United States Office of Water (WH-550) EPA 8104-82-010
Environmental Protection Office of Pesticides and February 1992
Agency • Toxic Substances (H-7501C)
QUALITY ASSURANCE PROJECT PLAN
FOR THE
NATIONAL PESTICIDE SURVEY OF DRINKING WATER WELLS
ANALYTICAL METHOD 1
Prepared by:
Environmental Chemistry Section
Office of Pesticide Programs
U.S. Environmental Protection Agency
NASA/SSC Bldg. 1105
Stennis Space Center, MS 39529-6000
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 (PH2J)
77 West Jackson Boulevard 12th Float
Chicago, IL 60604*3590
-------
APPROVAL PAGE
Robert Maxey
_, ECS Project Leader
_, EPA Technical Monitor
Aubry E. Dupuy, Jr. Section Chief, ECS
Danny McDaniel
_, Acting ECS QAC
Lora Johnson
, NFS QAO
Elizabeth Leovey
, OPPQA Officer
List for Distribution:
R. Maxey, OPP/ECS
A. Dupuy, OPP/ECS
D. McDaniel OPP/ECS
L Johnson, NPS QAO
E. Leovey, OPP/QAO
G. Gardner, OPP/ECS
C. Byrne, STI
R. Shaw, OPP/ECS
-------
Section No. 2
Revision No. 4
Date: December 1989
Page 1 of 6
NATIONAL PESTICIDE SURVEY
QUALITY ASSURANCE PROJECT PLAN FOR
ANALYTICAL METHOD 1
2. TABLE OF CONTENTS
Section Pages Revisions Date
1. TITLE AND APPROVAL PAGE 2 4 12/89
2. TABLE OF CONTENTS 6 4 12/89
3. PROJECT DESCRIPTION 1 4 12/89
4. PROJECT ORGANIZATION AND RESPONSIBILITIES 2 4 12/89
5. QUALITY ASSURANCE OBJECTIVES FOR
MEASUREMENT DATA 5 4 12/89
5.1 Initial Determination of Capabilities;
Determination of EDLs; Determination
of Reporting Levels
5.2 Determining and Reporting the Presence
of NPS Analytes Below the Minimal
Reporting Levels (MRL) and Identifying
Unknown Peaks
5.2.1 Procedure for Determining and
Reporting the Presence of
NPS Analytes Below the MRL
5.2.2 Procedure for Determining the
Identity of and Reporting
the Presence of Non-NPS
Analytes
5.3 Laboratory QC Requirements for Primary
Analysis
5.4 Laboratory QC Requirements for Secondary
Column Analysis
5.5 Laboratory QC and Extract Handling Related
to GC/MS Confirmation
5.6 Sample Management
6. SAMPLING PROCEDURES 4 4 12/89
6.1 Sample Requirements
6.2 Labelling of Sample Bottles
6.3 Field Sample Tracking Form
7. SAMPLE CUSTODY 6 4 12/89
7.1 Tracking and Notification of Sample
Shipments
7.2 Sample Requirements Following Receipt at
Laboratory
7.2.1 Storage Conditions
7.2.2 Holding Times
7.2.3 Disposal
-------
Section No. 2
Revision No. 4
Date: December 1989
Page 2 of 6
2. TABLE OF CONTENTS (continued)
Section Pages Revisions Date
7.3 Return of Sample Kits to EPA Contractor
(ICF)
7.4 Receipt of Extracts from Analytical Contractors
for GC/MS Confirmation at ECL
7.5 Internal Practices Concerning Sample Storage
8. CALIBRATION PROCEDURES AND FREQUENCY 7 4 12/89
8.1 Method 1 Standards
8.1.1 Calibration Solutions
8.1.2 Standards Prepared at ECL
8.1.3 QA for Diluting and Checking the
Standards
8.1.4 Calibration Solutions and ECL
Standards Verification
8.1.5 Frequency of Calibration Standards
Checks
8.1.6 Association of Calibration Standards
to Survey Sample Analysis
8.2 Instrumentation Checks and Quantitation Procedure
8.2.1 Calibration of HR QC/MS
8.2.2 Calibration of Low Resolution GC/MS
9. ANALYTICAL PROCEDURE 2 4 12/89
9.1 Summary of Method
9.2 Major Equipment/Instrumentation to Be Used With
Method 1
9.3 Analytical Method
9.3.1 Method as Developed by Battelle
9.3.2 Differences from Battelle Method
9.3.3 Requirement for Authorization to Deviate
from Battelle's Method
9.4 Sample Sets
10. DATA REDUCTION, VALIDATION AND REPORTING 6 4 12/89
10.1 Data Reduction
10.2 Data Validation
10.3 Data Reporting
10.4 Storage of Lab. Data
10.5 Fast-Track Reporting
10.6 GC/MS-Data Reduction, Validation, and Reporting
10.6.1 Data Reduction
10.6.2 Data Validation
10.6.3 Data Reporting
10.6.4 Filing and Storage of GC/MS Data
11. INTERNAL QUALITY CONTROL CHECKS 7 4 12/89
11.1 Primary Analyses
11.2 Confirmational (Secondary-Column) GC Analyses
11.2.1 Criteria for Peak Symmetry Factor (PSF)
11.3 GC/MS Confirmation
-------
Section No. 2
Revision No. 4
Date: December 1989
Page 3 of 6
2. TABLE OF CONTENTS (continued)
Section
11.4 Control Charts
11.4.1 Establishing Control Charts
11.4.2 Outliers
11.4.3 Plotting Data on Control Charts
11.4.4 Out-of-Control Situations
11.4.5 Updating Control Charts
11.5 Other QC Checks Performed at ECL
11.5.1 QC Data Sheet
11.5.2 NPS Groundwater QA Data Form
11.6 Exceptions to the QAPjP
11.6.1 Request for Approval
11.6.2 Documentation and Following
Requirements
12. AUDITS
12.1 Requirements
12.2 Frequency
12.3 Nature of Audits
12.3.1 Tech. Systems to be Addressed
12.3.2 Data Quality Audits
12.3.3 Performance Evaluation Audits
12.4 Standard
12.5 Reporting and use of Audit Results
13. PREVENTATIVE MAINTENANCE
13.1 Gas Chromatographs
13.2 GC/MS
14. SPECIFIC PROCEDURES FOR ASSESSING
MEASUREMENT SYSTEM DATA
14.1 Formulas Related to Instrument Control
Standards and Determination of
Chromatographic and Column
Performance
14.2 Formulas for Calculating Statistics
14.3 Formulas for Defining Control Limits
15. CORRECTIVE ACTION
16. QUALITY ASSURANCE REPORTS TO
MANAGEMENT
Pages Revisions Date
12/89
12/89
12/89
12/89
12*89
-------
Section No. 2
Revision No. 4
Date: December 1989
Page 4 of 6
2. TABLE OF CONTENTS (continued)
Appendices Pages
A.
B.
C.
D.
E.
F.
G.
H.
1.
*J.
*K.
SAMPLE CUSTODY
BATTELLE'S VERSION
DATA FLOW (REDUCTION, VALIDATION,
AND REPORTING)
SIGNIFICANT FIGURES AND ROUNDING OF NUMBERS
STORAGE OF NPS HARDCOPY DATA FILES AT ECL
DIXON'S TEST
ADDITIONAL QUALITY CONTROL CHECKS
ECL COMPUTER PROGRAMS
RAPID REPORTING NOTIFICATION
GC/MS CHARACTERISTIC IONS FOR METHOD 1
ADDENDA TO METHOD 1:
7
%0
12
4
3
3
9
3
6
4
Revisions
4
4
4
4
4
4
4
4
4
4
Date
12/89
12/89
12/89
12/89
12/89
12/89
12/89
12/89
12/89
12/89
JUNE 1988 TO DECEMBER 1989
11
12/89
* In this QAPjP Rev. 4, an asterisk in the left hand margin of the text indicates an addition or
revision to the ECS NPS QAPjP Rev. 3 of June 15,1988. The edited text will be followed by an
effective date in parenthesis and, when applicable, a reference to the addendum in Appendix K
which addressed the change.
-------
Section No. 2
Revision No. 4
Date: December 1989
Page 5 of 6
2. UST OF FIGURES
Figure
ECS ANALYTICAL TEAM - METHOD 1
LABEL OF SAMPLE BOTTLES
FIELD SAMPLE TRACKING FORM
SAMPLE RECEIPT SCREENS FOR NPS LABORATORIES
TEMPERATURE MONITOR CHART EPA/ECL
NPS EXTRACT SHIPMENT
STANDARD SOLUTION DATA FORM
CALIBRATION SOLUTION RECEIVING FORM
STANDARD DILUTION FORM
FLOW CHART FOR DATA REDUCTION, VALIDATION,
AND REPORTING
MASS SPEC CONFIRMATION SHEET
EXCEPTIONS TO NPS QAPjP
EQUATION USED TO CALCULATE PEAK SYMMETRY
FACTOR (PSF) AND PEAK GAUSSIAN FACTOR (PGF)
EPA REFEREE LABORATORY PROGRESS - QA REPORT
TECHNICAL MONITOR PROGRESS - QA REPORT
ANALYTICAL COORDINATOR STATUS REPORT
Figure No.
4-1
•6-1
6-2
7-1
7-2
7-3
8-1
8-2
8-3
10-1
10-2
11-1
14-1
16-1
16-2
16-3
Section
4
6
6
7
7
7
8
8
8
10
10
11
14
16
16
16
Page
2 of 2
3 of 4
4 Of 4
4 Of 6
5 Of 6
6 Of 6
5 Of 7
6 Of 7
7 Of 7
5 Of 6
6 Of 6
7 Of 7
3 Of 3
2of4
3 Of 4
4 Of 4
-------
Section No. 2
Revision No. 4
Date: December 1989
Page 6 of 6
2. LIST OF TABLES
Title
ENVIRONMENTAL CHEMISTRY LABORATORY SAMPLE
REQUIREMENTS
Table No. Section
6-1
2 of 4
-------
Section No. 3
Revision No. 4
Date: December 1989
Page 1 of 1
3. PROJECT DESCRIPTION
The National Pesticide Survey (NPS) of drinking water wells is a joint project between the EPA
Office of Pesticide Programs (OPP) and Office of Drinking Water (ODW). Expectations for the full
Survey are that well-water samples will be analyzed for over 100 pesticides or degradation products
*-
from approximately 1500 domestic and community water system wells. Over 40 of these analytes are
included in NPS Method 1 with which nitrogen - phosphorus containing pesticides will be determined.
There is a referee laboratory for each method; the OPP Environmental Chemistry Laboratory at
Bay St. Louis, MS will serve this function for NPS Method 1. The roles of the referee laboratory in this
Survey are:
• to analyze duplicates of samples sent to the analytical contractor (primary lab.)
limited to 20% or a maximum of 5 samples per week from those taken the first 6
months;
• to perform High Resolution GC/MS Confirmation of low concentration suspected
residues not amenable to analysis by Low Resolution GC/MS;
• to provide a Technical Monitor and/or EPA Project Officer to oversee analytical
and/or contractual aspects of work done by the analytical contractor;
• to evaluate any QC activities required of the analytical contractors, including
conducting and participating in NPS audits;
• to provide verification analyses of blind samples;
• and to verify prior to use all analytical standards prepared for use with this method
by EPA/Technical Support Division - Cincinnati or their contractor.
The nitrogen - phosphorus pesticides and/or degradation products included as analytes for this
method are:
Alachlor 1/ Disulfoton sulfoxide Pebulate
Ametryn EPTC Prometon
Atraton Ethoprop Prometryn
Atrazine Fenamiphos 1/ Pronamide
Bromacil Fenarimol Propazine
Butachlor Fluridone Simazine
Butylate Hexazinone Simetryn
Carboxin 1/ Merphos Stirofos
Chlorpropham Methyl paraoxon Tebuthiuron
Cycloate Metolachlor Terbacil
Demeton-S Metribuzin 1/ Terbufos
1/ Diazinon Mevinphos Terbutryn
Dichlorvos MGK 264 Triademefon
Diphenamid Molinate Tricyclazole
1/ Disulfoton Napropamide Vernolate
1/ Disulfoton sutfone Norflurazon
1/ Qualitatiave Analyte
-------
Section No. 4
Revision No. 4
Date: December 1989
Page 1 of 2
4. PROJECT ORGANIZATION AND RESPONSIBILITIES
Referee laboratory responsibilities for NPS Method 1 will be carried out by OPP's Environmental
Chemistry Lab. (ECS) which is managed by Dr. Aubry E. Dupuy, Jr. Section Chief. Mr. Robert Maxey,
chemist at ECS, will serve as both EPA Technical Monitor and Project Officer for the Method. Mr.
*
Maxey, as ECS Project Leader, will also be responsible for day-to-day management of NPS analytical
activities. Dr. Danny McDaniel, Acting ECS-QAC, will provide QA oversight (effective 050189; see
Appendix K; addendum of 050189). The Sample Custodian for ECS and for the NPS Project is Gerald
Gardner.
Dr. Christian Byrne will handle sample preparation, extraction, and GC analyses backed up by
Mr. Ray Shaw. Data handling and reporting will be handled similarly. Data review has been assigned
to Mr. William Mitchell and Mr. Joe Ferrario. Mr. Joe Ferrario will provide Low Resolution GC/MS
confirmation while Mr. Danny McDaniel will handle High Resolution GC/MS work (effective 050189; see
Appendix K; addendum of 050189).
Refer to the Method 1 Organization Chart, Figure 4-1, at the end of this Section.
Federal Express shipments of samples and of extracts for GC/MS analysis to ECS-Bay St. Louis,
MS should be addressed to ECS's Sample Custodian;
U.S. EPA
Environmental Chemistry Section
NASA/SSC Building 1105
STENNIS SPACE CENTER, MS 39529-6000
ATTN: Gerald Gardner
(601) 688-3170 (or 3217)
The Assistant Sample Custodians for NPS are:
Mr. John Cuevas Mr. Stanley Mecomber
(601) 688-3170 (or 3217) (601) 688-3170 (or 3217)
(effective 081288; see Appendix K; addendum of 081288)
The EPA telephone number for the Technical Monitor and Project Officer for NPS Method 1 is:
Mr. Robert Maxey
(601) 688-1225 (or 3217)
In Mr. Maxey's absence, Dr. Aubry Dupuy will serve as the appropriate EPA contact for
Technical Monitor and Project Officer responsibilities for Method 1.
Dr. Aubry E. Dupuy
(601) 688-3212
-------
FIGURE 4-1
ECS ANALYTICAL TEAM - METHOD 1
Section No 4
Revision No 4
Date- Oecemoer 1989
Page 2 of 2
NPS Project Leader
Bob Maxey (EPA)
ECS-QAC (Acting)
D. McDaniel (EPA)
Sample Custodian
G. Gardner (EPA)
I"
Assistant Sample
Custodians
J. Cuevas (EPA) |
S. Mecomber (EPA) 1
Data Review
W. Mitchell (AARP)
J. Ferrario (EPA)
Sample Prep. /Ext.
C. Byrne
(STI)*
R. Shaw (EPA)
GC
C. Byrne (STI)*
R. Shaw (EPA)
GC/MS
J. Ferrari o (EPA)
Data Hanoi ing
Reporting
C. Byrne (ST1)»
R. Shaw (EPA)
* * Sverdrup Technology Inc. (In-house Contractor for ECS)
ECS provides overall technical direction to Sverdrup Technology, Inc.
-------
Section No. 5
Revision No. 4
Date: December 1989
Page 1 of 5
5. QA OBJECTIVES FOR MEASUREMENT DATA
5.1 Initial Determination Of Capabilities; Determination Of EDLs; Determination Of
Reporting Levels
1. Determine concentration of standard necessary to produce an instrument detector
response with a 5/1 signal to noise ratio. *
2. Spike eight reagent water samples at the concentration determined above, and analyze in
a single analytical run.
3. Compute Minimum Detectable Level (MDL) by multiplying the standard deviation by the
student's t value, appropriate for a 99% confidence level, and a standard deviation
estimate with n-1 degrees of freedom.
4. The 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.
5. Determined EDLs must be no greater than twice those determined during methods
development.
6. The acceptability of EDLs exceeding the above limits will be determined by the ECS-NPS
Project Leader based on health effect values.
7. These eight EDL extracts will also be analyzed using the confirmation column. EDLs
determined on the confirmational column must equal those determined on the primary
column; if not, the higher of the two EDLs will prevail to assure that there is a minimal
response on both columns. Again, EDLs exceeding this requirement will be approved on
a case by case basis, by the ECS-NPS Project Leader.
8. To ensure adequate sensitivity the day QC/MS confirmations will be performed, a standard
of the analyte of interest will be prepared and analyzed at approximately the analyte
concentration that will be present when the sample extract is concentrated for GC/MS
analysis. See Appendix J for a Table of the three ions for each analyte (effective 06/15/88;
see Appendix K; Addendum of 072188).
9. The Minimum Reportable Level (MRL) for Method 1 is 4 X EDL
10. The lower concentration calibration standard must be prepared at a concentration equal
to the minimum reportable level.
5.2 Determining and Reporting the Presence of NFS Analytes Below the Minimal
Reporting Levels and Identifying Unknown Peaks
Background Information
The Office of Pesticide Programs (OPP) has requested that the NPS analytical contractors and
referee laboratories make an effort to report the presence of NPS analytes below the Minimal
Reporting Levels (MRL). We have also been requested to attempt to identify unknown peaks or
responses. To assure that spurious or ambiguous data is not reported and that a uniform system or
analytical routine is used at all laboratories to accomplish these requests, the following procedures will
be used.
-------
Section No. 5
Revision No. 4
Date: December 1989
Page 2 of 5
5.2.1 Procedure for Determlnlnlng and Reporting the Presence of NPS Analytes
Below the Minimal Reporting Level
1. For Method 1, only peaks with responses of between one-half the established MRL and
the MRL A/ on the primary column will be investigated. The first time such a response is
noted on the primary column, no further analytical work isjjnderdertaken; the second time
such a response is noted, analysis on the secondary QC column is required.
2. (a) For Method 1, if the response on the second column is positive, further analytical
work under (3) below is required.
(b) For Method 1, if the response on the second column is negative, that fact is noted.
After five attempts at second column confirmation have failed for the same analyte,
the ECL Project Leader is informed, and discussions with OPP personnel will take
place before continuation of analytical work on that analyte.
3. For responses meeting the requirements of (1) and 2(a), the laboratory will attempt LR
GC/MS B/ confirmation if the GC/MS analyst feels it is within the capability of his
instrument. If the confirmation is not within the capability of the LR GC/MS, the extracts
will be run on HR GC/MS. Copies of chromatograms, the related Method Blank and all
pertinent sample information must accompany the extracts. Correct volume level should
be clearly marked on the outside of the extract tube.
A/ = NPS Method 1 MRL = 4 X EDL
B/ = LR GC/MS = Low resolution mass spectrometry
HR GC/MS = High resolution mass spectrometry
4. Only analytes positively confirmed by GC/MS will be reported beyond the ECL Project
Leader for Method 1 and the Analytical Coordinators. No unconfirmed data will be
reported outside the NPS analytical system. Unsuccessful attempts at confirmation will
also be reported to the ECL Project Leader.
5. Following the successful GC/MS confirmation of two such responses for the same analyte
or two failures to confirm the analyte without any prior successful GC/MS Confirmation on
any samples, discussions with OPP personnel will take place before continuing low-level
analytical work on that particular analyte.
6. As a referee laboratory, ECL will also be receiving Method 1 sample extracts from the
contractor when HR GC/MS work is required. These extract shipments will be received
and logged in by the Sample Custodian or his Representative, and the ECL Project
Leader will be notified.
5.2.2 Procedure for Determining the Identity of and Reporting the Presence of Non-
NPS Analytes
It is expected that, over the course of the NPS Program, numerous extraneous responses will be
evident on chromatograms from the various methods. The referee laboratories will be required to
attempt identification of peaks or responses exhibiting the minimal criteria below.
1. For Method 1, if the response of an extraneous peak upon initial injection, exclusive of the
Method Blank, on the primary column is equal to or greater than the response of the
nearest NPS analyte on that column at 10X MRL (Minimal Reporting Level), an attempt
must be made to identify that peak by GC/MS. Full scan spectra and subsequent library
-------
Section No. 5
Revision No. 4
Date: December 1989
Page 3 of 5
search are expected and must be followed by comparison of the spectra of the unknown
compound with that of an authentic standard of the suspected compound.
2. The work in (1) must be attempted on the first occurrence of such a peak and the results
of the attempt at confirmation reported to the ECL Project Leader for Method 1. If the LR
GC/MS analyst feels his instrument is not capable of the confirmatory work, the extract is
submitted to the HR GC/MS analyst. Volume level of extract should be marked on the
outside of the extract vial.
Specific sample and analytical information must accompany each such extract.
• Sample i.d. number, weight of sample matrix contained in the vial copies of
chromatograms from the primary GC column, identification of the retention
window for the unknown peaks as defined by the last NFS analyte to elute
before the unknown peak and the first NFS analyte to elute following the
unknown peak. The related Method Blank extract must also be included.
3. Only those compounds positively confirmed by GC/MS will be reported beyond the ECL
Project Leader for Method 1 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 ECL Project Leader.
4. Following either the successful confirmation of two such extraneous peaks proving to be
the same compound or two failures to identify the same unknown peak, discussions with
OFF personnel will take place before continuation with identification work on that
particular compound.
5.3 Laboratory QC Requirements for Primary Analyses
1. Laboratory control standard mixes, which together contain all method analytes and the
surrogate, will be analyzed with each set of samples.
2. A set of samples is defined as all samples, blanks, spiked samples, etc. on which similar
analytical operations are performed at the same time and which are analyzed in a single
run.
3. The internal standard area checks detailed in Method 1, will be used but may not deviate
by more than +. 20% of the average peak height or area of the internal standard in the
calibration standard. The control limits will be reassessed following completion of the
initial demonstration of capabilities.
4. The measurement system is to be evaluated whenever any analyte is observed in a
Method Blank, at a concentration greater than or equal to 1/2 the minimum reportable
level. Method Blanks are to be analyzed with each set of samples.
A sample set in which the surrogate compound recovery of the Method Blank has failed to
meet the +. 30% criteria can be validated by use of a Field Sample, from that same
sample set, which meets all of the quality control requirements for a Method Blank.
Note: This is not a procedure to validate the surrogate or the Method Blank; rather, it is a
procedure to validate the sample set by use of a Field Sample as a Method Blank.
5. The requirement for surrogate recoveries from Field Samples and Method Blanks is the
Mean Recovery, R, on the applicable Control Chart ± 30 percentage points (i.e. R ±
30%). It is not R ± .30 R. (effective 081888)
-------
Section No. 5
Revision No. 4
Date: December 1989
Page 4 of 5
6. Quantitation is by comparison to a calibration standard, the response of which must be
within ± 20% of the response of the suspect analyte on the primary column, (effective
04/12/89; see Section 8.20 for exact procedure)
7. Samples failing any QC criteria must be reanalyzed.
8. Only qualitative analyses will be required for Diazinon, Disulfoton, Disulfoton sulfone,
Disulfoton sulfoxide, Merphos, Pronamide, and Terbufos. (effective 03/20/89) While these
analytes are to be analyzed in at least one of the concentration levels of the calibration
standards, they are not subject to any of the QC requirements.
9. Each time that new calibration standard dilutions are prepared they must be compared to
the existing calibration curve, and the observed concentration must agree within +/- 20%
of the expected concentration.
10. Any deviation from the analytical procedures or QC requirements must be approved by
the ECS-NPS Project Leader and documented in writ ing. by the ECS-NPS Project
5.4 Laboratory QC Requirements For Second Column Analyses
1. Quantitate by comparison to a calibration standard, which is within +/- 20% of the
concentration of the analyte(s) determined using the primary column.
2. The concentrations) for the anatyte(s) on the secondary column should quantitate within
+/- 25% of the result determined on the primary column (effective 03/20/89).
3. If the concentration determined on the secondary column does not agree within the limits
stated above, the analyst must confer with the ECS-NPS Project Leader concerning
resolution of the discrepancy prior to submitting the extract for GC/MS analysis.
4. If the concentration determined on the secondary GC column meets the criteria in (2)
above and GC/MS is positive, report the concentration of the analyte found on the primary
column.
5.5 Laboratory QC And Extract Handling Related To GC/MS Confirmation
1. The sample extract is to be compared to a standard prepared at the concentration
determined for the analyte on either the primary or secondary column, whichever
concentration is the lower.
2. If additional sample extract treatment is performed for GC/MS analysis (blowdown, etc.),
the standard and sample extract must both undergo the same treatment.
3. Results of the GC/MS analysts are simply reported as the presence or absence of the
analyte.
4. If low concentrations of the analyte(s) preclude confirmation using Low Resolution GC/MS,
High Resolution GC/MS Confirmation must be attempted. HRGC/MS may also be
required if the analyte concentration is greater than or equal to 1/2 the lowest adverse
health effect for that analyte or if requested by the Technical Monitor.
5.6 Sample Management
1. Samples must arrive at the laboratory with ice still remaining in the shipping box. If a
sample box arrives at the laboratory without any ice remaining, the Sample Custodian
should adhere to the following instructions (effective 11/06/89).
-------
Section No. 5
Revision No. 4
Date: December 1989
Page 5 of 5
a. Analyze the affected samples - you will receive payment for samples that arrive with
melted ice.
b. Take the temperature of the standing water in the bottom of the sample kit, record
the temperature in degrees Centigrade on the sample tracking form and input the
value into NPSIS. DO NOT TAKE THE TEMPERATUiE OF THE SAMPLE IN THE
BOTTLE.
c. Record any subjective observations you have about the samples and/or sample kit
(i.e. the bottle was warm to the touch).
d. Contact the ECS-NPS Project Leader if you have any further questions, (effective
11/06/89)
2. Strict adherence to sample and extract maximum holding times (14 days) is required for
both primary and secondary column analyses. All analyses should be completed as soon
as possible, but under extenuating circumstances, the maximum extract holding time may
be extended to 28 days for GC/MS analyses only, if approved by the ECS-NPS Project
Leader.
3. Water samples are to be disposed of after the 14 day sample holding time has been
exceeded. Sample extracts must be maintained until disposal is approved by the ECS
Project Leader and documented in writing.
-------
Section No. 6
Revision No. 4
Date: December 1989
Page 1 of 4
6. SAMPLING PROCEDURES
6.1 Sample Requirements
For this method, ECL will be provided one 1-Liter sample preserved with mercuric chloride at 10
mg/liter. This sample is to be shipped iced along with those needed for Methods 3 and 6, by
»-
overnight air and is to arrive iced at ECL This sample is for duplicate analysis of the field sample sent
to the primary analytical contractor. No 'backup" or reserve sample will be shipped.
ECL, as a referee laboratory, is envisioned to receive no more than 10% of the total 1500
samples now expected to be taken in the Survey. Table 6-1, found at the end of Section 6.0,
summarizes these sample requirements.
6.2 Labelling Of Sample Bottles
The Implementation Contractor, ICF, will supply information on the labels, sample numbering
system, and explanations for field coding or decoding at the laboratory. This label is shown in
Figure 6-1.
6.3 Field Sample Tracking Form
ICF will supply a copy of this form along with explanations for field coding or decoding at the
laboratory. This form is shown in Figure 6-2.
-------
Section No 6
Revision No. 4
Date. Decemoer 1989
Page 2 of 4
TABLE 6-1
ENVIRONMENTAL CHEMISTRY LABORATORY SAMPLE REQUIREMENTS
LAB KU£
KET TifPE
Ssaple Types
BOTTLE TYPE
BSL
Referee
lOOOoL 1 100QEL «
1
i • •*
I
<
60oL
! 6
Priaary
Rfiferee
Shipping Black
Backup Saaple
Lab Spi3ces
Tine/Storage
Total Bottle
lOOQaL * 300
2SOaL- N.A.
60mL= 150
Totals
Vo. oi Sites
TOTAL RQJ'D
1
ISO
ISO
1
ISO
ISO
1
ISO
ISO
-------
Section No 6
Revision No 4
Date. December 1989
Page 3 of 4
FIGURE 6-1
LABEL OF SAMPLE BOTTLES
SAMPLE #: PD-OOOO-6-1-01
BSL - METHOD* 1 KIT: 611
! FIELD SAMPLE
• PRESERVATIVE: HqC12
: DATE ! TIME 5 SAMPLER
NATIONAL PESTICIDE SURVEY
SAMPLE #: PD-0000-6-3-01- -
BSL — METHOD* 3 - KIJ:
FIELD SAMPLE
PRESERVATIVE: HgC12
DATE ! TIME ! SAMPLER
NATIONAL PESTICIDE SURVEY
SAMPLE *: PD-0000-6-6-01
BSL - METHOD* 6 KIT: 611
FIELD SAMPLE
PRESERVATIVE: HgC12
DATE '. TIME ! SAMPLER
UfiJJ 2L-rs- _££5T_:_cj pr: SURVEY
SAi-ir-'LlT « : PD— :••.->:—a-i-v::
BSL - METHOD* : KIT: 611
BACKUP SAMPLE
PRESERVATIVE: HgC12
DATE : TlMg I SAMPLER
-------
Section No. 6
Revision No 4
Date. December 1989
Page 4 of 4
FIGURE 6-2
FIELD SAMPLE TRACKING FORM
VEIL I.D. NO.: 0000
FSDS I.D. No. (CHS HELL ONLY):
SAMPLE COLLECTION DATE: / /.
TRACKING FORM COMPLETED BY:
LAB: BSL_
SCENARIO: J_
kIT NO.: PS-0000-fcll
BOX 1 of 1
'TO BE CQHPLETEIi BY:
1CF
SAMPLE
NUMBER
FO-0000-b-l-Oi
PO-CGGG-6-3-01
PD-OuOO-fc-c-01
Pt-OuGO-t-1-03
BOTTLE
SIZE
1000
1000
60
1000
SAMPLE
DESCRIPTION
FIELD SAHPLE
FIELD SAMPLE
FIELD SAMPLE
BACKUP SAMPLE
FIELS TEAR ; LAB
SAMPLER : TIRE 1 COMMENTS 111 :RECE1VED
(INITIAL) ! SAMPLED '.
! : '. ; H
1 • '
: : -. *
I
; : 1 i K
: : : > ! i.
COMMENIi
LHLGR If-jE TEST:
SHIPPED 9t:
SATE
SENT TO:
.
Ui FCR EXAMPLE:
\i\ FGR E1AMPLE:
'*•. era PtftSPtF?
i ; RECEIVE!- AT LAB BY:
i •
TIME ! : DATE TIr.E
! LAB ADIifcE:-: . C3KDITICN (3;
: SAY St. LlJls E^'ENVIFWJ'EJITAL I
; :HEBISTH ^t. -IK. 1105 :
, ,
: NSTL. i»S jSi:*
1 " '
S5T7.E BP.OKES, BGTTLE niSS:N&, OVERFU.EJ WTTlE. CAP KAS I-RDPFED
sOTTLE BSOKEK, BOTTLE HISSING. 83TTLE -IdiTfiaittTCD. TEMPERATURE CRITERIA KOT ".ET
'rr «',TfT) a.ri( ;ri«!U!;
I Li
Lib coMtnts should concur nth NPSIS SAKFLE RECEIPT
-------
Section No. 7
Revision No. 4
Date: December 1989
Page 1 of 6
7. SAMPLE CUSTODY
7.1 Tracking And Notification Of Sample Shipments
The proposed EPA system for notification of the laboratory of sample shipments and for
notification of the Implementation Contractor (ICF) of receipt of the samples is delineated on the flow
chart and diagram, Labelled Figure 7-1, 'SAMPLE RECEIPT SCREENsVoR NPS LABORATORIES' at
the end of Section 7.0. This system will be computerized.
7.2 Sample Requirements Following Receipt At Laboratory
Tracking of all samples arriving at the laboratory will begin upon receipt of any sample and will
continue through each phase of the analysis.
• Upon receipt of samples, each is identified according to its 'Field Sample Number1,
logged in and stored at 4°C. This information is documented on a 'NPS LOGGING
FORM'.
• The Sample Custodian or his/her Representative will compile 'sets' of samples for
Method 1 comprised of 5 samples and appropriate controls as covered in Section
9.4 of this QAPjP. The composition of each set is documented on a 'NPS SET
COMPOSITION FORM'.
• Transfer of samples into and out of storage will be documented on an internal
chain-of-custody record. Only those samples in the 'set* on which analytical work
will be done will be removed. This information is documented on a 'SAMPLE
CONTROL RECORD FORM". The analyst will sign and date this Record when
removing or returning samples to storage.
• After removal from storage, samples are tracked through extraction and G.C.
Analysis via a 'ECL/NPS SAMPLE TRACKING FORM'.
Following extraction, sample extracts are stored in a refrigerator at 4°C until
analyses are complete. Following analysis they are transferred to screw-cap
tubes (teflon liners), the extract level marked, and stored by set in a freezer at
0° to -20°C.
• An EXTRACT STORAGE DATA SHEET records chain-of-custody of extracts from GC
Analysis to GC/MS Confirmation, if required, and to disposal.
• Copies of all the above mentioned Forms and Records can be found in Appendix A.
7.2.1 Storage Conditions
Upon receipt at the laboratory, samples will be stored under refrigeration at 4°C and protected
from light.
7.2.2 Holding Times
Samples have a maximum holding time of 14 days from time of collection until the start of
extraction.
Extracts have a maximum holding time of 14 days from date of extraction to GC Analysis and
GC/MS Confirmation, if required. The holding time for GC/MS Analysis may be extended an additional
14 days upon approval of the ECL Project Leader.
-------
Section No. 7
Revision No. 4
Date: December 1989
Page 2 of 6
7.2.3 Disposal
Samples held longer than 14 days without being extracted are to be disposed of after approval
is given by the ECL Project Leader.
The samples arrive with a 10 rag/liter concentration of mercuric chloride which is added as a
*-
preservative. Disposal of these samples will be to an EPA-approved water treatment system capable
of handling these concentrations of mercuric chloride and which is connected to the ECS facility.
The sample extracts will be disposed of as hazardous waste by an EPA-approved hazardous
waste disposal firm or contractor at an EPA-approved disposal site.
7.3 Return Of Sample Kits To EPA Contractor (ICF)
ICF is to provide information on this.
* 7.4 Receipt and Tracking of Extracts from Analytical Contractors for GC/MS Confirmation
at ECS (effective 05/89)
To carry out its responsibilities as a referee lab. (see Section 3), ECS will be receiving from
Analytical Contractors sample extracts meeting the requirements of Section 5.2. For all such extracts
arriving at ECS, tracking will begin upon receipt and continue through final disposition according to
the following procedure.
• Upon receipt at ECS, the Sample Custodian or his representative will check extracts
against the NPS EXTRACT SHIPMENT form, filling in the Date Received at ECS,
Condition of Shipment, Number of Refrigerator where stored, the Container No. and
signing where appropriate. (A copy of this form is attached at the end of this
Section and is labeled Figure 7-2.) He should then place the extracts in containers
labeled by date and store in a refrigerator at 44°C.
• The Sample Custodian will make necessary copies of paperwork received with the
extract shipment, giving all the original paperwork to the NPS Technical Monitor for
the Analytical Contractor and a copy of the original paperwork to the GCMS analyst.
The Sample Custodian should keep on file, in the receiving room, a copy of the
NPS EXTRACT SHIPMENT form.
• The GC/MS analyst should remove extracts from the designated refrigerator,
analyze the extracts by GCMS, then complete the remainder of the NPS Extract
Shipment form and the GCMS Data Sheets. The analyst should give all completed
forms and GCMS spectra to the NPS Technical Monitor.
• The Technical Monitor will use the information from the NPS EXTRACT SHIPMENT
form to complete an overall tracking form, the NPS GCMS EXTRACT TRACKING
FORM. He will send a copy of the GCMS Data Sheets to the NPS Data Manager
and to the Analytical Contractor. He will also send the Analytical Contractor a copy
of the GCMS spectra ECS will maintain the original paperwork on file.
• GC/MS results will be reported as in Sections 10.5 and/or 10.63.
• The Technical Monitor for the appropriate Method will receive all results and reports
of GC/MS confirmation analyses and a monthly report from the ECL Sample
Custodian on the total number of extracts received for each Method.
-------
Section No. 7
Revision No. 4
Date: December 1989
Page 3 of 6
• The Technical Monitor will inform the Analytical Contractor, in writing, of the results
of each GO/MS confirmation attempt.
• Disposal of extracts wil be according to Section 7.23 and will be authorized by the
Technical Monitor.
7.5 Internal Practices Concerning Sample Storage •
The temperatures of coolers, refrigerators, and freezers where samples and/or extracts are
stored are monitored each working day, and this activity and the temperature are recorded in a log
book maintained for this purpose. A copy of this record is included as Figure 7-3 at the end of this
Section.
The ECS Sample Custodian, Gerald Gardner, or the Assistant Sample Custodians are
responsible for monitoring these storage areas (effective 081288; see Appendix K; addendum of
081288). ECS has an agreement with the facility contractor to provide weekly preventive maintenance
and emergency repair services on large coolers where samples will be
-------
Section No 7
Revision No. 4
Date. December 1989
Page 4 of 6
FIGURE 7-1
SAMPLE RECEIPT SCREENS FOR NPS LABORATORIES
0
(/> E
0 o
'H^
o ro
•*-' 73
^^T *•
V\J
^~ w
0
.Q
03
— 1
CO
D_
Z
'—
O
\^_
CO
c
0
0
o
CO
£.
*0
o
0
QC
^)
Q.
£
\^J
CO
E
3
73
C
!
<
C 5
i.
Z
}
. .
o
*o
^^
e
•i
«.
f
*
4
•
)
Y
)
! ,»
L "3
: u
ill
O^ o.
W *"
5 c =
•o o >
«/» u
^
r
> e
= 1
J S
I ~
1 X
to
1
o
1 —
1 ' x
1 UJ
"
i
j
'
:
<
J
L
i
]
H £
•° ?
• — •
T> ^
O
u..
L
3k
h.
^
UJ
o
1
J
^•^^^^•^
^^•i^^HH
1
1 •*
I °
1 A
I
=
1.
|
S
^
o
3
o
°
e
dlcalo 1
c
o
'. o.
1
>.
L
'
^
"^*
•»
S
O
O
-. *-
Z Z
> >
1 ^
o Z
i s
c k
e r
. £
0
2
" Z
*j j"
^ **•
Xi-
gs
o2
»- a
e e
j- S
S fl
II
2
«Sfc
>
o
S r
° C
c e
k. C
o =
£ S
•* o
O O
^
»
1
\
l\
E
o
o
o
c
o
o
Z
2£|| J I
5 >.! . i I
= "^*~~1 I
hill I
•3 "a
o o
"3
u
u
3
O
e =
"o
1
&
"o
0
o
1-_
1
o
2
— o
S. —
-z o «•>«•»« ^
"> ^ ~ — — "
* .... x
e o ooia c
S ^Soo °
c O ooo 5
~ & O.O.O. —
c
III!
i ill 11
o
o
o
Z
e
££
*l
M 'en
E\ ^
S \
\
n
52
"V3
S
£j.
e£ onoo
^*t iiJ.i
eE "-'—
at* ^.*.»-^
Xc ooeo
~ oooo;
-------
Section No. 7
Revision No. 4
Date: December 1989
Page 5 of 6
FIGURE 7-2
NFS EXTRACT SHIPMENT
JJ -O
*J *+ 9
9 Q.JJ
« 3
3 1
w =
a i
1
s-s
al
e
£1
i
a
m
2
u
•o o
2
o
goo
s
o
u
-------
Section No 7
Revision No, 4
Date: December 1989
Page 6 of 6
FIGURE 7-3
TEMPERATURE MONITOR CHART EPA/ECL
* WALK-IN
COOLERS/BLDG. 110!
WALK-IN/UPRIGHT
FREEZERS/BLOG. 2204/110!
REMARKS
PERSON CHECKING
PERSON CHECKING
-------
Section No. 8
Revision No. 4
Date: December 1989
Page 1 of 7
8. CALIBRATION PROCEDURES AND FREQUENCY
8.1 Method 1 Standards
8.1.1 Calibration Solutions
Calibration solutions will be provided and send to both the referee lab (ECL) and primary
analytical contractor by EPA/TSD-Cincinnati through their contractor Bionetics. The solutions are to
be in flamesealed glass ampules. These solutions will be sent iced by next-day air to ECL and will be
accompanied by a "STANDARD SOLUTION DATA FORM1. The ECL Sample Custodian or other
Designated Representative will receive these standards shipments, note whether or not they were iced
and date of receipt, and relinquish custody of the standards to a member of the Method 1 analytical
team. A sample copy of this form is attached at the end of this Section and is labeled Figure 8-1.
A 'CALIBRATION SOLUTION RECEIVING FORM' will be initiated to record the date solutions are
received, number of sets, condition, and place of storage at ECL These forms will be kept in a
designated folder. A copy is found at the end of this Section and labeled Figure 8-2.
8.1.2 Standards Prepared at ECL
ECL will prepare and maintain separately weighed stock standards of each analyte. These
stock standard materials should be from the same lot numbers as those used to prepare the
EPA/Bionetics-supplied calibration solutions. These ECL-prepared standards will be used to verify the
concentrations of the calibration solutions and resolve problems or questions that may arise
concerning any of the standards. A standards log book is maintained to record name of person
weighing the standard, chemical name of standard, date of preparation, purity, lot no., source,
balance calibration data, and standard weighing data
8.1.3 QA for Diluting and Checking the Standards
Prior to dilution, calibration solutions and/or EPA/ECL stock standards are removed from freezer
storage and allowed to reach room temperature.
Calibration solutions and all subsequent dilutions are labeled with the standard identifier, Batch
No, solvent, preparer, date and concentration. The Batch Nos. provide a means of tracking them to
origin. The EPA/ECL prepared standards are labeled with standard identifier, date standard was
weighed, solvent, preparer, and concentration. These standards can be tracked to origin by the date
the standard was weighed which will lead to a specific entry in the ECL standards log book as
covered in 8.1.2.
A 'STANDARD DILUTION FORM', Figure 8-3 at the end of this Section, is used to record all
information on dilutions and to facilitate the tracking of standards.
8.1.4 Calibration Solutions and ECL Standards Verification
Calibration solutions will be the stock material for all standards used in the NPS at both the
referee and analytical contractor laboratories. To verify their concentrations, they must by analyzed
against the ECL prepared standards before use. The calibration solutions and ECL prepared
-------
Section No. 8
Revision No. 4
Date: December 1989
Page 2 of 7
standards must differ by no more than ± 15%. Following the comparison, all values must be reported
to the ECS Project Leader. Standards with differences >.+ 15% require resolution at this point before
work with the standard can proceed.
8.1.5 Frequency of Calibration Standards Checks
»
Calibration standards must be checked against ECS prepared standards each time a new
calibration standard is prepared from a calibration solution. Criteria in 8.14 apply.
Concentrations of calibration solutions must be verified at ECS each time new Batch Nos. are
prepared at EPA/TSD-Cincinnati or Bionetics and before shipment to the analytical contractor. Criteria
in 8.14 apply.
8.1.6 Association of Calibration Standards to Survey Sample Analyses
Each calibration (bench) standard used in analytical determinations must be able to be traced
to its origin, and every field sample or control sample analyzed must be associated with the specific
calibration standard(s) used.
To facilitate these requirements, each standard mix with different components or different
concentrations of these components must have a uniquely different name and a date of preparation.
This standard identifier and date must appear on each chromatogram of the standard. It may also
appear on the computerized data printout.
8.2 Instrumentation Checks and Quantttatlon Procedure (effective 04/12/89)
A Hewlett-Packard 5890 A dual capillary GC with Nitrogen-Phosphorus Detectors (NPDs) is used
to analyze Method 1 samples. Standard techniques and quantitation procedures given below are
used.
The internal standard (IS) selected for use with Method 1 is o-nitrotoluene, and it is compatible
with the GC columns and chromatographic conditions for this method.
Initially, the current requirements of the Instrument Quality Control Standard must be met.
Two calibration standards will be prepared from each calibration standard mix. The first
calibration standard will be used as the 'single point* quantitation standard. It will contain
concentrations of each analyte of each mix at 10 x Minimal Reporting Level (MRL). Following the
injection of this standard, the relative response (RRstd) of each analyte to the IS is calculated with the
following equation:
RRstd = (Aa /Ais) / C, where
Aa = Area of the analyte
Ais = Area of the internal standard
C = Concentration of the analyte at 10 X MRL
In a similar manner a response factor (RRsamp) of each analyte to the IS of each sample is
calculated with the following equation:
-------
Section No. 8
Revision No. 4
Date: December 1989
Page 3 of 7
RRsamp = (Aa /Ais), where
Aa = Area of the analyte
Ais = Area of the internal standard.
The ratio of the RRsamp to the RRstd of a given analyte in a sample will result in the
»-
determination of the concentration of the analyte.
The second calibration standard will contain concentrations of the analytes at the Minimal
Reporting Level (MRL). The analysis of this standard will demonstrate that the instrument/detector
meets minimal response requirements for all analytes in the mix. Minimal Response Requirements are
detection of a response approximately equal to 1 x EDL for each analyte as defined in the QAPjP;
Section 5.1. These standards will span the range of concentrations expected in the sample extracts
and in the Laboratory Control Standards (LCS). The two calibration standards of each mix must be
analyzed at the start and conclusion of each sample set to ensure that the minimal response re-
quirements are met during the course of the analyses.
Where a response on the PRIMARY column indicates the possible presence of an analyte at
1/2 MRL or above in a sample extract, that sample extract must be reanalyzed on the PRIMARY
column against a checked and verified standard of the suspect analyte. The concentration or
response of the standard must be within +/- 20% of the concentration or response of the suspect
analyte. Quantitation may be by means of the INTERNAL STANDARD: if it is not, it is stated on the
QA DATA FORM EXCEPTIONS SHEET that the quantitation was accomplished by means of
comparison with an external standard'. Also, this information is included under "COMMENTS' on the
NPS DATA REPORT FORM for the sample.
The Laboratory Control Standards (LCS) must be quantitated against the calibration standard at
10 x MRL
The calibration standard at 10 x MRL, which contains the surrogate, must be analyzed in
association with the method blank and field sample extracts to determine the compliancy with
requirements for surrogate recovery. This standard is recalibrated before the analyses of each pair of
sample extracts.
8.2.1 Calibration of HR GC/MS
Scanning Mode - The instrument is calibrated by the MCAL and CAUB routines in the
MAT 312 operations manual
MID Mode - The instrument must be further calibrated by using the ESCAN and
ECAL routines in the manual
The instrument will be tuned for proper relative ion intensities by using DFTPP1 (if possible)
when library searches are indicated.
1 Eichelburger, J.W.,; Harris, L.E.; Budde, W.L 'Reference Compound to Calibrate Ion Abundance
Measurements in Gas Chromatography - Mass Spectrometry Systems' Anal. Chem. 1975.47(7), 955-1000.
-------
Section No. 8
Revision No. 4
Date: December 1989
Page 4 of 7
8.2.2 Calibration of Low Resolution GC/MS
The instrument is calibrated according to the manufacturer's recommendations using the
CALIBRATION (CAL) routines specified in the manual.
The mass spectrometer will be tuned to EPA's specifications using DFTPP (effective 06/88).
-------
Section No 8
Revision No 4
Date: December 1989
Page 5 of 7
FIGURE 8-1
STANDARD SOLUTION DATA FORM
0!OIO«OiO
0:0:010:0
~
.v,www.<_"<_>:a:c3iOiO:O:O:i
i^:z: i i i i I j ! i i : i : i i i j i i i I i i i I i 1 i ;
: :o; : i i ! i I • i i ! : t i • : I i i ; i i i • ; i • ; i
• tcj: ' : i '. i i ' : i ' ' '• ' ' ' ' ' ; : : i : ' i : I : i
fcS i U i U i i U i i I i I i i i i i i j i i i I i i
l>-l^ ' |O:.i!K>iO>«_!4ai—tf*-~te*- -».—..-^- - -
1
ir*:*^
.• .1*3
— OiO- •
:—:o«o«S
j ! i i i i
! IS!
i i
-------
Section No 8
Revision No 4
Date1 December 1989
Page 6 of 7
FIGURE 8-2
CALIBRATION SOLUTION RECEIVING FORM
CALIBRATION SOLUTION RECEIVING FORM
Date Received: Date Checked:
Person Receiving: Person Checking:
Were Samples Iced?_jj Relinquished Custodyy{Yes/No)
Method No: (1,3,or 61
(circle one)""
Coments:
Person Assuming Custody:_ Date:
Number of Sets:
Date Calibration Solutions arrived at EPA/ECL written
on individual standard cartons: (Yes/No)
Date Stored: Freezer No: Room No:
Ccrments on condition of Calibration Solutions:
-------
Section Nio 6
Revision No 4
Dale December 1989
Page 7 of 7
FIGURE 8-3
STANDARD DILUTION FORM
e
/; u
v.
e
o -c
»• o
*•* M
e a
fe °-
-c o
0
O
U W
-------
Section No. 9
Revision No. 4
Date: December 1989
Page 1 of 2
9. ANALYTICAL PROCEDURE
9.1 Summary Of Method
This Method is applicable to the determination of certain nitrogen and phosphorus-containing
pesticides in ground water. These compounds are listed in Section 3 of this QAPjP.
A measured volume of sample (approximately 1 Liter) is solvent extracted with methylene
chloride by shaking in a separatory funnel. The methylene chloride extract is isolated, dried, and
concentrated to a volume of 5 ml after solvent-exchange with methyl t-butyl ether (MTBE).
Capillary gas-chromatography with nitrogen-phosphorus detectors is used for both primary and
secondary analyses of the sample extracts.
For sample extracts with suspect-positive analytes, (i.e. - those with positive responses on both
the primary and secondary GC columns), such extracts will be analyzed by either Low Resolution
GC/MS (LRGC/MS) or High Resolution GC/MS (HRGC/MS) to confirm the presence or absence of the
analyte.
9.2 Major Equipment/Instrumentation To Be Used With Method 1
• Hewlett-Packard 5890A dual capillary gas chromatograph with dual nitrogen-
phosphorus detectors. Similar GC for back-up.
• Hewlett-Packard 7673A autosampler. Identical autosampler for backup.
• Hewlett-Packard 3354 data system.
Finnigan MAT 312 High Resolution GC/MS
• Finnigan MAT 5100 Low Resolution GC/MS
9.3 Analytical Method
9.3.1 Method As Developed By Battelle
This Method is presented in Appendix B .
9.3.2 Differences From Battelle Method
* 7.9 o-nitrotoluene is added as the internal standard (IS). The IS is prepared in
MTBE at a concentration of 25 mg. in 25 ml. 4 ml of this IS solution are
added to a 10 ml volumetric and diluted to volume. From this spiking solution
(400 ng/ul), 40 ul is added to each 5 ml vial of extract and to each 5 ml of
calibration (bench) standard. The concentration of IS in each extract or
calibration standard is 3.2 ug/ml or 3.2 ng/ul. This amount of o-nitrotoluene is
chosen to produce a peak 40 - 60 % full scale deflection on the
chromatogram.
* 10.6.1 Laboratory Control Spike contains mercuric chloride at a concentration of 10
mg/Liter. Spike Level is 10 x MRL NOT 15 x EDL
Denotes reference to Battelle's Method and is not part of the ECL numbering system.
-------
Section No, 9
Revision No. 4
Date: December 1989
Page 2 of 2
* 10.8 Method Blank contains mercuric chloride at a concentration of 10 mg/Uter.
Method Blank is rejected for interfering analyte at 1/2 MRL NOT 1/2 EDL.
* 10.5.2 ...deviates by more than 20 percent from...
* 10.2.1 Refer to ECL-QAPjP: Section 5.1 (7).
* 11.3.1 The Erlenmeyer flask containing the methylene chloride extract is placed in a
warm water bath (404°C) and concentrated via a stream of dry, filtered
nitrogen. The methylene chloride is concentrated to about 5 ml and
quantitatively transferred to a 25 ml K-D tube. (Total volume methylene
chloride in the tube should be < 20 ml, if possible.)
Add 2 boiling chips (Hengar granules) to the K-D, attach a Snyder column,
and place K-D on a steam bath to concentrate solvent. When the volume of
methylene chloride reaches 5 ml, add 10 ml of MTBE and further concentrate
to 3 ml. Add another 10 ml of MTBE and again concentrate to 3 ml.
Remove the K-D apparatus and allow to cool. Rinse the Snyder column with
a small amount of MTBE and adjust volume to exactly 5 ml.
The Internal Standard is now added per revision to *7.9 above.
9.3.3 Requirement for Authorization to Deviate From Battelle's Method
Any differences from the Method in Section 9.31 must be discussed with and approved by the
ECL Project Leader for this Survey. The ECL Project Leader may require that such requests be in
writing and be supported by a rationale, facts, or laboratory data
9.4 Sample Sets
Samples will be carried through the analytical work in discrete groups or 'sets'. A set is a
collection of field samples and QC checks or controls sufficient to assess the quality and validity of
any data generated from the set independently of any other set. Specific controls included in sets with
this Method are a Method Blank, and 3 Laboratory Control Spikes which together comprise all
analytes. At a maximum, five Field Samples may be run in a set. This maximum is based on logistical
limitations at the extraction phase.
Denotes reference to Battelle's Method and is not part of the ECL numbering system.
-------
Section No. 10
Revision No. 4
Date: December 1989
Page 1 of 6
10. DATA REDUCTION, VALIDATION, AND REPORTING
10.1 Data Reduction
ECL will use an H-P 3354 Data System to acquire, store, and analyze raw data from the
instrument and to generate data reports associated with each analysis. Information generated are
compound retention times, peak areas, relative response factors, and analyte concentrations. These
values plus sample i.d. and instrument parameters will comprise a DATA REPORT. Concurrent with
sample analyses, hardcopy chromatograms will be generated and along with the DATA REPORTS will
form a HARDCOPY DATA FILE. (Refer to Figure 10-1 at the end of this Section.)
Each sample chromatogram will be labelled with the Field Sample Number, final volume of
extract, ul injected, dilution information if applicable, mg-eq. of sample, date, and initials of analyst.
Each chromatogram of a standard must be labelled with the unique identifier of the bench or
calibration standard, amount injected, date of preparation of the standard, date of analysis, and initials
of the analyst.
10.2 Data Validation
Information from each DATA REPORT will be evaluated and verified by an analyst experienced
in chromatography and with this Method. Evaluation will include all QC CHECKS against
ACCEPTANCE CRITERIA as specified in Section 11.0 and the DATA MEASUREMENT requirements for
analyses as specified in Section 5.0.
Additionally, the following sampling and tracking data will be evaluated:
• Is the date from sampling to receipt at ECL within the NPS requirements? (1 day)
• Is the date from sampling to extraction within the NPS requirements? (14 days)
• Is the date from extraction to analysis, including GC/MS confirmation, within NPS
requirements? (14 days)
SAMPLE DATA REPORTS on all samples and controls within the set will be prepared along with
QC SUMMARIES of all QC DATA from the set. For these sample extracts that must be referred to
GC/MS confirmation, the GC analyst will prepare the 'GC/MS CONFIRMATION SHEEP which conveys
to the GC/MS operator information on the extract necessary for the confirmation work. See Figure
10.2 at the end of this Section.
All data generated under 10.1 and 10.2 will be PEER REVIEWED by an analyst under the
direction of the ECL Quality Assurance Coordinator (QAC) or his Designated Representative. This
review will include review of the HARDCOPY DATA FILE for the sample set and validation of all sample
data and QC checks from which SAMPLE DATA REPORTS and QC SUMMARIES are derived.
Discrepancies will be resolved by the ECL QAC, Project Leader, and the analyst. Upon completion of
all reviews, the PEER REVIEWER will sign and date all forms and records indicating validation of the
data.
-------
Section No. 10
Revision No. 4
Date: December 1989
Page 2 of 6
10.3 Data Reporting
Analytical sample data and QC data from the Instrument Control Standard (see Section 11.1)
will be reported via an ASCII text file on a floppy diskette. See Appendix C for instructions on the data
format and specific data to be keyed into the ASCII files. The data in the SAMPLE DATA REPORTS
and QC SUMMARIES will contain any data to be entered into the ASCll file.
A d-Base III program has been written to generate and manage these ASCII files.
Sampling data and tracking data will be entered into the files by the ECL Sample Custodian
and/or analytical team members who are completing analytical work with time limits (i.e. sample or
extract holding times).
The floppy diskettes containing these files will be sent each month to EPA/Cincinnati, Ohio to:
Christopher Frebis
EPA/Technical Support Division
26 W. Martin Luther King Drive
Cincinnati, Ohio 45268
Data for a set of samples are to be reported no later than 2 months from the earliest sample
collection date within that set.
Where rounding of numbers or determination of significant digits is required, ECL will adhere to
the procedures and criteria in Appendix D.
10.4 Storage of Lab. Data
The HARDCOPY DATA FILE (chromatograms of samples, controls, associated standards and
the related DATA REPORTS or computerized printouts) will be maintained and filed by Method and
set. The data file on a set will also contain all forms used in evaluating and QC SUMMARIES.
Sampling and tracking data will also be filed.
It is the responsibility of the analyst to assure that all elements of the HARDCOPY DATA FILE
are in the file. It is the responsibility of the PEER REVIEWER to see that these same elements remain
intact following review, and that they are stored by Method and Set in the RECORDS ROOM.
These files will be retained in storage until ECL is notified by NPS Management of further
disposition.
Raw data is acquired and stored on hard-disk and can be retrieved if necessary. There is no
provision for back-up magnetic tape storage. The HARDCOPY DATA FILE will contain all elements
needed to support a sample analysis. The Procedure for storage of NPS files is attached as Appendix
E.
10.5 Fast-Track Reporting
The NPS has determined that two situations will require "FastTrack Reporting* of data.
• Confirmed positive residues for certain anatytes to be specified by EPA. This data
will also be reported routinely with the appropriate set data.
-------
Section No. 10
Revision No. 4
Date: December 1989
Page 3 of 6
• A situation when results from the secondary GO column do not agree with results
from the primary column within criteria set forth in Section 5.4. This situation is to
be discussed with the ECL Project Leader prior to reporting the data.
A protocol has been provided by NPS on reporting the "confirmed positives" mentioned above.
See Appendix I for the NPS protocol and the list of analytes and their rapid reporting levels. The ECL
Project Leader will assume the duties and responsibilities assigned to the Technical Monitor in the
memo.
Also included in the Appendix are forms to be used at ECS in reporting analytes subject to
rapid reporting requirements. Forms for all three Methods being run at ECS are included with this
QAPjP since an action level in one Method triggers rapid reporting for ajj Methods.
It is the responsibility of the GC analyst for this Method to be aware of these rapid reporting
levels, to assure that the ECS report forms are initiated upon determining that a particular residue
associated with his/her Method is subject to rapid reporting, and to inform the ECS Project Leader
immediately.
10.6 GC/MS
10.6.1 Data Reduction
All HR GC/MS data are acquired by a Digital POP II/34 computer and stored on a CDC-CMO
disc drive. The LR GC/MS data are acquired by a Finnigan 5100 data system based on Superlncos
software. Identification is based on selected ion monitoring of EPA-designated ions and the retention
time of the analyte of interest. The GC/MS analyst will search for the analyte of interest at the proper
retention time of the standard and also look for characteristic ions. The peak areas of the selected
ions for the analyte of interest in the sample being confirmed are then compared to the same ions
generated from a standard of the analyte of interest at about the same concentration level. If marked
differences in relative abundance are observed, the analyst and Technical Monitor should account for
the discrepancy before a positive identification is established (effective 06/88). Hard copies of data
are made and kept on file. After all the results have been reviewed, the raw data is transferred to a
magnetic tape.
10.6.2 Data Validation
The hard copies of the MS data are reviewed by the mass spectrometrist for accuracy and
completeness. The data must also meet the other QA requirements in this QAPjP [See Section 5.1(8),
5.21, 5.22, 5.5, 5.6(2)], that apply. Then the Section Chief or the ECS Project Leader reviews the data,
and a decision is made as to whether or not the presence of a compound can be confirmed.
10.6.3 Data Reporting
The results of the GC/MS confirmatory analyses will be reported to the ECS Project Leader if the
sample(s) were extracted at ECS and to the appropriate Technical Monitor for the analytical contractor
if the extractions were done by the contractor. (See Figure 10.2 at the end of this Section.) One set
of hardcopy data supporting each confirmation should be attached to the form.
-------
Section No. 10
Revision No. 4
Date: December 1989
Page 4 of 6
10.6.4 Filing and Storage of GC/MS Data
The ECS Project Leader will be responsible for the initial filing and storage of GC/MS results and
data as described in Sections 10.4 and 10.6.3.
Raw data will be stored on magnetic tape by the GC/MS analyst as described in Section 10.61.
Any GC/MS analysis or confirmation can be reconstructed from this raw data.
STORAGE OF NPS HARDCOPY DATA FILES AT ECL
The HARDCOPY DATA FILES and all related reports will be filed according to NPS
Method No., and then by Sample Set.
ECL has a RECORDS ROOM available for this purpose. It is equipped with shelving
for storage, a smoke alarm, and a sprinkler system. Activation of the smoke alarm is
monitored 24 hours a day by the NSTL fire department which can respond within 2
minutes to an alarm. ECL will take precautions to protect from sprinkler syystem water
damage all files stored in this room.
The RECORDS ROOM is also the office of the ECL QAC and is locked when the
room is unoccupied. Access is limited to the ECL Laboratory Manager, the ECL QAC,
and Project/Team Leaders.
The STORED RECORDS LOG is used to log files into the RECORDS ROOM and to
record removal and subsequent return of these files.
-------
Section No. 1C
Revision No. 4
Date- Decemoer 1989
Page 5 of 6
FIGURE 10-1
FLOW CHART FOR DATA REDUCTION, VALIDATION, AND REPORTING
(7)
Sampling/
Tracking Data
(1)
Instrument
Response
(3)
Disk Storage
Analysis of Raw Date
By Data System
•
)atc
n
Chroma tog ram
(Hardcopy)
(2)
(5)
Data Report (Printout)
Hard Copy
Data File
(6)
Evaluation of Sample Data;
Evaluation of QC Checks
Against Acceptance Criteria
(8.)
Sample Data Reports
QC Summaries (by Set)
(9)
| Peer Review \ (10)
Data Packets
(ASCII Cards)
(11)
1
Monthly Reports | (12)
-------
Section No 10
Revision No 4
Date. Decemoer 1989
Page 6 of 6
FIGURE 10-2
MASS SPEC CONFIRMATION SHEET
P.r»o
Specific detail* of aample extracts
S»pl. No. _ . __ Sample Cone g/»l
- "
tlon
1.
2.
3.
4.
NO
Sp«c
«st. Cone
tion
1 • ^
2. "
3-: t—
4 . .—
NOC°nC
i.
2.
3.
4.
S«ple HO
Spec
««t. Cone
tlon
1.
2.
3.
4.
-------
Section No. 11
Revision No. 4
Date: December 1989
Page 1 of 7
11. INTERNAL QUALITY CONTROL CHECKS
Summarized in this Section are all the QC checks and controls required for analysis of NFS
samples. These QC checks are classified according to the analysis type (i.e. - primary column,
secondary column, GC/MS Confirmation).
11.1 Primary Analyses
Type of QC Check
• Instrument Control/
Standard
PSF
PGF
Resolution
Sensitivity
• Method Blank
• Lab. Control Standard
• Calibration Standards
• Field Samples
- Internal Standard
- Surrogate Spike
• Performance Eval.
Samples
• Shipping Blank
• Spiked Sample
• Time Storage Sample*
Frequency
1 day (or 1 set If
uninterrupted
analysis of the set
extends to 2 days)
1 set
1 nd. mix
Win, 1 day or each
working shift
MAX! mum o Mt
Each sample
Each sample
As needed
Criteria tor Acceptance
Refer to Section 11. Z1 -Criteria for
Peak Symmetry Factor (PSF) (effective
04/28/89; see Appendix K; Addendum
09/01/88)
0.80 < PGF < 1.20
>0.70
£ EDL for vemolate
No peaks wtthln the retention window
of any analyte £VjMRL for that
analyte. ~
Refer to Section 11.4.3
All analyte repsonses within ± 20% of
that predicted by current calibration
curve
See Individual QC checks.
Response msut be wtthln +. 20% of
average response of Internal standard
In calibration stds.
Recovery must fall within window of R
(recovery of surrogate from applicable
control chart) + 30 percentage points
(effective 08/18/88).
To be determined
Corrective Action
Reevaluatfon of GO System
Reevaluatjon of GC System
Reevaluation of GC System
Reevaluatjon of GC System
Out-of-control situation; Method Blank must be brought In
control before proceeding.
Out-of-control situation work must be stopped until
control Is establlhsed. Refer to Section 1 1 .4.3.
1. Prepare a fresh calibration standard, or
2. Prepare a new calibration curve
See Individual QC checks.
Refr to Appendix B, Section 10.5, In the written method.
1. Check calculations.
2. Check Internal and surrogate stt. spiking solutions.
3. Reanalyze the sample extract
4, If rsanarysls of extiact results in surrogate being In-
control,' submit only data from In-controT analysis.
5. If reanarysls falls to put surrogate In control,
reevaluate analytical method and measurement
system. Beextract failed sample when system Is
again In control.
analytical system put back In control as evldneced by
successfully analyzing a second P-E Sample.
NOT APPLICABLE TO ECL REFEREE RESPONSIBHJT1ES
NOT APPLICABLE TO ECL REFEREE RESFONSIBIUTIES
NOT APPLICABLE TO ECL REFEREE RESPONSIBILITIES
V Refer to SectJon 14.1 and to Appendix B, Table 10 on page 40 of Battelle's Method.
-------
Section No. 11
Revision No. 4
Date: December 1989
Page 2 of 7
11.2 Confirmations! (Secondary-Column) GC Analyses
Type of QC Check
• Calibration Standards
• Instrument Control
Standard
Sensitivity
• Method Blank
• Shipping Blank
• Quarrtitation
- Calibration Std.
- Anatyte Concentration
Value
Frequency
min. 1 day or
each working
shrft
1 day
1 set
Criteria for Acceptance
All analyte responses within +
20% of that predicted by current
calibration curve. *
> EDL for vernolate
No peak within retention window
of any analyte >. % MRL for that
analyte
Corrective Action
1 . Prepare a fresh calibration
standard, or
2. Establish a new calibration
curve
Reevaluation of QC System
Out-of-control situation; Method
Blank must be brought back in
control before proceeding.
NOT APPLICABLE TO ECL REFEREE RESPONSIBILTTIES
As required by
suspect
positives from
primary column
Per analyte
+_ 20% of cone, of the analyte
determined on the primary
column
± 25% of the cone, determined
on the primary column
Use proper std. cone.
Confer with ECL Project Leader.
I/ Refer to Section 14.1 and to Appendix B, Table 10, page 40 of Battelle's Method.
11.2.1 Criteria for Peak Symmetry Factor (PSF) (effective 04/26/89; see Appendix K;
addendum of 042689)
• Using PSF data points for the first 20 valid sets of Method 1 data, calculate x,
standard deviation, and RSD. If RSD <. 20% and no more than 3 outliers,
establish a 3 control chart around x, with x +. 2 RSD as warning limits; x ± 3
RSD as control limits.
• Plot the succeeding 5 PSF data points for the next 5 sets.
• Reconstruct control chart each 5 sets using the most recently generated PSF points
and dropping the 5 'oldest* data points.
RSD should be <. 20%
no more than 3 outliers
• Two successive data points outside control limits presents an out-of-control situation
which must be corrected before proceeding.
-------
Section No. 11
Revision No. 4
Date: December 1989
Page 3 of 7
11.3 GC/MS Confirmation
• GC/MS Confirmation will be required for all compounds confirmed by second
column GC analysis.
• The sample is to be compared to a standard prepared at the concentration
determined for the sample, on either the primary or secondary column, whichever
concentration is lower.
• If an analyte is confirmed by second column GC analysis but is not present when
analyzed by GC/MS, the analyst must demonstrate that the analyte was not lost
while concentrating the extract. A standard of the analyte should be prepared at
the concentration determined by GC analysis, and then concentrated and analyzed
in the same manner as the sample extract.
• The Method Blank should be prepared and analyzed using the same procedures as
those used for the sample.
• Confirmation is accomplished by comparison to the mass spectra of the authentic
standard and is based on characteristic EPA-designated ions and on the retention
time.
In the event that interferences preclude the use of the designated EPA ions, other
characteristic ions may be substituted on approval by the ECS-NPS Project Leader.
• Results of the GC/MS analysis are simply reported as the presence or absence of
the analyte.
• Mass Spectral Confirmation Codes
MIS - Three individual ions are scanned
SPECTRA - All or a significant portion of the spectra is scanned
11.4 Control Charts
11.4.1 Establishing Control Charts
A. ECU as a referee lab for Method 1, will be required to demonstrate control of the
measurement system via use of control charts. Control must be demonstrated for each
analyte for which quantitation is required and for the surrogate at a concentration equal to
that spiked into samples.
B. To establish the control charts, following initial demonstration of capability, 5 reagent
water samples will be spiked at 10 times the Minimal Reporting Level (MRL) for the
method and carried through extraction and analysis. Only results of analyses on the
primary column are used in establishing the control charts. An additional 15 samples will
be spiked and analyzed, 5 on each of 3 days. The data from these 20 spiked samples
will be used to construct control charts.
C. Criteria for Accuracy and Precision
1. The RSDs for any analyte must be <^ 20%, except where data, generated by Battelle
at the corresponding level, indicated poorer precision. The RSDs exceeding 20%
will be evaluated on a case-by-case basis by Technical Monitors for each method.
-------
Section No. 11
Revision No. 4
Date: December 1989
Page 4 of 7
2. The mean recovery (x) of each analyte must lie between Battelles' mean recovery
for each analyte (at the corresponding level) +. 3 times the RSD for that analyte as
determined by Battelle during methods development, but no greater than Battelle's
mean recovery +. 30%.
Example:
For an analyte "A"
• Battelle demonstrated recovery (x) of 80% for Analyte *A* with RSD of 5%.
Acceptable recoveries will be 80% ± 3 (5%) = 80% ± 15% = 65% - 95%;
• or, Battelle demonstrated recovery (x) of 80% with RSD of 15% for analyte 'A'.
The acceptable recovery would be limited to 80% +. 30% = 50% -110%.
3. Surrogate
In establishing the control chart for the surrogate, criteria in 0(1) and (2) above,
apply; it follows that one of the spike mixes must contain the surrogate at the
concentration as spiked into actual samples.
Surrogate recoveries from samples will be required to be within ± 30% of the mean
recovery determined for that surrogate during the initial demonstration of capabil-
ities.
An LCS in which the surrogate compound recovery has failed to meet the qualify
control limits can be validated if the following conditions are met.
a. The LCS meets all other quality control criteria; and
b. the surrogate compound recovery observed for the Method Blank, associated
with the same sample set, meets the quality control limits determined using
the control chart for that surrogate.
4. Warning Limits/Control Limits
The control charts will be drawn up so as to depict both warning limits (+ 2 o )and
control limits (+. 3 o )about the mean.
11.4.2 Outliers
Dixon's test will be used to determine outliers. There can be no more than 3 outliers per analyte
from the 20 spiked controls. The Dixon test for outliers can be found in Appendix F.
11.4.3 Plotting Data on Control Charts
Data (analyte recoveries in percent) from the LCS on the column will be plotted on the control
chart for each analyte.
11.4.4 Out-of-Control Situations
1. In the following instances, analytical work must be stopped until an 'in-control' situation is
established.
a More than 15% of the analytes of a particular method are outside ±3 a
-------
Section No. 11
Revision No. 4
Date: December 1989
Page 5 of 7
b. The same analyte is outside +. 3 o twice in a row, even though >85% of the total
analytes are in control.
2. An 'alert1 situation arises when one of the following occurs:
a. Three or more consecutive points for an analyte are^outside +. 2 o but inside the +.
30
b. A run of 7 consecutive points for an analyte above or below the mean.
c. A run of 7 points for an analyte in increasing or decreasing order.
The •alert' situation implies a trend toward an "out-ofcontrol" situation. The analyst
is required to evaluate his analytical system before proceeding. If 'alert' or 'out-of-
control' situations occur frequently, re-establishing control charts may be required
by the ECL Project Leader before analytical work can proceed.
11.4.5 Updating Control Charts
Following establishment of the control chart, a spiked controls) is part of each analytical or
sample 'set*. When 5 such controls have been run, the recoveries of these analytes will be
incorporated into the control chart by adding these 5 most recent recoveries to the 20 original points
and then deleting the first 5 of the original points. Accuracy and precision are re-calculated and the
chart re-drawn. The newly drawn chart will then apply to all data in sample sets subsequent to the
last one used to update the chart.
In the event there were 1-3 outliers when establishing the control chart, add the 5 most recent
points and delete only the first 2-4 points so that a total of 20 points are used in the up-dated control
chart.
11.5 Other QC Checks Performed at ECL
11.5.1 Quality Control Data Sheet
Information on all solvents, reagents, and solutions used during each NPS set extraction and
cleanup, must be kept on a 'QUALITY CONTROL DATA SHEET. This information sheet would also
record storage conditions and disposal. See Appendix G.
11.5.2 NPS Groundwater Quality Assurance Data Form
Before any work begins on samples or controls, a "NPS GROUNDWATER QUALITY
ASSURANCE DATA FORM', is initiated by the processing laboratory. After extraction, concentration,
and cleanup, all pertinent set information is recorded on this form. This form and information for
completing it are in Appendix G.
11.6 Exceptions to the QAPJP
11.6.1 Request for Approval
Occasionally, it may become necessary for personnel assigned to the NPS to request approval
for exceptions or deviations from this QAPjP. This approval must come from the ECL Project Leader
-------
Section No. 11
Revision No. 4
Date: December 1989
Page 6 of 7
and may be initially requested either verbally or in writing, but in either case, the request must be
supported by a clear rationale, laboratory data, and documentation. When approval is requested, the
particular issue or exception will be assigned a reference number consisting of the laboratory name,
NFS Method No., date, and a number to differentiate among the several discussions that may take
place on that day.
EXAMPLE: ECL 3-040888-1 indicates that an exception to the QAPjP for Method 3
was requested on April 8, and it was the first one that day.
11.6.2 Documentation and Following Requirements
The ECL Project Leader will enter into a log book the reference number, the exception
requested, and the information and documentation required to support approval of the exception to
the QAPjP.
The person requesting the exception to the QAPjP must prepare a folder labelled with the
reference number and his/her name, and within a time frame specified by the ECL Project Leader
have in the folder documentation of the problem/exception and all supporting information and data. A
form 'EXCEPTIONS TO NPS QAPjP' is included at the end of this Section as Figure 11-1. A completed
version must be included with each request for an exception to the QAPjP.
-------
Section No. 11
Revision No. 4
Date: December 1989
Page 7 of 7
FIGURE 11-1
EXCEPTIONS TO NFS QAPJP
Date Method
Reference No.
Suggested Exception(s):
Signature of Person Seeking Exception
Approved Disapproved
Comments:
Bob Maxey, Technical Monitor
-------
Section No. 12
Revision No. 4
Date: December 1989
Page 1 of 2
12. AUDITS (Technical Systems/Data Quality/Performance Evaluation)
12.1 Requirements
Technical Systems and Data Quality Audits shall be conducted by the ECL QAC on NFS
Method 1 analytical work to assess the adherence to the QA Project Plan and to assess the quality of
data generated by the analytical systems. Performance Evaluation Audits will be initiated by ECL's
QAC to evaluate the technical personnel and the analytical system.
12.2 Frequency
12.2.1 Technical Systems and Data Quality
These audits shall be conducted at the beginning of the survey after 30 samples have been
analyzed and at least once every six months thereafter, exclusive of external audits.
12.2.2 Performance
At least one audit every six months.
12.3 Nature of Audits
12.3.1 Technical Systems Audits shall include the following:
12.3.1.1 Project Management System
12.3.1.1.1 Personnel - Qualifications
12.3.1.1.2 Documentation - QAPjP and SOPs
12.3.1.1.3 Communications about changes in requirements
12.3.1.1.4 Analyst feedback
12.3.1.2 Sample Tracking System - receipt through disposal or storage
12.3.1.3 Systems for Sample Preparations, e.g. extractions, clean up, etc.
12.3.1.4 Systems for Analytical Operations
12.3.1.4.1 Standards
12.3.1.4.2 Calibrations
12.3.1.4.3 Documentation of Analytical Operations
12.3.1.4.4 Corrective Action Loop
12.3.1.4.5 Instrument Maintenance
12.3.1.5 Data Management Systems
12.3.1.5.1 Collections
12.3.1.5.2 Reduction
12.3.1.5.3 Verification
12.3.1.5.4 Internal Review
12.3.1.5.5 Reporting
12.3.1.5.6 Use of QC Data at Bench Level
12.3.1.5.7 Data Storage and Retrieval
-------
Section No. 12
Revision No. 4
Date: December 1989
Page 2 of 2
12.3.1.6 Laboratory Management Systems
12.3.1.6.1 Major Equipment Purchases
12.3.1.6.2 Services and Supplies (solvents, etc.)
12.3.1.6.3 Maintenance of Ancillary Equipment
*
12.3.1.6.4 General Physical Set Up - space, cross contamination, etc.
12.3.1.6.5 Cold Storage Facilities
12.3.2 Data Quality Audits
Shall include tracking 3 samples from Method 1 from log-in through preparation, primary and
confirmatory analyses (including related set QC checks and other information), data handling and
disposal.
12.3.3 Performance Evaluation Audits
Shall consist of providing a P-E sample every six months. The audit will consist of a P.E.
solution to be spiked into a water matrix and analyzed as a routine NPS sample. The concentration of
the analytes in the P.E. solution will be unknown to the analysts involved in the method.
12.4 Standard
ECL's Quality Assurance Project Plan for Method 1; Printed Analytical Procedure for Method 1
and ECL's Quality Assurance Facilities Plan.
12.5 Reporting and Use of Audit Results
Following any of the above audits, the ECL QAC shall report the results in writing to both the
Lab Section Chief and NPS Project Leader. If deficiencies are found, each shall be specifically
identified along with the cause, if known. The QAC will provide a written plan or suggestion for
corrective action to the NPS Project Leader with a copy to ECL's Section Chief. The QAC shall also
follow up with a limited audit to verify that deficiencies were resolved by the proposed corrective
action.
-------
Section No. 13
Revision No. 4
Date: December 1989
Page 1 of 2
13. PREVENTIVE MAINTENANCE
13.1 Gas Chromatographs
A Hewlett Packard 5890A gas chromatograph with dual NitrogenPhosphorous Detectors (NPD)
and an H-P 7673A autosampler will be used for Method 1 analytical work. Routine maintenance for
these instruments is described below. *
Maintenance Item Schedule
• change injection port septa • bi-weekly or as needed
• change compressed gas traps and filter • every 6 months or as required
dryers
• service or change injection port liner • as required by instrument performance
• bake-out or replacement of GC column • daily or as required by instrument
• detector replacement (collectors) • as required by instrument performance
Spare parts are maintained at ECL to accommodate the above maintenance requirements, and
at least one spare GC column of each required type is on hand. ECL has a blanket purchase order
with Hewlett-Packard. Through it, parts and service can be accessed by telephone and usually are
provided in 2-5 working days, if needed.
A log book will be maintained for each instrument. In it will be kept records of all daily or
routine maintenance, problems and their resolution, and major repairs. It is the responsibility of the
analyst to make the above entries, and sign and date them.
13.2 GC/MS
The following schedule of maintenance tasks and spare parts applies to the Varian Mat 312 and
the Finnigan 5100.
Routine maintenance will be performed on the GC/MS and purge and trap units in accordance
with the following schedule:
Tasks Frequency
Clean source Monthly or as required by performance
Bake out magnetic and Monthly or as required by performance
electric sectors
Bake out GC column Daily or as required
Change pump oil Every 6 months or as required by use
Change GC column As required by performance
Change injection port septa Weekly or as required
Clean injection port liner Monthly or as required by performance
Most maintenance is done inhouse. When a problem is encountered which cannot be resolved
here, Finnigan MAT is contacted and service is arranged. Critical spare parts are also available to
minimize downtime and the following list of replacement parts and consumable spares is maintained
within the laboratory at all times.
1) Columns (at least one of each type used)
2) Ferrules for columns
3) Syringes
-------
Section No. 13
Revision No. 4
Date: December 1989
Page 2 of 2
4) Filaments (at least two of each)
5) Gold gaskets
6) Injection port septa
7) Vacuum pump oil
-------
Section No. 14
Revision No. 4
Date: December 1989
Page 1 of 3
14. SPECIFIC PROCEDURES FOR ASSESSING MEASUREMENT SYSTEM DATA
The formulas in this section are those used to calculate internal QC checks and statistics related
to QC checks.
14.1 Formulas Related to Instrument Control Standards and Determination of
Chromatographlc and Column Performance *
• Peak Symmetry Factor (PSF). See Figure 14-1 at the end of this section.
PSF = WM/21
0.5 X W(1/2)
, where W(1/2) = the width of the front of the chromatographic peak at half-height,
assuming the peak is split at the highest point and W(1/2) is the
peak width at half height.
• Peak Gaussian Factor (PGF). See Figure 14-1 at the end of this section.
PGF = 1.83XWf1/a , where
W(1/2) = peak width at half-height
W(1/10) = peak width at tenth-height.
• Resolution (R)
R = t/W , where
t = the difference in elution times between two peaks, and
W = the average peak width, at the baseline, of the two peaks.
14.2 Formulas For Calculating Statistics
• Standard Deviation(s)
s= / S (xrx)2
.where
n-1
xv..xn = individual sample values
x = sample mean
n = sample size or no. of sample values
Coefficient of Variation (CV)
CV= s
-------
Section No. 14
Revision No. 4
Date: December 1989
Page 2 of 3
• Relative Standard Deviation (RSD)
RSD = CVX100
• Mean Recovery (R)
»
n
R = E R/n
i=1
• Percent Recovery (%R)
%R = (net value of spike) X 100
True value of spike .where
(net value of spike) = (gross value) - (value attributed to background or Blank)
• Minimum Detection Limit (MDL)
MDL = s X t(.99)(n.1} , where
t(.99) = 'Student's t-value appropriate for a one tailed test at 99% confidence level and a
standard deviation estimate with (n-1) degrees of freedom.
14.3 Formulas Defining Control Limits
• Upper Control Limit (UCL) = R + 3s
Upper Warning Limit (UWL) = R + 2s
• Lower Warning Limit (LWL) = R - 2s
• Lower Control Limit (LCL) = R - 3s .where
R = Mean Recovery
S = Standard Deviation
-------
Section No 14
Revision No 4
Date: December 1989
Page 3 of 3
FIGURE 14-1
EQUATION USED TO CALCULATE PEAK SYMMETRY FACTOR (PSF)
AND PEAK GAUSSIAN FACTOR (PGF)
PSF
PGf =.
J_
0.5 x W
1.03 x W
W
1/10
SJLCB
-------
Section No. 15
Revision No. 4
Date: December 1989
Page 1 of 1
15. CORRECTIVE ACTION
Corrective action is required when out-of-control situations develop regarding QC criteria,
procedures, or specific Survey requirements. Sections 5 and 11 contain specific QC objectives and
criteria for this Method, and Section 7 contains specific sampling and tracking requirements. All of
%-
these elements are evaluated as required by established NFS guidelines, and log books are
maintained as documentation.
An analyst, team member, or Sample Custodian experienced with this Method and involved in
day-to-day activities with it will be the first to be aware of a problem, inconsistency, or QC parameter
outside acceptance limits. It is his/her responsibility to note the nature and significance of the
problem and to bring it to the attention of the ECL Project Leader. Such problems shall be properly
documented through use of the 'SAMPLE RECEIPT SCREENS FOR NPS LABORATORIES' (refer to
end of Section 7) and a related log book in Sample Receiving or by means of the 'QUALITY
ASSURANCE DATA FORM' (see Appendix G).
The following areas will be addressed:
• specific exception to the QC requirement
• when the problem was first noted and by whom
• who was notified
• corrective or remedial action required
• action taken
• verification that a QC exception or problem was resolved and the date
• sample 'set" numbers and specific samples involved
If the ECL Project Leader cannot readily resolve the problem or provide guidance for corrective
action, the ECL Quality Assurance Coordinator (ECL QAC) must be notified. The QAC will take a lead
role in developing a strategy to resolve the problem. Verification that the problem has been resolved
must also be provided before analytical work continues.
All QC exceptions, problems, corrective actions, and verification documentation must be
reported monthly to the ECL Project Leader for this Method. For any problems requiring involvement
of the ECL QAC, the ECL Project Leader must be immediately informed.
-------
Section No. 16
Revision No. 4
Date: December 1989
Page 1 of 4
16. QA REPORTS TO MANAGEMENT
Internal Referee Laboratory QA Reporting System
The ECL NPS Project Leader will interact daily with the analyst performing the bench work and
data generation for Method 1. The analyst will inform the Project Leader immediately when any QA
problem or unusual situation develops. The analyst will follow the verbal notification with a written note
explaining the problem. The ECL Project Leader will keep ECL's QA Coordinator informed and will
discuss unresolved problems with him. The Project Leader will inform the ECL Section Chief of major
problems.
The analyst for Method 1 will complete an 'EPA Referee-Laboratories Progress QA Report". A
copy of this form, Figure 16-1, is included in this section. Copies of this form will be submitted monthly
to the Project Leader, who will in turn provide copies to the Section Chief and ECL QA Coordinator.
The ECL QA Coordinator will submit on a quarterly basis copies of these forms to OPP's Quality
Assurance Officer and to the NPS Quality Assurance Officer. Copies of the ECL internal audit reports
(refer to Section 12.5) will be sent to OPP's Quality Assurance Officer.
Referee Laboratory Responsibilities for External Contract Monitoring - QA Monitoring - QA
Reporting System
Six copies of the Primary Analytical Contractor Laboratory's report are to be provided monthly to
the ECL Technical Monitor for Method 1. These reports are to be provided within 15 calendar days
after the end of the month being reported. The format of this report is covered in the contractor's
QAPjP for Method 1.
The Technical Monitor for Method 1 will provide the ECL Analytical Coordinator with a quarterly
Technical Monitor Progress - QA Report1, Figure 16-2, a copy of which appears in this section.
Copies of the "Monthly Contract Monitoring QA Report" for that quarter will be attached to the
Technical Monitor Report. A copy of these reports will also be provided quarterly by the ECL
Analytical Coordinator to ECL's Quality Assurance Coordinator, to OPP's QAO and to the NPS QAO.
The ECL Analytical Coordinator will submit an 'Analytical Coordinator Status Report' through the
ECL Section Chief to the Director of the NPS. Copies of the quarterly reports from the Technical
Monitor will be attached to the Analytical Coordinator Status Report. A copy of the latter report, Figure
16-3, is included in this section.
-------
Section No '6
Revision No 4
Date. December 1989
Page 3 of 4
FIGURE 16-2
TECHNICAL MONITOR PROGRESS - QA REPORT
Hechod S
Laboratory
Report Period
Date
1. Progress: '»
0 samples received
ff samples analyzed
9 samples invalidated
No. for data sets sent to EPA Data Manager
2. Major Problems and Status
a. Technical:
b. Contractural:
3. Consents
-------
Section No 16
Revision No 4
Date' Decemder 1989
Page 4 of 4
FIGURE 16-3
ANALYTICAL COORDINATOR STATUS REPORT
V
Report r«rioa_
Prepared By _
Dace
Monthly - Financial States
- Contract Administrative Needs
Quarterly - Data Summary
- Copies of quarterly reports froo Technical Monitors
-------
Appendix A
Revision No 4
Date December 1989
Page 1 of 7
APPENDIX A
SAMPLE CUSTODY
-------
ENVIRONMENTAL CHEMISTRY LABORATORY
NFS SAMPLE LOGGING
(1,3,6)
PREPARED BY:
DATE:
LAB. I.D.
(FIELD SAMPLE I)
DATE SAMPLED
DATE SHIPPED
DATE RECEIVED I TIME SAMPLED OONDTT
-------
NFS SET COMPOSITION FORM
METHOD 1
APPROVED BY PROJECT OFFICER SET NO.
SIGNATURE
DATE
SET CONTROLS
»
1. Method Blank
2. Lab. Control Spike, MIX A
3. Lab. Control Spike, MIX B
4. Lab. Control Spike, MIX C
NPS FIELD SAMPLES
Field Sample No. Date Sampled Date Arrived ECL
6.
7.
e.
9.
-------
SAMPLE CONTROL RECORD
EPA/ECL
BORATORY
MPLE NO.
REMOVED
BY
DATE AND TIME
REMOVED
DATE AND TIME
RETURNED
.
1
—
I
r ~~
-------
ECL NFS SAMPLE TRACKING FORM
METHOD 1
Date
Sample
Taken
Date
Rec'd
at ECL
Date
Extracted
Date
Analysis
Completed
Date Removed
for QC/MS
Confirmation
GC/MS
Confirmation
Completed
-------
-------
Appendix 3
Revision No 4
Date December 1989
Page 1 of 50
APPENDIX B
BATTELLE'S VERSION
-------
Method 1. Determination of Nitrogen- and Phosphorus-Containing
Pesticides in Ground Water by Gas Chromatography with a
Nitrogen-Phosphorus Detector
SCOPE AND APPLICATION
1.1 This is a gas chromatographic (GC) method applicable to the
determination of certain nitrogen- and phosphorus-containing
pesticides in ground water. Analytes that can be determined
using this method are listed in Table It
1.2 This method has been validated in a single laboratory.
Estimated detection limits (EDLs) 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.
1.4 When this method is used to analyze unfamiliar samples for any
or all of the analytes above, analyte identifications must be
confirmed by at least one additional qualitative technique.
2- SUMMARY OF METHOD
2.1 A measured volume of sample of approximately 1 L is solvent
extracted with methylene chloride by mechanical shaking in a
separatory funnel or mechanical tumbling in a bottle. The
methylene chloride extract is isolated, dried and concentrated
to a volume of 5 ml after solvent substitution with methyl tert-
butyl ether (MTBE). Chromatographic conditions are described
which permit the separation and measurement of the analytes in
the extract by GC with a nitrogen-phosphorus detector (NPD).
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 analyte,
dissolved in an organic solvent, analyzed under the same
procedures and conditions used to analyze sample extracts
containing that analyte.
-------
3.3 Estimated detection limn (EDL) -- the minimum concentration of
a substance that can be measured and reported with confidence
that the analyte concentration is greater than zero as deter-
mined from the analysis of a sample in a given matrix containing
the analyte. The EDL is equal to the level calculated by
multiplying the standard deviation of replicate measurements
times the students' 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 witti signal-to-noise ratio
of approximately five, whichever value is higher.
3.4 Instrument quality control (QC) standard -- a MTBE 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 accep-
table 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 measure-
ments of other analytes that are sample components. The
internal standard must be a compound that is not a sample
component.
3.6 Laboratory control standard -- a solution of analytes prepared
in the laboratory by dissolving known amounts of pure analytes
in a known amount of reagent water. In this method, the
laboratory control standard is prepared by adding appropriate
volumes of the appropriate standard solution to reagent water.
3.7 Laboratory method blank -- a portion of reagent water analyzeo
as if it were a sample.
3.8 Performance evaluation sample •• A water-soluble solution of
method analytes distributed by the Quality Assurance Branch,
Environmental Monitoring and Support Laboratory, USEPA, Cincin-
nati, Ohio. A small measured volume of the solution is added to
a known volume of reagent water and analyzed using procedures
identical to those used for samples. Analyte true values are
unknown to the analyst.
3.9 Quality control check sample -- a water soluble solution
containing known concentrations of analytes prepared by a
laboratory other than the laboratory performing the analysis.
The performing laboratory uses this solution to demonstrate that
it can obtain acceptable identifications and measurements with a
method. A small measured volume of the solution is added to a
known volume of reagent water and analyzed with procedures
identical to those used for samples. True values of analytes
are known by the analyst.
-------
3.10 Stock standard solution -- a concentrated solution containing a
certified standard that is a method analyte, or a concentrated
solution of an analyte prepared in the laboratory with an
assayed reference compound.
3.11 Surrogate standard •- a pure compound added to a sample in a
known amount and used to detect gross abnormalities during
sample preparation. The surrogate standard must be a compound
that is not a sample component.
4. INTERFERENCES
4.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware and other sample processing apparatus that
lead to discrete artifacts or elevated baselines in gas chroma-
tograms. All reagents and apparatus must be routinely demon-
strated to be free from interferences under the conditions of
the analysis by running laboratory method blanks as described in
Section 10.8.
4.1.1 Glassware must be scrupulously cleaned.^ Clean all
glassware as soon as possible after use by thoroughly
rinsing with the last solvent used in it. Follow by
washing with hot water and detergent and thorough
rinsing with tap and reagent water. Drain dry, and heat
in an oven or muffle furnace at 400*C for 1 hour. Oo
not heat volumetric ware. Thermally stable materials
might not be eliminated by this treatment. Thorough
rinsing with acetone may be substituted for the heat-
ing. . After drying and cooling, seal and store glassware
in a clean environment to prevent any accumulation of
dust or other contaminants. Store inverted or capped
with aluminum foil.
4.1.2 The use of high purity reagents and solvents helps to
minimize interference problems. Purification of
solvents by distillation in all-glass systems may be
required.
4.2 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 HTBE can minimize sample cross contamination.
After analysis of a sample containing high concentrations of
analytes, one or more injections of HTBE should be made to
ensure that accurate values are obtained for the next sample.
4.3 Matrix interferences may be caused by contaminants that are
coextracted from the sample. The extent of matrix interferences
will vary considerably from source to source, depending upon the
to
-------
ground water sampled. Cleanup of sample extracts may be
necessary. Positive identifications should 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
identified2"4 for the information of the analyst.
6. APPARATUS AND EQUIPMENT (All specifications are suggested. Catalog
numbers are included for illustration only.)
6.1 SAMPLING EQUIPMENT
6.1.1 Grab sample bottle -- Borosil icate, 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
methanol overnight prior to use.
6.2 GLASSWARE
6.2.1 Separatory funnel -- 2000-mL, with TFE-fluorocarbon
stopcock, ground glass or TFE-fluorocarbon stopper.
6.2.2 Tumbler bottle -- 1.7-L (Wheaton Roller Culture Vessel),
with TFE-fluorocarbon lined screw cap. Cap liners are
cut to fit from sheets (Pierce Catalog No. 012736) and
extracted with methanol overnight prior to use.
6.2.3 Flask, Erlenmeyer -- 500-mL.
6.2.4 Concentrator tube, Kuderna-Oanish (K-D) -- 10- or 25-mL,
graduated (Kontes K-5700SO-2525 or K-S70050-1025 or
equivalent). Calibration must be checked at the volumes
employed in the test. Ground glass stoppers are used to
prevent evaporation of extracts.
-------
6.2.5 Evaporative flask, K-0 -- SOO-ml (Kontes K-570001-0500
or equivalent). Attach to concentrator tube with
springs.
6.2.6 Snyder column, K-D -- three-ball macro (Kontes
K-503000-0121 or equivalent).
6.2.7 Snyder column, K-0 -- two-ball micro (Kontes
K-569001-02J9 or equivalent).
»
6.2.8 Vials •- glass, 5- to 10-ml capacity with TFE-fluoro-
carbon lined screw cap.
6.3 Separatory funnel shaker -- Capable of holding eight 2-1 separa-
tory funnels and shaking them with rocking motion to achieve
thorough mixing of separatory funnel contents (available from
Eberbach Co. in Ann Arbor, MI).
6.4 Tumbler -- Capable of holding 4 to 6 tumbler bottles and
tumbling them end-over-end at 30 turns/min (Associated Design
and Mfg. Co., Alexandria, VA.).
6.5 Boiling stones •- carborundum, £12 granules (Arthur H. Thomas
Co. £'1590-033). Heat at 400*C for 30 min prior to use. Cool
and store in 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
stripchart recorder. A data system is recommended for measuring
peak areas.
6.8.1 Primary column -- 30 m long x 0.25 mm I.D. OB-5 bonded
fused silica column, 0.25 urn 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 urn film thickness
(available from J&W).
6.8.3 Detector -- Nitrogen-phosphorus (NPD). A NPD was used
to generate the validation data presented in this
method. Alternative detectors, including a mass
-------
spectrometer, may be used in accordance with the
provisions described in Section 10.3.
7. REAGENTS AND CONSUMABLE MATERIALS
7.1 Acetone, methylene chloride, HTEE -- Distil led-in-glass quality
or equivalent.
7.2 Phosphate buffer, pH7 -- Prepare by mixing 29.6 ml 0.1 N HCl 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 inter-
fering organic substances.
7.4 Sodium chloride (NaCl), crystal, ACS grade -- Heat treat in a
shallow tray at 450*C for a minimum of 4 hours to remove inter-
fering organic substances.
7.5 Triphenylphosphate (TPP) -- >98% purity, for use as internal
standard (available from Aldrich Chemical Co.).
7.6 1,3-Dimethyl-2-nitrobenzene -- >98% purity, for use as surrogate
standard (available from Aldrich Chemical Co.).
7.7 Reagent water -- Reagent water is defined as a water in which an
interferent is not observed at or above the EDL of any analyte.
Reagent water used to generate the validation data in this method
was distilled water obtained from the Magnetic Springs Water Co.,
Columbus, Ohio.
7.8 STOCK STANDARD SOLUTIONS (1.00 ug/uL) -- Stock standard solutions
may be purchased as certified solutions or prepared from pure
standard materials using the following procedure:
7.8.1 Prepare stock standard solutions by accurately weighing
approximately 0.0100 g of pure material. Dissolve the
material in MTBE and dilute to volume in a 10-mL volu-
metric flask. The stock solution for simazine should be
prepared in methanol. Larger volumes may be used at the
convenience of the analyst. If compound purity is certi-
fied at 96% or greater, the weight may be used without
correction to calculate the concentration of the stock
standard. Commercially prepared stock standards may be
used at -any concentration if they are certified by the
manufacturer or by an independent source.
7.8.2 Transfer the stock standard solutions into TFE-fluoro-
carbon-sealed screw cap vials. Store at room temperature
and protect from light.
-------
7.8.3 Stock standard solutions should be replaced after two
months or sooner if comparison with laboratory control
standards indicates a problem.
7.9 INTERNAL STANDARD SPIKING SOLUTION -- Prepare the internal
standard spiking solution by accurately weighing approximately
0.0500 g of pure TPP. Dissolve the TPP in MTBE and dilute to
volume in a 100-mL volumetric flask. Transfer the internal
standard spiking solution to a TFE-fluorocarbon-sealed screw cap
bottle and store at room temperature. Addition of 50 uL of the
internal standard spiking solution to 5 mL of sample extract
results in a final TPP concentration of 5.0 ug/mL. Solution
should be replaced when ongoing QC (Section 10) indicates a
problem.
7.10 SURROGATE STANDARD SPIKING SOLUTION -- Prepare the surrogate
standard spiking solution by accurately weighing approximately
0.0250 g of pure 1,3-dimethyl-2-nitrobenzene. Dissolve the 1,3-
dimethyl-2-nitrobenzene in MTBE end dilute to volume in a 100-mL
volumetric flask. Transfer the surrogate standard spiking
solution to a TFE-fluorocarbon-sealed screw cap bottle and store
at room temperature. Addition of 50 uL of the surrogate standard
spiking solution to a 1-L sample prior to extraction results in a
1,3-dimethyl-2-nitrobenzene concentration in the sample of
12.5 ug/L. Assuming quantitative surrogate recovery, addition of
50 uL of the surrogate standard spiking solution to a sample
results in a 1,3-dimethyl-2-nitrobenzene concentration in the
final extract of 2.5 pg/mL. Solution should be replaced when
ongoing QC (Section 10) indicates a problem.
7.11 INSTRUMENT QC STANDARD -- Prepare the instrument QC standard by
adding 5 pL of the vernolate stock solution, 0.5 mL of the
bromacil stock solution, 30 uL of the prometon stock solution,
15 uL of the atrazine stock solution, 1.0 mL of the surrogate
spiking solution, and 500 uL of the internal standard spiking
solution to a 100-mL volumetric flask. Dilute to volume with
MTBE and thoroughly mix the solution. Transfer the instrument QC
standard to a TFE-fluorocarbon-sealed screw cao 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 AND STORAGE
8.2.1 Add mercuric chloride to the sample bottle in amounts to
produce a concentration of 10 mg/L. Add 1 mL of a
solution containing 10 mg/ml of mercuric chloride in
7 ' '
-------
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 the sample is collected in a bottle containing
preservative, seal the bottle and shake vigorously for
1 min. • »
8.2.3 The samples must be iced or refrigerated at 4*C away from
light from the time of collection until extraction.
Preservation study results presented in Table 11 indicate
that most of the target analytes present in 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 preserva-
tion technique is applicable to the samples under study.
6.3 EXTRACT STORAGE
8.3.1 Extracts should be stored at 4*C away from light.
Preservation study results given in Table 11 indicate
that most analytes are stable for 28 days; however, a 14-
day maximum extract storage time is recommended. The
analyst should verify appropriate extract holding times
applicable to the samples under study.
CALIBRATION
9.1 Establish GC operating parameters equivalent to those indicated
in Table 3. The GC system must be calibrated using the internal
standard technique (Section 9.2).
9.2 INTERNAL STANDARD CALIBRATION PROCEDURE -- To use this approach,
the analyst must select one or more internal standards 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. TPP
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 known constant amount of one or more internal
standards, and dilute to volume with HTBE. 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
8
IS
-------
concentrations expected in the sample concentrates, or
should define the working range of the detector.
9.2.2 Inject 2 pi of each calibration standard and tabulate the
relative response for each analyte (RRa) to an internal
standard using the equation:
RRa = Aa/Ais
where:' Aa = the peak area of thre analyte, and
A^s = 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. Data presented in this report were generated
using TPP for quantification calculations.
9.2.3 The working calibration curve must be verified on each
working shift by the measurement of one or more calibra-
tion standards. If the response for any analyte varies
from the predicted response by more than +20%, 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 prepara-
tion; the monitoring of internal standard area counts or peak
heights in each and every sample as a continuing check on system
performance; the analysis of laboratory control standards, QC
samples, and performance evaluation (P£) 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 analytes.
Using a stock standard that differs from calibration
standard, prepare a laboratory control (LC) check sample
concentrate in methanol 1000 times more -concentrated
than the selected spike concentration.
-------
10.2.2 Using a syringe, add 1 ml of the LC sample concentrate
to each of a minimum of four 1-L aliquots of reagent
water. A representative ground water may be used in
place of the reagent water, but one or more unspiked
aliquots must be analyzed to determine background
levels, and the spike level must, at a minimum, exceed
twice the background level for the test to be valid.
Analyze the aliquots according to the method beginning
in Section 11.
10.2.3 Calculate the average percent recovery (R) and the
standard deviation of the percent recovery (SR)", for the
results. Ground water background corrections must be
made before R and SR 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 RSO or 20 percent, whichever
is greater, and your mean recovery lies within the
interval R±3S or R+30% whichever is greater.
10.3 In recognition" of the rapid advances occurring in chromato-
graphy, the analyst is permitted to modify GC columns, GC
conditions, or detectors to improve the separations or lower the
cost of measurements. Each time such modifications to the
method are made, the analyst is required to repeat the procedure
in Section 10.2.
10.4 ASSESSING SURROGATE RECOVERY
10.4.1 All samples and blanks must be fortified with the
surrogate spiking compound before extraction. A
surrogate standard determination must be performed on
all samples (including matrix spikes) and blanks.
10.4.2 Determine whether the measured surrogate concentration
(expressed as percent recovery) falls between 70 and 130
percent.
10.4.3 When the surrogate recovery for a laboratory method
blank is less than 70 or greater than 130 percent, the
laboratory must take the following actions:
'lO
-------
(1) Check calculations to make sure there are no
errors.
(2) Check internal standard and surrogate standard
spiking solutions for degradation, contamination,
or other obvious abnormalities.
(3) Check instrument performance.
»-
Reinject the laboratory method blank extract. If the
reanalysis fails the 70 to 130 percent recovery
criteria, the analytical system must be considered "out
of control." The problem must be identified and
corrected before continuing.
10.4.4 When the surrogate recovery for a sample is less than 70
percent or greater than 130 percent, the laboratory must
establish that the deviation is not due to laboratory
problems. The laboratory shall document deviations by
taking the following actions:
(1) Check calculations to make sure there are no
errors.
(2) Check internal standard and surrogate standard
spiking solutions for degradation, contamination,
or other obvious abnormalities.
(3) Check instrument performance.
Recalcalate or reanalyze the extract if the above steps
fail to reveal the cause of the noncompliant surrogate
recoveries. If reanalysis of the sample or extract
solves the problem, only submit the sample data from the
analysis with surrogate spike recoveries within the
required limits. If reanalysis of the sample or extract
fails to solve the problem, then report all data for
that sample as suspect.
10.5 ASSESSING THE INTERNAL STANDARD
10.5.1 An internal standard peak area or peak height check must
be performed on all samples. All sample extracts must
be fortified with the internal standard.
10.5.2 Internal standard recovery must be evaluated for
acceptance by determining whether the measured peak area
or peak height for the internal standard in any sample
deviates by more than 30 percent from the average peak
area or height for the internal standard- in the calibra-
tion standards.
• if
-------
10.5.3 When the internal'standard peak area or height for any
sample is outside the limit specified in 10.5.2, the
laboratory must investigate.
10.5.3.1 Single occurrence -- Reinject an aliquot of
the extract to ensure proper sample injection.
If the reinjected sample extract aliquot
displays an internal standard peak area or
height within specified limits, quantify and
report results. If the reinjected sample
extract aliquot displays an internal standard
peak area or height outside the specified
limits, but extract aliquots from other
samples continue to give the proper area or
height for the internal standard, assume an
error was made during addition of the internal
standard to the failed sample extract. Repeat
the analysis of that sample.
10.5.3.2 Multiple Occurrence -- If the internal
standard peak areas or heights for successive
samples fail the specified criteria (10.5.2),
check the instrument for proper performance.
After optimizing instrument performance, check
the calibration curve using a calibration
check standard (Section 9). If the calibra-
tion curve is still applicable and if the
calibration check standard internal standard
peak area or height is within ±30% of the
average internal standard peak area or height
for the calibration standards, reanalyze those
sample extracts whose internal standard failed
the specified criteria. If the internal
standard peak areas or heights now fall within
the specified limits, report the results. If
the internal standard peak areas or heights
still fail to fall within the specified limits
or if the calibration curve is no longer
applicable, then generate a new calibration
curve (Section 9) and reanalyze those sample
extracts whose internal standard failed the
peak area or height criteria.
10.6 ASSESSING LABORATORY PERFORMANCE
10.6.1 The laboratory must, on an ongoing basis, analyze at
least one laboratory control standard per sample set (a
sample set is all those samples extracted within a
24-hour period).
12
-------
10.6.1.1 The spiking concentration in the laboratory
control standard should be 15 times the EDI.
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 (R^) as (100xA)%/T,
where T is the'known true concentration of the
spike.
10.6.1.3 Compare the percent recovery (R^) for each
analyte with established QC acceptance
criteria. QC criteria are established by
initially analyzing five laboratory control
standards and calculating the average percent
recovery (R) and the standard deviation of the
percent recovery (Sp) using the following
equations:
and
rrn
n-l
/
.2\ .
. 1
n
where: n
number of measurements for each
analyte, and
individual percent recovery
value.
Calculate QC acceptance criteria as follows:
Upper Control Limit (UCL) - R +
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.
13
-------
Update the performance criteria on a con-
tinuous basis. After each five to ten new
recovery measurements (R^s), recalculate R and
SR using all the data, and construct new
control limits. When the total number of data
points reach twenty, update the control limits
by calculating R and SR using only the most
recent twenty data points.
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 analyti-
cal 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.
10.6.2 Each quarter, it is essential that the laboratory
analyze (if available) QC check standards. If the
criteria established by the U.S. Environmental Protec-
tion Agency (USEPA) and provided with the QC standards
are not met, corrective action needs to be taken and
documented.
10.6.3 The laboratory must analyze an unknown performance
evaluation sample (when available) at least once a year.
Results for each of the target analytes need to be
within acceptable limits established by USEPA.
10.7 ASSESSING ANALYTE RECOVERY
10.7*1 The laboratory must, on an ongoing basis, spike each of
the target analytes into ten percent of the samples.
10.7.1.1 The spiking concentration in the sample should
be one to five times the background concentra-
tion, or, if it is impractical to determine
background levels before spiking, 15 times the
EDL.
10.7.1.2 Analyze one sample aliquot to determine the
background concentration (B) of each analyte.
Spike a second sample aliquot with a labora-
tory control (LC) sample concentrate (the
14
-------
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 (R^ as 100(A-B)%/T,
where T is the known true concentration of the
spike.
10.7.1.3 Compare the percent recovery (Rj) for each
analyte with QC acceptance criteria esta-
blished from the analyses of laboratory
control standards.
Monitor all data from dosed samples. Analyte
recoveries must fall within the established
control limits.
10.7.1.4 If the recovery of any such analyte falls
outside the designated range, and the labora-
tory performance for that analyte is judged to
be in control, the recovery problem encoun-
tered 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 user
that the results are suspect due to matrix
effects.
10.8 ASSESSING LABORATORY CONTAMINATION (METHOD BLANKS) -- Before
processing any samples, the analyst must demonstrate that all
glassware and reagent interferences are under control. This is
accomplished by the analysis of a laboratory method blank. A
laboratory method blank is a 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 contam-
ination before processing samples and eliminate the interference
problem.
10.9 ASSESSING INSTRUMENT PERFORMANCE (INSTRUMENT QC STANDARD) --
Instrument performance should be monitored on a daily basis by
analysis of the instrument QC standard. The instrument QC
standard contains compounds designed to indicate appropriate
instrument sensitivity, column performance and chromatographic
performance. Instrument QC standard components and performance
criteria are listed in Table 10. Inability to demonstrate
acceptable instrument performance indicates the need for
reevaluation of the GC-NPD system. A GC-NPD chromatogram
• *
15
-------
generated from the analysis of the instrument QC standard is
shown in Figure 1. The sensitivity requirements are set based
on the EDLs published in this method. If laboratory EDLs differ
from those listed in this method, concentrations of the instru-
ment QC standard compounds must be adjusted to be compatible
with the laboratory EDLs. 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 tumbler.
11.1.1 Add preservative to 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 pL 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 NaCl 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 s to rinse the inner walls. Transfer
the solvent to the sample contained in the separatory
funnel or tumbler bottle, seal, and shake for 10 s,
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 mixing
of the organic and aqueous phases should be observed at
least 2 min after starting the mixing device.
16
-------
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
min. If the emulsion interface between layers is more
than one third the volume of the solvent layer, the
analyst must employ mechanical techniques to complete
the phase separation. The optimum technique depends
upon the sample, but may include ^tirring, filtration
through glass wool, centrifugation, or other physical
methods. Collect the methylene chloride extract in a
500-ml Erlenmeyer flask containing approximately 5 g
anhydrous sodium sulfate. Swirl flask to dry extract;
allow flask to sit for 15 min.
11.1.6 Determine the original sample volume by refilling the
sample bottle to the mark and transferring the water to
a 1000-mL graduated cylinder. Record the sample volume
to the nearest 5 ml.
11.2 MANUAL EXTRACTION METHOD -- Alternative procedure.
11.2.1 Add preservative to 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 pL of the surrogate
standard spiking solution. Pour the entire sample into
a 2-L ssparatory funnel.
11.2.2 Adjust the sample to pH 7 by adding 50 mL of phosphate
buffer.
11.2.3 Add 100 g NaCl to the sample, seal, and shake to
dissolve salt.
11.2.4 Add 60 mL methylene chloride to the sample bottle, seal,
and shake 30 s to rinse the inner walls. Transfer the
solvent to the separatory funnel and extract the sample
by vigorously shaking the funnel for 2 min with periodic
venting to release excess pressure. Allow the organic
layer to separate from the water phase for a minimum of
10 min. If the emulsion interface between layers is
more than one third the volume of the solvent layer, the
analyst must employ mechanical techniques to complete
the phase separation. The optimum technique depends
upon the sample, but may include stirring, filtration of
the emulsion through glass wool, centrifugation, or
other physical methods. Collect the methylene chloride
extract in a 500-mL Erlenmeyer flask containing approxi-
mately 5 g anhydrous sodium sulfate.
17
-------
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 Erlenmeyer
flask. Perform a third extraction in the same manner.
Swirl flask to dry extract; allow flask to sit for 15
min.
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 to a 500-ml evaporative flask. Decant
the methylene chloride extract into the K-D concen-
trator. Rinse the remaining sodium sulfate with two
25-mL portions of methylene chloride and decant the
rinses into the K-D concentrator.
11.3.2 Add 1 to 2 clean boiling stones to the evaporative flask
and attach a macro Snyder column. Prewet 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
70*C, 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 min. At the proper rate of 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 min.
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 HTBE 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 HTBE to
the top. Place the micro K-D apparatus 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 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 to the micro K-D and reconcentrate to 2 ml.
Remove the micro K-0 from the bath and allow it to drain
and cool. Remove the micro Snyder column, and rinse the
18
-------
walls of the concentrator tube while adjusting the
volume to 5.0 ml with MTBE.
11.3.4 Add 50 uL of the internal standard spiking solution to
the sample extract, seal, and shake to distribute the
internal standard. Transfer extract to an appropriate-
sized TFE-fluorocarbon-sealed screw-cap vial and store,
refrigerated at 4*C, until analysis by GC-NPO.
*
11.5 GAS CHROMATOGRAPHY
11.5.1 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 2-6. Other GC columns, chromatographic
conditions, or detectors may be used if the requirements
of Section 10.3 are met.
11.5.2 Calibrate the system daily as described in Section 9.
The standards and extracts must be in MTBE.
•11.5.3 -Inject 2 uL of the sample extract. Record the resulting
peak s^ie in area units.
11.5.4 The width of the retention time window used to make
identifications should be based upon measurements of
actual retention time variations of standards over the
course of a day. Three times the standard deviation of
a retention time can be used to calculate a suggested
window size for a compound. However, the experience of
the analyst should weigh heavily in the interpretation
of chromatograms.
11.5.5 If the response for the peak exceeds the working range
of the system, dilute the extract and reanalyze.
12. CALCULATIONS
12.1 Calculate analyte concentrations in the sample from the relative
response for the analyte 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 falls outside of the control limits in
Section 10, data for the affected analytes must be labeled as
suspect.
13. PRECISION AND ACCURACY
13.1 In a single laboratory, analyte recoveries from'reagent water
were determined at five concentration levels. Results were used
19
-------
to determine analyte EDls and demonstrate method range.
Analytes were divided into five spiking groups (A-E) for
recovery studies. EDL data are given in Table 2. Method range
data 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
five spiking groups (A-E) 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. Sample extracts were also
reanalyzed after they were stored for 28 days at -4*C and
protected from light. Results were used to predict expected
analyte stability in ground water samples and sample extracts.
Analytes were divided into five spiking groups (A-E) for
recovery studies. Analyte recoveries from the preserved, spiked
ground water samples and stored sample extracts are given in
Table 11.
20
-------
REFERENCES
1. ASTM Annual Book of Standards, Part 11, Volume 11.02, 03694-82,
"Standard Practice for Preparation of Sample Containers and for
Preservation", American Society for Testing and Materials Philadel-
phia, PA, p. 86, 1986.
2. "Carcinogens - Working with Carcinogens," Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National -Institute for Occupational Sa/ety and Health,
Publication No. 77-206, Aug. 1977.
3. "OSHA Safety and Health Standards, General Industry," (29 CFR 1910),
Occupational Safety and Health Administration, OSHA 2206, (Revised,
January 1976).
4. "Safety in Academic Chemistry Laboratories," American Chemical Society
Publication, Committee on Chemical Safety, 3rd Edition, 1979.
5. ASTM Annual Book of Standards, Part 11, Volume 11.01, D3370-82, "Stan-
dard Practice for Sampling Water," American Society for Testing and
Materials, Philadelphia, PA, p. 130, 1986.
' 21
-------
TABLE 1. METHOD ANALYTES
Analyte
Alachlor
Ametryn
Atraton
Atrazlne
Bromacil
Butachlor
Butyl ate
Carboxin
Chlorpropham
Cycloate
Demeton-S
Diazinon
Dichlorvos
Oiphenamid
Disul foton
Oisulfoton sulfone
Disulfoton sulfoxide (c)
EPTC
Ethoprop
Fenamiphos
Fenarimol
Fluridone
Hexazinone
Herphos
Methyl paraoxon
Hetolachlor
Metribuzin
Mevinphos
MGK 264
Hoi inate
Napropamide
Norflurazon
Pebulate
Prometon (c)
Prometryn
Pronamide (c)
Propazine
Simazine
Simetryn
Stirofos
Tebuthiuron
Terbacil
CAS No. (a)
15972-60-8
834-12-8
111-44-4
1912-24-9
314-40-9
23184-66-9
2008-41-5
5234-68-5
101-21-3
1134-23-2
126-75-0
333-41-5
62-73-7
957-51-7
298-04-4
2497-06-5
2497-07-6
563-12-2
13194-48-4
22224-92-6
60168-88-9
59756-60-4
51235-04-2
150-50-5
950-35-6
51218-45-2
21087-64-9
7786-34-7
113-48-4
2212-67-1
15299-99-7
27314-13-2
1114-71-2
1610-18-0
7287-19-6
23950-58-5
139-40-2
122-34-9
1014-70-6
22248-79-9
34014-18-1
5902-51-2
Ident. Code (b)
07
' A7
05
B3
08
CIO
02
Cll
04
A3
C3
Cl
El
Bll
A5
B12
01
61
82
AID
E13
E14
013
813
86
C7
C6
Al
C9
03
E9
C12
E2
A4
88 .
06
84
E5
E7
010
E3
E6
22
-------
TABLE 1. METHOD ANALYTES (continued)
Analyte CAS No. (a) Ident. Code (b)
Terbufos (c) 13071-79-9 C4
Terbutryn 886-50-0 B9
Triademefon ' 43121-43-3 BIO
Tricyclazole 41814-78-2 ' Oil
VernoUte 1929-77-7 C2
(a) CAS No. = Chemical Abstracts Service registry number.
(b) Code used for identification of peaks in figures; letter
indicates spiking mixture which contained each analyte; IS
TPP internal standard; SUR * 1,3-dimethyl-3-nitrobenzene
surrogate standard.
(c) Compound shows aqueous instability.
23
-------
TABLE 2. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 1) AND EDLs (a
Spiking
Level ,
Analyte pg/L
Alachlor
Ametryn
Atraton
Atrazine
Bromacil
Butachlor
Butyl ate
Carboxin
Chlorpropham
Cycloate
Oemeton-S
Oiazinon
Dichlorvos
Diphenamid
Disulfoton
Disulfoton sulfone (h)
Disulfoton sulfoxide
EPTC
Ethoprop
Fenamiphos
Fenarimol
Fluridone
Hexazinone
Merphos
Methyl paraoxon
Metolachlor
Metribuzin
Mevinphos
MGK 264
Hoi inate
Napropamide
Norflurazon
Pebulate
Prometon
Prometryn
Pronamide
Propazine
Simazine
Simetryn
0.38
2.0
0.60
0.13
2.5
0.38
0.15
0.60
0.50
0.25
0.25
0.25
2.5
0.60
0.30
3.8
0.38
0.25
0.19
1.0
0.38
3.8
0.76'
0.25
2.5
0.75
0.15
5.0
0.50
0.15
0.25
0.50
0.13
0.30
0.19
0.76
0.13
0.075
0.25
Amt in
Blank,
pg/L n(b)
NO (g)
NO
NO
NO
0.. 00 182
NO
NO
NO
0.0842
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
O.OS85
NO
NO
NO
NO
NO
NO
NO
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
7
7
8
8
8
8
7
8
8
8
8
8
8
8
8
8
8
8
7
8
8
8
8
8
.
R(c)
119*
100
120
101
113
99
93
101
124
101
90
94
78
84
100
94
110
87
108
91
92
78
127
101
100
94
114
92
101
117
97-
86
84
48
88
123
93
99
97
S(d) RSO(e)
0.0468
0.0678
0.0580
0.00505
0.229
0.0407
0.0178
0.0584
0.0669
0.00725
0.0129
0.0433
0.0933
0.0273
0.00955
0.202
0.0261
0.0266
0.00699
0.0386
0.0681
0.882
0.0508
0.0135
0.101
0.0619
0.00964
0.291
0.0628
0.0202
0.0230
0.0326
0.00719
0.0129
0.00801
0.0934
0.00455
0.00467
0.0118
10
3
8
4
8
11
13
10
11
3
6
18
5
5
3
6
6
12
3
4
19
30
5
5
4
9
6
6
12
12
9
8
7
9
5
10
4
6
5
~
EDL(f)
^^^^^^™^™»^—
0.38
2.0
0.60
0.13
2.5
0.38
0.15
0.50
0.50
0.25
0.25
0.25
2.5
0.50
0.30
3.8
0.38
0.25
0.19
l.C
0.38
3.8
0.75
0.25
2.5
0.75
0.15
5.0
0.50
0.15
0.25
0.50
0.13
0.30
0.19
0.76
0.13
0.075
0.25
24
3\
-------
TABLE 2. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 1)
AND EDLs (a) (continued)
Analyte
Stirofos
Tebuthiuron
Terbacil
Terbufos
Terbutryn
Triademefon
Tricyclazole
Vernolate
Spiking
Level ,
M/l
0.76
1.3
4.5
0.50
0.25
0.65
1.0
0.13
Amt in
Blank,
P9/L
0.0132
NO
NO
NO
NO
NO
NO
NO
n(b)
8
•8
8
8
8
8
8
8
R(c)
»
121
101
100
91
91
95
216
100
S(d)
0.0604
0.193
0.186
0.0190
0.0102
0.0311
0.0716
0.0184
RSO(e)
7
15
4
4
4
5
3
14
EDL(
• — .
0.7
1.3
4.5
0.5
0.2
O.c
l.C
0.1
(a) Data corrected for amount detected in blank; average recovery of 1,3-dimethyl-
2-nitrobenzene surrogate standard from 8 spiked reagent water samples
was 93% (6.3 percent relative standard deviation).
(b) n * number of recovery data points.
(c) R = average percent recovery.
(d) S * standard deviation.
(e) RSD = percent relative standard deviation.
(f) EDI = estimated detection limit in sample ,in ug/L; calculated by multiplying stand.
deviation (S) times the students' t value appropriate for a 99% confidence level ai
standard devi.ation estimate with n-1 degrees of freedom, or a level of compound in
sample yielding a peak in the final extract with signal-to-noise ratio of
approximately 5, whichever value is higher.
(g) NO = interference not detected in blank.
(h) EDL calculated using spiking level 2; analyte was not detected at spiking level 1.
25
32-
-------
TABLE 3. PRIMARY AND CONFIRMATION ANALYSIS CONDITIONS
Relative or Absolute Retention Time
Analyte
» t
Alachlor
Ametryn
Atraton
Atrazine
Bromacil
Butachlor
Butyl ate
Carboxin
Chlorpropham
Cycloate
Oemeton-S
Diazinon
Dichlorvos
1,3 -Dimethyl -2-nitrobenzene
Oiphenamid
Oisulfoton
Oisulfoton sulfone
Disulfoton sulfoxide
EPIC
Ethoprop
Fenamiphos
Fenarimol
Fluridone
Hexazinone
Herphos (f)
Methyl paraoxon
Hetolachlor
Metribuzin
Mevinphos
MGK 264 (g)
Molinate
Napropamide •
Norflurazon
Pebulate
Prometon
Prometryn
Pronamide
Primary (a,d)
0.765
0.766
0:665
0.676
0.792
0.882
0.478
0.910
0.619
0.608
0.663
0.707
0.352
(SUR) 0.308
0.827
0.711
0.879
0.406
0.427
0.608
0.889
1.092
1.206
0.991
0.901
0.757
0.803
0.749
0.479
0.824
0.546
0.890
0.977
0.498
0.672
0.769
0.697
Confirmation (b,e)
34.10
34.52
29.97
31.23
40.00
39.00
18.47
42.05
(c)
29.67
(c)
(c)
•15.35
(c)
37.97
30.90
42.42
(c)
16.57
26.42
41.00
50.02
59.07
47.80
39.28
34.10
35.70
34.73
21.92
36.73
22.47
(c)
47.58
19.73
30.00
34.23.
32.63
26
33
-------
TABLE 3. PRIMARY AND CONFIRMATION ANALYSIS CONDITIONS (continued)
Analyte
Relative or Absolute Retention Time
Primary (a,d)Confirmation (b,e)
Propazine
Simazine
Simetryn
Stirofos
Tebuthiuron
Terbacil
Terbufos
Terbutryn
Triademefon
Tricyclazole
Vernolate
0.681
0.670
0.760
0.878
0.535
0.719
0.693
0.783
0.811
0.899
0.488
31.13
31.32
34.55
39.65
42.77
(c)
(c)
34.80
37.00
44.33
19.25
(a) Retention time relative to TPP internal standard (IS2) which elutes
at approximately 47 min.
(b) Absolute retention time in minutes.
(c) Data not available.
(d) Primary conditions:
Column: 30 m long x 0.25 mm I.D. DB-5 bonded fused silica
column, 0.25 urn film thickness (J&W).
2 ul splitless with 45 second delay
He (? 30 cm/sec linear velocity
250'C
300'C
Program from 60*C to 300*C at 4'C/min
NPO
(e) Confirmation conditions:
Column: 30 m long x 0.25 mm I.D. 08-1701 bonded fused silica
column, 0.25 urn film thickness (JiW).
2 ul splitless with 45 second delay
He 0 30 cm/sec linear velocity
250'C
300'C
Program from 60*C to 300*C at 4'C/min
W^ te^WfeW* * Pi I W
(f) Herphos is converted to S,S,S-tributyl phosphorotrithioate (OEF) in
the hot GC injection port; OEF is actually detected using these
analyses conditions.
(g) HGK 264 gives two peaks; peak identified in this table used for
quantification.
Injection volume:
Carrier gas:
Injector temp:
Detector temp:
Oven temp:
Detector:
Injection volume:
Carrier gas:
Injector temp:
Detector temp:
Oven temp:
Detector:
27
-------
TABLE 4. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 2) (a)
Spiking Amt in
Level, Blank,
Analyte ug/i ug/i
Alachlor
Ametryn
Atraton
Atrazine
Bromacil
Butachlor
Butyl ate
Carboxin
Chlorpropham
Cycloate
Demeton-S
Diazinon
Dichlorvos
Diphenamid
Disulfoton
Disulfoton sulfone
Disulfoton sulfoxide
EPTC
Ethoprop
Fenamiphos
Fenarimol
Fluridone •
Kexazinone
Herphos
Methyl paraoxon
Metolachlor
Hetribuzin
Mevinphos
HGK 264
Holinate
Napropamide
Norflurazon
Pebulate
Prometon
Prometryn
Pronamide
Propazine
Simazine
Simetryn
1.9
10
3.0
0.63
13
3.8
0.76
6.0
2.5
1.3
2.5
2.5
13
3.0
1.5
3.8
1.9
1.3
1.0
5.0
1.9
19
. 3.8
1.3
13
7.5
1.5
25
5.0
0.76
1.3
5.0
0.63
1.5
1.0
3.8
0.63
0.38
1.3
NO (f)
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
HO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
n(b)
7
7
7
8
7
8
7
8
7
6
8
8
7
8
7
7
7
7
7
7
7
7
7
8
8
8
8
7
8
7
7
8
7
7
7
7
8
7
7
R(c)
*95
44
85
93
86
96
92
102
96
80
114
115
87
93
85
94
110
83
94
88
97
107
90
91
99
93
101
93
100
99
94
94
81
63
90
87
100
89
89
S(d) RSO(e)
0.118
1.16
0.158
0.0305
0.494
0.149
0.112
0.274
0.178
0.114
0.141
0.183
0.866
0.156
0.155
0.202
0.230
0.104
0.0798
0.610
0.0956
1.132
0.0968
0.0647
1.33
0.287
0.0703
3.20
0.220
0.0622
0.0569
0.232
0.0398
0.158
0.0441
0.203
0.0492
0.0221
0.0676
6
13
6
5
5
4
16
4
7
11
5
6
8
6
12
6
11
10
8
14
5
6
3
5
10
4
5
14
4
8
5
5
8
17
5
6
8
6
6
28
-------
TABLE 4. RECOVERY OF ANAIYTES FROM REAGENT WATER (SPIKING LEVEL 2) (a)
(continued)
Analyte
Spiking Amt in
Level, Blank,
pg/L pg/L n(b) R(c) S(d) RSD(e)
Stirofos 3.8 NO 7 82 0.146 5
Tebuthiuron 6.3 NO . 7 111 0.705 10
Terbacil 23 NO 7 88 1.89 9
Terbufos 2.5 NO 8 97 0.179 4
Terbutryn 1.3 NO .7 93 0.0530 4
Triademefon 3.3 NO 8 93 0.180 6
Tricyclazole 5.0 NO 7 83 0.157 4
Vernolate 1.3 NO 8 93 0.0702 6
(a) Data corrected for amount detected in blank.
(b) n = number of recovery data points.
(c) R = average percent recovery.
(d) S = standard deviation.
(e) RSD - percent relative standard deviation.
(f) NO = interference not detected in blank.
29
-------
TABLE 5. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 3)
Spiking Amt in
Level, Blank,
Analyte pg/L pg/L n(b)
Alachlor
Ametryn
Atraton
Atrazine
Bromacil
Butachlor
Butyl ate
Carboxin
Chlorpropham
Cycloate
Demeton-S
Diazinon
Oichlorvos
Diphenamid
Disulfoton
Disulfoton sulfone
Disulfoton sulfoxide
EPIC
Ethoprop
Fenamiphos
Fenarimol
Fluridone
Hexazinone
Merphos
Methyl paraoxon
Metolachlor
Metribuzin
Mevinphos
MGK 264
Molinate
Napropamide
Norflurazon
Pebulate
Prometon
Prometryn
Pronamide
Propazine
Simazine
3.8
20
6.0
1.3
25
3.8
1.5
6.0
5.0
2.5
2.5
2.5
25
6.0
3.0
7.5
3.8
2.5
1.9
10
3.8
38
7-. 6
2.5
25
7.5
1.5
50
5.0
1.5
2.5
5.0
1.3
3.0
1.9
7.6
1.3
0.75
NO (f)
ND
ND
NO
NO
NO
NO
NO
NO
NO
ND
NO
NO
NO
NO
NO
NO
ND
NO
NO
NO
ND
NO
NO
NO
NO
NO
NO
NO
NO
ND
ND
ND
NO
NO
NO
NO
NO
8
8
• 8
8
8
8
6
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
R(c)
95
91
91
92
91
96
97
102
93
89
114
115
97
93
89
98
87
85
103
90
99
87
90
96
98
93
101
95
100
98
101
94
94
78
93
91
92
100
S(d) RSO(e)
0.390
1.91
0.640
0.103
2.26
0.149
0.321
0.274
0.554
0.234
0.141
0.183
1.39
0.501
0.287
0.722
0.441
0.230
0.0889
0.840
0.185
3.28
0.532
0.201
2.47
0.287
0.0703
5.04
0.220
0.259
0.143
0.232
0.104
0.267
0.165
0.776
0.103
0.0508
11
11
12
9
10
4
22
4
12
10
5
6
6
9
11
10
13
11
5
9
5
10
8
8
10
4
5
11
4
18
6
5
9
11
9
11
9
7
30
J7
-------
TABLE 5. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL
(continued)
Analyte
Spiking Amt in
Level, Blank,
pg/L M9A
n(b)
R(c)
S(d)
RSO(e)
Simetryn
Stirofos
Tebuthiuron
Terbacil
Terbufos
Terbutryn
Triademefon
Tricyclazole
Vernolate
2.5
7.6
13
45
5.0
2.5
6.5
10
1.3
NO
NO
NO
NO
NO
NO
NO
NO
NO
8
8
8
8
8
8
8
8
8
99
98
84
97
97
94
93
86
93
0.131
0.459
,15
.41
,179
0.214
0.539
0.675
0.0673
1.
2.
0.
5
6
11
6
4
9
9
8
6
(a) Data corrected for amount detected in blank.
(b) n = number of recovery data points.
(c) R = average percent recovery.
(d) S = standard deviation.
(e) RSD = percent relative standard deviation.
(f) NO = interference not detected in blank.
31
3*
-------
TABLE 6. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 4)
Spiking
Level ,
Analyte \ig/l
Alachlor
Ametryn
Atraton
Atrazine
Bromacil
Butachlor
Butyl ate
Carboxin
Chlorpropham
Cycloate
Demeton-S
Diazlnon
Dichlorvos
Diphenamid
Disulfoton
Disulfoton sulfone
Disulfoton sulfoxide
EPTC
Ethoprop
Fenamiphos
Fenarimol
Fluridone
Hexazinone
Merphos
Methyl paraoxon
Metolachlor
Metribuzin
Mevinphos
MGK 264
Molinate
Napropamide
Norflurazon
Pebulate
Prometon
Prometryn
Pronamide
Propazine
Simazine
9.4
50
15
3.1
63
9.4
3.8
15
13
6.3
6.3
6.3
63
15
7.5
19
9.4
6.3
4.S
25
9.4
94
19
6.3
63
19
3.8
125
13
3.8
6.3
13
3.1
7.5
4.8
19
3.1
1.9
Amt in
Blank,
pg/l
NO (f)
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
NO
NO
NO
NO
0.582
NO
NO
NO
n(b)
8
8
8
7
8
7
8
7
8
8
7
7
8
7
8
7
8
7
7
8
8
7
8
7
7
7
7
8
7
8
8
7
8
8
7
8
7
8
R(c)
*95
104
94
96
94
96
62
89
92
104
96
97
92
93
105
91
104
90
88
102
84
88
96
95
90
98
97
99
95
101
84
85
86
102
129
96
92
86
S(d) RSO(e)
0.531
5.69
0.727
0 158
W • A «^W
3 00
•J • W w
0 261
W • C V A
0 341
v * w ~ A
0.598
0.668
0 724
W * / w •
0.394
0.350
5.31'
0.607
0.879
0.669
1.48
0 414
w • ™ A *
0 457
\J • ~ w »
2 60
b • W W
1 ng
i • V J
8.47
1 22
4 • fc fc
0.350
2 93
b • irf vrf
1.28
0.259
12.0
0.275
0.478
0.479
0.772
0.288
0.815
0.277
1.12
0.194
0.115
6
11
i 1
5
W
c
3
C
3
•5
J
1 C
i J
4
6
1 1
i i
7
c.
o
9
J
4
i i
j i
4
15
7
/
1 1
i i
10
4 W
10
1 w
7
6
5
W
7
7
10
2
^
12
9
j
7
11
11
4
6
7
7
32
31
-------
TABLE 6. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 4}
(continued)
Analyte
Spiking Amt in
Level, Blank,
ug/L ug/L
n(b)
R(c)
S(d) RSD(e)
Simetryn 6.3 NO
Stirofos 19 NO
Tebuthiuron 31 NO
Terbacil 113 NO
Terbufos 13 NO
Terbutryn 6.3 NO
Triademefon 16 NO
Tricyclazole 25 NO
Vernolate 3.1 NO
(a) Data corrected for amount detected i
(b) n - number of recovery data points.
(c) R « average percent recovery.
(d) S = standard deviation.
(e) RSD - percent relative standard devi
(f) NO * interference not detected in bl
8
'•8
8
8
7
7
7
8
7
n blank.
ation.
ank.
84
91
82
82
94
91
92
92
83
0.435
1.12
1.34
11.8
0.544
0.221
0.595
1.61
0.124
8
7
• 5
13
4
4
4
7
5
33
-------
TABLE 7. RECOVERY Of ANALYTES FROM REAGENT WATER (SPIKING LEVEL 5)
Spiking Amt in
Level , Blank,
Analyte ' ug/L ug/L
Alachlor
Ametryn
Atraton
Atrazine
Bromacil
Butachlor
Butyl ate
Carboxin
Chlorpropham
Cycloate
Oemeton-S
Oiazinon
Dichlorvos
Oiphenamid
Disulfoton
Oisulfoton sulfone
Oisulfoton sulfoxide
EPTC
Ethoprop
Fenamiphos
Fenarimol
Fluridone
Hexazinone
Merphos
Methyl paraoxon
Metolachlor
Metribuzin
Mevinphos
MGK 264
Molinate
Napropamide
Norflurazon
Pebulate
Prometon
Prometryn
Pr on amide
Propazine
Simazine
38
200
60
13
250
38
15
60
50
25
25
25
250
60
30
75
38
25
19
100
38
375
• 76
25
250
75
15
500
50
15
25
50
13
30
19
76
16
8
NO (f)
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
NO
NO
NO
NO
NO
NO
NO
NO
n(b)
8
8
• 8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
R(c)
. 94
98
90
93
93
90
78
96
93
100
86
88
96
94
99
88
84
88
93
98
104
98
93
101
92
92
91
89
90
87
102
101
88
85
94
93
73
101
S(d) RSO(e)
2.35
5.81
3.76
0.548
16.5
2.25
1.01
5.38
3.21
0.725
1.51
2.07
14.5
2.01
0.851
2.09
3.02
1.46
0.973
2.72
3.18
28.8
3.52
1.00
10.0
4.44
0.885
17.9
3.76
0.912
2.39
3.75
1.04
1.68
0.710
4.70
0.604
0.594
7
3
7
5
7
7
9
9
7
3
7
9
6
4
3
3
9
7
5
3
8
8
5
4
4
6
7
4
8
7
9
7
9
7
4
7
5
8
34
-------
TABLE 7. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 5)
(continued)
Analyte
Spiking
Level,
Amt in
Blank,
n(b) R(c)
(a) Data corrected for amount detected in blank.
(b) n - number of recovery data points.
(c) R - average percent recovery.
(d) S * standard deviation.
(e) RSD - percent relative standard deviation.
(f) NO - interference not detected in blank.
S(d) RSO(e)
Simetryn
Stirofos
Tebuthiuron
Terbacil
Terbufos
Terbutryn
Triademefon
Tricyclazole
Vernolate
25
76
125
450
50
25
65
100
13
NO
NO
NO
NO
NO
NO
NO
NO
NO
8
8
• 8
8
8
8
8
8
8
M03
97
87
101
93
93
98
89
88
1.99
6.64
10.5
34.7
3.79
0.909
2.41
4.18
0.797
8
9
10
8
8
4
4
5
7
35
-------
TABLE 8. RECOVERY OF ANALYTES FROM HARD ARTIFICIAL GROUND WATER
(SPIKING LEVEL 3) (a)
Spiking Amt in
Level, Blank,
Analyte M9/L M9A
Alachlor
Ametryn
Atraton
Atrazine
Bromacil
Butachlor
Butyl ate
Carboxin
Chlorpropham
Cycloate
Oemeton-S
Oiazinon
Dichlorvos
Oiphenamid
Oisulfoton
Disulfoton sulfone
Oisulfoton sulfoxide
EPIC
Ethoprop
Fenamiphos
Fenarimol
Fluridone
Hexazinone
Merphos
Methyl paraoxon
Metolachlor
Metribuzin
Mevinphos
MGK 264
Molinate
Napropamide
Norflurazon
Pebulate
Prometon
Prometryn
Pronamide
Propazine
Simazine
Simetryn
Stirofos
3.8
20
6.0
1.3
25
3.8
1.5
6.0
5.0
2.5
2.5
2.5
25
6.0
3.0
7.5
3.8
2.5
1.9
10
3.8
38
7.6
2.5
25
7.5
1.5
50
5.0
l.S
2.5
5.0
1.3
3.0
1.9
7.6
1.3
0.75
2.5
7.6
NO (f)
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
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
n(b)
7
7
7
8
7
8
7
8
7
7
8
8
8
8
7
8
7
8
8
7
8
8
7
8
8
8
8
7
8
7
8
8
8
7
8
7
8
8
8
7
R(c)
82
102
84
89
81
93
36
98
82
97
81
83
86
88
107
92
88
83
91
87
89
91
86
90
97
92
99
93
91
83
89
101
80
89
91
84
89
86
88
84
S(d) RSO(e)
0.214
2.30
0.382
0.0787
1.29
0.551
0.115
0.771
0.353
0.345
0.151
0.210
1.57
0.279
0.352
0.324
0.835
0.132
0.134
0.509
0.244
4.10
0.436
0.0972
1.87
0.765
0.142
2.76
0.555
0.116
0.126
0.781
0.0774
0.154
0.149
0.502
0.0787
0.0393
0.119
0.469
7
11
8
7
6
16
21
13
9
14
7
10
7
5
11
5
25
6
8
6
7
12
7
4
8
11
10
6
12
9
6
15
7
6
9
8
7
6
5
7
36
-------
TABLE 8. RECOVERY OF ANALYTES FROM HARD ARTIFICIAL GROUND WATER
(SPIKING LEVEL 3) (a) (continued)
Spiking Amt in
Level, Blank,
Analyte ug/L ug/L n(b) R(c) S(d) RSO(e)
Tebuthiuron
Terbacil
Terbufos
Terbutryn
Triaderoefon
Tricyclazole
Vernolate
13
45
5.0
2.5
6.5
10
1.3
NO
NO
NO
NO
NO
NO
NO
8
•8
8
8
8
7
8
'85
86
80
91
94
90
79
1.28
2.20
0.301
0.197
0.301
0.586
0.108
12
6
8
9
5
7
11
(a) Corrected for amount found in blank; artificial ground water was
Absopure Nature Artesian Spring Water Obtained from the Absopure Water
Company in Plymouth, Michigan.
(b) n - number of data points.
(c) R = average percent recovery.
(d) S = standard deviation.
(e) RSD * percent relative standard deviation.
(f) NO - interference not detected in blank.
37
-------
TABLE 9. RECOVERY OF ANALYTES FROM ORGANIC-CONTAMINATED ARTIFICIAL
GROUND WATER (SPIKING LEVEL 3) (a)
Spiking Amt in
Level, Blank,
Analyte ug/L ug/L
Alachlor
Ametryn
Atraton
Atrazine
Bromacil
Butachlor
Butyl ate
Carboxin
Chlorpropham
Cycloate
Oemeton-S
Diazinon
Dichlorvos
Oiphenamid
Disulfoton
Disulfoton sulfone
Disulfoton sulfoxide
EPTC
Ethoprop
Fenamiphos
Fenarimol •
Fluridone
Hexazinone
Merphos
Methyl paraoxon
Metolachlor
Metribuzin
Mevinphos
MGK 264
Molinate
Napropamide
Norflurazon
Peculate
Prometon
Prometryn
Pronamide
Propazine
Simazine
Simetryn
Stirofos
3.8
20
6.0
1.3
25
3.8
1.5
6.0
5.0
2.5
2.5
2.5
25
6.0
3.0
7.5
3.8
2.5
1.9
10
3.8
38'
7.6
2.5
25
7.5
1.5
50
5.0
l.S
2.5
5.0
1.3
3.0
1.9
7.6
1.3
0.75
2.5
7.6
NO (f)
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
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
n(b)
8
•8
8
7
8
8
8
8
8
8
8
8
8
7
8
7
7
7
7
8
8
8
8
7
7
8
8
8
8
8
8
8
8
8
7
8
7
8
8
8
R(b)
90
96
91
92
88
84
83
87
93
93
83
84
106
93
95
96
54
86
79
89
89
86
95
92
94
84
86
92
83
89
104
87
98
63
93
92
92
103
103
95
s(c) RSO(d)
0.312
0.710
0.486
0.0621
2.09
0.204
0.110
0.292
0.428
0.0815
0.130
0.0813
3.99
0.253
0.135
0.242
0.733
0.105
0.0582
0.247
0.236
3.58
0.665
0.0845
0.973
0.322
0.0627
1.86
0.270
0.131
0.434
0.219
0.197
0.0947
0.0740
0.617
0.0621
0.110
0.354
0.699
9
4
9
5
9
6
9
6
9
3
6
4
15
5
5
3
36
5
4
3
7
11
9
4
4
5
5
4
7
10
17
5
15
3
4
9
5
14
14
10
38
-------
TABLE 9. RECOVERY OF ANALYTES FROM ORGAN 1C-CONTAMINATED ARTIFICIAL
GROUND WATER (SPIKING LEVEL 3) (a) (continued)
Analyte
Spiking Amt in
Level, Blank,
ug/L ugA
n(b)
R(b)
$(c)
RSD(d)
Tebuthiuron 13 NO 8 98 1.64 13
Terbacil 45 NO 3 102 5.35 12
Terbufos 5.0 NO 8 77 0.353 9
Terbutryn 2.5 NO -7 92 0.0971 4
Triademefon 6.5 NO 7 95 0.285 5
Tricyclazole 10 NO 8 90 1.05 12
Vernolate 1.3 ND 8 81 0.0299 3
(a) Corrected for amount found in blank; artificial ground water was reagent
water spiked with fulvic acid at the 1 mg/L concentration level. A
well-characterized fulvic acid, available from the International Humic
Substances Society (associated with the united States Geological Survey
in Denver, Colorado); was used.
(b) n - number of data points.
(c) R - average percent recovery.
(d) S * standard deviation.
(e) RSD - percent relative standard deviation.
(f) NO - interference not detected in blank.
39
-------
a
C£
a
C
o
a*
cr
o
o e
e •>>»
O C7>
«_) 2.
o
C
o
fO
O
o
o.
O
00
o
o
CL. C
O
V —
O)
ro
QJ
-JOS
o o\ •—
QJ • o
•_> O wi
a> OJ
O er
o
o
o
vrt
O IT>
r*> —
O o
O)
-J
«5
»—
O
.— CO
— O C
VI
E E «>
s- o o w
O U t. -J
> CO O. <
u
o
V OI
o. o
C
O «W
^= u
o. o
C
o
=9
O1
o*
O)
3
•o
fO
3
O
1-
O
a*
Ol
— c;
QJ QJ
.— i-> O
ra JZ —
.C en —»
— o
— e
«« 0
u
01
CL
o -a
o
01 •—
— t_
J= O
•O «M «J
— ^ «fl
—.*C^ """c^
rvi o DC C -^
^x.jc— «« —
— «rf -O — •«—
•o" c «/• ac
x «« «« «/»
— 3 X
X —• fO
*n < •
o — o. «w —
—' CI
X -j CL
V)
OI OI
01 en c
"x J= c
OI
at
i-
3
cn
•O
O)
re
01
OI
01
u. 01
CM OI
•*x« 01 c
— <_>
QJ to
«/> QJ
ci a.
— o
o o
._ CI
c
CJ —
o •—
C OI
CI v\
i_ <*_
U_ OJ
X) —•
OI «->
OI
t-^i
01 «o
U= 01
X CL
40
-------
TABLE 11. PRESERVATION STUDY RESULTS
Day Extracted
Day Analyzed
0
0
Amount,
Analyte ug/L • R(b) RD(c)
Alachlor
Ametryn
Atraton
Atrazine
Bromacil
Butachlor
Butyl ate
Carboxin
Chlorpropham
Cycloate
Demeton-S
Diazinon
Dichlorvos
Oiphenamid
Oisulfoton
Disulfoton sulfone
Disulfoton sulfoxide
EPIC
Ethoprop
Fenamiphos
Fenarimol
Fluridone
Hexazinone
Merphos
Methyl paraoxon
Metolachlor
Metribuzin
Mevinphos
MGK 264
Holinate
Napropamide
Norflurazon
Pebulate
Prometon
Prometryn
Pronamide
3.8
20
6.0
1.3
25
3.8
1.5
6.0
5.0
2.5
2.5
2.5
25
6.0
3.0
7.5
3.8
2.5
1.9
10
3.8 '
38
7.6
2.5
25
7.5
1.5
50
5.0
1.5
2.5
5.0
1.3
3.0
1.9
7.6
76
95
76
79
74
75
51
81
76
91
81
79
78
82
98
83
83
80
82
92
82
90
78
82
85
76
79
88
77
76
81
82
76
60
81
71
0.7
1.9
1.1
0.1
4.2
0.3
0.3
0.3
1.0
0.3
0.1
0.2
3.2
0.6
0.2
0.9
0.7
0.3
0.2
0.5
0.1
1.5
1.2
0.3
2.5
0.6
0.1
3.5
0.4
0.3
0.1
0.4
0.1
0.4
0.2
1.5
0
28
R
73
86
82
83
72
72
18
97
73
83
85
76
60
92
83
88
72
85
86
92
54
62
99
87
81
76
79
92
76
76
81
77
60
99
61
59
RSD
2.0
1.1
2.3
0.2
11.8
0.2
1.7
1.6
2.2
0.2
0.1
0.1
2.2
0.6
0.1
1.0
1.4
0.3
0.3
0.6
0.1
0.9
2.7
0.3
3.3
0.2
0.1
1.8
0.1
0.7
0.1
0.1
0.0
0.2
0.3
4.5
14
14
R
84
70
85
86
89
60
85
97
84
86
73
93
93
90
87
97
8
89
92
94
101
94
86
93
93
95
95
86
94
86
85
100
100
21
84
4
RSO
0.2
7.8
0.3
0.1
2.3
1.6
0.1
0.8
0.3
0.2
• 0.5
0.4
1.1
0.3
0.2
0.4
0.9
0.2
0.1
0.7
0.3
2.8
0.4
0.1
1.0
1.1
0.2
4.2
0.8
0.1
0.4
0.8
0.1
0.5
0.1
1.8
28
28
R RSO
65
74
67
80
33
53
66
57
68
82
27
57
41
85
79
83
N0(a;
83
85
82
60
58
71
84
83
61
59
74
58
66
62
63
58
11
48
NO
0.0
1.5
0.1
0.1
0.5
0.4
0.0
0.6
0.0
0.1
0.8
0.3
17.7
0.5
0.2
0.6
0.2
0.1
l.C
2.3
26. <
o.;
o.;
i.:
1.1
0.
2.
0.
0.
1.
0.
0.
1.
0.
41
-------
TABLE 11. PRESERVATION STUDY RESULTS (continued)
Day Extracted
Day Analyzed
Analyte
Propazlne
Simazine
Simetryn
Stirofos
Tebuthiuron
Terbacil
Terbufos
Terbutryn
Triademefon
Tricyclazole
Vernolate
.ed
id
Amount,
yg/i .
1.3
0.75
2.5
7.6
i 13
45
5.0
2.5
i 6.5
e 10
1.3
0
0
R(a)
80
81
81
78
91
74
72
82
84
72
70
RSO(b)
0.1
0..0
0.1
1.3
0.2
3.1
0.2
0.3
0.7
1.5
0.1
0
28
14
14
28
28
RSD
RSD
RSD
86
60
81
91
58
59
77
84
82
92
72
0.1
0.0
0.0
4.9
3.4
0.7
0.5
0.3
0.6
2.5
0.1
99
99
100
83
101
99
ND
90
100
99
91
0.1
0.0
0.1
0.4
0.7
2.3
.
0.2
0.4
1.6
0.2
86
62
60
61
54
60
ND
85
83
68
57
0.
0.
1
.8
0.2
9.2
31.8
0.2
0.
0.
0.2
(a) ND •= not detected.
(b) R - average percent recovery.
(c) RSD = percent relative standard deviation.
-------
o
13
0
ui
in
ddi
CB
in
o
C£
O
SOJOUOJ
"»
H"» '«••« J i i ri pp-r-r-r | 1-1 -i i r i i r < y
• i i
CO
o-
u_
O
o
*—
-------
a
to
s
in
c
o
2IV
I SI
Utf
s
in
s
in
O)
•o
<-i
_j
UJ
e £
in
cv
s
CD
-------
z uj
— _i
« •
J " Q t3
5 * - z
1 " ^ -
' »— a.
z —
1 °
J — »» ^
5 H-
1 " ° £ -
. ° « 0
z
a.
-° *
I
<_)
o
r*>
UJ
ce
*r ^
45
-------
o
to
in
in
c
o
Z SI
B
in
OJ
•o
a>
TTT
CS
S
QJ
QJ
O
on
E ^
I— Q.
in
rv
CS O
z
&£
CL.
o
o
O
oe
ar
<_>
o
o.
z
•
o
i ai
I SI
T-I r-r-i
46
-------
o
1C
in
in
o
•o
a
in
SI
eia
ZtO
IIQ
TJ
OJ
ex
s-
o
flj
!Z
in
010
Q
es
60
80
3 -
90
SO
a
ui
a
a
frO
= *
~ c.
z —•
2 c
z **
ii z
e °
^
c.
eo
in
CJ
o
o
zo
O
ce
to
QC
O
t si
-rrii
47
-------
GS
o
c
o
s
in
CJ
•o
£13
G3
in
U3
Z SI
013
;n
O
.a
ro
O
O
63
z ans
s
63
83
o
z:
i£
c.
z
o
^£
o.
s
CM
Z3
(S
fv'
c
a
z
c
13
a
in
C
J
V
I «ns
i si
-------
18
. s
• st
• R
1 Si
' R
; rf
ce
o
>- u-
«^> O
Q.
uj ce
o. o
*—
UJ <_)
O <
»— O
o
fr-
ee
49
-------
Append;* C
Revision No 4
Date December 1989
Page 1 of 12
APPENDIX C
DATA FLOW (REDUCTION, VALIDATION, AND REPORTING)
-------
CFUEE FEPFESENBHTCN OF Dftl& FLOW
1. Samples are taken in the field.
2. Samples are iced and shipped to the laboratory.
3. Laboratory prepares and analyzes field sanples along with QC samples.
4. laboratory enters field and QC data on a conpiter in "sets" and it
enters instrument control standard data in^a separate file.
5. Laboratory creates an ASCII file of the data using the specified formats
on an HM PC cccpatible floppy disk.
6. laboratory sends the floppy disk to Christopher Frebis at the EPA in
Cincinnati, Ohio.
26 W. Martin Lather King Drive
Cincinnati, CH 45268
NOTE: The maximum time from item 1 to item 6 is two (2) months.
7. Conputer Sciences Corporation (CSC) personnel transfer the data from PC
to IEM 3090 mainframe in North Carolina (or possibly to IH1 Logical
Mainframe in Cincinnati).
8. The data is edited on the mainframe and then checked for compliance
with QC requirements using SAS, a statistical pioytdinning language.
9. A hard copy of the edjtpd data, with "suspect" data highlighted, is
sent to the technical monitor for their review.
10. The technical monitor returns the data to C. Frebis with comments,
deletions, etc. — this is the final data.
11. The data is re-edited per the technical monitor's review and a SAS data
set is created for the data.
12. The "approved" field samples are sent to ICF for their analyses.
13. All QC data is retained by C. Frebis to generate a QC report at the end
of the survey and to write monthly reports to Dave Munch.
-------
NOTES ON NFS DATA FC5RMAIS
1. "Die format for any date is mm/dd/yy
A missing date should be entered 01/01/60
2. The format for any tine is hh:mm in military time
A missing time' should be entered 00:00 ,~
3. Any other data that is missing should be entered with a period (.)
4. The number of Avrmai places should be as follows:
Concentration 3 (significant digits)
Percent Recovery 1
Internal Standard 0
Instrument Controls 2
PH 1
Temperatures 0
Volumes 0
5. The codes for Column are as follows:
Primary PRIM
Confirmatory CONF
Third GOMS
6. The codes for Lab are as follows:
TSD . TSD
OPP OPP
WERL WEK
Radian RAD
Battelle BCD
Janes M. Montgomery JMM
Alliance ALL
Environmental Sciences and Engineering ESE
7. The codes for Type are as follows:
Field Sample SAMP
Shipping Blank SBLK
Method Blank MBIK
Lab Control Standard LCS6
Lab Spike Sample LSS@*
Tine Storage for Extract HIES
Tine Storage for Sample HTS@
where @ is the mix letter (A,B,C or D)
and I is the spiking level (1,2 or 3)
-------
NOTES CN NFS DATA. FORMATS (oont.)
8. There should be at least one blank line between samples in the NFS data
file.
9. "Die codes for Concentrations and Percent Recoveries are as follows:
Not Analyzed
Not Detected (< Minimum Reporting Level) ^ -999
Saturated -777
Other -333
Below Report Limit, but Distinct Peak -111
Above Reporting Limit, but not Quantified f 888
10. If a reported value is greater than (>) some number in the NFS instrument
control data, then use a minus sign (-) instead of >
-------
REVISIONS TO FORMAT FOR NFS DATA FILES
- Format for National Pesticide Survey (NPS) Data
V
Line Column Revision
11 ' 52-62 i Revised "Enter Internal Standard" to "PERCENT
RECOVERY OF INTERNAL STANDARD AS COMPARED
AGAINST THE CALIBRATION STANDARD".
- Notes on NPS Format
4) Revised "Internal Standard 0 (area count)" to
Internal Standard 1 (percent recovery)
9) - 999 - revised to denote "Not Detected (< 1/2 MRL)"
- Ill - revised to denote "> 1/2 MRL but < MRL"
-------
TABLE 1: USES OF DATA. CODES IN NFS
SAMPLE TYPE
SAMP
(a)
-iii(c)
.333 ;dj
-444 (e)
-SSSW
-666(9)
-777 W
888 W
-999 (j)
concM
MBLK
.(a)
-m(c)
-333 W
****
-555 <*>
-777 ft)
888 (Jj
-9999)
concW
SBLK
'(a)c
-Sw
-444 (e)
-555 (f)
-666<9)
888 (J)
-999(3)
concW
LCS
.(b)
****
>***
****
****
****
-777^)
. ****
****
% recW
LSS,DTS
HIE, HIS
.(b)
****
-333 [d)
-444 (e)
****
****
-777 W
****
****
% rec(1)
(a) Analyte OiLKjed fron survey (Deanetcn-S and Carboxin sulfoxide) or not
analyzed on the second column or in GOB analysis.
(b) Analyte not in mix.
(c) Analyte 's concentration between URL/2 and MRL. (If no confirmation is run,
a counent as to why should be made. )
(d) A lab m-jghap, e.g. sample lost during extraction, or sample dropped, or
a QC failure which causes the entire sample to be lost and no data
reported. This is a unique situation. (A eminent should give further
explanation. )
(e) This analyte fails QC in this set (e.g. LCS out of control) and therefore
cannot be reported; however, the analyte does not require a qualitative
challenge. This code also applies to any spiXe sample in a set where
the LCS is out of control.
(f) GCMS only: Sent to referee lab for GCMS analysis.
(g) T»Hg analyte fails QC in this set (e.g. positive method blank) and
therefore cannot be reported; however, the analyte does require a
qualitative challenge.
(h) Analyte was saturated. Should be diluted and re-done, if observed in a
field sample. (Another sample with the exact same header information
should appear, analytes not saturated in the original sample should be
reported as . , and saturated analytes should be reported as their
ntzation. )
(i) Positive, can occur in two fashions: 1) any analyte in GCMS analysis; or
2) a qualitative only analyte on either of the first two columns.
(j) Analyte 's concentration below MKL/2.
Qc) Concentration above MRL for quantitative analytes, reported to three
significant figures.
(1) Percent recovery, reported to one ffc*^™*T place (even if recovery is 0.0%)
**** o?dg not
-------
-333
IJAIA K-truKi^iNu L.out.i <,cont.;
(Oualita£J.ve onlv analvte)
-999 888
-333 -999
888
PRIM
CCNF
-333 -555 -999 888 GQ-B
GCMS
(at referee)
Sarnnle (Quantitative analvte with OC failure)
-333
-444
-666
-333 -666 -999
-333 -555 • -999 888
-333 -999 888
PRIM
OCNF
oais
(at referee)
"''v
with no
-111
-333
-777s -999
cone
-111 -333 -999 core
PRIM
CONF
-333 -555 -999 888 -333 -555 -999 888 -333 -555 -999 888 -333 -555 -999 888 GCMS
-111 -333 -999 care
/T\
-333 -999 888 -333 -999 888 -333 -999 888 -333 -999 888 GCMS
(at referee)
a « Dilute and reanalyze
-------
DftIA CHECKS PERFORMED ON NPS DftIA Etf CSC
1. Is the instrument control standards 's signal to noise ratio greater than
the limit the method specifies?
2. Is the instrument control standard's peak syntnetry factor within the
limits set by the method?
3. Is the instrument control standard's peak geometry factor within the
limits set by the methods?
4. Is the instrument control standard's resolution within the limits set by
the method?
5. Is the date from sampling to receipt within the limits set by the survey
6. Is the date from sampling to extract within the limits set by the survey
7. Is the date from extract to analysis within the limits set by the survey
requirements?
8. Is the percent recovery of the surrogate within the limits set by the
survey requirements?
9. Is the concentration of a blank above the reporting limit?
10. Is the concentration of a field sample above the reporting limit?
A. If so, is there a confirmation analysis for the analyte?
B. Is the concentration of the confirmatory column within the limits
set by survey requirements?
11. Is the internal standard within the limits sex. by the method requirements?
12. Is the percent recovery of each analyte in the lab control standard within
the limits set by the survey requirements?
13. Is the percent recovery of each analyte in the lab. spike sample within
the limits set by the survey requirements?
-------
FOFMAT FOR NATIONAL PESTICIDE SURVEY (NPS) DATA
COLUMNS
I PI'ION
3
4
6
7
1-9 Well I.D.
13-20 Date_Sam
23-30 Date_Shp
33-40 Datejtec
43-50 Tiffle_Sam
53-60 Time.Ioe
[PDR METHODS 5 AND 9 ONLY]
64-65 pH
1-10 enter WELL IDEOTEFTCftTION NUMBER
13-20 enter DATE SAMPLED
23-30 enter DATE SHIPPED
33-40 enter DATE RECEIVED
43-50 enter TIME SAMPLED
53-60 enter TIME ICED
[FOR MEfflODS 5 AND 9 ONLY]
63-66 enter pH
BLANK
1-8
11-18
21-29
1-8
11-18
21-80
BLANK
1-6
9-11
14-18
21-28
31-38
41-48
51-56
59-64
1-6
9-11
14-18
21-28
31-38
41-48
51-56
59-64
Ini_Tenp
Stb_Tenp
Condition
enter INITIAL TEMPERATURE OF WATER
enter STABILIZED TEMPERATURE OF WATER
enter CONDITION OF SAMPLE UPON RECEIPT AT lABORATORY
Sanp f
Set #
Date Spk
Date.Ext
Date Ana
Site I
Column
enter SAMPLE IDENTIFICATION NUMBER
enter LAB ABBREVIATION
enter SET NUMBER
enter DATE SPIKED
enter DATE EXTRACTED
enter DATE ANALYZED
enter SITE NUMBER
enter ANALYSIS COLUMN
-------
PC534AT FOR NATIONAL ViSTlClDE SURVEY (NFS) DMCA (cant.)
UNE COLUMNS
9 BLANK
10
n
12
13
14
15
16
17-?
1-4
8-13
16-22
25-31
34-40
43-49
52-60
65-70
1-5
8-13
16-22
25-31
34-40
43-49
52-62
65-70
BLANK
1-8
1-80
BLANK
1-7
29-33
39-45
67-71
1-25
28-34
39-63
66-72
DESCRIPTION
Type
Splicer
Extract
Analyst
Ext Vol
Int. Std.
% Surr
enter SAMPLE TYPE
enter SFIKER'S INITIALS
enter EXTRACTOR'S INITIALS
enter ANALYST'S INITIALS
enter VOLUME OF SAMPLE
enter VOLUME OF EXTRACT
enter INTERNAL STANDARD
enter PERCENT RECOVERY OF SURROGATE
OoDEosnts
enter ANY PERTINENT COMMENTS ON SAMPLE AND ANALYSIS
Analyte
Cone.
Analyte
Cone.
enter ANALYTE'S NAME
enter CONCENTRATION OR PERCENT RECOVERY
enter ANALYTE'S NAME
enter CONCENTRATION OR PERCENT RECOVERY
-------
PQEMftT R31 NATIONAL HiTlClLE SURVEY (NFS) INSTRUMENT CONTROL DATA
T.THF. COLUMNS DESCRIPTION
1 1-3 lab
6-11 Method
14-21 Date Ana
24-30 Analyst
35-37 S/N •
42-44 PSF
49-51 PGF
55-58 Res.
2 BLANK
3-? 1-3 enter LAB ABBREVIATION
6-11 enter METHOD NUMBER
14-21 enter DATE ANALYZED
24-30 enter ANALYST'S INITIALS
33-37 enter SIGNAL TO NOISE KATIO
40-44 enter PEAK SYMMETRY FACTOR
47-51 enter PEAK GEOMETRY FACTOR
54-58 enter RESOLUTION
(,7
-------
«*** TSO FOREGROUND HARDCOPY ****
OSNAME=CPSFSOD.NPS.FORMAT.OATA
(HETH001
I Taap S_T«ap Oata.Saa Oate.Shp Data.Rac Ti««_Saa Tia«.Ic«
01/01/60 01/01/60 01/01/60
•caipt Condition
Sa«p *
Lab
TSD
Sat 9 Data.Spk Data.Ext Dat«_-Ana Column
01 . 01/01/60 04/30/87 05/03/87 PRIM
Typa Spikar Extract Analyst Saa.Vol Ext.Vol Int. Std. X Surr
HBLK . CM CM 1000 5 35 101.3
Coaaants
NONE.
Analyta
Alachor
Aa«tryn
Atraton
Atrazino
Broaacil
Butachlor
Butylat*
Carboxin
Chlorpropham
Cycloat*
0«a«ton-S
Oiarinon
Oichlorvos
Oiph«naaid
Disulf oton
Oisulfoton sulfone
Disulfoton sulfoxidt
EPIC
Ethoprop
F*naaiphos
Fluridon*
Haxazinone
Norphos
Cone. Analyta
-999 M«thyl paraoxon
-999 Hatolachlor
-999 Metribuzin
-999 Mevinohos
-999 MGK 264
-999 Holinat*
-999 Napropaaidtt
-999 Norflurazon
-999 P.bulat*
-999 Pro««ton
-999 Ppo«atryn
-999 Pronaaida
-999 Propazin*
-999 Sl»«tryn
-999 Siaazina
-999 Stiro-fos
-999 T«buthiuron
-999 Tarbacil
-999 Tarbufos
-999 Tarbutryn
-999 Triad««»fon
-999 Tricyclazole
-999 Varnolat*
-999
Cone.
-999
-999
-990
-999
-999
-999
-990
-999
-999
-999
-999
-999
-999
-999
-999
-999
.099
-999
-999
.999
-999
-999
-999
Z.Taap S_T««p
Data.Sa*
01/01/60
Oat*.Shp
01/01/60
Receipt Condition
Date_Rec
01/01/60
Ti««_Sam Tlm«_Ic«
Saap
Typa
LCSA.
Lab
TSO
Sat «
01
Spikar
CM
Extract
CM
Coavants
NONE.
Oata.Spk
04/30/87
Data.Ext
04/30/87
Data -Ana
05/03/87
Analyst
CM
Saa.Vol
1000
Ext.Vol
5
Colunn
PRIM
Int. Std.
31
1 Surr
99.4
-------
Appendix D
Revision No 4
Date: December 1989
Page 1 of 4
APPENDIX D
SIGNIFICANT FIGURES AND ROUNDING OF NUMBERS
-------
SIGNIFICANT FIGURES AND ROUNDING OF NUMBERS
1 Introduction
To obtain meaningful data on water quality, the sample collector must obtain a
representative sample and then deliver it unchanged for analysis. The analyst must perform
the proper analysis in the prescribed fashion, complete calculations, and convert results to
Final form for permanent recording of the analytical data in meaningful, exact terms. These
results are transferred ta a storage facility for future interpretation and use.
«•
The following sections discuss processing of actual values, recording and reporting of data in
the proper way, some means of quality control of data, and the storage and retrieval of data.
2 The Analytical Value
3 Significant figures
The term "significant figure" is used, sometimes rather loosely, to describe a judgment of
the reportable digits in a result. When the judgment is not soundly based, meaningful digits
are lost or meaningless digits are reported. On the other hand, proper use of significant
figures gives an indication of the reliability of the analytical method used.
The following discussion describes the process of retention of significant figures.
A number is an expression of quantity. A figure or digit is any of the characters 0, 1,1, 3, 4.
5, 6, 7, 8, 9, which, alone or in combination, serve to express a number. A significant figure
is a digit that denotes the amount of the quantity in the particular decimal place in which it
stands. Reported analytical values should contain only significant figures. A value is made
up of significant figures when it contains all digits known to be true and one last digit in
doubt. For example, if a value is reported as 18.8 mg/1, the 18 must be firm while the 0.8 is
somewhat uncertain, but presumably better than one of the values 0.7 or 0.9 would be.
The number zero may or may not be a significant figure depending on the situation.
Final zeros after a decimal point are always meant to be significant figures. For example. 10
the nearest milligram, 9.8 g is reported as 9.800 g.
Zeros before a decimal point with nonzero digits preceding them are significant. With no
preceding nonzero digit, a zero before the decimal point is not significant.
If there are no nonzero digits preceding a decimal point, the zeros after the decimal point
but preceding other nonzero digits are not significant. These zeros only indicate the position
of the decimal point.
Final zeros in a whole number may or may not be significant. In a conductivity
measurement of 1,000 pmho/cm, there is no implication by convention that the conductiv-
ity is 1,000 11 pmho. Rather, the zeros only indicate the magnitude of the number.
-------
A good measure of the significance of one or more zeros interspersed in a number is to
determine whether the zeros can be dropped by expressing the number in exponential form.
If they can, the zeros may not be significant. For example, no zeros can be dropped when
expressing a weight of 100.08 g in exponential form; therefore the zeros are significant.
However, a weight of 0.0008 g can be expressed in exponential form as 8 X 10~4 g, so the
zeros are not significant. Significant figures reflect the limits in accuracy of the particular
method of analysis. It must be decided whether the number of significant digits obtained for
resulting values is sufficient for interpretation purposes. If not, there is little that can be
done within the limits of the given laboratory operations to improve these values. If more
significant figures are needed, a further improvement in method or selection of another
method will be required. ,
Once the number of significant figures obtainable from a type of analysis is established, data
resulting from such analyses are reduced according to set rules for rounding off.
4 Rounding Off Numbers
Rounding off of numbers is a necessary operation in all analytical areas. It is automatically
applied by the limits of measurement of every instrument and all glassware. However, when
it is applied in chemical calculations incorrectly or prematurely, it can adversely affect the
final results. Rounding off should be applied only as described in the following sections.
5 Rounding-Off Rules
If the figure following those to be retained is less than 5, the figure is dropped, and the
retained figures are kept unchanged. As an example, 11.443 is rounded off to 11.44.
If the figure following those to be retained is greater than 5, the figure is dropped, and the
last retained figure is raised by 1. As an example, 11.446 is rounded off to 11.45.
If the figure following those to be retained is 5, and if there are no figures other than zeros
beyond the five, the figure 5 is dropped, and the last-place figure retained is increased by
one if it is an odd number or it is kept unchanged if an even number. As an example, 11.435
is rounded off to 11.44, while 11.425 is rounded off to 11.42.
6 Rounding Off Arithmetic Operations
\Vhen a series of numbers is added, the sum should be rounded off to the same number of
decimal places as the addend with the smallest number of places. However, the operation is
completed with all decimal places intact, and rounding off is done afterward. As an
example,
The sum must be rounded off to 33.4.
-------
When one number is subtracted from another, rounding off should be completed after the
subtraction operation, to avoid possible invalidation of the operation.
When two numbers are to be multiplied, all digits are carried through the operation, then
the product is rounded off to the number of significant digits of the multiplier with the
fewer significant digits.
When two numbers are to be divided, the division is carried out on the two numbers using
all digits. Then the quotient is rounded off to the number of significant digits of the divisor
or dividend, whichever has the fewer. „
When a number contains n significant digits, its root can be relied on for n digits, but its
power can rarely be relied on for n digits.
7 Rounding Off the Results of a Series of Arithmetic Operations
The preceding rules for rounding off are reasonable for most calculations; however, when
dealing with two nearly equal numbers, there is a danger of loss of all significance when
applied to a series of computations that rely on a relatively small difference in two values.
Examples are calculation of variance and standard deviation. The recommended procedure is
to carry several extra figures through the calculations and then to round off the final answer
to the proper number of significant figures.
-------
Appendix E
Revision No 4
Date- December 1989
Page 1 of 3
APPENDIX E
STORAGE OF NPS HARDCOPY DATA FILES AT ECL
-------
STORAGE OF NFS HARDOOPY DATA FILES AT ECL
The HARDOOPY DATA FILES and all related reports will be filed according
to NPS Method No., and then by Sample Set.
ECL has a RECORDS ROOM available for this purpose. It is equipped with
shelving for storage, a smoke alarm, and a sprinkler system. Activation of
the snoke alarm is monitored 24 hours a day by the NSTL fire department which
can respond within 2 minutes to an alarm. ECL will take precautions to;
protect from sprinkler system water damage all files stored in this room.
The RECORDS ROOM is also the office of the ECL QAC and is locked when
the room is unoccupied. Access is limited to the ECL Laboratory Manager, the
ECL QAC and Project/Team Leaders.
The STORED RECORDS LOG is used to log files into the RECORDS ROOM
and to record removal and subsequent return of these files.
-------
tn
o
c
o
u
UJ
CC
o
UJ
CC
o
fr-
X
en
CL
t t 1
1 1 1
1 1 t
1 1 1
1 01 1 1
1 X 1 1
1 CC 1 1
1C 1 1
J £ 1 I
1 IU 1 1
1 CC t 1
1 1 1 "-
to i i
t UJ 1 X 1
1 Z 1 03 I
1C 1 v 1
ID 1 Oi 1
II- 1 JJ 1
1 U» 1 « 1
1 CC 1 O 1
IQ 1 X 1
1 U 1 Oi 1
I > I x l
1 O 1 ID 1
i s: 1^1
t UJ 1 t 1
1 CC 101
1 6 i i
1 UI 1 X 1
f Z 1 OJ 1
1 CC 1 v I
ID 1 0) 1
1 H 1 .u 1
1 UI 1 1 X 1
1 O 1 U 1
1C 1 x< 1
1 UJ 1 « 1
1 CC 1 O 1
1 Q 1 1
1 UJ \ > \
1 Z 1 CD I
1 CC 1 v |
ID 1 01 1
II- 1 4J 1
1 UJ 111
1 CC 1 O 1
1 O 1 X 1
1 UJ 1 CD 1
i :> i x i
ID Ibt
i r i *• i
1 UJ 1 t 1
1 CC 101
1 _l UJ 1 XI
i a ID i oo i
i -• « i x i
1 1- CC 1 81
1 « O 1 *t 1
1 Z 1- 1 * 1
i —
-------
Appendix F
Revision No 4
Date December 1989
Page 1 of 3
APPENDIX F
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 :
2) Decide whether the smallest, Xlt 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 5% risk values (bolded) .
Example (from Taylor)
Given the following set of ranked data:
10.45, 10.47, 10.47, 10.48, 10.49, 10.50, 10.50, 10.53, 10.58
The value 10.58 is suspected of being an outlier.
1) Calculate rn
10.58 - 10.53 0.05
rn - ............. - ---- - 0.454
10.58 - 10.47 0.11
2) A 5% risk of false rejection (Table 2), rn - 0.477
3) Therefore there is no reason to reject the value 10.58.
4) Note that at a 10% risk of false rejection rn - 0.409, and the value
10.58 would be rejected.
-------
TABLE 1
CALCULATION OF RATIOS
For use if if Xn is
Ratio n is between suspect
(X» - X,,.!)
T- ^7 ..........
r!0 J - /
r a . in .-
(Xn - X2)
(Xn - Xn_2)
_ 1 1 1 ^ .......
r21 11 - IJ
(Xn - X2)
/ V V N
(.-^n " An-2/
r 1A - 9S .......
r22 1A--ZD
/Y Y ^
^•^n " A3^
if Xi is
suspect
(X2 - K!)
/V Y "1
\.A2 - A-i)
(X3 - XO
(Xg Xi)
(Xn-2 - Xx)
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
n 0.5% 1% 5% 10%
r22
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
0.994
0.926
0.821
0.740
0.080
0.725
0.677
0.639
0.713
0.675
0.649
0.674
0.647
0.624
0.605
0.589
0.575
0.562
0.988
0.889
0.780
0.698
0.637
0.683
0.635
0.597
0.679
0.642
0.615
-0.641
0.616
0.595
0.577
0.561
0.547
0.535
0.524
0.514
0.505
0.497
0.489
0.941
0.765
0.642
0.560
0.507
0.554
0.512
0.477
0.576
0.546
0.521
0.546
0.525
0.507
0.490
0.475
0.462
0.450
0.440
0.430
0.421
0.413
0.406
0.806
0.679
0.557
0.482
0.434
0.479
0.441
0.409
0.517
0.490
0.467
0.492
0.472
0.454
0.438
0.424
0.412
0.401
0.391
0.382
0.374
0.367
0.360
Note that for this QAPjP the 5% risk level will be used for ratio r22-
-------
Reference:
John K. Taylor, Quality Assurance of Chemical Measurements. Lewis
Publishers, Chelsea, MI, 1987.
-------
Appendix G
Revision No 4
Date December 1989
Page 1 of 9
APPENDIX G
ADDITIONAL QUALITY CONTROL CHECKS
-------
QUALITY ASSURANCE DATA FORM
NFS GROUND WATER
Sampling Date(s)
Arrival Date(s) at ECL
Method 1
Set No.
1.
2.
3.
5.
6.
Set Composition
sample wt. (gms)
7.
8.
9.
sample wt. (gms)
Method Blank
Surrogate
Standards and Set Controls Data
Name / Date of Std. Used Amt. Spiked Initials
r**
STOP!! . Has Sample Control Record been completed for both distribution and
return of samples?
. Has Set Composition Form been attached?
. Has ECL/NFS Sample Tracking Form been attached?
Signature:
Date:
-------
Sample Preparation
Initials of Employee(s)
Procedure Accomplished Doing Work Comments
Extraction «
GC Analysis
Date Begun: Analyst(s): Date Completed:
Internal Std. Spike Data:
Spiked By: Date:__ Amt. Used:_
Name / Date of Std. Used:
I.D. of Instrument Used for Analysis:
Analysis Dates
1. 4. 7.
2. 5. 8.
3. 6. 9.
STOP I! . Is GC work complete?
. Have NFS Data Report Forms on each sample been completed for each
GC column?
. Has remedial QC work been carried out with results attached?
.If any sample in this set will be reextracted/ list the 9 digit -
code no. of the sample.
. Is any sample in this set a reextracted sample?
Signature: Date: Disposition of Extracts:^
Data Reviewed By: Date:
* Final Disposition of Extracts: Signature:_
* Date of Final Disposition:
S3
-------
EXCEPTIONS TO QC REQUIREMENTS
NPS Method Set
*
State exception, when noticed, who notified, remedial action required, action taken:
sign and date for each separate incident.
-------
QUALITY ASSURANCE DATA FORM INSTRUCTIONS
To fill out the QA Data Form, refer to the Assignment Sheet and Sample
Tracking Form for the set.
Sampling Date(s);
»
This information is on the Sample Tracking Form.
Arrival Date(s) at ECLt
This information is on the bottom of the Sample Tracking Form under
Date Received.
Set No.;
This information is in the title of the Assignment Sheet.
Set Composition:
The correct order of the controls and samples is copied from the As-
signment Sheet onto the Set Composition portion of the Quality Assurance
Data Form. For each sample, write both the sample name and 9 digit sample-
code nurber. The number to the left of each control name or sample name in
this section is the Set Composition Number. It, in conjunction with the
Set Number, will be used to identify the controls and samples throughout
the extraction and G.C. Analysis. Set Composition Numbers are initially
assigned on the Assignment Sheet for each set. After determination, the
weight in grams and pH is recorded for each water sample. The weight for
all controls is 1000 gins. No pH is recorded for controls. Column Checks
are simply listed next to their Set Composition Numbers, pH and weight
data being inapplicable.
In the event that a Ground Vbter Sample is a reextraction, place an R
before the 9 digit sample - code number and follow it with the Set Number
and Set Composition Number, in parenthesis, of the original Ground Vbter
Sample.
Standards and Set Controls Data:
The purpose of this section is to provide information about the spik-
ing standards used in the set. Copy this information from the Assignment
Sheet. In the empty brackets to the right of the Method Blank, Laboratory
Control Spikes, Surrogate and Column Checks, write the date the control was
originated. This is the date of extraction for all but the Column Checks.
The Column Checks are originated on the date the florisil columns are begun.
For the Shipping Blanks and Laboratory Sample Spikes, the 9 digit sample -
code numbers are placed in the empty brackets.
-------
The information for the Name / Date of Std. Used and Amt. Spiked
section can be copied from the Assignment Sheet. The date in parenthesis
following the standard name indicates the date the standard was prepared.
The person who spikes a standard should write his initials behind it
in the Initials section.
*
Questions:
Has Sample Control Record been completed for both distribution
and return of samples?
The Sanple Control Record is kept in the Receiving Room. Vhen NFS
water samples are removed from the cooler for extraction, they are
signed out on the Sample Control Record. The empty sample bottles
are later returned to the Receiving Room and signed in on the Sample
Control Record.
Has Set Composition Form been attached?
The Assignment Sheet is prepared at EPA/ECL by the Project Manager
and sent to the Processing Laboratory at the start of each set
extraction.
Has ECL/NPS Tracking Form been attached?
The ECL/NPS Sample Tracking Form tracks the samples from storage
through extraction, and G.C. Analysis.
Signature:
The person completing this page of the form should sign and date the
form here.
Sample Preparation;
The NPS Method I Extraction Procedure is broken down into six parts
in this section. The Date Accomplished and Initials of Employee(s) Doing
Vbrfc should be provided for each. There is a section provided for comments
(exceptions to routine) if applicable.
Signatures:
Vhen sample extracts are delivered for GC analysis, the employee re-
linquishing the extracts and the employee receiving the extracts should
sign and date the OA Data Form.
-------
G.C. Analysis
Date Begun;
Write the date the extracts are spiked with the Internal Standard.
Analyst(s); *
Write the name of the person(s) who analyzed the samples on the ins-
trument (s) and performed the calculations on the set.
Date Completed;
Write the date all calculations and data forms for the G.C. analysis
are completed and submitted for review.
Internal Std. Spike Data;
This section provides information concerning the Internal Std., the
date the set was spiked, amount used and the name and date of standard used.
This date is the date the Internal Std. was prepared.
I.D. of Instrument Used for Analysis;
Write in the serial no(s). of the G.C.(s) used.
Analysis Dates;
In this section, the controls and samples are referred to by their
Set Composition numbers as written on the first page of this form. Beside
each set composition number, record the date of the last injection on a
Gas Chromatograph for each control or sample.
Questions;
Is G.C. work complete?
Is all analysis on the instrument completed?
Have NFS Data Report Forms on samples been completed for each G.C. coin
This includes the primary and confirmatory G.C. columns.
Has remedial CC work been carried out with results attached?
The analyst is responsible for conducting QC checks. If any portion
of the data falls out of the acceptable QC limits, remedial QC work
must be done. All QC checks and QC remedial work is outlined in the
QC Requirements and Criteria Attachment.
-------
If any sample in this set will be reextracted, list the 9 digit - code
no, of the sample.
Refer to the Set Composition section of this form to find the 9 digit -
code no. of the sample.
Is any sample in this set a reextracted .sample?
If the answer is Yes and additional information on the original sample
is needed, refer to the Set Composition section of this form. Any
reextracted sample will have an R preceding the 9 digit sample- code
number and be followed by the bracketed Set Number and Set Composition
Number of the original sample.
Signature;
The person completing this page of the form should sign and date the
form here.
Disposition of Extracts;
Following review of the G.C. Analysis Data, sample tubes are quanti-
tatively transferred to culture tubes and volumes marked. All information
on concentrator tubes is transferred to the culture tubes, which are then
stored in a cooler. At this time, the "EXTRACT STORAGE DATA SHEET",(See
Appendix A), is completed by recording all pertinent extract information.
Data Reviewed By;
Signature of person who reviewed completed data set. This must be
someone other than the person who analyzed the set.
Date;
Write the date the review was completed.
Final Disposition of Extracts;
Sample extracts will be held until the Technical Monitor approves of
their disposal (See 7.23 of the QAPP).
-------
u
T
n
u
0)
a. j
8
I
to
a
z
S 0£
12 C
<0 -^
O LO
•C O X U O OO«<0
IQ.W o j Iz a: H J
~ ~~_ rr~ nmzuzn^i —n~—nn «n—mniz —•" — ~~zn
fl)
U
0)
CO
•
•
1
« o
H
O «D
to o
O
n
<0 -^l
J to
-------
Appendix H
Revision No 4
Date December 1989
Page 1 of 3
APPENDIX H
ECL COMPUTER PROGRAMS
-------
HfiR 23, 1968 15:43:27
, WRITTEN FOR ECL BY WUD, QCT 1,1986
ieL£TN=T=Cl=C2=Dl=D2=0
26PRINT-ENTER COMPOUND NflME";
30IHMfi*[48]
35DIMUC160]
36DIMP[100]
37DIMXC1803
38DIMDC1603
39DIMGH0G3
40INPUTR*
50PR1NT-ENTER -1 flFTER YOUR LRST DfiTft POINT"
60FORI*1T036
70PRINTI
80PRINT"ENTER YOUR VfiLUE FOR X";
96INPUTUCI3
lieLETH=N+l
126PRINT"EHTER YOUR VftLUE FOR Y ";
l36INPUTPtn
140NEXTI
150PRINT
ICGPRIHT-ftRE ALL VftLUES CORRECT? (Y/-H)";
170INPUTBJ
180IFB**"Y"THEN260
190PRINT-EHTER THE NUMBER OF THE PftIR IN ERROR";
200INPUTI
210PRINT"£NTER THE CORRECT X";
220INPUTUU 3
230PRINT-ENTER THE CORRECT Y";
240INPUTPCI]
2SBCOT0160
260FORI*1TON
270LETC1*C1*UCI]
280LETC2=C2*
310NEXTI
320LETS*/-<48>|" -DIFFA2"
490FORI-1TON
500PRINTUCI3;TflB<12)5PCI3jTflB<20>;XCI3}TRB<33);DCI35 '
5iePRIHTTflB(48);GCI]
529LETT«T+CCn
538NEXTI
548PRINT-THE SUM OF DIFF^2 IS -|T
550PRINT
-------
VALUE. USE A -1 TO END THE OPERATION.
560PRINT
570PRINT
586LETZ = Z-H
59GGOT042G
6060UTBVC"T1",E
616PRIHT-INPUT A
620INPUTT
630IFT=-1THEN726
640LETV»xS
650PRINT"YOUR X
ee0pRiNT"YOUR Y
67eOUTDVC"LlM, E
686PRINT
696PRIHT"YOUR X
7eePRINT"YOUR Y
710GOT0666
720PRINT
73GOUTLVC"T1",E
746 1 FL» = " MANY" THEN 10
750PRIHTMF YOU HAVE SEVERAL GROUPS AMD WOULD LIKE TO OMIT";
766PRIHT"THE NEXT QUESTION, ENTER MANY INSTEAD OF Y OR N. "
770PRINT
780PRINT"IiO YOU WANT TO ENTER ANOTHER CROUP'-' ' Y^N/MANY) "
796INPUTLJ
800IFLJ="MANY"THENie
810IFLS="Y"THENie
820END
END OF FILE
VALUE
VALUE
VALUE
VALUE
IS
is
IS
IS
V
T
"V
"T
-------
Appendix I
Revision No 4
Date December 1989
Page 1 of 6
APPENDIX I
RAPID REPORTING NOTIFICATION
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
'•*. ,
-------
-2-
If you have any questions concerning these procedures, please let Bob
Kaxey or me know. Also, please pass on this information to your contract
and referee laboratories. They will need to have this information in hand
prior to their conducting the dry run.
Attachment l•
»
Addressees:
A. Dupuy
L. Kamphake
C. Madding
R. Haxey
R. Sorrell
R. Thomas
cc:
J. Kotas
H. Brass
A. Kroner
J. Orme
-------
METHOD II
ANALYTE RAPID REPORTING LEVEL
i ,
Alachlor 44*ug/L
Ametryn 300 ug/L
Atrazine 35 ug/L
Bromacil 2,500 ug/L
Butylate 700 ug/L
Carboxin 1.000 ug/L
Dipbenamid 300 ug/L
Fenamiphos 5.0 ug/L
Hexazinone * 1.050 ug/L
Metolachlor 300 ug/L
Ketribuzin 250 ug/L
Propazine 500 ug/L
Simazine 50 ug/L
Tebuthiuron 125 ug/L
Terbacil 250 ug/L
-------
BSL
NFS RAPID REPORTING NOTIFICATION
NFS METHODS 1,3 AND 6
Date:
Set No.:
NFS Field Sample No.:_
BSL Lcb. I.D. No.:
METHOD 1
ANALYTE
I
Rapid
Reporting
Level (ppb)
Analytical Results
Primary GC Column
(ppb)
Secondary GC Column
(PPb)
QC/MS
(pos. or neq. or N/
METHOD 3
ANALYTE
Rapid
Reporting
Level (pj±>)
Analytical Results
Primary GC Column
(PCb)
Secondary GC Column
(PPb)
GC/MS
(pos. , neq. , or N/]
NOT ANALYZED
-------
METHOD 6
ANALYTE
Rapid
Reporting
Level (ppt>) "
Analytical Results
Primary QC Column
i. (ppb)
Secondary QC Column
(Mb)
»
*
GC/MS
(pos. or neq. or fc
« NCT ANALYZED
QA Assessnent:
Is there any CC problera(s) with the set or the sample for either Method that may
adversely impact the identification or quantitation of the above analytes? If yes
describe.
R. Maxey, Project Lead
-------
Appendix J
Revision No 4
Date December 1989
Page 1 of 4
APPENDIX J
GC/MS CHARACTERISTIC IONS FOR METHOD 1
-------
I
£
U)
r
o
tte
VI
5
u
§
oc
^
Ul
A.
v»
I
1 <
&
t
1
M
"e
t
5
>
-
IA
C
U
»-
u
1
u
u
*•
3
oc
u
1
z
3
*•»
o
z
m
>•
EC
5
K
a.
t oc
) U)
3 5
d Z
x.
A
S
O
z
fN
>•
K
|
OC
«.
z
<
«n «.
X w%
S
O
w
u
UJ
-1 '
z
o
Q
£
w
X
<« «t O <« ••«•« O •*
<<<<<<
o » — o
o o o
0000000000
S
M
£ £
__
«MM O
o <
aetoeoo
-------
|
*•
y
u
a.
M
•
-
i
M
U
2
i
» ^
U 1
b
£
«
M
"e
v>
3
J
r-
n
K
El CIIARACTE
t-
1
a:
u
z
«^
o
z
<
o o £
-------
u e.
s
A
•• I
XlA
> o
*
oooooo eeeeeeeo
U O
x H
X »• J
O < O
bXM
1C 0
-------
Appendix K
Revision No 4
Date December 1989
Page 1 of 11
APPENDIX K
ADDENDA TO METHOD 1 - JUNE 1988 to DECEMBER 1989
-------
05/01/89
Environmental Chemistry Section
Addendum - Method 1
Revision to Section 4, page I/ paragraph 1, sentenced .
- Change "Dr. Y. A. Yonan, BCL-QAO" to "Mr. Danny McDaniel/
Acting ECS-QAC, ..."
Revision to Section 4, page 1, paragraph 2
- Delete first 3 sentences.
- Replace with "Dr. Christian Byrne will handle sample preparation, extraction,
and GC analyses backed up by Mr. Pay Shaw. Data handling and reporting will be
handled similarly. Data review has been assigned to Mr. William Mitchell and
Mr. Joe Ferrario."
Revision to Section 4, .Figure 4-1 - ECS ANALYTICAL TEAM - Method 1
- Delete ECS ANALYTICAL TEAM diagram from Figure 4-1.
- Replace with revised diagram on following page.
Approved
EPA/ECS-NPS Projec£/ Leader/
ECS Analytical Coordinator
Approved &$
-------
Project: NFS
Section No: 4
Revision No: 4
May 1989
Page of
Sample Custodian
G. Gardner (EPA)
Assistant Sample
Custodians
a. Cuevas (EPA)
S. Mecomber (EPA)
Sample Prep./Ext.
C. Byrne (STI)*
R. Shaw (EPA)
ECS ANALYTICAL TEAM
METHOD 1
NPS Project Leader
Bob Maxey (EPA)
GC
C. Byrne (STI)*
R. Shaw (EPA)
ECS-QAC (Acting)
D. McDaniel (EPA)
Data Review
VI. Mitchell (AARP)
J. Ferrario (EPA)
GC/MS
J. Ferrario (EPA)
Data Handling
Reporting
C. Byrne (ST]
R. Shaw (EPA!
Sverdrup Technology Inc. (In-house Contractor for ECS)
ECS provides overall technical direction to Sverdrup Technology/ Inc.
FIGURE 4-1: ECS ANALYTICAL TEAM - METHOD 1
-------
05/01/89
Environmental Chemistry Section
Addendum - Method 1
Revision to Section 11 * page 2, Chart 11.1 - PSF - Criteria for Acceptance
- Delete "0.90 < PSF > 1.10"
- Add "Refer to Section 11.21 - Criteria for Peak Symmetry Factor (PSF)"
Addition to Section 11, top of Page 4 of 11
- Add the following section:
Section 11.21 - Criteria for Peak Symmetry Factor (PSF)
o Using PSF data points for the first 20 valid sets of Method 1 data,
calculate x, standard deviation/ and RSO. If RSD <^ 20% and no more
than 3 outliers,
» •
- establish^ a 3cf control chart around x, with x ^ 2 RSD as warning
limits; x ± 3 RSD as control limits.
o Plot the succeeding 5 PSF data points for the next 5 sets.
o Reconstruct control chart each 5 sets using the most recently generated
PSF data points-and dropping the 5 "oldest" data points.
- RSD should be <_ 20%
_ no more than 3 outliers
o Two successive data points outside control limits presents an out-of-cor
situation which must be corrected before proceeding.
Approved
EPA/ECS-NPS ProjectO-eader/
CCS Analytical Coordinator
Approved
QAO-^g»S
7^^.
Approved.
Approved ^y7fr>
-------
\ UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
ENVIRONMENTAL CHEMISTRY SECTION
BUILDING 1105— JOHN C. STENNIS SPACE CENTER
STENNIS SPACE CENTER. MISSISSIPPI 3052»-6OOO
TELEPHONE (901) 6M-3216
Anril 26, 1989
MEMORANDUM
SUBJECT: Revision to Section 11.21: Criteria For Peak Symmetry Factor (PSF)'-
NPS Method 1
FROM- Bob Maxey, ECS-NPS Team Leader n^
TO: NPS Method 1 Personnel
To demonstrate that ECS has control over this PS Factor, the procedure
given below has been established to determine an acceptable range for the
Factor.
o Using PSF data points for the first 20 valid sets of Method 1 data,
calculate x, standard deviation, and RSD. If RSD <_ 20% and no more
than 3 outliers,
- establish a 3 control chart around x", with x~^ 2 RSD as warning
limits; x _+_ ? RSD as control limits.
o Plot the succeeding 5 PSF data points for the next 5 sets
o Reconstruct control chart each 5 sets using the most recently generated
PSF data points and dropping the 5 "oldest" data points
- RSD should be <_ 20%
- no more than 3 outliers
o Two successive data points outside control limits presents an out-of-
control situation wh.ich must be corrected before proceeding.
This procedure and these requirements must be added, via an addendum, to
the Method.1 QAPjP in Section 11 no later than May 15, 1989. Each sample set
must contain a copy o* the control chart and criteria in effect for that set.
For all data sent to the NPS Data Manager (Chris Frebis) in Cincinnati, the
appropriate PSF criteria must be included.
If you have any questions, let me know.
Addressees:
C. Byrne, STI
W. Dreher, STI
R. Shaw, ECS
cc- Aubry E. Dupuy. Jr.; Section Chief
Danny McDaniel; Acting ECS-QAC
-------
8/12/88
ENVIRONMENTAL CHEMISTRY LABORATORY
ADDENDUM - METHOD 1
Addition to Section 4, p'age 1, paragraph 2, sentence 2
-Add "Data review has been assigned to Mr. George Sand."
Addition to Section 4, page 1, paragraph 3
-Change "NASA/NSTL Bldg. 1105
NSTL,MS 39529"
to
MNASA/SSC Bldg. 1105
STENNIS SPACE CENTER, MS 39529-6OOO"
Addition to Section 4, page 1. paragraph 4
-Change "The Assistant Sample Custodian -for NFS is:
Mr. John Cuevas
(601)688-3170 (or 3217)"
•
to
"The Assistant Sample Custodians -for NPS are:
•
Mr. John Cuevas Mr. Stanley Mecomber
(601)688-3170 (or 3217) <6O1)688-3170 (or 3217)"
Figure 4-1: ECL ANALYTICAL TEAM was revised. The new chart is
enclosed.
Approved
fflfj^L
EPA/ECS-NPS Project
ECS Analytical Coordinate
i
» ' •
-------
Sample Custodian
I
I
I G. Gardner (EPA) |
I J. Cuevas (EPA) |
Sample Prep./Ext.
W. Dreher (STI)*
C. Byrne (STI)*
Project: NPS
Section No: 4
Revision No: 2
March 1988
Page of
ECL ANALYTICAL TEAM
METHOD 1
I I
| NPS Project Leader |
I I
I Bob Maxey (EPA) I
ECL QAC
Y.Yonan (EPA)
| Data Review |
.1 I
I George Sand (EPA) I
GC
W. Dreher (STI)*
QC/MS
D. McDaniel (HR)(EPA)
J. Ferrario (LR)(EPA)|
I
Data Handling/
Reporting
W. Dreher (STI)1
* STI *= Sverdrup Technology Inc. (In-house Contractor for ECL)
Sverdrup is providifng the ECL several person-years of support.
ECL provides overall technical direction to Sverdrup Technology/ Inc.
FIGURE 4-1: ECL ANALYTICAL TEAM - METHOD 1
-------
7/21/88
Environmental Chemistry Laboratory
Addendun - Method 1
Addition to Section 2, page 7, Appendix G
-Add "Internal Quality Control Checklist" below "QC Data Sheet"
-Add an Appendix "J: QC/MS CHARACTERISTIC IONS FOR METHOD 1"
Addition to Section 5, page I/ number 8, end of paragraph
-Add "See Appendix J for a Table of the three ions for each analyte"
Addition to Appendices
-Add a cover sheet for Appendix J: GC/MS CHARACTERISTIC IONS FOR METHOD 1.
(For the appendix contents, see the enclosed GC/MS Characteristic Ions
Table.)
Approved
Approved
t
Approved
-------
1
1
t
1
1
<
1
1
•
t
1
•
1
I
1
1
1
!
•
•
i
•
•
•
•
•
*
•
•
•
•
•
•
•
i *
M
O
gg
E
5
u
C
«t
u
*•
u
1
u
u
^
QC 1
+• 4
«
U '
^ :
M
f
•
I
1
1
4
I
*
t
1
1
1
1
1
1
*
§
e
u>
A
£
5
•X.
8
*•»
S
i
i
u
s
U O 5
t
i
•
•
i
•
•
•
•
•
t
•
•
t
i
•
•
i
•
*
t
%
•
*
t
i
•
•
*.
•
t
4
O
9
§
u
! "i
• s
• O
• M
I U
: 2
: s
• u
u
<
u
IA
u
O
-3
X M
........ O
*- S
-------
3
C
««
U
«•>
U
m
i-
Ct
SPECTRUM
1
;
I
S
*•
u
I
i
a i
i
«
M
M
X
3
J
M
•M
X
1*4
»-
CtlARAC
u
i-
X
HUHBCR
1
o
M
>•
*4
tt
•.
j S
.
A
r^
X
!•
X
*.
X
VI U
£
INJECTED.
NG
METHOD
NUMBER
AMA1YTC
n. ft •*
o
2
5
-------
is
=
i
8
Ck
u
i
5
yvn- 1,» w'f -,*
ijt
n fid .'-'t'
l-r
------- |