United State. Office of Water (WH-550) EPA 810-B«a-002
Environmental Protection Office of Pesticides and February 1982
Agency Toadc Substances (H-7501C)
QUALITY ASSURANCE PROJECT PLAN
FOR THE
NATIONAL PESTICIDE SURVEY OF DRINKING WATER WELLS
ANALYTICAL METHOD 1 - NITROGEN/PHOSPHOROUS
PESTICIDES AND ANALYTICAL METHOD 3 -
CHLORINATED ACID HERBICIDES
Prepared by:
Julie Zalikowski
Montgomery Laboratories
555 East Walnut Street
Pasadena, California 91109
Prepared for:
U.S. Environmental Protection Agency
Technical Support Division
Office of Drinking Water
26 W. Martin Luther King Drive
Cincinnati, Ohio 45268
U S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
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Section No. 1
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APPROVAL PAGE
U.S. ENVIRONMENTAL PROTECTION AGENCY
MONTGOMERY LABORATORIES
Project Officer and Technical Monitor Date Quality Assurance
Date
NPS Quality Assurance Officer Date Project Manager
Date
Program Manager Date
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Section No 2
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(
NATIONAL PESTICIDE SURVEY
QUALITY ASSURANCE PROJECT PLAN
ANALYTICAL METHOD 1 - NITROGEN/PHOSPHORUS
ANALYTICAL METHOD 3 - CHLORINATED ACID
FOR
PESTICIDES
HERBICIDES
AND
2. TABLE OF CONTENTS
Section
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
Pages Revisions
TITLE AND APPROVAL PAGE
TABLE OF CONTENTS
PROJECT DESCRIPTION
PROJECT ORGANIZATION AND RESPONSIBILITIES
QUALITY ASSURANCE OBJECTIVES FOR
MEASUREMENT DATA
SAMPLING PROCEDURES
SAMPLE CUSTODY
CALIBRATION PROCEDURES AND FREQUENCY
ANALYTICAL PROCEDURES
DATA REDUCTION, VALIDATION REPORTING
INTERNAL QUALITY CONTROL CHECKS
PERFORMANCE AND SYSTEM AUDITS
PREVENTIVE MAINTENANCE
SPECIFIC PROCEDURES FOR ASSESSING
MEASUREMENT SYSTEM DATA
CORRECTIVE ACTION
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16. QUALITY ASSURANCE REPORTS TO
MANAGEMENT
9/10/90
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2. TABLE OF CONTENTS (continued)
Appendices
A.
B.
C.
D.
E.
F.
G.
H.
I.
J.
K.
L.
M.
NFS METHODS 1 AND 3
FORMAT FOR NPS DATA FILES
MASS IONS FOR GCMS CONFIRMATION
DIXON'S TEST
ROUNDING AND SIGNIFICANT FIGURES
EXTRACTION SOP FOR METHOD 1
EXTRACTION SOP FOR METHOD 3
SOP FOR PREPARATION OF DIA2OMETHANE
SOP FOR PREPARATION OF SODIUM SULFATE
NPSIS SAMPLE RECEIPT SOFTWARE FOR
LABORATORIES
NELSON DATA SYSTEM CALCULATIONS
SOP FOR ARCHIVAL OF NPS DATA
SOP FOR NPS WASTE TREATMENT
Pages
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3. PROJECT DESCRIPTION
Project Summary
Montgomery Laboratories will provide analytical services to the U.S. EPA for analysis of samples
collected from well water sites throughout the country to assess the nature and scope of
contamination by pesticides and their by-products (National Pesticide Survey or NPS). These data will
be used to determine correlations between pesticide contamination and such factors as patterns of
pesticide usage and ground water vulnerability.
Background
During the planning stages of the NPS, EPA found that no combination of currently approved
methods could satisfy the need of the Survey for analyses of over 100 pesticides, degradation
products, and metabolites. A considerable method development effort was therefore initiated in
cooperation with the EPA Environmental Monitoring Systems Laboratory (EMSL) in Cincinnati. The lab
contracted with Battelle-Columbus for the development of one new method and revisions to five
existing EPA methods. Battelle used both real and simulated groundwaters as test matrices during
the development effort in order to approximate the type of sample that would be encountered during
actual Survey analyses. Prior to the NPS pilot, results of Battelle's efforts were subjected to peer
review by the Agency, States, universities, and commercial labs. During the pilot, the performance of
the methods was evaluated again and further improvements to the methods were made at this time.
Concurrent with the implementation of the Survey, a multilab validation study will be conducted.
Methods
Montgomery Laboratories will utilize the following NPS methods to perform the analyses:
NPS Method #1 - Determination of Nitrogen- and Phosphorus- Containing
Pesticides in Ground Water by Gas Chromatography with a Nitrogen- Phosphorus
Detector. (Appendix A)
Pesticides containing nitrogen and/or phosphorus are extracted from water at
neutral pH by methylene chloride and analyzed by capillary column gas
Chromatography equipped with a nitrogen-phosphorous detector. This method is
based on EPA Methods 622 and 633. Table 3.1 lists the pesticides to be analyzed
by this method.
The method involves adding 100 grams of NaCI to one liter of sample (adjusted to
pH 7) with 60 ml of methylene chloride. This extraction is performed three times
and the extracts are combined. The extract is dried over sodium sulfate. The
extract solvent is exchanged to methyl-t-butyl ether (MTBE). The 5 ml final extract is
injected into a GC equipped with a 30 M DB-5 fused silica capillary column and the
compounds detected with a Nitrogen-Phosphorus detector. The confirmation
column will be a 30 M DB-1701 fused silica capillary cciumn. Montgomery will use a
single injection, dual column-dual detector setup for automatic dual column
confirmation.
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NFS Method #3 - Determination of Chlorinated Acids in Ground Water By Gas
Chromatography with an Electron Capture Detector. (Appendix A)
Certain phenols and chlorophenoxy acid herbicides are extracted from water at an
acidic pH by ethyl ether. The extracts are esterified and analyzed by capillary
column gas Chromatography equipped with an electron capture detector. This
method is based on EPA Method 615. Table 3.2 lists the pesticides to be analyzed
by this method.
The method involves adding 250 grams of NaCI to one liter of sample which is then
adjusted to pH 12 with 6N NaOH. The sample is periodically shaken for one hour to
hydrolyze derivatives. The sample is then extracted three times with 60 ml of
methylene chloride. This basic extract contains extraneous organic material and is
therefore discarded. The pH is then adjusted to pH 2 or less with H2S04. The
sample is then extracted with 120 ml of diethyl ether. The sample is then extracted
two additional times with 60 ml of diethyl ether. The ether extracts are combined
and dried over sodium sulfate. The extract solvent is then exchanged to
Methyl-t-butyl ether (MTBE). This extract is then methylated using diazomethane.
Silicic acid is added to the extract to destroy any remaining diazomethane. The 5
ml final extract is injected into a GC equipped with a 30 M DB-5 fused silica capillary
column and the compounds detected with a Electron Capture Detector. The
confirmation column would be a 30 M DB-1701 fused silica capillary column.
Montgomery will use a single injection, dual column-dual detector setup for
automatic dual column confirmation. The method contains a special Florsil cleanup
procedure to be used on extracts of all samples.
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TABLE 3.1
PESTICIDES ANALYZED USING NFS METHOD 1
Alachlor Methyl paraoxon
Ametryn Metolachlor
Atraton Metribuzin
Atrazine Mevinphos
Bromacil MGK 264
Butachlor Molinate
Butylate Napropamide
Carboxin Norflurazon
Chlorpropham Pebulate
Cycloate Prometon
Diazinon Prometryn
Dichlorvos Pronamide
Diphenamid Propazine
Disulfoton Simazine
Disulfoton sulfone Simetryn
Disulfoton sulfoxide Stirofos
EPTC Tebuthiuron
Ethoprop Terbacil
Fenamiphos Terbufos
Fenarimol Terbutryn
Fluridone Triademefon
Hexazinone Tricyclazole
Merphos Vernolate
TABLE 3.2
PESTICIDES ANALYZED USING NPS METHOD 3
Acifluorfen Dichlorprop (2,4-DP)
Bentazon Dinoseb
Chloramben 5-Hydroxydicamba
2,4-D 4-Nitrophenol
2,4-DB PCP
Dalapon Picloram
DCPA Acid metabolites 2,4,5-T
Dicamba 2,4,5-TP (Silvex)
3,5-Dichlorobenzoic acid (DBA)
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Section No. 4
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Page 1 o< 4
4. PROJECT ORGANIZATION AND RESPONSIBILITIES
The staff organization and chain of command which Montgomery Laboratories will utilize for this
project is shown in Figure 4.1. Details of staff responsibilities and qualifications are summarized in this
Section.
PROJECT MANAGER: ANDREW D. EATON, Ph.D
As Laboratory Director, Dr. Eaton will serve as the Project Manager and have full responsibility
and authority for the project and serve as liaison with the U.S. EPA Project Officer. Dr. Eaton will
review all of the final data generated for the project, oversee any major decisions which must be
made, insure that the Program Manager has the necessary resources to accomplish the proposed
work within the allotted time and budget, and insure that all laboratory and EPA specified quality
control guidelines are being performed and are acceptable. Dr. Eaton will also insure that
appropriate corrective action is taken for any out-of-control events that occur. Dr. Eaton can be
reached at Montgomery's telephone number: (818) 796-9141.
PROGRAM MANAGER: JULIE ZALIKOWSKI
Julie Zalikowski will serve as the Program Manager and provide daily technical and managerial
guidance to insure that the analytical work is performed within EPA specified turn-around times and
conforms with the quality control guidelines specified by EPA and this QA Project Plan. Ms. Zalikowski
can be reached at Montgomery's telephone number: (818) 796-9141.
QUALITY ASSURANCE OFFICER: RICK A. MEALY
Mr. Mealy will insure that all contract specified and routine internal laboratory quality control
procedures are performed by the analysts for this project. He will also insure that all data and
supporting quality control parameters are reviewed and approved by an appropriate supervisor or
peer before the analyst is allowed to enter the data into the computer system. Approval is granted
upon verification that all quality control parameters lie within specified acceptance limits and no
analytical or computational errors appear on the analyst's data sheets. Mr. Mealy, as QA officer,
reports directly to the laboratory director. Mr. Mealy can be reached at Montgomery's telephone
number: (818) 796-9141.
ASSISTANT QUALITY ASSURANCE OFFICER: WAVERLY BRAUNSTEIN
Ms. Braunstein will serve as the Assistant Quality Assurance Officer, performing periodic audits.
She is currently the laboratories' Assistant QAO, reporting to Mr. Mealy.
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Page 2 of 4
GAS CHROMATOGRAPHY ANALYST: ROOBIK YAGHOUBI
Mr. Yaghoubi is an associate chemist/GC analyst and will perform GC analysis for Method 3.
He has been with Montgomery for the past 2 years.
GAS CHROMATOGRAPHY ANALYST: FRANKLIN CONSTANTINE
Mr. Constantine is a chemist/GC analyst and will perform GC analysis for Method 1. Mr.
Constantine has performed a wide variety of GC analyses of environmental samples and has over 4
years of experience.
EXTRACTIONS SUPERVISOR: RICHARD HANSEN
Mr. Hansen is the extractions supervisor. Mr. Hansen will supervise the extraction of the
samples, insuring that the proper QC samples are performed and that the extractions are performed in
the specified holding times. Mr. Hansen has been with Montgomery Laboratories for five years
performing extractions, TOC, TOX, THM, EDB/DBCP, pesticide and herbicide analyses on a variety of
drinking waters and ground waters.
EXTRACTION TECHNICIANS
The following persons will be performing extractions for Methods 1 and 3: Jeannie Park, Edy
Cosio, Lisa Loring, Stanley Kikkert, Enrique Gomez, Francisco Gomez.
SUPERVISING GAS CHROMATOGRAPHY/MASS SPEC ANALYST: CECILIA LEI
Cecilia Lei is the supervisor of the GC/MS group at Montgomery Laboratories. She has over 5
years of experience performing GC/MS analysis of environmental samples. Ms. Lei is proficient at
mass spectral interpretation and analysis of compounds in drinking water. Ms. Lei will perform the
confirmation of extracts by GC/MS.
GAS CHROMATOGRAPHY/MASS SPECTROMETRY ANALYST: DAN HAUN
Mr. Haun has three years of GC/MS experience and was a GC/MS operator at CompuChem
Laboratories before coming to Montgomery Laboratories. Mr. Haun will perform the confirmation of
extracts by GC/MS.
SAMPLE RECEIVING CLERK
Beverly Gaskins will be the primary Sample Receiving Clerk. The backup Sample Receiving
Clerk will be Bruce Havlik, who is Montgomery Laboratories current Sample Receiving Clerk. Both can
be reached at Montgomery's phone number during working hours. Montgomery's address for sample
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Section No. 4
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Page 3 of 4
receipt is 555 E. Walnut, Pasadena, CA, 91101. The phone number is (818) 796-9141. Normal
working hours are from 8 am to 5 pm local Pacific time.
DATA HANDLING AND REPORTING CLERK
Beverly Gaskins will be the Data Handling and Reporting Clerk. This will be the same person
who will be primary contact for sample receipt. Julie Zalikowski will serve as backup.
TECHNICAL MONITOR: ROBERT A. MAXEY
The EPA Technical Monitor for Methods 1 and 3 will be Robert Maxey of the EPA's office in
Mississippi. His telephone number is (601) 688-1225. Mr. Maxey will serve as primary contact for the
project for all technical matters concerning Methods 1 and 3.
EPA PROJECT OFFICER: ROBERT A. MAXEY
The EPA Project Officer for Methods 1 and 3 will be Bob Maxey of the EPA's office in
Mississippi. His telephone number is (601) 688-1225. Mr. Maxey will serve as primary contact for all
contractual matters concerning Methods 1 and 3.
SUMMARY
The following is a summary of the Montgomery Laboratories personnel assigned to this project:
Program Manager: Julie Zalikowski
QA Oversight: Rick Mealy
Waverly Braunstein
Sample Receipt: Beverly Gaskins
Backup: Bruce Havlik
Sample Preparation: Rick Hansen (supervisor)
Jeannie Park
Edy Cosio
Lisa Loring
Stanley Kikkert
Enrique Gomez
Francisco Gomez
Sample Analysis: Roobik Yaghoubi (Method 3)
Franklin Constantine (Method 1)
GCMS Confirmation: Celilia Lei
Dan Haun
Data Handling and Reporting: Beverly Gaskins
Backup: Julie Zalikowski
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Page 4 of 4
FIGURE 4.1
MONTGOMERY LABS
NPS STAFF ORGANIZATION
Project Manager
Andrew Eaton, PhD
Laboratory Director
Quality Assurance
Rick Mealy
W. Braunstein
Program Manager
Julie Zalikowski
Method 1
Franklin
Constantino
Method 9
Whitney Moore
Extractions
Rick Hansen (Suol
Stan Kikkert
Suzette LJrio
Glenn Okui
Usa Loring
Enrique Gomez
Francisco Gomez
Method 3
Roobik Yaghoubi
Data Clerk and
Sample Receiving
Beverly Gaskins
Bruce Havlik
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Section No. 5
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5. QUALITY ASSURANCE OBJECTIVES FOR MEASUREMENT DATA
Initial Demonstration of Capabilities: Determining Reporting Limits
The following procedure will be used to determine the estimated detection limits (EDL) and
minimum reporting limits (MRL).
1) Determine the 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.
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 estimated 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) The eight EDL extracts will also be analyzed using the confirmation column. EDLs
determined on the confirmation column must equal those determined on the primary
column. Again, EDLs exceeding this requirement will be approved on a case by
case basis, by the technical monitors.
8) The laboratory 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 and included as Appendix C. 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.
9) The minimum reporting levels (MRLs) found in Table 5.1, are computed with the
following multiples of the EDL:
Method 1 MRL = 4 times EDL
Method 3 MRL = 5 times EDL
10) Any chromatographic peak occurring at the proper retention time of an NPS analyte,
at a concentration level between the EDL and the MRL, is to be reported as an
occurrence of that analyte. However, no confirmations or quantifications are to be
performed. If this suspect analyte occurs frequently, the proper confirmations and
subsequent adjustment of the minimum reporting level may be required. Also, any
frequent occurrence of a non-NPS analyte at what appears to be a high
concentration, should be noted. Section 11 of this QAPjP contains the requirements
for monitoring these occurrences.
11) The lower concentration calibration standard must be prepared at a concentration
equal to the minimum reportable level.
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Establishment and Use of Control Charts
1) Montgomery Laboratories 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.
2) To establish the control charts, following initial demonstration of capability, 5 reagent
water samples will be spiked at 10 times the MRL for the method and carried
through extraction and analysis. 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.
3) Criteria for Accuracy and Precision
1) The Relative Standard Deviation (RSD) for any analyte must be less than or
equal to 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 the Technical Monitor for the method.
2) The mean recovery of each analyte must lie between Battelles' mean recovery
for each analyte (at the corresponding level) and plus or minus 3 times the
RSD for that analyte as determined by Battelle during methods development,
but no greater than Battelle's recovery plus or minus 30%.
Example: For an analyte "A"
Battelle demonstrated recovery of 80% for analyte A with RSD of
5%. Acceptable recoveries will be 80% plus or minus 3 times 5%
or 65% - 95%; or,
Battelle demonstrated recovery of 80% with RSD of 15%.
Acceptable recoveries will be limited to 80% plus or minus 30% or
50% - 110%.
3) Surrogate: In establishing the control chart for the surrogate, criteria in 3(1)
and (2) above apply; it follows that one of the spike mixes must contain the
surrogate at the concentration spiked into actual samples.
Surrogate recoveries from samples will be required to be within plus or minus
30% of the mean recovery determined for that surrogate during the initial
demonstration of capabilities.
If the surrogate spiked into the Method Blank or LCS should fail to meet the
quality control requirements for the recovery of that surrogate, this Method
Blank or LCS must be invalidated. This would result in the invalidation of all
samples associated with that Method Blank or LCS. In order to reduce the
possibility of this resulting in the loss of otherwise valid data, the following
procedures can be used:
a) A LCS in which the surrogate recovery has failed to meet the quality
control limits can be validated if the following conditions are met:
i) The LCS meets all other required quality control elements.
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ii) The surrogate recovery observed for the Method Blank associated
with that same sample set meets the quality control limits
determined using the control chart for that surrogate.
b) A Method Blank in which the surrogate recovery has failed to meet the
plus or minus 30% criteria can be validated if a field sample associated
with that same sample set meets all of the quality control requirements
for a Method Blank.
4) Warning Limits/Control Limits: The control charts will be drawn so as to
depict both warning limits (plus or minus 2 standard deviations (sd)) and
control limits (plus or minus 3sd) about the mean.
4) Outliers: Dixon's test will be used to determine outliers. The method for using
Dixon's test is included as Appendix D. There can be no more than 3 outliers per
analyte from the 20 spiked controls.
5) Out-of-Control Situations: Sections 5(1) and 5(2) below refer to the recovery of
analytes in the laboratory control standards (LCS) which are part of each sample
set.
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 the
control limits.
b) The same analyte is outside the control limit twice in a row, even though
more than 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 the warning
limits but inside the control limits.
b) A run of 7 consecutive points above or below the mean.
c) A run of 7 points for an analyte in increasing or decreasing order.
An "alert" situation implies a trend toward an "out-of-control" situation.
The laboratory is required to evaluate the analytical system before
proceeding. If "alert" or "out-of-control" situation occur frequently,
re-establishing control charts may be required by the Technical Monitor
before analytical work can proceed.
3) Other Factors:
a) Method Blank: If the method blank exhibits a peak within the retention
window of any analyte and is greater than or equal to one-half the MRL
for that analyte, an "out-of-control" situation has developed.
b) Performance-Evaluation Samples: If the laboratory fails on one of the
PE samples, an "out-of-control" situation is present.
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6) Updating Control Charts: Following the establishment of the control chart, a
Laboratory Control Standard (LCS) will be 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 charts by adding these 5 most recent recoveries to the
20 original points and then deleting the first 5 of the original points. If the chart was
generated using only 17 points, only 2 of the first points are discarded. Dixon's test
will be applied to the new data to evaluate outliers. The method for using Dixon's
test is presented in Appendix D. Accuracy and precision are recalculated and the
chart re-drawn. The newly drawn chart will then apply to all data in sample sets
subsequent to the last one used to update the chart.
Laboratory QC Requirements For Primary Analyses
1) Laboratory control standard mixes (LCS), which together contain all method
analytes, will be analyzed with each set of samples. Method 1 will contain 3 LCS
mixes and Method 3 will contain 2 LCS mixes. A list of the compounds for each
LCS mix is given in Table 5.2.
2) A set of samples is defined as all samples, blanks, spiked samples, LCS, etc. ,
which are extracted at the same time.
3) The internal standard area checks detailed in the methods will be used as stated
(Section 10.5 of the method) with the exception that the allowable limits will be plus
or minus 20 percent. However the control limits will be reassessed following
completion of the initial demonstration of capabilities.
4) The measurement system is to be evaluated whenever any analyte is observed in a
method blank, at a concentration greater than or equal to one-half the MRL
Method blanks are to be analyzed with each sample set.
A sample set in which the surrogate compound recovery of the Method Blank has
failed to meet the plus or minus 30% criteria can be validated by use of a Field
Sample, from that sample set, which meets all of the QC requirements for a Method
Blank. Note that this is not a procedure to validate the surrogate or the Method
Blank, but rather it is a procedure to validate the sample set by use of a Field
Sample as a Method Blank.
5) The criteria for monitoring instrument control standards will be utilized as stated in
the method (Section 10.9 of the method).
6) Surrogate recoveries from field samples will be required to be within plus or minus
30% of the mean recovery determined for that surrogate during the initial
demonstration of capabilities.
7) The requirement for monitoring calibration standard responses will be followed as
written in the methods (Section 9.2.3 of the method).
8) Samples failing any QC criteria must be reanalyzed at the contractors expense.
9) Only qualitative analyses will be required for the following Method 1 compounds:
Diazinon, Disulfoton, Disulfoton sulfone, Disulfoton sulfoxide, Merphos, Pronamide,
and Terbufos. Only qualitative analyses will be required for Acifluorfen, Chloramben,
Dalapon, and 4-Nitrophenol in Method 3. While these analytes are to be present in
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at least one of the concentration levels of the calibration standards, they are not
subject to any of the QC requirements.
10) Each time that new calibration standard dilutions are prepared they must be
compared to the existing calibration curve, and the observed concentration must
agree within plus or minus 20% of the expected concentration. For Method 1, the
Technical Monitor may change this requirement if the standards prove to be
unstable.
11) Any deviation from the analytical procedures or QC requirements must be approved
by the Technical Monitor and documented in writing.
Laboratory QC Requirements For Second Column Confirmation Analyses
1) Second column confirmation will be required for all compounds detected on the
primary column at concentrations above the MRL.
2) Quantitate by comparison to a calibration standard, which is within plus or minus
20% of the concentration of the sample determined using the primary column.
3) The concentration determined on the secondary column must agree within plus or
minus 25% of the result determined on the primary column.
4) If the concentration determined on the secondary column does not agree within the
limits stated above the laboratory must confer with the Technical Monitor concerning
resolution of the discrepancy, if the results on both columns are above the MRL.
Laboratory QC Requirements for Time-Storage
Time storage samples will be collected and analyzed during the NPS study to determine the
stability of the compounds in aqueous solution and in the extraction solvent. These samples will be
collected at a frequency of 10% over the period of the study.
One time storage site will consist of four aliquots collected for each spiking mixture. Therefore,
for Method 1, twelve 1 L bottles will be collected per time storage site and for Method 3, eight 1 L
bottles will be collected per time storage site. For each spiking mixture, two of the four replicate
aliquots will be spiked, extracted, and analyzed within a four-day time frame. They will then be
reanalyzed 10-18 days after the first analysis. The remaining two duplicates will be spiked at the
same time as the first two duplicated but will be allowed to sit 14 days before extraction. These
samples will then be analyzed within four days of extraction.
All time storage samples will be spiked at 10 X MRL. Results of the time storage samples will be
reported to EPA along with the corresponding regular sample. Any statistical analysis of time storage
data will be conducted by EPA.
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Laboratory QC Requirements for Lab Spikes
Lab spikes are duplicate field samples that have been spiked in the lab with known amounts of
the analytes of interest in order to monitor spike recoveries from that matrix. The frequency of spiked
samples will be 10% of all samples. Samples to be spiked and the concentration to be spiked will be
designated on sample receipt material. Montgomery will not make the decision of which samples to
spike. All laboratory QC requirements for primary analyses will apply to the analysis of lab spike
samples.
GC/MS Confirmation
1) GC/MS confirmation will be required for all compounds confirmed by second
column analysis.
2) 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 the lower.
3) If additional sample treatment is performed for GC/MS analysis (blowdown, etc.),
the standard and sample must both undergo the same treatment.
4) Results of the GC/MS analysis are simply reported as the presence or absence of
the analyte.
5) The sample extract is to be shipped to the referee laboratory for high resolution
GC/MS analysis if confirmation of the analyte is not possible using quadrupole
GC/MS due to the concentration of the analyte, and if the concentration is equal to
or greater than one-half the lowest adverse health effect level for that analyte, or if
requested by the Technical Monitor.
The sample extracts will be shipped in 1 ml screwcap vials, packed in ice and
shipped to the EPA Sample Custodian; Gerald Gardner, USEPA, Environmental
Chemistry Laboratory, NASA/NSTL, Building 105, NSTL Station, MS 39529. Each
vial will have the liquid level marked on it's side to determine if evaporation of
extract has occurred during shipment.
Miscellaneous Other QC Notes
1) The results of the Initial Demonstration of Capabilities will be reported to the
Technical Monitor for approval and inclusion into this QAPjP
2) Additional samples will be collected at 10% of the samples sites for spiking at the
laboratory. The data from these spikes will be used to assess the recovery of the
analytes from a variety of matrices. These samples are to be spiked at analyte
concentrations equal to 2, 10 or 20 times the minimum reportable level for each
analyte. Only one of the standard mixes will be spiked per spike sample. Samples
collected for the analyte stability studies are to be spiked at 10 times the minimum
reportable level for each analyte.
-------
Section No 5
Revision No. 8
Date. September 10, 1990
Page 7 of 10
TABLE 5.1
METHOD 1 MRLs
Compound
Alachlor
Ametryn
Atraton
Atrazine
Bromacil
Butachlor
Butylate
Carboxin
Chlorpropham
Cycloate
Diazinon
Dichlorvos
Diphenamid
Disulfoton
Disulfoton sulfone
Dislfoton sulfoxide
EPTC
Ethoprop
Fenamiphos
Fenarimol
Fluridone
Hexazinone
Merphos
Methyl paraoxon
Metolachlor
Metribuzin
Mevinphos
MGK-264
Molinate
Napropamide
Norflurazone
Pebulate
Prometon
Prometryn
Pronamide
Propazine
Simazine
Simetryn
Stirofos
Tebuthiuron
Terbacil
Terbufos
Terbutryn
Triademefon
Tricyclazole
Vernolate
MRL ug/l
1.00
0.260
0.336
0.240
2.216
1.472
0.600
1.032
0.700
0.400
0.084
0.240
0.432
0.200
0.200
0.352
0.30
0.120
0.297
0.404
1.776
0.268
0.420
0.300
1.50
0.364
0.300
2.08
0.360
0.500
0.356
0.384
0.292
0.200
1.34
0.196
0.752
0.104 •
0.360
0.448
3.492
0.200
0.297
0.320
1.20
0.368
-------
Section No. 5
Revision No 8
Date: September 10, 1990
Page 8 of 10
TABLE 5.1 (continued)
METHOD 3 MRLs
Compound MRL ug/l
Acifluorfen 0.20
Bentazon 0.50
Chloramben 0.50
2,4-D 0.50
2,4-DB 2.0
Dalapon 5.0
DCPA 0.20
Dicamba 0.20
3,5-Dichlorobenzoic acid 0.60
Dichlorprop (2,4-DP) 0.50
Dinoseb 2.5
5-Hydroxydicamba 0.20
4-Nitrophenol 5.0
Pentachlorophenol 0.20
Picloram 1.0
Silvex (2,4,5-TP) 0.20
2,4,5-T 0.20
-------
Section No. 5
Revision No 8
Date. September 10, 1990
Page 9 of 10
TABLE 5.2
METHOD 1 LCS MIXES
MIX A
Bromacil
Carboxin
Chlorpropham
Cycloate
Dichlorvos
Diphenamid
Disulfoton (qual)
Disulfoton sulfone (qual)
Disulfoton sulfoxide (qual)
EPTC
Fenarimol
Fluridone
Hexazinone
Merphos
Metribuzin
Mevinphos
Molinate
Norflurazon
Pebulate
Prometon (qual)
Prometryn
Pronamide (qual)
Propazine
Simetryn
Tebuthiuron
Triademefon
Tricyclazole
Vernolate
MIX B
Alachlor
Atrazine
Butylate
Ethoprop
Fenamiphos
Methyl paraoxon
MGK264
Striofos
Terbufos (qual)
Terbutryn
MIXC
Ametryn
Atraton
Butachlor
Diazinon (qual)
Metholachlor
Napropamide
Simazine
Terbacil
-------
Section No 5
Revision No 8
Dale: September 10, 1990
Page 10 of 10
TABLE 5.2 (continued)
METHOD 3 LCS MIXES
MIX A MIXB
Acifluorfen Chloramben (qual)
Bentazon Dinoseb
2,4-D 4-Nitrophenol
2,4-DB
Daiapon
DCPA Acid metabolites
Dicamba
3,5-Dichlorobenzoic Acid
Dichloroprop 2,4 DP
5-Hydroxy Dicamba
PCP
Pichloram
2,4,5-T
2,4,5-TP Silvex
-------
Section No 6
Revision No 8
Date. September 10, 1990
Page 1 of 2
6. SAMPLING PROCEDURES
Sample bottle preparation, sample collection, and sample shipping will be performed by an EPA
contractor (ICF). Samples will be shipped iced for overnight delivery to the laboratory.
The containers, preservatives, and maximum holding times specified in the methods for each
analytical group required for this contract are listed in Table 6.1. Any work orders supplied by the
EPA with the samples are used as a packing slip by the Sample Receiving Clerk to insure that the
correct number of bottles have been shipped and have been correctly labelled. Table 6.2 lists the
number of bottles to be shipped to Montgomery with each sample type.
TABLE 6.1
SAMPLE CONTAINERS, PRESERVATIVES, AND HOLDING TIMES
ANALYSIS SIZE PRESERVATIVE HOLDING TIME
NPS #1
NPS #3
1 L
1 L
HgCI2 -
HgCI2 -
10 ml
10 ml
Extract 14 Days
Analyze 14 Days
Extract 14 Days
Analyze 14 Days
All samples will be stored at 4<>C
All extracts will be stored at -20<>C
Mercuric chloride solution is 1 g/l in deionized water.
Sampling Paperwork
A) Figure 6.1 is a copy of the label to be used on the sample bottles. The label will
contain the following information: Sample number, Sample code, Date sampled,
and Sampler name. The following codes will be used for the sample number
identification:
The example sample number is PD-0415-1-3-6.
P = National Pesticide Survey Sample
D = Domestic well
C = Community well
R = Resampled well
B = PE sample
0415 = Site number
1 = Lab number
3 = Method number
6 = Analysis scenario
An additional code will be on each sample label. An example of this code is
JMM-#3-XXX, where JMM is Montgomery Laboratories, #3 is method 3, and XXX is
a code for the exact sample type. The following is a list of possible sample types
and their codes:
FS = Field Sample
FD = Field Duplicate
BU = Backup Sample
-------
Section No. 6
Revision No. 8
Date. September 10, 1990
Page 2 of 2
T/S = Time Storage, t = 14 days
T/SO = Time Storage dup , t = 0 days
T/S 14 = Time Storage dup, t = 14 days
LSS = Laboratory Spike, where
LSS-A1 = Lab spike, Mixture A, Level 1
LSS-B1 = Lab spike, Mixture B, Level 1
(LSS spiked at Level 2 (10 x MRL) will also serve as Time Storage, t=0 days.)
B) Figure 6.2 is a copy of the field sample tracking sheet which will be used.
TABLE 6.2
TOTAL SAMPLE BOTTLES REQUIRED
Kit Type
Sample type
Bottle size
Method #
Primary
Backup
Lab Spike
T/S DO
T/S D14
Totals
# sites
TOTAL
JMM #1
Regular
1000 ml
1
1
1
2
825
1650
1000 ml
3
1
1
2
825
1650
125 ml
9
1
1
2
825
1650
JMM #2
Reg. + L.S.
1000 ml
1
1
1
1
3
450
1350
1000 ml
3
1
1
1
3
150
1200
125 ml
9
1
1
1
3
150
1050
JMM #3
Reg. + L.S. + T/S
1000 ml
1
1
1
2
2
6
225
1080
1000 ml
3
1
1
2
2
6
150
870
125 ml
9
1
1
2
2
6
75
660
TOTAL BOTTLE REQUIRED:
1000ml = 7800
125 ml = 3360
-------
Section No 7
Revision No 8
Date. September 10, 1990
Page 1 of 7
7. SAMPLE CUSTODY
Laboratory Notification and Sample Receipt
The EPA implementation contractor (ICF, Inc. ) was responsible for maintaining and daily
updating of the NPSIS data base (Appendix J). The Sample Receiving Clerk would log-in via modem
on a daily basis and print out the sampling schedule. This schedule was utilized by both the Sample
Receiving Clerk and the Program Manager to schedule the laboratory work schedules. Upon receipt
of the samples at the laboratory, Sample Receiving Clerk will inspect the sample, note the sample
condition on the Field Sample Tracking Form. The Sample Receiving Clerk will then via the NPSIS
data base notify ICF, Inc. as to the condition of the sample bottles, ice, and discrepancies between
the sample labels and the Field Sample Tracking Form. In addition to notifying ICF, Inc. the Sample
Receiving Clerk will notify the Program Manager who will then notify the Technical Monitor.
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 laboratory will contact the Technical
Monitor immediately.
The sample bottles and boxes will be returned to the EPA implementation contractor (ICF, Inc)
as soon as possible after the arrival of the samples. ICF will provide return shipping to their
headquarters facility in Fairfax, Virginia via a commercial shipper. The sample bottles and boxes will
be returned in bulk and not tracked individually.
Holding Times and Storage
Samples will be held in the dark and in the refrigerator at 4oC until extraction. The extracts will
be held in a freezer at -2Q°C. Only the aliquot needed for analysis (usually 1 ml) will be removed from
the freezer. Strict adherence to sample and extract maximum holding times (14 days) is required for
both the primary and secondary column analyses. All analyses should be completed as soon as
possible, but under extenuating circumstances, the maximum extract holding time may be extended to
28 days for GC/MS analyses only, if approved by the Technical Monitor.
' Sample status will be monitored daily by the Data Handling and Reporting Clerk and the
Program Manager. This monitoring will insure that the samples are extracted and analyzed within the
proper holding times. Items to be checked daily will include: 1) sample holding times to insure that
all extraction and extract holding times are met; 2) completeness of data packages to insure that data
will be reported in the required amount of time; and 3) status of all outstanding QC problems.
Refrigerator and Freezer temperatures are monitored daily, Monday through Friday of each
week by the Sample Control Person. The temperature at the beginning of the day is recorded on the
record sheet taped to the front of the unit. Acceptance limits for the refrigerator are 2 to 8oC.
Acceptance limits for the freezer are -30 to -10oC. A copy of this form may be found at the back of
this section (Figure 7.1).
-------
FIGURE 7.1
Section No. 7
Revision No. 8
Date: September 10. 1990
Page 2 of 7
TZAR:
tnri
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If
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lt«l Jo
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4
1
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7
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tl
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-------
Section No 7
Revision No 8
Date: September 10, 1990
Page 3 of 7
Sample Disposal
Due to the use of mercuric chloride as a preservative, all samples are potentially hazardous.
Water samples will be disposed of after the 14 day holding time has been exceeded. The water
samples for disposal are first aerated to remove any ether. The pH of the water sample is them
adjusted to pH 8-11. After adjusting the pH all water sample are combined in a 55 gallon teflon drum
and treated with a 12% solution of sodium borohydride. After treatment the water is analyzed by
mercury cold vapor EPA Method 7471), if the mercury concentration is less than 100 ppb the water is
dumped and the precipitate is packed as hazardous waste.
Sample extracts will be held until the Technical Monitor approves of their disposal. Extracts will
be stored in the dark at -20oC. Extracts will be lab packed and disposed of as a hazardous waste.
Sample Tracking
Sample tracking will be performed by the Program Manager. When samples arrive they will be
entered in to a Sample Tracking & Summary File. This file contains all of the information about
sampling and shipping needed for the final sample report. ICF will supply much of this information.
The laboratory will use the sample identification number described in Section 6 instead of
assigning the sample a laboratory tracking number. The primary means of tracking the samples will
be by extraction or analysis set number.
Each extraction set will be assigned a unique number and will be tracked as a set. The number
will be in the form #-#### where the first number is the Method number (1, 3 or 9) and the other
number is assigned consecutively. The Sample Tracking Form includes spaces to check for the
completion of primary, secondary, and confirmation analysis as well as all of the required QC checks.
A master list of all extraction sets will be kept to track the progress of all sets (Sample Tracking Form,
Figure 7.2 and 7.3). This list will be used for determining when sample disposal can take place.
The Data Handling and Reporting Clerk and the Program Manager will monitor the status of all
sample analyses by examination of the Sample Tracking Forms and the Extraction Set Tracking
Forms. The Data Handling and Reporting Clerk will check the status of the outstanding extractions
and analyses daily by talking to the analysts involved. Any potential problems will be brought to the
attention of the Program Manager, who will then contact the appropriate supervisors.
Copies of all of the tracking and reporting forms are included at the back of this section. This
includes not only the tracking forms but the data reporting forms (Figure 7.4 and 7.5).
-------
Section No 7
Revision No 8
Date1 September 10 1990
Page 4 of 7
FIGURE 7.2
METHOD 1
H«tfcod: 1
D«t« function it<(t«d:
dtr.ct.d ly:
SJUtfli T1ACI11C fO«JI
0»t* Iltnction Ca«pi«t»d: /_
Sp»k*d iy:
AA«iyi«d ly
»apl« ID
1
MILI
1
LCIA
LC«i
LCJC
|fO-
|»C- -l-l-
»0-
l^re- - 1 - 1 -
iro-
»C- -l-l-
fo-
rc- -i-i-
|»D-
rc- -i-i-
1 ro-
te- -i-i-
1 ro-
te- -i-i-
iro-
re- -i-i-
1 ro-
te- -i-i-
|to-
Itc- -i-i-
0«t*
!••»!•
Anilyitd
COB«lt«
ecus
l*c
-
Std
ac
Anil
-------
Section No 7
Revision No 8
Date September 10, 1990
Page 5 of 7
FIGURE 7.3
METHOD 3
lUthod.
0*t« «itr«ction stirttd
lltricttd iy:
Stxdard luati«r:
D«c« Cittaction Coapl«c*d
Spik«d iy:
Analycvd ty
>••«!• ID
NIL!
LCSA
LCI*
ra-
re- -i-i-
ro-
rc- -i-i-
FO-
rc- ii
1 ro-
te- t i
ro-
rc- i i
iro-
irc- - 1 - 1 -
I
iro-
rc- -i-i-
iro-
rc- -i-i-
|ro-
rc- -i-i-
|ro-
rc- -i-i-
iro-
ire- -i-i-
1
1
I
1
1
ecus
• •c J
J
std J
<3C
An.l
-------
Section No. 7
Revision No. 8
Date: September 10, 1990
Page 6 of 7
FIGURE 7.4
SAMPLE RESULTS FORM
METHOD 1
Extraction Set Number: 1 -_
Date Extracted: / /_
Analyzed By:
GC Run Number:
Calibration Run Number:
Sample ID:
Date Analyzed: / /
Analysis: PRIM / CONF / GCMS
Standard Stock Number:
Mix - Compound
Cone.
Mix - Compound
Cone.
B
C
C
B
A
C
B
A
A
A
C
A
A
A
A
A
A
B
B
A
A
A
A
- Alachlor
- Ametryn
- Atraton
- Atrazine
- Bromacil
- Butachlor
- Butylate
- Carboxin
- Chlorpropham
- Cycloate
- Diazinon (qual)
- Dichlorvos
- Diphenamid
- Disulfoton (qual)
- Disulfoton sulfone (qual)
- Disulfoton sulfoxide(qual)
- EPTC
- Ethoprop
- Fenamiphos
- Fenarimol
- Fluridone
- Hexazinone
- Merphos (qual)
B
C
A
A
B
A
C
A
A
A
A
A
A
C
A
B
A
C
B
B
A
A
A
- Methyl paraoxon
- Metolachlor
- Metribuzin
- Mevinphos
- MGK 264
- Molinate
- Napropamide
- Norflurazon
- Pebulate
- Proneton
- Promecryn
- Pronamide (qual)
- Propazine
- Simazine
- Simetryn
- Stirofos
- Tebuthiuron
- Terbacil
- Terbufos (qual)
- Terbutryn
- Triademefon
- Tricyclazole
- Vernolate
Surrogate Recovery:
Comments:
Internal Standard:
LCSA QC OK? Y/N
Surrogate OK?
Saaple Holding time OK?
Analysis Checked By:
f\, . -i. . j «.. .
LCSB QC OK? Y/N LCSC QC OK? Y/N
Y/N IS OK? T/N
Y/N Extract Holding time OR? Y/N
Need further analysis? T/N
-------
Section No. 7
Revision No. 8
Date: September 10, 1990
Page 7 of 7
FIGURE 7.5
Extraction Set Number: 3 -
Date Extracted: / /_
Analyzed By:
GC Run Number:
Calibration Run Number:
SAMPLE RESULTS FORM
METHOD 3
Sample ID:
Date Analyzed: / /
Analysis: PRIM / CONP / GCMS
Standard Stock Number:
Mix - Compound Cone.
A - Acifluorfen (qual)
A - Bentazon
B - Chloraaben (qual)
A - 2,4-D
A - 2,4-DB
A - Dalapon (qual)
A - DCPA Acid metabolites
A - Dicamba
A - 3,5-Dichlorobenzoic
Acid
Mix - Compound
A - Dichloroprop
B - Oinoseb
A - 5-Hydroxy Dicamba
B - 4-Nitrophenol (qual)
A - PCP
A - Pichloram
A - 2,4,5-T
A - 2,4,5-TP
Cone.
Surrogate Recovery:
Comments:
Internal Standard:
LCSA QC OK?
Surrogate OK?
Saaple Holding time OK?
Analysis Checked By:
QC Checked By:
Y/N
Y/N
Y/N
LCSB QC OK? Y/N
IS OK? Y/N
Extract Holding time OK? Y/N
Need further analysis? Y/N
If Y: Which analysis? Conf/GCMS
-------
Section No 8
Revision No 8
Date September 10, 1990
Page 1 of 5
8. CALIBRATION PROCEDURES AND FREQUENCY
Calibration Solutions
The EPA will furnish NPS standards at a nominal concentration of 1000 mg/L for Methods 1 and
3 in sealed glass ampules marked with individual batch numbers. Separate dilutions will be made
from these stocks for the calibration standards and the laboratory control standards (LCS). The
standard dilutions will initially be checked by analyzing the new LCS dilutions compared to the new
standard dilutions. If the results of the LCS show the expected recoveries (within control limits, see
Section 5, Initial Demonstration, Control Charts) then both dilutions must be correct (or both have the
same error). Each time new calibration standard dilutions are prepared they must be compared to the
existing calibration curve, and the observed concentration must agree within plus or minus 20% of the
expected concentration. If Method 1 cannot meet this criteria the Technical Monitor must be informed.
Records shall be kept in the stock standard notebook indicating how, when, and by whom the
dilutions were made. An example page from this book is included at the end of this section (Figure
8.1). Each standard dilution will be assigned a standard number. This number will be recorded with
all sample sets analyzed with this standard dilution to provide traceability for the standard used on
any given analytical run. This will be the method of tracking each new standard dilution and stock
solutions.
The Stock Standard numbers will be assigned as per the following code: NPS#-001-P##-1A;
where NPS# is the NPS method number, 001 is the batch number of the NPS standards given to ML
by the EPA, P## is the standards notebook page number which describes the preparation of the
standard mix preparation, 1 is the level of the dilution (0=low, 1=medium, and 2=high), and A refers
to which standard mix. The following example, NPS3-009-P12-3A, refers to NPS3-009 or the lot
number 9 NPS stock standard shipped from the EPA. NPS3-009-P12 is a cocktail prepared on page
12 of the standards notebook, and NPS3-009-P12-3A is a high level standard of mix A prepared from
cocktail NPS-009-P12.
The stock standard solutions are stored in 3 ml vials with teflon seals and stored in the dark at
-20oC. The stock standards will be replaced by new stock standards whenever a new shipment of
NPS standard is obtained from the EPA every three to four months. Diluted standards will be
prepared as needed, however they will be remade whenever a new NPS standard is obtained. Diluted
standards will be stored in 10 ml vials with teflon seals and stored in the dark at -20oC. Standards will
be kept in separate freezers from sample extracts.
Calibration Curve
Both Methods 1 and 3 will be calibrated using the Internal Standard Calibration Procedure,
Section 9.2 of the Methods. This procedure calls for a minimum of three standards. The lowest
calibration standard must be at 2 x MRL and the others should correspond to the range of
-------
Section No 8
Revision No 8
Date: September 10, 1990
Page 2 of 5
concentrations expected in the sample concentrates. One of the other standards must be at a level
equivalent to the 10XMRL After the standards are injected the relative response (RRa) for each
analyte to an internal standard will be calculated using the equation:
RRa = Aa/Ais
where: Aa = area of the analyte
Ais = area of the internal standard
A calibration curve will be generated, RRa versus analyte concentration in the sample in ug/l.
The working calibration curve must be verified each day by measuring one or more calibration
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.
Each time that new calibration standard dilutions are prepared they must be compared to the
existing calibration curve, and the observed concentration must agree within plus or minus 20% of the
expected concentration. If Method 1 cannot meet this criteria the Technical Monitor must be informed.
Because Montgomery can analyze the sample extract on both the primary and secondary
columns simultaneously, a complete standard curve can be generated on the confirmation column.
All calibration curves will be filed separately. The plots of each compound will be hardcopied
along with the response factor data. The sample data reports will be cross-referenced to the
calibration curve file.
GCMS Analysis
For GCMS confirmation the sample is compared to a standard prepared at the concentration
determined for the sample on either the primary or secondary column, whichever concentration is the
lower. If additional sample treatment is performed (blowdown, etc. ) the standard and sample must
both undergo the same treatment. The results of the GCMS confirmation are simply reported as the
presence or absence of the analyte, no quantitation.
The GCMS must be shown to be properly tuned during each daily shift prior to analysis. This
insures that the masses and abundances which the data system determines are accurate. The
compound used for tuning will be Decafluorotriphenylphosphine (DFTPP). The tuning criteria is
presented below. An example of the form used to show tuning is presented at the end of this section
(Figure 8.2)
-------
Section No 8
Revision No. 8
Date: September 10, 1990
Page 3 of 5
Mass m/e Abundance criteria
51 30 to 60% of mass 198
68 <2% of mass 69
70 <2% of mass 69
127 40 to 60% of mass 198
197 < 1 % of mass 198
198 BASE PEAK, 100% RELATIVE ABUNDANCE
199 5 TO 9% OF MASS 198
275 10 TO 30% OF MASS 198
365 1% OF MASS 198
441 Present but less than mass 443
442 >40% of mass 198
443 17 to 23% Of mass 442
-------
Section No 8
Revision No. 8
Date- September 10, 1990
Page 4 of 5
Notebook 014
Page 25
FIGURE 8.1
SPIKE
NPS 3-014-P25
A in Acetone
ROY 11/1/88
Stock Mix A un-deriv.
EPA COMPOUNDS
BATCH IN ACETONE PURITY
689 Dalapon 99 2%
699 3,5-DBA 99.8%
680 Dicamba 99.5%
681 2,4-DP 99.1%
683 2,4-D 99.9%
600 5-Hydroxy dicamba 99.5%
691 PCP 99.2%
693 Silvex 99.3%
682 2,4,5-T 99.5%
679 2,4-DB 99 4%
687 Bentazon 99.3%
692 Picloram 99.8%
703 DCPA 95 5%
686 Acifluorfen 99.9%
ORIG. CONC.
1 ,000 ug/ml
1,000 ug/ml
1 ,000 ug/ml
1 ,000 ug/ml
1 ,000 ug/ml
1 ,000 ug/ml
1 ,000 ug/ml
1,000 ug/ml
1 ,000 ug/ml
1 ,000 ug/ml
1,000 ug/ml
1 ,000 ug/ml
1,000 ug/ml
1 ,000 ug/ml
ACETONE DILUTION
WITH PURITY
CORRECTION
1.26ml - 25ml
0.15 ml - 25 ml
0.05 ml - 25 ml
0.126 ml - 25 ml
0.125 ml - 25 ml
0.05 ml -. 25 ml
0.05 ml - 25 ml
0.05 ml - 25 ml
0 50 ml - 25 ml
0.50 ml - 25 ml
0.126ml - 25ml
0.25 ml - 25 ml
0.052 ml -. 25 ml
0.05 ml - 25 ml
CONC.
STOCK
50 ug/ml
6.0 ug/ml
2.0 ug/ml
5.0 ug/ml
5.0 ug/ml
2.0 ug/ml
2.0 ug/ml
2.0 ug/ml
2.0 ug/ml
20 ug/ml
5.0 ug/ml
10 ug/ml
2.0 ug/ml
2.0 ug/ml
Notebook 014
Page 25
NPS 3-014-P25
B in Acetone
ROY 11/1/88
Stock Mix B un-deriv.
EPA COMPOUNDS
BATCH IN ACETONE PURITY
690 PNP 98.7%
688 Chloramben 91 .9%
684 Dmoseb 98.8%
ORIG. CONC.
1 ,000 ug/ml
1,000 ug/mi
1 ,000 ug/ml
ACETONE DILUTION
WITH PURITY
CORRECTION
1 .27 ml -. 25 ml
0.136ml - 25ml
0.632 ml _ 25 ml
CONC.
STOCK
50 ug/ml
5.0 ug/ml
25 ug/ml
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Section No. 8
Revision No. 8
Date- September 10, 1990
Page 5 of 5
FIGURE 8.2
GC/MS TUNING AND MA'SS CALIBRATION
Decafluorotriphenylphosphine
Case Number: Laboratory:
Inst. ID: FINN Sens. Date: 09/07/89
Lab ID: BN407SEP89A Call Date:
Data release authorized by: JAZ 09/07/89
Contract:
Sens. Time: 09:29:00
Analyst: RLE
M/E Ion Abundance Criteria Spec #581
51 30 to 60% of mass 198 30.51
68 less than 2% of mass 69 0.00
69 mass 69 relative abundance 37.17
70 less than 2% of mass 69 0.00
127 40 to 60% of mass 198 40.04
197 less than 1% of mass 198 0.00
198 base peak, 100% relative abundance 100.00
199 5 to 9% of mass 198 6.12
275 10 to 30% of mass 198 24.13
365 greater than 1% of mass 198 1.58
441 less than mass 443 11.30
442 greater than 40% of mass 198 69.53
443 17 to 23% Of mass 442 13.07
1 - value in parenthesis is % of mass 69
2 - value in parenthesis is % of mass 442
0.00)
0.00)
(18.80)
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Section No 9
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Date: September 10, 1990
Page 1 of 6
9. ANALYTICAL PROCEDURES
The following NPS methods will be used for samples analyzed for this contract. The detailed
methods are attached to this QAPjP as Appendix A.
METHOD 1
Method Summary
NPS Method 1 is entitled "Determination of Nitrogen- and Phosphorus- Containing Pesticides in
Ground Water by Gas Chromatography with a Nitrogen-Phosphorus Detector". Pesticides containing
nitrogen and/or phosphorus are extracted from water at neutral pH by methylene chloride and
analyzed by capillary column gas Chromatography equipped with a nitrogen-phosphorous detector.
This method is based on EPA Methods 622 and 633.
The method involves adding 100 grams of NaCI to one liter of sample (adjusted to pH 7) with 60
ml of methylene chloride. This extraction is performed three times and the extracts are combined.
The extract is dried over sodium sulfate. The extract solvent is exchanged to methyl-t-butyl ether
(MTBE). The 5 ml final extract is injected into a GC equipped with a 30 M DB-5 fused silica capillary
column and the compounds detected with a Nitrogen-Phosphorus detector. The confirmation column
will be a 30 M DB-1701 fused silica capillary column. Montgomery will use a single injection, dual
column-dual detector setup for automatic dual column confirmation.
Equipment
Primary GC: Varian 3500
Dual Capillary columns with 2 ECD
Model 8034 autosampler
Dual channel Nelson 760 series A/D
Backup GC: HP 5980
Dual capillary columns with 2 ECD
Model 7673A autosampler
Dual channel Nelson 760 series A/D
Primary Data System: Nelson model 4430 chromatographic workstation
5 dual channel 760 series instrument module A/D's
3 Thinkjet printers
Color monitor
HP 9000 series 300 computer with floating point hardware
20 MB hard disk
130 MB hard disk
Tape Drive for file archival
Backup Data systems: Varian Vista 401
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Section No. 9
Revision No 8
Date- September 10, 1990
Page 2 of 6
Primary GCMS for confirmations: Finnigan 4021
Capillary column
NOVA 4X Incos computer
70 MB disk drive
Dual terminal
Backup GCMS: Finnigan 5100
Capillary column
NOVA 4X Incos computer
70 MB disk drive
Dual terminals
Analysis Types
The following table is a list of the analysis types and frequency of analysis for Method 1.
Analysis Type Frequency
PRIMARY ANALYSIS
Instrument Control Standards 1/Day
Lab Control Standard (LCS) (one LCS per standard mix) 1/Set
Method Blank 1/Set
Calibration Standards 1/Day
Field Sample 1/Site
Backup Sample As Needed
Spiked Sample 10%
Day 0 time Storage Sample 10%
Day 14 Time Storage Sample 10%
Day 14 Time Storage Extract 10%
Performance Evaluation Samples As Requested
CONFIRMATIONAL COLUMN ANALYSIS
Field Sample As Needed
Calibration Standards As Needed
GCMS CONFIRMATION
Field Sample As Needed
. Calibration Standard As Needed
Maximum Number of Samples Per Set
Based on the required QC, the maximum number of field samples which could be analyzed per
sample set is 10. Note that each "sample set" is defined as all samples, blanks, spiked samples, LCS,
etc. , which are extracted at the same time.
Method Deviations
There are several deviations from the published method. If the QAPjP differs from the
procedures listed in the method, the QAPjP rules. Several of the known deviations are:
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Section No 9
Revision No 8
Date: September 10, 1990
Page 3 of 6
10.7.1.1 The method states that the spiking concentration should be 1 to 5 times the
background level or 15 times the EDL This QAPjP states (Section 5) that the
samples will be spiked at 2, 5 or 10 times the MRL
10.8 The method states that a method blank should not contain any peaks within
the retention time window of any analyte which is greater than or equal to one
half of the EDL for that analyte. This QAPJP changes the EDL to MRL in that
statement.
10.6.1 The method defines a sample set as all those samples extracted within a 24
hour period. For the purposes of this QAPjP a sample set has been defined
as all samples, blanks, spiked samples, LCS, etc. , which are extracted at the
same time by the same analyst.
General Because Mercuric chloride is used as a preservative in all of the field samples,
10 mg/l Mercuric chloride is to be added to all LCS, Blanks, etc. prepared in
the laboratory.
At this time Montgomery proposes no other method deviations from the published method. Any other
proposed deviations will have to be discussed with and approved by the Technical Monitor before use
for survey samples.
METHOD 3
Method Summary
NPS Method 3 is entitled "Determination of Chlorinated Acids in Ground Water By Gas
Chromatography with an Electron Capture Detector". Certain phenols and chlorophenoxy acid
herbicides are extracted from water at an acidic pH by ethyl ether. The extracts are esterified and
analyzed by capillary column gas Chromatography equipped with an electron capture detector. This
method is based on EPA Method 615.
The method involves adding 250 grams of NaCI to one liter of sample which is then adjusted to
pH 12 (as measured with pH paper) with 6N NaOH. The sample is periodically shaken for one hour to
hydrolyze derivatives. The sample is then extracted three times with 60 ml of methylene chloride.
This basic extract contains extraneous organic material and is therefore discarded. The pH is then
adjusted to pH 2 (as measured with pH paper) or less with H2SO4. The sample is then extracted with
120 ml of diethyl ether. The sample is then extracted two additional times with 60 ml of diethyl ether.
The ether extracts are combined and dried over sodium sulfate. The extract solvent is then
exchanged to Methyl-t-butyl ether (MTBE). This extract is then methylated using diazomethane. Silicic
acid is added to the extract to destroy any remaining diazomethane. The 5 ml final extract is injected
into a GC equipped with a 30 M DB-5 fused silica capillary column and the compounds detected with
a Electron Capture Detector. The confirmation column would be a 30 M DB-1701 fused silica capillary
column. Montgomery will use a single injection, dual column-dual detector setup for automatic dual
column confirmation. The method contains a Florisil cleanup procedure to be used on all sample
extracts, standards and controls.
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Section No 9
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Page 4 of 6
Equipment
Primary GC: HP 5890
Dual capillary columns with 2 ECD
Model 7673A autosampler
Dual channel Nelson 760 series A/D
Backup GC: Varian 3500
Dual capillary columns with 2 ECD
Model 8000 autosampler
Dual channel Nelson 760 series A/D
Primary Data System: Nelson model 4430 chromatographic workstation
5 dual channel 760 series instrument module A/D's
3 Thinkjet printers
Color monitor
HP 9000 series 300 computer with floating point hardware
20 MB hard disk
130 MB hard disk
Tape Drive for file archival
Backup Data systems: 2 Varian Vista 401 's
Primary GCMS for confirmations: Finnigan 4021
Capillary column
NOVA 4X Incos computer
70 MB disk drive
Dual terminal
Backup GCMS: Finnigan 5100
Capillary column
NOVA 4X Incos computer
70 MB disk drive
Dual terminals
Analysis Types
The following table is a list of the analysis types and frequency of analysis for Method 3.
Analysis Type Frequency
PRIMARY ANALYSIS
Instrument Control Standards 1/Day
Lab Control Standard (LCS) (one LCS per standard mix) 1/Set
Method Blank 1/Set
Methylation Blank 1/Batch
Methylation Standards 3/Batch
Florisil Elution Standard 1/Set
Calibration Standards 1/Day
Field Sample 1/Site
Backup Sample As Needed
Spiked Sample 10%
Day 0 time Storage Sample 10%
Day 14 Time Storage Sample 10%
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Section No. 9
Revision No 8
Date: September 10, 1990
Page 5 of 6
Day 14 Time Storage Extract
Performance Evaluation Samples
CONFIRMATIONS. COLUMN ANALYSIS
Field Sample
Calibration Standards
GCMS CONFIRMATION
Field Sample
Calibration Standard
10%
As Requested
As Needed
As Needed
As Needed
As Needed
Maximum Number of Samples Per Set
Based on the required QC, the maximum number of field samples which could be analyzed per
sample set is 9. Note that each "sample set" is defined as all samples, blanks, spiked samples, LCS,
etc. , which are extracted at the same time.
Method Deviations
There are several deviations from the published method. If the QAPJP differs from the
procedures listed in the method the QAPjP rules. Several of the known deviations are:
10.7.1.1 The method states that the spiking concentration should be 1 to 5 times the
background level or 15 times the EDL This QAPjP states (Section 5) that the
samples will be spiked at 2, 5 or 10 times the MRL
10.8 The method states that a method blank should not contain any peaks within
the retention time window of any analyte which is greater than or equal to one
half of the EDL for that analyte. This QAPjP changes the EDL to MRL in that
statement. This QAPjP also allows the compound dalapon to fail this
requirement due to its retention time.
10.6.1 The method defines a sample set as all those samples extracted within a 24
hour period. For the purposes of this QAPjP a sample set has been defined
as all samples, blanks, spiked samples, LCS, etc. , which are extracted at the
same time by the same analyst.
General Because Mercuric chloride is used as a preservative in all of the field samples,
10 mg/l Mercuric chloride is to be added to all LCS, Blanks, etc. prepared in
the laboratory.
General A Methylation Blank will be run with each batch of methylation reagent
prepared. This blank should meet the same criteria as the method blank.
General Three Methylation standards will be run when a new batch of methylation
reagent is prepared. These will be non-extracted standards at 5 times the
concentration of the LCS and diluted 5 times before analysis. The mean of
these must meet the same recovery criteria as the LCS. The Methylation
standards will show that the methylation step is working correctly and proper
derivitization is occurring. *
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Page 6 of 6
General A Florisil Elution Standard will be run whenever a new batch of florisil is
activated. This will be used to determine the recovery of the compounds from
the Florisil. A non-extracted standard will be placed on the Florisil column at
the sample concentration of the LCS. The recovery should fall in the same
range as the LCS.
General There is a portion on each analytical run for Method 3 which is excluded from
the integration program. That portion of the chromatogram often has several
peaks which result from the extraction solvents. The uniterated portion is from
4.5 min to about 10 min for the primary DB-5 column and 5.5 min to 11.0 min
on the confirmation DB 1701 column. Dalapon is eluted in this region and as
a result the Technical Monitor removed dalapon as a Method 3 quantitative
analyte.
At this time Montgomery proposes no other method deviations from the published method. Any other
proposed deviations will have to be discussed with and approved by the Technical Monitor before use
for survey samples.
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Section No 10
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Page 1 of 11
10. DATA REDUCTION, VALIDATION AND REPORTING
Data Reduction
All data for Methods 1 and 3 will be collected by the Nelson 4430 chromatographic workstation
through the Nelson 760 series A/D converters. Standards will be run at the beginning of the day. The
analytical run will be calibrated as described in Section 8 of this QAPjP. When samples are run, the
software will detect peaks and identify them based on absolute retention times compared to the
standards. The area of the peaks will be determined and the concentration calculated from the
calibration plots. All outputs of the Nelson software will be filed for the duration of the project, or until
the Technical Monitor approves of its disposal. Note: The Nelson data system has been verified by
performance on known samples over the last 2 years.
The rounding of numbers and significant figures is addressed in Appendix E. This Appendix
was taken from Chapter 7 of EPA publication EPA-600/4-79-019, "Handbook for Analytical Quality
Control in Water and Wastewater Laboratories."
Data Verification
The Nelson data will be reviewed and checked by the primary analyst. The primary analyst will
review all of the raw data and calculation and insure that the QC criteria was met. Following
completion of each analysis set, the analytical raw data, chromatograms, and QC summary sheets are
reviewed by a peer analyst. The peer analyst will insure that the data produced by the primary
analyst is complete and correct. The completed data and QC are then submitted to the NPS project
Data Handling and Reporting Clerk and the Program Manager to verify that all quality control
parameters fall within acceptance limits and to review the analytical data for calculation errors or
inconsistencies. The Data Handling and Reporting Clerk will then enter the data into the computer
data system.
The following items are to be checked for each sample set:
1) Is the instrument control standard's signal to noise ratio greater than the limit the
method specifies?
2) Is the instrument control standard's peak symmetry factor within the limits set by the
method?
3) Is the instrument control standard's peak geometry factor within the limits set by the
method?
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 requirement
(1 day)?
6) Is the date from sampling to extraction within the limits set by the survey (14 days)?
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Section No 10
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Page 2 of 11
7) Is the date from extraction to analysis within the limits set by the survey
requirements (14 days)?
8) Is the percent recovery of the surrogate within the limits set by the survey
requirements?
9) Is the internal standard area count within the limits set by the method requirements?
10) Is the concentration of a blank greater than or equal to one-half of the MRL?
11) Is the concentration of a field sample above the reporting limit?
a) If so, is there a confirmation analysis of the analyte?
b) Is the concentration of the confirmatory column within the limits set by the
survey requirements?
c) If so, is there a GCMS confirmation analysis?
12) Is the percent recovery of each analyte in the lab control standard within the limits
of the appropriate control chart?
13) Is the percent recovery of each analyte in the lab spike sample within the limits of
the appropriate control chart?
14) Is the percent recovery of each analyte in the performance evaluation sample within
the limits set by the survey requirements?
15) Ensure that the Nelson data computer is correctly identifying each compound within
the Retention Time Windows.
16) Is the calibration standard within 20% of the previous calibration curve, or was a
new calibration curve run?
17) Were refrigerator and freezer temperatures within acceptable limits during storage of
samples and extracts?
Data Validation
Validation of analytical data is dependent on insuring that key procedural steps which impact
data quality are followed and that all quality control parameters fall within documented acceptance
criteria. The following procedural steps must be adhered to for all of the NPS methods since
deviations can have a serious impact on data quality.
Any data not contained on a QC form will be contained in the analysts' notebook.
A solvent blank is performed on each new lot of solvent utilized for extractable
organic analyses. The solvent cannot be used if the levels of analytes exceed the
established method detection limits for these compounds.
After analysis of a high concentration sample, a reagent water blank or solvent
blank should be run until there is no longer a memory effect. A high concentration
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Section No 10
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Page 3 of 11
is defined as the concentration of the highest standard analyzed, unless data shows
that lower concentrations can carryover at a measurable level (one-half the MRL).
• Instrument performance must be checked daily and routine and special
maintenance must be documented in the instrument maintenance log (example in
Figure 10.1). The data from the Instrument QC Standard (Section 10.9 of the
methods) used to examine peak tailing, poor peak geometry, poor resolution,
missing peaks, and poor peak response are all indicative of instrumentation
problems which must be corrected before samples can be analyzed. A copy of the
Instrument QC Standard reporting form is included as Figure 10.2.
Samples must be warmed to room temperature before performing extraction or
analysis.
For GC analyses, a record of retention times obtained on spikes and standards for
each compound is maintained. The average retention time and variance for each
compound is calculated daily from each day's run of standards and spikes. The
retention times of individual samples must fall within 3 standard deviations of the
average retention time for each compound.
All laboratory analysts go through an orientation and training program to insure that they are
performing all of the required steps and quality control parameters for their analysis. Training is
provided by the appropriate senior analyst and verification of proper training is provided by not
allowing the analyst to work on samples until performing acceptably on EPA performance samples
which are provided to the analyst by the QA Officer as single blind samples. Once an analyst is
trained, his work is continually reviewed by his immediate supervisor and the Manager of Analytical
Services. His/her work is always sporadically reviewed by the QA Officer through review of
performance on periodic double blind check samples and routine monthly laboratory system audits.
Data Reporting
All data will be reported as sample sets. A sample set is defined as all samples, blanks, spiked
samples, LSC, etc. , which are extracted at the same time. When the sample set is completed, an
ACSII file in the required format will be produced. A copy of the required format is provided as
Appendix B. All data for a sample set are to be reported as a complete data set, including all QC and
confirmatory data no later than two months form the date of sample collection. The data files will be
sent to Christopher Frebis at the EPA in Cincinnati, Ohio. The files will be on IBM compatible 5. 25
inch floppy disks. Exceptions to the standard reporting procedure are:
Situations when results from confirmation columns do not agree with results from
primary columns within 25 percent are to be reported and discussed with the
Technical Monitor.
• Any DCPA on both columns must be reported regardless of differences in
quantitation between the primary and confirmation columns.
Confirmed positives for certain levels of certain analytes. The Rapid Reporting
Levels are listed in Tables 10.1 and 10.2. If an analyte listed in the two tables is
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Section No 10
Revision No 8
Date- September 10, 1990
Page 4 of 11
observed in the primary analyses at or above the RRL the following actions will be
instituted:
1) The appropriate confirmation analyses (GC/MS) should be performed as soon
as practical.
2) The laboratory will telephone the Technical Monitor as soon as confirmation is
completed.
3) The laboratory will immediately document the observed results in a letter to
the Technical Monitor.
Determining and Reporting the Presence of NPS Analytes Below the MRL
The following procedure has been established for determining and reporting the presence of an
NPS analyte below the MRL:
1) Only peaks with responses of between one-half the MRL and the MRL on the
primary column will be investigated. A response on the secondary column,
indicating the presence of the analyte, is also required for additional work.
2) a) The first occurrence of a peak meeting the requirements of (1) will be noted
and the peak retention time is verified. Retention time verification requires the
calculation of the mean retention time of the three compound standards. A
retention time window is then calculated as 3x the standard deviation + the
mean of the three standards. If the peak in question falls within this window
for both the primary and confirmation column, the presences of the
compound is reported to the technical monitor and GCMS confirmation is
performed.
b) For responses meeting the requirements of (1) and (2), the laboratory will
attempt low-resolution GCMS confirmation if the GC/MS supervisor feels it is
within the capability of the instrument. If the confirmation is not within the
capability of Montgomery, such extracts will be sent weekly, under iced
conditions by next-day air, to the appropriate referee laboratory having
high-resolution GC/MS capabilities. Copies of chromatograms and all
pertinent sample information must be sent along with the extracts including
extracts of the related Method Blank. It is preferred that extracts be in sealed
glass ampules, but other vials and teflon-faced closures are acceptable if they
provide a tight seal and do not contribute interferences to the extracts.
Volume level must be marked on the outside of the vial or ampule.
3) Whether the identification of the analyte is attempted at Montgomery or the referee
laboratory, only analytes positively confirmed by GC/MS will be reported beyond the
Technical Monitor for the Method and the Analytical Coordinators. No unconfirmed
data will be reported outside the NPS analytical system. Unsuccessful attempts at
confirmation will also be reported to the Technical Monitor.
4) Following either the successful GC/MS confirmation of two such responses for the
same analyte or two successive failures to confirm the analyte by GC/MS without
any prior successful GC/MS confirmation on any samples, discussions with OPP
personnel will take place before continuing low level work on that analyte.
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Section No 10
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Procedure for Determining the Identity of Non-NPS Analytes
It is expected that, over the course of the NPS program, numerous extraneous responses will be
evident on chromatograms form the various methods. The laboratory will be required to attempt
identification of peaks or responses on the primary column exhibiting the minimal criteria below.
1) If, upon initial analyses, the response of an extraneous peak on the primary column
is equal to or greater than the response of the nearest NPS analyte on that column
at 10 times MRL, an attempt must be made to identify that unknown peak or
response by GC/Ms. Full scan spectra and subsequent library search are expected
and must be followed by comparison of the spectra of the unknown compound with
those of an authentic standard of the suspected compound.
2) The work in (1) must be attempted by the laboratory on the first such occurrence of
such a peak and the results of the attempt reported to the Technical Monitor. If the
laboratory feels their instrument is not capable of the confirmatory work, they must
send both that extract and that of the related Method Blank to the referee laboratory
under iced conditions by next-day air. It is preferred that extracts be in sealed glass
ampules, but other vials and teflon-faced closures are acceptable if they provide a
tight seal and do not contribute interferences to the extracts. Volume level must be
marked on the outside of the vial or ampule.
Specific sample and analytical information must accompany each such extract
including: Sample ID number, weight of sample matrix contained in the ampule,
copies of chromatograms from the primary GC column, identification of the retention
time window for the unknown response(s) as defined by the last NPS analyte to
elute before the unknown peak or response and the first NPS analyte to elute
following the unknown response.
3) Whether the identification of the unknown compound is attempted at Montgomery or
the referee laboratory, only compounds positively confirmed by GC/MS will be
reported beyond the Technical Monitor and the Analytical Coordinators. No
unconfirmed data will be reported outside the NPS analytical system. Unsuccessful
attempts at identification will also be reported to the Technical Monitor.
4) Following either the successful confirmation of two such extraneous peaks proving
to be the same compound or two failures to identify a response with the same
retention time without a prior successful GC/MS confirmation on a sample,
discussions with OPP personnel will take place before continuation with
identification work on that particular compound.
Storage of Data
All laboratory data and information pertaining to NPS will be stored for the duration of the
program. This includes all refrigerator and freezer temperature logs, sample receipt forms, sample
tracking forms, extraction logs, GC run logs, instrument control standard forms, chromatograms,
sample results forms, GCMS tunes, control charts, instrument maintenance logs, reagents and
standard preparation records, calibration data, and data and records related to corrective actions.
Note that all of raw data will be stored in hardcopy form. All hardcopy data will be stored in files
labeled with the sample set number for the method. The GC calibration runs will be stored in
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Section No. 10
Revision No 8
Date: September 10, 1990
Page 6 of 11
separate folders. A master log will be kept of all samples with reference to the sample set it was
analyzed with. All hardcopy data and backup computer tapes will be stbred in locked file cabinets.
Only the Program Manager, Data Tracking and Reporting Clerk Operations Manager will have keys to
the data. The exact storage system is detailed in the "Montgomery Laboratories Standard Operating
Procedure for the Archival of the National Pesticide Survey (NPS) Data" which is included as
Appendix L
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Section No 10
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Date: September 10, 1990
Page 7 of 11
TABLE 10.1
METHOD 1 RAPID REPORTING LEVELS
Analyte
Rapid Reporting Level
Alachlor
Ametryn
Atrazine
Bromacil
Butylate
Carboxin
Diphenamid
Fenamiphos
Hexazinone
Metolachlor
Metribuzin
Propazine
Simazine
Tebuthiuron
Terbacil
40 ug/l
300
50
3,000
1,000
1,000
300
5.0
1,000
500
300
500
50
700
300
TABLE 10.2
METHOD 3 RAPID REPORTING LEVELS
Analyte
Rapid Reporting Level
Acifluorfen
Bentazon
2,4-D
Dalapon
Dicamba
Dinoseb
Pentachlorophenol
Picloram
2,4,5-T
2,4,5-TP
100 ug/l
90
100
300
300
7.0
300
700
350
70
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Section No. 10
Revision No. 8
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Page 8 of 11
FIGURE 10.1
MAINTENANCE ON GC
DATE
3/30/89
4/10/89
4/13/89
4/13/89
4/13/89
4/20/89
4/20/89
6/1/89
6/5/89
6/16/89
6/20/89
6/27/89
6/30/89
7/4/89
7/12/89
Replaced
7/18/89
7/21/89
7/25/89
8/4/89
8/21/89
MAINTENANCE
Septum Replaced - Injector A
Septum Replaced - Injector A
Septum Replaced - Injector A
Changed the glass insert on Injector A
Septum Replaced
Changed the glass insert on Injector A and Septum Replaced
Changed the glass insert on Injector A and Septum Replaced
New Columns were installed and all the peaks are sharp and change in R.T.
Change the septic and glass insert
New columns were installed
Septum Replaced
Changed the glass insert and Septum Replaced
New columns were installed
Septum Replaced
New columns were installed and changed the glass insert and Septum
Septum Replaced
New columns and charged the glass insert and Septum Replaced
Column inlet to detector was broken, the whole line which carries N2 into the
detector had to be replaced
New columns and change the glass insert and Septum Replaced
Septum Replaced
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Section No. 10
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Page 9 of 11
FIGURE 10.2
INSTRUMENT QC STANDARD
Method 1
Dace:
Analyst:
1
TEST ! ANALYTE
1
Sensitivity Vernolate
1 1
!
t
Chromatographic | Bromacil
Performance I
I
I
REQUIREMENTS
Detection of
S/N > 5
0.90 < PSF <
0.80 < PGF <
analyte
1.10
1.20
VALUE
Y or N
S/N .
PSF »
PGF -
QC MET?
Column
Performance
Prometon
Atrazine
Resolution > 0.7
NOTES:
1) PSF - Peak Symmetry Factor
PSF
0.5 X V(l/2)
2) PGF
Peak Gaussian Factor
1.83 X V(l/2)
PGF
Where v(l/2) is the width of the front
of the peak at half height assuming the
peak is split at its highest point and
V(l/2) is the peak vldth at half height.
Where W(l/2) is the peak vidth at half
height and tf(l/10) is the peak vidth at
tenth height.
3) Resolution is defined as:
t
R
W
4) Concentrations of the Instrument QC Standard:
Vernolate: 0.05 ug/ml
Bromacil: 0.5 ug/mi
Prometon: 0.30 ug/ml
Atrazine: 0.15 ug/«l
Where t is the difference in elution
tines between the two peaks and V is the
average peak width at the baseline.
-------
Section No. 10
Revision No. 8
Date: September 10. 1990
Page 10 of 11
FIGURE 10.2 (continued)
INSTRUMENT QC STANDARD
Method 3
Date:
Analyst:
I
TEST I ANALYTE
I
Sensitivity | Dinoseb
I
I
Chromatographic | 4-NP
Performance |
I
I
Column | 3,5-DCBA
Performance | 4-NP
REQUIREMENTS
Detection of analyte
S/N > 5
0.70 < PSF < 1.05
0.70 < PGF < 1.05
Resolution > 0.4
VALUE
Y or N
S/N .
PSF -
PGF »
R .
QC MET?
NOTES :
1) PSF - Peak Symmetry Factor
PSF
0.5 X U(l/2)
2)
PGF - Peak Gaussian Factor
1.83 X W(l/2)
PGF
Where v(l/2) is the vidth of the front
of the peak at half height assuming the
peak is split at its highest point and
V(l/2) is the peak vidth at half height.
Where W(l/2) is the peak vidth at half
height and V(l/10) is the peak vidth at
tenth height.
3) Resolution is defined as:
t
R >
V
A) Concentrations of the Instrument OC Standard:
Where t is the difference in elution
times betveen the tvo peaks and W is the
average peak vidth at the baseline.
Dinoseb: fi.004 ug/ml
4-Nitrophenol (4-NP): 1.6 uf/al
3,5-Dichlorobenzoic acid (3.5-OCBA): 0.6 ug/ml
-------
Section No 10
Revision No. 8
Date: September 10. 1990
Page 11 of 11
FIGURE 10.3
MONTGOMERY LABS
NFS STAFF ORGANIZATION
AND WORK FLOW
EPA Project Officer
Method 1 and 3
Robert Maxey
EPA Project Officer
Method 9
David Munch
Project Manager
Andrew Eaton, PhD
Laboratory Director
Quality Assurance
Rick Mealy
W. Braunstein
EPA Tech Monitor
Method 1 and 3
Robert Maxey
Program Manager
Julie Zalikowski
EPA Tech Monitor
Method 9
Melanie Zuicker
Data handling and
reporting
Beverly Gaskins
Method 1
Franklin
Constantino
Method 9
Whitney Moore
Extractions
Rick Hansen
Stan Kikkert
Suzette Urio
Glenn Okui
UsaLoring
Enrique Gomez
Francisco Gomez
Method 3
Roobik Yaghoubi
Sample
Receiving
Beveriy Gaskins
Bruce Havlik
-------
Section No. 11
Revision No. 8
Date: September 10, 1990
Page 1 of 8
11. INTERNAL QUALITY CONTROL CHECKS
This sections lists the type and frequency of quality control checks to be done in conjunction
with this project. Any time a QC sample analyte falls outside of the acceptance criteria an
"out-of-control" situation exists. A corrective form must be filled out stating the appropriate information
(Section 15). The Program Manager must be informed and no further samples run until the system is
shown to be back in control. Data produced while the system is out-of-control are unacceptable and
cannot be used for any purpose. It is imperative that the QC discussed here is followed and the QC
results thoroughly documented.
Summary Of QC Requirements
Table 11.1 is a tabular summary of the QC requirements, frequency, criteria and response to QC
failure. Most of these points are spelled out in more detail below.
Response To QC Failure
If any QC requirements for a sample set are not met no further analysis of that sample set will
be performed until the system is shown to be back in control. Extraction sets extracted after the set in
question also can not be analyzed until they are shown to be in control. No further extractions should
be performed until the extraction QC samples are shown to be in control by reanalysis of the first set
in question or any subsequent sample set which had already been extracted. If the QC samples for a
subsequent set are in control then the system is shown to be in control for that set only. It is
anticipated that up to 5 sample sets will be between extraction and analysis and therefore could be
subject to problems of this type.
Frequency of QC Samples
The following table lists the frequency of field and QC samples to be analyzed for Methods 1
and 3.
Analysis Type Frequency
PRIMARY ANALYSIS
Instrument Control Standards 1/Day
Lab Control Standard (LCS) (one LCS per standard mix) 1/Set
Method Blank 1/Set
Calibration Standards 1/Day
Field Sample 1/Site
Backup Sample As Needed
Spiked Sample 10%
Day 0 Time Storage Sample 1 o%
Day 14 Time Storage Sample 1 o%
Day 14 Time Storage Extract 10%
Performance Evaluation Samples As Requested
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Section No 11
Revision No 8
Date- September 10, 1990
Page 2 of 8
CONFIRMATIONS. COLUMN ANALYSIS
Field Sample
Calibration Standards
GCMS CONFIRMATION
Field Sample
Calibration Standard
As Needed
As Needed
As Needed
As Needed
Control Charts
1)
Control charts will be kept for all analytes and the surrogate. The initial control
charts will be established as in Section 5 of this QAPjP, the Initial Demonstration of
Capabilities.
2) Updating Control Charts: Following the establishment of the control chart, an LCS
will be 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 charts by
adding these 5 most recent recoveries to the 20 original points and then deleting
the first 5 of the original points. If the chart was generated using only 17 points,
only 2 of the first points are discarded. Dixon's test will be applied to the new data
to evaluate outliers. Accuracy and precision are recalculated and the chart
re-drawn. The newly drawn chart will then apply to all data in sample sets
subsequent to the last one used to update the chart.
3) Out-of-Control Situations: Sections 3(1) and 3(2) below refer to the recovery of
analytes in the laboratory control standards (LCS) which are part of each sample
set.
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 the
control limits.
b) The same analyte is outside the control limit twice in a row, even though
more than 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 the warning
limits but inside the control limits.
b) A run of 7 consecutive points above or below the mean.
c) A run of 7 points for an analyte in increasing or decreasing order.
An "alert" situation implies a trend toward an "out-of-control" situation. The
laboratory is required to evaluate the analytical system before proceeding. If
an "alert" or "out-of-control" situation occurs frequently, re-establishing control
charts may be required by the Technical Monitor before analytical work can
proceed.
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Section No 11
Revision No 8
Date. September 10, 1990
Page 3 of 8
Laboratory QC Requirements For Primary Analyses
1) Laboratory control standard mixes (LCS), which together contain all method
analytes, will be analyzed with each set of samples. Method 1 will have 3 LCS
mixes and Method 3 will have 2 LCS mixes. (See Table 5.2) Results of the LCSs are
to be reported as a normal sample.
2) A set of samples is defined as all samples, blanks, spiked samples, LCS, etc. ,
which are extracted at the same time.
3) The internal standard area checks detailed in the methods will be used as stated
(Section 10.5 of the method). However the control limits will be reassessed
following completion of the initial demonstration of capabilities. The internal
standard checks will be reported with each sample set.
4) The measurement system is to be evaluated whenever any analyte is observed in a
method blank, at a concentration greater than or equal to one-half the MRL (see
Section 5 of this QAPjP). Method blanks are analyzed with each sample set. A
corrective action form will be filed whenever this occurs.
5) The criteria for monitoring instrument control standards will be analyzed with each
sample set as stated in the method (Section 10.9 of the method). The results of this
ICS will be reported with each sample set. If the ICS does not meet the criteria set
forth in the method a corrective action form will be filed.
6) Surrogate recoveries will be required to be within plus or minus 30% of the mean
recovery determined for that surrogate during the initial demonstration of
capabilities.
7) Time storage samples must be extracted within plus or minus 4 days of the proper
date, and analyzed within 4 days of extraction. For example, non-stored time
storage samples must be spiked within the 14 day holding time for samples and
must be analyzed within 4 days of that extraction. A stored time storage sample
must be extracted by no sooner than 10 days and no later than 18 days after being
spiked, and must be analyzed within 4 days of being extracted.
8) The requirement for monitoring calibration standard responses will be followed as
written in the methods (Section 9.2.3 of the method).
. 9) Samples failing any QC criteria must be reanalyzed at the contractors expense.
10) Only qualitative analyses will be required for the following Method 1 compounds:
Diazinon, Disulfoton, Disulfoton sulfone, Disulfoton sulfoxide, Merphos, Pronamide,
and Terbufos. There are four qualitative analytes in Method 3; Chloramben,
4-Nitrophenol,Acifluorfen, and Dalpon. 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 new calibration standard dilutions are prepared they must be
compared to the existing calibration curve, and the observed concentration must
agree within plus or minus 20% of the expected concentration. For Method 1, the
Technical Monitor may change this requirement if the standards prove to be
unstable.
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Section No 11
Revision No 8
Date. September 10, 1990
Page 4 of 8
12) Any deviation from the analytical procedures or QC requirements must be approved
by the Technical Monitor and documented in writing.
Laboratory QC Requirements For Second Column Confirmation Analyses
1) Second column confirmation will be required for all compounds detected on the
primary column at a concentration above the MRL.
2) Quantitate by comparison to a calibration standard, which is within plus or minus
20% of the concentration of the sample determined using the primary column.
3) The concentration determined on the secondary column must agree within plus or
minus 25% of the result determined on the primary column.
4) If the concentration determined on the secondary column does not agree within the
limits stated above, the laboratory must confer with the Technical Monitor
concerning resolution of the discrepancy, if the results on both columns are above
the MRL
GC/MS Confirmation
1) GC/MS confirmation will be required for all compounds confirmed by second
column analysis.
2) 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 the lower.
3) If additional sample treatment is performed for GC/MS analysis (blowdown, etc. ),
the standard and sample must both undergo the same treatment.
4) Results of the GC/MS analysis are simply reported as the presence or absence of
the analyte.
5) The sample extract is to be shipped to the referee laboratory for high resolution
GC/MS analysis if confirmation of the analyte is not possible using quadrupole
GC/MS due to the concentration of the analyte, and if the concentration is equal to
or greater than one-half the lowest adverse health effect level for that analyte, or if
requested by the Technical Monitor.
Florisil Preparation and Storage
Florisil will be prepared as per section 7. 15 of Method 3. The Florisil will be stored in a
desiccator until use. Each batch of activated Florisil will be tested for recovery by spiking a known
concentration of standard onto the Florisil and determining the recovery. • The recovery should be
within LCS limits as determined in Section 5.
-------
Section No 11
Revision No. 8
Date- September 10, 1990
Page 5 of 8
Methylation QC Checks
Each batch of Diazomethane will be checked for background contaminants by the methylation
of a solvent blank. This solvent blank must meet the same criteria as the Method Blank.
Each batch of Diazomethane will also be tested for recovery by methylating three standards.
The recovery of these methylation standards must be the same as for the LCS.
Miscellaneous Other QC Notes
1) Additional samples will be collected at 10% of the samples sites for spiking at the
laboratory. The data from these spikes will be used to assess the recovery of the
analytes from a variety of matrices. These samples are to be spiked at analyte
concentrations equal to 2, 10 or 20 times the minimum reportable level for each
analyte. Only one of the standard mixes will be spiked per spike sample. Samples
collected for the analyte stability studies are to be spiked at 10 times the minimum
reportable level for each analyte.
2) Other "Out-of-Control" events:
a) Method Blank: If the method blank exhibits a peak within the retention
window of any analyte and is greater than or equal to one-half the MRL for
that analyte, an "out-of-control" situation has developed.
b) Performance-Evaluation Samples: If the laboratory fails on one of the PE
samples, an "out-of-control" situation is present.
3) Surrogate Monitoring
a) The surrogate recovery observed for all Field Samples, LSS and Method
Blanks must fall within plus or minus 30% of the mean recovery of the
surrogate on the control charts. The surrogate recovery for the LCS must fall
within the control limits established on the control chart.
b) A LCS in which the surrogate recovery has failed to meet the quality control
limits can be validated, if the following conditions are met:
i) The LCS meets all other required quality control elements.
ii) The surrogate recovery observed for the Method Blank associated with
that same sample set, meets the quality control limits determined using
the control chart for that surrogate.
c) A Method Blank in which the surrogate recovery has failed to meet the plus or
minus 30% criteria can be validated, if a Field Sample associated with that
same sample set, meets all of the quality control requirements for a Method
Blank.
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Section No 11
Revision No 8
Date: September 10/1990
Page 6 of 8
Internal QC Checks
The NPS Quality Assurance Officer will provide quarterly performance check samples to the
laboratory Program Manager. The Program Manager will submit the check sample as a blind to the
GC analyst. Results of the quarterly performance check samples will be submitted to the Technical
Monitor. The acceptance criteria for the performance evaluation results will be established by the NPS
Quality Assurance Officer. The criteria utilized is detailed in Section 12 of this QAPjP.
-------
Section No. 11
Revision No. 8
Date: September 10, 1990
Page 7 of 8
TABLE 11.1
QA CRITERIA/RESPONSE
Q*\ Ch«ck Frequency
TiB*
IGCHS eonf irBation) I
TIB* storaq* Saapl* TiB* Storaq*
Holdinq TIB* Sa*pl»
Holdinq TIB* SaBpl* Cltract
1
Criteria
1
dat*.
Sensitivity | |
1 1
M*thod 1
M*thod 3
M*thod 1 |
Method 1
M*thod Blank 1 par i*t
Lot
"Out-of-Control"
I sp*c i I i*d
I
o »o < psr < 1.10
o . 10 < par i 1.20
• tc.
0.70 < PGr c 1.05 - M*v coluBn n**d*d?
1
- «•• coluBn a**d*d?
'
0*t*rBiB* *h*th*r n*» lot >k*«ld B*
purchaa*d or curr*nt let diatill«d.
profal**.
-------
Section No. 11
Revision No. 8
Date: September 10, 1990
Page 8 of 8
TABLE 11.1 (continued)
QA CRITERIA/RESPONSE
1
1
| Standard
| Area count 5
| Bocov.ry
1
1
1
1
1
I Sa»pl--.
1 .
1
1
1
1
) Methylatiin nlank chock
1
1
| Chock standards
1
1
1 por day
Standard Stock
Each saoipl*
A s n«*d*d
As n*«d«H
ETA
Each a«t
Each batch of
Cacti Qu* r t«r
Recovery should be within LCS linits
Sana ai LCS
Sana as Hothod Blank
Sane as LCS
Sot by UPS 9A Offlcor
soo Section 12 QAP)P
1
••peat Kith lev calibration ltd.
rt*aiake stock. If thi< doe«« • t vort.
Many tinoi - check calibration |
Control*. |
1
tf not - tonti ti CPA for Hlqh Hoi |
further analyses perforned.
Or obtain new lot ot rlotit.ll.
Same as LCS I
saaie •» LCS
«rs
-------
Section No 12
Revision No 8
Date. September 10, 1990
Page 1 of 2
12. PERFORMANCE AND SYSTEM AUDITS
Performance and System Audits
The Quality Assurance Officer will review this QAPjP with all personnel associated with this
project to insure that they have read and understand it. Each analyst will sign a statement saying that
they have read and understand the QAPJP and will conduct the analyses in accordance with it. The
QA Officer or his assistant will conduct monthly formal system and data audits during which they will
track a single sample set throughout the system to insure that the QAPJP is being implemented, that
all systems are operating as expected and that data can be verified. These system audits will not be
announced to the analytical staff prior to their being carried out. The analytical staff is expected to
cooperate fully with the QA Officer during the audit. Any deficiencies will be reported immediately to
the Program Manager, the Laboratory Director, the analyst's supervisor, and the Technical Monitor. A
corrective action form will be filled out for each deficiency. The QC auditor verifies that the deficiency
has been corrected during the next audit The frequency of system audits will be increased if the
frequency of QC problems increase.
A system audit will consist of tracking at least one sample set through every step of analysis
and reporting. All steps in the system will be evaluated, even if the sample set did not require their
use. For example, the maintenance logs will be checked during each audit, even if they were not
needed for this sample set. The content of the system audit will include (but not be limited to):
Sample receipt and recordkeepmg
Extraction/Analysis set assignment
Extraction recordkeeping
Sample and extract holding times
LCS and spike assignment
Standards preparation and recordkeeping
Random calculation checks
Check analysis forms for completeness
Instrumental log books
Instrument calibration
Instrument Control Standards and recordkeeping
Method Blank Results
Laboratory Spike sample results
Internal Standard results and recordkeeping
Surrogate Standard results and recordkeeping
Compound confirmation by confirmation column
Compound confirmation by GCMS
Compound Retention time recordkeeping
Internal QC sample results
Florisil check results and recordkeeping
Corrective action reports and followup
Reports to Management
Timeliness of reporting QC problems
Other QC related matters
Performance evaluation (PE) samples will be sent quarterly to the laboratory by the NPS Quality
Assurance Officer (QAO). Each quarter the QAO will consult the Technical Monitors for Montgomery
-------
Section No. 12
Revision No. 8
Date. September 10, 1990
Page 2 of 2
Labs for recommendations on the analytes and on the analyte levels that should be included in the
samples. The samples will be prepared in acetonitrile, verified by the EPA referee lab and then
shipped to the lab in sealed glass ampules with instructions for analysis. Montgomery will be
expected to report their results to the Technical Monitors in memo form by the study deadline as well
as in the standard format required for all Survey samples. A minimum of three weeks will be allotted
for the analysis and reporting activities associated with participation in the PE study.
The results will be evaluated both qualitatively and quantitatively. Qualitative acceptance criteria
will be based on correct identification of all analytes known to be present in the PE sample and no
false positives.
Quantitative acceptance criteria for the samples will be based on a statistical comparison of
Montgomery's results with those achieved by the referee lab. Specifically, the referee lab will be
asked to report seven values for the PE standard, so that using equation 12-1, a 99% confidence
interval using the Student's "T" distribution can be constructed around the mean of the referee
laboratory's results.
Equation 12-1: x + (((t^ ^ (s))/(n))
where: x = mean
t = value from Students "T" distribution for an a of. 005 and (n-1)
degrees of freedom.
s = standard deviation
n = sample size
A confidence interval will likewise be constructed around the single value reported by Montgomery.
However, rather than requesting multiple analyses to generate a value for standard deviation (s), the
standard deviation will be taken from the control charts that were in effect at the time the PE was
analyzed. Since the control charts are kept in terms of percent recovery, the PE results will be
converted to a percent recovery based on the theoretical "true" value. The confidence interval based
on percent recovery will then be converted to a range of concentrations. Criteria for acceptable
performance will be that the confidence intervals generated from the referee analysis must overlap by
at least one point with the confidence intervals generated from Montgomery's analysis.
A report of Montgomery's performance will be prepared by the NPS QAO in conjunction with a
Survey statistician. Distribution of the report will include the Radian project manager, the Method 1
and 3 technical Monitor, the Survey Director, and the ODW and OPP QAOs.
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Section No. 13
Revision No 8
Date. September 10, 1990
Page 1 of 2
13. PREVENTIVE MAINTENANCE
GC Analyses
Routine maintenance will be performed on the GC in accordance with the following schedule:
Task Frequency
Clean detector Monthly or as required (Method 1,3)
Change detector collector As required by performance (Method 1)
Change detector bead As required by performance
Bake out GC column Daily or as required
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
Change GC gas filter traps Every six months or as needed
The laboratory also maintains a service contract with Varian and a service representative is usually on
the premises the same day the call for service is placed.
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
4) Injection port septa
5) Detector collector (Method 1)
6) Detector beads (Method 1)
GCMS Analyses
The following schedule of maintenance tasks and spare parts applies to the Finnigan 5100, the
Finnigan 4000, and the Hewlett Packard MSD.
Routine maintenance will be performed on the GCMS and purge and trap units in accordance
with the following schedule:
Task Frequency
Clean source Monthly or as required by performance
Clean quadrapoles Monthly or as required by performance
Bake out GC column Daily or as required
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
Change GC gas filter traps Every six months or as needed
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Section No 13
Revision No 8
Date September 10, 1990
Page 2 of 2
Both of the instruments are under maintenance and service contracts which include emergency
service and preventive maintenance. Usually the preventive maintenance checks include changing
pump oil, source cleaning, disk alignment checks and others.
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
4) Filaments (at least two of each)
5) Copper gaskets
6) Injection port septa
7) Vacuum pump oil
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Section No 14
Revision No 8
Date. September 10. 1990
Page 1 of 2
14. SPECIFIC PROCEDURES FOR ASSESSING MEASUREMENT SYSTEM DATA
The following formulas are used to calculate the data for the QC checks and for statistics related
to QC checks.
Percent Recovery (R,)
(100 * Determined Value of Spike or Standard)
Percent Recovery (Rj) = — --
True Value of Spike or Standard
Average Recovery (R)
Average Recovery (R) = Z Ri/n
Standard Deviation (Sr)
Standard Deviation (Sr) =
where n =
R'
( S R-R)
i = 1
rvT
number of measurements for each analyte
individual percent recovery value
average percent recovery value
Control Limits
The control limits for control charts are calculated as follows:
Upper Control Limit (UCL) = R + 3Sr
Upper Warning Limit (UWL) = R + 2Sr
Lower Warning Limit (LWL) = R - 2Sr
Lower Control Limit (LCL) = R - 3Sr
Peak Symmetry Factor (PSF)
PSF =
0. 5 * W(1/2)
Where w(l/2) = width of front of peak at half height assuming peak is split at its highest point and
W(l/2) is the peak width at half height (see Figure 7 of Method 1).
-------
Section No 14
Revision No 8
Date: September 10, 1990
Page 2 of 2
Peak Gaussian Factor (PGF)
1. 83* W(1/2)
PGF =
Where W(l/2) is the peak width at half height and W(1/10) is the peak width at tenth height (see
Figure 7 of Method 1).
Resolution (R)
t
R
W
Where t is the difference in elution times between the two peaks and W is the average peak width at
the baseline of the two peaks.
-------
Section No. 15
Revision No. 8
Date: September 10, 1990
Page 1 of 3
15. CORRECTIVE ACTION
Corrective action is required in response to an out-of-control event. Out-of-control events are
signalled whenever a quality control sample or parameter falls outside of acceptance limits. The
specific out-of-control events are listed in Section 11 of this QAPjP. Quality control parameters are
evaluated for their acceptability on a daily basis according to the established acceptance limits and
are monitored with control charts to detect trends in accuracy and variability which are indicative of a
shift in the methodology caused by analytical error. The required frequency and acceptance limits for
these parameters have been discussed in other sections of this plan. The exact corrective actions are
also discussed in Section 11 of this QAPjP.
Any time a QC problem occurs the QC Officer, Program Manager and Sample Tracking and
Reporting Clerk must be informed. If the problem is analytical, the supervisor of the section will also
be informed.
The analyst or sample receipt clerk is the first to be aware when a QC parameter falls outside of
the acceptance limits and has primary responsibility for notifying the QC Officer and the Program
Manager and attempting to solve the problem. The analyst must keep the QC Officer and the Project
Manager informed of specifically which QC par3meter(s) were unacceptable and what area the analyst
feels is the probable source of error. The method of notification will usually be by corrective action
form. The analyst and the Program Manager then map out a strategy of diagnostic tests to verify
whether this assessment is correct. It will be the responsibility of the Program Manager to insure that
the QA problem was solved prior to sample analysis proceeding. An example of a corrective action
form is included as Figure 15.1.
The corrective action form will include the following information:
Date of out-of-control event
Environmental samples impacted
Brief description of the non-conformance
Actions taken to resolve the non-conformance
Conclusion/Disposition of the data
The corrective action form will be submitted to the QA Officer, Data Handling and Reporting Clerk, and
the Program Manager. This information is included in the monthly progress reports submitted to the
Technical Monitor (see Section 16 of this QAPjP).
-------
Section No. 15
Revision No. 8
Date: September 10, 1990
Page 2 of 3
FIGURE 15.1
CORRECTIVE ACTION REPORT
General Information:
Analysis Date:
Extraction Date
Analyst:
Analysis:
Matrix:
Instrument ID:
Environmental samples impacted (Client/JMM ID):
Brief description of the non-conformance: /Columns 1.2 &. 31
Actions taken to resolve the non-conformance: iRefer to Column 4f
Conclusions/Disposition of the data: /Reftr \o Column si
Analyst
Croup Leader
QA Officer
Date:
Date:
Date:
-------
Section No. 15
Revision No. 8
Date: September 10, 1990
Page 3 of 3
FIGURE 15.1 (continued)
IDENTIFICATION AND RESOLUTION OF QA PROBLEM EVENTS
•rrtoa MCVMBTATIMI ••«•!•••
• •••tt t* (••••'lit* •••••*l**c ••*• tk* Aa*lftlr*l
••»••* I
FK.n.1
c»c..«.d l.c.to. (••••••t. C*»»l*t* • CTMICTITI tCTl««
•••••» ll«tl*f tk* *«f*ct*« • ••*!• IB*, tmi Ik* i**
!•*••«•«• lot*. •••<•. ••••li/l*»l*c* •• i*t* ••• • •j»*tM«ti !• tk* •••c**tt*t* {••ti»»t
••••ltl»ttr k>4 !•••*. •*C***ICT. •*lBt*a*ac* »•«. ••!••• 4»t» k*** •••• $•••><
it •••••If** I *t mmtf if tkl* c*tt*«t* tk* tt**kl«, ••••If •••• • ••(• t*
1 ' «t«»««««. •••••ct it«*4«c«>. tk* CUB !•«. •• C*n*ett«* kctl** ••••ft t*«*lc*4
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-------
Section No 16
Revision No. 8
Date: September 10, 1990
Page 1 of 2
16. QA REPORTS TO MANAGEMENT
Each day the Program Manager will meet with the Data Handling and Reporting Clerk to discuss
the status of all samples sets. This will include the status of shipping, extractions, analysis, QC, data
reporting and sample disposal. If needed, the Program Manager will discuss problems with the
Laboratory Director, the Quality Assurance Officer and other Laboratory Managers. These problems
could include QC problems, turnaround time problems, missing data problems, and personnel
problems. It is our intention that these daily meetings will be able to keep all of these problems under
control before they can seriously affect the overall project.
QA Audit Reports
The in-house QA audit reports will be written by the QA Officer or the Assistant. The audit
report will be forwarded to the Project Manager, the Program Manager, and the Technical Monitor via
the monthly report. The audit report will include the deficiencies noted as "major11 or "minor". Both the
major and minor issues should be resolved immediately in a formal response. The response will come
from the Program Manager and will be forwarded to the Project Manager, the QA Officer, and the
Technical Monitor.
Monthly Report Format
Six copies of the monthly report are to be provided within 15 calendar days after the end of the
period being reported. The copies are to be sent to the appropriate Technical Monitor. The report
will be prepared by the Program Manager. The report will be reviewed by the Project Manager and
the QC Officer and signed off by the Project Manager and Program Manager.
The report format should contain the following information for the report period:
Summary of progress
samples, received, analyses in progress
status of data processing for analyzed sets of samples
• Reports on standards
new dilutions and results of check before using
Summary list of bench-level corrective actions
Identification of problems about any phase of the project
Copies of representative and unusual chromatograms
Information requested by the Technical Monitor because of specific methodology or
problems encountered
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Section No 16
Revision No 8
Dale: September 10, 1990
Page 2 of 2
Changes in any personnel working on the project
Results of in-house system audits
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Appendix A
Revision No. 8
Date September 10, 1990
Page 1 of 94
APPENDIX A
NPS METHODS 1 AND 3
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Method 1. Determination of Nitrogen- and Phosphorus-Containing
Pesticides in Ground Water by Gas Chromatography with a
Nitrogen-Phosphorus Detector
1. SCOPE AND APPLICATION
1.1 This is a gas chromatographic (GC) method applicable to the
determination of certain nitrogen- and phosphorus-containing
pesticides in ground water. Analytes that can be determined
using this method are listed in Table 1.
1.2 This method has been validated in a single laboratory. Estimated
detection limits (EDLs) have been determined and are listed in
Table 2. Observed detection limits may vary between ground
waters, depending upon the nature of interferences in the sample
matrix and the specific instrumentation used.
1.3 This method is restricted to use by or under the supervision of
analysts experienced in the use of GC and in the interpretation
of gas chroraatograms. Each analyst must demonstrate the ability
to generate acceptable results with this method using the
procedure described in Section 10.2.
1.4 When this method is used to analyze unfamiliar samples for any or
all of the analytes above, analyte identifications must be
confirmed by at least one additional qualitative technique.
2. SUMMARY OF METHOD
2.1 A measured volume of sample of approximately 1 L is solvent
extracted with methylene chloride by mechanical shaking in a
separatory funnel or mechanical tumbling in a bottle. The
methylene chloride extract is isolated, dried and concentrated to
a volume of 5 mL after solvent substitution with methyl tert-
butyl ether (MTBE). Chromatographic conditions are described
which permit the separation and measurement of the analytes in
the extract by GC with a nitrogen-phosphorus detector (NPD).
2.2 An alternative manual liquid-liquid extraction method using
separatory funnels is also described.
3. DEFINITIONS
3.1 Artificial ground water --an aqueous matrix designed to mimic a
real ground water sample. The artificial ground water should be
reproducible for use by others.
3.2 Calibration standard --a known amount of a pure analyte,
dissolved in an organic solvent, analyzed under the same
procedures and conditions used to analyze sample extracts
containing that analyte.
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3.3 Estimated detection limit (EDL) -- the minimum concentration of
substance that can be measured and reported with confidence that
the analyte concentration is greater than zero as determined from
the analysis of a sample in a given matrix containing the
analyte. The EDL is equal to the level calculated by multiplying
the standard deviation of replicate measurements times the
students' t value appropriate for a 99 percent confidence level
and a standard deviation estimate with n-1 degrees of freedom or
the level of the compound in a sample yielding a peak in the
final extract with signal-to-noise ratio of approximately five,
whichever value is higher.
3.4 Instrument quality control (QC) standard --a MTBE solution
containing specified concentrations of specified analytes. The
instrument QC standard is analyzed each working day prior to the
analysis of sample extracts and calibration standards. The
performing laboratory uses this solution to demonstrate accep-
table instrument performance in the areas of sensitivity, column
performance, and chromatographic performance.
3.5 Internal standard --a pure compound added to a sample extract in
a known amount and used to calibrate concentration measurements
of other analytes that are sample components. The internal
standard must be a compound that is not a sample component.
3.6 Laboratory control standard --a solution of analytes prepared in
the laboratory by dissolving known amounts of pure analytes in a
known amount of reagent water. In this method, the laboratory
control standard is prepared by adding appropriate volumes of the
appropriate standard solution to reagent water.
3.7 Laboratory method blank --a portion of reagent water analyzed as
if it were a sample.
3.8 Performance evaluation sample -- A water-soluble solution of
method analytes distributed by the Quality Assurance Branch,
Environmental Monitoring and Support Laboratory, USEPA, Cincin-
nati, Ohio. A small measured volume of the solution is added to
a known volume of reagent water and analyzed using procedures
identical to those used for samples. Analyte true values are
unknown to the analyst.
3.9 Quality control check sample --a water soluble solution
containing known concentrations of analytes prepared by a
laboratory other than the laboratory performing the analysis.
The performing laboratory uses this solution to demonstrate that
it can obtain acceptable identifications and measurements with a
method. A small measured volume of the solution is added to a
known volume of reagent water and analyzed with procedures
identical to those used for samples. True values of analytes are
known by the analyst.
3.10 Stock standard solution --a concentrated solution containing a
certified standard that is a method analyte, or a concentrated
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solution of an analyte prepared in the.laboratory with an assayed
reference compound.
3.11 Surrogate standard -- a pure compound added to a sample in a
known amount and used to detect gross abnormalities during sample
preparation. The surrogate standard must be a compound that is
not a sample component.
4. INTERFERENCES
4.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware and other sample processing apparatus that
lead to discrete artifacts or elevated baselines in gas chromato-
graas. All reagents and apparatus must be routinely demonstrated
to be free from interferences under the conditions of the
analysis by running laboratory method blanks as described in
Section 10.8.
4.1.1 Glassware must be scrupulously cleaned.1 Clean all
glassware as soon as possible after use by thoroughly
rinsing with the last solvent used in it. Follow by
washing with hot water and detergent and thorough
rinsing with tap and reagent water. Drain dry, and heat
in an oven or muffle furnace at 400 °C for 1 hour. Do
not heat volumetric ware. Thermally stable materials
might not be eliminated by this treatment. Thorough
rinsing with acetone may be substituted for the heat-
ing. After drying and cooling, seal and store glassware
in a clean environment to prevent any accumulation of
dust or other contaminants. Store inverted or capped
with aluminum foil.
4.1.2 The use of high purity reagents and solvents helps to
minimize interference problems. Purification of
solvents by distillation in all-glass systems may be
required.
4.2 Interfering contamination may occur when a sample containing low
concentrations of analytes is analyzed immediately following a
sample containing relatively high concentrations of analytes.
Between-sample rinsing of the sample syringe and associated
equipment with MTBE can minimize sample cross contamination.
After analysis of a sample containing high concentrations of
analytes, one or more injections of MTBE should be made to ensure
that accurate values are obtained for the next sample.
4.3 Matrix interferences may be caused by contaminants that are
coextracted from the sample. The extent of matrix interferences
will vary considerably from source to source, depending upon the
ground water sampled. Cleanup of sample extracts may be
necessary. Positive identifications should be confirmed using
the confirmation column specified in Table 3.
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5.
5.1 The toxicity or carcinogenicity of each reagent used in this
method has not been precisely defined; however, each chemical
compound must be treated as a potential health hazard. From this
viewpoint, exposure to these chemicals must be reduced to the
lowest possible level by whatever means available. The
laboratory is responsible for maintaining a current awareness
file of OSHA regulations regarding the safe handling of the
chemicals specified in this method. A reference file of material
safety data sheets should also be made available to all personnel
involved in the chemical analysis. Additional references to
laboratory safety are available and have been identified2"'1 for
the information of the analyst.
6. APPARATUS AND EQUIPMENT (All specifications are suggested. Catalog
numbers are included for illustration only.)
6.1 SAMPLING EQUIPMENT
6.1.1 Grab sample bottle -- Borosilicate, 1-L volume with
graduations (Wheaton Media/Lab bottle 219820) , fitted
with screw caps lined with TFE-fluorocarbon. Protect
samples from light. The container must be washed and
dried as described in Section 4.1.1 before use to
minimize contamination. Cap liners are cut to fit from
sheets (Pierce Catalog No. 012736) and extracted with
methanol overnight prior to use.
6.2 GLASSWARE
6.2.1 Separatory funnel -- 2000-mL, with TFE-fluorocarbon
stopcock, ground glass or TFE-fluorocarbon stopper.
6.2.2 Tumbler bottle -- 1.7-L (Wheaton Roller Culture Vessel),
with TFE-fluorocarbon lined screw cap. Cap liners are
cut to fit from sheets (Pierce Catalog No. 012736) and
extracted with methanol overnight prior to use.
6.2.3 Flask, Erlenmeyer -- 500-mL.
6.2.4 Concentrator tube, Kuderna-Danish (K-D) -- 10- or 25-raL,
graduated (Kontes K-570050-2525 or K-570050-1025 or
equivalent) . Calibration must be checked at the volumes
employed in the test. Ground glass stoppers are used to
prevent evaporation of extracts.
6.2.5 Evaporative flask, K-D -- 500-mL (Kontes K-570001-0500
or equivalent) . Attach to concentrator tube with
springs.
6.2.6 Snyder column, K-D -- three-ball macro (Kontes
K-503000-0121 or equivalent).
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6.2.7 Snyder column, K-D - - two-ball micro (Kontes
K-569001-0219 or equivalent).
6.2.8 Vials -- glass, 5- to 10-mL capacity with TFE-fluoro-
carbon lined screw cap.
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 and
Mfg. Co., Alexandria, VA.).
6.5 Boiling stones -- Carborundum, #12 granules (Arthur H. Thomas Co.
#1590-033). Heat at 400°C for 30 min prior to use. Cool and
store in desiccator.
6.6 Water bath -- Heated, capable of temperature control (±2°C). The
bath should be used in a hood.
6.7 Balance -- Analytical, capable of accurately weighing to the
nearest 0.0001 g.
6.8 GAS CHROMATOGRAPH -- Analytical system complete with GC suitable
for use with capillary columns and all required accessories
including syringes, analytical columns, gases, detector and
stripchart recorder. A data system is recommended for measuring
peak areas.
6.8.1 Primary column -- 30 m long x 0.25 mm I.D. DB-5 bonded
fused silica column, 0.25 um film thickness (available
from J&W). Validation data presented in this method
were obtained using this column. Alternative columns
may be used in accordance with the provisions described
in Section 10.3.
6.8.2 Confirmation column -- 30 ra long x 0.25 mm I.D. DB-1701
bonded fused silica column, 0.25 um film thickness
(available from J&W).
6.8.3 Detector -- Nitrogen-phosphorus (NPD). A NPD was used
to generate the validation data presented in this
method. Alternative detectors, including a mass
spectrometer, may be used in accordance with the
provisions described in Section 10.3.
7. REAGENTS AND CONSUMABLE MATERIALS
7.1 Acetone, methylene chloride, MTBE -- Distilled-in-glass quality
or equivalent.
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7.2 Phosphate buffer, pH7 -- Prepare by mixing 29.6 raL 0.1 N HC1 and
50 mL 0.1 M dipotassium phosphate.
7.3 Sodium sulfate, granular, anhydrous, ACS grade -- Heat treat in a
shallow tray at 450°C for a minimum of 4 hours to remove inter-
fering organic substances.
7.4 Sodium chloride (NaCl), crystal, ACS grade -- Heat treat in a
shallow tray at 450°C for a minimum of 4 hours to remove inter-
fering organic substances.
7.5 o-Nitrotoluene -- >98% purity, for use as an internal standard
(available from Aldrich Chemical Co.).
7.6 Triphenyl phosphate (TPP) -- >98% purity, for use as internal
standard (available from Aldrich Chemical Co.).
7.7 1,3-Dimethyl-2-nitrobenzene -- >98% purity, for use as surrogate
standard (available from Aldrich Chemical Co.).
7.8 9-Nitroanthracene -- >98% purity, for use as a surrogate standard
(available from Aldrich Chemical Co.).
7.9 Reagent water -- Reagent water is defined as a water in which an
interferent is not observed at or above the EDL of any analyte.
Reagent water used to generate the validation data in this method
was distilled water obtained from the Magnetic Springs Water Co.,
Columbus, Ohio.
7.10 STOCK STANDARD SOLUTIONS (1.00 ug/uL) -- Stock standard solutions
may be purchased as certified solutions or prepared from pure
standard materials using the following procedure:
7.10.1 Prepare stock standard solutions by accurately weighing
approximately 0.0100 g of pure material. Dissolve the
material in MTBE and dilute to volume in a 10-mL volu-
metric flask. The stock solution for simazine should be
prepared in methanol. Larger volumes may be used at the
convenience of the analyst. If compound purity is
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.
7.10.2 Transfer the stock standard solutions into TFE-fluoro-
carbon-sealed screw cap vials. Store at room
temperature and protect from light.
7.10.3 Stock standard solutions should be replaced after two
months or sooner if comparison with laboratory control
standards indicates a problem.
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7.11 INTERNAL STANDARD SPIKING SOLUTION -- Prepare the internal
standard spiking solution by accurately weighing approximately
0.0150 g of pure o-nitrotoluene and 0.0500 g of pure TPP.
Dissolve the o-nitrotoluene and TPP in MTBE and dilute to volume
in a 100-mL volumetric flask. Transfer the internal standard
spiking solution to a TFE-fluorocarbon-sealed screw cap bottle
and store at room temperature. Addition of 50 uL of the internal
standard spiking solution to 5 mL of sample extract results in
final o-nitrotolene and TPP concentrations of 0.3 ug/mL and
5.0 ug/mL. Solution should be replaced when ongoing QC (Section
10) indicates a problem.
7.12 SURROGATE STANDARD SPIKING SOLUTION -- Prepare the surrogate
standard spiking solution by accurately weighing approximately
0.0250 g of pure 1,3-dimethyl-2-nitrobenzene and 0.0010 g of 9-
nitroanthracene . Dissolve the 1,3-dimethyl-2-nitrobenzene and 9-
nitroanthracene in MTBE and dilute to volume in a 100-mL volumet-
ric 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
1, 3-dimethyl-2-nitrobenzene and 9-nitroanthracene concentrations
in the sample of 12.5 ug/L and 0.5 ug/L, respectively. Assuming
quantitative surrogate recovery, addition of 50 uL of the
surrogate standard spiking solution to a sample results in
1, 3-dimethyl-2-nitrobenzene and 9-nitroanthracene concentrations
in the final extract of 2.5 ug/mL and 0.1 ug/mL, respectively.
Solution should be replaced when ongoing QC (Section 10) indi-
cates a problem.
7.13 INSTRUMENT QC STANDARD -- Prepare the instrument QC standard by
adding 5 uL of the vernolate stock solution, 0.5 mL of the
bromacil stock solution, 30 uL of the prometon stock solution,
15 uL of the atrazine stock solution, 1.0 mL of the surrogate
spiking solution, and 500 uL of the internal standard spiking
solution to a 100-raL volumetric flask. Dilute to volume with
MTBE and thoroughly mix the solution. Transfer the instrument QC
standard to a TFE-fluorocarbon-sealed screw cao bottle and store
at room temperature. Solution should be replaced when ongoing QC
(Section 10) indicates a problem.
SAMPLE COLLECTION. PRESERVATION. AND STORAGE
8.1 Grab samples must be collected in glass containers. Conventional
sampling practices5 should be followed; however, the bottle must
not be prerinsed with sample before collection.
8.2 SAMPLE PRESERVATION AND STORAGE
8.2.1 Add mercuric chloride to the sample bottle in amounts to
produce a concentration of 10 mg/L. Add 1 mL of a
solution containing 10 mg/mL of mercuric chloride in
reagent water to the sample bottle at the sampling site
or in the laboratory before shipping to the sampling
-------
sice. A major disadvantage of mercuric chloride is that
it is a highly toxic chemical; mercuric chloride must be
handled with caution, and samples containing mercuric
chloride must be disposed of. properly.
8.2.2 After the sample is collected in a bottle containing
preservative, seal the bottle and shake vigorously for
1 min.
8.2.3 The samples must be iced or refrigerated at 4°C away
from light from the time of collection until extraction.
Preservation study results presented in Table 11
indicate that most of the target analytes present in
samples are stable for 14 days when stored under these
conditions. However, analyte stability may be affected
by the matrix; therefore, the analyst should verify that
the preservation technique is applicable to the samples
under study.
8.3 EXTRACT STORAGE
8.3.1 Extracts should be stored at 4°C away from light.
Preservation study results given in Table 11 indicate
that most analytes are stable for 28 days; however, a
14-day maximum extract storage time is recommended. The
analyst should verify appropriate extract holding times
applicable to the samples under study.
9. CALIBRATION
9.1 Establish GC operating parameters equivalent to those indicated
in Table 3. The GC system must be calibrated using the internal
standard technique (Section 9.2).
9.2 INTERNAL STANDARD CALIBRATION PROCEDURE -- To use this approach,
the analyst must select one or more internal standards compatible
in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal
standard is not affected by method or matrix interferences. TPP
has been identified as a suitable internal standard.
9.2.1 Prepare calibration standards at a minimum of three
(suggested five) concentration levels for each analyte
of interest by adding volumes of one or more stock
standards to a volumetric flask. To each calibration
standard, add a known constant amount of one or more
internal standards, and dilute to volume with MTBE. One
of the calibration standards should be representative of
an analyte concentration near, but above, the EDL. The
other concentrations should correspond to the range of
concentrations expected in the sample concentrates, or
should define the working range of the detector.
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9.2.2 Inject 2 uL of each calibration standard and tabulate
the relative response for each analyte (RRa) to an
internal standard using the equation:
where: Aa = the peak area of the analyte, and
A1S = the peak area of the internal standard.
Generate a calibration curve of analyte relative
response, RRa, versus analyte concentration in the
sample in ug/L. Data presented in this report were
generated using TPP for quantification calculations.
9.2.3 The working calibration curve must be verified on each
working shift by the measurement of one or more calibra-
tion standards. If the response for any analyte varies
from the predicted response by more than ±20%, the test
must be repeated using a fresh calibration standard.
Alternatively, a new calibration curve must be prepared
for that analyte .
10. QUALITY CONTROL
10.1 Each laboratory using this method is required to operate a
quality control (QC) program. The minimum requirements of this
program consist of the following: an initial demonstration of
laboratory capability; the analysis of surrogate standards in
each and every sample as a continuing check on sample prepara-
tion; the monitoring of internal standard area counts or peak
heights in each and every sample as a continuing check on system
performance; the analysis of laboratory control standards, QC
samples, and performance evaluation (PE) samples as continuing
checks on laboratory performance; the analysis of spiked samples
as a continuing check on recovery performance; the analysis of
method blanks as a continuing check on contamination; and
frequent analysis of the instrument QC standard to assure
acceptable instrument performance.
10.2 INITIAL DEMONSTRATION OF CAPABILITY -- To establish the ability
to perform this method, the analyst must perform the following
operations .
10.2.1 Select a representative spike concentration (suggest
15 times the EDL) for each of the target 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 raL of the LC sample concentrate
to each of a minimum of four 1-L aliquots of reagent
water. A representative ground water may be used in
place of the reagent water, but one or more unspiked
-------
aliquots must be analyzed to determine background
levels, and the spike level must, at a. minimum, exceed
twice the background level for the- test to be valid.
Analyze the aliquots according to the method beginning
in Section 11.
10.2.3 Calculate the average percent recovery (R) and the
standard deviation of the percent recovery (SR), for the
results. Ground water background corrections must be
made before R and SR calculations are performed.
10.2.4 Table 2 and Tables 4-9 provide single laboratory
recovery and precision data obtained for the method
analytes from reagent and artificial ground waters,
respectively. Similar results from dosed reagent and
artificial ground waters should be expected by any
experienced laboratory. Compare results obtained in
Section 10.2.3 to the single laboratory recovery and
precision data. If the results are not comparable,
review potential problem areas and repeat the test.
Results are comparable if the calculated percent
relative standard deviation (RSD) does not exceed 2.6
times the single laboratory 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 chromatography,
the analyst is permitted to modify GC columns, GC conditions, or
detectors to improve the separations or lower the cost of
measurements. Each time such modifications to the method are
made, the analyst is required to repeat the procedure in Section
10.2.
10.4 ASSESSING SURROGATE RECOVERY
10.4.1 All samples and blanks must be fortified with the
surrogate spiking compound before extraction. A
surrogate standard determination must be performed on
all samples (including matrix spikes) and blanks.
10.4.2 Determine whether the measured surrogate concentration
(expressed as percent recovery) falls between 70 and 130
percent.
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.
10
-------
(3) Check instrument performance.
Reinject the laboratory method blank extract. If the
reanalysis fails the 70 to 130 percent recovery
criteria, the analytical system must be considered "out
of control." The problem must be identified and
corrected before continuing.
10.4.4 When the surrogate recovery for a sample is less than 70
percent or greater than 130 percent, the laboratory must
establish that the deviation is not due to laboratory
problems. The laboratory shall document deviations by
taking the following actions:
(1) Check calculations to make sure there are no
errors.
(2) Check internal standard and surrogate standard
spiking solutions for degradation, contamination,
or other obvious abnormalities.
(3) Check instrument performance.
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, quan-
11
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tify and report results. If the reinjected
sample extract aliquot displays an internal
standard peak area or height outside the
specified limits, but extract aliquots from
other samples continue to give the proper
area or height for the internal standard,
assume an error was made during addition of
the internal standard to the failed sample
extract. Repeat the analysis of that sample.
10.5.3.2 Multiple Occurrence -- If the internal
standard peak areas or heights for successive
samples fail the specified criteria (10.5.2),
check the instrument for proper performance.
After optimizing instrument performance,
check the calibration curve using a
calibration check standard (Section 9). If
the calibration 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, re-
analyze those sample extracts whose internal
standard failed the specified criteria. If
the internal standard peak areas or heights
now fall within the specified limits, report
the results. If the internal standard peak
areas or heights still fail to fall within
the specified limits or if the calibration
curve is no longer applicable, then generate
a new calibration curve (Section 9) and
reanalyze those sample extracts whose
internal standard failed the peak area or
height criteria.
10.6 ASSESSING LABORATORY PERFORMANCE
10.6.1 The laboratory must, on an ongoing basis, analyze at
least one laboratory control standard per sample set (a
sample set is all those samples extracted within a
24-hour period).
10.6.1.1 The spiking concentration in the laboratory
control standard should be 15 times the EDL.
10.6.1.2 Spike a 1-L aliquot of reagent water with a
laboratory control (LC) sample concentrate
(the volume of the spike should be kept to a
minimum so the solubility of the analytes of
interest in water will not be affected) and
analyze it to determine the concentration
after spiking (A) of each analyte. Calculate
each percent recovery (Ri) as (100xA)2/T,
12
-------
where T is the known true concentration of
the spike.
10.6.1.3 Compare the percent recovery (Rt) for each
analyte with established QC acceptance
criteria. QC criteria are established by
initially analyzing five laboratory control
standards and calculating the average percent
recovery (R) and the standard deviation of
the percent recovery (SR) using the following
equations:
n
R = R,/n
1=1
and
n n 2
1
SR = — —
n-1 i-1
n
where; n - number of measurements for each
analyte, and
Rt - individual percent recovery
value.
Calculate QC acceptance criteria as follows:
Upper Control Limit (UCL) = R + 3SR
Lower Control Limit (LCL) = R - 3SR
Alternatively, the data generated during the
initial demonstration of capability (Section
10.2) can be used to set the initial upper
and lower control limits.
Update the performance criteria on a con-
tinuous basis. After each five to ten new
recovery measurements (R^), 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.
13
-------
If the recovery of any such analyte falls
outside the designated range, the laboratory
performance for that analyte is judged to be
out of control, and the source of the problem
must be immediately identified and resolved
before continuing the analyses. The analyti-
cal result for that analyte in samples is
suspect and must be so labeled. All results
for that analyte in that sample set must also
be labeled suspect.
10.6.2 Each quarter, it is essential that the laboratory
analyze (if available) QC check standards. If the
criteria established by the U.S. Environmental Protec-
tion Agency (USEPA) and provided with the QC standards
are not met, corrective action needs to be taken and
documented.
10.6.3 The laboratory must analyze an unknown performance
evaluation sample (when available) at least once a year.
Results for each of the target analytes need to be
within acceptable limits established by USEPA.
10.7 ASSESSING ANALYTE RECOVERY
10.7.1 The laboratory must, on an ongoing basis, spike each of
the target analytes into ten percent of the samples.
10.7.1.1 The spiking concentration in the sample
should be one to five times the background
concentration, 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 (Rt) as 100(A-B)%/T,
where T is the known true concentration of
the spike.
10.7.1.3 Compare the percent recovery (Ri) for each
analyte with QC acceptance criteria esta-
blished from the analyses of laboratory
control standards.
14
-------
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
encountered with the dosed sample is judged
to be matrix-related, not system-related.
The result for that analyte in the unspiked
sample is labeled suspect/matrix to inform
the user that the results are suspect due to
matrix effects.
10.8 ASSESSING LABORATORY CONTAMINATION (METHOD BLANKS) -- Before
processing any samples, the analyst must demonstrate that all
glassware and reagent interferences are under control. This is
accomplished by the analysis of a laboratory method blank. A
laboratory method blank is a 1-L aliquot of reagent water
analyzed as if it was a sample. Each time a set of samples is
extracted or there is a change in reagents, a laboratory method
blank must be processed to assess laboratory contamination. If
the method blank exhibits a peak within the retention time window
of any analyte which is greater than or equal to one-half the EDL
for that analyte, determine the source of contamination before
processing samples and eliminate the interference problem.
10.9 ASSESSING INSTRUMENT PERFORMANCE (INSTRUMENT QC STANDARD) --
Instrument performance should be monitored on a daily basis by
analysis of the instrument QC standard. The instrument QC
standard contains compounds designed to indicate appropriate
instrument sensitivity, column performance and chromatographic
performance. Instrument QC standard components and performance
criteria are listed in Table 10. Inability to demonstrate
acceptable instrument performance indicates the need for
reevaluation of the GC-NPD system. A GC-NPD chromatogram
generated from the analysis of the instrument QC standard is
shown in Figure 1. The sensitivity requirements are set based on
the 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.
15
-------
11. PROCEDURE
11.1 AUTOMATED EXTRACTION METHOD -- Validation data presented in this
method were generated using the automated extraction procedure
with the mechanical tumbler.
11.1.1 Add preservative to samples not previously preserved
(Section 8.2). Mark the water meniscus on the side of
the sample bottle for later determination of sample
volume. Spike the sample with 50 uL of the surrogate
standard spiking solution. If the mechanical separatory
funnel shaker is used, pour the entire sample into a 2-L
separatory funnel. If the mechanical tumbler is used,
pour the entire sample into a tumbler bottle.
11.1.2 Adjust the sample to pH 7 by adding 50 mL of phosphate
buffer.
11.1.3 Add 100 g NaCl to the sample, seal, and shake to
dissolve salt.
11.1.4 Add 300 mL methylene chloride to the sample bottle,
seal, and shake 30 s to rinse the inner walls. Transfer
the solvent to the sample contained in the separatory
funnel or tumbler bottle, seal, and shake for 10 s,
venting periodically. Repeat shaking and venting until
pressure release is not observed during venting. Reseal
and place sample container in appropriate mechanical
mixing device (separatory funnel shaker or tumbler).
Shake or tumble the sample for 1 hour. Complete mixing
of the organic and aqueous phases should be observed at
least 2 min after starting the mixing device.
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. Collect the methylene chloride extract in a
500-mL Erlenmeyer flask containing approximately 5 g
anhydrous sodium sulfate. Swirl flask to dry extract;
allow flask to sit for 15 min.
11.1.6 Determine the original sample volume by refilling the
sample bottle to the mark and transferring the water to
a 1000-mL graduated cylinder. Record the sample volume
to the nearest 5 mL.
16
-------
11.2 MANUAL EXTRACTION METHOD -- Alternative.procedure.
11.2.1 Add preservative to samples not previously preserved
(Section 8.2). Mark the water meniscus on the side of
the sample bottle for later determination of sample
volume. Spike the sample with 50 uL of the surrogate
standard spiking solution. Pour the entire sample into
a 2-L separatory funnel.
11.2.2 Adjust the sample to pH 7 by adding 50 mL of phosphate
buffer.
11.2.3 Add 100 g NaCl to the sample, seal, and shake to
dissolve salt.
11.2.4 Add 60 mL methylene chloride to the sample bottle, seal,
and shake 30 s to rinse the inner walls. Transfer the
solvent to the separatory funnel and extract the sample
by vigorously shaking the funnel for 2 rain with periodic
venting to release excess pressure. Allow the organic
layer to separate from the water phase for a minimum of
10 min. If the emulsion interface between layers is
more than one third the volume of the solvent layer, the
analyst must employ mechanical techniques to complete
the phase separation. The optimum technique depends
upon the sample, but may include stirring, filtration of
the emulsion through glass wool, centrifugation, or
other physical methods. Collect the methylene chloride
extract in a 500-mL Erlenmeyer flask containing approxi-
mately 5 g anhydrous sodium sulfate.
11.2.5 Add a second 60-mL volume of methylene chloride to the
sample bottle and repeat the extraction procedure a
second time, combining the extracts in the Erlenmeyer
flask. Perform a third extraction in the same manner.
Swirl flask to dry extract; allow flask to sit for 15
min.
11.2.6 Determine the original sample volume by refilling the
sample bottle to the mark and transferring the water to
a 1000-raL graduated cylinder. Record the sample volume
to the nearest 5 mL.
11.3 EXTRACT CONCENTRATION
11.3.1 Assemble a K-D concentrator by attaching a 25-mL
concentrator tube to a 500-mL evaporative flask. Decant
the methylene chloride extract into the K-D concen-
trator. Rinse the remaining sodium sulfate with two
25-mL portions of methylene chloride and decant the
rinses into the K-D concentrator.
17
-------
11.3.2 Add 1 to 2 clean boiling stones to the evaporative flask
and attach a macro Snyder column. Prewet the Snyder
column by adding about 1 mL methylene chloride to the
top. Place the K-D apparatus on a hot water bath, 65 to
70°C, so that the concentrator tube is partially
immersed in the hot water, and the entire lower rounded
surface of the flask is bathed with hot vapor. Adjust
the vertical position of the apparatus and the water
temperature as required to complete the concentration in
15 to 20 min. At the proper rate of distillation the
balls of the column will actively chatter, but the
chambers will not flood. When the apparent volume of
liquid reaches 2 mL, remove the K-D apparatus and allow
it to drain and cool for at least 10 min.
11.3.3 Remove the Snyder column and rinse the flask and its
lower joint into the concentrator tube with 1 to 2 mL of
MTBE. Add 10 mL of MTBE and a fresh boiling stone.
Attach a micro-Snyder column to the concentrator tube
and prewet the column by adding about 0.5 mL of MTBE to
the top. Place the micro K-D apparatus on the water
bath so that the concentrator tube is partially immersed
in the hot water. Adjust the vertical position of the
apparatus and the water temperature as required to
complete concentration in 5 to 10 minutes. When the
apparent volume of liquid reaches 2 mL, remove the micro
K-D from the bath and allow it to drain and cool. Add
10 mL MTBE to the micro K-D and reconcentrate to 2 mL.
Remove the micro K-D from the bath and allow it to drain
and cool. Remove the micro Snyder column, and rinse the
walls of the concentrator tube while adjusting the
volume to 5.0 raL with MTBE.
11.3.4 Add 50 uL of the internal standard spiking solution to
the sample extract, seal, and shake to distribute the
internal standard. Transfer extract to an appropriate-
sized TFE-fluorocarbon-sealed screw-cap vial and store,
refrigerated at 4°C, until analysis by GC-NPD.
11.5 GAS CHROMATOGRAPHY
11.5.1 Table 3 summarizes the recommended operating conditions
for the gas chromatograph. Included in Table 3 are
retention times observed using this method. Examples of
the separations achieved using these conditions are
shown in Figures 2-6. Other GC columns, chromatographic
conditions, or detectors may be used if the requirements
of Section 10.3 are met.
11.5.2 Calibrate the system daily as described in Section 9.
The standards and extracts must be in MTBE.
11.5.3 Inject 2 uL of the sample extract. Record the resulting
peak size in area units.
i P
-------
11.5.4 The width of the retention time window used to make
identifications should be based upon measurements of
actual retention time variations of standards over the
course of a day. Three times the standard deviation of
a retention time can be used to calculate a suggested
window size for a compound. However, the experience of
the analyst should weigh heavily in the interpretation
of chromatograms.
11.5.5 If the response for the peak exceeds the working range
of the system, dilute the extract and reanalyze.
12. CALCULATIONS
12.1 Calculate analyte concentrations in the sample f-rom the relative
response for the analyte to the internal standard (RRa) using the
calibration curve described in Section 9.2.2.
12.2 For samples processed as part of a set where the laboratory
control standard recovery falls outside of the control limits in
Section 10, data for the affected analytes must be labeled as
suspect.
13. PRECISION AND ACCURACY
13.1 In a single laboratory, analyte recoveries from reagent water
were determined at five concentration levels. Results were used
to determine analyte EDLs and demonstrate method range. Analytes
were divided into five spiking groups (A-E) for recovery studies.
EDL data are given in Table 2. Method range data are given in
Tables 4-7.
13.2 In a single laboratory, analyte recoveries from two artificial
ground waters were determined at one concentration level.
Results were used to demonstrate applicability of the method to
different ground water matrices. Analytes were divided into five
spiking groups (A-E) for recovery studies. Analyte recoveries
from the two artificial matrices are given in Tables 8 and 9.
13.3 In a single laboratory, analyte recoveries from a ground water
preserved with mercuric chloride were determined 0, 14, and 28
days after sample preparation. Sample extracts were also
reanalyzed after they were stored for 28 days at -4°C and
protected from light. Results were used to predict expected
analyte stability in ground water samples and sample extracts.
Analytes were divided into five spiking groups (A-E) for recovery
studies. Analyte recoveries from the preserved, spiked ground
water samples and stored sample extracts are given in Table 11.
19
-------
REFERENCES
1. ASTM Annual Book of Standards, Part 11, Volume 11.02, D3694-82,
"Standard Practice for Preparation of Sample Containers and for
Preservation", American Society for Testing and Materials, Philadelphia,
PA, p. 86, 1986.
2. "Carcinogens - Working with Carcinogens," Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, Aug. 1977.
3. "OSHA Safety and Health Standards, General Industry," (29 CFR 1910),
Occupational Safety and Health Administration, OSHA 2206, (Revised,
January 1976).
4. "Safety in Academic Chemistry Laboratories," American Chemical Society
Publication, Committee on Chemical Safety, 3rd Edition, 1979.
5. ASTM Annual Book of Standards, Part 11, Volume 11.01, D3370-82, "Stan-
dard Practice for Sampling Water," American Society for Testing and
Materials, Philadelphia, PA, p. 130, 1986.
20
-------
TABLE 1. METHOD ANALYTES
Analyte
Alachlor
Ametryn
Aspon (c)
Atraton
Atrazine
Azinphos methyl (c)
Bolstar (c)
Bromacil
Butachlor
Butylate
Carboxin
Chlprpropham
Cycloate
Deraeton-0 (c)
Deraeton-S
Diazinon
Dichlofenthion (c)
Dichlorvos
Diphenamid
Disulfoton
Disulfoton sulfone
Disulfoton sulfoxide (c)
EPN (c)
EPTC
Ethion (c)
Ethoprop
Ethyl parathion (c)
Famphur ( c )
Fenamiphos
Fenarimol
Fenitrothion (c)
Fensulfothion (c)
Fenthion (c)
Fonofos (c)
Fluridone
Hexazinone
Malathion (c)
Merphos
Methyl paraoxon
Methyl parathion (c)
Metolachlor
Metribuzin
Mevinphos
CAS No. (a)
15972-60-8
834-12-8
3244-90-4
111-44-4
1912-24-9
86-50-0
35400-46-4
314-40-9
23184-66-9
2008-41-5
5234-68-5
101-21-3
1134-23-2
298-03-3
126-75-0
333-41-5
97-17-6
62-73-7
957-51-7
298-04-4
2497-06-5
2497-07-6
2104-64-5
759-94-4
563-12-2
13194-48-4
56-38-2
52-85-7
22224-92-6
60168-88-9
122-14-5
115-90-2
55-38-9
944-22-9
59756-60-4
51235-04-2
121-75-5
150-50-5
950-35-6
298-00-0
51218-45-2
21087-64-9
7786-34-7
Ident. Code (b)
D7
A7
D9
D5
B3
D14
E10
D8
CIO
D2
Cll
D4
A3
A2
C3
Cl
C5
El
Bll
A5
B12
Dl
E12
Bl
A10
B2
A9
A12
A10
E13
A8
D12
C8
B5
E14
D13
E8
B13
B6
B7
C7
C6
Al
21
-------
TABLE 1. METHOD ANALYTES (continued)
Analyte CAS No. (a) Ident. Code (b)
MGK 264
MGK 326 (c)
Molinate
Napropamide
Norflurazon
Pebulate
Phorate (c)
Phosmet (c)
Prometon (c)
Prometryn
Pronamide (c)
Propazine
Simazine
Simetryn
Stirofos
Tebuthiuron
Terbacil
Terbufos (c)
Terbutryn
Triademefon
Tricyclazole
Vernolate
113-48-4
136-45-8
2212-67-1
15299-99-7
27314-13-2
1114-71-2
298-02-2
732-11-6
1610-18-0
7287-19-6
23950-58-5
139-40-2
122-34-9
1014-70-6
22248-79-9
34014-18-1
5902-51-2
13071-79-9
886-50-0
43121-43-3
41814-78-2
1929-77-7
C9
A6
D3
E9
C12
E2
E4
Ell
A4
B8
D6
B4
E5
E7
D10
E3
E6
C4
B9
BIO
Dll
C2
(a) CAS No. = Chemical Abstracts Service registry number.
(b) Code used for identification of peaks in figures; letter indicates spiking
mixture which contained each analyte; IS = TPP internal standard;
SUR = 1,3-dimethyl-3-nitrobenzene surrogate standard.
(c) Compound shows aqueous instability.
22
-------
TABLE 2. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 1)
AND EDLs (a)
Spiking
Level,
Analyte ug/L
Alachlor
Ametryn
Aspon
Atraton
Atrazine
Azinphos methyl
Bolstar
Btomacil
Butachlor
Butylate
Carboxin
Chlorpropham
Cycloate
Deraeton-0
Demeton-S
Diazinon
Dichlofenthion
Dichlorvos
Diphenamid
Disulfoton
Disulfoton sulfone (h)
Disulfoton sulfoxide
EPN
EPTC
Ethion
Ethoprop
Ethyl parathion
Famphur
Fenamiphos
Fenarimol
Fenitrothion
Fensulfothion
Fenthion
Fluridone
Fonofos
Hexazinone
Malathion
Merphos
Methyl paraoxon
Methyl parathion
Metolachlor
Metribuzin
0.38
2.0
0.25
0.60
0.13
2.2
0.13
2.5
0.38
0.15
0.60
0.50
0.25
0.60
0.25
0.25
0.10
2.5
0.60
0.30
3.8
0.38
0.050
0.25
0.30
0,19
0.45
0.60
1.0
0.38
0.45
2.5
0.10
3.8
0.65
0.76
0.38
0.25
2.5
0.19
0.75
0.15
Arat in
Blank,
ug/L n(b)
ND (g)
KD
ND
ND
ND
ND
ND
0.00182
ND
ND
ND
0.0842
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.217
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
8
8
8
8
8
8
8
8
8
8
8
3
8
8
3
8
8
8
3
3
7
7
8
8
8
8
8
8
8
8
8
8
8
7
8
8
8
a
8
8
8
8
RCc)
119
100
131
120
101
110
107
113
99
93
101
124
101
35
90
94
100
78
84
100
94
110
92
87
96
108
80
94
91
92
119
111
82
78
95
127
98
101
100
96
94
114
S(d)
0.0468
0.0678
0.0288
0.0580
0.00505
0.158
0.0131
0.229
0.0407
0.0178
0.0584
0.0669
0.00725
0 0360
0 0129
0.0433
0.0145
0.0933
0.0273
0.00955
0.202
0.0261
0.0136
0.0266
0.0167
0.00699
0.0317
0.0273
0.0386
0.0681
0.0244
0.191
0.00570
0.882
0.0581
0.0508
0.0343
0,0135
0.101
0.00582
0.0619
0,00964
RSD(e)
10
3
9
8
4
6
9
8
11
13
10
11
3
17
6
18
14
5
5
3
6
6
29
12
7
3
9
5
4
19
5
7
7
30
9
5
9
5
4
3
9
6
EDL(f)
0.38
2.0
0.25
0.60
0.13
2.2
0.13
2.5
0.38
0.15
0.60
0.50
0.25
0.60
0.25
0.25
0.1
2.5
0.60
0.30
3.8
0.38
0.050
0.25
0.30
0.19
0.45
0.60
1.0
0.38
0.45
2.5
0.10
3.8
0.65
0.76
0.38
0.25
2.5
0.19
0.75
0.15
-------
TABLE 2. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 1)
AND EDLs (a) (continued)
Analyte
Mevinphos
MGK 264
MGK 326
Molinate
Napropamide
Norflurazon
Pebulate
Phorate
Phosmet
Prometon
Prometryn
Pron amide
Propazine
Simazine
Simetryn
Stirofos
Tebuthiuron
Terbacil
Terbufos
Terbutryn
Triademefon
Tricyclazole
Vernolate
Spiking
Level,
ug/L
5.
0.
0.
0.
0.
0.
0
0
0
0
0
0,
0
0
0
0
1
4
0
0
0
1
0
0
,50
15
,15
,25
.50
.13
.30
.75
.30
.19
.76
.13
.075
.25
.76
.3
.5
.50
.25
.65
.0
.13
Amt in
Blank,
ug/L
ND
ND
ND
ND
ND
0.0585
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.0132
ND
ND
ND
ND
ND
ND
ND
n(b)
8
8
8
8
8
8
8
8
8
7
8
3
8
a
8
8
8
8
a
8
8
8
8
R(c)
92
101
90
117
97
86
84
87
101
48
38
123
93
99
97
121
101
100
91
91
95
216
100
0.
0.
0,
0,
0,
0.
0,
0.
0
0.
0
0.
0
0,
0.
0,
0
0,
0
0
0
0
0,
S(d)
,291
.0628
.0121
.0202
,0230
.0326
.00719
.0279
.0485
.0129
.00801
.0934
.00455
.00467
.0118
,0604
.193
.186
.0190
.0102
.0311
.0716
.0184
RSD(e)
6
12
9
12
9
8
7
11
6
9
5
10
4
6
5
7
15
4
4
4
5
3
14
EDL(f)
5
o.
0
0.
0.
0.
0
0.
0,
0.
0,
0.
0.
0.
0,
0,
1.
4 .
0.
0,
0.
1.
0.
.0
.50
.15
,15
.25
50
.13
.30
.75
.30
.19
.76
.13
.075
.25
.76
,3
,5
,50
,25
,65
.0
.13
(a) Data corrected for amount detected in blank; average recovery of
1.3-diraethyl-2-nitrobenzene surrogate standard from eight spiked reagent water samples
was 931 (6.3 percent relative standard deviation).
(b) n = number of recovery data points.
(c) R = average percent recovery.
(d) S = standard deviation.
(e) RSD = percent relative standard deviation.
(f) EDL = estimated detection limit in sample in ug/L; calculated by multiplying standard
deviation (S) times the students' t value appropriate for a 991 confidence level and a
standard deviation estimate with n-1 degrees of freedom, or a level of compound in a
sample yielding a peak in the final extract with signal-to-noise ratio of approximately
5, whichever value is higher.
(g) ND = interference not detected in blank.
(h) EDL calculated using spiking level 2; analyte was not detected at spiking level 1.
-------
TABLE 3. PRIMARY AND CONFIRMATION ANALYSIS CONDITIONS
Analyte
Alachlor
Ajnetryn
Aspon
Atraton
Atrazine
Azinphos methyl
Bolstar
Bromacil
Butachlor
Butylate
Carboxin
Chlorpropham
Cycloate
Demeton-0
Demeton-S
Diazinon
Dichlofenthion
Dichlorvos
1, 3 -Dimethyl -2 -nitrobenzene
Diphenamid
Disulfoton
Disulfoton sulfone
Disulfoton sulfoxide
EPN
EPTC
Ethion
Ethoprop
Ethyl parathion
Famphur
Fenamiphos
Fenarimol
Fenitrothion
Fensulfothion
Fenthion
Fluridone
Fonofos
Hexazinone
Malathion
Merphos (f)
Methyl paraoxon
Methyl parathion
Metolachlor
Relative or
Primary (a,d)
0.765
0.766
0.797
0.665
0.676
1.066
0.958
0.792
0.882
0.478
0.910
0.619
0.608
0.576
0.663
0.707
0.733
0.352
(SUR1) 0.308
0.827
0.711
0.879
0.406
1.031
0.427
0.948
0.608
0.799
0.967
0.889
1.092
0.774
0.937
0.796
1.206
0.677
0.991
0.789
0.901
0.757
0.742
0.803
Absolute Retention Time
Confirmation (b,e)
34.10
34.52
35.10
29.97
31.23
49.58
(c)
40.00
39.00
18.47
42.05
(c)
29.67
24.88
(c)
(c)
32.28
15.35
(c)
37.97
30.90
42.42
(c)
47.42
16.57
42.65
26.42
37.13
46.38
41.00
50.02
36.22
44.42
35.90
59.07
30.25
47.80
36.12
39.28
34.10
35.10
35.70
-------
TABLE 3. PRIMARY AND CONFIRMATION ANALYSIS CONDITIONS (continued)
Analyte
Metribuzin
Mevinphos
MGK 264 (g)
MGK 326
Molinate
Napropamide
9-Nitroanthracene (SUR2)
o-Nitrotoluene (IS1)
Norf lurazon
Pebulate
Phorate
Phosmet
Prometon
Prometryn
Pronamide
Propazine
Simazine
Simetryn
Stirofos
Tebuthiuron
Terbacil
Terbufos
Terbutryn
Triaderaefon
Tricyclazole
Vernolate
Relative or
Primary (a,d)
0.749
0.479
0.824
0.695
0.546
0.890
0.872
0.255
0.977
0.498
0.625
1.027
0.672
0.769
0.697
0.681
0.670 •
0.760
0.878
0.535
0.719
0.693
0.783
0.811
0.899
0.488
Absolute Retention Time
Confirmation (b,e)
34.73
21.92
36.73
33.53
22.47
(c)
(c)
(c)
47.58
19.73
27.73
47.93
30.00
34.23
32.63
31.13
31.32
34.55
39.65
42.77
(c)
(c)
34.80
37.00
44.33
19.25
-------
TABLE 3. PRIMARY AND CONFIRMATION ANALYSIS CONDITIONS (continued)
FOOTNOTES
(a) Retention time relative to TPP internal standard (IS2) which elutes at
approximately 47 min.
(b) Absolute retention time in minutes.
(c) Data not available.
(d) Primary conditions:
Column: 30 m long x 0.25 ram I.D. DB-5 bonded fused silica column,
0.25 urn film thickness (J&W).
Injection volume: 2 uL splitless with 45 second delay
Carrier gas: He @ 30 era/sec linear velocity
Injector temp: 250"C
Detector temp: 300°C
Oven temp: Program from 60°C to 300°C at 4°C/min
Detector: NPD
(e) Confirmation conditions:
Column: 30 m long x 0.25 mm I.D. DB-1701 bonded fused silica
column, 0.25 um film thickness (J&W).
Injection volume: 2 uL splitless with 45 second delay
Carrier gas: He (3 30 cm/sec linear velocity
Injector temp: 250"C
Detector temp: 300°C
Oven temp: Program from 60 °C to 300 "C at 4°C/min
Detector: NPD
(f) Merphos is converted to S,S,S-tributyl phosphorotrithioate (DEF) in the hot
GC injection port; DEF is actually detected using these analyses conditions.
(g) MGK 264 gives two peaks; peak identified in this table used for
quantification.
-------
TABLE 4. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 2) (a)
Spiking Amt in
Level, Blank,
Analyte ug/L ug/L
Alachlor
Ametryn
Asp on
Atraton
Atrazine
Azinphos methyl
Bo Is tar
Bromacil
Butachlor
Butylate
Carboxin
Chlorpropham
Cycloate
Demeton-0
Demeton-S
Diazinon
Dichlofenthion
Dichlorvos
Diphenamid
Disulfoton
Disulfoton sulfone
Disulfoton sulfoxide
EPN
EPTC
Ethion
Ethoprop
Ethyl parathion
Famphur
Fenamiphos
Fenarimol
Fenitrothion
Fensulfothion
Fenthion
Fluridone
Fonofos
Hexazinone
Malathion
Merphos
Methyl paraoxon
Methyl parathion
Metolachlor
Metribuzin
1.9
10
1.3
3.0
0.63
11
0.63
13
3.8
0.76
6.0
2.5
1.3
3.0
2.5
2.5
1.0
13
3.0
1.5
3.8
1.9
0.25
1.3
1.5
1.0
2.3
3.0
5.0
1.9
2.3
13
1.0
19
3.3
3.8
1.9
1.3
13
1.0
7.5
1.5
ND (f)
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
n(b)
7
7
8
7
8
8
7
7
8
7
8
7
6
6
8
8
8
7
8
7
7
7
7
7
7
7
7
7
7
7
7
8
7
7
8
7
7
8
8
8
8
8
R(c)
95
44
98
85
93
96
85
86
96
92
102
96
80
67
114
115
101
87
93
85
94
110
96
83
75
94
87
90
88
97
87
95
97
107
98
90
94
91
99
92
93
101
S(d) RSD(e)
0.118
1.16
0.0774
0.158
0.0305
0.411
0.0282
0.494
0.149
0.112
0.274
0.178
0.114
0.365
0.141
0.183
0.0470
0.866
0.156
0.155
0.202
0.230
0.0206
0.104
0.381
0.0798
0.285
0.382
0.610
0.0956
0.280
0.833
0.0632
1.132
0.239
0.0968
0.110
0.0647
1.33
0.0912
0.287
0.0703
6
13
6
6
5
4
5
5
4
16
4
7
11
18
5
6
5
8
6
12
6
11
9
10
34
8
14
14
14
5
14
7
7
6
7
3
6
5
10
10
4
5
28
-------
TABLE 4. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 2) (a)
(continued)
Analyte
Mevinphos
MGK 264
MGK 326
Molinate
Napropamide
Norf lurazon
Pebulate
Phorate
Phosmet
Prometon
Prometryn
Pronamide
Propazine
Simazine
Simetryn
Stirofos
Tebuthiuron
Terbacil
Terbufos
Terbutryn
Triademefon
Tricyclazole
Vernolate
Spiking Amt in
Level, Blank,
ug/L ug/L
25
5.0
1.5
0.76
1.3
5.0
0.63
1.5
3.8
1.5
1.0
3.8
0.63
0.38
1.3
3.8
6.3
23
2.5
1.3
3.3
5.0
1.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
n(b)
7
8
7
7
7
8
7
7
7
7
7
7
8
7
7
7
7
7
8
7
8
7
8
R(c)
93
100
38
99
94
94
81
92
99
63
90
87
100
89
89
82
111
88
97
93
93
83
93
S(d) RSD(e)
3.20
0.220
0.108
0.0622
0.0569
0.232
0.0398
0.101
0.212
0.158
0.0441
0.203
0.0492
0.0221
0.0676
0.146
0.705
1.89
0.179
0.0530
0.180
0.157
0.0702
14
4
19
8
5
5
8
7
6
17
5
6
8
6
6
5
10
9
4
4
6
4
6
(a) Data corrected for amount detected in blank.
(b) n = number of recovery data points.
(c) R = average percent recovery.
(d) S = standard deviation.
(e) RSD = percent relative standard deviation.
(f) ND - interference not detected in blank.
-------
TABLE 5. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 3)
Spiking Amt in
Level, Blank,
Analyte ug/L ug/L n(b)
Alachlor
Ame tryn
Aspon
Atraton
Atrazine
Azinphos methyl
Bolstar
Bromacil
Butachlor
Butylate
Carboxin
Chlorpropham
Cycloate
Demeton-0
Demeton-S
Diazinon
Dichlofenthion
Dichlorvos
Diphenamid
Disulfoton
Disulfoton sulfone
Disulfoton sulfoxide
EPN
EPTC
Ethion
Ethoprop
Ethyl parathion
Famphur
Fenamiphos
Fenarimol
Fenitrothion
Fensulfothion
Fenthion
Fluridone
Fonofos
Hexazinone
Malathion
Merphos
Methyl paraoxon
Methyl parathion
Metolachlor
Metribuzin
3.8
20
2.5
6.0
1.3
22
1.3
25
3.8
1.5
6.0
5.0
2.5
6.0
2.5
2.5
1.0
25
6.0
3.0
7.5
3.8
0.50
2.5
3.0
1.9
4.5
6.0
10
3.8
4.5
25
1.0
38
6.5
7.6
3.8
2.5
25
1.9
7.5
1.5
ND (f)
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
8
8
8
8
8
8
8
8
8
6
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
R(c)
95
91
97
91
92
94
77
91
96
97
102
93
89
78
114
115
101
97
93
89
98
87
90
85
91
103
92
93
90
99
94
97
96
87
89
90
84
96
98
97
93
101
S(d) RSD(e)
0.390
1.91
0.147
0.640
0.103
1.87
0.0900
2.26
0.149
0.321
0.274
0.554
0.234
0.523
0.141
0.183
0.0470
1.39
0.501
0.287
0.722
0.441
0.0201
0.230
0.262
0.0889
0.392
0.510
0.840
0.185
0.407
1.17
0.0680
3.28
0.534
0.532
0.189
0.201
2.47
0.177
0.287
0.0703
11
11
6
12
9
9
9
10
4
22
4
12
10
11
5
6
5
6
9
11
10
13
4
11
10
5
9
9
9
5
10
5
7
10
9
8
6
8
10
10
4
5
-------
TABLE 5. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 3)
(continued)
Analyte
Mevinphos
MGK 264
MGK 326
Molinate
Napropamide
Norflurazon
Pebulate
Phorate
Phosmet
Prometon
Prometryn
Pronamide
Propazine
Simazine
Simetryn
Stirofos
Tebuthiuron
Terbacil
Terbufos
Terbutryn
Triademefon
Tricyclazole
Vernolate
Spiking Amt in
Level, Blank,
ug/L ug/L
50
5.0
1.5
1.5
2.5
5.0
1.3
3.0
7.5
3.0
1.9
7.6
1.3
0.75
2.5
7.6
13
45
5.0
2.5
6.5
10
1.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
n(b)
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
R(c)
95
100
87
98
101
94
94
78
86
78
93
91
92
100
99
98
84
97
97
94
93
86
93
S(d) RSD(e)
5.04
0.220
0.146
0.259
0.143
0.232
0.104
0.173
0.310
0.267
0.165
0.776
0.103
0.0508
0.131
0.459
1.15
2.41
0.179
0.214
0.539
0.675
0.0673
11
4
11
18
6
5
9
7
5
11
9
11
9
7
5
6
11
6
4
9
9
8
6
(a) Data corrected for amount detected in blank.
(b) n = number of recovery data points.
(c) R = average percent recovery.
(d) S - standard deviation.
(e) RSD - percent relative standard deviation.
(f) ND = interference not detected in blank.
31
-------
TABLE 6. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 4)
Spiking Amt in
Level, Blank',
Analyte ug/L ug/L
Alachlor
Ametryn
Aspon
Atraton
Atrazine
Azinphos methyl
Bolstar
Broraacil
Butachlor
Butylate
Carboxin
Chlorpropham
Cycloate
Demeton-0
Demeton-S
Diazinon
Dichlofenthion
Dichlorvos
Diphenamid
Disulfoton
Disulfoton sulfone
Disulfoton sulfoxide
EPN
EPTC
Ethion
Ethoprop
Ethyl parathion
Faraphur
Fenamiphos
Fenarimol
Fenitrothion
Fensulfothion
Fenthion
Fluridone
Fonofos
Hexazinone
Malathion
Merphos
Methyl paraoxon
Methyl parathion
Metolachlor
Metribuzin
9.4
50
6.3
15
3.1
56
3.1
63
9.4
3.8
15
13
6.3
15
6.3
6.3
2.5
63
15
7.5
19
9.4
1.3
6.3
7.5
4.8
11
15
25
9.4
11
63
2.5
94
16
19
9.4
6.3
63
4.8
19
3.8
ND (f)
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
n(b)
8
8
8
8
7
8
7
8
7
8
7
8
8
8
7
7
7
8
7
8
7
8
8
7
8
7
8
8
8
8
8
8
6
7
7
8
7
7
7
7
7
7
R(c)
95
104
90
94
96
105
100
94
96
62
89
92
104
93
96
97
91
92
93
105
91
104
99
90
106
88
108
103
102
84
107
101
88
88
89
96
105
95
90
89
98
97
S(d)
0.531
5.69
0.356
0.727
0.158
4.53
0.400
3.00
0.261
0.341
0.598
0.668
0.724
1.89
0.394
0.350
0.124
5.31
0.607
0.879
0.669
1.48
0.162
0.414
0.762
0.457
1.22
1.54
2.60
1.09
1.18
5.26
8.47
8.47
1.18
1.22
1.16
0.350
2.93
0.232
1.28
0.259
RSD(e)
6
11
6
5
5
8
13
5
3
15
4
6
11
14
7
6
5
9
4
11
4
15
13
7
10
11
10
10
10
14
10
8
10
10
8
7
12
6
5
5
7
7
-------
TABLE 6. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 4)
(continued)
Analyte
Mevinphos
MGK 264
MGK 326
Molinate
Napropamide
Norflurazon
Pebulate
Phorate
Phosmet
Prometon
Prometryn
Pronamide
Propazine
Simazine
Simetryn
Stirofos
Tebuthiuron
Terbacil
Terbufos
Terbutryn
Triademefon
Tricyclazole
Vernolate
Spiking
Level ,
ug/L
125
13
3.8
3.8
6.3
13
3.1
7.5
19
7.5
4.8
19
3.1
1.9
6.3
19
31
113
13
6.3
16
25
3.1
Amt in
Blank,
ug/L
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.582
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
n(b)
8
7
8
8
8
7
8
7
8
8
7
8
7
8
8
8
8
8
7
7
7
8
7
R(c)
99
95
107
101
84
85
86
91
103
102
129
96
92
86
84
91
82
82
94
91
92
92
83
S(d)
12.0
0.275
0.379
0.478
0.479
0.772
0.288
1.02
2.46
0.815
0.277
1.12
0.194
0.115
0.435
1.12
1.34
11.8
0.544
0.221
0.595
1.61
0.124
RSD(e)
10
2
9
12
9
7
11
15
13
11
4
6
7
7
8
7
5
13
4
4
4
7
5
(a) Data corrected for amount detected in blank.
(b) n = number of recovery data points.
(c) R - average percent recovery.
(d) S - standard deviation.
(e) RSD - percent relative standard deviation.
(f) ND - interference not detected in blank.
33
-------
TABLE 7. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 5)
Spiking Amt in
Level, Blank,
Analyte ug/L ug/L n(b)
Alachlor
Ametryn
Aspon
Atraton
Atrazine
Azinphos methyl
Bolstar
Broraacil
Butachlor
Butylate
Carboxin
Chlorpropham
Cycloate
Demeton-0
Demeton-S
Diazinon
Dichlofenthion
Dichlorvos
Diphenamid
Disulfoton
Disulfoton sulfone
Disulfoton sulfoxide
EPN
EPTC
Ethion
Ethoprop
Ethyl parathion
Famphur
Fenamiphos
Fenarimol
Fenitrothion
Fensulfothion
Fenthion
Fluridone
Fonofos
Hexazinone
Malathion
Merphos
Methyl paraoxon
Methyl parathion
Metolachlor
Metribuzin
38
200
25
60
13
224
13
250
38
15
60
50
25
60
25
25
10
250
60
30
75
38
5.0
25
30
19
45
60
100
38
45
250
10
375
65
76
38
25
250
19
75
15
ND (f)
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
8
8
8
8
8
7
8
8
8
8
8
8
8
7
8
8
8
8
8
8
8
8
8
8
7
8
7
7
8
8
7
8
8
8
8
8
8
8
8
8
8
8
R(c)
94
98
93
90
93
64
95
93
90
78
96
93
100
85
86
88
90
96
94
99
88
84
95
88
94
93
93
99
98
104
96
91
89
98
94
93
97
101
92
94
92
91
S(d) RSD(e)
2.35
5.81
1.31
3.76
0.548
23.3
0.878
16.5
2.25
1.01
5.38
3.21
0.725
3.29
1.51
2.07
0.458
14.5
2.01
0.851
2.09
3.02
0.307
1.46
2.00
0.973
2.64
1.75
2.72
3.18
1.87
9.31
0.726
28.8
2.92
3.52
2.28
1.00
10.0
0.712
4.44
0.885
7
3
6
7
5
16
7
7
7
9
9
7
3
6
7
9
5
6
4
3
3
9
6
7
7
5
6
3
3
8
4
4
8
8
5
5
6
4
4
4
6
7
34
-------
TABLE 7. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 5)
(continued)
Analyte
Mevinphos
MGK 264
MGK 326
Molinate
Naproparaide
Norf lurazon
Pebulate
Phorate
Phosmet
Prometon
Prometryn
Pronamide
Propazine
Simazine
Simetryn
Stirofos
Tebuthiuron
Terbacil
Terbufos
Terbutryn
Triademefon
Tricyclazole
Vernolate
Spiking Amt in
Level, Blank,
ug/L ug/L
500
50
15
15
25
50
13
30
75
30
19
76
16
8
25
76
125
450
50
25
65
100
13
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
n(b)
8
8
7
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
R(c)
89
90
94
87
102
101
88
95
98
85
94
93
73
101
103
97
87
101
93
93
98
89
88
S(d) RSD(e)
17.9
3.76
0.794
0.912
2.39
3.75
1.04
3.35
4.64
1.68
0.710
4.70
0.604
0.594
1.99
6.64
10.5
34.7
3.79
0.909
2.41
4.18
0.797
4
8
6
7
9
7
9
12
6
7
4
7
5
8
8
9
10
8
8
4
4
5
7
(a) Data corrected for amount detected in blank.
(b) n = number of recovery data points.
(c) R = average percent recovery.
(d) S - standard deviation.
(e) RSD = percent relative standard deviation.
(f) ND - interference not detected in blank.
-------
TABLE 8. RECOVERY OF ANALYTES FROM HARD ARTIFICIAL GROUND WATER
(SPIKING LEVEL 3) (a)
Spiking Amt in
Level, Blank,
Analyte ug/L ug/L
Alachlor
Ametryn
Aspon
Atraton
Atrazine
Azinphos methyl
Bolstar
Bromacil
Butachlor
Butylate
Carboxin
Chlorpropham
Cycloate
Demeton-0
Demeton-S
Diazinon
Dichlofenthion
Dichlorvos
Diphenamid
Disulfoton
Disulfoton sulfone
Disulfoton sulfoxide
EPN
EPTC
Ethion
Ethoprop
Ethyl parathion
Famphur
Fenamiphos
Fenarimol
Fenitrothion
Fensulfothion
Fenthion
Fluridone
Fonofos
Hexazinone
Malathion
Merphos
Methyl paraoxon
Methyl parathion
Metolachlor
3.8
20
2.5
6.0
1.3
22
1.3
25
3.8
1.5
6.0
5.0
2.5
6.0
2.5
2.5
1.0
25
6.0
3.0
7.5
3.8
0.50
2.5
3.0
1.9
4.5
6.0
10
3.8
4.5
25
1.0
38
6.5
7.6
3.8
2.5
25
1.9
7.5
ND (f)
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
n(b)
7
7
7
7
8
7
8
7
8
7
8
7
7
7
8
8
8
8
8
7
8
7
8
8
7
8
7
7
7
8
7
7
8
8
8
7
8
8
8
8
8
R(c)
82
102
81
84
89
87
85
81
93
36
98
82
97
82
81
83
78
86
88
107
92
88
87
83
97
91
97
91.
87
89
96
87
79
91
87
86
88
90
97
89
92
S(d) RSD(e)
0.214
2.30
0.261
0.382
0.0787
2.27
0.0778
1.29
0.551
0.115
0.771
0.353
0.345
0.334
0.151
0.210
0.0647
1.57
0.279
0.352
0.324
0.835
0.0365
0.132
0.165
0.134
0.282
0.254
0.509
0.244
0.247
2.36
0.380
4.10
0.292
0.436
0.268
0.0972
1.87
0.0915
0.765
7
11
13
8
7
12
7
6
16
21
13
9
14
7
7
10
8
7
5
11
5
25
8
6
6
8
6
5
6
7
6
11
5
12
5
7
8
4
8
5
11
-------
TABLE 8. RECOVERY OF ANALYTES FROM HARD ARTIFICIAL GROUND WATER
(SPIKING LEVEL 3) (a) (continued)
Analyte
Metribuzin
Mevinphos
MGK 264
MGK 326
Molinate
Napropamide
Norflurazon
Pebulate
Phorace
Phosmet
Prometon
Prometryn
Pronamide
Propazine
Simazine
Simetryn
Stirofos
Tebuthiuron
Terbacil
Terbufos
Terbutryn
Triademefon
Tricyclazole
Vernolate
Spiking Amt in
Level, Blank,
ug/L ug/L
1.5
50
5.0
1.5
1.5
2.5
5.0
1.3
3.0
7.5
3.0
1.9
7.6
1.3
0.75
2.5
7.6
13
45
5.0
2.5
6.5
10
1.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
n(b)
8
7
8
7
7
8
8
8
8
8
7
8
7
8
8
8
7
8
8
8
8
8
7
8
R(c)
99
93
91
96
83
89
101
80
90
90
89
91
84
89
86
88
84
85
86
80
91
94
90
79
S(d) RSD(e)
0.142
2.76
0.555
0.0561
0.116
0.126
0.781
0.0774
0.188
0.449
0.154
0.149
0.502
0.0787
0.0393
0.119
0.469
1.28
2.20
0.301
0.197
0.301
0.586
0.108
10
6
12
4
9
6
15
7
7
7
6
9
8
7
6
5
7
12
6
8
9
5
7
11
(a) Corrected for amount found in blank; artificial ground water was Absopure
Nature Artesian Spring Water Obtained from the Absopure Water Company in
Plymouth, Michigan.
(b) n - number of data points.
(c) R - average percent recovery.
(d) S - standard deviation.
(e) RSD - percent relative standard deviation.
(f) ND = interference not detected in blank.
-------
TABLE 9. RECOVERY OF ANALYTES FROM ORGANIC-CONTAMINATED ARTIFICIAL
GROUND WATER (SPIKING LEVEL 3) (a)
Spiking Amc in
Level, Blank,
Analyte ug/L ug/L
Alachlor
Ametryn
Aspon
Atraton
Atrazine
Azinphos methyl
Bolstar
Bromacil
Butachlor
Butylate
Carboxin
Chlorpropham
Cycloate
Demeton-0
Demeton-S
Diazinon
Dichlofenthion
Dichlorvos
Diphenamid
Disulfoton
Disulfoton sulfone
Disulfoton sulfoxide
EPN
EPTC
Ethion
Ethoprop
Ethyl parathion
Famphur
Fenamiphos
Fenarimol
Fenitrothion
Fensulfothion
Fenthion
Fluridone
Fonofos
Hexazinone
Malathion
Merphos
Methyl paraoxon
Methyl parathion
Metolachlor
3.8
20
2.5
6.0
1.3
22
1.3
25
3.8
1.5
6.0
5.0
2.5
6.0
2.5
2.5
1.0
25
6.0
3.0
7.5
3.8
0.50
2.5
3.0
1.9
4.5
6.0
10
3.8
4.5
25
1.0
38
6.5
7.6
3.8
2.5
25
1.9
7.5
ND (f)
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
n(b)
8
8
8
8
7
8
8
8
8
8
8
8
8
8
8
8
8
8
7
8
7
7
8
7
8
7
8
8
8
8
8
8
8
8
7
8
8
7
7
7
8
R(c)
90
96
93
91
92
97
106
88
84
83
87
93
93
61
83
84
75
106
93
95
96
54
110
86
97
79
90
94
89
89
92
94
81
86
88
95
109
92
94
85
84
S(d) RSD(e)
0.312
0.710
0.302
0.486
0.0621
2.79
0.221
2.09
0.204
0.110
0.292
0.428
0.0815
0.255
0.130
0.0813
0.0747
3.99
0.253
0.135
0.242
0.733
0.0735
0.105
0.130
0.0582
0.112
0.160
0.247
0.236
0.131
2.86
0.0509
3.58
0.253
0.665
0.605
0.0845
0.973
0.0596
0.322
9
4
13
9
5
13
16
9
6
9
6
9
3
7
6
4
10
15
5
5
3
36
13
5
4
4
3
3
3
7
3
12
6
11
4
9
15
4
4
4
5
-------
TABLE 9. RECOVERY OF ANALYTES FROM ORGANIC-CONTAMINATED ARTIFICIAL
GROUND WATER (SPIKING LEVEL 3) (a) (continued)
Analyte
Metribuzin
Mevinphos
MGK 264
MGK 326
Molinate
Napropamide
Norflurazon
Pebulate
Phorate
Phosmet
Prometon
Prometryn
Pronamide
Propazine
S imaz ine
Simetryn
Stirofos
Tebuthiuron
Terbacil
Terbufos
Terbutryn
Triaderaefon
Tricyclazole
Vernolate
Spiking Amt in.
Level, Blank,
ug/L ug/L
1.5
50
5.0
1.5
1.5
2.5
5.0
1.3
3.0
7.5
3.0
1.9
7.6
1.3
0.75
2.5
7.6
13
45
5.0
2.5
6.5
10
1.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
n(b)
8
8
8
8
8
8
8
8
8
8
8
7
8
7
8
8
8
8
8
8
7
7
8
8
R(c)
86
92
83
76
89
104
87
98
106
107
63
93
92
92
103
103
95
98
102
77
92
95
90
81
S(d) RSD(e)
0.0627
1.86
0.270
0.507
0.131
0.434
0.219
0.197
0.509
0.958
0.0947
0.0740
0.617
0.0621
0.110
0.354
0.699
1.64
5.35
0.353
0.0971
0.285
1.05
0.0299
5
4
7
4
10
17
5
15
16
12
3
4
9
5
14
14
10
13
12
9
4
5
12
3
(a) Corrected for amount found in blank; artificial ground water was reagent
water spiked with fulvic acid at the 1 mg/L concentration level. A well-
characterized fulvic acid, available from the International Huraic Substances
Society (associated with the United States Geological Survey in Denver,
Colorado), was used.
(b) n - number of data points.
(c) R = average percent recovery.
(d) S = standard deviation.
(e) RSD = percent relative standard deviation.
(f) ND = interference not detected in blank.
-------
TABLE 10. INSTRUMENT QC STANDARD
Test
Sensitivity
Chromatographic performance
Column performance
Analyte
Dichlofenthion
Suiprofos
Vernolate
Cycloate
Femtrothion
Iriphenylphosphate
Pronamide
Fonofos
Cone,
g/mL
0
0
0
5
3
1
0
0
01
01
01
15
025
Requirements
Detection of
Detection of
Detection of
0.95 < PSF <
0.95 < PSF <
0.95 < PSF <
Resolution >
analyte
analyte
analyte
1.05; 0
1.05; 0
1.05; 0
1.4 (b)
S/N
S/N
S/N
95 <
95 <
95 <
>3
>3
>3
PGF <
PGF <
PGF <
1.05 (a)
1.05 (a)
1.05 (a)
(a) PSF = peak symmetry factor. Calculated using the equation:
PSF
0.5 x W(l/2)
where w(l/2) is the width of the front of the peak at half height assuming the peak is split at its
highest point and W(l/2) is the peak width at half height (see Figure 7).
PGF = peak Gaussian factor. Calculated using the equation:
1.83 x W(l/2)
WU/10)
PGF =
where W(l/2) is the peak width at half height and W(l/10) is the peak width at tenth height (see Figure
7).
(b) Resolution between the two peaks as defined by the equation:
t
R = —-
W
where t is the difference in elution times 'between the two peaks and W is the average peak width, at the
baseline, of the two peaks.
40
-------
TABLE 11. PRESERVATION STUDY RESULTS
Day Extracted
Day Analyzed
Amount ,
Analyte ug/L
Alachlor
Ametryn
Aspon
Atraton
Atrazine
Azinphos methyl
Bolstar
Biomacil
Butachlor
Butylate
Carboxin
Chlorpropham .
Cycloate
Demeton-0
Deroeton-S
Diazinon
Dichlofenthion
Dichlorvos
Diphenamid
Disulfoton
Disulfoton sulfone
Disulfoton sulfoxide
EPN
EPIC
Ethion
Ethoprop
Ethyl parathion
Famphur
Fenamiphos
Fenarimol
Fenitrothion
Fensulfothion
Fenthion
Fluridone
Fonofos
Hexazinone
Malathion
Merphos
Methyl paraoxon
Methyl parathion
3.
20
2.
6.
1.
22
1.
25
3.
1.
6.
5.
2.
6.
2.
2.
1.
25
6.
3.
7.
3.
0.
2.
3.
1.
4 .
6.
10
3.
4 .
25
1.
38
6.
7.
3.
2.
25
1.
3
.5
0
.3
3
.8
.5
0
.0
.5
a
,5
5
0
0
.0
.5
8
.50
.5
,0
.9
.5
.0
.8
.5
.0
,5
6
8
.5
,9
0
0
R(b) RDCc.
76
95
76
76
79
78
82
74
75
51
81
76
91
72
81
79
74
78
82
98
83
83
34
80
66
82
78
87
92
82
80
78
76
90
81
78
83
82
85
84
0
1,
0
i
0,
3
0.
4
0
0
0.
i
0
0
0
0.
0.
3
0.
0
0
0.
0.
0.
0.
0.
0.
o.
0.
0
0
3 ,
0
1.
0.
1.
0,
0.
2.
0
)
7
.9
4
1
.1
.4
.0
2
.3
.3
.3
0
2
.4
.1
.2
.0
.2
.6
.2
.9
7
.0
.3
.3
,2
.3
.4
.5
.1
.3
.6
.0
.5
.7
.2
.1
.3
.5
.2
0
28
R
73
86
134
82
33
108
72
72
72
18
97
73
33
95
E5
76
30
60
92
83
88
72
63
85
92
86
91
91
92
54
88
101.
81
62
106
99
58
87
81
82
RSD
2
1
0
2
0
9
0
11
0
^
1
2
0
0
0
0
0
2
o.
0
1
1.
0
0
0
0
0.
0.
0
0
0
7
0
0
0
2
0
0
3
0
.0
.1
8
.3
.2
.0
1
.8
.2
.7
.6
.2
2
2
.1
.1
.1
.2
.6
.1
.0
. 4
.0
.3
.2
.3
.1
.3
.6
.1
. 1
7
.1
.9
.9
.7
.2
.3
.3
.3
14
14
R RSD
84
70
5
85
86
ND(a)
N0
89
60
85
97
84
36
ND
73
93
1
93
90
87
97
8
ND
89
ND
92
5
7
94
101
7
12
29
94
ND
86
ND
93
93
10
0.2
7.8
0.2
0.3
0.1
-
-
2.3
1.6
0.1
0.8
0.3
0.2
-
0.5
0.4
0.7
1.1
0.3
0.2
0.4
0.9
-
0.2
-
0.1
2.8
3.1
0.7
0.3
2.0
2.8
0.2
2.8
-
0.4
-
0.1
1.0
0.1
28
28
R
65
74
16
67
80
ND
ND
33
53
66
57
68
82
ND
27
57
ND
41
85
79
83
ND
ND
83
ND
85
ND
ND
82
60
ND
18
ND
58
ND
71
ND
84
83
14
RSD
0.0
1.5
0.1
0.1
0 1
-
-
0.5
0.4
0.0
0.6
0.0
0 1
-
0.8
0.3
-
17.7
0.5
0.2
0.6
-
-
0.2
-
0.1
-
-
1.0
2.7
-
0.3
-
27
-
0.2
-
0.2
1.7
0.0
-------
TABLE 11. PRESERVATION STUDY RESULTS (continued)
Day Extracted
Day Analyzes
Analyte
Metolachlor
Metribuzin
Mevinphos
MGK 264
MGK 326
Molinate
Napropamide
Norflurazon
Pebulate
Phorate
Phosmet
Prometon
Prometryn
Pronamide
Propazine
Simazine
Simetryn
Stirofos
Tebuthiuron
Terbacil
Terbufos
Terbutryn
Triademefon
Tricyclazole
Vemolate
Amount ,
ug/L
7
1 .
50
5
1.
1.
2
5
1
3
7
3
1
7
1
0
2
7
13
45
5
2
6
10
1
.5
.5
.0
.5
5
.5
.0
.3
.0
.5
.0
.9
.6
.3
.75
.5
.6
.0
.5
.5
.3
0
0
R(a) RSD(b)
76
79
88
77
72
76
81
82
76
71
84
60
81
71
80
81
81
78
91
74
72
82
84
72
70
0
0
3
0
0
0
0
0
0
0
0
0
0
1
0
0
0
1
0
3
0
0
0
1
0
.6
.1
.5
.4
.2
.3
.1
.4
.1
.3
. 7
.4
.2
.5
.1
.0
.1
.3
.2
.1
.2
.3
.7
.5
.1
0
28
R
76
79
92
76
97
76
81
77
60
74
63
99
61
59
86
60
81
91
58
59
77
84
82
92
72
RSD
0.
0
1.
0.
0.
0.
0.
0.
0
0.
0
0
0
4
0.
0.
0.
4
3 .
0.
0.
0.
0.
2.
0.
2
1
3
1
1
7
.1
1
0
.1
5
2
3
5
1
.0
.0
9
.4
. 7
.5
.3
,6
.5
.1
14
14
R
95
95
86
94
ND
86
85
100
100
ND
ND
21
84
4
99
99
100
83
101
99
ND
90
100
99
91
RSD
1.
0.
4 .
0.
0.
0.
0.
0.
0.
0
1 .
3
0.
0,
0.
0.
2.
0.
0.
1.
0.
. 1
2
2
.8
-
1
i,
.8
1
-
-
5
1
.8
1
.0
.1
4
.7
.3
-
.2
,4
.6
.2
28
28
R
61
59
74
58
ND
66
62
63
58
ND
ND
11
48
ND
36
62
60
61
54
60
ND
85
83
68
57
RSD
1.0
0 2
2.6
0.7
-
0.0
1.8
0.6
0.9
-
-
1.6
0 3
-
0.1
0.5
1.8
0.2
9.2
31.8
-
0.2
0.5
0.3
0.2
(a) ND = not detected.
(b) R = average percent recovery.
(c) RSD = percent relative standard deviation.
-------
TABLE 1. METHOD 1 ANALYTES INCLUDED IN PHASE III STUDIES
Alachlor
Ametryn
Aspon
Atraton
Atrazine
Azinphos methyl
Bromacil
Butachlor
Butylate
Carboxin
Chlorpropham
Chlorpyrifos
Coumaphos
Cycloate
Deraeton-0
Demeton-S
Diazinon
Dichlofenthion
Dichlorvos
Dioxathion
Diphenamid
Disulfoton
Disulfoton sulfone
Disulfoton sulfoxide
EPN
EPTC
Ethion
Ethoprop
Ethyl parathion
Famphur
Fenarimol
Fenitrothion
Fensulfathion
Fenthion
Fluridone
Fonofos
Hexazinone
Malathion
Merphos
Methyl paraoxon
Methyl parathion
Metolachlor
Metribuzin
Mevinphos
MGK 264
MGK 326
Molinate
Napropamide
Norflurazon
Pebulate
Phorate
Phosmet
Prometon
Prometryn
Pronamide
Propazine .
Simazine
Simetryn
Stirofos
Tebuthiuron
Terbacil
Terbufos
Terbutryn
Triademefon
Tricycloazole
Vernolate
-------
TABLE 2. METHOD 1 IDLs AND PROPOSED VALIDATION SPIKING LEVELS
Analyte
Alachlor
Ametryn
Aspon
Atraton
Atrazine
Azinphos methyl
Bolstar
Bromacil
Butachlor
Butylate
Carboxin
Chlorpropham
Coumophos
Cycloate
Demeton-0
Dameton-S
Diazinon
Diehlofenthion
Dichlorvos
Diphenamid
Disulfoton
Disulfoton sulfone
Disuifoton sulfoxide
EPN
EPTC
Ethion
Ethoprop
Ethyl parathion
Famphur
Fenamiphos
Spiking
Mix
D
A
D
D
B
D
E
D
C
D
C
D
C
A
A
C
C
C
E
B
A
B
D
E
B
A
B
A
A
A
Spiking
Mix Cone ,
ug/n>L(a)
10
100
6.3
30
6.3
110
6.3
130
19
7.6
30
25
12
13
30
13
13
5.0
125
30
15
38
19
2.5
13
15
10
23
30
50
IDL,
Mg/mL
0.08
0.40
0.05
0.12
0.025
0 45
0.025
0.50
0 075
0.030
0 12
0 10
0.050
0 050
0 12
0.050
0.050
0.020
0.50
0.12
0.060
0.15
0.075
0.010
0.050
0.060
0.038
0.090
0.12
0.20
EMDL,
ug/L
0.
2.
0.
0.
0,
2.
0.
2.
a
0.
0
0
o
C
J
^
n
0.
2
0.
0.
0
0
0
0
0
0
0
0
1
38
.0
.25
.60
.13
.2
.13
.5
.38
.15
.60
50
.23
25
.60
.25
.25
.10
.5
.50
.30
.75
.38
.050
.25
.30
.19
.45
.60
.0
Validation Spiking Levels
0
2
0
0
0
2
0
2
0
0
0
0
0
0
0
0
0
0
2
0
0
0
0
0
0
0
0
Q
0
1
1
.38
.0
.25
.60
.13
.2
.13
.5
.38
.15
.60
.50
.23
.25
.60
.25
.25
.10
.5
.60
.30
.75
.38
.050
.25
.30
.19
.45
.60
.0
2
1.9
10
1.3
3.0
0.63
11
0.63
13
1.9
0.76
3.0
2.5
1.1
1.3
3.0
1.3
1.3
0.50
13
3.0
1.5
3.8
1.9
0.25
1.3
1.5
1.0
2.3
3.0
5.0
3
3.
20
2.
6.
1.
22
1.
25
3.
1.
6.
5.
2.
2.
6.
2.
2.
1.
25
6.
3.
7.
3.
0.
2.
3.
1.
4 .
6.
10
.8
.5
.0
.3
.3
.8
.5
.0
0
3
5
0
5
5
0
0
0
5
,8
.50
.5
.0
.9
,5
0
, Mg/L (b)
4
9
50
6
15
3
55
3
63
9
3.
15
13
5.
6.
15
6.
6.
2.
63
15
7.
19
9.
1.
6.
7,
4 ,
11
15
25
.4
.3
.1
.1
.4
.8
.7
.3
,3
.3
.5
.5
.4
.3
.3
.5
.8
5
19
200
25
60
13
220
13
250
38
15
60
50
23
25
60
25
25
10
250
60
30
75
38
5.0
25
30
19
45
60
100
-------
TABLE 2. METHOD 1 IDLs AND PROPOSED VALIDATION SPIKING LEVELS (continued)
Analyte
Fenarimol
Fenitrothion
Fensulfothion
Fenthion
Fluridone
Fonofos
Eexazinone
Malathion
Merphos
Methyl paraoxon
Methyl parathion
Metolachlor
Metribuzin
Mevinphos
MGK 264
MGK 326
Molinate
Napropamide
Norflurazon
Pebulate
Phorate
Phosmet
Prometon
Prometryn
Pronanude
Propazine
Simazine
Simetryn
Stirofos
Tebuthiuron
Spiking
Mix
E
A
D
C
E
B
D
E
3
B
B
C
C
A
C
A
D
E
C
E
E
E
A
B
D
B
E
E
D
E
Spiking
Mix Cone ,
Mg/mL(a) i.
19
23
130
5 0
190
33
38
19
13
130
10
38
7.5
250
25
7.5
7.6
13
25
6.3
15
38
15
10
38
6.3
3.8
13
38
63
IDL
'g/ral
0
o
0
0,
o.
0
o.
0
o.
0
0
0
0
1
0
0
0
0
0,
0.
0,
0.
0
0,
0
0,
0
0.
0
0
EMDL,
.075
.090
50
.020
.75
.13
,15
.075
,050
.50
.038
.15
.030
.0
10
.030
030
.050
.10
.025
,060
.15
.060
,038
.15
,025
.015
.050
.15
.25
0.
0.
2.
0.
3.
0.
0.
0.
0.
2.
0.
0.
0.
5.
0.
0,
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
Validation Spiking
38
45
5
10
8
65
76
38
25
5
19
75
15
0
50
15
15
25
50
13
30
75
30
19
76
13
075
25
76
3
1
0
0
2
0,
3.
0
0.
0
0.
2,
0
0
0
5
0
o ,
o ,
0
0,
0
0,
o.
0,
0.
0,
0.
0,
0.
0.
1.
.38
.45
.5
.10
.8
.65
.76
.38
.25
.5
.19
.75
.15
.0
50
.15
,15
.25
,50
.13
,30
,75
.30
,19
.76
,13
.075
,25
.76
.3
2
1
2
13
0
19
3
3
1
1
13
1
3.
0
25
2
0
0
1
2,
0
1,
3.
1,
1.
3,
0.
0
1 .
3.
6,
.9
3
.50
.3
.8
.9
.3
.0
.8
.75
.5
.75
76
.3
.5
.63
,5
.8
.5
.0
.8
,63
.38
,3
,8
,3
Levels. yg/L (b)
3
3 8
4.5
25
1.0
38
6.5
7.6
3.8
2.5
25
1.9
7.5
1.5
50
5.0
1.5
1.5
2.5
5.0
1.3
3.0
7.5
3.0
1.9
7.6
1.3
0.75
2.5
7.6
13
4
9
11
63
2,
94
16
19
9
6.
63
4,
19
3.
125
13
3.
0.
6.
13
3.
7.
19
7.
4.
19
3.
1.
6.
19
31
.4
.5
.4
,3
,8
8
8
76
,3
,1
5
5
8
1
9
3
5
38
45
250
10
380
65
76
38
25
250
19
75
15
500
50
15
15
25
50
13
30
75
30
19
76
13
7.5
25
76
125
45
-------
TABLE 2. METHOD 1 IDLs AND PROPOSED VALIDATION SPIKING LEVELS (continued)
Analyte
Terbacil
Terbufos
Terbutryn
Tnademefon
Tricyclazole
Vernolate
Spiking
Mix
E
C
B
B
D
C
Spiking
Mix Cone ,
IDL.
EMDL.
Validation Spiking Levels, wg/L (b)
Mg/mL(a) ag/mL ns/L 1
230
25
13
33
50
6.3
0
0
0
0
0
0
.90
.10
.050
.13
20
.025
4
0
0
0
1
0
5
.50
.25
.65
.0
.13
4
0
0
0
1
0
5
.50
.25
.65
.0
.13
2
23
2
1.
3.
5
0.
.5
.3
.3
.0
.63
3
45
5
2.
6.
10
1.
.0
.5
.5
.3
4
113
13
6.3
16
40
3.1
5
450
50
25
65
100
13
(a) Spiking mixture prepared in MTBE; 20 jtL of spiking mix was added to samples to achieve spiking level 1.
(b) Spiking level 3 used for matrix validation and preservation studies.
-------
R
o
r>
9
x
o
to
T3
X
V
yi _
s
O)
-------
R
1
o
o
2
I > i i L I u.
1. 1 .1
»
o
wt
08
U)
lr>
re
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b<
o-
re*
•o
re
Q.
re
s
s
w _
B
B
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s
IS 2
C13
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-------
OS
I-IS 1
-SUR 1
yi _
s
r»
i
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81
u»
B
o
tr
yi
S
IS 2
-------
o
o
s
1
o
o
TJ
LA
«
O
— rn
C5
re
re
B
B
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-------
I • • • • I I I • • I • • • • I • I I 1*1-1 I IJ 1 k J.l 1 U-J. t t I t J I I I I.J. t J_i
o»NUroto1uene
l,3»Di»xihyi»^-nitroben2ene
M
Ul
P
s
U!
01
s
e
- Vernoltte
Cycloate
Fonofos
Pronamide
Dichlofenthion
Fenitrothion
9-Nitroanthracene
Wl _
Sulprofos
TPP
3 •
•J
-------
jnqdurej
soqdutzv
uodsv sojouoj
snoanbv DNixvidsia SHXAIVNV i QOHIHW
-------
Figure 6
a
a
a
a
113
2 SI
63
ans
a
a
93
S3
o
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2
13
i i | r r IM | T f n T T 1-1 i p r
53
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-------
Figure 7
x «
X
1
oo
o
Q.
a. o
UJ «J
l/t U4
S 0.
54
-------
Method 3. Determination of Chlorinated.Acids in Ground
Water by Gas Chromatography with an Electron Capture Detector
1. SCOPE AND APPLICATION
1.1 This is a gas chromatographic (GC).method applicable to the
determination of certain chlorinated 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.
1.3 This method has been validated in a single laboratory. Estimated
detection limits (EDLs) have been determined and are listed in
Table 2. Observed detection limits may vary between ground
waters, depending upon the nature of interferences in the sample
matrix and the specific instrumentation used.
1.4 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
0.1 N sodium hydroxide and shaken for I 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 (ECD).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 of a pure analyte,
dissolved in an organic solvent, analyzed under the same
procedures and conditions used to analyze sample extracts
containing that analyte.
3.3 Estimated detection limit (EDL) -- the minimum concentration of a
substance that can be measured and reported with confidence that
the analyte concentration is greater than zero as determined from
the analysis of a sample in a given matrix containing the
analyte. The EDL is equal to the level calculated by multiplying
the standard deviation of replicate measurements times the
students' t value appropriate for a 99 percent confidence level
and a standard deviation estimate with n-1 degrees of freedom or
the level of the compound in a sample yielding a peak in the
final extract with signal-to-noise ratio of approximately five,
whichever value is higher.
3.4 Internal standard --a pure compound added to a sample extract in
a known amount and used to calibrate concentration measurements
of other analytes that are sample components. The internal
standard must be a compound that is not a sample component.
3.5 Instrument quality control (QC) standard -- a methyl tert-butyl
ether (MTBE) solution containing specified concentrations of
specified analytes. The instrument QC standard is analyzed each
working day prior to the analysis of sample extracts and
calibration standards. The performing laboratory uses this
solution to demonstrate 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 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.
3.9 Stock standard solution --a concentrated solution containing a
certified standard that is a method analyte, or a concentrated
solution of an analyte prepared in the laboratory with an assayed
reference compound.
-------
3.10 Surrogate standard --a pure compound added to a sample in a
known amount and used to detect gross abnormalities during sample
preparation. The surrogate standard must be a compound that is
not a sample component.
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 chromato-
grams. All reagents and apparatus must be routinely demonstrated
to be free from interferences under the conditions of the
analysis by running laboratory method blanks as described in
Section 10.7.
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 (1+9) 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.
4.4 Interferences by phthalate esters can pose a major problem in
pesticide analysis when using the ECD. These compounds generally
appear in the chromatogram as large peaks. Common flexible
plastics contain varying amounts of phthalates, that are easily
extracted or leached during laboratory operations. Cross
contamination of clean glassware routinely occurs when plastics
are handled during extraction steps, especially when sol-
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5.
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.3''1
4.5 Interfering contamination may occur when a sample containing low
concentrations of analytes is analyzed immediately following a
sample containing relatively high concentrations of analytes.
Between-sample rinsing of the sample syringe and associated
equipment with MTBE can minimize sample cross contamination.
After analysis of a sample containing high concentrations of
analytes, one or more injections of MTBE 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.
5.1 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
data handling sheets should also be made available to all
personnel involved in the chemical analysis. Additional
references to laboratory safety are available and have been
identified5"7 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.
5.2.3 Use mechanical pipetting aides.
5.2.4 Do not heat above 90°C -- EXPLOSION may result.
5.2.5 Avoid grinding surfaces, ground glass joints, sleeve
bearings, glass stirrers -- EXPLOSION may result.
5.2.6 Store away from alkali metals -- EXPLOSION may result.
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5.2.7 Solutions of diazomethane decompose 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/or 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, rinsed
with acetone, and dried before use to minimize contamin-
ation. Cap liners are cut to fit from sheets (Pierce
Catalog No. 012736) and extracted with methanol over-
night 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-D) -- 10- or 25-mL,
graduated (Kontes K-570050-2525 or Kontes K-570050-1025
or equivalent). Calibration must be checked at the
volumes employed in the test. Ground glass stoppers are
used to prevent evaporation of extracts.
6.2.4 Evaporative flask, K-D -- 500-mL (Kontes K-570001-0500
or equivalent). Attach to concentrator tube with
springs.
6.2.5 Snyder column, K-D -- three-ball macro (Kontes K-503000-
0121 or equivalent).
6.2.6 Snyder column, K-D -- two-ball micro (Kontes K-569001-
0219 or equivalent).
6.2.7 Flask, round-bottom -- 500-mL with 24/40 ground glass
joint.
6.2.8 Vials -- glass, 5- to 10-raL capacity with TFE-fluoro-
carbon lined screw cap.
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6.2.9 Disposable pipets -- sterile plugged borosilicate glass,
5-mL capacity (Corning 7078-5N 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/rain (Associated Design and
Mfg. Co., Alexandria, VA) .
6.5 Boiling stones -- Teflon, CHEMWARE (Norton Performance Plastics
No. 015021).
6.6 Water bath -- Heated, capable of temperature control (+2°C). The
bath should be used in a hood.
6.7 Balance -- Analytical, capable of accurately weighing to the
nearest 0.0001 g.
6.8 Diazomethane generator -- Diazomethane generator assembly as
shown in Figure 1.
6.9 Glass wool -- Acid washed (Supelco 2-0383 or equivalent) and
heated at 450°C for 4 hours.
6.10 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.
6.10.1 Primary column - - 30 m long x 0.25 mm I.D. SPB-5 bonded
fused silica column, 0.25 urn film thickness (available
from Supelco). Validation data presented in this method
were obtained using this column. Alternative columns
may be used in accordance with the provisions described
in Section 10.3.
6.10.2 Confirmation column - - 30 m long x 0.25 mm I.D. DB-1701
bonded fused silica column, 0.25 urn film thickness
(available from J&W).
6.10.3 Detector -- Electron capture. This detector has proven
effective in the analysis of spiked reagent and arti-
ficial ground waters. An ECD 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
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7.1 Acetone, methanol, methylene chloride, MTBE --'Pesticide quality
or equivalent.
7.2 Ethyl ether, unpreserved -- Nanograde, redistilled in glass if
necessary. Must be free of peroxides as indicated by EM Quant
test strips (available from Scientific Products Co., Cat. No.
P1126-8, 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 450°C for a minimum of 4 hours to remove inter-
fering 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 (NaOH), pellets -- ACS grade.
7.4.1 NaOH, 6 N -- Dissolve 216 g NaOH in 900 mL reagent
water.
7.5 Sulfuric acid (H2SO,,) , concentrated, ACS grade -- sp. gr. 1.84.
7.5.1 H2SO<,, 12 N -- Slowly add 335. mL concentrated H2S04 to
665 mL of reagent water.
7.6 Carbitol, ACS grade -- available from Aldrich Chemical Co.
7.7 Diazald, ACS grade -- available from Aldrich Chemical Co.
7.8 Sodium chloride (NaCl), crystal, ACS grade -- Heat treat in a
shallow tray at 450°C for a minimum of 4 hours to remove
interfering organic substances.
7.9 4,4'-Dibromooctafluorobiphenyl (DBOB) -- >99% purity, for use as
internal standard (available from Aldrich Chemical Co).
7.10 2,4-Dichlorophenylacetic acid (DCAA) -- >99% purity, for use as
surrogate standard (available from Aldrich Chemical Co).
7.11 Reagent water -- Reagent water used to generate the validation
data in this method was distilled water obtained from the
Magnetic Springs Water Co., Columbus, Ohio.
7.12 STOCK STANDARD SOLUTIONS (1.00 ug/uL) -- Stock standard solutions
may be purchased as certified solutions or prepared from pure
standard materials using the following procedure:
7.12.1 Prepare stock standard solutions by accurately weighing
approximately 0.0100 g of pure material. Dissolve the
material in MTBE and dilute to volume in a 10-mL volu-
metric flask. Larger volumes may be used at the conven-
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ience of the analyst. If compound purity is certified
at 96% or greater, Che 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.
7.12.2 Transfer the stock standard solutions into TFE-fluoro-
carbon-sealed screw cap vials. Store at room tempera-
ture and protect from light.
7.12.3 Stock standard solutions should be replaced after two
months or sooner if comparison with laboratory control
standards indicates a problem.
7.13 INTERNAL STANDARD SPIKING SOLUTION -- Prepare an internal
standard spiking solution by accurately weighing approximately
0.0010 g of pure DBOB. Dissolve the DBOB 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 results in
a final internal standard concentration of 0.25 ug/L.
7.14 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 sample prior to
extraction results in a surrogate standard concentration in the
sample of 5 ug/L and, assuming quantitative recovery of DCAA, a
surrogate standard concentration in the final extract of
0.5 ug/mL.
7.15 INSTRUMENT QC STANDARD -- Prepare a diluted dinoseb solution by
adding 10 uL of the 1000 ug/mL dinoseb stock solution to MTBE and
diluting to volume in a 10-mL volumetric flask. To prepare the
instrument QC standard, add 40 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 11.3. 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.
7.16 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.
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SAMPLE COLLECTION. PRESERVATION. AND STORAGE
8.1 Grab samples must be collected in glass containers. Conventional
sampling practices8 should be followed; however, the bottle must
not be prerinsed with sample before collection.
8.2 SAMPLE PRESERVATION AND STORAGE
8.2.1 The samples must be iced or refrigerated at 4°C from the
time of collection until extraction. Preservation study
results given in Table 11 indicate that samples stored
under these conditions are stable for at least 28 days
after collection.
8.3
8.2.2 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.
8.2.3 After the sample is collected in the bottle containing
preservative, seal the bottle and shake vigorously for
1 min.
EXTRACT STORAGE
1.3.1
Sample extracts should be stored at 4°C away from light.
Preservation study results given in Table 11 indicate
that sample extracts stored under these conditions are
stable for at least 28 days.
9.
CALIBRATION
9.1 Establish GC operating parameters equivalent to those indicated
in Table 3. The GC system must be calibrated using the internal
standard technique (Section 9.2).
9.2 INTERNAL STANDARD CALIBRATION PROCEDURE -- To use this approach,
the analyst must select one or more internal standards compatible
in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal
standard is not affected by method or matrix interferences.
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:
RRa = Aa/Ais
where: Aa = the peak area of the analyte, and
Ais = the peak area of the internal standard.
Generate a calibration curve of RRa versus analyte
concentration in the sample in ug/L.
9.2.3 The working calibration curve must be verified on each
working shift by the measurement of one or more calibra-
tion standards. If the response for any analyte varies
from the predicted response by more than +20%, the test
must be repeated using a fresh calibration standard.
Alternatively, a new calibration curve must be prepared
for that analyte.
10. QUALITY CONTROL
10.1 Each laboratory using this method is required to operate a
quality control (QC) program. The minimum requirements of this
program consist of the following: an initial demonstration of
laboratory capability; the analysis of surrogate standards in
each and every sample as a continuing check on sample prepara-
tion; the monitoring of internal standard area counts or peak
heights in each and every sample as a continuing check on system
performance; the analysis of QC samples, performance evaluation
(PE) samples, and 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 perfor-
mance .
10.2 INITIAL DEMONSTRATION OF CAPABILITY -- To establish the ability
to perform this method, the analyst must perform the following
operations.
10.2.1 Select a representative spike concentration (suggest
15 times the EDL) for each of the target analytes.
Using a stock standard that differs from calibration
standard, prepare a laboratory control (LC) check sample
concentrate in methanol 1000 times more concentrated
than the selected spike concentration.
10
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10.2.2 Using a syringe, add 1 mL of the LC sample concentrate
to each of a minimum of four 1-L aliquots of reagent
water. A representative ground water may be used in
place of the reagent water, but one or more unspiked
aliquots must be analyzed to determine background
levels, and the spike level must, at a minimum, exceed
twice the background level for the test to be valid.
Analyze the aliquots according to the method beginning
in Section 11.
10.2.3 Calculate the average percent recovery (R) and the
standard deviation of the percent recovery (SR), for the
results. Ground water background corrections must be
made before R and SR calculations are performed.
10.2.4 Table 2 and Tables 4-9 provide single laboratory
recovery and precision data obtained for the method
analytes from reagent and artificial ground waters,
respectively. Similar results from dosed reagent and
artificial ground waters should be expected by any
experienced laboratory. Compare your laboratory 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. Your laboratory results are comparable if
your 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 chromatography,
the analyst is permitted to modify GC columns, GC conditions, or
detectors to improve the separations or lower the cost of
measurements. Each time such modifications to the method are
made, the analyst is required to repeat the procedure in Section
10.2.
10.4 ASSESSING SURROGATE RECOVERY
10.4.1 All samples and blanks must be fortified with the
surrogate spiking compound before extraction. A
surrogate standard determination must be performed on
all samples (including matrix spikes) and blanks.
10.4.2 Determine whether the measured surrogate concentration
(expressed as percent recovery) falls between 70 and 120
percent.
10.4.3 When the surrogate recovery for a laboratory method
blank is less than 70 or greater than 120 percent, the
laboratory must take the following actions:
11
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(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 120 percent recovery
criteria, the analytical system must be considered "out
of control." The problem must be identified and
corrected before continuing.
10.4.5 When the surrogate recovery for a sample is less than 70
percent or greater than 120 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.
12
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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, quan-
tify and report results. If the reinjected
sample extract aliquot displays an internal
standard peak area or height outside the
specified limits, but extract aliquots from
other samples continue to give the proper
area or height for the internal standard,
assume an error was made during addition of
the internal standard to the failed sample
extract. Repeat the analysis of that sample.
10.5.3.2 Multiple Occurrence -- If the internal
standard peak areas or heights for successive
samples fail the specified criteria (10.5.2),
check the instrument for proper performance.
After optimizing instrument performance,
check the calibration curve using a
calibration check standard (Section 9). If
the calibration 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, re-
analyze 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 ANALYTE RECOVERY
10.6.1 The laboratory must, on an ongoing basis, spike each of
the target analytes into one sample per sample set (a
sample set is all those samples extracted within a
24-hour period) or ten percent of the samples, whichever
is of greater frequency.
10.6.1.1 The spiking concentration in the sample
should be one to five times the background
13
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concentration, or, if it is impractical to
determine background levels before spiking,
15 times the EDL.
10.6.1.2 Analyze one sample aliquot to determine the
background concentration (B) of each para-
meter. Spike a second sample aliquot with a
laboratory control (LC) sample concentrate
(the volume of the spike should be kept to a
minimum so the solubility of the analytes of
interest in water will not be affected) and
analyze it to determine the concentration
after spiking (A) of each parameter. Calcu-
late each percent recovery (Ri) as 100(A-
B)%/T, where T is the known true
concentration of the spike.
10.6.1.3 Compare the percent recovery (Ri) for each
parameter with established QC acceptance
criteria. QC criteria are established by
initially analyzing five spiked samples as in
Section 10.6.2, calculating the average
percent recovery (R) and the standard devia-
tion of the percent recovery (SR) using the
following equations:
i-l
and
n n 2
1
SR - — —
n-1 i-l
n
where : n — number of measurements for each
analy te , and
Rx - individual percent recovery
value .
Calculate QC acceptance criteria as follows:
Upper Control Limit (UCL) - R + 3SR
Lower Control Limit (LCL) - R - 3SR
Alternatively, the data generated during the
initial demonstration of capability (Section
10.2) can be used to set the initial upper
and lower control limits .
14
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Monitor all data from dosed samples. Analyte
recoveries must fall within the established
control limits.
Update the method performance criteria on a
continuous basis. After each five to ten new
recovery^measurements (R^s), recalculate R
and SR using all the data, and construct new
control limits. When the total number of
data points reach twenty, update the control
limits by calculating R and SR using only the
most recent twenty data points.
10.6.2 Each quarter, it is essential that the laboratory
analyze (if available) QC check standards. If the
criteria established by the U.S. Environmental Protec-
tion Agency (USEPA) and provided with the QC standards
are not met, corrective action needs to be taken and
documented.
10.6.3 If any parameter fails the acceptance criteria for
recovery in Section 10.6.1.3, a LC check standard
containing each parameter that failed must be prepared
and analyzed.
10.6.3.1 Prepare the LC check standard by adding 1 mL
of LC check sample concentrate to a 1-L
aliquot of reagent water. The LC check
standard needs only to contain the parameters
that failed the criteria in Section 10.6.1.3.
10.6.3.2 Analyze the LC check standard to determine
the concentration measured (A) of each
parameter. Calculate each percent recovery
(RJ as 100(A/T)%, where T is the true value
of the standard concentration.
10.6.3.3 Compare the percent recovery (Ri) for each
parameter with the QC acceptance criteria
found on your control chart. Only parameters
that failed the test in Section 10.6.2.4 need
to be compared with these criteria. If the
recovery of any such parameter falls outside
the designated range, the laboratory perfor-
mance for that parameter is judged to be out
of control, and the source of the problem
must be immediately identified and resolved
before continuing the analyses. The
analytical result for that parameter in the
unspiked sample is suspect and must be so
labeled. All results reported since the last
dosed sample shown to be in control must also
be labeled suspect.
15
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If the recovery of any such parameter falls
within the designated range, the laboratory
performance for that parameter is judged to
be in control, and the recovery problem
encountered with the dosed sample is judged
to be matrix-related, not system-related.
The result for that parameter in the unspiked
sample is labeled suspect/matrix to inform
the user that the results are suspect due to
matrix effects.
10.6.4 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 LABORATORY CONTAMINATION (METHOD BLANKS) -- Before
processing any samples, the analyst must demonstrate that all
glassware and reagent interferences are under control. This is
accomplished by the analysis of a laboratory method blank. A
laboratory method blank is a 1-L aliquot of reagent water
analyzed as if it was a sample. Each time a set of samples is
extracted or there is a change in reagents, a laboratory method
blank must be processed to assess laboratory contamination. If
the method blank exhibits a peak within the retention time window
of any analyte which is greater than or equal to one-half the EDL
for that analyte, determine the source of contamination before
processing samples and eliminate the interference problem.
10.8 ASSESSING INSTRUMENT PERFORMANCE (INSTRUMENT QC STANDARD) --
Instrument performance should be monitored on a daily basis by
analysis of the instrument QC standard. The instrument QC
standard contains compounds designed to indicate appropriate
instrument sensitivity, column performance and chromatographic
performance. Instrument QC standard components and performance
criteria are listed in Table 10. Inability to demonstrate
acceptable instrument performance indicates the need for
reevaluation of the GC-ECD system. A GC-ECD chromatogram
generated from the analysis of the instrument QC standard is
shown in Figure 2. 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.
10.9 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 2.
16
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10.10 ADDITIONAL OC - 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 - Validation data presented in this method were generated
using the mechanical separatory funnel shaker.
11.1 HYDROLYSIS AND CLEANUP
11.1.1 Mark the water meniscus on the side of the sample bottle
for later determination of sample volume. Spike sample
with 50 uL of the surrogate standard spiking solution.
If the mechanical separatory funnel shaker is used, pour
the entire sample into a 2-L separatory funnel. If the
mechanical tumbler is used, pour the entire sample into
a tumbler bottle.
11.1.2 Add 17 mL of 6 N NaOH to the sample, seal, and shake for
1 hour using the appropriate mechanical mixing device.
11.1.3 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.
11.1.4 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.
11.1.5 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.
17
-------
11.2 EXTRACTION AND CONCENTRATION
11.2.1 Add 17 mL of 12 N H2S04 to the sample, seal, and shake
to mix.
11.2.2 Add 250 g NaCl to the sample, seal, and shake to
dissolve salt.
11.2.3 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
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 rain
after starting the mixing device.
11.2.4 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 aqueous phase. Collect
the extract in a 500-mL round-bottom flask containing
about 5 g of acidified anhydrous sodium sulfate. Allow
the extract to remain in contact with the sodium sulfate
for approximately 2 hours.
11.2.5 Assemble a K-D concentrator by attaching a concentrator
tube to a 500-raL evaporative flask.
11.2.6 Pour the dried extract through a funnel plugged with
acid washed glass wool, and collect the extract in the
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.
11.2.7 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.
Place the K-D 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-D
18
-------
apparatus and allow it to drain and cool for at least 10
min.
11.2.8 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-D apparatus
on the water bath so that the concentrator tube is
partially immersed in the hot water. Adjust the
vertical position of the apparatus and the water
temperature as required to complete concentration in 5
to 10 min. When the apparent volume of liquid reaches
0.5 mL, remove the micro K-D from the bath and allow it
to drain and cool. Remove the micro Snyder column and
add 250 uL of methanol. Rinse the walls of the concen-
trator tube while adjusting the volume to 5.0 mL with
MTBE.
11.3 ESTERIFICATION OF ACIDS
11.3.1 Assemble the diazomethane generator (Figure 1) in a
hood.
11.3.2 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 Diazald to Tube 2. Immediately place the exit
tube into the concentrator tube containing the sample
extract. Apply nitrogen flow (10 mL/min) to bubble
diazomethane through the extract for 1 min. Immediately
remove first sample and replace with second 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 additional
samples.
11.3.3 Seal concentrator tubes with Teflon stoppers. Store at
room temperature in a hood for 30 min.
11.3.4 Destroy any unreacted diazoraethane 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. Adjust the sample volume to 5.0 mL with MTBE.
11.4 FLORISIL CLEANUP
11.4.1 Place a small plug of glass wool into a 5-mL disposable
glass pipet. Tare the pipet, and measure 1 g of
activated Florisil into the pipet.
11.4.2 Apply 5 mL of 5 percent methanol in MTBE to the
Florisil. Allow the liquid to just reach the top of the
19
-------
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.
11.4.3 Apply 5 mL methylated sample to the Florisil. Collect
eluate in K-D tube.
11.4.4 Add 1 mL of 5 percent methanol in MTBE to the sample
container, rinsing walls. Transfer the rinse to the
Florisil column. 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-D tube.
11.4.5 If necessary, dilute eluate to 10 mL with 5 percent
methanol in MTBE. Spike with 25 uL of internal standard
solution. Thoroughly mix sample and place aliquot in a
GC vial for subsequent analysis.
11.4.6 Seal the vial and store in a refrigerator if further
processing will not be performed immediately. Analyze
by GC-ECD.
11.5 GAS CHROMATOGRAPHY
11.5.1 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 2-4. Other GC columns, chromatographic condi-
tions, or detectors may be used if the requirements of
Section 10.3 are met.
11.5.2 Calibrate the system daily as described in Section 9.
The standards and extracts must be in MTBE.
11.5.3 Inject 2 uL of the sample extract. Record the resulting
peak size in area units.
11.5.4 The width of the retention time window used to make
identifications should be based upon measurements of
actual retention time variations of standards over the
course of a day. Three times the standard deviation of
a retention time can be used to calculate a suggested
window size for a compound. However, the experience of
the analyst should weigh heavily in the interpretation
of chromatograms.
11.5.5 If the response for the peak exceeds the working range
of the system, dilute the extract and reanalyze.
20
-------
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.
13. PRECISION AND ACCURACY
13.1 In a single laboratory, analyte recoveries from reagent water
were determined at five concentration levels. Results were used
to determine analyte EDLs and demonstrate method range. In cases
where analytes coeluted using primary analytical conditions,
results from confirmatory GC conditions were used. EDL results
are given in Table 2. Method range results are given in Tables
4-7.
13.2 In a single laboratory, analyte recoveries from two artificial
ground waters were determined at one concentration level.
Results were used to demonstrate applicability of the method to
different ground water matrices. 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.
REFERENCES
1. "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 45268.
2. ASTM Annual Book of Standards, Part 31, D3694, "Standard Practice for
Preparation of Sample Containers and for Preservation, " American
Society for Testing and Materials, Philadelphia, PA, p. 679, 1980.
3. Giam, C. S., Chan, H. S., and Nef, G. S. "Sensitive Method for Deter-
mination of Phthalate Ester Plasticizers in Open-Ocean Biota Samples,"
Analytical Chemistry. 47, 2225 (1975).
4. Giam, C. S., and Chan, H. S. "Control of Blanks in the Analysis of
Phthalates in Air and Ocean Biota Samples," U.S. National Bureau of
Standards, Special Publication 442, pp. 701-708, 1976.
21
-------
5. "Carcinogens - Working with Carcinogens," Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, Aug. 1977.
6. "OSHA Safety and Health Standards, General Industry," (29 CFR 1910),
Occupational Safety and Health Administration, OSHA 2206, (Revised,
January 1976).
7. "Safety in Academic Chemistry Laboratories," American Chemical Society
Publication, Committee on Chemical Safety, 3rd Edition, 1979.
8. ASTM Annual Book of Standards, Part 31, D3370, "Standard Practice for
Sampling Water," American Society for Testing and Materials,
Philadelphia, PA, p. 76, 1980.
22
-------
TABLE 1. METHOD ANALYTES
Analyte
Acif luorfen
Bentazon
Chloramben
2,4-D
Dalapon
2,4-DB
DCPA acid metabolites (c)
Dicamba
3 , 5-Dichlorobenzoic acid
Dichlorprop
Dinoseb
5 -Hydroxydicamba
4-Nitrophenol
PCP
Picloram
2,4,5-T
2,4,5-TP
CAS No. (a)
50594-66-6
25057-89-0
133-90-4
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
Ident.
Code (b)
17
14
9
6
1
12
16
4
2
5
13
10
3
7
15
11
8
(a) CAS No. - Chemical Abstracts Service Registry
Number.
(b) Code used for identification of peaks in figures; IS
= 4,4'-dibromooctafluorobiphenyl internal standard;
SUR — 2,4-dichlorophenylacetic acid surrogate
standard.
(c) DCPA monoacid and diacid metabolites included in
method scope; DCPA diacid metabolite used for
validation studies.
23
-------
TABLE 2. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 1)
AND EDLs (a)
Analyte
Acifluorfen
Bentazon (i)
Chloraraben (h,i)
2,4-D (i)
Dalapon
2,4-DB (h,i)
DGPA diacid metabolite
Dicamba (i)
2 ,4-Dichlorobenzoic acid
Dichlorprop
Dinoseb (h,i)
5-Hydroxydicamba (i)
4-Nitrophenol
PGP (j)
Picloram (i)
2,4,5-T (i)
2,4,5-TP (h,i)
Spiking
Le ve 1 ,
ug/L
0.020
0.20
0.080
0.20
1.0
0.80
0.020
0.080
0.060
0.20
0.080
0.040
0.10
0.040
0.12
0.080
0.040
Amt in
Blank,
ug/L n(b)
ND(f)
ND
ND
ND
ND
ND
ND
ND
0.00906
ND
ND
ND
ND
0.0500
ND
ND
ND
6
7
7
7
6
7
6
7
6
6
7
7
6
6
7
7
7
R(c)
139
92
118
90
90
37
50
155
69
77
118
49
89
130
166
87
140
S(d) RSD(e)
0.0306
0.0346
0.0310
0.0248
0.400
0.229
0.0052
0.0269
0.0194
0.0814
0.0623
0.00547
0.0399
0.0242
0.0468
0.0144
0.0249
110
19
33
14 '
45
78
53
22
38
53
66
28
45
24
24
21
44
EDL(f)
0.096
0.20
0.093
0.20
1.3
0.80
0.020
0.081
0.061
0.26
0.19
0.040
0.13
0.076
0.14
0.080
0.075
(a) Data corrected for amount detected in blank.
(b) n - number of recovery data points.
(c) R = average percent recovery.
(d) S - standard deviation.
(e) RSD = percent relative standard deviation.
(f) ND - interference not detected in blank.
(g) EDL = the level calculated by multipyling 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 a
final extract with signal-to-noise ratio of approximately five, whichever
value is greater.
(h) Results from confirmatory analysis conditions.
(i) Results from spiking level 2.
(j) Results from spiking level 3.
-------
TABLE 3. PRIMARY AND CONFIRMATION CHROMATOGRAPHIC CONDITIONS
Relative or Absolute Retention Time
for Given Conditions
Analyte Primary (a)(c) Confirmation (b)(d)
Acifluorfen
Bentazon
Chloramben
2,4-D
Dalapon
2,4-DB
DCPA acid metabolites (c)
Dicamba
3 , 5-Dichlorobenzoic acid
Dichlorprop
Dinoseb
5 -Hydroxydicamba
4-Nitrophenol
PCP
Picloram
2,4,5-T
2,4,5-TP
1.52
1.21
1.08
0.927
0.123
1.17
1.29
0.802
0.676
0.909
1.18
1.09
0.678
1.03
1.23
1.11
1.08
43.2
34.6
(e)
27.0
(e)
32.2
37.4
22.6
17.7
25.6
34.1
30.7
20.5
27.0
35.6
30.9
29.5
(a) Retention time relative to DBOB internal standard which elutes at approximately 27.5 mm.
(b) Absolute retention time in minutes.
(c) Primary conditions:
Column: 30 m long x 0.25 rim I.D. DB-5 bonded fused silica column, 0.25 urn film thickness
tJ&W)
Injection volume: 2 uL splitless with 45 second delay
Carrier gas: He @30 cm/sec linear velocity
Injector temp: 250"C
Detector temp: 320'C
Oven temp: Program from 60*C to 300 *C at 4*C/min
Detector: ECD
(d) Confirmation conditions:
Column: 30 m long x 0.25 mm I.D. DB-1701 bonded fused silica column, 0.25 urn film
thickness (J&W)
Injection volume: 2 uL splitless with 45 second delay
Carrier gas: He @30 cm/sec linear velocity
Injector temp: 250*C
Detector temp: 320'C
Oven temp: Program from 60'C to 300*C at 4'C/min
Detector: ECD
(e) Data not available.
25
-------
TABLE 4. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 2) (a)
Analyte
Acifluorfen
Bentazon
Chloramben (g)
2,4-D
Dalapon
2,4-DB (g)
DCPA diacid metabolite
Dicamba
3 , 5-Dichlorobenzoic acid
Dichlorprop
Dinoseb (g)
5 -Hydroxydicamba
4-Nitrophenol
PCP (h)
Picloram
2,4,5-T
2,4,5-TP (g)
Spiking Amt in
Level, Blank,
ug/L ug/L n(b)
0.040
0.20
0.080
0.20
2.0
0.80
0.040
0.080
0.12
0.40
0.080
0.040
0.20
0.0080
0.12
0.080
0.040
ND(f)
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
7
7
7
7
6
7
7
7
7
7
7
7
7
-
7
7
7
R(c)
88
92
118
90
107
37
89
155
85
110
118
49
148
-
166
87
140
S(d) RSD(e)
0.00826
0.0346
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
23
19
33
14
21
78
89
22
11
16
66
28
15
-
24
21
44
(a) Data corrected for amount detected in blank.
(b) n = number of recovery data points.
(c) R = average percent recovery.
(d) S - standard deviation.
(e) RSD - percent relative standard deviation.
(f) ND = interference not detected in blank.
(g) Results from confirmatory analysis conditions.
(h) Analyte not detected at this spiking level.
26
-------
TABLE 5. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 3) (a)
Analyte
Spiking Amt in
Level, Blank,
ug/L ug/L n(b)
R(c)
S(d) RSD(e)
Acifluorfen
Bentazon
Chloramben (g)
2,4-D
Dalapon
2,4-DB (g)
DCPA diacid metabolite
Dicamba
3 , 5-Dichlorobenzoic acid
Dichlorprop
Dinoseb (g)
5 -Hydroxydicamba
4-Nitrophenol
PCP
Picloram
2,4,5-T
2,4,5-TP (g)
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
0.00171
ND(f)
0.0222
0.00943
1.17
ND
ND
ND
0.00500
0.0847
0.113
ND
ND
0.0500
0.308
0.00218
0.00455
6
4
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
121
120
111
131
100
87
74
135
102
107
42
103
131
130
91
117
134
0.0318
0.163
0.0615
0.274
2.24
0.5182
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
24
17
14
23
(a) Data corrected for amount detected in blank.
(b) n = number of recovery data points.
(c) R = average percent recovery.
(d) S - standard deviation.
(e) RSD = percent relative standard deviation.
(f) ND - interference not detected in blank.
(g) Results from confirmatory analysis conditions,
27
-------
TABLE 6. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 4) (a)
Analyte
Acifluorfen
Bentazon
Chloramben (g)
2,4-D
Dalapon
2,4-DB (g)
DCPA diacid metabolite
Dicamba
3 , 5-Dichlorobenzoic acid
Dichlorprop
Dinoseb (g)
5 - Hydroxydicamba
4-Nitrophenol
PCP
Picloram
2,4,5-T
2,4,5-TP (g)
Spiking
Leve 1 ,
ug/L
0.50
2.5
1.0
2.5
25
10
0.50
1.0
1.5
5.0
1.0
0.50
2.5
0.10
1.5
1.0
0.50
Amt in
Blank,
ug/L n(b)
ND(f)
ND
0.0373
ND
1.33
ND
.ND
ND
0.0130
ND
ND
ND
0.121
0.0227
0.0313
0.0207
0.0132
6
6
6
6
6
6
6
6
6
6
5
6
6
6
6
6
6
R(c)
89
90
89
94
82
55
50
87
101
90
31
85
93
82
82
90
90
S(d)
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
RSD(e)
12
22
15
13
12
12
26
8
9
12
40
13
11
9
16
10
13
(a) Data corrected for amount detected in blank.
(b) n = number of recovery data points.
(c) R = average percent recovery.
(d) S — standard deviation.
(e) RSD - percent relative standard deviation.
(f) ND = interference not detected in blank.
(g) Results from confirmatory analysis conditions,
28
-------
TABLE 7. RECOVERY OF ANALYTES FROM REAGENT WATER (SPIKING LEVEL 5) (a)
Analyce
Acifluorfen
Bentazon
Chloramben (g)
2,4-D
Dalapon
2,4-DB (g)
DCPA diacid metabolite
Dicamba
3 , 5-Dichlorobenzoic acid
Dichlorprop
Dinoseb (g)
5 -Hydroxydicamba
4-Nitrophenol
PCP
Picloram
2,4,5-T
2,4,5-TP (g)
Spiking
Level ,
ug/L
2.0
10
4.0
10
100
40
2.0
4.0
6.0
20
4.0
2.0
10
0.40
6.0
4.0
2.0
Amt in
Blank,
ug/L
ND(f)
ND
ND
ND
1.77
ND
ND
ND
ND
ND
ND
ND
ND
0.0664
ND
ND
ND
n(b)
6
6
6
6
6
6
6
6
6
6
6
6
6
6
5
6
6
R(c)
90
80
55
74
81
59
23
79
88
78
74
67
73
73
73
77
84
S(d)
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
RSD(e)
4
13
4
6
5
5
74
4
6
4
9
13
5
6
12
6
5
(a) Data corrected for amount detected in blank.
(b) n = number of recovery data points.
(c) R = average percent recovery.
(d) S = standard deviation.
(e) RSD = percent relative standard deviation.
(f) ND = interference not detected in blank.
(g) Results from confirmatory analysis conditions.
?9
-------
TABLE 8. RECOVERY OF ANALYTES FROM HARD ARTIFICIAL GROUND WATER
(SPIKING LEVEL 3) (a)
Analyte
Acifluorfen
Bentazon
Chloramben (g)
2,4-D
Dalapon
2,4-DB (g)
DCPA diacid metabolite
Dicamba
3 , 5-Dichlorobenzoic acid
Dichlorprop
Dinoseb (g)
5-Hydroxydicamba
4-Nitrophenol
PCP
Picloram
2,4,5-T
2,4,5-TP (g)
Spiking
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
Amt in
Blank,
ug/L
ND(f)
ND
0.0157
0.0100
ND
ND
0.0200
ND
0.0650
0.0251
ND
0.0224
0.100
0.0177
ND
0.0419
ND
n(b)
5
5
7
5
5
7
5
6
6
5
5
5
7
7
5
5
6
R(c)
103
82
112
110
128
(h)
81
92
82
106
89
88
127
84
97
96
105
S(d)
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
RSD(e)
20
46
9
5
24
-
27
19
9
5
15
6
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 Water
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) RSD - percent relative standard deviation.
(f) ND = interference not detected in blank.
(g) Results from confirmatory analysis conditions.
(h) Analyte not recovered from hard artificial ground water.
30
-------
TABLE 9. RECOVERY OF ANALYTES FROM ORGANIC-CONTAMINATED ARTIFICIAL
GROUND WATER (SPIKING LEVEL 3) (a)
Analyte
Spiking Amt in
Level, Blank,
ug/L ug/L n(b)
R(c) S(d) RSD(e)
Acifluorfen
Bentazon
Chloramben (g)
2,4-D
Dalapon
2,4-DB (g)
DCPA diacid metabolite
Dicamba
3 ,5-Dichlorobenzoic acid
Dichlorprop
Dinoseb (g)
5 -Hydroxydicamba
4-Nitrophenol
PCP
Picloram
2,4,5-T
2,4,5-TP (g)
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
ND(f)
ND
ND
ND
ND
ND
0.00857
0.0740
ND
ND
ND
ND
0.0380
0.0137
0.197
0.00343
ND
7
7
7
7
7
7
7
7
7
7
5
7
7
5
7
7
5
110
111
104
112
109
79
78
107
96
106
71
102
118
133
86
108
108
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
0.028
11
8
12
8
11
19
11
5
5
5
13
6
9
6
6
6
13
(a) Data corrected for amount detected in blank; organic-contaminated
artificial ground water used to generate these results was reagent
water spiked with humic acid at the 1 mg/L concentration level. Humic
acid (sodium salt) obtained from Aldrich (HI,675-2) was used.
(b) n - number of recovery data points.
(c) R - average percent recovery.
(d) S - standard deviation.
(e) RSD — percent relative standard deviation.
(f) ND - interference not detected in blank.
(g) Results from confirmatory analysis conditions.
31
-------
TABLE 10. QUALITY CONTROL STANDARD
Test
Sensitivity
Chromatographic performance
Colum performance
Analyte
D i noseb
4-Nitrophenol
3,5-Dichtorobenzoic acid
4-Nitrophenol
Cone,
g/L
0.004
1.0
0.6
0.4
Requirements
Detection of analyte; S/N > 3
0.90 0.95 (c)
(a) PSF = peak symnetry factor. Calculated using the equation:
PSF =
0.5 x Wd/2)
where w(1/2) is the width of the front of the peak at half height assuming the peak is split at the
highest point and WO/2) is the peak width at half height.
(b) PGF = peak Gaussian factor. Calculated using the equation:
1.83 x WC1/2)
PGF =
WC1/10)
where Wd/2) is the peak width at half height and Wd/10) is the peak width at tenth height.
(c) Resolution between the two peaks as defined by the equation:
where t is the difference in elution times between the two peaks and W is the average peak width, at the
baseline, of the two peaks.
32
-------
TABLE 11. PRESERVATION STUDY RESULTS
Day Extracted
Day Analyzed
Ana lyre
Acif luorfen
Bentazon
Chloramben(c)
2,4-D
Dalapon
2,4-DB
-------
Figure 1
Nitrogen
Tubel
Tube 2
Sample
Tube
-------
Figure 2
c
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-------
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36
-------
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39
-------
Appendix B
Revision No. 8
Date. September 10, 1990
Page 1 of 5
APPENDIX B
FORMAT FOR NPS DATA FILES
-------
FORMAT FOR NFS INSTRUMENT CONTROL DATA
2
3-7?
COLUMNS DESCRIPTION
1-3 Lab
6-11 Method
14-21 Date Ana
24-30 Analyst
35-37 S/N
42-4* PSF
49-51 PGF
55-58 Res.
BLANK
1-3 enter LAB ABBREVIATION (JMM)
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
-------
Format for National Pesticide Survey (NFS) Data
(cont.)
LINE COLUMNS DESCRIPTION
10 1-4 Type
8-13 Spiker
16-22 Extract
25-31 Analyst
34-40 Sam Vol
43-49 Ext'Vol
52-60 IntT Std.
65-70 X Surr
11 1-5 enter SAMPLE TYPE
8-13 enter SPIKER'S INITIALS
16-22 enter EXTRACTOR"* INITIALS
25-31 enter ANALYST'S INITIALS
34-40 enter VOLUME OP SAMPLE
43-49 enter VOLUME OF EXTRACT
52-62 enter INTERNAL STANDARD
65-70 enter PERCENT RECOVERY OP SURROGATE
12 BLANK
13 1-8 Comments
14 1-80 enter ANY PERTINENT COMMENTS ON SAMPLE AND ANALYSIS
15 BLANK
16 1-7 Analyte
29-33 Cone.
39-45 Analyte
67-71 Cone.
17-7? 1-25 enter ANALYTE'S NAME
28-34 enter CONCENTRATION OR PERCENT RECOVERY
39-63 enter ANALYTE'S NAME
66-72 enter CONCENTRATION OR PERCENT RECOVERY
-------
NOTES ON NFS FORM,.!
1) The format for any date is mm/dd/yy. A m ssing date should be entered as
01/01/60.
2) The format for any time is hh:mm is 24 hou. format. A missing time should
be 00:00.
3) Any other data that is missing should be e: tered vith a period (.)•
4) The number of decimal places should be as ollovs:
Concentration 3 (significa: t figures)
Percent Recovery 1
Internal Standard 1 (percent r- covery)
Instrument Controls 2
pfl 1 (method 9 • nly)
Temperature 0
Volumes 0
5) The code for columns is as follovs:
Primary PRIM
Confirmatory CONF
Third GCMS
6) The laboratory code for Montgomery is JMM
7) The codes for Type are as f ollovs:
Field sample SAMP
Shipping blank SBLT
Method blank MBLK
Lab control standard LCS?
Lab spike sample LSSgf
Time storage extract day 14 BTE9
Time storage sample day 14 BTS9
Time storage sample day 0 DTS9
vhere @ is the mix letter (A, B, C)
and t is the spiking level (0, 1, ,or 3)
8) There should be at least one blank line between samples in the NFS data
file.
-------
9) The codes for Concentration and Percent Re- overies are as follows:
Not Analyzed . (period)
Not Detected (< 1/2 MRL) -999
Saturated -777
Compound failed LCS but positive by GC S -666
Compound failed LCS but negative -444
Compound failed LCS but postive,
no confirmation needed (spiked) -333
> 1/2 MRL but < MRL, not conf -222
> 1/2 MRL but < MRL, conf not needed -222
> 1/2 MRL but < MRL, conf by GCMS -111
Above MRL but not quantified 888
(as for GCMS or qualitative cmpds)
10) If a reported value is greater the (>) s- me number in the NFS instrument
control data, then use a minus sign (-) in. tead of >.
-------
Appendix C
Revision No. 8
Date. September 10, 1990
Page 1 of 5
APPENDIX C
MASS IONS FOR GCMS CONFIRMATION
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Appendix D
Revision No 8
Date- September 10, 1990
Page 1 of 5
APPENDIX D
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:
X: < X2 < X3 < ... < X,,.! < X,,
2) Decide whether the smallest, XL or the largest, X,,, is
suspected to be an outlier.
3) Select the risk you are willing to take for false rejection.
For use in this QAPP we will be using a 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
ru - - - 0.454
10.58 - 10.47 0.11
2) A 5% risk of false rejection (Table 2), rn - 0.477
3) Therefore there is no reason to reject the value 10.58.
4) Note that at a 10X risk of false rejection rn - 0.409, and the value
10.58 would be rejected.
-------
TABLE 1
CALCULATION OF RATIOS
For use if
Ratio n is between
•v-.. 3 . 7
if X,, is
suspect
v. • *,,>
if Xj is
suspect
-------
TABLE 2
VALUES FOR USE WITH THE DIXON TEST FOR OUTLIERS
Risk of False Rejection
n 0.5% 1% 51 10%
•10
L21
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
0.994
0.926
0.821
0.740
0.080
0.725
0.677
0.639
0.713
0.675
0.649
0.674
0.647
0.624
0.605
0.589
0.575
0.562
0.988
0.889
0.780
0.698
0.637
0.683
0.635
0.597
0.679
0.642
0.615
0.641
0.616
0.595
0.577
0.561
0.547
0.535
0.524
0.514
0.505
0.497
0.489
0.941
0.765
0.642
0.560
0.507
0.554
0.512
0.477
0.576
0.546
0.521
0.546
0.525
0.507
0.490
0.475
0.462
0.450
0.440
0.430
0.421
0.413
0.406
0.806
0.679
0.557
0.482
0.434
0.479
0.441
0.409
0.517
0.490
0.467
0.492
0.472
0.454
0.438
0.424
0.412
0.401
0.391
0.382
0.374
0.367
0.360
Note that for this QAPjP the 5% risk level will be used for ratio r22.
-------
Reference:
John K. Taylor, Quality Assurance of Chemical Measurements. Lewis
Publishers, Chelsea, MI, 1987.
-------
Chaptir 7
DATA HANDLING AND REPORTING
7.1 Introduction
To obtain meaningful data on water quality, the sample collector mist obtain
representative sample and then deliver it unchanged for analysis. The analyst must perfor
the proper analysis in the prescribed fashion, complete calculations, and convert results 1
final form for permanent recording of the analytical data in meaningful, exact terms. The:
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 \
the proper way, some means of quality control of data, and the storage and retrieval of dat
7.2 Thi Analytical Vilui
7.2.1 Significant Figure
The term "significant figure" is used, sometimes rather loosely, to describe a judgment
the reportabie digits in a result. NVhen the judgment is not soundly based, meaningful dig!
are lost or meaningless digits are reported. On the other hand, proper use of sigmfica
figures gives an indication of the reliability of the analytical method used.
The following discussion describes the process of retention of significant figures.
A number is an expression of quantity. A figure or digit is any of the characters 0, 1,2, 3,
S, 6, 7, 8, 9, which, alone or in combination, serve to express a number. A significant figu
is a digit that denotes the amount of the quantity in the particular decimal place in which
stands. Reported analytical values should contain only significant figures. A value is ma
up of significant figures when it contains all digits known to be true and one last digit
doubt. For example, if a value is reported as 18.8 mg/1, the 18 must be firm while the 0.8
somewhat uncertain, but presumably better than one of the values 0.7 or 0.9 would be.
The number zero may or may not be a significant figure depending on the situation.
Final zeros after a decimal point are always meant to be significant figures. For example,
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
preceding nonzero digit, a zero before the decimal point is not significant.
If there are no nonzero digits preceding a decimal point, the zeros after the decimal po
but preceding other nonzero digits are not significant. These zeros only indicate the positi
of the decimal point.
Final zeros in a whole number may or may not be significant. In a conductiv
measurement of 1,000 ^mho/cm, there is no implication by convention that the conduct
ity is 1,000 *1 ^mho. Rather, the zeros only indicate the magnitude of the number.
7.1
-------
Appendix E
Revision No. 8
Date: September 10, 1990
Page 1 of 3
APPENDIX E
ROUNDING AND SIGNIFICANT FIGURES
-------
Appendix F
Revision No 8
Date September 10, 1990
Page 1 of 13
APPENDIX F
EXTRACTION SOP FOR METHOD 1
-------
When one number is subtracted from another, rounding off should be completed after the
subtraction operation, to avoid possible invalidation of the operation.
When two numbers are to be multiplied, aii digits are earned through the operation, (hen
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 earned out on the two numbers using
all digits. Then the quotient is rounded off to the number of significant digits of the divisor
or dividend, whichever has the fewer.
When a number contains n significant digits, its root can be relied on for n digits, but us
power can rarely be relied on for n digits.
7.2.2.3 Rounding Off the Results of a Scries of Arithmetic Optritions
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 senes 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.
7.3 Glossary of Statistical Terms
To clarify the meanings of statistical reports and evaluations of water quality data, the
following statistical terms are introduced. They are derived in part from usage (1,2) of the
American Society for Quality Control.
Accuracy-The difference between an average value and the true value when the latter is
known or assumed.
Arithmetic mean-The arithmetic mean (or average) of a set of n values is the sum of the
values divided by n:
Bias-A systematic error due to the experimental method that causes the measured values to
deviate from the true value.
Confidence limit. 95 percent-The limits of the range of analytical values within which a
single analysis wdl be included 95 percent of the time.
95 percent CL * X t 1. 96S
where CL is the confidence level and S is the estimate of the standard deviation.
7-3
-------
SOP#:
Revision
Page:
Date:
NFS- 1
2
2 of 9
3/5/90
EXTRACTION NPS-1
LIQUID-LIQUID EXTRACTION
Scope and Application
This procedure can be used to measure certain nitrogen- and phosphorous-containing
pesticides. The following compounds can be determined using this method:
Alachlor
Ametryn
Atratph
Atrazine
Bromacil
Butachior
Butyiate
Carboxin
Chlorpropham
Cycloate
Demeton-S
Diazinon
Dichlorvos
Diphenamid
Disulfoton
Disulfoton sulfone
Disuifoton sulfoxide (c)
EPTC
Ethoprop
Fenamiphos
Fenarimol
Fl undone
Hexazinone
Merphos
Methyl paraoxon
Metoiachlor
Metribuzin
Mevinphos
MGK264
Molinate
Napropamide
Norflurazon
Pebulate
Prometon
Prometryn
Pronamide
Propazine
Simazine
Simetryn
Stirofos
Tebuthiuron
Terbacil
Terbufos
Terbutryn
Triademefon
Tricyclazole
Vemolate
This is a capillary gas chromotographic method.
Method Summary
A measured volume of approximately I L is solvent extracted with three portions of
methylene chloride. The methylene chloride extract is isolated, dried, and
concentrated to 5 ml after solvent substitution with MTBE. Separation and
measurement of the analytes is done by capillary GC with a nitrogen-phosphorous
detector.
-------
EXTRACTION NPS-1
Page
Revision #
Approved:
2
3
4
5
6
7
8
9 (last)
Group Leader:
QA Officer:
Laboratory Director:
Revision Date
•)
L.
1
1
1
1
^
1
I
I
1
;r:
Manager:
March 5.
March 5.
October 3 1 .
October 3 1 .
March 5.
October 3 1 .
October 3 1 .
October 3 1 .
October 3 1 .
1990
1990
1989
1989
1990
1989
1989
1989
1989
-------
SOP#: NPS-1
Revision #: 2
Page: 4 of 9
Date: 3/5/90
Reagents and Standards
I) Reagent water, organic-free
2) SodFum Sulfate - Anhydrous. ACS Certified. Baked @ 400°C for four
hours.
3) Acetone - Burdick and Jackson or equivalent
4) HC1 - ACS certified. Make O.I N HC1 by slowly adding 8.3 ml
concentrated HC1 to 900 ml DI and diluting to I L with DI.
5) Dipotassium phosphate - ACS grade. Make 0.1 M K,PO4 by diluting
17.42 g K:PO,to 1 L with DI.
6) Phosphate "buffer. pH 7 - Prepare by mixing enough solution at a ratio
of 29.6 ml 0.1 N HC1 to 50 ml 0. f M dipotassium phosphate to make
a total of 50 ml per sample (for example, for 14 samples use 266 ml
0.1 N HC1 and 450 ml 0.1 M K,POj.
7) 2-Nitrotoluene - Aldrich neat - internal standard
8) MTBE (methyl-ten-butyl-ether) - 99.9% EM Science
9) Methylene chloride - Pesticide quality or equivalent
10) 1.3-Dimethyl-2-nitro-m-benzene - AJdrich neat - surrogate standard.
ID Sodium Chloride, crystal. ACS certified. Baked @ 400°C for four
hours.
New spike solutions should be compared to old ones by the analyst. Values
should agree within 10%. If not. prepare new standards and compare all
three. If the two new ones agree the old solution may have been incorrect or
may have deteriorated. If the last solution agrees with the old one use it and
discard the other.
Sample Collection, Handling and Preservation
I) Samples are collected in 1 L amber glass bottles with Teflon septa.
2) Samples should be packed in ice and shipped to the laboratory for next
day delivery.
3) Samples should be extracted within 14 days of collection and analyzed
within 14 days of extraction.
Calibration Procedure
1) Reagent and extraction blanks are included in each analytical run.
2) An LCS standard for each ot the three mixes is extracted each day with
each set of samples.
Extraction Summary
Aqueous samples are extracted three times with 60 ml portions of methylene chloride
at a pH of 7. The extract is dried with sodium sulfate and concentrated to 5 mis
with a Kudema-Danish apparatus. The extract is solvent exchanged twice with
MTBE and taken to a final volume of 5 mis.
-------
SOP#:
Revision #
Page:
Date:
NP^
2
3 of 9
3/5/90
Interferences
Method interferences may be caused by contaminants in solvents, reagents, and
glassware: laboratory reagent blanks must be run in order to demonstrate that these
materials are free from interference.
Matrix interferences may be caused by contaminants that are co-extracted from the
sample.
Methylene Chloride enhances detector response of internal standard: the procedure
for the solvent exchange must be followed carefully.
Do not use PVC or rubber gloves.
Use only baked glassware and teflon screw caps: do not use plastic or rubber
materials.
Safety Considerations
The extent of toxicity or carcinogenicity of all of the reagents used has not yet been
precisely determined: however, each compound should be treated as hazardous.
There is' a file of material safety data sheets (MSDS) in the lab available to all. The
technician must familiarize him/herself with these before beginning the extraction.
Apparatus
I) Sample container - 1 L glass bottle uith Teflon faced septum and open
top screw cap.
2) Separatory funnel - 2 L. with teflon stopcock.
3) Water bath - heated, with concenetric ring cover, capable of
temperature control within 2°C. Should be in a hood.
4) Volumetric flask - 5 ml with glass stopper
5) 5 ml vial, with teflon-lined screw cap
6) 500 ml Erlenmeyer flask.
7) 500 ml Kuderna-Danish concentration apparatus
8) 1 L graduated cylinder.
9) 100 ml graduated cylinder.
-------
SOP#: NFS-1
Revision #: 2
Page: 5 of 9
Date: 3/5/90
Extraction Procedure
See special notes before beginning extraction procedure.
1) Prepare the log book, recording the following:
a) Sample number
b) Spike & Surrogate:
!)Amount 4HD Numbers
2)Preparers 5)Injector's initials
3)Date prepared
c) Weights!Initial.final.& net) of each sample
d) Lot # of chemicals used
e) NPS Set #
f) Date extracted
g) Initials of ones performing the extraction
2) Prepare the labels, recording on each the following:
a) NPS Set #
b) Sample #
c) Net weight
d) Final volume in MTBE
e) Date extracted
f) Initials of ones performing the extraction
3) Prepare a blank by adding 1000 ml Dl to a 2 L separator/ funnel with
a I L graduated cylinder: in a similar method, prepare one of each type
(a.b.& c) of LCS (laboratory control sample) for every set tested.
4) Dry the sample bottle: weigh and record the full bottle.
5) Check the pH of each sample: record in the log book if not pH 7.
6) Add 100 g NaCI and 50 ml phosphate buffer to each sep funnel.
7) Add 50 ul surrogate into each bottle (funnel for LCS and blank): record
the solution in the log book, including the number, amount used.
preparer. and the person adding the surrogate.
8) Add the spike solutions to the LCS standards and spike samples (see
Special Notes for amounts). Record the solutions in the log book.
including the number, amount used, preparer. and the person who
added the spike standards.
9) Add the sample to a 2 L separator* funnel: mix.
10) Check the pH. Adjust to pH " \( necessary. Record all adjustments in
the log book.
II) Add 60 ml methylene chloride to each sample bottle, seal, and shake
for 30 seconds. Pour the meth\lene chloride into the funnel, seal, and
swirl vent. Extract the sample bv shaking for 2 min. Allow the layers
to separate for at least 10 mm: dram the methylene chloride layer into
a 500 ml erlenmeyer flask. If there is an emulsion more than 1/3 the
volume of the solvent laver. the separation should be completed by
mechanical techniques such as re-?ep funneling. Record any emulsions
or extraction difficulties.
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SOP#: NPS-1
Revision #: 2
Page: 6 of 9
Date: 3/5/90
12) After allowing the methylene chloride to evaporate re-weigh the sample
bottle and record the weight.
13) Repeat the extraction procedure a second and third time, shaking for
only one minute. A minute before the third drain, swirl the funnel in
an upright position in order to ensure that all the MeCl, is in the lower
layer. Collect the extracts in a 500 mi erienmeyer flask."
14) Add "20 g anhydrous sodium sulfate to the extract and let sit for 20
min.
15) Assemble a K-D apparatus. Add 15 ml MTBE into the receiver.
16) Decant the extract into the K-D apparatus. Rinse the flask with two
30-ml portions of methylene chloride.
17) Add a boiling chip to the flask and attach a Snyder column. Place the
apparatus on a hot water bath @ 75-76°C so that the tube is partially in
the water. Concentrate to 3 ml and allow to drain and cool for 10 min.
Rinse the lower joint of the K-D with 0.5 ml MTBE.
18) Add a new boiling chip. 10 ml MTBE and attach a micro-snyder
column. Pre-wet the column and boil down to I ml at 75-76°C. gently
tapping the column until smooth boiling is attained to prevent
bumping. Let cool for 10 minutes.
19) Add a new boiling chip and 15 ml MTBE. Concentrate to 1 ml at
75-76°C. remembering to gently tap the column until there is smooth
boiling in order to prevent bumping.
20) Cool 10 minutes.
21) Rinse a 5 ml volumetric 3 times with acetone. 3 times with methylene
chloride, and 4 times with MTBE. Transfer the extract to the solvent-
cleaned 5 ml volumetric. Rinse the receiver with MTBE and transfer to
the volumetric while adjusting the final volume to 5 mis. Mix
thoroughly with a pipette and transfer to a 5 ml vial with a teflon liner.
Quality Control Requirements
1) The LCS. spike, and surrogate recovery should be within control limits.
If not. investigate.
2) A blank and one of each LCS should be prepared for each set of
samples.
3) Surrogate standard must be added to all samples.
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SOP#: NFS-1
Revision #: 2
Page: 7 of 9
Date: 3/5/90
Calculations see GC protocol
Special Notes
I) Spike levels: There are three spike levels used in this method:
Level 0 - 200 uI
Level 1 - 500 ul
Level 2 - 1.0 ml
Each LCS sample receives 1 ml spike solution (level 2).
2) Time Storage Samples (TS) : 5 duplicates of a sample are made.
There is one original and two spikes
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SOP#: NFS-1
Revision #: 2
Page: 8 of 9
Date: 3/5/90
5) Numbering Convention tor Samples:
Public comm. Site # Lab # Method Type'
Public domes. (JMM=1) num.
PC - 2497 - 1 - 3 - 01
' Types:
a) 01 Field sample d)!3 T.S. 0 day dup.
b) 03 Backup sample e»!4 T.S. 14 day(HTS)
c) 04-12 Spike sample f)l5 T.S. 14 day dup
(HTS dup)
6) Make sure that the septa ot the \iais is turned so that the teflon side is
on the inside of the cap!
7) A florisil(R) check is a comparison of a florisiled DMS A and B with an
unflorisiled DMS A and B. Do a tlorisil(R) check in the following
method:
a) Activate the florisil(R) by baking @ 150°C for 24-48 hrs prior
to the day of extraction. Record the activation date on the label
and in the standards book. Store in a dessicator. and reactivate
every 2 weeks. When a new batch of florisil(R) is activated, a
florisil(R) check is required.
b) Prepare an unflorisiled DMS A and B by spiking 0.5 ml
standard into a receiver for each DMS. Prepare a DMS A and
B for florisiling by spiking 0.5 ml standard into two other
receivers. Add 250 ul high purity methanol to each receiver.
Add 0.5 ml diazomethane. and dilute to 3 ml with MTBE. and
mix well.
c) Cover each receiver uith foil and allow to react for 1 hour. If
not yellow after ~IO minutes, remethylate by adding
diazomethane in 0.5 ml increments until it does stay yellow for
10 minutes. Note ihe remeth\lation in the tog book.
d) Slowly blow off (he diazomethane with a gentle stream of
nitrogen.
e) Adjust the DMS's to 4 ml \xith 99.9^ MTBE.
f) Assemble two columns to florisil two DMS's. Place a small
plug of acidified glass uool into a 5 mi pipette. Tare the
pipette and add I g acmaied florisiUR) into the pipette. Record
the florisiUR) test m the extraction log book, stating the lot
number and acmanon date of the florisil(R). Also record the
DMS standard numhcrv preparation date, amount used, and
initials of the injector
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SOP#: NFS-1
Revision #: 2
Page: 9 of 9
Date: 3/5/90
g) Add 5-10 ml of 5% MeOH in MTBE to each column. Do not
let the column go dry. Discard the eluate.
hi Apply each DMS to be florisiled (one of A and one of B) to a
column. Collect the eluate in a 10 ml volumetric. Do not let
the column go dry.
i) Rinse the receiver with 1 ml 5% MeOH in MTBE. and transfer
to the florisil(R) column. Repeat with another 1 ml 5% MeOH
in MTBE: again repeat, this time with 3 mi 5% MeOH in
MTBE.
j) Dilute to 10 ml with 5CTc MeOH in MTBE. mix with a pipette.
and transfer to a 10 ml vial with a teflon(R) septum.
8) The glassware must be acid-washed in the following manner:
a> Clean the glassware by rinsing once with the last solvent used in
it and washing with hot \vater~and detergent.
b) Dip once in a'bath of 0.8 N HC1.
c) Rinse three times with tap water.
d) Rinse three times with reagent water. Drain dry.
e) Seal with foil, and bake (2> 400°C for 4 hours. "Allow to cool.
9) Spike solution testing:
New spike solutions should have been compared to old ones by an analyst
before they are used as standards. These standards should be methylated by
the following procedure:
a) Obtain 2 acid-washed, baked receivers for each standard to be tested.
b) Spike 1 ml of the old standard into one receiver: into the other spike 1
ml of the new standard. Label the receivers with the correct solution.
amount, date, preparer. and tester.
c) Add 250 ul high purity MeOH into each receiver.
d) Add 0.5 ml diazomethane: dilute to 3 ml with 99.9% MTBE. Mix well.
cover with foil, and allow to react for one hour.
e) Blow off the yellow solution with a gentle stream of nitrogen.
f) Adjust the volume to 4 ml with 99.9% MTBE.
gj FIorisil(R) the sample by following the procedure in Step 27 of
Extraction Procedure.
h) Dilute to 10 ml with 5% MeOH in MTBE. mix with a pipette, and
transfer to a 10 ml vial with a teflon)R> septum.
i) Record the lot numbers and preparation dates of all chemicals used in
the log book, and send the samples to the analyst to be tested.
The analyst should compare the old and new solutions. The values should
agree within 20%. If not. the analyst should prepare new standards and
compare all three. If the two new ones agree, the old solution may have beerr
incorrect or may have deteriorated. If the last solution agrees with the old one
use it and discard the other.
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SOP#:
Revision ft'.
Page:
Date:
NPS-1
2
10 of 9
3/5/90
10) DMS Testing
New DMS standards should have been compared to old ones by an analyst
before they are used as standards. These standards should be methylated by
the following procedure:
a) Obtain 2 acid-washed, baked receivers for each standard to be tested.
b) Spike 0.5 ml of the old standard into one receiver: into the other spike
0.5 ml of the new standard. Label the receivers with the correct
solution, amount, date, preparer. and tester.
c) Add 250 ul high purity MeOH into each receiver.
d) Add 0.5 ml diazomethane: dilute to 3 ml with 99.9% MTBE. Mix well.
cover with foil, and allow to react tor one hour.
e) Blow off the yellow solution with a gentle stream of nitrogen.
f) Adjust the volume to 4 mi with ^ 0% MTBE.
g) Dilute to 10 ml with 5% MeOH in MTBE. mix with a pipette, and
transfer to a 10 ml vial with a tefloniR) septum.
h) Record the lot numbers and preparation dates of all chemicals used in
the log book, and send the samples to the analyst to be tested.
The analyst should compare the old and new solutions. The values should
agree within 20%. If not. the anahst should prepare new standards and
compare all three. If the two new ones agree, the old solution may have been
incorrect or may have deteriorated. It the'last solution agrees with the old one
use it and discard the other.
11) Diazomethane check:
1) Obtain four acid-washed receivers free of scratches or cracks. Label
one "blank", and the others 'PNP IV'PNP 2". and "PNP 3".
2) Add I ml MTBE to each receiver
3) To each PNP sample, add 25 ul PNP standard: to all samples, add 250
ul high-purity MeOH.
4) Add 0.5 ml newly-made diazomeihane to each sample. Adjust the
volume to 3 ml with 99.9CTc MTBE.
5) Mix. cover, and allow to react tor one hour. Record all lot numbers of
solutions used. PNP standard mtormaiion. diazomethane preparation
date, and preparer's initials m the NPS 3 log book.
6) Blow off the diazomethane -nth a gentle stream of nitrogen until the
solution is clear.
7) Adjust the volume to 4 ml .\\nh Q0 Qf~<- MTBE.
8) Bottle each sample, taking them 10 10 ml with 5% MeOH in MTBE.
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SOP#: NFS-1
Revision #\ 2
Page: 11 of 9
Date: 3/5/90
QUICK SUMMARY
PREPARATIONDr\- the sample bottles: weigh and record full weights.
Add 50 ul surrogate into each sample: spike LCS and recovery.
Add 100 g NaCl: mix.
Add 50 ml phosphate buffer. pH 7.
Pour the sample into a 2 L separatory funnel.
Remove stopper and rinse with DI.
EXTRACTION Extract 3X with 60 ml MeCl, (2 min first shake. 1 min other
shakes. Add MeCK to sample bottle, rinse walls, and
transfer to sep funnel.
Remove stopper, rinse with DI.
Dry extract with "20 g Na,SO4 for 20 min.
Weigh empty bottle: record empty and net weights.
CONCENTRATION Add 10 ml MTBE into the receiver as a keeper. Decant
extract into K-D. Rinse flask and Na:SO4 twice with 30 ml
portions of MeCU.
Prewet and concentrate to 3 ml @ 75°C.
Cool 10 minutes: rinse joint with 1 ml MTBE.
Add 10 ml MTBE and I boiling chip. Attach micro-snyder.
prewet with MTBE. and concentrate to 1 ml @ 75PC. Remove and
cool for 10 minutes.
Add 15 ml MTBE. prewet. and concentrate to 1 ml. Cool for
10 minutes, and rinse joint with 0.5 ml MTBE.
Transfer to a 5 mi volumetric. Mix and transfer to a 5 ml vial.
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SOP#: NPS-1
Revision #: 2
Page: 12 of 9
Date: 3/5/90
SOLUTIONS
Q.I N HC1: 8.3 mi HCL to 1 L with DI
0.1 M Dipotassium Phosphate: 17.42 g K:PO4 to 1 L with DI
Buffer:
* of samples: 10 12 14 16 18 20
0.1MK;PO4: 350 400 450 550 600 700
0.1NHC1: 207 237 266 325 355 414
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APPENDIX G
EXTRACTION SOP FOR METHOD 3
Appendix G
Revision No 8
Date: September 10, 1990
Page 1 of 15
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Appendix G
Revision No 8
Date: September 10, 1990
Page 2 of 15
Approved:
Group Lea<
Operations
QA Officer:
Laboratory
Paae
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15 (last)
Hpr
Manager
Direntnr
EXTRACTION - NPS 3
Revision #
2
2
1
1
1
2
1
1
1
1
1
1
1
1
1
Revision Date
March 5, 1990
March 5, 1990
November 6, 1989
Novembers, 1989
November 6, 1 989
March 5, 1990
November 6, 1989
Novembers, 1989
Novembers, 1989
Novembers, 1989
November 6, 1989
November 6, 1989
November 6, 1 989
November 6, 1989
November 6, 1989
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Appendix G
Revision No. 8
Date- September 10, 1990
Page3 of 15
EXTRACTION NPS-3
LIQUID-LIQUID EXTRACTION
Scope and Application
This procedure can be used to measure certain chlorinated acids in ground water. The
following compounds can be determined using this method:
Acifluorfen
Bentazon
Chloramben
2,4-D
Dalapon
2,4-DB
DCPA acid metabolites
Dicamba
3,5-Dichlorobenzoic acid
Dichlorprop
Dinoseb
5-Hydroxydicamba
4-Nitrophenol
PCP
Picloram
2,4,5-T
2,4,5-TP
This method may be used to determine the salts and esters of the above acids. The acid derivatives
are indistinguishable from each other; results are listed as the total free acid.
This is a capillary gas chromatographic method.
Method Summary
Aqueous samples of approximately 1L are made basic with 6N NaOH and allowed to sit for 1 hr
to hydrolyze derivatives. They are then extracted with methylene chloride in order to remove
extraneous material. The samples are acidified, concentrated, and then extracted with ethyl ether.
The acids are dried and converted to their methyl esters with the use of diazomethane. Excess
diazomethane is removed, and the esters are determined by capillary GC using an electron capture
detector.
Interferences
Method interferences may be caused by contaminants in solvents, reagents, and glassware;
laboratory reagent blanks must be run in order to demonstrate that these materials are free from
interference.
Matrix interferences may be caused by contaminants that are co-extracted from the sample;
florisil cleanup may be used to remove many of these interferences.
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Appendix G
Revision No. 8
Date. September 10, 1990
Page 4 of 15
Do not use PVC or rubber gloves. Let no plastic or rubber materials be used in the procedure.
Use acid-washed, baked glassware and teflon(R) caps only.
Safety Considerations
The extent of toxicity or carcinogenicity of all of the reagents used has not yet been precisely
determined; however, each compound should be treated as hazardous. There is a file of material
safety data sheets (MSDS) in the lab available to all.
Diazomethane is a toxic carcinogen which is explosive. Use only in a well-ventilated hood with a
safety screen. Do not heat above 70oC, avoid contact with ground or scratched glass surfaces, and
do not store with alkali metals, for an explosion may result. Always keep refrigerated; it is more stable
at cool temperatures.
Ethyl ether is extremely flammable and forms explosive peroxides.
Apparatus
All glassware must be acid-washed and baked. See Note 8 in Special Notes for directions.
1) Sample container - 1L glass bottle with Teflon(R) - faced septum and open top
screw cap.
2) Separatory funnel - 2L, with teflon(R) stopcock.
3) Water bath - heated, with concentric ring cover, capable of temperature control
within 2oC. Should be in a hood.
4) Volumetric flask - 10 ml.
5) Capillary column gas chromatograph with linearized electron capture detector and a
split/splitless injector.
6) Capillary column - Primary column: DBS, 30M x 0.24 mm i.d., 0.25 urn film
thickness.
7) Secondary column: DB1701, 30M x 0.24 mm i.d., 0.25 um film thickness.
8) 10 ml vial, with teflon(R)-lined screw cap.
9) 250 ml Erlenmeyer flask.
10) 500 ml Erlenmeyer flask.
11) 1L Erlenmeyer flask.
12) 500 ml Kuderna-Danish concentration apparatus.
13) Disposable transfer pipettes, with 2 ml bulbs.
14) Glass wool - Acid washed and heated @ 400oC for 4 hours.
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Appendix G
Revision No. 8
Date: September 10, 1990
Page 5 of 15
15) Alumina column - Solvent washed or baked @ 400°C for 4 hrs; for cleaning ether.
16) 5 ml serological pipettes.
17) 1L graduated cylinder.
18) 100 ml graduated cylinder.
19) 25 ml graduated cylinder.
20) Ring stand.
Reagents and Standards
1) Reagent water, organic-free.
2) Sodium Sulfate - Anhydrous, ACS Certified. Acidify by baking @ 400oC in a
shallow glass tray for four hours in the following manner:
a) For each 2 kg Na2SO4, slowly add 20 ml concentrated sulfuric acid to 600 ml
ethyl ether.
b) Add the acidified ether to cover the sodium sulfate and mix thoroughly with a
glass rod.
c) Air dry, and bake @ 400oC for four hours.
d) Mix 1g of the solid with 5 ml Dl and test the pH.
The pH must be below pH 4. Record the pH in the reagent log book.
3) Sodium hydroxide pellets - ACS certified. Make 6 N NaOH by dissolving 240g
NaOH into a total volume of 1L with reagent water.
4) Sulfuric acid - ACS certified. Make 12 N H2SO4 by slowly diluting 333.3 ml H2SO4
into 1L with reagent water in a 1L volumetric flask.
5) Ethyl ether, unpreserved - Nanograde, free of peroxides by cleaning with alumina.
Test a 4L container of ethyl ether for peroxides with a test strip; notify the lab safety
officer if the peroxide content is greater than 5 ppm. If the alumina column is not
baked, solvent-rinse it with acetone and alumina-cleaned ether. To clean the ether,
place a plug of glass wool (which has been baked at 400oC for 4 hours and stored
at iSOoQ in the bottom of an alumina column. Add a stopcock, making sure that
the rubber 0-nng is not exposed, and a florisil(R) tip. Into the tip of the column
place 37g alumina (which has been baked at 400oC for 4 hours, stored at 150oC,
cooled and desiccated before use). Add ether to fill the reservoir and allow 50 ml to
elute; discard the eluate. Place an empty 4L jug under the column. Tie tissue
along the narrow stem of the column in order to absorb spillage during transfer of
ether to the column; cover the open spaces with foil in order to prevent evaporation
and contamination, and collect the rest of the 4L ethyl ether. Record the lot
number, date cleaned, and preparer's initials on the bottle; indicate that the ether is
aluminized by writing (AL) on the bottle. Test the cleaned ether for peroxides with a
test strip; if peroxides are present at a level greater than or equal to 2 ppm, do not
use, and notify the lab safety officer.
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Appendix G
Revision No 8
Date September 10, 1990
Page 6 of 15
6) Diazald(R) - ACS Certified. See "Diazomethane Preparation" protocol for instructions
on preparation of diazomethane. Solution should be prepared and tested before
the day of extraction. This solution is stable for 1 month when stored at 0°C.
7) Sodium chloride - crystal, ACS grade. Bake @ 400oC in a shallow glass tray for 4
hours to remove interfering organics.
8) 4,4'-Dibromooctafluorobiphenyl (DBOB) - > 99% purity, for use as an internal
standard.
9) 2,4-Dichlorophenylacetic acid (DCAA) - > 99% purity, for use as a surrogate
standard.
10) Florisil(R) - 60-100/PR mesh. Activate by heating @ 150oC for 24-48 hpurs; store in
desiccator. Reactivate after two weeks.
11) Acetone - Pesticide quality or equivalent.
12) Methano! - Pesticide quality or equivalent.
13) Methylene chloride - Pesticide quality or equivalent.
14) MTBE (methyl-tert-butyl-ether) - 99.9%, EM Science. VWR Cat # EM-MX0826-1.
15) Basic alumina oxide, activity grade Super 1 (type w 200) - available from Fisher
Scientific, catalog # UA4571.
16) Methanol (high purity, purge & trap grade) - B&J Cat # 232-1DK. for methylation of
samples.
All spike solutions must be replaced after 90 days or earlier if a problem arises.
Sample Collection, Handling and Preservation
1) Samples are collected in 1L amber glass bottles with Teflon(R) septa.
2) Enough mercuric chloride must be added to the sample bottle to produce a
concentration of 10 mg/L. Add 1 ml of a 10 mg/ml solution of mercuric chloride to
the sample.
3) Samples should be packed in ice and shipped to the laboratory for next day
delivery.
4) The samples must be stored at 4oC away from light from the time of collection until
extraction.
5) Samples should be extracted within 14 days of collection and analyzed within 14
days of extraction.
Calibration Procedure
See GC protocol
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Appendix G
Revision No 8
Date: September 10, 1990
Page 7 of 15
Extraction Summary
Aqueous samples of approximately 1L are adjusted to pH 14 with 6N sodium hydroxide and
shaken a few times over a period of one hour to the hydrolyze derivatives. The samples are extracted
3 times with 60 ml portions of methylene chloride in order to remove extraneous organic material. The
samples are then acidified to pH 0 with 12 N H2S04 and extracted 3 times with ethyl ether; the ether
extracts are then dried with sodium sulfate and concentrated to 4 ml with a Kuderna-Danish
apparatus. The extract is solvent exchanged with MTBE and concentrated with a micro-snyder
column to a final volume of 0.5-1 ml.
DMS standards are prepared by spiking 0.5 mis each of DMS standards A and B into separate
vials and diluted to 3 mi with 99.9% MTBE. The samples are then derivatized with 250 ul MeOH and
0.5 ml diazomethane, brought to a volume of 4 ml with 99.9% MTBE, and cleaned with a florisil(R)
column. They are then taken to a final volume of 10 mis.
Extraction Procedure
See special notes before beginning extraction procedure.
Acid wash all glassware before use. See Note 8 in Special Notes for this procedure.
1) Write up the book, noting the following:
a) Sample numbers
b) Spike & Surrogate:
a) Number d) Amount used
b) Date prepped e) Initials of injector
c) Preparer
c) Weights (Initial, final, & Net) of each sample
d) Lot # of each chemical used
e) NPS Set #
f) Date extracted
g) Initials of ones performing the extraction
2) Prepare labels, indicating the following:
a) NPS Set #
b) Sample number
c) Initial weight
d) Final volume in 5% MeOH/MTBE
e) Date extracted
f) Preparers' initials
3) Dry the sample bottle; weigh and record the full bottle.
4) Prepare a blank by adding 1000 ml Dl to a 2 L separatory funnel with a 1L
graduated cylinder; in a similar method prepare one of each type (a & b) of LCS
(laboratory control sample) for every set tested.
5) Add the correct amount of spike standard to the appropriate samples (1 ml into
each of LCS A and B).
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Appendix G
Revision No 9
Date. September 10, 1990
Page 8 of 15
6) Add 50 ul surrogate into the water of each sample bottle (Spike into the sep
funnels for LCS samples and blank). Cap immediately and invert the samples
(Note: check to make sure that the caps are tefJon(R)-lined.
7) Add the sample to a 2 L separately funnel.
8) Add 250 g NaCI to the funnel.
9) Adjust the sample to pH 14 by adding 17 ml 6N NaOH; mix well and check the pH.
Allow the samples to sit for an hour, shaking periodically during that time.
10) Add 60 ml methylene chloride to the sample bottle, seal, and shake 30 sec. Pour
the methylene chloride into the funnel, seal, and swirl vent. Extract the sample by
shaking for 2 min. Allow the layers to separate for at least 10 min; drain the
methylene chloride into a waste container.
11) After allowing the methylene chloride to evaporate from the sample bottle, re-weigh
the sample bottle and record the weight.
12) Repeat the extraction procedure a second and third time, shaking for only one
minute. Discard the MeCI2 extracts. Swirl the funnel after the third shake to make
sure that all the methylene chloride is in the organic layer. Make sure that all the
methylene chloride is drained after the third shake.
13) Adjust the sample to pH 0 by adding 17 ml 12N H2SO4; mix well and check the pH.
14) Add 120 ml alumina-cleaned ethyl ether to the sample. Seal, and swirl vent. Extract
the sample by shaking for 2 min. Allow the layers to separate for at least 10 min.
Remove the aqueous (lower) phase to a 1L and a 250 ml Erlenmeyer flask; collect
the ether in a 500 ml flask.
15) Return the aqueous phase to the separatory funnel. Add a 60 ml portion of AL
ether and extract the sample a second time by shaking for one minute. Combine
the ether in the same flask as before. Perform a third extraction with 60 ml AL ether
in the same manner.
16) Add ~20g anhydrous acidified sodium sulfate to the extract, making sure to contact
the sides of the flask with the solid, and let sit for 2 hours.
17) Weigh the capped empty bottle; record the empty and net weights.
18) Assemble a K-D apparatus.
19) Decant the extract into the K-D apparatus. Rinse the flask with two 30-ml portions
of AL ethyl ether.
20) Add a boiling chip to the flask and attach a Snyder column. Place the apparatus on
a hot water bath @60-65oC so that the tube is partially in the water. Concentrate to
4 ml and allow to drain and cool for 10 mm. Rinse the lower joint of the K-D with
1-2 ml AL ethyl ether. Add 2 ml MTBE.
21) Add another boiling chip and attach a micro-snyder column. Pre-wet the column with
MTBE and boil down to 0.5 ml at 60°C. Lightly tap the receiver until the sample begins to
boil to prevent bumping. Let cool for 10 minutes.
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Appendix G
Revision No. 8
Date September 10, 1990
Page 9 of 15
22) Prepare Direct Methylated Standards (DMS standards). Both DMS standard A and
B must be prepared; they are spiked into separate receivers.
a) DMS A: Spike 0.5 ml (NPS3 underivatized calib. DMS standard A).
b) DMS B: Spike 0.5 ml (NPS3 underivatized calib. DMS standard B).
A florisil(R) check is required of these DMS standards when a new batch of florisil(R)
is activated. In a florisil(R) check, the normal DMS standards are compared to
florisiled DMS standards (both A & B). See Note 7 under Special Notes.
23) Add 250 ul high purity methanol to all samples.
24) Add 0.5 ml diazomethane solution to each sample; record the solution. Adjust the
volume to 3 ml with 99.9% MTBE. Mix well.
25) Cover with foil and allow to react for 1 hour. If not yellow after —10 minutes,
remethylate and note the remethylation in the log book.
26) Slowly blow off the diazomethane with a gentle stream of nitrogen.
27) Adjust the samples to 4 ml with 99.9% MTBE.
28) Florisil(R) all samples except the DMS standards by following this procedure:
a) Assemble the florisil(R) columns. Place a small plug of acidified glass wool
into a 5 ml pipette. Tare the pipette and add 1.0 g activated florisil into the
pipette. Record the flonsil(R) lot number and activation date.
b) Add 5-10 ml of 5% MeOH in MTBE to each column. Do not let the column go
dry. Discard the eluate.
c) Apply the sample to the column. Collect the eluate in a 10 ml volumetric. Do
not let the column go dry.
d) Rinse the receiver with 1 ml 5% MeOH in MTBE, and transfer to the florisil
column. Repeat with another 1 ml 5% MeOH in MTBE; again repeat, this time
with 3 ml 5% MeOH in MTBE.
29) Dilute to 10 ml with 5% MeOH in MTBE, mix with a pipette and transfer to a 10 ml
vial with a teflon(R) septum. Record the lot numbers and preparation dates of all
chemicals used.
Quality Control Requirements
1) The LCS, spike, and surrogate recovery should be within control limits. If not,
investigate.
2) A blank and 1 of each LCS should be prepared with each set of samples.
3) Surrogate standard must be added to all samples.
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Appendix G
Revision No. 8
Date- September 10, 1990
Page 10 of 15
Calculations
See GC protocol.
Special Notes
1) Spike levels: There are three spike levels used in this method:
Level 0 - 200 ul
Level 1 - 500 ul
Level 2 - 1.0 ml
Each LCS sample receives 1 ml spike solution (level 2).
2) Time Storage Samples (TS): 5 duplicates of a sample are made. There is one
original and two spikes (DTS) extracted the same day; the other two samples are
spiked and stored 14 days before extracting (HTS). All are spiked with the same
amount and type of mix. Always add surrogate on the day of extraction.
3) 50 ul surrogate is added to all samples, blank, and LCS.
4) Abbreviations:
MRL minimum reporting level
LCS laboratory control std.
LSS laboratory spike sample
TS time storage
DTS day 0 time storage dup.
HTS holding time storage
ETS Extract time storage
5) Numbering Convention for Samples:
Public comm./ Site # Lab # Method Type*
Public domes. (JMM=1) num.
PC 2497 1 3 01
* Types:
a) 01 Field sample d) 13T.S. 0 day dup.
b) 03 Backup sample e) 14T.S. 14 day (HTS)
c) 04-12 Spike sample f) 15T.S. 14 day dup (HTS dup)
6) Make sure that the septa of the vials is turned so that the teflon side is on the inside
of the cap!
7) A flonsil(R) check is a comparison of a florisiled DMS A and B with an unflorisiled
DMS A and B. Do a flonsil(R) check in the following method:
a) Activate the florisil(R) by baking @ 150oC for 24-48 hrs prior to the day of
extraction. Record the activation date on the label and in the standards book.
Store in a desiccator, and reactivate every 2 weeks. When a new batch of
florisil(R) is activated, a florisil(R) check is required.
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Appendix G
Revision No. 8
Date. September 10, 1990
Page 11 of 15
b) Prepare an unflorisiled DMS A and B by spiking 0.5 ml standard into a
receiver for each DMS. Prepare a DMS A and B for florisiling by spiking 0.5
ml standard into two other receivers. Add 250 ul high purity methanol to each
receiver. Add 0.5 ml diazomethane, and dilute to 3 ml with MTBE, and mix
well.
c) Cover each receiver with foil and allow to react for 1 hour. If not yellow after
~10 minutes, remethylate by adding diazomethane in 0.5 ml increments until
it does stay yellow for 10 minutes. Note the remethylation in the log book.
d) Slowly blow off the diazomethane with a gentle stream of nitrogen.
e) Adjust the DMS's to 4 ml with 99.9% MTBE.
f) Assemble two columns to florisil two DMS's. Place a small plug of acidified
glass wool into a 5 ml pipette. Tare the pipette and add 1 g activated
florisil(R) into the pipette. Record the florisil(R) test in the extraction log book,
stating the lot number and activation date of the florisil(R). Also record the
DMS standard numbers, preparation date, amount used, and initials of the
injector.
g) Add 5-10 ml of 5% MeOH in MTBE to each column. Do not let the column go
dry. Discard the eluate.
h) Apply each DMS to be florisiled (one of A and one of B) to a column. Collect
the eluate in a 10 ml volumetric. Do not let the column go dry.
i) Rinse the receiver with 1 ml 5% MeOH in MTBE, and transfer to the flonsil(R)
column. Repeat with another 1 ml 5% MeOH in MTBE; again repeat, this time
with 3 ml 5% MeOH in MTBE.
j) Dilute to 10 ml with 5% MeOH in MTBE, mix with a pipette, and transfer to a
10 ml vial with a teflon(R) septum.
8) The glassware must be acid-washed in the following manner:
a) Clean the glassware by rinsing once with the last solvent used in it and
washing with hot water and detergent.
b) Dip once in a bath of 0.8 N HCI.
c) Rinse three times with tap water.
d) Rinse three times with reagent water. Drain dry.
e) Seal with foil, and bake @ 400oC for 4 hours. Allow to cool.
9) Spike solution testing: New spike solutions should have been compared to old
ones by an analyst before they are used as standards. These standards should be
methylated by the following procedure:
a) Obtain 2 acid-washed, baked receivers for each standard to be tested.
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Appendix G
Revision No 8
Date: September 10, 1990
Page 12 of 15
b) Spike 1 ml of the old standard into one receiver; into the other spike 1 ml of
the new standard. Label the receivers with the correct solution, amount, date,
preparer, and tester.
c) Add 250 ul high purity MeOH into each receiver.
d) Add 0.5 ml diazomethane; dilute to 3 ml with 99.9% MTBE. Mix well, cover
with foil, and allow to react for one hour.
e) Blow off the yellow solution with a gentle stream of nitrogen.
f) Adjust the volume to 4 ml with 99.9% MTBE.
g) Florisil(R) the sample by following the procedure in Step 27 of Extraction
Procedure.
h) Dilute to 10 ml with 5% MeOH in MTBE, mix with a pipette, and transfer to a
10 ml vial with a teflon(R) septum.
i) Record the lot numbers and preparation dates of all chemicals used in the log
book, and send the samples to the analyst to be tested.
The analyst should compare the old and new solutions. The values should agree
within 20%. If not, the analyst should prepare new standards and compare all three.
If the two new ones agree, the old solution may have been incorrect or may have
deteriorated. If the last solution agrees with the old one use it and discard the
other.
10) DMS Testing: New DMS standards should have been compared to old ones by an
analyst before they are used as standards. These standards should be methylated
by the following procedure:
a) Obtain 2 acid-washed, baked receivers for each standard to be tested.
b) Spike 0.5 ml of the old standard into one receiver; into the other spike 0.5 ml
of the new standard. Label the receivers with the correct solution, amount,
date, preparer, and tester.
c) Add 250 ul high purity MeOH into each receiver.
d) Add 0.5 ml diazomethane; dilute to 3 ml with 99.9% MTBE.
Mix well, cover with foil, and allow to react for one hour.
e) Blow off the yellow solution with a gentle stream of nitrogen.
f) Adjust the volume to 4 ml with 99.9% MTBE.
g) Dilute to 10 ml with 5% MeOH in MTBE, mix with a pipette, and transfer to a
10 ml vial with a teflon(R) septum.
h) Record the lot numbers and preparation dates of all chemicals used in the log
book, and send the samples to the analyst to be tested.
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Appendix G
Revision No. 8
Date: September 10, 1990
Page 13 of 15
The analyst should compare the old and new solutions. The values should agree
within 20%. If not, the analyst should prepare new standards and compare all three.
If the two new ones agree, the old solution may have been incorrect or may have
deteriorated. If the last solution agrees with the old one use it and discard the
other.
11) Diazomethane check:
1) Obtain four acid-washed receivers free of scratches or cracks. Label one
"blank", and the others "PNP 1","PNP 2", and "PNP 3".
2) Add 1 ml MTBE to each receiver.
3) To each PNP sample, add 25 ul PNP standard; to all samples, add 250 ul
high-purity MeOH.
4) Add 0.5 ml newly-made diazomethane to each sample. Adjust the volume to
3 ml with 99.9% MTBE.
5) Mix, cover, and allow to react for one hour. Record all lot numbers of
solutions used, PNP standard information, diazomethane preparation date,
and preparer's initials in the NPS 3 log book.
6) Blow off the diazomethane with a gentle stream of nitrogen until the solution is
clear.
7) Adjust the volume to 4 ml with 99.9% MTBE.
8) Bottle each sample, taking them to 10 ml with 5% MeOH in MTBE.
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Appendix G
Revision No 8
Date: September 10, 1990
Page 14 of 15
QUICK SUMMARY
ACID-WASH ALL GLASSWARE
PREPARATION
BASIC CLEANUP
EXTRACTION
CONCENTRATION
DMS's
Dry and weigh bottle. Add 50 ul (DCAA) surrogate. Invert the bottle
and mix. Spike the LCS and spike samples. Record all solutions.
Pour sample into sep funnel.
Add 250.5+0.4 g NaCI.
Add 17 ml 6 N NaOH to pH 14. Record solution. Mix well.
Shake periodically for 1 hour.
Extract 3X with 60 ml MeCI2. Record lot #. Add MeCI2 to bottle, rinse
walls 30 seconds and transfer to the sep funnel. Shake 2 min.
Discard MeCI2 layer.
Add 17 ml 12 N H2SO4. Record solution. Mix and check that pH<2.
Extract 3X with 120, 60, and 60 ml Al Ethyl Ether. Record lot # date
cleaned, and AL lot #.
Dry extract with -20 g H + Na2SO4 for 2 hours.
Weigh empty bottle; determine and record empty and net weights.
Decant into K-D. Crush and rinse Na2SO4 twice with 30 ml ether.
Prewet and concentrate to 1 ml @ 60oC.
Cool 10 minutes; rinse joints with ether.
Add 2 ml MTBE, attach micro-snyder, prewet with ether, concentrate to
0.5-1.0 ml @ 60oC. Remove and cool 10 minutes.
An unflorisiled DMS A and DMS B is required for every set; when a new
batch of florisil is activated, two florisiled DMS's are compared to the
unflorisiled DMS's.
DMS A - Spike 0.5 ml (NPS 3 underivatized calib. std. A) into a
receiver. Record the spike solution in the book.
DMS B - Spike 0.5 ml (NPS 3 underivatized calib. std. B) into a
receiver. Record the spike solution in the log book.
Derivatize the DMS standards along with the rest of the samples. Final
volume is 10 ml.
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Appendix G
Revision No 8
Date: September 10, 1990
Page 15 of 15
DERIVATIZATION
FLORISIL
Add 250 ul High Purity MeOH to the samples and DMS.
Add 0.5 ml Diazomethane. Adjust to 3 ml with 99.9% MTBE. Record
solution. Cover with foil, mix and allow to react for 1 hour. Must remain
yellow for 10 min.
Slowly blow off diazomethane with nitrogen.
Adjust samples to ~4 ml with MTBE.
Bottle unflorisiled DMS's at 10 ml with 5% MeOH/MTBE and transfer to
vial.
Add H+ glass wool to 5 ml pipette. Tare, and add 1 g activated Fiorisil.
Record lot # and date activated.
Rinse florisil with 5-10 ml 5% MeOH/MTBE; discard eluate.
Without letting column go dry, add sample; collect in a clean 10 ml
volumetric.
Rinse receiver with 1 ml 5% MeOH/MTBE; transfer to column. Repeat
with another 1 ml and a 3 ml 5% MeOH/MTBE. Collect all.
Dilute to 10 ml in volumetric with 5% MeOH/MTBE; mix and transfer to
vial.
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Appendix H
Revision No. 8
Date. September 10, 1990
Page 1 of 7
APPENDIX H
SOP FOR PREPARATION OF DIAZOMETHANE
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Page
Appendix H
Revision No 8
Date- September 10, 1990
Page 2 of 7
DIAZOMETHANE PREPARATION
Revision #
Revision Date
1 1
2 1
3 1
4 1
5 1
6 1
7 (last) 1
December 4, 1989
December 4, 1 989
December 4, 1 989
December 4, 1 989
December 4, 1 989
December 4, 1 989
December 4, 1 989
Approved:
Group Leader:
Operations Manager:
QA Officer:
Laboratory Director:
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Appendix H
Revision No 8
Date: September 10, 1990
Page 3 of 7
DIAZOMETHANE PREPARATION
Scope and Application
This procedure can be used to prepare diazomethane, a chemical used in the NPS-3 and 615
herbicide extractions. Diazomethane is used to convert organic acids to their methyl esters.
Method Summary
A mixture of diazald(R) and aluminized ethyl ether is allowed to react in a reaction flask with 6g
potassium hydroxide, 10 ml Dl, and 35 ml EtOH in a heated water bath. The vapor product of
diazomethane is allowed to condense and drip into a cooled collection flask; it is then transferred to
an amber bottle; it is then stored in a freezer.
Safety Considerations
Diazald(R) is a highly carcinogenic compound. Gloves must be worn at all times when
preparing diazomethane. Any spill must be immediately cleaned and disposed in a sealed bag
marked "Hazardous - diazald(R)".
Prepare the diazomethane in a well-ventilated, explosion-proof hood. Ensure that the hood is in
correct operation.
Use a large safety shield to cover the apparatus as much as possible.
Diazomethane is highly explosive. All glassware used must be free of scratches, cracks, salts,
and ground glass joints. The diazomethane must never be heated above 70oC. Failure to do either
will result in an explosion of the diazomethane. If crystals are seen (especially at the collection end of
the condenser), an explosion is imminent; either remove the stopper on the top of the condenser and
flood with ethyl ether or prepare for the explosion.
Store below OoC immediately after using.
Only an experienced technician familiar with the hazards of safety techniques to follow should
use diazomethane.
Apparatus
1) Diazomethane generation kit - Aldrich chemical company. Contains the following:
Claisen adapter Round-bottom flask, 50 ml
Connecting adapter Round-bottom flask, 100 ml
Thermometer adapter Round-bottom flask, 250 ml
Vacuum distilling adapter Round-bottom flask, 500 ml
West condenser, 200 mm 125 ml Sep funnel
Distilling column, 200 mm Teflon(R) stopper
Round-bottom flask, 25 ml Gas inlet tubes (12)
2) Magnetic heating pad
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Appendix H
Revision No. 8
Date. September 10, 1990
Page 4 of 7
3) Amber bottle - 250 ml, with teflon(R)-lined screw cap.
4) Three 2L glass beakers.
5) Ring stand
6) Thermometer
7) Safety shield
8) 500 ml erlenrneyer flask
Reagents and Standards
1) Reagent water, organic-free
2) Redistilled EtOH - ACS Certified
3) Potassium hydroxide pellets - ACS certified.
4) Ethyl ether, unpreserved - Nanograde, free of peroxides by cleaning with alumina.
Test a 4L container of ethyl ether for peroxides with a test strip; notify the lab safety
officer if the peroxide content is greater than 5 ppm. Solvent-rinse an alumina
column with acetone and alumina-cleaned ethyl ether. To clean the ether, place a
plug of glass wool (which has been baked @ 400oC for 4 hours and stored at
150oQ in the tip of the alumina column. Add a stopcock - making sure that the
rubber O ring is not exposed - and a florisil(R) tip. Into the bottom of the column
place 37g alumina (which has been baked at 400oC for 4 hours and stored at
150oC). Add ether to fill the reservoir and allow 50 ml to elute; discard the eluate.
Place an empty 4L jug under the column. Tie tissue along the narrow stem of the
column to absorb spillage during transfer of the ether to the column; cover the open
spaces with foil in order to prevent evaporation and contamination. Collect the rest
of the 4L of ethyl ether. Record the lot number and date on the bottle; indicate that
the ether is aluminized by writing (AL) on the bottle. Test the cleaned ether for
peroxides with a test strip; if peroxides are present at a level greater than or equal
to 2 ppm, do not use; notify the lab safety officer.
5) Diazald(R) powder - ACS Certified.
6) Ice.
Generation Procedure
All glassware must be free of internal scratches/cracks; it must be kept behind a safety shield at
all times.
1) In a flammable, explosion-proof hood, set up the stand and a large safety shield.
2) Set up the glassware carefully, being sure to inspect and replace any scratched or
cracked materials.
3) If necessary, redistill 50-100 ml Ethanol. To do this, put the water bath at 95oC.
Set up distillation apparatus, making sure to turn on the condenser water. Distill the
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Appendix H
Revision No 8
Dale- September 10, 1990
Page 5 of 7
EtOH into a collection flask; transfer the EtOH to an amber bottle with a
teflon(R)-lined screw cap. Label the bottle "REDISTILLED" with the date and
preparer's initials.
4) Into the round-bottom flask weigh 6g KOH. Add 10 ml reagent water, 35 ml
redistilled ethanol, and 20 ml aluminized ethyl ether.
5) Prepare the water bath on top of the magnetic stirrer. The bath temperature should
be 55-60oC; the rheostat on the heating pad should be set between 2 and 2.2.
6) Prepare diazald(R) solution by weighing 21.4g diazold powder into a clean 500 ml
erlenmeyer flask and dissolving with 150 ml aluminized ethyl ether.
7) To the separatory funnel add ~20 ml diazald(R) solution (don't add more since the
diazald(R) will precipitate out of solution by collecting on the outside glass joints;
this will be kept to a minimum by keeping the joints tight).
8) Attach the reaction flask to the assembled apparatus so that it is immersed 3/4 in
the bath.
9) Immediately add the diazald(R) solution slowly to the round-bottom flask so that the
rate it enters the flask is the same as that in which it leaves.
10) Place the safety shield in front of the set-up. Close the hood, and allow distillation
to take place, making sure that the reaction is not vigorous. Carefully monitor the
water temperature.
11) When each portion has been transferred, close the stopcock on the 125 ml
separatory funnel. Continue adding the diazald(R) solution to the separatory funnel
in this manner until used up.
12) Rinse the solid diazald(R) from the 500 ml flask with 50 ml aluminized ethyl ether.
13) Transfer the solution to the separatory funnel and continue to add it until gone.
14) Allow the reaction to take place until the distillation of the diazomethane is complete
(20-30 minutes, or no more solution entering the collection flask).
15) When the distillation is complete, transfer the distillate to two 125 ml amber" bottles
free of cracks or scratches while wearing a full face shield. On the label, record the
solution, date, lot numbers, and preparer's initials; also indicate the intended use
(NPS or regular extractions). Write "NPS-r on one and "NPS-2" on the other.
16) Write up the book, indicating lot numbers of reagents used and the intended use.
In the solution notebook, write the procedure including the lot number and amount
of each chemical (diazald(R), EtOH, and ethyl ether) used. Indicate the intended
use (NPS or regular extractions). The diazomethane must be tested - see the
procedure below.
17) Make sure that the cap on the amber bottle is tight and store in the freezer until
needed.
18) Clean the apparatus. Wash the apparatus with aluminized ether and then with
deionized water, making sure to dump the waste into the red solvent drums. Place
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Appendix H
Revision No 8
Date: September 10, 1990
Page 6 of 7
the glassware in a salt tray and cover with foil to prevent breakage. Bake at 400oC
overnight.
19) After baking, wrap the internal joints in foil and the external joints with tissue.
20) Carefully place the glassware back into its case.
Diazomethane Test
1) Obtain four acid-washed receivers free of scratches or cracks. Label one 'blank",
and the others "PNP 1","PNP 2", and "PNP 3".
2) Add 1 ml MTBE to each receiver.
3) To each PNP sample, add 25 ul PNP standard (2000 ug/ml 4 nitrophenol); to all
samples, add 250 ul high-purity MeOH.
4) Add 0.5 ml newly-made diazomethane to each sample. Adjust the volume to 3 ml
with 99.9% MTBE. Mix, cover, and allow to react for one hour. Record all lot
numbers of solutions used, PNP standard information, diazomethane preparation
date, and preparer's initials in the NPS 3 log book.
6) Blow off the diazomethane with a gentle stream of nitrogen until the solution is clear.
7) Adjust the volume to 4 ml with 99.9% MTBE.
8) Bottle each sample, taking them to 10 ml with 5% MeOH in MTBE.
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Appendix H
Revision No. 8
Date September 10, 1990
Page 7 of 7
QUICK SUMMARY
PREPARATION:
Set up in an explosion-proof hood the stand and a large safety shield.
Set up the glassware; inspect and replace any scratched or cracked
materials.
GENERATION:
Redistill 50-100 ml EtOH at 95oC. Label the bottle "redistilled" with the
date and preparer's initials.
Prepare the water bath @ 55-60oC; the rheostat should be set @ 2-2.2.
Add 6g KOH, 10 ml Dl, 35 ml redistilled EtOH, and 20 ml AL ethyl ether
to a round-bottom flask.
Prepare diazold solution by adding 21.4 g Diazold powder and 150 ml
Al ethyl ether to a clean 500 ml flask.
Place the shield in front of the apparatus, close the hood, and allow to
distill. Carefully watch the temperature; keep the reaction non-vigorous.
Rinse the solid diazald from the 500 ml flask with 50 ml aluminized ethyl
ether. Transfer the solution to the sep funnel; add until gone. Allow the
reaction to proceed until complete.
Transfer the distillate into 2 125 ml amber glass bottles free of
scratches. Record solution, date lot numbers, preparer's units.,
intended use (NPS or regular extractions), and #1 and #2 on the
bottles.
CLEAN-UP:
DIAZOMETHANE TEST:
Write up the book and the solution notebook. Indicate lot numbers and
intended use.
Clean the apparatus by washing once with AL ether and once with Dl.
Dump the waste into the solvent drums. Bake the glassware at 400°C
overnight.
Wrap internal joints in foil, external joints in tissue.
Label 4 acid-washed receivers - "BLKVPNP 1","PNP 2","PNP 3". Add 1
ml MTBE to each.
Add 25 ul PNP standard to each PNP receiver.
Add 250 ul High-purity MeOH and 0.5 ml diazomethane (new) to each
receiver; dilute to 3 ml with 99.9% MTBE. Mix, cover, and react for 1
hour. Record lot numbers, PNP std. info, diazomethane prep date, and
preparer's initials in the NPS 3 log book.
Blow off diazomethane with a gentle stream of nitrogen.
Adjust to 4 ml with 99.9% MTBE. Bottle at 10 ml with 5% MeOH in
MTBE.
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Appendix I
Revision No. 8
Date: September 10, 1990
Page 1 of 3
APPENDIX I
SOP FOR PREPARATION OF SODIUM SULFATE
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Appendix I
Revision No 8
Date: September 10, 1990
Page 2 o< 3
ACIDIFIED SODIUM SULFATE 4 December 1989
Scope and Application
This procedure is used for the acidification of sodium sulfate, a drying agent used in the
process of preparing aqueous samples for gas chromatography. The acidified product is used in the
herbicide and phenol tests.
Method Summary
Sodium sulfate is weighed and poured into a clean shallow glass tray. A mixture of ethyl ether
with 10 ml H2SO4 per each kg Na2SO4 is prepared and added to cover the solid. The slurry is
mixed, allowed to dry under a hood, triple-wrapped with foil, and baked @ 400<>C for 4 hours. The
sample is cooled and broken into a fine powder with a clean mortar. It is then tested for acidification
by determining the pH of a mixture of 1g solid with 5 ml H2O; if the pH is below 4, it is then stored in
a large amber glass jar with a teflon-lined screw cap for use in extraction of herbicides or phenols.
Safety
Concentrated sulfuric acid is highly corrosive. Wear gloves at all times when handling acid.
Clean all spills with an acid spill kit; discard the waste in a method congruent with EPA standards.
Sulfuric acid reacts violently with ether. Pour slowly, and wear gloves and safety glasses during
the transfer.
Apparatus
1) A shallow glass tray, capable of holding up to 2 kg sodium sulfate.
2) A glass stirring rod.
3) A balance, capable of weighing up to 2 kg to 0.1 g.
4) A mortar with a teflon tip.
5) A large amber glass jar with a teflon-lined cap.
Reagents
1) Ethyl ether, ACS certified.
2) Sulfuric Acid, ACS certified.
3) Sodium Sulfate, ACS certified.
4) Aluminum foil.
Procedure
1) Weigh out 2 kg sodium sulfate. Pour into a shallow glass tray.
2) Into —600 ml ethyl ether slowly pour 20 ml concentrated sulfuric acid. Wear gloves
and safety glasses, as sulfuric acid reacts violently with ether. Mix well.
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Appendix I
Revision No. 8
Date: September 10, 1990
Page 3 of 3
3) Pour the ether/acid mixture on top of the salt. Mix well with a glass rod, making
sure to break up any chunks.
4) Add enough ether to cover the salt. Let the solvent evaporate in the hood.
5) Triple wrap the tray with aluminum foil.
6) Label the foil and bake in a muffle furnace @ 400oC for 4 hours.
7) Allow to cool. Test for acidification by mixing 1 g solid with 5 ml H20 and measuring
the pH. The pH must be less than pH 4.
8) Store in a large amber glass jar with a teflon-lined screw cap. Label "H+ Na2SO4",
with the date, lot number, and preparer's initials.
9) In the gray book mark the lot numbers and amounts of each solution, date, pH
when tested, and preparer's initials.
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Appendix J
Revision No. 8
Date: September 10, 1990
Page 1 of 16
APPENDIX J
NPSIS SAMPLE RECEIPT SOFTWARE FOR LABORATORIES
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4/S/St
TO: AKDROT EASTOH, JAMES K. MOHTCOMERT COHSULTARTS
FROM: CHIP LESTER, IC7 IHC.
RE: HFSIS SAMPLE RECEIPT SOFTWARE FOB. LABORATORIES
ICF's National Pesticide Survey Information System (NPSIS) is ready to
collect information from you regarding the receipt of well water saaples an<
their condition. Please find enclosed the following items: 1) A users memo
containing all operating iris true t i ons , and 2) A copy of Carbon Copy softvar-
which is necessary to establish communications with NPSIS over phone lines.
As mentioned previously, the software allows you to report the receipt of a
one or more sample kits. It also prompts you for details regarding the
condition of the saaples. Additional features include; a bulletin board wh
allows you to interactively send messages to ICF staff via your computer
keyboard, file transfer, and access to the ICF computerized mail system for
sending menos. It is also possible for you to speak over the phone to an I
staff member during your session.
It is important that you test the communications link between the NPSI
computer and yours. We have experienced trouble when using Carbon Copy
software with a computer which has a Kanzana 3.5 inch disk drive, and also
with computers which have a non-Hercules or non-EGA compatible graphics car
For testing purposes, your sample kit identification numbers and FedEx
airbill numbers (respectively) are: PD-0000-151 and 1111111111. PD-0000-15:
and 2222222222. and PD-0000-153 and 3333333333. Use these sample kit
identification numbers when trying out the NPSIS Sample Receipts Prograa.
'Vc:e -s Cr.ir: these vill be different far each lab."
tfe feel that it would be helpful to both parties if you could call us
when you are ready to test the NPSIS system, and we vill assist you over "
phone during your session. If you would like to do this, please call Betn
Estrada at (703) 934-3431. NPSIS will be available for access 24-hours a c
seven days a week. Ue appreciate hearing any comments you have regarding
NPSIS.
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THE NTS IS SAMPLE RECEIPT FROG8AM
NPSIS Is designed to keep crack of the day to day operations of the
National Pesticide Survey. You play an important role in NFS and your tise
notification of receiving a kit of samples is essential co the success of ."•
Ve have designed the Sample Receipt Program with your busy schedule in nine
NPSIS will obtain the minimum amount of information necessary while still
maintaining a secure systea. You will be entering data into the NPSZS
personal computer via your own computer, modem, and Carbon Copy software.
1.1 Hardware and Softvare Requirements^
The NFSIS Sample Receipt Prograa has a minimum hardware and software
requirement. Here is a list of items you will need:
Hardware:
One (1) IBM PC. XT. AT, or Personal System modal with at
least 640K memory.
On* (1) 2400 or 1200 baud Hayes or Hayes compatible modi
with cables. (See Carbon Copy guide for cabling requir-
ements and a description of usable modems)
One (1) data transmission phone line.
Software:
• NPSIS Sample Receipt Program access provided for you by
ICF.
• One (1) copy Carbon Copy software which is provided to %
by ICF for the duration of SPS.
Initial Tnstallation
Before you can access and use NPSIS. you must first load the Carbon Co-
software onto your PC. The directions are provided in the Carbon Copy manu.
One iteo you will want to include is an entry into the "Call Table". This
entry will include a name, telephone number, and password for the NPSIS
computer. To' enter these iceas into the Call Table, press "2" fron the Car!
Copy Parameters' Screen. The information you must enter consists of the
following:
-------
Same: MPS
Telephone Number: 703-961-0629
Password:
for
NPSIS will maintain a set configuration throughout operation. Any
changes due to updates in equipment or the system which will affect your
ability to communicate through Carbon Copy will be forwarded to you. The
parameters which will be maintained at this time are:
• 2400 baud modem speed.
• Answer ring count equal to one.
• Re-boot on exit after 5 minutes. (If there is a power
failure or some other type of interruption, you can log
back on to NPSIS and resume your session.)
• Five minute inactivity tine constraint.
• Two password attempts .
2 REPORTTHC A SAMPLE RECEIPT TO EPSIS.
2.1 Establishing a Co""ninieacions Link.
Once you have installed Carbon Copy and have ail of the necessary
Type: C:> CCHELP NPS in your directory containing Carbon Copy.
This command will automatically dial the NPSIS computer, send your password
for verification, and establish a data link between the two computers. You
will be able to discern what is taking place by messages to your screen.
2.2 Entering A Sample Receipt Into NPSIS.
Once you have established a data link. ( e.g., are 'logged on*), you w:
see on the screen exactly what is on the screen of the NPSIS computer. Thi:
screen you are viewing is the Bain MRU for the Sample Receipt Program.
Remember that, you are controlling the NPSIS computer via a 2400 baud phone
line and your typing will appear on the screen at a much slower rate than y<
are accustomed to. A few tips on how to use the system are outlined in the
next section.
-------
?.?.! Useful Tiaa on Hov co Use NPSIS.
Before you scare. a few things co remember are:
• Pressing the "Esc" key will cancel all change* for che screen you
art currently in and return you co che previous screen. Pressing
"Esc* at che Searching Screen recurns you co che main. menu.
• Pressing "PgDn" or 'PgUp' vill save che iceas you have entered in
che current screen and place you in che next or previous screen,
respectively. This feature is handy co use when you only have a f
iceas co enter in a screen which prompts for several iceas.
• Pressing "Enter", "arrow up*, or "arrow down" will move the cursor
froa field Co field in each screen. Remember chat using che
sideways arrows will not work.
• Pressing che "Alt" and "Right Shift" keys together will place che
Carbon Copy Control Screen over che NPSIS Saaple Receipt Program.
You can Chen use che communications features in Carbon Copy.
Pressing "F10" again when you are through will replace the NPSIS
Saaple Receipt Program screen you were currently in back on your
screen, and
• Because you will are most likely co be entering information
regarding a number of kits ac one time, after' you save or cancel
your entries for one kit. you will be placed at che initial Sample
Searching Screen for a new kit. If you are finished with your dat
entry, simply press "Esc" co exit che Saaple Searching screen and
placed in che main menu.
2.3 A Basle Outline of the ?airi'I* Receipt Pr
The NPSIS Sample Receipt Program has three basic feacures:
• Initial reporting of « .>'rs saspie kiz of saapl« bottles.
• Ability co edi: or re-edit an existing reporc of a kit
receipt, and
• Access co ICFs computerized mail systea which provides
ability co.send memoranda to 1C? staff.
The information obtained in an entry for a kit of bottles is:
• The kit identification number, the FedEx airbill number
and the last naae of the person making the entry.
• Any damage co che kit as a whole such as melted ice or
breakage of the cooler.
-------
Verification of which bottles belong in « kit or cooler.
notification of any missing bottles or any additional
bottles, and
Any damage to each sample bottle which renders it unusab!
for analysis and testing.
2 4 VPSIS S&mle ReceioC Program Screens
When you have completed the logon procedure, you will see the following
main menu on your computer screen:
NATIONAL PESTICIDE SURVEY INFORMATION SYSTEM
SELECTION MENU FOR REPORTING SAMPLE RECEIPTS 04/05/88
Report \ Edit a Sample Receipt
Send a Memo
Press to Logoff
use f ^ ar.c •»J to seiec: option.
The screens provided in chis memo will show all of the screens available
and thus represent the maximum nuaber of screens you will encounter with
NPSIS. It is most likely that you will not have the need to enter informatic
reporting daoaged kits or samples. Therefore, not all of the screens deplete
below will appear in your normal session.
If you choose che first itea on che menu, 'Report \ Edit a Sample
Receipt*, you will then be prompted for the kit identification nuaber and che
FedEx airbill number associated with the specified kit. The screen will
appear like this:
-------
NFS Sample Receipc Searching Screen
** Enter Che following items to access kit information **
To find the Kit information in NFSIS in the most complete
and accurate fashion, pleas* enter the Kit number and the
FedEx airbill number.
Enter kit number:
> PD-0001-151
Enter FedEx airbill *:
> 1111111111
Enter your Last name:
> CHIANG
Fress ESC to exit the searching *
If the kit number you have entered is incorrect, or if the kit number ai
FedEx airbill number combination is incorrect, NFSIS will prompt you to try '
enter these number again, as illustrated on the nexc page. 1C is possible
that the FedEx airbill number on the kit is not the same as the FedEx airbil
number which was entered into the HFSIS system. This could happen if the
field team loses or damages the airbill.
-------
ERROR!! The kit you entered cannot be found.
Kit number: PD-0001-151
AND
FedEx airbill number: 1111111111
Please check chese numbers and try again!
NPSIS is designed to track Kits and FedEx airbill numbers.
The Kit and FedEx airbill number combination you have entered
does not match what is currently in the system. Please enter
the correct combination. If you still have problems, cry
leaving the FedEx airbill » BLANK. Only enter the Kit number
Press any key to continue...
Then, you will encounter this screen insuring that you have entered the
FedEx airbill number:
Kit No.: PD-0001-151
Did you enter the correct Kit number and FedEx airbill number?
NFSIS is designed co score and crack ail Fedlx airbill numoers.
This Kit may have a different FedEx airbill .number than che
system, please enter che new FedEx airbill number:
Note: if che correct airbill number vas entered before, hit ENTER.
PgDn (Next page), PgUp (Previous page), Esc (Exit)
-------
Once you have correctly Identified the sample kic, NPSIS will ask you tf
chere is any damage co che kic aa a whole:
Kic No.: PD-0001-151
Was there any damage co che sample kic? (Y/N) T
PgDn (Next page), PgUp (Previous page), Esc (ExiC)
-------
Next. NPSIS wtll ask you co survey the contents of th« kit and cheek thai
which bocele* are contained within the kit. You should then look *t the
beetle label* and determine if any are missing. Don't forget to check and
determine if any bottles have been included in the kit which do not appear on
the list provided by NPSIS on this screen:
Kit No.: PD-0001-151
Please compare the following bottle numbers
with those in the sample kit.
Bottle No: PD-0001-1-1-01
Bottle No: PD-0001-1-1-03
Bottle No: PD-0001-1-3-01
Bottle No: PD-0001-1-3-03
Bottle No: PD-0001-1-9-01
Bottle No: PD-0001-1-9-03
Did you receive exactly these bottles in the sample kit? (Y/N) H
PgDn (Next page), PgUp (Previous page). Esc (Exit)
-------
If you have pressed •»•, indicating that you did noc receive exactly vhai
assuae* you have received, you will be prompted to enter che appropriat.
information. ThiJ information includes pressing * 'Y- or 4 'N« beside each
bocrle. and entering the bottle number found on the labels of *ny additional
bottles you have received:
Kit No.: PD-0001-151
Please Indicate vhich bottles you received:
Bottle No: Received (Y/H)
PD-OOOl-l-1-01
PD-0001-1-1-03
PD-0001-1-3-01
PD-0001-1-3-03
PD-0001-1-9-01
PD-0001-1-9-03
H
H
Y
Y
Y
Y
Please indicate any additional bottles you received:
Bottle No. PD-0002-1-1-05 2. Bottle No. PB-0002-2-2-01
Bottle No. PD-0004-4-4-01 4. Bottle No. • - - -
Bottle No. • ... 6. Bottle No.
7. Bottle No.:
8. Bottle No.:
PgDn (Next page), PgUp (Previous page), use f *or +-*t* select field.
Notice chat che user has indicated that he did not receive the first: cv
bottles on the list. Also note chat the user has indicated additional bottl
which have come in che sasple kit. but vhich were noc on che list.
-------
Next. NPSIS pro«pc« you co indicate If Any of the individual bottles ha-
been damaged and rendered unusable for analysis:
Kit So. : PD-0001-151
Was chere any damage co the sample Beetles? (Y/N) T
P§Dn (Next page), PgUp (Previous page), Esc (Exit)
-------
oust
In order to complece the appropriaca information on damaged stopUs, you
«.-,.. first press * "Y" or a "N" In the field labeled 'Damaged Y/N'. If you
have encered a "Y* in this field, you must chen idencify whac Che cauae of ch*
damage is, co che besc of your abilicies. As noced on che computer screen
below, che "Other* category should be used if che sample is unusable but is
not broken. Please cry co comaenc whenever possible.
Kit No.: PD-0001-151
Please'indicate which bottles are damaged by entering Y or N,
and for chose which are damaged, indicate che cause of damage.
---CAUSE --•
Bottle Ho: Damaged Broken Other Comment
(Y/N) (Y/N) (Y/N)
PD-0001-1-3-01 S
PD-0001-1-3-03 H
PD-0001-1-9-01 H
PD-0001-1-9-03 H
PD-0002-1-1-05 H
PD-0002-2-2-01 Y Y
PD-0004-A-4.01 H
The 'Other' cause category is for reporting contamination of a sample,
e.g. contamination noted on che Sample Tracking Form, air bubbles,
or ocher reasons a sample is unusable.
PgDn (Next p*ge) , PgUp (Previous page), use 4 ^ or
select field.
-------
Now you have conpleced &li of the necessary information needed Co verify
chat the proper staples h«ve reached cheir final destination in usable
condition. You may save your kit entry by pressing 'Enter'. If you wish to
cancel your kit entry and try again, press "N" and "Enter". If you wish to
view or edit che current kit entry, press "R" and "Enter" and NPSIS will plac
you back at che beginning of your entry.
You have completed all of the data entry screens for this Kit.
You may save your entry by pressing 'Enter' .
You may cancel your entry by pressing 'N' and 'Enter' .
You may verify or edit this entry by pressing 'R' and 'Enter'.
* * * Accept entries? * * *
to Save *
to Cancel *
to Verify or Edit * Y
* Press
* Press N and
* Press R and
By pressing "Enter" . you have saved all of the information necessary fc
a particular saaple kit. NPSIS assuaes chat you will enter more chan one kit
sr.tr/ ter session. Therefor*, "u v.ll :s Tliced s.~ -r.t ir.itiil "?ir:r.i"
Screen-1. If you are finisheo. press "Esc"1 and you will '->e returned co the
main menu. You can chen log off of NPSIS by pressing "Alt" and "Right shifc'
at the same ciae. You may also send a memo through the 1C? computerized sax
system. To do chis. cursor down co che second menu choice and press "Enter"
The next two pages of this memo describe how to us* the ICF electronic
sail system. Mote chat the password for you is NFS. The mail system softva
program will prompt you for chis password before it will allow access to the
syscea. Also, when you are selecting che recipients of your memo, please
press che space bar beside che initials "HPS". This will send your memo co
all ICF staff involved in the NFS project. If you wish to send meaos to a
particular ICF staff member, please call Beth Estrada for the identification
number of che desired ICF employee.
-------
ELECTRONIC MAIL
Function
Augment office communications
electronic transfer of notes and files.
with
Summary
Electronic Mail (E-Mail) allows you to send,
receive, read, and subsequently save or
discard notes and attached files.
When you power up your workstation you
will automatically enter E-Mail if you have
received any mail. Enter your password to
check your mail, or press twice to
avoid E-Mail and continue to the Assist
main menu.
Instructions
Operation of E-Mail is similar to Lotus
1-2-3. Press the Fl key to receive help at
any time during operation. If any more
help is needed contact workstation support
to receive a manual.
For more information on any feature of
electronic mail, use Network Courier's on-
line help or refer to the User's Manual.
Passwords
Your password will be 'password* until you
change it yourself. Once you have given
your password and entered E-Mail, you can
change your password by selecting Options.
then Password.
Reading Mail
1. Select 'Read' from your men
Highlight read,then pre:
.
1 Select the note to read:
a. Highlight the note (using
the arrow keys); and press
.
B. To save the note, select
'Storage*, then *Save*. Enter
the name of the file to which
the note should be saved.
3. Press to select another note.
Writing Mail
1. Select 'Compose1, then 'edit*.
2. Press when the highlig!
moves to TO".
3. Select the recipients^):
a. Move the highlight to the
first recipient's initials.
b. Press the space bar. A
small mark will appear.
c. Repeat steps a and b for all
recipients. Press the space b
twice to 'de-select* recipient
T>.t small mark will disapre
tc csncs; '"•
entire list.
4. Select the initials of those who »
receive copies:
a. Press the down arrow to r
to gc
-------
Writlnc Mall, cootiavcd
5. Eater a subject and priority.
(optional)
6. Select attachments (optional):
a. Press and type the
path for the document(s).
b. Press and select the
document(s) to be attached.
c. Repeat steps a and b for
documents in another directory.
7. Enter the text of your message.
S. Press when finished.
9. Select "Transmit* to post the note
and attachments.
Quitting the Mail Program
1. Press from the menu.
2. Select 'YES'.
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Appendix K
Revision No. 8
Date: September 10, 1990
Page 1 of 3
APPENDIX K
NELSON DATA SYSTEM CALCULATIONS
-------
Data System Calculations for NPS Method 1
1) The area response for a given compound is divided by the area response for the
internal standard to obtain the area response.
2) The area ratio for a given compound is then plotted against the concentration for
each calibration level.
A) Area ratio is plotted on the vertical (y) axis.
B) Concentration is plotted on the horizontal (x) axis.
C) Concentration is in units of ug/ml.
3) The data system then fits the data to a linear regression equation, (y = mx + b).
for each compound, and calculates the slope and the intercept.
A) The slope, usually designated as "m". is designated Cl.
B) The y-intercept. usually designated as "b*. is designated CO.
C) Therefore, the form of the equation is now "y = Clx 4- CO".
4) The concentration "x" is then determined by rearranging the equation to get *x =
(y - CO)/C1*.
5) Since "x" represents the concentration of the extract in ug/ml. it is necessary to
convert to ug/L to obtain the concentration in the original sample. This is
accomplished through the use of a multiplier.
A) The default multiplier is 5 ml/L. This is used whenever exactly one liter of
sample is extracted.
B) If a volume other than one liter is extracted, the multiplier is determined by •
dividing the final extract volume (which is always 5 ml) by the volume, in liters.
of the original sample.
- For example, if 1123 ml of original sample are extracted, the multiplier
is 5 ml/1.123 L, which is 4.4524 ml/L.
C) Therefore, the concentration "x" is then multiplied by the multiplier to
obtain the concentration of a given compound in the original water sample in
ug/L.
6) If the sample required dilution, the dilution factor is entered into the data sytem.
The data system then multiplies the number obtained in step 5C by this factor to
obtain the final concentration.
-------
Example
Mevinphos. Set 1-0144
Area Area (IS) Area Ratio Concentration
224303 1781233 0.1259256 O.l32ug/ml
616550 1783185 0.3457577 0.302 ug/ml
1290078 1747338 0.7383105 0.604 ug/ml
Fitting the data to the equation y = CIx + CO. (see Step 3C. previous page).
where:
y = Area Ratio
x = Concentration.
the data system provides:
Cl = 1.298
CO = -0.046.
This information will now be used to determine the concentration of Mevinphos in
LCS A.
Area Area (IS) Area Ratio
1072000 1731722 0.6190372
Therefore, the concentration of Mevinphos in the extract (x) is:
x = [0.6190372 - (-0.046)1/1.298 = 0.5123553 ug/ml.
To obtain the concentration in the original sample:
0.5123553 ug/ml X 5 ml/L = 2.5617765 ug/L. (Note that the default
multiplier was used since exactly I L of sample was extracted.)
The data system reported the concentration as 2,5611 ug/L. The difference in the
4th decimal place can be attributed to the difference in the number of significant
figures used by the computer vs. the number of significant figures used in the manual
calculation.
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Appendix L
Revision No 8
Date: September 10, 1990
Page 1 of 7
APPENDIX L
SOP FOR ARCHIVAL OF NPS DATA
-------
NPS Method 3 Quantltatlon Algorithm
The calibration protocol for NPS method 3 involves the use of a 2nd order polynomial fit of the
data generated from the analysis of the calibration standards, which makes it much more
difficult to ascertain the exact algorithm that Is used for sample quantitatton.
Initially, a calibration plot of instrument response (in this case the ratio of analyte area to
the area of the internal standard (A/AisJ) vs. concentration (in units of ug/mL) is prepared.
The datastation then calculates the curve that best fits the data using a standard 2nd order
polynomial fit function. The subsequent equation is in the form of:
Y« C2*2 + C^x + C0 where Y. response (A/Ais),
and X- concentration (ug/mL)
This equation can be convened into the standard form for a quadratic equation (Ax2 + Bx+ C«
0) as follows:
0. C2x2 + f^x + (C0-Y)
From here, the equation can be solved for X (concentration) for any given Y (A/AJs), using the
following formula:
2C2
We have independently verified the Nelson polynomial coefficients using a commercial
software program for the Macintosh computer. Consequently, we have assurance that the
calibration equation is generated using a 2nd order polynomial fit of the data. Figures 1
represents the calibration data for the three compounds that were detected in a sample in set
0145, as we! as the surrogate and the internal standard. The first set of polynomial
coefficients were taken directly from the Nelson printout using the number of significant
figures provided on the printout The next set of coefficients represents the coefficients
obtained using the independent software package, and serve as verification that this program
duplicates the algorithm used by the Nelson system. The final set of coefficients were obtained
by plotting concentration vs. area ratio (A/Ais) using the software program. By inverting the
plot, these coefficients can be used directly to convert area ratio to concentration.
-------
MONTGOMERY LABORATORIES STANDARD OPERATING
PROCEDURE FOR THE ARCHIVAL OF THE
NATIONAL PESTICIDE SURVEY (NFS) DATA
Introduction
A Standard Operating Procedure has been developed to allow
Montgomery Laboratories (ML) to retrieve all documentation
necessary to technically defend NPS analytical results. The
documents will be located on the first floor on ML premises in a
locked data storage room.
All data that have been collected in support of the National
Pesticide Survey will be stored until October of 1992 in a
systematic manner such that data may be retrieved in a timely
fashion for reference purposes.
The NPS project manager, Julie Zalikowski, will be the primary
manager for all archived documents. Ms. Zalikowski and Dr. Eaton,
the program manager, will maintain keys to the storage room.
Materials to Archive
1) Method 1 Initial demonstration of capabilities.
2) Since samples are filed by sets, a cross-reference list from
sample ID to set ID has been developed. The cross-reference
list includes:
Sample ID
Sample type
Date sampled
Date received
Date extracted
Set numbers
Date analyzed
3) Method 1 chromatograms listed in chronological order
1 - 0001 through 1 - 0196
-------
4) Method 1 Quantitation reports listed in numerical order.
1 - 0001 through 1 - 0196
For each Quantitation report the following materials are
available, as appropriate to a given method and /or set:
Set completion form
Method Blank (MBLK)
Corrective Action Forms
Lab control standards (LCS's)
Lab spike samples (LSS's)
Instrument control samples (ICS's)
Field samples
Time - storage samples
Control chart
GC/MS data (Extract shipping forms and spectras)
Extraction summary sheet
Sample tracking
Dbase hard copy
Analytical run sheet
5) Method 1 control charts
1 - 1 through 1 - 37
6) Method 3 Initial demonstration of capabilities
7) Method 3 Sample ID to set ID cross-reference list
8) Method 3 chromatograms
3 - 0002 through 3-0198
9) Method 3 Quantitation reports
3 - 0002 through 3 - 0198
10) Method 3 Control Charts
3 - 1 through 3 - 39
11) Method 9 Initial demonstration of capabilities
12) Method 9 sample ID to set ID cross-reference list
13) Method 9 Quantitation reports
9 • 01 through 9 • 36
-------
14) ICF sample receipt forms
15) Monthly status reports/Internal QA audit reports
16) Statement of qualification for personnel who participated in the
project
1 7) Log books
a. Extractions log book
b. Standards log book (Method 1 & Method 3)
Spiking Standards log
Internal Standards log
Surrogate log
Calibration standards log
c.
Method 9 log book
Daily log
Standard & Reagent log book
d. Instrument Maintenance log book
e. GCMS log book
f. Telephone log book and notes (M1, M3 & M9)
18) Forms and records
A Copy of the QAPjP M1, M3. M9
Temperature log
GCMS Extract shipping form
GCMS Reports
Copy of NFS formatted disc
Hardcopy of any specialized computer programs
Time storage extraction and analysis summary
19) Correspondence received from Technical Monitor
20) Performance evaluation results
21) NFS Contract
22) ICF Daily Sampling Schedule*
23) General NFS Information
-------
ORGANIZATION OF NFS MATERIALS
ACCORDING TO FILE CABINET NUMBER
a.
b.
c.
d.
b.
c.
d.
a.
b.
c.
d.
a.
b.
c.
d.
a.
b.
c.
d.
a.
b.
c.
d.
Method 1 Initial Demonstration of capabilities
Method 1 Sample Cross Reference List
Method 1 Chromatograms 1-0001 thru 1-0020
Method 1 Chromatograms 1-0021 thru 1-0038
Method 1 Chromatograms 1-0039 thru 1-0054
Method 1 Chromatograms 1-0055 thru 1-0070
Mecl2 test
Method 1 Chromatograms 1-0071 thru 1-0084
Method 1 Chromatograms 1-0085 thru 1-0103
Method 1 Chromatograms 1-0104 thru 1-0117
Method 1 Chromatograms 1-0118 thru 1-0132
Method 1 Chromatograms 1-0133 thru 1-0150
Method 1 Chromatograms 1-0151 thru 1-0169
Method 1 Chromatograms 1-0170 thru 1-0185
Method 1 Chromatograms 1-0186 thru 1-0196
Method 1 Quantitation Reports 1-0001 thru 1-0095
Method 1 Quantitation Reports 1-0096 thru 1-0196
Method 1 Control Charts 1-1 thru 1-37
Method 3 Initial Demonstration of
Method 3 Sample cross-reference
Method 3 Chromatograms 3-0002
Method 3 Chromatograms 3-0019
Method 3 Chromatograms 3-0047
Method 3 Chromatograms 3-0073
Capabilities
list
thru 3-0018
thru 3-0046
thru 3-0072
thru 3-0095
Method 3 Chromatograms 3-0096 thru 3-0120
Method 3 Chromatograms 3-0121 thru 3-0143
Method 3 Chromatograms 3-0144 thru 3-0169
DCPA Study
Method 3 Chromatograms 3-0170 thru 3-0195
Method 3 Chromatograms 3-0196 thru 3-0198
Method 3 Quantitation Reports 3-0002 thru 3-0113
-------
7.(con't.)
b. Method 3 Quantitation Reports 3-0114 thru 3-0198
c. Method 9 Initial Demonstration of Capabilities
Method 9 Sample Cross-reference list
Method 9 Quantitation Reports 9-0002 thru 9-0036
ICF Sample Tracking Forms
d. Monthly Status Reports/Internal QA Reports
NFS Personnel
NFS Method 1, 3 & 9 Log Books
GCMS Log Book
Telephone Log Books & Notes (M1, M3 & M9)
8. a. Copy of QAPP (M1, M3 & M9)
Temperature Log
Copy of NFS Formatted Disc
Specialized Computer Program
Time Storage Summary
Correspondence from Technical Monitor
Performance Evaluation Results
NFS Contract
ICF Daily Sampling Schedules
General NFS information
-------
Appendix M
Revision No 8
Date: September 10, 1990
Page 1 of 4
APPENDIX M
SOP FOR NPS WASTE TREATMENT
-------
Appendix M
Revision No, 8
Date- September 10, 1990
Page 2 of 4
NFS WASTE TREATMENT
Page
Revision #
Revision Date
1
2
3
4 (last)
1
1
1
1
October 3, 1 989
October 3, 1 989
October 3, 1 989
October 3, 1 989
Approved:
Group Leader:
Operations Manager:
QA Officer:
Laboratory Director:
-------
Appendix M
Revision No. 8
Date: September 10, 1990
Page 3 of 4
NPS WASTE TREATMENT
Scope and Application
This procedure is used to treat wastewater containing 10-50 mg/l HgCI2 in order to precipitate
the salt out of solution.
This is applicable to all treating water from all samples which have been preserved with mercuric
chloride.
Method Summary
Sample waste containing HgCI2 is aerated completely to remove any peroxides from ether. The
waste is adjusted to pH 8-11 by adding either 25% NaOH or 1 M H2SO4 to 15-20 liters of wastewater.
The pH'd wastewater is then poured into a 55-gallon teflon drum.
When the drum is 90% full, the salts in it are reduced by adding a sodium borohydride solution.
The water is mixed and allowed to sit.
A sample is tested for mercuric chloride; if it passes, the drum is pumped dry and the
precipitate poured into the solid waste drum.
Safety Considerations
Mercuric chloride is a neurotoxin and a nephrotoxin. Care must be taken to avoid inhalation of
dust; gloves must be worn as HgCl2 may be absorbed through the skin.
When opening the 55 gallon drums, be careful not to inhale ether or methylene chloride fumes;
the use of a respirator is recommended.
Material Safety Data Sheets (MSDS) are located in the lab and available for any to use. These
sheets describe the hazards of each chemical used and give the method required to treat any injury
or spill of such chemicals.
Apparatus
1) 500 ml Erlenmeyer flask.
2) 250 ml graduated cylinder.
3) Analytical balance.
4) Aeration apparatus - a teflon tube with an aeration stone on the end of it.
5) 55 gallon teflon drum, capped.
6) 10 ml pipette.
7) 10 ml glass vial, with teflon screw cap.
8) Pump, with a glass wool filter. Clean the filter by replacing the glass wool once a month.
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Appendix M
Revision No 8
Date- September 10, 1990
Page 4 of 4
Reagents and Standards
1) Reagent water, organic-free.
2) Sodium hydroxide pellets - ACS certified. Make 25% NaOH by mixing 250g NaOH
with enough reagent water to make 1L solution.
3) Sodium borohydride - ACS certified. Make 12% NaBH4 in 5% NaOH in the following
manner:
1) Weigh 7.5g NaOH into a 500 ml erlenmeyer flask.
2) Add ~ 50 ml Dl to dissolve the NaOH.
3) Add 18 g NaBH4 into the flask; mix well.
4) Pour the solution into a 250 ml graduated cylinder.
5) Rinse the flask with —20 ml Dl. Pour the rinse into the cylinder to complete the
transfer.
6) Add enough Dl to the cylinder to dilute the solution to 150 ml. Mix well, and
transfer to a 250 ml amber bottle.
Waste Removal Procedure
1) In a hood, aerate NPS-3 waste ~1 day or until any ether has evaporated; aerate
NPS-1 waste —2 hours.
2) Ph the waste to pH 8-11. Use 25% NaOH as the base to pH the waste; if the
resulting solution is too basic, use 1 NH2SO4 to acidify it.
3) Make 12% sodium borohydride solution in 5% NaOH by following the directions in
Reagents.
4) Pour the waste into a 55 gallon teflon drum. When the drum is —90% full, add the
150 ml sodium borohydride solution. Cap the barrel and shake to ensure
dissolution.
5) Let the barrel sit at least 3 days to allow settling of the precipitate.
6) On the fourth day, obtain a 10 ml sample and pour into a 10 ml glass vial with a
teflon screw cap. Label the sample "NPS WASTE" with the barrel number, date, and
preparer's initials.
7) Take the sample to a metals analyst so that the amt Hg++ ions may be tested.
Record the sample on the sheet provided.
8) If the sample passes, the supernatant in the drum can be drained by a pump with a
glass wool filter; if not, repeat steps 2-7. If the second sample fails, pump the
supernatant into a new drum and leave the solid; repeat steps 2-7 with the
supernatant and pour the solid into a solid waste drum.
9) Pour the solid into a solid waste drum.
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Appendix M
Revision No. 8
Date: September 10, 1990
Page 4 of 4
Reagents and Standards
1) Reagent water, organic-free.
2) Sodium hydroxide pellets - ACS certified. Make 25% NaOH by mixing 250g NaOH
with enough reagent water to make 1L solution.
3) Sodium borohydride - ACS certified. Make 12% NaBH4 in 5% NaOH in the following
manner:
1) Weigh 7.5g NaOH into a 500 ml erlenmeyer flask.
2) Add ~ 50 ml Dl to dissolve the NaOH.
3) Add 18 g NaBH4 into the flask; mix well.
4) Pour the solution into a 250 ml graduated cylinder.
5) Rinse the flask with —20 ml Dl. Pour the rinse into the cylinder to complete the
transfer.
6) Add enough Dl to the cylinder to dilute the solution to 150 ml. Mix well, and
transfer to a 250 ml amber bottle.
Waste Removal Procedure
1) In a hood, aerate NPS-3 waste —1 day or until any ether has evaporated; aerate
NPS-1 waste ~2 hours.
2) Ph the waste to pH 8-11. Use 25% NaOH as the base to pH the waste; if the
resulting solution is too basic, use 1 NH2SO4 to acidify it.
3) Make 12% sodium borohydride solution in 5% NaOH by following the directions in
Reagents.
4) Pour the waste into a 55 gallon teflon drum. When the drum is —90% full, add the
150 ml sodium borohydride solution. Cap the barrel and shake to ensure
dissolution.
5) Let the barrel sit at least 3 days to allow settling of the precipitate.
6) On the fourth day, obtain a 10 ml sample and pour into a 10 ml glass vial with a
teflon screw cap. Label the sample "NPS WASTE1 with the barrel number, date, and
preparer's initials.
7) Take the sample to a metals analyst so that the amt Hg++ ions may be tested.
Record the sample on the sheet provided.
8) If the sample passes, the supernatant in the drum can be drained by a pump with a
glass wool filter; if not, repeat steps 2-7. If the second sample fails, pump the
supernatant into a new drum and leave the solid; repeat steps 2-7 with the
supernatant and pour the solid into a solid waste drum.
9) Pour the solid into a solid waste drum.
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