ASTM D5175-91(2003)
(Test Method)Standard Test Method for Organohalide Pesticides and Polychlorinated Biphenyls in Water by Microextraction and Gas Chromatography
Standard Test Method for Organohalide Pesticides and Polychlorinated Biphenyls in Water by Microextraction and Gas Chromatography
SIGNIFICANCE AND USE
The extensive and widespread use of organochlorine pesticides and PCBs has resulted in their presence in all parts of the environment. These compounds are persistent and may have adverse effects on the environment. Thus, there is a need to identify and quantitate these compounds in water samples.
SCOPE
1.1 This test method (1,2,3) is applicable to the determination of the following analytes in finished drinking water, drinking water during intermediate stages of treatment, and the raw source water: AnalyteChemical Abstract Service Registry Number Alachlor5972-60-8Aldrin309-00-2Chlordane57-74-9Dieldrin60-57-1Endrin72-20-8Heptachlor76-44-8Heptachlor Epoxide1024-57-3Hexachlorobenzene118-74-1Lindane58-89-9Methoxychlor72-43-5Toxaphene8001-35-2Aroclor 101612674-11-2Aroclor 122111104-28-2Aroclor 123211141-16-5Aroclor 124253469-21-9Aroclor 124812672-29-6Aroclor 125411097-69-1Aroclor 126011096-82-5
Numbering system of CAS Registry Services, P.O. Box 3343, Columbus, OH 43210-0334.
Aroclor is a registered trademark of Monsanto Co.
1.2 Detection limits for most test method analytes are less than 1 μg/L. Actual detection limits are highly dependent on the characteristics of the sample matrix and the gas chromatography system. contains the applicable concentration range for the precision and bias statements. Only Aroclor 1016 and 1254 were included in the interlaboratory test used to derive the precision and bias statements. Data for other PCB products are likely to be similar.
1.3 Chlordane, toxaphene, and Aroclor products (polychlorinated biphenyls) are multicomponent materials. Precision and bias statements reflect recovery of these materials dosed into water samples. The precision and bias statements may not apply to environmentally altered materials or to samples containing complex mixtures of polychlorinated biphenyls (PCBs) and organochlorine pesticides.
1.4 For compounds other than those listed in or for other sample sources, the analyst must demonstrate the applicability of this test method by collecting precision and bias data on spiked samples (groundwater, tap water) (4)and provide qualitative confirmation of results by gas chromatography/mass spectrometry (GC/MS) (5) or by GC analysis using dissimilar columns.
1.5 This test method is restricted to use by or under the supervision of analysts experienced in the use of GC and in the interpretation of gas chromatograms. Each analyst must demonstrate the ability to generate acceptable results using the procedure described in Section 13.
1.6 Analytes that are not separated chromatographically, (analytes that have very similar retention times) cannot be individually identified and measured in the same calibration mixture or water sample unless an alternative technique for identification and quantitation exists (see section 13.4).
1.7 When this test method is used to analyze unfamiliar samples for any or all of the analytes listed in , analyte identifications and concentrations should be confirmed by at least one additional technique.
1.8 The values stated in SI units are to be regarded as the standard. The inch-pound units given in parentheses are for information only.
1.9 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific hazard statements, see Section 9.
General Information
Relations
Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D5175 – 91 (Reapproved 2003)
Standard Test Method for
Organohalide Pesticides and Polychlorinated Biphenyls in
Water by Microextraction and Gas Chromatography
This standard is issued under the fixed designation D5175; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope apply to environmentally altered materials or to samples
containing complex mixtures of polychlorinated biphenyls
1.1 This test method (1,2,3) is applicable to the determi-
(PCBs) and organochlorine pesticides.
nation of the following analytes in finished drinking water,
1.4 Forcompoundsotherthanthoselistedin1.1orforother
drinking water during intermediate stages of treatment, and the
sample sources, the analyst must demonstrate the applicability
raw source water:
of this test method by collecting precision and bias data on
Chemical Abstract Service
A
spiked samples (groundwater, tap water) (4) and provide
Analyte Registry Number
Alachlor 5972-60-8
qualitative confirmation of results by gas chromatography/
Aldrin 309-00-2
mass spectrometry (GC/MS) (5) or by GC analysis using
Chlordane 57-74-9
dissimilar columns.
Dieldrin 60-57-1
Endrin 72-20-8
1.5 This test method is restricted to use by or under the
Heptachlor 76-44-8
supervision of analysts experienced in the use of GC and in the
Heptachlor Epoxide 1024-57-3
Hexachlorobenzene 118-74-1 interpretation of gas chromatograms. Each analyst must dem-
Lindane 58-89-9
onstrate the ability to generate acceptable results using the
Methoxychlor 72-43-5
procedure described in Section 13.
Toxaphene 8001-35-2
B
1.6 Analytes that are not separated chromatographically,
Aroclor 1016 12674-11-2
B
Aroclor 1221 11104-28-2
(analytes that have very similar retention times) cannot be
B
Aroclor 1232 11141-16-5
individually identified and measured in the same calibration
B
Aroclor 1242 53469-21-9
B
Aroclor 1248 12672-29-6 mixture or water sample unless an alternative technique for
B
Aroclor 1254 11097-69-1
identification and quantitation exists (see section 13.4).
B
Aroclor 1260 11096-82-5
1.7 When this test method is used to analyze unfamiliar
A
Numbering system of CAS Registry Services, P.O. Box 3343, Columbus, OH
samples for any or all of the analytes listed in 1.1, analyte
43210-0334.
B identifications and concentrations should be confirmed by at
Aroclor is a registered trademark of Monsanto Co.
least one additional technique.
1.2 Detection limits for most test method analytes are less
1.8 The values stated in SI units are to be regarded as the
than 1 µg/L. Actual detection limits are highly dependent on
standard. The inch-pound units given in parentheses are for
the characteristics of the sample matrix and the gas chroma-
information only.
tography system. Table 1 contains the applicable concentration
1.9 This standard does not purport to address all of the
range for the precision and bias statements. OnlyAroclor 1016
safety concerns, if any, associated with its use. It is the
and 1254 were included in the interlaboratory test used to
responsibility of the user of this standard to establish appro-
derive the precision and bias statements. Data for other PCB
priate safety and health practices and determine the applica-
products are likely to be similar.
bility of regulatory limitations prior to use. For specific hazard
1.3 Chlordane, toxaphene, and Aroclor products (polychlo-
statements, see Section 9.
rinatedbiphenyls)aremulticomponentmaterials.Precisionand
bias statements reflect recovery of these materials dosed into
2. Referenced Documents
water samples. The precision and bias statements may not
2.1 ASTM Standards:
D1129 Terminology Relating to Water
D1193 Specification for Reagent Water
This test method is under the jurisdiction of ASTM Committee D19 on Water
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor
Organic Substances in Water.
Current edition approved Jan. 10, 2003. Published January 2003. Originally
´1 3
approved in 1991. Last previous edition approved in 1996 as D5175 – 91 (1996) . For referenced ASTM standards, visit the ASTM website, www.astm.org, or
DOI: 10.1520/D5175-91R03. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
The boldface numbers in parentheses refer to a list of references at the end of Standards volume information, refer to the standard’s Document Summary page on
this test method. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D5175 – 91 (2003)
A
TABLE 1 Test Method Precision and Bias as Functions of Concentration
BCDE
Water Type
Compound Applicable Concentration Range,µ g/L
Reagent water Ground water
Alachlor 0.50 to 37.50 S = 0.077X + 0.09 S = 0.075X + 0.05
o o
S = 0.107X + 0.15 S = 0.086X + 0.29
t t
X = 1.004C − 0.08 X = 1.059C + 0.03
Aldrin 0.04 to 1.42 S = 0.030X + 0.02 S =0.115X + 0.00
o o
S = 0.251X + 0.00 S = 0.189X + 0.01
t t
X = 1.066C + 0.00 X = 0.945C − 0.00
Chlordane 0.51 to 50.90 S = 0.083X + 0.06 S = 0.062X + 0.09
o o
S = 0.125X + 0.19 S = 0.147X + 0.24
t t
X = 1.037C + 0.06 X = 0.941C + 0.09
Dieldrin 0.10 to 7.53 S = 0.091X + 0.01 S = 0.089X + 0.04
o o
S = 0.199X + 0.02 S = 0.221X + 0.04
t t
X = 1.027C + 0.00 X = 0.961C + 0.01
Endrin 0.10 to 7.50 S =0.116X + 0.01 S = 0.045X + 0.15
o o
S = 0.134X + 0.02 S = 0.196X + 0.07
t t
X = 0.958C + 0.01 X = 0.958C + 0.05
Heptachlor 0.04 to 1.41 S = 0.104X + 0.01 S = 0.058X + 0.02
o o
S = 0.206X + 0.02 S = 0.153X + 0.02
t t
X = 1.002C + 0.02 X = 0.964C + 0.02
Heptachlor Epoxide 0.04 to 1.42 S = 0.031X + 0.02 S = 0.032X + 0.00
o o
S = 0.127X + 0.02 S = 0.103X + 0.02
t t
X = 0.952C + 0.00 X = 0.932C + 0.01
Hexachlorobenzene 0.01 to 0.37 S = 0.104X + 0.00 S = 0.148X + 0.00
o o
S = 0.231X + 0.00 S = 0.301X + 0.00
t t
X = 1.028C − 0.00 X = 0.901C − 0.00
Lindane 0.04 to 1.39 S = 0.056X + 0.01 S = 0.095X + 0.00
o o
S = 0.141X + 0.00 S = 0.134X − 0.00
t t
X = 1.009C − 0.00 X = 0.909C + 0.00
Methoxychlor 0.20 to 15.00 S =0.115X + 0.12 S = 0.179X + 0.02
o o
S = 0.122X + 0.21 S = 0.210X + 0.08
t t
X = 0.950C + 0.15 X = 1.014C + 0.07
Toxaphene 5.63 to 70.40 S = 0.132X − 0.32 S = 0.067X + 0.28
o o
S = 0.273X − 0.72 S = 0.181X + 1.52
t t
X = 1.087C + 0.24 X = 0.903C + 0.50
PCB-1016 0.50 to 49.80 S = 0.106X + 0.31 S = 0.141X + 0.13
o o
S = 0.144X + 0.46 S = 0.218X + 0.06
t t
X = 0.856C + 0.31 X = 0.958C + 0.07
PCB-1254 0.50 to 50.40 S = 0.122X + 0.12 S = 0.126X + 0.17
o o
S = 0.282X + 0.05 S = 0.396X + 0.02
t t
X = 0.872C − 0.01 X = 0.938C − 0.02
A
Bias =C−X.
B
X = Mean recovery.
C
C = True concentration value.
D
S = Overall standard deviation.
t
E
S = Single analyst standard deviation.
o
D3534 Test Method for Polychlorinated Biphenyls (PCBs) D4128 Guide for Identification and Quantitation of Organic
in Water Compounds in Water by Combined Gas Chromatography
D3856 Guide for Good Laboratory Practices in Laborato- and Electron Impact Mass Spectrometry
ries Engaged in Sampling and Analysis of Water D4210 Practice for Intralaboratory Quality Control Proce-
dures and a Discussion on Reporting Low-Level Data
E355 Practice for Gas Chromatography Terms and Rela-
4 tionships
Withdrawn. The last approved version of this historical standard is referenced
on www.astm.org. 2.2 EPA Standards:
D5175 – 91 (2003)
Method 505, Analysis of Organohalide Pesticides andAro- standard solutions and diluted as needed to prepare calibration
clors in Water by Microextraction and Gas Chromatogra- solutions and other needed analyte solutions.
phy 3.2.9 standard solution, stock,, n—a concentrated solution
Method 680, Determination of Pesticides and PCBs in containing a single certified standard that is an analyte or a
Water and Soil/Sediment by Gas Chromatography/Mass concentrated solution of a single analyte prepared in the
Spectrometry laboratory with an assayed reference compound. Stock stan-
dardsolutionsareusedtopreparesecondarydilutionstandards.
3. Terminology
3.2.10 quality control sample (QCS),, n—a sample contain-
3.1 Definitions—For definitions of terms used in this test
ing analytes or a solution of analytes in a water-miscible
method, refer to Terminology D1129 and Practice E355.
solventusedtofortifyreagentwaterorenvironmentalsamples.
3.2 Definitions of Terms Specific to This Standard:
The QCS must be independent of solutions used to prepare
3.2.1 field duplicates (FD 1 and FD 2),, n—two separate
standards and should be obtained from a source external to the
samples collected at the same time and placed under identical
laboratory. The QCS is used to check laboratory performance
circumstances and treated exactly the same throughout field
with externally prepared test materials.
and laboratory procedures. Analyses of FD 1 and FD 2 give a
4. Summary of Test Method
measure of the precision associated with sample collection,
preservationandstorage,aswellaswithlaboratoryprocedures.
4.1 This is a microextraction method in which 35 mL of
3.2.2 field reagent blank (FRB),, n—reagent water placed in
sample are extracted with 2 mL of hexane. Two µL of the
a sample container in the laboratory and treated as a sample in
extract are injected into a gas chromatograph equipped with a
all respects, including exposure to sampling site conditions,
linearizedelectroncapturedetectorforseparationandanalysis.
storage, preservation, and all analytical procedures. The re-
Aqueous calibration standards are extracted and analyzed in an
agent water must be transferred to an empty, clean sample
identical manner to compensate for possible extraction losses.
container in the field. The purpose of the FRB is to determine
4.2 The extraction and analysis time is 30 to 50 min per
if analytes or other interferences are present in the field
sample depending upon the analytes and the analytical condi-
environment.
tions chosen.
3.2.3 instrument performance check solution (IPC),, n—a
4.3 This test method is based largely on EPA Method 505.
solution of analytes used to evaluate the performance of the
5. Significance and Use
instrument system with respect to test method criteria.
3.2.4 laboratory duplicates (LD 1 and LD 2),, n—two
5.1 The extensive and widespread use of organochlorine
sample aliquots taken in the analytical laboratory and analyzed
pesticides and PCBs has resulted in their presence in all parts
separately with identical procedures.Analyses of LD 1 and LD of the environment. These compounds are persistent and may
2 give a measure of the precision associated with laboratory
have adverse effects on the environment. Thus, there is a need
procedures but not with sample collection, preservation, or to identify and quantitate these compounds in water samples.
storage procedures.
6. Interferences
3.2.5 laboratory fortified blank (LFB),, n—an aliquot of
reagent water to which known quantities of the analytes are 6.1 Interferences may be caused by contaminants in sol-
added in the laboratory. The LFB is analyzed exactly like a
vents, reagents, glassware, and other sample processing appa-
sample, and its purpose is to determine whether the method- ratus that lead to discrete artifacts or elevated baselines in gas
ology is in control, and whether the laboratory is capable of
chromatograms. All reagents and apparatus must be routinely
making accurate and precise measurements. demonstratedtobefreefrominterferencesundertheconditions
3.2.6 laboratory fortified sample matrix (LFM),, n—an
of the analysis by running laboratory reagent blanks as
aliquot of an environmental sample to which known quantities described in 12.2.
of the analytes are added in the laboratory. The LFM is
6.1.1 Glassware must be scrupulously cleaned (2). Clean all
analyzed as a sample, and its purpose is to determine whether glassware as soon as possible after use by thoroughly rinsing
the sample matrix contributes bias to the analytical results.The
with the last solvent used in it. Follow by washing with hot tap
backgroundconcentrationsoftheanalytesinthesamplematrix water and detergent and thoroughly rinsing with tap and
must be determined in a separate aliquot and the measured reagent water. Drain dry and heat in an oven or muffle furnace
values in the LFM corrected for background concentrations. at 400°C for 1 h. Do not heat volumetric ware. Thermally
3.2.7 laboratory reagent blank (LRB),, n—an aliquot of stable materials might not be eliminated by this treatment.
reagent water that is treated as a sample including exposure to Thorough rinsing with acetone may be substituted for the
all glassware, equipment, solvents, and reagents used with heating. After drying and cooling, seal and store glassware in
other samples. The LRB is used to determine if method a clean environment to prevent any accumulation of dust or
analytes or other interferences are present in the laboratory other contaminants. Store inverted or capped with aluminum
environment, the reagents, or the apparatus. foil.
3.2.8 standard solution, secondary dilution,, n—a solution 6.1.2 The use of high purity reagents and solvents helps to
of several analytes prepared in the laboratory from stock
minimize interference problems. Purification of solvents by
distillation in all-glass systems may be required.
6.2 Phthalate esters, frequently found in plastics, paints, and
Available from US EPA, Environmental Monitoring Systems Laboratory,
Cincinnati, OH 45268. othercommonlaboratoryitems,produceapositiveresponseon
D5175 – 91 (2003)
an electron capture detector. Therefore, samples and solvents 7.3 Automatic Sample Injector, for gas chromatograph,
should come in contact only with those materials specified in must not require more than 0.5 mL of solution per injection
this test method. (including rinsing and flushing).
7.4 Micro syringe, 10 and 100 µL.
6.3 Interfering contamination may occur when a sample
7.5 Micro syringe, 25 µL with a 50 by 0.15 mm (2 by
containing low concentrations of analytes is analyzed imme-
0.006-in.) needle.
diately following a sample containing relatively high concen-
7.6 Standard Solution Storage Containers, 15-mL bottles
trations of analytes. Between-sample rinsing of the sample
with PTFE-lined screw caps.
syringe and associated equipment with hexane can minimize
7.7 Gas Chromatograph, analytical system equipped with
sample cross contamination. After analysis of a sample con-
temperatureprogrammingcapability,splitlessinjector(0.5min
taining high concentrations of analytes, one or more injections
splitless mode), capilla
...
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