EPA-810/B-92-003
United State* Office of Water (WH-550) EPA 810-8-82-003
Envfaomnemal Protection Office of Peaikhiea and February 1902
Agency Toxic Subatancea (H-7501C)
QUALITY ASSURANCE PROJECT PLAN
FOR THE
NATIONAL PESTICIDE SURVEY OF DRINKING WATER WELLS
ANALYTICAL METHOD 2 - CHLORINATED PESTICIDES
Prepared by:
Clean Harbors, Inc.
213 Burlington Road
Bedford, Massachusetts 01730
Prepared for
U.S. Environmental Protection Agency
Technical Support Division
Office of Drinking Water
26 W. Martin Luther King Drive
Cincinnati, Ohio 45268
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
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Section No. 1 ,4
Revision No. 3 ,
Date: Februaiy 28, 1990
Page 2 of 2
APPROVAL PAGE
Clean Harbors Program Manager Date
Project Coordinator Date
Chemistry Division Manager Date
Clean Harbors QA Officer Date
EPA Project Officer Date
EPA Technical Monitor Date
EPA QA Officer Date
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Section No. 2
Revision No. 3
Date: February 28, 1990
Pag* 1 of 3
NATIONAL PESTICIDE SURVEY
QUALITY ASSURANCE PROJECT PLAN FOR
ANALYTICAL METHOD 2 - CHLORINATED PESTICIDES
O
2. TABLE OF CONTENTS
Section
TITLE AND APPROVAL PAGE
TABLE OF CONTENTS
PROJECT DESCRIPTION
1.
2.
3.
4.
PROJECT ORGANIZATION AND RESPONSIBILITIES
4.1 QA Officer's Responsibilities
4.2 Analytical QC Coordinator's Responsibilities
4.3 Laboratory Staff Responsibilities
5. QUALITY ASSURANCE OBJECTIVES FOR
MEASUREMENT DATA
5.1 Determination of Estimated Detection Limit
(EDL)
5.2 Determination of GC/MS Detection Limits
5.3 Construction of Control Charts
5.4 Frequency and Procedure for Matrix Spiking
6. SAMPLING PROCEDURES
7. SAMPLE CUSTODY
7.1 Notification of Laboratory
7.2 Holding Time, Storage and Disposal
Requirements
7.3 Custody Procedures at the Clean Harbors
Laboratory
8. CALIBRATION PROCEDURES AND FREQUENCY
8.1 Preparation of Surrogate and Internal
Standards
8.2 Preparation of Instrument QC Standard
8.3 Preparation of Calibration and LCS/Time
Storage
8.4 Instrument Calibrations
9. ANALYTICAL PROCEDURES
10. DATA REDUCTION, VALIDATION AND REPORTING
10.1 Data Reduction
10.2 Data Validation
10.3 Fast Track Reporting
10.4 Data Reporting
2
3
1
3
3
5
4
3
Revisions Date
3 2/28/90
3 2/28/90
3 2/28/90
3 2/28/90
3
3
3
3
2/28/90
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2/28/90
2/28/90
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Section No. 2
Revision No. 3
Dote: February 28, 1990
Page 2 of 3
2. TABLE OF CONTENTS (continued)
Section
11. INTERNAL QUALITY CONTROL CHECKS
11.1 Method Blanks
11.2 Calibration Check Samples
11.3 Replicate and Spiked Samples
11.4 Laboratory Control Samples
11.5 Surrogate Spikes
11.6 Internal Standard Checks
11.7 Instrument Quality Control Standards
12. PERFORMANCE AND SYSTEM AUDITS
12.1 Performance Audits
12.2 System Audits
12.3 External Audits
13. PREVENTIVE MAINTENANCE
14. SPECIFIC ROUTINE PROCEDURES USED TO ASSESS
DATA PRECISION, ACCURACY AND COMPLETENESS
15. CORRECTIVE ACTION
15.1 Immediate Corrective Action
15.2 Long-Term Corrective Action
16. QUALITY ASSURANCE REPORTS TO MANAGEMENT
16.1 Internal Reports
16.2 External Reports
1
4
Revisions Date
3 2/28/90
3
3
2/28/90
2/28/90
2/28/90
2/28/90
2/28/90
17.
ARCHIVAL OF RAW DATA
2/28/90
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Section No. 2
Revision No. 3
Date: February 28, 1990
Page 3 of 3
2. TABLE OF CONTENTS (continued)
Appendices
A.
B.
C.
D.
E.
F.
G.
H.
1.
J.
METHOD 2 (October 27, 1987)
GC/MS SPECTRAL INFORMATION
DIXON'S TEST
STANDARD OPERATING PROCEDURE FOR
MANUAL DATA ENTRY
STANDARD OPERATING PROCEDURE FOR
AUTOMATED DATA ENTRY
NPSIS SAMPLE RECEIPT SOFTWARE FOR
LABORATORIES DATED 4/5/88
NPS RAPID REPORTING SYSTEM 4/12/88
DATA REPORTING FORMAT CHANGES 4/18/88
NPS ANALYTE REPORTING BELOW MRL AND
IDENTIFYING UNKNOWN PEAKS 6/1/88
REVISIONS TO NPS RAPID REPORTING SYSTEM
Pages
32
28
5
19
4
17
3
2
5
4
Revisions
3
3
3
3
3
3
3
3
3
3
Date
2/28/90
2/28/90
2/28/90
2/28/90
2/28/90
2/28/90
2/28/90
2/28/90
2/28/90
2/28/90
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DISTRIBUTION UST
EPA Staff No. of Copies
EPA Technical Monitor, EPA/TSD 5 copies
Clean Harbors Staff
Laboratory Manager 1 copy
Richard Ravenelle
Program Manager 1 copy
Louis Macri
Laboratory Coordinator 1 copy
John Verban
Sample Prep. Manager 1 copy
Doug Buffington
GC Section Manager 1 copy
John Verban
GC Analyst 1 copy
Kate Duffy
Laboratory QC Coordinator 1 copy
Christine Johnson
Clean Harbors QA Director 1 copy
Richard Fix, Ph.D.
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Section No. 3
Revtolon No. 3
Date: February 28, 1990
Pag* 1 of 1
3.0 PROJECT DESCRIPTION
Clean Harbors, Inc. (Clean Harbors) has been contracted by the USEPA Office of Pesticide
Programs and Technical Support Division to provide analytical services in support of the National
Pesticide Survey (NPS). The NPS has been designed to meet two major objectives: (1) to determine
the degree to which the drinking water wells of the nation are contaminated by pesticides; and (2) to
better understand how pesticide concentrations in drinking water wells are associated with patterns of
pesticide usage and the vulnerability of ground water to pollution. Clean Harbors will analyze 750
samples from community water systems and 750 samples from domestic wells for the presence of
chlorinated pesticides using gas chromatography with an electron capture detector by Method 2
(revised Oct. 27, 1987).
This Quality Assurance Project Plan (QAPjP) has been prepared to ensure sample analysis and
reporting in accordance with Method 2 and contractual reports of work.
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Section No. 4
Revision No. 3
Date: February 28, 1990
Page 1 of 3
4. PROJECT ORGANIZATION AND RESPONSIBILITIES
Figure 4-1 represents Clean Harbors's organization chart for this program. As program
manager, Mr. Louis Maori will be responsible for technical and administrative direction of the overall
program. Mr. John Verban will coordinate and review all sample preparation and gas
chromatographic work. He will also be responsible for initiation of bench level corrective actions.
The key individual responsible for QA is the Director of Quality Assurance, Dr. Richard Fix, who
will serve as Program QA Officer. Dr. Fix reports directly to the President of Clean Harbors. The key
individual responsible for Analytical QC activities is Christine Johnson, Analytical QC Coordinator, who
reports directly to the QA Director. Ms. Johnson is thus independent of the technical groups
generating measurement data. The responsibilities of these key QA/QC individuals on this program
are briefly described below.
4.1 QA OFFICER'S RESPONSIBILITIES
The Division QA Director, Dr. Richard Fix, is the responsible Quality Assurance Officer for this
project. He will review and approve the proposed Project Plan for this contract. He will ensure that
any necessary revisions are made and will check on implementation of the QA Plan during the course
of this project, scheduling performance and/or system audits as necessary. Dr. Fix will initiate and/or
followup on corrective actions. He will aid in preparation of a section of each Monthly Report
summarizing QA/QC activities which include estimates of precision, accuracy, and completeness of
the required data Audits conducted, quality problems identified, and corrective actions taken will be
described.
4.2 ANALYTICAL QC COORDINATOR'S RESPONSIBILITIES
Ms. Christine Johnson, the Analytical QC Coordinator, oversees and implements the ongoing
QC program. She will be responsible for the implementation of the analytical QC measures specified
in this Plan. She will review all QC sample results and incorporate them in the appropriate monthly
Analytical Results report. She will have overall responsibility for preparing the QC section of these
reports.
4.3 LABORATORY STAFF RESPONSIBILITIES
The Program Manager, Louis Macri, will have responsibility for meeting budget and schedule
commitments, as well as the technical quality of the work. He will also be the Laboratory contact for
the EPA Technical Monitor, Mikki Bolyard ((513) 569-7939). Working directly with Mr. Macri will be
John Verban Mr. Verban will be responsible for coordinating sample extraction with Mr. Doug
Buffington and analysis by GC. Mr. Verban will also be responsible for primary data review and
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Section No. 4
FtovMon No. 3
D«te: February 28, 1990
Page 2 of 3
initiation of bench level corrective action as well as being backup analyst for Ms. Kate Duffy who will
perform the majority of the analysis and data reduction.
Ms. Naomi Beck is responsible for sample receipt. The shipping address for samples is:
Clean Harbors Analytical Services, Inc.
213 Burlington Road
Bedford, Massachusetts 01730
Ms. Beck can be reached at (617) 275-6111.
Steve Cappello will be acting project coordinator, assuming the responsibilities previously
assigned to John Verban, from March 3, 1990 until the close of the project.
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Section No. 4
Revision No. 3
Date: February 28, 1990
Page 3 of 3
FIGURE 4-1
PROGRAM ORGANIZATIONAL CHART
HARBCFS
ED FTXARI
PRESIDENT
SERVICES
^A DIRECTOR
31 RIOSVFD
C3GRDIA1CR
Z-3US JCWGCN
DIVISICN
RIOAFD RAVEMEXLE
LABCEVMCFY
PROC7AM MWGER
LOJ1S
SMVUEBMK
MOB
TECHNZQL
GOGRSNPOCR
JQRI VEFBAN
3C SECTTCU
231
VBRBM4
— «ATC DUfTY
— CGUG BUFTOCICN
I
SAMPLE PREP.
'DOUG BUfPINbll
— KZLUf
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Section No. 5
Revision No. 3
Date: February 28, 1990
Pag* 1 of 2
5. QA OBJECTIVES FOR MEASUREMENT DATA
5.1 DETERMINATION OF ESTIMATED DETECTION LIMIT (EDL)
A determination will be made of the standard concentration necessary to produce an ECD
response with a 5/1 signal to noise ratio. Two anatyte mixes will then be prepared and used to spike
eight (8) pairs of reagent water samples. These samples will be prepared and analyzed as a batch.
The standard deviation (SD) will then be calculated using the following equation.
SD - / — ( E x - x) 2
where: n = the number of measurements for each anatyte
X = individual measured value in \igJL, and
x = average measured value in i*g/L
The minimum detection level (MDL) will then be computed by the following equation:
MDL = SD x 3.500 (Student's t value).
The estimated detection limit (EDL) equals either the concentration of analyte yielding a detector
response with a 5/1 signal to noise ratio, or the calculated MDL, whichever is greater. The EDLs,
determined in this manner, must be no greater than two times those determined during methods
development, as listed in Appendix A, Table 2.
The minimum reportable level, MRL, will be calculated using the following equation:
MRL = 5 x EDL
5.2 DETERMINATION OF GC/MS DETECTION LIMITS
Six analyses of each analyte mix will be performed by Multiple-ion detection (MID) GC/MS, using
the three ions specified by EPA (Appendix B). The results of these analyses will be used to determine
the concentration at which a 5/1 signal to noise ratio, for the least intense of the ions, is obtained.
5.3 CONSTRUCTION OF CONTROL CHARTS
Control charts will be used to demonstrate control of the measurement system. Control charts
will be generated upon completion of the initial determination of reporting limits. To establish the
control charts, 5 reagent water samples for each of the two analyte mixes will be spiked at ten times
the MRL and carried through the Method 2 extraction and analysis procedure. An additional 3 sets of
5 spiked reagent water samples will be similarly generated and analyzed on each of 3 days. The data
from all 20 samples will be used to construct the control chart The mean recovery (R) and standard
deviation (SD) will be calculated as follows:
SD = / — ( Z R-R)2
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Section No. 5
Revision No. 3
Date: February 28, 1990
Page 2 of 2
where: R( = the individual recovery value,
R = average recovery value, and
n = the number of measurements.
ACCEPTANCE CRITERIA FOR ACCURACY AND PRECISION WILL BE THE FOLLOWING:
• The RSD for analytes must be less than or equal to 20%, except where data, listed
in Appendix A, Table 2, indicates that poorer precision was obtained by Battelle in
the method validation. Technical monitors will determine action to be taken if
criteria are not met.
• The mean recovery (R) of each analyte must be within R plus or minus 3x SDs as
determined by Battelle, but no greater than plus or minus 30 percent.
• Initial surrogate recovery control will also be demonstrated on 20 samples.
Surrogate control charts will be generated to provide control limits for surrogate
recovery in samples.
• Warning limits of 2 standard deviations and control limits of 3 standard deviations
will be depicted on control charts for both laboratory control standards and
surrogates.
Dixon's test will be used to determine a maximum of three outliers per analyte from the 20
spiked reagent waters. Appendix C provides a discussion of Dixon's test.
Established control charts will be updated with spiked samples prepared with sets of spiked
reagent waters when data from 5 spikes are available. Data from the 5 earliest spiked samples will be
deleted, the precision and accuracy recalculated and the control chart redrawn.
5.4 FREQUENCY AND PROCEDURE FOR MATRIX SPIKING
During the survey, EPA will provide field samples from 10% of the sites for the laboratory to
assess the recoveries of spiked analytes from a variety of matrices. These samples are to be spiked
at analyte concentrations equal to 2, 5 or 10 times the MRL for each analyte. The required spiking
level will be specified on the sample label.
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Section No. 6
Revision No. 3
Dote: February 28, 1990
Page 1 of 3
6. SAMPLING PROCEDURES
All sampling for the National Pesticide Survey will be performed under the direction of ICF.
Clean Harbors will receive 1-liter water samples, preserved with 10 mg/L of mercuric chloride
preservative. Sample bottles will be shipped, iced, to the Clean Harbors laboratory in Bedford,
Massachusetts for analysis by Method 2. Clean Harbors will be responsible for notifying the Technical
Monitor if a sample box arrives without any ice remaining.
ICF will be responsible for the collection of duplicate samples at 10% of the sites for spiking at
Clean Harbors. All samples will be clearly labelled to differentiate field samples (FS), backup samples
(BU), lab spikes (LS), and time storage samples (T/S). The field label is reproduced in Figure 6-1. All
samples will be accompanied by a field sample tracking sheet, depicted in Figure 6-2.
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Section No 6
Revisiion No 3
Date February 28. 1990
Page 2 of 3
FIGURE 6-1
TONAL PESTICIDE -JUR'.'E'r
tt: PC-2226- 1-9-03
JMM - METHOD** 9 KIT: Hi
BACKUP SAMPLE
PRESERVATIVE: H2S04
DATE ! TIME 1 SAMPLER
MATTONAL PESTICIDE SURVEY
SAMPLE **: PC-^22o-l-9-Ol
JMM - METHOD** v i-.'IT: ill
FIELD SAMPLE
PRESERVATIVE: H2S04
DATE ! TIME ! SAMPLER
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Section No. 6
Revision No. 3
Date: February 28, 1990
Page 3 of 3
FIGURE 6-2
NPS FIELD SAMPLE TRACKING SHEET
HELL I.D. HO.: 0000
FRDS I.D. No. (CHS HELL ONLY):
SAMPLE COLLECTION DATE: / /
TRACKING FORM COMPLETES BY:
LAB: SSL
SCENARIO: J_
M7 N5.: PM-000-6U
: ICF
SAMPLE
N'UMBER
; Sj-OOOO-B-i-01
; FD-wOO-b-3-01
I PD-')uOQ-fc-c-01
! PC-WOO-6-i-v3
BOHLE
SHE
1000
1000
60
1000
SAMPLE
DESCRIPTION
FIELD SAMPLE
FIELD SAMPLE
FIELD SAMPLE
BACKUP SAMPLE
TO BE CuVLETEIi fit:
FIELD TEAM , uj
SAMPLER : TIRE . luMENI! ilj .?.£C£iV£i. CCMMENFS
(INITIAL) ! SAMPLE?
: : : . : »:
: : : . . N:
i ' .1
: : . • N;
CHLORINE TEST:
SHIPPED BY:
3 ATE TIME
SENT TO:
,
,
LAI ADDRESS:
BAY St. LlI.'IJ est'?«Mf3*":.l«TAL
: *ECE:VE:- AT LAB BY:
: :ATE TI-E
' :2K3ITICH {35
:HEHISTR» JM. :.•.:••. :i.-s :
,
NSTL. « r-srs
1
.1) FOR EXAMPLE: S3TT.E BRQCEH, BOTTLE MiSSIafi, OVERFL.E2 JCTTiE. fj» lAi I-^FEJ
;2) F>;» E1ANPLE: iGTTLE BSOXEK, BOTTLE HISSIN6. S3TrL£ :cu:uiu:r3. TE!ffE*ATUP.E CRITERIA NCT rET
. * •. era ctAHBir. »rr »ct rrr. c,n* !r»viuc
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Section No. 7
Revision No. 3
Dote: February 28, 1990
Page 1 of 5
7. SAMPLE CUSTODY
This section provides information concerning laboratory notification of sample schedule; EPA
requirements for holding times, storage conditions and disposal; Clean Harbors's system for sample
receipt and tracking, and for monitoring refrigerator temperatures where samples are stored.
7.1 NOTIFICATION OF LABORATORY
ICF will provide a printout of the sample shipment schedule for each upcoming 2-week period.
ICF will also maintain a sample tracking system into which Clean Harbors will enter data concerning
sample receipt.
7.2 HOLDING TIME, STORAGE AND DISPOSAL REQUIREMENTS
The maximum extraction holding time for field samples is 14 days from sample collection.
Analysis on primary and confirmatory columns must be completed within 14 days after extraction. The
maximum holding time for GC/MS extracts may be extended by the Technical Monitor to 28 days.
Data from samples extracted or analyzed outside the holding times shall not be submitted to the EPA,
nor shall compensation be received by the laboratory.
Extraction and analysis holding times for time storage samples will differ from holding times
required for field samples. Table 7.1 depicts holding time requirements for time storage samples and
extracts.
All samples and extracts will be stored in the dark at 4 degrees Centigrade. Refrigerator
temperatures must be verified and recorded on each working day.
Water samples will be disposed of after the 14-day holding time has been exceeded. Sample
extracts will be maintained until disposal is approved by the TSD or OPP Laboratory Coordinator. All
sample containers and boxes will be returned collect to the EPA or ICF.
7.3 CUSTODY PROCEDURES AT THE CLEAN HARBORS LABORATORY
Clean Harbors, Inc. maintains a Sample Log-in area to implement custody procedures and to
provide proper storage for all samples collected by, and/or submitted to Clean Harbors. The log-in
area is located in the laboratory and is staffed by the Sample Log-in Coordinator who reports to the
Program Manager. The Sample Log-in Coordinator accepts custody of all samples received by Clean
Harbors.
Upon receipt at Clean Harbors, each sample shipment is inspected to assess the condition of
the shipping container and the individual samples. The enclosed custody records are
cross-referenced with all the samples and sample tags in the shipment; the custody records are
signed by the Sample Log-in Coordinator and placed in the project file. The Sample Log-in
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Section No. 7
Revision No 3
Date February 28. 1990
Page 2 of 5
TABLE 7.1 HOLDING TIMES FOR TIME STORAGE SAMPLES
PleanHarbors
ipiking Extraction Analysis Re-anaiysis
Sample I.D. DATE (A) Date (B) Date (C) Date (D)
(HTE)
TSo (DTS) Day 0 to 13 Day A to Day B to Day B + 10 to
Time Storage Day A * 4 Day B+A Day 3*18
t»0 days
TSo (DTS) Day 0 to 13 Day A to Day B to Day B -10 to
(Time Storage Dup; Day A * 4 Day B * 4 Day B * 18
t « 0 days)
TS. (HTS) Day 0 to 13 Day A-10 to Day B to No re-analysis
(Time Storage; Day A «• 18 Day B * 4
t = 14 days)
TS., (HTS) Day 0 to 13 Day A+10 to Day B to No re-analysis
(Time Storage Dup; Day A - 18 Day B * 4
t * 14 days)
Note: Above dates assume collection is on Day -1 and receipt at
the laboratory on Day 0.
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Section No. 7
Revision No. 3
Date: February 28, 1990
Page 3 of 5
Coordinator continues the custody by assigning a Clean Harbors Control Number to each sample on
receipt; this number identifies the sample through all further handling.
The physical appearance of the individual sample containers upon arrival at Clean Harbors is
noted by the Coordinator. A sample is labeled in 'good* condition when the following criteria are met:
• Sample identification tags and seals are securely attached and legible, and agree
with other custody records; and
• Samples are iced.
Each sample is then recorded in the bound Master Sample Log under its Clean Harbors Control
Number. Each page of the handwritten Master Log has the following format:
• Clean Harbors Control Number;
• Sample Description;
• Sample Condition;
• Signature of person completing sample record; and
• Date of Sample Receipt.
Each analyst working with the sample, records in the Master Sample Log their initials thereby
enabling the tracking of the samples throughout the lab. Figure 7-1 shows the organic sample prep
record, which is used to track initial sample volume, final extract volume, sample holding times and
other pertinent sample information as listed on the form. When samples are sent to the client or to
another laboratory for analysis, the External Transfer of Custody Form (Figure 7-2) is used, and the
recipient of the samples is requested to return a copy of the signed form for the Sample files.
Clean Harbors, Inc. maintains large, locked, refrigerated, and nonrefrigerated storage areas with
provision for hazardous material storage. After logging and necessary preservation or subdivision, the
Sample Coordinator stores each sample in the appropriate area under its Clean Harbors Control
Number.
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Section No. 7
Revision No. 3
Date: February 28. 1990
Page 3 of 4
FIGURE 7-1
NATIONAL PESTICIDE SURVEY ORGANIC SAMPLE PREP RECORD
: 3-779-
Citrcction Holding li
(imp:
illitnce | |lniti*t | Firwl
Control | Type/ | SOTDle | Eitrvct
»o. | Site •/ | voluv j voluv
| lottle «|(«() | (.i)
1 1 1
1 1 1
1 1 I
1 1 1
1 1 1
t 1 1
1 1 1
1 II
I 1 1
1 1 1
1 1 1
1 1 1
1 1 1
1 1 1
t II
-— 1 1 1
1
10/vot. Soi*i "9
Solution
natrti | turroqcte
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
| Analyst'*
| netceooc
| l*(crfnce
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Section No. 7
Revision No. 3
Date: February 28, 1990
Page 4 o< 4
FIGURE 7-2
CHAIN OF CUSTODY RECORD
fleanHarfaor^
Cloon Mareorj AnaMical 213 Btfkngnn M Bootaro MA 01730
Cllont: Project laa»:
laoort To: AOMreaa:
CHAIN Of CUSTOOV PCCOAO
Sameia Cuanoan (SI71 ?75 6111 Page of
Proiact/P.O. *: n.r..
Phona i:
Invoice To: Addreaa:
Oat* Saeelo* Collected:
bv:
Alrblll/llll of lading? T • eOfl: Saa*>ie* received uvreeorvad Kill b* preaervad uxn arrival
••Kntiilalwa)
0*1*:
Sarapllnf Intoraaitlon
Data
ri«
Station location
Tl«a:
l*c*l««e) Bv:
Pat*:
tiaa:
IwclMd bvt
Pat*: tia»:
ttanaard laboratory tumarou* tlau la 2 waka
*aa*a*Ml a atrcnart*. *cc*larat*d turnaroiM
*aaa»la lypa
MM Klal
Claaa aottla
•laatle tut.
•ra,.
VOllM
Data Saaplaa loccivod:
at CMS. ia«pl« Mra: Pra«*rvad Urpraaarvcd
Knalvtla
•r««*rv«tlen lav: A • Acldf'lad vltft
1 - Mltarad, C • S«apJ» d)UI*d, p • KaCX,
I - Mfhloautfata, w • taapla i**l*nt. f • other
ton data o» receipt.
raojMtODl:
Acc*l*r*tM turnaround mtf «•
*
of
con.
CoaMnta
ISpacial inatructiona,
cautiana, ate.)
OtAJ Savplt
.
MNMKSi (Saapia atorae*. naratandard Maple battle*,
•peclal Imtructlona)
Location of ie«Dl
Turnarauid: 24 ari 48 an 1 M*k 2 Uxka Otlwr:
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Section No. 8
Revision No. 3
Date: February 28, 1990
Page 1 of 2
8. CALIBRATION PROCEDURES AND FREQUENCY
8.1 PREPARATION OF SURROGATE AND INTERNAL STANDARDS
EPA will provide neat reference materials for 4,4'-Dichlorobiphenyl (DCB) for use as a surrogate
standard and Pentachloronitrobenzene (PCNB) for use as an internal standard. Spiking solutions will
be prepared by accurately (+ 0.01 mg) weighing approximately 0.0050 grams of DCB and 0.001
grams of PCNP into two 10.0 ml volumetric flasks and diluting to volume then serially diluting 1:5 with
MTBE. Acetone will be used as solvent for DCB and MTBE for PCNB. Aqueous samples will be
spiked with 5.0 ul of the DCB solution, prior to extraction. All standards and blank and sample
extracts will be spiked to contain 0.1 ug/mL of PCNB (5.0 ul added to 1 mL of sample). All stock
solutions will be entered into the Pesticide Stock Solution Logbook and assigned a unique
identification number traceable to the date of preparation, analyst, lot number of the stock used and
volume taken for dilution.
8.2 PREPARATION OF INSTRUMENT QC STANDARD
EPA will provide ampuls of reference material diluted in MTBE for QC standard preparation. The
instrument QC standard will be prepared by diluting the four stocks to the following concentrations:
• Heptachlor epoxkje - 0.0040 ug/mL
DCPA - 0.050 ug/mL
• Chlorothatonil - 0.050 ug/mL
HCH-detta - 0.040 ug/mL
All stock solutions will be entered into the Pesticide Stock Solution Logbook and assigned a
unique identification number traceable to the date of preparation, analyst, date of receipt of the stock
used and volume taken for dilution.
An instrument QC standard will be analyzed daily, or with each sample set, whichever is more
frequent.
8.3 PREPARATION OF CALIBRATION STANDARDS AND LCS/TIME STORAGE SPIKING
SOLUTIONS
Calibration standards will be prepared from stock solutions provided by EPA in sealed ampuls.
Two intermediate stock solutions will be prepared containing approximately 15 analytes in MTBE
which do not co-elute on the primary GC column. Five dilutions will then be prepared from these
independent stocks. The lowest dilution must be prepared at the minimum reporting level (MRL), as
determined in Section 3.
LCS spiking solutions will also be prepared from stock solutions provided by EPA, The solution
will be prepared in acetone at a concentration which will generate component concentrations at I0x
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Section No. 8
Revteion No. 3
Date: February 28, 1990
Page 2 of 2
the MRL when 0.5 to 1.0 ml is added to 1 liter of reagent water. This solution will also be used to
spike time storage samples at 10x the MRL
All stock solutions will be entered into the QC Standard Stock Solution Logbook and assigned a
unique identification number traceable to the date of preparation, analyst, date of receipt of the stock
used and volume taken for dilution.
8.4 INSTRUMENT CALIBRATION
8.4.1 GC/ECD Analysis
Analysis will be performed on a Hewlett-Packard 5890 gas chromatograph, equipped with dual
electron capture detectors and a 7673 automatic liquid sampler, capable of simultaneous injection
onto primary and confirmatory columns.
A primary and confirmatory calibration curve will be generated at a minimum of three
(suggested five) concentration levels, including the MRL for each analyte. Qualitative analyses will be
performed for the following compounds, Endosulfan I, Endosulfan II, Delta-BHC and Chlorobenzilate.
The relative response of each analyte (RRa) to the internal standard will be tabulated using the
equation:
RRa = A/Ais,
where: A = the peak area of the analyte, and
Ais = the peak area of the internal standard.
The calibration curve will then be generated by plotting the analyte relative response, RRa, versus
analyte concentration in the sample in ug/L
The working calibration curve will be verified at alternating concentrations every 24 hours during
analysis of NFS samples; occasionally, that concentration will be the MRL The response for any
analyte must agree with the predicted response within 25%, or a new calibration curve will be
prepared. Each time new calibration standard dilutions are prepared, they must be compared to the
existing calibration curve, and the observed concentration must agree within 25% of the expected
concentration.
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Section No. 9
Revision No. 3
Date: February 28, 1990
Page 1 of 4
9. ANALYTICAL PROCEDURES
Samples submitted to Clean Harbors by U.S. EPA from the National Pesticide Survey will be
prepared and analyzed in accordance with the October 27, 1987 version of Method 2 (Appendix A).
No deviations from this procedure will be made with respect to the following: reagents (Section 7)
apparatus and equipment (Section 6), procedure (Sections 11.2 and 12.3) and data reduction (Section
12). One deviation occurs in glassware cleaning (Section 4.1.1) with the replacement of heating
glassware at 400oC by a terminal acetone rinse. This procedure has been demonstrated to provide
glassware of a suitable quality at the Clean Harbors laboratory. Further precautions include the
segregation of glassware for the NPS analysis. The maximum number of samples (including QC) that
will be extracted and analyzed as a set is fifteen (15).
All samples submitted to Clean Harbors under this program for analysis via this method, as well
as method blanks, matrix spikes and laboratory control samples, will be preserved with mercuric
chloride, surrogate-spiked with 4,4'-Dichlorobiphenyl (DCB), buffered to pH 7, mixed with 100 g NaCI
and extracted in a 2-liter separatory funnel with methylene chloride. The methylene chloride extracts
from each of three extractions will be combined, dried over anhydrous sodium sutfate and
concentrated via Kudema-Danish apparatus to approximately 2 mL The extract will then be solvent
exchanged into methyl-t-butyl ether (MTBE) for gas chromatographic analysis.
The analysis for the compounds listed in Table 9-1 will be performed using a Hewlett-Packard
5890 gas chromatograph, equipped with dual Ni63 electron capture detectors and dual automatic
liquid samplers. This GC will be interfaced to a Hewlett-Packard 3359 data acquisition system. As
stated in Method 2, separation will be performed using an SPB-5 capillary column for primary analysis
and a DB-1701 for confirmatory analysis. Table 9.2 provides chromatographic conditions for this
analysis.
Prior to the injection of program samples, each gas chromatograph will be calibrated at three to
five concentration levels with the components of interest. Calibration solutions will also contain the
internal standard, PCNB. Calibration curves will be generated plotting the analyte concentration
versus relative response to the internal standard. Each sample extract will also be spiked with internal
standard solution prior to gas chromatographic analysis. Concentrations of anarytes in the samples
will be determined from the relative response to the internal standard via the calibration curve. The
analyst will monitor internal standard (IS) area count responses for all sample injections. A deviation
in a sample of greater than 30 percent of the average IS response of the calibration standards
indicates the possibility from method or matrix interferences with internal standard measurement.
Appendix A, Section 10.6.2 addresses analysis of QC check standards. This is not required by
the NPS protocol and therefore not done. Section 10.7.1, referring to spiking of the target anarytes
into ten percent of the samples was met by the NPS survey design with the LSS samples.
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Section No. 9
Revieion No. 3
Date: February 28, 1990
Page 2 of 4
The automated data entry system was implemented on November 16, 1989. Its application
began with set 126 and continued until the final set.
-------
Section No. 9
Revision No. 3
Date: Februwy 28,1990
Page 3 of 4
TABLE 9-1
ANALYTES INCLUDED IN GROUND WATER ANALYSIS METHOD 2,
MIX A AND MIX B WITH MRL AND MDL DATA
A. Mix A
Chlorneb
Propachlor
Alpha-BHC
Gamma-BHC
Chlorthalonil
Aldrin
Heptachlor epoxide
* Endosulfan I
Dieldrin
Endrin
* Endosulfan II
Endrin Aldehyde
p.p'-DDT
Cis-permethrin
B. MixB
Ethridiazole
Trifluralin
Hexachlorobenzene
Beta-BHC
* Delta-BHC
Heptachlor
DCPA
Qamma-Chlordane
Alpha-Chlordane
p,p'-DDE
* Chlorbenzilate
p,p'-DDD
Endosulfan Sulfate
Methoxychlor
Trans-Permethrin
MRL
1.4
1.3
0.12
0.085
0.12
0.12
0.12
0.12
0.12
0.25
0.25
0.25
0.3
1.8
MRL
0.25
0.25
0.12
0.12
0.12
0.12
0.12
0.12
0.12
0.12
0.68
0.25
0.25
0.6
3.9
MDL
0.276
0.261
0.012
0.107
0.017
0.021
0.022
0.019
0.025
0.033
0.029
0.033
0.06
0.36
MDL
0.002
0.005
0.005
0.009
0.005
0.01
0.016
0.007
0.008
0.007
0.136
0.015
0.013
0.111
0.779
* Qualitative analysis only.
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Section No. 9
Revteion No. 3
Deto: February 28, 1990
Page 4 of 4
TABLE 9-2
INSTRUMENT CONDITIONS FOR ANALYSIS OF GROUND WATER BY METHOD 2
Primary Conditions
Column:
Injection volume:
Carrier gas:
Injector temp:
Oven temp:
Confirmation Conditions
Column:
Injection volume:
Carrier gas:
Injector temp:
Oven temp:
30 m x 0.25 mm I.D. SPB-5 bonded fused silica column,
0.25 m film thickness (J&W)
2 uL splitless with 45 second delay
He 30 cm/sec linear velocity
250oC
Program from 60<>C to 300«C at 4<>C/min
30 m x 0.25 mm I.D. DB-1701 bonded fused silica column,
0.25 m film thickness (J&W)
2 uL splitless with 45 second delay
He 30 cm/sec linear velocity
250oC
Program from 60oC to 300°C at 4<>c/min
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Section No. 10
Revision No. 3
Date: February 28, 1990
Page 1 of 3
10. DATA REDUCTION, VALIDATION AND REPORTING
Proper collection and organization of accurate information followed by clear and concise
reporting of the data is a primary goal in all projects. This section describes the procedures routinely
followed at Clean Harbors for data reduction, validation and reporting. All hard copy data of
chromatograms, prep records, etc. will be stored together in the project file.
10.1 DATA REDUCTION
Analytical results will be reduced to concentration units specified in Method 2, using the
equations given therein. Actual blank values will be reported; blank corrections will not be applied.
10.2 DATA VALIDATION
Data validation is the process of filtering data and accepting or rejecting it on the basis of sound
criteria. Analytical supervisory and QC personnel will use validation methods and criteria appropriate
to the type of data and the purpose of the measurement. Records of all data will be maintained, even
that judged to be an 'outlying* or spurious value. The persons validating the data will have sufficient
knowledge of the technical work to identify questionable values. All chromatograms will be reviewed
by Clean Harbors's GC Section Head to ensure proper compound identification and as a general
quantitation check. Furthermore, approximately 25 percent of calculations and data transfer will be
checked during validation. If any errors are found, all calculations or data transfer of that type will be
checked.
Analytical data will be validated by the laboratory QC coordinator or supervisory personnel using
criteria specified and in this QA Plan. Clean Harbors routinely uses results from laboratory reagent
blanks, replicate samples and internal QC samples to validate analytical results. Generic criteria used
to evaluate analytical data are listed below:
• Use of approved analytical procedures;
• Use of property operating and calibrated instrumentation;
Acceptable results from analyses of Lab Control samples; and
• Precision and accuracy meeting QA objectives as stated in the methods and this
QA Plan.
10.3 FAST TRACK REPORTING
Since normal reporting requirements allow sample data to be provided 2 months after sample
collection, a mechanism for fast track reporting is necessary. Reports to the Technical Monitor will be
expedited when the following situations arise:
• Confirmed positives for a list of analytes to be specified by EPA.
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Section No. 10
Revision No. 3
Date: February 28, 1990
Page 2 of 3
• Lack of agreement of + 25 percent between results from primary and confirmatory
analysis by GC/ECO.
• Frequent occurrence of a peak or peaks which are not NFS analytes (excluding
pnthalates), or which are at levels between the EDL and MRL (no quantitation or
confirmation is performed).
• Refer to Rapid Reporting Memo of June 9, 1989 - Appendix J
10.4 DATA REPORTING
A flow chart depicting the analytical data validation and reporting scheme, routinely used at
Clean Harbors, is shown in Figure 10-1. Validation occurs at a minimum of two levels. For this
program, the Technical Coordinator, John Verban, will review all QC data as soon as possible. He will
initiate sample re-extraction if project QC criteria are not met. A second review by the Project
Manager will take place prior to final reporting of the data
All data for a set of samples, including QC and confirmatory data, will be reported by the
laboratory as a complete set. Data must be provided within 2 months of sample collection. Data are
to be provided as an ASCII file in the format specified by EPA on floppy disk. Hard copies of all data
will be kept with the project file by set number.
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Section No. 10
Revision No. 3
Date: February 28, 1990
Page 3 of 3
FIGURE 10-1
CLEAN HARBORS ANALYTICAL DATA VALIDATION AND REPORTING SCHEME
-°
r T
.^» .i« s. „
- A * A
r T
?REC:S:CN AND i
"X'l/" *™^^^t»Q* •"
-.lAC-i.- ..-Oui
i. » 3 AT A ,
ECISSARY
r
7ROC&I3 -ITH 2A7A i
•£Ducr:2s. REPORT ;
ALL VALLTS IN ;
APPROPRIATE 'JtJITS
T r
FRCJECT FIL£
2.
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Section No. 11
Reviaion No. 3
Date: February 28, 1990
Page 1 of 3
11. INTERNAL QUALITY CONTROL CHECKS
Quality control checks will be performed to ensure the generation of valid analytical results on
these samples. These checks as listed in Table 11.1 will be performed by appropriate personnel
throughout the program under the guidance of the QA Director and the Laboratory QC Coordinator. A
brief description of each of these elements is provided below.
11.1 METHOD BLANKS
Method blanks will be preserved with mercuric chloride and contain all the reagents used in the
preparation and analysis of samples. Method blanks are processed through the entire analytical
scheme to assess spurious contamination arising from reagents, glassware and other materials used
in the analysis. A method blank is processed with each set of samples extracted. If the method blank
exhibits a peak for any analyte (on both columns) which is greater than or equal to one-half the MRL,
the source of contamination must be determined and the sample set re-extracted.
11.2 CALIBRATION CHECK SAMPLES
A working calibration standard at alternating concentrations (occasionally at MRL) which is
repeated every 24 hours to verify the working calibration curve. If the response for any analyte varies
from the predicted response by more than 25%, a new calibration curve must be prepared for that
analyte.
11.3 REPLICATE AND SPIKED SAMPLES
Additional samples will be collected at 10% of the sample sites for spiking at the laboratory.
These samples are to be spiked at analyte concentrations equal to 2x, 5x, or 10x the MRL (level
specified on sample label). Samples for replicate analysis will also be submitted at the required
frequency.
11.4 LABORATORY CONTROL SAMPLES
A laboratory control sample must be prepared with preservative and analyzed with each set of
samples extracted. For Method 2, this will consist of two reagent water samples, each spiked with
one of the two calibration mixes, independently prepared in acetone. The concentration of these
samples will be 10x the MRL
An 'out of control" situation exists if more than 15 percent of the LCS analyte recoveries are
outside the control limit (3 standard deviations), or if the same analyte is outside the control limit twice
in a row. All analytical work must be stopped until control is re-established. Re-extraction of that
set/batch of samples is required.
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Section No. 11
Revision No. 3
Date: February 28, 1990
Page 2 of 3
TABLE 11.1
INTERNAL QC CHECKLIST
Is the instrument control standard's signal to noise ratio greater than the limit the method specifies?
Is the instrument control standard's peak symmetry, resolution and geometry factors within the limit
set by the method?
Is the date from sampling to receipt within the limits set by the survey requirements?
Is the date from sampling to extract within the limits set by the survey requirements?
Is the date from extract to analysis within the limits set by the survey requirements?
Is the percent recovery of the surrogate in the LCS within the Control Chart limits?
Is the concentration of a blank above half of the MRL?
Is the concentration of a field sample above 1/2 the minimum reporting limit?
A. If so, is there a confirmation analysis for the analyte?
B. Is the concentration of the confirmatory column within the limits set by survey
requirements?
Is the percent recovery of each analyte in the lab control standard within the upper and lower control
limits?
Is the percent recovery of each analyte in the lab spike sample within the upper and lower control
limits?
Is the percent recovery of each analyte in the performance evaluation sample within the limits set by
the survey requirements?
Is the internal standard area within + 30% from the average IS response of the calibration standards?
Does the calibration check standard compare within 25% of the Initial calibration curve?
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Section No. 11
Revision No. 3
Date: February 28, 1990
Page 3 of 3
11.5 SURROGATE SPIKES
All samples, blanks and laboratory control standards will be fortified with DCB before extraction.
A surrogate standard determination must be performed on all samples (including matrix spikes) and
blanks. The acceptance criteria for surrogate standard recoveries are +. 3 sigma for the lab control
samples and ± 30% from the mean as determined from the current control chart for all other sample
types. Control charts for surrogate recoveries in the LCS will be prepared and updated as detailed in
Section 3.3 When the surrogate recovery for a sample is outside control limits, the laboratory must
establish that the deviation is not due to laboratory problems. The laboratory shall document
deviations by taking the following actions:
(1) Checking calculations to make sure there are no errors.
(2) Checking internal standard and surrogate standard spiking solutions for
degradation, contamination, or other obvious abnormalities.
(3) Checking instrument performance.
Recalculation or reanalysis of the sample or extract will be performed if the above steps fail to reveal
the cause of the noncompliant surrogate recoveries. If reanalysis of the sample or extract solves the
problem, only the sample data from the analysis with surrogate spike recoveries within the required
limits will be submitted. If reanalysis of the sample extract fails to solve the problem, then both sets of
data for that sample will be reported.
If the surrogate recovery for an LCS is outside the control limits, then the analyst must evaluate
the sample set for blank surrogate recovery and LCS analyte recovery. The sample set/batch must be
re-analyzed only if the blank surrogate recovery or the LCS analyte recoveries do not meet
acceptance criteria
If the surrogate recovery for a method blank is outside the control limits, then the analyst must
check the sample set/batch for a sample free from analyte positives (i.e. a blank). If the surrogate
recovery from that sample meets criteria, then analysis of the set can proceed.
11.6 INTERNAL STANDARD CHECKS
Internal standard areas will be evaluated for acceptance by determining whether the measured
peak area or height in any sample deviates by more than 30% from the average for the internal
standard in the calibration standards. Corrective action for internal standard area count deviations is
detailed in Appendix A, Section 10.5.3.
11.7 INSTRUMENT QUALITY CONTROL STANDARDS
Instrument QC standards will be evaluated according to Table 10 in Appendix A for detection,
peak symmetry, resolution and peak Gaussian factor using the calculations provided with the table.
Analysis will not be performed if criteria are not met
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Section No. 12
RwWonNo. 3
Date: February 28,1990
Pago 1 of 1
12. PERFORMANCE, SYSTEM AND DATA AUDITS
12.1 DATA AUDITS
Ongoing data audits will be provided by the project coordinator, project manager or Laboratory
QC Coordinator. These audits will consist of a verification of 25% of the calculations generated under
this program and of all positive identifications.
12.2 SYSTEMS AUDITS
A system audit is a qualitative review to ensure that the quality measures and the analytical
procedures outlined in the QA Project Plan are in place and being followed. Clean Harbors's QA
Director selects projects representing different types of measurement activities for audit by the QA
staff. System audits of analytical work on this program will be scheduled in accordance with the
volume and diversity of the samples received, and the severity and number of problems uncovered in
early system audits but at a minimum will be held quarterly. Written summary reports for each audit
will be submitted as noted in Section 14.0.
12.3 EXTERNAL AUDITS
Clean Harbors will cooperate fully in any performance or system audits conducted or arranged
by EPA. The Project Manager, QA Director and QC Coordinator are available to aid in scheduling
such audits.
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Section No. 13
Revtoion No. 3
Date: February 28, 1990
Page 1 of 1
13. PREVENTIVE MAINTENANCE
Clean Harbors follows an orderly program of positive actions to prevent the failure of equipment
of instruments during use. In the analytical laboratories, preventive maintenance includes attention to
glassware, water supply, reagents and analytical balances as well as more complex instrumentation.
Table 13-1 summarizes the preventive maintenance procedures for the instruments to be used in this
project. Also listed in the table are the spare parts normally kept in inventory to minimize instrument
down time.
TABLE 13-1
MAINTENANCE PROCEDURES AND SCHEDULE FOR MAJOR INSTRUMENTATION
Instrument
Maintenance Procedure/Schedule
Spare Parts
Gas Chromatograph
(HP5890)
1. Change septa daily.
2. Check syringe for burrs daily.
3. Change gas line dryers quarterly.
4. Leak check when installing new analytical
column.
5. Periodically check inlet system for residue build-
up.
1. Syringes
2. Septa
3. Columns
Gas Chromatographs/
Mass Spectrometers
(Hewlett Packard 5970)
1. Replace pump oil annually.
2. Change septa daily.
3. Change gas line dryers quarterly.
4. Replace Electron Multiplier as needed.
1. Syringes
2. Septa
3. Column
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Section No 14
Revision No 3
Date February 28 1990
Page 1 of 1
14. SPECIFIC PROCEDURES FOR ASSESSING MEASUREMENT SYSTEM DATA
Compare the percent recovery (Ri) for each analyte with established QC acceptance criteria.
QC criteria are established by initially analyzing twenty (20) laboratory control standards and
calculating the average percent recovery (R) and the standard deviation of the percent recovery (SD)
using the following equations:
T— n
SD / — (I, R, - R )
n-1 1 = 1
where: n = the number of measurements for each analyte,
R( = individual percent recovery, and
R = average percent recovery.
The QC acceptance criteria is calculated as follows:
Upper Control Limit (UCL) = R + 3SD
Lower Control Limit (LCL) = R - 3SD
Upper Warning Limit (UWL) = R + 2SD
Lower Warning Limit (LWL) = R - 2SD
The data generated during the initial demonstration of capability (3.3) will be used to set the
initial upper and lower control and warning limits.
The performance criteria will be updated on a continuous basis. After each five new recovery
measurements, R and RSD will be recalculated using all the data, and new control charts
reconstructed, deleting the five earliest values. Qixon's Test (Appendix C) will be applied where
appropriate. Spiked samples will be corrected for concentrations of analytes native to that sample if
the analyte is present at > 1/2 the MRL
The instrument QC standard will be assessed using the calculations provided in Table 10
(Appendix A). Accuracy will be estimated from the analysis of laboratory control samples, and will be
expressed as percent recovery. The formula used to calculate percent recovery is as follows:
measured value
Percent Recovery = 100 x
true value
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Section No. 15
Revtoion No. 3
Date: Februwy 28, 1990
Page 1 of 4
15. CORRECTIVE ACTION
The acceptance limits for the analyses to be conducted in this program will be generated as
stated in Section 3. The corrective actions are likely to be immediate in nature and most often will be
implemented by the analyst or technical coordinator. The corrective action will usually involve
recalculation, or reanalyses. Clean Harbors' ongoing corrective action policy is described here.
15.1 IMMEDIATE CORRECTIVE ACTION
Specific QC procedures are designed to help analysts detect the need for corrective action.
Often the person's experience will be more valuable in alerting the analyst to suspicious data or
malfunctioning equipment. Instrument and equipment maffunctions are amenable to immediate
corrective action. The actions taken should be noted in laboratory notebooks, but no other formal
documentation is required, unless further corrective action is necessary. These on-the-spot corrective
actions are an everyday part of the QA/QC system. An example of bench level corrective action is
provided in Figure 13-1. This reextraction request will usually be initiated by the Technical
Coordinator. Additional corrective actions will be noted in instrument maintenance log books and
analysts' notebooks. These data will be filed in the project file to facilitate monthly reports about
bench-level problems to the EPA Technical Monitor that include the date, problem, action taken,
verification that the problem was solved, and identification of the sample sets analyzed just prior to
and immediately following the corrective action.
If a corrective action can be taken at this point, as part of normal operating procedures, the
collection of poor quality data can be avoided. If a problem is not solved in this way, more formalized
long-term corrective action may be necessary.
15.2 LONG-TERM CORRECTIVE ACTION
The need for this action may be identified by standard QC procedures, control charts,
performance or system audits. Any quality problem which cannot be solved by immediate corrective
action falls into the long-term category. Appropriate corrective actions may be similar in nature to
immediate corrective action; i.e., collecting a new set of samples or reanalyzing samples, but the
correction may proceed more slowly. Clean Harbors uses a system to ensure that the condition is
reported to a person responsible for correcting it who is part of the closed-loop action and follow-up
plan. The essential steps in the closed-loop corrective action system are:
Identify and define the problem.
• Assign responsibility for investigating the problem.
• Investigate and determine the cause of the problem.
• Determine a corrective action to eliminate the problem.
-------
Section No. 15
Revision No. 3
Date: February 28, 1990
Page 2 of 4
FIGURE 15-1
NATIONAL PESTICIDE SURVEY
Sample Re-extraction Worksheet
Date of Request: Requested by:
Charge Number: 3-729-
The following samples require re-extraction and analysis:
Clean Harbor Control Number Sample Identification Problem Code Holding Time Expiration
A LC sample recovery outside control limits.
B Sample surrogate recovery outside control limits.
C Method blank surrogate recovery outside control limit
0 Method blank contamination at 50% of EDL
E Matrix spike recovery outside control limits.
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Section No. 15
Revision No. 3
Date: February 28, 1990
Page 3 of 4
• Assign and accept responsibility for implementing the corrective action.
• Establish effectiveness of the corrective action and implement it.
• Verify that the corrective action has eliminated the problem.
Documentation of the problem is important to the system. A Corrective Action Request Form
(shown in Figure 15-2) is filled out by the person finding the quality problem. This form identifies the
problem, possible causes and the person responsible for action on the problem. The responsible
person may be an analyst, field team leader, QC Coordinator or the QA Director. If no person is
identified as responsible for action, the QA Director investigates the situation and determines who is
responsible in each case.
The Corrective Action Request Form includes a description of the corrective action planned and
the date ft was taken, and space for follow-up. The QA Director checks to be sure that initial action
has been taken and appears effective and, at an appropriate later date, checks again to see if the
problem has been fully solved. The QA Director receives a copy of all Corrective Action Forms and
then enters them in the Corrective Action Log. This permanent record aids the QA Director in
follow-up and makes any quality problems visible to management; the log may also prove valuable in
listing a similar problem and its solution.
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Section No. 15
Revision No. 3
Date: February 28, 1990
Page 4 of 4
FIGURE 15-2
CORRECTIVE ACTION REQUEST FORM
Corrective Action Request Form No.
Originator Date
Person Responsible for Replying Contract Involved
Description of problem and when identified:
State cause of problem, if known or suspected:
Sequence of Corrective Action: (If no responsible person is identified, bring this form directly to QA
Director.)
State Date, Person, and Action Planned:
CA Initially Approved By: Date:
Follow-up Dates:
Final CA Approval By: Date:
Information copies to:
RESPONSIBLE PERSON:
QA DIRECTOR:
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Section No. 16
Revtolon No. 3
Date: February 28,1990
Page 1 of 1
16. QA REPORTS
16.1 INTERNAL REPORTS
The QC Coordinator will prepare written monthly reports on QC activities for the Laboratory
Manager and the QA Director. These reports detail the results of quality control procedures, problems
encountered, and any corrective action which may have been required. As these reports pertain to
this project, they will be made available to the Program Manager and QA Officer.
All Corrective Action Forms are submitted to the QA Officer for initial approval of the corrective
action planned and a copy is provided to the Program Manager. All system audit reports are provided
to the Program Manager and may be presented to the Clean Harbors President.
16.2 EXTERNAL REPORTS
Six copies of the monthly report will be provided within 15 (calendar) days after the end of the
period being reported. The copies will be sent to the appropriate EPA Technical Monitor.
A copy of the cover letter which transmits the monthly report will be forwarded to Mona S.
Snyder, Contract Specialist for the NPS, EPA-CMD, Cincinnati, OH 45268.
The report format will contain the following information for the report period:
• Summary of progress
samples received, analyzed, in progress
- status of data processing for analyzed sets of samples
• Reports on standards
- new dilutions and results of check before using
• Summary list of bench-level corrective action
• Identification of problems about any phase of the project
• Copies of representative and, if applicable, unusual chromatograms.
• Information requested by the Technical Monitor because of specific methodology or
problems encountered
• Changes in personnel
• Any other comments.
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Section No. 17
Ftevtoion No. 3
Date: February 28, 1990
Pag« 1 of 1
17. ARCHIVAL OF RAW DATA
NPS ARCHIVAL PROCESS
1. The NPS data sets will be stored at the Clean Harbors of Bedford facility at 213
Burlington Road, Bedford, MA 01730 for a period of one year from the closeout
audit date of August 30,1990. After one year the data will be transferred to Clean
Harbors' warehouse at 10 Mercer Road, Natick, MA 01760. The data will remain at
this site for a period of seven years from the closeout audit date of August 30, 1990.
Laurian Carroll, Documents Manager for Clean Harbors, is responsible for all data
stored in the warehouse. After the seven year period, the data will be disposed of
unless otherwise requested by the EPA.
2. Each data set consists of the following:
2.1 Copy of the formattable
2.2 Copy of the ICDS
2.3 Copy of Clean Harbors' Chain of Custody
2.4 Copy of GC injection log run sheet
2.5 Copy of extraction log sheet
2.6 Copy of drying and concentrating log sheet
2.7 Internal Standard summary
2.8 Continuing Calibration
2.9 Standard curve data including retention time window data
2.10 Raw areas, concentrations, and percent recoveries for samples
2.11 Flag data for determining outliers
2.12 Internal Quality Control Check
2.13 GC chromatograms for standards and samples
2.14 Hand calculations and notes on set
3. The following information is archived in labeled boxes and will follow the same
storage procedures as the data sets.
3.1 Initial demonstration of capability
3.2 Index for EPA well ID number versus Clean Harbors' set number
3.3 Data sets 1 through 153
3.4 Copies of standard logbook pages
3.5 Copies of refrigerator logbook pages
3.6 Sample tracking forms
3.7 In-house audits
3.8 Corrective action forms
3.9 Monthly reports
3.10 Copies of instrument maintenance logbook pages
3.11 Standard Operating Procedure for NPS
3.12 Control Charts for Quality Control Limit
3.13 Statement of Qualification and copies of resume's for employees involved in NPS
3.14 Correspondence
3.15 Standard comparisons
3.16 NPS check lists for each set
3.17 NPS sample analysis tracking logbook
3.18 QA Plan for NPS
4. To access data by EPA well number, the Clean Harbors identification number and
data set that the number is grouped in must be determined. The index found in first
data set box can be used to determine the set number for any corresponding EPA
well number. The appropriate set should be obtained and the necessary
information for the sample can be acquired.
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APPENDIX A
METHOD 2. DETERMINATION OF CHLORINATED PESTICIDES IN
GROUND WATER BY GAS CHROMATOGRAPHY WITH AN ELECTRON CAPTURE DETECTOR
1. SCOPE AND APPLICATION
1.1 This is a gas chromatographic (GC) method applicable to the determination of certain
chlorinated pesticides in ground water. Analytes that can be determined by this method
are listed in Table 1.
1.2 This method has been validated in a single laboratory. Estimated detection limits (EDL's)
have been determined and are listed in Table 2. Observed detection limits may vary
between ground waters, depending upon the nature of interferences in the sample matrix
and the specific instrumentation used.
1.3 This method is restricted to use by or under the supervision of analysts experienced in
the use of GC and in the interpretation of gas chromatograms. Each analyst must
demonstrate the ability to generate acceptable results with this method using the
procedure described in Section 10.2.
2. SUMMARY OF METHOD
2.1 A measured volume of sample of approximately 1L is solvent extracted with methylene
chloride by mechanical shaking in a separatory funnel or mechanical tumbling in a bottle.
The methylene chloride extract is isolated, dried and concentrated to a volume of 5 mi-
after solvent substitution with methyl tertbutyl ether (MTBE). Chromatographic conditions
are described which permit the separation and measurement of the analytes in the
extract by GC with an electron capture detector (ECD).
2.2 An alternative manual liquid-liquid extraction method using separatory funnels is also
described.
3. DEFINITIONS
3.1 Artificial ground water - an aqueous matrix designed to mimic a real ground water
sample. The artificial ground water should be reproducible for use by others.
3.2 Calibration standard - a known amount of a pure anaryte, dissolved in an organic
solvent, analyzed under the same procedures and conditions used to analyze sample
extracts containing that anaryte.
3.3 Estimated detection limit (EDL) - the minimum concentration of a substance that can be
measured and reported with confidence that the anaryte concentration is greater than
zero as determined from the analysis of a sample in a given matrix containing the
analyte. The EDL is equal to the level calculated by multiplying the standard deviation of
replicate measurements times the student's t value appropriate for a 99 percent
confidence level and a standard deviation estimate with n-1 degrees of freedom or the
level of the compound in a sample yielding a peak in the final extract with signal-to-noise
ratio of approximately five, whichever is higher.
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3.4 Instrument quality control (QC) standard - a MBTE solution containing specified
concentrations of specified analytes. The instrument QC standard is analyzed each
working day prior to the analysis of sample extracts and calibration standards. The
performing laboratory uses this solution to demonstrate acceptable instrument
performance in the areas of sensitivity, column performance, and chromatographic
performance.
3.5 Internal standard - a pure compound added to a sample extract in a known amount and
used to calibrate concentration measurements of other analytes that are sample
components. The internal standard must be a standard compound that is not a sample
component.
3.6 Laboratory control (LC) standard - a solution of analytes prepared in the laboratory by
dissolving known amounts of pure anaiytes in a known amount of reagent water. In this
method, the LC standard is prepared by adding appropriate volumes of the appropriate
standard solution to reagent water.
3.7 Laboratory method blank - a portion of reagent water analyzed as if it were a sampJe.
3.8 Performance evaluation sample - a water-soluble solution of method analytes distributed
by the Quality Assurance Branch, Environmental Monitoring and Support Laboratory,
USEPA, Cincinnati, Ohio. A small measured volume of the solution is added to a known
volume of reagent water and analyzed using procedures identical to those used for
samples. AnaJyte true values are unknown to the analyst.
3.9 Quality control check sample - a water soluble solution containing known concentrations
of analytes prepared by a laboratory other than the laboratory performing the analysis.
The performing laboratory uses this solution to demonstrate that it can obtain acceptable
identifications and measurements with a method. A small measured volume of the
solution is added to a known volume of reagent water and analyzed with procedures
identical to those used for samples. True values of analytes are known by the analyst.
3.10 Stock standard solution - a concentrated solution containing a certified standard that is
a method analyte, or a concentrated solution of an analyte prepared in the laboratory
with an assayed reference compound.
3.11 Surrogate standard - a pure compound added to a sample in a known amount and
used to detect gross abnormalities during sample preparation. The surrogate standard
must be a compound that is not a sample component
4. INTERFERENCES
4.1 Method interference may be caused by contaminants in solvents, reagents, glassware
and other sample processing apparatus that lead to discrete artifacts or elevated
baselines in gas chromatograms. All reagents and apparatus must be routinely
demonstrated to be free from interferences under the conditions of the analysis by
running laboratory method blanks as described in Section 10.8.
4.1.1 Glassware must be scrupulously deaned.2 Clean all glassware as soon as possible
after use by thoroughly rinsing with the last solvent used in it. Follow by washing
with hot water and detergent and thorough rinsing with tap and reagent water.
Drain, dry, and heat in an oven or muffle furnace at 400oC for 1 hour. Do not heat
volumetric ware. Thermally stable materials such as PCB's might not be eliminated
by this treatment Thorough rinsing with acetone may be substituted for the
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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 Interference by phthalate esters can pose a major problem in pesticide analysis when
using the electron capture detector. These compounds generally appear in the
chromatograms as large peaks. Common flexible plastics contain varying amounts of
phthalates that are easily extracted or leached during laboratory operations. Cross
contamination of clean glassware routinely occurs when plastics are handled during
extraction steps, especially when solvent-wetted surfaces are handled. Interference from
phthalates can best be minimized by avoiding the use of plastics in the laboratory.
Exhaustive cleanup of reagents and glassware may be required to eliminate background
phthalate contamination.3,4
4.3 Interfering contamination may occur when a sample containing low concentrations of
analytes is analyzed immediately following a sample containing relatively high
concentrations of analytes. Between sample rinsing of the sample syringe and
associated equipment with MBTE can minimize sample cross contamination. After
analysis of a sample containing high concentrations of analytes, one or more injections of
MBTE should be made to ensure that accurate values are obtained for the next sample.
4.4 Matrix interferences may be caused by contaminants that are coextracted from the
sample. The extent of matrix interferences will vary considerably from source to source,
depending upon the ground water sampled. Cleanup of sample extracts may be
necessary. Positive identifications must be confirmed using the confirmation column
specified in Table 3.
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 awareness file of OSHA regulations regarding the safe handling of
the chemicals specified in this method. A reference file of material safety data sheets
should also be made available to all personnel involved in the chemical analysis.
Additional references to laboratory safety are available and have been identified 5-7 for
the information of the analyst.
6. APPARATUS AND EQUIPMENT (All specifications are suggested. Catalog numbers are
included for illustration only.)
6.1 SAMPLING EQUIPMENT
6.1.1 Grab sample bottle - Borosilicate, 1-L volume with graduations (Wheaton
Media/Lab bottle 219820), fitted with screw caps lined with TFE-fluorocarbon.
Protect samples from light. The container must be washed and dried as described
in Section 4.1.1 before use to minimize contamination. Cap liners are cut to fit from
sheets (Pierce catalog No. 012736) and extracted with methanot overnight prior to
use.
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6.2 GLASSWARE
6.2.1 Separatory funnel - 2000 ml_ with TFE-fluorocarbon stopcock, ground glass or
TFE-fluorocarbon stopper.
6.2.2 Tumbler bottle - 1.7-L (Wheaton Roller Culture Vessel), with TFE-fluorocarbon lined
screw cap. Cap liners are cut to fit sheets (Pierce Catalog No. 012736) and
extracted with methanol overnight prior to use.
6.2.3 Flask, Erlenmeyer - 500-mL
6.2.4 Concentrator tube, Kudema-Danish (K-D) - 10- or 25-mL, graduated (Kontes
K-570050-1025 or K-570050-2525 or equivalent). Calibration must be checked at
the volumes employed in the test. Ground glass stoppers are used to prevent
evaporation of extracts.
6.2.5 Evaporative flask, K-D - three 500-mL (Kontes K-570001-0500 or equivalent).
Attach to concentrator tube with springs.
6.2.6 Snyder column, K-D - three ball micro (Kontes K-503000-0121 or equivalent).
6.2.7 Snyder column, K-D - two ball micro (Kontes K-569001-0219 or equivalent).
6.2.8 Vials - Glass, 5- to 10-mL capacity with TFE-fluorocarbon lined screw cap.
6.3 Separatory funnel shaker - Capable of holding eight 2-L separately funnels and shaking
then with rocking motion to achieve thorough mixing of separatory funnel contents
(available from Eberbach Co. in Ann Arbor, Ml).
6.4 Tumbler - Capable of holding four to six tumbler bottles and tumbling them end-over-end
at 30 tums/min. (Associated Design and Mfg. Co., Alexandria, VA.).
6.5 Boiling stones - carborandum, #12 granules (Arthur H. Thomas Co. #1590-033). Heat
at 400oC for 30 min prior to use. Cool and store in a desiccator.
6.6 Water bath - Heated, capable of temperature control (+2<>C). The bath should be used
in a hood.
6.7 Balance - Analytical, capable of accurately weighing to the nearest 0.0001 g.
6.8 Gas Chromatograph - Analytical system complete with GC suitable for use with capillary
columns and all required accessories including syringes, analytical columns, gases,
detector and stripcnart recorder. A data system is recommended for measuring peak
areas.
6.8.1 Primary column - 30 m long x 0.25 mm I.D. DB-5 bonded fused silica column, 0.25
um film thickness (available from J&W). Validation data presented in this method
were obtained using this column. Alternative columns may be used in accordance
with the provisions described in Section 10.3.
6.8.2 Confirmation column - 30 m long x 0.25 mm I.D. DB-1701 bonded fused silica
column, 0.25 um film thickness (Available from J&W).
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6.8.3 Detector - Electron capture. This detector has proven effective in the analysis of
spiked reagent and artificial ground waters. An ECO was used to generate the
validation data presented in this method. Alternative detectors, including a mass
spectrometer, may be used in accordance with the provisions described in Section
10.3.
7. REAGENTS AND CONSUMABLE MATERIALS
7.1 Acetone, methylene chloride, MTBE - Distilled-in-glass quality or equivalent.
7.2 Phosphate buffer, pH7 - Prepare by mixing 29.6 ml 0.1 N HC1 and 50 mL 0.1 M
dipotassium phosphate.
7.3 Sodium sulfate, granular, anhydrous, ACS grade - Heat treat in a shallow tray at 450<>C
for a minimum of 4 hours to remove interfering organic substances.
7.4 Sodium chloride, crystal, ACS grade - Heat treat in a shallow tray at 450oC for a
minimum of 4 hours to remove interfering organic substances.
7.5 Pentachloronitrobenzene (PCNB) - >98% purity, for use as internal standard.
7.6 4,4'-Dichlorobiphenyl (DCB) - 96% purity, for use as surrogate standard (available from
Chemicals Procurement, Inc.).
7.7 Reagent Water - Reagent water is defined as water in which an interferant is not
observed at or above the EDL of any analyte. Reagent water used to generate the
validation data in this method was distilled water obtained from the Magnetic Springs
Water Co., Columbus, Ohio.
7.8 STOCK STANDARD SOLUTIONS (1.00 ug/uL) - Stock standard solutions may be
purchased as certified solutions or prepared from pure standards 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 MTBE and dilute to volume in a 10-mL
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....
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 approximately 0.0010 g of pure PCNB. Dissolve the
PCNB in MTBE and dilute to volume in a 10-mL volumetric flask. Transfer the internal
standard spiking solution to a TFE-fluorocarbon-sealed screw cap bottle and store at
room temperature. Addition of 5 uL of the internal spiking solution to 5 mL of sample
extract results in a final internal standard concentration of 0.1 ug/mL Solution should be
replaced when ongoing QC (Section 10) indicates a problem.
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7.10 SURROGATE STANDARD SPIKING SOLUTION - Prepare a surrogate standard spiking
solution by accurately weighing approximately 0.0050 g of pure DCS. Dissolve the DCB
in MTBE and dilute to volume in a 10-mL volumetric flask. Transfer the surrogate
standard spiking solution to a TFE- fluorocarbon-sealed screw cap bottle and store at
room temperature. Addition of 50 uL of the surrogate standard spiking solution to a 1-L
sample prior to extraction results in a surrogate standard concentration in the sample of
25 ug/L and, assuming quantitative recovery of TDBP, a surrogate standard
concentration in the final extract of 5.0 ug/mL Solution should be replaced when
ongoing QC (Section 10) indicates a problem.
7.11 INSTRUMENT QC STANDARD - Prepare instrument QC standard stock solutions by
accurately weighing 0.0010 g each of chlorothalonil, heptachtor epoxide, DCPA, and
HCH-delta Dissolve each analyte in MTBE and dilute to volume in individual 10-mL
volumetric flasks. Combine 2 uL of the heptachfor epoxide stock solution, 50 uL of the
DCPA stock solution, 50 uL of the chlorothalonil stock solution, and 40 uL of the
HCH-delta stock solution to a 100-mL volumetric flask and dilute to volume with MTBE.
Transfer the instrument QC standard solution to a TFE-fluorocarbon-sealed screw cap
bottle and store at room temperature. Solution should be replaced when ongoing QC
(Section 10) indicates a problem.
8. SAMPLE COLLECTION, PRESERVATION AND STORAGE
8.1 Grab samples must be collected in glass containers. Conventional sampling practices
should be followed; however, the bottle must not be prerinsed with sample before
collection.
8.2 SAMPLE PRESERVATION
8.2.1 Add mercuric chloride to the sample bottle in amounts to produce a concentration
of 10 mg/L Add 1 mL of a 10 mg/mL solution of mercuric chloride in reagent water
to the sample bottle at the sampling site or in the laboratory before shipping to the
sampling site. A major disadvantage of mercuric chloride is that it is a highly toxic
chemical; mercuric chloride must be handled with caution, and samples containing
mercuric chloride must be disposed of properly.
8.2.2 After adding the sample to the bottle containing preservative, seal the sample bottle
and shake vigorously for one minute.
8.2.3 Samples must be iced or refrigerated at 4«C from the time of collection until
extraction. Preservation study results presented in Table 11 indicate that most of
the target analytes present in the samples are stable for 14 days when stored
under these conditions. However, analyte stability may be affected by the matrix;
therefore, the analyst should verify that the preservation technique is applicable to
the samples under study.
8.3 EXTRACT STORAGE
8.3.1 Sample extracts should be stored at 4oC away from the light A 14-day maximum
extract storage time is recommended. The analyst should verify appropriate extract
holding times applicable to the samples under study.
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9. CALIBRATION
9.1 Establish GC operating parameters equivalent to those indicated in Table 3. The GO
system must be calibrated using the internal standard technique (Section 9.2).
9.2 INTERNAL STANDARD CALIBRATING PROCEDURE - To use this approach, the analyst
must select one or more internal standards compatible in analytical behavior to the
compounds of interest. The analyst must further demonstrate that the measurement of
the internal standard is not affected by method or matrix interferences. PCNB has been
identified as a suitable internal standard.
9.2.1 Prepare calibration standards at a minimum of three (suggested five) concentration
levels for each analyte of interest by adding volumes of one or more stock
standards to a volumetric flask. To each calibration standard, add a know constant
amount of one or more internal standard, and dilute to volume with MTBE. One of
the calibration standards should be representative of an analyte concentration near,
but above, the EDL 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 2 uL of each calibration standard and tabulate the relative response for each
analyte (RRa) to the internal standard using the equation: RRa = Aa/Ais where:
Aa = the peak area of the analyte, and Ais = the peak area of the internal
standard Generate a calibration curve of analyte relative response, 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 25%, the test must be repeated
using a fresh calibration standard. Alternatively, a new calibration curve must be
prepared for that analyte.
10. QUALITY CONTROL
10.1 Each laboratory using this method is required to operate a quality control (QC) program.
The minimum requirements of this program consist of the following: an initial
demonstration of laboratory capability; the analysis of surrogate standards in each and
every sample as a continuing check on sample preparation; the monitoring of internal
standard area counts or peak heights in each and every sample as a continuing check
on system performance; the analysis of laboratory control standards, QC samples, and
performance evaluation (PE) samples as continuing checks on laboratory performance;
the analysis of spiked samples as a continuing check on recovery performance, the
analysis of method blanks as a continuing check on contamination; and frequent analysis
of the instrument QC standard to assure acceptable instrument performance.
10.2 INITIAL DEMONSTRATION OF CAPABILITY - To establish the ability to perform this
method, the analyst must perform the following operations.
10.2.1 Select a representative spike concentration (suggest 15 times the EDL) for
each of the target anafytes. Using a stock standard that differs from
calibration standard, prepare a laboratory control (LC) check sample
concentrate in methanol 1000 times more concentrated than the selected
spike concentration.
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10.2.2 Using a syringe, add 1 mL of the LC sample concentrate to each of a
minimum of 4 1-L aliquots of reagent water. A representative groundwater
may be used in place of the reagent water, but one or more unspiked
aliquots must be analyzed to determine background levels, and the spike
level must, at a minimum, exceed twice the background level for the test to
be valid. Analyze the aliquots according to the method beginning in Section
11.
10.2.3 Calculate the average percent recovery (R) and the standard deviation of
percent recovery (RSD), for the results. Ground water background
corrections must be made before R and RSD calculations are performed.
10.2.4 Table 2 and Tables 4-9 provide single laboratory recovery and precision data
obtained for the method analytes from reagent and artificial ground waters,
respectively. Similar results from dosed reagent and artificial ground waters
should be expected by any experienced laboratory. Compare results
obtained in Section 10.2.3 to the single laboratory recovery and precision
data. If the results are not comparable, review potential problem areas and
repeat the test. Results are comparable if the calculated percent relative
standard deviation (RSD) does not exceed 2.6 times the single laboratory
RSD or 20 percent, whichever is greater, and your mean recovery lies within
the interval R + 30% whichever is greater.
10.3 In recognition of the rapid advances occurring in chromatography, the analyst is
permitted to modify GC columns, GC conditions, or detectors to improve the separations
or lower the cost of measurements. Each time such modifications to the method are
made, the analyst is required to repeat the procedure in Section 10.2.
10.4 ASSESSING SURROGATE RECOVERY
10.4.1 All samples and blanks must be fortified with the surrogate spiking
compound before extraction. A surrogate standard determination must be
performed on all samples (including matrix spikes) and blanks.
10.4.2 Determine whether the measured surrogate concentration (expressed as
percent recovery) falls between 70 and 130 percent of the mean from the
control charts.
10.4.3 When the surrogate recovery for a laboratory method blank is less than 70 or
greater than 130 percent of the mean from the control charts, the laboratory
must take the following actions: (1) Check calculations to make sure there
are no errors. (2) Check internal standard and surrogate standard spiking
solutions for degradation, contamination, or other abnormalities. (3) Check
instrument performance. Reinject the laboratory method blank extract If the
reanalysis fails the 70 to 130 percent recovery criteria, the analytical system
must be considered 'out of control.' The problem must be identified and
corrected before continuing.
10.4.4 When the surrogate recovery for a sample is less than 70 percent or greater
than 130 percent from the mean, the laboratory must establish that the
deviation is not due to laboratory problems. The laboratory shall document
deviations by taking the following actions: (1) Check calculations to make
sure there are no errors. (2) Check internal standard and surrogate
standard spiking solutions for degradation, contamination, or other obvious
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abnormalities. (3) Check instrument performance. Recalculate or reanalyze
the extract if the above steps fail to reveal the cause of the noncompliant
surrogate recoveries. If reanalysis of the sample or extract solves the
problem, only submit the sample data from the analysis with surrogate spike
recover is within the required limits. If reanalysis of the sample or extract
fails to solve the problem, then report all data for that sample as suspect.
10.5 ASSESSING THE INTERNAL STANDARD
10.5.1 An internal standard peak area or peak height check must be performed on
all samples. All sample extracts must be fortified with the internal standard.
10.5.2 Internal standard recovery must be evaluated for acceptance by determining
whether the measured peak area or peak height for that internal standard in
any sample deviates by more than 30 percent from average peak area or
height for the internal standard in the calibration standards.
10.5.3 When the internal standard peak area or height for any samples is outside
the limit specified in 10.5.2, the laboratory must investigate.
10.5.3.1 Single occurrence - Reinject an aliquot of the extract to insure
proper sample injection. If the reinjected sample extract aliquot
displays an internal standard peak area or height within specified
limits, quantify and report results. If the reinjected sample extract
aliquot displays an internal standard peak area or height outside
the specified limits, but extract aliquots from other samples
continue to give the proper area or height for the internal
standard, assume an error was made during addition of the
internal standard to the failed sample extract. Remove an another
aliquot of the sample extract and re-spike internal standard
solution. Repeat sample analysis.
10.5.3.2 Multiple Occurrence - If the internal standard peak areas or
heights for successive samples fail the specified criteria (10.5.2),
check the instrument for proper performance. After optimizing
instrument performance, check the calibration curve using a
calibration check standard (Section 9). If the calibration curve is
still applicable and if the calibration check standard internal
standard peak area or height is within 25 percent of the average
internal standard peak area or height for the calibration
standards, reanalyze those sample extracts whose internal
standard failed the specified criteria If the internal standard peak
areas or heights now fall within the specified limits, report the
results. If the internal standard peak areas or heights still fail to
fall within the specified limits or if the calibration curve is no
longer applicable, then generate a new calibration curve (Section
9) spike a fresh sample aliquot with the internal standard solution
for those extracts whose internal standard failed the peak area or
height criteria
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10.6 ASSESSING LABORATORY PERFORMANCE
10.6.1 The laboratory must, on an ongoing basis, analyze at least one laboratory
control standard per sample set (a sample set is all those samples extracted
within a 24-hour period).
10.6.1.1 The spiking concentration in the laboratory control standard
should be 15 times the EDL
10.6.1.2 Spike a 1-L aliquot of reagent water with a laboratory control (LC)
sample concentrate (the volume of the spike should be kept to a
minimum so the solubility of the analytes of interest in water will
not be affected) and analyze it to determine the concentration
after spiking (A) of each analyte. Calculate each percent recovery
(Ri as (100xA)%/T, where T is the known true concentration of the
spike.
10.6.1.3 Compare the percent recovery (Ri) for each analyte with
established QC criteria QC criteria are established by initially
analyzing five laboratory control standards and calculating the
average percent recovery (R) and the standard deviation of the
percent recovery (SR) using the following equations:
n
R = Ri/n
andSR =
where: n = number of measurements for each analyte, and
Ri = individual percent recovery value.
Calculate QC acceptance criteria as follows:
Upper Control Limit (UCL) = R + 3SR
Lower Control Limit (LCL) = R - 3SR
Alternatively, the data generated during the initial demonstration
of capability (Section 10.2) can be used to set the initial upper
and lower control limits. Update the performance criteria on a
continuous basis. After each five to ten new recovery
measurements (RiS), recalculate R and SR using all the data, and
construct new control limits. When the total number of data
points reach twenty, update the control limits by calculating R and
Sr using only the most recent data points. Monitor all data from
laboratory control standards. Analyte recoveries must fall within
the established control limits. If the recovery of any such analyte
falls outside the designated range, the laboratory performance for
that analyte is judged to be out of control, and the source of the
problem must be immediately identified and resolved before
continuing the analyses. The analytical result for that analyte in
samples is suspect and must be so labeled. All results for that
analyte in that sample set must also be labeled suspect
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10.6.2 Each quarter, it is essential that the laboratory analyze (if available) QC
check standards. If the criteria established by the U.S. Environmental
Protection Agency (USEPA) and provided with the QC standards are not
met, corrective action needs to be taken and documented.
10.6.3 The laboratory must analyze an unknown performance evaluation sample
(when available) at least once a year. Results for each of the target analytes
need to be within limits established by USEPA.
10.7 ASSESSING ANALYTE RECOVERY
10.7.1 The laboratory must, on an ongoing basis, spike each of the target analytes
into ten percent of the samples.
10.7.1.1 The spiking concentration in the sample should be one to five
times the background concentration, or, if it is impractical to
determine background levels before spiking, 15 times the EOL
10.7.1.2 Analyze one sample aliquot to determine the background
concentration (B) of each analyte. Spike a second sample aliquot
with a laboratory control (LC) sample concentrate (the volume of
the spike should be kept to a minimum so the solubility of the
analytes of interest in water will not be affected) and analyze it the
determine the concentration after spiking (A) of each analyte.
Calculate each percent recovery (Ri) as 100(A-B)%/T, where T is
the known true concentration of the spike.
10.7.1.3 Compare the percent recovery (Ri) for each analyte with QC
acceptance criteria established from the analyses of laboratory
control standards. Monitor all data from closed samples. Analyte
recoveries must fall within the established control limits.
10.7.1.4 If the recovery of any such analyte falls outside the designated
range, and the laboratory performance for that analyte is judged
to be in control, the recovery problem encountered with the
dosed sample is judged to be matrix related, not system related.
The result for that analyte in the unspiked sample is labeled
suspect/matrix to inform the \jser that the results are suspect due
to matrix effects.
10.8 ASSESSING LABORATORY CONTAMINATION (METHOD BLANKS) - Before processing
any samples, the analyst must demonstrate that all glassware and reagent interferences
are under control. This is accomplished by the analysis of a laboratory method blank. A
laboratory method blank is a 1-L aliquot of reagent water analyzed as if it was a sample.
Each time a set of samples is extracted or there is a change in reagents, a laboratory
method blank must be processed to assess laboratory contamination. If the method
blank exhibits a peak within the retention time window of any analyte which is greater
than or equal to one-half the EDL for that analyte, determine the source of contamination
before processing samples and eliminate the interference problem.
10.9 ASSESSING INSTRUMENT PERFORMANCE (INSTRUMENT QC STANDARD) Instrument
performance should be monitored on a daily basis by the analysis of the instrument QC
standard. The instrument QC standard contains compounds designed to indicate
appropriate instrument sensitivity, column performance and chromatographic
-------
Appendix A
BevWonNo. 3
D«te: February 28, 1990
P«g« 12 of 32
performance. Instrument QC standard components and performance criteria are listed in
Table 10. Inability to demonstrate acceptable instrument performance indicates the need
for re-evaluation of the GC-ECD system. A GC-ECD chromatogram generated from the
analysis of the instrument QC standard is shown in Figure 3. The sensitivity
requirements are set based on the EDL's published in this method. If the laboratory
EDL's differ from those listed in this method, concentrations of the instrument QC
standard compounds must be adjusted to be compatible with the laboratory EDL's. An
instrument QC standard should be analyzed with each sample set
10.10 ANALYTE CONFIRMATION - When doubt exists over the identification of a peak on the
chromatogram, confirmatory techniques such as mass spectrometry or a second gas
chromatography column must be used. A suggested confirmation column is described
in Table 3.
10.11 ADDITIONAL QC - It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices that are most
productive depend upon the needs of the laboratory and the nature of the samples.
11. PROCEDURE
11.1 AUTOMATED EXTRACTION METHOD - Validation data presented in this method were
generated using the automated extraction procedure with the mechanical separator/
funnel shaker.
11.1.1 Add preservative to any samples not previously preserved (Section 8.2).
Mark the water meniscus on the side of the sample bottle for later
determination of sample volume. Spike sample with 50 uL of the surrogate
standard spiking solution. If the mechanical separatory funnel shaker is
used, pour the entire sample into a 2-L separatory funnel. If the mechanical
tumbler is used, pour the entire sample into a tumbler bottle.
11.1.2 Adjust the sample to pH 7 by adding 50 mL of phosphate buffer.
11.1.3 Add 100 g NaCI to the sample, seal, and shake to dissolve salt.
11.1.4 Add 300 mL methylene chloride to the sample bottle, seal, and shake 30
seconds to rinse the inner walls. Transfer the solvent to the sample
contained in the separatory funnel or tumbler bottle, seal, and shake for 10
seconds, venting periodically. Repeat shaking and venting until pressure
release is not observed during venting. Reseal and place sample container
in appropriate mechanical mixing device (separatory funnel shaker or
tumbler). Shake or tumble the sample for 1 hour. Complete and thorough
mixing of the organic and aqueous phases should be observed at least 2
minutes after starting the mixing device.
11.1.5 Remove the sample container from the mixing device. If the tumbler is used,
pour contents of tumbler bottle into a 2-L separatory funnel. Allow the
organic layer to separate from the water phase for a minimum of 10 minutes.
If the emulsion interface between labels layers is more than one third the
volume of the solvent layer, the analysts must employ mechanical techniques
to complete the phase separation. The optimum technique depends upon
the sample, but may include stirring, filtration through glass wool,
centrifugation, or other physical methods. Collect the methylene chloride
-------
Appendix A
Revision No. 3
Date: February 28, 1990
Page 13 of 32
extract in a 500-mL Ertenmeyer flask containing approximately 5 g anhydrous
sodium sulfate. Swirl flask to dry extract; allow flask to sit for 15 minutes.
11.1.6 Determine the original sample volume by refilling the sample bottle to the
mark and transferring the water to a 1000-mL graduated cylinder. Record
the sample volume to the nearest 5mL
11.2 MANUAL EXTRACTION METHOD - Alternative procedure.
11.2.1 Add preservative to any samples not previously preserved (Section 8.2).
Mark the water meniscus on the side of the sample bottle for later
determination of sample volume. Spike the sample with 50 uL of the
surrogate standard spiking solution. Pour the sample the entire sample into
a 2-L separator/ funnel.
11.2.2 Adjust sample to pH 7 by adding 50 mL of phosphate buffer.
11.2.3 Add 100 g NaCI to the sample, seal, and shake to dissolve salt.
11.2.4 Add 60 ml methylene chloride to the sample bottle, seal, and shake 30
seconds to rinse the inner walls. Transfer the solvent to the separatory
funnel and extract the sample by vigorously shaking the funnel for 2 minutes
with periodic venting to release excess pressure. Allow the organic layer to
separate from the water phase for a minimum of 10 minutes. If the emulsion
interface between the layers is more than one third the volume of the solvent
layer, the analyst must employ mechanical techniques to complete the phase
separation. The optimum technique depends upon the sample, but may
include stirring, filtration through glass wool, centrifugation, or other physical
methods. Collect the methylene chloride extract in a 500-mL Erienmeyer
flask containing approximately 5 g anhydrous sodium sulfate.
11.2.5 Add a second 60-mL volume of methylene chloride to the sample bottle and
repeat the extraction procedure a second time, combining the extracts in the
Erienmeyer flask. Perform a third extraction in the same manner. Swirl flask
to dry extract; allow flask to sit for 15 minutes.
11.2.6 Determine the original sample volume by refilling the sample bottle to the
mark and transferring the water to a 1000-mL graduated cylinder. Record
the sample volume to the nearest 5 mL
11.3 EXTRACT CONCENTRATION
11.3.1 Assemble a K-D concentrator by attaching a 25-mL concentrator tube a
500-mL evaporative flask. Decant methylene chloride extract into K-D
concentrator. Rinse remaining sodium sulfate with two 25-mL portions of
methylene chloride and decant rinses into the K-D concentrator.
11.3.2 Add 1 to 2 dean boiling stones to the evaporative flask and attach a macro
Snyder column. Preset the Snyder column by adding about 1 mL methylene
chloride to the top. Place the K-D apparatus on a hot water bath, 65 to 70oC,
so that the concentrator tube is partially immersed in the hot water, and the
entire lower rounded surface of the flask is bathed with hot vapor. Adjust the
vertical position of the apparatus and the water temperature as required to
complete the concentration in 15 to 20 minutes. At the proper rate of
-------
Appendix A
Revision No. 3
Date: February 28, 1990
Page 14 of 32
distillation the balls of the column will actively chatter, but the chambers will
not flood. When the apparent volume of liquid reaches 2 mL, remove the
K-D apparatus and allow it to drain and cool for at least 10 minutes.
11.3.3 Remove the Snyder column and rinse the flask and its lower joint into the
concentrator tube with 1 to 2 mL of MTBE. Add 10 mL of MTBE and a fresh
boiling stone. Attach a micro-Snyder column to the concentrator tube and
prewet the column by adding about 0.5 mL of MTBE to the top. Place the
micro K-D on the water bath so that the concentrator tube is partially
immersed in the hot water. Adjust the vertical position of the apparatus and
the water temperature as required to complete the concentration in 5 to 10
minutes. When the apparent volume of liquid reaches 2 mL, remove the
micro K-D from the bath and allow it to drain and cool. Add 10 mL MTBE
and a boiling stone to the micro K-D and reconcentrate to 2mL Remove the
micro K-D from the bath and allow it to drain and cool. Remove the micro
Snyder column, and rinse the walls of the concentrator tube while adjusting
the volume to 5.0 mL with MTBE.
11.3.4 Transfer extract to an appropriately sized TFE-fluorocarbon-sealed screw-cap
vial and store, refrigerated at 4<>C, until analysis by GC-ECD.
11.4 GAS CHROMATOGRAPHY
11.4.1 Table 3 summarizes the recommended operating conditions for the gas
chromatograph. Included in Table 3 are retention times observed using this
method. Examples of the separations achieved using these conditions are
shown in Figures 1 and 2. Other GC columns, Chromatographic conditions,
or detectors may be used if the requirements of Section 10.3 are met.
11.4.2 Calibrate the system daily as described in Section 9. The standards and
extracts must be in MTBE.
11.4.3 Inject 2 uL of the sample extract. Record the resulting peak sizes in area
units.
11.4.4 The width of the retention time window use to make identifications should be
based upon measurements of the actual retention time variations of
standards over the course of the day. Three times the standard deviation of
a retention time can be used to calculate a suggested window size for a
compound. However, the experience of the analyst should weigh heavily in
the interpretation of chromatograms.
11.4.5 If the response for a peak exceeds the working range of the system, dilute
the extract and reanalyze.
12. CALCULATIONS
12.1 Calculate analyte concentrations in the sample from the relative response for the analyte
to the internal standard (RRa) using the calibration curve described in Section 9.2.2.
12.2 For samples processed as part of a set where the laboratory control standard recovery
fails outside the control limits in Section 10, data for the affected analytes must be
labeled as suspect
-------
Appendix A
Revtoion No. 3
Date: February 28, 1990
Page IS of 32
13. PRECISION AND ACCURACY
13.1 In a single laboratory, analyte recoveries from reagent water were determined at five
concentration levels. Results were used to determine analyte EDL's and demonstrate
method range. AnaJytes were divided into two spiking groups (A and B) for recovery
studies. EDL results are given in Table 2. Method range results are given in Tables 4-7.
13.2 In a single laboratory, analyte recoveries from two artificial ground waters were
determined at one concentration level. Results were used to demonstrate applicability of
the method to different ground water matrices. Analytes were divided into two spiking
groups (A and B) for recovery studies. 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 with mercuric
chloride were determined 0, 14, and 28 days after sample preparation. Results were
used to predict expected analyte stability in ground water samples. Analytes were
divided into two spiking groups (A and B) for recovery studies. Analyte recoveries from
the preserved, spiked ground water samples are given in Table 11.
-------
Appendix A
Revision No. 3
Date: February 28, 1990
Page 16 of 32
REFERENCES
1. ASTM Annual Book of Standards, Part 11, Volume 11.02, D3694-82, 'Standard Practice
for Preparation of Sample Containers and for Preservation', American Society for Testing
and Materilas, Philadelphia PA p.86, 1986.
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. Qiam, C.S., and Chan, H.S. and Net, Q.S. 'Sensitive Method for the Determination of
Phthalate Ester Plasticizers in Open-Ocean Biota Samples, "Analytical Chemistry, 47,
2225 (1975).
4. Giam, C.S., and Chan, H.S. 'Control of Blanks in the Analysis of Phthalates in Air and
Ocean Biota Samples, 'US National Bureau of Standards, Special Publication 442", pp.
701-708, 1976.
5. 'Carcinogens - Working with Carcinogens.'Departmerrt 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.
6. "OSHA Safety and Health Standards, General Industry,' (29 CFR 110), Occupational
Safety and Health Administration, OSHA 2206, (Revised, January 1976).
7. 'Safety in Academic Chemistry Laboratories, 'American Chemical Society Publication,
Committee on Chemical Safety, 3rd Edition, 1979.
8. ASTM Annual Book of Standards, Part 11, Volume 11.01, D3370-82, 'Standard Practice
for Sampling Water, 'American Society for Testing and Materials, Philadelphia, PA, p. 130,
1986.
-------
'iSLE 1. "E7HOO ANALYTES
- n a '> .• ' 2
Aldrin
Chloraane-a i:na
Chloraane-gamma
Chlorneo
Chlorooenzilate
Chi orotna i om i
DCPA
4, 4 '-COO
4,4'-CCE
4,4' -GOT
2 i e i d n n
Endosui fan ;
Enoosuifan II
Endosui fan suifate
Endnn
Endnn aicenyde
Etndiazoie
HCH-alona
HCH-beta
HCH-delta
HCH-gamma
Heotacnlor
Heptacnlor eooxide
Hexacnlorsoenzene
Metnoxycnlor
cis-Permetnnn
•.rans-rer-etnnn
?ro0acnlor
Tn f 1 urai :n
Chemical Abstracts
Service
Registry Numoer
309-00-2
5103-71-9
5103-74-2
2675-77-5
501-15-6
2921-88-2
1897-45-6
72-54-8
72-55-9
50-29-3
50-57-1
959-98-8
•3213-65-9
1031-07-8
72-20-8
7421-93-4
2593-15-9
319-84-6
319-85-7
319-86-8
58-89-9
76-44-8
1024-57-3
118-74-1
72-43-5
52645-53-1
52645-53-1
1918-16-7
1582-09-8
]:ent .
Ccce( a)
A7
59
38
Al
311
A6
37
312
310
A16
-11
A10
A14
313
A12
A15
Bl
A3
34
35
AS
36
A9
33
314
A17
315
A2
32
;a) Coce used for identification of oeaks in method f-gures:
'etter :naicates wmcn soiling mix (A or 8) contains the
snaiyte: IS - internal standard: SUR - surrogate standard.
-------
CF :NALYTES F«GM REAGENT WATER fSPIKING L£VEL
AND EDLs (a,
SsiKirg A, lit 'T
.eve 1 , 51 anic .
--a'.. :e jg/L -g/L i(
-'•Grin (h) 0.075
C'-iloraane-alpna C.015
Iniorcane-gamma 0.015
Chiorneo -^ 0.50
Chlorooenzilate (h) 5.0
Chlortnalonil 0.025
XPA 0.025
4,4' -000 0. 025
4. 4'- ODE 0.010
A.4'-ODT 0.060
;;elann C.C20
Eicosulfan I 0.015
Encosuifan sulfate 0.015
Enonn 0.015
Enonn aldehyde 0.025
Endosulfan II 0.015
Etndiazole 0.025
HCH-alpha (h) 0.025
HCH-beta 0.010
NO (g)
•JO
NO
NO
NO
NO
NO
NO
NO
NO
SO
NO
NO
NO
NO
NO
NO
NO
NO
HCH-delta 0.010 0.0036
HCH-gamma 0.015
-ieotacnlor 0.010
^eotacnlor epoxide 0.015
4exacn1orobenzene 0.0050
*etnoxycnlor 0.050
ci s-??rmethrin 0.50
•.rans-?ermethrin 0.50
3"9oacnlor 0.50
Tnfluralin 0.025
(a) Data corrected for amount found
'b) n • numoer of data points.
(c) 3 - average percent recovery.
Id) S - standard deviation.
(2) ^SO » percent relative standard
(f) £DL • estimated detection limit
NO
NO
NO
NO
NO
NO
NO
NO
NO
in blanic.
deviation
in samole
o)
7
7
'
7
3
7
7
T
7
^
*
^
•*
7
*
7
7
3'
7
7
7
7
*
7
1
7
~
7
7
.
in yq
^(c) si:) Rso(e) E:L;
56
117
109
47
99
119
112
115
127
87
77
78
129
72
95
148
96
94
95
84
80
67
71
115
120
64
122
90
108
/u
0.00456
0.00132
0.000515
0.0794
0.7076
0.00354
0.00102
0.00140
0.000797
0.0123
0.0034
0.00292
0.000779
0.00198
0.00355
0.00778
0.00416
0.00177
0.00113
0.000622
0.00190
0.000484
0.00189
0.00246
0.00685
0.0782
0.0581
0.0798
0.000816
calculated by
9
3
3
c2^~
5
12
4
5
6
CsS^
s22<
Cy^Jf
4
18
^*lf*S.
i/^
8
12
7
16
7
18
^yj^v
11
( "L&s
9'
18
3
mu 1 1 i p 1 y i
O.C
O.C
o.c
o.s
5.0
0.0
o.c
0.0
o.c
^ .
-------
CONFIRMATION CHROMATOGRAPHIC ::NOIT:ONS
ina;
elative Retention 7i.re -'or
C;iC''"ors ';'
(b)
lanfimation (c)
Aldrin
Chlordane-aiona
Chlordane-gamma
Chlorneo
Chlorobenzi late
Chlorotnalom 1
:CPA
4.4'- ODD
- . 4' -ODE
» . 4 ' -ODT
Dieldrin
Endosuifan I
Endosulfan II
Endosuifan sulfate
Enarin
Endrin aldehyde
Etndiazole
HCH-alpha
HCH-beta
HCH-delta
HCH-gamma
Heptachlor
yeotacnlor eooxide
Hexacnlorooenzene
Methoxycftlor
;: s -Permetnrin
trans-Pennetnrin
'rooacnlor
Tn flural in
(a) Retention time relative :o ?CNB --t«r'
approximately 34 mm.
(b) Primary conditions:
Column: 30 m long x 0.25 "« I
1.18
1.31
1.28
0.75
1.41
1.04
.21
.42
.35
.48
.35
.30
.40
.47
.38
1.43
0.69
0.93
0.98
1.03
0.99
1.11
1.24
0.94
.57
.72
.73
0.85
0.93
iai standara *hi
2. 38-5 bonced
1.12
1.31
1.29
0.77
1.42
1.17
1.21
1.38
1.32
1.48
1.35
1.28
1.45
(d)
1.38
1.52
0.67
0.97
1.18
1.22
1.04
1.08
1.24
(d)
1.53
(d)
(d)
0.91
(d)
en eiutes at
fused sil ica
Injection volume:
Carrier gas:
Injector temp:
Detector temo:
Oven temp:
Detector:
column. 0.25 jfl •"•'* t^cfcness (
2 uL soiitless •
-------
:; Cannrraf. on conditions:
.: . -inn
Oven :emo
Zetec'.cr
20 ^ 'anq x :.Z5 im 1.3. 33-1'Cl sonaed f-sea
:::umn. C.25 -m
: jL cri't'ess *itfi 45 secona ieiay
-e ?30 c^i/sec ', -near velocity
150'C
* ? n * *"
3-ogram from 60*C to 300*C at 4'C/inn
ECD
Data not available
-------
-ai.1 i
Cr ANAIYTES FROM REAGENT WATER (SPIKING LEVEL 2'
So i King A, nt ' n
.evei . 51 an*
-nai.:e jg/i -g/L
Aldnn 0.075
Ifiloraane-ai:na 0.075
Ihloraane-gamma 0.075
Chlorneo 2.5
Chlorooenzi! ate 5.0
Chlortnalom 1 0.13
3CPA 0.13
4.4'-000 0.13
4. 4 '-ODE 0.050
-.4 '-DDT 0.20 3,
3i slarin 0.10
•Inaosulfan : 0.075
Enaosulfan suifate 0.075
E.idrin 0.075
Enorin aldehyae 0. 13
Enaosulfan I'. 0.075
Etnduzole 0.13
HCH-alpha 0.025
HCH-beta 0.050
uCH-aelta 0.050
HCH-gamma 0.075
Heotacnlor 0.050
Heotacnlor eooxiae 0.075
Hexacnlorooenzene 4- 0.025
^ethoxycnlor 0.25
ci s-^ermethrrn 2.5
:rans-?ermetnnn 2.5
^opacnlor 2.5 0
"nfluralin 0.13
NO
NO
NO
NO
NO
NO
NO
NO
NO
' X 1
"NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
.524
NO
nib)
(f) 7
3
3
3
3
8
3
3
*
5
3
3
3
3
3
3
7
3
3
3
3
3
3
3
3
3
3
7
7
^(c) i(d) SSO(e)
55
93
92
95
99
100
93
94
96
95
9(5
93
96
96
99
99
92
94
34
100
93
30
37
138
97
98
112
103
37
0.00456
0.0110
0.0103
0.203
0.708
0.00916
0.0190
0.0163
0.00213
0.0445
0.00841
0.00593
0.00945
0.00618
0.0103
0.00658
0.0104
0.00177
0.00709
0.00698
0.00564
0.00716
0.00616
0.00885
0.0344
0.212
0.0985
0.223
0.0138
9
5
5
9
5
T
5
3
4
15
9
3
3
9
8
9
9
8
3
4
3
7
9
(jfo^)
^^T
9
d
9
12
(a) 3ata corrected for amount founa -i sianK.
',5) n » numoer of data points.
vc) R • average percent recovery
'd) S • stanaard deviation.
;e) SSD « percent relative stanoara
;f) NO - interference not detec:
ea •
cevuticn.
i :' an*.
-------
"ABLE 5. RECOVERY CF ANAUTES "SOM REAGENT WATER (SPIKING LEVEL 2]
$0 i < i no imt • n
^svei , 5
-naiyte -g/L
Aldnn 0.15
Chloraane-alona 0.15
Chloroane-gamma 3.15
Chlorned 5.0
Chlorooenzilate 10
Chlorthalonil 0.25
OCPA 0.25
4. 4'- 000 0.25
4. 4'- ODE 3.10
4.4'-OOT 3.50
Dieldrin 3.20
Endosulfan I 3.15
Enaosuifan sulfate 0.15
Endrin 0.15
Endrin aldehyde 0.25
Endosulfan II 0.15
Etridiazole 0.25
HCH-alpha 0.050
HCH-beta 0.10
HCH-delta 0.10
HCH -gamma 0.15
Heptachlor 0.10
Heptacnlor epoxide 0.15
Hexachlorobenzene-^- 0.050
Methoxycnlor 0.50
CTS-Permethrin 5.0
•.rans-Permethrin 5.0
3rooachlor 5.0
Trifluralin 0.25
(a) Oata corrected for amount f
(b) n « nuraoer of data points.
1 an*
.g/L
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
'-0
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
ound
T,(0)
(f) 3
3
3
5
7
3
3
7
3
^
2
a
5
3
3
3
5
3
7
7
3
7
3
5
3
3
6
T
7
•n 2lar.K.
;(cj
86
99
99
97
108
91
103
107
99
112
37
37
102
38
38
92
103
92
95
102
89
98
87
99
105
91
111
103
103
Sf3)
0.0142
0.0183
0.0181
0.601
0.535
0.0210
0.0307
0.0157
0.0118
0.0984
0.0173
0.0131
0.0221
0.0133
0.0191
0.0148
0.0166
0.00490
0.00661
0.0115
0.0150
0.0117
0.0134
0.0110
0.0655
0.473
0.306
0.440
0.0121
RSO(e)
11
12
12
12
5
9
12
6
12
15
10
10
15
10
9
11
6
11
7
11
11
12
10
6
9
5
(c) R • average percent recovery.
(d) S • stanoard deviation.
(e) RSO - percent relative stanoard ctviation.
(f) NO • interference not detec
ted •
i rlan«.
-------
"ABLE 5. -"ECCVERY CF ANALYSES FROM REAGENT WATER (SPUING -EYEL 4) (a)
3s i ki rto imt i n
_evei . 31 an*
- n a I y C e
ildrin
Chlordane-aioha
Chloraane-gamma
Chlorneo
Chlorooenzi late
Chlorthaloml
:CPA
4.4'-ODO
A, 4 '-ODE
4. 4 '-GOT
3ieldnn
i.naosuifan !
Endosuifan sulfate
Endnn
Endnn aldehyde
Endosuifan II
Etridiazole
HCH-alpha
HCH-beta
HCH-delta
HCH-gamma
Heptacnlor
Heptacnlor epoxide
Hexacnlorooenzene
Metnoxycnlor
CT s-Permetnnn
:rans-?ermetnrin
3fooachlor
~ri f 1 ural i n
-9/1
0.38
0.38
0.38
13
25
0.63
0.63
0.63
0.25
i C
0.50
0.33
0.33
0.33
0.63
0.38
0.63
0.13
0.25
0.25
0.38
0.25
0.38
0.13
1.3
13
13
13
0.63
(a) Data corrected for amount
(b) n • numoer of
data points
-3/L
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
0.526
NO
found
-;s)
(f) 8
5
6
7
6
3
6
6
5
7
3
3
6
6
7
3
6
7
6
6
3
6
3
6
6
7
6
7
7
in blanic.
R(c)
95
39
38
90
89
94
89
92
S3
99
100
101
93
100
98
101
34
91
96
34
93
37
83
35
96
101
94
S3
90
s ,' a ) R
0.0356
0.0109
0.00920
0.834
0.892
0.0540
0.0140
0.0248
0.00856
3.135
0.0505
0.0391
0.0184
0.0295
0.0547
0.0399
0.0245
0.00865
0.00820
0.0285
0.0335
0.00667
0.0318
0.00335
0.0614
0.986
0.511
0.925
0.0337
S0(e)
10
3
3
7
4
9
3
4
4
9
10
10
5
a
9
10
5
7
3
14
9
3
10
3
5
3
4
3
6
(c) R • average percent recovery.
(d) S - standard
te) RSD « percent
deviation.
relative standard
(f) NO - interference not detected
deviation.
in blanic.
-------
"ABLE ". -"ECCVERY
Cr ANALY'-i ,'
S 3 '.King Amt
•*OM REAGENT
; n
•A i cS
(SPIK
ING .EYEl
:) (a)
,ave i . si ann
~nai/te
Aldnn
Ihlordane-aioha
Chloraane-gamma
Chlorneo
Chlorooenzi 1 ate
Chlorthaloni 1
DCPA
4.4'- 000
4, 4'- DOE
4.4'-ODT
jieidrin
•ndosulfan I
•ndosulfan sulfate
Enorin
Endrin aldehyde
Endosulfan 11
Etridiazole
HCH-alpha
HCH-beta
HCH-delta
HCH -gamma
Heptacnlor
Heptachlor epoxide
Hexacnlorobenzene
Methoxychlor
cis-Permethrin
trans-Permetnrin
=rooacn1or
Triflural in
(a) Data corrected
'b) n - numoer of
-g/L -<
1.5
1.5
1.5
50
100
2.5
2.5
2.5
1.0
5.0 ;.
Z.3
'. . 5
I c
L5
2 5
1.5
2.5
0.50
1.0
1.0
1.5
1.0
1.5
0.50
5.0
50
50
50
2.5
for amount f
data points.
3/1 ^(0
NO (f)
NO
NO
NO
NO
NO
NO
NO
NO
1Z2
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
cunfl -n 3! am
i) -
3
3
3
3
3
3
3
3
3
3
a
3
3
3
3
3
3
3
3
3
3
8
3
3
3
8
a
I
3
(c)
95
90
90
97
93
97
93
91
89
93
95
95
91
96
95
94
39
95
91
91
96
36
96
77
91
93
91
98
38
S.-3)
0.0516
0.0904
0.0855
1.75
8.30
0.0966
0.176
0.189
0.0877
0.362
0.0875
0.0618
0.111
0.0691
0.163
0.0829
0.117
0.0170
0.0673
0.0669
0.0512
0.0474
0.0596
0.0241
0.3S8
3.80
4.72
1.78
0.149
=SO(e)
4
7
7
4
10
4
3
10
10
6
5
i
9
5
7
6
5
4
3
7
4
6
4
6
9
3
10
4
7
(d) R - average percent recovery.
'a) S • standard aeviation.
(e) RSO • percent
relative stancars :ev«t:cn.
;f) NO • interference not aetec
:ea •-• :'an<
-------
"A3LE 3. -"CCVERY OF iNALYTES FROM HARD ARTI
:r.<
-naiyte
ildrin
Chloraane-alpha
Chloraane-gamma
Chlorneo
Chlorooenzi late
Chlorthalonil
DC PA
4,4'-ODD
4,4' -DDE
4. 4 '-DOT
Dieldrtn
Endosulfan 1
Endosulfan II
Endosulfan suifate
Enorin
Endrin aldehyde
Etridiazole
HCH-alpha
HCH-beta
HCH-delta
HCH -gamma
Heptachlor
Heptacnlor epoxiae
Hexacnlorobenzene
Methoxycnlor
cis-Pennethrin
trans-Permethnn
Propachlor
Tri fl ural in
(a) Corrected for
• i"* CVCI " ' ' a 1
. <
f 11 i«L un
-rr,t • -i imt ' i
jg/L -g/L n(b) S(c)
3.15
0.15
0.15
5.0
10
0.25
0.25
0.25
3.10
3.15
3.CSO
0.15
0.15
0.15
0.15
0.25
15
0.050
0.050
0.10
0.15
0.10
0.050
0.050
0.50
5.0
5.0
5.0
0.25
amount found m
Absopure Nature Artesian Spri
Company in ?1
(b) n « number of
ymouth, Michigan
"data points.
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
bl
ng
,
(M 7
7
7
7
6
7
7
5
-
7
^
7
6
6
7
7
6
7
6
7
5
7
7
6
5
7
5
5
5
an*: artifi
100
96
96
95
98
103
100
96
96
98
103
102
94
98
103
98
91
106
92
99
115
85
103
82
101
96
97
116
36
OUND WATER
S(cJ) RSD(
0.0163
0.0189
0.0180
0.339
1.03
0.0262
0.0317
0.0221
0.0125
0.0169
0.00451
0.0124
0.0170
0.0141
0.0166
0.0265
0.992
0.00347
0.00282
0.0124
0.0104
0.0108
0.00382
0.00511
0.0502
0.594
0.487
0.206
0.0257
cial ground water was
water Obtained from
the Absopure
e)
11
13
13
7
11
10
13
9
13
12
9
8
12
10
11
11
7
7
6
12
6
13
7
12
10
12
10
4
12
Water
(c) R • average oercent recovery.
(d) S • standard
(e) RSO » cercent
deviation.
relative standard
(f) NO • interference not detected i
Deviation.
n olantc.
-------
•ABLE 9. RECOVERY OF ANALYTES FROM ORGANIC-CONTAMINATED
:ROUNO WATER (SPIKING LEVEL •; ;a)
imt in imt 'n
Samole, 31anK.
-nalyte ug/L ug/L
ildrin 0.15
Chlordane-alpha 0.15
Chlordane -gamma 0.15
Chlorneb 5.0
Chlorobenzilate 10
Chlorthaloml 0.25
OCPA 0.25
4. 4 '-ODD 0.25
4.4'-OOE 0.10
4.4'-DDT 0.15
Oieldrin 0.050
Endosulfan I 0.15
Endosulfan II 0.15
Endosulfan sulfate 0.15
Endrin 0.15
Endrin aldehyde 0.25
Etridiazole 15
HCH-alpha 0.050
HCH-beta 0.050
HCH-delta 0.10
HCH- gamma 0.15
Heptachlor 0.10
Heptachlor epoxide 0.050
Hexachlorobenzene 0.050
Methoxychlor 0.50
cis-Permethrin 5.0
trans-Permethrin 5.0
Pnjpachlor 5.0
Tnfluralin 0.25
(a) Corrected for amount found in
water spiked with fulvic acid
well -characterized fulvic acid
Substances Society (associated
in Denver, Colorado), was used
(b) n • number of data points.
(c) R « average percent recovery.
(d) S • standard deviation.
NO (f)
NO
NO
NO
NO
NO
NO
NO
SO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
blanic;
at the
, avai
with
•
(e) RSO « percent relative standard devi
(f) NO • interference not detected
in ol
n ( b ) R ( c )
^
•?
7
7
7
7
7
5
^
/
/
7
7
6
6
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
artificial
59
99
99
75
102
71
101
101
99
34
32
34
72
104
84
76
98
36
100
103
85
35
32
68
104
86
102
95
87
ground
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
S(d)
-------
<
z
vl
ss.
o
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— ^
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CT
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5 '
5
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gj w^
3 — '
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vi ci
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M« ^
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2 «"
• •
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I/I
3
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Ol
1
^ ^
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w
3
w
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^^ ^^
3 — «
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"-v Ol
M. VI
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M<
ot -r
- 91
at —
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^--
^^
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s;
•"•
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w
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vt
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3
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Ol
X
Ol
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v> as
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Ol
31
1
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Ol
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i*
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M<
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^M
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5
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^^
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a.
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M^
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« Q.
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'^ «£B
«.-! -—
-J
-»» ^_»
0) 3
C •
.—. ft;
Ol •—
W ^^
£ O)
Ol v»
u <-.
Ol — ^
«w
•— Ol
•— -S.
Ol — '
~ f
«»
-
v» «;
•^ M«
^V w
""* X
01
W M<
Ol -0
^ 11
Z 3.
-------
-OL1
STUDY RESULTS
: " a \ , : 2
-: dr i n
Inloraane-alpha
In 1 ore ane- gamma
Ihlorneo
Chlorobenzilate
Chlortnaloml
:CPA
4.4--OCD
•1.4' -ODE
4.4 '-GOT
:;eldr:n
Ndosulfan I
•ndosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Etndiazole
HCH-aloha
HCH-beta
HCH-delta
HCH-gamma
Heptacnlor
weptacnlor epoxide
uexacnlorobenzene
Methoxycnlor
:i s-?ertnethrin
:rans-Permetnrin
:-ooacnlor
~n fl ural in
Zominq
.sve i .
-g/L
0.15
0.15
0.15
5.0
10
0.25
0.25
0.25
0.10
0.15
0.050
0.15
0.15
0.15
0.25
15
0.050
0.050
0.10
0.15
0.10
0.050
0.050
0.50
5.0
5.0
5.0
0.25
;a) 3 « average oercent recovery
(D) RSO • percent
(c) 2ata not avail
Ta v
;(a>
"3
73
73
39
103
90
95
SO
S3
57
33
39
35
97
91
35
75
37
38
94
90
62
39
67
103
88
111
87
68
from
n
=SO(b)
4
10
10
2
9
2
10
S
10
*
3
i
9
4
5
10
2
3
9
1
11
3
11
9
5
9
3
10
tnol icate
"av '4
*
94
102
101
90
108
(c)
103
109
98
33
34
40
35
112
39
85
67
96
(c)
101
102
74
94
30
115
78
109
105
90
analyses.
RSO
9
12
14
6
15
.
11
15
14
5
c
dp
5
16
7
3
-Z_
5
19
3
4
9
17
3
21
3
4
-,
R
37
99
98
82
103
91
101
34
91
63
77
72
76
103
79
70
100
79
102^
^-Wf^
96
71
78
89
103
31
36
94
100
79
;so
24
12
13
9
14
7
12
9
14
11
&*
^*" *r^
/
15
9
2
IJ*.
S&
^ 14
II
9
10
i i
; 3
17
15
.
relative standard deviation
able; interferences
:resent.
-------
c
I a
e _-
e ""
.j -jj
x z
M
-------
i.'
Q.
o
-a
B u.
e *•
o —
-------
•«
5
z *
c >.
Z vo O
Va» —
Z fc J=
2 -• SJ
as «
— o< M
^ «
Z u SO
~ t <
t_>
• — ae o
e ^ a
m «
"C S3
- rf
41 O U
III
O O wo —
= 4< a
w-l s
i T T t f T i r i i r r
-------
J
i.
. I
»
li
ll
. a
53
a.
<£o
U^ ^J
Is
I/I U4
"
-------
Appendix B
Revision No. 3
Date: February 28, 1990
Page 1 of 28
APPENDIX B
GC/MS SPECTRAL INFORMATION
-------
§ «
X *•
•s -* « 3 x a
= c §
s
u
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M
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£3333:2 =3333333
-------
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Appendix C
Revision No. 3
Date: February 28, 1990
Page 1 of S
APPENDIX C
DIXON'S TEST
-------
DIXON'S TEST
Dixon's test is used to confirm the suspicion of outliers of a set of data
(for example, control chart data points). It is based on ranking the data
points and testing the extreme values for credibility. Dixon's test is based
on the ratios of differences between observations and does not involve the
calculation of standard deviations.
The procedure for Dixon's test is as follows (from Taylor, 1987):
1) The data is ranked in order of increasing numerical value. For
example:
Xi < X2 < X3 < ... < X^ < Xa
2) Decide whether the smallest, XL or the largest, X,,, is
suspected to be an outlier.
3) Select the risk you are willing to take for false rejection.
For use in this QAPP we will be using a 5X risk of false
rejection.
4) Compute one of the ratios in Table 1. For use in this QAPP we
will be using ratio 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 5Z risk values (bolded).
Example (from Taylor)
Given the following set of ranked data:
10.45, 10.47, 10.47, 10.48, 10.49, 10.50, 10.50, 10.53, 10.58
The value 10.58 is suspected of being an outlier.
1) Calculate ru
10.58 - 10.53 0.05
ru - - - 0.454
10.58 - 10.47 0.11
2) A 52 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 10X risk of false rejection ru - 0.409, and the value
10.58 would be rejected.
-------
TABLE 1
CALCULATION OF RATIOS
For use if if X, is if X: is
Ratio n is between suspect suspect
V \ / V
' Xn-l) (X2 '
:io 3-7
- Xa-t) (X2 -
rn 8-10 •
V N / V
" X2^ (Xn-1 •
Y \ /V
•"ri-2/ (.A3 "
r21 11 - 13 - •
- X2) (X,,-! -
Y > ^Y
An-2/ VA3
r22 14 - 25 •
- X3) (X.,.2 -
Note that for use in this QAPjP ratio r22 will be used.
-------
TABLE 2
VALUES FOR USE WITH THE DIXON TEST FOR OUTLIERS
Risk of False Rejection
Ratio n 0.5% 11 5Z 10%
•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 5Z risk level will be used for ratio r22.
-------
Reference:
John K. Taylor, Quality Assurance of Chemical Measurements. Lewis
Publishers, Chelsea, MI, 1987.
-------
Appendix D
Revision No. 3
Date: February 28, 1990
Page 1 of 19
APPENDIX D
STANDARD OPERATING PROCEDURE FOR MANUAL DATA ENTRY
-------
Summary Of NFS Data Package
The information generated by NFS samples is combined into data sets. A s
defined as a group of samples which have been extracted on the same day.
these samples are spiked with a surrogate (DCS) and an internal standard
"The data from these samples is entered into five seperate spreadsheets in
2020 software package and analyzed according to the following plan.
A) Calibration Curve
A three point calibration curve is obtained for each individual set by
analyzing three different concentrations of a group "A" pesticide stocJ
solution and three different concentrations of a group "B" pesticide st
solution. [The reason for having two stock solutions is that some of t
pesticides would co-elute if analyzed together. There are fourteen
individual pesticides in the group "A" mix and fifteen in the group "B*
The information generated by these chromatograms (date, time, retention
of compounds, peak areas, etc...) is entered into a spreadsheet in 2020
pg 3] named CRVXX-X where XX-X is the month and day the curve was run 4
From this information, the 2020 software calculates a calibration curve
each compound along with other statistical data which includes the
correlation efficient. The correlation coefficient must be > 0.995 ace
to the QA plan. Otherwise, a new calibration curve must be prepared (s
project manager) .
B) Instrument Quality Control Check (IQCC)
The IQCC is a standard pesticide solution which mooLtors column perform,
chromatography performance and sensitivity. The0.8 and <1.1!
satisfy QC requirements. Chlorothalonil and delta-BHC evaluates the pel
•resolution and must be >0.50. All of above criteria must be satisfied.
Otherwise, the analysis must be stopped and the problem rectified (see
project manager).
C) Continuing Calibration (CC)
The CC is one of the standard pesticide solutions used to make the
calibration curve. A CC must be run every 12 hours to verify the calibr
curve. If the response for any analytc varies from the predicted respon
'more than XTl, a new calibration curve must be prepared.
-a 51
-------
The information from the chromotogram is entered into the 2020 spreadi
[see pgs 13-14) named CCXX-X.
D) internal Standard Summary Table
In order for a sample, IQCC, CC, etc., to meet QC requirements, the Ii
Standard (I.S.) area, for that run, must be within 201 of the average
area of the standards used to make the calibration curve for that set.
data from the chromatogram is entered into the 2020 spreadsheet [see j
15-16] named ISXX-X.
E) Warning and Control Limit Flag Table
For every spiked sample, the percent recovery of each analyte must be
calculated to see if the recovery is between the allowable control lis
(Control limits are genterated by using data from previous sets and th
Oixon's Test). In order to meet QC requirements, each sample may have
more than 15% of the analytes outside the control limits.
The 2020 spreadsheet (see pgs 17-18] used to calculate these reeoverie
named FLAXX-X. The data entered into this spreadsheet is i~" *"* fro
percent recovery portion of the CRVXX-X spreadsheet.
-------
GENERAL LAYOUT OF CURVE SPREADSHEET
1) STWBARD CURVE DMA
REFER TO DIACSAMS LABELED (1) CN RAGES 4 AND 5.
IN IKES SECTION OF THE SPREADSHEET, DATA FROM THE CHROMAIOGRAMS USED
TO GENERATE THE CALIBRATION CURVE IS ENURED.
SEE PAGE 9 FOR INSTBDCITON5 ON INURING DATA. INTO THIS SECTION.
2) CORRELATION CUUIlClEtas & KETfNTTCN TUB WDBCWB
REFER TDDIA3WM LABELED (2) ON PAGE 4.
•mis SECTION OF THE SPREADSHEET AUTOMATICALLY /^][l^irAfnBB S'lXl'lSTJLCAL
DMA SUZ AS CORRELATION CZZTFIOENT^RElSiriGN TUB NOUNS AM) SLOPE.
3) EQUATICNS OF STANDARD CALIBRATION CURVES
REFER TO DIAGRAM LABELED (3) ON PACK 4.
IN THIS SECTION, THE DA3& THAT VM ENTERED DUO THE STANDARD CURVE
!KX STEP 1 IS USED TO GEMXATE THE STMGARD CALIBRATION CURVES FOR EACH
ANAUfTE. NO DMA IS ENTERED IN THIS SECTION BY THE USER.
4) SAMPLE PEAK AREAS
REFER TO DIAGRAMS LABELED (4) Of PAGES 4 AM) 6.
THIS PART OF THE SPREADSHEET IS USED TO ENTER THE PEAK AREAS OF THE
HBBU llfS THAT ARE PRESENT IN EACH SAMPLE.
SEE PAGE 9 FOR INSTfOCTIONS ON ENTERDC DATA INTO THIS SECTION.
5) CONCENTRATION SHL'l'lCN
REFER TO DIAGRAMS LABELED (5) ON PAGES 4 AM) 7.
IN *im& SECTION OF THE SPREADSHEET> ^Vf CONCENTRATION OF EACH
Ma>'i'l(,LLK THAT VAS ENHMD IN STEP 4 IS CALOJLAT1D AUIONATICALLY
BY THE SOFTWARE.
SEC PAGE 9 FOR INSTKdlONS CN ENTERQC DAXA INTO THIS SECTION.
6) PERCENT RECOVERY SECTION
REFER TO DIAGRAMS LABELED (6) ON PAGES 4 AM) 8.
T^gg Hjfl'UJN OF THE SPREADSHEET TAKES THE ^TT1 _fMimJlQg (FROM STEP 4)
OF SPTJOD SAMPLES ONLY AM) DIVIDES TREK BY THE THEORETICAL
CCNQDORMXON TO YIELD A PERCENT RECOVERY OF EACH ANALYS.
SEE PAGE 9 FOR INSTRUCTIONS CN ENTS01C DAI*. INTO THIS SECTION.
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Curve Spreadsheet - Std Crv, Areas, Cone, Percent recoveries
All data is to be obtained from chromatograms
1 ) Standard Curve
a) Bring cursor to AO position by hitting "HOME" key. Bring cursor
A-l and replace test with set number being worked on.
b) Bring cursor to C3 - replace XX with set number being worked on.
c) Analysis date: enter range of dates for the standard curve.
d) Enter the raw areas and retention times for the corresponding
concentrations at top of each section. Only the A spike cone ID
number is at the top of the columns. The B spikes are as follows
A B
A028 A032
A029 A033
A030 A034
e) Hit space bar to calc
2) Sample Peak Areas
a) Move cursor to "HONE" then move to right until at block BCS.
Edit and enter set I being worked on.
b) Analysis date: Enter range of dates for samples in set being
worked on.
c) In block BG4 - enter curve * ie crv-set t being worked on.
d) Analyst: Hit edit, end and enter JV/EOP
e) Page: XX- replace XX with logbook page number for set being
worked on.
f) Go to block BD13, hit /,W.,T,V this freezes the compounds so you
can tell where you are entering areas.
g) Go to BX9. Enter sample blank. All lines across for each sample
number gets entered for M/B, LCSA & B this is QC tttt, for all
other samples it will be NAOXXXX. IQ's and CC's are not entered
here.
h) Cell BI10 is for the sample type code. Refer to IS summary sectic
for these codes.
i) Enter heading info for all samples
j) Enter raw areas for each sample
3) Concentration
a) Go to B065 - update set I, date, CRV, page t.
b) Go to BI9, hit /, C, everything, . and highlight all the headings
ie BI9-11 BJ9-11... Target range will be BI69 enter
c) Go to BI69, hit space\bar. The concentrations will be calculated
4) Percent Recovery
a) The percent recoveries are only calced for spike samples. Any fie
samples are going to be ignored. Go to BI69. Hit /, copy, everyth
., highlight BI69..BI71. Target range BJ123. enter
b) Go to BK69 and repeat above step
-------
c) Next go down the line. Copy headings for A spikes next to th« CSA
and a spikes down the line from LCSB
d) Once headings are copied - go up to cone section for each spike
sample - write the column letter the values are in ie LCSA - BJ,
LCSA - BK NA03714 - 3M
-------
'nstrument Quality Control Check - (IQ)
All of the followed data is obtained from the chromatograms
a.) For eacn IQCC, 6 measurements must be taken on the chromatogram:
1.) Distance from start - d BHC peak (nun)
2.) base width d BHC (nun)
3.) Distance from start - chlorthal (mm)
4.) base width - chlorthal (ma)
5.) width at 1/2 height - 1/2 width DCPA (ma)
6.) width at 1/10 height - 1/10 width DCPA (ma)
b.) Hit "Home" key to get cursor located in cell AO. Key in set #
the IQ was run with by hitting the edit key and typing set I in
place of the X's. If there is more than one per set letter
then A,B,C etc.
c.) Analysis date:
hit "Edit" then "end" and enter the date the IQ was run on
d. ) Time:
repeat above step and enter time as appears on the chromat
e.) Move cursor down to "W(l/2)-" line and over to 0.5. Enter 1/2 of
the 1/2 peak width of OCPA (should always be 0.5)
f.) Move cursor down. Enter 1/2 peak width of DCPA should be 1.0
g.) Hove cursoe down. Enter 1/10 peak width of DCPA
h.) Move cursor down. Enter start - chlorthal value
i.) Move cursor down. Enter start - dBHC value
j.) Move cursor down. Enter base width chlorthal value
k.) Move cursor down. Enter base width dBHC value
1.) Hit space bar to calculate
m.) Move cursor to "RESULTS" column. Compare the results to the
requirements. If any fall outside the set limits, make a note
of IQ-sett, date, time, and report to project manager
n.) Hit /, S, W
o.) Entr IQ-set * & letter if needed
DU2:[EPA_workarea.users)IQ-sett & letter
hit enter
-------
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-------
'sntinuing Calibration (CO
All cf the following data is obtained from the chromtograms
a.) Hit "Home" key to get the cursor located in cell AO. Key
in set « CC was run by hitting the edit key and typing in the
set number. If there are more than one CC per set, label
then as above with A. B,C, etc. to differentiate.
b.) Contract No: 3-729-001 should be left alone
c.) Calibration date: Find the appropriate concentration in the std
curve data (ie same as the CC you are working on) Enter the month
day and year by moving the cursor to the begining of thi« cell an
striking the "edit" key. Move th cursor to the right by hitting
the "end" key and type in date.
d.) Cont. cal date:
Enter month, day, and year as above
e.) Laboratory: Clean Harbors
Leave as is
f.) Time: (calibration)
In the first time cell from the top of the spreadsheet, enter the
time as it appears on the chromatogram for the std curve cone.
g.) Time:
Enter as above
h.) Move cursor to line "MIX A & B-X" Hit "edit", "end" and replace
"X" with code for concentration (i.e. lb,3, 4b, L,M,H...) for botl
initial and daily columns
i.) Calc the mean I.S. value for the A and B spike compounds from
the std curve for the given concentration. Then enter the raw .
areas for each compound. Use the calc'd mean value for OCB.
j.) repeat above step for daily cont. cal
k. ) hit space bar to calculate % difference
1.) move cursor to percent difference column if any are over
20%, note sample t, compound and percent difference. Inform
project manager
m.) hit /,S,W
n.) enter cc - (set I & letter if any) at end of
DU2:(EPA_workarea.users|cc-
the cc-#~entered should be the same as cell AO
-------
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(0.064696
(0.038281
(0.044856
(0.044051
(0.023706
(0.045154
(0.028318
(0.047210
(0.100966
(0.011149
"332237
2638.80
2008.60
1924.40
2129.00
1859.90
1525.30
1397.90
1190.30
2036.80
2147.90
1947.90
1297.40
454.68
OoBB.60
4107.50
3043.90
9401.40
1140.70
1223.80
2725.90
1567.40
1733.60
1686.30
900.35
1668.20
1044.40
1725.00
3532.00
369.38
•(O.umw
(0.065563
(0.049905
(0.047813
(0.052897
(0.046210
(0.037673
(0.034732
(0.029574
(0.050606
(0.053366
(0.048397
(0.032123
(O.QU296
(0.171153
(0.102054
(0.075628
(0.233586
(0.028341
(0.030406
(0.067727
(0.038943
(0.043072
(0.041897
(0.022370
(0.041448
(0.025949
(0.042859
(0.087755
(0.009177
1.91)
3.511
10.2t|
5.9I|
15.8t|
16.4t|
ia.3%!
18.S%|
15.4%)
16.011
13.4*1
0.5%)
12.4*1
9.4%)
8.3*1
0.3%)
4.7%)
1.7I|
4.0I|
4.9%)
S.6%|
8.2*1
8.4*1
9.2%)
13.1*1
17.7%)
t •
iittivi
i.s.
.ilrutoai :
-------
Internal Standard Summary - IS
All of the following data is obtained from the chroroatogram
a.) Hit "Home" key to get cursor located in cell AO. Key in set # b
worked on by hitting "Edit" key, "Home" key and replace X's with
b.) Laboratory & Contract tt stay the same
c.) Enter "set number" by hitting "Edit" "End" and enter set I being
on
d.) The "I.S. X area * 10*3" is obtained from the standard curve in i
lower right corner. Enter this number in block F9.
e.) Enter date or date range of the set being worked on
f.) "Alliance Sample *"
Enter numbers from the log sheet (either QC, ? or A, NAO t)
The order should be IQCC, blank, LCSA, LCSB, samples
including CC's and IQCC's.
For each sample * the sample type in parenthesis must be entered
These are: DTS A or B - TS day 0 1st analysis
HTE A or B - TS day 0 2nd analysis
HTS A or B - TS day 14 analysis
LSSA 0,1, or 2 - Lab spike A with cone level
LSSB 0,1, or 2 - Lab spike B with cone level
FLS - Field Sample
LCSA - Lab control Spike A
LCSB • Lab control Spike B
g.) Enter the raw areas for the I.S. for each of the samples in the s<
h.) Enter the dates each sample was run
i.) "EPA sample »"
For each NAO f there is a corresponding CPA number. These are fot
in John Verban's office for each set. Enter each EPA number. Foi
cont calibrations enter "cont. cal." For IQ enter "Inst. check",-
method blank - "Meth. Blank" LCSA - "LCSA" and LCSB - "LCSB"
j.) hit space bar to calculate
k.) if any % difference is over 20, note sample number, and a differer
Report to project manager
1. ) hit /, S , w
m. ) enter IS - set * in place of ISX-XX
DU2[EPA workarea.userJlS-sett
-------
•S. SUMMARY TABLE
LABORATORY:
I.S. X AR£A»10~3
EPA t
SAMPLE *
:iean Harbors
44209
IINST. CHECK
ICCNT. CAL. (P193-2
ICONT. CAL. |P194-2
1 METHOD BLANK IQC3692
IPC-2497-2-2-01
QC3694
I COOT. CAL.
IPC-2002-2-2-01
IPC-2242-2-2-01
IPC-2242-2-2-06
IPC-2164-2-2-01
CHECK
CAL.
I COOT. CAL,
IPC-2164-2-2-08
IPC-2164-2-2-13
IPC-2584-2-2-01
IPC-2584-2-2-05
IPC-2S84-2-2-13
ID<20%
\ P194-4
INA07013 (
F/S)
(NA07016
|W7g-i
|P194-3
|NW)7017 (
INA07018
INA07021
Contracct 3-729-001
Set Number 12
DATE: 9/2-9/6/B8
AREA | QATT |
1 i i r
X10-3 | ANALYZED (DIFFERENCE! OF CRV. |
47066 (9/02/88 1
40388 (9/02/88 (
40107 [9/02/88 (
37369 (9/02/B8 (
40124 (9/02/88 |
37687 (9/02/38 |
37774 (9/02/88 (
38908 (9/02/88 (
40815 (9/03/88 |
44716 (9/03/88 |
37063 (9/D3/88 (
41022 (9/03/88 (
40858 (9/03/88 (
39348 (9/03/88 |
44682 (9/06/88 (
47777 (9/06/88 | '
47625 (9/06/88 (
45984 19/06/88 f
42888 19/06/88 |
42044 (9/06/88 (
39904 (9/06/88 (
40152 19/06/88 (
6-46%! 106%!
8.64%| 91%J
9.28%| 91%!
15.47%! 85%
9.24%| 91%!
14.75%f 85%
14.56%! 85%!
U.99%! 88%!
7.68% 92% 1
™ T *•» f
1.15% 101»l
* • *•*» f JLU4V 1
16.16%l 8411
^w " ^*» » f 9^9 ^
7.21%J 93%!
7.58%! 92%!
11.00%) 89%!
1.07%! ioi%!
8.07%! 108%|
7.73%| 108%f
4.02%! 104%(
2.99%! 97%!
4.90%! 95%J
9.74%| 90%!
9.18%! 91%|
-------
riaa crooram • Fla
Data is obtained from the curve program.
a) Bring up the curve program for the set being worked on. Move to
the percent recovery section.
b! The Flag program can evaluate 3 A spike samples and 3 B spike samp
per program. Therefore, when extracting information, keep in sets
three or less. To file extract hit /, S, C enter name ( NAME Al),
supersede enter range- you should be highlighting LCSA and next tw<
spikes - the headings and values. Once range is entered, you will
back to ready. (It may be helpful to write down your file names.
They will be needed.)
c) Continue until all A spikes have a cut file
d) Repeat above step for B spikes but extract 1st the labels than the
values seperatly. Name these files Name Bl, Nan* B2 ect.
e) Bring up flag program. Bring cursor to AO. "Edit" and replace
X's with set #. If there are more than one, name set I A, B,ete.
f) Enter set # being worked on.
g) Enter analysis date for set being worked on
h) Enter sane as in AO
i) Enter Troa CRV" enter curve * for set
j) Position cursor in H10 sample
k) Hit /, S, L
1) Enter consolidate, then enter 1st A file ie Name Al
m) Enter "Replace"
n) "Input Range" - hit enter
o) "Target Range" - hit enter
The headings & values from the LCSA & 2 A spikes should be in the
flag program
p) Repeat above steps for 1st 3 B spikes but position cursor in H30
for B values H47 for B labels
q) Hit the space bar to recalc
c) Hit /, S , w - replace FLAX-XX with Fla - set I
DU2: [EPA_Workarea.Users) Fla-s«t* & letter
s) Repeat above steps for each set of 3 A & 3 B spikes or less than 3
-------
-------
Appendix E
Ftovtoion No. 3
Date: Februaiy 28, 1990
Pag« 1 of 4
APPENDIX E
STANDARD OPERATING PROCEDURE FOR AUTOMATED DATA ENTRY
-------
HeanHartors
Standard Operating Procedure for Transferring
IPS rata from the Hewlett-Packard Laboratory Automation
System to a 20/20 worksheet on the DEC MicroVax
1.0 SCOPE AND APPLICATION
This is a process whereby retention times and area counts froi
standard runs are put in a file and transferred from the Labo
Automation System 'LAS) to an IBM PC and then into a 20/20
worksheet en the DEC MicroVax. The IBM PC is physically linkei
both the LAS and the DEC MicrcVax.
2.0 SUMMARY OF PROCEDURES
The LAS command RF (Report to File) is used to put compound n<
retention times, and area counts from the six standard result
into a file called CALNPS.RPT. A command file called FRO«LAS.<
then invoked from the IBM PC. This command file transfers the
CALNPS.RPT file from the LAS to the hard disk on the IBM via
(a common file transfer protocol). A command file called T020
then invoked on the IBM. This command file transfers the CALN:
file into a temporary 20/20 file called TEMP and from this fi
extracts the area counts and retention times and places them
the final worksheet.
3.0 STEP BY STEP PROCEDURES
3.1 Once the six standard result files exist, go to the direc
command line in LAS and type RF (Report to File). This wi
bring up the Report to File screen.
3.2 Hit fl to create a report rased on file names/masks. This
bring up the File Names *asxs screen. Enter the name of t
A standard result file and press the tab key to move the
to the next line. En'ter INIT 7AL in the Rep.Format line a
press the tab key to move tr the next line. Enter CALNPS
Rep.File line and press t*i* tab key to move the cursor to
Overwrite option. Type YES and then hit return, wait unti
File Names/Masks screen re-appears. Then type in the name
High 8 standard result file. Then tab to the Overwrite op
and type in NO. Tab to the Append option and type in YES.
hit return. Wait until the File Names/Masks screen re-app
Now enter the name of the MED B standard result file and
return. Repeat this step until all six of the result file
been entered. MOTE: It is VERY important that the result
-------
fleanHarixjrs
get entered in the correct order. The correct order is: Hi
High B; MED A; MED B; LOW A; LOW B. After all the result f
nave reen entered and the File Names/Masks screen re-appea
hit tne End Function softkey (f8).
3.3 Go to the I3M PC in the LABSAM computer room. If it says "
USE THIS TERMINAL", hit the ALT and S keys together. This
stop the automatic report generator program. If the terrain
looks busy, you will have to wait until it says "DO NOT US
TERMINAL". After hitting ALT-S you will get a green comman
at the bottom of the screen in which the cursor will be
blinking. Type INVOKE FROMLAS.CMD and hit enter. The PC wi
then make a few beeps, transfer the CALNPS.RPT file to the
and then log off. Wait until it is finished doing this (sh
only be about 30 seconds). Instructions on what to do next
appear en the screen as a reminder. When this happens, it
it is finished with this step.
3.4 Hit fiO, then hit f8 twice. A "C>" prompt will appear on tl
screen. Flip the switchbox to position B and type R3V and I
enter. This will stop the IBM from emulating an HP termina
start the DEC terminal emulation.
3.5 The Basic Configuration menu will appear on the screen. Hi'
to accept the default configuration.
3.6 Hit the ALT and Y keys together. This will make the green.
command line appear at the bottom of the screen. Type INVOf
T0202Q.CMD and hit enter.
3.7 Enter the name of the 20/20 template worksheet and hit ent<
NOTE: You DO NOT have to enter the file prefix
DU2:(EPA_WORKAREA.USERS 1 ; but you must spell the rest of tl
file name correctly or the program will bomb.
3.8 Enter the name you want to save the 20/20 worksheet under <
hit enter. Again, you DO NOT have to enter the file prefix
you must enter a file name that doesn't already exist or t."
program will bomb.
3.9 The program will then copy the CALNPS.RPT file from the PC
the DEC MicroVax, import that file into a temporary 20/20 f
import the information from the temporary 20/20 file into t
blank template file and save it under the name you specific
This will take about three minutes. When the program is
finished, instructions on what to do next will appear on tti
screen as a reminder.
3.10 Hit fS twice to stop the DEC terminal emulation. Turn the
switchbox back to the A position. At the "C>" prompt, type
-------
fleanHaitofs
and hit enter. When the screen turns blank, hit enter to <
"Login Name?" prompt. Login as user LABSAM with password >
At the "Module Selection:" prompt hit the ALT and Y keys
together. This will give you the green command line as be
Type INVOKE AREPT.CMD and hit enter. This will re-start t!
automatic report generator program that was running befor
3.11 Go back to your DEC MicroVax terminal and call up the ne<
created worksheet. You will have to CALC the worksheet am
analysis times, etc. The above process only enters retent
times and area counts for the six standard runs.
-------
Appendix F
Revision No. 3
Date: February 28, 1990
Page 1 of 17
APPENDIX F
NPSIS SAMPLE RECEIPT SOFTWARE FOR LABORATORIES DATED 4/5/88
-------
MEMORANDUM 4/5/88
TO: JOANNA HALL, ALLIANCE TECHNOLOGIES, INC.
FROM: CHIP LESTER. ICF ISC.
RE: NPSIS SAMPLE RECEIPT SOFTWARE FOE LABORATORIES
ICF's National Pesticide Survey Information System (NPSIS) is ready to
collect information from you regarding the receipt of well water samples and
cheir 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, che software allows you to report the receipt of a
one or more sample kits. It also prompts you for details regarding the
condition of che samples. Additional features include; a bulletin board whit
allows you to interactively send messages to ICF staff via your computer
keyboard, file transfer, and access to the ICF computerized mail system for
sending memos. It is also possible for you to speak over the phone to an 1C.'
staff member during your session.
It is important that you test the communications link between the NPSIS
computer and yours. We have experienced trouble when using Carbon Copy
software with a computer which has a Manzana 3.5 inch disk drive, and also
with computers which have a non-Hercules or non-EGA compatible graphics card
For testing purposes, your sample kit identification numbers and FedEx
airbill numbers (respectively) are: PD-0000-241 and 1111111111, and PD-0000-
242 and 2222222222. Use these sample kit identification numbers when trying
out che NPSIS Sample Receipts Program.
We feel chat 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 che
phone during your session. If you would like to do this, please call Beth
Estrad* at (703) 934-3431. NPSIS will be available for access 24-hours a da
seven days a week. We appreciate hearing any comments you have regarding
NPSIS.
-------
THE NPSIS SAMPLE RECEIPT PROGRAM
.VPSIS is designed to keep crack of che day co day operacions of Che
Macional Pescicide Survey. You play an imporcanc role in NPS and your ciae
notification of receiving a kit of samples is essencial co che success of N!
We have designed che Sample Receipt Program with your busy schedule in mind
NPSIS will obtain che minimum amount of information necessary while still
maintaining a secure system. You will be entering data into che NPSIS
personal computer via your own computer, modem, and Carbon Copy software.
I.I Hardware and Software Requirements,
The NPSIS Sample Receipt Program has a minimum hardware and software
requirement. Here is a list of icems you will need:
Hardware:
One (1) IBM PC. XT. AT, or Personal System modal with at
least 640K memory.
One (1) 2400 or 1200 baud Hayes or Hayes compatible nodei
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 co yo
by ICF for che duration of NPS.
1.2 Initial Installation Steos.
Before you can access and use SPSIS. you must first load the Carbon Copy
software onto your PC. The directions are provided in che 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 che Call Table, press "2" from the Carboi
Copy Parameters' Screen. The information you must enter consists of the
following:
-------
• Name: NFS
• Telephone Number: 703-^1-0629
• Password: MPS
1.3 Paraagrgrs for C"lBB1Jn1 cations .
NFS IS will maintain a sec configuration throughout operation. Any
changes due co updates in equipment or the system which will affect your
ability to communicate through Carbon Copy will be forwarded to you. The
paraaeters which will be maintained at this time are:
• 2400 baud modem speed.
• Answer ring count equal co 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 NFSIS and resume your session.)
• five minute inactivity time constraint.
• Two password attempts.
2—E&fiBXXEKLA
SAMPIJt RECKTPT TO HPSTS
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:> CCHELP 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.
2.2 Entering A Sfljy^t Receipt Into NPSIS.
Once you have established a data link, ( e.g., are "logged on"), you vil
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 Saaple Receipt Program.
Remember that you are controlling the NPSIS computer via a 2400 baud phone
line and your typing will appear on the screen ac a much slower race than yoi
are accustomed to. A few tips on how to use the system are outlined in the
next section.
-------
2.2.1 Useful Tips on How co Use MPSIS.
Before you scare, a few things Co remember are:
• Pressing che "Esc" key will cancel all changes for che screen you
are currently in and return you co che previous screen. Pressing
"Esc" ac che Searching Screen recurns you co che main menu.
• Pressing "PgDn" or "PgUp" will save the items you have entered in
che current screen and place you in the next or previous screen,
respectively. This feature is handy to use when you only have a 1
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 chat using the
sideways arrows will not work.
• Pressing che "Alt" and "Right Shift" keys together will place the
Carbon Copy Control Screen over che NFSIS Sample Receipt Program.
You can then use che communications features in Carbon Copy.
Pressing "F10* again when you are chrough will replace the NPSIS
Sample Receipt Program screen you were currently in back on your
screen, and
• Because you will are mosc likely co be entering information
regarding a number of kics ac one time, after you save or cancel
your entries for one kit. you will be placed at che initial Sample
Searching Screen for a new kic. If you are finished with your da.t:
entry, simply press "Esc" co exit che Sample Searching screen and t
placed in the main menu.
2.3 A Basic Outline of che S^Uffple Receioc Program.
The NPSIS Sample Receipt Program has chree basic features:
• Initial reporting of a SPS sample kit of sample bottles.
• AbiliBy co edic or re-edic an existing report of a kic
receipt, and
.• Access co ICFs computerized mail system which provides ch
ability to send memoranda to ICF staff.
The information obtained in an encry for a kit of bottles is:
• The kit identification number, the FedEx airbill number.
and the last name of che person making che entry.
• Any damage co che kic as a whole such as melted ice or an
breakage of che cooler.
-------
Verification of which boccles belong in a kit or cooler,
nocificacion of any missing boccles or any additional
boccles, and
Any damage co each sample boccle which renders ic unusab]
for analysis and Cescing.
SPSTS Sanml* Receine Prt
When you have completed the logon procedure, you will see che following
main menu on your computer screen:
NATIONAL PESTICIDE SURVEY INFORMATION SYSTEM
SELECTION MENU FOR REPORTING SAMPLE RECEIPTS 04/05/88
Report \ Edic a Sample Receipt
Send a Memo
Press
-------
N'PS Sample Receipt Searching Screen
** Encer :he following items co access kit information **
To find che Kit information in NPSIS in the most complete
and accurate fashion, please enter the Kit number and the
FedEx airbill number.
Enter kit number:
> PD-0001-151
Enter FedEx airbill «:
> 1111111111
Enter your Last name:
> CHIANG
Press ESC to exit the searching *
If the kit number you have entered is incorrect, or if the kit number ai
FedEx airbill number combination is incorrect, NPSIS will prompt you to try '
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.
-------
One* you have correctly identified the sample kit, NPSIS will ask you if
:here is any damage co che kit as a whole:
Kit No. : PD-0001-1S1
Uas there any damage to the sample kit? (Y/N)
PgDn (Next page), PgUp (Previous page), Esc (Exit)
-------
Next. NPSIS will ask you co survey the concents of the kit and check ch«
which bottles are contained within che kit. You should then look ac 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 01
the list provided by NPSIS on this screen:
Kit No.: PD-0001-151
Please compare the following bottle numbers
with those in the sample kit.
Bottle No:
Bottle No:
Bottle No:
Bottle No:
Bottle No:
Bottle No:
PD-0001-1-1-01
PD-0001-1-1-03
PD-0001-1-3-01
PD-0001-1-3-03
PD-0001-1-9-01
PD-0001-1-9-03
Did you receive exactly these bottles in the sample kit? (Y/N) H
PgDn (Next page), PgUp (Previous page), Esc (Exit)
-------
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!
NPSIS is designed to track Kits and FedEx airbill numbers.
The Kit and FedEx airbill number combination you have entered
does not match what is currently in the system. Please enter
the correct combination. If you still have problems, try
Leaving the FedEx airbill * BLANK. Only enter the Kit number.
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 encer the correct Kit numoer and FedEx airbill number?
SPSIS is designed to store and rrack 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)
-------
Next, NPSIS prompts you Co indicate if any of the individual bottles ha-
been damaged and rendered unusable for analysis:
Kit No.: PD-0001-151
Was there any damage to the sample Bottles? (Y/N) Y
PgDn (Next page), PgUp (Previous page), Esc (Exit)
-------
If you press "Y" , .VPSIS will then prompt you for the apparent cause of
damage:
Kit No.: PD-0001-151
Was chere any damage to the sample kit? (Y/N)
Please indicate the cause for damage:
Kit is broken (Y/N) Y
Ice is melted (Y/N)
Other Reason (Y/N)
Please enter any comments about the sample kit.
Comments: Broken upon arrival.
Comments:
PgDn (Next page), PgUp (Previous page), use f ^ or *-* to select field.
There may already be comments regarding the kit in the comment field
shown in the above screen. In this case, please enter your comments after an
which already appear. This insures that no information is destroyed.
-------
Sow you have completed all of the necessary information needed to verify
chac che proper samples have reached their final destination in usable
condition. You may save your kit entry by pressing "Enter". If you wish to
cancel your kic entry and cry again, press "N" and "Enter". If you wish co
view or edic :he current kit entry, press "R" and "Enter" and NPSIS will plact
you back ac che 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 chis entry by pressing 'R' and 'Enter'.
* * * Accept entries? * * *
* Press ^- co Save *
* Press N and ^—* co Cancel *
* Press R and -**-1 to Verify or Edit * Y
By pressing "Enter" , you have saved ail of the information necessary for
a particular sample kit. NPSIS assumes chat you will encer more Chan 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 che
main menu. You can then log off of NPS IS by pressing "Alt" and "Right shift"
at the same time. You may also send a memo through the ICF computerized mail
system. To do chis, cursor down co che second menu choice and press "Enter".
Th« next cwo pages of chis meao describe how to use the ICF electronic
mail system. Note that the password for you is NPS. The mail system software
program will prompt you for this password before it will allow access to the
system. Also, when you are selecting che recipients of your memo, please
press che space bar beside che initials "NPS". This will send your memo to
all ICF staff involved in the NPS project. If you wish to send memos to a
particular ICF staff member, please call 3eth Estrada for the identification
number of che desired ICF employee.
-------
If you have pressed "N", indicating chac you did noc receive exactly wha
NPSIS assumes you have received, you will be prompted to encer the appropriat
information. This information includes pressing a "Y" or a "N" beside each
bottle, and entering the bottle number found on the labels of any additional
bottles vou have received:
Kit
1.
3.
5.
7.
No.: PD-0001-151
Please indicate which
Bottle No:
PD-0001-1-1-01
PD-0001-1-1-03
PD-0001-1-3-01
PD-0001-1-3-03
PD-0001-L-9-01
PD-0001-1-9-03
bottles you received:
Received (Y/N)
N
H
Y
Y
Y
Y
Please indicate any additional bottles you received:
Bottle No.: PD-0002- 1- 1-05 2. Bottle No. PD- 0002- 2- 2- 01
Bottle No.: PD-OO04-4-4-01 4. Bottle No. - - - -
Bottle No.: - ... 6. Bottle No. - ...
Boctle No. : - - -
8. Bottle No. - .--
PgDn (Next page). PgUp (Previous page), use f |or •*—'co select field.
Notice chat the user has indicated that he did not receive the first rvo
bottles on the list. Also note that the user has indicated additional bottle
which have come in the sample kit, but which were not on the list.
-------
In order to complete the appropriate information on damaged samples, yoi
muse first press a. "Y" or a "N" in the field Labeled "Damaged Y/N". If you
have entered a "Y" in this field, you must then identify whac che cause of t!
damage is, to che 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 comment whenever possible.
Kit No.: PD-0001-151
Please indicate which bottles are damaged by entering Y or N,
and for those which are damaged, indicate the cause of daaage.
---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 H
PD-0002-1-1-05 H
PD-0002-2-2-01 Y Y
PD-0004-4-4-01 N
The 'Other' cause category is for reporting contamination of a. sample,
e.g. contamination noted on the Sample Tracking Form, air bubbles,
or other reasons a sample is unusable.
PgDn (Next page), PgUp (Previous page), use 4 I or
to select field.
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ELECTRONIC MAIL
Function
Augment office communications
electronic transfer of notes and files.
with
Reading Mail
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 givea
your password and entered E-Mail, you can
change your password by selecting Options,
then Password.
met
pr<
Select "Read* from your
Highlight read,then
.
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.
Press <£SC> to select another note.
Writing Mail
1. Select "Compose", then "edit".
2. Press when the highlig
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 b;
twice to "de-select" recipients
The small mark will disappej
d. Press to cancel the
entire list.
4. Select the initials of those who wi
receive copies:
a. Press the down arrow to m
to "CCT.
b. Select recipients as instruct*
above (step 3, a-d)
-------
Writing Mail, continued
5. Eater a. subject and priority.
(optional)
6. Select attachments (optional):
a. Press and type the
path for the document(s).
b. Press and select the
document(s) to be attached.
c. Repeat steps a and b for
documents in another directory.
7. Enter the text of your message.
8. Press when finished.
9. Select "Transmit" to post the note
and attachments.
Quitting tht Mail Program
1. Press from the menu.
2. Select "YES".
-------
App*ndbcG
Revision No. 3
D«to: February 28, 1990
Pafl*1 of 3
APPENDIX G
NFS RAPID REPORTING SYSTEM DATED 4/12/88
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pl- •• UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
v '* CINCINNATI OHIO *S268
MEMORANDUM
DATE: April 12, 1988
SUBJECT: KPS Rapid Reporting System
FROM: David J. Munch, Chemist
Drinking Water Quality Assessment Branch
TO: MPS Technical Monitors
Jerry Kotas has requested that any confirmed results of health
significance be reported as quickly as possible. Therefore, if an analy
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 aoalyte 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 th* occurrence of X?S analytes thi
may occur below the MRL, and are not listed on the attached tables, have
not yet been finalized.)
1. The appropriate confirmational analyses (GC/MS for methods 1-3,
6-1, second column for Method 5) should be performed as soon as
practical.
2. The laboratory should telephone their Technical Monitor, the sai
day the confirmation is completed. .
3. The laboratory should immediately document the observed result i
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 infer
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 ma
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 telepbon
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 sampl
site be conducted, and reported in writing, am soon am practical
-------
NZTBOD 12
AMALYTE JAPID REPOKTIlfG LXVIL
tlpht-Chlordtne 0.5 ug/L
gaaaa-Chlordtae 0.5 uff/L
Cblorotbtlonil 150 ug/L
Daethal (DCPA) 5,000 ug/L
Dieldrin 0.5 ug/L
Propacblor 130 ug/L
Triflurtlin 25 ug/L
-------
Appendix H
Revision No. 3
Date: February 28, 1990
Page 1 of 2
APPENDIX H
DATA REPORTING FORMAT CHANGES DATED 4/18/88
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DAT*: iprii is. 19M
SUBJECT: Oat* Rtporting Format Changes
mOB: David J. Hunch, Chemist
Drinking Rater Quality assessment Branch
TO: IPS Technical Monitors (See below)
The purpose of this Memorandum is to consolidate the changes to the
I?S data reporting format, which have occurred since it vas originally
constructed. Tou have preTiously been supplied vith most of these changes,
but please check to b« 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 pi measured in
the field. This data will b* found on the field sample tracking
sheet.
2. Line 2. columns 67-70 are to be used to record the pi measured
upon sample receipt at the laboratory. This oaly applies to
methods 5 and 9.
3. Line I, columns 1-13. Sample Identification lumber, have been
expanded to columns 1-14.
4. The data entered on line 10, columns 52-60, concerning the
internal standard, it should be entered mot 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" cod* (lime 11, columns 1-5).
the following codes should be used to designate the various types of
spiked samples.
LCSt
LSStff
OTS0
rrst
Laboratory Control Sample
Laboratory Spiked Sample
Day 0 Tim* Storage Sample
Extract Tim* Storage Sample
Sample Time Storage Sample
In addition, two clarification* have b*«m mad* to the codes for
analyt* concentration entries.
•9ft • lot Detected « 1/3 liaimum Importing Limit)
-111 • Below Minimum It porting Limit but greater than or *
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Appendix I
Revtelon No. 3
Date: February 28, 1990
Page 1 of 5
APPENDIX I
NPS ANALYTE REPORTING BELOW MRL AND IDENTIFYING UNKNOWN PEAKS DATED 6/1/88
-------
I UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
w
' CMvnioNMi«rrAi CHIMICTIV LASOHATOHY. MASA/NCT.
'•< ««J>»* SmUMMQ «•. MSTl. MB
June 1, 1988
MEMORANDUM
SUBJECT: NPS Anaiyte Reporting Below MRL and Identifying Unknown Peaks
FRCM: Bod Maxey, Analytical Coordinator
Environmental Chemistry Laboratory /^ I \juy4J*
TO: Dave Munch, Analytical Coordinator
TSD-Ci nci nnat i
Aubry E. Dupuy, Jr., Tecnnical 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 Liroits and to attempt ident
fication of unknown peaks. Please see that your contractors and Technical
Monitors get this information and that applicable parts are incorporated int<
their respective QAPPs.
If you have any questions, give me a call.
-------
Determining and Reporting the Presence of NPS Analytes Below The
".inimal Reporting Levels and Identifying Unknown Peaks
Background Information
The Office of Pesticide Programs (OPP) has requested that the NPS analyti-
cal contractors and referee laboratories make an effort to report the presence
of NPS analytes below the Minimal Reporting Levels (MRL). Me have also been re-
quested to attempt to identify unknown peaks or responses. To assure chat 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 Reoomng the Presence of NPS Analytes Below the
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 B/. 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 tak
place before continuing low-level analytical work on the analyta(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 confir
mation is not within the capability of the laboratory, such extracts are
sent weekly, under iced conditions by next-day air, to the appropriate re-
feree Laboratory having HR GC/MS c/ capabilities. Copies of chronatograms
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 th« extracts.
Volume level must be marked on the outside of the vial or ampule.
A/ * NPS method 1 MRL « 4 x EDL NPS method 5 MRL - 3 x EDL
NPS method 2 MRL - 5 x EDL NPS method 6 MRL » 3 x EDL
NPS method 3 MRL « 5 x EDL NPS method 7 MRL « 3 x EDL
NPS method 4 MRL « 5 x EDL
B/ * Method 6 has an MRL > the Health Advisory Laval. All suspect BID
responses of 1/2 MRL - MRL require additional work for this method.
C/ - LR « GC/MS « Low Resolution mass spectromatry.
HR GC/MS - High Resolution mass spactronacry.
-------
c. For Metnods 4 and 5, HPLC Methods, there ia no provision for GC/MS
confirmation. Suspect analytes between 1/2 MRL - MRL will be subject
"- (1) and (2a) above.
'revisions of (2b) also apply except references to GC/ns requirements.
3. Whether the identification of the analyte is attemoted at the contractoi
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 response;
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 cake place before continuing low
level analytical work on that analyte.
Procedure for Determining the Identity of Non-NPS Analytes
It is expected that, over the course of the NFS Program, numerous
extraneous responses will be evident on chromatograms from the various methoc
The contractor or referee laboratories will be required to attempt identifi-
cation of peaks or responses on the primary column exhibiting the minimal cm
below.
1. For Methods 1, 2, 3, 6, and 7, if, upon initial analyses, the respoi
of an extraneous peak on the primary column is equal to or greater
the response of the nearest NFS analyte on that column at 10 x MRL
(Minimal Reporting Level), an attenpt must be made to identify that
known peak or response by GC/MS. Pull scan spectra and subsequent
library search are expected and must be followed by comparison of t
spectra of the unknown compound with those of an authentic standard
the suspected compound.
2. The work in (1) must be attempted by the contractor and/or referee
oratories on the first occurrence of such a peak and the results of
attempt reported to the Technical Monitor for the Method. If the
analytical contractor feels his system or instrument is not capable
the confirmatory work, he oust send both that extract and that of t
related Method Blank t? 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 ti
seal and do not contribute interferences to the extracts. Volume 1
must be marked on the outside of the vial or ampule. (IPS will aba
costs of these shipments.)
-------
Specific sample and analytical information must accompany each such
extract.
o Sample i.d. number/ weiqht of sample matrix contained in the
ampule, copies of chroma tog rams from the primary GC col mm,
identification of the retention window for the unknown response!a]
as defined by the last NFS analyte to elute before the unknown
peak or response and the first NFS analyte to elute following the
unknown response.
3. Whether the identification of the unknown compound is attempted at the
Contractor Laboratory or at the referee laboratory/ only the compounds
positively confirmed by GC/MS will be reported beyond the Technical
Monitor for the Method and the Analytical Coordinators. No unconfirmed
data will be reported outside the NFS analytical system. Unsuccessful
attempts at identification will also be reported to the Technical
Monitor.
4. Following either the successful confirmation of two such extraneous peal
proving to be the same compound or two failures to identify a response
with the same retention time without a prior successful GC/MS confirmat:
on a sample/ discussions with OPP personnel will take place before cont:
with identification work on that particular compound.
THE QUALITY ASSURANCE PROJECT PLANS FDR BOTH THE ANALYTICAL CONTRACTORS
AND REFEREE LABORATORIES TOR METHODS 1, 2, 3, 6, AND 7 MUST REFLECT THE1
COMMITMaJTS TO THESE TWO REQOIREMHTTS.
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 NPS ANALYTES BELC
THE MRL.
-------
Appendix J
Revision No. 3
Date: February 28, 1990
Page 1 of 4
APPENDIX J
REVISIONS TO NPS RAPID REPORTING SYSTEM DATED 6/9/89
-------
\ 5J8R' UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
- -
KIMORANDUM
DATS: June 9, 1989
SUBJECT: Revisions to HPS Rapid Reporting System
rtOM: David J. Hunch. TSD Project Manager
National Pesticide Survey
TO: NPS Technical Monitors
Recently the health adTitory documents for priority UPS analytes were
finalized (at least as finalized as they ever get). In many cases, the
health effect value used to deteraioe the concentration of each analyta
that "tri90tred" the rapid reporting systea. has changed. The purpose of
this •••ora.advia is to transmit to you the final rapid reporting
concentration*, and to remind everyone of the provisions of the rapid
reporting system.
le you remember, if an aaalyte luted in the attached tables is
observed 10 the primary analyses, at or above the rapid reporting limit.
the following actions should be instituted, for thy listed antlyte where
the rapid reporting level is less than or equal to 1/2 the einiaui
reportiof level (KRU. aay occurrence at or above 1/2 the HXL should alto
be processed as belo*.
I. The appropriate confirmational analyses (CC/HS for methods
1-3,i-7. second eoluma for method b) should b* performed as soon
as practical.
:. The laboratory should telephone their Technical Monitor, the same
day the confirmation is completed.
J. The laboratory should immediately document the observed result in
a letter to their Technical Hoaitor.
4. &• quickly as possible oa the day the above telephone call IS
received from the laboratory, the Technical Monitor should inform
their laboratory Amelytieal Coordinator of the finding. The
Technical Monitor should forvard on to the Laboratory Analytical
Coordinator the above documentation, with aay comments he/she nay
have coaceraiaf the validity of the result.
5. Tae Laboratory Analytical Coordinator should inform the Surtey
Director and the second Analytical Coordinator of the finding by
telephone the sene day if possible, and in writing after the
docuaemtetiom ie received frost the Technical Monitor.
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
-------
HETBOD 12
JUULYTE RAPID REPORTIUC LTYIL
tlpbt-Chlordtne 0.5 ug/L
guaa-Chlordane 0.5 u0/L
CblorotbAloail 150 ug/L
Dtcthtl (DCPA) 5,000 ug/L
DicldriD 0.5 ug/L
Propacblor 130 ug/L
Triflurtlin 25 ug/L
-------
- 2 -
6. The Analytic*! Coordinators are to requeit,throuoh the
appropriite Technical Monitors, that all analy*** for this saaple
•it« b« conducted, and reported in writing. «* «oon a* practical.
II you ha»* any qutation* conc«rnmo th»t« proc«dur««, pl*a*e l«t lob
H«x»y or •• knot*. Xl«o, pl«a«» pass on thif information to your contract
and referte laboratories.
Attachjient
Addressees:
M. Bolyard
A. Dupuy
R. Haxey
I. Sorrell
M. Zuiker
cc:
J. Bolted
H- Brass
L. Jobnson
A. Kroner
C. Lester
L. Vac Den Berg
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