ASTM D5175-91(2024)

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

SIGNIFICANCE AND USE
5.1 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 (1-3)2 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:    
Analyte  
Chemical Abstract Service
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  
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. 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 (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 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 standard. The values given in parentheses are mathematical conversions to inch-pound units that are provided for information only and are not considered standard.  
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, health, and environmental practices and determine the applicability of regulatory limitations prior to use. For specific hazard statements, see Section 9.  
1.10 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for th...

General Information

• Status: Published
• Publication Date: 31-Mar-2024
• ICS: 13.060.50 - Examination of water for chemical substances
• Technical Committee: D19 - Water
• Drafting Committee: D19.06 - Methods for Analysis for Organic Substances in Water

Relations

• Replaces: ASTM D5175-91(2017)e1 - Standard Test Method for Organohalide Pesticides and Polychlorinated Biphenyls in Water by Microextraction and Gas Chromatography
• Effective Date: 01-Apr-2024
• Referred By: ASTM D4128-18 - Standard Guide for Identification and Quantitation of Organic Compounds in Water by Combined Gas Chromatography and Electron Impact Mass Spectrometry
• Effective Date: 01-Apr-2024
• Referred By: ASTM D5241-92(2024) - Standard Practice for Micro-Extraction of Water for Analysis of Volatile and Semi-Volatile Organic Compounds in Water
• Effective Date: 01-Apr-2024
• Referred By: ASTM D3694-96(2024) - Standard Practices for Preparation of Sample Containers and for Preservation of Organic Constituents
• Effective Date: 01-Apr-2024

Overview

ASTM D5175-91(2024): Standard Test Method for Organohalide Pesticides and Polychlorinated Biphenyls in Water by Microextraction and Gas Chromatography establishes procedures for the determination of specific organochlorine pesticides and PCBs (polychlorinated biphenyls) in various water matrices, including finished drinking water, treated water in process, and raw source water. The method utilizes microextraction techniques followed by gas chromatography (GC) analysis, ensuring reliable detection and quantitation of persistent, environmentally significant contaminants at low concentrations.

The standard is maintained by ASTM Committee D19 on Water and aligns with internationally recognized principles on standardization, following the requirements laid out by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

Key Topics

• Scope: The standard covers the quantitative analysis of multiple organohalide pesticides and PCBs, including alachlor, aldrin, chlordane, dieldrin, endrin, heptachlor, lindane, methoxychlor, toxaphene, and several Aroclor PCB mixtures. Chemical Abstract Service (CAS) registry numbers are specified for each analyte.
• Detection Limits: Typical detection limits are less than 1 μg/L, subject to sample matrix and instrumental performance.
• Sample Types: Applicable to finished drinking water, intermediate treatment waters, and raw source waters.
• Applicability: Analysts must confirm method suitability for compounds or matrices not specifically listed by demonstrating adequate precision and bias, with additional confirmation via GC/MS or alternate GC columns.
• Quality Assurance: Emphasizes laboratory control using reagent blanks, fortified blanks, fortified sample matrices, and quality control samples, ensuring accuracy and reliability of results.
• Analyst Competency: The method should only be applied by or under supervision of qualified personnel skilled in GC operation and chromatographic data interpretation.
• Limitations: Analytes not resolved chromatographically in a single mixture or water sample may require additional confirmation methods. The standard stresses the necessity of confirmatory analysis for unfamiliar sample matrices or analyte combinations.

Applications

This ASTM method is widely used in:

• Environmental Monitoring: Routine testing of water supplies for organohalide pesticides and PCBs, given their persistence and potential for environmental harm.
• Regulatory Compliance: Helping utilities and environmental agencies ensure drinking water and source water meet regulatory limits for pesticides and PCBs.
• Public Health & Safety: Identifying and quantifying trace levels of hazardous compounds to assess exposure risks to human populations and aquatic life.
• Water Treatment Evaluation: Assessing the effectiveness of treatment processes in removing or reducing levels of persistent organic pollutants.

Key benefits include:

• Sensitive Detection: Microextraction with GC offers low detection limits suitable for trace analysis.
• Versatile Matrix Compatibility: Applicable across various water types, including challenging environmental samples.
• Data Validation: Robust QC requirements promote reliable and valid data, supporting regulatory reporting and decision-making.

Related Standards

Implementing ASTM D5175-91(2024) may involve or reference several other important standards and methods:

• ASTM D1129 – Terminology Relating to Water
• ASTM D1193 – Specification for Reagent Water
• ASTM D3856 – Guide for Management Systems in Laboratories Engaged in Analysis of Water
• ASTM D4128 – Identification and Quantitation of Organic Compounds in Water by GC-MS
• EPA Method 505 – Analysis of Organohalide Pesticides and Aroclors in Water by Microextraction and GC
• EPA Method 680 – Determination of Pesticides and PCBs in Water and Soil/Sediment by GC/MS

These documents collectively enhance the framework for accurate, defensible analysis of organic contaminants in water, reinforcing laboratory best practices and data integrity.

---

Keywords: Organohalide pesticides, polychlorinated biphenyls, PCBs, water analysis, microextraction, gas chromatography, ASTM D5175, drinking water testing, environmental monitoring, regulatory compliance, trace contaminants.

Standards Content (Sample)

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D5175 − 91 (Reapproved 2024)
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 bias statements reflect recovery of these materials dosed into
water samples. The precision and bias statements may not
1.1 This test method (1-3) is applicable to the determina-
apply to environmentally altered materials or to samples
tion of the following analytes in finished drinking water,
containing complex mixtures of polychlorinated biphenyls
drinking water during intermediate stages of treatment, and the
(PCBs) and organochlorine pesticides.
raw source water:
Chemical Abstract Service
1.4 For compounds other than those listed in 1.1 or for other
Analyte
A
Registry Number
sample sources, the analyst must demonstrate the applicability
Alachlor 5972-60-8
of this test method by collecting precision and bias data on
Aldrin 309-00-2
Chlordane 57-74-9
spiked samples (groundwater, tap water) (4) and provide
Dieldrin 60-57-1
qualitative confirmation of results by gas chromatography/
Endrin 72-20-8
Heptachlor 76-44-8 mass spectrometry (GC/MS) (5) or by GC analysis using
Heptachlor Epoxide 1024-57-3
dissimilar columns.
Hexachlorobenzene 118-74-1
Lindane 58-89-9
1.5 This test method is restricted to use by or under the
Methoxychlor 72-43-5
supervision of analysts experienced in the use of GC and in the
Toxaphene 8001-35-2
B
Aroclor 1016 12674-11-2
interpretation of gas chromatograms. Each analyst must dem-
B
Aroclor 1221 11104-28-2
onstrate the ability to generate acceptable results using the
B
Aroclor 1232 11141-16-5
B
procedure described in Section 13.
Aroclor 1242 53469-21-9
B
Aroclor 1248 12672-29-6
B
Aroclor 1254 11097-69-1 1.6 Analytes that are not separated chromatographically,
B
Aroclor 1260 11096-82-5
(analytes that have very similar retention times) cannot be
individually identified and measured in the same calibration
A
Numbering system of CAS Registry Services, P.O. Box 3343, Columbus, OH
mixture or water sample unless an alternative technique for
43210-0334.
B
Aroclor is a registered trademark of Monsanto Co.
identification and quantitation exists (see 13.4).
1.2 Detection limits for most test method analytes are less
1.7 When this test method is used to analyze unfamiliar
than 1 μg/L. Actual detection limits are highly dependent on
samples for any or all of the analytes listed in 1.1, analyte
the characteristics of the sample matrix and the gas chroma-
identifications and concentrations should be confirmed by at
tography system. Table 1 contains the applicable concentration
least one additional technique.
range for the precision and bias statements. Only Aroclor 1016
1.8 The values stated in SI units are to be regarded as
and 1254 were included in the interlaboratory test used to
derive the precision and bias statements. Data for other PCB standard. The values given in parentheses are mathematical
conversions to inch-pound units that are provided for informa-
products are likely to be similar.
tion only and are not considered standard.
1.3 Chlordane, toxaphene, and Aroclor products (polychlo-
rinated biphenyls) are multicomponent materials. Precision and
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 appro-
This test method is under the jurisdiction of ASTM Committee D19 on Water
priate safety, health, and environmental practices and deter-
and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
mine the applicability of regulatory limitations prior to use.
Organic Substances in Water.
For specific hazard statements, see Section 9.
Current edition approved April 1, 2024. Published April 2024. Originally
ɛ1
approved in 1991. Last previous edition approved in 2017 as D5175 – 91 (2017) .
1.10 This international standard was developed in accor-
DOI: 10.1520/D5175-91R24.
2 dance with internationally recognized principles on standard-
The boldface numbers in parentheses refer to a list of references at the end of
this standard. ization established in the Decision on Principles for the
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5175 − 91 (2024)
A
TABLE 1 Test Method Precision and Bias as Functions of Concentration
B C D E
Water Type
Compound Applicable Concentration Range, μg/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
Development of International Standards, Guides and Recom- D1193 Specification for Reagent Water
mendations issued by the World Trade Organization Technical D3534 Test Method for Polychlorinated Biphenyls (PCBs)
Barriers to Trade (TBT) Committee. in Water (Withdrawn 2003)
D3856 Guide for Management Systems in Laboratories
2. Referenced Documents
Engaged in Analysis of Water (Withdrawn 2024)
2.1 ASTM Standards: D4128 Guide for Identification and Quantitation of Organic
Compounds in Water by Combined Gas Chromatography
D1129 Terminology Relating to Water
and Electron Impact Mass Spectrometry
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on The last approved version of this historical standard is referenced on
the ASTM website. www.astm.org.
D5175 − 91 (2024)
D4210 Practice for Intralaboratory Quality Control Proce- must be determined in a separate aliquot and the measured
dures and a Discussion on Reporting Low-Level Data values in the LFM corrected for background concentrations.
(Withdrawn 2002)
3.2.7 laboratory reagent blank (LRB), n—an aliquot of
E355 Practice for Gas Chromatography Terms and Relation-
reagent water that is treated as a sample including exposure to
ships
all glassware, equipment, solvents, and reagents used with
2.2 EPA Standards:
other samples. The LRB is used to determine if method
Method 505 Analysis of Organohalide Pesticides and Aro-
analytes or other interferences are present in the laboratory
clors in Water by Microextraction and Gas Chromatogra-
environment, the reagents, or the apparatus.
phy
3.2.8 standard solution, secondary dilution, n—a solution of
Method 680 Determination of Pesticides and PCBs in Water
several analytes prepared in the laboratory from stock standard
and Soil/Sediment by Gas Chromatography/Mass Spec-
solutions and diluted as needed to prepare calibration solutions
trometry
and other needed analyte solutions.
3. Terminology 3.2.9 standard solution, stock, n—a concentrated solution
containing a single certified standard that is an analyte or a
3.1 Definitions:
concentrated solution of a single analyte prepared in the
3.1.1 For definitions of terms used in this standard, refer to
laboratory with an assayed reference compound. Stock stan-
Terminology D1129 and Practice E355.
dard solutions are used to prepare secondary dilution standards.
3.2 Definitions of Terms Specific to This Standard:
3.2.10 quality control sample (QCS), n—a sample contain-
3.2.1 field duplicates (FD 1 and FD 2), n—two separate
ing analytes or a solution of analytes in a water-miscible
samples collected at the same time and placed under identical
solvent used to fortify reagent water or environmental samples.
circumstances and treated exactly the same throughout field
The QCS must be independent of solutions used to prepare
and laboratory procedures. Analyses of FD 1 and FD 2 give a
standards and should be obtained from a source external to the
measure of the precision associated with sample collection,
laboratory. The QCS is used to check laboratory performance
preservation and storage, as well as with laboratory procedures.
with externally prepared test materials.
3.2.2 field reagent blank (FRB), n—reagent water placed in
a sample container in the laboratory and treated as a sample in
4. Summary of Test Method
all respects, including exposure to sampling site conditions,
4.1 This is a microextraction method in which 35 mL of
storage, preservation, and all analytical procedures. The re-
sample are extracted with 2 mL of hexane. Two μL of the
agent water must be transferred to an empty, clean sample
extract are injected into a gas chromatograph equipped with a
container in the field. The purpose of the FRB is to determine
linearized electron capture detector for separation and analysis.
if analytes or other interferences are present in the field
Aqueous calibration standards are extracted and analyzed in an
environment.
identical manner to compensate for possible extraction losses.
3.2.3 instrument performance check solution (IPC), n—a
4.2 The extraction and analysis time is 30 min to 50 min per
solution of analytes used to evaluate the performance of the
sample depending upon the analytes and the analytical condi-
instrument system with respect to test method criteria.
tions chosen.
3.2.4 laboratory duplicates (LD 1 and LD 2), n—two
4.3 This test method is based largely on EPA Method 505.
sample aliquots taken in the analytical laboratory and analyzed
separately with identical procedures. Analyses of LD 1 and LD
5. Significance and Use
2 give a measure of the precision associated with laboratory
procedures but not with sample collection, preservation, or
5.1 The extensive and widespread use of organochlorine
storage procedures.
pesticides and PCBs has resulted in their presence in all parts
3.2.5 laboratory fortified blank (LFB), n—an aliquot of of the environment. These compounds are persistent and may
have adverse effects on the environment. Thus, there is a need
reagent water to which known quantities of the analytes are
added in the laboratory. The LFB is analyzed exactly like a to identify and quantitate these compounds in water samples.
sample, and its purpose is to determine whether the method-
ology is in control, and whether the laboratory is capable of 6. Interferences
making accurate and precise measurements.
6.1 Interferences may be caused by contaminants in
3.2.6 laboratory fortified sample matrix (LFM), n—an ali-
solvents, reagents, glassware, and other sample processing
quot of an environmental sample to which known quantities of apparatus that lead to discrete artifacts or elevated baselines in
the analytes are added in the laboratory. The LFM is analyzed
gas chromatograms. All reagents and apparatus must be rou-
as a sample, and its purpose is to determine whether the sample tinely demonstrated to be free from interferences under the
matrix contributes bias to the analytical results. The back-
conditions of the analysis by running laboratory reagent blanks
ground concentrations of the analytes in the sample matrix
as described in 12.2.
6.1.1 Glassware must be scrupulously cleaned (2). Clean all
glassware as soon as possible after use by thoroughly rinsing
Available from United States Environmental Protection Agency (EPA), William
with the last solvent used in it. Follow by washing with hot tap
Jefferson Clinton Bldg., 1200 Pennsylvania Ave., NW, Washington, DC 20460,
http://www.epa.gov. water and detergent and thoroughly rinsing with tap and
D5175 − 91 (2024)
reagent water. Drain dry and heat in an oven or muffle furnace made from the same vial. This type of outlying observation
at 400 °C for 1 h. Do not heat volumetric ware. Thermally normally is recognized. If encountered, additional analyses will
stable materials might not be eliminated by this treatment. be necessary.
Thorough rinsing with acetone may be substituted for the
7. Apparatus
heating. After drying and cooling, seal and store glassware in
a clean environment to prevent any accumulation of dust or 7.1 Sample Containers, 40 mL screw cap vials each
other contaminants. Store inverted or capped with aluminum
equipped with a size 24 cap with a flat, disc-like PTFE facing
foil. backed with a polyethylene film/foam extrusion. Prior to use,
6.1.2 The use of high purity reagents and solvents helps to wash vials and septa with detergent and rinse with tap and
reagent waters. Allow the vials and septa to air dry at room
minimize interference problems. Purification of solvents by
distillation in all-glass systems may be required. temperature. Place the vials in a 400 °C over for 1 h. Remove
and allow to cool in an area known to be free of organics.
6.2 Phthalate esters, frequently found in plastics, paints, and
7.2 Vials, auto sampler with septa and caps. Vials should be
other common laboratory items, produce a positive response on
compatible with automatic sample injector and should have an
an electron capture detector. Therefore, samples and solvents
internal volume of not greater than 2 mL.
should come in contact only with those materials specified in
this test method.
7.3 Automatic Sample Injector, for gas chromatograph, must
not require more than 0.5 mL of solution per injection
6.3 Interfering contamination may occur when a sample
(including rinsing and flushing).
containing low concentrations of analytes is analyzed imme-
diately following a sample containing relatively high concen- 7.4 Micro syringe, 10 μL and 100 μL.
trations of analytes. Between-sample rinsing of the sample
7.5 Micro syringe, 25 μL with a 50 mm by 0.15 mm (2 in.
syringe and associated equipment with hexane can minimize
by 0.006 in.) needle.
sample cross contamination. After analysis of a sample con-
7.6 Standard Solution Storage Containers, 15 mL bottles
taining high concentrations of analytes, one or more injections
with PTFE-lined screw caps.
of hexane should be made to ensure that accurate values are
obtained for the next sample.
7.7 Gas Chromatograph, analytical system equipped with
temperature programming capability, splitless injector (0.5 min
6.4 Matrix interferences may be caused by contaminants
splitless mode), capillary column, and linearized electron
that are coextracted from the sample. Also, note that all the
capture detector. A computer data system is recommended for
analytes listed in the scope are not resolved from each other on
measuring peak areas. Table 2 lists retention times observed
any one column; one analyte of interest may be an interferent
using the columns and conditions described below.
for another analyte of interest. The extent of matrix interfer-
7.7.1 Three gas chromatographic columns are recom-
ences will vary considerably from source to source depending
mended. Column 1 (see 7.7.2) should be used as the primary
upon the water sampled. Cleanup of sample extracts may be
analytical column unless routinely occurring analytes are not
necessary. Positive identifications should be confirmed (see
adequately resolved. Validation data presented in this test
13.4).
method were obtained using this column. Columns 2 and 3 are
6.5 It is important that samples and working standards be
contained in the same solvent. The solvent for working
TABLE 2 Retention Times for Method Analytes
standards must be the same as the final solvent used in sample
A
Retention Time, min
Analyte Primary
preparation. If this is not the case, chromatographic compara-
Confirm 1 Confirm 2
bility of standards to sample may be affected.
Hexachlorobenzene 11.9 13.4 15.6
Lindane 12.3 18.4 18.7
6.6 Caution must be taken in the determination of endrin
Alachlor 15.1 19.7 21.1
since it has been reported that the splitless injector may cause
Heptachlor 15.9 17.5 20.0
Aldrin 17.6 18.4 21.4
endrin degradation (6). The analyst should be alerted to this
Heptachlor Epoxide 19.0 24.6 24.6
possible interference resulting in an erratic response for endrin.
Dieldrin 22.1 45.1 27.8
Endrin 24.2 33.3 29.2
6.7 Variable amounts of pesticides and PCBs from aqueous
Methoxychlor 30.0 58.5 36.4
B
solutions adhere to glass surfaces. It is recommended that
Primary
Aroclor 1016 13.6, 14.8, 15.2, 16.2, 17.7
sample transfers and glass surface contacts be minimized.
Aroclor 1221 7.7, 9.0, 15.9, 19.1, 24.7
Aroclor 1232 11.2, 14.7, 13.6, 15.2, 17.7
6.8 Aldrin and methoxychlor are rapidly oxidized by chlo-
Aroclor 1242 11.2, 13.6, 14.7, 15.2, 17.7, 19.8
rine. Dechlorination with sodium thiosulfate at time of collec-
Aroclor 1248 14.8, 16.2, 17.1, 17.7, 19.8, 22.0
tion will retard further oxidation of these compounds.
Aroclor 1254 19.1, 21.9, 23.4, 24.9, 26.7
Aroclor 1260 23.4, 24.9, 26.7, 28.2, 29.9, 32.6
6.9 An interfering, erratic peak has been observed within the
Chlordane 15.1, 15.9, 20.1, 20.9, 21.3
Toxaphene 21.7, 22.5, 26.7, 27.2
retention window of heptachlor during many analyses of
A
reagent, tap, and groundwater. It appears to be related to Columns and analytical conditions are described in 7.7.2, 7.7.3, and 7.7.4.
B
Column and conditions described in 7.7.2. More than one peak listed does not
dibutyl phthalate; however, the specific source has not yet been
implicate the total number of peaks characteristic of the multicomponent analyte.
determined. The observed magnitude and character of this peak
Listed peaks indicate only the ones chosen for quantification.
randomly vary in numerical value from successive injections
D5175 − 91 (2024)
recommended for use as confirmatory columns when GC/MS
confirmation is not available. Alternative columns may be used
in accordance with the provisions described in 12.3.
7.7.2 Column 1 (Primary Column)—A 0.32 mm inside di-
ameter by 30 m long fused silica capillary with chemically
bonded methyl polysiloxane phase. Helium carrier gas flow is
about 25 cm ⁄s linear velocity, measured at 180° with 9 psi
column head pressure. The oven temperature is programmed
from 180 °C to 260 °C at 4 °C ⁄min and held at 260 °C until all
expected compounds have eluted. Injector temperature is
200 °C. Detector temperature is 290 °C. Sample chromato-
grams for selected pesticides are presented in Fig. 1 and Fig. 2.
Chromatograms of the PCBs, toxaphene, and technical chlor-
dane are presented in Figs. 3-11.
7.7.3 Column 2 (Alternative Column)—A 0.32 mm inside
diameter by 30 m long fused silica capillary with a 1:1 mixed
phase of dimethyl silicone and polyethylene glycol. Helium
carrier gas flow is about 25 cm ⁄s linear velocity and oven
temperature is programmed from 100 °C to 210 °C at 8 °C ⁄min
and held at 210 °C until all expected compounds have eluted.
Then the post temperature is programmed to 240 °C at
NOTE 1—Interlaboratory precision and bias data are not available for
8 °C ⁄min for 5 min. those compounds listed with an asterisk. They are shown for informational
purposes only.
7.7.4 Column 3 (Alternative Column)—A 0.32 mm inside
FIG. 2 Extract of Reagent Water Spiked at 20 μg/L with Atrazine,
diameter by 25 m long fused silica capillary with chemically
60 μg/L with Simazine, 0.45 μg/L with Cis-nonachlor, and 0.35
bonded 50:50 methyl-phenyl silicone. Helium carrier gas flow
μg/L with Hexachlorocyclopentadiene, Heptachlor, Alpha
is about 40 cm/s linear velocity, and the oven temperature is
Chlordane, Gamma Chlordane, and Trans-nonachlor
programmed from 100 °C to 260 °C at 4 °C ⁄min and held at
260 °C until all expected compounds have eluted.
8. Reagents and Materials
8.1 Purity of Reagents—Reagent grade chemicals shall be
used. Unless otherwise indicated, it is intended that all reagents
shall conform to the specifications of the Committee on
FIG. 3 Hexane Spiked at 11.4 μg/L with Aroclor 1016
Analytical Reagents of the American Chemical Society.
Other grades may be used, provided it is first ascertained that
the reagent is of sufficient purity to permit its use without
decreasing the accuracy of the test method.
NOTE 1—Interlaboratory precision and bias data are not available for
those compounds listed with an asterisk. They are shown for informational
purposes only. 6
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
FIG. 1 Hexane Spiked at 7.71 μg/L with Heptachlor and Lindane;
Standard-Grade Reference Materials, American Chemical Society, Washington,
9.14 μg/L with Heptachlor Epoxide; 11.4 μg/L with Aldrin and
DC. For suggestions on the testing of reagents not listed by the American Chemical
Hexachlorobenzene; 23 μg/L with Butachlor, Chlorpyrifos,
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
Chlorpyrifosmethyl, Diclobenil, Dieldrin, Endrin, Metolochlor, and U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
Propachlor; and 44.9 μg/L with Methoxychlor copeial Convention, Inc. (USPC), Rockville, MD.
D5175 − 91 (2024)
FIG. 7 Hexane Spiked at 57.1 μg/L with Aroclor 1248
FIG. 4 Hexane Spiked at 171.4 μg/L with Aroclor 1221
FIG. 8 Hexane Spiked at 42.9 μg/L with Aroclor 1254
FIG. 5 Hexane Spiked at 57.1 μg/L with Aroclor 1232
FIG. 9 Hexane Spiked at 34.3 μg/L with Aroclor 1260
FIG. 6 Hexane Spiked at 57.1 μg/L with Aroclor 1242
D5175 − 91 (2024)
the material in methanol and dilute to volume in a 10 mL
volumetric flask. Larger volumes can be used at the conve-
nience of the analyst. When compound purity is assayed to be
96 % or greater, the weight can be used without correction to
calculate the concentration of the stock standard. Commer-
cially prepared stock standards can be used at any concentra-
tion if they are certified by the manufacturer or by an
independent source.
8.8.2 Transfer the stock standard solutions into PTFE-sealed
screw-cap bottles. Store at 4 °C and protect from light. Stock
standard solutions should be checked frequently for signs of
degradation or evaporation, especially prior to preparing cali-
bration standards from them.
8.8.3 Stock standard solutions must be replaced after six
months, or sooner, if comparison with check standards indi-
cates a problem.
FIG. 10 Hexane Spiked at 28.6 μg/L with Chlordane 8.9 Standard Solutions, Secondary Dilution—Use stock
standard solutions to prepare secondary dilution standard
solutions that contain the analytes in methanol. The secondary
dilution standards should be prepared at concentrations that can
be easily diluted to prepare aqueous calibration standards in
11.2.1 that will bracket the working concentration range. Store
the secondary dilution standard solutions with minimal head-
space and check frequently for signs of deterioration or
evaporation, especially just before preparing calibration stan-
dards. The storage time described for stock standard solutions
in 8.8.3 also applies to secondary dilution standard solutions.
8.10 Instrument Performance Check (IPC) Solution—
Prepared by combining microlitre aliquots of appropriate
secondary dilution standard solutions in a hexane solvent.
Concentrations of the analytes should be approximately equal
to those shown in Figs. 1 and 11. Not all analyte
...