&EPA
United States Office of Water (WH-550) EPA 810-B-92-011
Environmental Protection Office of Pesticides and February 1992
Agency Toxic Substances (H-7501C)
QUALITY ASSURANCE PROJECT PLAN
FOR THE
NATIONAL PESTICIDE SURVEY OF DRINKING WATER WELLS
ANALYTICAL METHOD 3
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, II 60604-3590
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Section No 1
Revision No 4
Date- December 1989
Page 2 of 2
APPROVAL PAGE
4
Robert Maxey
_, ECS Project Leader
_, EPA Technical Monitor
Aubry E. Dupuy, Jr. Section Chief, ECS
_, Acting ECS QAC
Danny McDaniel
Lora Johnson
Elizabeth Leovey
, NPS QAO
, OPP QA Officer
List for Distribution:
R. Maxey, OPP/ECS
A. Dupuy, OPP/ECS
D. McDanie! OPP/ECS
L Johnson, NPS QAO
E. Leovey, OPP/QAO
G. Gardner, OPP/ECS
S. Mecomber, OPP/ECS
E. Flynt, OPP/ECS
J. Watkins, STI
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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 3
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 7 4 12/89
8.1 Method 3 Standards
8.1.1 Calibration Solutions
8.1.2 Standards Prepared at ECL
8.1.3 QA for Diluting and Checking the
Standards
8.1.4 Calibration Solutions and ECL
Standards Verification
8.1.5 Frequency of Calibration Standards
Checks
8.1.6 Association of Calibration Standards
to Survey Sample Analysis
8.2 Instrumentation Checks and Quantitation Procedure
8.2.1 Calibration of HR GC/MS
8.2.2 Calibration of Low Resolution GC/MS
9. ANALYTICAL PROCEDURE 4 4 12/89
9.1 Summary of Method
9.2 Major Equipment/Instrumentation to Be Used With
Method 3
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 11 4 12/89
11.1 Primary Analyses
11.2 Confirmational (Secondary-Column) GC Analyses
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
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 Diazomethane QC Check
11.5.2 Florisil Elution Check
11.5.3 QC Datasheet
11.5.4 QA Data Form
11.6 Exceptions to the QAPjP
11.6.1 Request for Approval
11.6.2 Documentation and Following
Requirements
AUDITS
12.1 Requirements
12.2 Frequency
12.3 Nature of Audits
12.3.1 Tech. Systems to be Addressed
12.3.2 Data Quality Audits
12.3.3 Performance Evaluation Audits
12.4 Standard
12.5 Reporting and use of Audit Results
Revisions
Date
12.
13.
14.
12/89
PREVENTATIVE MAINTENANCE
13.1 Gas Chromatographs
13.2 GC/MS
SPECIFIC PROCEDURES FOR ASSESSING
MEASUREMENT SYSTEM DATA
14.1 Formulas Related to Instrument Control
Standards and Determination of
Chromatographic and Column
Performance
14.2 Formulas for Calculating Statistics
14.3 Formulas for Defining Control Limits
15. CORRECTIVE ACTION
16. QUALITY ASSURANCE REPORTS TO
MANAGEMENT
12/89
12/89
12/89
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Section No 2
Revision No 4
Date December 1989
Page 4 of 6
2. TABLE OF CONTENTS (continued)
Appendices Pages
A.
B.
C.
D.
E.
F.
G.
H.
1.
J.
*K.
*L
SAMPLE CUSTODY
BATTELLE'S VERSION OF NPS METHOD 3
DIAZOMETHANE PREPARATION AND SAFETY
DATA FLOW (REDUCTION, VALIDATION, AND
REPORTING)
SIGNIFICANT FIGURES AND ROUNDING OF NUMBERS
STORAGE OF NPS HARDCOPY DATA FILES AT ECL
DIXON'S TEST
ADDITIONAL QUALITY CONTROL CHECKS
ECL COMPUTER PROGRAMS
RAPID REPORTING NOTIFICATION
GC/MS CHARACTERISTIC IONS FOR METHOD 3
ADDENDA TO METHOD 1 :
6
50
6
12
4
3
3
13
3
6
2
Revisions
4
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
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 L
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
ECL ANALYTICAL TEAM - METHOD 3
LABEL OF SAMPLE BOTTLES
FIELD SAMPLE TRACKING FORM
SAMPLE RECEIPT SCREENS FOR NPS LABORATORIES
TEMPERATURE MONITORING 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
DIAZOMETHANE QC FORM
ADSORBENT CHECK FORM
EXCEPTIONS TO NPS QAPjP
EQUATION USED TO CALCULATE PEAK SYMMETRY
FACTOR (PSF) AND PEAK GAUSSIAN FACTOR (PGF)
EPA REFEREE LABORATORY PROGRESS - QA REPORT
TECHNICAL MONITOR PROGRESS - QA REPORT
ANALYTICAL COORDINATOR STATUS REPORT
Figure No.
4-1
6-1
6-2
7-1
7-2
7-3
8-1
8-2
8-3
10-1
10-2
11-1
11-2
11-3
14-1
16-1
16-2
16-3
Section
4
6
6
7
7
7
8
8
8
10
10
11
11
11
14
16
16
16
Page
2 of 2
3 of 4
4 of 4
4 of 6
5 of 6
6 of 6
5 of 7
6 of 7
7 of 7
5 of 6
6 of 6
7 of 11
9 of 11
11 of 1 1
3 of 3
2 of 4
3 of 4
4 of 4
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Section No 2
Revision No. 4
Date December 1989
Page 6 of 6
2. LIST OF TABLES
Title
ENVIRONMENTAL CHEMISTRY LABORATORY SAMPLE
REQUIREMENTS
Table No.
6-1
Section
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. Seventeen of these analytes
are included in NPS Method 3 with which phenoxy and phenol compounds will be determined.
There is a referee laboratory for each method; the OPP Environmental Chemistry Laboratory at
Bay St. Louis, MS will serve this function for NPS Method 3. The roles of the referee laboratory in this
Survey are:
• to analyze duplicates of samples sent to the analytical contractor (primary lab.)
limited to 20% or a maximum of 5 samples per week from those taken the first 6
months;
to perform High Resolution GC/MS Confirmation of low concentration suspected
residues not amenable to analysis by Low Resolution GC/MS;
• to provide a Technical Monitor and/or EPA Project Officer to oversee analytical
and/or contractual aspects of work done by the analytical contractor;
to evaluate any QC activities required of the analytical contractors, including
conducting and participating in NPS audits;
• to provide verification analyses of blind samples;
• and to verify prior to use all analytical standards prepared for use with this method
by EPA/Technical Support Division - Cincinnati or their contractor.
The phenoxy - phenol pesticides and/or degradation products included as analytes for this
method are:
1/ Acifluoffen
Bentazon
1/ Chloramben (Amiben)
2,4-D
Dalapon
2,4-DB
DCPA acid metabolites
Dicamba
3,5-Dichlorobenzoic acid
Dichlorprop (2,4-DP)
Dinoseb
1/ 5-Hydroxy dicamba
1/ 4-Nitrophenol
PCP
Picloram
2,4,5-T
2,4,5-TP (Silvex)
1/ Qualitative Analyte
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Section No 4
Revision No. 4
Date. December 1989
Page 1 of 2
4. PROJECT ORGANIZATION AND RESPONSIBILITIES
Referee laboratory responsibilities for NPS Method 3 will be carried out by OPP's Environmental
Chemistry Lab. (ECS) which is managed by Dr. Aubry E. Dupuy, Jr., Section Chief. Mr. Robert Maxey,
chemist at ECS, will serve as both EPA Technical Monitor and Project Officer for the Method. Mr.
Maxey, as ECS Project Leader, will also be responsible for day-to-day management of NPS analytical
activities. Mr. Danny McDaniel, Acting ECS-QAO, will provide QA oversight (effective 050189; see
Appendix L; Addendum of 050189). The Sample Custodian for ECS and for the NPS Project is Gerald
Gardner.
Mr. Stanley Mecomber and Ms. Elizabeth Flynt will handle sample preparation. Analytical work
will be handled by Ms. Jan Watkins backed up by Ms. Elizabeth Flynt. Data review has been
assigned to Mr. William Mitchell and Mr. Joe Ferrario. Data handling and reporting will be handled by
Ms. Watkins 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 (effective 050189; see Appendix L;
Addendum of 050189). Refer to the Method 3 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 ECL's 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
(601) 688-3170 (or 3217)
Mr. Stanley Mecomber
(601) 688-3170 (or 3217)
(effective 081288; see Appendix L; Addendum of 081288)
The telephone number for the EPA Technical Monitor and Project Officer for NPS Method 3 is:
Mr. Robert Maxey
(601) 688-1225 (or 3217)
In Mr. Maxey's absence, Dr. Aubry Dupuy will serve as the appropriate EPA contact for
Technical Monitor and Project Officer responsibilities for Method 3.
Dr. Aubry E. Dupuy
(601) 688-3212
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Section No 4
Revision No 4
Date December 1989
Page 2 of 2
FIGURE 4-1
ECS ANALYTICAL TEAM - METHOD 3
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Section No 5
Revision No 4
Date' December 1989
Page 1 of 5
5. QA OBJECTIVES FOR MEASUREMENT DATA
5.1 Initial Determination Of Capabilities; Determination Of EDLs; Determination Of
Reporting Levels
1. Determine concentration of standard necessary to produce an instrument detector
response with a 5/1 signal to noise ratio.
2. Spike eight reagent water samples at the concentration determined above, and analyze in
a single day analyte 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 EDLs will prevail to assure that there is a minimal
response on both columns. Again, EDLs exceeding this requirement will be approved on
a case-by-case basis, by the Technical Monitors.
* 8. The laboratories will be required to perform up to six analyses per analyte mix by GC/MS,
for the appropriate Methods. These analyses will be performed by MID, using the three
ions specified by EPA. The purpose of these analyses are to determine the concentration
at which a 5/1 signal to noise ratio, for the least intense of the three ions, is obtained. See
Appendix K for a Table of the three ions for each analyte (effective 06/15/88; see
Appendix L; Addendum Of 07/12/88).
9. The Minimum Reportable Level (MRL) for Method 3 is 5 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 NPS Analytes Below the Minimal
Reporting Levels and Identifying Unknown Peaks
Background Information
The Office of Pesticide Programs (OPP) has requested that the NPS analytical contractors and
referee laboratories make an effort to report the presence of NPS analytes below the Minimal
Reporting Levels (MRL). We have also been requested to attempt to identify unknown peaks or
responses. To assure that spurious or ambiguous data is not reported and that a uniform system or
analytical routine is used at all laboratories to accomplish these requests, the following procedures will
be used.
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Section No. 5
Revision No 4
Date: December 1989
Page 2 of 5
5.2.1 Procedure for Determinining and Reporting the Presence of NPS Analytes
Below the Minimal Reporting Level
1. For Method 3, only peaks with responses of between one-half the established MRL and
the MRL A/ on the primary column will be investigated. The first time such a response is
noted on the primary column, no further analytical work is underdertaken; the second time
such a response is noted, analysis on the confirmatory GC column is required.
2. (a) For Method 3, if the response on the second column is positive, further analytical work
under (3) below is required.
(b) For Method 3, if the response on the second column is negative, that fact is noted. After
five attempts at second column confirmation have failed for the same analyte, the ECL
Project Leader is informed, and discussions with OPP personnel will take place before
continuation of analytical work on that analyte.
3. For responses meeting the requirements of (1) and 2(a), the laboratory will attempt LR
GC/MS B/ confirmation if the GC/MS analyst feels it is within the capability of his
instrument. If the confirmation is not within the capability of the LR GC/MS, the extracts
will be run on HR GC/MS. Copies of chromatograms the related Method Blank, and all
pertinent sample information must accompany the extracts. Correct volume level should
be clearly marked on the outsid^ of the extract tube.
A/ = NPS Method 3 MRL = 5 X EDL
B/ = LR GC/MS = Low resolution mass spectrometry
HR GC/MS = High resolution mass spectrometry
Only analytes positively confirmed by GC/MS will be reported beyond the ECL Project
Leader for Method 3 and the Analytical Coordinators. No unconfirmed data will be
reported outside the NPS analytical system. Unsuccessful attempts at confirmation will
also be reported to the ECL Project Leader.
5. Following either the successful GC/MS confirmation of two such responses for the same
analyte 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 sample extracts from the contractor
when HR GC/MS work is required. These extract shipments will be received and logged
in by the ECL Sample Custodian or his Representative, and the ECL Project Leader will be
notified.
5.2.2 Procedure for Determining The Identity of and Reporting the Presence of
NonNPS 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.
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Section No 5
Revision No 4
Date- December 1989
Page 3 of 5
1. For Method 3, if the response of an extraneous peak upon initial injection and
exclusive of the Method Blank, on the primary column is equal to or greater than the
response of the nearest NPS analyte on that column at 10X MRL (Minimal Reporting
Level), an attempt must be made to identify that peak by GC/MS. Full scan spectra
and subsequent library 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.
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
3. 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 NPS
analyte to elute before the unknown peak and the first NPS analyte to
elute following the unknown peak. The related Method Blank extract
must also be included.
3. Only those compounds positively confirmed by GC/MS will be reported beyond the
ECL Project Leader for Method 3 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 ECL Project Leader.
4. Following either the successful confirmation of two such extraneous peaks proving
to be the same compound or two failures to identify the same unknown peak,
discussions with OPP personnel will take place before continuation with
identification work on that particular compound.
5.3 Laboratory QC Requirements For Primary Analyses
1. Laboratory control standard mixes, which together contain all method analytes and the
surrogate, will be analyzed with each set of samples.
2. A set of samples is defined as all samples, blanks, spiked samples, etc., on which similar
analytical operations are performed at the same time and which are analyzed in a single
run.
3. The internal standard area checks detailed in Method 3, will be used but may not deviate
by more than +_ 20% of the average peak height or area of the internal standard in the
calibration standards. The control limits will be reassessed following completion of the
initial demonstration of capabilities.
4. The calibration curves, as defined in Section 8.12, are not used for quantitation, but for a
check of linearity. For quantitation, procedural standards (calibration standards prepared
by methylation of weighed acids or phenols) containing the method analytes and the
surrogate will be prepared for each set of samples. The concentration of each analyte in
each procedural mix will be 10xMRL These will be used as the "single point quantitation"
standards for the LCS's which have been spiked at 10xMRL Positives, analyte amounts
at 1/2 MRL or above, are analyzed by use of these procedural standards that are within.
+/- 20% of the .response of the suspect residue. The column check must be quantitated
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Section No 5
Revision No 4
Date. December 1989
Page 4 of 5
against the weighed ester standard at 10xMRL Refer to Section 8.20 for detailed
procedure (effective 06/88).
5. 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 instead 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.
6. The criteria for monitoring instrument control standards will be utilized as stated in the
method.
7. The requirement for surrogate recoveries from Field Samples and Method Blanks is the
Mean Recovery, R, on the applicable_~Control Chart H^ 30 percentage points (i.e. R ±
30%). It is not R ± .30 R. (effective 0~81888).
8. The requirements for monitoring calibration standard responses will be followed as written
in the method.
9. Samples failing any QC criteria must be reanalyzed.
10. Only qualitative analysis will be required for chloramben, 4-nitrophenol, 5-OH dicamba and
acifluorten. While these analytes are to be analyzed in at least one of the concentration
levels of the calibration standards, they are not subject to any of the QC requirements.
11. 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.
12. Any deviation from the analytical procedures or QC requirements, must be approved by
the appropriate ECS-NPS Project Leader 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 analyte(s) determined using the primary column.
2. The concentration(s) for the analyte(s) on the secondary column should quantitate within
+/- 25% of the result determined on the primary column (effective 03/20/89).
3. If the concentration determined on the secondary column does not agree within the limits
stated above, the analyst must confer with the ECS-NPS Project Leader concerning
resolution of the discrepancy prior to submitting the extract for GC/MS analysis (effective
06/88).
4. If the concentration determined on the secondary GC column meets the criteria in 2 above
and GCMS is positive, report the concentration of the analyte found on the primary
column (effective 06/88).
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Section No 5
Revision No 4
Date December 1989
Page 5 of 5
5.5 Laboratory QC And Extract Handling Related To GC/MS Confirmation
1. The sample extract is to be compared to a standard prepared at the concentration
determined for the analyte on either the primary or secondary column, whichever
concentration is the lower.
2. If additional sample extract treatment is performed for GC/MS analysis (blowdown, etc.),
the standard and sample extract must both undergo the same treatment.
3. Results of the GC/MS analysis are simply reported as the presence or absence of the
analyte.
4. If low concentrations of the analyte(s) preclude confirmation using Low Resolution GC/MS,
High Resolution GC/MS Confirmation must be attempted. HRGC/MS may also be
required if the analyte concentration is greater than or equal to 1/2 the lowest adverse
health effect for that analyte or if requested by the ECS-NPS Project Leader.
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.
c. Record any subjective observations you have about the samples and/or sample kit
(i.e. the bottle was warm to the touch).
d. Contact the ECS-NPS Project Leader if you have any further questions.
2. Strict adherence to sample and extract maximum holding times (14 days) is required for
both primary and secondary column analyses. All analyses should be completed as soon
as possible, but under extenuating circumstances, the maximum extract holding time may
be extended to 28 days for GC/MS analyses only, if approved by the ECS-NPS Project
Leader.
3. Water samples are to be disposed of after the 14 day sample holding time has been
exceeded. Sample extracts must be maintained until disposal is approved by the ECS-
NPS 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 1-Liter sample preserved with mercuric chloride at 10
mg/liter. This sample is to be shipped iced along with those needed for Methods 1 and 6, by
overnight air and is to arrive iced at ECL. This sample is for duplicate analysis of the field sample sent
to the primary analytical contractor. No "backup" or reserve sample will be shipped.
ECL, as a referee laboratory, is envisioned to receive no more than 10% of the total 1500
samples now expected to be taken in the Survey. Table 6-1, found at the end of Section 6.0,
summarizes these sample requirements.
6.2 Labelling Of Sample Bottles
The Implementation Contractor, ICF, will supply information on the labels, sample numbering
system, and explanations for field coding or decoding at the laboratory. This label is shown in
Figure 6-1.
6.3 Field Sample Tracking Form
ICF will supply a copy of this form along with explanations for field coding or decoding at the
laboratory. This form is shown in Figure 6-2.
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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 NAME
RCT TYPE
Saaple Types
BQTHETYPE
ANAL. HETBX
PriBary
Referee
Shipping Blank
Backup Saaple
Lab Spites
Tine/Storage
«»
Totals
ft>. of Sites
TOTAL RBQ'D
BSL I
Referee
ICOOoL lOOCtL 6QOL
1 3 6
111
111
ISO ISO ISO
ISO ISO ISO
Total Bottles:
lOOCttU-
2SOdL»
6CnL«
300
N.A.
150
-------
Section No. 6
Revision No. 4
Date. December 1989
Page 3 of 4
FIGURE 6-1
LABEL OF SAMPLE BOTTLES
SAMPLE *: PD-OOOO-6-i-Oi
BSL - METHOD* 1 KIT: 611
' FIELD SAMPLE
• PRESERVATIVE: HgC12
DATE 1 TIME '- SAMPLER
NATIONAL PESTICIDE SURVEY
SAMPLE #: PD-OOGO-6-3-OL- —
BSL - METHOD* 3 - KIT:
FIELD SAMPLE
PRESERVATIVE: Had 2
DATE ', TIME i SAMPLER
NATIONAL PESTICIDE SURVEY
SAMPLE *: PD-OOOO-6-6-O1
BSL - METHOD* 6 KIT: 611
FIELD SAMPLE
PRESERVATIVE: HqC12
DATE ', TIME ', SAMPLER
' J «J. lL PE5TTCI SS SURVEY
BSL - METHOD* 1 KIT: 611
BACKUP SAMPLE
PRESERVATIVE: HgC12
DATE ', TIME ! SAMPLER
-------
Section No 6
Revision No. 4
Date- December 1989
Page 4 of 4
FIGURE 6-2
FIELD SAMPLE TRACKING FORM
HELL I.D. WJ.: 0000
FRDS I.D. Mo. (US HELL ONLY):
SAMPLE COLLECTIH DATE: / /.
TRACKING FORM COMPLETED BY:
LftB: BSL
SCENARIO: J_
KIT NO.: PS-t-000-611
BQI I ot A
TO SE COMPLETED Bf:
Iff
SAMPLE
KUMBER
FIHWOO-6-1-01
PD-OOOO-b-3-01
PD-OOOO-6-e-Ol
PD-0000-t-i-')3
BOTTLE
SIZE
1000
1000
60
1060
SAMPLE
DESCRIPTION
FIELD SAMPLE
FIELD SAMPLE
FIELD SAMPLE
BACKUP SAMPLE
FIELS TEAR i LAB
sAHPLER : TIftE i UJIWENTS 11) iftEL-iVti CCMKEKIi ;
ilKITIALl : SAMPLED .
: : : : it
1
: : : • N
; : : : ><
: : : ! N:
CHLORINE TEST:
SHIPPED BY: i
OATE TIME
SEKT TO:
t
.
: F.ECElVEi- AT LAB BY:
.
: :ATE T:»E
LAB ADSRtSs: . ISttlTiai (l\
&AY St. LUIS EPA'EMV1PONȣHTAL ;
^EHISTF.- .At. •'.;£. 1105 :
NSTL. »S 3V.:*
1 '
i
il) FOP. EXAMPLE: E3TTLE BRWB, BOTTLE fCs-iiiS, QVERFU.Ev ?TtU£. CAf KA^ I-?.u?FE£
u) FQfi EUU9LE: BOTTLE BSOtH, BOTTLE MISSING. S3TTlE,:CftTM|tt7Cg. TEHPEF.ATURE CRITERIA KCT *£T
1:1 FM EXAflPLE: 1C£ RELTE9, £01 LEAklNS
( ub coMMti should concur Kith NFSIS SAKPLE RECEIPT )
-------
Section No 7
Revision No 4
Date: December 1989
Page 1 of 6
7. SAMPLE CUSTODY
7.1 Tracking And Notification Of Sample Shipments
The proposed EPA system for notification of the laboratory of sample shipments and for
notification of the Implementation Contractor (ICF) of receipt of the samples is delineated on the flow
chart and diagram, Labelled Figure 7-1, "SAMPLE RECEIPT 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 4oC. This information is documented on a "NPS LOGGING
FORM".
The Sample Custodian or his/her Representative will compile "sets" of samples for
Method 3 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 "NPS SET
COMPOSITION FORM'.
• Transfer of samples into and out of storage will be documented on an internal
chain-of-custody record. Only those samples in the "set" on which analytical work
will be done will be removed. This information is documented on a "SAMPLE
CONTROL RECORD FORM". The analyst will sign and date this Record when
removing or returning samples to storage.
After removal from storage, samples are tracked through extraction and G.C.
Analysis via an "ECL/NPS SAMPLE TRACKING FORM".
Following extraction, sample extracts are stored in a refrigerator at 4oC until
analyses are complete. Following analysis, they are transferred to screw-cap tubes
(teflon liners), the extract level marked, and stored by set in a freezer at 0' to -20'C.
An "EXTRACT STORAGE DATA SHEET" records chain-of-custody of extracts from
GC Analysis to GC/MS Confirmation, if required, and to disposal.
Copies of all the above mentioned Forms and Records can be found in
Appendix A .
7.2.1 Storage Conditions
Upon receipt at the laboratory, samples will be stored under refrigeration at 4oC and protected
from light.
7.2.2 Holding Times
Samples have a maximum holding time of 14 days from time of collection until the start of
extraction.
Extracts have a maximum holding time of 14 days from date of extraction to GC Analysis and
GC/MS Confirmation, if required. The holding time for GC/MS Analysis may be extended an additional
14 days upon approval of the ECL Project Leader.
-------
Section No 7
Revision No 4
Date December 1989
Page 2 of 6
7.2.3 Disposal
Samples held longer than 14 days without being extracted are to be disposed of after approval
is given by the ECL Project Leader.
The samples arrive with a 10 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.
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 ECS, tracking will begin upon receipt and continue through final disposition according to
the following procedure.
Upon receipt at ECS, the Sample Custodian or his representative will check extracts
against the NFS EXTRACT SHIPMENT form, filling in the Date Received at ECS,
Conditions of Shipment, Number of Refrigerator where strored, the Container
Number and signing where appropriate. (A copy of this form is attached at the end
of this Section and is labelled Figure 7-2.) He should then place the extracts in
containers labelled 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 NPS Technical Monitor for
the Analytical Contractor and a copy of the original paperwork to the GCMS analyst.
The Sample Custodian should keep on file, in the receiving room, a copy of the
NPS EXTRACT SHIPMENT form.
The GCMS analyst should remove extracts from the designated refrigerator, analyze
the extracts by GCMS, then complete the remainder of the NPS Extract Shipment
form and the GCMS Data Sheets. The analyst should give all completed forms and
GCMS spectra to the NPS Technical Monitor.
The Technical Monitor will use the information from the NPS EXTRACT SHIPMENT
form to complete an overall tracking form, the NPS GCMS EXTRACT TRACKING
FORM. He will send a copy of the GCMS Data Sheet to the NPS Data Manager and
to the Analytical Contractor. He will also send the Analytical Contractor a copy of
the GCMS spectra. ECS will maintain the original paperwork on file.
GC/MS results will be reported as in Sections 10.5 and/or 10.63.
The Technical Monitor for the appropriate Method will receive all results and reports
of GC/MS confirmation analyses and a monthly report from the ECS Sample
Custodian on the total number of extracts received for each Method.
The Technical Monitor will inform the Analytical Contractor, in writing, of the results
of each GC/MS confirmation attempt.
-------
Section No 7
Revision No 4
Date. December 1989
Page 3 of 6
• 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 081288; see Appendix L; 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
-------
Section No 7
Revision No 4
Date December 1989
Page 5 of 6
FIGURE 7-2
NPS EXTRACT SHIPMENT
(a
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-------
Section Mo. 7
Revision No 4
Date December 1989
Page 6 of 6
FIGURE 7-3
TEMPERATURE MONITOR CHART EPA/ECL
* WALK-IN
COOLERS/BLDG. 1105
DATE
TEMP.
PERSON CHECKING
* WALK-IN/UPRIGHT
FREEZERS/BLDG. 2204/1105
REMARKS
DATE TEMP
PERSON CHED'
•CING I
-t
T
L
-------
Section No 8
Revision No 4
Date December 1989
Page 1 of 7
8. CALIBRATION PROCEDURES AND FREQUENCY
8.1 Method 3 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 3 analytical
team. A sample copy of this form is attached at the end of this Section and is labeled Figure 8-1.
A "CALIBRATION SOLUTION RECEIVING FORM" will be initiated to record the date solutions are
received, number of sets, condition, and place of storage at ECL. These forms will be kept in a
designated folder. A copy is found at the end of this Section and labeled Figure 8-2.
8.1.2 Standards Prepared at ECL
ECL will prepare and maintain separately weighed stock standards of each analyte. These
stock standard materials should be from the same lot numbers as those used to prepare the
EPA/Bionetics-supplied calibration solutions. These ECL-prepared standards will be used to verify the
concentrations of the calibration solutions and resolve problems or questions that may arise
concerning any of the standards.
A standards log book is maintained to record name of person weighing the standard, chemical
identifier 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.
-------
Section No 8
Revision No 4
Date- December 1989
Page 2 of 7
8.1.4 Calibration Solutions and ECL Standards Verification
Calibration solutions will be the stock material for all standards used in the NFS at both the
referee and analytical contractor laboratories. To verify their concentrations, they must by analyzed
against the ECL prepared standards before use. The calibration solutions and ECL prepared
standards must differ by no more than +. 15%. Following the comparison, all values must be reported
to the ECS Project Leader. Standards with differences >± 15% require resolution at this point before
work with the standard can proceed.
8.1.5 Frequency of Calibration Standards Checks
Calibration standards must be checked against ECS prepared standards each time a new
calibration standard is prepared from a calibration solution. Criteria in 8.14 apply.
Concentrations of calibration solutions must be verified at ECS each time new Batch Nos. are
prepared at EPA/TSD-Cincinnati or Bionetics and before shipment to the analytical contractor. Criteria
in 8.14 apply.
8.1.6 Association of Calibration Standards to Survey Sample Analyses
Each calibration (bench) standard used in analytical determinations must be able to be traced
to its origin and every field sample or control sample analyzed must be associated with the specific
calibration standard(s) used.
To facilitate these requirements, each standard mix with different components or different
concentrations of these components must have a uniquely different name and a date of preparation.
This standard identifier and date must appear on each chromatogram of the standard. It may also
appear on the computerized data printout.
* 8.2 Instrument Calibration and Quantitation (effective 06/88)
A Hewlett-Packard 5890 A dual capillary GC with electron-capture detectors is used to analyze
Method 3 samples. The internal standard (ISTD) selected for use with Method 3 is 4,4-
dibromooctafluorobiphenyl (DBOB) and is compatible with the GC columns and chromatographic
conditions for this Method.
Weighed methyl ester standards are used for the calibration/ linearity check of the gas
chromatograph. A minimum of three standards will be diluted from an ECS-prepared standards mix,
and the lowest concentration 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). Thus, the standards for instrument calibration should range from
MRL to 10xMRL
Following injection of the ECS-prepared standards, the relative response (RRa) of each analyte
to the ISTD is calculated with the following equation:
-------
Section No 8
Revision No 4
Date: December 1989
Page 3 of 7
RRa = Aa / A,s ' Where
Aa = Area of the analyte
Ats = Area of the internal standard
The calibration curve is generated by plotting RRa versus analyte concentration in ug/liter.
Although a calibration curve is drawn for each analyte, it is not used for quantitation but only for
QC purposes. The working calibration curve must be verified previous to sample analysis and every
eight hours during an analysis sequence. If the response for any analyte varies from the predicted
response by more than +/- 20%, the GC injection should be repeated and/or a new calibration curve
prepared for that analyte. If the predicted response for an analyte continues to vary by more than +/-
20%, a new calibration standard mix should be prepared. If a new calibration standard is prepared,
the ECS Project Leader must be informed.
Initially, the current requirements of the Instrument Quality Control Standard must be met.
Procedural Standards are prepared at 10xMRL by methylating weighed acids or phenols. The
surrogate must be incorporated into one of the mixes. These analyte mixes are used as "single point
quantitation" standards. (See Section 5.3.)
Following injection of a standard, the relative response (RRstd) of each analyte to the internal
standard is calculated with the following equation:
RRstd = (Aa/Ais) /C, where
Aa = Area of the analyte
Ais = Area of the internal standard
C = Concentration of analyte at 10xMRL.
In a similar manner, a response factor (RRsamp) of each analyte to the internal standard of
each sample is calculated with the following equation:
RRsamp = (Aa/Ais), where
Aa = Area of the analyte
Ais = Area of the internal standard
The ratio of the RRsamp to the RRstd of a given analyte in a sample will result in the
determination of the concentration of the analyte.
If a new calibration curve must be prepared, the ECS Project Leader must be informed.
8.2.1 Calibration of HR GC/MS
Scanning Mode - The instrument is calibrated by the MCAL and CALIB routines in the
MAT 312 operations manual
MID Mode - The instrument must be further calibrated by using the ESCAN and
ECAL routines in the manual
-------
Section No 8
Revision No 4
Date December 1989
Page 4 of 7
The instrument will be tuned for proper relative ion intensities by using DFTPP-7 (if possible)
when library searches are indicated.
* 8.2.2 Calibration of Low Resolution GC/MS (effective 06/88)
The instrument is calibrated according to the manufacturer's recommendations using the
CALIBRATION (CAL) routines specified in the manual.
The mass spectrometer will be tuned to EPA's specifications using DFTPP (effective 06/88).
-' 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.
-------
FIGURE 8-1
STANDARD SOLUTION DATA FORM
Section No 8
Revision No 4
Date: December 1989
Page 5 of 7
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-12: j i I i i ! i i j j i | i i I i i
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-------
Section No 8
Revision No 4
Date Decemoer 1989
Daae 6 of 7
FIGURE 8-2
CALIBRATION SOLUTION RECEIVING FORM
Date Received: Date Checked:
Person Receiving: Person Checking:
Ware Samples Iced?J _ - _ Relinquished Custody; (Yes/No)
Method No: (If3 ror 6)
(circle one)
Comments:
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: Boon No:
Ccmrents on condition of Calibration Solutions:
-------
Section No 8
Revision No 4
Date Decemoer 1989
Page 7 of 7
FIGURE 8-3
STANDARD DILUTION FORM
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-------
Section No 9
Revision No a
Date December 198
Page 1 of 4
9. ANALYTICAL PROCEDURE
9.1 Summary Of Method
This Method is applicable to the determination in ground water of the phenoxy acid and phenol
analytes listed in Section 3 and their salts and esters.
A measured volume of sample (approximately 1-Liter) is adjusted to pH 12 or greater with 6N
sodium hydroxide and allowed to sit, with periodic shaking, for 1 hour to hydrolyze salts and esters of
the phenoxy/phenol analytes. Extraneous organic material is removed by dichloromethane solvent
washes. The sample is acidified, and the chlorinated acids are then extracted with diethyl ether by
shaking in a separatory funnel. Using diazomethane as a derivatizing agent, the acids are converted
to their methyl derivatives. Excess derivatizing reagent is removed, and the esters are determined by
electroncapture gas-chromatography (ECD).
A Florisif cleanup procedure is included to aid in the elimination of interferences that may be
encountered.
Capillary gas-chromatography with ECDs is used for both primary and secondary analyses of
the sample extracts.
For sample extracts with suspect-positive analytes, (i.e.-those with positive responses on both
the primary and secondary GC columns), such extracts will be analyzed by either Low Resolution
GC/MS (LRGC/MS) or High Resolution GC/MS (HRGC/MS) to confirm the presence or absence of the
analyte.
9.2 Major Equipment/Instrumentation To Be Used With Method 3
Hewlett-Packard 5890A dual capillary gas-chromatograph with dual ECD. Identical
instrument for backup.
• Hewlett-Packard 7673A autosampler. Identical unit for backup.
Hewlett-Packard 3359A Lab Automation 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.
-------
Section No. 9
Revision No 4
Date: December 1989
Page 2 of 4
9.3.2 Differences From Battelle Method
3.5 Instrument Quality Control (QC) Standard - use isooctane instead of methyl tert-
butyl ether (MTBE)
4.1.1 Glassware Cleaning and Preparation
1. All new glassware should be pre-soaked in Chromic-Sulfuric acid cleaning
solution.
2. Wash glassware with 2-5% Chem-solv, Micro*, or similar cleaning solution.
Pre-soak heavily soiled glassware.
3. Rinse will with tap water.
4. Rinse glassware with acetone, methylene chloride and hexane respectively.
(Safety note: wear rubber gloves not permeable to or attacked by solvents
and wear safety glasses.)
5. Bake glassware in oven overnight (approx. 12 hours) at 400'C. For this
purpose, glassware is stacked on aluminum or stainless steel trays and
loaded into the oven.
6. Upon cooling, rinse glassware with acetone, methylene chloride and hexane.
4.2 All clean baked glassware will be rinsed with acetone, methylene chloride, and
hexane prior to use. No acid-rinsing of glassware.
6.2.7 Flask - flat bottom - 250 ml with 24/40 ground glass joint. Fisher (or equiv.) cat no.
10-101B
6.9 See Appendix No. C for Diazald Kit for diazomethane generator apparatus and
procedure.
7.3 Acidified sodium sulfate - Acidify by slurrying lOOg of sodium sulfate (heated at
400oC overnight and stored in a desiccator) with enough acetone to just cover the
solid. Add 1 ml Ultrex concentrated sulfuric acid to slurry and mix thoroughly.
Remove the acetone under vacuum using a rotary evaporator. Bake dried acidified
sodium sulfate at 400'C overnight then store in desiccator until needed. Mix 1 g of
the resulting solid with 5 ml of reagent water and measure the pH of the mixture
with pH paper. The pH must be below pH 4.
7.1.6 Stock Standard Solutions are prepared in acetone.
7.1.7 Internal Standard Solutions are prepared in isooctane. Final internal standard
concentration should read 0.25 ug/ml.
7.1.8 Surrogate Standard Spiking Solutions are prepared in acetone; concentration will
differ.
Denotes reference to Battelle's Method and is not part of the ECL numbering system.
-------
Section No. 9
Revision No. 4
Date: December 1989
Page 3 of 4
7.1.9 Instrument QC Standards are prepared in isooctane from known amounts of methyl
derivatives, not acids; concentrations will differ.
10.6.1 The laboratory must, on an ongoing basis, analyze at least two laboratory controls
(all analytes) per sample set.
10.6.1.1 The spiking concentrations in the laboratory control standard should be 10 times
the MRL
10.6.1.2 Add mercuric chloride to the laboratory control sample in amounts to produce a
concentration of 10 mg/L See 8.21 Sample Preservation.
10.7 Will not be done at Referee Laboratory.
10.8 Add mercuric chloride to the Method Blank in amounts to produce a concentration
of 10 mg/L See 8.21 Sample preservation. Change EDL to MRL
10.10 Refer to Section 5.4 and 5.5.
11.1 Automated Hydrolysis, cleanup, and extraction Method is not used (11.2 Manual
Method used)
11.2.1 Spiking volume of the Surrogate Standard Solution may vary, but will not exceed
200 ul.
11.2.3 Let the sample sit at room temperature for 1 hour, shaking the separatory funnel
and contents periodically (every 15 min.).
11.2.7 Drain lower aqueous layer into a 2 Liter Ertenmeyer flask and combine ether extracts
in a 250 ml Erienmeyer flask over approximately 1 g of acidified sodium sulfate
(avoid getting water into the ether extract).
11.2.8 Periodically (every 15 min.) vigorously shake the sample and drying agent.
11.2.9 Record weight of filled water sample bottle. Pour contents into a 2 Liter separatory
funnel. Record weight of empty bottle and subtract difference to determine weight
of sample.
11.3 Extract Concentration - Using a warm (35o-40o) water bath and a stream of dry
filtered nitrogen, concentrate the ether extract to about 8 ml. Do not let ether
approach dryness. Quantitatively, transfer contents to a centrifuge tube with ethyl
ether and using a warm water bath (35o^40oQ and a stream of dry filtered nitrogen,
further concentrate extract to 0.5 ml. Add 2ml of MTBE and reconcentrate to 2 ml.
Add 250 ul of methanol and adjust volume to 4.5 ml with MTBE.
Note: Centrifuge tubes must be used instead of concentrator tubes. Avoid use of
ground-glass joints with diazomethane. (See 11.51 - Preparation of
diazomethane)
Denotes reference to Battelle's Method and is not part of the ECL numbering system.
-------
Section No 9
Revision No 4
Date December 1989
Page 4 of 4
11.4 The gaseous diazomethane method is not used.
11 5.1
and
11.5.2 Use Method, Appendix # C, for preparing diazomethane (alcoholfree ethereal
solutions). Diazomethane solution should remain tightly capped, have a yellow
color, and may be stored at 0'-5'C for a period of up to 6 months.
11.5.3 Add 1 ml of diazomethane solution to each centrifuge tube. Samples should turn
yellow after addition of the diazomethane solution and remain yellow for at least 2
mm. Repeat methylation procedure if necessary.
11.5.5 Do not use silicic acid. Use dry filtered nitrogen, and warm water bath to remove
any diazomethane that may remain. Adjust the volume to 5.0 ml with MTBE.
11.6 Preparation of Column Check - Prepare a Column Check by pipetting, onto a
Florisil® column, 1 ml of a standard containing the methyl derivatives of the analytes
of interest at 10 times the concentration of the bench or calibration standards. This
control is carried through the normal Florisil® cleanup.
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 Florisil® Cleanup Control, Method Blank, and 2 Laboratory Control Spikes which
together comprise all analytes. At a maximum, 8 Field Samples may be run in a set.
Denotes reference to Battelle's Method and is not part of the ECL numbering system.
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Section No 10
Revision No -l
Date December 1989
Page 1 of 6
10. DATA REDUCTION, VALIDATION, AND REPORTING
10.1 Data Reduction
ECL will use an H-P 3354 Data System to acquire, store, and analyze raw data from the
instrument and to generate data reports associated with each analysis. Information generated are
compound retention times, peak areas, relative response factors, and analyte concentrations. These
values plus sample i.d. and instrument parameters will comprise a DATA REPORT. Concurrent with
sample analyses, hardcopy chromatograms will be generated and along with the DATA REPORTS will
form a HARDCOPY DATA FILE. (Refer to Figure 10-1 at the end of this Section.)
Each sample chromatogram will be labelled with the Field Sample Number, final volume of
extract, ul injected, dilution information if applicable, mg-eq. of sample, date, and initials of analyst.
Each chromatogram of a standard must be labelled with the unique identifier of the bench or
calibration standard, amount injected, date of preparation of the standard, date of analysis, and initials
of the analyst.
10.2 Data Validation
Information from each DATA REPORT will be evaluated and verified by an analyst experienced
in chromatography and with this Method. Evaluation will include all QC CHECKS against
ACCEPTANCE CRITERIA as specified in Section 11.0 and the DATA MEASUREMENT requirements for
analyses as specified in Section 5.0.
Additionally, the following sampling and tracking data will be evaluated:
Is the date from sampling to receipt at ECL within the NPS requirements? (1 day)
Is the date from sampling to extraction within the NPS requirements? (14 days)
Is the date from extraction to analysis, including GC/MS confirmation, within NPS
requirements? (14 days)
SAMPLE DATA REPORTS on all samples and controls within the set will be prepared along with
QC SUMMARIES of all QC DATA from the set. For these sample extracts that must be referred to
GC/MS confirmation, the GC analyst will prepare the "GC/MS CONFIRMATION SHEET" 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 1989
Page 2 of 6
10.3 Data Reporting
Analytical sample data and QC data from the Instrument Control Standard (see Section 11.1)
will be reported via an ASCII text file on a floppy diskette. See Appendix C for instructions on the data
format and specific data to be keyed into the ASCII files. The data in the SAMPLE DATA REPORTS
and QC SUMMARIES will contain any data to be entered into the 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 E.
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 and QC
SUMMARIES. Sampling and tracking data will also be filed.
It is the responsibility of the analyst to assure that all elements of the HARDCOPY DATA FILE
are in the file. It is the responsibility of the PEER REVIEWER to see that these same elements remain
intact following review, and that they are stored by Method and Set in the RECORDS ROOM.
These files will be retained in storage until ECL is notified by NPS Management of further
disposition.
Raw data is acquired and stored on hard-disk and can be retrieved if necessary. There is no
provision for back-up magnetic tape storage. The HARDCOPY DATA FILE will contain all elements
needed to support a sample analysis. The Procedure for storage of NPS files is attached as
Appendix F.
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
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A situation when results from the secondary GC column do not agree with results
from the primary column within criteria set forth in Section 5.4. This situation is to
be discussed with the ECL Project Leader prior to reporting the data.
A protocol has been provided by NPS on reporting the "confirmed positives" mentioned above.
See Appendix_J_ for the NPS protocol and the list of analytes and their rapid reporting levels. The ECL
Project Leader will assume the duties and responsibilities assigned to the Technical Monitor in the
memo.
Also included in the Appendix are forms to be used at ECS in reporting analytes subject to
rapid reporting requirements. Forms for all three Methods being run at ECS are included with this
QAPJP since an action level in one Method triggers rapid reporting for all Methods.
It is the responsibility of the GC analyst for this Method to be aware of these rapid reporting
levels, to assure that the ECS report forms are initiated upon determining that a particular residue
associated with his/her Method is subject to rapid reporting, and to inform the ECS Project Leader
immediately.
10.6 GC/MS
10.6.1 Data Reduction
All HR GC/MS data are acquired by a Digital POP II/34 computer and stored on a CDC-CMD
disc drive. The LR GC/MS data are acquired by a Finnigan 5100 data system based on Superlncos
software. Identification is based on selected ion monitoring of EPA-designated ions and the retention
time of the analyte of interest. The GC/MS analyst will search for the analyte of interest at the proper
retention time of the standard and also look for characteristic ions. The peak areas of the selected
ions for the analyte of interest in the sample being confirmed are then compared to the same ions
generated from a standard of the analyte of interest at about the same concentration level. If marked
differences in relative abundance are observed, the analyst and Technical Monitor should account for
the discrepancy before a positive identification is established (effective 06/88). Hard copies of data
are made and kept on file. After all the results have been reviewed, the raw data is transferred to a
magnetic tape.
10.6.2 Data Validation
The hard copies of the MS data are reviewed by the mass spectrometrist for accuracy and
completeness. The data must also meet the other QA requirements in this QAPJP [See Section 5.1(8),
5.21, 5.22, 5.5, 5.6(2)], that apply. Then the Section Chief or the ECS Project Leader reviews the data,
and a decision is made as to whether or not the presence of a compound can be confirmed.
10.6.3 Data Reporting
The results of the GC/MS confirmatory analyses will be reported to the ECS Project Leader if the
sample(s) were extracted at ECS and to the appropriate Technical Monitor for the analytical contractor
if the extractions were done by the contractor. (See Figure 10-2 at the end of this Section.) One set
of hardcopy data supporting each confirmation should be attached to the form.
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Section No 10
Revision No ~
Date December 198S
Pane 4 of 6
10.6.4 Filing and Storage of GC/MS Data
The NPS Project Officer will be responsible for the initial filing and storage of GC/MS results and
data as described in Sections 10.4.
Raw data will be stored on magnetic tape by the GC/MS analyst as described in Section 10.61.
Any GC/MS analysis or confirmation can be reconstructed from this raw data.
STORAGE OF NPS HARDCOPY DATA FILES AT ECL
The HARDCOPY DATA FILES and all related reports will be filed according to NPS
Method No., and then by Sample Set.
ECL has a RECORDS ROOM available for this purpose. It is equipped with shelving
for storage, a smoke alarm, and a sprinkler system. Activation of the smoke alarm is
monitored 24 hours a day by the NSTL fire department which can respond within 2
minutes to an alarm. ECL will take precautions to protect from sprinkler syystem water
damage all files stored in this room.
The RECORDS ROOM is also the office of the ECL QAC and is locked when the
room is unoccupied. Access is limited to the ECL Laboratory Manager, the ECL QAC,
and Project/Team Leaders.
The STORED RECORDS LOG is used to log files into the RECORDS ROOM and to
record removal and subsequent return of these files.
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Section No 1C
Revision No 4
Date Decemoerl989
paae 5 of 6
FIGURE 10-1
FLOW CHART FOR DATA REDUCTION, VALIDATION, AND REPORTING
(7)
Sampling/
Tracking Data
(1)
Instrument
Response
Chromatogram
(Hardcopy)
(2)
(3)
Disk Storage
Analysis of Raw Data
By Data System
(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 Su«nmaries (by Set)
(9)
I Peer Review \ (10)
Data Packets
(ASCII Cards)
(11)
Monthly Reports (12)
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Section No ' C
Revision No 4
2ate Cecemoer 1989
Paae 6 or 6
FIGURE 10-2
MASS SPEC CONFIRMATION SHEET
Major project n*a«
Person requesting
Confirmation
Date submitted"
Sub-project name__
Person preforming
Confirmation _
Date completed" -
Sample No.
Specific details of sample extracts
Sample Cone g/ml
4
2
3
4
Compound Cone Mass Spec Mass Spec Mass Spec
Kg/ml Number Confirms- est Cone.
tion
Mass Spec
Confirmation
Code
Sample No.
Sample Cone g/ml
Compound Cone Haas Spec Mass Spec
Ng/al Number Confirtaa-
tion
Mass Spec
est. Cone
Mass Spec
Confirmation
Code
2.
3.
Sample No
Sample Cone g/ml
Compound Cone Mass Spec Mass Spec Mass Spec
Ng/ml Number Confirtaa- est. Cone
tion
Mass Spec
Confirmation
Code
Sample No.
Sample Cone g/«l_
Compound Cone Mass Spec Mass Spec Macs Spec Mass Spec
Kg/ml Number Confirms- est. Cone Confirmation
tion Code
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Section No ' 1
Revision No 4
Date December 1989
Page 1 of 11
11. INTERNAL QUALITY CONTROL CHECKS
Summarized in this Section are all the QC checks and controls required for analysis of NPS
samples. These QC checks are classified according to the analysis type (i.e.- primary column,
secondary column, GC/MS Confirmation).
11.1 Primary Analyses
Type of QC Check
• Instrument Control-7
Standard
PSF
PGF
Resolution
Sensitivity
• Method Blank
• Lab Control Standard
• Calibration Standards
- Field Samples
- Internal Standard
- Surrogate Spike
- Performance Eval
Samples
• Shipping Blank
• Spiked Sample
• Time Storage Samples
Frequency
1 day (or I set if
uninterrupted
analysis of the set
extends to 2 days)
1 set
1 std mix
Mm 1 day or each
working shift
Maximum 5 set
Each sample
Each sample
As needed
Criteria for Acceptance
0 70 < PSF < 1 05
0 70 < PGF < 1 05
> 040
_> EDL for dmoseb
No peaks within the retention window
of any analyte > Vi MRL for that
analyte
Refer to Section 1143
All analyte repsonses within jf 20% of
that predicted by current calibration
curve
See individual QC checks
Response must be wrthin + 20% of
average response of internal standard
in calibration stds.
Recovery must fall within window of R
(recovery of surrogate from applicable
control chart) + 30 percentage points
(effective 08/18/89)
To be determined
Corrective Action
Reevaluation of GC System
Reevaluation of GC System
Reevaluation of GC System
Reevaluation of GC System
Out-of-control situation, Method Blank must be brought in
control before proceeding
Out-of-control situation, work must be stopped until
control is establihsed Refer to Section 1143
1 Prepare a fresh calibration standard, or
2 Prepare a new calibration curve
See individual QC checks
Refr to Appendix C , Section 105, in the written method
1. Check calculations
2 Check mternal.and surrogate std spiking solutions
3 Reanalyze the sample extract
4 If reanalysrs of extract results tn surrogate being *in-
control," submit only data from 'm-control' analysis
5. If reanalysis fails to put surrogate in control,
reevaluate analytical method and measurement
system Reextract failed sample when system is
again in control
Out-of-control situation, problem must be corrected and
analytical system put back in control as evrdneced by
successfully analyzing a second P-E Sample
NOT APPLICABLE TO ECL REFEREE RESPONSIBILITIES
NOT APPLICABLE TO ECL REFEREE RESPONSIBILITIES
NOT APPLICABLE TO ECL REFEREE RESPONSIBILITIES
V Refer to Section 14 1 and to Appendix C . Table 10 on page 35 of the written Method
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Section No 11
Revision No 4
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Page 2 of 11
11.2 Confirmational (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
mm 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
> EDL for dinoseb
No peak within retention window
of any analyte >_ 'h MRL for that
analyte
Corrective Action
1 Prepare a fresh calibration
standard, or
2. Establish a new calibration
curve
Reevaluation 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 10 on page 35 of the written Method.
11.3 GC/MS Confirmation
• GC/MS Confirmation will be required for all compounds confirmed by second
column GC analysis.
• The sample is to be compared to a standard prepared at the concentration
determined for the sample, on either the primary or secondary column, whichever
concentration is lower.
If an analyte is confirmed by second column GC analysis but is not present when
analyzed by GC/MS, the analyst must demonstrate that the analyte was not lost
while concentrating the extract. A standard of the analyte should be prepared at
the concentration determined by GC analysis, and then concentrated and analyzed
in the same manner as the sample extract.
The Method Blank should be prepared and analyzed using the same procedures as
those used for the sample.
Confirmation is accomplished by comparison to the mass spectra of the authentic
standard and is based on characteristic EPA-designated ions and on the retention
time.
In the event that interferences preclude the use of the designated EPA ions, other
characteristic ions may be substituted on approval by the ECS-NPS Project Leader.
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Section No 11
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Page 3 of 11
Results of the GC/MS analysis are simply reported as the presence or absence of
the analyte.
Mass Spectral Confirmation Codes
MIS - Three individual ions are scanned
SPECTRA - All or a significant portion of the spectra is scanned
11.4 Control Charts
11.4.1 Establishing Control Charts
A. ECL, as a referee lab for Method 3, will be required to demonstrate control of the
measurement system via use of control charts. Control must be demonstrated for each
analyte for which quantitation is required and for the surrogate at a concentration equal to
that spiked into samples.
B. To establish the control charts, following initial demonstration of capability, 5 reagent
water samples will be spiked at 10 times the Minimal Reporting Level (MRL) for the
method and carried through extraction and analysis. Only results of analyses on the
primary column are used in establishing the control charts. An additional 15 samples will
be spiked and analyzed, 5 on each of 3 days. The data from these 20 spiked samples
will be used to construct control charts.
C. Criteria for Accuracy and Precision
1. The RSDs for any analyte must be <_ 20%, except where data, generated by Battelle
at the corresponding level, indicated poorer precision. The RSDs exceeding 20%
will be evaluated on a case-by-case basis by Technical Monitors for each method.
2. The mean recovery (x) of each analyte must lie between Battelles' mean recovery
for each analyte (at the corresponding level) +. 3 times the RSD for that analyte as
determined by Battelle during methods development, but no greater than Battelle's
mean recovery +_ 30%.
Example:
For an analyte "A"
Battelle demonstrated recovery (x) of 80% for Analyte "A" with RSD of 5%.
Acceptable recoveries will be 80% +_ 3 (5%) = 80% ± 15% = 65% - 95%;
or, Battelle demonstrated recovery (x) of 80% with RSD of 15% for analyte "A".
The acceptable recovery would be limited to 80% +_ 30% = 50% - 110%.
3. Surrogate
In establishing the control chart for the surrogate, criteria in 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.
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Section No 11
Revision No 4
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Page 4 of 11
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 (±20) 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 G.
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-Control Situations
1. In the following instances, analytical work must be stopped until an "in-control" situation is
established.
a. More than 15% of the analytes of a particular method are outside ± 3 a
b. The same analyte is outside +. 3 a 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 -h 2 o but inside the +_
3 a
b. A run of 7 consecutive points for an analyte above or below the mean.
c. A run of 7 points for an analyte in increasing or decreasing order.
The "alert" situation implies a trend toward an "out-ofcontrol" situation. The analyst
is required to evaluate his analytical system before proceeding. If "alert" or "out-of-
control" situations occur frequently, re-establishing control charts may be required
by the ECL Project Leader before analytical work can proceed.
11.4.5 Up-dating 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
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Section No 11
Revision No 4
Date December 1989
Page 5 of 11
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 Diazomethane QC Check
See "DIAZOMETHANE QC CHECK FORM" and Instructions at the end of this Section,
Figure 11-1.
11.5.2 Florisil® Elution Check
See the "ADSORBENT CHECK FORM" and Instructions at the end of this Section, Figure 11 -2.
11.5.3 Quality Control Data Sheet
Information on all solvents, reagents, and solutions used during each NFS 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 H.
11.5.4 NFS Groundwater Quality Assurance Data Form
Before any work begins on samples or controls, a "NFS GROUNDWATER QUALITY
ASSURANCE DATA FORM", is initiated by the processing laboratory. After extraction, concentration,
and cleanup, all pertinent set information is recorded on this form. This form and information for
completing it are in Appendix H.
11.6 Exceptions to the QAPjP
11.6.1 Request for Approval
Occasionally, it may become necessary for personnel assigned to the NFS 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,
NFS Method No., date, and a number to differentiate among the several discussions that may take
place on that day.
EXAMPLE: ECL 3-040888-1 indicates that an exception to the QAPjP for Method 3
was requested on April 8, and it was the first one that day.
11.6.2 Documentation and Following Requirements
The ECL Project Leader will enter into a log book the reference number, the exception
requested, and the information and documentation required to support approval of the exception to
the QAPJP.
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Section No 11
Revision No 4
Date December 1989
Page 6 of 11
The person requesting the exception to the QAPJP must prepare a folder labelled with the
reference number and his/her name, and within a time frame specified by the ECL Project Leader
have in the folder documentation of the problem/exception and all supporting information and data. A
form "EXCEPTIONS TO NPS QAPJP" is included at the end of this Section as Figure 11-3. A
completed version must be included with each request for an exception to the QAPjP.
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Section Nc 11
Revision No 4
Date December 1989
Page 7 of 11
FIGURE 11-1
DIAZOMETHANE QC FORM
PREPARATION:
Date Prepared: Analyst Preparing
Diazald Lot No. Date:
KOH Lot No. Date:
PROCESSING:
Date Methylated Analyst Methylating
' Standard Used Date:
1. Reagent Blank -
2. Spike A -
3. Spike B -
4. Spike C -
G.C. ANALYSIS:
Date Analyzed Analyst
Diazomethane Satisfactory? Yes No
G.C. Bench Standard Date:
COMMENTS:
Standard must have been prepared no longer than 30 days before Diazomethane check.
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Section No 11
Revision No 4
Date: December 1989
Page 8 of 11
FIGURE 11-1 (continued)
DIAZOMETHANE QC FORM/INSTRUCTION
INSTRUCTIONS FOR HE DIAZOMETHANE QC CHECK
For each batch of diazomethane prepared for use with NPS Method 3, complete
Part A of the "DIAZOMETHANE CHECK FORM".
To check the quality of the batch, prepare a BLANK (1 ml diazomethane w/no spike)
and 3 replicate SPIKES at the Method 3 Control Spike Level. Bring final volumes to 10.0
ml in isooctane following derivatization procedure. Analyze the BLANK and 3 replicate
SPIKES by GC. Mean recoveries of the analytes and the surrogate must be within the
control limits (except for chloramben) as reflected by the control chart in current use with
Method 3. There must also be no interfering peaks in the BLANK (for ANY Method 3
analytes) j> V* MRL If the diazomethane meets the above criteria, it can be used for NPS
analytical work.
For any exceptions to the above criteria, check with the ECL Project Leader before
using diazomethane.
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Section No 11
Revision No 4
Date December 1989
Page 9 of 11
FIGURE 11-2
ADSORBENT CHECK FORM
PROCESSING date:
Adsorbent checked: Silica-gel Florisil
Bottle date Jar letter
Lot No. Lot No.
Cat. No.
* Adsorbent Batch # Prepared by
** Standard Used Date:
G.C. ANALYSIS date:
G.C. Analyst G.C. Column
Adsorbent Satisfactory? Yes No
Bench Standard Date:
RESULTS/COMMENTS:
* Adsorbent Batch # - Silica-gel: The date deactivated.
Florisil: The date removed from oven and placed in desiccated
'* Florisil/lntermediate Standard used must match Bench Standard.
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Section No 11
Revision No 4
Date December 1989
Page 10 of 11
FIGURE 11-2 (continued)
ADSORBENT CHECK FORM/INSTRUCTIONS
INSTRUCTIONS FOR THE ADSORBENT CHECK FORM
A Florisil® QC check must be run each time new batches of Florisil® have been
activated (see Battelle Method, Section 7.1.5) and before use with NPS Method 3 work. A
Florisil* QC check is also run with each sample set.
To check a newly activated batch of Florisil® prior to use, pipette 2 ml of a recent
NPS3-7 procedural standard onto a column prepared according to Battelle Method 11.6,
and elute as per instructions in 11.6.2 - 11.6.6. Final volume is 10 ml. Compare to the
same procedural standard, and be aware that the concentration of the analytes in the
Florisil® eluate are now at half-concentration of the procedural standard. (5 ml -> 10 ml
final volume.)
Determine recoveries (%) and enter them on the "ADSORBENT CHECK FORM".
Recoveries must be 80% - 120% for all analytes EXCEPT chloramben, and there must be
no interfering peaks j> Vfe MRL for any Method 3 analyte.
For any exception to the above criteria, check with the ECL Project Leader before
using the Florisil®.
For the Florisil® QC check run with each set, the procedural standard from that set
must be used.
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Section No 11
Revision No 4
Date December 1989
Page 11 of 11
FIGURE 11-3
EXCEPTIONS TO NPS QAPjP
Date Method
Reference No.
Suggested Exception(s):
Signature of Person Seeking Exception
Approved Disapproved
Comments:
Bob Maxey, Technical Monitor
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Section No 12
Revision No 4
Date. December 1989
Page 1 of 2
12. AUDITS (Technical Systems/Data Quality/Performance Evaluation)
12.1 Requirements
Technical Systems and Data Quality Audits shall be conducted by the ECL QAC on NPS
Method 1 analytical work to assess the adherence to the QA Project Plan and to assess the quality of
data generated by the analytical systems. Performance Evaluation Audits will be initiated by ECL's
QAC to evaluate the technical personnel and the analytical system.
12.2 Frequency
12.2.1 Technical Systems and Data Quality
These audits shall be conducted at the beginning of the survey after 30 samples have been
analyzed and at least once every six months thereafter, exclusive of external audits.
12.2.2 Performance
At least one audit every six months.
12.3 Nature of Audits
12.3.1 Technical Systems Audits shall include the following:
12.3.1.1 Project Management System
12.3.1.1.1 Personnel - Qualifications
12.3.1.1.2 Documentation - QAPjP and SOPs
12.3.1.1.3 Communications about changes in requirements
12.3.1.1.4 Analyst feedback
12.3.1.2 Sample Tracking System - receipt through disposal or storage
12.3.1.3 Systems for Sample Preparations, e.g. extractions, clean up, etc.
12.3.1.4 Systems for Analytical Operations
12.3.1.4.1 Standards
12.3.1.4.2 Calibrations
12.3.1.4.3 Documentation of Analytical Operations
12.3.1.4.4 Corrective Action Loop
12.3.1.4.5 Instrument Maintenance
12.3.1.5 Data Management Systems
12.3.1.5.1 Collections
12.3.1.5.2 Reduction
12.3.1.5.3 Verification
12.3.1.5.4 Internal Review
12.3.1.5.5 Reporting
12.3.1.5.6 Use of QC Data at Bench Level
12.3.1.5.7 Data Storage and Retrieval
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Section No 12
Revision No. 4
Date: December 1989
Page 2 of 2
12.3.1.6 Laboratory Management Systems
12.3.1.6.1 Major Equipment Purchases
12.3.1.6.2 Services and Supplies (solvents, etc.)
12.3.1.6.3 Maintenance of Ancillary Equipment
12.3.1.6.4 General Physical Set Up - space, cross contamination, etc.
12.3.1.6.5 Cold Storage Facilities
12.3.2 Data Quality Audits
Shall include tracking 3 samples from Method 1 from log-in through preparation, primary and
confirmatory analyses (including related set QC checks and other information), data handling and
disposal.
12.3.3 Performance Evaluation Audits
Shall consist of providing a P-E sample every six months. The audit will consist of a P.E.
solution to be spiked into a water matrix and analyzed as a routine NPS sample. The concentration of
the analytes in the P.E. solution will be unknown to the analysts involved in the method.
12.4 Standard
ECL's Quality Assurance Project Plan for Method 1; Printed Analytical Procedure for Method 1
and ECL's Quality Assurance Facilities Plan.
12.5 Reporting and Use of Audit Results
Following any of the above audits, the ECL QAC shall report the results in writing to both the
Lab Section Chief and NPS Project Leader. If deficiencies are found, each shall be specifically
identified along with the cause, if known. The QAC will provide a written plan or suggestion for
corrective action to the NPS Project Leader with a copy to ECL's Section Chief. The QAC shall also
follow up with a limited audit to verify that deficiencies were resolved by the proposed corrective
action.
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Section No 1 3
Revision No 4
Date December 1989
Page 1 of 2
13. PREVENTIVE MAINTENANCE
13.1 Gas Chromatographs
Two Hewlett Packard 5890A dual EC/capillary Gas Chromatographs are used with Method 3
related analyses. An HP7673A autosampler is also used. Routine maintenance for these instruments
is described below. »
Maintenance Item Schedule
change injection port septa • following 2 days analytical work or as
change compressed gas traps and filter required
dryers • every 6 months or as required
• service or change injection port liner • as required by instrument performance
• bake-out or replacement of GC column • as required by instrument performance
replacement of EC detector • as required by lack of sensitivity or noise
Spare parts are maintained at ECL to accommodate the above maintenance requirements, and
at least one spare GC column of each required type is on hand. ECL has a blanket purchase-order
with Hewlett-Packard. Through it, parts and service can be accessed by telephone and usually are
provided in 2-5 working days, if needed.
A log book will be maintained for each instrument. In it will be kept records of all daily or
routine maintenance, problems and their resolution, and major repairs. It is the responsibility of the
analyst to make the above entries, and sign and date them.
13.2 GC/MS
The following schedule of maintenance tasks and spare parts applies to the Varian Mat 312 and
the Finnigan 5100.
Routine maintenance will be performed on the GC/MS and purge and trap units in accordance
with the following schedule:
Tasks Frequency
Clean source Monthly or as required by performance
Bake out magnetic and Monthly or as required by performance
electric sectors
Bake out GC column Daily or as required
Change pump oil Every 6 months or as required by use
Change GC column As required by performance
Change injection port septa Weekly or as required
Clean injection port liner Monthly or as required by performance
Most maintenance is done inhouse. When a problem is encountered which cannot be resolved
here, Finnigan MAT is contacted and service is arranged. Critical spare parts are also available to
minimize downtime and the following list of replacement parts and consumable spares is maintained
within the laboratory at all times.
1) Columns (at least one of each type used)
2) Ferrules for columns
3) Syringes
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Section No 13
Revision No 4
Date December 1989
Page 2 of 2
4) Filaments (at least two of each)
5) Gold gaskets
6) Injection port septa
7) Vacuum pump oil
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Revision No •!
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
Chromatographic and Column Performance
• Peak Symmetry Factor (PSF). See Figure 14-1 at the end of this section.
PSF = W(1/2)
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(1/2) is the
peak width at half height.
Peak Gaussian Factor (PGF). See Figure 14-1 at the end of this section.
PGF = 1.83X W(1/2) , 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)
s =
r * i '
.where
n-1
xr..xn = individual sample values
x = sample mean
n = sample size or no. of sample values
Coefficient of Variation (CV)
CV = s
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Section \c ' 4
Revision No 4
Date December 1989
Page 2 of 3
Relative Standard Deviation (RSD)
RSD = CVX 100
• Mean Recovery (R)
n r
R = 2 R/n
i=1
Percent Recovery (%R)
%R = (net value of spike) X 100
True value of spike .where
(net value of spike) = (gross value) - (value attributed to background or Blank)
Minimum Detection Limit (MDL)
MDL = s X t (.99) („_.,) , 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
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Section No 14
Revision No. 4
Dale December 1989
Page 3 of 3
FIGURE 14-1
EQUATION USED TO CALCULATE PEAK SYMMETRY FACTOR (PSF)
AND PEAK GAUSSIAN FACTOR (PGF)
o
a.
r 8
: *
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Section \c 1 5
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 NPS 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 H).
The following areas will be addressed:
specific exception to the QC requirement
when the problem was first noted and by whom
who was notified
corrective or remedial action required
action taken
• verification that a QC exception or problem was resolved and the date
sample "set" numbers and specific samples involved
If the ECL Project Leader cannot readily resolve the problem or provide guidance for corrective
action, the ECL Quality Assurance Coordinator (ECL QAC) must be notified. The QAC will take a lead
role in developing a strategy to resolve the problem. Verification that the problem has been resolved
must also be provided before analytical work continues.
Al| 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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Revision Nc 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 3. 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 3 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 3. 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 3.
The Technical Monitor for Method 3 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 Report" for that quarter will be attached to the
Technical Monitor Report. A copy of these reports will also be provided quarterly by the ECL
Analytical Coordinator to ECL's Quality Assurance Coordinator, to OPP's QAO and to the NPS QAO.
The ECL Analytical Coordinator will submit an "Analytical Coordinator Status Report" through the
ECL Section Chief to the Director of the NPS. Copies of the quarterly reports from the Technical
Monitor will be attached to the Analytical Coordinator Status Report. A copy of the latter report, Figure
16-3, is included in this section.
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Section No 15
Revision No 4
Date. December 1989
Page 2 of 4
FIGURE 16-1
EPA REFEREE LABORATORY PROGRESS - QA REPORT
Method 0
Report Period »
Analyst
\
Date
I. Progress:
9 samples received
# samples analyzed
samples invalidated
No. of data sets sent to EPA Data Manager
2. Standards: 8 stock standards diluted
Results of check befo.re using dilution
3. Bench Level Corrective Actions (s)
Date
Problem
Action Taken
Verification of Correction
Sample sec analyzed prior to problem ______________________________
(Use back of page and same for mac to report additional corrective
actions.)
4. Problems (Project-Related):
5. Information requested by Technical Monitor - (control charts, etc.)
6. Changes in Personnel:
7. Comments:
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Section No l 6
Revision No 4
Date December 1989
Page 3 of 4
FIGURE 16-2
TECHNICAL MONITOR PROGRESS - QA REPORT
Method S
Laboratory
Report Period
Date
1. Progress:
f samples received
9 samples analyzed
9 samples invalidated
No. for data sets 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 rerioo_
Prepared By _
Date
Monthly - Financial States
- Contract Administrative Needs
Quarterly - Data Summary
- Copies of quarterly reports from Technical Monitors
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Appendix A
Revision No 4
Date- December 1989
Page 1 of 6
APPENDIX A
SAMPLE CUSTODY
-------
ENVIRONMENTAL CHEMISTRY LABORATORY
NPS SAMPLE LOGGING
METHOD
PREPARED BY:
(1,3,6)
LAB. I.D.
(FIELD SAMPLE I)
i
DATE:
DATE SAMPLBD
1
'
DATE SHIPPED
I
1
1
1
1
1
1
1
DATE RECEIVED
»-
•
TIME SAMPLED
%
CONDr
-------
NPS SET COMPOSITION FORM
METHOD 3
APPROVED BY PROJECT OFFICER
SIGNATURE
DATE
Set No.
SET CONTROLS
1. Florisil elution check
2. Method Blank
3. Lab Control Spike A
4. Lab Control Spike B
Field Sample No.
NPS FIELD SAMPLES
Date Sampled
Date Arrived at ECL
9.
10.
11.
12.
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SAMPLE CONTROL RECORD
EPA/ECL
LABORATORY "
SAMPLE NO.
(REMOVED
BY
^DATE AND TIME
REMOVED
REASON
DATE AND TIME
RETURNED
-------
ECL NFS SAMPLE TRACKING FORM
METHOD 3
Date
Sample
Taken
Date
Rec'd
at ECL
Date
Extracted
Date
Analysis
Completed
Date Removed
for QC/MS
Confirmation
GC/MS
Confirmation
Completed
-------
NFS Method 0 3.Extract Storage Data Sheet
ctracts Relinquished By Date: Received By
Set:
Date:
••iisple Code
Who Stored
Date
Stored
Refrig. or
Freezer No.
Room No.
Removed
By
Purpose
Date
Removed
Returned
by
Date
Return'
Date Disposed:
Authorized by:
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Acpendix E
Revision No 4
Date December 1989
Page 1 of 50
APPENDIX B
BATTELLE'S VERSION
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Method 3. Determination of Chlorinated Acids in Ground
Water by Gas Chromatography with an Electron Capture Detector
1. SCOPE AMD APPLICATION
1.1 This is a gas chromatographic (GC) method applicable to the
determination of certain chlorinated acids in ground water.
Analytes that can be determined by this method are listed in
Table 1.
1.2 This method may be applicable to "the determination of salts and
esters of analyte acids. The form of each acid is not distin-
guished by this method. Results are calculated and reported for
each listed analyte as the total free acid.
i.3 This method has been validated in a single laboratory. Esti-
mated detection limits (EOLs) have been determined and are
listed in Table 2. Observed detection limits may vary between
ground waters, depending upon the nature of interferences in the
sample matrix and the specific instrumentation used.
1.4 This method is restricted to use by or under the supervision of
analysts experienced in the use of GC and in the interpretation
of gas chromatograms. Each analyst must demonstrate the ability
to generate acceptable results with this method using the
procedure described in Section 10.2.
1.5 When this method is used to analyze unfamiliar samples for any
or,all of the analytes above, analyte identifications must be
confirmed by at least one additional qualitative technique.
2. SUMMARY OF METHOD
2.1 A measured volume of sample of approximately 1 L is adjusted to
pH 12 with 6 N sodium hydroxide and shaken for 1 hour to
hydrolyze derivatives. Extraneous organic material is removed
by a solvent wash. The sample is acidified, and the chlorinated
acids are extracted with ethyl ether by mechanical shaking in a
separatory funnel or mechanical tumbling in a bottle. The acids
are converted to their methyl esters using diazomethane as the
derivatizing agent. Excess derivatizing reagent is removed, and
the esters are determined by GC using an electron capture
detector (ECO).1
2.2 The method provides a Florisil cleanup procedure to aid in the
elimination of interferences that may be encountered.
3. DEFINITIONS
3.1 Artificial ground water -- an aqueous matrix designed to mimic a
real ground water sample. The artificial ground water should be
•reproducible for use by others.
-------
3.2 Calibration standard -- a known amount or" a pure anaiyte,
dissolved in an organic solvent, analyzed under the same
procedures and conditions used to analyze sample extracts
containing that anaiyte.
3.3 Estimated detection limit (EDL) -- the minimum concentration of
* <-i'h«T?nco th«t ran be rr»??sured and reported with confidence
...„> cue anaiyie concentration is greater than zero as deter-
mined from the analysis of a sample in a given matrix containing
the anaiyte. The EDL is equal to the Teuel calculated by
multiplying the standard deviation of replicate measurements
times the students' t value appropriate for a 99 percent
confidence level and a standard deviation estimate with n-1
degrees of freedom or the level of the compound in a sample
yielding a peak in the final extract 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 measure-
ments 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 -- a methyl tert-butyl
ether (KTBE) 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 analytes
prepared in the laboratory by dissolving known amounts of pure
analytes in a known amount of reagent water. In this method,
the LC standard is prepared by adding appropriate volumes of the
appropriate standard solution to reagent water.
3.7 Laboratory method blank -- 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. Anaiyte 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 -- <. concentrated solution containing a
certified standard that is a method analyte, or a concentrated
solution of an analyte prepared in the laboratory with an
assayed reference compound.
.. .'.:.•.;;:>: -- i ^jre compound added to a sample in a
known amount and used to detect gross abnormalities during
sample preparation. The surrogate standard must be a compound
that is not a sample component.
4. INTERFERENCES
4.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware and other sample processing apparatus that
lead to discrete artifacts or elevated baselines in gas chroma-
togratns. All reagents and apparatus must be routinely demon-
strated to be free from interferences under the conditions of
the analysis by running laboratory method blanks as described in
Section 10.8.
4.1.1 Glassware must be scrupulously cleaned.2 Clean all
glassware as soon as possible after use by thoroughly
rinsing with the last solvent used in it. Follow by
washing with hot water and detergent and thorough
rinsing with dilute acid, tap and reagent water. Drain
dry, and heat in an oven or muffle furnace at 400"C for
1 hour. Do not heat volumetric ware. Thermally stable
materials such as PCBs might not be eliminated by this
treatment. Thorough rinsing with acetone may be substi-
tuted for the heating. After drying and cooling, seal
and store glassware in a clean environment to prevent
any accumulation of dust or other contaminants. Store
inverted or capped with aluminum foil.
4.1.2 The use of high purity reagents and solvents helps to
minimize interference problems. Purification of
solvents by distillation in all-glass systems may be
required.
4.2 The acid forms of the analytes are strong organic acids which
react readily with alkaline substances and can be lost during
sample preparation. Glassware and glass wool must be acid-
rinsed with (U9) hydrochloric acid and the sodium sulfate must
be acidified with sulfuric acid prior to use to avoid analyte
losses due to adsorption.
4.3 Organic acids and phenols, especially chlorinated compounds,
cause the most direct, interference with-the determination.
Alkaline hydrolysis and subsequent extraction of the basic
-------
sample remove many chlorinated hydrocarbons and phthalate esters
that might otherwise interfere with the electron capture
analysis.
4.£ Interferences by phthalate esters can pose a major problem in
pesticide analysis when using the ECO. These compounds general-
ly appear in the chromatogram as large peaks. Common flexible
plastics contai.n varying amounts of phthalates., that are easily
^•'erected c - " :;.ched curing laboratory operations. Cross
contamination of clean glassware routinely occurs when plastics
are handled during extraction steps, especially when sol-
vent-wetted surfaces are handled. Interferences from phthalates
can best be minimized by avoiding the use of plastics in the
laboratory. Exhaustive cleanup of reagents and glassware may be
required to eliminate background phthalate contamination.^'^
4.5 Interfering contamination nay occur when a sample containing low
concentrations of analytes is analyzed immediately following a
sample containing relatively high concentrations of analytes.
Between-sample rinsing of the sample syringe and associated
equipment with HTBE can minimize sample cross contamination.
After analysis of a sample containing high concentrations of
analytes, one or more injections of HTBE should be made to
ensure that accurate values are obtained for the next sample.
4.6 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. The cleanup procedures in Section 11 can
be used to overcome many of these interferences. Positive
identifications-should be confirmed using the confirmation
column specified in Table 3.
5. SAFETY
5.1 The toxicity or carcinogenicity of each reagent used in this
method has not been precisely defined; however, each chemical
compound must be treated as a potential health hazard. From
this viewpoint, exposure to these chemicals must be reduced to
the lowest possible level by whatever means available. The
laboratory is responsible for maintaining a current awareness
file of OSHA regulations regarding the safe handling of the
chemicals specified in this method. A reference file of
material safety data sheets should also be made available to all
personnel involved in the chemical analysis. Additional
references to laboratory safety are available and have been
identified^"' for the information of the analyst.
5.2 Diazomethane is a toxic carcinogen and can explode under certain
conditions. The following precautions must be followed:
5.2.1 Use only a well ventilated hood -- do not breath vapors.
5.2.2 Use a safety screen.
II
-------
5.2.3 Use mechanical pipetting aides.
5. 2.4 Do not heat above 9CTC -- EXPLOSION may result.
5.2.5 Avoid grinding surfaces, ground glass joints, sleeve
bearings, glass --
5.2.6 Store away from
Avoid grinding surfaces, ground glass joints, sleeve
bearings, glass stirrers -- EXPLOSION may result.
Store away from alkali metals -- EXPLOSION may result.
5.2.7 Solutions of diazomethane decompofe rapidly in the
presence of solid materials such as copper powder,
calcium chloride, and boiling chips.
5.3 Ethyl ether is an extremely flammable solvent. If a mechanical
device is used for sample extraction, the device should be
equipped with an explosion-proof motor and placed in a hood to
avoid possible damage and injury due to an explosion.
6. APPARATUS AND EQUIPMENT (All specifications are suggested. Catalog
numbers are included for illustration only.)
6.1 SAMPLING EQUIPMENT
6.1.1 Grab sample bottle -- Borosilicate, 1-L volume with
graduations (Wheaton Media/Lab bottle 219820), fitted
with screw caps lined with TFE-fluorocarbon. Protect
samples from light. The container must be washed and
dried as described in Section 4.1.1 before use to
minimize contamination. Cap liners are cut to fit from
sheets (Pierce Catalog No. 012736) and extracted with
methane! overnight prior to use.
6.2 GLASSWARE
6.2.1 Separatory funnel -- 2000-mL, with TFE-fluorocarbon
stopcocks, ground glass or TFE-fluorocarbon stoppers.
6.2.2 Tumbler bottle -- 1.7-L (Wheaton Roller Culture Vessel),
with TFE-fluorocarbon lined screw cap. Cap liners are
cut to fit from sheets (Pierce Catalog No. 012736) and
extracted with methanol overnight prior to use.
6.2.3 Concentrator tube, Kuderna -Danish (K-0) -- 10- or 25-mL,
graduated (Kontes K-570050-2525 or Kontes K-S700SO-102S
or equivalent). Calibration must be checked at the
volumes employed in the test. Ground glass stoppers are
used to prevent evaporation of extracts.
6.2.4 Evaporative flask, K-0 -- 500-mL (Kontes K-570001-0500
or equivalent). Attach to concentrator tube with
springs.
. 6.2.5 - Snyder column, K-0 -- three-ball macro (Konles K-503000-
0121 or equivalent).
-------
6.2.6 Snyder column, K-0 -- two-ball micro (Kontes K-569001-
0219 or equivalent).
6.2.7 Flask, round-bottom -- SOO-ml with 24/40 ground glass
joint.
6.2.8 Vials -- glass, 5- to 10-mL capacity with TFE-fluoro-
carboa lined screw cap.
6.2.9 Disposable pipets -- sterile plugged borosilicate glass,
5-ml capacity (Corning 70.78-5N or equivalent).
6.3 Separatory funnel shaker -- Capable of holding eight 2-L separa-
tory funnels and shaking them with rocking motion to achieve
thorough mixing of separatory funnel contents (available from
Eberbach Co. in Ann Arbor, MI).
6.4 Tumbler -- Capable of holding 4 to 6 tumbler bottles and
tumbling them end-over-end at 30 turns/min (Associated Design
ana Mfg. Co., Alexandria, VA).
6.5 Boiling stones -- Teflon, CHEKVARE (Norton Performance Plastics
No. 015021).
6.6 Water bath -- Heated, capable of temperature control (i2"C).
The bath should be used in a hood.
€.7 Balance -- Analytical, capable of accurately weighing to the
nearest 0.0001 g.
6.8 Gaseous diazomethane generator -- Diazomethane generator
assembly as shown in Figure 1 (available from Aldrich Chemical
Co.).
6.9 Diazomethane solution generator -- Assemble from two 20 x 150 mm
test tubes, two Meoprene rubber stoppers, and a source of
nitrogen. The diazomethane collector is cooled in an approx-
imately 2-L thermos for ice bath or a cryogenically cooled
vessel (Thermoelectrics Unlimited Model SK-12 or equivalent).
The generation/collection assembly is shown in Figure 2.
6.10 Glass wool -- Acid washed (Supelco 2-0383 or equivalent) and
heated at <50*C for 4 hours.
6.11 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.
6.11.1 Primary column -- 30 m long x 0.25 mm 1.0. DB-5 bonded
fused silica column, 0.25 urn film thickness (available
from JiW). Validation data"presented in this method-
/3
-------
were obtained using this column. Alternative columns
may be used in accordance with the provisions described
in Section 10.3.
6.11.2 Confirmation column -- 30 m long x 0.25 mm 1.0. 08-1701
bonded fused silica column, 0.25 urn film thickness
(available from JiW).
6.11.3 Detector -- Electron capture. This detector has proven
effective in the analysis of spiked reagent and arti-
ficial ground waters. An ECO was used to generate the
validation data presented in this method. Alternative
detectors, including a mass spectrometer, may be used in
accordance with the provisions described in
Section 10.3.
7. REAGENTS AND CONSUMABLE MATERIALS
7.1 Acetone, methanol, methylene chloride, KTBE -- Pesticide quality
or equivalent.
7.2 Ethyl ether, unpreserved -- Nanograde, redistilled in glass if
necessary. Must be free of peroxides as indicated by EH Quant
test strips (available from Scientific Products Co., Cat. No.
PI 126-8, and other suppliers). Procedures recommended for
removal of peroxides are provided with the test strips.
7.3 Sodium sulfate, granular, anhydrous, ACS grade -- Heat treat in
a shallow tray at 4SO*C for a minimum of 4 hours to remove
interfering organic substances. Acidify by slurrying 100 g
sodium sulfate with enough ethyl ether to just cover the solid.
Add 0.1 ml concentrated sulfuric acid and mix thoroughly.
Remove the ether under vacuum. Mix 1 g of the resulting solid
with 5 ml of reagent water and measure the pH of the mixture.
The pH must be below pH 4. Store at 130*C.
7.4 Sodium hydroxide (HaOH), pellets -- ACS grade.
7.4.1 NaOH, 6 N -- Dissolve 216 g NaOH in 900 ml reagent
water.
7.5 Sulfuric acid (l^SO^). concentrated, ACS grade -- sp. gr. 1.84.
7.S.I H?S04, 12 N -- Slowly add 335 ml concentrated H2S04 to
665 ml of reagent water.
7.6 Potassium hydroxide (KOH), pellets -- ACS grade.
7.6.1 KOH, 37% (w/v) -- Dissolve 37 g KOH pellets in reagent
water and dilute to 100 ml.
7.7 Carbitol (diethylene glycol monoethyl ether), ACS grade --
available from Aldr.ich Chemical Co.
-------
7.8 Oiazald, ACS grade -- available from Aldrich Chemical Co.
7.9 Chazald solution -- Prepare a solution containing 10 g Oiazald
in 100 ml of a 50:50 by volume mixture of ethyl ether and
carbitol. This solution is stable for one month or longer when
stored at 4*C in an amber bottle with a Teflon-lined screw cap.
7.10 Sodium chlorid.e (NaCl), crystal, ACS grade -- Heat, treat in a
shallow tray at 450"C for a minimum of 4 hours to remove
interfering organic substances.
" ' ' '-'-Oibromooctafluorobiphenyl (OBOB) -- >997. purity, for use as
- ........ ,. ....... ........ /..v.Vv.i, fr- •-•'•• '• ~ .
7.12 2,4-Oichlorophenylacetic acid (OCAA) -- >99% purity, for use as
surrogate standard (available from Aldrich Chemical Co).
7.13 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.
7.14 Silicic acid, ACS grade
7.15 Florisil -- 60-100/PR mesh (Sigma No. F-9127). Activate by
heating in a shallow container at 150'C for at least 24 and not
more than 48 hours.
7.!6 STOCK STANDARD SOLUTIONS (1.00 ug/pL) -- Stock standard solu-
tions may be purchased as certified solutions or prepared from
pure standard materials using the following procedure:
7.16.1 Prepare stock standard solutions by accurately weighing
approximately 0.0100 g of pure material. Dissolve the
material in HTBE and dilute to volume in a 10-mL volu-
metric flask. Larger volumes may be used at the conven-
ience of the analyst. If compound purity is certified
at 96% or greater, the weight may be used without
correction to calculate the concentration of the stock
standard. Commercially prepared stock standards may be
used at any concentration if they are certified by the
manufacturer or by an independent source.
7.16.2 Transfer the stock standard solutions into TFE-fluoro-
carbon-sealed screw cap vials. Store at room tempera-
ture and protect from light.
7.16.3 Stock standard solutions should be replaced after two
months or sooner if comparison with laboratory control
standards indicates a problem.
7.-17 INTERNAL STANDARD SPIKING SOLUTION — Prepare an internal
standard spiking solution by accurately weighing approximately
8
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0.0010 g of pure OBOB. Dissolve the D80B in MTBE and dilute to
volume in a 10-ml_ volumetric flask. Transfer the internal
standard spiking solution to a TFE-fluorocarbon-sealed screw cap
bottle and store at room temperature. Addition of 25 ul of the
internal standard spiking solution to 10 ml of sample extract
results in a final internal standard concentration of 0.25
Solution should be replaced when ongoing QC (Section 10)
indicates a problem.
7.18 SURROGATE STANDARD SPIKING SOLUTION -- Prepare a surrogate
standard spiking solution by accurately weighing approximately
0.0010 g of pure DCAA. Dissolve the DCAA in MTBE and dilute to
volume in a 10-mL volumetric flask. Transfer the surrogate
standard spiking solution to a TFE-fluorocarbon-sealed screw cap
bottle and store at room temperature. Addition of 50 uL of the
surrogate standard spiking solution to a 1-L sample prior to
extraction results in a surrogate standard concentration in the
sample of 5 ug/L and, assuming quantitative recovery of OCAA, a
surrogate standard concentration in the final extract of
0.5 pg/mL. Solution should be replaced when ongoing QC (Section
10) indicates a problem.
7.19 INSTRUMENT QC STANDARD -- Prepare a diluted dinoseb solution by
adding 10 pi of the 1.0 uc/uL dinoseb stock solution to MTBE and
diluting to volume in a 10-rcL volumetric flask. To prepare the
instrument QC standard, add <0 uL of the diluted dinoseb
solution, 16 ul of the 4-nitrophenol stock solution, 6 ul of the
3,5-dichlorobenzoic acid stock solution, 50 ul of the surrogate
standard spiking solution, 25 ul of the internal standard
spiking solution, and 250 ul of methanol to a 5-mL volumetric
flask and diluting to volume with MTBE. Methylate sample as
described in Section 11.<. Dilute the sample to 10 ml in MTBE.
Transfer the instrument QC standard to a TFE-fluorocarbon-
sealed screw cap bottle and store at room temperature. Solution
should be replaced when ongoing QC (Section 10) indicates a
problem.
8. SAMPLE COLLECTION. PRESERVATION. AND STORAGE
8.1 Grab samples must be collected in glass containers. Conven-
tional sampling practices8 should be followed; however, the
bottle must not be prerinsed with sample before collection.
8.2 SAMPLE PRESERVATION AND STORAGE
8.2.1 Add mercuric chloride to the sample bottle in amounts to
produce a concentration of 10 mg/L. Add 1 ml of a
10 mg/mL solution of mercuric chloride in water to the
sample bottle at the sampling site or in the laboratory
before shipping to the sampling site, A major dis-
advantage of mercuric chloride is that it is a highly
toxic chemical; mercuric chloride must be handled with
caution, and samples containing mercuric chloride must
be disposed of properly.
-------
8.2.2 After the sample is collected in the bottle containing
preservative, seal the bottle and shake vigorously for
1 mm.
8.2.3 The samples must be iced or refrigerated at 4"C awav
from light from the time of collection until extraction.
Preservation study results given in Table 11 indicate
that most analytes present in samples stored under these
conditions are stable for at least^S days after
collection. However, analyte stability may be affected
by the matrix; therefore, the analyst should verify that
the preseraation technique is applicable to the samples
under study.
8.3 EXTRACT STORAGE
8.3.1 Extracts should be stored at A'C away from light.
Preservation study results given in Table 11 indicate
that that most analytes are stable for 28 days; however,
the analyst should verify appropriate extract holding
times applicable to the samples under study.
CALIBRATION
9.1 Establish GC operating parameters equivalent to those indicated
in Table 3. The GC system must be calibrated using the internal
standard technique (Section 9.2).
9.2 INTERNAL STANDARD CALIBRATION PROCEDURE -- To use this approach,
the analyst must select one or more internal standards compat-
ible in analytical behavior to the compounds of interest. The
analyst must further demonstrate that the measurement of the
internal standard is not affected by method or matrix interfer-
ences.
9.2.1 Prepare calibration standards at a minimum of three
(suggested five) concentration levels for each analyte
of interest by adding volumes of one or more stock stan-
dards to a volumetric flask. To each calibration
standard, add a known constant amount of one or more
internal standards and 250 uL methanol, and dilute to
volume with MTBE. Esterify acids with diazomethane as
described in Section 11.3. One of the calibration
standards should be representative of an analyte
concentration near, but above, the EDL. The other
concentrations should correspond to the range of
concentrations expected in the sample concentrates, or
should define the working range of the detector.
9.2.2 Inject 2 uL of each calibration standard'and tabulate
the relative response for each analyte (RRa) to the
internal standard using the equation:
10
-------
a ~ a/ i s
where: Aa = the peak area of the analyte, and
A,s = the peak area of the internal standard.
Generate a calibration curve of RR, versus analyte
concentration in the sample in ug/L.
9.2.3 The working calibration curve must^be verified on each
working shift by the measurement of one or more calibra-
tion standards. If the response for any analyte varies
from the predicted response by more than ±20%, the test
must be repeated using a fresh calibration standard.
Alternatively, a new calibration curve must be prepared
for that analyte.
10. QUALITY CONTROL
iO.l Each laboratory using this method is required to operate a
quality control (QC) program. The minimum requirements of this
program consist of the following: an initial demonstration of
laboratory capability; the analysis of surrogate standards in
each and every sample as a continuing check on sample prepara-
tion; the monitoring of internal standard area counts or peak.
heights in each and every sample as a continuing check on system
performance; the analysis of laboratory control standards, QC
samples, and performance evaluation (PE) samples as continuing
checks on laboratory performance; the analysis of spiked samples
as a continuing check on recovery performance; the analysis of
method blanks as a continuing check on contamination; and
frequent analysis of the instrument QC standard to assure
acceptable instrument performance.
10.2 INITIAL DEMONSTRATION OF CAPABILITY -- To establish the ability
to perform this method, the analyst must perform the following
operations.
10.2.1 Select a representative spike concentration (suggest
15 times the EOL) for each of the target analytes.
Using a stock standard that differs from calibration
standard, prepare a laboratory control (LC) check sample
concentrate in methanol 1000 times more concentrated
than the selected spike concentration.
10.2.2 Using a syringe, add 1 ml of the LC sample concentrate
to each of a minimum of four 1-L aliquots of reagent
water. A representative ground water may be used in
place of the reagent water, but one or more unspiked
aliquots must be analyzed to determine background
levels, and the spike level must, at a minimum, exceed
twice the background level for the test to be valid.
Analyze the aliquots according to the method beginning
in Section 11. - •
11.
I*
-------
10.2.3 Calculate the average percent recovery (R) and the
standard deviation of the percent recovery (Sp), for the
results. Ground water background corrections must be
made before R and SR calculations are performed.
10.2.4 Table 2 and Tables 4-9 provide single laboratory
recovery and precision data obtained for the method
analytes from reagent and artificial ground waters,
respectively. Similar results from dosed reagent and
artificial ground waters should be expected by any
experienced laboratory. Compare results obtained in
Section 10.2.3 to the single laboratory recovery and
precision data. If the results are not comparable,
review potential problem areas and repeat the test.
Results are comparable if the calculated percent
relative standard deviation (RSD) does not exceed 2.6
times the single laboratory RSD or 20 percent, whichever
is greater, and your mean recovery lies within the
interval R+3S or R+30'/. whichever is greater.
10.3 In recognition of the rapid advances occurring in chromato-
graphy, the analyst is permitted to modify GC columns, GC
conditions, or detectors to improve the separations or lower the
cost of measurements. Each tme such modifications to the
method are made, the analyst is required to repeat the procedure
in Section 10.2.
10.4 ASSESSING SURROGATE RECOVERY
10.4.1 All samples and blanks must be fortified with the
surrogate spiking compound before extraction. A
surrogate standard determination must be performed on
all samples (including matrix spikes) and blanks.
10.4.2 Determine whether the measured surrogate concentration
(expressed as percent recovery) falls between 70 and 130
percent.
10.4.3 When the surrogate recovery for a laboratory method
blank is less than 70 or greater than 130 percent, the
laboratory must take the following actions:
(1) Check calculations to make sure there are no
errors.
(2) Check internal standard and surrogate standard
spiking solutions for degradation, contamination,
or other obvious abnormalities.
(3) Check instrument performance.
Reinject the laboratory method blank extract. If the
reanalysis fails-the 70 to 130 percent recovery
criteria, the analytical system must be considered "out
12
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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 from the
analysis with surrogate spike recoveries within the
required limits. If reanalysis of the sample or extract
fails to solve the problem, then report all data for
• that sample as suspect.
10.5 ASSESSING THE INTERNAL STANDARD
10-.5.1 An internal standard peak area or peak height check must
be performed on all samples. All sample extracts must
be fortified with the internal standard.
10.5.2 Internal standard recovery must be evaluated for
acceptance by determining whether the measured peak area
or peak height for the internal standard in any sample
deviates by more than 30 percent from the average peak
area or height for the internal standard in the calibra-
tion standards.
10.5.3 When the internal standard peak area or height for any
sample is outside the limit specified in 10.5.2, the
laboratory must investigate.
10.5.3.1 Single occurrence •- Reinject an aliquot of
^the extract to ensure proper sample injection.
If the reinjected sample extract aliquot
displays an internal standard peak area or
height within specified limits, quantify and
report results. If the reinjected sample
extract aliquot displays an internal standard
peak area or height outside the specified
limits, but-extract aliquots from other .
samples continue to give the proper area or
13
-------
height for the internal standard, assume an
erro<- was made during addition of the internal
standard to the failed sample extract. Repeat
the analysis of that sample.
10.5.2.2 Multiple Occurrence -- If the internal
standard peak areas or heights for successive
samples fail the specified criteria (JO.5.2),
check*the instrument for proper performance.
After optimizing instrument performance, check
the calibration curve using a calibration
check standard (Section 9). If the calibra-
tion curve is still applicable and if the
calibration check standard internal standard
peak area or height is within ±30% of the
average internal standard peak area or height
for the calibration standards, reanalyze those
sample extracts whose internal standard failed
the specified criteria. If the internal
standard peak areas or heights now fall within
the specified limits, report the results. If
the internal standard peak areas or heights
still fail to fall within the specified limits
or if the calibration curve is no longer
applicable, then generate a new calibration
curve (Section 9) and reanalyze those sample
extracts whose internal standard failed the
peak area or height criteria.
10.6 ASSESSING LABORATORY PERFORMANCE
10.6.1 The laboratory must, on an ongoing basis, analyze at
least one laboratory control standard per sample set (a
sample set is all those samples extracted within a
24-hour period).
10.6.1.1 The spiking concentration in the laboratory
control standard should be IS times the EDI.
10.6.1.2 Spike a 1-L aliquot of reagent water with a
laboratory control (LC) sample concentrate
(the volume of the spike should be kept to a
minimum so the solubility of the analytes of
interest in water will not be affected) and
analyze it to determine the concentration
after spiking (A) of each analyte. Calculate
each percent recovery (Rj) as (100xA)%/T,
where T is the known true concentration of the
spike.
10.6.1.3 Compare the percent recovery (R^J for each
analyte with established QC acceptance
criteria. QC criteria are established by
initially analyzing five laboratory control
U
-------
standards and calculating the averaae percent
recovery (P) ind the standard deviation of the
percent recovery (SpJ using the following
equations:
R,/n
\ / n \ 2 j
-iii ^-ii^i
ii*i . *. • i i
I n-l ! -
where: n = number of measurements for each
analyte, and
Rj = individual percent recovery
value.
Calculate OC acceptance criteria as follows:
Upper Control Limit (UCL) - R * 3Sp
Lower Control Limit (LCL) - 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 con-
tinuous basis. After each five to ten new
recovery measurements (RiS), recalculate R and
SR using all the data, and construct new
control limits. When the total number of data
points reach twenty, update the control limits
by calculating R and SR using only the most
recent twenty data points.
Monitor all data from laboratory control
standards. Analyte recoveries must fall
within the established control limits.
If the recovery of any such analyte falls
outside the designated range, the laboratory
performance for that analyte is judged to be
out of control, and the source of the problem
roust be immediately identified and resolved
before continuing the analyses. The analyti-
15
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cal result, for that analyte in samples is
suspect and must be so labeled. All results
for that analyte in that sample set must also
be labeled suspect.
10.6.2 Each Quarter, it is essential that the laboratory
analyze (if available) QC check standards. If the
criteria established by the U.S. Environmental Protec-
tion Agency (USEPA) and provided wvth the QC standards
are not met, corrective action needs to be taken and
documented.
10.6.3 The laboratory must analyze an unknown performance
evaluation sample (when available) at least once a year.
Results for each of the target analytes need to be
within acceptable limits established by USEPA.
10.7 ASSESSING AMAIYTE RECOVERY
10.7.1 The laboratory must, on an ongoing basis, spike each of
the target analytes into ten percent of the samples.
10.7.1.1 The spiking concentration in the sample should
be one to five times the background concentra-
tion, or, if it is'impractical to determine
background levels before spiking, 15 times the
EDL.
10.7.1.2 Analyze one sample aliquot to determine the
background concentration (B) of each analyte.
Spike a second sample aliquot with a labora-
tory control (LC) sample concentrate (the
volume of the spike should be kept to a
minimum so the solubility of the analytes of
interest in water will not be affected) and
analyze it to determine the concentration
after spiking (A) of each analyte. Calculate
each percent recovery (R^) as 100(A-B)%/T,
where T is the known true concentration of the
spike.
10.7.1.3 Compare the percent recovery (R,) for each
analyte with QC acceptance criteria esta-
blished from the analyses of laboratory
control standards.
Monitor all data from dosed samples. Analyte
recoveries must fall within the established
control limits.
10.7.1.4 If the recovery of any such analyte falls
outside the designated range, and the labora-
tory performance for that analyte is judged, to
be in control, the recovery problem encoun-
. 16
-Q
-------
tered with the dosed sample is judged to be
matrix-related, not system-related^ The
result for that analyte in the unspiked sample
is labeled suspect/matrix to inform the user
that the results are suspect due to matrix
effects.
10.8 ASSESSING LABORATORY CONTAMINATION (METHOD BLANKS) -- Before
processing any samples, the analyst must demonstrate that all
glassware and reagent interferences are under control. This is
accomplished by the analysis of 2 laboratory method blank. A
laboratory method blank is a 1-L aliquot of reagent water
analyzed as if it was a sample. Each time a set of samples is
extracted or there is a change in reagents, a laboratory method
blank must be processed to assess laboratory contamination. If
the method blank exhibits z peak within the retention time
window of any analyte which is greater than or equal to one-
half the EDL for that analyte, determine the source of contam-
ination before processing samples and eliminate the interference
problem.
10.9 ASSESSING INSTRUMENT PERFORMANCE (INSTRUMENT QC STANDARD) --
Instrument performance should be monitored on a daily basis by
analysis of the instrument QC standard. The instrument QC
standard contains compounds designed to indicate appropriate
instrument sensitivity, column performance and chromatographic
performance. Instrument QC standard components and performance
criteria are. listed in Table 10. Inability to demonstrate
acceptable instrument performance indicates the need for
revaluation of the GC-ECO system. A GC-ECD chromatogram
generated from the analysis of the instrument QC standard is
shown in Figure 3. The sensitivity requirements are set based
on the EDLs published in this method. If laboratory EDLs differ
from those listed in this method, concentrations of the instru-
ment QC standard compounds must be adjusted to be compatible
with the laboratory EDLs. An instrument QC standard should be
analyzed with each sample set.
10.10 ANALYTE CONFIRMATION - When doubt exists over the identification
of a peak on the chromatogram, confirmatory techniques such as
mass spectrometry or a second gas chromatography column must be
used. A suggested confirmation column is described in Table 3.
10.11 ADDITIONAL QC - It is recommended that the laboratory adopt
additional quality assurance practices for use with this
method. The specific practices that are most productive depend
upon the needs of the laboratory and the nature of the samples.
11. PROCEDURE
11.1 AUTOMATED HYDROLYSIS* CLEANUP,. AKO EXTRACTION METHOD -- Valida-
tion data presented in this method were generated using the
17
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automated extraction procedure with the mechanical separatory
funnel shaker.
11.1.1 Add preservative to any samples not previously preserved
(Section 8.2). Mark the water meniscus on the side of
the sample bottle for later determination of sample
volume. Spike sample with 50 pi of the surrogate
standard spiking solution. If the mechanical separatory
funnel shaker is used, pour the entire sample into a 2-1
separatory funnel. If the mechanical tumbler is used,
pour the entire sample into a tumbler bottle.
11.1.2 Add 250 g NaCl to the sample, .seal, and shake to
dissolve salt.
11.1.3 Add 17 ml of 6 N NaOH to the sample, seal, and shake.
Check the pH of the sample with pH paper; if the sample
does not have a pH greater than or equal to 12, adjust
the pH by adding more 6 N NaOH. Shake sample for 1 hour
using the appropriate mechanical mixing device.
11.1.4 .Add 300 ml methylene chloride to the sample bottle to
rinse the bottle, transfer the methylene chloride to the
separatory funnel or tumbler bottle, seal, and shake for
10 s, venting periodically. Repeat shaking and venting
until pressure release is not observed during venting.
Reseal and place sample container in appropriate
mechanical mixing device. Shake or tumble the sample
for 1 hour. Complete and thorough mixing of the organic
and aqueous phases should be observed at least 2 min
after starting the mixing device.
11.1.5 Remove the sample container from the mixing device. If
the tumbler is used, pour contents of tumbler bottle
into a 2-L separatory funnel. • Allow the organic layer
to separate from the water phase for a minimum of 10
min. If the emulsion interface between layers is more
than one third the volume of the solvent layer, the
analyst must employ mechanical techniques to complete
the phase separation. The optimum technique depends
upon the sample, but may include stirring, filtration
through glass wool, centrifugation, or other physical
methods. Drain and discard the organic phase. If the
tumbler is used, return the aqueous phase to the tumbler
bottle.
11.1.6 Add 17 ml of 12 N ^504 to the sample, seal, and shake
to mix. Check the pH of the sample with pH paper; if
the sample does not have a pH less than or equal to 2,
adjust the pH by adding more 12 N ^$04..
11.1.-7 Add 300 ml ethyl ether to the sample, seal, and shake
for 10 s, venting periodically. Repeat shaking and
venting until pressure release is not observed during
18
-------
venting. Reseal and place sample container in approp-
riate mechanical mixing device. Shake or tumble sample
for 1 hour. Complete and thorough mixing of the organic
and aqueous phases should be observed at least 2 mm
after starting the mixing device.
11.1.8 Remove the sample container from the mixing device. If
the tumbler is used, pour contents of tumbler bottle
into a-2-L separatory funnel. Allow the organic layer
;•„ -.:, .-.:'.. from the water phase for a minimum of 10
min. If the emulsion interface between layers is more
than one third the volume of the solvent layer, the
analyst must employ mechanical techniques to complete
the phase separation. The optimum technique depends
upon the sample, but may include stirring, filtration
through glass wool, centrifugation, or other physical
methods. Drain and discard the aqueous phase. Collect
the extract in a 500-ml round-bottom flask containing
about 10 g of acidified anhydrous sodium sulfate.
Periodically vigorously shake the sample and drying
agent. Allow the extract to remain in contact with the
sodium sulfate for approximately 2 hours.
11.1.9 Determine the original sample volume by refilling the
sample bottle to the mark and transferring the water to
a 1000-mL graduated cylinder. Record the sample volume
to the nearest 5 mL.
11.2 MANUAL HYDROLYSIS, CLEANUP, AND EXTRACTION METHOD -- Alternative
procedure.
11.2.1 Add preservative to any samples not previously preserved
(Section 8.2). Mark the water meniscus on the side of
the sample bottle for later determination of sample
volume. Pour the entire sample into a 2-L separatory
funnel. Spike sample with 50 uL of the surrogate
standard spiking solution.
11.2.2 Add 250 g NaCl to the sample, seal, and shake to
dissolve salt.
11.2.3 Add 17 mL of 6 N NaOH to the sample, seal, and shake.
Check the pH of the sample with pH paper; if the sample
does not have a pH greater than or equal to 12, adjust
the pH by adding more 6 N NaOH. Let the sample sit at
room temperature for 1 hour, shaking the separatory
funnel and contents periodically.
11.2.4 Add 60 mL methylene chloride to the sample bottle to
rinse the bottle, transfer the methylene chloride to the
separatory funnel and extract the sample-by vigorously
shaking the funnel for 2 min with periodic venting to
release excess pressure. Allow the organic layer to
separate from the water phase for a minimum of 10 min.
19
-------
If the emulsion interface between layers is more than
one third the volume of the solvent layer, the analyst
must employ mechanical techniques to complete the phase
separation. The optimum technique depends upon the
sample, but may include stirring, filtration through
glass wool, centrifugation, cr other physical methocs.
Discard the methylene chloride phase.
11.2.5 Add a second 60-mL volume of methylene chlori-^ 1.c : .
.c.«v^ uOtllc ^ad iepcat the extraction procedure o
second time, discarding the methylene chloride layer.
Perform a third extraction in the same manner.
11.2.6 Add 17 mL of 12 N ^50$ to the sample, seal, and «_: '•••••
to mix. Check the pH of the sample with pH paper; iv
the sample does not have a pH less than or equal to 2,
adjust the pH by adding more 12 N
11.2.7 Add 120 mL ethyl ether to the sample, seal, and extract
the sample by vigorously shaking the funnel for 2 min
with periodic venting to release excess pressure. Allow
the organic layer to separate from the water phase for a
minimum of 10 min. If the emulsion interface between
layers is more than one third the volume of the solvent
layer, the analyst must employ mechanical techniques to
complete the phase separation. The optimum technique
depends upon the sample, but tr,ay include stirring,
filtration through glass wool, centrifugation, or other
physical methods. Remove the aqueous phase to a 2-L
Erlenmeyer flask and collect the ethyl ether phase in a
500-mL round-bottom flask containing approximately 10 c
of acidified anhydrous sodium sulfate.
11.2.8 Return the aqueous phase to the separatory funnel, add a
60-mL volume of ethyl ether to the sample, and repeat
the extraction procedure a second time, conbining the
extracts in the 500-mL erlenmeyer flask. Perform a
third extraction with 60 mL of ethyl ether in the same
manner. Periodically vigorously shake the sample and
drying agent. Allow the extract to remain in contact
with the sodium sulfate for approximately 2 hours.
11.2.9 Determine the original sample volume by refilling the
sample bottle to the mark and transferring the water to
a 1000-mL graduated cylinder. Record the sample volume
to the nearest 5 mL.
11.3 EXTRACT CONCENTRATION
11.3.1 Assemble a K-0 concentrator by attaching a concentrator
tube to a 500-mL evaporative flask.
11.3.2 Pour the dried extract thrpugh a funnel plugged with
acid washed glass wool, and collect the extract in the
20
2.7
-------
K-D in concentrator. Use a glass rod to crush any caked
sodium sulfate during the transfer. Rinse the round-
bottom flask and funnel with 20 to 30 mL of ethyl ether
to complete the quantitative transfer.
11.3.3 Add 1 to 2 clean boiling stones to the evaporative flask
and attach a macro Snyder column. Prewet the Snyder
column by adding about 1 mL ethyl ether to the top.
. Uce the K-0 apparatus on a hot water bath, 60 to 65*C,
so that the concentrator tube is partially immersed in
the hot water, and the entire lower rounded surface of
the flask is bathed with hot vapor. At the proper rate
of distillation the balls of the column will actively
chatter but the chambers will not flood. When the
apparent volume of liquid reaches 1 mL, remove the K-0
apparatus and allow it to drain and cool for at least 10
min.
11.3.4 Remove the Snyder column and rinse the flask and its
lower joint into the concentrator tube with 1 to 2 mL of
ethyl ether. Add 2 mL of MTBE and a fresh boiling
stone. Attach a micro-Snyder column to the concentrator
tube and prewet the column by adding about 0.5 mL of
ethyl ether to the top. Place the micro K-0 apparatus
on the water bath so that the concentrator tube is
partially immersed in the hot water. Adjust the
vertical position of the apparatus and the water
temperature as required to complete concentration in 5
to 10-min. When the apparent volume of liquid reaches
O.S mL, remove the micro K-0 from the bath and allow it
to drain and cool. Remove the micro Snyder column and
add,250 uL of methanol. If the gaseous diazomethane
procedure (Section 11.4) is used for esterification of
pesticides, rinse the walls of the concentrator tube
while adjusting the volume to 5.0 mL with MTBE. If the
pesticides will be esterified using the diazomethane
solution (Section 11.5), rinse the walls of the concen-
trator tube while adjusting the volume to 4.5 mL with
MTBE.
11.4 ESTERIFICATION OF ACIDS USING GASEOUS OIA20METHANE -- Validation
results presented in this method were generated using the
gaseous diazomethane derivatization procedure.
11.4.1 Assemble the diazomethane generator (Figure 1) in a
hood.
11.4.2 Add 5 mL of ethyl ether to Tube 1. Add 1 mL of ethyl
ether, 1 ml of carbitol, 1.5 ml of 37% aqueous KOH, and
0.2 grams Oiazald to Tube 2. Immediately place the exit
tube into the concentrator tube containing the sample
extract. Apply nitrogen flow (10 ml/rain) to bubble
diazomethane through the extract for 1 min. Remove
first sample. Rinse the tip of the diaromethane
21
-------
generator with ethyl ether after methylation of each
sample. Bubble diazomethane through the second sample
extract for 1 min. Diazomethane reaction mixture should
be used to esterify only two samples; prepare new
reaction mixture in Tube 2 to esterify each two addi-
tional samples. Samples should turn yellow after
addition of diazomethane and remain yellow for at least
7 rain.. Repeat methylation procedure if necessary,.
»--
11.4.3 Seal concentrator tubes with stoppers. Store at room
ure in ?. hood for 30 min.
!..-.- ..." • any unreacted diazomethane by adding 0.1 -to
«..;. ^.iins silicic acid to the concentrator tubes. Allow
to stand until the evolution of nitrogen gas has stopped
(approximately 20 min). Adjust the sample volume to
5.0 ml with HTBE.
11.5 ESTERIFICATION OF ACIDS USING DIAZOMETHANE SOLUTION -- Alterna-
tive procedure.
11.5.1 Assemble the diazomethane generator (Figure 2) in a
hood. The collection vessel is a 10- or 15-ml vial,
equipped with a Teflon-lined screw cap and maintained at
0-5'C.
11.5.2 Add a sufficient amount of ethyl ether to tube 1 to
cover the first impinger. Add 5 mL of HTBE to the
collection vial. Set the nitrogen flow at 5-10 mL/min.
Add 2 ml Diazald solution (Section 7.9) and 1.5 ml of
37% KOH solution to the second impinger. Connect the
tubing as shown and allow the nitrogen flow to purge the
diazomethane from the reaction vessel into the collec-
tion vial for 30 min. Cap the vial when collection is
complete and maintain at 0-5'C. When stored at 0-5*C
this diazomethane solution may be used over a period of
48 h.
11.5.3 To each concentrator tube containing sample or standard,
add 0.5 ml diazomethane solution. Samples should turn
yellow after addition of the diazomethane solution and
remain yellow for at least 2 min. Repeat methylation
procedure if necessary.
11.5.4 Seal concentrator tubes with stoppers. Store at room
temperature in a hood for 30 min.
11.5.5 Destroy any unreacted diazomethane by adding 0.1 to
0.2 grams silicic acid to the concentrator tubes. Allow
to stand until the evolution of nitrogen gas has stopped
(approximately 20 min). Adjust the sample volume to
S.O ml with HTBE.
22
-------
11.6 FLOR1SIL CLEANUP
11.6.1 Place a small plug of glass wool into a 5-ml disposable
glass pipet. Tare the pipe!, and measure 1 g of
activated Florisil into the pipet.
11.6.2 Apply 5 ml of 5 percent methanol in HTBE to the
Florisil. Allow the liquid to just reach the top of the
Florisil. In this and subsequent steps, allow the
liquid level to just reach the top^of the Florisil
before applying the next rinse, however, do not allow
the Florisil to go dry. Discard eluate.
11.6.3 Apply 5 ml methylated sample to the Florisil leaving
silicic acid in the tube. Collect eluate in K-D tube.
11.6.4 Add 1 ml of 5 percent methanol in HTBE to the sample
container, rinsing walls. Transfer the rinse to the
Florisil column leaving silicic acid in the tube.
Collect eluate in a K-D tube. Repeat with 1-ml and 3-ml
aliquots of 5 percent methanol in MTBE, collecting
eluates in K-0 tube.
11.6.5 If necessary, dilute eluate to 10 mL with 5 percent
methanol in HTBE. Spike with 25 ul of internal standard
solution. Thoroughly mix sample and place aliquot in a
GC vial for subsequent analysis.
11.6.6 Seal the vial and store in a refrigerator if further
processing will not be performed immediately. Analyze
by GC-ECD.
11.7 GAS CHROHATOGRAPHY
11.7.1 Table 3 summarizes the recommended operating conditions
for the GC. Included in Table 3 are retention times
observed using this method. Examples of the separations
achieved using these conditions are shown in Figures £
and 5. Other GC columns, chromatographic conditions, or
detectors may be used if the requirements of Section
10.3 ere met.
11.7.2 Calibrate the system daily as described in Section 9.
The standards and extracts must be in MTBE.
11.7.3 Inject 2 uL of the sample extract. Record the resulting
peak size in area units.
11.7.4 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
23
-------
the analyst should weigh heavily in the interpretation
of chromatograms.
11.7.5 If the response for the peak exceeds the working range
of the system, dilute the extract and reanalyze.
12. CALCULATIONS
12.1 Calculate analyte concentrations in the sample from the relative
response for the analyte to the internal standard (RRa) using
the equation for the calibration curve described in Section
9.2.2.
12.2 For samples processed as part of a set where the laboratory
control standard recovery falls outside of the control limits in
Section 10, results for the affected analytes must be labeled as
suspect.
12. PRECISION AND ACCURACY
13.1 In a single laboratory, analyte recoveries from reagent water
were determined at five concentration levels. Results were used
to determine analyte EDLs and demonstrate method range. In
cases where analytes coeluted using primary analytical condi-
tions, results from confirmatory GC conditions were used. EDI
results are given in Table 2. Method range results are given in
Tables 4-7.
13.2 In a single laboratory, analyte recoveries from two artificial
ground waters were determined at one concentration level .
Results were used to demonstrate applicability of the method to
different ground water matrices. Analyte recoveries from the
two artificial matrices are given in Tables 8 and 9.
13.3 In a single laboratory, analyte recoveries from a ground water
preserved with mercuric chloride were determined 0, 14, and 28
days after sample preparation. Analyte recoveries were also
determined from sample extracts stored at 4*C for 14 and 28
days. Results were used to predict expected analyte stability
in ground water samples and sample extracts. Analyte recoveries
from the preserved, spiked ground water samples and stored
sample extracts are given in Table 11.
24
3\
-------
REFERENCES
"Pesticide Methods Evaluation," Letter Report £33 for EPA Contract NO.
68-03-2697. Available from U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio
'5268.
"T". .'-u-: P-;'-. ,• f :ttcrieri:, Pert, n, Volume n.02, 03694-82,
••• •-r.-iTr,J ;-,-ri irr ^or Pren?.r?t ion cf Sample Containers ?n
-------
TABLE 1. METHOD ANALYTES
Analyte
CAS Ho.
U)
Ident.
Code (b)
. t.i.0;.
U. lC.lt;..-....
2,4-D
Dal apon
2,4-OB
DCPA acid metabolites (c)
Dicamba
3,5-Dichlorobenzoic acid
Dichlorprop
Dinoseb
5-Hydroxyd i carcca
4-Nitrophenol
PC?
Picloran
2,4,5-T
2,4.5-7?
(a) CAS No. - Chenucal Abs
(b) Code used for Identi
I-i-j-bO-^
94-75-7
75-99-0
94-82-6
--
1918-00-9
51-36-5
120-36-5
88-85-7
7600-50-2
100-02-7
87-86-5
1918-02-1
93-76-5
93-72-1
tracts Service -Reg is try
fication of peaks in
9
' 6
1
12
16
4
2
5
13
10
3
7
15
11
8
Number.
figures;
IS
4,<'-d1brorr,ooctafluorobiphenyl internal standard; SUR
2,4-dichloropheoylacetic acid surrogate standard.
(c) DCPA monoacid and diacid metabolites included 1n method
scope; DC?A diacid metabolite used for validation
studies.
26
-------
TABLE 2. RECOVERY OF ANALY'ES FROM REAGENT WATER (SPIKING LEVEL 1) AND EDLs (a)
Analyte
Spiking
Level ,
yg/L
Arr.t i n
Blank,
pg/L n(b) R(c) S(d) RSD(e) EDL(
-------
TABLE: 3. PRIMARY AND CONFIRMATION CHROKATOGRAPHIC CONDITIONS
Relative Retention Time for Given Conditions
Priri?r
Confirmation (b)(c!)
-.ViK W«.4.U1>
Chloramben
2,4-D
Oalapon
2,4-DB
DCPA acid metabolites (c)
Dicamba
3,5-Oichlorobenzoic acid
Dichlorprop
Oinoseb
5-Hydroxydicamba
4-Nitrophenol
PCP
Picloran
2,4.5-T
2,4,5-TP
Surrogate
(a) Retention time relative
approximately 27.5 rnin.
(b) Retention time relative
approximately 27.6 min.
(c) Primary conditions:
i ri
l.Ofa
0.927
0.126
1.17
1.30
0.815
0.662
0.923
1.17
1.09
0.667
1.03
1.25
1.10
1.07
0.799
to OS03 internal
to DBOS internal
«
1C T
.53
1.27
1.19
1.02
0.171
1.19
1.37
0.876
0.705
0.971
1.25
1.14
0.805
1.02
1.36
1.15
1.10
0.540
standard which elutes «t
standard which elutes at
Column: 30 ra long x 0.25 isn I.D. 08-5 bonded fused silica
column,
0.25 ten film thickness (JiW)
2 uL splitless with 45 second delay
He 630 on/sec linear velocity
250-C
320 "C
Program from 60*C to 300'C at 4*C/min
ECO
Confirmation conditions:
Column: 30 m long x 0.25 ntn I.D. 08-1701 bonded fused silica
column, 0.25 um film thickness (JiW)
2 uL splitless with 45 second delay
He S30 cm/sec linear velocity
250*C
320-C
Program from 60'C to 300'C at 4'C/rain
ECO
Injection volume:
Carrier 'gas:
Injector temp
Detector temp
Oven temp
Detector
Injection volume:
Carrier gas:
Injector temp:
Detector temp:
Oven temp:
Detector:
-------
TABLE 4. RECOVERY Of ANALYTES FROM REAGENT WATER (SPIKING LEVEL ?) U)
Spiking Amt in
Level, Blank,
Analyte ug/L ug/L n(b)
Acifluorfen 0.040 N0(f) 7
Bentazon 0.20 NO 7
Chlorair-bcr, ( , 0.080 NO 7
2,4-0 " 0.20 NO 7
Dalapon " 2.0 NO 6
2,4-OB (g) 0.80 NO 7
DCPA di acid metabolite 0.040 NO 7
Oicamba 0.080 • NO - 7
3,5-Dichlorobenzoic acid 0.12 NO 7
Dichlorprop O.<0 NO 7
Dinoseb (g) 0.080 NO 7
5-Hydroxydicamba 0.040 NO 7
4-Nitrophenol 0.20 NO 7
PCP (h) 0.0080 NO
Picloram 0.12 NO 7
2,4,5-T 0.080 NO 7
2,4,S-7P (g) . - 0.040 NO 7
U) Data corrected for amount detected in blank.
(b) n • number of recovery data points.
(c) R • average percent recovery.
(d) S - standard deviation.
(e) RSD - percent relative standard deviation.
(f) NO - interference not detected in blank.
(c) Results from confirmatory analysis conditions
(h) Analyte not detected at this spiking level.
R(c)
88
92
118
90
107
37 '
89
155
85
no
118
49
148
-
166
87
140
.
S(d)
0.00826
0.03A6
0.0310
0.0248
0.457
0.229
0.0318
0.0269
0.0117
0.0689
0.0623
0.00547
0.0450
-
0.0468
0.0144
0.0249
RSO(e)
23
19
33
14
21
78
89
22
11
16
66
28
15
-
24
21
44
29
-------
TABLE 5. RECOVERY Or AMALYTES FP.OK REAGENT WATER (SPIKING LEVEL 3) (c)
Spiking Amt in
LeveK Blank,
Analyte ug/L ug/L n(b) R(c)
Acifluorfen 0.20
Bentazon 1.0
Chloic... --) 0.40
2,4-0 1.0
Oalapon 10
2,4-08 (a) 4.0
DCPA diacid metabolite 0.20
Dicamba 0.40
3,5-Dichlorobenzoic acid 0.60
Dichlorprop 2.0
Oinoseb (g) 0.40
5-Kydroxvoicamba 0.20
4-Nitrophenol 1.0
PCP 0.040 x
Picloram 0.60 0.
2,4,5-T 0.40
2,4,5-TP (g) 0.20
(a) Data corrected for amount detected
(b) n - number of recovery data points
(c) R - average percen.t recovery.
(d) S - standard deviation.
N0(f)
'HO
NO
HO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
,308
NO
NO
in bl
•
*-
6
4
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
ank.
121
120
111
131
100
87
74
135
102
107
42
103
131
130
91
117
134
- S(d) RSD(e)
0.0318
0.163
0.0615
0.274
2.24
0.518
0.0200
0.129
0.098
0.418
0.0971
0.0325
0.234
0.0242
0.149
0.0639
0.0631
13
14
13
21
20
15
13
24
16
19
34
16
18
47
17
14
23
(e) RSO - percent relative standard deviation.
(f) HO - interference not detected in
(c) Results from confirmatory analysis
blank.
condi
tions.
30
37.
-------
TABLE 6. RECOVERY OF AHALYTES FROM REAGENT WATER (SPIKING LEVEL 4) (a)
Spiking Ant in
LeveK Blank,
Analyte ug/L ug/L n(b) R(c)
Acifluorfen 0.50
Bentazon 2.5
Chloramnen (Q) 1.0
2,4-0 '" 2.5
Dalapon 25 1
2,4-DB (g) 10
DCPA dlacid metabolite 0.50
Dicamba 1.0
3,5-Dichlorobenzoic acid 1.5
Dichlorprop 5.0
Oinoseb (g) 1.0
5-Hydroxydicamba 0.50
4-Nitrophenol 2.5
PC? 0.10
Picloram 1.5
2,4,5-T 1.0
2,4,5-TP (g) 0.50
(a) Data corrected for amount detected
(b) n - number of recovery data points
(c) R • average percent recovery.
(d) S - standard deviation.
H0(f)
NO
NO
NO
.33
NO
NO
HO
NO
NO
NO
NO
NO
NO
NO
NO
NO
6
6
6
6
6
6
6
6
6
6
5
6
6
6
6
6
6
89
90
89
94
82
55
50
87
101
90
31
85
93
82
82
90
90
S(d) RSO(e)
0.0525
0.500
0.137
0.307
2.69
0.657
0.0652
0.0683
0.139
0.525
0.123
0.0567
0.267
0.00950
0.200
0.0948
0.0587
12
22
15
13
12
12
26
8
9
12
40
13
11
9
16
10
13
in blank.
•
(e) RSO - percent relative standard deviation.
(f) NO - interference not detected in
(g) Results frora confirmatory analysis
blank.
condi
tions.
31
-------
TABLE 7. RECOVERY Of AHALYTES FROM REAGENT WATER (SPIKING LEVEL 5) (a)
Analyte
Spiking Ant in
Level, Blank,
ug/L ug/L n(b) R(c)
S(d) RSD(e)
Acifluorfen 2.0 N0(f)
Bentazon 10 NO.
Chloramben (g) 4.0 NO
2,4-0 10 NO
Dalapon 100 NO
2,4-08 (a) <0 NO
OCPA diacid metabolite 2.0 NO
Oicamba 4.0 NO
3,5-Dichlorobenzoic acid 6.0 NO
Oichlorprop 20 NO
Dinoseb (a) 4.0 NO
S-Hydroxydicamba 2.0 NO
4-Nitrophenol 10 NO
PCP 0.40 NO
Picloram 6.0 NO
2,4,5-7 4.0 NO
2,4,S-7P (a) 2.0 NO
*-
6
6
6
6
6
6
6
6
6
6
6
6
6
6
5
6
6
90
80
55
74
81
59
23
79
88
78
74
67
73
73
73
77
84
0.0676
1.02
0.0888
0.481
4.28
1.30
0.-338
0.126
0.340
0.623
0.267
0.170
0.387
0.0208
0.518
0.181
0.0861
4
13
4
6
5
5
74
4
6
4
Q
13
5
6
12
6
-
(a) Data corrected for amount detected in blank.
(b) n • number of recovery data points.
(c) R - average percent recovery.
(d) S - standard deviation.
(e) RSO - percent relative standard deviation.
(f) NO • interference not detected in blank.
(g) Results from confirmatory analysis conditions.
32
-------
TABLE 8. RECOVERY OF AHALYTES FROM HARD ARTIFICIAL GROUND WATER
(SPIKING LEVEL 3) (a)
Analyte
« .L t i 1 Uci i C «•
Bentazon
Chloraraben (g)
2,4-0
Dalapon
2,4-DB (g)
DCPA dUcid metabolite
Dicaraba
3,5-Dichlorobenzoic acid
Oichlorprop
Dinoseb (g)
5-HydroxydiCcmba
4-Nitrophenol
PCP
Picloram
2,4,5-T
2,4,5-TP (g)
Spiking Amt in
Level, Blank,
ug/L ug/L n(b)
»--
0.20
1.0
0.40
1.0
10
4.0
0.20
0.40
0.60
2.0
0.40
0.20
1.0
0.040
0.60
0.40
0.20
..HD(f)
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
5
5
7
5
5
7
5
6
6
5
5
2
7
7
c
5
6
R(c)
103
82
112
no
128
(h)
81
92
82
106
89
88
127
84
97
96
105
S(d) RSD(e)
0.040
0.378
0.043
0.051
3.027
-
0.048
0.068
0.049
0.099
0.054
0.012
0.374
0.006
0.139
0.017
0.014
20
46
O
5
24
-
27
19
Q
^
15
5
27
11
24
4
6
(a) Data corrected for amount detected in blank; hard artificial ground water
used to generate these results was Absopure Natural Artesian spring v«ier
obtained from the Absopure Water Company in Plymouth, Michigan.
(b) n - number of recovery data points.
(c) R - average percent recovery.
(d) S - standard deviation.
(e) RSO • percent relative standard deviation.
(f) HO - interference not detected in blank.
(g) Results from confirmatory analysis conditions.
(h) Analyte not recovered from hard artificial ground water.
33
-------
TABLE 9. RECOVERY OF ANALYTES FROM ORGANIC-CONTAMINATED ARTIFICIAL
GROUND WATER (SPIKING LEVEL 3) (a)
Spiking
• ••"• • j - -
Acifluorfen
Bentaion
Chloranben (gj
2,4-0
Dalapon
2,4-DB (g)
OCPA diacid metabolite
Oicamba
3,5-Dichlorobenioic acid
Dichlorprop
Dinoseb (g)
5-Hydroxydicamba
4-Nitrophenol
PCP
Picloram
2,4,5-7
2,4,5-TP (g)
Level ,
ug/L
0.20
1.0
0.40
1.0
10
4.0
0.20
0.40
0.60
2.0
0.40
0.20
1.0
0.040
0.60
0.40
0.20
Air.t in
Blank,
ug/L
..H0(f)
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
0.197
NO
NO
n(b)
7
7
7
7
7
7
7
7
7
7
5
7
7
5
7
7
c
(a) Data corrected for amount detected in bl
artificial ground water
spiked with humic' acid
used to
at the
generate
these
1 mg/L concent
RU)
110
111
104
112
109
79
78
107
96
106
71
102
118
133
86
108
108
S(d)
0.024
0.089
0.049
0.093
1.140
0.583
0.018
0.026
0.029
0.105
0.035
0.013
0.102
0.004
0.044
0.027
RSO(e)
11
8
12
8
11
19
11
5
5
5
13
5
c
5
£
6
0.028 13
ank; organic-contaninated
result
ration
s was reagent water
level .
Humic
acid
(sodiun salt) obtained fros Aldrich (HI,675-2) wes used.
(b) n - number of recovery data points.
(c) R - average percent recovery. '
(d) S • standard deviation.
(e) RSD - percent relative standard deviation.
(f) HO • interference not detected in blank.
(g) Results from confirmatory analysis conditions.
34
-------
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-------
Nitrogen
Tube 1
FIGURE 1. GASEOUS DIAZOnETHAtlE GENERATOR
a?
-------
u
o
JO
JO
-------
"D -
o
c
o
c
o
c
_J O
UJ C.
> c.
— CJ
c_ —
o >->
< —
C —'
cs c
39
-------
r
J
rtf
0
5*
_J C
1_J CJ
=> C.
UJ Q.
c. ci
O
C3 t—
S C
O
._ c. o
»— <^> -a
o
~> S O
g S3
^ o •=
o o u
o ->
a. c
= o
o -c
QJ
O.
40
V7
-------
^
c.
e.
IS)
o
cr
a
g
«]
S
g
o
c
o
c
o
o
CO
o
u-
O
C£
O
O
<_>
o
•r:
e:
3
u
^ i i i
41
-------
Fa
T 8
' 8
. Si
o
o
c_ o
VJ <
< l^>
tj 1/1
z>
o <
o ^
wu <
C.
O
42
-------
Appendix C
Revision No 4
Date December 1989
Page 1 of 6
APPENDIX C
DIAZOMETHANE PREPARATION AND SAFETY
-------
ppendix: SAFETY;
All chemical compounds used in this method should be treated as
potential hazards unless known to be otherwise. Analysts should become
familiar with all the safety information provided here before attempting
the analysis. Material Safety Data Sheets and gather pertinent information
have been supplied for the more hazardous substances used in this method
(diazomethane, mercuric chloride, benzene, and ether). The individual labo-
ratories are responsible for maintaining a file of Material Safety Data
Sheets on all hazardous substances in use by that laboratory. All personnel
should be made aware of the existence of the file and it should be readily
available to them.
Precautions to be followed when handling or preparing diazomethane.
1. Use an efficient high draft hood - do not breath fumes.
2. Avoid use of ground-glass joints or any glassware which is
chipped, cracked or has not beer, carefully firepolished. Failure
to do so may result in an EXPLOSION. The DIA2ALD kit supplies such
glassware.
3. Use a sturdy explosion proof safety shield.
4. Use disposable PVC gloves.
Preparation of diazomethane (alcohol - free ethereal solutions)
Add 2-(2-Ethoxyethoxy)-ethanol (35 ml) and ether (20 ml) to a
solution of potassium hydroxide (6 g) in water (10 ml). This solution
is placed in a 500 ml round bottom distilling flask fitted with dropping
funnel and efficient condenser in a water bath at 65*C. As the distil-
lation of the ether starts* a solution of 21.5 g of Diazald in about
200 ml of ether is added through the dropping funnel over 20 min. During
the distillation, the solution is mixed continuously by a small magnetic
stir bar. The rate of distillation should approximately equal the rate of
addition. When the dropping funnel is empty, another 40 ml of ether is
added slowly and the distillation is continued until the distilling ether
is colorless. The combined ethereal distillate contains about 3 g of
diazomethane. A diagram of the diazomethane apparatus has been provided.
Before attempting this procedure read all safety information con-
cerning diazomethane preparation.
Diazomethane solution should remain tightly capped, and may be stored
at 0*-5*C for a period of up to 6 months. The intensity of the yellow
color is an indicator of the strength of the diazomethane / ether solution.
-------
CD
c
c
3
CL
O
V)
c
c
Q.
jc
o «»-
— i. O
-------
lo 1894, von Peehman esublished the
ctruoureCHtNi for the ydlow gas liberated
from nitrosomethylurcthane upon treat-
meat with alkali.' During the subsequent 90
yean, diazomethanc (less commonly re-
ferred to as azimcthylenc or diaiiranc) has
proven to be one of the most valuable and
versatile reagents available to the synthetic
chemist. It is easily the most common mcth-
jlating reagent for carboxyiic acids, and has
S'oUnfl wide* application in the methyUUon
of phenols, elcohols. cnols, and hetero-
atoms such as nitrogen and sulfur. Diazo-
methane effects the ring expansion (or chain
homologation) of ketones or. under suitable
conditions, forms cpoxides from the same
ketones in the manner of sulfur ylids. Acid
chlorides are converted to or-diazokctones
which are valuable synthetic intermediates
in their own right. In addition. CHiNt acts
as a powerful dipole in many cydoaddition'
reactions with unsaturated systems, and of-
ten the resulting nitrogen-containing hcterc-
cydic ring can be decomposed (either ther-
mally or pnotochcmically) to afford cyclo-
propane (or other) derivatives. Each of (he
above rcaoJon categories will be treated sep-
arately in the REACTIONS section.
STRUCTURE
The structure of diazomethane can be
represented by the valence uutomcrs 1
through S (Scheme I). Although the true
eketrank distribution over the the molecule
can be represented as a weighted sura of Ihe
five structures shown, the majority of di-
of the isomers of diazomethane were calcul-
ated.'
A gas at room temperature, diazometh-
ane liquifies at -23 «C (density MS) and
freezes at -1X5 "C. It can be protonatcd in
fluorosulfonic acid at very low tempera-
tures' and possesses an ionization potential
of 9.03cV.-
The most recent comprehensive-review of ,
.•diazomethane- chemistry appearccT.fiin'c
yean ago:1 the reader is directed to this work
for references to earlier reviews. Recently,
two reviews concerning diazoalkanes have
appeared; one involves organomctallic syn-
thesis4 and the other the synthesis of "un-
usual organic molecules".1
SAFETY CONSIDERATIONS
Although quite safe when handled as a
dilute solution in an inert solvent, diazo-
methane presents several safety hazards of
which all users of the reagent should be
aware. It is both extremely toxic* and highly
irritating.' causing pulmonary edema when
inhaled in high concentrations. Long-term.
tow-tod exposure may lead to sensnization,
resulting in asthma-like symptoms.'* Also.
diazomethane and Kveral of its chemical
precursors have been died as carcinogens."
Diazomethane has been known to ex-
plode quite unaccountably, both as a gas
and a liquid, although rough surfaces are
proven initiators of detonations." Thus.
ground-class joints and any glassware which
have not been carefully firepoUshed must
roe allowed to come in contact with di-
T. Ki
Aldrich Chemical Cospatty, «n<
azomethane or its solutions. In bdditioi
contact with alkali metals or drying agen
such as calcium sulfatc can result in an e:
plosion. If moisture must be removed fro
a solution containing diazomcthane, the re
ommcnded drying agent is potassium h
droxide pellets. Finally, solutions should n
be exposed to strong light, which has be
reported" to initiate detonations.
,'". Fortunately. if the reagent is generated i
ing the proper equipment and is handled c
ly as a dilute solution ai low temperature (<
0*O, the risks cited above are minimize
Of course, *ll reactions involving dia.
methane should be carried out in an ef fid
fume hood and behind a sturdy uf
chidd. Finally, it is recommended that sc
lions of diazomethane be used immedii
ly and not stored, even at low icmperatv
PREPARATION
By far, the most common and convcn
method for generating diazomcthane i:
the base-catalyzed decomposition of
mcthyl-N-nitroso amines of the gen
structure 6. where R represents a sulfo
carbonyl. or similar electron -withdraw
group. The mechanism of diazomett
generation is outlined in Scheme II. For i
ity. a specific chemical presunor is
ployed: A/-methyl-/V-nitrc-A/-nitn>»oj
idine (MNNG. 7). In the first step, t- <
aiomethane reactions are best conceptual-
(zed and explained by structure 1. Recently
the Urtalekoroi&cncrxics and energies of
Isooerization for the optimized geometries
•1983 by Aldrich ChcBk
*«fa» Aaa. yet. 16. Ho. 1.
-------
PO Bai 355 (U./wi
SAhcfr jiK
I AL U-t
A TIN:
t-PA
LNV1
NASA/NSL
BLDC 1105
NSTL STATION
RL/l3fcKT
JATC:
A i
RY L A U
Mb 3'v
K l A L
SAFETY DATA
COST « <^CO4« MLOU: -
WAIEK SPKAY.
CARBJN OiOAiUC. DRY CHEMICAL PGWOER, ALCOHCL OR POLYMER FOAM.
SPECIAL FlkE FlbHTING PROCEDURES:
HEAR iELF-CUNIAlNED BREATHING APPARAlUS AND PROTtCTIVE CLOTHING 10
PREVENT CUNTAcT WITH SKIN AND tYES.
ONUSOAL FlKt Mi«J EXPLOSION HAZARDS:
EMlTi lOXlc hOMfeS UNOEK FIRE CCNUITICNS.
SECTION V HEALTH HAZARD DATA
MAY bE HAKMI-UL dY INHALATION. INGEST ION* OR SKIN ABSORPTION.
CAUSED SfcVEKc IRRITATION.
MAY CAJSL ALLtKolC SKIN REACTION.
TU Tht o£SI U uUR KNOWLEDGE. THE CHEMICAL, PHYSICAL. AND
TOXICULuGICAL PROPERTIES HAVE NOT BEEN THOROUGHLY INVESTIGATED.
FIRST AIU:
IN CAiE Of CONTACT. IMMEDIATELY FLUSH EYES OR SKIN HiTH COPIOUS
AMOUNIi Ut- «A(tK FOR AT LEAST 15 MINUTES WHILE REMOVING CONTAMINATED
CLCTHlNi ANJ SHOES.
IF l.NHALtU. KertuVE TO FRESH AIR. IF NOT BREATHING GIVE ARTIFICIAL
RESPIRATION; PkEFERAdLY MCUTH-TO-MOUTH. IF BREATHING is DIFFICULT.
GIVE OXYGEN.
CALL A PHYSICIAN.
.
«« !'J 1MO
•?»*••.««•««•
:«Ce
C*.LM.
-------
HHH7338SO
,M A I b R I A L S A r T. I Y DATA ShfcET
DATE: OL/^O/bo CATALOG * 02000-0 GUST # S40048 P.O. * PAGf
DISCARD v.u NT AM la ATEO CLUThlNG AND SHOES.
SECTION VI REACTIVITY DATA
INCUMPAIIdlLIIY:
STRONv, AclDS
STRONo 6AStS
STRONo uXlLUZlNu AGENTS
STRONG REJUClNu AGENTS
MAZAKUUUS DECOMPOSITION PRODUCTS:
TOXIC FUMES UFi
CARBbN MUNOXiOE, CARBON DIOXIDE
NlTRuGEN UXIuES
SULFUR JXIDES
SECTION VII _SPILL CR LEAK PKCCECURES
SPILLS OK LEAKS:
EVACUATE AREA.
WEAR RESPIRATOR. CHEMICAL SAFETY GOGGLES, RUBBER 600TS AND HEAVY
RUBfabR GLOVES.
SwEEP UP, PLACE IN A BAG AND HOLD FOR WASTE DISPCSAL.
VENTILATE AKfcA AND *ASH SPILL SITE AFTER MATERIAL PICKUP IS COMPLETE.
WASTE DISPOSAL:
PLEASE LUNTALT THE TECHNICAL SERVICES OEPAR1MENT. BE SURE TO MENTluN
THE NAME, CATALOG NUMBER. AND THE QUANTITY OF THE MATERIAL.
OBSERVE ALL FEDERAL. STATE C LOCAL LAWS CONCERNING HEALTH C POLLUTION
SECTION VIU PRECAUTIONS TO BE TAKEN IN HANDLING AND STORAGE
CHEMICAL SAFETY GOGGLES.
RUBBER GLOVES
OSHA/MSHA-APPRUVED RESPIRATOR.
USE JNLY IN A CHEMICAL FUME HOOD.
DO NUT BREATHE UUST.
00 NUT GET IN EYES. ON SKIN, CN CLOTHING.
WASH THUkUUGMLY AFTER HANDLING.
SEVERE ikRHANC.
AVOIU ALL CONTACT.
KEEP TIGHTLY CLOSED.
STORE IN A COOL DRY PLACE.
SECTION IX SPECIAL_PR.ECAUTIONS_AND COMMENTS
NOT APPLICABLE
THE ABOVE INFORMATION IS BELIEVED TO BE CORRECT BUT DOES NOT PURPORT
TO Bt ALL INCLUSIVE AND SHALL BE OSED ONLY AS A GUIDE. ALDRtCH SHALL
NOT BE HELD LlAbLE FOR ANY DAMAGE RESULTING FROM HANDLING OR FROM
CONTACT «1TH THE ABOVE PRODUCT. SEE REVERSE SIDE OF INVOICE OR PACKl
SLIP FOR ADDITIONAL TERMS AND CONDITIONS OF SALE.
»ULA Mtto* CM*« f,
•<• W»M SL fMI AM. IMOCH Oww* CAJM.V imcri fTmi«M C* IM»HII rtmim
"•* • • — — -—- - - - - — ICinMH LM. tl
-------
Appendix H)
Revision No 4
Date. December 1989
Page 1 of 12
APPENDIX D
DATA FLOW (REDUCTION, VALIDATION, AND REPORTING)
-------
OSJDE RETRESENTATION OF DATA FLOW
1. Samples are taken in the field.
2. Samples are iced and shipped to the laboratory.
._.! ^.v-^™,^ ;,... ,. :'.•_-. : • field samples along with QC samples.
4. Laboratory-enters field and QC data on a computer in "sets" and it
enters instrument control standard data in a seperate file.
5. Laboratory creates an ASCII file of the data using the specified formats
on an ISA 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 TBA 3090 mainframe in North Carolina (or possibly to IEM Logical
Mainframe in Cincinnati).
8. The data is ^i**** 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 FORMATS
1. The format for any date is mm/dd/yy
A missing date should be entered 01/01/60
2. The format for any time is hh:mm in military time
A missing time should be entered 00:00 *
3. Any other data that is missing should be entered with a period (.)
4. The number of decimal places should be as follows:
Concentration 3 (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 I*h are as follows:
TSD . TSD
OPP OPP
WERL WER
Radian RAD
Battelle BCD
James M. Montgomery JMM
Alliance ALL
Environmental Sciences and Engineering ESE
7. The codes -for Type are as follows:
Field Sample SAMP
Shipping Blank SBLK
Method Blank MBLK
Lab Control Standard I£S@
Lab Spike Sample LSS@*
Time Storage for Extract HTE@
Time Storage for Sample HTS@
where @ is the mix letter (A,B,C or D)
and £ is the spiking level (1,2 or 3)
-------
NOTES ON NFS DATA POF3-RIS (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 (< Minimum Reporting Level) ^ -999
Saturated *' -777
Other -333
Below Report Limit, but Distinct Peak -111
Above Reporting Limit, but not ^lantified +888
10. If a reported value is greater than (>) sane 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 (NFS) Data
\
Line Column Revision
11 52-62 « Revised "Enter Internal Standard" to "PERCENT
RECOVERY OF INTERNAL STANDARD AS COMPARED
AGAINST THE CALIBRATION STANDARD".
Notes on NPS Format
4) Revised "Internal Standard 0 (area count)" to
Internal Standard 1 (percent recovery)
9) - 999 - revised to denote "Not Detected (< 1/2 MRL)"
- Ill - revised to denote "> 1/2 MRL but < MRL"
-------
TABLE 1: USES OF DATA CODES IN NFS
SAMPLE TYPE
LSS,DIS
SAMP MBLK SELK LCS HIE,HIS
(a) .(a) .(a)_
**** ****
**** -333 (d)
-444(6) **** -444(6) **** -444(6)
-555 (f) -555 (f) -555(f) **** ****
-666 fa) **** -666 ^) **** ****
-777ft) -777ft) -777ft) -777 W -777 (h>
888 d) 888 d) 888 d) **** ****
-999(J) -999(j) -999(j) **** ****
«W =nc
-------
-333
NFS DATA REPORTING CODES (cont.)
rm^y
-999
888
-333 -999 888
INN
HUM
OGHF
-333 -555 -999 888 GOTS
GCMS
(at referee)
-333 -999 888
-333
failure)
-444
-6.66
-333 -666 -999
-333 -555 • -999 888
-333 -999 888
HUM
CCNF
GCMS
OOS
(at referee)
vit^t TO nc ^fli
-111
-333
-777a -999
catx:
PRIM
-111 -333 -999 X-7W
-333^55 -999^888 -333^5-99^888 -SSS^SS -999 888 -SS'S -S^S -999 888 QCMS
/N /I\ XN /K
/
-333 -999 888
-333-999 888
-333-999 888
-333-999 888
a. - Dilute and reanalyze
-------
CHECKS PERFOrfrED 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
lijnits 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 extract 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?
i2. 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?
-------
FOFMftT FOR NATIONAL PESTICIDE SURVEY (NFS) DATA
LINE OOIIJKNS DESCRIPTION
1 1-9 Well I.D.
13-20 Date_Sam
23-30 Date_Shp
33-40 Date.Rec
43-50 Tine Sam
53-60 Timelloe
[FOR METHODS 5 AND 9 ONLY]
1-10 enter VEIL IDEOTIFICATION 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 METHODS 5 AND 9 ONLY]
63-66 enter pH
BIANK
1-8 Ini_Tenp
11-18 Stbjremp
21-29 Condition
1-8 enter INITIAL TEMPERATURE OF WATER
11-18 enter STABILIZED TEMPERATURE OF WATER
21-80 enter CONDITION OF SAMPLE UPON RECEIPT AT LABORATORY
BLANK
1-6 Sairp S
9-11 Lab
14-18 Set S
21-28 Date_Spk
31-38 Date_Ext
41-48 Date Ana
51-56 Site *
59-64 Column
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
-------
FOPtfAT FOR NATIONAL PESTICIDE SURVEY (NFS) DATA (cent.)
T.TNE COLUMNS
9 BLANK
- r.
11
12
13
14
15
16
17-?
8-13
16-22
25-31
34-40
43-49
52-60
65-70
1-5
0-13
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
DESCRrPripN
Spiker
Extract
Analyst
Sam Vol
Ext Vol
Int. Std.
% Surr
enter SAMPLE TYPE
enter SPIKER1 S INITIALS
enter EXTRACTOR'S INITIALS
enter ANALYST'S INITIALS
enter VOLUME OF SAMPLE
enter VOLUME OF EXTRACT
enter INTERNAL STANDARD
enter PERCENT RECOVERY OF SURROGATE
Comments
enter ANY PERTINENT COMMENTS ON SAMPLE AND ANALYSIS
Analyte
Cone.
Analyte
Cone.
enter ANALYTE'S NAME
enter CONCENTRATION OR PERCENT
enter ANALYTE'S NAME
_
enter CONCENTRATION OR PERCENT RECOVERY
-------
FOR NATIONAL PESTICIDE SURVEY (NPS) INSTRUMENT CONTROL DATA
LINE COLUMNS DESCRIPTION
1 1-3 Lab
6-11 Method
14-21 Date_Ana
24-30 Analyst
35-37 S/N '
42-44 PSF
49-51 PGF
55-58 Res.
2 BLANK
3-? 1-3 enter LAB ABBREVIATION
6-11 enter METHOD NUMBER
14-21 enter DATE ANALYZED
24-30 enter ANALYST'S INITIALS
33-37 enter SIGNAL TO NOISE RATIO
40-44 enter PEAK SYMMETRY FACTOR
47-51 enter PEAK GEOMETRY FACTOR
54-58 enter RESOLUTION
-------
•* TSO FOREGROUND HAROCOPY ****
OSNAME=CPSFSOO.NPS.FORHAT.QATA
CMETHOD3 )
I_Terap S_Tenp Dato_Saa Date_Shp Datc_Rec Tiue_Sa« Ti«ne_Ice
01/01/60 01/01/60 01/01/60
Receipt Condition
TSO
01
ui-\(._-uU Date_Ext Oat«_-Ana Column
01/01/60 04/30/87 05/03/87 PRIM
Type Spiker Extract Analyst Sae_Vol £xt_Yol» Int. Std. X Surr
..;_.. - . ... 1000 5 35 101.3
Coeaents
NONE.
Analyte Cone.
Acifluorfen -999
2*4-06 -999
Bentazon -999
Chlorauben -999
2*4-0 -999
Oslapon -999
DCPA acid metabolites -999
Oicamba -999
3*5-Dichlorbenzoic acid -999
Analyte
Dichloroprop
Oinoseb
5-Hydroxy Oicamba
4-Nitrophenol
PCP
Pichoram
2*4,5-T
Cone .
-999
-999
-090
-999
-999
-999
-999
-999
-Tenp S«-Temp Oate_Sa« Oate_Shp
01/01/60 01/01/60 01/01/60
Time_Sam Time_Ice
Receipt Condition
Samp #
Lab Set tt Oate.Spk Date.Ext Date_Ana Coluon
TSD 01 04/30/87 04/30/87 05/03/87 PRIM
Type Spiker Extract Analyst Sa« Vol Ext.Vol Int. Std.
LCSA CM CM CM 1000 5 31
Consents
NONE.
Analyte
Acifluorfen
2*4-08
Bentazon
Chloramben
2*4-0
Oalapon
DCPA acid aetabolites
Dicaaba •
3*5-Oichlorbenzoic acid
Cone.
100.6
94.7
•
97l 5
Analyte
OichloroproD
Dinoseb
5-Hydroxy Oicamba
4-Nitrophenol
PCP
Pichoraa
2*4*5-T
2*4*5-TP
2 Surr
99.4
Cone.
98.9
94.5
89.9
•
91.1
93.3
9
85.5
S_Te»p
»-* M c K»
-------
Appena;x -
Revision No 4
Date December 1989
Page 1 of 4
APPENDIX E
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 U 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, ^,
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 arc 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 arc 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 ^mho/cm, there is no implication by convention that the conductiv-
ity is 1,000 ± 1 pmho. Rather, the zeros only indicate the magnitude of the number.
-------
A good measure of the significance of one or more zeros interspersed in a number is to
determine whether the zeros can be dropped by expressing the number in exponential form.
If they can, the zeros may not be significant. For example, no zeros can be dropped when
expressing a weight of 100.08 g in exponential form; therefore the zeros are significant.
However, a weight of 0.0008 g can be expressed in exponential form as 8 X \Q~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.
7*0
-------
When one number is subtracted from another, rounding off should be completed after the
subtraction operation, to avoid possible invalidation of the'operation.
When tv/o 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
.. uigio. "t'nen 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.
1 I
-------
Revision No 4
Date December 1989
Page 1 of 3
APPENDIX F
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.
-------
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1 REMOVED
____J
RETURNED
[REMOVED
INITIAL
STORAGE
RECORD
IDENTIFICATION
i
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Date/By
Date/By
Date/By
Date/By
Date/ By
Date/By
Date/By
Method/Set No.
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-------
Appendix G
Revision No 4
Date December 1989
Page 1 of 3
APPENDIX G
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:
Xx < X2 <: X3 < ... < X,,.! < X,,
2) Decide whether the smallest, X^ or the largest, Xn, is
suspected to be an outlier.
3) Select the risk you are willing to take for false rejection.
For use in this QAPP we will be using a 5% risk of false
rejection.
4) Compute one of the ratios in Table 1. For use in this QAPP we
will be using ratio r22, since we will be using between 20 and
17 points for the control charts.
5) Compare the ratio calculated in Step 4 with the appropriate
values in Table 2. If the calculated ratio is greater than the
tabulated value, rejection may be made with the tbulated risk.
Fort his QAPP we will be using the 5% risk values (bolded).
Example (from Taylor)
Given the following set of ranked data:
10.45, 10.47, 10.47, 10.48, 10.49, 10.50, 10.50, 10.53, 10.58
The value 10.58 is suspected of being an outlier.
1) Calculate ru
10.58 - 10.53 0.05
rn - - - 0.454
10.58 - 10.47 0.11
2) A 5% risk of false rejection (Table 2), ru - 0.477
3) Therefore there is no reason to reject the value 10.58.
4) Note that at a 10% risk of false rejection ru - 0.409, and the value
10.58 would be rejected.
-------
TABLE 1
CALCULATION OF RATIOS
For use if if X,, is if Xj is
Ratio n is between suspect suspect
V \ / V
' *n-l) (X-2 ~
ru 3-7
:n 8 - 10
'21 11 *
r22 14 - 25
v '\ fv
~ *K-l) ^A2 "
- x2) (Vi -
Y ^ fv
- J^a-2J <-A3 ~
- X2)
V N / V
" Ao-2/ VA3
- X3) (X.,.2
Note that for use in this QAPjP ratio r22 will be used.
-------
TABLE 2
VALUES FOR USE WITH THE DIXON TEST FOR OUTLIERS
Risk of False, Rejection
Ratio n 0.5% 1% 5% 10%
-10
-ii
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
0.994
0.926
0.821
0.740
0.080
0.725
0.677
0.639
0.713
0.675
0.649
0.674
0.647
0.624
0.605
0.589
0.575
0.562
0.988
0.889
0.780
0.698
0.637
0.683
0.635
0.597
0.679
0.642
0.615
0.641
0.616
0.595
0.577
0.561
0.547
0.535
0.524
0.514
0.505
0.497
0.489
0.941
0.765
0.642
0.560
0.507
0.554
0.512
0.477
0.576
0.546
0.521
0.546
0.525
0.507
0.490
0.475
0.462
0.450
0.440
0.430
0.421
0.413
0.406
0.806
0.679
0.557
0.482
0.434
0.479
0.441
0.409
0.517
0.490
0.467
0.492
0.472
0.454
0.438
0.424
0.412
0.401
0.391
0.382
0.374
0.367
0.360
Note that for this QAPjP the 5% risk level will be used for ratio r
22-
-------
Reference:
John K. Taylor, Quality Assurance of Chemical Measurements. Lewis
Publishers, Chelsea, MI, 1987.
-------
Appendix H
Revision No 4
Date- December 1989
Page 1 of 13
APPENDIX H
ADDITIONAL QUALITY CONTROL CHECKS
-------
QUALITY ASSURANCE DATA FORM
NFS GROUND V«TER
Sampling Date(s)_
Method
Arrival Date(s) at ECL
Set No.
Set Composition
sample wt. (gins) pH
sample wt. (gms) pH
1.
2.
3.
4.
5.
6.
7.
8.
1
1
1
1
1
9- 1 1
10. |
11.
12.
13.
14.
1
15.
16.
Method Blank
Standards and Set Controls Data
Name / Date of Std. Used Mt. Spiked Initials
Shipping Blank
Shipping Blank
LCS
LCS
LCS
LSS
LSS
LSS
LSS
LSS
LSS
Surrogate
Column Check
Column Check
***
**•*
STOP! l . Has Sample 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
Hydrolysis
pH Adjustment
Extraction
Derivatization
Cleanup:
-Florisil
Accomplished
Sample Preparation
Initials of Employee(s)
Doing Work
Comments
Extracts Relinquished By:
Extracts Received By:
Date:
Date:
GC Analysis
Date Begun:
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.
Date Completed:
Arat. Used:
7.
8.
9.
Analysis Dates
10.
11.
12.
13. 16.
14.
15.
STOP!! . Is GC work complete?
. Have NFS Data Report Forms on each sample been completed for each
GC column?
. Has remedial QC work been carried out with results attached?
. If any sample in this set will be reextracted, list the/^tiigit -
code no. of the sample. ^-4
. IB any sample in this set a reextracted sample?
Signature:
Date:
Disposition of Extracts:
Data Reviewed By:
Date:
'Final Disposition of Extracts:
Date of Final Disposition:
Signature:
-------
EXCEPTIONS TO QC REQUIREMENTS
NFS Method Set
State exception, when noticed, who notified, remedial actib*h required, action taken;
sign and date for each separate incident. Attach to this QUALITY ASSURANCE DATA FORM
verification that the QC problem was resolved and the date it was resolved.
-------
QUALITY ASSURANCE DATA FORM INSTRUCTIONS
To fill out the QA Data Form, refer to the Assigmerit Sheet and Sample
Tracking Form for the set.
Sampling Date(s): »
This information is on the Sample Tracking Form.
Arrival Date(s) at ECL;
This information is on the bottom of the Sample Tracking Form under
Date Received.
Set No.:
This information is in the title of the Assignment Sheet.
Set Composition:
The correct order of the controls and samples is copied from the As-
signment Sheet onto the Set Composition portion of the Quality Assurance
Data Form. For each sample, write both the sample name and 9 digit sample-
code number. The number to the left of each control name or sample name in
this section is the Set Composition Number. It, in conjunction with the
Set Number, will be used to identify the controls and samples throughout
the extraction and G.C. Analysis. Set Composition Numbers are initially
assigned on the Assignment Sheet for each set. After determination, the
weight in grams and pH is recorded for each water sample. The weight for
all controls is 1000 gms. No pH is recorded for controls. Column Checks
are simply listed next to their Set Composition Numbers, pH and weight
data being inapplicable.
In the event that a Ground Vbter Sample is a reextraction, place an R
before the 9 digit sample - code number and follow it with the Set Number
and Set Composition Number, in parenthesis, of the original Ground Vbter
Sample.
Standards and Set Controls Data;
The purpose of this section is to provide information about the spik-
ing standards used in the set. Copy this information from the Assignment
Sheet. In the empty brackets to the right of the Method Blank, Laboratory
Control Spikes, Surrogate and Column Checks, write the date the control was
originated. This is the date of extraction for all but the Column Checks.
The Column Checks are originated on the date the florisil columns are begun.
For the Shipping Blanks and Laboratory Sample Spikes, t"he 9 digit sample -
code numbers are placed in the empty brackets.
-------
The information for the Name / Date of Std. Used and Amt. Spiked
action can be copied from the Assignment Sheet. The date in parenthesis
following the standard name indicates the date the standard was prepared.
The person who spikes a standard should writ* his initials behind it
in the Initials section.
Questions:
Has Sample Control Record been completed for both distribution
and return of samples?
The Sample Control Record is kept in the Receiving Room. Vfoen NFS
water samples are removed from the cooler for extraction, they are
signed out on the Sample Control Record. The empty sample bottles
are later returned to the Receiving Room and signed in on the Sample
Control Record.
Has Set Composition Form been attached?
The Assignment Sheet is prepared at EPA/ECL by the Project Manager
and sent to the Processing Laboratory at the start of each set
extraction.
Has ECL/NPS Tracking Form been attached?
The ECL/NPS Sample Tracking Form tracks the samples from storage
through extraction, and G.C. Analysis.
Signature:
The person completing this page of the form should sign and date the
form here.
Sample Preparation:
The NFS Method * O Extraction Procedure is broken down into six parts
in this section. The Date Accomplished and Initials of Bnployee(s) Doing
Vbrk should be provided for each. There is a section provided for comments
(exceptions to routine) if applicable.
Signatures;
Vhen sample extracts are delivered for GC analysis, the employee re-
linquishing the extracts and the employee receiving the extracts should
sign and date the QA Data Form.
-------
G.C. Analysis
Date tiequn:
Vfite the date the extracts are spiked with the Internal Standard.
Analyst (s); »
Write the name of the person(s) who analyzed the samples on the ins-
trument(s) and performed the calculations on the set.
Date Completed;
Write the date all calculations and data forms for the G.C. analysis
are completed and submitted for review.
Internal Std. Spike Data:
This section provides information concerning the Internal Std., the
date the set was spiked, amount used and the name and date of standard used.
This date is the date the Internal Std. was prepared.
I.D. of Instrument Used for Analysis:
Write in the serial no(s). of the G.C.(s) used.
Analysis Dates:
In this section, the controls and samples are referred to by their
Set Composition numbers as written on the first page of this form. Beside
each set composition number, record the date of the last injection on a
Gas Chromatograph for each control or sample.
Questions:
Is G.C. work complete?
Is all analysis on the instrument completed?
Have NFS Data Report Forms on samples been completed for each G.C. column'
This includes the primary and confirmatory G.C. columns.
Has remedial QC work been carried out with results attached?
The analyst is responsible for conducting QC checks. If any portion
of the data falls out of the acceptable QC limits,.remedial QC work
must be done. All QC checks and QC remedial work is outlined in the
QC Requirements and Criteria Attachment.
-------
If any sample in this set will be reextracted, list the 9 digit - code
no. of the sample.
Refer to the Set Composition section of this form to find the 9 digit -
code no. of the sample.
»-
Is any sample in this set a reextracted sample?
If the answer is Yes and additional information on the original sample
is needed, refer to the Set Composition section of this form. Any
reextracted sample will have an R preceding the 9 digit sample- code
number and be followed by the bracketed Set Number and Set Composition
Number of the original sample.
Signature;
The person completing this page of the form should sign and date the
form here.
Disposition of Extracts:
Following reviev of the G.C. Analysis Data, sample tubes are quanti-
tatively transferred to culture tubes and volumes marked. All information
on concentrator tubes is transferred to the culture tubes, which are then
stored in a cooler. At this tijne, the "EXTRACT STORAGE DATA SHEET",(See
Appendix A), is completed by recording all pertinent extract information.
Data Reviewed By:
Signature of person who reviewed completed data set. This must be
someone other than the person who analyzed the set.
Date:
Write the date the review was completed.
Final Disposition of Extracts:
Sample extracts will be held until the Technical Monitor approves of
their disposal (See 7.23 of the QAPP).
-------
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-------
INTERNAL QUALITY CONTROL CHECKLIST
Method 03/ Extraction Set *
CRITERIA FOR RESULTS
SURROGATE RECOVERY:
DCAA recovery must be within
+ 30% of mean recovery determined
during the initial demonstration
of capabilities.
ACCEPTABLE LIMITS*
PASS
FAIL
Mean: 84.6%
Range: 54.6 to 114.6%
INTERNAL STANDARD AREA:
Peak area for internal standard
in any sample must not deviate
by more than 20% from the mean
peak area for the calibration
standards it was analyzed
against.
PASS
FAIL
Mean:_
Mean:
LABORATORY CONTAMINATION:
Method blank should not contain
a peak greater than or equal to
one-half MRL for each analyte.
PASS
FAIL
Blank date_
Analyte
Amount found
INSTRUMENT PERFORMANCE:
See Section 11.1 of Method 3.
PASS_
R:
S/N:
PSF:
PGF:
FAIL
>0.4
>3.0
0.70 to 1.05
0.70 to 1.05
CALIBRATION STANDARD INTEGRITY:
A calibration curve based on newly
prepared standards must give
results which are within 20% of
the expected value for the most
recently prepared calibration
solutions.
PASS
FAIL
Calib. Curve
(date)
Calib. Level
*Note any exceptions to the Acceptable Limits.
Prepared by
Date
-------
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-------
Appendix I
Revision No 4
Date: December 1989
Page 1 of 3
APPENDIX I
ECL COMPUTER PROGRAMS
-------
BASIC F-P'OCRftM: REGVAP
MAR 23, 1988 15:43:27
5REM***REGVAR, WRITTEN FOR ECL BY UUD, OCT l,19So
10LETN = T = C1=C2 = H 1=1)2 = 0
28PRIHT"ENTER COMPOUND NAME";
3GDIMASC403
SSDIMUt 1C-<0>3
36DIMPC1G03
37DIMXC16G3
38DIMBC1GG3
39DIMGC1GG3
48INPUTA*
50PRINT"ENTER -1 AFTER YOUR LAST DATA POINT"
70PRINTI
86PR1 NT "ENTER YOUR VALUE FOR X";
96INPUTUCI3
ieeiFUCI3=-lTHEN150
12ePRINT"EHTER YOUR VALUE FOR Y " ;
I30INPUTP[ I 3
146NEXTI
156PRINT
166PRIHT-ARE ALL VALUES CORRECT? ";
17eiNPUTEt
18GIFB*="Y"THEN26G
!9ePRINT"EHTER THE NUMBER OF THE FAIR IN ERROR":
288 INPUT I
216PR1NT"ENTER THE CORRECT X";
228INPUTUCI3
238PRINT-ENTER THE CORRECT Y";
240INPUTPCI3
256GOTOieG
260FORI=1TON
278LETC1=C1*UCI3
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S18PRINTTRB(48>;CCn
S28LETT-T+GCI3
S38NEXTI
548PRINT"THE-SUM
358PRINT
-------
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END OF FILE
-------
Appendix „
Revision No 4
Date December 1989
Page 1 of 6
APPENDIX J
RAPID REPORTING NOTIFICATION
-------
\
I UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
*/,t ( ,t
-------
-2-
If you hive any questions concerning these procedures, please let Bob
Haxey or me knov. 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 13
AKALYTE RAPID REPORTING LEVEL
i .
V
Acifluorfen 130 ug/L
Bentazcm 87.5 ug/L
2,4-D 100 ug/L
Dalapon 800 ug/L
Dicamba 13 ug/L
Dinoseb 3.5 ug/L
Pentachlorophenol 300 ug/L
Picloram 700 ug/L
2.4,5-T * 105 ug/L
2,4,5-TP 70 ug/L
-------
METHOD 6
ANALXTE
Rapid
Reporting
Level (ppb)
Analytical Results
Primary GC Column
«- (ppb)
Secondary GC Column
(ppb)
*
GC/MS
(pos. or neq. or N/R*
.
NOT ANALYZED
QA Assessment:
Is there any QC problem(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
-------
BSL
NPS 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
(PCb)
•
Secondary GC Column
(PPb)
GC/MS
(pos. or neg. or N/R
•
METHOD 3
,
ANALXTE
Rapid
Reporting
Level (ppb)
Analytical Results
Primary GC Column
(PCb)
Secondary GC Column
(PCb)
GC/MS
(pos., neg., or N/R'
NOT ANALYZED
-------
Appendix K
Revision No 4
Date December 1989
Page 1 of 2
APPENDIX K
GC/MS CHARACTERISTIC IONS FOR METHOD 3
-------
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-------
Appendix L
Revision No 4
Date December 1989
Page 1 of 9
APPENDIX L
ADDENDA TO METHOD 3 - JUNE 1988 TO DECEMBER 1989
-------
05/01/89
Environmental Chemistry Section
Addendum - Method 3
Revision to Section 4, page'l/ paragraph 1, sentence 4*
- Change "Dr. Y. A. Yonan• ECL-QAO . . .• to "Mr. Danny McDaniel/
Acting ECS-QAC. . ."
Revision to Section 4, page I/ paragraph 2, sentence 2
- Change "..handled by Ms. Jan Watkins." to "...handled by Ms. Jan Watkins
backed up by Ms. Elizabeth Flynt."
Revision to Section 4; page 1, paragraph 2, sentence 3
- Change ". . . M. George Sand." to ". . .Mr. William Mitchell and
Mr. Joe Ferrario."
Revision to Section 4/ page 1« paragraph 2/ sentence 4
- Change "Data handling and reporting will be handled by Ms. Watkins backed up by
Mr. Mecomber and Ms. Flynt." to "Data handling and reporting will be handled by
Ms. Watkins backed up by Ms. Flynt."
Revision to Section 4, Figure 4-1 - ECS ANALYTICAL TEAM - Method 3
- Delete ECS ANALYTICAL TEAM diagram from Figure 4-1.
- Replace with revised diagram on following page.
Approved
EPA/ECS-NPS Project Deader/
F.CS Analytical Coordinator
Approved
QAO-NPS^
Approved Tn^a^^ /rfrd*
QAO-ODIQ
Approved
I
MPS Director
-------
Project: NFS
Section No: 4
Revision No: 4
May 1989
Page of
Sample Custodian
G. Gardner (EPA)
Assistant Sample
Custodians
J. Cuevas (EPA)
S. Mecomber (EPA)
Sample Prep./Ext.
E. Flynt (EPA)
S. Mecomber (EPA)
ECS ANALYTICAL TRAM
METHOD 3
NPS Project Leader
Bob Maxey (EPA)
GC
J. Watkins (STI)*
E. Flynt (EPA)
ECS-QAC (Acting)
D. McDaniel
Data Review
W. Mitchell (AARP)
J. Ferrario (EPA)
GC/MS
J. Ferrario (EPA)
Data Handling/
Reporting
J. WatJcina (STI
E. Flynt (EPA)
* = Sverdrup Technology Inc. (In-house Contractor for ECS)
ECS provides overall technical direction to Sverdrup Technology, Inc.
FIGURE 4-1: ECS ANALYTICAL TEAM - METHOD 3
-------
8/12/83
ENVIRONMENTAL CHEMISTRY LABORATORY
ADDENDUM - METHOD 3
Addition to Section 4, page 1, paragraph 2, sentence 3
»^ _
-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 39529-6OOO"
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 Cuevas
(601)688-3170 (or 3217)
Mr. Stanley Mecomber
(601)688-3170 (or 3217)
Figure 4-1: ECL ANALYTICAL TEAM was revised. The new chart is
enclosed.
Approved
Approved
Approved
' EPA/ECS-NPS Project leader/
ECS Analytical Coordinator
-------
Project: NFS
Section No: 4
Revision No: 3
June 1988
Page of
ECL ANALYTICAL TEAM
METHOD 3
I I
| NPS Project Leader |
I I
I Bob Haxev (EPA) 1
Sample Custodian
G. Gardner (EPA)
J. Cuevas (EPA)
1
I
1
1
1
1 1
1 1
I Y.Yonan (EPA) |
1 1
| Data Review |
1 I
I George Sand (EPA)
I
| Sample Prep./Ext.
I
I
| S. Hecomber (EPA)
GC
J. Watkins (STI)*
I
GC/MS
| D. McDaniel (HR)(EPA)|
I J. Ferrario (LR)EPA)I
| | Data Handling/
| | Reporting
I
I J. Watkins (STI)
I I
| Sample Prep./Ext. |
j Elizabeth Flynt, |
I (STI) * |
STI = Sverdrup Technology Inc. (In-house Contractor for ECL)
Sverdrup is providing the ECL several person years of support.
ECL provides overall technical direction to Sverdrup Technology,
FIGURE 4-1: ECL ANALYTICAL TEAM - METHOD 3
Inc.
-------
7/21/88
Environmental Chemistry Laboratory
Addendum - Method 3
Addition to Section 2, page 1, Appendix H
-Add "Internal Quality Control Checklist" below "QC Data Sheet"
-Add an Appendix "K: QC/MS CHARACTERISTIC IONS FOR METHOD 3"
Addition to Section 5, page 1, number 8, end of paragraph
-Add "See Appendix K for a Table of the three ions for each analyte"
Addition to Appendices
-Add Internal Quality Control Checklist (enclosed) to end of Appendix G
-Add a cover sheet for Appendix K: GC/MS CARACTERISTIC IONS FOR METHOD 3.
(For the appendix contents/ see the enclosed GC/MS Characteristic Ions
Table.)
Approved
N^TDirector
-------
INTERNAL QUALITY CONTROL CHECKLIST
Method 03/ Extraction Set f
CRITERIA FOR RESULTS
ACCEPTABLE LIMITS
SURROGATE RECOVERY:
DCAA recovery must be within
+ 30% of mean recovery determined
Airing the initial demonstration
of capabilities.
PASS
FAIL
Mean: 84.6%
Range: 54.6 to 114.6%
INTERNAL STANDARD AREA:
Peak area for internal standard
in any sample must not deviate
by more than 20% from the mean
peak area for the calibration
standards it was analyzed
against.
PASS
FAIL
Mean:_
Mean:_
Mean:
LABORATORY CONTAMINATION:
Method blank should not contain
a peak greater than or equal to
one- half MRL for each analyte.
PASS
FAIL
Blank date
Analyte
Amount found
INSTRUMENT PERFORMANCE:
See Section 11.1 of Method 3.
PASS
FAIL
R:
S/N:
PSF:
PGF:
>0.4
>3.0
0.70 to 1.05
0.70 to 1.05
CALIBRATION STANDARD INTEGRITY:
A calibration curve based on newly
prepared standards oust give
results which are within 20% of
the expected value for the most
recently prepared calibration
solutions.
PASS
FAIL
Calib. Curve
(date)
Calib. Level
*Note any exceptions to the Acceptable Limits.
Prepared by
Date
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