elements
b. The surrogate compound recovery observed for the MB
associated with that same sample set. meets the quality
control Halts determined using the control chart for that
surrogate.
2. A MB in which the surrogate compound recovery has failed to meet
the +/-30* criteria can be validated, if a field sample
associated with that same sample set, meets all of the quality
control requirements for a KB.
In addition to these changes, a mistake has been located in the
information which was disseminated to the laboratories at the February 3-4
meeting. It was stated in that information, that the procedures for
monitoring the internal standard as contained in the HPS methods would
apply. This is correct, except that the area of the internal standard must
be within +/-20%, instead of the */-JO% mentioned ia the methods.
-------
Alio, just to avoid tny Ut«r confusion, please aakt surt that your
laboratories rtalizt that thty aust add tat appropriate preservative to
all atthod blanks and laboratory control standards.
Please relay this inforaation to your contract and referee
laboratories, as soon as possible. If you have any questions concerning
pl'*st cont«ct us prior to comaunicatina with your
c.c: H. Brass
A. Dupuy
J. Kotas
A. Kroner
- 2 -
-------
Appendix E
Revision No 3
Date: August 1, 1990'
Page 1 of 3
APPENDIX E
SPIKING LEVEL CHANGES/DATA REPORTING FORMATS
-------
I UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
CINCINNATi QMlO 45268
HZKORANDUX
DATE: July 14. 1988
SUBJECT: Changes in HPS Laboratory Procedures
TROK: David J. Munch, TS2 Project Manager
National Pesticide Survey
TO: NTS Technical Monitors (See below;
T>.« following rinsr cr.ar.ces in laboratory operations are beir.; rad,..
'.. Spiking Levels 'Kithods 1-"'
Currently, selects: !.'~3 sartles ar- being spiked a: either Level
1 (5 tires X?L , Lev,! : ;i: ti: = s KP.L . cr Level 3 (22 tir.*s y.?L .
In rany cases, spikir.; a: Level 2 has crested analyte concer.traticr.c
in sar-les whicr. exce*: the linear range of the instru=sr.:a:ion. Ar.y
Level 3 spiked sazples currently or. har.i should be analyzed: howeve:,
no further requests v:ii be cad* to spixe sarples at Le-.'=l ?.
In order to .Tamtam three spiking levels, a Level 0 (2 tir.es
XRL) is bein; addei. Lc:::a::ry Central Standards and Tire Storare
Sa.r;lss are to contin-c tc be ssiics- at Level 2 (1C tir.es KSL' .
2. Spikin; Levels (Msthod 9)
Currently, saiple spiking levels used for Kethoc 9 are. Level '.
(2 times MRL) . Level 2 (10 times KRL) ._ and Level 3 (10,000 ug/L) . T:..
spiking levels are to remain the sare: however. Level 0 will now it :
tices KRL. Level 1 10 tices MRL, and Level 3 10,000 ug/L.
3. Data Reporting Format
In order for the data reporting forcat to match the requirements
for reporting suspected NFS analytes observed on the prirary colucn.
at a concentration between 1/2 KRL and KRL (see eemorandusr entitled
"Determining and Reporting the Presence of N7S Analytes below tht
Miniaux Reporting Levels anc Identifying Unknown Peaks," by Bob Kaxey
6/1/88), further clarification is required. la those cases where tU
presence of an NPS analyt* at a concentration between 1/2 MRL and thi
MP.L is successfully confirrtd, the primary and confiraational colur:.
data for that analyte should be reported as "-111". In those cases ,
where confiraational analyses are cither not required, or the
confiraational analyses did not confirm the presence of the analyte,
the primary column data for that analyte should be reported as "-222".
-------
-2-
Please transmit this information to both your contract aad refers
laboratories, as soon as possible. It you have any questions concern;
these ir**s, please let ae know.
Addressees:
A. Dupuy
L. Kacphake (TS2)
C. Kadding (?s:;
R. Maxey (OP?)
K. Sorrel! 'TS:1
R. Tho-as (7S:1
H. Brass ITS:'
C. Freebis (CS:
A. Kroner (TSZ'
-------
Appendix F
Revision No 3
Date August 1, 1990
Page 1 of 17
APPENDIX F
ICF SAMPLE RECEIPT SOFTWARE
-------
4/5/88
TO: LARRY OGLE. RADIAN, INC.
FROM: CHIP LESTER. ICF INC.
RE: NPSIS SAMPLE RECEIPT SOFTWARE FOR LABORATORIES
ICF's National Pesticide Survey Information System (NFSIS) is ready to
collect information from you regarding the receipt of well water samples and
their condition. Please find enclosed the following items: 1) A users memo
containing all operating instructions, and 2) A copy of Carbon Copy software
which is necessary to establish communications with NFSIS over phone lines.
As mentioned previously, the software allows you to report the receipt of a
one or more sample kits. It also prompts you for details regarding the
condition of the samples. Additional features include; a bulletin board which
allows you to interactively send messages to ICF staff via your computer
keyboard, file transfer, and access to the ICF computerized mail system for
sending memos. It is also possible for you to speak over the phone to an ICF
staff member during your session.
It is important that you test the communications link between the NPSIS
computer and yours. We have experienced trouble when using Carbon Copy
software with a computer which has a Manzana 3.5 inch disk drive, and also
with computers which have a non-Hercules or non-ECA compatible graphics card.
For testing purposes, your sample kitidentification numbers and FedEx
airbill numbers (respectively) are: PD-0000-341 and 1111111111, and PD-0000-
342 and 2222222222. Use these sample kit identification numbers when trying
out the NPSIS Sample Receipts Program.
We feel that it would be helpful to both parties if you could call us
when you are ready to test the HPSIS system, and we will assist you over the
phone during your session. If you would like to do this, please call Beth
Estrada ac (703) 934-3431. NPSIS will be available for access 24-hours a day,
seven days a week. We appreciate hearing any comments you have regarding
NPSIS.
-------
THE NPSIS SAMPLE RECEIPT PROGRAM
NFSIS is designed to keep crack of the day to day operations of the
National Pesticide Survey. You play an important role in NFS and your timely
notification of receiving a kit of samples is essential co the success of NFS.
We have designed the Sample Receipt Program with your busy schedule in mind.
NPSIS will obtain the minimum amount of information necessary while still
maintaining a secure system. You will be entering data into the NPSIS
personal computer via your own computer, modem, and Carbon Copy software.
I.I Hardware and Software Requirements.
The NPSIS Sample Receipt Program has a minimum hardware and software
requirement. Here is a list of items you will need:
Hardware:
One (1) IBM PC, XT, AT, or Personal System model with at
lease 640K memory.
One (1) 2400 or 1200 baud Hayes or Hayes compatible modem
with cables. (See Carbon Copy guide for cabling requir-
ements and a description of usable modems)
One (1) data transmission phone line.
Software:
NFSZS Sample Receipt Program access provided for you by
ICF.
One (1) copy Carbon Copy software which is provided to you
by ICF for the duration of NFS.
1.2 Initial Tnacallaclon Sc«t»a.
Before you can access and use NPSIS, you must first load the Carbon Copy
software onto your PC. The directions are provided in the Carbon Copy manual.
One item you will wane to include is an entry into the "Call Table*. This
entry will include a name, telephone number, and password for the NFSIS
computer. To enter these item* lac* the Call Table, press "2* from the Carbon
Copy Parameters' Screen. The information you must enter consists of the
following:
-------
Name: NPS
Telephone Number: 703-961-0629
Password: NPS
1.3 PflrameCBrs for Communications. i
NPSIS will maintain a set configuration throughout operation. Any
changes due to updates in equipment or the system which will affect your
ability to communicate through Carbon Copy will be forwarded to you. The
parameters which will be maintained at this time are:
2400 baud modem speed.
Answer ring count equal to one.
Re-boot on exic after 5 minutes. (If there is a power
failure or some other type of interruption, you can log
back on to NPSIS and resume your session.)
Five minute inactivity time constraint.
Two password attempts.
C A SAMPLE RECEIPT TO ffPSIS.
2 . 1 Establishing a Communications Link
Once you have installed Carbon Copy and have all of the necessary
hardware, you are ready to "log on" no the NPSIS computer at ICF. To do this:
Type: C:> COOELP UPS in your directory containing Carbon Copy.
This command will automatically dial the NPSIS computer, send your password
for verification, and establish a data link between the two computers. You
will be able to discern ---hat is taking place by messages to your screen.
2.2 Entering A Sample Receipt Into NPSIS.
Once you have established a data link, ( e.g., are "logged on*), you will
see on the screen exactly what is on the screen of the NPSIS computer.. This
screen you are viewing is the aain menu for the Saaple Receipt Program.
Remember that you are controlling the NPSIS computer via a 2600 baud phone
line and your typing will appear on the screen ac a much slower rate than you
are accustomed to. A few tipe on how to use the system are outlined in the
next section.
-------
2 2.1 Useful Tips on Hov to Uam NPSIS.
Before you start, a few things to remember are:
Pressing che "Esc" key will cancel all changes for the screen you
are currently in and return you to the previ._s screen. Pressing
"Esc" at. che Searching Screen returns you to the main menu.
Pressing "PgDn" or "PgUp" will save the items you have entered in
the current screen and place you in the next or previous screen,
respectively. This feature is handy to use when you only have a few
items to enter in a screen which prompts for several items.
Pressing "Enter", "arrow up", or "arrow down" will move the cursor
from field to field in each screen. Remember that using the
sideways arrows will not work.
Pressing the "Alt" and "Right Shift' keys together will place the
Carbon Copy Control Screen-over the NPSIS Sample Receipt Program.
You can then use the communications features in Carbon Copy.
Pressing "F10" again when you are through will replace the NFS IS
Sample Receipt Program screen you were currently in back on your
screen, and
Because you will are most likely to be entering information
regarding a number of kits at one time, after you save or cancel
your entries for one kit, you will b* placed ac the initial Sample
Searching Screen for a new kit. If you are finished with your data
entry, simply press "Esc" to exit the Sample Searching screen and be
placed in the main menu.
2.3 A Basle Outline of the Sainclft Receipt Prgyram,
The NPSIS Sample Receipt Program has three basic features:
Initial reporting of a NFS sample kit of sample bottles.
Ability to edit or re-edit an existing report of a kit
receipt, and
Access to ICFs computerized mail system which provides the
ability to send memoranda to ICF staff.
The information obtained in an entry for a kit of bottles is:
The kit identification number, the FedEx airbill number,
and the last name of the person making the entry.
Any damage to the kit as a whole such as melted ice or any
breakage of che cooler.
-------
Verification of which bottles belong in a kit or cooler,
notification of any missing bottles or any additional
bottles, and
Any damage to each sample bottle which renders it unusable
for analysis and testing.
2 4 VPSIS Sanmle Reeeint Prc
When you have completed the logon procedure, you will see che following
main menu on your computer screen:
NATIONAL PESTICIDE SURVEY INFORMATION SYSTEM
SELECTION MENU FOR REPORTING SAMPLE RECEIPTS 04/05/88
Report \ Edit a Sample Receipt
Send a Memo
Press to Logoff
use f land +* to select option.
The screens provided in this memo will show all of the screens available
and thus represent the maximum number of screens you will encounter with
NPSIS. Ic is most likely chat you will not have the need to enter information
reporting damaged kits or samples. Therefore, not all of the screens depicted
below will appear in your normal session.
If you choose the first Item on the menu, "Report \ Edit a Sample
Receipt", you will then be prompted for the kit identification number and the
FedEx airbill number associated with the specified kit. The screen will
appear like this:
-------
NFS Sample Receipc Searching Screen
** Encer the following items to access kic information **
To find the Kit information in NPSIS in che most complete
and accurate fashion, please enter the Kit number and the
FedEx airbill number.
Enter kit number:
> PD-0001-151
Enter FedEx airbill »:
> 1111111111
Enter your last name:
> CHIANG
Press ESC to exit the searching
If the kit number you have entered is incorrect, or if the kit number and
FedEx airbill number combination is incorrect, NPSIS will prompt you to try co
enter these number again, as illustrated on che next page. It is possible
that che FedEx airbill number on the kit is not the same as the FedEx airbill
number which was entered into the NPSIS system. This could happen if che
field team loses or damages the airbill.
-------
ERROR!! The kit you entered cannot be found. . .
Kit "number: PD-0001-151
AND
FedEx airbill number: 1111111111
Please check these numbers and try again!
****** J> ****** ***** *«***!> ***** *** *** *»> t***'***** ******** *** A It *****
NPSIS is designed to track Kits and FedEx airbill numbers.
The Kit and FedEx airbill number combination you have entered
does not match what is currently in the system. Please enter
the correct combination. If you still have problems, try
leaving the FedEx airbill « BLANK. Only enter the Kit number.
** * **«"* ********* * «********»***** ******* ********* it**** *** it ********
Press any key to continue...
Then, you will encounter this screen insuring that you have entered the
FedEx airbill number:
Kit No.: PD-0001-151
Did you enter the correct Kit number and FedEx airbill number?
NPSIS is designed to store and track all FedEx airbill numbers.
This Kit may have a different FedEx airbill number than the
system, please enter the new FedEx airbill number:
Note: if the correct airbill number was entered before, hit ENTER.
PgDn (Next page). PgUp (Previous page). Esc (Exit)
-------
Onct you h*v« correctly identified che sample kic, NPSIS will ask you if
char* is any damage Co che kit as a whole:
Kic Mo.: PD-0001-151
Uas ch*r« any damage co che sample kic? (Y/N) Y
PgDn (Nexc page), PgUp (Previous page). Esc (Exit)
-------
If you press "Y", NFS IS will then prompt you for ch« apparent cause of
damage:
Kit No.: PD-0001-151
Was there any damage to the sample kit? (Y/N)
Please indicate the cause for damage:
Kit is broken (Y/N) Y
Ice is melted (Y/N)
Other Reason (Y/N)
Please enter any comments about the sample kit.
Comments: Broken upon arrival.
Comments:
PgDn (Next page). PgUp (Previous page), us* t |or
to select field.
There may already be comments regarding the kit in the comment field
shown in the above screen. In this case, please enter your comments after any
which already appear. This insures that no information is destroyed.
-------
Next, IfPSIS will ask you to survey ch« contents of ch« kit and check that
which bottles are contained within th« kit. You should then look at ch«
bottle labels and determine tf any are missing. Don't forget to check and
determine if any bottles have been included in the kit which do not apn.ar on
the list provided by NPSIS on this screen:
Kit No.: PD-0001-151
Please compare the following bottle numbers
with those in the sample kit.
Bottle No:
Bottle No:
Bottle No:
Bottle No:
Bottle No:
Bottle No:
PD-0001-1-1-01
PD-0001-1-1-03
PD-0001-1-3-01
PD-0001-1-3-03
PD-0001-1-9-01
PD-0001-1-9-03
Did you receive exactly these bottles in the sample kit? (Y/N) If
PgDn (Next page), PgUp (Previous page), Esc (Exit)
-------
If you h»v« pressed "N", indicating that you did noc receive exactly what
NFS IS assumes you have received, you will be prompted to enter ch« appropriate
information. This information includes pressing a "Y" or a "N" beside each
bottle, arid entering the bottle number found on the labels of any additional
bottles you have received:
Kit No.: PD-0001-151
Please indicate vhich bottles you received:
Bottle No: Received (Y/N)
PD-0001-1-1-01
PD-0001-1-1-03
PD-0001-1-3-01
PD-0001-1-3-03
PD-0001-1-9-01
PD-0001-1-9-03
H
ft
Y
.Y
Y
Y
1.
3.
5.
7.
Please indicate any additional bottles you received:
Bottle No.: PD-0002-1-1-05 2. Bottle No.: PD-OO02-2-2-01
Boctle No.: PD-0004-4-4-01 4. Bottle No.: ...
Bottle No.: - - - - 6. Bottle No.: - ...
Bottle No.: - ... 8. Bottle No.: - ...
PgDn (Next page), PgUp (Previous page), use f ^or «'to select field.
Notice that the user has indicated that he did not receive the first rvo
bottles on the list. Also note chat the user has indicated additional bottles
vhich have com* in the sample kit. but vhich were not on the list.
-------
N«xt, NPSIS prompts you to Indicate If any of eh* Individual boccles have
been damaged and rendered unusable for analysis:
Kit No.: PD-0001-151
Was there any damage co the sample Beetles? (Y/N) Y
PgDn (Nexc page). PgUp (Previous page). Esc (Exit)
-------
In ord«r co complete che appropriate information on damaged saaplts, you
must first press a "Y" or a "N" in the field labeled "Damaged Y/N". If yQU
have entered a "Y" in this field, you muse Chen identify what the cause of che
damage is. to the best of your abilities. As noted on the computer screen
below, che "Other" category should be used if che sample is unusable but is
not broken. Please try t- comment whenever possible.
Kit No.: PD-0001-151
Please indicate which bottles are damaged by entering Y or N,
and for those which are damaged, indicate che cause of damage.
---CAUSE ---
Bottle No: Damaged Broken Other Comment
(Y/N) (Y/N) (Y/N)
PD-0001-1-3-01 n
PD-0001-1-3-03 K
PD-0001-1-9-01 N
PD-0001-1-9-03 N
PD-0002-1-1-05 H
PD-0002-2-2-01 Y Y
PD-0004-4-4-01 N
The 'Other' cause category is for reporting contamination of a sample,
e.g. contamination noted on the Sample Tracking Form, air bubbles,
or other reasons a sample is unusable.
PgDn (Next page), PgUp (Previous page), use 4 I or *-J co select field
-------
Now you have completed all of the necessary information needed to verify
chat the proper samples have reached cheir final destination in usable
condition. You may save your kit encry by pressing "Enter". If you wish to
cancel your kit entry and try again, press "N" and "Enter". If you wish co
view or adit the current kit antry, press "R" and "Enter" and NPSIS will place
you back at the beginning of your entry.
You have completed all of the data entry screens for this Kit.
You may save your entry by pressing 'Enter' .
You may cancel your entry by pressing 'N' and 'Enter'.
.You may verify or edit this entry by pressing 'R' and 'Enter'.
* * * Accept entries? * * *
to Save *
to Cancel *
to Verify 'or Edit * T
* Press
* Press N and
* Press R and
By pressing "Enter* , you have saved all of the information necessary for
a particular sample kit. NPSIS assumes that you will enter more than one kit
entry per session. Therefore, you will be placed at the initial "Searching
Screen*. If you are finished, press "Esc" and you will be returned to the
main menu. You can then log off of NPSIS by pressing "Alt" and "Right shift"
at the same time. You may also send a memo through the ICF computerized mail
system. To do this, cursor down to the second menu choice and press "Enter".
The next two pages of this memo describe hov to use the ICF electronic
mail system. Note that the password for you is NFS. The mail system software
program will prompt you for this password before it will allow access to the
system. Also, when you are selecting the recipients of your memo, please
press the space bar beside the initials "NPS". This will send your memo to
all ICF staff involved in the NPS project. If you wish to send memos to a
particular ICF staff member, please call Beth Estrada for the identification
number of the desired ICF employee.
-------
ELECTRONIC MAIL
Function
Augment office communications
electronic transfer of notes and files.
with
Summary
Electronic Mail (E-Mail) allows you to send,
receive, read, and subsequently save or
discard notes and attached files.
When you power up your workstation you
will automatically enter E-Mail if you have
received any mail. Enter your password to
check your mail, or press twice to
avoid E-Mail and continue to the Assist
main menu.
Instructions
Operation of E-Mail is similar to Lotus
1-2-3. Press the Fl key to receive help at
any time during operation. If any more
help is needed contact workstation support
to receive a manual.
For more information on any feature of
electronic mail, use Network Courier's on-
line help or refer to the User's Manual.
Passwords
Your password will be "password* until you
change it yourself. Once you have given
your password and entered E-Mail, you can
change your password by selecting Options,
then Password.
Reading Mail
1. Select "Read" from your menu.
Highlight read,then press
.
2. Select the note to read:
a. Highlight the note (using
the arrow keys); and press
.
B. To save the note, select
"Storage", then "Save". Enter
the name of the file to which
the note should be saved.
3. Press to select another note.
Writing Mail
1. Select 'Compose*, then "edit".
2. Press when the highlight
moves to "TO*.
3. Select the recipients(s):
a. Move the highlight to the
first recipient's initials.
b. Press the space bar. A
small mark will appear.
c. Repeat steps a and b for all
recipients. Press the space bar
twice to "de-select" recipients.
The small mark will disappear.
d. Press <£SC> to cancel the
entire list.
4. Select the initials of those who will
receive copies:
a. Press the down arrow to move
to *CCT.
b. Select recipients as instructed
above (step 3, a-d)
-------
Writing Mail, continued
5. Eater a subject and priority.
(optional)
6. Select attachments-(optional):
a. Press and type the
path for the document(s).
b. Press and select the
document(s) to be attached.
c. Repeat steps a and b for
documents in another directory.
7. Enter the text of your message.
8. Press when finished.
9. Select "Transmit" to post the note
and attachments.
Quitting to* Mail Program
1. Press from the menu.
2. Select 'YES'.
-------
Appendix G
Revision No 3
Date. August 1. 1990
Page 1 of 2
Appendix G
GUIDELINES FOR RECEIPT OF SAMPLE KITS
-------
MEMORANDUM
Date: November 6, 1989
To: NPS Analytical Laboratories
ICF Prep Room
From: Lora Johnson, QAO - NPS
Robert Maxey, Analytical Coordinator - OPP
David Munch, Analytical Coordinator - ODW
Subject: Guidelines for Receipt of Sample Kits
Recently, it has come to our attention that some discrepancies exist between
laboratories on how to handle NPS sample kits that arrive with the ice meltea.
The following guidelines are provided to give clear direction on the course of
action laboratories should take under the circumstance when no ice is present
in the sample kit.
1) Analyze the affected samples - you will receive payment for samples that
arrive with melted ice.
2} Take the temperature of the 'standing water in the bottom of the sample'
kit, record the temperature in degrees Centigrade on the sample tracking
form and input the value into NPS IS. DO NOT TAKE THE TEMPERATURE OF THE
SAMPLE IN THE BOTTLE.
3) Record any subjective observations you have about the samples and/or
sample kit (i.e. the bottle was warm to the touch).
4) Contact your technical monitor if you have any further questions.
Thank-you for your cooperation on this matter.
cc: J. Briskin
J. Bo land
M. Gomez -Taylor
E. Leovey
H. Lester
L. Macrl
M. Wlnslow
J. ZallkowsM . o . , ) .
D. Zimmerman OX. \C
L i
-------
Appendix I
Revision No 3
Date August 1. 1990
Page 1 of 5
Appendix H
NPS METHOD 4 REVISED CONFIRMATIONAL
ANALYSIS METHODOLOGY
-------
\
? UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
e
.CINCINNATI OH|O 45268
Technical Support Division
Office of Drinking Water
26 West Martin Luther King Drive
Cincinnati, Ohio 45268
March 10, 1989
Mr. Larry Ogle
Radian, Inc.
3501 Mo-Pac Boulevard
Austin, TJC 78766
Dear Larry:
Enclosed are the tvo confirmation standard mixes, Conf4-Std3B and
Conf4-Std3A. I have also sent a copy of the chroaatograas for both.
These were obtained with a J&V CM coluan and the conditions are as
follows:
Mobile Phase - Acetonitrile/Vater
Flow rate » 1.0 mL/min
Initial conditions * 15% Acetonitrile
Injection volume * 20 uL
Gradient Program "'Hold 4 am after injection, then
15% to 60% Acetonitrile in 20 mm
The last coapound elutes at 25 am, but I run the gradient up to 80%
(in 2 mm) and hold for 4 am to clear the column. After returning to the
initial conditions (15% CB3CN), allow 15 am for equilibration.
Should you hart any questions, please call.
Sincerely yours.
R. Kent Sorrell, Chemist
Drinking Water Quality
Assessaent Branch
Enclosure
-------
XA« wAiA JAV&iJ iff
r.-.comi.
03-03-1919 10:27:20 Version 4.1 *
Sample Mama: COMF.4 STD3B Data File: K:CONB1
Data: 03-03-1919 10:27:09 Method: K:COHT4B 03-03-1919 09:29:09 f 64
Interface: 2 Cycle*: 1 Operator JCW Channelf: 0 Vialf: H.A.
Starting Peak Width: 15 Threshold: .2 Area
Instrument Type: ABI HPLC-UV confirm Column Type: 5u CaTvSespher* 25cm
^ Solvent Oeaeription: water / aeetonitrile
CondXiona:
j Detector 0: 254UV Detector 1:
fiael :
* MiaeJt Information:
*** '* «*************
Starting Dalay:
Area reject:
Amount injaetad:
Sample Weight:
0.00
0
1.00
1.000000
Ending retention time: 25.00
One aampla per 1.000 sec.
Dilution factor: 1.00
»!K
IUK
:
4
4
5
a
*
1
?
1C
t
.4
M
14
15
m
3.
4.
7.
13.
12.
13.
IS.
17.
11.
1!.
2C.
21.
23.
24.
72
SI
t:
:?
10
10
OS
30
(2
il
92
12
10
SS
Hit COIC1RI1TTGI ia
UH ||/L
mini* OMII
umiictii 01
rn-oirni
cmnii
mnu
oinoi
r.j.
MOMIIL
mi
sniocm
min
TCTIL iionr *
i -at
&
11.7432
i.7Sfl
44LI01J
H>.2fllp
^Ufl
5.I2II
^31. (421
, yjifltO
i/&j|tti
I -'3 tall
3l'.i777
421.2274
C3IC
i
f
3
4
1
13
3
0
10
0
ss
0
1
0
1
.2flf!l
.43071
.427U
.37SU
.1114t
.4i20t
.02521
.04111
.47011
.iiOtl
.!1W
.42(71
.25111
.73HI
.14121
1IU/
1111 IIICI? Hlfin It
5117!
C12ii
11211
UI3S
1750!
1HI7
!124
2051
12721
11032
2271!
!252
17011
11351
10!03
3SS3
3S03
i4S
470
744
332
11!
m
177
III
ill
1005
11C2
7sr
14.5
2f.2
21.1
37.3
2(.S
27.5
17.2
25.4
11.3
2S.7
13.1
17.8
15.1
14.S
2
2
1
1
1
1
1
4
A
2
2
2
t
1
1
ur
mi
14
14
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14
14
14
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t BKfl
in rin
*
.2111
-.l<7!
.HIS
. 0
0
.1410
3
.Hi:
.132!
0
.1473
aiMiEi
.33001-94
.03331-04
.30:31-94
.'.'J3I-C1
.TII4M4
.27!'I-:i
.4im-:3
!:24l!-:3
.'5<8!-;i
.!:C"!-"»
J747K4
.;45'!-84
.'2r!-9f
.31Z1T-J3
Areaa, timea, and heights stored in: K:COMB1.ATB
Data File - K:CONB1.PTS Printed on 03-03-1919 et 10:27:46
Start time: 0.00 min. Stop time: 25.00 min. Offset:
Low Value: 1 uv High Value; 416« uv Scale factor;
* ^? 'SrrrS
0 mv.
1.0
-------
-------
-------
Appendix J
Revision No 3
Date: August 1, 1990
Page 1 of 4
Appendix I
DATA REPORTING CODES
-------
OME: septanber 9, 1988
SUBJECT: Data Reporting Codes
FPCM: Christopher Frebis, CSC Statistician
TO: Distribution
The purpose of this memorandum is to discuss the reporting codes used in
the National Pesticide Survey. There has been sane confusion over these crrV»g
as to when and where to use than and their exact meaning.
Table 1 identifies the unique sample types (SAMP - field sanple, MBLK -
method blank, SBLK - shipping blank, LCS - lab control standard, and LSS, DPS,
HTE, and HIS - spiJced field samples these last three are each a type of time
storage sanple). under each unique sample type are the only possible cnrles
that can appear for that sanple type. (Note: -555 has been artrted for the
situation where the contract lab sends the extract to the referee lab for QCMS
analysis, and the code -222 has been deleted.) There is aicn a type of
decision tree for field sanples since they are a little more complicated with
three analyses for confirmation and qualitative only analytes.
I hope this memorandum helps to put everyone on similar terms as well as
clearing the muddy water. If there are any questions of different scenarios
you wish to discuss, please call me at (513) 569-7498.
Distribution: Herb Brass, Technical Support Division
Aubry Dupuy, Brvironmental Chemistry laboratory
Carol Mailing, Technical Support Division
Bob Maxey, Environmental Chemistry Laboratory
Dave Munch, Technical support Division
Kent Sorrell, Technical Support Division
Bob Thomas, Technical Support Division
-------
TABLE 1: USES OF EMA <»'»"-JS IN NFS
SAMPLE TYPE
SAMP
.(a)
ill
_333(d)
.4446
_555(f)
-666 (9>
-777 <*
888 ^
_999(j)
conc<*>
MHLK
.
SBLK
_(a)
111 (^)
-333(|3)
.444(6)
_555
LCS
.(b)
***»
****
****
****
****
-777
-------
ff»p^rftri,|T
-333
-999
888
-333
-333 -555 -999
-333 -999 888
HUM
OUT
888 QCMS
GOG
(at referee;
le
with CC. ai
-333
-444
-666
-333 -666 -999
333 -555 -999 8
PRIM
OCNF
QCMS
00-E
(at referee)
-111 -333 -777* -999
-111 -333 -999
PRIM
OUT
-333 -555 -999 888 -333 -555 -999 888 -333 -555 -999 888 -333 -555 -999 888
-333 -999 888 -333 -999 888 -333 -999 888 -333 -999 888
(at referee)
a - Dilute and reanalyze
-------
Appendix K
Revision No 3
Date' August 1, 1990
Page 1 of 10
Appendix J
NFS DATA FORMAT/DATA FORMAT CHANGES
-------
FCRAT KF WKTICNNL t*«ru "- SURVEJf (NFS)
1-6 rid
9-14 i
17-24 Date_Sam
27-34 Date_Snp
37-44 Date.Rec
47-54 Tine.Sam
57-64 Tirae.Ice
[FGR VEKL& 5 MO 9 CNLY]
68-69 pH
1-6 enter pH CF YIELD
9-14 enter STABILIZED TEWERMURE CF
17-24 enter EME S^KJOJ
27-34 enter EME SHltKD
37-44 enter CASE RECEIVED
47-54 enter TBC S>*FLED
57-64 enter TDC ICED
[FCR IGHODS 5 MO 9 CNLY]
67-70 enter pH CF LAB SWPLE
3
4 1-17 Receipt condition
5 1-80 enter CCUDITICN CF SS*KZ UPCN KHI-JIrt* AT
6 HLAMC
7 1*6 Swp t
16-18 Lab
21-25 Sttt t
28-35 Dste.Spk
38-45
48-55 Dtt*.Mi
58-63 Oolom
enter S*fLE UtNi'JJlOiTICN
16-18 enter LAB AEEREVDOXCN
21-25 enter SB tOBTO
28-35 enter OME SPHCED
38-45 enter CMC
48-55 enter EME MALHZD
58-63 enter MfeLYSXS COJUMi
-------
FORA? FCR NMICXSSL mvi'irrrg SURVEY (NFS) EMA (cent.)
10 1-4 Type
8-13 SpUcer
16-22 Extract
25-31 Analyst
34-40 Sanv_Vol
43-49 EXtJJOl
52-60 Int. Std.
65-70 % SUTT
11 1-5 enter SWLE TYPE,
8-13 enter SPIKER'S INITIALS
16-22 enter E3ORACTQRfS INITIALS
25-31 enter ANALYST'S INTTIM-S
34-40 enter ^xxu^£ OF STOLE
43-49 enter VCH1C CF EXU^ACT
52-62 enter nngMtf. S3MIMD (as %of calibration standard)
65-70 enter PER3NT REC^ERY OF SURRDOJE
12 ELATK
13 1-8 Comnents
14 1-80 enter ANY PERTINENT CO-MENTS CN SMfJlZ AND ANALYSIS
15 BLANK
16 1-7 Analyte
29-33 Cone.
39-45 Analyte
67-71 Gone.
17-? 1-25 enter AWLYTE'S NVE _ _
28-34 enter OQNCENIRATICJJ GR PESCENT REODVERY
39-63 enter ANKLYTE'S »M£ _ _
66-72 enter CCNCENlFAnCN CR PE3ONT RED^ERY
-------
FORfKT FOR NATIONAL rti'l'lUUt SURVEY (NFS) QETRtMEHT OOOTHX EftTA
l 1-3 Lab
6-11 Method
14-21 Dste_Ana
24-30 Analyst
35-37 S/N
42-44 PST
4*-51 POT
55-58 RBS.
2 SANK
3-? 1-3 enter LAB AEEREUIAIXCN
6-11 enter MEHHZ) NUCER
14-21 enter OKIE ANALYZED-
24-30 enter ANALYST'S INITIALS
33-37 enter SIC2AL 10 NOISE RATIO
40-44 enter PEAK SYWMEESf FACTOR
47-51 enter PPK^gmETO FACTOR
54-58 enter RESOLUnON
-------
CRUDE FSFPtESEHIXnCN OF CKEA FLCW
l. samples are taken in the field.
2. Samples are iced and shipped to the laboratory.
3. Laboratory prepares and analyzes field samples along with QC samples.
4. Laboratory enters field and QC data on a computer in "sets" and it
enters instrument control standard data in a separate file.
5. Laboratory creates an ASCII file of the data using the specified formats
on an IB4 PC compatible floppy disk.
6. Laboratory sends the floppy disk to Christopher Frebis at the EPA in
Cincinnati, Cnio.
26 W. Jtertin Luther King Drive
Cincinnati, CH 45268
NOTE: The maximum tine from item 1 to item 6 is two (2) months.
7. computer Sciences corporation (CSC) personnel transfer the data from PC
to IBM 3090 mainframe in North Carolina (or possibly to IBi Logical
Minframe in Cincinnati).
8. The data is edited on the mainframe and then checked for compliance
with QC requirements using SAS, a statistical programming language.
9. A hard copy of the edited data, with "suspect11 data highlighted, is
sent to the technical monitor for their review.
10. The technical monitor returns the data to C. Frebis with comments,
deletions, etc. this is the **i data.
11. The data is re-edited per the technical monitor's review and a SAS data
set is created for the data.
12. A printout of the final sample data for each site will be provided to the
NFS
13. The "approved* field samples are sent to ICF for their analyses.
14. All QC data is retained by C. Frebis to generate monthly QC reports and
a final QC report at the end of the survey.
-------
NOTES CN NFS DMA P3WM5
1. The format for any date is mm/dd/yy
A missing date should be entered 01/01/60
2. The format for any tine is hh.:mn in military time
A missing time should be entered 00:00
3. Any other data that is missing should be entered with a period ( . )
4. TSie ranber of decimal places should be as follows:
OcuctsiUdtion 3
Percent Recovery l
Internal Standard 0
instrument Controls 2
PH 1
0
Voluies 0
5. The codes for Colum are as follows:
Primary PRIM
Confirmatory CQNF
Ttiird 006
6. The codes for Ldb are as follows:
TSD TSD
GPP CfP
WEPL HEK
Radian RAO
Battelle BCD
James M. Msntgonery JMM
Alliance All.
Bwirarwental Sciences and Eiigineering E5E
7. B» codes for Type are as follows:
Field sample
Shipping Blank SBLK
Method BlanX VOX.
Lab Control Standard LCSf
Lab Spike Sample LSSSt
Day 0 Time Storage DTSf
Time Storage for Extract HJEI
Time storage for Sample HXSt
where t is the mix letter (A.B or C)
and t is the spiking level (1,2 or 3)
-------
M7E5 ) some number in the NFS instrument
control data, then use a minus sign (-) instead of >
-------
oancs FESETRCD CM ws IMA BY cac
1. Is the instrument control standards's signal to noise ratio greater than
the iL^Li the method specifies?
2. Is the instrument control standard's peak symmetry factor within the
limits set by the method?
3. Is the instrument control standard's peak geometry factor within the
limits set by the methods?
4. is the instrument control standard's resolution within the limits set by
the method?
5. is the date from sampling to receipt within the limits set by the survey
requirements?
6. Is the date from sampling to extract within the limits set by the survey
requirements?
7. Is the date from extract to analysis within the limits set by the survey
requirements?
8. Is the percent recovery of the surrogate within the limits set by the
survey requirements?
9. Is the internal standard within the limits set by the method requirements?
10. is the concentration of a blank above one-half (1/2) the reporting limit?
11. Is the concentration of a field sample above the reporting limit?
A. If so, is there a confirmation analysis for the analyte?
B. Is the concentration of the confirmatory column within the limits
set by survey requirements?
C. If the confirmatory analysis is above the reporting limit, is there
a OC/I6 analysis for the analyte?
12. Is the percent recovery of each analyte in the lab control standard within
the limits set by the eurvey requirements?
13. Is the percent recovery of each analyte in the lab spike sample within
the limits set by the survey requirements?
14. Is the percent recovery of each analyte in the performance evaluation
sample within the limits set by survey requirements?
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i
'i
I UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
,/ CINCINNATI. OHIO 49268
01V*
MEMORANDUM
DATE: April 18. 1988
SUBJECT: Data Reporting Format Chaogts
FROM: David J. Munch, Chemist
Drinking Vattr Quality Assessment Branch
TO: . NFS Ttchaical Monitors (Set below)
Tat purpost of this aeaorandua is to consolidatt tht changts to the
NPS data, reporting format, which have occurred since it was originally
constructed. You have previously been supplied with aost of these changes,
but please check to be sure that they have all been relayed to your
contract and referee laboratories.
1. Line 2. columns 1-6 are to be used to record the pH measured in
the field. This data will be found on the field sample tracking
sheet.
2. Lin* 2, columns 67-70 are to b* used to record the pH measured
upon sample receipt at the laboratory. This only applies to
methods S and 9.
3. Line 8, columns 1-13. Sample Identified.... Number, have been
expanded to columns 1-14.
4. The data entered on line 10, columns 52-60, concerning the
internal standard, it should be entered not as the peak area but
as the "percent recovery" as compared to the mean observed for
the calibration curve.
In order to simplify the "Sample Type" code (line 11. columns 1-5),
the following codes should be used to designate the various types of
spiked samples.
LCSt
LSStl
DTSt
HTtt
BTSt
Laboratory Control Sample
Laboratory Spiked Sample
Day 0 Time Storage Sample
Extract Time Storage Sample
Sample Time Storage Sample
In addition, two clarifications have been Bade to the codes for
aaalyte concentration entries.
-999 Not Detected « 1/2 Minimum Reporting Limit)
-111 « Below Minimum Reporting Limit but greater than or equal to
1/2 tht Minimum Reporting Limit.
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Hopefully this will eltrify the format for data rtportiog. If you
have aay question* or suggestions, pltase let ie know.
Attachment
Addressees:
A. Dupuy
C. Madding
R. Haxey
R. Sorrell
R. Thomas
c.e:
B. Brass
C. Freebis
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Appendix L
Revision No 3
Date. August 1. 1990
Page 1 of 7
Appendix K
RAPID REPORTING SYSTEM/CHANGES
TO RAPID REPORTING SYSTEM
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UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI. OMIQ 49268
MZxotAnux
DATE: April 12, 19S8
SUBJECT: HPS Rapid Reporting Systea
FROM: David J. Munch, Chemist
Drinking Water Quality Assessment Branch
TO: NFS Technical Monitors
Jtrry Rotas hat requested that any confiratd result! of health
significance be reported as quickly as possible. Therefore, if an analyte
listed in the attached tables is observed in the priaary analyses, at or
.above the rapid reporting liait, the following actions should be
instituted. For any listed analyte where the rapid reporting level is
less than or equal to 1/2 the ainiaua reporting level (MIL), any
occurrence at or above 1/2 the MRL should also be processed as below.
(Note: The procedures for determining the occurrence of HPS analytes that
aay occur below the MRL, and are not listed on the attached tables, have
not yet been finalized.)
1. The appropriate confiraational analyses (CC/MS for methods 1-3,
6-7, second column for Method 5) should be perforaed as soon as
practical.
2. The laboratory should telephone their Technical Monitor, the saae
day the confirmation is coapleted.
3. The laboratory should iaaediately document the observed result in
a letter to their Technical Monitor.
4. As quickly as possible oa the day the above telephone call is
received from the laboratory, the Technical Monitor should inform
their Laboratory Analytical Coordinator of the finding. The
Technical Monitor should forward oa to the Laboratory Analytical
Coordinator the above docuaentation, with aay coaaents he/she may
have concerning the validity of the result.
5. The Laboratory Analytical Coordinator should infers Jerry Rotas
aad the second Analytical Coordinator of the finding by telephone
the saae day if possible, and in writing after the docuaentation
is received froa the Technical Monitor.
6. The Analytical Coordinators are to request, through the
appropriate Technical Monitors, that all analyses for this saaple
site be conducted, amd reported in writing, as soon as practical.
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If you hart any qut.tion. conctrning thts* proctdurts, pit*,, itt Bob
Htxty or at know. Also, pltast pass OB this information to your contract
*nd r.itr.t laboraton.s. Thty will n..d to h*T. this infor.»tion in hand
prior to thtir conducting tht dry run.
Attachatnt
Addresstts:
A. Dupuy
L. Kaaphakt
C. Madding
R. Maxty
R. Sorrtll
R. Thomas
cc:
J. Kotas
B. Brass
A. Krontr
J. Orat
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HZTHOD 14
AKALYTg UP Ip REPORTING LZVTL
Cyantzint u ug/L
Diuroa 70 ug/L
Fluomtturon 433
Propfata 595
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f
i
r UNITED STATES ENVIRONMENTAL PROTECTION AGE\C
.< CINCINNATI o~'C
HXMORAJIDUM
DATZ: June 9, 1989
SUBJZCT: Revisions to NPS Rapid Reporting System
FtOM: David J. Munch. TSD Project Manager
National Pesticide Survey
TO: NPS Technical Monitors
Recently the health advisory documents for priority NPS aaalytes were
finalised (at least as finalized as they ever get). In many cases, the
health effect value used to determine the concentration of each analyte
that "triggered" the rapid reporting system, has changed. The purpose of
this memorandum is to transmit to you th* final rapid reporting
concentrations, and to remind everyone of the provisions of the rapid
reporting system.
As you remember, if an analyte listed in the attached tables is
observed in the primary analyses, at or above the rapid reporting limit.
the following actions should be instituted. For any listed analyte where
the rapid reporting level is less than or equal to 1/2 the minimum
reporting level (HRL), any occurrence at or above 1/2 the KXL sbould also
be processed as below.
1. The appropriate confirmational analyses (CC/HS for methods
1-3,6-7, second column for method 5) should be performed as soon
a* practical.
2. The laboratory sbould telephone their Technical Monitor,, the same
day the confirmation is completed.
3. The laboratory sbould immediately document the observed result in
a letter to their Technical Monitor.
4. As quickly as possible on th* day the above telephone call is
received from tb* laboratory, th* Technical Monitor should inform
their Laboratory Analytical Coordinator of th* finding. The
Technical Monitor should forward on to th* Laboratory Analytical
Coordinator the above documentation, with any comments he/she »ay
have concerning the validity of th* result.
S. Tb* Laboratory Analytical Coordinator sbould inform tb* Survey
Director and tb* s*co*4 Analytical Coordinator of tb* finding by
telephone tb* same day if possible, and in writing after tb*
documentation is received from the Technical Monitor.
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6. Tbt Analytical Coordinators art to request.through tht
appropriate Ttebnical Monitors, that all analyses for this saipie
sit* be conducted, and reported in writing, as soon as practical.
If you hare any questions concerning these procedure*, please let Bob
Maxey or « know. Also, please pass on this information to your contract
and referee laboratories.
Attachment
Addressees:
M. Bolyard
A. Dupuy
C. Madding
R. Maxey
R. Sorrell
M. Zuiker
cc:
J. Boland
H. Brass
L. Johnson
A. Kroner
C. Lester
L. Van Den Berg
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RETBOD 14
**ALYTt RAPID IPOiTMG LEVEL
20
70 ug/L
400 ua/L
600 ug/L
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Appendix M
Revision No 3
Dale August 1 1990'
Page 1 of 4
Appendix L
METHOD FOR REPORTING BELOW MRL AND THE
ID OF UNKNOWN PEAKS
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|
I UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
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Determining and Reporting the Presence of NPS Analytea Below The
Minimal Reporting Levels and Identifying Unknown Peaks
Background information
The Office of Pesticide Programs (OPP) has requested that the NPS analyti-
cal contractors and referee Laboratories make an effort to report the presence
of NPS analytes below the Minimal Reporting Levels (MRL). Me have also been re-
quested to attempt to identify unknown peaks or responses. To assure that spur-
ious or ambiguous data is not reported and that a uniform system or analytical
routine is used at all laboratories to accomplish these requests, criteria have
been developed for handling both situations.
Procedure for Determining and Reporting the Presence of NPS Analytes Below the
MRL
1. For methods 1-7, only peaks with responses of between one-half the establish-
ed MRL and the MRL V on the primary column will be investigated. A respona*
on the "secondary* GC column, indicating the presence of the analyte, is alac
required for additional work.
2.a The first occurrence of a peak meeting the requirements of (1) is noted and
reported to the Technical Monitor, but no action is taken B/. Upon a-second
occurrence of the same suspect analyte, additional work is required as fol-
lows. After five successive failures to "confirm" on the secondary column
the response on the primary column, discussions with OPP personnel will take
place before continuing low-level analytical work on the analyte(a).
b With methods 1,2,3, 6 and 7, Cor responses meeting the requirements of (1)
and (2), the laboratory will attempt LR GC/MS c/ confirmation if the GC/MS
analyst feels it is within the capability of his instrument. If the confir-
mation is not within the capability of the laboratory, such extracts are
sent weekly, under ioed conditions by next-day air/ to the appropriate re-
feree laboratory having HR GC/MS c/ capabilities. Copies of chromatcgrams
and all pertinent sample information must be sant along with the extracts «
including extracts of the related Method Blank. (NPS will absorb the cost
of these shipments.) It is preferred that extracts be in sealed glass
ampules, but other vials and teflon-faced closures are acceptable if they
provide a tight seal and do not contribute interferences to the extracts.
volume level must be marked on the outside of the vial or ampule.
A/ " NPS method 1 MRL 4 x EDL NPS method 5 MRL « 3 x EDL
NPS method 2 MRL « 5 x EDL NPS method 6 MRL - 3 x EDL
NPS method 3 MRL » 5 x EDL NPS method 7 MRL - 3 r EDL
NPS method 4 MRL -«5 x O)L
B/ Method 6 has an MRL > the Health Advisory Level. All suspect BTO
of 1/2 MRL - MRL require additional work for this method.
C/ LR » GC/MS Low Resolution mass
HR GC/MS - High Resolution
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
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c. For Methods 4 and 5, HPLC Methods, there is no provision for GC/MS
confirmation. Suspect analytes between 1/2 MRL - MRL will be subject
to (1) and (2a) above.
Provisions of (2b) also apply except references to GC/MS requirements.
3. Whether the identification of the analyte is attempted at the contractor
laboratory or at the referee laboratory, only analytes positively con-
firmed by GC/MS will be reported beyond the Technical Monitor for the
Method and the Analytical Coordinators. No unconfirmed data will be
reported outside the NPS analytical system. Unsuccessful attempts at
confirmation will also be reported to the Technical Monitor.
4. Following either the successful GC/MS confirmation of two such responses
for the same analyte or two successive failures to confirm the analyte
by GC/MS without any prior successful GC/MS confirmation on any samples,
discussions with OPP personnel will take olace before continuing low
level analytical work on that analyte.
Procedure for Determining the Identity of Non-NPS Analytes
It is 'expected that, over the course of the NPS Program, numerous
extraneous responses will be evident on chromatograms from the various methods.
The contractor or referee laboratories will be required to attempt identifi-
cation of peaks or responses on the primary column exhibiting the minimal criteria
below.
1. For Methods 1, 2, 3, 6, and 7, if, upon initial analyses, the response
of an extraneous peak on the primary column is equal to or greater than
the response of the nearest NPS analyte on that column at 10 x MRL
(Minimal Reporting Level), an attempt must be made to identify that un-
known peak or response by GC/MS. Pull scan spectra and subsequent
library search are expected and must be followed by comparison of the
spectra of the unknown compound with those of an authentic standard of
the suspected compound.
2. The work in (1) must be attempted by the contractor and/or referee lab-
oratories on the first occurrence of such a peak and the results of the
attempt reported to the Technical Monitor for the Method. If the
analytical contractor feels his system or instrument is not capable of
the confirmatory work, he must send both that extract and that of the
related Method Blank to the appropriate referee lab under ioed
conditions by next-day air.
It is preferred that extracts be in sealed glass ampules, but other
vial* and teflon-faced closures are acceptable if they provide a tight
seal and do not contribute interferences to the extracts. Volume level
must be marked on the outside of the vial or ampul*. (NPS will absorb
costs of these shipments.)
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