EPA-810/B-92-007
Office of Water (WH-550) EPA 810-B-92-007
Environmental Protection Office of Pesticides and February 1992
Agency Toodc Substances (H-7501C)
QUALITY ASSURANCE PROJECT PLAN
FOR THE
NATIONAL PESTICIDE SURVEY OF DRINKING WATER WELLS:
ANALYTICAL METHOD 7 - FUMIGANTS
Prepared by:
Michael G. Winslow
Environmental Science & Engineering, Inc.
P.O. Box 1703
Gainesville, FL 32602
Prepared for:
U.S. Environmental Protection Agency
Technical Support Division
Office of Drinking Water
26 W. Martin Luther King Drive
Cincinnati, Ohio 45268
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
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Section No. 1
Revision No. 2
Date: July 29, 1990
Page 2 of 2
Paul Geiszler
C. Madding
Portia Pisigan
Lora Johnson
Elizabeth Leovey
APPROVAL PAGE
, ESE Project Leader
, EPA Technical Monitor
, ESE QAC
, NPS QAO
, OPP QA Officer
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Section No. 2
Revision No. 2
Date: July 29, 1990
Page 1 of 2
NATIONAL PESTICIDE SURVEY
QUALITY ASSURANCE PROJECT PLAN FOR
ANALYTICAL METHOD 7 - FUMIGANTS
2. TABLE OF CONTENTS
Section
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
TITLE AND APPROVAL PAGE
TABLE OF CONTENTS
PROJECT DESCRIPTION
PROJECT ORGANIZATION AND RESPONSIBILITIES
QUALITY ASSURANCE OBJECTIVES FOR
MEASUREMENT DATA
SAMPLING PROCEDURES
SAMPLE CUSTODY
CALIBRATION PROCEDURES AND FREQUENCY
ANALYTICAL PROCEDURES
DATA REDUCTION, VALIDATION REPORTING
INTERNAL QUALITY CONTROL CHECKS
PERFORMANCE AND SYSTEM AUDITS
PREVENTIVE MAINTENANCE
SPECIFIC PROCEDURES FOR ASSESSING
MEASUREMENT SYSTEM DATA
CORRECTIVE ACTION
QUALITY ASSURANCE REPORTS TO
MANAGEMENT
ARCHIVAL OF RAW DATA
Pages
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2
1
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3
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5
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Revisions
2
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Date
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18. ADDENDUM TO ESE QUALITY ASSURANCE PLAN
FOR METHOD 7
7/29/90
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Section No. 2
Revision No. 2
Date: July 29, 1990
Page 2 of 2
2. TABLE OF CONTENTS (continued)
Appendices Pages
A.
B.
C.
D.
E.
F.
G.
H.
I.
J.
K.
L.
NPS METHOD 7 (EPA METHOD 504) (10/27/87)
MEASUREMENT OF 1,2-DIBROMOETHANE (EDB)
AND 1,2-DiBROMO-3-CHLOROPROPANE (DBCP)
IN WATER BY MICROEXTRACTION AND GAS
CHROMATOGRAPHY 16
NPS ANALYTE REPORTING BELOW MRL AND
IDENTIFYING UNKNOWN PEAKS 5
GC/MS CONFIRMATION OF NPS SAMPLES 2
IDC RESULTS 2
CHANGES IN NPS LABORATORY PROCEDURES 3
NPSIS SAMPLE RECEIPT SOFTWARE FOR
LABORATORIES 17
FORMAT FOR NPS DATA 6
DATA REPORTING FORMAT CHANGES 3
DATA REPORTING CODES 4
NPS RAPID REPORTING SYSTEM 1 1
DIXON'S TEST 5
STANDARD OPERATING PROCEDURE: BATCH
Revisions Date
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FILING SYSTEM
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Section No. 3
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3. PROJECT DESCRIPTION
The National Pesticide Survey is intended to assess the extent and nature of pesticide presence
in well waters used in private and community water supply systems. The statistical design of the
survey will suggest from a manageable number of samples and analyses the nature of pesticide
presence in such water supplies throughout the nation.
Environmental Science and Engineering, Inc. (ESE) of Gainesville, Florida, has contracted with
the U.S. Environmental Protection Agency (EPA) to analyze the collected water samples for
carbamates (Method 5) and halogenated fumigants (Method 7). This project plan applies to Method
7, the determination of ethylene dibromide (EDB), dibromochloropropane (DBCP), 1,2-
dichloropropane, and cis- and trans-1,3-dichloropropene in ground waters. Method 7 involves
extraction of the analytes from water, capillary gas chromatographic separation, and electron capture
detection and quantitation. Positive results will be confirmed by the same method using a second GC
column analysis. GC/MS will be used to verify confirmed positive results above the reporting limits.
Method 7 is an adaptation of EMSL method 504, "1,2-Dibromoethane (EDB) and 1,2-Dibromo-3-
chloropropane (DBCP) in Water by Microextraction and Gas chromatography" (Appendix A).
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Section No. 4
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4. PROJECT ORGANIZATION AND RESPONSIBILITIES
The project organization chart is presented in Exhibit 4-1. The managing staff are:
Paul C. Geiszler Project Director
Michael G. Winslow Project Manager and Technical Contact
Portia O. Pisigan Quality Assurance Coordinator
Virgina C. O'Brien Data Management and Sample Control
Glenn T. Jackson Manager, GC Volatiles Department
T. James Yeh Associate Scientist, Lead Chemist
EXHIBIT 4-1
PROJECT ORGANIZATION CHART
EPA TECHNICAL MONITOR
C. Madding
ESE PROJECT DIRECTOR
P. Geiszler
ESE PROJECT MANAGER
M. Winslow
ESE DATA MANAGEMENT ESE QA COORDINATION
V. O'Brien P. Pisigan
METHOD 5 ESE TASK MANAGEMENT METHOD 7
B. Weichert G. Jackson
HPLC ESE ANALYSIS GC
W. Keeran J. Yeh
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Section No. 4
Revision No. 2
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Page 2 of 2
Certain specific project assignments are handled by others:
Vince Prem-Das Sample Check-in
D. Michael Ritter Computer Sample Check-in and Data File
Generation
Richard Ross Sample Custody and Coldroom Support
Samples will generally be received by Vince Prem-Das, ESE, 14220 Newberry Road, Gainesville,
FL, 32607; phone (904) 332-3318. It will generally be necessary to ask the ESE switchboard to page
Mr. Prem-Das. In his absence, ask for Michael G. Winslow, Project Manager.
The EPA Technical Monitor (primary contact) for Method 7 matters is Caroline Madding, phone
(513) 569-7945. The EPA Project Officer is David J. Munch.
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Section No. 5
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Date: July 29, 1990
Page 1 of 2
5. QUALITY ASSURANCE OBJECTIVES FOR MEASUREMENT DATA
The "estimated detection limit "(EDL) for Method 7 will be determined as follows:
1. Determine the concentration of each analyte which, when injected, yields a 5:1
signal-to-noise ratio, measured as the ratio of the center chromatographic peak
height to the edge-to-edge height ol the noise envelope.
2. Spike eight HPLC-grade water samples at the concentration determined in 1. and
analyze together.
3. Calculate the Estimated Detection Limit (EDL) by multiplying the standard deviation
of the concentrations from 2. by the Student t-value 2.998 (7 degrees of freedom,
alpha = 0.99, one-sided).
4. The EDL is the greater of the values calculated in 1. and 3.
5. The EDL shall be evaluated by the Technical Monitor.
6. Acceptance of ESE's calculated EDL's shall be judged by the Technical Monitor
based upon health effects data and the technical feasibility of achieving EDL's
suggested by such data.
7. Analyze the eight sample aliquots of 2. on the confirmatory column and calculate
EDLs as in 1 and 3. The resulting EDLs must roughly equal those of the primary
column.
8. Perform up to six GC/MS analyses on the five analytes to determine the 5:1 signal-
to-noise ratio for the least intense ion, using the following ions for each:
Analvte Masses (amu)
EDB (ethylene dibromide) 107, 109
DBCP (dibromochloropropane) 115, 157, 159
1,2-Dichloropropane 62, 63, 64, 65
cis-1,3-Dichloropropene 75, 77, 110, 112
trans-1,3-Dichloropropene 75, 77, 110, 112
For sample analysis:
1. Minimum Reporting Levels (MRL) are 3 times the EDL for each analyte.
2. Report as an occurrence (code -111) any peak matching an analyte retention time
at responses between one-half the MRL and the MRL Such frequent occurrences
may lead to confirmations and/or adjustment in the reporting limit. Frequent
occurrences of non-analyte peaks will be reported to the Technical Monitor. Criteria
for reporting these non-analyte peaks will be supplied by the EPA (Appendix B).
3. The lowest standard solution concentration will approximately equal the MRL for all
analytes.
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Section No. 5
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4. Initial demonstration of method performance will be accomplished by the analysis of
20 spiked samples at 10 times the MRL over a four day period (five spiked samples
per day). Mean recovery, variance and the standard deviation will be calculated.
Relative standard deviation (BSD) will be used to evaluate the precision of the
method using the acceptance criteria provided by the EPA.
5. Method performance data will be reviewed by the Technical Monitor.
6. Samples having any analyte concentration above that analyte's reporting limit will be
confirmed on a different GC column (see Section 8).
7. Samples found in the confirmatory analysis to have any analyte concentration above
that analyte's reporting limit will be qualitatively analyzed by GC/MS. If this cannot
be done by quadrupole GC/MS, the sample extracts will be shipped on ice to TSD
(Appendix C). The shipping blank will be analyzed for any samples meeting
second-column confirmation.
8. Performance evaluation samples will be analyzed quarterly.
Results from all of the above procedures in this Section will be reported to the Technical Monitor
for approval. Data from the Initial Demonstration of Method Performance will be appended to this Plan
(Appendix D).
During the survey, EPA will conduct a time-storage study and will provide extra field samples
(10% of sites) for ESE to assess analyte recoveries frpm a variety of matrices. Each sample will be
spiked with a stock solution in methanol to yield sample concentrations of 2, 10 or 20 times the
reporting limit for each analyte (the surrogate will also be added) (Appendix E). This sample will be
extracted and analyzed, and the data reported as a percent recovery. This data is not for laboratory
control, and the analysis will be judged to have failed only if the extra sample's surrogate recovery
fails the criterion for a regular sample.
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Section No. 6
Revision No 2
Date: July 29, 1990
Page 1 of 3
6. SAMPLING PROCEDURES
All samples for Method 7 will be received in 60-mL amber bottles. Samples for Method 7 will
include 10 mg/L mercuric chloride and will be shipped iced for overnight delivery. Each set received
from a field site will include the following: primary samples and one backup sample for each primary
sample, and one shipping blank sample for each primary sample. Matrix spikes will be performed on
10 percent of the sample sites. Some sets will include time-storage samples. Quarterly, sets will
include performance-evaluation samples provided by the NPS QAO.
Analysis types and frequency are described on the next page.
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Section No 6
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The analysis types for Method 7 are:
Primary Analysis:
Method Blank
Calibration Standards
Field Sample
Lab Spike (ESE Matrix Spike)
Day 0 Time-Storage Sample
Day 14 Time-Storage Sample
Day 14 Time-Storage Extract
Shipping Blank
Performance Evaluation Sample
Backup Sample
Confirmational Analysis:
Method Blank
Calibration Standards
Field Sample
Shipping Blank
GC/MS Confirmation:
Method Blank
Calibration Standards
Field Sample
Shipping Blank
1 per set
daily
1 per ESE
sample no.
10%
10%
10%
10%
(a)
Quarterly
(b)
1 per set
daily (when conf.
is performed)
(a)
(a)
1 per set
daily (when conf.
is performed)
(c)
(a)
Not chargeable
Not chargeable
Chargeable
Chargeable
Chargeable
Chargeable
Chargeable
Chargeable
(b)
Not chargeable
Not chargeable
Chargeable
Chargeable
Not chargeable
Not chargeable
Chargeable
Chargeable
(a) Analyzed when results of primary analyses are above one half the minimum reporting limit.
(b) Analyzed when results of initial analysis fails (not chargeable) or at the request of the
Technical Monitor (chargeable).
(c) Analyzed when results of confirmational analyses are above one half the minimum
reporting limit.
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Section No. 6
Revision No 2
Date: July 29, 1990
Page 3 of 3
Each sample's shipping label will be of the form below.
FIGURE 2
NATIONAL PESTICIDE SURVEY - NPS
PD-0415-4-7-6 DATE 2-11-88
ESE - #7 - T/S
SAMPLER NAME
The sample bottle number (PD-0415-4-7-6 in the above example) is constructed as follows:
PD Pesticide Survey Domestic Well
PC Pesticide Survey Community Well
PR Pesticide Survey Resampled Site
PB Pesticide Survey Performance Evaluation Sample
0415 is the site number
4 is the ESE lab number
7 is the fumigants method number
6 is the bottle number within this site number
The analysis type codes are given below:
FS Field Sample
FD Field Duplicate
SB Shipping Blank
BU Backup Sample
LS Lab Spike (The ESE Matrix Spike; "LS" will be followed by a numeric digit which
indicates spike level; 0=2xMRL, 1=5xMRL, 2=10xMRL These samples also serve
as samples for time storage, t = 0 days.)
T/S Time Storage (t = 14 days)
T/S0 Time Storage Duplicate (t = 0 days)
T/S14 Time Storage Duplicate (t = 14 days)
The sampling contractor will supply a copy of the field sample tracking sheet used for NPS
samples.
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Section No 7
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7. SAMPLE CUSTODY
The sampling contractor (ICF) will supply information about sample shipments and the protocol
ESE will follow to notify the sampling contractor about sample receipt and any problems associated
with samples received. The project Technical Monitor will also be notified concerning problems with
the receipt of samples from the sampling contractor (eg. no ice, etc).
Holding times for samples to be analyzed by Method 7 are: 14 days maximum holding time for
samples, counting day of sampling as Day 0; and 14 days maximum holding time for extracts,
counting the day of extraction as day 0. Sample disposal will be handled in accordance with Florida
regulation.
A series of time storage samples will be collected and analyzed during the NPS 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.
Each sample will be spiked at the 10X MRL level. Results of the time storage samples will be
reported to EPA along with the corresponding regular sample. For data reporting purposes, Day-0
samples (spiked, extracted and analyzed within 4 days of extraction) will be referred to as Day-0 Time
Storage (DTS). These samples serve a dual role, as lab spikes and DTS. Extracts from these Day-0
samples reanalyzed within 10 to 18 days will be referred to as Holding Time Extracts (HTE). Day-14
time storage samples (spiked, held for + 14 days, extracted and analyzed within 4 days) will be
referred to as Holding Time Samples (HTS). All of the holding time samples will be extracted and
analyzed in duplicate. Any statistical analysis of the time storage data will be conducted by EPA.
When samples are received at the ESE Receiving Station, 14420 Newberry Road, Gainesville,
FL, the receiving employee will deliver the samples to Vince Prem-Das at the sample check-in station,
the Hendrickson building. Mr. Prem-Das will then (1) mark the NPS sample tracking form with the
required information, (2) move the samples into a lockable refrigerator in ESE's volatile organic
analysis laboratory, and (3) submit the logsheets to Data Management. A Data Management
employee will enter the sample information to ESE's database, a process which automatically
generates Sample Arrival Notices for the Method 7 Task Manager, Glenn Jackson. Mr. Jackson then
schedules the analyses with the analyst, James Yeh, who analyzes them within the holding times, and
enters the analytical data into the ESE database. Samples and extracts will be stored between 0°C
and 6°C in the dark. At the end of the holding times, the water samples will be disposed in
accordance with Florida regulation. Extracts will be held in a freezer until EPA releases them for
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Section No. 7
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Page 2 of 2
disposal. Sample extracts will be shipped to TSD next day, on ice, if GC/MS confirmation of GC
confirmed positives is not possible at ESE. The shipping protocol will be appended.
The implementation contractors, ICF, will provide data on returning sample kits.
All ESE coldrooms, refrigerators, and freezers holding samples for chemical analysis are
monitored daily by ESE personnel, and records are kept daily. Samples are signed out of the
coldroom when removed to the laboratory and signed in when returned. The ESE coldrooms use a
"library" system where samples are returned to a Return Shelf, and Data Management personnel only
place samples on storage shelves. The coldroom is locked when no one is inside. ESE plans to
keep NPS samples on a separate shelf from other samples during the analytical effort (about 18
months).
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Section No. 8
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8. CALIBRATION PROCEDURES AND FREQUENCY
The instrumental analysis for Method 7 will be performed on a Hewlett-Packard 5890A gas
chromatograph. Primary analytical separations will be performed on a DB-1 fused silica capillary
column, 30 meters long, 0.32 millimeters internal diameter, and 0.25 micron film thickness. Secondary
analytical separations will be performed on a DB-17 fused silica capillary column, 30 meters long, 0.32
millimeters internal diameter, and 0.25 micron film thickness. Helium will be used as a carrier gas.
ESE analysts will prepare standard solutions in methanol from EPA concentrate solutions and
will keep detailed records of the means used to prepare them on each occasion. Spiking
concentrates will be generated by separate dilutions from those used to generate standard solutions.
Records of the generation of standards will be kept by the analyst in his permanent notebook. Each
set's analytical records will refer to the standard solutions actually used on that day. New standard
dilutions will be checked to insure that the QC criteria, +. 20% of initial calibration, is met. Standard
and spiking solutions will be stored in the dark at 0° to 4°C in a standards refrigerator.
ESE plans to calibrate the instrument each day a set is analyzed. For primary analysis, five
standards of various concentrations will be spaced periodically in the sample analysis set. The lowest
calibration standard will be near the MRL A solvent blank will also be analyzed. The correlation
coefficient between concentrations and response will be 0.995 or greater.
For second column confirmation, a single calibration standard will be used for quantitation. The
standard will contain analytes at concentrations near that detected during primary analysis. Results of
second column confirmation will be within +_ 25% of the primary analysis result. If this criteria is not
met the project Technical Monitor will be advised.
For GC/MS confirmation, a single calibration standard will be used which is prepared at the
concentration determined for the sample, on either the primary or secondary column, whichever
concentration is lower. If additional sample extract treatment is performed for the GC/MS analysis, the
calibration standard must also undergo the same treatment.
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Section No 9
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9. ANALYTICAL PROCEDURES
The primary analysis begins with the extraction of a 20-mL aliquot of water sample (to which the
surrogate, bromochloropropane, has been added) by 1-mL of hexane solvent. Elution through a
capillary column separates the analytes and other components, and electron-capture detection
quantitates the analytes and surrogate. In confirmatory analysis, the extract is chromatographed
through a somewhat different column, and electron-capture detection is used to verify any positive
results from the primary analysis. GC/MS confirmation is similar to GC confirmatory analysis except
that detection by mass spectrometry is used.
Primary and confirmatory analyses are performed using a Hewlett-Packard 5890A gas
chromatograph equipped with two electron-capture detectors and a Hewlett-Packard 3393A integrator.
Any GC/MS confirmations at ESE will be performed using a Hewlett-Packard 5987 gas
chromatograph/mass spectrometer.
All data will be transferred to the Chemistry Division database running on 65 AT-class computers
served by a 3-drive, 1600-Mbyte Novell network housed in the Chemistry Division.
ESE plans to include no more than 20 field samples in a set, and generally fewer.
ESE plans no significant differences from Method 504, revision dated October 27, 1987 as
provided to ESE in glassware cleaning, reagents, or data reduction. Three additional analytes will be
included in the determinations using Method 504, they are; 1,2-dichloropropane, cis- and trans-
dichloropropene. Differences in equipment are listed above in this Section. In the analytical
procedure, ESE plans to use a DB-1 column for the primary analysis and DB-1701 column for the
confirmatory analysis. ESE plans to extract 20-mL of sample with 1 -mL hexane rather that 35-mL of
sample with 2-mL of hexane. Because of contamination risk, salt was not used in the extraction
process. These changes are for the convenience of our analysts and causes no degradation in the
data quality or detection limits. Any deviations from these procedures or QC requirements after the
Plan is approved will only be used if approved by the EPA Technical Monitor in advance. Changes
will be documented, signed by the Technical Monitor and appended to the Plan.
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Section No. 10
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10. DATA REDUCTION, VALIDATION REPORTING
Calibration standard concentrations and raw instrument responses for calibration standards and
sample aliquots are entered into the ESE Chemistry Division's database. ESE data management will
support new in-house sample type codes that the numerous EPA sample types require. The analyst
will generate ESE set reports and will verify correct entry and QC data compliance with project criteria.
The Method 7 Task Manager will review data set reports before submission to the Data Management
department. When Data Management receives a signed copy of the set report, they will generate a
data file on floppy disk in the NPS format. The project manager will then examine a listing or
summary of the file and approve delivery of the floppy disk to EPA.
All data for a set of samples (including QC and confirmatory data) will be reported to the EPA
no later than two months from the date of sample collection. Any GC/MS confirmatory data will be
reported as "presence" or "absence" of target analytes.
The NPS file format is appended to this Plan (Appendices G, H and I).
Fast Track Reporting (immediate telephone call to the Technical monitor) will be needed for
confirmed positive sample concentrations of selected EPA analytes detected above known health
effect levels (Appendix J). When results from confirmation columns do not agree with results from
primary columns within criteria set by EPA (± 25%), or shipping blanks are found to be contaminated,
the Technical Monitor will be notified immediately. (Contaminated means a peak response at the
correct retention time for an MPS analyte at one-half the MRL or greater.)
Storage of laboratory data will be by ESE standard procedures. Standards and reagent
preparation data will reside in the analyst's permanent laboratory notebook. Chromatograms,
calibration data, and corrective action records, etc. will reside in an analysis set folder which will be
stored permanently in ESE's laboratory central filing system. ESE set folders currently reside in
archival files in ESE's central filing system.
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Section No. 11
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Page 1 of 5
11. INTERNAL QUALITY CONTROL CHECKS
No lab control spikes are required for Method 7. Analytical quality will be controlled largely by
the following means, which are summarized in Exhibit 11-1:
If the responses of the analytes in each set's standard chromatograms have
changed by ±_ 20 percent (%) of the previous calibration, the analyst will make new
standard solutions from the EPA concentrates. These new dilutions must be within
20 percent of the previous set. Each set must include a chromatogram of a
standard at or near the MRL for each analyte.
Each set's method blank must have analyte responses less than half the minimum
reporting limit. If any analyte is present at half or more of the MRL, a new method
blank will be generated and analyzed. A second method blank failure will require
the determination of the source of contamination before the analysis of samples
begins.
Surrogate recovery for each sample must be within 30 percent (absolute
percentage) of the mean surrogate recovery of the data generated in the initial
demonstration of capability and used in the control chart criterion generation or the
updated control chart. Failure to meet the criterion will require that the situation be
corrected before the sample data is accepted. Evaluation of calibration standards
and/or reanalysis of sample may be required.
Surrogate recovery in each set's method blank will be used as the set's control
point in the control chart and will be compared against the criterion developed in
the initial demonstration of capabilities or the current updated control chart. Thus,
there will be one control chart point for each set of samples extracted. The control
boundaries on surrogate control chart points will be originally determined from the
20 spiked samples analyzed during the initial demonstration of capability. The
mean and standard deviation of the 20 surrogate recovery percentages will be
calculated, then the relative standard deviation (RSD) will be calculated. The control
limits on the accuracy chart will be ±3 RSD about the mean. The warning limits will
be ±2. RSD about the mean. Dixons' test at the 99 percent confidence level will be
used to determine outliers (Appendix K). There can be no more than 3 outliers in
the original spiked controls.
Following establishment of the control chart, the surrogate recovery from the
method blank is determined with each analytical set. The percent recovery is then
checked on the chart. When 5 such controls have been run, these surrogate
recoveries will be incorporated into the control charts. From the 20 most recent
good points, accuracy will be recalculated as above and the chart will be redrawn.
The newly drawn chart will then apply to surrogate recoveries in the next five
sample sets. If a field sample qualifies as a blank and it's surrogate recovery meets
surrogate control chart limits, it can be substituted for the blank, if the blank
recovery does not meet criteria.
Analysis will be considered "out-of-control" if the surrogate recovery is outside ^3
RSD once. Analysis must be stopped until an "in-control" situation is reestablished.
An "alert" situation will arise if a run of 7 consecutive points is above or below the
mean, or a run of 7 consecutive points is increasing or decreasing. Also an "alert"
situation will arise if 3 or more consecutive percent recoveries are outside the
warning limits (±2 RSD).
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Section No 11
Revision No 2
Date: July 29, 1990
Page 2 of 5
EXHIBIT 11-1
INTERNAL QC CHECKS FOR METHOD 7
QC Type
Frequency
Concentration Criteria
Method Blank
Shipping Blank
Calibration Curve
Surrogate
Recovery
Surrogate
Recovery
Second Column
Confirmation
GC/MS
Qualitative
Confirmation
Each Set
Positives in
Sample
Daily
Each Sample
Method Blank
Each Set
All Positives
All Confirmed
Positives
0.5 ug/L
0.5 ug/L
up to 1/2 MRL
up to 1/2 MRL
+/- 20%
+/- 30% mean R
in CL on Chart
Calibration Std. +/- 25% of Prime
+/- 20% Prime Cone.
Cone.
+/-10%ofSIR
Masses at
Retention Times
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Section No. 11
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Date: July 29, 1990
Page 3 of 5
EXHIBIT 11-1 (continued)
INTERNAL QC CHECKS FOR METHOD 7
QC Type
Purpose and Corrective Action
Method Blank
Shipping Blank
Calibration Curve
Surrogate
Recovery/BCP
Second Column
Confirmation
GC/MS
Qualitative
Confirmation
Method Blank determines if system is free of contamination.
Action: Determine the source of contamination.
Determine if samples are free of contamination. If fails,
inform monitor.
Determine validity of standard curve. Action: Check system,
make new standard.
Monitors method efficiency for all samples. Action: Step-
wise review of sample extraction concentration and
chromatography to source of the error.
Report failure to technical monitor for next action.
Report failure to technical monitor for next action.
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Section No. 11
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Page 4 of 5
If any positives are determined in the samples, the shipping blank will be analyzed.
Second column confirmation must be within ±25 percent of the concentration
determined with the primary column.
GC/MS qualitative confirmation must be performed with a standard that is
approximately equal to the lowest concentration determined in the primary and
confirmation GC analyses. If quadrupole GC/MS is not sensitive enough, the
sample extracts will then be shipped on ice to TSD for analysis by magnetic sector
GC/MS.
Exhibit 11-2 shows ESE's Internal Quality Control Checklist which will be included with each set
file.
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Section No. 11
Revision No. 2
Date: July 29, 1990
Page 5 of 5
EXHIBIT 11-2
INTERNAL QUALITY CONTROL CHECKLIST
U. S. ENVIRONMENTAL PROTECTION AGENCY
NATIONAL PESTICIDE SURVEY
METHOD 7
EPA SET No.
DATE ANALYZED
INTERNAL QUALITY CONTROL CHECKS
ESE BATCH No._
ANALYST
1. DAILY STANDARD CALIBRATION RESPONSES
(each analyte +20% of previous day)
2. CHROMATOGRAM NEAR MRL INCLUDED
3. METHOD BLANK
(less than 1/2MRL for each analyte)
4. SHIPPING BLANK
(less than 1/2MRL for each an.alyte - only
if positives are found in samples)
5. SECOND COLUMN CONFIRMATION
(+25% of primary analysis)
6. SAMPLE SURROGATE RECOVERY
(within +_30% of control chart mean)
7. METHOD BLANK SURROGATE RECOVERY
(within +3RSD on control chart)
COMMENTS:
QUALITY ASSURANCE COORDINATOFj_
PROJECT MANAGER
YES
NO
DATE_
DATE
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Section No 12
Revision No. 2
Date- July 29, 1990
Page 1 of 1
12. PERFORMANCE and SYSTEM AUDITS
ESE's Quality Assurance Coordinator, independent of the Project Manager and reporting directly
to the ESE Laboratory Director, will perform audits of the following types:
Observation of the analyst analyzing samples during the initial demonstration of
capabilities and approximately quarterly thereafter. This audit will include verification
that no significant changes have occurred in procedure, instrumentation, analytical
environment, or in sample and reagent storage and labelling. The auditor will select
items for audit from this QA Plan at his discretion and generally without warning to
the analyst. Retrievable errors (those affecting no data yet sent to EPA), will be
corrected immediately and a means of assuring its long-term rectification
established. Irretrievable errors will prompt written notice to the EPA Technical
Monitor.
Examination of a data set, especially QC and instrument performance parameters.
This will be performed in detail during the initial demonstration of capabilities and
approximately quarterly thereafter. The latter examinations will be performed on
randomly selected data sets. The auditor may question the analyst at his discretion.
However, the analyst may postpone for up to 10 working days a prolonged
conference with the auditor if (1) the analyst or his department manager considers
the current backlog of samples, especially those near holding times, to be too great
to allow immediate consideration of the auditor's questions AND (2) if the auditor's
questions do not concern data due within a few working days of generation.
Discussion of QA reports when EPA conducts on-site audits.
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Section No. 13
Revision No. 2
Date: July 29, 1990
Page 1 of 1
13. PREVENTIVE MAINTENANCE
The instrumentation ESE specifies for the performance of Method 7 requires the following
preventive maintenance.
The injection septum will be replaced when daily inspection shows significant wear,
after 7 days of use, when analyte or surrogate retention times vary more than 2
percent between consecutive chromatograms, or daily when the instrument is in
heavy use (more than 50 injections per day).
The detector will be cleaned by heating when the analyst detects irreproducible or
otherwise irregular responses. This behavior is unusual for groundwater sample
extracts and is not expected during the duration of this project.
Gas cylinders will be changed when the cylinder pressure drops below 100 psig.
Molecular sieves and oxygen traps in the gas supply lines will be changed per
manufacturers recommendations.
Spare columns, instrument cables, and some PC boards are kept to minimize
instrument downtime.
The injection port liner will be replaced or cleaned if found to be contaminated.
However, this is not expected from the analysis of groundwater sample extracts.
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Section No 14
Revision No. 2
Date: July 29, 1990
Page 1 of 1
14. SPECIFIC PROCEDURES FOR ASSESSING MEASUREMENT SYSTEM DATA
Instrument performance control standards are not required for Method 7. As mentioned in
Section 10, a standard at or near the MRL will be analyzed daily and must have a response
distinguishable from the instrument background, measured as 15 times the signal-to-noise ratio. This
is not expected to be a problem for Method 7.
Each method blank surrogate percent recovery will be calculated as 100 times the measured
concentration divided by the nominal concentration. This recovery will be compared to control chart
criteria from the initial demonstration of capabilities to determine validity. The control chart criteria for
the surrogate compound will be calculated from the initial 20 spiked samples as follows:
The mean recovery is calculated as the sum of recoveries divided by the number of
recoveries included in the sum.
RSD is calculated as the standard deviation divided by the mean, where the
standard deviation is the square root of the variance. The variance is calculated as
the sum of the squares of differences between each recovery and the mean
recovery, divided by the number of recoveries less one.
The control chart limits are three times the RSD added to and subtracted from the
mean recovery; the warning limits are plus and minus two times the RSD about the
mean.
The control limits for SAMPLE surrogate recoveries are 30 percent (absolute) added
to and subtracted from the mean recovery.
Acceptability of the above will be determined by the Technical Monitor.
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Section No. 15
Revision No 2
Date: July 29, 1990
Page 1 of 2
15. CORRECTIVE ACTION
In general, bench-level corrective actions fall into three categories each with differing required
action.
Short-Term Action - Major and minor problems which can be corrected
immediately. Examples include failure to date or sign a field form and date entry
errors. Generally, the analyst or other employee committing the error can simply
correct it, and the record of this corrective action will directly reflect the error and its
resolution. This record will be kept with the analysis set file in ESE's central filing
system.
Long-Term Corrective Action - Minor and major problems which require a series of
actions to resolve the problem. Examples include a discovery that part of the
analytical or data-handling procedures were not being followed correctly. The
actions to be taken are coordinated by the QA Supervisor or his designate, and a
QA corrective action and routing form (Exhibit 15-1) is used to track the action.
These corrective actions and their resolutions will be included in monthly reports to
EPA.
Quality-Control Corrective Actions - Failure to meet QC criteria specified in this QA
plan. Actions consist of two kinds: Those resolved within each analytical
department by reanalysis, etc.; and those resolved outside the department.
Records of all QC corrective actions will be recorded in the analyst's notebook and
in the analysis set file and reported to EPA's Technical Monitor in the monthly
reports.
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Section No. 15
Revision No. 2
Date: July 29, 1990
Page 2 of 2
EXHIBIT 15-1
QUALITY ASSURANCE CORRECTIVE ACTION
AND REQUEST FORM
QUALITY ASSURANCE CORRECTIVE ACTION REQUEST
AND ROUTING FORM
1. Identification of a Problem: Date:
Originator:
Nature of Problem:
2. Determination of Required Action:
Responsibility Assigned to: Due Date:
Recommended Action:
3. Implementation of Required Action:
Responsibility Assigned to: Due Date:
4. Assuring Effectiveness of Action:
Responsibility Assigned to : Due Date:
Procedure to assure Effectiveness:
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Section No. 16
Revision No. 2
Date. July 29, 1990
Page 1 of 1
16. QUALITY ASSURANCE REPORTS TO MANAGEMENT
QA activities are reported to management by the QA Coordinator in three ways:
1. Verbal notification of significant QA deficiencies immediately upon discovering the
problem,
2. Written interim QA reports, and
3. Written final QA reports.
A final QA report will be prepared for this project. Interim reports will be prepared at the request
of ESE management, the Project Manager, or the Contracting Officer.
The contents of interim and final QA reports will be similar except final reports will include
summaries of the interim reports.
The following items will be addressed in the reports:
1. An assessment of the precision and accuracy data associated with sample data
generated during the report period.
2. Results of all QA audits performed during the report period.
3. Results of the QA data validations performed during the report period.
ESE will send monthly reports to the EPA Technical Monitor. These reports will be in the
following format:
Summary of progress - number of samples received and samples analyzed, (but
not necessarily validated) and status; of data processing for analyzed sets of
samples, and numbers for sets of data sent to the EPA.
Summary list of bench-level corrective actions (as in Sections 10 and 14 of this
Plan).
Identification of problems about any phase of the project.
Copies of representative and, if applicable, unusual chromatograms.
Any other chromatograms^or information requested by the Technical Monitor
because of specific methodology or problems encountered.
Changes in personnel.
Comments
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Section No. 17
Revision No. 2
Date: July 29, 1990
Page 1 of 2
17. ARCHIVAL OF RAW DATA
In order to assure the continued availability of all documentation necessary to defend NFS
Method 7 analytical results, the documentation for each analytical set will be contained in a separate
green file folder and will be comprised of the following:
GC set documentation checklist
Method 7 internal quality control checklist
A hard copy of the NFS formatted results
A hard copy of ESE's formatted results
All chromatograms and quantitation reports for the following:
Solvent blank
Field samples and shipping blank (if analyzed)
Method blanks
Calibration standards
Time-storage samples
Lab spike samples
Chromatographic analysis logs (Instrument logsheet)
Chromatographic logsheet(s)
Extraction logsheet(s)
Surrogate Control Chart
Copies of NFS sample tracking forms
Copies of pertinent analyst notebook pages
All set file folders will be stored in banker's boxes. Each box will be labeled with number, a
description of Its contents (NFS Method 7 set files), a listing of ESE internal batch numbers
corresponding to NFS well numbers, (sorted by NFS well number), the date placed in storage, and
the date to be destroyed.
A separate banker's box will contain the following, and be labeled as described above:
A copy of the QA Project Plan
Monthly reports to the Technical Monitor
Original NFS sample tracking forms With original Fed Ex airbills
Correspondence to and from EPA
Laboratory data from initial demonstration of capabilities and demonstration of
accuracy and precision
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Section No. 17
Revision No 2
Date- July 29, 1990
Page 2 of 2
Miscellaneous documentation such as audit reports, internal memos,
temperature logs, etc.
Resumes of NPS participants
All banker's boxes containing the NPS files will be stored for a period of seven years in the
Dead File Storage room located in the Maintenance building at ESE's Gainesville location. This room
is kept locked at all times and access is limited to its custodian, Virginia O'Brien, Manager of the
Information Services Department of ESE's Gainesville laboratory.
A Dead File Storage logsheet listing the same information that is written on bankers boxes will
be kept with the storage room custodian and a copy will be sent to the EPA Technical Monitor. In
addition, a list of all samples analyzed will be prepared, with cross references to the NPS set number,
the ESE batch number, and the ESE internal sample number. Appendix L provides a copy of ESE's
standard operating procedures for batch storage of data.
Any changes to the archival procedures described above will be communicated in writing to the
Technical Monitor.
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Section No. 18
Revision No 2
Date. July 29, 1990
Page 1 of 1
18. ADDENDUM TO ESE QUALITY ASSURANCE PROJECT PLAN FOR METHOD 7
1. Shipping Blanks - If any target analytes are found in a shipping blank by primary analysis,
ESE will call the Technical Monitor prior to performing confirmational analyses, (pp. 7, 23)
^
2. Preservative - Mercuric chloride will be added to all method blanks. Use the supply of the
compound provided by ICF and add to give the same concentration as in field samples.
(p. 20)
3. Analyte and Other Peaks Below the MRL - The procedures provided by EPA (6/1/88
Memo, "NPS Analyte Reporting Below MRL and Identifying Unknown Peaks") will be
referenced and appended to the plan. (pp. 7, 20)
4. Sample Shipments - The procedures provided by ICF (4/5/88 packet "NPSIS Sample
Receipt Software for Laboratories") will be referenced and appended to the plan. (p. 14)
5. Data Report Format - The format provided by EPA in February will be referenced and
appended to the plan along with the 4/18/88 Update Memo, "Data Reporting Format
Changes", (p. 21)
6. Surrogate Recovery - The Surrogate in the method blank will be the only control blank
that is used for control chart monitoring, (p. 23)
7. Outliers in Control Samples - Dixon's Test will also be used for the "observed" and
"background" terms in thre calculation. Only background peaks greater than one-half the
MRL need to be subtracted. To calculate recovery, the concentration of the spike will be
used to divide the difference of the peaks. Percent recovery equals the observed
concentration minus the background concentration times 100 divided by the concentration
of the spike added, (p. 23)
"NPS Rapid Reporting System" memo of 4/12/88 will be referenced and appended, (p 21)
Confirmation Column will be DB-1701. (p. 17)
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APPENDICES
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Appendix A
Revision No. 2
Date: July 29, 1990
Page 1 of 16
APPENDIX A
NPS METHOD 7
(EPA METHOD 504). MEASUREMENT OF 1,2-DIBROMOETHANE (EDB)
AND 1,2-DIBROMO-3-CHLOROPROPANE (DBCP) IN WATER BY
MICROEXTRACTION AND GAS CHROMATOGRAPHY
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METHOD 504. 1,2-DIBROMOETHANE (EDB) AND
l,2-QIBROMO-3-CHLOROPROPANE (DBCP) IN HATER
BY MICROEXTRACTION AND GAS CHROMAT06RAPHY
(1985, Ed. Rev. 1986)
1. SCOPE AND APPLICATION
1.1 This Method (1,2,3) 1s applicable to the determination of the
following conpounds 1n finished drinking water and unfinished
groundwater:
Analyte CAS No.
1,2-Oibroraoethane 106-93-4
l,2-01bromo-3-Chloropropane 96-12-8
1.2 For compounds other than the above mentioned analytes, or for other
sample sources, the analyst must demonstrate the usefulness of the
method by collecting precision and accuracy data on actual samples
(4) and provide qualitative confirmation of results -by Gas
Chromatography/Mass Spectrometry (GC/MS) (5).
1.3 The experimentally determined method detection limits (MDL) (6) for
EDB and OBCP were calculated to be 0.01 ug/l. The method has been
shown to be useful for these analytes over a concentration range
from approximately 0.03 to 200 ug/L. Actual detection limits are
highly dependent upon the characteristics of the gas chromato-
graphic system used.
2. SUWARY OF METHOD
2.1 Thirty-five nL of sample are extracted with 2 nL of hexane. Two uL
of the extract are then Injected Into a gas chromatograph equipped
with a linearized electron capture detector for separation and
analysis. Aqueous calibration standards are extracted and analyzed
in an identical Banner as the samples 1n order to compensate for
possible extraction losses.
2.2 The extraction and analysis time 1s 30 to 50 minutes per sample
depending upon the analytical conditions chosen. (See Table 1 and
Figure 1.)
2.3 Confirmatory evidence can be obtained using a dissimilar column
(see Table 1). When component concentrations are sufficiently high
(> 50 ug/L), Method 524.1 (7) may be employed for improved speci-
ficity.
3. INTERFERENCES
3.1 Impurities contained 1n the extracting solvent usually account for
the majority of the analytical problems. Solvent blanks should be
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analyzed on each new bottle of solvent before use. Indirect dally
checks on the extracting solvent are obtained by monitoring the
sample blanks (7.1.1). Whenever an interference is noted in the *
sample blank, the analyst should reanalyze the extracting solvent.
Low level Interferences generally can be removed by distillation or
column chromatography (3); however, it is generally more economical
to obtain a new source solvent. Interference-free solvent is
defined as a solvent containing less than 0.1 ug/L Individual
analyte Interference. Protect Interference-free solvents by
storing in an area known to be free of organochlorlne solvents.
3.2 Several Instances of accidental sample contamination have been
attributed to diffusion of volatile organic* through the septum
seal Into the sample bottle during shipment and storage. The
sample blank (7.1.1) 1s used to monitor for this problem.
3.3 This liquid/liquid extraction technique efficiently extracts a wide
boiling range of non-polar organic compounds and, in addition,
extracts polar organic components of the sample with varying
efficiencies.
3.4 EDB at low concentrations may be masked by very high levels of
dlbromochloromethane (DBCM), a common chlorinated drinking water
contaminant, when using the confirmation column (Sect. 5.8.2.2).
4. SAFETY
4.1 The toxicity and carcinogenlcity of chemicals used 1n this method
has not been precisely defined; each chemical should be treated as
a potential health hazard, and exposure to these chemicals should
be minimized. Each laboratory 1s responsible for maintaining
awareness of OSHA regulations regarding safe handling of chemicals
used in this method. Additional references to laboratory safety
are available (8-10) for the Information of the analyst.
4.2 EDB and DBCP have been tentatively classified as known or suspected
human or mammalian carcinogens. Pure standard materials and stock
standard solutions of these compounds should be handled 1n a hood
or glovebox. A NIOSH/MESA approved toxic gas respirator should be
worn when the analyst handles high concentrations of these toxic
compounds.
5. APPARATUS AND EQUIPMENT
5.1 SAMPLE CONTAINERS - 40-nL screw cap vials (Pierce #13075 or
equivalent) each equipped with a PTFE-faced si 11cone septum (Pierce
#12722 or equivalent). Prior to use, wash vials and septa with
detergent and rinse with tap and distilled water. Allow^the vials
and septa to air dry at room temperature, place in a 105"C oven for
one hour, then remove and allow to cool In an area known to be free
of organic*.
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5.2 VIALS, auto sampler, screw cap with PTFE-faced septa, 1.8 rat,
Varian W6-000099-00 or equivalent.
5.3 MICRO SYRINGES - 10 and 100 uL.
5.4 MICRO SYRINGE - 25 UL with a 2-1 nch by 0.006-inch needle -.Hamilton
702N or equivalent.
5.5 PIPETTES - 2.0 and 5.0 wL transfer.
5.6 VOLUMETRIC FLASKS - 10 and 100 «L, glass stoppered
5.7 STANDARD SOLUTION STORAGE CONTAINERS - 15-*L bottles with
PTFE-Hned screw caps.
5.8 GAS CHROMATOGRAPHY SYSTEM
5.8.1 The GC must be capable of temperature programming and should
be equipped with a linearized electron capture detector and a
capillary column split!ess injector.
5.8.2 Two gas chromatography columns are recommended. Column A 1s
a highly efficient column that provides separations for EDB
and DBCP without Interferences from trlhalomethanes (Sect.
3.4). Column A should be used as the primary analytical
column unless routinely occurring analytes are not adequately
resolved. Column 3 1s recommnded for use as a confirmatory
column when GC/MS confirmation is not available. Retention
times for EDB and DBCP on these columns are presented in
Table 1.
5.8.2.1 Column A - 0.32 m ID x 30M long fused silica
capillary with dimethyl $111cone nixed phase
(Durawax-DX3, 0.25 urn film, or equivalent). The
linear velocity of the helium carrier gas 1s
established at 25 ca/sec. The column temperature 1s
programmed to hold at 40*C for 4 min, to Increase to
190 C at B*C/m1n, and hold at 190*C for 25 orin or
until all expected compounds have eluted. Injector
temperature: 200*C. Detector temperature: 290*C.
(See Figure 1 for a sample chromatogram and Table 1
for retention data).
5.8.2.2 Column B (confirmation column) - 0.32mm ID x 30M
long fused silica capillary with methyl polysiloxane
phase (OB-1, 0.2S * film, or equivalent). The
linear velocity of the helium carrier gas 1s
established at 25 a/sec. The column temperature is
programmed to hold at *0*C for 4 min, to Increase to
270 C at lO"C/«1nut«, and hold at 270*C for 10 min
or until all expected compounds have eluted.
Injector temperature: 200*C. Detector tempera-
ture: 290"C. (S«t Table 1 for retention data).
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6. REAGENTS AW CONSUMABLE MATERIALS
6.1 REAGENTS
6.1.1 Hexane extraction solvent - UV Grade, Burdlck and Jackson
#216 or equivalent. ±
t
6.1.2 Methyl alcohol - ACS Reagent Grade, denonstratcd to be free
of analytes.
6.1.3 Sodium chloride, Had - ACS Reagent Grade - For pretreatment
before use, pulverize a batch of NaCl and place 1n a muffle
furnace at roan temperature. Increase the temperature to
400*C for 30 Minutes. Place 1n a bottle and cap.
6.2 STANDARD MATERIALS
6.2.1 l,2-01bromoethane - 992, available from Aldrich Chemical
Company.
6.2.2 l,2-01bromo-3-ch1oropropane - 99.4X, available from AMVAC
Chemical Corporation, Los Angeles, California.
6.3 REAGENT HATER - Reagent water 1s defined as water free of Inter-
ference when employed 1n the procedure described herein.
6.3.1 Reagent water can be generated by passing tap water through
a filter bed containing activated carbon. Change the
activated carbon whenever the criteria 1n Sect. 9.1.2 cannot
be met.
6.3.2 A M1111pore Super-Q Hater System or Its equivalent may be
used to generate delonlzed reagent water.
6.3.3 Reagent water may also be prepared by boiling water for 15
m1n. Subsequently, while maintaining the temperature at
90*C, bubble a contaminant-free Inert gas through the water
at 100 BL/minute for 1 hour. While still hot, transfer the
water to a narrow mouth screw cap bottle with a Teflon seal.
6.3.4 Test reagent water each day 1t 1s used by analyzing It
according to Sect. 10.
6.4 STANDARD STOCK SOLUTIONS - These solutions may be purchased as
certified solutions or prepared from pure standard materials using
the following procedures:
\
6.4.1 Place about 9.8 nL of methanol Into a 10-mL ground-glass
stoppered volumetric flask. Allow the flask to stand,
unstoppered, for about 10 mln and weigh to the nearest
0.1 mg.
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6.4.2 Use a 100-uL syringe and Immediately add two or more drops
of standard material to the flask. Be sure that the .
standard material falls directly Into the alcohol without
contacting the neck of the flask.
6.4.3 Rewelgh, dilute to volume, stopper, then mix by Inverting
the flask several times. Calculate the concentration 1n
mlcrograms per microliter from the net gain 1n weight.
6.4.4 Store stock standard solutions 1n 15-mL bottles equipped
with PTFE-Hned screw caps. Methanol solutions prepared
from liquid analytes are stable for at least four weeks when
stored at 4 C.
6.5 SECONDARY DILUTION STANDARDS Use standard stock solutions to
prepare secondary dilution standard solutions that contain both
analytes 1n methanol. The secondary dilution standards should be
prepared at concentrations that can be easily diluted to prepare
aqueous calibration standards (Sect. 8.1.1) that will bracket the
working concentration range. Store the secondary dilution standard
solutions with minimal headspace and check frequently for signs of
deterioration or evaporation, especially just before preparing
calibration standards. The storage time described for stock
standard solutions 1n Sect. 6.4.4 also applies to secondary
dilution standard solutions.
6.6 QUALITY CONTROL (QC) CHECK SAMPLE CONCENTRATE (0.25 wg/mL)
Prepare a QC check sample concentrate of 0.25 ng/mL of each analyte
from the standard stock solutions prepared 1n Sect. 6.4.
6.7 MOL CHECK SAMPLE CONCENTRATE (0.05 Bg/mL) Dilute 2 mL QC check
sample concentrate (Sect. 6.6) to 10 mL with methanol.
7. SAMPLE COLLECTION. PRESERVATION, AND STORAGE
7.1 SAMPLE COLLECTION
7.1.1 Replicate field blanks must be handled along with each
sample set, which 1s composed of the samples collected from
the same general sampling site at approximately the same
time. At the laboratory, fill a minimum of two sample
bottles with reagent water, seal, and ship to the sampling
site along with sample bottles. Wherever a set of samples
1s shipped and stored, 1t must be accompanied by the field
blanks.
7.1.2 Collect all samples 1n duplicate. Fill sample bottles to
overflowing. No air bubbles should pass through the sample
as the bottle 1s filled, or be trapped 1n the sample when
the bottle Is sealed.
7.1.3 When sampling from a water tap, open the tap and allow the
system to flush until the water temperature has stabilized
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(usually about 10 arm). Adjust the flow to about 500 mL/min
and collect duplicate sanples from the flowing stream.
7.1.4 When sampling from a well, fill a wide-mouth bottle or
beaker with sample, and carefully fill duplicate 40-mL
sample bottles.
7.2 SAMPLE PRESERVATION
7.2.1 The samples «ust be chilled to 4*C on the day of collection
and maintained at that temperature until analysis. Field
samples that will not be received at the laboratory on the
day of collection must be packaged for shipment with suffi-
cient ice to Insure that they will be below 4*C on arrival
at the laboratory.
7.2.2 The addition of sodium thiosulfate as a dechlorinatlng agent
and/or acidification to pH 2 with 1:1 HC1, common preserva-
tion procedures for purgeable compounds, have been shown to
have no effect on EDB and OBCP and, therefore, their use is
not recommended for samples to be analyzed for these
analytes.
7.3 SAMPLE STORAGE
7.3.1 Store samples and field blanks together at 4"C until
analysis. The sample storage area must be free of organic
solvent vapors.
7.3.2 Analyze all samples within 28 days of collection. Samples
not analyzed within this period must be discarded and
replaced.
8. CALIBRATION AND STANDARDIZATION
8.1 CALIBRATION
8.1.1 At least three calibration standards are needed. One should
contain EDB and DBCP at a concentration near to but greater
than the method detection limit (Table 1) for each compound;
the other two should be at concentrations that bracket the
range expected in samples. For example, If the MOL 1s
0.01 ug/L, and a sample expected to contain approximately
0.10 ug/L Is to be analyzed, aqueous standards should be
prepared at concentrations of 0.02 ug/L, 0.10 ug/L, and
0.20 ug/L.
8.1.2 To prepare a calibration standard, add an appropriate volume
of a secondary dilution standard solution to an aliquot of
reagent water in a volumetric flask. Do not add less than
20 uL of an alcoholic standard to the reagent water or poor
precision will result. Use a 25-uL micro syringe and
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rapidly Inject the alcoholic standard Into the exoanded area
of the filled volumetric flask. Remove the needle as -
quickly as possible after injection. Mix by Inverting the
flask several tines. Discard the contents contained 1n the
neck of the flask. Aqueous standards should be prepared
fresh dally unless sealed and stored without headswee as
described in Sect. 7.
8.1.3 Analyze each calibration standard according to Sect. 10 and
tabulate peak height or area response versus the
concentration 1n the standard. The results can be used to
prepare a calibration curve for each compound.
Alternatively, If the ratio of response to concentration
(calibration factor) 1s a constant over the working range
(<10S relative standard deviation), linearity through the
origin can be assumed and the average ratio or calibration
factor can be used in place of a calibration curve.
8.1.4 Single point calibration is a viable alternative to a
calibration curve. Prepare single point standards from the
secondary dilution standard solutions. The single point
calibration standard should be prepared at a concentration
that produces a response close (*20X) to that of the
unknowns.
8.2 INSTRUMENT PERFORMANCE - Check the performance of the entire
analytical system dally using data gathered from analyses of reagent
blanks, standards, duplicate samples, and the laboratory control
standard (Sect. 9.2.2).
8.2.1 Peak tailing significantly in excess of that shown In the
method chromatogram must be corrected. Tailing problems are
generally traceable to active sites on the GC column or the
detector operation.
8.2.2 Check the precision between replicate analyses. A properly
operating system should perform with an average relative
standard deviation of less than 10X. Poor precision 1s
generally traceable to pneumatic leaks, especially at the
Injection port.
9. QUALITY CONTROL
9.1 Each laboratory that uses this method 1s required to operate a
formal quality control program. The minimum requirements of this
program consist of an Initial demonstration of laboratory detection
limits capability and an ongoing analysis of spiked samples to
evaluate and document data quality. Ongoing data quality checks
are compared with established performance criteria to determine 1f
the results of analyses meet the performance characteristics of the
method. When results of sample spikes Indicate atypical method
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performance, a quality control check standard must be analyzed to
confirm that the Measurements were performed in an In-control node
of operation.
9.1.1. The analyst oust Make an Initial determination of the Method
detection limits and demonstrate the ability to generate
acceptable accuracy and precision with this method. *Th1s 1s
established as described In Section 9.2.
9.1.2 In recognition of advances that are occurring 1n
chromatography, the analyst 1s permitted certain options to
Improve the separations or lower the cost of Measurements.
Each time such a Modification 1s Hade to the Method, the
analyst 1s required to repeat the procedure 1n Section 9.2.
9.1.3 Each day, the analyst Must analyze a reagent water blank to
demonstrate that Interferences from the analytical system
are under control.
9.1.4. The laboratory must, on an ongoing basis, demonstrate
through the analyses of quality control check standards that
the operation of the measurement system 1s 1n control. This
procedure 1s described 1n Section 9.3. The frequency of the
check standard analyses Is equivalent to 5X of all samples
analyzed.
9.1.5 On a weekly basis, the laboratory oust demonstrate the
ability to analyze low level samples. The procedure for low
level check samples Is described 1n Sect. 9.4.
9.2 To establish the ability to achieve low detection limits and
generate acceptable accuracy and precision, the analyst must
perform the following operations:
9.2.1 Prepare seven HDL check smples at 0.05 «g/L by spiking
35 »g/L of the MOL check staple concentrate (Sect. 6.7) Into
35-mL allquots of reagent water 1n 40-mL bottles. Cap and
Mix well.
9.2.2 Analyze the we!1-«1xed NX. check samples according to the
Method beginning 1n Section 10.
9.2.3 Calculate the average concentration found (7) 1n wg/L, and
the standard deviation of the concentrations (s) 1n ug/l,
for each analyte using the seven results. Then calculate
the MOL at 99% confidence level for seven replicates (6) as
3.143s.
9.2.4 For each analyte, T oust be between 801 and 1201 of the true
value. Additionally, the «L May not exceed the 0.05 ug/L
spiked concentration. If both analytes meet the acceptance
criteria, the system performance 1s acceptable and analysis
of actual samples can begin. If either analyte falls to
-------
t a crfterian, repeat the test. It 1s recommended that
the laboratory repeat the MDL determination on a regular
basis.
9.3 The laboratory must demonstrate on a frequency equivalent to 101 of
the sample load that the measurement system 1s 1n control by
analyzing a QC check sample of both analytes at 0.25 "
9.3.1 Prepare a QC check sample (0.25 »g/L) by adding 35 »L of QC
check sample concentrate (Sect. 6.6} to 35 mL of reagent
water 1n a 40-rt. bottle.
9.3.2 Analyze the QC check sample according to Sect. 10 and
calculate the recovery for each analyte. The recovery must
be between 601 and 1401 of the expected value.
9.3.3 If the recovery for either analyte falls outside the
designated range, the analyte falls the acceptance
criteria. A second check standard containing each analyte
that failed must be analyzed. Repeated failure, however,
will confirm a general problem with the measurement system.
If this occurs, locate and correct the source of the problem
and repeat the test.
9.4 On a weekly basis, the laboratory must demonstrate the ability to
analyze low level samples.
9.4.1 Prepare an MOL check sample (0.05 ug/L) as outlined 1n Sect.
9.2.1 and analyze according to the method 1n Sect. 10.
9.4.2 The Instrument response must -Indicate that the laboratory's
HDL 1s distinguishable from Instrument background signal.
If not. repeat the MOL test In Sect. 9.2.1. For each
analyte, the recovery must be between 601 and 1401 of the
expected value, when either analyte falls the test, the
analyst must repeat the test only for that analyte which
failed to meet the criteria. Repeated failure, however,
will confirm a general problem with the measurement system
or faulty samples and/or standards. If this occurs, locate
and correct the source of the problem and repeat the test.
9.5 It 1s recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific
practices that are most productive depend upon the needs of the
laboratory and the nature of the samples. Field duplicates may be
analyzed to assess the precision of the environmental
measurements. Whenever possible, the laboratory should analyze
standard reference materials and participate 1n relevant
performance evaluation studies.
10. PROCEDURE
10.1 SAMPLE PREPARATION
-------
10.1.1 Remove stooles and standards from storage and allow them to
reach room temperature.
10.1.2 For samples and field blanks, contained 1n 40-mL bottles,
remove the container cap. Discard a 5-rt. volume using a
5-«i. transfer pipette. Replace the container cap and weigh
the container with contents to the nearest O.lg and record
this weight for subsequent sample volume determination
(Sect. 10.3).
10.1.3 For calibration standards, QC check standards and reagent
blank, measure a 35-mL volume using a 50-flL graduated
cylinder and transfer 1t to a 40-mL sample container.
10.2 WCROEXTRACTION AND ANALYSIS
10.2.1 Remove the container cap and add 7g NaCl (Sect. 6.1.3) to
the sample.
10.2.2 Recap the sample container and dissolve the NaCl by shaking
by hand for about 20 sec.
10.2.3 Remove the cap and, using a transfer pipette, add 2.0 ml of
hexane. Recap and shake vigorously by hand for 1 m1n.
Allow the water and hexane phases to separate. (If stored
at this stage, keep the container upside down.)
10.2.4 Remove the cap and carefully transfer 0.5 ml of the hexane
layer Into an autosampler using a disposable glass pipette.
10.2.5 Transfer the remaining hexane phase, being careful not to
Include any of the water phase, 1nto,a second autosampler
vial. Reserve this second vial at 4*C for a reanalysls If
necessary.
10.2.6 Transfer the first sample vial to an autosampler set up to
Inject 2.0 uL portions Into the gas chromatograph for
analysis. Alternately, 2 «L portions of samples, blanks and
standards may be manually Injected, although an auto-
sampler Is strongly recommended.
10.3 DETERMINATION OF SAMPLE VOLUME
10.3.1 For samples and field blanks, remove the cap from the sample
container.
10.3.2 Discard the remaining sample/hexane mixture. Shake off the
remaining few drops using short, brisk wrist movements.
10.3.3 Rewelgh the empty container with original cap and calculate
the net weight of sample by difference to the nearest
0.1 g. This net weight 1s equivalent to the volume of water
(1n mi) extracted. (Sect. 11.3)
-------
11. CALCULATIONS
11.1 Identify EDB and OBCP in the sample chromatogram by comparing the
retention time of the suspect peak to retention times generated by
the calibration standards and the laboratory control standard.
11.2 Use the calibration curve or calibration factor (Sect. 8.1.3) to
directly calculate the unconnected concentration (C-j) of each
analyte 1n the sanple (e.g., calibration factor x response).
11.3 Calculate the sample volume (Vs) as equal to the net sample
weight:
Vs . gross weight (Sect. 10.1.2) - bottle tare (Sect. 10.3.3).
11.4 Calculate the corrected sample concentration as:
Concentration, «g/L » C X
11.5 Report the results for the unknown samples 1n wg/L. Round off the
results to the nearest 0.01 wg/L or two significant figures. .
12. ACCURACY AND PRECISION
12.1 Single laboratory (EMSL-C1ncinnat1) accuracy and precision at
several concentrations 1n tap water are presented 1n Table 2 (11).
The method detection limits are presented in Table 1.
12.2 In a preservation study extending over a 1 week period, the average
percent recoveries and relative standard deviations presented 1n
Table 3 were observed for reagent water (acidified), tap water and
groundwater. The results for acidified and non-acidified samples
were not significantly different.
13. REFERENCES
1. Glaze, W.W., L1n, C.C., Optimization of Liquid-Liquid Extraction Methods
for Analysis of Organics 1n Hater, EPA-600/S4-83-052, January 1984.
2. Henderson, J.E., Peyton, 6.R. and Glaze, W.H. (1976). In "Ident1f1ct1on
and Analysis of Organic Pollutants 1n Water' (L.H. Keith ed.),
pp. 105-111. Ann Arbor Sc1. Pub!., Ann Arbor, Michigan.
3. Richard, J.J., G.A. Junk, "Liquid Extraction for Rapid Determination of
Halomethanes In Water," Journal AWV1A, 69, 62, January 1977.
4. "Handbook for Analytical QuaVlty Control in Water and Wastewater
Laboratories^EPA-600/ 4-79-019, U. S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory - Cincinnati, Ohio
45268, March 1979.
-------
5. Budde, W.L., J.U. Eichelberger, "Organic Analyses Using Gas
Chromatography-Mass Spectrometry," Ann Arbor Science, Ann Arbor,
Michigan 1979.
6. Glaser, J.A. et al., 'Trace Analyses for Wastewaters," Environmental
Science and Technology. 15, 1426 (1981).
7. 'Methods for the Detemrination of Organic Compounds 1n Finished Drinking
Hater and Raw Source Water," Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio, September 1986.
8. "Carcinogens-Working with Carcinogens," Department of Health, Education,
and Welfare, Public Health Service, Center for Disease Control, National
Institute of Occupational Safety and Health, Publication No. 77-206,
August, 1977.
9. "OSHA Safety and Health Standards, General Industry," (29CFR1910).
Occupational Safety and Health Administration, OSHA 2206, (Revised,
January 1976).
10. "Safety in Academic Chemistry Laboratories," American Chemical Society
Publication, Committee on Chemical Safety, 3rd Edition, 1979.
11. Winfleld, T.U., et al. "Analysis of Organohalide Pesticides in Drinking
Water by Microextraction and Gas Chromatography." In preparation.
-------
Title 1. CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION
LIMITS FOR 1.2-OIBROMOETHANE (EDB) AND
1.2-OIBROMO-3-CHLOROPROPANE (D6CP)
Analyte
EDB
DBCP
Retention
Column A
9.5
17.3
T1meT M1n
Column B
8.9
15.0
HDL. uq/L
0.01
0.01
Column A conditions: Durawax-OX 3 (0.25 iun film thickness) 1n a 30 long x
0.32 im ID fused silica capillary column with he Hua^ carrier gas at
25 on/sec. Column temperature 'held Isothermal at 40*C for 4 «1n, then
programed at 8"C/m1n to 180'C for final hold.
Column B conditions: OB-1 (0.25 urn film thickness) 1n a 30 long x 0.32 mm
ID fused silica capillary column with helium carrier gas at 25 on/sec.
Column temperature held Isothermal at 40*C for 4 »ln, then programmed at
10'C/min to 270*C for final hold.
Table 2. SINGLE LABORATORY ACCURACY AND PRECISION
FOR EDB AND DBCP IN TAP WATER
Analyte
WHMMMAH^BM
EDB
DBCP
Number
of
S ancles
7
7
7
7
7
7
Spike
Level
(»q/L)
0.03
0.24
50.0
0.03
0.24
50.0
Average
Accuracy
(«
114
98
95
90
102
94
Relative
Standard
Deviation
(X)
9.5
11.8
4.7
11.4
8.3
4.8
-------
Table 3. ACCURACY AND PRECISION AT 2.0 ug/L
OVER A 4-WEEK STUDY PERIOD
Analyte
EDB
DBCP
Ptatrlxl
RW-A
SW
6U-A
TW
TVM
RW-A
GW
6W-A
TW
TW-A
Nuober
of Samoles
16
IS
16
16
16
16
16
16
16
16
Average
Accuracy
(t Recovery)
104
101
96
93
93
105
10S
101
95
94
Relative
SW. Dev.
(«)
4.7
2.5
4.7
6.3
6.1
8.2
6.2
8.4
10.1
6.9
Identities
RW-A Reagent water at pH 2
GU Groundwater, aoblent pH
GW-A . Grounctaater at pH 2
TW m Tap water, ant lent pH
TH-A . Tap vater at pH 2.
-------
o
1
n K
o
« s
^» c^
o
V
L.
V
I
S
e
«j
u
£
en
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Appendix B
Revision No. 2
Date: July 29, 1990
Page 1 of 5
APPENDIX B
NPS ANALYTE REPORTING BELOW MRL AND
IDENTIFYING UNKNOWN PEAKS
-------
J^'ts
f A -
I HM? I UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
* ^W^ T
V <#* EWVIROWWIIEWTAI. CHEMISTIIV LABORATORY. MACA/NTa
' "^ MJIIUMMG IMi. NCTL. MKSISSim JM2t
June 1, 1988
MEMORANDUM
SUBJECT: NFS Analyte Reporting Below MRL and Identifying Unknown Peaks
FROM: Bob Maxey, Analytical Coordinator
Environmental Chemistry Laboratory o / Vn^^y^^
TO: Dave Munch, Analytical Coordinator
TSD-Cincinnati
Aubry E. Dupuy, Jr. , Technical Monitor
Environmental Chemistry Laboratory
Attached are the procedures that NFS analytical contractors and referee
laboratories must adhere to in complying with the OPP request to report the
presence of analytes below the Minimal Reporting Limits and to attempt identi
fication of unknown peaks. Please see that your contractors and Technical
Monitors get this information and that applicable parts are incorporated into
their respective QAPPs.
If you have any questions, give me a call.
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Determining and Reporting the Presence of NPS Analytes 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 establi:
ed MRL and the MRL V on the primary column will be investigated. A respo
on the "secondary" GC column, indicating the presence of the analyte, is a
required for additional work.
2.a The first occurrence of a peak meeting the requirements of (1) is noted an
reported to the Technical Monitor, but no action is taken B/. Upon a seco
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 tai
place before continuing low-level analytical work on the analyte(s).
b With methods 1,2,3, 6 and 7, for 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 confi
mation is not within the capability of the laboratory/ such extracts are
sent weekly, under iced conditions by next-day air, to the appropriate re-
feree laboratory having HR GC/MS c/ capabilities. Copies of chrcmatograms
and all pertinent sample information must be sent 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 x EDL
NPS method 4 MRL = 3 x EDL
B/ = Method 6 has an MRL > the Health Advisory Level. All suspect ETU
responses of 1/2 MRL - MRL require additional work for this method.
C/ * LR * GC/MS = Low Resolution mass spectrometry.
HR GC/MS * High Resolution mass spectrometry.
-------
c. For Methods 4 and 5, HPLC Methods, there is no provision for GC/MS
confirmation. Suspect analytes between 1/2 HRL - 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 Son-NPS Analytes
It is expected that, over the course of the NT'S 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 crite
below.
1. For Methods 1, 2, 3, 6, and 7, if, upon initial analyses, the respons<
of an extraneous peak on the primary column is equal to or greater th,
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 u
known peak or response by GC/MS. Full scan spectra and subsequent
library search are expected and must be followed by comparison of t.K.e
spectra of the unknown compound with those of an authentic standard o
the suspected compound.
2. The work in (1) must be attempted by the contractor and/or referee la
oratories on the first occurrence of such a peak and the results of t
attempt reported to the Technical Monitor for the Method. If the
analytical contractor feels his system or instrument is not capable c
the confirmatory work» he must send both that extract and that of the
related Method Blank to the appropriate referee lab under iced
conditions by next-day air.
It is preferred that extracts be in sealed glass ampules, but other
vials and tef 190-faced closures are acceptable if they provide a tigh
seal and do not contribute interferences to the extracts. Volume lev
must be marked on the outside of the vial or ampule. (tFS will absor
costs of these shipments.)
-------
Specific sample and analytical information must accompany each auch
extract.
o Sample i.d. number, weight of sample matrix contained in the
ampule, copies of chromatograms from the primary GC column,
identification of the retention window for the unknown response(s)
as defined by the last NFS analyte to elute before the unknown
peak or response and the first NFS analyte to elute following the
unknown response.
3. Whether the identification of the unknown compound is attempted at the
Contractor Laboratory or at the referee laboratory, only the compounds
positively confirmed 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 NFS analytical system. Unsuccessful
attempts at identification will also be reported to the Technical
Monitor.
4. Following either the successful confirmation of two such extraneous peaks
proving to be the same compound or two failures to identify a response
with the same retention time without a prior successful GC/MS confirmation
on a sample, discussions with OFF personnel will take place before continu
with identification work on that particular compound.
THE QUALITY ASSURANCE PROJECT PLANS FOR BOTH THE ANALYTICAL CONTRACTORS
AND REFEREE LABORATORIES FOR METHODS 1, 2, 3, 6, AND 7 MUST REFLECT THEIR
COMMITMENTS TO THESE TWO REQUIREMENTS.
THE QUALITY ASSURANCE PROJECT PLANS FOR BOTH THE ANALYTICAL CONTRACTORS
AND REFEREE LABORATORIES FOR METHODS 4 AND 5 MUST REFLECT THEIR COMMIT-
MENTS TO THE REQUIREMENT FOR DETERMINING AND REPORTING NFS ANALYTES BELOW
THE MRL.
-------
Appendix C
Revision No. 2
Date: July 29, 1990
Page 1 of 2
APPENDIX C
GC/MS CONFIRMATION OF NPS SAMPLES
-------
V
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI. OHIO 45268
MEMORANDUM
DATE:
SUBJECT:
FROM:
TO:
July 19, 1988
GC/MS Confirmation of NFS Samples
Caroline Madding, Chemist
Drinking Water Quality Assessment Branch
Robert F. Thomas, Chemist, DVQAB
Edward M. Click, Chemist, DVQAB
Dan Hautman, Chemist, TAX
I will be qualitatively analyzing by GC/MS any sample for Methods 2 or 7
found in the confirmatory analysis to have any analyte concentration above
that analyte's reporting limit. If you have a sample that needs confir-
mation, please forward to me the sample extract and the method blank
extract for the appropriate set. I will also need a high standard of the
allegedly present analyte/analytes and a standard near the sample's
concentration.
-------
Appendix D
Revision No. 2
Date: July 29, 1990
Page 1 of 2
APF'ENDIX D
IDC RESULTS
-------
Determination of EPA-NPS Method 7
Estimated Detection Limits (EDL)
Signal to Noise Ratio - DB1 Column
Compound (ug/L )
1, 2-Dichloropropane (0.51)
Cis-l,3-Dichloropropene (0.015)
Trans-1,3-Dichloropropene (0.035)
EDB (0.005)
DBCP (0.005)
Peak
ht. (cmj
0.5
2.7
) 0.7
1.0
1.2
Average
No i se (cm)
0.10
0.25
0.25
0.25
0.25
Signal to
Noise Ration
5.00
10.8
2.80
4.00
4.80
EDL (ug.'L
Replicate Spike Method - DB1 Column
Compound
Spike 1
2
3
4
5
6
7
8
Mean
UStd. Dev.
«DL (ug/L)
1,2-DCP
(0.51 ug/L)
area counts
2023
2371
1869
2212
1949
2613
2227
2160
2178
240
0.17
C13DCP
(0.015 ug/L)
cm
2.6
2.6
2.6
2.7
2.5
2.6
2.5
2.4
2.56
.092
.002
T13DCP
(0.035 ug/L)
cm
0.60
0.70
0.70
0.60
0.70
0.60
0.60
0.50
0.625
.071
0.012
EDB
(0.005 ug/L)
cm
1.0
1.0
1.0
1.0
0.90
0.90
0.90
0.90
0.950
.054
0.001
DBCP
(0.005 ug'L)
cm
0.90
1.1
1.0
0.90
1 .0
0.90
0.90
0.90
0.9^3
.07i
0.001
.11
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Appendix E
Revision No. 2
Date: July 29, 1990
Page 1 of 3
APPENDIX E
CHANGES IN NPS LABORATORY PROCEDURES
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI OHIO 45268
HEKORANDUM
DATE: July 14. 1988
SUBJECT: Changes in UPS Laboratory Procedures
TROM: David J. Munch. TSD Project Manager
National Pesticide Survey
TO: NPS Technical Monitors (See below;
Tr.« following nr.cr changes in laboratory operations are beir.; Ted...
'.. Spiking Levels 'Methods !-"
Currently, selected !.'?3 sar-les ar being spined at either Lev*.!
1 (5 tirts XFL . Levil : ;:: tires MF.L , cr Levtl 3 (23 tir*s MFL .
In rany cases, spih.ir.; at Level 3 has erected analyt-: concer.traticr.:
in sarples which exceed thi linear range cf the instrumentation. Any.
Level 3 spiked sarples currently or. hand should be analyzed; hovevc: , "
no further requests will be- cadr to spihe sarples at Level ?.
In order to .Tamtam three spihing levels, a Level 0 (2 tires
XRL) is being added. Lc:::a:rry Control Standards and Tire Storace
Sc~;les are to continue tc be spiked at Level 2 (1C tir.es M.'L' .
2. S?i>:in; Levels (Method 9)
Currently, sairple spiking levels used for Method 9 are. Level 1
(2 times MRL) , Level 2 (10 times KRL) . and Level 3 (10,000 ug/L) . 7:. .
spiking levels are to remain the sare; however. Level 0 will now bt I
tir.es MRL, Level 1 10 tices KRL. and Level 3 10,000 ug/L.
3. Data Reporting Format
In order for the data reporting forcat to catch the requirements
for reporting suspected NPS analyt es observed on the pnzary colurr. ,
at a concentration between 1/2 MRL and KRL (see cenoranduit entitled
"Determining and Reporting the Presence of NTS Analytes below the
Miniauz Reporting Levels and Identifying Unknown Peaks," by Bob Msxey
6/1/88), further clarification is required. In those cases where the
presence of an NPS analyte at a concentration between 1/2 XRL and th?
HP.L is successfully confirmed, the primary and confirzcational colun.
data for that analyte should be reported as "-111". In those cases
where conf irmational analyses are either not required, or the
confirmational 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 boti your contract and refers
laboratories, as soon as possible. If you have any questions conce-z-
these ifo-s, please let xe know.
Addressees:
A. Dupuy
L. Kacphake (TS3)
C. "adding (TSi:
R. Maxey (OP?)
K. Sorrel! 'T£T(
R. Thor.as (7S:-
H. Brass (TSI1
C-. Freeb:s (CS:
A. Kroner (TSr
-------
Appendix F
Revision No. 2
Date: July 29, 1990
Page 1 of 17
APPENDIX F
NPSIS SAMPLE RECEIPT SOFTWARE FOR LABORATORIES
-------
MEBOfiAHDOM 4/5/88
TO: DATA MANAGER. KPA/TSD LAB
FR«: CHIP LESTER, ICF IK.
RE: HPSIS SAMPLE RECEIPT SOFTWARE FOR LABORATORIES
ICF's National Pesticide Survey Information System (NPSIS) 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 NPSIS 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 whic
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 1C!
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-EGA compatible graphics card.
For testing purposes, your sample kit identification numbers and FedEx
airbill numbers (respectively) are: PD-0000-711 and 1111111111, and PD-9999-
711 and 2222222222. Use these sample kit identification numbers when trying
out the NPSIS Sample Receipts Program.
Ve feel that it would be helpful to both parties if you could call us
when you are ready to test the NPSIS system, and we will assist you over the
phone during your session. If you would like to do this, please call Beth
Estrada at (703) 934-3431. NPSIS will be available for access 24-hours a da]
seven days a week. Ve appreciate hearing any comments you have regarding
NPSIS.
-------
THE RPSIS SAMPLE RECEIPT PROGRAM
KPSIS is designed to keep track of the day to day operations of the
National Pesticide Survey. You play an important role in NPS and your timely
notification of receiving a kit of saaples is essential to the success of NPS.
We have designed the Sanple Receipt Program with your busy schedule in Bind.
NPSIS will obtain the minimum amount of infomation 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.
1 1 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
least 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:
NPSIS Sample Receipt Program access provided for you by
ICF.
One (1) copy Carbon Copy software which is provided to yo
by ICF for the duration of NFS.
1.2 Initial Installation Steps.
Before you can access and use NPSIS. you must first load the Carbon Cop;
software onto your PC. The directions are provided in the Carbon Copy manua
One item you will want to include is an entry into the "Call Table". This
entry will include a name, telephone number, and password for the NPSIS
computer. To enter these items into the Call Table, press "2* from the Carb
Copy Parameters' Screen. The information you must enter consists of the
following:
-------
Nane: NFS
Telephone Number: 703-^1-0629
Password: NFS
1.3 Pflirffeters for Copnl cat ions
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 exit 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 .
7 REPORTING A SAMPLE RECEIPT TO HPSIS.
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" to the NPSIS computer at ICF. To do this
Type: C:> CGHELP HPS 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 what 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 wi]
see on the screen exactly what is on the screen of the NPSIS computer. This
screen you are viewing is the main menu for the Sample Receipt Program.
Remember that you are controlling the NPSIS computer via a 2400 baud phone
line and your typing will appear on the screen at a much slower rate than yox
are accustomed to. A few tips on how to use the system are outlined in the
next section.
-------
2_1 1 Useful Tips on How to Use NPSIS.
Before you start, a few things to remember are:
Pressing the "Esc" key will cancel all changes for the screen you
are currently in and return you to the previous screen. Pressing
"Esc" at the 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 i
items to enter in a screen which prompts for several items.
Pressing "Enter", "arrow up", or "arrow down" will aove 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 NPSIS
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 be placed at the initial Sample
Searching Screen for a new kit. If you are finished with your da:
entry, simply press "Esc" to exit the Sample Searching screen and
placed in the main menu.
2.3 A Basic Outline of the Sample Receipt Program.
The NPSIS Sample Receipt Program has three basic features:
Initial reporting of a NPS 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 i
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.
a
Any damage to the kit as a whole such as melted ice or >
breakage of the 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 unusab
for analysis and testing.
U±NPSIS Sample Receipt Program Screens.
When you have completed the logon procedure, you will see the following
nain 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 avallab
and thus represent the maximum number of screens you will encounter with
NPSIS. It is most likely that you will not have the need to enter informat
reporting damaged kits or samples. Therefore, not all of the screens depic
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 t
FedEx airbill number Associated with the specified kit. The screen will
appear like this:
-------
NFS Sample Receipt Searching Screen
** Enter the following items to access kit information **
To find the Kit information in NFSIS in the 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 ar
FedEx airbill number combination is incorrect, NFSIS will prompt you to try t
enter these number again, as illustrated on the next page. It is possible
that the 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 the
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!
******** ******** **A*********************************************
NFS IS 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.
***
-------
Once you have correctly identified the sample kit, NFSIS will ask you if
there is any damage to the kit as a whole:
Kit No.: PD-0001-151
Was there any damage to the saaple kit? (Y/N)
PgDn (Next page), PgUp (Previous page), Esc (Exit)
-------
If you press "Y", NPSIS will then prompt you for the 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) T
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), use f |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 an
which already appear. This insures that no information is destroyed.
-------
Next, NFSIS will ask you co survey the contents of the kit and check tha
which bottles are contained within the kit. You should then look at the
bottle labels and determine if any are missing. Don't forget to check and
determine if any bottles have been included in the kit which do not appear on
the list provided by NFS IS on this screen:
Kit No.: PD-0001-151
Please compare the following bottle numbers
with those in the sample kit.
Bottle No: PD-0001-1-1-01
Bottle No: PD-0001-1-1-03
Bottle No: PD-0001-1-3-01
Bottle No: PD-0001-1-3-03
Bottle No: PD-0001-1-9-01
Bottle No: PD-0001-1-9-03
Did you receive exactly these bottles in the sample kit? (Y/N) H
PgDn (Next page). PgUp (Previous page), Esc (Exit)
-------
If you have pressed "N", indicating that you did not receive exactly whi
NPSIS assuaes you have received, you will be pronpted to enter the appropriat
information. This information includes pressing a "Y" or a "N" beside each
bottle, and entering the bottle number found on the labels of any additional
bottles you have received:
Kit
1.
3.
5.
7.
No.: PD-0001-151
Please indicate which
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
Please indicate any
Bottle No. : PD-0002-1-
bottles you received:
Received (Y/N)
H
FJ
T
Y
Y
Y
additional bottles you received:
1-05 2. Bottle No.: PD-OO02- 2- 2-01
Bottle No.: PD-OOO4-A-4-01 4. Bottle No.: - - - -
Bottle No. : - - -
Bottle No. :
6. Bottle No. : - ...
8. Bottle No. : - ...
PgDn (Next page), PgUp (Previous page), use f ^or *Jto select field.
Notice that the user has indicated that he did not receive the first two
bottles on the list. Also note that the user has indicated additional bottle
which have come in the sample kit, but which were not on the list.
-------
Next, NFS IS prompts you Co indicate if any of the individual bottles ha-v
been daaaged and rendered unusable for analysis:
Kit No.: PD-0001-151
Was there any damage to the sample Bottles? (Y/N) T
PgDn (Next page), PgUp (Previous page), Esc (Exit)
-------
In order to complete che Appropriate information on damaged samples, you
must first press a "Y" or a "N" in the field labeled "Danaged Y/N". If you
have entered a "Y" in this field, you oust then identify what the cause of the
damage is. to the best of your abilities. As noted on the computer screen
belov, the "Other" category should be used if the sample is unusable but is
not broken. Please try to 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 the cause of damage.
---CAUSE ---
Bottle No: Damaged Broken Other Comment
(Y/N) (Y/N) (Y/N)
PD-0001-1-3-01 R
PD-0001-1-3-03 N
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 H
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 Ls unusable.
PgDn (Next page), PgUp (Previous page), use 4 | or 4' to select field
-------
Now you have completed all of Che necessary information needed Co verify
chat che proper samples have reached cheir final descinacion in usable
condicion. You aay save your kic encry by pressing "Encer". If you wish co
cancel your kic encry and cry again, press "N* and "Sneer". If you wish co
view or edic che currenc kic encry, press "R" and "Encer" and NPSIS will plac
you back ac che beginning of your encry.
You have completed all of Che daca encry screens for chis Kic.
You may save your encry by pressing 'Encer' .
You may cancel your encry by pressing 'N' and 'Encer' .
You may verify or edit this entry by pressing 'R' and 'Enter' .
* * * Accept entries? * * *
* Press *- to Save *
* Press N and ^ ' to Cancel *
* Press R and ^-J to Verify or Edit * T
By pressing "Enter" , you have saved all of Che information necessary fo
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 Chen log off of NPSIS by pressing "Ale" and "Righc shifc"
ac che same time. You may also send a memo through the ICF computerized mail
system. To do chis, cursor down Co che second menu choice and press "Encer".
The next two pages of this memo describe how co use che ICF eleccronic
mail system. Note Chat che password for you is NPS. The mail system softwar
prograa will prompt you for chis password before ic will allow access Co che
system. Also, when you are selecting the recipients of your memo, please
press che space bar beside che inicials "NPS". This will send your memo co
all ICF staff involved in che NPS project. If you wish Co send memos co a
parcicular ICF scaff member, please call BeCh Estrada for che idencificacion
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 mem
Highlight read,then pres
.
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 highligh
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 ba
twice to "de-select" recipients.
The small mark will disappea
d. Press to cancel the
entire list.
4. Select the initials of those who wil
receive copies:
a. Press the down arrow to me
to "CC-.
b. Select recipients as instructed
above (step 3, a-d)
-------
Writing Mail, continued
5. Enter 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 the Mail Program
1. Press from the menu.
2. Select 'YES'.
-------
Appendix G
Revision No. 2
Date- July 29, 1990
Page 1 of 6
APF'ENDIX G
FORMAT FOR NPS DATA
-------
FCGMtt PCR NATIONAL HiTlClUE SURVEY (NFS) DATA
COLUMNS
1 1-6 I_Tatp
9-14 S.Taip
17-24 Date_Sam
27-34 Date_Shp
37-44 Date_Rec
47-54 Time_Sam
57-64 Time.lce
[FCR METHODS 5 AND 9 CNLY]
68-69 JH
2 1-6 enter INITIAL TiMHiHATORE CF
9-14 enter SITflTTJTID TEMPEKAIURE CF
17-24 enter EPME S^MPUD
27-34 enter ESME SHIPPED
37-44 enter EME RECEIVED
47-54 enter TIME SWPLED
57-64 enter TIME ICED
[FCR METHODS 5 AND 9 CNLY]
67-70 enter pH
3 BLANK
4 1-17 Receipt Condition
5 1-80 enter CCNDITICN CF SAMPLE UPON PH'-KIMI- AT IABCRATCRY
6 BLANK
7 1-6 Sarrp #
16-18 Lab
21-25 Set #
28-35 Date.Spic
38-45 Date.Ext
48-55 Date.Ana
58-63 Colutm
8 1-13 enter SAMPLE IDENTIFICATiaN NI&BER
16-18 enter LAB ABBREVIATICN
21-25 enter SET NIMER
28-35 enter EME SPIKED
38-45 enter DATE EXTRACTED
48-55 enter DATE ANALYZED
58-63 enter ANALYSIS CCUMI
9 BLANK
-------
FORMAT FOR NATIONAL W&T1CUJE SURVEY (MI'S) EftTA (corrt. )
T.TMF. CHIMB
10 1-4 Type
8-13 Spiker
16-22 Extract
25-31 Analyst
34-40 Sam_Vol
43-49 Ext.Vol
52-60 Int. Std.
65-70 % Surr
11 1-5 enter SAMPLE TYPE
8-13 enter SPIKER'S INITIALS
16-22 enter EXTRACTOR'S rNTTIALS
25-31 enter ANALYST'S INITIALS
34-40 enter VOLUME OF SAMFI£
43-49 enter VOLUME OF EXTRACT
52-62 enter INTERNAL STANCWRD
65-70 enter PERCENT RECOVERY OF SURROGATE
12 BLANK
13 1-8 Caments
14 1-80 enter ANY PERTINENT CCrWENTS CN SAMPLE AND ANALYSIS
15 BLANK
16 1-7 Analyte
29-33 Cone.
39-45 Analyte
67-71 Cone.
17-? 1-25 enter ANALYTE 'S NAME
28-34 enter CONCENTRATION OR PERCENT RECOVERY
39-63 enter ANALYTE »S NAME
66-72 enter CONCENTRATION OR PERCENT RECOVERY
-------
FCRAT'PCR NAHCXRL PESTICHE SURVEY (NFS) ZHSIRLMENT CONTRCL
T.TMF. CTTIMSE
1 1-3
6-11
14-21
24-30
35-37
42-44
49-51
55-58
Method
Date_Ana
Analyst
S/N
PST
PGF
Res.
3-?
BLANK
1-3
6-11
14-21
24-30
33-37
40-44
47-51
54-58
enter IAB AEBREVIATICN
enter MEHHD NU^BEI^
enter EKEE M^LYZED
enter AMALYST'S INITIALS
enter SIQBVL TO NOISE RATIO
enter PEMC SYM^E3RY FACTOR
enter FEWC GETHEnRY FACTOR
enter RESOLOTION
-------
NOTES CN NFS EKEA FOFMMS
1. The format for any date is nm/dd/yy
A missing date should be entered 01/01/60
2. The format for any time is hh:nm 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. "Ere number of decimal places should be as follows:
Concentration 3
Percent Recovery l
Internal Standard 0
Instrument Controls 2
pH l
Temperatures 0
Volumes 0
5. "Die codes for Column are as follows:
Primary PRIM
Confirmatory OUT
Third GCMS
6. The codes for Lab are as follows:
TSD TSD
QPP OPP
WERL WER
Radian RAD
Battelle BOD
James M. Montgomery JMM
Alliance ALL
Environmental Science:; and Engineering
7. The codes for Type are as follows:
Field Sample SWF
Shipping Blank SBLK
Method Blank MBLK
Lab Control Standard LCSf
Lab Spike Sample LSSCt
Time Storage for Detract HIES
Time Storage for Sample KTSC
where is the mix-' letter (A,B,C or D)
and f is the spiking level (1,2 or 3)
'( \ 6 K ' i 0 n <_ >«. \ A U $£- n
-------
NOTES CN NFS DMA FCRftTS (cent.)
8. There should be at least one blank line between sanples in the NFS data
file.
9. Tne codes for Concentrations and Percent Recoveries are as follows:
Not Analyzed
Not Detected « Estimated Detection Limit) -999
Saturated -777
Other ' -333
Below Reporting Limit, but above EEL -m
Above Reporting Limit, but not Quantified 888
10. If a reported value is greater than (>) some number in the NFS instrument
control data, then use a minus sign (-) instead of >
-------
Appendix H
Revision No 2
Date. July 29, 1990
Page 1 of 3
APPENDIX H
DATA REPORTING FORMAT CHANGES
-------
HKHORAirDtrH
DATE: April 18, 1988
SUBJECT: OatA Reporting Format
FROM: David J. Hunch, Chemist
Drinking Water Quality Assessment Branch
TO: UPS Technical Monitors (See below)
The purpose of this memorandum is to consolidate the changes to the
UPS data reporting format, which have occurred since it was originally
constructed. You have previously been supplied with most 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. Line 2, columns 67-70 are to be used to record the pH measured
upon sample receipt at the laboratory. This only applies to
methods 5 and 9.
3. Line 8, columns 1-13, Sample Identification lumber, 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
LSStf
DTSt
HTEt
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 be*m made to the codes for
analyte concentration entries.
-999 lot Detected « 1/2 Minimum Importing Limit)
-111 Below Minimum Reporting Limit bat greater than or e^ual to
1/2 the Minimum Reporti*g Limit.
-------
3
4
5
6
7
Note: Method 9 only
3*£-**i
Format for National Pesticide Survey (NPS) Data
COLUMNS DESCRIPTION
1-6
9-14
17-24
27-34
37-44
47-54
57-64
68-69
1-6
9-14
17-24
27-34
37-44
47-54
57-64
68-69
BLANK
1-17
1-80
BLANK
1-6
16-18
21-25
28-35
38-45
48-55
58-63
1-13
16-18
21-25
28-35
38-45
48-55
58-63
S~Temp
Date_Sao
Date~Shp
Date'Rec
Time'Saa
Tine'lce
pB ~
enter
enter STABILIZED TEMPERATURE OF VATER
enter DATE SAMPLED
enter DATE SHIPPED
enter DATE RECEIVED
enter TIME SAMPLED
enter TIME ICED
enter pB Note: Method 9 only
Receipt Condition
enter CONDITION OF SAMPLE UPON RECIEPT AT LABORATORY
Safflp I
Lab
Set t
Date_Spk
Date_Ext
Date~Ana
Column
enter SAMPLE IDENTIFICATION NUMBER
enter LAB ABBREVIATION (JMM)
enter SET NUMBER
enter DATE SPIKED
enter DATE EXTRACTED
enter DATE ANALYZED
enter ANALYSIS COLUMN
BLANK
-------
Appendix I
Revision No. 2
Date: July 29, 1990
Page 1 of 4
APPENDIX I
DATA REPORTING CODES
-------
DZVTE: September 9, 1988
SUBJECT: Data Reporting Codes
FRCM: 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 some confusion over these codes
as to when and where to use them and their exact meaning.
Table 1 identifies the unique sample types (SBMP - field sample, MBLK -
method blank, SBLK - shipping blank, DCS - lab control standard, and LSS, DTS,
HIE, and HTS - spiked field samples these last three are each a type of time
storage sample). Under each unique sample type are the only possible codes
that can appear for that sample type. (Note: -555 has been added for the
situation where the contract lab sends the extract to the referee lab for GCMS
analysis, and the code -222 has been deleted.) There is also a type of
decision tree for field samples 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, Environmental Chemistry Laboratory
Carol Madding, Technical Support Division
Bob Maxey, Environmental Chemistry Laboratory
Dave Mmch, Technical Support Division
Kent Sorrell, Technical Support Division
Bob Thomas, Technical Support Division
-------
TMLE 1: USES CF EM& COTES IN NFS
SAMPLE TYPE
Lss,nrs
SAMP
.(a)
i i i (C)
_333(d)
_444(e)
-555
****
_777(h)
888 (V
-999 (j)
conc(k)
SBLK
.(a)
lll^c'
-333 WJ-
_444e
-555
-------
-333
Sdimle Qalitative o
-999 888
-333 -999
OOLtMJ
PRIM
CCNF
-333 -555 -999 888 GCMS
GOMS
(at referee
-333 -999 888
Sample (Quantitative analvte with PC failure)
-333 -444 -666
-333 -666 -999
-333 -555 -999 888
-333 -999 888
PRIM
CCNF
GCMS
GCMS
(at referee
Sample (C\i^ntitafjv»? gnalvte vitji nn oc
-111 -333 -777* -999 cane
PRIM
CCNF
-333 -555 -999 888 -333 -555 -999 888 -333 -555 -999 888 -333 -555 -999 888 GCMS
-111 -333 -999 cane
-111 -333 -999 care
-333 -999 888 -333 -999 888
-333 -999 888
-333 -999 888 GCNS
(at referee
a = Dilute and reanalyze
-------
Appendix J
Revision No. 2
Date: July 29, 1990
Page 1 of 11
APPENDIX J
NPS RAPID REPORTING SYSTEM
-------
I UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
0«T CINCINNATI. OHIO 45268
MEMORANDUM
DATE: April 12, 1988
SUBJECT: NFS Rapid Reporting System
FROM: David J. Munch, Chemist
Drinking Water Quality Assessment Branch
TO: NFS Technical Monitors
Jerry Kotas has requested that any confirmed results of health
significance be reported as quickly as possible. Therefore, 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 (MRL), any
occurrence at or above 1/2 the KRL should also be processed as below.
(Note: The procedures for determining the occurrence of NFS analytes that
may occur below the MRL, and are not listed on the attached tables, have
not yet been finalized.)
1. The appropriate confirmational analyses (GC/MS for methods 1-3,
6-7, second column for Method 5) should be performed as soon as
practical.
2. The laboratory should telephone their Technical Monitor, the same
day the confirmation is completed.
3. The laboratory should immediately document the observed result in
a letter to their Technical Monitor.
4. As quickly as possible on 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 on to the Laboratory Analytical
Coordinator the above documentation, with any comments he/she may
have concerning the validity of the result.
5. The Laboratory Analytical Coordinator should inform Jerry Kotas
and the second Analytical Coordinator of the finding by telephone
the same day if possible, and in writing after the documentation
is received from the Technical Monitor.
6. The Analytical Coordinators are to request, through the
appropriate Technical Monitors, that all analyses for this sample
site be conducted, and reported in writing, as soon as practical.
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-2-
If you have any questions concerning these procedures, please let Bob
Haxey or me know. Also, please pass on this information to your contract
and referee laboratories. They will need to have this information in hand
prior to their conducting the dry run.
Attachment
Addressees:
A. Dupuy
L. Kamphake
C. Madding
R. Maxey
R. Sorrell
R. Thomas
cc:
J. Kotas
H. Brass
A. Kroner
J. Orme
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METHOD fl
AMALYTt RAPID REPORTING LEVEL
Alachlor 44 ug/L
Aaetryn 300 ug/L
Atrazine 35 ug/L
Bromacil 2,500 ug/L
Butylate 700 ug/L
Carboxin 1,000 ug/L
Dipbenamid 300 ug/L
Penamiphos 5.0 ug/L
Hexazinooe 1,050 ug/L
Metolachlor 300 ug/L
Metribuzin 250 ug/L
Propazine 500 ug/L
Simazine 50 ug/L
Tebutbiuron 125 ug/L
Terbacil 250 ug/L
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METHOD 12
AMALYTE RAPID REPORTIHG LEVEL
alpha-Chlordane 0.5 ug/L
ganuna-Chlordane 0.5 ug/L
Chlorothalonil 150 ug/L
Dacthal (DCPA) 5.000 ug/L
Dieldrin 0.5 ug/L
Propachlor 130 ug/L
Trifluralin 25 ug/L
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METHOD 13
ANALYTE RAPID REPORTING LZYEL
Acifluorfen 130 ug/L
Bentazon 87.5 ug/L
2,4-D 100 ug/L
Dalapon 800 ug/L
Dicamba 13 ug/L
Dinoseb 3.5 ug/L
Pentachlorophenol 300 ug/L
Picloram 700 ug/L
2,4,5-T 105 ug/L
2,4,5-TP 70 ug/L
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METHOD 14
AKALYTE RAPID REPORTING LEVEL
Cyanazine 13 ug/L
Diuron 70 ug/L
Fluooeturon 438 ug/L
Propham 595 ug/L
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METHOD |5
AHALYTE RAPID REPORTING LEVEL
Aldicarb 10 ug/L
Baygon 40 ug/L
Carbaryl 1,000 ug/L
Carbofuran 50 ug/L
Hethonyl 250 ug/L
Oxaayl 175 ug/L
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METHOD 16
AHALYTE RAPID REPORTING LEVEL
ethylene thiourea 1.05 ug/L
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METHOD 17
AMALYTE RAPID REPORTIMG LEVEL
dibroBOchloroproptne 2.5 ug/L
1,2-dichloropropmne 56 ug/L
cis/trans 1,3-dichloropropene 11 ug/L
ethylene dibromide 0.04 ug/L
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METHOD 19
AMALYTE
Nitrate/Nitrite
10,000 ug/L
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Appendix K
Revision No. 2
Date: July 29, 1990
Page 1 of 5
APPENDIX K
DIXON'S TEST
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DIXON'S TEST
Dixon's test is used to confirm the suspicion of outliers of a set of data
(for example, control chart data points). It is based on ranking the data
points and testing the extreme values for credibility. Dixon's test is based
on the ratios of differences between observations and does not involve the
calculation of standard deviations.
The procedure for Dixon's test is as follows (from Taylor, 1987):
1) The data is ranked in order of increasing numerical value. For
example:
Xi < X2 < X3 < ... < Vi < X,
2) Decide whether the smallest, X1( or the largest, X,,, is
suspected to be an outlier.
3) Select the risk you are willing to take for false rejection,
For use in this QAPP we will be using a 5X risk of false
rejection.
4) Compute one of the ratios in Table 1. For use in this QAPP we
will be using ratio TCZ2> 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 5Z risk values (bolded).
Example (from Taylor)
Given the following set of ranked data:
10.45, 10.47, 10.47, 10.48, 10.49, 10.50, 10.50, 10.53, 10.58
The value 10.58 is suspected of being an outlier.
1) Calculate rn
10.58 - 10.53 0.05
ru - - - 0.454
10.58 - 10.47 0.11
2) A 5% risk of false rejection (Table 2), ru - 0.477
3) Therefore there is no reason to reject the value 10.58.
4) Note that at a 10% risk of false rejection rn - 0.409, and the value
10.58 would be rejected.
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TABLE 1
CALCULATION OF RATIOS
For use if if X,, is if Xx is
Ratio n is between suspect suspect
V \ / V
' ^n-l/ \&2 ~
-10 3 - 7
Note that for use in this QAPjP ratio r22 will be used.
v \ / v
" Xn-l) (X2 -
rn 8-10
- Xn-2> (X3
C21 n - 13
- X2) (X,,.!
V S / V
Ati-2/ ^A3
r22 1^ - 25
- X3) (Xn.2
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TABLE 2
VALUES FOR USE WITH THE DIXON TEST FOR OUTLIERS
Ratio
-10
L21
0.5%
Risk of False Rejection
1* 5%
10%
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
0.994
0.926
0.821
0.740
0.080
0.725
0.677
0.639
0.713
0.675
0.649
0.674
0.647
0.624
0.605
0.589
0.575
0.562
0.988
0.889
0.780
0.698
0.637
0.683
0.635
0.597
0.679
' 0.642
0.615
0.641
0.616
0.595
0.577
0.561
0.547
0.535
0.524
0.514
0.505
0.497
0.489
0.941
0.765
0.642
0.560
0.507
0.554
0.512
0.477
0.576
0.546
0.521
0.546
0.525
0.507
0.490
0.475
0.462
0.450
0.440
0.430
0.421
0.413
0.406
0.806
0.679
0.557
0.482
0.434
0.479
0.441
0.409
0.517
0.490
0.467
0.492
0.472
0.454
0.438
0.424
0.412
0.401
0.391
0.382
0.374
0.367
0.360
Note that for this QAPjP the 5% risk level will be used for ratio r
22-
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Reference:
John K. Taylor, Quality Assurance of Chemical Measurements. Lewis
Publishers, Chelsea, MI, 1987.
u S Environmental Protection Agency
Region 5, Library (PL-UJ)
77 West Jackson Boulevard, 12th rloor
Chicago, IL 60604-3590
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Appendix L
Revision No 2
Date- July 29, 1990
Page 1 of 2
APPENDIX L
STANDARD OPERATING PROCEDURES;
BATCH FILING SYSTEM
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Appendix L
Revision No. 2
Dale: July 29, 1990
Page 2 of 2
APPENDIX L
STANDARD OPERATING PROCEDURE:
BATCH FILING SYSTEM
PURPOSE
To centralize the storage of ESE analytical data batches and all associated documentation
for each batch.
PROCEDURE
All data batches created by the various departments will be placed in clepartmentally assigned
colored batch files. All associated documentation for each batch will be included in each folder as
well as a documentation checklist. The checklist will be marked by the analyst noting everything
included in the batch file and will be signed and dated by the analyst and a review person.
The batch file must also have the "Computer QC Checks" and the "Internal QA/QC Batch
Checklist" section located at the end of each batch marked, signed and dated by the analyst. The
batch then must be reviewed, signed and dated by the Department Manager. If the batch fails any of
these checks, the corresponding Lab Coordinator(s) for all samples in the batch must also sign and
date the batch and may add comments.
The batch file is then signed-in to Information Services to document chain-of-custody of the raw
data.
Each batch will then be finalized and filed numerically by department in locked file cabinets
located in the Information Services department. Each department manager will have a key to his/her
file cabinet and Information Services will retain a key to all cabinets.
Since only the most recent batches can be filed in the file cabinets, all "older" batches are filed
by department in a separate, locked storage room with access available only to Information Services.
All data batches including those !ln the storage room are available for checkout at any time. All
batches are signed out to the individual with a hard copy as well as an electronic file kept of all
checkouts.
U.S. Environmental Protection Agency
Re?jor. 5, Library (FL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
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