EPA-810/B-92-005
United States Office of Water (WH-550) EPA 810-B-92-005
Environmental Protection Office of Pesticides and February 1992
Agency Toadc Substances (H-7501C)
QUALITY ASSURANCE PROJECT PLAN
FOR THE
NATIONAL PESTICIDE SURVEY OF DRINKING WATER WELLS
ANALYTICAL METHOD 5 - METHYL CARBAMATES
Prepared by:
Michael G. Winslow and David H. Greer
Environmental Science & Engineering, Inc.
P.O. Box 1703
Gainesville, PL 32602
Prepared for:
U.S. Environmental Protection Agency
Technical Support Division
Office of Drinking Water
26 W. Martin Luther King Drive
Cincinnati, Ohio 45268
US Environmental Protection Agency
5, Library (PL-12J)
iJackson Boulevard, 12th Floor
60604-3590
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Section No. 1
Revision No. 2
Date: July 29, 1990
Page 2 of 2
Paul Geiszler
R. Kent Sorrell
Portia Pisigan
Lora Johnson
APPROVAL PAGE
, ESE Project Leader
, TSD Technical Monitor
, ESE QAC
, NPS QAO
Elizabeth Leovey
, OPP QA Officer
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Section No. 2
Revision No. 2
Date: July 29, 1990
Page 1 of 2
•>t-
<0
-•4
NATIONAL PESTICIDE SURVEY
QUALITY ASSURANCE PROJECT PLAN FOR
ANALYTICAL METHOD 5 - METHYL CARBAMATES
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 DA - ,
Pages
2
2
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4
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2
1
2
Revisions
2
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2
2
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Date
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Section No. 2
Revision No. 2
Date: July 29, 1990
Page 2 of 2
2. TABLE OF CONTENTS (continued)
Appendices
A.
B.
C.
D.
E.
F.
G.
H.
1.
J.
METHOD 5. MEASUREMENT OF
N-METHYLCARBAMOYLOXIMES AND
N-METHYLCARBAMATES IN
GROUND WATER BY DIRECT
AQUEOUS INJECTION HPLC WITH
POST COLUMN DERIVATIZATION
NPS ANALYTE REPORTING BELOW MRL AND
IDENTIFYING UNKNOWN PEAKS
CHANGES IN NPS LABORATORY PROCEDURES
NPSIS SAMPLE RECEIPT SOFTWARE FOR
LABORATORIES
FORMAT FOR NPS DATA
DATA REPORTING FORMAT CHANGES
DATA REPORTING CODES
NPS RAPID REPORTING SYSTEM
DIXON'S TEST
STANDARD OPERATING PROCEDURE: BATCH
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FILING SYSTEM
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Section No 3
Revision No. 2
Date: July 29, 1990
Page 1 of 1
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
5, the determination of aldicarb, aldicarb sulfone, aldicarb sulfoxide, baygon, carbaryl, carbofuran, 3-
hydroxy-carbofuran, methiocarb, methomyl, and oxamyl in ground waters. Method 5 involves direct
injection of an aliquot of the water sample, high-pressure liquid chromatographic separation,
derivatization, and fluorescence detection and quantitation. Positive results will be confirmed by
second column analysis. Method 5 is an adaptation of EMSL Method 531.1, "Measurement of N-
Methylcarbamoyloximes and N-Methylcarbamates in Water by Direct Aqueous Injection HPLC with
Post Column Derivatization" (Appendix A).
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Section No. 4
Revision No. 2
Date: July 29, 1990
Page 1 of 2
4. PROJECT ORGANIZATION AND RESPONSIBILITIES
The project staff is specified in ESE's proposal to perform the contract. The project organization
chart is given 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
Bradley A. Weichert Manager, GC/HPLC Department
W. Scott Keeran Associate Scientist, Lead Chemist
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
Scott Poole 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 5 matters is
R. Kent Sorrell, phone (513) 569-7943. The EPA Project Officer is David J. Munch.
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Section No. 4
Revision No. 2
Date: July 29, 1990
Page 2 of 2
EXHIBIT 4-1
PROJECT ORGANIZATION CHART
EPA TECHNICAL MONITOR
K. Sorrell
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. Yen
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Section No. 5
Revision No. 2
Date: July 29, 1990
Page 1 of 2
5. QUALITY ASSURANCE OBJECTIVES FOR MEASUREMENT DATA
The "estimated detection limit" (EDL) for Method 5 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 of 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. Target EDLs shall be supplied to ESE by the Technical Monitor.
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. GC/MS analyses is not part of Method 5 confirmation.
9. Minimum Reporting Levels (MRL) are 3 times the EDL for each analyte.
10. 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).
11. The lowest standard solution concentration will approximately equal the MRL for all
analytes.
12. 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 (RSD) will be used to evaluate the precision of the
method using the acceptance criteria provided by the EPA.
13. The criteria values will be reviewed by the Technical Monitor.
Samples having any analyte concentration above that analyte's reporting limit will be confirmed
on a different HPLC column (see Section 9).
Performance evaluation samples will be analyzed quarterly as part of the overall NPS QA
program. The Technical Monitor will work with ESE to resolve any problems discovered as a result of
these analyses.
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Date: "\July" 29, 1
Page 2 of 2
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 is appended to this Plan.
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 from 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 C). This sample will be
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 4
6. SAMPLING PROCEDURES
All samples for Method 5 will be received in 250 ml_ bottles. Samples for Method 5 will include
pH 3 buffer and will be shipped iced for overnight delivery. Every set received from a field site will
include the following: primary samples and one backup sample for each primary sample. Some sets
will include time-storage samples. Some sets (about 10%) will include lab-spike samples (ESE matrix-
spikes).
Analysis types and frequency are described on the next page.
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The analysis types for Method 5
Primary Analysis:
Method Blank
Calibration Standards
Field Sample
Lab Spike (ESE Matrix Spike)
Day 0 Time-Storage Sample
Day 14 Time-Storage Sample
Performance Evaluation Sample
Backup Sample
Confirmational Analysis:
Method Blank
Calibration Standards
Field Sample
f*. V - *> "•
are:
1 per set
daily
1 per ESE
sample no.
10%
10%
10%
quarterly
(a)
1 per set
daily (when conf.
is performed)
(b)
— ^^^ ,_ . Section No. 6 . f -
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"Date: July 29, 1990
Page 2 of 4
Not chargeable
Not chargeable
Chargeable
Chargeable
Chargeable
Chargeable
Chargeable
(a)
Not chargeable ' — "- ~
Not chargeable
Chargeable
(a) Analyzed when results of initial analysis fails (not chargeable) or at request of Technical
Monitor (chargeable).
(b) Analyzed when results of primary analysis are above min. reporting limit.
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Section No. 6
Revision No. 2 •
"Date: July'SS, 1990
Page 3 of 4
Each sample's shipping label will be of the form below.
NATIONAL PESTICIDE SURVEY - NFS
PD-0415-4-5-6 DATE 2-11 -88
ESE - #5 - T/S0
SAMPLER NAME
The sample bottle number (PD-0415-4-5-6 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
5 is the carbamates method number
6 is the bottle number within this site number
The analysis type codes are given below:
FS Field Sample
FD Field Duplicate
BU Backup Sample
LS Lab Spike (ESE Matrix Spike; "LS" may be followed by a numeric digit which
T/S
T/S0
T/S
14
indicates spike level)
Time Storage (t = 14 days)
Time Storage Duplicate (t = 0 days)
Time Storage Duplicate (t = 14 days)
The sampling contractor will supply a copy of the field sample tracking sheet used for NFS
samples.
The spiking solution is prepared fresh daily in chloroacetic buffered water and is prepared from
a primary acetonitrile stock. The lab spike is prepared by adding the appropriate volume of the
spiking stock (AO = 200 uL; A1 = 500 uL; A2 = 1000 uL) to 250 uL of 2.5 M chloroacetic buffer and
enough HPLC water to yield a final volume of 25.0 mL Then 10 mL of this solution is filtered through
a 0.45 uM Acrodisc filter and spiked with 100 uL of the internal standard. All lab spikes are analyzed
on the same day that they are prepared.
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"Date: July'2§, 1390
Page 4 of 4
In addition, the time storage samples are prepared in exactly the same manner as the above lab
spikes. The Day 14 time storage samples are then transferred to a 40 ml amber VGA bottle and
stored in the freezer. On the day of analysis, the sample is thawed, filtered, and spiked with the
internal standard.
Using the above spiking schemes, the solutions should correspond to: AO = 2 x MRL; A1 = 5 x
MRL; A2 = 10 x MRL
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Section No. 7
Revision. No 2-
"Date: July'2§,
Page 1 of 1
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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 (Appendix D). The project Technical Monitor will also be notified concerning
problems with the receipt of samples from the sampling contractor (ie. no ice, incorrect pH, etc).
Holding times for samples to be analyzed by Method 5 are: 14 days maximum holding time for
samples, counting day of sampling as Day 0. Upon receipt of samples at the laboratory, a portion of
the sample will be removed to facilitate freezing and for pH measurement using disposable pH test
strips. Samples will be stored frozen in the dark. 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 will be collected. Two of the four
replicate-aliquots will be spiked and analyzed within 4 days of spiking and prior to the 14 day .holding-
time. The remaining two duplicates will be spiked at the same time as the first two duplicates, but will
be allowed to sit 14 +_ 4 days before analysis.
Each sample will be spiked with only one mix at the 10X MRL level. Results of the time storage
samples will be reported to EPA along with the corresponding regular sample. For data reporting
purposes, Day-0 samples (spiked and analyzed within 4 days of spiking) will be referred to as Day-0
Time Storage (DTS). These samples serve a dual role, as lab spikes and DTS. Day-14 time storage
samples (spiked and held for 14 +_ 4 days before analysis) will be referred to as Holding Time
Samples (HTS). All of the holding time samples will be analyzed in duplicate.
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 mark the NPS sample tracking form with the
required information, and 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 5 Task Manager. The GC/HPLC department schedules the analyses,
performs them within the 14-day holding times, and enters the analytical data into the ESE database.
All ESE coldrooms, refrigerators, and freezers holding samples for chemical analysis are
monitored daily by ESE personnel, and records are kept daily.
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Section No 8
Revisioh No. 2'
"Date: July'2!,
Page 1 of 1
8. CALIBRATION PROCEDURES AND FREQUENCY
The instrumental analysis for Method 5 will be performed on a HPLC instrument including an
Shimadzu Gradient HPLC System: 2 LC-6A pumps, SCL-6A system controller, SIL-6A autoinjector, a
Kratos post-column reactor, a Shimadzu RF535 fluorescence detector, and a PE/Nelson
chromatography data acquisition system. Primary analytical separations will be performed on Waters
Nova Pak ODS columns (25 cm length, 4.6 mm ID, 5 micron particle size) or equivalent, and
secondary analytical separations will be performed on Supelcosil LC-1 columns (25 cm length, 4.6 mm
ID, 5 micron particle size). The mobile phase gradient program will be that described in Method 5
which is appended to this Plan.
ESE analysts will prepare standard solutions in water/chloroacetic acid buffer from dilutions of
EPA concentrate solutions at the onset of each analytical set 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 in that day's analysis. New standard dilutions will be checke4-to
insure that the QC criteria, ± 20% of initial calibration, is met.
ESE plans to calibrate the instrument each day a set is analyzed using a calibration standard
concentration chosen, on a rotating basis, from the standard curve. The lowest calibration standard
will be at the MRL The standard relative response must agree within +_ 20% of the previous set's
calibration relative response.
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.
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Section No. 9
Revision No. 2- •
"Date: July 25, 1990
Page 1 of 1
9. ANALYTICAL PROCEDURES
Samples will be thawed and brought to room temperature in a warm water bath prior to
analysis. The primary analysis begins with the addition of internal standard to an aliquot of water
sample. Gradient elution down the reverse-phase HPLC column separates the analytes and other
components, and analytes are detected as follows: the analytes are hydrolyzed with 0.05 N sodium
hydroxide at 95 °C, the resulting methylamine is reacted with ortho-phthalaldehyde (OPA) and 2-
mercaptoethanol, and the resulting highly fluorescent derivative is detected in the flow cell of a
fluorescence detector. In confirmatory analysis, the sample aliquot is eluted down a somewhat
different column, detection in the same manner verifies or rules out any positive results from the
primary analysis.
Primary and confirmatory analyses are performed on an Shimadzu high-pressure liquid
chromatograph equipped with a Kratos post-column reaction cell, a Shimadzu fluorescence detector
(excitation wavelength = 235nm, emission wavelength = 435nm), and a PE/Nelson chromatography
data acquisition system. 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 24 field samples in a set (16 hour run), and generally fewer.
ESE plans no significant differences from Method 5, revision dated October 27, 1987 (attached)
as provided to ESE in glassware cleaning, reagents, or data reduction. Differences in equipment are
listed above in this Section. In the analytical procedure, ESE plans, to use Waters Nova Pak ODS
columns for the primary analysis and Supelcosil LC-1 columns for the confirmatory analysis.
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
Revision No. 2 •
"Date: July 2:9, 1S90
Page 1 of 1
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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.
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.
The NPS file format is appended to this Plan (Appendix E, F and G).
Fast Track Reporting (immediate telephone call to the Technical monitor) will be needed for
confirmed positive sample concentrations of selected EPA analytes above health advisory levels and
situations when results from confirmation columns do not agree with results from primary columns
within criteria set by EPA (+ 25%) (Appendix H.). —
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 central filing system. ESE set folders will reside in archival files in ESE's
central filing system after all samples have been analyzed.
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Section No. 1 1
Revision No. 2 -
* * -Y j .
Date: July 29, 1930
Page 1 of 3
'.f •,
11. INTERNAL QUALITY CONTROL CHECKS
No lab control spikes are required for Method 5. Analytical quality will be controlled largely by
five means:
Each set will include a chromatogram of a standard, selected on a rotating basis
from the calibration standards. The response factors for the standard must be
within +_ 20 percent (%) of the initial calibration. If the response factors fall outside
the +. 20% criteria, the standard will be reanalyzed, if the response factor is stilt
outside the criteria a new initial calibration will be performed.
Each set's method blank must have analyte responses less than half the minimum
reporting limit.
Internal standard response (peak area) for each sample must be within 20% of the
internal standard response from that day's calibration standard.
The instrument performance sample will meet the criteria described in Method 5,
Section 10.8., Table 10.
If the relative responses of the analytes in each set's standard chromatograms
appear to the analyst to have changed significantly (+_ 20%) from those of the.
previous set, lie will make new standard solutions from the EPA concentrates. The
stability of Method 5 analytes suggests that this may be a very unusual occurrence.
• Any analyte detected above the MRL in the primary analysis will be re-analyzed on
the confirmation column. Results of the confirmation analysis must agree within +_
25% of the primary analysis. Any deviation from this criteria will be reported to the
project Technical Monitor.
No laboratory control standards will be analyzed, and surrogates are not used. The internal
standard, 4-bromo-3,5-dimethylphenyl-N-methyl-carbamate (BDMC), supplied by USEPA, will be added
to every sample, standard, and method blank before analysis. Internal standard recovery must be
evaluated for every sample by determining whether the measured peak area for the internal standard
in any sample or method blank deviates by more than 20% from the peak area for the internal
standard in that day's calibration standard. In case of such disagreement, reinject the sample. If the
second analysis still shows disagreement, add internal standard to a second aliquot of the sample
and reanalyze.
However, if more than one sample shows disagreement with the internal standard response of
the calibration standard, reanalyze the instrument performance standard, the calibration standard, and
the samples which showed the disagreement. If the disagreement still persists, contact the Technical
Monitor.
A method blank is analyzed daily. If any analyte is present at half or more of the MRL, the test
is considered to have failed, and a new method blank will be generated and analyzed. -A second
consecutive method blank failure will require in-lab corrective action and reanalysis starting with
instrument performance standard and calibration standards.
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Section No. 1 1
Revision No. 2 •
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Date: July 29, 1990
Page 2 of 3
i f • '
* F 9
Each day that NPS Method 5 samples are analyzed, an instrument performance sample will be
analyzed and the instrument sensitivity (signal to noise ratio), chromatographic performance (peak
symmetry factor and peak gaussian factor), and the column performance (resolution) will be monitored
as described in Method 5.
During confirmational analyses, a method blank and standard will be analyzed prior to analysis
of samples. All quality control criteria which apply to the primary analysis, with the exception of the
instrument performance standard, will also apply to the confirmational analysis. All confirmation data
and QC data will be stored with the set in which the field sample number resides.
ESE plans to have in place an NPS option in the ESE set report program. This option will check
that all QC is performed, just as is done for all batches currently reported under ESE's standard QC
program.
Exhibit 11-1 presents ESE's Internal Quality Control Checklist.
Since (1) ESE will demonstrate its capability to accurately perform Method 5, (2) the
instrumental analysis will most often be performed within only hours of first opening the sample bottle,
(3) EPA-will be-sending check samples, (4) the internal standard response on each sampte will-be
controlled, (5) the instrument performance sample will be analyzed in each set, and (6) the above QC
checks will be performed on each set, ESE considers the above program sufficient to assure the
quality of the data and does not propose additional QC checks.
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. All corrective actions will be reported to EPA's Technical
Monitor.
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_ _ Section No. 11
{ V ' r" V ^ * ., ^ f*± t '. • Revision No. 2 . 'if-'
"' * " "Date: July &, 1990
Page 3 of 3
EXHIBIT 11-1
INTERNAL QUALITY CONTROL CHECKLIST
U. S ENVIRONMENTAL PROTECTION AGENCY
NATIONAL PESTICIDE SURVEY
METHOD 5
INTERNAL QUALITY CONTROL CHECKS
EPA SET No. ESE BATCH No._
DATE ANALYZED ANALYST
YES NO
CHROMATOGRAM OF DAILY STANDARD INCLUDED
METHOD BLANK (< 0.5 Minimum Reporting Limit)
3. INTERNAL STANDARD RESPONSE (Peak Area)
(Each Sample +. 20% of Daily Standard)
4. INSTRUMENT PERFORMANCE SAMPLE
A Sensitivity (Signal/Noise > 3.0)
B Chromatogivipluc Performance
(1) Peak Symmetry Factor (PSF) (0.9 1.0)
5. DAILY STANDARD ANALYTE RESPONSE
(Each Analyte +_ 20% of Previous Daily Std.)
6 CONFIRMATION (± 25 % of Primary Analysis)
COMMENTS:
QUALITY ASSURANCE COORDINATOR DATE_
PROJECT MANAGER DATE
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Section No 12
Revision No. 2
"Date: July 2*9,
Page 1 of 1
12. PERFORMANCE AND SYSTEM AUDITS
ESE's Quality Assurance Division, independent of the Chemistry Division and reporting directly
to the ESE president, 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.
In addition to the above in-house audits, EPA will perform audits of the data and systems as the
pertain to NPS Method 5. EPA audits will be scheduled approximately every six months during the
conduct of Method 5 analyses. ESE will cooperate with the EPA auditor to the extent that the audit
does not interfere with the laboratories ability to continue with routine operation.
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n
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 5 requires little preventive
maintenance.
• Check valves will be replaced as needed.
• Pumps are tested for flow rate accuracy when, (1) the analyte retention times
change between analytical sets or (3) the pumps are changed or serviced.
Analytical columns will be protected by use of 3 to 5 cm length pellicular guard
columns. Guard columns will be changed when deterioration of the analytical
column chromatography (e.g. poor peak shape, loss of resolution, etc.) becomes
evident.
• Spare columns, guard-column packing material, instrument cables, and some PC
boards are kept to minimize instrument downtime.
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Section No 14
Revise/No 2-
-Date: ju|y'j^
Page 1 of 1
14. SPECIFIC PROCEDURES for ASSESSING MEASUREMENT SYSTEM DATA
Relative response of each analyte is calculated as
RRa = Aa/Ais
where: Aa = peak area of the analyte, and
Ais = peak area of the internal standard from the same chromatogram.
During initial demonstration of capabilities, the mean recovery is calculated as the sum of
recoveries divided by the number of recoveries included in the sum. 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 standard deviation is the square root of the variance. The relative
standard deviation (RSD) is calculated to evaluate precision performance. RSD is calculated as:
RSD = (standard deviation of recoveries/mean recovery) X 100
Each sample's chromatogram's internal standard response (peak area) must be within a range
of 0.8 to 1.2 times the mean internal standard response for that day's calibration curve
chromatograms.
Asrnentroned in Section 11, a single standard will be analyzed daily as a check of instrument -
sensitivity.
Responses of peaks corresponding to the analytes of interest found in the samples (peak area
>1/2 MRL) will be subtracted from the responses of analytes found in the spiked samples to correct
for concentrations of analytes present in the sample prior to spiking. Found concentrations in the
spiked samples will be divided by the "true" value and multiplied by 100 percent to calculate recovery.
An instrument quality control standard will be analyzed with each analytical set and the criteria
listed in Method 5, Table 10 will be used to assess instrument performance. Due to coelution of
methiocarb and the internal standard on the confirmation, the resolution test can not be performed on
this column.
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r
Section No. 15
Revision No. 2- •
"Date: July'25, 1990
Page 1 of 2
15. CORRECTIVE ACTION
In general, bench-level corrective actions fall into two 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.
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 (Figure 15-1) is used to track the action.
These corrective actions and their resolutions will be included in monthly reports to
EPA.
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n
Section No. 15
Revision No. 2
"Date: July 29, 1§90
Page 2 o< 2
EXHIBIT 15-1
QUALITY ASSURANCE CORRECTIVE ACTION
AND REQUEST FORM
QUALITY ASSURANCE CORRECTIVE ACTION REQUEST
AND ROUTING FORM
1. Identification of a Problem:
Originator:
Nature of Problem:
2. Determination of Required Action:
Responsibility Assigned to:
Recommended Action:
3. Implementation of Required Action:
Responsibility Assigned to:
4. Assuring Effectiveness of Action:
Responsibility Assigned to :
Procedure to assure Effectiveness:
Date:
Due Date:
Due Date:
Due Date:
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__ Section No. 16
\ "* (** (P* V, *• ** \ ^^^ f\ t ' 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 - samples received and samples analyzed, but not
validated and status of data processing for analyzed
sets of samples and numbers for sets of data sent to
the EPA
• Reports on standards - new dilutions and results of checks before using
Summary list of bench - level corrective actions (as in Section 15 of this
Plan).
Identification of problems about any phase of the project.
• Copies of representative and, if applicable, unusual chromatograms (as
requested by Technical Monitor).
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 NJD 2
*Date: July 29,
Page 1 of 2
17. ARCHIVAL OF RAW DATA
In order to assure the continued availability of all documentation necessary to defend NFS
Method 5 analytical results, the documentation for each analytical set will be contained in a separate
orange file folder and will be comprised of the following:
• HPLC set documentation checklist
• Method 5 internal quality control checklist
• A hard copy of the NPS formatted results
A hard copy of ESE's formatted results
• All chromatograms and quantitation reports for the following:
Field samples
Blanks
Calibration standards
Instrument performance standard
Time-storage samples
-- ' Lab spike samples
Chromatographic Analysis logsheets
Instrument logsheet(s)
• Internal Standard Recovery summary
Copies of NPS sample tracking forms
• Copies of analyst notebook pages
Standard Curve data sheet
Instrument Configuration sheet
All set file folders will be stored in banker's boxes. Each box will be labeled with number, a
description of its contents (NPS Method 5 set files), a listing of set numbers, 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 NPS 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
Miscellaneous documentation such as audit reports, internal memos, temperature
logs, etc.
• Resumes of NPS participants
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M
Section No. 17
Rev'sion No. 2
"Date: July 2fe, 1990
Page 2 of 2
All banker's boxes containing the NFS 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 NFS set number,
the ESE batch number, and the ESE internal sample number.
Appendix J provides a copy of ESE's standard operating procedure 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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Appendix A
Revision No. 2 ", I
"Date: July'25, 1990 *'
Page 1 of 27
APPENDIX A
METHOD 5. MEASUREMENT OF N-METHYLCARBAMOYLOXIMES AND
N-METHYLCARBAMATES IN GROUND WATER BY DIRECT AQUEOUS
INJECTION HPLC WITH POST COLUMN DERIVATIZATION
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Method 5. Measurement of N-Methylcarbamoyloximes and
N-Methylcarbamates in Ground Water by Direct Aqueous
Injection HPLC with Post Column Derivatization
1. SCOPE AND APPLICATION
1.1 This is a high performance liquid chromatographic (HPLC)
method applicable to the determinations of certain
N-methylcarbamoyloximes and N-methylcarbamates in ground
water. Analytes that can be determined using this method are
listed in Table 1.
1.2 This method has been validated in a single laboratory.
Estimated detection limits (EDLs) have been determined and
are listed in Table 3. Observed detection limits may vary
between ground waters, depending upon the nature of
interferences in the sample matrix and the specific
instrumentation used.
1.3 This method is restricted to use by or under the supervision
of analysts experienced in the use of liquid chromatography
and in the interpretation of liquid chromatograms. Each
analyst must demonstrate the ability to generate acceptable
results with this method using the procedure described in
Section 10.2.
1.4 When this method is used to analyze unfamiliar samples for
any or all of the analytes above, analyte identifications
must be confirmed by at least one additional qualitative
technique.
2. SUMMARY OF METHOD
2.1 The water sample is filtered and a 400-uL aliquot is injected
into a reverse phase HPLC column. Separation of the analytes
is achieved using gradient elution chromatography. After
elution from the HPLC column, the analytes are hydrolyzed
with 0.05 N sodium hydroxide (NaOH) at 95°C. The methyl
amine formed during hydrolysis is reacted with
o-phthalaldehyde (OPA) and 2-mercaptoethanol to form a highly
fluorescent derivative which is detected by a fluorescence
detector.l
3. DEFINITIONS
Artificial ground water -- an aqueous matrix designed to mimic
characteristics of a real ground water sample. Artificial ground
waters should be reproducible for validations performed in other
laboratories.
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r •• n
Calibration standard -- a known amount of a pure analyte, dissolved
in an organic solvent, that is analyzed under the same procedures
and conditions that are used to analyze samples containing that
analyte. '
Estimated detection limit (EDL) -- the minimum concentration of a
substance that can be measured and reported with confidence that the
analyte concentration is greater than zero as determined from the
analysis of a sample in a given matrix containing the analyte.
Field duplicates -- two samples, collected at the same site, that
are treated exactly the same throughout field and laboratory
analytical procedures. Analysis of field duplicates provides a
measure of the precision associated with sample collection,
preservation and storage, as well as with laboratory procedures.
Instrument quality control (QC) standard --an aqueous solution
containing specified concentrations of specified analytes. The
instrument QC standard is analyzed each working day prior to the
analysis of sample extracts and calibration standards. The
performing laboratory uses this solution to demonstrate acceptable
instrument performance in the areas of sensitivity, column
performance, and chromatographic performance.
Internal standard - - a pure compound added to a sample in a known
amount and used to calibrate concentration measurements of other
analytes that are sample components. The internal standard must be
a compound that is not a sample component.
Laboratory control standard --a solution of analytes prepared in
the laboratory by dissolving known amounts of pure analytes in a
known amount of reagent water. In this method, the laboratory
control standard is prepared by adding appropriate volumes
of the appropriate standard solution to buffered reagent water.
Laboratory reagent blank -- an aliquot of buffered reagent water,
filtered, and analyzed as if it were a sample.
Quality control check sample --a water-soluble solution containing
known concentrations of analytes prepared by a laboratory other than
the laboratory performing the analysis. The performing laboratory
uses this solution to demonstrate that it can obtain acceptable
identifications and measurements with a method. A small measured
volume of the solution is added to a known volume of buffered
reagent water and analyzed with procedures identical to those used
for samples. True values of analytes are known by the analyst.
Stock standard solution --a concentrated solution containing a
certi-fied standard that is a method analyte, or a concentrated
solution of an analyte prepared in the laboratory with an assayed
reference compound.
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, ,
• *
4. INTERFERENCES
4.1 Method interferences may be caused by contaminants in
solvents, reagents, glassware and other sample processing
apparatus that lead to discrete artifacts or elevated
baselines in liquid chromatograms. Specific sources of
contamination have not been identified. All reagents and
apparatus must be routinely demon-strated to be free from
interferences under the conditions of the analysis by running
laboratory reagent blanks as described in Section 10.6.1.
4.1.1 Glassware must be scrupulously cleaned.2 Clean all
glass-ware as soon as possible after use by
thoroughly rinsing with the last solvent used in
it. Follow by washing with hot water and detergent
and thorough rinsing with tap and reagent water.
Drain dry, and heat in an oven or muffle furnace at
450°C for 1 hour. Do not heat volumetric ware.
Thermally stable materials might not be eliminated
by this treatment. Thorough rinsing with acetone
may be substituted for the heating. After drying
and cooling, seal and store glassware in a clean
environment to prevent any accumulation of dust or
other contaminants. Store inverted or capped~with
aluminum foil.
4.1.2 The use of high purity reagents and solvents helps
to minimize interference problems. Purification of
solvents by distillation in all-glass systems may be
required.
4.2 Interfering contamination may occur when a sample containing
low concentrations of analytes is analyzed immediately
following a sample containing relatively high concentrations
of analytes. A preventive technique is between-sample
rinsing of the sample syringe and filter holder with two
portions of reagent water. After analysis of a sample
containing high concentrations of analytes, one or more
laboratory reagent blanks should be analyzed.
4.3 Matrix interference may be caused by contaminants that are
present in the sample. The extent of matrix interference
will vary considerably from source to source, depending upon
the ground water sampled. Positive identifications must be
confirmed using the confirmation column specified in Table 2.
5. SAFETY
5.1 The toxicity or carcinogenicity of each reagent used in this
method has not been precisely defined; however, each chemical
compound must be treated as a potential health hazard. From
this viewpoint, exposure to these chemicals must be reduced
to the lowest possible level by whatever means available.
The laboratory is responsible for maintaining a current
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awareness file of OSHA regulations regarding the safe
handling of the chemicals specified in this method. A
reference file of material data handling sheets should also
be made available to all personnel involved in the chemical
analysis. Additional references to laboratory safety are
available and have been identified3"5 for the information of
the analyst.
6.
APPARATUS AND EQUIPMENT (All specifications are suggested.
numbers are included for illustration only.)
Catalog
6.1
6.2
6.3
6.4
SAMPLING EQUIPMENT
6.1.1 Grab sample bottle -- 60-mL screw cap vials (Pierce
No. 13075 or equivalent) and caps equipped with a
PTFE-faced silicone septa (Pierce No. 12722 or
equivalent). Prior to use, wash vials and septa
with detergent and rinse with tap and distilled
water. Allow the septa to air dry at room
temperature, place in a 105°C oven for 1 hour, then
remove and allow to cool in an area known to be free
of organics. Heat vials at 400°C for 1 hour to
remove organics.
Balance -- Analytical, capable of accurately weighing to the
nearest 0.0001 g.
FILTRATION APPARATUS
6.3.1 Macrofiltration -- to filter derivatization
solutions and mobile phases used in HPLC. Recommend
using 47 mm filters (Millipore Type HA, 0.45 urn for
water and Millipore Type FH, 0.5 urn for organics or
equivalent).'
6.3.2 Microfiltration -- to filter samples prior to HPLC
analysis. Use 13 mm filter holder (Millipore
stainless steel XX300/200 or equivalent), and 13 mm
diameter 0.2 urn polyester filters (Nuclepore 180406
or equivalent).
SYRINGES AND SYRINGE VALVES
6.4.1 Hypodermic syringe -- 10-mL glass, with Luer-Lok
tip.
6.4.2 S , _inge valve -- 3-way (Hamilton HV3-3 or
equivalent).
6.4.3 Syringe needle - - 7 to 10-cm long, 17-gauge, blunt
tip.
6.4.4 Micro syringes -- various sizes.
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6.5 MISCELLANEOUS
6.5.1 Solution storage bottles -- Amber glass, 10- to
15-mL capacity with TFE-fluorocarbon-lined screw
cap.
6.5.2 Helium, for degassing dissolved oxygen.
6.6 HIGH PERFORMANCE LIQUID CHROMATOGRAPH (HPLC)
6.6.1 HPLC system capable of injecting 200 to 400-uL
aliquots, and performing binary linear gradients at
a constant flow rate.
6.6.2 Primary column -- 250 mm x 4.6 mm I.D. stainless
steel packed with 5 urn Altex Ultrasphere ODS.
Validation data presented in this method were
obtained using this column. Alternate columns may
be used in accordance with the provisions described
in Section 10.2.
6.6.3 Confirmation column -- 250 mm x 4.6 mm I.D.
stainless steel packed with 5 urn Supelco LC-1.
6.6.3 Detector -- Post column derivatization detector
composed of a post column reactor and a fluorescence
detector. This detector has proven effective in the
analysis of spiked reagent and artificial ground
waters. The post column derivatization detector
(PCD) was used to generate the validation data
presented in this method. A block diagram of the
PCD is shown in Figure 2.
6.6.3.1 Post column reactor -- Capable of mixing
reagents into the mobile phase. Reactor
should be equipped with pumps to deliver
0.1 to 1.0 mL/min of each reagent; mixing
tees; two 1.0-mL delay coils, one thermo-
stated at 95°C; and constructed using PTFE
tubing (Kratos URS 051 and URA 100 or
equivalent).
6.6.3.2 Fluorescence detector - - Capable of
excitation at 230 nm and detection of
emission energies greater than 418 nm. A
Schoffel Model 970 fluorescence detector
was used to generate the validation data
presented in this method.
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7. REAGENTS AND CONSUMABLE MATERIALS
7.1 Reagent water -- reagent water used to generate the
validation data in this method was distilled water obtained
from the Magnetic Springs Water Co., 1801 Lone Eagle St.,
Columbus, Ohio 43228.
7.2 Methanol -- Distilled-in-glass quality or equivalent.
7.3 HPLC MOBILE PHASE
7.3.1 Water -- HPLC grade (available from Burdick and
Jackson).
7.3.2 Methanol -- HPLC grade. Filter and degas with
helium before use.
7.4 POST COLUMN DERIVATIZATION SOLUTIONS
7.4.1 Sodium hydroxide, 0.05 N -- Dissolve 2.0 g of sodium
hydroxide (NaOH) in reagent water. Dilute to 1.0 L
with reagent water. Filter and degas with helium
just before use.
7.4.2 2-Mercaptoethanol (1+1) -- Mix 10.0 mL of
2-mercapto- ethanol and 10.0 mL of acetonitrile.
Cap. Store in hood (CAUTION - stench).
7.4.3 Sodium borate (0.05 N) -- Dissolve 19.1 g of sodium
borate (Na2B(,07.10H20) in reagent water. Dilute to
1.0 L with reagent water. The sodium borate will
completely dissolve at room temperature if prepared
a day before use.
7.4.4 OPA reaction solution -- Dissolve 100 + 10 mg of
o-phthalaldehyde (mp 55-58°C) in 10 mL of methanol.
Add to 1.0 L of 0.05 N sodium borate. Mix, filter,
and degas with helium. Add 100 uL of
2-mercaptoethanol (1+1) and mix. Make up fresh
solution daily.
7.5 Monochloroacetic acid buffer (pH3) -- Prepare by mixing 156
mL of 1.0 M monochloroacetic acid and 100 mL 1.0 M potassium
acetate.
7.6 4-Bromo-3,5-dimethylphenyl N-methylcarbamate (BDMC) -- >98%
purity, for use as internal standard (available from Aldrich
Chemical Co.).
7.7 ARTIFICIAL GROUND WATERS -- Two artificial ground waters were
used to generate the validation data in this method. The
first artificial ground water was used to mimic a hard ground
water, and the second artificial ground water was used to
mimic a ground water with moderately high organic content.
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7.7.1 Hard artificial ground water -- The hard artificial
ground water used to generate the validation data in
this method was Absopure Natural Artesian Spring
Water obtained from the Absopure Water Company in
Plymouth, Michigan.
7.7.2 Organic-contaminated artificial ground water -- The
organic-contaminated artificial ground water used to
generate the validation data in this method was
reagent water spiked with fulvic acid at the 1 mg/L
concentration level. A very well-characterized
fulvic acid, available from the International Humic
Substances Society (associated with the United
States Geological Survey in Denver, Colorado), was
used.
7.8 STOCK STANDARD SOLUTIONS (1.00 ug/uL) -- Stock standard solu-
tions may be purchased as certified solutions or prepared
from pure standard materials using the following procedure:
7.8.1 Prepare stock standard solutions by accurately
weighing approximately 0.0100 g of pure material.
Dissolve the material in HPLC quality methanol and
dilute to volume in a 10-mL volumetric flask.
Larger volumes may be used at the convenience of the
analyst. If compound purity is certified at 96% or
greater, the weight may be used without correction
to calculate the concentration of the stock
standard. Commercially prepared stock standards may
be used at any concentration if they are certified
by the manufacturer or by an independent source.
7.8.2 Transfer the stock standard solutions into TFE-
fluorocarbon-sealed screw cap vials. Store at room
temperature and protect from light.
7.8.3 Stock standard solutions should be replaced after
two months or sooner if comparison with laboratory
control standards indicates a problem.
7.9 INTERNAL STANDARD SPIKING SOLUTION -- Prepare an internal
standard spiking solution by accurately weighing 0.0010 g of
pure BDMC. Dissolve the BDMC in pesticide-quality methanol
and dilute to volume in a 10-mL volumetric flask. Transfer
the internal standard spiking solution to a TFE-fluorocarbon-
sealed scr; , .ip bottle and store at room temperature.
Addition of 4L of the internal standard spiking solution to
50 mL of sample results in a final internal standard concen-
tration of 10 ug/L.
7.10 INSTRUMENT QC STANDARD -- Prepare instrument QC standard
concentrate by adding 20 uL of the 3-hydroxycarbofuran stock
standard solution, 1.0 mL of the aldicarb sulfoxide stock
standard solution, 200 uL of the methiocarb stock standard
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solution, and 1 mL of the internal standard spiking solution
to a 10-mL volumetric flask. Dilute to volume with methanol.
Thoroughly mix concentrate. Prepare instrument QC standard
by placing 100 uL of the concentrate solution into a 100-mL
volumetric flask. Dilute to volume with buffered reagent
water. Thoroughly mix instrument QC standard and transfer to
a sealed bottle. Store at room temperature.
SAMPLE COLLECTION. PRESERVATION AND HANDLING
8.1 Grab samples must be collected in glass containers.
Conventional sampling practices8 should be followed; however,
the bottle must not be prerinsed with sample before
collection.
8.2 SAMPLE PRESERVATION/PH ADJUSTMENT -- Oxamyl, 3-hydroxycarbo-
furan, and carbaryl can all degrade quickly in water held at
room temperature.6'7 This short term degradation is of
concern during the time samples are being shipped and the
time processed samples are held at room temperature in
autosampler trays. Samples targeted for the analysis of
these three analytes must be preserved at pH 3. The pH
adjustment also minimizes analyte biodegradation.
Preservation study results given in Table 10 indicate that
method analytes are stable in water samples for at least 28
days when stored using the following conditions:
8.2.1 The samples must be iced or refrigerated at 4°C from
the time of collection until extraction.
8.2.2 Add 0.6 mL of monochloroacetic acid buffer to the
60-mL sample bottle. Add buffer to the sample
bottle at the sampling site or in the laboratory
before shipping to the sampling site.
8.2.3 After sample is collected in bottle containing
buffer, seal the sample bottle and shake vigorously
for 1 min.
9. CALIBRATION
9.1 Establish HPLC operating conditions equivalent to those
indicated in Table 2. Calibrate the HPLC system using the
internal standard technique (Section 9.2).
9.2 INTERNAL STANDARD CALIBRATION PROCEDURE. The analyst must
select one or more internal standards similar in analytical
behavior to the analytes of interest. The analyst must
further demonstrate that the measurement of the internal
standard is not affected by method or matrix interferences.
BDMC has been identified as a suitable internal standard.
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9.2.1 Prepare calibration standards at a minimum of three
(suggested five) concentration levels for each
analyte of interest by adding volumes of one or more
stock standards to a volumetric flask. To each
calibration standard, add a known constant amount of
one or more internal standards, and dilute to volume
with buffered reagent water. To prepare buffered
reagent water, add 10 mL of 1.0 M monochloroacetic
acid buffer to 1 L of reagent water. One of the
standards should be representative of an analyte
concentration near, but above, the MDL. The other
concentrations should correspond to the range of
concentrations expected in the sample concentrates,
or should define the working range of the detector.
9.2.2 Inject 400 uL of each calibration standard and
tabulate the relative response for each analyte
(RRa) to the internal standard using the equation:
RRa = Aa/Als
where: Aa = the peak area of the analyte, and
Als = the peak area of the internal
standard.
Generate a calibration curve of analyte RRa versus
analyte concentration in the sample in ug/L.
9.2.3 The working calibration curve must be verified on
each working shift by the measurement of one or more
calibration standards. If the response for any
analyte varies from the predicted response by more
than 10%, the test must be repeated using a fresh
calibration standard. Alternatively, a new
calibration curve must be prepared for that analyte.
10. QUALITY CONTROL
10.1 Each laboratory using this method is required to operate a
formal quality control (QC) program. The minimum requirements
of this program consist of the following: an initial
demonstration of laboratory capability; the analysis of QC,
laboratory control, and spiked samples as a continuing check
on recovery performance; the analysis of field duplicates as
a continuing check on precision; the analysis of reagent
blanks as a continuing check on contamination; and frequent
analysis of the instrument QC standard to assure acceptable
instrument performance.
10.2 INITIAL DEMONSTRATION OF CAPABILITY -- To establish the
ability to perform this method, the analyst must perform the
following operations.
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10.2.1 Select a representative spike concentration for each
analyte to be measured. Using stock standards that
differ from calibration standards, prepare a
laboratory control check sample concentrate in
methanol 1000 times more concentrated than the
selected spike concentrations.
10.2.2 Using a syringe, add 50 uL of the check sample
concentrate to each of a minimum of four 50-mL
aliquots of reagent water. Add 0.5 mL of 1.0 M
monochloroacetic acid buffer to each spiked sample.
A representative ground water may be used in place
of the reagent water, but one or more unspiked
aliquots must be analyzed to determine background
levels, and the spike level must exceed twice the
background level for the test to be valid. Analyze
the aliquots according to the method beginning in
Section 11.
10.2.3 Calculate the average percent recovery (R), and the
standard deviation of the percent recovery (s), for
the results. Ground water background corrections
must be made before R and s calculations are
performed.
10.2.4 Tables 3-9 provide single operator recovery and
precision data obtained for the method analytes from
reagent and artificial ground waters. Similar
results should be expected from reagent water for
all compounds listed in the method. Compare the
results obtained in section 10.2.3 to the values
listed in Tables 3-9. If the results are not
comparable, review potential problem areas and
repeat the test.
10.3 In recognition of the rapid advances occurring in chromato-
graphy, the analyst is permitted certain options to improve
the separations or lower the cost of measurements. Each time
such modifications to the method are made, the analyst is
required to repeat the procedure in Section 10.2.
10.4 ASSESSING ANALYTE RECOVERY
10.4.1 Each quarter, it is essential that the laboratory
analyze (if available) QC check standards for each
contaminant. If the criteria established by USEPA
and provided with the QA standards are not met,
corrective action needs to be taken and documented.
10.4.2 After every 10 samples, and preferably in the middle
of each day, analyze a laboratory control standard.
Calibration standards may not be used for accuracy
assessments, and the laboratory control standard may
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not be used for calibration of the analytical
system.
10.4.2.1 Laboratory control standard concentrate --
Internally prepared laboratory control
standards are used to provide the routine
assessment of recovery. They should be
prepared from a separate set of stock
standards, i.e., different from calibra-
tion standards.
10.4.2.2 Laboratory control standard -- Add an
appropriate aliquot of the control
standard concentrate to 50 mL of buffered
reagent water in a 50 mL volumetric flask.
10.4.2.3 Analyze the 50 mL laboratory control
standard as described in Section 11. For
each analyte in the laboratory control
standard, calculate the percent recovery
(Pi) using the equation:
100S1
PI - ------
where: Si = the analytical result from
the laboratory control
standard in ug/L, and
Tx = the known spiked
concentration of the
laboratory control
standard in ug/L.
10.4.3 It is essential that the laboratory analyze an
unknown performance evaluation sample (when
available) once per year for all regulated
contaminants measured. Results need to be within
acceptable limits established by USEPA for each
analyte .
10.4.4 The laboratory is required to collect in duplicate a
portion of the samples to monitor spike recoveries.
The frequency of spiked sample analysis must be at
least 10 percent of all samples, or one spiked
sample per month, whichever is greater. One aliquot
of the sample must be spiked and analyzed as
described in Section 11.
-------
10.5 ASSESSING ANALYTE PRECISION
10.5.1 Precision assessments for this method are based upon
the analysis of field duplicates. Analyze field
duplicates for at least 10 percent of all samples.
To the extent practical, the duplicated sample
should contain reportable levels of method analytes.
10.5.2 For each analyte in each duplicate pair, calculate
the relative range (RR1) using the equation:
100R,
RR, =
X,
where: Rj = the absolute difference between
the duplicate measurements Xj^ and
X2 in ug/L, and
Xx = the average concentration found
([X: + X2]/2) in ug/L.
10.5.3 Individual relative range measurements are pooled to
determine the average relative range or to develop
an expression of relative range as a function of
concentration.
10.6 ASSESSING CONTAMINATION
10.6.1 Laboratory reagent blanks -- Before processing any
samples, the analyst must demonstrate that all
glassware and reagent interferences are under
control. This is accomplished by the analysis of a
laboratory reagent blank. A laboratory reagent
blank is a 50 mL aliquot of reagent water analyzed
as if it were a sample. Each time a set of samples
is extracted or there is a change in reagents, a
laboratory reagent blank must be processed to assess
laboratory contamination. If the reagent blank
exhibits a peak within the retention time window of
any analyte which is greater than or equal to one-
half the MDL for that analyte, determine source of
contamination before proceeding.
10.7 ASSESSING INSTRUMENT PERFORMANCE -- The laboratory is
required to demonstrate the ability to generate acceptable
HPLC performance for each analyte. Analyte peak shapes
comparable to those shown in Figure 1 should be
demonstrated. Instrument performance should be monitored on
a daily basis by analysis of the instrument QC standard.
-------
10.7.1 Instrument QC standard -- The instrument QC
standard contains compounds designed to indicate
appropriate instrument sensitivity, column
performance, and chromatographic performance.
Instrument QC standard components and performance
criteria are listed in Table 11. Inability to
demonstrate acceptable instrument performance
indicates the need for reevaluation of the HPLC-UV
system. An HPLC-UV chromatogram generated from the
analysis of the instrument QC standard is shown in
Figure 3.
ANALYTE CONFIRMATION -- When doubt exists over the identi-
fication of a peak on the chromatogram, confirmatory
techniques such as chromatography with a dissimilar column,
or ratio of absorbance at two or more wavelengths must be
used. A suggested confirmation column is described in Table
2.
10.9 ADDITIONAL QC -- It is recommended that the laboratory adopt
additional quality assurance practices for use with this
method. The specific practices that are most productive
depend upon the needs of the laboratory and the nature of the
samples.
11- PROCEDURE
11.1 PH ADJUSTMENT AND FILTRATION
11.1.1 Adjust the pH of the sample or standard to pH 3 +
0.2 by adding 0.5 mL of 1.0 M monochloroacetic acid
buffer to each 50 mL of sample. This step is not
necessary if sample pH was adjusted during sample
collection as a preservation precaution. Fill a
50-mL volumetric flask to the mark with the sample.
Add 5 uL of the internal standard spiking solution
and mix by inverting the flask several times.
11.1.2 Affix the three-way valve to a 10-mL syringe. Place
a clean filter in the filter holder and affix the
filter holder and the 7- to 10-cm syringe needle to
the syringe valve. Rinse the needle and syringe
with reagent water. Prewet the filter by passing 5
mL of reagent water through the filter. Empty the
syringe and check for leaks. Draw 10 mL of sample
into the syringe and expel through the filter. Draw
another 10 mL of sample into the syringe, expel
through the filter, and collect the last 5 ml for
analysis. Rinse the syringe with reagent water.
Discard the filter.
-------
11.2 LIQUID CHROMATOGRAPHY
11.2.1 Table 2 summarizes the recommended operating
conditions for the liquid chromatograph. Included
in Table 2 are retention times observed using this
method. An example of the separations achieved
using these conditions is shown in Figure 1. Other
HPLC columns, chromatographic conditions, or
detectors may be used if the requirements of Section
10.2 are met.
11.2.2 Calibrate the system daily as described in Section
9. The standards and extracts must be in pH3
buffered water.
11.2.3 Inject 400 uL of the sample extract. Record the
volume injected and the resulting peak size in area
units.
11.2.4 The width of the retention time window used to make
identifications should be based upon measurements of
actual retention time variations of standards over
the course of a day. Three times the standard
deviation of a retention time can be used to
calculate a suggested window size for a compound.
However, the experience of the analyst should weigh
heavily in the interpretation of chromatograms.
11.2.5 If the response for the peak exceeds the working
range of the system, dilute the extract and
reanalyze.
12. CALCULATIONS
12.1 Calculate analyte concentrations in the sample from the
relative response for the analyte (RRa) to the internal
standard using the equation the calibration curve described
in Section 9.3.2.
12.2 For samples processed as part of a set where the laboratory
control standard recovery falls outside of the control limits
in Section 10.4, data for the affected analytes must be
labeled as suspect.
13. PRECISION AND ACC1 »_CY
13.1 In a single laboratory, analyte recoveries from reagent water
were determined at five concentration levels. Results were
used to determine analyte EDLs and demonstrate method range.
EDL determination results are given in Table 3. Method range
results are given in Tables 4-7.
-------
13.2 In a single laboratory, analyte recoveries from two
artificial ground waters were determined at one concentration
level. Results were used to demonstrate applicability of the
method to different ground water matrices. Analyte
recoveries from the two artificial matrices are given in
Tables 8 and 9.
13.3 In a single laboratory, analyte recoveries from a ground
water preserved by adjusting to pH 3 with monochloroacetic
acid buffer were determined 0, 14, and 28 days after sample
preparation. Samples were stored at 4°C or -10°C and were
protected from light. Results were used to predict expected
analyte stability in ground water samples. Analyte
recoveries from the preserved, spiked ground water samples
are given in Table 10.
REFERENCES
1. Moye, H.A., S.J. Sherrer, and P.A. St. John, "Dynamic Labeling of
Pesticides for High Performance Liquid Chromatography: Detection of
N-Methylcarbamates and o-Phthalaldehyde," Anal. Lett. 10, 1049, 1977.
2. ASTM Annual Book of Standards, Part 31, D3694, "Standard Practice for
Preparation of Sample Containers and for Preservation," American
Society for Testing and Materials, Philadelphia, PA, p. 679, 1980.
3. "Carcinogens - Working with Carcinogens," Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, Aug. 1977.
4. "OSHA Safety and Health Standards, General Industry," (29 CFR 1910),
Occupational Safety and Health Administration, OSHA 2206, (Revised,
January 1976) .
5. "Safety in Academic Chemistry Laboratories," American Chemical Society
Publication, Committee on Chemical Safety, 3rd Edition, 1979.
6. Foerst, D.C. and H.A. Moye, "Aldicarb in Drinking Water via Direct
Aqueous Injection HPLC with Post Column Derivatization," Proceedings
of the 12th annual AWWA Water Quality Technology conference, in press
1985.
7. Hill, K.M., R.H. Hollowell, and L.A. DalCortevo, "Determination of
N-Methylcarbamate Pesticides in Well Water by Liquid Chromatography
and Post Column Fluorescence Derivatization," Anal. Chem, 56, 2465
(1984) .
8. ASTM Annual Book of Standards, Part 31, D3370, "Standard Practice for
Sampling Water," American Society for Testing and Materials, Philadel-
phia, PA, p.76, 1980.
-------
TABLE 1. METHOD ANALYTES
Analyte
Aldicarb
Aldicarb sulfone
Aldicarb sulfoxide
Baygon
Carbaryl
Carbofuran
3-Hydroxycarbofuran
Methiocarb
Me thorny 1
Oxamyl
Chemical
Abstracts Service
Registry Number
116-06-3
1646-88-4
1646-87-3
114-26-1
63-25-2
1563-66-2
16655-82-6
2032-65-7
16752-77-5
23135-22-0
Ident .
Code(a)
6
2
1
8
9
7
5
10
4
3
(a) Code used for identification of peaks in figures;
IS = internal standard.
-------
TABLE 2. PRIMARY AND CONFIRMATION CHROMATOGRAPHIC CONDITIONS
Retention Time for Given Conditions
Analyte
Primary (a)(c)
Confirmation (b)(d)
Aldicarb
Aldicarb sulfone
Aldicarb sulfoxide
Baygon
Carbaryl
Carbofuran
3 -Hydroxycarbof uran
Methiocarb
Methomyl
Oxamyl
0.429
0.421
0.834
0.867
0.824
0.657
0.984
0.518
0.489
0.761 21.4
12.2
17.5
23.4
25.4
24.4
19.0
28.6
14.8
14.6
(a) Retention time relative to BDMC internal standard which elutes
at 35.5 min.
(b) Absolute retention time in minutes.
(c) Primary conditions:
Column: 250 mm x 4.6 mm I.D. Altex Ultrasphere ODS
(5 urn)
Mobile phase: Linear gradient from 15:85 methanol:water to
methanol in 32 min
Flow rate: 1.0 mL/min
Injection volume: 400 uL
Detector: Fluorescence; excitation 230 nm; emission
418 nm
(d) Confirmation conditions:
Column:
Mobile phase:
Flow rate:
Injection volume:
Detector
250 mm x 4.6 mm I.D. Supelco LC-1 (5 urn)
Linear gradient from 15:85 methanol:water to
methanol in 32 min
1.0 mL/min
400 uL
Fluorescence; excitation 230 nm; emission
-+18 nm
-------
TABLE 3. RECOVERIES OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 1) AND EDLs (a)
Spiking Amt in
Level, Blank,
Analyte ug/L ug/L n(b) R(c)
Aldicarb 1.0 ND (g)
Aldicarb sulfone 2.0 ND
Aldicarb sulf oxide 2.0 ND
Baygon 1.0 ND
Carbaryl 2.0 ND
Carbofuran 1.5 ND
3-Hydroxycarbofuran 2.0 ND
Methiocarb 4.0 ND
Methomyl 0.50 ND
Oxamyl 2.0 ND
(a) Amounts corrected for levels detected in
(b) n = number of recovery data points.
(c) R = average percent recovery.
(d) S = standard deviation.
(e) RSD = percent relative standard deviation
8
8
8
7
8
7
8
8
7
8
blank
(f) EDL = estimated detection limit in sample
107
83
47
101
97
90
108
82
102
82
in ug/L
S(d) RSD(
0.0728
0.337
0.196
0.323
0.443
0.166
0.626
0.638
0.0931
0.287
; calculated
e) EDL(f)
7
20
21
32
23
12
29
19
18
17
by
1.0
2.0
2.0
1.0
2.0
1.5
2.0
4.0
0.50
2.0
multiplying standard deviation (S) times the students' t value appropriate
for a 99% confidence level and a standard deviation estimate with n-1
degrees of freedom, or a level of compound in sample yielding a peak in
the final extract with signal-to-noise ratio of approximately 5, whichever
value is higher.
(g) ND = interference not detected in blank.
-------
TABLE 4. RECOVERIES OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 2) (a)
Spiking Amt in
Level, Blank,
Analyte
Aldicarb
Aldicarb
Aldicarb
Baygon
Carbaryl
sulfone
sulfoxide
Carbofuran
3-Hydroxycarbofuran
Methiocarb
Me thorny 1
Oxamyl
(a) Amounts corrected
(b) n -
(c) R =
(d) S =
(e) RSD
(f) ND
ug
2
4
4
2
4
3
4
8
1
4
for
number of recovery
/L
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
amount
data
ug/L
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
found
points
n(b)
(f) 8
8
8
8
8
8
8
7
8
8
in blank.
R(c)
113
100
73
97
94
93
93
80
76
88
0
0
0
0
0
0
0
0
0
0
S(d)
.125
.251
.283
.181
.292
.151
.392
.246
.0893
.246
RSD(e)
6
6
10
9
8
5
11
4
12
7
average percent recovery.
standard deviation.
= percent relative
= interference
not
standard deviation.
detected in
blank.
-------
TABLE 5. RECOVERIES OF ANALYZES FROM REAGENT WATER (SPIKING LEVEL 3) (a)
Spiking Amt in
Level, Blank,
Analyte ug/L ug/L n(b)
Aldicarb 5.0 ND (f)
Aldicarb sulfone 10 ND
Aldicarb sulfoxide 10 ND
Baygon 5.0 ND
Carbaryl 10 ND
Carbofuran 7.5 ND
3-Hydroxycarbofuran 10 ND
Methiocarb 20 ND
Me thorny 1 2.5 ND
Oxamyl 10 ND
8
8
8
8
8
8
8
7
8
8
R(c)
115
101
97
106
97
102
102
94
105
100
S(d) RSD(e)
0.172
0.407
0.441
0.152
0.607
0.346
0.386
0.453
0.0951
0.423
3
4
5
3
6
5
4
2
4
4
(a) Amounts corrected for amount found in blank.
(b) n = number of recovery data points
(c) R = average percent recovery.
(d) S = standard deviation.
(e) RSD = percent relative standard deviation.
(f) ND = interference not detected in blank.
-------
TABLE 6. RECOVERIES OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 4) (a)
Spiking Amt in
Level, Blank,
Analyte ug/L ug/L
Aldicarb 10 ND (f)
Aldicarb sulfone 20 ND
Aldicarb sulfoxide 20 ND
Baygon 10 ND
Carbaryl 15 ND
Carbofuran 15 ND
3-Hydroxycarbofuran 20 ND
Methiocarb 40 ND
Me thorny 1 5.0 ND
Oxamyl 20 ND
(a) Amounts corrected for amount found in
(b) n = number of recovery data points
(c) R = average percent recovery.
(d) S = standard deviation.
n(b)
8
8
8
8
8
8
8
8
8
8
b 1 ank .
R(c)
105
91
92
94
112
96
92
83
96
90
S(d)
0.300
0.657
0.441
0.309
0.298
0.247
0.910
0.722
0.0912
0.501
RSD(e)
3
4
2
3
2
2
5
2
2
3
(e) RSD = percent relative standard deviation.
(f) ND = interference not detected in blank.
-------
TABLE 7. RECOVERIES OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 5) (a)
Spiking Amt in
Level ,
Analyte
Aldicarb
Aldicarb sulfone
Aldicarb sulfoxide
Baygon
Carbaryl
Carbofuran
3 -Hydroxycarbofuran
Methiocarb
Me thorny 1
Oxamyl
(a) Amounts corrected
Blank,
ug/L ug/L
25
50
50
25
50
38
50
100
13
50
for
(b) n = number of recovery
ND (f)
ND
ND
ND
ND
ND
ND
ND
ND
ND
amount found in
data points
n(b)
8
8
8
8
8
8
8
8
8
8
blank.
R(c)
98
92
96
91
83
91
90
82
98
89
1
2
2
1
1
1
2
5
0
1
S(d)
.31
.06
.76
.03
.76
.82
.00
.85
.529
.80
RSD(e)
5
4
6
4
4
5
4
7
4
4
(c) R = average percent recovery.
(d) S = standard deviation.
(e) RSD = percent relative
(f) ND = interference
not
standard deviation.
detected in blank.
-------
TABLE 8. RECOVERIES OF ANALYTES FROM HARD ARTIFICIAL GROUND WATER
(SPIKING LEVEL 3) (a)
Spiking Amt in
Level, Blank,
Analyte ug/L ug/L n(b)
Aldicarb 5.0 ND (f)
Aldicarb sulfone 10 ND
Aldicarb sulfoxide 10 ND
Baygon 5.0 ND
Carbaryl 10 ND
Carbofuran 7.5 ND
3-Hydroxycarbofuran 10 ND
Methiocarb 20 ND
Methomyl 2.5 ND
Oxamyl 10 ND
8
8
8
8
8
8
8
8
8
8
R(c)
106
98
105
96
94
102
98
102
98
97
S(d) RSD(e)
0.177
0.441
0.393
0.224
0.454
0.245
0.494
0.856
0.0863
0.269
3
4
4
5
5
3
5
4
4
3
(a) Amounts corrected for amount found in blank.
(b) n = number of recovery data points
(c) R = average percent recovery.
(d) S = standard deviation.
(e) RSD = percent relative standard deviation
(f) ND = interference not detected in blank.
-------
TABLE 9. RECOVERIES OF ANALYTES FROM ORGANIC-CONTAMINATED ARTIFICIAL
GROUND WATER (SPIKING LEVEL 3) (a)
Analyte
Aldicarb
Aldicarb
Aldicarb
Baygon
Carbaryl
Spiking
Level ,
Amt in
Blank,
ug/L ug/L n(b)
sulfone
sulfoxide
Carbofuran
3 -Hydroxycarbof uran
Methiocarb
Me thorny 1
Oxamyl
5
10
10
5
10
7.5
10
20
2.5
10
(a) Amounts corrected for
(b) n -
(c) R =
(d) S =
(e) RSD
(f) ND
number of
recovery
ND (f)
ND
ND
ND
ND
ND
ND
ND
ND
ND
8
8
8
7
8
7
8
7
8
8
R(c)
102
95
94
97
104
100
101
112
105
102
S(d) RSD(e)
0
0
1
0
1
0
0
0.
0.
1.
.406
.981
.05
.300
.08
.524
.969
.660
.244
.03
8
10
11
6
10
7
10
3
9
10
amount found in blank.
data points
average percent recovery.
standard deviation.
= percent
relative
= interference not
standard deviation
detected in blank.
-------
TABLE 10. RESULTS FROM METHOD 5 PRESERVATION STUDIES (c)
Spiking
Day 0
Day 14 (
:-10°C)
Day 14
(4°C)
Day 28
(-10°C) Day 28 (4°C)
Level,
Analyte
Aldicarb
Aldicarb sulfone
Aldicarb sulfoxide
Baygon
Carbaryl
Carbofuran
3-Hydroxycarbofuran
Methiocarb
Methomyl
Oxamyl
g/L
5.0
10
10
5.0
10
7.5
10
20
2.5
10
R(a)
100
99
100
98
100
100
95
110
110
98
RSD(b)
9
9
9
10
6
9
9
4
12
6
R
100
93
91
91
92
95
89
100
90
85
RSD
4
3
6
2
4
3
6
1
6
4
R
110
99
100
100
95
110
100
98
96
95
RSD
2
3
2
4
3
7
3
1
5
5
R
100
97
98
88
99
95
100
99
93
100
RSD
6
0
2
2
18
2
8
0
2
11
R
83
86
91
93
89
93
95
94
96
94
RSD
1
8
5
9
5
3
11
6
5
9
(a) R = average percent recovery.
(b) RSD = percent relative standard deviation.
(c) Storage temperature given in parentheses.
-------
TABLE 11. QUALITY CONTROL STANDARD
Test
Sensitivity
Chromatographic performance
Column performance
Analyte
3- Hydroxycarbof uran
Aldicarb sulfoxide
Methiocarb
4-Bromo-3,5-dimethylphenyl
N-methylcarbamate (IS)
Cone,
9/L
2
100
20
10
Requi rements
Detection of analyte; S/N > 3
0.95 1 .0 (c)
(a) PSF = peak symmetry factor. Calculated using the equation:
w(1/2>
PSF = ...........
0.5 x W(1/2)
where w(1/2) is the width of the front of the peak at half height and UC1/2) is the
peak width at half height.
(b) PGF = peak Gaussian factor. Calculated using the equation:
1.83 x W(1/2)
PGF = - ....... -----
where W(1/2) is the peak width at half height and U(1/10) is the peak width at tenth
height.
(c) Resolution between the two peaks as defined by the equation:
t
R = ---
U
where t is the difference in elution times between the two peaks and W is the average
peak width, at the baseline, of the two peaks.
-------
Appendix B
Revision No. 2
Date: July 29, 1990
Page 1 of 5
APPENDIX B
NPS ANALYTE REPORTING BELOW MRL AND
IDENTIFYING UNKNOWN PEAKS
-------
| UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
CHCMwmr L*«MIATO*Y. NASA/NCTL
•UILMMG UN, NTO. M«M*Sim «0
June 1, 1988
MEMORANDUM
SUBJECT: NFS Analyte Reporting Below MRL and Identifying Unknown Peaks
FROM: Bob Maxey/ Analytical Coordinator
Environmental Chemistry Laboratory
TO: Dave Munch, Analytical Coordinator
TSD-Cincinnati
Atfcry E. Dupuy, Jr., Technical Monitor
Environmental Chemistry Laboratory
Attached are the procedures that NPS 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.
-------
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 NFS analyti-
cal contractors and referee laboratories make an effort to report the presence
of NPS analytes below the Minimal Reporting Levels (MRL). We 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 establis
ed MRL and the MRL V on the primary column will be investigated. A respon
on the "secondary" GC column, indicating the presence of the analyte, is al
required for additional work.
2.a The first occurrence of a peak meeting the requirements of (1) is noted and
reported to the Technical Monitor, but no action is taken V. Upon a secon
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 tafc
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 conf ir
mat ion 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 chromatograms
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 H>L
NPS method 2 MRL « 5 x H)L NPS method 6 MRL = 3 x EDL
NPS method 3 MRL • 5 x HDL NPS method 7 MRL - 3 x H)L
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 spectronetry.
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 MRL - MRL will be subject
to (1) and (2a) above.
Provisions of (2b) also apply except references to GC/MS requirements.
3. Whether the identification of the analyte is attempted at the contractor
laboratory or at the referee laboratory, only analytes positively con-
firmed by GC/MS will be reported beyond the Technical Monitor for the
Method and the Analytical Coordinators. No unconfirmed data will be
reported outside the NFS 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-SPS Analytes
It is expected that, over the course of the NPS Program, numerous
extraneous responses will be evident on chromatograms from the various methods.
The contractor or referee laboratories will be required to attempt identifi-
cation of peaks or responses on the primary column exhibiting the minimal criter
below.
1. For Methods 1, 2, 3, 6, and 7, if, upon initial analyses, the response
of an extraneous peak on the primary column is equal to or greater thai
the response of the nearest NPS analyte on that column at 10 x MRL
(Minimal Reporting Level), an attempt must be made to identify that un-
known peak or response by GC/MS. Full scan spectra and subsequent
library search are expected and must be followed by comparison of the
spectra of the unknown compound with those of an authentic standard of
the suspected compound.
2. The work in (1) must be attempted by the contractor and/or referee lab
oratories on the first occurrence of such a peak and the results of th
attempt reported to the Technical Monitor for the Method. If the
analytical contractor feels his system or instrument is not capable of
the confirmatory work, he must send both that extract and that of the
related Method Blank to the appropriate referee lab under iced
conditions by next-day air.
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 lev*
must be marked on the outside of the vial or ampule. (NPS will absorb
coats of these shipments.)
-------
Specific aarople and analytical information must accompany each auch
extract.
o Sample i.d. number, weight of sample matrix contained in the
ampule, copies of chrotnatograms from the primary GC coluan/
identification of the retention window for the unknown response(s)
as defined by the last NPS analyte to elute before the unknown
peak or response and the first NPS 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 NPS 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 QC/MS confirmation
on a sample, discussions with OPP personnel will take place before continua
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 3
APPENDIX C
CHANGES IN NPS LABORATORY PROCEDURES
-------
if-—-*
I UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI OHIO 45268
KEXORANDUX
DATE: July 14. 1988
SUBJECT: Changes in NPS Laboratory Procedures
TKOX: David J. Hunch. TS2 Project Manager
National Pesticide Survey
TO: R?S Technical Heritors (See below;
T>.c- following rir.cr changes in laboratory operations are beir.g -« = >..
1. Spiking Levels 'Methods I-"'
Currently. selected !.*"3 sartles are being spined at either Lev«l
: (5 ti.-ts M?L . Lev;l : ;i: ti-bs MF.L . cr Level 3 (2: tires M-l .
In rany cases, spiking at Level 2 has crested analyt-: concer.traticn;
in sarples whirr, exceed tr.r linear range cf the instrumentation. Any
Level 3 spiked sample's currer.tly or. har.i should be analyred: howeve:,!
no further requests v-.;i be cad; to spir.e sarples at Level ?.
In order tc .raintair. three spihing levels, a Level 0 *2 tir.ss
XRL) is bein; adcei. Ls.::tat:ry Cor.trsl Standards and Tire Storace
Sa-;les,are to contin-c tc be ssiked at Level 2 (1C tires MHL' .
2. Spiking Levels (Method 9)
Currently, sairple spiking levels used for Method 9 are, Level '.
(2 times MRL) . Level 2 (10 times HRL) , and Level 3 (10.000 ug/L) . Tl..
spiking levels art to reaain the sars; however. Level 0 will now it I
tir.es MRL, Level 1 10 tices HRL, and Level 3 10,000 ug/L.
3. Data Reporting Forrat
In order for the data reporting forcat to satch the rec.uirerer.ts
for reporting suspected NFS analytes observed on the prirary colurr. ,
at a concentration between 1/2 HRL and HRL (see ceaorandun entitled
"Determining and Reporting the Presence of NTS Analytes below thi
Hiniaui Reporting Levels and Identifying Unknown Peaks," by Bob Haxey
fi/1/88), further clarification is required. In those cases where tl.c
presence of an NFS analyte at a concentration between 1/2 HRL and t.h~
HRL is successfully confirmed, the primary and conf irrcational colur:.
data for that analyte should be reported as "-111". In those cases
where conf irmational analyses are either not required, or the
conf irmational analyses did not confirm the presence of the analyte,
the primary column data for that analyte should be reported as "-222".
-------
-2-
Plcase transmit this information to bot- your contract and refere;
laboratories, as soon as possible. If you have any questions concern;
these ir«»s, please let T.e know.
Addressees:
A. Dupuy
L. Kacphake (TSD
C. "adding (TSr;
R. Maxey (OP?)
K. Sorrel! 'TST1
R. Tho-as (TS:1
H. Brass (TS:
C. Freebis (CSC
A. Kroner (?s:
-------
Appendix D
Revision No. 2
Dale: July 29, 1990
Page 1 o< 17
APPENDIX D
NPSIS SAMPLE RECEIPT SOFTWARE FOR LABORATORIES
-------
4/5/88
TO: DATA MANAGER, EFA/TSD LAB
FROM: CHIP LESTER, ICF IHC. (
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 whict
allows you to interactively send messages to ICF staff via your computer
keyboard, file transfer, and access to the ICF computerized mail system for
sending memos. It is also possible for you to speak over the phone to an ICF
staff member during your session.
It is important that you test the communications link between the NPSIS
computer and yours. We have experienced trouble when using Carbon Copy
software with a computer which has a Manzana 3.5 inch disk drive, and also
with computers which have a non-Hercules or non-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.
We 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 day,
seven days a week. Ve appreciate hearing any comments you have regarding
NPSIS.
-------
THE NPSIS SAMPLE RECEIPT PKOGBAM
NPSIS is designed to keep crack of the day co day operations of the
National Pesticide Survey. You play an important role in NTS and your timely
notification of receiving a kit of samples is essential to the success of NFS.
Me have designed the Sample Receipt Prograa with your busy schedule in aind.
NFSIS will obtain the minima amount of information necessary while still
maintaining a secure system. You will be entering data into the NPSIS
personal computer via your own computer, modem, and Carbon Copy software.
1.1 Hardware and Software Requirements.
The NPSIS Sample Receipt Prograa 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 you
by ICF for the duration of NPS.
1^2 Initial Installation Steps.
Before you can access and use NPSIS. you must first load the Carbon Copy
software onto your PC. The directions are provided in the Carbon Copy manual.
One item you will 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 Carboi
Copy Parameters' Screen. The information you must enter consists of the
following:
-------
Name: NPS
Telephone Number: 703->#1-0629
Password: NPS
1 . 3 Pan
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 .
A SAMPTJt 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:> CuiMJ* UPS in your directory containing Carbon Copy.
This command will automatically dial the NPSIS computer, send your password
for verification, and establish a data link between the two computers. You
will be able to discern what is taking place by messages to your screen.
Receipt Into NPSIS.
Once you have established a data link, ( e.g., are "logged on"), you will
see on the screen exactly what is on the screen of the NPSIS computer. This
screen you are viewing is the 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 you
are accustomed to. A few tips on how to use the system are outlined in the
next section.
-------
1 Useful Tins on How to Use KPSIS.
Before you start, a few thing* to reaember 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 «enu.
• 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 fe
items to enter in a screen which prompts for several items.
• Pressing "Enter", "arrow up", or "arrow down" will move the cursor
from field to field in each screen. Remember that using the
sideways arrows will not work.
• Pressing the "Alt" and "Right Shift" keys together will place the
Carbon Copy Control Screen over the NPSIS Sample Receipt Program.
You can then use the communications features in Carbon Copy.
Pressing "F10" again when you are through will replace the 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 data
entry, simply press "Esc" to exit the Sample Searching screen and be
placed in the main menu.
2.3 A Basic Outline of th« ^*»role Receipt Pr,?Era!Bi
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 the
ability to send memoranda to ICF staff.
The information obtained in an entry for a kit of bottles is:
• The kit identification number, the FedEx airbill number,
and the last name of the person making the entry.
A
• Any damage to the kit as a whole such as melted ice or any
breakage of the cooler.
-------
• Verification of which bottles belong in a kit or cooler,
notification of any Biasing bottles or any additional
bottles, and
• Any daaage to each sample bottle which renders it unusabli
for analysis and testing.
2 U NPSTS S«iimle Recetot Program Screens
When you have completed the logon procedure, you will see the following
main menu on your computer screen:
NATIONAL PESTICIDE SURVEY INFORMATION SYSTEM
SELECTION MENU FOR REPORTING SAMPLE RECEIPTS 04/05/88
Report \ Edit a Sample Receipt
Send a Memo
Press to Logoff
use f land 4-1 to select option.
The screens provided in this memo will show all of the screens available
and thus represent the maximum number of screens you will encounter with
NPSIS. It is most likely that you will not have the need to enter informacio
reporting damaged kits or samples. Therefore, not all of the screens deplete
below will appear in your normal session.
If you choose the first item on the menu, "Report \ Edit a Sample
Receipt*, you will then be prompted for the kit identification number and the
FedEx airbill number Associated with the specified kit. The screen will
appear like this:
-------
NFS Sample Receipt Searching Screen
** Enter the following itens to access kit information **
To find the Kit information in KPSIS in the no it 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 ant
FedEx airbill number combination is incorrect, NPSIS will prompt you to try tt
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********AAA*AA**********
NPSIS is designed to track Kits and FedEx airbill numbers.
The Kit and FedEx airbill number combination you have entered
does not aatch 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.
***********************************************"*****************
Press any key to continue.. .
Then, you will encounter this screen insuring that you have entered the
FedEx airbill number:
Kit No.: PD-0001-151
Did you enter the correct Kit number and FedEx airbill number?
NPSIS is designed to store and track all FedEx airbill numbers.
This Kit may have a different FedEx airbill number than the
system, please enter the new FedEx airbill number:
Note: if the correct airbill number was entered before, hit ENTER.
PgDn (Next page), PgUp (Previous page), Esc (Exit)
-------
Once you have correctly Identified the sample kit, NPSIS will ask you
there is any daaage to the kit a* a whole:
Kit No.: PD-0001-151
Was there any danage to the saople 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 saaple kit? (Y/N)
Please indicate the cause for damage:
Kit is broken (Y/N) Y
Ice is melted (Y/N)
Other Reason (Y/N)
Please enter any comments about the sample kit.
Comments: Broken upon arrival.
Comments:
PgDn (Next page), PgUp (Previous p«ge), 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 any
which already appear. This insures that no information is destroyed.
-------
Next, NPSIS 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 NPSIS 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 chat you did not receive exactly what
NFS IS assuaes you have received, you vill ba prompted Co enter Che appropriate
information. This information includes pressing a "Y" or a "N" beside each
bottle, and entering Che botcle number found on the labels of any additional
bottles you have received:
Kit No.: PD-0001-151
Please indicate which bottles you received:
Boccle No: Received (Y/N)
PD-0001-1-1-01
PD-0001-1-1-03
PD-0001-1-3-01
PD-0001-1-3-03
PD-0001-1-9-01
PD-0001-1-9-03
H
H
Y
Y
Y
Y
1.
3.
5.
7.
Please indicate any additional bottles you received:
Bottle No.: PD-0002-1-1-05 2. Bottle No.: PD-0002-2-2-01
Bottle No.: FD-0004-4-4-01 4. Bottle No.: - - - -
Bottle No.; - ... 6. Bottle No.: - ...
Botcle No.: - ... 8. Bottle No.: - ...
PgDn (Next page), PgUp (Previous page), use f |or ••—'to select field.
Notice that the user has indicated chat he did not receive the first two
bottles on the list. Also note chat the user has indicated additional bottles
which have come in the sample kit, but which were not on the list.
-------
N«xc. NPSIS pronpts you to indicate if any of the individual bottles have
been daaaged and rendered unusable for analysis:
Kit No.: PD-0001-151
Was there any daaage to the «aaple Bottles? (Y/N) T
PgDn (Next page), PgUp (Previous page), Esc (Exit)
-------
In order to complete the appropriate information on damaged samples, you
must first press a "Y" or a "N" in the field labeled "Damaged 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
below, che "Other" category should be used if the sample is unusable but is
not broken. Please try to connent 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 H
PD-0001-1-3-03 H
PD-0001-1-9-01 H
PD-0001-1-9-03 IT
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 is unusable.
PgDn (Next page), PgUp (Previous page), use 4 | or *-J to select field
-------
Now you have completed *11 of the necessary information needed to verify
chat che proper samples have reached their final destination in usable
condition. You aay save your kit entry by pressing "Enter". If you wish to
cancel your kit entry and try again, press "N" and "Enter". If you wish to
view or edit the current kit entry, press "R" and "Enter" and HPSIS will plac
you back at the beginning of your entry.
You have completed all of the data entry screens for this Kit.
You may save your entry by pressing 'Enter' .
You may cancel your entry by pressing 'N' and 'Enter'.
You may verify or edit this entry by pressing 'R' and 'Enter'.
* * * Accept entries? * * *
* Press *— to Save *
* Press N and •*•— ' to Cancel *
* Press R and ^-J to Verify or Edit * Y
By pressing "Enter" , you have saved all of the information necessary for
a particular sample kit. NFS IS assumes that you will enter more than one kit
entry per session. Therefore, you will be placed at the initial "Searching
Screen". If you are finished, press "Esc" and you will be returned to the
main menu. You can then log off of NPSIS by pressing "Alt" and "Right shift"
at the same time. You may also send a memo through the ICF computerized mail
system. To do this, cursor down to the second menu choice and press "Enter".
The next two pages of this memo describe how to use the ICF electronic
mail system. Note that the password for you is NFS. The mail system software
program will prompt you for this password before it will allow access to the
system. Also, when you are selecting the recipients of your memo, please
press the space bar beside the initials "NFS". This will send your memo to
all ICF staff involved in the NFS project. If you wish to send memos to a
particular ICF staff member, please call Beth Estrada for the identification
number of the desired ICF employee.
-------
ELECTRONIC MAIL
Function
Augment office communications
electronic transfer of notes and files.
with
Summary
Electronic Mail (E-Mail) allows you to send,
receive, read, and subsequently save or
discard notes and attached files.
When you power up your workstation you
will automatically enter E-Mail if you have
received any mail. Enter your password to
check your mail, or press twice to
avoid E-Mail and continue to the Assist
main menu.
Instructions
Operation of E-Mail is similar to Lotus
1-2-3. Press the Fl key to receive help at
any time during operation. If any more
help is needed contact workstation support
to receive a manual.
For more information on any feature of
electronic mail, use Network Courier's on-
line help or refer to the User's Manual.
Passwords
Your password will be "password* until you
change it yourself. Once you have given
your password and entered E-Mail, you can
change your password by selecting Options,
then Password.
Reading Mail
1. Select "Read" from your menu
Highlight read,then press
.
2. Select the note to read:
a. Highlight the note (using
the arrow keys); and press
.
B. To save the note, select
•Storage", then "Save". Enter
the name of the file to which
the note should be saved.
3. Press to select another note.
Writing Mail
1. Select "Compose", then "edit".
2. Press when the highlight
moves to TO".
3. Select the recipients(s):
a. Move the highlight to the
first recipient's initials.
b. Press the space bar. A
small mark will appear.
c. Repeat steps a and b for all
recipients. Press the space bar
twice to "de-select" recipients.
The small mark will disappear.
d. Press <£SC> to cancel the
entire list.
4. Select the initials of those who will
receive copies:
a. Press the down arrow to mo%
to "CC".
b. Select recipients as instructed
above (step 3, a-d)
-------
Writiaf Mail, continued
5. Enter t subject and priority.
(optional)
6. Select attachments (optional):
a. Press <£NT£R> 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 th* Mail Program
1. Press from the menu.
2. Select "YES".
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Appendix E
Revision No. 2
Date: July 29, 1990
Page 1 of 6
APPENDIX E
FORMAT FOR NPS DATA
-------
FORMAT FDR NATIONM, PfcSTICTrgr SURVEY (NFS) DATA
LBffi COOMB
1 1-6 l.Tenp
9-14 S_Tenp
17-24 Date_Sam
27-34 Date_Shp
37-44 Date_Rec
47-54 Time_Sam
57-64 Time_Ice
[FOR MEMDS 5 AND 9 ONLY]
68-69 pH
2 1-6 alter INITIAL TEMPHRA3URE OF
9-14 enter SIABHIZED TEMPEKAIURE CF
17-24 enter EME SftMFLEE
27-34 enter EME atTPPED
37-44 enter EftlE RhnT'.ivtu
47-54 enter TIME SAMPLED
57-64 enter TIME ICED
[FOR METHDS 5 AND 9 CKLY]
67-70 enter pH
3 BLANK
4 1-17 Receipt Condition
5 1-80 enter CONDITION OF SAMPLE UPON RECEIPT AT LABOFATORY
6 BLANK
7 1-6 Sanp #
16-18 Lab
21-25 Set #
28-35 Date_Spk
38-45 Date_Ext
48-55 Date.Ana
58-63 Colum
8 1-13 enter SAMPLE IDENTIFICATION NCM3ER
16-18 enter LAB ABBREVIATION
21-25 enter SET NIMER
28-35 enter DATE SPIKED
38-45 enter DATE EXTRACTED
48-55 enter DATE ANALYZED
58-63 enter ANALYSIS COLUM
9 BLANK
-------
FCWftT FCR NATIClttL PES'l'lClUE SURVEY (NFS) EKTA (cent.
LEE
10 1-4 Type
8-13 spiker
16-22 Detract
2S-31 Analyst
34-40 San\_Vbl
43-49 Bct_Vt>l
52-60 Int. Std.
65-70 % Surr
11 1-5 enter SAMPLE TYPE
8-13 enter SPIKER'S INITIALS
16-22 enter EXTRACTOR'S INITIALS
25-31 enter ANALYST'S INITIALS
34-40 enter \^LUME CF S>WFLE
43-49 enter VOLUME CF EXTRACT
52-62 enter INTETOPkL SIMJEftRD
65-70 enter PERCENT RECCVERY CF SURROGATE
12 BLANK
13 1-8 Connents
14 1-80 enter ANY PERTINENT CdMENTS ON 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 CCWCENIRATICN OR PERCENT RECOVERY
39-63 enter ANALYTE»S NAME
66-72 enter CCNZENTRATICN CR PERCENT RECOVERY
-------
PQRAT FOR NATIONAL ttifl'lClUE SURVEY (NFS) HJSIKMNr CONTROL DMA
T.TNTE CDLIMB
1 1-3 Lab
6-11 Method
14-21 Date_Ana
24-30 Analyst
35-37 S/N
42-44 PSF
49-51 Pty
55-58 Res.
2 BLANK
3-? 1-3 enter LAB ABBREVI7MICN
6-11 enter MEUHDD NUTBE3*
14-21 enter DAIE ATftLYZED
24-30 enter ANALYST'S INITIALS
33-37 enter SIOftL TO NOISE RATIO
40-44 enter PENH SYMMETRY FACTOR
47-51 enter FfWC GEOMETRY FACTOR
54-58 enter RESOLUTION
-------
NOTES CN NFS EftlA FCEMVTS
1. The format for any date is mm/dd/yy
A missing date should be entered 01/01/60
2. The format for any time is hh:mm 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. The number of decimal places should be as follows:
Concentration 3
Percent Recovery 1
Internal Standard 0
Instrument Controls 2
PH 1
Temperatures 0
Volumes 0
5. The codes for Column are as follows:
Primary PRIM
Confirmatory OUT
Third QCMS
6. The codes for Lab are as follows:
TSD TSD
CFP GPP
WERL WER
Radian RAD
Battelle BCD
James M. Montgomery JMM
Alliance ALL
Environmental Sciences and Engineering
7. The codes for Type are as follows:
Field Sample SWF
Shipping Blank SBLK
Method Blank «LK
Lab control Standard LCSt
Lab Spike Sample LSStt
Time Storage for Extract H1BP
Tune Storage for Sample KT9P
where § is the mixletter (A,B,C or D)
and # is the spiXing level (1,2 or 3)
\\
-------
NOTES CN NFS IMA FCE9AX5 (CCRt.)
8. There should be at least cne blank line between samples in the NFS data
file.
9. The 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 HX -ill
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 F
Revision No. 2
Date: July 29, 1990
Page 1 of 3
APPENDIX F
DATA REPORTING FORMAT CHANGES
-------
DATS: April 18, 1988
SUBJECT: Data Reporting Format Changes
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. Too 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, coloans 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
BTKt
BTSt
Laboratory Control Sample
Laboratory Spiked Sample
Day 0 Time Storage Sample
Extract Time Storage Sample
Sample Time Storage Sample
In additioa, two clarifications have b*«a made to the codes for
analyte concentration entries.
-999 » let Detected « 1/2 Minimum 1*sorting Limit)
-111 • Below Minimum Reporting Limit bet greater than or equal to
1/2 the Minimum Reporting Limit.
-------
3
4
5
6
7
8
Note: Method 9 only
Foraat for National Pesticide Survey (NFS) Data
COLUMNS DESCRIPTION
1-6
9-U
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_Saa
Date~Shp
Date'Rec
Ti«e~Sam
Time'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
Samp t
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 G
Revision No. 2
Date: July 29, 1990
Page 1 of 4
APPENDIX G
DATA REPORTING CODES
-------
DftTE: September 9, 1988
SUBJECT: Data Reporting Codes
FECM: Christopher Frebis, CSC Statistician
TO: Distribution
Hie purpose of this memorandum is to discuss the reporting codes used in
the National Pesticide Survey. There has been sane confusion over these codes
as to when and where to use them and their exact meaning.
Table 1 identifies the unique sample types (SAMP - field sample, MSLK -
method blank, SBLK - shipping blank, LCS - 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 QCMS
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 Munch, Technical Support Division
Kent Sorrell, Technical support Division
Bob Thomas, Technical Support Division
-------
TABLE 1: USES CF DATA CODES IN NFS
SAMPLE TYPE
LSS,DTS
SAMP
,(a)
_ i i i (C)
_333
-444 e
-555
-666
_777(h)
888 (V
-999 (j)
MBLK
.(a)
—111
-333
****
-777(11)
888 (V
-999(1))
PTHv(^)
SBLK
.(a)
_j_^j_(c)
-333(d)
-444(6)
-555
-666 (9>
-777 (W
888(V
_999(j)
rvM-ir" ikl
LCS
(b)
•
****
****
****
****
****
-777 (h)
****
****
4 rof ( 1 )
fflE,HES
.(b)
****
-333(d)
-444(6)
****
****
_777(h)
****
****
_ __ (1)
(a) Analyte dropped from survey (Daneton-s and Carboxin sulfoxide) or not
analyzed on the second colurm or in GC*E analysis.
(b) Analyte not in mix.
(c) Analyte's concentration between MRL/2 and M?L. (If no confirmation is run,
a coninent as to why should be made.)
(d) A lab mishap, e.g. sample lost during extraction or sample dropped etc.,
•Diis is a unique situation. (A comment should give further explanation.)
(e) Tliis analyte fails QC in this set (e.g. LCS out of control or positive
method blank or time to extraction or analysis is too long) and therefore
cannot be reported, however the analyte does not require a qualitative
challenge. TJiis code also applies to any spike sample in a set where the
LCS is out of control.
(f) GCMS only: Sent to referee lab for GOB analysis.
(g) Inis analyte fails QC in this set and therefore cannot be reported, however
the analyte requires a qualitative challenge.
(h) Analyte was saturated. Should be diluted and re-done, if observed in a
field sample. (Another sample with the exact same header information
should appear, analytes not saturated in the original sample should be
reported as ., and saturated analytes should be reported as their
concentration.)
(i) Positive, can occur in two fashions: 1) any analyte in GCMS analysis; or
2) a qualitative only analyte on either of the first two columns.
(j) Analyte's concentration below MRL/2.
(k) Concentration above M3L for quantitative analytes, reported to three
significant figures.
(1) Percent recovery, reported to one decimal place (even if recovery is 0.0%).
**** Code not applicable.
-------
Saocle (Qualitative cnlv analvte)
-333
-999
888
-333 -999 888
-333 -
-999 888
GOUMJ
FRIM
OUT
-999 888 GCMS
GCMS
(at referee)
Samplg (CV?ntL^t-?'t'iv'?
with CC
-333
-444
-666
-333 -666 -999
-333 -555 -999 888
-333 -999 888
FRIM
CCNF
GCMS
GCMS
(at referee)
Sarrle (Quantitative
rp nt
-Ill
-333
-777* -999
FRIM
CTKF
-333 -555 -999 888 -333 -555 -999 888 -333 -555 -999 888 -33'3 -5$5 -999 888 GCMS
333 ~999 c°nc
core
-333 -999 core:
-333 -999 888
-333 -999 088
-333 -999 888
-333 -999 888 GCMS
(at referee)
a = Dilute and reanalyze
-------
Appendix H
Revision No. 2
Date: July 29, 1990
Page 1 of 11
APPENDIX H
NPS RAPID REPORTING SYSTEM
-------
i
| UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI. OHIO 45268
MEMORANDUM
DATE: April 12, 1988
SUBJECT: NPS Rapid Reporting System
FROM: David J. Munch, Chemist
Drinking Vater Quality Assssment Branch
TO: NPS 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 MRL should also be processed as below.
(Note: The procedures for determining the occurrence of NPS 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 (CC/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.
-------
-2-
If you have any questions concerning these procedures, please let Bob
Maxey 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
-------
METHOD ffl
AMALYTI RAPID REPORTING LEVEL
Alacblor 44 Ug/L
Aaetryn 300 ug/L
Atrazine 35 ug/L
Broaacil 2,500 ug/L
Butylate 700 ug/L
Ctrboxio 1,000 ug/L
Diphenaaid 300 ug/L
Fenaaiphos 5.0 ug/L
Hexazinone 1,050 ug/L
Hetolachlor 300 ug/L
Hetribuzin 250 ug/L
Propazine 500 ug/L
Siaazine 50 ug/L
Tebuthiuron 125 ug/L
Terbacil 250 ug/L
-------
METHOD 12
AHALYTE RAPID REPORTING LEVEL
alpha-Chlordane 0.5 ug/L
gamna-Chlordane 0.5 ug/L
Cblorothalonil 150 ug/L
Oactbal (DCPA) 5.000 ug/L
Oieldrin 0.5 ug/L
Propacblor 130 ug/L
Trifluralin 25 ug/L
-------
METHOD 13
AMALYTE RAPID REPORTING LTYEL
Acifluorfen 130 ug/L
Bentazon 87.5 Uff/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
-------
METHOD f4
ANALYTE EAPID REPORTING LEVEL
Cyanazine 13 ug/L
Diuron 70 ug/L
Fluometuron 438 ug/L
Prophan 595 ug/L
-------
METHOD 15
AMALYTE RAPID REPORTING LEVEL
Aldicarb 10 ug/L
Baygon 40 ug/L
Ctrbtryl 1,000 ug/L
Carbofuran 50 ug/L
Hethomyl 250 ug/L
Oxamyl 175 ug/L
-------
KETEOD §6
XMALYTI RAPID REPORTING LEVEL
ethylene thiourea l.OS ug/L
-------
METHOD 17
AJfXLYTE RAPID REPORTING LEVEL
dibroaochloropropane 2.5 ug/L
1,2-dichloropropane 56 ug/L
cis/trans 1,3-dichloropropene 11 ug/L
ethylene dibromide 0.04 ug/L
-------
METHOD 19
AMXLYTI UPID IPOtTIMG
Nitrate/Nitrite 10,000 ug/L
-------
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:
2) Decide whether the smallest, X^ 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 5% risk of false
rejection.
4) Compute one of the ratios in Table 1. For use in this QAPP we
will be using ratio r22, since we will be using between 20 and
17 points for the control charts.
5) Compare the ratio calculated in Step 4 with the appropriate
values in Table 2. If the calculated ratio is greater than the
tabulated value, rejection may be made with the tbulated risk.
Fort his QAPP we will be using the 5% risk values (bolded) .
Example (from Taylor)
Given the following set of ranked data:
10.45, 10.47, 10.47, 10.48, 10.49, 10.50, 10.50, 10.53, 10.58
The value 10.58 is suspected of being an outlier.
1) Calculate ru
10.58 - 10.53 0.05
rn - ............. - ---- - 0.454
10.58 - 10.47 0.11
2) A 5% risk of false rejection (Table 2), ru - 0.477
3) Therefore there is no reason to reject the value 10.58.
4) Note that at a 10% risk of false rejection rn - 0.409, and the value
10.58 would be rejected.
-------
TABLE 1
CALCULATION OF RATIOS
Ratio
f. „
For use if
n is between
if Xn is
suspect
f V V \
(Xn ' Xn-i)
if X: is
suspect
/Y V \
\&2 ~ *-l)
Note that for use in this QAPjP ratio r22 will be used.
V \ / V
"n-1/ \A2 ~
8 - 10 -
- X2)
V \ / V
•"Ti-2^ ^A3
c2i 11 - 13
- x2) (Vi
• Xn.2) (X3 - Xj]
r22 14-25
' X3) (Xn-2 ' Xj
-------
•10
•11
L21
TABLE 2
VALUES FOR USE WITH THE DIXON TEST FOR OUTLIERS
Risk of False Rejection
n 0^5% 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-
-------
Reference:
John K. Taylor, Quality Assurance of Chemical Measurements. Lewis
Publishers, Chelsea, MI, 1987.
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
-------
Appendix J
Revision No. 2
Date: July 29, 1990
Page 1 of 2
APPENDIX J
STANDARD OPERATING PROCEDURE:
BATCH FILING SYSTEM
-------
Appendix J
Revision No. 2
Date: July 29, 1990
Page 2 of 2
APPENDIX J
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 departmentally
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 in 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
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
------- |