EPA Document #: EPA/600/R-12/010
METHOD 525.3 DETERMINATION OF SEMIVOLATILE ORGANIC CHEMICALS IN
DRINKING WATER BY SOLID PHASE EXTRACTION AND
CAPILLARY COLUMN GAS CHROMATOGRAPHY/ MASS
SPECTROMETRY (GC/MS)
Version 1.0
February, 2012
Jean W. Munch and Paul E. Grimmett (U.S. EPA, Office of Research and Development,
National Exposure Research Laboratory)
David J. Munch and Steven C. Wendelken (U.S. EPA, Office of Water, Office of Ground
Water and Drinking Water, Technical Support Center)
Mark M. Domino (Industrial and Environmental Services, LLC)
Alan D. Zaffiro and Michael L. Zimmerman (Shaw Environmental and Infrastructure,
Inc.)
NATIONAL EXPOSURE RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U. S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
525.3-1
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METHOD 525.3
DETERMINATION OF SEMIVOLATILE ORGANIC CHEMICALS IN DRINKING
WATER BY SOLID PHASE EXTRACTION AND CAPILLARY COLUMN GAS
CHROMATOGRAPHY/ MASS SPECTROMETRY (GC/MS)
1. SCOPE AND APPLICATION
1.1. This is a gas chromatography/mass spectrometry (GC/MS) method for the
determination of selected semivolatile organic compounds in drinking waters. Accu-
racy and precision data have been generated in reagent water, and in finished ground
and surface waters for the compounds listed in the table below. This method was
initially developed with full scan GC/MS, but performance has also been demonstrated
in the selected ion monitoring (SIM) mode using a subset of analytes. SIM is useful
when enhanced sensitivity is desirable. An example chromatogram which includes the
entire analyte list is shown in Figs, la-Id.
Analyte
Acenaphthylene
Acetochlor
Alachlor
Aldrin
Ametryn
Anthracene
Atraton
Atrazine
B enzo [a] anthracene
Benzo[&]fluoranthene
B enzo [k] fluoranthene
Benzo[a]pyrene
Benzo[g,/7,/']perylene
Bromacil
Butachlor
Butylate
Butylated hydroxytoluene (BHT)
Butylbenzylphthalate
Chlordane (tech grade)
cis-chlordane
trans-chlordane
trans-nonachlor
Chlorfenvinphos
Chloroneb
Chlorobenzilate
Chemical Abstract
Services Registry
Number (CASRN)
208-96-8
34256-82-1
15972-60-8
309-00-2
834-12-8
120-12-7
1610-17-9
1912-24-9
56-55-3
205-99-2
207-08-9
50-32-8
191-24-2
314-40-9
23184-66-9
2008-41-5
128-37-0
85-68-7
12789-03-6
5103-71-9
5103-74-2
39765-80-5
470-90-6
2675-77-6
510-15-6
525.3-2
-------
Analyte
Chloropropham
Chlorothalonil
Chlorpyrifos
Chrysene
Cyanazine
Cycloate
Dacthal (DCPA)
ODD, 4,4'-
DDE, 4,4'-
DDT, 4,4'-
DEET(N,N-Diethyl-meta-toluamide)
Dibenz[a,/z]anthracene
Di-n-butylpthalate
Dichlorvos
Dieldrin
Diethylphthalate
Di(2-ethylhexyl)adipate
Di(2-ethylhexyl)phthalate
Diisopropyl methylphosphonate (DIMP)
Dimethipin
Dimethylphthalate
Dinitrotoluene, 2,4-
Dinitrotoluene, 2,6-
Diphenamid
Disulfoton
Endosufan I
Endosufan II
Endosufan sulfate
Endrin
EPTC (S-Ethyl dipropylthiocarbamate)
Ethion
Ethoprop
Ethyl parathion
Etridiazole
Fenarimol
Fluorene
Fluridone
Heptachlor
Heptachlor epoxide
Hexachlorobenzene (HCB)
Hexachlorocyclohexane, alpha (a-HCH)
Hexachlorocyclohexane, beta (P-HCH)
Chemical Abstract
Services Registry
Number (CASRN)
101-21-3
1897-45-6
2921-88-2
218-01-9
21725-46-2
1134-23-2
1861-32-1
72-54-8
72-55-9
50-29-3
134-62-3
53-70-3
84-74-2
62-73-7
60-57-1
84-66-2
103-23-1
117-81-7
1445.75.6
55290-64-7
131-11-3
121-14-2
606-20-2
957-51-7
298-04-4
959-98-8
33213-65-9
1031-07-8
72-20-8
759-94-4
563-12-2
13194-48-4
56-38-2
2593-15-9
60168-88-9
86-73-7
59756-60-4
76-44-8
1024-57-3
118-74-1
319-84-6
319-85-7
525.3-3
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Analyte
Hexachlorocyclohexane, delta (5-HCH)
Hexachlorocyclohexane, gamma (y-HCH) (Lindane)
Hexachlorocyclopentadiene (HCCPD)
Hexazinone
Indeno [\.,2,3-c,d] pyrene
Isophorone
Methoxychlor
Methyl parathion
Metolachlor
Metribuzin
Mevinphos
MGK 264
Molinate
Napropamide
Nitrofen
Norflurazon
Oxyfluorfen
Pebulate
Pentachlorophenol
Phenanthrene
Permethrin, cis-
Permethrin, trans-
Prometon
Phorate
Phosphamidon
Profenofos
Prometryn
Pronamide
Propachlor
Propazine
Pyrene
Simazine
Simetryn
Tebuconazole
Tebuthiuron
Terbacil
Terbutryn
Tetrachlorvinphos
Tribufos
Toxaphene
Triadimefon
Trifluralin
Chemical Abstract
Services Registry
Number (CASRN)
319-86-8
58-89-9
77-47-4
51235-04-2
193-39-5
78-59-1
72-43-5
298-00-0
51218-45-2
21087-64-9
7786-34-7
113-48-4
2212-67-1
15299-99-7
1836-25-5
27314-13-2
42874-03-3
1114-71-2
87-86-5
85-01-8
54774-45-7
51877-74-8
1610-18-0
298-02-2
13171-21-6
41198-08-7
7287-19-6
23950-58-5
1918-16-7
139-40-2
129-00-0
122-34-9
1014-70-6
107534-96-3
34014-18-1
5902-51-2
886-50-0
22248-79-9
78-48-8
8001-35-2
43121-43-3
1582-09-8
525.3-4
-------
Analyte
Vernolate
Vinclozolin
Polychlorinated Biphenyl (PCB) Congeners (IUPAC #)
2-chlorobiphenyl (1)
4-chlorobiphenyl (3)
2,4'-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
2, 2 ', 3 , 5 '-tetrachlorobiphenyl (44)
2,2',5,5'-tetrachlorobiphenyl(52)
2, 3 ',4 ', 5 -tetrachloroobiphenyl (70)
2,3,3',4',6-pentachlorobiphenyl (110)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Chemical Abstract
Services Registry
Number (CASRN)
1929-77-7
50471-44-8
2051-60-7
2051-62-9
34883-43-7
37680-65-2
7012-37-5
41464-39-5
35693-99-3
32598-11-1
38380-03-9
31508-00-6
35065-28-2
38380-04-0
35065-27-1
35065-29-3
1.2. The Minimum Reporting Level (MRL) is the lowest analyte concentration that meets
Data Quality Objectives (DQOs) that are developed based on the intended use of this
method. The single laboratory lowest concentration MRL (LCMRL) (Sect. 3.12) is
the lowest true concentration for which the future recovery is predicted to fall, with
high confidence (99 percent), between 50 and 150 percent recovery. The LCMRL is
compound dependent and is also dependent on extraction efficiency, sample matrix,
fortification concentration, and instrument performance. The procedure used to
determine the LCMRL is described elsewhere.1;2 During method development,
LCMRLs were determined by two laboratories from the results of laboratory
fortified blanks (LFBs) in full scan mode for all method analytes. LCMRLs were
also determined for selected analytes in the SIM mode. These LCMRLs are
provided in Tables 15 and 23 for full scan and SIM analyses, respectively.
1.3 Laboratories using this method are not required to determine the LCMRL for this
method, but will need to demonstrate that their laboratory MRL for this method
meets the requirements described in Sect. 9.2.4.
1.4 Determining the Detection Limit (DL) for analytes in this method is optional
(Sect. 9.2.6). Detection limit is defined as the statistically calculated minimum
concentration that can be measured with 99% confidence that the reported value is
greater than zero.3 The DL is compound dependent and is also dependent on
extraction efficiency, sample matrix, fortification concentration, and instrument
performance. DLs have been determined for all analytes in two laboratories in full
525.3-5
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scan mode (Table 15) and by a single laboratory for selected analytes in SIM mode
(Table 23).
1.5 This method is intended for use by analysts skilled in solid phase extractions, the
operation of GC/MS instruments, and the interpretation of the associated data.
1.6 Analysts and laboratory managers are advised that analyzing for all of the method
analytes on a continuing basis while maintaining quality control criteria may be
difficult. It is highly recommended that analysts and laboratory managers consider
analyzing a subset of the analyte list that will meet their data collection needs.
1.7 Multi-Component Analytes
1.7.1 Toxaphene is a pesticide manufactured by the chlorination of camphene.
Over 1000 individual congeners, mainly chlorinated bornanes, have been
identified in the technical mixture, although over 30,000 are theoretically
possible. The most abundant of the individual components of the technical
mixture are typically less than 1% by weight of the total mass. Using the
instrument parameters in Method 525.3, technical toxaphene elutes as a
poorly defined group of peaks between 21 and 26 min (Fig. 2).
Toxaphene's complex composition introduces the potential for interferences
that could negatively affect the method performance for other analytes.
Therefore, all calibration standards and quality control procedures for
toxaphene must be prepared and analyzed in separate samples from all the
other method analytes. Toxaphene may be analyzed using this method in
either full scan or SIM mode. However, the authors have demonstrated the
method in SIM mode only. At the time of method development, the
enhanced sensitivity provided by SIM was necessary to meet the drinking
water monitoring trigger of 0.001 mg/L [40CFR 141.24 (h)(18)] and
maximum contaminant level (MCL) of 0.003 mg/L [40CFR 141.61 (c)].
Detailed instructions for the identification and quantitation of toxaphene are
in Sect. 12.3.3.
1.7.2 Aroclors - The PCB congeners selected as analytes in this method are
representative of the major components (by weight percent) of Aroclors
1016, 1221, 1232, 1242, 1248, 1254, and 1260.4'5 Analyzing for these
specific congeners allows the analyst to screen samples for possible Aroclor
contamination without complex pattern recognition protocols. This method
is designed for Aroclor screening only and not for qualitative or quantitative
analyses of specific Aroclors.
1.7.3 Technical chlordane - Technical chlordane is a multi-component analyte
regulated under the Safe Drinking Water Act (SDWA) at the time of
publication of this method. It contains at least 140 chlorinated components.
At the concentrations likely to be encountered in drinking water samples,
only two or three major components will typically be identified: cis- and
525.3-6
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trans-chlordane and trans-nonachlor. These major components are listed as
method analytes along with technical chlordane. Specific instructions for
quantification of technical chlordane are provided in Sect. 12.3.1.
1.8 METHOD FLEXIBILITY - In recognition of technological advances in analytical
systems and techniques, the laboratory is permitted to modify the GC inlet, inlet
conditions, column, injection parameters, and all other GC and MS conditions.
Changes may not be made to sample collection and preservation (Sect. 8), sample
extraction (Sect. 11) or to the Quality Control (QC) requirements (Sect. 9). Method
modifications should be considered only to improve method performance.
Modifications that are introduced in the interest of reducing cost or sample
processing time, but result in poorer method performance, should not be used. In all
cases where method modifications are proposed, the analyst must perform the
procedures outlined in the initial demonstration of capability (IDC, Sect. 9.2), verify
that all QC acceptance criteria in this method (Sect. 9) are met, and that method
performance in real sample matrices is equivalent to that demonstrated for
Laboratory Fortified Sample Matrices (LFSMs) in Sect. 17.
Note: The above method flexibility section is intended as an abbreviated summation
of method flexibility. Sects. 4-12 provide detailed information of specific portions
of the method that may be modified. If there is any perceived conflict between the
general method flexibility statement in Sect. 1.8 and specific information in Sects. 4-
12, Sects. 4-12 supersede Sect. 1.8.
2. SUMMARY OF METHOD
2.1. A 1-liter water sample is fortified with surrogate analytes and passed through a solid
phase extraction (SPE) device (Sects. 6.9-6.13) to extract the target analytes and
surrogates. The compounds are eluted from the solid phase with a small amount of
two or more organic solvents. The solvent extract is dried by passing it through a
column of anhydrous sodium sulfate, concentrated by evaporation with nitrogen gas,
and then adjusted to a 1-mL volume with ethyl acetate after adding the internal
standards. A splitless injection is made into a GC equipped with a high-resolution
fused silica capillary column that is interfaced to an MS. The analytes are separated
and identified by comparing the acquired mass spectra and retention times to
reference spectra and retention times for calibration standards acquired under
identical GC/MS conditions. The GC/MS may be operated in the full scan, SIM, or
selected ion storage (SIS) mode (Sects 3.19 and 3.20). The GC/MS may be
calibrated using standards prepared in solvent or using matrix-matched standards
(Sects. 3.15 and 7.2.4). The concentration of each analyte is calculated by using its
integrated peak area and the internal standard technique. Surrogate analytes are
added to all Field and Quality Control (QC) Samples to monitor the performance of
each extraction and overall method performance.
2.2 Some analytes in this method can be affected by matrix induced chromatographic
response enhancement (Sect. 3.14), when analyzed at low concentrations. Refer to
525.3-7
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the "comments" section of Table 1 for potentially affected analytes, and to Sect. 13
for information regarding method performance.
3. DEFINITIONS
3.1. ANALYSIS BATCH - A set of samples that is analyzed on the same instrument
during a 24-hour period that begins and ends with the analysis of the appropriate
Continuing Calibration Check (CCC) Standards. Additional CCCs may be required
depending on the length of the analysis batch and/or the number of Field Samples.
3.2. CALIBRATION STANDARD (CAL) - A solution prepared from the primary
dilution standard solution or stock standard solution(s) and the internal standards and
surrogate analytes. The CAL solutions are used to calibrate the instrument response
with respect to analyte concentration. In this method, traditional CAL standards
prepared in ethyl acetate may be used or matrix-matched standards (Sect. 3.15)
prepared in a concentrated laboratory reagent water (LRW) extract may be used.
This procedure is described in Sect. 7.2.4.2.
3.3. CONTINUING CALIBRATION CHECK (CCC) STANDARD - A calibration
standard containing one or more method analytes, which is analyzed periodically to
verify the accuracy of the existing calibration for those analytes.
3.4. DETECTION LIMIT (DL) - The minimum concentration of an analyte that can be
identified, measured and reported with 99% confidence that the analyte
concentration is greater than zero. This is a statistical determination (Sect. 9.2.6),
and accurate quantitation is not expected at this level.3
3.5. EXTRACTION BATCH - A set of up to 20 Field Samples (not including QC
samples) extracted together by the same person(s) during a work day using the same
lot of solid phase extraction devices, solvents, surrogate solution, and fortifying
solutions. Required QC samples include Laboratory Reagent Blank, Laboratory
Fortified Blank, Laboratory Fortified Sample Matrix, and either a Field Duplicate or
Laboratory Fortified Sample Matrix Duplicate.
3.6. FIELD DUPLICATES (FD1 and FD2) - Two separate samples collected at the same
time and place under identical circumstances, and treated exactly the same
throughout field and laboratory procedures. Analyses of FD1 and FD2 provide an
estimate of the precision associated with sample collection, preservation, and
storage, as well as with laboratory procedures.
3.7. INTERNAL STANDARD (IS) - A pure compound added to an extract or standard
solution in a known amount and used to measure the relative responses of the
method analytes and surrogates. In this method, the internal standards are
isotopically labeled analogues of selected method analytes.
525.3-8
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3.8. LABORATORY FORTIFIED BLANK (LFB) - An aliquot of reagent water or other
blank matrix to which known quantities of the method analytes and all the
preservation compounds are added. The LFB is processed and analyzed exactly like
a sample, and its purpose is to determine whether the methodology is in control, and
whether the laboratory is capable of making accurate and precise measurements.
3.9. LABORATORY FORTIFIED SAMPLE MATRIX (LFSM) - An aliquot of a Field
Sample to which known quantities of the method analytes and all the preservation
compounds are added. The LFSM is processed and analyzed exactly like a sample,
and its purpose is to determine whether the sample matrix contributes bias to the
analytical results. The background concentrations of the analytes in the sample
matrix must be determined in a separate aliquot and the measured values in the
LFSM corrected for background concentrations.
3.10. LABORATORY FORTIFIED SAMPLE MATRIX DUPLICATE (LFSMD) - A
duplicate Field Sample used to prepare the LFSM, which is fortified, extracted and
analyzed identically to the LFSM. The LFSMD is used instead of the Field
Duplicate to assess method precision and accuracy when the occurrence of a method
analyte is infrequent.
3.11. LABORATORY REAGENT BLANK (LRB) - An aliquot of reagent water that is
treated exactly as a sample including exposure to all glassware, equipment, solvents,
reagents, sample preservatives, internal standards, and surrogates that are used in the
extraction batch. The LRB is used to determine if method analytes or other
interferences are present in the laboratory environment, the reagents, or the
extraction apparatus.
3.12. LOWEST CONCENTRATION MINIMUM REPORTING LEVEL (LCMRL) - The
single-laboratory LCMRL is the lowest true concentration for which the future
recovery is predicted to fall, with high confidence (99 percent), between 50 and 150
percent recovery.1'2
3.13. MATERIAL SAFETY DATA SHEET (MSDS) - Written information provided by
vendors concerning a chemical's toxicity, health hazards, physical properties, fire,
and reactivity data including storage, spill, and handling precautions.
3.14. MATRIX-INDUCED CHROMATOGRAPHIC RESPONSE ENHANCEMENT -
This phenomenon occurs when, in the absence of matrix components, method
analytes in calibration solutions are degraded or absorbed in the GC injector or
column, resulting in poor peak shapes and low response. When subsequent sample
extracts containing the analytes and components from a complex sample matrix are
injected, peak shape and response improve. In this situation, quantitative data for
field samples may exhibit a high bias.6"13 Generally, overestimation of results is
more pronounced at low analyte concentrations.
525.3-9
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3.15. MATRIX-MATCHED CALIBRATION STANDARD - A calibration standard that
is prepared by adding method analytes to a concentrated extract of a matrix (reagent
water is used for this method) that has been prepared following all the extraction and
sample preparation steps of the analytical method. The material extracted from the
matrix reduces matrix-induced response enhancement effects and improves the
quantitative accuracy of sample results.12'13
3.16. MINIMUM REPORTING LEVEL (MRL) - The minimum concentration that can be
reported by a laboratory as a quantitated value for a method analyte in a sample
following analysis. This concentration must meet the criteria defined in Sect. 9.2.4
and must not be any lower than the concentration of the lowest continuing calibration
check standard for that analyte. The MRL may be determined by the laboratory
based upon project objectives, or may be set by a regulatory body as part of a
compliance monitoring program.
3.17. PRIMARY DILUTION STANDARD SOLUTION (PDS) - A solution containing
method analytes, internal standards, or surrogate analytes prepared in the laboratory
from stock standard solutions and diluted as needed to prepare calibration solutions
and other analyte solutions.
3.18. QUALITY CONTROL SAMPLE (QCS) - A solution prepared using a PDS of
method analytes obtained from a source external to the laboratory and different from
the source of calibration standards. The second source PDS and the surrogate PDS
are used to fortify the QCS at a known concentration. The QCS is used to verify the
accuracy of the primary calibration standards.
3.19. SELECTED ION MONITORING (SIM) - An MS technique where only one or a
few ions are monitored for each target analyte. When used with gas
chromatography, the set of ions monitored is usually changed periodically
throughout the chromatographic run, to correlate with the characteristic ions of the
analytes, SURs and ISs as they elute from the chromatographic column. The
technique is often used to increase sensitivity. Throughout this document, the term
"SIM" will be used to include both SIM as described here and SIS as described in
Sect. 3.20.
3.20. SELECTED ION STORAGE (SIS) - An MS technique typically used with ion trap
mass spectrometers where only one or a few ions are stored at any given time point.
When used with gas chromatography, the set of ions stored is usually changed
periodically throughout the chromatographic run, to correlate with the characteristic
ions of the analytes, SURs and ISs as they elute from the chromatographic column.
SIS can be used to enhance sensitivity. Throughout this document the term "SIM"
will be used to include both SIM (Sect. 3.19) and SIS.
3.21. STOCK STANDARD SOLUTION (SSS) - A concentrated solution containing one
or more method analytes prepared in the laboratory using assayed reference materials
or purchased from a reputable commercial source.
525.3-10
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3.22. SURROGATE ANALYTE (SUR) - A pure analyte, which is extremely unlikely to
be found in any sample, and which is added to a sample aliquot in a known amount
before extraction or other processing, and is measured with the same procedures used
to measure other sample components. The purpose of the SUR is to monitor method
performance with each sample.
4. INTERFERENCES
4.1. All glassware must be meticulously cleaned. Wash glassware with detergent and tap
water, rinse with tap water, followed by reagent water. Rinse with methanol and/or
acetone. Non-volumetric glassware may be heated in a muffle furnace at 400 °C for
two hours as a substitute for solvent rinsing. Volumetric glassware should not be
heated in an oven above 120 °C.
4.2. Method interferences may be caused by contaminants in solvents, reagents
(including reagent water), sample bottles and caps, and other sample processing
hardware that lead to discrete artifacts and/or elevated baselines in the chromato-
grams. All items such as these must be routinely demonstrated to be free from
interferences (less than Vs the MRL for each target analyte) under the conditions of
the analysis by analyzing laboratory reagent blanks as described in Sect. 9.3.1.
Subtracting blank values from sample results is not permitted.
4.3. Matrix interferences may be caused by contaminants that are co-extracted from the
sample. The extent of matrix interferences will vary considerably from source to
source, depending upon the nature of the water. Water samples high in total organic
carbon (TOC) may have elevated baselines or interfering peaks. Matrix components
may directly interfere by producing a signal at or near the retention time of an
analyte peak. They can also enhance the signal of method analytes (Sect. 3.14).
Analyses of LFSMs are useful in identifying matrix interferences.
4.4. Relatively large quantities of the buffer and preservatives (Sect. 8.1.2) are added to
sample bottles. The potential exists for trace-level organic contaminants in these
reagents. Interferences from these sources should be monitored by analysis of
laboratory reagent blanks, particularly when new lots of reagents are acquired.
4.5. Solid phase extraction media have been observed to be a source of interferences.14
The analysis of field and laboratory reagent blanks can provide important
information regarding the presence or absence of such interferences. Brands and lots
of solid phase extraction devices should be tested to ensure that contamination does
not preclude analyte identification and quantitation.
Analyte carryover may occur when a relatively "clean" sample is analyzed
immediately after a sample (or standard) that contains relatively high concentrations
of compounds. Syringes and GC injection port liners must be cleaned carefully or
replaced as needed. After analysis of a sample (or standard) that contains high
concentrations of compounds, a laboratory reagent blank should be analyzed to
525.3-11
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ensure that accurate values are obtained for the next sample. The analyst should be
especially careful to check for carryover of polycyclic aromatic hydrocarbons
(PAHs) and PCBs.
4.7. Silicone compounds may be leached from punctured autosampler vial septa,
particularly when particles of the septa sit in the vial. This can occur after repeated
injections from the same autosampler vial. These silicone compounds, which appear
as regularly spaced chromatographic peaks with similar MS fragmentation patterns,
can unnecessarily complicate the total ion chromatograms and may cause
interferences at high levels.
4.8. Quantitation of bromacil should be reviewed for potential common interferences.
The quantitation ion (QI) m/z 205 suggested in Table 1 can be found in SPE media;
therefore, method blanks should be carefully examined for this potential interference.
The ion at m/z 207 may be used as an alternate QI; however, this ion is associated
with column bleed. Laboratories should select the QI depending on the sorbent
being used and the amount of bleed associated with the GC column. If both types of
interferences are present, some laboratories may not be able to analyze for bromacil
at low concentrations. Manual inspection of all bromacil data reported in field
samples is mandatory.
4.9. There are many potential sources of phthalate contamination in the laboratory,
especially from plastics and chemicals that may have been stored in plastic
containers. If phthalates are to be reported as method analytes, care must be taken to
minimize sources of contamination, and the QC criteria for LRBs must be met
(Sect. 9.3.1). Special precautions must also be taken when creating calibration
curves for analytes consistently found in LRBs (Sect. 10.2.5).
4.10. In cases where the SPE disks or cartridges are dried by pulling room air through the
media using vacuum, it may be possible for the media to become contaminated by
components in room air. This was not observed during method development. If
laboratories encounter contamination problems associated with room air, compressed
gas cylinders of high purity nitrogen may be used for drying SPE media during
sample processing.
4.11. If samples are to be analyzed for DEET, sample collection personnel should be
cautioned against the use of insect repellents containing DEET.
5. SAFETY
5.1. The toxicity or carcinogenicity of each reagent used in this method has not been
precisely defined. Each chemical should be treated as a potential health hazard, and
exposure to these chemicals should be minimized. Each laboratory is responsible for
maintaining an awareness of OSHA regulations regarding safe handling of chemicals
used in this method. A reference file of MSDSs should be made available to all
525.3-12
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personnel involved in the chemical analysis. Additional references to laboratory
safety are available.15"17
5.2. Pure standard materials and stock standard solutions of these compounds should be
handled with suitable protection to skin and eyes, and care should be taken not to
breathe the vapors or ingest the materials.
6. EQUIPMENT AND SUPPLIES
References to specific brands or catalog numbers are included for illustration only, and do
not imply endorsement of the product. Other brands of equivalent quality may be used. The
SPE sorbents described in Sects. 6.9-6.11 are proprietary products that have been fully
evaluated for use in this method by two laboratories. The sorbents described in Sects. 6.12
and 6.13 are proprietary products with demonstration data provided by the vendor. Due to
their proprietary status, some aspects of the chemistry of all of these sorbents are unknown
making equivalency difficult to determine. The EPA document "Technical Notes on
Drinking Water Methods"18 provides criteria for judging equivalency of SPE products.
Before analyses are performed for compliance under the Safe Drinking Water Act, questions
regarding equivalency of alternate sorbent materials must be addressed to the Office of
Ground Water and Drinking Water Alternate Test Procedure Coordinator.19
6.1. SAMPLE CONTAINERS - 1 -L or 1 -qt amber glass bottles fitted with
polytetrafluoroethylene (PTFE)-lined screw caps are preferred. Clear glass bottles
with PTFE-lined screw caps may be substituted if sample bottles are wrapped with
foil, stored in boxes, or otherwise protected from light during sample shipping and
storage.
6.2. VIALS - Various sizes of amber glass vials with PTFE-lined screw caps for storing
standard solutions and extracts. Amber glass 2-mL autosampler vials with PTFE-
faced septa.
6.3. VOLUMETRIC FLASKS - Class A, suggested sizes include 1, 5, and 10 mL for
preparation of standards and dilution of extract to final volume.
6.4. GRADUATED CYLINDERS - Suggested sizes include 5, 10, 250 and 1000 mL.
6.5. MICRO SYRINGES - Suggested sizes include 10, 25, 50, 100, 250, 500, and
1000 |iL.
6.6. DRYING COLUMN - The drying column must be able to contain 10-12 g of
anhydrous sodium sulfate (Na2SO/t). The drying column should not leach interfering
compounds or irreversibly adsorb method analytes. Any small glass or
polypropylene column may be used, such as Supelco #57176.
525.3-13
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6.7. COLLECTION TUBES - 15 to 50 mL, conical tubes (Fisher #05-569-6C) or other
glassware suitable for collection of the eluent from the solid phase after extraction
and for collecting extract from drying tube.
6.8. ANALYTICAL BALANCE - Capable of weighing to the nearest 0.0001 g.
6.9. SPE APPARATUS USING PTFE DISKS; MANUAL EXTRACTION
6.9.1. SPE DISKS - 47-mm diameter and 0.5-mm thick, manufactured with a
styrene divinylbenzene (SDVB) sorbent (Empore SDB-XC, #2240 or
equivalent).
Note: Several brands of SDVB and modified SDVB media in cartridge
format were evaluated during method development and did not provide
satisfactory performance. Therefore, SDVB cartridges are not included in
this method.
6.9.2. SPE DISK EXTRACTION GLASSWARE - glass funnel, PTFE-coated
support screen, PTFE gasket, base, and clamp used to support SPE disks
and contain samples during extraction. May be purchased as a set
(Fisher #K971100-0047, Kontes #971000-6047, or equivalent) or
separately.
6.9.3. VACUUM EXTRACTION MANIFOLD - Designed to accommodate
extraction glassware and disks (Kontes #971000-6047, or UCT
#ECUCTVAC6, or equivalent).
6.9.4. An automatic or robotic system designed for use with PTFE disks may be
used if all quality control requirements discussed in Sect. 9 are met.
Automated systems may use either vacuum or positive pressure to process
samples and solvents through the disk. All sorbent washing, conditioning.
sample loading, rinsing, drying and elution steps must be performed as
closely as possible to the manual procedure. The solvents used for washing.
conditioning, and sample elution must be the same as those used in the
manual procedure: however, the amount used may be increased as
necessary to achieve the required data quality. Solvent amounts may not be
decreased. Sorbent drying times prior to elution may be modified to
achieve the required data quality. Caution should be exercised when
increasing solvent volumes. Increased extract volume will likely
necessitate the need for additional sodium sulfate drying, and extended
evaporation times which may compromise data quality. Caution should
also be exercised when modifying sorbent drying times. Excessive drying
may cause losses due to analyte volatility, and excessive contact with room
air may oxidize some method analytes. Insufficient drying may leave
excessive water trapped in the disk and lead to poor recoveries.
525.3-14
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6.10. SPE APPARATUS USING SPEEDISKS; MANUAL EXTRACTION
6.10.1. SPEEDISKS - J.T. Baker H2O Phobic Divinylbenzene (DVB) Speedisk,
regular capacity (part #8068-06).
6.10.2. VACUUM EXTRACTION MANIFOLD - J.T. Baker #8095-06
6.10.3. An automatic or robotic system designed for use with SPEEDISKS may be
used if all quality control requirements discussed in Sect. 9 are met.
Automated systems may use either vacuum or positive pressure to process
samples and solvents through the disk. All sorbent washing, conditioning,
sample loading, rinsing, drying and elution steps must be performed as
closely as possible to the manual procedure. The solvents used for washing,
conditioning, and sample elution must be the same as those used in the
manual procedure: however, the amount used may be increased as
necessary to achieve the required data quality. Solvent amounts may not be
decreased. Sorbent drying times prior to elution may be modified to
achieve the required data quality. Caution should be exercised when
increasing solvent volumes. Increased extract volume will likely
necessitate the need for additional sodium sulfate drying, and extended
evaporation times which may compromise data quality. Caution should
also be exercised when modifying sorbent drying times. Excessive drying
may cause losses due to analyte volatility, and excessive contact with room
air may oxidize some method analytes. Insufficient drying may leave
excessive water trapped in the disk and lead to poor recoveries.
6.11. SPE APPARATUS USING SPE CARTRIDGES (6-mL COLUMNS); MANUAL
EXTRACTION
6.11.1. SPE CARTRIDGES - Modified DVB polymer (not SDVB polymer-see
note below).
Note: Several brands of SDVB and modified SDVB media in cartridge
format were evaluated during method development and did not provide
satisfactory performance. Therefore, SDVB cartridge products are not
included in this method.
6.11.1.1. Waters Oasis HLB, 500 mg (Waters #186000115) -
divinylbenzene N-vinylpyrrolidone copolymer
6.11.1.2. J.T. Baker Speedisk Column H2O Phobic DVB, 200 mg
(#8109-09) - divinylbenzene polymer
6.11.2. VACUUM EXTRACTION MANIFOLD - Equipped with flow/vacuum
control (Supelco #57030-U or equivalent).
525.3-15
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6.11.3. SAMPLE DELIVERY SYSTEM - Use of a transfer tube system (Supelco
"Visiprep", #57275 or equivalent), which transfers the sample directly from
the sample container to the SPE cartridge is recommended.
6.11.4. An automatic or robotic system designed for use with SPE cartridges may
be used if all quality control requirements discussed in Sect. 9 are met.
Automated systems may use either vacuum or positive pressure to process
samples and solvents through the cartridge. All sorbent washing,
conditioning, sample loading, rinsing, drying and elution steps must be
performed as closely as possible to the manual procedure. The solvents
used for washing, conditioning, and sample elution must be the same as
those used in the manual procedure: however, the amount used may be
increased as necessary to achieve the required data quality. Solvent
amounts may not be decreased. Sorbent drying times prior to elution may
be modified to achieve the required data quality. Caution should be
exercised when increasing solvent volumes. Increased extract volume will
likely necessitate the need for additional sodium sulfate drying, and
extended evaporation times which may compromise data quality. Caution
should also be exercised when modifying sorbent drying times. Excessive
drying may cause losses due to analyte volatility, and excessive contact
with room air may oxidize some method analytes. Insufficient drying may
leave excessive water trapped in the disk and lead to poor recoveries.
6.12. SPE APPARATUS USING SPE CARTRIDGES (83-mL COLUMNS); MANUAL
EXTRACTION
6.12.1. SPE CARTRIDGES - United Chemical Technologies (UCT) 525 Universal
cartridge, #ECUNI525, 1500 mg octadecyl unendcapped bonded silica,
carbon loading 15-18%, surface area approximately 500 m2/g, or
equivalent.
6.12.2. VACUUM EXTRACTION MANIFOLD - Designed to accommodate
extraction glassware and cartridges (Varian #1214-6001 or
UCT # ECUCTVAC6 or equivalent).
6.12.3. CARTRIDGE ADAPTER - UCT #ECUCTADP
6.12.4. BOTTLE HOLDER - UCT #ECUNIBHD
6.12.5. An automatic or robotic system designed for use with SPE cartridges may
be used if all quality control requirements discussed in Sect. 9 are met.
Automated systems may use either vacuum or positive pressure to process
samples and solvents through the cartridge. All sorbent washing.
conditioning, sample loading, rinsing, drying and elution steps must be
performed as closely as possible to the manual procedure. The solvents
used for washing, conditioning, and sample elution must be the same as
525.3-16
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those used in the manual procedure: however, the amount used may be
increased as necessary to achieve the required data quality. Solvent
amounts may not be decreased. Sorbent drying times prior to elution may
be modified to achieve the required data quality. Caution should be
exercised when increasing solvent volumes. Increased extract volume will
likely necessitate the need for additional sodium sulfate drying, and
extended evaporation times which may compromise data quality. Caution
should also be exercised when modifying sorbent drying times. Excessive
drying may cause losses due to analyte volatility, and excessive contact
with room air may oxidize some method analytes. Insufficient drying may
leave excessive water trapped in the disk and lead to poor recoveries.
6.13. SPE APPARATUS USING HORIZON ATLANTIC DVB DISKS WITH
AUTOMATED OR MANUAL EXTRACTION
6.13.1. SPE DISKS - Horizon Atlantic DVB disk, 50 mm diameter, 4mm thick,
#47-2346-06, or equivalent
6.13.2. DISK HOLDER ASSEMBLY - 50 mm disk holder with extended riser,
Horizon #50-2629 or equivalent
6.13.3. VACUUM EXTRACTION MANIFOLD - Equipped with flow/vacuum
control (Supelco #57030-U) or equivalent
6.13.4. SPE-DEX 4790 Automated Extraction System, Horizon Technology
6.14. EXTRACT CONCENTRATION SYSTEM - Extracts are concentrated by
evaporation with nitrogen gas using a water bath set at 40 °C (N-Evap, Model 11155,
Organomation Associates, Inc., or equivalent).
6.15. LABORATORY OR ASPIRATOR VACUUM SYSTEM - Sufficient capacity to
maintain a vacuum of approximately 15 to 25 inches of mercury.
6.16. GAS CHROMATOGRAPH/MASS SPECTROMETER (GC/MS) SYSTEM
6.16.1. FUSED SILICA CAPILLARY GC COLUMN - 30 m x 0.25-mm inside
diameter (i.d.) fused silica capillary column coated with a 0.25 jim bonded
film of poly(dimethylsiloxy)poly(l,4-bis(dimethylsiloxy)phenylene)-
siloxane (Restek RXI-5sil-MS or equivalent). Any capillary column that
provides adequate capacity, resolution, accuracy, and precision may be
used. A nonpolar, low-bleed column is recommended for use with this
method to provide adequate resolution and minimize column bleed.
6.16.2. GC INJECTOR AND OVEN - Some of the target compounds included in
this method are subject to thermal breakdown in the GC injection port. This
problem is exacerbated when the injector and/or the injection port liner is
525.3-17
-------
not properly deactivated or is operated at excessive temperatures. The
injection system must not allow analytes to contact hot stainless steel or
other metal surfaces that promote decomposition. The performance data in
Sect. 17 were obtained using hot, splitless injection using a 4 or 5-mm i.d.
glass deactivated liner. Other injection techniques such as temperature pro-
grammed injections, cold on-column injections and large volume injections
may be used if the QC criteria in Sect. 9 are met. Equipment designed
appropriately for these alternate types of injections must be used if these
options are employed.
6.16.3. GC/MS INTERFACE - The interface should allow the capillary column or
transfer line exit to be placed within a few millimeters of the ion source.
Other interfaces are acceptable as long as the system has adequate
sensitivity and QC performance criteria are met.
6.16.4. MASS SPECTROMETER (MS) - Any type of MS may be used (i.e.,
quadrupole, ion trap, time of flight, etc.) with electron impact ionization.
The instrument may be operated in full scan mode or in SIM mode for
enhanced sensitivity. The minimum scan range capability of the MS must
be 45 to 450 m/z, and it must produce a full scan mass spectrum that meets
all criteria in Table 2 when a solution containing 5 ng (or less) of
decafluorotriphenylphosphine (DFTPP) is injected into the GC/MS
(Sect. 10.2.1).
6.16.5. DATA SYSTEM - An interfaced data system is required to acquire, store,
and output MS data. The computer software should have the capability of
processing stored GC/MS data by recognizing a GC peak within a given
retention time window. The software must allow integration of the ion
abundance of any specific ion between specified time or scan number
limits. The software must be able to construct linear regressions and
quadratic calibration curves, and calculate analyte concentrations.
7. REAGENTS AND STANDARDS SUPPLIES (References to specific brands or catalog
numbers are included for illustration only, and do not imply endorsement of the product.)
7.1. REAGENTS AND SOLVENTS - Reagent grade or better chemicals should be used
in all tests. Unless otherwise indicated, it is intended that all reagents will conform
to the specifications of the Committee on Analytical Reagents of the American
Chemical Society (ACS), where such specifications are available. Other grades may
be used, if the reagents are demonstrated free of analytes and interferences, and all
method requirements in the Initial Demonstration of Capability (IDC) are met.
7.1.1. HELIUM - 99.999 % or better, GC carrier gas.
525.3-18
-------
7.1.2. LABORATORY REAGENT WATER (LRW) - Purified water which does
not contain any measurable quantities of any target analytes or interfering
compounds at or above Vs the MRL for each compound of interest.
7.1.3. METHANOL (MeOH) (CASRN 67-56-1) - High purity, demonstrated to be
free of analytes and interferences (Fisher Optima or equivalent).
7.1.4. ETHYL ACETATE (EtOAc) (CASRN 141-78-6) - High purity,
demonstrated to be free of analytes and interferences (Tedia Absolv or
equivalent).
7.1.5. DICHLOROMETHANE (DCM) (CASRN 75-09-02) - High purity,
demonstrated to be free of analytes and interferences (Fisher GC Resolv or
equivalent).
7.1.6. ACETONE (CASRN 67-64-1) - High purity, demonstrated to be free of
analytes and interferences (Tedia Absolv or equivalent).
7.1.7. SODIUM SULFATE (Na2SO4), ANHYDROUS (CASRN 7757-82-6) -
Soxhlet extracted with DCM for a minimum of four hours or heated to
400 °C for two hours in a muffle furnace. An "ACS grade, suitable for
pesticide residue analysis," is recommended.
7.1.8. SAMPLE PRESERVATION REAGENTS - The following preservatives
are solids at room temperature and may be added to the sample bottle before
shipment to the field.
7.1.8.1. POTASSIUM DIHYDROGEN CITRATE (CASRN 866-83-1) -
The sample must be buffered to pH 3.8 to inhibit microbial growth
and analyte degradation.20
7.1.8.2. L-ASCORBIC ACID (CASRN 50-81-7) - Ascorbic acid reduces
free chlorine at the time of sample collection (ACS Reagent Grade
or equivalent).21
7.1.8.3. ETHYLENEDIAMINE TETRAACETIC ACID (EDTA),
TRISODIUM SALT (CASRN 10378-22-0) - Trisodium EDTA is
added to inhibit metal-catalyzed hydrolysis of analytes.20'21
7.2. STANDARD SOLUTIONS - Standard solutions of internal standards, surrogates
and method analytes may be prepared gravimetrically or from commercially
available stock solutions. When a compound purity is assayed to be 96% or greater,
the weight can be used without correction to calculate the concentration of a
gravimetrically prepared stock standard. Solution concentrations listed in this
section were those used to develop this method and are included as an example only.
Solution preparation steps may be modified as needed to meet the needs of the
525.3-19
-------
laboratory. Often, standard mixes appropriate to the method become commercially
available subsequent to method publication. Even though stability times for
standard solutions are suggested in the following sections, laboratories should
use standard QC practices to determine when their standards need to be
replaced. In addition, signs of evaporation and/or discoloration are indicators
that a standard should be replaced.
7.2.1.
7.2.2.
INTERNAL STANDARD (IS) SOLUTIONS - This method uses four IS
compounds listed in the table below. ISs 1-3 are the same as those used in
previous versions of this method and are available individually and as a
mixture from many commercial sources. A commercial mixture of ISs 1-3
was used for method development, and it is highly recommended that other
analysts use a commercial mix as well. However, if an analyst chooses to
prepare a gravimetric stock solution, it should be prepared in acetone using
a procedure similar to the preparation of analyte stocks as outlined in Sect.
7.2.3.1. The PDS mix for ISs 1-3 has been shown to be stable for at least
one year when stored in amber glass screw cap vials at -5 °C or less. The
PDS for IS 4, 13C-pentachlorophenol, was prepared from neat material in
methanol at 1000 jig/mL. The neat material was obtained from CDN
Isotopes. This IS PDS has been shown to be stable for at least nine months
when stored in amber glass screw cap vials at -5 °C or less. Using 10 jiL of
the PDS for ISs 1-3 and 4 |iL of the PDS for IS 4 to fortify the final 1-mL
extracts (Sect. 11.9) will yield a concentration of 5 |ig/mL each for ISs 1-3
and 4 |ig/mL of IS 4 for full scan analysis. Lower concentrations of ISs 1-3
should be used for SIM analysis. For SIM analysis during method
development, ISs 1-3 were added to extracts such that their final
concentration was 1 |ig/mL. The IS 4 concentration remained at 4 |ig/mL
for most analyses due to the low abundance of the m/z 276 QI. IS 4 should
be omitted if pentachlorophenol is not being measured as an analyte.
Note: Stock standard solutions and PDSs should be brought to room
temperature and sonicated for few minutes prior to use. This ensures that
components are dissolved and the solution is homogeneous.
Internal Standards
acenaphthene-t/io (IS 1)
phenanthrene-t/io (IS 2)
chrysene-t/i2 (IS 3)
13C-pentachlorophenol (IS 4)
CASRN
15067-26-2
1517-22-2
1719-03-5
85380-74-1
Solvent
acetone
acetone
acetone
methanol
PDS cone.
500 |ig/mL
500 |ig/mL
500 |ig/mL
1000 |ig/mL
SURROGATE ANALYTE STANDARD SOLUTIONS - The surrogate
analytes used in this method are listed in the table below. All SUR PDSs
were used at the same concentration and were prepared in acetone. The
525.3-20
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SURs may be prepared or purchased (if available from commercial
suppliers) as individual PDSs or a single PDS. The SUR PDSs have been
shown to be stable for at least one year when stored in amber glass screw
cap vials at -5 °C or less. For full scan analysis, 10 jiL of each of these
solutions was added to each 1L aqueous QC and Field Sample prior to
extraction, for an expected final extract concentration of 5 jig/L of each
SUR. For SIM analyses the QC and Field Samples were fortified such that
the expected final extract concentration was 1 |ig/L for each SUR.
Surrogates
l,3-dimethyl-2-nitrobenzene (SUR 1)
triphenyl phosphate (SUR 2)
benzo[a]pyrene-t/i2 (SUR 3)
CASRN
81-20-9
115-86-6
63466-71-7
Solvent
acetone
acetone
acetone
PDS cone.
500 ng/mL
500 ng/mL
500 ng/mL
Notes:
• Stock standard solutions and PDSs should be brought to room
temperature and sonicated for a few minutes prior to use. This ensures
that components are dissolved and the solution is homogeneous.
• Stock standard solutions that will be used for aqueous sample
fortification generally should be prepared at a concentration such that
only a small volume (e.g., 5-100 jiL) needs to be added to achieve the
desired final concentration. This will minimize the quantity of organic
solvent added to aqueous samples.
7.2.3. ANALYTE STOCK SOLUTIONS
7.2.3.1. ANALYTE STOCK STANDARD SOLUTIONS (SSS)
(0.5-5.0 mg/mL) - Analyte standards may be purchased
commercially as ampulized solutions prepared from neat materials.
Commercially prepared SSSs are widely available for most method
analytes. Exceptions are DIMP, which at the time of method
development was available only from Cerilliant, and the 14 PCB
congeners. During method development, custom PCB mixes were
obtained from Accustandard and Chem Service, Inc. Many groups
of analytes can also be purchased as PDSs, making the preparation
of individual SSSs unnecessary. To prepare gravimetric stock
standard solutions, add 10 mg (weighed on analytical balance to
0.1 mg) of the pure material to 1.9 mL of solvent in a 2-mL
volumetric flask, dilute to the mark, and transfer the solution to an
amber glass vial. The suggested solvent for each analyte is
identical to the PDS solvent listed in the "comments" portion of
Table 1. If the neat material is only available in quantities less
than 10 mg, reduce the volume of solvent accordingly. If
compound purity is confirmed by the supplier to be > 96%, the
525.3-21
-------
weighed amount can be used without correction to calculate the
concentration of the solution. Store at 4 °C or less to guard against
degradation and evaporation.
Note: Stock standard solutions and PDSs should be brought to
room temperature and sonicated for a few minutes prior to use.
This ensures that components are dissolved and the solution is
homogeneous.
7.2.3.2. ANALYTE PRIMARY DILUTION STANDARD / ANALYTE
FORTIFICATION SOLUTION (50 jig/mL for most compounds) -
Prepare the 50-|ig/mL Analyte PDS by volumetric dilution of the
Analyte Stock Standard Solutions (Sect. 7.2.3.1) in acetone or
methanol (see notes below) to make a 50-|ig/mL solution. Analyte
PDSs containing PCBs, PAHs, and other nonpolar compounds
must be diluted in acetone rather than methanol. The PDS can be
used to fortify the LFBs and LFSMs with method analytes and to
prepare calibration solutions. Care should be taken during storage
to prevent evaporation. The Analyte PDS/Analyte Fortification
Solutions used during method development were stable for
6 months when prepared in the solvents indicated in the
"comments" portion of Table 1, and stored in an amber glass screw
cap vials at -5 °C or less.
Notes:
• It may be necessary to prepare multiple Analyte PDS mixtures
based on the laboratory's specific compounds of interest. For
example, the method was developed using an Analyte PDS mix
containing analytes from Method 525.2 in acetone, a PCB PDS
mix in acetone, a PDS mix containing analytes from EPA's
Drinking Water Contaminant Candidate List 3 (CCL 3) in
methanol, and a PDS mix containing the remaining analytes in
methanol. The solvent used for the PDS solution for each
analyte is listed in the "comments" portion of Table 1.
• During method development, PDS solutions contained most
analytes at the same concentration. However, analytes can be
combined in PDS solutions at any desired concentrations. It
may be desirable to include some analytes at increased
concentrations if they have a relatively low instrument
response compared with other analytes. For example, during
method development, pentachlorophenol was added to PDS
solutions at four times the concentration of most other analytes.
• Standard solutions that will be used for aqueous sample
fortification generally should be prepared at a concentration
such that only a small volume (e.g., 5-100 jiL) needs to be
525.3-22
-------
added to achieve the desired final concentration. This will
minimize the quantity of organic solvent added to aqueous
samples.
• Stock standard solutions and PDSs should be brought to room
temperature and sonicated for a few minutes prior to use. This
ensures that components are dissolved and the solution is
homogeneous.
7.2.4. CALIBRATION SOLUTIONS - Calibration standards may be prepared in
EtOAc or as matrix-matched calibration standards (Sect. 3.15). This option
is provided so that the analyst has the flexibility to prepare calibration
curves that will be appropriate for the various types of analytes and the
calibration range of interest. If the analyses to be performed include only
those analytes that are not susceptible to matrix induced response
enhancement, and/or the concentrations to be measured are relatively high
(e.g., > 5|ig/L), it is likely that accurate data can be obtained with the use of
traditional CAL standards prepared in EtOAc. If low concentrations of
analytes susceptible to matrix induced response enhancement need to be
measured, it is likely that matrix-matched standards will be required to
obtain accurate quantitative data. Whichever type of CAL solutions are
selected, those CAL solutions should be used for all calibration and QC
procedures described in the method.
Note: Analytes observed to be susceptible to matrix induced response
enhancement during method development are indicated in the "comments"
portion of Table 1. However, the occurrence and degree of enhancement
will depend upon the GC injector design, and the history of the injector,
injector liner and GC column. It is highly recommended that prior to the
initial demonstration of capability, separate calibration curves be generated
using EtOAc CALs and matrix-matched CALs for each analyte to be
measured. A careful evaluation of the relative peak areas using each type of
CAL, especially low concentration CALs, can serve as a guide to the
possible occurrence and extent of matrix enhancement, and thus an
indicator of which type of standards should be used.
Note: Technical toxaphene CAL standards must be prepared so that they
contain only technical toxaphene and ISs and SURs. Do not mix technical
toxaphene with other analytes.
7.2.4.1. CALIBRATION SOLUTIONS PREPARED IN SOLVENT -
Prepare a series of six concentrations of calibration solutions in
EtOAc, which contain the analytes of interest. The suggested
concentrations in this paragraph are a description of the
concentrations used during method development, and may be
modified to conform with instrument sensitivity. For full scan
analyses, concentrations ranging from 0.10-5.0 ng/uL are
525.3-23
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suggested for each analyte, with IS and SUR concentrations as
described in Sect. 7.2.1 and 7.2.2. For SIM analysis, six
concentrations in the range of 0.005-0.5 ng/uL are suggested, with
reduced concentrations of the ISs and SURs (Sect. 7.2.1 and 7.2.2).
The six CAL standards (CAL1 through CAL6) are prepared by
combining appropriate aliquots of the Analyte PDS solution (Sect.
7.2.3.2) and the IS and SURPDSs (Sects. 7.2.1. and 7.2.2). All
calibration solutions should contain at least 60% EtOAc to avoid
gas chromatographic anomalies such as poor peak shape, split
peaks, etc. During method development, all analytes were
prepared in a single set of calibration solutions. However, multiple
sets of calibration standards may be prepared at the discretion of
the analyst if more separation of the analytes is desired.
Calibration solutions were stable for six months when stored at
-5 °C in amber screw top vials.
7.2.4.2. MATRIX-MATCHED CALIBRATION SOLUTIONS - Prepare a
series of six calibration solutions in the same manner as in Sect.
7.2.4.1, but instead of preparation in EtOAc, calibration solutions
are prepared in final solvent extracts derived from laboratory
reagent water. One-liter aliquots of reagent water with sample
preservatives added, are extracted using the sorbent selected for
sample analysis, dried with sodium sulfate, and evaporated to <1
mL following the same procedure used for samples (Sects. 11.3-
119) However, the ISs, SURs, and analyte PDSs are added to
the extract at appropriate concentrations immediately before
the adjustment of the extract to 1 mL, i.e., they are not
extracted.
7.2.5. GC/MS TUNE CHECK SOLUTION (5 |ig/mL or less)
(CASRN 5074-71-5) - Prepare a DFTPP solution in DCM. DFTPP is more
stable in DCM than in acetone or EtOAc. Store this solution in an amber
glass screw cap vial at 4 °C or less.
7.2.6. 4,4'-DDT BREAKDOWN CHECK SOLUTION (5ng/|iL in EtOAc) -
Prepare a solution of 4,4'-DDT in EtOAc. Store this solution in an amber
glass screw cap vial at 4 °C or less. The solution is used for the DDT
breakdown check described in Sect. 10.2.2.
8. SAMPLE COLLECTION. PRESERVATION. AND STORAGE
8.1. SAMPLE BOTTLE PREPARATION
8.1.1. Grab samples must be collected using 1 -liter or 1 -quart sample bottles that meet
the requirements in Sect. 6.1.
525.3-24
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Note: Larger samples must not be collected. The performance of this method has
not been verified with sample volumes greater than 1L. Samples larger than 1L
may not be portioned or split because some analytes may adhere to the glass
surface. These analytes are recovered in the SPE procedural steps that solvent
rinse the sample bottle and include that rinsate in the extract. If only a partial
sample were to be analyzed, the resulting data would be biased high if the bottle
rinsate were added to the extract, and biased low if it was not.
. 1.2. Preservation reagents, listed in the table below, are added to each sample bottle as
dry solids prior to shipment to the field (or prior to sample collection).
Compound
L-Ascorbic acid
Ethylenediaminetetraacetic acid, trisodium
salt
Potassium dihydrogen citrate
Amount
O.lOg/L
0.35 g/L
9.4 g/L
Purpose
Dechlorination
Inhibit metal -catalyzed
hydrolysis of targets
pH 3. 8 buffer,
microbial inhibitor
8.1.2.1. Residual chlorine must be reduced at the time of sample collection with
01
100 mg of ascorbic acid per liter.
8.1.2.2. Trisodium EDTA must be added to inhibit metal-catalyzed hydrolysis of
method analytes, principally, chlorpyrifos, parathion, vinclozolin, atrazine,
and propazine.20"22 There may be additional method analytes that also
benefit from addition of EDTA.
8.1.2.3. The sample must be buffered to pH 3.8 using potassium dihydrogen citrate.
This is added to inhibit microbial degradation of analytes, and to reduce
base catalyzed hydrolysis of some of the method analytes.20
8.2. SAMPLE COLLECTION
8.2.1. Open the tap and allow the system to flush until the water temperature has
stabilized (usually 3-5 min). Collect samples from the flowing system.
8.2.2. Fill sample bottles, taking care not to flush out the sample preservation
reagents. Samples do not need to be collected headspace free.
8.2.3. After collecting the sample, cap the bottle and agitate by hand until
preservatives are dissolved. Immediately place in ice or refrigerate.
8.3. SHIPMENT AND STORAGE - Samples must be chilled during shipment and must
not exceed 10 °C during the first 48 hours after collection. Sample temperature must
be confirmed to be at or below 10 °C when they are received at the laboratory, with
525.3-25
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the following exception. Samples arriving at the laboratory on the day of sampling
may not have had time to achieve a temperature of less than 10 °C. This is
acceptable as long as the cooling process has begun. Samples stored in the lab must
be held at or below 6 °C until extraction, but should not be frozen. Sample holding
time data are discussed in Sect. 13.4.
Note: Samples that are significantly above 10 °C at the time of collection, may need
to be iced or refrigerated for a period of time, in order to chill them prior to shipping.
This will allow them to be shipped with sufficient ice to meet the above
requirements.
8.4. SAMPLE AND EXTRACT HOLDING TIMES - Water samples should be extracted
as soon as possible after collection but must be extracted within 14 days of
collection. Exceptions to the 14 day sample holding time are samples being
analyzed for dichlorvos and/or cyanazine which must be extracted within 7 days. All
extracts must be stored at -5 °C or less, protected from light and analyzed within 28
days after extraction (Sect. 13.5).
9. QUALITY CONTROL
9.1. QC requirements include the Initial Demonstration of Capability (IDC) and ongoing
QC requirements that must be met when preparing and analyzing Field Samples.
This section describes QC parameters, their required frequency, and the performance
criteria that must be met in order to meet EPA quality objectives. The QC criteria
discussed in the following sections are summarized in Tables 24 and 25. These QC
requirements are considered the minimum acceptable QC criteria. Laboratories are
encouraged to institute additional QC practices to meet their specific needs.
Note: If toxaphene is being measured by this method in addition to other analytes,
all QC steps described in Sect. 9 must be performed for toxaphene in fortified
samples that are prepared and analyzed separately from other analytes. The
frequency of each QC requirement and the acceptance criteria for toxaphene are the
same as the general criteria for other analytes. Measured values for technical
toxaphene to meet QC criteria should be obtained as described in Sect. 12.3.3.
9.2. INITIAL DEMONSTRATION OF CAPABILITY - The IDC must be successfully
performed prior to analyzing any Field Samples. Prior to conducting the IDC, the
analyst must first generate an acceptable Initial Calibration following the procedure
outlined in Sect. 10.2. The IDC must be repeated if the laboratory changes the
type or brand of SPE sorbent being used.
9.2.1. INITIAL DEMONSTRATION OF LOW SYSTEM BACKGROUND -
Any time a new lot of SPE cartridges or disks is used, it must be
demonstrated that a Laboratory Reagent Blank is reasonably free of
contamination and that the criteria in Sect. 9.3.1 are met.
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9.2.2. INITIAL DEMONSTRATION OF PRECISION (IDP) - Prepare, extract,
and analyze four to seven replicate LFBs fortified near the midrange of the
initial calibration curve according to the procedure described in Sect. 11.
Sample preservatives as described in Sect. 8.1.2 must be added to these
samples. The relative standard deviation (RSD) of the results of the
replicate analyses must be < 20%.
9.2.3. INITIAL DEMONSTRATION OF ACCURACY - Using the same set of
replicate data generated for Sect. 9.2.2, calculate average recovery. The
average recovery expressed as the mean of the replicate values must be
within 70-130 % of the true value for all analytes except dimethipin,
HCCPD and HCB which may be within 60-130% of the true value.
9.2.4. MINIMUM REPORTING LEVEL (MRL) CONFIRMATION - Establish a
target concentration for the MRL based on the intended use of the method.
The MRL may be established by a laboratory for their specific purpose or
may be set by a regulatory agency. Establish an Initial Calibration
following the procedure outlined in Sect. 10.2. The lowest calibration
standard used to establish the Initial Calibration (as well as the low-level
Continuing Calibration Check standard) must be at or below the
concentration of the MRL. Establishing the MRL concentration too low
may cause repeated failure of ongoing QC requirements. Confirm the MRL
following the procedure outlined below.
Note: Setting an MRL for method analytes that are consistently present in
the background (e.g., phthalates) is particularly important so that false
positive data are not reported for Field Samples. See Sect. 9.3.1 for
guidance in setting an MRL for these analytes.
9.2.4.1. Fortify, extract, and analyze seven replicate Laboratory Fortified
Blanks (LFBs) at the proposed MRL concentration. These LFBs
must contain all method preservatives described in Sect. 8.1.2.
Calculate the mean and standard deviation for these replicates.
Determine the Half Range for the Prediction Interval of Results
(HRpiR) using the equation below
HRpm =3.9638
where:
S = the standard deviation, and 3.963 is a constant value for seven
replicates.1
9.2.4.2. Confirm that the upper and lower limits for the Prediction Interval
of Result (PIR = Mean + HR.PIR) meet the upper and lower
recovery limits as shown below:
525.3-27
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The Upper PIR Limit must be <150 percent recovery.
Mean + HRnrD
-xlOO%<150%
Fortified Concentrat ion
The Lower PIR Limit must be > 50 percent recovery.
Mean~HR^ x looo/o > 500/c
FortifiedConcentrat ion
9.2 A3. The MRL is validated if both the Upper and Lower PIR Limits
meet the criteria described above (Sect. 9.2.4.2). If these criteria
are not met, the MRL has been set too low by the laboratory and
must be demonstrated again at a higher concentration. If a
required MRL set by a regulatory body has not been met, the
analyst should evaluate possible problems in the execution of the
extraction steps, and/or possible problems with instrument
sensitivity. Reattempt MRL validation at the required MRL after
problems have been addressed.
9.2 A A. Confirmation of the MRL Using Fortified Matrix Samples
(optional)- This validation procedure may be used in addition to
the reagent water confirmation described above. It may be useful
in assessing any matrix induced quantitative bias at the MRL.
Obtain replicate 1 L aliquots of a water sample similar in nature to
the ones planned for analysis. If tap waters from both ground and
surface water sources are to be analyzed, it is recommended that a
surface water sample be selected for verification. Analyze one
aliquot using the procedures in this method to verify the absence of
analytes of interest. Fortify seven remaining aliquots with the
analytes to be measured near the expected MRL, and verify the
MRL as described in Sects. 9.2.4.1 through 9.2.4.3.
9.2.5. CALIBRATION CONFIRMATION - Analyze a Quality Control Sample as
described in Sect. 9.3.9 to confirm the accuracy of the standards/calibration
curve.
9.2.6. DETECTION LIMIT DETERMINATION (optional) - While DL
determination is not a specific requirement of this method, it may be
required by various regulatory bodies associated with compliance
monitoring. It is the responsibility of the laboratory to determine ifDL
determination is required based upon the intended use of the data.
525.3-28
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Replicate analyses for this procedure should be done over at least three days
(both the sample extraction and the GC analyses should be done over at
least three days). Prepare at least seven replicate LFBs at a concentration
estimated to be near the DL. This concentration may be estimated by
selecting a concentration at 2-5 times the noise level. The DLs in Tables 15
and 23 were calculated from LFBs fortified at various concentrations as
indicated in the table. The appropriate fortification concentrations will be
dependent upon the sensitivity of the GC/MS system used. All preservation
reagents listed in Sect. 8.1.2 must also be added to these samples. Analyze
the seven (or more) replicates through all steps of Sects. 1 1 and 12.
Note: If an MRL confirmation data set meets these requirements, a DL may
be calculated from the MRL confirmation data, and no additional analyses
are necessary.
Calculate the DL using the following equation:
= sxt(n-l,l-a=0.99)
where:
t (n-i, i-a=o.99) = Student's t value for the 99% confidence level with n-1
degrees of freedom
n = number of replicates
s = standard deviation of replicate analyses.
Note: Do not subtract blank values when performing DL calculations.
9.3 . ONGOING QC REQUIREMENTS - This section summarizes the ongoing QC
criteria that must be followed when processing and analyzing Field Samples.
9.3.1. LABORATORY REAGENT BLANK (LRB) - An LRB is required with
each extraction batchto confirm that potential background contaminants are
not interfering with the identification or quantitation of target analytes. If
the LRB produces a peak within the retention time window of any analyte
that would prevent the determination of that analyte, locate the source of
contamination and eliminate the interference before processing samples.
Background contamination must be reduced to an acceptable level before
proceeding. Background from method analytes or other contaminants that
interfere with the measurement of method analytes must be at or below l/j
of the MRL. Blank contamination may be estimated by extrapolation, if the
concentration is below the lowest calibration standard. Although this
procedure is not allowed for sample results as it may not meet data quality
objectives, it can be useful in estimating background concentrations. If any
of the method analytes are detected in the LRB at concentrations greater
525.3-29
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than Vs of the MRL, then all data for the problem analyte(s) must be
considered invalid for all samples in the extraction batch.
Note: It is extremely important to evaluate background values of analytes
that commonly occur in LRBs. The MRL must be set at a value greater
than three times the mean concentration observed in replicate LRBs. If
LRB values are highly variable, setting the MRL to a value greater than the
mean LRB concentration plus three times the standard deviation may
provide a more realistic MRL.
9.3.2. CONTINUING CALIBRATION CHECK (CCC) - CCC Standards are
analyzed at the beginning of each analysis batch, after every ten Field
Samples, and at the end of the analysis batch. See Sect. 10.3 for
concentration requirements and acceptance criteria.
9.3.3. LABORATORY FORTIFIED BLANK (LFB) - An LFB is required with
each extraction batch. The fortified concentration of the LFB must be
rotated between low, medium, and high concentrations from batch to batch.
The low concentration LFB must be as near as practical to, but no more
than two times the MRL. Similarly, the high concentration LFB should be
near the high end of the calibration range established during the initial cal-
ibration (Sect. 10.2). Results of the low-level LFB analyses must be
50-150% of the true value. Results of the medium and high-level LFB
analyses must be 70-130% of the true value for all analytes except
dimethipin, HCCPD and HCB, which may be between 60-130% of the true
value. If the LFB results do not meet these criteria for target analytes, then
all data for the problem analyte(s) must be considered invalid for all sam-
ples in the extraction batch.
9.3.4. MS TUNE CHECK - A complete description of the MS Tune Check is
found in Sect. 10.2.1. The acceptance criteria for the MS Tune Check are
summarized in Table 2. The MS Tune Check must be performed each time
a major change is made to the mass spectrometer, and prior to establishing
and/or re-establishing an initial calibration (Sect. 10.2). Daily DFTPP
analysis is not required.
Note: The tune check is performed in full scan mode, even if samples will
be analyzed in SIM mode.
9.3.5. INTERNAL STANDARDS (IS) - The analyst must monitor the peak areas
of the ISs in all injections during each analysis day. The peak area for each
IS in any chromatographic run must not deviate by more than ±50% from
the mean response in the CAL solutions analyzed for the initial analyte
calibration. In addition, the peak areas of ISs 1-3 must not deviate by more
than ± 30% from the most recent CCC. IS 4, 13C-pentachlorophenol, is
expected to have greater area count variability, and therefore is not subject
525.3-30
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to the most recent CCC criterion. If the IS areas in a chromatographic run
do not meet these criteria, inject a second aliquot of that standard or extract.
9.3.5.1. If the reinjected aliquot produces acceptable internal standard
responses, report results for that aliquot.
9.3.5.2. If the reinjected aliquot is a sample extract and fails again, the
analyst should check the calibration by evaluating the CCCs within
the analysis batch. If the CCCs are acceptable, extraction of the
sample may need to be repeated provided the sample is still
available and within the holding time. Otherwise, report results
obtained from the reinjected extract, but annotate as suspect.
Alternatively, collect a new sample and reanalyze.
9.3.5.3. If the reinjected aliquot is a CAL standard, take remedial action
(Sect. 10.3.3).
9.3.6. SURROGATE RECOVERY - Surrogate standards are fortified into the
aqueous portion of all samples, LRBs, CCCs, LFSMs, and LFSMDs prior to
extraction. They are also added to the calibration standards. The surrogates
are a means of assessing method performance from extraction to final
chromatographic measurement. Calculate the recovery (%R) for each
surrogate using the equation
( A\
%R = — xlOO
UJ
where:
A = calculated surrogate concentration for the QC or Field Sample, and
B = fortified concentration of the surrogate.
9.3.6.1. Surrogate recovery must be with 70-130% of the true value. When
surrogate recovery from a sample, blank, or CCC is less than 70%
or greater than 130%, check 1) calculations to locate possible
errors, 2) the integrity of the surrogate analyte solution, 3)
contamination, and 4) instrument calibration. Correct the problem
and reanalyze the extract.
9.3.6.2. If the extract reanalysis meets the surrogate recovery criterion,
report only data for the reanalyzed extract.
9.3.6.3. If the extract reanalysis fails the 70-130% recovery criterion, the
analyst should check the calibration by evaluating the CCCs within
the analysis batch. If the CCCs fail the criteria of Sect. 9.3.6.1,
recalibration is in order per Sect. 10.2. If the calibration standard is
525.3-31
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acceptable, extraction of the sample should be repeated provided
the sample is still available and within the holding time. If the re-
extracted sample also fails the recovery criterion, report all data for
that sample as suspect/surrogate recovery to inform the data user
that the results are suspect due to surrogate recovery.
9.3.7. LABORATORY FORTIFIED SAMPLE MATRIX (LFSM) - Within each
analysis batch, analyze a minimum of one LFSM. The native concentrations of
the analytes in the sample matrix must be determined in a second duplicate
sample and subtracted from the measured values in the LFSM. If a variety of
different sample matrices are analyzed regularly, for example, drinking water
from ground water and surface water sources, performance data must be collected
for each source.
9.3.7.1. Prepare the LFSM by fortifying a Field Duplicate with an
appropriate amount of analyte PDS (Sect. 7.2.3.2). Select a
fortification concentration that is greater than or equal to the matrix
background concentration, if known. Selecting a duplicate sample
that has already been analyzed aids in the selection of an
appropriate fortification concentration. If this is not possible, use
historical data. If historical data are unavailable, rotate the
fortifying concentrations for LFSMs between low, medium and
high concentrations based on the calibration range.
9.3.7.2. Calculate the percent recovery (%R) for each analyte using the
equation
C
where:
A = measured concentration in the fortified sample
B = measured concentration in the unfortified sample
C = fortification concentration.
Note: LFSMs and LFSMDs fortified at concentrations near the
MRL, where the associated Field Sample contains native analyte
concentrations above the DL but below the MRL, should be
corrected for the native levels in order the obtain meaningful %R
values. This example, and the LRB extrapolation (Sect. 9.3.1), are
the only permitted uses of analyte results below the MRL.
9.3.7.3. Analyte recoveries may exhibit matrix bias. For samples fortified
at or above their native concentration, recoveries should be within
70-130% (60-130% for dimethipin, HCCPD and HCB), except for
525.3-32
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low-level fortification near or at the MRL (within a factor of two
times the MRL concentration) where 50-150% recoveries are
acceptable. If the accuracy of any analyte falls outside the
designated range, and the laboratory performance for that analyte
is shown to be in control in the CCCs, the recovery is judged to be
matrix biased. The quantitative result for that analyte in the
unfortified sample is labeled "suspect/matrix" to inform the data
user that the quantitative results may be suspect due to matrix
effects.
9.3.8. FIELD DUPLICATE OR LABORATORY FORTIFIED SAMPLE
MATRIX DUPLICATE (FD or LFSMD) - Within each extraction batch,
analyze a minimum of one Field Duplicate (FD) or Laboratory Fortified
Sample Matrix Duplicate (LFSMD). Duplicates check the precision
associated with sample collection, preservation, storage, and laboratory
procedures. If target analytes are not routinely observed in Field Samples,
an LFSMD should be analyzed rather than an FD.
9.3.8.1. Calculate the relative percent difference (RPD) for duplicate
measurements (FD1 and FD2) using the equation
FD1-FD2
RPD =
9.3.8.2. RPDs for Field Duplicates should be < 30 %. Greater variability
may be observed when Field Duplicates have analyte
concentrations that are within two times the MRL. At these
concentrations, Field Duplicates should have RPDs that are < 50%.
If the RPD of any analyte falls outside the designated range, and
the laboratory performance for that analyte is shown to be in
control in the CCC, the recovery is judged to be affected by the
matrix. The result for that analyte in the unfortified sample is
labeled "suspect/matrix" to inform the data user that the
quantitative results may be suspect due to matrix effects.
9.3.8.3. If an LFSMD is analyzed instead of a Field Duplicate, calculate the
relative percent difference (RPD) for duplicate LFSMs (LFSM and
LFSMD) using the equation
\LFSM -LFSMDl
- -
- -
IFSM + LFSMD J2
9.3.8.4. RPDs for duplicate LFSMs should be < 30% for samples fortified
at or above their native concentration. Greater variability may be
observed when LFSMs are fortified at analyte concentrations that
525.3-33
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are within two times the MRL. LFSMs fortified at these
concentrations should have RPDs that are < 50% for samples
fortified at or above their native concentration. If the RPD of any
analyte falls outside the designated range, and the laboratory
performance for that analyte is shown to be in control in the CCC,
the recovery is judged to be affected by the matrix. The result for
that analyte in the unfortified sample is labeled suspect/matrix to
inform the data user that the quantitative results may be suspect
due to matrix effects.
9.3.9. QUALITY CONTROL SAMPLES (QCS) - As part of the IDC (Sect. 9.2),
each time a new Analyte PDS (Sect. 7.2.3.2) is prepared, or at least
quarterly, analyze a QCS sample from a source different from the source of
the calibration standards. If a second vendor is not available then a different
lot of the standard should be used. The QCS should be prepared and
analyzed just like a CCC. Acceptance criteria for the QCS are identical to
the CCCs; the calculated amount for each analyte must be ± 30% of the
expected value. If measured analyte concentrations are not of acceptable
accuracy, check the entire analytical procedure to locate and correct the
problem. If the discrepancy is not resolved, one of the standard materials
may be degraded or otherwise compromised and a third standard must be
obtained.
9.4. METHOD MODIFICATION QC REQUIREMENTS - The analyst is permitted to
modify GC columns, GC conditions, GC injection techniques, extract evaporation
techniques, MS conditions and QIs. However, each time such method modifications
are made, the analyst must repeat the procedures of the IDC (Sect. 9.2).
9.4.1. Each time method modifications are made, the analyst must repeat the
procedures of the IDC (Sect. 9.2) and verify that all QC criteria can be met
in ongoing QC samples (Sect. 9.3).
9.4.2. Each time method modifications are made, the analyst is also required to
evaluate and document method performance for the proposed method
modifications in real matrices that span the range of waters that the
laboratory analyzes. This additional step is required because modifications
that perform acceptably in the IDC, which is conducted in reagent water,
can fail ongoing method QC requirements in real matrices. This is
particularly important for methods subject to matrix effects. If, for
example, the laboratory analyzes finished waters from both surface and
groundwater municipalities, this requirement can be accomplished by
assessing precision and accuracy (Sects. 9.2.2 and 9.2.3) in an analyte
fortified surface water with moderate to high TOC (e.g., 2 mg/L or greater)
and an analyte fortified hard groundwater (e.g., 250 mg/L or greater as
calcium carbonate).
525.3-34
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9.4.3. The results of Sects. 9.4.1 and 9.4.2 must be appropriately documented by
the analyst and should be independently assessed by the laboratory's
Quality Assurance (QA) officer prior to analyzing Field Samples. When
implementing method modifications, it is the responsibility of the
laboratory to closely review the results of ongoing QC, and in particular, the
results associated with the LFSMs (Sect. 9.3.7), FDs or LFSMDs
(Sect. 9.3.8), CCCs (Sect. 9.3.2), and the IS area counts (Sect. 9.3.5). If
repeated failures are noted, the modification must be abandoned.
10. CALIBRATION AND STANDARDIZATION
10.1. Demonstration and documentation of acceptable mass spectrometer tune and initial
calibration is required before performing the IDC and prior to analyzing Field
Samples. The MS tune check and initial calibration must be repeated each time a
major instrument modification is made, or maintenance is performed.
10.2. INITIAL CALIBRATION
10.2.1. MS TUNE/MS TUNE CHECK - Calibrate the mass and abundance scales
of the MS with calibration compounds and procedures prescribed by the
manufacturer with any modifications necessary to meet tuning
requirements. Inject 5 ng or less of the DFTPP solution (Sect. 7.2.5) into
the GC/MS system. Acquire a mass spectrum that includes data for m/z 45
to 450. The scan time should be set so that a minimum of five scans are
acquired during the elution of the chromatographic peak. Seven to ten
scans per chromatographic peak are recommended. Use a single spectrum
at the apex of the DFTPP peak, an average spectrum of the three highest
points of the peak, or an average spectrum across the entire peak to evaluate
the performance of the system. If the DFTPP mass spectrum does not meet
all criteria in Table 2, the MS must be retuned and adjusted to meet all
criteria before proceeding with the initial calibration. The tune check
should be conducted as described above for both full scan and SIM MS
operation.
10.2.2. DDT BREAKDOWN CHECK -
Note: This procedure is only required if the DDT degradation products
DDD and DDE are being reported. The DFTTP tune check and the DDT
degradation check may be performed simultaneously with a single injection
of a standard containing both analytes.
4,4'-DDT is subject to thermal degradation in the GC. Because the thermal
degradation products 4,4'-DDE and 4,4'-DDD are also environmental
contaminants and method analytes, it is important to determine their source
if they are observed in sample chromatograms. Inject a standard of 4,4'-
DDT at a concentration near 5 ng/jiL, and acquire data in the full scan mode
525.3-35
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using instrument conditions similar to those in Sect. 10.2.3. Evaluate the
chromatogram for the presence of 4,4'-DDE and 4,4'-DDD using the
retention times and ions listed in Table 1 as a guide. If either 4,4'-DDE or
4,4'-DDD are observed, calculate the percentage breakdown of 4,4'-DDT
using peak areas from the Total Ion Current (TIC) with the following
equation:
% DDT breakdown =
X TIC area of DDT degradation peaks (DDE+DDD) X 100
X TIC area of total DDT peaks (DDT+DDE+DDD)
If the degradation of 4,4'-DDT exceeds 20%, perform maintenance on the
GC injection port and possibly other areas of the GC prior to proceeding
with the calibration. If GC maintenance does not correct the problem, a
new 4,4'-DDT standard should be obtained from a different source to ensure
that the standard material has not degraded.
10.2.3. INSTRUMENT CONDITIONS - Operating conditions used during method
development are described below. Conditions different from those
described may be used if QC criteria in Sect. 9 are met. Different
conditions include alternate GC columns, temperature programs, MS
conditions, and injection techniques and volumes, such as cold on-column
and large volume injections. Equipment specifically designed for alternate
types of injections must be used if these alternate options are selected.
10.2.3.1. GC Conditions - Inject a l-|iL aliquot into a hot, splitless injection
port held at 275 °C with a pressure pulse of 30 psi and a split delay
of 1 min. The temperature program is as follows: initial oven
temperature of 70 °C, hold for 1.5 min, ramp at 10 °C/min to 200
°C, ramp at seven °C/min to a final temperature of 320 °C and hold
for 3 min. The GC was operated at a constant flow rate of
1.2 mL/min. Total run time is approximately 32 min. Begin data
acquisition at about seven min.
10.2.3.2. Full Scan MS Acquistion Parameters - Select a scan range that
allows the acquisition of a mass spectrum for each of the method
analytes, which includes all of the major fragments m/z 45 and
above. Adjust the cycle time to measure at least five spectra
during the elution of each GC peak. Seven to ten scans across each
GC peak are recommended. The chromatogram may be divided
into time windows, also known as segments or periods, with
different scan ranges for each time window. Minimizing the scan
range for each time window may enhance sensitivity. If the
chromatogram is divided into time windows, the laboratory must
ensure that each method analyte elutes entirely within the proper
525.3-36
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window during each analysis. This can be achieved by carefully
monitoring the retention times of all ISs and SURs in each sample,
and carefully monitoring the retention times of all method analytes
in CCCs, LFBs and LFMs. This requirement does not preclude
continuous operation by sequencing multiple analysis batches;
however, the entire analysis batch is invalid if one or more analyte
peaks have drifted outside of designated time windows in the CCC
at the beginning or end of the analysis batch.
10.2.3.3. SIM MS Acquistion Parameters - Prior to selecting SIM
parameters, analyze a mid- to high-concentration CAL in full scan
mode. Select one primary QI and at least one secondary ion for
confirmation. If possible, select a second confirmation ion.
Suggested QIs and secondary ions for all method analytes are
designated in Table 1, but these may be modified. An internal
standard for each analyte is also designated in Table 1. Verify that
the primary ion is free from interferences due to an identical
fragment ion in any overlapping peak(s). Selection of the QI
should be based on the best compromise between the intensity of
the signal for that ion and the likelihood and intensity of
interferences. The most intense ion may not be the best QI.
Adjust the cycle time to measure at least five spectra during the
elution of each GC peak. If the chromatogram is divided into time
windows, the laboratory must ensure that each method analyte
elutes entirely within the proper window during each analysis.
This can be achieved by carefully monitoring the retention times of
all ISs and SURs in each sample, and carefully monitoring the
retention times of all method analytes in CCCs, LFBs and LFMs.
This requirement does not preclude continuous operation by
sequencing multiple analysis batches; however, the entire analysis
batch is invalid if one or more analyte peaks have drifted outside of
designated time windows in the CCC at the beginning or end of the
analysis batch. The SIM parameters used during method
development for selected analytes are provided in Table 16 as an
example.
10.2.3.4. Alternating Full and SIM Scan Modes - Alternating full and SIM
scan modes during a single sample acquisition is permitted if the
minimum number of scans across each GC peak acquired in each
mode is maintained (as specified in Sect. 10.2.3.2 and 10.2.3.3),
i.e., a minimum of five scans in full scan mode and a minimum of
five scans in SIM mode. If the chromatogram is divided into time
windows, the laboratory must ensure that each method analyte
elutes entirely within the proper window during each analysis.
This can be achieved by carefully monitoring the retention times of
all ISs and SURs in each sample, and carefully monitoring the
525.3-37
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retention times of all method analytes in CCCs, LFBs and LFMs.
This requirement does not preclude continuous operation by
sequencing multiple analysis batches; however, the entire analysis
batch is invalid if one or more analyte peaks have drifted outside of
designated time windows in the CCC at the beginning or end of the
analysis batch.
10.2.4. CALIBRATION SOLUTIONS - To establish a calibration range extending
two orders of magnitude, prepare a set of at least six calibration standards as
described in Sect. 7.2.4. The lowest concentration CAL must be at or below
the MRL for each method analyte. The MRL must be confirmed using the
procedure outlined in Sect. 9.2.4 after establishing the initial calibration.
Note: This method contains many analytes that vary widely with regard to
instrument sensitivity. If the analytes of interest differ in response, and the
CAL standards have been prepared such that all analytes are at the same
concentration, more standards may be needed to obtain the minimum five
CAL points for each analyte. Analytes with poor response may not be
observed in the low concentration standards, and the most responsive
analytes may saturate the detector at the higher concentrations. It is likely
that the calibration range for all analytes will not be the same. The use of
custom calibration standards with varying analyte concentrations based on
their relative instrument response is a possible alternative.
10.2.5. CALIBRATION - Calibrate the GC/MS system using the internal standard
technique in either full scan, SIM or alternating full scan/SIM mode.
Subsequent sample analysis must be performed in the same calibration
mode using identical instrument conditions and parameters. Internal
standard designations and suggested QIs for all method analytes are listed in
Table 1. Table 16 contains example scanning parameters for selected
analytes in SIM mode. Linear or quadratic calibrations may be used.
Weighting may be used at the discretion of the analyst. In general, forcing
zero as part of the calibration is not recommended. However, zero must be
forced for all analytes that are routinely observed as contaminants in
LRBs. Forcing zero allows for a better estimate of the background level of
contaminants in the blank. An accurate estimate of background
contamination is necessary to set MRLs for method analytes when blank
levels are problematic (Sect. 9.3.1). For example, phthalates are a chemical
class which is typically problematic with regard to background
contamination.
10.2.5.1. Toxaphene calibration - Analyze a minimum of five calibration
standards of technical toxaphene. These calibrations standards
must contain only toxaphene and the ISs and SURs. Select a
minimum of four chromatographic peaks from the toxaphene
chromatograms to use for calibration. See Fig. 2 as an example of
525.3-38
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suggested peak selection, and Table 16 as an example of suggested
SIM parameters. Create a calibration curve for each selected peak,
using the total technical toxaphene concentration in each CAL
standard as the calibration concentration. See Sect. 12.3.3 for
utilizing the curves to calculate the concentration of toxaphene in
CCCs, LFBs, Field Samples, LFSMs, QCSs, FDs, and LFSMDs.
10.2.6. CALIBRATION ACCEPTANCE CRITERIA - Validate the initial
calibration curves by using the regression equations to calculate the
concentration of each analyte as an unknown in each of the analyses used to
generate the curves. Calibration points that are < MRL must calculate to be
within ± 50% of their true value. All other calibration points must calculate
to be within ± 30% of their true value. If these criteria cannot be met, the
analyst may eliminate either the highest or lowest point on the curve and
reassess the acceptance criteria. If the acceptance criteria still cannot be
met, the analyst will have difficulty meeting ongoing QC criteria. It is
highly recommended that corrective action be taken before proceeding.
This may include one or more of the following actions: analyze the
calibration standards, further restrict the range of calibration, or select an
alternate method of calibration. The data presented in this method were
obtained using either linear regression or quadratic fits. Quadratic fit
calibrations should be used with caution, because the non-linear area of the
curve may not be reproducible.
10.3. CONTINUING CALIBRATION CHECK (CCC) - Analyze a CCC to verify the
initial calibration at the beginning of each analysis batch, after every tenth Field
Sample, and at the end of each analysis batch. The beginning CCC for each analysis
batch must be at or below the MRL. This CCC verifies instrument sensitivity prior
to the analysis of samples. Alternate subsequent CCCs between the remaining
calibration levels.
Notes:
• If standards have been prepared such that all analytes are not in the same
calibration standard (or all low CAL points are not in the same CAL
standard), it may be necessary to analyze more than one CCC to meet this
requirement. Alternatively, it may be cost effective to prepare or obtain a
customized standard to meet this criterion.
• Separate CCCs must be analyzed for toxaphene if it is one of the analytes
being measured. The frequency of analysis, the concentration rotation
requirements and acceptance criteria are the same for toxaphene as for other
analytes.
10.3.1. Verify that the peak area of the QI of each IS has not changed by more than
± 50% from the mean peak area measured for that IS during initial
calibration. In addition, verify that the peak area of the QI of each of the
ISs 1-3 are within ± 30% from the most recently analyzed CCC. If these
525.3-39
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limits are exceeded, remedial action must be taken (Sect. 10.3.3). Control
charts are useful aids in documenting system sensitivity changes.
10.3.2. Calculate the concentration of each analyte and surrogate in the CCC. The
calculated amount for each analyte for medium and high level CCCs must
be ± 30% of the true value. The calculated amount for the lowest
calibration level for each analyte must be within ± 50% of the true value. If
these criteria are not met, then all data for the problem analyte must be
considered invalid, and remedial action (Sect. 10.3.3) must be taken.
Recalibration may be required. Any Field Sample extracts that have been
analyzed since the last acceptable calibration verification should be
reanalyzed after adequate calibration has been restored, with the following
exception. If the CCC at the end of an analysis batch fails because the
calculated concentration is greater than 130% (150% for the low-level
CCC) for a particular target analyte, and Field Sample extracts show no
detection for that target compound, non-detects may be reported without
reanalysis.
10.3.3. REMEDIAL ACTION - Failure to meet CCC QC performance criteria may
require remedial action. Major maintenance such as cleaning an ion source,
cleaning the mass analyzer, replacing filament assemblies, or replacing the
GC column, etc., will likely require returning to the initial calibration step
(Sect. 10.2).
11. PROCEDURE
11.1. This section describes the procedures for sample preparation, SPE, final extract
preparation and storage, and extract analysis. Important aspects of this analytical
procedure include proper preparation of laboratory glassware, sample containers
(Sect. 4.1), and sample collection and storage (Sect. 8). Procedures for data analysis
and calculations are described in Sect. 12.
11.2. SAMPLE PREPARATION
11.2.1. Samples are preserved, collected and stored as described in Sect. 8. All
field and QC samples, including LRBs and LFBs, must contain the
preservatives listed in Sect. 8.1.2. Before extraction, verify that the sample
pH is < 4. If the sample pH does not meet this requirement, discard the
sample. If the sample pH is acceptable, proceed with the analysis. Mark
the level of the sample on the outside of the sample bottle for later sample
volume determination. If using weight to determine volume (Sect. 11.10),
weigh the bottle and sample contents before extraction.
11.2.2. Add an aliquot of the SUR PDS(s) to each sample to be extracted. For
method development work, a 10-jiL aliquot of each of the 500-|ig/mL SUR
525.3-40
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PDSs (Sect. 7.2.2) was added to 1 L samples for a final concentration of
5.0
1 1.2.3. If the sample is an LFB, LFSM, or LFSMD, add the necessary amount of
Analyte Fortification Solution(s) (Sect. 7.2.3.2). Swirl each sample to
ensure all components are mixed.
1 1.2.4. Proceed with sample extraction using one of the SPE options described in
Sects. 11.3-11.7.
11.3. CARTRIDGE SPE (6 mL) PROCEDURE - This cartridge extraction procedure may
be carried out in a manual mode or by using a robotic or automatic sample
preparation device. This section describes the SPE procedure using the equipment
outlined in Sect. 6. 1 1 in its simplest, least expensive mode without the use of a
robotic system. The manual mode described below was used to collect data presented
in Sect. 17. The extraction steps are written for an individual sample, but multiple
samples may be extracted simultaneously depending upon the extraction equipment
used.
Automated systems may use either vacuum or positive pressure to process samples
and solvents through the cartridge. All sorbent washing, conditioning, sample
loading, rinsing, drying and elution steps must be performed as closely as possible to
the manual procedure. The solvents used for washing, conditioning, and sample
elution must be the same as those used in the manual procedure: however, the
amount used may be increased as necessary to achieve the required data quality.
Solvent amounts may not be decreased. Sorbent drying times prior to elution may be
modified to achieve the required data quality. Caution should be exercised when
increasing solvent volumes. Increased extract volume will likely necessitate the
need for additional sodium sulfate drying, and extended evaporation times which
may compromise data quality. Caution should also be exercised when modifying
sorbent drying times. Excessive drying may cause losses due to analyte volatility,
and excessive contact with room air may oxidize some method analytes. Insufficient
drying may leave excessive water trapped in the cartridge and lead to poor
recoveries. Compressed gas cylinders of high purity nitrogen may be used with
systems that use positive pressure for sample processing.
11.3.1. CARTRIDGE CLEANUP - Install the SPE cartridge (Oasis HLB or J.T.
Baker H^O Phobic DVB as described in Sect. 6.11.1) into the vacuum
manifold. Wash the cartridge with 5 mL of EtOAc by adding the solvent to
the cartridge; draw about half through the sorbent, soak for about one min,
then draw the remaining solvent through the cartridge.
11.3.2. CARTRIDGE CONDITIONING - Polymeric SPE sorbents are water
wettable (unlike C-18 SPE sorbents). Many manufacturers of polymeric
SPE media suggest that their products do not need to be kept wet during
conditioning and sample processing. However, little data have been shown
525.3-41
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to demonstrate performance under those conditions for the wide variety of
environmental contaminants using these media. Therefore, in the interest of
providing a single procedure for the sorbents and analytes in this method,
the authors chose to use procedures similar to those used with C-18 where
the sorbent is kept wet.
11.3.2.1. CONDITIONING WITH METHANOL - Add lOmLMeOHto
the cartridge and allow it to soak for about one min. Then draw
most of the MeOH through. A layer of MeOH must be left on the
surface of the cartridge. Do NOT let the cartridge go dry from this
point on until the end of sample extraction, otherwise recondition
the cartridge with 10 mL MeOH.
11.3.2.2. CONDITIONING WITH WATER - Rinse the cartridge by adding
10 mL of reagent water to the cartridge and drawing most through,
again leaving a layer on the surface of the cartridge. Do NOT let
the cartridge go dry from this point on until the end of sample
extraction, otherwise recondition the cartridge starting with step
11.3.2.1.
11.3.3. SAMPLE EXTRACTION - Attach a PTFE transfer line to the top of the
cartridge. Insert the opposite end of the transfer line into the sample to be
extracted. Apply vacuum to begin the extraction. Adjust the vacuum so
that the sample passes through the cartridge at a rate of about 10 mL/min.
Pass the entire sample volume through the cartridge, draining as much
water from the sample container as possible. Rinse the bottle with 10 mL
LRW and transfer to the cartridge under full vacuum. Rinsing the sorbent
with LRW prior to drying helps remove sample preservatives from the
sorbent so they are not transferred to the extract. Remove the sample
transfer line from the cartridge and dry by maintaining vacuum for about
10 min.
11.3.4. CARTRIDGE ELUTION - Remove the manifold lid (but do not remove the
cartridge) and insert a suitable collection tube to contain the eluent (15 mL
collection vial). Reassemble the apparatus. Add 5 mL of EtOAc to the
sample bottle, and rinse the inside walls thoroughly. Allow the solvent to
settle to the bottom of the bottle, and then transfer to the cartridge by
applying vacuum. Draw about half of the solvent through the cartridge, cut
off vacuum at the cartridge, and allow the cartridge to soak for one min.
Draw the remaining solvent through the cartridge. Repeat the above step
with DCM. Shut off vacuum, remove the transfer line, and remove the
collection vial. Proceed to Sects. 11.8 and 11.9 to dry and concentrate the
extract.
11.4. CARTRIDGE SPE (83 ML) PROCEDURE - This cartridge extraction procedure
may be carried out in a manual mode or by using a robotic or automatic sample
525.3-42
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preparation device. This section describes the SPE procedure using the equipment
outlined in Sect. 6.12 in its simplest, least expensive mode without the use of a
robotic system. The manual mode described below was used to collect data presented
in Sect. 17.
Automated systems may use either vacuum or positive pressure to process samples
and solvents through the cartridge. All sorbent washing, conditioning, sample
loading, rinsing, drying and elution steps must be performed as closely as possible to
the manual procedure. The solvents used for washing, conditioning, and sample
elution must be the same as those used in the manual procedure: however, the
amount used may be increased as necessary to achieve the required data quality.
Solvent amounts may not be decreased. Sorbent drying times prior to elution may be
modified to achieve the required data quality. Caution should be exercised when
increasing solvent volumes. Increased extract volume will likely necessitate the
need for additional sodium sulfate drying, and extended evaporation times which
may compromise data quality. Caution should also be exercised when modifying
sorbent drying times. Excessive drying may cause losses due to analyte volatility,
and excessive contact with room air may oxidize some method analytes. Insufficient
drying may leave excessive water trapped in the cartridge and lead to poor
recoveries. Compressed gas cylinders of high purity nitrogen may be used with
systems that use positive pressure for sample processing.
11.4.1. CARTRIDGE CLEANUP - Assemble the extraction system by adding
cartridge adaptors, UCT Universal 525 cartridges and bottle holders to the
six station manifold. Wash the bottle holders and cartridges with 5 mL 1:1
EtOAc:DCM, draw half through, soak the sorbent for one min, then draw
the remaining solvent through, maintaining the vacuum for two additional
min.
11.4.2. CARTRIDGE CONDITIONING
11.4.2.1. CONDITIONING WITH METHANOL - Add 10 mL MeOH to
each cartridge. Soak for one min. Then draw most of the MeOH
through, leaving a thin layer of MeOH on the surface of the
cartridge. Do NOT let the cartridge go dry from this point on until
the end of sample extraction, otherwise recondition the cartridge
with lOmLMeOH.
11.4.2.2. CONDITIONING WITH WATER - Add 10 mL LRW to each
cartridge. Then draw most through, leaving a thin layer on the
surface of the cartridge. Do NOT let the cartridge go dry from this
point on until the end of sample extraction, otherwise recondition
the cartridge starting with step 11.4.2.1.
11.4.3. SAMPLE EXTRACTION - Load the sample bottles onto the bottle holders.
Turn on the vacuum; adjust the flow at a fast drop-wise fashion. A flow
525.3-43
-------
rate of 10 mL/min provides optimum recoveries. After passing the entire
volume of each sample through the cartridges, add 10 mL LRW to the
sample bottle, rinse and pass the water through the cartridges. Rinsing the
sorbent with LRW prior to drying helps remove sample preservatives from
the sorbent so they are not transferred to the extract. Remove the sample
bottles. Dry the cartridges under full vacuum for 10 min.
11.4.4. CARTRIDGE ELUTION - Remove cartridge adaptors and insert 40-mL
glass vials into the manifold to collect the eluent. Replace the cartridge
adaptors, cartridges and bottle holders on the manifold. Rinse each bottle
holder and cartridge with 5 mL EtOAc, draw half through the sorbent, soak
one min, then draw the remaining through. Repeat with 5 mL DCM. Again,
rinse each sample bottle thoroughly with 5 mL EtOAc. Then pour the
rinsing solvent into the cartridge. Repeat with 5 mL DCM. Proceed to
Sects. 11.8 and 11.9 to dry and concentrate the extract.
11.5. SPEEDISK SPE PROCEDURE - The Speedisk extraction procedure may be carried
out in a manual mode or by using a robotic or automatic sample preparation device.
This section describes the SPE procedure using the equipment outlined in Sect. 6.10
in its simplest, least expensive mode without the use of a robotics system. The
manual mode described below was used to collect data presented in Sect. 17. The
extraction steps are written for an individual sample, but multiple samples may be
extracted simultaneously depending upon the extraction equipment used.
Note: All automated extraction systems may not be suitable for use with Speedisks.
See the warning concerning excessive water content in extracts in Sect. 13.6.6.
Automated systems may use either vacuum or positive pressure to process samples
and solvents through the disk. All sorbent washing, conditioning, sample loading.
rinsing, drying and elution steps must be performed as closely as possible to the
manual procedure. The solvents used for washing, conditioning, and sample elution
must be the same as those used in the manual procedure: however, the amount used
may be increased as necessary to achieve the required data quality. Solvent
amounts may not be decreased. Sorbent drying times prior to elution may be
modified to achieve the required data quality. Caution should be exercised when
increasing solvent volumes. Increased extract volume will likely necessitate the
need for additional sodium sulfate drying, and extended evaporation times which
may compromise data quality. Caution should also be exercised when modifying
sorbent drying times. Excessive drying may cause losses due to analyte volatility,
and excessive contact with room air may oxidize some method analytes.
Insufficient drying may leave excessive water trapped in the disk and lead to poor
recoveries. Compressed gas cylinders of high purity nitrogen may be used with
systems that use positive pressure for sample processing.
11.5.1. SPEEDISK CLEANUP - Insert a J.T. Baker Speedisk disk (DVB H2O
Phobic, 55 mm) onto a J.T. Baker Speedisk manifold apparatus. Wash the
525.3-44
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disk with 5 mL of EtOAc by adding the solvent to the disk, drawing about
half through the disk, allowing it to soak the disk for about one min, then
drawing the remaining solvent through the disk.
11.5.2. SPEEDISK CONDITIONING
11.5.2.1. CONDITIONING WITH METHANOL - Pre-wet the disk with
10 mL MeOH by adding the MeOH to the disk and allowing it to
soak for about one min, then drawing most of the remaining
MeOH through. A layer of MeOH must be left on the surface of
the disk, which should not be allowed to go dry from this point
until the end of the sample extraction. Note that it may be
necessary to briefly remove the disk from the manifold to prevent
residual vacuum from pulling the remaining MeOH through and
unintentionally allowing the disk to dry out.
11.5.2.2. CONDITIONING WITH WATER - Rinse the disk with 10 mL
reagent water by adding the water to the disk and drawing most
through, again leaving a layer on the surface of the disk. Add a
sample reservoir adaptor to the top of the Speedisk.
11.5.3. SAMPLE EXTRACTION - Add the water sample to the reservoir and
apply full vacuum to begin the extraction. Particulate-free water may pass
through the disk in as little as five min without reducing analyte recoveries.
Pass the entire sample through the disk, draining as much water from the
sample container as possible. Rinse the bottle with 10 mL LRW and transfer
to the disk under full vacuum. Rinsing the sorbent with LRW prior to
drying helps remove sample preservatives from the sorbent so they are not
transferred to the extract. Dry the disk by maintaining vacuum for about
three min.
11.5.4. SPEEDISK ELUTION - Remove the reservoir adaptor and Speedisk disk,
and add the collection vial adaptor and insert a suitable collection tube to
contain the eluent (40 to 60-mL collection vial). Reassemble the apparatus.
Add ~2 mL of acetone to the sample bottle, and rinse the inside walls
thoroughly. Allow the solvent to settle to the bottom of the bottle, then
transfer it to the disk. Draw the solvent through the disk by applying
vacuum. Add 5 mL of EtOAc to the sample bottle, and rinse the inside
walls thoroughly. Allow the solvent to settle to the bottom of the bottle,
then transfer it to the Speedisk disk. A disposable pipette or syringe may be
used to do this, rinsing the sides of the glass filtration reservoir in the
process. Draw about half of the solvent through the disk, release the
vacuum, and allow the disk to soak for one min. Draw the remaining
solvent through the disk. Repeat the above step with 5 mL DCM. Proceed
to Sects 11.8 and 11.9 to dry and concentrate the extract.
525.3-45
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11.6. EMPORE DISK SPE PROCEDURE - The disk extraction procedure may be carried
out in a manual mode or by using a robotic or automatic sample preparation device.
This section describes the SPE procedure using the equipment outlined in Sect. 6.9 in
its simplest, least expensive mode without the use of a robotics system. The manual
mode described below was used to collect data presented in Sect. 17. The extraction
steps are written for an individual sample, but multiple samples may be extracted
simultaneously depending upon the extraction equipment used.
Automated systems may use either vacuum or positive pressure to process samples
and solvents through the disk. All sorbent washing, conditioning, sample loading,
rinsing, drying and elution steps must be performed as closely as possible to the
manual procedure. The solvents used for washing, conditioning, and sample elution
must be the same as those used in the manual procedure: however, the amount used
may be increased as necessary to achieve the required data quality. Solvent amounts
may not be decreased. Sorbent drying times prior to elution may be modified to
achieve the required data quality. Caution should be exercised when increasing
solvent volumes. Increased extract volume will likely necessitate the need for
additional sodium sulfate drying, and extended evaporation times which may
compromise data quality. Caution should also be exercised when modifying sorbent
drying times. Excessive drying may cause losses due to analyte volatility, and
excessive contact with room air may oxidize some method analytes. Insufficient
drying may leave excessive water trapped in the disk and lead to poor recoveries.
Compressed gas cylinders of high purity nitrogen may be used with systems that use
positive pressure for sample processing.
11.6.1. EMPORE DISK CLEANUP - Insert the disk (3M SDB-XC, 47mm) into the
filter manifold apparatus. Wash the disk with 5 mL EtOAc by adding the
solvent to the disk, drawing about half through the disk, allowing it to soak
the disk for about one min, then drawing the remaining solvent through the
disk.
11.6.2. EMPORE DISK CONDITIONING
11.6.2.1. CONDITIONING WITH METHANOL - Pre-wet the disk with 10
mL MeOH by adding the MeOH to the disk and allowing it to soak
for about one min, then drawing most of the remaining MeOH
through. A layer of MeOH must be left on the surface of the disk,
which should not be allowed to go dry from this point until the end
of the sample extraction.
11.6.2.2. CONDITIONING WITH WATER - Rinse the disk with 10 mL
reagent water by adding the water to the disk and drawing most
through, again leaving a layer on the surface of the disk.
11.6.3. SAMPLE EXTRACTION - Add the water sample to the reservoir and
apply full vacuum to begin the extraction. Particulate-free water may pass
525.3-46
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through the disk in as little as five min without reducing analyte recoveries.
Pass the entire sample through the disk, draining as much water from the
sample container as possible. Rinse the bottle with 10 mL LRW and transfer
to the disk under full vacuum. Rinsing the sorbent with LRW prior to
drying helps remove sample preservatives from the sorbent so they are not
transferred to the extract. Dry the disk by maintaining vacuum for about 10
min.
11.6.4. DISK ELUTION - Remove the filtration top (but do not disassemble the
reservoir and fritted base) and insert a suitable collection tube to contain the
eluent (40-mL collection vial). Reassemble the apparatus. Add 5 mL
EtOAc to the sample bottle, and rinse the inside walls thoroughly. Allow
the solvent to settle to the bottom of the bottle, then transfer it to the disk. A
disposable pipette or syringe may be used to do this, rinsing the sides of the
glass filtration reservoir in the process. Draw about half of the solvent
through the disk, release the vacuum, and allow the disk to soak for one
min. Draw the remaining solvent through the disk. Repeat this step with
DCM. Using a syringe or disposable pipette, rinse the filtration reservoir
with 5 mL 1:1 EtOAc:DCM. Draw the solvent through the disk and into the
collection vial. Proceed to Sects. 11.8 and 11.9 to dry and concentrate the
extract.
11.7. HORIZON ATLANTIC DVB DISK PROCEDURE - This extraction procedure may
be carried out in a manual mode or by using a robotic or automatic sample
preparation device. The following section describes the SPE procedure using the
automated extraction equipment outlined in Sect. 6.13. The automated procedure
described below was used to collect data presented in Sect. 17. The use of a manual
system is allowed; however, all sorbent washing, conditioning, sample loading.
rinsing, drying and elution steps must be performed as closely as possible to the
automated procedure. The solvents used for washing, conditioning, and sample
elution must be the same as those used in the manual procedure: however, the amount
used may be increased as necessary to achieve the required data quality. Solvent
amounts may not be decreased. Note that in the automated procedure each solvent
"prewet" step is approximately 10 mL and each solvent elution "rinse" is 4-5 mL.
Sorbent drying times prior to elution may be modified to achieve the required data
quality. Caution should be exercised when increasing solvent volumes. Increased
extract volume will likely necessitate the need for additional sodium sulfate drying,
and extended evaporation times which may compromise data quality. Caution should
also be exercised when modifying sorbent drying times. Excessive drying may cause
losses due to analyte volatility, and excessive contact with room air may oxidize some
method analytes. Insufficient drying may leave excessive water trapped in the disk
and lead to poor recoveries. Compressed gas cylinders of high purity nitrogen may
be used with systems that use positive pressure for sample processing.
525.3-47
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Step#
1
2
O
4
5
6*
7*
8
9
10
11
Description
Prewet
Prewet
Prewet
Prewet
Sample Load
Wash
Wash
Air Dry
Rinse
Rinse
Rinse
Solvent
EtOAc
DCM
MeOH
LRW
LRW
LRW
EtOAc
DCM
DCM
Soak Time
(mm:ss)
1:00
1:00
1:00
0.05
0:10
0:10
1:30
1:30
1:30
Air Dry Time
(mm:ss)
0:30
0:30
0.00
0.00
0:30
0:30
1:00
0:30
0:30
0:30
* Steps 6 and 7 of this procedure were added subsequent to the collection of the data
shown in Tables 13 and 14. The procedure has been tested with these additional
steps, with no negative effect on the resulting data. These steps are optional, but
highly recommended. Rinsing the sorbent with LRW before air drying and solvent
elution removes any residual preservatives from the sorbent so that they are not
eluted into the extract.
Proceed to Sects. 11.8 and 11.9 to dry and concentrate the extract.
11.8. DRYING THE EXTRACT - Transfer the combined eluent through a drying tube
containing about 10 g of anhydrous sodium sulfate. Rinse the collection tube with
5 mL DCM, and then put the DCM through the sodium sulfate. Collect the dried
extract and DCM rinse in a clean collection tube (15- or 40-mL tube depending on
the extract volume).
Note: Speedisk disk extracts may contain higher amounts of water due to the
acetone in the elution steps. If extracts appear wet after completing Sect. 11.8 or
11.9, additional sodium sulfate may be used. If additional sodium sulfate is used the
5 mL DCM rinse may need to be increased by a proportional amount.
11.9. EXTRACT CONCENTRATION - Concentrate the extract to about 0.7 mL under a
gentle stream of nitrogen gas in a warm water bath (at ~ 40 °C). Do not blow down
samples to less than 0.5 mL, because the more volatile compounds will exhibit
diminished recovery. Transfer the extract to a 1 -mL volumetric flask and add the
internal standards (Sect. 7.2.1). Rinse the collection tube that held the dried extract
with small amounts of EtOAc and add to the volumetric flask to bring the volume up
to the 1-mL mark. Transfer to an autosampler vial. Store extracts at -5 °C or less
until analysis.
11.10. SAMPLE VOLUME OR WEIGHT DETERMINATION - Use a graduated cylinder
to measure the volume of water required to fill the original sample bottle to the mark
made prior to extraction (Sect. 11.2.1). Determine volume to the nearest 10 mL for
use in the final calculations of analyte concentration (Sect. 12.2). If using weight to
525.3-48
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determine volume, reweigh the empty sample bottle. Subtract the empty bottle
weight from the weight of the original combined bottle/sample weight measured in
Sect. 11.2.1. To calculate the sample volume from its weight, assume a sample
density of Ig/mL. Use the calculated sample volume for analyte concentration
calculations in Sect. 12.2.
11.11. ANALYSIS OF SAMPLE EXTRACTS
11.11.1. Establish operating conditions as described in Sect. 10.2.3. Confirm that
compound separation and resolution are similar to those summarized in
Table 1 and Figures la-Id.
11.11.2. Establish a valid initial calibration following the procedures outlined in
Sect. 10.2 or confirm that the calibration is still valid by running a CCC as
described in Sect. 10.3. If establishing an initial calibration for the first
time, complete the IDC as described in Sect. 9.2.
11.11.3. Analyze aliquots of Field and QC Samples at appropriate frequencies
(Sect. 9) with the GC/MS conditions used to acquire the initial calibration
and the CCC. At the conclusion of data acquisition, use the same software
that was used in the calibration procedure to tentatively identify peaks in
predetermined retention time windows of interest. Use the data system
software to examine the ion abundances of components of the chromato-
gram.
12. DATA ANALYSIS AND CALCULATIONS
12.1. COMPOUND IDENTIFICATION - Identify sample components by comparison of
their retention times and mass spectra to the reference retention times and spectra in
the user-created data base as follows:
12.1.1. Establish an appropriate retention time window for each analyte, internal
standard and surrogate analyte to identify them in QC and Field Sample
chromatograms. Ideally, the retention time window should be based on
measurements of actual retention time variation for each compound in
standard solutions collected on each GC/MS over the course of time. The
suggested variation is plus or minus three times the standard deviation of
the retention time for each compound for a series of injections. The
injections from the initial calibration and from the IDC (Sect. 9.2) may be
used to calculate a suggested window size. However, the experience of the
analyst should weigh heavily on the determination of an appropriate
retention window size.
12.1.2. Each compound should be identified from its reference spectrum obtained
during the acquisition of the initial calibration curve. The mass spectrum
used for identification of each compound may have been acquired in the full
525.3-49
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scan or SIM mode. In general, all ions that are present above 30% relative
abundance in the mass spectrum of the reference standard obtained during
calibration should be present in the mass spectrum of the sample component
and should agree within an absolute 20%. For example, if an ion has a
relative abundance of 30% in the standard spectrum, its abundance in the
sample spectrum should be in the range of 10-50%.
12.1.3. Identification is hampered when sample components are not resolved
chromatographically and produce mass spectra containing ions contributed
by more than one analyte. When GC peaks obviously represent more than
one sample component (i.e., broadened peak with shoulder(s) or valley
between two or more maxima), appropriate analyte spectra and background
spectra can be selected by examining plots of characteristic ions.
Comparing a background subtracted spectrum to the reference spectrum is
suggested. If two or more analytes coelute but only one GC peak is
apparent, the identification criteria can be met but each analyte spectrum
will contain extraneous ions contributed by the coeluting compound.
12.1.4. Structural isomers that produce very similar mass spectra can be explicitly
identified only if they have sufficiently different GC retention times.
Acceptable resolution is achieved if the height of the valley between two
isomer peaks is < 25% of the average height of the two isomer peaks.
Otherwise, combine the peak areas of the isomers and quantify and identify
as an isomeric pair.
12.1.5. Tribufos is the oxidation product of merphos. When analyzed by GC/MS
under the conditions used during method development, the retention time
and mass spectrum produced by merphos is identical to that of tribufos.
Therefore, when tribufos is identified as a sample component in this
method, it is possible that the original contaminant may have been merphos.
12.1.6. For specific instructions on identification and quantitation of the multi-
component analytes chlordane and toxaphene, and for instructions on
screening for Aroclors, see Sect. 12.3.
12.2. QUANTITATION AND CALCULATIONS
12.2.1. Calculate analyte and surrogate concentrations using the multipoint
calibration established in Sect. 10.2. Invalidating this method,
concentrations were calculated by measuring the characteristic ions listed in
Table 1. Other ions may be selected at the discretion of the analyst. Do not
use daily continuing calibration check data to quantitate analytes in
samples. Adjust the final analyte concentrations to reflect the actual sample
volume determined in Sect. 11.10. Field Sample extracts that require
dilution should be treated as described in Sect. 12.2.2.
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12.2.2. If the calculated amount of any analyte exceeds the calibration range of the
curve, the extract must be diluted with EtOAc, with the appropriate amount
of additional internal standard added to match the original concentration.
Analyze the diluted extract. Acceptable surrogate performance (Sect. 9.3.6)
should be determined from the undiluted sample extract. Incorporate the
dilution factor into final concentration calculations. The resulting sample
should be documented as a dilution, and MRLs should be adjusted
accordingly. If matrix-matched calibration standards are being used, the
dilution may be made with EtOAc but care should be taken to dilute just
enough to position the analyte within the calibration range. Excessive
dilution and resulting low concentration may affect the accuracy of the final
measurement.
12.2.3. Calculations must utilize all available digits of precision, but final reported
concentrations should be rounded to an appropriate number of significant
figures (one digit of uncertainty), typically two, and not more than three
significant figures.
Note: Some data in Sect. 17 of this method are reported with more than two
significant figures. This is done to better illustrate the method performance
data.
12.3. MULTI-COMPONENT ANALYTES
12.3.1. Technical Chlordane - Technical chlordane is a multi-component analyte
regulated under the Safe Drinking Water Act (SDWA) at the time of
publication of this method. It contains at least 140 chlorinated components.
At the concentrations likely to be encountered in drinking water samples,
only two or three major components will typically be identified: cis- and
trans-chlordane and trans-nonachlor. If one or more of these components is
identified in a Field Sample, and a quantitative value for technical
chlordane is required, the analyst may choose from the following options:
Option 1: Obtain a standard of technical chlordane and use it to prepare
calibration curves for each major component observed in the Field Sample.
Assign the concentration of technical chlordane in the calibration standard
to each peak selected for quantitation. Quantitate each of the major
components observed in the Field Sample from the technical chlordane
calibration and report a technical chlordane amount by averaging the values
found for the components.
Option 2: If trans-chlordane is present as the major chlordane component,
multiply the concentration of trans-chlordane (determined from calibration
with a trans-chlordane standard) by seven to obtain a value for technical
chlordane. (A multiplier of seven was determined from the average weight
percent of trans-chlordane in multiple standards of technical chlordane.) If
525.3-51
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trans-chlordane is not the major chlordane component observed, Option 1
must be used.
12.3.2. Aroclor screening - Aroclors are complex mixtures of polychlorinated
biphenyls (PCBs). If any of the 14 PCB congeners in the analyte list are
identified in a Field Sample, presume that one or more Aroclors are present.
A quantitative value for "total PCBs" can be obtained by analyzing a
duplicate sample by Method 508A23.
12.3.3. Toxaphene - Identify the toxaphene peaks selected during calibration using
the procedures in Sects. 12.1.1 and 12.1.2. Use the calibration curves
created in Sect. 10.2.5.1 to quantitate each toxaphene peak. If all four peaks
are present, use the mean concentration of the four as the reported
concentration of technical toxaphene. All four peaks must be present in
calibration standards and all fortified samples, i.e., LFBs and LFSMs. If
one or more, but not all of the selected component peaks are present in a
Field Sample, it may be an indication that weathering has taken place. In
this case, calculate the amount of technical toxaphene to be reported as the
mean of ONLY the target peaks present (do not include any user-defined
value, or use zero in the mean calculation to represent missing peaks).
Annotate the reported technical toxaphene concentration with the range of
concentrations observed for the individual target peaks.
13. METHOD PERFORMANCE
13.1. METHOD DEVELOPMENT AND PERFORMANCE DATA COLLECTION - This
method was developed by USEPA's National Exposure Research Laboratory
(NERL) chemists and staff from Shaw Environmental and Infrastructure, Inc.
(SHAW) and Industrial and Environmental Services, LLC (IES) under contract to
USEPA's Office of Ground Water and Drinking Water (OGWDW). The method
was developed using the four types of SPE media described in Sects. 6.9-6.11. Most
data collected during the development phase of the method were duplicated in both
the NERL lab and the SHAW/IES lab by different analysts using different
instrumentation. This verified that the method procedures were transferable between
labs. The majority of the data presented in Sect. 17 were generated with these four
types of SPE media. Subsequent to the method development, Horizon Technologies,
Inc. and United Chemical Technologies (UCT) each generated data using the method
procedures with additional types of SPE media (Sects. 6.12-6.13). These additional
SPE products were added to the method to further extend the SPE options available
for use with this method. Data demonstrating the performance of these additional
sorbents are in Tables 11-14.
13.1.1. GC/MS INSTRUMENTATION - The instruments described in this section
were used to collect method performance data as cross-referenced in the
footnotes of the tables in Sect. 17.
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13.1.1.1. Thermo DSQ quadrupole mass spectrometer equipped with a
Thermo Trace Ultra GC and a Restek RXI-5sil-MS 30 m x 0.25
mm x 0.25 jam column. A 5-mm i.d. single gooseneck injection
port liner with Siltek deactivation was used (Restek #20946-214).
Calibration standards and sample extracts were injected in the hot,
splitless mode using a pressure pulse. See Sect. 10.2.3.1 for GC
oven temperature program.
13.1.1.2. Agilent 5975C MSD equipped with a 7890A GC and a Restek
RXI-5sil-MS 30 m x 0.25 mm x 0.25 jim column. A 4-mm i.d.
single gooseneck injection port liner with intermediate polarity
deactivation was used (Restek #20798). Calibration standards and
sample extracts were injected in the hot, splitless mode using a
pressure pulse. See Sect. 10.2.3.1 for GC oven temperature
program.
13.1.1.3. Agilent 5973 MSD equipped with a 6890 GC and a Restek RXI-
5sil-MS 30 m x 0.25 mm x 0.25 |im column. A drilled Uniliner
(Restek #21055) was used in the injector, installed with the hole on
top. One microliter pulsed (1 min) splitless injections were made
with the injector at 275 °C. The GC oven temperature program
was as follows: initial oven temperature 50 °C, hold for 1.5 min,
ramp a 10 °C/min to 130 °C, ramp at 2 °C/min to 142 °C, ramp at
20 °C/min to 270 °C, ramp at 7 °C/min to 320 °C, hold for 1 min.
13.1.1.4. Agilent 5975C MSD with a 6890N GC, equipped with a Restek
RXI-5sil-MS 30m x 0.25 mm x 0.25 jim column. A 4-mm i.d.
splitless gooseneck injection port liner (UCT#GCLGN4MM) was
used, with the injection port at 250 °C. One microliter injections
were made with a 1 min split delay. The GC oven temperature
program was as follows: initial oven temperature of 55 °C, hold for
1 min, ramp at 10 °C/min to 200 °C, ramp at 7 °C/min to a final
temperature of 320 °C, hold for 0.36 min.
13.2. PRECISION AND ACCURACY DATA
13.2.1. FULL SCAN GC/MS - Precision and accuracy data were collected from
LFBs at three concentration levels using each of the six sorbents described
in Sects. 6.9-6.13. Precision and accuracy data were also collected at a
single fortified concentration using two challenging water matrices. Water
matrices were selected to be representative of ground water with high
mineral content and surface water with a moderate level of TOC. Precision
and accuracy data in both fortified reagent water and fortified matrices are
presented in Tables 3-14. These data were generated using matrix-matched
calibration standards. Performance is similar for most analytes on most
sorbents, especially considering that the data were obtained by different
525.3-53
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analysts using different instrumentation. A notable exception is dimethipin.
The data generated for dimethipin using the J.T. Baker H2O Phobic DVB
Speedisk or the Oasis HLB cartridge provided the best performance. The
other sorbent options do not retain dimethipin sufficiently to meet the
method acceptance criteria for recovery. If dimethipin data are to be
reported, either the Oasis HLB cartridge or the J.T. Baker H2O Phobic DVB
Speedisk must be used.
13.2.2. SIM GC/MS - The SIM GC/MS analysis option may be used with extracts
from any of the options described in Sects. 6.9-6.13. To demonstrate the
enhanced sensitivity and overall method performance using SIM, two
sorbents were selected. Waters Oasis HLB cartridges and J.T. Baker H2O-
Phobic DVB Speedisks were specifically selected so that acceptable
performance data could be obtained for dimethipin, a compound of
particular interest to EPA at the time of method development. Precision and
accuracy data were collected by two laboratories using LFBs fortified at
three concentration levels. Additional precision and accuracy data were
collected by the same laboratories using LFSMs created by fortifying two
challenging tap water matrices with selected analytes at either one or two
concentrations. Tap water matrices were selected to be representative of
ground water with high mineral content and surface water with a moderate
level of TOC. Precision and accuracy data in both fortified reagent water
and fortified matrices are presented in Tables 17-20. These data were
generated using matrix-matched calibration standards.
13.2.3. Toxaphene data - Precision and accuracy data for toxaphene in the SIM
mode was generated using five sorbent options in reagent water (Table 21)
and using four sorbents in challenging drinking water matrices (Table 22).
Toxaphene data were not generated in the full scan mode due to poor
sensitivity relative to regulatory requirements (Sect. 1.7).
13.3. LCMRLsandDLs
13.3.1. FULL SCAN GC/MS - The values in Table 15 were generated by the
NERL and SHAW/IES laboratories. Sorbents were selected based on their
convenience of use by each of the laboratories. The use of these specific
brands of SPE media for generating LCMRLs and DLs does not imply any
specific preference or endorsement of the products. Because the data were
generated in two laboratories by different personnel using different sorbent
options and instrumentation, minor variations between the data sets should
be expected.
13.3.2. SIM GC/MS - The values for DLs in Table 23 were generated by the NERL
using Oasis HLB cartridges. Table 23 also includes two sets of LCMRL
data; one generated by NERL using Oasis HLB cartridges and one
generated by SHAW/IES using J.T. Baker H2O Phobic DVB Speedisks.
525.3-54
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These sorbents were selected because they provided acceptable performance
data for dimethipin, a compound of particular interest to EPA at the time of
method development.
13.4. SAMPLE STORAGE STABILITY STUDIES - Drinking water samples from a
chlorinated surface source were used as a representative matrix for an analyte
holding time study in aqueous solution. Replicate samples in amber bottles were
preserved as described in Sect. 8, fortified with method analytes, then stored for 48
hours at 10 °C, followed by storage at 6 °C until analysis. Randomly selected
samples were analyzed in replicate (n=4) on day 0 and at several time points up to
and beyond the 14 day holding time. Data from days 0, 7 and 14 are presented in
Figs. 3a-3c. These data were used to establish the 14 day aqueous holding time for
most method analytes (Sect. 8.4).
Notes:
• Surrogate analytes were not stored in this study, but added at the time of
extraction. The data in Figs. 3a-c for SURs are same day data, obtained for QC
purposes.
• Holding time studies conducted during method development indicated significant
analyte losses (more than 20% in 14 days, with increasing loss at subsequent
time points) for the two compounds listed below using the sample collection,
preservation and holding time procedures in this method. Dichlorvos exhibited a
loss of 25% at 7 days, 39% at 14 days and 56% at 28 days. Cyanazine exhibited
a loss of 16% at 7 days, 22% at 14 days, and 44% at 28 days. (All losses are
relative to the day 0 measurement.) Degradation of these compounds in aqueous
samples has been previously reported.24"26
• Toxaphene holding time data were collected in separate LFSMs. After 14 days
of storage under the conditions described above, the toxaphene recovery was
105% with an RSD of 7.1%. Aqueous holding time data for toxaphene are not
shown in Fig. 3.
13.5. EXTRACT STORAGE STABILITY STUDIES - Replicate sample extracts (n=4)
that were stored at -5 °C and protected from light, were analyzed on day 0, and at
five additional time points up to and beyond 28 days. Data from these analyses
validate the 28 day extract holding time and are presented in Figs. 4a-4c. Extract
holding time data for toxaphene were collected in separate sample extracts. After 28
days of storage under the conditions described above, the recovery of toxaphene was
104% with an RSD of 3.6. Extract holding time data for toxaphene are not shown in
Fig. 4.
13.6. POTENTIAL PROBLEMS/ PROBLEM COMPOUNDS
13.6.1. MATRIX INDUCED CHROMATOGRAPHIC RESPONSE
ENHANCEMENT - Some method analytes have the potential to exhibit a
high bias. This has been attributed to this phenomenon. Examples of this
are shown in Table 20a for oxyfluorfen and tebuconazole, which have
525.3-55
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recovery data for a fortified tap water (from a surface water source) that is
> 130% of the fortified amount. Data in Table 20b show that this
phenomenon is related to analyte concentration, since the high bias is not
observed at the higher fortified concentration. Compounds with the
potential for matrix induced chromatographic response enhancement are
noted in Table 1. Although the use of matrix-matched standards will
improve quantitative accuracy for these analytes, a bias may still be
observed. In addition to the use of matrix matched standards, "priming" the
GC system by injecting one or more sample extracts at the beginning of
each analytical sequence was found to reduce matrix enhancement effects.
The data presented in Tables 19, 20a and 20b were obtained using this type
of priming sequence. Literature citations suggest that temperature
programmed or cold injections may also reduce matrix enhancement,12'13'27
although trials of these types of injections during method development
showed little or no improvement. The biased data was instrument
dependent, and not related to the sorbent used. Similar tap water extracts
generated using different sorbent options listed in this method, showed
similarly high biased data on the same instrument.
Depending upon the intended use of the data, the analyst should consider
performing the MRL verification (Sect. 9.2.4.4) in fortified matrices similar
to the samples being analyzed.
HIGH BACKGROUND - Phthalates and adipates commonly appear in
LRBs, either from their presence in laboratory reagent water, or in
chemicals and solvents used in the sample preparation process. BHT was
also noted to have intermittently high background values during method
development. Compounds observed to have high background values are
noted in Table 1.
13.6.3. HCCPD - This compound is sometimes recovered at lower rates than other
method analytes. It is known to be highly reactive, and degrades relatively
quickly via photolysis and hydrolysis.28 The performance of this compound
during method development was influential in establishing lower
acceptance criteria for its recovery in LFBs.
13.6.4. HCB - This compound is sometimes recovered at lower rates than other
method analytes. Although there are literature references to
photodegradtion of HCB29'30, there was no direct evidence during method
development that this was the cause of low recovery. The performance of
this compound during method development was influential in establishing
lower acceptance criteria for its recovery in LFBs.
13.6.5. PENT ACHLOROPHENOL - Pentachlorophenol i s prone to peak tailing
and changes in response due to changes in the GC column and injector. In
this method the isotopically labeled 13C-pentachlorophenol has been used as
525.3-56
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an internal standard for pentachlorophenol to minimize inaccuracies in
quantitation. Assuming that there is not complete chromatographic
separation between pentachlorophenol and the isotopically-labeled IS, the
QI used for 13C-pentachlorophenol must be m/z 276 (Table 1). Although
this ion has low abundance, it is the only ion free of interferences from the
chlorine isotope ions of pentachlorophenol.
Some GC/MS instrumentation may have too many active sites for
acceptable analysis of pentachloro-phenol by this method. Alternate
methods that employ derivatization procedures to methylate
pentachlorophenol to its methyl ether prior to analysis are available for
drinking water compliance monitoring.31'32
13.6.6. EXCESSIVE WATER CONTENT IN EXTRACTS - This is most often
seen using the Speedisk, and is exacerbated by the use of some automated
extraction devices. Excessive water will typically result in low recoveries
of triazines. Not all automated extraction systems may be suitable for use
with the Speedisk option.
13.6.7. OVERDRYING SPE MEDIA PRIOR TO ELUTION - If SPE media is
over dried between sample loading and solvent elution by drawing
excessive amounts of room air through the media, analytes that can undergo
oxidation may be observed to have low recoveries. Benzo(a) pyrene is an
example of an analyte that may be affected.
13.7. MULTIPLE LABORATORY DEMONSTRATION - In addition to the two
laboratories in which this method was developed, the performance of this method in
the SIM mode for a subset of analytes (those listed in Table 18) was demonstrated by
three independent laboratories (two commercial laboratories and a drinking water
utility laboratory). These laboratories produced acceptable results and provided the
authors with valuable comments and method performance data. The authors wish to
acknowledge the assistance of the analysts and managers at the laboratories listed
below for their participation in the multi-laboratory study.
13.7.1. Dr. Yongtao Li and Mr. William Davis of Underwriters Laboratories, South
Bend, IN.
13.7.2. Mr. Kevin Durk and Ms. Annmarie Walsh of Suffolk County Water
Authority, Hauppauge, NY.
13.7.3. Dr. Andrew Eaton, Mr. Charles Grady, Mr. Ali Haghani and Mr. Patrick
Chapman of MWH Laboratories, Monrovia, CA.
14. POLLUTION PREVENTION
525.3-57
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14.1. This method utilizes SPE to extract analytes from water. It requires the use of very
small volumes of organic solvent and very small quantities of pure analytes, thereby
minimizing the potential hazards to both the analyst and the environment as
compared to the use of large volumes of organic solvents in conventional liquid-
liquid extractions.
14.2. For information about pollution prevention that may be applicable to laboratory
operations, consult "Less is Better: Guide to Minimizing Waste in Laboratories"
available on-line from the American Chemical Society at http://portal.acs.org/portal/
fileFetch/C/WPCP_012290/pdf/WPCP_012290.pdf accessed November 8, 2011.
15. WASTE MANAGEMENT
15.1. The analytical procedures described in this method generate relatively small amounts
of waste since only small amounts of reagents and solvents are used. The matrices
of concern are finished drinking water or source water. However, the Agency
requires that laboratory waste management practices be conducted consistent with all
applicable rules and regulations, and that laboratories protect the air, water, and land
by minimizing and controlling all releases from fume hoods and bench operations.
Also, compliance is required with any sewage discharge permits and regulations,
particularly the hazardous waste identification rules and land disposal restrictions.
16. REFERENCES
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Minimum Reporting Levels for Drinking Water Methods, Environ. Sci. Technol., 2006, 40,
281-288.
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and Human Services, Public Health Service, Agency for Toxic Substances and Disease
Registry (1999). Available at http://www.atsdr.cdc.gov/ToxProfiles/tpl 12.pdf (accessed
Octobers, 2011).
29. Yamada, M., Naito, N, Takada, M., Nakai, S., Hosomi, M., Photodegradation of
Hexachlorobenzene and Theoretical Prediction of its Degradation Pathways Using Quantum
Chemical Calculation, Chemosphere, 2008, 70, 731-736.
30. Plimmer, J.R., Klingebiel, U.I., Photolysis of Hexachlorobenzene, J. Agric. FoodChem.,
1976, 24, 721-723.
31. Pawlecki-Vonderheide, A.M., Munch, D.J., Method 515.3. Determination of Chlorinated
Acids in Drinking Water by Liquid-Liquid Extraction, Derivatization and Gas
525.3-60
-------
Chromatography with Electron Capture Detection. 1996. Available on-line at
http://www.nemi.gov (accessed October 5, 2011).
32. Wendelken, S.C., Bassett, M.V., Dattilio. T.A., Pepich, B.V., Method 515.4. Determination
of Chlorinated Acids in Drinking Water by Liquid-Liquid Microextraction, Derivatization,
and Fast Gas Chromatography with Electron Capture Detection. 2000. Available on-line at
http://www.nemi.gov (accessed October 5, 2011).
33. Standard Operating Procedure for Disinfectant Sample Preparation, SOP MB-22-00, 2008.
USEPA, Office of Pesticide Programs, Environmental Service Center, Ft. Meade, MD.
Available on-line at http://www.epa.gov/pesticides/methods/atmpmethods/MB-22-00.pdf
(access November 10, 2011).
525.3-61
-------
17. TABLES, FIGURES AND VALIDATION DATA
Table 1. Retention Times (RTs), Suggested Quantitation Ions (QIs), Suggested
Confirmation Ions, and Suggested Internal Standard Reference
Peak
Identification
#, Figure 1
15
41
47
116
1
2
o
J
4
5
6
7
8
9
10
11
12
13
14
16
17
18
19
20
21
22
23
24
25
26
RT (min)
13.21
16.35
16.73
24.29
7.24
8.20
9.13
9.97
11.21
11.53
12.44
12.48
12.71
12.74
12.77
12.84
12.87
12.88
13.43
13.45
13.47
13.69
13.79
13.92
14.31
14.44
14.46
14.53
14.68
Internal Standards, Analytes and
Surrogates
acenaphthene-^io (IS 1)
13C-pentachlorophenol (IS 4)
phenanthrene-^io (IS 2)
chrysene-^12 (IS 3)
DIMP
isophorone
l,3-dimethyl-2-nitrobenzene (SUR)
dichlorvos
HCCPD
EPTC
mevinphos
butylate
vernolate
dimethylphthalate
etridiazole
2,6-dinitrotoluene
acenaphthylene
pebulate
2-chlorobiphenyl
BHT
chloroneb
tebuthiuron
2,4-dinitrotoluene
molinate
DEBT
diethylphthalate
4 -chlorobiphenyl
fluorene
propachlor
IS Ref.
#
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
QI (m/z)
162
276
188
240
97
82
77
109
237
128
127
57
128
163
211
165
152
128
188
205
193
156
165
126
119
149
188
165
120
Confirmation
Ion(s) (nt/z)
164
-
160*
236*
123
138*
134
185*
235,239
86
109*, 192*
146, 156
86
77*
183
63,89
-
57,72
152
220
191
171
63,89
55
91, 190
177*
152
166
77, 176
Comments
a
b,c,d
a
a
b
a
a
a,d,e
a
a
a,d,e,f
a
a
a
a
a
a
a
a
b,g
a
a
a
a
b
a,g
a
a
a
525.3-62
-------
Table 1. Retention Times (RTs), Suggested Quantitation Ions (QIs), Suggested
Confirmation Ions, and Suggested Internal Standard Reference
Peak
Identification
#, Figure 1
27
28
29
30
31
32
33
34
35
36
37
38
39
40
42
43
44
45
46
48
49
50
51
52
53
54
55
56
57
58
RT (min)
15.00
15.03
15.27
15.34
15.66
15.75
15.81
15.83
16.08
16.20
16.21
16.28
16.29
16.30
16.35
16.36
16.46
16.66
16.69
16.79
16.81
16.91
16.91
17.01
17.06
17.53
17.68
17.71
17.73
17.79
Internal Standards, Analytes and
Surrogates
ethoprop
cycloate
chlorpropham
trifluralin
phorate
a-HCH
2,4'-dichlorobiphenyl
hexachlorobenzene
atraton
simazine
prometon
dimethipin
atrazine
P-HCH
pentachlorophenol
propazine
y-HCH (lindane)
pronamide
2,2',5-trichlorobiphenyl
phenanthrene
chlorothalonil
disulfoton
anthracene
terbacil
5-HCH
phosphamidon
acetochlor
metribuzin
2,4,4'-trichlorobiphenyl
vinclozolin
IS Ref.
#
1
1
1
1
1
1
1
1
2
2
2
2
2
2
4
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
QI (m/z)
97
83
213
264
75
181
222
284
196
201
225
54
200
181
266
214
183
173
256
178
266
88
178
117
181
127
146
198
186
212
Confirmation
Ion(s) (m/z)
126, 139, 158
55, 154
127
306
121
109, 183,219
152, 224
142, 249
169,211
173, 186
168,210
53
215
109, 183,219
264, 268
58, 229
109, 181,219
145
186
152*
264, 268
61*, 97*
-
161
109, 183,219
72, 264
59, 162, 223
-
256
124, 285
Comments
a,d
a
a
a,d
b,d
a
a
a
a
a
a
b
a
a
a,c,d
a
a,e
a
a
a
a,e
a
a
a,d
a
b,d
a
a
a,e
b,e
525.3-63
-------
Table 1. Retention Times (RTs), Suggested Quantitation Ions (QIs), Suggested
Confirmation Ions, and Suggested Internal Standard Reference
Peak
Identification
#, Figure 1
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
RT (min)
17.84
17.87
17.96
18.04
18.05
18.10
18.39
18.47
18.53
18.56
18.72
18.76
18.84
18.87
18.87
18.91
18.92
19.01
19.27
19.30
19.59
19.72
19.74
19.85
20.27
20.38
20.46
20.54
20.58
20.59
Internal Standards, Analytes and
Surrogates
methyl parathion
alachlor
simetryn
ametryn
heptachlor
prometryn
terbutryn
2,2',5,5'-tetrachlorobiphenyl
dibutyl phthalate
bromacil
metolachlor
chlorpyrifos
aldrin
cyanazine
dacthal (DCPA)
2,2',3,5'-tetrachlorobiphenyl
ethyl parathion
triadimefon
diphenamid
MGK 264(a)
MGK 264(b)
heptachlor epoxide
chlorfenvinphos
2,3',4',5-tetrachlorobiphenyl
trans-chlordane
tetrachlorvinphos
butachlor
pyrene
cis-chlordane
endosulfan I
IS Ref.
#
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
QI (m/z)
109
188
213
227
100
241
226
220
149
205, 207
162
97
66
225
301
220
109
208
72
164
164
353
267
220
375
109
176
202
375
241
Confirmation
Ion(s) (m/z)
125, 263
160
155, 170
212
272, 274
184, 226
170, 185, 241
290, 292
-
207, 205
238
197, 199
79, 263
68, 172, 198
332
255, 292
97, 291
57
167, 239*
66, 111
66, 111
81,355
269, 323
110,292
237, 272
329,331
57, 160
-
373, 377
195, 207
Comments
b,d
a
a
a
a
a
a
a
a
a
a
a,e
a
a
a
a
b,d
a,d,e
a
a,h
a,h
a,e
b,d
a
a
a,d
a,d
a
a
a
525.3-64
-------
Table 1. Retention Times (RTs), Suggested Quantitation Ions (QIs), Suggested
Confirmation Ions, and Suggested Internal Standard Reference
Peak
Identification
#, Figure 1
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
117
118
119
RT (min)
20.65
20.76
21.00
21.12
21.17
21.23
21.25
21.26
21.69
21.72
21.81
21.90
21.91
21.99
22.11
22.11
22.40
22.82
22.91
22.91
23.03
23.06
23.17
23.38
23.39
23.48
24.26
24.37
24.40
24.67
Internal Standards, Analytes and
Surrogates
trans-nonachlor
napropamide
profenofos
4,4'-DDE
tribufos (+merphos)
dieldrin
oxyfluorfen
2,3,3',4',6-pentachlorobiphenyl
nitrofen
endrin
2,2',3,4',5',6-hexachlorobiphenyl
chlorobenzilate
2,3',4,4',5-pentachlorobiphenyl
endosulfan II
4,4'-DDD
ethion
2,2',4,4',5,5'-hexachlorobiphenyl
norflurazon
butylbenzylphthalate
endosulfan sulfate
4,4'-DDT
2,2',3,4,4',5'-hexachlorobiphenyl
hexazinone
di(2-ethylhexyl)adipate
tebuconazole
triphenyl phosphate (SUR)
benzo [a] anthracene
chrysene
methoxychlor
2,2',3,4,4',5,5'-heptachlorobiphenyl
IS Ref.
#
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
QI (m/z)
409
72
339
246
57
79
252
326
283
263
360
251
326
195
235
231
360
145
149
272
235
360
171
129
125
77
228
228
227
394
Confirmation
Ion(s) (m/z)
407,411
100, 128
97, 139, 208
176,318
169
81
63,361
184, 254
139, 202
81,281
218,290
111, 139
184, 254
207, 241
165
97, 153
218,290
102, 303
91,206
237, 387
165
218,290
83*
57,70
83, 250
169, 326
226*
226*
-
252, 324
Comments
a
a,d
b,d
a
b,d,i
a,e
b,d
a
b,d
a
a
a
a
a
a,d
b,d,e
a
a,d
a,g
a,e
a,e
a
a,d
a,g
b,d,e
a,e
a
a
a,d
a
525.3-65
-------
Table 1. Retention Times (RTs), Suggested Quantitation Ions (QIs), Suggested
Confirmation Ions, and Suggested Internal Standard Reference
Peak
Identification
#, Figure 1
120
121
122
123
124
125
126
127
128
129
130
131
RT (min)
24.93
25.79
26.64
26.82
27.49
27.54
28.22
28.28
28.50
30.72
30.80
31.20
Internal Standards, Analytes and
Surrogates
di(2-ethylhexyl)phthalate
fenarimol
cis-permethrin
trans-permethrin
benzo[6]fluoranthene
benzo [k] fluoranthene
benzo[a]pyrene-<5?i2 (SUR)
benzo[a]pyrene
fluridone
indeno[l,2,3-c,c/|pyrene
dibenzo[a,/z]anthracene
benzo [g, h, /'Jperylene
IS Ref.
#
3
3
3
3
3
3
3
3
3
3
3
3
QI (m/z)
149
107
183
183
252
252
264
252
328
276
278
276
Confirmation
Ion(s) (m/z)
167
139,219
163*
163*
126*
126*
132*
126*
329
138*
139*
138*
Comments
a,g
a
a,d,e
a,d,e
a
a
a
a
a,c,d
a
a
a
* Confirmation ions may be at or below 30% relative abundance depending on instrument tune.
~ Compounds without values do not have qualifier ions of significant relative abundance.
Comment Key
a. PDS solvent, acetone
b. PDS solvent, methanol
c. May exhibit peak tailing
d. Potential to exhibit matrix induced chromatographic response enhancement was observed during method
development. This assessment was done based on a peak area comparison of a standard prepared in solvent
compared to a matrix-matched standard, both at a concentration of 0.2 ng/uL. If the matrix-matched standard
area was > 130% of the solvent prepared standard, the analyte was flagged as having the potential for matrix
induced chromatographic response enhancement.
e. Literature references 11 and 12 indicate that this compound may exhibit matrix induced response enhancement.
f Mevinphos exists as two isomers, cis and trans that will partially or completely coelute in this method. Partial
coelution results in distorted peak shape.
g. Commonly occurs in LRBs
h. MGK 264 consists of two isomers, endo and exo. In this method, a standard of mixed isomers was used. The
resulting chromatographic peaks have been designated by the authors as (a) and (b) throughout this document,
where (a) is the first eluting isomer and (b) is the second eluting isomer. The amounts of each isomer listed in
subsequent tables are based on the relative peak areas of the two isomers. Users of this method who need to
specifically identify each isomer, must obtain and analyze standards of each isomer.
i. Tribufos + merphos. Some fortified samples were fortified with tribufos and merphos together because of the
configuration of standards used. Subsequent analysis of individual standards of merphos and tribufos showed
an identical retention time, mass spectrum and response for each compound when analyzed at the same
concentration. The mass spectrum observed matched the NIST MS library for tribufos.
525.3-66
-------
Table 2. Ion Abundance Criteria for Decafluorotriphenyl Phosphine (DFTPP)"
Mass (m/z)
68
69
70
197
198
199
365
441
442
443
Relative Abundance Criteria
< 2% of m/z 69
present
< 2% of m/z 69
<2%ofWzl98
present c
5-9% of m/z 198
>1% of base peak
< 150%ofWz443
present c
15-24% of m/z 442
Purpose of Checkpoint11
Low-mass resolution
Low-mass resolution
Low-mass resolution
Mid-mass resolution
Mid-mass resolution and sensitivity
Mid-mass resolution and isotope ratio
Baseline threshold
High-mass resolution
High-mass resolution and sensitivity
High-mass resolution and isotope ratio
a. These ion abundance criteria have been developed specifically for target compound analysis
as described in this method. Adherence to these criteria may not produce spectra suitable for
identifying unknowns by searching commercial mass spectral libraries. If the analyst intends
to use data generated with this method to identify unknowns, adherence to stricter DFTPP
criteria as published in previous methods22 is recommended.
b. All ions are used primarily to check the mass accuracy of the mass spectrometer and data
system, and this is the most important part of the performance test. The three resolution
checks, which include natural abundance isotope ratios, constitute the next most important
part of the performance test, followed by the correct setting of the baseline threshold, as
indicated by the presence of m/z 365.
c. Either m/z 198 or 442 is typically the base peak.
525.3-67
-------
Table 3. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using Oasis HLB SPE Cartridges; Full
Scan GC/MS Analyses"
Analytes
acenaphthylene
acetochlor
alachlor
aldrin
ametryn
anthracene
atraton
atrazine
benzo [a] anthracene
benzo[a]pyrene
benzo[6]fluoranthene
benzo \g, h, /'Jperylene
benzo[&]fluoranthene
BHT
bromacil
butachlor
butylate
butylbenzylphthalate
chlordane, cis
chlordane, trans
chlorfenvinphos
chlorobenzilate
chloroneb
chlorothalonil
chlorpropham
chlorpyrifos
chrysene
cyanazine
Fortified Cone.
0.25 jig/Lb
n=4
Mean %
Recovery
87.1
102
106
96.2
105
90.1
108
103
90.9
95.4
98.2
97.0
103
NDe
119
106
91.2
105
99.1
91.7
101
109
91.8
102
119
112
95.6
107
RSD
2.8
4.6
3.6
2.0
4.6
4.6
11
1.3
7.0
5.5
3.1
13
5.6
2.1
4.8
4.2
5.9
2.9
1.4
6.8
1.1
5.5
2.7
11
13
8.3
9.4
Fortified Cone.
2.0 jig/Lc
n=8
Mean %
Recovery
95.8
108
107
87.1
102
98.5
109
106
104
96.4
96.8
94.9
102
NDe
103
106
104
123
105
99.3
105
109
97.5
101
105
99.8
107
111
RSD
2.2
6.8
5.6
6.2
7.1
2.7
6.6
7.2
2.8
5.7
3.8
5.6
4.5
12
3.5
6.0
7.4
3.7
3.6
3.9
4.5
5.0
2.9
5.6
6.3
2.3
6.3
Fortified Cone.
5.0 ng/Ld
n=4
Mean %
Recovery
88.7
95.2
102
86.4
95.0
98.4
99.9
102
89.2
89.0
90.8
90.3
92.8
92.8
99.5
94.5
88.6
92.9
99.8
105
108
96.8
94.9
106
92.7
94.4
89.8
95.5
RSD
1.7
2.0
3.0
2.0
3.0
0.66
1.3
1.1
0.75
5.1
2.4
5.9
3.3
1.3
1.4
2.5
1.9
2.2
0.86
3.8
2.6
2.0
2.4
2.6
2.0
2.3
0.39
1.0
525.3-68
-------
Table 3. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using Oasis HLB SPE Cartridges; Full
Scan GC/MS Analyses"
Analytes
cycloate
dacthal (DCPA)
ODD, 4,4'-
DDE, 4,4'-
DDT, 4,4'-
DEET
di(2-ethylhexyl)adipate
di(2-ethylhexyl)phthalate
dibenzo[a,/z]anthracene
dibutyl phthalate
dichlorvos
dieldrin
diethylphthalate
dimethipin
dimethylphthalate
DIMP
dinitrotoluene, 2,4-
dinitrotoluene, 2,6-
diphenamid
disulfoton
endosulfan I
endosulfan II
endosulfan sulfate
endrin
EPTC
ethion
ethoprop
ethyl parathion
Fortified Cone.
0.25 jig/Lb
n=4
Mean %
Recovery
90.4
91.5
101
98.1
106
102
106
144
97.3
81.0
101
97
108
107
99.3
104
109
NDf
104
85.2
101
106
98.7
94.7
87.9
103
109
101
RSD
2.7
7.3
6.0
1.2
5.0
4.1
5.2
27
17
11
9.2
2.0
7.2
15
3.0
5.3
6.7
4.4
1.3
13
7.0
6.2
14
1.8
6.0
21
16
Fortified Cone.
2.0 jig/Lc
n=8
Mean %
Recovery
99.6
103
103
100
104
101
104
112
83.9
119
98.3
100
104
95.2
101
96.2
96.8
110
109
85.6
101
113
106
107
99.8
104
103
89.8
RSD
5.0
4.4
5.7
5.9
6.1
2.9
3.2
4.6
11
6.8
5.9
5.0
2.6
5.5
3.6
1.6
4.4
5.2
6.6
4.9
6.0
9.6
6.2
5.9
6.9
3.6
8.6
3.8
Fortified Cone.
5.0 ng/Ld
n=4
Mean %
Recovery
90.7
101
92.5
95.0
95.7
94.2
94.9
91.3
98.6
104
91.2
91.6
94.2
61.1
95.5
90.6
91.1
90.7
93.0
89.3
97.9
93.9
96.5
95.8
91.1
93.0
92.1
95.8
RSD
1.8
1.5
0.70
2.4
0.80
0.81
3.9
1.8
5.8
2.8
2.5
2.1
1.4
7.3
1.1
2.1
0.59
2.4
1.4
1.9
1.7
0.70
1.5
3.2
1.5
0.59
2.1
1.6
525.3-69
-------
Table 3. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using Oasis HLB SPE Cartridges; Full
Scan GC/MS Analyses"
Analytes
etridiazole
fenarimol
fluorene
fluridone
HCCPD
HCH, a
HCH, (3
HCH, 5
HCH, y (lindane)
heptachlor
heptachlor epoxide
hexachlorobenzene
hexazinone
indeno[l,2,3-c,
-------
Table 3. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using Oasis HLB SPE Cartridges; Full
Scan GC/MS Analyses"
Analytes
pebulate
pentachlorophenol
permethrin, cis
permethrin, trans
phenanthrene
phorate
phosphamidon
profenofos
prometon
prometryn
pronamide
propachlor
propazine
pyrene
simazine
simetryn
tebuconazole
tebuthiuron
terbacil
terbutryn
tetrachlorvinphos
triadimefon
tribufos+merphos
trifluralin
vernolate
vinclozolin
PCB congeners (by IUPAC#)
2-chlorobiphenyl (1)
Fortified Cone.
0.25 jig/Lb
n=4
Mean %
Recovery
92.2
92.9
101
100
84.2
95.8
112
104
93.5
109
102
102
99.6
95.7
96
107
105
105
95.9
111
109
99.6
111
94.4
95.3
94.9
83.4
RSD
2.7
5.6
5.4
5.1
7.7
5.3
7.8
16
13
8.7
2.4
7.6
5.1
2.6
1.2
4.7
1.6
4.0
6.2
4.6
6.3
7.5
2.8
1.1
1.6
7.3
3.2
Fortified Cone.
2.0 jig/Lc
n=8
Mean %
Recovery
101
85.8
109
101
101
89.8
112
109
110
104
104
103
107
102
84.8
107
107
109
104
107
104
110
105
104
96.5
99.7
92.6
RSD
4.3
5.5
5.2
4.5
2.2
2.4
4.2
7.1
7.5
6.7
6.8
4.4
4.4
2.4
5.2
6.7
5.0
5.0
7.1
5.8
7.8
6.8
4.2
5.2
5.1
4.7
5.4
Fortified Cone.
5.0 ng/Ld
n=4
Mean %
Recovery
92.7
93.9
88.5
90.5
95.6
91.0
97.8
99.7
92.4
101
100
92.9
99.2
93.6
100
107
96.1
96.8
98.7
100
94.8
98.0
99.1
90.7
92.3
96.9
88.6
RSD
1.1
2.7
3.2
1.6
1.1
1.5
2.0
0.92
2.1
3.6
1.9
1.2
2.8
1.3
2.7
1.3
0.87
2.1
3.4
1.4
2.4
2.7
1.3
0.72
0.82
2.2
1.5
525.3-71
-------
Table 3. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using Oasis HLB SPE Cartridges; Full
Scan GC/MS Analyses"
Analytes
4-chlorobiphenyl (3)
2,4'-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
2,2',3,5'-tetrachlorobiphenyl(44)
2,2',5,5'-tetrachlorobiphenyl(52)
2,3 ',4',5-tetrachloroobiphenyl (70)
2,3,3 ',4',6-pentachlorobiphenyl (1 10)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Surrogate Analytes
1 , 3 -dimethyl-2 -nitrobenzene
benzo [a] pyrene-c/i 2
triphenyl phosphate
Fortified Cone.
0.25 jig/Lb
n=4
Mean %
Recovery
82.4
78.5
83.4
83.2
91.2
84.3
89.9
98.2
92.5
94.5
96.1
92.2
88.5
91.5
101
102
RSD
3.0
3.5
11
6.0
5.3
4.4
7.3
6.7
5.1
4.0
5.8
0.9
4.1
3.7
4.7
2.8
Fortified Cone.
2.0 ug/Lc
n=8
Mean %
Recovery
94.0
92.2
94.1
93.6
99.4
102
98.5
98.1
99.3
98.7
103
101
107
94.0
86.5
105
RSD
4.4
4.7
4.2
6.9
4.3
3.7
5.2
4.3
4.4
5.0
4.5
4.3
3.6
2.5
3.5
3.2
Fortified Cone.
5.0 ng/Ld
n=4
Mean %
Recovery
86.2
90.8
92.5
90.3
94.6
94.5
95.0
94.6
96.2
95.1
97.6
99.1
100
91.3
91.2
88.3
RSD
1.0
2.1
2.8
1.1
1.8
1.5
0.73
0.60
1.5
1.3
0.74
2.0
3.0
1.7
3.0
1.8
a. Data obtained on the instrumentation described in Sect. 13.1.1.1.
b. Exceptions to the stated concentration are as follows: Surrogate concentrations are 5.0 ug/L, pentachlorophenol
is 1.0 ug/L, tebuconazole is 1.2 ug/L, c-permethrin is 0.14 ug/L, t-permethrin is 0.36 ug/L, MGK 264(a) is 0.20
ug/L and MGK 264(b) is 0.050 ug/L.
c. Exceptions to the stated concentration are as follows: Surrogate concentrations are 5.0 ug/L, pentachlorophenol
is 8.0 ug/L, tebuconazole is 10.0 ug/L, c-permethrin is 1. lug/L, t-permethrin is 2.9ug/L, and MGK 264(a) is 1.6
ug/L and MGK 264(b) is 0.40 ug/L.
d. Exceptions to the stated concentration are as follows: Surrogate concentrations are 5.0 ug/L, pentachlorophenol
is 20.0 ug/L, tebuconazole is 25.0 ug/L, c-permethrin is 2.8 ug/L, t-permethrin is 7.2 ug/L, and MGK 264(a) is
4.0ug/L and MGK 264(b) is 1.0 ug/L.
e. ND = Not determined. Analyte could not be determined because of high laboratory reagent blank values.
f. ND = Not determined. Analyte could not be determined because of the low concentration.
525.3-72
-------
Table 4. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
Oasis HLB SPE Cartridges; N=4 for Each Matrix; Full Scan GC/MS Analysesa
Analytes
acenaphthylene
acetochlor
alachlor
aldrin
ametryn
anthracene
atraton
atrazine
benzo [a] anthracene
benzo[a]pyrene
benzo[6]fluoranthene
benzo [g, h, /'Jperylene
benzo[&]fluoranthene
BHT
bromacil
butachlor
butylate
butylbenzylphthalate
chlordane, cis-
chlordane, trans
chlorfenvinphos
chlorobenzilate
chloroneb
chlorothalonil
chlorpropham
chlorpyrifos
chrysene
cyanazine
cycloate
Fortified
Cone. (jig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Ground Water
Mean %
Recoveryd
90.5
102
104
80.3
91.8
96.5
96.5
100
99.1
91.1
93.9
95.3
97.2
NDe
89.4
102
101
110
96.9
92.0
104
105
87.9
98.1
100
97.7
102
103
92.9
RSD
1.7
3.8
6.2
3.2
6.7
1.3
1.8
2.2
4.0
4.2
3.3
5.9
2.7
2.3
4.0
1.9
4.7
3.9
4.0
3.3
4.1
3.7
3.4
2.3
3.1
3.1
2.7
2.2
Surface Water0
Mean %
Recoveryd
99.3
128
115
91.6
97.8
101
94.1
106
104
99.9
105
113
96.7
NDd
108
117
114
99.8
112
106
102
116
95.5
108
120
110
104
102
105
RSD
2.5
2.3
3.8
2.0
4.7
3.3
4.7
3.6
3.7
1.2
3.4
2.9
4.6
2.9
4.8
2.6
4.0
2.4
3.3
3.6
4.0
2.3
2.2
5.2
3.7
3.1
1.8
2.0
525.3-73
-------
Table 4. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
Oasis HLB SPE Cartridges; N=4 for Each Matrix; Full Scan GC/MS Analysesa
Analytes
dacthal (DCPA)
ODD, 4,4'-
DDE, 4,4'-
DDT, 4,4'-
DEET
di(2-ethylhexyl)adipate
di(2-ethylhexyl)phthalate
dibenzo[a,/z]anthracene
dibutyl phthalate
dichlorvos
dieldrin
diethylphthalate
dimethipin
dimethylphthalate
DIMP
dinitrotoluene, 2,4-
dinitrotoluene, 2,6-
diphenamid
disulfoton
endosulfan I
endosulfan II
endosulfan sulfate
endrin
EPTC
ethion
ethoprop
ethyl parathion
etridiazole
fenarimol
Fortified
Cone. Qig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Ground Water
Mean %
Recoveryd
98.7
95.2
93.7
102
103
101
101
85.6
114
94.3
96.0
90.5
94.9
97.7
93.4
100
103
102
73.0
99.4
106
94.3
107
96.1
104
97.9
87.1
98.8
101
RSD
2.8
2.8
3.5
4.5
1.7
2.9
3.7
5.8
4.5
1.6
3.0
1.2
6.7
2.7
2.0
0.40
2.6
3.1
5.1
3.2
2.8
9.1
5.2
1.2
3.7
2.4
4.0
2.0
3.0
Surface Water0
Mean %
Recoveryd
108
105
104
117
103
106
99.8
102
109
118
101
102
85.3
108
98.4
115
124
109
82.6
109
108
102
118
110
105
122
93.8
121
112
RSD
2.7
2.9
2.7
2.2
2.4
3.8
6.3
2.4
8.5
2.2
3.8
2.5
2.9
2.5
4.5
2.9
3.8
4.1
5.9
3.2
4.0
2.9
2.0
2.6
2.4
2.3
10
4.1
4.1
525.3-74
-------
Table 4. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
Oasis HLB SPE Cartridges; N=4 for Each Matrix; Full Scan GC/MS Analysesa
Analytes
fluorene
fluridone
HCCPD
HCH, a
HCH, (3
HCH, 5
HCH, y (lindane)
heptachlor
heptachlor epoxide
hexachlorobenzene
hexazinone
indeno[l,2,3-c,t/|pyrene
isophorone
methoxychlor
methyl parathion
metolachlor
metribuzin
mevinphos
MGK 264(a)
MGK 264(b)
molinate
napropamide
nitrofen
nonachlor, trans
norflurazon
oxyfluorfen
pebulate
pentachlorophenol
permethrin, trans
Fortified
Cone. (jig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
1.6
0.4
2.0
2.0
2.0
2.0
2.0
2.0
2.0
8.0
1.1
Ground Water
Mean %
Recoveryd
94.9
88.8
99.1
96.3
86.8
93.8
98.6
105
100
81.5
98.5
96.0
92.4
102
102
102
89.4
94.9
98.1
97.8
91.3
103
96.8
96.7
92.5
106
95.9
81.9
95.8
RSD
1.1
3.9
2.8
2.6
2.6
1.7
2.7
4.3
1.7
2.6
3.6
4.8
1.2
1.8
o o
5.5
1.6
5.9
3.2
3.0
4.0
3.5
1.3
3.5
4.2
4.6
4.1
2.3
13
3.0
Surface Water0
Mean %
Recoveryd
100
116
111
111
110
95.1
111
113
110
95.3
108
111
106
120
108
114
92.1
116
110
110
107
112
102
107
114
112
109
96.3
107
RSD
3.8
4.4
4.3
2.9
2.8
0.6
7.2
2.6
1.8
3.0
1.9
1.1
3.2
4.4
4.2
2.7
6.2
2.9
2.7
3.6
4.7
3.3
3.4
3.6
1.7
3.0
1.9
7.3
2.9
525.3-75
-------
Table 4. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
Oasis HLB SPE Cartridges; N=4 for Each Matrix; Full Scan GC/MS Analysesa
Analytes
permethrin, trans
phenanthrene
phorate
phosphamidon
profenofos
prometon
prometryn
pronamide
propachlor
propazine
pyrene
simazine
simetryn
tebuconazole
tebuthiuron
terbacil
terbutryn
tetrachlorvinphos
triadimefon
tribufos+merphos
trifluralin
vernolate
vinclozolin
PCB congeners (by IUPAC#)
2-chlorobiphenyl (1)
4-chlorobiphenyl (3)
2,4-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
Fortified
Cone. (jig/L)
2.9
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
10.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Ground Water
Mean %
Recoveryd
93.2
97.0
92.5
108
105
94.7
96.9
101
99.5
101
97.1
78.9
96.9
112
105
108
101
102
104
105
101
91.3
98.8
85.8
96.0
87.8
86.2
87.8
RSD
4.3
2.5
2.3
5.6
2.5
1.9
3.2
2.8
1.9
2.0
4.3
2.0
3.2
1.1
2.5
3.9
4.5
4.2
3.1
2.4
2.4
0.8
2.9
1.2
1.7
2.3
3.5
7.4
Surface Water0
Mean %
Recoveryd
104
99.6
96.9
103
110
88.3
100
114
114
105
100
79.9
99.8
107
106
121
106
110
109
110
116
106
99.5
97.0
99.5
96.6
94.8
100
RSD
3.3
3.7
1.5
3.4
4.3
5.5
3.7
2.8
2.7
3.5
3.2
2.9
2.0
1.2
3.3
6.5
4.7
4.4
3.7
1.9
3.2
2.6
2.9
2.3
4.4
3.3
5.2
2.8
525.3-76
-------
Table 4. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
Oasis HLB SPE Cartridges; N=4 for Each Matrix; Full Scan GC/MS Analysesa
Analytes
2,2',3,5'-tetrachlorobiphenyl(44)
2,2',5,5'-tetrachlorobiphenyl(52)
2,3 ',4',5-tetrachloroobiphenyl (70)
2,3,3 ',4',6-pentachlorobiphenyl (1 10)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Surrogate Analytes
l,3-dimethyl-2-nitrobenzene (SUR)
benzo [a] pyrene-^i 2
triphenyl phosphate (SUR)
Fortified
Cone. (jig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
5.0
5.0
5.0
Ground Water
Mean %
Recoveryd
93.6
104
92.8
93.2
91.2
88.2
95.7
93.1
97.7
92.3
88.4
108
RSD
3.4
4.7
1.8
2.6
3.7
6.7
0.8
5.2
1.8
1.7
3.2
2.5
Surface Water0
Mean %
Recoveryd
105
103
103
102
102
97.5
106
103
107
97.9
88.0
103
RSD
2.7
3.7
2.1
2.0
4.4
4.2
4.2
3.1
2.5
2.8
3.9
2.7
a. Data obtained on the instrumentation described in Sect. 13.1.1.1.
b. Tap water from a ground water source with high mineral content. Tap water hardness was 290 mg/L as calcium
carbonate.
c. Tap water from a surface water source. TOC of 2.8 mg/L.
d. Recoveries have been corrected to reflect the native amount in the unfortified matrix water.
e. ND= Not determined. Analyte could not be determined because of high laboratory reagent blank values.
525.3-77
-------
Table 5. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using J.T. Baker Speedisk HiO Phobic DVB
SPE Columns (Cartridges); Full Scan GC/MS Analyses'1
Analytes
acenaphthylene
acetochlor
alachlor
aldrin
ametryn
anthracene
atraton
atrazine
benzo [a] anthracene
benzo[a]pyrene
benzo[6]fluoranthene
benzo \g, h, /'Jperylene
benzo[&]fluoranthene
BHT
bromacil
butachlor
butylate
butylbenzylphthalate
chlordane, cis
chlordane, trans
chlorfenvinphos
chlorobenzilate
chloroneb
chlorothalonil
chlorpropham
chlorpyrifos
chrysene
cyanazine
Fortified Cone.
0.25 jig/Lb
n=4
Mean %
Recovery
84.9
102
96.0
95.6
97.6
89.4
107
100
89.1
89.9
94.1
89.9
92.5
81.7
104
103
91.0
103
97.2
93.7
92.7
99.9
92.9
90.9
97.9
92.2
90.4
93.2
RSD
1.9
4.0
5.0
2.5
3.2
3.2
12
6.7
0.43
11
2.6
10
7.4
11
8.2
2.1
2.6
5.8
5.2
5.3
5.3
4.7
2.9
5.6
12
13
7.9
6.4
Fortified Cone.
2.0 jig/Lc
n=8
Mean %
Recovery
88.2
94.7
94.6
88.3
95.7
91.1
101
99.3
95.8
89.7
97.6
92.8
92.9
86.0
97.5
92.0
95.5
96.5
97.9
106
99.1
98.2
95.9
97.6
98.9
94.7
96.2
19.2
RSD
2.4
1.9
2.2
7.1
3.9
2.9
3.3
1.0
2.9
5.2
3.8
9.0
3.9
3.2
17
2.2
1.6
3.1
2.6
2.3
4.6
3.7
2.5
2.8
2.9
2.2
3.8
3.8
Fortified Cone.
5.0 ng/Ld
n=4
Mean %
Recovery
90.7
97.0
103
96.5
96.0
104
97.9
100
92.4
100
96.6
98.7
99.7
86.0
97.7
99.6
92.7
101
103
105
98.9
102
95.2
99.5
93.3
99.5
94.7
99.1
RSD
1.8
3.0
3.2
4.5
4.1
2.7
2.5
3.4
1.9
3.5
0.81
5.1
1.6
0.53
2.9
1.3
0.59
4.3
2.2
1.2
3.3
3.8
1.9
3.2
2.2
4.4
1.6
3.7
525.3-78
-------
Table 5. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using J.T. Baker Speedisk HiO Phobic DVB
SPE Columns (Cartridges); Full Scan GC/MS Analyses'1
Analytes
cycloate
dacthal (DCPA)
ODD, 4,4'-
DDE, 4,4'-
DDT, 4,4'-
DEET
di(2-ethylhexyl)adipate
di(2-ethylhexyl)phthalate
dibenzo[a,/z]anthracene
dibutylphthalate
dichlorvos
dieldrin
diethylphthalate
dimethipin
dimethylphthalate
DIMP
dinitrotoluene, 2,4-
dinitrotoluene, 2,6-
diphenamid
disulfoton
endosulfan I
endosulfan II
endosulfan sulfate
endrin
EPTC
ethion
ethoprop
ethyl parathion
Fortified Cone.
0.25 jig/Lb
n=4
Mean %
Recovery
86.1
91.2
98.4
90.9
99.7
95.9
96.2
NDe
85.8
94.7
94.4
94.8
88.4
85.1
97.6
98.1
ND
ND
101
90.7
98.5
98.8
98.2
86.8
88.2
97.5
85.9
79.2
RSD
3.4
8.3
1.2
4.9
4.0
4.8
7.8
14
32
5.0
7.8
5.5
17
6.7
2.5
4.4
5.5
2.6
4.2
7.5
8.6
5.7
7.0
4.2
14
Fortified Cone.
2.0 jig/Lc
n=8
Mean %
Recovery
93.8
100
98.1
93.4
99.1
97.9
101
106
89.7
105
101
98.2
98.6
36.8
96.8
92.7
97.9
95.7
95.3
73.9
95.3
91.6
97.6
101
96.5
94.0
98.6
99.9
RSD
1.7
3.0
2.9
2.5
2.0
2.1
6.2
9.1
10
4.2
2.0
3.6
1.4
6.5
1.8
o o
J.J
4.1
1.7
3.4
6.0
4.2
4.9
4.4
4.8
2.6
3.0
3.1
2.4
Fortified Cone.
5.0 ng/Ld
n=4
Mean %
Recovery
94.6
99.6
98.5
103
98.7
93.9
95.2
92.5
101
102
93.8
101
94.1
25.2
95.1
91.7
92.1
92.1
98.5
94.2
100
104
99.7
101
92.8
97.4
93.3
96.1
RSD
1.9
2.8
3.2
2.8
2.8
2.2
1.3
3.0
5.6
3.3
4.9
1.2
0.60
1.8
2.6
2.1
1.3
3.1
3.2
5.1
2.5
2.4
4.6
4.5
1.3
3.8
3.3
3.0
525.3-79
-------
Table 5. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using J.T. Baker Speedisk HiO Phobic DVB
SPE Columns (Cartridges); Full Scan GC/MS Analyses'1
Analytes
etridiazole
fenarimol
fluorene
fluridone
HCCPD
HCH, a
HCH, (3
HCH, 5
HCH, y (lindane)
heptachlor
heptachlor epoxide
hexachlorobenzene
hexazinone
indeno[l,2,3-c,
-------
Table 5. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using J.T. Baker Speedisk HiO Phobic DVB
SPE Columns (Cartridges); Full Scan GC/MS Analyses'1
Analytes
pebulate
pentachlorophenol
permethrin, cis
permethrin, trans
phenanthrene
phorate
phosphamidon
profenofos
prometon
prometryn
pronamide
propachlor
propazine
pyrene
simazine
simetryn
tebuconazole
tebuthiuron
terbacil
terbutryn
tetrachlorvinphos
triadimefon
tribufos+merphos
trifluralin
vernolate
vinclozolin
PCB congeners (by IUPAC#)
2-chlorobiphenyl (1)
Fortified Cone.
0.25 jig/Lb
n=4
Mean %
Recovery
90.3
85.8
91.6
93.6
86.9
90.4
109
99.9
83.1
103
94.1
94.5
107
92.0
88.0
92.4
106
91.7
82.6
99.4
96.8
102
119
92.5
92.0
98.8
84.7
RSD
3.3
6.0
4.4
3.8
1.1
1.6
8.6
11
4.0
4.7
6.0
0.94
4.1
2.7
9.3
6.0
3.2
5.6
9.0
2.8
5.6
11
2.2
3.3
1.2
6.6
4.6
Fortified Cone.
2.0 jig/Lc
n=8
Mean %
Recovery
92.9
95.4
99.3
92.8
94.9
87.1
97.2
95.6
98.6
99.8
99.1
98.6
98.9
96.0
98.3
97.3
96.9
97.0
102
99.0
88.6
112
90.4
98.9
96.7
101
92.9
RSD
2.2
2.5
3.2
3.2
2.8
2.1
4.0
6.9
2.8
2.5
2.2
1.2
2.2
2.3
2.2
2.1
2.8
2.5
5.7
1.7
o o
J.J
3.4
2.7
1.3
2.0
3.1
2.4
Fortified Cone.
5.0 ng/Ld
n=4
Mean %
Recovery
92.5
98.5
91.2
92.2
96.3
90.0
95.2
102
90.4
99.3
95.8
96.5
97.3
100
96.4
108
94.2
95.2
97.7
100
99.1
96.4
100
93.9
94.0
97.9
90.5
RSD
2.3
4.5
2.8
1.7
2.0
1.7
2.8
4.1
4.2
2.5
1.6
0.77
3.3
2.3
1.7
3.5
1.1
2.3
3.0
3.1
3.3
4.1
3.4
0.71
0.71
3.8
0.78
525.3-81
-------
Table 5. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using J.T. Baker Speedisk HiO Phobic DVB
SPE Columns (Cartridges); Full Scan GC/MS Analyses'1
Analytes
4-chlorobiphenyl (3)
2,4'-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
2,2',3,5'-tetrachlorobiphenyl(44)
2,2',5,5'-tetrachlorobiphenyl(52)
2,3 ',4',5-tetrachloroobiphenyl (70)
2,3,3',4',6-pentachlorobiphenyl (1 10)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Surrogate Analytes
1 , 3 -dimethyl-2 -nitrobenzene
benzo [a] pyrene-^i 2
triphenyl phosphate
Fortified Cone.
0.25 jig/Lb
n=4
Mean %
Recovery
81.8
85.4
80.4
85.0
88.7
84.5
89.2
93.6
92.8
94.0
94.6
97.5
93.6
88.3
92.2
99.7
RSD
6.5
5.6
2.3
7.6
4.2
3.6
3.5
3.0
4.1
0.77
4.2
2.5
9.9
1.0
3.7
2.2
Fortified Cone.
2.0 jig/Lc
n=8
Mean %
Recovery
92.8
93.8
93.9
91.5
91.6
93.4
94.6
99.1
99.2
99.8
100
99.3
102
92.5
88.8
94.0
RSD
2.2
1.7
3.9
4.8
3.5
2.7
2.1
1.8
1.6
3.5
3.1
3.5
5.9
1.5
4.3
2.2
Fortified Cone.
5.0 ng/Ld
n=4
Mean %
Recovery
90.0
91.5
92.9
94.9
101
98.5
101
102
104
103
104
104
99.9
95.7
94.6
91.1
RSD
1.2
1.0
4.2
3.9
2.9
3.3
2.3
2.0
4.5
3.7
3.3
2.9
1.1
1.0
3.9
2.1
a. Data obtained on the instrumentation described in Sect. 13.1.1.1.
b. Exceptions to the stated concentration are as follows: Surrogate concentrations are 5.0 ug/L, pentachlorophenol
is 1.0 ug/L, tebuconazole is 1.2 ug/L, c-permethrin is 0.14 ug/L, t-permethrin is 0.36 ug/L, MGK 264(a) is 0.20
ug/L and MGK 264(b) is 0.05 ug/L.
c. Exceptions to the stated concentration are as follows: Surrogate concentrations are 5.0 ug/L, pentachlorophenol
is 8.0 ug/L, tebuconazole is 10.0 ug/L, c-permethrin is 1. lug/L, t-permethrin is 2.9ug/L, and MGK 264(a) is 1.6
ug/L and MGK 264(b) is 0.4 ug/L.
d. Exceptions to the stated concentration are as follows: Surrogate concentrations are 5.0 ug/L, pentachlorophenol
is 20.0 ug/L, tebuconazole is 25.0 ug/L, c-permethrin is 2.8 ug/L, t-permethrin is 7.2 ug/L, and MGK 264(a) is
4.0ug/L and MGK 264(b) is 1.0 ug/L.
e. ND = Not determined. Analyte could not be determined because of the low concentration.
525.3-82
-------
Table 6. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Water from Ground and Surface Water Sources, and Extracted Using
J.T. Baker Speedisk H2O Phobic DVB SPE Columns (Cartridges); N=4 for Each Matrix;
Full Scan GC/MS Analysesa
Analytes
acenaphthylene
acetochlor
alachlor
aldrin
ametryn
anthracene
atraton
atrazine
benzo [a] anthracene
benzo[a]pyrene
benzo[6]fluoranthene
benzo [g, h, /'Jperylene
benzo[&]fluoranthene
BHT
bromacil
butachlor
butylate
butylbenzylphthalate
chlordane, cis-
chlordane, trans
chlorfenvinphos
chlorobenzilate
chloroneb
chlorothalonil
chlorpropham
chlorpyrifos
chrysene
cyanazine
Fortified
Cone. (fig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Ground Water
Mean %
Recoveryd
84.8
106
108
90.6
92.2
97.7
94.2
97.3
101
105
101
121
106
96.4
104
103
100
116
99.5
92.6
101
106
84.4
97.2
89.7
104
105
108
RSD
1.5
2.2
3.4
4.0
6.5
3.2
2.7
2.4
2.6
4.8
3.1
2.4
3.5
1.6
2.2
3.1
1.6
3.9
2.4
2.8
2.6
3.9
1.0
1.8
3.3
6.4
3.2
1.2
Surface Water0
Mean %
Recoveryd
91.5
103
104
85.5
87.5
99.3
86.0
90.9
96.4
97.5
100
118
102
109
123
104
97.8
208
98.3
93.0
102
105
83.4
96.2
100
99.9
101
98.0
RSD
2.0
2.7
1.0
4.2
5.3
2.8
4.8
2.0
2.3
6.0
2.1
3.2
1.7
2.0
16
2.8
2.8
94
3.5
3.2
5.4
5.8
1.8
3.2
2.2
4.4
2.8
3.0
525.3-83
-------
Table 6. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Water from Ground and Surface Water Sources, and Extracted Using
J.T. Baker Speedisk H2O Phobic DVB SPE Columns (Cartridges); N=4 for Each Matrix;
Full Scan GC/MS Analysesa
Analytes
cycloate
dacthal (DCPA)
ODD, 4,4'-
DDE, 4,4'-
DDT, 4,4'-
DEET
di(2-ethylhexyl)adipate
di(2-ethylhexyl)phthalate
dibenzo[a,/z]anthracene
dibutyl phthalate
dichlorvos
diethylphthalate
dimethipin
dimethylphthalate
DIMP
dinitrotoluene, 2,4-
dinitrotoluene, 2,6-
diphenamid
disulfoton
endosulfan I
endosulfan II
endosulfan sulfate
endrin
EPTC
ethion
ethoprop
ethyl parathion
etridiazole
Fortified
Cone. (jig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Ground Water
Mean %
Recoveryd
97.0
96.0
97.5
94.4
109
101
99.7
106
116
122
82.3
94.3
49.2
92.7
91.2
78.9
102
109
81.4
97.8
98.9
101
105
92.6
106
97.2
87.4
100
RSD
1.9
4.0
3.4
1.8
3.6
2.9
3.8
1.7
3.8
3.7
3.2
3.5
11
1.4
2.3
3.8
4.8
3.9
2.4
5.1
3.0
4.8
5.7
2.9
3.3
0.57
4.1
3.4
Surface Water0
Mean %
Recoveryd
94.4
97.8
98.2
95.0
109
97.5
123
126
102
114
92.1
94.4
34.9
94.1
87.7
96.3
111
98.2
74.5
95.8
103
98.6
110
91.9
106
93.2
88.0
103
RSD
1.3
2.0
3.4
3.7
3.5
0.63
24
29
7.2
2.7
2.0
3.5
4.6
2.7
1.9
3.1
4.7
4.7
1.9
4.0
8.3
3.7
6.2
0.36
4.1
4.3
4.8
2.4
525.3-84
-------
Table 6. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Water from Ground and Surface Water Sources, and Extracted Using
J.T. Baker Speedisk H2O Phobic DVB SPE Columns (Cartridges); N=4 for Each Matrix;
Full Scan GC/MS Analysesa
Analytes
fenarimol
fluorene
fluridone
HCCPD
HCH, a
HCH, (3
HCH, 5
HCH, y (lindane)
heptachlor
heptachlor epoxide
hexachlorobenzene
hexazinone
indeno[l,2,3-c,
-------
Table 6. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Water from Ground and Surface Water Sources, and Extracted Using
J.T. Baker Speedisk H2O Phobic DVB SPE Columns (Cartridges); N=4 for Each Matrix;
Full Scan GC/MS Analysesa
Analytes
pentachlorophenol
permethrin, cis
permethrin, trans
phenanthrene
phorate
phosphamidon
profenofos
prometon
prometryn
pronamide
propachlor
propazine
pyrene
simazine
simetryn
tebuconazole
tebuthiuron
terbacil
terbutryn
tetrachlorvinphos
triadimefon
tribufos+merphos
trifluralin
vernolate
vinclozolin
PCB congeners (by IUPAC#)
2-chlorobiphenyl (1)
4-chlorobiphenyl (3)
Fortified
Cone. (fig/L)
8.0
1.1
2.9
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
10.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Ground Water
Mean %
Recoveryd
87.7
95.7
94.4
98.6
89.1
106
109
92.1
95.5
105
100
102
105
75.4
93.0
108
92.1
105
101
98.9
102
108
100
92.9
98.7
83.5
91.9
RSD
3.9
0.88
2.0
2.4
0.39
4.8
3.8
3.9
3.4
2.5
1.8
2.2
5.6
0.82
3.2
3.9
2.5
4.8
o o
J.J
2.7
3.7
4.0
2.6
0.68
2.7
1.0
2.6
Surface Water0
Mean %
Recoveryd
92.5
102
97.8
98.5
97.3
105
102
83.6
89.3
99.8
97.6
93.3
102
74.0
90.7
108
84.2
108
94.5
101
99.1
110
103
90.4
100
83.8
89.3
RSD
2.6
2.8
2.1
1.5
2.7
5.6
13
3.2
2.2
1.6
1.4
3.1
4.0
2.1
5.3
1.9
2.8
6.9
4.3
4.3
5.5
4.6
2.3
2.1
0.61
2.0
2.3
525.3-86
-------
Table 6. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Water from Ground and Surface Water Sources, and Extracted Using
J.T. Baker Speedisk H2O Phobic DVB SPE Columns (Cartridges); N=4 for Each Matrix;
Full Scan GC/MS Analysesa
Analytes
2,4'-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
2,2',3,5'-tetrachlorobiphenyl(44)
2,2',5,5'-tetrachlorobiphenyl(52)
2,3 ',4',5-tetrachloroobiphenyl (70)
2,3,3 ',4',6-pentachlorobiphenyl (1 10)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Surrogate Analytes
1 , 3 -dimethyl-2 -nitrobenzene
benzo [a] pyrene-c/i 2
triphenyl phosphate
Fortified
Cone. (jig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
5.0
5.0
5.0
Ground Water
Mean %
Recoveryd
85.1
89.5
91.6
96.9
93.5
95.6
93.5
92.0
93.4
97.9
97.0
89.1
83.3
94.0
104
RSD
1.8
3.9
2.6
3.6
1.9
2.6
1.6
2.5
2.7
1.2
o o
J.J
3.3
6.4
4.2
4.0
Surface Water0
Mean %
Recoveryd
87.4
90.9
88.9
96.2
93.5
96.1
92.2
94.9
93.5
101
97.2
99.0
91.4
90.5
107
RSD
1.8
2.8
2.0
2.0
2.4
2.3
3.1
3.5
4.6
2.2
2.5
4.9
0.40
2.6
1.9
a. Data obtained on the instrumentation described in Sect. 13.1.1.1.
b. Tap water from a ground water source with high mineral content. Tap water hardness was 342 mg/L as calcium
carbonate.
c. Tap water from a surface water source. TOC of 2.8 mg/L.
d. Recoveries have been corrected to reflect the native amount in the unfortified matrix water.
525.3-87
-------
Table 7. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using J.T. Baker Speedisk HiO Phobic DVB
SPE; Full Scan GC/MS Analyses"
Analytes
acenaphthylene
acetochlor
alachlor
aldrin
ametryn
anthracene
atraton
atrazine
benzo [a] anthracene
benzo[a]pyrene
benzo[6]fluoranthene
benzo \g, h, /'Jperylene
benzo[&]fluoranthene
BHT
bromacil
butachlor
butylate
butylbenzylphthalate
chlordane, cis
chlordane, trans
chlorfenvinphos
chlorobenzilate
chloroneb
chlorothalonil
chlorpropham
chlorpyrifos
chrysene
cyanazine
Fortified Cone.
0.25 jig/Lb
n=4
Mean %
Recovery
87.9
110
107
92.7
96.6
85.6
96.4
96.8
85.6
94.5
90.2
89.5
103
50.4
102
103
91.5
91.3
106
101
106
106
95.5
96.0
77.3
101
96.5
101
RSD
1.9
4.0
5.0
2.5
3.2
3.2
12
6.7
0.43
11
2.6
10
7.4
11
8.2
2.1
2.6
5.8
5.2
5.3
5.3
4.7
2.9
5.6
12
13
7.9
6.4
Fortified Cone.
2.0 jig/Lc
n=8
Mean %
Recovery
84.6
99.4
92.5
82.2
89.5
86.7
92.1
94.2
94.0
81.3
88.6
93.0
90.1
107
99.6
95.5
87.6
121
94.9
89.6
99.3
96.7
82.0
83.8
88.7
98.7
95.4
91.8
RSD
5.1
3.5
3.8
3.8
7.3
4.3
4.9
2.6
4.9
5.9
6.5
7.5
4.7
2.6
28
2.7
3.6
5.7
4.9
5.2
2.7
4.4
6.0
5.6
11
4.2
5.2
6.7
Fortified Cone.
5.0 ng/Ld
n=4
Mean %
Recovery
90.4
105
110
104
99.2
104
100
103
90.1
94.6
94.3
96.6
94.1
85.4
106
105
95.8
108
105
104
104
107
94.3
103
102
110
94.2
106
RSD
1.8
3.1
2.4
3.5
5.7
2.4
2.0
2.9
0.88
3.5
2.5
3.8
2.8
1.8
1.8
2.0
1.4
1.5
4.3
4.4
0.78
1.7
1.8
2.5
1.4
3.0
0.73
2.5
525.3-88
-------
Table 7. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using J.T. Baker Speedisk HiO Phobic DVB
SPE; Full Scan GC/MS Analyses"
Analytes
cycloate
dacthal (DCPA)
ODD, 4,4'-
DDE, 4,4'-
DDT, 4,4'-
DEET
di(2-ethylhexyl)adipate
di(2-ethylhexyl)phthalate
dibenzo[a,/z]anthracene
dibutylphthalate
dichlorvos
dieldrin
diethylphthalate
dimethipin
dimethylphthalate
DIMP
dinitrotoluene, 2,4-
dinitrotoluene, 2,6-
diphenamid
disulfoton
endosulfan I
endosulfan II
endosulfan sulfate
endrin
EPTC
ethion
ethoprop
ethyl parathion
Fortified Cone.
0.25 jig/Lb
n=4
Mean %
Recovery
94.0
93.2
95.8
95.2
98.2
98.7
96.1
NDe
101
99.1
109
106
90.8
83.7
93.3
101
77.5
NDf
105
80.0
109
99.6
96.6
110
93.8
98.4
108
90.6
RSD
3.4
8.3
1.2
4.9
4.0
4.8
7.8
14
32
5.0
7.8
5.5
17
6.7
2.5
3.3
4.4
5.5
2.6
4.2
7.5
8.6
5.7
7.0
4.2
14
Fortified Cone.
2.0 jig/Lc
n=8
Mean %
Recovery
89.1
89.8
94.5
89.2
86.5
89.4
105
104
90.9
110
100
95.9
87.7
76.1
87.2
84.6
87.4
97.3
95.4
80.4
92.3
96.8
90.0
120
85.0
98.7
95.9
90.0
RSD
2.4
3.5
3.5
3.2
6.5
6.0
8.3
9.3
10
3.5
9.5
3.9
4.8
5.5
5.8
7.2
16
14
4.9
10
5.6
3.7
5.7
8.4
5.7
2.8
7.7
9.6
Fortified Cone.
5.0 ng/Ld
n=4
Mean %
Recovery
98.8
101
102
106
104
99.3
97.6
94.4
106
107
102
109
98.8
64.6
96.2
97.0
99.8
92.2
108
96.7
107
110
103
107
94.8
101
103
104
RSD
1.7
1.9
2.2
3.4
3.0
0.64
0.91
3.7
3.1
2.9
2.3
4.6
1.0
4.1
1.2
0.36
3.5
1.1
1.9
2.7
2.4
2.3
2.0
2.5
0.59
1.1
2.8
2.3
525.3-89
-------
Table 7. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using J.T. Baker Speedisk HiO Phobic DVB
SPE; Full Scan GC/MS Analyses"
Analytes
etridiazole
fenarimol
fluorene
fluridone
HCCPD
HCH, a
HCH, (3
HCH, 5
HCH, y (lindane)
heptachlor
heptachlor epoxide
hexachlorobenzene
hexazinone
indeno[l,2,3-c,
-------
Table 7. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using J.T. Baker Speedisk HiO Phobic DVB
SPE; Full Scan GC/MS Analyses"
Analytes
pebulate
pentachlorophenol
permethrin, cis
permethrin, trans
phenanthrene
phorate
phosphamidon
profenofos
prometon
prometryn
pronamide
propachlor
propazine
pyrene
simazine
simetryn
tebuconazole
tebuthiuron
terbacil
terbutryn
tetrachlorvinphos
triadimefon
tribufos+merphos
trifluralin
vernolate
vinclozolin
PCB congeners (by IUPAC#)
2-chlorobiphenyl (1)
Fortified Cone.
0.25 jig/Lb
n=4
Mean %
Recovery
95.0
93.5
89.5
91.6
87.8
86.5
103
116
76.7
99.7
96.8
98.3
95.0
99.2
89.5
99.1
107
94.1
98.2
103
108
110
126
84.3
97.2
95.0
90.2
RSD
3.3
6.0
4.4
3.8
1.1
1.6
8.6
11
4.0
4.7
6.0
0.9
4.1
2.7
9.3
6.0
3.2
5.6
9.0
2.8
5.6
11
2.2
3.3
1.2
6.6
4.6
Fortified Cone.
2.0 jig/Lc
n=8
Mean %
Recovery
84.6
111
96.3
90.4
93.4
86.3
105
99.0
97.3
91.4
95.6
88.0
88.5
98.0
83.8
91.2
100
84.1
95.1
91.2
97.5
94.4
96.3
89.6
85.9
96.1
78.9
RSD
3.4
3.9
7.0
6.7
3.3
2.5
4.3
5.2
4.6
5.0
3.7
4.4
3.9
2.3
5.8
3.9
8.2
4.0
3.6
4.7
4.0
4.9
5.3
8.7
5.8
3.5
4.7
Fortified Cone.
5.0 ng/Ld
n=4
Mean %
Recovery
94.2
101
93.8
96.1
98.1
94.4
108
104
91.7
101
101
103
102
103
99.6
112
100
101
110
105
110
103
107
95.5
95.0
102
91.0
RSD
1.8
4.2
1.5
2.7
2.5
1.2
1.9
2.1
4.7
2.4
2.7
1.0
2.6
0.91
3.7
2.9
0.91
0.19
2.6
2.9
3.8
3.4
2.0
0.67
2.8
1.4
2.2
525.3-91
-------
Table 7. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using J.T. Baker Speedisk HiO Phobic DVB
SPE; Full Scan GC/MS Analyses"
Analytes
4-chlorobiphenyl (3)
2,4-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
2,2',3,5'-tetrachlorobiphenyl(44)
2,2',5,5'-tetrachlorobiphenyl(52)
2,3 ',4',5-tetrachloroobiphenyl (70)
2,3,3 ',4',6-pentachlorobiphenyl (1 10)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Surrogate Analytes
1 , 3 -dimethyl-2 -nitrobenzene
benzo [a] pyrene-c/i 2
triphenyl phosphate
Fortified Cone.
0.25 jig/Lb
n=4
Mean %
Recovery
87.9
85.3
90.7
93.2
97.5
89.0
102
98.0
96.0
93.7
96.4
98.3
87.2
98.0
101
103
RSD
6.5
5.6
2.3
7.6
4.2
3.6
3.5
3.0
4.1
0.8
4.2
2.5
9.9
1.0
3.7
2.2
Fortified Cone.
2.0 ug/Lc
n=8
Mean %
Recovery
80.5
78.6
85.9
90.0
89.5
95.0
89.6
89.1
90.3
90.9
92.4
90.0
88.4
95.5
82.1
110
RSD
5.8
5.5
4.7
6.7
3.9
3.1
3.8
2.7
3.5
o o
J.J
2.0
5.3
6.5
3.9
3.1
3.8
Fortified Cone.
5.0 ng/Ld
n=4
Mean %
Recovery
92.7
94.2
94.9
103
108
103
106
102
105
105
103
104
95.3
102
91.9
97.0
RSD
0.82
1.5
4.0
2.1
2.4
1.7
3.6
2.4
1.6
3.4
2.8
3.5
2.2
2.4
2.2
2.1
a. Data obtained on the instrumentation described in Sect. 13.1.1.1.
b. Exceptions to the stated concentration are as follows: Surrogate concentrations are 5.0 ug/L, pentachlorophenol
is 1.0 ug/L, tebuconazole is 1.2 ug/L, c-permethrin is 0.14 ug/L, t-permethrin is 0.36 ug/L, MGK 264(a) is 0.20
ug/L and MGK 264(b) is 0.05 ug/L.
c. Exceptions to the stated concentration are as follows: Surrogate concentrations are 5.0 ug/L, pentachlorophenol
is 8.0 ug/L, tebuconazole is 10.0 ug/L, c-permethrin is 1. lug/L, t-permethrin is 2.9ug/L, and MGK 264(a) is 1.6
ug/L and MGK 264(b) is 0.4 ug/L.
d. Exceptions to the stated concentration are as follows: Surrogate concentrations are 5.0 ug/L, pentachlorophenol
is 20.0 ug/L, tebuconazole is 25.0 ug/L, c-permethrin is 2.8 ug/L, t-permethrin is 7.2 ug/L, and MGK 264(a) is
4.0ug/L and MGK 264(b) is 1.0 ug/L.
e. ND = Not determined. Analyte could not be determined because of the low fortified concentration relative to
theLRB.
f. ND = Not determined. Analyte could not be determined due to poor instrument sensitivity at this concentration.
525.3-92
-------
Table 8. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Water from Ground and Surface Water Sources, and Extracted Using
J.T. Baker Speedisk H2O Phobic DVB SPE; N=4 for Each Matrix; Full Scan GC/MS
Analyses21
Analytes
acenaphthylene
acetochlor
alachlor
aldrin
ametryn
anthracene
atraton
atrazine
benzo [a] anthracene
benzo[a]pyrene
benzo[6]fluoranthene
benzo [g, h, /'Jperylene
benzo[&]fluoranthene
BHT
bromacil
butachlor
butylate
butylbenzylphthalate
chlordane, cis-
chlordane, trans
chlorfenvinphos
chlorobenzilate
chloroneb
chlorothalonil
chlorpropham
chlorpyrifos
chrysene
cyanazine
Fortified
Cone. (jig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Ground Water
Mean %
Recoveryd
98.8
123
116
102
113
103
114
119
93.6
80.2
89.5
90.7
88.6
121
99.1
114
104
115
118
114
116
123
95.8
102
100
123
95.0
121
RSD
2.4
4.2
5.8
3.1
2.0
3.2
4.3
5.9
2.6
4.5
2.8
3.5
2.3
3.6
2.6
o o
J.J
4.0
2.4
7.2
4.3
3.7
2.9
2.1
4.8
5.5
2.5
6.3
4.4
Surface Water0
Mean %
Recoveryd
87.5
101
91.6
80.5
82.7
88.6
83.0
93.0
95.2
85.6
88.8
92.9
87.8
109
115
99.1
92.0
95.9
93.1
85.1
95.9
95.2
82.9
82.8
99.3
88.4
93.9
84.4
RSD
1.1
4.4
3.8
4.3
2.0
3.9
6.4
4.8
2.1
11
6.1
5.0
3.4
0.46
4.4
5.6
4.6
4.4
6.0
4.4
7.4
5.5
2.5
5.0
1.1
3.3
2.9
6.2
525.3-93
-------
Table 8. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Water from Ground and Surface Water Sources, and Extracted Using
J.T. Baker Speedisk H2O Phobic DVB SPE; N=4 for Each Matrix; Full Scan GC/MS
Analyses21
Analytes
cycloate
dacthal (DCPA)
ODD, 4,4'-
DDE, 4,4'-
DDT, 4,4'-
DEET
di(2-ethylhexyl)adipate
di(2-ethylhexyl)phthalate
dibenzo[a,/z]anthracene
dibutyl phthalate
dichlorvos
dieldrin
diethylphthalate
dimethipin
dimethylphthalate
DIMP
dinitrotoluene, 2,4-
dinitrotoluene, 2,6-
diphenamid
disulfoton
endosulfan I
endosulfan II
endosulfan sulfate
endrin
EPTC
ethion
ethoprop
ethyl parathion
Fortified
Cone. (jig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Ground Water
Mean %
Recoveryd
105
116
119
113
112
106
112
113
90.4
132
116
126
103
98.6
103
111
87.9
110
121
91.9
121
117
112
103
100
112
112
95.4
RSD
3.2
4.2
3.4
4.1
3.5
1.9
6.4
7.4
3.8
4.2
4.2
4.0
3.8
7.0
4.1
4.7
3.7
7.9
5.1
4.8
1.7
6.1
5.1
8.8
3.1
1.4
2.3
5.7
Surface Water0
Mean %
Recoveryd
91.9
89.9
94.1
87.4
87.5
95.4
102
108
90.0
102
112
101
89.1
77.8
89.1
88.7
100
110
95.5
84.9
90.4
93.9
84.9
115
89.5
102
104
99.8
RSD
1.9
4.6
4.9
5.2
6.0
1.2
1.9
5.2
5.3
5.1
2.7
5.8
1.7
3.1
2.6
4.9
4.9
1.3
5.3
1.8
5.8
12
6.0
3.3
3.1
4.4
1.2
1.1
525.3-94
-------
Table 8. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Water from Ground and Surface Water Sources, and Extracted Using
J.T. Baker Speedisk H2O Phobic DVB SPE; N=4 for Each Matrix; Full Scan GC/MS
Analyses21
Analytes
etridiazole
fenarimol
fluorene
fluridone
HCCPD
HCH, a
HCH, (3
HCH, 5
HCH, y (lindane)
heptachlor
heptachlor epoxide
hexachlorobenzene
hexazinone
indeno[l,2,3-c,
-------
Table 8. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Water from Ground and Surface Water Sources, and Extracted Using
J.T. Baker Speedisk H2O Phobic DVB SPE; N=4 for Each Matrix; Full Scan GC/MS
Analyses21
Analytes
pebulate
pentachlorophenol
permethrin, cis
permethrin, trans
phenanthrene
phorate
phosphamidon
profenofos
prometon
prometryn
pronamide
propachlor
propazine
pyrene
simazine
simetryn
tebuconazole
tebuthiuron
terbacil
terbutryn
tetrachlorvinphos
triadimefon
tribufos+merphos
trifluralin
vernolate
vinclozolin
PCB congeners (by IUPAC#)
2-chlorobiphenyl (1)
Fortified
Cone. (jig/L)
2.0
8.0
1.1
2.9
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
10.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Ground Water
Mean %
Recoveryd
98.0
118
93.9
94.8
110
94.8
126
120
117
118
119
104
113
119
103
116
105
101
120
113
115
121
121
110
105
117
94.2
RSD
4.6
2.3
4.8
4.7
5.1
3.7
5.2
4.8
4.6
3.7
3.7
1.9
4.1
2.1
2.4
4.0
2.6
4.3
4.1
2.5
5.6
3.4
2.1
2.7
2.2
4.6
2.8
Surface Water0
Mean %
Recoveryd
84.4
110
93.4
92.7
92.2
89.1
97.6
97.7
82.6
86.2
94.6
94.2
85.2
96.8
81.6
88.3
97.8
81.9
101
85.9
95.8
93.9
102
94.8
91.0
96.1
81.3
RSD
1.7
3.8
4.8
2.5
4.0
2.4
3.9
8.0
3.5
4.9
4.4
1.3
3.2
4.3
6.7
6.5
4.2
3.7
4.7
3.6
6.0
5.4
6.1
2.7
1.1
5.1
2.0
525.3-96
-------
Table 8. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Water from Ground and Surface Water Sources, and Extracted Using
J.T. Baker Speedisk H2O Phobic DVB SPE; N=4 for Each Matrix; Full Scan GC/MS
Analyses21
Analytes
4-chlorobiphenyl (3)
2,4-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
2,2',3,5'-tetrachlorobiphenyl(44)
2,2',5,5'-tetrachlorobiphenyl(52)
2,3 ',4',5-tetrachloroobiphenyl (70)
2,3,3 ',4',6-pentachlorobiphenyl (1 10)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Surrogate Analytes
1 , 3 -dimethyl-2 -nitrobenzene
benzo [a] pyrene-^i 2
triphenyl phosphate
Fortified
Cone. (jig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
5.0
5.0
5.0
Ground Water
Mean %
Recoveryd
92.9
93.2
109
118
112
121
114
113
113
116
119
112
90.9
111
79.8
115
RSD
1.3
1.9
4.7
8.4
3.2
2.4
4.2
3.7
3.1
3.6
3.1
5.2
7.7
o o
J.J
3.4
3.7
Surface Water0
Mean %
Recoveryd
85.3
80.4
86.4
88.3
89.1
95.4
91.4
88.3
89.2
88.3
93.8
88.4
83.8
102
86.0
115
RSD
1.9
1.2
4.9
4.4
6.3
5.3
6.2
4.5
5.9
6.8
4.1
5.3
3.4
1.5
2.8
2.3
a. Data obtained on the instrumentation described in Sect. 13.1.1.1.
b. Tap water from a ground water source with high mineral content. Tap water hardness was 342 mg/L as calcium
carbonate.
c. Tap water from a surface water source. TOC of 2.8 mg/L.
d. Recoveries have been corrected to reflect the native amount in the unfortified matrix water.
525.3-97
-------
Table 9. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using Empore SDB-XC Disks; N=4 for Each
Concentration; Full Scan GC/MS Analyses'1
Analytes
acenaphthylene
acetochlor
alachlor
aldrin
ametryn
anthracene
atraton
atrazine
benzo [a] anthracene
benzo[a]pyrene
benzo[6]fluoranthene
benzo \g, h, /'Jperylene
benzo [k] fluoranthene
BHT
bromacil
butachlor
butylate
butylbenzylphthalate
chlordane, cis
chlordane, trans
chlorfenvinphos
chlorobenzilate
chloroneb
chlorothalonil
chlorpropham
chlorpyrifos
chrysene
cyanazine
cycloate
Fortified Cone.
0.20 jig/Lb
Mean %
Recovery
90.0
106
98.8
91.3
106
98.8
109
105
95.0
96.3
106
108
111
97.5
124
115
100
131
96.3
96.3
123
105
283
98.8
113
96.3
72.5
101
90.0
RSD
4.5
4.5
6.4
5.2
5.9
4.8
4.4
3.9
4.3
7.8
5.9
6.0
4.3
8.9
2.0
3.5
4.1
6.5
5.0
5.0
2.4
3.9
10
2.5
5.7
5.0
12
4.7
4.5
Fortified Cone.
2.0 jig/Lc
Mean %
Recovery
87.9
94.5
92.0
80.5
90.8
91.1
90.2
91.1
91.6
88.0
90.6
87.0
89.4
81.0
90.2
92.1
88.6
94.1
90.7
90.8
92.4
92.9
101
88.6
90.5
93.3
89.2
88.8
90.1
RSD
2.6
2.6
1.9
3.1
4.6
2.3
2.3
3.5
1.9
3.5
1.5
5.4
1.6
4.4
3.5
3.7
3.6
o o
J.J
2.9
3.0
3.5
3.7
4.1
2.8
3.0
3.1
5.7
5.8
0.99
Fortified Cone.
5.0 ng/Ld
Mean %
Recovery
86.4
90.0
92.3
86.6
94.3
89.4
91.8
91.6
91.0
88.9
91.9
89.4
89.4
81.7
96.4
93.2
87.1
96.3
88.8
89.3
95.9
92.9
96.6
88.4
90.2
89.6
89.4
90.5
91.6
RSD
5.4
7.6
8.2
7.1
9.2
5.7
7.3
8.0
5.1
5.9
6.2
6.9
5.6
7.0
7.2
8.0
6.9
7.4
7.9
7.3
7.0
8.4
7.1
7.3
6.7
7.3
5.2
9.0
7.1
525.3-98
-------
Table 9. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using Empore SDB-XC Disks; N=4 for Each
Concentration; Full Scan GC/MS Analyses'1
Analytes
dacthal (DCPA)
ODD, 4,4'-
DDE, 4,4'-
DDT, 4,4'-
DEET
di(2-ethylhexyl)adipate
di(2-ethylhexyl)phthalate
dibenzo[a,/z]anthracene
dibutyl phthalate
dichlorvos
dieldrin
diethylphthalate
dimethipin
dimethylphthalate
DIMP
dinitrotoluene, 2,4-
dinitrotoluene, 2,6-
diphenamid
disulfoton
endosulfan I
endosulfan II
endosulfan sulfate
endrin
EPTC
ethion
ethoprop
ethyl parathion
etridiazole
fenarimol
Fortified Cone.
0.20 jig/Lb
Mean %
Recovery
95.0
92.5
98.8
113
103
129
160
104
741
101
103
97.5
23.8
90.0
103
116
108
111
98.8
77.5
83.8
104
111
100
120
114
121
110
123
RSD
4.3
3.1
6.4
4.4
4.9
4.9
5.1
4.6
9.8
4.7
4.9
6.6
11
4.5
6.3
5.4
6.0
4.3
4.8
3.7
5.7
4.6
5.7
4.1
3.4
2.2
3.9
3.7
5.3
Fortified Cone.
2.0 jig/Lc
Mean %
Recovery
92.7
93.3
90.8
87.8
92.7
90.9
98.9
90.7
105
86.6
91.0
90.7
8.52
90.2
64.0
90.5
88.9
93.3
87.1
92.8
93.5
90.9
94.5
89.0
94.2
94.0
91.2
90.2
93.0
RSD
2.7
2.7
2.8
2.7
2.9
3.4
2.7
4.2
2.9
o o
J.J
3.0
3.0
9.0
3.2
3.5
2.2
o o
J.J
2.9
4.1
2.9
3.7
o o
5.5
1.8
3.1
3.1
2.5
3.0
1.7
4.9
Fortified Cone.
5.0 ng/Ld
Mean %
Recovery
89.6
88.7
90.5
92.5
90.1
96.4
102
90.2
125
88.6
90.4
88.6
6.7
87.0
67.8
90.4
90.1
92.2
85.4
89.5
91.0
90.0
93.4
88.2
93.7
92.3
93.1
87.1
95.7
RSD
7.5
7.9
7.2
7.9
7.2
9.0
8.5
7.9
7.5
6.5
7.7
7.3
11
7.4
6.1
6.7
6.7
7.3
7.2
8.1
7.3
8.1
7.0
6.8
8.1
6.5
7.8
7.1
7.3
525.3-99
-------
Table 9. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using Empore SDB-XC Disks; N=4 for Each
Concentration; Full Scan GC/MS Analyses'1
Analytes
fluorene
fluridone
HCCPD
HCH, a
HCH, (3
HCH, 5
HCH, y (lindane)
heptachlor
heptachlor epoxide
hexachlorobenzene
hexazinone
indeno[l,2,3-c,
-------
Table 9. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using Empore SDB-XC Disks; N=4 for Each
Concentration; Full Scan GC/MS Analyses'1
Analytes
permethrin, trans
phenanthrene
phorate
phosphamidon
profenofos
prometon
prometryn
pronamide
propachlor
propazine
pyrene
simazine
simetryn
tebuconazole
tebuthiuron
terbacil
terbutryn
tetrachlorvinphos
triadimefon
tribufos+merphos
trifluralin
vernolate
vinclozolin
PCB congeners (by IUPAC#)
2-chlorobiphenyl (1)
4-chlorobiphenyl (3)
2,4'-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
Fortified Cone.
0.20 jig/Lb
Mean %
Recovery
107
95.0
121
126
125
111
111
118
96.3
103
98.8
108
119
126
116
120
111
125
105
116
109
100
105
85.0
90.0
88.8
82.5
91.3
RSD
4.1
4.3
3.9
3.8
3.3
5.7
4.3
5.5
5.0
6.3
4.8
2.7
5.3
2.0
7.3
3.4
4.3
3.3
8.7
3.7
2.3
4.1
3.9
4.8
4.5
7.1
6.1
6.9
Fortified Cone.
2.0 jig/Lc
Mean %
Recovery
92.8
92.2
88.2
94.7
93.4
91.4
92.3
94.4
91.2
91.5
92.5
90.7
93.6
89.5
94.0
92.3
93.0
92.1
93.9
93.6
88.1
90.0
89.3
88.4
89.2
88.8
90.3
90.4
RSD
2.8
2.1
2.1
3.8
2.5
3.1
o o
J.J
3.6
2.7
3.1
2.1
o o
J.J
3.1
1.5
4.4
3.4
2.7
3.4
2.4
2.8
2.6
2.9
3.4
2.9
2.6
2.0
3.1
2.3
Fortified Cone.
5.0 ng/Ld
Mean %
Recovery
91.8
90.0
85.7
99.7
94.9
93.5
92.0
93.9
87.7
91.4
91.0
91.0
93.6
95.6
100
95.2
93.1
97.4
94.5
100
86.5
87.2
89.8
84.8
85.6
86.1
88.3
89.4
RSD
7.5
5.9
7.5
6.1
7.3
7.7
8.1
7.6
7.0
7.5
6.0
7.9
7.9
9.9
5.0
7.8
7.9
7.2
7.6
7.3
7.4
6.9
7.7
6.2
6.1
6.5
6.8
6.7
525.3-101
-------
Table 9. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using Empore SDB-XC Disks; N=4 for Each
Concentration; Full Scan GC/MS Analyses'1
Analytes
2,2',3,5'-tetrachlorobiphenyl(44)
2,2',5,5'-tetrachlorobiphenyl(52)
2,3 ',4',5-tetrachloroobiphenyl (70)
2,3,3',4',6-pentachlorobiphenyl (1 10)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Surrogate Analytes
1 , 3 -dimethyl-2 -nitrobenzene
benzo [a] pyrene-^i 2
triphenyl phosphate
Fortified Cone.
0.20 jig/Lb
Mean %
Recovery
91.3
95.0
91.3
93.8
97.5
90.0
93.8
95.0
88.8
93.8
79.6
86.4
RSD
6.9
4.3
6.9
6.7
6.6
4.5
5.1
4.3
5.4
3.6
3.8
5.2
Fortified Cone.
2.0 ug/Lc
Mean %
Recovery
91.1
90.6
91.1
90.6
91.2
91.3
91.1
91.2
92.5
93.3
90.2
102
RSD
3.1
2.9
2.9
2.4
2.3
3.1
3.0
1.7
1.9
3.5
2.0
4.2
Fortified Cone.
5.0 ng/Ld
Mean %
Recovery
89.9
89.6
90.5
91.1
91.4
91.1
91.5
91.6
90.9
87.9
91.2
94.9
RSD
7.6
6.6
7.0
6.5
6.7
7.6
7.0
7.6
5.2
7.1
4.2
7.3
a. Data obtained on the instrumentation described in Sect. 13.1.1.2.
b. Exceptions to the stated concentration are as follows: Surrogate concentrations are 5.0 ug/L, pentachlorophenol
is 0.80 ug/L, MGK 246(a) is 0.067 ug/L, MGK 246(b) is 0.13 ug/L, tribufos+merphos is 0.40 ug/L,
c-permethrin is 0.12 ug/L, and t-permethrin is 0.29 ug/L.
c. Exceptions to the stated concentration are as follows: Surrogate concentrations are 5.0 ug/L, pentachlorophenol
is 8.0 ug/L, MGK 246(a) is 0.67 ug/L, MGK 246(b) is 1.3 ug/L, tribufos+merphos is 4.0 ug/L, c-permethrin is
1.2 ug/L, and t-permethrin is 2.9 ug/L.
d. Exceptions to the stated concentration are as follows: Surrogate concentrations are 5.0 ug/L, pentachlorophenol
is 20 ug/L, MGK 246(a) is 1.7 ug/L, MGK 246(b) is 3.3 ug/L, tribufos+merphos is 10 ug/L, c-permethrin is
2.9 ug/L, and t-permethrin is 7.2 ug/L.
525.3-102
-------
Table 10. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
Empore SDB-XC Disks; N=4 for Each Matrix; Full Scan GC/MS Analyses21
Analytes
acenaphthylene
acetochlor
alachlor
aldrin
ametryn
anthracene
atraton
atrazine
benzo [a] anthracene
benzo[a]pyrene
benzo[6]fluoranthene
benzo \g, h, /Jperylene
benzo [k] fluoranthene
BHT
bromacil
butachlor
butylate
butylbenzylphthalate
chlordane, cis-
chlordane, trans
chlorfenvinphos
chlorobenzilate
chloroneb
chlorothalonil
chlorpropham
chlorpyrifos
chrysene
cyanazine
cycloate
Fortified
Cone. (jig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Ground Waterb
Mean %
Recoveryd
94.1
95.6
98.1
87.0
101
96.0
100
99.1
105
95.1
96.0
97.3
124
91.3
100
98.3
96.4
99.1
94.9
94.0
102
100
94.8
95.8
97.4
97.0
84.8
101
99.0
RSD
2.4
2.2
o o
J.J
1.8
2.2
2.9
3.8
3.1
2.4
3.4
2.6
4.2
3.5
3.7
3.5
2.5
3.0
3.1
2.3
2.6
3.5
3.2
1.9
3.0
2.8
2.9
2.8
2.3
3.6
Surface Water0
Mean %
Recoveryd
87.4
92.0
92.4
84.9
92.0
90.3
93.9
91.4
99.8
91.5
92.9
97.9
118
87.5
96.8
94.3
90.5
95.6
89.6
89.8
96.8
96.3
95.6
91.8
91.9
90.0
79.5
79.4
93.0
RSD
7.8
7.1
7.2
6.4
9.2
8.2
7.5
7.1
8.4
9.8
9.9
10
8.2
7.3
6.3
6.9
7.8
9.4
6.7
6.3
8.0
9.3
7.7
6.4
7.5
6.9
9.3
4.9
7.1
525.3-103
-------
Table 10. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
Empore SDB-XC Disks; N=4 for Each Matrix; Full Scan GC/MS Analyses21
Analytes
dacthal (DCPA)
ODD, 4,4'-
DDE, 4,4'-
DDT, 4,4'-
DEET
di(2-ethylhexyl)adipate
di(2-ethylhexyl)phthalate
dibenzo[a,/z]anthracene
dibutyl phthalate
dichlorvos
dieldrin
diethylphthalate
dimethipin
dimethylphthalate
DIMP
dinitrotoluene, 2,4-
dinitrotoluene, 2,6-
diphenamid
disulfoton
endosulfan I
endosulfan II
endosulfan sulfate
endrin
EPTC
ethion
ethoprop
ethyl parathion
etridiazole
fenarimol
Fortified
Cone. Qig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Ground Waterb
Mean %
Recoveryd
95.4
92.8
94.9
102
97.9
97.0
109
100
106
96.8
96.8
96.1
9.0
94.5
87.3
97.5
96.1
100
91.6
95.0
93.5
96.4
104
97.3
98.3
103
96.8
99.9
106
RSD
3.2
3.1
2.7
3.6
2.7
3.1
2.9
3.3
3.0
2.6
3.2
2.6
24
3.1
3.1
2.7
2.3
3.4
2.5
3.7
2.9
4.5
o o
J.J
2.5
3.6
1.1
3.7
2.7
2.4
Surface Water0
Mean %
Recoveryd
89.4
86.5
90.0
102
92.9
93.3
104
102
96.8
90.9
92.6
89.9
8.50
88.1
76.6
93.3
90.6
94.6
81.5
90.4
88.4
91.4
101
90.6
95.6
98.9
92.9
95.8
103
RSD
7.1
7.0
6.4
7.8
7.3
10
6.3
11
7.4
7.1
6.5
8.5
25
7.9
6.5
7.6
8.0
7.2
7.2
6.3
7.5
8.1
8.0
7.6
8.1
9.5
8.4
7.4
9.4
525.3-104
-------
Table 10. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
Empore SDB-XC Disks; N=4 for Each Matrix; Full Scan GC/MS Analyses21
Analytes
fluorene
fluridone
HCCPD
HCH, a
HCH, (3
HCH, 5
HCH, y (lindane)
heptachlor
heptachlor epoxide
hexachlorobenzene
hexazinone
indeno[l,2,3-c,
-------
Table 10. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
Empore SDB-XC Disks; N=4 for Each Matrix; Full Scan GC/MS Analyses21
Analytes
permethrin, trans
phenanthrene
phorate
phosphamidon
profenofos
prometon
prometryn
pronamide
propachlor
propazine
pyrene
simazine
simetryn
tebuconazole
tebuthiuron
terbacil
terbutryn
tetrachlorvinphos
triadimefon
tribufos+merphos
trifluralin
vernolate
vinclozolin
PCB congeners (by IUPAC#)
2-chlorobiphenyl (1)
4-chlorobiphenyl (3)
2,4'-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
Fortified
Cone. (jig/L)
2.9
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
4.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Ground Waterb
Mean %
Recoveryd
101
93.0
96.0
105
100
99.3
102
101
96.4
98.4
95.5
98.5
99.8
110
105
104
101
105
102
95.9
95.0
95.9
93.0
93.3
93.1
93.3
94.8
94.6
RSD
2.9
2.7
2.8
3.7
2.7
3.1
3.2
3.0
3.0
2.8
2.9
o o
J.J
3.4
4.5
3.9
2.2
2.7
3.6
3.7
3.2
3.5
3.1
3.1
2.9
2.4
2.9
3.1
3.4
Surface Water0
Mean %
Recoveryd
96.9
87.5
90.9
101
96.3
92.6
90.8
95.9
91.1
91.4
91.0
91.0
92.6
112
96.1
99.4
95.3
100
96.6
91.4
90.5
89.5
88.4
86.1
86.5
87.0
87.3
88.6
RSD
9.1
7.8
7.0
7.3
8.5
7.5
7.3
6.9
8.0
7.1
7.8
6.3
6.7
9.8
9.3
5.9
7.5
7.0
7.2
7.0
7.9
7.6
6.6
8.0
8.0
8.4
8.7
7.3
525.3-106
-------
Table 10. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
Empore SDB-XC Disks; N=4 for Each Matrix; Full Scan GC/MS Analyses21
Analytes
2,2',3,5'-tetrachlorobiphenyl(44)
2,2',5,5'-tetrachlorobiphenyl(52)
2,3 ',4',5-tetrachloroobiphenyl (70)
2,3,3',4',6-pentachlorobiphenyl (1 10)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Surrogate Analytes
1 , 3 -dimethyl-2 -nitrobenzene
benzo [a] pyrene-c/i 2
triphenyl phosphate
Fortified
Cone. (jig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
5.0
5.0
5.0
Ground Waterb
Mean %
Recoveryd
94.5
94.3
95.5
94.9
95.0
94.3
95.1
94.1
97.3
96.6
95.0
100
RSD
2.6
3.0
2.7
2.8
2.7
2.9
2.8
2.9
2.7
2.7
4.0
2.7
Surface Water0
Mean %
Recoveryd
89.0
88.8
89.6
88.8
89.3
89.0
89.6
90.5
90.6
89.2
91.0
91.2
RSD
7.6
7.1
8.1
7.7
8.1
8.0
7.1
8.7
8.0
7.8
11
8.4
a. Data obtained on the instrumentation described in Sect. 13.1.1.2.
b. Tap water from a ground water source with high mineral content. Tap water hardness was 334 mg/L as calcium
carbonate.
c. Tap water from a surface water source. TOC of 2.8 mg/L.
d. Recoveries have been corrected to reflect the native amount in the unfortified matrix water.
525.3-107
-------
Table 11. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using UCT 525 Universal Cartridges; N=4
for Each Concentration; Full Scan GC/MS Analyses21
Analytes
acenaphthylene
acetochlor
alachlor
aldrin
ametryn
anthracene
atraton
atrazine
benzo [a] anthracene
benzo[a]pyrene
benzo[6]fluoranthene
benzo \g, h, /'Jperylene
benzo [k] fluoranthene
BHT
bromacil
butachlor
butylate
butylbenzylphthalate
chlordane, cis
chlordane, trans
chlorfenvinphos
chlorobenzilate
chloroneb
chlorothalonil
chlorpropham
chlorpyrifos
chrysene
cyanazine
cycloate
Fortified Cone.
0.25 jig/Lb
Mean %
Recovery
101
99.0
100
77.0
105
106
112
111
112
109
119
112
105
NDe
102
107
85.0
122
98.0
103
113
82.0
93.0
116
109
102
117
99.0
102
RSD
2.0
3.9
7.3
5.0
4.8
3.8
2.9
3.5
5.1
5.5
5.0
2.9
1.9
9.3
3.6
7.1
1.9
5.3
1.9
1.8
9.3
2.2
2.8
3.5
5.1
1.7
3.9
3.9
Fortified Cone.
2.0 jig/Lc
Mean %
Recovery
93.6
93.6
89.8
78.4
93.1
92.3
90.3
96.1
99.1
103
102
102
103
ND
98.9
86.3
83.0
95.9
102
103
110
99.8
92.0
106
93.1
93.4
97.1
88.1
87.4
RSD
0.51
2.1
0.72
2.9
1.3
1.0
4.1
3.2
3.8
1.7
1.2
4.3
2.4
0.86
1.1
2.2
3.7
2.5
2.3
2.5
5.1
2.9
3.8
2.5
3.3
1.7
4.9
1.0
Fortified Cone.
5.0 ng/Ld
Mean %
Recovery
99.8
104
92.8
85.0
95.8
104
96.8
97.3
112
111
114
113
113
ND
103
99.4
84.0
114
101
96.6
111
94.1
100
105
98.6
97.2
114
106
88.8
RSD
0.88
2.1
1.0
3.4
1.1
0.71
2.2
1.5
3.6
1.2
2.4
2.8
3.1
2.1
1.4
3.0
3.6
1.3
0.71
3.9
1.3
1.4
1.5
1.1
2.5
2.1
2.4
1.2
525.3-108
-------
Table 11. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using UCT 525 Universal Cartridges; N=4
for Each Concentration; Full Scan GC/MS Analyses21
Analytes
dacthal (DCPA)
ODD, 4,4'-
DDE, 4,4'-
DDT, 4,4'-
DEET
di(2-ethylhexyl)adipate
di(2-ethylhexyl)phthalate
dibenzo[a,/z]anthracene
dibutyl phthalate
dichlorvos
dieldrin
diethylphthalate
dimethipin
dimethylphthalate
DIMP
dinitrotoluene, 2,4-
dinitrotoluene, 2,6-
diphenamid
disulfoton
endosulfan I
endosulfan II
endosulfan sulfate
endrin
EPTC
ethion
ethoprop
ethyl parathion
etridiazole
fenarimol
Fortified Cone.
0.25 jig/Lb
Mean %
Recovery
105
107
99.0
116
103
112
137
110
115
104
103
111
24.0
110
112
126
121
106
79.0
95.0
103
112
89.0
89.0
106
110
117
118
110
RSD
3.6
3.6
3.9
2.8
1.9
4.1
3.7
3.6
3.3
3.1
1.9
1.8
14
3.6
5.8
1.8
1.7
2.2
2.5
5.3
1.9
7.1
5.7
2.2
2.2
2.1
4.3
3.4
4.7
Fortified Cone.
2.0 jig/Lc
Mean %
Recovery
102
85.8
82.3
87.6
98.3
96.6
97.6
95.4
101
91.6
87.4
111
29.5
113
90.0
105
106
95.1
91.5
88.4
89.6
96.5
82.9
88.0
100
91.3
97.6
90.6
87.1
RSD
3.5
0.75
1.3
2.8
3.2
3.1
1.3
2.5
1.5
1.7
0.55
2.3
6.5
0.25
1.9
2.6
0.71
0.90
8.9
1.3
3.5
2.4
3.4
0.80
2.7
1.6
2.3
2.2
2.0
Fortified Cone.
5.0 ng/Ld
Mean %
Recovery
101
105
101
112
104
111
110
109
114
88.8
98.1
114
24.9
113
93.7
113
111
97.8
85.3
101
103
106
91.3
85.8
108
96.2
105
101
91.7
RSD
1.7
1.4
1.0
0.83
2.0
1.8
2.4
1.5
2.6
2.7
0.39
1.4
2.5
0.78
3.0
2.5
0.67
0.69
1.5
1.0
1.0
0.75
4.0
0.60
3.1
1.4
3.5
1.5
3.4
525.3-109
-------
Table 11. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using UCT 525 Universal Cartridges; N=4
for Each Concentration; Full Scan GC/MS Analyses21
Analytes
fluorene
fluridone
HCCPD
HCH, a
HCH, (3
HCH, 5
HCH, y (lindane)
heptachlor
heptachlor epoxide
hexachlorobenzene
hexazinone
indeno[l,2,3-c,
-------
Table 11. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using UCT 525 Universal Cartridges; N=4
for Each Concentration; Full Scan GC/MS Analyses21
Analytes
permethrin, trans
phenanthrene
phorate
phosphamidon
profenofos
prometon
prometryn
pronamide
propachlor
propazine
pyrene
simazine
simetryn
tebuconazole
tebuthiuron
terbacil
terbutryn
tetrachlorvinphos
triadimefon
tribufos+merphos
trifluralin
vernolate
vinclozolin
PCB congeners (by IUPAC#)
2-chlorobiphenyl (1)
4-chlorobiphenyl (3)
2,4'-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
Fortified Cone.
0.25 jig/Lb
Mean %
Recovery
115
94.0
94.0
88.0
105
129
119
106
129
85.0
104
110
115
94.0
94.0
88.0
105
129
119
106
129
85.0
104
75.0
85.0
85.0
104
81.0
RSD
3.3
2.5
2.5
3.7
3.6
3.0
3.2
2.2
1.6
8.0
4.1
3.6
3.3
2.5
2.5
3.7
3.6
3.0
3.2
2.2
1.6
8.0
4.1
2.7
2.4
2.4
3.1
2.5
Fortified Cone.
2.0 jig/Lc
Mean %
Recovery
96.1
75.5
82.8
89.4
89.9
106
103
91.9
93.9
84.5
100
107
96.1
75.5
82.8
89.4
89.9
106
103
91.9
93.9
84.5
100
81.0
84.4
82.5
89.3
88.6
RSD
3.1
1.9
0.35
1.2
2.4
2.7
2.3
1.6
2.9
1.7
1.3
1.3
3.1
1.9
0.35
1.2
2.4
2.7
2.3
1.6
2.9
1.7
1.3
2.6
2.8
2.2
2.9
3.3
Fortified Cone.
5.0 ng/Ld
Mean %
Recovery
97.0
88.3
92.3
88.9
99.2
113
96.2
102
111
84.7
96.0
107
97.0
88.3
92.3
88.9
99.2
113
96.2
102
111
84.7
96.0
85.0
88.9
87.1
95.3
92.4
RSD
1.5
4.1
0.80
2.1
1.5
3.9
1.0
1.6
3.5
2.4
3.6
2.2
1.5
4.1
0.80
2.1
1.5
3.9
1.0
1.6
3.5
2.4
3.6
1.1
1.5
0.51
4.0
0.48
525.3-111
-------
Table 11. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using UCT 525 Universal Cartridges; N=4
for Each Concentration; Full Scan GC/MS Analyses21
Analytes
2,2',3,5'-tetrachlorobiphenyl(44)
2,2',5,5'-tetrachlorobiphenyl(52)
2,3 ',4',5-tetrachloroobiphenyl (70)
2,3,3',4',6-pentachlorobiphenyl (1 10)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Surrogate Analytes
1 , 3 -dimethyl-2 -nitrobenzene
benzo [a] pyrene-^i 2
triphenyl phosphate
Fortified Cone.
0.25 jig/Lb
Mean %
Recovery
85.0
84.0
84.0
81.0
90.0
86.0
87.0
79.0
101
92.9
112
107
RSD
9.7
3.9
3.9
2.5
2.6
4.7
5.8
2.5
2.0
4.0
2.1
2.5
Fortified Cone.
2.0 ug/Lc
Mean %
Recovery
91.1
90.3
92.4
94.3
94.5
99.0
96.5
96.9
93.1
98.9
101
97.9
RSD
3.1
4.4
3.4
3.2
3.7
3.2
4.3
2.8
2.9
3.1
2.6
4.1
Fortified Cone.
5.0 ng/Ld
Mean %
Recovery
93.4
96.4
97.0
97.1
98.8
105
101
101
91.6
88.8
101
104
RSD
1.6
1.1
0.94
0.90
1.1
1.3
1.2
1.1
2.2
4.0
4.9
3.2
a. Data obtained on the instrumentation described in Sect. 13.1.1.4.
b. Exceptions to the stated concentration are as follows: Surrogate concentrations are 5.0 ug/L, pentachlorophenol
is 1.0 ug/L, c-permethrin is 0.13 ug/L, t-permethrin is 0.38 ug/L, MGK 264 (a) is 0.085 ug/L and MGK 264 (b)
is 0.17 ug/L.
c. Exceptions to the stated concentration are as follows: Surrogate concentrations are 5.0 ug/L, pentachlorophenol
is 8.0 ug/L, c-permethrin is 1.0 ug/L, t-permethrin is 3.0 ug/L, MGK 264 (a) is 0.67 ug/L and MGK 264 (b) is
1.3 ug/L.
d. Exceptions to the stated concentration are as follows: Surrogate concentrations are 5.0 ug/L, pentachlorophenol
is 20.0 ug/L, c-permethrin is 2.5 ug/L, and t-permethrin is 7.5 ug/L, MGK 264 (a) is 1.7 ug/L and MGK 264 (b)
is 3.3 ug/L.
e. ND = Not determined. Analyte could not be determined because of the low fortified concentration relative to the
LRB.
525.3-112
-------
Table 12. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
UCT 525 Universal Cartridges; N=4 for Each Matrix; Full Scan GC/MS Analyses'1
Analytes
acenaphthylene
acetochlor
alachlor
aldrin
ametryn
anthracene
atraton
atrazine
benzo [a] anthracene
benzo[a]pyrene
benzo[6]fluoranthene
benzo \g, h, /Jperylene
benzo [k] fluoranthene
BHT
bromacil
butachlor
butylate
butylbenzylphthalate
chlordane, cis-
chlordane, trans
chlorfenvinphos
chlorobenzilate
chloroneb
chlorothalonil
chlorpropham
chlorpyrifos
chrysene
cyanazine
cycloate
Fortified
Cone. (jig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Ground Waterb
Mean %
Recoveryd
99.3
97.4
93.5
94.9
98.9
102
92.6
100
104
106
104
101
103
95.5
98.9
96.4
87.6
107
96.1
94.5
93.1
101
104
108
95.9
97.8
106
97.4
92.3
RSD
5.7
5.5
3.5
4.0
5.7
4.7
5.9
4.6
1.5
3.2
3.3
3.9
3.0
1.2
5.5
2.9
3.2
4.1
6.2
5.9
3.9
5.6
2.0
1.5
5.6
5.3
2.2
5.2
5.6
Surface Water0
Mean %
Recoveryd
95.1
106
95.0
81.1
93.4
101
87.3
95.6
102
100
100
101
101
114
104
95.6
83.6
107
98.0
98.3
111
97.1
108
110
98.1
103
100
91.0
95.1
RSD
1.8
4.9
3.3
0.59
6.2
1.6
5.3
1.5
2.4
2.7
3.9
5.3
2.6
1.9
4.6
3.3
1.8
2.9
5.9
7.3
3.4
4.3
4.0
2.2
2.4
4.1
3.2
11
1.6
525.3-113
-------
Table 12. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
UCT 525 Universal Cartridges; N=4 for Each Matrix; Full Scan GC/MS Analyses'1
Analytes
dacthal (DCPA)
ODD, 4,4'-
DDE, 4,4'-
DDT, 4,4'-
DEET
di(2-ethylhexyl)adipate
di(2-ethylhexyl)phthalate
dibenzo[a,/z]anthracene
dibutyl phthalate
dichlorvos
dieldrin
diethylphthalate
dimethipin
dimethylphthalate
DIMP
dinitrotoluene, 2,4-
dinitrotoluene, 2,6-
diphenamid
disulfoton
endosulfan I
endosulfan II
endosulfan sulfate
endrin
EPTC
ethion
ethoprop
ethyl parathion
etridiazole
fenarimol
Fortified
Cone. Qig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Ground Waterb
Mean %
Recoveryd
92.1
93.1
90.0
91.4
101
102
107
106
110
90.4
96.0
110
29.4
111
89.6
95.6
95.6
98.5
79.6
96.9
98.5
102
97.9
89.0
95.8
94.9
97.6
104
93.5
RSD
7.3
3.7
3.6
3.7
1.8
5.8
2.7
6.2
3.7
7.3
5.4
2.5
8.7
2.4
5.9
7.0
6.2
5.6
5.9
7.0
5.7
2.8
2.6
7.2
6.9
5.7
5.9
2.4
4.4
Surface Water0
Mean %
Recoveryd
107
91.0
85.6
90.4
109
106
104
102
107
88.8
96.3
107
38.1
111
99.6
105
101
101
103
93.0
94.3
100
88.1
85.8
98.9
103
103
104
86.6
RSD
4.3
2.0
2.7
3.5
1.1
3.4
2.2
2.2
1.5
2.3
2.6
1.1
4.2
1.0
5.9
4.1
5.0
2.3
6.3
4.5
4.1
2.1
3.4
3.0
4.3
3.9
3.0
3.1
3.3
525.3-114
-------
Table 12. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
UCT 525 Universal Cartridges; N=4 for Each Matrix; Full Scan GC/MS Analyses'1
Analytes
fluorene
fluridone
HCCPD
HCH, a
HCH, (3
HCH, 5
HCH, y (lindane)
heptachlor
heptachlor epoxide
hexachlorobenzene
hexazinone
indeno[l,2,3-c,
-------
Table 12. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
UCT 525 Universal Cartridges; N=4 for Each Matrix; Full Scan GC/MS Analyses'1
Analytes
permethrin, trans
phenanthrene
phorate
phosphamidon
profenofos
prometon
prometryn
pronamide
propachlor
propazine
pyrene
simazine
simetryn
tebuconazole
tebuthiuron
terbacil
terbutryn
tetrachlorvinphos
triadimefon
tribufos+merphos
trifluralin
vernolate
vinclozolin
PCB congeners (by IUPAC#)
2-chlorobiphenyl (1)
4-chlorobiphenyl (3)
2,4'-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
Fortified
Cone. (jig/L)
3.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
4.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Ground Waterb
Mean %
Recoveryd
91.4
106
95.5
100
98.4
96.9
98.8
95.1
106
101
106
101
98.6
94.4
88.5
101
97.3
97.5
99.3
96.6
90.8
88.0
98.6
90.8
96.1
97.9
101
101
RSD
7.1
3.7
2.0
3.3
4.4
2.1
4.9
5.5
1.4
2.8
1.2
3.7
4.2
5.4
7.1
5.6
5.1
6.6
2.1
7.3
2.2
6.0
7.0
1.7
0.65
0.87
3.8
2.2
Surface Water0
Mean %
Recoveryd
100
104
98.9
114
108
88.4
94.6
96.6
110
96.4
107
96.1
87.9
96.0
101
95.8
87.4
104
101
107
90.0
88.3
111
96.3
99.9
86.6
90.9
86.1
RSD
2.3
2.5
4.8
2.8
1.7
5.7
4.9
3.4
3.4
2.5
2.2
3.0
3.8
5.2
1.8
10
5.1
5.4
3.0
2.0
4.5
1.8
1.7
5.6
5.4
6.3
7.5
4.9
525.3-116
-------
Table 12. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
UCT 525 Universal Cartridges; N=4 for Each Matrix; Full Scan GC/MS Analyses'1
Analytes
2,2',3,5'-tetrachlorobiphenyl(44)
2,2',5,5'-tetrachlorobiphenyl(52)
2,3 ',4',5-tetrachloroobiphenyl (70)
2,3,3',4',6-pentachlorobiphenyl (1 10)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Surrogate Analytes
1 , 3 -dimethyl-2 -nitrobenzene
benzo [a] pyrene-c/i 2
triphenyl phosphate
Fortified
Cone. (jig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
5.0
5.0
5.0
Ground Waterb
Mean %
Recoveryd
93.0
97.1
107
107
108
110
106
108
99.6
91.7
103
104
RSD
3.0
3.1
1.5
1.3
1.2
2.0
1.4
0.89
1.0
7.5
2.7
0.58
Surface Water0
Mean %
Recoveryd
88.1
87.8
88.1
92.0
91.3
93.8
91.5
91.3
87.6
89.0
104
112
RSD
6.9
6.6
5.2
6.3
6.4
5.3
6.0
6.3
7.2
6.5
3.0
3.5
a. Data obtained on the instrumentation described in Sect. 13.1.1.4.
b. Tap water from a ground water source with high mineral content. Tap water hardness was 300 mg/L as calcium
carbonate.
c. Tap water from a surface water source. TOC of 2.4 mg/L.
d. Recoveries have been corrected to reflect the native amount in the unfortified matrix water.
525.3-117
-------
Table 13. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using Horizon Atlantic DVB Disks; N=5 for
Each Concentration; Full Scan GC/MS Analyses21
Analytes
acenaphthylene
acetochlor
alachlor
aldrin
ametryn
anthracene
atraton
atrazine
benzo [a] anthracene
benzo[a]pyrene
benzo[6]fluoranthene
benzo \g, h, /'Jperylene
benzo [k] fluoranthene
BHT
bromacil
butachlor
butylate
butylbenzylphthalate
chlordane, cis
chlordane, trans
chlorfenvinphos
chlorobenzilate
chloroneb
chlorothalonil
chlorpropham
chlorpyrifos
chrysene
cyanazine
cycloate
Fortified Cone.
0.25 jig/Lb
Mean %
Recovery
87.3
92.3
95.6
85.6
91.4
87.2
93.2
94.5
93.6
88.9
87.9
88.3
91.1
89.8
96.9
94.9
86.9
104
92.1
91.2
89.1
96.0
89.7
89.0
93.7
89.1
90.7
101
90.0
RSD
3.4
4.0
8.0
1.2
3.5
4.6
5.2
7.4
2.5
3.5
3.6
4.2
3.8
5.0
1.9
5.0
2.4
19
6.5
5.0
7.7
4.0
4.2
4.8
7.7
2.6
2.3
8.6
4.9
Fortified Cone.
2.0 jig/Lc
Mean %
Recovery
86.6
93.9
93.4
84.7
93.9
90.2
94.9
92.9
90.6
85.8
85.1
79.8
85.9
84.9
94.3
91.5
88.0
94.5
89.2
89.4
94.0
93.8
90.9
94.3
92.5
91.3
92.0
108
89.6
RSD
1.1
2.6
2.0
5.7
2.9
2.2
5.3
2.9
2.1
3.0
3.0
3.9
2.7
1.5
2.8
2.8
2.4
3.9
4.9
4.2
4.3
4.4
1.4
1.6
2.3
3.2
2.6
3.3
1.7
Fortified Cone.
5.0 ng/Ld
Mean %
Recovery
90.5
95.2
94.6
90.4
95.8
92.9
98.5
95.0
91.3
88.2
89.0
84.5
87.2
87.6
96.6
93.0
91.5
93.6
89.7
88.9
95.3
92.4
93.6
97.3
95.8
94.4
90.9
114
92.4
RSD
1.3
1.4
1.4
1.2
1.5
1.4
2.4
1.9
1.7
3.9
4.0
3.8
3.9
1.2
3.6
2.4
1.5
1.2
2.5
2.3
2.4
1.9
1.3
2.3
0.75
2.1
1.4
3.7
0.32
525.3-118
-------
Table 13. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using Horizon Atlantic DVB Disks; N=5 for
Each Concentration; Full Scan GC/MS Analyses21
Analytes
dacthal (DCPA)
ODD, 4,4'-
DDE, 4,4'-
DDT, 4,4'-
DEET
di(2-ethylhexyl)adipate
di(2-ethylhexyl)phthalate
dibenzo[a,/z]anthracene
dibutyl phthalate
dichlorvos
dieldrin
diethylphthalate
dimethipin
dimethylphthalate
DIMP
dinitrotoluene, 2,4-
dinitrotoluene, 2,6-
diphenamid
disulfoton
endosulfan I
endosulfan II
endosulfan sulfate
endrin
EPTC
ethion
ethoprop
ethyl parathion
etridiazole
fenarimol
Fortified Cone.
0.25 jig/Lb
Mean %
Recovery
93.9
91.0
83.9
88.8
91.6
84.1
NDe
85.3
ND
93.2
93.6
93.6
36.0
89.4
89.9
88.6
89.3
93.8
71.0
87.9
94.8
95.1
88.1
85.8
96.1
91.9
92.9
84.6
99.8
RSD
3.3
3.4
4.3
6.0
5.5
8.6
5.0
4.4
9.2
5.4
13
5.3
5.3
5.8
5.7
3.2
5.0
9.2
5.8
4.8
2.1
3.5
4.3
4.1
7.8
6.7
5.9
Fortified Cone.
2.0 jig/Lc
Mean %
Recovery
94.3
91.8
87.9
88.3
92.9
76.2
77.0
76.7
111
86.7
91.3
91.4
32.8
90.0
83.9
92.1
89.1
94.7
77.4
89.6
91.5
93.4
92.5
86.2
93.5
92.1
88.8
88.8
95.9
RSD
2.1
3.4
6.8
4.2
2.0
3.3
2.7
3.7
2.2
0.98
6.2
2.2
25
1.0
2.7
1.4
2.1
2.1
4.9
o o
J.J
6.7
2.7
4.7
0.96
3.9
2.7
3.1
1.4
3.7
Fortified Cone.
5.0 ng/Ld
Mean %
Recovery
96.0
88.3
85.6
86.4
94.5
76.5
72.7
81.5
95.0
89.3
91.1
94.2
28.4
92.6
86.8
97.0
94.0
96.2
77.8
91.1
90.6
93.4
93.0
90.5
92.7
95.7
93.4
92.3
100
RSD
1.2
1.8
3.0
2.4
0.82
3.1
2.8
4.5
0.96
2.3
2.8
0.90
9.6
1.0
1.8
1.3
0.67
1.4
4.8
1.4
3.0
1.7
2.3
1.8
2.8
0.71
2.8
1.1
3.4
525.3-119
-------
Table 13. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using Horizon Atlantic DVB Disks; N=5 for
Each Concentration; Full Scan GC/MS Analyses21
Analytes
fluorene
fluridone
HCCPD
HCH, a
HCH, (3
HCH, 5
HCH, y (lindane)
heptachlor
heptachlor epoxide
hexachlorobenzene
hexazinone
indeno[l,2,3-c,
-------
Table 13. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using Horizon Atlantic DVB Disks; N=5 for
Each Concentration; Full Scan GC/MS Analyses21
Analytes
permethrin, trans
phenanthrene
phorate
phosphamidon
profenofos
prometon
prometryn
pronamide
propachlor
propazine
pyrene
simazine
simetryn
tebuconazole
tebuthiuron
terbacil
terbutryn
tetrachlorvinphos
triadimefon
tribufos
trifluralin
vernolate
vinclozolin
PCB congeners (by IUPAC#)
2-chlorobiphenyl (1)
4-chlorobiphenyl (3)
2,4'-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
Fortified Cone.
0.25 jig/Lb
Mean %
Recovery
89.3
88.6
83.7
98.3
92.0
90.0
94.0
92.3
88.8
95.5
92.2
93.9
95.1
93.2
95.4
91.4
96.5
95.6
94.5
82.0
91.0
87.3
94.3
85.3
88.2
87.1
89.4
84.4
RSD
3.2
3.9
4.2
6.5
8.6
3.8
2.0
4.0
5.2
3.3
4.3
3.8
2.1
5.3
11
6.1
5.1
4.9
2.4
5.2
5.8
2.5
8.5
5.2
4.0
5.8
2.5
6.8
Fortified Cone.
2.0 jig/Lc
Mean %
Recovery
82.3
90.1
88.8
95.2
93.7
93.9
98.9
93.5
91.5
93.5
91.8
94.2
93.8
94.7
91.3
94.5
93.7
92.3
96.1
95.8
91.2
87.0
94.7
87.2
88.1
90.8
91.0
90.6
RSD
2.2
2.4
2.3
2.9
2.8
3.2
3.9
1.7
2.8
2.6
3.8
1.8
2.8
2.0
9.5
1.9
3.0
3.1
o o
J.J
4.4
2.1
1.1
4.6
1.8
1.3
2.0
2.9
3.1
Fortified Cone.
5.0 ng/Ld
Mean %
Recovery
83.2
92.6
91.1
95.5
94.7
96.0
102
96.1
94.7
95.7
92.3
98.7
95.4
97.0
99.6
96.2
95.5
93.0
96.7
93.7
95.9
90.7
94.9
90.0
92.0
92.5
92.0
90.8
RSD
2.0
1.7
0.97
2.0
4.2
0.79
2.2
1.9
0.89
0.55
2.1
2.9
1.0
2.3
8.9
2.9
1.5
2.8
2.6
1.6
0.75
1.8
2.2
0.53
1.1
0.43
0.54
0.41
525.3-121
-------
Table 13. Precision and Accuracy Data Obtained for Method Analytes Fortified in Reagent
Water at Three Concentrations and Extracted Using Horizon Atlantic DVB Disks; N=5 for
Each Concentration; Full Scan GC/MS Analyses21
Analytes
2,2',3,5'-tetrachlorobiphenyl(44)
2,2',5,5'-tetrachlorobiphenyl(52)
2,3 ',4',5-tetrachloroobiphenyl (70)
2,3,3',4',6-pentachlorobiphenyl (1 10)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Surrogate Analytes
1 , 3 -dimethyl-2 -nitrobenzene
benzo [a] pyrene-^i 2
triphenyl phosphate
Fortified Cone.
0.25 jig/Lb
Mean %
Recovery
87.2
89.4
87.8
87.1
85.5
85.9
84.3
83.1
81.9
86.4
89.6
87.8
RSD
7.5
5.4
8.3
3.2
3.4
5.7
6.6
4.4
6.0
4.0
3.5
2.6
Fortified Cone.
2.0 ug/Lc
Mean %
Recovery
89.6
88.8
88.3
90.5
89.0
88.6
88.0
87.7
87.1
86.2
93.5
93.3
RSD
2.8
2.2
5.0
4.1
4.3
3.9
4.5
4.7
4.5
1.9
5.1
2.9
Fortified Cone.
5.0 ng/Ld
Mean %
Recovery
90.3
89.4
89.4
88.5
84.3
86.4
86.7
85.1
86.5
88.0
98.9
99.9
RSD
1.7
2.7
1.7
3.4
4.1
2.8
3.6
4.6
2.9
0.92
4.2
1.8
a. Data obtained on the instrumentation described in Sect. 13.1.1.3.
b. Exceptions to the stated concentration are as follows: Surrogate concentrations are 5.0 ug/L, pentachlorophenol
is 1.0 ug/L, MGK 264 (a) is 0.200 ug/L and MGK 264 (b) is 0.050 ug/L.
c. Exceptions to the stated concentration are as follows: Surrogate concentrations are 5.0 ug/L, pentachlorophenol
is 8.0 ug/L,, MGK 264 (a) is 1.6 ug/L and MGK 264 (b) is 0.4 ug/L.
d. Exceptions to the stated concentration are as follows: Surrogate concentrations are 5.0 ug/L, pentachlorophenol
is 20.0 ug/L,, MGK 264 (a) is 4.0 ug/L and MGK 264 (b) is 1.0 ug/L.
e. ND = Not determined. Analyte could not be determined because of high laboratory reagent blank values relative
to the fortification concentration.
525.3-122
-------
Table 14. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
Horizon Atlantic DVB Disks; N=5 for Each Matrix; Full Scan GC/MS Analyses'1
Analytes
acenaphthylene
acetochlor
alachlor
aldrin
ametryn
anthracene
atraton
atrazine
benzo [a] anthracene
benzo[a]pyrene
benzo[6]fluoranthene
benzo \g, h, /Jperylene
benzo [k] fluoranthene
BHT
bromacil
butachlor
butylate
butylbenzylphthalate
chlordane, cis-
chlordane, trans
chlorfenvinphos
chlorobenzilate
chloroneb
chlorothalonil
chlorpropham
chlorpyrifos
chrysene
cyanazine
cycloate
Fortified
Cone. (jig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Synthetic Hard Waterb
Mean %
Recoveryd
90.9
98.7
96.9
93.3
90.8
95.3
85.8
92.2
92.1
87.4
85.7
79.1
87.9
92.6
95.4
93.5
95.0
92.8
89.0
89.7
95.2
94.3
95.6
97.1
97.1
95.2
94.8
98.7
94.4
RSD
2.2
0.47
1.2
3.4
4.2
2.2
5.7
3.2
2.4
2.3
3.6
1.6
o o
5.5
1.6
4.2
3.6
2.0
3.2
1.7
1.6
4.1
4.1
1.2
1.9
1.4
2.5
2.7
7.1
2.3
Surface Water0
Mean %
Recoveryd
92.1
97.0
95.0
93.2
90.0
94.8
88.2
93.3
91.9
86.8
85.8
78.4
85.1
93.8
96.1
93.4
95.8
92.5
89.8
90.3
95.1
93.2
95.6
97.8
97.4
95.0
91.8
97.4
94.5
RSD
1.8
2.6
1.6
2.9
3.2
1.6
4.5
0.82
1.7
2.4
3.0
6.1
3.5
2.4
2.7
2.1
3.4
1.9
2.3
1.3
2.3
1.7
1.5
1.6
2.0
2.2
2.3
5.4
2.0
525.3-123
-------
Table 14. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
Horizon Atlantic DVB Disks; N=5 for Each Matrix; Full Scan GC/MS Analyses'1
Analytes
dacthal (DCPA)
ODD, 4,4'-
DDE, 4,4'-
DDT, 4,4'-
DEET
di(2-ethylhexyl)adipate
di(2-ethylhexyl)phthalate
dibenzo[a,/z]anthracene
dibutyl phthalate
dichlorvos
dieldrin
diethylphthalate
dimethipin
dimethylphthalate
DIMP
dinitrotoluene, 2,4-
dinitrotoluene, 2,6-
diphenamid
disulfoton
endosulfan I
endosulfan II
endosulfan sulfate
endrin
EPTC
ethion
ethoprop
ethyl parathion
etridiazole
fenarimol
Fortified
Cone. Qig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Synthetic Hard Waterb
Mean %
Recoveryd
97.5
86.5
83.6
82.4
99.3
72.1
73.0
75.8
116
90.0
90.4
96.7
45.0
94.3
84.6
93.4
92.9
95.5
80.0
68.1
90.6
92.6
90.6
93.0
92.8
99.1
95.4
96.1
98.7
RSD
1.7
3.5
1.7
2.1
2.4
1.4
3.6
2.1
2.3
3.6
4.9
2.3
24
1.8
3.5
5.6
3.3
2.6
5.1
2.7
6.2
3.2
3.4
2.0
3.2
2.1
1.9
2.6
4.5
Surface Water0
Mean %
Recoveryd
98.0
87.5
84.2
82.5
99.3
73.4
74.7
75.2
114
91.4
88.3
96.4
34.8
95.2
88.3
98.2
95.5
95.2
73.4
59.4
89.7
92.1
93.0
94.6
89.3
98.7
96.3
95.1
94.4
RSD
0.56
1.4
2.6
0.57
2.9
2.0
3.1
6.3
1.0
2.2
1.8
1.1
17
1.9
5.1
3.0
1.1
1.8
10
7.7
4.8
2.4
2.5
2.0
1.1
2.6
6.8
2.8
1.8
525.3-124
-------
Table 14. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
Horizon Atlantic DVB Disks; N=5 for Each Matrix; Full Scan GC/MS Analyses'1
Analytes
fluorene
fluridone
HCCPD
HCH, a
HCH, (3
HCH, 5
HCH, y (lindane)
heptachlor
heptachlor epoxide
hexachlorobenzene
hexazinone
indeno[l,2,3-c,
-------
Table 14. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
Horizon Atlantic DVB Disks; N=5 for Each Matrix; Full Scan GC/MS Analyses'1
Analytes
permethrin, trans
phenanthrene
phorate
phosphamidon
profenofos
prometon
prometryn
pronamide
propachlor
propazine
pyrene
simazine
simetryn
tebuconazole
tebuthiuron
terbacil
terbutryn
tetrachlorvinphos
triadimefon
tribufos
trifluralin
vernolate
vinclozolin
PCB congeners (by IUPAC#)
2-chlorobiphenyl (1)
4-chlorobiphenyl (3)
2,4'-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
Fortified
Cone. (jig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Synthetic Hard Waterb
Mean %
Recoveryd
80.1
93.8
92.0
92.7
94.2
87.4
93.3
95.7
97.1
93.8
93.0
91.8
88.4
97.0
97.7
96.1
92.4
91.7
97.6
95.2
100
92.6
97.5
90.8
91.8
94.9
95.2
93.6
RSD
2.9
1.2
1.5
5.3
2.9
6.1
4.5
2.3
2.8
1.8
2.5
2.7
3.8
2.3
6.1
2.0
5.4
3.9
3.9
3.7
1.8
2.4
1.1
2.0
2.3
2.0
2.2
1.9
Surface Water0
Mean %
Recoveryd
79.1
94.3
93.0
94.6
95.7
86.1
91.5
96.4
96.3
93.0
93.7
92.9
89.6
96.8
98.8
96.5
89.6
91.8
93.8
93.5
99.1
94.0
97.6
92.0
92.4
95.0
94.4
92.9
RSD
1.8
2.3
4.1
1.7
2.0
3.6
2.8
1.7
1.3
3.0
1.4
2.7
3.4
2.4
8.0
2.6
4.2
3.1
4.2
2.3
2.0
2.5
3.9
2.4
3.2
2.7
1.8
3.4
525.3-126
-------
Table 14. Precision and Accuracy Data Obtained for Method Analytes Fortified into
Finished Drinking Waters from Ground and Surface Water Sources, and Extracted Using
Horizon Atlantic DVB Disks; N=5 for Each Matrix; Full Scan GC/MS Analyses'1
Analytes
2,2',3,5'-tetrachlorobiphenyl(44)
2,2',5,5'-tetrachlorobiphenyl(52)
2,3 ',4',5-tetrachloroobiphenyl (70)
2,3,3',4',6-pentachlorobiphenyl (1 10)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Surrogate Analytes
1 , 3 -dimethyl-2 -nitrobenzene
benzo [a] pyrene-c/i 2
triphenyl phosphate
Fortified
Cone. (jig/L)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Synthetic Hard Waterb
Mean %
Recoveryd
94.4
91.1
87.8
86.6
83.3
82.6
82.5
81.5
79.3
88.7
94.1
92.2
RSD
3.8
3.6
1.2
1.3
2.9
1.8
2.0
1.8
2.6
2.9
2.4
1.8
Surface Water0
Mean %
Recoveryd
92.1
91.4
89.4
88.0
86.9
84.7
85.9
83.4
81.3
90.6
93.4
92.4
RSD
2.1
2.5
1.2
1.8
1.7
2.2
2.8
2.9
1.6
3.8
3.2
1.7
a. Data obtained on the instrumentation described in Sect. 13.1.1.3.
b. A synthetic hard water sample was prepared as described in Sect. 16, Reference 33 by adding calcium carbonate,
magnesium carbonate, and sodium bicarbonate to tap water. The resulting synthetic hard water was > 350 mg/L
as calcium carbonate.
c. Tap water from a surface water source. TOC of 2.6 mg/L.
d. Recoveries have been corrected to reflect the native amount in the unfortified matrix water.
525.3-127
-------
Table 15. DLs and LCMRLs (ug/L) Calculated from Replicate Analyses of Fortified
Reagent Water Samples Analyzed in Full Scan GC/MS Mode
Analytes
acenaphthylene
acetochlor
alachlor
aldrin
ametryn
anthracene
atraton
atrazine
benzo [a] anthracene
benzo[a]pyrene
benzo[6]fluoranthene
benzo \g, h, /Jperylene
benzo[&]fluoranthene
BHT
bromacil
butachlor
butylate
butylbenzylphthalate
chlordane, cis
chlordane, trans
chlorfenvinphos
chlorobenzilate
chloroneb
chlorothalonil
chlorpropham
chlorpyrifos
chrysene
cyanazine
Laboratory 1
Oasis HLB SPEab
DL
0.015
0.037
0.035
0.056
0.038
0.018
0.016
0.030
0.021
0.043
0.031
0.021
0.048
0.092
NDe
0.028
0.024
0.068
0.10
0.027
0.095
0.034
0.068
0.036
0.026
0.091
0.017
0.032
Fortified
cone, of
DL
replicates
0.050
0.050
0.10
0.10
0.050
0.050
0.10
0.050
0.050
0.050
0.050
0.10
0.050
0.10
0.050
0.050
0.10
0.10
0.050
0.10
0.050
0.10
0.10
0.050
0.10
0.050
0.050
LCMRL
NCd
0.19
0.25
0.30
0.17
0.12
0.12
0.29
0.12
0.18
0.14
0.31
0.18
0.32
0.31
0.39
0.16
0.40
0.33
0.28
0.52
0.30
0.16
0.17
0.21
0.45
0.15
0.33
Laboratory 2
Empore PSDVB SPEC
DL
0.0029
0.011
0.0084
0.010
0.017
0.0078
0.0055
0.010
0.0062
0.035
0.013
0.011
0.026
0.0064
0.037
0.0043
0.0053
0.016
0.0094
0.010
0.0062
0.0042
0.19
0.0074
0.013
0.026
0.010
0.19
Fortified
cone, of
DL
replicates
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.050
0.025
0.025
0.025
0.050
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.050
0.050
LCMRL
0.028
0.054
0.097
0.420
0.12
0.059
0.12
0.086
0.043
0.11
0.11
0.047
0.190
0.50
0.10
0.089
0.089
0.20
0.068
0.043
0.098
0.091
0.90
0.11
0.14
0.076
0.035
0.15
525.3-128
-------
Table 15. DLs and LCMRLs (ug/L) Calculated from Replicate Analyses of Fortified
Reagent Water Samples Analyzed in Full Scan GC/MS Mode
Analytes
cycloate
dacthal (DCPA)
ODD, 4,4'-
DDE, 4,4'-
DDT, 4,4'-
DEET
di(2-ethylhexyl)adipate
di(2-ethylhexyl)phthalate
dibenzo[a,/z]anthracene
dibutyl phthalate
dichlorvos
dieldrin
diethylphthalate
dimethipin
dimethylphthalate
DIMP
dinitrotoluene, 2,4-
dinitrotoluene, 2,6-
diphenamid
disulfoton
endosulfan I
endosulfan II
endosulfan sulfate
endrin
EPTC
ethion
ethoprop
ethyl parathion
Laboratory 1
Oasis HLB SPEab
DL
0.039
0.018
0.019
0.033
0.036
0.019
0.079
ND
0.014
ND
0.021
0.064
0.037
0.045
0.026
0.039
0.026
0.056
0.033
0.12
0.039
0.14
0.068
0.045
0.037
0.010
0.13
0.15
Fortified
cone, of
DL
replicates
0.050
0.050
0.050
0.050
0.050
0.050
0.10
0.050
0.050
0.050
0.050
0.10
0.050
0.050
0.050
0.050
0.050
0.10
0.050
0.10
0.050
0.10
0.10
0.050
0.050
0.050
0.10
0.10
LCMRL
0.27
0.44
0.35
0.32
0.25
0.14
0.38
0.29
0.30
0.88
0.46
0.28
0.074
0.27
0.11
0.19
0.23
0.31
0.29
0.12
0.62
0.38
0.39
0.40
0.13
0.29
0.39
0.46
Laboratory 2
Empore PSDVB SPEC
DL
0.018
0.0055
0.0031
0.0023
0.022
0.0042
0.013
0.020
0.014
0.13
0.0051
0.017
0.018
ND
0.0048
0.0036
0.0076
0.053
0.010
0.0066
0.015
0.024
0.025
0.033
0.0048
0.013
0.0048
0.013
Fortified
cone, of
DL
replicates
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.075
0.025
0.025
0.050
0.050
0.050
0.050
0.025
0.025
0.025
0.050
LCMRL
0.14
0.040
0.092
0.088
0.12
0.066
0.083
0.40
0.14
1.4
0.081
0.084
0.13
NC
0.046
>5.0
0.19
0.20
0.089
0.11
0.11
NC
0.12
0.12
0.068
0.13
0.12
0.19
525.3-129
-------
Table 15. DLs and LCMRLs (ug/L) Calculated from Replicate Analyses of Fortified
Reagent Water Samples Analyzed in Full Scan GC/MS Mode
Analytes
etridiazole
fenarimol
fluorene
fluridone
HCCPD
HCH, a
HCH, (3
HCH, 5
HCH, y (lindane)
heptachlor
heptachlor epoxide
hexachlorobenzene
hexazinone
indeno[l,2,3-c,c/|pyrene
isophorone
methoxychlor
methyl parathion
metolachlor
metribuzin
mevinphos
MGK 264(a)
MGK 264(b)
molinate
napropamide
nitrofen
nonachlor, trans
norflurazon
oxyfluorfen
Laboratory 1
Oasis HLB SPEab
DL
0.024
0.10
0.016
0.11
0.012
0.036
0.10
0.019
0.036
0.034
0.039
0.016
0.025
0.11
0.014
0.024
0.036
0.019
0.036
0.035
0.072
0.023
0.062
0.077
0.093
0.035
0.057
0.037
Fortified
cone, of
DL
replicates
0.050
0.10
0.050
0.10
0.050
0.050
0.10
0.050
0.050
0.050
0.10
0.050
0.050
0.10
0.050
0.050
0.050
0.050
0.050
0.10
0.080
0.020
0.10
0.10
0.10
0.050
0.10
0.050
LCMRL
0.24
0.28
0.08
0.33
0.24
0.31
0.24
0.31
0.24
0.27
0.11
0.40
0.26
0.40
0.11
0.23
0.28
0.11
0.076
0.21
0.32
0.09
0.29
0.44
0.39
0.35
0.26
0.34
Laboratory 2
Empore PSDVB SPEC
DL
0.012
0.041
0.0058
0.045
0.0066
0.0037
0.021
0.015
0.014
0.0032
0.0053
0.0094
0.012
0.039
0.0043
0.0064
0.0088
0.0042
0.0070
0.0040
0.0026
0.0096
0.0036
0.025
0.042
0.0062
0.062
0.015
Fortified
cone, of
DL
replicates
0.025
0.050
0.025
0.050
0.025
0.025
0.050
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.050
0.025
0.025
0.025
0.025
0.025
0.025
0.050
0.050
0.025
0.050
0.050
LCMRL
0.17
0.20
0.051
0.27
0.084
0.062
0.11
0.099
0.078
0.029
0.063
0.087
0.14
0.20
0.063
0.061
0.16
0.14
0.11
0.093
0.031
0.083
0.074
0.11
0.13
0.049
0.14
0.28
525.3-130
-------
Table 15. DLs and LCMRLs (ug/L) Calculated from Replicate Analyses of Fortified
Reagent Water Samples Analyzed in Full Scan GC/MS Mode
Analytes
pebulate
pentachlorophenol
permethrin, cis
permethrin, trans
phenanthrene
phorate
phosphamidon
profenofos
prometon
prometryn
pronamide
propachlor
propazine
pyrene
simazine
simetryn
tebuconazole
tebuthiuron
terbacil
terbutryn
tetrachlorvinphos
triadimefon
tribufos+merphos
trifluralin
vernolate
vinclozolin
PCB congeners (by IUPAC#)
2-chlorobiphenyl (1)
Laboratory 1
Oasis HLB SPEab
DL
0.020
0.060
0.015
0.031
0.025
0.032
0.040
0.11
0.065
0.021
0.017
0.029
0.023
0.013
0.023
0.037
0.24
0.027
0.082
0.029
0.048
0.053
0.12
0.027
0.038
0.029
0.021
Fortified
cone, of
DL
replicates
0.050
0.20
0.028
0.072
0.10
0.050
0.10
0.10
0.10
0.050
0.050
0.050
0.050
0.050
0.050
0.050
0.50
0.050
0.10
0.050
0.10
0.050
0.10
0.050
0.050
0.050
0.050
LCMRL
0.20
0.56
0.13
0.10
0.097
0.20
0.23
0.31
0.22
0.24
0.13
0.27
0.20
0.17
0.12
0.28
2.1
0.21
0.41
0.18
0.35
0.35
0.53
0.28
0.11
0.34
0.14
Laboratory 2
Empore PSDVB SPEC
DL
0.0053
0.069
0.0026
0.012
0.0069
0.052
0.0029
0.055
0.010
0.012
0.0077
0.0076
0.0065
0.0045
0.0059
0.013
0.053
0.060
0.039
0.0051
0.0042
0.048
0.013
0.019
0.0051
0.016
0.0061
Fortified
cone, of
DL
replicates
0.025
0.025
0.025
0.025
0.025
0.050
0.025
0.050
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.050
0.075
0.075
0.025
0.025
0.050
0.025
0.025
0.025
0.050
0.025
LCMRL
0.040
0.16
0.036
0.087
0.51
0.15
0.11
0.11
0.12
0.10
0.13
0.068
0.055
0.062
0.083
0.12
0.18
0.13
0.13
0.093
0.14
0.11
0.18
0.12
0.080
0.12
0.054
525.3-131
-------
Table 15. DLs and LCMRLs (ug/L) Calculated from Replicate Analyses of Fortified
Reagent Water Samples Analyzed in Full Scan GC/MS Mode
Analytes
4-chlorobiphenyl (3)
2,4'-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
2,2',3,5'-tetrachlorobiphenyl(44)
2,2',5,5'-tetrachlorobiphenyl(52)
2,3 ',4',5-tetrachloroobiphenyl (70)
2,3,3',4',6-pentachlorobiphenyl (1 10)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Laboratory 1
Oasis HLB SPEab
DL
0.019
0.024
0.024
0.036
0.029
0.043
0.043
0.026
0.046
0.19
0.020
0.029
0.058
Fortified
cone, of
DL
replicates
0.050
0.050
0.050
0.050
0.050
0.10
0.050
0.050
0.050
0.10
0.050
0.050
0.10
LCMRL
0.24
0.18
0.086
0.069
0.23
0.092
0.30
0.36
0.36
0.41
0.37
0.38
0.31
Laboratory 2
Empore PSDVB SPEC
DL
0.0059
0.0037
0.028
0.0073
0.0079
0.0055
0.0044
0.0030
0.0050
0.0071
0.0039
0.0033
0.0066
Fortified
cone, of
DL
replicates
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
LCMRL
0.065
0.088
0.14
0.036
0.041
0.078
0.046
0.084
0.095
0.058
0.056
0.092
0.036
a. DL calculated from eight replicates.
b. Data obtained on the instrumentation described in Sect. 13.1.1.1.
c. Data obtained on the instrumentation described in Sect. 13.1.1.2.
d. NC= Not calculated. A sufficient number of data points were not available to calculate a valid LCMRL.
e. ND= Not determined. DLs were not determined when a response was not detected in all replicates at a given
concentration, or when a high background concentration or an interference was present that prevented accurate
quantitation at the fortified concentration.
525.3-132
-------
Table 16. Example SIM Parameters for Selected Method Analytes
SIM
Segment
# 1
#2
#3
#4
#5
#6
#7
#8
#9
# 10
#11
Compound
l,3-dimethyl-2-nitrobenzene (SUR)
HCCPD
acenaphthene-
-------
Table 16. Example SIM Parameters for Selected Method Analytes
SIM
Segment
#12
# 13
#14
#15
# 16
#17
Compound
profenofos
tribufos
oxyfluorfen
2,3,3',4',6-pentachlorobiphenyl
endrin
2,2',3,4',5',6-hexachlorobiphenyl
2,3',4,4',5-pentachlorobiphenyl
toxaphene, peak 1
2,2',4,4',5,5'-hexachlorobiphenyl
toxaphene, peak 2
toxaphene, peak 3
2,2',3,4,4',5'-hexachlorobiphenyl
tebuconazole
di(2-ethylhexyl)adipate
triphenyl phosphate (SUR)
chrysene-^2 (IS #3)
methoxychlor
2,2',3,4,4',5,5'-heptachlorobiphenyl
toxaphene, peak 4
di(2-ethylhexyl)phthalate
c-permethrin
t-permethrin
benzo(a)pyrene-<5?i2 (SUR)
benzo(a)pyrene
RT
(min)
20.77
20.91
21.02
21.03
21.46
21.57
21.68
21.74
22.18
22.47
22.67
22.81
23.12
23.17
23.26
24.03
24.18
24.44
24.55
24.72
26.42
26.60
27.90
28.03
Qi
(m/z)
339
57
252
326
263
360
326
159
360
305
159
360
125
129
77
240
227
394
159
149
183
183
264
252
Confirmation
Ion(s) (m/z)
97, 139
169
361
254, 256
81,281
218,290
254, 256
125, 305*
218,290
125
125, 305*
218,290
83, 250
57,70
169, 325
236*
-
252, 324
125, 305*
167
163*
163*
132*
126*
Dwell
Time
(ms)
45
50
50
75
125
125
Scan
Time
(sec/scan)
0.61
0.60
0.60
0.55
0.57
0.57
* Confirmation ions may be at or below 30% relative abundance depending on instrument tune.
525.3-134
-------
Table 17. Precision and Accuracy Data Obtained for Selected Method Analytes Fortified in
Reagent Water at Three Concentrations and Extracted Using Oasis HLB SPE Cartridges;
SIM GC/MS Analyses21
Analytes
acetochlor
alachlor
atrazine
benzo[a]pyrene
chlordane, cis
chlordane, trans
di(2-ethylhexyl)adipate
di(2-ethylhexyl)phthalate
dimethipin
endrin
ethoprop
HCCPD
HCH, a
HCH, y (lindane)
heptachlor
heptachlor epoxide
hexachlorobenzene
methoxychlor
metolachlor
molinate
nonachlor, trans
oxyfluorfen
pentachlorophenol
permethrin, cis
permethrin, trans
profenofos
simazine
tebuconazole
tribufos
vinclozolin
Fortified Cone.
0.025 jig/Lb
n=4
Mean %
Recovery
103
114
117
81.0
110
89.9
NDe
ND
91.5
97.5
89.4
102
112
104
104
108
90.2
113
114
104
98.9
114
79.0
91.5
94.6
102
85.2
82.6
96.2
93.1
RSD
1.8
2.7
5.7
4.8
4.1
1.4
4.1
6.1
19
7.6
5.6
6.9
9.3
3.8
9.6
8.4
1.0
5.7
2.8
12
7.9
9.7
2.5
8.4
12
7.4
7.8
4.4
Fortified Cone.
0.10 fig/Lc
n=4
Mean %
Recovery
109
112
118
103
102
99.4
114
113
108
105
109
108
114
110
99.9
103
95.3
116
115
109
96.4
115
96.3
113
104
92.0
101.3
116.0
101.2
110
Mean %
Recovery
1.9
1.1
3.6
2.2
2.9
5.3
4.2
33
7.4
3.7
3.2
1.2
o o
5.5
2.0
3.4
4.6
2.1
2.8
4.3
2.3
5.5
5.2
6.7
3.2
2.0
2.3
13.0
1.9
3.5
2.0
Fortified Cone.
0.25 jig/Ld
n=4
Mean %
Recovery
105
104
111
97.4
100
100
111
118
112
100
112
100
99.6
100
89.2
98.2
90.6
104
107
109
99.9
124
97.2
105
103
112
124
117
105
104
RSD
2.2
3.1
1.8
7.5
3.0
2.8
1.7
7.8
3.2
1.6
1.7
4.3
4.5
6.2
2.7
3.3
2.7
1.6
1.7
1.4
3.4
6.3
2.0
2.0
1.5
1.7
1.9
0.69
3.9
2.4
525.3-135
-------
Table 17. Precision and Accuracy Data Obtained for Selected Method Analytes Fortified in
Reagent Water at Three Concentrations and Extracted Using Oasis HLB SPE Cartridges;
SIM GC/MS Analyses21
Analytes
PCB congeners (by IUPAC#)
2-chlorobiphenyl (1)
4-chlorobiphenyl (3)
2,4'-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
2,2',3,5'-tetrachlorobiphenyl(44)
2,2',5,5'-tetrachlorobiphenyl(52)
2,3 ',4',5-tetrachloroobiphenyl (70)
2,3,3 ',4',6-pentachlorobiphenyl (1 10)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Surrogate Analytes
1 , 3 -dimethyl-2 -nitrobenzene
benzo [a] pyrene-^i 2
triphenyl phosphate
Fortified Cone.
0.025 jig/Lb
n=4
Mean %
Recovery
99.9
96.8
109
101
90.8
94.5
97.0
88.3
92.0
86.2
86.7
95.3
86.8
99.7
101
87.9
103
RSD
2.7
4.8
12
6.1
10.0
4.2
4.6
15
3.7
8.8
3.7
4.7
2.0
9.5
2.2
3.0
1.9
Fortified Cone.
0.10 fig/Lc
n=4
Mean %
Recovery
106
105
110
106
105
108
105
103
99.9
96.5
96.1
97.4
98.7
97.6
105
92.1
106
Mean %
Recovery
1.1
1.0
7.1
3.0
1.7
5.7
1.3
6.5
4.9
3.7
4.4
3.1
0.79
4.3
3.6
2.4
3.2
Fortified Cone.
0.25 jig/Ld
n=4
Mean %
Recovery
98.8
109
102
99.9
101
98.5
101
100
99.2
97.6
96.3
95.4
97.2
95.7
93.6
94.5
101
RSD
2.6
1.8
2.4
0.82
1.3
3.1
2.5
2.5
1.6
2.5
1.5
2.3
1.4
2.0
4.4
8.8
1.4
a. Data obtained on the instrumentation described in Sect. 13.1.1.1.
b. Exceptions to the stated concentration are as follows: Surrogate concentrations are 1.0 ug/L, pentachlorophenol
is 0.10 ug/L, tebuconazole is 0.12 ug/L, c-permethrin is 0.014 ug/L, and t-permethrin is 0.036 ug/L.
c. Exceptions to the stated concentration are as follows: Surrogate concentrations are 1.0 ug/L, pentachlorophenol
is 0.40 ug/L, tebuconazole is 0.50 ug/L, c-permethrin is 0.056 ug/L, and t-permethrin is 0.144 ug/L.
d. Exceptions to the stated concentration are as follows: Surrogate concentrations are 1.0 ug/L, pentachlorophenol
is 1.0 ug/L, tebuconazole is 1.02 ug/L, c-permethrin is 0.14 ug/L, and t-permethrin is 0.36 ug/L.
e. ND = Not determined. Analyte could not be determined because of the low concentration relative to the LRB.
525.3-136
-------
Table 18. Precision and Accuracy Data Obtained for Selected Method Analytes Fortified
into Finished Drinking Waters from Ground and Surface Water Sources, and Extracted
Using Oasis HLB SPE Cartridges; N=4 for Each Matrix; SIM GC/MS Analyses'1
Analytes
acetochlor
alachlor
atrazine
benzo[a]pyrene
chlordane, cis
chlordane, trans
di(2-ethylhexyl)adipate
di(2-ethylhexyl)phthalate
dimethipin
endrin
ethoprop
HCCPD
HCH, a
HCH, y (lindane)
heptachlor
heptachlor epoxide
hexachlorobenzene
methoxychlor
metolachlor
molinate
nonachlor, trans
oxyfluorfen
pentachlorophenol
permethrin, cis
permethrin, trans
profenofos
simazine
tebuconazole
tribufos
Fortified
Cone. (jig/L)
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.40
0.06g
0.14h
0.10
0.10
0.50
0.10
Ground Water
Mean %
Recoveryd
109
110
112
86.3
98.1
101
116
NDf
96.0
112
111
122
111
100
90.9
96.5
90.4
116
112
120
93.3
122
90.5
106
101
107
101
115
107
RSD
9.6
5.9
11
2.7
3.4
4.3
7.4
7.4
4.4
9.6
7.4
8.4
5.5
5.9
4.5
4.9
4.1
6.3
7.2
3.8
6.5
8.2
5.0
3.6
3.5
10
5.6
5.9
Surface Water0
Mean %
Recoveryd
NAe
112
101
104
97.9
102
114
ND
103
107
102
82.8
84.5
108
85.3
103
83.8
128
NA
NA
NA
123
94.9
102
108
110
105
99.9
110
RSD
3.6
0.45
7.6
3.9
3.7
4.8
18
3.3
3.6
7.3
7.2
4.6
5.8
1.4
3.3
1.3
4.6
0.88
5.1
3.0
6.8
3.0
4.5
3.5
525.3-137
-------
Table 18. Precision and Accuracy Data Obtained for Selected Method Analytes Fortified
into Finished Drinking Waters from Ground and Surface Water Sources, and Extracted
Using Oasis HLB SPE Cartridges; N=4 for Each Matrix; SIM GC/MS Analyses'1
Analytes
vinclozolin
PCB congeners (by IUPAC#)
2-chlorobiphenyl (1)
4-chlorobiphenyl (3)
2,4'-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
2,2',3,5'-tetrachlorobiphenyl(44)
2,2',5,5'-tetrachlorobiphenyl(52)
2,3 ',4',5-tetrachloroobiphenyl (70)
2,3,3',4',6-pentachlorobiphenyl (1 10)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Surrogate Analytes
1 , 3 -dimethyl-2 -nitrobenzene
benzo [a] pyrene-^i 2
triphenyl phosphate
Fortified
Cone. (jig/L)
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
1.0
1.0
1.0
Ground Water
Mean %
Recoveryd
103
87.8
104
110
93.0
97.2
96.8
94.2
95.4
92.8
91.5
101
93.6
92.1
92.1
106
84.4
103
RSD
8.3
9.6
6.4
5.9
4.0
6.1
3.9
4.4
4.9
4.6
5.6
4.6
4.4
4.8
3.7
5.4
2.6
2.7
Surface Water0
Mean %
Recoveryd
104
95.8
96.5
90.0
92.7
91.4
81.6
95.3
98.8
97.5
92.3
96.9
96.6
94.5
92.6
95.3
100
106
RSD
4.2
4.5
3.5
4.9
3.2
2.1
5.2
5.0
0.85
3.0
3.0
3.5
1.5
0.86
2.1
5.7
5.6
2.0
a. Data obtained on the instrumentation described in Sect. 13.1.1.1.
b. Tap water from a ground water source with high mineral content. Tap water hardness was 393 mg/L as calcium
carbonate.
c. Tap water from a surface water source. TOC of 2.0 mg/L.
d. Recoveries have been corrected to reflect the native amount in the unfortified matrix water.
e. NA = Not analyzed. Matrix sample was not fortified with this analyte.
f. ND = Not determined. Recovery could not be determined because high LRB concentrations were observed
relative to the fortified concentration.
g. The concentration in ground water is as listed in the table. The concentration in surface water is 0.030 ug/L.
h. The concentration in ground water is as listed in the table. The concentration in surface water is 0.070 ug/L.
525.3-138
-------
Table 19. Precision and Accuracy Data Obtained for Selected Method Analytes Fortified in
Reagent Water at Three Concentrations and Extracted Using J.T. Baker HiO Phobic
Speedisks; SIM GC/MS Analyses"
Analytes
acetochlor
alachlor
atrazine
benzo[a]pyrene
chlordane, cis
chlordane, trans
di(2-ethylhexyl)adipate
di(2-ethylhexyl)phthalate
dimethipin
endrin
ethoprop
HCCPD
HCH, a
HCH, y (lindane)
heptachlor
heptachlor epoxide
hexachlorobenzene
methoxychlor
metolachlor
molinate
nonachlor, trans
oxyfluorfen
pentachlorophenol
permethrin, cis
permethrin, trans
profenofos
simazine
tebuconazole
tribufos
vinclozolin
Fortified Cone.
0.025jig/Lb
n=4
Mean %
Recovery
99.0
111
106
89.6
100
100
102
NDe
86.0
105
104
85.8
101
102
96.7
103
94.7
104
104
110
99.5
107
99.5
97.0
95.8
109
105
125
95.0
89.2
RSD
1.7
2.3
5.0
2.4
1.3
0.60
1.1
9.9
3.6
4.1
5.1
2.0
1.8
3.2
2.0
2.1
2.9
1.5
13
1.0
1.4
1.4
5.0
2.5
1.7
0.71
2.8
5.2
6.7
Fortified Cone.
0.10 fig/Lc
n=4
Mean %
Recovery
98.7
100
98.6
93.3
98.0
96.5
94.9
ND
105
105
101
86.6
96.8
96.3
90.6
99.3
88.0
101
101
95.7
97.3
107
93.6
95.6
95.5
105
99.7
114
96.9
82.7
Mean %
Recovery
1.9
1.1
6.0
2.9
2.4
2.5
5.1
6.9
1.5
2.7
3.5
2.0
3.3
3.4
1.9
2.2
4.0
2.3
2.6
2.6
5.7
2.4
5.4
5.1
3.6
5.1
4.1
4.3
6.3
Fortified Cone.
0.25 jig/Ld
n=4
Mean %
Recovery
98.8
100
99.3
91.8
99.2
97.5
96.2
ND
98.8
104
98.0
87.4
96.2
97.0
89.9
101
91.2
101
101
96.1
97.4
105
92.8
93.1
96.0
105
100
112
98.7
87.1
RSD
0.67
1.0
1.2
2.3
1.6
1.6
2.8
1.5
0.76
1.0
1.3
2.0
2.1
1.5
1.9
1.8
2.1
1.3
1.3
1.6
2.2
1.6
2.4
2.1
1.5
0.74
2.3
1.2
6.6
525.3-139
-------
Table 19. Precision and Accuracy Data Obtained for Selected Method Analytes Fortified in
Reagent Water at Three Concentrations and Extracted Using J.T. Baker HiO Phobic
Speedisks; SIM GC/MS Analyses"
Analytes
PCB congeners (by IUPAC#)
2-chlorobiphenyl (1)
4-chlorobiphenyl (3)
2,4'-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
2,2',3,5'-tetrachlorobiphenyl(44)
2,2',5,5'-tetrachlorobiphenyl(52)
2,3 ',4',5-tetrachloroobiphenyl (70)
2,3,3 ',4',6-pentachlorobiphenyl (1 10)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Surrogate Analytes
1 , 3 -dimethyl-2 -nitrobenzene
benzo [a] pyrene-^i 2
triphenyl phosphate
Fortified Cone.
0.025jig/Lb
n=4
Mean %
Recovery
96.4
97.3
95.0
97.2
94.8
98.4
96.5
97.6
98.7
97.9
101
96.8
95.9
92.8
96.2
89.0
100
99.0
RSD
1.6
1.7
1.8
2.0
1.2
2.2
2.2
1.8
1.4
1.5
1.1
1.3
1.0
1.5
2.5
2.2
2.6
1.7
Fortified Cone.
0.10 fig/Lc
n=4
Mean %
Recovery
94.5
93.4
93.2
94.6
92.9
94.3
93.6
95.7
95.0
95.4
91.9
94.7
94.2
87.9
96.4
92.0
101
98.7
Mean %
Recovery
2.8
2.5
2.9
2.7
2.3
2.3
2.4
2.4
2.3
2.5
2.3
2.4
2.4
2.1
1.2
1.8
2.0
1.9
Fortified Cone.
0.25 jig/Ld
n=4
Mean %
Recovery
95.3
93.2
92.4
93.7
94.8
95.5
95.2
96.8
96.1
96.3
94.6
95.2
94.5
87.1
95.4
91.6
100
98.8
RSD
2.9
1.1
1.8
1.5
1.3
1.7
1.5
3.6
1.4
1.7
2.8
1.7
1.9
2.6
2.4
2.1
2.9
0.67
a. Data obtained on the instrumentation described in Sect. 13.1.1.2.
b. Exceptions to the stated concentration are as follows: Surrogate concentrations are 1.0 ug/L, pentachlorophenol
is 0.10 ug/L, c-permethrin is 0.014 ug/L, and t-permethrin is 0.036 ug/L.
c. Exceptions to the stated concentration are as follows: Surrogate concentrations are 1.0 ug/L, pentachlorophenol
is 0.40 ug/L, c-permethrin is 0.058 ug/L, and t-permethrin is 0.14 ug/L.
d. Exceptions to the stated concentration are as follows: Surrogate concentrations are 1.0 ug/L, pentachlorophenol
is 1.0 ug/L, c-permethrin is 0.14 ug/L, and t-permethrin is 0.36 ug/L.
e. ND = Not determined. Matrix spike recovery could not be determined due to the low fortification concentration
relative to the background concentration.
525.3-140
-------
Table 20a. Precision and Accuracy Data Obtained for Selected Method Analytes Fortified
into Finished Drinking Waters from Ground and Surface Water Sources, and Extracted
Using J.T. Baker H2O Phobic Speedisks; N=4 for Each Matrix; SIM GC/MS Analyses'1
Analytes
acetochlor
alachlor
atrazine
benzo[a]pyrene
chlordane, cis
chlordane, trans
di(2-ethylhexyl)adipate
di(2-ethylhexyl)phthalate
dimethipin
endrin
ethoprop
HCCPD
HCH, a
HCH, y (lindane)
heptachlor
heptachlor epoxide
hexachlorobenzene
methoxychlor
metolachlor
molinate
nonachlor, trans
oxyfluorfen
pentachlorophenol
permethrin, cis
permethrin, trans
profenofos
simazine
tebuconazole
tribufos
Fortified
Cone. (jig/L)
NAd
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
NA
NA
NA
0.10
0.40
0.058
0.14
0.10
0.10
0.50
0.10
Ground Water
Mean %
Recoveryd
90.4
112
84.8
91.0
90.4
67.0
NDe
69.6
95.3
91.0
82.4
90.9
88.2
90.6
93.8
87.3
98.9
100
90.2
87.1
86.3
96.8
84.9
109
95.9
RSD
6.6
5.3
5.1
4.5
4.1
7.9
9.7
4.2
4.4
8.9
4.2
4.8
5.1
4.3
5.6
5.6
6.2
5.5
4.5
4.9
5.5
7.1
5.6
9.0
Surface Water0
Mean %
Recovery °
104
125
83.1
98.4
98.5
81.0
NDe
70.8
108
109
163
96.9
91.9
101
104
90.8
121
141
89.0
108
105
119
97.2
138
117
RSD
1.4
0.94
6.1
1.8
1.8
8.2
6.7
2.9
1.8
4.2
1.7
0.73
1.3
1.5
1.9
1.8
1.3
1.8
4.3
3.5
2.1
2.7
2.5
3.2
525.3-141
-------
Table 20a. Precision and Accuracy Data Obtained for Selected Method Analytes Fortified
into Finished Drinking Waters from Ground and Surface Water Sources, and Extracted
Using J.T. Baker H2O Phobic Speedisks; N=4 for Each Matrix; SIM GC/MS Analyses'1
Analytes
vinclozolin
PCB congeners (by IUPAC#)
2-chlorobiphenyl (1)
4-chlorobiphenyl (3)
2,4'-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
2,2',3,5'-tetrachlorobiphenyl(44)
2,2',5,5'-tetrachlorobiphenyl(52)
2,3 ',4',5-tetrachloroobiphenyl (70)
2,3,3',4',6-pentachlorobiphenyl (1 10)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Surrogate Analytes
1 , 3 -dimethyl-2 -nitrobenzene
benzo [a] pyrene-^i 2
triphenyl phosphate
Fortified
Cone. (jig/L)
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
1.0
5.0
1.0
Ground Water
Mean %
Recoveryd
90.3
85.8
85.3
87.0
90.2
87.7
87.7
87.3
84.1
84.8
83.6
77.4
81.6
76.9
67.9
102
119
99.1
RSD
4.9
4.7
4.8
4.7
2.2
4.3
3.9
4.0
3.6
3.4
2.4
2.6
2.7
2.9
4.4
1.0
2.0
3.4
Surface Water0
Mean %
Recovery °
104
88.1
89.1
89.9
90.4
91.0
89.9
90.8
88.2
88.7
88.1
79.9
84.7
77.8
67.9
109
112
110
RSD
1.5
1.4
1.7
1.8
1.3
1.8
2.0
1.8
2.1
2.2
3.1
4.3
3.6
4.7
8.7
0.60
5.0
2.6
a. Data obtained on the instrumentation described in Sect. 13.1.1.2.
b. Tap water from a ground water source with high mineral content. Tap water hardness was 325 mg/L as calcium
carbonate, TOC was 0.73 mg/L.
c. Tap water from a surface water source. Tap water hardness was 137 mg/L as calcium carbonate, TOC was 2.52
mg/L.
d. NA = Not analyzed. Matrix sample was not fortified with this analyte.
e. ND = Not determined. Recovery could not be determined because high LRB concentrations were observed
relative to the fortified concentration.
525.3-142
-------
Table 20b. Precision and Accuracy Data Obtained for Selected Method Analytes Fortified
into Finished Drinking Waters from Ground and Surface Water Sources, and Extracted
Using J.T. Baker H2O Phobic Speedisks; N=4 for Each Matrix; SIM GC/MS Analyses'1
Analytes
acetochlor
alachlor
atrazine
benzo[a]pyrene
chlordane, cis
chlordane, trans
di(2-ethylhexyl)adipate
di(2-ethylhexyl)phthalate
dimethipin
endrin
ethoprop
HCCPD
HCH, a
HCH, y (lindane)
heptachlor
heptachlor epoxide
hexachlorobenzene
methoxychlor
metolachlor
molinate
nonachlor, trans
oxyfluorfen
pentachlorophenol
permethrin, cis
permethrin, trans
profenofos
simazine
tebuconazole
tribufos
Fortified
Cone. (jig/L)
NAd
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
NA
NA
NA
0.50
2.0
0.15
0.35
0.10
0.50
2.5
0.50
Ground Water
Mean %
Recoveryd
90.8
90.5
92.3
92.5
91.9
73.5
NDe
72.3
96.1
91.7
89.1
92.4
91.3
92.8
94.6
89.3
99.7
93.0
92.3
81.1
82.2
93.3
82.8
96.5
91.4
RSD
1.1
0.85
2.8
1.1
0.98
1.1
6.0
1.3
1.6
2.2
1.4
1.0
1.2
1.4
1.7
1.3
0.83
1.3
1.4
0.97
2.1
1.0
1.3
1.0
Surface Water0
Mean %
Recovery °
95.8
92.1
79.6
94.6
94.1
76.3
NDe
69.7
102
97.7
114
92.6
90.7
97.7
97.6
90.0
104
107
89.7
86.1
84.9
99.4
85.0
103
98.0
RSD
3.3
3.7
6.6
2.8
2.6
9.9
7.8
3.0
2.9
1.6
3.6
3.0
2.3
2.7
3.2
2.6
2.7
2.8
4.4
3.8
3.0
3.3
2.7
2.5
525.3-143
-------
Table 20b. Precision and Accuracy Data Obtained for Selected Method Analytes Fortified
into Finished Drinking Waters from Ground and Surface Water Sources, and Extracted
Using J.T. Baker H2O Phobic Speedisks; N=4 for Each Matrix; SIM GC/MS Analyses'1
Analytes
vinclozolin
PCB congeners (by IUPAC#)
2-chlorobiphenyl (1)
4-chlorobiphenyl (3)
2,4'-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
2,2',3,5'-tetrachlorobiphenyl(44)
2,2',5,5'-tetrachlorobiphenyl(52)
2,3 ',4',5-tetrachloroobiphenyl (70)
2,3,3',4',6-pentachlorobiphenyl (1 10)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Surrogate Analytes
1 , 3 -dimethyl-2 -nitrobenzene
benzo [a] pyrene-^i 2
triphenyl phosphate
Fortified
Cone. (jig/L)
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
1.0
5.0
1.0
Ground Water
Mean %
Recoveryd
91.3
89.7
87.7
89.7
90.9
90.6
90.5
90.2
90.6
88.5
86.1
80.6
83.5
79.1
71.0
103
117
102
RSD
1.0
1.8
1.9
1.9
1.5
1.1
1.1
1.4
1.7
2.2
1.2
0.86
0.84
0.82
0.72
0.65
2.6
1.8
Surface Water0
Mean %
Recovery °
94.7
87.8
87.5
89.4
90.2
90.8
90.0
90.1
88.8
86.6
86.0
78.9
81.5
76.1
64.9
108
112
112
RSD
2.7
4.7
3.7
3.3
3.0
2.9
3.1
2.9
3.2
3.7
3.2
3.1
3.0
3.2
2.8
0.93
5.1
0.84
a. Data obtained on the instrumentation described in Sect. 13.1.1.2.
b. Tap water from a ground water source with high mineral content. Tap water hardness was 325 mg/L as calcium
carbonate, TOC was 0.73 mg/L.
c. Tap water from a surface water source. Tap water hardness was 137 mg/L as calcium carbonate, TOC was
2.52 mg/L.
d. NA = Not analyzed. Matrix sample was not fortified with this analyte.
e. ND = Not determined. Recovery could not be determined because high LRB concentrations were observed
relative to the fortified concentration.
525.3-144
-------
Table 21. Precision and Accuracy Data for Toxaphene Extracted from Fortified Reagent
Water; Sample Extracts Analyzed in SIM GC/MS Mode
Sorbent
Oasis-HLBa
J.T. Baker H2O Phobic
cartridge3
J.T. Baker H2O Phobic
Speediskb
Empore SDB-XC3
UCT 525 Universal
Cartridge3
Fortified Cone.
l.Ofig/L
n=4
Mean %
Recovery
82.9
100
114
107
NAC
RSD
5.0
3.63
1.0
5.3
Fortified Cone.
lOfig/L
n=4
Mean %
Recovery
101
104
103
111
111
RSD
3.3
3.8
3.4
2.1
1.8
Fortified Cone.
25u£/L
n=4
Mean %
Recovery
89.5
98.5
98.5
101
NA
RSD
8.8
1.7
2.8
0.15
a. Data obtained on the instrumentation described in Sect. 13.1.1.1.
b. Data obtained on the instrumentation described in Sect. 13.1.1.2.
c. NA = Not analyzed. Data using the UCT 525 Universal cartridge was obtained at a single concentration of
10 ug/L.
Table 22. Precision and Accuracy Data for Toxaphene Extracted from Fortified Drinking
Water Samples; Sample Extracts Analyzed in SIM GC/MS Mode
Sorbent
Oasis-HLBc
J.T. Baker H2O Phobic
cartridge0
J.T. Baker H2O Phobic
Speediskd
Empore SDB-XCC
Ground Water a
Fortified Cone.
10 jig/L, n=4
Mean % Recovery
95.4
102
120
106
RSD
3.7
5.6
2.4
4.6
Surface Water b
Fortified Cone.
10 jig/L, n=4
Mean % Recovery
94.2
103
124
104
RSD
5.9
3.5
1.9
0.46
a. Tap water from a ground water source with high mineral content. Hardness was determined to be 323-360 mg/L
as calcium carbonate.
b. Tap water from surface water sources. Fortified water samples extracted on Oasis-HLB cartridges had a TOC of
2.05 mg/L. Fortified water samples extracted on other sorbents had a TOC of 3.12 mg/L.
c. Data obtained on the instrumentation described in Sect. 13.1.1.1.
d. Data obtained on the instrumentation described in Sect. 13.1.1.2.
525.3-145
-------
Table 23. DLs and LCMRLs Calculated from Replicate Analyses of Fortified Reagent Water
Samples Extracted on Oasis HLB Cartridges, and LCMRLs Calculated from Replicate
Analyses of Fortified Reagent Water Samples Extracted on J.T. Baker HiO Phobic Speedisks,
All Samples Analyzed in SIM Mode, All concentrations in ug/L
Analytes
acetochlor
alachlor
atrazine
benzo[a]pyrene
chlordane, cis
chlordane, trans
di(2-ethylhexyl)adipate
di(2-ethylhexyl)phthalate
dimethipin
endrin
ethoprop
HCCPD
HCH, a
HCH, y (lindane)
heptachlor
heptachlor epoxide
hexachlorobenzene
methoxychlor
metolachlor
molinate
nonachlor, trans
oxyfluorfen
pentachlorophenol
permethrin, cis
permethrin, trans
profenofos
simazine
tebuconazole
Oasis HLBa
DLC
0.0047
0.0045
0.0062
0.0069
0.0016
0.0028
NDd
ND
0.0093
0.0081
0.0082
0.0055
0.0068
0.0040
0.0034
0.0026
0.0092
0.0025
0.0035
0.0057
0.0029
0.0038
0.047
0.0041
0.0080
0.0081
0.010
0.042
Fortified cone, of
DL replicates
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.100
0.006
0.014
0.010
0.025
0.12
LCMRL
0.011
0.016
0.023
0.036
0.0073
0.0097
0.38
0.43
0.022
0.014
0.036
0.014
0.021
0.031
0.010
0.017
0.014
0.021
0.019
0.010
0.0061
0.035
0.068
0.012
0.020
0.029
0.048
0.20
Baker Speedisk"
LCMRL
0.0091
0.013
0.015
0.0060
0.0039
0.0020
0.020
ND
0.065
0.011
0.0084
0.0026
0.0040
0.0071
0.0024
0.0031
0.0065
0.0011
0.004
0.029
0.0066
0.031
0.0086
0.0015
0.0023
0.012
0.018
0.037
525.3-146
-------
Table 23. DLs and LCMRLs Calculated from Replicate Analyses of Fortified Reagent Water
Samples Extracted on Oasis HLB Cartridges, and LCMRLs Calculated from Replicate
Analyses of Fortified Reagent Water Samples Extracted on J.T. Baker HiO Phobic Speedisks,
All Samples Analyzed in SIM Mode, All concentrations in ug/L
Analytes
toxaphene
tribufos
vinclozolin
PCB congeners (by IUPAC#)
2-chlorobiphenyl (1)
4-chlorobiphenyl (3)
2,4'-dichlorobiphenyl (8)
2,2',5-trichlorobiphenyl (18)
2,4,4'-trichlorobiphenyl (28)
2,2',3,5'-tetrachlorobiphenyl(44)
2,2',5,5'-tetrachlorobiphenyl(52)
2,3 ',4',5-tetrachloroobiphenyl (70)
2,3,3',4',6-pentachlorobiphenyl (1 10)
2,3',4,4',5-pentachlorobiphenyl (118)
2,2',3,4,4',5'-hexachlorobiphenyl(138)
2,2',3,4',5',6-hexachlorobiphenyl(149)
2,2',4,4',5,5'- hexachlorobiphenyl (153)
2,2',3,4,4',5,5'-heptachlorobiphenyl(180)
Oasis HLBa
DLC
0.32
0.0033
0.0064
0.0024
0.0049
0.0045
0.0038
0.0056
0.0063
0.0027
0.013
0.0030
0.0077
0.0081
0.0063
0.0092
0.0029
Fortified cone, of
DL replicates
1.0
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.025
0.010
0.010
0.010
0.010
0.010
0.010
LCMRL
1.4
0.023
0.0098
0.0080
0.0073
0.023
0.013
0.014
0.025
0.0078
0.036
0.0092
0.013
0.016
0.012
0.013
0.015
Baker Speedisk"
LCMRL
NFe
0.0063
0.095
0.0063
0.0056
0.0022
0.0012
0.0084
0.0020
0.0012
0.0022
0.0035
0.0026
0.015
0.0021
0.0038
0.0026
a. Data obtained on the instrumentation described in Sect. 13.1.1.1.
b. Data obtained on the instrumentation described in Sect. 13.1.1.2.
c. DL calculated from eight replicates.
d. ND = Not determined. DLs and LCMRLs were not determined when a high background concentration or an
interference was present that prevented accurate quantitation at the fortified concentration.
e. NF = Not fortified.
525.3-147
-------
Table 24. Initial Demonstration of Capability (IDC) and Quality Control (QC) Requirements (Summary)
Method
Reference
Sect. 9.2.1
& 9.3.1
Sect. 9.2.2
Sect. 9.2.3
Sect. 9.2.4
Sect. 9.2.5
&9.3.9
Requirement
Initial Demonstration of
Low Background
Initial Demonstration of
Precision (IDP)
Initial Demonstration of
Accuracy (IDA)
Minimum Reporting
Limit (MRL)
Confirmation
Calibration Confirmation,
Quality Control Sample
(QCS)
Specification and Frequency
Analyze LRB prior to any other IDC steps. When a new
lot of SPE media is obtained, verify that background is
at acceptable limits.
Analyze 4-7 replicate LFBs fortified near the midrange
calibration concentration.
Calculate average recovery for replicates used in IDP.
Fortify, extract and analyze 7 replicate LFBs at the
proposed MRL concentration. Calculate the mean,
standard deviation and HRPIR for each analyte. Confirm
that the upper and lower limits for the Prediction
Interval of Result (Upper PIR, and Lower PIR, Sect.
9.2.4.2) meet the recovery criteria.
Analyze a standard from a second source (QCS) to
verify the initial calibration curve.
Acceptance Criteria
Demonstrate that the method analytes are < 1/3 the
MRL, and that possible interferences from
extraction media do not prevent the identification
and/or quantification of any analytes, SURs or ISs.
Note: This includes the absence of interferences at
both the QIs and confirmation ions at the RTs of
interest.
%RSDmustbe<20%
Mean recovery ± 30% of the true value for all
analytes except dimethipin, HCCPD and HCB
which must be within 60-130% of the true value
Upper PIR < 150%
Lower PIR > 50%
± 30% of the expected value.
NOTE: Table 24 is intended as an abbreviated summary of QC requirements provided as a convenience to the method user. Because the information has been
abbreviated to fit the table format, there may be issues that need additional clarification, or areas where important additional information from the method text
is needed. In all cases, the full text of the QC in Sect. 9 supersedes any missing or conflicting information in this table.
525.3-148
-------
Table 25. Ongoing Quality Control (QC) Requirements (Summary)
Method
Reference
Requirement
Specification and Frequency
Acceptance Criteria
Sample Holding Time
14 days for most analytes with appropriate preservation
and storage as described in Sects. 8.1-8.3. See Sect 8.4
for exceptions.
Sample results are valid only if samples are
extracted within sample hold time.
Extract Holding Time
28 days stored at -5 °C and protected from light
Sample results are valid only if extracts are
analyzed within extract hold time.
Sect. 9.3.1
Laboratory Reagent Blank
(LRB)
One LRB with each extraction batch of up to 20 Field
Samples.
Demonstrate that the method analyte concentration
is < V3 the MRL, and confirm that possible
interferences do not prevent quantification. If the
background concentration exceeds V3the MRL,
results for the extraction batch are invalid.
Sect. 9.3.3
Laboratory Fortified
Blank (LFB)
One LFB is required for each extraction batch of up to
20 Field Samples. Rotate the fortified concentrations
between low, medium, and high amounts.
Results of LFB analyses at medium and high
fortifications must be ± 30% of the true value for all
analytes except dimethipin, HCCPD and HCB
which may be 60-130% of the true value. Results
of the low-level LFB must be ± 50% of the true
value.
Sect. 9.3.5
Internal Standard (IS)
Compare IS area to the mean IS area from the analysis
of each C AL in the initial calibration and the area in the
most recent CCC.
Peak area counts for all ISs in all injections must be
within ± 50% of their mean peak area calculated
during the initial calibration. Peak areas of ISs 1-3
must also be ± 30% from the most recent CCC. If
the ISs do not meet these criteria, target analyte
results are invalid. Consult Sect. 9.3.5 for further
information.
Sect. 9.3.6
Surrogate (SUR)
Standards
The SUR standards are added to all calibration standards
and samples, including QC samples prior to extraction.
Calculate SUR recoveries.
SUR recovery must be ± 30% of the true value. If
any SUR fails this criterion, report all results for
sample as suspect/SUR recovery.
Sect. 9.3.7
Laboratory Fortified
Sample Matrix (LFSM)
Analyze one LFSM per extraction batch (of up to 20
Field Samples) fortified with the method analytes at a
concentration close to but greater than the native
concentration. Calculate LFSM recoveries.
See Sect. 9.3.7.3 for instructions on the
interpretation of LFSM results.
525.3-149
-------
Table 25. Ongoing Quality Control (QC) Requirements (Summary) (Continued)
Sect. 9.3.8
Laboratory Fortified
Sample Matrix Duplicate
(LFSMD) or Field
Duplicates (FD)
Extract and analyze at least one FD or LFSMD with
each extraction batch of up to 20 Field Samples. An
LFSMD may be substituted for a FD when the
frequency of detects for analytes of interest are low.
Calculate RPDs.
Method analyte RPDs for the LFSMD or FD should
be < 30% at mid and high levels of fortification and
< 50% at concentrations within 2 times the MRL.
Failure to meet this criterion may indicate a matrix
effect.
Sect. 9.3.9
Quality Control Sample
(QCS)
Analyze a QCS during the IDC, and each time new CAL
solutions or PDSs are prepared. A QCS must be
analyzed at least quarterly.
Results must be ±30% of the expected value.
Sect. 10.2
Initial Calibration
Use the IS calibration technique to generate a linear or
quadratic calibration curve for each analyte. A
minimum of six standards should be used for a
calibration range of two orders of magnitude. Suggested
concentrations can be found in Sect. 7.2.4. Check the
calibration curve against the acceptance criteria in Sect.
10.2.6.
When each calibration standard is calculated as an
unknown using the calibration curve, the result
should be ± 30% of the true value for all except the
lowest standard, which should be ± 50% of the true
value. If this criterion is not met, reanalyze CALs,
select a different method of calibration or
recalibrate over a shorter range.
Sects. 10.1
and 10.2.1
MS Tune Check
Analyze DFTPP to verify the MS tune after instrument
maintenance and each time the instrument is mass
calibrated. The MS tune must also be verified prior to
analyzing CAL stds and establishing calibration curves
for method analytes.
Acceptance criteria are given in Table 2.
Sect. 10.3
Continuing Calibration
Check (CCC)
Verify initial calibration by analyzing a calibration
standard at the beginning of each analysis batch prior to
analyzing samples, after every 10 Field Samples, and
after the last sample of each analysis batch. The first
CCC daily must be at or below the MRL. Subsequent
CCCs alternate between medium and high
concentrations.
Low CCC - at or below the MRL concentration
Mid CCC - near midpoint in the initial calibration curve
High CCC - near the highest calibration standard.
Low: ±50% of true value
Mid: ±30% of true value
High: ±30% of true value
Note: Table 25 is intended as an abbreviated summary of QC requirements provided as a convenience to the method user. Because the information has been
abbreviated to fit the table format, there may be issues that need additional clarification, or areas where important additional information from the method text is
needed. In all cases, the full text of Sects. 8-10 in the method supersedes any missing or conflicting information in this table.
525.3-150
-------
Figure la. Example chromatogram of a calibration standard (concentration of 5 ng/uL injected for most analytes). Peak
identification numbers correspond to those in Table 1.
105^
100E
95 E
90-E
85E:
80 E
75^
8 65|
| 60EE
1 55EE
o> E
J5 E
Q> ,1 »- —
ce 45—
35^
30EE
25E^
20E^
15E:
0-
2
1
|
i_ , -
V.
I
J -
3
4
( ., A
A A
5
I «|
6
. ™ , ^-, . __ ».j 1 . ^j --~..-^ -~~..~-., _„-__. '-.^-_ ...,^, 1 •— —,-.,_. "V-__J X^__r-_^ ~_,._~V --— -^ -- «.-,_^- -,J -, v. .__-_~-
1 1 1 ! ' 1 1 i > 1 < I ! 1 ' I ! 1 i 1 I 1 1 1 ' ] < 1 i 1 1 1 1 1 1 1 ' 1 I I 1 1 1 1 1 i i 1 i ] I
6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0
Time (min)
525.3-151
-------
Figure Ib. Example chromatogram of a calibration standard (concentration of 5 ng/uL injected for most analytes). Peak
identification numbers correspond to those in Table 1.
41-43
CU
ce
100-
95^
90-
85i
75^
65^
55^
5CH
45^
40^
35 ^E
30^
25E
20-E
15^
10 E
5^;
O~"
7,
l!
I
J
, L.—p,,- T- - T -^ j
16-
15
12-14
9-11
8
/
I J
I
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L j
18
25
23,24
22
21
20
19
A
I AJ
ii i i i i i iii
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UJ
27
26
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l f — r — r —
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— T — T — "i" — r — r — r~
31
30
U
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33
32
38-40
36,;
34 35
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u
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41
46
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r
J1
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52
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1 i '
12.5 13.0 13.5 14.0
14.5 15.0
Time (min)
15.5 16.0 16.5 17.0
525.3-152
-------
Figure Ic. Example chromatogram of a calibration standard (concentration of 5 ng/uL injected for most analytes). Peak
identification numbers correspond to those in Table 1.
ioo^
90^
85^
80^
75^
70-E
60^
-S 45-
o:
40-
35-
30
25-
20
15-
10-
62,63
67,68 72, 73
56,57
82
80,81
79
87,88
85
86
83
84
94-96
93
92
89
90
91
103,104
100,101
99
98
97
102
105
17.5 18.0 18.5
19.0 19.5 20.0
Time (min)
20.5 21.0 21.5 22.0
525.3-153
-------
Figure Id. Example chromatogram of a calibration standard (concentration of 5 ng/uL injected for most analytes). Peak
identification numbers correspond to those in Table 1.
J
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cc
10O—
95^:
90^
85-
70-
65^E
55^
45-E
35^
25^
20
112,113
107,108
109,
110'
106
111
115,116
114
119
123
23
24
122
ptTp-t-rprrr-prtrp-rT-, n T| rr Ty
26 27
128
124,125
126,
127
28
Time (min)
29
129,
130 131
30
31
32
525.3-154
-------
Figure 2. Example extracted ion current profiles of toxaphene at m/z 125, 305, and 159.
RT: 20.71 -25.66
40000-
_a
Peak 1
RT:21.72
Peak 3
RT: 22.66
Peak 4
RT: 24.52
21.0 21.5 22.0 22.5 23.0 23.5
Time (min)
24.0
24.5
25.0
Base Peak
m/z=
158.50-159.50
Base Peak
m/z=
304.50-305.50
Base Peak
m/z=
124.50-125.50
25.5
525.3-155
-------
Figure 3a. Results of Aqueous Holding Time Study (Sect. 13.4)
140%
120%
•II ill ill ill ill ill ill ill ill ill ill
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f */////////j ///*//
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525.3-156
-------
Figure 3b. Results of Aqueous Holding Time Study (Sect. 13.4)
140%
120%
525.3-157
-------
Figure 3c. Results of Aqueous Holding Time Study (Sect. 13.4)
o>
o
o
CD
CO
CD
E
140%
120%
100%
hi
i
mi
I
mini
////*
*fy /
/
<+>
V
r
-------
Figure 4a. Results of Extract Holding Time Study (Sect. 13.5)
CO
CD
140%
120%
100%
80%
60%
40%
20%
0%
•t=0 days(n=4)
•t=7 days(n=4)
•t=14days(n=4)
Dt=21 days(n=4)
•t=28 days(n=4)
525.3-159
-------
Figure 4b. Results of Extract Holding Time Study (Sect. 13.5)
140%
120%
•t=0 days(n=4)
•t=7 days(n=4)
•t=14days(n=4)
Dt=21 days(n=4)
•t=28 days(n=4)
525.3-160
-------
Figure 4c. Results of Extract Holding Time Study (Sect. 13.5)
140%
120%
100%
80%
60%
40%
20%
i
o>
o
o
CD
to
CD
E
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