ASTM D5175-91(1996)e1

Standard Test Method for Organohalide Pesticides and Polychlorinated Biphenyls in Water by Microextraction and Gas Chromatography

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:  Chemical Abstract Service Analyte Registry Number A Alachlor 5972-60-8 Aldrin 309-00-2 Chlordane 57-74-9 Dieldrin 60-57-1 Endrin 72-20-8 Heptachlor 76-44-8 Heptachlor Epoxide 1024-57-3 Hexachlorobenzene 118-74-1 Lindane 58-89-9 Methoxychlor 72-43-5 Toxaphene 8001-35-2 Aroclor B 1016 12674-11-2 Aroclor B 1221 11104-28-2 Aroclor B 1232 11141-16-5 Aroclor B 1242 53469-21-9 Aroclor B 1248 12672-29-6 Aroclor B 1254 11097-69-1 Aroclor B 1260 11096-82-5 A Numbering system of CAS Registry Services, P.O. Box 3343, Columbus, OH 43210-0334. B Aroclor is a registered trademark of Monsanto Co.
1.2 Detection limits for most test method analytes are less than 1 [mu]g/L. Actual detection limits are highly dependent on the characteristics of the sample matrix and the gas chromatography system. Table 1 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 1.1 or for other sample sources, the analyst must demonstrate the applicability of this test method by collecting precision and bias data on spiked samples (that is, 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, that is, 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 13.4).
1.7 When this test method is used to analyze unfamiliar samples for any or all of the analytes listed in 1.1, 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 problems, 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

• Status: Historical
• Publication Date: 31-Dec-1995
• Technical Committee: D19 - Water
• Drafting Committee: D19.06 - Methods for Analysis for Organic Substances in Water

Relations

• Replaced By: ASTM D5175-91(2003) - Standard Test Method for Organohalide Pesticides and Polychlorinated Biphenyls in Water by Microextraction and Gas Chromatography
• Effective Date: 10-Jan-2003

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.
e1
Designation: D 5175 – 91 (Reapproved 1996)
AMERICAN SOCIETY FOR TESTING AND MATERIALS
100 Barr Harbor Dr., West Conshohocken, PA 19428
Reprinted from the Annual Book of ASTM Standards. Copyright ASTM
Standard Test Method for
Organohalide Pesticides and Polychlorinated Biphenyls in
Water by Microextraction and Gas Chromatography
This standard is issued under the fixed designation D 5175; 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 (e) indicates an editorial change since the last revision or reapproval.
e NOTE—Footnotes were deleted editorially in December 1996.
1. Scope containing complex mixtures of polychlorinated biphenyls
(PCBs) and organochlorine pesticides.
1.1 This test method (1,2,3) is applicable to the determi-
1.4 For compounds other than those listed in 1.1 or for other
nation of the following analytes in finished drinking water,
sample sources, the analyst must demonstrate the applicability
drinking water during intermediate stages of treatment, and the
of this test method by collecting precision and bias data on
raw source water:
spiked samples (groundwater, tap water) (4) and provide
Chemical Abstract Service
A
qualitative confirmation of results by gas chromatography/
Analyte Registry Number
Alachlor 5972-60-8
mass spectrometry (GC/MS) (5) or by GC analysis using
Aldrin 309-00-2
dissimilar columns.
Chlordane 57-74-9
Dieldrin 60-57-1 1.5 This test method is restricted to use by or under the
Endrin 72-20-8
supervision of analysts experienced in the use of GC and in the
Heptachlor 76-44-8
interpretation of gas chromatograms. Each analyst must dem-
Heptachlor Epoxide 1024-57-3
Hexachlorobenzene 118-74-1 onstrate the ability to generate acceptable results using the
Lindane 58-89-9
procedure described in Section 13.
Methoxychlor 72-43-5
1.6 Analytes that are not separated chromatographically,
Toxaphene 8001-35-2
B
Aroclor 1016 12674-11-2 (analytes that have very similar retention times) cannot be
B
Aroclor 1221 11104-28-2
individually identified and measured in the same calibration
B
Aroclor 1232 11141-16-5
B mixture or water sample unless an alternative technique for
Aroclor 1242 53469-21-9
B
Aroclor 1248 12672-29-6 identification and quantitation exists (see section 13.4).
B
Aroclor 1254 11097-69-1
1.7 When this test method is used to analyze unfamiliar
B
Aroclor 1260 11096-82-5
samples for any or all of the analytes listed in 1.1, analyte
A
Numbering system of CAS Registry Services, P.O. Box 3343, Columbus, OH
identifications and concentrations should be confirmed by at
43210-0334.
B least one additional technique.
Aroclor is a registered trademark of Monsanto Co.
1.8 The values stated in SI units are to be regarded as the
1.2 Detection limits for most test method analytes are less
standard. The inch-pound units given in parentheses are for
than 1 μg/L. Actual detection limits are highly dependent on
information only.
the characteristics of the sample matrix and the gas chroma-
1.9 This standard does not purport to address all of the
tography system. Table 1 contains the applicable concentration
safety concerns, if any, associated with its use. It is the
range for the precision and bias statements. Only Aroclor 1016
responsibility of the user of this standard to establish appro-
and 1254 were included in the interlaboratory test used to
priate safety and health practices and determine the applica-
derive the precision and bias statements. Data for other PCB
bility of regulatory limitations prior to use. For specific hazard
products are likely to be similar.
statements, see Section 9.
1.3 Chlordane, toxaphene, and Aroclor products (polychlo-
rinated biphenyls) are multicomponent materials. Precision and
2. Referenced Documents
bias statements reflect recovery of these materials dosed into
water samples. The precision and bias statements may not
2.1 ASTM Standards:
apply to environmentally altered materials or to samples
D 1129 Terminology Relating to Water
D 1193 Specification for Reagent Water
D 3534 Test Method for Polychlorinated Biphenyls (PCBs)
This test method is under the jurisdiction of ASTM Committee D-19 on Water
in Water
and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water.
Current edition approved Sept. 15, 1991. Published February 1992.
2 3
The boldface numbers in parentheses refer to a list of references at the end of Annual Book of ASTM Standards, Vol 11.01.
this test method. Annual Book of ASTM Standards, Vol 11.02.
NOTICE:¬This¬standard¬has¬either¬been¬superseded¬and¬replaced¬by¬a¬new¬version¬or
discontinued.¬Contact¬ASTM¬International¬(www.astm.org)¬for¬the¬latest¬information.¬
D 5175
A
TABLE 1 Test Method Precision and Bias as Functions of Concentration
BCDE
Water Type
Compound Applicable Concentration Range, μg/L
Reagent water Ground water
Alachlor 0.50 to 37.50 S 5 0.077X + 0.09 S 5 0.075X + 0.05
o o
S 5 0.107X + 0.15 S 5 0.086X + 0.29
t t
X 5 1.004C − 0.08 X 5 1.059C + 0.03
Aldrin 0.04 to 1.42 S 5 0.030X + 0.02 S 5 0.115X + 0.00
o o
S 5 0.251X + 0.00 S 5 0.189X + 0.01
t t
X 5 1.066C + 0.00 X 5 0.945C − 0.00
Chlordane 0.51 to 50.90 S 5 0.083X + 0.06 S 5 0.062X + 0.09
o o
S 5 0.125X + 0.19 S 5 0.147X + 0.24
t t
X 5 1.037C + 0.06 X 5 0.941C + 0.09
Dieldrin 0.10 to 7.53 S 5 0.091X + 0.01 S 5 0.089X + 0.04
o o
S 5 0.199X + 0.02 S 5 0.221X + 0.04
t t
X 5 1.027C + 0.00 X 5 0.961C + 0.01
Endrin 0.10 to 7.50 S 5 0.116X + 0.01 S 5 0.045X + 0.15
o o
S 5 0.134X + 0.02 S 5 0.196X + 0.07
t t
X 5 0.958C + 0.01 X 5 0.958C + 0.05
Heptachlor 0.04 to 1.41 S 5 0.104X + 0.01 S 5 0.058X + 0.02
o o
S 5 0.206X + 0.02 S 5 0.153X + 0.02
t t
X 5 1.002C + 0.02 X 5 0.964C + 0.02
Heptachlor Epoxide 0.04 to 1.42 S 5 0.031X + 0.02 S 5 0.032X + 0.00
o o
S 5 0.127X + 0.02 S 5 0.103X + 0.02
t t
X 5 0.952C + 0.00 X 5 0.932C + 0.01
Hexachlorobenzene 0.01 to 0.37 S 5 0.104X + 0.00 S 5 0.148X + 0.00
o o
S 5 0.231X + 0.00 S 5 0.301X + 0.00
t t
X 5 1.028C − 0.00 X 5 0.901C − 0.00
Lindane 0.04 to 1.39 S 5 0.056X + 0.01 S 5 0.095X + 0.00
o o
S 5 0.141X + 0.00 S 5 0.134X − 0.00
t t
X 5 1.009C − 0.00 X 5 0.909C + 0.00
Methoxychlor 0.20 to 15.00 S 5 0.115X + 0.12 S 5 0.179X + 0.02
o o
S 5 0.122X + 0.21 S 5 0.210X + 0.08
t t
X 5 0.950C + 0.15 X 5 1.014C + 0.07
Toxaphene 5.63 to 70.40 S 5 0.132X − 0.32 S 5 0.067X + 0.28
o o
S 5 0.273X − 0.72 S 5 0.181X + 1.52
t t
X 5 1.087C + 0.24 X 5 0.903C + 0.50
PCB-1016 0.50 to 49.80 S 5 0.106X + 0.31 S 5 0.141X + 0.13
o o
S 5 0.144X + 0.46 S 5 0.218X + 0.06
t t
X 5 0.856C + 0.31 X 5 0.958C + 0.07
PCB-1254 0.50 to 50.40 S 5 0.122X + 0.12 S 5 0.126X + 0.17
o o
S 5 0.282X + 0.05 S 5 0.396X + 0.02
t t
X 5 0.872C − 0.01 X 5 0.938C − 0.02
A
Bias 5C−X.
B
X 5 Mean recovery.
C
C 5 True concentration value.
D
S 5 Overall standard deviation.
t
E
S 5 Single analyst standard deviation.
o
D 3856 Guide for Good Laboratory Practices in Laborato- E 355 Practice for Gas Chromatography Terms and Rela-
3 5
ries Engaged in Sampling and Analysis of Water tionships
D 4128 Practice for Identification of Organic Compounds in 2.2 EPA Standards:
Water by Combined Gas Chromatography and Electron
Method 505, Analysis of Organohalide Pesticides and Aro-
Impact Mass Spectrometry
clors in Water by Microextraction and Gas Chromatogra-
D 4210 Practice for Intralaboratory Quality Control Proce-
phy
dures and a Discussion on Reporting Low-Level Data
Annual Book of ASTM Standards, Vol 14.02.
Available from US EPA, Environmental Monitoring Systems Laboratory,
Cincinnati, OH 45268.
NOTICE:¬This¬standard¬has¬either¬been¬superseded¬and¬replaced¬by¬a¬new¬version¬or
discontinued.¬Contact¬ASTM¬International¬(www.astm.org)¬for¬the¬latest¬information.¬
D 5175
Method 680, Determination of Pesticides and PCBs in dard solutions are used to prepare secondary dilution standards.
Water and Soil/Sediment by Gas Chromatography/Mass 3.2.10 quality control sample (QCS), n—a sample contain-
Spectrometry ing analytes or a solution of analytes in a water-miscible
solvent used to fortify reagent water or environmental samples.
3. Terminology
The QCS must be independent of solutions used to prepare
3.1 Definitions—For definitions of terms used in this test
standards and should be obtained from a source external to the
method, refer to Terminology D 1129 and Practice E 355.
laboratory. The QCS is used to check laboratory performance
3.2 Definitions of Terms Specific to This Standard:
with externally prepared test materials.
3.2.1 field duplicates (FD 1 and FD 2), n—two separate
4. Summary of Test Method
samples collected at the same time and placed under identical
4.1 This is a microextraction method in which 35 mL of
circumstances and treated exactly the same throughout field
sample are extracted with 2 mL of hexane. Two μL of the
and laboratory procedures. Analyses of FD 1 and FD 2 give a
extract are injected into a gas chromatograph equipped with a
measure of the precision associated with sample collection,
linearized electron capture detector for separation and analysis.
preservation and storage, as well as with laboratory procedures.
Aqueous calibration standards are extracted and analyzed in an
3.2.2 field reagent blank (FRB), n—reagent water placed in
identical manner to compensate for possible extraction losses.
a sample container in the laboratory and treated as a sample in
4.2 The extraction and analysis time is 30 to 50 min per
all respects, including exposure to sampling site conditions,
sample depending upon the analytes and the analytical condi-
storage, preservation, and all analytical procedures. The re-
tions chosen.
agent water must be transferred to an empty, clean sample
4.3 This test method is based largely on EPA Method 505.
container in the field. The purpose of the FRB is to determine
if analytes or other interferences are present in the field
5. Significance and Use
environment.
5.1 The extensive and widespread use of organochlorine
3.2.3 instrument performance check solution (IPC), n—a
pesticides and PCBs has resulted in their presence in all parts
solution of analytes used to evaluate the performance of the
of the environment. These compounds are persistent and may
instrument system with respect to test method criteria.
have adverse effects on the environment. Thus, there is a need
3.2.4 laboratory duplicates (LD 1 and LD 2), n—two
to identify and quantitate these compounds in water samples.
sample aliquots taken in the analytical laboratory and analyzed
6. Interferences
separately with identical procedures. Analyses of LD 1 and LD
2 give a measure of the precision associated with laboratory 6.1 Interferences may be caused by contaminants in sol-
procedures but not with sample collection, preservation, or vents, reagents, glassware, and other sample processing appa-
storage procedures. ratus that lead to discrete artifacts or elevated baselines in gas
3.2.5 laboratory fortified blank (LFB), n—an aliquot of chromatograms. All reagents and apparatus must be routinely
reagent water to which known quantities of the analytes are demonstrated to be free from interferences under the conditions
added in the laboratory. The LFB is analyzed exactly like a
of the analysis by running laboratory reagent blanks as
sample, and its purpose is to determine whether the method- described in 12.2.
ology is in control, and whether the laboratory is capable of 6.1.1 Glassware must be scrupulously cleaned (2). Clean all
making accurate and precise measurements. glassware as soon as possible after use by thoroughly rinsing
3.2.6 laboratory fortified sample matrix (LFM), n—an ali- with the last solvent used in it. Follow by washing with hot tap
quot of an environmental sample to which known quantities of water and detergent and thoroughly rinsing with tap and
the analytes are added in the laboratory. The LFM is analyzed reagent water. Drain dry and heat in an oven or muffle furnace
as a sample, and its purpose is to determine whether the sample at 400°C for 1 h. Do not heat volumetric ware. Thermally
matrix contributes bias to the analytical results. The back- stable materials might not be eliminated by this treatment.
ground concentrations of the analytes in the sample matrix Thorough rinsing with acetone may be substituted for the
must be determined in a separate aliquot and the measured heating. After drying and cooling, seal and store glassware in
values in the LFM corrected for background concentrations. a clean environment to prevent any accumulation of dust or
3.2.7 laboratory reagent blank (LRB), n—an aliquot of other contaminants. Store inverted or capped with aluminum
reagent water that is treated as a sample including exposure to foil.
all glassware, equipment, solvents, and reagents used with 6.1.2 The use of high purity reagents and solvents helps to
other samples. The LRB is used to determine if method minimize interference problems. Purification of solvents by
analytes or other interferences are present in the laboratory distillation in all-glass systems may be required.
environment, the reagents, or the apparatus. 6.2 Phthalate esters, frequently found in plastics, paints, and
3.2.8 standard solution, secondary dilution, n—a solution other common laboratory items, produce a positive response on
of several analytes prepared in the laboratory from stock
an electron capture detector. Therefore, samples and solvents
standard solutions and diluted as needed to prepare calibration should come in contact only with those materials specified in
solutions and other needed analyte solutions. this test method.
3.2.9 standard solution, stock, n—a concentrated solution 6.3 Interfering contamination may occur when a sample
containing a single certified standard that is an analyte or a containing low concentrations of analytes is analyzed imme-
concentrated solution of a single analyte prepared in the diately following a sample containing relatively high concen-
laboratory with an assayed reference compound. Stock stan- trations of analytes. Between-sample rinsing of the sample
NOTICE:¬This¬standard¬has¬either¬been¬superseded¬and¬replaced¬by¬a¬new¬version¬or
discontinued.¬Contact¬ASTM¬International¬(www.astm.org)¬for¬the¬latest¬information.¬
D 5175
syringe and associated equipment with hexane can minimize temperature programming capability, splitless injector (0.5 min
sample cross contamination. After analysis of a sample con- splitless mode), capillary column, and linearized electron
taining high concentrations of analytes, one or more injections capture detecto
...