EPA-810/B-92-006
United States Office of Water (WttSSO) EPA 810-B42406
Environmental Protection Office of PetUddea and February 1992
Agency Tojdc Substances (H-7501C)
QUALITY ASSURANCE PROJECT PLAN
FOR THE
NATIONAL PESTICIDE SURVEY OF DRINKING WATER WELLS
ANALYTICAL METHOD 6
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 (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
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Section No. 1
Revision No. 4
Dote: December 1989
Page 2 of 2
APPROVAL PAGE
_, ECS Project Leader
Robert Maxey
, EPA Technical Monitor
Aubry E. Dupuy, Jr. Section Chief, ECS
, Acting ECS; QAC
Danny McDaniel
, NPSQAO
Lora Johnson
Elizabeth Leovey
List for Distribution:
A. Dupuy, OPP/ECS
R. Maxey, OPP/ECS
D. McDaniel, OPP/ECS
L Johnson, NPS QAO
E. Leovey, OPP/QAO
G. Gardner, OPP/ECS
C. Byrne, STI
S. Mecomber, OPP/ECS
, OPPQA Officer
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
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Section No. 2
Revision No. 4
Date: December 1989
Page 1 of 6
NATIONAL PESTICIDE SURVEY
QUALITY ASSURANCE PROJECT PLAN FOR
ANALYTICAL METHOD 6
t; 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
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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 6 4 12/89
8.1 Method 6 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 Calibration of Instrumentation
8.2.1 Calibration of Gas Chromatograph
8.2.2 Calibration of GC/MS
9. ANALYTICAL PROCEDURE 2 4 12/89
9.1 Summary of Method
9.2 Major Equipment/Instrumentation to Be Used With
Methods
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 Gaussian Factor (PGF)
11.3 GC/MS Confirmation
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Section No. 2
Revision No. 4
Date: December 1989
Page 3 of 6
2. TABLE OF CONTENTS (continued)
Section Pages Revisions Date
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 2 4 12/89
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 2 4 12/89
13.1 Gas Chromatographs
13.2 GC/MS
14. SPECIFIC PROCEDURES FOR ASSESSING
MEASUREMENT SYSTEM DATA 3 4 12/89
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 1 4 12/89
16. QUALITY ASSURANCE REPORTS TO
MANAGEMENT 4 4 1289
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Section No. 2
Revision No. 4
Date: December 1989
Page 4 of 6
2. TABLE
Appendices
A
B.
C.
D.
E.
F.
G.
H.
I.
*J.
*K
OF CONTENTS (continued)
I
SAMPLE CUSTODY
BATTELLE'S VERSION OF NPS METHOD 6
DATA FLOW (REDUCTION, VALIDATION, AND
REPORTING)
SIGNIFICANT FIGURES AND ROUNDING OF NUMBERS
STORAGE OF NPS HARDCOPY DATA FILES AT ECS
DIXON'S TEST
ADDITIONAL QUALITY CONTROL CHECKS
ECS COMPUTER PROGRAMS
RAPID REPORTING NOTIFICATION
GC/MS CHARACTERISTIC IONS FOR METHOD 6
ADDENDA TO METHOD 6:
3aqes
6
27
11
4
3
3
6
3
6
2
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
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.
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Section No. 2
Revision No. 4
Date: December 1989
Page 5 of 6
2. LIST OF FIGURES
Figure
ECS ANALYTICAL TEAM - METHOD 6
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
11-3
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
3of4
4 Of 4
4of 6
5 Of 6
6 Of 6
4 Of 6
5 Of 6
6of 6
5 Of 6
6 Of 6
7of 7
3 Of 3
2 Of 4
3 Of 4
4 Of 4
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Section No. 2
Revision No. 4
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Page 6 of 6
2. LIST OF TABLES
Title
ENVIRONMENTAL CHEMISTRY LABORATORY SAMPLE
REQUIREMENTS
Table Mo. Section Page
6-1
2 of 4
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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. One compound, Ethylene
thiourea, (ETU), will be determined by NPS Method 6.
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 6. 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.
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Section No. 4
Revision No. 4
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Page 1 of 2
4. PROJECT ORGANIZATION AND RESPONSIBILITIES
Referee laboratory responsibilities for NFS Method 6 will be carried out by OPP's Environmental
Chemistry Lab. (ECS) which is managed by Dr. Aubry E. Dupuy, Jr. Section Chief. The latter will also
be Technical Monitor for Method 6. Mr. Robert Maxey, Chemist at ECS, will serve as Project Officer for
the Method. Mr. Maxey, as ECS Project Leader, will also be responsible for day-to-day management
of NPS analytical activities. Mr. Danny McDaniel, Acting ECS-QAC, will provide QA oversight (effective
05/01/89; see Appendix K; Addendum of 05/01/89). The Sample Custodian for ECS and for the NPS
Project is Gerald Gardner.
Dr. Christian Byrne and Mr. Stanley Mecomber will handle sample preparation, analysis, data
handling and reporting (effective 05/01/89; see .Appendix K; Addendum of 05/01/89). Data review has
been assigned to Mr. Henry Shoemaker. Data handling and reporting will be backed up by Ms. Flynt.
Mr. Joe Ferrario will provide Low Resolution GC/MS confirmation while Mr. Danny McDaniel will handle
High Resolution GC/MS work. Refer to the Method 6 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' Sample Custodian:
* U.S. EPA
Environmental Chemistry Section
NASA/SSC Bldg. 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 telephone number for the EPA Technical Monitor for NPS Method 6 is:
Dr. Aubrey E. Dupuy
(601) 688-3212
who will also serve as the back-up contact on Method 6 for the EPA Project Officer.
The telephone number for the EPA Project Officer for NPS Method 6 is:
Mr. Robert Maxey
(601) 688-1225 (or 3217)
who will also serve as the back-up contact on Method 6 for the EPA Technical Monitor.
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Section No. 4
Revision No. 4
Date: December 1989
Page 2 of 2
FIGURE 4-1
ECS ANALYTICAL TEAM - METHOD 6
Sample Custodian
G. Gardner (EPA)
Assistant Sample
Custodians
J. Cuevas (EPA)
S. Mecomber (EPA)
Sample Prep./Ext.
C. Byrne (STI)*
S. Mecomber (EPA)
NPS Project Leader
Bob Haxey (EPA)
ECS-QAC (Acting)
D.McDaniel (EPA)
Data Review
H. Shoemaker (EPA)
GC
C. Byrne (STI)*
S. Mecomber (EPA)
I
GC/MS
J. Ferrario (EPA)
Cata Har
Reportir
C. Byrne
S. Mecomt
Sverdrup Technology Inc. (In-house Contractor for ECS)
ECS provides overall technical direction to Sverdrup Technology, Inc.
(effective 05/01/89; see Appendix K; Addendum of 05/01/89)
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Section No. 5
Revision No. 4
Dote: 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 Technical
Monitor, 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 EDIs 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 Technical Monitors.
* 8. To ensure adequate sensitivity the day GC/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).
9. The Minimum Reportable Level (MRL) for Method 6 is 3 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 einalytical 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.
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Section No. 5
Revision No. 4
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Page 2 of 5
5.2.1 Procedure for Determlnlnlng and Reporting the Presence of ETU Below the
Minimal Reporting Level
1. For Method 6, only suspected ETU peaks with responses of between one-half the
established MRL and the MRL A/ on the primary column will be investigated.
2. (a) For Method 6, if the response on the second column is positive, further analytical work
under (3) below is required.
(b) For Method 6, if the response on the second column is negative, that fact is noted. After
five attempts at second column confirmation have failed for ETU, 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.
4. Only analytes positively confirmed by GC/MS will be reported beyond the ECL Project
Leader for Method 6 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.
A/=NPS Method 6 MRL = 3 X EDL
B/=LR GC/MS = Low resolution mass spectrometry
HR GC/MS = High resolution mass spectrometry
5. Following the successful GC/MS confirmation of two such responses for ETU or two
successive 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 ETU 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 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 6, if the response of an extraneous peak, exclusive of the Method Blank, on
the primary column is greater than or equal to that of ETU at the Spiking Level (10 X MRL)
upon initial injection, an attempt must be made to identify that peak by GC/MS. Full scan
spectra and subsequent library search is expected and must be followed by comparison
of the spectra of the unknown compound with that of an authentic standard of the
suspected compound.
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Section No. 5
Revision No. 4
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Page 3 of 5
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 6. 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. 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 the Method, and the Analytical Coordinators. No unconfirmed data will
be reported outside the NPS analytical system. Unsuccessful attempts at identification will
also be reported to the Technical Monitor.
4. Following either the successful confirmation of two such extraneous peaks proving to be
the same compound or two failures to identify 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. A laboratory control standard mix, containing ETU and the surrogate (PTU), 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 6, will be used but may not deviate
by more than ± 20% of the area of the the internal standard in the nearest calibration
standard (effective 06/88). 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 criteria for monitoring instrument control standards will be utilized as stated in the
method.
6. 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 ± 0.30 R. (effective 081888).
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Section No. 5
Revision No. 4
Date: December 1989
Page 4 of 5
7. The requirements for monitoring calibration standard responses will be followed as written
in the method.
8. Samples failing any QC criteria must be reanalyzed.
9. Each time that a new calibration standard dilution is prepared, it 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 appropriate Technical Monitor, and documented in writing.
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 ETU determined using the primary column.
2. The concentration for ETU 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 Technical Monitor 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 an ETU standard prepared at the concentration
of ETU determined from the sample extract, 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 analysis are simply reported as the presence or absence of ETU.
4. If the low concentration of ETU in the extract precludes use of Low Resolution GC/MS,
High Resolution GC/MS Confirmation must be attempted. HRGC/MS may also be
required if the ETU Concentration is greater than or equal to 1/2 its lowest adverse health
effect 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).
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 TEMPERATURE OF THE SAMPLE IN THE
BOTTLE
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Section No. 5
Revision No. 4
Date: December 1989
Page 5 of 5
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 your Technical Monitor 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 Technical Monitor.
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 ECL
Project Leader.
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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 60-ml sample preserved with mercuric chloride at 10
mg/liter. This sample is to be shipped iced along with those needed for Methods 1 and 3, 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. The 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. The form is shown in Figure 6-2.
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Section No. 6
Revision No. 4
Date: December 1989
Page 2 of 4
TABLE 6-1
ENVIRONMENTAL CHEMISTRY LABORATORY SAMPLE REQUIREMENTS
LAB
JOT TYPE
Sasple Types
BOTTLE TYPE
HOL. KETttX
Prioary
teferee
Shipping Blank
Backup Saoplc:
Lab Spikes
Tine/Storage
"totals
lia. of Sices
TOISLRBO'D
BSL t
Referee
lOOOoL lOOCfaL 60niL
1 3 6 '
1 1 1
111
ISO 150 ISO
ISO - 150 ISO
"total Bottles:
100CtaL« 300
2SOoL» N.A.
60nL« ISO
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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-O1
BSL - METHOD* 1 KIT: 611
FIELD SAMPLE
PRESERVATIVE: HgC12
DATE ', TIME 5 SAMPLER
NATIONAL PESTICIDE SURVEY
SAMPLE #: PD-OOOO-6-3-01- -
BSL - METHOD* 3 - \ IT: £
FIELD SAMPLE
PRESERVATIVE: H=C12
DATE '. TIME '. SAMPLER
NATIONAL PESTICIDE SURVEY
SAMPLE #: PD-0000-6-6-01
BSL - METHOD** 6 KIT: 611
FIELD SAMPLE
PRESERVATIVE: HgC12
DATE ! TIME ', SAMPLER
NfiTJONrW _££5JJ -PJ SS SURVEY
i'-LE «: PC-- •• .-.•-3-i--vr.:
BSL - METHOD* 1 KIT: 611
BACKUP SAMPLE
PREBERVAT I V£ : HgC 1 2
DATE ! T I !1g \ SAMPLER
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Section No. 6
Revision No. 4
Date: December 1989
Page 4 of 4
FIGURE 6-2
FIELD SAMPLE TRACKING FORM
WELL I.D. NO.: 0000
FRDS I.D. No. (CHS HELL ONLY):
SAMPLE COLLECTION DATE: /
TRACKING FORM COMPLETED BY:
LAB: SSL
SCE.1AR10: _l
EOi 1 o: 1
TO BE CCHPLETED B*:
ICF
SAMPLE
NUMBER
F3-0000-6-1-01
FD-uOOO-6-3-01
PD-OOOO-fe-e-01
PE-0'JOO-6-i-03
1
BOTTLE
SIZE
1000
1000
aO
10CO
SAMPLE
DESCRIPTION
FIELD SAMPLE
FIELD SAMPLE
FIELD SAMPLE
BACKUP SAMPLE
FIELD TEAM
SAMPLER
'INITIAL)
i
TIRE 1 COMMENTS ill .RECEIVES; COMMENTS
SAMPLES . ;
: ; : T :;;
i
: I Ni
: . : , ft:
: • N;
CHLORINE TEST:
SHIPPED BY:
. RECEIVE:- AT LAB BY:
! SATE TIME
; SENT TO:
J
J
i
; :-ATE
LAB ADDRESS: lihiJITIiX i3
BAY St. LCjIS tsfi'E«Mt3H»EJ»TAl.
CHEMISTS .Ai. :.;£. ll.S :
.
NSTL. P.S -3;5:<
.
TIRE
:
, ,li FDS EiAMPLE: SOTT.E BROKEK, 5CTTLE BiSSl.lS, CVERFL.E5 -CTTu. f.t» MS :S5?FEB
: 12) F3R EiiiMPLE: BOTTLE BSOfcES, BOTTLE HISSING, SETTLE ICfcTiMMTES. TEflfiEfiATUftE CRITERIA KCT ".E7
I Ci FM ElAflPLE: III MELTED, BOi LEAKING
: i lid coaunts should concur with NPSIS SAMFLE RECEIPT i
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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 SCREENS FOR 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 Number",
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 6 comprised of 8 samples and appropriate controls as covered in Section
9.4 of this QAPjP. The composition of each set is documented on a "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 'set1 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 an '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 Qo to -20oC.
An 'E)CrRACT 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 win 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.
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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 mg/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 ECL facility.
The sample extracts will be disposed of as hazardous waste by an EPA-approved hazardous
waste disposal firm or contractor at an EPAapproved dispsosal 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 Confirmations
at ECS (effective 06/05/89)
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 ECL, 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 NFS EXTRACT SHIPMENT form, filling in the Date Received at ECS,
Condition of Shipment, Number of Refrigerator where stored, the Container Number,
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 jthen place the extracts in containers
labeled by date and store in a refrigerator at 4°C.
• The Sample Custodian will make necessary copies of paperwork received with the
extract shipment giving all the original paperwork to the NFS 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
NFS EXTRACT SHIPMENT form.
• The GCMS analyst should remove extracts from the designated refrigerator, analyze
the extracts by GCMS, then complete the remainder of the NFS Extract Shipment
form and the GCMS Data Sheets. The analyst should give all completed forms and
GCMS spectra to the Technical Monitor.
• The Technical Monitor will use the information from the NFS EXTRACT SHIPMENT
form to complete an overall tracking form, the NFS GCMS EXTRACT TRACKING
FORM. He will send a copy of the GCMS Data Sheet to the NFS 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.
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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 GC/MS confirmation attempt.
• Disposal of extracts will 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 081299; 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 stored.
-------
Section No. 7
Revision No. 4
Date: December 1989
Page 4 of 6
FIGURE 7-1
SAMPLE RECEIPT SCREENS FOR NPS LABORATORIES
I ill 11 |
C O OOO
— Q. Q. ift. O. =
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Section No. 7
Revision No. 4
Date: December 1989
Page 5 of 6
FIGURE 7-2
NPS EXTRACT SHIPMENT
£
fr>4
X
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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. 1105
» WALK-IN/UPRIGHT
FREEZERS/BLDG. 2204/110!
REMARKS
PERSON CHECKING
PERSON CHECKING
-------
Section No. 8
Revision No. 4
Date: December 1989
Page 1 of 6
8. CALIBRATION PROCEDURES AND FREQUENCY
8.1 Method 6 Standards
8.1.1 Calibration Solutions
Calibration solutions will be provided and sent 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 FORM*. 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 6 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 FORM1 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 anatyte. 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 8.12.
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
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Section No. 8
Revision No. 4
Date: December 1989
Page 2 of 6
against the ECL prepared standards before use. The calibration solutions and ECL prepared
standards must differ by no more than ± 15%. Following the comparison, all values must be reported
to the ECL 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 ECL 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 ECL 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 Calibration of Instrumentation
8.2.1 Calibration of Gas Chromatograph
A Hewlett-Packard 5890 A dual capillary GC with Nitrogen-Phosphorus Detectors (NPDs) will be
used to analyze Method 6 samples. The internal standard technique below will be used.
The internal standard (IS) selected for use with Method 6 is 2,4,5,6-tetrahydro-2-pyrimidinethiol,
and it is compatible with the GC columns and chromatographic conditions for this method.
A minimum of three calibration standards will be used with each calibration standards mix, and
the lowest concentratbn of each must be at the Minimum Reporting Level (MRL). The higher
concentrations will span the range of concentrations expected in the sample extracts and in the
Laboratory Control Spikes (LCS).
Following injection of the calibration standards, the relative response (RRJ of each analyte to
the IS is calculated with the following equation:
RRa = Aa / Aj, , where
Aa = Area of the analyte
AJ, = Area of the interred standard
The calibration curve is generated by plotting RRa vs. analyte concentration in ug/liter.
The working calibration curve must be verified each day or each working shift. If the response
for any analyte varies from the predicted response by more than ± 20%, the test must be repeated
-------
Section No. 8
Revision No. 4
Date: December 1989
Page 3 of 6
using a freshly prepared calibration standard. Alternatively, a new calibration curve must be prepared
for that analyte if, in using the freshly prepared calibration standard, the predicted response for the
anafyte continues to vary by more than ± 20%.
If a new calibration curve must be prepared, the ECL Project Leader must be informed.
8.2.2 Calibration of HR GC/MS
Scanning Mode - The instrument is calibrated by the MCAL and CALJB routines in the
MAT 312 oprations manual
MID Mode - The instrument must be further calibrated by using ESCAW 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), 995-1000.
-------
Section No. 8
Revision No. 4
Date: December 1989
Page 4 of 6
FIGURE 8-1
, STANDARD SOLUTION DATA FORM
CO
o
to
to
• d.
II— ^
• <: i^l
:=!. i i
!°;?1 i°i
I M 3
| ||i JS!
io: 1"^.
i-iic.;
JS;—. IOI
:-«
il2! II
;O:
fc!
V)
-------
Section No. 8
Revision No 4
Date: December 19B9
Page 5 of 6
FIGURE 8-2
CALIBRATION SOLUTION RECEIVING FORM
Date Received: °*te Checked:.
Person Receiving Person Checking:.
Mare Samples Iced?J_^ Relinquished Custody: (Yes/No)
Method No: (1,3,or 6) .
(circle one)
Contents:
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:
Contents on condition of Calibration Solutions:
-------
Section No. 8
Revision No. 4
Date: December 1989
Page 6 of 6
FIGURE 8-3
STANDARD DILUTION FORM
0
b
e
c
ea
o
h.
O
V)
-------
Section No. 9
Revision No. 4
Dote: December 1989
Page 1 of 2
9. ANALYTICAL PROCEDURE
9.1 Summary Of Method
This Method is applicable to the determination of ethylene thiourea (ETU) in ground water.
The ionic strength and pH of a measured 50 ml volume of sample are adjusted by addition of
ammonium chloride and potassium flouride. The sample is poured onto an Extrelut\ column. ETU is
eluted from the column in 400 ml of methylene chloride. The extract is solvent exchanged to ethyl
acetate and concentrated to a volume of 5 ml.
Capillary gas-chromatography with nitrogen-phosphorus detectors is used for both primary and
secondary analyses of the sample extracts.
For sample extracts with suspected-positive ETU residues, (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
ETU.
9.2 Major Equipment/Instrumentation To Be Used With Method 6
• Hewlett-Packard 5890A dual capillary gas chromatograph with dual nitrogen-
phosphorus detectors. Similar GC for backup.
• Hewlett-Packard 7673A autosampler. Identical autosampler for backup.
• Hewlett-Packard 3359A 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
* 4.1.1 Follow by washing with tap water... Thorough rinsing with acetone, methylene
chloride, and hexane following oven heating.
* 6.1.1 120 ml bottles
* 6.1.1 caps with PTFE-liners
* 6.2.4 Glass, 1 to 1.5 ml capacity with TFE septa
* 6.3 Hengar granules, amphoteric alurdum granules (Henry Troemner)
Denotes reference to Battelle's Method and is not part of the ECL numbering system.
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Section No. 9
Revision No. 4
Dote: December 1989
Page 2 of 2
6.7 Hewlett Packard Gas Chromatograph 5890 (2643A10048) with Autoinjector 7673A
(2730A09113) with Omniscribe recorder (Model D5118-1; 134310-10070) utilizing an
A/D 18652A convenor (2135A12210) and a 3359A Laboratory Automation System
(2219A11648).
6.7.1 Primary column -15m long X 0.25 mm
6.7.2 Confirmation column - 30 m long X 0.25 mm I.D. SPB-35
7.1 Reagent water - Reagent water was prepared by passing tap water through a
Millipore - MILLIR04/MILUQ water purification system (Resistance => 10
megaohms/cm
The propylene thiourea was prepared and supplied by Battelle-Columbus.
Instrument QC Standard - 25 ul of the ETU stock standard solution
Select a representative spike concentration (suggest 10 times the MRL)
.falls between 80 and 120 percent.
is less than 80 or greater than 120 percent,.... (3) If the reanalysis fails the 80
to 120 percent recovery....
*
*
*
*
*
7.9
7.1.4
10.2.1
10.4.2
10.4.3
The
Instn
Sele
10.4.4
10.6.1.1
11.1.1
TABLE 1
When the surrogate recovery for a sample is less than 80 per
or greater than 120 percent
cent
The spiking concentration in the laboratory control standard should be 10 times the
MRL
Add preservative to all Method Blanks, Laboratory Control Standards, and any
Samples not previously preserved (Section 8.2). Pipet 50 ml
Primary conditions - Column: 15 m long Confirmation conditions - Column: 30 m
long X 0.25 mm I.D. SPB-35
* TABLES Sensitivity Ethylene thiourea (ETU) 0.025 ug/ml
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 a Laboratory Control Spike. At a maximum, 8 Field Samples may
be run in a set.
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Section No. 10
Revision No. 4
Date: December 1989
Page 1 of 6
10. DATA REDUCTION, VALIDATION, AND REPORTING
10.1 Data Reduction
ECS will use an H-P 3359A 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 anatyte 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 * e.q. 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 those sample extracts that must be referred to
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.
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Section No. 10
Revision No. 4
Date: December 1988
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 ASCII 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 samples and QC checks
related to the set and the SAMPLE DATA FORMS 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 by 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 analytes to be specified by EPA. This data
will also be reported routinely with the appropriate set data.
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Section No. 10
Revision No. 4
Date: DecembeM989
Page 3 of 6
• A situation when results from the secondary QC 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 NFS on reporting the "confirmed positives' mentioned above.
See Appendix I for the NFS 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 ECL in reporting analytes subject to rapid
reporting requirements. Form for all three Methods being run at ECL are included with this QAPjP
since an action level in one Method triggers rapid reporting for aN Methods.
It is the responsibility of the GC analyst for this Method to be aware of these rapid reporting
levels, to assure that the ECL report forms are initiated upon determining that a particular residue
associated with his/her Method is subject to rapid reporting, and to inform the ECL Project Leader
immediately.
10.6 GC/MS
10.6.1 Data Reduction
All HR GC/MS data are acquired by a Digital PDP 11/34 computer and stored on a CDC-CMD
disc drive. The LR GC/MS data are acquired by a Finnigan 5100 data system based on Supertncos
software. The data is initially manipulated by computerized routines. Identification is based on the
mass spectra and retention time of the analyte of interest (ETU). The GC/MS computer software will
search for ETU at the proper retention time and also look for characteristic ions. The ETU peak area in
the sample being confirmed and the area generated from a standard of ETU at about the same
concentration level are compared. Hard copies of data are made and kept on file. After all the results
have been received, the raw data is transferred to a magnetic tape for storage.
10.6.2 Data Validation
The hard copies of the MS data are reviewed by the mass spectroscopist 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 NFS Project Leader reviews the data,
and a decision is made 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 ECL Project Leader if the
sample(s) were extracted at ECL 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.
10.6.4 Filing and Storage of GC/MS Data
The ECL Project Leader will be responsible for the initial filing and storage of GC/MS results and
data as described in Section 10.4.
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Section No. 10
Revision No. 4
Date: December 1989
Page 4 of 6
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 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.
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Section No. 10
Revision No. 4
Date: December 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
(4)
Analysis of Raw Data
By Data System
t fhrftmat
(Hardc
)ata
n
ogram
.opy)
(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)
Monthly Reports [ (12)
-------
Section No. 10
Revision No. 4
Date: December 1989
Page 6 of 6
FIGURE 10-2
MASS SPEC CONFIRMATION SHEET
Specific details of sample extract*
Sample No. SaroP1<( C°nC g/ml-
Compound Cone Ma« Spec Ka«. Spec Ha«e Spec Ma.. Spec
NO/«1 Hinber Conftrwa- ««t Cone. Confirmation
coae
tion
1.
2.
3.
Sample No. - SanlPle C°nC
Compound Cone Mass Spec Mass Spec Mass Spec
Number Confiraa- est. Cone
tion
1.
2 .
3 .
4 .
Saiaple No.
Mass Spee
est. Cone
tion
Sample Mo.ConC 0/"1'
Co.poun. cj- H^rc H..- Spec
(ion
-------
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 Cheek
• Instrument Control—
Standard
PSF
PQF
Sensitivity
• Field Samples
- Internal Standard
- Surrogate Spike
• Performance Eval.
Sam pie*
• Shipping Blank
it_-J
• Time Storage Sample*
Frequency
1 day (or I tet If
uninterrupted
analytic of the est
extends to 2 days)
working ihHt
Maximum 8 eet
Each sample
Each »am pie
As needed
Criteria for Acceptance
0.95 < PSF < 1.05
Refer to Section 11. 21 -Criteria for
Peak Gaussian Factor (PQF) (effective
07/1 1/80; see Appendix K; Addendum
07/11/80)
£EDLforETU
No peaks wtthln the retention window
anaryte.
Rotor to Section 11 4.3
thai predicted by current calibration
curve
Response must be within +. 20% of
In calibration stds.
Recovery must fall within window of R
(recovery of surrogate from applicable
control chart) + 30 percentage points
(effective 08/18/80).
To be determined
NOT APPLICABLE TO ECLREFI
NOT APPLICABLE TO EOL REFI
Corrective Action
Raevaluatlon of QC System
Heevaluaoon of QC system
Reevaluatton of QC System
control Is establlhsed. Refer to Section 11.4.3.
2. Prepare a new calibration curve
See Individual QC checks.
Reft to Appendix _C_, Section 10.5, In the written method.
1. Check calculations.
2. Check internal and surrogate std. spiking solutions.
3. Reanalyze the sample extract
4. If reanarysts of extract remits In surrogate being 1n-
oontrol,' submit only data from IrMWitroT analysis.
5. freanarysls Mis to put surrogate In control,
reewaluate analytical method and measurement
system. Reextrejct failed sample when system is
again in control.
Out-of-contrel situation; problem must be corrected and
analytical system put beck In control as evldneced by
successfully analyzing a second P-E Sample.
EREE RESPONSIBILITIES
EREE RESPONSIBILITIES
I/ Refer to Section 14.1 and to Appendix _C_, Table Son page 24 of the written Method.
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Section No. 11
Revision No. 4
Dele: December 1989
Page 2 of 7
11.2 Conflrmatlonal (Secondary-Column) GC Analyses
Type of QC Check
• Calibration Standards
• Instrument Control
Standard
Sensitivity
• Method Blank
• Shipping Blank
• Quantitation
- Calibration Std.
- Analyte Concentration
Value
Frequency
min. 1 day or
each working
shift
1 day
1 set
Criteria for Acceptance
All analyte responses within +
20% of that predicted by current
calibration curve.
> EDLforETU
No peak within retention window
of any analyte >. V4 MRL for that
analyte
Corrective Action
1 . Prepare a fresh calibration
standard, or
2. Establish a new calibration
curve
Revaluation of GC System
Out-of-control situation; Method
Blank must be brought back in
control before proceeding.
NOT APPLICABLE TO ECL REFEREE RESPONSIBILITIES
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 C . Table 5 on page 24 of the written Method.
11.2.1 Criteria for Peak Gaussian Factor (PGF) (effective 07/11/89; See Appendix K;
Addendum 07/11/89)
• Using PGF data points for the first 20 valid sets of Method 6 data, calculate x, standard
deviation, and RSD. if BSD <. 20% and no more than 3 outliers,
establish a 3 o control chart around x, with x +. 2 RSD as warning limits; x ± 3 RSD
as control limits.
• Plot the succeeding 5 PGF data points for the next 5 sets.
• Reconstruct control charts for each 5 sets using the most recently generated PGF data
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.
11.3 GC/MS Confirmation
• GC/MS Confirmation will be required for all compounds confirmed by second column GC
analysis.
-------
Section No. 11
Revision No. 4
Dote: December 1989
Page 3 of 7
• 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 additional sample treatment is performed for GC/MS analysis (blowdown, etc.), the
standard and sample must both undergo the same treatment.
• 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 are scanned
11.4 Control Charts
11.4.1 Establishing Control Charts
A. ECU, as a referee lab for Method 6, 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 analytes 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.
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%.
-------
Section No. 11
Revision No. 4
Date: December 1989
Page 4 of 7
3. Surrogate
In establishing the control chart for the surrogate, criteria in C(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 quality
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 primary column will be plotted on the
control chart for each analyte.
11.4.4 Out-of-Corrtrol Situations
1. In the following instances, analytical work must be stopped until an "in-control" situation is
established.
a. The same analyte is outside ± 3 o twice in a row, even though > 85% of the total
analytes are in control.
2. An 'alert* situation arises when one of the following occurs:
a. Three or more consecutive points for an analyte are outside +. 2 o but inside the ±
3o
b. A run of 7 consecutive points for an analyte above or below the mean.
c. A run of 7 points for an analyle in increasing or decreasing order.
The 'alert" situation implies a trend toward an 'out-ofcontrof 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.
-------
Section No. 11
Revision No. 4
Date: December 1989
Page 5 of 7
11.4.5 Updating Control Charts
Following establishment of the control chart, a spiked control (s) 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 'NFS GROUNDWATER QUALITY
ASSURANCE DATA FORM1, 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
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,
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 6
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
-------
Section No. 11
Revision No. 4
Date: December 1989
Page 6 of 7
have in the folder documentation of the problem/ exception and all supporting information and data.
A form 'EXCEPTIONS TO NPS QAPjP1 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
Dale Method
Reference No.
Suggested Exception(s):
Signature of Person Seeking Exception
Approved Disapproved
Comments:
Bob Maxey, Technical Monitor
-------
Section No. 12
Revision No. 4
Dote: 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 6 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
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Section No. 12
Revision No. 4
Dote: 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 6 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 ETU 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 6; Printed Analytical Procedure for Method 6
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 6 analytical work. Ftoutine 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.
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 pants 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
4) Filaments (at least two of each)
-------
Section No. 13
Revision No. 4
Dote: December 1989
Page 2 of 2
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= VW1/2)
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(l/2) is the
peak width at half height.
• Peak Gaussian Factor (PGF). See Figure 14-1 at the end of this section.
PGF = 1.83XVW1/2) , 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)
n
S (xr~x)2
i=1 .where
n-1
x^.x,, = 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
Dote: December 1989
Page Z of 3
• Relative Standard Deviation (BSD)
RSD = CVX100
• Mean Recovery (R)
n
R= S Rj/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 = sXt(.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)
H
PSF
PGF =.
0.5 x W
i
1.03 x W
M/IO
sn
sa. as
N I H II t C 8
-------
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 'set1 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.
;•-
AH 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.
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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 6. 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 6 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 6. 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 6.
The Technical Monitor for Method 6 will provide the ECL Analytical Coordinator with a quarterly
TECHNICAL MONITOR PROGRESS - QA REPORT, Figure 16-2, a copy of which appears in this
section. Copies of the 'MONTHLY CONTRACT MONITORING - QA REPORT1 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 E-CL'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, Figure 16-
3. A copy of this report is included in this section.
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Section No. 16
Revision No. 4
Date: December 1989
Page 2 of 4
Method 0
FIGURE 16-1
EPA REFEREE LABORATORY PROGRESS - QA REPORT
Report Period
Analyst
Date
I. Progress:
0 samples received
S samples analyzed
9 samples invalidated
No. of data sets sent to EPA Data Manager
2. Standards: 9 stock standards diluted
Results of check before using dilution
3. Bench Level Corrective Actions (s)
Date
Problem
Action Taken
Verification of Correction
Sample set analyzed prior to problem
(Use back of page and same format co report additional corrective
actions.)
A. Problems (Project-Related):
5. Information requested by Technical Monitor - (control charts, etc.)
6. Changes la Personnel:
7. Comments:
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Section No. 16
Revision No. 4
Date. December 1989
Page 3 of 4
FIGURE 16-2
TECHNICAL MONITOR PROGRESS - QA REPORT
Method
Laboratory
Report Period
Date
I. Progress:
* samples received
t samples analyzed
t samples invalidated •
No. for data sees sent to EPA. Data Manager
2. Major Problems and Status
a. Technical:
b. Contractural:
3. Comments
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Section No. 16
Revision No. 4
Date: December 1989
Page 4 of 4
FIGURE 16-3
ANALYTICAL COORDINATOR STATUS REPORT
Report r«±rioa_
Prepared By _
Date
Monthly - Financial States
- Contract Administrative Needs
Quarterly - Data Summary
- Copies of quarterly reports from Technical Monitors
-------
Appendix A
Revision No. 4
Date: December 1989
Page 1 of 6
APPENDIX A
SAMPLE CUSTODY
-------
ENVIRONMENTAL CHEMISTRY LABORATORY
NPS SAMPLE LOGGING
METHOD
(1,3,6)
PREPARED BY:
DATE:
LAB. I.D.
(FIELD SAMPLE f)
I
DATE SAMPLBD
DATE SHIPPED I DATE RECEIVED
TIME SAMPLED | CONDI
-------
NFS SET COMPOSITION FORM
METHOD 6
APPROVED BY PROJECT OFFICER Set No.
SIGNATURE
DATE
SET CONTROLS
1. Method Blank
2. Lab Control Spike
NFS FIELD SAMPLES
Field Sample No. Date Sampled Date Arrived At ECL
3.
4.
5.
6.
8.
9.
10.
-------
SAMPLE CONTROL RECORD
EPA/ECL
LABORATORY
SAMPLE NO.
REMOVED
BY
DATE AND TIME
REMOVED
REASON
DATE AND TIME
RETURNED
"T"
-
-------
ECL NFS SAMPLE TRACKING FORM
METHOD 6
Set #
Sample Nurcber
Date
Sample
Taken
Date
Rec'd
at ECL
Date
Extracted
Date
Analysis
Completed
Date Removed
for GC/MS
Confirmation
GC/MS
Confirmation
Completed
-------
NFS Method #6.Extract Storage Data Sheet
Extracts Relinquished By Date: Received By
Set:
Date:
.•tap le Code
ho Stored
Date
Stored
lefrig. or
reezer No.
loom No.
lemoved
By
urpose
Date
Removed
Returned
by
Date
Return
Date Disposed:
Authorized by:
-------
Appendix B
Revision No. 4
Date: December 1989
Page 1 of 27
APPENDIX B
BATTELLE'S VERSION
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Method 6. Determination of Ethylene Thiourea (ETU) in Ground
Water by Gas Chromatography with a Nitrogen-Phosphorus Detector
1 . SCOPE AND APPLICATION
1.1 This is a gas chromatographic (GC) method applicable to the
determination of ethylene thiourea (ETU, Chemical Abstracts
Registry No. 96-45-7) in ground water.
1.2 This method has been validated in a single laboratory. The
estimated detection limit (EDL) has been determined and is
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 chromatogrctr.s. 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 ETU,
identification must be confirmed by at least one additional
qualitative technique.
2. SUMMARY OF METHOD
2.1 The ionic strength and pH of a measured 50-mL volume of sample
are adjusted by addition of ammonium chloride and potassium
fluoride. The sample is poured onto an Extrelut column. ETU is
eluted from the column in 400 mL of methylene chloride. The
extract is solvent, exchanged to ethyl acetate and concentrated
to a volume of 5 mL. Chromatographic conditions are described
which permit the separation and measurement of ETU in the
extract by GC with a nitrogen-phosphorus detector (NPO).
3. DEFINITIONS
3.1 Artificial ground water -- sn 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 limit (EDt) -- The minimum concentration of
a substance that can be measured and reported with confidence
that the analyte concentration is greater than, zero as
determined from the analysis of a sample in a given matrix
• . • • •
1
-------
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 v.Uh
n-1 degrees of freedom or the level of the compound in a sample
yielding a peak in the final extract 'with signal-to-noise ratio
of approximately five, whichever value is higher.
3.4 Internal standard -- a pure compound added to a sample extract
in a known amount and used to calibrate concentration
measurements of other analytes that are sample components. The
internal standard must be a compound that is not a sample
component.
3.5 Instrument quality control (QC) standard -- an ethyl acetate
solution containing specified concentrations of specified
analytes. The instrument QC standard is analyzed each working
day prior to the analysis of sample extracts and calibration
standards. The performing laboratory uses this solution to
demonstrate acceptable instrument performance in the areas of
sensitivity, column performance, and chromatographic
performance.
3.6 Laboratory control (LC) standard -- a solution of ETU prepared
in the laboratory by dissolving a known amount of pure ETU in a
known amount of reagent water. In this method, the 1C standard
is prepared by adding an appropriate volumes of the ETU standard
solution to reagent water.
3.7 Laboratory reagent blank -- an aliquot of reagent water analyzed
as if it were a sample.
3.8 Performance evaluation sample -- A water-soluble solution of
method analytes distributed by the Quality Assurance Branch.
Environmental Monitoring and Support Laboratory, USEPA, Cincin-
nati, Ohio. A small measured volume of the solution is added to
a known volume of reagent water and analyzed using procedures
identical to those used for samples. Analyte true values are
unknown to the analyst.
3.9 Quality control check sample -- a water soluble solution
containing known concentrations of analytes prepared by a
laboratory other than the laboratory performing the analysis.
The performing laboratory uses this solution to demonstrate that
it can obtain acceptable identifications and measurements with a
method. A small measured volume of the solution is added to a
known volume of reagent water and analyzed with procedures
identical to those used for samples. True values of analytes
are known by the analyst.
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 w^h 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 - • .
A.I 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 chrom-
atograms. " 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.
A.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 AOO'C for 1 hour. Do
not heat volumetric ware. Thermally stable materials
might not be eliminated by this treatment. Thorough
rinsing with acetone and methylene chloride may be
substituted for the heating. After drying and cooling,
seal and store glassware in a clean environment to
prevent any accumulation of dust or other contaminants.
Store inverted or capped with aluminum foil.
4.1.2 The use of high purity reagents and solvents helps to
minimize interference problems. Purification of
solvents by distillation in all-glass systems may be
required.
A.2 Interfering contamination may occur when a sample containing z
low concentration of ETU is analyzed immediately following a
sample containing a relatively high concentration of ETU.
Between-sample rinsing of the sample syringe and associated
equipment with ethyl acetate can minimize sample cross contamin-
ation. After analysis of a sample containing high concentra-
tions of ETU, one or more injections of ethyl acetate should be
made to ensure that accurate values are obtained for the next
sample.
A.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
ground water sampled. Positive identifications must be confirm-
ed using the confirmation column specified in Table 1.
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5. SAFETY
5.1 ETU is a cancer suspect agent and teratogen. Primary standaids
of ETU should be prepared in a hood. A NIOSH/KESA approved
toxic gas respirator should be worn when the analyst handles
high concentrations of ETU. Each laboratory is responsible for
maintaining a current awareness file of OSHA regulations
regarding the .safe handling of the chemicals specified in this
method. A reference file of material safety data sheets should
also be made available to all personnel involved in the chemical
analysis. Additional references to laboratory safety are
^
available and have been identified for t^e 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 -- 60-ml screw cap vials (Pierce No.
13075 or equivalent) and caps equipped with a PTFE-faced
silicone septa (Pierce No. 12722 or equivalent). Prior
to use, wash and heat vials and septa as described in
Section 4.1.1.
6.2 GLASSWARE
6.2.1 Concentrator tube, Kuderna-Oanish (K-0) -- 10- or 25-ir,L,
graduated (Kontes K-5700SO-2S25, K-S700SO-102S or
equivalent). Calibration must be checked at the volurr.es
employed in the test. Ground glass stoppers are used tc
prevent evaporation of extracts.
6.2.2 Evaporative flask, K-0 -- 500-tnL (Kontes K-570001-0500
or equivalent). Attach to concentrator tube with
springs.
6.2.3 Snyder column, K-0 -- three-ball macro (Kontes K-503000-
0121 or equivalent).
6.2.4 Vials -- Glass, 5- to 10-ml capacity with TFE-fluoro-
carbon lined screw cap.
6.3 Boiling stones -- carborundum,' S12 granules (Arthur H. Thomas
Co. S1590-033). Heat at 400'C for 30 rain prior to use. Cool
and store in a desiccator.
6.4 Water bath -- Heated, capable of temperature control (±2'C).
The bath should be used in a hood.
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6.5 Balance -- Analytical, capable of accurately weighing to the
nearest 0.0001 g.
6.6 Tube heater -- Capable of holding eight K-0 concentrator tubes
and heating the mid-section of the tubes to 3S-40*C while
applying a nitrogen stream.
6.7 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.
6.7.1 Primary column -- 10 m long x 0.25 mm 1.0. 03-Wax 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.
6.7.2 Confirmation column --5m long x 0.25 mm 1.0. 06-1701
bonded fused silica column, 0.25 urn film thickness
(available from J&U).
6.7.3 Detector -- Nitrogen-phosphorus detector (NPO). This
detector has proven effective in the analysis of spiked
reagent and artificial ground waters. 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. P.£AG£NTS AND CONSUMABLE KATEP.IALS
7.1 Reagent water -- Reagent water is defined as 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.
7.2 Acetone, methylene chloride, ethyl acetate -- Oistilled-in-glass
quality or equivalent.
7.3 Nitrogen gas -- high purity.
7.< Extraction column, Extrelut QE -• Obtained from EH Science
(Catalog No. 902050-1).
7.5 Ammonium chloride, granular, ACS grade •- for pH and ionic
strength adjustment of samples (available from Baker Chemical
Co.)-
-------
7.6 Potassium fluoride, anhydrous, ACS grade -- for ionic strength
adjustment of sample (available from Baker Chemical Co )
7.7 Mercuric chloride, granular, ACS grade -- used as sample preser-
vative (available from Hallinckrodt).
t
7.8 Dithiothreitol (OTT) -- for use as a free-radical scavanger
(available from Aldrich Chemical Co.).
7.8.1 OTT in ethyl acetate, 1000 ug/mL -- Prepare by adding
1 g OTT to a 1-L volumetric flask and diluting to volume
with ethyl acetate. Store at room temperature.
7.9 Propylene thiourea (PTU) ••- for use as a surrogate standard.
Prepared from carbon disulfide and 1,2-diaminopropane using the
procedure published by Hardtmann, et. al. (Journal of Medicinal
Chemistry, 18(5), 447-453, 1975).
7.10 3,4,S,6-Tetrchycro-2-pyrimicinethiol (THP) -- >98% purity, for
use as an internal standard (available from Aldrich Chemical
Co.).
7.11 STOCK STANDARD SOLUTION (0.10 ug/uL) - The stock standard
solution may be purchased as a certified solution or prepared
from pure standard material using the following procedure:
7.11.1 Prepare stock standard solution by accurately weighing
approximately 0.0010 g of pure ETU. Dissolve the ETU in
ethyl acetate containing 1000 ug/mL of OTT and dilute to
volume in a 10-mL volumetric flask. Larger volumes may
be used at the convenience of the analyst. If ETU
purity, is certified at 96% or greater, the weight may be
used without correction to calculate the concentration
of the stock standard. Commercially prepared stock
standards may be used at any concentration if they are
certified by the manufacturer or by an independent
source.
7.11.2 Transfer the stock standard solution into a TFE-fluoro-
carbon-sealed screw cap vial. Store at 4*C and protect
from light.
7.11.3 The stock standard solution should be replaced after two
weeks qr sooner if comparison with laboratory control
standards indicates a .problem.
7.1Z INTERNAL STANDARD SPIKING SOLUTION -- Prepare an internal
standard spiking solution by accurately weighing approximately
0.0010 g of pure THP. Dissolve the THP in ethyl acetate
containing 1000 ug/mL of OTT and dilute to volume in a 10-raL
volumetric flask. Transfer the internal standard spiking
solution to a TFE-fluorocarbon-sealed screw cap' bottle and store
* 6 '
-------
at A'C and protect from light. Addition of 50 ul_ of the
internal standard spiking solution to 5 ml of sample extract
results in a final internal standard concentration of 1.0
Solution should be replaced when ongoing QC (Section 10)
indicates a problem.
7.13 SURROGATE STANDARD SPIKING SOLUTION -- Prepare a surrogate
standard spiking solution by accurately weighing approximately
0.0010 g of pure PTU. Dissolve the PTU in ethyl acetate
containing 1000 ug/mL of DTT and dilute to volube in a 10-mL
volumetric flask. Transfer the surrogate standard spiking
solution to a TFE-fluorocarbon-sealed screw cap bottle and store
at <*C and protect from light. Addition of 5 uL of the
surrogate standard spiking solution to a 50-mL sample prior to
extraction results in a surrogate .standard concentration in the
sample of 10 ug/L and, assuming quantitative recovery of PTU, a
surrogate standard concentration in the final extract of
0.10 ug/ml.
7.14 INSTRUMENT QC STANDARD -- Prepare the instrument QC standardly
adding 10 uL of the ETU stock standard solution, 1.0 ml of the
internal standard spiking solution, and 100 uL of the surrogate
standard spiking solution to a 100-mL volumetric flask and
diluting to volume'with ethyl acetate containing 1000 ug/mL of
OTT. Transfer the instrument QC standard to a TFE-fluoroccrbon-
sealed screw cap bottle and store at room temperature.
Solution should be replaced when ongoing QC (Section 10)
indicates a problem.
8. SAMPLE COLLECTION. PRESERVATION. AND STORAGE
8.1 Grab samples must be collected in 60-ml screw cap glass vials
(Section 6.1.1). 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 rog/L. Add 60 uL of a
solution containing 10 mg/ml of mercuric chloride in
water to the sample bottle at the sampling site or in
the laboratory before shipping to the sampling site.
Mercuric chloride is a highly toxic chemical. Mercuric
chloride must be handled with caution, and samples
containing mercuric chloride must be properly disposed.
8.2.2 After the sample is collected in the bottle containing
preservative, seal the sample bottle and shake vigor-
ously for 1 min.
-------
8.2.3. £TU can degrade quickly in water even when the sample is
refrigerated. Samples should be extracted as soon as
possible and must be extracted within 14 days of
collection. The samples must be iced or refriaerated at
4*C and protected from light from the time of "col lection
until extraction. Preservation study results given in
Table 4 indicate that samples are stable for 14 days
when stored under these conditions. However, analyte
stability may be affected by the matrix, therefore, the
analyst should verify that the preservation technique is
applicable to the samples under study.
8.3 EXTRACT STORAGE
8.3.1 Extracts should be stored at 70*C away from light.
Preservation study results given in Table 4 indicate
that extracts are stable for at least 28 days when
stored under these conditions. The analyst should
verify appropriate extract holding tines applicable to
the samples under study.
8. CALIBRATION
9.1 Establish GC operating parameters equivalent to those indicated
in Table 1. 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 compat-
ible in analytical behavior to the compound of interest. The
analyst must further demonstrate that the measurement of the
internal standard is not affected by method or matrix interfer-
ences. THP has been identified as a suitable internal standard.
9.2.1 Prepare ETU calibration standards at a minimum of three
(suggested five) concentration levels by adding volumes
of the ETU stock standard to a volumetric flask. To
each calibration standard, add a known constant amount
of one or more internal standards, and dilute to volume
with ethyl acetate containing 1000 ug/mL of OTT. One of
the calibration standards should be representative of an
ETU concentration near, but above, the EOL. The other
concentrations should correspond to the range of concen-
trations expected in the sample concentrates, or should
define the working range of the detector.
9.2.2 Inject 2 uL of each calibration standard and tabulate
the relative response for ETU to the internal standard
(RRa) using the equation:
RRa • Aa/Ais
. •
8
-------
where: Aa = the peak area of ETU, and
AJS = the peak area of the internal standard.
Generate a calibration curve of RR2 versus £TU concen-
tration in the sample in pg/L.
9.2.3 The working calibration curve must be verified on each
workipg shift by the measurement of one or more calibra-
tion standards. If the ETU response varies from the
predicted response by more than ±20%, the test must be
repeated using a fresh calibration standard. Alterna-
tively, a new ETU calibration curve must be prepared.
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 QC samples, laboratory control
standards, and performance evaluation (PE) samples as continuing
checks on laboratory performance; the analysis of spiked samples
as a continuing check on recovery performance; the analysis of
method blanks as a continuing check on contamination; and
frequent analysis of the instrument QC standard to assure
acceptable instrument performance.
10.2 INITIAL DEMONSTRATION OF CAPABILITY -- To establish the ability
to perform this method, the analyst must perform the following
operations.
10.2.1 Select a representative spike concentration (suggest
IS times the EDL) for ETU. 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 concen-
tration.
10.2.2 Using a syringe, add SO uL of the LC sample concentrate
to each of a minimum of four SO-mL 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) an
-------
•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.
Recalculate or reanalyze the extract if the above steps
fail to reveal the cause of the noncompliant surrogate
recoveries. If reanalysis of the sample or extract
solves the problem, only submit the sample data fron 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 percant from the average peak
area or height for the internal standard in the calibra-
tion standards.
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
.
11
-------
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 t'he 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 p£rformance.
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 +307. 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).
10.6.1.1 The spiking concentration in the laboratory
control standard should be 15 times the £01.
10.6.1.2 Spike a reagent water aliquot with a labora-
tory 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 parameter. Calcu-
late each percent recovery (Ri) as (lOOxA)VT,
• •
12
-------
where I is the known true concentration of the
spike.
10.6.1.3 Compare the percent recovery (R^) for each
parameter 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:
Rj/n
and
where:
/ ; 'n \ .- n \2
I-(I. «,*)-( I «,)
n-1 \i = l / \i = l /
= number of measurements for each
analyte, and
= individual percent recovery
value.
Calculate QC acceptance criteria as follows:
Upper Control Limit (UCL) « R * 3SR
Lower Control Limit (LCL) = R - 3$R
Alternatively, the data generated during the
initial demonstration of capability (Section
10.2) can be used to set the initial upper and
lower control limits.
Update the performance criteria on a contin-
uous basis. After each five to ten new
recovery measurements (R^s), recalculate R and
So 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.
13
-------
Monitor all data from laboratory control
standards. Analyte recoveries must fall
within the established control limits.
If the recovery of ETU falls outside the
designated range, the laboratory performance
for ETU is judged to be out of control, and
the source of the problem must be immediately
identified and resolved before continuing the
analyses. The analytical result for ETU in
samples is suspect and must be so labeled.
All results for ETU for 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
ire 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
w\thin 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.K1 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
EOL.
10.7.1.2 Analyze one sample aliquot to determine the
background concentration (8) of each para-
meter. Spike a second sample aliquot with a
laboratory control (LC) sample concentrate
(the volume of the spike should be kept to a
minimum so the solubility of the analytes of
interest in water will not be affected) and
analyze it to determine the concentration
after spiking (A) of each parameter. Calcu-
late each percent recovery (Rj) as
100(A-8)%/T, where T is the known true •
concentration of the spike.
10.7.1.3 Compare the percent recovery (R^) for each
parameter with QC acceptance criteria deter-
14
-------
mined by the analysis 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 ETU falls outside the
designated range, and the laboratory perfor-
mance for ETU is judged to be in control, the
recovery problem encountered with the dosed
sample is judged to be matrix-related, not
system-related. The result for ETU 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 50-mL 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 ETU which is greater than or equal to one-half the EOL
for ETU, determine the source of contamination before processing
samples and eliminate the interference problem.
10.9 -ASSESSING INSTRUMENT PERFORMANCE (INSTRUMENT QC STANDARD) --
Instrument performance should be monitored on a daily basis by
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 5. Inability to demonstrate
acceptable instrument performance indicates the need for
reevaluation of the GC-NPO system. A GC-NPD chromatogram
generated from the analysis of the instrument QC standard is
shown in Figure 1. The sensitivity requirements are set based
on the EDL published in this method. If the laboratory EDL
differs from that listed in this method, concentrations of the
instrument QC standard compounds must be adjusted to be com-
patible with the laboratory EOL. 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 1.
IS
-------
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.
1. PROCEDURE
11.1 SAMPLE EXTRACTION
11.1.1 Add preservative to any samples not previously preserved
(Section 8.2). Pipet 50..mL of water sample into a 60-mL
bottle containing 1.5 g of ammonium chloride and 25 g of
potassium fluoride. Close bottle and shake vigorously
until salts are dissolved. Spike sample with 5 uL of
the surrogate standard spiking solution.
11.1.2 Pour contents of bottle onto Extrelut. column. Allow the
column to stand undisturbed for 15 min.
11.1.3 Add 5 mL of 1000 ug/mL DTT in ethyl acetate to a K-D
concentrator tube equipped with a 500-mL flask.
11.1.4 Add 400 mL cf methylene chloride in 50-75 mL portions to
the Extrelut column and collect the eluant in the K-D
• apparatus (Section 11.1.3). The water, ammonium
chloride and potassium fluoride remain on the Extrelut
column while the ETU is removed from the column in the
methylene chloride eluate. Discard the Extrelut column.
11.2 EXTRACT CONCENTRATION
11.2.1 Add 1'or 2 clean boiling stones to the K-0 apparatus and
attach a macro Snyder column. Prewet the Snyder column
by adding about 1 mL of methylene chloride to the top.
Place the K-0 apparatus in a 65-70'C water bath so that
the K-0 tube is partially immersed in the hot water, and
the entire lower rounded surface of the flask is bathed
with hot vapor. When the~apparent volume of liquid
reaches S mL, remove the K-0 apparatus and allow it to
drain and cool for at least 10 min.
11.2.2 Reduce the liquid volume in the K-0 tube to approximat-
ely 1 mL by placing the sample extract in a tube heater
at 35-40*C under a stream of nitrogen. The tube heater
heats the solvent in the K-0 tube at volume markings
between 1 and 10 mL.
11.2.3 Dilute sample extract to 5 ml with ethyl acetate; rinse
walls of K-0 tube while adding ethyl acetate. Immed-
iately spike sample extract with 50 uL of internal
standard spiking solution. Agitate sample extract to
disperse internal standard. Transfer sample extract to
.
16
-------
a GC vial and determine ETU by GC-NPO as described in
Section 11.3. Sample extracts should be protected from
light and analyzed within 24 hours of extraction.
Sample extracts can be stored for up to 28 days, frozen
at -10*C and protected from light.
11.3 GAS CHROMATOGRAPHY
11.3.1 Table 1 summarizes the recommended GC operating condi-
tions. Included in Table 1 are retention times observed
using this method. An example of the separations
achieved using these conditions are shown in Figure 1.
Other GC columns, .chromatographic conditions, or
detectors may be used if the requirements of
Section 10.1 are met.
11.3.2 Calibrate the system daily as described in Section 9.
The standards and extracts must be in ethyl acetate
containing 1000 ug/mL DTT.
11.3.3 Inject 2 uL of the sample extract. Record the resulting
peak size in area units.
11.3.4 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.
11.3.5 If the response for the peak exceeds the working range
of the system, dilute the extract with ethyl acetate
containing 1000 ug/mL OTT and reanalyze.
12. CALCULATIONS -- Calculate the ETU concentration in the sample from the
ETU relative response (RRa) to the internal standard using the
calibration curve described in Section 9-.Z.2.
13. PRECISION AND ACCURACY
13.1 In a single laboratory, ETU recoveries from reagent water were
determined at five concentration levels. Results were used to
determine the ETU £01 and demonstrate method range. EDI and
method range data are given in Table 2.
13.2 In a single laboratory, ETU 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. ETU recoveries from the two
artificial matrices are given in Table 3.
» * * *
17
-------
13.3 In a single laboratory, ETU recoveries from a ground water
preserved with mercuric chloride were determined 0, 14, and 28
days after spiking the sample with ETU. Sample extracts were
also reanalyzed after they were stored for 28 days at -10*C and
protected from light. Results were used to predict expected £TU
stability in ground water samples and sample extracts; ETU
recoveries from the preserved, spiked ground water samples and
stored extracts, are given in Table 4.
18
-------
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 Safety 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, 03370-82, "Stan-
dard Practice for Samplina Water," American Society for Testing and
Materials, Philadelphia, PA, p. 130, 1986.
6". Mitz, S., Moz, P. and P. Korte, "A Capillary Gas-Liquid Chromatographic
Method for Determination of Ethylenethiourea and Propylenethiourea in
Hops, Beer, and Grapes," J. Agric. Food Chem., 1982, 30, 593-596.
19
-------
TABLE 1. PRIMARY AND CONFIRMATION CHROMATOGRAPHIC CONDITIONS
Retention Time, cnin
Analyte
Primary column
Confirmation column
ITU
THP (internal standard)
PTU (surrogate standard)
3.5
5.1
2.7
4.5
5.0
2.2
Primary conditions:
Column:
Carrier gas:
Makeup gas:
Detector gases:
Injector temperature:
Detector temperature:
Oven temperature:
Sample:
Detector:
Confirmation conditions:
10 m long x 0.25 mm I.D. OB-Wax bonded fused
silica column (J&W), 0.25 m film thickness
He @ 30 cm/sec linear velocity
He @ 30 mL/min flow
Air
-------
TABLE 2. RESULTS FROM EOL AND METHOD RANGE STUDIES (a)
Spiking
Level ,
ug/L
5.0
10
25
100
Amt in
Blank,
P9/L
0.492 '
HO (b)
NO
NO
n(d)
7
7
7
7
R(e)
97 (c)
102
94
97
S(f)
0.845
0.886
1.31
5.96
RSO(g)
17
9
6
6
EDL(h)
5.0
-
-
-
(a) Studies conducted in reagent water; average recovery of PTU
surrogate from seven spiked reagent water samples was 100%
(RSO was 8.5%).
(b) NO = not detected.
(c) .Data corrected for amount detected in blank.
(d) n = number of recovery data points.
(e) R = average percent recovery.
(f) S - standard deviation.
(g) RSO = percent relative standard deviation.
(h) EDL = estimated detection limit in sample in ug/L; calculated by
multiplying standard deviation (S) times the students' t value
appropriate for a 99% confidence level and a standard deviation
estimate with n-1 degrees of freedom, or level of compound in
sample yielding a peak in the final extract with signal-to-noise
ratio of approximately 5, whichever value is higher.
21
-------
TABLE 3. RESULTS FROM MATRIX EVALUATION STUDIES (a)
. Amt in
Blank,
Matrix ug/L • n(e) R(f) S(g) RSO(h)
Hard (b) HO (d) 7 93 0.372 e,
Organic-contaminated (c) NO • 7 93 0.253 3
(a) Samples were spiked with at the 10 ug/L level with ETU.
(b) Absopure Natural Artesian Spring Water obtained from the Absopure
Water Company in Plymouth Michigan.
(c) Reagent water spiked with fulvic acid at the 1 mg/L concentration
level. A wel1-characterized fulvic acid, available from the
International Humic Substances Society (associated with the United
States Geological Survey in Denver, Colorado), was used.
(d) NO = not detected.
(e) n = number of recovery data points.
(f) R = Average percent recovery.
(g) S = standard deviation.
(h) RSD = percent relative standard deviation.
-------
TABLE 4. RESULTS FROM PRESERVATION STUDY
Extraction Date
Day 0
Day 0
Day 14
Day 28
Analysis Date
Day 0
Day 28 (c)
Day 14
Day 28
R(a)
86
87 r
80
45
RSD(b)
2
2
6
10
(a) R = percent recovery; average of triplicate analyses.
(b) RSO = percent relative standard deviation of triplicate
analyses.
(c) Sample extract stored for 28 days at 4*C and protected
from 1ight.
23
-------
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26
-------
Appendix C
Revision No. 4
Date: December 1989
Pagel of 11
APPENDIX C
DATA FLOW (REDUCTION, VALIDATION, AND REPORTING)
-------
CPDDE REPRESENTATION OF DATA FLOW
1. Samples are taken in the field.
2. Samples are iced and shipped to the laboratory.
3. Laboratory prepares and analyzes -field samples along with. QC sanples.
4. laboratory enters, field and QC data on a ocnpiter 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 IEM PC compatible floppy disk.
6. Laboratory sends the floppy disk to Christopher Frebis at the EPA in
Cincinnati, Ohio.
26 W. Martin Luther King Drive
Cincinnati, OH 45268
NOTE: The maximum time from item 1 to item 6 is two (2) months.
7. Computer Sciences Corporation (CSC) personnel transfer the data from PC
to IBM 3090 mainframe in North Carolina (or possibly to IEM Logical
Mainframe in Cincinnati).
8. The data is edited on the mainframe and then checked for compliance
with QC requirements using SAS, a statistical programming language.
9. A hard copy of the edited data, with "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 POEMATS
1. Hie format for any date is mm/dd/vy
A missing date should be entered 01/01/60
2. Hie format for any time is hh:mra in military time
A missing time should be entered 00:00
3. Any other data that is missing should be entered with a period (.)
4. The number of decimal places should be as follows:
Concentration 3 (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 GCMS
6. The codes for lab are as follows:
ISO . TSD
OPP OPP
WERL WER
Radian PAD
Battelle BCD
James M. Montgomery JMM
Alliance AIL
Environmental Sciences and Engineering ESE
7. The codes for Type are as follows:
Field Sample SAMP
Shipping Blank SBLK
Method Blank MBLK
Lab Control Standard I£S@
Lab Spike Sample LSS6I
Time Storage for Extract HTE@
Time Storage for Sample HZS@
where 6 is the mix letter (A,B,C or D)
and # is the spiking level (1,2 or 3)
-------
NOTES ON NPS DATA. FORMATS (cont.)
8. There should be at least one blank line between samples in the NPS data
file.
9. The codes for Concentrations and Percent Recoveries are as follows:
Not Analyzed *
Not Detected (< MiniJtum Reporting Level) -999
Saturated -777
Other -333
Below Report Lunit, but Distinct Peak -111
Above Reporting Lunit, but not Quantified f 888
10. If a reported value is greater than (>) some number in the NPS 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 t Revised "Enter Internal Standard" to "PERCENT
RECOVERY OF INTERNAL STANDARD AS COMPARED
AGAINST THE CALIBRATION STANDARD".
Motes 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. OOOES IN NFS
SAMPLE TYPE
SAMP
.(a)
— ill (^)
-333 <0)
-444 (J)
-666(9)
-777 (h)
888 (f )
-999 (?)
ooncW
MBLK
.(a)
— ill (^)
-333(d)
****
-555 (*>
****
-777W
sss a
-999 UJ
concW
SBLK
.(a)
••ill (^)
-333(0)
-444 W
-555 (f)
•-666(9)
888 (*)
-SsSo)
concW
ICS
.W
****
****
****
-* j-^^~
•J M H IV
****
-777 W
. ****
****
%rectt)
LSS,DIS
HIE, HIS
.(b)
****
-333(0)
-444 («)
****
****
-777 W
****
****
% reed)
(a) Analyte drunjed from survey (Daaeton-S and Carboxin sulfoxide) or not
analyzed on the second column or in GCMS analysis.
(b) Analyte not in mix.
(c) Analyte's concentration between MRI/2 and MRL. (If no 'confirmation is run,
a ounmtit as to why should be made.)
(d) A lab mishap, 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 cauiaait should give further
explanation.)
(e) This analyte fails QC in this set (e.g. ICS out of control) and therefore
cannot be reported; however, the analyte does not require a qualitative
challenge. This code also applies to any spike sample in a set where
the ICS is out of control.
(f) GCMS only: Sent to referee lab for GCMS analysis.
(g) This analyte falls 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
entration.)
(i) Positive, can occur in two fashions: 1) any analyte in C5CMS analysis; or
2) a qualitative only analyte on either of the first two columns.
(j) Analyte's concentration below MRI/2.
(k) Concentration above MRL for quantitative analytes, reported to three
significant figures.
(1) Percent recovery, reported to one decimal place (even if recovery is 0.0%).
-------
-333
NFS DATA REPORTING CODES (cont.)
Sarrcole (Qualitative onlv analvte)
-999 888
-333 -999
PRIM
CCNF
-333 -555 -999 888 GCHS
GCMS
(at referee)
-333 -999 888
Samole (Quantitative analvte with OC failure)
-333
-444
-666
-333 -666 -999
-333 -555 • -999 888
-333 -999 888
PRIM
CONE-
GCMS
(at referee)
Sample (Quantitative an^lvt*-* with no OC faj^VT?)
-Ill -333 -; -777a -999 cone
-333 -999 00«:
PRIM
CCNF
-333 -555 -999 888 -333 -555 -999 888 -333 -555 -999 888 -333 -555 -999 888 GCK5
-111 -333 -999 cone
-333 -999 888 -333 -999 888
-333 -999 888
-333 -999 888 GCMS
(at referee)
a = Dilute and reanalyze
-------
DMA CHECKS PERFORMED ON NFS DATA BY 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 symmetry factor within the
limits set by the method?
3. Is the instrument control standard's peak geometry factor within the
limits set by the methods?
4. Is the instrument control standard's resolution within the limits set by
the method?
5. Is the date from sampling to receipt within the limits set by the survey
requirements?
6. Is the date from sampling to eictract within the limits set by the survey
requirements?
7. Is the date from extract to analysis within the limits set by the survey
requirements?
8. Is the percent recovery of the surrogate within the limits set by the
survey requirements?
9. Is the 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 set 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?
-------
FORMAT FOR NATIONAL PESTICIDE SURVEY (NFS) DATA.
CME QQII3MNS DESCRIPTION
L 1-9 Well I.D.
13-20 Date_Sam
23-30 Date_Shp
33-40 Date_Rec
43-50 • TimeTsam
53-60 Tiioe_Ioe
[FOR MEIHODS 5 AND 9 ONLY]
64-65 pH
2 1-10 enter WELL IDENTIFICATION 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 MEIHODS 5 AND 9 ONLY]
63-66 enter pH
3 BLANK
4 1-8 IniJTenp
11-18 StbJTenp
21-29 Condition
5 1-8 enter INITIAL TEMPERATURE OF WATER
11-18 enter STABILIZED TEMPERATURE OF WATER
21-80 enter -CONDITION OF SAMPLE UPON RECEIPT AT LABORATORY
6 BLANK
7 1-6 Sanp #
9-11 Lab
14-18 Set S
21-28 Date_Spk
31-38 Date_Ext
41-48 Date Ana
51-56 Site f
59-64 Column
8 1-6 enter SAMPLE IDENTIFICATION NUMBER
9-11 enter LAB ABBREVIATION
14-18 enter SET NUMBER
21-28 enter DATE SPIKED
31-38 enter DATE EXTRACTED
41-48 enter DATE ANALYZED
51-56 enter SITE NUMBER
59-64 enter ANALYSIS COLUMN
-------
FORMAT FOR NATIONAL PESTICIDE SURVEY (NFS) DATA (cant.)
LINE COLUMNS
9 BLANK
10
11
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
Spiker
Extract
Analyst
Sean Vol
Ext_Vol
Int. Std.
% Surr
enter SAMPLE TYPE
enter SPIKER1 S INITIALS
enter EXTRACTOR'S TNTTIALS
enter ANALYST'S INITIALS
enter VOLUME OF SAMPLE
enter VOLUME OF EXTRACT
enter INTERNAL STANDARD
enter PERCENT RECOVERY OF SURROGATE
Comments
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
-------
FORMAT FOR NATIONAL PESTICIDE SURVEY (NFS) INSTRUMENT CONTROL DATA
LINE
1
COLUMNS
1-3
6-11
14-21
24-30
35-37
42-44
49-51
55-58
DESCRIPT]
I ah
Method
Date.Ana
Analyst
S/N '
PSF
PGF
Res.
2
3-?
BLANK
1-3
6-11
14-21
24-30
33-37
40-44
47-51
54-58
enter IAB ABBREVIATION
enter METHOD NUMBER
enter DATE ANALYZED
enter ANALYST'S INITIALS
enter SIGNAL TO NOISE RATIO
enter PEAK SYMMETRY FACTOR
enter PEAK GEOMETRY FACTOR
enter RESOLUTION
-------
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 to 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.
Tne 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, 2, 3. A,
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, to
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 ± 1 jimho. 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
When 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 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 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
a
ff
5
u
UJ
Q
UJ
CC
o
I-
•Ji
01
1 1 1
1 1 !
1 1 1
1 1 1
1 01 1 1
1 X 1 1
1 CC 1 I
1 - 1
1 Z 1 CD 1
1 CC 1^1
ID 1 Hi 1
1 )- 1 .u 1
1 Ul 1 1 >. 1
IO 1 Q) 1
IH 14-11
1 UJ 1 <5 1
i cc i a i
O 1 1
1 UJ 1 > 1
1 Z 1 CD 1
1 CC 1^1
ID i ai i
1 t- 1 4J 1
1 UJ 1 * 1
1 CC 1 Q 1
10 1 X 1
1 UJ 1 CO 1
1 > \ ^ I
1 O 1 O 1
1 £ 1 -u 1
1 UJ 1 • 1
1 Z 1 CO 1
1 CC 1 X 1
ID 1 01 1
1 !- 1 4J 1
1 UJ 1 • 1
1 UJ 1 Ok 1.
1 > 1^1
1 O 1 Q 1
IE 1 .u 1
1 UJ 1 <0 1
1 CC 1 O 1
1 _! UJ 1 >. I
1 C CO 1 CD I
1 *- « 1 >. 1
1 t- CC 1 O 1
! ~ a i *j i
1 Z H 1 <6 1
1 — 01 1 O 1
RECORD
IDENTIFICATION
Method/Set No.
•
f
i
i
i
i
i
i
i
•
i
i
i
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:
Xj < X2 < X3 < ... < Vj < Xa
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 5Z risk values (bolded).
Example (from Taylor)
Given the following set of ranked data:
10.45, 10.47, 10.47, 10.48, 10.49, 10.50, 10.50, 10.53, 10.58
The value 10.58 is suspected of being an outlier.
1) Calculate ru
10.58 - 10.53 0.05
ru - - - 0.454
10.58 - 10.47 0.11
2) A 5X 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 10X risk of false rejection ru - 0.409, and the value
10.58 would be rejected.
-------
TABLE 1
CALCULATION OF RATIOS
For use if if Xn is
Ratio n is between suspect
_ o 7
rio J - /
m ° iu
(Xn - X2)
/Y Y 'S
(•^a -^n-Z/
_ 11-1^
r21 ii - iJ
(Xn - X2)
_ IA . 95
(Xn - X3)
if Xi is
suspect
(X2 - X^)
/Y Y N
\"2 ~ ^l/
(Xn-! - Xx)
av ^
3 " *M/
/Y Y N
\An-l " Al/
/Y Y ^
\A.$ - A.^}
(Xn-2 * Xi)
Note that for use in this QAPjP ratio r22 will be used.
-------
TABLE 2
VALUES FOR USE WITH THE DIXON TEST FOR OUTLIERS
Risk of False Rejection
Ratio a P_5Z IX 5% 10%
3
4 .
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
0.994
0.926
0.821
0.740
0.080
0.725
0.677
0.639
0.713
0.675
0.649
0.674
0.647
0.624
0.605
0.589
0.575
0.562
0.988
0.889
0.780
0.698
0.637
0.683
0.635
0.597
- 0.679
0.642
0.615
- 0 . 641
0.616
0.595
0.577
0.561
0.547
0.535
0.524
0.514
0.505
0.497
0.489
0.941
0.765
0 „ 642
0 .. 560
0 . 507
0.554
0 . 512
0.477
0.576
0.546
0.521
0.546
0.525
0.507
0.490
0.475
0.462
0.450
0.440
0.430
0.421
0.413
0.406
0.806
0.679
0.557
0.482
0.434
0.479
0.441
0.409
0.517
0.490
0.467
0.492
0.472
0.454
0.438
0.424
0.412
0.401
0.391
0.382
0.374
0.367
0.360
Note that for this QAPjP the 5Z 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 6
APPENDIX G
ADDITIONAL QUALITY CONTROL CHECKS
-------
QUALITY ASSURANCE DATA FORM
NFS GROUND VftTER
Sampling Date(s)
Method
Arrival Date(s) at ECL
Set No
Set Composition
sample vol. (ml) sample vol. (ml)
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
Standards and Set Controls Data
Name / Date of Std. Used Amt. Spiked Initials
Method Blank
LCS
LCS
LSS
LSS
LSS
LSS
LSS
LSS
LSS
Surrogate
«**
***
STOP!! . Has Sanple Control Record been completed for both distribution and
return of samples?
. Has Set Composition Form been attached? ~
. Has ECL/NPS Sample Tracking Form been attached?
Signature:
Date:
-------
Procedure
Column
Extraction
Accomplished
Sample Preparation
Initials of Bnployee(s)
Doing Wbrk
Comments
Date Begun:
GC Analysis
Analyst(s):
Internal Std. Spike Data:
Spiked By:
Date:
Name / Date of Std. Used:
I.D. of Instrument Used for Analysis:
1.
2.
3.
4.
5.
6.
Analysis Dates
7. 10.
8. 11.
9. 12.
Date Completed:
Amt. Used:
13.
14.
1.5.
16.
STOP! l . Is GC work complete?
. Have NPS 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:
Data Reviewed By:
*** Final Disposition of Extracts:_
*** Date of Final Disposition:
Disposition of Extracts:
Date:
Signature:
_ n
-------
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.
-------
is i
a,
D
j|
"
y
S
^^
Cd
§j
s
1
i2 C OJ
JJ O O C § o
0) Q
^ §
/rt ^j
3"
. 3
fsH
a rt, „
> c 3 o
d -<-i Cu X
•
5c i|
U -r^ £ X
0) C
« fi
J
& o &3
u JJ Z
•«
•J en
3S
. ti «
fr'B §
353
-------
Extraction Set
Extracted
IKTERXAL
PSf: t.«S to 1.16
PCF: C.«3 to 1.17
OUBRATIOK STAXOMD ItOBSUTT
If the iyiUe «• not r^tlibnUo*. Lerel of Ck SU _
or is r«ca(ibrmU4 using CM« Acceptable rang*
•tandaH*, at feast one previou«ly
prepared standard tust be run. t«d _ U
ana (7 ted M a taeple, g'tring • result
vithin MX of the exp«ct«d value.
Range:
IKTERKAL STAXOARO AREA
IS peak area for any saeple tuit Files:
not deviate by eor« than 7« percent (Expressed as recovery relative
froe the ««in peak area for the to the eean area of the Range:
calibration standards. calibration standards.)
Uth Blk file Mo.
A*t of ETU found
Inst 9.C file Ho.
PSF
PCF
Ck sU file Ko.
Result
Coetents
CQKTRQL CHARTS Control Chart ________________ LCS fit* Ko. _
ETU recovery fro* the US and PTU
recovery fro. the US or Vth Blk PTU tUiU U PW ( US / BUC )
•ust be vithin the 3 SU lieit*
of the current control chart. ETU lieiU U ETU xie«/9«
Alert condition* occur «h«n:
pass
fail
pass
fail
pass fait
pass
pass
pass
fail
fail
fail
pass fail
-------
Appendix H
Revision No. 4
Date: December 1989
Page 1 of 3
APPENDIX H
ECL COMPUTER PROGRAMS
-------
BASIC PROGRAM: REGVftR
MAR 23, 1983 15:43:27
5REM***REGVAR, WRITTEN FOR ECL BY UWD, OCT 1,1 98e
10LETN=T=C1=C2=D1=D2=0
20PRIHT"ENTER COMPOUND NAME";
30DIMAJ C403
35DIMUC100]
36DIHPC1003
37DIMXC1003
38DIMDC1003
39DIMGC100J
40IHPUTA*
50PRINT"ENTER -1 AFTER YOUR LAST DATA POINT"
60FORIMT030
7SPRINTI
S0PRINT"ENTER YOUR VALUE FOR X";
90INPUTUCI3
100IFUCI]=-1THEH150
110LETH=H+1
120PRINT-EMTER YOUR VALUE FOR Y ";
130INPUTPCH
140HEXTI
150PRINT
lb0PRIHT"ARE ALL VALUES CORRECT? ";
170INPUTB*
180IFB**"Y"THEN26e
190PRINT"EHTER THE NUMBER OF THE PAIR IN ERROR";
200INPUTI
216PRINT"EHTER THE CORRECT X";
220INPUTUCI]
230PRINT"ENTER THE CORRECT YM;
240INPUTPCIJ
250GOT0160
26QFORI=1TON
270LETC1=C1+UCI]
290LETDl*Dl+Ptn
300LETD2«D2+
310NEXTI
330LETY=jXCI];TAB<33);DCI];
5I0PRINTTRB<48>;Gm
520LETT-T+CCI3
530NEXTI
540PRINT"THF SUM OP T1TFF-2 IS "
-------
5S0PRINT
576PRINT
580LETZ = 2M
598GOT0420
6000UTDVC"T1",E
610PRINTMNPUT A V VALUE. USE A -1 TO EMU THE OPERATION."
620INPUTT
630IFT=-1THEN72G
e40LETV=<-S
650PRINT"YOUR X VflLUE IS "V
£60PR1NT"YOUR V VflLUE IS "T
6700UTDVC"L1",E
680PRINT
690PRINT"YOUR X VflLUE IS "V
700PRINT"YOUR Y VALUE IS "T
7ieGOT0600
720PRINT
7300UTDVC"T1",E
748IFL$="MfiNY"THEMlG
75ePRIHT"IF YOU HflVE SEVERAL GROUPS AND WOULD LIKE TO OMIT";
76QPRINT"THE NEXT QUESTION, ENTER MANY INSTEAD OF Y OR N. "
770PRINT
780PRINT-DQ YOU WANT TO ENTER ANOTHER GROUP'' < Y.'N-'MflHY) "
790INPUTLJ
8001FL**"MANY"THEN 10
810IFL$="Y"THENie
320EHD
END OF FILE
-------
Appendix I
Revision No. 4
Date: December 1989
Page 1 of 6
APPENDIX I
RAPID REPORTING NOTIFICATION
-------
r
5 UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI. OHIO 45268
MEMORANDUM
DATE: April 12, 1988
SUBJECT: NFS Rapid Reporting System
FROM: David J. Munch, Chemist
Drinking Water Quality Assessment Branch
TO: NFS Technical Monitors
Jerry Kotas has requested that any confirmed results of health
significance be reported as quickly as possible. Therefore, if an analyte
listed in the attached tables is observed in the primary analyses, at or
above the rapid reporting limit, the.following actions should be
instituted. For any listed analyte where the rapid reporting level is
less than or equal to 1/2 the minimum reporting level (MRL), any
occurrence at or above 1/2 the MRL should also be processed as below.
(Note: The procedures for determining the occurrence of NFS analytes that
may occur below the MRL, and are not listed on the attached tables, have
not yet been finalized.)
1. The appropriate confirnational analyses (GC/MS for methods 1-3,
6-7, second column for Method 5) should be performed as soon as
practical.
2. The laboratory should telephone their Technical Monitor, the same
day the confirmation is completed.
3. The laboratory should immediately document the observed result in
a letter to their Technical Monitor.
4. As quickly as possible on the day the above telephone call is
received from the laboratory, the Technical Monitor should inform
their Laboratory Analytical Coordinator of the finding. The
Technical Monitor should forward on to the Laboratory Analytical
Coordinator the above documentation, with any comments he/she may
have concerning the validity of the result.
5. The Laboratory Analytical Coordinator should inform Jerry Kotas
and the second Analytical Coordinator of the finding by telephone
the sane day if possible, and in writing after the documentation
is received from the Technical Monitor.
6. The Analytical Coordinators are to request, through the
appropriate Technical Monitors, that all analyses for this sample
site be conducted, and reported in writing, as soon as practical.
-------
-2-
If you have any questions concerning these procedures, please let Bob
Maxey or me know. Also, please pass on this information to your contract
and referee laboratories. They will need to have this information in hand
prior to their conducting the dry run.
Attachment - '•
Addressees:
A. Dupuy
L. Kamphake
C. Madding
R. Maxey
R. Sorrell
R. Thomas
cc:
J. Kotas
H. Brass
A. Kroner
J. Orme
-------
METHOD 16
ANALYTE RAPID REPORTING LEVEL
ethylene thiourea 1.05 ug/L
-------
BSL
NFS RAPID REPORTING NOTIFICATION
NPS METHODS 1,3 AND 6
Date:
Set No.:
NPS Field Sample No.:,
BSL Lab. I.D. No.:
METHOD 1
ANALYTE
Rapid
Reporting
Level (ppb)
Analytical Results
Primary GC Column
(PPb)
•
Secondary GC Column
(ppb)
GC/MS
(pos. or neq. or N/F
METHOD 3
ANALYTE
Rapid
Reporting
Level (pcb)
Analytical Results
Primary GC Column
(PPb)
Secondary GC Column
(PPb)
GC/MS
(pos., neg., or N/R
NOT ANALYZED
-------
METHOD 6
ANALYTE
Rapid
Reporting
Level (ppb)
Analytical Results
Primary QC Column
l- (ppb)
Secondary GC Column
(ppb)
%
GC/MS
(pos. or neq. or N/
* —
= NOT ANALYZED
QA Assessment:
Is there any QC 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 Leader
-------
Appendix J
Revision No. 4
Date: December 1989
Page 1 of 2
APPENDIX J
GC/MS CHARACTERISTIC IONS FOR METHOD 6
-------
El CHARWTTERISTIC IONS FOR BTO
I
1 Analy te
1
lETU
1
iMethod *
1
I 6
1
I Amt. Injected
1
I 100 ng
El Characteristic -Ions m/z
M.W.
'
102
1
Primary |
I
102 |
2nd
73
3rd
72
-------
Appendix K
Revision No. 4
Date: December 1989
Page 1 of 6
APPENDIX K
ADDENDA TO METHOD 3 - JUNE 1988 TO DECEMBER 1989
-------
05/01/89
Environmental Chemistry Section
Addendum - Method 6
Revision to Section 4, page 1, paragraph 1, sentence 5
- Change "Dr. Y. A. Yonan, ECL-QAO, ..." to "Mr. Danny McDaniel,
Acting ECS-QAC,"
Revision to Section 4, page 1, paragraph 2, sentence 1
- Delete first two sentences.
- Add "Dr. Christian Byrne and Mr. Stanley Mecomber will handle sample
preparation/ analysis, data handling and reporting."
Revision to Section 4, page 1, paragraph 2, sentence ?.
- Change.". . . Mr. George Sand." to ". . . Mr. Henry Shoemaker"
Revision to Section 4, Figure 4-1 - ECS ANALYTICAL TEAM - Method 6
- Delete ECS ANALYTICAL TEAM diagram from Figure 4-1.
- Replace with revised diagram on following page.
Approved
EPA/ECS-NPS Project L#der/
PCS Analytical Coordinator
Approved
Approved wlf f>j A**, f*J fft^\* •~~\ajLAfitV
QACKJDWVSQ
Approved >£ (L**-~~~**
/
NFS Director
/73
-------
Project: NPS
Section No: 4
Revision No: 3
June 1988
Page of
Sample Custodian
G. Gardner (EPA)
Assistant Sample
Custodians
J. Cuevas (EPA)
S. Mecomber (EPA)
Sample Prep./Ext.
C. Byrne (STI)*
S. Mecomber (EPA)
ECS ANALYTICAL TEAM
METHOD 6
NPS Project Leader
Bob Maxey (EPA)
GC -
C.Byrne (STI)*
S. Mecomber (EPA)
ECS-QAC (Acting)
D. McDaniel (EPA)
Data Review
H. Shoemaker (EPA)
GC/MS
J. Ferrar io (EP A)
Data Handling,
Reporting
C. Byrne (STI)*
S. Mecomber (EP
Sverdrup Technology Ino; (In-house Contractor for ECS)
ECS provides overall technical direction to Sverdrup Technology/ Inc.
FIGURE 4-1: ECS ANALYTICAL TEAM - MFTHOD 6
-------
e/12/aa
ENVIRONMENTAL CHEMISTRY LABORATORY
ADDENDUM - METHOD 6
Addition to Section 4, page 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
"NASA/SSC Bldg. 1105
STENNIS SPACE CENTER, MS 39529-60OO"
Addition to Section 4, page 1, paragraph 4
-Change "The Assistant Sample Custodian -for NPS is:
Mr. John Cuevas
(601)688-3170 (or 3217)"
to
"The Assistant Sample Custodians -for NPS are:
Mr. John Cuev&s
(601)683-3170 (or 3217)
Mr. Stanley Mecomber
(6OD688-317O (or 3217)
Figure 4-1 s ECU ANALYTICAL TEAM Mas revised. The new chart is
enclosed.
Approved
Approved
EPA/ECS-NPS Project Lflader
ECS Analytical Coordinator
-------
Project: NFS
Section No: 4
Revision No: 3
June 1988
Page of
Sample Custodian
G. Gardner (EPA)
J. Cuevas (EPA)
'I
I
ECL ANALYTICAL TEAM
METHOD 6
I I
| NPS Project Leader |
I I
I Bob Maxey (EPA) \
GC
I I I
I Sample Prep./Ext. | |
I I I
| C. Byrne (STI)* | | C.Byrne (STI)*
I I 1
ECL QAC
Y.Yonan (EPA)
| Data Review j
.1 I
I George Sand (EPA) I
I I
I GC/MS |
I !
I D. McDaniel (HR)(EPA)|
I J. Ferrario (LR)(EPA)|
Data .Handling/
Reporting
C. Byrne (STI)*
* STI = Sverdrup Technology Inc. (In-house Contractor for BCL)
Sverdrup is providing the ECL severeal person-Years of support.
ECL provides overall technical direction to Sverdrup Technology/ Inc.
FIGURE 4-1: ECL ANALYTICAL TEAM - METHOD 6
-------
7/21/88
Environmental Chemistry Laboratory
Addendum - Method 6
Addition to Section 2, page 1, Appendix G
-Add "Internal Quality Control Checklist" below "QC Data Sheet".
-Add an Appendix "J: GC/MS CHARACTERISTIC IONS FOR METHOD 6".
Addition to Section 5, page 1, number 8, end of paragraph
-Add "See Appendix J for a table of the three ions for ETU".
Addition to Section 9, page 3, below 10.6.1.1
-Add " *11.1.1 Add preservative to all Method Blanks, Laboratory Control
Standards, and any Samples not previously preserved (Section 8.2) Pipet
50 ml
-Change "TABLE 5 Sensitivity Ethylene thiourea (ETU) 0.025"
to
"TABLE 5 Sensitivity Ethylene thiourea (ETU) 0.025 ug/ml"
Delete Section 11, page 7, II "a" and make "b" the new "a"
Addition to Appendices
-Add internal Quality Control Checklist (enclosed) to end of Appendix G.
-Add a cover sheet for Appendix J: GC/MS CHARACTERISTIC IONS FOR METHOD 6.
(For the appendix contents, see the enclosed GC/MS Characteristic Ions
Table.)
Approved
US Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th rloor
Chicago, IL 60604-3590
------- |